United States Patent ;,., Luberoff et al. 4,006,194 Feb. 1, 1977 ny (45) [54] PRODUCTION OF PHENOLS (75] Inventors: Benjamin J. Luberoff, Summit; Todd S. Simmons, Montelair, both of NJ. (73) Assignee: ‘The Lummus Company, Bloomfield, Nu [22] Filed: May 17, 1971 [21] Appl. No.: 143,845 52] US. Ch... 260/621 C3 260/593 A; 260/601 R; 260/606; 260/610 R; 260/632 R: 260/624 R; 260/626 T {St} Int. CL? snes COTE 37/00 {58] Field of Search 0/621 C, 610 R, 632R (56) References Cited UNITED STATES PATENTS 2.628.983 2/1953 Alten eta. 260/621 C 2,883,430 4/1989 De Jorg 260/621. 21906.789 9/1959 MeNaughian 260/621 C 33365375 1/1968 Nixon 260/621. Primary Examiner—Norman Morgenstern Attorney, Agent, or Firm—Marn & Jangarathis (57) ABSTRACT Phenols are produced from a-aralkyl peroxides, prefer- ably alkyl- a -phenalkyl peroxides or diphenalkyl per- oxides, by heating the peroxide in the presence of an id catalyst and continuously separating volatile reac- tion products other than the phenol; i.e., a carbonyl compound and alcohol if formed, from the reaction mixture, preferably by bubbling a stripping gas there- through. Phenol may be produced from an alkyl ben- zene by reacting the alkyl benzene with t-butyl hydro- peroxide to produce a t-butyl- a -phenalkyl peroxide which is then decomposed in the presence of an acid ‘catalyst. The reaction co-products include t-butanol and a carbonyl compound corresponding to the alkyl group. 7 Claims, 1 Drawing FigureU.S. Patent Feb. 1, 1977 4,006,194 23 2 24 2 20 oo on 18 “ a7 a TS 26 15. 7 a —______ INVENTORS Benjamin J. Luberoff BY Todd S. Simmons Marn & fangarathis ATTORNEYS4,006,194 1 PRODUCTION OF PHENOLS ‘This invention relates to the production of phenols and more particularly to the production of phenols from a-aralkyl peroxides. This invention further relates to an overall process for producing phenols from an alkyl substituted aromatic compound and an alkyl hy- droperoxide. Phenol has been produced by the oxidation of cu- ‘mene to cumyl hydroperoxide which is then decom- posed in the presence of an acid catalyst to phenol and acetone. There is a continuing need for new processes for producing phenol in particular, processes which are capable of producing byproducts other than acetone and are also capable of producing phenol through @ ‘more stable intermediate ‘Accordingly, an object of this invention is to provide aa new process for producing phenols. “Another object of this invention is to provide a pro- cess for producing a phenol by the decomposition of an ‘ecaralkyl peroxide. ‘A further object of this invention is to provide a process for producing phenols from an alkyl substituted aromatic compound and an alkyl hydroperoxide. ‘These and other objects of the invention should be ‘more apparent from reading the following detailed description thereof with reference to the accompany- ing drawing, wherein ‘The drawing is a simplified schematic diagram of a reactor to be used in an embodiment of the invention. ‘The objects of this invention are broadly accom- plished in one aspect by decomposing an aromatic peroxide characterized by having as one or both of its moieties an a-aralkykl group, and if applicable as its other, an alkyl group, in the presence of a suitable catalyst and in a manner such that the volatile products of reaction; ie., the carbonyl compound corresponding to the alkyl portion of the a-aralkyl moiety and alcohol, if formed, corresponding to the alkyl moiety, are con- tinuously separated from the reaction environment; ive., such reaction products are separated from the reaction mixture as formed, Tn another aspect, the objects of the invention are accomplished by reacting an alkyl substituted aromatic ‘compound with an alkyl hydroperoxide to produce an ‘caralkyl peroxide which is then decomposed to phe- nol. ‘More particularly, the a-aralkyl alkyl peroxide, is decomposed at a temperature from about 20° to about 150° C., preferably from about 70° to about 110°C., in the presence of an acid catalyst, either a protonic acid or a Lewis acid, in a manner