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United States Patent (19) 11 Patent Number: 4,487.978 Kruse Et Al

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United States Patent (19) 11 Patent Number: 4,487.978 Kruse Et Al United States Patent (19) 11 Patent Number: 4,487.978 Kruse et al. 45) Date of Patent: Dec. 11, 1984 54 HIGH YELD PROCESS FOR PREPARING 4, 9,544 2/1979 Rutledge ............................. 260/396 4,4'-BIPHENOL AND , 50,243 4/1979 Bruck et al. ........................ 568/805 TERTALKYLATED-ALKYLBENZENES 4, 195,189 2/1979 Earley ................................. 568/730 4,205,187 5/1980 Gardenas et al. ................... 563/730 (75) Inventors: Walter M. Kruse, Wilmington, Del.: 4,243,822 6/1981 Demler et al. ...................... 568/730 John F. Stephen, West Chester, Pa. 4,354,047 10/1982 Strom .................................. 568/730 4,354,048 10/1982 Strom.................................. 568/730 73) Assignee: ICI Americas Inc., Wilmington, Del. 4,414,422 11/1983 Ash et al. ............................ 568/724 21 Appl. No.: 514,256 OTHER PUBLICATIONS 22 Filed: Jul. 15, 1983 M. Tashiro, "Selective Synthesis of Aromatic Cmpds. (51) Int. Cl. .............................................. C07C39/15 Using Positional Protective Groups', Synthesis, (1949), 52) U.S. Cl. ..................................... 568/730; 585/319 pp. 921-924. (58) Field of Search ......................... 568/730; 585/319 Primary Examiner-Werren B. Lone (56) References Cited Attorney, Agent, or Firm-Richard A. Rowe U.S. PATENT DOCUMENTS (57) ABSTRACT 2,792,427 5/1957 Houtson et al. .................... 260/613 Biphenol and para substituted alkylbenzene derivatives 3,562,338 2/1971 Zaweski .............................. 260/62O are produced in high yield and purity by heating alkyl 3,631,208 12/1971 Hay ............ ... 260/619 R 4,100,205 7/1978 Rutledge ... ... 568/730 benzene solvent solutions of tetraalkyl substituted 4,4'- 4, 101,561 7/1978 Rutledge ... ... 260/396 biphenols in the presence of strong acid catalyst. 4,108,908 8/1978 Rutledge .... ... 568/730 4,132,722 1/1979 Rutledge ............................. 260/206 7 Claims, No Drawings 4,487,978 1. 2 of a tetra-substituted diphenoquinone characterized by HIGH YELD PROCESS FOR PREPARING the steps: 4,4'-BIPHENOL AND (a) forming a tetraalkyl biphenol by the hydrogena TERTALKYLATED-ALKYLBENZENES tion of a diphenoquinone having the general for mula: The invention relates to a new improved process for hydrogenating 3,3',5,5'-tetra-alkyl-4,4'-diphenoquinone to the corresponding biphenol and the subsequent deal kylation thereof in the presence of an alkylbenzene to provide a high yield of completely dealkylated biphenol 10 and a para substituted tert-alkylalkylbenzene derivative. Biphenols, and particularly substituted biphenols have wide utility as bactericides, chemical intermedi R R ates, as monomers in making copolymers and as antioxi dants. The 2,6-disubstituted biphenols are used to stabi 15 wherein R is a tertiary alkyl group having 4-8 lize such materials as animal and vegetable fats or oils, carbon atoms employing hydrogen gas and a heter gasoline, lubricants, rubber compositions and as mono ogeneous catalyst in a solvent solution of an alkyl mers for the preparation of high performance resins. benzene, Moreover unsubstituted biphenols such as 4,4'-biphenol (b) removing said catalyst from the tetraalkyl bi is a very useful monomer in the preparation of high 20 phenol containing solution, performance resins such as polysulfones, polyketones, (c) heating said solution in the presence of a strong polycarbonates, polyesters and polyurethanes wherein acid catalyst in an inert atmosphere to form bi the biphenol is used as the dihydroxyl compound which phenol and an R substituted tert-alkylalkylbenzene is reacted with phosgene, dibasic acids, polyepoxides derivative, and and polyisocyanates etc. When used in this way aro 25 (d) recovering biphenol and said R-substituted alkyl matic resins are produced which exhibit good physical benzene from said solution. mechanical products combined with superior oxidation The hydrogenation step is carried out in an alkylben and solvent resistance. Zene solvent solution of a diphenoquinone having the The tert-alkylated alkylbenzenes are also useful prod general formula: ucts such as for example tert-butylethylbenzene which 30 is an intermediate in the synthesis of tert-butyl styrene, a valuable monomer in the manufacture of modified styrene resins as described in U.S. Pat. No. 4,334,115. Additional intermediates such as tert-butyltoluene can be made economically for use in fragrances and insecti 35 cides. Previously biphenols have been rather difficult and R R costly to produce because of the involved procedures required, the tendency to produce undesirable by-pro wherein R is a tertiary alkyl group having 4 to 8 carbon ducts, the difficulty in obtaining a pure product and 40 atoms such as tert-butyl, tert pentyl, and tert-octyl. The color characteristics needed for resin use, low yield and diphenoquinone materials are readily obtainable by the the necessity for employing expensive equipment. As a oxidative coupling of the corresponding 