United States Patent (19) 11 Patent Number: 4,931,573 Wada et al. 45 Date of Patent: Jun. 5, 1990

54 METHOD FOR PRODUCING ALACTONE FOREIGN PATENT DOCUMENTS 75) Inventors: Keisuke Wada, Yokohama; Yoshinori 2195374 8/1987 Japan ...... 549/325 Hara, Machida; Koushi Sasaki, Primary Examiner-Glennon H. Hollrah Kawasaki, all of Japan Assistant Examiner-Susan P. Treanor 73) Assignee: Mitsubishi Kasei Corporation, Attorney, Agent, or Firm-Oblon, Spivak, McClelland, Tokyo, Japan Maier & Neustadt 57 ABSTRACT 21 Appl. No.: 177,363 A method for producing a lactone by hydrogenating a dicarboxylic acid, a dicarboxylic acid anhydride and/or 22 Filed: Apr. 4, 1988 a dicarboxylic acid ester in the presence of a catalyst, wherein the hydrogenation reaction is conducted in the 30 Foreign Application Priority Data liquid phase in the presence of (1) ruthenium, (2) an Apr. 18, 1987 JP Japan ...... 62-95682 organic phosphine and (3) a compound of a metal se lected from the group consisting of Groups IVA, VA 511 Int. Cli...... COTD 307/28 and IIIB in the Periodic Table. 52 U.S. C...... 549/325; 549/326; According to the present invention, for the production 502/213 of a lactone by hydrogenating a dicarboxylic acid, a 58 Field of Search ...... 549/325, 326; 502/213 dicarboxylic acid anhydride and/or a dicarboxylic es ter, the reaction is conducted in a homogeneous liquid 56) References Cited phase reaction by using the ruthenium, organic phos U.S. PATENT DOCUMENTS phine and compound of a metal selected from the group 3,312,7i8 4/1967 Woskow ...... 549/325 consisting of Groups IVA, VA and IIIB, of the present 3,957,827 5/1976 Lyons ...... 549/325 invention as the catalyst, whereby the desired lactone 3,997,569 12/1976 Powell ...... 549/273 product can be obtained at high selectivity under a mild 4,268,689 5/1981 Knifton ...... 502/213 condition as compared with the conventional methods. 4,415,740 1 1/1983 Kaufman ...... 549/325 4,620,017 10/1986 Drake...... 549/325 20 Claims, No Drawings 4,931,573 1 2 METHOD FOR PRODUCING ALACTONE DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIELD OF THE INVENTION Now, the present invention will be described in de The present invention relates to a method for produc 5 tail. ing a lactone by hydrogenating a dicarboxylic acid, a The dicarboxylic acid, the dicarboxylic anhydride dicarboxylic acid anhydride and/or a dicarboxylic acid and/or a dicarboxylic acid ester used as a starting mate rial of the present invention, is a saturated or unsatu ester. rated dicarboxylic acid having from 3 to 7 carbon atoms DISCUSSION OF BACKGROUND 10 and/or its derivative. Specific examples of the dicarboxylic acid include A method for producing a lactone by hydrogenating succinic acid, fumaric acid, maleic acid, glutaric acid a dicarboxylic acid, dicarboxylic acid anhydride and/or and methylsuccinic acid. The dicarboxylic acid anhy a dicarboxylic acid ester, has been studied since long dride includes succinic anhydride, maleic anhydride, ago, and various catalysts have been found. 15 glutaric anhydride and methylsuccinic anhydride. As For example, many proposals have been made on a the dicarboxylic acid ester, an alkyl ester is preferred, process for producing a lactone by a fixed bed or liquid and particularly preferred is a dicarboxylic acid deriva phase or suspension phase hydrogenation reaction sys tive having 4 carbon atoms. For example, dimethyl tem by using e.g. a nickel-type catalyst (e.g. Japanese maleate, diethyl fumarate and di-n-butyl succinate, may Examined Patent Publication No. 6947/1968), a cobalt 20 be mentioned. type catalyst (e.g. Japanese Unexamined Patent Publi The catalyst used in the method of the present inven cation No. 95057/1976), a copper-chromium-type cata tion is a catalyst comprising (1) ruthenium, (2) an or lyst (e.g. Japanese Examined Patent Publication No. ganic phosphine and (3) a compound of a metal selected 20119/1963) and a copper-zine-type catalyst (e.g. Japa from the group consisting of Groups IVA, VA, and nese Examined Patent Publication No. 14463/1967). On 25 IIIB of the Periodic Table. the other hand, it is also known to produce a lactone by Here, the ruthenium may be used in the form of metal conducting the above-mentioned hydrogenation reac ruthenium or a ruthenium compound. As the