JP2015059100A - Method for producing oxime - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an oxime compound (II) at a good selectivity by oxidizing an amine compound (I) with oxygen.SOLUTION: The method for producing an oxime compound (II) is characterized by bringing an amine compound (I) into contact with oxygen in the presence of at least one catalyst selected from the group comprising (A) a titanium-carrying catalyst, obtained by subjecting a carrier to a contact treatment with a titanium compound and then performing a heat treatment at 150°C or more, (B) a catalyst containing at least one selected from tungsten and molybdenum, and tin, (C) an inosilicate catalyst, and (D) an amorphous titanosilicate catalyst.

Description

  In the present invention, an oxime represented by the formula (II) described below [hereinafter sometimes referred to as oxime compound (II)]. ] About the method of manufacturing.

  Oxime is useful as a raw material for lactam, and as a raw material for synthetic fibers. As a method for producing the oxime compound (II), for example, Patent Document 1 discloses a method of oxidizing a primary amine with oxygen in the presence of a hydrazyl radical or a hydrazine compound and an oxidation accelerator such as titanium oxide. Has been proposed.

International Publication No. 2005/009613

  An object of the present invention is to provide a novel method capable of producing the oxime compound (II) with good selectivity.

  Under such circumstances, as a result of intensive studies, the present inventors have completed the present invention. That is, this invention consists of the following structures.

［式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、置換されていてもよい炭化水素基又は置換されていてもよい複素環基を表す（但し、Ｒ^１及びＲ^２が共に水素原子であることはない。）か、あるいは
Ｒ^１及びＲ^２は一緒になって、Ｒ^１及びＲ^２が結合する炭素原子と共に置換されていてもよい炭素数３〜１２の脂環式炭化水素基を形成する。］
で示されるアミン〔以下、アミン化合物（Ｉ）ということがある〕と、酸素とを接触させることを特徴とする下記式（ＩＩ）

（式中、Ｒ^１及びＲ^２は、それぞれ前記と同じ意味を表す。）
で示されるオキシムの製造方法。
（Ａ）担体をチタン化合物で接触処理した後に１５０℃以上で熱処理して得られるチタン担持触媒
（Ｂ）タングステン及びモリブデンからなる群より選ばれる少なくとも一種とスズとを含む触媒
（Ｃ）イノケイ酸塩触媒
（Ｄ）非晶質チタノシリケート触媒
（２）前記担体が、シリカアルミナである前記（１）に記載の製造方法。
（３）前記イノケイ酸塩触媒が、セピオライト触媒及びパリゴルスカイト触媒からなる群より選ばれる少なくとも一種の触媒である前記（１）又は（２）に記載の製造方法。
（４）前記イノケイ酸塩触媒が、第４族金属元素、第５族金属元素、第６族金属元素、ゲルマニウム、第４族金属元素の酸化物、第５族金属元素の酸化物、第６族金属元素の酸化物及び酸化ゲルマニウムからなる群より選ばれる少なくとも一種を含有する前記（１）〜（３）のいずれかに記載の製造方法。
（５）前記非晶質チタノシリケート触媒が、非晶質のメソポーラスチタノシリケート触媒である前記（１）〜（４）のいずれかに記載の製造方法。
（６）前記（１）〜（５）のいずれかに記載の製造方法により製造された前記式（ＩＩ）で示されるオキシムをベックマン転位反応させることを特徴とする下記式（ＩＩＩ）

［式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、置換されていてもよい炭化水素基又は置換されていてもよい複素環基を表す（但し、Ｒ^１及びＲ^２が共に水素原子であることはない。）か、あるいは
Ｒ^１及びＲ^２は一緒になって、Ｒ^１が結合する窒素原子と、Ｒ^２が結合する炭素原子と共に置換されていてもよい炭素数３〜１２の脂肪族複素環を形成する。］
で示されるアミド〔以下、アミド化合物（ＩＩＩ）ということがある。〕の製造方法。 (1) In the presence of at least one catalyst selected from the group consisting of the following (A), (B), (C) and (D), the following formula (I)

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group (provided that R ¹ and R ² are both Or R ¹ and R ² together may be substituted with the carbon atom to which R ¹ and R ² are bonded, and the C 3-12 alicyclic carbonization. Form a hydrogen group. ]
A compound represented by the following formula (II), wherein oxygen is contacted with an amine represented by formula (hereinafter sometimes referred to as amine compound (I)):

(In the formula, R ¹ and R ² each have the same meaning as described above.)
The manufacturing method of oxime shown by this.
(A) Titanium-supported catalyst obtained by subjecting a support to contact treatment with a titanium compound and then heat-treating at 150 ° C. or higher (B) A catalyst containing at least one selected from the group consisting of tungsten and molybdenum and tin (C) Inosilicate Catalyst (D) Amorphous titanosilicate catalyst (2) The production method according to (1), wherein the carrier is silica alumina.
(3) The production method according to (1) or (2), wherein the inosilicate catalyst is at least one catalyst selected from the group consisting of a sepiolite catalyst and a palygorskite catalyst.
(4) The inosilicate catalyst includes a Group 4 metal element, a Group 5 metal element, a Group 6 metal element, germanium, an oxide of a Group 4 metal element, an oxide of a Group 5 metal element, The manufacturing method in any one of said (1)-(3) containing the at least 1 type chosen from the group which consists of the oxide of a group metal element and germanium oxide.
(5) The production method according to any one of (1) to (4), wherein the amorphous titanosilicate catalyst is an amorphous mesoporous titanosilicate catalyst.
(6) A Beckmann rearrangement reaction of the oxime represented by the formula (II) produced by the production method according to any one of (1) to (5), wherein the following formula (III)

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group (provided that R ¹ and R ² are both R ¹ and R ² may be combined together to form a nitrogen atom to which R ¹ is bonded and a carbon atom having 3 to 3 carbon atoms which may be substituted together with the carbon atom to which R ² is bonded. 12 aliphatic heterocycles are formed. ]
An amide represented by the formula [hereinafter sometimes referred to as an amide compound (III). ] Manufacturing method.

  ADVANTAGE OF THE INVENTION According to this invention, the novel method which can manufacture oxime compound (II) with favorable selectivity can be provided.

Hereinafter, the present invention will be described in detail. In the present invention, in the presence of at least one catalyst selected from the group consisting of the following (A), (B), (C) and (D) [hereinafter sometimes referred to as an oxidation catalyst], an amine compound ( The oxime compound (II) is produced by bringing I) into contact with oxygen.
(A) Titanium-supported catalyst obtained by subjecting a support to contact treatment with a titanium compound and then heat-treating at 150 ° C. or higher (B) A catalyst containing at least one selected from the group consisting of tungsten and molybdenum and tin (C) Inosilicate Catalyst (D) Amorphous titanosilicate catalyst

In the above formulas (I), (II) and (III), R ¹ and R ² each independently represent a hydrogen atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group. When represented, R ¹ and R ² are not both hydrogen atoms. Here, “optionally substituted” means a hydrocarbon group or heterocyclic group in which part or all of the hydrogen atoms in the hydrocarbon group or heterocyclic group may be substituted with other substituents. I mean. In R ¹ and R ² , examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and an aryl group.

  As the alkyl group, an alkyl group having 1 to 24 carbon atoms is preferable. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, eicosyl, heicosyl , Heneicosyl group, docosyl group, tricosyl group, tetracosyl group and the like.

  The alkenyl group is preferably an alkenyl group having 2 to 24 carbon atoms, for example, vinyl group, allyl group, 2-methylallyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3 -Butenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-1-butenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 1-methyl-2-butenyl group, 2-methyl- 2-butenyl group, 3-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pen Nyl group, 2-methyl-1-pentenyl group, 4-methyl-3-pentenyl group, 2-ethyl-1-butenyl group, 2-heptenyl group, 2-octenyl group, 2-nonenyl group, 2-decenyl group, 2-undecenyl group, 2-dodecenyl group, 2-tridecenyl group, 2-tetradecenyl group, 2-pentadecenyl group, 2-hexadecenyl group, 2-heptadecenyl group, 2-octadecenyl group, 2-nonadecenyl group, 2-icosenyl group, A 2-eicosenyl group, a 2-henecocenyl group, a 2-henecocenyl group, a 2-docosenyl group, a 2-tricocenyl group, a 2-tetracocenyl group, and the like can be given.

  The alkynyl group is preferably an alkynyl group having 2 to 24 carbon atoms. For example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl 2-propynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-hexynyl group, 2 -Hexynyl group, 3-hexynyl group, 4-hexynyl group, 5-hexynyl group, 2-heptynyl group, 2-octynyl group, 2-noninyl group, 2-decynyl group, 2-undecynyl group, 2-dodecynyl group, 2 -Tridecynyl group, 2-tetradecynyl group, 2-pentadecynyl group, 2-hexadecynyl group, 2-heptadecynyl group, 2-octadecynyl group, 2-nonadecini Group, 2-Ikoshiniru group, 2-Eikoshiniru group, 2-Hen'ikoshiniru group, 2-Hen'eikoshiniru group, 2-Dokoshiniru group, 2-Torikoshiniru group, 2-Tetorakoshiniru group and the like.

  The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  As a cycloalkenyl group, a C3-C8 cycloalkenyl group is preferable, for example, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group etc. are mentioned.

  Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a tolyl group, and a xylyl group.

