JP2004307480A - Method for producing oxygenated compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To oxidize an olefin having a carbon-carbon double bond bonded to a methyl group or a methylene group to produce oxygen-containing compounds such as alcohols, aldehydes, ketones and carboxylic acids more industrially advantageously. SOLUTION: An olefin having a carbon-carbon double bond bonded to a methyl group or a methylene group is reacted with an organic hydroperoxide in the presence of an ionic liquid and a selenium compound. For producing oxygen-containing compounds.
[Selection diagram] None

Description

  The present invention relates to a method for producing an oxygen-containing compound.

  For example, olefins having a carbon-carbon double bond bonded to a methyl group or a methylene group such as a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group (hereinafter abbreviated as olefins). Oxygen-containing compounds such as alcohols, ketones, aldehydes, and carboxylic acids obtained by oxidizing the methyl group or methylene group are extremely important compounds as various chemical products and synthetic intermediates thereof. For example, 3,3-dimethyl-2 obtained by oxidizing the methyl group of the 2-methyl-1-propenyl group at the 2-position of 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylic acid esters. -E- (2-carboxy-1-propenyl) cyclopropanecarboxylic acid ester is a chrysanthemic acid derivative which is important as an acid moiety in household epidemics and insecticides known as second chrysanthemic acid (for example, non-patented). Literature 1), E, E-2,6-dimethyl-2,6-octadiene-1,8-diol-8-acetate in which the terminal methyl group of geranyl acetate is oxidized is an intermediate for natural product synthesis. It is useful (for example, see Non-Patent Document 2).

  The methyl group or methylene group bonded to the carbon-carbon double bond of the olefin is an allylic methyl or methylene group, and the allylic methyl or methylene group is oxidized to produce an oxygen-containing compound. Examples of the method include a method of reacting the olefin with selenium dioxide (for example, see Non-Patent Documents 3 and 4) and a method of reacting an olefin with an organic hydroperoxide in the presence of a selenium dioxide catalyst. (For example, see Non-Patent Document 5). However, the former method uses a large amount of selenium dioxide, and since it becomes selenium metal after the reaction, it has been necessary to oxidize the selenium metal again for reuse. Further, the latter methods are not industrially satisfactory in that methylene chloride, which has problems in occupational safety and health, is used as a solvent, and it is difficult to recover and reuse selenium dioxide as a catalyst. Did not.

Synthetic Pyrethroid Insecticides: Structure and Properties, 3 (1990) Tetrahedron Letters, 42, 2205 (2001) Comprehensive Organic Synthesis, 7, 83 (1991) Proc. Japan Acad., 32, 353 (1956) J. Amer. Chem. Soc., 99, 5526 (1977)

  Under such circumstances, the present inventors oxidize olefins having a carbon-carbon double bond bonded to a methyl group or a methylene group to form alcohols, aldehydes, ketones, carboxylic acids, and the like. After extensive studies to develop a method for producing an oxygen-containing compound more industrially and advantageously, the olefins and an organic hydroperoxide were reacted in the presence of an ionic liquid and a selenium compound, whereby The present inventors have found that the oxidation reaction of the methyl group or methylene group at the allyl position of the olefin proceeds efficiently, and that an oxygen-containing compound can be obtained, and that the selenium compound can be easily recovered and reused.

  That is, the present invention provides an oxygen-containing compound comprising reacting an olefin having a carbon-carbon double bond bonded to a methyl group or a methylene group with an organic hydroperoxide in the presence of an ionic liquid and a selenium compound. A method for producing a compound is provided.

  According to the present invention, the allyl position of the olefins can be oxidized with high selectivity, and oxygen-containing compounds such as alcohols, aldehydes, ketones, and carboxylic acids can be obtained. Moreover, it is easy to recover and reuse the ionic liquid and the selenium compound, which is industrially advantageous.

（式中、Ｒ^１は置換されていてもよいアルキル基、置換されていてもよいアリール基または置換されていてもよいアラルキル基を表わす。Ｒ^２、Ｒ^３およびＲ^４はそれぞれ同一または相異なって、置換されていてもよいアルキル基、置換されていてもよいアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基、置換されていてもよいアラルキル基、置換されていてもよいアラルキルオキシ基、置換されていてもよいアルキルカルボニル基、置換されていてもよいアリールカルボニル基、置換されていてもよいアラルキルカルボニル基、置換されていてもよいアルコキシカルボニル基、置換されていてもよいアリールオキシカルボニル基、置換されていてもよいアラルキルオキシカルボニル基、カルボキシル基、ハロゲン原子または水素原子を表わす。ここで、Ｒ^１とＲ^３、Ｒ^２とＲ^４、Ｒ^１とＲ^２およびＲ^３とＲ^４のうちの少なくとも一組が結合して、その結合炭素原子とともに環を形成してもよい。）
で示される化合物（以下、化合物（１）と略記する。）や式（４）

