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. acids. The present invention is of significant value in many The process of this invention can also be utilized to and various processes. The use of the organic sulfur convert a keto group attached to an aryl moiety to a compounds is found to be most efficient and beneficial hydroxy group. In accordance with this invention the in the selective hydrogenation of organic compounds 30 aryl compound which contains a keto group can con which contain acetylenic unsaturation. Any liquid or tain aliphatic side chains which may have at least one Solid organic compound having at least four carbon triple bond as well as one or more conjugated or non atoms and containing acetylenic unsaturation can be conjugated double bonds. The reaction of this inven partially hydrogenated to reduce the triple bond to a tion converts the keto group to a hydroxy group double bond in accordance with this invention. Among 35 without effecting the double bonds within the com the acetylenic unsaturated compounds which can be pound. For example, the quinone Vitamin K can be utilized in accordance with this invention are included converted into the corresponding hydroquinone com aliphatic hydrocarbons containing from four to 45 car pound in which the ethylenic bonds in the side chain bon atoms and having one or more triple bonds such as 40 are preserved. Generally, these aryl compounds con mono-alkyl acetylenes, dialkyl acetylenes, etc., and tain from six to 45 carbon atoms. aliphatic hydrocarbons containing four to 45 carbon The hydrogenation reaction of this invention is car atoms having one or more triple bonds and one or more ried out in a liquid medium. If the acetylenically un conjugated or non-conjugated double bonds. Also in saturated organic compound and the aryl keto com cluded among the acetylenically unsaturated com 45 pound is a liquid, then no solvent need be present. On pounds which can be selectively hydrogenated in ac the other hand, if the acetylenically unsaturated or cordance with this invention are aryl or cycloalkyl ganic or aryl keto compound is a solid, then the reac compounds containing an acetylenically unsaturated tion of this invention should take place in the presence aliphatic side chain. The aryl moiety can be phenyl, of an inert organic solvent. Even in the case of where napthyl, etc. Both the aryl and cycloalkyl moieties can 50 these compounds are liquids, an inert organic solvent be substituted with one or more aliphatic side chains. can, if desired, be present in the reaction medium. Generally this aryl or cycloalkyl compound can contain The manner in which the present invention is carried from eight to 45 carbon atoms. Among the aryl or out will be readily apparent to persons skilled in the art. cycloalkyl compounds containing acetylenic unsatura In general, partial hydrogenation processes utilizing the tion which can be treated in accordance with this in 55 organic sulfur compounds disclosed herein are carried vention are included those compounds having a side out in the same manner as the known prior art chain which contains in addition to the triple bond, processes. Thus, for example, the hydrogenations can conjugated or non-conjugated double bonds such as be effected in the presence or in the absence of a sol 15, 15'-dehydro-carotene etc. Among the organic com vent, Moreover, the hydrogenation reactions can be pounds containing acetylenic unsaturation which can 60 carried out at room temperature, or at a temperature be utilized in accordance with this invention are in somewhat above or below room temperature, and at at cluded aliphatic alcohols, i.e., hydroxy substituted mospheric, or a higher pressure. Ordinarily, the reac aliphatic hydrocarbons, containing from four to 45 car tion mixture is stirred or agitated during the hydrogena bon atoms which include primary propargyl alcohols tion reaction. such as 1-butyne-4-ol, 3-methyl-1-butyne-4-ol, 4-pen 65 As a general rule, any suitable solvent can be em ten-1-yne-5-ol; secondary propargyl alcohols such as 1 ployed in the hydrogenation procedure. Thus, for ex butyne-3-ol, 4-penten-1-yne-3-ol, 7-methyl-6-octen-1- ample, one can use as the solvent aliphatic and aro 3,715,404 5 6 matic hydrocarbons, such as, petroleum other, paraffin For a fuller understanding of the nature