Regioselective addition of O,O-diethyldithiophosphoric acid to 1-aryl-1,3-butadienes

Journal Article · Tue Oct 20 00:00:00 EDT 1987 · J. Gen. Chem. USSR (Engl. Transl.); (United States)

OSTI ID:6961683

Obushak, N D; Vovk, M V; Vengrzhanovskii, V A; Mel'nik, Ya I; Ganushchak, N I

The authors have investigated the interaction of 1-aryl-1,3-butadienes with the diethyl ester of dithiophosphoric acid under conditions facilitating both free radical and ionic reaction mechanisms. It has been shown that O,O-diethyldithiophosphoric acid adds only to the terminal double bond in 1-aryl-1,3-butadienes. The chemical shifts and signal structures unequivocally prove the direction of addition. The CH/sub A/=CH/sub B/-CH/sub X/ arrangement gives rise to an ABX spin pattern, in which the signal due to proton A appears as a doublet at 6.46-6.52 ppm, and the B proton as a doublet of doublets (J/sub Bx/ * Hz). The value of the spin-spin coupling constant for protons A and B (J/sub AB/ 16 HZ) is indicative of a trans (E)-configuration of the resulting adducts. The signal due to proton X is superimposed on the signal of the OCH/sub 2/ group and gives rise to a complex multiplet centered at 4.00-4.06 ppm. The methyl group, arising via addition of a proton to the fourth carbon atom of the diene, appears as a doublet of 1.45-1.47 ppm with a spin-spin coupling constant of 6.5 Hz, whereas the methyl groups of the (CH/sub 3/CH/sub 2/O)P fragment are a doublet of triplets (J 1.8-3 HZ), which is evidence of their astereotopic nature.

• Research Organization: I. Franko L'vov State Univ. (USSR)
• OSTI ID: 6961683
• Journal Information: J. Gen. Chem. USSR (Engl. Transl.); (United States), Vol. 57:5; Other Information: Translated from Zh. Obshch. Khim.; 57: No. 5, 1078-1080(May 1987)
• Country of Publication: United States
• Language: English

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37 INORGANIC
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PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
DIENES
ISOMERIZATION
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CHEMICAL BONDS
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Molecular & Chemical Physics- Atomic & Molecular Properties & Theory