WO2005009613A1 - 酸化触媒 - Google Patents
酸化触媒 Download PDFInfo
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- WO2005009613A1 WO2005009613A1 PCT/JP2004/010399 JP2004010399W WO2005009613A1 WO 2005009613 A1 WO2005009613 A1 WO 2005009613A1 JP 2004010399 W JP2004010399 W JP 2004010399W WO 2005009613 A1 WO2005009613 A1 WO 2005009613A1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/006—Catalysts comprising hydrides, coordination complexes or organic compounds comprising organic radicals, e.g. TEMPO
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to an oxidation catalyst effective for chemical synthesis. More specifically, the present invention is an oxidation catalyst for oxidizing a reaction substrate with molecular oxygen, comprising at least one selected from the group consisting of a specific hydrazyl radical and a specific hydrazine compound. Oxidation catalyst.
- the reaction substrates eg, hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds, and heterocyclic compounds
- the present invention also relates to a method for producing a compound using the oxidation catalyst.
- the oxidation reaction is one of the most basic substance conversion methods in organic synthesis, and many oxidation processes have been put to practical use.
- many oxidation reactions, such as oxygen oxidation reactions require high temperature and high pressure conditions to activate molecular oxygen, resulting in many byproducts with low selectivity for the target compound. Therefore, there are disadvantages such as the necessity of various separation processes, and the present situation cannot be said to have reached a level that is satisfactory from the practical viewpoints such as economy, safety, and environmental friendliness.
- the development of highly efficient, highly selective and inexpensive new oxidation methods has been awaited.
- oxidation reactions for example, oxidation of alkanes, oxidation of alcohols, epoxidation of olefins, oxidation of ketones, oxidation of aldehydes, oxidation of ethers, hydroxylation of aromatic compounds, amines
- oxidizing agents such as hydrogen peroxide and organic and inorganic peroxides that can provide high chemical potential and can supply active oxygen species (electrophilic oxygen species) are used. Used and useful chemicals can be produced with high selectivity and high efficiency under mild conditions (see “New Experimental Chemistry Lecture 15 Oxidation and Reduction” G.
- t-butyl hydroperoxide As a useful organic peroxide, t-butyl hydroperoxide is known. Methods for producing t-butyl hydroperoxide include, for example, organic peroxides produced by the reaction of hydrogen peroxide with a strong acid such as sulfuric acid using t-butanol or isobutylene as a raw material, and organic peroxides. (Japanese Edition), page 220, 1972, Japan.
- these conventionally known methods require expensive hydrogen peroxide, and furthermore, require a high concentration aqueous solution of sulfuric acid (60-70 wt%) and a mixed solution of hydrogen peroxide aqueous solution (30-50 wt%). Because of the reaction, it is hard to say that it is an advantageous method from the viewpoint of economy and safety.
- reaction system in which the product phenol is more active than benzene
- a great deal of effort has been made so far in the oxygen oxidation of the above reaction to improve its selectivity.
- it has not yet reached a satisfactory level in terms of economics and safety.
- the reason that the above-mentioned reaction does not proceed selectively in oxygen oxidation is that electron transfer from the catalyst is always involved when activating oxygen molecules, and the nucleophilic oxygen anion species becomes the main active species. It is considered that the addition of the electrophile is difficult to proceed. (Catalysis Today, 45, 3-12, 1998).
- a method of oxidizing alkanes, alcohols, ketones, and the like with molecular oxygen using an imide compound such as N-hydroxyphthalimide as an oxidation catalyst has been proposed (for example, See Japanese Patent Application Laid-Open No. 10-286467 (corresponding to U.S. Pat. No. 5,981,420 and European Patent No. 858835).
- the amount of the imide compound used is as low as about 10 mol% with respect to the substrate, which makes it possible to selectively oxidize the substrate under mild conditions.
- the production cost is increased due to decomposition and consumption.
- a nitroxyl radical such as 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO)
- TEMPO 2,2,6,6-tetramethylpiperidine N-oxyl
- alcohols are selectively converted to carbonyl compounds and the like using a catalyst composed of a combination of TEMPO and a ruthenium compound, but the catalytic activity is insufficient, and the nitroxyl radical reacts. There is a problem of denaturation in the inside.
- a metal vorphyrin complex or a metal salen complex as a catalyst, for example, a oxidative acetoxylide reaction of gen (Angew. Chem. Int. Ed. Engl., 32, 263, 1993), oxidation of primary alcohols to aldehydes and oxidation of secondary alcohols to ketones using ternary system of Ru complex-Co salen complex-noid mouth quinone G. Chem. Soc., Chem.
- Oxime compounds and nitro compounds are important compounds as various chemical products and intermediates for fine and pharmaceutical synthesis.
- a method for producing an oxime compound by oxidizing a primary amine for example, a method using dimethyloxysilane as an oxidizing agent (J. Org. , 57, 6759, 1992), a method using hydrogen peroxide as an oxidizing agent, a method using sodium tungstate hornworm medium (Angew. Chem., 72, 135, 1960), a methino-rhenium trioxide catalyst (Bull. Chem. Soc. Jpn., 70, 877, 1997) and a method using titanium silicalite molecular sieves (TS-1) catalyst (J. Chem. Soc.
- a method for producing a nitro compound by oxidizing a primary amine for example, a method using a peracid such as m-chloroperbenzoic acid or pertrifluoroacetic acid ti. Org. Chem., 5 8, 1372, 1993), a method using potassium permanganate (Org. Synth., 52, 77, 1972), a method using ozone (Synthetic Commun., 20, 1073, 1990), tert_ Chem. Soc.
- cyclohexanone oxime which is an oxime compound, is a raw material for nylon_6.
- ⁇ -Caprolactam is a compound useful as an intermediate.
- Cyclohexanone oxime can be synthesized by using cyclohexenoleamine as a raw material and reacting it with an oxidizing agent.
- a method of using hydrogen peroxide as an oxidizing agent (l) a method of conducting in the presence of a catalyst containing at least one metal selected from the group consisting of Mo, W and U (US Pat. 2, 706, 204), (2) a method of using titanium silicalite or vanadium silicalite as a hornworm medium (Tetrahedron, 51 (41), 11305, 1995), Catal.
- organic hydroperoxide as an oxidizing agent includes (3) Ti, V, Cr, Se, Zr, Nb, Mo, Te, Ta, W, Re and U A method in the presence of a catalyst containing at least one metal selected from the group consisting of strong metals (see US Pat. No. 3,960,954) and the like.
- Examples of the method of using molecular oxygen as an oxidizing agent include (4) SiO gel and ⁇ -A1 ⁇ .
- the methods (1) to (3) have a problem that expensive hydrogen peroxide or organic hydroperoxide is used as an oxidizing agent.
- operational hazard explosion hazard
- an organic hydroperoxide a product derived from reduction of the hydroperoxide is included in the reaction solution, so that there is a problem that separation and purification operations are complicated.
- molecular oxygen such as air or oxygen as an oxidizing agent
- the methods (4) and (5) use relatively severe gas-phase operating conditions at a reaction temperature of 120 to 250 ° C. According to the study of the present inventor, under a gas phase operating condition at a reaction temperature of 160 ° C. or higher, tar-like by-products and high-boiling organic carbonaceous materials accumulate on the surface of the catalyst, and the catalyst is easily prepared. It was found that it had a problem of deactivation. In addition, the selectivity of the resulting cyclohexanone oxime is as low as about 50-60% at a conversion of 20%, and there is also a problem that the amount of reaction products per reaction space, that is, the productivity is low.
- the reaction is performed under relatively mild conditions at a reaction temperature of 50 to 150 ° C under liquid phase conditions.
- the method (6) uses t-butanol as the reaction solvent and phosphotungstic acid as the catalyst.
- the reaction examples used are indicated.
- the yield of cyclohexanone oxime is as low as several percent.
- the method (7) shows a reaction example using a titanium conjugate as a catalyst and using ethylene glycol dimethyl ether (diglyme), t-butanol, dimethylformamide, acetonitrile, triethylamine, and water as a reaction solvent.
- the selectivity of the generated cyclohexanone oxime is about 30_50. If the catalyst activity is low as low as / o, there is a problem.
- ditron compounds which can be induced by oxidation of amines are important compounds as synthetic intermediates for pharmaceuticals, agricultural chemicals and fine chemicals such as substituted amine compounds, amino acids and alkaloids.
- a method for producing such a dithrone conjugate a method of reacting secondary amine with hydrogen peroxide is known. Examples of such a production method include a method using a sodium tungstate catalyst (see JP-A-59-164762 (corresponding to US Pat. No. 4,596,874)) and a selenium dioxide catalyst.
- a known method see Japanese Patent Application Laid-Open No. 63-63651
- a method using a methylrhenium trioxide catalyst (Bull. Chem. Soc.
