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United States Patent (19) (11 3,715,404 Lindlar Et Al

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United States Patent (19) (11 3,715,404 Lindlar Et Al United States Patent (19) (11 3,715,404 Lindlar et al. (45) Feb. 6, 1973 54 PROCESS FOR SELECTIVE 2,681,938 6, 1954 Lindlar............................, 260/677 H HYDROGENATION 2,992,278 7 1961 Tedeschi..... .............260/635 M 3,075,024 111963 Frevel et al....................... 2601677 H (75) Inventors: Herbert Lindlar, Reinach; Robert 3,336,239. 8/1967 Bailey et al....................... 260/617 C Dubuis, Morges, both of Switzerland 3,450,776 6/1969 Di Cio et al.......................... 260/642 73) Assignee: Hoffmann-La Roche, Inc., Nutley, N.J. FOREIGN PATENTS OR APPLICATIONS (22) Filed: Sept. 19, 1968 288,271 10/1915 Germany.............................. 260/642 (21). Appl. No.:760,980 Related U.S. Application Data OTHER PUBLICATIONS Taylor et al., “J. Am. Chem. Soc.", Vol. 63, (1941), 63. Continuation-in-part of Ser. No. 380,038, July 2, pp. 2756, 2757, Q01A5. 1964, abandoned. Primary Examiner-Leon Zitver 30 Foreign Application Priority Data Assistant Examiner-Joseph E. Evans June 3, 1964. Switzerland - w w w w a 7260/64 Attorney-Samuel L. Welt, Jon S. Saxe, Bernard S. (52) U.S. Cl................ 260/642, 252/430, 260/526 N, Leon and William H. Epstein 260/598, 260/617 C, 260/624 B, 260/631.5, 260/635 M, 260/666 A, 260/668 R, 260/677 57 ABSTRACT - H, 260/690 (51 Int. Cl.....C07c33/02, C07c35/02, C07c57/02 A process for selective hydrogenation of unsaturated 58 Field of Search.260/642, 635 M, 617 C, 618 H, organic compounds having at least four carbon atoms 260/690, 677 H, 666 A, 668 R, 526 N, 624 by carrying out said hydrogenation in a liquid phase in B, 631.5; 252/428,430,439 the presence of an organic sulfur compound utilizing a partially deactivated palladium catalyst. 56 References Cited UNITED STATES PATENTS 8 Claims, No Drawings 2,300,598 11/1942 Schnabel et al..................260/635 M 3,715,404 2 PROCESS FOR SELECTWE HYDROGENATION ygen, sulfur or nitrogen. Additionally, the symbols R. CROSS-REFERENCE TO RELATED and R2 each represent aryl groups, such as, phenyl or APPLICATIONS napthyl which, if desired, can be substituted with, for example, an alkyl group and/or the previously named This application is a continuation-in-part of U.S. 5 patent application Ser. No. 380,038, filed July 2, 1964, oxygen-, sulfur- and nitrogen-containing substituents. Lindlar etal and now abandoned. Furthermore, the symbols R and R. each represent heterocyclic groups, such as, pyridine and quinoline BACKGROUND OF THE INVENTION groups. Finally, the symbols R and R, each represent . It is well known in the art that certain unsaturated or 10 araliphatic groups, especially a benzyl radical. ganic compounds, for example, compounds having tri Where, in Formula I, the symbol in represents the in ple bonds in their structure or quinones having a dou teger 1, the symbol R, represents also a hydrogen atom. ble-bond-containing side chain, can be hydrogenated, Additionally, groups represented by the symbols R1 and selectively, by means of the use of special hydrogena R, may form, with a sulfur atom, a heterocyclic group, tion catalysts. Palladium catalysts are especially valua 15 such as, thiophene. The number of members constitut ble for use in such selective hydrogenations, it being ing such ring is variable, for example, from 3 to 6. well known that the activity of palladium can be Thus, for example, Formula I which has been set reduced, and its selectivity thus enhanced, by its use in forth heretofore embraces within its scope the follow combination with a second metal, such as lead, ing groups of compounds: bismuth, copper, zinc, tin, mercury, cadmium or thori 20 a. Thiols, such as, thioalcohols, mercaptans, um. One such partially deactivated palladium catalyst thiophenols, etc. having the formula is the palladium-lead catalyst described, for example, in Helv. Chim. Acta. 35,446 (1952). Moreover, it is also R-SH (a) known in the art that the selectivity of such catalysts in which the symbol R has the same meaning as in For can be improved when an organic nitrogen base, for ex 25 mula I. ample, a tertiary amine, such as, pyridine or quinoline, b. Thioethers of the formula is added to the hydrogenation mixture. R-S-R. (b) BRIEF SUMMARY OF THE INVENTION in which the symbols R and Rs have the same 30 meanings as in Formula I. in accordance with this invention, it has been found that acetylenically unsaturated organic compounds c. Organic disulfides of the formula having about four carbon atoms, aryl-containing com R-S-S-R. (Ic) pounds having at least one keto group attached directly in which the symbols R and R. have the same to the aryl moiety and having an ethylenically unsatu 35 meanings as in Formula I. rated side chain can be selectively hydrogenated Included among the thiols which are represented by without effecting any ethylenic unsaturation by carry Formula Ia are alkylmercaptans, such as, n-butylmer ing out the