JPH0778055B2 - Method for producing lactone - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a lactone by hydrogenating a dicarboxylic acid, a dicarboxylic acid anhydride and / or a dicarboxylic acid ester.

[Conventional technology]

A method for hydrogenating a dicarboxylic acid, a dicarboxylic acid anhydride and / or a dicarboxylic acid ester to produce a lactone has been studied for a long time, and various catalysts have been found so far.

For example, a nickel catalyst (for example, Japanese Patent Publication No. 43-6947), a cobalt catalyst (for example, Japanese Patent Publication No. 51-95057), a copper-chromium catalyst (for example, Japanese Patent Publication No. 38-20119), and a copper- Many proposals have been made for a method for producing lactones by using a zinc-based catalyst (for example, Japanese Patent Publication No. 42-14463) by a hydrogenation reaction system such as a fixed bed or a liquid suspension phase. On the other hand, a method for producing lactones in which the above hydrogenation reaction is carried out using a homogeneous ruthenium catalyst is also known. For example, for U.S. Pat.No. 3,957,827, [RuXn (PR ₁ R ₂ R ₃ ) xLy] type catalyst is used to carry out the hydrogenation reaction under the conditions of 40 to 400 psi, and U.S. Pat.No. 4,485,246 describes the hydrogenation reaction using the same catalyst in the presence of an organic amine. It is described to do.

[Problems to be solved by the invention]

However, in the conventional methods using the above nickel-based catalysts, cobalt-based catalysts, copper-chromium-based catalysts, copper-zinc-based catalysts, etc., it is inevitable to adopt harsh conditions of several tens of atmospheres or more. There was a problem that it did not exist. on the other hand,
The conventional method using the above-mentioned homogeneous ruthenium catalyst is characterized in that the hydrogenation reaction proceeds under relatively mild conditions, but on the other hand, the catalytic activity is rather low and the catalyst life is significantly long. There was a problem that it was short.

An object of the present invention is to solve all the above-mentioned conventional problems, and to provide a method for producing a lactone capable of hydrogenating a dicarboxylic acid, a dicarboxylic acid anhydride, and / or a dicarboxylic acid ester in an industrially advantageous manner. To do.

[Means for solving problems]

The present inventors have conducted extensive studies to achieve such an object, and as a result, in a method for producing a lactone by hydrogenating a dicarboxylic acid, a dicarboxylic acid anhydride and / or a dicarboxylic acid ester, ruthenium, an organic phosphine and a periodic table When a conjugated base of an acid having a metal compound pka selected from the group consisting of IV ^A , V ^A and III ^B groups smaller than 2 is used as a catalyst, not only the hydrogenation catalytic activity is increased but also the activity stability of the catalyst is improved. Found to be effective for
The present invention has been reached.

Hereinafter, the present invention will be described in detail.

As the dicarboxylic acid, dicarboxylic acid anhydride and / or dicarboxylic acid ester used as a raw material in the present invention, a saturated or unsaturated dicarboxylic acid having 3 to 7 carbon atoms in the dicarboxylic acid skeleton and / or a derivative thereof is used. Specific examples of the dicarboxylic acid, succinic acid, fumaric acid, maleic acid, glutaric acid (glutaric acid), methylsuccinic acid, etc., as the dicarboxylic acid anhydride, succinic anhydride, maleic anhydride, glutaric anhydride, methylsuccinic anhydride Etc. The dicarboxylic acid ester is preferably an alkyl ester, and particularly preferably a dicarboxylic acid derivative having a dicarboxylic acid skeleton with 4 carbon atoms. For example, dimethyl maleate, diethyl fumarate, succinic acid-di-n
-Butyl and the like.

As a raw material for producing γ-butyrolactone, maleic acids such as maleic acid, maleic anhydride and maleic acid ester, and succinic acids such as succinic acid, succinic anhydride and methylsuccinic acid are preferable.