- the reaction substrate For example, hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds and heterocyclic compounds
- the reaction substrate can be efficiently oxidized, and useful compounds can be produced at high selectivity and economically. No possible oxidation catalyst has been obtained.
- the inventor of the present invention has intensively studied to solve the problems of the prior art. As a result,
- An oxidation catalyst comprising a hydrazine compound such as 2,2-diphenyl-1-picrylhydrazine, or an oxidation catalyst comprising a combination of the hydrazinol radical and / or hydrazine compound and an oxidation accelerator such as a transition metal compound.
- Oxidation of reaction substrates e.g., hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds and heterocyclic compounds
- reaction substrates e.g., hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds and heterocyclic compounds
- one object of the present invention is to provide a reaction substrate (for example, hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds and complex compounds) under a mild condition by molecular oxygen.
- a reaction substrate for example, hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds and complex compounds.
- An object of the present invention is to provide an oxidation catalyst capable of efficiently oxidizing a cyclic compound and efficiently producing a useful compound with high selectivity.
- Another object of the present invention is to provide a method for producing a compound using the oxidation catalyst.
- the reaction substrate for example, hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds, Since the cyclic compound can be efficiently oxidized, a useful compound can be produced economically with high selectivity.
- an oxidation catalyst for oxidizing a reaction substrate with molecular oxygen which is represented by the following formula (1) and a hydrazinole radical represented by the following formula (2)
- An oxidation catalyst comprising at least one member selected from the group consisting of hydrazine compounds is provided.
- R 1 ,, and R ° each independently represent an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, or an azo group.
- a method for producing a compound which comprises oxidizing a compound by contacting a reaction substrate with a molecular oxygen in the presence of the oxidation catalyst to form a compound.
- An oxidation catalyst for oxidizing a reaction substrate with molecular oxygen which is a group consisting of a hydrazinole radical represented by the following formula (1) and a hydrazine compound represented by the following formula (2):
- An oxidation catalyst comprising at least one member selected from the group consisting of:
- R 1 and R z are each independently an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group Group, carbonyl group, alkoxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxy group, alkoxy group, aryloxy group, haloalkyl group, mercapto group, alkylthio group, arylthio group, sulfo group, sulfiel group , A sulfonyl group or a complex ring group, or a group containing at least two of these atoms and groups; and, if desired, two members selected from the group consisting of R 1 , R 2 and R 3 are bonded to each other. They form a ring.
- R 4 , R 5 , R 6 , R 7 , and R 8 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxy group, a nitro group, a nitroso group, A cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxy group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, Arylthio, sulfo, sulfinyl, sulfo R 1 and R 2 are the same as defined for each of R 4 to R 8 except that neither R 1 nor R 2 is a hydrogen atom.
- R 1 and R 2 are the same as defined for each of R 4 to R 8 except that
- R 1 and R 2 optionally forms a ring bonded to each other, also, the set of substituents R 4 and R 5, the substituents R 5 and the set of R 6, the substituents R 6 and R 7 And one or two of the groups selected from the group consisting of the groups of the substituents R 7 and R 8 , the substituents of the or each group may be bonded to each other to form one ring or 2 Form two rings.
- Hydrazine compound power 2, 2-diphenyl 1-picrylhydrazine, 2, 2-diphenyl 1_
- a hydrazyl radical force is 2,2-diphenyl-2-picrylhydrazyl
- the hydrazine-conjugated compound is 2,2_diphenyl-2-picrylhydrazine. 13
- the oxidation catalyst according to any one of the above items 1-3.
- R 1 , R 2 and R 9 each independently represent an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, Azo group, carbonyl group, carboxyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, haloalkyl group, mercapto group, thioalkylthio group, arylthio group, sulfo group, Sulfinyl group, sulfonyl group or hetero
- the hydrazyl radical is composed of 1-phenylpyrazolidone-1 (3) -radical and 3,4-dihydro
- the hydrazine compound is 1-phenylpyrazolidine-3-one, 1-phenyl-1,2-dihydr-one-pyridazine-1,6-dione, and 2_phenyl-2,3-dihydro-phthalazine Selected from the group consisting of one 1, 4-dione,
- R 10 , R 11 and R 12 each independently represent a hydrogen atom, an oxygen atom, a sulfur atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxy group, a nitro group, a nitroso group, a cyano group.
- R 13 is defined similarly to each of R 1Q R 12 except that it is not a hydrogen atom; and, if desired, two members selected from the group consisting of R 11 , R 12 and R 13 are bonded to each other to form a ring are doing.
- the transition metal is a lanthanoid element, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Item 12.
- a method for producing a compound comprising: bringing a reaction substrate into contact with molecular oxygen in the presence of the oxidation catalyst according to any one of the above items 1 to 12 to carry out an oxidation reaction to form a compound.
- reaction substrate is selected from the group consisting of hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds and heterocyclic compounds.
- R 1 and R 2 each independently represent a hydrogen atom, an aliphatic group, an aromatic group or an aralkyl group, provided that R 1 and R 2 are not simultaneously hydrogen atoms;
- R 1 and R 2 can be linked together to form a ring.
- R 1 and R 2 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or an aralkyl group.
- R 3 is defined as each of R 1 and R 2 except that it is not a hydrogen atom;
- two members selected from the group consisting of R 1 , R 2 and R 3 are bonded to each other to form a ring.
- Nitrile analog At least selected from the group consisting of acetonitrile and benzonitrile
- the amount of at least one selected from the group consisting of hydrazyl radicals and hydrazinide conjugates is 0.0001-1 mol per 1 mol of the reaction substrate.
- the oxidation catalyst of the present invention is an oxidation catalyst for oxidizing a reaction substrate with molecular oxygen, and is represented by the following formula (1) and the following hydrazinole radical: At least one member selected from the group consisting of hydrazine compounds is included. [0083]
- R 1 , R 2 , and R 3 each independently represent an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, Azo group, carbonyl group, carbonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, rubamoyl group, alkoxy group, aryloxy group, haloalkyl group, mercapto group, alkylthio group, arylthio group, sulfo group, Represents a sulfiel group, a sulfonyl group, a complex ring group, or a group containing at least two of these atoms and groups; and if desired, two members selected from the group consisting of R 1 , R 2 and R 3 are bonded to each other To form a ring ing.
- the aliphatic group may be saturated or unsaturated, substituted with a substituent, or unsubstituted or linear, cyclic or branched.
- the aliphatic group may also contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms.
- the aromatic group may be substituted or unsubstituted, and may contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms.
- the hydroxyl group may form a salt with a metal atom.
- the aryloxy group, the haloalkyl group, the mercapto group, the alkylthio group, the arylthio group, the sulfo group, the sulfiel group, the sulfonyl group, and the heterocyclic group may be substituted or unsubstituted. It may contain oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms.
- examples of the substituent include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, Carbonyl group, carboxyl group, asinole group, alkoxycarbonyl group, aryloxycarbonyl group, levamoyl group, alkoxy group, aryloxy group, haloalkyl group, mercapto group, alkylthio group, arylthio group, sulfo group, sulfiel group, Examples include a sulfonyl group or a heterocyclic group.
- the carbon number of the aliphatic group is usually 11 to 15, preferably 1 to 10, the carbon number of the aromatic group is usually 5 to 12, preferably 6 to 10, and the carbon number of the acyl group is usually 1 to 10.
- the carbon number of the alkoxycarbonyl group is usually 110, preferably 116, the carbon number of the aryloxycarbonyl group is usually 510, and the carbon number of the alkoxy group is The number is usually 110, preferably 116, the carbon number of the aryloxy group is usually 5-10, the carbon number of the haloalkyl group is usually 116, and the carbon number of the alkylthio group is usually 116.
- heterocyclic group refers to a heterocyclic monocyclic compound such as furan, thiophene, pyrroline, ⁇ -pyran, thiopyran, pyridine, monoreforin, thiazole, imidazole, pyrimidine, and 1,3,5-triazine.
- indole quinoline, purine, pteridine, chroman, carbazo-nore benzothiazo, mono-benzoto ⁇ -azonore besozonozono ⁇ sokieno ⁇ , It means a substituent composed of a fused heterocyclic compound.
- examples of R 1 and R 2 are preferably an aliphatic group, an aromatic group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxy group.
- examples include a carbonyl group, a haloalkyl group and a heterocyclic group.
- examples of R 3 include preferably an aliphatic group, an aromatic group, a cyano group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a haloalkyl group. And heterocyclic groups.
- substituents may be substituted or unsubstituted with one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms. Les ,.
- the substituent includes an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, and a carbonyl group.
- Preferred examples of the hydrazyl radical of the formula (1) and the hydrazine compound of the formula (2) include compounds represented by the following formulas (3) and (4), respectively.
