1 reaction intermediates in organic chemistry: the big picturecareerchem.com/cv/cjc2005b-s5.pdf ·...
TRANSCRIPT
1
Reaction Intermediates in Organic Chemistry: the "Big Picture"
John Andraos
Department of Chemistry, York University, Toronto, ON M3J 1P3
FAX: 416-736-5936
Supplementary Material
Table S5. Table summarizing reactions that lead to the suggestion, discovery, and identification of various reaction intermediates
Acylium ions (oxocarbonium ions)
C OR C OR++
Reviews:Olah, G.A.; Germain, A.; White, A.M. in Carbonium Ions (G.A. Olah; P.v.R. Schleyer, eds.) Wiley-Interscience: New York, 1976, Vol. 5, p. 2049- 2133
COOH C
O
H2SO4
+
HSO4- + H2O
Treffers, H.P.; Hammett, L.P. J. Am. Chem. Soc. 1937, 59, 1708Burton, H.; Praill, P.F.G. J. Chem. Soc. 1955, 729Chmiel, C.T.; Long, F.A. J. Am. Chem. Soc. 1956, 78, 3326Ladenheim, H.; Bender, M.L.. J. Am. Chem. Soc. 1960, 82, 1895Bender, M.L.; Feng, M.S. J. Am. Chem. Soc. 1960, 82, 6318Bender, M.L.; Ladenheim, H.; Chen, M.C. J. Am. Chem. Soc. 1961, 83, 123Yamase, Y. Bull. Chem. Soc. Jpn. 1961, 34, 484Cook, D. Can. J. Chem. 1961, 40, 445
2
N-Acylonium ions (acylammonium ions)
O
R1 N
R4
R2
R3
+
Reviews:Beckwith, A.L.J. in The Chemistry of Amides (Zabicky, J.; ed.) Wiley-Interscience: New York, 1970, Chapter 2, p. 77-81
Kröhnke, F.; Heffe, W. Chem. Ber. 1937, 70B, 1720Prey, A. Chem. Ber. 1942, 75, 537Adkins, H.; Thompson, Q.E. J. Am. Chem. Soc. 1949, 71, 2242Klages, F.; Zange, E. Ann. Chem. 1957, 607, 35Cook, D. Can. J. Chem. 1962, 40, 2362
Alleneoxide
O
R2
R1R3
R4
Reviews:Chan, T.H.; Ong, B.S. Tetrahedron 1980, 36, 2269
3
O
tBu
H
tBu
tBu
H
tBu
H
mCPBA
Camp, R.L.; Greene, F.D. J. Am. Chem. Soc. 1968, 90, 7349
O
O
OAcOH
CH3(CO)OOH
64%
+
27%
Crandall, J.K.; Paulson, D.R.; Bunnell, C.A. Tetrahedron Lett. 1968, 5063
O
O
OAc
O
OH
O
OAcHO O
O O
HOOAc
Crandall, J.K.; Machleder, W.H. J. Am. Chem. Soc. 1968, 90, 7292
Aromatic π-complexes
4
X
Reviews:Stock, L.M. Adv. Phys. Org. Chem. 1963, 1, 35Berliner, E. Prog. Phys. Org. Chem. 1964, 2, 253Baciocchi, E.; Illuminati, G. Prog. Phys. Org. Chem. 1967, 5, 1Olah, G.A. Acc. Chem. Res. 1971, 4, 240Lenoir, D. Angew. Chem. Int. Ed. 2003, 42, 854
(i) Charge transfer complexes
Reviews:Dewar, M.J.S. Electronic Theory of Organic Chemistry, Oxford University Press: New York, 1949Kosower, E.M. Prog. Phys. Org. Chem. 1965, 3, 81Blatchly, J.M. Educ. Chem. 1970, 7, 62Ruasse, F. Adv. Phys. Org. Chem. 1993, 28, 207
NH2
NH
NH2NH
H
NH2
HN
H
+
+ +
Dewar, M.J.S. Nature 1945, 156, 784 (first suggestion)Dewar, M.J.S. J. Chem. Soc. 1946, 406; 777
5
CH3 CH3
HAlCl4 H+ AlCl4-
Brown, H.C.; Brady, J.D. J. Am. Chem. Soc. 1952, 74, 3570
Al Br
Br
Br
AlBr3
Brown, H.C.; Wallace, W.J. J. Am. Chem. Soc. 1953, 75, 6265
+N N+
O
O
O -
- O
Addison, C.C. Rec. Trav. Chim. Pays-Bas 1956, 75, 626
OH
NO2O2N
NO2
Ar
Kross, R.D.; Fassel, V.A. J. Am. Chem. Soc. 1957, 79, 38
6
R
CHCl3
R2
R1
CHCl3
Reeves, L.W.; Schneider, W.G. Can. J. Chem. 1957, 35, 251(proton NMR signal of chloroform as function of concentration of aromatic or olefinic compound)
Brown, H.C.; Stock, L.M. J. Am. Chem. Soc. 1957, 79, 1421
CNNC
NC CN
R2
R1R1 = H, R2 = H
R1 = H, R2 = CH3
R1 = CH3, R2 = CH3
Merrifield, R.E.; Phillips, W.D. J. Am. Chem. Soc. 1958, 80, 2778Cairns, T.L.; Carboni, R.A.; Coffman, D.D.; Engelhardt, V.A.; Heckert, R.E.; Little, E.L.; McGeer, E.G.; McKusik, B.C.; Middleton, W.J.;Scribner, R.M.; Theobold, C.W.; Windberg, H.E. J. Am. Chem. Soc. 1958, 80, 2775
W
CO
OCCO
OC Me6
Me6
+ W(CO)6- 2 CO
W(CO)3- CO
Manuel, T.A.; Stone, F.G.A. Chem. Ind. 1959, 1349
7
R
HX X = Cl, Br
Brown, H.C.; Melchiore, J.J. J. Am. Chem. Soc. 1965, 87, 5269
O
NO2O2N
NO2
Ar
Schenk, G.H.; Vance, P.W.; Pietrandrea, J.; Mojzis, C. Anal. Chem. 1965, 37, 372
(ii) "Sandwich" complexes (metallocenes)
Reviews:Jutzi, P. Pure Appl Chem. 1989, 61, 1731Grebenik, P.; Grinter, R.; Perutz, R.N. Chem. Soc. Rev. 1988, 17, 453Jonas, K. Pure Appl. Chem. 1984, 56, 63Schloegel, K. Pure Appl. Chem. 1970, 23, 413Schloegel, K. Top. Stereochem. 1967, 1, 39
Hein, F. Chem. Ber. 1919, 52, 195
8
H ClH MgBr
Fe+2
H MgBr
3- 3 MgBrCl- FeCl2
2 FeCl3
EtBrMg
EtMgBr- EtH
_
_+
Kealy, T.J.; Pauson, P.L. Nature 1951, 168, 1039Wilkinson, G.; Rosenblum, M.; Whiting, M.C.; Woodward, R.B. J. Am. Chem. Soc. 1952, 74, 2125Woodward, R.B.; Rosenblum, M.; Whiting, M.C. J. Am. Chem. Soc. 1952, 74, 3458Eiland, P.F.; Pepinsky, R. J. Am. Chem. Soc. 1952, 74, 4971Wilkinson, G. J. Am. Chem. Soc. 1954, 76, 209
M = Co, Rh; X = Cl, Br
[MC6Me6]+n [AlX 4-]nMXn + n AlCl3 + 2 Me6C6
Fischer, E.O.; Lindner, H.H. J. Organometallic Chem. 1964, 1, 307
Aromatic σ-complexes (see Meisenheimer-Jackson complexes and Janovsky complexes for negatively charged complexes;Wheland intermediates for positively charged complexes)
9
E R4
R1
R6 R2
R5 R3
E R4
R1
R6 R2
R5 R3
E R4
R1
R6 R2
R5 R3
Reaction with electrophiles, E+
+
+ +
R1 Nu
R2
R3
R4
R5
R6
R1 Nu
R2
R3
R4
R5
R6
R1 Nu
R2
R3
R4
R5
R6_
_
_
Reaction with nucleophiles, Nu-
Reviews:Ross, S.D. Prog. Phys. Org. Chem. 1963, 1, 31Stock, L.M. Adv. Phys. Org. Chem. 1963, 1, 35Berliner, E. Prog. Phys. Org. Chem. 1964, 2, 253Baciocchi, E.; Illuminati, G. Prog. Phys. Org. Chem. 1967, 5, 1
Buncel, E.; Norris, A.R.; Russell, K.E. Quart. Rev. Chem. Soc. 1968, 22, 123Olah, G.A. Acc. Chem. Res. 1971, 4, 240
10
H H
+ HF + BF3 + BF4-
Kilpatrick, M.; Luborsky, F.E. J. Am. Chem. Soc. 1953, 75, 577Olah, G.A.; Kuhn, S.J.; Pavlath, A. Nature 1956, 178, 693Olah, G.A.; Kuhn, S.J.; Pavlath, A. J. Am. Chem. Soc. 1958, 80, 6535; 6541Doering, W.v.E.; Saunders, M.; Boyton, H.G.; Earhart, H.W.; Wadley, E.F.; Edwards, W.R.; Laber, R. Tetrahedron 1958, 4, 178
Arylium ions (see phenyl cation)
Aziridinium ions
N+
R R
R1 R2
Reviews:Crist, D.R.; Leonard, N.J. Angew. Chem. Int. Ed. 1969, 8, 962
11
NClCl
N+Cl
NClHO
N+OH
NOHHO
- Cl- H2O
- H+
- Cl-
H2O
- H+
Golumbic, C.; Fruton, J.S.; Bergmann, M. J. Org. Chem. 1946, 11, 518Fruton, J.S.; Bergmann, M. J. Org. Chem. 1946, 11, 543Golumbic, C.; Stahlmann, M.A.; Bergmann, M. J. Org. Chem. 1946, 11, 550
N
Cl
R R
N+
R
R
Cl
NR
R
Cl-
Kerwin, J.F.; Ullyot, G.E.; Fuson, R.C.; Zirkle, C.L. J. Am. Chem. Soc. 1947, 69, 2961Hanby, W.E.; Hartley, G.S.; Powell, E.O.; Rydon, H.N. J. Chem. Soc. Abstr. 1947, 519Schultz, E.M.; Sprague, J.M. J. Am. Chem. Soc. 1948, 70, 48Fuson, R.C.; Zirkle, C.L. J. Am. Chem. Soc. 1948, 70, 2760Freundlich, H.; Salomon, G. Z. Physik. Chem. 1933, 166A, 161Bartlett, P.D.; Ross, S.D.; Swain, C.G. J. Am. Chem. Soc. 1947, 69, 2971
Benzyne (arynes)
Reviews:Fields, E.K.; Meyerson, S. Adv. Phys. Org. Chem. 1968, 6, 1
12
Gilcrist, T.L.; Rees, C.W. Carbenes, Nitrenes, and Arynes, Appleton-Century Crofts: New York, 1969Fields, E.K. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 449Brown, R.F.C. Eur. J. Org. Chem. 1999, 3211Sander, W. Acc. Chem. Res. 1999, 32, 669 (m-benzyne and p-benzyne)Pellissier, H.; Santelli, M. Tetrahedron 2003, 59, 701 (arynes in syntheses)
pyrolysisCH4 + + other products
Berthelot, A. Compt. Rend. 1866, 63, 790Berthelot, A. Ann. Chem. 1867, 142, 254Berthelot, A. Bull. Soc. Chim. Fr. 1867, 7[2], 218Badger, G.M.; Spotswood, T.M. J. Chem. Soc. 1960, 4420
SO3R OHNaOH
∆+ RSO3Na + H2O
Kekule, A. Compt. Rend. 1864, 64, 753
Cl
RO3S
ClRO3S
OHHONaOH
∆
- RSO3Na- H2O
Limpricht, H. Chem. Ber. 1874, 7, 1439
13
Br
Br
CH3
NH2
NHNH
+ 2 NaOH
- 2 HBr
Kym, O. J. Prakt. Chem. 1895, 51[2], 325
Cl
Cl
Ph2N NPh2ClCl
Cl
Cl
+ 2 KCl2 Ph2N- K+
Haeussermann, C. Chem. Ber. 1900, 33, 939Haeussermann, C. Chem. Ber. 1901, 34, 38
O
Br
O O
OEt
EtOHKOH / EtOH
- HBr
14
Stoermer, R.; Kahlert, B. Chem. Ber. 1902, 35, 1633 (first suggestion of existence of triple bond in small ring compounds)
Cl
ClCl
300 C
- HCl
Ph-Cl
+
Meyer, K.H.; Bergius, F. Chem. Ber. 1914, 47, 3159
Bachmann, W.E.; Clarke, H.T. J. Am. Chem. Soc. 1927, 49, 2089 (first suggestion of existence of benzyne)
Lüttringhaus, A.; Saaf, G. Ann. Chem. 1930, 542, 250 (aryl-phenol rearrangement)
Cl NH2
NH2
* + KNH2
* * *
- KCl
50% 50%
Roberts, J.D.; Simmons, H.E. Jr.; Carlsmith, L.A.; Vaughan, W.C. J. Am. Chem. Soc. 1953, 75, 3290Roberts, J.D.; Semenov, D.A.; Simmons, H.E. Jr.; Carlsmith, L.A. J. Am. Chem. Soc. 1956, 78, 601Roberts, J.D.; Vaughan, C.W. Jr.; Carlsmith, L.A.; Semenov, D.A. J. Am. Chem. Soc. 1956, 78, 611Scardiglia, F.; Roberts, J.D. Tetrahedron 1957, 1, 343Bottini, A.T.; Roberts, J.D. J. Am. Chem. Soc. 1957, 79, 1458
F F
Li
Li
Ph
Ph-Li
- Ph-H - LiF
Ph-Li
Wittig, G.; Fuhrmann, G. Chem. Ber. 1940, 73, 1197
15
Br
F
Li
F
O
O
OH
OH+
H2/ Pd
H+
- LiF
Li(Hg)
Wittig, G. Naturwiss. 1942, 30, 696Wittig, G.; Harborth, G. Chem. Ber. 1944, 77, 306; 316Wittig, G.; Pohmer, L. Angew. Chem. 1955, 67, 348Wittig, G.; Pohmer, L. Chem. Ber. 1956, 89, 1334Wittig, G. Pure Appl. Chem. 1963, 7, 173
F
F
Ph (COOH)
COOH (Ph)Ph-Li
- Ph-H- LiF
Ph-LiCO2
Huisgen, R.; Rist, H. Naturwiss. 1954, 41, 358Huisgen, R.; Rist, H. Ann. Chem. 1955, 594, 137
16
Huisgen, R.; Knorr, R. Tetrahedron Lett. 1963, 1017
Levine, R.; Leake, W.W. Science 1955, 121, 780
Müller, E.; Roscheisen, G. Chem. Ztg. 1956, 80, 101
Cl RRNa
R = amyl
Morton, A.A.; Davidson, J.B.; Hakan, B.L. J. Am. Chem. Soc. 1942, 64, 2242Morton, A.A. J. Org. Chem. 1956, 21, 593
Heaney, H.; Mann, F.G.; Millar, I.T. J. Chem. Soc. 1957, 3930
17
O
O
O
O
O
O
O
O
O
O
O
O
O
O O
Obenzyne
- CO
+
benzyne
. .- CO
..
- CO
- CO
FVP
Brown, R.F.C.; Solly, R.K. Austr. J. Chem. 1966, 19, 1045
NO
O
O
N
- CO- CO2
hνAr / 10 K
18
Nam, H.H.; Leroi, G.E. J. Am. Chem. Soc. 1988, 110, 4096 (first observation of 3,4-pyridyne)
Betaines (phosphonium betaines)
PR3
R3
R4
- O
R1
R2
+
Reviews:Wittig, G. Pure Appl. Chem. 1964, 9, 245Vedejs, E. Science 1980, 207, 42Wittig, G. Science 1980, 210, 600
Br PPh3PPh3
- nBuH- LiBr
nBuLi
_
+
Br-+
+ PPh3
ylide
O
R H
PPh3- O
R
PPh3
PPh3- O
R R- LiOtBu- O=PPh3
tBuOH
betaine
_
+
+
+ +
_ Li+PhLi
- PhH
Wittig, G.; Schöllkopf, U., Chem. Ber. 1954, 87, 1318Wittig, G.; Haag, W. Chem. Ber. 1955, 88, 1654Wittig, G.; Pommer, H. DE 32741 BASF (1954)
Biradicals
19
OH
R1
R2
R3CH2 CH2
O
CH2
....
.. .. . .
CH2CH2 OCH2
.
.
.. . . ..
O
C CR1
R2
R4
R3
..
Reviews:Kuivila, H.G. Acc. Chem. Res. 1968, 1, 299 (organotin hydrides and organic free radicals)Borden, W.T. (ed.) Diradicals, Wiley: New York, 1982Platz, M.S. (ed.) Kinetics and Spectroscopy of Carbenes and Biradicals, Plenum Press: New York, 1990Cramer, J. Chem. Soc. Perkin Trans. 2 1998, 1007 (biradicals - Paul Dowd)Arnold, B.R.; Bucher, G.; Netto-Ferreira, J.C.; Platz, M.S.; Scaiano, J.C. Biradicals, Radicals in Excited States, Carbenes, and Related Species,Springer-Verlag: Weinheim, 1998Sander, W. Acc. Chem. Res. 1999, 32, 669 (m-benzyne and p-benzyne)
Thiele hydrocarbon (biradical)
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
..Thiele, J.; Balhorn, H. Chem. Ber. 1904, 37, 1463
Chichibabin hydrocarbon (biradical)
20
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Cl
Ph
Cl
Ph
. .Na or K
- NaCl orKCl
Chichibabin, A.E. Zh. Russ. Fiz.-Khim., Obshchestva 1907, 39, 925Chichibabin, A.E. Chem. Ber. 1907, 40, 1810
Schlenk-Brauns hydrocarbon (biradical)
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Cl Cl . .Na or K
- NaCl orKCl
Ph
PhPh
PhCl Cl Ph
PhPh
Ph ..Na or K
- NaClor - KCl
Schlenk, W.; Brauns, M. Chem. Ber. 1915, 48, 661; 716
21
Müller hydrocarbon (biradical)
Cl
Cl
Cl
Cl
Ph
Ph
Ph
Ph
..
Müller, E.; Neuhoff, H. Chem. Ber. 1939, 72, 2063Müller, E.; Tietze, E. Naturwiss. 1940, 28, 189Müller, E.; Tietze, E. Chem. Ber. 1941, 74, 807
Ph
Ph
Ph
Ph
Ph Ph
PhPh
O O
ClPh
Cl Cl
Ph Ph
PhPh
HO OH
- CuClor AgCl
Cu or Ag
FeHCl
2 PhLi
AlCl3
2 PhCOCl
..
22
Müller, E.; Pfanz, H. Chem. Ber. 1941, 74, 1051
Wittig, G.; von Lupin, F. Chem. Ber. 1928, 61B, 1627Wittig, G.; Leo, M. Chem. Ber. 1929, 62B, 1405Schönberg, A.; von Vargha, L. Chem. Ber. 1931, 64B, 1390Wittig, G.; Leo, M. Chem. Ber. 1931, 64B, 2395Schönberg, A.; Cernik, D.; Urban, W. Chem. Ber. 1931, 64B, 2577Schönberg, A. Chem. Ber. 1934, 67B, 1404Dufraisse, C. Chem. Ber. 1934, 67B, 2018Schönberg, A. Chem. Ber. 1935, 68B, 162Schönberg, A. Ann. Chem. 1935, 518, 299
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
. .paramagnetism of biradicals:Müller, E. Z. Elektrochem. 1934, 40, 542Müller, E.; Klemm, W.; Schuth, W. Naturwiss. 1934, 22, 335Müller, E.; Müller-Rodloff, I. Ann. Chem. 1935, 517, 134Müller, E.; Müller-Rodloff, I. Chem. Ber. 1935, 68B, 1276Müller, E.; Müller-Rodloff, I. Ann. Chem. 1936, 521, 81Müller, E.; Bunge, W. Chem. Ber. 1936, 69, 2164; 2168Müller, E. Naturwiss. 1937, 25, 545
Müller, E.; Dammerau, I. Chem. Ber. 1937, 70B, 2561Müller, E.; Sok, G. Chem. Ber. 1937, 70B, 1990Clar, E. Chem. Ber. 1935, 68B, 2066Schönberg, A. Trans. Faraday Soc. 1936, 32, 514Allen, F.L.; Sugden, S. J. Chem. Soc. 1936, 440Dufraisse, C. J. Am. Chem. Soc. 1936, 58, 858Hückel, E. Z. Physik. Chem. 1936, B34, 339
23
O O
CO
CHO
..hν
+ CO
+ CO
+ CH2=CH2 + CO
Hα abstraction
Hδ abstractionα cleavage
Norrish Type I
O
R1
R2
O
R1
R2OH
R1
R2OH
R1
R2
Norrish Type II
+
Hγ abstraction
..*3
hν β cleavage
Bamford, C.H.; Norrish, R.G.W. J. Chem. Soc. 1935, 1504Norrish, R.G.W.; Bamford, C.H. Nature 1936, 138, 1016Norrish, R.G.W.; Bamford, C.H. Nature 1937, 140, 195Norrish, R.G.W. Trans. Faraday Soc. 1937, 33, 1521
Bawn, C.E.H.; Hunter, R.F. Trans. Faraday Soc. 1938, 34, 608Fuson, R.C.; Lundquist, W.E. J. Am. Chem. Soc. 1938, 60, 1889Enderlin, L. Ann. Chim. Phys. 1938, 10, 5Bawn, C.E.H.; Milsted, J. Trans. Faraday Soc. 1939, 35, 889
24
N N
O
- CO
hν..- N2
hν
Dowd, P. J. Am. Chem. Soc. 1966, 88, 2587 (first observation of biradicals by ESR)
R4
R3
R1
R2
OR
R3
R4
R1
R2
R1
R2
R3
R4
ROH
.
.
Bergman, R.G.; Jones, R.R., J. Am. Chem. Soc. 1972, 94, 660 (Bergmann cyclization)
CH2 CH2..
Pagni, R.; Burnett, M.N.; Dodd, J.R. J. Am. Chem. Soc. 1977, 99, 1972
O CH2..
25
Rule, M.; Matlin, A.R.; Dougherty, D.A.; Hilinski, E.; Berson, J.A. J. Am. Chem. Soc. 1979, 101, 5098
O O O O
. .CH2=CH2
*3
hν
Freilich, S.F.; Peters, K.S. J. Am. Chem. Soc. 1981, 103, 6255; 1985, 107, 3819 (evidence for biradical in Paterno-Büchi reaction)
Bridged carbocations (see halonium ions, non-classical ions, and phenonium ions)
+
Nevell, T.P.; de Salas, E.; Wilson, C.L. J. Chem. Soc. 1939, 1188 (first suggestion)
Carbanions
R1 C
R2
R3
_
:
Reviews:Szwarc, M. (ed.) Carbanions: living polymers and electron transfer processes, Wiley: New York, 1968Kaiser, E.M.; Slocum, D.W. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 337Hogen-Esch, T.E. Adv. Phys. Org. Chem. 1977, 15, 154Stowell, J.C. Carbanions in Organic Synthesis, Wiley: New York, 1979Buncel, E.; Durst, T. (eds.) Comprehensive Carbanion Chemistry, Part A: structure and reactivity, Elsevier: Amsterdam, 1980Gau, G.; Assadourian, L.; Veracini, S. Prog. Phys. Org. Chem. 1987, 16, 237Nibbering, N.M.M. Adv. Phys. Org. Chem. 1988, 24, 1
26
Harder, S. Chem. Eur. J. 2002, 8, 3229
Buncel, E.; Dust, J.M. Carbanion Chemistry: structures and mechanisms, Oxford University Press: Oxford, 2003
stabilities of carbanions:Breslow, R.; Balasubramanian, K. J. Am. Chem. Soc. 1969, 91, 5182 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R.; Chu, W. J. Am. Chem. Soc. 1970, 92, 2165 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R.; Chu, W. J. Am. Chem. Soc. 1973, 95, 411 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R.; Mazur, M. J. Am. Chem. Soc. 1973, 95, 584 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R.; Drury, R.F. J. Am. Chem. Soc. 1974, 96, 4702 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R. Pure Appl. Chem. 1974, 40, 493 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Wasielewski, M.R.; Breslow, R. J. Am. Chem. Soc. 1976, 98, 4222 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R.; Goodin, R. J. Am. Chem. Soc. 1976, 98, 6077 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Bank, S.; Ehrlich, C.L.; Zubieta, J.A. J. Org. Chem. 1979, 44, 1454 (trityl carbanions)Bank, S.; Ehrlich, C.L.; Mazur, M.; Zubieta, J.A. J. Org. Chem. 1981, 46, 1243 (trityl carbanions)
organomagnesium compoundsHallwachs, W.; Schafarik, F. Ann. Chem. 1859, 109, 206Cahours, A. Ann. Chem. 1859, 114, 227Grignard, V. Ann. Chim. Phys. 1901, 24, 433
Zincke, T.; Suhl, R.S. Chem. Ber. 1907, 39, 4148Fromberz, K.; Meigen, W. Chem. Ber. 1907, 40, 403Schiff, H. Ann. Chem. 1907, 352, 73
Ph
Ph Ph
Ph
H H_ NMe4
++NMe4_
Schlenk, W. Ann. Chem. 1910, 372, 1
Wren, H. J. Chem. Soc. 1910, 95, 1583Wren, H. J. Chem. Soc. 1910, 95, 1593Tarbouriech, P.J. Compt. Rend. 1910, 149, 862Freylon, G. Ann. Chim. Phys. 1910, 19, 551
27
Mitchell, A.D.; Thorpe, J.F. Proc. Chem. Soc. 1911, 26, 248Mitchell, A.D.; Thorpe, J.F. Proc. Chem. Soc. 1911, 26, 2261Dieckmann, W. Chem. Ber. 1911, 44, 981Busch, M.; Limpach, O. Chem. Ber. 1911, 44, 1573Locquin, R. Compt. Rend. 1911, 153, 284
Curtius, T. Chem. Ztg. 1912, 35, 249Tarbouriech, P.J. Compt. Rend. 1913, 156, 75Wislicenus, W.; Elvert, H.R.; Kurtz, P. Chem. Ber. 1914, 46, 3395Curtius, T. J. Prakt. Chem. 1914, 87, 513Heiduschka, A.; Langkammerer, H. J. Prakt. Chem. 1914, 88, 425Hiller, S. J. Prakt. Chem. 1914, 88, 731Busch, M.; Lotz, H. J. Prakt. Chem. 1914, 90, 257Brady, O.L.; Dunn, F.P. J. Chem. Soc. 1914, 105, 2409; 2872Brady, O.L.; Dunn, F.P. Proc. Chem. Soc. 1914, 30, 240; 292Raffo, M.; Rossi, G. Gazz. Chim. Ital. 1915, 45, 28von Meyer, F. J. Prakt. Chem. 1915, 92, 255Chattaway, F.D.; Clemo, G.R. J. Chem. Soc. 1916, 109, 89Poccianti, P. Atti Accad. Lincei 1915, 24, 1135Poccianti, P. Gazz. Chim. Ital. 1915, 45, 111Brady, O.L.; Dunn, F.P. J. Chem. Soc. 1916, 109, 650Andreasch, R. Monatsch. Chem. 1917, 38, 203
organolithium compoundsSchlenk, W.; Holtz, J. Chem. Ber. 1917, 50, 271Andreasch, R. J. Chem. Soc. 1918, 114, 80
Conant, J.B.; Wheland, G.W. J. Am. Chem. Soc. 1932, 54, 1212 (stabilities of carbanions from hydrocarbon acidities)
Carbanions via E1cb (elimination unimolecular carbanion) mechanism
28
Ar
NMe3
Ar
NMe3
Ar
NMe3
Ar
Ar = p-NO2-C6H4
+ NMe3
+_
+ H3O+
_ ++ H2O
+
Hughes, E.D.; Ingold, C.K. J. Chem. Soc. 1933, 523Hughes, E.D.; Ingold, C.K.; Patel, C.S. J. Chem. Soc. 1933, 526
Carbenes or methylenes (general)
Reviews:Huisgen, R. Angew. Chem. 1955, 67, 439Knunyants, I.L.; Gambaryan, N.P.; Rokhin, E.M. Usp. Khim. 1958, 27, 1361Kirmse, W. Angew. Chem. 1959, 71, 537Kirmse, W. Angew. Chem. 1961, 73, 161Zollinger, H. Azo and Diazo Chemistry: aliphatic and aromatic compounds, Interscience Publications, Inc.: New York, 1961Miginiac, P. Bull. Soc. Chim. Fr. 1962, 2000Chinoporos, E. Chem. Rev. 1963, 63, 235Parham, W.E.; Schweizer, E.E. Org. Reactions 1963, 13, 55Hine, J. Divalent Carbon, Ronald Press: New York, 1964Kirmse, W. Carbene Chemistry, Academic Press: New York, 1964DeMore, W.B.; Benson, S.W. Adv. Photochem. 1964, 2, 219Frey, H.M. Prog. Reaction Kinetics 1964, 2, 131Bell, J.A. Prog. Phys. Org. Chem. 1964, 2, 1Closs, G.L. Top. Stereochem. 1968, 3, 193Gilcrist, T.L.; Rees, C.W. Carbenes, Nitrenes, and Arynes, Appleton-Century-Crofts: New York, 1969Bethell, D. Adv. Phys. Org. Chem. 1969, 7, 153Jones, M. Jr.; Moss, R.A. Carbenes, Wiley-Interscience: New York, Vol. 1 - 2, 1973Bethell, D. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 61Bethell, D. Org. Reactive Intermed. 1973, 61
29
Connor, J.A. J. Organometallic Chem. 1975, 4, 235 (carbenes and carbynes)Moss, R.A.; Jones, M. (eds.) Carbenes, Vol. 1, 2, Wiley: New York, 1975Moss, R.A. Acc. Chem. Res. 1980, 13, 58
Griller, D.; Nazran, A.S.; Scaiano, J.C. Acc. Chem. Res. 1984, 17, 283Platz, M.S. (ed.) Kinetics and Spectroscopy of Carbenes and Biradicals, Plenum Press: New York, 1990Tomioka, H. Res. Chem. Intermediates 1994, 20, 605Liu, M.T.H. Acc. Chem. Res. 1994, 27, 287Regitz, M. Angew. Chem. Int. Ed. 1996, 35, 725Zaragoza, F. Tetrahedron 1997, 53, 3425Tomioka, H. Acc. Chem. Res. 1997, 30, 315Tomioka, H. Bull. Chem. Soc. Jpn 1998, 71, 1501Arnold, B.R.; Bucher, G.; Netto-Ferreira, J.C.; Platz, M.S.; Scaiano, J.C. Biradicals, Radicals in Excited States, Carbenes, and Related Species,Springer-Verlag: Weinheim, 1998Böhm, V.P.W.; Herrmann, W.A. Angew. Chem. Int. Ed. 2000, 39, 4036 (stable carbenes)Bertrand, G. (ed.) Carbene Chemistry: from fleeting intermediates to powerful reagents, Marcel Dekker, Inc.: New York, 2002
P2O5
CH3OH CH2:Dumas, J.B.; Peligot, E. Ann. Chim. Phys. 1835, 58, 5 (attempt)Regnault, H.V. Ann. Chim. Phys. 1839, 71, 427
- HCl: CCl2
baseCHCl3
Geuther, A. Ann. Chem. 1862, 123, 121 (suggestion)
CH2:CH2=CH2: CH2
Cu
∆CH2I2
Butlerov, A. Ann. Chem. 1858, 107, 110Butlerov, A. Ann. Chem. 1859, 111, 242
Nef, J.U. Ann. Chem. 1897, 298, 202 (general methylene theory)
30
N2
R1 R2R1 R2
R1 R2
C
O
- CO
hν or ∆:
- N2
hν or ∆
Staudinger, H.; Kupfer, O. Chem. Ber. 1911, 44, 2197Staudinger, H.; Kupfer, O. Chem. Ber. 1912, 45, 501 (from diazomethanes and diazoketones)Meerwein, H.; Rathjen, H.; Werner, H. Chem. Ber. 1942, 75, 1610 (discovery of insertion reactions of carbenes in XH bonds)Doering, W.v.E.; Knox, L.H. J. Am. Chem. Soc. 1956, 78, 4947 (coining of name)
:CCl2 + Cl-CCl3-
H2O + CCl3-CHCl3 + OH-
Hine, J. J. Am. Chem. Soc. 1950, 72, 2438 (haloform hydrolysis)Hine, J.; Dowell, A.M. Jr. J. Am. Chem. Soc. 1954, 76, 2688Hine, J.; Dowell, A.M. Jr.; Singley, J.E. Jr. J. Am. Chem. Soc. 1956, 78, 479
R R R R
Y
X
X
Y
X
Y
RR
X
Y
RR
X
RR
Y
..:
31
Doering, W.v.E.; Hoffmann, A.K. J. Am. Chem. Soc. 1954, 76, 6162 (trapping of carbenes with olefins)Skell, P.S.; Garner, A.Y. J. Am. Chem. Soc. 1956, 78, 3409 (connection between multiplicity of carbene and stereochemistry of cyclopropane trappedproduct)Skell, P.S.; Garner, A.Y. J. Am. Chem. Soc. 1956, 78, 5430 (connection between multiplicity of carbene and stereochemistry of cyclopropane trappedproduct)
O
RO
N2
H
O
ROH COOR
ROOC
COOR
COOR
- N2 :
Doering, W.v.E.; Knox, L.H. J. Am. Chem. Soc. 1956, 78, 4947 (coining of "carbene" name)Doering, W.v.E.; Henderson, W.A. Jr. J. Am. Chem. Soc. 1958, 80, 5274
N2
Ph Ph Ph Ph
Ph Ph
Ph Ph
H
T > 77 K
T = 77 K
..+ R
+ Ph2C=CPh2
R-H
R-H
:
- N2
254 nm
32
Gibbons, W.A.; Trozzolo, A.M. J. Am. Chem. Soc. 1966, 88, 172 (matrix isolation EPR)
N2H
.- R
.R-H
:
- N2
hν
Moritani, I.; Murahashi, S.; Nishino, N.B.; Kimura, K.; Tsubomura, H. Tetrahedron Lett. 1966, 373 (flash photolysis of diazo compounds - nokinetics)
N2
Ph Ph
Ph Ph
Ph Ph
H
λ(max) = 340 nm
λ(max) = 300 nm
...
cyclohexane
benzene
hν
hν
Closs, G.L.; Rabinow, B.E. J. Am. Chem. Soc. 1976, 98, 8190 (first absolute rate constant measurement of carbene reaction by flash photolysis)
Moss, R.A.; Mallon, C.B. J. Am. Chem. Soc. 1975, 97, 344 (Hammett analysis of carbene + olefin reaction)Moss, R.A.; Joyce, M.A.; Huselton, J.K. Tetrahedron Lett. 1975, 16, 4621
Ar Cl
:
Turro, N.J.; Butcher, J.A. Jr.; Moss, R.A.; Guo, W.; Munjal, R.C.; Fedorynski, M. J. Am. Chem. Soc. 1980, 102, 7576Gould, I.R.; Turro, N.J.; Butcher, J. Jr.; Doubleday, C. Jr.; Hacker, N.P.; Lehr, G.F.; Moss, R.A.; Cox, D.P.; Guo, W.; Munjal, R.C.; Perez, L.A.;Fedorynski, M. Tetrahedron 1985, 41, 1587
33
:
Zupanic, J.J.; Schuster, G.B. J. Am. Chem. Soc. 1980, 102, 5958Lapin, S.C.; Brauer, B.E.; Schuster, G.B. J. Am. Chem. Soc. 1984, 106, 2092
Ph Ph..
Hadel, L.M.; Platz, M.S.; Scaiano, J.C. J. Am. Chem. Soc. 1984, 106, 283 (quenching of triplet diphenylcarbene)
Griller, D.; Nazran, A.S.; Scaiano, J.C. Tetrahedron 1985, 41, 1525
N2
Np HNp H
N
O+
Np
H
N+
Np
H
N+
Np
H
NEt3
Np
H
+_
Et3N
_
_
_
CH3CN
(CH3)2C=O
:
- N2
hν
34
Barcus, R.L.; Hadel, L.M.; Johnston, L.J.; Platz, M.S.; Savino, T.G.; Scaiano, J.C. J. Am. Chem. Soc. 1986, 108, 3928(trapping of carbenes via ylide formation)
X+
_
Griller, D.; Hadel, L.M.; Nazran, A.S.; Platz, M.S.; Wong, P.C.; Savino, T.G.; Scaiano, J.C. J. Am. Chem. Soc. 1984, 106, 2227(trapping of carbenes via ylide formation)
O
N2
RR
R R
O
RR
R R
O
R
R
R
R
R = H, F
...hν- N2
.
Sander, W.; Bucher, G.; Reichel, F.; Cremer, D. J. Am. Chem. Soc. 1991, 113, 5311Bucher, G.; Sander, W. J. Org. Chem. 1992, 57, 1346Wenk, H.H.; Hübert, R.; Sander, W. J. Org. Chem. 2001, 66, 7994Sander, W.; Hübert, R.; Kraka, E.; Grafenstein, J.; Cremer, D. Chem. Eur. J. 2000, 6, 4567
Carbenes (singlet)
R1 R2
..Reviews:
35
Kirmse, W. Angew. Chem. Int. Ed. 2004, 43, 1767
Herzberg, G.; Shoosmith, J. Nature 1959, 183, 1801
Herzberg, G. Proc. Roy. Soc. London 1961, 262A, 291Mackay, C.; Wolfgang, R. J. Am. Chem. Soc. 1961, 83, 2399Gutsche, C.D.; Bachman, G.L.; Coffey, R.S. Tetrahedron 1962, 18, 617Bradley, J.N.; Ledwith, A. J. Chem. Soc. 1963, 3480Schoellkopf, U.; Lerch, A.; Paust, J. Chem. Ber. 1963, 96, 2266Skatteboel, L. Acta Chem. Scand. 1963, 17, 1683Bradley, J.N.; Cowell, G.W.; Ledwith, A. J. Chem. Soc. 1964, 353Hamilton, G. J. Am. Chem. Soc. 1964, 86, 3391Sargeant, P.B.; Shechter, H. Tetrahedron Lett. 1964, 3957
Herzberg, G.; Johns, J.W.C. Proc. Roy. Soc. London 1967, 295A, 107
Carbenes (triplet)
R1 R2..
