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United States Patent (19) (11) 3,855,105 Diveley (45) Dec. 17, 1974

54 THOPHOSPHORYLATING ASATURATED 3,284,540 1 1/1966 D'Alelio...... 260/869 GROUP 75 Inventor: William R. Diveley, Oakwood Hills, Primary Examiner-Benjamin R. Padgett Del. Attorney, Agent, or Firm-George H. Hopkins 73 Assignee: Hercules incorporated, Wilmington, (57) ABSTRACT Del. Disclosed is a process for making certain organo thio 22) Filed: June 16, 1969 phosphates and dithiophosphates, a number of which 21 ) Appl. No.: 833,741 have utility as insecticides. The process comprises ef fecting by free radical catalysis at about 0-150°C. re Related U.S. Application Data action of an organic compound characterized by a sat (63) Continuation-in-part of Ser. No. 514,652, Dec. 17, urated carbon with at least one hydrogen replaceable 1965, abandoned. under free radical conditions, and halo-thiophosphate of the formula: 52 U.S. C...... 204/162 R, 204/158 R, 260/329 R, 260/329 P, 260/340.6, 260/347.2, 260/958, 7, OR . 1 / 260/963, 260/971 X-S-P (51) Int. Cl...... B01j 1/10 N 58 Field of Search ...... 204/162, 158; 260/329, OR 260/340.6, 347.2,958, 963,971 wherein X is a halo radical, Z is selected from the (56) References Cited group consisting of the oxo and thioxo radicals, and R UNITED STATES PATENTS and R' are organic radicals. 3,256,370 6/1966 Fitch et al...... 260/972 24 Claims, No Drawings 3,855, 105 2 THIOPHOSPHORYLATING ASATURATED rated carbons, each of which has one or more hydrogen HYDROCARBON GROUP radicals replaceable under free radical conditions. In The application is a continuation-in-part of the co general, a saturated carbon with a hydrogen radical re pending application, Ser. No. 514,652, filed Dec. 17, placeable under free radical conditions undergoes sub 1965, for Method Of Thiophosphorylation Of Organic stitution halogenation under free radical conditions Compounds and now abandoned. when contacted with chlorine or bromine. If a satu This invention is in the chemical arts. It resides in rated carbon with a hydrogen radical results in bromine that part of organic chemistry pertaining to organic decolorization in the presence of light, but not in the thio and dithiophosphates. dark, with formation of hydrogen bromide, the hydro In summary, this invention in one aspect comprises gen radical is replaceable under free radical conditions. a process for the thiophosphorylation of organic com pounds characterized by a saturated carbon having at Examples of an organic compound containing a satu least one hydrogen replaceable under free radical con rated carbon with a hydrogen radical replaceable under ditions. As used in this specification, thiophosphoryla free radical conditions include: tion means the substitution of a thiophosphate radical, 15 Series a dithiophosphate radical or both radicals for hydrogen in a molecule. , , , , , pen The process of this invention comprises effecting by tane, , , , 2 free radical catalysis at about 0-150°C. reaction of methylpentane, 3-methylpentane, 2,2-dimethylbutane, such a compound and a halothiophosphate of the for 20 2,3-dimethylbutane, , 2,4-dimethyl , mula: , docecane, kerosene, paraffin, polyethylene, polypropylene, and the like, Ethers Diethyl ether, dibutyl ether, polyoxyethylene, poly 25 oxypropylene, and the like, OR Acids, Anhydrides, Esters, Amides and Imides Acetic acid, methyl acetate, acetic anhydride, adipic wherein X is a halo radical, Z is selected from the group acid, dimethyl adipate, stearic acid, tristearin, stearic consisting of the oxo and thioxo radicals, and R and R' anhydride, glutaric acid, glutaric anhydride, poly(- are each organic radicals. The overall reaction that 30 methyl methacrylate), ethyl pivalate, N takes place is expressed by the following equation: methylphthalimide, N,N-dimethylpivalamide, and the like, Z, OR Z, OR Nitro-derivatives 1 / 1. -C-I - X-S-P . --> -C-S-P -- IX Nitromethane, nitroethane, and the like, N Free Radical } 35 Halo-derivatives OR' Conditions OR 1,4-dichlorobutane, chlorinated paraffin, butyl chlo ride, and corresponding fluoro, bromo and iodo com wherein pounds, and the like, Aralkane Series . 