Patent GB-807119-A (GB)
Title: Phosphate esters
IPC: C07F9/113
Filed: 1956-12-27
Abstract: The invention comprises esters of the formula <FORM:0807119/IV (b)/1> wherein R,R1 represent hydrogen or a hydrocarbon group, R2 represents an aliphatic hydrocarbon group, R3 represents an oxygen-containing group, a is 0, 1 or 2, with the proviso that a + b = 2, and c is 0 or 1, with the proviso that c + d = 1, and b + d is 1, 2 or 3.  R1 is preferably hydrogen or a C1-8 hydrocarbon group, preferably alkyl and R is preferably a hydrocarbon group as for R1.  R2 is preferably an alkylene group, preferably having not more than 10 carbon atoms. Suitable R3 groups include hydroxyl, ether, carboxyl and ester, such as are derived from hydroxycarboxylic acids such as glycollic and lactic acids and esters thereof; aldehyde; keto, including e.g. acetyl, benzoyl, anisoyl, caproyl, acrylyl and crotonyl groups, and substituted groups such as alanyl, anthranoyl, benziloyl and oxamyl; pivalyl; alkoxalyl; glycolyl; glyoxylyl; sulphonic acid group and esters thereof; nitro; nitroso; carbamyl and hydrocarbon substituted derivatives thereof; acyloxy.  More than one group R3 may be substituted on the group R2.  It is preferred that R3 is composed of C, H and O only, and contains not more than 10 C atoms.  The preferred esters are those of b -phosphato-a ,b -olefinically unsaturated monocarboxylic acids with aliphatic polyhydric alcohols, especially glycols, and derivatives thereof, such as partial esters or ethers.  Two subgroups are of particular utility as insecticides, viz. those in which c = 0, a = 2, and in which R, R1, R2, R3 contain not more than 6 C atoms, and those in which c = 1, a = 0 or 1, R not being hydrogen in either group.  The compounds are conveniently prepared by (a) ester-interchange between an ester of a hydrocarbon-substituted b -oxo fatty acid and an alcohol or phenol, R3-R2-OH or an alcohol R-OH; (b) reaction of the products of (a) with sulphuryl chloride to give the a -chlorosubstituted compounds; (c) reaction of these with a phosphite <FORM:0807119/IV (b)/2> wherein a + b = 2, a = 0, 1 or 2 and Rx is generally an alkyl group to give the desired products.  Reaction (c) is effected by adding about an equimolar amount of the phosphite to the chloroester, usually slowly. The reaction may be started at about 20-25 DEG  C., but for the most part is conducted at about 60-150 DEG  C.  Heated may be used to start the reaction and cooling may be necessary to control it.  The formed alkyl chloride is preferably removed by application of vacuum. An inert solvent such as xylene may be used.  Substantially anhydrous conditions are used.  After the addition of the phosphite, the reaction mixture is heated within the indicated temperature range for a sufficient time.  An alternative to reaction (a) is to react the hydroxy compound with diketene or a substituted diketene in the presence of acidic or basic catalysts such as acidic or basic resins, tertiary amines or sulphonic acids, usually at 100-150 DEG  C.  In examples 2-acetoxyethyl acetoacetate is prepared from diketene and 2-hydroxyethyl acetate in the presence of a sulphonic acid ion exchange resin; the following phosphates of the invention are prepared: 2-(2-acetoxyethoxycarbonyl) - 1 - methylvinyl diethyl phosphate from 2-acetoxyethyl 2-chloroacetoacetate and triethyl phosphite, 2-(2-(benzoyloxy) ethoxycarbonyl) - 1 - methylvinyl dimethyl phosphate from 2-benzoyl-oxyethyl 2-chloroacetoacetate and trimethyl phosphite, 2 - (21 - methoxyethoxycarbonyl) 1 - methylvinyl dimethyl phosphate from 2-methoxylethyl 2 - chloroacetoacetate and trimethyl phosphite, diethyl 2 - (methoxyethoxycarbonyl) - 1 - methylvinyl phosphate from 2-methoxyethyl 2 - chloroacetoacetate and triethyl phosphite, 2-carbethoxy-1-methylvinyl ethyl 2-methoxyethyl phosphate from ethyl 2-chloroacetoacetate and diethyl 2-methoxyethyl phosphite, and bis (2-methoxyethyl)-2-(2-methoxyethoxycarbonyl) 1 - methylvinyl phosphate from 2-methoxyethyl 2-chloroacetoacetate and tris (2-methoxyethyl) phosphite.ALSO:Pesticidal compositions comprise esters of the formula <FORM:0807119/VI/1> wherein R, R1 represent hydrogen or a hydrocarbon group, R2 represents an aliphatic hydrocarbon group, R3 represents an oxygen-containing group, a is 0, 1 or 2, with the proviso that a+b=2, and c is 0 or 1, with the proviso that c+d=1, and b+d is 1, 2 or 3.  R1 is preferably hydrogen or a C1-8 hydrocarbon group, preferably alkyl and R is preferably a hydrocarbon group as for R1.  R2 is preferably an alkylene group, preferably having not more than 10 carbon atoms. Suitable R3 groups include hydroxyl; ether; carboxyl and ester, such as are derived from hydroxycarboxylic acids such as glycollic and lactic acids and esters thereof; aldehyde; keto, including, e.g. acetyl, benzoyl, anisoyl, caproyl, acrylyl and crotonyl groups, and substituted groups such as alanyl, anthanoyl, benziloyl and oxamyl; pivalyl; alkoxalyl; glycolyl; glyoxylyl; sulphonic acid group and esters thereof; nitro; nitroso; carbamyl and hydrocarbon substituted derivatives thereof; acyloxy.  More than one group R3 may be substituted on the group R2. It is preferred that R3 is composed of C, H and O only, and contains not more than 10 C atoms.  The preferred esters are those of b  - phosphato - a ,b  - olefinically unsaturated monocarboxylic acids with aliphatic polyhydric alcohols, especially glycols, and derivatives thereof, such as partial esters or ethers.  Two subgroups are of particular utility as insecticides viz. those in which c=0, a=2, and in which R, R1, R2, R3 contain not more than 6 C atoms, and those in which c=1, a=0 or 1, R not being hydrogen in either group (for preparation, see Group IV (b)).  Liquid or solid carriers may be used such as neutral hydrocarbons, e.g. kerosene, talc, bentonite, lime, gypsum, and pyrophyllite.  Solutions may be dispersed in water. Adjuvants, such as spreading or wetting agents may be included, e.g. soaps, rosin salts, saponins, gelatin, casein, long-chain fatty alcohols, sulphonates, phenolethylene condensates and ammonium salts. The proportion of active compound according to the invention is generally 0.01 to 0.5 per cent based on the total weight of the composition, but 0.00001 to 2 per cent or more may be used.  Other active ingredients may be, e.g. pyrethrum, rotenone, sebadilla, D.D.T., benzene hexachloride, aldrin, dieldrin, endrin, thiodiphenylamine, cyanide, tetra ethyl pyrophosphate, diethyl - p - nitrophenyl thiophosphate, azobenzene and various compounds of arsenic, lead and/or fluorine.