~y+ ehssPh fl Phs/~ + ehs_/KA/~1 + p~S~Se~. (I). (II). (:I!)--('Vl) ... J = 7 Hz), 3.33 m (SCH2C=C), 5.33-5.55 m (CH=CH), 7.2 m (C6Hs). Mass spectrum, m/z (rela-.
ACTIVATION OF THE S-S BOND IN DIPHENYL DISULFIDE BY NICKEL COMPLEXES AND ITS REACTION WITH BUTADIENE U. M. Dzhemilev, R. V. Kunakova, N. Z. Baibulatova, ~. M. Mustafina, E. G. Galkin, and G. A. Tolstikov
UDC 542.97:547.569.4:547.315.2
We are the first to demonstrate the possibility of obtaining unsaturated mono- and disulfides (I)-(VI) by the reaction of diphenyl disulfide with butadiene taken in 1:20 ratio in DMF. The reaction is carried out at 150~ for 20 h in the presence of Ni(acac) 2Ph2PCH2CH2PPh 2 as catalyst (Ni:P = 1:2). The introduction of small molecules such as CO= and NH 3 into the catalytic system is a necessary condition for obtaining sulfides (I)-(VI) in yields of about 80% (Ni:CO2:NH 3 = 1:500:300). In the absence of such small molecules, the yield of (I)-(Vl) does not exceed 20%. Products (I)-(IV) were isolated as pure compounds by distillation on a Widmer column, while (V) and (VI) were detected only by mass spectrometry due to their low content in the reaction mixture. Under optimal conditions, the (I):(II):(III):(IV):(V):(VI) ratio was 30:32:20:15:2:1.
~y+
ehssPhfl P h s / ~ + ehs_/KA/~1 + (I)
,~ = i ( n i l
(II)
p~S~Se~ (:I!)--('Vl)
2 (Iv), 3 (v), 4 (vI).
Phenylthio-2-butene (I), bp 64-66~ (2 man), PMR spectrum (6, ppm): 1.56 d (CH3C=C, J = 7 Hz), 3.33 m (SCH2C=C), 5.33-5.55 m (CH=CH), 7.2 m (C6Hs). Mass spectrum, m/z (relative intensity, %): [H] + 164 (53.7), [Ph+CH2] 123 (28.1), [PhS+H] ii0 (100), [Phi 77 (12. I), [C~HT] + 55 (80.1), [HCS] + 45 (18.7). Phenylthio-2,7-octadiene (II)~ bp 133-135~ (2 mm). PMR spectrum (6, ppm): 1.46 m (CH2), 1.92 m (4H, C H 2 C ~ ) , 3.38 m (SCH2C=C), 4.755.48 m (CH=CH, CH=C, CH2=C) , 7.12 m (C6Hs). Mass spectrum, m/z: [M] + 218, [PhS+CsHs] 177, [PhS+C4H6] 163, [PhS+C3H~] 149, [PhS+C2H 2] 135, [PhS+CH2] 123. 1,4-Bis(phenylthio)-2butene (III), bp 166-168~ (2 mm). PMR spectrum (6, ppm): 3.4 m (4H, SCH2C=C), 5.255.58 m (CH=CH), 7.10 m (2C6H5). Mass spectrum, m/z: [M] + 272, [PhS+C4Hs] 162, [PhS +] 109. l~8-Bis(phenylthio)-2,6-octadiene (IV), bp 183-185~ (2 man). PMR spectrum (6, ppm): 1.96 m (4H, CH2C=C) , 3.43 m (4H, SCH2C=C) , 5.33 m (4H, CH=CH), 7.11 m (2C6H~). Mass spectrum, m/z: [M] + 326, [PhS+CsH12] 217, [PhS+C4Hs] 163. l~12-Bis(phenylthi0)dodecatriene (V). Mass spectrum, m/z: [M] + 380, [PhS+Cl2Hls] 271. 1,16-Bis(phenylthio)hexadecatetraene (VI). Mass spectrum, m/z: [M] + 434, [PhS+CI6H2~] 325.
Institute of Chemistry, Bashkir science Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, p. 747, March, 1989. Original article submitted September 22, 1988. 0568-5230/89/3803-
0675512.50
9 1989 Plenum Publishing Corporation
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