ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Condensation of the tetrahydropyranyl ether of the α-hydroxyalkyl-thioamides with 3-bromo-4-hydroxy-2-pentanones yields DL-2-(α-hydroxyalkyl)-4-methyl-5-(β-hydroxyethyl)-thiazoles. By oxidation with chromic anhydride 2-hydroxymethyl-4-methyl-5-(β-acetoxyethyl)-thiazole yields the corresponding 2-formyl derivative. The latter compound reacted with GRIGNARD complexes gives the homologous DL-2-(α-hydroxyalkyl)-4-methyl-5-(β-hydroxyethyl)-thiazoles. This is a general method for the synthesis of the thiazole part of the «active aldehydes».2-Acetyl-4-methyl-5-(β-hydroxyethyl)-thiazole is also obtained by chromic oxidation of the suitable methylthiazol-2-yl-carbinol.The condensation of the thioamides obtained from the α-ethoxycarbonyl-nitriles with 3-bromo-5-acetoxy-2-pentanone results in the DL-2-(α-ethoxycarbonyl-alkyl)-4-methyl-5-(β-acetoxyethyl)-thiazoles. The α-hydroxyl function is introduced into the 2-(α-ethoxycarbonyl-alkyl) group by chlorination with sulfuryl chloride and replacement of the introduced chlorine by acetate. The latter compounds are the esters of the thiazole part of the «active α-oxo-carboxylic acids» (e.g. active pyruvate, etc.).The reaction of 2-(α-hydroxyalkyl)-4-methyl-5-(β-hydroxyethyl)-thiazoles and 2-(α-ethoxycarbonyl-α-acetoxy-alkyl)-4-methyl-5-(β-acetoxyethyl)-thiazoles, respectively, with alkyl, alkenyl and aralkyl haloids, or with 2-methyl-4-amino-5-bromomethyl-pyrimidine hydrobromide results in the quaternary thiazolium compounds belonging to the group of the active aldehydes, active α-oxo-carboxylic acids, etc. According to this method 2-hydroxymethyl-thiamine bromide hydro-bromide has been synthesized, which can be considered as the pyrophosphate-free «active formal-dehyde».The 2-α-hydrogen atom in 2-(α-hydroxyalkyl)-thiazolium compounds cannot be replaced by deuterium under conditions similar to those used for the H → D exchange in thiamine.The main peaks in the mass spectra of 2-(α-hydroxyalkyl) substituted thiazoles and thiazolium quaternary salts are listed.
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19680510211
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