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United States Patent (19) 11) 4,251,675 Engel 45 Feb United States Patent (19) 11) 4,251,675 Engel 45 Feb. 17, 1981 (54) PREPARATION OF DIPHENYLMETHANE OTHER PUBLICATIONS 75 Inventor: Dusan J. Engel, Des Plaines, Ill. M. Robert Jenny, Comptes Reuda 250, 1659-1661, 73) Assignee: UOP Inc., Des Plaines, Ill. 1960. 21 Appl. No.: 21,043 Primary Examiner-Veronica O'Keefe a. Attorney, Agent, or Firm-James R. Hoatson, Jr.; (22 Filed: Mar. 15, 1979 Raymond H. Nelson; William H. Page, II 5251) Int,U.S.C. Cl’.............................................. .585/22,585,446. C07C 15/16 57 ABSTRACT 585/454; 585/469 Diphenylmethane is synthesized by reacting benzene 58 Field of Search ................................ 585/469,422 and benzyl chloride at elevated temperatures in a Frie o del-Crafts type reaction using catalytic amounts of a 56) References Cited Friedel–Crafts metal halide catalyst such as ferric chlo U.S. PATENT DOCUMENTS ride whereby the desired product is obtained with a 3,006,972 10/1961 Fields et al. ......................... 585/422 good selectivity and a high conversion rate. 3,079,448 2/1963 Jenny ................................... 585/422 3,833,677 9/1974 Grard ................................... 585/422 1 Claim, No Drawings 4,251,675 2 in the presence of a catalytic amount of ferric chloride, PREPARATHON OF DEPHENYLMETHANE As another indication of the relative inactivity of an unsubstituted aromatic compound such as benzene, BACKGROUND OF THE INVENTION H.C. Brown in the Journal of Organic Chemistry, Vol It is known in the prior art that aromatic compounds 5 ume 23, pages 414-416 discloses on page 415 that when which are rich in electrons, such as those which contain using nitrobenzene as a solvent, benzene has a relative various substituents on the aromatic ring, may be re rate of only 1/154 as compared to the rate of toluene acted in Friedel-Crafts type reaction. For example, which has been given a relative rate of 1.00 in a benzoy benzophenone may be synthesized by reacting benzene lation reaction. The same author in the Journal Of The plus benzoyl chloride, benzoic anhydride or benzoic 10 American Chemical Society, Volume 81, pages acid in the presence of metal halides such as aluminum 3308-3310 also discloses at Table 2 in page 3309 when chloride, titanium tetrachloride, antimony pentachlo using ethylene chloride or benzoyl chloride as the sol ride, molybdenum pentachloride, etc. However, it has vent, the benzene is relatively inactive as opposed to been reported in the prior art that a combination of toluene and the xylenes in a benzoylation reaction. aluminum chloride with ferric chloride as the catalyst 15 These references would also teach away from the pro gave a detrimental action to obtaining desired yields of cess of the present invention, that is, that benzene may benzophenone. However, the catalysts which are used be reacted with a benzyl halide in the presence of a in this reaction are present in stoichiometrical amounts, catalytic amount of ferric chloride inasmuch as benzene thus adding to the cost of the desired product. is an unreactive or electron poor aromatic compound. It has also been reported in the literature that ferric 20 This invention relates to a process for synthesizing chloride may be used as a catalyst for Friedel-Crafts diphenylmethane by reacting benzene with a benzyl reactions involving benzene. However, the ferric chlo halide in the presence of a catalytic amount of a Friedel ride was always present in stoichiometric amounts Crafts catalyst. when used as a catalyst for reactions involving benzene, The desired product of the present invention con due to the relative unreactiveness of the benzene, which 25 prises diphenylmethane which is a precursor to benzo is an electron poor aromatic compound. In constradis phenone. The latter product can be synthesized from tinction to this, when using electron rich aromatic com diphenylmethane by an air oxidation step using an or pounds such as toluene, the isomeric xylenes, anisole, ganometallic complex in a catalytic amount. However, etc., wherein the benzene is provided with a reactive heretofore this was not a preferred method inasmuch as substituent, it is possible to use ferric chloride in less 30 it has been relatively expensive to prepare diphenyl than stoichiometric amounts. For example, U.S. Pat. methane. By utilizing the process of the present inven No. 3,933,917 discloses a process for the production of dimethylbenzophenone. However, the starting material tion, it is possible to obtain diphenylmethane in a rela for the preparation of this compound consists of a tively inexpensive manner, thus considerably lowering highly substituted benzene. The reference teaches that a 35 the cost of preparing the desired product. dimethylbenzene such as m-xylene or o-xylene is butyl Benzophenone is a compound which is assuming ated to obtain a highly activated t-butyl dimethylben increasing importance in the chemical industry. This zene, and, therefore, the reaction can employ relatively compound, namely, benzophenone, is used in perfum small amounts of ferric chloride as a catalyst due to the ery due to its mild aromatic and fixitive properties. In electron rich tri-substituted benzene. Thereafter, when addition to its use in perfumery, it also finds use as an the benzoylation has been effected, the intermediate anthelmintic, bacteriostatic agent, as well as a fungicide compound is then debutylated by means of aluminum and insecticide. In industry it is also used as an interne chloride to form the desired product. Other references diate for various processes, for discoloration of petro which have been found in the literature also disclose leum waxes and for copolymerization of drying oils and processes for the benzoylation of aromatic compounds. 