ruthenium tion by using a ruthenium catalyst for a homogeneous compound, an oxide, hydroxide, inorganic acid salt, system. For example, U.S. Pat. No. 3,957,827 discloses a organic acid salt or complex compound of ruthenium hydrogenation reaction under a condition of from 40 to 30 may be used. Specifically, there may be mentioned 400 psi by using a catalyst of RuX(PRR2R3 type. ruthenium dioxide, ruthenium tetraoxide, ruthenium U.S. Pat. No. 4,485,246 discloses that a hydrogenation dihydroxide, ruthenium chloride, ruthenium bromide, reaction by means of a similar catalyst is conducted in ruthenium iodide, ruthenium , ruthenium acetate, the presence of an organic amine. . tris(acetylacetone)ruthenium, sodium hexachlororuthe However, such conventional methods wherein the 35 nate, dipotassium tetracarbonylruthenate, pentacar nickel-type catalyst, the cobalt-type catalyst, the cop bonylruthenium, cyclopentadienyldicarbonylru per-chromium-type catalyst and the copper-zinc-type thenium, dibromotricarbonylruthenium, chlorotris(tri catalyst was used, all had a problem that it was neces phenylphosphine)hydridoruthenium, bis(tri-n-butyl sary to employ a severe condition of few tens atm. or phosphine)tricarbonylruthenium, dodecacarbonyltriru higher. On the other hand, the conventional method thenium, tetrahydridedecacarbonyltetraruthenium, wherein a ruthenium catalyst for a homogeneous system dicesium octadecacarbonylhexaruthenate, tetraphenyl was used, had not only a drawback that the catalytic phosphonium, undecacarbonylhydridetriruthenate. activity was slightly low, but also fatal problems that Such metal ruthenium of ruthenium compound is the catalytically useful life was extremely short, and the used in an amount such that the concentration in the reactor was likely to be corroded by the use of halogen, 45 reaction solution will be 0.0001 to 100 mol, preferably although the method has a feature that the hydrogena from 0.001 to 10 mol, as ruthenium in one liter of the tion reaction proceeds under a relatively mild condi reaction solution. tion. In the method of the present invention, it is necessary SUMMARY OF THE INVENTION to use the organic phosphine together with the ruthe 50 nium. The organic phosphine is considered to contrib It is an object of the present invention to overcome ute to the control of the electron state of ruthenium of the above-mentioned conventional problems and to the the stabilization of the activity of ruthenium. Spe provide a method for producing a lactone whereby a cific examples of such an organic phosphine include a dicarboxylic acid, a dicarboxylic acid anhydride and/or trialkylphosphine such as tri-n-butylphosphine or di a dicarboxylic acid ester can be hydrogenated industri 55 methyl-n-octylphosphine, a tricycloalkylphosphine ally more advantageously than ever. such astricyclohexylphosphine, a triarylphosphine such The present inventors have conducted extensive re as triphenylphosphine, an alkylarylphoshine such as search to accomplish the above object, and as a result, dimethylphenylphosphine, and a polyfunctional phos have found that in a method for producing a lactone by phine such as 1,2-bis(diphenylphosphino)ethane. hydrogenating a dicarboxylic acid, a dicarboxylic acid Such as organic phosphine is used in an amount anhydride and/or a dicarboxylic acid ester, if a catalyst within a range of from 0.1 to 1,000 mol, preferably from comprising (1) ruthenium, (2) an organic phosphine and 1 to 100 mol, per mol of ruthenium. The organic phos (3) a compound of a metal selected from the group phine may be supplied to the reaction system by itself or consisting of Groups IVA, VA, and IIIB, is used as the in the form of a composite with ruthenium. catalyst, not only the catalytic activity for hydrogena 65 By using a compound of a metal selected from the tion increases, but also the stability in the activity of the group consisting of Groups IVA, VA and IIIB of the catalyst can be improved. The present invention has Periodic Table as an additional accelerator for the ru been accomplished on the basis of this discovery. thenium constituting the main catalyst for the hydroge 4,931,573 3 4. nation reaction of the present invention, it is possible to thallium, trimethyl thallium, thallium hydroxide, thal have