Method for producing 3-methylcycloalkenone compound

Abstract

The present invention relates to a method for producing a 3-methylcycloalkenone compound and a method for producing muscone. In the presence of a zirconium oxide catalyst, a diketone represented by the following general formula (1): ##STR00001##
wherein in formula (1), n represents 8, 9, 10, 11 or 12,
is subjected to a vapor-phase intramolecular condensation reaction, whereby a 3-methylcycloalkenone compound can be produced with high reaction efficiency. When a 3-methylcyclopentadecenone compound produced by this method is hydrogenated in a known manner, muscone can be produced efficiently.

Claims

1. A method for producing a 3-methylcycloalkenone compound represented by the following general formula (2), comprising vaporizing a diketone represented by the following general formula (1): ##STR00015## wherein in formula (1), n represents 8, 9, 10, 11 or 12, and contacting the vaporized diketone of formula (1) with a catalyst consisting of zirconium oxide and an optional additional metal oxide, wherein an amount of the optional additional metal oxide in the catalyst is 3 mass % or less, to cause a vapor-phase intramolecular condensation reaction thereby producing a 3-methylcycloalkenone compound represented by the following general formula (2): ##STR00016## wherein in formula (2), among the three double lines each consisting of solid and dotted lines, one represents a double bond and the other two represent single bonds, in which the configuration of the double bond may be either cis or trans, and n is as defined in general formula (1), wherein a mass ratio of the vaporized diketone of formula (1) to the catalyst is 0.2 or more.

2. The method according to claim 1, wherein the catalyst consists of zirconium oxide.

3. The method according to claim 1, wherein the catalyst consists of zirconium oxide and an additional metal oxide, wherein an amount of the additional metal oxide in the catalyst is 3 mass % or less.

4. The method according to claim 3, wherein the additional metal oxide is alumina.

5. The method according to claim 1, wherein the diketone represented by general formula (1) is 2,15-hexadecanedione, and the 3-methylcycloalkenone compound represented by general formula (2) generated upon the intramolecular condensation reaction is a 3-methylcyclopentadecenone compound.

6. The method according to claim 1, wherein the catalyst is filled into a reactor, and wherein the method comprises continuously feeding the vaporized diketone represented by general formula (1) to the reactor in an amount of 0.01 to 50 g/hr relative to 1 g of the catalyst filled into the reactor to effect the intramolecular condensation reaction.

7. A method for producing muscone, comprising vaporizing 2,15-hexadecanedione; and contacting the vaporized 2,15-hexadecanedione with a catalyst consisting of zirconium oxide and an optional additional metal oxide, wherein an amount of the optional additional metal oxide in the catalyst is 3 mass % or less, to cause a vapor-phase intramolecular condensation reaction thereby producing a 3-methylcyclopentadecenone compound represented by the following general formula (2′): ##STR00017## wherein among the three double lines each consisting of solid and dotted lines, one represents a double bond and the other two represent single bonds, the configuration of the double bond may be either cis or trans, and n′ represents 10, wherein a mass ratio of the vaporized diketone of formula (1) to the catalyst is 0.2 or more, and hydrogenating the produced 3-methylcyclopentadecenone compound.

8. The method for producing muscone according to claim 7, filling wherein the catalyst is filled into a reactor, and wherein the method comprises continuously feeding 2,15-hexadecanedione to the reactor in an amount of 0.01 to 50 g/hr relative to 1 g of the catalyst filled into the reactor to effect the intramolecular condensation reaction.

9. The method for producing muscone according to claim 7, wherein the catalyst consists of zirconium oxide.

10. The method for producing muscone according to claim 7, wherein the catalyst consists of zirconium oxide and an additional metal oxide, wherein an amount of the additional metal oxide in the catalyst is 3 mass % or less.

11. The method for producing muscone according to claim 10, wherein the additional metal oxide is alumina.

12. The method of claim 1, wherein the catalyst is in a molded form.

13. The method of claim 12, wherein the catalyst is in a form of a pellet.

14. The method of claim 13, wherein the pellet has a size of 1 to 10 mm.

15. The method of claim 6, wherein the vaporized diketone is fed into the reactor with a carrier gas.

16. The method of claim 1, wherein the vapor-phase intramolecular condensation reaction is performed at atmospheric pressure.

