[go: up one dir, main page]

WO2015133247A1 - Procédé de production d'ester d'acide carbamique - Google Patents

Procédé de production d'ester d'acide carbamique Download PDF

Info

Publication number
WO2015133247A1
WO2015133247A1 PCT/JP2015/053954 JP2015053954W WO2015133247A1 WO 2015133247 A1 WO2015133247 A1 WO 2015133247A1 JP 2015053954 W JP2015053954 W JP 2015053954W WO 2015133247 A1 WO2015133247 A1 WO 2015133247A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
isomer
metal alkoxide
carbamate
alkoxide compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/053954
Other languages
English (en)
Japanese (ja)
Inventor
準哲 崔
俊也 小野澤
訓久 深谷
弘之 安田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
National Institute of Advanced Industrial Science and Technology AIST
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Institute of Advanced Industrial Science and Technology AIST filed Critical National Institute of Advanced Industrial Science and Technology AIST
Priority to JP2016506403A priority Critical patent/JP6270180B2/ja
Publication of WO2015133247A1 publication Critical patent/WO2015133247A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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 by reacting carbon dioxide, an amine and a metal alkoxide compound.
  • Polyurethane is a typical general-purpose polymer that is used as life / building materials, automobile parts, paints, and the like.
  • polyurethane is produced by reacting a polyfunctional isocyanate with a polyfunctional alcohol.
  • Isocyanates are synthesized from amines and phosgene.
  • phosgene is extremely toxic and a large amount of hydrogen chloride is by-produced in the reaction of phosgene, development of an isocyanate synthesis method with a lower environmental impact has been strongly desired.
  • Non-Patent Document 1 a method in which a nitro compound is reacted with carbon monoxide in the presence of alcohol
  • a method in which an amine is reacted with carbon monoxide in the presence of alcohol (1) a method in which an amine is reacted with carbon monoxide in the presence of alcohol (Non-Patent Document 1), and (2) a method in which an amine is reacted with carbon monoxide in the presence of alcohol.
  • Non-patent document 1 (3) Method of reacting amine and organic halogen compound with carbon dioxide (Non-patent document 2), (4) Method of reacting amine with carbonate (Non-patent document 3), (5) A method of reacting carbon dioxide with an amine and alcohol in the presence of a dehydrating agent (Non-Patent Document 4) is known.
  • the object of the present invention is to overcome the above-mentioned problems in the synthesis of conventional carbamic acid esters using carbon dioxide and amine as raw materials, and to use carbamines including aromatic carbamic acid esters without using organic halogen compounds or carbonate esters.
  • An object of the present invention is to provide an industrially advantageous method for producing a carbamic acid ester capable of obtaining an acid ester with high yield and high selectivity.
  • a method for producing a carbamate ester comprising a step of reacting carbon dioxide, an amine and a metal alkoxide compound.
  • R 1 is an alkoxy group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.
  • R 2 may be an alkoxy group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or 1 carbon atom.
  • R 3 , R 4 , R 5 and R 6 are an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
  • M 2 and M 3 represent a metal atom of Group 4 or Group 14 of the periodic table, and M 2 and M 3 may be the same or different.
  • R 7 , R 8 , R 9 , R 10 , R 11 and R 12 represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group, and R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are the same.
  • E, f, g and h are each an integer of 0 to 2
  • i and j are each an integer of 1 to 3
  • e + f 0 to 2
  • ⁇ 4> reacting carbon dioxide, an amine and a metal alkoxide compound to form a reaction mixture containing a carbamate, Separating a carbamate from the reaction mixture to obtain a residual liquid; Reacting the residual liquid with alcohol to regenerate the metal alkoxide compound;
  • the method for producing a carbamic acid ester according to ⁇ 1> comprising a step of reacting carbon dioxide, an amine and the regenerated metal alkoxide compound.
  • ⁇ 5> The method for producing a carbamate according to ⁇ 4>, wherein the alcohol is represented by the following general formula (IV). (In the formula, R 13 represents a hydrocarbon group.)
  • ⁇ 6> The method for producing a carbamate according to ⁇ 4>, wherein the residual liquid contains a metal compound of Group 4 or Group 14 of the periodic table having a metal-oxygen bond or a metal-nitrogen bond.
