Patent GB-807896-A (GB)
Title: Production of spiro heterocyclic phosphorus-containing compounds
IPC: C07F9/6574
Filed: 1955-07-20
Abstract: The invention comprises spiro heterocyclic phosphorus-containing halides having the structure <FORM:0807896/IV (b)/1> wherein R1, R2, R3, R4, R5, R6, R7 and R8 respectively designate an hydrogen or a halogen atom or an alkyl or aryl radical, X is an hydrogen atom, or the two X's collectively represent a second bond between the adjacent carbon atoms, Y is an oxygen or sulphur atom and Hal is a halogen atom.  They may be obtained by reacting a phosphoryl or thiophosphoryl halide, e.g. the chloride, bromide or fluoride with a 1,3-diol having the structure  <FORM:0807896/IV (b)/2> The reaction may, if desired, be carried out in the presence of an inert solvent, e.g. benzene, toluene, xylene, ethylene dichloride, heptane, hexane, ethyl ether and butyl ether.  An excess of either reactant may be used but the use of equimolecular proportions is preferred.  When a phosphoryl halide is used the reaction temperature may be between - 10 DEG  C. and +60 DEG  C. and preferably about 25 DEG  C.  When a thiophosphoryl halide is used the reaction is preferably carried out in the presence of an hydrogen halide acceptor or acid binding agent, e.g. a tertiary amine such as pyridine or dimethylaniline, and in the presence of an inert solvent, e.g. ethylene dichloride or a benzenoid hydrocarbon and the reaction may be conducted at between 10 DEG  and 120 DEG  C. and preferably at 35-45 DEG  C.  Examples are given for the production of spiro-[2-chloro-2-thiono-1,3,2-dioxaphosphorinane) - 5,31 - cyclohexene]; spiro - [(2 - chloro - 2 - oxo - 1,3,2 - dioxaphosphorinane) - 5,31 - cyclohexene]; spiro - [(2 - chloro - 2 - oxo - 1,3,2 - dioxaphosphorinane) - 5,11 - cyclohexane]; spiro - [(2 - chloro - 2 - thiono - 1,3,2 - dioxaphosphorinane) - 5,11 - cyclohexane; spiro - [(2 - chloro - 2 - thiono - 1,3,2 - dioxaphosphorinane) - 5,31 - (41 - methylcyclohexene)]; spiro - [(2 - chloro - 2 - thiono - (or 2-oxo) - 1,3,2 - dioxaphosphorinane) - 5,31 - (21,41,61 - trimethylcyclohexene)] and spiro - [(2 - chloro - 2 - oxo - 1,3,2 - dioxaphosphorinane) - 5,31 - (61 - chlorocyclohexene)]. Other products which may be obtained are spiro-[(2 - chloro - 2 - oxo - 1,3,2 - dioxaphosphorinane) - 5,31 - (21 - phenylcyclohexene)]; spiro - [(2 - chloro - 2 - oxo - 1,3,2 - dioxaphosphorinane) - 5,31 - (21 - methyl - 21 - phenylcyclohexene)]; spiro - [(2 - chloro - 2 - oxo - 1,3,2 - dioxaphosphorinane) - 5,31 - (11 - chloro - 41 - methylcyclohexene)] and spiro-[(2-chloro-2-oxo-1,3,2 - dioxaphosphorinane) - 5,31 - (21,51 - di phenyl - 41 - methylcyclohexene)].  The products are stated to react with alcohols, phenols, amines, alkali metal salts of alcohols and phenols, and ammonia to yield neutral compounds having potential utility as pesticides plasticisers for synthetic resins, hydraulic fluids and oil and gasoline additives.  They may also be converted to monobasic substituted phosphoric acids by controlled hydrolysis.  The 1,3-diols used as starting materials may be obtained by reacting a conjugated diene with an a ,b -unsaturated aldehyde followed by reaction of the resultant aldehyde product with formaldehyde.  Thus, butadiene-1,3 reacts with acrolein to yield 3-cyclohexene-1-carboxaldehyde which then reacts with formaldehyde and aqueous caustic soda to yield 3-cyclohexene-1,1-dimethanol which may be catalytically hydrogenated to form the corresponding cyclohexane-1,1-dimethanol.  Other 1,3-diol preparations mentioned are 6-methyl-3-cyclohexene-1,1-dimethanol from butadiene-1,3, crotonaldehyde and formaldehyde; 2-phenyl-3-cyclohexene-1,1-dimethanol from 1-phenyl butadiene-1,3, acrolein, and formaldehyde; 4 - chloro - 3 - cyclohexene-1,1-dimethanol from chloroprene, acrolein and formaldehyde; 2,4,6-trimethyl-3-cyclohexene - 1,1 - dimethanol from 2 - methyl - 1,3-pentadiene, crotonaldehyde and formaldehyde; 4,6 - dimethyl - 3 - cyclohexene - 1,1 - dimethanol from isoprene, crotonaldehyde and formaldehyde; and 4 - chloro - 6 - methyl - 3 - cyclohexene - 1,1 - dimethanol from chloroprene and crotonaldehyde.