17. The method of claim 1, wherein the diketone is vaporized in a pristine form.

18. The method of claim 1, wherein the diketone is vaporized in a solution comprising the diketone and a solvent, which is a hydrocarbon.

19. The method of claim 1, wherein the zirconium oxide is uncalcinated zirconium oxide.

20. The method of claim 1, wherein the zirconium oxide is calcinated zirconium oxide.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 schematically illustrates an embodiment of a production apparatus which may be effectively used in the method of the present invention for producing a 3-methylcycloalkenone compound.

DESCRIPTION OF EMBODIMENTS

(2) The present invention will be described in more detail below.

(3) The present invention is directed to a method for producing a 3-methylcycloalkenone compound represented by the following general formula (2), comprising performing a vapor-phase intramolecular condensation reaction in the presence of a catalyst comprising zirconium oxide on 0.2-fold or more mass, relative to the catalyst, of a diketone represented by the following general formula (1):

(4) ##STR00008##
wherein in formula (1), n represents 8, 9, 10, 11 or 12,

(5) ##STR00009##
wherein in formula (2), among the three double lines each consisting of solid and dotted lines, one represents a double bond and the other two represent single bonds, the configuration of the double bond may be either cis or trans, and n is as defined in general formula (1).

(6) <Starting Material Compound>

(7) A diketone used as a starting material compound in the present invention is represented by the following general formula (1):

(8) ##STR00010##
wherein in formula (1), n represents 8, 9, 10, 11 or 12.

(9) The diketone used as a starting material compound in the present invention is specifically exemplified by 2,13-tetradecanedione, 2,14-pentadecanedione, 2,15-hexadecanedione, 2,16-heptadecanedione and 2,17-octadecanedione. In the present invention, these diketones may be used either alone or in combination.

(10) Such a starting material diketone may be produced in any manner. For example, it is possible to use a diketone produced by reacting an aliphatic halide with ketones in the presence of a base.

(11) It should be noted that when 2,15-hexadecanedione is used as a starting material diketone in the present invention, a 3-methylcyclopentadecenone compound obtained therefrom upon intramolecular condensation reaction may be hydrogenated to thereby obtain muscone that is useful as a perfume.

(12) The amount of the diketone used as a starting material compound in the present invention is 0.2-fold or more mass, preferably 0.3-fold or more mass, more preferably 1-fold or more mass, relative to the catalyst. When the diketone is used in an amount of 0.2-fold or more mass relative to the catalyst, the desired 3-methylcycloalkenone compound can be produced with high reaction efficiency. Moreover, the desired 3-methylcycloalkenone compound can be produced with high conversion and high selectivity while maintaining a high feed rate of the starting material. In terms of maintaining high conversion, the amount of the diketone to be used is, but not limited to, preferably 1000-fold or less mass, more preferably 500-fold or less mass, relative to the catalyst.

(13) <Catalyst>

(14) The catalyst used in the present invention may be of single component consisting of zirconium oxide (zirconium dioxide (ZrO.sub.2), also referred to as zirconia) or may comprise zirconium oxide and one or more additional components. When the catalyst comprises zirconium oxide and one or more additional components, the catalyst may be a physical mixture of zirconium oxide and an additional component(s), or zirconium oxide and an additional component(s) may form a composite. When zirconium oxide and an additional component(s) form a composite, the morphology of the composite is not limited in any way. For example, zirconium oxide and an additional component(s) may form a composite at the atomic level, or an additional component(s) may be supported, e.g., on the surface of zirconium oxide to form a composite. Such a composite of zirconium oxide and an additional component(s) may be produced in any manner, for example, by impregnation, kneading or coprecipitation techniques as appear in Non-patent Literature 4.