  • ⁇ 7> The method for producing a carbamic acid ester according to ⁇ 4>, wherein in the step of obtaining the metal alkoxide compound, the residual liquid and the alcohol are reacted while removing generated water from the reaction system.
  • a carbamic acid ester useful as a raw material for polyurethane can be obtained with high yield and high selectivity by reacting carbon dioxide with an amine and a metal alkoxide compound.
  • the metal alkoxide compound which can be used for the said reaction can also be obtained by making the reaction residual liquid resulting from the said reaction react with alcohol.
  • the method of the present invention uses carbon dioxide that is harmless to the environment and non-toxic, an amine that is inexpensive and easy to handle, and a metal alkoxide compound that can be easily and efficiently recycled and recycled from the reaction system. Therefore, the carbamate can be obtained with safe and simple equipment, which can be said to be an extremely industrially advantageous method.
  • the method for producing a carbamic acid ester of the present invention includes at least a step of reacting carbon dioxide, an amine and a metal alkoxide compound.
  • the carbamic acid ester obtained by this production method is preferably an N-substituted carbamic acid ester.
  • the obtained carbamic acid ester is preferably an aliphatic carbamic acid ester, an alicyclic carbamic acid ester, or an aromatic carbamic acid ester, and more preferably an aromatic carbamic acid ester.
  • the obtained carbamic acid ester is preferably a monocarbamic acid ester or a dicarbamic acid ester. Industrially, dicarbamic acid esters, particularly aromatic dicarbamic acid esters are advantageous.
  • examples of the carbamate obtained by this production method include methyl N-butylcarbamate, ethyl N-butylcarbamate, propyl N-butylcarbamate, butyl N-butylcarbamate, and N-butyl.
  • the amine used in the above carbamic acid ester formation reaction is preferably an aliphatic amine, an alicyclic amine, or an aromatic amine, and more preferably an aromatic amine.
  • the amine to be used is preferably a primary amine or a secondary amine, and more preferably a primary amine.
  • the amine used is preferably a monoamine or a diamine. Industrially, it is advantageous to use a diamine, particularly an aromatic diamine.
  • the amine to be used is preferably represented by the following general formula (I).
  • R 1 is an alkoxy group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, 1 carbon atom) Substituted with up to 6 acyloxy groups, carbonyl groups, hydroxyl groups, nitro groups, nitroso groups, cyano groups, hydrocarbon groups having 1 to 20 carbon atoms (eg, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, aralkyl groups) An optionally substituted amino group and a hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, which may be substituted with one or more substituents selected from the group consisting of halogen atoms (eg alkyl R 2 represents an alkoxy group having 1 to 6 carbon atoms, an alkylsulfony
  • a hydrocarbon group having 1 to 20 carbon atoms for example, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group
  • the halogen atom is a halogen atom selected from F, Cl, Br and I.
  • R 1 is an optionally substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, or an aryl group having 6 to 30 carbon atoms, more preferably an aryl group.
  • R 2 is hydrogen.
  • Preferred aryl groups include phenyl group, tolyl group, xylyl group, naphthyl group and the like.
  • amines examples include methylamine, ethylamine, propylamine, isopropylamine, butylamine, t-butylamine, cyclohexylamine, dimethylamine, diethylamine, aniline, aminotoluene (each isomer), and chloroaniline (each isomer).
  • Bromoaniline (each isomer), iodoaniline (each isomer), cyanoaniline (each isomer), nitroaniline (each isomer), trifluoromethylaniline (each isomer), methoxyaniline (each isomer) , Dimethylaniline (each isomer), diethylaniline (each isomer), dipropylaniline (each isomer), aminonaphthalene (each isomer), aminomethylnaphthalene (each isomer), dimethylnaphthylamine (each isomer) , Trimethylnaphthylamine (each isomer), di Minobenzene (each isomer), diaminotoluene (each isomer), methylenedianiline (each isomer), diaminomesitylene (each isomer), diaminobiphenyl (each isomer), diaminodibenz
  • the metal alkoxide compound used in the above carbamic acid ester formation reaction is preferably selected from metal alkoxide compounds represented by the following general formula (II) and metal alkoxide compounds represented by the following general formula (III). Of these, metal alkoxide compounds represented by the following general formula (II) are preferred. In this reaction, a metal alkoxide compound is used as a reactant.