- R 4 , R 5 , R 6 , R 7 , and R 8 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxy group, a nitro group, a nitroso group, A cyano group, an amino group, an imino group, an azo group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkoxy group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, Arylthio, sulfo, sulfinyl, sulfo R 1 and R 2 are the same as defined for each of R 4 to R 8 except that neither R 1 nor R 2 is a hydrogen atom.
- R 1 and R 2 are the same as defined for each of R 4 to R 8 except that
- R 1 and R 2 optionally forms a ring bonded to each other, also, the set of substituents R 4 and R 5, the substituents R 5 and the set of R 6, the substituents R 6 and R 7 And one or two of the groups selected from the group consisting of the groups of the substituents R 7 and R 8 , the substituents of the or each group may be bonded to each other to form one ring or 2 Form two rings.
- the aliphatic group may be saturated or unsaturated, may be substituted with a substituent, or may be unsubstituted, and may have a chain, cyclic or branched structure.
- the aliphatic group may also contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms.
- the aromatic group may be substituted or unsubstituted, and may contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms.
- the hydroxyl group forms a salt with a metal atom.
- An aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfiel group, a sulfonyl group, or a heterocyclic group may be substituted or unsubstituted with one or more oxygen atoms.
- Nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms When substituted with a substituent, examples of the substituent include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, and a carbonyl group.
- the number of carbon atoms of each substituent is the same as described above for formulas (1) and (2).
- examples of R 1 and R 2 is preferably an aliphatic group, an aromatic group, a carbonyl group, a carboxyl group, Ashiru group, an alkoxycarbonyl group, Ariruoki Examples include a cyclocarbonyl group, a haloalkyl group and a heterocyclic group.
- examples of R 4 , R 5 , R 6 , R 7 and R 8 are preferably a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, a nitro group, a cyano group, an amino group, an imino group, and a carbonyl group.
- These groups may be substituted or unsubstituted, and may contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron, or halogen atoms.
- substituents include an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, and a carboxy group.
- hydrazyl radical represented by the formula (3) include, for example, triphenylhydrazyl, 2,2-diphenyl-1- (5'-phenyl-2-m-terfenol-1-yl) 2'-Innole) hydrazyl, 2,2-dipheninole (2-nitro-one-phenyl) hydrazyl, 2,2-diphenylenoleate (2,4-dinitro-phenyl) hydrazinole, 2,2-diphenylone- Picrylhydrazyl, 2,2-dipheninole 1— (3—black 2,4,6_trinitro-pheninole) hydrazyl, 1_ [3— (4-morphinole) 2,4,6 Trinitropheninole] _2,2-Dipheninolehydrazyl, 2-Dipheninole-1_ (2,6-Dinitro_4_Fluoromethylphenyl) hydrazyl, 1_ (2,4-Dinitro_6_
- Preferred examples of the hydrazyl radical of the formula (3) include 2,2-diphenyl-1-picryl hydride Radinore, 2, 2-dipheninole 1- (2,6-dinitro-4-fluoromethylpheninole) hydrazyl, 2,2-dipheninole 1_ (4-cyano 2,6-dinitropheninole) hydrazyl , 2,2-diphenolinole 1- (2,6-dinitro-1-methoxycarbonylinolephene) hydrazyl, 2,2-diphenebinole 1- (2,6-dinitro-1-sulfophene 2,2-diphenyl-1,2- (2,4,6-tricyanophenyl) hydrazyl, 2,2-diphenyl-1- (2,4,6_tricyano-3,5-difluoro Phenyl) hydrazyl, 1,3,5-tris (N, N-diphenylhydrazyl) _2,4,6_tricyanbenzonole, 1,
- 2,2-diphenyl-1-picrylhydrazyl Particularly preferred is 2,2-diphenyl-1-picrylhydrazyl.
- the hydrazine compound of the formula (4) include, for example, triphenylinolehydrazine, 2,2-diphenyl_1_ (5'_phenyl_m-terphenyl-1'-yl) hydrazine, 2,2- Dipheninole _ (2-nitro-phenyl) hydrazine, 2, 2-dipheninole _ (2,4-dinitro-phenyl) hydrazine, 2, 2-diphenyl 1-picrylhydrazine, 2,2-diphenyl 1_ (3-chloro-2,4,6-trinitro-phenyl) hydrazine, 1— [3- (4-morpholinyl) —2,4,6-trinitrophenyl] — 2,2-diphenyl-1-hydrazine, 2,2-diphenyl_1_ (2,6-dinitto mouth—4_fluor
- Preferred examples of the hydrazine compound of the formula (4) include, for example, 2,2_diphenyl-1-picrylhydrazine, 2,2-diphenyl_1- (2,6-dinitro-4-fur- (2-methylphenyl) hydrazine, 2,2-diphenyl-1- (4-cyano-1,2,6-dinitrophenyl) hydrazine, 2,2_diphenyl-1,4- (2,6-dinitro-1-methoxy) Carbonyl-1-phenyl) hydrazine, 2,2-diphenyl-1- (2,6-dinitro-4-sulfo-phenyl) hydrazine, 2,2-diphenyl-1- (2,4,6_ Tricyanphenyl) hydrazine, 2,2-diphenyl 1_ (2,4,6_tricyanore 3,5—difluorophenyl) hydrazine, 1,3,5-tris (N, N-diphenylhydrazino)
- R 1, R 2, R 9 are each independently an aliphatic group, an aromatic group, a halogen atom, hydroxy group, nitro group, nitroso group, Shiano group, an amino group, an imino group, ⁇ Azo group, carbonyl group, carboxyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, haloalkyl group, mercapto group, thioalkylthio group, arylthio group, sulfo group, Sulfinyl group, sulfonyl group or hetero A ring group or a group containing at least two of these atoms and groups; and, if desired, two members selected from the group consisting of R 1 , R 2 and R 9 are bonded to each other to form a ring .
- the aliphatic group may be saturated or unsaturated, may be substituted with a substituent, or may be unsubstituted, and may have a chain, cyclic or branched structure.
- the aliphatic group may also contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms.
- the aromatic group may be substituted or unsubstituted, and may contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms.
- the hydroxyl group may form a salt with a metal atom.
- One or more oxygen atoms which may be substituted or unsubstituted with a aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfyl group, a sulfonyl group, or a heterocyclic group.
- the substituent includes an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, and a carbonyl group.
- examples of R 1 and R 2 are preferably an aliphatic group, an aromatic group, a carbonyl group, a carboxyl group, an acyl group, an alkoxycarbonyl group, an aryloxy group.
- examples include a carbonyl group, a haloalkyl group and a heterocyclic group.
- examples of R 9 preferably include an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group, a haloalkyl group and a heterocyclic group. These groups may contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms, which may be substituted or unsubstituted with substituents.
- the substituent When substituted with a substituent, the substituent may be an aliphatic Group, aromatic group, halogen atom, hydroxy group, nitro group, nitroso group, cyano group, amino group, imino group, azo group, carbonyl group, carboxyl group, acyl group, alkoxycarbonyl group, arylo group Examples thereof include a xycarbonyl group, a sulfamoyl group, an alkoxy group, an aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a snorejo group, a sulfier group, a sulfonyl group and a heterocyclic group.
- hydrazyl radical of the formula (5) include, for example, N-benzoyl-N, N, -diphenyl-hydrazyl, 1_ (3,5-dinitrobenzoyl) _2,2-diphenyl -Hydrazinole, N— (2-nitro-benzoinole) -1-N ,, N, 1-diphenyl-2-hydrazyl, N-benzoyl-N ,, N, —bis— (4-nitro-phenyl) hydrazine, 1— ( Trifluoroacetyl) -2,2-bis (3,5_ditetra-butylphenyl) hydrazyl, tribenzoylhydrazolyl radical, 1-phenylpyrazolidone-1 (3) -radical, 5_methyl_1-phenyl 1,3-pyrazolidone radical, 2,5-dioxo—4_feneru [1,3,4] oxaziazolidine_3_yl,
- Preferred examples of the hydrazyl radical of the formula (5) include 1_ (3,5-dinitrobenzoyl) —2,2-diphenyl-hydrazyl, tribenzoylhydrazoylradicanole, and 1-phenyl Nilpyrazolidone-1 (3) -radical, 2,5-dioxo-4_phenyl [1,3,4] oxaziazolidine-1_3,3,4-dihydro-1,4-dioxo-1 3-phenyl-2-phthaladyl, 3,4-dihydro-1- (4-nitrophenyl) -1,4-dioxo-2-phthaladyl, and more preferably 1-phenylpyrazolidone-1 (3) — Radicals, such as 3,4-dihydro-11,4-dioxo-3-phenyl-12-phthalazyl.