hydrogenation in a liquid state utilizing a captan, n-hexylmercaptan, etc.; monothioglycols, such partially deactivated palladium hydrogenation catalyst as, monothioethyleneglycol, etc.; dithioglycols, such as, in the presence of an organic sulfur compound or a 40 mixture of organic sulfur compounds, derived from dithiopropyleneglycol, etc.; arylmercaptans hydrogen sulfide or hydrogen disulfide. The use of the (thiophenols), such as, thiophenol itself and its nuclear organic sulfur compounds in accordance with this in substitution products, such as, thiocresol, etc.; vention considerably improves the selectivity of par dithiobenzols, such as, dithioresorcin, etc.; mercapto tially deactivated hydrogenation catalysts, such as pal 45 substituted heterocyclics, such as, mercaptopyridine, ladium lead catalysts and, accordingly, increases the mercaptopyrimidine, etc. yields of the derived partially hydrogenated product. As examples of the thioethers, which are encom passed by Formula Ib, there can be mentioned dialkyl DETAILED DESCRIPTION sulfides, such as di-n-butyl sulfide, di-tertiary butyl sul The organic sulfur compounds which are used in the 50 fide, etc.; dihydroxyalkyl sulfides, such as, practice of this invention are those having the formula thiodiethyleneglycol S(CHCHOH)), thiodipropyleneglycol, etc.; diaryl sulfides, such as, R-(S)-R diphenyl sulfide, etc.; diaralkyl sulfides, such as, in which formula, the symbol in represents the integer 1 dibenzyl sulfide, etc.; alkyl ethers of thiophenols, such or 2; R and R, being the same or different, each 55 representing an organic residue, which is aliphatic or as, thioanisole, etc.; cyclic thioethers, and substituted aromatic in nature, which is bound to the sulfur derivatives thereof, such as, ethylene sulfide, through a carbon atom of said residue. thiophene, thiazole, thiopyran, thioxanthone, thiox Thus, for example, the symbols R and R, in Formula I anthydrol, 1,4-thioxane, etc.; S-alkyl ethers of mercap each represent a saturated, straight chain, branched 60 to-substituted heterocyclics, such as, 2-methyl-thio chain or cyclicaliphatic hydrocarbon. Such hydrocar 4,6-diamino pyrimidine, etc. bon can be unsubstituted or substituted, for example, A class of compounds which is especially well suited with an oxygen-, sulfur- or a nitrogen-containing group, for use in the practice of this invention is that, contain such as, a hydroxy, alkoxy, carboxy, carbalkoxy, oxo, ing at least two thioether groups in the molecule, hav thio, alkylthio, imino, amino, alkylamino, dial 65 ing the following formula: kylamino, etc. group. The chain of the hydrocarbon HO-(CH2)-S-(CH)-S-(CH2)-OH II residue can also contain a hetero atom, such as, ox in which r represents an integer from 1 to 6, inclusive. 3,715,404 3 4 Especially well suited for use is the compound of For yne-3-ol; and tertiary propargyl alcohols such as 3 mula II in which the symbol x represents the integer 2, methyl-1-butyne-3-ol, 3-methyl-4-penten-1-yne-3-ol, that is, 1,2-bis-(2-hydroxyethylthio)-ethane having the 3,7-dimethyl-6-octen-1-yne-3-ol, that is, formula dehydrolinalool, 3,7,11,15-tetramethyl-1-hexadecyne 3-ol, that is, dehydroisophytol, 3-methyl-1-pentyne-3,5 -diol, etc. The compounds of Formula II are obtained by the reac Other organic compounds which can be selectively tion of one mole of a-a-dihalogenoalkane with 2 moles hydrogenated in accordance with this invention are of a mono-thio alkyleneglycol. cycloalkyl compounds containing hydroxy substituted Illustrative of the organic disulfide compounds which 10 aliphatic side chains, wherein the side chain has one or are represented by Formula Ic are dialkyl disulfides, more triple bonds and can contain conjugated or non such as, di-n-butyl disulfide; diaryl disulfides, such as, conjugated double bonds in addition to the triple bond. diphenyl disulfide, di-(o-carboxyphenyl)-disulfide, An example of such a compound is 3,7-dimethyl-9-(2- etc.; diaralkyl disulfides, such as, dibenzyl disulfide. 6,6'-trimethylcyclohexene-(1)-yl)-2,7-nonadiene Moreover, since it is known that organic disulfide com 5 4yne-1,6-diol. Also included among the organic com pounds are converted, easily, by reductive cleavage pounds containing acetylenic unsaturation which can into the corresponding thiols and since such thiols can, be utilized in accordance with this invention are in turn, be reconverted into disulfides by the action of aliphatic acids, i.e., carboxy substituted aliphatic mild oxidation agents, according to the reaction 20 hydrocarbons, having from four to 45 carbon atoms mechanism shown in the following equation containing one or more triple bonds and which can contain conjugated or non-conjugated double bonds in addition to the triple bond. As examples of such acids it will be understood that all of the disulfides, cor are the acetylenic precursors of arachidonic acid, responding to the thiols specifically mentioned hereto 25 linoleic acid, y-linolenic acid and other essential fatty fore, can be used in the practice of this invention.
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