  • R 3 , R 4 , R 5 and R 6 may be the same or different, linear or branched alkyl group having 1 to 14 carbon atoms, carbon number A cycloalkyl group having 5 to 14 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 19 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, including R 3 , R 4 , R 5 and R 6 may be the same or different and are preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and a and b are each an integer of 0 to 2.
  • a + b 0 to 3
  • M 2 and M 3 may be the same or different.
  • R 7 , R 8 , R 9 , R 10 , R 11 and R 12 may be the same.
  • M 1 in the general formula (II) and M 2 and M 3 in the general formula (III) are not particularly limited as long as they are metals included in Group 4 or Group 14 of the Periodic Table.
  • titanium, tin, and zirconium are preferable, and titanium is particularly preferable from the viewpoints of safety, yield, recycling, and the like.
  • the metal alkoxide compound represented by the general formula (II) is not particularly limited.
  • the metal alkoxide compound represented by the general formula (III) is not particularly limited, and examples thereof include 1,1,3,3-tetrabutyl-1,3-distanoxide, 1,1,3,3-terolabutyl. -1- (methoxy) -3- (2-ethyl-1-hexyloxy) -di-stannoxane, 1,1,3,3-tetrabutyl-1,3-di-ethoxy-di-stannoxane, 1,1, 3,3-tetrabutyl-1,3-di- (2-ethyl-1-hexyloxy) -distanoxane, 1,1,3,3-tetrabutyl-1,3-dipropoxy-distanoxane, 1,1,3,3-tetrabutyl-1,3-di-pentyloxy-di-stannoxane, 1,1,3,3-tetrabutyl-1,3-di-hexyloxy-di-stannoxane,
  • the above-mentioned carbamic acid ester formation reaction is not particularly limited in its reaction method, but can be performed, for example, by charging carbon dioxide into a reaction apparatus charged with an amine and a metal alkoxide compound.
  • the amount of amine and metal alkoxide compound used is not particularly limited and varies depending on the type of raw material used.
  • the amount of metal alkoxide compound used is, for example, 1/4 molar equivalent or more, preferably 1 molar equivalent of amine. Is 1/3 molar equivalents or more, more preferably 1/2 molar equivalents or more, and even more preferably 1 molar equivalents or more (the upper limit is not particularly limited, but is preferably 10 molar equivalents or less).
  • the reaction temperature of the above carbamic acid ester formation reaction is not particularly limited, but from the viewpoint of sufficiently proceeding the reaction and suppressing the formation of by-products such as urea, for example, room temperature to 300 ° C., preferably 100 to 200 ° C, more preferably 130 to 200 ° C, still more preferably 150 to 180 ° C.
  • the reaction pressure is not particularly limited and is determined depending on the production cost of the pressure device used for the reaction, but is usually 1 to 1000 atm, preferably 5 to 500 atm, and more preferably 10 to 100 atm. Specifically, for example, it is 1 to 100 MPa, preferably 2 to 50 MPa, more preferably 3 to 20 MPa.
  • the above carbamic acid ester formation reaction can proceed even at a relatively low pressure compared to conventional reactions.
  • the reaction time varies depending on various conditions such as the type of amine or metal alkoxide compound used as a raw material, the reaction temperature, and the reaction pressure, but 0.1 to 24 hours is sufficient. Specifically, the time is, for example, 10 minutes to 2 hours, preferably 10 to 60 minutes, from the viewpoint of sufficiently allowing the reaction to proceed and suppressing the formation of by-products such as urea.
  • the above carbamic acid ester formation reaction may be solventless, but a solvent that does not inhibit the reaction can also be used.
  • solvents include hydrocarbons and ethers, and specific examples include benzene, toluene, hexane, tetrahydrofuran, diethyl ether, dioxane, acetonitrile, dichloromethane, and the like.
  • a solvent other than alcohol methanol, ethanol, etc.
  • the method for producing a carbamic acid ester of the present invention may further include a step of regenerating and reusing the metal alkoxide compound.
  • the present production method comprises a step of reacting carbon dioxide, an amine and a metal alkoxide compound to form a reaction mixture containing a carbamate ester, and separating the carbamate ester from the reaction mixture to obtain a residual liquid. It may include a step of obtaining, a step of reacting the residual liquid with alcohol to regenerate the metal alkoxide compound, and a step of reacting carbon dioxide, the amine and the regenerated metal alkoxide compound.