In R ¹ and R ² , the hydrocarbon group may be substituted. When the hydrocarbon group is an alkyl group, alkenyl group or alkynyl group, examples of the substituent include halogen atoms such as fluorine, chlorine and bromine; cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, A cycloalkyl group having 3 to 6 carbon atoms such as 1-methylcyclopentyl group and cyclohexyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, s-butoxy group, isobutoxy group, t-butoxy group and the like An alkoxy group having 1 to 4 carbon atoms; a thioalkoxy group having 1 to 4 carbon atoms such as a thiomethoxy group, a thioethoxy group, a thiopropoxy group, or a thiobutoxy group; an allyloxy group, a 2-propenyloxy group, a 2-butenyloxy group, Alkenyloxy having 3 to 4 carbon atoms such as 2-methyl-3-propenyloxy group An aralkyloxy group having 7 to 20 carbon atoms; an aryl group having 6 to 18 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group; an aryloxy group such as a phenyloxy group and a naphthyloxy group; An alkanoyl group having 2 to 7 carbon atoms; an aryloyl group having 7 to 19 carbon atoms; an alkoxycarbonyl group having 1 to 6 carbon atoms; When the hydrocarbon group is an alkyl group, examples of the alkyl group substituted with an aryl group having 6 to 18 carbon atoms include benzyl group, phenethyl group, 3-phenylpropyl group, benzhydryl group, trityl group, and triphenylethyl. And aralkyl groups such as a group, (1-naphthyl) methyl group, (2-naphthyl) methyl group and the like.

In R ¹ and R ² , when the hydrocarbon group is a cycloalkyl group, a cycloalkenyl group or an aryl group, examples of the substituent include the halogen atom described above, a cycloalkyl group having 3 to 6 carbon atoms, and a carbon number. Is an alkoxy group having 1 to 4 carbon atoms, a thioalkoxy group having 1 to 4 carbon atoms, an alkenyloxy group having 3 to 4 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, and an aryl group having 6 to 18 carbon atoms , Aryloxy group, alkanoyl group having 2 to 7 carbon atoms, allyloyl group having 7 to 19 carbon atoms, alkoxycarbonyl group having 1 to 6 carbon atoms, methyl group, ethyl group, propyl group, isopropyl group, butyl Group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group and other alkyl groups having 1 to 6 carbon atoms, vinyl group, 1-propenyl group, 2-propenyl 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4 Carbon number such as -pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, etc. Are alkenyl groups having 2 to 6 carbon atoms, aralkyl groups having 7 to 20 carbon atoms such as benzyl, phenethyl, and naphthylmethyl groups.

In R ¹ and R ² , examples of the heterocyclic group include a heteroaryl group and a heteroaralkyl group. The heteroaryl group is preferably a heteroaryl group having 3 to 9 carbon atoms, and examples thereof include a pyridyl group, a quinonyl group, a pyrrolyl group, an imidazolyl group, a furyl group, an indolyl group, a thienyl group, and an oxazolyl group. The heteroaralkyl group is preferably a heteroaralkyl group having 5 to 10 carbon atoms, and examples thereof include a pyridylmethyl group, a quinolylmethyl group, an indolylmethyl group, a furylmethyl group, and a pyrrolylmethyl group.

In R ¹ and R ² , the heterocyclic group may be substituted. Examples of the substituent in the heterocyclic group include the above-described halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a thioalkoxy group having 1 to 4 carbon atoms, and a carbon number. Are alkenyloxy groups having 3 to 4 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, aryl groups having 6 to 18 carbon atoms, aryloxy groups, alkanoyl groups having 2 to 7 carbon atoms, and 7 to 19 carbon atoms. Allyloyl groups, alkoxycarbonyl groups having 1 to 6 carbon atoms, alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and the like. It is done.

In the formula (I), when R ¹ and R ² each independently represents a hydrogen atom or an optionally substituted hydrocarbon group, examples of the amine compound (I) include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, Tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosylamine, eicosylamine, heicosylamine, heneicosylamine, docosylamine, tricosylamine, tetra Silamine, 1-methylbutylamine, 2-methylbutylamine, cyclopropylmethylamine, cyclohexylmethylamine, benzylamine, 2-methylbenzylamine, 4-methylbenzylamine, 1-phenylethylamine, 2-phenylethylamine, 3-aminomethyl Pyridine, 1- (4-chlorophenyl) ethylamine, 2- (2-chlorophenyl) ethylamine, 1- (3-methoxyphenyl) ethylamine, 1- (4-methoxyphenyl) ethylamine, 2- (2-methoxyphenyl) ethylamine, 2- (3-methoxyphenyl) ethylamine, 2- (4-methoxyphenyl) ethylamine, 1- [3- (trifluoromethyl) phenyl] ethylamine, 1- (1-naphthyl) ethylamine, 1- (2-naphthyl) Echi Luamine, 1-phenylpropylamine, 3-phenylpropylamine and the like.

In the above formulas (I) and (II), R ¹ and R ² are taken together, and the alicyclic hydrocarbon having 3 to 12 carbon atoms which may be substituted with the carbon atom to which R ¹ and R ² are bonded. When forming a group, the carbon number is preferably 6-12. Here, a C3-C12 alicyclic hydrocarbon group means a 3-12 membered alicyclic hydrocarbon group, and "it may be substituted" means this alicyclic hydrocarbon. This means an alicyclic hydrocarbon group in which part or all of the hydrogen atoms in the methylene group in the group may be substituted with other substituents. When it is substituted with another substituent, the carbon number of the substituent is not included in the above carbon number. Examples of the substituent in the alicyclic hydrocarbon group having 3 to 12 carbon atoms include the above-described halogen atom, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 carbon atom. -4 thioalkoxy group, alkenyloxy group having 3 to 4 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, aryl group having 6 to 18 carbon atoms, aryloxy group, 2 to 7 carbon atoms An alkanoyl group, an aryloyl group having 7 to 19 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a carbon number Examples thereof include 7 to 20 aralkyl groups.

In the formula (I), R ¹ and R ² together form an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may be substituted with the carbon atom to which R ¹ and R ² are bonded. In this case, examples of the amine compound (I) include cyclohexylamine, cyclooctylamine, cyclopentylamine, cycloheptylamine, cyclododecylamine, 2-methylcyclohexylamine, 4-methylcyclohexylamine and the like.

  Among the amine compounds (I), when cyclohexylamine is used as a raw material, the method of the present invention is advantageously employed in that cyclohexanone oxime is finally obtained in a high yield. The cyclohexylamine may be obtained, for example, by hydrogenating aniline, nitrobenzene, nitrocyclohexane, or the like, or obtained by amination reaction of cyclohexene or cyclohexanol with ammonia. May be.

  As an oxygen source of oxygen used for the contact, an oxygen-containing gas is preferably used. The oxygen-containing gas may be, for example, air, pure oxygen, or air or pure oxygen diluted with an inert gas such as nitrogen, argon, or helium. Good. Further, oxygen-enriched air obtained by adding pure oxygen to air can also be used. When an oxygen-containing gas is used, the oxygen concentration is preferably 1 to 30% by volume.

The titanium-supported catalyst can be obtained by heat-treating the support at 150 ° C. or higher after contact-treating the support with a titanium compound. Examples of the titanium compound used in the contact treatment include an inorganic compound of titanium and an organic compound of titanium. As an inorganic compound of titanium, for example, titanium trichloride (TiCl ₃ ), titanium tetrachloride (TiCl ₄ ), titanium tetrabromide (TiBr ₄ ), titanium tetrafluoride (TiF ₄ ), titanium tetraiodide (TiI ₄₎ Titanium halides such as titanium tetranitrate (Ti (NO ₃ ) ₄ ); Titanium sulfates such as titanium disulfate (Ti (SO ₄ ) ₂ ); Titanium phosphate (Ti ₃ (PO ₄ ) Titanium phosphates such as ₄ ); and the like. Examples of titanium organic compounds include titanium alkoxide compounds such as Ti (OR ′) ₄ (hereinafter, R ′ represents an alkyl group having 1 to 4 carbon atoms); TiCl (OR ′) ₃ , TiCl ₂ (OR _{') 2, TiCl 3 (OR} ') halide alkoxide compounds of titanium, and the like; tetraacetic acid titanium _{(Ti (CH 3 COO) 4} ) acetate titanium and the like; and the like. The titanium compound may use the hydrate as needed, and may use 2 or more types thereof. Among the titanium compounds, titanium halide, titanium sulfate, and titanium alkoxide compound are preferable, and titanium halide is more preferable.

  Examples of the carrier used for the contact treatment include oxides such as silica, alumina, silica-alumina, and magnesia; carbons such as activated carbon, graphite, and hard carbon; alkaline earth metal carbonates such as calcium carbonate, strontium carbonate, and barium carbonate. Salt; and the like. Of these, oxides are preferable, and silica-alumina is more preferable.

  In the contact treatment, the titanium compound is preferably used as a solution containing a titanium compound. Examples of the solvent used for preparing the solution containing the titanium compound include water, methanol, ethanol, propanol, tetrahydrofuran, toluene, hexane and the like. Only 1 type may be used for a solvent and it may use 2 or more types together. In the contact treatment, the temperature during the treatment is preferably 0 to 200 ° C. Such contact treatment can be performed in an air atmosphere or in an inert gas atmosphere such as nitrogen, helium, argon, or oxygen dioxide.

  Examples of the contact treatment include impregnation and immersion. Examples of the method for bringing the carrier into contact with the titanium compound include (a) a method in which the carrier is impregnated with a solution containing the titanium compound, and (b) a method in which the carrier is immersed in a solution containing the titanium compound. Such impregnation or immersion may be performed with stirring.

  After the contact treatment, before the heat treatment at 150 ° C. or higher, it is subjected to treatment such as washing and drying as necessary. When the mixture obtained after the contact treatment is in a slurry state, the solid may be recovered by drying the slurry, or separated by filtration, decantation, etc., washed as necessary, and dried. The solid may be recovered. Washing is preferably performed after the contact treatment in that a titanium-supported catalyst exhibiting high catalytic activity can be obtained. Such drying can be performed under normal pressure or reduced pressure. The drying temperature is preferably 20 to 200 ° C., and the drying time is preferably 0.5 to 100 hours. The drying may be performed in an atmosphere of an oxygen-containing gas such as air, or may be performed in an atmosphere of an inert gas such as nitrogen, helium, argon, or oxygen dioxide.

