Isothiazole 4- phenyl

Irradiation of isothiazole gives thiazole in low yield. In phenyl-substituted derivatives an equilibrium is set up between the isothiazole (59) and the thiazole (61) via intermediate (60) (72AHC(14)l). 

Isothiazole behaves as a typical stable aromatic molecule. Thermolysis of substituted isothiazoles at 590 °C leads to the formation of thioketenes (80MI41700) and phenyl-isothiazoles undergo photoisomerism (Section 4.17.6.2) (73BSF1743, 81T3627). 1,2-Benzisothiazole boils at 220 °C without appreciable decomposition, and the 2,1-isomer... 

Both 1,2- and 2,1-benzisothiazoles react with electrophiles to give 5- and 7-substituted products (see Section 4.02.3.2). The isothiazole ring has little effect on the normal characteristics of the benzene ring. C-Linked substituents react almost wholly normally, the isothiazole ring having little effect except that phenyl substituents are deactivated (see Section 4.17.2.1). There are, however, considerable differences in the ease of decarboxylation of the carboxylic acids, the 4-isomer being the most stable (see Section 4.02.3.3). 

The isothiazole ring causes deactivation of phenyl substituents, particularly in 3-phenyl-isothiazoles. Nitration of arylisothiazoles, however, occurs only in the benzene ring, the pattern of substitution varying greatly with the position of the aryl group on the isothiazole... 

Isothiazole-4,5-dicarboxylic acid, 3-phenyl-dimethyl ester synthesis, S, 150 Isothiazole-5-glyoxylic acid ethyl ester reduction, 6, 156 Isothiazole-4-mercurioacetate reactions, 6, 164 Isothiazole-5-mercurioacetate reactions, 6, 164 Isothiazoles, 6, I3I-I75 acidity, 6, 141 alkylation, 6, 148 aromaticity, S, 32 6, 144-145 basicity, 6, I4I biological activity, 6, 175 boiling points, 6, I43-I44, 144 bond fixation, 6, 145 bond orders, 6, I32-I34 calculated, 6, 133 bromination, S, 58 6, 147 charge densities, 6, 132-134 cycloaddition reactions, 6, 152 desulfurization, S, 75 6, 152 deuteration, S, 70... 

Certain dithiolium salts have been reported by Leaver and Robertson to form isothiazoles on treatment with ammonia thus, 3,5-diphenyl-l,2-ditholium perchlorate (15) gives a 50% yield of 3,5-diphenylisothiazole (16). The method does not appear to be generally applicable, and the analogous 3-methyl-5-phenyl-l,2-dithiolium salt did not give an isothiazole. 

In the presence of various metal ions, 2-(fluoroenone)benzothiazoline has been found to rearrange to A-2-mercaptophenylenimine, while a free radical mechanism involving the homolysis of C-S and C-N bonds has been invoked to explain the formation of 3-phenyl-1,2,4-triazole derivatives from the thermal fragmentation and rearrangement of 2-(arylidenehydrazino)-4-(5//)-thiazolone derivatives. The cycloadducts (36) formed from the reaction of 3-diethylamino-4-(4-methoxyphenyl)-5-vinyl-isothiazole 1,1-dioxide (34) with nitric oxides or miinchnones (35) have been found to undergo pyrolytic transformation into a, jS-unsaturated nitriles (38) by way of pyrrole-isothiazoline 1,1-dioxide intermediates (37). 

A series of five-membered heterocycles with two and three heteroatoms were synthesized. 4-Hydroxyisothiazoles 57 were prepared from a-amino ketones with sulfur monochloride (1968BCJ959). Polar solvents, especially N,Af-dimethylfor-mamide, were preferable (Scheme 28). In a similar reaction of 1-amino-l-phenyl-2-propanone with sulfur monochloride 5-chlorinated isothiazole 58 was obtained in high yield. 

Dihydro-4,5-dimethyl-3-(hydroperoxy)-2-[4-(methoxycarbonyl)phenyl]isothiazole 1,1-dioxide (AFUPOG) 1.461 1.417 106.6 97... 

Dithiolylium salts may be converted into pyrazoles, pyrazolium salts and isothiazoles (see Section 3.4.1.6.2.ii). For example, 3-phenyl-1,2-thiolylium salt (74) with hydrazine, methylhydrazine or phenylhydrazine yielded the corresponding pyrazoles (75). 3,4-Dimethyl-1,2-dithiolylium perchlorate (76) with ammonia gave 4,5-dimethylisothiazole (77). 

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