1.2.4- Triazole 3-amino-5-chloro

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... 

The reaction of iV-amino-2-chloro-5-phenyl[l,2,4]triazole 364 with malonodinitrile, in the presence of triethylamine, in refluxing ethanol gives intermediate 365 that spontaneously cyclized to give 6-amino-7-cyano-3-phenyl-pyrazolo[5,l-c][l,2,4]triazole 62 in 70% yield (Equation 69) <1996SC3827>. 

Agrawal and co-workers have reported the synthesis of A,A -bis(l,2,4-triazol-3-yl)-4,4 -diamino-2,2, 3,3, 5,5, 6,6 -octanitroazobenzene (17) (BTDAONAB) via nitration-oxidative coupling of 4-chloro-3,5-dinitroaniline (152) followed by nucleophilic displacement of the chloro groups with 3-amino-1,2,4-triazole. BTDAONAB has the unique distinction of being the most thermally stable explosive reported so far (DTA exotherm 550 °C) as compared to well known thermally stable explosives such as TATB ( 360 °C), TACOT ( 410 °C), NONA ( 440 50 °C), and PYX ( 460 °C). 

Carboxy-l,3-diamino-2,4,6-trinitrobenzene 5-Nitro-2(3,5-diamino-2,4,6-trinitrophenol)-1,2,4-triazole 5-Nitroterazolecopper salt 5-Ureido-l,3-diamino-2,4,6-trinitrobenzene 7-Amino-4,6-dinitrobenzofuroxan 10-Chloro-5,10-dihydrophenarsazine Acetyltrinitro-cyclotetramethylene tetramine Acquinite... 

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). 

The reactions of 7-chloro-pyrimido[5,4-/][l,2,4]triazolo[3,4- ]l,3,4] thiadiazepines 81a-c with different nucleophiles were described in order to obtain new derivatives with possible antitumor activity <2003MI46>. The substituted 81a-c were prepared by cyclocondensation of 4,6-dichloro-2-methylthiopyrimidine-5-carbaldehyde 82 with the corresponding 3-substituted 4-amino-l,2,4-triazole-5-thiones 83. The different reactions as well as the corresponding yields are described in Scheme 8. Interestingly, hydrolysis occurred even during 111 NMR experiments in DMSO at 80 °C. 

A solution of 158.5 g of 2-chloro-2, 4 -difluoroacetophenone and 88.8 g of 4-amino-4H-l,2,4-triazole in 1,600 ml of cyanomethane was heated at reflux for 16 hours, cooled down, and filtered. The solid thus obtained was then washed with 500 ml of ethyl ether once to afford 2-(lH-l,2,4-triazol-l-yl)-2, 4 -difluoroacetophenone salt. 

The halogen metal exchange reaction between 7-bromo or 7-iodo-3-phenyltriazolopyrimidine 165 and butyllithium in iV,N,N, N -tetra-methylethylenediamine afforded the 7-lithio compound 166, whereas a similar reaction with the 7-chloro derivative 165 (R = H) gave the ring-fission product, 5-amino-l-phenyl-l//-l,2,3-triazole-4-carbonitrile 169 (91 CPB2793). Reaction of 166 with electrophiles such as benzaldehyde and ketones gave 170 and 167 respectively, together with 7,7 -bis[3-phenyl-3//-1,2,3-triazolo[4,5-d]pyrimidine] 168 (Scheme 34). 

Another nitrification inhibitor that has received much attention in Japan is 2-ami no-4-chloro-6-methyl pyrimidine. It is manufactured by Mitsui Toatsu Chemicals, Inc. (formerly Toyo Koatsu Industries, Inc.) under the trade name AM. Other nitrification inhibitors that have been used in Japan in compound fertilizers are sulfathiazole, dicyandiamide, thiourea, N-2, 5-dichorphenyl succinamide, 4-amino-l, 2, 4-triazole hydrochloride, and guanylthiourea.50... 

To build up the desired cyclic key precursors, containing an amide bond as an anchor to connect the triazole moiety, different strategies can be pursued. Cyclization of y-amino acids directly yields pyrroli-dones, whereas P-amino alcohols allow access to two different chiral bicyclic frameworks. They can form either oxazolidin-2-ones (Enders and Kallfass 2001) or morpholinones upon treatment with phosgene or chloro acetylchloride, respectively (Scheme 3). 

Various picryl and picrylamino substituted 1,2,4-triazoles which were formed by condensing 1,2,4-triazole or amino-1,2,4-triazole with picryl chloride (1-chloro-... 

A daring expedient to obtain the right starting material was the alkaline cleavage of a similarly substituted purine (0.5 N NaOH, room temp, 1 h) to give 6-chloro-5-formamido-4[(2,3-0-isopropylidene-D-ribofuranosyl)-amino]pyrimidine, from which the formyl group was removed by acid hydrolysis, followed by formation of the triazole ring with aqueous nitrous acid (optical purity was retained). ... 

Alkaline conditions favor the formation of triazolo[4,3-c]pyrimidines (91). Thus, on heating in an aqueous solution of NaHCOj, 4-chloro-5-amino-6-(ethoxycarbonyl)hydrazinopyrimidine (95) is converted to triazole 96. The action of diethoxymethylacetate on 95, followed by heating in hydrochloric acid, gives 9-aminopurine 97 (63JOC2257). 

The hydrazinium salt (10.2) of a l-amino-l,2,3-triazole-5-lhiol is cyclized by heating with an a-chloro ketone [B-45],... 

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 ... 

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. ... 

Aryl-6-phenyl-2-methylthio/secondary amino substituted-4(3//)-pyrimidinones were derived from a reaction of N-arylamino substituted 1,3-diaza-1,3-butadienes with substituted ketenes that was analyzed by computational methods <97T13829>. 1,3-Diazines related to 6-amino-4-chloro-5-cyano-2-(dimethylamino)pyrimidine were prepared in one-pot fashion from 1,1-diamino-2,2-dicyanoethylene and phosgeniminium chloride <97SC1223>. Pyrazolo[3,4- /]pyrimidines were derived from 4-substituted 5-aminopyrazole-l-carbothioamides <97JCR(S)352>. Amino-5-(trifluoromethyl)-l,2,4-triazole gave polysubstituted 2-... 

---