JPS6041659B2 - Manufacturing method of ethylidene diacetate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing ethylidene diacetate, which is characterized by subjecting methyl acetate or dimethyl ether, carbon monoxide, and hydrogen to a hydrocarbonylation reaction.

Conventionally, methods for synthesizing ethylidene diacetate include a method using acetylene and acetic acid as raw materials and a method of synthesizing ethylidene diacetate by reacting acetaldehyde and acetic anhydride.

In contrast, in recent years, methyl acetate or dimethyl ether is used as a raw material and carbon monoxide and hydrogen are used as catalysts. A method of synthesizing ethylidene diacetate through the reaction was proposed in JP-A-51-115409. The present inventors have also filed Japanese Patent Application No. 117660/1984. The specification of JP-A-51-115409 describes hydrocarboni,
IL 1L++ 11-1 ＾J-＾ 3L-1
Arml p11C114) and halides are disclosed as both essential components, and further states that the reaction is "promoted by the combined use of a co-catalyst" and details the reaction co-catalyst (p11c416-p13C414). or,
Examples 1 to 29 of the specification all use a limited specific noble metal such as rhodium or palladium as the main catalyst, and furthermore, in the absence of an organic or inorganic co-catalyst, no ethylidene diacetate was produced. No (Example 58). J In summary, JP-A-51-1
No. 1544 discloses the synthesis of ethylidene diacetate from methyl acetate or dimethyl ether in the presence of a halide using a catalyst system using rhodium or palladium as a main catalyst and a specific organic or inorganic compound as a co-catalyst. be.

However, these metals are expensive [Hydro
carbonProcess, 54, June 83 (1
975)], to prevent rhodium complexes and the like from being reduced to metals in a reducing atmosphere during industrial implementation,
[Kagaku to Kogyo, 29 (5), p. 376 (1975)] or by distillation separation of the product to prevent it from volatilizing and dissipating from the reaction system.
The complexity of the process, such as the need for special measures such as 204), has been one of the major obstacles to the industrial production of ethylidene diacetate. In view of the above points, the present inventors have conducted extensive research into a rational method for producing ethylidene diacetate using an inexpensive catalyst, eliminating the drawbacks of the above methods.

As a result, a new catalyst system using nickel and ruthenium was discovered, and the present invention was completed. That is, in the present invention, substantially all of This is a method for producing ethylidene diacetate, which is characterized by reacting methyl acetate or dimethyl ether with carbon monoxide and hydrogen in an anhydrous state. Although the detailed reaction operation of the hydrocarbonylation reaction of methyl acetate or dimethyl ether according to the present invention is not clear, the overall reaction can be represented by the following chemical reaction formula.

(1) When methyl acetate is used as a raw material (2) When dimethyl ether is used as a raw material The catalyst of the present invention uses nickel and ruthenium as main catalysts, and uses a halide such as iodide or bromide as a promoter.

Organic and inorganic nickel and ruthenium compounds can be used as the nickel or ruthenium compound component and the ruthenium or ruthenium compound component used as the main catalyst.

For example, 2. Various -nickel compounds such as nickel powder, nickel acetate, nickel halide, nickel acetylacetone, nickel tetracarbonyl, nickel dicarbonyl, nickel dicarbonyl bistriphenylphosphine, tetramethylammonium nickel genide,
and ruthenium metal, ruthenium halide, ruthenium hydroxide, ruthenium oxide, ruthenium nitrate, ruthenium acetylacetone, ruthenium acetate, ruthenium carbonyl iodide, ruthenium carbonyl, ruthenium sulfate, ruthenium sulfide ruthenium phosphate, dichlorotris(triphenylphosphine)ruthenium, Various ruthenium compounds are used. The nickel compound or ruthenium compound is effective as a main catalyst even when used alone, but the activity is low, and when both metals or metal compounds are used in combination, the activity becomes extremely high. Although the process of the invention requires the presence of a halide along with nickel and ruthenium catalysts, the preferred halide is bromide or iodide or a mixture thereof, preferably iodide.

