Europaisches Patentamt J European Patent Office (jy Publication number: 0 458 21 6 A1 Office europeen des brevets EUROPEAN PATENT APPLICATION © Application number: 91108057.0 © Int. CI.5: C07C 49/04, C07C 45/73 © Date of filing: 17.05.91 © Priority: 21.05.90 JP 130553/90 © Applicant: MITSUBISHI KASEI CORPORATION 5-2, Marunouchi 2-chome Chiyoda-ku @ Date of publication of application: Tokyo 100(JP) 27.11.91 Bulletin 91/48 © Inventor: Ushikubo, Takashi © Designated Contracting States: 1-1-66, Tachibanadai, Midori-ku DE FR GB NL Yokohama-shi, Kanagawa-ken(JP) Inventor: Kakuno, Yumiko 43-5-205, Chigusadai, Midori-ku Yokohama-shi, Kanagawa-ken(JP) Inventor: Tsujiura, Hisako 243-2, Ariyoshi-cho Shiba-shi Chiba-ken(JP) © Representative: Wachtershauser, Giinter, Dr. Tal29 W-8000 Mlinchen 2(DE) © Method for producing methyl isobutyl ketone. © A method for producing methyl isobutyl ketone, which comprises contacting acetone and hydrogen in the the presence of palladium and a metal oxide and/or metal hydroxide treated with an organosilicon compound of formula (I): K (OR2)bXoSi (I) wherein each of R1 and R2 is a group selected from the group consisting of hydrogen, and alkyl, vinyl and aryl R2 be the groups having a total carbon number of at most 30, which may have substituents, and R1 and may same or different from each other, X is an element selected from the group consisting of hydrogen, fluorine, chlorine, bromine and iodine, and a, b and c are 0 £ a S 4, 0 < b £ 4 and 0 ^ c £ 4, respectively, and a + b + c = 4. < CO 00 in a. UJ Rank Xerox (UK) Business Services EP 0 458 216 A1 The present invention relates to a method for producing methyl isobutyl ketone by a one step reaction from acetone and hydrogen. Methyl isobutyl ketone (hereinafter referred to simply as MIBK) is industrially useful as a raw material for e.g. organic solvents, coating materials or stabilizers. 5 MIBK is industrially produced usually by the following three step process using acetone and hydrogen as starting materials. condensation 7° acetone > diacetone alcohol * dehydration * > mesityl oxide ** hydrogenation ** > methyl isobutyl ketone 75 This method is characterized in that the steps of condensation, dehydration and hydrogenation as shown by the above formulas are sequentially conducted and thus the method requires a long process. In the first step, acetone is catalytically reacted in a liquid phase under atmospheric pressure at a temperature * 20 of from 10 to 20 C by means of a solid alkali catalyst such as barium hydroxide to obtain diacetone alcohol. Then, diacetone alcohol obtained by the condensation is separated from unreacted acetone. The separated diacetone alcohol is heated at a temperature of from 100 to 120°C in a liquid phase in the presence of an acid catalyst such as sulfuric acid or phosphoric acid for dehydration to obtain mesityl oxide. Then, this mesityl oxide is separated and purified, and it is hydrogenated, for example, in the 25 presence of a palladium catalyst to obtain MIBK. This method is widely used on an industrial scale. However, its process is long including the steps of condensation, dehydration and hydrogenation. Further the operation is cumbersome as it is required to separate intermediates such as diacetone alcohol and mesityl oxide during the process. Further, the condensation reaction from acetone to diacetone alcohol is an equilibrium reaction, and the conversion is as 30 low as about 15%. Under these circumstances, various studies have been made on a method for producing MIBK directly from acetone and hydrogen in one step. Such a method is very advantageous from the equilibrium point of view, and it is thereby possible to increase the conversion of the raw material per pass. It is economically advantageous over the three step process. The following methods have been reported for the production of 35 MIBK in one step: (1) a method for synthesizing MIBK using an acid-type ion exchange resin and palladium-carbon as catalysts (German Patent No. 1233453) (2) a method of using a catalyst having palladium supported on zirconium phosphate (Japanese Examined Patent Publication No. 6994/1974) 40 (3) a method of using a catalyst having palladium supported on H-type zeolite (Japanese Examined Patent Publication No. 4643/1971) (4) a method of using palladium-Group IVB metal oxide as catalyst (Japanese Examined Patent Publication No. 15574/1977), and (5) a method of using a palladium-niobic acid catalyst (Japanese Unexamined Patent Publication No. 45 78745/1986). However, in these methods, it is impossible to increase the reaction temperature in the case of a resin catalyst, and the preparation of the catalyst is cumbersome. Further, the selectivity for desired MIBK is low, or the catalytic activities are insufficient. Because