反応例 13.1 ハロアルカンの求核置換反応(sn2反応)...反応例 13.1...
TRANSCRIPT
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反応例 13.1 ハロアルカンの求核置換反応(SN2反応)
シアノ化
+ KCN!"#$%&'(
+ KBrCH3(CH2)10CH2Br CH3(CH2)10CH2CN
J.R. Ruhoff, Organic Syntheses, Coll. Vol. 2, 292 (1943).
HOCH2CH2Cl + NaCN HOCH2CH2CN NaCl+
45-50 °C
!79-80%
E.C. Kendall, B. McKenzie, Organic Syntheses, Coll. Vol. 1, 256 (1941).
CH3CH2OCH2CH2Br NaCN+
!"#$%&'
140 °C
CH3CH2OCH2CH2CN
52-58%
NaBr+
G.C. Harrison, H. Diehl, Organic Syntheses, Coll. Vol. 3, 557 (1955).
C6H5CH2Cl NaCN C6H5CH2CN + NaCl
!-"#$%&'()80-90%
+
R. Adams, A.F. Thal, Organic Syntheses, Coll. Vol. 1, 107 (1941).
CH3
CH3
H3C
CH2Cl
NaCN+
!"#$%&'
100 °C
CH3
CH3
H3C
CH2CN
NaCl+
89-93%
R.C. Fuson, N. Robjohn, Organic Syntheses, Coll. Vol. 3, 557 (1955).
BrCH2CH2CH2Br + 2 NaCN NCCH2CH2CH2CN + 2 NaBr
!"#$%&'
()77-86%
C.S. Marvel, E.M. McColm, Organic Syntheses, Coll. Vol. 1, 536(1941).
-
ClCH2CH2CH2Br KCN ClCH2CH2CH2CN+ KBr
!-"#$%&'()40-47%
+
C.F.H. Allen, Organic Syntheses, Coll. Vol. 1, 156 (1941).
CH2=CHCH2Br CuCN CH2=CHCH2CN + CuBr
80-84%!"
+
J.V. Supniewski, P.L. Salzberg, Organic Syntheses, Coll. Vol. 1, 46 (1941).
O
CH2Cl
+
!
10 °C"#$
NCCH2CH(OH)CH2CN
54-62%
KCl KOH+ +
O
CH2Cl
NC
O
NC
Cl
O
NCCN
O
NC CN
2 KCN
–
–
–
–
(エポキシドの開環から反応が進んでいる.)
Organic Syntheses, Coll. Vol. 5, 614.
炭素求核剤(エノラートイオンのアルキル化は 17章を見よ)
S
S!"#n-C4H9Li$#%&'()*+',-./
0"#Cl(CH2)3Br
1"#n-C4H9Li S
S
65-84% Organic Syntheses, Coll. Vol. 6, 316.
ClCH2CH2CH2CN
!"#NaOH$%&'()*
+"#,$%&'()*COOH
74-79%-),./0
Organic Syntheses, Coll. Vol. 3, 221.
-
C6H5CHBrCCHBrC6H5
O
!"##$%&
N(CH2CH3)3
O
C6H5 C6H5
44%
'(
Organic Syntheses, Coll. Vol. 5, 514.
O O
BrH2C CH2Cl
KNH2, NH3
!"#$%-50 °C
55-70%
O O
Organic Syntheses, Coll. Vol. 8, 173.
窒素求核剤
CH3CHBrCO2H CH3CH(NH2)CO2H NH4Br+
65-70%
!"#$%"&
'()*+,-
W.C. Tobie, G.B. Ayres, Organic Syntheses, Coll. Vol. 1, 23 (1941).
CH3(CH2)3CHBrCO2H50-55 °C, 20-30!"
+ NH4Br
62-67%
CH3(CH2)3CH(NH2)CO2H#$%&'$(
C.S. Marvel, V. du Vigneaud, Organic Syntheses, Coll. Vol. 1, 48 (1941).
BrCH2CH2SO3Na
!"#$%"&'(
+ NH3 H2NCH2CH2SO3H NaBr+
48-55% Organic Syntheses, Coll. Vol. 2, 563.
