L-Chloro-1.2,4-triazole

Unsubstituted 1,2,4-triazole and its derivatives with electron-donating substituents in the 3(5) position of the ring react with chlorine in alkali to give 1-chloro- and 1,3-dichlorotriazoles 40, 41 (67ZC184 69ZC325). 1,3-Dichlorotriazole 41 was also obtained by chlorination of 3-chloro-l,2,4- triazole (69ZC325) (Scheme 15). 

Reaction of DCT with cyclohexene in the presence of AIBN gives a mixture of rrrtm-l-ch]oro-2-(3-chloro-l,2,4-triazol-l-yl)cyclohexane and 3-chlorocyclohexene-1 (69ZC325) (Scheme 73). 

Amino-l-nitro-l,2,4-triazole (581), obtained by nitration of 5-amino-triazole with acetyl nitrate, rearranges, on heating, to the nitramino-triazole (582). ° The combined action of sodium hydroxide, potassium iodide, tri-ethylamine, and sodium dihydrogen phosphite on the chloro-nitro-triazole (583) results in a mixture of the rearranged triazole (584), 3-chloro-l,2,4-triazole, and the coupled product (585). The stable betaine (586) has been prepared by treatment of 4-phenyl-1,2,4-triazole with phenacyl bromide, followed by tri-ethylamine. The meso-ionic triazolium thiolate (537 X = S) reacts with chlorine to form the dichloride (587 X = SCU), which has been converted into the betaine (588) by the action of diethyl bromomalonate in the presence of triethylamine. ... 

When treated with NaN02 in aqueous HCl (a), 24 is transformed to 3-chloro-l,2,4-triazole (26) due to nucleophilic displacement of the -group in the diazoniumion25 by chloride... 

Halogeno-l-methyl-l,2,3-triazoles undergo substitution reactions with amines, but the 4-halogeno analogs do not. 5-Chloro-l,4-diphenyl-l,2,3-triazole with sodium cyanide in DMSO gives the cyano derivative (63JCS2032). 1-Substituted 3-chloro- and 5-chloro-l,2,4-triazoles both react with amines. 

The action of hydrazine on l-acetonyl-5-chloro[l,2,4]triazole 777 or 778 gave (77JOC1018 82KGS1113) 779 and 780, respectively. Dehydrogenation of 779 gave 781. Condensation of 3-hydrazino[l,2,4]triazole 782 with... 

Agrawal and co-workers have reported the synthesis of N,N -bis(l,2,4-triazol-3-yl)-4,4 -diamino-2,2, 3,3, 5,5, 6,6 -octanitroazobenzene (BTDAONAB) [Structure (2.39)] via nitration-oxidative coupling of 4-chloro-3,5-dinitroaniline followed by nucleophilic displacement of the chloro groups with 3-amino-l,2,4-triazole. BTDAONAB has the unique distinction of being the most thermally stable explosive reported so far (DTA exotherm 550 °C) as compared with well-known thermally stable explosives such as TATB (-360°C), TACOT (-410°C), NONA (-440-450°C) and PYX (-460 °C) [25]. 

Schiff bases (112) derived from 4-chlorobenzaldehyde and 1-substituted-5-amino-3-methylthio-l,2,4-triazoles (111) underwent cyclization with phe-noxyacetyl chloride or dichloroacetic acid in the presence of phosphoryl chloride and dimethylformamide to give the 7-(4-chlorophenyl)-fram-6,7-dihydro-3-methylthio-6-phenoxy-l-substituted-l,2,4-triazolo[4,3-a]pyrimidin-5-one 113 and l-substituted-6-chloro-7-(4-chlorophenyl)-3-methylthio 1,2,4-triazolo[4,3-a]pyrimidin-5-one 114, respectively (88JHC173) (Scheme 47). 

From a coned soln of chloroauric acid and diazotized aminopropylrriazoie, there was separated 5-diazo-3-fi-propyl-1,2,4-triazole chloroaurate, [(Q HjNg AuCl3)2.H20], which darkened on heating and melted. at 135° (dec) and 5-diazo-3-isopropyl-l,2,4-triazole chloro-... 

