Method for producing carbonyl compound

Abstract

This method for producing a carbonyl compound comprises reacting an active hydrogen-containing compound which has, in a molecule, an active hydrogen-containing group obtained by bonding a hydrogen atom to an atom selected from among an oxygen atom, a nitrogen atom, and a sulfur atom with a carbonic acid diester compound in the presence of a quaternary ammonium salt represented by general formula (1) or (2), and thereby introducing a carbonyl group into the active hydrogen-containing compound. In general formulae (1) and (2), R1 represents an organic group having a chemical formula amount of at least 65. R2-R4 represent alkyl groups, and at least two among R2-R4 are alkyl groups having at most 6 carbon atoms. R5 represents an alkyl group having 1-20 carbon atoms and n is an integer of 0-2. Y- represents a counter ion.

Description

Method for producing carbonyl compounds

[0001] The present invention relates to a method for producing a carbonyl compound.

[0002] Carbonyl halide compounds such as phosgene are known as reactants for introducing carbonyl groups into various compounds containing active hydrogen. For example, isocyanate compounds, urea compounds, etc. can be obtained by reacting phosgene with primary amines. Carbonate compounds, chloroformates, etc. can be obtained by reacting phosgene with alcohols. Furthermore, chlorothioformates can be obtained by reacting phosgene with thiols. However, carbonyl halide compounds are highly toxic, and many of them are gaseous at room temperature, so they must be handled with extreme care.

[0003] In order to introduce a carbonyl group into an active hydrogen-containing compound without using a carbonyl halide compound, a method is also known in which a carbonate diester compound such as diphenyl carbonate having a highly electron-withdrawing leaving group is reacted with the active hydrogen-containing compound. The use of a dialkyl carbonate having a lower alkyl group instead of diphenyl carbonate has also been investigated. For example, Patent Document 1 discloses a method for introducing a carbonyl group into an active hydrogen-containing compound without using a carbonyl halide compound, in which a dialkyl carbonate having a lower alkyl group is reacted with a quaternary ammonium salt having a specific structure ([Me(n-C １２ H ２５ ) ３ N] ＋ [OCO ２ Me] － In the method described in Patent Document 1, methanol, which is a by-product, has a low boiling point, and therefore, it is easy to remove methanol from the reaction system.

[0004] JP 2012-106982 A

[0005] An object of the present invention is to provide a method for producing a carbonyl compound, which can highly efficiently introduce a carbonyl group into an active hydrogen-containing compound by reacting a carbonate diester compound with an active hydrogen-containing compound, thereby enabling the target carbonyl compound to be obtained highly efficiently.

[0006] The present inventors have conducted extensive research to efficiently introduce carbonyl groups into active hydrogen-containing compounds by reacting a carbonic acid diester compound with an active hydrogen-containing compound. As a result, they have found that the catalytic activity of quaternary ammonium salts such as those described in Patent Document 1 is insufficient, and that the efficiency of introducing carbonyl groups into active hydrogen-containing compounds can be significantly improved by using a specific combination of four substituents on the quaternary ammonium salt. Based on these findings, the present invention has been completed through further research.

[0007] The above-mentioned problems of the present invention are solved by the following means: [1] A method for producing a carbonyl compound, comprising reacting an active hydrogen-containing compound having an active hydrogen-containing group in the molecule, the active hydrogen-containing group being formed by bonding a hydrogen atom to an atom selected from oxygen, nitrogen, and sulfur atoms, with a carbonic acid diester compound in the presence of a quaternary ammonium salt represented by the following general formula (1) or (2), thereby introducing a carbonyl group into the active hydrogen-containing compound: In the above general formulas (1) and (2), R １ R represents an organic group with a formula weight of 65 or more. ２ ~R ４ represents an alkyl group, and R ２ ~R ４ At least two of R are alkyl groups having 6 or less carbon atoms. ５ represents an alkyl group having 1 to 20 carbon atoms, and n is an integer of 0 to 2. － represents a counter ion. [2] In the general formulas (1) and (2), the R １ [3] In the general formulas (1) and (2), the R １is a polymer structure having a crosslinked structure. [4] A method for producing a carbonyl compound according to any one of [1] to [3], in which the quaternary ammonium salt is present as a solid in the reaction system of the reaction. [5] A method for producing a carbonyl compound according to any one of [1] to [4], in which the reaction is carried out in a flow reaction system. [6] A method for producing a carbonyl compound according to [5], which comprises passing a liquid containing the active hydrogen-containing compound and the carbonate diester compound through a column packed with the quaternary ammonium salt. [7] A method for producing a carbonyl compound according to [5], which comprises passing a liquid containing the active hydrogen-containing compound and the carbonate diester compound through a column packed with the quaternary ammonium salt. [8] A method for producing a carbonyl compound according to [5], in which in the general formula (1), R ２ ~R ４ [8] In the general formulas (1) and (2), at least two of Y are methyl. － is selected from a halide anion, a sulfonate anion, a phosphate anion, a phosphonate anion, a perchlorate anion, and a fluorophosphate anion. [9] The method for producing a carbonyl compound according to any one of [1] to [8], wherein the carbonate diester compound is a dialkyl carbonate compound.

[10] The method for producing a carbonyl compound according to [9], wherein the carbonate diester compound is dimethyl carbonate.

[11] The method for producing a carbonyl compound according to any one of [1] to

[10] , wherein the active hydrogen-containing compound is selected from a polyhydric alcohol compound, a polyhydric amine compound, and a polyhydric thiol compound.

[12] The method for producing a carbonyl compound according to any one of [1] to

[11] , wherein the carbonyl compound obtained by the method is a monomer and / or a polymer.

[13] The method for producing a carbonyl compound according to any one of [1] to

[12] , comprising heating the reaction system of the reaction by microwave irradiation.

[0008] In the present invention, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In the present invention, groups that are not specified as substituted or unsubstituted include those that have any substituent within the range that does not impair the intended effect. For example, "alkyl group" means to include substituted alkyl groups and unsubstituted alkyl groups. Furthermore, for example, "phenyl" means to include substituted phenyl and unsubstituted phenyl.

