To A-4-thiazoline-2-one

Recently, Koitai et al. (17) have shown that 5,5-diphenyl-2,4-thiazolidinedithione (15) with aluminum chloride in refluxing toluene gives 4,5-diphenyl-A-4-thia2oline-2-thione (16) (Scheme 7). 3-Methyl-4,5-diphenyl (17) and 4,5-diphenyl-A-4-thia2oline-2-thiones (16) are obtained in very low yields (1 to 5%) as by-products of the reaction between deoxybenzoin. benzoin. l,2-diphenyl-1.2-ethanediol. 1.2-diphenylethanol, or benzil, and Sg in hexamethylphosphoamide (18), The transformation of A-4-thiazoline-2-ones to the corresponding thiones by P2S5 (19) is of little synthetic value since the latter are more easily prepared. 

Ring opening and further ring closure of 2-imino-oxythiolan-l,3 derivatives (32) by water and/or methanol lead to the corresponding A-4-thiazoline-2-one (26) (Scheme 14) (30-32). 

Decomposition of diazonium salts obtained from 2-aminothiazole (4) (29, 34. 35) could be an interesting reaction to introduce O in A-4-thiazoline-2-one. Acidic hydrolvsis of ethers (36. 37). oxidative hydrolysis... 

Thiazolium derivatives unsubstituted at the 2-position (35) are potentially interesting precursors of A-4-thiazoline-2-thiones and A-4-thiazoline-2-ones. Compound 35 in basic medium undergoes proton abstraction leading to the very active nucleophilic species 36a and 36b (Scheme 16) (43-46). Special interest has been focused upon the reactivity of 36a and 36b because they are considered as the reactive species of the thiamine action in some biochemical reaction, and as catalysts for several condensation reactions (47-50). 

Compound 36 when treated by sulfur under nitrogen, leads to the thiazoline-2-thione (37) (Scheme 16) (43). Oxidation by O- or air of 36 (43) or 38 (45, 46) leads to the corresponding thiazoiine (39 or 40). Consequently, condensation reactions using catalysts like 36 must be run in strictly oxygen-free atmosphere (47-50). The isolation of traces of 3-benzyl-4-methyl-A-4-thiazoline-2-one (42) as a product of the oxidation of... 

A-4-thiazoline-2-one is expected to be far more basic than the ground state. 

The infrared spectra of A-4-thiazoline-2-ones are characterized by a strong absorption around 1650 cm (55, 86, 103, 107. 870). For the N-H derivatives, the whole range 2700 to 3200 cm is covered by a strong absorption related to the dimeric and oligomeric states of the hydrogen-bonded structures (85, 86). 

Alkylation of A-4-thiazoline-2-one may yield O-R or N-R derivatives according to experimental conditions. With diazomethane in ethanol O-raethylation takes place (29. 36. 214). N-Methylation is reported when a basic solution of A-4-thiazoline-2-one reacts with methyl iodide or dimethylsulfate (21, 29, 215, 216), Reaction of l-chloro-2-dimethyl-aminoethane with the sodium salt of 4 R-A-4-thiazoline-2-one (91) in alcohol, first claimed to yield the aminoalkylether (217, 218), was shown after infrared investigation to give the N-substituted derivative (92) (107), even when R Ph (Scheme 45). More probably the site of reaction in... 

The electrophilic character of the C-2 atom is more clearly evident in A-4-thiazoline-2-ones than in A-4-thiazoline-2-thiones. 3-Mcthyl-A-4-thiazoline-2-one is cleaved in alcaline medium to give methylaraine (36). This reaction probably starts with the nucleophilic attack of OH on C-2. 

Methoxythiazoles are converted to the corresponding N-methyl-A-4-thiazoline-2-ones by heating with excess methyl iodide (29, 243). The reaction mechanism can be considered initially as the formation of a... 

Imino-A-4-thiazoline (29) reacts with sodium nitrite to give a nitroso derivative (30) that decomposes on heating to the A-4-thiazoline-2-one (31) (Scheme 13) (29). 

Dry HC1 in ether converts 4-aryJ-A-4-thiazoline-2-one (96) to the corresponding 2-chlorothiazole (97) (Scheme 48) (230- 233. 234). Elec-... 

On heating the neat sample or a solution in a variety of solvents, 2-allyloxythiazole (125) undergoes a thermal rearrangement to N-allyl-A-4-thiazoline-2-one (126) in excellent yield (Scheme 64) (283). Deuterium labeling reveals the complete inversion or the allylic moiety in the rearrangement. First-order rate law is found, and activation parameters show a negative entropy in accord with that measured in most of Claisen rearrangements. 

A-4-thiazoline-2-one, 402 Phosphorus pentasulfide, in transformation of A-4-thiazoline-one to thiazoline-thione, 373... 

Schiff bases, 256-259, 268, 270 to amines. 40 from aminothiazoles, 98 with 2-amino thiazoles, 30, 40 complexes of, 99 cyclization to, 42 IR spectra of, 41 in reduction by AlLiH,. 14 in reduction by NaBH4, 14 LTV spectra of, 41 see also Thiazolylamidines Schistosomacidal, 141 Schistosomiasis japonica, 145 Schotten-Bauman reaction. 51. 123 Sedative, 145. 148,438 Selective herbicide, 135 Self association, effect of, on UV spectra of A-4-thiazoline-2-thione. 381 A-4-thiazoline-2-one, relation with protomery, 377... 

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