Phosphoryl chloride, diphenyl

The cyclization of diethyl /V-[2-(l-pyrrolyl)phenyl]aminomethylene-malonate by heating in diphenyl ether for 8 min gave 8-pyrrolylquinoline-3-carboxylate (570) in 23% yield, while its reaction in boiling phosphoryl chloride for 15 min afforded the tricyclic pyrroloquinoxaline (571) in 76% yield [75JCS(P1)2409). 

The cyclization of /V-(6-methyl-2-pyridyl)aminomethylenemalonate (1001, R = Me, R1 = H), labeled on one of the carboxyl groups with l4C, gave labeled 1,8-naphthyridine (1003, R = Me, R1 = H) in boiling diphenyl ether and labeled pyrido[l,2-a]pyrimidine (1002, R = Me, R1 = H) in a mixture of phosphoryl chloride and polyphosphoric acid in 77% and 85% yields, respectively (73MI2 75MI2). 

Regioselective cyclization of /V-(4-benzoyl-5-benzimidazolyl)amino-methylenemalonates (969, R = H, Me) was observed. When the cyclization was carried out in polyphosphoric acid, then 4-phenylimidazo-[4,5-/]quinoline-5-carboxylates (970) were obtained, while the thermal cyclization in diphenyl ether at 200°C, or the cyclization in a mixture of phosphoryl chloride and polyphosphoric acid afforded 4-benzoyl-8-hydroxyimidazo[5,4-g]quinoline-7-carboxylates (971) (89KFZ692). 

When methyl 4,6-benzylidene-2-desoxy-a-D-galactoside (LXXXVI)126 was treated with phosphorus oxychloride in pyridine at —40°, followed by barium hydroxide,236 it gave amorphous barium methyl 4,6-benzyli-dene-2-desoxy-a-D-galactoside 3-phosphate (LXXXVII). If diphenyl-phosphoryl chloride [diphenylchlorophosphonate, (PhO)2POCl]236 240 in pyridine was used as the phosphorylating agent, then crystalline (methyl... 

Benzamido-4//-pyrido[l,2-a]pyrimidin-4-ones 180 (R = H) were also prepared from compound 178 (R = H) by heating in diphenyl ether in quantitative yield [R1 = 4(8)-Me] (81GEP2932703) and by heating in a mixture of phosphoryl chloride-polyphosphoric acid in 64-71% yields [R1 = H, 6(6)-Me] (84S152). 

Chloro-2,S-dimethylpyrazine was not isolated from the reaction of DL-alanine anhydride with a mixture of phosphoryl chloride and phosphorus pentachloride, but the reaction gives a poor yield of (48, X = Q) and a small quantity of (48, X = OH). Gallagher et al. (282) found that DL-phenylglycine with phosphoryl chloride gave 2,5-dichloro-3,6-diphenylpyrazine and 3-hydroxy-2,5-diphenyl-pyrazine (presumably formed by loss of the elements of hydrogen chloride from an intermediate 2-chloro-5-hydroxy-3,6-diphenyldihydropyrazine) and Dunn et al. (95) from DL-leucine anhydride and phosphoryl chloride prepared flavacol, 3-hydroxy-2,5-diisobutylpyrazine, and a mature of chloropyrazines, whereas Ohta (101) used phosphoryl chloride and phosphorus pentachloride and obtained flavacol and a little 2[Pg.26]

Chloro-3-methylpyrazine (101,535) and 2-chloro-5-phenylpyrazine (363, 365a, 377, 824, 825) have been prepared from the corresponding hydroxy compound and phosphoryl chloride, 2-chloro-6-methylpyrazine from 2-hydroxy-6-methylpyrazine and phosphoryl chloride with one drop of dimethylformamide (681), and 2-benzyl(or s-butyl, isobutyl, or isopropyl)-3phosphoryl chloride with a trace of concentrated sulfuric acid (80). 2-Chloro-6-methyl-3-propyl- (826), 3[Pg.99]

