JP4147741B2 - Method for producing carbonyl compound by dehydrogenation of alcohol - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a carbonyl compound by dehydrogenating an alcohol. More specifically, the present invention relates to a method for producing a carbonyl compound by dehydrogenating an alcohol in the presence of a complex catalyst containing ruthenium and a specific organic phosphine. A preferred example to which the method of the present invention is applied is the production of gamma butyrolactone from 1,4-butanediol.
[0002]
[Prior art]
Conventionally, several methods for producing a carbonyl compound by dehydrogenating an alcohol in the presence of a complex catalyst in which a specific transition metal and a specific organic phosphine are combined have been proposed. For example, J. et al. Orgmet. Chem. , 429 (1992) 269-274 describes a reaction in which a diol is obtained by dehydrogenating a diol using an iridium-triisopropylphosphine complex, a ruthenium-triphenylphosphine complex and a rhenium-triisopropylphosphine complex as a catalyst. . Org. Chem. 1987, 52, 4319-4327 and Tetrahedron Let. 1981, 22, 5327 to 5330 describe a reaction in which a lactone compound is obtained by dehydrogenating a ruthenium-triphenylphosphine complex different from the above to obtain a lactone compound. Soc. Japan, 1982, 1179 to 1182 describes a reaction in which a diol is obtained by dehydrogenating a diol using a ruthenium-bis (diphenylphosphino) butane compound complex as a catalyst.
[0003]
However, these promote the dehydrogenation reaction of the alcohol substrate by allowing a hydrogen acceptor such as acetone to be present in the reaction system, and if the hydrogen acceptor is not present, the catalytic activity is significantly reduced. It was.
[0004]
Bull. Chem. Soc. Jpn. , 61, 2291 to 2294 (1988) describe a reaction for dehydrogenating methanol using a ruthenium-ethyldiphenylphosphine complex or a ruthenium-diethylphenylphosphine complex as a catalyst. However, this method has a problem that the catalytic activity is extremely low. Further, there is no description or suggestion about a method for efficiently producing gamma-butyrolactone by dehydrogenating 1,4-butanediol and causing intramolecular cyclization.
[0005]
A reaction that requires a large amount of hydrogen acceptor is extremely disadvantageous for industrial practice, and the hydrogen acceptor is converted to another compound by the dehydrogenation reaction of alcohol. This is not a practical method.
[0006]
JP-B-4-17954 uses a copper-chromium-manganese catalyst or copper-chromium-zinc catalyst, and JP-A-3-232874 uses a catalyst containing copper, chromium and barium. In the gas phase, 1,4-butanediol is dehydrogenated to produce gamma-butyrolactone. However, these methods have not yet solved the problems such as selectivity and catalyst deterioration. In addition, since it is a gas phase method, equilibrium limitation due to reverse reaction cannot be avoided, and the problems of selectivity and catalyst deterioration have not been completely solved.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a carbonyl compound industrially advantageously with high selectivity and high yield under mild reaction conditions in producing a carbonyl compound by dehydrogenating alcohol. is there.
[0008]
Further, another object of the present invention is to dehydrogenate 1,4-butanediol to cyclize, and to produce gamma-butyrolactone with high selectivity and industrially advantageous under mild reaction conditions. Is to provide a method.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors include ruthenium and an organic phosphine in which aliphatic carbon is bonded to two or more of three bonds of a phosphorus atom. It has been found that the complex catalyst can be a catalyst for efficiently dehydrogenating alcohol to produce a carbonyl compound. In particular, it has been found that the above complex catalyst can be a suitable catalyst for producing gamma-butyrolactone from 1,4-butanediol. The present invention has been completed based on the above findings.
[0010]
That is, the gist of the present invention is ruthenium,TrialkylphosphineIn the method for producing a carbonyl compound, the alcohol is dehydrogenated in the presence of a complex catalyst containing.