such that the volatile reaction products, (the carbonyl compound and alco- hol, if formed) are continuously separated from the reaction mixture. The volatile reaction products a pref- erably separated from the reaction mixture by the use of a stripping gas which continuously strips the volatile products from the mixture. It is to be understood, how- ever, that techniques other than the use of a stripping gas are within the spirit and scope of the invention e.g., distillation, although the use of a stripping gas is pre- ferred. Its also to be understood that the material used as a stripping gas may also be a catalyst for the reac- tion; e.g. sulfur dioxide functions as both catalyst and stripping gas. ‘The material employed as the stripping gas may be ‘comprised of any of a wide variety of materials which do not adversely affect the decomposition reaction, 1s 20 2s 30 35 4s so 35 Cy 6s 2 and as representative examples of such gases, there ‘may be mentioned: The lower hydrocarbons, nitrogen, alkyl aromatic compounds (preferably the alkyl aro- matic compound from which the peroxide is derived) and the like. The stripping gas may also be formed from ‘a material which catalyzes the reaction; e.g., sulfur dioxide, in which case no additional catalyst need be added. The choice of a stripping gas for a particular decomposition reaction is deemed to be well within the scope of those skilled in the art from the teachings herein, ‘The decomposition reaction may be effected in the presence or absence of solvent as a batch or continuous process. The solvent, if employed, is preferably either ‘an alkyl aromatic compound from which the peroxide is derived or a mixture of such an aromatic compound with the alcohol reaction product of the decomposi- tion. Iti to be understood, however, that any one of a wide variety of solvents which do not adversely affect the decomposition reaction are included within the spirit and scope of the invention. The process of the invention is applicable to the decomposition of a wide variety of a-aralkyl peroxides ‘with the term a-aralkyl peroxides as used herein denot- ing the class of compounds having as one or both of its moieties an aromatic nucleus substituted with an or- ganic peroxymethyl group wherein the methylene ‘group is unsubstituted or one or both of the hydrogens of the methyl group is substituted with an alkyl group ‘and the aromatic nucleus may be free of substituent groups other than the alkyl peroxymethyl group or Contain other substituent groups and if applicable as other moiety an alkyl group; the following structural formula is representative of such compounds: % Aeg-00— Rs & wherein R, and Ry may be the same or different groups and are either hydrogen or alkyl (preferably lower alkyl); Rs is alkyl (preferably lower alkyl, with tertiary ower’ alkyl being particularly preferred) or phen (lower) alkyl; and Ar is either a phenyl, naphthyl (a or @naphthyl,) anthranyl (1,2 or 9 anthranyl), or phenan- thranyl (1-, 2-,3- or 9-phenanthranyl) radical, (prefer- ably a phenyl radical) or substituted derivatives of such radicals wherein the substituent groups are either halo (preferably chloro-), lower alkyl, lower alkoxy, nitro or ‘cyano. The term lower alkyl as used herein includes up to about six carbon atoms. ‘The preferred peroxides are the lower alkyl- a-phen (lower) alkyl peroxides and the di- a-phen (lower) alkyl peroxides and as representative examples of such preferred peroxides, there may be mentioned: t-butyl- ‘a-phenethyl peroxide; t-butyl-a-tolyl peroxide; tbutyl- 2phenylisobutyl peroxide; t-butyl cumyl peroxide; di-a-phenethyl peroxide; dicumylperoxide; cumyl phenethyl peroxide, and the like. Its to be understood that the hereinabove noted representative examples are only illustrative and, therefore, the scope of the inven- tion is not to be limited thereby. ‘The catalyst which is employed may be any one of the wide variety of acid catalysts which are generally employed to decompose aromatic hydroperoxides; ie., any material which provides an acidic pH in water, and