Usually the halides are mostly in the form of mether halides, acetyl halides, hydrogen halides or any mixtures thereof, preferably methyl iodide, acetyl iodide, hydrogen iodide or any mixtures thereof. may be introduced into the reaction form. However, if any one or more of these halides, ie, methyl halide, acetyl halide, or hydrogen halide, preferably methyl iodide, acetyl iodide, or hydrogen iodide, is introduced, a compound is produced in the reaction system. Good too. Compounds that react with other components in the reaction system to produce methyl halides, acetyl halides, and hydrogen halides include inorganic halides, such as alkali metal salts such as lithium, sodium, and potassium, and salts of alkali metals such as magnesium and calcium. There are alkaline earth metals or metal salts such as aluminium, zinc, copper, lanthanum or cerium, and iodine and bromine. In the present invention, the reaction can be suitably carried out by combining the above-mentioned main catalyst and co-catalyst, but in order to further speed up the reaction rate, a promoter can be used. Nitrogen compounds can be used as promoters.

Suitable nitrogen group compounds include organic compounds containing nitrogen, phosphorus, antimony or arsenic, or ammonia. Non-limiting examples of compounds effective as accelerators are grouped into groups.

(1) Trivalent nitrogen group compound (A) General formula M<? : Nitrogen group compounds (
However, M represents N, P, Sb, and As.

) (a) Rl, R2, R3 are hydrogen or have 1 to 1 carbon atoms
0 saturated alkyl group, cycloalkyl group or aryl group, which may be the same or different from each other
=N Ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, dimethylethylamine, tri-n-propylamine, tri-IsO-propylamine, tri-n-butylamine, tri-tert-ditylamine, aniline, dimethylaniline, diethylaniline , dimethylbenzylamine, toluidine, triphenylamine,
Amines such as cyclohexylamine M=P tri-n-propylphosphine, tri-1s0-propylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, tri-cyclohexylphosphine, tri-
Phosphine such as phenylphosphine M=Sb tri-1s0-propylstipine, ethyl-zi IsO
- Stipines such as propylstipine, triphenylstipine, tri(0-tolyl)stipine, phenyludiamylstipine, etc. M=M trimethylarsine, trimethylarsine, tricyclohexylarsine, phenyludi IsO-propylarsine, Arsines (b) R such as diphenylarsine
1 represents hydrogen or a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group, R2, R3
are connected by a polymethylene group having 1 to 5 carbon atoms; cyclic compounds such as pyrrolidine, N-methylpyrrolidine, piperidine, and N-phenylpiperidine; (c) Rl and R2 are hydrogen or a saturated alkyl group having 1 to 10 carbon atoms; It represents a cycloalkyl group or an aryl group, and may be the same or different.

R3 is a compound representing a saturated aliphatic acyl group having 1 to 10 carbon atoms, and R1 is hydrogen or a saturated alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms, and R2,
Lactam compound in which R3 is linked with a carboxypolymethylene group: acetamide, N,N-dimethylacetamide,
Carboxylic acid amides such as acetalinide, N-methyl-N-phenylacetamide, and lactams such as N-methyl-pyrodinone (d) At least one of Rl, R2, and R3 is a carboxymethyl group, and the rest are hydrogen or carbon Compounds N representing 1 to 10 saturated alkyl groups, cycloalkyl groups, or aryl groups, which may be the same or different
, N-dimethylglycine, N,N-diethylglycine, iminodiacetic acid, N-methyldiiminoacetic acid, nitrilotriacetic acid, etc. (e) R1 has 1 to 1 carbon atoms
0 saturated alkyl group, cycloalkyl group, or aryl group, R2 and R3 are nitriles bonded to M=N Nitriles such as acetonitrile, probionitrile, benzonitrile (B) General formula 1〉M1-R5- M2〈
An organic nitrogen group compound represented by 1 (where M1 and M2 are N, P, Sb, and As, and may be the same or different).

