WO2014092161A1 - Procédé de production de composé carbamate - Google Patents

Procédé de production de composé carbamate Download PDF

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WO2014092161A1
WO2014092161A1 PCT/JP2013/083369 JP2013083369W WO2014092161A1 WO 2014092161 A1 WO2014092161 A1 WO 2014092161A1 JP 2013083369 W JP2013083369 W JP 2013083369W WO 2014092161 A1 WO2014092161 A1 WO 2014092161A1
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group
carbon atoms
compound
bis
carbamate
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PCT/JP2013/083369
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Japanese (ja)
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克生 鈴木
麻友美 荒木
吉田　洋一
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宇部興産株式会社
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Priority to JP2014552087A priority Critical patent/JP6292124B2/ja
Priority to CN201380065090.6A priority patent/CN104837813B/zh
Publication of WO2014092161A1 publication Critical patent/WO2014092161A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups

Definitions

  • the present invention relates to a method for producing a carbamate compound by reacting a carbonate compound and an amine compound.
  • the carbamate compound is useful as a raw material for producing an isocyanate compound, for example.
  • a method for producing a carbamate compound a method using phosgene has been known.
  • a method of reacting an amine compound and a carbonate compound for example, see Patent Document 1 has become popular. It has been studied.
  • Patent Document 1 in the presence of a basic catalyst containing a metal, the total amount of water contained in the carbonate ester and the amine is controlled to 0.001 to 50 ppm together with the carbamate ester.
  • a method for producing a reaction product containing the metal is disclosed.
  • Patent Document 2 discloses a method for producing a carbamate compound by reacting an amine compound and a carbonate compound using a hydrolase catalyst.
  • Patent Document 1 a large amount of basic metal impurities are mixed unless the water content is controlled to a very low value of 0.001 to 50 ppm. There was a problem of coming. This method is thus unsuitable as an industrial production method because it requires complicated operations such as strict control of moisture.
  • the method of Patent Document 2 has a problem of enzyme degradation, and it is difficult to say that it is an industrially advantageous production method from the viewpoint of efficiency.
  • the object of the present invention is to solve the above-mentioned problems and to produce a carbamate compound having a quality suitable for the production of an isocyanate compound by reacting a carbonate compound and an amine compound without requiring a complicated operation.
  • An industrially suitable method for producing a carbamate compound is provided.
  • An object of the present invention is to react an amine compound and a carbonate compound in the presence of at least one base selected from the group consisting of alkali metal alkoxides and alkaline earth metal alkoxides, and then react the amino group of the amine compound. This is solved by a method for producing a carbamate compound, wherein 0.01 to 0.5 mol of water is added to 1 mol and further reacted.
  • a carbamate compound can be obtained with a high yield without requiring a complicated operation, and in particular, a carbamate compound with reduced impurities can be produced.
  • the amine compound and the carbonate compound are reacted in the presence of at least one base selected from the group consisting of alkali metal alkoxides and alkaline earth metal alkoxides, and then 1 mol of the amino group of the amine compound.
  • Carbamate compounds are obtained by adding 0.01 to 0.5 mol of water to the reaction mixture and further reacting.
  • the amine compound as a raw material of the present invention is an organic compound having one or more amino groups in one molecule, and is selected from alicyclic groups and aromatic groups having at least one amino group in the molecule.
  • An aliphatic amine optionally substituted with a group and / or interrupted with a group selected from an alicyclic group and an aromatic group; and having at least one amino group in the molecule; Examples include alicyclic amines that may be substituted with an aliphatic group.
  • the amino group in an amine compound means a primary amino group unless otherwise specified.
  • the amine compound may be substituted with an alicyclic group or aromatic group having at least one amino group in the molecule, or may be interrupted with an alicyclic group or aromatic group.
  • at least one amine compound selected from the group consisting of a good aliphatic amine and an alicyclic amine optionally having an aliphatic group and having at least one amino group in the molecule is used. .
