WO2003062193A1 - Procede de fabrication d'un compose nitrone et d'un compose n-oxyl - Google Patents

Procede de fabrication d'un compose nitrone et d'un compose n-oxyl Download PDF

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Publication number
WO2003062193A1
WO2003062193A1 PCT/JP2003/000243 JP0300243W WO03062193A1 WO 2003062193 A1 WO2003062193 A1 WO 2003062193A1 JP 0300243 W JP0300243 W JP 0300243W WO 03062193 A1 WO03062193 A1 WO 03062193A1
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group
tungsten
molybdenum
compound
metal
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PCT/JP2003/000243
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English (en)
Japanese (ja)
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Koji Hagiya
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Sumitomo Chemical Company, Limited
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    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
    • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
    • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/94—Oxygen atom, e.g. piperidine N-oxide

Definitions

  • the present invention relates to a method for producing a thiol compound and an N-oxyl conjugate, and a catalyst thereof.
  • Ditron compounds and N-oxyl compounds are important compounds as various chemical products, their synthetic intermediates or polymerization inhibitors for unsaturated compounds, light stabilizers for resins, and co-oxidants for oxidation reactions (for example, Kaisho 63-63651, International Publication No.
  • the method (1) is complicated in the preparation of the catalyst, the method (2) is low in the yield depending on the type of amine, and the method (3) is toxic.
  • the method (4) was not necessarily industrially advantageous because the method (4) was expensive because the catalyst was expensive.
  • a metal oxide obtained by reacting hydrogen peroxide with at least one selected from the group consisting of tungsten metal, molybdenum metal, a certain kind of tungsten compound and molybdenum compound, which is inexpensive and easily available is a secondary amine.
  • the inventors have found that an oxyl compound can be obtained, and have led to the present invention.
  • the present invention relates to a tungsten metal, a molybdenum metal, a tungsten compound comprising tungsten and a group Ilb element, a group IVb element, a group Vb element or a group VIb element excluding oxygen, and a molybdenum and a group Ilb element,
  • a metal oxide catalyst obtained by reacting at least one selected from the group consisting of molybdenum compounds consisting of a group IVb element, a group Vb element or a group VIb element excluding oxygen with hydrogen peroxide.
  • the present invention provides a method for producing a nitrone compound and an N-oxylyl conjugate, wherein a secondary amine is reacted with hydrogen peroxide.
  • the present invention includes a tungsten metal, a molybdenum metal, a tungsten compound composed of tungsten and a Group Illb element, a Group IVb element, a Group Vb element or a Group VIb element excluding oxygen, and a molybdenum and a Group Illb element; At least one member selected from the group consisting of molybdenum compounds consisting of a group IVb element, a group Vb element or a group VIb element excluding oxygen (hereinafter abbreviated as a metal or a metal compound) and hydrogen peroxide A metal oxide catalyst that has been reacted is used.
  • tungsten compound composed of an Illb group element for example, Tungsten compounds such as tungsten boride and tungsten and a Group IVb element include, for example, tungsten carbide and tungsten silicate, and tungsten compounds such as tungsten and a Group Vb element such as nitride
  • Tungsten compounds such as tungsten boride and tungsten and a Group IVb element include, for example, tungsten carbide and tungsten silicate, and tungsten compounds such as tungsten and a Group Vb element such as nitride
  • Examples of the tungsten compound in which tungsten, tungsten phosphide, and the like are made of tungsten and a Group VIb element other than oxygen include, for example, tungsten sulfide.
  • a molybdenum compound composed of molybdenum and an Illb group element is, for example, molybdenum boride
  • a molybdenum compound composed of molybdenum and a group IVb element is, for example, molybdenum carbide, molybdenum silicate, etc.
  • molybdenum nitride, molybdenum phosphide, and the like include molybdenum nitride and molybdenum phosphide
  • molybdenum compounds that include the group VIb element except molybdenum and oxygen include molybdenum sulfide, for example. No.
  • tungsten metal tantalum boride, and tungsten sulfide are preferable.