40 -C- Hydrocarbons , , cymenes, , durene, diiso propylbenzene, triisopropylbenzene, , depicts a saturated carbon in a molecule, which carbon o-methylnaphthalene, (3-methylnaphthalene, polysty has a hydrogen that is replaceable under free radical rene, dibenzyl, and the like, conditions. 45 Ethers The organic compounds that are thiophosphorylated Benzyl ethyl ether, dibenzyl ether, and the like, by the process of this invention comprise compounds Acids, Anhydrides, Esters, Amides and Imides represented by the formulas: Phenylacetic acid, methyl benzoate, methyl phenyl 50 acetate, oy and 6-naphthylacetic acids, o, m, and p R - methyl toluates N,N-dimethyl o, m, and p-toluamide, R'-C-H and R'-C-II N,N-dimethyl acetamide, phenylacetic anhydride, N RVI methylphthalimide, and the like, RIV N- l/ Nitro derivatives 55 Nitrophenylacetic acids (o-, m- and p-), nitrotoluene wherein H is replaceable under free radical conditions, (o-, m- and p-), trinitrotoluene, and the like, R', R'' and R'' are selected from the group consisting Halo derivatives of the hydrogen radical and the aliphatic, cycloali p-chlorotoluene, chlorocumenes, chlorocymenes, phatic, aromatic and heterocyclic, unsubstituted and - and corresponding fluoro, bromo and iodo compounds, substituted radicals, and R' and R'' are organic moi and the like, eties. While under the concepts of this invention the or 60 Alicyclic Series ganic compounds to be thiophosphorylated must have Hydrocarbons at lelast one saturated carbon with at least one hydro , methylcyclopentane, , gen radical replaceable under free radical conditions, , dimethylcyclohexanes, pinane, the process of this invention encompasses organic com trimethylcyclohexanes, camphane, p-menthane, cy pounds having a saturated carbon with two or more hy 65 clooctane, decahydronaphthalene, tetrahydro drogen radicals replaceable under free radical condi , norbornane, tetrahydrodicyclopentadi tions, and organic compounds having two or more Satu ene, , and the like, 3,855, 105 3 4. Halo-derivatives In the process of this invention the organic com Chloropinanes, chlorocamphanes, and correspond pound and the thiophosphorylating agent are admixed ing fluoro, bromo and iodo compounds, and the like, at 0-150°C., preferably at 50-80°C. A normally liquid Heterocyclic Series reaction medium is not necessary, but is desirable par 2-methylthiophene, 3-methylthiophene, 2 ticularly when the organic compound at optimum reac methylfuran, 3-methylfuran, tetrahydrothiophene, tet tion temperatures is a solid or, if liquid, does not func rahydrofuran, dioxane, dithiane, N,N'-dimethylpipera tion as a good liquid reaction medium. When a liquid zine, and the like. As is evident from the foregoing, the reaction medium is used, it preferably is not readily thi process of this invention has broad scope. Not only are ophosphorylated under the particular reaction condi monomeric organic compounds thiophosphorylated 1O tions selected. Chloroform is a suitable liquid reaction thereby, but also polymeric organic compounds are thi medium because it is not readily thiophosphorylated ophosphorylated thereby. under the conditions of the process of this invention. Regarding the thiophosphorylating agent of this in For the same reason, carbon tetrachloride is also a suit vention, which is the halothiophosphate of the formula: able liquid reaction medium. In any event the thiophos 15 phorylation is carried out in the absence of water. Reaction of the thiophosphorylating agent and satu rated carbons with hydrogen radicals replaceable under free radical conditions is effected by free radical catalysis. This kind of catalysis is achieved in some em 20 bodiments of the process of this invention by exposing to ultraviolet light the mixture of organic compound examplels of X comprise the fluoro, chloro, bromo and and thiophosphorylating agent. In other embodiments iodo radicals with the chloro radical usually being pre of the process of this invention it is achieved by admix ferred. R and R' are organic radicals that can be the ing with the mixture free radical generating material. same or different. Examples of such organic radicals 25 This is material which upon the application of heat, ul include unsubstituted and substituted hydrocarbon rad traviolet light or both heat and ultraviolet light reacts icals, and unsubstituted and substituted heterocyclic to form free radicals. Such