) (a) Rl, R2, R3. R4 represents hydrogen or a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and R5 represents a polymethylene group, phenylene group, or carbonyl group having 1 to 10 carbon atoms; a compound ethylenebis(diphenylphosphine); Phenylenebis(dimethylphosphine), bis(diphenylarsino)ethane, bis(di-1s0-propylacino)hexane, bis(diethylstivino)pentane, N,N,N″
,N″-tetramethylethylenediamine, N,N,N″
,N″-tetraethylethylenediamine, N,N,N″
,N″-tetra n-propylethylenediamine, N,
N,N'',N''-tetramethylmethylenediamine, N,
Compounds (b) R such as N,N″,N″-tetramethylurea, N-methyl-2-pyrodinone, triethylenediamine, etc.
l, R3 is hydrogen or a saturated alkyl group having 1 to 10 carbon atoms,
Cycloalkyl group or aryl group, R2, R4
are connected by a polymethylene group having 1 to 5 carbon atoms, and R5 is a polykylmethylene group having 1 to 5 carbon atoms. Piperazine, N-methyl-piperazine, N-ethyl-piperazine, 2-methyl-N,N''-dimethyl Cyclic compounds such as piperazine (C) Other compounds tris(diethylaminomethyl)stipine, 2,5-dicarboxypiperazine, cyclohexane-1,2-diamine-N,N,N″,N! -tetraacetic acid and salts and tetramethyl ester, ethylenediaminetetraacetic acid and salts and tetramethyl ester, 1,4-azabicyclo[2,2,2]octane, methyl-substituted 1,4-diazacyclo[2,2,2]octaneazide Compounds such as ponitrile and N-methylformoline (■) Heterocyclic compounds pyridine and alkylpyridines; pyridine, α-picoline, β-picoline, γ-picoline, 2-ethylpyridine, 3-ethylpyridine, 4-ethyl Pyridine 2-propylpyridine, 4-propylpyridine, 4-butylpyridine, 4-isobutylpyridine, 4-t-butylpyridine, 2,6-lutidine, 2,4-lutidine 2,5-lutidine, 3,4-lutidine, 3,5-lutidine 2,4,6
-collidine, 2-methyl-4-ethylpyridine, 2-methyl-5-ethyl, lupyridine, 3-methyl-4-ethylpyridine, 3-ethyl-4-methylpyridine, 3,4-
Diethylpyridine, 3,5-diethylpyridine, 4-pentylpyridine, 4-(5-nonyl)-pyridine, 2,
6-dipropylpyridine, 2-methyl-3-ethyl-6
-propylpyridine, 2,6-diethylpyridine, 2,
6-dipropylpyridine, 2,6-dibutylpyridine,
2,6-di-t-butylpyridine, pyridines containing functional groups; 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine
Cyanopyridine 2,6-dicyanopyridine 3,5-dicyanopyridine, 2-cyano6-methyl-pyridine, 3
-cyano-5-methyl-pyridine, picolinic acid amide,
Nicotinic acid amide, isonicotinic acid amide, pi-4-cholinic acid, nicotinic acid, isonicotinic acid, dipicolinic acid, dinicotinic acid, cinchometronic acid, 5-butyl-picolinic acid, nicotinic acid alkyl ester, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,
3-diaminopyridine, 2,5-diaminopyridine, 2
, 6-diaminopyridine, 2,3,6-triaminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 2- Amino 4-
