Method for producing oxime

Abstract

Provided is a method for producing an oxime compound with satisfactory selectivity. Provide is a method for producing an oxime represented by the following formula (II): ##STR00001##
wherein R.sup.1 and R.sup.2 are respectively the same as defined below, the method including oxidizing an amine represented by the following formula (I): ##STR00002##
wherein R.sup.1 and R.sup.2 each independently represents a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group (provided that R.sup.1 and R.sup.2 are not simultaneously hydrogen atoms), or
R.sup.1 and R.sup.2, together with the carbon atom to which R.sup.1 and R.sup.2 are attached, form an optionally substituted alicyclic hydrocarbon group having 3 to 12 carbon atoms [hereinafter sometimes referred to as the amine compound (I)],
with oxygen in the presence of a layered silicate.

Claims

1. A method for producing an oxime represented by the following formula (II): ##STR00006## wherein R.sup.1 and R.sup.2 are respectively the same as defined below, the method comprising oxidizing an amine represented by the following formula (I): ##STR00007## wherein R.sup.1 and R.sup.2 each independently represents a hydrogen atom, an optionally substituted hydrocarbon group, or an optionally substituted heterocyclic group (provided that R.sup.1 and R.sup.2 are not simultaneously hydrogen atoms), or R.sup.1 and R.sup.2, together with the carbon atom to which R.sup.1 and R.sup.2 are attached, form an optionally substituted alicyclic hydrocarbon group having 3 to 12 carbon atoms, with oxygen in the presence of a layered silicate.

2. The method according to claim 1, wherein the layered silicate is smectite.

3. The method according to claim 1, wherein the layered silicate contains at least one selected from the group consisting of hydrogen ions, ammonium ions, quaternary ammonium ions, cations of group 4 metal elements, cations of group 5 metal elements, cations of group 6 metal elements, germanium ions, oxides of positively charged group 4 metal elements, oxides of positively charged group 5 metal elements, oxides of positively charged group 6 metal elements, and positively charged germanium oxides.

4. The method according to claim 1, wherein the layered silicate contains at least one selected from the group consisting of cations of group 4 metal elements, germanium ions, oxides of positively charged group 4 metal elements, and positively charged germanium oxides.

5. The method according to claim 1, wherein the layered silicate contains at least one selected from the group consisting of titanium ions, germanium ions, positively charged titanium oxides, and positively charged germanium oxides.

6. The method according to claim 3, wherein the layered silicate further contains at least one selected from the group consisting of cations of group 8 metal elements, cations of group 9 metal elements, cations of group 10 metal elements, cations of group 11 metal elements, cations of group 12 metal elements, cations of group 13 metal elements, oxides of positively charged group 8 metal elements, oxides of positively charged group 9 metal elements, oxides of positively charged group 10 metal elements, oxides of positively charged group 11 metal elements, oxides of positively charged group 12 metal elements, oxides of positively charged group 13 metal elements, and oxides of positively charged silicon.

7. The method according to claim 1, wherein the layered silicate is calcined at 150 C. to 600 C.

Description

EXAMPLES

(1) The present invention will be described by way of the following Examples and Comparative Examples, but it is not construed to limit the present invention thereto. In the following Examples, cyclohexylamine [compound in which R.sup.1 and R.sup.2 are taken together with the carbon atom to which R.sup.1 and R.sup.2 are attached to form a cyclohexane ring in the formula (I)] and cyclohexanone oxime [compound in which R.sup.1 and R.sup.2 are taken together with the carbon atom to which R.sup.1 and R.sup.2 are attached to form a cyclohexane ring in the formula (II)] in the reaction solution were analyzed by gas chromatography, and the conversion ratio of cyclohexylamine as well as the selectivity of cyclohexanone oxime were calculated based on the results of the analysis.

Reference Example 1

Preparation of Catalyst

(2) In a 2 L poly beaker, 687 g of 1,2-dimethoxyethane (manufactured by Wako Pure Chemical Industries, Ltd.) and 13.24 g of 35% by weight hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and 15 g of montmorillonite (Kunipia F, manufactured by KUNIMINE INDUSTRIES CO., LTD., montmorillonite containing sodium ions, potassium ions, and calcium ions as interlayer cations) was added while stirring the obtained mixture. After stirring at room temperature for 5 minutes, a vapor phase portion in the poly beaker was replaced by nitrogen. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker, 17.97 g of a 20% by weight titanium trichloride solution (dilute hydrochloric acid solution of TiCl.sub.3, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. After completion of the dropwise addition, stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst A (montmorillonite containing titanium ions between layers).