  • an aliphatic amine is a compound having at least one primary amino group directly bonded to a carbon atom of an aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group includes an alicyclic group and an aromatic group. It may be substituted with a group selected from groups and / or interrupted with a group selected from alicyclic groups and aromatic groups.
  • the aliphatic hydrocarbon group is a hydrocarbon group which is linear or branched and may have an unsaturated bond, and is an alkyl group having 1 to 20 carbon atoms, 2 to 20 carbon atoms. And alkynyl groups having 2 to 20 carbon atoms.
  • the valence of the aliphatic hydrocarbon group can vary depending on the number of amino groups and the like. Thus, when a specific valence group is illustrated, other corresponding valence groups may also be used.
  • An aliphatic amine substituted with an alicyclic group is a compound in which the hydrocarbon group of the aliphatic amine defined above is substituted with an alicyclic group.
  • the alicyclic group is a hydrocarbon group containing a ring structure, for example, a saturated or unsaturated monocyclic or polycyclic (for example, 2 to 4 ring) hydrocarbon group having 3 to 20 carbon atoms in total.
  • the cycloalkyl group and the cycloalkenyl group include monocyclic or polycyclic residues.
  • examples of the aliphatic hydrocarbon group substituted with an alicyclic group include an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group having 3 to 20 carbon atoms.
  • An aliphatic amine substituted with an aromatic group is a compound in which the hydrocarbon group of the aliphatic amine defined above is substituted with an aromatic group, and is also referred to as an araliphatic.
  • the aromatic group is, for example, a hydrocarbon group having 6 to 20 carbon atoms and a monocyclic or polycyclic aromatic ring structure such as a benzene ring or a naphthalene ring.
  • examples of the aliphatic hydrocarbon group substituted with an aromatic group include an alkyl group having 1 to 20 carbon atoms substituted with an aryl group having 6 to 20 carbon atoms.
  • An aliphatic amine interrupted with an alicyclic group is a compound in which the carbon-carbon bond of the hydrocarbon group of the aliphatic amine defined above is interrupted with a divalent alicyclic group.
  • the divalent alicyclic group include a divalent group obtained by removing one hydrogen atom from the alicyclic group defined above.
  • a cycloalkylene group having 3 to 20 carbon atoms, a carbon atom examples thereof include a cycloalkenylene group of 3 to 20.
  • examples of the aliphatic hydrocarbon group interrupted by an alicyclic group include alkylene having 1 to 15 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, and alkylene group having 1 to 15 carbon atoms. It is done.
  • An aliphatic amine interrupted with an aromatic group is a compound in which the carbon-carbon bond of the hydrocarbon group of the aliphatic amine defined above is interrupted with a divalent aromatic group.
  • the divalent aromatic group include a divalent group obtained by removing one hydrogen atom from the aromatic group defined above, and examples thereof include an arylene group having 6 to 20 carbon atoms.
  • the aliphatic hydrocarbon group interrupted by an aromatic group include alkylene having 1 to 15 carbon atoms-arylene having 3 to 20 carbon atoms and alkylene group having 1 to 15 carbon atoms.
  • an alicyclic amine is a compound having one or more primary amino groups directly bonded to carbon atoms on the ring of a monocyclic or polycyclic alicyclic group, and an aliphatic group May be substituted.
  • Examples of the alicyclic group in the alicyclic amine include the same groups as the alicyclic group defined above.
  • the valency of the alicyclic group can vary depending on the number of primary amino groups and the like. Thus, when a specific valence group is illustrated, other corresponding valence groups may also be used.
  • the alicyclic amine substituted with an aliphatic group is a compound in which the alicyclic group of the alicyclic amine defined above is substituted with an aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group include the aliphatic hydrocarbon groups defined above.
  • the alicyclic group substituted with an aliphatic group include a cycloalkyl group having 3 to 20 carbon atoms substituted with an alkyl group having 1 to 20 carbon atoms.
  • An alicyclic amine having a primary amino group to be bound is included in the alicyclic amine.