  • the carbamate can be regenerated and reused by the following steps (a) to (d).
  • the steps (a) to (d) are continuously repeated twice or more, whereby the carbamic acid ester can be obtained continuously, which is industrially advantageous.
  • C A step of reacting the residual liquid with alcohol to obtain a metal alkoxide compound.
  • D A step of circulating the metal alkoxide compound obtained in step (c) to step (a).
  • the above reaction can be represented by the following formula. (1) CO 2 + amine + metal alkoxide compound ⁇ used metal alkoxide compound + carbamate (2) used metal alkoxide compound + alcohol ⁇ metal alkoxide compound + water (3) metal alkoxide compound of (2) ⁇ (1 When the metal alkoxide compound is recycled and reused, only CO 2 , amine and alcohol are consumed as a whole process as shown in the above formula, and products other than the target product are mainly water. It is only environmentally and economically advantageous.
  • Step (a) is a step of reacting carbon dioxide with an amine and a metal alkoxide compound to produce a reaction mixture containing a carbamate.
  • the reaction method, reaction conditions, etc. are as described above.
  • step (b) from the reaction mixture containing the carbamic acid ester and the used metal alkoxide compound obtained in the reaction step (b), a residual liquid containing the target product carbamic acid ester and the used metal alkoxide compound is obtained. To separate. This separation operation is performed by a conventionally known method such as distillation.
  • Step (c) is a step of obtaining a metal alkoxide compound from the residual liquid.
  • This step consists of reacting the used metal alkoxide compound with alcohol.
  • a metal alkoxide compound metal-oxygen-carbon bond
  • the metal alkoxide compound is a compound having a metal-oxygen bond.
  • metal hydroxide or metal oxide, or a compound having a metal-nitrogen bond such as a metal amide in which a raw material amine is bonded to a metal. That is, the used metal alkoxide compound contains, for example, metal hydroxide, metal oxide or metal amide.
  • a metal compound having such a metal-oxygen bond or metal-nitrogen bond is reacted with an alcohol to convert it into a corresponding metal alkoxide compound.
  • distillation or membrane separation may be used, but a dehydrating agent may be used.
  • the alkyl group represented by R 14 , R 15 and R 16 is preferably a lower alkyl group, more preferably 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, n-butyl and the like.
  • the aralkyl group represented by R 14 , R 15 and R 16 preferably has 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms, and examples thereof include benzyl and phenethyl.
  • the aryl group represented by R 14 , R 15 and R 16 preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and examples thereof include phenyl, tolyl, anisyl, naphthyl and the like.
  • acetal compounds for example, benzaldehyde dimethyl acetal, acetaldehyde dimethyl acetal, formaldehyde dimethyl acetal, acetone dimethyl acetal, acetone diethyl acetal, acetone dibenzyl acetal, diethyl ketone dimethyl acetal, benzophenone dimethyl acetal, benzyl phenyl Ketones dimethyl acetal, cyclohexanone dimethyl acetal, acetophenone dimethyl acetal, 2,2-dimethoxy-2-phenylacetophenone acetal, 4,4-dimethoxy-2, 5-cyclohexadien-1-one acetal, dimethylacetamide diethyl acetal, etc. .
  • zeolites such as molecular sieve (3A) and molecular sieve (4A), calcium chloride (anhydrous), calcium sulfate (anhydrous), magnesium chloride (anhydrous), magnesium sulfate (anhydrous), potassium carbonate (anhydrous) ), Potassium sulfide (anhydrous), potassium sulfite (anhydrous), sodium sulfate (anhydrous), sodium sulfite (anhydrous), inorganic anhydrous salts such as copper sulfate (anhydrous), and the like.
  • the reaction temperature of the reaction for obtaining the metal alkoxide compound in the step (c) is not particularly limited, but is performed at room temperature to 300 ° C., preferably 80 to 200 ° C. for 1 to 100 hours.
  • step (d) the metal alkoxide compound obtained in step (c) is circulated to step (b).
  • Example 1 An autoclave having a volume of 10 mL equipped with a stirrer was charged with aniline (0.8 mmol), tetramethoxytitanium (0.8 mmol) as a metal alkoxide compound, and acetonitrile (3 mL) as a solvent, and then liquefied carbon dioxide from a carbon dioxide cylinder. (About 0.5 MPa) was filled and sealed. Thereafter, the inside of the autoclave was heated to 150 ° C. with stirring, and further filled with carbon dioxide, thereby increasing the internal pressure to 5 MPa and allowing the reaction to proceed for 20 minutes. After cooling, the remaining carbon dioxide was released and the reaction mixture was analyzed by liquid chromatography. The yield of aromatic carbamic acid ester based on aniline was 61%.
