JPS5829938B2 - Method for producing allyl carbonate compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing allyl carbonate compounds with good selectivity.

That is, in the present invention, when producing an allyl carbonate compound by reacting a reaction product of an alcohol, a group II metal carbonate, and carbon dioxide with an allylide in the presence of a catalyst, the group III metal carbonate is reacted with the hydroxyl group of the alcohol. This is a method for producing an allyl carbonate compound, in which the reaction temperature is maintained at 70°C to 110°C.

Various methods have been proposed for producing allyl carbonate compounds.

For example, a method of reacting alcohol and phosgene,
Alternatively, it can be obtained by reacting allylnolide with sodium carbonate in the presence of a catalyst.

However, these known methods cannot be said to be industrially satisfactory techniques due to drawbacks such as the extremely strong toxicity of the raw material (phosgene) and the inability to obtain asymmetric carbonates with good selectivity.

As a result of intensive research into a method to eliminate the above-mentioned drawbacks, the present inventors have found that an organic carbonate compound can be produced with excellent reaction rate and selectivity by reacting a group (III) metal carbonate, an alcohol, and an organic halide in the presence of a catalyst. I have already found out what can be achieved and proposed it.

Furthermore, as a result of repeated research to obtain industrially useful compounds based on these findings, it was discovered that the desired product obtained was greatly affected by both the reaction rate and selectivity depending on the raw material composition ratio and reaction temperature, and the present invention was made. We have come to propose this.

That is, in the present invention, when producing an allyl carbonate compound by reacting a reaction product of an alcohol, a group Ⅰ metal carbonate, and carbon dioxide gas with an allyl halide in the presence of a catalyst, the group Ⅰ metal carbonate is reacted in an amount equivalent to the hydroxyl group of the alcohol. This is a method for producing an allyl carbonate compound using the above method and carrying out the reaction while maintaining the reaction temperature at 70°C to 110°C.

The present invention will be explained in detail below.

The alcohol used in the present invention may be m-alcohol or polyhydric alcohol without particular limitation as long as it is a compound having an alcoholic OH group.

Specific examples include methyl alcohol, ethyl alcohol, n-propyl alcohol, 1so-7' propyl alcohol, n-phthyl alcohol, iso-7'' alcohol, tert-butyl alcohol, allyl alcohol, meta-allyl alcohol, and benzyl. Monohydric alcohols such as alcohols or polyhydric alcohols represented by the general formula R1(R-0)n-H (where R is an aliphatic hydrocarbon residue and n is an integer of 1 or more) such as ethylene glycol , diethylene glycol, triethylene glycol, phlopylene gelicol.

1,3-propanediol, ■,4-butanediol,
Polyethylene glycol and the like are preferably used.

Further, unsaturated alcohols such as 2-butenoto-4-diol or alcohols such as glycerin can also be suitably used.

As a general tendency, when the alcohol has a high molecular weight, a long time is required for the reaction between the alcohol and the group I metal carbonate (hereinafter simply referred to as carbonate), and the selectivity of the product also tends to decrease. Generally, it is preferable to use an alcohol having a molecular weight of 2000 or less.

Furthermore, since 12-diols such as ethylene glycol and glopylene glycol may produce alkylene carbonate as a by-product during the reaction, it is preferable to determine the alcohol in advance according to the purpose.

The carbonate used in the present invention may be any carbonate as long as it can contribute to the production of the allyl carbonate compound described below, but from an industrial standpoint sodium carbonate and potassium carbonate are preferred.

Generally, when using chloride as the allyl halide, sodium carbonate tends to show good reactivity, and when using bromide, potassium carbonate tends to show good reactivity.

The carbon dioxide gas used in the present invention does not necessarily have to be pure carbon dioxide gas; for example, a carbon dioxide-containing gas obtained by burning heavy oil or a carbon dioxide-containing gas diluted with an inert gas such as air can also be used.

Furthermore, the allyl halide used in the present invention is not particularly limited as long as it has a halogen bonded to the allyl position.

Typical examples of those most preferably used include allyl chloride, allyl bromide, allyl iodide,
Metaallyl chloride, metaallyl bromide, metaallyl iodide, etc.

The catalyst used in the present invention is not particularly limited and may be any catalyst known for the production of allyl carbonate involving carbon dioxide gas and/or carbonate.