  • the amine compound may contain, for example, a stable bond such as an ether bond or a thioether bond in its molecular skeleton, such as a halogen atom, an alkoxy group, a dialkylamino group, a cyano group, a nitro group, an acetyl group, an aromatic group. It may be substituted with a stable substituent such as an amino group directly bonded to a ring carbon atom.
  • a stable bond such as an ether bond or a thioether bond in its molecular skeleton, such as a halogen atom, an alkoxy group, a dialkylamino group, a cyano group, a nitro group, an acetyl group, an aromatic group. It may be substituted with a stable substituent such as an amino group directly bonded to a ring carbon atom.
  • the amine compound is preferably a compound having one or two primary amino groups.
  • an amine compound having one or two primary amino groups for example, the general formula (1):
  • R 1 may have a substituent, a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched chain group having 2 to 20 carbon atoms.
  • a monoamine compound having one amino group in the molecule represented by hereinafter referred to as “monoamine compound”), or the general formula (4):
  • R 3 is an optionally substituted linear or branched alkylene group having 1 to 20 carbon atoms, linear alkylene having 1 to 4 carbon atoms, and 3 to 20 carbon atoms.
  • diamine compound having two amino groups in the molecule hereinafter referred to as “diamine compound”).
  • Examples of the linear or branched alkyl group having 1 to 20 carbon atoms in R 1 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Examples include heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, isopropyl group, isobutyl group, t-butyl group, etc., preferably 1 carbon atom To 12 linear or branched alkyl groups, and more preferably methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-dodecyl, isopropyl and t- It is a butyl group.
  • Examples of the linear or branched alkenyl group having 2 to 20 carbon atoms in R 1 include an allyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, an isopropanyl group, and the like. Is a linear or branched alkenyl group having 2 to 12 carbon atoms, more preferably an allyl group.
  • Examples of the linear or branched alkynyl group having 2 to 20 carbon atoms in R 1 include an ethynyl group, a propargyl group, a butenyl group, a 1-methyl-2-propynyl group, and preferably a carbon atom.
  • a linear or branched alkynyl group of 2 to 12 is preferable, and an ethynyl group or a propargyl group is more preferable.
  • the cycloalkyl group having 3 to 20 carbon atoms in R 1 is a monocyclic or polycyclic group, and may be substituted with an alkyl group having 1 to 4 carbon atoms, and may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group or the like.
  • Examples of the cycloalkylalkyl group having 4 to 24 carbon atoms in R 1 include a linear alkyl group having 1 to 4 carbon atoms substituted with a cycloalkyl group having 3 to 20 carbon atoms as defined above. Examples thereof include a cyclohexylmethyl group, a cyclohexylethyl group, a trimethylcyclohexylmethyl group, a norbornylmethyl group, and the like. Preferably, it has 1 to 4 carbon atoms substituted with a cycloalkyl group having 3 to 10 carbon atoms. An alkyl group, more preferably a cyclohexylmethyl group.
  • Examples of the aralkyl group having 7 to 21 carbon atoms in R 1 include an alkyl group having 1 to 9 carbon atoms substituted with an aryl group having 6 to 12 carbon atoms.
  • Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, and a biphenyl group.
  • examples of the aralkyl group having 7 to 21 carbon atoms include a benzyl group, a phenethyl group, and a naphthylmethyl group, preferably an aralkyl group having 7 to 11 carbon atoms, and more preferably a benzyl group. . These groups include various isomers.
  • R 1 may have further substituents.
  • the further substituent in R 1 include an alkoxy group having 1 to 4 carbon atoms such as a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • R 1 is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, n-dodecyl, fluoromethyl, difluoromethyl, trifluoro It has a substituent such as methyl group, cyanomethyl group, nitromethyl group, fluoroethyl group, trifluoroethyl group, trichloroethyl group, cyanoethyl group, nitroethyl group, methoxyethyl group, ethoxyethyl group, t-butoxyethyl group, etc.
  • the monoamine compound represented by the general formula (1) preferably includes n-hexylamine, n-dodecylamine, cyclohexylmethylamine, and benzylamine.
