JPH069601A - Production of lactones by hydrogenation - Google Patents

Abstract

PURPOSE:To provide the process for enabling high-selectivity production of lactones, particularly gamma-butyrolactone which is useful as a solvent for an organic electrically conductive solution or as a starting substance for organic syntheses of pyrrolidone, etc., because the process can be operated under mild conditions, even when saturated and/or unsaturated dicarboxylic acid are used. CONSTITUTION:In the hydrogenation of saturated and/or unsaturated acids, nickel, or a combination thereof with at least one element selected from the elements in group VIb, VIIb and VIII of the periodic table is used as a catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing lactones, and more particularly to a method for producing .gamma.-butyrolactone. [gamma] -butyrolactone is a compound useful as a solvent for an organic electroconductive solution, a synthetic raw material for pyrrolidones and the like.

[0002]

2. Description of the Related Art Hitherto, many proposals have been made regarding a method for producing a lactone by hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative in a liquid phase.

For example, as a catalyst, a method using an activated carbon-supported palladium catalyst (hereinafter abbreviated as Pd / C) (US Pat. No. 3,113,138) and a method using a nickel-based catalyst (for example, JP-B-43-6947). , A method using a cobalt-palladium-based catalyst (for example, JP-B-58-29).
No. 142) is known.

However, the method using Pd / C is
When succinic anhydride is used as a raw material, γ-butyrolactone is obtained in a relatively high yield, but when maleic anhydride is used, a two-step reaction is required, and in addition, a catalyst is added during operation. There's a problem.

The method using a nickel-based catalyst or a cobalt-palladium-based catalyst has the advantage that the cost of the catalyst is relatively low, but the reaction conditions are 250 ° C. and 100 kg /
Since it is as rigorous as cm ² G, side reactions such as formation of cyclic ether and decarboxylation proceed, and the selectivity of lactones is not satisfactory.

[0006]

The object of the present invention is to provide a milder condition than a conventionally known catalyst in a one-step hydrogenation reaction, regardless of whether a saturated or unsaturated dicarboxylic acid derivative is used as a raw material. It is an object of the present invention to provide a method for producing lactones, particularly γ-butyrolactone, with high selectivity.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by performing a hydrogenation reaction in the presence of an alkali metal salt with nickel as a catalyst, The present invention has been completed by finding that lactones can be produced with high selectivity in a single-stage hydrogenation reaction under mild conditions regardless of whether a saturated or unsaturated dicarboxylic acid derivative is used as a raw material.

That is, in the present invention, when hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative, nickel or at least one element selected from nickel and elements of the VIb group, VIIb group and VIII group is used as a catalyst. The present invention relates to a method for producing lactones, which comprises using an element catalyst and carrying out a hydrogenation reaction in the presence of an alkali metal salt.

The present invention will be described in detail below.

The raw materials used in the present invention are saturated and / or unsaturated dicarboxylic acid derivatives. Specifically, maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, methylsuccinic anhydride, anhydrides of saturated and / or unsaturated dicarboxylic acids such as glutaric anhydride, maleic acid, succinic acid, fumaric acid. , Itaconic acid, citraconic acid,
Examples thereof include saturated and / or unsaturated dicarboxylic acids such as mesaconic acid, methylsuccinic acid, and glutaric acid. Particularly when .gamma.-butyrolactone is intended, maleic anhydride, maleic acid, succinic anhydride, succinic acid and fumaric acid can be mentioned.

The saturated or unsaturated dicarboxylic acid derivatives which are the starting materials may be mixed in any proportion as long as the hydrogenation products are the same.

In the method of the present invention, the saturated and / or unsaturated dicarboxylic acid derivative is preferably dissolved in a solvent and then subjected to the reaction. The solvent is not particularly limited as long as it is inert to the hydrogenation reaction and does not react with the product lactone, for example, ether such as diethyl ether, dimethoxyethane, diglyme, triglyme, tetrahydrofuran or dioxane. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetophenone, esters such as methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate, methanol, ethanol, n-butanol, iso- Butanol, ter
Alcohols such as t-butanol and 1,4-butanediol, aliphatic hydrocarbons such as n-hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, ethylbenzene and cumene, acidic solvents such as acetic acid, γ-butyrolactone. And amides such as 2-pyrrolidone and N-methylpyrrolidone. Among them, preferable examples include dimethoxyethane and tetrahydrofuran, which have a relatively low boiling point and are easily recovered, or γ-butyrolactone which does not require solvent recovery.

