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United States Patent Office Patented Apr 2,933,525 United States Patent Office Patented Apr. 19, 1960 i 2 2,933,525 of this invention is to provide a method of preparing PRE PARATION OF TETRACARBOXYLCACDS tetracarboxylic acids and diketodicarboxylic acids, and AND DIKETO-D CARBOXYLIC ACDS compositions of matter containing same, by the reaction John B. Braunwarth, Crystal Lake, and Gifford W. of alpha-beta-unsaturated carboxylic acids with cyclic Crosby, River Forest, Ill., assignors to The Pure Oil peroxides and hydroperoxides under redox conditions. Company, Chicago, Ill., a corporation of Ohio - The reactions involved in the process of this invention No Drawing. Application December 27, 1957 may be represented broadly as follows: - Serial No. 705,490 21 Claims. (C. 260-537) O R.' (CH2).(=0 This invention relates to a method of preparing tetra X O OE R R77 carboxylic acids and diketo-dicarboxylic acids and, more N / . / R’-CH-C(R') COOH (C ) --R'C=C- N -->. R-CH-C (R') COOH particularly, to the preparation of these products by the R COOH - reaction of cycloalkanol hydroperoxides or alkylcyclo - . R (pH), alkyl hydroperoxides with alpha, beta-unsaturated car 15 boxylic acids under reduction-oxidation conditions. CaO Many reactions of hydroperoxides are known in the X prior art. E. G. E. Hawkins in his article entitled, "Reac Peroxide Unsaturated Acid or ketone product tions of Organic Peroxides, Part II, Reactions of a,c-Di (redox) acid methylbenzyl Hydroperoxide ('Iso-Propylbenzene Hydro 20 wherein X is selected from the group of C to Cs alkyl peroxide'),” (J. Chem. Soc. 1950, 21.69), shows the de radicals, which may be straight-chain or branched-chain, composition of a,c-dimethylbenzyl hydroperoxide by fer or a hydroxyl group; R is a divalent organo radical con rous sulfate under the influence of various catalysts and taining from 3 to 9 carbon atoms in the unsubstituted under thermal conditions to form mixtures of 2-phenyl portion of the diradical, and may consist of unsubstituted propan-2-ol, acetophenone, and a-methylstyrene. The 25 methylene groups or polymethylene groups, or it may hydroperoxides were first shown by Hock and Lang, Ber. contain one or more substituents of the group consisting 77, 257 (1944), to be formed by the oxidation of iso of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, benzyl, propylbenzene with air to give Ph.CMeOOH. Improved phenyl, cyclohexyl, chloro, fluoro, hydroxy, or alkoxy methods for their preparation are described by Armstrong, groups such as methoxy; R may be an alkyl radical con Hall and Quin, British Patents 610,293 and 630,286; J. 30 taining from 1 to 6 carbon atoms or may be an aryl group Chem. Soc. 1950, 666. E. G. E. Hawkins and P. P. i.e., the phenyl group or an alkaryl group; R'' and R' Young (J. Chem. Soc. 1950, 2804), state that the reac may be hydrogen or alkyl radicals containing from 1 to tion of methylcyclopentyl hydroperoxide with ferrous 6 carbonatoms or may be an aryl group, or an alkaryl sulfate solution gives rise to the formation of dodecane group; and n is an integer of from 3 to 9. From this 2,11-dione. However, the use of methylcyclohexyl hydro 3. 5 definition, it is seen that when X is an alkyl group, the peroxide gives poorer yields of tetradecane-2,13-dione. end product is a diketo-dicarboxylic acid and when X N. Brown et al., J. Am. Chem. Soc. 77, 1756 (1955), is the hydroxyl group, the end product is a tetracarboxylic describe the preparation of "cyclohexanone peroxide” by acid. In each instance the number of carbon atoms in the autocatalyzed, liquid-phase oxidation of cyclohexanol the divalent R group governs the value of n in the end with oxygen. Reaction of these peroxides with the ferrous 40 product. Examples of C1 to Cs alkyl groups included in ion in hydrocarbon solution is said by Brown et al. to the definition X are methyl, ethyl, propyl, isopropyl, butyl, produce a 68% yield of 1,12-dodecanedoic acid. M. S. isobutyl, tertiary butyl, pentyl, isopentyl, hexyl and iso Kharasch and W. Nudenberg in their article entitled, hexyl groups. "Detection of Free Radicals in Solution, III, Formation Examples of R groups in the above equations and for of Long-Chain, a,c)-Dicarboxylic Acids” (J. Org. Chem. 45 mula include: . - . - 19, 1921 (1954)), indicate that unsaturated dicarboxylic acids of 20 carbon atoms are formed from cyclohexanone peroxide and butadiene. - . --CHCHCHC(CH3)- The formation of diketones and dibasic acids is assumed . CH-CH to take place by the rearrangement of an alkoxy radical 50 % N to an open-chain carbon radical, followed by dimerization, -CH-CH-C-CHCH- -o-c-c CH thus: ce JCH, c YoHYc-c?, CH-CH YoH-cí EO O. O. O O Ho, 2 o N/ N/ C - -CH-C=C-CH, CH,- 55 . / N Hol CH re-d YoH-cí Feh- O -C=C-CHCHCH- -CH-CH-CHCHCH / N / N in the case of the Cao