Thiamin Analogs. II. 4-Methylthiazole Analogs^1,2

Abstract

<* Method I. 1 Method II. Equal molar amounts of reactants were used. 6 Method II. One molar excess of aliphatic diamine used. d Synthesized according to Method II. Two molar excess of aliphatic diamine used. * Hydrochloride. 1 Picrate derivative. » Yield based on the amount of aliphatic diamine used. * This material solidified on standing to a white, low melting solid. * The abbreviation p. a. is used for picric acid, CiH2N30r.

Synthesis of 3a,4,5,6,7a‐Hexahydro‐3a‐hydroxy‐3‐substitutedamino‐2‐benzothiazolinethiones and Related Compounds

“…7.70;N,9.66;0,5.79;S,22.29. 4,5,6,7-Tetrahydro-3-pyrrolidinyl-2-benzothiazo~inethione (3,4,5,6,7-Tetrahydro-3-morpholino-2-benzothiazolinethione (8), 4,5,6,7-Tetrahydro-3-piperidino-2-benzothiazolinethione (9) and 4,5,6,7-Tetrahydro-3jhexahydro-l~lH)-azepinyl)-2-benzothiazolinethione (10).…”

“…It was anticipated that since the reaction of potassium dithiocarbazate with 2-chlorocyclohexanone furnished the six-membered heterocycle, 11, replacing the above electrophile with 3-chloro-2,4-pentanedione [4] should under the same conditions result in formation of structure B. c"3cFN:" ; s-xs strvcturs B However, this postulate was not substantiated and the product isolated in this reaction was 5-acetyl-3-amino-4-methyl-4-thiazolin-2-thione (12). In the above reaction, no evidence for the formation of B…”

Electrochemical Reduction of 3‐Chloro‐2,4‐pentanedione at Carbon Cathodes in Acetonitrile

“…In spite of these contradictory results, nickel electrode- [1] position from a concentrated electrolyte such as the usual Watts bath appears to be a good experimental system for the identification of the specific effects of a magnetic field on electrocrystallization, owing to the considerable amount of knowledge which has been accumulated. It is known that the overall deposition rate is governed by interfacial reactions;'4 thus, nickel ion transport has practically no influence on the deposition process.…”

Chlorination of butanone

“…A USEFUL intermediate in the preparation of a variety of heterocycles (5,11) is 3-chloro-2-butanone. However, an attempt to prepare 4,5-dimethyl-2-aminothiazole from this ketone by standard procedures (1,3) resulted in an intractable mixture of isomers, from which the desired heterocycle was obtained in low yield. Apparently the starting ketone was impure.…”

“…Chlorinations with Sulfuryl Chloride. These were based on earlier methods employed for the chlorination of 2pentanone (1,3,14). The following variations were introduced: (C) sulfuryl chloride (2 equiv.)…”