ii. A. E. Gordon and A. Frigeto, J. Chromatogr., 73, 401 (1972). 12. A. N. Terepin, The Photonics of Dye Molecules [in Russian], Nauka, Leningrad (1967),

p. 181.

OXIDATION OF UNSATURATED TERTIARY AMINES, AMIDES, AND IMIDES

BY MOLECULAR OXYGEN CATALYZED BY PALLADIUM COMPLE>~S

G. A. Dzhemileva, V. N. Odinokov, and U. M. Dzhemilev

UDC 542.943.7:541.49:546.362: 547.333.3

The oxidation of olefins by molecular oxygen in the presence of palladium salts has potential as a route for the synthesis of ketones of various structures [1-5]. On the other hand, there is very little information in the literature on the application of this method to the conversion of unsaturated tertiary amines, amides, and imides into the corresponding carbonyl compounds. This is evidently connected with the fact that amines, added to a PdCI 2- CuCI catalyst composition, completely block the oxidation of olefins by molecular O 2 on ac- count of the formation of coordination-saturated complexes of Pd and Cu which are only feebly active in the oxidation of unsaturated compounds.

It might be expected that introduction of protonic acids, capable of bonding with the nitrogen in the initial unsaturated amine, amide, or imide molecule into the palladium cata- lyst composition would make'it possible to oxidize these compounds to the corresponding ke- tones.

We have established that the presence of a protonic acid in the system, with a ratio amine:acid = 1:3 and amide or imide:acid = i:i, is a necessary condition for the conversion of the amine, amide, or imide to a ketone. Oxidation by O 2 is carried out in the presence of a PdCI2-CuCI catalyst (Pd:Cu:amine/amide/imide = 1:10:5 to 20) at a temperature of 60-65~ with a reaction time of 6 h in THF as solvent. The highest yields of amino-, amido-, and imidoketones are obtained on oxidation of the unsaturated amine, amide, or imide in the pres- ence of a catalyst and CF2CO2H

[I'd], CF,CO211 1 B ~ - - N ~ / ~ / ' ~ o, '" R ~ - - N / N ~ " ' / N ' / ~ " o

I J R 2 R 2

( I a - m ) ( I I a - m ) t t l ___ R ~ = (CHs)(a); ICD + tl~ = (CH=)5(b); R 1 ~ R 2 = (CH2)2--O--(CH2)2(c); R1 ----- CH3, I t = = C-HJd: '~- P J = C O C , H ~ t t ~ = C e H ~ ( e ) ; B I = C O C H 3 . }t:-----C6Hs(fi; R I = C O C H s , II= = C H s i g ) ~ ' t t l = COCHs', tt~ = o-C.HaCns(h) ; t/1 = COCH3, tl~ = ,n-C,H4F(~.); R 1 = COCHs, R2 = p_C~HaO2(j), 17/1 = COH, tl 2 := H(k) ; H 1 = COH, t/2 = C.HI~(~,); R 1 + R~ = (COCH2)2(m).

On oxidation of N-methyl-N-(2E,7-octadienyl)aniline (Id), 1,3E-6E-octatriene and methyl- aniline were formed in addition to (lid), these being the decomposition products of the ori- ginal amine (Id).

On oxidation of N,N-bis(2E,7-octadienyl) derivatives of methylamine (Ilia) and benzyl- amine (lllb), the corresponding mono- and diketones (IVa-c) and (Va-b) were formed~

Institute of Chemistry, Bashkir Science Center. Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2148-2151, September, 1988. Original article submitted April 16, 1987.

