Phosphorus chloride complexes

Chlorination. When 75 was treated with chlorine in the presence of aluminium chloride, initial chlorination took place at the 5-position, but the reaction was rather unselective 5,8-di-, 5,7,8-tri-, and 5,6,7,8-tetra-chloroisoquinolines were also formed (64JOC329). Perchlorination has been achieved by initial reaction of the isoquinoline-aluminium chloride complex with chlorine, as above, followed by treatment with phosphorus pentachloride at 270°C in an autoclave [66JCS(C)2328]. Treatment of 1,8-dimethylisoquinoline with NCS gave the 5-chloro derivative (91NKK-1193). Meisenheimer reaction of isoquinoline 2-oxides with phosphoryl chloride gave 1-chloroisoquinoline (84MI2). 

Aluminum chloride-phosphorus oxychloride complex, 31, 88 Amberlite IR-4B resin, 32, 13 Amidation, of isocyanic acid with bromo-aniline and other aromatic amines, 31,8... 

Controlled alkylation of phosphorus oxychloride may also be accomplished using a modification of this approach. Reaction of alkyl-aluminum dichloride with phosphorus oxychloride generates the aluminum chloride complex of the alkylphosphonodichlori-date,54 which may be isolated as the simple compound or directly used in reaction to generate other derivatives of the alkylphospho-nic acid. 

The nickel chloride complex(X) of the spiro-cyclic phosphazene(V) is diamagnetic suggesting a square planar coordination around nickel. The P=N stretching vibration for the complex appears as two split bands(1215 and 1183 cm-1) compared to a single band at 1200 cm-1 observed for the ligand. The phosphorus chemical shifts move upfield compared to those of the ligand the spiro phosphorus atom is the one most affected [complex SpR 21.9 Sp(spir0) 25.5 ... 

The nickel chloride complex(VIII) of N P (NHMe)g is paramagnetic (3.2 B.M.). The phosphorus NMR spectrum shows a single line which shifts upfield by 4.0 6 compared to the ligand. A tetrahedral structure is proposed for this complex in whioh the metal is coordinated to two antipodal nitrogen atoms of the ligand (Figure 2). 

Dodecylbenzenesulfonyl chlorides have been prepared from the corresponding acids using chlorosulfonic acid,4 phosphorus oxychloride,2 and thionyl chloride.5 The use of catalytic amounts of DMF in conjunction with thionyl chloride is based on the work of H. Bosshard, et al. The insolubility of the DMF/thionyl chloride complex in the reaction solvent permits easy removal at the end of reaction. Extraction with dilute base removes the last trace of acids and the solution is pure enough for the next step. 

Chloro-(/7-cyanophenyl)phenylphosphine 349 Dichloro(phenyl)phosphine (60 g) is added to a slurry of i -cyanobenzenediazonium tetrafluoroborate (72 g) and copper(i) bromide (2.4 g) in dry isopropyl acetate (300 ml). After about 20 min a violent reaction sets in which is moderated by external cooling so that the temperature remains between 20° and 40°. When gas evolution ceases, aluminum turnings (8 g) are added and the mixture is stirred for 2 h at 40-50°. Then the liquid is decanted from unused aluminum, and phosphorus oxychloride (51 g) is added to decompose the aluminum chloride complex. Distillation then affords a forerun (5 g), followed by the main fraction (39 g, 47%) between 15870.7 mm and 195°/ 3.1 mm (owing to unavoidable decomposition the pressure does not remain constant during the distillation). Further distillation gives a product boiling at 16270.2 mm. 

The procedure by which phosphorus chlorides react with acetic acid or anhydride was explored by Van Druten and the existence at room temperature of a number of complex esters established. Presumably these are Cl ... 

See also Phosphorus(V) chloride-boron chloride complex, synthesis 24 Phosphorus(V) chloride-gallium(III) chloride complex, synthesis 25... 

The phosphorus (V) chloride-boron chloride complex has been prepared by the chlorination of the phosphorus(III) bromide-boron bromide complex at room temperature, by chlorinating an equimolar mixture of phosphorus (III)... 

Phosphorus(V) chloride-gallium(III) chloride is a moisture-sensitive white crystalline solid melting at 368 to 371°. It is insoluble in carbon tetrachloride and chloroform, reacts with acetone, and is immediately hydrolyzed by water. In comparison with the corresponding phosphorus (V) chloride-boron chloride complex, it is much more difficult to sublime. Indications are that the structure is ionic, [PCl4]+[GaCl4]-. 

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