阅读说明：本技术 双酰氧基化外向亚甲基化合物的制造方法 (Method for producing bisacyloylated exomethylene compound ) 是由 村田裕辅 源直也 金子充雅 清水亮佑 于 2018-07-23 设计创作，主要内容包括：一种下述通式(III)所示的双酰氧基化外向亚甲基化合物的制造方法,其中,在催化剂和根据需要的溶剂的存在下,使下述通式(I)所示的单酰氧基化外向亚甲基化合物、下述通式(II)所示的羧酸和氧在液相中发生反应。<Image he="513" wi="700" file="DDA0002367871070000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(A process for producing a bisacylated exomethylene compound represented by the following general formula (III), wherein a monoacylated exomethylene compound represented by the following general formula (I), a carboxylic acid represented by the following general formula (II) and oxygen are reacted in a liquid phase in the presence of a catalyst and optionally a solvent.)

1. A process for producing a bisacylated exomethylene compound represented by the following general formula (III), which comprises reacting a monoacylated exomethylene compound represented by the following general formula (I), a carboxylic acid represented by the following general formula (II) and oxygen in a liquid phase in the presence of a catalyst and optionally a solvent,

in the formula, R¹And R²Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms or an optionally substituted aryl group having 6 to 14 carbon atoms; r³Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms and optionally having a substituent, a cycloalkyl group having 3 to 8 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 6 carbon atoms and optionally having a substituent, an aryl group having 6 to 14 carbon atoms and optionally having a substituent, an alkoxy group having 1 to 8 carbon atoms and optionally having a substituent, or an aryloxy group having 6 to 14 carbon atoms and optionally having a substituent; r⁴Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms and optionally having a substituent, a cycloalkyl group having 3 to 8 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 6 carbon atoms and optionally having a substituent, or an aryl group having 6 to 14 carbon atoms and optionally having a substituent; n represents an integer of 1 to 8.

2. The manufacturing method according to claim 1, comprising: and supplying the carboxylic acid to the reaction solution during the reaction.

3. The production process according to claim 2, wherein all of the carboxylic acid used is continuously fed to the reactor.

4. The production method according to any one of claims 1 to 3, which comprises carrying out the reaction in the presence of a solvent.

5. The production method according to any one of claims 1 to 4, wherein the total amount of the solvent and the carboxylic acid used is more than 1 mol and 50 mol or less based on 1 mol of the monoacylated exomethylene compound.

6. The production method according to any one of claims 1 to 5, wherein the solvent is at least 1 selected from the group consisting of hydrocarbons, heterocyclic compounds, ethers, ketones, esters, amides, nitriles, and alcohols.

7. The production process according to claim 6, wherein the solvent is an ester represented by the following general formula (IV),

in the formula, R⁴As shown in the above definition, R⁵Represents an optionally substituted alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 14 carbon atoms.

8. The production method according to claim 7, wherein R⁴Is methyl, R⁵Is an alkyl group having 1 to 4 carbon atoms.

9. The production method according to claim 7 or 8, wherein the amount of the carboxylic acid used is 0.1 mol or more and 0.6 mol or less relative to 1 mol of the monoacylated exomethylene compound.

10. The production method according to any one of claims 1 to 9, wherein R is³And R⁴Is methyl and n is 1 or 2.

11. The production method according to any one of claims 1 to 10, wherein R is¹And R²Is a hydrogen atom.

Technical Field

The present invention relates to a method for producing a bisacyloylated exomethylene compound.

Background

The bisacylated exomethylene compound has a 2, 2-substituted carbon-carbon unsaturated bond applicable to a radical addition reaction, a hydrosilylation reaction, a hydroformylation reaction, or the like, and 2 acyl groups applicable to a saponification reaction, a transesterification reaction, or the like in the same molecule, and thus can be used as a raw material for producing various chemicals due to its reactivity (for example, patent documents 1 and 2).

Several methods for producing diacyloxylated exomethylene compounds have been known.

For example, non-patent document 1 describes a method for producing 1, 3-diacetoxy-2-methylene propane by reacting 1, 3-dichloro-2-methylene propane with sodium acetate.

