JPS62195374A - Production of lactone or such - Google Patents

Abstract

PURPOSE:In obtaining a lactone by hydrogenating a dicarboxylic acid, an acid anhydride, an ester, etc., thereof, a Ru catalyst, an organic phosphine and an alkaline (earth) metallic chloride, ammonium chloride, etc., as an additional promoter are present. CONSTITUTION:In obtaining a lactone by hydrogenating a dicarboxylic acid (preferably 4C), an acid anhydride and/or an ester thereof in the presence of a Ru catalyst and an organic phosphine (e.g., tri-n-butylphosphine), 0.5-20mol based on 1mol Ru in the catalyst of a compound selected from an alkaline (earth) metallic chloride and ammonium chloride is present to carry out the reaction. EFFECT:Catalytic activity is increased, a catalytic life is extremely prolonged and reaction can be advanced under a mold condition.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to dicarboxylic acids, dicarboxylic anhydrides, and/or dicarboxylic acid anhydrides.
Alternatively, the present invention relates to a method for producing lactones by hydrogenating dicarboxylic acid esters.

(Prior Art) Conventionally, several methods are known for hydrogenating dicarboxylic acids, dicarboxylic acid anhydrides, and/or dicarboxylic acid esters to produce lactones. That is, nickel-based catalysts (for example, Japanese Patent Publication No. 43-6947),
Cobalt-based catalysts (e.g., JP-A-51-95057), copper-chromium-based catalysts (e.g., JP-A-38-20119)
(Japanese Patent Publication No. 42-1), and copper-zinc catalysts (for example, Japanese Patent Publication No. 42-1
A number of proposals have been made regarding methods for producing lactones by a hydrogenation reaction method such as a fixed bed or a liquid phase suspension phase using the method (Japanese Patent Publication No. 4463). On the other hand, there are also known methods for producing lactones in which the above hydrogenation reaction is carried out using a homogeneous ruthenium catalyst; for example, U.S. Pat.
In the specification of No. 957,827, (RuXn (PRI
4O-400p using a catalyst of type R2R3)xLy)
It is described that the hydrogenation reaction is carried out under si conditions, and US Pat. No. 4,485,246 describes that the hydrogenation reaction is carried out using a similar catalyst in the presence of an organic amine. There is.

(Problems to be Solved by the Invention) However, in the conventional methods using nickel-based catalysts, cobalt-based catalysts, copper-chromium-based catalysts, copper-zinc-based catalysts, etc. as described above, all of them require tens of atmospheric pressures. There was a problem in that the adoption of the above harsh conditions was unavoidable. on the other hand,
The conventional method using the homogeneous ruthenium catalyst described above has the characteristic that the hydrogenation reaction proceeds under relatively mild conditions, but the catalyst activity is at a rather low level and the catalyst life is significantly shortened. It had the fatal problem of being short.

The present invention aims to solve all of the above-mentioned conventional problems and to provide a method for producing lactones that can hydrogenate dicarboxylic acids, dicarboxylic acid anhydrides, and/or dicarboxylic acid esters with unprecedented industrial advantage. shall be.

(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors found that combining a specific halogen compound with a ruthenium catalyst not only increases the hydrogenation catalyst activity, but also The present invention was achieved by discovering for the first time that the life of a catalyst can be significantly extended. That is, the present invention provides a method for producing lactones by hydrogenating dicarboxylic acids, dicarboxylic acid anhydrides, and/or dicarboxylic acid esters in the presence of a ruthenium catalyst and an organic phosphine, in which an alkali metal as an additional promoter is used. The gist of the present invention is a method for producing lactones, which is characterized by carrying out a hydrogenation reaction in the presence of a compound selected from the group consisting of chlorides, alkaline earth metal chlorides, and ammonium chlorides.

The dicarboxylic acids, dicarboxylic anhydrides, and dicarboxylic esters used as raw materials in the production method of the present invention are saturated or unsaturated dicarboxylic acid derivatives having 3 to 7 carbon atoms, and the esters are preferably alkyl esters, particularly As the carboxylic acid skeleton, a derivative having 4 carbon atoms is preferable. Specifically, for example, fumaric acid, succinic acid, maleic anhydride,
Examples include succinic anhydride, dimethyl maleate, diethyl fumarate, and 1-n-butyl succinate.