  • Examples of the linear or branched alkylene group having 1 to 20 carbon atoms in R 3 include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, Linear alkylene groups such as n-heptylene group, n-octylene group, n-nonylene group, n-decylene group, n-dodecylene group, 2-methylpropylene group, 2-methylhexylene group, tetramethylethylene group
  • a branched alkylene group such as a linear alkylene group having 1 to 20 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.
  • the cycloalkylene group having 3 to 20 carbon atoms in R 3 is a monocyclic or polycyclic group and may be substituted with 1 to 4 carbon atoms, and may be a cyclopropylene group, a cyclobutylene group, or a cyclopentylene group.
  • Group, cyclohexylene group, and bicyclo [2.2.1] heptane-2,6-diyl group preferably a cycloalkylene group having 3 to 12 carbon atoms, more preferably a cyclohexylene group.
  • a bicyclo [2.2.1] heptane-2,6-diyl group A bicyclo [2.2.1] heptane-2,6-diyl group.
  • alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.
  • Straight chain alkylene having 1 to 4 carbon atoms-cycloalkylene having 3 to 20 carbon atoms-linear alkylene group having 1 to 4 carbon atoms include methylene-cyclopentylene-methylene group, ethylene- Examples thereof include cyclopentylene-ethylene group, methylene-cyclohexylene-methylene group, etc., preferably linear alkylene having 1 to 4 carbon atoms, cyclohexylene having 3 to 12 carbon atoms, and 1 to 1 carbon atoms. 4 linear alkylene group, more preferably methylene-cyclohexylene-methylene group.
  • the linear alkylene having 1 to 4 carbon atoms and the cycloalkylene group having 3 to 20 carbon atoms in R 3 is preferably a linear alkylene having 1 to 4 carbon atoms and having 1 to 4 carbon atoms.
  • the linear alkylene group having 1 to 4 carbon atoms—the arylene group having 6 to 20 carbon atoms—the linear alkylene group having 1 to 4 carbon atoms is preferably one having 1 to 4 carbon atoms.
  • the hydrocarbon group for R 3 may have a substituent.
  • substituents in R 3 include the same groups as the substituents of the hydrocarbon group in R 1 .
  • R 3 is straight-chain alkylene of 1 to 4 carbon atoms - from 6 to 20 carbon atoms arylene - if a straight-chain alkylene group having 1 to 4 carbon atoms, as the substituents for R 3 And a primary amino group directly bonded to the aromatic carbon atom of the arylene group.
  • R 3 is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, a linear alkylene group having 1 to 4 carbon atoms, and a cycloalkylene carbon having 3 to 20 carbon atoms.
  • a substituted cycloalkylene group having 3 to 12 carbon atoms more preferably a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, A dodecylene group, a cyclohexylene group, a methylene-trimethylcyclohexylene group, a cyclohexylenedimethylene group, and a xylylene group;
  • the amine compound that is the raw material of the present invention may be used alone or in combination of two or more.
  • the amine compound is preferably an amine compound having two amino groups from the viewpoint of obtaining a biscarbamate compound as a raw material for diisocyanate, and among them, a diamine compound represented by the general formula (4) is preferable, and 1,6- Hexamethylenediamine, 1,12-dodecamethylenediamine, isophoronediamine, 1,3-bis (aminomethylcyclohexane), 1,4-bis (aminomethylcyclohexane), 4,4'-methylenebis (cyclohexaneamine), 2, 5-bis (aminomethyl) bicyclo [2,2,1] heptane, 2,6-bis (aminomethyl) bicyclo [2,2,1] heptane, 1,3-bis (aminomethyl) benzene, 1,4 -Bis (aminomethyl) benzene, which may be used alone or in combination of
  • the carbonate compound as a raw material of the present invention is not particularly limited as long as it is a compound having a carbonate bond, and may be used alone or in combination of two or more.
  • carbonate compounds examples include general formula (2):
  • R 2 is a monovalent hydrocarbon group which may have a substituent).
