Patent GB-806638-A (GB)
Title: Organic derivatives of phosphoric acid
Inventor: SCHRADER GERHARD
IPC: C07F9/6571
Filed: 1955-06-17
Abstract: The invention comprises derivatives of phosphoric acid having the general formula <FORM:0806638/IV (b)/1> in which X stands for alkoxy which may be substituted by one or more halogen atoms, aryloxy, alkylmercapto, arylmercapto, or disubstituted amino group, Y is O or S, R1, R2, R3 and R4 are hydrogen or alkyl or aryl radicals, and R5, R6 are hydrogen, halogen, or alkyl radicals.  They may be obtained by reacting a cyclic phosphite of the formula <FORM:0806638/IV (b)/2> with an a -halogenated aldehyde of the formula Hal-C(R5)(R6)-CHO wherein X and Y and the radicals R1 to R6 are as defined above.  The cyclic phosphite may be obtained by reacting the appropriate glycol with phosphorus trichloride and then reacting the product with the appropriate alcohol, phenol, mercaptan, or secondary amine.  Suitable cyclic phosphites are those obtainable from ethylene glycol, 1,2-propylene glycol, 1,2- or 2,3-butylene glycols, hydrobenzoin and thioglycol.  Specified halogenated aldehydes are chloral, bromal, mono- and di - chloro - (and bromo -) acetaldehyde, a -chloro- and a -di-chloropropionaldehyde, and a -chloro and a -bromobutyraldehyde. The reaction temperatures are generally from about 20 DEG  to 100 DEG C. and the reaction may be carried out in an inert solvent, e.g. a hydrocarbon, such as benzene or toluene. Examples are given for the production of (1) O-b -chloroethyl-O-b ,b -dichlorovinyl - O - n - hexylphosphate; (2) O-b  - chloroethyl - O, - b ,b ,b  - trichloroethyl - O-b ,b  - dichlorovinyl phosphate; (3) O - b -chloroethyl - O - b ,b  - dichlorovinyl - O - 2,4 - dichlorphenyl phosphate; (4) O - 4 - chlorophenyl - O - b ,b  - dichlorovinyl - O - b  - chloroethyl phosphate; (5) O - b  - chloroethyl - O - b ,b  - dichlorovinyl - S - methyl thiol phosphate; (6) and (7) the O - b  - chloroethyl, O - b ,b  - dichlorovinyl esters of ethyl and phenyl-thiolphosphoric acids respectively; (8) O-b -chloroethyl - O - b ,b  - dichlorvinylphosphoric acid dimethyl amide; and (9) O - b  - chloroethyl-O - b ,b  - dichlorovinyl - O - methyl phosphate.  The vinyl phosphate products have strong insecticidal properties (see Groups I and VI).  Specifications 783,697 and 784,985 are referred to.ALSO:Plant foods or fertilizers comprise vinyl phosphates of the general formula:- <FORM:0806638/I/1> wherein X is an alkoxy group which may be substituted by one or more halogen atoms, or an aryloxy, alkyl-mercapto, arylmercapto or disubstituted amino group, Y is O or S, R1, R2, R3, and R4 are hydrogen or alkyl or aryl radicals and R5 and R6 are hydrogen, halogen, or alkyl radicals (see Group IVb). Specified vinyl phosphates are those of the above formula wherein Y is oxygen, R5 and R6 are each chlorine, Hal is chlorine, R1, R2, R3 and R4 are each hydrogen and X is O-methyl, O-n-hexyl, O-b ,b ,b ,-trichloroethyl, O-2, 4-di-chlorophenyl, O-4-chlorophenyl, S-methyl, S-ethyl, S-phenyl, and dimethylamino respectively.  Specifications 783,697 and 784,985 [both in Group IV(b)] are referred to.ALSO:Pesticidal and fungicidal compositions comprise vinyl phosphates having the general formula <FORM:0806638/VI/1> wherein X is an alkoxy group which may be substituted by one or more halogen atoms, or an aryloxy, alkylmercapto, arylmercapto or disubstituted amino group, Y is O or S, R1, R2, R3, and R4 are hydrogen or alkyl or aryl radicals and R5, R6 are hydrogen, halogen or alkyl radicals (see Group IV (b)).  Other pesticides or fungicides may be present, e.g. lead arsenate, nicotine, rotenone, pyrethrum, benzene hexachloride, 1,1,1-trichloro-2-2-di(p-chlorophenyl)-ethane, dodecyl thiocyanate, pheno-thiazine, sulphur, copper compounds, and mercury salts.  They may also be used in conjunction with solid carriers, e.g. talc, the bentonites, and chalk, or with liquid carriers, e.g. water, alcohols and saturated, unsaturated, and halogenated hydrocarbons.  They may also be used in the form of liquid suspensions containing an emulsifier.  Specified vinyl phosphates are those of the above general formula wherein Y is oxygen, R5 and R6 are each chlorine, Hal is chlorine, R1, R2, R3 and R4 are each hydrogen, and X is O-methyl, O-n-hexyl, O-b ,b ,b -trichloroethyl, O-2,4-dichlorophenyl, O-4-chlorophenyl, S-methyl, S-ethyl, S-phenyl, and dimethylamino respectively.  Specifications 783,697 and 784,985, [Group IV (b)], are referred to.