the present invention is a water soluble highly active dimethoate formulation that is less toxic than known dimethoate formulations . the formulations of this invention comprise o , o - dimethyl s -( n - methylcarbamyl ) phosphorodithioate in a solvent system comprising an aliphatic c 1 - c 8 alcohol and an acetate ester of an aliphatic c 1 - c 8 alcohol . the active ingredient , o , o - dimethyl s -( n - methylcarbamyl ) phosphorodithioate ( dimethoate ) is well known in the art . formulations containing dimethoate are diluted in water and subsequently sprayed for agricultural applications . typical commercially available formulations of dimethoate contain from about 20 . 0 % to about 45 % by weight dimethoate . the dimethoate formulations of the present invention contain from about 1 to about 70 % by weight of dimethoate based on the weight of the formulation , preferably from about 45 . 0 to about 60 . 0 % by weight , most preferably from about 56 . 5 to about 57 . 5 % by weight . the solvent system used in the formulations of the present invention comprise a lower alkyl alcohol and a lower alkyl acetate ester . suitable lower alkyl groups are those containing from 1 to 8 carbon atoms , preferably 1 to 4 carbon atoms , most preferably 2 to 4 carbon atoms . useful alcohols include methanol , ethanol , propanol , isopropyl alcohol and all isomers of butanol , pentanol , hexanol , heptanol , and octanol . the preferred alcohols are ethanol , propanol , isopropyl alcohol and butanol . to avoid degradation problems with the alcohol component of the solvent mixture of the present invention , the alcohol used is essentially anhydrous and contains no more than 0 . 15 % water by weight . suitable acetate esters include methyl acetate , ethyl acetate , propyl acetate and all isomers of butyl acetate . the preferred esters are ethyl acetate , propyl acetate and butyl acetate . the solvent mixture should be essentially anhydrous and relatively pure to assure maximum shelf life of the formulation . the ratio of ester to alcohol will vary for different ester / alcohol combinations and according to the amount of dimethoate present . the ratio of ester to alcohol is about 5 : 95 to about 95 : 5 . the optimum ratio is determined by preparing small portions of solutions containing the desired amount of dimethoate and adding various ratios of ester / alcohol mixtures to each and then evaluate the resulting solution for temperature stability and water solubility . for example , the optimum ratio of ester to alcohol for a mixture of ethyl acetate and ethanol for a 58 . 0 % by weight formulation of dimethoate is 1 : 4 . in formulations containing 20 . 5 % by weight of dimethoate , the ratio of ethyl acetate and ethanol would be about 4 : 1 . other ingredients can be added to the formulations of the present invention to enhance product performance or stability of the dimethoate . stabilizers such as those described in u . s . pat . no . 3 , 716 , 636 , herein incorporated by reference , can be added to the formulation . acetic anhydride is an example of a useful stabilizer . the stabilizers are typically added in an amount from about 0 . 50 to about 3 . 5 % by weight of the formulation . formulations containing such a stabilizer are useful in applications involving storage in hot humid areas as in parts of the world having tropical climates . as noted previously , the formulations of the invention do not require the use of emulsifiers or dispersing agents for water solubility or dispersion . known dimethoate concentrates presently available are insoluble in water and require the use of emulsifying agents to disperse the dimethoate concentrate in water . the dimethoate formulations according to the present invention are 100 % water soluble and result in a true solution when the formulation is mixed with water . as a result , prolonged agitation is not required and a more uniform and consistent spray mix is obtained without stratification of the active ingredient from top to bottom . there is improved compatibility of the dimethoate formulation with other possible ingredients in the spray mix such as fertilizers and plant micronutrients . since a true solution is formed , the spray mix is not sensitive to factors such as water hardness , salt content , ph , and silt content that can be detrimental to the emulsions formed from known dimethoate concentrates . formulations according to the present