[0011]
Another aspect of the present invention is ruthenium,Trialkylphosphine1,4-butanediol is dehydrogenated in the presence of a complex catalyst containing
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The catalyst used in the present invention is a complex catalyst containing ruthenium and an organic phosphine in which aliphatic carbon is bonded to two or more bonds of three phosphorus atoms. The catalyst may be prepared in advance and used for the reaction, or each component constituting the catalyst may be present in the reaction system to generate the catalyst in the reaction system.
[0013]
The supply form of ruthenium metal 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. Specifically, for example, ruthenium dioxide, ruthenium tetroxide, ruthenium hydroxide, ruthenium chloride, odor Ruthenium iodide, ruthenium iodide, ruthenium nitrate, ruthenium acetate, tris (acetylacetonato) ruthenium, sodium hexachlororuthenate, dipotassium tetracarbonylruthenate, pentacarbonylruthenium, cyclopentadienyldicarbonylruthenium, dibromotricarbonylruthenium, chlorotris (Triphenylphosphine) hydridoruthenium, tetra (triphenylphosphine) dihydrodorenium, tetra (trimethylphosphine) dihydridolthenium, bis (tri-n-butylphosphine) Li ruthenium, tetra hydrido dodecacarbonyltriruthenium tetra ruthenium, dodecacarbonyl tri ruthenium, octadecanol carbonyl hexa ruthenate Jiseshiumu, undecalactone carbonyl hydride tri ruthenate tetraphenyl phosphonium, and the like. These compounds may be commercially available, or may be synthesized by a known method.
[0014]
The organic phosphine used in the present invention is one in which aliphatic carbon is bonded to two or more bonds of three phosphorus atoms. The organic phosphine is, for example, a trialkylphosphine in which an alkyl group is bonded to all three bonds of a phosphorus atom, an alkyl group is bonded to two of the three bonds of a phosphorus atom, and the remaining one is And dialkylarylphosphine having an aryl group bonded thereto. There may be one or a plurality of phosphorus atoms in one molecule of the organic phosphine, and they may be monodentate or multidentate with respect to ruthenium.
[0015]
The alkyl group is an optionally substituted, 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, saturated or unsaturated, linear, branched or cyclic. Is an aliphatic hydrocarbon. Although it does not restrict | limit especially as a substituent of this alkyl group, For example, aromatic hydrocarbons, such as a phenyl group and a tolyl group, etc. are mentioned. Specific examples of such an alkyl group include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl, normal hexyl, 2-methylpentyl, 2-ethylbutyl, cyclohexyl, normal heptyl, normal octyl, and normal nonyl. , Normal decanyl, benzyl and the like.
[0016]
An aryl group is an optionally substituted aromatic hydrocarbon having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples of the substituent of the aromatic hydrocarbon include alkyl groups such as methyl, ethyl, normal propyl, isopropyl, normal butyl and isobutyl; alkoxy groups such as methoxy and ethoxy; halogen atoms such as chlorine and bromine; nitro groups; Etc. Specific examples of such aryl groups include phenyl, o-, m-, p-tolyl, o-, m-, p-methoxyphenyl, n-, sec-, tert-butyl, o-, m-, Examples thereof include p-chlorophenyl and naphthyl.
[0017]
Two or more alkyl groups may be bonded to form an alkylene group.
[0018]
In the organic phosphine of the present invention, the functional groups bonded to the phosphorus atom may be the same or different from each other, or any two or three may form a ring structure. The carbon bonded to the phosphorus atom may be primary or secondary, but is preferably primary.
