KR820002182B1 - Process for preparation of diester from unsaturated dicarboxylic acids - Google Patents

Abstract

Dicarboxylic acid diesters were prepd. by the reaction of aliph. or cycloaliph. alkenses or alkynes with CO and alcs. in the presence of Pd and a N oxide, HNO3, or nitrate or nitrite ester. Thus CH2:CH2 treated with CO and MeOH in-Me adipate in the presence of Pd-C(2% Pd) and HNO3(and O) at 85≰gave MeO2CCH2CH2CO2Me.

Description

Process for preparing diesters of dicarboxylic acids

The present invention relates to a method for producing a diester of dicarboxylic acid having two carbons more than aliphatic or cycloaliphatic unsaturated hydrogen carbonate having 2 to 20 carbon atoms as a starting material, wherein the method refers to the above unsaturated hydrocarbon , Carbon monoxide, and alcohols are reacted in the presence of a catalyst system in which at least one compound selected from nitric acid, nitrogen dioxide, and nitrite esters is mixed with a white metal metal in the presence of molecular oxygen in the reaction system as necessary. Can also give

According to the process of the present invention, the use of ethylene as unsaturated hydrocarbons produces diesters of succinic acid, and the use of unsaturated hydrocarbons other than ethylene as starting materials is substituted succinic acid, substituted or unsubstituted maleic acid and cycloalkane di Diesters of carboxylic acids are produced. For example, the use of propylene as unsaturated hydrocarbon produces small amounts of diesters of glutaric acid in some cases, but usually produces diesters of methylsuccinic acid, and cyclohexane is also used to produce 1,2- and 1,3-cyclohexane. Mixtures of diesters of dicarboxylic acids are produced and the use of acetylene produces diesters of maleic acid.

Processes for preparing diesters of dicarboxylic acids having two carbons more than these hydrocarbons using unsaturated hydrocarbons as starting materials have already been known, in which case unsaturated hydrocarbons, carbon monoxide and alcohols are reacted with molecular oxygen as necessary. Many catalysts are also known.

For example, US Pat. No. 3,397,226 describes the invention of a redox agent containing a polyvalent metal salt such as copper and iron and a method of using a platinum group metal salt as a catalyst. However, this reaction should be maintained in anhydrous state by using a large amount of isocyanate, diimide, ortho alkylester as a preferred dehydrating agent, and the reason for maintaining the anhydrous state as described above is due to the increase of by-products such as water and carbon dioxide generated during the reaction. It is because the yield of the diester of the dicarboxylic acid which is a target compound falls by this. In practice, it is difficult to maintain the reaction system in anhydrous state, and there is a drawback that regeneration is impossible because the dehydrating agent once used is converted into a completely different substance. In addition, using a conventional method is expensive to prepare a diester of dicarboxylic acid, and also from the standpoint of the catalyst used, although the catalytic efficiency of the platinum group metal and polyvalent metal chloride is excellent, but the corrosion of the chloride is high and special equipment equipment And maintenance was expensive.

For these reasons, the use of a catalyst system using a mixture of amino acids, nickel compounds, and transition metals (periodic table II, Group VIII, Group VIII) as a third substance instead of the dehydrating agent has been proposed as an advanced form of the prior art. These catalysts also had increased water resistance, but did not improve the selectivity of the target compound satisfactorily. Moreover, the conventional catalyst system has a problem in that a third material is used and the catalyst system is complicated by the multi-component system, and thus, processes such as separation, recovery and regeneration of expensive catalysts are complicated.

In order to alleviate the above drawbacks, studies have continued to produce diesters of dicarboxylic acids having industrially excellent yields using unsaturated hydrocarbons as starting materials by reacting hydrocarbons, carbon monoxide alcohols, etc. while injecting molecular oxygen as necessary. Has been. As a result of these efforts, the inventors have invented a method for producing diesters of dicarboxylic acids with industrially high selectivity.

That is, the present invention is industrially required in the presence of a catalyst in which at least one compound selected from nitric acid, nitrogen dioxide, and nitrite ester is mixed with an aliphatic or alicyclic unsaturated hydrocarbon having 2 to 20 carbon atoms, carbon monoxide, alcohol and the like. Therefore, the present invention relates to a method for producing a diester of dicarboxylic acid having two more carbon atoms than the above-mentioned unsaturated hydrocarbon by reacting while supplying molecular oxygen.