  • Examples 2-4 An aromatic carbamic acid ester was synthesized in the same manner as in Example 1 except that the following metal alkoxide compound was used instead of tetramethoxytitanium as the metal alkoxide compound. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 2 Tetraethoxytitanium (Yield: 57%)
  • Example 3 Tetra-i-propoxytitanium (Yield: 50%)
  • Example 5 1,4-dioxane (yield: 50%)
  • Example 6 Diethyl ether (Yield: 47%)
  • Example 7 Tetrahydrofuran (Yield: 48%)
  • Example 8 Dichloromethane (Yield: 46%)
  • Example 9-12 The aromatic carbamic acid ester was synthesized under the same conditions as in Example 1, except that the amount of tetramethoxytitanium, which is a metal alkoxide compound, was different. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 12 1.6 mmol (yield: 66%)
  • Example 13-15 The raw materials and reaction conditions were the same as in Example 1, and aromatic carbamic acid esters were synthesized under conditions with different reaction times. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 16-20 The raw materials and reaction conditions were the same as in Example 1, and aromatic carbamic acid esters were synthesized under conditions where reaction temperatures were different. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 16 110 ° C. (Yield: 1%)
  • Example 17 Example 17; 130 ° C. (Yield: 20%)
  • Example 18 Example 18; 170 ° C. (Yield: 76%)
  • Example 19 180 ° C. (Yield: 81%)
  • Example 20 200 ° C. (Yield: 77%)
  • Example 21 The raw materials and reaction conditions were the same as in Example 1, and the aromatic carbamic acid ester was synthesized under conditions where the internal pressure of carbon dioxide was different. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 21 1 MPa (yield: 42%)
  • Example 22 2 MPa (yield: 52%)
  • Example 23 3 MPa (yield: 57%)
  • Example 24 8 MPa (yield: 56%)
  • Example 25 10 MPa (Yield: 59%)
  • Example 26 15 MPa (Yield: 57%)
  • Example 27 An aromatic carbamic acid ester was synthesized in the same manner as in Example 19 (reaction temperature 180 ° C.) except that tetrabutoxytitanium was used instead of tetramethoxytitanium as the metal alkoxide compound. As a result, the yield of aromatic carbamic acid ester based on aniline was 82%.
  • Example 28-31 The raw materials and reaction conditions were the same as in Example 19 (reaction temperature 180 ° C.), and aromatic carbamic acid esters were synthesized under conditions with different reaction times. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 32-37 The raw materials and reaction conditions were the same as in Example 29 (reaction temperature 180 ° C., reaction time 30 minutes), and aromatic carbamic acid esters were synthesized under conditions where the internal pressure of carbon dioxide was different. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 32 1 MPa (yield: 52%) Example 33; 2 MPa (yield: 72%) Example 34; 3 MPa (yield: 73%) Example 35; 4 MPa (Yield: 82%) Example 36; 8 MPa (Yield: 82%) Example 37; 10 MPa (yield: 84%)
  • Example 38-39 The raw materials and reaction conditions were the same as in Example 29 (reaction temperature 180 ° C., reaction time 30 minutes), and aromatic carbamic acid esters were synthesized under conditions where the amount of tetramethoxytitanium, which is a metal alkoxide compound, was different. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 38 0.4 mmol (yield: 47%)
  • Example 39 1.6 mmol (yield: 86%)
  • Examples 40-49 A carbamic acid ester was synthesized in the same manner as in Example 28 (reaction temperature 180 ° C., reaction time 30 minutes) except that the following various amines were used instead of aniline. The result is shown as the yield (%) of carbamic acid ester based on amine.
  • Example 40 4-methylaniline (p-aminotoluene) (yield: 90%)
  • Example 41 4-bromoaniline (yield: 80%)
  • Example 42 4-cyanoaniline (yield: 61%)
  • Example 43 4-nitroaniline (yield: 53%)
  • Example 44 4-trifluoromethylaniline (yield: 69%)
  • Example 45 4-methoxyaniline (yield: 98%)
  • Example 46 3-methoxyaniline (yield: 85%)
  • Example 47 2-methoxyaniline (yield: 66%)
  • Example 48 ; cyclohexylamine (yield: 86%)
  • Example 49 t-butylamine (yield: 87%)
  • Examples 50-51 An aromatic dicarbamic acid ester was synthesized in the same manner as in Example 28 (reaction temperature 180 ° C., reaction time 30 minutes) except that the following various diamines were used instead of aniline. The results are shown as the yield (%) of aromatic dicarbamic acid ester based on diamine.