  • the powerful metal or metal compound may be used alone or in combination of two or more.
  • an aqueous solution is usually used as the hydrogen peroxide to be reacted with such a metal or a metal compound.
  • an organic solvent solution of hydrogen peroxide may be used, but from the viewpoint of easy handling, it is preferable to use aqueous hydrogen peroxide.
  • the concentration of hydrogen peroxide in the hydrogen peroxide solution or the solution of hydrogen peroxide in the organic solvent is not particularly limited, but is practically 1 to 60% by weight in consideration of volumetric efficiency and safety.
  • a commercially available solution may be used as it is, or a solution whose concentration has been adjusted by diluting or concentrating as necessary.
  • an organic solvent solution of hydrogen peroxide for example, a method of extracting hydrogen peroxide solution with an organic solvent or a method of distilling hydrogen peroxide water in the presence of an organic solvent may be used. What was prepared by the means may be used.
  • the amount of hydrogen peroxide to be reacted with the metal or metal compound is usually at least 3 mol, preferably at least 5 mol, per mol of the metal or metal compound, and there is no particular upper limit.
  • the reaction between the metal or metal compound and hydrogen peroxide is usually carried out in an aqueous solution.
  • ether solvents such as getinol ether, methinole tert-butynoleatenole, and tetrahydrofuran
  • ester solvents such as ethyl acetate
  • alcohol solvents such as methanol, ethanol, and tert-butanol
  • the reaction may be carried out in an organic solvent such as a nitrile solvent such as acetonitrile and propionitrile or in a mixed solvent of the organic solvent and water.
  • the reaction between a metal or metal compound and hydrogen peroxide is usually carried out by mixing and contacting the two.
  • a metal oxide preparation is performed. It is preferable to carry out the reaction with stirring so that the metal or metal compound is sufficiently dispersed in the liquid.
  • a metal or a metal compound having a small particle size such as a powdered metal or a metal compound. It is preferable to use
  • the preparation temperature at the time of preparing the metal oxide is usually 110 to 100 ° C.
  • a metal oxide By reacting a metal or a metal compound with hydrogen peroxide in water, an organic solvent or a mixed solvent of an organic solvent and water, a part or all of the metal or the metal compound dissolves to form a metal oxide.
  • the metal oxide may be taken out of the prepared solution by, for example, concentration treatment, and used as a catalyst, or the prepared solution may be used as a catalyst as it is. Is also good.
  • the first secondary amine is one in which two substituents are bonded to an amino group, and at least one of the two carbon atoms bonded to the amino group has at least one hydrogen atom. Is not particularly limited as long as it has Further, it may have one such amino group in the molecule, or may have two or more such amino groups.
  • the second secondary amine is not particularly limited as long as two substituents are bonded to the amino group and the two carbon atoms bonded to the amino group do not have a hydrogen atom. Further, it may have one such amino group in the molecule. However, it may have two or more.
  • R 3 is a substituted Represents an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, wherein any two or three of RR 2 and R 3 are taken together May form a ring structure
  • alkyl group which may be substituted include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, n-decyl group, pendecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecinole group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, 2,2-dimethylcyclopropyl group, A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as a cyclopentyl group, a cyclohexyl group and a menthyl
  • aryloxy groups such as phenoxy groups, and aryloxy groups such as pentinoleoxy groups
  • Oxy group for example, halogen atom such as fluorine atom, chlorine atom, for example, acetyl group, benzoyl group, etc., for example, methoxycarbonyl group, ethoxycarbonyl group, etc., alkoxycarbonyl group, for example, phenoxy force
  • Examples include an aryloxycarbonyl group such as a rupinoxy group, for example, an alkyl group substituted with a substituent such as an aralkyloxycarbonyl group such as a benzyloxycarbonyl group, and a propyloxyl group.
  • Specific examples include a fluoromethyl group, a chloromethyl group, a trifluoromethyl group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and a methoxymethylcarbonyl group.