0568-5230/88/3709-1929512.50 �9 1989 Plenum Publishing Corporation 1929

TABLE i. Yields and Properties of Compounds Prepared

Compound

(Ila) (IIb) (IIc) (I] d) (If e)

( I I f ) (ii~) (n 19 (n ~ *

(IIk) (I~m) (Ira) (IV~

(IVc) (V~

(VlIa)

Bp, ~ (p~, .,m

�9 ~ Hg)

89 tt0(2) 90 107 (2) O0 t21 (2) 60i 150 (2) 781Chromato.

i ~aphica113 00 t45(t) ' 831 it5(~) 56 t52(1) 591 t59(t) 60 Chromato- I ~raphical i~

42 t08(1) 85 t48 (I) 66 t46 (1) t5 Zhromato- Igraphicall~

15 ~> 34( 161 (I) 781Chromato- lgraphical i,

t51 )> "

2O nD

[,4895 .4849 [,4839 .,53221 L,56491

,5305i ,47351 ,52~1 ,523~ I ,572t

.48811 ,5o591 ,477t I ,453t I

,55t41 ,4919 i ,52711

,48101

Found, %

C H

7t.08 lt.i6 74,63 11,0~ 68,22 9,97 77,9i 6,07 78,55 7,t41

74,tt 8,t~ 57,08 9,58 74,70 8,44 69,25 7,27 63A2 6,60

63,82 8,59 ~4,52 7,67 77,50 tt,06 8t,40 9,7t

81,t5 9,58 73,tl t0.37 77,72 9,32

75,45 10,71

N

Empirical formula

CIoH~gNO CI~H~aNO CI2Hz~NO~ CIgH2~NO C=iH~aNO=

CteH=INO~ CttH,~NO~ CtvH=aNO~ C~H2oNO~F CI~HzoN~O~

CgHtsNO2 Ci:~Hv~N03 C17H29NO C~H,~NO

C2=H~INO CITH29N02 C2~H~NOz

C2oH34N~O

Calculated, %

c H N

7t,00 74.64 68,24 77,92 78,5O

74,13 BT,O0 7432 S9,3t S3A5

33.90 34,57 77.56 81,41

Bt.30 73,t2 77,74

75,47

M§

169 2O9 211 231 32!

259 197 273 277 3O4

169 223 263 339

325 279 355

318

*Found: F 6.85%. Calculated: F 6.82%.

l ~ - - N ( / k 2 " , , / ~ / % , ) , ( I I Ia -c)

R = CH,(a), CH2--CeHs(b),CsHs(c).

R [Pd], CF, CO,H [ [

~- ~ ' , , / ~ / % / ~ N / ~ 2 " , , / k / ' ~ O, " ' b (Iva-c) ~ (Va-b) O/2

N,N-bis(2E,7-Octadienyl)aniline (IIIc) on oxidation gives only the monoketone (IVc) in 15% yield. N,N'-bis(2E,7-Octadienyl)piperazine (Via) behaves in a similar way:

(Via) ~ _. ' O, / / " ' / ~ / ~ ' / ~ N , , x . _ . ~ N / ~ " ( V l I a ) / ~ / ~ O "

EXPERIMENTAL

The initial amines (Ia-d), (IIIa-c), and (IVa), amides (Ie-h, j-l), and imide (Im) were prepared by the methods of [6-8]. Their purity, as determined by GLC, was 99Z. GLC

analyses were carried out on a Crom-5 chromatograph with flame-ionization detector, 1.2-m column with SE-30, helium carrier gas. Proton ~ spectra were run on a Tesla BS-487B instrument as solutions in CCI~ with HMDS as internal standard. IR spectra were run on a UR-20 spectrophotometer as thin films or mulls. Mass spectra were recorded on an MX-13-06 instrument with ionization energy 70 eV at 200~

Oxidation of Unsaturated Amines~ Amides, and Imides. To 85~oles of starting material was added i00 ml THF, and CF3COOH: 26.5 g (255 ~oles) for the amines and 8.8 g (85 mmoles) for amides and imides. The reaction mixture was thoroughly stirred for 3 h at room tempera- ture, or in the case of (Ia, d), (IIIa-c), and (Via) at 60~ PdCI 2 (1.49 g, 8.5 mmoles) and CuCl (8.36 g, 85 mmoles) were then introduced into the reactionmixture, 5 ml H2Owere poured in and oxygen was bubbled through the mixture at 5 liters/h for 6 h while stirring at 60~ The reaction mixture was neutralized with NaHCOs, extracted with CHCI s and the extract waswashed with water until the washings were neutral; it was then dried over MgS04. The solvent was evaporated and the residue distilled in vacuum or chromatographed (silica gel, 40 x I00, 9:1 benzene-methanol eluent)o Spectroscopic data for the compounds prepared are given in Table 2 and yields and physicochemical properties in Table i.