Reviews:Tomioka, H. Acc. Chem. Res. 1997, 30, 315Kirmse, W. Angew. Chem. Int. Ed. 2003, 42, 2117
Herzberg, G.; Shoosmith, J. Nature 1959, 183, 1801
Herzberg, G. Proc. Roy. Soc. London 1961, 262A, 291Skell, P.S.; Klebe, J. J. Am. Chem. Soc. 1960, 82, 247MacKay, C.; Wolfgang, R. J. Am. Chem. Soc. 1961, 83, 2399Schoellkopf, U.; Lerch, A.; Pitteroff, W. Tetrahedron Lett. 1962, 241D'yakonov, I.A.; Danilkina, L.P. Zh. Obshch. Khim. 1962, 32, 1008Bradley, J.N.; Ledwith, A. J. Chem. Soc. 1963, 3480
36
Cowan, D.O.; Couch, M.M.; Kopecky, K.R.; Hammond, G. J. Org. Chem. 1964, 29, 1922Sloan, M.F.; Prosser, T.J.; Newburg, N.R.; Breslow, D.S. Tetrahedron Lett. 1964, 2945Hamilton, G.A. . J. Am. Chem. Soc. 1964, 86, 3391Frey, H.M. Chem. Commun. 1965, 260Padwa, A.; Layton, R. Tetrahedron Lett. 1965, 2167Moritani, I.; Obata, N. Tetrahedron Lett. 1965, 2817
Carbene (Arduengo)
Reviews:Arduengo, A.J. III Acc. Chem. Res. 1999, 32, 913 (stable carbenes)Arduengo, A.J. III Tetrahedron 1999, 55, 14523 (imidazolylidenes and imidazolinylidenes)
NN NN+
Cl-
KOtBuTHF
:
- KCl- tBuOH
Arduengo, A.J. III; Harlow, R.L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361Dixon, D.A.; Arduengo, A.J. III J. Phys. Chem. 1991, 95, 4180Arduengo, A.J. III; Dias, H.V.R.; Harlow, R.L.; Kline, M. J. Am. Chem. Soc. 1992, 114, 5530
Carbene (Bertrand)
Reviews:Bertrand, G. Chem. Rev. 2000, 100, 39 (stable carbenes)
N2
Me3Si Li
N2
Me3Si P
N(iPr)2
N(iPr)2
- LiCl
THF- 78oC
+ (iPr2N)2PCl
37
N2
Me3Si P
N(iPr)2
N(iPr)2
Me3Si P
N(iPr)2
N(iPr)2
Me3Si P
N(iPr)2
N(iPr)2
C PMe3Si
N(iPr)2
N(iPr)2
_+
:
hν
- N2
Baceiredo, A.; Bertrand, G.; Sicard, G. J. Am. Chem. Soc. 1985, 107, 4781Igau, A.; Grützmacher, H.; Baceiredo, A.; Bertrand, G. J. Am. Chem. Soc. 1988, 110, 6463Igau, A.; Baceiredo, A.; Trinquier, G.; Bertrand, G. Angew. Chem. Int. Ed. 1989, 28, 621
Dicarbenes
N2N2
hν
- 2 N2
:: ..
Trozzolo, A.M.; Murray, R.W.; Smolinsky, G.; Yager, W.A.; Wasserman, E. J. Am. Chem. Soc. 1963, 85, 2526
N2 N2
PhPh PhPhhν
- 2 N2
: :
Wasserman, E.; Murray, R.W.; Yager, W.A.; Trozzolo, A.M.; Smolinksy, G. J. Am. Chem. Soc. 1967, 89, 5076
Carbocations
38
R1
R3 R2+
Reviews:Ingold, C.K. Ann. Rep. Prog. Chem. (Chem. Soc. London) 1927, 24, 156Whitmore, F.C. Ann. Rep. Prog. Chem. (Chem. Soc. London) 1933, 30, 177Whitmore, F.C. Chem. Eng. News 1948, 26, 688Deno, N.C. Prog. Phys. Org. Chem. 1964, 2, 129Olah, G.; Pittman, C.U. Jr. Adv. Phys. Org. Chem. 1966, 4, 305Bethell, D.; Gold, V. Carbonium Ions: an introduction, Academic Press: London, 1967More O'Ferrall, R.A. Adv. Phys. Org. Chem. 1967, 5, 331Olah, G.A.; Schleyer, P.v.R., eds. Carbonium Ions, Wiley-Interscience: New York, 1968 - 1976, Vol. I - IV, 1968 - 1973Nenitzescu, C.N. in Carbonium Ions (G.A. Olah; P.v.R. Schleyer, eds.) Wiley-Interscience: New York, 1968, Vol. 1, p. 1 - 75Cacace, F. Adv. Phys. Org. Chem. 1970, 8, 79Brouwer, D.M.; Hogeveen, H. Prog. Phys. Org. Chem. 1972, 9, 179Hogeveen, H. Adv. Phys. Org. Chem. 1972, 10, 29Cabell-Whiting, P.W.; Hogeveen, H. Adv. Phys. Org. Chem. 1972, 10, 129McManus, S.P.; Pittman, C.U. Jr. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 193Olah, G.A. Carbocations and Electrophilic Reactions, Wiley: New York, 1974Ahlberg, P.; Jönsall, G.; Engdahl, C. Adv. Phys. Org. Chem. 1983, 19, 223Olah, G.A.; Prakash, G.K.S.; Sommer, J. Superacids, Wiley: New York, 1985Vogel, P. Carbocation Chemistry, Elsevier: Amsterdam, 1985Traynham, J.G. J. Chem. Educ. 1986, 63, 930 (carbocation names)Traynham, J.G. J. Chem. Educ. 1989, 66, 451 (carbocation names)Prakash, G.K.S.; Schleyer, P.v.R. Stable Carbocation Chemistry, Wiley: New York, 1997Rappoport, Z.; Stang, P.J. Diccoordinated Carbocations, Wiley: New York, 1997Abboud, J.L.M.; Herreros, M.; Notario, R.; Lomas, J.S.; Mareda, J.; Müller, P.; Rossier, J.C. J. Org. Chem. 1999, 64, 6401 (bridgeheadcarbocations)Richard, J.P.; Amyes, T.L.; Lin, S.S.; O'Donoghue, A.C.; Toteva, M.M.; Tsuji, Y.; Williams, K.B. Adv. Phys. Org. Chem. 2000, 35, 67Olah, G.A. J. Org. Chem. 2001, 65, 5943Abboud, J.L.M.; Alkorta, I.; Dávalos, J.Z.; Müller, P.; Quintanilla, E. Adv. Phys. Org. Chem. 2002, 37, 57
stabilities of carbocations:
39
Deno, N.C.; Jaruzelski, J.; Schriescheim, A. J. Am. Chem. Soc. 1955, 77, 3044 (triarylcarbonium ions by HR acidity function)Jenson, E.D.; Taft, R.W. J. Am. Chem. Soc. 1964, 86, 116 (triarylcarbonium ions by potentiometric measurements)Taft, R.W.; McKeever, L.D. J. Am. Chem. Soc. 1965, 87, 2489 (triarylcarbonium ions by potentiometric measurements)Diffenbach, R.A.; Sano, K.; Taft, R.W. J. Am. Chem. Soc. 1966, 88, 4747 (triarylcarbonium ions by potentiometric measurements)Feldman, M.; Flythe, W.C. J. Am. Chem. Soc. 1969, 91, 4577 (triarylcarbonium ion reduction potentials)Breslow, R.; Balasubramanian, K. J. Am. Chem. Soc. 1969, 91, 5182 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R.; Chu, W. J. Am. Chem. Soc. 1970, 92, 2165 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R.; Chu, W. J. Am. Chem. Soc. 1973, 95, 411 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R.; Mazur, M. J. Am. Chem. Soc. 1973, 95, 584 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R.; Drury, R.F. J. Am. Chem. Soc. 1974, 96, 4702 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R. Pure Appl. Chem. 1974, 40, 493 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Wasielewski, M.R.; Breslow, R. J. Am. Chem. Soc. 1976, 98, 4222 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Breslow, R.; Goodin, R. J. Am. Chem. Soc. 1976, 98, 6077 (thermodynamic stabilities of cations and anions via electrochemical oxidations)Bank, S.; Ehrlich, C.L.; Zubieta, J.A. J. Org. Chem. 1979, 44, 1454 (trityl carbonium ions)Bank, S.; Ehrlich, C.L.; Mazur, M.; Zubieta, J.A. J. Org. Chem. 1981, 46, 1243 (trityl carbonium ions)
Cl OHH2Oacid catalyst
Stieglitz, J. Am. Chem. J. 1899, 21, 101
Ph
Ph Ph
ClPh
Ph Ph
AlCl4-++ AlCl3
MeO C Cl MeO C+
H2SO4
3 3
HSO4-
- HCl
Norris, J.F.; Sanders, W.W. Am. Chem. J. 1901, 25, 54Norris, J.F. Am. Chem. J. 1901, 25, 117Norris, J.F. Am. Chem. J. 1907, 38, 627
40
Ph
Ph Ph
ClPh
Ph Ph
Ph
Ph Ph
SO4-2
2
+HCl
HSO4-
+
H2SO4
Gomberg, M. Chem. Ber. 1902, 35, 2397; 2405Walden, P. Chem. Ber. 1902, 35, 2018Hantzsch, A. Z. Physik. Chem. 1907, 61, 257Hantzsch, A. Chem. Ber. 1921, 54, 2573; 2578
NH2
H2N
H2N
NH2
H2N
H2N
fuchsine+
X -X -
+
41
NMe2
Me2N
Me2N
NMe2
Me2N
Me2N
+
X - X -
+ crystal violet
Kehrmann, F.; Wentzel, F. Chem. Ber. 1901, 34, 3815Baeyer, A.; Villiger, V. Chem. Ber. 1902, 35, 1189Baeyer, A.; Villiger, V. Chem. Ber. 1902, 35, 3013Baeyer, A.; Villiger, V. Chem. Ber. 1903, 36, 2774Baeyer, A.; Villiger, V. Chem. Ber. 1904, 37, 597Baeyer, A.; Villiger, V. Chem. Ber. 1904, 37, 1183Baeyer, A.; Villiger, V. Chem. Ber. 1904, 37, 2848Baeyer, A.; Villiger, V. Chem. Ber. 1904, 37, 3191Baeyer, A. Chem. Ber. 1905, 38, 569Baeyer, A. Chem. Ber. 1905, 38, 1156
Ph
ClPh Ph
OR
Cl
Ph Ph Ph Ph
OR
Ph Ph
+- Cl-
H2O80% EtOH
H2O80% EtOH
- Cl-
+R = H, Et
42
Ward, A.M. J. Chem. Soc. 1927, 445; 2285
Ph Cl Ph OH- Na+
NaOH+
- Cl-Ph-CH2
Ingold, C.K.; Rothstein, E. J. Chem. Soc. 1928, 1217Steigman, J.; Hammett, L.P. J. Am. Chem. Soc. 1937, 59, 2536Whitmore, F.C. J. Am. Chem. Soc. 1932, 54, 3274
Cl
ClCl- Cl-
Cl-
Cl-+H+ +
Wagner, G.; Brickner, W. Chem. Ber. 1899, 32, 2302Meerwein, H.; van Emster, K. Chem. Ber. 1922, 55, 2500Meerwein, H.; Hammel, O.; Serini, A.; Vorster, J. Ann. Chem. 1927, 453, 16
Ziegler, K.; Wollschitt, H. Ann. Chem. 1930, 479, 104 (stabilities of cations in SO2)
R = tBu, iPrR+ BF4-R-F + BF3
Olah, G.A.; Kuhn, S.J.; Opal, J. J. Chem. Soc. 1957, 2174
43
O
tBu F
O
tBuMe3C+ SbF6
-
- COSbF6
-++ SbF5
Olah, G.A.; Kuhn, S.J.; Tolgyesi, W.S.; Baker, E.B. J. Am. Chem. Soc. 1962, 84, 2733Olah, G.A. Rev. Roum. Chim. 1962, 7, 1129
R
R
R
H R3C+ FSO3- + H2
FSO3H-SbF5
Olah, G.A.; Lukas, J. J. Am. Chem. Soc. 1967, 89, 2227; 4743Olah, G.A.; Tolgyesi, W.S.; Kuhn, S.J.; Moffatt, M.E.; Bastien, I.J.; Baker, E.B. J. Am. Chem. Soc. 1963, 85, 1328Olah, G.A.; Comisarow, M.B.; Cupas, C.A.; Pittman, C.U. Jr. J. Am. Chem. Soc. 1965, 87, 2997Olah, G.A.; Schlosberg, R.H. J. Am. Chem. Soc. 1968, 90, 2726Olah, G.A. J. Am. Chem. Soc. 1972, 94, 808 (proposal to change definition of carbonium ion; introduction of carbenium ion terminology)
Carbynes
R C
.
:
Reviews:Connor, J.A. J. Organometallic Chem. 1975, 4, 235 (carbenes and carbynes)
N2
EtOOC
EtOOC C.
:Hg + 2 N2 + 2 hν
2
_Hg+2
44
Strausz, O.P.; Kennepohl, G.J.A.; Garneau, F.X.; DoMinh, T.; Kim, B.; Valenty, S.; Skell, P.S. J. Am. Chem. Soc. 1974, 96, 5723
2,4- and 2,5-Cyclohexadienones
O
R
H
O
R
H
Reviews:Schuster, D.I. Acc. Chem. Res. 1978, 11, 65
Crowther, H.L.; McCombie, H. J. Chem. Soc. 1913, 103, 536Crowther, H.L.; McCombie, H. Proc. Chem. Soc. 1913, 29, 68
O - Na+
Br
O
+- NaBr
Curtin, D.Y.; Crawford, R.J. Chem. Ind. 1956, 313
2,4- and 2,5-Cyclohexadienimines
N
R2
H
N
R2
H
R1
R1
45
Reviews:None
NH2
FF
F F
R
N
R Cl
F
F
F
F
Cl
2 tBuOCl
- 2 tBuOH
R = Me, MeO, nBu
Andreevskaya, O.I.; Markovskii, L.N.; Poleshchuk, O.K.; Furin, G.G.; Shermolovich, Y.G.; Yakobson, G.G. Zh. Org. Khim. 1980, 16, 817
H2N
COOHO
N
pTolSO2
OO
O
O
pTolSO2Cl
- HCl- 2 H+
- 2 e-
H2O /alumina
- pTolSO2NH2
Coutts, I.G.C.; Edwards, M.; Musto, D.R.; Richards, D.J. Tetrahedron Lett. 1980, 21, 5055
N+
tBu
tBu O-
R2
R3
R1
N
O
HR1
R2
R3
tBu
tBu
N
OtBu
tBu
R1
R2
R3
+H+
46
Doepp, D.; Krueger, C.; Makedakis, G.; Nour-el-Din, A.M. Chem. Ber. 1985, 118, 510
Cyclopropenyl cations
R1
R2 R3
R1
R2 R3
R1
R2 R3
R1
R2 R3
+
+
++
Reviews:Krivun, S.V.; Alferova, O.F.; Sayapina, S.V. Usp. Khim. 1974, 43, 1739Allen, A.D.; Tidwell, T.T. Chem. Rev. 2001, 101, 1333Komatsu, K.; Kitagawa, T. Chem. Rev. 2003, 103, 1371
Ph
Ph Ph
Ph
Ph
N2
Ph Cl
ClPh
Ph Ph
OtBuPh
Ph Ph
O
Ph
Ph
Ph
PhPh
Ph
HBF4H2O
- HCl
tBuOH
- N2
+
+ BF4-
Breslow, R. J. Am. Chem. Soc. 1957, 79, 5318
47
Breslow, R.; Yuan, C. J. Am. Chem. Soc. 1958, 80, 5991Breslow, R.; Höver, H. J. Am. Chem. Soc. 1960, 82, 2644Breslow, R.; Bahary, W.; Reinmuth, W. J. Am. Chem. Soc. 1961, 83, 1763Breslow, R.; Lockhart, J.; Chang, H.W. J. Am. Chem. Soc. 1961, 83, 2375Breslow, R.; Höver, H.; Chang, H.W. J. Am. Chem. Soc. 1962, 84, 3168Breslow, R.; Groves, J.T.; Ryan, G. J. Am. Chem. Soc. 1967, 89, 5048
Dications
Reviews:Nenajdenko, V.G.; Shevchenko, N.E.; Balenkova, E.S.; Alabugin, I.V. Chem. Rev. 2003, 103, 229
(i) Benzidine rearrangement
NH NH
H2N NH2
NH2 NH2
H2N NH2
H
H
+ +2 H+
+ + - 2 H+
Hofmann, A.W. Proc. Roy. Soc. London 1863, 12, 576Jacobson, P.; Henrich, F.; Klein, J. Chem. Ber. 1893, 26, 688Olah, G.A.; Dunne, K.; Kelly, D.P.; Mo, Y.K. J. Am. Chem. Soc. 1972, 94, 7438
(ii) Dications synthesized in magic acid
+O C (CH2)n C O+(CH2)n
O
HO
O
OH
(CH2)n
O
H2O
O
OH2
- 2 H2O
++
FSO3H/SbF5/SO2
[SbF6-]2
48
Olah, G.A.; Comisarow, M.B. J. Am. Chem. Soc. 1966, 88, 3313
N+H
R1
R2
N
R1
R2
OH N+
R1
R2
OH2H
FSO3H/SbF5/SO2 +
- H2O[SbF6
-]2+
Olah, G.A.; Calin, M. J. Am. Chem. Soc. 1968, 90, 943
R
R
R
R
R
R
R
X
X
R
- 2 HX
FSO3H/SbF5/SO2
+2 [SbF6-]2
R = H, Ph
X = Cl, Br
Olah, G.A.; Bollinger, J.M.; White, A.M. J. Am. Chem. Soc. 1969, 91, 3667Olah, G.A.; Mateescu, G.D. J. Am. Chem. Soc. 1970, 92, 1430
FSO3H/SbF5/SO2
+ + [SbF6-]2
Bollinger, J.M.; Olah, G.A. J. Am. Chem. Soc. 1969, 91, 3380
(iii) Violenes
R2N CH CH CH CH NR2 R2N CH CH CH CH NR2 R2N CH CH CH CH NR2
n n
+.- e- - e-
n
+ +
49
Hunig, S. Ann. Chem. 1964, 676, 32Hunig, S.; Balli, H.; Conrad, H.; Schott, A. Ann. Chem. 1964, 676, 36; 52Hunig, S. Chem. Eng. News 1966, 44, 102Hunig, S.; Geiger, H.; Kaupp, G.; Kniese, W. Ann. Chem. 1966, 697, 116
(iv) Wallach intermediate
N N+ +
N N+Ar
Ph
O-
N NAr
OH
N NAr
H
N NAr OH+ + H2O +2 H+
- H2O - H+ - H+
Wallach, O.; Belli, E. Chem. Ber. 1880, 13, 525Buncel, E.; Lawton, B.T. Chem. Ind. 1963, 1835Buncel, E.; Lawton, B.T. Can. J. Chem. 1965, 43, 862Olah, G.A.; Dunne, K.; Kelly, D.P.; Mo, Y.K. J. Am. Chem. Soc. 1972, 94, 7438
Cox, R.A.; Fung, D.Y.K.; Csizmadia, I.G.; Buncel, E. Can. J. Chem. 2003, 81, 535
(v) Wurster salts
NH2H2N++
50
NMe2Me2N NMe2Me2N
NH2Me2N NH2Me2N
Wurster's red
+ Br-.+
HOAc
Br2
Br2
HOAc
+.+ Br-
Wurster's blue
Wurster, C. Chem. Ber. 1879, 12, 522Wurster, C.; Sendtner, R. Chem. Ber. 1879, 12, 1803Wurster, C.; Schobig, E. Chem. Ber. 1879, 12, 1807Wurster, C. Chem. Ber. 1879, 12, 2071Wurster, C. Chem. Ber. 1886, 19, 3195
NMe2
NMe2
NMe2
NMe2
NMe2
NMe2
.- e-
+
- e-
+
+
Michaelis, L. J. Am. Chem. Soc. 1931, 53, 2953Katz, H. Z. Physik 1933, 87, 238Michaelis, L.; Schubert, M.P.; Granick, S. J. Am. Chem. Soc. 1939, 61, 1981
1,3-Dioxolenium salts
51
O
O R+ BF4
-
Reviews:Paulsen, H. Pure Appl. Chem. 1975, 41, 69
O
O
BrO
O
+ AgBr+ AgBF4 + BF4-
Meerwein, H.; Wunderlich, K. Angew. Chem. 1957, 69, 481
O
O PhN2
+
Cl
Cl
Cl
O
O Ph
H
Cl
Cl
Cl H++BF4-
+ BF4-
Meerwein, H.; Allendorfer, H.; Beckmann, P.; Kunert, F.; Morschel, H.; Pawellek, F.; Wunderlich, K. Angew. Chem. 1958, 70, 211
O
O R
O
O R
+ AgBr + Et-H+ AgBF4 + Et-Br BF4-+
Meerwein, H.; Hederich, V.; Wunderlich, K. Arch. Pharm. 1958, 291, 541
O
O H
O
O
+ Ph3CH+ Ph3C+ BF4-
+ BF4-
52
Meerwein, H.; Hederlich, V.; Morschel, H.; Wunderlich, K. Ann. Chem. 1960, 635, 1
1,3-Dipoles
XR1
R2
R3
R4
O
R1
R2 O -
X R1
R3
R2
R4
R5
C NR1
R2
R3
nitrile ylides
_+
carbene traps
+
_+
carbonyl oxide
carbonyl ylide (X = O)thiocarbonyl ylide (X = S)azomethine ylide (X = N-R)
+_
:
Reviews:Smith, L.I. Chem. Rev. 1938, 23, 193Huisgen, R. Proc. Chem. Soc. 1961, 357
(i) Azomethine ylideReviews:Surpateanu; Karzazi Heterocycles 1999, 51, 863 (cyclic azomethine ylides)Eberbach, W. Science of Synthesis 2004, 27, 441
Huisgen, R. Angew. Chem. 1963, 75, 604Huisgen, R. Angew. Chem. 1963, 75, 742
(ii) Carbonyl oxide (Criegee zwitterion)Reviews:Criegee, R. Record Chem. Prog. 1957, 18, 111Bailey, R.S. Chem. Rev. 1958, 58, 925Criegee, R. in Peroxide Reaction Mechanisms (J.O. Edwards, ed.) Interscience Publishers, Inc.: New York, 1962, p. 32
53
Huisgen, R. Angew. Chem. Int. Ed. 1963, 2, 565Kuczkowski, R.L. in 1,3-Dipolar Cycloaddition Chemistry, (A. Padwa, ed.) Wiley: New York, 1984, Vol. 2, p. 197 - 276Sander, W. Angew. Chem. 1990, 102, 362Bunnelle, W.H. Chem. Rev. 1991, 91, 335Ishiguro, K.; Nojima, T.; Sawaki, Y. J. Phys. Org. Chem. 1997, 10, 787Block, K.; Kappert, W.; Kirschfeld, A.; Muthusamy, S.; Schroeder, K.; Sander, W.; Kraka, E.; Sosa, C.; Cremer, D. in Peroxide Chemistry, (W.Adam, ed.) Wiley-VCH: Weinheim, 2000, p. 139 - 156
2 Ph2C=O + N2Ph2C=N=N+ _
+ Ph2C=O-O
_+
+ _
Ph2C=O-O:Ph2C + O2
:N2 + Ph2Chν_+
Ph2C=N=N
O+
R
R
O - O
R
R
O - OOH
R
R
MeO
O O
OR
R
O O
OOR
R
R
R
+MeOH
CH2=Odimerization
Bartlett, P.D.; Traylor, T.G. J. Am. Chem. Soc. 1962, 84, 3408
54
O O
OPh
Ph
R
H
RCHO_+Ph2C-O-O
- N2
hνPh2CN2
Murray, R.W.; Suzui, A. J. Am. Chem. Soc. 1971, 93, 4963
N
R
R
N
NR
R O O -
N
O+
R
R
O -
O O
NNR
R
O O
OR
R
R'
H
+_1O2
+
- N2
- N2
N2O + R2C=O
R'-CHO
Higley, D.P.; Murray, R.W. J. Am. Chem. Soc. 1974, 96, 3330
(iii) Carbonyl ylideReviews:Padwa, A. Acc. Chem. Res. 1991, 24, 22Padwa, A. Trends Org. Chem. 1993, 4, 139McMills, M.C.; Wright, D. Chem. Heterocyclic Compounds 2002, 59, 253Tomioka, H. in Nitrogen, Oxygen and Sulfur Ylide Chemistry, (J.S. Clark, ed.) Oxford University Press: Oxford, 2002, p. 213 - 218 Ph
PhPh Ph Ph PhO
O+Ph Ph
_
∆ or hνmCPBAhν+
55
Arnold, D.R.; Karnischky, L.A. J. Am. Chem. Soc. 1970, 92, 1404
O
Ph
PhO+Ph
Ph
O
Ph Ph
O+Ph PhO+
PhPh
_
+_
hν
hν _
Thap, D.M.; Trozzolo, A.M.; Griffin, G.W. J. Am. Chem. Soc. 1970, 92, 1402
O+ CN
CN
PhO+ CN
COOEt
Ph
O
Ph
CN
CN
O
Ph
COOEt
CN
__
Robert, A.; Pommeret, J.J.; Foucaud, A. Compt. Rend. 1970, 270, 1739Pommeret, J.J.; Robert, A. Compt. Rend. 1971, 272, 333Pommeret, J.J.; Robert, A. Tetrahedron 1971, 27, 2977Robert, A.; Pommeret, J.J.; Foucaud, A. Tetrahedron 1972, 28, 2085
56
O
O
Ph
Ph
O
O+
Ph
Ph
O
O
PhR
R
Ph
_
RCH=CHR
Lown, J.W.; Matsumoto, K. Can. J. Chem. 1971, 49, 3443
Vukov, V.; Crawford, R.J. Can. J. Chem. 1975, 53, 1367 (secondary deuterium kinetic isotope effects)
O+ Ph
CN
PhNC
CN
PhC CPh
O
Ph
CN
Ph
O
Ph Ph
NC
Ph
CN
Ph
_
Hamsberger, H.; Huisgen, R. Chem. Commun. 1971, 1190
O
N2
OMe
O
O
OMe
O
O
OMe
O+
MeOOC-C C-COOMe
OCOOMe
COOMe
O
MeO
Cu
- N2
: _
Ueda, K.; Ibata, T.; Takebayashi, M. Bull. Chem. Soc. Jpn 1972, 45, 2779
57
N2
Ph Ph
O
Ph Ph
Ph PhO+Ph
Ph Ph
Ph O
PhPh
Ph Ph
hνtBuOH matrix/
- 196 C
- N2
: _
Tomioka, H.; Miwa, T.; Suzuki, S.; Izawa, Y. Bull. Chem. Soc. Jpn 1980, 53, 753
(iv) Nitrile ylideReviews:Huisgen, R.; Grashey, R.; Sauer, J. in The Chemistry of Alkenes, (S. Patai, ed.) Wiley-Interscience: New York, 1964, p. 806Padwa, A.; Carlsen, P.H.J. Reactive Intermediates 1982, 2, 55Hansen, H.J.; Hiemgartner, H. in 1,3-Dipolar Cycloaddition Chemistry, (A. Padwa, ed.) Wiley: New York, 1984, p. 177Wentrup, C.; Reisinger, A.; Qiao, G.G.; Visser, P. Pure Appl. Chem. 1997, 69, 847
N
Ph Cl NO2
Ph N+
H
NO2
CN
NPh
CN
NO2
_
- Et3NH+ Cl-
NEt3
Huisgen, R.; Stangl, H.; Sturm, H.J.; Wagenhofer, H. Angew. Chem. 1962, 74, 31Huisgen, R.; Stangl, H.; Sturm, H.J.; Wagenhofer, H. Angew. Chem. Int. Ed. 1962, 1, 50Huisgen, R. Angew. Chem. Int. Ed. 1963, 2, 565; 633Huisgen, R.; Raab, R. Tetrahedron Lett. 1966, 649Huisgen, R. Helv. Chim. Acta 1967, 50, 2421Huisgen, R. J. Org. Chem. 1968, 33, 2291Huisgen, R. J. Org. Chem. 1976, 41, 403
58
Turro, N.J.; Cha, Y.; Gould, I.R.; Padwa, A.; Gasdaska, J.R.; Thomas, M. J. Org. Chem. 1985, 50, 4415
N CH2CH3
A B
A B
N
B A
N_+CH3CNhν
- N2
CH2:CH2N2
Padwa, A.; Gasdaska, J.R.; Thomas, M.; Turro, N.J.; Cha, Y.; Gould, I.R. J. Am. Chem. Soc. 1986, 108, 6739Turro, N.J.; Cha, Y.; Gould, I.R. J. Am. Chem. Soc. 1987, 109, 2101
N
Cl
Ar
R2
R1
NAr
R1
R2 N
Ar R1
R2
Ar = p-NO2-C6H4; R1 = {H, CF3}; R2 = {H, CF3}
hν+
- HCl
_
Hegarty, A.F.; Eustace, S.J.; Tynan, N.M.; Pham-Tran, N.N.; Nguyen, M.T. J. Chem. Soc. Perkin Trans. 2 2001, 1239Fergus, S.; Eustace, S.J.; Hegarty, A.F. J. Org. Chem. 2004, 69, 4663
(v) Thiocarbonyl ylide
Reviews:Mloston, G.; Heingartner, H. Pol. J. Chem. 2000, 74, 1503 (thiocarbonyl ylides)Mloston, G.; Heingartner, H. Chem. Heterocyclic Compounds 2002, 59, 315 (thiocarbonyl ylides)
59
S+
R
R
O
O
O
S
OR
RO
O
_
+
Wittig, G.; Knaus, E.; Niethammer, K. Ann. Chem. 1960, 630, 10Mayer, R.; Kleinert, H.; Richter, S.; Gewald, K. Angew. Chem. 1962, 74, 118Pedersen, C.T. Acta Chem. Scand. 1966, 20, 2314
NN
SR1 R2 S+R1 R2
S
R1 R2
R3C CR4
SR1 R2
R3 R4- N2
_
Kellogg, R.M.; Wassenaar, S. Tetrahedron Lett. 1970, 1987Buter, J.; Wassenaar, S.; Kellogg, R.M. J. Org. Chem. 1972, 37, 4045
Ueno, Y.; Okawara, M. Bull. Chem. Soc. Jpn 1972, 45, 1797Kellogg, R.M. J. Org. Chem. 1973, 38, 844Buter, J.; Raynolds, P.W.; Kellogg, R.M. Tetrahedron Lett. 1974, 2901
60
Ph Ph
S
tBu tBu
SPh Ph
S+
tBu
tBu
S+ Ph
Ph
:
_
_+
McGimpsey, W.G.; Scaiano, J.C. Tetrahedron Lett. 1986, 27, 547
XR1
R2
N
R3
N N
R2
N R3
R1
N O
N R2
R1
C NR1 N
R2
nitrosoimines::
+
_
azonium imines
_
+
::carbonyl imines (X = O)
thiocarbonyl imines (X = S)azomethine imines (X = N-R)
_ ::
+
nitrene traps
::nitrilimines
+ _
(i) AzomethinesReviews:Boyer, J.H. Mechanisms of Molecular Migrations 1969, 2, 267
61
Bach, F.L. Jr.; Karliner, J.; van Lear, G.E. Chem. Commun. 1969, 1110
Boyer, J.H.; Frints, P.J.A. J. Heterocyclic Chem. 1970, 7, 59; 71 Ph
O
N
O
Ph
Ph
O
O
PhN+
hν_
Barik, R.; Kumar, C.V.; Das, P.K.; George, M.V. J. Org. Chem. 1985, 50, 4309
N3
CN
CN
NC
NC
N+
NC
CN
CN
NC
+hν
- N2
_
Murata, S.; Abe, S.; Tomioka, H. J. Org. Chem. 1997, 62, 3055
(ii) Azonium iminesReviews:None.
(iii) Carbonyl iminesReviews:Kayam, R.; Shizuka, H.; Sekiguchi, S.; Matsui, K. Bull. Chem. Soc. Jpn 1975, 48, 3309Tomioka, H. Bull. Chem. Soc. Jpn 1998, 71, 1501
(iv) Nitrilimines
62
Reviews:Granier, M.; Baceiredo, A.; Gruetzmacher, H.; Pritzkow, H.; Bertand, G. Angew. Chem. Int. Ed. 1990, 102, 671
(v) NitrosoiminesReviews:Akiba, K.; Inamoto, N. Heterocycles 1977, 7, 1131Challis, B.C.; Challis, J.A. in The Chemistry of Amino, Nitroso, Nitro Compounds and Their Derivatives (S. Patai, ed.) Wiley: Chichester, 1982,Vol. 2, p. 1151
(vi) Thiocarbonyl iminesReviews:None.