Non-patent document 2 describes a method for producing 1, 4-diacetoxy-2-methylbutanes by reacting methyl itaconate with lithium aluminum hydride and then with acetic anhydride.

However, in these production methods, inorganic by-products which become waste are generally generated in an equimolar amount or more with respect to the product. Therefore, a production method which does not generate inorganic by-products is desired from the viewpoint of reducing environmental load.

On the other hand, as a production method without generating inorganic by-products, a method of producing a bisacylated exomethylene compound by reacting a terminal olefin compound, a carboxylic acid and oxygen in a gas phase in the presence of a palladium catalyst is known.

For example, patent document 3 describes a method for producing 1, 3-diacetoxy-2-methylenepropane by reacting methallyl acetate, acetic acid, water, and oxygen in a gas phase in the presence of a specific catalyst. Patent document 3 describes: nitrogen was introduced at two atmospheres relative to 900mL of supported catalyst: oxygen: methallyl acetate: acetic acid: water (40.0: 2.0: 1.2: 5.0: 3.0) was reacted in a gas phase at a reaction temperature of 140 ℃ to obtain 1, 3-diacetoxy-2-methylenepropane (1, 3-diacetoxy-2-methylenepropane production efficiency of 55g/{ L (catalyst) · hr }) at a conversion of 25% methallyl acetate and a selectivity of 95%.

Patent document 4 describes a method for producing 1, 3-diacetoxy-2-methylene propane by introducing a mixed gas containing isobutylene, acetic acid, and oxygen in a vapor phase onto a palladium catalyst to cause a reaction, and describes that methallyl acetate by-produced is recycled and added to the reaction gas. Patent document 4 describes: for the supported catalyst 10mL, acetic acid was passed through at a rate of 4L per hour: oxygen: isobutene: methallyl acetate: steam was changed to a mixed gas of 20: 10v 50: 10 and gas-phase reaction was carried out at a reaction temperature of 155 ℃ to obtain 1, 3-diacetoxy-2-methylenepropane with a production efficiency of 67g/{ L (catalyst) · hr }.

Disclosure of Invention

Problems to be solved by the invention

Conventional methods for producing diacyloxylated exomethylene compounds that do not produce inorganic by-products are all reactions under gas phase conditions. Under the gas phase condition, from the viewpoint of safety, it is necessary to forcibly operate the apparatus at a low substrate conversion rate while keeping the oxygen concentration below the limit oxygen concentration, and a substrate recovery apparatus is essential. Further, a gasification apparatus for the raw material, a reaction tube filled with a catalyst, and further a large amount of energy for gasifying the raw material are required, and there is a large margin for improvement from any viewpoint of production efficiency, facility cost, and energy consumption.

In view of the above-mentioned current situation, an object of the present invention is to provide a method for producing a bisacylated exomethylene compound, which does not produce inorganic by-products and is improved in production efficiency and cost.

Another object of the present invention is to provide a method for producing a bisacylated exomethylene compound, which does not produce inorganic by-products and has a further improved yield.

Means for solving the problems

The present inventors have conducted intensive studies and, as a result, have found that: the above problems can be solved by producing a bisacyloylated exo-methylene compound under specific liquid phase conditions, and further studies have been made based on this finding, thereby completing the first invention of the present application.

Further, the present inventors have conducted extensive studies and, as a result, have found that: when a monoacylated exomethylene compound, a carboxylic acid and oxygen are reacted under specific liquid phase conditions to produce a bisacylated exomethylene compound, the carboxylic acid or the like to be used is supplied in a semi-batch manner, and a part (the remainder) of the total carboxylic acid to be finally used is supplied to the reaction solution in the reaction process, whereby the monoacylated exomethylene compound as a raw material and the target bisacylated exomethylene compound can be inhibited from being hydrolyzed by water produced by the reaction, and the yield can be further improved.

The present invention relates to the following [1] to [11 ].

