WO2012176930A1 - Procédé de production d'un ester d'acide carboxylique - Google Patents

Procédé de production d'un ester d'acide carboxylique Download PDF

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Publication number
WO2012176930A1
WO2012176930A1 PCT/JP2012/066312 JP2012066312W WO2012176930A1 WO 2012176930 A1 WO2012176930 A1 WO 2012176930A1 JP 2012066312 W JP2012066312 W JP 2012066312W WO 2012176930 A1 WO2012176930 A1 WO 2012176930A1
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group
substituent
group optionally
formula
optionally
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PCT/JP2012/066312
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English (en)
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Koji Hagiya
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Sumitomo Chemical Company, Limited
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups

Definitions

  • the present invention relates to a process for
  • a carboxylic acid ester is a compound important as various chemical products.
  • a carboxylic acid ester such as a ketocarboxylic acid ester is known to be useful as an intermediate for producing an amino acid and the like.
  • Non-Patent As a process for producing a carboxylic acid ester, a process for producing a carboxylic acid ester from an aldehyde has been developed. For example, Non-Patent
  • Patent Literature 1 (see, for example, Table 1) describes a' process for producing methyl 4-nitrobenzoate, by reacting 4-nitrobenzaldehyde which is an aldehyde, an alcohol, iodine and sodium nitrite with one another.
  • Non-Patent Literature 2 (for example, Supporting information, page 2) describes a process for producing a cinnamic acid ester, by reacting a cinnamic aldehyde, with quinone, in the presence of a catalyst prepared from a triazolium salt and 1,8- diazabicyclo [5.4.0] undec-7-ene .
  • Non-Patent Literature 1 Synthesis, pp. 276-28-2 (2010)
  • Non-Patent Literature 2 Journal of the American
  • An object of the present invention is to provide a new process which can produce a carboxylic acid ester from an aldehyde.
  • the present invention provides as follows:
  • a process for producing a carboxylic acid ester including the step of: mixing a compound represented by the formula (2-1) :
  • X represents an anion) , a base, an alcohol, oxygen and an aldehyde to oxidize the aldehyde.
  • R 1 represents a hydrocarbon group optionally having a substituent or a heteroaryl group optionally having a substituent; and n represents 0 or 1)
  • the alcohol is a compound represented by the formula
  • R 9 represents an alkyl group optionally having a substituent
  • the carboxylic acid ester is a compound represented by the formula (3) :
  • R 2 , Y and X " are each as defined above; R 6 and R 7 -each represent independently a hydrogen atom, an alkyl group optionally having a substituent or an aryl group optionally having a substituent, or R 6 and R 7 are taken together with a carbon atom to which they are bound to form a ring, or R 6 represents a hydrogen atom, an alkyl group optionally having a substituent or an aryl group optionally having a substituent, and R 7 is taken together with R 5 to form a divalent hydrocarbon group optionally having a substituent; and represents a single bond or a double bond) , or
  • R 2 represents an alkyl group optionally having a substituent or an aryl group optionally having a substituent
  • R 3 and R 4 each represent independently an alkyl group optionally having a substituent or an aryl group optionally having a substituent, or R 3 and R 4 are taken together to form a divalent hydrocarbon group
  • X represents an anion
  • R represents a hydrocarbon group optionally having a substituent or a heteroaryl group optionally having a substituent; and n represents 0 or 1)
  • the alcohol is a compound represented by the formula
  • R 6 and R 7 each represent independently a hydrogen atom, an alkyl group optionally having a substituent or . an aryl group optionally having a substituent, or R 6 and R 7 are taken together with a carbon atom to which they are bound to form a ring, or R 6 represents a hydrogen atom, an alkyl group optionally having a substituent or an aryl group optionally having a substituent, and R 7 is taken together with R 5 to form a divalent hydrocarbon group optionally having a substituent; and : represents a single bond or a double bond) , or
  • the process for producing a carboxylic acid ester in the present invention is a process for producing a
  • the process for producing a carboxylic acid ester in the present invention is a process for producing a corresponding carboxylic acid ester from an aldehyde, and includes the step of oxidizing an aldehyde, in the presence of a compound obtained by contacting the compound (2-1) with a base, an alcohol and oxygen .
  • aldehyde a compound having a group represented by the -CHO can be used without any limitation.
  • aldehyde a compound represented by the formula (1)
  • compound (1) (hereinafter, referred to as compound (1) in some cases) is preferably used.
  • examples of the hydrocarbon group optionally having a substituent represented by R 1 include an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent and an aryl group optionally having a substituent.
  • examples of the alkyl group, in the alkyl group optionally having a substituent include linear or branched C1-C12 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a decyl group, and cyclic C3-C12 alkyl groups such as a cyclopropyl group, a 2,2- dimethylcyclopropyl group, a cyclopentyl group, a
  • Examples of the substituent which the alkyl group optionally has include groups selected from the following group Gl.
  • a C1.-C.10 alkoxy group optionally having a fluorine atom
  • a C7-C20 aralkyloxy group optionally having a C1-C10 alkoxy group
  • a C6-C10 aryloxy group having a C6-C10 aryloxy group a C2-C10 acyl group optionally having a C1-C10 alkoxy group, a Ci-Cio alkylthio group,
  • examples of the C1-C10 alkoxy group optionally having a fluorine atom include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group and a trifluoromethyloxy group,
  • examples of the C 7 -C 2 o aralkyloxy group optionally having a C1-C10 alkoxy group include a benzyloxy group, a 4- methylbenzyloxy group and a 4-methoxybenzyloxy group,
  • examples of the C7-C20 aralkyloxy group having a C 6 -Cio aryloxy group include a 3-phenoxybenzyloxy group
  • examples of the C 3 -Ci 0 aryloxy group optionally having a C1-C10 alkoxy group include a phenoxy group, a 2-- methylphenoxy group, a 4-methylphenoxy group and a 4- methoxyphenoxy group,
  • examples of the C 6 -Cio aryloxy group having a C 6 -Ci 0 aryloxy group include a 3-phenoxyphenoxy group
  • examples of the C 2 -Ci 0 acyl group optionally having a C1-C10 alkoxy group include an acetyl group, a propionyl group, a benzylcarbonyl . group, a 4-methylbenzylcarbonyl group, a 4-methoxybenzylcarbonyl group, a benzoyl, group, a 2-methylbenzoyl group, a 4-methylbenzoyl group and a 4- methoxybenzoyl group,
  • Ci-Cio alkylthio group examples include a methylthio group, an ethylthio group and an isopropylthio group,
  • examples of the C 2 -Ci 0 alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group,
  • examples of the C6-C20 aryl group include a phenyl group, a 1-naphthyl group and a 2-naphthyl group,
  • examples of the C5-C20' heteroaryl group include a 2- pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2- quinolyl group, a 3-quinolyl group and a 4-quinolyl group, and
  • halogen atom examples include a fluorine atom, a chlorine atom, and a bromine atom.