and objects oils, cyclohexane, benzene, toluene, etc.; halogenated of this invention, reference may be had to the following hydrocarbons, such as, methylene chloride, examples which are given merely as further illustration chloroform, chlorobenzene, etc.; alcohols, such as, of the invention and are not to be construed in a limit methanol, ethanol, isopropanol, etc.; esters, such as, ing sense. ethyl acetate; ethers, such as, dimethyl ether, tetrahydrofuran, etc.; ketones, such as, acetone. EXAMPLE 1 Furthermore, where a water-soluble starting material is to be used, water, or a water-containing solvent, can be In this example, 500 grams of 3-methyl-1-butyne-3- employed. 10 ol were diluted with 100 ml. of a low viscosity paraffin Furthermore, the partial hydrogenation can be car oil (boiling range 60°-90° C. at 12 mm.). To the solu ried out using, in addition to the organic sulfur com tion, thus obtained, there was added 10.0 grams of the pounds disclosed herein, deactivating agents already palladium-lead catalyst and 2.0 grams of dibenzylsul known in the prior art, such as, tertiary amines. fide. After the theoretical quantity of hydrogen (about 15 147 liters) had been taken up, the reaction proceeded Pyridine and quinoline are representative of the tertia further, but only at a very slow rate. The hydrogenation ry amine deactivating agents which can be employed. was discontinued at this point and the catalyst was The preferred hydrogenation catalyst which is used removed by filtration. The 3-methyl-1-buten-3-ol boil in the practice of this invention, is that described in ing point at 50-55° C. at 70 mm. was separated from Helv. Chim. Acta. 35,446 (1952) in which palladium 20 the solvent by distillation. The compound was obtained supported on calcium carbonate as a carrier, is partially in a yield of about 98 percent of theory and, by gas deactivated by the addition of lead. Such a catalyst is chromatographic methods, determined to be 99 per described also in U.S. Pat. No. 2,681,938. For con cent pure. venience, this preferred catalyst will be referred to in The dibenzylsulfide which remained in the paraffin the specification and in the claims simply as a palladi 25 um-lead catalyst. As the carrier material for these oil residue was, without refinement, suitable for use in catalysts there can be used in place of the preferred cal subsequent hydrogenation operations. So used, for ex cium carbonate, barium carbonate, barium sulfate, ample, after repeating the hydrogenation process clay, calcium sulfate, magnesium oxide or charcoal. In described in this example three times, the reaction was the alternative, the catalyst can also be employed 30 effected with the same selectivity and the same rapidity without a carrier material. as was noted the first time the catalyst was used. The quantity of sulfur compound which is used in the Outstanding selectivity was observed in the above practice of this invention is variable within rather wide described partial hydrogenation process when methyl limits. The optimum amount of the organic sulfur com butynol was converted to a methyl butenol using the pound which is to be used in any particular instance 35 palladium-lead catalyst and the following named or can be determined readily by preliminary experiment. ganic sulfur compounds: In general, however, there will be employed at least Organic Sulfur Compounds Quantities in about 0.1 percent by weight of sulfur compound, based Percentages based on the weight of the hydrogenation catalyst. Quantities on the weight of 40 the Catalyst of sulfur compound, slightly or greatly in excess of 0.1 Di-n-butylsulfide 3%-50% percent by weight, based on the weight of the catalyst, Ditertiary butylsulfide 5% - Mercaptopyridine 0.2% can, however, be used, if desired. In the preferred em Thiophenol 0.3% - 3% bodiment of the invention, wherein 1,2-bis-(2-hydrox D,-methionine 5% - 10% yethylthio)-ethane is the sulfur compound employed Methylisothiourea sulfate 100% 45 2-Methylmercapto-4,6-diaminopyrimidine 0.3% - 20% and a palladium-lead catalyst is used, generally, there Phenothiazine 2%. 