JPH05279352A - Production of lactones by hydrogenation - Google Patents

Abstract

PURPOSE:To enable production of lactones, particularly gamma-butyrolactone in high selectivity by hydrogenation of a saturated and/or unsaturated dicarboxylic acid under mild conditions. CONSTITUTION:The hydrogenation of a saturated and/or unsaturated dicarboxylic acid is effected in the presence of a catalyst of a noble metal in group VIII supported on a carrier and an alkali metal salt of an organic compound bearing 2 or more functional groups.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing lactones, and more particularly to a method for producing γ-butyrolactone. γ-Butyrolactone is a compound useful as a raw material for the synthesis of organic electroconductive solution solvents and pyrrolidones.

[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. The present invention is to provide a method for producing lactones, particularly γ-butyrolactone, with high selectivity.

[0007]

As a result of intensive studies to solve the above problems, the inventors of the present invention have two or more functional groups using a noble metal of Group VIII supported on a carrier as a catalyst. By carrying out the hydrogenation reaction in the presence of an alkali metal salt of an organic compound, it is possible to obtain a highly selective reaction under mild conditions with a one-step hydrogenation reaction regardless of whether a saturated or unsaturated dicarboxylic acid derivative is used as a raw material. As a result, they have found that lactones can be produced and completed the present invention.

That is, in the present invention, when hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative, an alkali metal salt of an organic compound having two or more functional groups is catalyzed by a Group VIII noble metal supported on a carrier. The present invention relates to a method for producing lactones, which comprises performing a hydrogenation reaction in the coexistence of

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 may 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 lactones, for example, diethyl ether, dimethoxyethane, diglyme, triglyme, tetrahydrofuran, ethers such as dioxane, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetophenone and other ketones, methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate and other esters, methanol, ethanol, n
Alcohols such as -butanol, iso-butanol, tert-butanol, 1,4-butanediol, n-
Aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, ethylbenzene and cumene, acidic solvents such as acetic acid, lactones such as γ-butyrolactone, acid amides such as 2-pyrrolidone and N-methylpyrrolidone And the like. 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. It is not necessary to dry these solvents before use, and conversely, water may coexist as long as they are about 1 molar equivalent to the raw materials.

The catalyst used in the present invention is a Group VIII noble metal supported on a carrier. In the present invention, a Group VIII noble metal supported on a carrier is used as a catalyst. Such a catalyst can be obtained by subjecting a noble metal compound and a carrier to physical and chemical treatments. V to use
The group III noble metal compound is not particularly limited as long as it can be converted into a metallic group VIII noble metal during the hydrogenation reaction or before being used in the reaction.

