Phosphoryl chlorides dichlorides

General preparative procedures for the preparation of A -alkyl phos-phoramidic dichlorides (10) and A TV -dialkyl phosphorodiamidic chlorides (11) from the appropriate amine and phosphoryl chloride have been described. With weakly basic amines, pyrophosphoryl chloride was... 

In absence of diluent or other effective control of reaction rate, the sulfoxide reacts violently or explosively with the following acetyl chloride, benzenesul-fonyl chloride, cyanuric chloride, phosphorus trichloride, phosphoryl chloride, tetrachlorosilane, sulfur dichloride, disulfur dichloride, sulfuryl chloride or thionyl chloride [1], These violent reactions are explained in terms of exothermic polymerisation of formaldehyde produced under a variety of conditions by interaction of the sulfoxide with reactive halides, acidic or basic reagents [2], Oxalyl chloride reacts explosively with DMSO at ambient temperature, but controllably in dichloromethane at -60°C [3]. 

Benzo derivatives of the pyrido[l,2-f][l,3,2]oxazaphosphorine ring system, [l,3,2]oxazaphosphorino[4,3- ]isoquino-lines 195, 196, were synthesized by the reaction of hydroxyethyl isoquinoline derivatives 183, 184 with phenylphos-phonic dichloride, bis(2-chloroethyl)phosphonic dichloride or phosphoryl chloride. In almost all cases, the products were formed in about a 1 1 diastereomeric ratio. The only exception observed was when phosphoryl chloride was used as the reagent (X = C1) in this reaction one single diastereomer 196 (R2 = R3 = H) was obtained (Scheme 28) <2000JST(554) 119, 2000JOC316>. 

Nonmetal Halides. Vigorous or explosive reactions occur with phosphorus tribromide on addition of drops of water,20 phosphorus trichloride, phosphorus pentachloride,21 diselenium dichloride,22 sulfur dichloride, boron tribromide, sulfur dibromide,17 seleninyl bromide,23 phosphoryl chloride, sulfinyl fluoride, silicon tetrachloride, and silicon tetrafluoride.24... 

Carbonyl dichloride (phosgene) phosphoryl chloride/ phosphorus trichloride thiophosgene, thionyl chloride/ sulfur dichloride and cyanuric chloride react with carbodiimides to give the expected chloroformamidine derivatives. In the reaction of carbodiimides with two equivalents of carbonyl chloride N,N -disubstituted chloroformamidine N-carbonyl chlorides 703 are obtained. 

With phosphoryl chloride in alkali, imidazole gives the diphosphoryl imidazole (71) while 1-methylimidazole gives an analogous product. Such iV-phosphorylimidazoles play an important role in enzymic transphosphorylation. When two moles of imidazole (or benzimidazole) react with one mole of dialkyl (or diaryl) phosphoric acid chloride, the compounds (72) are formed, and di- and tri-imidazolides of phosphoric acid (e.g. 73) can be obtained similarly from phosphoric acid dichloride or from phosphoryl chloride (Scheme... 

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). 

Conversions of hydroxypyrazines to halogenopyrazines by phosphoryl chloride, phenylphosphonic dichloride, phosphorus pentachloride, sulfuryl chloride, thionyl chloride, phosphorus bromides, and other reagents have been discussed in Sections V.IC-V.IF. 

HETEROCYCLES Copper phcnylace-tylide. Dichlorobis(benzonitrile)palladium. N-Dichloromethylene-N,N-dimcthylammo-nium chloride. Diiminosuccinonitrile. Dimethyl acetylenedicarboxylate. Dipotassium cyanodithioimidocarbonate. Ethoxy-carbonyl isothiocyanate. Ethyldiisopropyl-amine. Ethylene oxide. Hydrogen fluoride. Isocyanomethane-phosphoric acid diethyl ester. Lead tetraacetate. Lithium aluminium hydride. Methylhydrazine. Phosphoryl chloride. Polyphosphate ester. Polyphosphoric acid. Potassium amide. Potassium hydroxide. Tolythiomethyl isocyanide. Tosylmethyl isocyanide, Trichlo-romethylisocyanide dichloride. Trimethyl-silyldiazomethane. 

Hydroxysteroids and 17/8-hydroxysteroids can be directly phosphorylated to monoesters with phosphoryl chloride in good yield. The intermediate dichloride from androstenolone has been characterized. 

Phosphoryl chloride reacts with cholesterol in pyridine to give the 3-phospho-dichloridate, which has been used as a source of other cholesteryl phosphate derivatives. Elimination of the ester group occurred only on heating in dioxan, to give cholesta-3,5-diene. 

