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WO2013081157A1 - Procédé de fabrication de carbonate cyclique - Google Patents

Procédé de fabrication de carbonate cyclique Download PDF

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Publication number
WO2013081157A1
WO2013081157A1 PCT/JP2012/081217 JP2012081217W WO2013081157A1 WO 2013081157 A1 WO2013081157 A1 WO 2013081157A1 JP 2012081217 W JP2012081217 W JP 2012081217W WO 2013081157 A1 WO2013081157 A1 WO 2013081157A1
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group
reaction
nmr
amine compound
cyclic
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Japanese (ja)
Inventor
直人 青柳
遠藤　剛
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Fujifilm Wako Pure Chemical Corp
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Wako Pure Chemical Industries Ltd
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Priority to JP2013547261A priority Critical patent/JP6146312B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C07D317/38—Ethylene carbonate

Definitions

  • the present invention relates to a method for producing a cyclic carbonate that is widely used in various applications such as an electrolytic solution of a lithium ion secondary battery and a plastic raw material. More specifically, the present invention relates to a method for producing a cyclic carbonate using carbon dioxide.
  • carbon dioxide in the atmosphere has been steadily increasing and is regarded as a problem as a cause of global warming.
  • carbon dioxide can be effectively utilized and converted into a functional material or the like, carbon dioxide can be regarded as one of resources that can be obtained inexhaustibly.
  • Non-Patent Document 1 a method using, for example, lithium bromide which is a metal salt (for example, Non-Patent Document 1) requires a high temperature condition under normal pressure conditions, for example, a method using a quaternary ammonium salt (for example, Non-Patent Document 2).
  • Etc. require high-pressure conditions in addition to high-temperature conditions while being metal-free (metal-free).
  • various methods for synthesizing cyclic carbonates are known (for example, Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, Non-Patent Document 3, Non-Patent Document 4, (Non-Patent Document 5, Non-Patent Document 6, etc.) and any of the synthesis methods require high temperature, high pressure, or both conditions.
  • Non-Patent Document 7 a composite catalyst having both the characteristics of a metal and a quaternary ammonium salt has been developed and used for a carbonate reaction under normal temperature and normal pressure conditions.
  • this composite catalyst is an expensive metal coordination catalyst that requires multiple steps for its synthesis, there is a difficulty in practicality.
  • the present invention has been made in view of the above-mentioned situation, and not only can produce a wide variety of cyclic carbonates with high yield even when the reaction is performed under mild conditions such as normal temperature and normal pressure, but also the environment.
  • An object of the present invention is to provide a practical cyclic carbonate production method in consideration of load reduction.
  • the present inventors have found that in the reaction of epoxide (oxirane) with carbon dioxide, the primary to tertiary amine having a pKa of 8 or more, a monoamine, By using an amine compound selected from cyclic amidine and guanidine and hydrogen iodide, it has been found that the above-described object can be achieved, and the present invention has been completed.
  • an epoxide and carbon dioxide are reacted in the presence of hydrogen iodide with an amine compound selected from monoamine, cyclic amidine and guanidine, which is a primary to tertiary amine having a pKa of 8 or more. It is invention of the manufacturing method of cyclic carbonate characterized by these.
  • a cyclic carbonate by the reaction of epoxide (oxirane) and carbon dioxide, a primary or tertiary amine having a pKa of 8 or more, an amine compound selected from monoamine, cyclic amidine and guanidine, and hydrogen iodide
  • epoxide oxirane
  • carbon dioxide a primary or tertiary amine having a pKa of 8 or more
  • an amine compound selected from monoamine, cyclic amidine and guanidine and hydrogen iodide
  • a primary to tertiary amine having a pKa of 8 or more when an amine compound selected from monoamines, cyclic amidines and guanidines and hydrogen iodide are used, the reason why the above-described effects can be obtained. It is considered as follows. That is, it is a primary to tertiary amine having a pKa of 8 or more and is selected from monoamines, cyclic amidines and guanidines (hereinafter sometimes abbreviated as amine compounds according to the present invention) and iodide.
  • An amine compound salt prepared from hydrogen and having a proton and iodine anion (hereinafter sometimes abbreviated as the amine compound salt according to the present invention) is a catalyst (hereinafter referred to as “catalyst”) in a reaction of epoxide (oxirane) with carbon dioxide. It is considered that the cyclic carbonate can be produced in good yield even under mild conditions such as normal temperature and normal pressure.
  • an amine compound salt having proton and iodine anion can be synthesized easily and inexpensively in one step from the amine compound according to the present invention and hydrogen iodide, and is also a metal-free (metal-free) catalyst. Therefore, the production method of the present invention using the catalyst (amine compound salt) is useful from the viewpoint of green chemistry, and is a practical production method considering reduction of environmental burden.
  • the method for producing a cyclic carbonate of the present invention comprises a reaction between an epoxide (oxirane) and carbon dioxide, a primary to tertiary amine having a pKa of 8 or more, and an amine compound selected from monoamine, cyclic amidine and guanidine. And in the presence of hydrogen iodide.
  • the amine compound according to the present invention is an amine having at least one amino group and a pKa of 8 or more, may have a plurality of amino groups, and has other functional groups such as a hydroxyl group. You may do it.
  • Specific examples of such amine compounds include those selected from, for example, monoamines represented by the following general formula [1], cyclic amidines represented by the following general formula [2], and guanidines represented by the following general formula [3]. Can be mentioned.
  • R 1 represents a branched or cyclic alkyl group having 3 to 10 carbon atoms or an aralkyl group having 7 to 12 carbon atoms
  • R 2 and R 3 each independently represents a hydrogen atom or a carbon number 1 to 10 linear, branched or cyclic alkyl groups.
  • R 4 and R 5 are bonded to each other to represent an alkylene chain having 2 to 5 carbon atoms, and together with the nitrogen atom bonded thereto and the carbon atom bonded to the nitrogen atom, 5- to 8-membered members
  • Each of R 6 and R 7 independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R 6 and R 7 , And may form a ring structure.
  • R 8 represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a hetero atom, or an aralkyl group having 7 to 12 carbon atoms;
  • R 9 , R 10 , R 11 and R 12 each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , R 11 and R 12 or R 8 and R 12 may form a cyclic structure.
  • branched or cyclic alkyl group having 3 to 10 carbon atoms represented by R 1 in the general formula [1] include isopropyl group, isobutyl group, s-butyl group, t-butyl group, Cyclobutyl group, isopentyl group, s-pentyl group, t-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, isohexyl group, s-hexyl group, t -Hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, isoheptyl group, s-heptyl group, t-heptyl group, Neohept
  • a cyclic alkyl group having 5 to 8 carbon atoms such as a cyclooctyl group is preferred, and among them, a t-butyl group and a cyclohexyl group are more preferred.
  • s- represents a sec-form and t- represents a tert-form.
  • the aralkyl group having 7 to 12 carbon atoms represented by R 1 and R 8 in the general formulas [1] and [3] may be either monocyclic or condensed polycyclic. Examples include benzyl group, phenethyl group, methylbenzyl group, phenylpropyl group, 1-methylphenylethyl group, phenylbutyl group, 2-methylphenylpropyl group, tetrahydronaphthyl group, naphthylmethyl group, naphthylethyl group, etc. However, for example, an aralkyl group having 7 carbon atoms such as a benzyl group is preferred.
  • Specific examples of the branched or cyclic alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, and cyclobutyl.
  • n-pentyl group isopentyl group, s-pentyl group, t-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, Isohexyl group, s-hexyl group, t-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group, n-heptyl , Isoheptyl group, s-heptyl group, t-heptyl group, neoheptyl group, cycloheptyl group, n-octyl group, isooctyl group, s-octyl group
  • linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a hetero atom represented by R 8 in the general formula [3] include, for example, a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, s-pentyl group, t-pentyl group, Neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, s-hexyl group, t-hexyl group, neohexyl group, 2-methylpentyl Group, 1,2-dimethylbutyl group, 2,
  • a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms having no hetero atom such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, Hydroxyheptyl group, hydroxyoctyl group, hydroxynonyl group, hydroxydecyl group Methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl Group, ethoxypentyl group, ethoxyhexyl group, ethoxyheptyl group, ethoxyocty
  • R 4 and R 5 in the general formula [2] are bonded together to represent an alkylene chain having 2 to 5 carbon atoms
  • R 4 and R 5 form an alkylene group having 2 to 5 carbon atoms
  • a 5- to 8-membered ring is formed together with a nitrogen atom bonded to an alkylene group and a carbon atom bonded to the nitrogen atom.
  • Specific examples of the alkylene group having 2 to 5 carbon atoms include dimethylene group (ethylene group), trimethylene group (propane-1,3-diyl group), tetramethylene group (butane-1,4- Diyl group), pentamethylene group (pentane-1,5-diyl group) and the like.
  • trimethylene group (propane-1,3-diyl group) which is an alkylene group having 3 carbon atoms is preferable.
  • a 5- to 8-membered ring include, for example, 2-imidazoline ring, 1,4,5,6-tetrahydropyrimidine ring, 4,5,6,7-tetrahydro-1H-1,3- Examples thereof include a diazepine ring, among which a 1,4,5,6-tetrahydropyrimidine ring which is a 6-membered ring is preferable.
  • R 6 and R 7 in the general formula [2] may form a cyclic structure.
  • R 6 and R 7 form an alkylene group having 3 to 6 carbon atoms and bond to the alkylene group. This means that a 5- to 8-membered ring may be formed together with the nitrogen and carbon atoms.
  • Specific examples of such an alkylene group having 3 to 6 carbon atoms include trimethylene group (propane-1,3-diyl group), tetramethylene group (butane-1,4-diyl group), and pentamethylene group. (Pentane-1,5-diyl group) and the like, hexamethylene group (hexane-1,6-diyl group), and the like.
  • pentamethylene group which is an alkylene group having 5 carbon atoms is mentioned.
  • -Diyl group is preferred.
  • Specific examples of such a 5- to 8-membered ring include, for example, a pyrrolidine ring, a piperidine ring, a hexamethyleneimine ring (azepane ring), a heptamethyleneimine ring (azocan ring), and among others, a pyrrolidine ring.
  • a hexamethyleneimine ring (azepane ring) is preferable, and among them, a hexamethyleneimine ring (azepane ring) that is a seven-membered ring is more preferable.
  • R 8 and R 9 , R 10 and R 11 , or R 8 and R 12 in the general formula [3] may form a cyclic structure as R 8 and R 9 , R 10 and R 11 or R 8 and R 12 form an alkylene group having 2 to 5 carbon atoms, and together with the nitrogen atom bonded to the alkylene group and the carbon atom bonded to the nitrogen atom, forms a 5- to 8-membered ring. It means that you may.
  • alkylene group having 2 to 5 carbon atoms include dimethylene group (ethylene group), trimethylene group (propane-1,3-diyl group), tetramethylene group (butane-1,4- Diyl group), pentamethylene group (pentane-1,5-diyl group) and the like.
  • dimethylene group ethylene group
  • trimethylene group propane-1,3-diyl group
  • tetramethylene group butane-1,4- Diyl group
  • pentamethylene group pentamethylene group
  • pentamethylene group pentamethylene group
  • pentamethylene group pentamethylene group
  • 5- to 8-membered rings include, for example, 2-imidazoline ring, imidazolidine ring, 1,4,5,6-tetrahydropyrimidine ring, hexahydropyrimidine ring, 4,5,6,7 -Tetrahydro-1H-1,3-diazepine ring, hexahydro-1H-1,3-diazepine ring and the like are mentioned, among which 1,4,5,6-tetrahydropyrimidine ring and hexahydropyrimidine ring are preferable.
  • R 9 and R 10 or R 11 and R 12 may form a cyclic structure that R 9 and R 10 or R 11 and R 12 have 4 to 6 carbon atoms.
  • Specific examples of the alkylene group having 4 to 6 carbon atoms include a tetramethylene group (butane-1,4-diyl group), a pentamethylene group (pentane-1,5-diyl group), and hexamethylene. Group (hexane-1,6-diyl group) and the like.
  • a pentamethylene group which is an alkylene group having 5 carbon atoms is preferable.
  • a 5- to 7-membered ring include, for example, a pyrrolidine ring, a piperidine ring, a hexamethyleneimine ring (azepane ring), and among them, a piperidine ring is preferable.
  • R 1 is an aralkyl group having 7 to 12 carbon atoms
  • R 2 and R 3 are both linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms. It is preferable that
  • R 6 in the general formula [2] a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable when a cyclic structure is not formed with R 7. Groups are preferred.
  • R 6 and R 7 in the general formula [2] are preferably those in which R 6 and R 7 form a cyclic structure.