Doering-Zeiss intermediate H
O
RR1
R3R2
X H O
R
63
CH3
Et
O
O
HOOC
CH3
EtiPrCH2
O O
Me
HO
Ar
H OMe
CH3
EtiPrCH2
O+
Me
H
CH3
MeO Et
CH2iPr
CH3
EtiPrCH2
O
Me
HO
Me
H
CH3
EtiPrCH2
O+
Me
H
CH3
OMeEt
iPrCH2
MeOH
- ArCOO-
- H+- H+
- MeOH
- MeOH
- ArCOOH- OMe-
Doering, W.v.E.; Zeiss, H.H. J. Am. Chem. Soc. 1953, 75, 4733
Enols and Enolates
OH
R1
R2
R3
O -
R1
R2
R3 + H+
64
Reviews:Toullec, J. Adv. Phys. Org. Chem. 1982, 18, 1Rappoport, Z.; Biali, S.E. Acc. Chem. Res. 1988, 21, 442 (sterically crowded simple enols)Rappoport, Z. (ed.) The Chemistry of Enols, Wiley: Chichester, 1990
Kresge, A.J. Acc. Chem. Res. 1990, 23, 43Rochlin, E. Pure Appl. Chem. 1997, 69, 1933Wirz, J. Pure Appl. Chem. 1998, 70, 2221
Erlenmeyer, E. Chem. Ber. 1875, 8, 309 (first suggestion)Erlenmeyer, E. Chem. Ber. 1881, 14, 320Wheeler, A.S.; Edwards, V.C. Ann. Chem. 1895, 286, 27Knorr, L. Ann. Chem. 1899, 306, 363Lapworth, A.; Hann, A.C.O. J. Chem. Soc. 1902, 1508Lapworth, A. J. Chem. Soc. 1904, 30Moore, T.S. J. Chem. Soc. 1907, 91-92, 1373Dimroth, O. Chem. Ber. 1907, 40, 2404Zelinsky, N.; Schlesinger, N. Chem. Ber. 1907, 40, 2886Wohl, A.; Claussner, P. Chem. Ber. 1907, 40, 2308Wohl, A. Chem. Ber. 1907, 40, 2282Stoermer, R.; Martinsen, O. Ann. Chem. 1907, 352, 322Petrenko-Kritshenko, P. J. Russ. Phys. Chem. Soc. 1907, 39, 179Hantzsch, A. Chem. Ber. 1907, 40, 15; 23; 42
Stobbe, H. Ann. Chem. 1907, 352, 132Henle, F. Ann. Chem. 1907, 352, 45Piutti, A. Gazz. Chim. Ital. 1907, 36, 364Bulow, C.; Busse, F. Chem. Ber. 1906, 39, 3861Kohler, E.P. Am. Chem. J. 1907, 36, 529Meyer, K.H. Ann. Chem. 1911, 380, 212;220Meyer, K.H.; Kappelmeier, P. Chem. Ber. 1911, 44, 2718Meyer, K.H. Chem. Ber. 1912, 45, 2843;2864Meyer, K.H. Chem. Ber. 1914, 47, 826Dieckmann, W. Chem. Ber. 1922, 55B, 2470Conant, J.B.; Thompson, A.F. Jr. J. Am. Chem. Soc. 1932, 54, 4039Ingold, C.K.; Wilson, C.L. J. Chem. Soc. 1934, 773
65
Pedersen, K.J. J. Phys. Chem. 1934, 38, 581Bartlett, P.D.; Stauffer, C.H. J. Am. Chem. Soc. 1935, 57, 2580Hsu, S.K.; Wilson, C.L. J. Chem. Soc. 1936, 623Reitz, O. Z. Phys. Chem. A 1937, 179, 119Hsu, S.K.; Ingold, C.K.; Wilson, C.L. J. Chem. Soc. 1938, 78
OH
OH
H2N
Polce, M.J.; Wesdemiotis, C. J. Mass. Spectrom. 2000, 35, 251
Episulfonium ions (thiiranium ions)
S+
R1
R3 R4
R2 R5
Reviews:
Schmid, G.H.; Garratt, D. in The Chemistry of Double Bonded Functional Groups, (S. Patai, ed.) Wiley: New York, 1977, Chapter 9Smit, W.A.; Zefirov, N.S.; Bodrikov, I.V.; Krimer, M.Z. Acc. Chem. Res. 1979, 12, 282Smit, V.A.; Zefirov, N.S.; Bodrikov, I.V. in Organic Sulfur Chemistry, Invited Lecture Int. Symp., (R.K. Friedlina; A.E. Skorova, eds.) Pergamon:Oxford, 1981, p. 159Harring, S.R.; Edstrom, E.D.; Livinghouse, T. Adv. Heterocyclic Natural Product Synthesis 1992, 2, 299Pasquato, L.; Destro, R.; Lucchini, V.; Modena, G. Phosphorus, Sulfur, Silicon and the related Elements 1999, 153-154, 235
66
S+
Br
S+ S
Me2S + BrCH2CH2Br Br- CH3Br + CH3SCH2CH2Br
CH3SCH2CH2BrBr-
CH3Br +
Cahours, A. Ann. Chem. 1865, 135, 354Cahours, A. Ann. Chem. 1865, 136, 151Cahours, A. Compt. Rend. 1865, 60, 620; 1174Ray, F.E.; Levine, I. J. Org. Chem. 1937, 2, 267
Cl
S
ClS+ClCH2CH2
Cl
S
OHH2O
- Cl-
Peters, R.A.; Walker, E. Biochem. J. 1923, 17, 260Ogston, A.G.; Holiday, E.R.; St. L. Philpot, J.; Stocken, L.A. Trans. Faraday Soc. 1948, 44, 45Bartlett, P.D; Swain, G. J. Am. Chem. Soc. 1949, 71, 1406
OHEtS OH2EtSS+
Et
Et
S
Cl
Cl-
- H2O
H+
+
Fuson, R.C.; Speziale, A. J. Am. Chem. Soc. 1940, 71, 1582Fuson, R.C.; Price, C.C.; Burness, D.M. J. Org. Chem. 1946, 11, 475
Sulfenium ions
67
R S+
Reviews:Parker, A.; Kharasch, N. Chem. Rev. 1959, 59, 583Kharasch, N. in Organic Sulfur Compounds, (N. Kharasch, ed.) Pergamon Press: London, 1961, p. 375 - 396Okuyama, T. in Chemistry of Sulfenic Acids and their Derivatives, (S. Patai, ed.) Wiley: Chichester, 1990, p. 743 - 763
S
NO2
O2N
Cl
S+
NO2
O2N
Cl
H
S+
NO2
O2N100 % H2SO4
HSO4-
+ Cl-
Kharasch, N.; Buess, C.M.; King, W. J. Am. Chem. Soc. 1953, 75, 6035Robinson, E.A.; Zaidi, S.A.A. Can. J. Chem. 1966, 46, 3927
R-S-S-R' + H+R-S+ + R'-SH
R-S-S-R' + R'-S+R-S+ + R'-S-S-R'
R-S+ + R-SHR-S-S-R + H+
Benesch, R.E.; Benesch, R. J. Am. Chem. Soc. 1958, 80, 1666
68
S+
Me
NMe2
NMe2
HOSO3-
Neunhöffer, O.; Nowak, A. Naturwiss. 1958, 45, 491
COOH
SH
COOH
SOH
COOH
S+
COOH
S
Br
S
O
Br
H2SO4
- OH-
Ph-Br
- H+ - H2O
Gilman, H.; Diehl, J.W. J. Org. Chem. 1959, 24, 1914
69
Ph S COOH
X1
X
X2
X3Ph S+
X1
XCOOH
X2
X3+ _
X2, X3 = H, Ph
Iskander, Y.; Tewfik, R. J. Chem. Soc. 1961, 2393
S
R
Ar
Ar
Ar
Ar
Ar = p-O2N-C6H4
+ R-S+_
Iskander, Y.; Riad, Y. J. Chem. Soc. 1961, 2397
SO3- Ag+
NO2O2N
NO2
SO3- +SCH3
NO2O2N
NO2
N
SO3-
NO2O2N
NO2
N+
SCH3
+ CH3Br- AgBr
Helmkamp, G.K.; Owsley, D.C. Quart. Rep. Sulfur Chem. 1967, 2, 303Helmkamp, G.K.; Owsley, D.C.; Barnes, W.M.; Cassey, H.N. J. Am. Chem. Soc. 1968, 90, 1635
Sulfonium Ions
70
R2
S+
R1 R3
Reviews:Stirling, C.J.M. in Organic Chemistry of Sulfur, (S. Oae, ed.) Plenum: New York, 1977, p. 473Barrett, G.C. Compr. Org. Chem. 1979, 3, 105Stirling, C.J.M. (ed.) Chemistry of the Sulphonium Group, Vol. 1, 2, Wiley: Chichester, 1981Wilson, G.E. Jr. Tetrahedron 1982, 38, 2597Capozzi, G.; Modena, G. Studies in Org. Chem. (Amsterdam) 1985, 19, 246Anklam, E.; Margaretha, P. Res. Chem. Intermed. 1989, 11, 127Ando, W.; Matsuyama, H. in Nitrogen, Oxygen, and Sulfur Ylide Chemistry, (J.S. Clark, ed.) Oxford University Press: Oxford, 2002, p. 175Nenaidenko, V.G.; Balenkova, E.S. Russ. J. Org. Chem. 2003, 39, 291
Et3S+ I-Et2S + Et-I
von Oefele, A. Ann. Chem. 1864, 132, 82
Me
S+
PhCH2 CH2Ph
Me
S+
PhCH2 Me
Me3S+ I-Me2S + MeI
PhCH2I + Me2SI-
PhCH2SMe + MeI
PhCH2I + PhCH2SMeI-PhCH2SCH2Ph + MeI
Schöller, C. Chem. Ber. 1874, 7, 1274Ray, F.E.; Levine, I. J. Org. Chem. 1937, 2, 267
71
Et3S+ I- + H2S3 EtSH + HI
Cahours, A. Compt. Rend. 1875, 80, 1317Cahours, A. Compt. Rend. 1875, 81, 1163Ray, F.E.; Levine, I. J. Org. Chem. 1937, 2, 267
Collier, H.B.; Allen, D.E. Can. J. Res. 1942, 20B, 284
Et
S+
Me Me
HO
O2N
O2N
NO2 - O
O2N
O2N
NO2- HNO3
Me2S++Me3S+ NO3-
Me3S+ NO3-Me2S + CH3NO3
EtNO3 + Me2SNO3-CH3NO3 + MeSEt
Ray, F.E.; Szasz, G.J. J. Org. Chem. 1943, 8, 121
Hughes, E.D.; Ingold, C.K.; Maw, G.A. J. Chem. Soc. 1948, 2072Hughes, E.D.; Ingold, C.K.; Maw, G.A.; Woolf, L.I. J. Chem. Soc. 1948, 2077
Extended Cumulenones
Reviews:Runge, W. Prog. Phys. Org. Chem. 1981, 13, 315
Propadienones (methyleneketenes)
72
C
R1
R2
C O
Reviews:Brown, R.F.C.; Eastwood, F.W. in The Chemistry of Ketenes, Allenes, and Related Compounds, Part 2, (S. Patai, ed.) Wiley: New York, 1980,Chapter 19, p. 757Brown, R.F.C.; Eastwood, F.W. Synlett 1993, 9Gaber, A. El-A.; McNab, H. Synthesis 2001, 2059
O
O
PhCH
O
O
PhC CH
O
O
CHPhPhCH
430 CPhCH=C=C=O
- CO2- acetone
550 C- CO2- CO- acetone
PhNH2
MeOH
PhCH=CH(CO)NHPh
PhCH=CHCOOMedimerization
Brown, R.F.C.; Eastwood, F.W.; Harrington, K.J. Austr. J. Chem. 1974, 27, 2373
73
O
OPh
O
O
C
Ph
HH
C O C
Ph
H
HPh:560 C
- CO2- acetone
- CO
Brown, R.F.C.; Eastwood, F.W.; Harrington, K.J.; McMullen, G.L. Austr. J. Chem. 1974, 27, 2393
O
O
O
O
O
O
O
O
O O
O
O
O
O
COOH
OO
O
O
O
O
O
C
H
H
C O
CO
OO
CH2=C=O: - CO
- CO2- acetone
540 C
mCPBA
- CO2- acetone
495 C+
H2O
- acetone
CH2=C=C=O
Brown, R.F.C.; Eastwood, F.W.; McMullen, G.L. J. Am. Chem. Soc. 1976, 98, 7421Brown, R.F.C.; Eastwood, F.W.; McMullen, G.L. Austr. J. Chem. 1977, 30, 179
74
N
O
NC C O
COOMe COOMe
MeOH+
254 nm
Mazzocchi, P.H.; Bowen, M.W.; Kachinsky, J. Chem. Commun. 1977, 53
O
O
O
O
C C O- CO2- acetone
FVT(CH2)n
n = 2, 3, 4, 5, 6, 10
(CH2)n
Baxter, G.J.; Brown, R.F.C. Austr. J. Chem. 1978, 31, 327
H
Ph O
Ph
O
O
O
H
CH=CH2
O
Ph2C=O + CH2=C=C=O
HOOC-CH=CH2 + CH2=C=C=O
Blackman, G.L.; Brown, R.D.; Brown, R.F.C.; Eastwood, F.W.; McMullen, G.L.; Robertson, M.L. Austr. J. Chem. 1978, 31, 209
75
O
O
N2
O
O
OC
OHC CH
650 C
- N2
major
minor
CH2=C=C=O + CO2
O=C=C=C=O + CH2=O
CO +
Chapman, O.L.; Miller, M.D.; Pitzenberger, S.M. J. Am. Chem. Soc. 1987, 109, 6867
Br
COOH
R1
R2
C
R1
R2
C O
Br
COCl
R1
R2
C
R1
R2
C O
C
R1
R2
C O
O
O
R1
R2
R2
R1
R1 = Me, Ph, H; R2 = Me, Ph, Me
2
+ Mn(CO)5Br + [Ph3P-N=PPh3]+ Cl-
+ Mn(CO)5Br + [Ph3P-N=PPh3]+ Cl-
1. SOCl22. [Ph3P-N=PPh3]+ [Mn(CO)5]-
[Ph3P-N=PPh3]+ [Mn(CO)5]-
Masters, A.P.; Sorensen, T.S.; Tran, P.M. Can. J. Chem. 1987, 65, 1499
76
O
O
O
CO
C C O:
:- CO2- CO
- CO2 CO
77
O
O
O
O
O
O
O
CF3
H O
C C OO
OO
O
C C O
O
CF3
O
- CF3COOH
- CH2=CH2
- CH2=CH2
- CF3COOH
- CO2- acetone
FVPFVP
- CH2=CH2- CO2- acetone
Brown, R.F.C.; Browne, N.R.; Coulston, K.J.; Eastwood, F.W.; Irvine, M.J.; Pullin, D.E.; Wiersum, U.E. Austr. J. Chem. 1989, 42, 1321
F
F
O
O
C
F
F
C O
2
Brahms, J.C.; Dailey, W.P. J. Am. Chem. Soc. 1989, 111, 3071
78
O
O
O
C
F
F
C O
F
F
FVP
- CO2
Brahms, J.C.; Dailey, W.P. J. Am. Chem. Soc. 1989, 111, 8940
OR
R
O
N2
O C
R
R
C O+- N2
FVP
Brahms, J.C.; Dailey, W.P. Tetrahedron Lett. 1990, 31, 1381
S
S
C C O
S
S
O
O
O
O
FVT
- CO2- acetone
Chuburn, F.; Lacombe, S.; Pfister-Guillouzo, G.; Chiek, A.B.; Chuche, J.; Pommelet, J.C. J. Am. Chem. Soc. 1991, 113, 1954
Butatrienones
79
C
R1
R2
C C O
Reviews:None.
C
O
O
O
CF3H
+ CF3COOHCH2=C=C=C=OFVP
Brown, R.D.; Brown, R.F.C.; Eastwood, F.W.; Godfrey, P.D.; McNaughton, D. J. Am. Chem. Soc. 1979, 101, 4705
X
O
O
O
O
X
X = CH2, O
+ CO2 + Me2C=O + CH2=C=C=C=OFVP
Brown, R.F.C.; Coulston, K.J.; Eastwood, F.W.; Gatehouse, B.M.; Guddatt, L.W.; Pfenninger, M.; Rainbow, I. Austr. J. Chem. 1984, 37, 2509
80
O O
COOH
O O
C
C
O
C C C O
C
H
COOH
C C C O- H2O
- CO- CH2=O
- H2O
Brown, R.F.C.; Coulston, K.J.; Eastwood, F.W.; Irvine, M.J. Austr. J. Chem. 1991, 44, 87
O O
Cevasco, G.; Pardini, R.; Thea, S. Eur. J. Org. Chem. 1998, 665
Heterocumulenones (iminopropadienones)
Reviews:Wentrup, C.; Kappe, C.O.; Wong, M.W. Pure Appl. Chem. 1995, 67, 749Yranzo, G.I.; Elguero, J.; Flammang, R.; Wentrup, C. Eur. J. Org. Chem. 2001, 2209
N
NHN
O
R O
O
ORNH
R1
O
O
R = Me, Ph; R1 = MeS, Me2N
FVPR-N=C=C=C=O
FVP
81
Mosandl, T.; Kappe, C.O.; Flammang, R.; Wentrup, C. Chem. Commun. 1992, 1571Mosandl, T.; Stadtmuller, S.; Wong, M.W.; Wentrup, C. J. Phys. Chem. 1994, 98, 1080Kappe, C.O.; Flammang, R.; Wentrup, C. Heterocycles 1994, 37, 1615
O
ORNH
X
O
O
O
O
C
O
O
RN
RN C
X
O
C O
X
RN
R = Ph, iPr, tBuX = SMe, NMe2, OMe, tBu-NH
FVT
- HX - CO2- acetone
RN=C=C=C=O
FVT- CO2- acetone
[1,3]-X
Moloney, D.W.J.; Wong, M.W.; Flammang, R.; Wentrup, C. J. Org. Chem. 1997, 62, 4240
N
N
O
X
N N=C=C=C=O
X = SMe, Cl, NMe2, NEt2, OMe
FVP
Plug, C.; Frank, W.; Wentrup, C. J. Chem. Soc. Perkin Trans. 2 1999, 1087
82
N N
N NHAr
O
N N
N+ N-Ar
O
O
O
O
O
Ar-NH
R1
N
NHN
O
Ar O
_
R-N=C=C=C=O
Shtaiwi, M.; Wentrup, C. J. Org. Chem. 2002, 67, 8558
Halonium Ions
X
R2 R3
R1 R4X = Cl, Br, I
+
Reviews:Sandin, R.B. Chem. Rev. 1943, 32, 249Banks, D.F. Chem. Rev. 1966, 66, 243Crist, D.R.; Leonard, N.J. Angew. Chem. Int. Ed. 1969, 8, 962Peterson, P.E. Acc. Chem. Res. 1971, 4, 407Olah, G.A. Aldrichimica Acta 1973, 6, 7
83
Olah, G.A. Halonium Ions, Wiley-Interscience: New York, 1975Grushin, V.V. Acc. Chem. Res. 1992, 25, 529Ruasse, F. Adv. Phys. Org. Chem. 1993, 28, 207Koser, G.F. in The Chemistry of Halides, Pseudo-Halides, Azides (S. Patai, Z. Rappoport, eds.) Wiley: Chichester, 1983, Vol. 2, p. 1265Koser, G.F. in The Chemistry of Halides, Pseudo-Halides, Azides (S. Patai, Z. Rappoport, eds.) Wiley: Chichester, 1995, Vol. 2, p. 1173
COOHHOOC COOHHOOC
Br+ Br
Br
COOH
HOOC
COOH
HOOC
COOH
HOOC
Br+ Br
Br
COOH
HOOC
Br
Br COOH
HOOC
Br-Br2
Br-Br2
McKenzie, A. Proc. Chem. Soc. 1911, 27, 150McKenzie, A. J. Chem. Soc. 1912, 101, 1196Frankland, P.F. J. Chem. Soc. 1912, 101, 673Kuhn, R.; Wagner-Jauregg, T. Chem. Ber. 1928, 61, 519
COOHCH3CH CHCOOH
I+
COOH
Cl I
Cl-ICl
Ingold, C.K.; Smith, H.G. J. Chem. Soc. 1931, 2742
Roberts, I.; Kimball, G.E. J. Am. Chem. Soc. 1937, 59, 947
84
Ph
Br+
Ph
Br
Ph
Br
Ph
Br
Ph
MeO OMe
Ph
Br
Br2 +
- Br-
+ MeOH
majorBartlett, P.D.; Tarbell, D.S. J. Am. Chem. Soc. 1936, 58, 466
COO -
- OOC Cl+
COO -
- OOC
O
O
COO -
Cl
- Cl-
Cl2
Tarbell, D.S.; Bartlett, P.D. J. Am. Chem. Soc. 1937, 59, 407
Lucas, H.J.; Winstein, S. J. Am. Chem. Soc. 1939, 61, 1576; 2845Lucas, H.J.; Garner, H.K. J. Am. Chem. Soc. 1950, 72, 2145Lucas, H.J.; Gould, C.W. Jr. J. Am. Chem. Soc. 1941, 63, 2541Barton, D.H.R.; Miller, E.; Young, H.T. J. Chem. Soc. 1951, 2698
Lemieux, R.U.; Fraser-Reid, B. Can. J. Chem. 1965, 43, 1458Olah, G.A.; Bollinger, J.M. J. Am. Chem. Soc. 1967, 89, 4744
Cl+ Br+I- Cl-
85
Sandin, R.B.; Hay, A.S. J. Am. Chem. Soc. 1952, 74, 274 (first stable bromonium and chloronium salts)
Hydronium ions
H
O
H H
+
Reviews:Williams, J.H. in Hydrogen Bond (P. Schuster, G. Zundel, C. Sandorfy, eds.) North-Holland: Amsterdam, 1976, Vol. 2, p. 655Lundgren, J.O.; Olovsson, I. in Hydrogen Bond (P. Schuster, G. Zundel, C. Sandorfy, eds.) North-Holland: Amsterdam, 1976, Vol. 2, p. 471
Giguere, P.A. J. Chem. Educ. 1979, 56, 571
(SO2 solvent)H3O+ Br-H2O + HBr
Bagster, L.S.; Cooling, G. J. Chem. Soc. 1920, 117, 693
H3O+ HBF3-H3O+ NO3
-H3O+ ClO4-
Volmer, M. Ann. Chem. 1924, 440, 200Klinkenberg, L.J.; Ketelaar, J.A.A. Rec. Trav. Chim. 1935, 54, 959Richards, R.E.; Smith, J.A.S. Trans. Faraday Soc. 1951, 47, 1261Kakiuchi, H.; Shono, H.; Komatsu, K.; Kigoshi, K. J. Chem. Phys. 1951, 19, 1069Bethell, D.E.; Sheppard, N. J. Chem. Phys. 1953, 21, 1421
Iminium Ions
N
R1
R2
R4
R3
+
86
Reviews:Paukstelis, J.V. in Enamines: synthesis, structure, and reactivity (G. Stork, ed.) Marcel Dekker: New York, 1969, p. 169Pihlaja, K. in The Chemistry of Amidines, Imidates (S. Patai, Z. Rappoport, eds.) Wiley: Chichester, 1991, Vol. 2, p. 323
Stewart, T.D.; Bradley, W.E. J. Am. Chem. Soc. 1932, 54, 4172Julg, A.; Carles, P. Compt. Rend. 1960, 251, 1782
Janovsky complex
Reviews:None.
O
R
NO2
O2N O2N
NO2
H O
R+ _NaX
Na+
- HX
Janovsky, J.V. Chem. Ber. 1886, 19, 2155
Ketenes
C C
R1
R2
O
Reviews:Staudinger, H. Die Ketene, Verlag Enke: Stuttgart, 1912Patai, S. (ed.) The Chemistry of Ketenes, Allenes, and Related Compounds, Wiley: Chichester, 1980Dötz, K.H.; Fuengen-Koester, B. Chem. Ber. 1980, 113, 1449
Tidwell, T.T. Ketenes, Wiley: New York, 1995Kollenz, G.; Heilmayer, W.; Kappe, C.O.; Wallfisch, B.; Wentrup, C. Croatica Chem. Acta 2001, 74, 815
87
Kirmse, W. Eur. J. Org. Chem. 2002, 2193Singh, G.S.; Mdee, L.K. Curr. Org. Chem. 2003, 7, 1821
C C
R1
R2
O
O
R1
N2
R2
O
R1
R2
:
hν or ∆
- N2
O
ClPh
PhCl
C C
Ph
Ph
O- ZnCl2
Zn
Staudinger, H. Chem. Ber. 1905, 38, 1735Staudinger, H. Chem. Ber. 1907, 40, 1145Staudinger, H. Ann. Chem. 1908, 356, 51Wilsmore, N.T.M. Proc. Chem. Soc. 1908, 23, 229Wilsmore, N.T.M. J. Chem. Soc. 1908, 91-92, 1938Collie, J.N. Proc. Chem. Soc. 1908, 23, 280Wilsmore, N.T.M.; Stewart, A.W. Proc. Chem. Soc. 1908, 23, 309Collie, J.N. J. Chem. Soc. 1908, 91-92, 1806Smith, L.I.; Hoehn, H.H. Org. Synth. Coll. Vol. 1955, 3, 356Taylor, E.C.; McKillop, A.; Hawks, G.H. Org. Synth. 1972, 52, 36
Staudinger, H.; Klever, H.W. Chem. Ber. 1908, 41, 594Staudinger, H.; Klever, H.W. Chem. Ber. 1908, 41, 906Wilsmore, N.T.M.; Stewart, A.W. Chem. Ber. 1908, 41, 1025Staudinger, H.; Klever, H.W. Chem. Ber. 1908, 41, 1516Staudinger, H. Chem. Ber. 1908, 41, 1355
88
Staudinger, H. Chem. Ber. 1908, 41, 1493Staudinger, H.; Ott, E. Chem. Ber. 1908, 41, 2208Schroeter, G. Chem. Ber. 1909, 42, 2336Staudinger, H.; Kubinsky, J. Chem. Ber. 1909, 42, 4213Staudinger, H.; Bereza, S. Chem. Ber. 1909, 42, 4908Staudinger, H.; Klever, H.W.; Kober, P. Ann. Chem. 1910, 374, 1Leuchs, H.; Theodorescu, G. Chem. Ber. 1910, 43, 1239Schmidlin, J.; Bergman, M. Chem. Ber. 1910, 43, 2821Schmidlin, J.; Huber, M. Chem. Ber. 1910, 43, 2824Staudinger, H.; Jelagin, S. Chem. Ber. 1911, 44, 365Staudinger, H. Chem. Ber. 1911, 44, 521; 533; 543Staudinger, H.; Bereza, S. Ann. Chem. 1911, 380, 243Staudinger, H.; Ruzicka, L. Ann. Chem. 1911, 380, 278Staudinger, H. Chem. Ber. 1911, 44, 1619Staudinger, H.; Ott, E. Chem. Ber. 1911, 44, 1631Staudinger, H.; Kupfer, O. Chem. Ber. 1911, 44, 1638; 2194Staudinger, H.; Kon, N. Ann. Chem. 1912, 384, 38Staudinger, H. Ann. Chem. 1912, 387, 254Staudinger, H.; Kupfer, O. Chem. Ber. 1912, 45, 501Staudinger, H. Z. Angew. Chem. 1914, 27, 354Staudinger, H.; Gohring, O.; Scholler, M. Chem. Ber. 1914, 47, 40Staudinger, H.; Maier, J. Ann. Chem. 1914, 401, 292Staudinger, H.; Hirzel, H. Chem. Ber. 1916, 49, 2522
O O
H
OH
..hν
89
O
RO
H
RO
O
H
hν
Quinkert, G.; Wegemund, B.; Blanke, E. Tetrahedron Lett. 1962, 221
O
CHCl2
O
CHCl2
hν
O
Cl
Cl
Cl
Cl
O
Cl
Cl
Cl
Cl
hν
Chapman, O.L.; Lassila, J.D. J. Am. Chem. Soc. 1968, 90, 2449
Metal Ketenides
C C
M
M
O
Reviews:None.
90
O
O- Ag+
O
O
O
C C
Ag
Ag
O
O
OH
+ 32pyridine
+
Blues, E.T.; Bryce-Smith, D.; Hirsch, H.; Simons, M.J. J. Chem. Soc. D 1970, 699Bryce-Smith, D.; Blues, E.T. DE 2,047,373 (1971)Bryce-Smith, D. Chem. Ind. 1975, 154
C C
Cu
Cu
O
Blues, E.T.; Bryce-Smith, D.; Kettlewell, B.; Roy, M. Chem. Commun. 1973, 921
C C
Au
Au
O
Blues, E.T.; Bryce-Smith, D.; Lawston, I.W.; Wall, G.D. Chem. Commun. 1974, 513
Ketene zwitterions
R1
R2
O -
N+ R5
R3 R4
R1
R2
O -
N
R1
R2
O -
P+ R5
R3 R4
R1
R2
O -
S+ R4
R3
+
91
Reviews:None.
C C
EtOOC
EtOOC
O
N
R
O
EtOOC
EtOOCN+
R+
_
Gompper, R.; Wolf, U. Ann. Chem. 1979, 1388
C
O
NHN
C- O N
NHO N2
hν
- N2
+
+
Pacansky, J.; Chang, J.S.; Brown, D.W.; Schwarz, W. J. Org. Chem. 1982, 47, 2233
C
O
- O3SN
C
- O
- O3S
N+
+
Barra, M.; Fisher, T.A.; Cenigliaro, G.J.; Sinta, R.; Scaiano, J.C. J. Am. Chem. Soc. 1992, 114, 2630
92
Ketyl Radicals and Ketyl Radical Ions
OH
R1 R2
O -
R1 R2
+ H+..Reviews:Michaelis, L. Chem. Rev. 1935, 16, 243Holy, N.L.; Marcum, J.D. Angew. Chem. Int. Ed. 1971, 10, 115Netto-Ferreira, J.C.; Scaiano, J.C. Res. Chem. Intermediates 1989, 12, 187
O
Ar Ar
O - Na+
Ar Ar
Na+ - O
O- Na+
Ar
Ar
Ar
Ar
.Na orMg-MgI2
O
Ar
O
Ar
O -
Ar
O
ArKOH
K+
.Laurent, A. Ann. Chim. Phys. 1835, 59, 367Laurent, A. Ann. Chim. Phys. 1836, 17, 89; 91Liebermann, C.; Homeyer, J. Chem. Ber. 1879, 12, 1971Bamberger, E. Chem. Ber. 1885, 18, 865Beckmann, E. Chem. Ber. 1889, 22, 912Beckmann, E.; Paul, T. Ann. Chem. 1891, 266, 1Schlenk, W.; Weichel, T. Chem. Ber. 1911, 44, 1182Schlenk, W.; Thal, A. Chem. Ber. 1913, 46, 2840Schlenk, W.; Appenrodt, J.; Michael, A.; Thal, A. Chem. Ber. 1914, 47, 473
93
O
O
O
O
O
OH
O
O
O -
O
O
O .KOH/EtOH
K+
Fischer, E. Ann. Chem. 1882, 211, 314
Weitz, E.; Schwechten, H.W. Chem. Ber. 1926, 59, 2307Weitz, E.; Schwechten, H.W. Chem. Ber. 1927, 60, 545; 1203
Hantzsch, A. Chem. Ber. 1921, 54B, 1267
O
Ph
O
Ph
O
Ph
OH
Ph
O - K+
Ph
O
Ph
.+ KOH
2
Scholl, R. Chem. Ber. 1899, 32, 1809Scholl, R.; Hahle, H. Chem. Ber. 1923, 56B, 918
94
O - [MgBr]+
Ar Ar
O
Ar Ar
O - [MgBr]+
Ar Ar
O - [MgBr]+
Ar
[BrMg]+ - O
Ar
Ar
Ar
2 .
.+ Ph3C+ Ph3C-MgBr .
Gomberg, M.; Bachmann, W.E. J. Am. Chem. Soc. 1927, 49, 236Bachmann, W.E. J. Am. Chem. Soc. 1931, 53, 2758Bachmann, W.E. J. Am. Chem. Soc. 1933, 55, 770Bachmann, W.E. J. Am. Chem. Soc. 1933, 55, 1179Arbuzov, A.E.; Arbuzova, I.A. J. Gen. Chem. USSR 1932, 2, 388Nazarov, N. Compt. Rend. Acad. Sci. URSS 1934, 1, 123Nazarov, N. Compt. Rend. Acad. Sci. URSS 1934, 1, 325
magnetic susceptibility measurements:Sugden, S. Trans. Faraday Soc. 1934, 30, 18Wooster, C.R.; Dean, J.G. J. Chem. Soc. 1935, 57, 112Müller, E.; Teschner, F. Ann. Chem. 1936, 525, 1Anschutz, L. Chem. Ber. 1938, 71B, 1902Müller, E.; Wiesemann, W. Chem. Ber. 1936, 69, 2156Müller, E. Ann. Chem. 1938, 537, 86Müller, E. Angew. Chem. 1938, 51, 657Müller, E.; Janke, W. Z. Elektrochem. 1939, 45, 380Bowden, S.T.; John, T. J. Chem. Soc. 1940, 213
Meisenheimer-Jackson Complexes
95
O2N NO2
NO2
R1 R2
O2N NO2
NO2
R1 R2
O2N NO2
NO2
R1 R2
O2N N
NO2
R1 R2O -
O -
O2N NO2
N
R1 R2
- O O -
N NO2
NO2
R1 R2O -
- O
_
_
_
+
+
+
Reviews:Huisgen, R.; Sauer, J. Angew. Chem. 1960, 72, 91Huisgen, R.; Sauer, J. Angew. Chem. 1960, 72, 294Ross, S.D. Prog. Phys. Org. Chem. 1963, 1, 31Crampton, M.R. Adv. Phys. Org. Chem. 1969, 7, 211
96
NO2O2N
NO2
NO2O2N
NO2
H S
O
O
O -
- 2 Na+
Na2SO3
Jackson, C.L.; Robinson, W.S. Am. Chem. J. 1889, 11, 93Jackson, C.L.; Gazzolo, F.H. Am. Chem. J. 1900, 23, 376Jackson, C.L.; Earle, R.B. Am. Chem. J. 1903, 29, 89Meisenheimer, J., Ann. Chem. 1902, 323, 205
Servis, K. J. Am. Chem. Soc. 1965, 87, 5495 (NMR studies)
Mercurinium ions
Hg+
R2 R3
R1 R4
OAc
Reviews:Zefirov, N.S. Usp. Khim. 1965, 34, 1272Zefirov, N.S. Russ. Chem. Rev. 1965, 34, 527Chatt, J. Chem. Rev. 1951, 48, 7Kitching, W. Organometallic Chem. Rev. 1968, 3, 61
97
Hg+2
Hg+ OH + H++ Hg+2 + H2O
+ Hg+2
Lucas, H.J.; Hepner, F.R.; Winstein, S. J. Am. Chem. Soc. 1939, 61, 3102
Hg+
R
R
OAc
R AcO
HgOAc R
HO
HgOAc R
HO
NaBH4
- Hg- B(OH)3- NaOAc
- HOAc
H2OOAc-
- OAc-
Hg(OAc)2
Brook, A.G.; Wright, G.F. Can. J. Res. 1950, 28B, 623
Wright, G.F. Chemistry in Canada 1950, 2(9), 29
Wright, G.F. Ann. N.Y. Acad. Sci. 1957, 65, 436
Abercrombie, M.J.; Rodgman, A.; Bharucha, K.R.; Wright, G.F. Can. J. Chem. 1959, 37, 1328
Hg+ X HgX
ORX -ROH
HgX2
98
Traylor, T.G.; Baker, A.W. J. Am. Chem. Soc. 1963, 85, 2746
MeO
HgI
MeO+
HgI
H
HgI
CH2 CH2
MeO
HgI2
MeO+
HgI2
H
HgI2
MeO
HgI3
MeO+
HgI3
H
HgI3
CH2 CH2
CH2 CH2
- I-
I-
+ HgI2
+ HgI2
___
_ _
H+- MeOH
I-I-
H+- MeOH
I-I-
+ HgI2
+
- MeOHH+
Kreevoy, M.M.; Stokker, G.; Kretchmer, R.A.; Ahmed, A.K. J. Org. Chem. 1963, 28, 3184
Ichikawa, K.; Nishimura, N.; Takayama, S. J. Org. Chem. 1965, 30, 1593
99
PhCH2CH CH2
Hg+
OAc
PhCH2
AcO
PhCH2
HgOAc
OAc-+ Hg(OAc)2
Wolfe, S.; Campbell, P.G.C. Tetrahedron Lett. 1966, 4203Treibs, W.; Lucius, G.; Hogler, H.; Breslauer, H. Ann. Chem. 1953, 581, 59Treibs, W.; Bast, H. Ann. Chem. 1949, 561, 165
C
Hg+
X
C
HgX
RO
H
RO
HgX
H
RO- HgX+
H+
+
- H+
ROH
- X-
HgX2
100
Waters, W.L.; Kiefer, E.F. J. Am. Chem. Soc. 1967, 89, 6261Bach, R.D. Tetrahedron Lett. 1968, 5841Bach, R.D. J. Am. Chem. Soc. 1969, 91, 1771
Metal carbenoids
R1 R2
MLn
R1 R2
MLn
+
_
:
Reviews:Koebrich, G. Angew. Chem. Int. Ed. 1972, 11, 473Wulfman, D.S.; Poling, B. Reactive Intermediates 1980, 1, 321Miller, D.J.; Moody, C.J. Tetrahedron 1995, 51, 10811Bruce, M.I. Chem. Rev. 1998, 98, 2797
O
Ph
N2
O
Ph
O
Ph
H OR
∆
- N2 :
Cu ROH
Cu
Yates, P. J. Am. Chem. Soc. 1952, 74, 5376
101
Cl Cl
Li
H
Cl Cl
Li
H
Cl H
Cl
R
RCH=CH2:- LiCl
R-H + R-Li + CH2Cl2
Closs, G.L.; Closs, L.E. J. Am. Chem. Soc. 1960, 82, 5723Closs, G.L.; Schwartz, G.M. J. Am. Chem. Soc. 1960, 82, 5729Closs, G.L.; Moss, R.A.; Coyle, J.J. J. Am. Chem. Soc. 1962, 84, 4985 (sterics)Closs, G.L. J. Am. Chem. Soc. 1962, 84, 809Closs, G.L.; Moss, R.A. J. Am. Chem. Soc. 1964, 86, 4042
Li
Cl H
Cl
Li
Cl H - LiCl- LiCl
:
:
Closs, G.L.; Closs, L.E. J. Am. Chem. Soc. 1961, 83, 1003Closs, G.L.; Closs, L.E. J. Am. Chem. Soc. 1961, 83, 2015
102
Closs, G.L.; Closs, L.E. J. Am. Chem. Soc. 1963, 85, 99
Cl H
O- Li+ ClO- Li+
Cl
O- Li+
Cl
O
- LiCl
Ph-O- Li+
- LiCl- Me-H
:
MeLi + CH2Cl2
Closs, G.L.; Closs, L.E. J. Am. Chem. Soc. 1961, 83, 599
Cl
Ph Cl
Cl
Ph Cl Ph Cl
LiMe
Ph Cl
LiMe
Ph Me
Li
MePhClPh
- LiCl
MeLi
- LiCl
- MeLi
- LiCl
LiCl
- LiCl
MeLiMeLi:- LiCl- Me-H
MeLi
Closs, G.L.; Coyle, J.J. J. Org. Chem. 1966, 31, 2759
Nicholas cation
103
R1
R2
R3
(CO)3Co Co(CO)3
+
Reviews:Nicholas, K.M. Acc. Chem. Res. 1987, 20, 207
R1
R2
OH
R3
R1
R2
R3
OH
(CO)3Co Co(CO)3
R1
R2
R3
(CO)3Co Co(CO)3
R1
R2
R3
Nu
(CO)3Co Co(CO)3
R1
R2
Nu
R3
Co2(CO)8
- 2 CO
H+
- H2O
+Nu-
[O]
Nicholas, K.M.; Pettit, R. Tetrahedron Lett. 1971, 37, 3475Nicholas, K.M.; Pettit, R. J. Organometallic Chem. 1972, 44, C21Connor, R.E.; Nicholas, K.M. J. Organometallic Chem. 1977, 125, C45
Nitrenes
R N R N
triplet
..
:
singlet
::
Reviews:Kirmse, W. Angew. Chem. 1959, 71, 540Horner, L.; Christmann, A. Angew. Chem. 1963, 75, 707Abramovitch, R.A.; Davis, B.A. Chem. Rev. 1964, 64, 149Lwowski, W. Angew. Chem. Int. Ed. 1967, 6, 897Gilcrist, T.L.; Rees, C.W. Carbenes, Nitrenes, and Arynes, Appleton-Century Crofts: New York, 1969Lwowski, W. (ed.) Nitrenes, Wiley: New York, 1970Abramovitch, R.A. Chem. Soc. Spec. Publ. 1970, 24, 323
104
Abramovitch, R.A.; Sutherland, R.G. Forsch. Chem. Forsch. 1970, 16, 1Wasserman, E. Prog. Phys. Org. Chem. 1971, 8, 319Abramovitch, R.A. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 127Tomioka, H. Bull. Chem. Soc. Jpn 1998, 71, 1501Gritsan, N.P.; Platz, M.S. Adv. Phys. Org. Chem. 2001, 36, 255
O
R NH
Br
O
R N N C
R
O
O
RNH OR'
R'OH::- HBr
O
R1 NH
O
O
R2 R1NH2 + CO2 + R2COOH+ H2O
Lossen, W., Ann. Chem. 1872, 161, 347 (Lossen rearrangement)Tiemann, F. Chem. Ber. 1891, 24, 4162 (first proposed as transients in Lossen rearrangement)Lengfeld, F.; Stieglitz, J. Am. Chem. J. 1893, 15, 215Stieglitz, J. Am. Chem. J. 1896, 18, 751Stieglitz, J. Am. Chem. J. 1903, 29, 49
H
N
Ph3C X
Ph3C N N
Ph
Ph Ph
::
- HX
Morgan, A.F. J. Am. Chem. Soc. 1916, 38, 2095Vosburgh, I. J. Am. Chem. Soc. 1916, 38, 2081Stagner, B.A. J. Am. Chem. Soc. 1916, 38, 2069
105
Staudinger, H.; Miescher, K. Arch. Sci. Phys. Nat. 1917, 44, 387Staudinger, H.; Miescher, K. Helv. Chim. Acta 1919, 2, 554Curtius, T.; Schmidt, F. Chem. Ber. 1922, 55, 1571Curtius, T. Z. Angew. Chem. 1913, 26(3), 134Bertho, A. J. Prakt. Chem. 1928, 120[2], 89Taylor, T.W.J.; Owen, J.S.; Whittaker, D. J. Chem. Soc. 1938, 206
Dinitrenes
N X N
quintet
.. .
: :.
Reviews:Nimura, S.; Yabe, A. in Magnetic Properties of Organic Materials, (P.M. Lahti, ed.) Marcel Dekker: New York, 1999, Chapter 7, p. 127
N NN3 N3 NN
::
::
hν
- 2 N2
::
::
Trozzolo, A.M.; Murray, R.W.; Smolinsky, G.; Yager, W.A.; Wasserman, E. J. Am. Chem. Soc. 1963, 85, 2526
N3
N3
N
N
CN
CN- 2 N2
::
::hν
Hall, J.H. J. Am. Chem. Soc. 1965, 87, 1147
106
N3N3 NN. ..- 2 N2
hν : :
.
Wasserman, E.; Murray, R.W.; Yager, W.A.; Trozzolo, A.M.; Smolinsky, G. J. Am. Chem. Soc. 1967, 89, 5076 (first quintet nitrene observed)
Chapyshev, S.V.; Tomioka, H. Bull. Chem. Soc. Jpn 2003, 76, 2075
Trinitrenes
N X N
N. .:
.::
...septet
Reviews:None.
N3
CNNC
N3 N3
CN
N
CNNC
N3 N3
CN
N
CNNC
N N
CN
. .
.
. .
...hν
77 K- N2
- 2 N2
Wasserman, E.; Schueller, K.; Yager, W.A. Chem. Phys. Lett. 1968, 2, 259
Chapyshev, S.V.; Walton, R.; Sanborn, J.A.; Lahti, P.M. J. Am. Chem. Soc. 2000, 122, 1580
107
Chapyshev, S.V.; Kuhn, A.; Wong, M.; Wentrup, C. J. Am. Chem. Soc. 2000, 122, 1572Chapyshev, S.V. Mendeleev Commun. 2002, 168Oda, N.; Nakai, T.; Sato, K.; Shiomi, D.; Kozaki, M.; Okada, K.; Takui, T. Synth. Met. 2001, 121, 1840
N3
N3N3
N
N3N3
N
N3N
N
NN
HCN + NC-N=C=N-CN
hνhνhν
....
..
..
....