The catalyst used in the method of the present invention contains ruthenium, an organic phosphine, a compound of a metal selected from the group consisting of groups IV ^A , V ^A and III ^{B of} the periodic table, and a conjugate base of an acid having a pka of less than 2. To do.

As the ruthenium catalyst, both metallic ruthenium and ruthenium compounds can be used. As the ruthenium compound in this case, an oxide of ruthenium, a hydroxide, an inorganic acid salt, an organic acid salt or a complex compound is used, and specifically, for example, ruthenium dioxide, ruthenium tetroxide, ruthenium dihydroxide, Ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium acetate, tris (acetylacetone) ruthenium, sodium hexachlororuthenate, dipotassium tetracarbonyl ruthenate, pentacarbonyl ruthenium, cyclopentadienyl dicarbonyl ruthenium, dibromotricarbonyl ruthenium Chlorotris (triphenylphosphine) hydridoruthenium, bis (tri-n-butylphosphine) tricarbonylruthenium,
Examples thereof include dodecacarbonyltriruthenium, tetrahydridodecacarbonyltetraruthenium, octadecacarbonylhexaruthenate dicesium, and undecacarbonylhydridotriruthenate tetraphenylphosphonium.

The amount of these metal ruthenium and ruthenium compounds used is such that the concentration in the reaction solution is 0.0001 to 100 mol, preferably 0.001 to 10 mol as ruthenium in 1 liter of the reaction solution.

In the method of the present invention, the use of an organic phosphine together with a ruthenium catalyst is an essential requirement, which contributes to controlling the electronic state of ruthenium which is the main catalyst and stabilizing the active state of ruthenium. It is considered to be a thing. Specific examples of such an organic phosphine include tri-
trialkylphosphines such as n-butylphosphine and dimethyl-n-octylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, triarylphosphines such as triphenylphosphine,
Examples thereof include alkylarylphosphines such as dimethylphenylphosphine and polyfunctional phosphines such as 1,2-bis (diphenylphosphino) ethane.

The amount of these organic phosphines used is in the range of 0.1 to 1000 mol, preferably 1 to 100 mol, per 1 mol of ruthenium as the main catalyst. Also, these organic phosphines can be supplied to the reaction system by themselves or in the form of a complex with a ruthenium catalyst.

In the present invention, as an additional promoter for ruthenium catalysts for the hydrogenation reaction main catalyst, periodic table IV ^A, V
^A, but using a metal compound selected from the group consisting of III ^B Group, whereby, in terms of can proceed hydrogenation reaction under relatively mild conditions by utilizing the advantage of the main catalyst, in particular, hydrogen It is possible to improve the oxidization catalyst activity, the activity stability, and the daily product selectivity.

The metals selected from the group consisting of groups IV ^A , V ^A , and III ^{B of} the periodic table include Group IV ^A : titanium, zirconium, and hafnium Group ^VA : vanadium, niobium, tantalum Group III ^B daughter: boron, Examples include aluminum, gallium, indium, and thallium. Of these, titanium, zirconium,
Vanadium is preferable, and zirconium and vanadium are particularly preferable. Examples of these metal compounds include carboxylates, nitrates, halides, oxohalides, sulfates, hydroxides, carbonates, oxalates, phosphates, chromates, silicates, cyanides, and oxides. Compounds, metal alkoxides, acetylacetone salts, organometallic compounds, and the like. Among them, in consideration of solubility and thermal stability,
It is preferably added in the form of metal halides, metal alkoxides, acetylacetone salts, carboxylates, hydroxides or oxides.

