Патент USA US2108133код для вставки
.2,108,133 Patented Feb. 15, 1938 ‘UNITED STATES PATENT’ OFFICE PROCESS FOR PRODUCING HIGH MOLECU LAB ALCOHOLS FROM THE CORRESPOND ma xa'rorms Francis John McCall, Wilmington, Del., assignor to E. 1. du Pont de N monrs a Company,'Wll ‘mini-ton, Del., a cor ration of Delaware No Drawing. Application November 25, 1936, ‘ Serial No. 112,709 14 Claims. (Cl. 260-150) This invention relates to the process of cata lytically hydrogenating ketones to produce the corresponding secondary alcohols and, speci?cally, to the process of producing straight-chain, sec 5 ondary, aliphatic alcohols by catalytically hy drogenating the corresponding ketones of the type 0 CH3(0H|)n_-g-(C H1) ‘CH! 10 where "n” and “m" may be any integers from zero to fourteen, inclusive, the values of “n” and “m” being subject to the further limitation that "11” plus “m” must be equal toten, eleven, twelve, ) thirteen, or fourteen. The phrase “straight chain aliphatic ketone having approximately 2 ?fteen carbon atoms" is for the present purpose de?ned as, and will hereinafter be used to refer to any ketone belonging to the above class, or any mixture which contains only ketones belong ing tothe above class. Furthermore, an alcohol will be said to ‘fcorrespond” to a given 'ketone when the former differs from the latter only in having a carbinol group in place of the carbonyl 2 group of the ketone. the presence of a platinum-black catalyst (Vavon, Ann. Chim. 1 (9), 144 (1914)). The literature shows, however, that more vigorous conditions have had to be used in attempts to hydrogenate the higher ketones, and that, under these more vigorous conditions, side reactions such as hydro .carbon formation and polymerization have pre vented the successful use of the catalyst proce dure in preparing alcohols from the straight-chain ketones of higher molecular weight. Thus, Hal 10 ler and Lassieur (Compt. rend. 150, 1017 (1910)) in attempting to convert undecanone-2 to the cor responding secondary alcohol by hydrogenation at 300° C. over a nickel catalyst obtained, in addi tion to unchanged ketone, a hydrocarbon and a 15 condensation product having twenty-two car bons per molecule-but they obtained no'eleven carbon alcohol. Other workers have observed the formation of hydrocarbons and condensation products during the catalytic hydrogenation of 20 higher ketones, and, as will be pointed out later, one of the. objects of the present invention is the avoidance of these side reactions. This invention has as an object the conversion of straight-chain aliphatic ketones or mixtures 26 The prior art discloses numerous methods for‘ thereof having approximately 13 to 1''! carbon atoms into the corresponding straight-chain sec the synthesis of secondary alcohols. The Grig ondary alcohols or mixtures thereof. A further nard method may be used quite generally, but be object is to accomplish the conversion by means cause it is such an expensive and laborious pro cedure it is not practical for the commercial of catalytic hydrogenation. A still further object 80 30 is to accomplish the conversion in such a man preparation of alcohols. The most practical and direct method?for/ ner as to avoid side reactions which result in the production of secondary alcohols involves the the formation of hydrocarbons and condensation chemical reduction or the hydrogenation of a products, so that, if desired, the alcohols can ketone. Thus, pentadecanol-B has been prepared readily be obtained in nearly theoretical yield, 85 from the ketone by a sodium-alcohol reduction in a high state of purity, and with a minimum of (Kipping, Jour. Chem. Soc., 63, 455 (1893)). The reaction involved may be represented by the effort and expense. Other objects will appear hereinafter. These objects are accomplished by bringing a mixture of hydrogen and ketone or mixture of all) ketones in intimate contact with a catalyst in such a temperature range that the carbonyl group is selectively converted into the carbinol following general equation: ' w 4 It has long been known that acetone, methyl ethyl ketone, and other ketones of low molecular weight can be catalytically hydrogenated to the corresponding secondary alcohols in either the liquid or vapor phase and in the presence of any of a wide variety of noble or base metal hydro genation catalysts. For example, acetone has ‘been completely converted into propanol-2 by 5 O hydrogenation in the presence of an‘ Iactive nickel catalyst at drogen pressure of and Adkins, Jour. (1932)). Similarly as 23° C., and under a hy 2 to 3 atmospheres (Covert Am. Chem. Soc. 54, 4117 heptanone-4 has been con verted into heptanol-4 under mild conditions in group. ‘ Ketones suitable for use in carrying out this 45 invention may be prepared according to a wide variety of procedures. For example,- pentadec anone-8 can be prepared by ketonization of capryllc acid from coconut oil. Similarly, ke tonization of the mixture of enanthic, caprylic, and pelargonic acids obtained from the oxidation of oleic acid gives a mixture of tridecanone-‘l, tetradecanone-7, pentadecanone-7, pentadecan one-8, hexadecanone-S, and heptadecanone-Q. Likewise, ketonization of coconut oil acids with so. 2 9,108,188 acetic acid gives a mixture from which tri ‘decanone-2, pentadecanone-2, heptadecanone-2, tridecanone-6, pentadecanone-6, heptadecanone 6, pentadecanone-8, and heptadecanone-8 may be