  • alkyl group having a group selected from the group Gl examples include a chloromethyl group, a
  • methoxymethyl group an ethoxymethyl group, a 1- methoxyethyl group, a 2-methoxyethyl group, a
  • methoxycarbonylmethyl group a phenylmethyl group, a 2- pyridylmethyl group, a 3-pyridylmethyl group, a 1- ethoxycarbonyl-2 , 2-dimethyl-3-cyclopropyl group and a 2- methylthioethyl group.
  • examples of the alkenyl group, in the alkenyl group optionally having a substituent include linear, branched or cyclic C2-C12 alkenyl groups such as a vinyl group, a 1-propenyl group, a 1-butenyl group, a 2-methyl-l- propenyl group, and a 1-cyclohexenyl group.
  • Examples of a substituent which the alkenyl group optionally has include groups selected from the group Gl .
  • alkenyl group having a group selected from the group Gl examples include a 2-chlorovinyl group and a 2- trifluoromethylvinyl group.
  • examples of the aryl group, in the aryl group optionally having a substituent include C6-C20 aryl groups such as a phenyl group, a 2-methylphenyl group, a 4- methylphenyl group, a 1-naphthyl group, a 2-naphthyl group and a styryl group.
  • Examples of the substituent which the aryl group optionally has include groups selected from the following group G2.
  • a C1-C10 alkoxy group optionally having a fluorine atom or a C ' l-Cio alkoxy group
  • a C6-C10 arylox.y group optionally having a C1-C10 alkoxy group, a C 6 -Cio aryioxy group having a C e -Ci 0 aryioxy group, a C 2 -Cio acyl group optionally having a Ci-Cio alkoxy group,
  • examples of the Ci-Cio alkoxy group optionally having a fluorine atom or a Ci-Cio alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a cyclopentyloxy group, a fluoromethoxy group, a
  • examples of the ' C 6 -Cio aryioxy group optionally having a Ci-Cio alkoxy group include a phenoxy group, a 2- methylphenoxy group, a 4-methylphenoxy group and a 4- methoxyphenoxy group,
  • examples of the CQ-C IO aryioxy group having a C 6 -Cio aryioxy group include a 3-phenoxyphenoxy group
  • examples of the C 2 -Ci 0 acyl group optionally having a Ci-Cio alkoxy group include an acetyl group, a propionyl group, a benzylcarbonyl group, a 4-methylbenzylcarbonyl group and a 4-methoxybenzylcarbonyl group,
  • examples of the i-C ⁇ alkylenedioxy group include a methylenedioxy group and an ethylenedioxy group, and
  • halogen atom examples include a fluorine atom and a chlorine atom.
  • Examples of the aryl group having a group selected from the group G2 include a 4-chlorophenyl group, a 4- methoxyphenyl group and a 3-phenoxyphenyl group.
  • Examples ' of the heteroaryl group, in the heteroaryl group optionally having a substituent represented by R 1 include C4-C10 heteroaryl groups having at. least one
  • heteroatom such as a nitrogen atom, - an oxygen atom or a sulfur atom.
  • heteroatom such as a nitrogen atom, - an oxygen atom or a sulfur atom.
  • Specific examples thereof include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-furyl group, a 3-furyl group, a 5-methyl-2-furyl group and a 2- chloro-3-pyridinyl group.
  • examples of the compound (1) include benzaldehyde, 4-chlorobenzaldehyde, 2-methylbenzaldehyde, 4-fluorobenzaldehyde, 2- methoxybenzaldehyde , 2 , 4-dichlorobenzaldehyde , 2- nitrobenzaldehyde, 2-naphthylaldehyde, 2-pyridylaldehyde, acetaldehyde, n-propylaldehyde , isopropylaldehyde, n- butylaldehyde, n-pentylaldehyde, n-hexylaldehyde, n- heptylaldehyde , n-octylaldehyde, cyclohexylaldehyde, 4- (methylthio) -1-butanal, acrolein and 3-phenyl-2-
  • examples of the compound (1) include phenylglyoxal, 4- chlorophenylglyoxal, 2-methylphenylglyoxal, 4- fluorophenylglyoxal, 2-methoxyphenylglyoxal , 2,4- dichlorophenylglyoxal , 2-nitrophenylglyoxal , 2- naphthylglyoxal , 2-pyridineglyoxylaldehyde, methylglyoxal , ethylglyoxal, . n-propylglyoxal , isopropylglyoxal ,
  • the compound (1) may be a commercially available product, or may be produced according to any known method such as a method of oxygen-oxidizing a ketoalcohol in the presence of a metal catalyst (see, for example, JP-A No. 2000-336055) .
  • the alcohol can be used without any limitation.
  • a compound represented by the formula (4) (hereinafter, referred to as compound (4) in some cases) is preferably used.
  • examples of the alkyl group, in the alkyl group optionally having a substituent represented by R 9 include linear or branched C1-C12 alkyl groups such . as a methyl group, an ethyl group, a propyl group, an
  • Examples of the substituent which the alkyl group optionally has include groups selected from the following group G3.
  • a C1-C10 alkoxy group optionally having a fluorine atom
  • a C7-C20 aralkyloxy group optionally having a C1-C10 alkoxy group
  • examples of the Ci-Cio alkoxy group optionally having a fluorine atom include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group and a trifluoromethyloxy group,
  • examples of the C 7 -C 2 o aralkyloxy group optionally having a Ci-Ci 0 alkoxy group include a benzyloxy group, a 4- methylbenzyloxy group and a 4-methoxybenzyloxy group,
  • examples of the C 7 -C 20 aralkyloxy group having a C 6 -Cio aryloxy group include a 3-phenoxybenzyloxy group
  • examples of the C 6 -Ci 0 aryloxy group optionally having a Ci-Cio alkoxy group include a phenoxy group, a 2- methylphenoxy group, a 4-methylphenoxy group and a 4- methoxyphenoxy group,
  • examples of the C 6 -Ci 0 aryloxy group having a C 6 -C 10 aryloxy group include a 3-phenoxyphenoxy group
  • examples of the C 2 -C 10 acyl group optionally having a Ci-Cio alkoxy group include an acetyl group, a propionyl group, a benzylcarbonyl group, a 4-methylbenzylcarbonyl group, a 4-methoxybenzylcarbonyl group, a benzoyl group, a 2-methylbenzoyl group, a 4 -methylbenzoyl group and a 4- methoxybenzoyl group,
  • Ci-Cio alkylthio group examples include a .
  • examples of the C 2 -Ci 0 alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group,
  • examples of the C 6 -C2o aryl group include a phenyl group, a 1-naphthyl group and a 2-naphthyl group,
  • examples of the C5-C20 heteroaryl group include a 2- pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2- quinolyl group, a 3-quinolyl group and a. 4-quinolyl group, and
  • halogen atom examples include a fluorine atom, a chlorine atom and a bromine atom.