(15) Examples of additional components include, but are not limited to, SO.sub.4, PO.sub.4, B.sub.2O.sub.3 and metal oxides (except for zirconium oxide), etc. Specific examples of metal oxides include Al.sub.2O.sub.3(alumina), SiO.sub.2, WO.sub.3, CaO, MgO, BeO, Na.sub.2O, K.sub.2O, Li.sub.2O, Cs.sub.2O, TiO.sub.2, CeO.sub.2, VO.sub.2, V.sub.2O.sub.5, Cr.sub.2O.sub.3, MnO, MnO.sub.2, Mn.sub.2O.sub.3, Fe.sub.2O.sub.3, Co.sub.3O.sub.4, NiO, CuO, Ga.sub.2O.sub.3, GeO.sub.2, Rb.sub.2O, SrO, Y.sub.2O.sub.3, Nb.sub.2O.sub.5, In.sub.2O.sub.3, SnO.sub.2, MoO.sub.3, Sb.sub.2O.sub.5, ThO.sub.2, CdO, ZnO, BaO, Ta.sub.2O.sub.5, Bi.sub.2O.sub.3, La.sub.2O.sub.3, Pr.sub.2O.sub.3, Nd.sub.2O.sub.3, Sm.sub.2O.sub.3, Eu.sub.2O.sub.3, Gd.sub.2O.sub.3, Tb.sub.2O.sub.3, Dy.sub.2O.sub.3, Ho.sub.2O.sub.3, Tm.sub.2O.sub.3, Yb.sub.2O.sub.3, and Lu.sub.2O.sub.3, etc. Among them, Al.sub.2O.sub.3 is preferred in terms of reactivity and stability.

(16) The amount of such a metal oxide(s) contained in the catalyst is not limited in any way, but it is preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less, based on the total weight of the catalyst.

(17) Zirconium oxide for use as a catalyst or a catalyst comprising zirconium oxide may be used in the uncalcined state or may be subjected to calcination treatment before use. The temperature for calcination treatment of the catalyst is preferably 400° C. to 1000° C., more preferably 600° C. to 900° C., and particularly preferably 700° C. to 900° C. Likewise, the calcination time is preferably 1 to 48 hours, more preferably 2 to 36 hours, and particularly preferably 3 to 12 hours.

(18) The crystal structure of zirconium oxide for use as a catalyst or a catalyst comprising zirconium oxide is not limited in any way, and it is possible to use any structure of monoclinic, tetragonal, cubic or amorphous system.

(19) Zirconium oxide for use as a catalyst or a catalyst comprising zirconium oxide may be used in either powder or molded form, but is preferably used in molded from in terms of its handling. The molded form may be of any size and any shape. For example, it is possible to use the catalyst in molded form of pellet (i.e., short columnar), spherical, cubic, rectangular, discal, ellipsoidal or cylindrical shape having a size of 1 to 10 mm, preferably around 1 to 5 mm.

(20) The BET specific surface area of zirconium oxide for use as a catalyst or a catalyst comprising zirconium oxide is not limited in any way, but it is preferably 10 m.sup.2/g to 200 m.sup.2/g, and more preferably 10 m.sup.2/g to 100 m.sup.2/g. It should be noted that the specific surface area tends to be smaller at a higher calcination temperature in most cases.

(21) <Reactor>

(22) Any type of reactor may be used, as long as it is a reaction apparatus in which the starting material diketone can be vaporized and contacted to the catalyst to effect an intramolecular condensation reaction.

(23) Above all, a catalyst packed bed reactor is preferred for use as a reactor. A catalyst packed bed reactor is designed such that a catalyst is filled in layered form into a cylindrical container, into one end of which a starting material is fed and from the other end of which a reaction product is discharged. FIG. 1 schematically illustrates an embodiment of a catalyst packed bed reactor. The starting material may be fed into starting material feeding line 1, vaporized in vaporizer 2 (equipped with a heater), continuously fed into one end of catalyst packed reactor 3 (equipped with a heater), and contacted with the catalyst in the vapor phase state to cause a reaction. The product may be continuously discharged from the other end of catalyst packed reactor 3 (equipped with a heater), cooled with condenser 4, and collected into reaction product receiver 5. In the present invention, such a catalyst packed bed reactor may have any inner diameter and any length, and may be designed to have a size suitable for each situation.