Example 1

(3) In a reactor made of SUS316 (volume: 200 mL) equipped with a thermocouple, a magnetic stirrer, a gas feed line, and a gas discharge line, 0.30 g of the catalyst A obtained in Reference Example 1, 1.52 g (15.3 mmol) of cyclohexylamine (manufactured by Wako Pure Chemical Industries, Ltd.), and 7.07 g of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and a vapor phase portion in the reactor was replaced by nitrogen. After the reactor was sealed, a mixed gas of oxygen and nitrogen (oxygen concentration: 7% by volume) was introduced into the vapor phase portion in the reactor to thereby 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 was 1.05 MPa (gauge pressure). After keeping the reactor warm at 80 C. for 4 hours while continuing to stir, cooling was performed. The obtained reaction mixture was diluted by the addition of methanol and filtrated, and then the obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 0.9% and the selectivity of cyclohexanone oxime was 84.6%.

Example 2

(4) The same operation as in Example 1 was performed, except that temperature rise to 80 C. was replaced by temperature rise to 90 C. and the reactor kept warm at 90 C. for 4 hours. The pressure in the reactor was 1.10 MPa (gauge pressure) when the temperature was raised to 90 C. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 2.3% and the selectivity of cyclohexanone oxime was 80.3%.

Example 3

(5) The same operation as in Example 1 was performed, except that 0.14 g (0.36 mmol) of 2,2-diphenyl-1-picrylhydrazyl (manufactured by Aldrich) was charged in the reactor, in addition to the catalyst A, cyclohexylamine, and acetonitrile. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 19.8% and the selectivity of cyclohexanone oxime was 91.8%.

Example 4

(6) The same operation as in Example 3 was performed, except that the use amount of 2,2-diphenyl-1-picrylhydrazyl was changed from 0.14 g to 0.014 g (0.036 mmol). The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 2.1% and the selectivity of cyclohexanone oxime was 86.5%.

Example 5

(7) The same operation as in Example 3 was performed, except that 7.03 g of t-butanol (manufactured by Wako Pure Chemical Industries, Ltd., water content: 2,000 ppm by weight) was used in place of 7.07 g of acetonitrile. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 9.6% and the selectivity of cyclohexanone oxime was 94.5%.

Example 6

(8) The same operation as in Example 3 was performed, except that 7.05 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of 7.07 g of acetonitrile. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 14.3% and the selectivity of cyclohexanone oxime was 88.6%.

Example 7

(9) The same operation as in Example 3 was performed, except that 7.04 g of a mixed solution of t-butanol and water [t-butanol/water=7/1 (weight ratio)] was used in place of 7.07 g of acetonitrile. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 2.2% and the selectivity of cyclohexanone oxime was 87.8%.

Example 8

(10) The same operation as in Example 3 was performed, except that 7.14 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd., water content: 1,000 ppm by weight) was used in place of 7.07 g of acetonitrile. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 7.2% and the selectivity of cyclohexanone oxime was 86.9%.

Example 9

(11) The same operation as in Example 3 was performed, except that 0.31 g of montmorillonite KSF (manufactured by Aldrich) was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 9.5% and the selectivity of cyclohexanone oxime was 59.3%.

Example 10

(12) The same operation as in Example 3 was performed, except that 0.30 g of activated clay (manufactured by Sigma-Aldrich Japan K.K.) was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 7.4% and the selectivity of cyclohexanone oxime was 57.3%.

Reference Example 2

Preparation of Catalyst

(13) The same operation as in Reference Example 1 was performed, except that 36.18 g of a 20% by weight titanium trichloride solution was used in place of 17.97 g of the 20% by weight titanium trichloride solution, a catalyst B (montmorillonite containing titanium ions between layers) was prepared.

