Reaction of 2-Alkoxymethylthiiranes with Lithium Aluminum Hydride and with Secondary Amines

Abstract

The reduction of 2-alkoxymethylthiiranes with lithium aluminum hydride has been found to result in the formation of 1alkoxy-2-mercaptopropanes, the isomers expected from normal ring fission. The reaction of triethyl phosphite with the 1alkoxy-2-mercaptopropanes was found to result in the formation of the corresponding alkyl propyl ethers and triethyl thionophosphate. The reaction of 2-alkoxymethylthiiranes with the secondary amines, piperidine, morpholine, and diethylamine w-as also investigated. The yield of the amino mercaptan was found to be quite sensitive to the mole ratio of amine to thiirane, the nature of the product formed, the presence or absence of a solvent, and the type of solvent. The reaction of triethyl phosphite with the products isolated from the reactions of amines with 2-alkoxymethylthiiranes were found to result in the formation of amidothionophosphates and alkyl allvl ethers.

Thiiranes

“…The yields of mercaptans amounted to 72% for propene sulfide (22), 73% for 1-hexene sulfide (22), 20% for 1-octene sulfide (153), and 75-85% for a number of 3-alkoxypropene sulfides (110). The reduction of cyclohexene sulfide (22,159) and carbohydrate thiiranes (36) with L1AIH4 was also reported.…”

Photochemical synthesis of aromatic chloro compounds from aromatic iodo compounds

“…Thus, photolysis of aromatic iodides has led to syntheses of biphenyls, phenanthrenes, and organophosphorus and organoboron compounds, all in acceptable yields. 3 Aromatic iodo compounds are now readily accessible from a wide variety of aromatic hydrocarbons through initial thallation with thallic trifluoroacetate followed by treatment with aqueous potassium iodide,4 and we (1) We gratefully acknowledge partial financial support of this work by the Smith Kline and French Laboratories, Philadelphia, Pa.…”