J.Org. Chem., Vol. 44, No. 1,1979
Codimerization of Acetylenes and Halides ture was heated a t reflux overnight. The reaction mixture was washed with 10 mL of water and solvent removed by distillation. The residue was distilled to give 4.1 g (44%) of product, bp 115 "C (9 mm). This material was purified by preparative GLC on a 9 f t x 1/4 in. column packed with 20% SE-30 on 60/80 Chromosorb W before use. This material showed a rotation of [(~]2O313-6.3 f 0.2 (c 0.0285, absolute ethanol). A solution of 2 g of this pyrrolidinone in 300 mL of 2-propanol was irradiated until 50% of the starting material was consumed (GLC). Solvent was removed by distillation and unreacted starting material purified by preparative GLC. This material showed a rotation [aI2O313 -6.3 (0.0286, absolute ethanol). Quantum Yields. Samples consisted of the pyrrolidinone (2 M) in 2-propanol or 2-methyl-2-propanol containing either nonane or decane internal standards. All pyrrolidinones were purified by preparative GLC. Samples were placed in 1.0 X 16 cm quartz tubes, subjected to three freeze--pump-thaw cycles to remove dissolved gases, and sealed a t 10+ torr. Samples were irradiated, in triplicate, in a merry-go-round apparatus surrounded by a bank of ten GE 15-T8 germicidal lamps whose principal emission is a t 254 nm. The formation of pentenal from cyclopentanone was used as a ~ t i n o m e t e rSince .~ the pyrroles produced in these reactions have molar absorptivities approximately 100 times larger than those of the pyrrolidinones at the irradiating wavelength (254 nm), conversions were held to below 1%to prevent product competition for the light. Samples were analyzed by GLC on either of the following columns: 20% SE-30 on 100/120 Chromosorb WHP, 6 ft X '14 in.; 3% OV-17 on 100/120 Chromosorb WHP, 6 ft X in. Quantum yield data are presented in Table 111.
Acknowledgment. We are indebted to the Center of Materials Research of the University of Maryland for partial support of this work. Registry No.-la, 932-07-0; Ib, 68036-46-4; Id, 3470-98-2; methylamine, 74-89-5; 2-pyrrolidinone, 616-45-5; 1-bromo-2-methylbutane, 10422-35-2; 1-(2-methylbutyI)-2-pyrrolidinone, 58244-31-8; I-methylazetidine, 4923-79-9; y - butyrolactone-5,6-d?, 68036-47-5; succinic anhydride, 108-30-5.
References and Notes (1)
NSF Science Faculty Fellow 1971
(2) Preliminary communications covering portions of this work have been published: P. H. Mazzocchi and J. J. Thomas, J. Am. Chem. SOC.,94,828
55
(1976);P. H. Mazzocchi, J. J. Thomas, and F. Danisi. J. Polym.Sci., Polym. Lett. Ed.. 13, 737 (1975). (3) A. T. Blades, Can. J. Chem., 48,2270 (1970). (4)C.Y. Mok, J. Phys. Chem., 74, 1432(1970). (5)P. Dunion and C. N. Trumbore, J. Am. Chem. SOC.,87,421 1 (1965). (6)R. Srinivasan, J. Am. Chem. SOC.,81, 1546 (1959). (7) F. E. Blacet and A. Miller, J. Am. Chem. SOC.,79, 4327 (1957). (8) S. W. Benson and G. B. Kistiakowsky, J. Am. Chem. SOC., 64, 80 (1942). (9)J. Graymore, J. Chem. Soc,, 1492 (1931). (IO) A.M. Duffield, H. Budzikwicz, andC. Djerassi. J. Am. Chem. Soc.,86,5536 (1964). (11)J. J. Bloomfield and S.L. Lee, J. Org. Chem., 32,3919 (1967). (12)L. Rudolph and D. Vaclav, Chem. Listy, 51, 139 (1957). (13)W. J. Lehman, J. Mol. Spectrosc., 7, 3 (1961). (14)To show that incwporation did not occur after product formation,we carried out two checks. Equimolar quantities of 1 and D 2 0 were irradiated in the mercury free apparatus for 102 h. Mass spectral analysis showed that the product pyrrole contained 12% dj and NMR indicated that it was incorporated in the p position. NMR of the recovered starting material showed a >IO% incorporationof deuterium in the 3 position, indicating that deuterium incorporation resulted from starting material exchange and not from exchange at the product stage. When pyrrole was allowed to stand for 11 days at 25 O C in the presence of D 2 0 and methylamine,no exchange oc-
curred.
(15)C:C-&dcock, M. J. Perona, G. 0. Pritchard, and B. Rickborn, J. Am. Chem. SOC.. 91. 543 (1969). J. D. Coyle, J. &e&. SOC.6, 1736 (1971).
