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United States Patent (19) 11) 4,046,656 Davis Et Al

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United States Patent (19) 11) 4,046,656 Davis Et Al United States Patent (19) 11) 4,046,656 Davis et al. 45) Sept. 6, 1977 (54) PHOTOCHLORINATION PROCESS FOR 56) References Cited METHYL AROMATIC COMPOUNDS U.S. PATENT DOCUMENTS (75) Inventors: Ralph A. Davis; R. Garth Pews, both 2,607,802 8/1952 Britton et al. ................ 204/158 HA of Midland, Mich. 3,816,287 6/1974 Bockman et al. ... ..., 204/163 R (73) Assignee: The Dow Chemical Company, Primary Examiner-Howard S. Williams Midland, Mich. Attorney, Agent, or Firm-James B. Guffey (57) ABSTRACT (21) Appl. No.: 747,859 The rate of photochlorination of methyl aromatic con pounds, such as toluene, cresol, xylene, toluenesulfonyl 22 Filed: Dec. 6, 1976 chloride, methylnaphthalene, diphenylmethane, etc., is (51) Int. Cl. ................................................ B01 1/10 increased when carried out in the presence of bromine. (52) U.S. C. ......................... 204/158 HA; 204/163 R (58) Field of Search ..................... 204/158 HA, 163 R 15 Claims, No Drawings 4,046,656 1. 2 zylic hydrogen of the aromatic reactant is replaced by a PHOTOCHLORNATION PROCESS FOR chlorine atom. METHYL AROMATIC COMPOUNDS Methyl aromatic reactants for the photochlorination of which the improved process of the invention is useful BACKGROUND OF THE INVENTION 5 include those of the formula I or II (preferably I). This invention relates to photochlorination of methyl aromatic compounds. H H H Photochlorination of methyl aromatic compounds such as toluene, o- or p-toluenesulfonyl chloride, 3 Arel-R). (R-FA-so-Are-R). chloro-4-methylbenzenesulfonyl chloride, and o-, m- or 10 p-xylenesulfonyl chlorides, is known. See for example (I) (II) British Pat. No. 956,857; British Pat. No. 1,401,038; U.S. Pat. No. 3,230,268; Miller et al., "The Displacement of In the methylated aromatic reactant () or (II) each Aromatic Substituents by Halogen Atoms', Journal of Aris individually an aromatic radical; each R is individ the American Chemical Society, Vol. 79, pp. 4187-4191 15 ually a Y substituent or an aromatic radical, preferably (1957); and Miller, "A Regiospecific Synthesis of 4 a Y substituent; each Y substituent is individually hy Chloroalkylbenzenes", Journal of Organic Chemistry, drogen, chlorine or bromine, preferably hydrogen or Vol. 38, No. 6, pp. 1243-1245 (1973). Although good chlorine, most preferably hydrogen; and each n is indi yields of certain chlorinated products have been re vidually a positive integer, suitably from 1 to 5, prefer ported, the time required to produce chlorinated prod 20 ably from 1 to 3, more preferably 1 or 2, most preferably ucts, in which the benzylic hydrogens have each been 1. replaced by chlorine, are unduly long. As used herein "aromatic radical' includes radicals It would therefore be highly desirable to provide a such as phenyl, biphenyl, naphthyl, phenoxyphenyl, photochlorination process wherein reasonable yields of naphthoxyphenyl, phenylthiophenyl, phenylthionapht methyl aromatic products exhibiting total benzylic hy 25 hyl, aa-dichlorobenzylphenyl, a,a-difluorobenzylphe drogen displacement by chlorine is achieved in reduced nyl and the like, preferably phenyl, biphenyl or naph reaction times, thyl, most preferably phenyl. SUMMARY OF THE INVENTION In the aforementioned aromatic reactants the integer, This invention is an improved process for the photo 30 n, cannot exceed the number of ring positions on the chlorination of methyl aromatic compounds. Such pro aromatic radical, Ar. Further, it is understood that cess comprises contacting the methyl aromatic con when the integer n is less than the number of available pound (hereinafter also referred to as the aromatic reac ring positions on the aromatic radical Ar with which tant) with chlorine in the presence of ultraviolet radia such integer is associated, each of the remaining ring tion and an accelerating amount of bromine. 35 positions is individually occupied by an inert substituent As used herein an "accelerating amount" means an or by a chlorine displaceable (i.e., photodisplaceable) amount of bromine sufficient to measurably increase substituent. (preferably by at least about 25 percent, more prefer Similarly in reactants of the formula I or II wherein ably by at least about 50 percent) the rate of formation the radical R is an aromatic radical, each available ring of a-chloro-substituted methyl aromatic product. position of such radical is individually occupied by an In such process each benzylic hydrogen of the aro inert substituent or by a chlorine displaceable substitu matic reactant is replaced by a chlorine atom, thereby ent. forming the aforementioned a-chloro-substituted aro As used herein the term "inert substituent' means a rnatic product. radical which