United States Patent Office Patented Feb

3,305,570 United States Patent Office Patented Feb. 21, 1967 2 3,365,570 carbon radicals may be the same or different aliphatic, HALOGENAEON OF PENTAWALENT-PHOSPHO cycloaliphatic, and/or aromatic radicals. RUS COMPOUNDS-POSYWALENT METAL HA. Examples of the hydrocarbon aliphatic and cycloali HLIDE COMPLEXES WITH POLY HALOMETHANES phatic radicals are methyl, ethyl, propyl, isobutyl, n Willian E. Bacon, Eeni, Ohio, assignor to The Lubrizo 5 hexyl, cyclohexyl, chloro-ethyl, nitro propyl, chloro Corporation, Wickiife, Ohio, a corporation of Ohio cyclohexyl, etc. No Drawing. Fied Gcf. 8, 1963, Ser. No. 314,614 Examples of aromatic radicals are the organic radicals 23 Clains. (C. 260-448) containing at least 1 resonant ring structure such as phenyl, naphthyl, anthracy, phenanthryl, triphenylenyl, The present invention relates to a novel method for O biphenyl, and terphenyl radicals, and the substitution preparing certain phosphorus- and chlorine-containing in products of these such as alkylation products, halogena termediates. More particularly, it relates to a halogena tion products, nitration products, etc. Examples of the tion process. alkylation products include tolyl, cresyi, xylyl, mesityl Compounds which contain phosphorus within their enyl, di-ethyl phenyl, isopropylphenyl, tert-butyl phenyl, molecular structure are, in general, quite useful as addi paraffin wax-substituted phenyl, dodecyl phenyl, etc. tives in insecticides, lubricating oils, hydrocarbon fuels, Examples of the halogenation products include chloro asphalts, plastics and paints. The higher molecular phenyl, dichlorophenyl, bromophenyl, mono- and poly weight, oil-soluble organophosphorus compounds, when chloro Xenyl, mono- and poly-chloro naphthyl, ethyl added in Small proportions to a lubricating oil, impart chlorophenyl, etc. Examples of nitration products in eXtreme pressure properties and tend to diminish the de 20 clude nitro benzene, nitro xenyl, methyl nitrophenyl, etc. composition and Subsequent corrosive properties of such Although any of the above aromatic radicals can be lubricating oils. Consequently, these compounds have utilized, organic radicals containing but one resonant ring been used extensively throughout the broad field of lubri Structure are preferred. cation. The intermediates which result from the novel The phosphorus- and sulfur-containing reactants useful process described herein are useful in the preparation of in the process of this invention may be phosphinomono other phosphorus-containing compositions. Although thioic acids (Y is -OH), phosphinodithioic acids (Y is other methods may be utilized for the preparation of -SH), the esters, anhydrides, and halides of such acids the desired intermediates, those methods suffer from the (Y is -OR, -SR, -O-P(S)RR, -S-P(S)RR', relative unavailability of the starting materials or alter -X, respectively), and phosphinothioic disulfides (Y is natively, produce the desired phosphorus-containing com -S-S-P(S) RR'), and phosphine sulfides (Y is --R). positions in low yields. Phosphinodithioic acids can be prepared by the reac Accordingly, it is an object of this invention to pro tion of Grignard reagents (e.g., butylmagnesium bromide, vide an eficient and low cost method for preparing or Cyclohexyl magnesium iodide) with phosphorus penta ganophosphorus compounds. Sulfide (see Organophosphorus Compounds, G. M. Koso Another object is to provide a process for the prepara lapoff, p. 135, John Wiley and Sons, New York, 1950). tion of halophosphorus compounds. The diaromatic phosphinodithioic acids can also be pre Still another object is to provide a process for the prep pared by heating an aromatic compound (e.g., benzene, aration of organophosphorus acids, esters, oxides, and Xylene, chlorobenzene) a phosphorus sulfide in the pres halides. ence of an aluminum halide as described in U.S. Patent These and other objects of the invention are achieved No. 2,797,238. by a process for preparing halophosphorus comprising The preparation of alkyl aryl phosphinodithioic acids reacting at a temperature of from about 0 to 150° C., is illustrated by the reaction of an alkyl thionophosphine a mixture of sulfide (e.g., (RPS2)2) with an aromatic compound in (a) a phosphorus- and Sulfur-containing complex hav the presence of aluminum chloride as described by ing the formula Newallis et al. in vol. 27, Journal of Organic Chemistry, page 3829. For example, phenylmethyl phosphinodi R. S thioic acid is easily prepared by the reaction of methyl Yp aMX thionophosphine sulfide with benzene in the presence of R / Y aluminum chloride. 