  • R 8 is preferably a linear, branched or cyclic alkyl group having 4 to 10 carbon atoms which may have a hetero atom
  • R 8 is a linear, branched or cyclic alkyl group having 4 to 10 carbon atoms which may have a hetero atom
  • the monoamine represented by the general formula [1] include various monoamines such as monoisopropylamine, mono-t-butylamine, monocyclohexylamine, dicyclohexylamine, and benzyldimethylamine.
  • a monoamine represented by the following general formula [1-I] is preferable in that a cyclic carbonate can be obtained with a higher yield.
  • R 1a represents a t-alkyl group having 4 to 6 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms
  • R 2a represents a hydrogen atom, a t-alkyl group having 4 to 6 carbon atoms, or a carbon atom.
  • t-alkyl group having 4 to 6 carbon atoms represented by R 1a and R 2a in the general formula [1-I] include, for example, a t-butyl group, a t-pentyl group, a t-hexyl group, and the like. Among them, a t-butyl group which is a t-alkyl group having 4 carbon atoms is preferable. In the above specific examples, t- represents a tert-isomer.
  • cycloalkyl group having 5 to 8 carbon atoms represented by R 1a and R 2a in the general formula [1-1] include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Of these, a cyclohexyl group which is a cycloalkyl group having 6 carbon atoms is preferable.
  • monoamine represented by the general formula [1-I] include, for example, mono-t-butylamine, di-t-butylamine, mono-t-pentylamine, di-t-pentylamine, and mono-t-hexylamine. , Di-t-hexylamine, monocyclopentylamine, dicyclopentylamine, monocyclohexylamine, dicyclohexylamine, monocycloheptylamine, dicycloheptylamine, monocyclooctylamine, dicyclooctylamine, etc.
  • Mono-t-butylamine and dicyclohexylamine are preferred in that a cyclic carbonate can be obtained with a higher yield.
  • t- represents a tert-isomer.
  • the monoamines represented by the general formula [1] and the general formula [1-I] may be commercially available products or those appropriately synthesized by a general method performed in this field.
  • cyclic amidine represented by the general formula [2] include, as an example, 1-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine.
  • various cyclic amidines such as 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) and 1,8-diazabicyclo [5.4.0] -7-undecene (DBU).
  • a cyclic amidine represented by the following general formula [2-1] is preferable in that a cyclic carbonate can be obtained with a higher yield.
  • n represents an integer of 1 to 4.
  • M in the general formula [2-I] usually represents an integer of 1 to 4, preferably 2.
  • N in the general formula [2-I] usually represents an integer of 1 to 4, preferably 1 or 3, and more preferably 3.
  • cyclic amidine represented by the general formula [2-I] include, for example, 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), 1,8-diazabicyclo [5.4.0]. ] -7-undecene (DBU) and the like. Among them, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) is particularly preferable in that a cyclic carbonate can be obtained with higher yield. preferable.
  • the cyclic amidines represented by the above general formula [2] and general formula [2-1] may be commercially available products or those appropriately synthesized by general methods performed in this field.
  • guanidine represented by the general formula [3]
  • guanidine 1- (1-n-butyl) guanidine, 1- (1-n-butyl) -3-methylguanidine, 1- (1 -n-butyl) -2,3-dimethylguanidine, 1- (1-n-butyl) -2,3,3-trimethylguanidine, 2- (1-n-butyl) -1,1,3,3- Tetramethylguanidine, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1- (1-n-octyl) guanidine, 1,1-dicyclohexylguanidine, 1- Benzylguanidine, 1- (2-hydroxyethyl) guanidine, 1- (2-methoxyethyl) guanidine, 1- (2-dimethylaminoethyl) guanidine, 1-benzyl-2,3,3-trimethylguanidine, 1- ( 2-Dimethylamino
  • 1- (1-n-butyl) guanidine, 1- (1-n-butyl) is preferable in that a cyclic carbonate can be obtained with higher yield.
  • -2,3,3-trimethylguanidine and 1-benzyl-2,3,3-trimethylguanidine are preferred.
  • n- represents a normal-body.
  • the guanidine represented by the above general formula [3] may be a commercially available product or a product appropriately synthesized by a general method performed in this field.
  • Examples of the hydrogen iodide according to the present invention include those in a gaseous state such as hydrogen iodide gas, and those in a solution state in which hydrogen iodide gas such as hydroiodic acid is dissolved in a liquid (solvent) such as water.
  • a gaseous state such as hydrogen iodide gas
  • a solution state in which hydrogen iodide gas such as hydroiodic acid is dissolved in a liquid (solvent) such as water.
  • a liquid (solvent) such as water
  • hydroiodic acid include, for example, a commercially available 57% aqueous solution of hydroiodic acid.
  • the reason why the amine is selected from monoamines, cyclic amidines and guanidines and hydrogen iodide is used as follows. It is. That is, as a result of intensive studies on a method for producing a cyclic carbonate using carbon dioxide, the present inventors have prepared an amine compound having protons and iodine anions prepared from the amine compound according to the present invention and hydrogen iodide. It has been found that the salt effectively acts as a catalyst in the reaction of epoxide (oxirane) with carbon dioxide.
  • the catalyst (amine compound salt) according to the present invention is an epoxide (oxirane) in which a proton bonded to an amine having an appropriate basicity in the catalyst (amine compound salt) even under mild conditions such as room temperature and normal pressure. It has a coordination action similar to that of a metal ligand with respect to oxygen atoms of iodine, and the iodine anion in the catalyst (amine compound salt) has an action of opening the epoxide (oxirane) effectively. It is considered that the cyclic carbonate can be produced with good yield even under mild conditions such as normal temperature and normal pressure.
  • the proton needs to be bonded to an amine having an appropriate basicity. Therefore, the pKa of the amine compound according to the present invention is 8 or more.
  • the amine compound preferably has a pKa of 10 or more. If an amine compound having a pKa of 10 or more is used, a cyclic carbonate can be produced with a higher yield.
  • An amine compound having a proton and iodine anion which is prepared from hydrogen iodide and a primary to tertiary amine having a pKa of 8 or more used in the present invention, which is selected from monoamines, cyclic amidines and guanidines
  • Specific examples of the salt include, for example, a salt of monoamine and hydrogen iodide having a pKa of 8 or more, represented by the following general formula [1 ′], and represented by the following general formula [2 ′].
  • the salt of monoamine having a pKa of 8 or more and hydrogen iodide represented by the general formula [1 ′] include monoisopropylamine hydrogen iodide, mono-t-butylamine hydrogen iodide, Various monoamine hydrogen iodides such as monocyclohexylamine hydrogen iodide, dicyclohexylamine hydrogen iodide, benzyldimethylamine hydrogen iodide, and the like can be mentioned. Among them, cyclic carbonate can be obtained with higher yield.
  • the monoamine hydrogen iodide salt represented by the following general formula [1′-I] is preferable.
  • monoamine hydrogen iodide represented by the general formula [1′-I] include, for example, mono-t-butylamine hydrogen iodide, di-t-butylamine hydrogen iodide, mono-t-pentylamine Hydrochloride, di-t-pentylamine hydrogen iodide, mono-t-hexylamine hydrogen iodide, di-t-hexylamine hydrogen iodide, monocyclopentylamine hydrogen iodide, dicyclopentylamine iodide Hydrogen salt, monocyclohexylamine hydrogen iodide, dicyclohexylamine hydrogen iodide, monocycloheptylamine hydrogen iodide, dicycloheptylamine hydrogen iodide, monocyclooctylamine hydrogen iodide, dicyclooctylamine In particular, a cyclic carbonate can be obtained with a higher yield.
  • Specific examples of the salt of cyclic amidine having a pKa of 8 or more and hydrogen iodide represented by the general formula [2 ′] include, for example, -methyl-1,4,5,6-tetrahydropyrimidine iodide salt 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine hydroiodide, 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) hydroiodide, 1,8- Various cyclic amidine hydrogen iodides such as diazabicyclo [5.4.0] -7-undecene (DBU) ⁇ ⁇ iodide can be mentioned, and among them, a cyclic carbonate can be obtained at a higher yield.
  • a cyclic amidine hydrogen iodide salt represented by the following general formula [2′-I] is preferable.
  • cyclic amidine hydrogen iodide represented by the general formula [2′-I] include, for example, 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) hydrogen iodide, 1,8 -Diazabicyclo [5.4.0] -7-undecene (DBU) hydroiodide, and the like.
  • DBN 1,5-diazabicyclo [4.3.0] -5-nonene
  • DBU 1,8 -Diazabicyclo [5.4.0] -7-undecene
  • DBU 1,8-diazabicyclo [5. 4.0] -7-undecene
  • Specific examples of the salt of guanidine and hydrogen iodide represented by the general formula [3 ′] having a pKa of 8 or more include, as an example, guanidine iodide salt, 1- (1-n-butyl) guanidine iodide.
  • n- represents a normal-body.
  • catalysts (amine compound salts) those selected from a monoamine hydrogen iodide salt represented by the general formula [1 ′] and a cyclic amidine hydrogen iodide salt represented by the general formula [2 ′] are preferable, Among these, those selected from monoamine hydrogen iodides represented by the general formula [1′-I] and cyclic amidine hydrogen iodides represented by the general formula [2′-I] are more preferable.
  • the reaction system of epoxide (oxirane) and carbon dioxide contains a primary or tertiary amine having a pKa of 8 or more and an amine compound selected from monoamine, cyclic amidine and guanidine and iodinated.
  • the catalyst (amine compound salt) according to the present invention which is a salt of an amine compound having protons and iodine anions, is generated from the amine compound according to the present invention and hydrogen iodide.
  • the catalyst (amine compound salt) according to the present invention may be prepared in use in the reaction system, or the amine compound according to the present invention and hydrogen iodide may be reacted in another system to produce the present invention.
  • the catalyst (amine compound salt) is prepared in advance, and the catalyst (amine compound salt) thus prepared and isolated is reacted with epoxide (oxirane) and carbon dioxide. It may be allowed to coexist within. That is, in the present invention, the reaction of epoxide (oxirane) and carbon dioxide may be carried out in the same system as the reaction for preparing the catalyst (amine compound salt) according to the present invention and reacted in one pot.
  • the catalyst (amine compound salt) is isolated by performing a reaction (step) in which the catalyst (amine compound salt) according to the present invention is prepared in advance in another system. An epoxide (oxirane) and carbon dioxide may be reacted with each other.
  • the reaction of epoxide (oxirane) and carbon dioxide in the presence of the catalyst (amine compound salt) according to the present invention prepared from the amine compound according to the present invention and hydrogen iodide can also be carried out by “pKa of 8 or more. It is a primary to tertiary amine and is included within the range expressed as “reacting with an amine compound selected from monoamine, cyclic amidine and guanidine in the presence of hydrogen iodide”. In addition, the preparation method of the catalyst (amine compound salt) concerning this invention is mentioned later.
  • the amine compound according to the present invention is reacted with hydrogen iodide in a separate system, and the catalyst (amine compound salt) according to the present invention is prepared and isolated in advance, and this is used as the catalyst. It is preferable.
  • the catalyst amine compound salt
  • the amine compound according to the present invention and hydrogen iodide coexist in the reaction system of epoxide (oxirane) and carbon dioxide
  • hydroiodic acid is used as a hydrogen iodide source
  • the coexisting water becomes epoxide (oxirane).
  • hydrogen iodide gas can be used as a hydrogen iodide source.
  • the method of preparing and isolating the catalyst (amine compound salt) according to the present invention in a separate system in advance can make the present invention easier. That is, the catalyst (amine compound salt) according to the present invention can be prepared in advance by a so-called one-step simple and inexpensive synthesis method in which the amine compound according to the present invention is reacted with hydroiodic acid which is easy to handle.
  • the catalyst (amine compound salt) according to the present invention can be prepared in advance by a so-called one-step simple and inexpensive synthesis method in which the amine compound according to the present invention is reacted with hydroiodic acid which is easy to handle.
  • most of the amine compound salt (catalyst according to the present invention) obtained by this preparation method is in a solid state, it can be easily isolated from the reaction system.
  • the amine compound salt which is a catalyst according to the present invention, can be synthesized in one step from the amine compound according to the present invention and hydrogen iodide, whether it is prepared at the time of use or prepared in advance and isolated. If used as a catalyst, it is useful in that cyclic carbonates can be produced in a yield equivalent to or higher than that of expensive metal coordination catalysts that require multiple steps for synthesis even under mild conditions such as room temperature and atmospheric pressure. is there. Moreover, since the catalyst (amine compound salt) concerning this invention is also a metal free (metal free) catalyst, the removal process of a metal (metal) is not required and it is useful also from a viewpoint of green chemistry.
  • the amine compound salt that is a catalyst according to the present invention may be supported on a carrier such as silica or alumina, or is incorporated in a polymer (polymer), that is, polymerized. It may be what has been done.