[1] A process for producing a bisacylated exomethylene compound represented by the following general formula (III) (hereinafter, sometimes referred to as "bisacylated exomethylene compound (III)") which comprises reacting a monoacylated exomethylene compound represented by the following general formula (I) (hereinafter, sometimes referred to as "monoacylated exomethylene compound (I)") with a carboxylic acid represented by the following general formula (II) (hereinafter, sometimes referred to as "carboxylic acid (II)") and oxygen in a liquid phase in the presence of a catalyst and optionally a solvent.

[ chemical formula 1]

(in the formula, R¹And R²Each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms or an optionally substituted aryl group having 6 to 14 carbon atoms; r³Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms and optionally having a substituent, a cycloalkyl group having 3 to 8 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 6 carbon atoms and optionally having a substituent, an aryl group having 6 to 14 carbon atoms and optionally having a substituent, an alkoxy group having 1 to 8 carbon atoms and optionally having a substituent, or an aryloxy group having 6 to 14 carbon atoms and optionally having a substituent; r⁴Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms and optionally having a substituent, a cycloalkyl group having 3 to 8 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 6 carbon atoms and optionally having a substituent, or an aryl group having 6 to 14 carbon atoms and optionally having a substituent; n represents an integer of 1 to 8. )

[2] The production method according to [1], which comprises: and supplying the carboxylic acid to the reaction solution in the reaction process.

[3] The production process according to [2], wherein all of the carboxylic acid to be used is continuously supplied to the reactor.

[4] The production process according to any one of [1] to [3], wherein the reaction is carried out in the presence of a solvent.

[5] The production method according to any one of [1] to [4], wherein the total amount of the solvent and the carboxylic acid used is more than 1 mol and 50 mol or less based on 1 mol of the monoacylated exomethylene compound.

[6] The production process according to any one of [1] to [5], wherein the solvent is at least 1 selected from the group consisting of hydrocarbons, heterocyclic compounds, ethers, ketones, esters, amides, nitriles, and alcohols.

[7] The production process according to [6], wherein the solvent is an ester represented by the following general formula (IV).

[ chemical formula 2]

(in the formula, R⁴As shown in the above definition, R⁵Represents an optionally substituted alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 14 carbon atoms. )

[8]According to [7]The production process described in (1), wherein R⁴Is methyl, R⁵Is an alkyl group having 1 to 4 carbon atoms.

[9] The production process according to [7] or [8], wherein the amount of the carboxylic acid used is 0.1 to 0.6 mol based on 1 mol of the monoacylated exomethylene compound.

[10]According to [1]～[9]The production process of any one of the above, wherein R³And R⁴Is methyl and n is 1 or 2.

[11]According to [1]～[10]The production process of any one of the above, wherein R¹And R²Is a hydrogen atom.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the first invention of the present application, a method for producing a bisacylated exomethylene compound which does not generate an inorganic by-product and is improved in production efficiency and cost can be provided.

In addition, according to the second invention of the present application, it is possible to provide a method for producing a bisacylated exomethylene compound in which inorganic by-products are not produced and the yield is further improved.

Detailed Description

The present invention will be described in detail below.

While the preferred embodiments of the present invention have been described while specific matters of the present invention are described, an embodiment in which 2 or more preferred embodiments of the present invention are combined is also a preferred embodiment of the present invention. In the case where there are several numerical ranges for items represented by numerical ranges, the preferable mode may be one in which the lower limit value and the upper limit value are selectively combined.

In one embodiment shown in the first invention of the present application relating to the method for producing the bisacylated exomethylene compound (III), the monoacyloxyated exomethylene compound (I), the carboxylic acid (II) and oxygen are reacted in a liquid phase in the presence of a catalyst and, if necessary, a solvent. Here, the one aspect of the second invention of the present application includes a step of supplying a carboxylic acid (II) to the reaction solution in the reaction process.

In the above reaction, in the form, the monoacylated exomethylene compound (I) is oxidized and subjected to dehydration condensation with the carboxylic acid (II), while the bisacylated exomethylene compound (III) and water are produced.

The reaction formula in the preferred embodiment of the present invention is as follows.