material comprises one or radicals. Preferred hydrocarbon radicals include the more compounds having this capability. Examples of alkyl, cycloalkyl, aryl, alkaryl and aralkyl, unsubsti such a compound include organic peroxides of all tuted and substituted radicals. Particularly preferred 30 kinds, e.g., benzoyl peroxide, cumyl peroxide, perben are the C-C alkyl radicals such as, for example, the zoic acid, and the like, and inorganic compounds such methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, as persulfates and peroxides of metals. In still other em pentyl (and its isomers), hexyl (and its isomers), and bodiments of the process of this invention both ultravi heptyl (and its isomers) radicals. The thiophos 35 olet light and free radical generating material are em phorylating agent can be made by a number of known ployed. The process of this invention is generally carried out procedures. When Z is the oxo radical one such proce under atmospheric pressure. However, carrying it out dure is that of Michalski, Chem. Abstr. 60, 9135, under subatmospheric and superatmospheric pressures (1964), which is based on the following reaction: are within the broader concepts of this invention. 40 The reaction time employed in the process of this in Rol RO g vention depends upon the organic compound being thi RO - E S -- SO2Cl2 --> P-s Cl - Riv'Cl -- SO2 ophosphorylated. In some embodiments reaction and R v O. RO its completion occur almost instantaneously. In other 45 embodiments reaction is slow and substantial comple wherein R'' is an organic radical that can be the same tion of the reaction can take up to as much as a week. as or different from either one or both of R and R' Generally, however, in such embodiments, the reaction When Z is the thioxo radical one such procedure is that time is in a range from about 1 hour to about 24 hours of Almasi and Paskucz Chem. Ber. 98, 613, (1965). with about 1 hour to about 10 hours being preferred. The quantity of thiophosphorylating agent of this in 50 The thiophosphorylating agent generally has a charac vention relative to the organic compound to be thio teristic color which is different from the color of the phosphorylated is generally such as to enable the de thiophosphorylated compound formed in the reaction. sired extent of thiophosphorylation to be accom Consequently, in many embodiments of the process of plished. In this connection it should be noted that in the this invention the progress of the reaction can be foll 55 lowed by observation of the color of the reaction mix case of unsaturated hydrocarbons and their derivatives ture. Also, in a number of these and other embodi the thiophosphorylating agent of this invention reacts ments the progress of the reaction can be followed by under the conditions of the process of this invention the rate of evolution of hydrogen halide formed in the not only with saturated carbons with hydrogen radicals reaction. replaceable under free radical conditions, but also with 60 Isolation of thiophosphorylated organic compounds unsaturated carbons. Moreover, the thiophosphorylat from the reaction mixture is effected by conventional ing agent under the conditions of the process of this in ways and means. In one procedure, for instance, the vention reacts with basic amino groups in addition to liquid reaction medium and excess organic compound reaction with saturated carbons with hydrogen radicals are removed by aspiration or distillation, and the mate replaceable under free radical conditions. Hence, these rial that remains is distilled or topped in vacuo. other reactions should be taken into account in deter 65 The thiophosphorylated organic compounds ob mining the quantity of thiophosphorylating agent to use tained by the process of this invention are useful com in practicing the process of this invention. pounds. The thiophosphorylated monomeric and low 3,855,105 S 6 polymeric (dimeric, trimeric, tetrameric, etc.) organic These compounds are generally normally liquid. compounds are useful in general as insecticides, as lu They are made by the process of this invention. bricant additives (antioxidants, corrosion inhibitors, The best mode now contemplated of carrying out this sludge dispersants, extreme pressure agents, and the invention is illustrated