The synthesis of 3,5-dibromo-l-(thietan-3-yl)-l,2,4-triazole 135 was performed by the reaction of 2-chloro-methylthiirane 99 with 3,5-dibromo-l,2,4-triazole yielding the product in 50% <2005RJ01847> (Equation 38). 

The molecule of 3-nitro-3 -chloro-l//-bi-l,2,4triazole-5,l -yl has transoid conformation, where the substituents (chlorine and nitro group) are most distant from each other and the rotation angle of two triazole rings is 5°, while the nitro group is rotated by 4° with respect to the triazole cycle [156], Molecular and crystalline structures of 1-methyl-3,5-dinitro-l, , 4-triazole [153] and l-(mesityl-2-sulfonyl)-3-nitro-l,2,4-triazole were determined [119]. 

The analogical fragmentation way shows the isomeric 1-chloro- and 5-chloro-3-nitro-l,2,4-triazoles herewith that the isomers have some differences. 5-Chloro... 

The alkylation products of A -chloro-3-nitro-l,2,4-triazole [580], heterylation products of nitrotriazoles [612], glycosylation products of 3-bromo-5-nitro-l,2,... 

In addition to the Dimroth rearrangement of [l,2,4]triazolo[3,4-c][l,2,4]triazines discussed in the last section, derivatives of (42) would probably be accessible by the general application of a special case which involved the reaction of l-acetonyl-5-chloro-l,2,4-triazole (356) with hydrazine to produce the dihydro compound (357). Lead tetraacetate oxidation of (357) formed (358) (77JOC1018). 

In contrast to other azoles whose stability decreases from A-iodo to A-bromo and further to A-chloro derivatives, l-chloro-3-nitro-l,2,4-triazoles are more stable that their 1-bromo and 1-iodo analogs. In this series the stability order is reversed (96UP1). Rearrangement of A-halo-1,2,4-triazoles is described in Section IV,B,2. 

The reaction of 7V-(a-chlorobenzylidene)carbamyl chloride (180) with sodium azide gave (74JOC1226), among other products, 3,6-diphenyl-1,2,4-triazolo[3,4-b] 1,3,4-oxadiazole (182) and not the other possible product 181. The former product was unequivocally prepared (74JOC1226) by cyclization of 4-benzoylamino-5-chloro-3-phenyl-l,2,4-triazole (184) with aqueous sodium carbonate and found to be identical with that obtained by the previous method. 2-Hydrazino-1,3,4-oxadiazoles (185) with carboxylic... 

Amino-l,2,4-triazole can be diazotized, but when treated with sodium nitrite and hydrochloric acid, 3-chloro-1,2,4-triazole is formed due to dediazoniation ... 

Chlorobenzotriazole in didiloromethane added to a stirred soln. of deserpidine in the same solvent, and the product isolated after 15 min. 7-chloro-7H-deserpidine. Y 93.5%. F. e. s. K. V. Lidiman, Soc. (C) 1971, 2539 1-chlorobenzotriazole and 1,3-dichloro-l,2,4-triazole as chlorinating agents s. H. Oel-sdilager and E. Ehlers, Pharm. Acta Helv. 47, 1 (1972). 

The presence of catalytic tetrabutylammonium bromide was necessary for the reaction of sodium salt of l-phenyl-3-hydroxy-l,2,4-triazole M7 with l-(chloro-acetoxy)alkylphosphonates M3 to get better yields. The experiment also showed that this reaction was affected by reaction temperamre, base, and water. We observed that both the carboxylate ester bond and phosphonate ester bond in compounds M3 or IK were easy to cleave by hydrolysis in the presence of base and water at a higher temperature. It was found that the carboxylate ester bond was easier to cleave than the phosphonate ester bond in diethyl phosphonate however, the phosphonate ester bond was easier to cleave than the carboxylate ester bond in... 

V-[[l-[4-chloro-2-(2-chlorobenzoyl)phenyl]-3-[(dimethyl-amino)carbonyl]-l/f-l,2,4-triazol-5-yl]methyl]-l,3-dihy-dro-l,3-dioxo-2H-isoindole-2-acetamide (C29H22CI2NSO5 65699-00-5) see Rilmazafone... 

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