Process for producing a carbonyl compound

Abstract

A method for manufacturing a carbonyl compound includes the following steps: reacting an active hydrogen-containing compound having an active hydrogen group formed by the bonding of hydrogen atoms with atoms selected from oxygen, nitrogen, and sulfur atoms within the molecule with a carbonate 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 Represents an organic group with a molecular weight of 65 or higher. R 2 ~R 4 R represents an alkyl group. 2 ~R 4 At least two of them are alkyl groups with six or fewer carbon atoms. R 5 Y represents an alkyl group with 1 to 20 carbon atoms, where n is an integer from 0 to 2. ‑ Indicates counterions.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a carbonyl compound. Background Technology

[0002] Halogenated carbonyl compounds, such as phosgene, are known as reactants for introducing carbonyl groups into various compounds containing active hydrogen. For example, isocyanate compounds and urea compounds can be obtained by reacting phosgene with primary amines. Furthermore, carbonate compounds and chloroformate compounds can be obtained by reacting phosgene with alcohols. Additionally, chlorothiocarbamates can be obtained by reacting phosgene with thiols. However, halogenated carbonyl compounds are highly toxic and are often gaseous at room temperature, requiring careful handling.

[0003] To introduce a carbonyl group into a compound containing active hydrogen without using a halogenated carbonyl compound, methods are known to react a diester compound, such as diphenyl carbonate, with an electron-withdrawing leaving group with an active hydrogen compound. Furthermore, the use of dialkyl carbonates having lower alkyl groups instead of diphenyl carbonates has been investigated. For example, Patent Document 1 describes the following: [Me(nC] quaternary ammonium salts with a specific structure ([Me(nC)]...] 12 H 25 )3N] + [OCO2Me] - The transesterification reaction of dimethyl carbonate with 1-adamantanol, a tertiary alcohol, was carried out in the presence of (Me: methyl). In the method described in Patent Document 1, methanol, as a byproduct, has a low boiling point and is therefore easily removed from the reaction system.

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2012-106982 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] The objective of this invention is to provide a method for manufacturing carbonyl compounds, which involves reacting a diester compound with a compound containing active hydrogen to more efficiently introduce a carbonyl group into the compound containing active hydrogen, thereby obtaining the target carbonyl compound with high efficiency.

[0009] means for solving technical problems

[0010] The inventors have repeatedly studied methods to efficiently introduce carbonyl groups into compounds containing active hydrogen by reacting carbonate diesters with such compounds. As a result, they discovered that the catalytic activity of quaternary ammonium salts, as described in Patent Document 1, is insufficient; however, by setting a specific combination of the four substituents of the quaternary ammonium salt, the efficiency of introducing carbonyl groups into the active hydrogen-containing compounds can be significantly improved. This invention was completed based on further repeated research based on these insights.

[0011] The above-mentioned problems of the present invention are solved by the following solution.

[0012] [1]

[0013] A method for manufacturing a carbonyl compound includes the following steps: reacting an active hydrogen compound having an active hydrogen group formed by the bonding of hydrogen atoms with atoms selected from oxygen atoms, nitrogen atoms and sulfur atoms within the molecule with a carbonate 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 above-mentioned active hydrogen compound.

[0014] [Chemical Formula 1]

[0015] In the above general formulas (1) and (2), R1 represents an organic group with a molecular weight of 65 or more. R2 to R4 represent alkyl groups, and at least two of R2 to R4 are alkyl groups with 6 or fewer carbon atoms. R5 represents an alkyl group with 1 to 20 carbon atoms, and n is an integer from 0 to 2. Y- represents a counter ion.

[0016] [2]

[0017] According to the method for manufacturing carbonyl compounds described in [1], wherein, In the above general formulas (1) and (2), R1 represents an alkyl or polymer structure with 5 to 30 carbon atoms.

[0018] [3]

[0019] According to the method for manufacturing carbonyl compounds described in [1] or [2], wherein, In the above general formulas (1) and (2), R1 is a polymer structure with a cross-linked structure.

[0020] [4]

[0021] The method for manufacturing a carbonyl compound according to any one of [1] to [3], wherein, The above quaternary ammonium salt is present in the reaction system of the above reaction in solid form.

[0022] [5]

[0023] The method for manufacturing a carbonyl compound according to any one of [1] to [4], wherein, The above reaction is carried out in a flow reaction system.

[0024] [6]

[0025] The method for manufacturing the carbonyl compound according to [5] includes the following steps: The liquid containing the above-mentioned active hydrogen compound and the above-mentioned diester compound is circulated in a column filled with the above-mentioned quaternary ammonium salt.

[0026] [7]

[0027] The method for manufacturing a carbonyl compound according to any one of [1] to [6], wherein, In the above general formula (1), at least two of R2 to R4 are methyl groups.

[0028] [8]

[0029] The method for manufacturing a carbonyl compound according to any one of [1] to [7], wherein, In the above general formulas (1) and (2), Y- is selected from halide anions, sulfonic acid anions, phosphate anions, phosphonic acid anions, perchloric acid anions and fluorophosphate anions.

[0030] [9]

[0031] The method for manufacturing a carbonyl compound according to any one of [1] to [8], wherein, The aforementioned diester compound is a dialkyl carbonate compound.

[0032]

[10]

[0033] According to the method for manufacturing carbonyl compounds described in [9], wherein, The aforementioned carbonate diester compound is dimethyl carbonate.

[0034]

[11]

[0035] The method for manufacturing a carbonyl compound according to any one of [1] to

[10] , wherein, The above-mentioned active hydrogen compounds are selected from polyol compounds, polyamine compounds, and polythiols.

[0036]

[12]

[0037] The method for manufacturing a carbonyl compound according to any one of [1] to

[11] , wherein, The carbonyl compounds obtained by the above manufacturing method are monomers and / or polymers.

[0038]

[13]

[0039] The method for producing the carbonyl compound according to any one of [1] to

[12] includes the step of heating the reaction system of the above reaction by irradiating it with microwaves.

[0040] In this invention, the numerical range represented by “~” refers to the range including the values ​​recorded before and after “~” as the lower limit and upper limit values.