by the following examples of like), and as intermediates for the synthesis of other various aspects of this invention, which include specific useful compounds. embodiments of the invention. The invention is not lim The thiophosphorylated, so-called high polymers ited to these specific embodiments. In the examples all such as, for example, normally solid polyethylene, nor percentages are by weight, unless otherwise expressly mally solid polypropylene, normally solid polyoxyethyl indicated. In addition, all parts by weight are expressed ene, normally solid polyoxypropylene, and the like, by O as “w,' all parts by volume are expressed as "v,' and the process of this invention give modified polymers all parts by weight (w) and all parts by volume (v) bear that are more receptive to dyes, that can be cross the same relationship as the kilogram to the liter. linked, that can be bonded to various substitutes, that can more readily be graft polymerized with various EXAMPLE 1 monomers, that have increased oxidative stability, and 15 This example illustrates how to make O,O-diethyl that have greater flame resistance. S-chlorophosphorothioate, a thiophosphorylating This invention in another aspect comprises new and agent employed in preferred specific embodiments of useful groups of compounds. These groups of com the process of this invention. pounds, and examples of specific compounds in the Sulfuryl chloride (27.0w) is added dropwise over groups, are listed as follows: O,O-Di(C-C alkyl). S about 30 minutes under anhydrous conditions to well (C-C, alkylbenzyl) phosphorothioates and dithioates. stirred mixture of O,O,O-triethyl phosphorothioate (39.6w) and 75 v) established and maintained O.O-Diethyl S-(2-methylbenzyl) phosphorothioate at-5 - 0°C. The reaction mixture thus formed is main O,O-Diethyl S-(3-methylbenzyl) phosphorothioate tained at -5°- 0°C. for 15 minutes, and then permitted O,O-Diethyl S-(4-methylbenzyl) phosphorothioate 25 to warm to 20-25°C. Benzene is removed by aspira O,O-Dimethyl S-(2-methylbenzyl) phosphorodithio tion, and the residue is distilled in vacuo. The desired ate product (36.4w) is collected at 62-63°C. at a pressure The first, second and fourth specific compounds are of 0.3 millimeter of mercury. This product, consisting useful as insecticides and the third is useful as a lubri essentially of O,O-diethylS-chloro phosphorothioate, cant additive. O,O-Di(C-C alkyl) S-(C-C8 cycloal 30 tpyically is a yellow liquid. It is hereinafter referred to kyl) phosphorothioates and dithioates as Example 1 product. O,O-Diethyl S-cyclohexyl phosphorothioate O,O-Diethyl S-cyclopentyl phosphorothioate EXAMPLE 2 O,O-Dimethyl S-cyclobutyl phosphorodithioate 35 This example illustrates the product of O,O-diethyl All of these specific compounds are useful as lubricant S-benzyl phosphorothioate by a preferred specific em additives. O,O-Di(C-C alkyl) S-norbornyl phos bodiment of the process of this invention. phorothioates and dithioates Toluene (36.8w) and carbon tetrachloride (125 v) O,O-Diethyl S-norbornyl phosphorothioate are charged to a reactor. While the resulting mixture is O,O-Dimethyl S-norbornyl phosphorodithioate 40 stirred, it is illuminated with ultraviolet light and heated These specific compounds are useful as inseciticides. to reflux temperatures. While a stream of nitrogen is O,O-Di(C-C alkyl) S-(2-furanylmethyl) phosphoro passed slowly through the reactor, a solution of Exam thioates and dithioates ple 1 product (15.34 w) in carbon tetrachloride (25 v) O,O-Diethyl S-(2-furanylmethyl) phosphorothioate is added dropwise to the mixture over a period of 1 O,O-Dimethyl S-(2-furanylmethyl) phosphorodithio 45 hour. The temperature is maintained at 65°-80°C. Soon ate after addition of the solution is started, hydrochloric These specific compounds are useful as insecticides. acid copiously evolved from the resulting reaction mix O,O-Di(C-C alkyl) S-(acetoxymethyl) phosphorothi ture. For quite some time after the addition of the solu oates and dithioates tion is started, its yellow color instantly disappears O,O-Diethyl S-(acetoxymethyl) phosphorothioate 50 upon mixing with the water white reaction mixture, but O,O-Dimethyl S-(acetoxymethyl) phosphorodithio as the addition proceeds, this no longer occurs and the ate reaction