Triazoles phosphorylated

N,N -oxalyldi( 1,2,4-triazole) phosphoryl tris( 1,2,4-triazole) tris( 1,2,4-triazol-1 -yl)phosphine... 

Esters of a-diazoalkylphosphonic acids (95) show considerable thermal stability but react with acids, dienophiles, and triphenylphosphine to give the expected products. With olefinic compounds in the presence of copper they give cyclopropane derivatives (96), but with no such compounds present vinylphosphonic esters are formed by 1,2-hydrogen shift, or, when this route is not available, products such as (97) or (98) are formed, resulting from insertion of a carbenoid intermediate into C—C or C—H bonds. The related phosphonyl (and phosphoryl) azides (99) add to electron-rich alkynes to give 1,2,3-triazoles, from which the phosphoryl group is readily removed by hydrolysis. 

Various chlorophenoxyphosphorylditriazoles, prepared analogously to the phosphoryldiimidazoles from phosphordichloridate and triazole, are frequently used as reagents in the phosphorylation of nucleosides (see Chapter 12). 

Analogously, the corresponding tristriazolide of phosphoric acid was prepared from POCI3 and IV-trimethylsilyl-1,2,4-triazole in 60% yield.1261 Both trisazolides are used for the phosphorylation of nucleosides. 

The phosphorylation of the 3 -OH of a 5 -substituted thymidine was achieved with 2,4,6-triisopropylbenzenesulfonyl-3-nitro-1,2,4-triazole [49a]... 

This shows that the combination of diphenylphosphate and arylsulfonyl-3-nitro-triazole is a powerful phosphorylating agent in pyridine solution. 

Phosphorylated 2,3-diamino-2//-indazoles (172) are well suited for the annulation of a 1,2,4-triazole ring by a combination of an aza-Wittig and an intramolecular trapping reaction. As shown in Scheme 66, CS2 and CO2 are good reaction partners in the case of acid halides, however, no ring closure occurs, and 173 was obtained (89TL6237 90JOC4724). 

Ribavirin is reversibly phosphorylated by all nucleated cells. It is also metabolized in the liver to a triazole carboxylic acid metabolite that is eliminated in the urine along with the parent compound. The plasma half-life of ribavirin is 9.5 hours when it is administered by aerosol (2.5 hours/day for 3 days), whereas its half-life is around 12.5 days at steady state. The drug accumulates in erythrocytes, with a half-life of 40 days. 

Heating 1-phenyl- and 5-methy 1-1-phenyl-1,2,4-triazol-3-ones with phosphoryl bromide gave 45% yields of the 3-bromo derivatives (75BSF647). 

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). 

AIXOOO CAS 1031-47-6 HR 3 5-AMINO-1 -BIS(DIMETHYLAMIDE)-PHOSPHORYL-3-PHENYL-1,2,4-TRIAZOLE... 

AMINO-l-BIS(DIMETHYLAMIDE)PHOSPHORYL-3-PHENYL-l,2,4-TRIAZOLE see AIXOOO 5-AMINO-l-BIS(DIMETHYLAMIDO)PHOSPHORYL-3-PHENYL-1,2,4-TRIAZOLE see AIXOOO 5-AMINO-l- IS(DIMETHYLAMINO)PHOSPHINYL)-... 

AMINO-3-PHENYL-1-BIS (DIMETHYL-AMINO)-PHOSPHORYLE-1,2,4-TRIAZOLE (FRENCH) see AIXOOO... 

AMINO-3-PHENYL-l-BISpiMETHYLAxMINO)-PHOSPHORYL-lH-l,2,4-TRIAZOL (GERMAN) see AIXOOO... 

JCS(P1)1171] and Sung (81CC1089 82JOC3623) found that these 1,2,4-triazole derivatives of uridine can be readily prepared at room temperature with excess 1,2,4-triazole and phosphoryl chloride and triethylamine or with 0-chlorophenyldi-(l//-l,2,4-triazol-l-yl)phosphine oxide in acetonitrile. These stable, often crystalline 1,2,4-triazole derivatives react readily with aqueous ammonia and primary or secondary amines at room temperature to afford the corresponding cytidines in high yields. 

Complexation of the latter at phosphorus with borane, followed by methanolysis of the siloxyether function, gives the related o-hydroxyaryl diazaphospholidines. The cage-like triaminophosphine (109) has been obtained from the reaction of tri(2-pyrrolyl)methane with phosphorus trichloride, in the presence of triethylamine. This compound is stable to methanolysis, hydrolysis, and aerial oxidation at room temperature. Phosphorylation of various 1,2,4-triazoles with halophosphines has given a route to the heterocyclic system (110), and routes to various [2,4,l]benzodiazaphosphinines, e.g., (Ill), have also been developed. ... 

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