The amount of the solvent used is not limited as long as the raw materials are dissolved at the reaction temperature. These solvents do not have to be particularly dried before use, and conversely water may coexist as long as they are about 1 molar equivalent to the raw materials.

As the catalyst in the present invention, nickel,
Alternatively, nickel and VIb, VIIb and VI
A catalyst composed of at least one element selected from Group II elements is used. Also, these catalysts
It may be carried on a carrier.

The compound that can be used to prepare the nickel catalyst is not particularly limited as long as it can be converted into metallic nickel during or before the hydrogenation reaction. Specifically, nickel carbonate, nickel chloride,
Various inorganic or organic nickel compounds such as nickel hydroxide, nickel nitrate, nickel oxide, nickel sulfate, nickel acetate and nickel oxalate can be used.

In a catalyst using nickel and at least one element selected from the group consisting of VIb, VIIb and VIII, molybdenum is a VIb element and rhenium is a VIIb element. Further, noble metals such as palladium and platinum can be cited as an example of the Group VIII element.

Specific examples of raw materials that can be used for preparing the catalyst include ammonium molybdate, molybdenum acetate, molybdenum hexacarbonyl, and VI in the case of molybdenum, which is an example of the VIb group element.
In the case of rhenium, which is an example of the Group Ib element, rhenium chloride, rhenium oxide, perrhenic acid, ammonium perrhenate, and the like, and as an example of the Group VIII element, for example, in the case of palladium, hexachloropalladic acid Ammonium, ammonium tetrachloropalladate, dinitrodiaminepalladium, palladium bromide, chlorocarbonylpalladium, palladium chloride, palladium iodide, palladium nitrate, palladium oxide, palladium sulfate, palladium acetate, potassium dinitrosulfite palladium, potassium hexachloropalladate ,
Potassium tetrabromopalladate, potassium tetrachloropalladate, sodium hexachloropalladate, sodium tetrachloropalladate, tetraamminepalladium chloride, tetraamminepalladium nitrate, cis-dichlorodiaminepalladium, trans
Examples thereof include dichlorodiamine palladium, dichloro (ethylenediamine) palladium, and potassium tetracyanopalladate.

Nickel and VIb group, VIIb as catalyst
When a catalyst composed of at least one element selected from the group VIII and VIII elements is used, the atomic ratio of the elements contained other than nickel (for example, M
o, Re or Pd / Ni) may be 0.01 to 0.5.

When nickel supported on a carrier is used as a catalyst, the carrier may be a porous substance, and specific examples include silica, alumina, magnesia, titania, silica alumina, zeolite, diatomaceous earth, silica magnesia, etc. Crystalline or non-crystalline metal oxides or complex oxides, layered clay compounds such as teniolite and hectorite,
Activated carbon etc. are mentioned. The shape of the catalyst is not particularly limited, and it can be used in the form of powder as it is or according to the reaction mode. Powders or granules are used for the suspension bed, and tablet compression molded products, spherical or rod-shaped extrusion molded products, and the like are used for the fixed bed.

The amount of nickel supported on the catalyst to be used is 1 to 60 as nickel metal based on the total weight of the catalyst including the carrier.
% By weight, preferably 5 to 50% by weight. in this case,
When the catalyst comprises nickel and further a catalyst comprising at least one element selected from the group consisting of VIb, VIIb and VIII, the atomic ratio of the elements contained other than nickel (eg Mo, Re or Pd / Ni) may be 0.01 to 0.5.

The method for producing the catalyst used in the present invention is not particularly limited, and a catalyst produced by a known method can be used. For example, it can be prepared by a precipitation method, a kneading method, an impregnation method, an ion exchange method, a deposition method or the like. When preparing by the impregnation method,
For example, a nickel compound, and in some cases, a compound such as palladium or rhenium is dissolved in a suitable solvent, a carrier is added thereto, and if necessary, the mixture is allowed to stand for a predetermined time and then dried. The reduction may be performed directly after drying, or in some cases, reduction may be performed after firing. Of course, it may be reduced in the reaction system. The reduction method is not particularly limited as long as metallic nickel is obtained. For example, hydrogen may be used for the gas phase reduction, or hydrazine or the like for the liquid phase reduction.