(24) When the present invention is carried out using a catalyst packed bed reactor, it is preferred, but not limited to, that zirconium oxide for use as a catalyst or a catalyst comprising zirconium oxide is filled in layered form into a cylindrical reactor, into which the starting material diketone vaporized with a vaporizer or the like is continuously fed through one end of the catalyst packed bed reactor, and contacted in the vapor phase state with the zirconium oxide for use as a catalyst or the catalyst comprising zirconium oxide to cause an intramolecular condensation reaction, while a product comprising a 3-methylcycloalkenone compound is continuously discharged from the other end of the catalyst packed bed reactor.

(25) <Solvent>

(26) The starting material diketone may be used directly or may be dissolved in a solvent before use. As a solvent, a hydrocarbon is generally used and, in particular, an aliphatic hydrocarbon containing 6 to 14 carbon atoms is preferred, but any solvent may be used as long as it is inert to the intended reaction. Specific examples include toluene, xylene, mesitylene, decane, dodecane, isododecane, decalin, and tetradecane, etc.

(27) The amount of such a solvent to be used is not limited in any way, but it is 0- to 100-fold mass, preferably 5- to 50-fold mass, particularly preferably 5- to 30-fold mass, relative to the starting material diketone.

(28) <Carrier Gas>

(29) A carrier gas is not limited in any way, as long as it is inert to the intended reaction. For example, nitrogen or carbon dioxide may be used for this purpose. The amount of such a carrier gas to be used is generally 0.2 L to 20 L relative to 1 g of the starting material, because too high an amount is not cost-effective while too low an amount is of no help in controlling side reactions.

(30) <Evaporation Unit Temperature>

(31) The temperature of a vaporizer where the starting material diketone is vaporized, i.e., the temperature of an evaporation unit is generally 250° C. to 500° C., but it is not limited to this range and may be a temperature at which the starting material diketone is completely vaporized.

(32) <Feed Rate of Starting Material>

(33) When the starting material diketone is continuously fed to the reactor to effect an intramolecular condensation reaction, the feed rate of the starting material diketone to the reactor may be adjusted as appropriate depending on the type of the starting material diketone, the type and structure of the reactor, etc. For example, the starting material diketone may be continuously fed to the reactor in an amount of 0.01 to 50 g/hr, preferably 0.05 to 20 g/hr, particularly preferably 0.05 to 5 g/hr, relative to 1 g of the catalyst filled into the reactor, to effect an intramolecular condensation reaction with high reaction efficiency. The production method of the present invention allows intramolecular condensation with high reaction efficiency even when increasing the feed rate of the starting material as mentioned above. Further, in a preferred embodiment, the present invention enables the production of a 3-methylcycloalkenone compound with high conversion and high selectivity and with high reaction efficiency even when increasing the feed rate of the starting material.

(34) <Reaction Temperature>

(35) The reaction temperature is preferably in the range of 250° C. to 500° C., and particularly preferably in the range of 300° C. to 450° C., because the reaction does not proceed at too low a temperature while side reactions will proceed at too high a temperature.

(36) <Product Collection>

(37) The reaction product may be collected by being cooled to between 0° C. and 60° C. This reaction product (hereinafter referred to as a reaction product solution) is mainly composed of the solvent used, the 3-methylcycloalkenone compound generated, and the starting material diketone remaining unreacted. From the resulting reaction product solution, the 3-methylcycloalkenone compound and the starting material diketone remaining unreacted can be separated individually by any known separation techniques such as crystallization separation or distillation.

(38) The unreacted diketone collected by known separation techniques such as crystallization separation or distillation from the resulting reaction product solution may be recycled.

(39) The thus obtained 3-methylcycloalkenone compound is represented by the following general formula (2):

(40) ##STR00011##
wherein in formula (2), among the three double lines each consisting of solid and dotted lines, one represents a double bond and the other two represent single bonds, the configuration of the double bond may be either cis or trans, and n is as defined in general formula (1). In more detail, it is (E)-3-methyl-2-cycloalkenone, (Z)-3-methyl-2-cycloalkenone, (E)-3-methyl-3-cycloalkenone, (Z)-3-methyl-3-cycloalkenone, or 3-methylene-cycloalkanone.