  • a carrier such as silica or alumina
  • polymer polymer
  • Such an amine compound salt has the advantage that it can be easily separated from the product cyclic carbonate in the process of isolating the cyclic carbonate from the reaction system, and can be recovered and reused. Since it also has the advantage of being, it is a practical catalyst that is useful from the viewpoint of green chemistry and that takes into consideration the reduction of environmental impact.
  • the carbon dioxide according to the present invention is used as a raw material for producing a cyclic carbonate.
  • the carbon dioxide is industrially produced by collecting, purifying, etc., carbon dioxide produced as a by-product in the production of electric power, gas, etc., but there is no particular limitation on the supply form, origin, and the like.
  • the purity of carbon dioxide is not necessarily high and may be diluted with an inert gas such as nitrogen gas or argon gas. However, since the reaction volume tends to increase if the purity of carbon dioxide is low, the carbon dioxide is preferably highly pure.
  • the purity of carbon dioxide is preferably 95% or more, particularly 99% or more.
  • the epoxide (oxirane) according to the present invention is used as a raw material for producing a cyclic carbonate in the same manner as the carbon dioxide described above.
  • the epoxide (oxirane) is not particularly limited as long as it is usually used in this field, and may have at least one oxirane ring, and may have two or more oxirane rings. You may have other functional groups, such as an ether group and an acyl group.
  • Specific examples of the epoxide (oxirane) include those selected from the epoxide (oxirane) represented by the following general formula [4] or the epoxide (oxirane) represented by the following general formula [5].
  • a 1 , A 2 , A 3 and A 4 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom.
  • a 1 and A 2 , A 1 and A 4 or A 3 and A 4 may form a cyclic structure.
  • a 5 , A 6 , A 7 , A 8 , A 9 and A 10 are each independently a monovalent hydrocarbon having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom.
  • T represents a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hetero atom, wherein A 5 and A 6 , A 5 and A 7 , A 8 and A 10 Alternatively, A 9 and A 10 may form a cyclic structure.
  • the monovalent hydrocarbon groups represented by A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 in the general formulas [4] and [5] Specific examples include an alkyl group, an alkenyl group, an aryl group, and an aralkyl group.
  • hetero atom represented by A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 in the general formulas [4] and [5].
  • Specific examples of the hetero atom in the monovalent hydrocarbon group having 1 to 20 carbon atoms may include, for example, an oxygen atom, a sulfur atom, for example, a halogen atom such as a fluorine atom and a chlorine atom.
  • the monovalent hydrocarbon groups represented by A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 in the general formulas [4] and [5] are alkyl. Specific examples in the case of a group, that is, A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 in the general formulas [4] and [5]
  • the alkyl group which may have a hetero atom shown may be linear, branched or cyclic.
  • alkyl group has no hetero atom
  • the alkyl group has no hetero atom
  • examples of the case where the alkyl group has no hetero atom include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, Cyclobutyl group, n-pentyl group, isopentyl group, s-pentyl group, t-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group , Isohexyl group, s-hexyl group, t-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-di
  • a 1, A 2, A 3 , A 4, A 5, A 6, A 7, A 8, A 9 and an alkyl group which may have a hetero atom is a heteroatom represented by A 10
  • a 10 Specific examples in the case of having, for example, methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, methoxyhexyl group, methoxyheptyl group, methoxyoctyl group, methoxynonyl group, methoxydecyl group, Methoxyundecyl group, methoxydodecyl group, methoxytridecyl group, methoxytetradecyl group, methoxypentadecyl group, methoxyhexadecyl group, methoxyheptadecyl group, methoxyoctadecyl group, methoxynonadecyl group, eth
  • methoxymethyl group methoxyethyl group, Methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, methoxyheptyl, methoxyoctyl, methoxynonyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxy Xyl group, ethoxyheptyl group, ethoxyoctyl group, propoxymethyl group, propoxyethyl group, propoxypropyl group, propoxybutyl group, propoxypentyl group, propoxyhexyl group, propoxyheptyl group, butoxymethyl group, butoxyethyl group, butoxypropyl group , Butoxybutyl group, butoxypentyl group, butoxyhexyl group, pentyloxymethyl group, pentyl
  • Ruoro group fluorine atom having 1 to 10 straight with an alkyl group branched or cyclic are preferred.
  • the alkyl group is not limited to the normal-form, but may be a branched or cyclo-form alkyl group such as a sec-form, tert-form, iso-form, or neo-form. May be.
  • the monovalent hydrocarbon groups represented by A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 in the general formulas [4] and [5] are alkenyl. Specific examples in the case of a group, that is, A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 in the general formulas [4] and [5]
  • the alkenyl group which may have a hetero atom shown may be linear, branched or cyclic.
  • alkenyl group has no hetero atom
  • the alkenyl group has no hetero atom
  • examples of the case where the alkenyl group has no hetero atom include, for example, a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group.
  • Tridecenyl group Tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group and the like, and examples thereof include vinyl group, propenyl group, butenyl group.
  • a linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms such as a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group and a decenyl group is preferred.
  • alkenyl group having a hetero atom examples include, for example, vinyloxymethyl group, vinyloxyethyl group, vinyloxypropyl group, propenyloxymethyl group, propenyloxyethyl group, propenyloxypropyl group, butenyl Ether groups such as oxymethyl group, butenyloxyethyl group, butenyloxypropyl group, pentenyloxymethyl group, pentenyloxyethyl group, pentenyloxypropyl group, hexenyloxymethyl group, hexenyloxyethyl group, hexenyloxypropyl group ( An oxygen atom) having 3 to 20 carbon atoms, such as acryloyloxymethyl group, acryloyloxyethyl group, acryloyloxypropyl group, methacryloyloxymethyl group, methacryloyloxyethyl group, Tacryloyloxypropyl group, Crotonoyloxy
  • alkenyl groups having 2 to 20 carbon atoms having a fluoro group fluorine atom
  • a straight chain having 3 to 10 carbon atoms and having an ether group (oxygen atom) such as a xylpropyl group, a pentenyloxymethyl group, a pentenyloxyethyl group, a pentenyloxypropyl group, a hexenyloxymethyl group, a hexenyloxyethyl group, a hexenyloxypropyl group , Branched or cyclic alkenyl groups
  • the alkyl group and alkenyl group are not limited to normal-forms, but are branched or cycloalkenyl such as sec-form, tert-form, iso-form, neo-form, etc. It may be a group.
  • the position of the double bond in the alkenyl group is not limited to the 1st position, and may be an alkenyl group having a double bond at a position different from the 1st position such as the 2nd position, the 3rd position, and the ⁇ position.
  • the monovalent hydrocarbon groups represented by A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 in the general formulas [4] and [5] are aryl. Specific examples in the case of a group, that is, A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 in the general formulas [4] and [5] Specific examples of the aryl group having 1 to 20 carbon atoms which may have a heteroatom may be monocyclic or condensed polycyclic.
  • aryl group having no hetero atom examples include, for example, a phenyl group, a naphthyl group, an azulenyl group, a biphenylyl group, an indacenyl group, an acenaphthylenyl group, a phenanthryl group, an anthryl group (anthracenyl group) and the like.
  • an aryl group having 6 to 14 carbon atoms such as a phenyl group is preferable.
  • aryl group having a hetero atom examples include, for example, a perfluorophenyl group, a perfluoronaphthyl group, a perfluoroazurenyl group, a perfluorobiphenylyl group, a perfluoroindacenyl group, and a perfluoroacena group.
  • aryl groups having 6 to 14 carbon atoms having a fluoro group (fluorine atom) such as a phthalenyl group, a perfluorophenanthryl group, and a perfluoroanthryl group (perfluoroanthracenyl group).
  • An aryl group having 6 carbon atoms having a fluoro group (fluorine atom) such as a perfluorophenyl group is preferable.
  • the monovalent hydrocarbon group represented by A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 in the general formulas [4] and [5] is aralkyl.
  • aralkyl Specific examples in the case of a group, that is, A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 and A 10 in the general formulas [4] and [5]
  • the aralkyl group which may have a hetero atom shown may be either monocyclic or condensed polycyclic.
  • aralkyl group has no hetero atom
  • examples of the case where the aralkyl group has no hetero atom include, for example, benzyl group, phenethyl group, methylbenzyl group, phenylpropyl group, 1-methylphenylethyl group, phenylbutyl group, 2-methylphenylpropyl group, Examples thereof include aralkyl groups having 7 to 20 carbon atoms such as a tetrahydronaphthyl group, a naphthylmethyl group, a naphthylethyl group, an indenyl group, and a fluorenyl group.
  • the aralkyl group has a hetero atom examples include, for example, a phenyloxymethyl group, a phenyloxyethyl group, a phenyloxypropyl group, a benzyloxymethyl group, a benzyloxyethyl group, a benzyloxypropyl group, a phenethyloxy group.
  • Examples thereof include an aralkyl group having 7 to 20 carbon atoms having a hetero atom such as an oxygen atom such as a sulfur atom, and a sulfur atom.
  • divalent hydrocarbon group represented by T in the general formula [5] examples include an alkylene group (alkanediyl group), an alkenylene group, an arylene group, and an aralkylene group.
  • hetero atom in the divalent hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom represented by T in the general formula [5] include, for example, an oxygen atom, a sulfur atom, such as fluorine Examples thereof include halogen atoms such as atoms and chlorine atoms.
  • divalent hydrocarbon group represented by T in the general formula [5] is an alkylene group (alkanediyl group), that is, having a heteroatom represented by T in the general formula [5]
  • alkylene group alkanediyl group
  • Specific examples of the alkylene group (alkanediyl group) may be linear, branched or cyclic.
  • alkylene group (alkanediyl group) having no hetero atom examples include, for example, a methylene group (methanediyl group), an ethylene group (ethane-1,2-diyl group), a propylene group (propane-1, 2-diyl group), trimethylene group (propane-1,3-diyl group), tetramethylene group (butane-1,4-diyl group), pentamethylene group (pentane-1,5-diyl group), hexamethylene group (Hexane-1,6-diyl group), heptamethylene group (heptane-1,7-diyl group), octamethylene group (octane-1,8-diyl group), nonamethylene group (nonane-1,9-diyl group) ), Decamethylene group (decane-1,10-diyl group), undecane methylene group (undecane-1,10
  • alkylene group (alkanediyl group) having a hetero atom examples include, for example, a methylene bis (oxymethyl) group, a methylene bis (oxyethyl) group, a methylene bis (oxypropyl) group, a methylene bis (oxybutyl) group, and a methylene bis.
  • (Oxypentyl) group ethylenebis (oxymethyl) group, ethylenebis (oxyethyl) group, ethylenebis (oxypropyl) group, ethylenebis (oxybutyl) group, ethylenebis (oxypentyl) group, trimethylenebis (oxymethyl) ) Group, trimethylenebis (oxyethyl) group, trimethylenebis (oxypropyl) group, trimethylenebis (oxybutyl) group, trimethylenebis (oxypentyl) group, tetramethylenebis (oxymethyl) group, tetramethylenebis ( Oxy Til) group, tetramethylene bis (oxypropyl) group, tetramethylene bis (oxybutyl) group, tetramethylene bis (oxypentyl) group, pentamethylene bis (oxymethyl) group, pentamethylene bis (oxyethyl) group, pentamethylene bis And an alkylene group having 3 to 20 carbon atoms (alkanediyl group) having an ether
  • alkylene group is not limited to the normal-form, but is branched such as sec-form, tert-form, iso-form, neo-form, or cyclic form such as cyclo-form. May be an alkylene group (alkanediyl group).
  • divalent hydrocarbon group represented by T in the general formula [5] is an alkenylene group, that is, as an alkenylene group optionally having a hetero atom represented by T in the general formula [5] May be linear, branched or cyclic.
  • alkenylene group having no hetero atom examples include, for example, vinylene group, propenylene group, butenylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, nonenylene group, decenylene group, undecenylene group, dodecenylene group
  • An alkenylene group having 2 to 20 carbon atoms such as a tridecenylene group, a tetradecenylene group, a pentadecenylene group, a hexadecenylene group, a heptadecenylene group, an octadecenylene group, a nonadecenylene group, and an icosenylene group.
  • alkenylene group has a hetero atom
  • the alkenylene group has a hetero atom
  • a perfluorovinylene group a perfluoropropenylene group, a perfluorobutenylene group, a perfluoropentenylene group, a perfluorohexenylene group, Perfluoroheptenylene group, perfluorooctenylene group, perfluorononenylene group, perfluorodecenylene group, perfluoroundecenylene group, perfluorododecenylene group, perfluorotridecenylene group, perfluoro Tetradecenylene group, perfluoropentadecenylene group, perfluorohexadecenylene group, perfluoroheptadecenylene group, perfluorooctadecenylene group, perfluorononadecenylene group, perfluoroicoseni group 2
  • the alkenylene group is not limited to a normal-form, but is a branched alkenylene group such as a sec-form, tert-form, iso-form, or neo-form, or a cyclo-form. May be.
