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

Abstract

. 58,2784 (1980). The reactions of ethyl(trichloromethyl)carbinol, dimethyl(trichloromethyl)carbinol, (trichloromethyl)vinylcarbinol, ethynyl (trichloromethyl)carbinol, and 1,1,1,-trichloro-3-nonyn-2-01 have been studied with the following reagents. Methanolicpotassium hydroxide: a-methoxy acids are formed in 70 and 79% yields with the ethyl-and vinylcarbinols respectively. Double bond migration to the conjugated position was observed with the vinylcarbinol. Thiourea: substituted 2-imino-4-thiazolidinones are formed in 27 to 66% yield with the first three carbinols with double bond migration in the case of the vinylcarbinol. Cyanamide: the saturated carbinols were converted to substituted ethyl 2-imino-4-0x0-I-imidazolidinecarboximidates in 30 to 60% yield. Aqueouspotassium hydroxide: a-chloro acids were formed from the ethyl-and vinylcarbinols in 23 and 24% yields respectively, again with double bond migration in the case of the vinylcarbinol.The results are discussed in terms of the known parallel reactions with phenyl (trichloromethyl)carbinol, and provide information which illustrates the usefulness and defines the llmits of certain known synthetic reactions when applied to the alkyl, alkenyl, and alkynyl trichloromethylcarbinols.WILKINS REEVE et THOMAS F. STECKEL. Can. J. Chem. 58,2784Chem. 58, (1980. On a etudie les reactions des alcools Cthyl(trichloromethyl)carbinol, dim6thyl(trichlorom~thyI)carbinol, (trichloromethy1)vinylcarbinol, ethynyl(tnchloromethyI)carbinol et trichloro-1,1,1 nonyne-3 01-2 avec divers rkactifs. Par reaction avec une solution methanolique d'hydroxyde de potassium, on obtient les a-methoxy acides avec des rendements respectifs de 70 et 79% dans le cas des alcools ethylique et vinylique. On a observe une migration de la double liaison vers la position conjuguke avec le carbinol vinylique. Avec la thiourke, il se forme des imino-2 thiazolidinones-4 substituees avec des rendements allant de 27 B 66% pour les trois premiers carbinols et une migration de la doubleliaison dans le cas du vinylcarbinol. Avec la cyanamide, les carbinols saturks se I transforment en imino-2 oxa-4 imidazolidinecarboximidates-1 substituks avec des rendements allant de 30 a 60%. Avec I'hydroxyde de potassium aqueux il y a format~on des acides a-chlorks avec des rendements respectifs de 23 et 24% dans les cas des carbinols ethylique et vinylique. On observe Ogalement une migration de la double liaison dans le cas du carbinol vinylique.On discute des rksultats en fonction des reactions paralelles connues du phenyl(trichloromethyl)carbinol. Ces rksultats fournissent des in&ormations qui illustrent I'utilitk et definissent les limites de certalnes reactions connues quand on les applique aux alkyl, alkenyl et alkynyl tr~chloromethylcarbinols [Traduit par le journal]

Practical Approach to α- or γ-Heterosubstituted Enoic Acids

“…They also reported the first preparation of asymmetric trichloromethyl carbinols using an enantioselective oxazaborolidine-based reduction of the corresponding trichloromethyl ketones . Although these investigators have made notable contributions toward the application of trichloromethyl carbinols in Jocic-type reactions, examinations into the reactivity of alkenyl trichloromethyl carbinols in such reactions are conspicuously lacking …”