[0009] According to the method for producing a carbonyl compound of the present invention, a carbonyl group can be introduced into the active hydrogen-containing compound with high efficiency by reacting a carbonic acid diester compound with an active hydrogen-containing compound, and as a result, the target carbonyl compound can be obtained with high efficiency.

[0010] FIG. 1 is a diagram schematically illustrating an example of a flow reaction system.

[0011] [Method for Producing Carbonyl Compounds] The method for producing carbonyl compounds of the present invention (hereinafter referred to as the "production method of the present invention") comprises reacting a compound (active hydrogen-containing compound) having an active hydrogen-containing group in the molecule, where the active hydrogen-containing group is formed by bonding a hydrogen atom to an atom selected from oxygen, nitrogen, and sulfur atoms, with a carbonic acid diester compound in the presence of a quaternary ammonium salt of a specific structure, thereby introducing a carbonyl group into the active hydrogen-containing compound. The reaction of reacting an active hydrogen-containing compound with a carbonic acid diester compound to introduce a carbonyl group into the active hydrogen-containing compound is known per se. The present invention is characterized by the use of a quaternary ammonium salt of a specific structure, described below, whose catalytic activity for this reaction has not previously been known. The production method of the present invention will now be described in detail.

[0012] <Active Hydrogen-Containing Compound> The active hydrogen-containing compound is not particularly limited as long as it is a compound having active hydrogen in the molecule. For example, —OH, —COOH, —NH ２A wide variety of compounds having at least one group selected from -NHR (R is a substituent), and -SH can be used. Examples of active hydrogen-containing compounds include at least one of primary amine compounds, secondary amine compounds, hydroxy compounds (the term "hydroxy compounds" is used to encompass both compounds having an alcoholic hydroxy group and compounds having a phenolic hydroxy group), thiol compounds, carboxylic acid compounds, and amino acid compounds. Of these, at least one of primary amine compounds, secondary amine compounds, hydroxy compounds, and thiol compounds is preferred. The molecular weight of the active hydrogen-containing compound is preferably 40 to 1,000, and more preferably 60 to 500. When the carbonyl compound obtained by the production method of the present invention is used as a monomer or prepolymer (when used as a raw material for a polymer), the active hydrogen-containing compound can be selected from polyhydric hydroxy compounds (compounds having two or more hydroxy groups), polyhydric amine compounds (compounds having two or more amino groups (preferably unsubstituted amino groups)), and polyhydric thiol compounds (compounds having two or more thiol groups), and among these, it is preferable to use a compound selected from diol compounds (the two hydroxy groups of the diol compound may be alcoholic or phenolic), diamine compounds, and dithiol compounds. For example, when the carbonyl compound obtained by the production method of the present invention is used as a monomer or prepolymer for obtaining a polycarbonate compound, the active hydrogen-containing compound can be a polyhydric hydroxy compound, and preferably a diol compound. Furthermore, when the carbonyl compound obtained by the production method of the present invention is used as a monomer or prepolymer for obtaining a polyurea compound, the active hydrogen-containing compound can be a polyhydric amine compound, and more preferably a diamine compound. When used as a monomer or prepolymer for obtaining a polythioamide compound, a polyvalent thiol can be used as the active hydrogen-containing compound, and a dithiol compound is more preferably used.Furthermore, a plurality of types of the active hydrogen-containing compounds (for example, a diol compound and a diamine compound) may be used, or a single compound may contain a plurality of types of active hydrogen (for example, a hydroxy group and an amino group).

[0013] <Carbonate diester compound> The carbonate diester compound is R ａ OC(=O)-OR ｂ It is a compound represented by the formula: R ａ and R ｂ represents a substituent, and is preferably an alkyl group or an aryl group. ａ and R ｂ may be the same or different, and are preferably the same. ａ and R ｂ The alkyl group that can be taken as R preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms. ａ and R ｂ When the alkyl group that can be taken as R has 3 or more carbon atoms, it may be linear or branched. ａ and R ｂ The alkyl group that can be taken as R is more preferably methyl or ethyl, and even more preferably methyl. ａ and R ｂ The aryl group that can be taken as R is preferably phenyl or naphthyl, and more preferably phenyl. ａ and R ｂ The alkyl group or aryl group (preferably phenyl or naphthyl) that can be taken as R may have a substituent within the range that does not impair the effects of the present invention. ａ and R ｂ The alkyl group or aryl group which can be taken as the alkyl group is preferably an unsubstituted alkyl group or an unsubstituted aryl group.

[0014] The carbonate diester compound is preferably a dialkyl carbonate compound or a diphenyl carbonate compound. From the viewpoint of being able to carry out the reaction with the active hydrogen-containing compound at a lower temperature while efficiently removing by-products, a dialkyl carbonate compound having an alkyl group with 1 to 4 carbon atoms is preferred, diethyl carbonate (which produces low-boiling ethanol as a by-product) or dimethyl carbonate (which produces low-boiling methanol as a by-product) is more preferred, and dimethyl carbonate is even more preferred. Furthermore, when a dialkyl carbonate compound is used, diethyl carbonate or dimethyl carbonate is preferred, and dimethyl carbonate is more preferred, also from the viewpoint of the efficiency of introducing a carbonyl group.

[0015] <Quaternary Ammonium Salt> In the production method of the present invention, the active hydrogen-containing compound and the carbonate diester compound are reacted using a quaternary ammonium salt represented by the following general formula (1) or (2) as a reaction catalyst.

[0016]

[0017] In the above general formulas (1) and (2), R １ R represents an organic group with a formula weight of 65 or more. ２ ~R ４ represents an alkyl group, and R ２ ~R ４ At least two of R are alkyl groups having 6 or less carbon atoms. ５ represents an alkyl group having 1 to 20 carbon atoms, and n is an integer of 0 to 2. － indicates a counter ion.