[0019]
Examples of the trialkylphosphine having an alkyl group described above include tri-normal decanyl phosphine, tri-normal nonyl phosphine, tri-normal octyl phosphine, tri-normal heptyl phosphine, tri-normal hexyl phosphine, tricyclohexyl phosphine, tri-normal pentyl phosphine, Normal butylphosphine, triisobutylphosphine, trinormalpropylphosphine, triisopropylphosphine, triethylphosphine, trimethylphosphine, dimethylnormaloctylphosphine, dinormaloctylmethylphosphine, dimethylnormalheptylphosphine, dinormalheptylmethylphosphine, dimethylnormalhexylphosphine, Dinormal hexylmethylphosphine, dimethyl Trialkylphosphine having one phosphorus atom in one molecule such as lucyclohexylphosphine, dicyclohexylmethylphosphine, dimethylbutylphosphine, dinormalbutylmethylphosphine, tribenzylphosphine; 1,1,2,2-tetrakis (dimethylphosphine Fino) ethane, 1,1,2,2-tetrakis (dimethylphosphino) propane, 1,1,2,2-tetrakis (dimethylphosphino) butane, 1,1,2,2-tetrakis (dioctylphosphino) Ethane, 1,1,2,2-tetrakis (dioctylphosphino) propane, 1,1,2,2-tetrakis (dioctylphosphino) butane, 1,1,2,2-tetrakis (dihexylphosphino) ethane, 1,1,2,2-tetrakis (dihexylphosphino) propane 1,1,2,2-tetrakis (dihexylphosphino) butane, 1,1,2,2-tetrakis (dibutylphosphino) ethane, 1,1,2,2-tetrakis (dibutylphosphino) propane, 1, A trialkylphosphine having a plurality of phosphorus atoms in one molecule, such as 1,2,2-tetrakis (dibutylphosphino) butane; 1,1-diphosphinane, 1,4-dimethyl-1,4-diphosphinophane, 1,3-dimethylphosphorinane, 1,4-dimethylphosphorinane, 8-methyl-8-phosphinobicyclooctane, 4-methyl-4-phosphotetracyclooctane, 1-methylphosphorane, 1-methyl Phosphonan 1,4-diphosphabicyclo [2.2.2] octane, 1,3-dimethylphosphorinane, 1,4-dimethylphosphorinane 1-methylphosphonan, 1-methylphosphorane, 1-methylphosphorinane, 1-phosphabicyclo [2.2.2] octane, 1-phosphabicyclo [2.2.1] heptane, Examples thereof include those in which a phosphorus atom is a constituent element of a ring.
[0020]
Among these, tri-normal decanyl phosphine, tri-normal nonyl phosphine, tri-normal octyl phosphine, tri-normal heptyl phosphine, tri-normal hexyl phosphine, tri-normal pentyl phosphine, tri-normal butyl phosphine, tri-normal propyl phosphine, triethyl phosphine, trimethyl Trialkylphosphine having one phosphorus atom in one molecule such as phosphine, dimethyl normal octyl phosphine, dinormal octyl methyl phosphine, dimethyl normal heptyl phosphine, dinormal heptyl methyl phosphine, dimethyl normal hexyl phosphine, dinormal hexyl methyl phosphine preferable.
[0021]
Examples of the dialkylarylphosphine include dimethylphenylphosphine, diethylphenylphosphine, dinormalpropylphenylphosphine, diisopropylphenylphosphine, dinormalhexylphenylphosphine, dinormaloctylphenylphosphine, dimethyltolylphosphine, diethyltolylphosphine, dinormalpropyltolyl. Examples include monophosphines such as phosphine, diisopropyltolylphosphine, dinormal hexyl tolyl phosphine, and dinormal octyl tolyl phosphine; polyphosphines such as methylphenylphosphinoethane, ethylphenylphosphinoethane, and methylphenylphosphinopropane.
[0022]
As a method for obtaining the organic phosphine described above, a commercially available one may be used, but if necessary, it can be synthesized by a known method and used. Examples of the method for synthesizing the organic phosphine include, for example, Experimental Chemistry Course, 4th edition, volume 24, page 229, H.C. Hibert. Chem. Ber. , 39, 160 (1906), etc., Grindard reaction and the like can be mentioned. Alternatively, a desired organic phosphine may be synthesized by reacting a phosphine having a phenyl group such as dialkylphenylphosphine with lithium metal and further reacting with an alkyl bromide to substitute the phenyl group with an alkyl group.
