Method for producing cyclic diketone compounds

Abstract

To provide a method for high-yield oxidative cleavage of a bicyclic tetrasubstituted olefin compound.SOLUTION: A method for producing a compound represented by formula (I) comprises a step of oxidative cleavage of a compound represented by formula (II) by using an oxidizer in the presence of a metal catalyst including at least one metal element selected from the group consisting of vanadium, iron and molybdenum. [The formula -A1- is a substituted / unsubstituted C2-C6 alkylene group; and the formula -A2- is a substituted / unsubstituted C4-C10 alkylene group.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a compound represented by general formula (I). [Background technology]

[0002] Macrocyclic compounds are known to exhibit useful activities in pharmaceuticals, fragrances, and pesticides. Muscenone, a macrocyclic ketone, is a fragrance material with excellent biodegradability, long-lasting fragrance, and an elegant texture. In response to the growing need for easily biodegradable synthetic musk materials in recent years, various manufacturing methods have been disclosed.

[0003] Patent Document 1 discloses the production of cyclopentadecane-1,5-dione by oxidative cleavage of the tetrasubstituted double bond of 14-methylbicyclo[10.3.0]pentadecene[1(12)] with ozone or potassium permanganate.

[0004] Patent Document 2 discloses a production method in which a diketone compound is oxidatively cleaved using hydrogen peroxide in the presence of an acid catalyst or a tungstic acid compound. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 51-24498 [Patent Document 2] Patent Publication No. 2016-124867 Summary of the Invention [Problem to be solved by the invention]

[0006] The method of Patent Document 1 uses ozone, and therefore has low versatility and is not suitable for industrial use.

[0007] An object of the present invention is to provide a method for producing a compound represented by general formula (I) by oxidative cleavage of a compound of formula (II), which is a bicyclic tetrasubstituted olefin compound. [Means for solving the problem]

[0008] In order to solve the above-mentioned problems, the present inventors have conducted extensive research into the oxidative cleavage of tetra-substituted olefin compounds using oxidizing agents and have surprisingly found that, in the presence of a specific metal catalyst, an oxidative cleavage reaction of bicyclic tetra-substituted olefin compounds proceeds.

[0009] That is, the present invention is a method for producing a compound represented by general formula (I), which comprises a step of oxidatively cleaving a compound represented by general formula (II) using an oxidizing agent in the presence of a metal catalyst containing one or more metal elements selected from the group consisting of vanadium, iron, and molybdenum to obtain a compound represented by general formula (I).

[0010] [ka]

[0011] In the formula (I) and formula (II), Formula-A 1 -(However, the previous bond is the carbon atom C 1 The latter bond is the carbon atom C 2 (meaning a bond bonded to) is an alkylene group having from 2 to 6 carbon atoms, which may be substituted and may include an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these; Formula-A 2 -(However, the previous bond is the carbon atom C 1 The latter bond is the carbon atom C 2 (meaning a bond bonded to) is an alkylene group having from 4 to 10 carbon atoms, which may be substituted and may include an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these. [Effects of the Invention]

[0012] According to the present invention, a compound represented by general formula (I) can be produced by oxidative cleavage of a compound of formula (II), which is a bicyclic tetrasubstituted olefin compound. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention is a method for producing a compound represented by general formula (I), which comprises a step of oxidatively cleaving a compound represented by general formula (II) (hereinafter, sometimes referred to as "a compound of formula (II)") using an oxidizing agent in the presence of a metal catalyst containing one or more metal elements selected from the group consisting of vanadium, iron, and molybdenum, to obtain a compound represented by general formula (I) (hereinafter, sometimes referred to as "a compound of formula (I)").

[0014] [ka]

[0015] In the formula (I) and formula (II), Formula-A 1 -(However, the previous bond is the carbon atom C 1 The latter bond is the carbon atom C 2 (meaning a bond bonded to) is an alkylene group having from 2 to 6 carbon atoms, which may be substituted and may include an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these; Formula-A 2 -(However, the previous bond is the carbon atom C 1 The latter bond is the carbon atom C 2 (meaning a bond bonded to) is an alkylene group having from 4 to 10 carbon atoms, which may be substituted and may include an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these.

[0016] The reason why the compound represented by general formula (I) can be produced by oxidative cleavage of a bicyclic tetrasubstituted olefin compound using an oxidizing agent in the presence of a metal catalyst is not clear, but it is thought that the oxidative cleavage is made possible by the restriction of the degrees of freedom of the four bonds connected to the double bond by the two ring structures.

[0017] [Compounds of formula (I) and compounds of formula (II)] In the formula (II) and formula (I), the formula -A 1 The "alkylene group having 2 to 6 carbon atoms" in the "alkylene group having 2 to 6 carbon atoms, which may be substituted and which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" is represented, for example, by the formula -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, and -(CH2)6-, with the formula -(CH2)3- and -(CH2)4- being preferred. Furthermore, the optionally substituted alkylene group having 2 to 6 carbon atoms is preferably an optionally substituted alkylene group having 3 or 4 carbon atoms.

[0018] In the formula (II) and formula (I), the formula -A 1The "alkylene group having from 2 to 6 carbon atoms and which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" in the "alkylene group having from 2 to 6 carbon atoms and which may be substituted and which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" refers to an alkylene group having from 2 to 6 carbon atoms and which contains in combination one or more selected from the group consisting of an ether bond (-O-), an ester bond (-C(=O)-O- or -OC(=O)-), a secondary amino group (-NH-), and a thioether group (-S-). However, the number of carbon atoms of the ester bond is not included in the number of carbon atoms of from 2 to 6. Examples of the "alkylene group having 2 to 6 carbon atoms which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group or any of these" include groups represented by the formula -CH2-O-CH2-, -CH2-C(=O)-O-CH2-, -CH2-NH-CH2-, -CH2-S-CH2-, -(CH2)2-O-CH2-, -(CH2)2-NH-(CH2)2-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5- and -(CH2)6-, with -(CH2)3- and -(CH2)4- being preferred.

[0019] In the formula (II) and formula (I), the formula -A 2 The "alkylene group having 4 to 10 carbon atoms" in the "alkylene group having 4 to 10 carbon atoms which may be substituted and which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" includes, for example, groups of the formula -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, and -(CH2) 10 -, and is represented by the formula -(CH2)4-, formula -(CH2)6-, formula -(CH2)8-, formula -(CH2) 10 - is preferred, and the formula -(CH2)4-, the formula -(CH2)6-, the formula -(CH2) 10Furthermore, the optionally substituted alkylene group having from 4 to 10 carbon atoms is preferably an optionally substituted alkylene group having 4, 6, 8, or 10 carbon atoms, more preferably an alkylene group having 4, 6, or 10 carbon atoms.

[0020] In the formula (II) and formula (I), the formula -A 2 The "alkylene group having 4 to 10 carbon atoms and which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" in the "alkylene group having 4 to 10 carbon atoms and which may be substituted and which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" refers to an alkylene group having 4 to 10 carbon atoms and which contains in combination one or more selected from the group consisting of an ether bond (-O-), an ester bond (-C(=O)-O- or -OC(=O)-), a secondary amino group (-NH-), and a thioether group (-S-). However, the number of carbon atoms of the ester bond is not included in the number of carbon atoms of 4 to 10. Examples of the "alkylene group having 4 to 10 carbon atoms and which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" include groups represented by the formula -(CH2)2-O-(CH2)2-, -(CH2)2-NH-(CH2)2-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, and -(CH2) 10 -, and the like, include the formula -(CH2)2-O-(CH2)2-, the formula -(CH2)4-, the formula -(CH2)6-, the formula -(CH2)8-, the formula -(CH2) 10 - is preferred, and the formula -(CH2)4-, the formula -(CH2)6-, the formula -(CH2) 10 - is more preferred.

[0021] Formula-A 1 "an alkylene group having 2 to 6 carbon atoms which may be substituted and which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" and formula -A 2The "alkylene group having from 4 to 10 carbon atoms, which may be substituted and may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" in the preceding paragraph means an "alkylene group having from 2 to 6 carbon atoms, which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these," and an "alkylene group having from 4 to 10 carbon atoms, which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these," each of which may have one or more, preferably one or two, substituents. Examples of the substituent include an alkyl group, an alkoxy group, an alkylamino group, an alkoxycarbonyl group, an alkanoyl group, an aryl group, an aralkyl group, an aryloxy group, an acyloxy group, a carboxy group, a halogen atom, a carbocyclic ring, and a heterocyclic ring. An alkyl group, an alkoxycarbonyl group, and an alkoxy group are preferred, and an alkyl group is more preferred.

[0022] The alkyl group may be, for example, an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 or 2 carbon atoms.

[0023] Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms, preferably alkoxy groups having 1 to 4 carbon atoms, and more preferably alkoxy groups having 1 or 2 carbon atoms.

[0024] Examples of the alkylamino group include alkylamino groups having from 1 to 6 carbon atoms, preferably alkylamino groups having from 1 to 4 carbon atoms, and more preferably alkylamino groups having 1 or 2 carbon atoms. The alkylamino group may be a monoalkylamino group or a dialkylamino group.