  • the position of the double bond in the alkenylene group is not limited to the 1-position, and may be an alkenylene group having a double bond at a position different from the 1-position such as the 2-position, the 3-position, and the ⁇ -position.
  • the divalent hydrocarbon group represented by T in the general formula [5] is an arylene group, that is, the arylene group optionally having a heteroatom represented by T in the general formula [5] As a specific example, it may be monocyclic or condensed polycyclic.
  • the arylene group having no hetero atom include arylene groups having 6 to 12 carbon atoms such as a phenylene group, a naphthylene group, and a biphenylene group.
  • arylene group having a hetero atom examples include arylene having 6 to 12 carbon atoms having a fluoro group (fluorine atom) such as a perfluorophenylene group, a perfluoronaphthylene group, and a perfluorobiphenylene group. Groups and the like.
  • the divalent hydrocarbon group represented by T in the general formula [5] is an aralkylene group, that is, the aralkylene group optionally having a hetero atom represented by T in the general formula [5] As a specific example, it may be monocyclic or condensed polycyclic. Specific examples of the case where the aralkylene group does not have a hetero atom include, for example, benzylene group, phenethylene group, phenylpropylene group, phenylbutylene group, tetrahydronaphthylene group, naphthylmethylene group, naphthylethylene group, etc. There are 20 aralkylene groups.
  • aralkylene group having a hetero atom examples include, for example, a methylene bis (phenoxymethyl) group, a methylene bis (phenoxyethyl) group, a methylene bis (phenoxypropyl) group, an ethylene bis (phenoxymethyl) group, an ethylene bis ( Phenoxyethyl) group, ethylenebis (phenoxypropyl) group, dimethylmethylenebis (phenoxymethyl) group, dimethylmethylenebis (phenoxyethyl) group, diperfluoromethylmethylenebis (phenoxymethyl) group, diperfluoromethylmethylenebis ( Phenoxyethyl) group, trimethylene bis (phenoxymethyl) group, trimethylene bis (phenoxyethyl) group, tetramethylene bis (phenoxymethyl) group, tetramethylene bis (phenoxyethyl) group, pentamethyl 15 carbon atoms having hetero atoms such as oxygen atoms and fluorine atoms such as bis (phenoxymethyl)
  • a 1 and A 2 , A 1 and A 4 , A 3 and A 4 , A 5 and A 6 , A 5 and A 7 , A 8 and A 10 , A 9 and A in the general formulas [4] and [5] 10 may form a cyclic structure with A 1 to A 10 and a carbon atom bonded to these A to form a cyclic structure (5 to 12-membered ring) having 3 to 10 carbon atoms. It means that it may be.
  • cyclic structure having 3 to 10 carbon atoms include, for example, a cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, And cyclododecane ring.
  • a cyclopentane ring cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, And cyclododecane ring.
  • Monocycles, polycycles, spiro rings, bridged rings, and substituents such as alkyl groups are further substituted on these rings. Also included.
  • epoxide (oxirane) represented by the general formula [4] include, for example, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, styrene. Examples thereof include those represented by the following formulas such as oxide, phenyl glycidyl ether, naphthyl glycidyl ether and the like.
  • the epoxide (oxirane) represented by the following formula is merely an example of a specific example, and is not limited to the specific example illustrated here.
  • epoxide (oxirane) represented by the general formula [5] include, for example, 1,2-bis (glycidyloxy) ethane ⁇ 1,2-ethylene glycol diglycidyl ether ⁇ , 1,3-bis (glycidyloxy).
  • epoxides represented by the general formulas [4] and [5] may be commercially available products or those appropriately synthesized by general methods performed in this field.
  • the structure of the cyclic carbonate which is a product is not limited.
  • Specific examples of the cyclic carbonate include, for example, the above general formula [4] As a cyclic carbonate generated from the epoxide (oxirane) represented by the following general formula [6], or as a cyclic carbonate generated from the epoxide (oxirane) represented by the general formula [5], the following general formula What is shown by [7] is mentioned.
  • cyclic carbonate represented by the general formula [6] include, for example, (methoxymethyl) ethylene carbonate, (ethoxymethyl) ethylene carbonate, (propoxymethyl) ethylene carbonate, (butoxymethyl) ethylene carbonate, (pentyloxymethyl) Ethylene carbonate, (hexyloxymethyl) ethylene carbonate, (2-oxo-1,3-dioxolan-4-yl) methyl acrylate, (2-oxo-1,3-dioxolan-4-yl) methyl methacrylate, (phenyl) What is shown by following formulas, such as ethylene carbonate, (phenoxymethyl) ethylene carbonate, (naphthyloxymethyl) ethylene carbonate, is mentioned.
  • the cyclic carbonate shown by the following formula is an example of a specific example to the last, Comprising: It is not limited to the specific example illustrated here.
  • cyclic carbonate represented by the general formula [7] examples include 1,2-ethylenedioxybis [(methyl) ethylene carbonate], 1,3-propylenedioxybis [(methyl) ethylene carbonate], 1 , 4-Butylenedioxybis [(methyl) ethylene carbonate], 1,5-pentylenedioxybis [(methyl) ethylene carbonate], 1,6-hexylenedioxybis [(methyl) ethylene carbonate], methylenebis [ (P-phenoxymethyl) ethylene carbonate] ⁇ bisphenol F diglycidyl ether biscarbonate ⁇ , 1,1-ethylenebis [(p-phenoxymethyl) ethylene carbonate] ⁇ bisphenol E diglycidyl ether biscarbonate ⁇ , 2,2-propylene Bis [(p-phenoxime ) Ethylene carbonate] ⁇ bisphenol A diglycidyl ether ⁇ ⁇ biscarbonate ⁇ , 2,2-hexafluoropropylenebis [(p-phenoxymethyl) ethylene carbonate] ⁇ bisphenol AF
  • epoxide (oxirane), carbon dioxide, the amine compound according to the present invention and hydrogen iodide are charged into the reaction system.
  • epoxide (oxirane) the amine compound according to the present invention and hydrogen iodide are sequentially charged into the reaction system, and a method of blowing carbon dioxide gas into the reaction system into which these are charged, the amine compound according to the present invention and After reacting hydrogen iodide to obtain a catalyst according to the present invention, epoxide (oxirane) and the catalyst according to the present invention are sequentially charged into the reaction system, and carbon dioxide gas is introduced into the reaction system into which these are charged.
  • the method of blowing in is mentioned.
  • the production method of the present invention is desirably performed under the following conditions.
  • the amount of carbon dioxide used in the present invention is not particularly limited as long as it is a practical amount. For example, it is usually 0.9 equivalent or more, preferably 0.95 equivalent or more, relative to the number of moles of epoxide (oxirane), More preferably, it is 1.0 equivalent or more, and there is no particular upper limit. However, for economic reasons, 20 equivalent or less is preferable.
  • the amount of the amine compound used in the present invention is usually 0.1 to 30 mol%, preferably 0.5 to 20 mol%, based on 1 mol of epoxide (oxirane).
  • epoxide oxirane
  • the amount of hydrogen iodide used in the present invention is usually 0.1 to 30 mol%, preferably 0.5 to 20 mol%, based on 1 mol of epoxide (oxirane).
  • epoxide oxirane
  • the amount of the catalyst (amine compound salt) used in the present invention is usually 0.1 to 30 mol%, preferably 0.5 to 20 mol%, based on 1 mol of epoxide (oxirane).
  • the usage-amount of the said catalyst (amine compound salt) is very small, it exists in the tendency for the yield of a cyclic carbonate to fall.
  • the production method of the present invention may be performed in an organic solvent in which an organic solvent is added to the reaction system, or may be performed in a system in which no organic solvent is added.
  • the raw material epoxide (oxirane) and the product cyclic carbonate also serve as a solvent.
  • organic solvent may be any solvent that does not adversely affect the raw material epoxide (oxirane) and carbon dioxide, and the product cyclic carbonate.
  • aliphatic carbonization such as hexane, heptane, and octane.
  • Hydrogen solvents such as aromatic hydrocarbon solvents such as benzene, toluene and xylene, halogen solvents such as dichloromethane, trichloromethane (chloroform) and tetrachloromethane (carbon tetrachloride) such as diethyl ether, diisopropyl ether and methyl Ether solvents such as t-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, such as 2-propanone (acetone), 2-butanone (ethyl methyl ketone), 4-methyl-2-pentanone (Mechi Ketone solvents such as isobutyl ketone) such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, s-butyl acetate, t-but
  • organic solvents such as polar organic solvents, nonpolar organic solvents, protic organic solvents, aprotic organic solvents, and the like. It is desirable to select appropriately considering the solubility of the compound salt) in the organic solvent.
  • polar organic solvents such as polar organic solvents, nonpolar organic solvents, protic organic solvents, aprotic organic solvents, and the like. It is desirable to select appropriately considering the solubility of the compound salt) in the organic solvent.
  • polar organic solvents such as polar organic solvents, nonpolar organic solvents, protic organic solvents, aprotic organic solvents, and the like. It is desirable to select appropriately considering the solubility of the compound salt) in the organic solvent.
  • nonpolar organic solvents such as polar organic solvents, nonpolar organic solvents, protic organic solvents, aprotic organic solvents, and the like. It is desirable to select appropriately considering the solubility of the compound salt) in the organic solvent.
  • amine compound salt for example, N, N-dimethylformamide
  • an amide solvent such as 1-methyl-2-pyrrolidinone (N-methylpyrrolidone), 1,3-dimethyl-2-imidazolidinone (dimethylethyleneurea), and the catalyst according to the present invention
  • an aliphatic hydrocarbon solvent such as hexane, heptane, octane
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, such as diethyl ether, diisopropyl ether, methyl t- Ether solvents such as tilether, cyclopentylmethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, such as ethyl acetate, n-propyl acetate,
  • the above organic solvents may be used alone or in combination of two or more.
  • the amount of the organic solvent used is not particularly limited as long as it is a practical amount, and is usually 0.01 to 500 mL, preferably 0.1 to 100 mL, with respect to 1 mmol of epoxide (oxirane), for example.
  • the temperature during the reaction is desirably set to a temperature at which the raw material epoxide (oxirane) and carbon dioxide efficiently react to obtain a cyclic carbonate in good yield. Since the present invention is characterized in that a cyclic carbonate can be obtained in good yield even under mild conditions such as normal temperature and normal pressure, among such desirable reaction temperatures, for example, usually 0 to 65 ° C.
  • the reaction is preferably carried out at 20 to 60 ° C., more preferably 40 to 60 ° C.
  • the pressure at the time of reaction in the present invention is desirably set to a pressure at which the epoxide (oxirane) as a raw material and carbon dioxide efficiently react to obtain a cyclic carbonate in a high yield. Since the present invention is characterized in that a cyclic carbonate can be obtained in a high yield even under mild conditions such as normal temperature and normal pressure, among such desirable pressures, for example, 0.09 to 0.00. It is desirable to carry out the reaction at 11 MPa.
  • reaction temperature and pressure described above are reaction conditions that have been difficult to achieve with conventional production methods. Since the manufacturing method of the present invention does not require the high temperature and high pressure conditions required by the conventional manufacturing method, compared with the conventional manufacturing method, it requires less heat energy to maintain the temperature and has a high strength. There is an advantageous effect suitable for production on an industrial scale such that a pressure vessel is not required.
  • the reaction time in the present invention is the kind of the epoxide (oxirane) and the amine compound according to the present invention, the amount of carbon dioxide used with respect to the epoxide (oxirane), and the amount of amine compound and hydrogen iodide according to the present invention with respect to the epoxide (oxirane).
  • the presence or absence of addition of an organic solvent, the type and amount of the organic solvent used, the reaction temperature, and the pressure during the reaction may be affected.
  • the desired reaction time cannot be generally stated, but is usually 0.1 to 120 hours, preferably 1 to 72 hours, for example.
  • the cyclic carbonate obtained by the production method of the present invention can be isolated by general post-treatment operations and purification operations usually performed in this field.
  • the isolation method for example, if necessary, after distilling off the organic solvent in the reaction system, the resulting residue is subjected to recrystallization, distillation, column chromatography, etc. It can be isolated.
  • the cyclic residue can be isolated by performing an extraction operation on the obtained residue and removing impurities, followed by recrystallization, distillation, column chromatography, or the like.