  In the titanium-supported catalyst, the heat treatment temperature is preferably 150 to 600 ° C, more preferably 250 to 500 ° C. The heat treatment time is preferably 0.1 to 100 hours. The heat treatment may be performed in an atmosphere of an oxygen-containing gas such as air, or may be performed in an atmosphere of an inert gas such as nitrogen, helium, argon, or oxygen dioxide. Water vapor may be contained in the oxygen-containing gas or the inert gas. Further, the heat treatment may be performed in multiple stages in an atmosphere of an oxygen-containing gas or an inert gas. The heat treatment may be performed in a fluidized bed type or a fixed bed type. The apparatus used for the heat treatment is not particularly limited as long as it can be heated. For example, a hot-air circulating firing furnace, a stationary firing furnace, a tunnel furnace, a rotary kiln, a far infrared furnace, a microwave heating furnace, or the like is used. can do.

  In the titanium-supported catalyst, the content of titanium with respect to the total amount of the catalyst is preferably 0.1 to 50% by weight, more preferably 0.5 to 50% by weight.

  The titanium-supported catalyst may be used after being molded using a binder as necessary. Such forming treatment may be performed at the time of preparing the carrier, may be performed after the contact treatment, or may be performed after the heat treatment. The molding process can be performed by a method such as extrusion, compression, tableting, flow, rolling, spraying, etc., and a desired shape, for example, granular, pellet, spherical, cylindrical, plate, ring, clover It can be formed into a shape or the like.

  In the catalyst containing tin and at least one selected from the group consisting of tungsten and molybdenum, each of tungsten, molybdenum and tin may be included in the form of a single metal or in the form of a compound. Also good. When included in the form of compounds, the compounds include oxoacids, oxoacid salts, oxides, hydroxides, nitrates, carbonates, hydroxides, halides, isopolyacids, isopolyacid salts, heteropolyacids, heteropolyacids. Examples include acid salts.

  Examples of the method for preparing a catalyst containing tin and at least one selected from the group consisting of tungsten and molybdenum include an adsorption method, an impregnation method, a coprecipitation method, and a sol-gel method. Preparation by the adsorption method or impregnation method, for example, after contacting a solution obtained by mixing at least one compound selected from the group consisting of a tungsten compound and a molybdenum compound and a solvent with a solid tin compound, If necessary, it can be performed by washing and drying. After the drying, firing may be performed as necessary. Preparation by the coprecipitation method or the sol-gel method is, for example, mixing at least one compound selected from the group consisting of a tungsten compound and a molybdenum compound, a tin compound, and a solvent, and adjusting pH and temperature as necessary. The solids in the resulting slurry can be recovered by performing operations such as addition of other components, and drying after washing as necessary. After the drying, firing may be performed as necessary.

  Examples of the tungsten compound used as a raw material compound in the preparation of a catalyst containing tin and at least one selected from the group consisting of tungsten and molybdenum include tungsten oxide, tungsten oxytetrachloride, tungstic acid, tungstate, and tungsten. Hexacarbonyl, tungsten pentaethoxide, tungsten hexaphenoxide, metatungstic acid, metatungstate, paratungstic acid, paratungstate, silicotungstic acid, silicotungstate, phosphotungstic acid, phosphotungstate, cobalt tungsten Acid, cobalt tungstate, manganese tungstic acid, manganese tungstate, lintongue molybdate, lintongue molybdate, catalyst Ribuden acid, Keita ring strike molybdates, manganese molybdate tungstate, manganese molybdate tungstate salt and the like, when the hydrates thereof there may also be used hydrates. Among these, tungstic acid and tungstate are preferable. Examples of tungstate include sodium tungstate, zinc tungstate, cobalt tungstate, cesium tungstate, manganese tungstate, and ammonium tungstate.

  Examples of the molybdenum compound used as a raw material compound for preparing a catalyst containing tin and at least one selected from the group consisting of tungsten and molybdenum include, for example, molybdenum oxide, molybdenum chloride, molybdenum 2-ethylhexanoate, hexacarbonylmolybdenum. , Bis (acetylacetonato) molybdenum oxide, molybdic acid, molybdate, molybdophosphoric acid, molybdophosphate, molybdosilicate, molybdosilicate, cobalt molybdate, cobalt molybdate, manganese molybdate, manganese molybdate, vana Examples thereof include domolybdophosphoric acid, vanadomolybdophosphate, manganese vanadium molybdate, manganese vanadium molybdate, manganese vanadomolybtriic acid, and manganese vanadomolybtriphosphate. If hydrate al there can be used the hydrates. Of these, molybdic acid and molybdate are preferable. Examples of molybdate include sodium molybdate, zinc molybdate, cobalt molybdate, cesium molybdate, manganese molybdate, and ammonium molybdate.

  Examples of the tin compound used as a raw material compound for the preparation of a catalyst containing at least one selected from the group consisting of tungsten and molybdenum and tin include stannous chloride, stannic chloride, stannous oxide, and oxidation. A hydrate can also be used when stannic etc. are mentioned and those hydrates exist.

  In the preparation by the coprecipitation method or the sol-gel method, the drying can be performed under normal pressure or reduced pressure, the drying temperature is preferably 0 to 200 ° C., and the drying time is 0.5 to 100 hours. Is preferred. The drying may be performed in an atmosphere of an oxygen-containing gas such as air, or may be performed in an atmosphere of an inert gas such as nitrogen, helium, argon, or carbon dioxide. Water vapor may be contained in the oxygen-containing gas or the inert gas. The drying may be performed in multiple stages under an atmosphere of an oxygen-containing gas or an inert gas. The drying may be performed in a fluidized bed type or a fixed bed type. The apparatus used for the drying is not particularly limited as long as it can be dried. For example, a hot-air circulating firing furnace, a stationary firing furnace, a tunnel furnace, a rotary kiln, a far infrared furnace, a microwave heating furnace, or the like is used. can do.

  The content of at least one selected from the group consisting of tungsten and molybdenum in the catalyst containing tin and at least one selected from the group consisting of tungsten and molybdenum is based on the total amount of the catalyst in terms of metal elements. 1 to 60% by weight is preferable, and 5 to 50% by weight is more preferable. When tungsten and molybdenum are contained in the catalyst, the total content may be in the above range. The tin content in the catalyst is preferably from 30 to 80% by weight, more preferably from 40 to 75% by weight, based on the total amount of the catalyst, in terms of metal elements. Moreover, as for content of tin in this catalyst, 1-15 mol is preferable with respect to at least 1 type of 1 mol chosen from the group which consists of tungsten and molybdenum in this catalyst. When tungsten and molybdenum are contained in the catalyst, the content of tin may be in the above range with respect to the total number of moles.

  The catalyst containing tin and at least one selected from the group consisting of tungsten and molybdenum may be used after being molded using a binder as necessary, or may be used by being supported on a carrier. Good. The molding process can be performed by a method such as extrusion, compression, tableting, flow, rolling, spraying, etc., and a desired shape, for example, granular, pellet, spherical, cylindrical, plate, ring, clover It can be formed into a shape or the like.

The inosilicate catalyst has a chain crystal structure in which SiO ₄ tetrahedrons share two oxygens and are connected indefinitely. Examples of the inosilicate catalyst include magnesium inosilicate catalyst such as sepiolite catalyst and palygorskite catalyst; calcium inosilicate catalyst such as wollastonite catalyst and the like. It can also be used. Among them, a magnesium inosilicate catalyst is preferable, and among the magnesium inosilicate catalysts, at least one catalyst selected from the group consisting of a sepiolite catalyst and a palygorskite catalyst in terms of the selectivity of the oxime compound (II) obtained. preferable. The inosilicate catalyst may be a natural product, a synthetic product synthesized artificially, or a mixture thereof. The magnesium inosilicate catalyst has a ribbon structure (chain structure) by periodically reversing the apex oxygen of the SiO tetrahedral sheet, and the direction of the apex oxygen of the tetrahedron sheet is the period of the ribbon width. In order to reverse, characteristic voids are formed in the structure. Moreover, the form has a fibrous form.

  The inosilicate catalyst may be used for contacting the amine compound (I) with oxygen after calcination. The firing temperature is preferably 150 to 600 ° C., and the firing time is preferably 0.1 to 100 hours. The firing may be performed in an atmosphere of an oxygen-containing gas such as air, or may be performed in an atmosphere of an inert gas such as nitrogen, helium, argon, or oxygen dioxide. Water vapor may be contained in the oxygen-containing gas or the inert gas. Further, the calcination may be performed in multiple stages in an atmosphere of an oxygen-containing gas or an inert gas. The firing may be performed by a fluidized bed method or a fixed bed method. The apparatus used for the firing is not particularly limited as long as it can be heated. For example, a hot-air circulating firing furnace, a stationary firing furnace, a tunnel furnace, a rotary kiln, a far infrared furnace, a microwave heating furnace, or the like is used. can do.

  The inosilicate catalyst may be used after being molded using a binder as necessary. When performing the ion exchange process mentioned later, this shaping | molding process may be performed before this ion exchange process, and may be performed after an ion exchange process. The molding process can be performed by a method such as extrusion, compression, tableting, flow, rolling, spraying, etc., and a desired shape, for example, granular, pellet, spherical, cylindrical, plate, ring, clover It can be formed into a shape or the like.