45 styrene monomer. Lately, it has become used to a great In this respect, it is noted that in the Journal Of The extent in ultra-violet cured coatings and inks as a photo American Chemical Society, Volume 80, pages initiator. 2296-2300 the relative rates of aluminum chloride cata It is therefore an object of this invention to provide lyzed benzoylation of benzene derivatives is set forth. an improved process for the preparation of diphenyl Table I on page 2297 of the Journal sets forth the rate 50 methane. constants and compares the relative rates of benzene A further object of this invention is to provide a with substituted benzenes. The benzoylation rates process for synthesizing diphenylmethane by reacting which are given disclose that benzene has a relative rate benzene with a benzyl halide in the presence of certain of 1.00 and chlorobenzene has a relative rate of 0.01.15. Friedel-Crafts catalysts. As opposed to this, other substituted benzenes such as 55 In one aspect an embodiment of this invention resides toluene shows a relative rate of reaction of 110 while in a process for the preparation of a diphenylmethane the xylenes have relative rates ranging from 140 for which comprises reacting benzene with a benzyl halide p-xylene up to 3940 for m-xylene. Even while utilizing in the presence of a catalytic amount of a Friedel–Crafts aluminum chloride, which is a more active catalyst than metal halide at reaction conditions, and recovering the ferric chloride, the table would teach away from the reactant diphenylmethane. reaction of the present invention in which it has been A specific embodiment of this invention is found in a discovered that benzene, which is an electron poor process for the preparation of diphenylmethane which compound, may be benzylated in the presence of a comprises reacting benzene with benzyl chloride in the catalytic amount of ferric chloride. Likewise, a Russian presence of a catalytic amount of anhydrous ferric chlo reference, namely Yuldashev et al in Nauch. Tr. Tasch 65 ride at a temperature in the range of from about 50 to kent Univ., 1972, No. 419, pages 176-179 discloses that about 150° C. and a pressure in the range of from about cinnamoyl chloride did not react with toluene, which, atmospheric to about 100 atmospheres, and recovering as hereinbefore set forth is more reactive than benzene, the desired diphenylmethane. 4,251,675 3 4. Other objects and embodiments will be found in the inert atmosphere in order to counteract the presence of following further detailed description of the present the hydrohalic acid such as hydrochloric acid which is invention. evolved during the reaction and which may act in a As hereinbefore set forth, the present invention is deleterious manner as a catalyst for any side reactions concerned with the process for preparing or synthesiz which may occur during the condensation. When utiliz ing diphenylmethane by reacting benzene with a benzyl ing this inert atmosphere, it may be employed as a purge halide in the presence of a Friedel–Crafts metal halide by bubbling the gas such as nitrogen through the reac catalyst. In the preferred embodiment, the Friedel tants to entrap the hydrogen halide and remove the Crafts metal halide catalyst which is employed will same from the reaction vessel or, if so desired, the inert comprise ferric chloride, said catalyst being present in 10 atmosphere may also be employed as a blanket. How catalytic amounts which are less than stoichiometric ever, in the preferred embodiment in the invention, the amounts, the latter having heretofore been required former is preferred. when attempting to react a relatively inert aromatic The process of the present invention may be effected compound such as benzene or chlorobenzene which are in any suitable manner and may comprise either a batch electron poor. By utilizing ferric chloride in an anhy 15 or continuous type operation. In one embodiment of the drous state and also by using elevated temperatures, it invention, the two reactants comprising the benzyl hal has now been found possible to employ catalytic ide and benzene are placed in a reaction vessel such as amounts of the metal halide rather than the stoichiomet a flask which may be equipped with a thermometer, ric amounts which heretofore have been equired.
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