  • alkyl group having a group selected from the group G3 examples include a chloromethyl group, a
  • methoxymethyl group an ethoxymethyl group, a 1- methoxyethyl group, a 2-methoxyethyl group, a
  • methoxycarbonylmethyl group a phenylmethyl group, a 2- pyridylmethyl group, a 3-pyridylmethyl group, a 1- ethoxycarbonyl-2 , 2-dimethyl-3-cyclopropyl group and a 2- methylthioethyl group.
  • Examples of the compound (4) include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, 1-pentanol, 1-hexanol, cyclohexanol, benzyl alcohol, 2-phenylethanol " and 2-pyridinemethanol .
  • the alcohol such as the compound (4) may be a
  • the amount of the alcohol to be used is preferably 1 mol or more based on 1 mol of the ' aldehyde, and an upper limit thereof is not limited, but is preferably 100 mol or less from the viewpoint of economy.
  • examples of the alkyl group, in the alkyl group optionally having a substituent represented by R 3 and the alkyl group optionally having a substituent represented by R 4 include linear or branched C 1 -Ci 2 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a decyl group, and cyclic C3-C12 alkyl groups such as a
  • cyclopropyl group a 2 , 2-dimethylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a menthyl group.
  • Examples of the substituent which the alkyl group in R 3 and R 4 optionally has include groups selected from the ' following group G3.
  • Ci-Cio alkoxy group optionally having a fluorine atom
  • a benzyloxy group optionally having at least one kind of a group selected from the group consisting of a Ci-Cio alkoxy group, a Ci-Cio alkyl group and a C6-C10 aryloxy group, a C 6 -Cio aryloxy . group optionally having a Ci-C 10 alkoxy group,
  • examples of the C 6 -Ci 0 aryl group optionally having a Ci-Cio alkoxy group include a phenyl group, a naphthyl group, a 4-methylphenyl group and a 4- methoxyphenyl group,
  • Ci-Cio alkoxy group optionally having a fluorine atom examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group and a trifluoromethoxy group,
  • benzyloxy group optionally having at least one kind of a group selected from the group
  • Ci-Cio alkoxy group consisting of a Ci-Cio alkoxy group, a Ci-Cio alkyl group and a C 6 -Cio aryloxy group
  • a benzyloxy group consisting of a benzyloxy group, a 4- methylbenzyloxy group, a 4-methoxybenzyloxy group and a 3- phenoxybenzyloxy group,
  • examples of the C 6 -Ci 0 aryloxy group optionally having a Ci-Cio alkoxy group include a phenoxy group, a 2- methylphenoxy group, a 4 -methylphenoxy group and a 4- methoxyphenoxy group,
  • examples of the C 6 -Ci 0 aryloxy group having a C 6 -Ci 0 aryloxy group include a 3-phenoxyphenoxy group
  • examples of the C 2 -Ci 0 acyl group optionally having a Ci-Cio alkoxy group include an acetyl group, a propionyl group, a benzylcarbonyl group, a 4-methylbenzylcarbonyl group, a 4-methoxybenzylcarbonyl group, a benzoyl group, a 2-methylbenzoyl group, a 4-methylbenzoyl group and a 4- methoxybenzoyl group.
  • alkyl group having a group selected from the group G3 examples include a fluoromethyl group, a
  • ethoxymethyl group a methoxyethyl group, a benzyl group, a 4-fluorobenzyl group, a 4-methylbenzyl group, a
  • phenoxymethyl group a 2-oxopropyl group, a 2-oxobutyl group, a phenacyl group and a 2-carboxyethyl - group .
  • examples of the aryl group, in the aryl group optionally having a substituent represented by R 3 and the aryl group optionally having a substituent represented by R 4 include Cg-Cio aryl groups such as a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, and a naphthyl group.
  • Examples of the substituent which the aryl group optionally has include groups selected from the group G2.
  • Examples of the aryl group having a group selected from the group G2 include a 4-chlorophenyl group and a 4- methoxyphenyl group.
  • hydrocarbon group optionally having a substituent, which is formed by R 3 and R 4 together include an ethylene group, a vinylene group, a propane-1 , 2-diyl group, a propene-1,2- diyl group, a butane-1, 2-diyl group, a 2-butene-l , 2-diyl group, a cyclopentane-1 , 2-diyl group, a cyclohexane-1 , 2- diyl group, an o-phenylene group, a 1 , 2-diphenylethylene group and a 1 , 2-diphenylvinylene group.
  • substituent which the divalent hydrocarbon group optionally has include groups selected from the group G2.
  • Examples of the alkyl group, in the alkyl group optionally having a group selected from the group G2, include linear or branched C1 -.C12 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a decyl group, and cyclic C3-C12 alkyl groups such as a cyclopropyl group, a 2,2- dimethylcyclopropyl group, a cyclopentyl group, a
  • R 3 and R 4 are preferably taken together to form a divalent hydrocarbon group optionally having a substituent.
  • examples of the alkyl group, in the alkyl group optionally having a substituent represented by R 2 and the alkyl group optionally having a substituent represented by R 5 include linear or branched C1-C12 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl .
  • cyclic C3-C12 alkyl groups such a cyclopropyl group, a 2 , 2-dimethylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, a menthyl group and an adamantyl group.
  • Examples of the substituent which the alkyl group optionally has include groups selected from the following group G4.
  • a C1-C10 alkoxy group optionally having a fluorine atom
  • a C7-C20 aralkyloxy group optionally having a C1-C10 alkoxy group
  • a C 2 -Cio acyl group optionally having a C1-C10 alkoxy group .
  • examples of the C 6 -Cio aryl group optionally having a C1-C10 alkoxy group include a phenyl group, a naphthyl group, a 4-methylphenyl group, and a 4- methoxyphenyl group,
  • examples of the C1-C10 alkoxy group optionally having a fluorine atom include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a. tert-butoxy group and a trifluoromethoxy group,
  • examples of the C7-C20 aralkyloxy group optionally having a C1-C10 alkoxy group include a benzyloxy group, a 4- methylbenzyloxy group and a 4-methoxybenzyloxy group,
  • examples of the C7-C20 aralkyloxy group having a C6-C10 aryloxy group include a 3-phenoxybenzyloxy group
  • examples of the C6-C10 aryloxy group optionally having a C1-C10 alkoxy group include a phenoxy group, a 2- methylphenoxy group, a 4-methylphenoxy group and a 4- methoxyphenoxy group,
  • C 6 -Cio aryloxy group having a C6-C10 aryloxy group examples include a 3-phenoxyphenoxy group
  • examples of the C 2 -Cio acyl group optionally having a C1-C10 alkoxy group include an acetyl group, a propionyl group, a benzylcarbonyl group, a 4-methylbenzylcarbonyl group, a 4-methoxybenzylcarbonyl group, a benzoyl group, a 2-methylbenzoyl group, a 4-methylbenzoyl group and a 4- methoxybenzoyl group.