mixture acquires a light yellow color. Illumina These specific compounds are useful as insecticides. tion of the reaction mixture with ultraviolet light is con O,O-Di(C-C alkyl) thio and dithiophosphorylated tinued for two hours after completion of the addition chlorinated camphene 55 of the solution. Typically at this time a few drops of the O,O-Diethyl thiophosphorylated 60-72 weight % reaction mixture added to a 10% aqueous potassium chlorinated camphene iodide solution (3v)-carbon tetrachloride (3v) mixture O,O-Dimethyl dithiophosphorylated 60-72 weight % fails to liberate iodine, thereby indicating substantially chlorinated camphene These specific compounds are complete consumption of O,O-diethyl S-chloro phos useful as insecticides. 60 phorothioate, and thus substantial completion of the alkyl) S-(2-carboxy-2-methylpropyl) reaction. phosphorothioates and dithioates. The carbon tetrachloride is removed by aspiration O,O-Diethyl S-(2-carboxy-2-methylpropyl) phos and the residue distilled in vacuo. After discarding a phorothioate small forerun, a light tan liquid fraction (13.9 w) is col 65 lected at 125-132C. at a pressure of 0.4 millimeter of O,O-Dimethyl S-(2-carboxy-2-methylpropyl) phos mercury. phorodithioate This fraction is redistilled and the desired product, a These specific compounds are useful as insecticides. water-white liquid (10.75 w), is collected at 3,855, 105 7 8 1 16-120°C. at a pressure of 0.1 millimeter of mercury. uct (21.4 w), which distills at 128-135C. at 0.15 milli This product consists essentially of O,O-diethyl S meter of mercury pressure is obtained. This product, benzyl phosphorothioate. It typically analyzes: S = typically a tan liquid analyzing: S = 12.3% (Calculated: 13.0%, P = 12.6% (Calculated: S= 12.3%, P = 11.9%). S = 11.7%) consists essentially of O,O-diethyl S-(4- 5 methylbenzyl) phosphorothioate. This product is useful as an insecticide and as a fungi This product is useful as a lubricant additive. cidal. EXAMPLE 7 EXAMPLE 3 This example illustrates O,O-diethyl S-cyclohexyl This example illustrates the making of O,O-diethyl O phosphorothioate and its synthesis by a preferred spe S-benzyl phosphorothioate by another preferred spe cific embodiment of the process of this invention. cific embodiment of the process of this invention. Following the Example 4 reaction and product sepa The reactants, quantities of reactants, reaction pro ration procedures, cycohexane (42 w) in carbon tetra cedure and product isolation procedure of Example 2 chloride (125 v), and Example 1 product (18.0 w) in are the same, except that ultraviolet light illumination 15 carbon tetrachloride (25 v) are reacted, and the de is omitted while benzoyl peroxide (0.05 w) is added to sired end product (8.75 w), boiling at 105-115°C. at the initial mixture of toluene and carbon tetrachloride 0.15 millimeter of mercury pressure is obtained. This prior to adding the solution of O,O-diethyl product, typically a water-white liquid analyzing: S = S-chlorophosphorothioate and carbon tetrachloride. 13.2%, P = 12.8% (Calculated: S = 12.7%, P = 12.3%), The results typically are substantially the same as in Ex 20 consists essentially of O,O-diethyl S-cyclohexyl phos ample 2. phorothioate. EXAMPLE 4 This product is useful as a lubricant additive. This example illustrates O,O-diethyl S-(2- EXAMPLE 8 methylbenzyl) phosphorothioate and its synthesis by a 25 O,O-Diethyl S-cyclopentyl phosphorothioate and its preferred specific embodiment of the process of the in synthesis by a preferred specific embodiment of the vention. Following the Example 2 reaction procedure and the process of this invention are illustrated by this example. Example 2 product isolation procedure, but omitting Following the Example 4 reaction and product sepa the redistillation step, o- (53 w) in carbon tetra 30 ration procedures, cyclopentane (35 w) in carbon tet chloride (100 v), and Example, 1 product (17.5 w) in rachloride (125 v), and Example 1 product (18.5 w) in carbon tetrachloride (25 v) are reacted, and the de carbon tetrachloride (25 v) are reacted, and the de sired end product (18.3 w) collected at 128-140°C. at sired end product (12.0 w), distilling at 102°-107°C. at a pressure of 0.2 millimeter of mercury. The product, 0.5 millimeter of mercury pressure, is obtained. This . typically a light tan liquid, consists essentially of O,O- 35 product, typically a tan liquid analyzing: S = 13.8%, P diethyl S-(2-methylbenzyl) phosphorothioate. A typi = 13.4% (Calculated: S = 13.4%, P = 13.0%), consists cal analysis of the product is: S = 12.0%, Cl = 0.33% essentially of O,O-diethyl S-cyclopentyl phosphorothi (Calculated: S = | 1.7%, C = 0.0%). date. This product is useful as an insecticide. 