[0018] The above R １ The organic group having a chemical formula weight of 65 or more is preferably an alkyl group, an aromatic group, or a polymer structure. １ The organic group having a chemical formula weight of 65 or more is preferably an organic group having a chemical formula weight of 70 or more. １ The alkyl group that can be taken as R is not particularly limited as long as the chemical formula weight is 65 or more. １ The alkyl group that can be taken as R is an alkyl group having 5 or more carbon atoms, preferably an alkyl group having 5 to 30 carbon atoms, more preferably an alkyl group having 6 to 28 carbon atoms, still more preferably an alkyl group having 8 to 26 carbon atoms, and particularly preferably an alkyl group having 10 to 24 carbon atoms.１ The alkyl group that can be taken as R may be linear or branched. １ When the alkyl group that can be taken as R has a branch, the number of branches is preferably 1 (single-branched structure) or 2 (double-branched structure), and more preferably a single-branched structure. １ The alkyl group that can be taken as R may have a substituent within a range that does not impair the effects of the present invention. In this case, if the chemical formula weight of the entire alkyl group including the substituent is 65 or more, it corresponds to the above-mentioned "organic group with a chemical formula weight of 65 or more." １ The alkyl group which can be taken as the alkyl group is preferably an unsubstituted alkyl group or an alkyl group having an aryl group (preferably phenyl) as a substituent, and more preferably an unsubstituted alkyl group.

[0019] The above R １ The aromatic group that can be used as R is an aryl group or a heteroaryl group, with an aryl group being preferred. The aromatic group may be a monocyclic or condensed ring, with a monocyclic group being preferred. The number of ring members in the ring of the aromatic group (in the case of a condensed ring, the number of ring members in each monocyclic ring constituting the condensed ring) is preferably 5 or 6. The aromatic group is more preferably phenyl. The R １ The aromatic group which can be taken as R may have a substituent within the range that does not impair the effects of the present invention. １ is preferably an alkyl group having a chemical formula weight of 65 or more, or a polymer structure.

[0020] The above R １ The polymer structure that can be adopted as R is not particularly limited as long as it is a polymer structure. This polymer structure may be a sequential polymerization structure or an addition polymerization structure, and is preferably an addition polymerization structure of a monomer having a carbon-carbon double bond. For example, an addition polymerization structure (polystyrene compound structure) containing a styrene compound as a monomer component can be adopted as R １ The polymer structure R １ The polymer structure that can be adopted as R is preferably a hydrocarbon structure (hydrocarbon polymer structure). １The polymer structure that can be adopted as the catalyst preferably has a crosslinked structure. By introducing this crosslinked structure, it is also preferable to react the active hydrogen-containing compound with the carbonate diester compound while the quaternary ammonium salt is present in the reaction system as a solid in the production method of the present invention. In this case, the polymer structure also functions as a carrier for supporting the catalyst.

[0021] In the above general formula (1) or (2), R １ In the case where the quaternary ammonium salt represented by the general formula (1) or (2) has a polymer structure, it is preferable that the polymer structure also has one or more structural parts corresponding to the quaternary ammonium salt represented by the general formula (1) or (2). That is, it is preferable that a plurality of quaternary ammonium salts represented by the general formula (1) or (2) have the same structure as each R １ For example, the quaternary ammonium salt "A-11" described in the examples below has a structure in which R １ is a crosslinked polystyrene compound structure, and in this crosslinked polystyrene compound structure, R １ Such structures are also included in the quaternary ammonium salts represented by the general formula (1). １ When is a polymer structure, R １ The bond between the polymer structure and the N atom in general formula (1) or (2) may be via a linking group. In this case, the linking group is R １ For example, the quaternary ammonium salt "A-11" described in the examples below is a -N ＋ (Me) ３ can be interpreted as being bonded to the polystyrene compound structure via a methylene, and this methylene is to be interpreted as a group contained in the polystyrene compound structure. ＋ (Me) ３ can be interpreted as being directly bonded to p-methylstyrene, a styrene compound, and subjected to addition polymerization. １ and a polymer structure in which -N ＋ (Me) ３In either interpretation, it is clear that the quaternary ammonium salt "A-11" is included in the above general formula (1), and therefore the technical scope of the present invention is objectively clear. １ The molecular weight of the polymer structure that can be used is not particularly limited and can be set appropriately. For example, the weight average molecular weight can be set to 1,000 to 1,000,000.

[0022] R in the above general formula (1) ２ ~R ４ represents an alkyl group as described above, and R ２ ~R ４ At least two of R are alkyl groups having 6 or less carbon atoms. ２ ~R ４ It is also preferred that all of R are alkyl groups having 6 or less carbon atoms. ２ ~R ４ The alkyl group having 6 or less carbon atoms that can be taken as R preferably has 5 or less carbon atoms, more preferably has 4 or less carbon atoms, and even more preferably has 3 or less carbon atoms, and is preferably ethyl or methyl, and particularly preferably methyl. ２ ~R ４ Preferably, at least two of R are methyl. ２ ~R ４ When one of R is an alkyl group having 7 or more carbon atoms, the alkyl group preferably has 7 to 30 carbon atoms, more preferably 8 to 22 carbon atoms, and even more preferably 10 to 22 carbon atoms. ２ ~R ４ In the above formula, when the alkyl group has 3 or more carbon atoms, it may be linear or branched, and linear alkyl groups are preferred. When branched, a monobranched structure is preferred. ２ ~R ４ In the formula, the alkyl group may have a substituent within the range that does not impair the effects of the present invention, but an unsubstituted alkyl group is preferred. ２ ~R ４ In the above formula, when the alkyl group has a substituent, the number of carbon atoms is the total number of carbon atoms including the substituent.