（式中、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ上記と同一の意味を表わす。ここで、Ｒ^２とＲ^４またはＲ^３とＲ^４が結合して、その結合炭素原子とともに環を形成してもよい。）
で示される化合物（以下、化合物（４）と略記する。）等が挙げられる。 The olefins in the present invention have a structure in which a methyl group or a methylene group is bonded to a carbon-carbon double bond such as a 1-propenyl group, a 2-propenyl group, or a 2-methyl-1-propenyl group in the molecule. There is no particular limitation as long as it is an olefin having the formula:

(In the formula, R ¹ represents an alkyl group which may be substituted, an aryl group which may be substituted, or an aralkyl group which may be substituted. R ² , R ³ and R ⁴ are the same or different. An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted aralkyl group, Optionally substituted aralkyloxy group, optionally substituted alkylcarbonyl group, optionally substituted arylcarbonyl group, optionally substituted aralkylcarbonyl group, optionally substituted alkoxycarbonyl group, substituted An optionally substituted aryloxycarbonyl group, an optionally substituted aralkyloxycarbonyl group, Sill group, a halogen atom or a hydrogen atom. Here, with ^{R 1} and ^R 3, ^{R 2} and ^R 4, at least one pair of ^{R 1} and ^{R 2} and ^{R 3} and ^{R 4} are bonded, the bond A ring may be formed together with the carbon atom.)
(Hereinafter abbreviated as compound (1)) and formula (4)

(Wherein, R ² , R ³ and R ⁴ each have the same meaning as described above. Here, R ² and R ⁴ or R ³ and R ⁴ are bonded to form a ring together with the bonded carbon atom. May be.)
(Hereinafter abbreviated as compound (4)), and the like.

  Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-decyl, and cyclopropyl. Linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms such as a group, a 2,2-dimethylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a menthyl group. Such an alkyl group may be an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted aralkyloxy group, a halogen atom, an optionally substituted alkylcarbonyl group, Optionally substituted arylcarbonyl group, optionally substituted aralkylcarbonyl group, optionally substituted alkoxycarbonyl group, optionally substituted aryloxycarbonyl group, optionally substituted aralkyloxycarbonyl group May be substituted with a carboxyl group or the like, examples of the alkyl group substituted with such a substituent include a chloromethyl group, a fluoromethyl group, a trifluoromethyl group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, And a methoxycarbonylmethyl group.

  Examples of the optionally substituted alkoxy group include those composed of the above-mentioned optionally substituted alkyl group and an oxygen atom, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n -Butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, n-decyloxy group, cyclopentyloxy group, cyclohexyloxy group, menthyloxy group, chloromethoxy group, fluoromethoxy group, trifluoro Examples include a methoxy group, a methoxymethoxy group, an ethoxymethoxy group, and a methoxyethoxy group.

  Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aryl group include the aforementioned optionally substituted alkyl group, the aforementioned optionally substituted alkoxy group, the aforementioned aryl group, the aforementioned optionally substituted aralkyl group, and the aforementioned optionally substituted aryloxy And an optionally substituted aralkyloxy group described below, and a substituent such as a halogen atom described below. Examples of the substituted aryl group include a 2-methylphenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, and a 3-phenoxyphenyl group. Examples of the optionally substituted aryloxy group include those composed of the aforementioned optionally substituted aryl group and an oxygen atom, such as a phenoxy group, a 2-methylphenoxy group, a 4-chlorophenoxy group, Examples include a 4-methylphenoxy group, a 4-methoxyphenoxy group, and a 3-phenoxyphenoxy group.