[0041] In this invention, the term "substituted or unsubstituted group" includes groups having any substituents to the extent that they do not impair the target effect. For example, "alkyl" refers to a group containing both substituted and unsubstituted alkyl groups. Similarly, "phenyl" refers to a group containing both substituted and unsubstituted phenyl groups.

[0042] Invention Effects

[0043] According to the method for producing carbonyl compounds of the present invention, the carbonyl group can be introduced more efficiently into the carbonyl group by reacting a diester compound with a compound containing active hydrogen, thereby obtaining the target carbonyl compound with high efficiency. Attached Figure Description

[0044] Figure 1 The attached figure is a schematic representation of an example of a flow reaction system. Detailed Implementation

[0045] [Methods for manufacturing carbonyl compounds]

[0046] The method for producing the carbonyl compound of the present invention (hereinafter referred to as "the method of the present invention") includes the following steps: introducing a carbonyl group into the aforementioned compound by reacting a compound having an active hydrogen group (containing an active hydrogen compound) formed by bonding a hydrogen atom to an atom selected from oxygen, nitrogen, and sulfur atoms within the molecule with a diester compound in the presence of a quaternary ammonium salt with a specific structure. The reaction of introducing a carbonyl group into the active hydrogen compound by reacting an active hydrogen compound with a diester compound is itself known. The present invention is characterized by using a quaternary ammonium salt with a specific structure described later, the catalytic activity of which is currently unknown. The detailed description of the method of the present invention will now be provided.

[0047] (Contains active hydrogen compounds)

[0048] There are no particular limitations on compounds containing active hydrogen, as long as they have active hydrogen in their molecules. For example, compounds having at least one group selected from -OH, -COOH, -NH2, -NHR (where R is a substituent), and -SH can be widely used. Compounds containing active hydrogen include, for example, at least one of primary amine compounds, secondary amine compounds, hydroxyl compounds (the term "hydroxyl compound" is used to encompass both compounds with alcoholic hydroxyl groups and compounds with phenolic hydroxyl groups), thiols, carboxylic acid compounds, and amino acid compounds, with preference given to at least one of primary amine compounds, secondary amine compounds, hydroxyl compounds, and thiols.

[0049] The molecular weight of the active hydrogen-containing compound is preferably 40 to 1000, more preferably 60 to 500.

[0050] When the carbonyl compound obtained by the manufacturing method of the present invention is used as a monomer or prepolymer (when used as a raw material for a polymer), the aforementioned active hydrogen-containing compound can be selected from polyhydroxy compounds (compounds having two or more hydroxyl groups), polyamine compounds (compounds having two or more amino groups (preferably unsubstituted amino groups)), and polythiols (compounds having two or more thiol groups), wherein, preferably, it is selected from diol compounds (the two hydroxyl groups of the diol compound can be alcoholic or phenolic), diamine compounds, and dithiols. For example, when the carbonyl compound obtained by the manufacturing method of the present invention is used as a monomer or prepolymer for obtaining a polycarbonate compound, a polyhydroxy compound can be used as the aforementioned active hydrogen-containing compound, and a diol compound is preferred. Furthermore, for example, when the carbonyl compound obtained by the manufacturing method of the present invention is used as a monomer or prepolymer for obtaining a polyurea compound, a polyamine compound can be used as the aforementioned active hydrogen-containing compound, and a diamine compound is more preferred. Furthermore, when used as a monomer or prepolymer for obtaining a polythioamide compound, a polythiol can be used as the aforementioned active hydrogen-containing compound, and a dithiol compound is more preferred. Furthermore, a variety of the above-mentioned active hydrogen compounds (e.g., diol compounds and diamine compounds) can be used, or multiple active hydrogens (e.g., hydroxyl and amino groups) can be present in the same compound.

[0051] <Dice carbonate compounds>

[0052] Dicarbonate compounds are composed of R a OC (=O) - OR b The compound represented by R. a and R b This indicates a substituent, preferably alkyl or aryl. R a With R b They can be the same or different, but the same is preferred.

[0053] As R a and R b The alkyl group that can be used preferably has 1 to 10 carbon atoms, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 4, and even more preferably 1 to 3. As R a and R b When the alkyl group has 3 or more carbon atoms, it can be straight-chain or branched. As R a and R b The alkyl group that can be used is further preferably methyl or ethyl, and even more preferably methyl.

[0054] As R a and R b The aryl group that can be used is preferably phenyl or naphthyl, and more preferably phenyl.

[0055] Within the scope that does not impair the effects of the present invention, as R a and R b The alkyl or aryl groups that can be used (preferably phenyl or naphthyl) may have substituents. As R a and R b The alkyl or aryl groups that can be used are preferably unsubstituted alkyl or unsubstituted aryl groups.

[0056] The aforementioned diester compounds are preferably dialkyl carbonate compounds or diphenyl carbonate compounds. From the viewpoint of being able to react with compounds containing active hydrogen at a lower temperature while efficiently removing byproducts, dialkyl carbonate compounds with 1 to 4 carbon atoms in the alkyl group are preferred, more preferably diethyl carbonate (which produces low-boiling-point ethanol as a byproduct) or dimethyl carbonate (which produces low-boiling-point methanol as a byproduct), and even more preferably dimethyl carbonate. Furthermore, when using dialkyl carbonate compounds, from the viewpoint of carbonyl group introduction efficiency, diethyl carbonate or dimethyl carbonate are also preferred, and more preferably dimethyl carbonate.

[0057] Quaternary ammonium salts

[0058] In the manufacturing method of the present invention, a quaternary ammonium salt represented by the following general formula (1) or (2) is used as a reaction catalyst to react the above-mentioned active hydrogen compound with the above-mentioned diester compound.

[0059] [Chemical Formula 2]

[0060] In the above general formulas (1) and (2), R 1 Represents an organic group with a molecular weight of 65 or higher. R 2 ~R 4 R represents an alkyl group. 2~R 4 At least two of them are alkyl groups with six or fewer carbon atoms. R 5 Y represents an alkyl group with 1 to 20 carbon atoms, where n is an integer from 0 to 2. - Indicates counterions.

