Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-08-21
2002-12-10
Powers, Fiona T. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S273000, C549S295000
Reexamination Certificate
active
06492532
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a method for producing a carbonyl compound by dehydrogenating an alcohol. More particularly, it relates to a method for producing a carbonyl compound by dehydrogenating an alcohol in the presence of a complex compound catalyst comprising ruthenium and a specific organic phosphine. A suitable example to which the method of the invention is applied is production of &ggr;-butyrolactone from 1,4-butanediol.
BACKGROUND ART
Hitherto, there have been proposed several methods for producing a carbonyl compound by dehydrogenating an alcohol in the presence of a complex compound catalyst wherein a specific transition metal and a specific organic phosphine are combined. For example, a reaction of obtaining a lactone compound by dehydrogenating a diol using iridium-triisopropylphosphine complex, ruthenium-triphenylphosphine complex and rhenium-triisopropylphosphine complex as catalysts is described in J. Orgmet. Chem., 429 (1992) 269-274, a reaction of obtaining a lactone compound by dehydrogenating a diol using ruthenium-triphenylphosphine complex different from the above as a catalyst is described in J. Org. Chem., 1987, 52, 4319-4327 and Tetrahedron Let., 1981, 22, 5327-5330, and a reaction of obtaining a lactone compound by dehydrogenating a diol using ruthenium-bis(diphenylphosphino)butane compound complex as a catalyst is described in Chem. Soc. Japan, 1982, 1179-1182.
However, in these reactions, the dehydrogenation of the alcohol substrate is accelerated by the presence of a hydrogen acceptor such as acetone in the reaction system, and the catalyst activity is remarkably decreased when the hydrogen acceptor is not present.
In Bull. Chem. Soc. Jpn., 61, 2291-2294 (1988), a reaction of dehydrogenating methanol using rutheniumethyldiphenylphosphine complex or ruthenium-diethyl-phenylphosphine complex as a catalyst is described. In this method, however, there is a problem that the catalyst activity is remarkably low. In addition, there is no description or no suggestion of a method for producing &ggr;-butyrolactone effectively by the dehydrogenation of 1,4-butanediol and successive intramolecular cyclization.
The reaction requiring a large amount of the hydrogen acceptor is extremely disadvantageous for industrial practice. In addition, since the hydrogen acceptor is converted to other compound through the dehydrogenation of the alcohol, the acceptor cannot be reused. Therefore, the method is regarded to be industrially impractical.
Moreover, there are described methods for producing &ggr;-butyrolactone by dehydrogenating 1,4-butanediol in a vapor phase using copper-chromiummanganese catalyst or copper-chromium-zinc catalyst in Japanese Patent Publication No. 17954/1992 or using a catalyst containing copper, chromium and barium in Japanese Patent Laid-Open No. 232874/1991. These methods, however, do not solve the problems of selectivity and deterioration of the catalysts, or, owing to the vapor phase process, it is difficult to avoid the limitation derived from the equilibrium with the reverse reaction and the problems of the selectivity and the deterioration of the catalyst can be not completely solved.
An object of the invention is to provide a method for producing a carbonyl compound by dehydrogenating an alcohol, wherein the carbonyl compound is produced industrially advantageously at a good selectivity in high yields under mild reaction conditions.
Furthermore, another object of the invention is to provide a method for producing &ggr;-butyrolactone industrially advantageously at a good selectivity in high yields under mild reaction conditions by dehydrogenation of 1,4-butanediol and successive cyclization.
DISCLOSURE OF THE INVENTION
As a result of the extensive studies for solving the above problems, the present inventors have found that a complex compound catalyst comprising ruthenium and an organic phosphine wherein aliphatic carbons are bonded to two or more of the three bonding hands of the phosphorus atom can be used as a catalyst for efficiently dehydrogenating an alcohol to produce a carbonyl compound. Especially, they have found that the above complex compound catalyst can be used as a suitable catalyst for producing &ggr;-butyrolactone from 1,4-butanediol. The invention has been accomplished based on the above findings.
Namely, a gist of the invention is a method for producing a carbonyl compound, which comprises dehydrogenating an alcohol in the presence of a complex compound catalyst comprising ruthenium and an organic phosphine wherein aliphatic carbons are bonded to two or more of the three bonding hands of the phosphorus atom.
Moreover, another gist of the invention is a method for producing &ggr;-butyrolactone, which comprises dehydrogenating 1,4-butanediol in the presence of a complex compound catalyst comprising ruthenium and an organic phosphine wherein aliphatic carbons are bonded to two or more of the three bonding hands of the phosphorus atom.
Best Mode for Carrying Out the Invention
The catalyst for use in the invention is a complex compound catalyst comprising ruthenium and an organic phosphine wherein aliphatic carbons are bonded to two or more of the three bonding hands of the phosphorus atom. The catalyst may be prepared beforehand and used for the reaction, or each component constituting the catalyst may be incorporated into the reaction system to form the catalyst in the reaction system.
The form of ruthenium metal to be fed is not particularly limited and may be metal ruthenium or a ruthenium compound. Examples of the ruthenium compound include oxides, hydroxides, inorganic acid salts, organic acid salts, complex compounds, and the like, and specific examples include ruthenium dioxide, ruthenium tetraoxide, ruthenium hydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium acetate, tris(acetylacetonato)ruthenium, sodium hexachlororuthenate, dipotassium tetracarbonylruthenate, pentacarbonylruthenium, cyclopentadienyldicarbonylruthenium, dibromotricarbonylruthenium, chlorotris(triphenylphosphine)hydridoruthenium, tetra(triphenylphophine)dihydridoruthenium, tetra(trimethylphophine)dihydridoruthenium, bis(tri-n-butylphosphine)tricarbonylruthenium, tetrahydridododecacarbonyltetraruthenium, dodecacarbonyltriruthenium, dicesium octadecacarbonylhexaruthenate, tetraphenylphosphonium undecacarbonyl hydridotriruthenate, and the like. Commercially available compounds may be used as these compounds, or they may be synthesized according to known methods.
The organic phosphine for use in the invention is a phosphine wherein aliphatic carbons are bonded to two or more of the three bonding hands of the phosphorus atom. Examples of the organic phosphine include a trialkylphosphine wherein alkyl groups are bonded to all the three bonding hands of the phosphorus atom, a dialkylarylphosphine wherein alkyl groups are bonded to two of the three bonding hands of the phosphorus atom and an aryl group is bonded to the remaining one hand, and the like. One or two or more phosphorus atom(s) may be present in one molecule of the organic phosphine, and the phosphorous atom may be monodentate or polydentate toward ruthenium.
The alkyl group is a saturated or unsaturated, linear, branched chain or cyclic aliphatic hydrocarbon having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, which may be substituted. The substituent of the alkyl group is not particularly limited but, for example, an aromatic hydrocarbon such as phenyl, tolyl, and the like may be mentioned. Specific examples of such alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-pentyl, n-hexyl, 2-methylpentyl, 2-ethylbutyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl, benzyl, and the like.
The aryl group is an aromatic hydrocarbon having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which may be substituted. The substituent of the aromatic hydrocarbon includes alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, etc.; alkoxy groups
Amano Souichi
Orita Souichi
Seto Yoko
Takahashi Kazunari
Utsunomiya Masaru
Mitsubishi Chemical Corporation
Powers Fiona T.
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