Such periodic table IV ^A, V ^A, as a specific example of a III ^B metal compound is titanium tetrachloride, titanium tetraethoxide, titanium tetra-isopropoxide, titanium tetrabutoxide,
Titanium compounds such as titanium ammonium oxalate, titanyl acetylacetonate, titanium hydroxide; zirconyl dichloride, zirconium tetrachloride, zirconium acetylacetonate, zirconium carbonate, zirconium naphthenate, zirconium octate, dicyclopentadiene zirconium dimethoxide, dicyclo. Pentadiene zirconium diethoxide, zirconocene, tetrabutoxy zirconium, tetraethoxy zirconium, zirconium oxyacetate, zirconium oxystearate,
Zirconium compounds such as zirconium phosphate, zirconium oxynitrate, zirconium sulfate, dicyclopentadiene zirconium dicarbonyl; hafnium chloride, tetramethoxyhafnium, tetraethoxyhafnium, dicyclopentadienehafnium dicarbonyl, tetrabenzylhafnium, tetracyclopentadienehafnium, etc. Haunium compounds; vanadium chloride, vanadium acetylacetonate, vanadyl nitrate, vanadyl sulfate, vanadyl acetylacetonate, vanadyl oxalate, vanadium oxalate, ammonium metavanadate, vanadium hexacarbonyl, etc .; , Niobium oxide ethoxide, niobium pentamethoxide, niobium pentaisop Niobium compounds such as xide; tantalum chloride, tantalum oxide, tantalum pentamethoxide, tantalum pentaisoproxide, cyclopentadienyl tetracarbonyl tantalum, biscyclopentadienyl trimethyl tantalum, pentabenzyl tantalum; boron trichloride, Trimethoxyboron, triphenoxyboron, boric acid, boron oxide, orthoboric acid, pyroboric acid, metaboric acid, methylboronic acid, phenylboronic acid, diphenylborinic acid, triphenylborane, tricyclohexylborane, tetraethyldiborane, dimethyl (dimethylamino) Borane, borazine, triethylboroxine, tricyclohexylboroxine, triphenylboroxine, sodium tetraphenylborate, ammonium tetraphenylborate, a Boron compounds such as monium tetraoxoboric acid; aluminum compounds such as aluminum chloride, triethoxy aluminum, tributoxy aluminum, triethyl aluminum, aluminum acetate, aluminum acetylacetonate, aluminum benzoate and aluminum stearate; gallium chloride, gallium oxide, Gallium compounds such as gallium triisoproxide, gallium isoproxy acetylacetonate, hydroxydimethylgallium, trimethylgallium, methoxydimethylgallium, dimethylgallium acetate; indium chloride, indium trimethoxide, indium triisoproxide, triisopropylindium, trimethylindium. , Indium compounds such as phenylindium diacetate; tariu chloride , Methyl oxo thallium, hydroxy dimethyl thallium, methane sulfonate dimethyl thallium, trimethyl thallium, thallium hydroxide, thallium carbonate, thallium acetate, methyl thallium diacetate, triethoxy thallium, butoxydimethyl thallium, diethylaminodimethyl thallium, dimethyl thallium acetylacetonate And thallium compounds. The amount of these metal compounds used is 0.01 to 1000 per 1 mol of ruthenium in the main catalyst.
Mol, preferably 0.1 to 100 mol, more preferably 0.5.
~ 20 moles.

An additional pka of 2 as an additional promoter for ruthenium catalysts
By using a conjugate base of a smaller acid, the hydrogenation catalyst activity can be improved, the activity stability and the selectivity of the target product can be improved.

The conjugate base of an acid having a pka of less than 2 may be any as long as it produces such a conjugate base during catalyst preparation or in the reaction system, and the supply form thereof is Bronstedt acid having a pka of less than 2 or various such acids. Salt or the like is used. Specifically, nitric acid, perchloric acid, fluoroboric acid, hexafluorophosphoric acid, inorganic acids such as fluorosulfonic acid, tricarboxylic acetic acid, dichloroacetic acid, halogen carboxylic acid such as trifluoroacetic acid, methanesulfonic acid, dodecylsulfonic acid, Organic sulfonic acids such as octadecyl sulfonic acid, trifluoromethane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, sulfonated styrene-
Examples thereof include Bronsted acids such as organic acids such as divinylbenzene copolymers, alkali metal salts, alkaline earth metal salts, ammonium salts and silver salts of these acids, and organic sulfonic acids are particularly preferable.