- hydrazine compound of the formula (6) include, for example, benzoic acid— ( ⁇ ,, ⁇ , —diphenyl-hydrazide), 1- (3,5-dinitrobenzoyl) -2 , 2—diphenil-hi Drazine, 2-nitro-benzoic acid mono ( ⁇ ', ⁇ '-diphenylinohydrazide), benzoic acid mono [ ⁇ ,, ⁇ '-bis (4-nitro-phenyl) monohydrazide], 1— ( Trifluora cetyl) _2, 2_bis (3,5_ditetra-butylphenyl) hydrazide, tribenzylhydrazine, 1_phenyl-2-pyrazolidine-3-one, 5-methyl-1_phenyl-3-ylpyrazolidine-3-one, 3_Fenilou [1,3,4] oxaziazolidine-1 2,5-dione, 4,4-dimethinolene 1_Feniluppyrazol
- Preferred examples of the hydrazine compound of the formula (6) include 1_ (3,5-dinitrobenzoyl) _2, 2-diphenylenolhydrazine, tribenzoylhydrazine, 1_pheninolevirazolidine One 3_one, 3-phenylenolone [1,3,4] oxaziazolidine 1,2,5-dione, 1-phenyl-1,2-dihydropyridazine-1,3,6-dione, 2-phenylenol , 3-dihydro-phthalazine-l, 4-dione, 2- (4-nitrophenyl) -l, 3-dihydro-phthalazine-l, 4-dione, and more preferably, 1- Examples include phenyl-1-bilazolidine-3-one, 1-phenyl-1,2-dihydro-1-pyridazine-1,3-dione, 2-phenylenoleate 2,3-dihydro-phthalazine
- hydrazyl radical of the formula (1) and the hydrazine compound of the formula (2) include compounds represented by the following formulas (7) and (8), respectively.
- each of R 10 , R 11 , and R 12 independently represents a hydrogen atom, an oxygen atom, a sulfur atom, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, or a cyano group.
- R 13 is defined the same as each of R 1Q —R 12 except that it is not a hydrogen atom; and, if desired, two members selected from the group consisting of R 11 , R 12 and R 13 are linked together to form a ring Has formed.
- the aliphatic group may be saturated or unsaturated, may be substituted with a substituent, or may be unsubstituted, and may have a chain, cyclic or branched structure.
- the aliphatic group may also contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms.
- the aromatic group may be substituted or unsubstituted, and may contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms.
- the hydroxyl group may form a salt with a metal atom.
- One or more oxygens which may be substituted or unsubstituted with a aryloxy group, a haloalkyl group, a mercapto group, an alkylthio group, an arylthio group, a sulfo group, a sulfiel group, a sulfonyl group or a heterocyclic group.
- the substituent includes an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, and a carbonyl group.
- examples of R 1Q , R 11 and R 12 are preferably a hydrogen atom, an oxygen atom, a sulfur atom, an aliphatic group, an aromatic group, a nitro group.
- Preferred examples of R 13 are, except for excluding hydrogen atom is the same as defined in R 1Q, R ", and R 12.
- substituents may be substituted with a substituent May contain or contain one or more oxygen, nitrogen, sulfur, silicon, phosphorus, boron or halogen atoms.
- the substituent includes an aliphatic group, an aromatic group, a halogen atom, a hydroxy group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, Carbonyl group, carboxyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, levamoyl group, alkoxy group, aryloxy group, haloalkyl group, mercapto group, alkylthio group, arylthio group, sulfo group, sulfinyl Group, a sulfonyl group or a heterocyclic group.
- hydrazyl radical of the formula (7) include, for example, 2,4,6_triphenyl-2,4-dihydro-2H- [1,2,4,5] tetrazine-1 —Yl, 1,3,5-tris— (p-cloth phenol) Ferdazil, 2,6-diphenyl _4_pentafluorophenylferdazyl, 2,4_bisperfluorophenyl _6_fue Nilferdazil, 2,4,6-Tris-perfluoro Mouth-phenylferdazyl, 2_ (2,3,4,5,6_pentafluoro-pheninole) _4,6-Diphenylenol 1,2,3,4-tetrahydro [1,2,4,5] phenoredazinole, 2,4,6-tripheninole 1,2,3,4-tetrahydro- [1,2,4,5] ferdazyl, 1_ (4-nitro-phenyl)
- hydrazyl radical of the formula (7) include 2,4,6_triphenyl-2,4-dihydro_2H_ [1,2,4,5] tetrazine_1_yl and 2_ ( 2,3,4,5,6_pentafluoro-phenyl) — 4,6-diphenyl—1,2,3,4-tetrahydro— [1,2,3,4] ferdazyl, 1_ (4—nitro— (Fenil) —3,5-Diphenyl-Ferdazil, 6—Anthracene—9yl—2,4- 1,2,3,4-tetrahydro- [1,2,4,5] phenoleta, dinole, 1,3,5,6-tetraphenylferdazyl, 6-methyl-3-nitro-5 _Diufuerdazil, 1,3,5-trifuninole 6-oxofoldazil, 1,3,5_trifeninole 6-thioxoferd
- hydrazine compound of the formula (8) examples include 2,4,6_triphenyl-1,2,3,4-tetrahydro-1- [1,2,3,4] tetrazine, 3,5-tris (p-chlorophenyl) tetrazine, 2,6-diphenyl-4_pentafluoro_1,2,3,4-tetrahydro-1-tetrazine, 2,4-bis (perfluorophenyl) -1 —Phenyl-1-, 2,3,4-tetrahydro-1-tetrazine, 2,4,6-tris (perfluorophenyl) -1,2,3,4-tetrahydro-1-tetrazine, 2 -— (2,3,4,5) 1,6-pentafluorene-1,2,3,4-tetrahydro [1,2,4,5] tetrazine, 2,4,6-triphenyl-1,2,3 1,4-tetrahydro- [1,2,4,5] tetrazine, 2,
- Preferred examples of the hydrazine compound of the formula (8) include 2,4,6-triphenyl 1,2,3,4 —Tetrahydro— [1,2,3,4] tetrazine, 2_ (2,3,4,5,6_pentafluoro-phenyl) —4,6-diphenyl—1,2,3,4-tetrahydro- [1, 2,4,5] tetrazine, 2,4,6-triphenyl 1,2,3,4-tetrahydro-1 [1,2,4,5] tetrazine, 2_ (4-nitro-phenyl) _4,6 —Dipheninole 1, 2,3,4—tetrahydro— [1,2,4,5] tetrazine, 6_anthracene _9inole-1,2,4-dipheninole 1,2,3,4—tetrahydro 2,4,5 ] Tetrazine, 2,3,4,6-tetraphenyl-1,2,3,4-tetrahydro-1 [1,2,4,5] tetraz
- 2,4,6_triphenylinole_1,2,3,4-tetrahydro- [1,2,3,4] tetrazine 2,3,4,6-tetraphenyl- 1,2,3,4-tetrahydro- [1,2,4,5] tetrazine, 1,3,5_triphenyl-1-6-oxotetrazine, 1,3,5_triphenyl-16-thioxotetrazine and the like.
- These compounds can be used as a single compound, and two or more It can also be used as a mixture of compounds.
- the amount of at least one selected from the group consisting of the hydrazinol radical of the formula (1) and the hydrazinide conjugate of the formula (2) varies depending on the type of the oxidation reaction, and a desired catalytic effect can be obtained.
- the amount is usually in the range of 0.0001 to 1 monol, preferably 0.0005 to 0.5 monol, and more preferably 0.001 to 0.3 mol per mol of the reaction substrate. .
- the amount of each compound used is, with respect to one compound of one compound, the binding force of the other compound is usually 0.001 to 0.99, preferably, The range is from 0.01 to 0.99, more preferably from 0.1 to 0.9.
- At least one selected from the group consisting of the hydrazinole radical of the formula (1) and the hydrazinyl conjugate of the formula (2) may be used in a form supported on a carrier.
- a carrier a porous inorganic carrier such as organic polymer silica, silica-alumina, zeolite and activated carbon can be used. Further, it is also possible to carry the compound in a complex with an oxidation promoter such as a transition metal compound described later.
- the hydrazinole radical of the formula (1) and the hydrazinide conjugate of the formula (2) are prepared by a conventional reaction method. Can be prepared.
- a hydrazine compound of formula (2) a hydrazine compound having a substituent corresponding to R 1 in formula (2) and a halogen compound having a substituent corresponding to R 3 in formula (2)
- the hydrazine ridge of the formula (2) is obtained by reacting the ridge and condensing both compounds.
- the obtained hydrazine compound is oxidized with an oxidizing agent such as PbO, KMnO, or CrO to obtain a hydrazyl radical of the formula (1).