  • Examples of the monovalent hydrocarbon group for R 2 include the same groups as those defined for R 1 defined in general formula (1).
  • the hydrocarbon group for R 2 is preferably a straight chain having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl or n-butyl, and more preferably 1 to 6 carbon atoms. Or it is a branched alkyl group, More preferably, it is a methyl group or an ethyl group.
  • the hydrocarbon group for R 2 may have a substituent.
  • substituent of the hydrocarbon group in R 2 include those having 1 to 4 carbon atoms such as halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), methoxy group, ethoxy group, propoxy group, butoxy group and the like.
  • dialkylamino group disubstituted with an alkyl group having 1 to 4 carbon atoms such as an alkoxy group, a dimethylamino group, a diethylamino group, and a dipropylamino group, a cyano group, and a nitro group.
  • the compound represented by the general formula (2) is preferably dimethyl carbonate or diethyl carbonate.
  • an amine compound and a carbonate compound are reacted in the presence of at least one base selected from the group consisting of alkali metal alkoxides and alkaline earth metal alkoxides, and then 1 mol of an amino group of the amine compound. Further, 0.01 to 0.5 mol of water is added to cause further reaction, and water can be allowed to act on the reaction mixture of the amine compound and the carbonate compound.
  • the amount of the carbonate compound used can be set such that the carbonate bond of the carbonate compound is 1 to 100 mol with respect to 1 mol of the amino group of the amine compound. 1 to 50 moles.
  • the method for producing a carbamate compound of the present invention is represented by the following reaction formula [I].
  • the monocarbamate compound represented by the general formula (3) is represented by the general formula (1) in the presence of at least one base selected from the group consisting of alkali metal alkoxides and alkaline earth metal alkoxides.
  • 0.01 to 0.5 mol of water is then added to 1 mol of the amino group of the amine compound and further reacted. Can be obtained.
  • reaction Formula II when an amine compound is a diamine compound, the manufacturing method of the carbamate compound of this invention is shown by following Reaction formula [II].
  • the biscarbamate compound represented by the general formula (5) is represented by the general formula (4) in the presence of at least one base selected from the group consisting of alkali metal alkoxides and alkaline earth metal alkoxides.
  • 0.01 to 0.5 mol of water is then added to 1 mol of the amino group of the amine compound and further reacted. Can be obtained.
  • the amount of the carbonate compound represented by the general formula (2) is preferably 1 to 100 moles, more preferably 1 to 50 moles per mole of the monoamine compound represented by the general formula (1). Mol, more preferably 2 to 20 mol, particularly preferably 2 to 10 mol. In the reaction formula [II], the amount of the carbonate compound represented by the general formula (2) is preferably 2 to 200 mol, more preferably 2 to 100, per 1 mol of the diamine compound represented by the general formula (4). Mol, more preferably 4 to 40 mol, particularly preferably 4 to 20 mol.
  • alkali metal alkoxides and alkaline earth metal alkoxides used in the present invention such as lithium methoxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide.
  • Alkaline metal alkoxides such as calcium methoxide, alkaline earth metal alkoxides such as calcium ethoxide, etc. are mentioned, preferably lithium methoxide, sodium methoxide, potassium methoxide, more preferably sodium methoxide, potassium methoxide. used.
  • These metal alkoxides can be used in the state of an alcohol solution, and can be used as a catalyst as they are even in the state of a commercially available alcohol solution.
  • the amount of the base used can be an amount that is 0.5 mol or less with respect to 1 mol of the amino group of the amine compound, and is preferably 0.0001 to 0.2 mol.
  • the amount of the base used is preferably 0.001 to 0.1 mol, more preferably 0.03 to 0.1 mol, relative to 1 mol of the amine compound.
  • the amount is preferably 0.01 to 0.2 mol, more preferably 0.03 to 0.2 mol, relative to 1 mol of the amine compound.
  • the water used in the reaction of the present invention is not particularly limited as long as it is generally available water.