invention are prepared by dissolving dimethoate in the solvent mixture . for ease of mixing , the following order of adding the ingredients is preferred : alcohol , ester then dimethoate . as the concentrations of dimethoate approach the 40 to 60 % range , the temperature of the formulation drops about 6 ° to 10 ° c . to maintain the solubility of the dimethoate , external heat can be applied to the mixing vessel to maintain the temperature in the range of about 32 ° to about 38 ° c . during mixing . the presence of sufficient amounts of ferric and ferrous ions can catalyze decomposition of the dimethoate , therefore , the formulations are preferably prepared in equipment made from stainless steel , polyethylene , polypropylene , or glass . to avoid degradation problems and maximize shelf life , the moisture content of the dimethoate formulation should not exceed about 0 . 25 % by weight of the formulation . in some applications of the dimethoate insecticide concentrates , the addition of surfactants is desired because of the high tension values and hydrophobic surface of most plant tissues . the compositions of the present invention provide a means of delivering such surfactants as integral components of dimethoate concentrates since the compositions require no emulsifiers and the solvent system is compatible with the surfactants . the surfactants are selected from the following known surfactants : ( 1 ) ethoxylated fatty acids ## str1 ## r = alkyl group with 6 to 12 carbons n = 1 - 20 moles of ethylene oxide ( 3 ) alkyl phenol ethoxylates ## str2 ## r = h or c 6 to c 12 alkyl r 1 = h or c 6 to c 12 alkyl ( 4 ) ester ethoxylates ## str3 ## r = c 6 to c 20 n = 1 to 20 ( 5 ) alkyl aryl polyethoxylated phosphate esters ## str4 ## r = c 6 - c 12 n = 4 to 6 ( 6 ) block copolymers ## str5 ## n = 1 to 20 moles of ethylene oxide m = 1 to 20 moles of propylene glycol ( 7 ) alkyl benzene sulfonates ## str6 ## r = linear c 1 - c 6 alkyl group m += counter ion --( ca + 2 , mg + 2 ) ( na + 1 ) the formulations of this invention provide an improved method of diluting dimethoate concentrates for application to plants in order to control damage caused by several species of insects and mites . a detailed listing of those pests controlled by dimethoate can be found in u . s . pat . no . 3 , 987 , 169 . for applications by equipment on the ground , typically about 3 to about 51 . 2 ounces are used in 5 - 400 gallons of spray solution per acre . if application is being made by aerial equipment , about 3 to about 51 . 2 ounces should be applied in 5 - 15 gallons of water . in both cases , the formulation concentration should not exceed 7 . 0 % by volume . the following examples are illustrative of the invention but are not intended in any way to place any limitations on the scope of the invention . a water soluble dimethoate concentrate containing 5 lb . per gallon dimethoate was prepared at room temperature by mixing the following ingredients with mild stirring in a 2 liter glass beaker : ______________________________________component % grams per liter______________________________________dimethoate 60 . 0 630 . 0ethyl alcohol ( anhydrous ) 33 . 0 346 . 5ethyl acetate ( anhydrous ) 7 . 0 73 . 5 100 . 0 1 , 050 . 0______________________________________ for ease of mixing , the following addition order is preferred : ( 1 ) ethyl alcohol --( 2 ) ethyl acetate --( 3 ) dimethoate . after 25 minutes of mild agitation , a clear solution resulted exhibiting the following chemical and physical properties : ______________________________________parameter results______________________________________ % dimethoate 57 . 0grams of dimethoate / liter 598 . 5lbs . of dimethoate / gallon 5 . 0grams per ml 1 . 050water solubility 6 . 5 gms / 100 ccwater miscibility 100 % degradation test @ 30 days @ 45 ° c . ( less than 2 . 0 % dimethoate decompo - sition ) freeze point 38 ° f . ______________________________________ a water soluble dimethoate concentrate containing 4 lb . per gallon dimethoate was prepared at room temperature by mixing the following ingredients with mild stirring in a 2 liter glass beaker : ______________________________________component % grams per liter______________________________________dimethoate ( 95 ) 44 . 70 471 . 6ethyl alcohol ( anhydrous ) 41 . 40 436 . 4ethyl acetate ( anhydrous ) 13 . 90 147 . 1 100 . 00 1 , 055 . 