When 2,4(1//,3//)-quinazolinedione reacts with phosphoryl chloride in the presence of excess of iV-alkyl cyclic amines, mixtures of 2,4-dichloroquinazolines, and 4-chloro-2-(A-alkyl-co-chloro-alkylamino)quinazolines (120) result. Bulky amines favor dichloride formation. Almost exclusive formation of 2-aminated product results from A-methyl pyrrolidine, indicating that either 4-oxo-... 

Partial reaction of phosphoryl chloride with amines can be used for synthesis of phosphonic acids 392,393 if applied to phosphonic dichlorides it affords unsymmetrical phosphinic acids.396... 

Trichloroethyl dihydrogen phosphate (2). This substance can be prepared as a crystalline solid (m.p. 120-121°) in good yield by the following procedure The alcohol and phosphoryl chloride are refluxed with a catalyst (AICI3, KCl, or pyridine) for 4 hr. (HCl is evolved). The resulting phosphoro-dichloridate (1) is then heated with a small excess of water for 1 hr. at 80°. 

A series of experiments in which a catalyst affected the composition of the product mixture were reported recently. With a large excess of phosphoryl chloride, phosphonic dichlorides, phosphinic chlorides, and... 

The preparation of the compounds (25), (26), and (27) from phosphoryl chloride and triphenylphosphinimine has been described a similar reaction takes place with the trichloride (28) but not with the trichloride (29) nor with phosphonic dichlorides. ... 

Triphenyl)aminophosphonium chloride, synthesis 19 (Dimethylamido)phosphoryl dichloride, synthesis 20 Bis(dimethylamido)phosphoryl chloride, synthesis 21 Octamethylpyrophosphoramide, synthesis 22 Methylbromoarsines, sjmthesis 26... 

Barium iodate 1-hydrate, synthesis 4 Indium(I) bromide, synthesis 6 Hexachlorodisiloxane, synthesis 7 Trichlorosilanethiol, synthesis 8 Tris(acetylacetonato)silicon chloride, synthesis 9 Titanium(III)chloride, synthesis 11 Bis[tris(acetylacetonato)titanium(IV)] hexachloro-titanate(IV), synthesis 12 Zirconium(IV) iodide, synthesis 13 (Triphenyl) aminophosphonium chloride, synthesis 19 (Dimethylamido)phosphoryl dichloride, synthesis 20 Bis(dimethylamido)phosphoryl chloride, synthesis 21 Trimeric and tetrameric phosphonitrilic bromides, synthesis 23 Phosphorus(V) chloride-boron trichloride complex, synthesis 24... 

PON(CH3)2Cl2 (Dimethylamido)-phosphoryl dichloride, 7 69 PO(N(CH))2l2Cl Bis(dimethyl-amido)phosphoryl chloride,... 

Perfluoro-n-hexane Perfluoro-n-octane 7. Aprotic inorganic solvents Phosphoryl chloride Sulfur dichloride Sulfur dioxide Sulfur monochloride Sulfuryl chloride Thionly chloride... 

Phosphamides, A-Sulfates and Related Esters - 5- -,3-0-Cyclic phos-phamides have been prepared by reaction of 5-amino-5-deoxy-l,2-0-isopropyl-idene-a-D-xylofuranose with either phenylphosphonic dichloride or phosphoryl chloride, and their conformations determined. Chemo-selective -sulfation of 2-amino-2-deoxy-P-D-glucopyranose derivatives with a single free hydroxy-group was achieved with phenyl chlorosulfate followed by hydrolysis in aqueous NaHC03. ... 

A major use for phosphoryl chloride is in the synthesis of phosphoryl esters (Chapter 6). It will also react with Grignard reagents to give phosphine oxides (6.112), and with secondary amines to give amino-substituted phosphine oxides or phosphonic dichlorides (7.96). 

Thio)phosphoryl chloride yields oxides and sulfides 33 which upon treatment with alcohols produces the corresponding alkoxides 3410 or amino derivatives 35, ° both with retention of configuration at the P atom. ° Substituted analogues 36 are prepared from (thio)phosphonic dichlorides. 

Reaction of the chlorinated Lewis acids carbonic dichloride, phosphoryl chloride, chloroiminium chloride, and chlorine with hexamethylphosphoric triamide... 

Chlorine is readily soluble in sulfiir-chlorine compounds, which can be used as industrial solvents for chlorine. Disulfiir dichloride U0025-67-9], S2CI2, is converted to sulfur dichloride (SCI2) and sulfiir tetrachloride (SCI4). Some metallic chlorides and oxide chlorides, such as vanadium oxide chloride, chromyl chloride, titanium tetrachloride, and tin(IV) chloride, are good solvents for chlorine. Many other chlorine-containing compounds dissolve chlorine readily. Examples are phosphoryl chloride, carbon tetrachloride (Fig. 7), tetrachloroethane, pentachloroethane, hexachlorobutadiene... 

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