1 -Methyl-4-chloro triazolo

As previously mentioned, the methyl group of 2-(p-tolyl)-s-triazolo-[l,5-a]pyridine is inert under the conditions of the Anil Synthesis. However, introduction of a chlorine atom in ortho position to this methyl group enables reaction to be carried out at 20°-30°C (Section II,E,3). Thus, for example, from 2-(3-chloro-4-methylphenyl)-j-triazolo[l,5-a]pyridine (19) and Schiff s base 171, the stilbene 172 is formed. In the case of 2-phenyl-7-methyl-j-triazolo[l,5-a]pyridine (173), however, reaction with 171 gives the styryl derivative 174, without additional activation of the methyl group.19... 

Reaction of arylhydrazones 216 of piperidin-2-ones with methyl chloro-formate, phosgene, or thiophosgene yielded (80USP4213773) the fused-ring system 217. Reaction of 2,2 -azopyridine (218) with diazoalkanes afforded [66JCS(C)78 73LA2088] the 2-(pyrid-2-yl)-l,2,4-triazolo[4,3-a]-... 

Chemicel Name 8-Chloro-1 methyl-6-phenyl-4H-s-triazolo[4,3-a] [1,4]benzodiazepine Common Name —... 

Chloro-1 -methyl-5-phenyl-s-trizolo[4,3-a]quinoline A stirred mixture of 6triethyl-orthoacetate (0.925 g,0.0057 mol) and xylene (100 ml) was refluxed, under nitrogen, for 2 hours 40 minutes. During this period the ethanol formed in the reaction was removed by distillation through a short,glass helix-packed column. The mixture was concentrated to dryness In vacuo and the residue was crystallized from methanol-ethyl acetate to give 1.28 g of 7-chloro-1-methyl-5-phenyl-s-triazolo[4,3-a]-quinoline (83.9% yield). The analytical sample was crystallized from methylene chloride methanol and had a melting point 252.5°-253.5°C. 

Chloro-1 -methyl-6-phenyl4H-s-triazolo-[4,3-a] [1,4] -benzodiazepine A stirred suspension of 5-chloro-2-[3-(bromomethyl)-5-methyl4H-1,2,4-triazol4-yl] -benzophenone (391 mg, 0.001 mol) in tetrahydrofuran (15 ml) was cooled in an ice-bat hand treated with a saturated solution of ammonia in methanol (12.5 ml). The resulting solution was allowed to warm to ambient temperature and stand for 24 hours. It was then concentrated in vacuo. The residue was suspended in water, treated with a little sodium bicarbonate and extracted with methylene chloride. The extract was washed with brine, dried with anhydrous potassium carbonate and concentrated. The residue was crystallized from methylene chloride-ethyl acetate to give... 

Chloro-2-[l-methyl-4-phenyl(thiosemicarbazido)]quinoxaline (275) gave 7-chloro-3-methyl[ 1,2,4]triazolo[4,3-fl]quinoxalin-3-ium-1 -thiolate (276) (Me2... 

For testing sedative hypnotic drugs of the triazolam type the preparation was undertaken of 8-chloro-6-(o-chlorophenyl)-4ff-.y-triazolo[4,3-a][l,4]benzodiazepin-1 -valeric acid methyl ester as an intermediate, with subsequent cyclization and amida-... 

Reaction of 4-chloro-5-methyl-6-phenyl-2-pyrimidinamine (566) with formylhydrazine yielded a mixture of triazolo[4,3 c]pyrimidine (567) and its [l,5-c]isomer 568 (83USP4405780), and boiling 566 with formylhydrazine in DMF containing a 3-A molecular sieve afforded 567 (81GEP3029871) (Scheme 110). 

Methyl-5-oxo-l,5-dihydro-8-carbamoyl-l,2,4-triazolo[4,3-c]pyrimidines 577 and 578 were prepared by the cyclization of 576 with acetic anhydride and ethyl oxalate, respectively (89PHA604).The 4-methyl-l,2-dihydropyra-zolo[3,4-d]pyrimidine-3,6-dione 579 also was obtained in the latter case, as a consequence of breaking the amide bond and releasing the amine moiety. Coupling ethyl dithioacetate and 5-chloro-4-hydrazinopyrimidine (580) afforded the triazolo[4,3-c]pyrimidine 581 (89H239) (Scheme 114). 

Chloro-2-(3-methyl-4H-l,2,4-triazol-4-yl)benzophenone (Oxidation of 7-chloro-l-methyl-5-phenyl-s-trizolo[4,3-a]quinoline) A stirred suspension of 7-chloro-l-methyl-5-phenyl-s-triazolo[4,3-a] quinoline (2,94 g, 0.01 mol) in acetone (110 ml) was cooled in an ice-bath and treated slowly with a solution prepared by adding sodium periodate (2 g) to a stirred suspension of ruthenium dioxide (200 mg) in water (35 ml). The mixture became dark. Additional sodium periodate (8 g) was added during the next 15 minutes. The ice-bath was removed and the mixture was stirred for 45 minutes. Additional sodium periodate (4 g) was added and the mixture was stirred at ambient temperature for 18 hours and filtered. The solid was washed with acetone and the combined filtrate was concentrated in vacuum. The residue was suspended in water and extracted with methylene chloride. The extract was dried over anhydrous potassium carbonate and concentrated. The residue was chromatographed on silica gel (100 g) with 10% methanol and 90% ethyl acetate 50 ml fractions were collected. The product was eluted in fractions 10-20 and was crystallized from ethyl acetate to give 0.405 g of melting... 

Chloro-2-[3-(hydroxymethyl)-5-methyl-4H-l,2,4-triazol-4-yl]benzophenone A stirred mixture of 5-chloro-2-(3-methyl-4H-l,2,4-triazolo-4-yl)benzophenone, (2.98 g, 0.01 mol) paraformaldehyde (3 g) and xylene (100 ml) was warmed under nitrogen, in a bath maintained at 125°C for 7 hours. The mixture was then concentrated in vacuum. The residue was chromatographed on silica gel (150 g) with 3% methanol-97% chloroform. 

Chemical Name 8-Chloro-l-methyl-6-(o-chlorophenyl)-4H-s-triazolo[4,3-a][l,4]-benzodiazepine... 

Studies of allyl ether migrations in this system have stemmed solely from the efforts of Makisumi.23,24 By reacting 5-methyl-7-chloro-s-triazolo-(l,5-a)pyrimidine with sodium allyloxide in allyl alcohol at room temperature, the corresponding 7-allyloxy derivative was obtained. When this was rearranged at 150°, during 30 minutes, seven different products were obtained. These were separated into chloroform-soluble and chloroform-insoluble material. Out of the latter, by fractional crystallization two products were isolated. One of these was... 

Chloro-6-(2-chlorophenyl)-1 -methyl-4. f-l, 2,4-triazolo[4,3-a]-l, 4-benzodiazepine Ci7Hi2Cl2N4 = 343.2... 

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