[0061] As mentioned above, R 1 The organic group with a chemical formula weight of 65 or more is preferably an alkyl group, an aromatic group, or a polymer structure. As described above, R... 1 The organic groups with a chemical formula weight of 65 or more are preferably organic groups with a chemical formula weight of 70 or more.

[0062] As mentioned above, R 1 There are no particular restrictions on the alkyl groups that can be used, as long as their molecular weight is 65 or higher. Therefore, as the aforementioned R... 1 The alkyl group that can be used is an alkyl group with 5 or more carbon atoms, preferably an alkyl group with 5 to 30 carbon atoms, more preferably an alkyl group with 6 to 28 carbon atoms, even more preferably an alkyl group with 8 to 26 carbon atoms, and particularly preferably an alkyl group with 10 to 24 carbon atoms. As described above, R... 1 The alkyl group that can be used can be straight-chain or branched. As for the aforementioned R... 1 When the alkyl group used has a branched chain, the number of branches is preferably one (one branched structure) or two (two branched structures), more preferably one branched structure. Without impairing the effects of the present invention, the above-mentioned R... 1 The alkyl group that can be used may have substituents. In this case, if the alkyl group containing the substituent has a total chemical weight of 65 or more, it is equivalent to the aforementioned "organic group with a chemical weight of 65 or more". As R 1 The alkyl group that can be used 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.

[0063] As mentioned above, R 1 The aromatic group that can be used is aryl or heteroaryl, preferably aryl. The aromatic group can be monocyclic or fused ring, preferably monocyclic. The number of ring members in the aromatic group (in the case of a fused ring, the number of ring members of each monocyclic ring constituting the fused ring) is preferably 5 or 6. The aromatic group is more preferably phenyl. Without impairing the effects of the present invention, the above-mentioned R... 1 The aromatic groups that can be used may have substituents.

[0064] In the case of quaternary ammonium salts represented by general formula (2), R 1 Preferably, it has an alkyl or polymer structure with a chemical formula weight of 65 or more.

[0065] As mentioned above, R 1The polymer structure that can be used is not particularly limited, as long as it is a polymer structure. This polymer structure can be a step-polymer 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 containing a styrene compound as a monomer component (a polystyrene compound structure) is preferably used as R... 1 Possible polymer structures. As for the aforementioned R... 1 The preferred polymer structure is a hydrocarbon structure (hydrocarbon polymer structure). Furthermore, as described above, R... 1 The polymer structure that can be used is preferably cross-linked. By introducing this cross-linked structure, in the manufacturing method of the present invention, it is also preferable to allow the above-mentioned quaternary ammonium salt to exist in a solid state in the reaction system so that the active hydrogen-containing compound reacts with the diester compound. In this case, the polymer structure also functions as a support for the catalyst.

[0066] In the above general formula (1) or (2), R 1 In the case of a polymer structure, the polymer structure preferably has one or more structural portions corresponding to the quaternary ammonium salt represented by the above general formula (1) or (2). That is, multiple quaternary ammonium salts represented by the above general formula (1) or (2) preferably share one polymer structure as each R 1 For example, in the quaternary ammonium salt "A-11" described in the later examples, corresponding to R 1 The polymer structure is a cross-linked polystyrene compound structure, which has multiple R elements removed from the above general formula (1). 1 The structural part. This structure is also included in the quaternary ammonium salt represented by the above general formula (1).

[0067] In R 1 In the case of a polymer structure, as R 1 The polymer structure can be bonded to the N atom in general formula (1) or (2) via a linker. In this case, the linker acts as R 1 The structure is positioned accordingly. For example, the quaternary ammonium salt "A-11" described in the later examples can be interpreted as -N + (Me)3 is bonded to the polystyrene compound structure via a methylene group, which can be interpreted as a group contained within the polystyrene compound structure. Alternatively, it can be interpreted as the -N group in the quaternary ammonium salt "A-11". + (Me)3 undergoes addition polymerization by direct bonding with p-methylstyrene, a styrene compound. According to this explanation, as R... 1 The polymer structure and -N +(Me)3 is directly bonded. Under any interpretation, 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.

[0068] As mentioned above, R 1 There are no particular limitations on the molecular weight of the polymer structures that can be used; they can be set appropriately. For example, the weight-average molecular weight can be set to 1,000 to 1,000,000.

[0069] As described above, R in the above general formula (1) 2 ~R 4 R represents an alkyl group. 2 ~R 4 At least two of them are alkyl groups having 6 or fewer carbon atoms. R is also preferred. 2 ~R 4 All are alkyl groups with 6 or fewer carbon atoms. As R 2 ~R 4 The alkyl group with 6 or fewer carbon atoms is preferably 5 or fewer carbon atoms, more preferably 4 or fewer carbon atoms, and even more preferably 3 or fewer carbon atoms. Ethyl or methyl groups are preferred, with methyl groups being particularly preferred. Therefore, R is preferred. 2 ~R 4 At least two of them are methyl groups.

[0070] In R 2 ~R 4 When one of the alkyl groups is an alkyl group with 7 or more carbon atoms, the carbon number of the alkyl group is preferably 7 to 30, more preferably 8 to 22, and even more preferably 10 to 22.

[0071] In R 2 ~R 4 When the alkyl group has 3 or more carbon atoms, it can be straight-chain or branched, with straight-chain alkyl groups being preferred. When branched, a single branched structure is preferred. In R 2 ~R 4 In this context, alkyl groups may have substituents within a range that does not impair the effects of the invention, but unsubstituted alkyl groups are preferred. Additionally, in R... 2 ~R 4 When the alkyl group has a substituent, the above number of carbon atoms refers to the total number of carbon atoms including the substituent.

