Triphenyl aminophosphonium Chloride

Tetraammonium pyrophosphate is a colorless, water-soluble crystalline compound which loses ammonia very slowly when exposed to the atmosphere. 

Submitted by Harry H. Sisler and Nathan L. Smith Checked by Peter BarnaI 

The chloramidation of tertiary amines by introducing gaseous chloramide (chloramine) into the anhydrous amine or a solution of the amine in an inert solvent results in the formation of 1,1,1-trisubstituted hydrazonium chlorides. It has been found that a similar chloramidation reaction with tertiary phosphines can be made to yield analogous compounds of the general formula [R3PNH2]C1, i.e., F,P,P-trisubstituted aminophosphonium chlorides. The following aminophosphonium chlorides were prepared by this reaction P,P,P-triphenyl P,P,P-tri-n-butyl P-phenyl-P,P-(cyclotetramethylene) and P-phenyl-P,P-(cyclopenta-methylene). The methodforthe preparation of (triphenyl)-aminophosphonium chloride is given as representative of the procedure. 

The apparatus used for the generation of chloramide is the same as described previously d The gaseous effluent of the chloramide generator (at a flow rate of ca. 0.1 mol of chloramide per hour) is passed into a solution of 5.0 g. (0.19 mol) of triphenylphosphine in 35 ml. of dry benzene maintained at 15 to 25°. Crystallization of (triphenyl)-aminophosphonium chloride begins to occur as the chloramide is passed through the solution. The reaction is continued for 10 to 15 minutes. The reaction mixture is filtered and the residue washed thoroughly with ethyl ether and dried. The washed residue (4.8 to 5.2 g.) consists of (triphenyl) aminophosphonium chloride contaminated with 2 to 4% of ammonium chloride. The yield of aminophosphonium salt is better than 95%. The product, which melts at 224 to 227°, is sufficiently pure for most synthetic work. 

It may be purified by the following procedure. The crude aminophosphonium chloride is dissolved in a conveniently small volume (ca. 25 ml.) of chloroform, leaving most of the ammonium chloride undissolved. After filtration, aminophosphonium crystals of high purity (m.p. 238 to 240° uncor.) are obtained by the addition of cyclohexane to the chloroform solution. The identity of these crystals was checked by elementary analysis. Anal. Calcd. for [(C6H6)3PNH2]C1 C, 68.90 H, 5.42 N, 4.46 P, 9.89 Cl, 11.32. Found C, 68.50 H, 5.75 N, 4.40 P, 9.78 Cl, 11.18. 

---

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... 

P(C6H6)(C4H,)NH2]C1 Phenyl-(cyclotetramethylene)amino-phosphonium chloride, 7 67 [P(C6H5)(C5H4 )NH2]C1 Phenyl-(cyclopentamethylene) amino-phosphonium chloride, 7 67 [P(C6H6)3NH2]C1 (Triphenyl)-aminophosphonium chloride,... 

---