the hydrogenation reaction proceeded under a lium carbonate, thallium acetate, methylthallium diace relatively mild condition by utilizing the merits of the tate, triethoxy thallium, butoxydimethyl thallium, die ruthenium as the main component, and it is also possible thylaminodimethyl thallium or dimethyl thallium ace to improve the catalytic activity for hydrogenation and tylacetonate. Such a metal compound is used in an to improve the stability of the activity and the selectiv amount within a range of from 0.01 to 1000 mols, prefer ity for the desired product. ably from 0.1 to 100 mols, more preferably from 0.5 to The metal selected from the group consisting of 20 mols, per mol of ruthenium in the main catalyst. Groups IVA, VA and IIIB of the Periodic Table. in By using a conjugate base of an acid having a pKa of cludes titanium, zirconium and hafnium if Group IVA; 10 less than 2 as an additional accelerator for the ruthe vanadium, niobium and tantalum in Group VA; and nium, it is possible to improve the catalystic activity for boron, aluminum, gallium, indium and thallium in hydrogenation and to improve the stability of activity Group IIIB. The compound of such a metal includes a and the selectivity for the desired product. carboxylate, a nitrate, a halide, an oxohalide, a sulfate, a The conjugate base of an acid having a pKa of less hydroxide, a carbonylate, an oxalate, a phosphate, a 15 than 2 may be materialso long as it is capable of forming chromate, a silicate, a cyano compound, an oxide, a such a conjugate base during the preparation of the metal alkoxide, an acetylacetonate and an organometal catalyst or in the reaction system. It may be supplied in lic compound. From the viewpoint of its solubility, the form of a Brinsted acid having a pKa of less than 2, corrosion property and thermal stability, it is perferably or a salt of such an acid. Specifically, there may be added in the form of its metal alkoxide, acetylacetonate, 20 mentioned Brinsted acids including inorganic acids carboxylate, hydroxide or oxide to the reaction system. such as nitric acid, perchloric acid, borofluoric acid, . Specific examples of the compound of a metal se hexafluorophosphoric acid and fluorosulfonic acid, and lected from the group consisting of Groups IVA, VA organic acids suchas trichloroacetic acid, dichloroace and IIIB, include a titanium compound such as titanium tic acid, trifluoroacetic acid, methanesulfonic acid, tetraethoxide, titanium tetraispropoxide, titanium tet 25 dodecylsulfonic acid, octadecylsulfonic acid, tri rabutoxide, ammonium titanium oxalate, titanyl acetyl fluoromethanesulfonic acid, benzenesulfonic acid, p-tol acetonate or titanium hydroxide, a zirconium com uenesulfonic acid and a sulfonated styrene-divinylben pound such as zirconium acetylacetonate, zirconium zene copolymer, or alkali metal salts, alkaline earth carbonate, zirconium napthenate, zirconium octate, metal salts, ammonium salts or silver salts of these dicyclopentadiene zirconium dimethoxide, dicyclopen 30 Brønsted acids. tadiene zirconium diethoxide, zirconocene, tetrabutoxy It may be added in the form of an acid derivative zirconium, tetraethoxy zirconium, zirconium oxyace which is capable of forming such a conjugate base in the tate, zirconium oxystearate, zirconium phosphate, zir reaction system. For example, it may be added in the conium oxynitrate, zirconium sulfate or dicyclopenta form of an acid halide, an acid anhyride, an ester or an diene zirconium dicarbonyl; a hafnium compound such 35 acid amide to the reaction system to obtain similar ef as tetramethoxy hafnium, tetraethoxy hafnium, dicyclo fects. pentadiene hafnium dicarbonyl, tetrabenzyl hafnium or Such an acid or base is used in an amount within a tetracyclopentadiene hafnium; a vanadium compound range of from 0.01 to 1,000 mol, preferably from 0.1 to such as vanadium acetylacetonate, vanadyl nitrate, 100 mol, relative to ruthenium. vanady sulfate, vanadyl acetylacetonate, vanadyl oxa 40 The method of the present invention may be con late, ammonium methavanadate or vanadium hexacar ducted in the absence of a solvent i.e. by using the start bonyl; a niobium compound such as niobium oxide, ing material for the reaction or the reaction product as dicyclopentadienetrihydride