US-12623999-B2 - Carbamate production method, carbamate ester production method, and urea derivative production method

Abstract

A method for producing a carbamic acid salt, including contacting a carbon dioxide-containing mixed gas having a partial pressure of carbon dioxide of 0.001 atm or more and less than 1 atm with an amino group-containing organic compound in the presence of a base in at least one organic solvent selected from the group consisting of an organic solvent having 2 or more and 8 or less carbon atoms, and a method for producing a carbamic acid ester or a urea derivative using the carbamic acid salt.

Inventors

• Katsuhiko Takeuchi
• Kazuhiro Matsumoto
• Norihisa Fukaya
• Hiroki Koizumi
• Jun-Chul Choi
• Masahito Uchida
• Seiji Matsumoto
• Satoshi Hamura

Assignees

• NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY
• TOSOH CORPORATION

Dates

Publication Date

20260512

Application Date

20210603

Priority Date

20200605

Claims (11)

1. 1 . A method for producing a carbamic acid ester, comprising a reaction step of producing a carbamic acid ester having a structure represented by the following formula (a-1) or (a-2), from a carbamic acid salt and a metal alkoxide: in the formulae, R 1b each independently represents a hydrogen atom, or an unsubstituted or a substituted monovalent hydrocarbon group, R 2b and R 3b each independently represents an unsubstituted or a substituted monovalent hydrocarbon group, and R 20b represents an unsubstituted or a substituted divalent hydrocarbon group.
2. 2 . The method for producing a carbamic acid ester according to claim 1 , wherein the carbamic acid salt is a carbamic acid salt represented by formula (B-1), the metal alkoxide is a metal alkoxide represented by formula (C-1), and the carbamic acid ester having the structure represented by the formula (a-1) is a carbamic acid ester represented by formula (A-1): in the formulae, R 11b represents a hydrogen atom, or an unsubstituted or a substituted monovalent hydrocarbon group; R 21b and R 31b each independently represents an unsubstituted or a substituted monovalent hydrocarbon group; R 41b each independently represents an unsubstituted or a substituted hydrocarbon ligand, an unsubstituted or a substituted alkoxy ligands, amide ligands, and halide ligands different from —OR 31b ; M represents a metal atom or a semimetal atom; n2 represents the oxidation number of M and (n2−m2) is an integer of 1 to 6; m2 represents an integer of 0 or more and (n2−1) or less; Q b represents a q2-valent counter cation; and q2 is 1 or 2.
3. 3 . The method for producing a carbamic acid ester according to claim 2 , wherein Q b is a cation selected from the group consisting of an ammonium cation, an amidinium cation, a guanidinium cation, a phosphonium cation, a phosphazenium cation, a carbocation, an alkali metal cation, and an alkaline earth metal cation.
4. 4 . The method for producing a carbamic acid ester according to claim 1 , wherein the carbamic acid salt is a carbamic acid salt represented by formula (B-2), the metal alkoxide is a metal alkoxide represented by formula (C-2), and the carbamic acid ester having the structure represented by the formula (a-2) is a carbamic acid ester represented by formula (A-2): in the formulae, R 12b each independently represents a hydrogen atom, or an unsubstituted or a substituted monovalent hydrocarbon group; R 22b represents an unsubstituted or a substituted divalent hydrocarbon group; R 32b each independently represents an unsubstituted or a substituted monovalent hydrocarbon group; R 42b each independently represents an unsubstituted or a substituted hydrocarbon ligand, an unsubstituted or a substituted alkoxy ligands, amide ligands, and halide ligands different from —OR 32b ; M′ represents a metal atom or a semimetal atom; n2′ represents the oxidation number of M′ and (n2′−m2′) is an integer of 1 to 6; m2′ represents an integer of 0 or more and (n2′−1) or less; Q b′ represents a (2/q2′)-valent counter cation; and q2′ is 1 or 2.
5. 5 . The method for producing a carbamic acid ester according to claim 4 , wherein Q b′ is a cation selected from the group consisting of an ammonium cation, an amidinium cation, a guanidinium cation, a phosphonium cation, a phosphazenium cation, a carbocation, an alkali metal cation, and an alkaline earth metal cation.
6. 6 . The method for producing a carbamic acid ester according to claim 1 , wherein the metal alkoxide is at least one selected from the group consisting of a titanium compound and a silicon compound.
7. 7 . The method for producing a carbamic acid ester according to claim 1 , wherein the metal alkoxide is an alkoxysilane, and the reaction step is performed in the presence of a catalyst.
8. 8 . The method for producing a carbamic acid ester according to claim 7 , wherein the catalyst is at least one selected from the group consisting of an organic base carboxylic acid salt, an alkali metal salt, a zinc compound, a titanium(IV) compound, and a zirconium(IV) compound.
9. 9 . The method for producing a carbamic acid ester according to claim 1 , wherein the reaction step is performed in the presence of an aprotic solvent.
10. 10 . The method for producing a carbamic acid ester according to claim 1 , further comprising a carbamic acid salt production step of contacting an amino group-containing organic compound with a carbon dioxide-containing mixed gas in the presence of a base in a solvent to produce the carbamic acid salt, wherein a volume of carbon dioxide in the carbon dioxide-containing mixed gas is 0.01% or more.