[ chemical formula 3]

(in the formula, R¹～R⁴And n is as defined above. )

By adopting the liquid phase condition, the costs of the equipment and the energy can be suppressed, respectively. Further, the present inventors have made studies to clarify that: under the gas phase conditions, the bisacylated exomethylene compound as a product is adsorbed on the catalyst due to its high boiling point to inhibit the reaction, and the catalyst is deactivated at a high temperature for maintaining the product in a gaseous state. That is, it is difficult to improve productivity under the gas phase condition, and the liquid phase condition is also advantageous from the viewpoint of production efficiency and yield.

Further, by including the step of supplying the carboxylic acid (II) to the reaction liquid in the above-mentioned reaction process (i.e., the reaction process of the monoacylated exocarpium methylene compound (I), the carboxylic acid (II) and oxygen in the liquid phase), it is possible to suppress hydrolysis of the monoacylated exocarpium methylene compound (I) as a raw material and the target bisacylated exocarpium methylene compound by water generated by the reaction, thereby further improving the yield.

[ starting materials and target products ]

In the Mono-and bisacylated Exo methylene Compounds (I) and (III), R is¹And R²Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, and n-octyl groups.

The above alkyl group optionally has a substituent. Examples of such a substituent include a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, and a silyl group. When a substituent is present, the number of the substituent is preferably 1 to 3.

Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a t-butyldiphenylsilyl group, and a triphenylsilyl group.

R¹And R²The cycloalkyl group having 3 to 8 carbon atoms may be a monocyclic group or a fused ring group, and examples thereof include cyclopropyl, cyclopentyl and cyclohexyl.

The above cycloalkyl group may have a substituent. Examples of such a substituent include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, and the above silyl group. When a substituent is present, the number of the substituent is preferably 1 to 3.

R¹And R²The aryl group having 6 to 14 carbon atoms may be monocyclic or fused ring, and examples thereof include phenyl, naphthyl, anthryl and phenanthryl.

The above aryl group optionally has a substituent. Examples of such a substituent include those mentioned above as R¹And R²The same substituents as those mentioned above as the substituents optionally having in the case of cycloalkyl. When a substituent is present, the number of the substituent is preferably 1 to 3.

From the viewpoint of acquisition easiness and the like, R¹And R²Each independently preferably represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably represents a hydrogen atom.

In the Mono-and bisacylated Exo methylene Compounds (I) and (III), R is³Examples of the alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms and the aryl group having 6 to 14 carbon atoms include¹And R²The same applies to the substituents as in the foregoing groups.

As R³Examples of the alkenyl group having 2 to 6 carbon atoms include vinyl (ethenyl group), 1-methylvinyl, 1-propenyl, 2-propenyl (allyl group), 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, and 3-butenyl.

The above alkenyl group may have a substituent. Examples of such a substituent include those mentioned above as R¹And R²The same substituents as those mentioned above as the substituents optionally having in the case of an alkyl group. When a substituent is present, the number of the substituent is preferably 1 to 3.

As R³Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and n-pentoxy.

The above alkoxy group optionally has a substituent. Examples of such a substituent includeAt R¹And R²The same substituents as those mentioned above as the substituents optionally having in the case of an alkyl group. When a substituent is present, the number of the substituent is preferably 1 to 3.

That is, the above alkoxy group may be, for example, an aralkyloxy group having an aryl group as a substituent. Examples of such aralkyloxy groups include benzyloxy, 1-phenylethoxy, 2-phenylethoxy, 1-phenylpropoxy, 2-phenylpropoxy, 3-phenylpropoxy, 4-phenylbutoxy, 1-naphthylmethoxy and 2-naphthylmethoxy.

R³The aryloxy group having 6 to 14 carbon atoms may be a monocyclic group or a fused ring group, and examples thereof include a phenoxy group, a tolyloxy group, a xylyloxy group, and a naphthyloxy group.

The above aryloxy group may have a substituent. Examples of the substituent include those mentioned above as R¹And R²The same substituents as those mentioned above as the substituents optionally having in the case of cycloalkyl. When a substituent is present, the number of the substituent is preferably 1 to 3.