[0023] R in the above general formula (2) ５ As described above, R represents an alkyl group having 1 to 20 carbon atoms. ５R preferably has 1 to 18 carbon atoms, more preferably 1 to 16, even more preferably 1 to 14, still more preferably 1 to 12, even more preferably 1 to 10, still more preferably 1 to 8, and particularly preferably 1 to 6. ５ As described above, n is 0 to 2, and preferably 0 or 1. When n is 1 or 2, R ５ is preferably bonded to the meta or para position relative to the N atom constituting the pyridinium ring. ５ When n, which indicates the number of ５ is preferably bonded to the para position relative to the N atom constituting the pyridinium ring. ５ In R, the alkyl group having 1 to 20 carbon atoms may be linear or branched. ５ In the formula, the alkyl group having 1 to 20 carbon atoms may have a substituent within the range that does not impair the effects of the present invention, but an unsubstituted alkyl group is preferred. ５ In the above formula, when the alkyl group has a substituent, the number of carbon atoms is the total number of carbon atoms including the substituent.

[0024] R １ ~R ５ Each of the groups which can be taken as the group preferably has a hydrocarbon structure as a whole.

[0025] Y － There are no particular limitations on the counter ion (anion) that can be used for Y. Examples of counter ions include those selected from halide anions, sulfonate anions, phosphate anions, phosphonate anions, perchlorate anions, and fluorophosphate anions (preferably tetrafluorophosphate anions or hexafluorophosphate anions). － The counter ion that can be taken for is preferably a halide anion, and the halide anion is preferably a bromide ion or a chloride ion.

[0026] Specific preferred examples of the quaternary ammonium salts represented by the above general formula (1) or (2) are shown below, where Me represents methyl, Bu represents n-butyl, and OTs represents a tosylate anion.

[0027]

[0028] <Carbonyl Group Introduction Reaction> In the production method of the present invention, the active hydrogen-containing compound and the carbonate diester compound are reacted using a quaternary ammonium salt having a unique structure represented by the general formula (1) or (2) as a reaction catalyst (this reaction is referred to as the "reaction of the present invention"). By using the quaternary ammonium salt, the efficiency of introducing the carbonyl compound into the active hydrogen-containing compound can be further improved when diphenyl carbonate having a highly electron-withdrawing leaving group is used as the carbonyl group source. Furthermore, even when a dialkyl carbonate having a less electron-withdrawing leaving group is used, the efficiency of introducing the carbonyl group into the active hydrogen-containing compound can be sufficiently improved. While the reason for this is unclear, one possible reason is that the quaternary ammonium salt has a structure represented by the general formula (1) or (2), which reduces steric hindrance at certain sites while increasing solubility or affinity with raw materials at other sites, thereby improving the efficiency of catalytic action.

[0029] The reaction of reacting the active hydrogen-containing compound with the carbonic acid diester compound to introduce a carbonyl group into the active hydrogen-containing compound is known per se. As an example, two reaction formulas for the reaction of a carbonic acid diester compound with a monoalcohol compound are shown below. Ａ OC(=O)-OR Ａ is, for example, dimethyl carbonate or diphenyl carbonate (R Ａ methyl or phenyl), and R Ｂ -OH is, for example, 1-decanol (R Ｂ : decyl). Ａ OC(=O)-OR Ａ + R Ｂ -OH ⇔ R Ａ OC(=O)-OR Ｂ + R Ａ -OH R Ａ OC(=O)-OR Ａ + 2R Ｂ -OH ⇔ R Ｂ OC(=O)-OR Ｂ + 2R Ａ -OH Two reaction formulas are shown above, but in the first formula, "RＡ OC(=O)-OR Ｂ " and the second equation "R Ｂ OC(=O)-OR Ｂ " can be regarded as the target carbonyl compound in the present invention. In addition, since the production of the target carbonyl compound is an equilibrium reaction with the raw material, Ａ OC(=O)-OR Ａ " and "R Ｂ By controlling the amount ratio of "R -OH", reaction time, reaction temperature, concentration, etc., Ａ OC(=O)-OR Ｂ " and "R Ｂ OC(=O)-OR Ｂ In the present invention, the use of a quaternary ammonium salt represented by the above general formula (1) or (2) as a reaction catalyst can significantly increase the efficiency of producing the target carbonyl compound.

[0030] As examples of reactions other than those described above, three examples of reaction formulas between a carbonic acid diester compound and a diol compound are shown below. Ａ is as defined above, and HO-L Ｂ -OH is, for example, 1,4-butanediol (L Ｂ : butylene). Ａ OC(=O)-OR Ａ + HO-L Ｂ -OH ⇔ R Ａ OC(=O)-OL Ｂ -OH + R Ａ -OH 2R Ａ OC(=O)-OR Ａ + HO-L Ｂ -OH ⇔ R Ａ OC(=O)-OL Ｂ -OC(=O)-OR Ａ + 2R Ａ -OH R Ａ OC(=O)-OR Ａ + 2HO-L Ｂ -OH ⇔ HO-L Ｂ -OC(=O)-OLＢ -OH + 2R Ａ -OH Three reaction formulas are shown above, but in the first formula, "R Ａ OC(=O)-OL Ｂ -OH" and "R" in the second formula Ａ OC(=O)-OL Ｂ -OC(=O)-OR Ａ " and the third equation "HO-L Ｂ -OC(=O)-OL Ｂ Each of the "R -OH" can be regarded as a target carbonyl compound (for example, a monomer for obtaining polycarbonate) in the present invention. Ａ OC(=O)-OR Ａ " and "HO-L Ｂ The composition of the reaction product can also be controlled by controlling the ratio of the amounts of —OH, the reaction time, the reaction temperature, the concentration, etc. Furthermore, by using a quaternary ammonium salt represented by the above general formula (1) or (2) as a reaction catalyst, the efficiency of producing the target carbonyl compound can be significantly increased.

[0031] The reactions of the present invention are equilibrium reactions, and for example, by reacting an excess amount of a carbonate diester compound, the equilibrium of each of the above reaction formulas can be shifted to the right, thereby more efficiently producing the target carbonyl compound.

[0032] In the reaction between a carbonate diester compound and a diol compound, the types of products actually obtained are not limited to those shown in the above reaction formula. For example, taking the case where dimethyl carbonate is used as the carbonate diester compound and C-2, which is used in the examples described below, as the diol compound, the reaction of the present invention can produce the following reaction products, including unreacted ones. All reaction products other than the unreacted diol compound are considered to be the target carbonyl compound of the present invention. Furthermore, by adjusting the reaction conditions, the reaction product can also contain oligomers or polymers that are formed by further polymerization of the following reaction products.