- 2,2-diphenyl-1-picrylhydrazine is obtained by heating and refluxing diphenylhydrazine, picrinolechloride and sodium hydrogen carbonate in an ethanol solvent, and then crystallizing with benzene-ethanol.
- 2,2-diphenyl-1-picrylhydrazyl is obtained by reacting the 2,2-diphenyl-1-picrylhydrazine obtained above with hydrazine in the presence of sodium sulfate in a benzene solvent in the presence of sodium sulfate. — Obtained by oxidation with 20 times (mol) of Pb ⁇ .
- the oxidation promoter optionally used in the present invention is an oxidizing agent which is added to the reaction system together with (at least one selected from the group consisting of hydrazyl radical of formula (1) and hydrazine compound of formula (2)). It promotes the reaction.
- the oxidation promoter can be used in the form of various metals, metal oxides, metal salts, or organometallic compounds, which can be any of the metal elements of Group 116 of the periodic table. It is preferably a metal compound containing at least one element selected from the elements.
- the transition metal of the transition metal compound is preferably at least one selected from the group consisting of elements belonging to Groups 3 to 12 of the periodic table.
- the elements belonging to Group 3 are lanthanoid elements represented by the element symbols La, Ce, Sm, Eu, Ac, Th, etc.
- the Group 4 elements are element symbols Ti, Zr, Hf
- the group 5 element is an element represented by an element symbol V, Nb, Ta.
- the group 6 element is an element represented by an element symbol Cr, Mo, W
- Group 7 elements are elements represented by element symbols Mn and Re.
- Group 8 elements are elements represented by element symbols Fe, Ru, and Os.
- Group 9 elements are element symbols C It is an element represented by o, Rh, and Ir.
- a Group 10 element is an element represented by an element symbol of Ni, Pd, and Pt.
- a Group 11 element is an element represented by an element symbol of Cu, Ag, and Au.
- Group 12 elements are element symbols Zn and Cd, and are preferably at least one element selected from these element groups.
- transition metal compound examples include simple substances, hydroxides, oxides (including complex oxides), halides (fluorides, chlorides, bromides, iodides) of the above-mentioned transition metal elements, and oxo acid salts ( Inorganic metal compounds such as nitrates, sulfates, phosphates, borates, perchlorates, carbonates), oxo acids, polyacids (isopoly acids, heteropoly acids), and organic acid salts (e.g., Organic metal compounds such as acetate, propionate, thiocyanate, naphthenate, and stearate), and complexes.
- Inorganic metal compounds such as nitrates, sulfates, phosphates, borates, perchlorates, carbonates
- oxo acids such as nitrates, sulfates, phosphates, borates, perchlorates, carbonates
- oxo acids such as nitrate
- ligands that form the complex include hydroxyl, alkoxy, acyl, alkoxycarbonyl, acetylacetonato, cyclopentagenenyl, halogen atom, carbonyl, oxygen atom, H ⁇ (acco), and phosphine. , CN, NO, NO, NO
- metal compounds can be used alone or in combination of two or more. These metal elements or metal compounds may form salts or complexes with the hydrazyl radical of the formula (1) or the hydrazine conjugate of the formula (2), which is the oxidation catalyst of the present invention. ,.
- transition metal compound examples include, for example, a tungsten compound, such as metal tungsten, tungsten oxide, tungsten oxide, tungsten acid, sodium tungstate, zinc tungstate, and tungsten tungsten.
- a tungsten compound such as metal tungsten, tungsten oxide, tungsten oxide, tungsten acid, sodium tungstate, zinc tungstate, and tungsten tungsten.
- titanium compounds include titanium metal, titanium oxide, titanium tetrachloride, dititanium sulfate, titanium acetyl acetonate, titanium tetraethoxide, titanium tetra-iso-propoxide, titanium tetra- iso -butoxide. , Titanium naphthenate, titanium silica light molecular sieves, titanium phosphate, zirconium titanate, sodium titanate, barium titanate and the like.
- Examples of the molybdenum compound include metal molybdenum, molybdenum oxide, molybdenum chloride, molybdenum 2-ethylhexanoate, molybdenum hexacarbonyl, molybdenum bis (acetinoleacetonato) oxide, molybdic acid, sodium molybdate, Examples include molybdophosphate, molybdate, cobalt molybdate, manganese molybdate, vanadomolybdate, manganese vanadium molybdate, manganese vanadomolybdate, and the like. Examples of the compound of another metal element include a compound corresponding to the tungsten, titanium, or molybdenum compound.
- the transition metal compound may be a homogeneous or heterogeneous system, or a heterogeneous (solid) metal component supported on a suitable carrier.
- ⁇ , SiO / Al ⁇ , Ti ⁇ , Zr ⁇ , Zn ⁇ , barium sulfate, potassium carbonate, diatomaceous earth, zeolite and the like can be used.
- a known supporting method used for producing a supported catalyst for example, an adsorption method, an impregnation method, a coprecipitation method, a sol-gel method, etc. can do.
- the loading amount of the metal component is 0.0001 to 0.8 part by weight, preferably 0.001 to 0.5 part by weight, more preferably 0.01 to 0.3 part by weight based on 1 part by weight of the carrier. is there.
- the amount of the oxidation promoter used is usually 0.0005 to 0.8 monol, preferably 0.0001 to 0.4 monol, more preferably 0.0005 to 1 mol of the reaction substrate. — It is in the range of 0.2 monoles.
- the periodic table in the present invention is a periodic table defined by the International Union of Pure and Applied Chemistry Inorganic Chemistry Nomenclature (1989).
- reaction substrate used in the oxidation reaction method of the present invention include various reaction substrates effective for the selective oxidation reaction described in the section of the background art, for example, hydrocarbons, alcohols, carbonyl compounds, and ethers. , Amines, sulfur compounds, heterocyclic compounds and the like.
- reaction substrates include various substituents, for example, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, and a carbohydrate.
- substituents for example, an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group, an amino group, an imino group, an azo group, and a carbohydrate.
- Nyl group carboxyl group, acylole group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, alkoxy group, aryloxy group, haloalkyl group, mercapto group, alkylthio group, arylthio group, sulfo group, sulfiel group , A sulfonyl group or a heterocyclic group may be substituted.
- hydrocarbons include propane, n-butane, isobutane, n-pentane, n-xane, 2-methylpentane, 3-methylpentane, propylene, 2-butene, isobutene, butadiene, isoprene, 1 _ Saturated or unsaturated, straight-chain and branched aliphatics such as pentene, 1-hexene, 1-heptene, 3-methynolei 1-butene, 2,3-dimethyl-1-butene, and saltedaryl Hydrocarbon, cyclopentane, cyclohexane, cycloheptane, cyclooctane, methinolecyclohexane, ethinolecyclohexane, dimethinolecyclohexane, chlorocyclohexane, methoxycyclohexane, cyclopentene, cyclohexene,
- alcohols include methanol, ethanol, n_propanol, isopropanol, n-butanol, s-butanol, t-butanol, n-pentanol, n-hexanol, n-ptanol, and aryl.
- Saturated and unsaturated alcohols and crotyl alcohols Saturated and unsaturated alicyclic alcohols such as saturated aliphatic alcohols, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclohexanol, cyclohexen-1-ol, ethylene glycol, propylene glycol, trimethylene glycol
- 1,3-butanediol 1,2-cyclohexanediol, 1,4-cyclohexanediol and other aliphatic and alicyclic polyhydric alcohols, benzyl alcohol, salicyl alcohol, benzhydrol, etc. Alcohols and the like.
- the carbonyl compound has at least one carbonyl group in the molecule.
- Specific examples of the carbonyl compound include honolemuanolaldehyde, acetoaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 1_pentanal, 1-hexanal, 1_heptanal, 1-otatanal, 1-nonanal, Aldehydes such as 1-decanal, acrolein, methacrolein, benzaldehyde, nitrobenzaldehyde, aminobenzanolaldehyde, guanoletanoleanolaldehyde, adipaldehyde, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, Methyl butyl ketone, methyl isobutyl ketone, cyclopentanone,
- ethers include getyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methylethyl ether, methylbutylether, ethylbutylether, diarylether, methylbutylether, anisol, dibenzylether, Phenylbenzyl ether and the like.
- amines include methinoleamine, dimethylamine, trimethylamine, ethylamine, getylamine, triethynoleamine, propylamine, dipropylamine, trippropinoleamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, and triptylamine.
- Alicyclic amines such as aliphatic amines such as arolinoleamine, diarylamine and triallylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine and cyclooctylamine, aniline, N-methylaniline, N, N-dimethylaniline And aromatic amines such as toluidine, benzylamine and phenylenediamine.