  The inosilicate catalyst includes a Group 4 metal element, a Group 5 metal element, a Group 6 metal element, germanium, an oxide of a Group 4 metal element, an oxide of a Group 5 metal element, and a Group 6 metal element. It is preferable to contain at least one selected from the group consisting of oxides of germanium and germanium oxide, and it is more preferable to contain at least one selected from the group consisting of Group 4 metal and Group 4 metal element oxides. Examples of the Group 4 metal element include titanium and zirconium. Examples of the Group 5 metal element include vanadium, niobium, and tantalum. Examples of the Group 6 metal element include chromium, molybdenum, tungsten, and the like. In particular, the method of the present invention is advantageously employed when using an inosilicate catalyst containing at least one selected from the group consisting of titanium and titanium oxide in view of the selectivity of the resulting oxime compound (II). The

  The inosilicate catalyst includes a Group 4 metal element, a Group 5 metal element, a Group 6 metal element, germanium, an oxide of a Group 4 metal element, an oxide of a Group 5 metal element, and a Group 6 metal element. And a group 4 metal element, a group 5 metal element, a group 6 metal element, germanium, an oxide of a group 4 metal element, At least one selected from the group consisting of group metal element oxides, group 6 metal element oxides and germanium oxide may be incorporated in the inosilicate skeleton, and in the vacancies in the inosilicate It may be carried or may be carried on the outer surface of inosilicate.

  From Group 4 metal element, Group 5 metal element, Group 6 metal element, germanium, Group 4 metal element oxide, Group 5 metal element oxide, Group 6 metal element oxide and germanium oxide As the inosilicate catalyst containing at least one selected from the group consisting of, for example, an inosilicate having an exchangeable cation, a Group 4 metal element compound, a Group 5 metal element compound, Group 6 What is obtained by ion-exchange-processing with the at least 1 type of compound chosen from the group which consists of a compound of a metal element and a germanium compound can be used conveniently. This ion exchange treatment is a solution containing inosilicate and at least one compound selected from the group consisting of compounds of Group 4 metal elements, compounds of Group 5 metal elements, compounds of Group 6 metal elements, and germanium compounds. It is preferable to carry out by making it contact. In addition to a Group 4 metal element compound, a Group 5 metal element compound, a Group 6 metal element compound, and a germanium compound, the solution may contain compounds of other elements. Further, before and / or contacting with a solution containing at least one compound selected from the group consisting of a group 4 metal element compound, a group 5 metal element compound, a group 6 metal element compound and a germanium compound. Thereafter, contact with a solution containing a compound of another element may be performed.

  From Group 4 metal element, Group 5 metal element, Group 6 metal element, germanium, Group 4 metal element oxide, Group 5 metal element oxide, Group 6 metal element oxide and germanium oxide In the inosilicate catalyst containing at least one selected from the group consisting of, the total content of Group 4 metal element, Group 5 metal element, Group 6 metal element and germanium is preferably 0.01 to 50% by weight More preferably, it is 0.1-25 weight%, More preferably, it is 0.2-10 weight%. When such an inosilicate catalyst includes at least one selected from the group consisting of an oxide of a Group 4 metal element, an oxide of a Group 5 metal element, an oxide of a Group 6 metal element, and germanium oxide, Group 4 metal element oxides are Group 4 metal elements, Group 5 metal element oxides are Group 5 metal elements, Group 6 metal element oxides are Group 6 metal elements, and Germanium oxide is In terms of germanium, the total content of the Group 4 metal element, Group 5 metal element, Group 6 metal element and germanium in the inosilicate catalyst may be in the above range. The respective contents of the Group 4 metal element, Group 5 metal element, Group 6 metal element, and germanium can be determined by, for example, inductively coupled plasma (ICP) emission analysis.

Examples of the group 4 metal element compound used in the ion exchange treatment include inorganic compounds of group 4 metal elements and organic compounds of group 4 metal elements. Examples of inorganic compounds of Group 4 metal elements include titanium trichloride (TiCl ₃ ), titanium tetrachloride (TiCl ₄ ), titanium tetrabromide (TiBr ₄ ), titanium tetrafluoride (TiF ₄ ), and tetraiodide. Titanium (TiI ₄ ), zirconium trichloride (ZrCl ₃ ), zirconium tetrachloride (ZrCl ₄ ), zirconium tribromide (ZrBr ₃ ), zirconium tetrabromide (ZrBr ₄ ), zirconium tetrafluoride (ZrF ₄ ), four Group 4 metal element halides such as zirconium iodide (ZrI ₄ ); Group 4 metal element nitrates such as titanium tetranitrate (Ti (NO ₃ ) ₄ ) and zirconium tetranitrate (Zr (NO ₃ ) ₄ ) ; zirconyl nitrate (ZrO _{(NO 3) 2)} a group 4 metal elements oxy nitrates such as; disulfate titanium _{(Ti (SO 4) 2)} , disulfate zirconium (Zr _{(SO 4) 2)} sulfate group 4 metal elements such as; titanium phosphate _{(Ti 3 (PO 4) 4} ), zirconium phosphate _{(Zr 3 (PO 4) 4} ) Group 4 metal, such as Elemental phosphates; and the like. Examples of organic compounds of Group 4 metal elements include Group 4 metals such as Ti (OR ³ ) ₄ (hereinafter, R ³ represents an alkyl group having 1 to 4 carbon atoms), Zr (OR ³ ) _{4, and the} like. Elemental alkoxide compounds; TiCl (OR ³ ) ₃ , TiCl ₂ (OR ³ ) ₂ , TiCl ₃ (OR ³ ), ZrCl (OR ³ ) ₃ , ZrCl ₂ (OR ³ ) ₂ , ZrCl ₃ (OR ³ ), etc. Halogenated alkoxide compounds of Group 4 metal elements; acetates of Group 4 metal elements such as titanium tetraacetate (Ti (CH ₃ COO) ₄ ) and zirconium tetraacetate (Zr (CH ₃ COO) ₄ ); It is done. Moreover, the hydrate of the compound of a group 4 metal element may be used as needed, and 2 or more types thereof may be used. As the Group 4 metal element compound, among them, a Group 4 metal element halide, a Group 4 metal element sulfate, a Group 4 metal element alkoxide compound, a Group 4 metal element oxynitrate is preferable, More preferred are halides of Group 4 metal elements.

Examples of the Group 5 metal element compound used for the ion exchange treatment include inorganic compounds of Group 5 metal elements and organic compounds of Group 5 metal elements. Examples of inorganic compounds of Group 5 metal elements include vanadium trichloride (VCl ₃ ), vanadium tetrachloride (VCl ₄ ), vanadium tribromide (VBr ₃ ), vanadium trifluoride (VF ₃ ), and tetrafluoride. Vanadium (VF ₄ ), vanadium triiodide (VI ₃ ), niobium trichloride (NbCl ₃ ), niobium pentachloride (NbCl ₅ ), niobium tribromide (NbBr ₃ ), niobium pentabromide (NbBr ₅ ), five Niobium fluoride (NbF ₅ ), niobium pentaiodide (NbI ₅ ), tantalum trichloride (TaCl ₃ ), tantalum pentachloride (TaCl ₅ ), tantalum pentabromide (TaBr ₅ ), tantalum pentafluoride (TaF ₅ ) And halides of Group 5 metal elements such as tantalum pentaiodide (TaI ₅ ). Examples of organic compounds of Group 5 metal elements include alkoxide compounds of Group 5 metal elements such as Nb (OR ³ ) ₅ and Ta (OR ³ ) ₅ . Moreover, the hydrate of the compound of a Group 5 metal element may be used as needed, and 2 or more types thereof may be used.

Examples of the Group 6 metal element compound used for the ion exchange treatment include inorganic compounds of Group 6 metal elements and organic compounds of Group 6 metal elements. Examples of inorganic compounds of Group 6 metal elements include chromium dichloride (CrCl ₂ ), chromium trichloride (CrCl ₃ ), chromium dibromide (CrBr ₂ ), chromium tribromide (CrBr ₃ ), and difluoride. Chromium (CrF ₂ ), chromium trifluoride (CrF ₃ ), chromium diiodide (CrI ₂ ), chromium triiodide (CrI ₃ ), molybdenum trichloride (MoCl ₃ ), molybdenum pentachloride (MoCl ₅ ), three Molybdenum bromide (MoBr ₃ ), molybdenum tetrafluoride (MoF ₄ ), molybdenum hexafluoride (MoF ₆ ), tungsten tetrachloride (WCl ₄ ), tungsten hexachloride (WCl ₆ ), tungsten pentabromide (WBr ₅ ) , halides of the group 6 metal element such as tungsten hexafluoride (WF _6); trinitrate chromium (Cr _{(NO 3) 3)} of the group 6 metal elements such as Salt; Chromium sulfate _{(III) (Cr 2 (SO} 4) 3), sulfates of Group 6 metal element and the like; and the like. Examples of organic compounds of Group 6 metal elements include alkoxide compounds of Group 6 metal elements such as Mo (OR ³ ) ₅ , W (OR ³ ) ₅ , and W (OR ³ ) ₆ ; chromium triacetate (Cr ( CH ₃ COO) ₃ ) group 6 metal element acetates; and the like. Moreover, the hydrate of the compound of a group 6 metal element may be used as needed, and 2 or more types thereof may be used.

Examples of germanium compounds used in the ion exchange treatment include germanium inorganic compounds and germanium organic compounds. Examples of germanium inorganic compounds include germanium halides such as germanium tetrachloride (GeCl ₄ ), germanium tetrabromide (GeBr ₄ ), germanium tetrafluoride (GeF ₄ ), and germanium tetraiodide (GeI ₄ ); And germanium sulfides such as germanium sulfide (GeS). Examples of germanium organic compounds include germanium alkoxide compounds such as Ge (OR ³ ) ₄ ; germanium halogenated alkoxides such as GeCl (OR ³ ) ₃ , GeCl ₂ (OR ³ ) ₂ , and GeCl ₃ (OR ³ ). Compound; and the like. Moreover, the hydrate of a germanium compound may be used as needed, and those 2 or more types may be used. Of these, germanium halides and germanium alkoxide compounds are preferred as the germanium compound.