- N2 - N2 - N2
Sato, T.; Narazaki, A.; Kawaguchi, Y.; Niino, H.; Bucher, G. Angew. Chem. Int. Ed. 2003, 42, 5206Sato, T.; Narazaki, A.; Kawaguchi, Y.; Niino, H.; Bucher, G.; Grote, D.; Wolff, J.J.; Wenk, H.H.; Sander, W.W. J. Am. Chem. Soc. 2004, 126,7846
Nitrenium Ions
R1
N
R2+
:
Reviews:Gassman, P.G. Acc. Chem. Res. 1970, 3, 26Abramovitch, R.A.; Jerayaman, R. in Azides and Nitrenes: reactivity and utility, (E.F.V. Scriven, ed.) Academic Press: Orlando, FL, 1984, p.297Simonova, T.P.; Nefedov, V.D.; Toropova, M.A.; Kirillov, N.F. Russ. Chem. Rev. 1992, 61, 584McClelland, R.A. Tetrahedron 1996, 52, 6823Novak, M.; Rajagopal, S. Adv. Phys. Org. Chem. 2001, 36, 167
OH
N
Ph3C R
OH2
N
Ph3C R
N
Ph3C R Ph2C
N+
Ph
RPh2C=O + Ph-NHR
H2O
: : :
+
- H2O
+
H+
108
Cl
N
Ph3C R
N
Ph3C R Ph2C
N+
Ph
R- Cl-
+
::H2O
Ph2C=O + Ph-NHR
Stieglitz, J.; Leech, P.N. Chem. Ber. 1913, 46, 2147Stieglitz, J.; Leech, P.N. J. Am. Chem. Soc. 1914, 36, 272Stieglitz, J.; Stagner, B.A. J. Am. Chem. Soc. 1916, 38, 2046
Heller, H.E.; Hughes, E.D.; Ingold, C.K. Nature 1951, 168, 909 (first kinetic evidence)
NH NCl
N N N
MeO
MeOH+
+- Cl-
NaOCl
Gassman, P.G.; Fox, B.L. Chem. Commun. 1966, 153Gassman, P.G.; Fox, B.L. J. Am. Chem. Soc. 1967, 89, 338
N
Cl
N N
NMeO
NCl
MeOH
Cl-
++
109
Gassman, P.G.; Cryberg, R.L. J. Am. Chem. Soc. 1968, 90, 1355Gassman, P.G.; Cryberg, R.L. J. Am. Chem. Soc. 1969, 91, 2047; 5176
N
Y
OSO3-Ac
Y
NAc
N
Y
HAc
+SO4
-2
HII-
- I2- SO4
-2
Pelecanou, M.; Novak, M. J. Am. Chem. Soc. 1985, 107, 4499
Fishbein, J.C.; McClelland, R.A. J. Am. Chem. Soc. 1987, 109, 2824
Novak, M.; Kahley, M.J.; Lin, J.; Kennedy, S.A.; Swanegan, L.A. J. Am. Chem. Soc. 1994, 116, 11626Novak, M.; Kennedy, S.A. J. Am. Chem. Soc. 1995, 117, 574Novak, M.; Kahley, M.J.; Lin, J.; Kennedy, S.A.; James, T.J. J. Org. Chem. 1995, 60, 8294
McClelland, R.A.; Davidse, P.A.; Hadzialic, G. J. Am. Chem. Soc. 1995, 117, 4173
NO
Ph
O
SO3- N
Ph
O
Ph
N
O
- SO4-2
+
+
Novak, M.; Kahley, M.J.; Eiger, E.; Helmick, J.S.; Peters, H.E. J. Am. Chem. Soc. 1993, 115, 9453
110
Novak, M.; Lin, J. J. Org. Chem. 1999, 64, 6032
Nitrilium Ions
R1 N C R2
+
Reviews:Hegarty, A.F. Acc. Chem. Res. 1980, 13, 448
N
R1 R2
OH
O
R1 NHR2
N
R1 R2
OP
O
OP
O
OOH
N+ - OP
O
OP
O
OOH
R1
R2
N
R1
R2
OP
O
OP
O
OOH
N
R1
R2
OH
P2O5
- P2O5
Beckmann, E., Chem. Ber. 1886, 19, 988 (Beckmann rearrangement)
Klages, F.; Grill, W. Ann. Chem. 1956, 594, 21Ugi, I.; Beck, F.; Fetzer, U. Chem. Ber. 1962, 95, 126Hassner, A.; Levy, L.A.; Gault, R. Tetrahedron Lett. 1966, 27, 3119
Nitronium Ions
O N O+
Reviews:
111
Ridd, J.H. Studies in Chemical Structure and Reactivity 1966, 133Stock, L.M. Prog. Phys. Org. Chem. 1976, 12, 21Ridd, J.H. Adv. Phys. Org. Chem. 1978, 16, 1Olah, G.A. Acc. Chem. Res. 1980, 13, 330Olah, G.A.; Narang, S.C.; Olah, J.A.; Lammertsma, K. Proc. Natl. Acad. Sci. USA 1982, 79, 4487Ridd, J.H. Chem. Soc. Rev. 1991, 20, 149Eberson, L.; Hartshorn, M.P.; Radner, F. Acta Chem. Scand. 1994, 48, 937
Lauer, K.; Oda, R. J. Prakt. Chem. 1937, 148, 287Hughes, E.D.; Ingold, C.K.; Reed, R.I. Nature 1946, 158, 448
Gillespie, R.J.; Graham, J.; Hughes, E.D.; Ingold, C.K.; Peeling, E.R.A. Nature 1946, 158, 480Ingold, C.K.; Millen, D.J.; Poole, H.G. Nature 1946, 158, 480Goddard, D.R.; Hughes, E.D.; Ingold, C.K. Nature 1946, 158, 480Titov, A.I. J. Gen. Chem. USSR 1947, 17, 382
Nitrosonium Ions
N O+
:Reviews:Kreher, R. Angew. Chem. Int. Ed. 1973, 12, 1022Mocella, M.T.; Okamoto, M.S.; Barefield, E.K. Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry 1974, 4, 69Ridd, J.H. Adv. Phys. Org. Chem. 1978, 16, 1Olah, G.A. Acc. Chem. Res. 1980, 13, 330Williams, D.L.H. Adv. Phys. Org. Chem. 1983, 19, 381Bobbitt, J.M.; Flores, M.G.L. Heterocycles 1988, 27, 509
Blackall, E.L.; Hughes, E.D.; Ingold, C.K. J. Chem. Soc. 1952, 28Deschamps, J. Mem. Services Chim. Etat (Paris) 1953, 38, 335Lang, F.M. Chim. Industrie 1954, 71, 913Lewis, J.; Wilkins, R.G. Chem. Ind. 1954, 634Szabo, Z.G.; Bartha, L.G.; Lakatos, B. J. Chem. Soc. 1956, 1784Bayliss, N.S.; Watts, D.W. Austral. J. Chem. 1956, 9, 319Beattie, I.R. . J. Chem. Soc. 1957, 367
112
Sharp, D.W.A.; Thorley, J. J. Chem. Soc. 1963, 3557 (IR spectrum of nitrosonium ion)
Non-classical ions (hypercoordinate carbocations, sigma-bridged cations)
BsO
OBs
AcO
OAc
HOAc
HOAc
126
12 6
[1,6-H]
III
II
I
II
II
I
I
6 21
621
[1,6-H]
+
[1,6-H]
- OBs-
[1,2-H]
+
++
++
- OBs- +
+
Reviews:Winstein, S. Quart. Rev. (London) 1969, 23, 1411Bartlett, P.D. Non-classical Ions: reprints and commentary, W.A. Benjamin, Inc.: New York, 1965Kramer, G.M. Adv. Phys. Org. Chem. 1975, 11, 177Brown, H.C. The Non-classical Ion Problem, Plenum Press: New York, 1977
113
Brown, H.C. Top. Curr. Chem. 1979, 80, 1Saltzman, M.D.; Wilson, C.L. J. Chem. Educ. 1980, 57, 289 (non-classical name)Brown, H.C. Acc. Chem. Res. 1983, 16, 432Olah, G. Acc. Chem. Res. 1983, 16, 440Walling, C. Acc. Chem. Res. 1983, 16, 448
Nevell, T.P.; de Salas, E.; Wilson, C.L. J. Chem. Soc. 1939, 1188 (first suggestion of bridged carbocations)Winstein, S.; Trifan, D. J. Am. Chem. Soc. 1949, 71, 2953Winstein, S.; Morse, B.K.; Grunwald, E.; Jones, H.W.; Corse, J.; Trifan, D.; Marshall, H. J. Am. Chem. Soc. 1952, 74, 1127Winstein, S.; Trifan, D. J. Am. Chem. Soc. 1952, 74, 1147; 1154Olah, G.A.; White, A.M. J. Am. Chem. Soc. 1969, 91, 3954; 3958; 5801
CH2
+
Roberts, J.D.; Mazur, R.H. J. Am. Chem. Soc. 1951, 73, 3542
Brown, H.C. Science 1946, 103, 385Brown, H.C.; Fletcher, R.S. J. Am. Chem. Soc. 1949, 71, 1845Brown, H.C.; Berneis, H.L. J. Am. Chem. Soc. 1953, 75, 10
tBu
tBu Cl
tBu
tBu
tBu
tBu
CH3+
- Cl- +
Bartlett, P.D. J. Chem. Educ. 1953, 30, 22
114
OTs
H+- OTs-
+
Heck, R.; Prelog, V. Helv. Chim. Acta 1955, 38, 1541
Oxenium ions R O +
Reviews:Dimroth, K. Top. Current Chem. 1985, 129, 99
OCl O
AlCl3
Cl
O+ AlCl4-+ AlCl3
Martin, D.; Weise, A.; Becker, J. Chem. Ber. 1966, 99, 1266
O
tBuR1
R2
N C
R3
R4
O +
tBuR1
R2
N C
R3
R4
O
R1tBu
N
R2
C
R3
R4
R1
R2N
O R3
R4
..
+ +_
Rieker, A. Tetrahedron Lett. 1969, 2611
115
N+ O NO2
NO2
O +
NO2
O
O2N
O
OMe
MeOO2N
OH
+
BF4-
Ph-OMe
- pyridine +
Abramovitch, R.A.; Inbasekaran, M.; Kato, S. J. Am. Chem. Soc. 1973, 95, 5428Abramovitch, R.A.; Alvernhe, G.; Inbasekaran, M.N. Tetrahedron Lett. 1977, 1113Abramovitch, R.A.; Inbasekaran, M.N. Chem. Commun. 1978, 149Abramovitch, R.A.; Alvernhe, G.; Bartnik, R.; Dassanayake, N.L.; Inbasekaran, M.N.; Kato, S. J. Am. Chem. Soc. 1981, 103, 4558Abramovitch, R.A.; Bartnik, R.; Cooper, M.; Dassanayake, N.L.; Hwang, H.Y.; Inbasekaran, M.N.; Rusek, G. J. Org. Chem. 1982, 47, 4817Abramovitch, R.A.; Bartnik, R.; Besse, J.; Kato, S. Nouveau J. Chim. 1984, 8, 571Li, Y.; Abramovitch, R.A.; Houk, K.N. J. Org. Chem. 1989, 54, 2911
ONH
Ts O+OH
Ph
OH
Ph
O
H
- TsNH2
H+
+
Endo, Y.; Shudo, K.; Okamoto, T. J. Am. Chem. Soc. 1977, 99, 7721Shudo, K.; Orihara, Y.; Ohta, T.; Okamoto, T. J. Am. Chem. Soc. 1981, 103, 943Endo, Y.; Shudo, K.; Okamoto, T. J. Am. Chem. Soc. 1982, 104, 6393
RO+ + 2 e-RO-
Bursey, M.M.; Hass, J.R.; Harvan, D.J.; Parker, C.E. J. Am. Chem. Soc. 1979, 101, 5489
116
O
O
O
HO
O
O
H+
+
- H+
Deslongchamps, P.; Rowan, D.D.; Pothier, N. Heterocycles 1981, 15, 1093
Deslongchamps, P.; Rowan, D.D.; Pothier, N. Can. J. Chem. 1981, 59, 2787
N
O
O
O
Ph
N
O-
O
AlCl3
AlCl3
+ Ph-O+
Uto, K.; Miyazawa, E.; Ito, K.; Sakamoto, T.; Kikugawa, Y. Heterocycles 1998, 48, 2593
OH
tButBu
tBu
O
R tBu
tBu tBu
O
tBu
tBu tBu
O
tBu OH
tBu tBuBr2KBr
CH3CNH2O
+
Hegarty, A.F.; Keogh, J.P. J. Chem. Soc. Perkin Trans. 2 2001, 758
117
O
Ph OAc
O
Ph
O +
Ph
OPh
OH
OH
Ph
N3
HO N3 +- OAc-
+
H2O
N3-
Novak, M.; Glover, S.A. J. Am. Chem. Soc. 2004, 126, 7748
Oxirene
O
R1 R2
Reviews:Hopkinson, A.C.; Lien, M.; Yates, K.; Csizmadia, I.G. Prog. Theor. Org. Chem. 1977, 2, 230Lewars, E.G. Chem. Rev. 1983, 83, 519
OCrO3
Berthelot, M. Bull. Soc. Chim. Fr. 1870, 14, 113 (first claim; proven false)Madelung, W.; Oberwegner, M.E. Naturwissenshaften 1929, 17, 430 (coining of acetylene oxide name)Madelung, W.; Oberwegner, M.E. Ann. Chem. 1931, 490, 201 (second claim; proven false)
118
nBu nBu
O
nBu nBu
CH3(CO)OOH
Schubach, H.; Franzen, V. Ann. Chem. 1952, 557, 60 (third claim; proven false)
O
R1 R2
O
R1
N2
R2
O
R1
R2
:
hν or ∆
- N2
McDonald, R.N.; Schwab, P.A. J. Am. Chem. Soc. 1964, 86, 4866Stille, J.K.; Whitehurst, D.D. J. Am. Chem. Soc. 1964, 86, 4871Barnes, M.F.; MacMillan, J. J. Chem. Soc. C 1967, 361
O
C*
N2
O
C* C*
O
C* C O C* O Me2C*: + CO + Me2C: + C*Ohν
:- N2
hν
Csizmadia, I.G.; Font, J.; Strausz, O. J. Am. Chem. Soc. 1968, 90, 7360Clark, D.T. Theor. Chim. Acta 1969, 15, 225Thornton, D.E.; Gosavi, R.K.; Strausz, O. J. Am. Chem. Soc. 1970, 92, 1768
119
Dewar, M.J.S.; Trinajstic, N. Theor. Chim. Acta 1970, 17, 235Rowland, F.S.; Russell, R.L. J. Am. Chem. Soc. 1970, 92, 7508
O
R1
N2
R2
O
R1
R2
O
R1 R2
O
R2
R1
O C
R1
R2
O C
R1
R2
O
RO
R1
R2
O
RO
R1
R2
*
hν
- N2 * : * :
*
**
ROH ROH
**
Zeller, K.P.; Meier, H.; Kolshorn, H.; Mueller, E. Chem. Ber. 1972, 105, 1875Meier, H.; Zeller, K.P. in Proc. 7th IUPAC Symp. Photochem., Katholieke U. Louvain: Louvain, Belgium, 1978, p. 234Zeller, K.P. Chem. Ber. 1979, 112, 678Zeller, K.P. Ann. Chem. 1979, 2036Haiss, P.; Zeller, K.P. Z. Naturforsch. B 2003, 58, 595
Tanigaki, K.; Ebbesen, T.W. J. Am. Chem. Soc. 1987, 109, 5883 (proven to be false)
Tanaka, K.; Yoshimine, M. J. Am. Chem. Soc. 1980, 102, 7635 (ab initio calculations at 4-31G)
120
N
OO N
O
OO
O
+.- HCN - HCN
- CO2
Hop, C.E.C.A.; Holmes, J.L.; Terlouw, J.K. J. Am. Chem. Soc. 1989, 111, 441
Oxocarbons
O O
OO
O
O
O
O
O
O
O
OO
O O
O
O O
deltate
2_
croconate
2_
rhodizonatesquarate
_22_
Reviews:West, R. Aldrichimica Acta 1968, 1, 3West, R.; Niu, J. in Chemistry of the Carbonyl Group, (J. Zabicky, ed.) Interscience: New York, 1970, Vol. 2, p. 241 - 275West, R. Isr. J. Chem. 1980, 20, 300West, R. (ed.) Oxocarbons, Academic Press: New York, 1980
121
O
O
OHHO
HO OH
O
O
O
O
O
O
KOMeMeOH
_4
4 K+
West, R.; Niu, H.Y. J. Am. Chem. Soc. 1962, 84, 1324
CnOn-m
West, R.; Powell, D.L. J. Am. Chem. Soc. 1963, 85, 2577Ito, M.; West, R. J. Am. Chem. Soc. 1963, 85, 2580 (squarate, croconate)
Patton, E.; West, R. J. Phys. Chem. 1970, 74, 2512 (rhodizonate)
West, R.; Eggerding, D.; Perkins, J.; Handy, D.; Tuazon, E.C. J. Am. Chem. Soc. 1979, 101, 1710 (deltate)
Oxonium ions
R1
O
R2 R3
+
Reviews:Perst, H. Oxonium Ions in Organic Chemistry, Verlag Chemie: Weinheim, 1971Perst, H. in Carbonium Ions, (G. Olah, P.v.R. Schleyer, eds.) Wiley: New York, 1976, Vol. 5, p. 1961
(i) Acetoxonium ionsReviews:None.
122
OTs
O O O O
OH
O O
H2O
- OTs-
+
Winstein, S.; Hess, H.V.; Buckles, R.E. J. Am. Chem. Soc. 1942, 64, 2796Winstein, S.; Buckles, R.E. J. Am. Chem. Soc. 1942, 64, 2780; 2787; 1943, 65, 613
(ii) Flavinium saltsReviews:None.
Blackburn, M.; Sankey, G.B.; Robertson, A.; Whalley, W.B. J. Chem. Soc. 1957, 1573Dudley, K.H.; Ehrenberg, A.; Hemmerich, P.; Mueller, F. Helv. Chim. Acta 1964, 47, 1354Dudley, K.H.; Hemmerich, P. Helv. Chim. Acta 1964, 47, 355Walker, W.H.; Hemmerich, P.; Massey, V. Helv. Chim. Acta 1967, 50, 2269
(iii) Flavylium saltsReviews:Jurd, L. Recent Adv. Phytochem. 1972, 5, 135Iacobucci, G.A.; Sweeny, J.G. Tetrahedron 1983, 39, 3005
123
O
OH
HO
OH
OH
R1
R2
R1 R2 Name
H H pelargoninH OH cyanidinOH OH delphinidinOMe OMe enidin (malvidin, syringidin) Cl-
+
Pratt, D.D.; Robinson, R.; Williams, P.N. J. Chem. Soc. 1924, 125, 199Robertson, A.; Robinson, R. J. Chem. Soc. 1926, 1713Robertson, A.; Robinson, R. J. Chem. Soc. 1927, 242; 1710Robertson, A.; Robinson, R. J. Chem. Soc. 1928, 1455; 1460
(iv) Meerwein saltsReviews:Kreher, R. Angew. Chem. Int. Ed. 1973, 12, 1022
Et
O
Et Et
Me
O
Me Me
X -+ + X - X = BF4, SbCl6, AuCl4, Bi2I7, HgI3, picrate, 1/2 SnCl6, 1/2 PtCl6
O
ClO
Cl
EtO
B3 + 4 Et2O...BF3 + 2 Et2O
3
+ 3 Et3O+ BF4-
124
O+
Et
BF4-
Me2O + BF3 + Et-F
NO2O2N
NO2
O -
Et3O+
Meerwein, H.; Hinz, G.; Hofmann, P.; Kronig, E.; Pfeil, E. J. Prakt. Chem. 1937, 147, 257
O RO OMCln-1
+ R3O+ MCln+1+ 2 R-O-R...MCln
Meerwein, H.; Battenberg, E.; Gold, H.; Pfeil, E.; Willfang, G. J. Prakt. Chem. 1939, 154, 83Meerwein, H. Org. Synth. 1966, 46, 120
(v) Methoxonium ionsReviews:None.
OMe
Br
OMe
O+
Me
OMe OMe
OH
- Br-+
+ H2O
Winstein, S.; Ingraham, L.L. J. Am. Chem. Soc. 1952, 74, 1160
(vi) Pyrylium salts
125
Reviews:Balaban, A.T.; Schroth, W.; Fischer, G.W. Adv. Heterocyclic Chem. 1969, 10, 241Balaban, A.T. Studies in Org. Chem. 1979, 3, 79
O O
O O
O
O
O+
OH
O
COOEt
∆2
H3O+
- CO2
HXX -
X = Cl, Br, I, PtCl6, NO3, oxalate, tartrate, picrate, salicylate
Collie, J.N.; Tickle, T. J. Chem. Soc. Trans. 1899, 75, 710Werner, A. Chem. Ber. 1901, 34, 3300Decker, H.; von Fellen, T. Ann. Chem. 1907, 356, 281Baeyer, A. Chem. Ber. 1910, 43, 2337Willstätter, R. Sitzber. Preuss. Akad. Wissensch. 1914, 402Willstätter, R.; Mallison, H. Sitzber. Preuss. Akad. Wissensch. 1914, 769Dilthey, W. J. Prakt. Chem. 1916, 94, 53Pfeiffer, P. Ann. Chem. 1917, 412, 253Hanztsch, A. Chem. Ber. 1919, 52, 1535; 1544Dilthey, W. J. Prakt. Chem. 1921, 102, 209Gastaldi, C. Gazz. Chim. Ital. 1921, 5, 169Dilthey, W. J. Prakt. Chem. 1922, 104, 28
R3
R2
R1
O
R4 O
O
R4O+
R2
R3R1
R4 R4
O
R4 OH
ClO4-
+ 2
HClO4
- H2O+
Balaban, A.T.; Nenitzescu, C.D. Ann. Chem. 1959, 625, 74
126
Balaban, A.T.; Nenitzescu, C.D. J. Chem. Soc. 1961, 3553; 3561; 3564Praill, P.F.G.; Whitear, A.L. J. Chem. Soc. 1961, 3573Praill, P.F.G.; Whitear, A.L. Proc. Chem. Soc. 1961, 312
Phenonium Ions
R2 R3
R1R4
R2 R3
R1 R4
R2 R3
R1 R4
R2 R3
R1 R4
R2 R3
R4R1
+
+
+
+
+
Reviews:None.
Cram, D.J. J. Am. Chem. Soc. 1949, 71, 3863Cram, D.J. J. Am. Chem. Soc. 1949, 71, 3871Cram, D.J. J. Am. Chem. Soc. 1949, 71, 3875Cram, D.J. J. Am. Chem. Soc. 1949, 71, 3883Winstein, S.; Morse, B.K.; Grunwald, E.; Schreiber, K.C.; Corse, J. J. Am. Chem. Soc. 1952, 74, 1113Winstein, S.; Brown, M.; Schreiber, K.C.; Schlesinger, A.H. J. Am. Chem. Soc. 1952, 74, 1140Cram, D.J.; Elhafez, F.A.A.; Weingartner, H. J. Am. Chem. Soc. 1953, 75, 2293Cram, D.J.; Elhafez, F.A.A. J. Am. Chem. Soc. 1953, 75, 3189Laurent, A.; Mison, P. Bull. Soc. Chim. Fr. 1962, 956
Kresge, A.J.; Barry, G.W.; Charles, K.R.; Chiang, Y. J. Am. Chem. Soc. 1962, 84, 4343Cram, D.J. J. Am. Chem. Soc. 1964, 86, 3767Seidl, G.; Huisgen, R.; Wimmer, I. Ann. Chem. 1964, 677, 34Olah, G.A.; Pittman, C.U. Jr. J. Am. Chem. Soc. 1965, 87, 3509
Olah, G.A.; Head, N.J.; Rasul, G.; Prakash, G.K.S. J. Am. Chem. Soc. 1995, 117, 875
127
Phenyl Cation (phenylium ion, arylium ion, benzene cation)
R
+
Reviews:Ambroz, H.B.; Kemp, T.J. Chem. Soc. Rev. 1979, 8, 353
N2+
RX
RR
+ X-
- N2
+X -
Sandmeyer, T., Chem. Ber. 1884, 17, 1633Sandmeyer, T., Chem. Ber. 1884, 17, 2650
Lewis, E.S. J. Am. Chem. Soc. 1958, 80, 1371Kursanov, D.N.; Vol'pin, M.E.; Parnes, Z.N. Khim. Nauka i Prom. 1958, 3, 159Franzen, V. Chem. Ztg. 1959, 83, 677 R
N2+
R R
etc.
.
. ++- N2
X -
Taft, R.W. Jr. J. Am. Chem. Soc. 1961, 83, 3350Hey, D.H.; Liang, K.S.Y.; Perkins, M.J. Tetrahedron Lett. 1967, 1477Vul'fson, N.S.; Puchkov, V.A.; Nekrasov, Y.S. Izv. Akad. Nauk SSSR Ser. Khim. 1967, 1881Friedman, L.; Chlebowski, J. J. Org. Chem. 1968, 33, 1633Evleth, E.M.; Horowitz, P.M. J. Am. Chem. Soc. 1971, 93, 5636Gleiter, R.; Hoffmann, R.; Stohrer, W.D. Chem. Ber. 1972, 105, 8Kamigata, N.; Kobayashi, M.; Minato, H. Bull. Chem. Soc. Jpn. 1972, 45, 2047Boettcher, H.; Becker, H.G.O.; Inanov, V.L.; Kusmin, M.G. Chimia 1973, 27, 437
128
N2
++ + N2
Swain, C.G.; Sheats, J.E.; Harbison, K.G. J. Am. Chem. Soc. 1975, 97, 783Swain, C.G.; Sheats, J.E.; Gorenstein, D.G.; Harbison, K.G. J. Am. Chem. Soc. 1975, 97, 791
Phosphenium ions
R1
PR2
+
Reviews:Cowley, A.H.; Kemp, R.A. Chem. Rev. 1985, 85, 367Mazieres, M.R.; Roques, C.; Khim, T.; Majoral, J.P.; Wolf, R.; Sanchez, M. Phosphorus, Sulfur, and Silicon and the related elements 1990, 49-50, 309Burford, N.; Clyburne, J.A.C.; Losier, P.; Parks, T.M.; Cameron, T.S.; Richardson, J.F. Phosphorus, Sulfur, and Silicon and the related elements1994, 53-54, 301Guerret, O.; Bertrand, G. Acc. Chem. Res. 1997, 30, 486Nakazawa, H. J. Organometallic Chem. 2000, 611, 349Nakazawa, H. Adv. Organometallic Chem. 2004, 50, 108
P Cl
R2N
R2N
P+
R2N
R2N
P H
R2N
R2N
N
P
N
R
R
Cl
N
P+
N
R
R
N
P
N
R
R
H
- Cl-
LiAlH 4
"H -"
- Cl- "H -"
LiAlH 4
R = iPr, Et
R = tBu
129
King, R.B.; Sundaram, P.M. J. Org. Chem. 1984, 49, 1784Kibardin, A.M.; Litvinov, I.A.; Naumov, V.A.; Struchkov, Yu.T.; Gryaznova, T.V.; Mikhailov, Yu.B.; Pudovnik, A.N. Dokl. Akad. Nauk SSSR1988, 298, 369Wrackmeyer, B.; Schiller, J. Z. Naturforsch. 1992, 47B, 662Kibardin, A.M.; Litvinov, I.A.; Naumov, V.A.; Struchkov, Yu.T.; Gryaznova, T.V.; Mikhailov, Yu.B.; Pudovnik, A.N. Dokl. Akad. Nauk SSSR1994, 312, 623
N
P+
N
tBu
tBu
N
P+
N
tBu
tBu
Cl-AgPF6
PF6- + AgCl
N
P
N
tBu
tBu
N
P+
N
tBu
tBu
Cl
: PF6- + AgCl
AgPF6
Denk, M.K.; Gupta, S.; Lough, A.J. Eur. J. Inorg. Chem. 1999, 41
Phosphonium ions
OR
P+RO OR
R'
Reviews:
130
Smith, D.J.H. Organophosphorus Chem. 1972, 4, 1Smith, D.J.H. Organophosphorus Chem. 1973, 5, 1Smith, D.J.H. Organophosphorus Chem. 1974, 6, 1Smith, D.J.H. Organophosphorus Chem. 1976, 7, 1Allen, D.W. Organophosphorus Chem. 1977, 8, 1Allen, D.W. Organophosphorus Chem. 1978, 9, 1Allen, D.W. Organophosphorus Chem. 1979, 10, 1Smith, D.J.H. in Comprehensive Organic Chemistry, (I.O. Sutherland, ed.) Pergamon Press: Oxford, 1979, Vol. 2, p. 1127 - 1187Allen, D.W. Organophosphorus Chem. 1980, 11, 1Allen, D.W. Organophosphorus Chem. 1981, 12, 1Allen, D.W. Organophosphorus Chem. 1983, 14, 1Allen, D.W. Organophosphorus Chem. 1984, 15, 1Allen, D.W. Organophosphorus Chem. 1985, 16, 1Allen, D.W. Organophosphorus Chem. 1986, 17, 1Allen, D.W. Organophosphorus Chem. 1987, 18, 1Allen, D.W. Organophosphorus Chem. 1988, 19, 1Allen, D.W. Organophosphorus Chem. 1989, 20, 1Allen, D.W. Organophosphorus Chem. 1990, 21, 1Allen, D.W. Organophosphorus Chem. 1991, 22, 1Allen, D.W. Organophosphorus Chem. 1992, 23, 1Allen, D.W. Organophosphorus Chem. 1993, 24, 1Allen, D.W. Organophosphorus Chem. 1994, 25, 1Cristan, H.J.; Plenat, F. in Chemistry of Organophosphorus Compounds, (F.R. Hartley, ed.) Wiley: Chichester, 1994, p. 45 - 183Allen, D.W. Organophosphorus Chem. 1995, 26, 1Allen, D.W. Organophosphorus Chem. 1996, 27, 1Allen, D.W. Organophosphorus Chem. 1997, 28, 1Allen, D.W. Organophosphorus Chem. 1999, 29, 1Allen, D.W. Organophosphorus Chem. 2000, 30, 1Stephan, D.W. Angew. Chem. Int. Ed. 2000, 39, 501Allen, D.W. Organophosphorus Chem. 2001, 31, 1Allen, D.W. Organophosphorus Chem. 2002, 32, 1Allen, D.W. Organophosphorus Chem. 2003, 33, 1
131
P+PCH3O
OCH3
OCH3 CH3O
OCH3
OCH3
CH3
PCH3O
OCH3
O
CH3
- CH3II-+ CH3I
Michaelis, A.; Kaehne, R. Chem. Ber. 1898, 31, 1048Arbuzov, A.E. J. Russ. Phys. Chem. Soc. 1906, 38, 687
o-Quinodimethanes (o-Xylylenes)
CH2
CH2
.
.
Reviews:Segura, J.L.; Martin, N. Chem. Rev. 1999, 99, 3199
CH2
CH2
.
.
Willstätter, R.; Veraguth, H. Chem. Ber. 1907, 40, 959Bamberger, E.; Reber, E. Chem. Ber. 1907, 40, 2258Fecht, H. Chem. Ber. 1907, 40, 3883Ipatiev, V. Chem. Ber. 1908, 41, 993Tshitshibabin, A.E. Chem. Ber. 1908, 41, 2770Scholtz, M.; Wolfrum, R. Chem. Ber. 1910, 43, 2304Chelintzev, V.V. Bull. Soc. Chim. Fr. 1936, 3, 1035Esafov, V.I. J. Gen. Chem. USSR 1939, 9, 1841Beilenson, B.; Hamer, F.M.; Rathbone, R.J. J. Chem. Soc. 1945, 222
132
Lu're, S.I.; Shemyakin, M.M. J. Gen. Chem. USSR 1947, 17, 1356Meyer, A.; Bouchet, G. Compt. Rend. 1948, 227, 345Wittig, G.; Mangold, R.; Felletschin, G. Ann. Chem. 1948, 560, 116
CHBr2
CHBr2
Br
Br Br
Br
Br
Br
- 2 NaBr- I2
.
.2 NaI
Cava, M.P.; Napier, D.R. J. Am. Chem. Soc. 1957, 79, 1701
p-Quinodimethanes (p-Xylylenes)
CH2
H2C
.
.Reviews:None.
Schlenk, W.; Meyer, E. Chem. Ber. 1919, 52B, 8
CH3 CH3 CH2 CH2.- 2 H n
p-xylenepyrolysis
Szwarc, M. Nature 1947, 160, 403
133
Szwarc, M. Disc. Faraday Soc. 1947, 2, 46Szwarc, M. J. Chem. Phys. 1951, 16, 319
Farmer, J.B.; Marsden, D.G.H.; Lossing, F.P. J. Chem. Phys. 1955, 23, 403Errede, L.A.; Landrum, B.F. J. Am. Chem. Soc. 1957, 79, 4952
o-Quinonemethides and p-Quinonemethides
OO
Reviews:Fries, K.; Brandes, E. Ann. Chem. 1939, 542, 48Wagner, H.U.; Gompper, R. in The Chemistry of Quinonoid Compounds, (S. Patai, ed.) Wiley: Chichester, 1974, p. 1145Volod'kin, A.A.; Ershov, V.V. Usp. Khim. (Russ. Chem. Rev.) 1988, 57, 595Wagner, H.U.; Gompper, R. in The Chemistry of Quinonoid Compounds, (S. Patai, Z. Rappoport, eds.) Wiley: Chichester, 1988. Vol. 2.Amouri, H.; Le Bras, J. Acc. Chem. Res. 2002, 35, 501
Staudinger, H.; Bereza, S. Ann. Chem. 1911, 380, 243Gomberg, M. J. Am. Chem. Soc. 1913, 35, 1035Schlenk, W.; Brauns, M. Chem. Ber. 1914, 46, 4061Pummerer, R.; Melamed, D.; Puttfarcken, H. Chem. Ber. 1922, 55B, 3116Lindemann, H. Ann. Chem. 1923, 431, 270Lindemann, H.; Forth, H. Ann. Chem. 1923, 435, 219Shoruigin, P. Chem. Ber. 1927, 60B, 2373Goldschmidt, S.; Sadler, A.; Gelber, E.; Schlosser, H.; Vogt, A. Chem. Ber. 1928, 61B, 829Shorigin, P. Chem. Ber. 1928, 61B, 2516
134
HO I Li+ -O Li
O
Ar
ArO
Ar
Ar
2 nBuLi
- nBuI- nBuOH
Hünig, S.; Schweeberg, H.; Schwarz, H. Ann. Chem. 1954, 587, 132Hünig, S.; Schwarz, H. Ann. Chem. 1956, 599, 131
XX
FVT
X = O, S, NH
Pfister-Guillouzo, G.; Gracian, F.; Senio, A.; Letulle, M.; Ripoll, J.L. Tetrahedron Lett. 1992, 33, 5753
HO
OH
R2R1
O
R1
R2
- H2O
hν
Wan, P.; Barker, B.; Diao, L.; Fischer, M.; Shi, Y.; Yang, C. Can. J. Chem. 1996, 74, 465
Chiang, Y.; Kresge, A.J.; Zhu, Y. J. Am. Chem. Soc. 2000, 122, 9854
Chiang, Y.; Kresge, A.J.; Zhu, Y. J. Am. Chem. Soc. 2002, 124, 6349
Chiang, Y.; Kresge, A.J.; Zhu, Y. Photochem. Photobiol. Sci. 2002, 1, 67
135
Chang, J.A.; Kresge, A.J.; Zhan, H.Q.; Zhu, Y. J. Phys. Org. Chem. 2004, 17, 579
O O
Cevasco, G.; Pardini, R.; Thea, S. Eur. J. Org. Chem. 1998, 665
Radicals
Reviews:Gomberg, M. Chem. Rev. 1925, 1, 91Trans. Faraday Soc. 1934, 30, 1 - 246 (symposium on radicals)Hey, D.H.; Waters, W.A. Chem. Rev. 1937, 21, 169
Steacie, E.W.R. Free Radical Mechanisms, Reinhold Publishing Corp.: New York, 1946
Steacie, E.W.R. Atomic and Free Radical Reactions, 2nd ed., Reinhold Publishing Corp.: New York, 1954
Lossing, F.P. Ann. N.Y. Acad. Sci. 1957, 67, 499Waters, W.A. (ed.) Vistas in Free-Radical Chemistry, Pergamon Press: New York, 1959Symons, M.C.R. Adv. Phys. Org. Chem. 1963, 1, 284Friedlina, R.K. Adv. Free Radical Chem. 1965, 1, 211Norman, R.O.C. Adv. Phys. Org. Chem. 1967, 5, 53Forrester, A.R.; Hay, J.M.; Thomson, R.H. Organic Chemistry of Stable Free Radicals, Academic Press: New York, 1968Janzen, E.G. Acc. Chem. Res. 1969, 2, 279Bennett, J.E.; Mile, B.; Thomas, A.; Ward, B. Adv. Phys. Org. Chem. 1970, 8, 1Kochi, J.K. (ed.) Free Radicals, Wiley: New York, Vol. 1 - 2, 1973Huyser, E.S. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 1Zahradnik, R.; Carsky, P. Prog. Phys. Org. Chem. 1973, 10, 327Neta, P. Adv. Phys. Org. Chem. 1976, 12, 224
Griller, D.; Ingold, K.U. Acc. Chem. Res. 1976, 9, 13
Griller, D.; Ingold, K.U. Acc. Chem. Res. 1980, 13, 193Ballester, M. Acc. Chem. Res. 1985, 18, 380 (inert free radicals)
136
Russell, G.A. Adv. Phys. Org. Chem. 1987, 23, 271Ballester, M. Adv. Phys. Org. Chem. 1989, 25, 307; 321 (inert free radicals)Fossey, J.; Lefort, D.; Sorba, J. Free Radicals in Organic Chemistry, Wiley: New York, 1995Arnold, B.R.; Bucher, G.; Netto-Ferreira, J.C.; Platz, M.S.; Scaiano, J.C. Biradicals, Radicals in Excited States, Carbenes, and Related Species,Springer-Verlag: Weinheim, 1998Saveant, J.M. Adv. Phys. Org. Chem. 2000, 35, 117Rathore, R.; Kochi, J.K. Adv. Phys. Org. Chem. 2000, 35, 193
Tidwell, T.T. Adv. Phys. Org. Chem. 2001, 36, 1Zipse, H. Adv. Phys. Org. Chem. 2003, 38, 111Power, P.P. Chem. Rev. 2003, 103, 789 (stable radicals of heavier main group elements)
Hicks, R.G. Can. J. Chem. 2004, 82, 1119 (stable radicals)
stabilities of free radicals:Bowden, S.T.; Jones, W.J. J. Chem. Soc. 1928, 1149 (from dimer dissociation equilibria)Bent, H.E.; Cline, J.E. J. Am. Chem. Soc. 1936, 58, 1624 (from thermochemical techniques)Cohen, S.G.; Cohen, F.; Wang, C.H. J. Org. Chem. 1953, 28, 1749 (from kinetic techniques)Henglein, A. Electroanal. Chem. 1976, 9, 163 (from pulse radiolysis polarography)
Carbon centred radicals
(i) Gomberg radical
Ph
Ph Ph
ClPh
Ph Ph
Zn .+ Cl.