dicarboxylic acids, the inter 60 HC CH CR oH, mediate radical adds to the butadiene before dimerization. CH-CH CH-CH It has been found in accordance with this invention . that when compounds of a cyclic structure having a peroxide grouping attached directly to one of the carbon -CH,C-CH, CH,- -CH, CH(OCH) CHCH, CH,- atoms in the cyclic structure, as cycloalkanol hydroper e. 9 ‘. .'; ... --:... oxide and alkyl cycloalkyl hydroperoxide, are decom 65 posed by the presence of reduction-oxidation conditions -CHCH (CoH) CH-CH- -CH, CH=CH-CH,- in the presence of alpha, beta-unsaturated carboxylic O acids, the main products are tetracarboxylic acids or -CHCH(COCH) CHCH, CH- -CHCH(OH) CH, CH,- diketo-dicarboxylic acids. The resulting products are use- 70 ful as intermediates in the preparation of synthetic lubri cants, plasticizers, resins and fibers. The primary object OCH 2,988,525 3 é The preferred R groups are trimethylene, tetramethyl low atmospheric may be used. Pressures higher than ene, pentamethylene and hexamethylene groups; since the atmospheric are advantageous where a relatively volatile carbon atom attaching to the X group and to the OOH solvent is used in the liquid phase. In general, the reac group is not included in the definition of R, the number tion proceeds at atmospheric pressure and at temperatures of carbon atoms in the cyclic group becomes 4 to 10. in the range of -100° C. to 100° C. The preferred The peroxide or hydroperoxide starting materials used temperature range is -30°C. to 60° C. in this invention are well known and their properties fairly in order to illustrate the invention, a number of ex Well defined. The term "peroxide compound will be used amples are given: herein to broadly cover compounds of formulas set forth Example I above and to include compounds which in a strict sense O are defined as hydroperoxides. The preferred starting This example describes the reaction of "cyclohexanone materials are the peroxides of the type obtainable by peroxide' and crotonic acid to form 7,8-dimethyltetradec treating cycloalkanols or alkyl cycloalkanes with oxygen ane - 1,6,9,14-tetracarboxylic acid. "Cyclohexanone or by the reaction of cycloalkanones with hydrogen per peroxide” (0.49 mole) in 750 cc. of methyl alcohol was oxide. Examples are the peroxide compounds obtained 5 cooled to 0° C., and 43 gm. (0.5 mole) of crotonic acid by reacting hydrogen peroxide with cyclopentancine and were added, with stirring. A solution containing 147gm. cyclohexanone where R is -(CH2)4- and -(CH2)5-, (0.53 mole) of ferrous sulfate heptahydrate, 25 cc. of con respectively, particularly the reaction products of hy. centrated sulfuric acid and 250 cc. of distilled water was drogen peroxide and cycloalkanones and the oxidation added dropwise to the reaction mixture over a period of products of cycloalkanols and alkyl cycloalkanes. Fol 20 2 hours. lowing the above definitions for R and X, these prod After standing overnight, the reaction mixture was ucts include cyclopentanone peroxide, cyclohexanone diluted with 750 cc. of water and the organic phase which peroxide, cycloheptanone peroxide, methylcyclohexane separated was collected. The aqueous alcohol solution hydroperoxide, ethylcyclopentane hydroperoxide, etc. was extracted with a 75-25 mixture of benzene and The alpha, beta-unsaturated carboxylic acids used as 25 ether, respectively. The combined organic phases were reactants in accordance with this invention include the then water-washed until neutral to litmus, and distilled to following unsaturated acids: remove ether and benzene. The residue was then distilled Crotonic acid, iso-crotonic acid, 2-hexenoic acid, cin under water-pump vacuum to remove unreacted cyclo namic acid, beta-ethyl acrylic acid, beta-beta-dimethyl hexanone (the cyclohexanone peroxide used in this reac acrylic acid, angelic acid and its isomer tiglic acid, iso 30 tion was prepared in an excess of cyclohexanone). In hydrosorbic acid and homologs thereof having alpha, beta order to assure complete esterification, the remaining resi unsaturation. Those acids, such as acrylic and methyl due was diluted with 100 cc. of methyl alcohol, 7.5gm. of acrylic, having a terminal methylene group are excluded p-toluene sulfonic acid was added as catalyst, and the mix because of the ease with which they polymerize. ture was refluxed for five and a half hours. Thereafter, The use of reduction-oxidation conditions is essential 35 mixture was diluted with 100 cc. of distilled water and ex to convert the peroxide compounds to the diketo-dicar tracted with benzene. The combined benzene extraction boxylic acid or tetracarboxylic acid products by reaction phases were water-washed until neutral to litmus, dried with the alpha-beta unsaturated carboxylic acids. The over CaSO4, and filtered.
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