niobium, niobium oxide the solvent. However, it is possible to use a solvent ethoxide, niobium pentamethoxide or niobium pentaiso other than the starting material for the reaction or the proxide; a tantalum compound such as tantalum oxide, 45 reaction product. Such a solvent includes an ether such tantalum pentamethoxide, tantalum pentaisoproxide, as diethyl ether, , tetrahydrofuran, ethylene gly cyclopentadienyltetracarbonyl tantalum, biscyclopen col dimethyl ether or dioxane; a ketone such as acetone, tadienyltrimethyl tantalum or pentabenzyl tantalum; a methyl ethyl ketone or acetophenone; an alcohol such boron compound such as trimethoxy boron, triphenoxy as methanol, ethanol, n-butanol, benzylalcohol, , boron, boric acid, boron oxide, orthoboric acid, pyro 50 ethylene glycol or diethylene glycol; a carboxylic acid boric acid, metaboric acid, methylboronic acid, phenyl such as formic acid, acetic acid, propionic acid or toluy boronic acid, diphenylborinic acid, triphenyl boran, lic acid: an ester such as methyl acetate, n-butyl acetate tricyclohexylboran, tetraethyl diboran, dimethyl(dime or benzyl benzoate; an aromatic hydrocarbon such as thylamino) boran, borazine, triethylboroxine, tricy benzene, toluene, ethylbenzene or tetralin; an aliphatic clohexyl boroxine, triphenyl boroxine, sodium tetra 55 hydrocarbon such as n-hexane, n-octane or cyclohex phenylborate, ammonium tetraphenylborate or ammo ane; a halogenated hydrocarbon such as dichlorometh nium tetraoxoborate; an aluminum compound such as ane, trichloroethane or chlorobenzene; a nitro com triethoxy aluminum, tributoxy aluminum, triethyl alu pound such as nitromethane or nitrobenzene; a carbox minum, aluminum acetate, aluminum acetylacetone, lic acid amide such as N,N-dimethylformamide, N,N- aluminum benzoate or aluminum stearate; a gallium 60 dimethylacetamide or N-mehtylpyrrolidone; other compound such as gallium oxide, gallium triisoproxide, amide such as hexamethylphosphoric acid triamide or gallium isoproxyacetylacetonate, hydroxydimethyl gal N,N,N',N'-tetraethylsulfanide; a urea such as N,N'- lium, trimethyl gallium, methoxydimethyl gallium or dimethylimidazolidone or N,N,N,N-tetramethylurea; a dimethyl gallium acetate; an indium compound such as sulfone such as dimethylsulfone or tetramethylenesul indium trimethoxide, indium triisoproxide, triisopropyl 65 fone; a sulfoxide such as dimethylsulfoxide or diphenyl indium, trimethyl indium or phenyl indium diacetate; sulfoxide; a lactone such as y-butyrolactone or e and a thallium compound such as methyloxo thallium, caprolactone; an polyether such as tetraglyme or 18 hydroxydimethyl thallium, methanesulfonate dimethyl crown-6; a nitrile such as or benzonitrile; 4,931,573 5 6 and a carbonate such as dimethylcarbonate or ethylene TABLE 1. carbonate. - Metal compound - Formed The hydrogenation reaction of the present invention Amount GBL may be conducted by introducing the starting material Type (mmol) (mmol) 5 for the reaction, the catalyst component and, if neces Example 2 Boric acid 0.50 24.1 sary, a solvent, into the reactor, and supplying hydro Example 3 Zirconium phosphate 0.22 17.7 gen thereto. It is preferred to conduct heat-treatment of Example 4 Ammonium tetraoxoborate 0.23 20.4 Example 5 Titanyl acetylacetonate 0.25 13. the catalyst prior to the introduction of the starting Example 6 Titanium tetraisoproxide 0.25 15.6 material, by introducing the catalyst component, if nec Example 7 Tri-n-octadecyl borate 0.50 15.1 essary together with a solvent, into the reactor and 10 Example 8 Tricyclohexylboroxine 0.50 22.3 heat-treating it under a hydrogen or argon atmosphere, Example 9 Aluminum triethoxide 0.25 14.8 Example 10 Aluminum tributoxide 0.50 6.4 whereby the formation of by-products will be low and Example ll Zirconium oxystearate 0.13 20.5 the selectivity will be improved. Such heat-treatment is Example 12 Zirconium acetylacetonate 0.25 18.0 conducted usually at a temperature of from 100 to 300 Example 13 Ammonium zirconium 0.25 19.8 15 carbonate C., preferably from 150 to 250 C., for at least 0.5 hour. Example 14 Vanadium acetylacetonate 0.13 23.9 The hydrogen may be the one diluted with a gas inert to Compa- Not added --- 12.0 the reaction, such as nitrogen or carbon dioxide. rative The reaction is conducted