1______________________________________ after 25 minutes of mild agitation , a clear solution resulting exhibiting the following chemical and physical properties : ______________________________________parameter results______________________________________ % dimethoate 42 . 5grams of dimethoate / liter 448lbs . of dimethoate / gallon 4 . 0grams per ml 1 . 055water solubility 7 gms / 100 ccwater miscibility 100 % degradation test @ 30 days @ 45 ° c . ( less than 2 . 0 % dimethoate decompo - sition ) freeze point 34 ° f . ______________________________________ a water soluble dimethoate concentrate containing 2 . 67 lb . per gallon dimethoate was prepared at room temperature by mixing the following ingredients with mild stirring in a 2 liter glass beaker : ______________________________________component % grams per liter______________________________________dimethoate ( 95 ) 32 . 1 336 . 7ethyl alcohol ( anhydrous ) 10 . 0 104 . 9ethyl acetate ( anhydrous ) 57 . 9 607 . 4 100 . 00 1 , 049 . 0______________________________________ after 25 minutes of mild agitation , a clear solution resulting exhibiting the following chemical and physical properties : ______________________________________parameter results______________________________________ % dimethoate 30 . 5grams of dimethoate / liter 320lbs . of dimethoate / gallon 2 . 67grams per ml 1 . 049water solubility 7 . 6 gms / 100 ccwater miscibility 100 % degradation test @ 30 days @ 45 ° c . ( less than 1 % decay ) freeze point less than 32 ° f . ______________________________________ a composition ( composition a ) containing the ingredients shown below was prepared following the process used in examples 1 , 2 and 3 . the ethyl alcohol utilized in examples 1 , 2 and 3 was substituted with the solvent system utilized in conventional dimethoate formulations . ______________________________________component % grams per liter______________________________________dimethoate ( 95 ) 60 . 0 613 . 2xylene range hydrocarbons 33 . 0 337 . 3ethyl acetate 7 . 0 71 . 5 100 . 00 1 , 022 . 0______________________________________ after 25 minutes of mild agitation , the resulting mixture was turbid and found not to be a complete solution . this situation remained even after additional vigorous agitation of the mixture &# 39 ; s components . this indicates that a solution of dimethoate equivalent to that of example 1 was not possible without the ethanol . the incomplete solution produced by comparative example a was allowed to stand undisturbed . a sample of the clear liquid remaining after the undissolved dimethoate had settled out was collected and evaluated for the parameters described in examples 1 , 2 and 3 . ______________________________________parameter results______________________________________ % dimethoate 39 . 7grams of dimethoate / liter 397 . 0lbs . of dimethoate / gallon 3 . 3grams per ml 1 . 0water solubility less than 2 . 0 gms / 100 mlwater miscibility zerodegradation test @ 30 days @ 45 ° c . less than 1 % freeze point 40 ° f . ______________________________________ a composition ( composition b ) containing the ingredients shown below was prepared following the process in example 1 . the ethyl acetate utilized in example 1 , however , was replaced with additional ethanol . ______________________________________component % grams per liter______________________________________dimethoate 95 60 . 00 606 . 0ethyl alcohol ( anhydrous ) 40 . 00 404 . 0 100 . 00 1 , 010 . 0______________________________________ after 25 minutes of mild agitation , the resulting mixture was turbid and not in complete solution . additional agitation was applied for 25 minutes longer and a clear solution was obtained . it was noted , however , that 3 - 5 % of the dimethoate remained undissolved . a sample of the solution was removed from the mixture and evaluated for the following parameters : ______________________________________parameter results______________________________________ % dimethoate 52 . 1grams of dimethoate / liter 526lbs . of dimethoate / gallon 4 . 3grams per ml 1 . 010water solubility 8 grams / literwater miscibility 100 % degradation test @ 30 days @ 45 ° c . 2 . 5 % freeze point 41 ° f . ______________________________________ a review of the values exhibited by comparative examples a and b reveals significant differences between those of example 1 . these differences point out the advantages of utilizing the formulation outlined in example 1 . these advantages are outlined by the following table : ______________________________________ comparative comparativeparameter example 1 example a example b______________________________________ % maximum 57 . 