Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
  • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/42—Platinum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/745—Iron
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
  • C07D213/46—Oxygen atoms
  • C07D213/50—Ketonic radicals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/18—Carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the present invention relates to a method for producing an a-ketoaldehyde compound, and so on.
• ⁇ -ketoaldehyde compounds are known to be used for synthesis of compounds useful in the treatment of diabetes and the like (For example,, see Patent Document 1) .
• Non-Patent Document 1 describes a method of oxidizing 2-aryl-2-oxoethanol , which is a 2-oxo-primary alcohol compound, in the presence of a catalyst of copper acetate to obtain 2-aryl-2-oxoacetaldehyde
• Patent Document 2 describes a method of oxidizing 4- (methylthio) -2-oxo-l-butanol , which is a 2-oxo-primary alcohol compound, in the presence of a catalyst of copper acetate to obtain 4- (methylthio) -2-oxo-l-butanal .
• Non-Patent Document 2 and Patent Document 3 describe a method of gas-phase Oxidizing
• NPLT1 Org. Pro. Res. Dev. , Vol .14 , pp. 1254-1263 (2010) Supplementary Data pp. 14
• An object of the present invention is to provide a new method for producing an a-ketoaldehyde compound from a 2-oxo-primary alcohol compound.
• the present inventor has made intensive investigations to accomplish the present invention.
• the present invention is as follows. [1] A method for producing an a-ketoaldehyde compound comprising a step of oxidizing a 2-oxo-primary alcohol compound in the presence of platinum, a platinum compound, iron or an iron compound.
• R a is. a Ci-C6 alkyl group which may have a substituent or a C6-C 20 aryl group which may have a substituent,
• ⁇ -ketoaldehyde compound is a compound represented by the formula (2a) , R a —C-CHO
• R a is the same as the above,
• the present invention can provide a new method for producing an a-ketoaldehyde compound from a 2-oxo-primary alcohol compound.
• a method for producing an a-ketoaldehyde compound according to the present invention comprises a step of oxidizing a 2-oxo-primary alcohol compound in the presence of platinum, a platinum compound, iron or an iron compound.
• the 2-oxo-primary alcohol compound is converted into an ⁇ -ketoaldehyde compound.
• the oxidation of the 2-oxo-primary ' alcohol compound may be referred to as "the present reaction”.
• the 2-oxo-primary alcohol compound can be a 2-oxoethanol which may have a substituent at a second position.
• Examples of the 2-oxo-primary alcohol compound include a compound represented by the formula (1),
• R is a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom.
• hydrocarbon group which may have a substituent examples include an alkyl group which may have a substituent, an alkenyl group which may have a substituent and an aryl group which may have a substituent.
• examples of the alkyl group include a straight or branched C1-C12 alkyl group such as a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and decyl group, and a cyclic C3-C12 alkyl group such as a cyclopropyl,
• alkyl group 2-dimethylcyclopropyl, cyclopentyl, cyclohexyl and menthyl group.
• substituent which the alkyl group may have include a group selected from the following Group Gl .
• a C1-C10 alkoxy group which may have a fluorine atom
• a C7-C20 aralkyloxy group which may have a C1-C10 alkoxy group
• a C7-C20 aralkyloxy group which has a C6-C10 aryloxy group
• a C6-C10 aryloxy group which may have a C1-C10 alkoxy group
• a C6-C10 aryloxy group which has a C 6 -Ci 0 aryloxy group
• a C 2 -Cio acyl. group which may have a C1-C10 alkoxy group, a C1-C10 alkylthio group
• Examples of the C1-C10 alkoxy group which may have a fluorine atom in Group Gl include a methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and trifluoromethyloxy group.
• Examples of the C7-C20 aralkyloxy group which may have a 1-C10 alkoxy group in Group Gl include a benzyloxy, 4-methylbenzyloxy and 4-methoxybenzyloxy group.
• Examples of the C7-C20 aralkyloxy group which has a C6-C10 aryloxy group in Group Gl include a 3-phenoxybenzyloxy group.