[0023]
The amount of the organic phosphine used is usually in the range of 0.1 to 1000, preferably 1 to 100 in terms of phosphorus atom / metal atomic ratio with respect to ruthenium metal. However, when a compound containing phosphine in which two or more aryl groups are bonded to a phosphorus atom, such as triphenylphosphine, is used as a compound for supplying ruthenium metal, phosphorous is used so that the phosphine is substituted with the above organic phosphine. It is preferable to increase the atomic ratio of atom / metal.
[0024]
The catalyst used in the present invention is characterized by containing ruthenium as described above and an organic phosphine in which aliphatic carbon is bonded to two or more of three bonds of phosphorus atoms. A neutral ligand or the like may be further contained as an optional component. Examples of such optional components include hydrocarbons having an ethylenically unsaturated bond such as ethylene, propylene, butene, cyclopentene, cyclohexene, butadiene, cyclopentadiene, cyclooctadiene, norbornadiene; diethyl ether, anisole, dioxane, tetrahydrofuran, etc. Ethers of propionic acid, caproic acid, butyric acid, benzoic acid, methyl benzoate, ethyl acetate, allyl acetate, and the like; dimethyl sulfide, tributylphosphine oxide, ethyldiphenylphosphine oxide, triphenylphosphine oxide, Trioctylphosphine oxide, diethylphenyl phosphinate, diphenylethyl phosphinate, triethyl phosphate, triphenyl phosphite, trio Chiruhosufeto, organophosphorus compounds such as hexamethylphosphoric triamide; and carbon monoxide, ethylene glycol, carbon disulfide, etc. caprolactam. Accordingly, in some cases, a reaction raw material, a reaction product, or a solvent may be a constituent component of the catalyst.
[0025]
Furthermore, the catalyst can also be used in the form of a cationic complex using a conjugate base of an acid having a pka of less than 2. Catalytic complexation may sometimes give favorable results such as stabilization of the catalyst and improvement of activity.
[0026]
As a compound that provides a conjugate base of an acid having a pka smaller than 2, a Bronsted acid or a salt thereof having a pka smaller than 2 is usually used. Specifically, for example, inorganic acids such as nitric acid, perchloric acid, borohydrofluoric acid, hexafluorophosphoric acid, fluorosulfonic acid; trichloroacetic acid, dichloroacetic acid, trifluoroacetic acid, dodecylsulfonic acid, octadecylsulfonic acid, trifluoromethane Organic acids such as sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, tetra (pentafluorophenyl) boronic acid, sulfonated styrene-divinylbenzene copolymer; alkali metals of these inorganic acids and organic acids, alkaline earth metals Salt, ammonium salt, silver salt, etc. are mentioned. In addition, compounds capable of providing a conjugate base of these acids, such as acid halides, acid anhydrides, esters, and acid amides, can also be used. These compounds giving a conjugate base of an acid having a pka of less than 2 are usually used in an amount of 1000 times mol or less, preferably 100 times mol or less with respect to the ruthenium metal.
[0027]
When the catalyst of the present invention is prepared and used in advance, the preparation method is not particularly limited, but one example is ruthenium tris (acetylacetonato), and 5 to 20 mol times relative to this. When the trialkylphosphine is added to the reaction raw material alcohol and stirred in a hydrogen atmosphere, a complex catalyst alcohol solution is generated. In order to make this a cationic complex, the compound containing the catalyst obtained above gives a compound having a pka of 2 or less acid conjugate base in an amount of 0.1 to 20 moles, preferably 1 to 10 times the ruthenium. What is necessary is just to add so that it may become mole times. A cationic complex catalyst can be synthesized by adding and stirring ruthenium tris (acetylacetonato), a trialkylphosphine, and a compound giving a conjugate base of an acid having a pka of 2 or less to the reaction raw material alcohol.