  • Example 50 4,4′-methylenedianiline (yield: 77%)
  • Example 51 2,4-diaminotoluene (yield: 63%)
  • Example 53 An aromatic carbamic acid ester was synthesized in the same manner as in Example 52 except that dibutyltin dibutoxide was used as the metal alkoxide compound instead of dibutyltin dimethoxide. As a result, the yield of aromatic carbamic acid ester based on aniline was 35%.
  • Examples 54-55 The aromatic carbamic acid ester was synthesized under the same conditions as in Example 52, except that the amount of dibutyltin dimethoxide as a metal alkoxide compound was different. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 54 0.8 mmol (yield: 34%)
  • Example 55 1.6 mmol (yield: 68%)
  • Example 56 The raw materials and reaction conditions were the same as in Example 52, and aromatic carbamic acid esters were synthesized under conditions where reaction temperatures were different. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 56 100 ° C. (Yield: 1%)
  • Example 57 110 ° C. (Yield: 10%)
  • Example 58 130 ° C. (Yield: 37%)
  • Example 60 The raw materials and reaction conditions were the same as in Example 52, and the aromatic carbamic acid ester was synthesized under conditions where the internal pressure of carbon dioxide was different. The results are shown as the yield (%) of the aromatic carbamic acid ester based on aniline.
  • Example 60 1 MPa (yield: 68%)
  • Example 61 2 MPa (yield: 77%)
  • Example 62 10 MPa (Yield: 78%)
  • Example 63 An aromatic dicarbamic acid ester was synthesized in the same manner as in Example 52 except that 2,4-diaminotoluene was used instead of aniline. As a result, the yield of aromatic dicarbamic acid ester based on 2,4-diaminotoluene was 46%.
  • Example 64 The raw materials and reaction conditions were the same as in Example 63, and an aromatic dicarbamic acid ester was synthesized with dibutyltin dimethoxide (4.8 mmol), which is a metal alkoxide compound. As a result, the yield of aromatic dicarbamic acid ester based on 2,4-diaminotoluene was 65%.
  • Example 65 An aromatic dicarbamic acid ester was synthesized in the same manner as in Example 63 except that dibutyltin dibutoxide was used in place of dibutyltin dimethoxide as the metal alkoxide compound. As a result, the yield of aromatic dicarbamic acid ester based on 2,4-diaminotoluene was 44%.
  • Example 66 A 10 mL volume autoclave equipped with a stirrer was charged with cyclohexylamine (0.8 mmol), tetraalkoxytitanium (0.8 mmol) as a metal alkoxide compound, and acetonitrile (3 mL) as a solvent, and then liquefied carbon dioxide from a carbon dioxide cylinder. Filled with carbon (about 3 MPa) and sealed. Thereafter, the inside of the autoclave was heated to 150 ° C. with stirring, and further filled with carbon dioxide, thereby increasing the internal pressure to 5 MPa and allowing the reaction to proceed for 20 minutes. After cooling, the remaining carbon dioxide was released and the reaction mixture was analyzed by liquid chromatography. The yield of aliphatic carbamic acid ester based on cyclohexylamine was 33%.
  • Step (2) The titanium butoxide compound obtained in the above step (c) was reused by circulating it to the step (a). The result is shown as the yield (%) of carbamic acid ester based on aniline.
  • Example 67 Yield: 50% (initial) Example 68; Yield: 55% (first reuse) Example 69; Yield: 53% (second reuse) Example 70; Yield: 51% (3rd reuse) Example 71; Yield: 50% (4th reuse) Example 72; Yield: 51% (5th reuse) Example 73; Yield: 52% (6th reuse) Example 74; Yield: 55% (7th reuse) Example 75; Yield: 55% (8th reuse) Example 76; Yield: 54% (9th reuse) Example 77; Yield: 52% (10th reuse)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé industriellement avantageux de production d'ester d'acide carbamique, moyennant lequel il devient possible de produire un ester d'acide carbamique, tel qu'un ester d'acide carbamique aromatique, avec un rendement élevé et une sélectivité élevée sans nécessiter l'utilisation d'un composé halogène organique ni d'ester carbonate. C'est-à-dire, la présente invention concerne un procédé de production d'ester d'acide carbamique comportant la réaction de dioxyde de carbone, d'une amine et d'un composé alcoxyde métallique les uns avec les autres.
PCT/JP2015/053954 2014-03-07 2015-02-13 Procédé de production d'ester d'acide carbamique Ceased WO2015133247A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016506403A JP6270180B2 (ja) 2014-03-07 2015-02-13 カルバミン酸エステルの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-045037 2014-03-07
JP2014045037 2014-03-07

