Process for preparing alkyl or aryl phosphorus halides and mixed isomers thereof

Abstract

Alkyl or aryl phosphonic or phosphonothioic dihalides and phosphinic or phosphinothioic monohalides are prepared by reacting an alkyl halide or aryl halide respectively with a tri-valent phosphorus compound having at least two halogens attached thereto, and preferably three two halogens such as phosphorus trihalide, in the presence of P 4 O 10 or P 4 S 10 under at least autogenous pressure at a temperature of from 200° C. to 450° C. The compounds obtained are useful as constituents in insecticides, fungicides, pharmaceuticals, and as intermediates in preparation of other organophosphorus compounds.

What is claimed is: 
     
       1. A method for preparing compounds of the formula: ##STR23## wherein R is a C 1  to C 20  alkyl radical, cycloalkyl of 5-6 carbons in the ring, an aryl radical of up to 3 fused rings, and biphenyl, R 1  represents a C 1  to C 20  alkyl radical, cycloalkyl of 5-6 carbons on the ring, an aryl radical of up to 3 fused rings, biphenyl, or a halogen of chlorine, or bromine, X is a halogen of chlorine or bromine, and Y is a chalcogen of oxygen or sulfur, and m is an integer between 1 and n, defined hereinafter, inclusive, comprising reacting, under at least an autogenous pressure .Iadd.in a reaction zone capable of withstanding elevated pressure .Iaddend.at a temperature of from about 200° C. to about 450° C. an alkyl or aryl halide of the formula:   RX.sub.n     wherein R is as defined above, and X is a halogen of chlorine, or bromine, and n is an integer and represents the number of halogens attached to the R group, with a trivalent phosphorus compound of the formula     R.sub.1 P(X).sub.2     wherein R 1  and X are as defined above, in the presence of a phosphorus compound of the formula:     P.sub.4 Y.sub.10     wherein Y is a chalcogen of oxygen or sulfur.   
     
     
       2. The method as recited in claim 1 wherein R 1  is halogen. 
     
     
       3. The method as recited in claim 1 wherein R 1  and X are chlorine. 
     
     
       4. The method as recited in claim 1 wherein Y is oxygen. 
     
     
       5. The method as recited in claim 1 wherein Y is sulfur. 
     
     
       6. The method as recited in claim 1 wherein R is a C 1  to C 4  alkyl. 
     
     
       7. The method as recited in claim 1 wherein R is aryl of one ring. 
     
     
       8. The method as recited in claim 1 wherein n is 1 and m is 1. 
     
     
       9. The method as recited in claim 1 wherein said reaction is conducted at a temperature of from about 250° C. to about 350° C. 
     
     
       10. The method as recited in claim 1 wherein R is a C 2  alkyl and n is 1 and wherein the reaction mixture further includes a hydrocarbon diluent selected from the group consisting of benzene, ethane, cyclohexane, and ethylene. 
     
     
       11. The method as recited in claim 10 wherein said diluent is ethylene. 
     
     
       12. The method as recited in claim 1 wherein R is an aryl radical of up to 3 fused rings, and wherein the reaction mixture further includes a compound of the formula RH wherein R is the same parent radical forming the R(X) n  used in the reaction. 
     
     
       13. The method as recited in claim 12 wherein said aryl halide is chlorobenzene. 
     
     
       14. The method as recited in claim 12 wherein the trivalent phosphorus compound is phosphorus trichloride. 
     
     
       15. The method as recited in claim 12 wherein the phosphorus compound is P 4  O 10 . 
     
     
       16. The method as recited in claim 12 wherein said phosphorus compound is P 4  S 10 . 
     
     
       17. The method as recited in claim 12 wherein said diluent is benzene. 
     
     
       18. The method as recited in claim 12 wherein said reaction is conducted at a temperature of from 250° C. to 350° C. 
     
     
       19. The method as recited in claim 15 wherein the reaction is conducted in the presence of glass wool. 
     
     
       20. The method as recited in claim 12 wherein said aryl halide is chlorobenzene, said trivalent phosphorus compound is phosphorus trichloride, and said diluent is benzene. 
     
     
       21. Compounds of the formula: ##STR24## wherein n' is an integer of 2 or more, n" equals 0 or 1, n'" is 0 when n" is 0, n'" is 0 or 1 when n" is 1; wherein Y is a chalcogen of oxygen or sulfur, X is a halogen of chlorine, or bromine, and R 1  is a C 1  to C 20  alkyl, cycloalkyl of 5-6 carbons in the ring, an aryl radical of up to 3 fused rings, or biphenyl. 
     
     
       22. Compounds as recited in claim 21 wherein Y is oxygen. 
     
     
       23. Compounds as recited in claim 21 wherein Y is sulfur. 
     
     
       24. Compounds as recited in claim 21 wherein n" is 0. 
     
     
       25. Compounds as recited in claim 21 wherein n' is 2. 
     
     
       26. Compounds of the formula: ##STR25## wherein R 1  is a C 1  to C 20  alkyl radical, cycloalkyl of 5-6 carbons in the ring, an aryl radical of up to 3 fused rings, or biphenyl, R 2  is an alkylene linkage of 2-10 carbons, and X is a halogen of chlorine, or bromine. 
     