[0028]
The alcohol as the reaction raw material may be a monohydric alcohol or a polyhydric alcohol as long as it has a primary or secondary hydroxyl group. Further, the alcohol may be saturated or unsaturated, and may further have a substituent. Some of them are exemplified by monohydric alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, and 1-hexanol. 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 1-nonanol, 2-nonanol, 3 -Nonanol, 4-nonanol, 5-nonanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, allyl alcohol, 1-butenol, 2-butenol, 1-pentenol, 2-pen Tenol, 1-hexenol, 2-hexeno 3-hexenol, 1-heptenol, 2-heptenol, 3-heptenol, 1-octenol, 2-octenol, 3-octenol, 4-octenol, 1-nonenol, 2-nonenol, 3-nonenol, 4-nonenol, Examples include 1-decenol, 2-decenol, 3-decenol, 4-decenol, 5-decenol, cyclohexanol, cyclopentanol, cycloheptanol, 1-phenethyl alcohol, 2-phenethyl alcohol, methanolamine, and ethanolamine. . In the case of an unsaturated alcohol, the position of the unsaturated bond is arbitrary.
[0029]
Examples of the polyhydric alcohol include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, , 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1-hydroxymethyl-2-hydroxyethylcyclohexane, 1-hydroxy-2-hydroxypropylcyclohexane, 1-hydroxy-2-hydroxyethylcyclohexane, 1-hydroxymethyl Examples include dihydric alcohols such as 2-hydroxyethylbenzene, 1-hydroxymethyl-2-hydroxypropylbenzene, 1-hydroxy-2-hydroxyethylbenzene, 1,2-benzyldimethylol, 1,3-benzyldimethylol. When an alcohol having two primary hydroxyl groups is used as a raw material, a polyester may be generated by an intermolecular ester bond through a reaction process. However, 2 to 4 carbon atoms are bonded between carbon atoms to which the primary hydroxyl group is bonded. When carbon atoms are present, a lactone compound can be formed by intramolecular cyclization.
[0030]
Among the alcohol raw materials described above, preferably an alcohol having 4 or more carbon atoms, more preferably 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, It is a diol having 4 or more carbon atoms such as 1,8-octanediol. In particular, the present invention is suitable for dehydrogenation and cyclization reactions for producing gamma-butyrolactone from 1,4-butanediol.
[0031]
The alcohol dehydrogenation reaction according to the present invention is usually carried out in the absence of a solvent, that is, without the presence of a solvent other than the starting alcohol or the product carbonyl compound, but other solvents can be used if desired. Examples of such solvents include ethers such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and dioxane; methanol, ethanol, n-butanol, benzyl alcohol, ethylene glycol, diethylene glycol Alcohols such as phenol; phenols such as phenol; carboxylic acids such as formic acid, acetic acid, propionic acid and toluic acid; esters such as methyl acetate, butyl acetate and benzyl benzoate; aromatics such as benzene, toluene, ethylbenzene and tetralin Hydrocarbons; aliphatic hydrocarbons such as n-hexane, n-octane and cyclohexane; halogens such as dichloromethane, trichloroethane and chlorobenzene Nitro compounds such as nitromethane and nitrobenzene; carboxylic acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; other amide compounds such as hexamethylphosphoric triamide; Urea such as N-dimethylimidazolidinone; sulfones such as dimethyl sulfone; sulfoxides such as dimethyl sulfoxide; lactones such as gamma butyrolactone and caprolactone; carbonates such as dimethyl carbonate and ethylene carbonate; triglyme and tetraglyme And the like.
[0032]
Of these, ethers and polyethers are preferred.
[0033]
The reaction temperature is usually 20 to 350 ° C., preferably 100 to 250 ° C., more preferably 150 to 220 ° C. The catalyst concentration may be such that the desired activity is industrially desired, but the reaction is usually carried out so that the ruthenium metal is 0.0001 to 100 mol / L, preferably 0.001 to 10 mol / L with respect to the reaction solution. It only has to exist in the system. The reaction usually proceeds as a homogeneous catalytic reaction.
[0034]
The catalyst used in the present invention is capable of proceeding with a highly active and highly selective dehydrogenation reaction of alcohol, so that it is not particularly necessary to have a hydrogen acceptor in the reaction system, but it may be present if desired. Examples of the hydrogen acceptor include acetone, diphenylacetylene, vinyl methyl ketone, benzal acetone, ethyl methyl ketone, parabenzoquinone, nitrobenzene, acetonitrile, vinyl chloride, benzonitrile, acetaldehyde, carbonyl such as formaldehyde, butyraldehyde, benzaldehyde, Examples include alkene or alkyne compounds.