  • alkyl group having a group selected from the group G4 examples include a methoxymethyl group, an
  • ethoxymethyl group a methoxyethyl group, a benzyl group, a 4 -fluorobenzyl group-, a 4-methylbenzyl group, a
  • examples of the aryl group, in the aryl group optionally having a substituent represented by R 2 and the aryl group optionally having a substituent represented by R 5 include C6-C20 aryl groups such as a phenyl group, a naphthyl group, a 2-methylphenyl group, a ⁇ 4-methylphenyl group, a 2 , 6-dimethylphenyl group, a 2,4,6- trimethylphenyl group, and a 2 , 6-diisopropylphenyl group.
  • Examples of the substituent which the aryl group optionally has include groups selected from the following group G5.
  • a C1 -C10 alkoxy group optionally having a fluorine atom or a C1 -C 10 alkoxy group
  • examples of the C1 -C10 alkoxy group optionally having a fluorine atom or a C1 -C10 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a cyclopentyloxy group, a fluoromethoxy group, a
  • halogen atom examples include a fluorine atom and a chlorine atom.
  • Examples of the aryl group having a group selected from the group G5 include a 4-chlorophenyl group, a 4- methoxyphenyl group and a 2 , 6-dichlorophenyl group.
  • R 5 may be taken together with R 4 to form a divalent hydrocarbon group optionally having , a substituent.
  • the divalent hydrocarbon group include polymethylene groups such as an ethylene group, a trimethylene group and a tetramethylene group, a vinylene group, a propane-1, 2-diyl group, a propene-1 , 2-diyl group, a butane-1, 2-diyl group, a 2-butene-l, 2-diyl group, a cyclopentane-1, 2-diyl group, a cyclohexane-1, 2-diyl group and an o-phenylene group.
  • the substituent which the divalent hydrocarbon group optionally has include groups selected from the group G2.
  • X ⁇ include halide ions ' such as a chloride ion, a bromide ion and an iodide ion; alkanesulfonate ions optionally having a fluorine atom such as methanesulfonate and trifluoromethanesulfonate; acetate ions optionally having a halogen atom such as . trifluoroacetate and
  • trichloroacetate ions nitrate ions; perchlorate ions; ' tetrahaloborate ions such as tetrafluoroborate and tetrachloroborate ; hexahalophosphate ions such as
  • hexafluorophosphate hexahaloantimonate ions such as hexafluoroantimonate and hexachloroantimonate ;
  • pentahalostannate ions such as pentafluorosutannate -and pentachlorosutannate; as well as tetraarylborates
  • substituen ' t such as tetraphenylborate, tetrakis (pentafluorophenyl ) borate and tetrakis [ 3 , 5- bis (trifluoromethyl ) phenyl] borate .
  • the compound (2-1) is preferably a compound
  • compound (2-2) represented by the formula (2-2) (hereinafter, referred to as “compound (2-2)" in some cases) or a compound
  • compound 2-3 represented by the formula (2-3) (hereinafter, referred to as "compound 2-3" in some cases), more preferably a
  • the oxidizing of an aldehyde is preferably performed by mixing the compound (2-2) or the compound (2- 3), a base, an alcohol, oxygen and an aldehyde, and is more preferably performed by mixing the compound (2-2), a base, an alcohol, oxygen and an aldehyde.
  • the oxidizing of an aldehyde is preferably performed in the presence of a compound obtained by contacting the compound (2-2) or the compound (2-3) with a base, an alcohol, and oxygen, and is more preferably performed in the presence of a compound obtained by contacting the compound (2-2) with a base, an. alcohol, and oxygen.
  • R 2 has the same meaning as that of R 2 in the formula (2-1)
  • Y has the same meaning as that of Y. in the formula (2-1)
  • Y in the formula (2-2) and the formula (2-3) is a group represented by -N(R 5 )-
  • R 5 has the same meaning as that of R 5 in the formula (2-1)
  • X ⁇ has the same meaning as that of X " in the formula (2-1) .
  • R 2 is preferably a bulky group.
  • Y is a group represented by -N(R 5 )-, it is preferable that either of R 2 and R 5 is a bulky group, and it is more preferable that both of R 2 and R 3 are a bulky group.
  • R 2 and R 5 may be the same group, or may be different groups.
  • Examples of the bulky group in R 2 and R 5 include C4-C12 tertiary alkyl groups such as a tert-butyl group and a tert-pentyl group; C3-C10 cycloalkyl groups such as a cyclopropyl group, a 2 , 2-dimethylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, a menthyl group and an adamantyl group; phenyl groups having a substituent at least on a 2-position and a 6-position (2 , 6-disubstituted phenyl groups) such as a 2 , 6-dimethylphenyl group, a 2,6- dichlorophenyl group, a 2 , 6-dibromophenyl group, a 2,4,6- trimethylphenyl group and a 2 , ⁇ -diisopropylphenyl group; as well as a naph
  • a tert-butyl group, a tert-pentyl group, a cyclohexyl group, an adamantyl group or a 2 , 6-disubstituted phenyl group is preferable, a 2,6- disubstituted phenyl group is more preferable, and a 2,6- dibromophenyi group or a 2 , 6-diisopropylphenyl group is further preferable.
  • Examples of the alkyl group, in the alkyl group optionally having a substituent represented by R 6 in the formula (2-2) and the alkyl group optionally having a substituent represented by R 7 in the formula (2-2) and .the formula (2-3) include linear, branched or cyclic C1-C10 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an
  • Examples of the substituent which the alkyl group optionally has include groups selected from the group G3.
  • Examples of the alkyl group having a group selected from the group G3 include a fluoromethyl group, a trifluoromethyl group, a, methoxymethyl group, an
  • ethoxymethyl group a methoxyethyl group, a benzyl group, a 4-fluorobenzyl group, a 4-methylbenzyl group, a
  • phenoxymethyl group a 2-oxopropyl group, a 2-oxobu ' tyl group, a phenacyl group and a 2-carboxyethyl group.
  • C6-C10 aryl groups such as a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, and a naphthyl group.
  • Examples of the substituent which the aryl group optionally has include groups selected from the group G2.
  • Examples of the aryl group having a group selected from the group G2 include a 4 -chlorophenyl group and a 4- methoxyphenyl group.
  • R 6 and R 7 may be taken together with a carbon atom to which they are bound to form a ring.
  • a ring examples include a cyclopentane ring, a cyclohexane ring and a benzene ring.
  • R 6 and R 7 each are independently a hydrogen atom or an alkyl group optionally having a substituent, and it is more preferable that R 6 and R 7 are both a hydrogen atom.
  • R 2 is a linear, branched or cyclic Ci-Cio alkyl group or a C6-C10 aryl group.
  • Y in the formula (2-3) represents -N(R 5 )-, it is preferable that R 5 is a linear, branched or cyclic C1 -C10 alkyl group or a C6-C10 aryl group.