The method of the present invention not only improves the selectivity and yield of the diester of the dicarboxylic acid, which is the target compound, but also the catalyst of the present invention is more stable against moisture than the conventional method, so that the reaction system can be maintained in anhydrous state. It is simple and economical because it does not require expensive dehydrating agent and complicated process. In addition, the catalyst device of the present invention also has the advantage of not having a special material container because it is not corrosive. In addition, the catalyst system of the present invention is simple because it is composed of at least one compound selected from a platinum group metal, nitric acid, nitric oxide, nitrite ester, and the like. As a result, it is easy to separate, recover and regenerate the catalyst from the reaction system, and also to separate and obtain the target compound. For the above reason, the method of the present invention has an advantage that it is extremely superior to other methods.

A specific example of the present invention is as follows. The unsaturated hydrocarbons used in the present invention are aliphatic and alicyclic hydrocarbons having 2 to 20 carbon atoms, and examples thereof include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, undecene, dodecene, tridecane and tetradecene. , Pentadecene, nucleodecene, heptadecene, octadecene, octadecene, nonadecene, isogenes and their isomers, cyclopentene, cyclohexene, cycloheptene, cyclooctene, indene, styrene, alkylbenzene, allene, methylene, butadiene, pentadiene, Nucleadiene, cyclopentadiene and the like and acetylene or alkyl derivatives thereof.

Alcohols used in the present invention include mono- or di-alcohols such as alkyl, cycloalkyl, aralkyl and aryl, and in particular, aliphatic alcohols such as methanol, ethanol, propanol, butanol, petanol, hexanol, Heptanol, octanol, nonanol, decanol, ethylene glycol, diethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, butanediol and the like are preferred. In addition, cyclic alcohols (e.g., cyclopentanol, cyclohexanol, cyclo Heptanol, phenol, naphthol, cresol, cumenol, xyleneol, benzyl alcohol, β-phenylethanal alcohol and the like) are also used.

Palladium is the most ideal platinum group metal used as the catalyst of the present invention, but platinum, rhodium, ruthenium, iridium, osmium, and the like may also be used. The above platinum group metal is used in the form of a catalyst supported on a carrier such as activated carbon, graphite, silica gel, alumina silica alumina, diatomaceous earth, magnesia, pumice, molecular sieve, etc. to easily recover the platinum group metal or the target compound and prevent loss thereof.

Such platinum group metal catalyst is used in an amount of 10 ^-5 to 10% by weight, preferably 10 ^-4 to 1.0% by weight of the reaction medium. Silver nitric acid is used in the range of 10 ^-4 to 10 moles, preferably 10 ^-3 to 0.5 moles per liter of the reaction medium. The amount of nitric oxide is used in an amount of 0.1 to 100 mol%, preferably 1 to 50 mol%, based on the unsaturated hydrocarbon used, and the nitrite ester is 10 ^-4 to 10 mol, preferably 10 ^-3 to 1 mol per liter of the reaction medium. Use As nitrogen oxides, NO is the best, but N ₂ O ₃ , N ₂ O ₄ N ₂ O ₅ , and the like can also be used.

As the nitrite ester used in the present invention, all of the nitrite esters made of the above-mentioned alcohols used as starting materials can be used. Among them, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite, pentyl nitrite and hexyl nitrite , Heptyl nitrite is preferred. In addition, nitrite esters in the gaseous state at room temperature, such as methyl nitrite and ethyl nitrite, can be effectively used in solution in the corresponding alcohol.

The reaction of the present invention can proceed in the presence or absence of a solvent that does not inhibit the reaction. Such solvents include ethers (e.g., methyl ethyl ether, dieth ether, dipropyl ether, dimethyl ether, dichloroethyl ether, ethylphenyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether, etc.) , Esters (e.g., methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, etc., adipic acid, succinic acid, maleic acid, fumaric acid, propionic acid, acetoacetic acid, oxalic acid, benzoic acid, etc. Esters), aromatic hydrocarbons (eg benzene, nitrobenzene, chlorobenzene, toluene, etc.) and alicyclic hydrocarbons (eg cyclohexane).