From the viewpoint of acquisition easiness and the like, R³Preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, more preferably 1 selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, a vinyl group and a 1-methylvinyl group, even more preferably a methyl group or a 1-methylvinyl group, and most preferably a methyl group.

In the monoacylated exocarpium methylene compound (I) and the bisacylated exocarpium methylene compound (III), n is an integer of 1 to 8, preferably an integer of 1 to 4, and more preferably 1 or 2, from the viewpoint of ease of acquisition and the like.

In the carboxylic acid (II) and the bisacyloylated exomethylene compound (III), as R⁴Examples of the alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, the alkenyl group having 2 to 6 carbon atoms and the aryl group having 6 to 14 carbon atoms include³The same applies to the substituents as in the foregoing groups.

From the viewpoint of acquisition easiness and the like, R⁴Preferably C1-C8 alkyl or C2The alkenyl group of (6) is more preferably 1 selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, a vinyl group and a 1-methylvinyl group, still more preferably a methyl group or a 1-methylvinyl group, and most preferably a methyl group.

[ catalyst ]

The catalyst used in the production method of the present invention may be any catalyst that promotes the reaction between the monoacyloxyated exomethylene compound (I) and the carboxylic acid (II), and is preferably a catalyst in which a noble metal is supported on a carrier. The catalyst may be a commercially available catalyst or a catalyst synthesized by a known method.

Examples of the noble metal include palladium, gold, silver, platinum, rhodium, and ruthenium. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among them, palladium is preferable. The palladium may be metallic palladium or a palladium compound. The palladium compound is not particularly limited, and examples thereof include palladium chloride, palladium acetate, palladium nitrate, palladium sulfate, sodium chloropalladate, potassium chloropalladate, and barium chloropalladate.

When a catalyst in which palladium is supported on a carrier is used, the carrier may support a transition metal of groups 8 to 11 of the periodic table, such as iron, rhodium, copper, or gold, in addition to palladium; base metals of groups 12 to 15 of the periodic table of elements such as zinc, indium, tin, bismuth and the like; semimetals of groups 13 to 16 of the periodic table of elements such as arsenic and tellurium. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

When a catalyst in which a noble metal is supported on a carrier is used, examples of the carrier include solid oxides such as silica, alumina, zeolite, and titanium oxide, and mixtures thereof; high molecular compounds such as polystyrene, polyethylene, polyamide, cellulose and the like, and mixtures thereof; activated carbon, and the like. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among them, solid oxides and mixtures thereof or activated carbon are preferable, silica or alumina is more preferable, and silica is further preferable.

The particle diameter of the carrier is not particularly limited, but is preferably 10 μm to 10mm, more preferably 30 μm to 8 mm. When the particle diameter is 10mm or less, the raw material can sufficiently permeate into the catalyst, and the reaction can be easily and efficiently carried out. When the particle size is 10 μm or more, the carrier function is more likely to be sufficiently exhibited.

The amount of the catalyst is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the monoacylated exomethylene compound (I), the carboxylic acid (II) and the solvent.

[ catalyst activator ]

In the production method of the present invention, a catalyst activator may be added to the catalyst as needed. Examples of the catalyst activator include hydroxides, nitrates, carboxylates and carbonates of alkali metals such as sodium, potassium and cesium; hydroxides, nitrates, carboxylates, or carbonates of alkaline earth metals such as magnesium, calcium, and barium. Among them, a salt of the carboxylic acid (II) is preferable, an alkali metal salt of the carboxylic acid (II) is more preferable, and potassium acetate is further preferable from the viewpoint of availability and reactivity.

The amount of the catalyst activator is not particularly limited, but is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, based on the catalyst.

The catalyst activator may be used in a state of being supported in advance on a catalyst, or may be charged into a reaction apparatus together with the reaction mixture.