CONCLUSIONS

Oxidation of higher unsaturated tertiary amines, amides, and imides hasbeen carried out using PdCI2-CuCI-CFsCOOH catalyst system and molecular oxygen, the products being the corresponding amino-, amido-, and imidoketones.

1930

TABLE 2.

IR

and

Proton

NH

R Spectra

of Compounds

Prepared

Com

poun

d

(lla

) (l

ib)

(llc

)

(lld)

(lle)

(IlO

(Jig

)

(n~

(ii~

(Ilk)

(IIm)

(IV~

(lVb)

(lVd

(V~

(Vb)

(VII

a)

CH

= C

H~

920

920

920

920

IR spectra

"( V,"cm -I)

Prot

on NM

R spectra

( 6, ppm)

Ctt

=C

H

980,

30

30

980,

30

30

980,

303

0

980,

303

0

980,

303

0 98

0,

3030

98

0, 3

030

980,

303

0

980,

303

0 98

0,

3030

980,

30

30

980,

30

30

980,

303

0

980,

30

30

980,

303

0

I}80

, 30

30

980,

303

0

080,

30

30

C=

O

aro

mat

ic

1720

17

15

1715

1715

t630

, t7

t0

1660

, t7

20

t660

, 17

10

rin

g

t620

, 17

10

1670

, t7

20

t670

, t7

20

t660

, 17

i0

t7t5

, 17

70

1720

-

1715

- m

710,

77

0,

3010

710,

770

7t0,

77

0

CH

2 C

H2-

-C~

CHa--CO

CH

a--P

h C

II2-

-CO

C

H3N

1715

1720

17

15

1715

700,

74

5

7i0,

77

0,

3010

700,

75

0

t,55

m

t,4

t ~n

1,

51

m

t,56

m

1,51

m

1,

5t

m

1,53

m

t,51

m

1,5t

m

1,51

m

t,61

.m

i

1,53

m I

t,58

m

i,55

:m

1,55

m

1,58

m

t,55

m

1,51

m

1,91

m

1,

92

m

1,83

m

t,9

t m

1,82

m

1,

81

m

1,81

m

1,81

m

1,63

,m

t,65

m

i,96

m

1,91

m

1,96

m

t,91

m

t,83

m

1,96

m

1,

9t

m

t,9

6,

m

2,01

s

2,06

s

1,95

s

t,96

s

2,0

s 2,

0 :s

1

,96

s

2,00

s

2,21

s

2,00

s

1,82

s

2,00

s

2,10

s

1,96

s

2,13

s

2,00

s

2,00

s

2,06

s

2,00

s

2,00

s

2,2t

m

2,33

m

2,26

m

2,25

m.~

2,t6

m

2,.t

2m

2,30

m

2,36

m

2,31

m

2,3i

m

2,44

n

2,32

n

2,41

u

2,31

' n

2,25

n

2,31

2

,31

n

2,3t

2,35

s

2,86

s

1,61

s

2,03

s

2,75

d

t,66

s

t,8

25

2,18

s

2,08

s

2,72

s

--N

--C

H2-

-C~

C

H2-

-N--

Ph

3,08

d

2,75

d

2,65

d

3.45

m

3

,75

d

2,20

m

3.