The reaction of the present invention proceeds in an extremely gentle state. The reaction temperature is from room temperature to 250 ° C., in particular from 50 to 150 ° C., and the reaction pressure is from about atmospheric pressure to about 300 atmospheres, in particular less than 200 atmospheres. The molar ratio of carbon monoxide to unsaturated hydrocarbons is 0.002 to 50, in particular 0.01 to 50.

In the present invention, in order to further improve the yield and selectivity of the target compound, molecular oxygen may be added. Molecular oxygen at this time means oxygen gas, air and other oxygen-containing gas (oxygen diluted with an inert gas such as nitrogen). In general, as the amount of oxygen in the molecular is increased, the yield of the target compound is increased. Therefore, molecular oxygen must be added to prevent the mixed gas in the reactor from reaching the explosion limit.

In the following, examples are listed to explain the present invention in more detail.

Example 1

To a 300 ml stainless steel autoclave with a magnetic rotary stirrer is poured 50 ml of methanol, 50 ml of dimethyladipate as solvent, 2 g of palladium (2% by weight palladium) on activated carbon and 10 mmol of nitric acid at 61% by weight. After sealing, 36 atmospheres of ethylene and 24 atmospheres of carbon monoxide were added thereto, and heated at 85 ° C., and then continuously pressurized twice with 3 atmospheres of oxygen, and the reaction was performed at 85 ° C. for 5 hours. After the reaction is completed, the reaction mixture is analyzed by gas chromatography.

Example 2

Except for pressurizing 18 atm of carbon methoxide, the experiment was carried out in the same manner as in Example 1 and the reaction was carried out for 3 hours.

Example 3

50 ml of methanol, 50 ml of dimethyl adipate, 2 g of palladium on activated carbon (2% by weight palladium) are poured into a 300 ml stainless steel autoclave with a magnetic rotary stirrer. After sealing, 45 atmospheres of ethylene and 15 atmospheres of carbon monoxide were added to the vessel. After heating at 85 ° C., the reaction was carried out continuously for 3 hours with the addition of 61 mmol of nitric acid 30 mmol in 5 portions.

Example 4

The experiment was conducted in the same manner as in Example 1 except that 20 mmol of nitrogen dioxide was used instead of nitric acid and the reaction was performed for 3 hours.

Example 5

The experiment was carried out in the same manner as in Example 1, except that palladium (10% by weight) on activated carbon was used as a catalyst, using a gas mixture composed of 45 atm of ethylene and 15 atm of carbon monoxide, and the reaction was performed at 98 ° C. for 1 hour. do.

Comparative Example 1

The experiment was conducted in the same manner as in Example 1 except that no nitric acid was used.

Comparative Example 2

A 300 ml stainless steel autoclave with a magnetic stirrer is charged with 100 ml of methanol, 0.94 mmol of palladium-black, 12,5 mmol of copper nitrate and 0.24 mmol of nickel nitrate. After sealing, the mixture was pressurized to 36 atm and 24 atm of carbon monoxide, heated at 85 ° C., and subsequently pressurized twice at 3 atmospheres of oxygen, respectively, and the reaction was performed at 85 ° C. for 3 hours.

The results of quantitative analysis of the product by gas chromatography after completion of the reaction in Examples 1 to 5 and Comparative Examples 1 and 2 are shown in Table 1 below.

TABLE 1

* In Comparative Example 2, 4.0 mmol of methyl β-methoxypropionate and 10.6 mmol of dimethyl acetal of acetaldehyde, which are hardly produced in Examples 1 to 5, were produced as by-products.

Example 6

80 ml of methanol, 20 ml of styrene, 2 g of palladium (10 wt% palladium) on graphite and 20 mmol of nitric acid (20 wt%) are poured into a 300 ml stainless steel autoclave equipped with a magnetic rotary stirrer. After sealing, the mixture was pressurized to 60 atm of carbon monoxide, heated at 85 ° C., and then pressurized twice at 3 atmospheres of oxygen, respectively, and the reaction was carried out at 85 ° C. for 3 hours. After completion of the reaction, quantitative analysis of the reaction mixture by gas chromatography yields 7.3 mmol of dimethyl phenylsuccinate.