It is also possible to add the conjugate base of these acids in the form of an acid derivative which is considered to be produced in the reaction system. For example, similar effects can be expected even when added to the reaction system in the form of acid halide, acid anhydride, ester, acid amide, or the like.

The amount of these acids or salts thereof used is in the range of 0.01 to 1000 mol, preferably 0.1 to 100 mol, and more preferably 0.5 to 20 mol, per 1 mol of ruthenium.

The method of the present invention can be carried out in the absence of a solvent, that is, using the reaction raw material or the reaction product itself as a solvent, but a solvent other than these can also be used. Examples of such a solvent include ethers such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol diethyl ether and dioxane, ketones such as acetone, methyl ethyl ketone and acetophenone, methanol, ethanol, n-butanol, benzyl alcohol, phenol and ethylene. Alcohols such as glycol and diethylene glycol, carboxylic acids such as formic acid, acetic acid, propionic acid and toluic acid, methyl acetate,
Esters such as n-butyl acetate and benzyl benzoate, aromatic hydrocarbons such as benzene, toluene, ethylbenzene and tetralin, aliphatic hydrocarbons such as n-hexane, n-octane and cyclohexane, dichloromethane, trichloroethane, chlorobenzene and the like. Halogenated hydrocarbons, nitro compounds such as nitromethane and nitrobenzene, N, N-
Dimethylformamide, N, N-dimethylacetamide,
Carboxylic acid amides such as N-methylpyrrolidone, hexamethylphosphoric triamide, other amides such as N, N, N ', N'-tetraethylsulfamide, N, N'-dimethylimidazolidone, N, N, Urea such as N, N-tetramethylurea, dimethyl sulfone, sulfone such as tetramethylene sulfone, dimethyl sulfoxide, sulfoxides such as diphenyl sulfoxide, γ-butyrolactone, lactones such as ε-caprolactone, tetraglyme, 18- Polyethers such as Crown-6, nitriles such as acetonitrile and benzonitrile, and carbonic acid esters such as dimethyl carbonate and ethylene carbonate.

In order to carry out the hydrogenation reaction by the method of the present invention, the reaction raw material, the catalyst component and, if desired, a solvent may be charged into a reaction vessel, and hydrogen may be introduced therein. Hydrogen may be diluted with a reaction-inert gas such as nitrogen or carbon dioxide.

Prior to charging the reaction raw materials, a catalyst component and optionally a solvent are charged into a reaction vessel, and heat treatment of the catalyst is carried out under an atmosphere of hydrogen or argon, since the production of by-products is small and the selectivity is improved, which is preferable. . Heat treatment is usually 100-300 ℃,
It is preferably carried out at 150 to 250 ° C for at least 0.5 hours.

The reaction temperature is generally 50 to 250 ° C, preferably 100 to 200 ° C. The hydrogen partial pressure in the reaction system is usually 0.1 to 100 kg / cm ² , preferably 1 to 30 kg / cm ² . Of course, it is not impossible to carry out at lower or higher pressure,
Not industrially advantageous.

The reaction can be carried out in either a batch system or a continuous system. The reaction time required for the batch method is usually 1
~ 20 hours.

The target lactone can be recovered from the reaction product solution by a usual separation and purification means such as distillation and extraction. Also. The distillation residue can be circulated to the reaction system as a catalyst component.

〔Example〕

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1 In a 200 ml sus autoclave with an induction stirrer, ruthenium acetylacetonate 0.08 gr (0.2 mmol), trioctylphosphine 0.74 gr (2.0 mmol), p-toluenesulfonic acid 0.33 gr (1.76 mmol), zirconium oxystearate. Charge 2.01 gr (3.0 mmol) and 40 ml of tetraethylene glycol dimethyl ether, 200 at a hydrogen pressure of 20 kg / cm ² .
Heat treatment was performed at ℃ for 2 hours. After that, the hydrogen pressure was raised to 30 kg / cm ² and 25 wt% of maleic anhydride dissolved in tetraethylene glycol dimethyl ether was used at 24 ml / H using a liquid pump.
It is injected into the autoclave at an injection rate of r
The reaction was carried out at 0 ° C for 2 hours.