[0072] As mentioned above, R in the above general formula (2) 5 R indicates an alkyl group having 1 to 20 carbon atoms. 5 The number of carbon atoms is preferably 1 to 18, more preferably 1 to 16, even more preferably 1 to 14, even more preferably 1 to 12, even more preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 6. As described above, R represents... 5The quantity n is 0 to 2, preferably 0 or 1. When n is 1 or 2, R 5 Preferably, it is bonded to the N atom constituting the pyridinium ring at the meta or para position. Furthermore, in the representation of R... 5 When the quantity n is 1, R 5 Preferably, it is bonded in the para position to the N atom constituting the pyridinium ring. In R 5 In this context, alkyl groups with 1 to 20 carbon atoms can be straight-chain or branched. Furthermore, in R... 5 In this invention, alkyl groups having 1 to 20 carbon atoms may have substituents within a range that does not impair the effects of the invention, but unsubstituted alkyl groups are preferred. Additionally, in R... 5 When the alkyl group has a substituent, the above number of carbon atoms refers to the total number of carbon atoms including the substituent.

[0073] Can be used as R 1 ~R 5 Each group is preferably a hydrocarbon structure as a whole.

[0074] Can be used as Y - There are no particular limitations on the counter ion (anion). For example, counter ions selected from halide anions, sulfonic acid anions, phosphate anions, phosphonic acid anions, perchloric acid anions, and fluorophosphate anions (preferably tetrafluorophosphate or hexafluorophosphate anions) can be used as Y. - The preferred counter ion is a halide anion. Bromine or chloride ions are preferred as halide anions.

[0075] Preferred examples of quaternary ammonium salts represented by the above general formula (1) or (2) are shown below. Me represents methyl, Bu represents n-butyl, and OTs represents toluenesulfonate anion.

[0076] [Chemical Formula 3]

[0077] <Carbonyl Introduction Reaction>

[0078] In the manufacturing method of the present invention, a quaternary ammonium salt with a specific structure represented by the above general formula (1) or (2) is used as a reaction catalyst to react the above-mentioned active hydrogen compound with the above-mentioned diester carbonate compound (this reaction is referred to as "the reaction of the present invention"). By applying the above-mentioned quaternary ammonium salt, when using diphenyl carbonate with a high electron-withdrawing leaving group as the carbonyl group supply source, the efficiency of carbonyl compound introduction into the above-mentioned active hydrogen compound can be further improved, and even when using dialkyl carbonate with a low electron-withdrawing leaving group, the efficiency of carbonyl group introduction into the above-mentioned active hydrogen compound can be sufficiently improved. The reason for this is not yet clear, but it is believed that one of the reasons is that the quaternary ammonium salt has a structure represented by the above general formula (1) or (2), which reduces steric hindrance at a specific site while increasing solubility or affinity for the raw material at another site, thereby maximizing the efficiency of the catalytic action.

[0079] The reaction of the above-mentioned active hydrogen-containing compound with the above-mentioned diester carbonate compound to introduce a carbonyl group into the above-mentioned active hydrogen-containing compound is itself well known. As an example, two reaction formulas for the reaction of diester carbonate compound with monool compound are shown below. R A OC (=O) - OR A For example, it can be set as dimethyl carbonate or diphenyl carbonate (R). A (Methyl or phenyl), R B -OH is, for example, 1-decyl alcohol (R) B : guiji).

[0080] R 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 the first formula's "R" A OC (=O) - OR B "and the second formula "R B OC (=O) - OR B"All of them can be identified as the target carbonyl compound in this invention. Furthermore, the formation of the target carbonyl compound is an equilibrium reaction with the starting material; therefore, by controlling the "R" as the starting material..." A OC (=O) - OR A "and "R B The ratio of -OH, reaction time, reaction temperature, or concentration can be controlled to act as "R". A OC (=O) - OR B "and "R B OC (=O) - OR B The ratio of the mixture to be formed.

[0081] Moreover, in this invention, by using the quaternary ammonium salt represented by the above general formula (1) or (2) as a reaction catalyst, the generation efficiency of the target carbonyl compound can be significantly improved.

[0082] As examples of reactions different from those described above, the following show three examples of reaction formulas for carbonate diesters and diols. R A The meaning is the same as above, HO-L B -OH is, for example, 1,4-butanediol (L... B (Adenky).

[0083] R 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)-OL B -OH+2R A -OH The above shows three reaction formulas, the first formula "R"A OC (=O) - OL B -OH”, the second formula “R” A OC (=O) - OL B -OC (=O) -OR A "and the third form "HO-L" B -OC(=O)-OL B "-OH" can all be positioned as the target carbonyl compound in this invention (e.g., a monomer used to obtain polycarbonate). Furthermore, by controlling the "R" as a raw material... A OC (=O) - OR A "and "HO-L B The composition of the reaction products can also be controlled by factors such as the ratio of -OH, reaction time, reaction temperature, or concentration.

[0084] Moreover, by using the quaternary ammonium salt represented by the above general formula (1) or (2) as the reaction catalyst, the generation efficiency of the target carbonyl compound can be significantly improved.

[0085] Furthermore, the reactions of the present invention are equilibrium reactions. For example, by reacting the diester compound in excess, the equilibrium of the above reaction formulas can be shifted to the right, thereby generating the target carbonyl compound more efficiently.

[0086] Regarding the reaction between the diester compound and the diol compound, the types of products actually obtained are not limited to those shown in the above reaction formula. For example, if dimethyl carbonate is used as the diester compound and the diol compound is C-2 as used in the examples described later, the reaction of the present invention can produce the following reaction products, including unreacted compounds. All reaction products except the unreacted diol compound are identified as the target carbonyl compounds in the present invention. Furthermore, by adjusting the reaction conditions, compounds that further polymerize the following reaction products to become oligomers or polymers can also be included in the reaction products.

[0087] [Chemical Formula 4]

[0088] In the above, an example of a reaction formula when a hydroxyl compound is used as a compound containing active hydrogen has been described. However, when the compound containing active hydrogen is a compound other than a hydroxyl compound (amine compound, thiol compound, etc.), reaction products are also generated according to the above reaction formula, as will be understood by those skilled in the art.