  In the ion exchange treatment described above, the amount of at least one compound selected from the group consisting of Group 4 metal element compounds, Group 5 metal element compounds, Group 6 metal element compounds, and germanium compounds is 4 An exchangeable cation in terms of a metal element contained in at least one compound selected from the group consisting of a group metal element compound, a group 5 metal element compound, a group 6 metal element compound and a germanium compound 0.01-100 weight part is preferable with respect to 100 weight part of inosilicate which has, and 0.05-50 weight part is more preferable. When using two or more kinds of compounds selected from the group consisting of compounds of Group 4 metal elements, compounds of Group 5 metal elements, compounds of Group 6 metal elements, and germanium compounds, the total amount used is within the above range. It only has to be.

  For the above-described ion exchange treatment, an inosilicate having an exchangeable cation is selected from the group consisting of a Group 4 metal element compound, a Group 5 metal element compound, a Group 6 metal element compound, and a germanium compound. As a solvent used in the preparation of the solution, for example, a polar solvent such as water, methanol, ethanol, acetone, 1,2-dimethoxyethane, and the like is used. Two or more of them can be used as necessary. The solution may be acidic, basic, or neutral, but is preferably acidic or basic from the viewpoint of dispersibility of the inosilicate in the solution. Examples of the acid used for the preparation of the acidic solution include inorganic acids and organic acids. Examples of the inorganic acid include hydrogen chloride, sulfuric acid, phosphoric acid, nitric acid, nitrous acid, and the like. Examples of the organic acid include acetic acid and trifluoromethanesulfonic acid. Examples of the base used for preparing the basic solution include inorganic bases and organic bases. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like. Examples of the organic base include methylamine, dimethylamine, trimethylamine, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, pyridine, hexamethyleneimine, piperidine and the like.

  In the case of using the acidic solution or the basic solution, at least one compound selected from the group consisting of a group 4 metal element compound, a group 5 metal element compound, a group 6 metal element compound, and a germanium compound As a compound that is hydrolyzed under acidic or basic conditions such as hydrolyzable halide, alkoxide compound, oxynitrate, etc., the compound is hydrolyzed to become an oxide. An inosilicate catalyst containing at least one selected from the group consisting of an oxide of an element, an oxide of a Group 5 metal element, an oxide of a Group 6 metal element, and germanium oxide can be prepared. The acidic solution or the basic solution contains compounds of other elements in addition to compounds of Group 4 metal elements, compounds of Group 5 metal elements, compounds of Group 6 metal elements, and germanium compounds. May be. Moreover, you may perform the contact with the acidic solution or basic solution containing the compound of another element before and / or after making it contact with the said acidic solution or the said basic solution. When a compound that is hydrolyzed under acidic or basic conditions, such as a hydrolyzable halide, alkoxide compound, or oxynitrate, is used as the compound of the other element, the compound is hydrolyzed to become an oxide. Inosilicate catalysts containing oxides of other elements can be prepared. Examples of compounds containing other elements include silicon alkoxide compounds. Examples of silicon alkoxide compounds include tetraalkyl orthosilicates such as tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, and tetrabutyl orthosilicate. Can be mentioned.

  The above-described ion exchange treatment may be performed batchwise or continuously. As a batch method, for example, inosilicate is selected from the group consisting of a Group 4 metal element compound, a Group 5 metal element compound, a Group 6 metal element compound, and a germanium compound in a stirring tank. And a method of soaking and mixing in a solution containing at least one kind of compound. As a continuous method, for example, in a tubular container filled with inosilicate, a group 4 metal element compound, a group 5 metal element compound, a group 6 metal element compound, and a germanium compound are used. A method of circulating a solution containing at least one selected compound, a group 4 metal element compound, a group 5 metal element compound, a group 6 metal element compound, and germanium in a stirring tank containing inosilicate Examples thereof include a method of extracting the liquid phase of the mixture while supplying a solution containing at least one compound selected from the group consisting of compounds.

  As for the temperature in the above-mentioned ion exchange process, 0-150 degreeC is preferable, More preferably, it is 10-100 degreeC, More preferably, it is 30-70 degreeC. The time for the ion exchange treatment is usually 0.1 to 240 hours, preferably 0.5 to 120 hours. The pressure during the ion exchange treatment is preferably 0.1 to 1 MPa in absolute pressure, more preferably atmospheric pressure. Moreover, the usage-amount of the said solution in the above-mentioned ion exchange process is suitably set with respect to inosilicate. In addition, you may perform the above-mentioned ion exchange process in multiple times as needed. Moreover, you may perform combining the process by an acidic solution, the process by a basic solution, and the process by a neutral solution.

  The inosilicate catalyst obtained after performing the above-described ion exchange treatment is subjected to treatment such as washing and drying as necessary. When the inosilicate catalyst obtained after the treatment is in a slurry state, the inosilicate catalyst may be recovered by drying the slurry, or separated by filtration or decantation, and then washed as necessary. The inosilicate catalyst may be recovered by drying. The inosilicate catalyst obtained after the treatment is preferably washed in that an inosilicate catalyst exhibiting high catalytic activity is obtained. The drying can be performed under normal pressure or reduced pressure, the drying temperature is preferably 20 to 250 ° C., and the drying time is preferably 0.5 to 100 hours. The drying may be performed in an atmosphere of an oxygen-containing gas such as air, or may be performed in an atmosphere of an inert gas such as nitrogen, helium, argon, or oxygen dioxide.

  The amorphous titanosilicate catalyst may be an amorphous mesoporous titanosilicate catalyst or an amorphous titanosilicate catalyst having no regular pores. A crystalline mesoporous titanosilicate catalyst is preferred. The mesoporous titanosilicate here means a mesoporous titanosilicate having a pore diameter of about 2 to 50 nm. Specific examples of the amorphous mesoporous titanosilicate catalyst include an amorphous titanosilicate catalyst having an MCM-41 type structure (hereinafter sometimes referred to as Ti-MCM-41), and an HMS type structure. An amorphous titanosilicate catalyst (hereinafter sometimes referred to as Ti-HMS) having The presence or absence of a mesoporous structure can be confirmed by the presence or absence of a peak at 2θ = 0.2 to 4.0 ° in XRD (X-ray diffraction) measurement using copper Kα rays.

  The above amorphous titanosilicate catalyst contains titanium, silicon and oxygen, and may be substantially composed only of titanium, silicon and oxygen, and further boron, aluminum, gallium, It may contain elements other than iron, chromium, titanium, silicon and oxygen.

  The content of titanium in the above amorphous titanosilicate catalyst is usually 0.0001 or more, preferably 0.005 or more, expressed as an atomic ratio (Ti / Si) to silicon, and usually 1.0. Hereinafter, it is preferably 0.5 or less. When the amorphous titanosilicate catalyst contains an element other than titanium, silicon and oxygen, the content of the element is usually 1.0 or less, preferably 0.5 or less, expressed as an atomic ratio with respect to silicon. It is. Oxygen can be present corresponding to the content and oxidation number of each element other than oxygen. A typical composition of an amorphous titanosilicate catalyst can be represented by the following formula with silicon as the reference (= 1).

SiO ₂ · xTiO ₂ · yM ⁿ O _{n / 2}
(In the formula, M represents at least one element other than silicon, titanium and oxygen, n is the oxidation number of the element, x is 0.0001 to 1.0, and y is 0 to 1.0. .)

  In the above formula, M is an element other than titanium, silicon, and oxygen, and examples thereof include boron, aluminum, gallium, iron, and chromium.

  The amorphous mesoporous titanosilicate catalyst is prepared, for example, by mixing a titanium compound, a silicon compound and a structure directing agent (template) in an aqueous solvent in the presence of an acidic compound or a basic compound, By aging under the pressure condition or under the conditions of changing the temperature and / or pressure within the temperature and pressure range described later, a titanosilicate incorporating a structure-directing agent is obtained, and the structure is obtained from this titanosilicate. Prepared by removing the defining agent.

  The structure of the amorphous mesoporous titanosilicate catalyst can be adjusted by the type and amount of the structure-directing agent used. For example, when preparing Ti-MCM-41, cetyltrimethyl bromide When a quaternary ammonium salt such as ammonium is used and Ti-HMS is prepared, a primary amine such as n-dodecylamine is used. On the other hand, examples of the titanium compound include tetraalkyl orthotitanates such as tetra-n-butyl orthotitanate, peroxytitanates such as tetra-n-butylammonium peroxytitanate, and titanium halides. Examples of the compound include tetraalkyl orthosilicates such as tetraethyl orthosilicate, silica and the like. Examples of the acidic compound include inorganic acids such as hydrochloric acid, and organic acids such as acetic acid. Examples of the basic compound include inorganic bases such as alkali hydroxide and ammonia, and organic bases such as pyridine. . Furthermore, examples of the aqueous solvent include water-soluble organic solvents such as methanol, ethanol, propanol and 2-propanol, water or a mixed solvent of water and the water-soluble organic solvent.

  The aging temperature in the aging is usually 0 to 200 ° C, preferably 20 to 100 ° C. The pressure is usually 0.1 to 1.0 MPa in absolute pressure, preferably 0.1 to 0.8 MPa. The aging time is usually 0.5 to 170 hours, preferably 4 to 72 hours.