usually at a temperature of Example 1 from 50 to 250 C, preferably from 100 to 200° C. The hydrogen partial pressure in the reaction system is usu 20 ally from 0.1 to 100 kg/cm2, preferably from 1 to 30 EXAMPLE 1.5 kg/cm2. It is, of course, possible to conduct the reaction The reaction was conducted in the same manner as in at a lower or higher pressure, but such is not advanta Example 1 except that 4.72 g (40 mmol) of succinic acid geous from the industrial point of view. 25 was used instead of succinic anhydride charged as the The reaction may be conducted either in a batch starting material for the reaction, whereby the conver system or in a continuous system. In the case of a batch sion of succinic acid was 52.5%, and the yield of GBL system, the required reaction time is usually from 1 to was 51.7%. 20 hours. EXAMPLES 16 to 20 The desired lactone may be recovered from the reac 30 tion solution by a usual separation and purification The reaction was conducted in the same manner as in means such as distillation or extraction. Further, the Example 1 except that the solvent as specified in Table distillation residue may be recycled to the reaction sys 2 was used instead of tetraglyme used as the solvent in tem as a catalyst component. Example 1. The results are shown in Table 2. s Now, the present invention will be described in detail 35 TABLE 2 with reference to Examples. However, it should be Formed GBL understood that the present invention is by no means Solvent (16 ml) (mmol) restricted to such specific Examples. Example 16 Dodecylbenzene 28.0 Example 17 Sulfolane 24.4 EXAMPLE 1. Example 18 N-methylpyrrolidone 21.2 Into 70 ml SUS microautoclave, 0.0199 g (Ru: 0.05 Example 19 Acetic acid 18.8 mmol) of ruthenium acetylacetonate, 0.185 g (0.5 mmol) Example 20 Dimethyl phthalate 12.8 of trioctylphosphine, 0.031 g (0.13 mmol) of zirconium oxyacetate and 16 ml of tetraglyme were charged, and EXAMPLE 21 heat-treated under an argon atmosphere at 200 C. for 2 45 hours. To the heat-treated catalyst solution, 4.0 g (40 Into a bubble tower type SUS reactor, 0.0796 g (Ru: mmol) of succinic anhydride as the starting material for 0.2 mmol) of ruthenium acetylacetonate, 0.74 g (2.0 the reaction was charged, and hydrogen gas was intro mmol) of trioctylphosphine, 0.242 g (0.92 mmol) of duced under a pressure of 30 atm. The mixture was ammonium tetraoxoborate, 20 ml of tetraglyme and, as 50 the starting material for the reaction, 20.0 g (200 mmol) heated at 200 C. for 2 hours for the reaction. of succinic anhydride, were charged. While supplying After the reaction for a predetermined period of time, hydrogen gas under normal pressure at a rate of 20 NTP the autoclave was opened. The reaction product was liter/hr, the mixture was heated at 200 C. for 2 hours analyzed by gas chromatography, whereby the conver for reaction, whereby, 27.2 mmol of GBL was obtained. sion of succinic anhydride was 75.5%, and the yield of 55 ty-butyrolactone (hereinafter referred to simply as EXAMPLE 22 “GBL') was 71.8%. The reaction was conducted in the same manner as in EXAMPLES 2 to 14 and COMPARATIVE Example 21 except that 0.044 g (Ru: 0.1 mmol) of ruthe EXAMPLE 1. nium acetate was used instead of ruthenium acetylac etonate used in Example 21, whereby 16.0 mmol of The reaction was conducted in the same manner as in GBL was obtained. Example 1 except that a metal of Group IVA, VA or IIIB in the Periodic Table as identified in Table 1 was EXAMPLE 23 used instead of zirconium oxyacetate in Example 1. The reaction was conducted in the same manner as in Further, for the purpose of comparison, the reaction 65 Example 21 except that 0.53 g (2.0 mmol) of triphenyl was conducted in the same manner without adding such phosphine was used instead of trioctylphosphine used in a specific metal compound. The results are shown in Example 21, and the reaction temperature was changed Table 1. to 170° C., whereby 12.2 mmol of GBL was obtained. 4,931,573 7 8 in Table 3 was used instead of 2.01 g of zirconium oxys EXAMPLE 24 tearate. The results are shown in Table 3. TABLE 3 Reaction Results Selectivity Amount of for the total Selectivity Compound of metal maleic Conversion of GBL and for Name of anhydride of maleic succinic propionic Yield metal com- Amount supplied anhydride anhydride acid of GBL pound (minol) (g) (%) (%) (%) (%) Example 28 Zirconium 2.0 12.7 96.3 78.2 3.3 30.1 chloride Example 29 Titanium 1.0 12.8 93.6 48.1 44.2 6.5 acetylaceto nate Example 30 Vanadium 5.0 12.7 95.1 67.2 25.3 23.2 acetylaceto late