[0089] In the reaction of the present invention, the molar ratio of the active hydrogen compound to the diester carbonate compound is not particularly limited as long as the target reaction is carried out. As a molar ratio, for example, it is preferably set to [active hydrogen compound] / [diester carbonate compound] = 1 / 100 to 1 / 0.1, more preferably set to [active hydrogen compound] / [diester carbonate compound] = 1 / 30 to 1 / 1, even more preferably set to [active hydrogen compound] / [diester carbonate compound] = 1 / 20 to 1 / 2, and also preferably set to [active hydrogen compound] / [diester carbonate compound] = 1 / 10 to 1 / 3.

[0090] In the reaction of the present invention, the amount of the quaternary ammonium salt (catalyst) represented by the above general formula (1) or (2) present in the reaction system is not particularly limited as long as it is the amount required to catalyze the target reaction. As a molar ratio, for example, it is preferably set to [catalyst] / [diesel carbonate compound] = 1 / 10 to 1 / 10000, more preferably set to [catalyst] / [diesel carbonate compound] = 1 / 10 to 1 / 2000, even more preferably set to [catalyst] / [diesel carbonate compound] = 1 / 10 to 1 / 1000, and also preferably set to [catalyst] / [diesel carbonate compound] = 1 / 12 to 1 / 500.

[0091] While the reaction temperature of the present invention also depends on the type of diester carbonate compound used, it is preferably carried out in the range of 70 to 250°C. This temperature is preferably set above the boiling point of the byproduct alcohol, phenol, etc. Therefore, when dimethyl carbonate is used as the diester carbonate, the byproduct is methanol with a low boiling point, so even if the reaction is carried out at a low temperature, the methanol byproduct can be removed efficiently. Furthermore, by carrying out the reaction under reduced pressure, the byproduct is removed more easily. If the reduction of environmental impact is considered while ensuring reaction efficiency, the above-mentioned reaction temperature is more preferably 70 to 220°C, more preferably 80 to 200°C, and even more preferably 80 to 150°C. In the reaction of the present invention, the quaternary ammonium salt represented by the above general formula (1) or (2) is used as the reaction catalyst, so it is possible to appropriately apply diester carbonate compounds that can remove byproducts at this reaction temperature.

[0092] The reaction temperature is preferably controlled by irradiating the reaction system with microwaves. Heating by microwave irradiation allows for efficient acquisition of the target carbonyl compound, even with a shortened reaction time (e.g., approximately one-quarter or less of the heating time compared to oil bath-based heating). The microwaves can be single-mode or multi-mode. Furthermore, heating can be performed using either an electric field or a magnetic field.

[0093] The reaction time of the present invention is not particularly limited as long as the target reaction can be carried out. For example, it can be set to 1 minute to 10 hours. In batch reactions, it is preferred to set it to 5 minutes to 10 hours, but it can also be set to 20 minutes to 5 hours, or preferably 30 minutes to 3 hours.

[0094] Furthermore, when using the flow-type reaction described later, carbonyl compounds can be obtained efficiently in a shorter reaction time. Therefore, when using a flow-type reaction, it is preferable to set the reaction time to 5 seconds to 30 minutes, or 10 seconds to 20 minutes, or preferably 30 seconds to 10 minutes.

[0095] When the reaction of the present invention is carried out in a batch manner, the above-mentioned active hydrogen compound, the above-mentioned diester compound, and the quaternary ammonium salt represented by the above-mentioned general formula (1) or (2) can be added to the reaction vessel and the reaction can be carried out at the above-mentioned reaction temperature. For example, the reaction can be carried out while heating under atmospheric reflux conditions. A solvent can be used appropriately, but if the raw materials are liquid under the reaction conditions, a solvent-free reaction system can also be set up.

[0096] When the reaction of the present invention is carried out in a flow-type manner, it is preferable to use the quaternary ammonium salt represented by the above general formula (1) or (2) as a solid-phase catalyst (solid catalyst). For example, by using R of the above general formula (1) or (2) 1 By configuring it as a cross-linked polymer structure, the aforementioned quaternary ammonium salt can exist as a solid in the reaction system. That is, it enables R... 1 It functions as a carrier insoluble in the reaction solution. By packing this insoluble catalyst into a column and circulating the mixture of the aforementioned active hydrogen-containing compound and the aforementioned diester compound within the column, the reaction of introducing the carbonyl group of the aforementioned active hydrogen-containing compound takes place during the column flow. An example of a flow reaction system used to carry out this flow reaction is schematically shown below. Figure 1 In the middle. Additionally, if R 1 For a polymer structure to be insoluble in the reaction solution, it is not necessarily required to have a cross-linked structure. Such an insoluble polymer structure can be appropriately designed.

[0097] exist Figure 1 In the flow reaction system (10) shown, liquid I containing the above-mentioned active hydrogen compound is introduced into flow path (1) through inlet (Ia), and liquid II containing the above-mentioned carbonate diester compound is introduced into flow path (2) through inlet (Ib). A liquid delivery pump (not shown) such as a syringe pump or diaphragm pump is typically connected to inlets (Ia) and (Ib). By operating this pump, it is possible to configure the flow of each liquid in each flow path at a desired flow rate.

[0098] Liquid I and liquid II are combined in the confluence section (3), and the combined liquid is guided into a column (C1) filled with a catalyst insoluble in the above reaction liquid, thereby enabling the carbonyl introduction reaction of the above-mentioned active hydrogen compound to take place in the column (C1). The reaction liquid after the carbonyl introduction reaction can be taken out through the pipe (4), and the target carbonyl compound can be obtained in the reaction liquid.

[0099] The materials and dimensions of each flow path or confluence section used in a flow reaction can be appropriately set considering the target reaction scale.

[0100] In the reaction of the present invention, when the above-mentioned active hydrogen-containing compound is, for example, a polyol compound, a polyamine compound, or a polythiol compound, if the reaction time is extended, the polymerization reaction of the generated carbonyl compound can also proceed over time, and oligomers or polymers can also be obtained. For example, when a diol is used as the active hydrogen-containing compound, polycarbonate compounds can also be obtained by appropriately adjusting the reaction time, reaction temperature, reaction pressure, etc. That is, the quaternary ammonium salt represented by the above general formula (1) or (2) not only has excellent catalytic activity for carbonyl introduction reaction, but can also act as a polymerization catalyst for compounds incorporating carbonyl groups through this reaction. Therefore, according to the manufacturing method of the present invention, it is possible to appropriately obtain monomeric carbonyl compounds or polymeric carbonyl compounds (oligomers or polymers of more than one dimer) or mixtures thereof, depending on the purpose.