2,6-dialkyl result of the present invention both 4,4'-bis(2,6-di-tert phenol derivatives in the presence of an appropriate butylphenol) or 4,4'-biphenol along with a valuable 45 oxidative coupling catalyst and oxygen at a temperature coproduct such as a tertiary-butylated alkyl aromatic ranging from 30 to 150 C. hydrocarbon can be produced in high yields in rela The alkylbenzene solvent may be selected from tolu tively inexpensive equipment at low temperatures and ene, ethylbenzene and propylbenzene and others pressures. wherein said alkyl group has up to about 10 carbon Previously tetrasubstituted biphenols have been gen atoms. The amount of solvent required is dependent erally prepared by the oxidative dimerization of disub upon the solubility of the diphenoquinone and the reac stituted phenol reactants in the presence of a metallic or tion rate desired. Usually a diphenoquinone concentra strongly alkaline catalyst to form the corresponding tion of 5-50% by weight is economical. tetrasubstituted diphenoquinone. The quinones are re The hydrogenation is carried out in the presence of covered and then reduced with hydrogen to the corre 55 from 0.1-10% by weight of a heterogeneous catalyst sponding substituted biphenol. More recent descrip selected from a nobel metal such as ruthenium, platinum tions of these reactions can be found in U.S. Pat. Nos. and palladium and transition metals such a nickel and 4,354,047; 4,354,048; 4,205,187; 4,085,124 and 4,096, 190. copper which may be deposited on an inert substrate It is an object of the present invention to provide for such as carbon, silica, alumina, diatomaceous earth, clay an improved process for carrying out the hydrogena 60 etc. These catalyst are well known and may be pur tion of a tetra-substituted diphenoquinone to form the chased commercially. corresponding tetra-substituted biphenol in high yields. The reaction is carried out at temperatures of 25 to It is another object to provide a transalkylation process 150° C. and preferably about 5-10 C. below the boil of tetra-alkylbiphenol in alkylbenezene solution to pro ing point of the solvent at hydrogen pressures ranging vide high yields of biphenol and para tert-alkylated 65 from atmospheric to 100 psi. Most favorable reaction alkylbenezene. Another object is to provide an inte rates are obtained at temperatures of 125 to 145 C. and grated process for forming biphenol and an R-alkylated preferably 130° C. The reaction is usually complete at alkylbenzene derivative from an alkylbenzene solution these temperatures within about 2 hours. 4,487,978 3 4 In the general operation of the invention the hetero The biphenol solvent solutions remaining after the geneous hydrogenation catalyst was placed into a suit separation of the heterogeneous catalyst may be further ably designed reaction vessel fitted with a reactant inlet subjected to a dealkylation/transalkylation reaction for and product outlet along with heating means as well as the purpose of preparing pure biphenol and an alkylben an entrance and exit means for the hydrogen containing 5 zene derivative substituted in the para position with a gas. The reactor was also equipped with an agitator. tertiary or secondary alkyl group in high yields. The reactor vessel was next charged with a solution The dealkylation/transalkylation reaction is carried of the tetraalkyl diphenoquinone in the alkylbenzene out in an alkylbenzene solvent solution of a tetraalkyl solvent, sealed and heated to the desired reaction tem substituted biphenol having the general formula: perature and thereafter controlled at that temperature O and pressure with hydrogen gas under agitation for a R R period of about 2 hours. Complete reduction is indi cated by the decoloration of the solvent. The heteroge neous catalyst may be removed from the hot solvent by filtration after which the solution containing the tetraal 15 kyl biphenol is cooled to ambient temperature at which point the product precipitates from solution and is easily R R removed by further filtration. The solvent may be recy wherein R is a tertiary alkyl group having 4-8 carbon cled for reuse or retained with the biphenol for the 20 atoms such as tert-butyl, tert-pentyl and tert-octyl. The purposes of performing a transalkylation reaction. If alkylbenzene solvent may be selected from toluene, preferred the solvent can be removed by distillation at a ethylbenzene and propylbenzene and alkyl benzenes temperature below the thermal decomposition point of having up to about 10 carbon atoms in the alkyl group. the tetraalkylbiphenol derivative after the catalyst is The amount of solvent required is dependent on the removed. 25 solubility of the biphenol derivative and the reaction A better understanding of the invention may be had rate desired. Normally a biphenol concentration rang by reference to the following examples which are in ing from 5 to 50% by weight is economical. tended to illustrate but not limit the invention. All pro The dealkylation/transalkylation reaction is carried portions are expressed in parts by weight unless other out in the presence of a strong acid catalyst in concen -wise specified.
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