Phosphine reaction with, phosgene

Amines of phosphonic and phosphinic acids, on reaction with phosgene, are partially cleaved at the P-N bond. Thus, in addition to the formation of isocyanates. Equation (10.42), a number of by-products (such as the chlorides of the corresponding acids)... 

Triphenylphosphine oxide from the commercial production of vitamin A by a Wittig reaction is recycled by reaction with phosgene to give the phosphine dichloride and reduction of the dichloride to triphenylphosphine with elemental phosphorus (461. Polymeric phosphine oxides have been converted to phosphine dichlorides with oxalyl chloride and then reduced to phosphine with diisobutylaluminum hydride (471. 

A sterically hindered (2,4,6-tri-t-butylphenyl)[bis(trimethylsilyl)]phosphine (9), whose crystal structure has been reported84, was utilized to form a 1-phosphabuta-l,3-diene (equation 67)36. Mes -substituted phosphaketene was obtained from the reaction of 9 with phosgene (equation 68)4. Reaction of 9 with thiophosgene afforded dimeric phosphathioketene, [Mes P=C=S]2 (equation 69)85. A."V3-Dithioxophosphorane was also isolated by introduction of the bulky substituent (equation 70)86. 

The mechanism of the reaction of phosgene with alkyl phosphinates. Equation (10.40),... 

Carbonyl bis(diphenylphosphide) (21), which is stable at room temperature, has been isolated from the reaction of phosgene with diphenyl(trimethyl-silyl)phosphine at —110 °C. 

The reactions of ferrocenylphosphines and tris(diethylamino)phosphine with iodine lead to the formation of iodotri(organo)phosphonium iodides. The related chlorophosphonium chloride obtained from the reaction of tris(dimethyl-amino)phosphine with phosgene has been used as a dehydrating agent for the preparation of A-protected amino-acid amides. ... 

Recently, a polymeric trisubstituted phosphine dichloride (14) was prepared by the reaction of phosgene with polymeric trisubstituted phosphine oxide (13) (Scheme 12-7) (Relies and Schluenz, 1974). This polymeric phosphine dichloride (14) was used for the preparation of acid chlorides. The by-product polymer was also regenerate. 

Preparations and reactions of some mono(trialkylsilyl)phosphines, which derived from bis(trialkylsilyl)phosphines, were described in Sections II.A and II.B. Other preparative methods of mono(trialkylsilyl)phosphines are described in Reference 10. Reactions of some mono(trialkylsilyl)phosphines with hexachloroethane or phosgene lead to chloro-phosphines (equation 42)66. It should be noted that treatment of bis(trialky lsilyl)phosphines... 

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