Specifically, ammonium hexachloropalladate, ammonium tetrachloropalladate,
Dinitrodiamine palladium, palladium bromide, chlorocarbonyl palladium, palladium chloride, palladium iodide, palladium nitrate, palladium oxide, palladium sulfate, palladium acetate, potassium dinitrosulfite palladium, potassium hexachloropalladate, potassium tetrabromopalladate, tetra Potassium chloropalladate, sodium hexachloropalladate,
Sodium tetrachloropalladate, tetraamminepalladium chloride, tetraamminepalladium nitrate,
Palladium compounds such as cis-dichlorodiaminepalladium, trans-dichlorodiaminepalladium, dichloro (ethylenediamine) palladium, potassium tetracyanopalladate, ammonium hexachlororhodate, ammonium pentachloroacharodiate, potassium pentachloroacharodiate, rhodium bromide ,
Rhodium chloride, rhodium hydroxide, rhodium iodide, rhodium nitrate, rhodium oxide, sodium hexabromorhodate, sodium hexachlororhodate, mel-trichlorotriammine rhodium, chloropentaammine rhodium chloride, dichlorobis (ethylenediamine) rhodium nitrate, cis -Dichlorobis (ethylenediamine) rhodium nitrate, tris (ethylenediamine) rhodium chloride, trans-dichlorotetrapyridine rhodium chloride, rhodium compounds such as dodecacarbonyltetrarhodium, hexadecacarbonylhexalodium, ammonium oxydecachlorodiruthenate, pentachloro Ammonium aquathenate, ammonium ruthenate chloride, potassium oxydecachlorodiruthenate, pentachloro Potassium aquarthenate, potassium perruthenate, ruthenium bromide, ruthenium chloride, ruthenium iodide, ruthenium nitrate nitrosyl ruthenium, ruthenium oxide, sodium oxydecachlorodiruthenate, hexaammine ruthenium chloride, pentaammine chloro ruthenium chloride, hexa Ammine ruthenium bromide, dodecacarbonyltriruthenium, hexacarbonyltetrachlorodiruthenium, ruthenium compounds such as cesium tricarbonyltrichlororuthenate, ammonium hexabromoiridate, ammonium hexachloroiridate, hexachloroiridate,
Iridium bromide, iridium chloride, iridium oxide, potassium hexabromoiridate, potassium hexachloroiridate, sodium hexabromoiridate, sodium hexachloroiridate, chloropentaammineiridium chloride, cis-dichlorobis (ethylenediamine) iridium chloride, trans −
Dichlorobis (ethylenediamine) iridium chloride,
Iridium compounds such as dodecacarbonyltetriridium, trans-octacarbonyloctachlorotetriridium acid, ammonium hexabromoplatinate, ammonium tetrachloroplatinate, dinitrodiamineplatinum,
Dinitrosulfite platinic acid, hexabromoplatinic acid, hexachloroplatinic acid, hexahydroxyplatinic acid, platinum bromide, platinum chloride, platinum iodide, platinum oxide, potassium hexabromoplatinate, potassium hexachloroplatinate, potassium hexahydroxoplatinate, Potassium hexaiodoplatinate, potassium tetrabromoplatinate, potassium tetrachloroplatinate, sodium hexabromoplatinate, sodium hexachloroplatinate, sodium hexahydroxoplatinate, sodium tetrachloroplatinate, tetraammineplatinum chloride, tetraammineplatinum hydroxide, tetracyano Platinum compounds such as sodium platinate may be mentioned. Preferred is a palladium compound.

The amount of the Group VIII noble metal supported on the catalyst used is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the total weight of the catalyst. Even if it is more than 20% by weight, the increase in activity per unit weight of the noble metal of Group VIII becomes small, which is not preferable. If it is less than 0.1%, sufficient activity cannot be obtained.

The carrier may be a porous substance, and specific examples include silica, alumina, silica-alumina, zeolite, diatomaceous earth, silica magnesia, silica zirconia, magnesia, zirconia, titania and other crystalline or non-crystalline metals. Examples thereof include oxides or complex oxides, layered clay compounds such as teniolite and hectorite, activated carbon and the like. 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 in the suspension bed, and tablet compression molded products, spherical or rod-shaped extrusion molded products and the like are used in the fixed bed.

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 physical mixing method, an impregnation method, an ion exchange method or the like. In the case of the impregnation method, the noble metal compound of Group VIII is dissolved in a suitable solvent, a carrier is added thereto, and if necessary, the mixture is left standing 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, and the metallic VI
Once the Group II noble metal is obtained, it may be reduced in the gas phase using, for example, hydrogen, or in the liquid phase using hydrazine. The reduction temperature is not particularly limited as long as the noble metal of Group VIII is reduced to a metal. Generally, a temperature of up to 500 ° C is sufficient. In the case of production by the ion exchange method, ion exchange can be performed using a noble metal compound of Group VIII having a desired concentration, and thereafter the same method as the impregnation method can be used.

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 in that an alkali metal salt of an organic compound having two or more functional groups is made to coexist as an additive together with a Group VIII noble metal supported on a carrier. An organic compound having two or more functional groups is a carboxyl group as one functional group, or a saturated or unsaturated aliphatic or aromatic organic acid having a sulfone group, in addition to this, a hydroxyl group, a carboxyl group, It is an organic compound having one or more functional groups selected from an alkoxycarbonyl group, a formyl group, a sulfone group, and an amino group.