50 Examples of the foregoing phosphinodithioic acids are wherein X is a halogen diphenyl phosphinodithioic acid, ditoly phosphinodithioic Y is a radical selected from the class consisting of -OH, acids, di-(chlorophenyl) phosphinodithioic acid, phenyl -OR, -SH, -SR, -O-P(S) RR', tolyl phosphinodithioic acid, di- (wax phenyl) phosphino dithioic acid, phenyl isopropyl phosphinodithioic acid, a is a number from 1 to 2, phenyl methyl phosphinodithioic acid, diethyl phosphino M is a metal selected from the class consisting of alumi dithioic acid, di-(n-propyl) phosphinodithioic acid, and num, iron, tin, and titanium, di-dodecyl phosphinodithioic acid. n is the valence of M, and The organic phosphinomonothioic acids can be pre RandR are hydrocarbon radicals, and pared by the controlled hydrolysis of the corresponding (b) a polyhalomethane having at least three halogen 60 phosphinodithioic acids. radicals. Examples of such phosphinomonothioic acids include The hydrocarbon radicals R and R' of the phosphorus diphenyl phosphinomonothioic acid, ditolyl phosphino reactant (a) are radicals containing preferably from 1 monothioic acid, di-(chlorophenyl) phosphinomonthioic to 30 carbon atoms. These radicais may also contain acid, phenyl isopropyl phosphinomonothioic acid, diethyl polar groups provided, however, that the polar groups 65 phosphinomonothioic acid, and di-(-n-propyl) phosphino are not present in proportions sufficiently large to alter monothioic acid. significantly the hydrocarbon character of this radical. The phosphinodithioic and phosphinomonothioic acid Generally the radicals will contain no more than two esters can be prepared by the reaction of the phosphino polar groups for every ten carbon atoms. Such polar dithioic acid with alcohols and phenols according to the groups are exemplified by the chloro, bromo, keto, ether, procedure described in U.S. Patent No. 2,881,200. Ex aldehyde, nitro, etc. groups. Additionally, the hydro amples of Such esters include methyl diphenylphosphino 3,305,570 3. 4. dithioate, methyl ditolylphosphinodithioate, isobutyl di desired to maintain a constant temperature. A constant tolylphosphinodithioate, phenyl diethylphosphinodithio temperature is not essential, however, for the success of ate, octyl phenyl-methylphosphinodithioate, and cyclo the process. The molar ratio of polyhalomethane to hexyl phenyl-methylphosphinodithioate, methyl ditolyl metal halide complex (a) should be at least 1:1 and is phosphinomonothioate, methyl diethylphosphinomono generally from 1:1 to 2:1. The progress of the reaction thioate, octyl di- (n-propyl) phosphinomonothioate, iso in most cases can be ascertained by the observance of butyl phenyl methylphosphinomonothioate, and phenyl carbon disulfide evolution from the reaction mass. ditolylphosphinomonothioate. Although the exact mechanism by which the reaction The anhydrides of the phosphinothioic acids are easily proceeds is not known, the products of the reaction, which prepared by heating the corresponding acid at a tempera is a halogenation reaction, have in some instances, been ture of about 170° C. for about 5 hours. The phosphino identified. The nature of the particular product, a metal thioic sulfides (i.e., 1,4-disulfido-2,3-dithiatetraphospho halide complex, is dependent upon the nature of the start ranes) which are also useful as the phosphorus- and sul ing phosphorus- and sulfur-containing reactant. In most fur-containing reactant in the process of this invention are instances, sulfur radicals are replaced by halogen radicals. prepared from the corresponding phosphinodithioic acids Thus, the reaction of carbon tetrachloride with the metal by heating with an aqueous solution of hydrogen peroxide. halide complexes of phosphinodithioic acids, phosphin The preparation of the phosphinothioic halides useful othioic halides, phosphinothioic disulfides, and the anhy in the process of this invention may be accomplished eith drides of phosphinodithioic acids produces the correspond er by Sulfurization of the corresponding monochlorophos ing metal halide complexes of trihalophosphoranes as il phine with sulfur or thiophosphoryl chloride, by a Friedel 20 lustrated below in Table I (reactions I-IV). Crafts reaction of an aromatic compound with thiophos The remaining phosphorus- and sulfur-containing com phoryl chloride in the presence of aluminum chloride, or plexes of (a) react with polyhalomethanes to give metal by the reaction of a phosphinodithioic acid with hydrogen complexes of dihalophosphoranes as indicated in reactions chloride. V-IX, Table I. The tertiary phosphine sulfides which are useful in the TABLE I process of this invention as reactant (a) may be prepared by the procedures described in Chapter 6 of Organophos Reaction Starting Material Product phorus Compounds, G. M. Kosolapoff, John Wiley and I-------------- RR'PSSH-aMXn-...----- RR'PClgaMXin Sons, New York, 1950. Suitable examples of such phos - RRPCl2XiaMXi

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