Example 11

(14) 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 in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 1.2% and the selectivity of cyclohexanone oxime was 77.0%.

Reference Example 3

Preparation of Catalyst

(15) The same operation as in Reference Example 1 was performed, except that 72.76 g of a 20% by weight titanium trichloride solution was used in place of 17.97 g of the 20% by weight titanium trichloride solution, a catalyst C (montmorillonite containing titanium ions between layers) was prepared.

Example 12

(16) The same operation as in Example 1 was performed, except that 0.60 g of the catalyst C obtained in Reference Example 3 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 2.7% and the selectivity of cyclohexanone oxime was 78.0%.

Reference Example 4

Preparation of Catalyst

(17) In a 1 L separable flask, 600 g of 2 mol/L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 60 g of montmorillonite (Kunipia F, manufactured by KUNIMINE INDUSTRIES CO., LTD., montmorillonite containing sodium ions, potassium ions, and calcium ions as interlayer cations) were charged, followed by stirring at room temperature for 5 minutes stirring. Using an oil bath, the temperature was raised to 90 C. while stirring the mixture in the separable flask, and stirring was continued at 90 C. for 12 hours. After 12 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst D (montmorillonite containing hydrogen ions between layers).

Example 13

(18) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst D obtained in Reference Example 4 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 6.7% and the selectivity of cyclohexanone oxime was 65.1%.

Reference Example 5

Preparation of Catalyst

(19) In a 2 L poly beaker, 700 g of 1,2-dimethoxyethane (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and 1.71 g of a 20% by weight titanium trichloride solution (dilute hydrochloric acid solution of TiCl.sub.3, manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring, followed by stirring at room temperature for 5 minutes stirring. To the obtained mixed solution, 15 g of montmorillonite (Kunipia F, manufactured by KUNIMINE INDUSTRIES CO., LTD., montmorillonite containing sodium ions, potassium ions, and calcium ions as interlayer cations) was added. After stirring at room temperature for 5 minutes, a vapor phase portion in the poly beaker was replaced by nitrogen. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker, and stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst E (montmorillonite containing titanium ions between layers).

Example 14

(20) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst E obtained in Reference Example 5 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 19.8% and the selectivity of cyclohexanone oxime was 88.1%.

Reference Example 6

Preparation of Catalyst

(21) In a 2 L poly beaker, 1,400 g of 1,2-dimethoxyethane (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and 4.82 g of zirconyl nitrate dihydrate (ZrO(NO.sub.3).sub.2.2H.sub.2O.sub.r manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring, followed by stirring at room temperature for 5 minutes stirring. To the obtained mixed solution, 30 g of montmorillonite (Kunipia F, manufactured by KUNIMINE INDUSTRIES CO., LTD., montmorillonite containing sodium ions, potassium ions, and calcium ions as interlayer cations) was added. After stirring at room temperature for 5 minutes, a vapor phase portion in the poly beaker was replaced by nitrogen. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker, and stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst F (montmorillonite containing positively charged zirconia between layers).

Example 15

(22) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst F obtained in Reference Example 6 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 4.8% and the selectivity of cyclohexanone oxime was 51.8%.

Reference Example 7

Preparation of Catalyst

(23) In a 2 L poly beaker, 700 g of 1,2-dimethoxyethane (manufactured by Wako Pure Chemical Industries, Ltd.) and 15 g of Saponite (Sumecton SA, manufactured by KUNIMINE INDUSTRIES CO., LTD.) were charged. After stirring at room temperature for 5 minutes stirring, a vapor phase portion in the poly beaker was replaced by nitrogen. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker, and 17.97 g of a 20% by weight titanium trichloride solution (dilute hydrochloric acid solution of TiCl.sub.3, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. After completion of the dropwise addition, stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst G (Saponite containing titanium ions between layers).

Example 16

(24) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst G obtained in Reference Example 7 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 3.7% and the selectivity of cyclohexanone oxime was 82.0%.