Propylpyridine, 2-amino-4-propylpyridine 2-amino-4(5-nonyl)-pyridine, 4-amino-4,6-dimethylpyridine, 2,6-diamino-4methylpyridine, 2,2-dipyridylamine, 4- Dimethylaminopyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,6-hydroxypyridine, 3-hydroxy-6-methylpyridine, 2-chloropyridine, 2,6-dichloropyridine,
4-chloropyridine, 2-amino-5-chloropyridine, 2-amino-3,5-dichloropyridine, 2-methyl-3,5-dichloro-6-methylpyridine, 2-amino-5-chloro-3-methylpyridine, 2-amino-3 ,5
-dichloro-4-methylpyridine, 2-amino-3,5
-dichloro4,6-dimethylpyridine4-amino3
,5-dichloropyridine, pyridine-N-oxide, α
-Picoline-N-oxide, β-picoline-N-oxide, β-picoline-N-oxide, γ-picoline-N-
Oxy, 2,6-lutidine-N-oxide, 3,5-lutidine-N-oxide, 4-phenylpropylpyridine-N-oxide, 1,3-di(4-pyridine)-propane di-N-oxide, 4-(5- nonyl)-pyridine-N-oxide, 2-chloropyridine-N-oxide,
4-cyanopyridine-N-oxide, 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, 2,6-pyridinemethanol, 2pyridinemethanol, 4-pyridinemethanol, 3-picolylamine,
4-picolylamine, 2-methylaminoethylpyridine, 4-alkylaminoethylpyridine, 4-piperidinoethylpyridine, 4-(4-bipecorinoethyl)-pyridine, 4-morpholinoethylpyridine, pyridines including cyclic compounds; 2-phenylpyridine, 4-phenylpyridine, 2-benzylpyridine, 4-benzylpyridine, 4-phenylpropylpyridine, 4,4″-dipyridyl, 4,4″-dimethyl-2,2″-dipyridyl, 1,
3-di(4-pyridyl)propane, 1,2-di(4
-pyridyl) monoethane, 1,2-di(4-pyridyl)
monoethylene, 1,2,3-tri(4-pyridyl)propane, 2,4,6-tri(4-pyridyl)-S-triazine, 2,4-di(4-pyridyl)-6-methyl-S- Triazine, 2,5-di(4-pyridyl)-S-
Tetrazine, alkenylpyridine and high molecular weight pyridines; 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methyl-pyridine, 2-vinyl-5-ethylpyridine, 4-butenylpyridine, 4-vinylpyridine homopolymer, 2-vinylpyridine vinylpyridine homopolymer, 2-vinylpyridine copolymer, 4-vinylpyridine-acrylonitrile copolymer, 4-vinylpyridine-styrene-copolymer, 4-vinylpyridine-divinylbenzene-copolymer, 2-vinylpyridine-dipinylbenzene copolymer, 4-vinylpyridine homopolymer N-
Oxides; Pyrroles: Pyrrolines; Pyrimidines;
Pyrazines; pyrazoles; pyrazolines; pyridazines; imidazoles; 1,10-phenanthroline and its derivatives; 1,10-phenanthroline, 4-chloro-1,10-phenanthroline, 5-(thiabenzel) )
-1,10-phenanthroline; quinoline and its derivatives, quinoline, 2-(dimethylamino)-6-methoxyquinoline, 8-hydroxyquinoline, 2-carboxyquinoline (■), pentavalent nitrogen group compound ammonium acetate, Of the above compound groups such as ammonium propionate and triphenylphosphineiminium chloride, organic compounds containing nitrogen or phosphorus are preferred.