• Examples of the C6-C10 aryloxy group which may have a C1-C10 alkoxy group in Group Gl include a phenoxy, 2-methylphenoxy, 4-methylphenoxy and 4-methoxyphenoxy group.
• Examples of the C ' 6-Cio aryloxy group which has a C6-C10 aryloxy group in Group Gl include a 3-phenoxyphenoxy group.
• Examples of the C 2 -Ci 0 acyl group which may have a C1-C10 alkoxy group in Group Gl include an acetyl, propionyl, benzylcarbonyl , 4-methylbenzylcarbonyl ,
• Examples of the C1-C10 alkylthio group in Group Gl include a methylthio, ethylthio and isopropylthio group.
• Examples of the C 2 -Ci 0 alkoxycarbonyl group in Group Gl include a methoxycarbonyl and ethoxycarbonyl group.
• Examples of the C 6 -C2o aryl group in Group Gl include a phenyl, 1-naphthyl and 2-naphthyl group..
• Examples of the C 5 -C 2 o heteroaryl group in Group- Gl include a 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 3-quinolyl and 4-quinolyl group.
• halogen atom in Group- Gl examples include a fluorine, chlorine and bromine atom.
• alkyl group which has a group selected from Group Gl examples include -a chloromethyl , fluoromethyl , trifluoromethyl , methoxymethyl, ethoxymethyl, 1-methoxyethyl, 2-methoxyethyl, methoxycarbonylmethyl , phenylmethyl , 2-pyridylmethyl ,
• alkenyl group which may have a substituent
• examples of the alkenyl group include a straight, branched or cyclic C 2 -Ci2 alkenyl group such as a vinyl, 1-propenyl, 1-butenyl, 2-methyl-l-propenyl and 1-cyclohexenyl grou .
• Examples of the- - substituent which the alkenyl group may have include a group selected from the above Group Gl .
• examples of the aryl group include a C6-C20 aryl group such as a phenyl, 2-methylphenyl , 4 -methylphenyl , l-naphthyl,- 2-naphthyl and styryl group.
• substituent which the aryl group may have include a group selected from the following Group G2.
• a C1-C10 alkoxy group which may have a fluorine atom or a C1-C10 alkoxy group
• a C 6 -C 10 aryloxy group which may have a C1-C10 alkoxy group
• a C 6 -Cio aryloxy group which has a C 6 -Cio aryloxy group
• a C2-Cio-acyl group which may have a C1-C10 alkoxy group
• a Ci-C 6 alkylenedioxy group
• Examples of the C1-C10 alkoxy group which may have a fluorine atom or a ⁇ C1-C10 alkoxy group in Group G2 include a methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, cyclopentyloxy,
• Examples of the C 6 -Cio aryloxy group which may have a C1-C10 alkoxy group in Group G2 include a phenoxy, 2-methylphenoxy, 4 -methylphenoxy and 4-methoxyphenoxy group.
• Examples of the C 6 -Cio aryloxy group which has a C6-C10 aryloxy group in Group G2 include a 3-phenoxyphenoxy group.
• Examples of the C 2 -Cio acyl group which may have a Ci-Cio alkoxy group in Group G2 include an acetyl, propionyl, benzylcarbonyl , 4-methylbenzylcarbonyl and
• Ci-C 6 alkylenedioxy group in Group G2 examples include a methylenedioxy and ethylenedioxy group.
• Examples of the halogen atom in Group G2 include a fluorine and chlorine atom.
• Examples of the aryl group which has a group selected from Group G2 include. a 4-chlorophenyl, 4-methoxyphenyl and 3-phenoxyphenyl group.
• heterocyclic group which may have a substituent
• examples of the heterocyclic group include a C -C10 heteroaryl group having at least one hetero atom such as a nitrogen, oxygen and sulfur atom, and specific examples thereof include a 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-furyl, 3-furyl,
• R is preferably a Ci-C 6 alkyl group which may have a substituent or a C 6 -C 2 o aryl group which may have a substituent.
• the 2-oxo-primary alcohol compound is preferably a compound represented by the formula (la),
• R a is a Ci ⁇ C6 alkyl group which may have a substituent or a C 6 -C 2 o ⁇ aryl group which may have a substituent
• a-ketoaldehyde compound is preferably a compound represented by the formula (2a) ,
• R a is the same as the above.
• examples of the Ci-C 6 alkyl group include a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and pentyl group.
• substituent which the Ci-C 6 alkyl group may have include a group selected from the above Group Gl .
• examples of the C6-C20 aryl group include a phenyl, 2-methylphenyl ,