of these drawbacks, they are not satisfactory from the industrial point of view. so The present inventors have conducted an extensive research to solve such problems of the prior art and to develop a method for producing MIBK in a single step in good yield from acetone and hydrogen. As a result, the present invention has been accomplished. The present invention provides a method for producing methyl isobutyl ketone, which comprises contacting acetone and hydrogen in the presence of palladium and a metal oxide and/or metal hydroxide 55 treated with an organosilicon compound of the formula (I): Ri (OR2)bXcSi (I) EP 0 458 216 A1 wherein each of R1 and R2 is a group selected from the group consisting of hydrogen, and alkyl, vinyl and R2 aryl groups having a total carbon number of at most 30, which may have substituents, and R1 and may be the same or different from each other, X is an element selected from the group consisting of hydrogen, fluorine, chlorine, bromine and iodine, and a, b and c are 0 £ a < 4, 0 i b S 4 and 0 £ c & 4, respectively, 5 and a + b + c = 4. Now, the present invention will be described in detail with reference to the preferred embodiments. The method of the present invention is characterized by contacting acetone and hydrogen in the of presence of palladium and a metal oxide and/or metal hydroxide treated with an organosilicon compound the formula (I): 10 K (OR2)bXcSi (I) wherein each of R1 and R2 is a group selected from the group consisting of hydrogen, and alkyl, vinyl and R2 aryl groups having a total carbon number of at most 30, which may have substituents, and R1 and may 75 be the same or different from each other, X is an element selected from the group consisting of hydrogen, fluorine, chlorine, bromine and iodine, and a, b and c are 0 £ a S 4, 0 £ b £ 4 and 0 £ c i 4, respectively, and a + b + c = 4. With respect to the organosilicon compound of the above formula (I), each of R1 and R2 is a group selected from the group consisting of (1) hydrogen, (2) an alkyl group having a total carbon number of at 20 most 30, which may have substituents, (3) a vinyl group having a total carbon number of at most 30, which may have substituents, and (4) an aryl group having a total carbon number of at most 30, which may have substituents. The respective substituents may contain a carbon-carbon double bond, and they may further contain hetero atoms such as oxygen, nitrogen, sulfur and silicon. Further, the organosilicon compound of the formula (I) may be the one wherein a plurality of silicon 25 atoms are linked. Specific examples of such an organosilicon compound include the following: Trimethylchlorosilane Me3SiCl 30 Dimethyldichlorosilane Me2SiCl2 Methyltrichlorosilane MeSiCl3 35 Methyldichlorosilane MeHSiCl2 40 45 50 55 EP 0 458 216 A1 Dimethylchlorosilane Me2HSiCl Dimethylvinylchlorosilane Me2ViSiCl 5 Methylvinyldichlorosilane MeViSiCl2 Methylchlorodisilane MenSi2Cl6_n(n = 2-3) 70 Triphenylchlorosilane Ph3SiCl Methyldiphenylchlorosilane MePh2SiCl Diphenyldichlorosilane Ph2SiCl2 75 Methylphenyldichlorosilane MePhSiCl2 Phenyltrichlorosilane PhSiCl3 20 Chlororaethyldimethylchlorosilane ClCH2Me2SiCl Vinyltrichlorosilane ViSiCl3 25 /-chloropropyltrimethoxysilane Cl(CH2)3Si(OMe)3 7-chloropropylmethyldichlorosilane Me Cl(CH7USiCl«, 30 i i i /-chloropropylmethyldimethoxysilane Me Cl(CH2)3Si(OMe)2 7-chloropropylraethyldiethoxysilane Me 35 Cl(CH2)3Si(OEt)2 Methyldiraethoxysilane MeHSi(0Me)2 Methyldiethoxysilane MeHSi(OEt)2 40 Dimethylethoxysilane Me2HSiOEt In the above formulas, Me represents a methyl group, Vi represents a vinyl group, Ph represents a 45 phenyl group and Et represents an ethyl group. The same applies hereinafter. It is preferred to use an organosilicon compound of the formula (I) wherein c = 0, i.e. the one which does not contain X. Specific examples of such an organosilicon compound include the following: 50 55 EP 0 458 216 A1 Trimethylmethoxysilane Me3SiOMe Trimethylethoxysilane Me3SiOEt Dimethyldimethoxysilane Me2Si(OMe)2 Dimethyldiethoxysilane Me2SiMe2Si(OEt)2 (OEt ) 2 Methyltrimethoxysilane MeSi(OMe)3 10 Tetramethoxysilane Si(OMe)4Si (OMe) 4 Methyltriethoxysilane MeSi(OEt)3 75 Tetraethoxysilane Si(OEt)4 Vinyltriethoxysilane ViSi(OEt)3 Dimethylvinylmethoxysilane Me2ViSi0Me 20 Dimethylvinylethoxysilane Me2ViSiOEt Methylvinyldime thoxysilane MeViSi ( OMe ) 2 25 Methylvinyldiethoxysilane MeviSi (OEt)(OEt ) 2 Diphenyldimethoxysilane Ph2Si(OMe)2 Phenyltriraethoxysilane PhSi(OMe)3 30 Diphenyldiethoxysilane Ph2Si(OEt)2Ph2Si (OEt ) 2 Phenyltriethoxysilane PhSi(OEt)3 35 y-Aminopropylt r iethoxysilane H2N ( CH2 ) 3Si ( OEt ) 3 N- (/?-Aminoethy 1 ) -y- aminopropyltrimethoxysilane H2N(CH2)2NH(CH2)3Si(OMe)3 40 N- (^-Aminoethyl ) -y- aminopropylmethyldimethoxysilane Me H2N ( CH2 ) 2NH ( CH2