(41) <Method for Producing Muscone>

(42) When 2,15-hexadecanedione is used as a starting material diketone, the reaction product is mainly composed of a 3-methylcyclopentadecenone compound-containing solution comprising the solvent used, the 3-methylcyclopentadecenone compound generated, and 2,15-hexadecanedione remaining unreacted. After removal of the unreacted 2,15-hexadecanedione by crystallization or distillation from the 3-methylcyclopentadecenone compound-containing solution obtained as the reaction product solution, the 3-methylcyclopentadecenone compound may be used directly, i.e., in the form of the 3-methylcyclopentadecenone compound-containing solution comprising the solvent used, or the 3-methylcyclopentadecenone compound-containing solution may further be treated to replace the solvent used with an appropriate solvent, followed by hydrogenation of the olefin moiety in a known manner to give muscone. Alternatively, the 3-methylcyclopentadecenone compound-containing solution obtained as the reaction product solution may be used directly, i.e., in the form of the 3-methylcyclopentadecenone compound-containing solution comprising the solvent used and 2,15-hexadecanedione remaining unreacted. or the 3-methylcyclopentadecenone compound-containing solution may be treated to replace the solvent used with an appropriate solvent, followed by hydrogenation of the olefin moiety in a known manner to give muscone.

(43) The olefin moiety of the 3-methylcyclopentadecenone compound may be hydrogenated in any manner. For example, the olefin moiety may be hydrogenated in the presence of a palladium catalyst, as described in Patent Literature 2, or the olefin moiety may be hydrogenated in the presence of a ruthenium catalyst, as described in Patent Literature 3.

(44) Namely, the present invention also encompasses a method for producing muscone, comprising performing a vapor-phase intramolecular condensation reaction in the presence of a catalyst comprising zirconium oxide on 0.2-fold or more mass, relative to the catalyst, of 2,15-hexadecanedione to generate a 3-methylcyclopentadecenone compound represented by the following general formula (2′):

(45) ##STR00012##
wherein among the three double lines each consisting of solid and dotted lines, one represents a double bond and the other two represent single bonds, the configuration of the double bond may be either cis or trans, and n′ represents 10, and

(46) hydrogenating the 3-methylcyclopentadecenone compound.

(47) Moreover, the present invention also encompasses a method for producing muscone, comprising performing a vapor-phase intramolecular condensation reaction in the presence of a catalyst comprising zirconium oxide on 0.2-fold or more mass, relative to the catalyst, of 2,15-hexadecanedione to generate a 3-methylcyclopentadecenone compound-containing solution comprising a 3-methylcyclopentadecenone compound represented by the following general formula (2′):

(48) ##STR00013##
wherein among the three double lines each consisting of solid and dotted lines, one represents a double bond and the other two represent single bonds, the configuration of the double bond may be either cis or trans, and n′ represents 10, and

(49) hydrogenating the 3-methylcyclopentadecenone compound contained in the 3-methylcyclopentadecenone compound-containing solution.

(50) Moreover, the present invention also encompasses a method for producing muscone, comprising performing a vapor-phase intramolecular condensation reaction in the presence of a catalyst comprising zirconium oxide on 0.2-fold or more mass, relative to the catalyst, of 2,15-hexadecanedione to generate a 3-methylcyclopentadecenone compound-containing solution comprising a 3-methylcyclopentadecenone compound represented by the following general formula (2′):

(51) ##STR00014##
wherein among the three double lines each consisting of solid and dotted lines, one represents a double bond and the other two represent single bonds, the configuration of the double bond may be either cis or trans, and n′ represents 10,

(52) subjecting the 3-methylcyclopentadecenone compound-containing solution to crystallization separation to remove the starting material 2,15-hexadecanedione, and

(53) hydrogenating the 2,15-hexadecanedione-free 3-methylcyclopentadecenone compound-containing solution.

