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 HYDROCARBON 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 Alkane Series a dithiophosphate radical or both radicals for hydrogen Hydrocarbons in a molecule. Methane, ethane, propane, butane, isobutane, pen The process of this invention comprises effecting by tane, isopentane, neopentane, hexane, 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, heptane, 2,4-dimethyl pentane, mula: octane, 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 Toluene, cumene, cymenes, xylenes, durene, diiso propylbenzene, triisopropylbenzene, mesitylene, 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 Cyclopentane, methylcyclopentane, cyclohexane, gen radical replaceable under free radical conditions, methylcyclohexane, 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 naphthalene, norbornane, tetrahydrodicyclopentadi tions, and organic compounds having two or more Satu ene, adamantane, 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