  • the optionally substituted aryl group examples include, for example, a phenyl group, a naphthyl group and the like, and an aromatic ring constituting such a phenyl group, a naphthyl group and the like, wherein the optionally substituted alkyl group, aryl group and aralkyl group (Alkyl groups substituted by aryl groups such as phenyl group and naphthyl group), alkoxy groups, aryloxy groups, arylalkyl groups, halogen atoms, aryl groups substituted with an acyl group, and the like.
  • Examples of the optionally substituted aralkyl group include those composed of the above-mentioned optionally substituted aralkyl group and the above-mentioned optionally substituted alkyl group.
  • Examples thereof include a benzinole group and a 4- Black benzene group, 4-methinobenzene group, 4-methoxybenzyl group, 3-phenoxybenzene group, 2,3,5,6-tetraphenylbenzene group, 2,3,5,6-tetraphenylolene 4 —Methinolevene 7 groups, 2,3,5,6-tetrafluoro-4-methoxybenzyl group, and 2,3,5,6-tetrafuronolo-4-methoxymethylbenzyl group.
  • R 1 and R 2 are connexion cyclopentane ring such together, to cyclo Represents a xane ring, a cycloheptane ring or a cyclododecane ring, or R 1 and R 3 or R 2 and R 3 together represent a pyrrolidine ring or a piperidine ring, or R 1 R 2 , R 3
  • Such secondary amines include, for example, N, N-dimethylamine, N, N-diethylamine, N, N-di (n-propyl) amine, N, N-di (n_butyl) amine, N, N- Di (n-aminole) amine, N, N-di (n-hexyl) amine, N, N-di (n-heptyl) amine, N, N-di (n-octynole) amine, N, N- Di (n-nonyl) amine, N, N-di
  • n-decyl N, N-di (n-dodecyl) amine, N, N-diisopropylamine, N, N-diisobutynoleamine, N, N-di (sec-butynole) amine, N , N-diisomyramine, N-ethyl-tert-butylamine, N, N-dibenzinoleamine, N-benzinole-tert-ptizoleamine, N-penzinolealine, 1,2,3,4-tetrahydroy Soquinoline, 6,7-methylenedioxy-1,2,3,4-tetrahydroisoquinoline, pyrrolidine, 2-methylpyrrolidine, 2-methoxycarbonylpyrrolidine, 3,4-dimethoxypyrrolidine, piperidine, 2-methylbiperidine, 2- Examples thereof include methoxycarbylbiperidine and 2,6-dimethylbiperidine.
  • a secondary amine for example, a salt of a secondary amine with an acid such as a secondary amine / hydrochloride or a secondary amine / sulfuric acid may be used.
  • R 4 , R 5 , R 6 and R 7 are the same or different and each represents a lower alkyl group, a lower alkenyl group, an aryl group, an aralkyl group or an asinole group; 2 COCH 2 _,-COCH 2 (CH 2 ) n -or-CHXCHY (CH
  • n - group represents a represented by; wherein, n represents 0 or 1, X, Y and Z are each the same or different, a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, Ashiruamino group, Represents a carbamoyl group, a lower alkoxy group, a lower alkenyloxy group, an aryloxy group, an aralkyloxy group or an acyloxy group.
  • Examples of the lower alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isoptyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, and cyclopentyl.
  • Linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms such as a group, n-hexyl group and cyclohexyl group.
  • Examples of the lower alkenyl group include a linear or branched alkenyl group having 1 to 6 carbon atoms such as a butyl group, an aryl group, an isopropyl group, a 4-pentenyl group, and a 5-hexenyl group. Is mentioned.
  • Examples of the aryl group include a phenyl group and a naphthyl group
  • examples of the aralkyl group include a benzyl group, a phenylethyl group, a diphenylmethynole group, and a phenylpropyl group.
  • examples of the acyl group include, for example, Examples thereof include an aliphatic or aromatic acyl group such as a nore group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a bivaloyl group, and a benzoyl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • acylamino group examples include an amino group substituted with an aliphatic or aromatic acetyl group such as an acetylamino group or a benzoylamino group.