The main catalyst in the method of the invention is a ruthenium catalyst.

As the ruthenium catalyst, both metal ruthenium and ruthenium compounds can be used. As the ruthenium compound in this case, ruthenium oxides, hydroxides, inorganic acid salts, organic acid salts, complex compounds, etc. are used.
Specifically, for example, ruthenium dioxide, ruthenium tetroxide, ruthenium trihydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium nitrate, ruthenium acetate, tris(acetylacetone)ruthenium, sodium hexachlororuthenate, tetracarbonylruthenic acid. Dipotassium, pentacarbonylruthenium, cyclopentadienyldicarbonylruthenium, cyfuromotricarbonylruthenium, chlorotris() IJ phenylphosphine)hydridoruthenium, bis(tri-n-butylphosphine)tricarbonylruthenium, totecacarbonyltriruthenium, tetrahydride Examples include decacarbonyltetraruthenium, dicesium octadecacarbonylhexarthenate, and tetraphenylphosphonium tecacarbonylhydridotriruthenate.

The amount of these metal ruthenium and ruthenium compounds to be used is such that the concentration in the reaction solution is 0.0001 to 100 moles of ruthenium per liter of the reaction solution, preferably 0.0
The amount is 0.01 to 10 moles.

The method of the present invention requires the use of an organic phosphide in conjunction with the ruthenium catalyst, which controls the electronic state of the main catalyst ruthenium and stabilizes the form of chlorine as a promoter. It is thought that this contributes. Specific examples of such organic phosphines include tree n
- trialkylphosphines such as butylphosphine and dimethyl-n-octylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, triarylphosphines such as triphenylphosphine, alkylarylphosphine such as dimethylphenylphosphine, 1, Examples include polyfunctional phosphines such as 2-bis(diphenylphos-7))etay.

The amount of these organic phosphines used is in the range of 0.1 to 1000 mol, preferably 1 to 100 mol, based on 1 mol Klt of ruthenium as the main catalyst. Further, these organic phosphines can be supplied to the reaction system either alone or in the form of a complex with a ruthenium catalyst.

(Function) The method of the present invention comprises dicarboxylic acid, dicarboxylic acid anhydride,
and/or by using a compound selected from alkali metal chlorides, alkaline earth metal chlorides, and ammonium chlorides as an additional promoter for the ruthenium catalyst that is the main catalyst for the hydrogenation reaction of dicarboxylic acid esters. In addition to being able to proceed with the hydrogenation reaction under relatively mild conditions by taking advantage of its advantages, it is particularly characterized in that it improves the hydrogenation catalyst activity and significantly extends its life. Specific examples of the above-mentioned chlorides that serve as such additional promoters include lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, ammonium chloride, and tetraethylammonium chloride.

Examples include magnesium chloride, calcium chloride, strontium chloride, barium chloride, and the like. The amount of these chlorides used is 0.0 per mole of ruthenium in the main catalyst.
1 to 1,000 mol, preferably 0.1 to 100 mol,
More preferably, it is in the range of 0.5 to 20 mol.

The method of the present invention can be carried out in the absence of a solvent, that is, using the reaction raw material itself as a solvent, but it is also possible to use a solvent other than the reaction raw material. Examples of such solvents include ethers such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol dimethyl ether, and dioxane, ketones such as acetone, methyl ethyl ketone, and aceto 2-enone, methanol, ethanol, n-butanol, benzyl alcohol, phenol, Alcohols such as ethylene glycol and diethylene glycol, carboxylic acids such as formic acid, acetic acid, propionic acid, and toluic acid, esters such as methyl acetate, n-butyl acetate, and benzyl benzoate, benzene, toluene,
Aromatic hydrocarbons such as ethylbenzene and tetralin, n-
Aliphatic hydrocarbons such as hexane, n-octane, and cyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, and chlorobenzene; nitro compounds such as nitromethane and nitrobenzene; N,N-dimethylborumamide; N,N-dimethylacetamide; -Carboxylic acid amides such as methylpyrrolidone, hexamethylphosphoric acid triamide, other amides such as N,N,N',N'-tetraethylsulfamide, N,N'-dimethylimidazolitone, N,N.