Reference Example 8

Preparation of Catalyst

(25) In a 5 L poly beaker, 2,801 g of deionized water and 71.97 g of a 20% by weight titanium trichloride solution (dilute hydrochloric acid solution of TiCl.sub.3, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by stirring at room temperature for 5 minutes stirring. To the obtained mixed solution, 60 g of montmorillonite (Kunipia F, manufactured by KUNIMINE INDUSTRIES CO., LTD., montmorillonite containing sodium ions, potassium ions, and calcium ions as interlayer cations) was added. After stirring at room temperature for 5 minutes, a vapor phase portion in the poly beaker was replaced by nitrogen. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker, and stirring was continued at 50 C. for 12 hours. After 12 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst H (montmorillonite containing titanium ions between layers).

Example 17

(26) In a reactor made of SUS316 (volume: 1 L) equipped with a thermocouple, a magnetic stirrer, a gas feed line, and a gas discharge line, 7.53 g of the catalyst H obtained in Reference Example 8, 106 g (1.1 mol) of cyclohexylamine (manufactured by Wako Pure Chemical Industries, Ltd.), and 106 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and a vapor phase portion in the reactor was replaced by a nitrogen gas. After the reactor was sealed, a nitrogen gas was introduced into the vapor phase portion in the reactor to thereby 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 was 0.90 MPa (gauge pressure). While continuing to stir, a mixed gas of oxygen and nitrogen (oxygen concentration: 7% by volume) was allowed to flow through the reactor by blowing into a liquid phase of the mixture in the reactor at a flow rate of 450 mL/minute to thereby initiate the reaction. While maintaining the pressure in the reactor at 0.90 MPa (gauge pressure), the reaction was continued for 5 hours while discharging the gas from the vapor phase portion in the reactor via a gas discharge line and then feed of the mixed gas of oxygen and nitrogen was stopped, followed by cooling. The obtained reaction mixture was diluted by the addition of methanol and filtrated, and then the obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 1.9% and the selectivity of cyclohexanone oxime was 60.1%.

Example 18

(27) The same operation as in Example 17 was performed, except that temperature rise to 80 C. was replaced by temperature rise to 90 C. and the reaction was continued at 90 C. for 5 hours. The pressure in the reactor was 0.90 MPa (gauge pressure) when the temperature was raised to 90 C. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 2.7% and the selectivity of cyclohexanone oxime was 61.8%.

Example 19

(28) The same operation as in Example 17 was performed, except that temperature rise to 80 C. was replaced by temperature rise to 100 C. and the reaction was continued at 100 C. for 5 hours. The pressure in the reactor was 0.90 MPa (gauge pressure) when the temperature was raised to 100 C. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 3.0% and the selectivity of cyclohexanone oxime was 60.3%.

Example 20

(29) The same operation as in Example 17 was performed, except that temperature rise to 80 C. was replaced by temperature rise to 120 C. and the reaction was continued at 120 C. for 5 hours. The pressure in the reactor was 0.90 MPa (gauge pressure) when the temperature was raised to 120 C. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 6.2% and the selectivity of cyclohexanone oxime was 60.6%.

Reference Example 9

Preparation of Catalyst

(30) In a 1 L poly beaker, 716.1 g of deionized water and 5.06 g of germanium tetrachloride (GeCl.sub.4, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by stirring at room temperature for 5 minutes. To the obtained mixed solution, 15 g of montmorillonite (Kunipia F, manufactured by KUNIMINE INDUSTRIES CO., LTD., montmorillonite containing sodium ions, potassium ions, and calcium ions as interlayer cations) was added. After stirring at room temperature for 5 minutes, a vapor phase portion in the poly beaker was replaced by nitrogen. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker, and stirring was continued at 50 C. for 12 hours. After 12 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst I (montmorillonite containing positively charged germanium oxides between layers).

Example 21

(31) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst I obtained in Reference Example 9 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 9.1% and the selectivity of cyclohexanone oxime was 81.0%.

Reference Example 10

(32) In a 500 mL recovery flask, 150.2 g of deionized water and 15.1 g of the catalyst H obtained in Reference Example 8 were charged, followed by stirring at room temperature for 10 minutes. To the obtained mixture, 5.0 g of platinum nanocolloid (manufactured by Nippon Sheet Glass Co. Ltd.) was added, followed by stirring at room temperature for 5 minutes. Next, a solid was separated by distilling off water from the obtained mixture at 50 C. under reduced pressure using a rotary evaporator. This solid was calcined at 450 C. under air flow for 6 hours to prepare a catalyst J.