H
Ph
Ph
Ph
Ph
Ph
Ph
Ph Ph.2
Gomberg, M., J. Am. Chem. Soc. 1900, 22, 757
137
Gomberg, M. Chem. Ber. 1900, 33, 3150Gomberg, M. Chem. Ber. 1901, 34, 2726Gomberg, M.; Bachmann, W.E. J. Am. Chem. Soc. 1924, 46, 2339Lankamp, H.; Nauta, W.T.; MacLean, C. Tetrahedron Lett. 1968, 249 (correct structure of radical dimer product). Ph3C-O-O-CPh32 Ph3C + O2
Gomberg, M.; Cone, L.H. Chem. Ber. 1904, 37, 3538Schmidlin, J. Chem. Ber. 1908, 41, 2471
(ii) Alkyl radicals
Reviews:
Steacie, E.W.R. Atomic and Free Radical Reactions, 2nd ed., Reinhold: New York, 1954Norrish, R.G.W.; Thrush, B.A. Quart. Rev. Chem. Soc. 1956, 10, 149Davidson, N. J. Chem. Educ. 1957, 34, 126Ramsay, D.A. Ann. N.Y. Acad. Sci. 1957, 67, 485
Lossing, F.P. Ann. N.Y. Acad. Sci. 1957, 67, 499
Kutschke, K.O.; Steacie, E.W.R. in Vistas in Free Radical Chemistry, (W.A. Waters, ed.) Pergamon Press: New York, 1959, p. 162
R O Cl
Ohν
RCl +
Chattaway, F.D.; Backeberg, O.G. J. Chem. Soc. 1923, 123, 2999
Ph-H + PhCOOR + CO2
Ph-R + PhCOOH + CO2(PhCOO)2 + R-H
138
Gelissen, H.; Hermans, P.H. Chem. Ber. 1925, 58, 984
..R + PbR3
∆R4Pb
Paneth, F.; Hofeditz, W. Chem. Ber. 1929, 62, 1335 (gas phase)Paneth, F.; Lautsch, W. Chem. Ber. 1931, 64, 2702Paneth, F.; Herzfeld, K. Z. Elektrochem. 1931, 37, 577Paneth, F. Trans. Faraday Soc. 1934, 30, 179
CH3Cl, CH2Cl2, CHCl3, CCl4CH4 + Cl2
Pease, R.N.; Walz, F. J. Am. Chem. Soc. 1931, 53, 3728
O
Cl3C ClCl2C=CCl2 + 1/2 O2
Dickinson, R.A.; Leermakers, P.A. J. Am. Chem. Soc. 1932, 54, 3852
Br Br
Br
Br BrBr
O2
HBr
(absence of O2)HBr
Kharasch, M.S.; Mayo, F.R. J. Am. Chem. Soc. 1933, 55, 2468 (peroxide effect)Kharasch, M.S.; Engelmann, H.; Mayo, F.R. J. Org. Chem. 1937, 2, 288Kharasch, M.S.; Mayo, F.R. J. Am. Chem. Soc. 1938, 60, 3097
139
chlorination of aliphatic hydrocarbons:Hass, H.B.; McBee, E.T.; Weber, P. Ind. Eng. Chem. 1935, 27, 1190Hass, H.B.; McBee, E.T.; Weber, P. Ind. Eng. Chem. 1936, 28, 333Vaughan, W.E.; Rust, F.F. J. Org. Chem. 1940, 6, 449Rust, F.F.; Vaughan, W.E. J. Org. Chem. 1941, 7, 479
Kharasch, M.S.; Mansfield, J.V.; Mayo, F.R. J. Am. Chem. Soc. 1937, 59, 1155
COOMe
CH2 C
COOMe
n
hν
Melville, H.W. Proc. Roy. Soc. London 1937, 163A, 511
O
Ph OO
O
Ph
Brodie, B.C. Ann. Chem. 1858, 108, 79
R H
O
Ph OO
O
Ph
R Cl + SO2 + HCl + 2 CO2 + 2 PhCl+ SO2Cl2
Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1939, 61, 2142; 3432Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1940, 62, 925
R H R SO2Cl + HClhν
+ SO2 + Cl2
140
Reed, C.F. US 2,174,494 (1939)Kharasch, M.S.; Chao, T.H.; Brown, H.C. J. Am. Chem. Soc. 1940, 62, 2393
R H
O
R Cl
O
Cl Cl
R H
O
R Cl
O
Cl
O
Clhν
+ + HCl + CO
+ HCl+hν
Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1940, 62, 454
OH
Ph
Br
Ph Ph
PhPh
.2
ZnBr2
Zn2
- H2O
HBr2
Ziegler, K.; Deparade, W. Ann. Chem. 1950, 567, 123
Cl
Cl
Cl
Cl
4 CH2=N2 + CCl4 4 N2 +
Urry, W.H.; Eiszner, J.R. J. Am. Chem. Soc. 1952, 75, 5822
141
N NNC
OOH
CN
+ O2
(AIBN)
Jones, G.G. US 2,681,936 (1954)
detection of free radicals in solution:
Kharasch, M.S.; Mulley, R.D.; Nudenberg, W. J. Org. Chem. 1954, 19, 1477Kharasch, M.S.; Holton, P.G.; Nudenberg, W. J. Org. Chem. 1954, 19, 1600Kharasch, M.S.; Nudenberg, W. J. Org. Chem. 1954, 19, 1921Kharasch, M.S.; Holton, P.G.; Nudenberg, W. J. Org. Chem. 1955, 20, 920
Herzberg, G.; Shoosmith, J. Can. J. Phys. 1956, 34, 523 (detection of methyl radical)
O
O
Ph
O
Ph OEt
H2O2
Huyser, E.S.; Garcia, Z. J. Org. Chem. 1962, 27, 2716
X = Cl, BrX3C-CH2-CHXRCX4 + CH2=CHR
Walling, C.; Huyser, E.S. Org. React. 1963, 13, 122
N NPh Ph Ph .2 - N2
Nelsen, S.F.; Bartlett, P.D. J. Am. Chem. Soc. 1966, 88, 137Nelsen, S.F.; Bartlett, P.D. J. Am. Chem. Soc. 1966, 88, 143
142
CH3 CH2
tBu-O-O-tBu 2 tBu-O.+ tBuO. tBuOH + .
Kochi, J.K.; Krusic, P.J.; Eaton, D.R. J. Am. Chem. Soc. 1969, 91, 1877Kochi, J.K.; Krusic, P.J.; Eaton, D.R. J. Am. Chem. Soc. 1969, 91, 1879
N CH3 N CH2.tBuOH +.+ tBuO
.2 tBu-OtBu-O-O-tBu
Danen, W.C.; West, C.T.; Kensler, T.T. J. Am. Chem. Soc. 1973, 95, 5716Danen, W.C.; West, C.T. J. Am. Chem. Soc. 1974, 96, 2447
(iii) Aryl radical (phenyl radical)Reviews:
Taylor, G.W. Can. J. Chem. 1957, 35, 739Williams, G.H. Homolytic Aromatic Substitution, Pergamon Press: London, 1960Porter, G.G. in Molecular Spectroscopy (P. Hepple, ed.) Proc. Conf. 4th, 1968, 305Bolton, R.; Williams, G.H. Chem. Soc. Rev. 1986, 15, 261Galli, C. Chem. Rev. 1988, 88, 765Brown, R.F.C. Eur. J. Org. Chem. 1999, 3211
R
.
143
O
NPh
NO
N N O
O
Ph Ph-Ph + HOAcPh-H. .Ph + OAc
- N2
Bamberger, E. Chem. Ber. 1895, 28, 403Bamberger, E. Chem. Ber. 1897, 30, 366Waters, W.A. J. Chem. Soc. 1937, 113
N N O - Na+O2N
O
R ClN N OO2N
O
R
+
- NaCl
N N OO2N
O
R
O2N
O
O R
O2N
O
HO RPh
+Ph-H
.. + - N2
Kühling, O. Chem. Ber. 1895, 28, 41Kühling, O. Chem. Ber. 1896, 29, 165
144
R1
X
R1 R1
R1
R1
. 2 X-2 X + 2 e-
Cu+2 + 2 e-Cu
.
.+ X.
2
Ullmann, F. Ann. Chem. 1904, 332, 38 (Ullmann coupling reaction)Rapson, W.S.; Shuttleworth, R.G. Nature 1941, 147, 675
Ar1 N2+ Ar2 H Ar1 Ar2 + N2 + HXNaOH
+ X -
Gomberg, M.; Bachmann, W.E. J. Am. Chem. Soc. 1924, 46, 2339Gomberg, M.; Pernert, J.C. J. Am. Chem. Soc. 1926, 48, 1372
Levy, J. Bull. Soc. Chim. Fr. 1923, 33, 1655Reihlen, H.; Illig, R.; Wittig, R. Chem. Ber. 1925, 58B, 12Levy, J. Bull. Soc. Chim. Fr. 1926, 39, 67Tiffeneau, M.; Levy, J. Bull. Soc. Chim. Fr. 1931, 49, 1806
Bates, J.R.; Taylor, H.S. J. Am. Chem. Soc. 1927, 49, 2438 (first free radical chain mechanism for gas phase polymerization of ethylene)
.. .
Ph2Hg2 Ph + Hg
Ph-PhPh + Ph
.4 Ph + PbPbPh4
145
Dull, M.F.; Simons, J.H. J. Am. Chem. Soc. 1933, 55, 3898 Ph Br .Ph + NaBr+ Na (g)
Horn, E.; Polanyi, M. Z. Physik. Chem. 1934, 25B, 151
N NPh CPh3
O
Ph OO
O
PhO
Ph O
.+ PhCOO Ph-Ph + PhCOOHPh-H
2- CO2
Ph. .
Ph-H. .Ph + Ph3C- N2
+ Ph-H Ph-Ph + Ph3CH
N NPh OAc . .Ph + OAc
- N2
N NPhCH2 OAc
- N2
PhCH2 + OAc..
PhN
NO
O
PhCH2
N
NO
O
+ Ph-H Ph-Ph + N2 + CH3COOH
+ Ph-H PhCH2Ph + N2 + CH3COOH
Grieve, W.S.M.; Hey, D.H. J. Chem. Soc. 1934, 1797 (homolytic aromatic substitution)Hey, D.H. J. Chem. Soc. 1934, 1966
146
Ph-S-S-Ph + SnS2150 C .PhPh4Sn + S
Ph-S-S-Ph + PbSPh.150 CPh4Pb + S
2 Ph-H + Hg + Ph-N=N-Ph.Ph150 C
Ph2Hg + Ph-NH-NH-Ph
Razuvaev, G.A.; Koton, M.M. Zh. Obshchei Khim. 1935, 5, 361Koton, M.M. Zh. Obshchei Khim. 1932, 2, 345
R H
O
Ph OO
O
Ph
R Cl + SO2 + HCl + 2 CO2 + 2 PhCl+ SO2Cl2
Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1939, 61, 2142; 3432Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1940, 62, 925
N2+ Cl-
N N
Ph+- N2- HCl
Haworth, J.W.; Heilbron, I.M.; Hey, D.H. J. Chem. Soc. 1940, 349Hey, D.H.; Stirling, C.J.M.; Williams, G.H. J. Chem. Soc. 1955, 3963
N NAr NMe2 Ar-R + Me2NHR-H. .Ar + Me2N
- N2
Elks, J.; Hey, D.H. J. Chem. Soc. 1943, 441
147
Hardie, R.L.; Thomson, R.H. J. Chem. Soc. 1958, 1286
Basterfield, S.; Dyck, A.J. Can. J. Res. 1942, 20B, 240
Tiffeneau, M.; Tchoubar, B.; Le Tellier, S. Compt. Rend. 1943, 217, 588
Huisgen, R.; Horeld, G. Ann. Chem. 1949, 562, 137
Szwarc, M.; Williams, D. J. Chem. Phys. 1952, 20, 1171Jacquiss, M.T.; Szwarc, M. Nature 1952, 170, 312
Ingold, K.U.; Lossing, F.P. Can. J. Chem. 1953, 31, 30
.. Ph-Ar + HPh + Ar-H
[PhCOO]4Pb 4 Ph + 4 CO2 + Pb.
Hey, D.H. Stirling, C.J.M.; Williams, G.H. J. Chem. Soc. 1954, 2747
N
Ph
Ph
NHPh
NH
Ph
Ph
NHPh
N
Ph
Ph
NPh
H2O2LiAlH 4
N
Ph
Ph
NPh
major
major
Ph-H + Ph2CH-CHPh2
Ph-H + Ph2CH-CHPh2
Ph2CH2
decalin
148
Cohen, S.G.; Wang, C.H. J. Am. Chem. Soc. 1955, 77, 3628
OH
H
Ph-Ph.2 Ph
. .Ph-H +Ph + EtOH
.Ph + Ag + Ph3PbNO3Ph4Pb + AgNO3
Spice, J.E.; Twist, W. J. Chem. Soc. 1956, 3319
Ph I
O(CO)Ph
O(CO)Ph
O
Ph O
.- PhI .
Ar-HPhCOOAr + H
- CO2
PhAr-H
Ph-Ar + H. .Hey, D.H.; Stirling, C.J.M.; Williams, G.H. J. Chem. Soc. 1956, 1475
N NPh H
.
Ph-H
Ph-Ar + H
Ar-H
Ph-Ph
. .Ph + H- N2- H2O
- 2 Ag
Ag2OPhNHNH2
Hardie, R.L.; Thomson, R.H. J. Chem. Soc. 1957, 2512
149
N NPh C
O
Ph N NPh C
O
Ph
N NHPh C
O
PhCH3O
Ph-H ..Ph + H
- N2
+
.+.CH3OH
H+
Cohen, S.G.; Nicholson, J. J. Am. Chem. Soc. 1964, 86, 3892Cohen, S.G.; Nicholson, J. J. Org. Chem. 1965, 30, 1162
Porter, G.; Ward, B. Proc. Roy. Soc. London A 1965, 287, 457 (UV spectrum in gas phase)Cercek, B.; Kongshaug, M. J. Phys. Chem. 1970, 74, 4319 (UV spectrum in aqueous solution)Ikeda, N.; Nakashima, N.; Yoshihara, K. J. Am. Chem. Soc. 1985, 97, 3381 (UV spectrum in gas phase)
OH
tButBu
Br
OH
tButBu
+ Brhν .
.
150
OH
tButBu
OH
tButBu
Br
OH
tButBu
O
tButBu
Br
++
.
.
Lappin, G.R.; Zannucci, J.S. Tetrahedron Lett. 1969, 5085
. .Ph + N=OAr 12 K
308 nmPh-N=O
Engbert, J.M.; Dick, B. Appl. Phys. B 1996, 63, 531Engbert, J.M.; Slenczka, A.; Kensy, U.; Dick, B. J. Phys. Chem. 1996, 100, 11883
(iv) Benzoyl radical
O
.Reviews (acyl or acetyl radicals):Vinogradov, M.G.; Nikishin, G.I. Usp. Khim. 1971, 40, 1960Caronna, T.; Minisci, F. Rev. Reactive Species in Chemical Reactions 1976, 1, 263Boger, D.L. Isr. J. Chem. 1997, 37, 9349Chatgilialoglu, C.; Crich, D.; Komatsu, M.; Ryu, I. Chem. Rev. 1999, 99, 1991
151
O
Ph Cl
O
Ph
O
Ph
O
Ph O
O
Ph
+ 1/2 O2.2
2 + Zn + ZnCl22 .
Norris, J.F.; Franklin, D.R. Am. Chem. J. 1903, 29, 141 (suggestion)
O
Ph Ph
O
Ph
hν . + Ph.
O
Ph
O
Ph
O
Ph
2 .Ph-Ph2 Ph.
Glazebrook, H.H.; Pearson, T.G. J. Chem. Soc. 1939, 589
O
Ph
N N
Ph
Ph
N N
Ph
Ph O
Ph
.+.
152
Kharasch, M.S.; Zimmerman, M.; Zimmt, W.; Nudenberg, W. J. Org. Chem. 1953, 18, 1045
O
Ph
O
Ph O Ph
O
PhN N
O
Ph
.+.
.+ Ph-CHO.
Kharasch, M.S.; Schwartz, D.; Zimmerman, M.; Nudenberg, W. J. Org. Chem. 1953, 18, 1051 O
Ph NN
O
Ph
O
Ph
.2- N2
∆
Mackay, D.; Marx, U.F.; Waters, W.A. J. Chem. Soc. 1964, 4793
O
Br
R
O
R
hν .- Br.
R = H, Cl, OMe
Schmidt, U.; Kabitzke, K.H.; Markau, K. Angew. Chem. 1965, 77, 378Schmidt, U.; Kabitzke, K.H.; Markau, K. Monatsh. Chem. 1966, 97, 1000
153
O
O
O
OOtBu
tBuO
O
Ph NR
O..
Ph-C=O + R-N=O
.tBuOH + Ph-C=O.tBuO + Ph-CHO
.2 CO2 + 2 tBuO
Mackor, A.; Wajer, T.A.J.W.; de Boer, T.J. Tetrahedron 1968, 24, 1623
Krusic, P.J.; Rettig, T.A. J. Am. Chem. Soc. 1970, 92, 724 (ESR)
C O
Ph
I
...
.
.
+ IPh-C=O + I2
Ph-C=O + HIPh-CHO + I
2 II2
Solly, R.K.; Benson, S.W. J. Am. Chem. Soc. 1971, 93, 1592
O
Ph
OR
Ph
O
Ph
OR
Phhν . + .
154
O
Ph
O
NtBu
O
NPh
O
Ph. +
.
Ledwith, A.; Russell, P.J.; Sutcliffe, L.H. J. Chem. Soc. Perkin Trans. 2 1972, 1925
Simoes, J.A.M.; Griller, D. Chem. Phys. Lett. 1989, 158, 175 (photoacoustic calorimetry of benzoyl radical)
(v) Acyl radical
O
R
.Reviews:Vinogradov, M.G.; Nikishin, G.I. Usp. Khim. 1971, 40, 1960Caronna, T.; Minisci, F. Rev. Reactive Species in Chemical Reactions 1976, 1, 263Chatgilialoglu, C.; Crich, D.; Komatsu, M.; Ryu, I. Chem. Rev. 1999, 99, 1991
1o
. . COCOCl + Cl(COCl)2hν
hν .2 COCl(COCl)2
155
2o
COCl CO + Cl... .RCOCl + COClR + (COCl)2
.R + HClRH + Cl
. .2 CO + ClCOCOCl
. .CO + ClCOCl
.
Kharasch, M.S.; Brown, H.C. J. Am. Chem. Soc. 1942, 64, 329Kharasch, M.S.; Kane, S.S.; Brown, H.C. J. Am. Chem. Soc. 1942, 64, 1621
O
CH3
CH2
O
CH3
CH2
(CH3)2C=Ohν
CH3 + CH3-C=O . .CH3-C=O
.CO + CH3
..CH3-C=O + O2 CH3COO + O. .CH3 + (CH3)2C=O.
CH4 + .. + O2 CH3COOH + H-C=O
.
?
CH3 + O2. H-C=O + H2O.
156
.H-C=O CO + H..
H-C=O + O2 CO2 + OH.H + O2 HOO..Marcotte, F.B.; Noyes, W.A. Jr. J. Am. Chem. Soc. 1952, 74, 783
.tBu + CO2+ COtBuO. .CH3-C=O.CH3 + CO
.CH3 + (CH3)2C=O.tBuO
.2 tBuOtBu-O-O-tBu
Porter, G.B.; Benson, S.W. J. Am. Chem. Soc. 1953, 75, 2773
N N
OO O
.- N2
2
Cramer, R. J. Am. Chem. Soc. 1957, 79, 6215
.
. ....
RCOCl + CCl3
HCl
RClRH
- HRCHO
k2CCl4
k1CO + RRCO
157
Applequist, D.E.; Kaplan, L. J. Am. Chem. Soc. 1965, 87, 2194
O
R X
O
RO
R
O
R H
O
R
O
R
O
R R
.+ R..R-H + nBu3Sn.R + nBu3Sn-H
.R + CO.
.+ H.
+ nBu3Sn-X..+ nBu3Sn
..nBu3Sn + HnBu3Sn-H
R = PhCH2, Ph3C, PhCH2O
Kuivila, H.G.; Walsh, E.J. Jr. J. Am. Chem. Soc. 1966, 88, 571Walsh, E.J. Jr.; Kuivila, H.G. J. Am. Chem. Soc. 1966, 88, 576
158
O
PhPh
O
Ph
O
Ph
Ph-CH2-O-O-CH2-Ph+ Ph-CH2
.Ph-CH2O-O.
.Ph-CH2O-O+ O2
. Ph-CH2
PhCH2CH2Ph.
Ph-CH2
.+ Ph-CH2
+ Ph-CH2
.CO .
. .+ Ph-CH2
hν
Maillard, B.; Ingold, K.U.; Scaiano, J.C. J. Am. Chem. Soc. 1983, 105, 5095Lunazzi, L.; Ingold, K.U.; Scaiano, J.C. J. Phys. Chem. 1983, 87, 529
(vi) Benzyl radical
CH2
.
Reviews:Porter, G. Chem. Soc. Special Publ. 1957, 9, 139Lei, X. Res. Chem. Intermediates 1990, 14, 15
(PhCH2)2AsCl3 + 2 PhCH2CH2Ph(PhCH2)3As + 3 PhCH2Cl
(PhCH2)3As + 6 NaCl3 PhCH3Cl + AsCl3 + 6 Na
159
Michaelis, A.; Paetow, U. Ann. Chem. 1886, 233, 60
Dodonov, J.; Medox, H. Chem. Ber. 1935, 68B, 1254
CH3 CH2BrhνBr2
Kharasch, M.S.; Margolis, E.; White, P.C.; Mayo, F.R. J. Am. Chem. Soc. 1937, 59, 1405Kharasch, M.S.; White, P.C.; Mayo, F.R. J. Org. Chem. 1938, 3, 3
Blades, A.T.; Steacie, E.W.R. Can. J. Chem. 1954, 32, 1142 (pyrolysis of toluene)
Norman, I.; Porter, G. Proc. Roy. Soc. London 1955, 230A, 399Porter, G.; Wright, F. Trans. Faraday Soc. 1955, 51, 1469Beckwith, A.L.J.; Waters, W.A. J. Chem. Soc. 1957, 1001 (benzyl radicals reacting with anthracene)Porter, G.; Windsor, M.W. Nature 1957, 180, 187Porter, G.; Strachan, E. Trans. Faraday Soc. 1958, 54, 1595Porter, G.; Strachan, E. Spectrochim. Acta 1958, 12, 299
. PhCH2-CH2Ph2 PhCH2
.2 PhCH2 + Fe+22 PhCH2+ + Fe
PhCH2+ + Cl-PhCH2-Cl
Sisido, K.; Udo, Y.; Nozaki, H. J. Am. Chem. Soc. 1960, 82, 434
Hodgkins, J.E.; Megarity, E.D. J. Am. Chem. Soc. 1965, 87, 5322 (EPA solid matrix)
160
R
CH3
R
CH2
2 tBuO.tBuOOtBu
.+ tBuOH.+ tBuO
Kennedy, B.R.; Ingold, K.U. Can. J. Chem. 1966, 44, 2381
(vii) Koelsch radical
Ph
.
Koelsch, C.F. J. Am. Chem. Soc. 1932, 54, 4744Koelsch, C.F. J. Am. Chem. Soc. 1957, 79, 4439
Group IV centred radicals except carbon (Si, Ge, Sn)
(i) Silyl
R1
Si
R3 R2.
Reviews:Jackson, R.A. Adv. Free Radical Chem. 1969, 3, 231
161
Jackson, R.A. Chem. Soc. Special Publ. 1970, 295Sakurai, H. in Free Radicals, (J.K. Kochi, ed.) Wiley: New York, 1973, Vol. 2, p. 741Arthur, N.L.; Bell, T.N. Rev. Chem. Intermediates 1978, 1, 37Alberti, A.; Pedulli, G.F. Rev. Chem. Intermediates 1987, 8, 207Dohmaru, T. in Reactions of Special Radicals in Chemical Kinetics of Small Organic Radicals, (Z.B. Alfassi, ed.) CRC Press: Boca Raton, 1988,Vol. 3, p. 165Chatgilialoglu, C. NATO ASI Ser. Ser. C. 1989, 257, 119Chatgilialoglu, C. NATO ASI Ser. Ser. C. 1989, 260, 115Chatgilialoglu, C. Chem. Rev. 1995, 95, 1229Korolev, V.A.; Nefedov, O.M. Adv. Phys. Org. Chem. 1995, 30, 1Chatgilialoglu, C.; Schiesser, C.H. in The Chemistry of Organic Silicon Compounds, (Z. Rappoport, S. Patai, eds.) Wiley: Chichester, 2001, Vol. 3,p. 341
H3Si SiH3
H3Si SiH2 SiH3 H3Si SiH2
H3Si SiH2 :+ H2Si. H3Si..+ H3Si
∆ ..∆
2 H3Si
Emeleus, H.J.; Reid, C. J. Chem. Soc. 1939, 1021 (pyrolysis of disilane and trisilane)
Cl3SiCl3SiH +
5
(CH3COO)2
5hν
(CH3COO)2 2 CH3COO.CH3COO CH3 + CO2.CH3 + HSiCl3 CH4 + Cl3Si..
162
R-CH=CH2 + Cl3Si. R-CH-CH2SiCl3
..
R-CH-CH2SiCl3 + HSiCl3 R-CH2-CH2SiCl3 + Cl3Si.
Sommer, L.H.; Pietrusza, E.W.; Whitmore, F.C. J. Am. Chem. Soc. 1947, 69, 188 (first suggestion)Burkhard, C.A.; Krieble, R.H. J. Am. Chem. Soc. 1947, 69, 2687Barry, A.J.; DePree, L.; Gilkey, J.W.; Hook, D.E. J. Am. Chem. Soc. 1947, 69, 2916
HC CH
SiCl3
RCH CH2 RCH2
SiCl3via
+ Cl3SiH(PhCOO)2
(PhCOO)2+ Cl3SiH
Cl3Si.
Burkhard, C.A.; Krieble, R.H. J. Am. Chem. Soc. 1947, 69, 2687
F
F
F
F
SiCF2
CF2HMe
MeH
SiCF2
CF2
Me
MeH
CF2CF2H
Me
SiMe CF2CF2H
CF2CF2H
Me2SiH2 + hν
Geyer, A.M.; Haszeldine, R.N. J. Chem. Soc. 1957, 1038
Menapace, L.W.; Kuivila, H.G. J. Am. Chem. Soc. 1964, 86, 3047Walling, C.; Cooley, J.H.; Ponaras, A.A.; Racah, E.J. J. Am. Chem. Soc. 1966, 88, 5361
Bennett, S.W.; Eaborn, C.; Hudson, A.; Hussain, H.A.; Jackson, R.A. J. Organometallic Chem 1969, 16, P36Bennett, S.W.; Eaborn, C.; Hudson, A.; Jackson, R.A.; Root, K.D.J. J. Chem. Soc. A 1970, 348Krusic, P.J.; Kochi, J.K. J. Am. Chem. Soc. 1969, 91, 3938
163
. .(tBu)3Si(iPr)3Si
Jackson, R.A.; Weston, H. J. Organometallic Chem. 1984, 277, 13 (ESR)
R
N
O
O
Si(SiMe3)3
. .(Me3Si)3Si + RNO2
. .tBuOH + (Me3Si)3SitBuO + (Me3Si)3SiH
.2 tBuOhν
tBuO-OtBu
R
N
O
O
Si(SiMe3)3
.(Me3Si)3SiOH + (Me3Si)3Si+ (Me3Si)3SiH.(Me3Si)3SiO
.R-N=O + (Me3Si)3SiO
.
Ballestri, M.; Chatgilialoglu, C.; Lucarini, M.; Pedulli, G.F. J. Org. Chem. 1992, 57, 948
(ii) Germyl
R1
Ge
R3 R2.
Reviews:Korolev, V.A.; Nefedov, O.M. Adv. Phys. Org. Chem. 1995, 30, 1
164
Me3Ge
tBuO. + Me3GeH Me3Ge. + tBuOH
.Me3Ge + .
tBuO-OtBuhν
2 .tBuO
Kawamura, T.; Kochi, J.K. J. Organometallic Chem. 1973, 47, 79
(iii) Stannyl
R1
Sn
R3 R2.
Reviews:
Baines, K.; Dicke, R.; Neumann, W.P.; Vorspohl, K. NATO ASI Ser. Ser. C 1989, 260, 107.H3Sn
Morehouse, R.L.; Christiansen, J.J.; Gordy, W. J. Chem. Phys. 1966, 45, 1751 (ESR, 4.2 K, Kr matrix)Jackel, G.S.; Gordy, W. Phys. Rev. 1968, 76, 443
.R'-CH2-CH2SnR3 + R3Sn+ R3Sn-HR'-CH-CH2SnR3
..
R'-CH-CH2SnR3.R'-CH=CH2 + R3Sn
Neumann, W.P.; Albert, H.J.; Kaiser, W. Tetrahedron Lett. 1967, 2041
165
R = (Me3Si)2CH
:..R3Sn + RSn::R2Sn + R2Sn
Davidson, P.J.; Hudson, A.; Lappert, M.F.; Lednor, P.W. Chem. Commun. 1973, 829
nBu3Sn
tBuO. + nBu3SnH nBu3Sn. + tBuOH
.nBu3Sn + .
tBuO-OtBuhν
2 .tBuO
Kawamura, T.; Kochi, J.K. J. Organometallic Chem. 1973, 47, 79
R = Me3Si, tBu
R = (Me3Si)2CH
..
(R2N)3Sn
R3Sn
Hudson, A.; Lappert, M.F.; Lednor, P.W. J. Chem. Soc. Dalton Trans. 1976, 2369
S
S
S
S
S
S
R3Sn ..R3Sn +
.2 R3Snhν
R3Sn-SnR3
166
S
S
S
S S
S
R3SnS
S
.R3Sn + CH2=CH2 + .Forrest, D.; Ingold, K.U. J. Am. Chem. Soc. 1978, 100, 3868
R = PhC(CH3)2CH2, Ph, Mes, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl
.R3Sn
Lehnig, M.; Buschhaus, H.U.; Neumann, W.P.; Apoussidis, T. Bull. Soc. Chim. Belges 1980, 89, 907
Sn
iPr
iPr
iPrSn
iPr
iPr
iPr Sn
iPr
iPr
iPr 2
33
.3
Lehnig, M.; Apoussidis, T.; Neumann, W.P. Chem. Phys. Lett. 1983, 100, 189 (ESR)
Group V centred radicals (N, P)Nitrogen centred radicals:
Reviews:Nelsen, S.F. in Free Radicals (J.K. Kochi, ed.) Wiley: New York, 1973, Vol. 2, p. 527Michejda, C.J.; Campbell, D.H.; Sieh, D.H.; Koepke, S.R. ACS Symp. Ser. 1978, 69, 292Miura, Y. Trends Org. Chem. 1997, 6, 197Alfassi, Z.B. (ed.) N-Centered Radicals, Wiley: New York, 1998
(i) Aminyl
167
R1
N
R2
.Reviews:Danen, W.C.; Neugebauer, F.A. Angew. Chem. 1975, 87, 823.
Ph2N-CPh3
Ph2N-NONO
Ph3C
.2 Ph2N∆
Ph2N-NPh2
PbO22 Ph2NH
Wieland, H. Ann. Chem. 1911, 381, 200Wieland, H.; Gambajarin, S. Chem. Ber. 1906, 36, 1499
N NH2
R1
R2
N N
R1
R2
N N
R1
R2
N
R1
R2
R1 = Me, R2 = Me; R1 = Me, R2 = Ph
.2∆- N2
HgO2
Erusalimskii, B.L.; Dolgoplosk, B.A.; Kavunenko, A.P. Zh. Obshchei Khim. 1957, 27, 267; 301
O2N N
R
O
O
OtBuO2N N
R ..- CO2
+ tBuO
Pedersen, C.J. J. Org. Chem. 1958, 23, 255
168
NH2
tBu tBu
tBu
NH
tBu tBu
tBu
..R
Atherton, N.M.; Land, E.J.; Porter, G. Trans. Faraday Soc. 1963, 59, 818
N N NN
Ph Ph
O O
N
Ph
O
N
Ph
O
Cl N
Ph
O77 KCCl4
hν
hν
77 KCCl4
N2 + 2 .
.+ Cl.
Johnston, K.M.; Williams, G.H.; Williams, H.J. Chem. Ind. 1966, 991Johnston, K.M.; Williams, G.H.; Williams, H.J. J. Chem. Soc. Sect. B 1966, 1114
N NR2N NR2.N2 + 2 R2N
hν
Kochi, J.K.; Krusic, P.J. J. Am. Chem. Soc. 1969, 91, 6161Danen, W.C.; Kensler, T.T. J. Am. Chem. Soc. 1970, 92, 5235
169
NH N.tBuOH +.+ tBuO
.2 tBu-OtBu-O-O-tBu
Danen, W.C.; Kensler, T.T. Tetrahedron Lett. 1971, 2247
N
tBu
.Nelsen, S.F.; Landis, R.T.; Kiehle, L.H.; Leung, T.H. J. Am. Chem. Soc. 1972, 94, 1610
(ii) N-alkoxy-N-alkylamino radicals
R1
N
OH
.Reviews:None.
N
R1
R2
OH
N
R1
R2
OH
HO NH
R1
R2
O
HO
..+ .HO
.Ti+4 + OH- + HOTi+3 + H2O2
Smith, P.; Fox, W.M. Can. J. Chem. 1969, 47, 2227
170
O
NH O
OtBu
RR
NOtBu
.hν
Danen, W.C.; West, C.T. J. Am. Chem. Soc. 1971, 93, 5582
R
NH
OtBu R
N
OtBu
tBu-O-O-tBu 2 tBu-O.+ tBuO. tBuOH +
.
R
NH
OtBu R
N
OtBu
.CH4 +.+ CH3
.N2 + 2 CH3CH3-N=N-CH3
Danen, W.C.; West, C.T.; Kensler, T.T. J. Am. Chem. Soc. 1973, 95, 5716
(iii) Amido radicals
O
R1 N
R2
.Reviews:Goosen, A. South African J. Chem. 1979, 32, 37
O
R1 NCl
R2
O
R1 NR2
R1 R2tBu MeMe tBu
hν+ Cl..
171
Danen, W.C.; Gellert, R.W. J. Am. Chem. Soc. 1972, 94, 6853
O
R N
OtBu
.Koenig, T.; Hoobler, J.A.; Mabey, W.R. J. Am. Chem. Soc. 1972, 94, 2514
O
CH3 NH
Br
O
CH3 NH
O
CH3 NH
O
CH3 N
OH
CH3 N.+ H+_..
+ Br-.+ e- (aq)
Fessenden, R.W. Chem. Lett. 1974, 29, 364
(iv) Hydrazyl
R1
N
N
R3
R2
.
Reviews:Nelsen, S.F. ACS Symp. Ser. 1978, 69, 309
172
N N
Ph
Ph2N
Ph
NPh2
Ph2N N
Ph
NO
Ph2N N
Ph
CPh3
.Ph3C NO
.2 Ph2N-NPh
PbO22 Ph2N-NHPh
Goldschmidt, S. Chem. Ber. 1920, 53, 44
N ClPh2N.
Goldschmidt, S.; Wolf, A.; Wolffhardt, E.; Drimmer, I.; Nathan, S. Ann. Chem. 1924, 437, 194
O2N
NO2
NO2
N
N Ph
Ph
N+
NO2
NO2
N
N Ph
Ph
- O
- O
O2N
NO2
NO2
N
N Ph
Ph
.+_
....
+..
Turkevich, J.; Oesper, P.F.; Smyth, C.P. J. Am. Chem. Soc. 1942, 64, 1179 (dipole moment measurement)
173
N NAr Ar
Ph
ArN
NAr
Ph
.+
hν
Wan, J.K.S.; Hess, L.D.; Pitts, J.N. J. Am. Chem. Soc. 1964, 86, 2069
O2N
NO2
NO2
N
N Ph
Ph
O2N
NO2
NO2
NH
N Ph
Ph
KMnO4nBu4N+ Br- .
Brown, K.C.; Weil, J.A. Can. J. Chem. 1986, 64, 1836
O
PR1
R1
N N
R2
R2
R1 R2OEt MeEt MeOEt H, tBuOPh H, tBuEt H, tBu
.
Tordo, P. NATO ASI Ser. Ser. C 1986, 189, 191
NX NH
R
R
R
R
P
O
OEt
OEt
NX N
R
R
R
R
P
O
OEt
OEt
X = O, CH2; R = H, Me
tBuO-OtBuhν
.
174
Lucarini, M.; Pedulli, G.F. J. Org. Chem. 2000, 65, 2723
(v) Nitroxide radicals
N+ O -
R1
R2
.Reviews:Keana, J.F.W. Chem. Rev. 1978, 78, 37Perkins, M.J. Adv. Phys. Org. Chem. 1980, 17, 1Volodarsky, L.B.; Reznikov, V.A.; Ovcharenko, V.I. Synthetic Chemistry of Stable Nitroxides, CRC Press: Boca Raton, FL, 1994
O -
N+
K+ - O3S SO3 - K+
OH
N
K+ - O3S SO3 - K+- KOHKNO2 + 2 KHSO3
KMnO4 orPbO2 .
Fremy, E. Ann. Chim. Phys. 1845, 15[3], 408; 459
N+
NH
O -
HN
NH
N+
NH
O -
HN
NH
N
NH
O
HN
NH
.. .
Piloty, O.; Schwerin, B.G. Chem. Ber. 1901, 34, 1870; 2354
175
N+
NH
N
O -
HN
N
- O
HN
N+
NH
N+
NH
N
O -
HN
N
- O
HN
N+
NH
. .
Piloty, O.; Vogel, W. Chem. Ber. 1907, 36, 1283
N+
NH
O -
N+
HN
- O
N
NH
O
N
HN
O... .
Niementowski, S. Chem. Ber. 1910, 43, 3012Kuhn, R.; Blau, W. Ann. Chem. 1958, 615, 99
(vi) Thioaminyl radicals
R1 N
S R2
.Reviews:Bassindale, A.R.; Ipey, J. in Chemistry of Sulphenic Acids and Their Derivatives, (S. Patai, ed.) Wiley: Chichester, 1990, p. 101Miura, Y. Trends in Org. Chem. 1997, 6, 197Miura, Y. Recent Res. Development Org. Chem. 1998, 2(Pt. 2), 251
176
tBu
tBu
N S Cl.
Miura, Y.; Katsura, Y.; Kinoshita, M. Chem. Lett. 1977, 409
N S.
Miura, Y.; Asada, H.; Kinoshita, M.; Ohta, K. J. Phys. Chem. 1983, 87, 3450
N S R
Ph
Ph
Ph
R = alkyl, aryl.