Ureas such as N, N-tetramethylurea, sulfo compounds such as dimethylsulfone and tetramethylenesulfone, sulfoxides such as dimethylsulfoxide and diphenylsulfoxide, lactones such as γ-butyrolactone and -monocaprolactone, 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 in the method of the present invention, it is sufficient to charge a reaction material, a catalyst component, and, if desired, a solvent into a reaction vessel, and then introduce hydrogen into the reaction vessel. Hydrogen may be diluted with a gas inert to the reaction, such as nitrogen or carbon dioxide.

The reaction temperature is usually 50 to 250°C, preferably 100 to 250°C.
The temperature is 200°C. The hydrogen partial pressure in the reaction system is usually 0.1 to
100 kgfaA, preferably 1-10 to 9/cIA
It is. Of course, it is not impossible to carry out the process under lower or higher pressures, but it is not industrially advantageous.

The reaction can be carried out either batchwise or continuously. In the case of batch method, the required reaction time is usually 1~
It is 20 hours.

The desired lactones can be recovered from the reaction product liquid by conventional separation and purification means such as distillation and extraction. Further, the distillation residue can be recycled to the reaction system as a catalyst component.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

Example 1 Ruthenium trichloride 0.052 in a bubble column glass reactor
05' (Ru:O12mmoJ), triphenylphosphine 70.5249 (ZOmmOJ), lithium chloride 0, 08702 (ZOmmoJ), tetraglyme 2
0nBB, and succinic anhydride 20.0nBB as a reaction raw material. O
f (zoomrno#) and hydrogen gas at normal pressure.
While introducing oNTP-1/br, the mixture was heated to 170°C and reacted. Since the reaction raw material decreases due to consumption and evaporation during the reaction, it was replenished at regular intervals to maintain the amount of succinic anhydride in the reaction system at around 150 mmoJ. Since chlorine ions also dissipate, lithium chloride was added as appropriate so that it was present in an amount of 2 moles or more per 1 mole of Ru. The production rate of γ-butyrolactone (hereinafter abbreviated as "GBL") was initially 20 mmoJ/hr, gradually decreased, and reached a steady value of 14.4 mmoJ/hr after 10 hours.

Comparative Example 1 has a high rate of 20 mmo4/hr, but the ruthenium catalyst deteriorates rapidly as chlorine ions dissipate, and after 10 hours, the G
The BL production rate was significantly reduced to 3 mmad/hr.

From the results of Example 1 and Comparative Example 1 above, in the case of continuous reaction,
It can be seen that the method of the present invention is significantly superior to the conventional method of not replenishing chlorine ions in that the deterioration of the ruthenium catalyst is extremely small and the GBL production rate reaches a high steady-state value.

Example 2 Ru2(O□CC2H4C0
2) 2 (P-Ph3)4o, 148t (Ru:
o, 2 m rnoe ), triphenylphosphine 0
．． 262? (1,0 m mad ), lithium chloride O,o 17 Of (0,4 mmol), succinic anhydride 10. (1 (100mmoJ) and 10m of tetraglyme!, under normal pressure, hydrogen gas at 5N)
The reaction was carried out at 170° C. for 2 hours while introducing at a rate of TP-g/hr. A total of 34.1 mmoJ in the reactor and distillate
GBL was generated.

Comparative Example 2 When the same experiment as in Example 2 was conducted without adding lithium chloride, the amount of GBL produced was significantly reduced to 14.0 mm071.

Moreover, since the GBL generation rate in Comparative Example 2 is comparable to the GBL generation rate in Comparative Example 1, RuC
Even in the case of Comparative Example 1 in which J3 was used as the ruthenium catalyst, it was presumed that in the steady state, the ruthenium catalyst was in the form of a succinic acid-coordinated complex as used in Comparative Example 2 without the addition of CI. . In fact, this was subsequently confirmed by isolating the steady-state complex and using IR, NMR, etc. methods.