The catalyst, the solvent and the starting material for the reaction were the same as in Example 21, and the 20 reaction condition was changed as follows.ple Z1, Namely, EXAMPLE 31 while supplying hydrogen gas under a pressure of 10 Into a 200 ml induction agitation type SUS autoclave, atm. at a rate of 100 NTP liter/hr, the mixture was 0.08 g (0.2 mmol) of ruthenium acetylacetonate, 0.74g heated at 200 C. for 4 hours for the reaction, whereby (2.0 mmol) of trioctylphosphine, 0.33 g (1.76 mmol) of the conversion of succinic anhydride was 97.8%, and 25 p-toluenesulfonic acid, 2.01 g (3.0 mmol) of zirconium the yield of GBL was 92.4%. oxystearate and 64 ml of tetraethyleneglycol dimethyl ether were charged. The mixture was heat-treated at EXAMPLE 25 200 C. under a hydrogen pressure of 20 kg/cm2 for 2 The reaction was conducted in the same manner as in hours. Example 24 except that 20 ml of y-butyrolactone was 30 The autoclave was cooled and opened under argon used instead of tetraglyme used in Example 24, whereby atomosphere, and 16 g (160 mmol) of succinic anhy the conversion of succinic anhydride was 96.5%, and dride was added thereto. Then, the reaction was con the yield of GBL was 84.0%. ducted at 200 C. under a hydrogen pressure of 30 kg/cm2 for 2 hours. EXAMPLE 26 35 After completion of the reaction, the raction solution Into a 200 ml induction agitation type SUS autocalve, was taken out, and analyzed, whereby the conversion of 0.08 g (0.2 mmol) of ruthenium acetylacetonate, 0.74g succinic anhydride was 74.0%, and the selectivity for (2.0 mmol) of trioctylphosphine, 0.67 g (1.0 mmol) of GBL was 94.5%. zirconium oxystearate and 40 ml of tetraethyleneglycol What is claimed is: dimethyl ether were charged. The mixture was heat- 40 1. A method for producting a lactone, which com treated at 200 C. under a hydrogen pressure of 20 prises hydrogenating in the liquid phase a dicarboxylic kg/cm2 for 2 hours. Then, the hydrogen pressure was acid, a dicarboxylic acid anhydride or a dicarboxylic raised to 30 kg/cm, and a solution prepared by dis acid ester or a combination thereof in the presence of a solving 25% by weight of maleic anhydride in tetrae catalyst, said catalyst comprising (1) ruthenium, (2) an thyleneglycol dimethyl ether, was introduced into the 45 organic phosphine selected from the group consisting of autoclave at an injection rate of 24 ml/hr by a liquid tri-n-butylphosphine, dimethyl-n-octylphosphine, tricy pump. The mixture was reacted at 200 C. for 2 hours. clohexylphosphine, triphenylphosphine, dimethyl The total amount of maleic anhydride introduced into phenylphosphine and 1,2-bis(diphenylphosphino) eth the autoclave during the reaction, was 14.8 g (151.4 ane and (3) a compound of a metal selected from the mmol). After completion of the reaction, the reaction 50 group consisting of groups IVA, VA and IIIB of the solution was taken out, and analyzed, whereby the con Periodic Table. version of maleic anhydride was 97.1%, and the selec 2. The method according to claim 1, wherein the tivity for GBL was 18.6%. ruthenium is ruthenium metal or a ruthenium com pound. EXAMPLE 27 55 3. The method according to claim 1, wherein the The reaction was conducted in the same manner as in ruthenium compound is an oxide, hydroxide, inorganic Example 26 except that an amount of zirconium oxys salt, organic salt or complex compound of ruthenium. tearate was changed to 2.01 g (3.0 mmol), and 0.33 g 4. The method according to claim 1, wherein the (1.76 mmol) of p-toluenesulfonic acid was added. The ruthenium is present in an amount of from 0.0001 to 100 total amount of maleic anhydride introduced into the 60 mols in one liter of the reaction solution. autoclave was 12.9 g (132.4 mmol). After completion of 5. The method according to claim 1, wherein the the reaction, the analysis was conducted, whereby the molar ratio of (1) the ruthenium: (2) an organic phos conversion of maleic anhydride was 96.7%, and the phine; (3) the compound of a metal selected from the selectivity for GBL was 