Miura, Y.; Isogai, M.; Kinoshita, M. Bull. Chem. Soc. Jpn 1987, 60, 3065
(vii) Sulfonamidyl radicals
SO2
N
R2
R1
.Reviews:Bassindale, A.R.; Iley, J.N. in Chemistry of Sulphonic Acids, Esters, and Their Derivatives (S. Patai, ed.) Wiley: Chichester, 1991, p. 197 - 247
177
SO2
NH2
O
SK+ - O
O
O O S
O
O
O - K+
SO2
NH
SO2
NH.
- K2SO4, - H2SO4
Dewar, P.S.; Forrester, A.R.; Thomson, R.H. J. Chem. Soc. Perkin Trans. 1 1972, 2862
tBu SO2
N OR.
Teeninga, H.; Engberts, J.B.F.N. Rec. Trav. Chim. Pays-Bas 1978, 97, 59
SO2
NHOMe
O
SK+ - O
O
O O S
O
O
O - K+
SO2
N-OMe
SO2
N-OMe
X X X
- K2SO4, - H2SO4
.
Forrester, A.R.; Johansson, E.M.; Thomson, R.H. J. Chem. Soc. Perkin Trans. 1 1979, 1112
178
RSO2 N
Y
Br
RSO2 N
Y
RSO2 N
Y
H
Y = alkyl, alkoxy
.- tBuOH
tBuO
.hν
RSO2 N
tBu
H
RSO2 N
tBu
N
O
RSO2 tBu
..RSO2 + tBu-N=O.- tBuOH
tBuO.
Teeninga, H.; Zomer, B.; Engberts, J.B.F.N. J. Org. Chem. 1979, 44, 4717
NMeSO2
R
Cl
NMeSO2
R
R = Me, Et, CHMe2..- Cl
hν
Danen, W.C.; Gellert, R.W. J. Am. Chem. Soc. 1980, 102, 3264
(viii) N-Thiosulfonamidyl radicals
SO2
N
S
R1 R2
.Reviews:None.
179
SO2 N
SAr
SAr
SO2 N
SAr
H
SO2 N
SAr
.PbO2
hν
Miura, Y.; Kunishi, T.; Kinoshita, M. J. Org. Chem. 1985, 50, 5862Miura, Y.; Kunishi, T.; Kinoshita, M. Bull. Chem. Soc. Jpn. 1985, 58, 1696
(ix) VerdazylsReviews:Power, P.P. Chem. Rev. 2003, 103, 789
N
Ph
N N-Ph
PhNH N
Ph
N N-Ph
N
Ph
N
NN
HN
PhPh
Ph
N
NN
N
PhPh
Ph
.[O]MeI
Kuhn, R.; Trischmann, H. Angew. Chem. Int. Ed. 1963, 8, 155Kuhn, R.; Trischmann, H. Monatsh. Chem. 1964, 95, 457Kuhn, R.; Neugebauer, F.A.; Trischmann, H. Monatsh. Chem. 1966, 97, 846
180
N
Ar1
Ar2
NH2
OAr1
Ar2
N
Ar1
Ar2
NH CH
Ar1
Ar2
N
Ar1
Ar2
N CH
Ar1
Ar2
N
Ar1
Ar2
N CH
Ar1
Ar2
2 + 2[O]
2.
2
Kuhn, R.; Neugebauer, F.A. Monatsh. Chem. 1963, 94, 1
N NH2
Ar1
Ar2
N N
Ar1
Ar2
CH NH N
Ar1
Ar2
N N
Ar1
Ar2
CH N N
Ar1
Ar2
.[O]BF3
+ HC(OEt)32
Kuhn, R.; Neugebauer, F.A.; Trischmann, H. Angew. Chem. Int. Ed. 1964, 3, 232Kuhn, R.; Trischmann, H. Monatsh. Chem. 1966, 97, 554
N N
NN
(CH2)4
N N
NN
Ph
Ph
Ph
Ph
Ph
Ph
H
H NN
NNN
N
NN
Ph
Ph
Ph
Ph..
.
.Kuhn, R.; Fischer-Schwarz, G. Monatsh. Chem. 1966, 97, 517
181
NN
N
N
NN
N
N
Ph
Ph
Ph
Ph
N+N+
N
N
NN
N
N
Ph
Ph
Ph
Phn
n
.. _ _
R1R1
R1
R2
R2
N
NN
N
PhPh
N
NN
N
PhPh
R1 = . R2 = .Kuhn, R.; Neugebauer, F.A.; Trischmann, H. Monatsh. Chem. 1966, 97, 525Kuhn, R.; Neugebauer, F.A.; Trischmann, H. Angew. Chem. Int. Ed. 1965, 4, 72Kurusu, Y.; Yoshida, H.; Okawara, M. Tetrahedron Lett. 1967, 3595
N
NN
N
R1 R1
R3
R2
N
NN
N
R1 R1
O
R2
..
Neugebauer, F.A. Angew. Chem. Int. Ed. 1973, 12, 455
182
Neugebauer, F.A.; Fischer, H.; Siegel, R. Chem. Ber. 1988, 121, 815
Phosphorus centred radicals:
Reviews:Bentrude, W.G. in Free Radicals, (J.K. Kochi, ed.) Wiley: New York, 1973, Vol. 2, p. 595Walling, C.; Pearson, M.S. Topics Phosphorus Chem. 1966, 3, 1Cadogan, J.I.G. Adv. Free Radical Chem. 1967, 2, 203Bentrude, W.G. Ann. Rev. Phys. Chem. 1967, 18, 283
(i) Phosphinoyl (phosphonyl, phosphono) radicals O
P
R1 R2.
Reviews:Rachon, J. Pol. J. Environ. Studies 1996, 5, 62
O
POP
O
OR
OR
OR
O
P
RO OR
O
PRO
OR
ORP
RO
RO
R = Et, nPr, nBu
2∆
.
Michalski, J.; Stec, W.; Zwierzak, A. Chem. Ind. 1965, 345
O
P
R R
O
P
EtO Et.R = NMe2, Et, Me(CH2)5.
Davies, A.G.; Dennis, R.W.; Griller, D.; Ingold, K.U.; Roberts, B.P. Molecular Physics 1973, 25, 989
183
O
PRO OH
OR
O
PRO
OR
O
PRO
O -
R = Me, Et
..γ-rays
Kerr, M.C.L.; Webster, K.; Williams, F. Molecular Physics 1973, 25, 1461Geoffroy, M.; Ginet, L.; Lucken, E.A. Molecular Physics 1976, 31, 745
O
P
X X.
Roberts, B.P.; Singh, K. J. Organometallic Chem. 1978, 159, 31 (ESR spectrum)
O
tBuO OO
O
OtBu .2 tBuO + 2 CO2
O
PRO H
OR
O
PRO
OR
+ tBuO + tBuOH. .
184
O
PRO
OR
CN
S-tBuPO
ORRO
CN
S-tBu
. +.
Stella, L.; Merenyi, R.; Janousek, Z.; Viehe, H.G. J. Phys. Chem. 1980, 84, 304
O
P Ph
Ph
O
R
O
R
O
PPh Ph
hν
.+ .
O
RN O
O
PPh
N O
O
R
Ph N O N O P Ph
O
Ph
+ ..
.+.
Baxter, J.E.; Davidson, R.S.; Hageman, H.J.; Overeem, T. Makromolec. Chem. Rapid Commun. 1987, 8, 311 (first nitroxide trapping ofphosphinoyl radicals)
185
C P
O
R2
R3
O
R1 C
O
R1 P
O
R2
R3
C P
O
OR2
OR3
O
R1 C
O
R1 P
O
OR2
OR3
hν . .+
+ ..hν
Majima, T.; Schnabel, W. J. Photochem. Photobiol. A: Chem. 1989, 50, 31Majima, T.; Konishi, Y.; Bottcher, A.; Kuwata, K.; Kamachi, M.; Schnabel, W. J. Photochem. Photobiol. A: Chem. 1991, 58, 239
O
Ar P
O
Ph
Ph O
Ar
P
O
Ph
Ph
P
O
Ph
Ph
X
COOMe
COOMe
P
O
Ph
Ph .R-X
.. + hν
Sluggett, G.W.; McGarry, P.F.; Koptyug, I.V.; Turro, N.J. J. Am. Chem. Soc. 1996, 118, 7367Weber, M.; Khudyakov, I.V.; Turro, N.J. J. Phys. Chem. A 2002, 106, 1938
186
Weber, M.; Turro, N.J. J. Phys. Chem. A 2003, 107, 3326
O
PC C
OO
Ar Ar
R
C
O
Ar
O
P C
O
Ar
R
+ ..hν
O
P C
O
Ar
R
O
P C
O
Ar
R
O-O
O
P C
O
Ar
R
H
O
P C
O
Ar
R
Br
O
P C
O
Ar
R
R'OOC
N+ N+ O
P C
O
Ar
R
N N+.
++
.
.CH2=CHCOOR'
.- Cl3C
Br-CCl3
.- Ph-S
Ph-SH
O2
.
Jockusch, S.; Turro, N.J. J. Am. Chem. Soc. 1998, 120, 11773
187
O P
O
Ph
PhO P
O
Ph
Ph
O OPPh2
hν
..
Zhao, N.; Strehmel, B.; Gorman, A.A.; Hamblett, I.; Neckers, D.C. J. Phys. Chem. A 1999, 103, 7757
O
PPh
Ph
CH2Ph
O
PPh
Ph
.CH2-Ph. +hν
Zhao, N.; Neckers, D.C. J. Org. Chem. 2000, 65, 2145
(ii) Phosphinyl radicals
P
R1 R2.
Reviews:Bentrude, W.G. Ann. Rev. Phys. Chem. 1967, 18, 283
O
OO
O
O
O+ CO2 + CH3
..
188
CH3 + PCl3 CH3-Cl + PCl2..R-CH=CH2 + PCl2. R-CH-CH2-PCl2
..
R-CH-CH2-PCl2 + R-CH=CH2 R-CH-CH2-CHR-CH2-PCl2
.R-CH-CH2-PCl2.
+ PCl3 R-CHCl-CH2-PCl2 + PCl2..
R-CH-CH2-CHR-CH2-PCl2 + PCl3 .R-CHCl-CH2-CHR-CH2-PCl2 + PCl2
Kharasch, M.S.; Jensen, E.V.; Urry, W.H. J. Am. Chem. Soc. 1945, 67, 1864
N NNC CN NC
NC NC H
R2P
R2P
R2P
R2P
- N2
2 .
. + R2P-H + R2P.
.+ R2P . . + R2P.R2P-H
=
.- R2P
189
Pellon, J. J. Am. Chem. Soc. 1961, 83, 1915
R
P
R
.R = Cl, Br
Andrews, L.; Frederick, D.L. J. Phys. Chem. 1969, 73, 2774 (IR spectra in solid Ar matrix)
P P
Ph
Ph
Ph
PhPh
P
Ph
hν .2
Wong, S.K.M.; Wan, J.K.S. Spectrosc. Lett. 1970, 3, 135
P
R RR = NMe2, Et, EtO, Me(CH2)5.
Davies, A.G.; Dennis, R.W.; Griller, D.; Ingold, K.U.; Roberts, B.P. Molecular Physics 1973, 25, 989
77 KR3P R2P + R. .60Co γ-rays
R = H, iPr, OMe, SMe, Ph, Cl, SPr, SEt
Fullam, B.W.; Mishra, S.P.; Symons, M.C.R. J. Chem. Soc. Dalton Trans. 1974, 2145Fullam, B.W.; Symons, M.C.R. J. Chem. Soc. Dalton Trans. 1975, 861
hνPh3P Ph2P + Ph. .Cook, W.T.; Vincent, J.S.; Bernal, I.; Ramirez, F. J. Chem. Phys. 1974, 61, 3479
190
R
P
RP P
R
R
R
R
P P
R
R
R
R
tBuO
R
P
tBuO R
R = OEt, NMe2
tBu-O-O-tBuhν
2 tBuO.+ tBuO. . .
+
Griller, D.; Roberts, B.P.; Davies, A.G.; Ingold, K.U. J. Am. Chem. Soc. 1974, 96, 554
77 KP(OR)3
60Co γ-raysP(OR)2 + RO..
Kerr, C.M.L.; Webster, K.; Williams, F. J. Phys. Chem. 1975, 79, 2650
Cl
P
N N
SiMe3
SiMe3
Me3Si
SiMe3
P
N N
SiMe3
SiMe3
Me3Si
SiMe3
- NaCl
.Na
Cl
P SiMe3
SiMe3
Me3Si
SiMe3
P SiMe3
SiMe3
Me3Si
SiMe3
Na
.- NaCl
Gynane, M.J.S.; Hudson, A.; Lappert, M.F.; Power, P.P. Chem. Commun. 1976, 623
191
Gynane, M.J.S.; Hudson, A.; Lappert, M.F.; Power, P.P.; Goldwhite, H. J. Chem. Soc. Dalton Trans. 1980, 2428Cowley, A.H.; Kemp, R.A. Inorg. Chem. 1983, 22, 547
CH3
P
CH3
.Roberts, B.P.; Singh, K. J. Organometallic Chem. 1978, 159, 31 (ESR spectrum)
P SiMe3
SiMe3
Me3Si
SiMe3
Fe(CO)4
P SiMe3
SiMe3
Me3Si
SiMe3
.+ Fe(CO)5+ Fe2(CO)9
.
P SiMe3
SiMe3
Me3Si
SiMe3
P SiMe3
SiMe3
Me3Si
SiMe3
Co(CO)3(CO)3Co
+ 2 CO
..+ Co2(CO)8
Cowley, A.H.; Kemp, R.A.; Wilburn, J.C. J. Am. Chem. Soc. 1982, 104, 331
(iii) Phosphoranyl radicals
R
PR
R
R.
192
Reviews:Bentrude, W.G. ACS Symp. Ser. 1978, 69, 321Roberts, B.P. Adv. Free Radical Chem. 1980, 6, 225Bentrude, W.G. Acc. Chem. Res. 1982, 15, 117Bentrude, W.G. Reactive Intermediates 1983, 3, 199
R-SH + S=P(OEt)3R-S-H + P(OEt)3
Hoffman, F.W.; Ess, R.J.; Simmons, T.C.; Hanzel, R.S. J. Am. Chem. Soc. 1956, 78, 6414hν
.+[Ph3P-CHBr2]Br- + Br2CHBr3CH+Ph3P-CHBr2
.
. .Br2CH + BrBr3CH ..Ph3P-CHBr2Ph3P + Br2CH
Ramirez, F.; McElvie, N. J. Am. Chem. Soc. 1957, 79, 5829
. R-S-R+ R R-S..R + S=P(OEt)3R-S-P(OEt)3
..
R-S-P(OEt)3
..R-S + P(OEt)3
2 R-SR-S-S-R
Walling, C.; Rabinowitz, R. J. Am. Chem. Soc. 1957, 79, 5326Walling, C.; Rabinowitz, R. J. Am. Chem. Soc. 1959, 81, 1243Walling, C.; Basedow, O.H.; Savas, E.S. J. Am. Chem. Soc. 1960, 82, 2181Buckler, S.A. J. Am. Chem. Soc. 1962, 84, 3093
193
hν
R3P + tBuO
tBuO-OtBu 2 tBuO
R3P-OtBu
(RO)3P + tBuO (RO)3P-OtBu
....
.Krusic, P.J.; Mahler, W.; Kochi, J.K. J. Am. Chem. Soc. 1972, 94, 6033
OR
P
RO OR
P OR
RO
RO
tBuO O P
OR
OR
OR
.tBu +
R = Et, Me
tBu-O-O-tBuhν
2 tBuO.+ tBuO. .
Griller, D.; Roberts, B.P.; Davies, A.G.; Ingold, K.U. J. Am. Chem. Soc. 1974, 96, 554
OMe
PMeO OMe
OtBu
.
Roberts, B.P.; Singh, K. J. Organometallic Chem. 1978, 159, 31 (ESR spectrum)
(iv) Thiophosphinoyl (phosphinothioyl) radicals S
P
R1 R2.
194
Reviews:None.
S
PR
R
Cl
S
PR
R
S
PR
R
S
PR
R
N
O
tBu
.+ tBu-N=O.
.+ Cl.hν
Karlsson, H.; Lagercrantz, C. Acta Chem. Scand. 1970, 24, 3411
S
P
EtO OEt.
Davies, A.G.; Dennis, R.W.; Griller, D.; Ingold, K.U.; Roberts, B.P. Molecular Physics 1973, 25, 989
Group VI centred radicals (O, S, Se)
Oxygen centred radicals:(i) Acetoxy (acetoxyl) radicals
O
R O.Reviews:
195
None. O
Ph OO
O
PhO
Ph O
.. 2 Ph- CO2
2
Brodie, B.C. Ann. Chem. 1858, 108, 79Hey, D.H. J. Chem. Soc. 1934, 1966Waters, W.A. J. Chem. Soc. 1937, 113Roberts, J.S.; Skinner, H.A. Trans. Faraday Soc. 1949, 45, 339
McDowell, C.A.; Thomas, J.H. J. Chem. Soc. 1949, 2208; 2217
Marcotte, F.B.; Noyes, W.A. Jr. J. Am. Chem. Soc. 1952, 74, 783Volman, D.H.; Graven, W.M. J. Chem. Phys. 1952, 20, 919Nicholson, A.J.C. J. Chem. Phys. 1952, 20, 1811Norrish, R.G.W. Z. Elektrochem. Angew. Physik. Chem. 1952, 56, 705Porter, G.B.; Benson, S.W. J. Am. Chem. Soc. 1953, 75, 2773Nicholson, G.R.; Szwarc, M.; Taylor, J.W. J. Chem. Soc. 1954, 2767
Ausloos, P.; Steacie, E.W.R. Can. J. Chem. 1955, 33, 47
Farmer, J.B.; Lossing, F.P.; Marsden, D.G.H.; Steacie, E.W.R. J. Chem. Phys. 1955, 23, 1169
O O
O
(fast)
(slow)
.CO + CH3.
∆ .+ CH3.
Szwarc, M.; Taylor, J.W. J. Chem. Phys. 1955, 23, 2310
196
N
S
O
O
R
O
O
RN
S
O
O
RN
SR
.
.
..
+
+R
Barton, D.H.R.; Crich, D.; Motherwell, W.B. Tetrahedron 1985, 41, 3901
(ii) Alkoxy radicals R O.Reviews:Walling, C. Pure Appl. Chem. 1967, 15, 69
Griller, D.; Wayner, D.D.M. Pure Appl. Chem. 1989, 61, 717Orlando, J.J.; Tyndall, G.S.; Wallington, T.J. Chem. Rev. 2003, 103, 4657
OO-OH
- Fe(CN)6-3
H+
Fe(CN)6-4
+ H2O.Fordham, J.W.L.; Williams, H.L. J. Am. Chem. Soc. 1950, 72, 4465Kharasch, M.S.; Fono, A.; Nudenberg, N. J. Org. Chem. 1950, 15, 763
197
O O O O
O O Ph O O Ph+. .
..+
Kharasch, M.S.; Fono, A.; Nudenberg, W. J. Org. Chem. 1951, 16, 105Kharasch, M.S.; Nudenberg, N.; Arimoto, F.S. Science 1951, 113, 392 (addition to olefins)Boardman, H. J. Am. Chem. Soc. 1953, 75, 4268
..
RO- + Fe+3RO + Fe+2
RO + Fe+3ROOH + Fe+2
Orr, R.J.; Williams, H.L. J. Am. Chem. Soc. 1955, 77, 3715
O OH O
O O OH O O OH+.+.
hν .+ HO.
Zwolenik, J.J. J. Phys. Chem. 1967, 71, 2464
198
O O O.2
Niki, E.; Kamiya, Y.; Ohta, N. Bull. Chem. Soc. Jpn 1968, 41, 1466
O
O
β-scission+ CH3..
Howard, J.A.; Ingold, K.U. Can. J. Chem. 1969, 47, 3797
(iii) Iminoxyl radicals
N
OR1
R2
.
Reviews:Rozantsev, E.G. Usp. Khim. 1966, 35, 1549
N
R1
R2
OH
N
R1
R2
OR1 R2t-Bu Mei-Pr i-Pri-Bu i-Pr
.or PbO2or AgO
K3[Fe(CN)6]
Fedtke, M.; Mitternacht, H. Z. Chem. 1964, 4, 389
199
N
OHR1
R2
N
OR1
R2
.Pb(OAc)4
Lemaire, H.; Rassat, A. Tetrahedron Lett. 1964, 2245
N
OHR1
R2
N
OR1
R2
NH4(NO3)
Ce(NO3)4
.
Thomas, J.R. J. Am. Chem. Soc. 1964, 86, 1446
N
R1
R2
OH
N
R1
R2
OPbO2
.
Gilbert, B.C.; Norman, R.O.C. J. Chem. Soc. (Phys. Org.) 1966, 86
NOH
NO .Pb(OAc)4
Ar
NOH
Ar
NO
Ar
NO
OAc
_.Pb(OAc)4
.
200
Lown, J.W. J. Chem. Soc. B 1966, 441
NH
N
R OH
NH
N
R OH
NH
N
R O
+ Br2-.
+.+ H+
.
- 2 Br-
Everett, S.A.; Naylor, M.A.; Stratford, M.R.L.; Patel, K.B.; Ford. E.; Mortensen, A.; Ferguson, A.C.; Vojnovic, B.; Wardman, P. J. Chem. Soc.Perkin Trans. 2 2001, 1989
(iv) Nitroxyl radicals
O
N
R1 R2
.
Reviews:Rozentsev, E.G. Free Nitroxyl Radicals, (translated by B.J. Hazzard) Plenum: New York, 1970Rozantsev, E.G.; Sholle, V.D. Synthesis 1971, 190Rozantsev, E.G.; Sholle, V.D. Synthesis 1971, 401Volodarsky, L.B.; Reznikov, V.A.; Ovcharenko, V.I. Synthetic Chemistry of Stable Nitroxides, CRC Press: Boca Raton, FL, 1994
Ar1 N O
OH
N
Ar1 Ar2
O
N
Ar1 Ar2
.[O]
- HOMgX
H2O
+ Ar2-MgX
201
R N
O
R
.
Wieland, H.; Roseeu, A. Chem. Ber. 1912, 45, 494Wieland, H.; Offenbächer, M. Chem. Ber. 1914, 47, 2111Wieland, H.; Roseeu, A. Chem. Ber. 1915, 48, 1117Wieland, H.; Roth, K. Chem. Ber. 1920, 53, 210Wieland, H.; Kögel, F. Chem. Ber. 1922, 55, 1798
OR
O -
N+ ORRO
O -
N ORRO
2Zn
ClO4-
+
1. HNO3/H2SO4
2. HClO4
Meyer, K.H.; Gottlieb-Billroth, H. Chem. Ber. 1919, 52, 1476Meyer, K.H.; Reppe, W. Chem. Ber. 1921, 54, 327
NO NHO Ph
NO Ph.
PhMgBr [O]
Hückel, W.; Liegel, W. Chem. Ber. 1938, 71, 1442
202
Johnson, D.; Rogers, M.; Trappe, G. J. Chem. Soc. 1956, 1093 (postulated existence of free nitroxyl radicals)Rogers, M. J. Chem. Soc. 1956, 2784
N+
NH
O -
N+
HN
- O
N
NH
O
N
HN
O... .
Niementowski, S. Chem. Ber. 1910, 43, 3012Kuhn, R.; Blau, W. Ann. Chem. 1958, 615, 99
N O.
Lebedev, O.L.; Kazarnovskii, S.N. Treatises on Chemistry and Chemical Technology, Gorky, 1959, 3, 649Il'yasov, A.V. Zh. Strukt. Khim. 1962, 3, 95Garif'yasov, I.S.; Il'yasov, A.V.; Yablokov, Yu. V. Dokl. Akad. Nauk SSSR 1963, 149, 876
N O
tBu
tBu
.
N NR R∆
N2 + 2 R
.
203
N O
tBu
R
R + tBu-N=O
. .
Hoffmann, A.K.; Henderson, A.T. J. Am. Chem. Soc. 1961, 83, 4671Hoffmann, A.K.; Hodgson, W. J. Am. Chem. Soc. 1961, 83, 4675Hoffmann, A.K.; Hodgson, W.; Maricle, D.; Jura, W. J. Am. Chem. Soc. 1964, 86, 631Hoffmann, A.K.; Feldman, A.; Gelblum, E.; Hodgson, W. J. Am. Chem. Soc. 1964, 86, 639Hoffmann, A.K. FR 1,357,477 (1964)Hoffmann, A.K. US 3,253,015 (1966)
N NO O. .Rozantsev, E.G.; Golubev, V.A.; Neiman, M.B. Izv. Akad. Nauk SSSR, Ser. Khim. 1965, 393
N
(CH2)6
N
CC
O O
N
O
OH
O
O NH(CH2)6
NH
O
O
NNO O..
.+ 2
O
NH NH
NHHN O
NH NH
NNO O. .
MnO2
204
Rozantsev, E.G.; Golubev, V.A.; Neiman, M.B.; Kokhanov, Yu.V. Izv. Akad. Nauk SSSR, Ser. Khim. 1965, 572
NR O R = H, OH, O=, =NOH, OAc.
Briere, R.; Lemaire, H.; Rassat, A. Bull. Soc. Chim. Fr. 1965, 3273
NH N
O
[O]
.
Rozantsev, E.G. Usp. Khim. 1966, 35, 1549
NH
O
N
O
O
[O]
.Rozantsev, E.G. Izv. Akad. Nauk SSSR, Ser. Khim. 1966, 770Rozantsev, E.G.; Neiman, M.B. Tetrahedron 1964, 20, 131
205
R1
NH
R2 R1
N
R2
O
[O]
.
Lebedev, O.L.; Khidekel, M.L.; Razuvaev, G.A. Dokl. Akad. Nauk SSSR 1961, 140, 1327Rozantsev, E.G.; Neiman, M.B. Tetrahedron 1964, 20, 131Rozantsev, E.G.; Krinitzkaya, L.A. Tetrahedron 1965, 21, 491Rozantsev, E.G.; Burmistrova, R.M. Dokl. Chem. 1966, 166, 38Rozantsev, E.G.; Kokhanov, Yu.V. Bull. Acad. Sci. USSR 1966, 1422
N+
O -
N+
OH
R
H N+
O -
R
N
OH
R
R' N
O
R
R'
RMgX [O] R'MgX [O]
.Bonnett, R.; Brown, R.F.C.; Clark, V.M.; Sutherland, I.O.; Todd, A. J. Chem. Soc. 1959, 2094Brown, R.F.C.; Clark, V.M.; Lamchen, M.; Todd, A. J. Chem. Soc. 1959, 2116Keanu, J.F.W.; Lee, T.D.; Bernard, E.M. J. Am. Chem. Soc. 1976, 98, 3052
(v) Kenyon-Banfield radical
N+
N
O
Ph
- O Ph
N
ON
O
Ph
Ph
..
206
Ph
NH
OH
O Ph
N+
- O
Ph
N+
- O
CH2 -
+- H2O
Ph
N+
- O
N
OH
Ph
Ph
N+
- O
N
O
Ph[O]
.
Banfield, F.H.; Kenyon, J. J. Chem. Soc. 1926, 1612Baldry, P.J.; Forrester, A.R.; Thomson, R.H. J. Chem. Soc. Perkin Trans. 2 1976, 76
(vi) Peroxy radicals
R
O
O.Reviews:
Ingold, K.U. Acc. Chem. Res. 1969, 2, 1Swern, D. (ed.) Organic Peroxides, Wiley-Interscience: New York, Vol. 1 - 3, 1970 - 1981Ando, W. (ed.) Organic Peroxides, Wiley: New York, 1992Alfassi, Z.B. (ed.) Peroxyl Radicals, Wiley: New York, 1997
Foner, S.N.; Hudson, R.L. J. Chem. Phys. 1953, 21, 1608 (detection of hydroperoxide radical)
207
O O.Bersohn, M.; Thomas, J.R. J. Am. Chem. Soc. 1964, 86, 959 (detection by ESR)
O OH O
O O OH O O OH+.+.
hν .+ HO.
Zwolenik, J.J. J. Phys. Chem. 1967, 71, 2464
Howard, J.A.; Ingold, K.U. Can. J. Chem. 1969, 47, 3797
(vii) Phenoxy (phenoxyl) radicals
O
R
.
Reviews:Becconsall, J.K.; Clough, S.; Scott, G. Trans. Faraday Soc. 1960, 56, 459 (ESR of phenoxy radicals)Müller, E. Revista Portuguesa de Quimica 1972, 14, 129Iley, J.; Taylor, P.G. in The Chemistry of Hydroxyl, Ether Peroxide Groups, (S. Patai, ed.) Wiley: Chichester, 1993, p. 241Prokof'ev, A.I. Russ. Chem. Rev. 1999, 68, 727
.2 ArO + 2 NaI2 ArO- Na+ + I2
208
Müller, E.; Ley, K.; Kiedaisch, W. Chem. Ber. 1954, 87, 1605Hunter, W.H.; Seyfried, L.M. J. Am. Chem. Soc. 1921, 43, 151
HO
t-Bu
t-Bu
t-Bu O
t-Bu
t-Bu
t-Bu
K3[FeIII (CN)6] .
Müller, E.; Ley, K. Z. Naturforsch. 1953, 8B, 694Müller, E.; Ley, K. Chem. Ber. 1954, 87, 922Müller, E.; Ley, K.; Kiedaisch, W. Chem. Ber. 1954, 87, 1605Müller, E.; Ley, K. Chem. Ber. 1955, 88, 601Cook, C.D. J. Am. Chem. Soc. 1953, 18, 261Cook, C.D.; Kuhn, D.A.; Fianu, P. J. Am. Chem. Soc. 1956, 78, 2002Blanchard, H.S. J. Org. Chem. 1960, 25, 264
O
PhPh
Ph
OH
tButBu
tBu
OH
PhPh
Ph
O
tButBu
tBu
..+ +
Dimroth, K.; Kalk, F.; Sell, R.; Schlömer, K. Ann. Chem. 1959, 624, 51
209
HO
tBu
tBu
CH2 OH
tBu
tBu
O CH
tBu
tBu
tBu
tBu
OPbO2
ether.
Coppinger, G.M. J. Am. Chem. Soc. 1957, 79, 501Joshi, B.S. Chem. Ind. 1957, 525Bartlett, P.D.; Funahashi, T. J. Am. Chem. Soc. 1962, 84, 1605ESR:Besev, C.; Lund, A.; Vanngard, T.; Hakansson, R. Acta Chem. Scand. 1963, 17, 2281Hyde, J.S. J. Chem. Phys. 1965, 43, 1806Hausser, K.H.; Brunner, H.; Jochims, J.C. Mol. Phys. 1966, 10, 253
O
O
tBu
tBu
O
.
.
Yang, N.; Kastro, A. J. Am. Chem. Soc. 1960, 82, 6208
210
OH
tButBu
tBu
O
tButBu
tBu
O
tButBu
tBu
OH
tButBu
tBu
..+ +
Kreilick, R.W.; Weissman, S.I. J. Am. Chem. Soc. 1962, 84, 306
O
tButBu
R1
OH
R2
O
O
tBu
tBu
R1
R2
OH
O
tBu
R1
R2
.H...- H - tBu
Matsuura, T.; Nishinaga, A.; Cahnmann, H.J. J. Org. Chem. 1962, 27, 3620
.PhOH2O2 / Ti+2
PhOH
Dixon, W.T.; Norman, R.O.C. Proc. Chem. Soc. 1963, 97 (ESR of phenoxy radical)
211
O
tBu
tBu
N
NMe2
NMe2
.
Neuhoeffer, O.; Heitmann, P. Chem. Ber. 1963, 96, 1027
O
I
I
COOH
HO
.
Matsuura, T.; Kon, H.; Cahnmann, H.J. J. Org. Chem. 1964, 29, 3058.. CH4 + PhOCH3 + HOPh
Mulcahy, M.F.R.; Williams, D.J. Austr. J. Chem. 1965, 18, 20
212
N
NO2
NO2O2N
NPh2
OH
tButBu NH
NO2
NO2O2N
NPh2
O
tButBu.
+ +
.
Ayscough, P.B.; Russell, K.E. Can. J. Chem. 1967, 45, 3019
O
tButBu
tBu
OH
R
OH
tButBu
tBu
O
R
..
++
O
tButBu
tBu
O
R
O
tButBu
tBu O
+
..
Mahoney, L.R.; DaRooge, M.A. J. Am. Chem. Soc. 1970, 92, 890
213
OH
tButBu
O
tButBu
.1/4 PbO2
- 1/4 Pb- 1/2 H2O
Stebbins, R.; Silicio, F. Tetrahedron 1970, 26, 291
Sulfur centred radicals:
Reviews:Kice, J.L. in Free Radicals, (J.K. Kochi, ed.) Wiley: New York, 1973, Vol. 2, p. 711Davies, D.L.; Parrott, M.J. in Int. Rev. Sci.: Org. Chem. Ser. 2 Butterworth: London, 1975, Vol. 10, p. 47Asmus, K.D. NATO ASI Ser. A 1990, 197, 155Griller, D.; Simoes, J.A.M. NATO ASI Ser. A 1990, 197, 327Alfassi, Z.B. (ed.) S-Centered Radicals, Wiley: New York, 1999
(i) Sulfanyl (mercapto, thiyl) radicals R S.Reviews:Kooijman, E.C. Pure Appl. Chem. 1967, 15, 81Kellogg, R.M. Methods in Free Radical Chem. 1969, 2, 1Ito, O. Trends Phys. Chem. 1992, 3, 245Chatgilialglu, C.; Guerra, M. The Chemistry of Sulphur Containing Functional Groups, (Z. Rappoport, ed.) Wiley: Chichester, 1993, p. 363Ito, O. Res. Chem. Intermediates 1995, 21, 69
S
R
. R = H, p-MeO, p-Me2N, p-COOEt, p-Ph, o-OH
214
Schmidt, U.; Müller, A.; Markau, K. Tetrahedron Lett. 1963, 1091
MeS
tBuO.2hν
tBuO-OtBu
.+ MeS.+ tBuOH.MeS+ MeSH.tBuO
Kawamura, T.; Kochi, J.K. J. Organometallic Chem. 1973, 47, 79
S
R R
S
R
R
S-R'..
.2 R'-Shν
R'-S-S-R'
+ R'-S
Alberti, A.; Bonini, B.F.; Pedulli, G.F. Tetrahedron Lett. 1987, 28, 3737
(ii) Sulfinyl radicals
R S
O
.Reviews:Chatgilialoglu, C. in Chemistry of Sulphones and Sulfoxides, (S. Patai, Z. Rappoport, C. Stirling, eds.) Wiley: New York, 1988, p. 1081 - 1087
215
Ar S
OH
SAr
.+ Cl.
Ar-S=Ohν
Ar-S(O)Cl
. . .Ar-S=O.HO
Ar-S-OHH2O2
Ar-S- H2O
Ar-SH + HO
...
Ar-S=O- H+
- ArS-
Ar-S-S-Ar + HO
Gilbert, B.C.; Kirk, C.M.; Norman, R.O.C.; Laue, H.A.H. J. Chem. Soc. Perkin Trans. 2 1977, 497...R-S=O + other productsR-S-O-OR-S + O2
NH2
COOHHS
NH2
COOH
O
NH
O NH
COOH
HS
cysteine
glutathione
Sevilla, M.D.; Becker, D.; Swarts, S.; Herrington, J. Biochem. Biophys. Res. Commun. 1987, 144, 1037Becker, D.; Swarts, S.; Champagne, M.; Sevilla, M.D. Int. J. Radiat. Biol. 1988, 53, 767
216
R S
O
O S
O
O
R
R S SO S
O
SR
O
O
RR
R S
O
O S
O
O
R
O
R = Ph
2 RSO2-Cl 2 RSO2 R-S=O + R-SO2-O. . .
2 R-S=O RS + RSO2
. . .
R-SO2-O + RSO2..
Bennett, J.E.; Brunton, G.; Gilbert, B.C.; Whittall, P.E. J. Chem. Soc. Perkin Trans. 2 1988, 1359
R'-S=O + R'S-OH+ R'-SH.
R'-S-O-O.
. .R'-S-O-OR'-S + O2
..R-OOH + R'-SR-OO + R'-SH
Swarts, S.G.; Becker, D.; De Bolt, S.; Sevilla, M.D. J. Phys. Chem. 1989, 93, 155 (gamma irradiation in Cl2FC-CF2Cl at 77 K; ESR of radicals)
(iii) Sulfonyl radicals
R S
O
O
.Reviews:
217
Freeman, F.; Keindl, M.C. Sulfur Reports 1985, 4, 231Chatgilialoglu, C. in The Chemistry of Sulphones and Sulphoxides, (S. Patai, Z. Rappoport, C. Stirling, eds.) Wiley: Chichester, 1988, p. 1089Bertrand, M.P. Org. Prep. Proced. Inter. 1994, 26, 257Crich, D. in Organosulfur Chemistry, (P. Page, ed.) Academic Press: London, 1995, p. 49
. ...
.
Et3Si-Cl + Ph-SO2Et3Si + Ph-SO2Cl
tBuOH + Et3SitBu-O + Et3SiH
2 tBu-Ohν
tBu-O-O-tBu
Chatgilialglu, C.; Gilbert, B.C.; Norman, R.O.C. J. Chem. Soc. Perkin Trans. 2 1979, 770Chatgilialglu, C.; Gilbert, B.C.; Norman, R.O.C. J. Chem. Soc. Perkin Trans. 2 1980, 1429Bennett, J.E.; Brunton, G.; Gilbert, B.C.; Whittall, P.E. J. Chem. Soc. Perkin Trans. 2 1988, 1359
(iv) Sulfuranyl radicals
R1
S
R2 R3.
Reviews:Anklam, E.; Margaretha, P. Res. Chem. Intermed. 1989, 11, 127Chatgilialoglu, C. in Chemistry of Sulphenic Acids and Their Derivatives (S. Patai, ed.) Wiley: Chichester, 1990, p. 549 - 569Margaretha, P. in S-Centered Radicals (Z.B. Alfassi, ed.) Wiley: Chichester, 1999, p. 277 - 288
. .RO-SF4RO + SF4
. .RO + Clhν
RO-Cl
218
Gregory, A.R.; Karavelas, S.E.; Morton, J.R.; Preston, K.F. J. Am. Chem. Soc. 1975, 97, 2206
MeO
S
OMe MeO
S
OMe
OMe
.+ .MeO
Cooper, J.W.; Roberts, B.P. Chem. Commun. 1977, 228
S RR
R R
S RR
R R
O-SiMe3
S RR
R R
Me3Si-O.+
.
Me3Si-OH + .Gara, W.B.; Roberts, B.P. J. Organometallic Chem. 1977, 135, C20
S RR
S RR
O-CMe3
S RR
Me3C-O.+
.