40 This product is useful as a lubricant additive. EXAMPLE 5 EXAMPLE 9 This example illustrates O,O-diethyl S-(3- This example illustrates O,O-diethyl S-norbornyl methylbenzyl) phosphorothioate, and its preparation phosphorothioate, and its production by a preferred by a preferred specific embodiment of the process of 45 specific embodiment of the process of this invention. this invention. Following the Example 4 reaction and product sepa Following the reaction and product separation proce ration procedures, norbornane (48.0 w) in carbon tet dures of Example 4, m-xylene (53 w) in carbon tetra rachloride (125 v), and Example 1 product (18.8 w) in chloride (100 v), and Example 1 product (17.5 w) in carbon tetrachloride (25 v are reacted, and the desired carbon tetrachloride (25 v) are reacted, and the de end product (9.6 w), distilling at 106°-125°C. at 0.15 sired end product (16.4 w), which distills at 50 millimeter of mercury pressure is obtained. This prod 128-134°C. at 0.15 millimeter of mercury pressure, is uct, typically a yellow liquid analyzing: S = 13.0%, P = obtained. This product, typically a light pink liquid, 12.7% (Calculated: S = 12.1%, P = 1 1.7%), consists es consists essentially of O,O-diethyl S-(3-methylbenzyl) sentially of O,O-diethyl S-norbornyl phosphorothioate. phosphorothioate. A typical analysis of this product is: S = 12.2%, C = 0.29% (Calculated: S = 1 1.7%, Cl = 55 This product is useful as an insecticide. 0.0%). This product is useful as an insecticide. EXAMPLE 10 This example illustrates the synthesis of O,O-diethyl EXAMPLE 6 S-hexyl phosphorothioate by a preferred specific em This example pertains to O,O-diethyl S-(4- 60 bodiment of the process of this invention. methylbenzyl) phosphorothioate, and its production by By the reaction and product separation procedures of a preferred specific embodiment of the process of this Example 4, n-hexane (43.0 w) in carbon tetrachloride invention. (100 v), and Example 1 product (18.0 w) in carbon tet By the reaction and product separation procedures of 65 rachloride (25 v), are reacted, and the desired end Example 4, p-xylene (53 w) in carbon tetrachloride product (7.4 w), distilling at 95-115°C. at 0.4 millime (100 v), and Example 1 product (18w) in carbon tetra ter of mercury pressure, is obtained. This product, typi chloride (25 v) are reacted, and the desired end prod cally a water-white liquid analyzing: S = 12.8%, P =

3,855,105 10 13.1%, Cl= 0.79% (Calculated: S = 12.6%, P = 12.2%, reacted. However, the reaction mixture is treated Cl = 0.0%), consists essentially of O,O-diethyl S-hexyl somewhat differently to obtain the desired end prod phosphorothioate. uct. The excess pivalic acid is distilled off, and the resi This product is useful as a lubricant additive. due (28.2 w) is dissolved in benzene (200 v). Water (50 v) is added to the benzene solution and then 1 M EXAMPLE 11 aqueous solution (91 v) of potassium hydroxide is This example relates to O,O-diethyl added. The water layer that forms is separated and furanylmethyl) phosphorothioate, and its synthesis by made strongly acid with 5% aqueous hydrochloric acid a preferred specific embodiment of the process of this solution. Typically an organic layer separates. This or invention. 