[0033]

[0034] Although the above describes an example of a reaction formula when a hydroxy compound is used as the active hydrogen-containing compound, it will be understood by those skilled in the art that a reaction product will be produced in accordance with the above reaction formula even when the active hydrogen-containing compound is a compound other than a hydroxy compound (e.g., an amine compound, a thiol compound, etc.).

[0035] In the reaction of the present invention, the ratio of the amounts of the active hydrogen-containing compound and the carbonic acid diester compound is not particularly limited as long as the desired reaction proceeds. For example, the molar ratio is preferably [active hydrogen-containing compound] / [carbonic acid diester compound]=1 / 100 to 1 / 0.1, more preferably [active hydrogen-containing compound] / [carbonic acid diester compound]=1 / 30 to 1 / 1, even more preferably [active hydrogen-containing compound] / [carbonic acid diester compound]=1 / 20 to 1 / 2, and even more preferably [active hydrogen-containing compound] / [carbonic acid diester compound]=1 / 10 to 1 / 3.

[0036] In the reaction of the present invention, the amount of the quaternary ammonium salt (catalyst) represented by the general formula (1) or (2) present in the reaction system is not particularly limited as long as it is an amount that catalyzes the target reaction. For example, the molar ratio of [catalyst] / [carbonate diester compound] is preferably 1 / 10 to 1 / 10,000, more preferably 1 / 10 to 1 / 2,000, still more preferably 1 / 10 to 1 / 1,000, and even more preferably 1 / 12 to 1 / 500.

[0037] The reaction temperature of the reaction of the present invention varies depending on the type of carbonate diester compound used, but is preferably in the range of 70 to 250°C. This temperature is preferably set to a temperature above the boiling point of the by-products, such as alcohol and phenol. Therefore, when dimethyl carbonate is used as the carbonate diester, the by-product is methanol, which has a low boiling point, and therefore the by-product can be removed efficiently even at a lower reaction temperature. Furthermore, by-product removal is made easier by carrying out the reaction under reduced pressure. Considering the need to ensure reaction efficiency while reducing environmental impact, the reaction temperature is more preferably 70 to 220°C, more preferably 80 to 200°C, and even more preferably 80 to 150°C. Since the reaction of the present invention uses a quaternary ammonium salt represented by the general formula (1) or (2) as the reaction catalyst, a carbonate diester compound capable of removing by-products at such a reaction temperature can be appropriately applied. The reaction temperature can also be controlled by irradiating the reaction system with microwaves. By heating by microwave irradiation, it is possible to obtain the target carbonyl compound with high efficiency even if the reaction time is shortened (for example, the heating time is about 1 / 4 of the heating time using an oil bath or even shorter). Microwaves may be used in single mode or multimode. Furthermore, electric field heating or magnetic field heating may be used.

[0038] The reaction time for the reaction of the present invention is not particularly limited as long as the desired reaction proceeds. For example, it can be 1 minute to 10 hours. In a batch reaction, the reaction time is preferably 5 minutes to 10 hours, but can also be 20 minutes to 5 hours, and preferably 30 minutes to 3 hours. Furthermore, when a flow reaction, which will be described later, is employed, a carbonyl compound can be obtained highly efficiently in a shorter reaction time. Therefore, when a flow reaction is employed, the reaction time is preferably 5 seconds to 30 minutes, but can also be 10 seconds to 20 minutes, and preferably 30 seconds to 10 minutes.

[0039] When the reaction of the present invention is carried out in a batch system, the active hydrogen-containing compound, the carbonic acid diester compound, and the quaternary ammonium salt represented by the general formula (1) or (2) are charged into a reaction vessel and reacted at the reaction temperature. For example, the reaction can be carried out while heating under reflux conditions in the atmosphere. A solvent can be used as appropriate, but a solvent-free reaction system is also possible if the raw materials are liquid under the reaction conditions.

[0040] When the reaction of the present invention is carried out in a flow system, it is preferable to use a quaternary ammonium salt represented by the above general formula (1) or (2) as a solid-phase catalyst (solid catalyst). For example, R １ By forming a crosslinked polymer structure, the quaternary ammonium salt can be present as a solid in the reaction system. １ can function as a carrier insoluble in the reaction solution. This insoluble catalyst is packed into a column, and a mixed solution of the active hydrogen-containing compound and the carbonic acid diester compound is passed through the column, whereby the reaction of introducing a carbonyl group into the active hydrogen-containing compound proceeds while the mixture is passing through the column. An example of a flow reaction system for carrying out this flow reaction is shown in FIG. 1. Note that R １ As long as the polymer structure is insoluble in the reaction solution, the polymer structure does not necessarily have to have a crosslinked structure. Such an insoluble polymer structure can be appropriately designed.

[0041] In the flow reaction system (10) shown in FIG. 1 , liquid I containing the active hydrogen-containing compound is introduced into flow path (1) through inlet (Ia), and liquid II containing the carbonic acid diester compound is introduced into flow path (2) through inlet (Ib). Inlets (Ia) and (Ib) are typically connected to liquid delivery pumps (not shown), such as syringe pumps or diaphragm pumps, and by operating these pumps, each liquid can be circulated through each flow path at a desired flow rate. Liquid I and liquid II are merged at confluence (3), and the merged liquid is introduced into column (C1) filled with a catalyst insoluble in the reaction liquid. The carbonyl group introduction reaction into the active hydrogen-containing compound can proceed within column (C1). The reaction liquid after the carbonyl group introduction reaction can be withdrawn through pipe (4), and the target carbonyl compound can be obtained in this reaction liquid. The materials, sizes, etc. of each flow path and confluence used in the flow reaction can be appropriately selected taking into account the desired reaction scale.