  By the aging, a titanosilicate incorporating a structure-directing agent is obtained, and then the structure-directing agent is removed from the titanosilicate. Examples of the removing method include a method of washing with an organic solvent such as methanol, acetone and toluene, a method of washing with hydrochloric acid (aqueous hydrogen chloride solution), an aqueous solution of sulfuric acid, an aqueous nitric acid solution, and a method of baking at 200 to 800 ° C. It is done. Any one of the removal methods may be employed, or two or more may be employed in combination.

  Firing as the removal method may be performed in an atmosphere of an oxygen-containing gas such as air, or may be performed in an atmosphere of an inert gas such as nitrogen, helium, argon, or oxygen dioxide. Water vapor may be contained in the oxygen-containing gas or the inert gas. Further, the calcination may be performed in multiple stages in an atmosphere of an oxygen-containing gas or an inert gas. The firing may be performed in a fluidized bed type or a fixed bed type. The apparatus used for the firing is not particularly limited as long as it can be heated. For example, a hot-air circulating firing furnace, a stationary firing furnace, a tunnel furnace, a rotary kiln, a far infrared furnace, a microwave heating furnace, or the like is used. can do.

  The amorphous mesoporous titanosilicate catalyst can be prepared, for example, according to the method described in JP-A-2000-117101, and Ti-MCM-41 can be prepared, for example, by microporous and It can be prepared according to the method described in Mesoporous Materials, 2007, P312-321, and Ti-HMS is prepared according to the method described in Nature, 1994, P321-323, for example. be able to.

  The amorphous titanosilicate catalyst having no regular pores, for example, after mixing a titanium compound and a silicon compound in an aqueous solvent in the presence of an acidic compound or a basic compound, It is prepared by aging under conditions of pressure or under the conditions of changing the temperature and / or pressure within the range of temperature and pressure described below, washing as necessary, and drying. After the drying, firing may be performed as necessary. Examples of titanium compounds include tetraalkyl orthotitanates such as tetra-n-butyl orthotitanate, peroxytitanates such as tetra-n-butylammonium peroxytitanate, titanium halides, and the like. And tetraalkyl orthosilicates such as tetraethyl orthosilicate, silica and the like. Examples of the acidic compound include inorganic acids such as hydrochloric acid, and organic acids such as acetic acid. Examples of the basic compound include inorganic bases such as alkali hydroxide and ammonia, and organic bases such as pyridine. . Furthermore, examples of the aqueous solvent include water-soluble organic solvents such as methanol, ethanol, propanol and 2-propanol, water or a mixed solvent of water and the water-soluble organic solvent. The aging temperature in such aging is usually 0 to 200 ° C. The pressure is usually 0.1 to 1.0 MPa in absolute pressure. The aging time is usually 0.5 to 170 hours.

  The amorphous titanosilicate catalyst may be contact-treated with a silicon compound. Examples of such silicon compounds include organic silicon compounds and inorganic silicon compounds, and among them, organic silicon compounds are preferable. The contact treatment with the silicon compound can be performed, for example, according to the method described in JP2012-20966A.

  The amorphous titanosilicate catalyst may be used after being molded using a binder as necessary. In the case where the above-described contact treatment with the silicon compound is performed, the forming treatment may be performed before the contact treatment with the silicon compound or after the contact treatment with the silicon compound. The molding process can be performed by a method such as extrusion, compression, tableting, flow, rolling, spraying, etc., and a desired shape, for example, granular, pellet, spherical, cylindrical, plate, ring, clover It can be formed into a shape or the like.

  The contact between the amine compound (I) and oxygen in the presence of an oxidation catalyst is preferably performed using a solvent. Examples of the solvent include an organic solvent, water, and a mixed solvent of an organic solvent and water. Among them, an organic solvent or a mixed solvent of an organic solvent and water is preferable, and an organic solvent is more preferable. Examples of organic solvents include methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, n-hexanol, 2-ethylhexanol, n-dodecanol and other alcohols; pentane, hexane, heptane, octane, petroleum ether, Aliphatic hydrocarbons such as ligroin; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, o-xylene, m-xylene, and p-xylene; dichloromethane, chloroform, 1 Halogenated hydrocarbons such as 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethylene, 1,1,2,2-tetrachloroethylene, chlorobenzene, o-dichlorobenzene; acetonitrile, benzonitrile, etc. Nitrile; nitro compounds such as nitrobenzene; ethyl acetate, isopropyl acetate, butyl acetate, ester compounds such as ethyl benzoate and the like, can also be used two or more of them as required. Of these, alcohol, aromatic hydrocarbon, and nitrile are preferable. Among alcohols, methanol, ethanol, and t-butanol are preferable. Among aromatic hydrocarbons, toluene, o-xylene, m-xylene, and p-xylene are preferable. Among nitrites, acetonitrile is preferable.

  When using a solvent, the quantity is 0.1-300 weight part normally with respect to 1 weight part of amine compound (I), Preferably it is 0.5-100 weight part.

  The contact between the amine compound (I) and oxygen may be carried out in a batch system, a semi-batch system, a continuous system, or a combination of a batch system, a semi-batch system and a continuous system. May be. For continuous operation, fixed bed method, fluidized bed method, moving bed method, suspension bed method, and the method of extracting the liquid phase of the reaction mixture while supplying the reaction raw material into the stirring / mixing type or loop type reactor. It can implement by various methods, such as.

  The contact temperature in the contact between the amine compound (I) and oxygen is preferably 50 to 200 ° C, more preferably 70 to 150 ° C. Moreover, a pressure is 0.1-10 MPa normally in absolute pressure, Preferably it is 0.2-7.0 MPa. Such contact is preferably performed under pressure. In this case, the pressure may be adjusted using an inert gas such as nitrogen or helium. When such contact is carried out in a stirred-mix reactor in a batch or continuous manner using an oxygen-containing gas under liquid phase conditions, the oxygen-containing gas is supplied to the gas phase portion of the reactor. Alternatively, the oxygen-containing gas may be supplied into the liquid phase, or the oxygen-containing gas may be supplied into the gas phase portion and the liquid phase of the reactor.

  In the contact between the amine compound (I) and oxygen, a radical initiator, a phenol chain transfer agent and the like may coexist if necessary. Examples of the radical initiator include hydrazyl radicals and hydrazine compounds disclosed in International Publication No. 2005/009613; azo compounds and peroxides disclosed in JP 2005-15381 A; If necessary, two or more kinds of radical initiators may be used. Examples of the hydrazyl radical include 2,2-diphenyl-1-picrylhydrazyl, 2,2-di (4-tert-octylphenyl) -1-picrylhydrazyl and the like. Examples of the hydrazine compound include 1,1-diphenyl-2-picrylhydrazine. As said phenol type chain transfer agent, the compound etc. which are disclosed by Unexamined-Japanese-Patent No. 2005-15382 are mentioned, for example.

  By contacting amine compound (I) with oxygen in the presence of an oxidation catalyst, amine compound (I) is oxidized with oxygen, and a reaction mixture containing oxime compound (II) is obtained. The post-treatment operation of the reaction mixture can be appropriately selected, and after purifying the oxime compound (II) by combining treatments such as filtration, washing, distillation, crystallization, extraction, recrystallization, chromatography and the like, if necessary. Can be used for various purposes. The catalyst recovered after the oxidation can be reused after being subjected to treatments such as washing, calcination and ion exchange treatment as necessary. Moreover, when a solvent and an unreacted raw material are contained in the reaction mixture, the recovered solvent and unreacted raw material can be reused.

  The obtained oxime compound (II) is suitably used as a raw material for producing the amide compound (III) by, for example, Beckmann rearrangement reaction.

In the amide compound (III), R ¹ and R ² are combined together, and the aliphatic complex having 3 to 12 carbon atoms which may be substituted together with the nitrogen atom to which R ¹ is bonded and the carbon atom to which R ² is bonded. the case of forming the ring, oxime compound (II) is, R ¹ and R ² together fat of R ¹ and R ² having 3 to 12 carbon atoms which may be substituted together with the carbon atom bonded In the case of forming a cyclic hydrocarbon group, it means the corresponding amide compound (III) obtained by subjecting the oxime compound (II) to a Beckmann rearrangement reaction.

  Examples of such Beckmann rearrangement include a method performed under liquid phase conditions and a method performed under gas phase conditions. The Beckmann rearrangement reaction under liquid phase conditions includes, for example, a method performed in the presence of a strong acid such as fuming sulfuric acid, and can be performed according to the method described in Japanese Patent Publication No. 48-4791. The Beckmann rearrangement reaction under gas phase conditions includes, for example, a method performed in the presence of a solid catalyst such as zeolite, and can be performed according to the method described in JP-A-5-170732. For example, when cyclohexylamine is used as the amine compound (I), ε-caprolactam can be produced by subjecting cyclohexanone oxime obtained by the oxidation to Beckmann rearrangement reaction.

Hereinafter, although the Example and comparative example of this invention are shown, this invention is not limited by this. In the Examples, cyclohexylamine in the reaction solution wherein (I), R ¹ and R ² together, the compound to form a cyclohexane ring together with the carbon atoms to which R ¹ and R ² are attached] and cyclohexanone oxime wherein (II), R ¹ and R ² together, compound to form a cyclohexane ring together with the carbon atoms to which R ¹ and R ² are bonded] analysis was performed by gas chromatography.

Reference example 1
[Preparation of catalyst]
In a 100 mL beaker, 40 g of water and 4 g of powdered silica alumina (manufactured by JGC Catalysts & Chemicals Co., Ltd .: SAL) were placed. Next, the mixture in the beaker was stirred and heated to 50 ° C. using a water bath, and then a 20 wt% titanium trichloride solution (a dilute hydrochloric acid solution of TiCl ₃ , manufactured by Wako Pure Chemical Industries, Ltd.). 29 g was gradually added dropwise using a pipette. After completion of the dropping, stirring was continued at 50 ° C. for 1 hour. After 1 hour, stirring was stopped and cooled to room temperature. The obtained mixture was subjected to pressure filtration to separate a solid, and this solid was repeatedly washed with water until the pH of the washing filtrate became 5 or more by pressure filtration. The washed solid was dried under vacuum for 1 hour at room temperature. The obtained dried product was filled in a quartz tube, and heat-treated at 450 ° C. for 6 hours while flowing air at a flow rate of 100 mL / min (0 ° C., 0.1 MPa conversion) to prepare catalyst A.