[0025] Examples of the alkoxycarbonyl group include alkoxycarbonyl groups having 1 to 6 carbon atoms in the alkyl portion, preferably alkoxycarbonyl groups having 1 to 4 carbon atoms in the alkyl portion, and more preferably alkoxycarbonyl groups having 1 or 2 carbon atoms in the alkyl portion.

[0026] Examples of the alkanoyl group include alkanoyl groups having 1 to 6 carbon atoms in the alkyl portion, preferably alkanoyl groups having 1 to 4 carbon atoms in the alkyl portion, and more preferably alkanoyl groups having 1 or 2 carbon atoms in the alkyl portion.

[0027] The aryl group includes, for example, an aryl group having 6 to 10 carbon atoms.

[0028] The aralkyl group refers to an arylalkyl group, and examples thereof include aralkyl groups having 6 to 10 carbon atoms in the aryl portion and 1 to 6 carbon atoms in the alkyl portion, preferably aralkyl groups having 6 to 10 carbon atoms in the aryl portion and 1 to 4 carbon atoms in the alkyl portion, and more preferably aralkyl groups having 6 to 10 carbon atoms in the aryl portion and 1 or 2 carbon atoms in the alkyl portion.

[0029] The aryloxy group includes, for example, an aryloxy group having 6 to 10 carbon atoms.

[0030] Examples of the acyloxy group include alkylcarbonyloxy groups having 1 to 6 carbon atoms in the alkyl portion, preferably alkylcarbonyloxy groups having 1 to 4 carbon atoms in the alkyl portion, and more preferably alkylcarbonyloxy groups having 1 or 2 carbon atoms in the alkyl portion.

[0031] The halogen atoms include fluorine, chlorine, bromine and iodine.

[0032] The carbocyclic ring means a saturated or unsaturated cyclic hydrocarbon, and examples thereof include saturated cyclic hydrocarbons having 3 to 10 carbon atoms and unsaturated cyclic hydrocarbons having 4 to 10 carbon atoms.

[0033] The heterocycle refers to a saturated or unsaturated cyclic hydrocarbon containing a heteroatom (e.g., oxygen, nitrogen, sulfur, etc.), and examples thereof include saturated cyclic hydrocarbons containing a heteroatom and having 3 to 10 carbon atoms, and unsaturated cyclic hydrocarbons containing a heteroatom and having 4 to 10 carbon atoms.

[0034] Two or more of the above substituents may be linked together to form a carbocyclic or heterocyclic ring.

[0035] Formula-A 1 Examples of the "alkylene group having from 2 to 6 carbon atoms, which may be substituted and which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" include optionally substituted groups of the formula -CH2-O-CH2-, -CH2-C(=O)-O-CH2-, -CH2-NH-CH2-, -CH2-S-CH2-, -(CH2)2-O-CH2-, -(CH2)2-NH-(CH2)2-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, and -(CH2)6-, among which optionally substituted groups of the formula -(CH2)3- and -(CH2)4- are preferred, and -(CH2)3-, -(CH2)4-, and -CH2-CH(CH3)-CH2- are more preferred.

[0036] Formula-A 2 Examples of the "alkylene group having 4 to 10 carbon atoms which may be substituted and which may further contain an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these" include optionally substituted groups of the formula -(CH)-O-(CH)-, -(CH)-NH-(CH)-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, -(CH)-, and -(CH) 10 -, and the like, optionally substituted, formula -(CH2)2-O-(CH2)2-, formula -(CH2)4-, formula -(CH2)6-, formula -(CH2)8-, formula -(CH2) 10- is preferred, and the formula -(CH2)2-O-(CH2)2-, the formula -(CH2)4-, the formula -(CH2)6-, the formula -(CH2)8-, and the formula -(CH2) 10 - is more preferred, and the formula -(CH2)4-, the formula -(CH2)6-, and the formula -(CH2) 10 - is even more preferable.

[0037] Formula-A 1 -(However, the previous bond is the carbon atom C 1 The latter bond is the carbon atom C 2 From the viewpoint of utilizing the resulting compound of general formula (I) as a precursor of a fragrance compound, the group (meaning a bond bonded to) is preferably an optionally substituted alkylene group having 3 or 4 carbon atoms, more preferably a group of the formula -(CH2)3-, -CH2-CH(CH3)-CH2-, or -(CH2)4-, and even more preferably a group of the formula -CH2-CH(CH3)-CH2-.

[0038] Formula-A 2 -(However, the previous bond is the carbon atom C 1 The latter bond is the carbon atom C 2 From the viewpoint of utilizing the resulting compound of general formula (I) as a precursor of a fragrance compound, the group (meaning a bond bonded to) is preferably an optionally substituted alkylene group having 4, 6, 8 or 10 carbon atoms, more preferably a group represented by the formula -(CH2)4-, -CH2-CH(CH3)-CH2-CH2-, -CH2-CH2-CH(CH3)-CH2-, -(CH2)6-, -(CH2)8-, -(CH2) 10 -, more preferably -(CH2)4-, -(CH2)6-, -(CH2)8-, -(CH2) 10 -, more preferably -(CH2)4-, -(CH2)6-, -(CH2) 10 -, more preferably -(CH2) 10 -It is.

[0039] The compound represented by the general formula (II) is, for example, represented by the following formula. From the viewpoint of utilizing the obtained compound of general formula (I) as a precursor of a fragrance compound, the compound represented by formula (i), the compound represented by formula (iii), the compound represented by formula (vii), and the compound represented by formula (viii) are preferred, and the compound represented by formula (vii) is more preferred. The compound represented by formula (vii) is 14-methylbicyclo[10.3.0]pentadecene[1(12)].

[0040] [ka]

[0041] An example of the compound represented by the general formula (I) is 3-methyl-1,5-cyclopentadecanedione represented by the following formula (1).

[0042] [ka]

[0043] [Metal catalyst] The oxidative cleavage is carried out in the presence of a metal catalyst containing one or more metal elements selected from the group consisting of vanadium, iron, and molybdenum. Examples of the metal catalyst include vanadium(IV) compounds, vanadium(V) compounds, molybdenum(VI) compounds, iron(II) compounds, and iron(III) compounds, and these may be used alone or in combination. The metal catalyst is preferably molybdenum(VI) oxide, molybdic acid, a dioxomolybdenum(VI) complex, polymolybdic acid, or heteropolymolybdic acid.

[0044] Examples of the vanadium(IV) compound and the vanadium(V) compound include vanadium(V) oxide, vanadate(V), vanadate(V) oxytrialkoxide, and vanadate(IV) complex. Examples of the vanadate(V) include ammonium orthovanadate(V), ammonium metavanadate(V), sodium orthovanadate(V), and sodium metavanadate(V). Examples of the vanadium oxytrialkoxide include vanadium(V) oxytrimethoxide, vanadium(V) oxytriethoxide, vanadium(V) oxytriisopropoxide, vanadium(V) oxytri-tert-butoxide, and vanadium(V) oxytri-sec-butoxide. Examples of the vanadium(IV) complex include vanadium(IV) oxide acetylacetonato complex VO(acac)2, vanadium(IV) oxide phthalocyanine complex, vanadium(IV) oxide porphyrin complex, and vanadium(IV) oxide salen complex.

[0045] Examples of the molybdenum (VI) compound include molybdenum (VI) oxide (MoO3), molybdic acid (H2MoO4), polymolybdic acid, heteropolymolybdic acid, and dioxomolybdenum (VI) complexes. Examples of the dioxomolybdenum (VI) complex include dioxomolybdenum (VI) acetylacetonato complex MoO2(acac)2, dioxomolybdenum (VI) porphyrin complex, and dioxomolybdenum (VI) salen complex. The polymolybdic acid has a structure in which molybdic acid is condensed, and examples thereof include metamolybdic acid H6[H2Mo 12 O 40 ]), paramolybdic acid (H6[H 10 Mo 12 O 46 The heteropolymolybdic acid has a structure in which heteroatoms such as phosphorus and silicon are condensed with molybdic acid, and examples thereof include phosphomolybdic acid (HPMo 12 O 40 (nH2O)), silicomolybdic acid (H4[SiMo 12 O 40 ]·(nH2O)), phosphorus vanadomolybdic acid (H15-X [PV 12-X Mo x O 40 ]·(nH2O)) etc.

[0046] Examples of the iron(II) compound and the iron(III) compound include iron(II) oxide, iron(III) oxide, iron(II) nitrate, iron(III) nitrate, iron(II) sulfate, iron(III) sulfate, iron alkoxides, iron carboxylates, iron halides, and iron complexes. Examples of the iron alkoxides include iron(II) methoxide, iron(III) methoxide, iron(II) ethoxide, iron(III) ethoxide, iron(II) isopropoxide, iron(III) isopropoxide, iron(II) tert-butoxide, iron(III) tert-butoxide, iron(II) sec-butoxide, and iron(III) sec-butoxide. Examples of the iron carboxylates include iron(II) formate, iron(III) formate, iron(II) acetate, iron(III) acetate, iron(II) trifluoroacetate, and iron(III) trifluoroacetate. Examples of the iron halides include iron(II) chloride, iron(III) chloride, iron(II) bromide, iron(III) bromide, etc. Examples of the iron complexes include iron(II) acetylacetonato complexes, iron(III) acetylacetonato complexes, iron porphyrin complexes, and iron salen complexes.