Example 22

(33) The same operation as in Example 3 was performed, except that 0.31 g of the catalyst J obtained in Reference Example 10 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 29.1% and the selectivity of cyclohexanone oxime was 90.9%.

Reference Example 11

(34) In a 500 mL recovery flask, 50.7 g of deionized water and 5.1 g of the catalyst A obtained in Reference Example 1 was charged, followed by stirring at room temperature for 5 minutes. To the obtained mixture, 0.12 g of ruthenium chloride hydrate (manufactured by FURUYA METAL Co., Ltd., Ru content of 40.75% by weight) was added, followed by stirring at room temperature for 5 minutes. Next, a solid was separated by distilling off water from the obtained mixture at 50 C. under reduced pressure using a rotary evaporator. This solid was calcined at 450 C. under air flow for 6 hours to prepare a catalyst K.

Example 23

(35) The same operation as in Example 1 was performed, except that 0.30 g of the catalyst K obtained in Reference Example 11 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 2.1% and the selectivity of cyclohexanone oxime was 78.1%.

Example 24

(36) The same operation as in Example 3 was performed, except that 0.31 g of the catalyst K obtained in Reference Example 11 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 40.5% and the selectivity of cyclohexanone oxime was 94.9%.

Reference Example 12

(37) The same operation as in Reference Example 11 was performed, except that 0.07 g of silver chloride (AgCl, manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of 0.12 g of ruthenium chloride hydrate, a catalyst L was prepared.

Example 25

(38) The same operation as in Example 1 was performed, except that 0.30 g of the catalyst L obtained in Reference Example 12 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 1.6% and the selectivity of cyclohexanone oxime was 82.7%.

Example 26

(39) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst L obtained in Reference Example 12 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 43.0% and the selectivity of cyclohexanone oxime was 94.3%.

Reference Example 13

(40) The same operation as in Reference Example 11 was performed, except that 0.07 g of palladium chloride (PdCl.sub.2, manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of 0.12 g of ruthenium chloride hydrate, a catalyst M was prepared.

Example 27

(41) The same operation as in Example 1 was performed, except that 0.30 g of the catalyst M obtained in Reference Example 13 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 1.8% and the selectivity of cyclohexanone oxime was 83.9%.

Example 28

(42) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst M obtained in Reference Example 13 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 38.3% and the selectivity of cyclohexanone oxime was 93.7%.

Reference Example 14

(43) The same operation as in Reference Example 11 was performed, except that 0.10 g of iridium chloride (IrCl.sub.4, manufactured by Wako Pure Chemical Industries, Ltd.) was used in place of 0.12 g of ruthenium chloride hydrate, a catalyst N was prepared.

Example 29

(44) The same operation as in Example 3 was performed, except that 0.31 g of the catalyst N obtained in Reference Example 14 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 42.5% and the selectivity of cyclohexanone oxime was 94.7%.

Reference Example 15

Preparation of Catalyst

(45) In a 2 L poly beaker, 1,200 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and 32.13 g of a 20% by weight titanium trichloride solution (dilute hydrochloric acid solution of TiCl.sub.3, manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring, followed by stirring at room temperature for 5 minutes. To the obtained mixed solution, 26.88 g of montmorillonite (Kunipia F, manufactured by KUNIMINE INDUSTRIES CO., LTD., montmorillonite containing sodium ions, potassium ions, and calcium ions as interlayer cations) was added. After stirring at room temperature for 5 minutes, a vapor phase portion in the poly beaker was replaced by nitrogen. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker, and stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. and the obtained dried substance was calcined under air flow at 450 C. for 6 hours to prepare a catalyst 0.

Example 30

(46) The same operation as in Example 3 was performed, except that 0.31 g of the catalyst 0 obtained in Reference Example 15 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 29.3% and the selectivity of cyclohexanone oxime was 93.9%.