-
C6H5CH2Cl + C6H5NH2!"90-95 °C
85-87%
C6H5CH2NHC6H5
NaHCO3
Organic Syntheses, Coll. Vol. 1, 102.
C6H5CH2Cl NH
O
O
+ NCH2C6H5
O
O
K2CO3
190 °C
72-79%
Organic Syntheses, Coll. Vol. 2, 83.
CH2Br
CH2Br
+
SO2NH2
CH3
60-70 °C
!"!#$%&'(')*+,N SO2 CH3
75-84%
+ H2 +
2 NaH
2 NaBr
Organic Syntheses, Coll. Vol. 5, 1064.
C6H5CH2Br +
NH
KOH
!"#$%$&'()*+
N
CH2C6H5
85-89% Organic Syntheses, Coll. Vol. 6, 104.
NH3+Cl-Cl
N
N2
NH
75%
Organic Syntheses, Coll. Vol. 6, 666.
-
Cl O O ClC6H5CH2NH2+
120 °C NH
O O NH
C6H5C6H5
85-95%
NH
O O NH
C6H5C6H5
N
O O
N
O O
PhPh
I O O I+
Na2CO3, NaI
!"#$#%&'()*
67-71% Organic Syntheses, Coll. Vol. 8, 152.
C6H5CH2N
O
O NCH2CH3
NCH2CH3
I O O I+
K2CO3
!"#$#%&'(
C6H5CH2N
O
O N
CH2CH3
N
CH2CH3
O
O
72-75% Organic Syntheses, Coll. Vol. 6, 34.
CH2=CH CO2Me
BrCH3 NaN3
CH2=CH CO2Me
N3CH3
!"#$%&'(
F. A. Carey and R. J. Sundberg, Advanced Organic Chemistry, 4th ed., Kluwer Academic/Plenum Publihers,
Part B, p. 151.
B. B. Snider, J. V. Duncia, J. Org. Chem., 46, 3223 (1981).
-
CH3(CH2)3CH2ICH3CH2OCH2CH2OCH2CH2OH, H2O
NaN3CH3(CH2)3CH2N3
84%
F. A. Carey and R. J. Sundberg, Advanced Organic Chemistry, 4th ed., Kluwer Academic/Plenum Publihers,
Part B, p. 151.
酸素求核剤
H3CC CHCH2Cl
Cl
!"# Na2CO3$%&
'(H3CC CHCH2OH
Cl
63% Organic Syntheses, Coll. Vol. 4, 128.
OH
H
H
Cl
NaOHO
!
70-73%
NaCl+
O
H
H
Cl
OHO
H
H
ClO
H
H
–
H–
Organic Syntheses, Coll. Vol. 1, 185.
CH2ClCHOHCH2ClNaOH O
C CH2ClH2C
H
NaCl+
!"#$40-45 °C, 4%&
76-81%
Organic Syntheses, Coll. Vol. 1, 233.
-
KOHCCl H
CH2OH
CH3
OH
CH3!" 20-30 °C
65-70%
Organic Syntheses, Coll. Vol. 8, 434.
C6H5OH + BrCH2CH2CH2Br C6H5OCH2CH2CH2Br + NaBrNaOH
!"#$1.3%&'( 84-85%
Organic Syntheses, Coll. Vol. 1, 435.
K2CO3PhCH2Cl +
OH
CH3
NO2!"!#$%&'(')*+,
90 °C
OCH2C6H5
CH3
NO2
90%
Organic Syntheses, Coll. Vol. 7, 34.
NO2
CH2Cl
+
!"#$%
NO2
CH2OCCH3
NaCl+
89-93%
CH3CO2Na
O
Organic Syntheses, Coll. Vol. 3, 650.
BrCH2(CH2)9CO2H
O
O
79-83%
K2CO3
!"#$%$&'()
100 °C
Organic Syntheses, Coll. Vol. 6, 698.
-
O
O
OH
OH
O
O
O
O
O
O
Cl
O
Cl
O
+
!"#$%&'#()*+,
KOH
38-44%
Organic Syntheses, Coll. Vol. 6, 301.
O
O
O
O
O
OCl
O
Cl
OH
OH
+!"#$%
&'
NaOH
39-48%
Organic Syntheses, Coll. Vol. 6, 395.