[0035]
The reaction pressure is arbitrary as long as the reaction system is kept in a liquid phase, but the alcohol dehydrogenation reaction of the present invention is a reaction that generates hydrogen, and thus is performed while extracting the hydrogen out of the system. Therefore, it is preferable to carry out in an open system under atmospheric pressure. When carried out in a closed system, the atmosphere is preferably an inert gas such as nitrogen, argon, helium or carbon dioxide. The reaction can be carried out either batchwise or continuously. The carbonyl compound produced by distillation is distilled off from the reaction product solution, and the catalyst is dissolved in the residual solution, so that it can be recovered and used as a catalyst in the next reaction.
[0036]
A carbonyl compound, particularly a lactone compound, obtained by the method of the present invention can be reacted with alkylamines to produce pyrrolidones. For example, N-methylpyrrolidone is produced by reacting gammabutyrolactone and methylamine, and can be widely used industrially as a cleaning agent, a solvent, and the like. The method for producing methylamine and N-methylpyrrolidone is not particularly limited, and a known and commonly performed method may be employed. Examples of the method for producing methylamine include methods described in, for example, US Pat. No. 3,387,032 and JP-A-9-12514. Usually, methanol and ammonia are mixed with silica and / or alumina. Or it can manufacture by making it react in presence of catalysts, such as a zeolite. As a method for producing N-methylpyrrolidone, for example, the method described in Japanese Patent Publication No. 47-18751 or Japanese Patent Publication No. 6-78305 can be used, and mono-, di- and / or trimethylamine and gamma-butyrolactone can be used. Can be obtained by heating reaction.
[0037]
Further, as described in JP-A-11-97062 or JP-A-11-135374, carbonyl compounds obtained by the method of the present invention, particularly gamma-butyrolactone, are disclosed in JP-A-9-176695 as a solvent for an electrolytic solution. Can be used as a polyurethane cleaning solution or the like.
[0038]
【Example】
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples. The conversion rate and the selectivity were obtained by analyzing the reaction solution by gas chromatography using an internal standard method.
[0039]
Example 1
Into a 500 mL SUS autoclave, introduced 17.68 g of ruthenium tris (acetylacetonato), 162.95 g of 10 molar equivalents of trinormal octylphosphine, and introduced hydrogen gas at a hydrogen pressure of 0.8 MPa. Heated and heat treated for 5 hours.
[0040]
93.31 g of 1,4-butanediol was added to a 300 mL four-necked flask equipped with a stirrer, a condenser, a temperature measuring device, and a sampling port, and the temperature was raised to 205 ° C. Thereto was added 8.19 g of the ruthenium catalyst synthesized by the above preparation method, and the mixture was heated and stirred at 203 ° C. for 6 hours (Ru metal concentration 2000 ppm by weight). As a result, the conversion of 1,4-butanediol was 99.7 mol%, and the selectivity of gamma butyrolactone was 98.0 mol%.
[0041]
Example 2
4.00 g of the ruthenium catalyst prepared in Example 1, 86.80 g of triglyme as a solvent, and 9.39 g of 1,5-pentanediol were heated and stirred at 203 ° C. for 3 hours. As a result, the conversion of 1,5-pentanediol was 100%, and the selectivity of valerolactone was 88.9 mol%.
[0042]
Example 3
A ruthenium catalyst was prepared by the same preparation method as in Example 1 using trinormal hexylphosphine as a ligand. 6.15 g of the prepared catalyst was added to 93.33 g of 1,4-butanediol, and heated to 203 ° C. and reacted for 4.5 hours as in Example 1 (Ru metal concentration 2000 ppm by weight). As a result, the conversion of 1,4-butanediol was 100.0 mol%, and the gamma butyrolactone selectivity was 96.6 mol%.