The formation of 1-phenylpyrrole from 1-phenyl-2-pyrrolidinone on irradiation in solution was first observed by M. Fischer. M. Fischer, Chem. Ber., 102,342 (1969). J. C. Dalton, K. Dawes, N. J. Turro, D. S. Weiss, J. A. Barltrop, and J. D. Coyle, J, Am. Chem. SOC., 93,7213 (1971). Y. Kanaoka, Y. Migita, K. Koyama, Y. Sato, H. Nakai, and T. Mizoguchi, Tetrahedron Lett., 1193 (1973). Y. Kanaoka and Y. Hatanaka, J. &g. Chem., 41,400 (1976). L. Crombie and S. H. Harper, J. Cbem. SOC.,2688 (1950). M. Fischer, Chem. Ber., 101, 2669 (1968). C. H. Nicholls and P. Leermakers. J. Org. Chem., 35,2754 (1970). P. H. Mazzocchi and M. Bowen, J. Org. Chem.. 40,2689(1975). P. J. Wagner, Acc. Chem. Res., 4, 169 (1971). A. Scala and G. Hussey, J. Am. Chem. SOC.,96,4069(1974). R. Ditchfield.J. E. Del Bene, and J. A. Pople, J. Am. Chem. SOC.,94,703 (1972). P. H. Mazzocchi and C. W. Jameson. unpublished results. The system is similar to one described in the literature3' with two additional features. Liquid returns from the condenser via a Pyrex return tube centered in the quartz reactor. A heater, fan, and thermostat allow the temperature of the apparatus to be adjusted so that no liquid condenses on the quartz surface. I. S.Krull, Mol. Photochem., 5, 8389 (1973). R. H. Higgins, N. H. Cromwell, and W. H. Paudler, J. Heterocycl. Chem.. 8 , 961 (1971).
Selective Codimerization of Acetylenes and Allyl Halides Catalyzed by Palladium Complexes Kiyotomi Kaneda,* Tetsuya Uchiyama, Yuzo Fujiwara, Toshinobu Imanaka, and Shiichiro Teranishi Department of Chemical Engineering, Faculty of Engineering Science, Osaka Uniuersity, Toyonaka, Osaka, Japan Received J u n e 20, 1978 The reaction of various acetylenes and allyl halides with palladium complexes selectively gives substituted 1,4diene codimers. The PdXZ(PhCN)Z complex is the most active catalyst. In contrast to substituted acetylenes, the cotrimer besides codimers. The reaction of acetylene itself and allyl halides gives a l-halogeno-1,3,6-heptatriene catalytic reaction proceeds via Pd-halogen bond recycle; initially acetylene inserts into a Pd-halogen bond and subsequently allyl halide inserts into a Pd-vinyl bond, followed by the @-halogenelimination to give a codimer. The successive insertions of acetylene and allyl halide into the Pd-vinyl bond give a cotrimer. This codimerization provides a very convenient synthetic method for halogeno-substituted mono- and/or diolefins.
Homooligomerization of acetylenes or olefins using transition metal catalysts has been extensively studiedelHowever, only a few examples are known of cooligomerization of acetylenes and monoolefins2-6 probably because of the difficulty caused by the large difference in coordination ability between acetylenes and olefins to metal center; acetylenes are much more reactive to metals than olefins are, which results in exclusive polymerization of the acetylenes. Concerning palladium catalysts, only two examples have been reported. One is a linear cotrimerization of diphenylacetylene and olefins,j 0022-3263/79/1944-0055$01.00/0
and the other is a cyclic cotrimerization of dimethoxycarbonylacetylenes and norbornene.6 The diphenylacetylene and dimethoxycarbonylacetylene used above have a relatively lower reactivity to palladium when compared with common acetylenic compounds. Therefore, in order to accomplish the cooligomerization of acetylenes and olefins, it is very important to select suitable acetylenic or olefinic compounds with similar orders of coordination ability to a metal, or to devise reaction conditions in which extensive acetylene polymerization is prevented. We have found that the selective codi-
0 1979 American Chemical Society
56
Kaneda e t al.
J. Org. Chem., Vol. 44, No. 1, 1979 Table I. Codimerization of Substituted Acetylenes and Allyl Halides" registry acetvlene
allyl halide
no.
H C E ~ C C ~ H693-02-7 ~ CH2=CHCHZC1
registry no.
catalvstb
registry no.
product, yield,c % (isolated vield) /C
14220-64-5 CH =( HCH CH=C
107-05-1
registry no.