10% will be used from about 0.1 percent to about 2.0 per Phenothiazine-N-acetic acid ester 50% - 100% Thioanisole 60% cent by weight of the sulfur compound based upon the Thiodiethyleneglycol 50% weight of the catalyst employed. Thiophene 0.3% - 3% Under normal circumstances, there will be incor 50 1,4-Thioxane 5% - 50% Thioxanthone 250% porated into the reaction mixture only one of the previ Thioxanthydrol 250% ously identified organic sulfur compounds. If desired, Di-(o-carboxyphenyl)-disulfide 0.2% - 3% however, a mixture of two or more different organic sulfur compounds can be used to effect the hydrogena tion batch. 55 EXAMPLE 2 It has been found that, as a general rule, the sulfur In this example, 1000 grams of 3-methyl-1-butyne-3- compound, or compounds, which is used in the various ol were hydrogenated in the presence of 50 grams of hydrogenation reactions can be recovered and that palladium-lead catalyst and 14 grams of thiodiethylene i such compound or compounds can be used in sub glycol, i.e., S(CHCHOH), at a temperature of 20 to sequent batches without any preceptible loss of, or 60 22°C. and under a water pressure of 10 cm. After the reduction in, its activity. Thus, for example, where a theoretical quantity of hydrogen had been taken up, particular hydrogenation process has been carried out further absorption of hydrogen was practically nil. The in the absence of a solvent, and after the partially hydrogenation reaction was discontinued at this point, hydrogenated product has been removed, the residue, 65 the catalyst was removed by filtration and the filtrate containing the organic sulfur compound, is recovered was subjected to distillation. There was, thus obtained, and added, as is, to the new starting material together about 1,000 grams of 3-methyl-1-buten-3-ol of about with the hydrogenation catalyst. 99 percent purity. The compound had a boiling point of 3,715,404 7 8 94 to 96° C. at 742 mm. The residue consisted essen The partially crystalline 15,15'-all-trans-g-apo-8'- tially of the starting thiodiethyleneglycol, boiling point carotinal was brought into solution by the addition of at 168 C. at 14 mm. approximately 50 ml. of methylene chloride to the The sulfur compound which remained in the residue reaction mixture. The catalyst was removed by filtra was, without distillation, used in the hydrogenation of 5 tion and the filtrate subsequently was evaporated al subsequent batches. most to dryness. The residue was brought into solution EXAMPLE 3 using 80 ml. of petroleum ether and approximately 20 ml. of ethylene chloride. Thereafter, the solution was 384 Grams of 3-methyl-4-penten-1-yn-3-ol, dis- 10 concentrated to a volume of about 60 ml. By this solved in 650 ml. of methylene chloride, was procedure, crystallization of the 15, 15'-all-trans-3-apo hydrogenated in the presence of 10 ml. of 8'-carotinal was accomplished slowly. The compound, triethylamine, 20 grams of palladium-lead catalyst and melting at 138°C., was obtained in a yield of 9.6 grams, 0.4 grams of 1,2-bis-(2-hydroxyethylthio)-ethane at a or 86.5 percent of theory; purity of 99.7 percent temperature of 20°C., with vigorous stirring. After the (U.V.). absorption of 1 mole of hydrogen, further absorption of 15 hydrogen ceased. The theoretical takeup was 98 liters EXAMPLE 7 of hydrogen, 201729 Torr. Subsequently, the solution 200 Grams of dehydroisophytol was mixed with 600 was filtered to remove the catalyst therefrom, following ml. of methylene chloride, 10 grams of sodium car which the methylene chloride solvent was separated, 20 bonate, 10 grams of palladium-lead catalyst and 0.1 from the thus obtained 3-methyl-1,4-pentadiene-3-ol, gram of 1,2-bis-(2-hydroxy-ethylthio)-ethane. by distillation. Hydrogenation of the dehydroisophytol was, thereafter, accomplished at a temperature of 20° C. EXAMPLE 4 with vigorous stirring. After a period of about 5 hours, 685 Grams of 3-methyl-1-pentyne-3,5-diol, dissolved 25 absorption of hydrogen had ceased. The solution was in 600 ml. of methylene chloride, was hydrogenated in then filtered and the methylene chloride removed by the presence of 3 ml. of triethylamine, 30 grams of pal vacuum distillation. There was, thus obtained, 202 ladium-lead catalyst and 0.15 gram of 1,2-bis-(2- grams of crude isophytol. The crude product did not hydroxyethylthio)-ethane, under the conditions contain any of the dehydroisophytol starting material described in Example 3, to form 3-methyl-1-penten-3,5 30 or any traces of products resulting from excessive -diol. The quantity of hydrogen absorbed during