Reference Example 16

Preparation of Catalyst

(47) In a 1 L poly beaker, 390 g of methanol (special grade chemical, manufactured by Wako Pure Chemical Industries, Ltd.) and 50.2 g of montmorillonite (Kunipia F, manufactured by KUNIMINE INDUSTRIES CO., LTD., montmorillonite containing sodium ions, potassium ions, and calcium ions as interlayer cations) were charged. Using a water bath, the temperature was raised to 50 C. while stirring, and 59.9 g of a 20% by weight titanium trichloride solution (dilute hydrochloric acid solution of TiCl.sub.3, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. After completion of the dropwise addition, stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst P (montmorillonite containing titanium ions between layers).

Example 31

(48) The same operation as in Example 1 was performed, except that 0.30 g of the catalyst P obtained in Reference Example 16 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 3.4% and the selectivity of cyclohexanone oxime was 82.3%.

Example 32

(49) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst P obtained in Reference Example 16 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 27.4% and the selectivity of cyclohexanone oxime was 91.5%.

Reference Example 17

Preparation of Catalyst

(50) In a 1 L poly beaker, 388 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 50.1 g of montmorillonite (Kunipia F, manufactured by KUNIMINE INDUSTRIES CO., LTD., montmorillonite containing sodium ions, potassium ions, and calcium ions as interlayer cations) were charged. Using a water bath, the temperature was raised to 50 C. while stirring, and 62.1 g of a 30% by weight titanium sulfate solution (dilute sulfuric acid solution of Ti(SO.sub.4).sub.2, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. After completion of the dropwise addition, stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst Q (montmorillonite containing titanium ions between layers).

Example 33

(51) The same operation as in Example 1 was performed, except that 0.30 g of the catalyst Q obtained in Reference Example 17 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 3.1% and the selectivity of cyclohexanone oxime was 69.5%.

Example 34

(52) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst Q obtained in Reference Example 17 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 26.4% and the selectivity of cyclohexanone oxime was 91.7%.

Reference Example 18

Preparation of Catalyst

(53) In a 50 mL beaker, 12.1 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 6.1 g of 2 mol/L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were charged. While stirring the obtained mixture, 25.3 g of tetraethyl orthosilicate (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Using a water bath, the temperature was raised to 70 C. while stirring, and stirring was continued at 70 C. for 1 hour to prepare a solution a. Meanwhile, 36.2 g of 2 mol/L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.6 g of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) were charged in a 50 mL beaker, followed by stirring at room temperature for 1 hour to prepare a solution b.

(54) In a 500 mL poly beaker, 187.5 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 30.5 g of montmorillonite (Kunipia F, manufactured by KUNIMINE INDUSTRIES CO., LTD., montmorillonite containing sodium ions, potassium ions, and calcium ions as interlayer cations) were charged, followed by stirring at room temperature for 5 minutes. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker and then a mixed solution of the total amount of the solution a and the total amount of the solution b was added dropwise over 1 hour. After completion of the dropwise addition, stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst R.

Example 35

(55) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst R obtained in Reference Example 18 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 22.2% and the selectivity of cyclohexanone oxime was 89.8%.

Reference Example 19

Preparation of Catalyst

(56) In a 50 mL beaker, 12.6 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.1 g of 2 mol/L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were charged. While stirring the obtained mixture, 6.1 g of tetraethyl orthosilicate (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Using a water bath, the temperature was raised to 70 C. while stirring, and stirring was continued at 70 C. for 1 hour to prepare a solution c. Meanwhile, 18.1 g of 2 mol/L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.9 g of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) were charged in a 50 mL beaker, followed by stirring at room temperature for 1 hour to prepare a solution d.

(57) In a 300 mL poly beaker, 93.7 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 15.1 g of Saponite (Sumecton SA, manufactured by KUNIMINE INDUSTRIES CO., LTD.) were charged, followed by stirring at room temperature for 5 minutes. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker and then a mixed solution of the total amount of the solution c and the total amount of the solution d was added dropwise over 1 hour. After completion of the dropwise addition, stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst S.

Example 36

(58) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst S obtained in Reference Example 19 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 28.4% and the selectivity of cyclohexanone oxime was 88.3%.