For example, US Patent No. 2,648,697, British Patent No. 666
Although disclosed in No. 560 and the like, compounds containing nitrogen and/or phosphorus, particularly quaternary salts, or nitrogen-containing compounds and phosphorus-containing compounds that produce quaternary salts in the reaction system are particularly suitable.

Typical of these are shown in the general formula (however, in these general formulas, R1, R2, R3, R4 represent a saturated or unsaturated alkyl group, a cyclic alkyl group, an aromatic group, an aralkyl group, etc., and R6 is Represents the same group or hydrogen as R1 to R4 above.

In addition, X represents an anion and is generally a halogen ion or a hydroxide ion) Among these catalysts, examples of catalysts that are generally preferably used include triethylamine, tri-n-propylamine, diethylbutylamine, N-N
-dimethylbenzylamine, N-N-ditylaniline, tetraethylammonium chloride, allyltriethylammonium chloride dimethylformamide, triethylphosphine, etc. Triethylamine and its quaternary salts in particular give good results.

The production of the allyl carbonate compound in the present invention requires reacting the reaction product of alcohol, carbonate, and carbon dioxide with allyl halide in the presence of a catalyst, but it is not necessarily necessary to adopt a separate reaction system. .

Even if the raw material components of the present invention, such as alcohol, carbonate, carbon dioxide, and allylide, are supplied in the presence of a catalyst, the alcohol, carbonate, and carbon dioxide first react to produce these reaction products, and then The reaction product and allyl halide react to produce an allyl carbonate compound.

In the present invention, it is advantageous to have all the components of the raw materials in advance, since allyl halide acts suitably as a solvent during the reaction of alcohol, carbonate, and carbon dioxide gas, so that generally favorable results can be obtained. .

This is a great advantage when carrying out the present invention as a continuous reaction.

In addition, the reaction in the present invention can be carried out in batch mode, semi-batch mode,
A continuous method can be selected as necessary, and the following embodiments of the raw material supply reaction may be adopted as necessary.

(1) React alcohol, carbonate and carbon dioxide★★
After separating the reaction product, the reaction product is reacted with allyl halide in the presence of a catalyst.

(2) Alcohol, carbonate, and carbon dioxide gas are reacted, and a catalyst and allyl halide are added to the reaction system without separating the reaction products.

(3) Alcohol, carbonate, carbon dioxide gas, and allyl halide are supplied in the presence of a catalyst and reactions are carried out in the same reaction system.

These reaction methods are not particularly limited as long as the optimum method is determined in advance as necessary, and the ratio of the main raw material components is within the range described below, and the allyl carbonate compound is produced within the temperature range described below.

Although it is not necessarily clear what kind of reaction mechanism each raw material in the present invention reacts through.

It is estimated as follows.

(However, R, R' are alkyl groups, M is group II metal, and
(indicates a halogen atom) The most important feature of the present invention is the control of the amounts of the main raw materials, alcohol and carbonate, and the reaction temperature during production of the allyl carbonate compound.

In the present invention, it is necessary to use the carbonate in an amount equal to or more than the hydroxyl group of the alcohol.

If the amount of carbonate used is less than equimolar to the hydroxyl group of the alcohol, it is not preferable because the formation of ether is promoted and the selectivity for allyl carbonate, which is the object of the present invention, is reduced.

Conversely, if the amount of carbonate used is larger than the above, there will be no adverse effect on the allyl carbonate production reaction itself, but if it is extremely large, unreacted carbonate mixed into the reaction product will increase. Therefore, it is not a good idea when separating reaction products.

Furthermore, the production of by-products also tends to increase with the amount of carbonate.

Therefore, it is generally preferable that the amount of carbonate used be limited to about 2 times the mole of the hydroxyl group of the alcohol, preferably in the range of 1.05 to 1.5 times the mole.

Due to the nature of the reaction of the present invention, the larger the surface area of the carbonate used in the present invention, the better.

Preferably, ground carbonates are used for this purpose.

However, it is preferable to use light ash obtained by roasting sodium bicarbonate obtained by the Solvay process, that is, soda carbonate, which is generally referred to as light ash, because it exhibits an excellent reaction even without pulverization.

When the light ash is used, it is easy to separate the solids from door to door after the reaction, wash the solids, etc., and has great industrial significance.