The reduction temperature is not particularly limited as long as at least nickel is reduced to metal. Generally 6
Temperatures up to 00 ° C are sufficient.

When the ion exchange method is used,
The desired concentration of nickel compound, and optionally further
Ion exchange may be performed using a compound such as palladium or rhenium, and then the same method as the impregnation method may be used.

In the case of further preparing by the deposition method, for example, a nickel compound, and in some cases, a compound such as palladium and rhenium is dissolved in a suitable solvent such as water, and the above-mentioned carrier is added and stirred. While adding a precipitant gradually or all at once to deposit nickel, palladium and rhenium components, dry the resulting mixture,
After that, the catalyst can be obtained by the same method as the impregnation method.

The amount of the catalyst used is not particularly limited, but is preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight, based on the raw material.

The present invention is characterized by the presence of an alkali metal salt as an additive together with a nickel catalyst. The alkali metal in the present invention is an alkali metal of Group Ia of the periodic table, for example, lithium, sodium, potassium, rubidium and cesium.

Alkali metal salts include various inorganic salts,
Organic alkali metal salts can be used. For example,
Examples of the inorganic salt include alkali metal chlorides, nitrates, carbonates, sulfates, phosphates, hydroxides and the like. Further, a layered compound represented by clay containing an alkali metal and various zeolites ion-exchanged with an alkali metal can also be used.

Specifically, chlorides such as lithium chloride, sodium chloride, potassium chloride, rubidium chloride and cesium chloride, nitrates such as lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate and cesium nitrate, lithium nitrite and nitrite. Sodium, potassium nitrite, rubidium nitrite, nitrite such as cesium nitrite, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Carbonate such as cesium carbonate, lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, sulfate such as cesium sulfate, lithium phosphate, sodium phosphate, potassium phosphate, rubidium phosphate, cesium phosphate and other phosphates Hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide.

Further, clay such as sodium-type, potassium-type, rubidium-type or cesium-type montmorillonite and caryonite, and various zeyrites in which the ion-exchangeable cation is an alkali cation such as potassium, rubidium or cesium are mentioned. For example, Philip Sight, Harmotome, Merleneute,
Jismondin, Amysite, Gallonite, Govinsite, Anal Sime, Wairakite, Paulingite, Laumontite, Yugawaralite, Shabasite,
Wilhender Sonite, Gmelinite, Faujasite, Elionite, Offretite, Levin, Mazzite, Natrolite, Tetrasoda Fluorite, Parasoda Fluorite, Mesolite, Scholesite, Tomsonite, Gonnaldite, Edingtonite, Mordenite, Duckardite, Episulile Bite , Ferrierite,
Bikitite, hurlandite, clino tyrolite, still bite, zutellite, barler light,
Natural zeolite such as brewsterite, korensite, goose creakite, A type, X type, Y type, USY
Type (also referred to as US-Y type), L type, HS type, ZK
-5 type, B type, R type, S type, G type, D type, T type, W type,
C type, Zeolon type, ZSM-5, mordenite, ferrierite and the like.

Examples of the organic salts include alkali metal carboxylates and sulfonates. As carboxylates, carboxylates such as formate, acetate, propionate, dicarboxylates such as maleate and succinate, dicarboxylates such as monomethyl maleate and monoethyl succinate. Acid monoester salts, hydroxybutyrate, hydroxycarboxylates such as salicylate, aminobenzoates, aminocarboxylates such as aminoisobutyrate, formylbenzoate, formylcinnamate, formylpropionic acid Formyl carboxylates such as salts, sulfoacetates, sulfocarboxylates such as 5-sulfoisophthalates.