Particularly effective are phosphines containing trivalent phosphorus, amines containing trivalent nitrogen, or heterocyclic compounds typified by pyridine. Moreover, these compounds can also be used in combination. In the present invention, the amounts of nickel and ruthenium used as main catalysts are 10-6 to 5 mol per 1' based on the total volume of the reaction solution, respectively.
Preferably 10-4 mol, more preferably 10-3 to
A range of 2 mol, most preferably 5 x 10-3 to 1.0 mol is generally selected.

The molar ratio of nickel and ruthenium is 30:1 to 1:
The range is 1. The amount of the halide used as a cocatalyst is 10-6 to 20 mol per 1', preferably 10-6 to 20 mol per 1' based on the total volume of the reaction solution based on the halogen atom.
It is used in a range of 4 to 10 moles. Further, the amount of promoter used is related to the amount of main catalyst metal in the reaction system, but the amount is usually 10-6 to 10 per 1e based on the total volume of the reaction solution.
mol, preferably in the range of 10-4 to 5 mol.
For carrying out the method of the invention, the reaction temperature is, for example, 20
A suitable temperature range is 500°C to 500°C, preferably 80 to 350°C, and more preferably 100°C to 300°C. The total reaction pressure may be sufficient to maintain the reaction solution in a liquid phase and to maintain carbon monoxide and hydrogen at appropriate partial pressures. The preferred partial pressure for carbon monoxide and hydrogen is 0.5 to 7 atm, the optimum partial pressure is 1 to 6 (4) atm, and the optimal partial pressure is 3 to 5 atm, but wider than 0. Partial pressures in the range of .05 to 100 msec are also acceptable. The stoichiometric amount of the raw material gas in the above reaction formula for producing ethylidene diacetate is the molar ratio of carbon monoxide to hydrogen of 2: depending on whether methyl acetate, dimethyl ether, or a mixture is used as the raw material. It varies between 1 and 4:1. However, in practice the molar ratio of carbon monoxide to hydrogen ranges much wider, from 1:100 to 100:1, preferably 1:50.
~50:1, more preferably 1:10 to 10:1 can be used. A molar ratio of carbon monoxide to hydrogen in the range 0.5:1 to 5:1 is particularly preferred since the best results are obtained when the gas mixture is close to the stoichiometric ratio of carbon monoxide to hydrogen. . Furthermore, the carbon monoxide and hydrogen used in the seventh invention may be individually pressurized into the reaction zone, or may be introduced in the form of a mixture of carbon monoxide and hydrogen, so-called ゜゜synthesis gas. Furthermore, these raw material gases do not necessarily have to be of high purity to begin with, and may contain carbon dioxide, methane, nitrogen, and rare gases. However, raw material gas of extremely low purity is undesirable because it increases the pressure of the reaction system. In the method of the present invention, the raw materials methyl acetate and dimethyl ether and the product ethylidene diacetate themselves also serve as reaction solvents, so a solvent does not necessarily need to be used. It is also possible to use dilute catalysts.

Commonly used solvents include organic acids such as acetic acid, propionic acid, butyric acid, octanoic acid, phthalic acid, and benzoic acid, methyl acetate, ethyl acetate, ethylene glycol diacetate, propylene glycol diacetate, dimethyl adipate, and methyl benzoate. , organic acid esters such as ethyl benzoate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, phenyl acetate, tolyl acetate, dodecane,
Hydrocarbons such as hexadecane, benzene, naphthalene, and biphenyl; inorganic acid esters such as triphenyl phosphate, tricresyl phosphate, dibutylphenyl phosphate, tetramethyl orthosilicate, and tetrabutyl silicate; aromatic ethers such as diphenyl ether; Examples include ketones such as acetone, methyl ethyl ketone, dibutyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone. A preferred embodiment is to use acetic acid or acetic anhydride, which are analogs of the reaction product ethylidene diacetate, as the solvent. The reaction of the present invention is intended to produce ethylidene diacetate, but since ethylidene diacetate has the property of promoting decomposition by water, it is particularly important to avoid using solvents and raw material esters or ethers that are likely to contain water. It is supplied to the reaction system in an anhydrous state, and the reaction system itself is brought into a substantially anhydrous state. It is essential to do so.

The presence of water in the reaction raw materials is a common phenomenon, but the presence of a small amount of water, such as that contained in commercially available synthesis gas and methyl acetate or dimethyl ether, is acceptable and does not cause any problems.

but. However, usually one or more reaction materials contain 10
Mixing more than mol% of water should be avoided,
Introducing a large excess of water into the reaction system tends to lead to product decomposition. In this respect, it is desirable that the water content be 5 mol% or less, more preferably 3 mol% or less. Since water is not a reaction product, maintaining near-anhydrous conditions in the liquid phase reaction medium is easily achieved by maintaining the necessary reactants introduced into the reaction zone as well as the reaction liquid in a suitably dry state. achieved. Although the process of the invention is preferably carried out in a liquid phase reaction medium enclosed in a reaction zone, the process itself can be carried out batchwise, semi-continuously or continuously.