Example 1
In a reactor made of SUS316 (capacity: 200 mL) equipped with a thermocouple, a magnetic stirrer, a gas supply line, and a gas discharge line, 0.30 g of catalyst A obtained in Reference Example 1 and cyclohexylamine (Wako Pure Chemical Industries, Ltd. ( 1.49 g (15.0 mmol), 2,2-diphenyl-1-picrylhydrazyl (Aldrich) 0.15 g (0.38 mmol) and acetonitrile (Wako Pure Chemical Industries, Ltd.) Made), the gas phase in the reactor was replaced with nitrogen gas, and then sealed, and a gas mixture of oxygen and nitrogen (oxygen concentration: 7% by volume) was sealed in the gas phase in the reactor. The pressure inside the reactor was adjusted to 0.90 MPa (gauge pressure). Next, the temperature in the reactor was raised to 80 ° C. while stirring, and kept at 80 ° C. for 4 hours, and then cooled. The resulting reaction mixture was diluted with methanol and then filtered, and the obtained filtrate was analyzed. The conversion of cyclohexylamine was 19.5% and the selectivity for cyclohexanone oxime was 89.6%. there were.

Reference example 2
[Preparation of catalyst]
In a 100 mL beaker, 40 g of water and 4 g of powdery γ-alumina (manufactured by Sumitomo Chemical Co., Ltd .: GO-24) were placed. Next, while stirring the mixture in the beaker, the temperature was raised to 50 ° C. using a water bath, and then a 20 wt% titanium trichloride solution (a dilute hydrochloric acid solution of TiCl ₃ , manufactured by Wako Pure Chemical Industries, Ltd.). 22 g was gradually added dropwise using a pipette. After completion of the dropwise addition, stirring was continued at 50 ° C. for 6 hours. After 6 hours, stirring was stopped and cooled to room temperature. The obtained mixture was subjected to pressure filtration to separate a solid, and this solid was repeatedly washed with water until the pH of the washing filtrate became 5 or more by pressure filtration. The washed solid was dried under vacuum for 1 hour at room temperature. The obtained dried product was filled in a quartz tube, and heat-treated at 450 ° C. for 6 hours while flowing air at a flow rate of 100 mL / min (0 ° C., 0.1 MPa conversion) to prepare catalyst B.

Example 2
The same operation as in Example 1 was performed except that 0.30 g of the catalyst B obtained in Reference Example 2 was used instead of 0.30 g of the catalyst A. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 7.3% and the selectivity of cyclohexanone oxime was 60.8%.

Reference example 3
[Preparation of catalyst]
Catalyst 4 was prepared in the same manner as in Reference Example 2 except that 4 g of silica gel (Wako Pure Chemical Industries, Ltd .: Wakogel [registered trademark] Q-63) was used instead of 4 g of powdered silica alumina. Was prepared.

Example 3
The same operation as in Example 1 was performed except that 0.30 g of the catalyst C obtained in Reference Example 3 was used instead of 0.30 g of the catalyst A. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 8.7% and the selectivity for cyclohexanone oxime was 72.3%.

Reference example 4
[Preparation of catalyst]
In a 300 mL eggplant flask, 30 g of water and 4.94 g (15.0 mmol) of sodium tungstate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature until uniform. Next, 10.52 g (30.0 mmol) of tin (IV) chloride pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained mixture, and the mixture was stirred at room temperature for 1 hour. After stirring, 120 g of water was added, and the mixture was further stirred at room temperature for 24 hours. The obtained mixture was subjected to pressure filtration to separate a solid, and this solid was repeatedly washed with water until the pH of the washing filtrate became 6 or more by pressure filtration. The washed solid was dried overnight at 40 ° C. to prepare catalyst D.

Example 4
In a reactor made of SUS316 (capacity: 100 mL) equipped with a thermocouple, a magnetic stirrer, a gas supply line, and a gas discharge line, 0.30 g of catalyst D obtained in Reference Example 4 and cyclohexylamine (Wako Pure Chemical Industries, Ltd. ( 2.61 g (26.2 mmol), 0.15 g (0.37 mol) of 2,2-diphenyl-1-picrylhydrazyl (Aldrich) and acetonitrile (Wako Pure Chemical Industries, Ltd.) 7.07 g was added, and the gas phase portion in the reactor was replaced with nitrogen gas, and then sealed, and a gas mixture of oxygen and nitrogen (oxygen concentration: 7 vol%) was sealed in the gas phase portion in the reactor. The pressure inside the reactor was adjusted to 0.90 MPa (gauge pressure). Next, the temperature in the reactor was raised to 80 ° C. while stirring, and the temperature was kept at 80 ° C. for 5 hours, followed by cooling. The resulting reaction mixture was diluted with methanol and then filtered, and the obtained filtrate was analyzed. The conversion of cyclohexylamine was 42.6% and the selectivity of cyclohexanone oxime was 86.9%. there were.

Reference Example 5
[Preparation of catalyst]
A catalyst E was prepared in the same manner as in Reference Example 4 except that the washed solid was dried overnight at 110 ° C.

Example 5
The same operation as in Example 4 was performed except that 0.30 g of the catalyst E obtained in Reference Example 5 was used instead of 0.30 g of the catalyst D. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 39.4% and the selectivity for cyclohexanone oxime was 86.2%.

Reference Example 6
[Preparation of catalyst]
A catalyst F was prepared in the same manner as in Reference Example 4 except that the amount of sodium tungstate dihydrate was changed from 4.94 g to 2.47 g (7.5 mmol).

Example 6
The same operation as in Example 4 was performed except that 0.30 g of the catalyst F obtained in Reference Example 6 was used instead of 0.30 g of the catalyst D. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 43.0% and the selectivity of cyclohexanone oxime was 88.8%.

Reference Example 7
[Preparation of catalyst]
In a 300 mL eggplant flask, 15 g of water and 0.99 g (3.0 mmol) of sodium tungstate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature until uniform. Next, 5.26 g (15.0 mmol) of tin (IV) chloride pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained mixture, and the mixture was stirred at room temperature for 1 hour. After stirring, 285 g of water was added, and the mixture was further stirred at room temperature for 24 hours. The obtained mixture was subjected to pressure filtration to separate a solid, and this solid was repeatedly washed with water until the pH of the washing filtrate became 6 or more by pressure filtration. The washed solid was dried overnight at 40 ° C. to prepare catalyst G.

Example 7
The same operation as in Example 4 was performed except that 0.30 g of the catalyst G obtained in Reference Example 7 was used instead of 0.30 g of the catalyst D. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 35.3% and the selectivity of cyclohexanone oxime was 85.4%.

Reference Example 8
[Preparation of catalyst]
Catalyst H was prepared in the same manner as in Reference Example 7 except that the amount of sodium tungstate dihydrate was changed from 0.99 g to 0.50 g (1.5 mmol).

Example 8
The same operation as in Example 4 was performed except that 0.30 g of the catalyst H obtained in Reference Example 8 was used instead of 0.30 g of the catalyst D. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 13.0% and the selectivity of cyclohexanone oxime was 77.5%.

Reference Example 9
[Preparation of catalyst]
In a 300 mL eggplant flask, 15 g of water and 1.82 g (7.5 mmol) of sodium molybdate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature until uniform. Next, 5.26 g (15.0 mmol) of tin (IV) chloride pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained mixture, and the mixture was stirred at room temperature for 1 hour. After stirring, 60 g of water was added, and the mixture was further stirred at room temperature for 24 hours. The obtained mixture was subjected to pressure filtration to separate a solid, and this solid was repeatedly washed with water until the pH of the washing filtrate became 6 or more by pressure filtration. The washed solid was dried overnight at 40 ° C. to prepare Catalyst I.

Example 9
The same operation as in Example 4 was performed except that 0.30 g of the catalyst I obtained in Reference Example 9 was used instead of 0.30 g of the catalyst D. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 27.6% and the selectivity of cyclohexanone oxime was 67.7%.

Reference Example 10
[Preparation of catalyst]
In a 50 mL beaker, 12.7 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), 2 g / L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 3.0 g, and tetraethyl orthosilicate (Wako Pure Chemical Industries, Ltd. ( 6.3 g) was added and heated to 70 ° C. using a water bath while stirring, and then stirred at 70 ° C. for 1 hour to prepare α liquid. On the other hand, 18.0 g of 2 mol / L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.8 g of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a 50 mL beaker at room temperature. Stir for 30 minutes to prepare β solution.

  In a 500 mL beaker, 93.9 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and 15.1 g of sepiolite (Sepiorb 400 manufactured by Sepio Japan Co., Ltd.) was added with stirring, and the mixture was stirred at room temperature for 5 minutes. Next, using a water bath, the mixture in the poly beaker was heated to 50 ° C. while stirring, and then a mixed solution of α liquid total amount and β liquid total amount was dropped over 30 minutes. And stirring was continued for 6 hours. After 6 hours, the mixture was cooled to room temperature and stirring was stopped. The obtained mixture was subjected to pressure filtration to separate a solid, and this solid was washed and filtered with water by pressure filtration, and washed repeatedly until the pH of the washing filtrate became 5 or more. After washing, the resulting solid was dried at 110 ° C. overnight to prepare Catalyst J.