- sulfur compound examples include methanethiol, ethanethiol, 1-propanethiol, 1-butanethiol, 1-hexanethiol, 1-octanethiol, ethylenethioglycol, propylenethioglycol, and cyclopentanethiol.
- Thiols such as cyclohexanethiol, methylcyclohexanethiol, phenylmethanethiol, 2-phenylethanethiol, getyl sulfide, dipropyl sulfide, diisopropyl
- heterocyclic compound examples include furan, thiophene, pyrrole, thiopyran, pyridin, piperidine, morpholine, thiazole, imidazole, pyrimidine, 1,3,5-triazine, indole, quinoline, purine, and chroman.
- Carbazole, benzothiazole, and benzoisoquinoline examples include furan, thiophene, pyrrole, thiopyran, pyridin, piperidine, morpholine, thiazole, imidazole, pyrimidine, 1,3,5-triazine, indole, quinoline, purine, and chroman.
- Carbazole, benzothiazole, and benzoisoquinoline examples of the heterocyclic compound.
- reaction substrates can be used alone or as a mixture of two or more. Also, a mixture with another organic compound or inorganic compound which does not necessarily need to be purified may be used.
- reaction substrates are preferred as reaction substrates.
- the amines used in the present invention are preferably primary amines and secondary amines.
- the primary amine is not particularly limited as long as one substituent is bonded to the amino group and the carbon atom bonded to the amino group has at least one hydrogen atom.
- Amamine has one or more such amino groups in the molecule.
- Examples of such a primary amine include a primary amine represented by the following formula (9). [0146] [Formula 21]
- R 1 and R 2 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or an aralkyl group, provided that R 1 and R 2 are not simultaneously a hydrogen atom;
- R 1 and R 2 can be linked together to form a ring.
- the above-mentioned aliphatic group refers to a saturated or unsaturated linear or branched aliphatic hydrocarbon group, or a saturated or unsaturated alicyclic hydrocarbon group.
- the aliphatic group, the aromatic group, or the aralkyl group may be any of various substituents, for example, an aliphatic group, an aromatic group, an aralkyl group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group.
- examples of the ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclododecane ring and the like.
- the carbon number of the aliphatic group is usually 120, preferably 115, and more preferably 110, and the carbon number of the aromatic group is usually 5-12, preferably 6-10.
- the number of carbon atoms is usually 120, preferably 115.
- Examples of such primary amines include methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-otatinoleamine, n-nonylamine, and n-nonylamine.
- a primary amine is brought into contact with molecular oxygen to carry out an oxidation reaction, thereby producing an oxime compound or a nitro compound in which the amino group of primary amine is oxidized.
- R 1 and R 2 are the same as defined for the above formula (9).
- Examples of such an oxime compound include formaldehyde oxime, acetoaldehyde deoxydoxime, propionaldehyde oxime, n-butyl aldehyde oxime, n-pentyl aldehyde oxime, n-hexyl aldehyde oxime, and n-hexyl aldehyde oxime.
- nitro compound examples include nitromethane, nitroethane, 1-nitropropane, 1_nitrobutane, 1_nitropentane, 1_nitrohexane, 1_nitroheptane, and 1_nitroproha.
- the primary amine particularly preferably used in the present invention is cyclohexylamine, and cyclohexanone oxime is obtained as an oxidation product.
- the second amine is one in which two substituents are bonded to an amino group, and at least one of the two carbon atoms to which the amino group is bonded has at least one hydrogen atom. If there is, it is not particularly limited. Secondary amines have one or more such amino groups in the molecule.
- Examples of such a secondary amine include a secondary amine represented by the following formula (10).
- R 1 and R 2 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or an aralkyl group
- R 3 represents each of R 1 and R 2 except that it is not a hydrogen atom Is defined as; and If desired, two members selected from the group consisting of R 1 , R 2 and R 3 are bonded to each other to form a ring.
- the above-mentioned aliphatic group refers to a saturated or unsaturated linear or branched aliphatic hydrocarbon group, or a saturated or unsaturated alicyclic hydrocarbon group.
- the aliphatic group, the aromatic group, or the aralkyl group may be any of various substituents, for example, an aliphatic group, an aromatic group, an aralkyl group, a halogen atom, a hydroxyl group, a nitro group, a nitroso group, a cyano group.
- examples of the ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclododecane ring, Examples include a pyrrolidine ring, a piperidine ring, a tetrahydroisoquinoline ring, and the like.
- the carbon number of the aliphatic group is usually 120, preferably 115, and more preferably 110, and the carbon number of the aromatic group is usually 5-12, preferably 6-10.
- the number of carbon atoms is usually 120, preferably 115.
- Examples of such secondary amines include N, N-dimethylamine, N, N-diethylamine, N, N-di (n-propyl) amine, N, N-di (n-butyl) amine, N , N-di (n-pentyl) amine, N, N-di (n-hexyl) amine, N, N-di (n-heptyl) amine, N, N-di (n-octyl) amine, N, N-di (n-nonyl) amine, N, N-di (n-decyl) amine, N, N-diisopropylamine, N, N-isobutylamine, N, N-di (sec-butyl) amine, N-ethynole_tert-butylamine, N, N-dibenzylamine, N-benzyl_tert_butylamine, N-benzylamine
- the secondary amine include optically active amines having an asymmetric carbon in the molecule, and salts of the secondary amine with an acid (such as hydrochloric acid, sulfuric acid, and nitric acid).
- an acid such as hydrochloric acid, sulfuric acid, and nitric acid.
- Formulas R 2 and R 3 are the same as defined for formula (10) above.
- Examples of such a ditron compound include N-methylidenemethylamine N-oxide, N-ethylidenemethylamine N-oxide, N-propylidenemethylamine N-oxide, and N-oxide.
- the oxidation reaction system of the secondary amine in the present invention when an acceptor of a product, a nitrone-conjugated product, particularly an olefin, is present, an adduct of a dithrone can be directly synthesized.
- the dithrone conjugate obtained by the oxidation reaction method of the present invention is an excellent 1,3-dipole, and undergoes an addition reaction with various olefins to give a 1,3-dipole adduct, which is an alkaloid.
- Is a precursor of a physiologically active substance such as, and a useful compound. Therefore, in the present invention, it is industrially very advantageous to carry out the oxidation reaction of secondary amine in the presence of olefin.
- the oxidation reaction in the present invention can be performed in a gas phase or a liquid phase, and it is particularly preferable to perform the reaction in a liquid phase.
- the reaction is performed in a liquid phase, specifically, the oxidation reaction is performed in at least one reaction medium selected from the group consisting of water and an organic solvent, or the oxidation reaction is performed using a reaction substrate as a reaction medium. It can be carried out.
- the organic solvent means a protic or aprotic organic solvent, and any organic solvent can be used in the present invention.
- the protic solvent include organic solvents such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol and other primary, secondary and tertiary alcohols having 110 carbon atoms, formic acid, acetic acid and propionic acid. Carboxylic acids.
- aprotic solvent examples include aliphatic hydrocarbons such as hexane and otatan, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chlorophonolem, dichloromethane, carbon tetrachloride, and chlorobenzene, and acetonitrile.
- Nitriles such as propionitrile and benzonitrile, nitro compounds such as nitrobenzene, nitromethane and nitroethane; ethers such as dimethyl ether, getyl ether, diisopropyl ether and dioxane; esters such as ethyl acetate and butyl acetate; Examples include amides such as formamide, acetoamide, dimethylformamide, dimethylacetamide, getylacetamide, and hexamethylphosphoric triamide.
- Is preferably an aprotic solvent, and in particular, nitriles, nitro compounds, compounds, ethers, and amides are preferably used. More preferably, as nitriles, acetonitrile, benzonitrile, and as amides, dimethinolehonolemamide and dimethylacetamide are used.
- any of the above solvents can be used alone or as a mixture of two or more.
- the concentration of the reaction substrate is usually 0.1 to 95% by weight, preferably based on the total weight of the water and / or the organic solvent and the reaction substrate. It can be 1 to 30% by weight.
- a method in which a reaction substrate is brought into contact with molecular oxygen in the presence of an oxidation catalyst to perform an oxidation reaction is used.
- the reaction can be performed in a fixed bed or a suspension bed by a known system such as a batch system, a semi-batch system, and a continuous system.
- Molecular oxygen is usually used in the form of pure oxygen, air or a mixture with nitrogen and an inert gas such as helium.
- the concentration of oxygen in the mixture is preferably in the range of 2 to 23% by volume, more preferably in the range of 3 to 11% by volume.
- the oxygen concentration is preferably in a range where the reaction system does not have an explosive composition.
- the oxidation reaction of the reaction substrate is preferably performed in a liquid phase. Therefore, it is necessary that molecular oxygen introduced as a gas into the reaction system is dissolved at a predetermined concentration in the liquid phase in which the catalyst exists under the reaction conditions.