  • R 7 is a linear, branched or cyclic C1-C10 alkyl group or Cg-Cio aryl group.
  • R 5 and R 7 may be taken together to form a divalent hydrocarbon group optionally having a substituent.
  • the divalent hydrocarbon group include polymethylene groups such as an ethylene group, a trimethylene group and a tetramethylene group, a vinylene group, a propane-1, 2-diyl group, a propene-1,2- ' diyl group, a butane-1, 2-diyl group, a 2-butene-l, 2-diyl group, a cyclopentane-1 , 2-diyl group, a cyclohexane-1, 2- diyl group as well as an o-phenylene group.
  • the substituent which the divalent hydrocarbon group optionally has include groups selected from the group G2.
  • the compound (2-2) include
  • R 2 and R 5 are independently a C 4 -Ci 2 tertiary alkyl group, a cyclic C 3 -C 10 alkyl group, a phenyl group having a substituent at least on a 2-position and a 6-position or a naphthyl group having a Ci-Cio alkyl group on a 2-position;
  • R 2 and R 5 are independently a C4-C12 tertiary alkyl group, a cyclic C 3 -Ci 0 alkyl group, a phenyl group having a substituent at least on a 2-position and a 6-position or a naphthyl group having a Ci-C 10 alkyl group on a 2-position, and is a single bond;
  • Y is -N(R 5 )-
  • R 2 and R 5 are independently a C 4 -Ci 2 tertiary alkyl group, a cyclic C3-C10 alkyl group, a phenyl group having a Ci-C 10 alkyl group or a halogen atom at least on a 2-position- and a 6- position, or a naphthyl group having a C1 -C10 alkyl group on a 2-position;
  • R 2 and R 5 are independently a C 4 -Ci 2 tertiary alkyl group, a cyclic C3-C10 alkyl group, a phenyl group having a C1 -C10 alkyl group or a halogen atom at least on a 2-position and a ⁇ -position, or a naphthyl group having a Ci-Ci 0 alkyl group on a 2-position, and is a single bond;
  • R 2 and R 5 are independently a tert-butyl group, a tert-pentyl group, a cyclohexyl group, an adamantyl group, a 2,6- dimethylphenyl group, ' a 2 , 6-dichlorophenyl group, a 2,6- dibromophenyl group, a 2 , 4 , 6-trimethylphenyl group or a 2 , 6-diisopropylphenyl group;
  • R 2 and R 5 are independently a tert-butyl group, a tert-pentyl group, a cyclohexyl group, an adamantyl group, a 2 , 6-dimethylphenyl group, a 2 , 6-dichlorophenyl group, a 2 , 6-dibromophenyl group, a 2 , 4 , 6-trimethylphenyl group or a 2,6- diisopropylphenyl group, and is a single bond;
  • R 2 and R 5 are independently a C 4 -Ci 2 tertiary alkyl group, a cyclic C 3 -Ci 0 alkyl group, a phenyl group having a Ci—Cio alkyl group or a halogen atom at least on a 2-position and a 6-position or a naphthyl group having a C x -C 10 alkyl group on a 2-position,
  • ⁇ is a single bond
  • R 5 and R 7 are independently a hydrogen atom or a linear, branched or cyclic Ci-Ci 0 alkyl group optionally having a group selected from the group G3; the compound (2-2) wherein Y is -N(R 5 )-, R 2 and R 5 are independently a C 4 -C 12 tertiary alkyl group, a cyclic C 3 -Ci 0 alkyl group, a phenyl group having, a Ci-Ci 0. alkyl group or a halogen atom at least on a 2-position and a 6-position or a naphthyl group having a C !
  • cyclohexyl group an adamantyl group, a 2 , 6-dimethylphenyl group, a 2 , 6-dichlorophenyl group, a 2 , 6-dibromophenyl group, a 2 , 4 , 6-trimethylphenyl group . or a 2,6- diisopropylphenyl group, is a single bond, and R 6 and
  • R 7 are independently a hydrogen atom or a linear, branched or cyclic Cx-Cio alkyl group optionally having a group selected from the group G3;
  • R 2 and R 5 are independently a tert-butyl group, a tert-pentyl group, a cyclohexyl group, an adamantyl group, a 2 , 6-dimethylphenyl group, a 2 , 6-dichlorophenyl group, a 2 , 6-dibromophenyl group, a 2 , 4 , 6-trimethylphenyl group or a 2,6- diisopropylphenyl group, ⁇ is a single bond, and R 6 and
  • R 7 are hydrogen atoms
  • R 2 is a C 4 -C 12 tertiary alkyl group, a cyclic C 3 -C 10 alkyl group, a phenyl group having a substituent at least on a 2-position and a ⁇ -position or a naphthyl group having a Ci-Cio alkyl group on a 2-position, and is a double bond;
  • Y is -S-
  • R 2 is a C 4 -Ci 2 tertiary alkyl group, a cyclic C 3 -Ci 0 alkyl group, a phenyl group having a Ci-C 10 alkyl group or a halogen atom at least on. a 2-position and a 6-position, or a naphthyl group having a Ci-Ci 0 alkyl group on a 2-position;
  • R 2 is a C 4 -Ci 2 tertiary alkyl group, a cyclic C 3 -C 10 alkyl group, a phenyl group having a Ci-Ci 0 alkyl group or a halogen atom at least on a 2-position and a 6-position, or a naphthyl group having a Ci-Ci 0 alkyl group on a 2-position, and is a double bond;
  • Y is -S-
  • R 2 is a tert- butyl- group, a tert-pentyl group, a cyclohexyl group, an. adamantyl ' group, a 2 , 6-dimethylphenyl group, a 2,6- dichlorophenyl group, a 2 , 6-dibromophenyl group, a 2,4,6- trimethylphenyl group or a 2 , 6-diisopropylphenyl group; the .
  • Y is -S-
  • R 2 is a tert- butyl group, a tert-pentyl group, a cyclohexyl group, an adamantyl group, a 2 , 6-dimethylphenyl group, a 2,6- dichlorophenyl group, a 2 , 6-dibromophenyl group, a 2,4,6- trimethylphenyl group, or a 2 , 6-diisopropylphenyl group, and is a double bond;
  • R 2 is a C 4 -C 12 tertiary alkyl group, a cyclic C 3 -C 10 alkyl group, a phenyl group having a C 1 -C 10 alkyl group or a halogen atom at least on a 2-position and a 6-position or a naphthyl group having a Ci-Cio alkyl group on a 2-position, is a double bond
  • R 6 and R 7 are -independently a hydrogen atom or a linear, branched or cyclic Ci-Gio alkyl group optionally having a group selected from the group G3;
  • R 2 is a C 4 -Ci 2 tertiary alkyl group, a cyclic C 3 -G 10 alkyl group, a phenyl group having a Ci-Cio alkyl group or a halogen atom at least on a 2-position and a 6-position or a naphthyl group having a Ci-Cio alkyl group on a 2-position, is a double bond, and R 6 and R 7 are hydrogen atoms;
  • R 2 and R 5 are independently a tert-butyl group, a tert-pentyl group, a cyclohexyl group, an adamantyl group, a 2, 6-dimethylphenyl group, a 2 , 6-dichlorophenyl group, a 2 , 6-dibromophenyl group, a 2 , , 6-trimethylphenyl group or a 2,6- diisopropylphenyl group, and R 6 and R 7 are independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a decyl group, a cyclopropyl group, a 2 , 2-d
  • R 2 and R 5 are independently a tert-butyl group, a tert-pentyl group, a cyclohexyl group, an adamantyl group, a 2 , 6-dimethylphenyl group, a 2 , 6-dichlorophenyl group, a 2 , 6-dibromophenyl ' group, a 2 , 4 , 6-trimethylphenyl group or a 2,6- diisopropylphenyl group, is a single bond, and R 6 and
  • R 7 are independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a decyl group, a cyclopropyl group, - a 2 , 2-dimethylcyclopropyl group, a cyclopentyl group, a cyclohexyl group or a menthyl group.