35.1%. group consisting of Groups IVA, VA and IIIB of the 65 Periodic Table is 1:01-1000;0.01-1000. EXAMPLES 28 to 30 6. The method according to claim 1, wherein the The reaction was conducted in the same manner as in molar ratio of (1) the ruthenium: (2) an organic phos Example 27 except that a metal compound as identified phine; (3) the compound of a metal selected from the 4,931,573 9 10 group consisting of Groups IVA, VA and IIIB of the ide, ruthenium tetraoxide, ruthenium dihydroxide, ru Periodic Table is 1:1-100:0.1-100. thenium chloride, ruthenium bromide, ruthenium io 7. A method for producing a lactone, which com dide, ruthenium nitrate, ruthenium acetate, tris prises hydrogneating in the liquid phase a dicarboxylic (acetylacetone)ruthenium, sodium hexachlororuthe acid dicarboxylic acid anhydride or a dicarboxylic acid 5 nate, dipotassium tetracarbonylruthenate, pentacar ester or a combination thereof in the presence of cata bonylruthenium, cyclopentadienyldicarbonylru lyst, said catalyst comprising (1) ruthenium, (2) an or thenium, dibromotricarbonylruthenium, chlorotris(tri ganic phosphine selected from the group consisting of phenylphosphine)hydridoruthenium, bis(tri-n-butyl tri-n-butylphosphine, dimethyl-n-octylphosphine, tricy phosphine)tricarbonylruthenium, dodecacarbonyltriru clohexylphosphine, triphenylphosphine, dimethyl 10 thenium, tetrahydridedecacarbonyltetraruthenium, phenylphosphine and 1,2-bis(diphenylphosphino)ethane dicesium, octadecacarbonylhexaruthenate and tetra (3) a compound of a metal selected from the group phenylphosphonium undecacarbonylhydridetriruthe consisting of Group IVA, VA and IIIB of the Periodic nate. Table, and (4) a conjugate base of an acid having a pKa 18. The method according to claim 7, wherein said of less than 2. 15 metal of Group IVA is titanium, zirconium or hafnium, 8. The method according to claim 7, wherein the said metal of Group VA is vanadium, niobium or tanta conjugate base of an acid having a pKa of less than 2 is lum; and said metal of Group IIIB is boron, aluminum, a p-toluenesulfonic acid anion. gallium, indium, or thallium. 9. The method according to claim 7, wherein the 19. The method according to claim 14, wherein the conjugate base of an acid having a pKa of less than 2 is 20 compound of said metal is a C1-C3 carboxylate, nitrate, a tetrafluoroborate anion or a trifluoromethanesulfonic halide, oxyhalide, sulfate, hydroxide, C1-C3 carbony acid anion. late, oxalate, phosphate, chromate, silicate, nitrile, ox 10. The method according claim 7, wherein the con ide, C1-C3 alkoxide, acetylacetonate or an organometal jugate base of an acid having a pKa of less than 2 is a lic compound selected from the group consisting of nitric acid anion, a methanesulfonic acid anion, an oc 25 titanium tetraethoxide, titanium tetraisopropoxide, tita tadecylsulfonic acid anion or a dodecylsulfonic acid nium tetrabutoxide, ammonium titanium oxalate, zirco anion. nium carbonate, zirconium naphthenate, zirconium oc 11. The method according to claim 7, wherein the tate, dicyclopentadiene zirconium dimethoxide, dicy molar ratio of (1) the ruthenium: (2) the organic phos clopentadiene zirconium, diethoxide, zirconium, tet phine: (3) the compound of a metal selected from the 30 rabutoxy zirconium, tetraethoxy zirconium, zirconium group consisting of Groups IVA, VA and IIIB: (4) the oxyacetate, zirconium oxystearate, dicyclopentadiene conjugate base of an acid having a pKa of less than 2 is zirconium dicarbonyl, tetramethoxy hafnium, tetrae 1:0.1-1000;0.01-1000:0.1-100. thoxy hafnium, tetracyclopentadiene hafnium, vana 12. The method according to claim 1, wherein said dium hexacarbonyl, dicyclopentadienetrihydride nio dicarboxylic acid, dicarboxylic acid anhydride and di 35 bium, niobium oxide ethoxide, niobium pentamethox carboxylic acid ester are each saturated or unsaturated ide, niobium pentaisoproxide, tantalum pentamethox and have from 3 to 7 carbon atoms. ide, tantalum pentaisoproxide, cyclopentadienylteracar 13. The method according to claim 3, wherein said bonyl tantalum, biscyclopentadienyltrimethyl tantalum, ruthenium compound is selected from the group con pentabenzyl tantalum, trimethoxy boron, triphenoxy sisting of rutheniun dioxide, ruthenium tetraoxide, ru boron, methylboronic