- a molecular oxygen-containing gas is introduced under reduced pressure or normal pressure under a temperature condition in which a mixture of a reaction substrate, a product, and a solvent is in a reflux state, the amount of oxygen dissolved in the liquid phase is small. Therefore, as a method for dissolving oxygen at a predetermined concentration in the liquid phase, a method in which the molecular oxygen-containing gas is brought into contact with the liquid phase under a pressure condition exceeding normal pressure (up to 20 MPa) is preferable.
- the reaction pressure of a desired substrate may vary depending on the catalyst and reaction conditions used.
- a mixed gas with an inert gas having a predetermined oxygen concentration may be supplied at a desired total pressure for the reaction.
- the total pressure in the reaction system is generally in the range of 0.1 to 20 MPa, preferably in the range of 11 lOMPa.
- the molecular oxygen-containing gas may be directly blown into a liquid phase formed in the reaction system, or may be a gas phase existing in contact with the liquid phase. May be introduced into the department.
- pure oxygen, air, or diluted oxygen gas is continuously or intermittently maintained so as to maintain a predetermined gaseous oxygen partial pressure.
- the reaction can be continued for a predetermined time until the target reaction yield is reached without performing the reaction.
- the reaction temperature in the present invention is usually 0 200 ° C, more preferably 40 180 ° C, most preferably 60 160 ° C.
- the temperature is higher than 200 ° C due to the reaction to be carried out, the sequential decomposition of the product or the sequential oxidation reaction proceeds, and the reaction selectivity of the target compound tends to decrease due to the increase of high-boiling by-products
- the reaction rate tends to decrease.
- the reaction time is not particularly limited as long as a target value of the selectivity and the yield of the target compound is determined and appropriately selected according to the target value, and is usually several seconds to several hours.
- the reaction product is easily separated from the reaction mixture by a conventional method, for example, a separation method such as distillation, extraction, concentration, filtration, crystallization, recrystallization, or column chromatography, or a separation method combining these methods. Can be separated and purified. Generally, it is preferred that unreacted substrate be recycled to the reactor. When the catalyst is contained in the reaction medium after separating the product, the reaction medium can be recycled to the reactor and reused in the reaction.
- the hydrazyl radical of the formula (1) which is an oxidation catalyst of the present invention for example, a free radical such as 2,2_diphenyl-1-picrylhydrazyl (DPPH) is used as the organic substrate C-H , N—H, P hO-H, S_H, etc., abstract hydrogen atoms and selectively give the corresponding radical species.
- DPPH 2,2_diphenyl-1-picrylhydrazyl
- DPPH 2,2-diphenyl-1-picrylhydrazine
- DPPH acts as an acceptor of hydrogen radicals in the reaction with the organic substrate.
- the present inventor has found that when the hydrazyl radical of the formula (1) having such a reaction characteristic is brought into contact with a reaction substrate in the presence of molecular oxygen, the hydrazinol radical functions as a catalyst, thereby reducing mild conditions. It was found that the desired oxidation product could be produced with high selectivity and high efficiency. The same effect can be obtained by using the hydrazine conjugate of the formula (2) or the mixture of the hydrazinole radical of the formula (1) and the hydrazine conjugate of the formula (2) as the oxidation catalyst.
- DPPH and DPPH act as a hydrogen mediator while reversibly interconverting. More specifically, DPPH generated from the reaction between the substrate and DPPH in the reaction system directly activates oxygen molecules to generate electrophilic oxygen-active species and DPPH, and the reaction substrate It is presumed that a catalytic cycle has been established in which DPPH extracts hydrogen atoms from the reaction intermediate in which oxygen atoms have been added to DPPH and DPPH is regenerated.
- DPPH was found to act catalytically when subjected to high-pressure oxygen conditions in the presence of (pro-oxidant). In addition, the reaction proceeds catalytically even if DPPH is used instead of DPPH under the same conditions. This result indicates that DPPH and DPPH reversibly interconvert and act as a hydrogen mediator, and the use of a reaction substrate as a hydrogen source allows efficient activation of oxygen molecules as shown in formula (ii). Suggest that it is done. In other words, it is presumed that the oxygen molecules are reduced by DPPH, and the reduced oxygen molecules generate oxygen active species on the metal of the oxidation promoter and participate in the oxidation reaction of the reaction substrate.
- the oxygen active species generated on the metal of the oxidation promoter has different oxidizing ability depending on the type of the metal compound as the oxidation promoter. Therefore, in this reaction system, the reaction substrate and The oxidation reaction can be arbitrarily controlled by selecting an oxidation promoter according to the type of oxidation product desired. For example, as shown in Examples 14 and 15 below, in the oxidation reaction of cyclohexynoleamine, each of cyclohexanone oxime and nitrocyclohexane is selectively synthesized by changing the type of oxidation promoter. It can be.
- the hydrazyl radical of formula (1) such as DPPH or DPPH
- the hydrazine compound of the formula (2) functions as a catalyst in the oxidation reaction of an organic substrate in the presence of oxygen.
- DPPH and DPPH are reversibly interconverted by electrochemical experiments
- the oxidation catalyst of the present invention is applicable to the oxygen oxidation of many organic substrates. It is possible to do.
- the conversion rate of the reaction substrate and the selectivity of the oxidation product used for evaluating the result of the oxidation reaction of the reaction substrate in Examples and Comparative Examples are respectively defined by the following formulas.
- Measuring device GC-14A gas chromatograph manufactured by Shimadzu Corporation of Japan (including Flame Ion Dani Detector (FID))
- Carrier gas helium
- the amount of metal contained in the solid powder was measured using a fluorescent X-ray analyzer under the following conditions.
- Measuring device RIX-3000 manufactured by Nippon Rigaku Denki Kogyo
- the tablet was prepared by placing it in an aluminum ring (mold) and compressing it using a tableting machine at a pressure of 20 tons.
- Example 1 was repeated except that 0.077 g (0.125 mmol) of 2,2-di (4_t-octylphenyl) -1-picrylhydrazyl (Sigma-Aldrich Japan KK) was used as the oxidation catalyst.
- the reaction was carried out in the same manner as described above. As a result, the conversion of cyclohexylamine was 62.4%, and the selectivity for cyclohexanone oxime was 95.6%.
- Example 1 was repeated except that 0.087 g (0.125 mmol) of 1,3,5-tris (N, N-diphenylhydrazino) -2,4,6_tricyanbenzole was used as the oxidation catalyst.
- the reaction was carried out in the same manner as in 1.
- the conversion of cyclohexylamine was 60.1%, and the selectivity for cyclohexanone oxime was 92.7%.
- the reaction was carried out in the same manner as in Example 1 except that 0.17 g (0.25 mmol) of 1-yl (manufactured by Sigma-Aldrich Japan) was used. As a result, the conversion of cyclohexylamine was 20.5%, and the selectivity of cyclohexanone oxime was 83.7%.
- Example 1 As shown in Table 1, the reaction was carried out in the same manner as in Example 1 except that the type and amount of the oxidation promoter were changed.
- the WO / Al 2 O (ie, tantalum oxide supported on alumina) in the table used was the one prepared in Example 1.
- WO / ZrO (ie, tungsten oxide supported on zirconia) and WO / TiO (ie, tungsten oxide supported on titanium oxide) in the table were prepared by the following methods.
- Ti ⁇ (acac) is titanium (II) acetyl acetonate and is represented by the following formula: Ti ⁇ (CH COCHCOCH).
- Ti ( ⁇ i—Pr) is titanium tetraisopropoxide and is represented by the following formula: Ti [ ⁇ CH ( ⁇ )
- Dry ZrO (RC100, manufactured by Daiichi Nippon Daiichi Element Co., Ltd.) at 120 ° C overnight and use it as a carrier.
- Ammonium paratungstate pentahydrate (Nippon Kokuwa Wako Pure Chemical Industries, Ltd.) 1.4 g was dissolved in 60 g of water, and 10 g of dried Zr ⁇ was added to form a suspension.
- This suspension was placed in a glass flask, placed on a rotary evaporator, immersed in an oil bath at a temperature of 90 ° C under normal pressure, and slowly stirred and mixed for 1.5 hours to obtain a slurry.
- the slurry is heated at 100 ° C under normal pressure on an oil bath while stirring to evaporate water.
- a predetermined amount of the powder is put into a glass tubular furnace, and calcined at 500 ° C for 4 hours while supplying air under normal pressure to obtain a tantalum oxide.
- a solid powder (WZ / Zr ⁇ ) in which ZrO was carried on the substrate was obtained. When analyzed by X-ray fluorescence, it was found to contain 9.2% by weight of tungsten.