[0042] In the reaction of the present invention, when the active hydrogen-containing compound is, for example, a polyhydric alcohol compound, a polyamine compound, or a polythiol compound, the polymerization reaction of the resulting carbonyl compound can be allowed to proceed over time by extending the reaction time, thereby producing an oligomer or polymer. For example, when a diol is used as the active hydrogen-containing compound, a polycarbonate compound can be obtained by appropriately adjusting the reaction time, reaction temperature, reaction pressure, etc. In other words, the quaternary ammonium salt represented by the general formula (1) or (2) not only has excellent catalytic activity for the carbonyl group introduction reaction, but can also function as a polymerization catalyst for the compound into which the carbonyl group has been introduced by this reaction. Therefore, according to the production method of the present invention, a monomeric carbonyl compound, a polymeric (dimer or higher oligomer or polymer) carbonyl compound, or a mixture thereof can be appropriately obtained depending on the purpose.

[0043] <Solvent> When a solvent is used in the reaction of the present invention, a solvent capable of dissolving raw materials such as the active hydrogen-containing compound and the carbonate diester compound, as well as the carbonyl compound product, is preferred. Examples of such solvents include halogen-containing solvents, ether solvents having a linear, branched, or cyclic structure, and hydrocarbon solvents. Examples of halogen-containing solvents include methylene chloride, chloroform, dichloroethane, carbon tetrachloride, chlorobenzene, and o-dichlorobenzene. Examples of ether solvents include tetrahydrofuran, dioxane, methyl tertiary butyl ether, cyclopentyl methyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and derivatives thereof. Examples of hydrocarbon solvents include hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, mesitylene, decalin, tetralin, and derivatives thereof. Further, as the solvent, ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, methyl isobutyl ketone, etc., nitrile solvents such as acetonitrile, lactone solvents such as γ-butyrolactone, ester solvents such as ethyl acetate, butyl acetate, etc., amide solvents such as dimethylacetamide, dimethylformamide, etc. The above solvents may be used alone or in combination of two or more.

[0044] The present invention will be described in more detail based on examples, but the present invention should not be construed as being limited to these examples except as defined in the present invention.

[0045] Example 1 A batch reaction was carried out as follows. A 50 mL eggplant-shaped flask was charged with 1.8 g (20 mmol) of C-1 below as an active hydrogen-containing compound, 18.0 g (200 mmol) of dimethyl carbonate as a carbonate diester compound, and 0.348 g (1 mmol) of A-1 below as a catalyst, and the mixture was reacted at 100°C for 1 hour under reflux conditions in the atmosphere. The reaction solution was cooled to room temperature, and the components present in the reaction solution were analyzed by gas chromatography. Based on this analysis, the ratios (area %) of the peak areas of a compound in which only one of the two hydroxy groups in C-1 was converted to a methyl carbonate group (mono-substituted compound), a compound in which both hydroxy groups were converted to methyl carbonate groups (di-substituted compound), and unreacted C-1 (unsubstituted compound) to the total peak area were measured, and the conversion rate of the hydroxy groups in C-1 to methyl carbonate groups was calculated using the following formula. As a result, the conversion rate was 96%. Conversion rate (%)=100×[(area %) of monosubstituted compound+(area %) of disubstituted compound×2] / [(area %) of unsubstituted compound×2+(area %) of monosubstituted compound×2+(area %) of disubstituted compound×2]

[0046] Example 2 A batchwise reaction was carried out in the same manner as in Example 1, except that 23.6 g of diethyl carbonate was used instead of dimethyl carbonate as the carbonate diester compound. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in C-1 to ethyl carbonate groups was calculated.

[0047] Example 3 A batchwise reaction was carried out in the same manner as in Example 1, except that 34.8 g of dibutyl carbonate was used instead of dimethyl carbonate as the carbonate diester compound. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in C-1 to butyl carbonate groups was calculated.

[0048] Example 4 A batchwise reaction was carried out in the same manner as in Example 1, except that 42.8 g of diphenyl carbonate was used instead of dimethyl carbonate as the carbonate diester compound. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in C-1 to phenyl carbonate groups was calculated.

[0049] Example 5 A batch reaction was carried out in the same manner as in Example 1, except that 8.76 g of the following C-2 was used as the active hydrogen-containing compound instead of the above C-1. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in the above C-2 to methyl carbonate groups was calculated.

[0050] Example 6 A batch reaction was carried out in the same manner as in Example 5, except that 0.252 g of the following A-2 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0051] Example 7 A batch reaction was carried out in the same manner as in Example 5, except that 0.166 g of the following A-3 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0052] Example 8 A batch reaction was carried out in the same manner as in Example 5, except that 0.404 g of the following A-4 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0053] Example 9 A batch reaction was carried out in the same manner as in Example 5, except that 0.474 g of the following A-5 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0054] Example 10 A batch reaction was carried out in the same manner as in Example 5, except that 0.363 g of the following A-6 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0055] Example 11 A batch reaction was carried out in the same manner as in Example 5, except that 0.308 g of the following A-7 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0056] Example 12 A batchwise reaction was carried out in the same manner as in Example 5, except that 0.474 g of the following A-8 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0057] Example 13 A batchwise reaction was carried out in the same manner as in Example 5, except that 0.312 g of the following A-9 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0058] Example 14 A batch reaction was carried out in the same manner as in Example 5, except that 0.424 g of the following A-10 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0059] Example 15 A batch reaction was carried out in the same manner as in Example 5, except that 0.400 g of the following A-11 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated. In Example 15, the catalyst A-11 was not dissolved in the reaction solution but was present as solid particles, and the reaction solution was in the form of a slurry.