The reason why ether production is suppressed when carbonate is used in an amount equal to or more than the hydroxyl group of alcohol is not clear.

However, when the carbonate is used in equal moles or more, the reaction proceeds smoothly because the alcohol turns into a carbonate ester salt without producing water that adversely affects the reaction.

In addition, the temperature during the production of allyl carbonate is 70 to 110% in combination with the reaction temperature and the amount of raw materials used.
It is necessary to keep it at ℃.

By satisfying these two requirements, the present invention not only prevents the production of ether and various by-product reactions, but also
It is also possible to obtain asymmetric carbonates with high Ti selectivity.

If the reaction temperature during production of allyl carbonate is lower than the above, it is not preferable because not only will it take a long time to obtain the target product, but also the yield will decrease even if the amount of catalyst is increased.

On the other hand, if the reaction temperature is higher than the above, there is an advantage that the amount of catalyst can be reduced, but the reaction rate of carbonate and bicarbonate coexisting in the reaction system also increases, by-products increase, and the selectivity of the target product decreases. Therefore, it is not desirable.

The amounts of carbon dioxide gas, catalyst, and allyl halide used in the present invention are not particularly limited and may be determined in advance and used as necessary.

It is generally assumed that carbon dioxide gas reacts with alcohol to produce carbonic acid monoester, which is neutralized by carbonate and fixed as an ester salt.

Therefore, if carbon dioxide gas is applied under pressure, the reaction will be accelerated.

Of course, the higher the partial pressure of carbon dioxide is, the more desirable it is, and generally it is 3 to 50 kg/crA, preferably 10 kg/c, calculated at room temperature.
rrt or higher is preferably used.

Further, the amount of the catalyst varies depending on the type of catalyst, differences in reaction conditions, etc., and cannot be absolutely limited, but in general, a range of 1 to 20 mol % based on the hydroxyl group of the alcohol is most widely used.

Of course, in general, when the amount of catalyst is small, a long reaction time is required, so from an industrial perspective, it is preferable to use 5 to 10 mol % based on the hydroxyl group of the alcohol, since the reaction can be completed within several hours.

Furthermore, the amount of allyl halide to be used is not particularly limited, and it is generally preferred to use it in an amount equal to or more than the hydroxyl group of the alcohol.

Allyl halide itself serves the purpose as a solvent as mentioned above, so the amount to be used can be determined as necessary.Industrially, it is used in an amount equal to or more than the hydroxyl group of the alcohol, preferably more than 1.2 times the mole or more, and preferably 10 times the mole relative to the hydroxyl group of the alcohol. The following criteria may be used.

Although the production reaction time of allyl carbonate in the present invention cannot be definitively stated because it varies depending on the reaction method, type of catalyst, reaction conditions, etc., it is generally preferable to complete the reaction within several hours to several tens of hours.

In the reaction of alcohol, carbonate, and carbon dioxide gas in the present invention, under the above conditions, it is common to use more carbonate, which is a solid phase, than alcohol, which is a liquid phase, and these reaction products are also solid. Therefore, it is preferable to choose a method that makes the reaction system uniform.

For this reason, methods such as bubbling the reaction system with carbon dioxide gas or carbon dioxide-containing gas, providing a stirrer, or using a solvent are generally employed.

It is most preferable to use allyl halide, which is one of the raw material components, as the solvent, but in addition to allyl halide, it is also preferable to use non-aqueous polar solvents such as propylene carbonate and dimethylformamide.

Alternatively, the reaction product can be produced by gradually adding carbonate powder into alcohol under pressure of carbon dioxide gas or into a solvent in which alcohol is dissolved, or by gradually adding alcohol to a solvent or slurry liquid in which carbonate is dissolved. It is also possible to apply operations such as preventing the growth of large clumps.

In the present invention, the catalyst may be added at any time during the reaction of alcohol, carbonate, and carbon dioxide as long as it is not particularly limited before allyl...ride participates in the reaction; They can be added simultaneously or in advance.

In addition, the reaction of alcohol, carbonate, and carbon dioxide gas does not necessarily require high temperatures and can be carried out satisfactorily even at room temperature, so the reaction can also be carried out during the process of raising the temperature of the reaction system.