For example, maleic acid, succinic acid, oxalic acid,
Glutaric acid, dicarboxylic acids such as phthalic acid, monomethyl maleate, monoethyl succinate, monoethyl oxalate, dicarboxylic acid monoesters such as monopropyl glutarate, 4-hydroxybutyric acid, 3-hydroxybutyric acid,
Hydroxycarboxylic acid such as salicylic acid, aminobenzoic acid, 2-aminoisobutyric acid, aminocarboxylic acid such as 5-aminovaleric acid, formylbenzoic acid, formylcarboxylic acid such as 4-formylcinnamic acid and 3-formylpropionic acid. Acid, sulfoacetic acid, sulfocarboxylic acid such as 5-sulfoisophthalic acid, p-hydroxybenzenesulfonic acid, hydroxysulfonic acid such as 2-hydroxyethane-1-sulfonic acid, 2-aminoethane-1-sulfonic acid, 3 -Aminosulfonic acid such as amino-2- (4-chlorophenyl) -propylsulfonic acid, formylsulfonic acid such as 2-formylbenzenesulfonic acid, methyl sulfoacetate, sulfocarboxylic acid such as ethyl 5-sulfoisophthalate Esters, disulfones such as m-benzenedisulfonic acid Acid, sulfo hydroxy carboxylic acids such as 5-sulfosalicylic acid, hydroxyamino acids such as 2-hydroxy-4-aminobenzoic acid.

As additives, lithium, sodium,
Various salts of alkali metals such as potassium, rubidium and cesium can be used.In this case, even if all the functional groups capable of forming salts are alkali metal salts, or partially alkali metal salts. There is no problem even if you do.

Specifically, lithium maleate, sodium maleate, potassium maleate, rubidium maleate, cesium maleate, monomethyl lithium maleate, monomethyl sodium maleate, monomethyl potassium maleate, monomethyl rubidium maleate, maleic acid. Maleates such as monomethyl cesium,
Succinates such as lithium succinate, sodium succinate, potassium succinate, rubidium succinate, cesium succinate, monomethyl lithium succinate, monomethyl sodium succinate, monomethyl potassium succinate, monomethyl rubidium succinate, monomethyl cesium succinate, Lithium oxalate, sodium oxalate, potassium oxalate, rubidium oxalate, cesium oxalate, monomethyl lithium oxalate, monomethyl sodium oxalate, monomethyl potassium oxalate, monomethyl rubidium oxalate, oxalates such as monomethyl cesium oxalate, Lithium malonate, sodium malonate, potassium malonate, rubidium malonate, cesium malonate,
Malonates such as monomethyl lithium malonate, sodium monomethyl malonate, monomethyl potassium malonate, monomethyl rubidium malonate and monomethyl cesium malonate, lithium glutarate, sodium glutarate,
Potassium glutarate, rubidium glutarate, cesium glutarate, monomethyl lithium glutarate, sodium monomethyl glutarate, monomethyl potassium glutarate, monomethyl rubidium glutarate, monomethyl cesium glutarate, etc., lithium phthalate,
Sodium phthalate, potassium phthalate, rubidium phthalate, cesium phthalate, monomethyl lithium phthalate, monomethyl sodium phthalate, monomethyl potassium phthalate, monomethyl rubidium phthalate, monomethyl cesium phthalate and other phthalates, lithium isophthalate, Sodium isophthalate, potassium isophthalate, rubidium isophthalate, cesium isophthalate,
Isophthalic acid salts such as monomethyl lithium isophthalate, monomethyl sodium isophthalate, monomethyl potassium isophthalate, monomethyl rubidium isophthalate, monomethyl cesium isophthalate, lithium 3-hydroxypropionate, sodium 3-hydroxypropionate, potassium 3-hydroxypropionate , Rubidium 3-hydroxypropionate, propionate such as cesium 3-hydroxypropionate, lithium 4-hydroxybutyrate, sodium 4-hydroxybutyrate, potassium 4-hydroxybutyrate, rubidium 4-hydroxybutyrate,
Butyrate such as cesium 4-hydroxybutyrate, lithium salicylate, sodium salicylate, potassium salicylate,
Salicylates such as rubidium salicylate, cesium salicylate, lithium 5-sulfosalicylate, sodium 5-sulfosalicylate, potassium 5-sulfosalicylate, rubidium 5-sulfosalicylate, and cesium 5-sulfosalicylate, lithium 3-formylpropionate, 3-
Formyl propionates such as sodium formyl propionate, potassium 3-formyl propionate, rubidium 3-formyl propionate, and cesium 3-formyl propionate can be mentioned.