Publications (1)

Publication Number Publication Date
WO2015133247A1 true WO2015133247A1 (fr) 2015-09-11

Family

ID=54055057

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/053954 Ceased WO2015133247A1 (fr) 2014-03-07 2015-02-13 Procédé de production d'ester d'acide carbamique

Country Status (2)

Country Link
JP (1) JP6270180B2 (fr)
WO (1) WO2015133247A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016177761A1 (fr) * 2015-05-06 2016-11-10 Basf Se Procédé de préparation d'un composé isocyanate
WO2018043658A1 (fr) * 2016-09-02 2018-03-08 国立研究開発法人産業技術総合研究所 Procédé de production d'un ester d'acide carbamique
US10517849B2 (en) 2016-10-26 2019-12-31 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and medical uses thereof
US10526287B2 (en) 2015-04-23 2020-01-07 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and uses thereof
CN113201316A (zh) * 2021-04-25 2021-08-03 西南石油大学 温度/CO2/pH多重响应性乳化剂和乳状液及其应用
JP2021116252A (ja) * 2020-01-24 2021-08-10 国立研究開発法人産業技術総合研究所 カルバミン酸エステルの製造方法
WO2021246485A1 (fr) * 2020-06-05 2021-12-09 国立研究開発法人産業技術総合研究所 Procédé de fabrication de sel d'acide carbamique, procédé de fabrication d'ester d'acide carbamique, et procédé de fabrication de dérivé d'urée
JP2021191734A (ja) * 2020-06-05 2021-12-16 国立研究開発法人産業技術総合研究所 尿素誘導体の製造方法
JP2021191741A (ja) * 2020-06-05 2021-12-16 国立研究開発法人産業技術総合研究所 カルバミン酸塩の製造方法
CN115703721A (zh) * 2021-08-09 2023-02-17 深圳有为技术控股集团有限公司 新型氨基甲酸酯化合物和其制备方法以及在制备异氰酸酯中的应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6399808B1 (en) * 1999-02-26 2002-06-04 University Of South Florida Efficient carbamate synthesis
JP2002212159A (ja) * 2001-01-18 2002-07-31 National Institute Of Advanced Industrial & Technology カルバミン酸エステルの製造方法
JP2004189728A (ja) * 2002-11-28 2004-07-08 National Institute Of Advanced Industrial & Technology カルバミン酸エステルの製造方法
JP2009513592A (ja) * 2005-10-28 2009-04-02 グラクソ グループ リミテッド Ｎ，ｎ−置換カルバモイルハライドの製造方法
JP2012250930A (ja) * 2011-06-02 2012-12-20 Showa Denko Kk カーバメートの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6399808B1 (en) * 1999-02-26 2002-06-04 University Of South Florida Efficient carbamate synthesis
JP2002212159A (ja) * 2001-01-18 2002-07-31 National Institute Of Advanced Industrial & Technology カルバミン酸エステルの製造方法
JP2004189728A (ja) * 2002-11-28 2004-07-08 National Institute Of Advanced Industrial & Technology カルバミン酸エステルの製造方法
JP2009513592A (ja) * 2005-10-28 2009-04-02 グラクソ グループ リミテッド Ｎ，ｎ−置換カルバモイルハライドの製造方法
JP2012250930A (ja) * 2011-06-02 2012-12-20 Showa Denko Kk カーバメートの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MAHMUT ABLA ET AL.: "Halogen-free process for the conversion of carbon dioxide to urethanes by homogeneous catalysis", CHEMICAL COMMUNICATIONS, no. 21, 2001, pages 2238 - 2239, XP055223388, ISSN: 1359-7345 *

