Patent GB-759396-A (GB)
Title: Heterocyclic phosphorus-containing compounds and the production thereof
IPC: C07F9/6571
Filed: 1954-02-22
Abstract: The invention comprises amido derivatives of heterocyclic phosphorus-containing compounds having the formula <FORM:0759396/IV(a)/1> wherein R, R1, R2, R3 and R4 represent a hydrogen atom or an alkyl radical; R5 and R6 represent a hydrogen atom or an alkyl, aralkyl, cyanoalkyl, alkaryl, monocyclic aryl or haloaryl radical, or together represent the atoms necessary to complete a morpholinyl or a piperidinyl ring; n is 1 or 0.  The novel compounds are prepared by reacting a compound having a HN= group, such as ammonia, or a primary or secondary alkyl, aralkyl, or cyanoalkyl amine, an aryl, alkaryl or haloaryl amine, or a heterocyclic amine such as morpholine or piperidine, with the corresponding 2-halo-2-oxa-1,3,2-dioxaphospholane or 2-halo-2-oxo-1,3,2-dioxaphosphorinane.  The halogen atom may be chlorine, bromine or iodine.  Suitable amines are mono- and di-methyl, ethyl, butyl, octyl, heptadecyl, 2-cyanoethylphenyl, cresyl, benzyl, p - chlorophenyl or o - bromophenyl amines. Reaction temperatures between - 30 DEG  C. and 130 DEG  C., preferably 10 DEG C. to 80 DEG  C., may be used, and the reaction may be effected in the presence of a hydrogen halide sequestering agent, e.g. pyridine, and a volatile inert solvent such as ethyl ether.  Numerous examples of the process are given, typical products being 2-amido - 5 - ethyl - 4 - propyl -, 2 - di - isopropylamido - 5 - ethyl - 4 - propyl -, 4 - methyl - 2-morpholido -, 2[di(21cyanoethyl)amido] - 5-ethyl - 4 - propyl -, 2(p - chlorophenylamido)-5,5 - diethyl - and 5 - ethyl - 4 - propyl - 2-piperidido - derivatives of 2 - oxo - 1,3,2 - dioxahphosphorinane and 2 - dibutylamido - 4-methyl - 2 - oxo - 1,3,2 - dioxaphospholane.  The 2 - halo - 2 - oxo - 1,3,2 - dioxaphosphorinanes and the corresponding 1,3,2-dioxaphospholanes may be prepared by reacting a phosphoryl halide, such as the chloride or bromide, with a 1,2- or 1,3-alkanediol, such as 1,2-propanediol or 1,3-hexanediol, preferably in the presence of a hydrogen halide sequestering agent and an inert solvent for the reactant.  The reaction is preferably conducted at temperatures of 50 DEG  C. or below, more preferably - 10 DEG  C. to 25 DEG  C.  Detailed examples are given of the preparation of 2-chloro-4-methyl-2-oxo-1,3,2-dioxaphospholane and 2-chloro-5-ethyl-4-propyl - 2 - oxo - 1,3,2 - dioxaphosphorinane from phosphoryl chloride with 1,2-propanediol and 2-ethyl - 1,3 - hexanediol respectively.  Other suitable diols are 2,3- and 2,4-pentanediols, 2-butyl - 2 - ethyl - 1,3 - propanediol, 2,2 - diethyl - 1,3 - propanediol, 2 - methyl - 2,4 - pentanediol, 1,3- and 2,3-butanediols, 1,3-isopentanediol, 1,2-isobutanediol and 2,3-pentanediol.  The 2-halo-starting material may also be prepared by reacting a 2-alkoxy-substituted1,3,2-dioxaphosphorinane or the corresponding dioxaphospholane with a halogen, such as chlorine, bromine or iodine, at a temperature between - 30 DEG  C. and 50 DEG C.  Detailed examples are given of the preparation of 2-bromo5 - butyl - 5 - ethyl - 2 - oxo - 1,3,2 - dioxaphosphorinane and 5 - butyl - 5 - ethyl - 2 - iodo - 2 - oxo - 1,3,2 - dioxaphosphorinane.