[ solvent ]

The production method of the present invention may be carried out in the presence of a solvent. Examples of the solvent include hydrocarbons (aliphatic hydrocarbons, aromatic hydrocarbons, etc.) such as hexane, heptane, methylcyclohexane, and benzene; heterocyclic compounds such as pyridine and quinoline; ethers such as diethyl ether, tetrahydrofuran, methyl t-butyl ether, and cyclopentyl methyl ether; ketones such as acetone, methyl ethyl ketone, and isobutyl methyl ketone; esters such as carboxylic acid esters, diethyl carbonate, and propylene carbonate; amides such as dimethylformamide and dimethylacetamide; nitriles such as acetonitrile and benzonitrile; alcohols such as methanol, ethanol, isopropanol, and phenol. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds. Among them, a carboxylic acid ester is preferable, and the ester (IV) is more preferable from the viewpoint of production efficiency and yield of the bisacylated exomethylene compound (III).

In the ester (IV), R⁴Is reacted with carboxylic acid (II) and R in bisacyloylated exomethylene compound (III)⁴The same groups.

In the ester (IV), as R⁵Examples of the alkyl group having 1 to 8 carbon atoms or the aryl group having 6 to 14 carbon atoms include the group represented by¹And R²The same applies to the substituents as in the foregoing groups.

From the viewpoints of easiness of obtaining, production efficiency, yield of the bisacyloylated exomethylene compound (III), and the like, R⁵Preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

[ oxygen ]

As the oxygen used in the production method of the present invention, atomic oxygen and/or molecular oxygen can be used, and molecular oxygen is preferable. When molecular oxygen is used, it is preferably used in the form of a mixed gas with an inert gas such as nitrogen, argon, helium, or carbon dioxide. In this case, it is more preferable to adjust the oxygen concentration to a range where the gas in the reaction system does not have an explosive composition.

Examples of the method of supplying molecular oxygen or a mixed gas containing molecular oxygen to the reaction system include a method of supplying molecular oxygen to a liquid phase portion in the reaction system, a method of supplying molecular oxygen to a gas phase portion, and a method of supplying molecular oxygen to both of the liquid phase portion and the gas phase portion.

When molecular oxygen or a mixed gas containing molecular oxygen is supplied to the reaction system, the oxygen partial pressure is preferably 0.01 atm or more, more preferably 0.1 atm or more, and further preferably 0.2 atm or more, and further preferably 200 atm or less, more preferably 100 atm or less, and further preferably 80 atm or less, in terms of gauge pressure, and may be 20 atm or less, 10 atm or less, and 8 atm or less.

[ reaction conditions ]

In the production method of the present invention, the total amount of the solvent and the carboxylic acid (II) to be used is preferably more than 1 mol and 50 mol or less, more preferably 1.5 mol or more and 35 mol or less, and still more preferably 2 mol or more and 10 mol or less, based on 1 mol of the monoacylated exo-methylene compound (I). By setting the total amount to more than 1 mole, hydrolysis of the monoacylated exomethylene compound (I) and the bisacylated exomethylene compound (III) by water generated by the reaction is suppressed, and the production efficiency and the yield of the bisacylated exomethylene compound (III) become more excellent. By setting the total amount of the solvent to 50 mol or less, the recovery step of the excessive solvent and the carboxylic acid (II) becomes short, which is economically advantageous.

The present inventors have found that: even when the ester (IV) is used as a solvent in the production method of the present invention, higher production efficiency and yield can be obtained when the amount of the carboxylic acid (II) to be used is reduced to 0.1 mol or more and 0.6 mol or less relative to 1 mol of the monoacylated exomethylene compound (I). When the amount of the carboxylic acid (II) is within the above range, corrosion of the apparatus can be suppressed, and introduction of the raw material can be simplified, which is industrially very advantageous.

The reaction conditions such as the reaction temperature, the reaction pressure and the reaction time in the production method of the present invention may be appropriately set depending on the kind and combination of the monoacylated exocrine methylene compound (I), the carboxylic acid (II) and the solvent, the composition of the catalyst, etc., and are not particularly limited, and the reaction temperature is preferably in the range of 80 to 200 ℃. By setting the reaction temperature to 80 ℃ or higher, the reaction rate is not excessively slow, and the bisacylated exomethylene compound (III) can be efficiently produced. On the other hand, by setting the reaction temperature to 200 ℃ or lower, side reactions including combustion are less likely to occur, the bisacylated exomethylene compound (III) can be efficiently produced, and corrosion of the reaction apparatus by the carboxylic acid can be suppressed.