is not readily displaced from an aromatic Certain of the products thereby produced are valu 45 nucleus by chlorine under photochlorination condi able intermediates for the preparation of selective herbi tions. Suitable inert substituents include, for example, cides, such as N,N-dimethyl-N'-(m-trifluoromethyl hydrogen, fluorine, chlorine, -CF, -OH, -OCF, phenyl)urea; N-ethyl-N-(2-methyl-2-propenyl)-2,6-dini -OCCl3, -SCF, -SCCl3, -SOCF, -SOCCl3 tro-4-(trifluoromethyl)-benzenamine; N-(cyclopropyl -COCF, -COCC -NO, -CN, -NF, and the methyl)-2,6-dinitro-N-propyl-4-(trifluoromethyl)-ben like. Preferred inert substituents includehydrogen, fluo zenamine; N',N'-diethyl-2,6-dinitro-4-(trifluoromethyl)- rine, chlorine, -CF, -OH, -OCF, -OCCl3, - 1,3-benzenediamine; N-(2-chloroethyl)2,6-dinitro-N- NO, and -CN. The most preferred inert substituents propyl-4-(trifluoromethyl)-benzenamine; N-butyl-N- are hydrogen, fluorine and chlorine, especially hydro ethyl-2,6-dinitro-4-(trifluoromethyl)-benzenamine; 2,6- gen and chlorine. dinitro-N,N-dipropyl-4-(trifluoromethyl)-benzenamine; 55 As used herein a "chlorine displaceable substituent” is and the like. a radical which is displaced from an aromatic ring by The presence of bromine in the aforementioned pro chlorine under photochlorination conditions. Examples cess substantially reduces the reaction time required to of such chlorine displaceable substituents include bro obtain the aforementioned a-chloro-substituted methy mine, -SOCl, -SOBr, -SOCH, and -COCH. lated aromatic product in reasonable yields (e.g., at least Preferred chlorine displaceable substituents are bro about 40 percent, more commonly at least about 90 mine, -SOCL and -SOBr, especially -SOCl. percent) based upon the methylated aromatic reactant. In the aforementioned reactants the relative ring posi tions of the -CHRY groups and any inert or photodis DETAILED DESCRIPTION OF THE placeable substituents among themselves (e.g., INVENTION 65 -CHRY relative to -CHRY) and between each other This invention is an improved process for the photo (e.g., -CHRY group relative to an inert or photodis chlorination of methyl aromatic reactants to form a placeable substituent) are not critical. Thus, for exam chloro-substituted aromatic products wherein each ben ple, a -CHRY radical can be ortho, meta or para to 4,046,656 3 4. another such radical or to another ring substituent and rine under photochlorination conditions thereby form other ring substituents can be ortho, meta or para to ing two ring chlorinated aromatic moieties. Thus, such each other. reactants are not generally desirable for the preparation Examples of methyl aromatic reactants of the formula of chloro-substituted aromatic products wherein ring I include methyl benzenes such as toluenes (e.g., tolu 5 chlorination is not desired. ene, a-chlorotoluene, p-chloro-a,c-dibromotoluene, m-bromotoluene, methyl p-tolyl sulfone, methyl m-tolyl Further, since each mole of reactant of the formula II ketone, p-toluenesulfonyl chloride, p-cresol, 3,5-dini or IV provides two moles of chloro-substituted aro trotoluene, 3-cyano-5-(trifluoromethoxy)toluene, di matic product and since a single product is generally phenylmethane, etc.), xylenes (e.g., o-xylene, aa'- desired rather than a product mixture, the two reactant dichloro-m-xylene, a,a-dibromo-p-xylene, 1,3-dimeth 10 moieties (i.e., (CHRYAr- or (CHYid-) are prefer yl-5-nitro-benzene, etc.), trimethylbenzenes (e.g., 1,3,5- ably selected such that the photochlorinated product of trimethylbenzene, 5-bromomethyl-1,3-dimethylben the two moieties will be the same. Most preferably both zene, 1,3,5-tris(chloromethyl)benzene, etc.); methyl reactant moieties in such methyl aromatic reactants are naphthalenes such as 2-methylnaphthalene, 1 themselves the same (i.e., the identity and ring positions (bromomethyl)-3-cyano-naphthalene, 4-bromo-2- 15 of the CHRY- or CHY, groups and the remaining methylnaphthalene, 4-methyl-1-naphthalenesulfonyl substituents on both such moieties are identical). bromide, etc.; methyl biphenyls such as p-phenyltol Bromine is employed as an accelerator in the practice uene, m-(4-bromophenyl)toluene, etc.; methyl di of the invention. The source of bromine can be elemen phenyloxides such as p-(phenoxy)toluene, a-bromo tal bromine or a brominated organic or inorganic com meta-(phenoxy)toluene, etc.; methyl diphenyl sulfides pound which releases bromine under photochlorination such as p-(phenylthio)toluene, 1,3-dimethyl-5-(phenyl conditions. Suitable brominated organic compounds thio)benzene, etc.; and the similar methyl aromatic reac include, for example, carbon tetrabromide, bromoform, tants. dibromodichloromethane, bromobenzene, etc. Suitable The methyl aromatic reactants of the formula II in inorganic bromine compounds include for example, clude methylaryl methylaryl sulfones such as bis(p-
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