  • it is purified in advance by distillation or the like to remove a small amount of impurities (metal ions, halogen ions, etc.) Purified water or distilled water is preferably used.
  • At least one base selected from the group consisting of alkali metal alkoxides and alkaline earth metal alkoxides, an amine compound and a carbonate compound are mixed, and preferably 20 ° C. to 90 ° C., more preferably After reacting with stirring at 40 ° C. to 90 ° C., the target carbamate compound is then reacted by adding 0.01 to 0.5 mol of water with respect to 1 mol of the amino group of the amine compound. Can be manufactured.
  • the reaction pressure is not particularly limited, but is preferably under normal pressure or reduced pressure.
  • the carbamate compound obtained by the reaction of the present invention (in the case of reaction formula [I], it is a monocarbamate compound represented by general formula (3), and in the case of reaction formula [II], a biscarbamate represented by general formula (6) Compound) is a carbamate compound with reduced impurities, particularly basic metal impurities such as alkali metals and alkaline earth metals.
  • the carbamate compound obtained by the reaction of the present invention can be isolated and purified by general methods such as distillation, liquid separation, extraction, crystallization, recrystallization, column chromatography, etc., and impurities are further reduced. In order to obtain the carbamate compound, it can be purified with an ion exchange resin or the like.
  • the carbamate compound obtained by the reaction of the present invention contains only 15 to 350 ppm of alkali metal and / or alkaline earth metal relative to the carbamate compound, which is useful as a raw material for producing an isocyanate compound. It is.
  • the isocyanate compound can be produced from the carbamate compound by a known method, and can be carried out by thermally decomposing the carbamate compound in the presence of a catalyst (for example, silicon oxide).
  • Target product (carbamate compound); gas chromatography or liquid column chromatography (internal standard method) Water; Karl Fischer moisture meter (MKC-610 type; manufactured by Kyoto Electronics Industry Co., Ltd.) Sodium; ICP-AES equipment (SPS5100 type; manufactured by SII Nanotechnology)
  • Example 3 Synthesis of 1,3-bis (methoxycarbonylaminomethyl) cyclohexane
  • Into a 300-mL flask equipped with a stirrer and a thermometer 36.4 g (255.9 mmol) of 1,3-bisaminomethylcyclohexane, 71.2 g (790.1 mmol) of dimethyl carbonate and 28% sodium methoxide, Methanol solution 1.5 g (7.9 mmol) was added. When the water content of the mixed solution at this time was measured, it was about 217 ppm. The mixture was reacted at 50 ° C. for 5 hours with stirring.
  • Example 4 Synthesis of 1,3-bis (methoxycarbonylaminomethyl) cyclohexane
  • 1,3-bisaminomethylcyclohexane dimethyl carbonate and 28% sodium methoxide / methanol solution
  • 107.8 g of acetone and 0.45 g (24.8 mmol) of purified water were used.
  • Example 5 Synthesis of 1,3-bis (methoxycarbonylaminomethyl) cyclohexane After reacting 1,3-bisaminomethylcyclohexane, dimethyl carbonate and a 28% sodium methoxide / methanol solution in the same manner as in Example 3, 26.0 g of n-propanol and 0.43 g (23. 7 mmol; 0.049 mol per mol of amino group of 1,3-bis (methoxycarbonylaminomethyl) cyclohexane) was added, and the mixture was further reacted at 50 ° C. for 30 minutes.
  • Example 6 Synthesis of 1,3-bis (methoxycarbonylaminomethyl) cyclohexane After reacting 1,3-bisaminomethylcyclohexane, dimethyl carbonate and 28% sodium methoxide / methanol solution in the same manner as in Example 3, 25.9 g of methyl ethyl ketone and 0.47 g (26.2 mmol; purified water); 0.054 mol) per 1 mol of amino group of 1,3-bis (methoxycarbonylaminomethyl) cyclohexane was added and further reacted at 50 ° C. for 30 minutes.