Me3C-OH + .Gara, W.B.; Giles, J.R.M.; Roberts, B.P. J. Chem. Soc. Trans. Perkin 2 1979, 1444
219
SMe
O
OO
tBu
SMe
O
OO
S
O
...hν
- tBuO
Perkins, C.W.; Martin, J.C.; Arduengo, A.J.; Lau, W.; Alegria, A.; Kochi, J.K. J. Am. Chem. Soc. 1980, 102, 7753Nakanishi, W.; Kusuyama, Y.; Ikeda, Y.; Iwamura, H. Bull. Chem. Soc. Jpn. 1983, 56, 3123
O
Et S
O
tBu S
R1
S
R2
R1
SR2
R1
SR2
R1
SR2
S(CO)tBu
S-CF3
S(CO)Et
.
.
.
.
.
.CF3S
Giles, J.R.M.; Roberts, B.P. J. Chem. Soc. Perkin Trans. 2 1980, 1497
(v) Thionitroxide radicals
N S
R1
R2
.
220
Reviews:None.
N S
N SO
N S NS
N S NS OO
∆2
2∆ .
.
Bennett, J.E.; Sieper, H.; Tavs, P. Tetrahedron 1967, 23, 1697
N S NS N S.2∆
N S S NN+
NO
Ph
- O Ph
N S
N+
NO
Ph
- O Ph
SN
.+ . +
Danen, W.C.; Newkirk, D.D. J. Am. Chem. Soc. 1976, 98, 516
221
N S S N N S.hν2
Maillard, B.; Ingold, K.U. J. Am. Chem. Soc. 1976, 98, 520
(vi) Thiophenoxy (phenylthio, phenylthiyl, benzenethiyl) radicals
S
R
.Reviews:None.
X
SS
X
X
S
X = H, MeO, Me2N, OH, EtOOC, Ph
hν2
.
Schmidt, U.; Müller, A.; Markau, K. Chem. Ber. 1964, 97, 405
Selenium centred radicals:
Reviews:Deryagina, E.N.; Voronkov, M.G.; Korchevin, N.A. Usp. Khim. 1993, 62, 1173Deryagina, E.N.; Voronkov, M.G. Sulfur Reports 1995, 17, 89
222
(i) Phenylselanyl (phenylseleno) radical
Se .Reviews:None.
Schmidt, U.; Müller, A.; Markau, K. Tetrahedron Lett. 1963, 1091 (ESR)
Ph Se
Se Ph
Ph
Se
Se
Ph ..
2 Ph-Se
2 PhCH2Se
hν
hν
Schmidt, U.; Müller, A.; Markau, K. Chem. Ber. 1964, 97, 405
.R-C(OO )H-CH2-SePh+ O2R-CH-CH2-SePh.. .
R-CH-CH2-SePhPh-Se + R-CH=CH2
.2 Ph-SePh-Se-Se-Ph
Ito, O. J. Am. Chem. Soc. 1983, 105, 850
223
COOMeR
PhSe
R
COOMe PhSe
R COOMe
PhSe
R
COOMe PhSe
R COOMeSePh
SePh
.- Ph-Se
Ph-Se-Se-Ph
..+ .Ph-Se
.2 Ph-SePh-Se-Se-Ph
Back, T.G.; Krishna, M.V. J. Org. Chem. 1988, 53, 2533
(ii) Selanyl R Se.Reviews:None.
X = Cl, Br..Ph2Se-X + Ph
X-irradiationPh3Se-X
Franzi, R.; Geoffroy, M.; Ginet, L.; Leray, N. J. Phys. Chem. 1979, 83, 2898
Radical Anions
Reviews:Kaiser, E.T.; Kevan, L. (eds.) Radical Anions, Interscience Publishers: New York, 1968Szwarc, M. Prog. Phys. Org. Chem. 1968, 6, 323Melby, L.R. in The Chemistry of the Cyano Group (Z. Rappoport, ed.) Wiley-Interscience: London, 1970. Vol. 2, p. 639Russell, G.A.; Norris, R.K. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 423Rossi, R.A. Acc. Chem. Res. 1982, 15, 164Hertler, W.R.; Mahler, W.; Melby, L.R.; Miller, J.S.; Putscher, R.E.; Webster, O.W. Molecular Crystals & Liquid Crystals 1988, 171, 205Saveant, J.M. Adv. Phys. Org. Chem. 2000, 35, 117
224
Rathore, R.; Kochi, J.K. Adv. Phys. Org. Chem. 1998, 31, 193Webster, O.W. J. Polym. Sci. A 2002, 40, 210 (tetracyanoethylene radical anion)Todres, Z.V. Organic Ion Radicals, Marcel Dekker, Inc.: New York, 2003
K2 K+
- 2_
KK+
.
Berthelot, M. Compt. Rend. 1866, 63, 836Berthelot, M. Ann. Chim. Phys. 1867, 12, 1955
Na
_.Na+
Schlenk, W.; Appenrodt, J.; Michael, A.; Thal, A. Chem. Ber. 1914, 47, 473
Weitz, E.Z. Z. Elektrochem. 1928, 34, 538Willstätter, R.; Seitz, F.; Bumm, E. Chem. Ber. 1928, 61, 871Schlenk, W.; Bergmann, E. Ann. Chem. 1928, 463, 1; 1928, 464, 1Scott, N.D.; Walker, J.F.; Hansley, V.L. J. Am. Chem. Soc. 1936, 58, 2442Walker, J.F.; Scott, N.D. J. Am. Chem. Soc. 1938, 60, 951Hueckel, W.; Bretschneider, H. Ann. Chem. 1939, 540, 157Lipkin, D.; Paul, D.E.; Townsend, J.; Weissman, S.I. Science 1953, 117, 534Weissman, S.I.; Townsend, J.; Paul, D.E.; Pake, G.E. J. Chem. Phys. 1953, 21, 2227Wertz, J.E.; Vivo, J.L. J. Chem. Phys. 1955, 23, 2441
NC
NC
CN
CN
NC
NC
CN
CN
.+ A+
._+ A
225
Webster, O.W.; Mahler, W.; Benson, R.E. J. Org. Chem. 1960, 25, 1470Webster, O.W.; Mahler, W.; Benson, R.E. J. Am. Chem. Soc. 1962, 84, 3678Phillips, W.D.; Rowell, J.C.; Weissman, S.I. J. Chem. Phys. 1960, 33, 626 (ESR spectrum)
NC
NC
CN
CN
._
Acker, D.S.; Hertler, W.R. J. Am. Chem. Soc. 1962, 84, 3770
(tBu)2N-OtBu.+ tBu(tBu)2N-O..(tBu)2N-O.tBu-N=O + tBu
tBu-N=O + tBuO-.+ tBu._tBu-NO2
.NO2- + tButBu-NO2
_.._tBu-NO2tBu-NO2 + e-
Hoffmann, A.K.; Hodgson, W.G.; Jura, W.H. J. Am. Chem. Soc. 1961, 83, 4675
Radical Cations
Reviews:Michaelis, L. Chem. Rev. 1935, 16, 243Kaiser, E.T.; Kevan, L. (eds.) Radical Ions, Interscience Publishers: New York, 1968Szwarc, M. Prog. Phys. Org. Chem. 1968, 6, 323Ledwith, A. Acc. Chem. Res. 1972, 5, 133Russell, G.A.; Norris, R.K. in Organic Reactive Intermediates, (S.P. McManus, ed.) Academic Press: New York, 1973, p. 423Bard, A.J.; Ledwith, A.; Shine, H.J. Adv. Phys. Org. Chem. 1976, 13, 156Bard, A.J.; Faulkner, L.R. Electrochemical Methods, Wiley: New York, 1980Mattes, S.L.; Farid, S. Org. Photochem. 1983, 6, 233
226
Yoshida, K. Electro-oxidation in Organic Chemistry, Wiley: New York, 1984Hammerich, O.; Parker, V.D. Adv. Phys. Org. Chem. 1984, 20, 55Mattay, J. Angew. Chem. Int. Ed. 1987, 26, 825Roth, H.D. Top. Curr. Chem. 1992, 163, 131Eberson, L. Adv. Phys. Org. Chem. 1998, 31, 91Saveant, J.M. Adv. Phys. Org. Chem. 2000, 35, 117Rathore, R.; Kochi, J.K. Adv. Phys. Org. Chem. 1998, 31, 193Werst, D.W.; Trifunac, A.D. Acc. Chem. Res. 1998, 31, 651Todres, Z.V. Organic Ion Radicals, Marcel Dekker, Inc.: New York, 2003Wiest, O.; Oxgaard, J.; Saettel, N.J. Adv. Phys. Org. Chem. 2003, 38, 87
.+Ph2NHH2SO4
Ph2NH
Laurent, A. Ann. Chim. Phys. 1835, 59, 367Laurent, A. Ann. Chem. Phys. 1836, 17, 89
Wurster salts
NH2H2N NH2H2NNH2H2N
- e-- e-
[O].+
[O] + +
NMe2Me2N NMe2Me2N
Wurster's blue
+ Br-.+
HOAc
Br2
NH2Me2N NH2Me2NBr2
HOAc
+.+ Br-
Wurster's red
227
Baeyer, A. Chem. Ber. 1875, 8, 614Wurster, C. Chem. Ber. 1879, 12, 522Wurster, C.; Sendtner, R. Chem. Ber. 1879, 12, 1803Wurster, C.; Schobig, E. Chem. Ber. 1879, 12, 1807Wurster, C. Chem. Ber. 1879, 12, 2071Wurster, C., Chem. Ber. 1886, 19, 3195Willstätter, R.; Piccard, J. Chem. Ber. 1908, 41, 1458Piccard, J. Chem. Ber. 1911, 46, 1843Michaelis, L. J. Am. Chem. Soc. 1931, 53, 2953Katz, H. Z. Physik 1933, 87, 238Michaelis, L.; Schubert, M.P.; Granick, S. J. Am. Chem. Soc. 1939, 61, 1981
N N
Ar
Ar
Ar
Ar
N N+
Ar
Ar
Ar
Ar
.1/2 X2
X -
Wieland, H. Chem. Ber. 1907, 40, 4260; 4263.Ar3N+ Br-Ar3N + 1/2 Br2
Wieland, H.; Wecker, E. Chem. Ber. 1910, 43, 699
.+SbF5
SbF5
+.
228
Meyer, K.H. Chem. Ber. 1910, 43, 161Hilpert, S.; Wolf, L. Chem. Ber. 1913, 46, 2215
S
NH
S
NH
S
NH- e-- e-
+ + 2.
Kehrmann, F.; Speitel, J.; Grandmougin, E. Chem. Ber. 1914, 47, 2976Kehrmann, F.; Diserens, L. Chem. Ber. 1915, 48, 318
Weitz, E.Z. Z. Elektrochem. 1928, 34, 538Weitz, E.; Meitzner, E. Chem. Ber. 1931, 64B, 2909Giusa, R. Gazz. Chim. Ital. 1945, 75, 162Hughes, G.K.; Hush, N.S. J. Proc. Roy. Soc. New South Wales 1947, 81, 48Holden, A.N.; Yager, W.A.; Merritt, F.R. J. Chem. Phys. 1951, 19, 1319
.+H2SO4
NN
O
O
O
O
NN
O
O
O
O
+.H2SO4
Hirschon, G.M.; Gardner, D.M.; Fraenkel, G.K. J. Am. Chem. Soc. 1953, 75, 4115Hoijtink, G.J.; Weijland, W.P. Rec. Trav. Chim. Pays-Bas 1957, 76, 836Kon, H.; Blois, M.S. J. Chem. Phys. 1958, 28, 743
229
.+ArNH2
SbF5Ar-NH2
Kainer, H.; Hausser, K.H. Chem. Ber. 1957, 86, 1563Lewis, I.C.; Singer, L.S. J. Chem. Phys. 1965, 43, 2712Lewis, I.C.; Singer, L.S. J. Chem. Phys. 1966, 44, 2082
R2N CH CH CH CH NR2 R2N CH CH CH CH NR2 R2N CH CH CH CH NR2
n n
+.- e- - e-
n
+ +
N+
S
CH CH
N+
S
..
N+
CH CH CH CH
N.Hünig, S. Ann. Chem. 1964, 676, 32Hünig, S.; Balli, H.; Conrad, H.; Schott, A. Ann. Chem. 1964, 676, 36; 52Hünig, S. Chem. Eng. News 1966, 44, 102Hünig, S.; Geiger, H.; Kaupp, G.; Kniese, W. Ann. Chem. 1966, 697, 116
230
N Cl
R1
R2
N+
R1
R2
H.H2SO4
hν
Danen, W.C.; Rickard, R.C. J. Am. Chem. Soc. 1972, 94, 3254
CN
O
Ph Ph
CN
O
Ph Ph
CN
O
Ph Ph
B+ .B+ . A- .A- .
+
_
+
...
.+
+
_
hν
Ph Ph Ph Ph
PhPh
Ph
Ph Ph
Ph
Ph PhPh Ph
O+R
H
Ph Ph
OR
+ AA- .
+ AA- .
..+ ROH
+.
.+
+.+
Neutefel, R.A.; Arnold, D.R. J. Am. Chem. Soc. 1973, 95, 4080Pincock, J.A. Can. J. Chem. 2003, 81, 413
231
N X N X X = CR3, NR2, OMe, Cl, NMe3+
- e-
Nelsen, S.F.; Kessel, C.R.; Brien, D.J. J. Am. Chem. Soc. 1980, 102, 702
N N COORROOC N N COORROOC
N N COORROOC N N
COOR
PPh3
ROOC
N N
COOR
PPh3
ROOC N N COORROOC N N
COOR
PPh3
ROOC N N COORROOC
N N COORROOC N N
COOR
PPh3
ROOC
N N
COOR
PPh3
ROOC N N
COOR
PPh3
ROOC
N N
COOR
PPh3
ROOC
+
_
+ Ph3P+.+
+
_+ Ph3P
.+
.+
+ Ph3P+.
_.+
_
+
+
+
..
+
+ Ph3P. _
_ ..+ Ph3P++ Ph3P
Camp, D.; Hanson, G.R.; Jenkins, I.D. J. Org. Chem. 1995, 60, 2977
232
Br
OMeO
OMeO
OHMeO
hν
- Br..
H+ .+
Schepp, N.P. J. Org. Chem. 2004, 69, 4931
Distonic radical cations
Reviews:Radom, L.; Bouma, W.J.; Nobes, R.H. Pure Appl. Chem. 1984, 56, 1831Yates, B.F.; Bouma, W.J.; Radom, L. Tetrahedron 1986, 42, 6225
Westwood, N.P.C. J. Molecular Struct. 1988, 173, 227Bouchoux, G. Mass Spectrometry Rev. 1988, 7, 1Hammerum, S. Mass Spectrometry Rev. 1988, 7, 123Bouchoux, G. Mass Spectrometry Rev. 1988, 7, 203Stirk, K.M.; Kiminikenen, L.K.M.; Kenttaemaa, H.I. Chem. Rev. 1992, 92, 1649Bouchoux, G. Trends in Org. Chem. 1993, 4, 161Kenttaemaa, H.I. Org. Mass Spectrometry 1994, 29, 1Smith, R.L.; Chou, P.K.; Kenttaemaa, H. in Structure, Energetics, and Dynamics of Organic Ions, (T. Baer, C.Y. Ng, I. Powis, eds.) Wiley:Chichester, 1996, p. 197Audier, H.E.; Fossey, J.; Leblanc, D.; Mourgues, P.; Troude, V. NATO ASI Ser., Ser. C 1999, 521, 27Gebecki, J.; Marcinek, A. in General Aspects of the Chemistry of Radicals, (Z.B. Alfassi, ed.) Wiley: Chichester, 1999, p. 175
Golding, B.T.; Radom, L. J. Am. Chem. Soc. 1976, 98, 6331 (prediction of stability in gas phase)Bouma, W.J.; MacLeod, J.K.; Radom, L. Nouv. J. Chim. 1978, 2, 439
233
CH2 XH
Cl+
H
Cl
H
CH2 O
H
CH3
+..
.X = OH, NH2, SH, Cl, Br
+
Holmes, J.L.; Lossing, F.P.; Terlouw, J.K.; Burgers, P.C. J. Am. Chem. Soc. 1982, 104, 2931
Terlouw, J.K.; Heerma, W.; Dijkstra, G.; Holmes, J.L.; Burgers, P.C. Int. J. Mass Spectrom. Ion Phys. 1983, 47, 147
CH2 OH2 CH2 OH2
.+ e-
++_
Yates, B.F.; Bouma, W.J.; Radom, L. J. Am. Chem. Soc. 1984, 106, 5805
NH3 CH2 NH3 + CH2=CH2
. +.+
+ NH3.+
Sack, T.M.; Cerny, R.L.; Gross, M.L. J. Am. Chem. Soc. 1985, 107, 4562
Z = bond, CH2, CHMe, CH2CH2; X = OH, NH2
+..CH3-Z-CH2-XCH2-Z-CH2-X-H+
Wesdemiotis, C.; Danis, P.O.; Feng, R.; Tso, J.; McLafferty, F.W. J. Am. Chem. Soc. 1985, 107, 8059
234
Ar
ArAr
Ar
Ar
ArO
O
Cl
Cl
Cl
Cl
O
O
Cl
Cl
Cl
Cl
OO
OO
ArAr
Ar
Ar
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
acetone-d6 .
+
+.hν
Miyashi, T.; Takahashi, Y.; Mukai, T.; Roth, H.D.; Schilling, M.L.M. J. Am. Chem. Soc. 1985, 107, 1079
OH2. +
Postma, R.; Ruttink, P.J.A.; Van Baar, B.; Terlouw, J.K.; Holmes, J.L.; Burgers, P.C. Chem. Phys. Lett. 1986, 123, 409
235
NH2
NH2.+.+
Qin, X.Z.; Williams, F. J. Am. Chem. Soc. 1987, 109, 5957
O
O2N
O
O2N
O
O2N
+
.- CH3- e-
.+
Moraes, L.A.B.; Eberlin, M.N. J. Am. Chem. Soc. 1998, 120, 11136
Silylenes and germylenes
R1
Si
R2
:
Reviews:
Denk, M.; West, R.; Hayashi, R. in Organosilicon Chemistry II: from molecules to materials, (N. Auner; J. Weis, eds.) VCH: Weinheim,1994, p. 251Weidenbruch, M. Coord. Chem. Rev. 1994, 130, 275Becerra, R.; Walsh, R. Res. Chem. Intermediates 1995, 3, 263Korolev, V.A.; Nefedov, O.M. Adv. Phys. Org. Chem. 1995, 30, 1
West, R.; Denk, M. Pure Appl. Chem. 1996, 68, 785Gehrhus, B.; Lappert, M.F. Phosphorus, Sulfur, Silicon and Related Elements 1997, 124-125, 537Gaspar, P.P.; West, R. in The Chemistry of Silicon Compounds, (Z. Rappoport; Y. Apeloig, eds.) Wiley: Chichester, 1998, Vol. 2 (Pt. 3), p. 2463
236
Kira, M. Pure Appl. Chem. 2000, 72, 2333Veszpremi, T. Adv. Molecular Structure Res. 2000, 6, 267Haaf, M.; Schmedake, T.A.; West, R. Acc. Chem. Res. 2000, 33, 704Tokitoh, N.; Okazaki, R. Coord. Chem. Rev. 2000, 210, 251 (silylenes, germylenes, stannylenes, plumbylenes)Gehrhus, B.; Lappert, M.F. J. Organometallic Chem. 2001, 617-618, 209 (stable bis(amino)silylenes)Gaspar, P.P.; Xiao, M.; Pae, D.H.; Berger, D.J.; Haile, T.; Chen, T.; Lei, D.; Winchester, W.R.; Jiang, P. J. Organometallic Chem. 2002, 646, 68
Gaspar, P.P.; Pate, B.D.; Eckelman, W. J. Am. Chem. Soc. 1966, 88, 3878Atwell, W.H.; Weyenberg, D.R. J. Am. Chem. Soc. 1968, 90, 3438Atwell, W.H.; Weyenberg, D.R. Angew. Chem. Int. Ed. Engl. 1969, 8, 469Atwell, W.H.; Mahone, L.G.; Hayes, S.F.; Uhlmann, J.G. J. Organometal. Chem. 1969, 18, 69Gaspar, P.P.; Hwang, R.J. J. Am. Chem. Soc. 1974, 96, 6198Henis, J.M.S.; Stewart, G.W.; Gaspar, P.P. J. Chem. Phys. 1974, 61, 4860Hwang, R.J.; Gaspar, P.P. J. Am. Chem. Soc. 1978, 100, 6626Gaspar, P.P. React. Intermed. 1978, 1, 229
R1
Ge
R2
:
Reviews:Lappert, M.F.; Rowe, R.S. Coordin. Chem. Rev. 1990, 100, 267 (germylenes, stannylenes, plumbylenes)Neumann, W.P. Chem. Rev. 1991, 91, 311 (germylenes and stannylenes)Neumann, W.P.; Weisbeck, M.P.; Wienken, S. Main Group Metal Chem. 1994, 17, 151Korolev, V.A.; Nefedov, O.M. Adv. Phys. Org. Chem. 1995, 30, 1Tokitoh, N.; Okazaki, R. Coord. Chem. Rev. 2000, 210, 251 (silylenes, germylenes, stannylenes, plumbylenes)
- Ca(OH)2GeH2
2 H2O
- H2
CaGe950 C
CaH2 + Ge
Royen, P.; Schwarz, R. Z. Anorg. Allgem. Chem. 1933, 211, 412 (first claim, later refuted)
237
H
Ge
H H
Ph Br Ph HH
Ge
H+
:
NaBr + Na+ + _
Glarum, S.N.; Kraus, C.A. J. Am. Chem. Soc. 1950, 72, 5398
Silylium ions (silylenium ions, silicenium ions, silyl cations, silicocations)
R1
Si+
R2 R3
Reviews:Lambert, J.B.; Kania, L.; Zhang, S. Chem. Rev. 1995, 95, 1191Corriu, R.J.P.; Henner, M. J. Organometallic Chem. 1974, 74, 1Reed, C.A. Acc. Chem. Res. 1998, 31, 325
X = Cl, I
Ph3CH + (iPr)3Si+ [CB11H6X6]-(iPr)3SiH + Ph3C+ [CB11H6X6]-
Xie, Z.; Manning, J.; Reed, R.W.; Mathur, R.; Boyd, P.D.W.; Benesi, A.; Reed, C.A. J. Am. Chem. Soc. 1996, 118, 2922Reed, C.A.; Xie, Z.; Bau, R.; Benesi, A. Science 1993, 262, 402
Ph3CH + R3Si+ X-Ph3C+ X- + R3SiH
Me(iPr)2Si+ X-
Et3Si+ X-
(Me3Si)3Si+ X-
X = [B(F5Ph)4]
238
Lambert, J.B.; Zhang, S.; Ciro, S.M. Organometallics 1994, 13, 2430
(tBu)2MeSi+ [Br6-CB11H6]-
R = Et, iPr, tBuR3Si+ [Br6-CB11H6]-
Xie, Z.; Bau, R.; Benesi, A.; Reed, C.A. Organometallics 1995, 14, 3933
Si
Mes
Mes
MesSi
R
R
R
R = Ph, Et
Mes3Si+ [B(F5Ph)4]- + + R3Si+ [B(F5Ph)4]-
Lambert, J.B.; Zhao, Y. Angew. Chem. Int. Ed. 1997, 36, 400
Si
Mes
Mes
Mes
Si
Et
Et
Et
+ Et3Si+ [HCB11Me5Br6]- Mes3Si+ [HCB11Me5Br6]- +
Kim, K.C.; Reed, C.A.; Elliott, D.W.; Mueller, L.J.; Tham, F.; Lin, L.; Lambert, J.B. Science 2002, 297, 825
OH
Si R2
R1
Me3Si
SiMe3
Me3Si
SiMe3
Si R2
R1
Me3Si
SiMe3
Me3SiSi R2
R1
SiMe3
SiMe3
Me3Si
Si R2
R1
SiMe3
Me3Si
MeO
- H+
MeOH+
+
- H2O
H+
Sternberg, K.; Michalik, M.; Oehme, H. J. Organometallic Chem. 1997, 533, 265
239
Tetrahedral Intermediates
Reviews:Jencks, W.P. Prog. Phys. Org. Chem. 1964, 2, 63Johnson, S.L. Adv. Phys. Org. Chem. 1967, 5, 237Jencks, W.P. Catalysis in Chemistry and Enzymology, McGraw-Hill: New York, 1969Jencks, W.P. Chem. Rev. 1972, 72, 705Barnett, R.E. Acc. Chem. Res. 1973, 6, 41Capon, B.; Ghosh, A.K.; Grieve, D.M.A. Acc. Chem. Res. 1981, 14, 306McClelland, R.A.; Santry, L.J. Acc. Chem. Res. 1983, 16, 394Capon, B.; Dosunmu, M.I.; De Nazare, M.; Sanchez, M. Adv. Phys. Org. Chem. 1985, 21, 37Bowden, K. Adv. Phys. Org. Chem. 1993, 28, 171Perrin, C.L. Acc. Chem. Res. 2002, 35, 28
O
C
R1 R2
O -
CR1 R2
Nu +
O
S
R1 R2
O -
SR1 R2
Nu +
O
P
R1 R2
O -
PR1 R2
Nu +
+ Nu
+ Nu
+ Nu
240
N
R OEt
PhN
R OEt
PhH
Br
NHPh
R OH
OEt
O
R NHPh- HBr
HBr H2O
+ EtOH
Stieglitz, J. Am. Chem. J. 1899, 21, 101
O
CF3 OEtCF3
O - Na+
OEt
OEt
+ NaOEt
Swarts, F. Bull. Soc. Chim. Belg. 1926, 35, 414Helferich, B.; Muller, A. Chem. Ber. 1930, 63B, 2142Bender, M.L. J. Am. Chem. Soc. 1951, 73, 1626Bender, M.L. J. Am. Chem. Soc. 1953, 75, 5986Zaugg, H.E.; DeNet, R.W.; Michaels, R.J. Jr. J. Org. Chem. 1961, 26, 4828Cordes, E.H.; Childers, M. J. Org. Chem. 1964, 29, 968Bender, M.L.; Kezdy, F.J. J. Am. Chem. Soc. 1964, 86, 3704Martin, R.B.; Hedrick, R.I.; Parcell, A. J. Org. Chem. 1964, 29, 3197
Jencks, W.P.; Gilchrist, M. J. Am. Chem. Soc. 1964, 86, 5616Fedor, L.R.; Bruice, T.C. J. Am. Chem. Soc. 1964, 86, 5697Kirby, A.J.; Jencks, W.P. J. Am. Chem. Soc. 1965, 87, 3217Fedor, L.R.; Bruice, T.C. J. Am. Chem. Soc. 1965, 87, 4138Caplow, M. J. Am. Chem. Soc. 1965, 87, 5774Biffin, M.E.C.; Crombie, L.; Elvidge, J.A. J. Chem. Soc. 1965, 7500
ONH2- O OH HO NHOH
NOH
+ NH2OH
+
- H2O
HA
241
Reimann, J.E.; Jencks, W.P. J. Am. Chem. Soc. 1966, 88, 3973DeJersey, J.; Zerner, B. Biochem. Biophys. Res. Commun. 1967, 28, 173Robinson, D.R.; Jencks, W.P. J. Am. Chem. Soc. 1967, 89, 7098Robinson, D.R.; Jencks, W.P. J. Am. Chem. Soc. 1967, 89, 7088
Thiirenium Ions
S+
R3R2
R1
Reviews:Pasquato, L.; Destro, R.; Lucchini, V.; Modena, G. Phosphorus, Sulfur, and Silicon and the related elements 1999, 153-154, 235Lucchini, V.; Modena, G.; Pasquato, L. Gazz. Chim. Ital. 1997, 127, 177Modena, G.; Pasquato, L.; Lucchini, V. Phosphorus, Sulfur, and Silicon and the related elements 1994, 95-96, 265Capozzi, G.; Lucchini, V.; Modena, G. Rev. Chem. Intermediates 1979, 2, 347
C* C
Ph
XC6H4S
OSO2C6H4p-Br
Ph
C* C
S+
PhPh
C6H4X
S
C*
X
Ph
PhS
C*
X
Ph
Ph
BF3
- pBrC6H4SO3H
C* = 14C
pBrC6H4SO3-
242
C*H2
CH
X
Ph
PhCH2
C*H
X
Ph
Ph C*H
C
X
Ph
PhCH
C*
X
Ph
Ph
O
C
X
Ph
O
C*
X
Ph
NBS KMnO4
H2Raney Ni
+ PhCOOH + PhC* OOH+
Capozzi, G.; Melloni, G.; Modena, G.; Tonellato, U. Chem. Commun. 1969, 1520Modena, G.; Tonellato, U. J. Chem. Soc. B 1971, 381 (stereochemical evidence)Modena, G.; Tonellato, U. J. Chem. Soc. B 1971, 374 (kinetic evidence)Burighel, A.; Modena, G.; Tonellato, U. Chem. Commun. 1971, 1325
C+
HS
H
H
S+
HH
H65.9 kcal/mol
Denes, A.S.; Csizmadia, I.G.; Modena, G. Chem. Commun. 1972, 8
243
R1
R3-S
O3SAr
R2
R2
R3-S
O3SAr
R1
S+
R2R1
R3
R1
R3-S
Cl
R2
R2
R3-S
Cl
R1
R2R1 + R3-SCl
Cl-
- ArSO3H
HCl
Modena, G.; Scorrano, G.; Tonellato, U. J. Chem. Soc. Perkin Trans. 2 1973, 493
Transition Metal Carbene Complexes
[Ln]M
R1
R2Reviews:Fischer, E.O. in Advances in Organometallic Chemistry, (F.G.A. Stone, R. West, eds.), Academic Press: Orlando, FL, 1976; Vol. 14, p. 1 - 32(carbene and carbyne complexes)Schrock, R.R. Acc. Chem. Res. 1979, 12, 98Dötz, K.H.; Fischer, H.; Hofmann, P.; Kreissl, F.R.; Schubert, U.; Weiss, K. Transition Metal Carbene Complexes, Verlag Chemie: Weinheim,1983Dötz, K.H. Angew. Chem. Int. Ed. 1984, 23, 587Roper, W.R. NATO ASI Series, Ser. C. 1989, 269, 27Harvey, D.F.; Sigano, D.M. Chem. Rev. 1996, 96, 271
244
de Meijere, A. Pure Appl. Chem. 1996, 68, 61Barluenga, J. Pure Appl. Chem. 1996, 68, 543Hegedus, L.S. Tetrahedron 1997, 53, 4105Aumann, R.; Nienhaber, H. Adv. Organometallic Chem. 1997, 41, 163Barluenga, J. Pure Appl. Chem. 1999, 71, 1385Herndon, J.W. Tetrahedron 2000, 56, 1257de Meijere, A.; Schirmer, H.; Duetsch, M. Angew. Chem. Int. Ed. 2000, 39, 3964Barluenga, J.; Fananas, F.J. Tetrahedron 2000, 56, 4597Sierra, M.A. Chem. Rev. 2000, 100, 3591Bernasconi, C.F. Adv. Phys. Org. Chem. 2002, 37, 137
Fischer carbene
M
OMe
Ph
CO
CO
OC
OC
CO
M
CO
CO
OC
OC
CO
CO M
CO
CO
OC
OC
CO
C
O -
M
CO
CO
OC
OC
CO
C
O -
M
CO
CO
OC
OC
CO OH
Ph
Ph Ph
M = W, Cr, Mo
PhLi / Et2OLi+
Me4N+ Cl- Me4N+
- LiCl
HX- Me4N+ X-
CH2N2
- N2
Me3O+ BF4-- LiBF4
- Me2O
Fischer, E.O.; Maasbol, A. Angew. Chem. Int. Engl. Ed. 1964, 3, 580Fischer, E.O.; Maasbol, A. Angew. Chem. 1964, 76, 645Aumann, R.; Fischer, E.O. Angew. Chem. Int. Ed. 1967, 6, 879Fischer, E.O. Adv. Organomet. Chem. 1976, 14, 1
245
(OC)5M
O - K+
R1
(OC)5M
OR2
R1
O
R1 NR3
R4
O - K+
(OC)5M N
R1
R3
R4
(OC)5M
N
R1
R4
R3
Me3SiCl
K+
_
R2-X
R1-COClK2[M(CO)5]
C8KM(CO)6
Semmelhack, M.F.; Lee, G.R. Organometallics 1987, 6, 1839Imwinkelried, R.; Hegedus, L.S. Organometallics 1988, 7, 702
Schrock carbene
246
M
H
CMe3
Me3CCH2
Me3CCH2
Me3CCH2
M = Ta, Nb
- 2 LiCl- CMe4
M[CH2CMe3]3Cl2 + 2 LiCH2CMe3
- 3 ZnCl2
2 M[CH2CMe3]3Cl22 MCl5 + 3 Zn[CH2CMe3]2
Schrock, R.R.; Meakin, P. J. Am. Chem. Soc. 1974, 96, 5288Schrock, R.R. J. Am. Chem. Soc. 1974, 96, 6796Schrock, R.R.; Fellmann, J.D. J. Am. Chem. Soc. 1978, 100, 3359Schrock, R.R. J. Organometallic Chem. 1976, 122, 209
Ta
H
H
CH3
Cp
Cp
Schrock, R.R. J. Am. Chem. Soc. 1975, 97, 6577Schrock, R.R.; Guggenberger, L.J. J. Am. Chem. Soc. 1975, 97, 6578
Transition Metal Carbyne Complexes [Ln]M C R
Reviews:Fischer, E.O. in Advances in Organometallic Chemistry, (F.G.A. Stone, R. West, eds.), Academic Press: Orlando, FL, 1976; Vol. 14, p. 1 - 32(carbene and carbyne complexes)
247
W C Ph
CO
CO
I
OC
CO
W
Ph
OMe
CO
CO
OC
OC
CO
+ CO + BI2OMe+ BI3
Fischer, E.O.; Kreis, G.; Kreiter, C.G..; Cornelius, G.; Müller, J.; Huttner, G.; Lorenz, H. Angew. Chem. 1973, 85, 618Fischer, E.O.; Kreiter, C.G.; Müller, J.; Huttner, G.; Lorenz, H. Angew. Chem. Int. Ed. 1973, 12, 564Fischer, E.O.; Kreis, G.; Kreissl, F.; Kalbfus, W.; Winkler, E. J. Organometallic Chem. 1974, 65, C53
Transition Metal Ketenyl Complexes
O
R1 R2
[M]
Reviews:Geoffrey, G.L.; Bassner, S.L. Adv. Organometallic Chem. 1988, 28, 1 (ketenyl complexes, heterovinylidene complexes)Gibson, S.E.; Peplow, M.A. Adv. Organometallic Chem. 1999, 44, 275 (vinylketenyl complexes)Kirmse, W. Eur. J. Org. Chem. 2002, 2193Singh, G.S.; Mdee, L.K. Curr. Org. Chem. 2003, 7, 1821
248
W
C
OC CO WMe3P PMe3OOC
2 PMe3
Kreissl, F.R.; Frank, A.; Schubert, U.; Lindner, T.L.; Hutner, G. Angew. Chem. 1976, 88, 649Kreissl, F.R.; Eberl, K.; Uedelhoven, W. Chem. Ber. 1977, 110, 3782Kreissl, F.R.; Uedelhoven, W.; Eberl, K. Angew. Chem. 1978, 90, 908Uedelhoven, W.; Eberl, K.; Kreissl, F.R. Chem. Ber. 1979, 112, 3376Eberl, K.; Uedelhoven, W.; Karsch, H.H.; Kreissl, F.R. Chem. Ber. 1980, 113, 3377
N
N
W
CO
CO
C
Br
Ph
N
N
W
CN
CO O
Ph
NC
1. 2 KCN
(- KBr)
2. [Ph3P-N=PPh3]+ X-
( - KX)
_
[Ph3P-N=PPh3]+
Fischer, E.O.; Filippou, A.C.; Alt, H.G.; Ackermann, K. J. Organometallic Chem. 1983, 254, C21 (first anionic ketenyl transition metal complex)
249
CH2 C O
Fe(CO)2(Cp)
(Cp)(CO)2Fe
OMe
(Cp)(CO)2Fe
Cl
(Cp)(CO)2Fe CH2
(Cp)(CO)2Fe CH2 PF4-
CO
BF4-
+
- MeOH
+
HBF4
- AgCl
AgPF6
- MeOH
HCl
+
PF4-
Bodnar, T.W.; Cutler, A.R. J. Am. Chem. Soc. 1983, 105, 5926
Transition Metal Keteniminium Complexes
N+
R1 R2
[M]-
R3
N+
R1 R2
[M]-
R3R3 R
Reviews:Aumann, R. Angew. Chem. 1988, 100, 1512
Ir
CO
Ph3P PPh3
Cl
N C
CN
CN
N C
CN
CN
Ir
PPh3
OC
PPh3
- KClK+
_+
250
Lenarda, M.; Baddley, W.H. J. Organometallic Chem. 1972, 39, 217
Marchand-Brynaert, J.; Ghosez, L. J. Am. Chem. Soc. 1972, 94, 2869; 2870
NMe2
Cl
NMe2
Re(CO)5
NMe2
Cl
N+
NMe2
Fe(CO)2(Cp)
N+
+ Na[Re(CO)5]- NaCl
+ Na[Fe(CO)2(Cp)]- NaCl
NMe2
Cl
N+
NMe2
Cl
N+
Co(CO)3
N+ N+
Mo(CO)2(Cp)
- CO
_
- CO
_
+ Na[Co(CO)4]- NaCl
+ Na[Mo(CO)3(Cp)]- NaCl
King, R.B.; Hodges, K.C. J. Am. Chem. Soc. 1974, 96, 1263
251
(CO)5Cr
CH3
OCH3
Cr(CO)5 + Cy-N=C=C(Me)(OMe)(OC)5Cr[Cy-N=C=C(Me)(OMe)]+ Cy-NC
Kreiter, C.G.; Aumann, R. Chem. Ber. 1978, 111, 1223
(CO)5W
OEt
Ph N
N(CO)5W
OEtPh
R
OCy
N
NO
OEtPh
R
OCy
Fe(NO3)3
KMnO4R-N=C=OW(CO)5[Cy-N=C=C(OEt)(Ph)]+ Cy-NC
Aumann, R.; Kuckert, E. Chem. Ber. 1986, 119, 156
Cp2V[R2C=C=N-R1]Cp2V + R2C=C=N-R1
Sielisch, T.; Behrens, U. J. Organometallic Chem. 1986, 310, 179
(CO)5W
Ph
OEt
N C
Cy
(CO)5W OEt
Ph
HR
N
(CO)5W
Cy
RHOEt
PhN
(CO)5W
Cy
PhEtOH
R+ Cy-NC
Aumann, R.; Kuckert, E. Chem. Ber. 1987, 120, 1939
Transition Metal Iminium Complexes
252
N+
R1
R2
R3
R4M[Ln]
Reviews:None.
