1, 2, 4, Thiadiazole diazonium salts preparation

In their detailed study of thiadiazole diazonium salts (292) Goerdeler and his co-workers have succeeded in isolating these compounds in the solid state by the following preparative methods ... 

Chloro- and bromo-l,3,4-thiadiazoles are usually prepared by nucleophilic processes, e.g., Sandmeyer reactions of diazonium salts [56CB1534 68AHC(9)165 86CHE1148], and reactions of thiadiazolinones with phosphorus halides [68AHC(9)165]. The halogeno derivatives are important... 

The equilibrium existing between nitrosamines and diazonium salts of 1,2,4-thiadiazoles in acid media was mentioned in Section III,E. Diazonium salt solutions may be directly prepared from the amines in concentrated sulfuric, phosphoric, or acetic acid.6 80> 17°-191 Most of... 

Amino-l,2,4-thiadiazoles are usually prepared by treating amidine hydrochlorides with halogen and thiocyanates to yield the 3-alkyl derivatives or treating alkylisothiouronium salts similarly to yield the 3-alkylthio derivatives (56CB2742). Diazonium salts derived from 5-amino-l,2,4-thiadiazole derivatives, which are prepared in acetic acid, are extremely reactive and are capable of coupling with m -xylene (60CB397). 

By contrast, 3-hydrazino-l,2,4-thiadiazoles (163), which are prepared by ring closure methods, are very sensitive to acids and undergo elimination of sulfur with formation of 5-arylamino-l,2,4-triazoles (164) as indicated in Scheme 61 (63JCS4566). The mechanism of this conversion is not known but presumably involves the attack of a hard nucleophile at the 5-position followed by ring opening, loss of sulfur and recyclization as has been observed with the quaternary salts (77JCS(P1)1791) (see Schemes 22, 23, and 24). Hydrazine (163) reacts with aldehydes to produce hydrazones (165) and with dimethyl malonate to yield pyrazoles (166). Diazonium salts of type (153) have been prepared by the methods... 

Azine approach. Diazotization of 2-amino-3-hydroxypyridines might be expected to yield the bicyclic ring system (631) by bond formation between the oxygen and the diazonium group in the first formed diazonium salt fused 1,2,3-thiadiazoles and -triazoles are formed by this type of reaction. Compounds prepared by this method, however, are highly unstable and have spectroscopic properties consistent with the pyridodiazooxide structure (630) (74CS(6)222>. 

The first 1,2,3-thiadiazole synthesized, 1,2,3-benzothiadiazole, was prepared by diazotiz-ation of o-aminothiophenol with nitrous acid (equation 31) (B-61MI42400), and recently sodium nitrite-acetic acid has been substituted for nitrous acid (B-79MI42400),. Another modification, thermal decomposition of diazonium acetate (34), affords benzothiadiazole in good yield in contrast to the variable yields usually experienced in the diazotization of o-aminothiophenols (equation 32) (78SST(5)43l). Benzothiadiazoles are also available directly from aromatic amines (equation 33) (70JCS(C)2250). Sulfur monochloride reacts with the amine to form a benzothiazothiolium salt which reacts with nitrous acid to yield a chlorinated 1,2,3-benzothiadiazole (35). This process, depending on the aromatic ring substitution, may afford a number of products, and yields are variable. 

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