Example 7

An autoclave made of 300 ml of stainless steel with a magnetic rotary stirrer is charged with 50 ml of methanol, 50 ml of dimethyl adipate as a solvent, and 0.1 g (2% by weight of palladium) on activated carbon. After sealing, the reaction was carried out at 30 atm and at a reaction temperature of 110 ° C. for 1 hour, and a mixed gas consisting of 90.4% by volume of ethylene, 7.8% by volume of carbon monoxide and 1.7% by volume of oxygen was placed in a vessel at a rate of 1.35 Nℓ / min. Was passed through and fed with methanol at 90 millimoles per hour. After completion of the reaction, the reaction mixture was quantitatively analyzed by gas chromatography to obtain 45.6 mmol of dimethyl succinate.

Example 8

An autoclave made of 300 ml stainless steel with a magnetic rotary stirrer is charged with 50 ml of ethanol, 50 ml of dimethyl adipate as a solvent and 1 g of palladium (2% by weight Pd) on activated carbon. After sealing, the reaction was conducted at 30 ° C. at 90 ° C. for 1 hour, during which time the mixture was passed through the vessel at a rate of 1.2 N l / min of a mixed gas consisting of 80.4 vol% ethylene, 13.1 vol% carbon monoxide and 6.5 vol% oxygen. And nitric acid dissolved in ethanol at a rate of 100 mmol / hour. After completion of the reaction, the reaction mixture was quantitatively analyzed by gas chromatography to yield 23.8 mmol of diethyl succinate.

Example 9

Pour 75 ml of ethylene glycol, 75 ml of methyl isobutyl ketone, 1 g of palladium (10% by weight Pd) on activated carbon and 62 mmol of nitrate 70% by weight into an autoclave of 500 ml stainless steel with a magnetic rotary stirrer. . After sealing, it is pressurized to 35 atmospheres of ethylene and 20 atmospheres of carbon monoxide. After heating at 115 ° C., it was continuously pressurized twice with 3 atmospheres of oxygen and the reaction was carried out at 115 ° C. for 45 minutes. After completion of the reaction, the reaction mixture was treated with excess n-butanol to trans esterify to n-butyl ester and quantitatively analyzed by gas chromatography to yield 7.2 mmol of the diester of succinic acid.

Example 10

Proceeding in the same manner as in Example 8, except that 150 ml of ethylene glycol monomethyl ether was used instead of ethylene glycol and no isobutyl ketone was used as a solvent, as a result, 25.8 mmol of a diester of succinic acid was produced.

Example 11

30 ml of 1,4-butanediol in an autoclave made of 300 ml stainless steel with a magnetic rotary stirrer, 75 ml of dioxane as a solvent, 1 g of palladium (10 wt. Pd) on activated carbon and 41 mmol of nitrate 98 wt% Pour it. After sealing, the reaction was carried out for 1 hour at 105 ° C. under 30 atmospheres, and a mixed gas consisting of 90.5% by volume of ethylene, 4.6% by volume of carbon monoxide, and 4.9% by volume of oxygen was placed in the vessel at a rate of 0.59 Nℓ / min. Pass it through. After completion of the reaction, the reaction product was transesterified by treatment with methanol and the product obtained was quantitatively analyzed by gas chromatography to yield 13.8 mmol of the diester of succinic acid.

Example 12

Into an autoclave made of 300 ml stainless steel with a magnetic rotary stirrer is poured 90 ml of methanol, 10 ml of cyclohexene, palladium on activated carbon (5% by weight Pd) and 98% by weight of 25 mmol of nitric acid. After sealing, the mixture was pressurized to 40 atm of carbon monoxide and heated at 115 ° C., and subsequently pressurized four times at 3 atmospheres of oxygen, and the reaction was carried out at 115 ° C. for 4 hours. After the reaction was completed, the reaction mixture was quantitatively analyzed by gas chromatography to obtain 4,4-mmol of dimethyl cis-1,2-cyclohexane dicarboxylate and 3.0 mmol of dimethyl cis-1,3-cyclohexane dicarboxylate. Is generated.

