Reactions of Phosphorus Pentachloride with Ethyl-, Vinyl-, and Ethynyl(trichloromethyl)carbinol and with 1,1,1-Trichloro-3-nonyn-2-ol

Abstract

Reactions of phosphorus pentachloride with ethyl(trichloromethyI)carbinol (2), (trichloromethyl)-vinylcarbinol(7), ethynyl(trichloromethyl)carbinol (lla), and 1,l.l-trichloro-3-nonyn-2-01 ( l l b ) have been studied. Whereas the reaction of phenyl(trichloromethyl)carbinol with phosphorus pentachloride leads to a nearly quantitative replacement of the hydroxyl group by chlorine, the reactions of the aliphatic (trichloromethyl)carbinols are more complicated. Thus the reaction of 2 with phosphorus pentachloride gave 18% of the normal product, 1,1,1,2-tetrachlorobutane (3), 13% of 1,1,2-trichloro-1-butene (4) from a dehydrohalogenation, and a higher boiling phosphate ester -acid chloride mixture. The alkynylcarbinols (11) gave tetrachlorobutynes (12) as well as tetrachloroallenes (13) by allylic rearrangement. A crystalline phosphate ester of 110 was also isolated. Several examples are given of catalytic rearrangements in the vapor phase of 1,1, I-trichloro-2-alkenes to 1,1,3-trichloro-I-alkenes.On a CtudiC les rCactions du pentachlorure de phosphore avec 1'Cthyl (trichloromCthy1) carbinol (2), le (trichloromCthyl) vinylcarbinol (7), I'Cthknyl (trichloromCthyl) carbinol (110) et le trichloro-1 , I , I nonyn-3 01-2 (llb). Alors que la rCaction du phCnyl (trichloromCthyl) carbinol avec le pentachlorure de phosphore conduit pratiquement quantitativement B la substitution du groupe hydroxyle par unchlore, la rCaction avec les (trichloromCthyl) carbinols aliphatiques semble Ctre beaucoup plus compliqde. Ainsi, la rCaction de 2 avec le pentachlorure de phosphore conduit B la formation du produit normal (l8%), tCtrachloro-1,1,1,2 butane, (3) ainsi qu'B la formation du trichloro-1,1,2 butkne-1 (4) (13%), provenant d'une dChydrohalogknation, et d'un mClange phosphate d'ester -chlorure d'acide ayant un point d'Cbullition plus Clev6. Les carbinols posskdant des groupes alcynes (11) produisent des tCtrachlorobutynes (12) de mZme que des tCtrachloroallknes (13) selon un mtcanisme impliquant un riarrangement allylique. Un phosphate d'ester cristallin de l l n a aussi CtC isolC. Plusieurs exemples de rkarrangements catalytiques en phase vapeur sont rapportCs pour les trichloro-l,l, 1 alcknes-2 entrainant la formation de trichloro-1,1,3 alcknes-1.[Traduit par le journal]Can.

The reactions of ethyl-, vinyl-, and ethynyl(trichloromethyl)carbinols with aqueous and methanolic potassium hydroxide, thiourea, and cyanamide

“…3 5~ of product (66% of Ethynyl(trichloromethyl)carbinol, I, l,l-trichloro-3-nonyn-2-01, (trichloromethyl)vinylcarb~nol, and ethyl(trich1oro-methy1)carbinol were synthesized as previously described (9).…”

“…Accordingly, we report here on the reactions of these carbinols with methanolic potassium hydroxide, thiourea, cyanamide, and cold aqueous potassium hydroxide solution. We have previously reported on the reactions of the aliphatic-(trichloromethyl)carbinols with phosphorus pentachloride and shown that a wide variety of compounds are formed (9).…”