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, the progress of side reaction only increases, and if it is lower than this, 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 varies depending on the setting method of temperature, pressure, amount of catalyst and the like or the reaction method, so that it is difficult to determine the range unconditionally, 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.

[0030]

[Examples] Hereinafter, the present reaction will be described in more detail with reference to Examples, but the present reaction is not limited to these Examples.

Example 1 0.44 g of palladium chloride (PdCl ₂ ) is dissolved in 40 ml of 2N hydrochloric acid. To this solution is added 4.94 g of activated carbon ground to 200 mesh or less.

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 powder was placed in a gas flow type reduction device and nitrogen 1 was added.
A gas mixed with 00 ml / min and 10 ml / min of hydrogen was used for reduction at 400 ° C. for 2 hours to obtain a 5% Pd / C catalyst.

98 mg (1 mmol) of maleic anhydride and 5% Pd were placed in a 10 ml stainless steel autoclave.
/ C (21 mg), potassium maleate (10 mg) and dimethoxyethane (1 ml) 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 16 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 91.9 mol% based on the maleic anhydride as a raw material. At this time, by-products such as THF and 1,4-BDO were not found at all.

Examples 2 to 11 Reactions and analyzes were carried out in the same manner as in Example 1 except that the compounds shown in Table 1 were used in place of potassium maleate as an additive and the reaction time was 2 hours. The results are shown in Table 1.

Example 12 A reaction was carried out in the same manner as in Example 1 except that 116 mg (1 mmol) of maleic acid was used as a raw material.

As a result of the same analysis as in Example 1, the yield of γ-butyrolactone was 85.8 with respect to the maleic acid as a raw material.
%Met. At this time, by-products such as THF and 1,4-BDO were not found at all.

Example 13 The reaction and analysis were carried out in the same manner as in Example 12 except that cesium maleate was used as an additive instead of potassium maleate and the reaction time was 2 hours. The results are shown in Table 1.

Examples 14 to 15 The reaction was carried out in the same manner as in Example 2 except that the compounds shown in Table 1 were used instead of maleic anhydride as a raw material. The results are shown in Table 1.

Example 16 Reaction and analysis were carried out in the same manner as in Example 2 except that THF was used instead of dimethoxyethane as a solvent. The results are shown in Table 1.

[0042]

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

Comparative Example 2 The reaction and analysis were carried out in the same manner as in Comparative Example 1 except that the reaction time was 2 hours. The results are shown in Table 2.

Comparative Examples 3 to 5 Reactions and analyzes were carried out in the same manner as in Comparative Example 2 except that the compounds shown in Table 2 were used instead of maleic anhydride as a raw material. The results are shown in Table 2.

Comparative Example 6 Reaction and analysis were carried out in the same manner as Comparative Example 2 except that THF was used instead of dimethoxyethane as the solvent. The results are shown in Table 2.

[0046]

[Table 2]

[0047]

INDUSTRIAL APPLICABILITY According to the present invention, when hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative, a noble metal of Group VIII supported on a carrier is used as a catalyst to form an organic compound having two or more functional groups. By carrying out the hydrogenation reaction in the presence of an alkali metal salt, lactones can be produced with high yield and high selectivity under mild conditions as compared with conventional heterogeneous catalysts.

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

Claims (2)

[Claims] 1. When hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative, in the presence of an alkali metal salt of an organic compound having two or more functional groups, using a Group VIII noble metal supported on a carrier as a catalyst. A method for producing lactones, characterized in that hydrogenation reaction is carried out. 2. When hydrogenating a succinic acid and / or maleic acid derivative, a noble metal of Group VIII supported on a carrier is used as a catalyst in the presence of an alkali metal salt of an organic compound having two or more functional groups. A method for producing γ-butyrolactone, which comprises performing a hydrogenation reaction.