  • Examples of the compound (2-2) include 1,3-di-tert- butylimidazolium chloride, 1 , 3-di-tert-butylimidazolinium chloride, 1 , 3-dicyclohexylimidazolium chloride, 1,3- dicyclohexylimidazolinium chloride, 1,3- diadamantylimidazolium chloride, 1,3- diadamantylimidazolinium chloride, 1 , 3-diphenylimidazolium chloride, 1, 3-diphenylimidazolinium chloride, 1, 3-bis
  • phenyl] imidazolinium chloride 1-tert- butyl-3-phenylimidazolium chloride, l-tert-butyl-3- phenylimidazolinium chloride, l-cyclohexyl-3- [ ( 2 , 6- diisopropyl) phenyl] imidazolium chloride, l-cyclohexyl-3- [ (2, 6-diisopropyl) phenyl] imidazolinium chloride, 1-phenyl- 3- [ (2 , 4 , 6-trimethyl) phenyl] imidazolium chloride, 1-phenyl- 3- [( 2 , 4 , 6-trimethyl ) phenyl ] imidazolinium chloride, 1-tert- butyl-3- [ (2, 6-diisopropyl) phenyl] imidazolium chloride, 1- tert-butyl-3- [ ( 2 , 6-diisopropyl ) phenyl
  • the compound (2-3) include
  • Examples of the compound (2-3) include 1 , 4-dimethyl- lH-1, 2, 4-triazol-4-ium chloride, 1, 3, 4-triphenyl-lH-l , 2, 4- triazol- -ium chloride, 6, 7-dihydro-2-pentafluorophenyl-5H- pyrrolo [2, . 1-c] -1, 2, 4-triazolium chloride, , 3, 5-diphenyl- 1, 3, 4-thiadiazolium chloride, and 3-methyl-5-phenyl-l , 3, 4- thiadiazolium chloride.
  • Examples of the compound (2-2) and the compound (2-3) also include the compound (2-2) and the compound (2-3) in which the "chloride" ' is replaced with, for example,
  • Examples of the compound (2-1). include commercially available products or compounds produced according to the process described in, for example, J. Organometallic . Chem., 606, 49 (2000) and J. Org. Chem., 73, 2784 (2008).
  • the amount of the compound (2-1) to be used is the amount of the compound (2-1) to be used.
  • the base is at least one kind selected from the group consisting of an organic base and an alkali metal alkoxide.
  • organic base examples include tertiary amines such as triethylamine, trioctylamine, diisopropylethylamine and 4-dimethylaminopyridine; nitrogen-containing aliphatic cyclic compounds such as 1 , 8-diazabicyclo [ 5 , , 0 ] -7-undecene and 1, 5, 7-triazabicyclo [4, 4, 0] -5-decene; as well as
  • nitrogen-containing aromatic compounds such as pyridine and imidazole .
  • alkali metal of the alkali metal alkoxide examples include lithium, sodium, and potassium.
  • examples of the alkoxide include methoxide, ethoxide, n-propoxide, isopropoxide, t-butoxide, and sec- butoxide. It is preferable that the alkoxide is at least one kind of an alkali metal alkoxide selected from the group consisting of lithium alkoxide, sodium alkoxide and potassium alkoxide.
  • the alkali metal alkoxide may be used alone, or may be used in an alcohol solution obtained by dissolving the alkali metal alkoxide in an alcohol solvent. In this case, it is preferable in obtaining a carboxylic acid ester at a high purity that the alcohol solvent contained in the alcohol solution is the same as the alcohol such as the compound ( 4 ) .
  • the amount of the base to be used is, for example, in a range of 0.1 mol to 10 mol, preferably in a range of 0.5 mol to 3 mol based on 1 mol of the compound (2-1) .
  • Oxygen may be an oxygen gas, an oxygen gas diluted with an inert gas such as nitrogen, or oxygen contained in the atmosphere.
  • oxygen may be a gas
  • the amount of oxygen to be used is preferably in a range of 1 mol to 100 mol based on 1 mol of the aldehyde.
  • the. mixing of the compound (2-1) , a base, an alcohol, oxygen and an aldehyde is performed in the presence of carbon dioxide.
  • Carbon dioxide may be gaseous, solid (dry ice) or in the supercritical state.
  • Gaseous carbon dioxide may be carbon dioxide diluted with an inert gas such as nitrogen.
  • the amount of carbon dioxide to be used is preferably 1 mol or more based on 1 mol of the aldehyde, and an upper limit thereof is not limited. However, it is, for example, 100 mol or less from the viewpoint of productivity. [0087]
  • the mixing may be further performed in the presence of a solvent.
  • the solvent is not limited as far as it does not inhibit the oxidizing of the aldehyde.
  • the solvent include ether solvents such as tetrahydrofuran, methyl tert-butyl ether, cyclopentyl methyl ether, and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, aromatic solvents such as toluene and chlorobenzene, nitrile solvents such as acetonitrile and propionitrile, and a mixed solvent of these.
  • ether solvents such as tetrahydrofuran, methyl tert-butyl ether, cyclopentyl methyl ether, and diisopropyl ether
  • ester solvents such as ethyl acetate and butyl acetate
  • aromatic solvents such as toluene and chlorobenzene
  • nitrile solvents such as acetonitrile and propionit
  • the amount of the solvent to be used is not limited. It is practical that the amount to be used is, for example, 100 parts by weight or less based on 1 part by weight of the aldehyde.
  • the order of mixing reaction reagents is not limited. Preferable embodiments thereof include a ⁇ method of mixing an aldehyde, the compound (2-1), oxygen, if necessary, carbon dioxide, an alcohol, and if necessary, a solvent, and adding a base to the resulting mixture. ⁇ [0089]
  • the mixing is performed under any condition of under reduced pressure, under normal pressure and under pressure, and is preferably performed under normal pressure or under pressure .