[0101] <Solvent>

[0102] When using a solvent in the reaction of the present invention, a solvent capable of dissolving the above-mentioned active hydrogen-containing compound, the above-mentioned diester compound, or the carbonyl compound of the product is preferred. Examples of such solvents include halogen-containing solvents, ether solvents having straight-chain, branched-chain, or cyclic structures, and hydrocarbon solvents.

[0103] Examples of halogenated solvents include dichloromethane, chloroform, dichloroethane, carbon tetrachloride, chlorobenzene, and o-dichlorobenzene.

[0104] Examples of ether solvents include tetrahydrofuran, dioxane, methyl tert-butyl ether, cyclopentyl methyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and their derivatives.

[0105] Examples of hydrocarbon solvents include hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, mesitylene, decahydronaphthalene, tetrahydronaphthalene, and their derivatives.

[0106] Furthermore, as the aforementioned solvents, ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, and methyl isobutyl ketone, nitrile solvents such as acetonitrile, lactone solvents such as γ-butyrolactone, ester solvents such as ethyl acetate and butyl acetate, and amide solvents such as dimethylacetamide and dimethylformamide can also be used.

[0107] The above solvents can be used alone or in combination of two or more solvents.

[0108] The present invention will be further described in detail with reference to the embodiments, but the present invention is not limited to these embodiments except as provided herein.

[0109] Example

[0110] [Example 1]

[0111] The batch reaction was carried out as follows.

[0112] In a 50 mL flask, 1.8 g (20 mmol) of C-1 was added as an active hydrogen compound, 18.0 g (200 mmol) of dimethyl carbonate was added as a diester compound, and 0.348 g (1 mmol) of A-1 was added as a catalyst. The reaction was carried out under reflux at 100 °C for 1 hour. 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 peak surface area (area %) of the compound in which only one of the two hydroxyl groups of C-1 was converted to a methyl carbonate group (monosubstituted), the compound in which both hydroxyl groups were converted to a methyl carbonate group (disubstituted), and the unreacted C-1 (unsubstituted) were determined relative to the total peak surface area. The conversion rate of the hydroxyl groups of C-1 to the methyl carbonate group was calculated using the following formula. The result showed that the conversion rate was 96%.

[0113] Conversion rate (%) = 100 × [(area percentage of monosubstituted product) + (area percentage of disubstituted product) × 2] / [(area percentage of unsubstituted product) × 2 + (area percentage of monosubstituted product) × 2 + (area percentage of disubstituted product) × 2]

[0114] [Example 2]

[0115] As the diester compound, 23.6 g of diethyl carbonate was used instead of dimethyl carbonate, and the batch reaction was carried out in the same manner as in Example 1. The reaction solution was analyzed, and the conversion rate of the hydroxyl group of C-1 to the ethyl carbonate group was calculated.

[0116] [Example 3]

[0117] As the carbonate diester compound, 34.8 g of dibutyl carbonate was used instead of dimethyl carbonate, and the batch reaction was carried out in the same manner as in Example 1. The reaction solution was analyzed, and the conversion rate of the hydroxyl group of C-1 to the butyl carbonate group was calculated.

[0118] [Example 4]

[0119] As the diester compound, 42.8 g of diphenyl carbonate was used instead of dimethyl carbonate, and the batch reaction was carried out in the same manner as in Example 1. The reaction solution was analyzed, and the conversion rate of the hydroxyl group to the phenyl carbonate group in C-1 was calculated.

[0120] [Example 5]

[0121] As a compound containing active hydrogen, 8.76 g of the following C-2 was used instead of C-1, and the batch reaction was carried out in the same manner as in Example 1. The reaction solution was analyzed, and the conversion rate of the hydroxyl group of the above-mentioned C-2 to the methyl carbonate group was calculated.

[0122] [Example 6]

[0123] As a catalyst, 0.252 g of A-2 described below was used instead of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups of C-2 to methyl carbonate groups was calculated.

[0124] [Example 7]

[0125] As a catalyst, 0.166 g of A-3 was used instead of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl group to the methyl carbonate group in C-2 was calculated.

[0126] [Example 8]

[0127] As a catalyst, 0.404 g of A-4 was used instead of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl group to the methyl carbonate group in C-2 was calculated.

[0128] [Example 9]

[0129] As a catalyst, 0.474 g of A-5 was used instead of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl group to the methyl carbonate group in C-2 was calculated.

[0130] [Example 10]

[0131] As a catalyst, 0.363 g of A-6 was used instead of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl group to the methyl carbonate group in C-2 was calculated.

[0132] [Example 11]

[0133] As a catalyst, 0.308 g of A-7 was used instead of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl group to the methyl carbonate group in C-2 was calculated.

[0134] [Example 12]

[0135] As a catalyst, 0.474 g of A-8 was used instead of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl group to the methyl carbonate group in C-2 was calculated.

[0136] [Example 13]

[0137] As a catalyst, 0.312 g of A-9 was used instead of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl group to the methyl carbonate group in C-2 was calculated.

[0138] [Example 14]

[0139] As a catalyst, 0.424 g of A-10 was used instead of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups to methyl carbonate groups in C-2 was calculated.

[0140] [Example 15]

[0141] As a catalyst, 0.400 g of A-11 was used instead of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups to methyl carbonate groups in C-2 was calculated. In addition, in Example 15, A-11, as a catalyst, was not dissolved in the reaction solution but existed in the form of solid particles, and the reaction solution was in slurry form.

[0142] [Example 16]

[0143] use Figure 1 The flow reaction system shown is implemented as follows.