Example 13

To an autoclave made of 300 ml stainless steel with a magnetic rotary stirrer, 75 ml of methanol, 2 g of palladium (10 wt% Pd) on activated carbon and 53 mmol of nitric acid (61 wt%) were poured. After sealing, press 34g of propylene and continuously pressurize carbon monoxide so that the total pressure is 40 atm. After heating at 85 ° C., it was continuously pressurized 7 times with 4 atmospheres of oxygen and the reaction was carried out at 85 ° C. for 5 hours. After the reaction was completed, the reaction mixture was quantitatively analyzed by gas chromatography to produce 20.6 mmol of dimethyl methyl succinate.

Example 14

In a 300 ml autoclave equipped with a magnetic rotary stirrer, 50 ml of methanol, 50 ml of dimethyl adipate as a solvent, 1 g of palladium on activated carbon (2% by weight Pd) and 21 millimoles of n- Fill with butyl nitrite. After sealing, the mixture was compressed by injecting 40 atm of mixed gas containing 91.6% by volume of ethylene and 8.3% by volume of carbon monoxide. Subsequently, the temperature is raised to 105 ° C., and when the pressure reaches 50 atm, 4 atm of oxygen is injected and compressed, and the reaction is further performed for 40 minutes at ionicity.

Example 15

The experiment was conducted in the same manner as in Example 14 except that 25 mmol of ethyl nitrate dissolved in ethanol was used instead of n-butyl nitrite.

Example 16

The experiment was conducted in the same manner as in Example 14 except that 100 ml of n-butanol was used instead of methanol and dimethyl adipate was not used as the solvent.

Example 17

A 300 ml autoclave, equipped with a magnetic rotary stirrer, is filled with 100 ml of ethanol and 0.1 g of palladium (2% by weight Pd) on activated carbon. After sealing, 20atm of mixed gas consisting of 86.3% by volume of ethylene, 10.3% by volume of carbon monoxide and 3.2% by volume of oxygen is injected and compressed. Subsequently, the temperature was raised to 145 ° C., the pressure was 30 atm, and the reaction was performed for 1 hour while continuously supplying the ethyl nitrite solution dissolved in ethanol. Arithmetic mixed gas of 30 atm is passed through the autoclave at a rate of 38 Nl per hour. The amount of ethyl nitrite supplied during the reaction is 60 mmol.

Example 18

In a 500 ml autoclave equipped with a magnetic rotary stirrer in a stainless steel, 100 ml of methanol, 50 ml of dimethyl adipate as solvent, 1 g of palladium on activated carbon (2% by weight Pd) and 37.8 mmol Fill with n-butyl nitrite. After sealing, 23.3 g of propylene is injected and compressed, followed by injection of carbon monoxide so that the total pressure is 22 atm. Then, the temperature was increased to 91 ° C., when the pressure reached 35 atm, 2 atm of oxygen was injected and compressed, and then the reaction was performed at this temperature for 5 hours. When no decompression was observed during the reaction, 2 atm of oxygen was injected twice into the reaction system and compressed.

Example 19

A 300 ml autoclave, equipped with a magnetic rotary stirrer, was charged with 100 ml of n-butanol and 1.5 g of palladium (2% by weight Pd) on activated carbon. After sealing, the mixture is compressed by injecting 45 atm of mixed gas consisting of 81.2% by volume of ethylene, 14.1% by volume of carbon monoxide and 4.6% by volume of oxygen.

Subsequently, after raising the temperature to 118 ° C. and reaching the pressure of 60 atm, the reaction was carried out while supplying 7.9 g of n-butyl nitrite solution dissolved in n-butanol and continuously passing 60 atm of the above-described mixed gas through the vessel. Run for hours. The amount of n-butyl nitrite supplied during the reaction is 30.3 mmol.

