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Jeacocke, Gilbert James (1959) Certain reactions of esters of phosphorus acid and of phosphoric acid. Doctoral thesis, Northern Polytechnic.
The work described is a contribution to a comprehensive investigation into the mutual replacement of alkoxyl (or aryloxyl) attached to an atom of a non-metal such as phosphorus, sulphur, silicon and boron, by halogen attached to an atom of the same, or a different, non-metal. Of especial interest are the examples in which the non-metals are different.
Thus, the interaction of a dialkyl sulphite and phosphoryl chloride led. to stepwise replacement,
(RO)2SO + POCl3 ——> ROSOCl + ROP(O)Cl2
(ROP(O)Cl2 ——> ROSOCl + (RO)2P(O)Cl
(RO)2SO + (RO)2P(O)Cl ——> ROSOCl + (RO)3PO
the alkoxyl group in the chlorosulphinate, ROSOCl, could not be replaced by a chlorine atom attached to phosphorus. Results are explained in terms of the nucleophilic power of oxygen and are correlated with results of experiments on other systems.
The technical production of trialkyl phosphites is of importance, but difficult; as is the process of attaching alkyl groups to phosphorus, which suffers from certain restrictions. Protracted attempts were made to effect both these preparations by the interaction of a dialkyl sulphite and phosphorus trichloride as in the phosphate system.
The system proved extremely difficult to analyse, as was the system in which the Interaction of an alkyl chlorosulphinate with a trialkyl phosphite was examined in order to effect the formation of an alkyl phosphonate, RP(O)(OR')2' or a sulphur compound such as RP(O)S(O)OR or (RO)2P(O)S(O)OR.
Sulphur dioxide, alkyl chloride and a trialkyl phosphate were the established products, but great con fusion was caused by the presence of elusive sulphur compounds probably of the sulphide, mercaptan or thiophosphate type. Mutual replacement
(RO)2SO + PCl3 ——> ROPCl2 + ROSOCl
etc. occurred, but the system was confused in the end by the above mentioned interaction of the trialkyl phosphite and alkyl chlorosulphinate.
Attempts to use amidates for the identification of relevant chloro-esters of phosphorus led to interesting results on the alkylation of amines; while experiments using silicon tetrachloride afforded compounds containing only phosphorus, silicon and oxygen.
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