1,2,5-Thiadiazole-3,4-dicarbonyl

It was reported that polymers from 2,5-dimethylpiperazine and dicarboxylic acid derivatives were useful as membranes for reverse osmosis in water desalination. Towards this end, trans-2,5-dimethyIpiperazine, 3,4-thiofurazan dicarbonyl chloride (1,2,5-thiadiazole-3,4-dicarbonyl... 

Filter paper impregnated with dicarbonyl(benz-2,l,3-thiadiazole)rhodium chloride gives characteristic colorations with the aminophenol isomers after fixation and can be used as an indicator paper (99). 

A useful strategy for the formation of fused thiadiazoles is the annulation of suitably functionalized 1,2,5-thiadiazoles. Common routes involve the use of 3,4-difluoro-l,2,5-thiadiazole, 3,4-diamino-1,2,5-thiadiazole, l,2,5-thiadiazole-3,4-dicarbonyls, l,2,5-thiadiazole-3,4-dicarbonitrile, amino-1,2,5-thiadiazole-3-carboxamides and carboxamidines. These afford heteroarene-fused 1,2,5-thiadiazoles (which are covered in Volume 9). Below follows a brief description of fused thiadiazoles that fall within the scope of this chapter. 

Aminotriazoles which are appropriately substituted at the C(5)-position are important intermediates for the synthesis of 8-azapurines. These reactions have been reviewed <86AHC(39)ll7>. The pharmaceutically useful acyclonucleosides bearing 1,2,3-triazolines and 8-azapurines have been synthesized <888879). 4,5-Diaminotriazoles react with 1,2-dicarbonyl reagents to give 1,2,3-triazolo[4,5- )]pyrazines. 4,5-Diamino-2-phenyltriazole and sulfur monochloride afford the triazolo[4,5-c][l,2,5]thiadiazole (855) <86AHC(40)129>. The synthesis of triazolopyridines from triazoles has been described in a review <83AHC(34)79>. For further applications of substituted triazoles in preparations of complex heterocycles, see Section 4.01.4. 

Keywords 1,4-dicarbonyl compound, Lawesson s reagent, microwave irradiation, 2-alkoxythiophene, 1,3-thiazole, 1,3,4-thiadiazole... 

Disubstituted and unsubstituted l,2,5-thiadiazolo[3,4- ]quinoxaline-4,9-diones (110) have been prepared in good yield by condensation of 5,6-diaminobenzo[c][l,2,5]thiadiazole with a-dicarbonyl reagents (Equation (62)) <92H(33)337>. These quinones were then converted into 1,2,5-thiadiazolo-, pyrazino-fused TCNQ analogues by condensation with malononitrile in the presence of TiCl4 in dry pyridine. The x-ray crystal structure determination of the product derived from compound (110 R1 = R2 = H) has been accomplished. 

The reaction of unsubstituted 2-amino-1,3,4-thiadiazole (131) with 1,3-dicarbonyl compounds is dependent on the nature of the dicarbonyl compound (Scheme 13). Thus, reaction of (131) with pentane-2,4-dione gives the 4,6-dimethyl-2-thiocyanatopyrimidine (132). The formation of (132) may proceed via the cation (132a). With ethyl acetoacetate, however, a mixture of (133) and (134) is formed, (133) also being converted into (134) on heating. 

Azole approach. 2-Amino-l,3,4-thiadiazoles react with appropriately substituted a,/3-unsaturated carbonyl compounds to form fused pyrimidines (729). The orientation of the substituents in the fusion products suggests that the reaction is initiated by Michael addition of the amino group. 1,3-Dicarbonyl compounds will condense in the same manner to yield the salt (729) from a /3-keto ester the 5-oxo derivative (730) is formed (73ABC1197). 

Azole approach. 3,4-Diamino-l,2,5-thiadiazole reacts with 1,2-dicarbonyl compounds to form pyrazines (747) (76JHC13). From the reaction of 1,2,5-thiadiazole 1,1-oxides such as (748) with o-phenylenediamine, the l,3-dihydro[l,2,5]thiadiazolo[3,4-Z>]quinoxaline 2,2-dioxide (749) is formed. To understand this reaction it is pointed out that the 1,2,5-thiadiazole 1,1-dioxide ring is to be regarded as alicyclic rather than aromatic and is strongly 7r-electron deficient. Substituents with leaving properties in the 3,4-positions are therefore readily displaced as in the reaction of (748) (75JOC2743). 

In 1975, Russo reported that when N,N -diphenylbenzidine or N,N -diphenyl-l,4-phenylene diamine were interfacially polymerized with a mixture of 1,2,5-thiadiazole and 3,4-furan dicarbonyl chloride, co-polyamides were obtained having good heat resistance, dielectric properties, and mechanical properties, "comparable to those of other construction materials."... 

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