Comparative Example 3

A 300 ml autoclave, equipped with a magnetic rotary stirring period, of stainless steel was charged with 1.13 mmol of palladium chloride, 7.44 mmol of chloride, and 50 ml of dimethyladipate. After sealing, 24 atm of carbon monoxide and 36 atm of ethylene were injected and compressed. Subsequently, when the temperature is raised to 100 ° C. and the pressure reaches 61 atm, 3 atm of oxygen is injected and compressed, and then the reaction is carried out for 2.5 hours at an ionic degree. When no decompression was observed during the reaction, 3 atm of oxygen was injected three times and compressed.

The following Table 2 shows the results of the quantitative analysis of Examples 14 to 19 and Comparative Example 3 by gas chromatography after the reaction was terminated.

TABLE 2

In Comparative Example 3, 13.1 mmol of formate (methylformate), which is rarely produced in Examples 14 to 19, and a large amount of dimethylacetal and carbon dioxide of acetaldehyde are produced as by-products.

Example 20

100 ml of ethanol and 2 g of catalyst (2% by weight, palladium on activated charcoal) are placed in a 300 ml autoclave equipped with a magnetic rotary stirring period and made of stainless steel. After sealing, a mixed gas consisting of 86.3% by volume of ethylene, 10.3% by volume of carbon monoxide and 3.2% by volume of oxygen was injected into the autoclave (20atm, room temperature) and compressed, and the autoclave was heated to 108 ° C. A mixed gas was injected through a reaction vessel at a rate of 0.6 Nl split and the reaction was carried out at this temperature for 1 hour while injecting a solution of nitric acid (42 mmol) and ethyl nitrite (43 mmol) dissolved in 25 ml of ethanol. Quantification of the product by gas chromatography after the reaction showed that 8.9 mmol of diethyl succinate was produced.

Example 21

In a 300 ml autoclave equipped with a magnetic rotary stirrer, 50 ml of methanol 50 ml of dimethyl adipate, 21 mmol of butyl nitrite and 1 g of catalyst (2% by weight, palladium on activated carbon) Fill it with After being sealed, a mixed gas consisting of 91.6 vol% ethylene and 8.4 vol% carbon monoxide is injected into the reaction vessel to bring the pressure to 60 atm. The autoclave was left at 150 ° C. for 1 hour and the reaction mixture analyzed by gas chromatography to show 3.8 mmol of dimethyl succinate and 1.7 mmol of dimethyl oxalate.

Example 22

A 300 ml autoclave equipped with a magnetic rotary stirring period and made of stainless steel, 50 ml of methanol, 50 ml of dimethyl adipate, 0.1 g of catalyst (8% by weight of Pd-2% by weight of Pt on activated carbon). ) And 36 mmol 98% nitric acid. After closing, the vessel was filled with a mixed gas consisting of 89.5% by volume ethylene, 7.5% by volume carbon monoxide and 2.7% by volume oxygen. (20 atm, room temperature) The autoclave is heated to 107 ° C., and then the mixture gas described above is passed through the reaction vessel for 1 hour at this temperature. Analysis of the reaction mixture by gas chromatography showed that 21.5 mmol of dimethyl succinate was produced.

Example 23

In a 500 ml stainless steel autoclave equipped with a magnetic rotary stirring period, 1.5 g of Pd, 38 mmol butyl nitrite, 75 ml n-butylol and 75 ml dibutyl in 2 wt% carbon Fill in the adipate. After sealing the autoclave, 43atm of ethylene and 19atm of carbon monoxide were injected, pressed and heated. The reaction is carried out at 105 DEG C for 1 hour without adding oxygen. After completion of the reaction, the reaction mixture was analyzed to show that 18.0 mmol of dibutyl succinate and 4.3 mmol of dibutyl oxalate were produced.

Claims (1)

Platinum group metal catalysts selected from palladium (Pd), platinum (Pt), rhodium (Rh), osmium (Os), iridium (Ir) and ruthenium (Ru) with aliphatic or alicyclic unsaturated hydrocarbons having 2 to 20 carbon atoms 1 selected from nitric acid, nitric oxide and nitrite esters in the catalyst system for producing diesters of dicarboxylic acids having 2 carbon atoms more than the above-mentioned aliphatic or cycloaliphatic unsaturated hydrocarbons having 2 to 20 carbon atoms which are reacted in the presence of A process for producing a diester of dicarboxylic acid characterized by at least two compounds.