In continuous operation, the reactants and catalyst are preferably fed to a suitable reaction zone, the reaction mixture is continuously distilled to separate a predetermined amount of volatile organic components, and the distillation bottoms containing the catalyst are recycled. It can also be used in circulation. Another preferred method is to convert the vinyl acetate to acetic acid by feeding the reaction mixture containing ethylidene diacetate continuously flowing from the reactants to another suitable reactant and distilling these reaction mixtures. Methyl acetate, acetic acid and vinyl acetate can be separated and recovered, and the distillation bottoms containing catalyst can be recycled for further reaction. The method of the present invention described in detail above produces ethylidene diacetate through a hydrocarbonylation reaction using an inexpensive catalyst, and has extremely high industrial significance.

Hereinafter, this will be explained in more detail with reference to Examples.

Example 1 In a pressure reactor, 20 g of methyl acetate, 15 g of acetic acid,
Methyl iodide 13g 1 Nickel powder 0.5g 1 Ruthenium chloride 0.25g 1 and triphenylphosphine 5.6
Add 1g of carbon monoxide and hydrogen mixed gas (volume ratio 2:
1) was press-fitted to 180k9/d. Heat to 175:
C and continued stirring at this temperature for 4 hours. After cooling, the liquid contained 2.32 g of ethylidene diacetate, 1 acetic anhydride, and 5.
It contained 26g. Example 2 Dodecacarbonyltriruthenium (RU3(CO)1) was used instead of ruthenium chloride.
2) The same operation as in Example 1 was performed except that 0.254 g was used.

After the reaction, 2.27 g of ethylidene diacetate was found in the solution.
It contained 5.26 g of acetic anhydride. Example 3 20 g of methyl acetate 1 15 g of acetic acid 1 1 methyl iodide in a reactor
3g1 nickel powder 0.5g1 basic ruthenium acetate 0
．． 280g1 and triphenylphosphine 7.65g
was added, and the reaction was carried out in the same manner as in Example 1.

After the reaction, the solution contained 2.58 g of ethylidene diacetate,
It contained 13.9 g of acetic anhydride. Example 4 In a reactor, 20 g of methyl acetate, 15 g of acetic acid, 13 g of methyl iodide, 0.25 g of nickel powder, and 0.5 g of ruthenium chloride were added.
was added, and the reaction was carried out in the same manner as in Example 1.

The solution after the reaction contained 0.39 g of ethylidene diacetate and 1.23 g of acetic anhydride. Example 5 20 g of methyl acetate, 15 g of acetic acid, 13 g of methyl iodide in a reactor.
0.5 g of nickel powder, 0.5 g of ruthenium chloride, and 6.0 g of triphenylphosphine were added, and a reaction was carried out in the same manner as in Example 1.

After the reaction, 3.76 g of ethylidene diacetate was found in the solution.
It contained 1.68 g of acetic anhydride.

Example 6 20 g of methyl acetate, 15 g of acetic acid, 13 g of methyl iodide, 0.5 g of nickel powder, 0.256 g of dodecacarbonyl triruthenium (RU3(CO)12) and 4.17 g of 2,6-lutidine were placed in a reactor, and the same reaction mixture as that of Example 1 was added. The reaction was carried out in the same manner for 8 hours.

The solution after the reaction contained 0.56 g of ethylidene diacetate. Example 7 20 g of methyl acetate 1 15 g of acetic acid 1 1 methyl iodide in a reactor
0g. , Ni(P(C6H5)3)2(CO)20.5
g and 0.25 g of ruthenium chloride were added, and the reaction was carried out in the same manner as in Example 1.