As mentioned above, the present invention not only allows asymmetric carbonates to be obtained in high yield and high selectivity, but also allows for easy separation and purification of the obtained carbonates, making the industrial effects of the present invention very large. be.

In order to explain the present invention more specifically, the present invention will be explained in detail below using Examples and Comparative Examples.

However, the present invention is not limited to these examples.

Note that the alcohol used in the examples is anhydrous MgS.
O4 was added, refluxed, and then distilled, and allyl halide was dried with anhydrous CAC12, and then distilled.

As the carbonate, use an anhydrous special grade reagent pulverized with a porcelain ball mill, or light soda ash (manufactured by Tokuyama Soda) at 100%
It was used after vacuum drying at ℃.

The conversion rates shown in the examples are values based on carbonate, and the amount of halogen and alkali in the solid material remaining after the reaction was measured by titration using the method described below. The amount of group metal carbonate was determined using the following formula.

The solids in the reaction product were sweated off, thoroughly washed with ethanol, and dried under vacuum at 60° C. for about 16 hours.

After making about 0.6P of the solid into a 10cc aqueous solution,
The amount of rogene was determined by silver nitrate titration using an aqueous potassium chromate solution as an indicator, and the amount of alkali was determined by neutralization titration using methyl orange as an indicator.

In addition, the selectivity is determined by gas chromatography (
(hereinafter abbreviated as G and C) was obtained from analysis.

In charts G and C, when the raw materials alcohol, allyl halide, and solvent were used, the ratio of the peak area of the target substance to the total peak area excluding the peaks caused by the alcohol, allyl halide, and solvent is shown.

C and C were measured using GC-6A manufactured by Shimadzu Corporation.

The column was 3m long and packed with 5ilicone SE-
30 (trade name: manufactured by Gascro Industries Co., Ltd.) was used.

Hydrogen was used as the carrier gas.

Comparative Example 1 Ethanol 0.5M and pulverized sodium carbonate 0.5M were placed in an autoclave with a stirrer and a capacity of 500CC and a material of 5VS32.
25M, allyl chloride 1.5M, and triethylamine 3.21C0.032M as a catalyst were added, and the system was sufficiently purged with carbon dioxide gas.

Carbon dioxide pressure was 10 kg/cniG.

Heated to 120℃ using an electric heater and heated at 1000r, p for 4 hours.
The reaction was carried out while stirring at , m.

The conversion rate was 66.2%, the selectivity was 84.1% for allyl ethyl carbonate, 13.0% for allyl ethyl ether, and 1.2% for diallyl carbonate.

Comparative Example 2 The same reaction as Comparative Example 1 was carried out except that the amount of ground sodium carbonate was increased to 0.5 M.

The conversion rate was 67.3%, and the selectivity was 76.8% for allyl ethyl carbonate, 3.9% for allyl ethyl ether, and 18.1% for diallyl carbonate.

Comparative Example 3 The same reaction as Comparative Example 1 was carried out except that the reaction temperature was 100°C.

The conversion rate was 23.2%, and the selectivity was 91.0% for allyl ethyl carbonate, 5.7% for allyl ethyl ether, and 0.3% for diallyl carbonate.

Example 1 The same reaction as in Comparative Example 2 was carried out except that the reaction temperature was 100°C.

The conversion rate was 33.6%, the selectivity was 95.5% (allyl ethyl carbonate), 2.1% allyl ethyl ether, and 0.4% diallyl carbonate.

Example 2 The same reaction as in Example 1 was carried out except that 0.5 M light ash was used instead of ground sodium carbonate.

The conversion rate was 52.0%, and the selectivity was 93.9% for allyl ethyl carbonate, 1.0% for allyl ethyl ether, and 3.3% for diallyl carbonate.

Example 3 The same reaction as in Example 2 was carried out except that the reaction temperature was 90°C.

The conversion rate was 40.8%, and the selectivity was 97-4% for allyl ethyl carbonate, 1.0% for allyl ethyl ether, and 0.3% for diallyl carbonate.

Example 4 The same reaction as in Example 2 was carried out except that 0.25 M of ethylene glycol was used as alcohol (.CO2) and 30 ky/crAG reaction time was changed to 6 hours.