EXAMPLES

(54) The present invention will be further described in more detail by way of the following examples and comparative examples, which are not intended to limit the present invention.

(55) In the following examples and comparative examples, the reaction products were measured by gas chromatography (GLC).

(56) Analytical instrument used: GC2010 gas chromatograph (Shimadzu Corporation, Japan)

(57) Column: Agilent BC-WAX (0.25 mm×30 m×0.3 μm)

(58) Detector: FID

(59) Moreover, in the following examples, conversion, selectivity and yield were determined according to the following equations.
Conversion (%)={(W.sub.0−W.sub.1)/W.sub.0}×100
Selectivity (%)={W.sub.a/(W.sub.0−W.sub.1)}×100
Yield (%) {W.sub.a/W.sub.0}×100

(60) It should be noted that W.sub.0, W.sub.1 and W.sub.a in the above equations are as defined below.

(61) W.sub.0=the number of moles of the starting material (the total number of moles of the starting material fed to the reactor)

(62) W.sub.1=the remaining number of moles of the starting material (the number of moles of the starting material remaining in the reaction product)

(63) W.sub.a=the number of moles of the desired product (i.e., a corresponding 3-methylcycloalkenone compound) in the reaction product

Example 1

(64) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 70 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 100 g of uncalcined zirconium oxide pellets (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 63.6 m.sup.2/g) was then filled as a catalyst, onto which 70 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 12 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(65) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 0.2-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 2

(66) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 70 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 100 g of uncalcined zirconium oxide pellets (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 63.6 m.sup.2/g) was then filled as a catalyst, onto which 70 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 12 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(67) This reaction was continued for 100 hours. The 2,15-hexadecanedione was used in an amount of 1.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 3

(68) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 20 g of uncalcined zirconium oxide pellets (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 63.6 m.sup.2/g) was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 12 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(69) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 1.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 4

(70) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 20 g of uncalcined zirconium oxide pellets (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 63.6 m.sup.2/g) was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 12 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(71) This reaction was continued for 6 hours. The 2,15-hexadecanedione was used in an amount of 0.3-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 5

(72) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 20 g of uncalcined zirconium oxide pellets (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 63.6 m.sup.2/g) was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 300° C. and the catalyst packed bed reactor was heated to 300° C. While passing nitrogen as a carrier gas at a rate of 30 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(73) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 1.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 6

(74) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 20 g of calcined zirconium oxide pellets obtained by calcining zirconium oxide pellets (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area 63.6 m.sup.2/g) in air at 700° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 300° C. and the catalyst packed bed reactor was heated to 300° C. While passing nitrogen as a carrier gas at a rate of 30 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(75) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 1.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 7

(76) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 20 g of calcined zirconium oxide pellets obtained by calcining zirconium oxide pellets (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 63.6 m.sup.2/g) in air at 900° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 300° C. and the catalyst packed bed reactor was heated to 300° C. While passing nitrogen as a carrier gas at a rate of 30 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(77) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 1.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 8

(78) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 20 g of calcined composite zirconium oxide pellets containing 0.24% by mass of alumina obtained by calcining composite zirconium oxide pellets containing 0.24% by mass of alumina (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 80.5 m.sup.2/g) in air at 550° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 300° C. and the catalyst packed bed reactor was heated to 300° C. While passing nitrogen as a carrier gas at a rate of 30 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(79) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 1.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 9

(80) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 20 g of calcined composite zirconium oxide pellets containing 0.24% by mass of alumina obtained by calcining composite zirconium oxide pellets containing 0.24% by mass of alumina (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 80.5 m.sup.2/g) in air at 800° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 30 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(81) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 1.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 10

(82) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 20 g of calcined composite zirconium oxide pellets containing 0.70% by mass of alumina obtained by calcining composite zirconium oxide pellets containing 0.70% by mass of alumina (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 89.3 m.sup.2/g) in air at 550° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled.

(83) A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 300° C. and the catalyst packed bed reactor was heated to 300° C. While passing nitrogen as a carrier gas at a rate of 30 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(84) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 1.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 11

(85) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 20 g of calcined composite zirconium oxide pellets containing 0.74% by mass of alumina (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 27.4 m.sup.2/g) which had been calcined in air at 800° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled.