0 39 . 7 52 . 1dimethoate con . maximum lbs . of 5 . 0 3 . 3 4 . 3dimethoate per gallonwater miscibility 100 % zero 100 % maximum water 6 . 5 2 . 0 8 . 0solubility in grams / 100 mlfreeze point in ° f . 36 ° f . 40 ° f . 41 ° f .% dimethoate 2 . 0 1 . 0 2 . 5degradation @ 45 ° c . for thirty days______________________________________ comparison of the above values shows that example 1 offers higher levels of dimethoate concentration , 100 % water miscibility , lower temperature stability , and enhanced water solubility when compared to the values found for comparative example a . even though comparative example b provides both enhanced water solubility and miscibility , the omission of the acetate ester from the formulation limits the maximum amount of dimethoate concentration and raises the composition &# 39 ; s freeze point . the solvent system of example 1 significantly enhanced the solubility of dimethoate in water . the maximum solubility of dimethoate in water reported in the literature is 25 grams per liter at 21 ° c . ( agrochemicals handbook , 2nd ed . royal society of chemists 1987 ). this solubility limit is raised by employing the solvent system described in example 1 . this characteristic is illustrated by the following solubility results : test solutions of known dimethoate concentration were prepared in distilled water buffered to a ph of 2 . 1 . these solutions were maintained at ambient temperature ( 73 ° f .± 1 ° f .) and analyzed by gas liquid chromotography ( glc ) for actual dimethoate content . the % solution is the amount of &# 34 ; pure &# 34 ; dimethoate used to prepare the test solution . this &# 34 ; pure &# 34 ; dimethoate was reported by the manufacturer to contain 98 . 0 % dimethoate . the theoretical % is obtained by multiplying the % solution by the amount of dimethoate ( 0 . 98 ). the actual % dimethoate is the value analyzed by glc . the accuracy of the method utilized was determined to be ± 2 % so the actual amounts can exceed the theoretical amounts . these values were compared to the theoretical ones and categorized in the table below : ______________________________________dimethoate solubility dimethoate theoretical % actual solubility % solution dimethoate dimethoate in gramsby weight by weight by weight per liter______________________________________1 . 0 . 98 . 95 9 . 52 . 0 1 . 96 2 . 10 21 . 03 . 0 2 . 94 2 . 20 22 . 04 . 0 3 . 92 2 . 50 25 . 05 . 0 4 . 90 2 . 30 23 . 06 . 0 5 . 90 2 . 50 25 . 07 . 0 6 . 86 2 . 10 21 . 08 . 0 7 . 84 2 . 50 25 . 0______________________________________ the following table shows the solubility of the dimethoate formulation prepared in example 1 containing 57 . 0 % by weight dimethoate ______________________________________dimethoate solubility of formulation of example 1 theoretical % actual solubility % solution dimethoate dimethoate in gramsby weight by weight by weight per liter______________________________________3 . 0 1 . 71 1 . 78 17 . 84 . 0 2 . 30 2 . 21 22 . 15 . 0 2 . 85 2 . 90 29 . 06 . 0 3 . 42 3 . 41 34 . 17 . 0 3 . 99 3 . 75 37 . 58 . 0 4 . 60 3 . 70 37 . 09 . 0 5 . 10 3 . 60 36 . 0______________________________________ the % solution is the amount of dimethoate formulation used to prepare the test solution . the theoretical % is obtained by multiplying the % solution by the amount of dimethoate in the formulation ( 0 . 57 ). the actual % dimethoate is the value analyzed by glc . the accuracy of the method utilized was determined to be ± 1 - 5 %. the dimethoate solubility achieved with the formulations of example 1 ranged from 34 . 1 to 37 . 5 grams per liter at its maximum limit . this is 27 - 28 % higher than the 25 grams per liter reported for dimethoate in water in agrochemicals handbook .
a water soluble , highly active formulation of o , o - dimethyl s - phosphorodithioate in a solvent system comprising a lower alkyl alchol and a lower alkyl acetate ester is disclosed . the formulations of the present invention are completely water soluble , even in the absence of emulsifiers or other dispersing agents . they contain greater amounts of the active ingredient and display greater tolerance to low temperatures . the mixed solvent system used in these formulations is desirable since it is less toxic than the known solvents .