As the sulfonate, benzene sulfonate, sulfonate such as p-toluene sulfonate,
Hydroxysulfonates such as hydroxybenzenesulfonate, aminosulfonates such as 2-aminoethane-1-sulfonate, formylsulfonates such as formylbenzenesulfonate, methyl sulfoacetate salts, sulfo Salts of sulfocarboxylic acid esters such as salts of ethyl isophthalate, disulfonates such as m-benzenedisulfonate, sulfohydroxycarboxylates such as sulfosalicylate, 2-hydroxy-4-aminobenzoate Hydroxyaminocarboxylic acid salts such as

Specifically, acetates such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate and cesium acetate, lithium trifluoroacetate, sodium trifluoroacetate, potassium trifluoroacetate, rubidium trifluoroacetate and cesium trifluoroacetate. Such as trifluoroacetate, lithium propionate, sodium propionate, potassium propionate, rubidium propionate, cesium propionate, lithium 3-hydroxypropionate, sodium 3-hydroxypropionate, potassium 3-hydroxypropionate, 3- Rubidium hydroxypropionate, propionates such as cesium 3-hydroxypropionate, lithium benzoate,
Benzoates such as sodium benzoate, potassium benzoate, rubidium benzoate and cesium benzoate, lithium maleate, sodium maleate, potassium maleate, rubidium maleate, cesium maleate, monomethyllithium maleate, monomethyl sodium maleate. , Maleic acid salts such as monomethyl potassium maleate, monomethyl rubidium maleate and monomethyl cesium maleate, succinates such as lithium succinate, sodium succinate, potassium succinate, rubidium succinate, cesium succinate, monomethyl lithium succinate , Oxalates such as lithium oxalate, sodium oxalate, potassium oxalate, rubidium oxalate, cesium oxalate and monomethyllithium oxalate.

Further, salicylates such as lithium salicylate, sodium salicylate, potassium salicylate, rubidium salicylate and cesium salicylate, lithium 3-formylpropionate, sodium 3-formylpropionate, potassium 3-formylpropionate, 3-formylpropionate. Rubidium, carboxylate such as formylpropionate such as cesium 3-formylpropionate, methylsulfonate such as lithium methylsulfonate, sodium methylsulfonate, potassium methylsulfonate, rubidium methylsulfonate and cesium methylsulfonate Salts, benzene sulfonates such as sodium benzene sulfonate, potassium benzene sulfonate, rubidium benzene sulfonate, cesium benzene sulfonate, p-toluene Sodium sulfonate, potassium p- toluenesulfonic acid, p- toluenesulfonic acid rubidium, p- toluenesulfonic acid salt of such p- toluenesulfonic acid cesium, lithium 5-sulfosalicylic acid, 5-
Examples thereof include sodium sulfosalicylate, potassium 5-sulfosalicylate, rubidium 5-sulfosalicylate, cesium 5-sulfosalicylate, and other sulfonates such as sulfosalicylates.

These additives are sufficiently effective when used alone, but may be used as a mixture of two or more if necessary.

The amount of the additive used is not particularly limited, but is 0.1 to 100% by weight, preferably 1 to 100% by weight based on the raw materials.
50% by weight is good. If the amount is larger than this, the reactor is unnecessarily increased in size, and in the suspension bed, the removal operation after the reaction is burdened, and conversely, the effect is diminished.

In the present invention, the reaction can be carried out in a batch system using a suspension bed, a semi-batch system, a continuous system, or a fixed bed flow system.

The reaction according to the method of the present invention is carried out under heating and hydrogen pressure. The reaction temperature is usually 50 to 300 ° C,
120-250 degreeC is selected preferably. If it is higher than this, only the progress of side reactions is increased, and if it is lower, there is a disadvantage in the reaction rate. The pressure of hydrogen is usually 10
~ 150 kg / cm ² G, preferably 15-120 kg
/ Cm ² G is selected. In the method of the present invention, since the desired reaction proceeds sufficiently within this range, a high pressure exceeding this is unnecessary, and a pressure lower than this is disadvantageous in terms of reaction rate.

The reaction time is difficult to unconditionally determine because it varies depending on the method of setting the temperature, pressure, amount of catalyst and the like or the reaction method, but in the batch system and the semi-batch system, it is usually 1 hour or more. Necessary, preferably 1-20
Good time It may be longer than this, but it is meaningless since the reaction is completed within this range. If it is shorter than this, a high conversion rate may not be obtained. In addition, in a continuous reaction using a suspension bed or a fixed bed flow reaction, the residence time may be 0.1 to 10 hours.

[0039]

EXAMPLES Hereinafter, this reaction will be described in more detail with reference to Examples, but it goes without saying that this reaction is not limited to these Examples.

[0040] Example 1 Nickel nitrate _{(Ni (NO 3) 2 ·} 6H 2 O) 1.49
g is dissolved in 10 ml of water. 2.72 g of silica (Carrieract 10 manufactured by Fuji Devison Co., Ltd.) ground to 200 mesh or less is added to this solution.