the hydrogenation. reaction corresponded to the quantity theoretically required, namely, 153 liters of hydrogen at 20°/737 EXAMPLE 8 Torr. 35 '6,6'-trimethylcyclohexen-(1")-yl)-2,7-nonadiene-4-In this example, 600 grams of 3,7-dimethyl-9-(2 EXAMPLE 5 yne-1,6-diol, in 900 ml. of methylene chloride, was 500 Grams of 3,7-dimethyl-6-octen-1-yn-3-ol was hydrogenated in the presence of a mixture of 50 grams hydrogenated in the presence of 25 grams of palladi of palladium-lead catalyst, 0.36 gram of 1,2-bis-(2- um-lead catalyst and 2.5 grams of thiodiethylene glycol 40 hydroxyethylthio)-ethane, 0.6 gram of at a temperature within the range of from about 20° C. thioethyleneglycol and 14.4 ml. of dimethyl to about 23° C. and a water pressure of 10 cm. The ethanolamine at a temperature of 20° C. At the end of reaction was attended with continuous stirring. After a about 7% hours, absorption of 44 liters of the hydrogen period of about 8 hours, the takeup of hydrogen had, had taken place and further absorption had ceased. for all practical purposes, ceased. The hydrogen reac 45 The catalyst was then removed by filtration and washed tion was discontinued, the catalyst was removed by fil with methylene chloride. After removal of the tration and the, thus obtained, linalool, that is 3,7- methylene chloride by vacuum distillation and after dimethyl-1,6-octadien-3-ol was agitated for a period of crystallization from petroleum ether, there was ob about 1 hour with 100 ml. of water. Thereafter, the tained 3,7-dimethyl-9-2',6',6'-trimethylcyclohexen water was removed and the linalool was dried over 50 (1')-yl)-2,4,7-nonatriene-1,6-diol, in a yield of at least sodium sulfate. about 94 percent of theory. We claim: EXAMPLE 6 1. A process for the hydrogenation of organic com In this example, 11.1 grams of 15, 15'-dehydro-e-8'. 55 pounds selected from the group consisting of aliphatic carotinal was introduced, with 3.0 grams of palladium hydrocarbons containing from four to 45 carbon atoms lead catalyst, in an atmosphere of carbon dioxide gas, and having one or more triple bonds, aryl and cycloal into a shaking vessel. To this mixture there was added kyl hydrocarbons containing from eight to 45 carbon 0.2 ml. of triethylamine and 3.0 mg. of 1,2-bis-(2- atoms and having an aliphatic side chain with one or hydroxyethylthio)-ethane dissolved in 3 ml. of ethanol. 60 more triple bonds, hydroxy substituted aliphatic The mixture, thus obtained, was diluted with 100 liters hydrocarbons containing from four to 45 carbon atoms of methanol. Hydrogenation of the unsaturated com and one or more triple bonds, cycloalkyl hydrocarbons pound was then effected at a temperature of 20° C. containing from eight to 45 carbon atoms having a After about 8 hours, there had been absorbed the quan hydroxy substituted aliphatic side chain with one or 65 more triple bonds, carboxy substituted aliphatic tity of hydrogen theoretically required and, sub hydrocarbons containing from four to 45 carbon atoms sequently, little additional hydrogen was taken up. The and having one or more triple bonds and aryl contain hydrogenation reaction was, therefore, discontinued. ing hydrocarbons containing six to 45 carbon atoms 3,715,404 9 0 and at least one keto group directly attached to the aryl of said catalyst, is used. moiety comprising hydrogenating said organic com 4. The process of claim 1 wherein said sulfur deriva pound in a liquid medium in the presence of a palladi tive is 1,2-bis-(2-hydroxyethylthio)-ethane. um catalyst partially deactivated with lead, bismuth, 5. The process of claim 1 wherein said organic com sulfurcopper, derivative zinc, tin ofmercury, the formula: cadmium or thorium; and a 5 pound is a hydroxy substituted hydrocarbon. 6. The process of claim 5 wherein said organic com pound is 3-methyl-butyn-(1)-ol-(3). wherein x is an integer of from 1 to 6 inclusive. 7. The process of claim 5 wherein said palladium 2. The process of claim 1 wherein said palladium 10 catalyst is partially deactivated with lead. catalyst is partially deactivated with lead. 8. The process of claim 5 wherein said sulfur deriva 3. The process of claim 1 wherein at least 0.1 percent tive is 1,2-bis-(2-hydroxyethylthio)-ethane. by weight of said sulfur derivative, based on the weight k sk k ; : 15

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