  • the preparation method of the catalyst (amine compound salt) according to the present invention mainly includes three preparation methods. Specifically, [1] a method of reacting an amine compound according to the present invention with hydroiodic acid, [2] an amine according to the present invention such as a hydrochloride or trifluoromethanesulfonate of the amine compound according to the present invention A method of reacting a salt of a compound with an alkali metal iodide salt such as sodium iodide to exchange anions, [3] After reacting a thiourea derivative with an alkyl iodide to give an isothiourea salt, mono or diamine The method of making it react with is mentioned.
  • the catalyst (amine compound salt) according to the present invention in the case of reacting the amine compound according to the present invention with hydroiodic acid may be prepared according to a general neutralization reaction.
  • Specific examples of the preparation method include, for example, in the reaction system containing the amine compound according to the present invention, usually 0.9 to 5.0 equivalents, preferably 1.0, in terms of hydrogen iodide, relative to the amine compound. It is sufficient to react with ⁇ 3.0 equivalents of hydroiodic acid.
  • the catalyst (amine compound salt) according to the present invention, which is the target product is often in a solid state at normal temperature, and since the reaction system contains water derived from hydroiodic acid, It is desirable to carry out in an organic solvent compatible with water.
  • amine compound according to the present invention include, as described above, for example, a monoamine represented by the general formula [1], a cyclic amidine represented by the general formula [2], and the general formula [3]. Those selected from guanidine.
  • hydroiodic acid For example, commercially available 57% hydroiodic acid may be used as the hydroiodic acid.
  • organic solvent compatible with water examples include ether solvents such as tetrahydrofuran and 1,4-dioxane, such as 2-propanone (acetone) and 2-butanone.
  • ether solvents such as tetrahydrofuran and 1,4-dioxane
  • 2-propanone (acetone) and 2-butanone examples thereof include ketone solvents such as (ethyl methyl ketone), and nitrile solvents such as acetonitrile.
  • the said organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the organic solvent compatible with water is not particularly limited as long as it is a practical amount.
  • the amount is usually 0.01 to 500 mL, preferably 0.1 to 100 mL per 1 mmol.
  • reaction temperature a temperature at which the amine compound according to the present invention and hydroiodic acid are reacted.
  • the temperature is preferably 10 to 50 ° C.
  • the pressure during the reaction in the preparation method [1] described above is not particularly limited as long as it is a pressure at which the amine compound according to the present invention and hydroiodic acid react, and is, for example, 0.09 to 0.11 MPa.
  • the reaction time in the preparation method of [1] described above is the kind of amine compound according to the present invention, the amount of hydroiodic acid used for the amine compound according to the present invention, the kind and amount of organic solvent used, the reaction temperature, and It may be affected by the pressure during the reaction. For this reason, the desired reaction time cannot be generally stated, but is usually 0.1 to 120 hours, preferably 1 to 60 hours, for example.
  • the catalyst (amine compound salt) according to the present invention obtained by the preparation method of [1] described above can be isolated by general post-treatment operations and purification operations usually performed in this field.
  • the isolation method for example, after distilling off an organic solvent compatible with water and water derived from hydroiodic acid in the reaction system, the obtained residue is vacuum-dried to thereby obtain the present invention.
  • the catalyst (amine compound salt) can be isolated.
  • the catalyst (amine compound salt) concerning this invention can be isolated also by performing recrystallization, distillation, column chromatography etc. about the obtained residue as needed.
  • the preparation of the catalyst (amine compound salt) according to the present invention in the case of anion exchange by reacting the salt of the amine compound according to the present invention with an alkali metal iodide salt is in accordance with a general anion exchange reaction. Just do it.
  • a specific example of the preparation method for example, in the reaction system containing the salt of the amine compound according to the present invention, usually 0.9 to 3.0 equivalents, preferably 0.95 to 2 with respect to the salt of the amine compound. It is sufficient to react 0.0 equivalent of an alkali metal iodide salt.
  • the salt of the amine compound and alkali metal iodide salt according to the present invention as raw materials and the catalyst according to the present invention as the target (amine compound salt) are often in a solid state at room temperature, they are prepared. Is preferably carried out in an organic solvent.
  • salt of the amine compound according to the present invention used for anion exchange by reacting with an alkali metal iodide salt include, as an example, monoisopropylamine hydrochloride, monoisopropylamine acetate, monoisopropylamine Trifluoromethane sulfonate, mono-t-butylamine ⁇ ⁇ hydrochloride, mono-t-butylamine acetate, mono-t-butylamine trifluoromethanesulfonate, monocyclohexylamine ⁇ ⁇ hydrochloride, monocyclohexylamine acetate, monocyclohexylamine Trifluoromethane sulfonate, dicyclohexylamine ⁇ hydrochloride, dicyclohexylamine ⁇ acetate, dicyclohexylamine trifluoromethanesulfonate, benzyldimethylamine ⁇ ⁇ hydrochloride, benzyl dimethyl
  • the salt of the amine compound concerning this invention shown by the above-mentioned specific example is an example of a specific example to the last, Comprising: It is not limited to the specific example illustrated here.
  • n- represents a normal-form and t- represents a tert-form.
  • n- represents a normal-form
  • t- represents a tert-form.
  • what is necessary is just to use what was synthesize
  • alkali metal iodide salts include lithium iodide, sodium iodide, potassium iodide, cesium iodide and the like. Moreover, the said alkali metal iodide salt should just use a commercial item.
  • organic solvent examples include ether solvents such as diethyl ether, diisopropyl ether, methyl t-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, Ketone solvents such as 2-propanone (acetone), 2-butanone (ethyl methyl ketone), 4-methyl-2-pentanone (methyl isobutyl ketone), such as methanol, ethanol, isopropanol, t-butanol, 2-methoxyethanol, etc. Alcohol solvents such as nitrile solvents such as acetonitrile. In the above specific examples, t- represents a tert-isomer. Moreover, the said organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • ether solvents such as diethyl ether, diisopropyl ether, methyl t-butyl ether, tetrahydro
  • the amount of the organic solvent used is not particularly limited as long as it is a practical amount.
  • the amount is usually 0.01 to 500 mL, preferably 0.1 to 100 mL.
  • reaction temperature in the preparation method [2] described above is not particularly limited as long as it is a temperature at which the salt of the amine compound according to the present invention reacts with the alkali metal iodide salt. -150 ° C, preferably 10-100 ° C.
  • the pressure during the reaction in the preparation method [2] is not particularly limited as long as the salt of the amine compound according to the present invention is reacted with the alkali metal iodide salt. 11 MPa.
  • the reaction time in the preparation method of [2] described above is the kind of the salt of the amine compound according to the present invention, the amount of the alkali metal iodide salt used with respect to the salt of the amine compound according to the present invention, the kind of the organic solvent and the amount of its use. ,
  • the reaction temperature, and the pressure during the reaction may be affected.
  • the desired reaction time is not generally known, but is usually 0.1 to 120 hours, preferably 1 to 60 hours, for example.
  • the catalyst (amine compound salt) according to the present invention obtained by the above-described preparation method [2] can be isolated by general post-treatment operations and purification operations usually performed in this field.
  • the isolation method for example, the organic solvent in the reaction system is distilled off, followed by an extraction operation, and then the residue obtained by distilling off the extraction solvent in the extract is vacuum-dried.
  • the catalyst (amine compound salt) according to the present invention can be isolated.
  • the catalyst (amine compound salt) concerning this invention can be isolated also by performing recrystallization, distillation, column chromatography etc. about the obtained residue as needed.
  • a preparation method in which a thiourea derivative and an alkyl iodide are reacted to form an isothiourea salt and then reacted with a mono- or diamine is a general formula [3 ′] of the catalyst (amine compound salt) according to the present invention.
  • a specific example of the preparation method for example, in a reaction system containing a thiourea derivative, usually 0.9 to 3.0 equivalents, preferably 0.95 to 2.0 equivalents of an alkyl iodide with respect to the thiourea derivative.
  • an isothiourea salt and then 0.9 to 3.0 equivalents, preferably 0.95 to 2.0 equivalents of mono- or diamine may be reacted with the isothiourea salt.
  • the isothiourea salt that is an intermediate and the catalyst (amine compound salt) according to the present invention that is an object are often in a solid state at room temperature, the preparation is preferably performed in an organic solvent. .
  • thiourea derivative examples include thiourea, N-methylthiourea, N, N-dimethylthiourea, N, N, N-trimethylthiourea, N, N, N, N-tetramethylthiourea and the like.
  • the thiourea derivative shown by the above-mentioned specific example is an example of a specific example to the last, Comprising: It is not limited to the specific example illustrated here.
  • the thiourea derivative may be a commercially available product.
  • alkyl iodide examples include alkyl iodides such as methyl iodide, ethyl iodide, and propyl iodide. Moreover, what is necessary is just to use a commercial item for the said alkyl iodide.
  • mono or diamine examples include, for example, mono or di n-butylamine, mono or di n-octylamine, mono or dicyclohexylamine, mono or dibenzylamine, mono or bis (2-hydroxyethyl) amine, mono or bis (2-methoxyethyl) amine, mono- or bis (2-dimethylaminoethyl) amine and the like can be mentioned.
  • the mono- or diamine shown in the above specific examples is merely an example of specific examples, and is not limited to the specific examples illustrated here.
  • n- represents a normal-body.
  • the said mono or diamine should just use a commercial item.
  • organic solvent examples include aliphatic hydrocarbon solvents such as hexane, heptane, and octane, such as benzene, Aromatic hydrocarbon solvents such as toluene and xylene, for example, halogen solvents such as dichloromethane, trichloromethane (chloroform), tetrachloromethane (carbon tetrachloride), such as diethyl ether, diisopropyl ether, methyl t-butyl ether, tetrahydrofuran, 2 Examples include ether solvents such as 1-methyltetrahydrofuran and 1,4-dioxane, alcohol solvents such as methanol, ethanol, isopropanol, t-butanol, and 2-methoxyethanol, and nitrile solvents such as aceton
  • the amount of the organic solvent used is not particularly limited as long as it is a practical amount. On the other hand, it is usually 0.01 to 500 mL, preferably 0.1 to 100 mL.
  • organic solvent examples include aliphatic carbonization such as hexane, heptane, and octane.
  • Hydrogen solvents such as aromatic hydrocarbon solvents such as benzene, toluene and xylene, halogen solvents such as dichloromethane, trichloromethane (chloroform) and tetrachloromethane (carbon tetrachloride) such as diethyl ether, diisopropyl ether and methyl
  • halogen solvents such as dichloromethane, trichloromethane (chloroform) and tetrachloromethane (carbon tetrachloride)
  • diethyl ether diisopropyl ether and methyl
  • ether solvents such as t-butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and nitrile solvents such as acetonitrile.
  • t- represents a tert-isomer.
  • the said organic solvent may be used individually by 1 type,
  • the amount of the organic solvent used is not particularly limited as long as it is a practical amount.
  • the amount of the organic solvent used is usually 0.01 to 500 mL, preferably 0.1 to 100 mL.
  • reaction temperature in the reaction for synthesizing the isothiourea salt, which is an intermediate in the above preparation method [3], is particularly limited as long as it is a temperature at which the thiourea derivative reacts with alkyl iodide.
  • reaction temperature is usually 0 to 100 ° C., preferably 10 to 80 ° C.
  • reaction temperature in the reaction for synthesizing the catalyst (amine compound salt) according to the present invention, which is the object of the preparation method of [3] above, is the reaction of isothiourea salt with mono- or diamine.
  • the temperature is not particularly limited as long as it is a temperature to be used, for example, usually 0 to 100 ° C., preferably 10 to 80 ° C.
  • the reaction pressure in the reaction for synthesizing the isothiourea salt which is an intermediate in the preparation method of the above [3] is not particularly limited as long as it is a pressure at which the thiourea derivative reacts with alkyl iodide. 0.09 to 0.11 MPa.
  • the reaction pressure in the reaction for synthesizing the catalyst (amine compound salt) according to the present invention which is the object of the preparation method of [3] above, may be a pressure at which the isothiourea salt reacts with mono- or diamine. For example, it is 0.09 to 0.11 MPa.
  • the reaction time in the reaction for synthesizing the isothiourea salt which is an intermediate in the preparation method of [3] above, is the kind of thiourea derivative, the amount of alkyl iodide used for the thiourea derivative, the kind of organic solvent and its It may be affected by the amount used, reaction temperature, and pressure during the reaction. For this reason, the desired reaction time cannot be generally stated, but is usually 0.1 to 120 hours, preferably 1 to 60 hours, for example.
  • the reaction time in the reaction for synthesizing the catalyst (amine compound salt) according to the present invention is the type of isothiourea salt, the amount of mono- or diamine used relative to the isothiourea salt. It may be affected by the type and amount of organic solvent used, the reaction temperature, the pressure during the reaction, and the like. For this reason, the desired reaction time cannot be generally stated, but is usually 0.1 to 60 hours, preferably 1 to 30 hours, for example.