Excess water was removed under reduced pressure by a rotary evaporator, and the obtained paste was dried under reduced pressure at 80 ° C. for 2 hours and further at 110 ° C. for 2 hours to obtain a catalyst powder.

The above powder was put into a gas flow type reduction device,
Using a gas mixed with 100 ml / min of nitrogen and 10 ml / min of hydrogen, each was reduced at 400 ° C. for 2 hours,
A 10% Ni / SiO ₂ catalyst was obtained.

98 mg (1 mmol) of maleic anhydride and 10% N in a 10 ml stainless steel autoclave.
After charging 21 mg of i / silica, 10 mg of MS3A and 1 ml of dimethoxyethane and sufficiently replacing the system with hydrogen,
Hydrogen was injected under pressure so that the pressure was 50 kg / cm ² G. The temperature was raised to 180 ° C. with heating and stirring, and a hydrogenation reaction was carried out for 2 hours.

After completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction liquid was taken out. After the catalyst and the like were filtered off, the filtrate was analyzed by gas chromatography. As a result, the yield of γ-butyrolactone was 80.0 mol% based on the maleic anhydride as a raw material.

Examples 2 to 7 Reactions and analyzes were carried out in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of MS3A as an additive. The results are shown in Table 1.

Examples 8-9 10% Ni / silica instead of 10% Ni / silica as catalyst
The reaction and analysis were performed in the same manner as in Example 1 except that activated carbon and 10% Ni / diatomaceous earth were used. The results are shown in Table 1.

Example 10 A reaction was carried out in the same manner as in Example 1 except that 100 mg (1 mmol) of succinic anhydride was used as a raw material.

As a result of analysis in the same manner as in Example 1, the yield of γ-butyrolactone was 74.
It was 5%.

Example 11 THF was used in place of dimethoxyethane as a solvent,
Further, the reaction and analysis were carried out in the same manner as in Example 1 except that cesium maleate was used instead of MS3A. The results are shown in Table 1.

[0050]

[Table 1] Example 12 Nickel nitrate _{(Ni (NO 3) 2 ·} 6H 2 O) 1.49
g and 0.12 g of palladium acetate are dissolved in 10% aqueous ammonia. Silica crushed to 200 mesh or less in this solution (Carrieract 10 manufactured by Fuji Devison Co., Ltd.) 2.7
Add 2 g. After standing for a predetermined time, excess water was removed under reduced pressure with a rotary evaporator, and the obtained paste was dried under reduced pressure at 80 ° C for 2 hours, and further dried at 110 ° C.
And dried for 2 hours to obtain a catalyst powder.

The above powder was put into a gas flow type reduction device,
Using a gas mixed with 100 ml / min of nitrogen and 10 ml / min of hydrogen, each was reduced at 400 ° C. for 2 hours,
To obtain a Ni-Pd / SiO ₂ catalyst.

98 mg (1 mmol) of maleic anhydride and Ni-P were placed in a 10 ml autoclave made of stainless steel.
21 mg of d / silica, 10 mg of cesium sulfate and 1 ml of dimethoxyethane were charged, the system was sufficiently replaced with hydrogen, and then hydrogen was injected under pressure to 50 kg / cm ² G.
The temperature was raised to 180 ° C. with heating and stirring, and a hydrogenation reaction was carried out for 2 hours.

After completion of the reaction, the autoclave was cooled to room temperature, and then hydrogen was purged to take out the reaction solution. After filtering off the catalyst and the like, the filtrate was analyzed by gas chromatography. As a result, the yield of γ-butyrolactone was 92.9 mol% based on the maleic anhydride as a raw material.

Examples 13 to 17 Reactions and analyzes were carried out in the same manner as in Example 12 except that the raw materials and additives were changed. The results are shown in Table 2.

[0055] Example 18 Nickel nitrate _{(Ni (NO 3) 2 ·} 6H 2 O) 1.49
g and 0.13 g of perrhenic acid are dissolved in distilled water. 2.72 g of silica (Carrieract 10 manufactured by Fuji Devison Co., Ltd.) ground to 200 mesh or less is added to this solution.