9i

d 3,

75

d

3,81

d

3,92

s

3,95

d

3,81

d

2,53

s

3,86

d

2,95

d

2,85

d

3,51

s

3,71

d

2,81

2,

85

d d 3,

5i

S 3,

06

d

CH

2=C

--

0H~

CH

--

5,56

" m

5,

43 m

5,

36

m

5,4t

.m

5,51

m

5,32

m

5,40

m

5,41

: m

5,53

m

5,

49

m

5,53

:m

5,36

m

5,08

m

5,

55

m

4,9t

m

5,

41

m

4,75

m

5,

4t

m

5,42

m

5,

51

m

4,85

5,

52

C,,I

Is

6,62

m

7,12

m

7,12

m

7,12

m

7,22

m

7,3t

m

7,55

m

7,20

s. -

N

H

8,t2

m

- tt

CO

7,t2

6,55

m

6,95

m .

7,21

m

b~

L~

b.a

LITERATURE CITED

i. I. I. Moiseev, n-Complexes in Liquid-Phase Oxidation of Olefins [in Russian], Nauka, Moscow (1970).

2. J. Smidt, W. Hafnez, R. Jira, et al., Angew. Chem., 71, 176 (1959). 3. J. Tsuji, M. Kaito, T. Yamada, and T. Manadai, Bull. Chem. Soc. Jpn., 51, 1915 (1978). 4. G. A. Dzhemileva, V. N. Odinokov, U. M. Dzhemilev, and G. A. Tolstikov, Izv. Akad. Nauk

SSSR, Set. Khim., 343 (1983). 5. G.A. Dzhemileva, V. N. Odinokov, U. M. Dzhemilev, Izv. Akad. Nauk SSSR, Ser. Khim., 149 (1987).

6. U. M. Dzhemilev, R. N. Fakhretdinov, and A. G. Telin, Izv. Akad. Nauk SSSR, Ser. Khim., 163 (1980).

7. Uo M. Dzhemilev, A. Z. Yakupova, and Go A. Tolstikov, Izv. Akad. Nauk SSSR, Ser. Khim., 1068 (1978).

8. R. N. Pakhretdinov, A. G. Telin, and R. M. Safuanova, 4th International Symposium on Homogeneous Catalysis, Leningrad, Vol. 1 (1984), p. 263.

NEW HYDROCARBONS IN THE SYNTHESIS OF ADAMANTANOIDS

R. I. Khusnutdinov, V. A. Dokichev, . D. K. Galeev, N. F. Asylguzhina, S. Z. Sultanov, and U. M. Dzhemilev

UDC 542.97:542.952.1:547.642+ 547.315.71:547.518

For obtaining adamantane, diamantane, and their derivatives mainly hydrogenated dimers of cyclopentadiene, norbornadiene, and their derivatives have been used.

In a search for new accessible hydrocarbons capable of being transformed by catalytic skeletal isomerization into adamantane and diamantane, we have investigated thermal and catalytic [2~ + 4~]-homo- and codimerization of spiro[2.4]hepta-4,6-diene (I) with propylene, butadiene, and cyclopentadiene.

Considering that thermal dimerization of (I) to dispiro{cyclopropan-5,1'-endotricyclo- [5o2.1.02,6]deka-3,8-dien-10,1"-cyclopropane} (II), which is of interest in the synthesis of cage hydrocarbons, proceeds with very low yields [8], we have tried to carry out a cata- lytic version of this reaction using Lewis acids. The best results were obtained using the complex AiCl3-dicyclohexyl-18-crown-6 which catalyzes formation of homodimer (II) with yields of 55%.

(I) (II) (I)

H~ ~

( 'III) ( IV )

H2 = ~ ~ CnH z

(v) .(x)

+ . ~ + (IO

(Vl) (vii) Institute of Chemistry, Bashkir Scientific Center. Ural Branch, Academy of Sciences

of the USSR, Ufa. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2152-2155, September, 1988. Original article submitted April 23, 1987.

1932 0568-5230/88/3709-1932512.50 �9 1989 Plenum Publishing Corporation