  • the isothiourea salt obtained by the reaction for synthesizing the isothiourea salt which is an intermediate in the preparation method of the above [3] is usually isolated by a general post-treatment operation and purification operation performed in this field. be able to.
  • the isolation method for example, the unreacted alkyl iodide and the organic solvent in the reaction system are distilled off, and then the resulting residue is vacuum dried to isolate the isothiourea salt. .
  • an isothiourea salt can be isolated also by performing recrystallization, distillation, column chromatography etc. about the obtained residue as needed.
  • the catalyst (amine compound salt) according to the present invention obtained by the reaction for synthesizing the catalyst (amine compound salt) according to the present invention which is the object of the preparation method of [3] above, is usually carried out in this field. It can be isolated by general post-treatment operations and purification operations. As a specific example of the isolation method, for example, unreacted mono- or diamine and the organic solvent in the reaction system are distilled off, and then the resulting residue is vacuum-dried, whereby the catalyst according to the present invention (amine compound salt). Can be isolated. Moreover, the catalyst (amine compound salt) concerning this invention can be isolated also by performing recrystallization, distillation, column chromatography etc. about the obtained residue as needed.
  • the preparation method is not particularly limited, You may prepare by methods other than the manufacturing method mentioned above.
  • a compound having a highly active hydrogen atom may coexist during the reaction.
  • the compound having a highly active hydrogen atom means a compound having a hydrogen atom capable of hydrogen bonding with an oxygen atom of an epoxide capable of hydrogen bonding with an oxygen atom of an epoxide (oxirane) as a raw material. More specifically, the compound has a hydroxyl group, carboxyl group, thiol group, thiocarboxyl group, primary or secondary amino group, primary or secondary amide group, sulfo group, ureylene group, thioureylene in the molecule. Having at least one group selected from a group and a hydroxyboryl group.
  • the compound having a hydroxyl group in the molecule include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, perfluoromethanol, perfluoroethanol, perfluoro.
  • aliphatic alcohols such as n-propanol, hexafluoroisopropanol, perfluoroisopropanol, methoxymethanol, methoxyethanol, ethoxymethanol, ethoxyethanol, such as phenol, 4-methylphenol, 4-methoxyphenol, 4-nitrophenol, 2, Aromatic alcohols such as 2′-biphenol, 2-hydroxypyridine, and 3-hydroxypyridine are exemplified.
  • n- represents a normal isomer
  • s- represents a sec isomer
  • t- represents a tert isomer.
  • the compound having a carboxyl group in the molecule include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid and lauric acid.
  • aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid and lauric acid.
  • Acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids such as lactic acid, malic acid, tartaric acid and citric acid
  • An aliphatic tricarboxylic acid such as aconitic acid, an aliphatic oxocarboxylic acid such as pyruvic acid, an aromatic monocarboxylic acid such as benzoic acid, an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, etc.
  • Aromatic hydroxy carboxylic acids such as salicylic acid and gallic acid, for example aromatic hex such as melittic acid A carboxylic acid.
  • a carboxylic acid having one or more hydroxyl groups in the molecule is referred to as a hydroxycarboxylic acid regardless of the number of carboxyl groups.
  • the compound having a thiol group in the molecule include fats such as methanethiol, ethanethiol, n-propanethiol, isopropanethiol, n-butanethiol, isobutanethiol, s-butanethiol, and t-butanethiol.
  • Group thiols for example, aromatic thiols such as thiophenol.
  • n- represents a normal isomer
  • s- represents a sec isomer
  • t- represents a tert isomer.
  • the compound having a thiocarboxyl group in the molecule include aliphatic thiocarboxylic acids such as thioformic acid, thioacetic acid, thiopropionic acid, thiobutyric acid, thiovaleric acid, and thiocaproic acid, and aromatics such as thiobenzoic acid. Examples thereof include thiocarboxylic acid.
  • the compound having a primary or secondary amino group in the molecule include aliphatic primary amines such as methylamine, ethylamine, propylamine, butylamine and ethanolamine, for example, aromatic primary amines such as aniline, Examples thereof include aliphatic secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine and diethanolamine, and aromatic secondary amines such as diphenylamine.
  • the compound having a primary or secondary amide group in the molecule include primary amides such as formamide, acetamide, and propanamide, such as N-methylformamide, N-ethylformamide, N-methylacetamide, N- Secondary amides such as ethylacetamide, N-methylpropanamide, N-ethylpropanamide and the like can be mentioned.
  • the compound having a sulfo group in the molecule include aliphatic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and trifluoromethanesulfonic acid, such as benzenesulfonic acid and toluenesulfonic acid. And aromatic sulfonic acids such as
  • Specific examples of the compound having a ureylene group in the molecule include 1- [3,5-bis (trifluoromethyl) phenyl] -3-phenyl-2-urea.
  • Specific examples of the compound having a thioureylene group in the molecule include 1- [3,5-bis (trifluoromethyl) phenyl] -3-phenyl-2-thiourea.
  • Specific examples of the compound having a hydroxyboryl group in the molecule include methyl boronic acid, ethyl boronic acid, propyl boronic acid, butyl boronic acid, propenyl boronic acid, phenyl boronic acid, 2-thiophene boronic acid and the like.
  • the compound having a highly active hydrogen atom not only a monomer but also a polymer can be used.
  • a polymer has a structure (functional group) containing a hydrogen atom capable of hydrogen bonding with an oxygen atom of the epoxide in the structure.
  • Such a polymer include, for example, a structure containing a hydrogen atom capable of hydrogen bonding with a vinyl group and an oxygen atom of an epoxide in the molecule, such as 4-hydroxystyrene, (meth) acrylic acid, and (meth) acrylamide.
  • a homopolymer composed of monomer units derived from a compound having (functional group) or a copolymer thereof for example, a copolymer composed of monomer units derived from 4-hydroxystyrene and monomer units derived from styrene, (meth) A structure (functional group) containing a hydrogen atom capable of hydrogen bonding with a vinyl group and an oxygen atom of epoxide in the molecule, such as a copolymer comprising a monomer unit derived from acrylic acid and a monomer unit derived from methacrylic acid ester A monomer unit derived from a compound having a hydrogen atom having a vinyl group in the molecule and capable of hydrogen bonding with an oxygen atom of an epoxide Structure (functional group) to have no compound copolymer comprising monomer units derived from including the child and the like.
  • the compounds having a highly active hydrogen atom one of them may be used alone, or two or more of them may be used in combination.
  • the reason why the reaction is accelerated when a compound having a highly active hydrogen atom is used is as follows. That is, since a compound having a highly active hydrogen atom has a coordination action similar to that of a metal ligand with respect to the oxygen atom of the epoxide (oxirane), protonation of the epoxide (oxirane) tends to occur more effectively. Thus, it is considered that the ring opening of the epoxide (oxirane) by the iodine anion in the catalyst (amine compound salt) according to the present invention is facilitated.
  • Synthesis Example 9 Synthesis of S-methylisothiourea hydrogen iodide salt In a suspension of 7.61 g (100 mmol; manufactured by Aldrich) of thiourea in 100 mL of dry ethanol, 17.0 g of methyl iodide (120 mmol; Kanto Chemical Co., Inc.) at room temperature The product was further reacted by stirring at room temperature for 12 hours. After completion of the reaction, the residue obtained by distilling off the solvent was vacuum-dried at 40 ° C. for 12 hours to obtain 21.8 g (yield: 100%) of S-methylisothiourea hydrogen iodide salt as a colorless powder. It was.
  • Synthesis Example 12 Synthesis of 1- (1-butyl) -3-methylguanidine hydrogen iodide [3′-B] To a solution of n-butylamine 731 mg (10 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) in dry tetrahydrofuran 10 mL, 25 2.32 g (10 mmol) of 23.2 g of N′-methyl-S-methylisothiourea hydrogen iodide salt obtained in Synthesis Example 11 was added at °C, and further stirred at 25 ° C. for 6 hours to react. I let you. After completion of the reaction, the residue obtained by distilling off the solvent was washed with diethyl ether, and the residue was vacuum-dried at 40 ° C.
  • Synthesis Example 14 Synthesis of 1- (1-butyl) -2,3-dimethylguanidine hydrogen iodide [3′-C] To a solution of n-butylamine 731 mg (10 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) in 10 mL of dry tetrahydrofuran Then, 2.46 g (10 mmol) of 24.6 g of N, N′-dimethyl-S-methylisothiourea hydrogen iodide obtained in Synthesis Example 13 was added at 25 ° C., and then at 25 ° C. for 6 hours. The reaction was stirred.
  • Synthesis Example 15 Synthesis of N, N ′, N′-trimethyl-S-methylisothiourea hydrogen iodide A solution of 23.7 g of trimethylthiourea (200 mmol; manufactured by Tokyo Chemical Industry Co., Ltd.) in 200 mL of dry ethanol at room temperature After adding 34.1 g of methyl iodide (240 mmol; manufactured by Kanto Chemical Co., Inc.), the mixture was further reacted by stirring at room temperature for 12 hours. After completion of the reaction, the residue obtained by distilling off the solvent was vacuum-dried at 40 ° C.
  • Synthesis Example 16 Synthesis of 1- (1-butyl) -2,3,3-trimethylguanidine hydroiodide [3′-D] N, N ′, N′-trimethyl-S— obtained in Synthesis Example 15 After adding 731 mg (10 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of n-butylamine at 25 ° C. to a solution of 2.60 g (10 mmol) of 52.0 g of methylisothiourea iodide in 10 mL of dry tetrahydrofuran, The reaction was stirred at 25 ° C. for 6 hours.
  • Synthesis Example 18 Synthesis of 2- (1-butyl) -1,1,3,3-tetramethylguanidine hydrogen iodide [3′-E] of n-butylamine 731 mg (10 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) 2.74 g (10 mmol) of 13.7 g of N, N, N ′, N′-tetramethyl-S-methylisothiourea hydroiodide salt obtained in Synthesis Example 17 at 25 ° C. in a dry tetrahydrofuran 10 mL solution Then, the mixture was further stirred at 25 ° C. for 12 hours for reaction.
  • Synthesis Example 20 Synthesis of 1,1-dicyclohexylguanidine hydrogen iodide [3′-G] Synthesis Example 9 was carried out at 25 ° C. in a solution of 1.81 g of dicyclohexylamine (10 mmol; manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 mL of tetrahydrofuran. 2.18 g (10 mmol) of 21.8 g of the S-methylisothiourea hydrogen iodide obtained in the above was added, and the mixture was further reacted by stirring at 25 ° C. for 6 hours.
  • Synthesis Example 21 Synthesis of 1-benzylguanidine hydrogen iodide [3′-H] Obtained in Synthesis Example 9 in a solution of 10.7 g of benzylamine (10 mmol; manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 mL of dry tetrahydrofuran at 25 ° C. After adding 2.18 g (10 mmol) of 21.8 g of the obtained S-methylisothiourea hydrogen iodide salt, the mixture was further reacted by stirring at 25 ° C. for 6 hours. After completion of the reaction, the residue obtained by distilling off the solvent was washed with diethyl ether, and the residue was vacuum-dried at 40 ° C.
  • Synthesis Example 24 Synthesis of 1- (N, N-dimethylaminoethyl) guanidine hydroiodide [3′-K] Then, 2.18 g (10 mmol) of 21.8 g of the S-methylisothiourea hydrogen iodide obtained in Synthesis Example 9 was added at 25 ° C., and the mixture was further reacted by stirring at 25 ° C. for 6 hours. After completion of the reaction, the residue obtained by distilling off the solvent was washed with diethyl ether, and the residue was vacuum-dried at 40 ° C. for 12 hours to give 1- (N, N-dimethylamino) as a pale yellow oil.
  • Synthesis Example 25 Synthesis of 1-benzyl-2,3,3-trimethylguanidine hydrogen iodide [3′-L] To a solution of 1.07 g of benzylamine (10 mmol; manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 mL of dry tetrahydrofuran, 25 2.60 g (10 mmol) of 52.0 g of N, N ′, N′-trimethyl-S-methylisothiourea hydroiodide obtained in Synthesis Example 15 was added at 5 ° C., and then 6 ° C. at 25 ° C. The reaction was stirred for an hour.
  • Synthesis Example 26 Synthesis of 1- (N, N-dimethylaminoethyl) -2,3,3-trimethylguanidine hydrogen iodide [3′-M] N, N-dimethylethylenediamine 882 mg (10 mmol; Tokyo Chemical Industry Co., Ltd.) Of the N, N ′, N′-trimethyl-S-methylisothiourea hydrogen iodide 52.0 g obtained in Synthesis Example 15 at 25 ° C. in a 10 mL dry tetrahydrofuran solution. Then, the mixture was further reacted by stirring at 25 ° C. for 6 hours.