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10526287B2 (en) 2015-04-23 2020-01-07 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and uses thereof
WO2016177761A1 (fr) * 2015-05-06 2016-11-10 Basf Se Procédé de préparation d'un composé isocyanate
WO2018043658A1 (fr) * 2016-09-02 2018-03-08 国立研究開発法人産業技術総合研究所 Procédé de production d'un ester d'acide carbamique
CN109641835A (zh) * 2016-09-02 2019-04-16 国立研究开发法人产业技术综合研究所 氨基甲酸酯的制造方法
JPWO2018043658A1 (ja) * 2016-09-02 2019-06-24 国立研究開発法人産業技術総合研究所 カルバミン酸エステルの製造方法
US10752579B2 (en) 2016-09-02 2020-08-25 National Institute Of Advanced Industrial Science And Technology Production method of carbamic acid ester
CN109641835B (zh) * 2016-09-02 2021-07-20 国立研究开发法人产业技术综合研究所 氨基甲酸酯的制造方法
US10517849B2 (en) 2016-10-26 2019-12-31 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and medical uses thereof
US11013718B2 (en) 2016-10-26 2021-05-25 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and medical uses thereof
US11547695B2 (en) 2016-10-26 2023-01-10 Constellation Pharmaceuticals, Inc. LSD1 inhibitors and medical uses thereof
JP2021116252A (ja) * 2020-01-24 2021-08-10 国立研究開発法人産業技術総合研究所 カルバミン酸エステルの製造方法
JP7458058B2 (ja) 2020-01-24 2024-03-29 国立研究開発法人産業技術総合研究所 カルバミン酸エステルの製造方法
WO2021246485A1 (fr) * 2020-06-05 2021-12-09 国立研究開発法人産業技術総合研究所 Procédé de fabrication de sel d'acide carbamique, procédé de fabrication d'ester d'acide carbamique, et procédé de fabrication de dérivé d'urée
JP2021191734A (ja) * 2020-06-05 2021-12-16 国立研究開発法人産業技術総合研究所 尿素誘導体の製造方法
JP2021191741A (ja) * 2020-06-05 2021-12-16 国立研究開発法人産業技術総合研究所 カルバミン酸塩の製造方法
CN115956067A (zh) * 2020-06-05 2023-04-11 国立研究开发法人产业技术总合研究所 氨基甲酸盐的制造方法、氨基甲酸酯的制造方法、以及尿素衍生物的制造方法
EP4169901A4 (fr) * 2020-06-05 2024-06-05 National Institute Of Advanced Industrial Science and Technology Procédé de fabrication de sel d'acide carbamique, procédé de fabrication d'ester d'acide carbamique, et procédé de fabrication de dérivé d'urée
JP7525112B2 (ja) 2020-06-05 2024-07-30 国立研究開発法人産業技術総合研究所 尿素誘導体の製造方法
JP7670282B2 (ja) 2020-06-05 2025-04-30 国立研究開発法人産業技術総合研究所 カルバミン酸塩の製造方法
CN113201316A (zh) * 2021-04-25 2021-08-03 西南石油大学 温度/CO2/pH多重响应性乳化剂和乳状液及其应用
CN115703721A (zh) * 2021-08-09 2023-02-17 深圳有为技术控股集团有限公司 新型氨基甲酸酯化合物和其制备方法以及在制备异氰酸酯中的应用

Also Published As

Publication number Publication date
JP6270180B2 (ja) 2018-01-31
JPWO2015133247A1 (ja) 2017-04-06

Similar Documents

Publication Publication Date Title
JP6270180B2 (ja) カルバミン酸エステルの製造方法
KR101654731B1 (ko) 고분자 수지에 고정된 이온성 액체계 촉매 및 이를 이용한 n,n''-치환 우레아의 제조 방법
CA2724634C (fr) Methode de production d'ester d'acide carbamique n-substitue et methode de production d'isocyanate au moyen dudit ester
JP2012250930A (ja) カーバメートの製造方法
JPH0115498B2 (fr)
JP6770272B2 (ja) カルバミン酸エステルの製造方法
TW201900606A (zh) 異氰酸酯的製造方法
US8440860B2 (en) Process for manufacturing N, N-dialkyl lactamide
JP5322183B2 (ja) イソシアナート化合物の製造方法
JP5711350B1 (ja) アミンと二酸化炭素及びエポキシ化合物からの置換ウレア及びカルバメート類化合物の製造方法
CN101245001A (zh) 氯代甲酸9-芴甲酯的合成方法
JP2004262835A (ja) 芳香族イソシアネートの製造方法
JP6150347B2 (ja) アミノ基および／または水酸基を有する化合物の製造方法
WO1998035936A1 (fr) Procede de production de carbamates aryliques
CN101468959A (zh) 一种环己氨基甲酸酯的合成方法
JPS6242896B2 (fr)
JP2004531577A (ja) シクロヘキサノール誘導体の調製法
JP2004262834A (ja) 芳香族ウレタン化合物の製造方法
JP7458058B2 (ja) カルバミン酸エステルの製造方法
JP2002212159A (ja) カルバミン酸エステルの製造方法
JP4521027B2 (ja) ジアルキルジカーボネートの製造方法
KR20110028628A (ko) 만델로니트릴 화합물의 제조 방법
JPS6312059B2 (fr)
JPH06128215A (ja) アルキル−ｎ−アリ−ルカルバメ−トの製造法
CN101269341A (zh) 用于合成芳香氨基甲酸酯的催化剂及制法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15758456

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016506403

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15758456

Country of ref document: EP

Kind code of ref document: A1