  • lower alkoxy group those composed of the above-mentioned lower alkyl group and oxygen atom, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert group -A straight-chain, branched or cyclic C1-C6 alkoxy group such as -butoxy group, n_pentynoleoxy group, n-hexyloxy group and cyclohexyloxy group.
  • lower alkenyloxy group those composed of the above-mentioned lower alkenyl group and an oxygen atom, for example, a direct group such as a vinyloxy group, an aryloxy group, an isopropyloxy group, a 4-pentenyloxy group, a 5-hexyloxy group, etc.
  • a direct group such as a vinyloxy group, an aryloxy group, an isopropyloxy group, a 4-pentenyloxy group, a 5-hexyloxy group, etc.
  • Examples thereof include a chain or branched alkenyloxy group having 1 to 6 carbon atoms.
  • Examples of the aryloxy group include those composed of the above aryl group and an oxygen atom, such as a phenoxy group.
  • Examples of the aralkyl group include the above-mentioned aralkyl group and an oxygen atom, such as a benzyloxy group and a phenylenoxy group.
  • As the acyloxy group those composed of the above-mentioned asinole group and oxygen atom, for example, an acetoxy group, a propionyloxy group, a benzoyloxy group and the like can be mentioned.
  • Such secondary amines include, for example, 2,2,6,6-tetramethylpiperidine, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-propionyloxy-2,2,6,6 -Tetramethinolebiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4
  • Such a secondary amine may be used as it is, or an addition salt of a secondary amine with an acid such as a secondary amine 'hydrochloride, a secondary amine / sulfuric acid, and the like may be used.
  • the amount of metal oxide used in the reaction between secondary amine and hydrogen peroxide is usually at least 0.01 mol per mol of secondary amine, and there is no particular upper limit. In consideration of this, practically, it is 1 mol or less per 1 mol of the secondary amine.
  • Hydrogen peroxide is usually used as an aqueous solution.
  • an organic solvent solution of hydrogen peroxide may be used.
  • the concentration of hydrogen peroxide in the aqueous solution of hydrogen peroxide or organic solvent is not particularly limited, but is practically 1 to 60% by weight in consideration of volumetric efficiency and safety.
  • Hydrogen peroxide water is usually available commercially or as needed It is used after adjusting the concentration by dilution, concentration, etc., as appropriate.
  • the organic solvent solution of hydrogen peroxide can be prepared by, for example, extracting the aqueous hydrogen peroxide with an organic solvent, or distilling the aqueous hydrogen peroxide in the presence of the organic solvent. it can.
  • the amount of hydrogen peroxide used is usually 1.5 moles or more per mole of the amino group of the secondary amine, and there is no particular upper limit on the amount of hydrogen peroxide. Is 10 mol or less per 1 mol of the amino group of the secondary amine.
  • the amount of hydrogen peroxide used may be set, including the amount of hydrogen peroxide in the preparation solution.
  • This reaction is usually carried out in water, an organic solvent or a mixed solvent of an organic solvent and water.
  • organic solvent include ether solvents such as getyl ether, methyl tert-butyl ether, and tetrahydrofuran; ester solvents such as ethyl acetate; and alcohol solvents such as methanol, ethanol, and tert-butanol.
  • -tolyl solvents such as acetonitrile and propionitrile
  • aromatic hydrocarbon solvents such as toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbons such as cyclohexane and n-heptane Solvents and the like
  • the amount of water or organic solvent used is not particularly limited, but is practically not more than 100 times the weight of the secondary amine in consideration of volumetric efficiency and the like.
  • reaction temperature is too low, the reaction does not proceed easily, and if the reaction temperature is too high, side reactions such as decomposition of the raw material secondary amine and the decomposition of N-oxyl compound and N-oxyl compound may proceed. Therefore, the practical reaction temperature is in the range of 120 to 100 ° C.
  • This reaction may be carried out in the presence of ammonia.
  • ammonia any of ammonia water, ammonia gas, and an ammonia / organic solvent solution may be used.
  • the amount of use is not particularly limited, but it is practically not more than 10 moles per 1 mole of secondary amine, because too much amount is not likely to be economically disadvantageous.