Conversion rate is 57.2%, selectivity is diethylene glycol bis(allyl ether-1-) 80.4%, diethylene glycol mono(allyl carbonate) 51%, diethylene glycol mono(allyl carbonate) mono(allyl ether) 2.6%, The diallyl carbonate content was 9.3%.

Comparative Example 4 The same procedure as in Example 4 was carried out except that the amount of light ash charged in Example 4 was changed to 0.35M.

As a result, the conversion rate was 41.8% and the selection rate was 1 (G, C,
%) are diethylene glycol bis(allyl carbonate) 14.8%, diethylene glycol mono(allyl carbonate) 15.9%, diethylene glycol mono(allyl carbonate) mono(allyl ether 44%, diallyl carbonate) 18.4%, diethylene glycol mono(allyl carbonate) 18.4%, (ethylene glycol) carbonate was 11.9% and diethylene glycol mono(allyl ether) was 7.1%.

Comparative Example 5 The same procedure as Comparative Example 4 was carried out except that the amount of light ash charged in Comparative Example 4 was changed to 0.45M.

As a result, the conversion rate was 52.4%, and the selection rate (G, C,
%) are diethylene glycol bis(allyl carbonate) 59.7%, diethylene glycol mono(allyl carbonate) 8.4%, diethylene glycol mono2.
3%, diallyl carbonate 13.9%, di(diethylene glycol) carbonate 1.5% and diethylene glycol mono(allyl ether) 0.4%.

Example 5 The exact same reaction as in Example 4 was repeated, all the reactants were decomposed with water, and the organic layer was extracted with chloroform.

Low-boiling substances were distilled off from the extracted organic layer using a rotary evaporator.

Concentrated liquid 65 containing diethylene glycol bis(allyl carbonate) with gas chromatography purity of 82.8%? I got it.

Example 6 The same reaction as in Example 5 was carried out except that the light ash was increased to 0.75M and the reaction time was 5 hours.

631 reaction concentrates containing diethylene glycol bis(allyl carbonate) with gas chromatography purity of 92.7% were obtained.

The selectivity was 87.2% for diethylene glycol bis(allyl carbonate), 2.5% for diethylene glycol mono(allyl carbonate) mono(allyl ether), and 10.2% for diallyl carbonate.

Comparative Example 6 A reaction was carried out under the same conditions as in Example 1 except that the reaction temperature was 60°C.

The extract was extracted with chloroform and low-boiling substances were distilled off using a rotary evaporator.

Although the residue was exposed to G, C, and carbon, the target carbonate could hardly be detected.

Comparative Example 7 The same reaction as in Example 4 was carried out except that the reaction temperature was 120°C and the reaction was carried out in the dark for 4 hours.

Conversion rate is 62.6%, selectivity is diethylene glycol bis(allyl carbonate)) 66.9%, diethylene glycol mono(allyl carbonate)) 4.6%, diethylene glycol mono(allyl carbonate) mono(allyl ether) 4° 6%, diallyl carbonate 18.8%
Met.

Comparative Example 8 The same reaction as in Example 4 was carried out except that the light ash was reduced to 0.25M.

Conversion rate is 40.5%, selectivity is diethylene glycol bis(allyl carbonate) 3.5%, diethylene glycol mono(allyl carbonate) 17.1%, diethylene glycol mono(allyl carbonate) mono(allyl ether) 2.6%, diallyl Carbonate 13.4%
, di(diethylene glycol) carbonate 19.4%
, diethylene glycol mono(allyl ether) 11.
It was 7%.

Comparative Example 9 The same reaction as Comparative Example 8 was carried out except that the reaction temperature was 120°C.

Conversion rate is 62.7%, selectivity is diethylene glycol bis(allyl carbonate) 9.3%, diethylene glycol mono(allyl carbonate)) 26.8%, diethylene glycol mono(allyl carbonate) mono(allyl ether) 7.2% , diallyl carbonate 18.4%
, di(diethylene glycol) carbonate 3.4%,
Diethylene glycol mono(allyl ether) 10.
It was 0%.

Example 7 1,3-propanediol 0,25 as alcohol
The same reaction as in Example 4 was carried out except that M was used and the reaction time was changed to 4 hours.

Conversion rate is 40.7%, selectivity is 1,3-propanediol bis(allyl carbonate) 67.9%, 4-hydroxypropyl allyl carbonate 4.4%, 4-allyloxypropyl carbonate 4.7%, diallyl The carbonate content was 8.7%.