[0060] Example 16 A flow reaction was carried out as follows using the flow reaction system shown in FIG. 1 . Dimethyl carbonate was fed from inlet (Ia) into flow path (1) (SUS tubing, inner diameter 1.00 mm, length 500 mm, temperature 30°C) at a rate of 0.35 mL / min, and a cyclopentyl methyl ether solution (0.033 g / mL) of C-2 was fed from inlet (Ib) into flow path (2) (SUS tubing, inner diameter 1.00 mm, length 500 mm, temperature 30°C) at a rate of 5.9 mL / min. The two solutions were mixed at confluence (3) (a stainless steel (SUS) T-shaped mixer (inner diameter 0.5 mm, temperature 130°C)). This mixture was passed through a SUS column (inner diameter 10 mm, length 100 mm, temperature 130°C) packed with the solid catalyst A-11 described below, allowing the carbonyl group introduction reaction to proceed inside the column. The reaction solution that had passed through the column was analyzed by liquid chromatography (detection wavelength: 254 nm), and the conversion rate of the hydroxy group in C-2 to a methyl carbonate group was calculated in the same manner as above. As a result, the conversion rate was 99%.

[0061] Example 17 A flow reaction was carried out in the same manner as in Example 16, except that the active hydrogen-containing compound C-3 below was used instead of C-2 above, and a cyclopentyl methyl ether solution of this C-3 (0.017 g / mL) was fed into flow path (2) at a rate of 5.9 mL / min. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in C-3 to methyl carbonate groups was calculated.

[0062] Example 18 A flow reaction was carried out in the same manner as in Example 16, except that the active hydrogen-containing compound C-4 below was used instead of C-2 above, and a cyclopentyl methyl ether solution of this C-4 (0.020 g / mL) was fed into flow path (2) at a rate of 5.9 mL / min. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in C-4 to methyl carbonate groups was calculated.

[0063] Example 19 A flow reaction was carried out in the same manner as in Example 18, except that a cyclopentyl methyl ether solution (0.1 g / mL) of diphenyl carbonate was fed at a rate of 2.3 mL / min instead of dimethyl carbonate as the carbonate diester compound. The reaction solution was analyzed, and the conversion rate of the hydroxy group in C-4 to a phenyl carbonate group was calculated.

[0064] Example 20 A flow reaction was carried out in the same manner as in Example 16, except that the active hydrogen-containing compound C-5 below was used instead of C-2 above, and a cyclopentyl methyl ether solution of this C-5 (0.020 g / mL) was fed into flow path (2) at a rate of 5.9 mL / min. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in C-5 to methyl carbonate groups was calculated.

[0065] Example 21 A flow reaction was carried out in the same manner as in Example 16, except that the active hydrogen-containing compound C-6 was used instead of C-2, and a cyclopentyl methyl ether solution of C-6 (0.023 g / mL) was fed into flow path (2) at a rate of 5.9 mL / min. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in C-6 to methyl carbonate groups was calculated.

[0066] Example 22 A batchwise reaction was carried out in the same manner as in Example 5, except that 0.34 g of the following A-12 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0067] Example 23 A batchwise reaction was carried out in the same manner as in Example 1, except that 4.56 g of the following C-3 was used instead of the above C-1 as the active hydrogen-containing compound, and 0.412 g of the following A-13 was used instead of the above A-1 as the catalyst. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in the above C-3 to methyl carbonate groups was calculated.

[0068] Example 24 A batch reaction was carried out in the same manner as in Example 1, except that 5.36 g of the following C-4 was used instead of the above C-1 as the active hydrogen-containing compound, and 0.484 g of the following A-14 was used instead of the above A-1 as the catalyst. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in the above C-4 to methyl carbonate groups was calculated.

[0069] Example 25 A batch reaction was carried out in the same manner as in Example 1, except that 6.20 g of the following C-6 was used instead of the above C-1 as the active hydrogen-containing compound, and 0.393 g of the following A-15 was used instead of the above A-1 as the catalyst. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in the above C-6 to methyl carbonate groups was calculated.

[0070] Example 26 A batchwise reaction was carried out in the same manner as in Example 5, except that 0.440 g of the following A-16 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0071] Example 27 A batch reaction was carried out in the same manner as in Example 1, except that 3.00 g of the following C-7 was used instead of the above C-1 as the active hydrogen-containing compound. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-7 to a methyl carbonate group was calculated. Note that, since the above C-7 is a monoalcohol (monohydric phenol compound), the calculation formula for the conversion rate in Example 27 is as follows: Conversion rate (%) = 100 × [(area %) of substituted product] / [(area %) of unsubstituted product + (area %) of substituted product]

[0072] Example 28 A batchwise reaction was carried out in the same manner as in Example 27, except that 3.16 g of the following C-8 was used as the active hydrogen-containing compound instead of the above C-1. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in the above C-8 to methyl carbonate groups was calculated.

[0073] Example 29 A batch reaction was carried out in the same manner as in Example 27, except that 2.14 g of the following C-9 was used instead of the above C-1 as the active hydrogen-containing compound. The reaction solution was analyzed, and the conversion rate of the amino group in the above C-9 to a methyl carbonate group was calculated.

[0074] Example 30 A batchwise reaction was carried out in the same manner as in Example 27, except that 1.98 g of the following C-10 was used as the active hydrogen-containing compound instead of the above C-1. The reaction solution was analyzed, and the conversion rate of the amino groups in the above C-10 to methyl carbonate groups was calculated.

[0075] Example 31 A batchwise reaction was carried out in the same manner as in Example 27, except that 3.48 g of the following C-11 was used instead of the above C-1 as the active hydrogen-containing compound. The reaction solution was analyzed, and the conversion rate of the thiol group in the above C-11 to a methyl carbonate group was calculated.

[0076] Example 32 A batchwise reaction was carried out in the same manner as in Example 1, except that 0.172 g of the following A-17 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in the above C-1 to methyl carbonate groups was calculated.

[0077] Example 33 A batchwise reaction was carried out in the same manner as in Example 1, except that 0.160 g of the following A-18 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy groups in the above C-1 to methyl carbonate groups was calculated.

[0078] Comparative Example 1 A batch reaction was carried out in the same manner as in Example 5, except that 0.166 g of the following A-101 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0079] Comparative Example 2 A batch reaction was carried out in the same manner as in Example 5, except that 0.278 g of the following A-102 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0080] Comparative Example 3 A batchwise reaction was carried out in the same manner as in Example 5, except that 0.727 g of the following A-103 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0081] Comparative Example 4 A batch reaction was carried out in the same manner as in Example 5, except that 0.612 g of the following A-104 was used as the catalyst instead of the above A-1. The reaction solution was analyzed, and the conversion rate of the hydroxy group in the above C-2 to a methyl carbonate group was calculated.