[0047] The molar ratio of the metal catalyst to the compound of formula (II) [metal catalyst / compound of formula (II)] is, from the viewpoint of improving the reaction yield, for example, 0.0001 or more, preferably 0.001 or more, more preferably 0.01 or more, and from the viewpoint of reducing the production cost, it is, for example, 1 or less, preferably 0.7 or less, more preferably 0.3 or less. The molar ratio of the metal catalyst to the compound of formula (II) [metal catalyst / compound of formula (II)] is, from the viewpoint of improving the reaction yield, for example, 0.0001 or more and 1 or less, preferably 0.001 or more and 0.7 or less, more preferably 0.01 or more and 0.3 or less.

[0048] [Oxidizing agent] Examples of the oxidizing agent include peroxides, halogen acids or salts thereof, and perhalogen acids or salts thereof. One type of oxidizing agent may be used, or multiple types may be used in combination. Examples of peroxides include peracids or salts thereof, non-peracid organic peroxides, and non-peracid inorganic peroxides. Examples of peracids include percarboxylic acids, persulfuric acids, percarbonates, perphosphoric acids, and hypoperhalogen acids. Examples of non-peracid organic peroxides include tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dimethyldioxirane, acetone peroxide, methyl ethyl ketone peroxide, and hexamethylene triperoxide diamine. Examples of non-peracid inorganic peroxides include hydrogen peroxide, lithium peroxide, sodium peroxide, potassium peroxide, and permanganates. Examples of halogen acids include chloric acid, bromic acid, and iodic acid. Examples of perhalogen acids include perchloric acid, perbromic acid, and periodic acid. Although there are no limitations on the oxidizing agent, it is preferable to use hydrogen peroxide or tert-butyl hydroperoxide (TBHP) from the viewpoints of production cost and ease of handling.

[0049] The molar ratio of the oxidizing agent to the compound represented by general formula (II) [oxidizing agent / compound represented by general formula (II)] is, from the viewpoint of yield, for example, 0.5 or more, preferably 1 or more, and more preferably 1.2 or more, and from the viewpoint of reducing production costs, it is, for example, 20 or less, preferably 10 or less, and more preferably 5 or less. The molar ratio of the oxidizing agent to the compound represented by general formula (II) [oxidizing agent / compound represented by general formula (II)] is, from the viewpoint of yield, for example, 0.5 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1.2 or more and 5 or less.

[0050] When hydrogen peroxide is used as the oxidizing agent, the concentration of hydrogen peroxide is not particularly limited, but may be selected, for example, from the range of 1 to 80% by mass, preferably from the range of 30 to 60% by mass from the viewpoints of safety and reaction yield.

[0051] [Additives] In the present invention, the oxidative cleavage may be carried out in the presence of an additive. Examples of the additive include inorganic acids such as phosphoric acid, sulfuric acid, and hydrochloric acid; polycarboxylic acids such as oxalic acid; organic acids such as p-toluenesulfonic acid; and compounds represented by the following formula (III). In particular, it is preferable to use a compound represented by the following formula (III) as the additive.

[0052] [ka]

[0053] In the formula (III), R is COOH or OH; R 1 , R 2 , R 3 , R 4 , and R 5 are each independently hydrogen, halogen atoms, NO2, OH, COOH, NR 6 R 7 (In the formula, R 6 and R 7 are each independently selected from the group consisting of hydrogen, an alkyl group having from 1 to 3 carbon atoms, or an alkyl group having from 1 to 3 carbon atoms substituted with OH, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, and a phenyl group (which may be substituted), or R 1 , R 2 , R 3 , R 4 , and R 5 Two of these groups together with the carbon atoms that support them form a saturated or unsaturated hydrocarbon ring, and the remaining three groups are each independently hydrogen, halogen atoms, NO2, OH, COOH, or NR 6 R 7 (In the formula, R 6 and R 7are each independently selected from the group consisting of hydrogen, an alkyl group having from 1 to 3 carbon atoms, or an alkyl group having from 1 to 3 carbon atoms substituted with OH, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, and a phenyl group (which may be substituted).

[0054] In the formula (III), the alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms.

[0055] In the formula (III), the alkyl group having 1 to 3 carbon atoms is preferably an alkyl group having 1 to 2 carbon atoms, and more preferably an alkyl group having 1 carbon atom.

[0056] In the formula (III), the alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 or 2 carbon atoms.

[0057] In the formula (III), the halogen atom includes fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, more preferably chlorine.

[0058] In the formula (III), examples of the saturated or unsaturated hydrocarbon ring include saturated cyclic hydrocarbons having 3 to 10 carbon atoms and unsaturated cyclic hydrocarbons having 4 to 10 carbon atoms.

[0059] In the formula (III), examples of the substituent of the phenyl group (which may be substituted) include a halogen atom, OH, COOH, and a methyl group. Examples of the substituted phenyl group include a 2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 2-bromophenyl group, a 3-bromophenyl group, a 4-bromophenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-carboxyphenyl group, a 3-carboxyphenyl group, a 4-carboxyphenyl group, a 3-carboxy-4-hydroxyphenyl group, and a 2-hydroxy-3-carboxyphenyl group, with a 3-carboxy-4-hydroxyphenyl group and a 2-hydroxy-3-carboxyphenyl group being preferred.

[0060] The additive is represented by the formula (III): R is COOH, R 1 , R 2 , R 3 , R 4 , and R 5 are preferably each independently selected from the group consisting of hydrogen, a halogen atom, NO, COOH, OH, and an alkoxy group having from 1 to 6 carbon atoms; R is COOH, R 1 , R 2 , R 3 , R 4 , and R 5 more preferably, one of the groups is OH, and the rest are each independently selected from the group consisting of hydrogen, a halogen atom, NO, and an alkoxy group having from 1 to 6 carbon atoms; R is COOH, R 1 is OH and R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of hydrogen, a halogen atom, NO and an alkoxy group having 1 to 6 carbon atoms (in this case, represented by the following formula (ix)), R is COOH, R 2 is OH and R 1 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of hydrogen, a halogen atom, NO2, and an alkoxy group having 1 to 6 carbon atoms (in this case, represented by the following formula (x)), or R is COOH, R 3 is OH and R 1 , R 2 , R 4 , and R 5 are each more preferably independently selected from the group consisting of hydrogen, a halogen atom, NO2, and an alkoxy group having 1 to 6 carbon atoms (in this case, represented by the following formula (xi)).

[0061] [ka]

[0062] The additive represented by formula (ix) is R 2 is a hydrogen atom, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms, R 3 is hydrogen, a halogen atom, or NO2, R 4 is hydrogen, a halogen atom, or NO2, R 5 is more preferably hydrogen. The additive represented by formula (xii) is more preferably represented by, for example, formulas (101) to (108) below.

[0063] [ka]

[0064] R is COOH and R 1 , R 2 , R 3 , R4 , and R 5 are each independently hydrogen, halogen atoms, NO2, OH, COOH, NR 6 R 7 (In the formula, R 6 and R 7are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms substituted with OH), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group (the phenyl group may be substituted). Examples of the additive of formula (III) include benzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, 2,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 3,5-dibromobenzoic acid, p-methylbenzoic acid, p-tert-butylbenzoic acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3-chloro-4-methoxybenzoic acid,3-Bromo-4-methoxybenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 3-fluorophthalic acid, 3-chlorophthalic acid, 3-bromophthalic acid, 3-methoxyphthalic acid, 3-methylphthalic acid, 4-fluorophthalic acid, 4-chlorophthalic acid, 4-bromophthalic acid, 4-methoxyphthalic acid, 4-methylphthalic acid, trimesic acid, salicylic acid, 3-methylsalicylic acid, 4-methylsalicylic acid, 5-methylsalicylic acid, 6-methylsalicylic acid, 3-ethylsalicylic acid, 4-ethylsalicylic acid, 5-ethylsalicylic acid, 6-ethylsalicylic acid, 3-isopropyl Salicylic acid, 4-isopropyl salicylic acid, 5-isopropyl salicylic acid, 6-isopropyl salicylic acid, 3-tert-butyl salicylic acid, 4-tert-butyl salicylic acid, 5-tert-butyl salicylic acid, 6-tert-butyl salicylic acid, 3-fluorosalicylic acid, 4-fluorosalicylic acid, 5-fluorosalicylic acid, 6-fluorosalicylic acid, 4-fluorosalicylic acid, 5-fluorosalicylic acid, 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid , 5-Bromosalicylic acid, 6-Bromosalicylic acid, 3-Iodosalicylic acid, 4-Iodosalicylic acid, 5-Iodosalicylic acid, 6-Iodosalicylic acid, 3-Nitrosalicylic acid, 4-Nitrosalicylic acid, 5-Nitrosalicylic acid, 6-Nitrosalicylic acid, 3-Methoxysalicylic acid, 4-Methoxysalicylic acid, 5-Methoxysalicylic acid, 6-Methoxysalicylic acid, 3-Ethoxysalicylic acid, 4-Ethoxysalicylic acid, 5-Ethoxysalicylic acid, 6-Ethoxysalicylic acid, 3,5-Difluorosalicylic acid, 3,5-Dichlorosalicylic acid, 3,5-Dibromosalicylic acid , 3,5-diiodosalicylic acid, 3,5-dimethoxysalicylic acid, 3-phenylsalicylic acid, biphenyl-2-carboxylic acid, biphenyl-3-carboxylic acid, benzoic acid, 3,5-dichlorobenzoic acid, 3,5-dibromobenzoic acid, 3-chloro-4-methoxybenzoic acid, 3-bromo-4-methoxybenzoic acid, salicylic acid, 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, 3-methoxysalicylic acid, 4-methoxysalicylic acid, 5-methoxysalicylic acid, 3,Preferably, the group consisting of 5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, 3-chloro-5-bromosalicylic acid, 3-bromo-5-chlorosalicylic acid, 4-nitrosalicylic acid, and 5-nitrosalicylic acid is selected from the group consisting of 5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, 3-chloro-5-bromosalicylic acid, 3-bromo-5-chlorosalicylic acid, 4-nitrosalicylic acid, and 5-nitrosalicylic acid. 1 , R 2 , R 3 , R 4 , and R 5 In formula (III), preferably 1 to 3 are halogen atoms, and more preferably 1 to 2 are halogen atoms. 1 , R 2 , R 3 , R 4 , and R 5 Preferably, 1 to 2 of these are nitro groups and / or alkoxy groups having 1 to 6 carbon atoms, and more preferably, 1 is a nitro group and / or an alkoxy group having 1 to 6 carbon atoms.