bp, "C (mmHa)
59973-83-6 54-55 (7)
'C! 1A YO (70)
,C.H,
HCGECC~H~
CHZ=CHCH2Br
15003-43-7 CH =CHCH CH=C
106-95-6
68091-89-4 53-54 (3.5) B 'r
1B
H C ~ ~ X B H 627-l9-0 T CH2=CHCHzCl
95 ti()'
CH =( I V H CH==C
/C
59937-82-5 47-48 (6)
c'1 2 A 'XI (701
HCECC~H~
CH =CHCH
CH=C
/c
68091-90-7
B 'r 2 8 RO
HCrECPh
536-74-3 CHZ=CHCH&l
(
H
=(
fTt H CH=C /Ph
52917-14-3 95-96 (7.5) I
\(
HC-CPh
CH2=CHCH2Cld
HC=CPh
CHZ=CHCHzBr
3A '12 V 3A ii)
/Ph
CH =( H( H CH=C
68091-91-8
'8,
3B '15 (
HC=CPh
(
H =V(
H
I
(H
H i'l'
563-47-3
(H
I
=CCH CH=(
/
68091 -92 -9 I
('
4A 48
('H
HC-CPh
CHsCHcCHCH&ld
591-97-9
A
563-52-0
A
I
('H =I'HCHCH=C,
/Ph
68091-93-0
("
I
HC-CPh
CH.=('HCHCI
CI
CI
I CH.=OCH.CI
HC==CPh
HC=CCHzCl
68091-94-1
78-88-6
A
I
('H =CCH ('H==C
/
Ph
52917-16-5
\
624-65-7 CH2=CHCHZCl
A
68091-95-2 62 (3.8)
HCECCH~OH 107-1.9-7 CHZ=CHCHZCl
A
68091-96-3
68091 -97 -4 9 A?.' 8
CH.
I
CHj
HC=C-~--OH
I CH, HC-CC02CH:r
CHZ=CHCHzCl
A
68091-98-5
922-67-8 CHZ=CHCHzCl
A
68091-99-6 65-66 (10)
15-1!3-5
J.Org. Chem., Vol. 44, No. I , 1979
Codimerization of Acetylenes and Halides
57
Table I (continued)
~ acetylene _ _ _ _ -
registry no.
allyl halide
registry no.
registry catalystb
no.
product, yield,c % (isolated yield)
registry no.
bp, "C (mmHg)
('OOH
HC=CCOOH
471-2h-0 CHz=CHCHzCl
A
I
12A. 13 CH,
1
CH3CsCCzH.j 627-21 -4 CHp=CHCH&l
A
68092-00-2
CH=( HCH C=CHCI
,C.H.
68092-01-3
CH, =CHCH,C=C, 'Ci
13A :1 60 CH
1
CHt
68092-02-4 69-70 (4.5)
CH =CHCH C = c / C' l
13A?: 30 CH3
C H ~ C S C C ~ H764-35-2 ~ CHz=CHCHzCl
A
I FH-
CH =CHCH C 4 ,
68092-03-5
57-58 ( 5 ) 68092-04-6 14A-2.' 3(i CH ,
C H ~ C S C C ~ H1119-635-9 ~ CHz=CHCHZCl
A
I
CH.=CHCH
C=C
FH
68092-05-7
C 'i
C,H, /C"
I CH =CHCH.C=C,
PhCzCCHB
673-3:!-5
CHZ=CHCHzCl
A
72-73 (4) 68092-06-8
59937-79-0 68-69 (2)
CH
PhC5CCzHS
622-76-4 CHz=CHCHzCl
A
68092-07-9
CH =CHCH C=(, \
CI
17A-I.' ii
68092-08-0
("
PhCzCCzH5
B
I
CH =CHCH C=C\
/Ph
68092-09-1
B 'r 17B-1.' 55
Ph CHI=CHCHIC=CCH,CH,
I Br
68092-10-4
17B-2.* 27
PhC=-CCzH;
4250-61-1 CH2=CHCHzCI
A
68092-11-5
68092-12-6
58
J . Org. Chem., Vol. 44, No. 1, 1979 Table I (continued)
___
regismtry acetylene
Kaneda et al.
no.
allyl halide
registry no.
catalyst6
registry no.
product, yield,' % (isolated yield)
registry no.
bp, "C (mmHd
68092-13-7
4250-52-2 CH,+?HCH2CI 19A. R ?
928-49-4 CH2=C"CH2Cl
CH =CHCH
b=C'
59937-84-7 51-52 (2)
a' 20A. 41 ($2)
68092-14-8
1942-46-7 CH2=CHCH2Cl "C, 21A. YO
Ph
I
501 -65-5 CHZ=CHCH&l
CHI=CHCH.C=C
/Ph
52917-15-4
c' .1
CH~O~CCEC-762-42-5 CH2=CHCH2Cl COzCH3
A
68092-15-9
a Reaction with Pd complex (4 mmol), acetylenic compound (80 mmol), and allyl halide (80 mL) at 20 "C for 2 h. Satisfactory analytical data (f0.4%for C, H, C1, Br) were reported for all new compounds. b A is PdCl*(PhCN)2.B is PdBrt(PhCN)2. Yields were based on acetylenes used and determined by GC analysis. Nitromethane (30 mL) was the solvent. Reaction with Pd complex (1 mmol), phenylacetylenr (10 mmol), and allyl chloride (50 mmol). e These isomers could not be well separated by GC and yields were determined by NMR analysis. f Reaction time was 24 h.
merization of various acetylenes and allyl halides proceeds smoothly with palladium complex catalysts under mild conditions.T*8Recently there appeared selective 1,4-diene syntheses which, however, used mixed metals as the reagent and are stoichiometric with respect to the metals u~ed.9-1~ The present catalytic codimerization provides a facile and useful 1&diene synthesis without isomerization to 1,3-diene.l3,l4 We report herein an investigation of the scope of the reaction with a variety of ticetylenes and allyl halides together with mechanistic investig.