[0144] Dimethyl carbonate was fed into flow path (1) (SUS tubing, 1.00 mm inner diameter, 500 mm length, 30 °C) at a rate of 0.35 mL / min through inlet (Ia), and the above-mentioned C-2 cyclopentyl methyl ether solution (0.033 g / mL) was fed into flow path (2) (SUS tubing, 1.00 mm inner diameter, 500 mm length, 30 °C) at a rate of 5.9 mL / min through inlet (Ib). The two liquids were mixed through confluence section (3) (a stainless steel (SUS) T-mixer (0.5 mm inner diameter, 130 °C)). The carbonyl introduction reaction was carried out inside the column by passing the mixture through an SUS column (10 mm inner diameter, 100 mm length, 130 °C) filled with A-11 as a solid catalyst. The reaction solution passing through the column was analyzed using liquid chromatography (detection wavelength: 254 nm), and the conversion rate of the hydroxyl group to the methyl carbonate group in C-2 was calculated in the same manner as described above. The result showed a conversion rate of 99%.

[0145] [Example 17]

[0146] Using C-3 instead of C-2 as the active hydrogen-containing compound, a cyclopentyl methyl ether solution of C-3 (0.017 g / mL) was fed into flow path (2) at a rate of 5.9 mL / min. Otherwise, the flow reaction was carried out in the same manner as in Example 16. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups of C-3 to methyl carbonate groups was calculated.

[0147] [Example 18]

[0148] Using C-4 instead of C-2 as the active hydrogen-containing compound, a cyclopentyl methyl ether solution of C-4 (0.020 g / mL) was fed into flow path (2) at a rate of 5.9 mL / min. Otherwise, the flow reaction was carried out in the same manner as in Example 16. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups of C-4 to methyl carbonate groups was calculated.

[0149] [Example 19]

[0150] The flow-through reaction was carried out in the same manner as in Example 18, except that a solution of diphenyl carbonate in cyclopentyl methyl ether (0.1 g / mL) was used at a flow rate of 2.3 mL / min instead of dimethyl carbonate as the carbonate compound. The reaction solution was analyzed, and the conversion rate of the hydroxyl group to the phenyl carbonate group in C-4 was calculated.

[0151] [Example 20]

[0152] Using C-5 instead of C-2 as the active hydrogen-containing compound, a cyclopentyl methyl ether solution of C-5 (0.020 g / mL) was fed into flow path (2) at a rate of 5.9 mL / min. Otherwise, the flow reaction was carried out in the same manner as in Example 16. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups of C-5 to methyl carbonate groups was calculated.

[0153] [Example 21]

[0154] Using C-6 instead of C-2 as the active hydrogen-containing compound, 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. Otherwise, the flow reaction was carried out in the same manner as in Example 16. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups of C-6 to methyl carbonate groups was calculated.

[0155] [Example 22]

[0156] The catalyst was A-12 (0.34 g) described below, which was used in place of A-1. Otherwise, the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups of C-2 to methyl carbonate groups was calculated.

[0157] [Example 23]

[0158] 4.56 g of the following C-3 was used instead of C-1 as the active hydrogen compound, and 0.412 g of the following A-13 was used instead of A-1 as the catalyst. Otherwise, the batch reaction was carried out in the same manner as in Example 1. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups of the above-mentioned C-3 to methyl carbonate groups was calculated.

[0159] [Example 24]

[0160] The following C-4 was used instead of C-1 as the active hydrogen compound, and 0.484 g of the following A-14 was used instead of A-1 as the catalyst. Otherwise, the batch reaction was carried out in the same manner as in Example 1. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups of the above-mentioned C-4 to methyl carbonate groups was calculated.

[0161] [Example 25]

[0162] The following C-6 was used instead of C-1 as the active hydrogen compound, and 0.393 g of the following A-15 was used instead of A-1 as the catalyst. Otherwise, the batch reaction was carried out in the same manner as in Example 1. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups of the above-mentioned C-6 to methyl carbonate groups was calculated.

[0163] [Example 26]

[0164] The catalyst was A-16 (0.440 g) described below, used in place of A-1. Otherwise, the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups to methyl carbonate groups in C-2 was calculated.

[0165] [Example 27]

[0166] Using 3.00 g of the following C-7 instead of the above-mentioned C-1 as the active hydrogen-containing compound, the batch reaction was carried out in the same manner as in Example 1. The reaction solution was analyzed, and the conversion rate of the hydroxyl group of the above-mentioned C-7 to the methyl carbonate group was calculated. In addition, the above-mentioned C-7 is a monool (a 1-valent phenolic compound), therefore the conversion rate calculation formula in Example 27 is as follows.

[0167] Conversion rate (%) = 100 × [(area of ​​substituted product %)] / [(area of ​​unsubstituted product %) + (area of ​​substituted product %)]

[0168] [Example 28]

[0169] 3.16 g of the following C-8 was used instead of the above-mentioned C-1 as the active hydrogen-containing compound, and the batch reaction was carried out in the same manner as in Example 27. The reaction solution was analyzed, and the conversion rate of the hydroxyl group of the above-mentioned C-8 to the methyl carbonate group was calculated.

[0170] [Example 29]

[0171] Using 2.14 g of the following C-9 instead of the above C-1 as the active hydrogen-containing compound, the batch reaction was carried out in the same manner as in Example 27. The reaction solution was analyzed and the conversion rate of the amino group to the methyl carbonate group of the above C-9 was calculated.

[0172] [Example 30]

[0173] 1.98 g of the following C-10 was used instead of the above-mentioned C-1 as the active hydrogen-containing compound, and the batch reaction was carried out in the same manner as in Example 27. The reaction solution was analyzed, and the conversion rate of the amino group to the methyl carbonate group of the above-mentioned C-10 was calculated.

[0174] [Example 31]

[0175] 3.48 g of the following C-11 was used instead of the above-mentioned C-1 as the active hydrogen-containing compound. Otherwise, the batch reaction was carried out in the same manner as in Example 27. The reaction solution was analyzed and the conversion rate of the thiol group to the methyl carbonate group of the above-mentioned C-11 was calculated.

[0176] [Example 32]

[0177] The catalyst was A-17 (0.172 g) described below, which was used in place of A-1 above. Otherwise, the batch reaction was carried out in the same manner as in Example 1. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups to methyl carbonate groups in C-1 above was calculated.