[0082]

[0083]

[0084] The results of the above examples and comparative examples are summarized in the table below.

[0085]

[0086] The above results show that even when a quaternary ammonium salt is used as a catalyst, if its chemical structure does not satisfy the requirements of the present invention, the efficiency of introducing a carbonyl group into an active hydrogen-containing compound is poor (Comparative Examples 1 to 4).In contrast, when an active hydrogen-containing compound is reacted with a carbonate diester compound in the presence of a quaternary ammonium salt represented by the above general formula (1) or (2), the efficiency of introducing a carbonyl group into the active hydrogen-containing compound is significantly improved, regardless of whether the reaction is performed in a batch or flow mode (Examples 1 to 33).

[0087] Example 34 A glass vessel (volume 5 mL) dedicated to microwave synthesis apparatus was filled with 0.36 g of the above C-1 as the active hydrogen-containing compound, 3.6 g of dimethyl carbonate as the carbonate diester compound, and 0.070 g of the above A-1 as the catalyst, and sealed with a septum. Subsequently, using a microwave reaction apparatus (Biotage Initiator+, maximum output 400 W), microwaves were irradiated while stirring the glass vessel, heating the liquid in the glass vessel to 130°C, and the reaction was carried out in that state for 15 minutes. The reaction solution was analyzed, and the conversion rate of the hydroxy group in C-1 to a methyl carbonate group was calculated, resulting in a conversion rate of 95%. This result demonstrates that by employing microwave heating, carbonyl groups can be introduced into active hydrogen-containing compounds with high efficiency in a short period of time.

[0088] Example 35 A 50 mL eggplant-shaped flask was charged with 1.8 g (20 mmol) of the above C-1 as an active hydrogen-containing compound, 18.0 g (200 mmol) of dimethyl carbonate as a carbonate diester compound, and 0.348 g (1 mmol) of the above A-1 as a catalyst, and the mixture was reacted at 100°C under reflux conditions in the atmosphere for 1 hour. The mixture was then reacted at 110°C for 1 hour under atmospheric pressure, followed by 1.5 hours at 150°C under reduced pressure (20 Torr). The reaction solution was cooled to room temperature and analyzed by gel permeation chromatography. A polymer having a weight-average molecular weight of 5100 was formed. This result demonstrates that by appropriately controlling the reaction conditions, it is possible to obtain a low molecular weight carbonyl compound (monomer) and a polymer (prepolymer or polymer) of this low molecular weight carbonyl compound.

[0089] While the present invention has been described in connection with embodiments thereof, we do not intend to limit our invention to any of the details of the description unless otherwise specified, and believe that the claims should be construed broadly without departing from the spirit and scope of the invention as set forth in the appended claims.

[0090] This application claims priority based on Japanese Patent Application No. 2024-018711, filed on February 9, 2024, the contents of which are incorporated herein by reference as part of the present specification.

[0091] 10 Flow type reaction system Ia Ib Inlet 1 2 Flow path 3 Junction 4 Piping C1 Solid phase catalyst (solid catalyst packed in a column)

Claims

1. A method for producing a carbonyl compound, comprising reacting an active hydrogen-containing compound having an active hydrogen-containing group in the molecule, the active hydrogen-containing group being formed by bonding a hydrogen atom to an atom selected from oxygen, nitrogen, and sulfur atoms, with a carbonic acid diester compound in the presence of a quaternary ammonium salt represented by the following general formula (1) or (2), thereby introducing a carbonyl group into the active hydrogen-containing compound: In the general formulas (1) and (2), R １ R represents an organic group with a formula weight of 65 or more. ２ ~R ４ represents an alkyl group, and R ２ ~R ４ At least two of R are alkyl groups having 6 or less carbon atoms. ５ represents an alkyl group having 1 to 20 carbon atoms, and n is an integer of 0 to 2. － indicates a counter ion.

2. In the general formulas (1) and (2), the R １ The method for producing a carbonyl compound according to claim 1, wherein represents an alkyl group having 5 to 30 carbon atoms or a polymer structure.

3. In the general formulas (1) and (2), the R １ The method for producing a carbonyl compound according to claim 2, wherein is a polymer structure having a crosslinked structure.

4. The method for producing a carbonyl compound according to claim 3, wherein the quaternary ammonium salt is present as a solid in the reaction system of the reaction.

5. The method for producing a carbonyl compound according to claim 4, wherein the reaction is carried out in a flow reaction system.

6. A method for producing a carbonyl compound according to claim 5, comprising passing a liquid containing the active hydrogen-containing compound and the carbonic acid diester compound through a column packed with the quaternary ammonium salt.

7. In the general formula (1), R ２ ~R ４ The method for producing a carbonyl compound according to any one of claims 1 to 6, wherein at least two of the above are methyl.

8. In the general formulas (1) and (2), Y － is selected from a halide anion, a sulfonate anion, a phosphate anion, a phosphonate anion, a perchlorate anion, and a fluorophosphate anion.

9. The method for producing a carbonyl compound according to any one of claims 1 to 6, wherein the carbonic acid diester compound is a dialkyl carbonate compound.

10. The method for producing a carbonyl compound according to claim 9, wherein the carbonic acid diester compound is dimethyl carbonate.

11. The method for producing a carbonyl compound according to any one of claims 1 to 6, wherein the active hydrogen-containing compound is selected from the group consisting of polyhydric alcohol compounds, polyhydric amine compounds, and polyhydric thiol compounds.

12. The method for producing a carbonyl compound according to claim 11, wherein the carbonyl compound obtained by the method is a monomer and / or a polymer.

13. A method for producing a carbonyl compound according to any one of claims 1 to 6, comprising heating the reaction system of the reaction by irradiating it with microwaves.

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