  • This reaction is usually performed by mixing and contacting a secondary amine, hydrogen peroxide and a metal oxide catalyst, and the mixing order is not particularly limited.
  • a metal or metal compound, hydrogen peroxide and a secondary amine are mixed and brought into contact with each other to form a metal acid.
  • the operation for preparing the oxide catalyst and the reaction between the secondary amine and hydrogen peroxide may be performed simultaneously.
  • This reaction may be carried out under normal pressure conditions or may be carried out under pressurized conditions. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR, and IR.
  • the reaction solution is left as it is, or if necessary, the remaining hydrogen peroxide is decomposed with a reducing agent such as sodium thiosulfate, followed by concentration, crystallization, etc. Can be taken out.
  • a reducing agent such as sodium thiosulfate
  • water and / or an organic solvent insoluble in water are added to the reaction solution, and the mixture is subjected to an extraction treatment, and the resulting organic layer is concentrated to obtain a nitrone compound and an N-oxyl compound. You can also.
  • the removed nitrone compound may be further purified by, for example, distillation, column chromatography, or the like.
  • water-insoluble organic solvent examples include aromatic hydrocarbon solvents such as toluene, xylene, and benzene benzene, for example, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, and chloroform, and Examples thereof include ether solvents such as tyl ether, methyl tert-butyl ether, and tetrahydrofuran, and ester solvents such as ethyl acid, and the amount thereof is not particularly limited.
  • the aqueous layer obtained by extracting the filtrate and the reaction solution after removing the target etron compound and N-oxyl compound by crystallization treatment contains the metal oxide catalyst of this reaction, and After concentrating as necessary, it can be used again in the present reaction.
  • Examples of the thus obtained -throne compound include N-methylidenemethylamine N-oxide, N-ethylidenemethylamine N-oxide, N-propylidenemethylethylamine N-oxide, N-butylidenebutylamine N-oxide. -N-oxide, N-pentylidene-amylamine N-oxide, N-hexylidene-hexylamine N-oxide,
  • N-oxyl compound examples include 2,2,6,6-tetramethylbiperidine-N-oxyl and 4-acetoxy-2,2,6,6-tetramethinolepiperidine-N- 4-propionyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpyridine-N-oxyl, 4-methoxy -2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-ethoxy-2,2,6, 6-tetramethylpiperidine-N-oxyl, 4-benzyloxy 2,2,6,6-tetramethinolepiperidine-N-oxyl, 4-acetoamide, -2,2,6,6-tetramethylpiperidine-N- Oxil, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,5,5-tetra Chirupir
  • tungsten metal 16mg and 30 weight 0 /.
  • the prepared solution was cooled to an internal temperature of 20 ° C., and 3 g of methanol and 355 mg of N-benzyl-tert-butylamine were charged. After 1150 mg of a 30% by weight aqueous hydrogen peroxide solution was added dropwise over 5 minutes, the mixture was stirred and maintained at the same temperature for 5 hours to be reacted.
  • a 50 mL flask was charged with 74 mg of tungsten metal and 500 mg of 30% by weight hydrogen peroxide solution, heated to an internal temperature of 40 ° C, and stirred and maintained at the same temperature for 0.5 hour to prepare a tungsten oxide catalyst aqueous solution.
  • the prepared solution was cooled to an internal temperature of 0 ° C., and charged with 4 g of water, 600 mg of 28% by weight aqueous ammonia and 850 mg of piperidine. After 3.4 g of 30% by weight aqueous hydrogen peroxide was added dropwise over 30 minutes, the mixture was stirred and maintained at the same temperature for 3 hours to react.
  • Example 2 The procedure of Example 2 was repeated, except that 16 mg of molybdenum metal was used instead of 16 mg of tungsten metal, and 3 g of methanol was used instead of water as the solvent. 410 mg of white crystals of min N-oxide were obtained. Melting point: 81-83 ° C.
