JPS5934165B2 - Production method of carboxylic acid ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing a carboxylic acid ester, particularly for producing a carboxylic acid ester from carbon monoxide, alcohol, and a specific halogenated organic compound. This invention relates to a method for producing a carboxylic acid ester using an acetone solution of cobalt tetracarbonyl anion obtained by reaction in a solvent as a catalyst.

Conventionally, various methods for producing carboxylic acid esters have been proposed, but for example, as described in Japanese Patent Publication No. 4010967, carbon monoxide, rogogenated organic compounds, and alcohols are used as a catalyst, and a cobalt tetracarbonyl salt is used as a catalyst.
There is a method of using an inorganic base or an organic nitrogen base and carrying out the reaction under basic reaction conditions.

In other words, this method involves reacting carbon dioxide, alcohol, and a halogenated organic compound using the reaction product of dicobalt octacarbonyl and sodium amalgam as a catalyst, but the yield is low and the method for producing the catalyst is not practical. Moreover, there is a problem with the activity.

The present invention aims to solve these drawbacks, and uses an acetone solution of cobalt tetracarbonyl anion obtained by reacting cobalt salt, carbon monoxide, and hydrogen in an acetone solvent as a catalyst, and uses carbon monoxide as a catalyst. , proposes a method for producing carboxylic acid esters in high yield by reacting alcohols and halogenated organic compounds in the presence of a basic substance.

That is, the present invention provides the following general formula (1), () or ()
When reacting a halogenated carboxylic acid ester, a halogenated alkyl compound, or a halogenated aryl compound shown respectively with carbon monoxide and alcohol in the presence of a basic substance, the cobalt salt, carbon monoxide, and hydrogen are reacted in an acetone solvent. This is a method for producing a carboxylic acid ester, which is characterized by using an acetone solution of cobalt tetracarbonyl anion obtained by the reaction as a catalyst.

(In the formula, A group that, as the case may be, has a double bond, ether group, nitrile group, or carbonyl group in its carbon chain, or has a halogen group bonded to the terminal carbon, & is hydrogen or the number of carbon atoms 1 to 3 alkyl groups, Ar is a benzene nucleus, naphthalene nucleus, or other mononuclear or higher aryl group, R5 is hydrogen,
It is at least one selected from halogen, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxycarbonyl alkyl group having an alkylene group having 1 to 3 carbon atoms, an alkoxy group, and a halogenated alkyl group.

) Specific examples include the following compounds, but the present invention is not limited thereto.

Examples of the halogenated carboxylic acid ester include methyl chloroacetate, ethyl chloroacetate, isopropyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, methyl-3chloropropionate, and the like.

Examples of halogenated alkyl compounds include methyl chloride, methylene chloride, ethyl chloride, ethyl bromide, ethylene dichloride, amyl chloride,
-chloropropane, amyl iodide, octyl iodide, 2-iodooctane, oleyl chloride,
Stearyl bromide, dichlorobutane, chlorinated kerosene, allyl chloride, allyl bromide, crotyl chloride, crotyl fluoride, meta-allyl chloride, pentenyl chloride, pentenyl iodide,
Undecenyl chloride, dichlorobenzene, 3-chloropropionitrile, chloroacetonitrile, 3-bromobutyronitrile, β-chloroethyl ethyl ether,
β・β7~dichlorodiethyl ether, chloromethyl isobutyl ether, β-bromoethyl vinyl ether,
α-chloropropylpropyl ether, cyclohexyl chloride, cyclopentyl bromide, tetrahydrofurfuryl chloride, chloroacetone, diethyl 4-chlorobutyraldehyde acetal and the like.

Halogenated aryl compounds include benzyl chloride, ortho-, meta- and para-methoxybenzyl chloride, α-monochloroxylene and α・α7-dichloroxylene (ortho, meta or para), α-chloromethoxylunaphthalene, β -chloromethylnaphthalene,
α-chloromesitylene, benzyl fluoride, benzyl bromide, benzyl iodide, para-tolyl chloride, α-iodoxylene (ortho, meta or para) and the like.