  • the reaction temperature of the mixing differs from
  • the mixing temperature is lower than -20°C, there is a tendency that the reaction rate of the oxidizing of the aldehyde is lowered, and when the mixing temperature is higher than 150°C, there is a tendency that selectivity of the
  • the progress of the oxidizing of the aldehyde can be confirmed by an analysis means such as gas chromatography, high performance liquid chromatography, thin layer
  • a carboxylic acid ester can be taken out by, for example, subjecting the resulting reaction mixture to a concentration treatment as necessary and, thereafter, performing a cooling treatment or the like.
  • the carboxylic acid ester taken out can be purified by a purification means such as distillation, column
  • the carboxylic acid ester is a compound represented by the formula (3) (hereinafter, referred to as compound (3) in some cases) is obtained, when the aldehyde is the compound (1) and the alcohol is the compound (4) .
  • examples of the compound (3) include methyl benzoate, methyl 4-chlorobenzoate, methyl 2-methylbenzoate, methyl 4-fluorobenzoate, methyl 4-methoxybenzoate, methyl 2-nitrobenzoate, methyl 2 , 4-dichlorobenzoate, methyl 2- naphthalenecarboxylate, methyl 2-pyridinecarb ' oxylate, methyl acetate, methyl propionate, methyl butanoate, methyl pentanoate, methyl hexanoate, methyl heptanoate, methyl octanoate, methyl cyclohexanoate; methyl 4-
  • examples of the compound (3) include methyl benzoylformate, methyl 4 -chlorobenzoylformate , methyl 2- methylbenzoylformate, methyl 4-fluorobenzoylformate, methyl -methoxybenzoylformate , methyl 2-nitrobenzoylformate, methyl 2 , 4-dichlorobenzoylformate, methyl 2- naphthoylformate, methyl ⁇ - ⁇ -2-pyridineacetate, methyl pyruvate, methyl 2-oxobutanoate, methyl 2-oxopentanoate, methyl 3-methyl-2-oxobutanoate, methyl a-oxo- cycl.ohexaneacetate, methyl 4- (methylthio) -2-oxo-butanoate, methyl 2-oxo-3-butenoate, methyl 2-oxo-4-phenyl-3-butenoate, ethyl benzoylformate, ethy
  • a 100 mL stainless pressure-resistant reaction tube equipped with a magnetic rotor was charged with 150 mg of methylglyoxal monohydrate, 35 mg of 3- (2, 6- diisopropyl ) phenyl-4 , 5-dimethylthiazolium chloride, 500 mg of methanol and 3 g of tetrahydrofurari, and the resulting mixture was cooled in a dry ice bath of -70°C while a nitrogen gas was blown into the mixture. After 2 g of dry ice and 6 mg of sodium methylate were added to the cooled mixture, the pressure-resistant reaction tube was sealed.
  • the resulting mixture was stirred to react at 60°C for 4 hours .
  • a 100 mL stainless pressure-resistant reaction tube equipped with a magnetic rotor was charged with 100 mg of 4- (methylthio) -2-oxo-l-butanal, 20 mg of 3- (2, 6- diisopropyl) phenyl-4 , 5-dimethylthiazolium chloride, 500 mg of methanol and 3 g of tetrahydrofuran, and the resulting mixture was cooled in a dry ice bath of -70°C while a nitrogen gas was brown into the mixture. After 2 g of dry ice and ⁇ mg of sodium methylate were added to the cooled mixture, the pressure-resistant reaction tube was sealed. The resulting mixture was stirred to react at 60°C for 4 hours .
  • a 100 mL stainless pressure-resistant reaction tube equipped with a magnetic rotor was charged with 130 mg of phenylglyoxal monohydrate, 36 mg of 1 , 3-bis [ ( 2 , 4 , 6- tribromo) phenyl ] imidazolinium chloride, 300 mg of methanol and 3 g of tetrahydrofuran, and the resulting mixture was cooled in a dry ice bath of -70°C while a nitrogen gas was brown into the mixture. After 2 g of dry ice and 10 mg of a 28% solution of sodium methylate in methanol were added to the cooled mixture, the pressure-resistant reaction tube was sealed..
  • Example 3 According to the same manner as that of Example 3 except that 18 mg of 3- ( 2 , 6-diisopropyl ) phenyl-4 , 5- dimethylthiazolium chloride was used in place of 36 mg of 1 , 3-bis [( 2 , 4 , 6-tribromo) phenyl ] imidazolinium chloride in Example 3, the experiment was carried out. When a yield of methyl benzoylformate was obtained, the yield was found to be 60%. Unreacted phenylglyoxal remained in an amount of 15%. in the reaction mixture after completion of the
  • Example 3 According to the same manner as that of Example 3 except that 7 mg of 1 , 8-diazabicyclo [ 5 , 4 , 0 ] -7-undecene was used in place of . 10 mg of a 28% solution of sodium
  • phenylglyoxal remained in an amount of 50% in the reaction mixture after completion of the " reaction.
  • a 100 mL Schlenk tube equipped with a magnetic rotor was charged with 130 mg of phenylglyoxal monohydrate, 36 mg of 1, 3-bis [ (2, 4, 6-tribromo) phenyl] imidazolinium chloride, 300 mg of methanol and 3 g of tetrahydrofuran, 10 mg of a 28% solution of sodium methylate in methanol was added to the resulting mixture, and the mixture was stirred to react at 60°C for 3 hours in the air atmosphere.
  • a 100 mL stainless pressure-resistant reaction tube equipped with a magnetic rotor was charged with 100 mg of 4- (methylthio) -2-oxo-l-butanal, 18 mg of 3- (2, 6- diisopropyl) phenyl-4 , 5-dimethylthiazolium chloride, 300 mg of methanol and 3 g of tetrahydrofuran, and the resulting mixture was cooled in a dry ice bath of -70°C while a nitrogen gas was blown into the mixture. After 2 g of dry ice and 10 mg of a 28% solution of sodium methylate in methanol were added to the cooled mixture, the pressure- resistant reaction tube was sealed. The resulting mixture was pressurized to 1 Pa with the air, and the mixture was stirred to react at 60°C for 3 hours.
  • reaction was cooled to room temperature, and thereafter, the pressure was allowed to be reduced back to the normal pressure.
  • the resulting reaction mixture was analyzed by a gas
  • Example 7 According to the same manner as that of Example 7 except that 36 mg of 1, 3-bis [ (2, 4, 6- tribromo) phenyl] imidazolinium chloride was used in place of 18 mg of 3- (2, 6-diisopropyl) phenyl-4, 5-dimethylthiazolium chloride in Example 7, the experiment was carried out.
  • a 100 mL Schlenk tube equipped with a magnetic rotor was charged with 100 mg of 4- (methylthio) -2-oxo-l-butanal, 36 mg of 1 , 3-bis [ ( 2 , 4 , 6-tribromo ) phenyl ] imidazolinium chloride, 300 mg of methanol and 3 g of tetrahydrofuran, 10 mg of a 28% solution of sodium methylate in methanol was added to the resulting mixture, and the mixture was stirred to react at 60°C for 3 hours under the air atmosphere.