Example 8 The same reaction as in Example 5 was carried out except that 0.25M of 1.4-butanediol was used as the alcohol.

The conversion rate was 35.0%, the selectivity was 1,4-butanediol bis(allyl carbonate) 6.9.3%, 4-hydroxybutyl allyl carbonate 12.5%, 4-allyloxybutyl allyl carbonate. -) 4.6% and diallyl carbonate 2.3%.

Example 9 The same reaction as in Example 5 was carried out except that 0.25M alcohol triethylene glycol was used.

Conversion rate is 43.7% 1 Selectivity is triethylene glycol (allyl carbonate) 54.4%, triethylene glycol mono (allyl carbonate) 1.9%, triethylene glycol mono (allyl carbonate) mono (allyl ether) 5 .1%.

15.3% of diallyl carbonate and 4.1% of triethylene glycol mono(allyl ether) were torn.

Example 10 The same reaction as in Example 4 was carried out except that 1.5 M of meta-allyl halide was used as the allyl halide and the reaction time was 5 hours.

Conversion rate is 4667%, selectivity is diethylene glycol bis(methallyl carbonate) 72.5%, diethylene glycol mono(methallyl carbonate) 12.4
%, diethylene glycol mono(methallyl carbonate) mono(methallyl ether) 4.1%, and dimethallyl carbonate 3.8%.

Example 11 Using the autoclave of Comparative Example 1, diethylene glycol 0.15M, ground potassium carbonate 0.3M, allyl bromide 0.9M were mixed with CO210kg/Cr/iG, triethylamine 3.2P (0,032M), and 100°C.
The mixture was allowed to react for 4 hours.

Conversion rate is 65.9%, selectivity is diethylene glycol bis(allyl carbonate) 47.5%, diethylene glycol mono(allyl carbonate) 5.0%, diethylene glycol mono(allyl carbonate) mono(allyl ether) 16.7%, diallyl carbonate 13,5
%Met.

Example 12 Tetraethylammonium chloride as catalyst 5.3
The same reaction as in Example 4 was carried out except that 1 was used and the reaction time was changed to 4 and a half hours.

Conversion rate is 39.0%, selectivity is diethylene glycol bis(allyl carbonate) 72.8%, diethylene glycol mono(allyl carbonate) 2.6%, diethylene glycol mono(allyl carbonate) mono(allyl ether) 3.3%, diallyl Carbonate 11.8%
Met.

Example 13 The same reaction as in Example 9 was carried out except that 5.91% of tri-n-butylamine was used as the catalyst.

Conversion rate is 54.4%, selectivity is diethylene glycol bis(allyl carbonate)) 68.1%, diethylene glycol mono(allyl carbonate)) 2.7%, diethylene glycol mono(allyl carbonate) mono(allyl ether) 1. 9% and diallyl carbonate 8.7%.

Example 14 The same reaction as in Example 4 was carried out except that light ash (16M, allyl chloride 0.6M), dimethylformamide 100CC was used as the solvent, and the reaction time was 4 hours.

Conversion rate is 35.2%, selectivity is diethylene glycol bis(allyl carbonate) 44.1%, diethylene glycol mono(allyl carbonate) 8.4%, diethylene glycol mono(allyl carbonate) mono(allyl ether) 2.5%, diallyl The carbonate content was 7.3%.

Claims (1)

[Claims] 1. When producing an allyl carbonate compound by reacting a reaction product of an alcohol, a group II metal carbonate, and carbon dioxide gas with an allyl halide in the presence of a catalyst, the group III metal carbonate is converted into a hydroxyl group of the alcohol. 1. A method for producing an allyl carbonate compound, characterized in that the reaction is carried out in an amount equal to or more than the same mole as that of the allyl carbonate compound, and the reaction temperature is maintained at 70 to 110°C. 2. The method according to claim 1, wherein the alcohol is diethylene glycol. 3.Claim 1 in which the group metal carbonate is a light group metal carbonate.
Method described. 4. The method according to claim 1, wherein the allyl halide is allyl chloride or meta-allyl chloride. 5 Group I metal carbonate to the hydroxyl group of alcohol 1-
The method according to claim 1, wherein the method is used in a molar amount of 0.5 to 1.5 times.