10 ganic layer is extracted with diethyl ether and the ex . By the reaction and product separation procedures of tract dried over sodium sulfate. The diethyl ether is re Example 4, 2-methylfuran (41.0 w) in carbon tetra moved by aspiration and the residue topped at 60°C. at chloride (100 v), and Example 1 product (18.0 w) in less than 1 millimeter of mercury pressure. The residue carbon tetrachloride (25 v) are reacted, and a crude (18.1 w), typically a viscoustan liquid, is the desired product (10.9 w), distilling at 1 1 0°-123°C. at 0.5 milli 15 end product. It consists essentially of O,O-diethyl meter of mercury pressure, typically a brown liquid, is S-(2-carboxy-2-methylpropyl) phosphorothioate. obtained. This crude product is redistilled to give the This product is useful as an insecticide. desired end product (9.0 w), distilling at 98°-105°C. at 0.15 millimeter of mercury pressure. This end product EXAMPLES 15-49 typically is a yellow liquid analyzing: S = 13.0%, P = 20 These examples illustrate other specific embodi 13.4%, Cl- 0.17% (Calculated: S = 12.8%, P = 12.4%, ments of the process of this invention, and of other thi Cl = 0.0%). It consists essentially of O,O-diethyl S-(2- ophosphorates of this invention. furanylmethyl) phosphorothioate. By following the reaction and product separation This product is useful as an insecticide. procedures of Example 4 with Example 1 product as 25 the thiophosphorylating agent, the corresponding thio EXAMPLE 12 phosphate derivatives of the following tabulated or This example illustrates O,O-diethyl S ganic compounds are obtained. The utilities of these (acetoxymethyl) phosphorothioate and its preparation derivatives are indicated in the table. by a preferred specific embodiment of the process of this invention. 30 By the reaction and product separation procedures of Example 4, methyl acetate (74 w) in carbon tetrachlo Example Organic Compound Utility of Thiophos ride (125 v), and Example 1 product (18.25 w) in car phate Derivatives 15 m-isopropylphenyl N-methyl insecticide bon tetrachloride (25 v) are reacted, and the desired carbamate end product (6.1 w), distilling at 117-130°C. at 35 16 Adduct of and Insecticide Hexachloro cyclopentadiene 0.5-0.6 millimeter of mercury pressure, is obtained. 17 dimethyl glutarate insecticide This product, which typically analyzes: S = 13.2% (Cal 18 methyl p-toluate insecticide culated: S = 13.2%), consists essentially of O,O-diethyl 2019 p-tolylNSSE N-methyl phthalimide carbamate Insecticideinsecticide S-(acetoxymethyl) phosphorothioate. 21 m-tolyl N-methyl carbamate Insecticide This product is useful as an insecticide. 40 22 p-isopropylphenyl N-methyl Insecticide carbamate EXAMPLE 13 23 bornyl chloride Insecticide 24 durene Lubricant additive . This example illustrates the O,O-diethyl thiophos 25 mesitylene Lubricant additive 26 dimethyl sebacate lnsecticide phorylated chlorinated camphene, and its synthesis by 27 methyl decanoate Lubricant additive a preferred specific embodiment of the process of this 45 28 methyl stearate Lubricant additive 29 N,N-diethyl-m-toluamide Lubricant additive invention. 30 a.o-dimethylpentanoic acid Insecticide By the reaction and product separation procedures of 31 methyl-o-toluate Insecticide 32 2,4-dichlorotoluene Insecticide Example 4, chlorinated camphene (40 w) (saturated), 33 3,4-dichlorotoluene Insecticide analyzing 64% chlorine, in carbon tetrachloride (75 v), 34. dioxane Insecticide 50 35 2,3-dichlorodioxane Insecticide and Example 1 product (18.5% w) in carbon tetrachlo 36 tetrahydrodicyclopentadiene insecticide. ride (25 v) are reacted, and the desired end product 37 N-methylphthalimide insecticide (54.4 w), distilling at 58-84°C. at 0.25 millimeter of 38 tetrahydrofuran insecticide 39 6-methylnaphthalene Lubricant additive mercury pressure, is obtained. This product, typically 40 2-methylthiophene Insecticide a tan liquid analyzing: S = 4.4%, Cl = 49.9% (Calcu 41 p-menthane Insecticide lated: S = 6.2%, Cl = 41.6%), consists essentially of 42 decahydronaphthalene Insecticide O,O-diethyl thiophosphorylated chlorinated cam 43 OOO-triethylphosphorothioate. Lubricant additive phene. 44 indane Insecticide 45 Cuee Insecticide This product is useful as an insecticide. 46 N,N-dimethylpivalamide Insecticide 47 l,1,1,5-tetrachloropentane Insecticide EXAMPLE 14 60 48 methyl 4-chlorobutyrate Insecticide This example pertains to O,O-diethyl S-(2-carboxy 49 1,4-dichlorobutane Insecticide 2-methylpropyl) phosphorothioate and its synthesis by a preferred specific embodiment of the process of this invention. EXAMPLE 50 By the reaction procedure of Example 2, pivalic acid 65 This example illustrates how to make O,O-diethyl S (40.8 w) in carbon tetrachloride (125 v), and Example benzyl phosphorodithioate by a preferred specific em 2 product (18.0 w) in carbon tetrachloride (25 v) are bodiment of the process of this invention.