The solution after the reaction contained 1.27 g of ethylidene diacetate. Example 8 In a reactor, 20 g of methyl acetate, 15 g of acetophenone, 13 g of methyl iodide, 0.5 g of nickel powder, 0.25 g of ruthenium chloride, and trinium
After 3.86 g of -butylamine was introduced and a mixed gas of carbon monoxide and hydrogen (volume ratio 1.1) was introduced under pressure to 180 k9/Clt, a reaction was carried out at a ratio of 175 C for 4 hours.

The solution after the reaction contained 0.63 g of ethylidene diacetate. Example 9 Into the reactor, 35g of methyl acetate1 13g of methyl iodide1 0.5g of nickel acetylacetone1 0.25g of ruthenium chloride
g1 and 4.20 g of tri-n-butylphosphine were added, and the reaction was carried out in the same manner as in Example 1.

After the reaction, the solution contained 2.21 g of ethylidene diacetate/
) were included. Example 10 In a reactor, 20 g of methyl acetate, 15 g of acetic acid, 10 g of calcium iodide, 0.5 g of nickel iodide, 0.5 g of ruthenium chloride.
Add 25g1 and 1.47g of triphenylphine,
Mixed gas of carbon monoxide and hydrogen (volume ratio 3:1) at 180%
The mixture was pressurized to k9/Clt and the reaction was carried out at 185 C for 8 hours.

The solution after the reaction contained 1.33 g of ethylidene diacetate. Example 11 In a reactor, 20 g of acetic acid, 13 g of methyl iodide, 0.5 g of nickel powder, and 0 g of ruthenium chloride were added.
．． 25 g and 5.61 g of triphenylphosphine were added, and 20 g of dimethyl ether was introduced.

Mixed gas of carbon monoxide and hydrogen (volume ratio 4:1)
It was press-fitted to k9/Cll. Heat to 1751C,
Stirring was continued at this temperature for 8 hours. The cooled liquid contained 1.22 g of ethylidene diacetate. Comparative Example 1 20g of methyl acetate 16g of acetic acid in a reactor. ．． Methyl iodide 13g 1 nickel powder 0.58g 1 lithium iodide 0.6
7g1 and tri-n-butylphosphine 4.5g, and mixed gas of carbon monoxide and hydrogen (volume ratio 1:1) were added.
It was press-fitted to 00 kg/CIL.

The mixture was heated to 2000C, and the reaction was carried out at this temperature for a predetermined period of time. After cooling, ethylidene diacetate was detected along with 4.96 g of acetic anhydride. Comparative Example 2 20g of methyl acetate, 15g of acetic acid, 13g of methyl iodide in a reactor
0.25 g of ruthenium monochloride and 5.61 g of triphenylphosphine were added, and a reaction was carried out in the same manner as in Example 1.

After the reaction, there was 9.5 m9 of ethylonodene diacetate in the solution.
, 3.7 mg of acetic anhydride were contained. Comparative Example 3 The same reaction as in Example 1 was carried out except that 0.5 g of chromium powder was used instead of 0.5 g of nickel powder.

・(In other words, in this example, 0.5g of chromium powder was added to Comparative Example 2.
This corresponds to an example in which . ) The solution after the reaction contained 9.2 m of ethylidene diacetate and 4.1 m9 of acetic anhydride.

Comparative Example 4 The same reaction as in Example 1 was carried out except that 0.5 g of chromium carbonyl powder was used instead of 0.5 g of nickel powder.

Claims (1)

[Claims] 1 Substantially anhydrous state in the presence of a catalyst containing at least one halide, which is an iodide or a bromide, and nickel and ruthenium, in which ruthenium is present in a molar ratio of 1 to 1/30 to nickel. A method for producing ethylidene diacetate, which comprises reacting methyl acetate or dimethyl ether with carbon monoxide and hydrogen.