Example 10
In a reactor made of SUS316 (capacity: 200 mL) equipped with a thermocouple, a magnetic stirrer, a gas supply line, and a gas discharge line, 0.30 g of catalyst J obtained in Reference Example 10 and cyclohexylamine (Wako Pure Chemical Industries, Ltd. ( Co., Ltd.) 1.49 g (15.0 mmol) and acetonitrile (Wako Pure Chemical Industries, Ltd.) 6.99 g were added, and the gas phase in the reactor was replaced with nitrogen gas, and then sealed, A gas mixture of oxygen and nitrogen (oxygen concentration: 7% by volume) was introduced into the gas phase portion in the reactor to adjust the pressure in the reactor to 0.90 MPa (gauge pressure). Next, the temperature in the reactor was raised to 80 ° C. while stirring. The pressure in the reactor at this time was 1.04 MPa (gauge pressure). Next, the mixture was kept at 80 ° C. for 4 hours while continuing stirring, and then cooled. The resulting reaction mixture was diluted with methanol and then filtered, and the obtained filtrate was analyzed. The conversion of cyclohexylamine was 0.3% and the selectivity of cyclohexanone oxime was 38.4%. there were.

Example 11
Example 10 except that 0.15 g (0.38 mmol) of 2,2-diphenyl-1-picrylhydrazyl (manufactured by Aldrich) was added to the reactor in addition to catalyst J, cyclohexylamine and acetonitrile. Was performed. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 21.2% and the selectivity of cyclohexanone oxime was 92.0%.

Reference Example 11
[Preparation of catalyst]
In a 300 mL beaker, 78.0 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added, 10.0 g of sepiolite (Sepisorb 400 manufactured by Sepio Japan Co., Ltd.) was added with stirring, and the mixture was stirred at room temperature for 5 minutes. Next, using a water bath, the mixture in the poly beaker was heated to 50 ° C. while stirring, and then a 20 wt% titanium trichloride solution (a dilute hydrochloric acid solution of TiCl ₃ , manufactured by Wako Pure Chemical Industries, Ltd.). 0g was dripped over 30 minutes, and stirring was continued at 50 degreeC after completion | finish of dripping for 6 hours. After 6 hours, the mixture was cooled to room temperature and stirring was stopped. The obtained mixture was subjected to pressure filtration to separate a solid, and this solid was washed and filtered with water by pressure filtration, and washed repeatedly until the pH of the washing filtrate became 5 or more. After washing, the resulting solid was dried at 110 ° C. overnight to prepare Catalyst K.

Example 12
The same operation as in Example 10 was performed except that 0.30 g of the catalyst K obtained in Reference Example 11 was used instead of 0.30 g of the catalyst J. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 0.2% and the selectivity of cyclohexanone oxime was 27.1%.

Example 13
The same operation as in Example 11 was performed except that 0.30 g of the catalyst K obtained in Reference Example 11 was used instead of 0.30 g of the catalyst J. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 13.8% and the selectivity of cyclohexanone oxime was 78.2%.

Reference Example 12
[Preparation of catalyst]
Catalyst L was prepared in the same manner as in Reference Example 11 except that 10.0 g of palygorskite was used instead of 10.0 g of sepiolite.

Example 14
The same operation as in Example 10 was performed except that 0.30 g of the catalyst L obtained in Reference Example 12 was used instead of 0.30 g of the catalyst J. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 1.5% and the selectivity of cyclohexanone oxime was 46.1%.

Example 15
The same operation as in Example 11 was performed except that 0.30 g of the catalyst L obtained in Reference Example 12 was used instead of 0.30 g of the catalyst J. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 21.3% and the selectivity for cyclohexanone oxime was 80.7%.

Reference Example 13
[Preparation of catalyst]
In a dropping funnel, 35 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), 85 g of tetrabutyl orthotitanate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 52 g of tetraethyl orthosilicate (manufactured by Wako Pure Chemical Industries, Ltd.) are added. Mixed. On the other hand, 721 g of ion-exchanged water and 51 g of 25% ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a 2 L poly beaker and stirred at room temperature for 5 minutes. After stirring for 5 minutes, the liquid mixture in the dropping funnel was dropped into the liquid mixture in the poly beaker over 30 minutes while continuing the stirring. After completion of the dropping, stirring was further continued at room temperature for 30 minutes, and the resulting mixture was subjected to pressure filtration to separate a solid, and this solid was washed with water by pressure filtration and filtered. After washing, the obtained solid was dried at 110 ° C. overnight to prepare catalyst M (amorphous titanosilicate).

Example 16
In a reactor made of SUS316 (capacity: 1 L) equipped with a thermocouple, a magnetic stirrer, a gas supply line, and a gas discharge line, 7.5 g of the catalyst M obtained in Reference Example 13 and cyclohexylamine (Wako Pure Chemical Industries, Ltd. ( 106 g (1.1 mol) and 106 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the gas phase in the reactor was replaced with nitrogen gas, then sealed, and the reactor was sealed. Nitrogen gas was introduced into the gas phase to adjust the pressure in the reactor to 0.90 MPa (gauge pressure). Subsequently, it heated up at 80 degreeC, stirring. The pressure in the reactor at this time was 0.90 MPa (gauge pressure). Next, while stirring is continued, a mixed gas of oxygen and nitrogen (oxygen concentration: 7% by volume) is blown into the liquid phase of the mixture in the reactor at a flow rate of 450 mL / min, and the inside of the reactor is circulated. The reaction was started. While maintaining the pressure in the reactor at 0.90 MPa (gauge pressure) and continuing the reaction at 80 ° C. for 5 hours while discharging the gas from the gas phase portion in the reactor through the gas discharge line, oxygen and The supply of the mixed gas with nitrogen was stopped and the mixture was cooled. The obtained reaction mixture was diluted with methanol and then filtered, and the obtained filtrate was analyzed. The conversion of cyclohexylamine was 0.4% and the selectivity of cyclohexanone oxime was 27.9%. there were.

Example 17
Example 16 except that 7.5 g of amorphous titanosilicate having mesopores prepared in accordance with the method described in JP-A-2000-117101 was used instead of 7.5 g of catalyst M The same operation was performed. The pressure in the reactor when the temperature was raised to 80 ° C. was 0.90 MPa (gauge pressure). When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 0.6% and the selectivity of cyclohexanone oxime was 29.7%.

Example 18
The same operation as in Example 16 was performed except that 7.5 g of Ti-HMS was used instead of 7.5 g of the catalyst M. The pressure in the reactor when the temperature was raised to 80 ° C. was 0.90 MPa (gauge pressure). When the obtained filtrate was analyzed, the conversion rate of cyclohexylamine was 0.6% and the selectivity of cyclohexanone oxime was 32.4%.

Comparative Example 1
The same operation as in Example 1 was performed except that 0.30 g of titanium oxide (TiO ₂ , ST-01 manufactured by Ishihara Sangyo Co., Ltd.) was used instead of 0.30 g of catalyst A. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 3.1% and the selectivity of cyclohexanone oxime was 46.3%.

Comparative Example 2
The same operation as in Comparative Example 1 was performed except that 2,2-diphenyl-1-picrylhydrazyl was not used. When the obtained filtrate was analyzed, the conversion of cyclohexylamine was 0.2% and the selectivity of cyclohexanone oxime was 5.6%.

Comparative Example 3
The same operation as in Example 16 was performed except that 7.5 g of titanium oxide (TiO ₂ , ST-01 manufactured by Ishihara Sangyo Co., Ltd.) was used instead of 7.5 g of the catalyst M. The pressure in the reactor when the temperature was raised to 80 ° C. was 0.90 MPa (gauge pressure). When the obtained filtrate was analyzed, the conversion rate of cyclohexylamine was 0.2% and the selectivity of cyclohexanone oxime was 10.6%.

Claims (6)

In the presence of at least one catalyst selected from the group consisting of the following (A), (B), (C) and (D), the following formula (I)

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group (provided that R ¹ and R ² are both Or R ¹ and R ² together may be substituted with the carbon atom to which R ¹ and R ² are bonded, and the C 3-12 alicyclic carbonization. Form a hydrogen group. ]
Wherein the amine represented by formula (II) is brought into contact with oxygen:

(In the formula, R ¹ and R ² each have the same meaning as described above.)
The manufacturing method of oxime shown by this.
(A) Titanium-supported catalyst obtained by subjecting a support to contact treatment with a titanium compound and then heat-treating at 150 ° C. or higher (B) A catalyst containing at least one selected from the group consisting of tungsten and molybdenum and tin (C) Inosilicate Catalyst (D) Amorphous titanosilicate catalyst   The production method according to claim 1, wherein the carrier is silica alumina.   The production method according to claim 1 or 2, wherein the inosilicate catalyst is at least one catalyst selected from the group consisting of a sepiolite catalyst and a palygorskite catalyst.   The inosilicate catalyst includes a Group 4 metal element, a Group 5 metal element, a Group 6 metal element, germanium, an oxide of a Group 4 metal element, an oxide of a Group 5 metal element, and a Group 6 metal element. The manufacturing method in any one of Claims 1-3 containing at least 1 type chosen from the group which consists of an oxide and germanium oxide.   The manufacturing method according to claim 1, wherein the amorphous titanosilicate catalyst is an amorphous mesoporous titanosilicate catalyst. A Beckmann rearrangement reaction of the oxime represented by the formula (II) produced by the production method according to any one of claims 1 to 5 is carried out:

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an optionally substituted hydrocarbon group or an optionally substituted heterocyclic group (provided that R ¹ and R ² are both R ¹ and R ² may be combined together to form a nitrogen atom to which R ¹ is bonded and a carbon atom having 3 to 3 carbon atoms which may be substituted together with the carbon atom to which R ² is bonded. 12 aliphatic heterocycles are formed. ]
The manufacturing method of amide shown by these.