3,855,105 11 12 A dithiophosphorylation agent consisting essentially chloro radical, Z is the oxo radical, and R and R" are of O,O-diethyl S-(chlorophosphorodithioate) is made Cr-C, alkyl radicals. by the procedure of Almasi and Paskucz, Chem. Ber. 5. A process according to claim 4, wherein said or 98, 613 (1965). ganic compounds is a hydrocarbon. Following the reaction and product separation proce 6. A process according to claim 5, wherein said or dures of Example 4, toluene (56.8 w) in carbon tetra ganic compound is n-hexane. - chloride (125 v), and the dithiophosphorylating agent 7. A process according to claim 5, wherein said or-. (16.5 w) in carbon tetrachloride (25 v) are reacted and ganic compound is cyclohexane. the desired end product is obtained. This product con 8. A process according to claim 5, wherein said or sists essentially of O,O-diethyl S-benzyl phosphorodi 10 ganic compound is cyclopentane. thioate. 9. A process according to claim 5, wherein said or This product is useful as an insecticide. ganic compound is toluene. Thus, this invention provides a new and useful pro 10. A process according to claim 5, wherein said or cess, and new and useful compounds. ganic compound is a xylene selected from the group Other features, advantages and specific embodiments 15 consisting of o-, m- and p-xylenes. of this invention will be readily apparent to those exer 11. A process according to claim 5, wherein said or cising ordinary skill in the art after reading the forego- . ganic compound is mesitylene. ing disclosures. Such specific embodiments are within 12. A process according to claim 5, wherein said or the scope of the claimed subject matter, unless other ganic compound is norbornane. wise expressly indicated. Also, while specific embodi 20 ments of this invention have been described in consid 13. A process according to claim 5, wherein said or erable detail, variations and modifications of them can ganic compound is p-menthane. be effected without departing from the spirit and scope 14. A process according to claim.4, wherein said or of the invention substantially as disclosed and claimed. ganic compound is a heterocyclic compound. 25 15. A process according to claim 14, wherein said or The term "consisting essentially of as used in this ganic compound is 2-methylfuran. specification excludes any unrecited substance at a 16. A process according to claim 14, wherein said or concentration sufficient to substantially adversely af ganic compound is 2-methylthiophene. fect the essential properties and characteristics of the 17. A process according to claim 14, wherein said or composition of matter being defined, while permitting 30 ganic compound is dioxane. the presence of one or more unrecited substances at 18. A process according to claim 4, wherein said or concentrations insufficient to substantially adversely ganic compound is methyl acetate. affect said essential properties and characteristics. 19. A process according to claim 4, wherein said or What I claim and desire to protect by letters Patent ganic compound is pivalic acid. S. 35 20. O,O-Di(C-C, alkyl) S-(C-C, alkylbenzyl) phos 1. A process for thiophosphorylating a saturated car phorodithioates. bon of an organic compound, which carbon is charac 21. O,O-Di(C-C alkyl) S-norbornyl phosphorodi terized by at least one hydrogen radical replaceable thioates. under free radical conditions, which comprises effect 22. O,O-Di(C-C alkyl) thio and dithiophos ing by free radical catalysis at about 0-150°C. reaction 40 phorylated chlorinated camphenes. of said organic compound and a halothiophosphate of 23. O,O-Di(C-C, alkyl) S-(2-carboxy-2- the formula methylpropyl) phosphorothioates and dithioates. 24. A process for thiophosphorylating a saturated carbon of an organic compound, which carbon is char 45 acterized by at least one hydrogen radical replaceable under free radical conditions, which comprises expos ing at 0-150°C. to ultraviolet light a mixture of said or ganic compound and a halothiophosphate of the for wherein X is a halo radical, Z is selected from the group mula: consisting of the oxo and thioxo radicals, and R and R' 50 are organic radicals. 2. A process according to claim 1, wherein said free X-S-P3 or radical catalysis is obtained at least by admixing said N organic compound and halothiophosphate with an ef OR ----- fective quantity of free radical generating material. 55 3. A process according to claim 2, wherein said free wherein X is halo, Z is selected from the group consist radical generating material comprises an organic per ing of oxo and thioxo, and R and R' are organic radi oxide. cals. 4. A process according to claim 1, wherein X is the ck xk xk xk xk 60

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