[0065] Furthermore, the additive of formula (III) is preferably benzenecarboxylic acid (benzoic acid), benzenedicarboxylic acid (including phthalic acid, isophthalic acid, and terephthalic acid), or benzenehydroxycarboxylic acid (including salicylic acid), which may be substituted with a halogen atom, NO, or an alkoxy group having from 1 to 6 carbon atoms, and more preferably salicylic acid, which may be substituted with a halogen atom, NO, or an alkoxy group having from 1 to 6 carbon atoms.

[0066] The additive is represented by formula (III), wherein R is COOH, R 1 , R 2 , R 3 , R 4 , and R 5 One of them is COOH, and the rest are independently hydrogen, halogen atoms, NO2, OH, COOH, NR 6 R 7 (In the formula, R 6 and R 7are preferably each independently selected from the group consisting of hydrogen, an alkyl group having from 1 to 3 carbon atoms, or an alkyl group having from 1 to 3 carbon atoms substituted with OH, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, and a phenyl group (the phenyl group may be substituted). Examples of such additives include phthalic acid, isophthalic acid, terephthalic acid, 3-fluorophthalic acid, 3-chlorophthalic acid, 3-bromophthalic acid, 3-methoxyphthalic acid, 3-methylphthalic acid, 4-fluorophthalic acid, 4-chlorophthalic acid, 4-bromophthalic acid, 4-methoxyphthalic acid, 4-methylphthalic acid, and trimesic acid.

[0067] The additive may be a compound represented by the formula (III): 1 , R 2 , R 3 , R 4 , and R 5 Two of these groups form an unsaturated hydrocarbon ring together with the carbon atoms that support them, and the remaining three groups independently represent hydrogen, halogen atoms, NO2, OH, COOH, or NR 6 R 7 (In the formula, R 6 and R 7 are preferably each independently selected from the group consisting of hydrogen, an alkyl group having from 1 to 3 carbon atoms, or an alkyl group having from 1 to 3 carbon atoms substituted with OH, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, and a phenyl group (the phenyl group may be substituted). Examples of such additives include 1-naphthoic acid and 2-naphthoic acid.

[0068] The additive may further comprise a compound represented by formula (III), wherein R is OH, R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of hydrogen and NO. R is OH and R 1 , R 2 , R 3 , R 4, and R 5 are each independently selected from the group consisting of hydrogen and NO2. Examples of additives of formula (III) include o-nitrophenol, m-nitrophenol, p-nitrophenol, and the like.

[0069] The polycarboxylic acid is preferably an aliphatic dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, or adipic acid. The number of carbon atoms in the polycarboxylic acid is preferably 2 or more, 10 or less, and more preferably 6 or less.

[0070] The molar ratio of the additive to the compound represented by general formula (II) [additive / compound represented by general formula (II)] is, for example, 0.001 or more, preferably 0.01 or more, more preferably 0.05 or more from the viewpoint of improving the reaction yield, and is preferably 10 or less, 1 or less, or 0.5 or less from the viewpoint of reducing the production cost. The molar ratio of the compound represented by general formula (II) to the additive [compound represented by general formula (II):additive] is, for example, 0.001 or more and 10 or less, preferably 0.01 or more and 1 or less, more preferably 0.05 or more and 0.5 or less from the viewpoint of improving the reaction yield.

[0071] From the viewpoint of improving the reaction yield, the molar ratio of the additive to the metal catalyst [additive / metal catalyst] is, for example, 0.01 or more, preferably 0.5 or more, more preferably 1 or more, and from the viewpoint of reducing the production cost, it is, for example, 100 or less, preferably 30 or less, more preferably 10 or less. From the viewpoint of improving the reaction yield, the molar ratio of the additive to the metal catalyst [additive / metal catalyst] is, for example, 0.01 or more and 100 or less, preferably 0.5 or more and 30 or less, more preferably 1 or more and 10 or less.

[0072] The reaction temperature in the method of the present invention is generally 0°C or higher and 100°C or lower, and from the viewpoint of safely improving the reaction yield, is preferably 20°C or higher, and is preferably 80°C or lower, more preferably 50°C or lower.

[0073] The reaction pressure in the method of the present invention is not particularly limited, but is generally normal pressure. The method of the present invention may be pressurized or reduced as necessary.

[0074] The reaction time in the method of the present invention depends on the yield, but is preferably 1 hour or more, more preferably 10 hours or more, and preferably 100 hours or less, more preferably 60 hours or less.

[0075] In the method of the present invention, the reaction may be carried out in the presence of an organic solvent. The organic solvent is not particularly limited as long as it is a solvent that makes the reaction solution homogeneous. Examples of the organic solvent include ethers and alcohols. Among them, from the viewpoint of reaction yield, it is preferable to use alcohols, more preferably saturated aliphatic alcohols, and even more preferably t-butyl alcohol.

[0076] In the method of the present invention, the mass ratio of the solvent to the compound of formula (II) [solvent / compound of formula (II)] is, from the viewpoint of improving the reaction yield, for example, 1 or more, preferably 2 or more, and more preferably 3 or more, and from the viewpoint of reducing the production cost, it is, for example, 30 or less, preferably 10 or less, more preferably 7 or less, and even more preferably 5 or less. In the method of the present invention, the mass ratio of the solvent to the compound of formula (II) [solvent / compound of formula (II)] is, from the viewpoint of improving the reaction yield, for example, 1 or more and 30 or less, preferably 1 or more and 10 or less, more preferably 2 or more and 7 or less, and even more preferably 3 or more and 5 or less.

[0077] [Step of oxidatively cleaving a compound represented by general formula (II) using an oxidizing agent in the presence of a metal catalyst containing one or more metal elements selected from the group consisting of vanadium, iron, and molybdenum to obtain a compound represented by general formula (I)] In this step, for example, the metal catalyst, the oxidizing agent, the compound represented by general formula (II), an organic solvent, and optionally the additives are mixed in a reactor and reacted at a predetermined temperature, usually with stirring. The order of addition of the metal catalyst, oxidizing agent, compound represented by general formula (II), organic solvent, and optional additives is not particularly limited. However, from a safety standpoint, the reaction may be carried out by continuously adding the oxidizing agent dropwise to a mixed solution of the metal catalyst, compound represented by general formula (II), optional additives, and organic solvent. Alternatively, a catalyst solution may be prepared in advance by mixing the metal catalyst, optional additives, and oxidizing agent, and then the catalyst solution may be added to a mixed solution of the compound represented by general formula (II) and organic solvent to carry out the reaction.

[0078] After the reaction is completed, the oxide remaining in the reaction system can be decomposed, for example, with a reducing agent, and then the compound represented by general formula (I) can be purified by separating the oil-water layer, removing the solvent, distilling, silica gel column chromatography, or the like.

[0079] The present invention further provides a method for producing a cyclic ketone compound represented by formula (3). The cyclic ketone compound represented by formula (3) is a mixture of 3-methyl-4-cyclopentadecen-1-one and 3-methyl-5-cyclopentadecen-1-one, and is known as Muscenone (manufactured by Firmenich). The cyclic ketone compound represented by formula (3), which is a musk fragrance material, is a cyclic compound that is highly biodegradable and has a long-lasting fragrance and an elegant texture. In response to the growing need for synthetic musk fragrances in recent years, there is a need for the development of a production method that is highly safe and efficient in production. The method for producing the cyclic ketone compound represented by formula (3) using 3-methyl-1,5-cyclopentadecanedione (1) obtained by the method of the present invention comprises any one of the following steps (a), (b), or (c):

[0080] [ka]

[0081] (a) a step of partially reducing 3-methyl-1,5-cyclopentadecanedione and then dehydrating it to obtain a cyclic ketone compound represented by formula (3); (b) reduction of 3-methyl-1,5-cyclopentadecanedione followed by enol etherification and subsequent ring opening to give mucenone; or (c) Partial reduction and enol etherification of 3-methyl-1,5-cyclopentadecanedione, followed by ring-opening to give mucenone.