The catalyst used in the present invention is a cobalt tetracarbonyl anion, which has high activity and, compared to known catalysts, the reaction proceeds satisfactorily even with a small amount of catalyst.

Further, the counter ions of the cobalt tetracarbonyl anion used in the present invention are mostly hydrogen cations, and although it is presumed that a small amount of cobalt cations are present, there are no side reactions at all. The catalyst used in the present invention is in acetone,
Conditions similar to those for producing dicobalt octacarbonyl with cobalt salt, carbon monoxide and hydrogen (e.g. 160
The homogeneous solution of acetone obtained by reaction at 200 k9/leak) can be used as is.

The alcohol used in the present invention is not particularly limited as long as it is an aliphatic alcohol, and examples thereof include methanol, ethanol, isopropanol, and n-butanol.

Furthermore, in addition to alcohol, inert solvents such as aliphatic saturated hydrocarbons, aromatic hydrocarbons, pyridine, picoline, and alcohol esters of organic acids may be coexisting.

The molar ratio of the catalyst and the organic logenide is 1:1 to 1:
4'00, preferably l:4 to l:100.

The basic substance has the role of capturing hydrogen halide, which is produced as a by-product in the reaction.Therefore, it may be anything that reacts with hydrogen halide, such as ammonia, hydrazine, and aliphatic substances. , aromatic secondary, secondary, and tertiary amines, aliphatic and aromatic alcohols, metal alcoholades, alkali metals, alkaline earth metals carbonates, bicarbonates, oxides, hydroxides, and other known compounds. is used.

The reaction temperature is 30-100°C, preferably 40-70°C.
It is. Also, the reaction pressure is 2 to 50 kg/c? Preferably it is 5 to 30k9/Cd. The carbon monoxide used does not need to be of particularly high purity, and even if hydrogen and inert gas are used together, the yield will not decrease. In the method of the present invention, when the base used is a compound that easily reacts with the raw material organic halide, such as alcoholade, ammonia, or caustic soda, the base is added in small portions to carry out the reaction.

When using other bases, there are no restrictions on the preparation method; an acetone solution of cobalt tetracarbonyl may be added in portions to the organic halide, basic substance, and alcohol solution, or a cobalt tetracarbonyl anion may be added in portions to the organic halide, basic substance, and alcohol solution. The organic halide may be added in portions to the acetone solution, basic substance, and alcohol, and even if all the raw materials are charged at once and the reaction is carried out, there is little change in yield. As explained above, the present invention uses an acetone solution of cobalt tetracarbonyl anion as a catalyst in producing a carboxylic acid ester from carbon monoxide, alcohol, and a halogenated organic compound. is easy to use, has high catalytic activity,
Moreover, since no by-products are produced, it is an excellent method for producing carboxylic acid esters with good yield.

Reference Example: Method for producing an acetone solution of cobalt tetracarbonyl anion Internal volume: 1. 0.0 in a pressure-resistant reactor equipped with a stirrer.
5f! of acetone and 0.2 mol of cobalt hydroxide are charged.

The reactor was heated with a mixed gas of carbon monoxide and hydrogen (molar ratio 10:
After replacing the air in the reactor in step 3), the mixed gas is pressurized and heating and stirring are started. Internal temperature 160℃, pressure 2
Increase the pressure to 00kg/Cd.