[0043]
Example 4
A ruthenium catalyst was prepared by the same preparation method as in Example 1 using trinormalbutylphosphine as the ligand. 5.19 g of the prepared catalyst was added to 100.47 g of 1,4-butanediol, and heated to 203 ° C. and reacted for 4 hours in the same manner as in Example 1 (Ru metal concentration 2000 ppm by weight). As a result, the conversion of 1,4-butanediol was 100.0 mol%, and the gamma butyrolactone selectivity was 97.0 mol%.
[0044]
Example 5
2.49 g of the catalyst of Example 4 was added to 100.31 g of 1,4-butanediol, and heated to 203 ° C. and reacted for 5 hours in the same manner as in Example 1 (Ru metal concentration 1000 ppm by weight). As a result, the conversion of 1,4-butanediol was 100.0 mol%, and the gamma butyrolactone selectivity was 98.9 mol%.
[0045]
Example 6
1.25 g of the catalyst of Example 4 was added to 99.09 g of 1,4-butanediol, and heated to 203 ° C. and reacted for 7.5 hours as in Example 1 (Ru metal concentration 500 ppm by weight). As a result, the conversion of 1,4-butanediol was 100.0 mol%, and the selectivity was 99.3 mol%.
[0046]
Example 7
2.18 g of the ruthenium catalyst prepared in Example 4, 88.16 g of triglyme as a solvent, and 9.44 g of 1,5-pentanediol were heated and stirred at 203 ° C. for 3 hours. As a result, the conversion of 1,5-pentanediol was 98.6%, and the selectivity of valerolactone was 84.5 mol%.
[0047]
Example 8
A ruthenium catalyst was prepared in the same manner as in Example 1 using trimethylphosphine as the ligand. 1.40 g of the prepared catalyst was added to 43.67 g of 1,4-butanediol and heated to 203 ° C. and reacted for 4 hours in the same manner as in Example 1 (Ru metal concentration 2000 ppm by weight). As a result, the conversion of 1,4-butanediol was 99.8 mol%, and the gamma butyrolactone selectivity was 99.5 mol%.
[0048]
Example 9
A ruthenium catalyst was prepared in the same manner as in Example 1 using tribenzylphosphine as the ligand. 2.56 g of the prepared catalyst was added to 45.63 g of 1,4-butanediol, and the mixture was heated to 203 ° C. and reacted for 6 hours as in Example 1 (Ru metal concentration 2000 ppm by weight). As a result, the conversion of 1,4-butanediol was 99.8 mol%, and the gamma butyrolactone selectivity was 99.2 mol%.
[0049]
Example 10
A 500 mL round bottom flask was charged with 0.32 g of ruthenium tris (acetylacetonato), 3.2 g of trinormaloctylphosphine, 300 mL of triglyme, and 2.8 g of paratoluenesulfonic acid, and then heated to 200 ° C. and heat-treated for 2 hours.
[0050]
90 mL of this catalyst solution was transferred to a 300 mL round bottom flask, 10 g of 1,4-butanediol was added, and the mixture was heated to 200 ° C. and reacted for 4 hours. As a result, the conversion rate of 1,4-butanediol was 100 mol%, and the selectivity of gamma butyrolactone was 75.3 mol%.
[0051]
Example 11
A 500 mL SUS autoclave was charged with 0.32 g of ruthenium tris (acetylacetonato), 3.2 g of trioctylphosphine and 300 mL of triethylene glycol dimethyl ether, and maintained at 170 ° C. for 2 hours while being pressurized to 5 MPa with hydrogen. A liquid was prepared.
[0052]
A 300 mL round bottom flask was charged with 90 mL of the catalyst solution prepared above and 10 g of 1,4-butanediol, and reacted at 200 ° C. for 4 hours. The conversion of 1,4-butanediol was 99.7% and the selectivity of gamma butyrolactone was 98.0%.
[0053]
Example 12
To a 300 mL round bottom flask, 45 mL of the catalyst solution prepared in Example 11 and 50 g of 1,4-butanediol were added, and the mixture was heated to 200 ° C. and reacted for 6 hours. The conversion rate of 1,4-butanediol was 99.8%, and the selectivity of gamma butyrolactone was 99.0%.