11. 11 . The method for producing a carbamic acid ester according to claim 1 , wherein the carbamic acid salt is produced by contacting a carbon dioxide-containing mixed gas having a partial pressure of carbon dioxide of 0.001 atm or more and less than 1 atm with an amino group-containing organic compound in the presence of a base in at least one organic solvent selected from the group consisting of an organic solvent having 2 or more and 8 or less carbon atoms.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS The present application is a 35 U.S.C. § 371 national stage patent application of International patent application PCT/JP2021/021188, filed on Jun. 3, 2021, which is based on and claims the benefits of priority to Japanese Application No. 2020-098388, filed on Jun. 5, 2020, Japanese Application No. 2020-098490, filed on Jun. 5, 2020, Japanese Application No. 2020-098497, filed on Jun. 5, 2020, Japanese Application No. 2021-027268, filed on Feb. 24, 2021, and Japanese Application No. 2021-027277, filed on Feb. 24, 2021. The entire contents of all of the above applications are incorporated herein by reference. TECHNICAL FIELD The present invention relates to a method for producing a carbamic acid salt, a method for producing a carbamic acid ester, and a method for producing a urea derivative. BACKGROUND ART Carbamic acid salts are useful compounds having a wide range of applications for medical drugs, agricultural chemicals, various fine chemicals, and synthetic raw materials thereof. There have been heretofore studied methods for synthesizing carbamic acid salts from amines and CO2. For example, Patent Document 1 relates to a method for producing a carbamate (carbamic acid ammonium salt) from CO2 in a flue gas, in which N-(2-aminoethyl)carbamate is obtained as a white crystal by introducing (bubbling) an exhaust gas having a content of CO2 of 5 to 21% by volume, into a 0.75 to 1.00 mol/L ethylenediamine/methanol solution under ice bath conditions at 0° C.±1° C., and separating, washing, and purifying a reaction product. Patent Document 2 discloses a method for producing a carbamic acid derivative powder, which is a method for obtaining various ammonium carbamates as solids by reacting carbon dioxide and various liquid amines such as ethylenediamine and benzylamine in solvents under conditions of a temperature range from −30 to 500° C. and a pressure range from 0.3 to 100 MPa. Patent Document 3 relates to an absorber and a generator of air-derived carbon dioxide, and discloses a method for absorbing carbon dioxide in the air by leaving a specific alkylamine substituted with a hydroxy group or an amino group which may be substituted, in an air atmosphere. Non-Patent Document 1 reports a synthesis of ammonium carbamate which is a novel carbamic acid-based ionic liquid by reacting various primary to tertiary amines in solvents in the presence of an organic super strong base such as diazabicycloundecene (DBU (registered trademark)), tetramethylguanidine (TMG) and/or the like under a carbon dioxide atmosphere at a temperature ranging from room temperature to 40° C. and a pressure of 5 to 60 bar, as well as studies about the reaction conditions. Carbamic acid esters are known as derivatives of carbamic acid salts. Carbamic acid esters are useful compounds having a wide range of applications for medical drugs, agricultural chemicals, various fine chemicals, and synthetic raw materials thereof. There have been heretofore proposed methods for producing carbamic acid esters by use of carbon dioxide at ordinary pressure. For example, Non-Patent Document 2 studies as a method for synthesizing a carbamate derivative, a multicomponent synthesis using ammonium carbamate synthesized in situ from a reaction of amine and CO2, as a carbonyl source, a stoichiometric amount of triphenylphosphine, and a stoichiometric amount of trichloroisocyanuric acid (TCCA). In Non-Patent Document 2, a CO2 gas at 1 atm is used and a non-renewable sacrificial reagent is used. Non-Patent Document 3 reports a method for synthesizing a carbamic acid ester via a carbamic acid by use of a CO2 gas at 1 atm and 1,8-diazabicyclo[5.4.0]undec-7-ene as a catalyst. In Non-Patent Document 3, PBu3 and DBAD (di-tert-butyl azodicarboxylate) as non-renewable sacrificial reagents are used. Non-Patent Document 4 reports a synthesis of a carbamic acid ester from amine and a CO2 gas by use of KO2/Et4NBr or the like as a non-renewable sacrificial reagent. Non-Patent Document 5 reports a synthesis of a carbamic acid ester via a carbamic acid according to the Mitsunobu reaction by use of a CO2 gas at 1 atm and Ph3P and DEAD (diethyl azodicarboxylate) as sacrificial reagents. Urea derivatives are known as analogs of carbamic acid salts. Urea derivatives are useful compounds having a wide range of applications for medical drugs, agricultural chemicals, various fine chemicals, and synthetic raw materials thereof. For example, 1,3-dimethyl-2-imidazolidinone, N,N′-dimethylpropylene urea, and the like as aprotic polar solvents can be used as alternative solvents for carcinogenic HMPA (hexamethylphosphoric triamide). Ethylene urea is used in woven finishing materials, paints, and the like. For example, urea derivatives having the following structure, as anti-HIV agents, are reported as basic skeletons of pharmaceutical products. Urea derivatives have been conventionally produced industrially by reacting amines and ureas or phosgenes. Ho