[0082] The step (a) may be, for example, (a-1) Partial reduction of 3-methyl-1,5-cyclopentadecanedione (1) to obtain 3-methylcyclopentadecanol-5-one (2), (a-2) A step of dehydrating the 3-methylcyclopentadecanol-5-one (2) to obtain a cyclic ketone compound represented by formula (3).

[0083] [ka]

[0084] The step (b) may be, for example, (b-1) 3-methyl-1,5-cyclopentadecanedione (1) is reduced to give 3-methylcyclopentadecane-1,5-diol (4), (b-2) the 3-methylcyclopentadecane-1,5-diol (4) is partially oxidized and enol etherified to obtain 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5); (b-3) A step of ring-opening the 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5) to obtain a cyclic ketone compound represented by formula (3).

[0085] [ka]

[0086] The step (c) may be, for example, (c-1) 3-methyl-1,5-cyclopentadecanedione (1) is partially reduced and enol etherified to give 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5), (c-2) A step of ring-opening the 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5) to obtain a cyclic ketone compound represented by formula (3).

[0087] [ka]

[0088] The 3-methyl-1,5-cyclopentadecanedione (1) can be obtained by the method for producing the compound represented by formula (I) of the present invention.

[0089] First, a method for producing a cyclic ketone compound represented by formula (3) including step (a) will be described.

[0090] (a) The process (a-1) Partial reduction of 3-methyl-1,5-cyclopentadecanedione (1) to obtain 3-methylcyclopentadecanol-5-one (2), (a-2) A step of dehydrating the 3-methylcyclopentadecanol-5-one (2) to obtain a cyclic ketone compound represented by formula (3).

[0091] [ka]

[0092] The partial reduction of 3-methyl-1,5-cyclopentadecanedione (1) in the step (a-1) can be carried out using a metal hydride such as sodium borohydride or sodium hydride, or by hydrogenation in the presence of a metal catalyst. From the viewpoints of safety and reaction yield, the partial reduction is preferably carried out by hydrogenation in the presence of a metal catalyst.

[0093] The metal catalyst that can be used in the hydrogenation method includes palladium carbon, Raney nickel, etc. From the viewpoint of enabling hydrogenation under mild reaction conditions, it is preferable to use Raney nickel as the metal catalyst in the hydrogenation method.

[0094] In the step (a-1), the amount of the metal catalyst used relative to the 3-methyl-1,5-cyclopentadecanedione (1) is preferably in the molar ratio of 3-methyl-1,5-cyclopentadecanedione (1) to the metal catalyst [3-methyl-1,5-cyclopentadecanedione (1):metal catalyst] of 1:0.01 to 1:1, more preferably 1:0.1 to 1:0.5, from the viewpoints of reaction yield and cost.

[0095] The reaction temperature in the step (a-1) is preferably 0°C or higher from the viewpoint of improving the reaction yield, and is preferably 100°C or lower, more preferably 50°C or lower, and even more preferably 30°C or lower from the viewpoint of suppressing side reactions.

[0096] From the viewpoint of improving the reaction yield, the reaction time in the (a-1) step is preferably 0.1 hours or more, more preferably 0.5 hours or more, and is preferably 10 hours or less, more preferably 3 hours or less, and even more preferably 1 hour or less.

[0097] From the viewpoints of safety and reaction selectivity, the hydrogen pressure in the hydrogenation is preferably 0.1 MPa or more, and is preferably 2.0 MPa or less, more preferably 1.0 MPa or less.

[0098] The reaction in step (a-1) may be carried out in the presence of an organic solvent. The organic solvent is not particularly limited as long as it dissolves the reaction substrate. Examples of the organic solvent include alcohols, and from the viewpoints of production efficiency and cost, it is more preferable to use a lower alcohol having 1 to 3 carbon atoms.

[0099] In the step (a-2), the 3-methylcyclopentadecanol-5-one (2) can be dehydrated in the presence of an acid.

[0100] Examples of the acid used in the step (a-2) include sulfuric acid, phosphoric acid, and benzenesulfonic acid, and from the viewpoints of equipment load and reaction yield, benzenesulfonic acid is preferred.

[0101] In the step (a-2), the amount of acid used relative to 3-methylcyclopentadecanol-5-one (2) is preferably in the molar ratio of 3-methylcyclopentadecanol-5-one (2) to acid [3-methylcyclopentadecanol-5-one (2):acid] of 1:0.01 to 1:1, more preferably 1:0.05 to 1:0.3, from the viewpoints of production cost and reaction yield.

[0102] The reaction temperature in the step (a-2) is preferably 20°C or higher, more preferably 50°C or higher, and even more preferably 70°C or higher from the viewpoint of improving the reaction yield, and is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 130°C or lower from the viewpoint of safety.

[0103] From the viewpoint of improving the reaction yield, the reaction time in the (a-2) step is preferably 0.25 hours or more, more preferably 0.5 hours or more, and is preferably 20 hours or less, more preferably 10 hours or less, and even more preferably 3 hours or less.

[0104] The reaction in step (a-2) may be carried out in the presence of an organic solvent. The organic solvent is not particularly limited as long as it is a solvent that forms an azeotrope with water. Examples of the organic solvent include hydrocarbons, and toluene is more preferably used from the viewpoint of dehydration efficiency.

[0105] Also, a method for producing a cyclic ketone compound represented by formula (3), which includes step (b), will be described.

[0106] (b) The process (b-1) 3-methyl-1,5-cyclopentadecanedione (1) is reduced to give 3-methylcyclopentadecane-1,5-diol (4), (b-2) 3-methylcyclopentadecane-1,5-diol (4) is partially oxidized and enol etherified to give 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5), (b-3) A step of ring-opening the 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5) to obtain a cyclic ketone compound represented by formula (3).

[0107] [ka]

[0108] The method for partially reducing 3-methyl-1,5-cyclopentadecanedione (1) in the step (b-1) includes a method using a metal hydride such as sodium borohydride or sodium hydride, and a method of hydrogenation in the presence of a metal catalyst. From the viewpoints of safety and reaction yield, the method of hydrogenation in the presence of a metal catalyst is preferred.

[0109] As the metal catalyst for the hydrogenation method, palladium carbon, Raney nickel, etc. can be used. From the viewpoint of enabling hydrogenation under mild reaction conditions, it is preferable to use Raney nickel.

[0110] In the step (b-1), the amount of the metal catalyst used relative to the 3-methyl-1,5-cyclopentadecanedione (1) is preferably in the molar ratio of 3-methyl-1,5-cyclopentadecanedione (1) to the metal catalyst [3-methyl-1,5-cyclopentadecanedione (1):metal catalyst] of 1:0.01 to 1:1, more preferably 1:0.1 to 1:0.5, from the viewpoints of reaction yield and cost.

[0111] The reaction temperature in the step (b-1) is preferably 0°C or higher from the viewpoint of improving the reaction yield, and is preferably 100°C or lower, more preferably 50°C or lower, and even more preferably 30°C or lower from the viewpoint of suppressing side reactions.

[0112] From the viewpoint of improving the reaction yield, the reaction time in the (b-1) step is preferably 1 hour or more, more preferably 5 hours or more, and even more preferably 10 hours or more, and is preferably 30 hours or less, and more preferably 25 hours or less.

[0113] From the viewpoints of safety and reaction selectivity, the hydrogen pressure in the hydrogenation is preferably 0.1 MPa or more, and is preferably 2.0 MPa or less, more preferably 1.0 MPa or less.

[0114] The reaction in step (b-1) may be carried out in the presence of an organic solvent. The organic solvent is not particularly limited as long as it dissolves the reaction substrate. Examples of the organic solvent include alcohols, and from the viewpoints of production efficiency and cost, it is more preferable to use a lower alcohol having 1 to 3 carbon atoms.

[0115] The method for partially oxidizing and enol-etherifying 3-methylcyclopentadecane-1,5-diol (4) in the step (b-2) can be a method for partially oxidizing and enol-etherifying in the presence of a metal catalyst.

[0116] The metal catalyst used in the step (b-2) may be a metal catalyst having oxidizing ability, such as aluminum oxide, iron oxide, or Raney copper, but from the viewpoint of improving the reaction yield, it is preferable to use Raney copper.

[0117] In the step (b-2), the amount of the metal catalyst used relative to the 3-methylcyclopentadecane-1,5-diol (4) is preferably such that the molar ratio of the 3-methylcyclopentadecane-1,5-diol (4) to the metal catalyst [3-methylcyclopentadecane-1,5-diol (4):metal catalyst] is 1:0.01 to 1:1 from the viewpoints of reaction yield and cost, and more preferably 1:0.05 to 1:0.3 from the viewpoints of shortening the reaction time and reducing waste.

[0118] The reaction temperature in the step (b-2) is preferably 100°C or higher, more preferably 120°C or higher, from the viewpoint of improving the reaction yield, and is preferably 300°C or lower, more preferably 200°C or lower, and even more preferably 180°C or lower, from the viewpoint of suppressing side reactions.