[0178] [Example 33]

[0179] The catalyst was A-18 (0.160 g) described below, used in place of A-1, and the batch reaction was carried out in the same manner as in Example 1. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups to methyl carbonate groups in C-1 was calculated.

[0180] [Comparative Example 1]

[0181] The catalyst was A-101 (0.166 g) described below, used in place of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups to methyl carbonate groups in C-2 was calculated.

[0182] [Comparative Example 2]

[0183] The catalyst was A-102 (0.278 g) described below, used in place of A-1. Otherwise, the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups to methyl carbonate groups in C-2 was calculated.

[0184] [Comparative Example 3]

[0185] The catalyst was A-103 (0.727 g) described below, used in place of A-1. Otherwise, the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups to methyl carbonate groups in C-2 was calculated.

[0186] [Comparative Example 4]

[0187] The catalyst was A-104 (0.612 g) described below, used in place of A-1, and the batch reaction was carried out in the same manner as in Example 5. The reaction solution was analyzed, and the conversion rate of the hydroxyl groups to methyl carbonate groups in C-2 was calculated.

[0188] [Chemical Formula 5]

[0189] [Chemical Formula 6]

[0190] The results of the above embodiments and comparative examples are summarized in the table below.

[0191] [Table 1]

[0192] The results above show that even when using quaternary ammonium salts as catalysts, if their chemical structure does not meet the requirements of this invention, the efficiency of introducing carbonyl groups into compounds containing active hydrogen is poor (Comparative Examples 1-4).

[0193] In contrast, it was shown that when a quaternary ammonium salt represented by the above general formula (1) or (2) is reacted with a diester compound containing active hydrogen, the efficiency of introducing carbonyl groups into the active hydrogen compound is significantly improved regardless of whether the reaction is batch or flow-through (Examples 1-33).

[0194] [Example 34]

[0195] A 5 mL glass container specifically designed for microwave synthesis was filled with 0.36 g of C-1 (as the active hydrogen compound), 3.6 g of dimethyl carbonate (as the diester compound), and 0.070 g of A-1 (as the catalyst), and sealed with a diaphragm. The container was then heated to 130°C using a microwave reactor (Initiator+ manufactured by Biotage Japan Ltd., maximum output 400W) while stirring, and allowed to react for 15 minutes. Analysis of the reaction mixture and calculation of the conversion rate of the hydroxyl groups in C-1 to the methyl carbonate groups showed a conversion rate of 95%. This result demonstrates that microwave heating enables efficient and rapid introduction of carbonyl groups into the active hydrogen compound.

[0196] [Example 35]

[0197] 1.8 g (20 mmol) of the above-mentioned C-1 as the active hydrogen compound, 18.0 g (200 mmol) of dimethyl carbonate as the diester compound, and 0.348 g (1 mmol) of the above-mentioned A-1 as the catalyst were packed into a 50 mL flask and reacted at 100 °C for 1 hour under atmospheric reflux. The reaction was then carried out at 110 °C for 1 hour under atmospheric pressure, followed by a reaction under reduced pressure (20 Torr) at 150 °C for 1.5 hours. The reaction solution was cooled to room temperature and analyzed by gel permeation chromatography, yielding a polymer with a weight-average molecular weight of 5100. This result indicates that by appropriately controlling the reaction conditions, low-molecular-weight carbonyl compounds (monomers) or polymers (prepolymers or polymers) containing such low-molecular-weight carbonyl compounds can be obtained.

[0198] The invention has been described in conjunction with its embodiments, but we believe that, unless otherwise specified, the invention should not be limited to any details in the description, but should be interpreted broadly without departing from the spirit and scope of the invention as set forth in the appended claims.

[0199] This application claims priority based on Japanese Patent Application 2024-018711, filed in Japan on February 9, 2024, the contents of which are incorporated herein by reference and are part of the description herein.

[0200] Symbol Explanation

[0201] 10 - Flow reaction system, Ia, Ib - Inlet, 1, 2 - Flow path, 3 - Merging section, 4 - Piping, C1 - Solid catalyst (solid catalyst packed in the column).

Claims

1. A method for manufacturing a carbonyl compound, comprising the steps of: reacting an active hydrogen compound with a 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 compound, wherein the active hydrogen compound has an active hydrogen group formed by hydrogen atoms bonded to atoms selected from oxygen, nitrogen and sulfur atoms within the molecule. [Chemical Formula 1] In the general formulas (1) and (2), R 1 R represents an organic group with a chemical formula weight of 65 or higher. 2 ~R 4 R represents an alkyl group. 2 ~R 4 At least two of them are alkyl groups with 6 or fewer carbon atoms, R 5 Represents alkyl groups with 1 to 20 carbon atoms, where n is an integer from 0 to 2, and Y - Indicates counterions.

2. The method for manufacturing the carbonyl compound according to claim 1, wherein, In the general formulas (1) and (2), the R 1 It represents alkyl or polymer structures with 5 to 30 carbon atoms.

3. The method for manufacturing the carbonyl compound according to claim 2, wherein, In the general formulas (1) and (2), the R 1 It is a polymer structure with cross-linking.

4. The method for manufacturing the carbonyl compound according to claim 3, wherein, The quaternary ammonium salt is present in the reaction system in solid form.

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

6. The method for manufacturing the carbonyl compound according to claim 5, comprising the following steps: The liquid containing the active hydrogen compound and the carbonate diester compound is circulated within a column filled with the quaternary ammonium salt.

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

8. The method for producing the carbonyl compound according to any one of claims 1 to 6, wherein, In the general formulas (1) and (2), Y - Selected from halide anions, sulfonic acid anions, phosphate anions, phosphonic acid anions, perchloric acid anions, and fluorophosphate anions.

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

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

11. The method for producing the carbonyl compound according to any one of claims 1 to 6, wherein, The active hydrogen-containing compound is selected from polyol compounds, polyamine compounds, and polythiols.

12. The method for producing the carbonyl compound according to claim 11, wherein, The carbonyl compound obtained by the manufacturing 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 the step of heating the reaction system by irradiating it with microwaves.

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