Dithiazolylium salt

Dithiazolones, chloro-chlorination, 6, 915 Dithiazolylium salts antifertility activity, 6, 944 as chemosterilants, 6, 944 as herbicides, 6, 944 IR spectra, 6, 907 reduction, 6, 918 Dithiazolylium salts, amino-reactions... 

The primary route to 1,3,2-dithiazolium salts involves the cyclocondensation of l,2-bis(sulfenyl chlorides) with trimethylsilyl azide, which is illustrated for benzo-fused derivatives in Eq. 11.11. ° This method can be extended to the synthesis of bis( 1,3,2-dithiazolylium) salts. 

While the Herz reaction provides a convenient route to many dithiazolylium salts, the propensity for chlorination of the aromatic substituent has led to the development of several other approaches to 1,2,3-dithiazolylium salts and... 

For 1,2,4-dithiazolylium salts containing substituents which are not good leaving groups, nucleophilic addition is followed by ring opening with extrusion of sulfur, the subsequent... 

Scheme 13 Nucleophilic attack at carbon in 1,2,4-dithiazolylium salts I...

Dithiazolylium salts and related compounds with S—S bonds are readily reduced both to thiols and to radicals. Thus, the thione (30) is reduced quantitatively to thiourea and CS2 by Sn/HCl (1897JCS607), and for the electrochemical reduction of the salt (31) to dithiobiuret (80) at a Pt electrode, the half-cell potential E q -0.251 V at pH 0 decreases with increasing pH, indicating that the equilibrium favours the cation (31) (47JA2632). The same cation, when refluxed in EtOH with dithiomalonamide, is converted quantitatively... 

Dithiazolylium salts (83), having R3 = NH2, react with ketones (67IJC216), presumably via an intermediate enamine, e.g. (117), to give 1,3-thiazoles (118 Scheme 26). Mild... 

Oxidation of thioamides with I2, Br2 or H202 to diimino disulfides, followed by acid-catalyzed cyclization with elimination of amine, is an important route to symmetrically substituted 1,2,4-dithiazolylium salts (43) (79NKK389), and structures (47) (79CHE1187). The preparation of the 3-phenyl-l,2,4-thiazolines (35), and thus (36), is a related reaction. 

An important class of chemosterilants are the dithiazolylium salts (228), many of which show high activity against Musca domestica, the example having NR R2 = 4-methylpiperazino being selectively active against males (73M143402) (see also Chapter 1.07). 

The dithiazolylium salts (228), besides being insect chemosterilants, cause atrophy of the prostate gland and seminal vesicles in male rats, as well as inhibiting ovulation and interrupting pregnancy in females. The results of a detailed study have recently been... 

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