[0054]
Example 13
A 500 mL SUS autoclave is charged with 0.32 g of ruthenium tris (acetylacetonato), 3.2 g of trioctylphosphine and 300 mL of triethylene glycol dimethyl ether, and maintained at 200 ° C. for 5 hours while being pressurized to 0.8 MPa with hydrogen. Thus, a catalyst solution was prepared.
[0055]
To the 300 mL round bottom flask, 45 mL of the catalyst solution prepared above and 50 g of 1,4-butanediol were added, and the mixture was heated to 200 ° C. and reacted for 6 hours. The conversion of 1,4-butanediol was 99.7% and the selectivity of gamma butyrolactone was 98.0%.
[0056]
Comparative Example 4
A ruthenium catalyst was prepared in the same manner as in Comparative Example 1 using dimethylphenylphosphine as the ligand. 5.81 g of the prepared catalyst solution was added to 95.34 g of 1,4-butanediol, and heated to 203 ° C. and reacted for 7 hours as in Example 1 (Ru metal concentration of about 2000 ppm by weight). As a result, the conversion of 1,4-butanediol was 97.8 mol%, and the gamma butyrolactone selectivity was 95.0 mol%.
[0057]
Comparative Example 1
A ruthenium catalyst was prepared in the same manner as in Example 1 in toluene solvent using triphenylphosphine as the ligand. 7.48 g of a catalyst obtained by removing toluene from the prepared catalyst toluene solution under reduced pressure was added to 124.89 g of 1,4-butanediol, and the mixture was heated to 203 ° C. and reacted for 8 hours as in Example 1 ( Ru metal concentration about 2000 ppm by weight). As a result, the conversion of 1,4-butanediol was 84.0 mol%, and the gamma butyrolactone selectivity was 68.1 mol%.
[0058]
Comparative Example 2
A ruthenium catalyst was prepared in the same manner as in Comparative Example 1 using methyldiphenylphosphine as the ligand. 1.94 g of the prepared catalyst solution was added to 48.66 g of 1,4-butanediol, and the mixture was heated to 203 ° C. and reacted for 12 hours in the same manner as in Example 1 (Ru metal concentration: about 2000 ppm by weight). As a result, the conversion of 1,4-butanediol was 85.0 mol%, and the gamma butyrolactone selectivity was 54.2 mol%.
[0059]
Comparative Example 3
Using the same catalyst preparation method as in Example 1, an Ir catalyst was synthesized from 0.635 g of iridium tris (acetylacetonato) and 4.84 g of 10 mol equivalent of tri-n-octylphosphine. 3.71 g of this iridium catalyst was added to 81.5 g of 1,4-butanediol heated to 205 ° C. in the same manner as in Example 1, and the mixture was heated and stirred at 203 ° C. for 10 hours. As a result, the conversion of 1,4-butanediol was 5.2%, and the selectivity for gamma butyrolactone was 0.0 mol%.

Claims (8)

A method for producing a carbonyl compound, comprising dehydrating an alcohol in the presence of a complex catalyst containing ruthenium and a trialkylphosphine . The process according to claim 1, wherein the complex catalyst contains a conjugate base of an acid having a pka of less than 2. The method according to claim 1 or 2, wherein the alcohol is a polyhydric alcohol having a plurality of primary hydroxyl groups. The method according to any one of claims 1 to 3, wherein the carbonyl compound is a compound having an ester bond. The method according to any one of claims 1 to 4 , wherein the alcohol is 1,4-butanediol and the carbonyl compound is gamma butyrolactone. The method according to any one of claims 1 to 5, wherein the alkyl group of the trialkylphosphine has 1 to 30 carbon atoms. The process according to any one of claims 1 to 6, wherein the reaction temperature for dehydrogenating the alcohol is 100 to 250 ° C. The method according to any one of claims 1 to 7, wherein the dehydrogenation reaction of alcohol is carried out without the presence of a hydrogen acceptor in the reaction system.