[0119] The reaction time in the (b-2) step is preferably 1 hour or longer, more preferably 2 hours or longer, from the viewpoint of improving the reaction yield, and is preferably 20 hours or shorter, more preferably 10 hours or shorter, and even more preferably 5 hours or shorter, from the viewpoint of improving productivity.

[0120] In the step (b-3), the ring-opening of 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5) can be carried out in the presence of an acid.

[0121] Examples of the acid used in the step (b-3) include sulfuric acid, phosphoric acid, and benzenesulfonic acid, and from the viewpoints of ease of handling and reaction yield, phosphoric acid is preferred.

[0122] In the step (b-3), the amount of acid to be used relative to 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5) is, from the viewpoint of production efficiency and reaction yield, preferably in a molar ratio of 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5) to acid [16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5):acid] of 1:0.01 to 1:1, more preferably 1:0.1 to 1:0.5.

[0123] The reaction temperature in the step (b-3) is preferably 20°C or higher, more preferably 50°C or higher, and even more preferably 70°C or higher, from the viewpoint of improving the reaction yield, and is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 130°C or lower, from the viewpoint of suppressing side reactions.

[0124] From the viewpoint of improving the reaction yield, the reaction time in the (b-3) step is preferably 0.5 hours or more, more preferably 1 hour or more, and is preferably 20 hours or less, more preferably 10 hours or less, and even more preferably 5 hours or less.

[0125] The reaction in the step (b-3) may be carried out in the presence of an organic solvent. The organic solvent is not particularly limited as long as it is a solvent that forms an azeotrope with water. Examples of the organic solvent include hydrocarbons, and it is more preferable to use toluene from the viewpoint of dehydration efficiency.

[0126] Also, a method for producing a cyclic ketone compound represented by formula (3), which includes step (c), will be described.

[0127] (c-1) 3-methyl-1,5-cyclopentadecanedione (1) is partially reduced and enol etherified to give 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5), (c-2) A step of ring-opening the 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5) to obtain a cyclic ketone compound represented by formula (3).

[0128] [ka]

[0129] The method for partially reducing and enol-etherifying 3-methyl-1,5-cyclopentadecanedione (1) in the step (c-1) includes a method in which the reaction is carried out in the presence of a metal catalyst containing one or more metal elements selected from the group consisting of magnesium, aluminum, zirconium, titanium, and samarium, and an alcohol containing one or more alcohols selected from the group consisting of primary alcohols and secondary alcohols.

[0130] The metal catalyst is a metal catalyst containing one or more metal elements selected from the group consisting of magnesium, aluminum, zirconium, titanium, and samarium. The metal catalyst preferably contains one or more metal elements selected from the group consisting of aluminum, zirconium, and titanium. Examples of the metal catalyst include aluminum alkoxide, zirconium alkoxide, titanium alkoxide, and zirconium oxide. Examples of the aluminum alkoxide include aluminum ethoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum sec-butoxide, and aluminum tert-butoxide. Examples of the zirconium-containing catalyst include zirconia (zirconium dioxide) and zirconium alkoxide. Examples of the zirconium alkoxide include zirconium(IV) ethoxide, zirconium(IV) isopropoxide, zirconium(IV) n-propoxide, zirconium(IV) n-butoxide, zirconium(IV) sec-butoxide, and zirconium(IV) tert-butoxide. Because of their high catalytic activity (i.e., high reaction rate and high reaction yield), aluminum alkoxides, zirconium alkoxides, and titanium alkoxides are preferred, with aluminum alkoxides and zirconium alkoxides being more preferred. Because the amount used can be reduced to the catalytic amount, zirconium alkoxides are preferred, with zirconium(IV) n-butoxide, zirconium sec-butoxide, and zirconium tert-butoxide being more preferred. Because of their ease of industrial availability, zirconium(IV) n-butoxide is preferred.

[0131] The alcohol includes one or more alcohols selected from the group consisting of primary alcohols and secondary alcohols. Examples of the primary alcohols include ethanol, 1-propanol, 1-butanol, 2-methylpropanol, 1-pentanol, 2-methylbutanol, 3-methylbutanol, 1-hexanol, 2-methylpentanol, 3-methylpentanol, 2-ethylbutanol, 1-heptanol, 2-methylhexanol, 1-octanol, 1-nonanol, and 1-decanol. The secondary alcohols are not limited in terms of valence, and are not particularly limited as long as they have one or more secondary hydroxyl groups. The secondary alcohols may have a linear, branched, or cyclic aliphatic group, an aromatic group, or a combination of both. Examples of the secondary alcohol include isopropyl alcohol, 2-butanol, 2-pentanol, 3-pentanol, cyclopentanol, 2-hexanol, 3-hexanol, cyclohexanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-heptanol, 3-heptanol, 4-heptanol, 3-methyl-2-hexanol, 4-methyl-2-hexanol, 5-methyl-2-hexanol, cycloheptanol, 2-octanol, 3-octanol, 4-octanol, cyclooctanol, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol, etc. As the secondary alcohol, cyclohexanol and 2-octanol are preferred because the reaction rate can be increased by raising the temperature.

[0132] The alcohol is preferably a secondary alcohol. The alcohol preferably has a boiling point of 100°C or higher, because the reaction proceeds while removing by-product water from the system, thereby improving reaction selectivity and shortening the reaction time. Furthermore, the alcohol preferably has a boiling point of 200°C or lower, because its moderate boiling point prevents excessive reaction during azeotropic distillation with water, thereby preventing a decrease in reaction selectivity. The alcohol preferably has a boiling point of 150°C or higher and 200°C or lower, because the reaction rate can be increased by heating. Specific boiling points are isopropanol 82.4°C, cyclohexanol 161.8°C, 2-butanol 100°C, and 2-octanol 174°C. As an alcohol containing one or more selected from the group consisting of primary alcohols and secondary alcohols, 2-octanol or cyclohexanol is preferred because it is easily available industrially.

[0133] <Reaction temperature> In the present invention, the step of reacting the compound of formula (1) in the presence of the metal catalyst and the alcohol to obtain the compound of formula (5) is carried out, for example, at 80°C or higher, preferably 100°C or higher, more preferably 150°C or higher, and for example, 280°C or lower, preferably 250°C or lower, more preferably 190°C or lower.

[0134] <Reaction time> In the present invention, the reaction time for the step of reacting the compound of formula (1) in the presence of the metal catalyst and the alcohol to obtain the compound of formula (5) is, for example, 2 hours to 5 days, preferably 4 hours to 2 days, and from the viewpoints of production cost and production efficiency, more preferably 6 hours to 24 hours.

[0135] <Amount> In the present invention, in the step of obtaining a compound of formula (5) by reacting a compound of formula (1) in the presence of the metal catalyst and the alcohol, the molar ratio of the compound of formula (1) to the alcohol [compound of formula (1):alcohol] is, for example, 1:1 to 1:100, preferably 1:1 to 1:50, and more preferably 1:1.5 to 1:5 from the viewpoints of production cost and production efficiency.

[0136] In a specific embodiment, the metal catalyst, alcohol, and compound represented by general formula (1) are mixed in a reactor and reacted at a predetermined temperature, usually with stirring. The metal catalyst, alcohol, and compound represented by general formula (1) may be added in any order, and additives may be added as needed. It is more preferable to carry out the reaction in a reactor equipped with a Dean-Stark apparatus or a rectification column. After the reaction is complete, the compound represented by general formula (5) can be purified by distillation.

[0137] In the step of reacting a compound of formula (1) in the presence of the metal catalyst and the alcohol to obtain a compound of formula (5), the molar ratio of the compound of formula (1) to the metal catalyst [compound of formula (5):metal catalyst] is, for example, 1:0.001 to 1:1.5, preferably 1:0.01 to 1:1.2, and more preferably 1:0.05 to 1:1.1 in terms of production costs, when the metal catalyst contains zirconium. Furthermore, when the metal catalyst contains one or more metal elements selected from the group consisting of magnesium, aluminum, titanium, and samarium, the molar ratio of the compound of formula (1) to the metal catalyst [compound of formula (1):metal catalyst] is, for example, 1:0.3 to 1:3, preferably 1:0.5 to 1:1.5, and more preferably 1:0.8 to 1:1.2 in terms of production costs.

[0138] <Additives> In the present invention, the step of reacting the compound of formula (1) in the presence of the metal catalyst and the alcohol to obtain the compound of formula (5) may be carried out in the presence of an additive. Examples of the additive include acids, diols, diamines, and aminoalcohols. Examples of the acid include phosphoric acid, sulfuric acid, paratoluenesulfonic acid, acetic acid, chloroacetic acid, and trifluoroacetic acid (TFA). Examples of the diol include ethylene glycol (EG), 1,2-cyclohexanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Examples of the diamine include ethylenediamine, 1,2-diaminocyclohexane, and 1,2-phenylenediamine. Examples of the aminoalcohol include 2-aminoethanol, 3-aminopropanol, 2-aminopropanol, 1-amino-2-propanol, valinol, and phenylalaninol. The additives are preferably acids and diols, more preferably TFA and EG, from the viewpoint of shortening the reaction time. When the acid is used as the additive, the molar ratio of the metal catalyst to the acid [metal catalyst:acid] is, for example, 1:0.05 to 1:5, preferably 1:1 to 1:3. When the diol is used as the additive, the molar ratio of the metal catalyst to the diol [metal catalyst:diol] is, for example, 1:0.1 to 1:5, preferably 1:1 to 1:3. When the acid and diol are used as the additive, the molar ratio of the metal catalyst to the acid to the diol [metal catalyst:acid:diol] is, for example, 1:0.1 to 5:0.1 to 5, preferably 1:1 to 3:1 to 3.