separated, etc. The following examples are instances of the application of this invention. They are not to be considered as limitations of the invention since many modi?cations may be made without de 10 parting from the spirit and scope thereof. In addition to the above, the following alco hols have been prepared by hydrogenating the proper ketone under conditions similar to those of ,Example I: tridecanol-7, B. P. 130° to 131° C. at 9 mm. pressure, M. P. 41° C.; heptadecanol-Q, B. P. 174;’ C. at 9 mm. pressure, M. P. 595° C.; pentadecanol-‘i, B. P. 155° to 156° C. at 10 mm., M. P. 31° C.; and pentadecanol-2, B. P. 166° C. to 170° C. at 14 mm. pressure, M. P. (crude) 27° to 28° C. ‘ 10 Although in the above examples certain de? nite conditions of pressure, temperature, catalyst ratio, etc., have been mentioned, it is to be Example I A solution of 141 grams of pentadecanone-8 in 47 grams of 95% ethanol was charged into a understood that these conditions are'by no means 16 pressure tube equipped with a shaking device and critical except as hereinafter speci?ed. 15 15 grams of ‘unsupported nickel catalyst was ‘In general, the process is operable between added. Hydrogen was then admitted to the ves ‘the temperature limits of about 75° to about sel and maintained at a pressure of 2000 to 2400 200° C. Temperatures of about 100° to about pounds per square inch during the hydrogenation 150° C. are preferred, however, for the reasons 20 which, at 150° 0., required ?fteen minutes. that the reaction is less rapid at the lower op The product from this and a similar run were erable temperatures, and at the higher operable 20 combined and ?ltered while still warm. The temperatures side reactions such as hydrocarbon ?ltrate, upon distillation, gave a 97% yield of formation begin to be important. pentadecanol-8, B. P. 172° to 177° C. at 23 mm. Hydrogen pressures from about atmospheric 25 pressure, of which 93% boiled at 175° to 177° C. pressure up to and above 5000 pounds per square at 23 mm. pressure. The product was a white, waxy solid: M. P. 485° C.; hydroxyl number, found, 241.0, 238.7 (calculated value, 246.0). Example I! A 100-gram sample of pentadecanone-8 was hydrogenated under conditions similar to those ‘of Example I, except that absolute alcohol was used as solvent and the hydrogenation proceeded 85 at a temperature of 100° to 120° C. A 91 per cent yield of pentadecanol-8, B. P. 172° to 177° C. at 23 mm. pressure, was isolated. . Example HI About one-third of a commercial sample of coconut oil acids was distilled to give a dis tillate consisting mainly of caproic, caprylic, and capric acids. Ketonization of the distillate gave a mixture which consisted of thirteen, ?fteen, 45 and seventeen carbon straight-chain ketones. Hydrogenation of this crude ketone mixture, according to the procedure described in Ex ample I, gave a corresponding mixture of sec ondary alcohols, a white waxy solid having a 50. slight fatty odor: B. P. 135° to 208° C. at 15 mm. pressure, freezing point 39° to 41° C. The run required 425 hours at a pressure of about 2000 pounds per square inch and a temperature of 150° C. 55 6.0 65 70 75 ‘ _ Example IV A mixture of ketones similar to that described in Example III was hydrogenated at 125° C., inch may be used. It is preferable to use pres sures of about 100 to about 3000 pounds per square inch, because at lower pressures there is 25 a tendency toward polymerization and higher pressures necessitate the use of more expensive 80 equipment. ' It is preferable to use a solvent such as ethanol, methanol, dioxane, or any other solvent which does not react with the ketone, alcohol, or cat alyst. The use of a solvent appears to accelerate 86 the hydrogenation somewhat and, since the higher alcohols are usually solids, a solvent'as sists in the removal of the catalyst from the ‘ product. However, it has been shown that the reaction proceeds readily in the absence of a solvent; 40 under certain circumstances, therefore, (for ex ample, when the product is to _be used directly without puri?cation) the use of a solvent may be quite undesirable. The ketone to be hydrogenated does not need 45 to be pure. It is only necessary that it contain no large amount of materials which poison the catalyst (for example, acids, organic sulfur, etc.). Since the product is usually white or colorless and corresponds in purity to that of the ke 60 tone hydrogenated it is unnecessary, for most purposes, that the product be puri?ed. When a puri?cation is desired it may be accomplished by distillation, recrystallization, or by other known methods. 4 In the practice of this invention any hydro in the absence of a solvent and in the presence genating catalysts, such as platinum, palladium, of 5 per cent of a nickel-on-kieselguhr catalyst. copper (or oxide), iron (or oxide), or mixtures This run required ?ve hours at a pressure range - of the above may be used, but nickel is pre 60 of 300 to 500 pounds per square inch and gave ferred because of its high degree of activity, low cost, and ease with which it is prepared in a product similar to that described under Ex very active form. _ ample III. It'is preferred to allow the reaction to pro Emample V ceed until no more hydrogen is being absorbed A sample of mixed enanthic, caprylic, and in order that the product may be of the highest pelargonic acids was obtained by the oxidation purity. However, since