W
N
COPPPh2OC
COPhPh
W
NH
COPPPh2OC
COPhPh
W
NH
COCOCl
PPh2PPh2
Cl
HCl+
Cl-HCl
Ainscough, E.W.; Brodie, A.M.; Burrell, A.K.; Kennedy, S.M.F. J. Am. Chem. Soc. 2001, 123, 10391
Transition Metal Silene Complexes
[Ln]M Si
R
R
Reviews:Lickliss, P.D. Chem. Soc. Rev. 1992, 21, 271Ogino, H. The Chemical Record 2002, 2, 291
253
NEt2
SiH CH3
CH3
(CO)4Fe Si
CH3
CH3
NHEt2- CO
hνFe(CO)5 +
Schmid, G.; Welz, E. Angew. Chem. Int. Ed. 1977, 16, 785
Cl
SitBuO Cl
OtBu
O
PN
N(CH3)2
N(CH3)2
OtBu
OtBu
Si(CO)4Fe
O
P(CH3)2N
N(CH3)2
N(CH3)2Na2Fe(CO)4 + - 2 NaCl
+
Zybill, C.; Muller, G. Angew. Chem. Int. Ed. 1987, 26, 669
Ru+ Si
PMe3
PMe3
Ph
Ph
OTf Ru+2 Si
PMe3
PMe3
Ph
Ph
NCCH3_ + NaBPh4
CH3CN
- NaOTf
_ BPh4-
Straus, D.A.; Tilley, T.D.; Rheingold, A.L.; Geib, S.J. J. Am. Chem. Soc. 1987, 109, 5872
254
Si(CO)4Os
S
Ru+
_
Pt Si
SEt
SEt
PCy3
H
PCy3
BPh4-
+
Cy = cyclohexyl
Grumbine, S.D.; Tilley, T.D.; Rheingold, A.L. J. Am. Chem. Soc. 1993, 115, 358Grumbine, S.D.; Tilley, T.D.; Arnold, E.P.; Rheingold, A.L. J. Am. Chem. Soc. 1993, 115, 7884Grumbine, S.D.; Tilley, T.D.; Arnold, E.P.; Rheingold, A.L. J. Am. Chem. Soc. 1994, 116, 5495
H Si
NMe2
NMe2
NMe2 (CO)4Fe Si
NMe2
NMe2
NHMe2
hν
- COFe(CO)5 +
Bodensieck, U.; Braunstein, P.; Deck, W.; Faure, T.; Knorr, M.; Stern, C. Angew. Chem. Int. Ed. 1994, 33, 2440
Transition metal vinyl cation complexes
R1
R2
[Ln]M
[Ln]M
R1
R2
R1 R2
M[Ln]+ + +
Reviews:
Chisholm, M.H.; Clark, H.C. Acc. Chem. Res. 1973, 6, 202
255
Pt
QCl
Q Me
R
R
Pt
Q
Q Me
R
R
Pt
Q
Q Me
R
R
Pt
Q
R
Q Me
R
R
R
PtMe
Q
Q
+ + AgPF6- AgCl
+
[PF6-]
+
++
Clark, H.C.; Puddephatt, R.J. Chem. Commun. 1970, 92
Clark, H.C.; Puddephatt, R.J. Inorg. Chem. 1970, 9, 2670
Clark, H.C.; Ruddick, J.D. Inorg. Chem. 1970, 9, 1226
Chisholm, M.H.; Clark, H.C. Chem. Commun. 1970, 763
Clark, H.C.; Puddephatt, R.J. Inorg. Chem. 1971, 10, 18
Chisholm, M.H.; Clark, H.C. Inorg. Chem. 1971, 10, 1711; 2557
Chisholm, M.H.; Clark, H.C. J. Am. Chem. Soc. 1972, 94, 1532
Transition Metal Vinylidene Complexes
256
[Ln]M C C
R1
R2Reviews:King, R.B. Acc. Chem. Res. 1970, 3, 417Herrmann, W.A. Adv. Organometallic Chem. 1982, 20, 159Bruce, M.I.; Swincer, A.G. Adv. Organometallic Chem. 1983, 22, 59Sailor, M.L.; Shriver, D.F. Acc. Chem. Res. 1988, 21, 374 (heterovinylidene complexes)Bruce, M.I. Chem. Rev. 1991, 91, 197Bruce, M.I. Chem. Rev. 1998, 98, 2797Puerta, M.C.; Valegra, P. Coord. Chem. Rev. 1999, 193-195, 977Lin, Y.C. J. Organometallic Chem. 2001, 617-618, 141 (Ru)Bruneau, C. Topics Organometallic Chem. 2004, 11, 125 (Ru, Os)King, R.B. Coord. Chem. Rev. 2004, 248, 1533Selegue, J.P. Coord. Chem. Rev. 2004, 248, 1543Watatsuki, Y. J. Organometallic Chem. 2004, 689, 4092
Fe2(µ-C=CPh2)(CO)8 + CO2Ph2C=C=O + Fe2(CO)9
Mills, O.S.; Redhouse, A.D. Chem. Commun. 1966, 444Mills, O.S.; Redhouse. A.D. J. Chem. Soc. A 1968, 1282 NC
NC
Cl
M(CO)3Cp
M
Cp
R3P C
PR3
CN
CNCl
M = W, Mo; R = PPh3, P(OMe)3, P(OPh)3, P(OEt)3, AsPh3, SbPh3
+ 3 CO+ 2 PR3
King, R.B.; Saran, M.S. Chem. Commun. 1972, 1053
257
CN
CN
Cl
X
CN
CN
(CO)5M
X
CN
CN
(CO)3(Cp)M
X
X = H, Cl, CN; M = Mo, W
M(CO)5-
+ Cl-
M(Cp)(CO)3- + Cl-
King, R.B.; Saran, M.S. J. Am. Chem. Soc. 1972, 94, 1784King, R.B.; Saran, M.S. J. Am. Chem. Soc. 1973, 95, 1811King, R.B.; Saran, M.S. J. Am. Chem. Soc. 1973, 95, 1817
Transition Metal Vinylidenecarbene (allenylidene) Complexes
[Ln]M C C C
R1
R2
Reviews:Bruce, M.I.; Swincer, A.G. Adv. Organometallic Chem. 1983, 22, 59Bruce, M.I. Chem. Rev. 1991, 91, 197Werner, H. J. Organometallic Chem. 1994, 475, 45Werner, H. Chem. Commun. 1997, 903Bruce, M.I. Coord. Chem. Rev. 1997, 166, 91Cadiero, V.; Gamasa, M.P.; Gimeno, J. Eur. J. Inorg. Chem. 2001, 571Werner, H.; Ilg, K.; Lass, R.; Wolf, J. J. Organometallic Chem. 2002, 661, 137Winter, R.F.; Zalis, S. Coord. Chem. Rev. 2004, 248, 1565Rigaut, S.; Touchard, D.; Dixneuf, P.H. Coord. Chem. Rev. 2004, 248, 1585
258
M = Cr, W EX3 = BF3 (when M = Cr), AlEt3 (when M = W)
M(CO)5[=C=C=C(Ph)(NEt2)] + [EtOEX3]- H+M(CO)5[=C(OEt)CH=C(Ph)(NEt2)] + EX3
Berke, H. Angew. Chem. Int. Ed. Engl. 1976, 15, 624Fischer, E.O.; Kalder, H.J.; Frank, A.; Köhler, F.H.; Huttner, G. Angew. Chem. Int. Ed. 1976, 15, 623
[Ru(=C=C=CPh2)(PMe3)2Cp]+
Selengue, J.P. Organometallics 1982, 1, 217
Triplet Ketones (excited state)
O
R1 R2
*3
Reviews:Brand, J.C.D.; Williamson, D.G. Adv. Phys. Org. Chem. 1963, 1, 365Yang, N.C. Reactivity of the Photoexcited Organic Molecule, Proc. Conf. Chem. 1965, 145Parker, C.A. Ber. Bunsen-Gesell. 1969, 73, 764Stephenson, L.M.; Hammond, G.S. Angew. Chem. Int. Ed. 1969, 8, 261Davidson, R.S. Organic Reaction Mechanisms 1971, 467Ireland, J.F.; Wyatt, P.A.H. Adv. Phys. Org. Chem. 1976, 12, 132Davidson, R.S. Adv. Phys. Org. Chem. 1983, 19, 1Pedulli, G.F. Rev. Chem. Intermediates 1986, 7, 155Chan, I.Y. Rev. Chem. Intermediates 1987, 8, 339
Wan, J.K.S.; Depew, M.C. Res. Chem. Intermediates 1992, 18, 227Armesto, D.; Ortiz, M.J.; Agarrabeitia, A.R. in CRC Handbook of Organic Photochemistry and Photobiology, 2nd ed., (W. Horspool; F. Lenci,eds.) CRC Press: Boca Raton, FL, 2004, p. 77/1Wagner, P.J.; Klan, P. in CRC Handbook of Organic Photochemistry and Photobiology, 2nd ed., (W. Horspool; F. Lenci, eds.) CRC Press: BocaRaton, FL, 2004, p. 52/1
259
Lewis, G.N.; Kasha, M. J. Am. Chem. Soc. 1945, 67, 994
Triplet olefins (excited state)
R1
R2
R4
R3
*3
Reviews:Brand, J.C.D.; Williamson, D.G. Adv. Phys. Org. Chem. 1963, 1, 365Stephenson, L.M.; Hammond, G.S. Angew. Chem. Int. Ed. 1969, 8, 261Caldwell, R.A. in Kinetics and Spectroscopy of Carbenes and Biradicals, (M.S. Platz, ed.) Plenum: New York, 1990, p. 77Wilbrandt, R.; Langkilde, F.W. NATO ASI Ser. Ser. C 1973, 410, 567Ireland, J.F.; Wyatt, P.A.H. Adv. Phys. Org. Chem. 1976, 12, 132Davidson, R.S. Adv. Phys. Org. Chem. 1983, 19, 1Unett, D.J.; Caldwell, R.A. Res. Chem. Intermediates 1995, 21, 665
Tropylium ion
260
R R R R
RR R
R
+
+
+
+
+
+
+
+
Reviews:Harmon, K.M. in Carbonium Ions (G.A. Olah, ed.) Wiley: New York, 1973, Vol. 4, p. 1579Lifshitz, C. Acc. Chem. Res. 1994, 27, 138Abraham, W.; Kharlanov, V. in Handbook of Photochemistry and Photobiology, (H.S. Nalwa, ed.) American Scientific Publishers: CA, 2003, Vol.2, p. 299
Br
Br
Br2
- HBr+ Br-
Doering, W.v.E.; Knox, L.H. J. Am. Chem.Soc. 1954, 76, 3203 (also first use of inscribed circle to indicate aromaticity)
261
CH3
+. + e-
electronimpact
Rylander, P.N.; Meyerson, S.; Grubb, H.M. J. Am. Chem. Soc. 1957, 79, 842
Vinyl cations
C
R2
R3
R1
+
Reviews:Hanack, M. Acc. Chem. Res. 1970, 3, 209Modena, G.; Tonellato, U. Adv. Phys. Org. Chem. 1971, 9, 185Stang, P.J. Prog. Phys. Org. Chem. 1973, 10, 205Grob, C.A. Angew. Chem. Int. Ed. 1972, 11, 544Stang, P.J. Prog. Phys. Org. Chem. 1973, 10, 205Subramanian, L.R.; Hanack, M. J. Chem. Educ. 1975, 52, 80Hanack, M. Acc. Chem. Res. 1976, 9, 364Rappoport, Z. Acc. Chem. Res. 1976, 9, 265Stang, P.J.; Rappoport, Z.; Hanack, M.; Subramanian, L.R. Vinyl Cations, Academic Press: New York, 1979Rappoport, Z. Reactive Intermediates 1983, 3, 427Wan, P.; Yates, K. Rev. Chem. Intermediates 1984, 5, 157Rappoport, Z.; Stang, P.J. (eds.) Dicoordinated Carbocations, Wiley: Chichester, 1997Okuyama, T.; Lodder, G. Adv. Phys. Org. Chem. 2002, 37, 1Okuyama, T. Acc. Chem. Res. 2002, 35, 12
262
Cl ClCl+
Cl
CF3CO2
CF3COO-+
H+
Peterson, P.E.; Duddey, J.E. J. Am. Chem. Soc. 1963, 85, 2865
TsO
CF3CO2
- HOTs +
+H+ CF3CO2-
Peterson, P.E.; Kamat, R.J. J. Am. Chem. Soc. 1966, 88, 3152Peterson, P.E.; Duddey, J.E. J. Am. Chem. Soc. 1966, 88, 4990
Jones, W.M.; Miller, F.W. J. Am. Chem. Soc. 1967, 89, 1960Fahey, R.C.; Lee, D.J. J. Am. Chem. Soc. 1967, 89, 2780Nishimura, A.; Kato, H.; Ohta, M. J. Am. Chem. Soc. 1967, 89, 5083Bly, R.S.; Ballentine, A.R.; Koock, S.U. J. Am. Chem. Soc. 1967, 89, 6993Noyce, D.S.; Matesich, M.A.; Peterson, P.E. J. Am. Chem. Soc. 1967, 89, 6225
Ph
Ph
X X++
Miller, L.L.; Kaufman, D.A. J. Am. Chem. Soc. 1968, 90, 7282
263
- OOC Ph
X
C+ Ph
- OOC - OOC Ph
OH
Ph
O
- OOC
Ph
O
Ph
- X-
H2O
- CO2- CO2
Grob, C.A. Bull. Soc. Chim. Fr. 1960, 1360
X
Br
X
X
EtO
X
O
X
80% EtOH/H2O
- H+
+
- Br-
Grob, C.A.; Cseh, G. Helv. Chim. Acta 1964, 47, 194Grob, C.A.; Csapilla, J.; Cseh, G. Helv. Chim. Acta 1964, 47, 1590Huang, S.J.; Lessard, M.V. J. Am. Chem. Soc. 1968, 90, 2432Grob, C.A.; Spaar, R. Helv. Chim. Acta 1970, 53, 2119Grob, C.A.; Pfaendler, H.R. Helv. Chim. Acta 1971, 54, 2060Grob, C.A.; Nussbaumer, R. Helv. Chim. Acta 1971, 54, 2528Grob, C.A. Chimia 1971, 25, 87
264
R1
OSO2CF3
R2 R1
R2
R1
OMe
R2
R1, R2 = alkyl
- H+
MeOH+
- CF3SO3-
Summerville, R.H.; Senkler, C.A.; Schleyer, P.v.R.; Deuber, T.E.; Stang, P.J. J. Am. Chem. Soc. 1974, 96, 1100Stang, P.J.; Deuber, T.E. Org. Synth. 1974, 54, 79
Vinylidenes (methylene carbenes, alkylidene carbenes)
C C
R1
R2
:
Reviews:Hartzler, H.D. in Carbenes, (R. A. Moss, M. Jones Jr.; eds.) Wiley-Interscience: New York, 1975, Vol. 2Stang, P.J. Chem. Rev. 1978, 78, 383Stang, P.J. Acc. Chem. Res. 1978, 11, 107Stang, P.J. Acc. Chem. Res. 1982, 15, 348
Br
Ph
Ph
H
C
Ph
Ph
PhPh + KBr:KNH2/NH3 (l)
Coleman, G.H.; Maxwell, R.D. J. Am. Chem. Soc. 1934, 56, 132
Emschwiller, G. Bull. Soc. Chim. Fr. 1935, 2, 1625
265
Kobrich, G. Angew. Chem. Int. Ed. 1967, 6, 41
ON
O
ON
R
R
R
R
:
Newman, M.S.; Okorududu, A.O. J. Am. Chem. Soc. 1968, 90, 4189Newman, M.S.; Okorududu, A.O. J. Org. Chem. 1969, 34, 1220Newman, M.S.; Din, Z. J. Org. Chem. 1973, 38, 547
OSO2CF3
R
R
R
R
R
R
H
R
R OtBuR
R
tBuO-
- HOtBu:
+
- CF3SO3-
tBuO-
Stang, P.J.; Mangum, M.G.; Fox, D.P.; Haak, P. J. Am. Chem. Soc. 1974, 96, 4562
Vinylidenecarbenes (allenylidenes, alkenylidene carbenes)
266
C C
R1
R2
C :
Reviews:None.
H
Cl Cl
Ph
K+
- HOtBu
PhCH=CH2:
- KCl
_KOtBu
Hartzler, H.D. J. Am. Chem. Soc. 1961, 83, 4990Hartzler, H.D. J. Org. Chem. 1964, 29, 1311
le Noble, W.J.; Chiou, D.M.; Okaya, Y. J. Am. Chem. Soc. 1979, 101, 3244
Wallach intermediate (see Dications)
Wanzlich carbenes
Reviews:Arduengo, A.J. III Tetrahedron 1999, 55, 14523 (imidazolylidenes and imidazolinylidenes)
N
N
N
N
Ph
Ph
Ph
Ph
N
N
Ph
Ph
2 :
267
Wanzlich, H.W.; Schikora, E. Angew. Chem. 1960, 72, 494Wanzlich, H.W.; Schikora, E. Chem. Ber. 1961, 94, 2389Wanzlich, H.W. Angew. Chem. Int. Ed. 1962, 1, 75Wanzlich, H.W.; Schönherr, H.J. Angew. Chem. Int. Ed. 1968, 80, 153
Wheland Intermediates (arenium ions, benzenium ions)
R R
H
E
R
H
E
R
H
E
+ E+
+
++
R = EDG, para substitution
R R
H
E
R
H
E
R
H
E
+ E+ ++
+
R = EDG, ortho substitution
R RH
E
RH
E
RH
E
R = EWG, meta substitution
+ E+
+
+ +
Reviews:Olah, G.A. Acc. Chem. Res. 1970, 4, 240
268
Wheland, G.W.; Pauling, L. J. Am. Chem. Soc. 1935, 57, 2086Wheland, G.W. J. Am. Chem. Soc. 1942, 64, 900Matlow, S.L.; Wheland, G.W. J. Am. Chem. Soc. 1955, 77, 3653
R R
R
R
H R
H
H
H
HH
R
H RH
R
R
R
H
H
R
HBr / Al2Br6 +
+
+
+
+
+
- H+
H+
Nightingale, D.V. Chem. Rev. 1939, 25, 329McCaulay, D.A.; Lien, A.P. J. Am. Chem. Soc. 1951, 73, 2013McCaulay, D.A.; Lien, A.P. J. Am. Chem. Soc. 1953, 75, 2411Brown, H.C.; Smoot, C.R. J. Am. Chem. Soc. 1956, 78, 2176
H H
+
269
Gold, V.; Tye, F.L. J. Chem. Soc. 1952, 2172 (first direct spectroscopic evidence for protonation of aromatics)Reid, C. J. Am. Chem. Soc. 1954, 76, 3264
H H
R
BF4-+
Olah, G.A.; Kuhn, S.J. Nature 1956, 178, 693Olah, G.A.; Kuhn, S.J. J. Am. Chem. Soc. 1958, 80, 6535
AlCl4-+
Doering, W.v.E.; Saunders, M.; Boyton, H.G.; Earhart, H.W.; Wadley, E.F.; Edwards, W.R.; Laber, R. Tetrahedron 1958, 4, 178
270
R
R
NO
R
R
R
RNO NO
+ + +
R = Me, Et, Ph
Hubig, S.M.; Kochi, J.K. J. Am. Chem. Soc. 2000, 122, 8279
Ylides (1,2-Dipoles)
Reviews:Johnson, A.W. Ylid Chemistry, Academic Press: New York, 1966Nesmeyanov, N.A. Mendeleev Chem. 1967, 12, 35Lowe, P.A. Chem. Ind. 1970, 1070Wittig, G. J. Organometallic Chem. 1975, 100, 279Morris, D.G. in Recent Advances in the Chemistry of Ylides, (G.G. Wubbels, ed.) Butterworths: London, Vol. 10, 1983, p. 189Lloyd, D. Non-Benzenoid Conjugated Carbocyclic Compounds, Elsevier Press: Amsterdam, 1984, p. 32Johnson, A.W. Ylides and Imines of Phosphorus, Wiley: New York, 1993Clark, J.S. (ed.) Nitrogen, Oxygen, and Sulfur Ylide Chemistry, Oxford University Press: Oxford, 2002
(i) Ammonium ylides
N
R3
R5
R4
R1
R2
_+
Reviews:Zugravescu, I.; Petrovanu, M. N-Ylid Chemistry, (translated by C. Stoicescu) McGraw-Hill International Book Co.: New York, 1976Clark, J.S. (ed.) Nitrogen, Oxygen, and Sulfur Ylide Chemistry, Oxford University Press: Oxford, 2002
271
H NMe3NMe3
+Br-
Ag2O
+
_
Ingold, C.K.; Jessop, A.J. J. Chem. Soc. 1929, 2357
H NMe3NMe3
- PhH- LiBr
_
+
PhLi
Br-+
Wittig, G.; Felletschin, G. Ann. Chem. 1944, 555, 133
Me3N+ CH2
O
R1 R2
R2
OH
R1NMe3
OH-
+1.
2. H2O- Ph-H- LiX
_Me4N+ X- + Ph-Li
Me3P+ CH2
R1 R2
O
R1 R2
+ O=PMe3
_
- Ph-H- LiX
Me4P+ X- + Ph-Li
272
R1 R2
Ph3P+ CH2
O
R1 R2Ph3P-CH3
+X - + Ph-Li
- Ph-H- LiX
_
+ O=PPh3
Wittig, G.; Wetterling, M.H. Ann. Chem. 1947, 557, 193Wittig, G.; Rieber, M. Ann. Chem. 1949, 562, 177; 187Wittig, G.; Geissler, G. Ann. Chem. 1953, 580, 44
N2 N+ PhMe2N Ph
∆
- N2
:PhCH2NMe2
_
Bamford, W.R.; Stevens, T.S. J. Chem. Soc. 1952, 1975
N N
Cl
Cl
Cl
Cl
N+Et Et
H
+ Et2NHhν
- N2
_
Bonneau, R.; Liu, M.T.H. J. Am. Chem. Soc. 1991, 113, 9872
273
West, F.G.; Glaeske, K.W.; Kevin, W.; Naidu, B.N. Synthesis 1993, 977
Ph
N2
NMe2
N+
Ph
N+
PhH
hν
- N2
_CHCl3
- : CCl2 Cl-
Tomioka, H.; Yamada, S.; Hirai, K. J. Org. Chem. 1995, 60, 1298
(ii) Oxonium ylides
Reviews:West, F.G.; Clark, J.S. in Nitrogen, Oxygen, and Sulfur Ylide Chemistry, (J.S. Clark, ed.) Oxford University Press: Oxford, 2002, p. 115 - 134
O Ph
NN
TsO+
Ph
H H_ Na+
hν
- NaTs- N2
nn
_
Kirmse, W.; Kund, K. J. Am. Chem. Soc. 1989, 111, 1465
(iii) Phosphonium ylides
P
R3
R5
R4
R1
R2
+_
Reviews:Gruetzmacher, H.; Heim, U.; Schoenberg, H.; Pritzkow, H. Phosphorus, Sulfur, Silicon, and Related Elements 1993, 76, 281
274
Ph3P+ COOEt Ph3P COOEt Ph3P+ COOEt
_KOH
Cl-
Michaelis, A.; Gimborn, H.V. Chem. Ber. 1894, 27, 272Aksnes, G. Acta Chem. Scand. 1961, 15, 438
Ph3P+ COR Ph3P COR Ph3P+ COR
R = Me, Ph
Cl-
KOH_
Michaelis, A.; Kohler, E. Chem. Ber. 1899, 32, 1566Ramirez, F.; Dershowitz, S. J. Org. Chem. 1957, 22, 41
Ph3P
Ph
Ph
+_Ph3P=CPh2
∆- N2
Ph3P=N-N=CPh2Ph3P + Ph2CN2
Staudinger, H.; Meyer, J. Helv. Chim. Acta 1919, 2, 635
Ph3P
Ph
PhPh3P+ Ph
Ph
H
- nBuH- LiBr
nBuLi
Br-
Ph3P=CPh2_
+
Coffmann, D.D.; Marvel, C.S. J. Am. Chem. Soc. 1929, 51, 3496
275
H PPh3
PPh3+
X -
NH4OH
+
_
Pinck, L.A.; Hilbert, G.E. J. Am. Chem. Soc. 1947, 69, 723
(iv) Pyridine ylides R1
N
R2
R
N N_
++_
Reviews:Zugravescu, I.; Petrovanu, M. N-Ylid Chemistry, (translated by C. Stoicescu) McGraw-Hill International Book Co.: New York, 1976Platz, M.S.; White, W.R. III; Modarelli, D.A.; Celebi, S. Res. Chem. Intermediates 1994, 20, 175
O+
Ph
Ph N+
Ph
Ph
HNPh
N+
Ph
Ph
NPh
I-
PhNHNH2
- H2O
I-
NaOH
- H2O- NaI
_
Scheider, W.; Seebach, F. Chem. Ber. 1921, 54, 2285Scheider, W. Ann. Chem. 1924, 438, 115
276
O
ArN+
O -
ArN+
H O
ArN+
H
Br-NaOH
- H2O- NaBr
_
Krollpfeiffer, F.; Müller, A. Chem. Ber. 1933, 66, 739Krollpfeiffer, F.; Müller, A. Chem. Ber. 1935, 68, 1169Kröhnke, F. Chem. Ber. 1935, 68, 1177Kröhnke, F.; Heffe, W. Chem. Ber. 1967, 70, 864Kröhnke, F. Angew. Chem. 1953, 65, 605
N+
_
Pinck, L.A.; Hilbert, G.E. J. Am. Chem. Soc. 1946, 68, 2011
277
O
Ph
N2+
H
N+
H O
PhN+
O
PhH
H
O
PhN+
_
I-
:
_- N2
HI
I-
King, L.C.; Miller, F.M. J. Am. Chem. Soc. 1948, 70, 4154
N+
Ph
Ph
Ph
-
Lloyd, D.; Singer, M.I.C. J. Chem. Soc. Sect. C 1971, 2941
N+
R1
Ph
Ph
Ph
R2-
R1 = H, Ph; R2 = H, Me
Duerr, H.; Heu, B.; Ruge, B.; Scheppers, G. Chem. Commun. 1972, 1257
278
(v) Sulfimine ylides
N S+
R2
R3
R1
_
Reviews:None.
SO2NH2 SO2 N S+
Et
Et
_+ Et2S
Mann, F.; Pope, W.J. J. Chem. Soc. 1922, 121, 1052 (first sulfimine)
SO2NH2 SO2 N S+
R
R
O
S
R R
+- H2O
_
Tarbell, D.S.; Weaver, C. J. Am. Chem. Soc. 1941, 63, 2939
(vi) Sulfonium ylides
S
R3
R4
R1
R2
_+
Reviews:Trost, B.M.; Melvin, L.S. Jr. Sulfur Ylides: emerging synthetic intermediates, Academic Press: New York, 1975Ando, W. Acc. Chem. Res. 1977, 10, 179Ando, W. in The Chemistry of Diazonium and Diazo Groups, (S. Patai, ed.) Wiley: New York, 1978, Chapter 9
279
Doyle, M.P. Chem. Rev. 1986, 86, 919Padwa, A.; Hornbuckle, S.F. Chem. Rev. 1991, 91, 263Padwa, A.; Weingarten, M.D. Chem. Rev. 1996, 96, 223Doyle, M.P. Chem. Rev. 1998, 98, 911Clark, J.S. (ed.) Nitrogen, Oxygen, and Sulfur Ylide Chemistry, Oxford University Press: Oxford, 2002
S+
_
Ingold, C.K.; Jessop, J.A. J. Chem. Soc. 1930, 713
O
Ph
N2+
H
SH
HN NH2 O
PhS
HN NH2
SN
O
PhH
Ph
NH2O
PhS+
HN NH2
H
H__
:- N2- H2O
King, L.C.; Miller, F.M. J. Am. Chem. Soc. 1949, 71, 367
(vii) Trapping of carbenes generated by flash photolysisReviews:Jackson, J.E.; Platz, M.S. in Adv. Carbene Chem. (U. Brinker, ed.) JAI Press: Greenwich, CT, 1994, p. 89
280
X+
_
Griller, D.; Hadel, L.M.; Nazran, A.S.; Platz, M.S.; Wong, P.C.; Savino, T.G.; Scaiano, J.C. J. Am. Chem. Soc. 1984, 106, 2227(trapping of carbenes via ylide formation)
N2
Np HNp H
N
O+
Np
H
N+
Np
H
N+
Np
H
NEt3
Np
H
+_
Et3N
_
_
_
CH3CN
(CH3)2C=O
:
- N2
hν
Barcus, R.L.; Hadel, L.M.; Johnston, L.J.; Platz, M.S.; Savino, T.G.; Scaiano, J.C. J. Am. Chem. Soc. 1986, 108, 3928(trapping of carbenes via ylide formation)
281
tBu Cl
N N
tBu Cl
N
N+
tBu
Cl
_
:
- N2
hν
Jackson, J.E.; Soundarajan, N.; Platz, M.S.; Liu, M.T.H. J. Am. Chem. Soc. 1988, 110, 5595
N
N
S+
R1
R2
Ph H
NN
Ph H S+
R1
R2
Ph
H
hν
- N2
:R1-S-R2
_
- N2
hν : R1-S-R2 _
Romashin, Y.N.; Liu, M.T.H.; Hill, B.T.; Platz, M.S. Tetrahedron Lett. 2003, 44, 6519
Ynols (hydroxyacetylenes) R OH
Reviews:
Kresge, A.J. Acc. Chem. Res. 1990, 23, 43
Staudinger, H.; Klever, H.W. Chem. Ber. 1908, 41, 594 (confirmation that ketene structure is not that of hydroxyacetylene) R OH RCH C O
Meinert, R.N.; Hurd, C.D. J. Am. Chem. Soc. 1930, 52, 4540 (coining of names "ynol" and "keteno-ynol" isomerism akin to keto-enol isomerism)
282
H OH
von Baar, B.; Weiske, T.; Terlouw, J.K.; Schwarz, H. Angew. Chem. Int. Ed. 1986, 25, 282Hochstrasser, R.; Wirz, J. Angew. Chem. 1989, 101, 183
Ph
O
OH
OHPh PhCH C O- CO
hν
Chiang, Y.; Kresge, A.J.; Hochstrasser, R.; Wirz, J. J. Am. Chem. Soc. 1989, 111, 2355
Craig, D.; Regenass, F.A.; Fowler, R.B. J. Org. Chem. 1959, 24, 240Julia, M.; Descoins, C. Bull. Soc. Chim. Fr. 1962, 1939Eugster, C.H.; Kuser, P. Chimia (Aarau) 1964, 18, 358Baker, C.S.L.; Landor, P.D.; Landor, S.R.; Patel, A.N. J. Chem. Soc. 1965, 4348
283
Index
Acylium ions (oxocarbonium ions)...........................................................................................1N-Acylonium ions (acylammonium ions)....................................................................................2Alleneoxide......................................................................................................................2Aromatic pi-complexes.........................................................................................................3
Charge transfer complexes............................................................................................4Sandwich complexes (metallocenes).................................................................................7
Aromatic sigma complexes (see Meisenheimer-Jackson, Janovsky, Wheland).........................................8Arylium ions (see phenyl cation)..............................................................................................10Aziridinium ions.................................................................................................................10Benzyne (arynes)................................................................................................................11Betaines (phosphonium betaines).............................................................................................18Biradicals.........................................................................................................................18
Thiele hydrocarbon.....................................................................................................19Chichibabin hydrocarbon.............................................................................................19Schlenk-Brauns hydrocarbon........................................................................................20Müller hydrocarbon...................................................................................................21Norrish Type I.........................................................................................................23Norrish Type II........................................................................................................23
Bridged carbocations (see halonium, non-classical, phenonium).........................................................25Carbanions.......................................................................................................................25Carbanions via E1cb............................................................................................................27Carbenes (methylenes).........................................................................................................28Carbenes (singlet)...............................................................................................................34Carbenes (triplet)................................................................................................................35Carbenes (Arduengo)...........................................................................................................36Carbenes (Bertrand)............................................................................................................36Dicarbenes.......................................................................................................................37Carbocations.....................................................................................................................37Carbynes.........................................................................................................................432,4- and 2,5-Cyclohexadienones..............................................................................................442,4- and 2,5-Cyclohexadienimines............................................................................................44Cyclopropenyl cations..........................................................................................................46Dications..........................................................................................................................47
Benzidine rearrangement...............................................................................................47Dications synthesized in magic acid..................................................................................47Violenes..................................................................................................................48Wallach intermediate....................................................................................................49
284
Wurster salts.............................................................................................................491,3-Dioxolenium ions...........................................................................................................501,3-Dipoles (carbene traps).....................................................................................................52
Azomethine ylide........................................................................................................52Carbonyl oxide (Criegee zwitterion)..................................................................................52Carbonyl ylide...........................................................................................................52Nitrile ylide..............................................................................................................57Thiocarbonyl ylide......................................................................................................58
1,3-Dipoles (nitrene traps)......................................................................................................59Azomethines.............................................................................................................59Azonium imines.........................................................................................................60Carbonyl imines.........................................................................................................61Nitrilimines..............................................................................................................61Nitrosoimines............................................................................................................62Thiocarbonyl imines....................................................................................................62
Doering-Zeiss intermediate......................................................................................................62Enols and enolates...............................................................................................................63Episulfonium ions................................................................................................................65
Sulfenium ions..........................................................................................................65Sulfonium ions..........................................................................................................69
Extended cumulenones..........................................................................................................71Propadienones (methyleneketenes)...................................................................................71Butatrienones............................................................................................................78Iminopropadienones....................................................................................................80
Halonium ions....................................................................................................................82Hydronium ions..................................................................................................................85Iminium ions......................................................................................................................85Janovsky complex...............................................................................................................86Ketenes............................................................................................................................86
Metal ketenides..........................................................................................................89Ketene zwitterions...............................................................................................................90Ketyl radicals and ketyl radical ions...........................................................................................91Meisenheimer-Jackson complexes.............................................................................................95Mercurinium ions................................................................................................................96Metal carbenoids.................................................................................................................100Nicholas cation...................................................................................................................102Nitrenes...........................................................................................................................103
Dinitrenes................................................................................................................105Trinitrenes................................................................................................................106
285
Nitrenium ions....................................................................................................................107Nitrilium ions.....................................................................................................................110Nitronium ions...................................................................................................................110Nitrosonium ions.................................................................................................................111Non-classical ions (hyperco-ordinate carbocations, sigma-bridged cations)..............................................112Oxenium ions.....................................................................................................................114Oxirene............................................................................................................................117Oxonium ions.....................................................................................................................121
Acetoxonium ions.......................................................................................................121Flavinium ions...........................................................................................................122Flavylium salts..........................................................................................................122Meerwein salts...........................................................................................................123Methoxonium ions......................................................................................................124Pyrylium salts...........................................................................................................124
Phenonium ions..................................................................................................................125Phenyl cation (phenylium ion, arylium ion, benzene cation)...............................................................126Phosphenium ions...............................................................................................................128Phosphonium ions...............................................................................................................129o-Quinodimethanes (o-xylylenes)..............................................................................................131p-Quinodimethanes (p-xylylenes)..............................................................................................132o-Quinonemethides and p-Quinonemethides..................................................................................133Radicals...........................................................................................................................134
Carbon centred..........................................................................................................136Gomberg radical................................................................................................136Alkyl radicals...................................................................................................137Aryl radical (phenyl radical)..................................................................................142Benzoyl radical.................................................................................................150Acyl radicals....................................................................................................154Benzyl radical...................................................................................................158Koelsch radical.................................................................................................160
Group IV (Si, Ge, Sn).................................................................................................160Silyl..............................................................................................................160Germyl..........................................................................................................163Stannyl..........................................................................................................164
Group V (N, P).........................................................................................................166Aminyl...........................................................................................................166N-Alkoxy-N-alkylamino radicals............................................................................169Amido radicals..................................................................................................170Hydrazyl........................................................................................................171
286
Nitroxide radicals..............................................................................................174Thioaminyl radicals............................................................................................175Sulfonamidyl radicals..........................................................................................176N-Thiosulfonamidyl radicals.................................................................................178Verdazyls........................................................................................................179Phosphinoyl radicals...........................................................................................182Phosphinyl radicals............................................................................................187Phosphoranyl radicals.........................................................................................191Thiophosphinoyl (phosphinothioyl) radicals...............................................................193
Group VI (O, S, Se)....................................................................................................194Acetoxy (acetoxyl) radicals...................................................................................194Alkoxy radicals.................................................................................................196Iminoxyl radicals...............................................................................................198Nitroxyl radicals................................................................................................200Kenyon-Banfield radical......................................................................................205Peroxy radicals.................................................................................................206Phenoxy (phenoxyl) radicals.................................................................................207Sulfanyl (mercapto, thiyl) radicals...........................................................................213Sulfinyl radicals................................................................................................214Sulfonyl radicals...............................................................................................216Sulfuranyl radicals.............................................................................................217Thionitroxide radicals..........................................................................................219Thiophenoxy (phenylthio, phenylthiyl, benzenethiyl) radicals...........................................221Phenylselanyl radical..........................................................................................222Selanyl...........................................................................................................223
Radical anions....................................................................................................................223Radical cations....................................................................................................................225
Wurster salts.............................................................................................................226Distonic...................................................................................................................232
Silylenes and germylenes.......................................................................................................235Silylium ions (silylenium ions, silicenium ions, silyl cations, silicocations).............................................237Tetrahedral intermediates........................................................................................................239Thiirenium ions...................................................................................................................241Transition metal carbene complexes...........................................................................................243Transition metal carbyne complexes...........................................................................................246Transition metal ketenyl complexes............................................................................................247Transition metal keteniminium complexes....................................................................................249Transition metal iminium complexes...........................................................................................251Transition metal silene complexes..............................................................................................252
287
Transition metal vinyl cation complexes.......................................................................................254Transition metal vinylidene complexes........................................................................................255Transition metal vinylidenecarbene complexes...............................................................................257Triplet ketones (excited state)...................................................................................................258Triplet olefins (excited state)....................................................................................................259Tropylium ion....................................................................................................................259Vinyl cations......................................................................................................................261Vinylidenes (methylene carbenes, alkylidene carbenes).....................................................................264Vinylidenecarbenes (allenylidenes, alkenylidene carbenes).................................................................265Wallach intermediate (see Dications)...........................................................................................266Wanzlich carbenes...............................................................................................................266Wheland intermediates (arenium ions, benzenium ions)....................................................................267Ylides (1,2-dipoles)..............................................................................................................270
Ammonium ylides.......................................................................................................270Oxonium ylides..........................................................................................................273Phosphonium ylides....................................................................................................273Pyridine ylides...........................................................................................................275Sulfimine ylides.........................................................................................................278Sulfonium ylides........................................................................................................278Trapping of carbenes generated by flash photolysis................................................................279
Ynols (hydroxyacetylenes)......................................................................................................281