During that time, the amount of maleic anhydride injected into the autoclave was 12.9 gr (132.4 mmol).

After the reaction, the reaction solution was taken out and analyzed, and the conversion of maleic anhydride was 97.6%, the total selectivity of succinic anhydride and γ-butyrolactone was 83.4%, and the selectivity of propionic acid was 10.4.
%Met. The yield of γ-butyrolactone was 33.9%.

Comparative Example 1 The same operation as in Example 1 was performed except that zirconium oxystearate was not added.

The amount of maleic anhydride charged into the autoclave is 120 gr
(123.2 mmol).

After the reaction, analysis revealed that the conversion of maleic anhydride was 9
The total selectivity for γ-butyrolactone and succinic anhydride was 44.4%. Propionic acid was a by-product with a selectivity of 50.8%. The yield of γ-butyrolactone was 5.2%.

Examples 2 to 4 The same procedure as in Example 1 was carried out except that 2.01 g of zirconium oxystearate was replaced with the compounds of the metals shown in Table 1. The results are shown in Table 1.

Example 5 In a 200 ml SUS autoclave equipped with an induction stirrer, ruthenium acetylacetonate 0.08 gr (2.0 mmol), trioctylphosphine 0.74 gr (2.0 mmol), p-toluenesulfonic acid 0.33 gr (1.76 mmol), zirconium oxystearate. Charge 2.01 gr (3.0 mmol) and 64 ml of tetraethylene glycol dimethyl ether, 200 at a hydrogen pressure of 20 kg / cm ² .
Heat treatment was performed at ℃ for 2 hours.

The autoclave was cooled, the autoclave was opened under an argon atmosphere, 16 g (160 mmol) of succinic anhydride was added, and the reaction was carried out at 200 ° C. for 2 hours at a hydrogen pressure of 30 kg / cm ² .

After the reaction, the reaction solution was taken out and analyzed, and the conversion rate of succinic anhydride was 74.0% and the selectivity of γ-butyrolactone was 9%.
It was 4.5%.

〔The invention's effect〕

According to the present invention, when a dicarboxylic acid, a dicarboxylic acid anhydride and / or a dicarboxylic acid ester is hydrogenated to produce a raketone, the ruthenium of the present invention, an organic phosphine, the periodic table IV ^A , V ^A , III ^B By conducting the reaction in the liquid phase using a compound of a metal selected from the group consisting of the group and a conjugate base of an acid having a pka of less than 2, the yield is high and the selection is high under milder conditions than conventional methods. The desired lactone can be obtained at a specific rate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07B 61/00 300

Claims (2)

[Claims] 1. A method for producing a lactone by hydrogenating a dicarboxylic acid, a dicarboxylic acid anhydride and / or a dicarboxylic acid ester in the presence of a catalyst, comprising: ruthenium organic phosphine, Group IV ^A , V ^A and III ^{B of the} periodic table. A method for producing a lactone, which comprises performing a hydrogenation reaction in a liquid phase in the presence of a catalyst containing a conjugate base of an acid having a metal compound pka selected from the group consisting of: 2. A method for producing γ-butyrolactone by hydrogenating a dicarboxylic acid having a carbon number of 4 in the dicarboxylic acid skeleton in the presence of a catalyst, dicarboxylic acid anhydride and / or its ester, wherein ruthenium organophosphine titanium, zirconium And a method for producing γ-butyrolactone, which comprises performing a hydrogenation reaction in a liquid phase in the presence of a catalyst containing an organic sulfonic acid having a metal pka selected from vanadium smaller than 2.