硫黄求核剤
(CH3)2CHBr + KSCN!"#$%&'(
(CH3)2CHSCN KBr+
76-79% Organic Syntheses, Coll. Vol. 2, 366.
CH3C(O)CH2Cl + CH3SNa!"#$%
74-76%
CH3C(O)CH2SCH3
5 °C&'( Organic Syntheses, Coll. Vol. 6, 601.
CH2=CHCH2Br
S
N
HS+N(CH2CH3)3
!"#$%&'#()*
S
N
CH2=CHCH2S
69-70% Organic Syntheses, Coll. Vol. 6, 704.
-
CH2Cl2 + 2 C6H5SHN(CH2CH3)3
!"##$%&
25 °C
SC6H5H2C
SC6H5
56-65% Organic Syntheses, Coll. Vol. 6, 737.
C6H5SH C6H5SCH2CH2Br!"#CH3CH2ONa, CH3CH2OH
$"#BrCH2CH2Br
C6H5SCH2CH2BrCH3CH2ONa, CH3CH2OH
%&C6H5SCH=CH2
50-65%
Organic Syntheses, Coll. Vol. 7, 453.
!"#$%&'(+BrCH2CH2Br HSCH2CH2SH
2 NaOCH2CH3
S
S
2 NaBr+
55-60%
Organic Syntheses, Coll. Vol. 4, 396.
HSCH2CH2CH2SH + 2 ClCH2CH2OHCH3CH2ONa, CH3CH2OH
!"OH HO
SS
71-82%
+ 2 (H2N)2C=S
BrCH2CH2CH2Br+
#$ %&'(!"
)$ KOH*+,(!"
53%
-*-./012324567
55-60 °C
58-62%
OH HO
SS
SH HS
SS
SH HS
SS
S S
SS2 Cs2CO3
Organic Syntheses, Coll. Vol. 8, 592.
-
HSCH2CH2SH+ClC(O)CH2Cl
S
S ON(CH2CH3)3
!"##$%&
0-10 °C
60%
Organic Syntheses, Coll. Vol. 6, 72.
N(CH2CH3)3CH3C(O)CHBrCH3 + CH3CH2CH2C(O)SH
!"#$%&'CH3C(O)CHCH3
SC(O)CH2CH2CH3
98-100%
Organic Syntheses, Coll. Vol. 6, 776.
!"
C6H5CH2Cl + Na2S#$%&'()*
C6H5CH2SCH2C6H5 2 NaCl+
80% Organic Syntheses, Coll. Vol. 6, 404.
2 HOCH2CH2Cl Na2S+
90-95 °C
!HOCH2CH2SCH2CH2OH 2 NaCl+
79-86%
Organic Syntheses, Coll. Vol. 2, 576.
BrCH2CH2NH2•HBr H2NCH2CH2SO3H 2 NaBr+
!" Na2SO3#$%
&"$'(68-73%
Organic Syntheses, Coll. Vol. 2, 564.
(CH3)2CHBr + Na2S2O3!-"#$%&
'(
(CH3)2CH S SO3Na NaBr+
Organic Syntheses, Coll. Vol. 6, 235.
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リン求核剤
BuLi
Ph3P CH2Et2O
O
!
Ph3P+CH3 Br
–
CH2
G. Wittig, U. Schoelkopf, Org. Synth., Coll. Vol. 5, 751 (1973).
CH3Br + Ph3P!"#$%&'
99%
35~40%
(Wittig )*+
CH3I + (i-PrO)3P (i-PrO)2PCH3
O
+ i-PrI
A.H. Ford-Moore, B.J. Perry, Org. Synth., Coll. Vol. 4, 325 (1963).
reflux, 1 h85~90%
ハロゲン化物の交換
CH3(CH2)4CH2Br + KFHOCH2CH2OH
160-170 °C
CH3(CH2)4CH2F + KBr
40-45%
Organic Syntheses, Coll. Vol. 6, 525.
(CH3)3SiCH2CH2CH2ClNaI
!"#$%&'(CH3)3SiCH2CH2CH2I
72-81% Organic Syntheses, Coll. Vol. 8, 486.