The reaction form in the production method of the present invention may be any of a continuous type and a batch type, and is not particularly limited. For example, when a batch type is employed as the reaction form, the catalyst may be charged into the reaction apparatus together with the raw material, and when a continuous type is employed as the reaction form, the catalyst may be charged into the reaction apparatus in advance or may be continuously charged into the reaction apparatus together with the raw material. The catalyst may be used in any form of a fixed bed, a fluidized bed, or a suspended bed.

In one embodiment of the second invention of the present application, the method comprises a step of supplying the carboxylic acid (II) to a reaction solution in a process of reacting the monoacylated exomethylene compound (I), the carboxylic acid (II) and oxygen in a liquid phase (that is, in a state where a part of the monoacylated exomethylene compound (I) is already reacted with the carboxylic acid (II) and oxygen, and unreacted monoacylated exomethylene compound (I) remains). This step can be performed by supplying the carboxylic acid (II) to the reactor in a semi-batch manner, and more specifically, can be performed by supplying the carboxylic acid (II) to the reactor continuously and/or in a plurality of times without substantially removing the bisacylated exomethylene compound (III) from the reactor during the above-mentioned reaction (for example, without removing 5% by mass or more of the finally obtained bisacylated exomethylene compound (III) from the reactor during the above-mentioned reaction).

In the above operation, all of the carboxylic acid (II) to be used may be continuously supplied to the reactor, or all of the carboxylic acid (II) to be used may be supplied to the reactor in a plurality of times, and for example, the reaction may be started in a state where a part of the carboxylic acid (II) to be used is previously charged into the reactor, and thereafter the remaining amount may be supplied to the reactor continuously and/or in a plurality of times. From the viewpoint of operability, yield, and the like, it is preferable that all of the carboxylic acid (II) used is continuously supplied to the reactor.

For example, in the case of a method in which the reaction is started in a batch manner after raw materials such as the monoacylated exomethylene compound (I), the carboxylic acid (II) and the catalyst are all put into a reactor, or the reaction is started in a continuous manner while raw materials such as the monoacylated exomethylene compound (I) and the carboxylic acid (II) are supplied to the upstream portion thereof by a cylindrical reactor or the like, and the carboxylic acid (II) is supplied to the reaction liquid during the reaction, the yield of the bisacylated exomethylene compound (III) is easily decreased by hydrolyzing the monoacylated exomethylene compound (I) as the raw materials and the target bisacylated exomethylene compound (III) due to water produced by the reaction, and the carboxylic acid (II) is supplied to the reaction liquid during the reaction, the yield can be improved.

In one embodiment of the second invention of the present application, the supply method of the raw materials other than the carboxylic acid (II), such as the monoacyloxyated exomethylene compound (I), is not particularly limited, and the raw materials may be supplied to the reactor all at once and then the reaction may be started, or may be supplied to the reactor continuously. When the reaction is started after the reaction is collectively supplied to the reactor, the catalyst may be charged into the reactor together with the monoacylated exo-methylene compound (I) or the like, or when the reaction is continuously supplied to the reactor, the catalyst may be charged into the reactor in advance or may be continuously charged into the reactor together with the monoacylated exo-methylene compound (I) or the like. The catalyst may be used in any form of a fixed bed, a fluidized bed, or a suspended bed.

The bisacylated exomethylene compound (III) produced by the production method of the present invention can be isolated by separating the catalyst and then purifying the reaction solution. The purification means is not particularly limited, and distillation, extraction, column chromatography, or the like can be used. These methods may be implemented in combination. Among them, a distillation method or an extraction method is preferable.

The raw materials and the solvent separated by the above purification can be used again for the reaction. In addition, the separated catalyst can also be reused for the reaction.