(86) A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 30 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(87) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 1.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 12

(88) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 10 g of calcined composite zirconium oxide pellets containing 0.74% by mass of alumina (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 27.4 m.sup.2/g) which had been calcined in air at 800° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 30 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(89) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 2.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 13

(90) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 10 g of calcined composite zirconium oxide pellets containing 1.01% by mass of alumina obtained by calcining composite zirconium oxide pellets containing 1.01% by mass of alumina (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 106 m.sup.2/g) in air at 800° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 30 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(91) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 2.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 14

(92) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 10 g of calcined composite zirconium oxide pellets containing 2.98% by mass of alumina obtained by calcining composite zirconium oxide pellets containing 2.98% by mass of alumina (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 182 m.sup.2/g) in air at 800° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 30 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(93) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 2.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 15

(94) Into the bottom of a catalyst packed bed reactor (21.5 mm+, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 10 g of calcined composite zirconium oxide pellets containing 0.76% by mass of alumina (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (2 mm+, BET specific surface area: 31.1 m.sup.2/g) which had been calcined in air at 800° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 400° C. and the catalyst packed bed reactor was heated to 380° C. While passing nitrogen as a carrier gas at a rate of 12 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 77 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(95) This reaction was continued for 20 hours. The 2,15-hexadecanedione was used in an amount of 5.6-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

Example 16

(96) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 85 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 20 g of calcined composite zirconium oxide pellets containing 0.76% by mass of alumina (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (2 mmϕ, BET specific surface area: 31.1 m.sup.2/g) which had been calcined in air at 800° C. for 3 hours was then filled as a catalyst, onto which 85 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 410° C. and the catalyst packed bed reactor was heated to 392° C. While passing nitrogen as a carrier gas at a rate of 24 L/hr, a solution containing 7.04% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 142 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(97) This reaction was continued for 100 hours. The 2,15-hexadecanedione was used in an amount of 50.0-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 1 described later.

(98) TABLE-US-00001 TABLE 1 Catalyst comprising zirconium oxide Mass BET Intramolecular condensation ratio of specific reaction of diketone diketone Alumina Calcination surface Feed rate Condensation Reaction relative Reaction product content temperature area.sup.1) of starting temperature time to catalyst Conversion Selectivity Yield (% by mass) (° C.) (m.sup.2/g) material.sup.2) (° C.) (hour) (fold mass) (%) (%) (%) Example 1 0.0 — 63.6 0.01 340 20 0.2 99 4 4 Example 2 0.0 — 63.6 0.01 340 100 1.0 91 45 41 Example 3 0.0 — 63.6 0.05 340 20 1.0 60 63 37 Example 4 0.0 — 63.6 0.05 340 6 0.3 81 42 34 Example 5 0.0 — 63.6 0.05 300 20 1.0 43 51 22 Example 6 0.0 700 — 0.05 300 20 1.0 63 57 36 Example 7 0.0 900 — 0.05 300 20 1.0 40 82 33 Example 8 0.24 550 — 0.05 300 20 1.0 80 46 37 Example 9 0.24 800 — 0.05 340 20 1.0 73 74 54 Example 10 0.70 550 — 0.05 300 20 1.0 88 44 39 Example 11 0.74 800 27.4 0.05 340 20 1.0 95 65 62 Example 12 0.74 800 27.4 0.10 340 20 2.0 77 72 55 Example 13 1.01 800 — 0.10 340 20 2.0 75 71 53 Example 14 2.98 800 — 0.10 340 20 2.0 72 66 48 Example 15 0.76 800 31.1 0.28 380 20 5.6 91 75 68 Example 16 0.76 800 31.1 0.50 392 100 50.0 88 78 69 .sup.1)“—” means not measured .sup.2)Feed rate (g) of the starting material per hour relative to 1 g of the catalyst (unit: g/g-cat .Math. hr)

Comparative Example 1

(99) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 70 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 100 g of uncalcined zirconium oxide pellets (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 63.6 m.sup.2/g) was then filled as a catalyst, onto which 70 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 12 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(100) This reaction was continued for 6 hours. The 2,15-hexadecanedione was used in an amount of 0.06-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 2 described later.