  • a 100 mL stainless pressure-resistant reaction tube equipped with a magnetic rotor was charged with 150 mg of n-hexylaldehyde, 60 mg of 1 , 3-bis [ (2 , 4 , 6- trimethyl) phenyl] imidazolinium tetrafluoroborate , 500 mg of methanol and 3 g of tetrahydrofuran, and the resulting mixture was cooled in a dry ice bath of -70°C while a nitrogen gas was blown into the mixture. After 2 g of dry ice and 16 mg of sodium methylate were added to the cooled mixture, the pressure-resistant reaction tube was sealed. The resulting mixture was stirred to react at 60°C for 4 hours .
  • a 100 mL stainless pressure-resistant reaction tube equipped with a magnetic rotor was charged with 150 mg of n-hexylaldehyde, 64 mg of 1 , 3-bis [ ( 2 , 6- diisopropyl ) phenyl ] imidazolium chloride, 500 mg of methanol and 3 g of tetrahydrofuran, and the resulting mixture was cooled in a dry ice bath of -70°C while a nitrogen gas was blown into the mixture. After 2 g of dry ice and 16 mg of sodium methylate were added to the cooled mixture, the pressure-resistant reaction tube was sealed-. The resulting mixture was stirred to react at 60°C for 4 hours. After completion of the reaction, carbon dioxide, and carbon monoxide which had been generated as a byproduct were removed as a gas from the reaction mixture. The resulting reaction mixture was analyzed by a gas
  • a 100 mL stainless pressure-resistant reaction tube equipped with a magnetic rotor was charged with 150 mg of n-hexylaldehyde, 34 mg of 1, 4-dimethyl-lH-l, 2, 4-triazol-4- ium chloride, 500 mg of methanol and 3 g of tetrahydrofuran, and the resulting mixture was cooled in a dry ice bath of - 70°C while a nitrogen gas was blown into the mixture.
  • a 100 mL stainless pressure-resistant reaction tube equipped with a magnetic rotor was charged with 150 mg of n-hexylaldehyde, 36 mg of 1 , 3-bis [ ( 2 , 4 , 6- tribromo ) phenyl ] imidazolinium chloride, 300 mg of methanol and 3 g of tetrahydrofuran, and the resulting mixture was cooled in a dry ice bath of -70°C while a nitrogen gas was blown into the mixture. After 2 g of dry ice and 3 mg of sodium methylate were added to the cooled mixture, the pressure-resistant reaction tube was sealed. The resulting mixture was pressurized to 1 MPa with the air, and the mixture was stirred to react at 60°C for 3 hours.
  • reaction was cooled to room temperature, and thereafter, the pressure was allowed to be reduced back to the normal pressure.
  • the resulting reaction mixture was analyzed by a gas
  • a 100 mL stainless pressure-resistant reaction tube equipped with a magnetic rotor was charged with 200 mg of n-hexylaldehyde, 35 mg of 3- (2, 6-diisopropyl) phenyl-4, 5- dimethylthiazolium chloride, 900 mg of ethanol and 3 g of toluene, and the resulting mixture was cooled in a dry ice bath of -70°C while a nitrogen gas was blown into the mixture.
  • the pressure-resistant reaction tube was sealed.
  • the resulting mixture was pressurized to 0.5 MPa with the air, and the mixture was stirred to react at 60°C for 3 hours.
  • reaction was cooled to room temperature, and thereafter, the pressure was allowed to be reduced back to the normal, pressure.
  • the resulting reaction mixture was analyzed by a gas
  • a 100 mL stainless pressure-resistant reaction tube equipped with a magnetic rotor was charged with 180 mg of benzaldehyde, 30 mg of 3- (2 , 6-diisopropyl ) phenyl-4 , 5- dimethylthiazolium chloride, 500 mg of , methanol and 2 g of toluene, and the resulting mixture was cooled in a dry ice bath of -70°C while a nitrogen gas was blown into the mixture. After 2 g of dry ice and 13 mg of 1,8- diazabicyclo [5, 4, 0] -7-undecene were added to the cooled mixture, the pressure-resistant reaction tube was sealed. The resulting mixture was pressurized to 1 MPa with the air, and the mixture was stirred to react at 60°C for 3 hours.
  • reaction was cooled to room temperature, and thereafter, the pressure was allowed to be reduced back to the normal pressure.
  • the resulting reaction mixture was analyzed by a gas
  • a carboxylic acid ester is a compound important as various chemical products.
  • a carboxylic acid ester such as a ketocarboxylic acid ester is known to be useful also as an intermediate for producing amino acids and the like.
  • the present invention is industrially applicable as a process for producing. such a carboxylic acid ester.

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Abstract

Cette invention concerne un nouveau procédé de production d'un ester d'acide carboxylique à partir d'un aldéhyde. Le procédé consiste à mélanger un composé de formule (2-1) : (R2 représente un groupe alkyle comportant éventuellement un substituant ou autre ; R3 et R4 représentent chacun indépendamment un groupe alkyle comportant éventuellement un substituant ou autre ; ou R3 et R4 forment ensemble un groupe divalent hydrocarboné contenant éventuellement un substituant ou autre ; Y représente un groupe représenté par -S- ou un groupe représenté par -N(R5)- ; R5 représente un groupe alkyle comportant éventuellement un substituant ou autre, ou R5 forme avec R4 un groupe divalent hydrocarboné comportant éventuellement un substituant ; et X- représente un anion), une base, un alcool, un oxygène et un aldéhyde pour oxyder l'aldéhyde.
PCT/JP2012/066312 2011-06-20 2012-06-20 Procédé de production d'un ester d'acide carboxylique WO2012176930A1 (fr)

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CN113866290A (zh) * 2021-09-08 2021-12-31 上海凌凯医药科技有限公司 3,6-二氮杂环[3.1.1]庚烷-6-羧酸叔丁酯的气相检测法
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ES2408113A1 (es) * 2011-12-14 2013-06-18 Sumitomo Chemical Company, Limited Método para producir metionina
CN113866290A (zh) * 2021-09-08 2021-12-31 上海凌凯医药科技有限公司 3,6-二氮杂环[3.1.1]庚烷-6-羧酸叔丁酯的气相检测法
CN113866290B (zh) * 2021-09-08 2023-06-06 上海凌凯医药科技有限公司 3,6-二氮杂环[3.1.1]庚烷-6-羧酸叔丁酯的气相检测法
CN115057776A (zh) * 2022-06-15 2022-09-16 必维申瓯质量技术服务温州有限公司 2-萘甲酸乙酯衍生物的合成方法
CN115057776B (zh) * 2022-06-15 2023-08-22 必维申瓯质量技术服务温州有限公司 2-萘甲酸乙酯衍生物的合成方法

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