     
       27. Compounds as recited in claim 26 wherein X is chlorine. 
     
     
       28. Compounds as recited in claim 26 wherein R 2  is ethylene. 
     
     
       29. Compounds of the formula: ##STR26## wherein Y is a chalcogen of oxygen or sulfur, R 1  is a C 1  to C 20  alkyl radical, cycloalkyl of 5-6 carbons in the ring, an aryl radical of up to 3 fused rings, biphenyl, or a halogen of chlorine, or bromine, X is a halogen of chlorine or bromine and n"" is an integer of 1-5. 
     
     
       30. Compounds as recited in claim 29 wherein Y is oxygen. 
     
     
       31. Compounds as recited in claim 29 wherein Y is sulfur. 
     
     
       32. Compounds as recited in claim 29 wherein R 1  is halogen. 
     
     
       33. Compounds as recited in claim 29 wherein R 1  is chlorine. 
     
     
       34. Compounds as recited in claim 29 wherein X is chlorine. 
     
     
       35. Compounds as recited in claim 29 wherein n"" is an integer of from 1 to 2. 
     
     
       36. Compounds of the formula: ##STR27## wherein R 1  is a C 1  to C 20  alkyl radical, cycloalkyl of 5-6 carbons in the ring, an aryl radical of up to 3 fused rings, biphenyl, or a halogen of chlorine or bromine, X is a halogen of chlorine or bromine, and n'"" is an integer of 2 or more. 
     
     
       37. Compounds as recited in claim 36 wherein R 1  is halogen. 
     
     
       38. Compounds as recited in claim 36 wherein R 1  is chlorine. 
     
     
       39. Compounds as recited in claim 36 wherein X is chlorine. 
     
     
       40. Compounds as recited in claim 36 wherein n'"" is 2. 
     
     
       41. A process for preparing compounds of the formula: ##STR28## wherein R 1  is a C 1  to C 20  alkyl radical, cycloalkyl of 5-6 carbons in the ring, an aryl radical of up to 3 fused rings, biphenyl, or a halogen of chlorine or bromine, and X is a halogen of chlorine or bromine, the free valence bonds being satisfied by hydrogen or C 1  --C 4  alkyl, comprising reacting, under at least autogenous pressure .Iadd.in a reaction zone capable of withstanding elevated pressure .Iaddend.at a temperature of from about 200° C. to about 450° C. an alkyl monohalide of the formula: ##STR29## with a phosphorus compound of the formula:   R.sub.1 P(X).sub.2     in the presence of phosphorus pentasulfide, R 1  and X being as defined hereinbefore.   
     
     
       42. The process as recited in claim 41 wherein R 1  and X are chlorine. 
     
     
       43. The process as recited in claim 41 wherein the free bonds of the alkyl monohalide are satisfied by hydrogens. 
     
     
       44. A process for preparing compounds of the formula: ##STR30## wherein R 1  is a C 1  to C 20  alkyl radical, cycloalkyl of 5-6 carbons in the ring, an aryl radical of up to 3 fused rings, biphenyl, or a halogen of chlorine or bromine, Y is a chalcogen of oxygen or sulfur, and X is a halogen of chlorine, or bromine, .[.the free valence bonds being satisfied by hydrogen or C 1  --C 4  alkyl,.]. comprising reacting .Iadd.ethylene.Iaddend., under at least autogenous pressure .Iadd.in a reaction zone capable of withstanding elevated pressure.Iaddend., at a temperature of from about 200° C. to about 450° C. .[.an ethylenically unsaturated compound of the formula:.]. ##STR31## with a phosphorus compound of the formula:   R.sub.1 P(X).sub.2     in the presence of a phosphorus compound of the formula     P.sub.4 Y.sub.10     R 1 , X and Y being as defined hereinbefore.   
     
     
       45. The process as recited in claim 44 wherein the free valence bonds of the ethylenically unsaturated compound are satisfied by hydrogens. 
     
     
       46. The process as recited in claim 44 wherein R 1  and X are chlorine. 
     
     
       47. The process as recited in claim 44 wherein Y is sulfur. 
     
     
       48. Compounds of the formula: ##STR32## wherein R 3  is cycloalkyl of 5-6 carbons in the ring, R 1  is a C 1  to C 20  alkyl radical, cycloalkyl of 5-6 carbons in the ring, an aryl radical of up to 3 fused rings, biphenyl, or a halogen of chlorine or bromine, X is a halogen of chlorine or bromine and n""" is an integer of 2. 
     
     
       49. Compounds as recited in claim 48 wherein R 1  is halogen. 
     
     
       50. Compounds as recited in claim 48 wherein R 1  is chlorine. 
     
     
       51. Compounds as recited in claim 48 wherein X is chlorine.