Comparative Example 2

(101) Into the bottom of a catalyst packed bed reactor (21.5 mmϕ, 700 mm long), 70 g of magnetic Raschig rings (TO-TOKU Engineering Corporation, Japan) was filled, onto which 100 g of uncalcined zirconium oxide pellets (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Japan) (5 mmϕ, BET specific surface area: 63.6 m.sup.2/g) was then filled as a catalyst, onto which 70 g of the magnetic Raschig rings was further filled. A vaporizer was equipped on the top of the catalyst packed bed reactor, and the vaporizer was heated to 340° C. and the catalyst packed bed reactor was heated to 340° C. While passing nitrogen as a carrier gas at a rate of 12 L/hr, a solution containing 3.65% by mass of 2,15-hexadecanedione in xylene was introduced at a rate of 27 g/hr through the vaporizer into the catalyst packed bed reactor to effect an intramolecular condensation reaction. This reaction product was cooled to 10° C. or below and collected.

(102) This reaction was continued for 12 hours. The 2,15-hexadecanedione was used in an amount of 0.12-fold mass relative to the catalyst. The collected reaction product solution was analyzed by gas chromatography to determine conversion, 3-methylcyclopentadecenone compound selectivity and yield. The results obtained are shown in Table 2 described later.

(103) TABLE-US-00002 TABLE 2 Catalyst comprising zirconium oxide Intramolecular condensation Mass BET reaction of diketone ratio of specific Feed diketone Alumina Calcination surface rate of Condensation Reaction relative Reaction product content temperature area starting temperature time to catalyst Conversion Selectivity Yield (% by mass) (° C.) (m.sup.2/g) material.sup.1) (° C.) (hour) (fold mass) (%) (%) (%) Comparative 0 — 63.6 0.01 340  6 0.06 100 0 0 Example 1 Comparative 0 — 63.6 0.01 340 12 0.12 100 0 0 Example 2 .sup.1)Feed rate (g) of the starting material per hour relative to 1 g of the catalyst (unit: g/g-cat .Math. hr)

(104) As described in Patent Literature 3, even in the case of using zirconium oxide as a catalyst, any desired 3-methylcyclopentadecenone compound was not obtained at all when the feed rate of the starting material was low and the reaction time was not sufficient.

[Example 17] Method for Producing Muscone

(105) The reaction product solution obtained in Example 16 was concentrated and 1200 g of heptane was added thereto, followed by warming to 50° C. The mixture was then cooled slowly to precipitate 2,15-hexadecanedione remaining unreacted. After cooling to −10° C., the precipitated crystal was removed by filtration separation to obtain 1690 g of a heptane solution containing a 3-methylcyclopentadecenone compound. The heptane solution contained 614 g of the 3-methylcyclopentadecenone compound and was free from 2,15-hexadecanedione. The dry weight of the resulting crystal was 132 g, and the content of 2,15-hexadecanedione was 123 g.

(106) The thus obtained heptane solution containing the 3-methylcyclopentadecenone compound was taken in an amount of 138 g and concentrated, followed by addition of 5% by mass of palladium on carbon (0.1 g) as a catalyst and 2-propanol (80 g) as a solvent to effect a reaction under 2.0 MPa hydrogen pressure at 25° C. for 20 hours. After the reaction, 5% by mass of palladium on carbon as a catalyst was removed by filtration separation, and the filtrate was concentrated and rectified to obtain 40 g of muscone with a purity of 99% by mass.

INDUSTRIAL APPLICABILITY

(107) The present invention provides efficient production methods for muscone which is useful as a perfume, 3-methylcyclopentadecenone which is a synthetic intermediate for muscone, and other 3-methylcycloalkenone compounds.

REFERENCE SIGNS LIST

(108) 1 Starting material feeding line 2 Vaporizer (equipped with a heater) 3 Catalyst packed reactor (equipped with a heater) 4 Condenser 5 Reaction product receiver