After that, the pressure starts to drop, and when the pressure drops by 20 kg/Cd, the pressure increases again to 200 k9/CrA. This method was repeated, and after confirming that there was no drop in pressure after about 4 hours, the reaction was stopped. After the reaction, the reaction solution was cooled and returned to normal pressure, and transferred to another glass pressure-resistant container. No precipitate was observed at all, and a homogeneous solution was obtained. This solution, infrared absorption spectrum, and iodine decomposition method, which is a method for analyzing dicobalt octacarbonyl and cobalt tetracarbonyl anions [Anal. Chem. Volume 24 A6. l, 1952
January 2015, pp. 174-176].
All cobalt carbonyl in the reaction solution is CO(CO)4
- It was confirmed that

Example 1 1f with stirrer! 108y of monochloroacetic methyl ester, 0.5 mol of soda carbonate, and 300cc of methanol were placed in a pressure-resistant reactor, and after replacing the air with carbon monoxide,
Heating and stirring were started, and when the temperature was 50°C and the pressure was increased to 5k9/Cd, 160 cc of an acetone solution of cobalt tetracarbonyl anion produced in the same manner as in the reference example (
CO (containing CO4-107) was added by pump within 4 hours.

Simultaneously with the start of the fractional addition, the reaction was carried out while continuously purging at a rate of 30 cc/Mm, and the mixture was aged for 1 hour after the fractional addition. After the reaction, the reaction solution was taken out, made acidic with sulfuric acid, and analyzed by gas chromatography.
237 (yield: 93.6%) was produced, and the amount of unreacted monochloroacetic acid methyl ester was 3.39. Example 2 Same as Example 1, but the catalyst solution was charged first, and 350 cc of a methanol solution of NH3 (3 M/l) was added in portions over 5 hours to carry out the reaction.

After the reaction, it was acidified with sulfuric acid in the same manner as in Example 1, and analyzed by gas chromatography. As a result, 1187 dimethyl malonate (yield 89.8%) was produced, and unreacted monochloroacetic acid methyl ester was 2. It was .9y.
Example 3 Same as Example 1, except that 136y1 of monochloroacetic acid isofropyl ester and 300cc of isopropanol were used, and 160cc of an acetone solution of cobalt tetracarbonyl anion (containing CO(CO)4-10y) was added as a catalyst solution for 5 hours. It dripped in between.

After the reaction, analysis was performed in the same manner as in Example 1, and it was found that diisopropyl malonate 165y (yield 88.1%) was produced, and that unreacted was monochloroacetic acid isopropyl ester 11.5'F7. Example 4 Same as Example 1, but the catalyst liquid was charged first, and monochloroacetic acid methyl ester was added portionwise over 3 hours.

After the reaction, analysis in the same manner as in Example 1 revealed that 1247 dimethyl malonates (yield 94.4%) were produced, and the amount of unreacted methyl monochloroacetate was 3.47.

Examples 5-23 Table 1 shows the results of experiments conducted in the same manner as in Examples 1-4.

All catalysts were CO-(CO)4 acetone solutions, and Examples 5, 6, 11, 12, 14, 18, 19, 20
, 21124, an organic halide was added during the reaction.

Claims (1)

[Scope of Claims] 1 A halogenated carboxylic acid ester, a halogenated alkyl compound, or a halogenated aryl compound represented by the following general formula (I), (II), or (III), respectively, is monoxidized in the presence of a basic substance. A method for producing a carboxylic acid ester, characterized in that when reacting with carbon and alcohol, an acetone solution of cobalt tetracarbonyl anion obtained by reacting a cobalt salt, carbon monoxide, and hydrogen in an acetone solvent is used as a catalyst. . ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, X is halogen, R_1 is hydrogen or an alkyl group having 13 carbon atoms, R_2 is a carbon number 1 to 8
The alkyl group R_3 is a straight chain, branched or alicyclic alkyl group having 1 to 8 carbon atoms, and in some cases, a double bond, ether group, nitrile group or carbonyl group is present in the carbon chain. or a halogen group bonded to the terminal carbon, R_4 is hydrogen or an alkyl group having 1 to 3 carbon atoms, Ar is a benzene nucleus, naphthalene nucleus, or other mononuclear or higher aryl group, R_5 is hydrogen, Halogen, carbon number 1~
It is at least one selected from a straight chain or branched alkyl group having 8 carbon atoms, an alkoxycarbonyl alkyl group having an alkylene group having 1 to 3 carbon atoms, an alkoxy group, and a halogenated alkyl group. ).