the last 0-20 per cent of of oleic acid. Ketonization of these acids gave hydrogen absorption usually takes place at a a mixture which consisted of the thirteen, four lower rate than that of the initial absorption, teen, ?fteen, sixteen, and seventeen carbon ke it is sometimes economical from the time stand tones. Hydrogenation of the mixture of ketones, point to interrupt the hydrogenation before it 70 according to the procedure of Example I, gave is complete. a mixture of the corresponding secondary al Those skilled in the chemical art will recog cohols: B. P. 152° to 185° C. at 14 mm. pressure, nlre the importance of alcohols as one of the freezing point 48° to 50° C. most fundamental intermediates in the prepara 76 3 tion of a wide variety of organic chemicals. It characterized in that the reaction is carried out at a temperature of about 100° to about 150° C. and under a pressure of about 100 to about 1000 pared by direct sultation of the alcohols, and _ pounds per square inch. 5. The process which comprises bringing a which are valuable as textile assistants, wetting, penetrating, emulsifying,‘ and cleansing agents. mixture of hydrogen and a saturated straight The higher secondary alcohols, as such, may be chaln aliphatic ketone having from 13 to 17 car used as wax-modifying agents, lubricants, etc. bon atoms dissolved in ethanol in contact with a ~ The present invention furnishes a simple, di highly active nickel catalyst at a temperature of ' about 100° to about 150° C. and under a pres—; 10 10 rect, economical synthesis for certain of the higher secondary alcohols. sure of about 100 to about 3000 pounds per square By the use of the present invention certain inch. , advantages are obtained. These may be enu 6. A process which comprises bringing a mix merated as follows: ture of hydrogen and a saturated straight-chain 1. The invention enables one to proceed from, aliphatic ketone having 15 carbon atoms in con 15 15 an abundant naturally-occurring raw material tact with a highly active nickel catalyst at a tem is su?icient to mention here the higher second ary alkyl sulfates, which are advantageously pre (fatty acid) to the higher secondary alcohols perature between 75° and 200° C. by a procedure which consists of only two stages. 7. The process in accordance with claim 6 characterized in that the reaction is carried out at a temperature of about 100° to about 150° C. 20 2. ‘The process of the present invention is superior to the purely chemical reductions of the prior art in that it employs hydrogen, obviously the most economical of reducing agentsand one 8. The process in accordance with claim 6 characterized in that the reaction is carried out under a pressure between 100 and 3000 pounds 20 which gives rise to no by-products. As a result of the latter feature,‘ the product may be used ~without puri?cation or after only a very simple puri?cation. I _3. The process of the present invention makes 30 it possible to convert the higher straight-chain ketones into the corresponding secondary alco hols in practically quantitative (97 per 'cent) yields. As a result the process entails no appre ciable weight loss, and puri?cation of the prod uct becomes unnecessary or, where desired, be comes a relatively simple procedure.v It is apparent that many widely different em bodiments of this invention may be made with out departing from the spirit and scope thereof 40 and therefore it is not intended to be limited ex cept as indicated in the appended claims. I claim: 1. The process which comp-rises bringing a mixture of. hydrogen and a saturated straight 45 chain aliphatic ketone having from 13 to 17 car bon atoms in contact with a highly active nickel catalyst at a temperature between ‘75° and 200° C". 2. The, process in accordance with claim 1 characterized in that the reaction is carried out 50 at a temperature of about 100° to about 150° C. 3. The process in accordance with claim 1 characterized in that the reaction is carried out per square inch. v . ' 9. The process in accordance with claim 6 25 characterized in that the reaction is carried out at a temperature of about 100° to about 150° C. and under a pressure of about 100 to about 1000 pounds per-square inch. 10. The process which comprises bringing a 30 mixture of hydrogen and a saturated straight chain aliphatic ketone having 15 _carbon atoms dissolved in ethanol in contact with a highly ac tive nickel catalyst at a temperature of about 100° to about 150° C. and under a pressure of about 100 to about 3000 pounds per square inch. 11. The process which comprises bringing a mixture of hydrogen and pentadecanone-B in contact with a nickel catalyst at a temperature 40 between 75° and 200° C. 12. A process which comprises bringing a mix ture of hydrogen and pentadecanone-8 dissolved in ethanol in contact with a nickel catalyst at a temperature of about 150° C. and at a pressure of about 2000 to about 2400 pounds per square‘ inch. - under a pressure between 100 and 3000 pounds 13. A process which comprises bringing a mix ture of hydrogen and pentadecanone-4 in con tact with a nickel catalyst at a temperature be 60 tween 75° and 200° C. 14. A process which comprises bringing a mix ture of hydrogen and pentadecanone-2 in con tact with a nickel catalyst at a temperature be per square inch. tween 75° and 200° C. . 4. The process in accordance with- claim 1 ‘ FRANCIS JOHN McCALL.