Reference Example 20

Preparation of Catalyst

(59) In a 1 L poly beaker, 117 g of methanol (special grade chemical, manufactured by Wako Pure Chemical Industries, Ltd.) and 15.8 g of hectorite (LUCENTITE SWF, manufactured by Co-op Chemical Co., Ltd.) were charged. Using a water bath, the temperature was raised to 50 C. while stirring, and 18.0 g of a 20% by weight titanium trichloride solution (dilute hydrochloric acid solution of TiCl.sub.3, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 15 minutes. After completion of the dropwise addition, stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst T (hectorite containing titanium ions between layers).

Example 37

(60) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst T obtained in Reference Example 20 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 19.8% and the selectivity of cyclohexanone oxime was 85.2%.

Reference Example 21

Preparation of Catalyst

(61) In a 50 mL beaker, 6.0 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.0 g of 2 mol/L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were charged and 12.6 g of tetraethyl orthosilicate (manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring the obtained mixture. Using a water bath, the temperature was raised to 70 C. while stirring and stirring was continued at 70 C. for 1 hour to prepare a solution e. Meanwhile, 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.) were charged in a 50 mL beaker, followed by stirring at room temperature for 1 hour to prepare a solution f.

(62) In a 500 mL poly beaker, 93.6 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 15.0 g of hectorite (LUCENTITE SWF, manufactured by Co-op Chemical Co., Ltd.) were charged, followed by stirring at room temperature for 5 minutes. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker and then a mixed solution of the total amount of the solution e and the total amount of the solution f was added dropwise over 1 hour. After completion of the dropwise addition, stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst U.

Example 38

(63) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst U obtained in Reference Example 21 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 20.5% and the selectivity of cyclohexanone oxime was 88.7%.

Reference Example 22

Preparation of Catalyst

(64) In a 1 L poly beaker, 156 g of methanol (special grade chemical, manufactured by Wako Pure Chemical Industries, Ltd.) and 20.0 g of stevensite (Sumecton ST, manufactured by KUNIMINE INDUSTRIES CO., LTD.) were charged. Using a water bath, the temperature was raised to 50 C. while stirring, and 24.0 g of 20% by weight titanium trichloride solution (dilute hydrochloric acid solution of TiCl.sub.3, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 25 minutes. After completion of the dropwise addition, stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst V (stevensite containing titanium ions between layers).

Example 39

(65) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst V obtained in Reference Example 22 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 17.1% and the selectivity of cyclohexanone oxime was 86.2%.

Reference Example 23

Preparation of Catalyst

(66) In a 100 mL beaker, 15.9 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 8.0 g of 2 mol/L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were charged, and 33.6 g of tetraethyl orthosilicate (manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring the obtained mixture. Using a water bath, the temperature was raised to 70 C. while stirring and stirring was continued at 70 C. for 1 hour to prepare a solution g. Meanwhile, 48.0 g of 2 mol/L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.8 g of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) were charged in a 100 mL beaker, followed by stirring at room temperature for 1 hour to prepare a solution h.

(67) In a 1 L poly beaker, 250 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) and 40.0 g of stevensite (Sumecton ST, manufactured by KUNIMINE INDUSTRIES CO., LTD.) were charged, followed by stirring at room temperature for 5 minutes. Using a water bath, the temperature was raised to 50 C. while stirring the mixture in the poly beaker and then a mixed solution of the total amount of the solution g and the total amount of the solution h was added dropwise over 1 hour. After completion of the dropwise addition, stirring was continued at 50 C. for 6 hours. After 6 hours have elapsed, cooling to room temperature was performed and stirring was stopped. A solid was separated by pressure filtration of the obtained mixture, and this solid was washed with water and filtered by pressure filtration and then repeatedly washed until the pH of the washing filtrate becomes 5 or higher. After washing, the obtained solid was dried overnight at 110 C. to prepare a catalyst W.

Example 40

(68) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst W obtained in Reference Example 23 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 11.5% and the selectivity of cyclohexanone oxime was 93.7%.

Reference Example 24

(69) In a 1 L recovery flask, 200 g of deionized water and 0.51 g of ruthenium chloride hydrate (manufactured by FURUYA METAL Co., Ltd., Ru content: 40.75% by weight) were charged, followed by stirring at room temperature for 5 minutes. To the obtained mixture, 20.1 g of the catalyst P obtained in Reference Example 16 was added, followed by stirring at room temperature for 1 hour. Next, a solid was separated by distilling off water from the obtained mixture at 50 C. under reduced pressure using a rotary evaporator. This solid was calcined at 450 C. under air flow at a flow rate of 50 mL/minute for 6 hours to prepare a catalyst X.