  • Example ⁇
  • N-benzylidenebenzylamine was obtained in the same manner as in Example 2, except that 20 mg of tungsten sulfide was used instead of 16 mg of tungsten metal and 3 g of methanol was used instead of water as a solvent. 425 mg of -oxide white crystals were obtained. Melting point: 81-83 ° C.
  • a 50 mL flask is charged with 15 mg of tungsten metal and 150 mg of 30% by weight hydrogen peroxide solution, heated to an internal temperature of 40 ° C, stirred and maintained at the same temperature for 0.5 hour to prepare a tungsten oxide catalyst aqueous solution. did.
  • the prepared solution was charged with 3 g of water and 480 mg of 4-hydroxy-2,2,6,6-tetramethylpiperazine. 30 weight 0/0 Hydrogen peroxide solution (100 mg) was added dropwise over 5 minutes, and the mixture was stirred at 50 ° C for 6 hours, maintained, and reacted to give 4-hydroxy-2,2,6,6-tetramethylpiperidine- A reaction solution containing N-oxyl was obtained. Analysis by GC internal standard method showed that the yield of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl was 99%.
  • Example 9 2,2,6,6-tetramethylpiperidine-N-oxyl is obtained in the same manner as in Example 9, except that tungsten boride is used instead of tungsten metal.
  • Example 9 2,2,6,6-tetramethylpiberidine-N-oxyl is obtained in the same manner as in Example 9, except that tungsten sulfide is used instead of tungsten metal. Individuals for industrial use
  • a metal oxide catalyst obtained by reacting a tungsten compound such as tungsten metal, molybdenum metal, and tungsten boride, which is easily available at a low cost, with a molybdenum compound such as molybdenum boride and hydrogen peroxide.
  • a tungsten compound such as tungsten metal, molybdenum metal, and tungsten boride
  • a molybdenum compound such as molybdenum boride and hydrogen peroxide.

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Abstract

L'invention concerne un procédé de fabrication d'un composé nitrone ou d'un composé N-oxyl, consistant à faire réagir une amine secondaire et du peroxyde d'hydrogène en présence d'un catalyseur d'oxyde métallique formé par réaction de peroxyde d'hydrogène avec au moins un composé du groupe suivant : tungstène métallique ; molybdène métallique ; composé tungstène contenant du tungstène et un élément du groupe IIIb, IVb, Vb ou VIb à l'exception de l'oxygène ; et, composé molybdène contenant du molybdène et un élément du groupe IIIb, IVb, Vb ou VIb à l'exception de l'oxygène.
PCT/JP2003/000243 2002-01-24 2003-01-15 Procede de fabrication d'un compose nitrone et d'un compose n-oxyl WO2003062193A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2136422A (en) * 1983-03-09 1984-09-19 Univ Osaka Synthesis of nitrones and nitrone addition products from secondary amines
EP0122804A1 (fr) * 1983-04-15 1984-10-24 Montedison S.p.A. Procédé de préparation d'acides carboxyliques à partir d'oléfines ou des composés dihydroxy vicinaux
JP2001019674A (ja) * 1999-07-06 2001-01-23 Hakuto Co Ltd ２，２，６，６−テトラメチルピペリジン−ｎ−オキシル類の製造方法。
EP1188735A1 (fr) * 2000-08-11 2002-03-20 Sumitomo Chemical Company, Limited Procédé de préparation de composés carbonylés ou hydroxylés

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2136422A (en) * 1983-03-09 1984-09-19 Univ Osaka Synthesis of nitrones and nitrone addition products from secondary amines
EP0122804A1 (fr) * 1983-04-15 1984-10-24 Montedison S.p.A. Procédé de préparation d'acides carboxyliques à partir d'oléfines ou des composés dihydroxy vicinaux
JP2001019674A (ja) * 1999-07-06 2001-01-23 Hakuto Co Ltd ２，２，６，６−テトラメチルピペリジン−ｎ−オキシル類の製造方法。
EP1188735A1 (fr) * 2000-08-11 2002-03-20 Sumitomo Chemical Company, Limited Procédé de préparation de composés carbonylés ou hydroxylés

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