[0139] (c-2) As a method including a step of ring-opening the 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (5) to obtain the cyclic ketone compound represented by formula (3), a method of ring-opening in the presence of an acid, similar to step (b-3), can be mentioned. The method of ring-opening in the presence of an acid is as explained in step (b-3).

[0140] In relation to the above-mentioned embodiment, the present invention further discloses a method for producing a compound represented by general formula (I) and a method for producing a cyclic ketone compound represented by formula (3).

[0141] [1] The method includes a step of oxidatively cleaving a compound represented by general formula (II) using an oxidizing agent in the presence of a metal catalyst containing one or more metal elements selected from the group consisting of vanadium, iron, and molybdenum to obtain a compound represented by general formula (I). A method for producing a compound represented by general formula (I).

[0142] [ka]

[0143] In the formula (I) and formula (II), Formula-A 1 -(However, the previous bond is the carbon atom C 1 The latter bond is the carbon atom C 2 (meaning a bond bonded to) is an alkylene group having from 2 to 6 carbon atoms, which may be substituted and may include an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these; Formula-A 2 -(However, the previous bond is the carbon atom C 1 The latter bond is the carbon atom C 2 (meaning a bond bonded to) is an alkylene group having from 4 to 10 carbon atoms, which may be substituted and may include an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these.

[0144] [2] Formula-A 1 - is an optionally substituted alkylene group having 3 or 4 carbon atoms, Formula-A 2 The method according to [1], wherein - is an optionally substituted alkylene group having 4, 6, 8 or 10 carbon atoms.

[0145] [3] Formula-A 1- is a group of the formula -CH2-CH(CH3)-CH2-, and 2 - is a group of the formula -(CH2) 10 The method according to [1] or [2], wherein the - group is a - group.

[0146] [4] The method according to any one of [1] to [3], wherein the oxidative cleavage is carried out using a compound represented by the following formula (III) as an additive:

[0147] [ka]

[0148] In the formula (III), R is COOH or OH; R 1 , R 2 , R 3 , R 4 , and R 5 are each independently hydrogen, halogen atoms, NO2, OH, COOH, NR 6 R 7 (In the formula, R 6 and R 7 are each independently selected from the group consisting of hydrogen, an alkyl group having from 1 to 3 carbon atoms, or an alkyl group having from 1 to 3 carbon atoms substituted with OH, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, and a phenyl group (which may be substituted), or R 1 , R 2 , R 3 , R 4 , and R 5 Two of these groups together with the carbon atoms that support them form a saturated or unsaturated hydrocarbon ring, and the remaining three groups are each independently hydrogen, halogen atoms, NO2, OH, COOH, or NR 6 R 7 (In the formula, R 6 and R 7are each independently selected from the group consisting of hydrogen, an alkyl group having from 1 to 3 carbon atoms, or an alkyl group having from 1 to 3 carbon atoms substituted with OH, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, and a phenyl group (which may be substituted).

[0149] [5] R is COOH; R 1 , R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of hydrogen, a halogen atom, NO2, COOH, OH, and an alkoxy group having 1 to 6 carbon atoms.

[0150] [6] R is COOH and R 1 , R 2 , R 3 , R 4 , and R 5 The method according to any one of [3] to [5], wherein one of the groups is OH and the rest are each independently selected from the group consisting of hydrogen, a halogen atom, NO2, and an alkoxy group having 1 to 6 carbon atoms.

[0151] [7] The method according to any one of [3] to [6], wherein the additive comprises one or more selected from benzenecarboxylic acid, benzenedicarboxylic acid and benzenehydroxycarboxylic acid, each of which may be substituted with a halogen atom, NO2, or an alkoxy group having from 1 to 6 carbon atoms, and preferably comprises salicylic acid, which may be substituted with a halogen atom, NO2, or an alkoxy group having from 1 to 6 carbon atoms.

[0152] [8] The method according to any one of [1] to [7], wherein the metal catalyst is selected from the group consisting of vanadium (IV) compounds, vanadium (V) compounds, molybdenum (VI) compounds, iron (II) compounds, and iron (III) compounds.

[0153] [9] The method according to any one of [1] to [8], wherein the metal catalyst is selected from the group consisting of vanadium(V) oxide, vanadate(V), vanadium(V) oxytrialkoxide, and vanadium(IV) complex.

[0154]

[10] The method according to any one of [1] to [9], wherein the metal catalyst is selected from the group consisting of molybdenum(VI) oxide, molybdic acid, polymolybdic acid, heteropolymolybdic acid, and dioxomolybdenum(VI) complexes.

[0155]

[11] The method according to any one of [1] to

[10] , wherein the metal catalyst is selected from the group consisting of iron(II) oxide, iron(III) oxide, iron(II) nitrate, iron(III) nitrate, iron(II) sulfate, iron(III) sulfate, iron alkoxide, iron carboxylate, iron halide, and iron complex.

[0156]

[12] The method according to any one of [1] to

[11] , wherein the oxidizing agent is at least one selected from the group consisting of tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dimethyldioxirane, acetone peroxide, methyl ethyl ketone peroxide, hexamethylene triperoxide diamine, hydrogen peroxide, lithium peroxide, sodium peroxide, potassium peroxide, and permanganate.

[0157]

[13] The method according to any one of [1] to

[11] , wherein the oxidizing agent comprises hydrogen peroxide or tert-butyl hydroperoxide.

[0158]

[14] The method according to any one of [1] to

[13] , wherein the molar ratio of the metal catalyst to the compound represented by general formula (II) [metal catalyst / compound represented by general formula (II)] is 0.0001 or more and 1 or less.

[0159]

[15] The method according to any one of [1] to

[14] , wherein the molar ratio of the metal catalyst to the compound represented by general formula (II) [metal catalyst / compound represented by general formula (II)] is 0.001 or more and 0.7 or less.

[0160]

[16] The method according to any one of [1] to

[15] , wherein the molar ratio of the metal catalyst to the compound represented by general formula (II) [metal catalyst / compound represented by general formula (II)] is 0.01 or more and 0.3 or less.

[0161]

[17] The method according to any one of [1] to

[16] , wherein the molar ratio of the oxidizing agent to the compound represented by general formula (II) [oxidizing agent / compound represented by general formula (II)] is 0.5 or more and 20 or less.

[0162]

[18] The method according to any one of [1] to

[17] , wherein the molar ratio of the oxidizing agent to the compound represented by general formula (II) [oxidizing agent / compound represented by general formula (II)] is 1 or more and 10 or less.

[0163]

[19] The method according to any one of [1] to

[18] , wherein the molar ratio of the oxidizing agent to the compound represented by general formula (II) [oxidizing agent / compound represented by general formula (II)] is 1.2 or more and 5 or less.

[0164]

[20] The method according to any one of [1] to

[19] , wherein the oxidative cleavage is carried out at 0 to 100°C.

[0165]

[21] The method according to any one of [1] to

[20] , wherein the compound represented by general formula (II) is 14-methylbicyclo[10.3.0]pentadecene[1(12)] and the compound represented by general formula (I) is 3-methyl-1,5-cyclopentadecanedione.

[0166]

[22] 3-methyl-1,5-cyclopentadecanedione is obtained by the method described in

[21] . (a) a step of partially reducing 3-methyl-1,5-cyclopentadecanedione and then dehydrating it to obtain a cyclic ketone compound represented by formula (3); (b) reducing 3-methyl-1,5-cyclopentadecanedione, followed by enol etherification, and then ring-opening to obtain a cyclic ketone compound represented by formula (3); or (c) a step of partially reducing and enol-etherifying 3-methyl-1,5-cyclopentadecanedione, followed by ring-opening to obtain a cyclic ketone compound represented by formula (3). A method for producing a cyclic ketone compound represented by formula (3).