From the above examples, it is clear that lithium chloride activates the succinic acid-coordinated ruthenium complex, which has low activity, into a more highly active species.

Example 3 When the same experiment as in Example 2 was conducted for 4 hours using succinic acid as a reaction raw material instead of succinic anhydride, GBLI 6
．． 1 mmoJ was generated.

Comparative Example 3 When the same experiment as in Example 3 was conducted without adding lithium chloride, 6.3 mmol of GBL was produced.

Examples 4 to 5 The same experiment as in Example 2 was conducted by changing the amount of lithium chloride added. The amount added was 0.211 f (5.0 mmoJ)
Example 4 and 0.00862 (0.2 mmoJ)
In the case of Example 5, the amount of GBL produced was aa in Example 4, smmo4. In Example 5, it was 28.2 mm0J.

Examples 6-11 Same experiment as Example 2 but using 0.0
21Of ammonium chloride (Example 6), 0.021
5f sodium chloride (Example 7), 0.178f cesium chloride (Example 8), 0.1Of magnesium chloride (Example 9), 14g calcium chloride (Example 1o), 0. x7f using tetraethylammonium chloride (Example 11), GB
The production amount of L was 35.8 m moJ in Example 6,
In Example 7, it was 14.6 mmo7I, and in Example 8, it was 20.
8 m mop, 30.2 mmoJ in Example 9, 16.0 mmoJ in Example 10, and 23.0 mmoJ in Example 11.
It was 1mm0J.

Example 12 Ruthenium trichloride 0,0 s in a bubble column glass reactor
20 f (Ru: 0.2 mmol), triphenylphosphine yo, sz+f (λOmmoJ), lithium chloride 0.0435f (1, Ommol), reaction raw material GuA/p/l/acid 13.2f (100mm
oJ) and Tetra Climb 20m/! was charged and heated at normal pressure while introducing hydrogen gas at a rate of tONTP-J/hr.
The reaction was carried out at 70°C for 4 hours. δ-valerolactone zsm
mo4 was generated.

Example 13 Ruthenium trichloride o, os2 in a bubble column glass reactor
(1 (Ru: 0.2 mmojl)
, ) Li-n-hexylphosphine 70.70 ml (ZOm mail), lithium chloride 0.0870 f (ZOm mol), succinic anhydride as a reaction raw material 20. Of(200mmo7)
and 20ml of tetraglyme and heated to 170℃ under normal pressure while introducing hydrogen gas at 1oNTP@14/hr.
The mixture was allowed to react for 2 hours. GBL6.9mmON was generated.

Example 14 The same experiment as Example 1 was conducted except that succinic acid was used as the reaction raw material, and the GBL production rate in steady state was 5.
．． There was 4 m mail hr f.

Examples 15-16 The experiment of Example 14 was repeated, but the reaction temperature was changed to 160℃ in Example 15.
Example 14 except that the temperature was 180°C in Example 16.
When conducted in the same manner as above, the GBL production rate in the steady state was 3.6 m mop /hr in Example 15,
In Example 16, it was 8.2 mmoJ/hr.

(Effect of the invention) As is clear from the above results, it is novel in that it uses a compound selected from alkali metal chlorides, alkaline earth metal chlorides, and ammonium chlorides as an additional promoter for the ruthenium catalyst as the main catalyst. In addition, the method for producing lactones by hydrogenation reaction of the present invention allows the hydrogenation reaction to proceed under mild conditions in either a continuous or batch reaction system, and also uses a ruthenium catalyst as a hydrogenation catalyst. By increasing the activity and significantly extending the life of the hydrogenation catalyst, this method has the remarkable effect of making it possible to obtain lactones with unprecedented industrial advantage.

Claims (1)

[Claims] (1) an alkali metal chloride as an additional promoter in a method for hydrogenating a dicarboxylic acid, a dicarboxylic acid anhydride, and/or a dicarboxylic acid ester to produce lactones in the presence of a ruthenium catalyst and an organic phosphine;
A method for producing lactones, which comprises carrying out a hydrogenation reaction in the presence of a compound selected from the group consisting of alkaline earth metal chlorides and ammonium chlorides.