acid, phenylboronic acid, di thenium dihydroxide, ruthenium chloride, ruthenium phenylborinic acid, triphenyl boran, tricyclohexyl bo bromide, ruthenium iodide, rithenium nitrate, ruthe ran, tetraethyl diboran, dimethyl(dimethylamino) bo nium acetate, tris(acetylacetone)ruthenium, sodium ran, triethylboroxine, tricyclohexyl boroxine, triphenyl hexachlororuthenate, dipotassium tetracarbonylruthe boroxine, sodium tetraphenylborate, ammonium tetra nate, pentacarbonylruthenium, cyclopentadienyldicar 45 phenylborate, triethoxy aluminum, tributoxy aluminum, bonylruthenium, dibromotricarbonylruthenium, chlo triethyl aluminum, aluminum benzoate, aluminum stea rotris(triphenylphosphine)hydridoruthenium, bis(tri-n- rate, gallium triisoproxide, gallium isoproxyacetylace butylphosphine)tricarbonylruthenium, dodecacar tonate, hydroxydimethyl gallium, trimethyl gallium, bonyltriruthenium, tetrahydridedecacarbonyltetraru methoxydimethyl gallium, dimethyl gallium acetate, thenium, dicesium octadecacarbonylhexaruthenate and 50 indium trimethoxide, indium triisoproxide, triisopropyl tetraphenylphosphonium undecacarbonylhydride indium, trimethyl indium, phenyl indium diacetate, me triruthenate. thyloxo thallium, hydroxydimethyl thallium, methane 14. The method according to claim 1, wherein said sulfone dimethyl thallium, trimethyl thallium, thallium metal of Group IVA is titanium, zirconium or hafnium, carbonate, methyl thallium diacetate, triethoxy thal said metal of Group VA is vanadium, niobium or tanta 55 lium, butoxydimethyl thallium, diethylaminodimethyl lum; and said metal of Group IIIB is boron, aluminum, thallium and dimethyl thallium acetylacetonate. gallium, indium or thallium. 20. The method according to claim 7, wherein the 15. The method according to claim 1, wherein said compound of said metal is a C1-C3 carboxylate, nitrate, hydrogenation is conducted at a temperature of from halide, oxyhalide, sulfate, hydroxide, C1-C3 carbony about 50 to 250 C. with a hydrogen partial pressure of 60 late, oxalate, phosphate, chromate, silicate, nitrile, ox from 0.1 to 100 kg/cm2. ide, C1-C3 alkoxide, acetylacetonate or an organometal 16. The method according to claim 7, wherein said lic compound selected from the group consisting of dicarboxylic acid, dicarboxylic acid anhydride and di titanium tetraethoxide, titanium tetraisopropoxide, tita carboxylic acid ester are each saturated or unsaturated nium tetrabutoxide, ammonium titanium oxalate, zirco and have from 3 to 7 carbon atoms. 65 nium carbonate, zirconium naphthenate, zirconium oc 17. The method according to claim 7, wherein said tate, dicyclopentadiene zirconium dimethoxide, dicy ruthenium is ruthenium metal or a ruthenium cmpound clopentadiene zirconium diethoxide, zirconocene, tet selected from the group consisting of ruthenium diox rabutoxy zirconium, tetraethoxy zirconium, zirconium 4,931,573 11 12 oxyacetate, zirconium oxystearate, dicyclopentadiene phenylborate, triethoxy aluminum, tributoxy aluminum, zirconium dicarbonyl, tetramethoxy hafnium, tetrae triethyl aluminum, aluminum benzoate, aluminum stea thoxy hafnium, tetracyclopentadiene hafnium, vana rate, gallium triisoproxide, gallium isoproxyacetylace dium hexacarbonyl, dicyclopentadienetrihydride nio tonate, hydroxydimethyl gallium, trimethyl gallium, bium, niobium oxide ethoxide, niobium pentamethox 5 methoxydimethyl gallium, dimethyl gallium acetate, ide, niobium pentaisoproxide, tantalum pentamethox indium trimethoxide, indium triisoproxide, triisopropyl ide, tantalum pentaisoproxide, cyclopentadienylteracar indium, trimethyl indium, phenyl indium, diacetate, bonyl tantalum,biscyclopentadienyltrimethyl tantalum, methyloxo thallium, hydroxydimethyl thallium, me pentabenzyl tantalum, trimethoxy boron, triphenoxy thanesulfone dimethyl thallium, trimethyl thallium, boron, methylboronic acid, phenylboronic acid, di O thallium carbonate, methyl thallium diacetate, triethoxy phenylborinic acid, triphenyl boran, tricyclohexyl bo thallium, butoxydimethyl thallium, die ran, tetraethyl diboran, dimethyl(dimethylamino) bo thylaminodimethyl thallium and dimethyl thallium ace ran, triethylboroxine, tricyclohexyl boroxine, triphenyl tylacetonate. boroxine, sodium tetraphenylborate, ammonium tetra : 15

20

25

30

35

45

50

55

60

65