[0167] [ka] [Example]

[0168] [Compound yield] The yield of the compound obtained in the examples was calculated by measuring the mass of the compound in the crude product by gas chromatography internal standard quantitative analysis and dividing the number of moles of the compound by the number of moles of the raw material. <Gas chromatography equipment and analytical conditions> GC equipment: HEWLETT PACKARD, model: HP6850 Column: J&W DB-1 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm) Carrier gas: He, 1.5 mL / min Injection conditions: 300°C, split ratio 1 / 100 Detection conditions: FID method, 300°C Column temperature conditions: 80°C → 10°C / min temperature increase → 300°C for 10 minutes Internal standard compound: n-tridecane

[0169] [Compound Identification] Each compound obtained in the following Examples and Comparative Examples was identified by spectral analysis using a gas chromatograph mass spectrometer (GC-MS, manufactured by Shimadzu Corporation, model: GC-2010). <GC-MS Apparatus and Analysis Conditions> GC apparatus: manufactured by Shimadzu Corporation, model: GC-2010 MS apparatus: manufactured by Shimadzu Corporation, model: GCMS-QP2010 Plus Column: manufactured by J&W, DB-1 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm) Carrier gas: He, 1.8 mL / min Injection conditions: 300 °C, split ratio 1 / 50 Detection conditions: FID mode, 250 °C Column temperature conditions: 90 °C → heating up at a rate of 5 °C / min → 150 °C → heating up at a rate of 10 °C / min → 250 °C and holding for 28 minutes Ion source temperature: 200 °C

[0170] (Example 1) To 0.0072 g (0.05 mmol) of molybdenum trioxide (MoO3), 0.1417 g (2.5 mmol) of 60% by mass hydrogen peroxide solution and an were added, and the mixture was stirred at 20 °C for 20 minutes. To the mixture, 0.86 g of t-butyl alcohol and 0.22 g (1.0 mmol) of 14-methylbicyclo[10.3.0]pentadecene[1(12)] were added, and the reaction was stirred at a reaction temperature of 40 °C for 28 hours. After completion of the reaction, 10 ml of a 10% by mass aqueous sodium sulfite solution was added to the mixture in an ice bath to quench it. The organic layer was extracted from the mixture with 30 ml of diethyl ether, the organic layer was dried over magnesium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to obtain 0.3 g of a crude product. The yield of 3-methyl-1,5-cyclopentadecanedione (the compound of formula (1)) contained in the crude product was 10%. The reaction formula is shown below.

[0171]

Chemical formula

[0172] (Examples 2 - 9) Regarding the production of 3-methyl-1,5-cyclopentadecanedione (the compound of formula (1)), the reaction was carried out in the same manner as in Example 1 except that the conditions were changed as shown in Table 1. The results are shown in Table 1.

[0173] [Table 1]

[0174] From the results in Table 1 above, it was confirmed that the method of the present invention can produce the compound of formula (I) in the presence of a metal catalyst containing one or more metal elements selected from the group consisting of vanadium, iron, and molybdenum.

[0175] <Production of cyclic ketone compound represented by formula (3)> Example 10

[0176] [ka]

[0177] To 0.15 g (0.594 mmol) of 3-methyl-1,5-cyclopentadecanedione (compound of formula (1)) obtained in Example 1, 3 ml of methanol, 0.06 g (0.1 mmol) of a 10% by mass alcoholic suspension of Raney nickel catalyst, and 0.03 ml of a 10% by mass aqueous sodium hydroxide solution were added. The mixture was then stirred for 45 minutes at room temperature (25°C) under hydrogen at atmospheric pressure (0.1 MPa). The solvent was removed from the filtrate obtained by filtration under reduced pressure. The residue was diluted with diethyl ether and washed with a 10% by mass aqueous sodium bicarbonate solution and water. The organic layer was extracted, dried over magnesium sulfate, and filtered. The solvent was removed from the filtrate under reduced pressure to obtain 0.2 g of crude product. Gas chromatography analysis of the crude product revealed that the yield of the obtained 3-methylcyclopentadecanol-5-one (compound of formula (2)) was 50.0%.

[0178] To 0.07 g (0.275 mmol) of 3-methylcyclopentadecanol-5-one (compound of formula (2)), 3 mL of toluene and 0.004 g (0.027 mmol) of benzenesulfonic acid were added and stirred under reflux (110 °C) for 1 hour. Then, 10% by mass aqueous sodium bicarbonate solution was added at room temperature (25 °C), and the organic layer was extracted, dried over magnesium sulfate, filtered, and the solvent was removed from the filtrate under reduced pressure to obtain 0.06 g of crude product. Analysis of the crude product by gas chromatography revealed that the yield of the cyclic ketone compound represented by formula (3) was 80.0%.

[0179] Example 11

[0180] [ka]

[0181] To 0.15 g (0.594 mmol) of 3-methyl-1,5-cyclopentadecanedione (compound of formula (1)) obtained in Example 1, 3 ml of methanol, 0.06 g (0.1 mmol) of a 10% by mass alcoholic suspension of Raney nickel catalyst, and 0.03 ml of a 10% by mass aqueous sodium hydroxide solution were added. The mixture was then stirred at room temperature (25°C) and under normal pressure (0.1 MPa) of hydrogen for 24 hours, and the solvent was removed from the filtrate obtained by filtration under reduced pressure. The residue was diluted with diethyl ether and washed with a 10% by mass aqueous sodium bicarbonate solution and water. The organic layer was extracted, dried over magnesium sulfate, and filtered. The solvent was removed from the filtrate under reduced pressure to obtain 0.2 g of a crude product. Gas chromatography analysis of the crude product revealed that the yield of the resulting 3-methylcyclopentadecane-1,5-diol (compound of formula (4)) was 80.0%.

[0182] To 0.12 g (0.46 mmol) of 3-methylcyclopentadecane-1,5-diol (compound of formula (4)), 0.06 g (0.09 mmol) of a 10% by mass aqueous suspension of Raney copper was added, and the mixture was stirred at 165°C under a reduced pressure of 45 mmHg for 3 hours. The mixture was then distilled under a reduced pressure of 2 mmHg, yielding 0.06 g of a distillate fraction. Analysis of the distillate fraction by gas chromatography revealed that the yield of the resulting 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (compound of formula (5)) was 50.0%.

[0183] To 0.05 g (0.21 mmol) of 16-oxa-3-methylbicyclo[10.3.1]pentadec-1-ene (compound of formula (5)), 1 mL of toluene and 0.01 g (0.08 mmol) of 80% by weight aqueous phosphoric acid solution were added, and the mixture was stirred for 3 hours under reflux (110 °C) while continuously removing the by-product water. After cooling, the mixture was washed with water and 10% by weight aqueous sodium carbonate solution, and the organic layer was extracted. The solvent was removed under reduced pressure to obtain 0.05 g of crude product. Analysis of the crude product by gas chromatography revealed that the yield of the cyclic ketone compound represented by formula (3) was 85.0%. [Industrial Applicability]

[0184] According to the production method of the present invention, a method can be provided for producing a compound represented by general formula (I) by oxidative cleavage of a compound of formula (II), which is a bicyclic tetrasubstituted olefin compound.

Claims

1. The method includes a step of oxidatively cleaving the compound represented by general formula (II) using an oxidizing agent in the presence of a metal catalyst containing one or more metal elements selected from the group consisting of vanadium, iron, and molybdenum (excluding molybdenum chloride), to obtain the compound represented by general formula (I). A method for producing a compound represented by general formula (I). 【Chemical 21】 [In the formula (I) and formula (II), Formula-A 1 - (where the previous bond is the carbon atom C 1 The latter bond is the carbon atom C 2 (meaning a bond bonding to) is an alkylene group having from 2 to 6 carbon atoms, which may be substituted and may include an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these; Formula-A 2 - (where the previous bond is the carbon atom C 1 The latter bond is the carbon atom C 2 (meaning a bond bonded to) is an alkylene group having from 4 to 10 carbon atoms, which may be substituted, and which may include an ether bond, an ester bond, a secondary amino group, a thioether group, or any of these.

2. Formula-A 1 - represents an optionally substituted alkylene group having 3 or 4 carbon atoms, Formula-A 2 The method according to claim 1, wherein - is an optionally substituted alkylene group having 4, 6, 8 or 10 carbon atoms.

3. 3. The method according to claim 1, wherein the metal catalyst is selected from the group consisting of vanadium (IV) compounds, vanadium (V) compounds, molybdenum (VI) compounds, iron (II) compounds, and iron (III) compounds.

4. The method according to any one of claims 1 to 3, wherein the metal catalyst is selected from the group consisting of molybdenum (VI) oxide, molybdic acid, dioxomolybdenum (VI) complexes, polymolybdic acid, and heteropolymolybdic acid.

5. The method according to any one of claims 1 to 4, wherein the oxidizing agent comprises hydrogen peroxide or tert-butyl hydroperoxide.

6. The method according to any one of claims 1 to 5, wherein a molar ratio of the metal catalyst to the compound represented by general formula (II) [metal catalyst / compound represented by general formula (II)] is 0.0001 or more and 1 or less.

7. The method according to any one of claims 1 to 6, wherein the molar ratio of the oxidizing agent to the compound represented by general formula (II) [oxidizing agent / compound represented by general formula (II)] is 0.5 or more and 20 or less.

8. The method according to any one of claims 1 to 7, wherein the oxidative cleavage is carried out at a temperature of 0 to 100°C.

9. The method according to any one of claims 1 to 8, wherein the compound represented by general formula (II) is 14-methylbicyclo[10.3.0]pentadecene[1(12)], and the compound represented by general formula (I) is 3-methyl-1,5-cyclopentadecanedione.

10. 3-methyl-1,5-cyclopentadecanedione is obtained by the method according to claim 9, (a) a step of partially reducing 3-methyl-1,5-cyclopentadecanedione and then dehydrating it to obtain a cyclic ketone compound represented by formula (3); (b) reducing 3-methyl-1,5-cyclopentadecanedione, followed by enol etherification, and then ring-opening to obtain a cyclic ketone compound represented by formula (3); or (c) a step of partially reducing and enol-etherifying 3-methyl-1,5-cyclopentadecanedione, followed by ring-opening to obtain a cyclic ketone compound represented by formula (3). A method for producing a cyclic ketone compound represented by formula (3). 【Chemical 22】

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