Dichloropyrazines have also been prepared from the corresponding hydroxy compounds as follows 2,3-dihydroxypyrazine with phosphoryl chloride containing pyridine (481, 757) [see Schneller and May (828) re the use of phenylphosphonic dichloride at 150-170°] 2,3-dihydroxypyrazine and its methyl, dimethyl, phenyl, diphenyl, and 5-methy 1-6-phenyl derivatives with phosphoryl chloride (483, 829) [N.B. error in work of Minovici and Bente (830)] 2-chloro-5-hydroxypyrazine with phosphoryl chloride (831) 2-chloro-6-hydroxypyrazine with phosphoryl chloride at reflux for 6hours (832) and 2,5-dihydroxy-3-phenylpyrazine and3,5-dihydroxy-2-phenylpyrazine with phosphoryl chloride at 180-200° (829). 

Bromo-3-hydroxy-5,6-dimethylpyrazine and 2-bromo-5-hydroxy-3,6-diphenyl-pyrazine with phosphoryl chloride afforded 2,3-dichloro-5,6-dimethylpyrazine and 2,5-dichloro-3,6-diphenylpyrazine, respectively (817) and the bromo substituent in 2-amino-3-bromo-5,6-dimethylpyrazine and its p-aminobenzenesulfonyl derivative have been replaced by chlorine on treatment with aqueous hydrochloric acid in ethanol (812). 

Dehydrogenations of piperazines to pyrazines have been described in Section II.6, and the conversion of piperazine over catalysts (e.g., CuO) to give mostly pyrazine (90-94%) has been studied (1718). The oxidation of 1,4-diphenylpiperazine with manganese dioxide in chloroform at 20° to yield A, A -diformyl-A(, -diphenyl-ethylenediamine has been reported (1719). Formylpiperazines have been reported as formylating agents. Thiophene, 1,4-diformylpiperazine, and phosphoryl chloride are reported to give 2-formylthiophene (1720). 

Phenyl phosphoro chloridate (diphenyl phosphoryl chloride)... 

Phosphorylation O-Benzyl phosphorus 0,0-diphenylphosphoric anhydride. 2-Cyanomethyl phosphate. Dibromomalonamide. Di-p-nilrobenzylphosphoryl chloridate. Dioxane diphosphate. Diphenylphosphorochloridate. Ethoxyacetylene. Metaphosphoric acid. o-Phenyl-ene phosphorochloridate. Phosphoric acid, anhydrous. Phosphorodimorpholidic chloride. Phosphorus pentoxide-Phosphoric acid. Phosphoryl chloride. Polyphosphoric acid. Pyro-phosphoryl tetrachloride. Silver dibenzyl phosphate. Silver diphenyl phosphate. Tetra-p-nitrophenyl pyrophosphate. 

Dichloro-2,3-diphenyl- and 5,8-dichloropyrazino[2,3-t/]pyndazine are obtained by treatment with phosphorus pentachloride/phosphoryl chloride in the presence of a small amount of dimethylformamide (1 drop) at 125 °C for one hour in a yield of 87% [mp 202-204 °C purified by chromatography (silica gel, CH,CI2)],8J or by refluxing for 8 hours in a yield of 34%,86 respectively. 

Diphenyl phosphoro chloridate (diphenyl phosphoryl chloride) [2524-64-3] M 268.6, b 141"/lmm,... 

Synonyms Diphenyl phosphorochloridate Diphenyl phosphoryl chloride DPCP Phosphorochlorendic acid diphenyl ester... 

Diphenyl phosphonate. See Diphenyl phosphite Diphenyl phosphorochloridate Diphenyl phosphoryl chloride. See Diphenyl chlorophosphate Diphenyl phthalate... 

Mixed alkyl aryl esters may be obtained by reacting phosphorochloridates with sodium derivatives of phenols or alcohols (5.297, 5.298). Octyl diphenyl phosphate is obtained commercially by reaction (5.298), the starting material having been obtained from octyl alcohol and phosphoryl chloride by a reaction of type (5.295). 

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