• 2 -oxo—primary alcohol compound examples include 2-phenyl-2-oxoethanol ,
• These 2-oxo-primary alcohol compounds may be commercially available products or those produced by known methods .
• Examples of such known methods include a method of reacting an aldehyde with paraformaldehyde in the presence of a thiazolium salt and a base (for example, JP 2008-44929 A).
• Platinum, a platinum compound, iron or an iron compound for use in the present invention is not limited as long as it has oxidation activity, but preferably one in fine particles, more preferably one supported on a carrier.
• platinum, a platinum compound, iron or an iron compound which is supported on a carrier may be referred to as a "supported catalyst".
• the carrier of the supported catalyst include at least one selected from the group consisting of activated carbon, alumina, silica, zeolite, diatomite and zirconium oxide. It is preferred for such a carrier to have a larger surface area in terms of enhanced reactivity.
• the carrier include preferably activated carbon and zirconium oxide, more preferably activated carbon.
• the present reaction is carried out in the presence of platinum, a platinum compound, iron or an iron compound.
• the present invention may.be carried out in the presence of both of platinum and iron.
• the present invention may be carried out in the presence of both of a platinum compound and iron.
• the present invention may. be carried out in the presence of both of platinum and an iron compound.
• the present invention may be carried out in the presence of both of a platinum compound and an iron compound.
• platinum compound examples include a nitrate, sulfate, . formate, acetate, carbonate, halide, acid halide, hydroxide and oxide of platinum, and a complex of platinum and acetylacetone or the like.
• The. platinum compound may be a compound with a valence of 0, 2, 4 or 6.
• iron compound examples include a nitrate, sulfate, formate, acetate, carbonate, halide, acid halide, hydroxide and oxide of iron, and a complex of iron and acetylacetone, carbon - monoxide or the like.
• the iron compound may be a compound with a valence of 2 or 3.
• the supported catalyst is preferably one in which platinum, a platinum compound, iron or an iron compound is supported on the above-mentioned carrier.
• the supported catalyst may be a commercially available product or may be prepared by using a solution containing platinum nanocolloid, the above-mentioned platinum compound, iron nanocolloid or the above-mentioned iron compound and allowing the ⁇ above-mentioned carrier to support platinum, a platinum compound, iron or an iron compound by a coprecipitation method or an impregnation method, and then subjecting it to calcination.
• the supported catalyst prepared by calcination may or may not be reduced with hydrogen.
• the support may be added into the reaction system without previously preparing the supported catalyst , and in such case, preferable support is activated carbon.
• the amount of platinum, a platinum compound,- iron or an iron compound to be supported in the supported catalyst is, f-or example, in the range of 0.01% to 10% by weight, preferably 0.1% to 5% by weight based on the carrier.
• the amount of platinum, a platinum compound, iron or an iron compound to be used is preferably in the range of 0.00001 to 0.5 mol based on 1 mol of a 2-oxo-primary alcohol compound.
• the amount of the supported catalyst to be used varies depending on the amount of platinum, a platinum compound, iron or an iron compound to be supported and its type of usage; however, it is in the range of 0.1% to 200% by weight based on a 2-oxo-primary alcohol compound.
• the present reaction is preferably carried out in the presence of oxygen.
• the oxygen used in the present reaction may be an oxygen gas, an oxygen gas diluted with an inert, gas such as nitrogen, or oxygen contained in the air. Also, oxygen contained in the air may be diluted with an inert gas such as nitrogen.
• the amount of oxygen to be used is preferably in the range of 1 to 100 mol based on 1 mol of a 2-oxo-primary alcohol compound .
• the present reaction is preferably carried out in the presence of a solvent.