- Example 17 The reaction was carried out in the same manner as in Example 16 except that the reaction temperature was 90 ° C. As a result, the conversion of cyclohexylamine was 62.5%, and the selectivity of nitrocyclohexane was 76.3%.
- the reaction was carried out in the same manner as in Example 1 except that the reaction time was changed to 3 2 and the reaction time was changed to 2 hours.
- the reaction product was analyzed by gas chromatography, cyclohexanone oxime was selectively obtained as shown in Table 6.
- a reaction was carried out in the same manner as in Example 1 except that 0-646 g (5 mmol) of dibutylamine (manufactured by Sigma-Aldrich Japan Co., Ltd.) was used as a reaction substrate, and the reaction time was changed to 8 hours. As a result, the conversion of dibutylamine was 43.5%, and the selectivity for N-butylidenebutylamine N-oxide was 72.1%.
- Example 26 The same procedure as in Example 1 was performed except that 0.66 g (5 mmol) of 1,2,3,4-tetrahydroisoquinoline (manufactured by Sigma-Aldrich Japan) was used as a reaction substrate, and the reaction time was changed to 8 hours. The reaction was performed. As a result, the conversion of 1,2,3,4-tetrahydroisoquinoline was 39.0%, and the selectivity of 3,4-dihydroisoquinoline N-oxide was 78.4%.
- 1,2,3,4-tetrahydroisoquinoline manufactured by Sigma-Aldrich Japan
- Example 31 The reaction was carried out in the same manner as in Example 1 except that 0.41 g (5 mmol) of 11-butanethiol (Wako Pure Chemical Industries, Ltd., Japan) was used as a reaction substrate. As a result, the conversion of 1-butanethiol was 9.5%, and the selectivity of butyl disulfide was 96.1%.
- N-hydroxyphthalimide Nippon Kokuwa Wako Pure Chemical Industries, Ltd.
- 0.082 g N-hydroxyphthalimide
- the oxidation catalyst of the present invention causes various problems in the conventional oxidation process, that is, use of an expensive oxidizing agent or an oxidizing agent having a risk of explosion, low yield and selectivity of a target compound, Problems such as the complexity of the purification process for removing a large amount of by-products and the large consumption of energy can be overcome.
- the oxidation catalyst of the present invention can be advantageously used particularly for the selective oxidation reaction of hydrocarbons, alcohols, carbonyl compounds, ethers, amines, sulfur compounds, heterocyclic compounds and the like.
- a primary amine carboxylic compound or a nitro compound is converted into a secondary amine by a selective oxidation reaction with molecular oxygen without using an expensive oxidizing agent such as hydrogen peroxide or an organic hydroperoxide.
- an expensive oxidizing agent such as hydrogen peroxide or an organic hydroperoxide.
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Abstract
Description
Claims
Priority Applications (5)
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US10/565,886 US20060229471A1 (en) | 2003-07-25 | 2004-07-22 | Oxidation catalyst |
EP04747810.2A EP1655070B1 (en) | 2003-07-25 | 2004-07-22 | Oxidation catalyst |
CN2004800230296A CN1835800B (zh) | 2003-07-25 | 2004-07-22 | 氧化催化剂 |
JP2005512017A JP4895610B2 (ja) | 2003-07-25 | 2004-07-22 | 酸化触媒 |
US12/591,266 US8133834B2 (en) | 2003-07-25 | 2009-11-13 | Oxidation catalyst |
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US12/591,266 Continuation US8133834B2 (en) | 2003-07-25 | 2009-11-13 | Oxidation catalyst |
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EP (1) | EP1655070B1 (ja) |
JP (1) | JP4895610B2 (ja) |
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Cited By (5)
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US7638587B2 (en) * | 2006-04-18 | 2009-12-29 | University of Victoria Innovation and Development Corporatin | Verdazyl agents for the production of free standing polymers |
WO2014103850A1 (ja) | 2012-12-27 | 2014-07-03 | 住友化学株式会社 | オキシムの製造方法 |
WO2014157020A1 (ja) | 2013-03-27 | 2014-10-02 | 住友化学株式会社 | オキシムの製造方法 |
US10005718B2 (en) | 2014-02-07 | 2018-06-26 | Sumitomo Chemical Company, Limited | Catalyst, and method for producing oxidation product |
WO2020194633A1 (ja) * | 2019-03-27 | 2020-10-01 | シャープ株式会社 | 表示装置 |
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PL2326401T3 (pl) * | 2008-09-02 | 2017-01-31 | 3M Innovative Properties Company | Gazowy filtr powietrza pozbawiony amoniaku |
US9735371B2 (en) * | 2011-04-18 | 2017-08-15 | Merck Patent Gmbh | Compounds for electronic devices |
CN103012302B (zh) * | 2012-12-31 | 2016-02-10 | 南通宝叶化工有限公司 | 一种四螨嗪的生产工艺 |
US20190338429A1 (en) * | 2016-11-22 | 2019-11-07 | Asahi Kasei Kabushiki Kaisha | Electrode for electrolysis |
CN109206339B (zh) * | 2017-06-29 | 2021-04-27 | 湘潭大学 | 一种环己胺氧化制备环己酮肟的方法 |
CN112675908A (zh) * | 2020-12-23 | 2021-04-20 | 清华大学 | 一种醇类的有氧氧化方法 |
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US2966455A (en) * | 1957-08-14 | 1960-12-27 | Sun Oil Co | Refining hydrocarbons with hydrazines and hydrogenation catalysts |
US3095394A (en) * | 1960-05-03 | 1963-06-25 | Union Carbide Corp | Polyolefin oxides stabilized with 1, 1-diphenyl-2-picrylhydrazine and 1, 1-diphenyl-2-picrylhydrazyl |
ATE229499T1 (de) * | 1998-02-26 | 2002-12-15 | Massachusetts Inst Technology | Metallkatalysierte arylierungen und vinylierungen von hydrazinen, hydrazonen, hydroxylaminen und oximen |
JPH11342340A (ja) * | 1998-06-01 | 1999-12-14 | Daicel Chem Ind Ltd | 酸化触媒系及びそれを用いたケトイソホロンの製造方法 |
JP3687736B2 (ja) * | 2000-02-25 | 2005-08-24 | 日本電気株式会社 | 二次電池 |
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2004
- 2004-07-22 US US10/565,886 patent/US20060229471A1/en not_active Abandoned
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- 2004-07-22 WO PCT/JP2004/010399 patent/WO2005009613A1/ja active IP Right Grant
- 2004-07-22 EP EP04747810.2A patent/EP1655070B1/en active Active
- 2004-07-22 CN CN2004800230296A patent/CN1835800B/zh active Active
- 2004-07-22 KR KR1020067001401A patent/KR100676115B1/ko active IP Right Grant
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JPS4426281B1 (ja) * | 1965-11-22 | 1969-11-05 | ||
JP2002511093A (ja) * | 1997-07-02 | 2002-04-09 | クエイカー ケミカル コーポレイション | アミナール化合物の再生のための方法および組成物 |
JP2003144936A (ja) * | 2001-11-19 | 2003-05-20 | Daicel Chem Ind Ltd | 有機化合物製造用触媒、及びこの触媒を用いた有機化合物の製造法 |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US7638587B2 (en) * | 2006-04-18 | 2009-12-29 | University of Victoria Innovation and Development Corporatin | Verdazyl agents for the production of free standing polymers |
WO2014103850A1 (ja) | 2012-12-27 | 2014-07-03 | 住友化学株式会社 | オキシムの製造方法 |
US9533944B2 (en) | 2012-12-27 | 2017-01-03 | Sumitomo Chemical Company, Limited | Method for producing oxime |
WO2014157020A1 (ja) | 2013-03-27 | 2014-10-02 | 住友化学株式会社 | オキシムの製造方法 |
US9656950B2 (en) | 2013-03-27 | 2017-05-23 | Sumitomo Chemical Company, Limited | Method for producing oxime |
US10005718B2 (en) | 2014-02-07 | 2018-06-26 | Sumitomo Chemical Company, Limited | Catalyst, and method for producing oxidation product |
WO2020194633A1 (ja) * | 2019-03-27 | 2020-10-01 | シャープ株式会社 | 表示装置 |
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EP1655070A4 (en) | 2009-11-11 |
CN1835800A (zh) | 2006-09-20 |
KR100676115B1 (ko) | 2007-02-02 |
EP1655070B1 (en) | 2015-07-15 |
JPWO2005009613A1 (ja) | 2007-09-20 |
US20100069670A1 (en) | 2010-03-18 |
JP4895610B2 (ja) | 2012-03-14 |
KR20060027407A (ko) | 2006-03-27 |
CN1835800B (zh) | 2010-04-28 |
EP1655070A1 (en) | 2006-05-10 |
US20060229471A1 (en) | 2006-10-12 |
US8133834B2 (en) | 2012-03-13 |
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