  • Example 7 Synthesis of 1,3-bis (methoxycarbonylaminomethyl) cyclohexane After reacting 1,3-bisaminomethylcyclohexane, dimethyl carbonate and 28% sodium methoxide / methanol solution in the same manner as in Example 3, 26.0 g of methyl isobutyl ketone and 0.46 g (25. 7 mmol; 0.052 mol relative to 1 mol of amino group of 1,3-bis (methoxycarbonylaminomethyl) cyclohexane) was added, and the mixture was further reacted at 50 ° C. for 30 minutes.
  • Reference Example 1 Synthesis of 1,3-bis (isocyanatomethyl) cyclohexane (Apparatus for producing isocyanate compounds from carbamate compounds)
  • a glass tube (3) having a diameter of 10 mm and a length of 42 cm is used as a reactor, and an electric furnace (4 ) And branch into two lines at the bottom of the reaction tube.
  • Receivers for methanol acquisition (with cold ethanol) Cooling) Via both (9) and (15), both lines were connected to a vacuum pump, and the vacuum lines were connected. Switching between the two lines was performed by opening only one of the valves (5 and 10, and 11 and 16) (closing the other line).
  • FUJI SILICIA CHEMICAL CARTOECT Q50 (average pore size 50 nm, particle size 1.1 to 2.2 mm) was filled in the glass tube (3), and the vacuum pump (17) was started. The pressure was reduced to 1.33 kPa, the valves (5) and (10) were opened, the valves (11) and (16) were closed, and heat and melted at 150 ° C. -Bis (methoxycarbonylaminomethyl) cyclohexane (1) was fed at 4.4 g / h by syringe pump (2). It heated so that the temperature of a catalyst layer might be 350 degreeC with an electric furnace (4).
  • Comparative Reference Example 1 Synthesis of 1,3-bis (isocyanatomethyl) cyclohexane
  • the same operation as in Reference Example 1 was carried out except that 1,3-bis (methoxycarbonylaminomethyl) cyclohexane obtained in Comparative Example 2 was used as the carbamate compound.
  • 1,3-bis (methoxycarbonylaminomethyl) cyclohexane obtained in Comparative Example 2 was used as the carbamate compound.
  • the line connecting the substrate supply pump (2) and the tubular reactor (3) filled with the catalyst was blocked shortly after the start of substrate supply, and the product was not recovered.
  • the present invention relates to a method for producing a carbamate compound by reacting a carbonate compound and an amine compound.
  • the carbamate compound is useful, for example, as a raw material for producing an isocyanate compound.

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Abstract

La présente invention a pour objet de proposer un procédé pour la production d'un composé carbamate approprié de façon industrielle sans nécessiter une opération compliquée, où un composé carbamate d'une qualité appropriée pour la production d'un composé isocyanate est produit par réaction d'un composé carbonate et d'un composé amine. À cet effet, un procédé de production d'un composé carbamate est caractérisé par la réaction d'un composé amine et d'un composé carbonate en présence d'au moins une base choisie dans un groupe comprenant des alcoxydes de métal alcalin et des alcoxydes de métal alcalino-terreux, puis l'ajout de 0,01 à 0,5 mole d'eau à 1 mole d'un groupe amino du composé amine, et la réaction supplémentaire du composé amine et du composé carbonate.
PCT/JP2013/083369 2012-12-14 2013-12-12 Procédé de production de composé carbamate WO2014092161A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
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JP2015137255A (ja) * 2014-01-22 2015-07-30 宇部興産株式会社 カルバメート化合物の製造方法
JP2021513504A (ja) * 2017-12-21 2021-05-27 パフォーマンス・ポリアミデス，エスアエス コルベ電解カップリング反応によって第一級ジアミンを調製するための方法

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CN110128297B (zh) * 2018-02-02 2021-01-12 中国科学院过程工程研究所 1，6-六亚甲基二氨基甲酸甲酯的制备方法
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JP2021513504A (ja) * 2017-12-21 2021-05-27 パフォーマンス・ポリアミデス，エスアエス コルベ電解カップリング反応によって第一級ジアミンを調製するための方法

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