Patent GB-762125-A (GB)
Title: Improvements in production of heterocyclic phosphorus-containing compounds
IPC: C07F9/6574
Filed: 1954-02-22
Abstract: The invention comprises heterocyclic phosphorus-containing compounds having the formula <FORM:0762125/IV(b)/1> wherein R, R1, R2, R3 and R4, respectively, each designates a hydrogen atom or an alkyl group; n = 0 or 1; and X is a hydrocarbon radical or a halogen-substituted, alkoxy-substituted or nitro-substituted hydrocarbon radical. Preferably X is an alkyl, alkenyl, haloalkyl, alkoxyalkyl, aryl, nitroaryl or haloaryl radical.  The novel compounds may be prepared by reacting a dihalophosphate ester, derived from a hydroxy compound XOH where X is as defined above, with a solution, in a volatile solvent inert to the reactants, of a glycol having the formula HO.CR2R4.(CRR1)n.CHR3OH, wherein R,R1,R2,R3,R4 and n have the above-defined significance, preferably at a temperature up to 125 DEG C.  The mixture is then refluxed under vacuum before neutralizing the acid by-products with methanolic sodium hydroxide.  Suitable diols are specified.  The novel compounds may also be prepared by reacting a monohydric aliphatic alcohol, a phenyl-paraffin alcohol, a phenol, or a halo-derivative of the alcohol or phenol, or a nitro-derivative of the phenol or phenyl-paraffin alcohol, or the corresponding alkali metal alkoxide or aryloxide, with a 2-halo-2-oxo-1,3,2-dioxaphosphorinane or a 2-halo-2-oxo-1,3,2-dioxaphospholane, and eliminating the by-product hydrogen-halide as formed, e.g. by using a suitable sequestering agent such as pyridine.  The reaction may be effected in the presence of an inert diluent such as benzene, toluene, diethyl ether, dibutyl ether, ethylene dichloride or benzyl chloride, at temperatures ranging from 0-125 DEG  C., depending on the nature of the reactants. Many suitable compounds containing a single alcoholic or phenolic hydroxy group are specified.  The 2-halo-2-oxo-1,3,2-dioxaphosphorinanes or the corresponding dioxaphospholanes may be prepared by reacting an alkane-1,3-diol or an alkane-1,2-diol with phosphoryl chloride or bromide in the presence of a hydrogen halide sequestering agent such as pyridine and an inert volatile solvent such as ether.  The preparation of 2-chloro-5-ethyl-4-propyl-2-oxo - 1,3,2 - dioxaphosphorinane by reacting 2-ethyl-1,3-hexanediol with phosphoryl chloride is described.  Detailed examples are given of the preparation of the (1) 2 - (21 - ethylhexyloxy) - 5 - ethyl - 4 - propyl -; (3) 2 - ethoxy - 5 - methyl - 5 - propyl -; (5) 5 - ethyl - 2 - [21 (211-ethylhexoxy) ethoxy] - 4 - propyl -; (6) 2 - [21-(211 - chloroethoxy) ethoxy] - 5,5 - diethyl -; (7) 2 - [21 - (211,411 - dichlorophenoxy) ethoxy]-5 - ethyl - 4 - propyl -; (8) 2 - allyloxy - 5 - ethyl-5 - butyl -; (9) 5 - ethyl - 2 - phenoxy - 4 - propyl -; (10) 5 - butyl - 5 - ethyl - 2 - phenoxy -; (11) 2 - (p - tert. - butylphenoxy) - 5 - ethyl - 4 - propyl -; (12) 5 - butyl - 2 - (21,41 - dichlorophenoxy) - 5 - ethyl -; (13) 5 - butyl - 5 - ethyl-2 -(p - nitrophenoxy) -; (14) 5 - methyl - 2 - (21-propoxy) - 5 - propyl -; (15) 5 - ethyl - 2 - phenoxy - 4 - propyl -; and (16) 2 - methoxy - 4,4,6-trimethyl-derivatives of 2-oxo-1,3,2-dioxaphosphorinane; and (2) 2 - (21 - ethylhexoxy) - 4-methyl - 2 - oxo - 1,3,2 - dioxaphospholane. The production of many similar compounds is outlined.  Example (4) also describes the preparation of 2-ethylhexyl dichlorophosphate from phosphoryl chloride and 2-ethylhexanol.  The novel products are useful as solvents, plasticizers for synthetic resins and as intermediates.