  • Synthesis Example 28 Synthesis of guanidine hydrogen iodide [3′-O] In a mixed solution of 1.91 g of guanidine hydrochloride (20 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) in 4 mL of methanol and 6 mL of acetone, 3.00 g of sodium iodide After adding a mixed solution of methanol (4 mL) and acetone (6 mL) (20 mmol; manufactured by Kanto Chemical Co., Inc.), the mixture was further heated to reflux at 70 ° C. for 12 hours to be reacted. After completion of the reaction, the cooled reaction solution was filtered, and the sodium chloride residue was washed with acetone.
  • Comparative Synthesis Example 16 Synthesis of 1- (1-butyl) -1,2,2,3,3-pentamethylguanidine iodide salt [30′-A] 2- (1-butyl) obtained in Comparative Synthesis Example 15 ) After adding 284 mg (2 mmol; manufactured by Kanto Chemical Co., Inc.) of methyl iodide at 25 ° C. to a solution of 171 mg (1 mmol) of 853 mg of 1,1,3,3-tetramethylguanidine in 2 mL of dry dichloromethane, The reaction was further stirred at 25 ° C. for 12 hours. After completion of the reaction, diethyl ether was added to the residue obtained by distilling off the solvent to precipitate crystals.
  • Comparative Synthesis Example 18 Synthesis of 1- (1-butyl) -2,3,3-trimethylguanidine hydrochloride [30′-B] 1- (1-butyl) -2,3 obtained in Comparative Synthesis Example 17 , 3-Trimethylguanidine (782 mg), 315 mg (2 mmol) of 1,4-dioxane (4 mL) at 25 ° C., 1% of 35% aqueous hydrochloric acid (ca.12 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) for 10 minutes After dropwise addition, the mixture was further reacted by stirring at 25 ° C. for 12 hours.
  • the reaction solution is separated into an ionic liquid layer and an organic layer (diethyl ether layer), then the ionic liquid layer is washed with diethyl ether, and the washed ionic liquid layer is vacuum-dried at 40 ° C. for 12 hours.
  • 598 mg (yield: 97%) of 1- (1-butyl) -2,3,3-trimethylguanidine trifluoromethanesulfonate as a colorless oil was obtained.
  • the measurement results of 1 H-NMR and 13 C-NMR are shown below.
  • [1′-D] represents dicyclohexylamine hydrogen iodide
  • [10′-A] represents aniline hydrogen iodide
  • [10′-B] represents dicyclohexylamine hydrochloride
  • [10′-C] represents dicyclohexylamine hydrobromide
  • [10′-D] represents N, N-dimethyldicyclohexylammonium iodide
  • TBAI represents tetra n-butylammonium iodide.
  • NMP in the organic solvent represents 1-methyl-2-pyrrolidinone (N-methylpyrrolidone)
  • DMAc represents N, N-dimethylacetamide
  • DMF represents N, N-dimethylformamide.
  • n- represents a normal-form
  • t- represents a tert-form.
  • Examples 7 to 10 and Comparative Examples 7 to 11 Synthesis of cyclic carbonates using various amidine catalysts or aromatic heterocyclic amine catalysts Various amidine catalysts or aromatic heterocyclic amine catalysts 0.05 mmol of organic solvent 0.2 mL After adding 150 mg (1 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of phenylglycidyl ether at 25 ° C. to the solution (or suspension), the reaction system is sealed with a balloon filled with carbon dioxide gas, and carbon dioxide gas The reaction was carried out under an atmosphere (0.1 MPa) by stirring at 25 ° C. for 24 hours under the same atmosphere.
  • [2′-A] in the amidine catalyst or aromatic heterocyclic amine catalyst represents 1-methyl-1,4,5,6-tetrahydropyrimidine hydrogen iodide
  • [2′-B] 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine represents a hydrogen iodide salt
  • [2′-C] represents 1,5-diazabicyclo [4.3.0] -5-nonene hydrogen iodide salt
  • [2′-D] represents 1,8-diazabicyclo [5.4.0] -7-undecene hydrogen iodide
  • [10′-E] represents pyridine hydrogen iodide
  • [20 '-A] represents 1-methylimidazole hydrogen iodide salt
  • [20'-B] represents N, N-dimethyl-N'-octylacetamidine hydrogen iodide salt.
  • MTHF in the organic solvent represents 2-methyltetrahydrofuran
  • NMP represents 1-methyl
  • Examples 11 to 14 and Comparative Examples 12 to 21 Anion effect of cyclic amidine catalyst in carbonate reaction Phenylglycidyl in 25 mL of an organic solvent 0.2 mL (or suspension) of various cyclic amidine catalysts at 25 ° C. After adding 150 mg of ether (1 mmol; manufactured by Wako Pure Chemical Industries, Ltd.), the reaction system was sealed with a balloon filled with carbon dioxide gas to form a carbon dioxide gas atmosphere (0.1 MPa). And reacted for 24 hours.
  • [2′-A] in the cyclic amidine catalyst represents 1-methyl-1,4,5,6-tetrahydropyrimidine hydrogen iodide
  • [2′-D] represents 1,8-diazabicyclo [ 5.4.0] -7-undecene hydrogen iodide salt
  • [20′-C] represents 1-methyl-1,4,5,6-tetrahydropyrimidine hydrogen chloride salt
  • [20′-D] Represents 1-methyl-1,4,5,6-tetrahydropyrimidine hydrobromide
  • [20′-E] represents 1-methyl-1,4,5,6-tetrahydropyrimidine trifluoromethanesulfonate.
  • [20'-F] represents 1,8-diazabicyclo [5.4.0] -7-undecene hydrochloride
  • [20'-G] represents 1,8-diazabicyclo [5.4.0]- 7-undecene hydrogenbromide salt
  • [20′-H] is 1,8-diazabicyclo [5.4.0] -7-unde
  • It represents emissions acetate, representing a [20'-I] is 1,8-diazabicyclo [5.4.0] -7-undecene trifluoromethanesulphonate.
  • NMP in the organic solvent represents 1-methyl-2-pyrrolidinone (N-methylpyrrolidone)
  • MTHF represents 2-methyltetrahydrofuran.
  • aromatic hydrocarbon solvents such as toluene, ether solvents such as cyclopentylmethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran, and ketone solvents such as 2-propanone (acetone).
  • Ester solvents such as ethyl acetate, amide solvents such as N, N-dimethylformamide, 1-methyl-2-pyrrolidinone (N-methylpyrrolidone), such as isopropanol, t-butanol, 2-methoxyethanol, etc. It was found that even when the reaction was carried out in various organic solvents such as alcohol solvents, the reaction proceeded with good yield. In particular, it was found that the reaction proceeds quantitatively with an aromatic hydrocarbon solvent, an ether solvent, a ketone solvent, and an ester solvent.
  • [4-A] in epoxide (oxirane) represents phenyl glycidyl ether
  • [4-B] represents n-butyl glycidyl ether
  • [4-C] represents glycidyl methacrylate
  • [4- D] represents styrene oxide
  • [5-A] represents 2,2-bis (4-glycidyloxyphenyl) propane ⁇ bisphenol A diglycidyl ether ⁇ .
  • THF in the organic solvent represents tetrahydrofuran
  • NMP represents 1-methyl-2-pyrrolidinone (N-methylpyrrolidone)
  • MTHF represents 2-methyltetrahydrofuran.
  • n- represents a normal-body.
  • Example 31 when examined using 1-methyl-2-pyrrolidinone (N-methylpyrrolidone) as a highly polar solvent, carbonate [7-A] was not precipitated, but the reactivity decreased. .
  • This problem is solved by mixing 1-methyl-2-pyrrolidinone (N-methylpyrrolidone) with a low-polarity solvent, and the yield is improved without precipitating carbonate [7-A] during the reaction. (Examples 32 and 33).
  • the bulk reaction is more reactive than the reaction in tetrahydrofuran (Example 34).
  • the reaction using epoxide [4-C] is quantitatively performed without generating a by-product.
  • the reaction proceeded (Example 35). From these results, it was found that cyclic carbonates can be produced from various epoxides (oxiranes) by changing the organic solvent or using different conditions such as a mixed solvent system and a bulk system.
  • Example 37 Isolation and synthesis of (phenoxymethyl) ethylene carbonate under normal temperature and normal pressure conditions using amidine catalyst [2′-D] Phenylglycidyl ether 3.00 g (20 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) To a mixed solution of tetrahydrofuran 3.6 mL / 1-methyl-2-pyrrolidinone (N-methylpyrrolidone) 0.4 mL at 25 ° C., 1,8-diazabicyclo [5.4.0] -7-undecene hydrogen iodide 280 mg After adding (1 mmol), the reaction system was sealed with a balloon filled with carbon dioxide gas to form a carbon dioxide gas atmosphere (0.1 MPa), and the reaction was stirred at 25 ° C.
  • This example has a reaction scale 20 times that of Example 17 in Table 4, but the reactivity is hardly reduced.
  • 1,8-diazabicyclo [5.4.0] -7-undecene boroiodide which is a metal-free (metal-free) and inexpensive catalyst, was used, the target carbonate was quantitatively obtained. The carbonate reaction was proved to be a practical reaction.
  • Example 38 Isolation and synthesis of (2-oxo-1,3-dioxolan-4-yl) methyl methacrylate using an amidine catalyst [2′-D] under normal temperature and atmospheric pressure 2.84 g (20 mmol) of glycidyl methacrylate And 280 mg (1 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene hydrogen iodide at 25 ° C. in a balloon filled with carbon dioxide gas. was sealed in a carbon dioxide gas atmosphere (0.1 MPa), and the reaction was stirred at 25 ° C. for 48 hours in the same atmosphere.
  • This example has a reaction scale 20 times that of Example 35 in Table 5, but the reactivity is hardly reduced. Since the reaction proceeded quantitatively, the product could be isolated only by a liquid separation operation without performing a purification operation. Since the reaction proceeded under mild conditions such as 25 ° C. and 1 atm, even a highly polymerizable epoxide (oxirane) such as glycidyl methacrylate did not produce a polymer by-product, and only carbonate could be obtained.
  • Examples 39 to 43, and Comparative Examples 22 to 25 Synthesis of cyclic carbonates using various guanidine catalysts Phenyl phenyl in 25 mL of an organic solvent (or suspension) containing 0.05 mmol of various guanidine catalysts at 25 ° C. After adding 150 mg (1 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of glycidyl ether, the reaction system was sealed with a balloon filled with carbon dioxide gas to form a carbon dioxide gas atmosphere (0.1 MPa). The reaction was stirred for 24 hours at ° C.
  • [3'-C] represents 1- (1-butyl) -2,3-dimethylguanidine hydrogen iodide
  • [3'-D] represents 1- (1-butyl) -2.
  • [3′-E] represents 2- (1-butyl) -1,1,3,3-tetramethylguanidine hydrogen iodide
  • [30 ′ -A] represents 1- (1-butyl) -1,2,2,3,3-pentamethylguanidine iodide salt
  • TBAI represents tetra-n-butylammonium iodide.
  • NMP in the organic solvent represents 1-methyl-2-pyrrolidinone (N-methylpyrrolidone), and MTHF represents 2-methyltetrahydrofuran.
  • n- represents a normal-body.
  • Examples 44 to 50 Solvent effect of guanidine catalyst in carbonate reaction 150 mg (1 mmol) of phenylglycidyl ether in 25 mL of organic solvent (or suspension) of 0.05 mmol of various guanidine catalysts at 25 ° C. After that, the reaction system was sealed with a balloon filled with carbon dioxide gas to make a carbon dioxide gas atmosphere (0.1 MPa), and the reaction was stirred at 25 ° C. for 24 hours in the same atmosphere. .
  • DMI in an organic solvent represents 1,3-dimethyl-2-imidazolidinone (dimethylethyleneurea)
  • DMAc represents N, N-dimethylacetamide
  • DMF represents N, N-dimethylformamide
  • MTBE represents methyl t-butyl ether.
  • t- represents a tert-isomer.
  • amide solvents such as 1,3-dimethyl-2-imidazolidinone (dimethylethyleneurea), N, N-dimethylacetamide, N, N-dimethylformamide, such as isopropanol It can be seen that the reaction proceeds in a good yield even when the reaction is carried out in various organic solvents such as an ether solvent such as methyl t-butyl ether, an aromatic hydrocarbon solvent such as toluene. It was.
  • [3′-D] in the guanidine catalyst represents 1- (1-butyl) -2,3,3-trimethylguanidine hydrogen iodide
  • [30′-B] represents 1- (1- Butyl) -2,3,3-trimethylguanidine hydrochloride
  • [30′-C] represents 1- (1-butyl) -2,3,3-trimethylguanidine trifluoromethanesulfonate.