After standing for a predetermined time, excess water was removed under reduced pressure by a rotary evaporator, and the obtained paste was dried under reduced pressure at 80 ° C. for 2 hours and further at 110 ° C. for 2 hours to obtain a catalyst powder. Got

The above powder was put into a gas flow type reduction device,
Using a gas mixed with 100 ml / min of nitrogen and 10 ml / min of hydrogen, each was reduced at 400 ° C. for 2 hours,
To obtain a Ni-Re / SiO ₂ catalyst.

98 mg (1 mmol) of maleic anhydride and Ni-R were placed in a 10 ml autoclave made of stainless steel.
e / Silica (21 mg), cesium sulfate (10 mg) and dimethoxyethane (1 ml) were charged, and the inside of the system was sufficiently replaced with hydrogen, and then hydrogen was press-fitted to 50 kg / cm ² G.
The temperature was raised to 180 ° C. with heating and stirring, and a hydrogenation reaction was carried out for 2 hours.

After completion of the reaction, the autoclave was cooled to room temperature, and then hydrogen was purged to take out the reaction liquid. After filtering off the catalyst and the like, the filtrate was analyzed by gas chromatography. As a result, the yield of γ-butyrolactone was 79.3 mol% based on maleic anhydride as a raw material. At this time, by-products such as THF and 1,4-BDO were not found at all.

Examples 19 to 21 Reactions and analyzes were carried out in the same manner as in Example 18 except that the raw materials and additives were changed. The results are shown in Table 2.

[0061]

[Table 2] Comparative Example 1 Reaction and analysis were carried out in the same manner as in Example 1 except that MS3A was not used. The results are shown in Table 3.

Comparative Examples 2 to 3 Reactions and analyzes were carried out in the same manner as Comparative Example 1 except that the compounds shown in Table 3 were used instead of 10% Ni / silica as the catalyst. The results are shown in Table 3.

Comparative Example 4 Reaction and analysis were carried out in the same manner as Comparative Example 1 except that succinic anhydride was used instead of maleic anhydride as a raw material. The results are shown in Table 3.

Comparative Example 5 Reaction and analysis were carried out in the same manner as in Comparative Example 1 except that THF was used instead of dimethoxyethane as the solvent. The results are shown in Table 3.

Comparative Example 6 The reaction and analysis were carried out in the same manner as in Example 12 except that MS3A was not used. The results are shown in Table 3.

Comparative Example 7 The reaction and analysis were carried out in the same manner as in Example 12 except that the raw material was changed to succinic anhydride and no additive was used. The results are shown in Table 3.

Comparative Example 8 The reaction and analysis were carried out in the same manner as in Example 18 except that cesium sulfate was not used. The results are shown in Table 3.

Comparative Example 9 Reaction and analysis were carried out in the same manner as in Example 18 except that the raw material was changed to succinic anhydride and no additive was used. The results are shown in Table 3.

[0069]

[Table 3]

[0070]

According to the present invention, when hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative, the hydrogenation reaction is carried out in the presence of an alkali metal salt using nickel as a catalyst to obtain a conventional heterogeneous compound. It is possible to produce lactones in high yield and high selectivity under mild conditions as compared with the system catalyst.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location // C07B 61/00 300 (72) Inventor Atsushi Fujimura Yokkaichi, Mie Alias 6-7-8 ( 72) Inventor Takashi Okada 1-6-17 Hatunaka, Yokkaichi-shi, Mie (72) Inventor Hiroyuki Sasakihara 6618-12 Sakuramachi, Yokkaichi-shi, Mie (72) Takanori Miyake Another name 3-5-1, Yokkaichi-shi, Mie (72) Yoshiaki Kano, Miyukigaoka, 2-chome, Yokkaichi, Mie 1504-67 (72) Inventor, Toshihiro Saito Yokkaichi, Mie Also known as 4-14-22

Claims (3)

[Claims] 1. A method for producing a lactone, which comprises hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative in the presence of an alkali metal salt with nickel as a catalyst. 2. When hydrogenating a succinic acid and / or maleic acid derivative, a hydrogenation reaction is carried out in the presence of an alkali metal salt with nickel as a catalyst.
-A method for producing butyrolactone. 3. Nickel and VIb group, VIIb as catalyst
3. The method according to claim 1 or 2, wherein at least one element selected from Group VIII and Group VIII elements is used.