• the solvent is not limited as long as it is inert to the present reaction, and examples thereof include preferably an alcohol or an aromatic solvent, more preferably an alcohol.
• the alcohol include an alcohol having 1 to 6 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol , n-pentanol and n-hexanol , preferably methanol and ethanol , more preferably methanol.
• the aromatic solvent include toluene,. xylene, chlorobenzene and fluorobenzene .
• solvents may be a mixture with a small amount of water or other organic solvents.
• the amount of the solvent to be used is not limited, but preferably 1 part by weight or more based on 1 part by weight of a 2-oxo-primary alcohol compound in terms of operability and 100 parts by weight or less in terms of practicality.
• reaction reagents there is no limitation on the order of mixing reaction reagents in the present reaction.
• a method of mixing a 2-oxo-primary alcohol compound, platinum, a platinum compound, iron or an iron compound, and a solvent and thereafter mixing the obtained mixture with oxygen.
• the present reaction is carried out under any conditions of reduced pressure, normal pressure or increased pressure, but preferably under normal pressure or increased pressure.
• the reaction temperature at which the present reaction is carried out varies depending on the amount of platinum, a platinum compound, iron or an iron compound to be used, the amount of oxygen to be used, and the like, but preferably in the range of 0 to 150°C, more preferably 20 to 100°C.
• ⁇ the present reaction tends to proceed at a lower rate.
• 150°C the present reaction tends to have a lower selectivity .
• the obtained reaction mixture is, for example, filtered to remove platinum, a platinum compound, iron or an iron compound from the reaction mixture, . and then subjected to distillation to remove the solvent, so that an a-ketoaldehyde compound can be extracted.
• the extracted ⁇ -ketoaldehyde compound can be purified by distillation, column chromatography, crystallization or other purification means.
• Examples of the thus-obtained a-ketoaldehyde compound include 2-oxo-2-phenylethanal ,
• 2-oxo-l-octanal cyclohexylglyoxal and 4- (methylthio) -2-oxo-l-butanal .
• reaction tube was pressurized to 2 MPa with air.
• the obtained mixture was stirred at 60°C for 6 hours.
• the reaction mixture was cooled to room temperature and allowed to be under normal pressure by release of the pressure, and then filtered.
• the obtained filtrate was analyzed by the gas chromatography internal standard method. The yield of
• 2-phenyl-2-oxoethanol 100 mg of 1 wt% Pt - 0.2 wt% Fe-supported activated carbon, (product manufactured by ' Evonik Degussa Corporation, water content: 50% by weight) and 3 g of methanol. Then, the reaction tube was pressurized to 2 MPa with air. The obtained mixture was stirred at 60°C for 6 hours. The reaction mixture was cooled to room temperature and allowed to be under normal pressure by release of the pressure, and then filtered. The obtained filtrate was analyzed by the gas chromatography internal standard method. The yield, of 2-oxo-2-phenylethanal was calculated, and it was 91%.
• the reaction mixture was cooled to room temperature and allowed to be under normal pressure by release of the pressure, and then filtered. The obtained filtrate was analyzed by the gas chromatography internal standard method. The yield of 2-oxo-2-phenylethanal was calculated,, and it was 56%.
• 4- (methylthio) -2-oxo-l-butanal was calculated, and it was 37% .
• a-ketoaldehyde compounds are known to be used for synthesis of compounds useful in the treatment of diabetes and the like.
• the present invention is industrially available as a method for producing an ⁇ -ketoaldehyde compound.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Applications Claiming Priority (4)

Publications (1)

Family

ID=46650842

Family Applications (1)

Country Status (2)

Cited By (1)

Citations (4)

• 2012
  • 2012-07-12 JP JP2012156256A patent/JP2013177360A/ja active Pending
  • 2012-07-19 WO PCT/JP2012/068899 patent/WO2013018626A1/en active Application Filing

Patent Citations (4)

Non-Patent Citations (5)

Also Published As

Similar Documents

Legal Events