Example 41

(70) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst X obtained in Reference Example 24 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 38.1% and the selectivity of cyclohexanone oxime was 93.6%.

Reference Example 25

(71) In a 500 mL recovery flask, 50.5 g of deionized water and 0.12 g of nickel(II) chloride (anhydrous, NiCl.sub.2, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by stirring at room temperature for 5 minutes. To the obtained mixture, 5.0 g of the catalyst P obtained in Reference Example 16 was added, followed by stirring at room temperature for 1 hour. Next, a solid was separated by distilling off water from the obtained mixture at 50 C. under reduced pressure using a rotary evaporator. This solid was calcined at 450 C. under air flow at a flow rate of 50 mL/minute for 6 hours to prepare a catalyst Y.

Example 42

(72) The same operation as in Example 1 was performed, except that 0.30 g of the catalyst Y obtained in Reference Example 25 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 0.3% and the selectivity of cyclohexanone oxime was 61.1%.

Example 43

(73) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst Y obtained in Reference Example 25 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 34.2% and the selectivity of cyclohexanone oxime was 94.6%.

Reference Example 26

(74) The same operation as in Reference Example 25 was performed, except that 0.10 g of gold(III) chloride acid tetrahydrate (HAuCl.sub.4.4H.sub.2O, manufactured by Kanto Chemical Co., Inc.) was used in place of 0.12 g of nickel (II) chloride, a catalyst Z was prepared.

Example 44

(75) The same operation as in Example 1 was performed, except that 0.30 g of the catalyst Z obtained in Reference Example 26 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 2.1% and the selectivity of cyclohexanone oxime was 82.7%.

Example 45

(76) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst Z obtained in Reference Example 26 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 31.2% and the selectivity of cyclohexanone oxime was 91.7%.

Reference Example 27

(77) In a 200 mL recovery flask, 40.0 g of deionized water and 1.14 g of aluminum nitrate octahydrate (Al(NO.sub.3).sub.3.9H.sub.2O, manufactured by Wako Pure Chemical Industries, Ltd.) were charged, followed by stirring at room temperature to obtain a solution. To the obtained solution, 4.0 g of the catalyst P obtained in Reference Example 16 was added and then a mixed solution of 0.36 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 30.0 g of deionized water was added dropwise, followed by stirring at room temperature for 2 hours. Next, a solid was separated by pressure filtration of the obtained mixture, and this solid was washed with 400 mL of water and filtered by pressure filtration. After washing, the obtained solid was dried overnight at 110 C. and the obtained dried substance was calcined at 200 C. under air flow at a flow rate of 50 mL/minute for 6 hours to prepare a catalyst a.

Example 46

(78) The same operation as in Example 3 was performed, except that 0.30 g of the catalyst a obtained in Reference Example 27 was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 28.1% and the selectivity of cyclohexanone oxime was 93.1%.

Comparative Example 1

(79) The same operation as in Example 1 was performed, except that 0.30 g of titanium oxide (TiO.sub.2, ST-01, manufactured by ISHIHARA SANGYO KAISHA, LTD.) was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 0.2% and the selectivity of cyclohexanone oxime was 5.6%.

Comparative Example 2

(80) The same operation as in Example 3 was performed, except that 0.30 g of titanium oxide (TiO.sub.2, ST-01, manufactured by ISHIHARA SANGYO KAISHA, LTD.) was used in place of 0.30 g of the catalyst A. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 3.1% and the selectivity of cyclohexanone oxime was 46.3%.

Comparative Example 3

(81) The same operation as in Example 17 was performed, except that 7.50 g of titanium oxide (TiO.sub.2, ST-01, manufactured by ISHIHARA SANGYO KAISHA, LTD.) was used in place of 7.53 g of the catalyst H. The obtained filtrate was analyzed. As a result, the conversion ratio of cyclohexylamine was 0.2% and the selectivity of cyclohexanone oxime was 10.6%.