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Patel, J. K. (1959) Interaction of boron halides with esters of phosphorus. Doctoral thesis, Northern Polytechnic.
The interaction of boron halides, e.g. boron trichloride, boron tribromide, boron trifluoride with aryl esters of certain acids of phosphorus are described.
Triphenyl phosphite reacts with boron trichloride to give phenyl phosphorodichloridite and triphenyl borate via phenyl chloroboronate which undergoes redistribution. There is no reaction between triphenyl borate and phosphorus trichloride; triphenyl phosphite and boron trichloride were sealed in the tube and heated at 24°, 60-65°, 90-100° (100 hr.). The yield of phosphorus trichloride increased and the yield of phenyl phosphorodichloridite decreased as the temperature rose. Boron tribromide and the phosphite at 100° (40 hr.) gave phosphorus tribromide and triphenyl borate.
Diphenyl bromoboronate was prepared from triphenyl borate (2 mol.) and boron tribromide (1 mol.). The redistribution reaction was studied. The diphenyl bromoboronate dipyridine complex was prepared. The attempt to prepare phenyl dibromoboronite was unsuccessful, but its dipyridine complex was obtained.
Triaryl phosphates, chloridates, dichloridates and phosphoryl chloride formed co-ordination compounds with boron trichloride. Thermal stability, alcoholysis, reaction with pyridine and their infrared spectra were also studied.
The dichloridate-boron trichloride complex on heating up to 300° gave phosphoryl chloride-boton trichloride complex, diphenyl phosphorochloridate and boron trichloride. Similarly the chloridate-boron trichloride complex on heating gave phosphoryl chloride-boron trichloride complex, triaryl phosphate and boron trichloride. Phosphoryl chloride-boron trichloride on heating gave the same complex on sublimation (60%) and the remaining complex (40%) dissociated.
Boron tribromide also formed a complex with triaryl phosphates, and with phosphoryl bromide.
Boron trifluoride formed a complex with triphenyl, m-cresyl, and with p-cresyl phosphate, but failed to do so with p-chlorophenyl and with 2.4-dichlorophenyl phosphates.
Relevant comments on the reaction mechanisms, and properties of the compounds are presented, and attention is drawn to outstanding correlations with other related systems.
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