  • MTHF in the organic solvent represents 2-methyltetrahydrofuran.
  • [3′-F] in the guanidine catalyst represents 1- (1-octyl) guanidine hydrogen iodide
  • [3′-G] represents 1,1-dicyclohexylguanidine hydrogen iodide
  • [3′-H] represents 1-benzylguanidine hydrogen iodide
  • [3′-I] represents 1- (2-hydroxyethyl) guanidine hydrogen iodide
  • [3′-J] represents 1- (2-methoxyethyl) guanidine represents hydrogen iodide
  • [3′-K] represents 1- (N, N-dimethylaminoethyl) guanidine hydrogen iodide
  • [3′-L] represents 1-benzyl.
  • [3'-M] represents 1- (N, N-dimethylaminoethyl) -2,3,3-trimethylguanidine hydrogen iodide
  • [3′-N] is 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-eneio.
  • NMP in the organic solvent represents 1-methyl-2-pyrrolidinone (N-methylpyrrolidone)
  • MTHF represents 2-methyltetrahydrofuran.
  • reaction proceeds even when guanidine catalysts [3′-I] to [3′-K] containing other functional groups such as hydroxyl groups are used, and in particular, guanidine catalysts [3′-J] and [3 ′ -K] showed higher reactivity than the guanidine catalyst [3′-A] (Examples 56 to 58).
  • guanidine catalysts [3′-I] to [3′-K] containing other functional groups such as hydroxyl groups are used, and in particular, guanidine catalysts [3′-J] and [3 ′ -K] showed higher reactivity than the guanidine catalyst [3′-A] (Examples 56 to 58).
  • the reaction was carried out using guanidine hydroiodide (guanidine catalyst) having two proton sources.
  • Examples 62 to 68 Carbonate reaction of various epoxides (oxiranes) using guanidine catalyst [3′-A] 1- (1-butyl) guanidine hydroiodide 12.0 mg (0.05 mmol) of organic solvent
  • guanidine catalyst [3′-A] 1- (1-butyl) guanidine hydroiodide 12.0 mg (0.05 mmol) of organic solvent
  • the reaction system is sealed with a balloon filled with carbon dioxide gas, (0.1 MPa), and the reaction was performed by stirring at 25 ° C. or 45 ° C. for 24 hours under the same atmosphere.
  • [4-A] in epoxide (oxirane) represents phenyl glycidyl ether
  • [4-B] represents n-butyl glycidyl ether
  • [4-C] represents glycidyl methacrylate
  • [5- A] represents 2,2-bis (4-glycidyloxyphenyl) propane ⁇ bisphenol A diglycidyl ether ⁇
  • [5-B] represents 1,4-bis (glycidyloxy) butane ⁇ 1,4-butylene glycol di- Glycidyl ether ⁇
  • NMP in the organic solvent represents 1-methyl-2-pyrrolidinone (N-methylpyrrolidone).
  • n- represents a normal-body.
  • [4-A] in epoxide (oxirane) represents phenyl glycidyl ether
  • [4-B] represents n-butyl glycidyl ether
  • [4-C] represents glycidyl methacrylate
  • [5- A] represents 2,2-bis (4-glycidyloxyphenyl) propane ⁇ bisphenol A diglycidyl ether ⁇
  • [5-B] represents 1,4-bis (glycidyloxy) butane ⁇ 1,4-butylene glycol di- Glycidyl ether ⁇ .
  • MTHF in the organic solvent represents 2-methyltetrahydrofuran
  • MTBE represents methyl t-butyl ether
  • NMP represents 1-methyl-2-pyrrolidinone (N-methylpyrrolidone).
  • n- represents a normal-form
  • t- represents a tert-form.
  • Examples 77 and 78 Carbonate reaction of various epoxides (oxiranes) using guanidine catalyst [3'-O] Guanidine hydrogen iodide [3'-O] 9.3 mg (0.05 mmol) of organic solvent 0.2 mL
  • the reaction system was sealed with a balloon filled with carbon dioxide gas, and a carbon dioxide gas atmosphere ( 0.1 MPa) and the reaction was carried out by stirring at 45 ° C. for 24 hours under the same atmosphere.
  • Example 79 Isolation and synthesis of (phenoxymethyl) ethylene carbonate under normal temperature and normal pressure conditions using a guanidine catalyst [3'-O] 6.01 g (40 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of phenyl glycidyl ether
  • a guanidine catalyst [3'-O] 6.01 g (40 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of phenyl glycidyl ether
  • 1-methyl-2-pyrrolidinone N-methylpyrrolidone
  • the reaction system was sealed with a balloon filled with carbon dioxide gas. Under a carbon gas atmosphere (0.1 MPa), the reaction was carried out by stirring at 45 ° C. for 48 hours in the same atmosphere.
  • This example is a reaction similar to Example 77 in Table 12, but the reaction time was longer because the reaction scale was 40 times. However, since the reaction proceeds quantitatively, the product could be isolated by simply throwing the reaction solution into water without performing a purification operation.
  • guanidine hydrogen iodide which is a metal-free (metal-free) and inexpensive catalyst, was used, the reaction proceeded under mild conditions such as 45 ° C. and 1 atmosphere, and the desired cyclic carbonate was quantitatively obtained. This proved that this carbonate reaction is a practical reaction.
  • Example 80 Isolation of 2,2-propylenebis [(p-phenoxymethyl) ethylene carbonate] ⁇ bisphenol A diglycidyl ether biscarbonate ⁇ under normal temperature and pressure conditions using a guanidine catalyst [3′-A] Synthesis 2,2-bis (4-glycidyloxyphenyl) propane ⁇ bisphenol A diglycidyl ether ⁇ 3.40 g (10 mmol; manufactured by Nippon Steel Chemical Co., Ltd.) 4 mL of 1-methyl-2-pyrrolidinone (N-methylpyrrolidone) After adding 243 mg (1 mmol) of 1- (1-butyl) guanidine hydrogen iodide salt to the solution at 25 ° C., the reaction system was sealed with a balloon filled with carbon dioxide gas, and a carbon dioxide gas atmosphere (0.
  • Comparative Example 37 Synthesis of cyclic carbonate using metal salt and amidine as catalyst 1-methyl-2-pyrrolidinone of 0.05 mmol of lithium bromide and 0.05 mmol of 1,8-diazabicyclo [5.4.0] -7-undecene
  • phenylglycidyl ether After adding 150 mg (1 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) of phenylglycidyl ether to a 0.2 mL solution of (N-methylpyrrolidone) at 25 ° C., the reaction system is sealed with a balloon filled with carbon dioxide gas. Under a carbon dioxide gas atmosphere (0.1 MPa), the reaction was carried out by stirring at 25 ° C. for 24 hours in the same atmosphere.
  • the extracted reaction solution was diluted with deuterated chloroform, and the reaction solution was analyzed with reference to tetramethylsilane contained in deuterated chloroform, and the yield of the produced (phenoxymethyl) ethylene carbonate was calculated. did.
  • the yield of the produced (phenoxymethyl) ethylene carbonate was 31%. Further, almost no by-products were confirmed (5% or less), and the raw materials other than the produced carbonate were unreacted raw materials.
  • 1,8-diazabicyclo [5.4.0] -7-undecene has a function of taking in carbon dioxide, it has higher reactivity than the case where the metal salt shown in Table 13 is used alone. I can hear. However, under mild conditions such as normal temperature and normal pressure, the yield of carbonate is low, which is not sufficient from the viewpoint of industrial use.
  • the present invention is a combination of hydrogen iodide and an amine compound selected from monoamine, cyclic amidine and guanidine, which is an amine having a pKa of 8 or more among primary to tertiary amines.
  • the catalyst amine compound salt
  • a catalyst (amine compound salt) consisting only of a specific combination can efficiently promote the carbonate reaction.
  • the present invention using such a catalyst (amine compound salt) has revealed that a cyclic carbonate can be produced in a high yield even under mild conditions such as normal temperature and normal pressure.
  • the catalyst (amine compound salt) according to the present invention is also a metal-free (metal-free) catalyst (amine compound salt)
  • the present invention using the catalyst (amine compound salt) according to the present invention is based on green chemistry. It was clarified that it is useful from the viewpoint and is a practical manufacturing method considering reduction of environmental load.
  • the production method of the present invention for example, in producing a cyclic carbonate widely used in various applications such as an electrolyte of a lithium ion secondary battery, a plastic raw material, etc. by reaction of epoxide (oxirane) with carbon dioxide, This makes it possible to produce the cyclic carbonate with high yield under mild conditions such as normal pressure. Furthermore, the production method of the present invention makes it possible to practically produce a cyclic carbonate in consideration of reducing the environmental load.
  • epoxide oxirane

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Abstract

L'invention a pour objectif de fournir un procédé de fabrication pratique prenant en compte une réduction de l'impact sur l'environnement, et selon lequel un carbonate cyclique largement mis en œuvre pour divers usages tels que pour un électrolyte d'accumulateur au lithium-ion, une matière première de plastique, ou similaire, est fabriqué par réaction d'un époxyde (oxyrane) et d'un dioxyde de carbone, et peut être fabriqué selon un rendement satisfaisant sous des conditions clémentes de température et de pression normale, ou similaire. Plus précisément, l'invention concerne un procédé de fabrication de carbonate cyclique caractéristique en ce qu'un époxyde et un dioxyde de carbone sont mis en réaction en présence d'un acide iodhydrique et un composé amine constitué d'une amine primaire à tertiaire de pKa supérieur ou égal à 8, et choisi parmi une monoamine, une amidine cyclique et une guanidine.
PCT/JP2012/081217 2011-12-02 2012-12-01 Procédé de fabrication de carbonate cyclique Ceased WO2013081157A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017216498A1 (fr) 2016-06-17 2017-12-21 Veolia Recherche Et Innovation Valorisation du co2
CN107626308A (zh) * 2017-08-30 2018-01-26 江南大学 一种用于co2环加成反应和合成双酚f的水滑石负载掺杂金催化剂及制备方法
JP2020019745A (ja) * 2018-08-03 2020-02-06 日油株式会社 シクロカーボネート基含有（メタ）アクリレートモノマー
JPWO2021144996A1 (fr) * 2020-01-15 2021-07-22
CN117567425A (zh) * 2023-11-20 2024-02-20 南京工业大学 一种无卤素离子液体制备环状碳酸酯的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6245584A (ja) * 1985-08-16 1987-02-27 ヘキスト・アクチエンゲゼルシヤフト ２−オキソ−１、３−ジオキソランの製造方法
WO2008031864A1 (fr) * 2006-09-15 2008-03-20 Shell Internationale Research Maatschappij B.V. Procédé de préparation de carbonate d'alkylène
JP2010100539A (ja) * 2008-10-21 2010-05-06 Jsr Corp 環状カーボナート化合物の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6245584A (ja) * 1985-08-16 1987-02-27 ヘキスト・アクチエンゲゼルシヤフト ２−オキソ−１、３−ジオキソランの製造方法
WO2008031864A1 (fr) * 2006-09-15 2008-03-20 Shell Internationale Research Maatschappij B.V. Procédé de préparation de carbonate d'alkylène
JP2010100539A (ja) * 2008-10-21 2010-05-06 Jsr Corp 環状カーボナート化合物の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NAOTO AOYAGI ET AL.: "Remarkably Effect Catalysis of Amidine Hydroiodides for the Synthesis of Cyclic Carbonates from Carbon Dioxide and Epoxides under Mild Conditions", CHEMISTRY LETTERS, vol. 41, no. 3, 2012, pages 240 - 241, XP003031316 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017216498A1 (fr) 2016-06-17 2017-12-21 Veolia Recherche Et Innovation Valorisation du co2
CN107626308A (zh) * 2017-08-30 2018-01-26 江南大学 一种用于co2环加成反应和合成双酚f的水滑石负载掺杂金催化剂及制备方法
CN107626308B (zh) * 2017-08-30 2020-08-04 江南大学 一种用于co2环加成反应和合成双酚f的水滑石负载掺杂金催化剂及制备方法
JP2020019745A (ja) * 2018-08-03 2020-02-06 日油株式会社 シクロカーボネート基含有（メタ）アクリレートモノマー
JP7094493B2 (ja) 2018-08-03 2022-07-04 日油株式会社 シクロカーボネート基含有（メタ）アクリレートモノマーの製造方法
JPWO2021144996A1 (fr) * 2020-01-15 2021-07-22
JP7486721B2 (ja) 2020-01-15 2024-05-20 日油株式会社 シクロカーボネート基含有（メタ）アクリレートモノマーおよび重合体
CN117567425A (zh) * 2023-11-20 2024-02-20 南京工业大学 一种无卤素离子液体制备环状碳酸酯的方法

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