  Examples of the optionally substituted aralkyl group include those composed of the above-mentioned optionally substituted aryl group and the above-mentioned alkyl group, such as a benzyl group, a 4-chlorobenzyl group and a 4-methylbenzyl group. , 4-methoxybenzyl group, 3-phenoxybenzyl group, 2,3,5,6-tetrafluorobenzyl group, 2,3,5,6-tetrafluoro-4-methylbenzyl group, 2,3,5,6 -Tetrafluoro-4-methoxybenzyl group, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl group and the like. Examples of the aralkyloxy group which may be substituted include those composed of an aralkyl group which may be substituted and an oxygen atom, such as a benzyloxy group, a 4-chlorobenzyloxy group and a 4-methylbenzyl group. Oxy, 4-methoxybenzyloxy, 3-phenoxybenzyloxy, 2,3,5,6-tetrafluorobenzyloxy, 2,3,5,6-tetrafluoro-4-methylbenzyloxy, 2 , 3,5,6-tetrafluoro-4-methoxybenzyloxy group, and 2,3,5,6-tetrafluoro-4-methoxymethylbenzyloxy group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The optionally substituted alkylcarbonyl group, the optionally substituted arylcarbonyl group and the optionally substituted aralkylcarbonyl group include a carbonyl group and the optionally substituted alkyl group, And an aralkyl group which may be substituted, such as an acetyl group, an ethylcarbonyl group, a benzoyl group, and a benzylcarbonyl group.

  The optionally substituted alkoxycarbonyl group, the optionally substituted aryloxycarbonyl group and the optionally substituted aralkyloxycarbonyl group are respectively a carbonyl group and the optionally substituted alkoxy group, And an aralkyloxy group which may be substituted, such as a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, and a benzyloxycarbonyl group. .

  Examples of such olefins include geranyl acetate, geranyl benzoate, geranyl methyl ether, geranyl benzyl ether, geranyl phenyl sulfone, geranylacetone, prenyl acetate, methyl 7-octenoate, 1-hexene, 1-heptene, 1-octene, -Dodecene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3-chlorocyclopentene, 1-methylcyclohexene, 1,4-dimethylcyclohexene, 3-methylcyclohexene , 2-hexene, 1,7-octadiene, 1,2,3,4-tetrahydrophthalic anhydride, indene, α-methylstyrene, β-methylstyrene, β-benzyls Len, 4-methoxy-6-methyl-2H-pyran-2-one, methylenecyclobutane, methylenecyclopentane, β-pinene, α-methylene-γ-butyrolactone, cyclohexylidenecyclohexane, pulegone, isophorone, 2-carene, 3 -Carene, α-pinene and the like.

  In this reaction, an olefin and an organic hydroperoxide are reacted in the presence of an ionic liquid and a selenium compound, and a methyl group or a methylene group bonded to a carbon-carbon double bond of the olefin is oxidized. The resulting oxygenated compound is obtained. When an olefin having a structure in which a methylene group is bonded to a carbon-carbon double bond is used, alcohols and / or ketones are obtained. The production ratio depends on the amount of the organic hydroperoxide used and the reaction conditions. Depends on etc. When an olefin having a structure in which a methyl group is bonded to a carbon-carbon double bond is used, at least one oxygen-containing compound selected from the group consisting of alcohols, aldehydes, and carboxylic acids is obtained. The production ratio varies depending on the amount of organic hydroperoxide used, reaction conditions, and the like.

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は上記と同一の意味を表わす。）
で示される化合物および／または式（３）

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は上記と同一の意味を表わす。）
で示される化合物が得られる。さらに具体的に化合物を挙げて説明すると、オレフィン類として、シクロヘキセンを用いた場合には、２−シクロヘキセノールおよび／または２−シクロヘキセノンが得られる。 When the compound (1) is used as the olefin, for example, the compound represented by the formula (2)

(Wherein, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above.)
And / or formula (3)

(Wherein, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above.)
Is obtained. More specifically, a compound will be described. When cyclohexene is used as the olefin, 2-cyclohexenol and / or 2-cyclohexenone can be obtained.

（式中、Ｒ^２、Ｒ^３およびＲ^４は上記と同一の意味を表わす。）
で示される化合物；
式（６）

（式中、Ｒ^２、Ｒ^３およびＲ^４は上記と同一の意味を表わす。）
で示される化合物；
式（７）

（式中、Ｒ^２、Ｒ^３およびＲ^４は上記と同一の意味を表わす。）
で示される化合物；
からなる群から選ばれる少なくとも１つの化合物が得られる。さらに具体的に化合物を挙げて説明すると、オレフィン類として、例えばイソホロンを用いた場合には、３−ヒドロキシメチル−５，５−ジメチル−２−シクロヘキセン−１−オンおよび／またはホルミルイソホロンおよび／または５，５−ジメチル−３−オキソ−１−シクロヘキセン−１−カルボン酸が得られる。 When the compound (4) is used as the olefin, for example, the compound represented by the formula (5)

(Wherein, R ² , R ³ and R ⁴ represent the same meaning as described above.)
A compound represented by the formula:
Equation (6)

(Wherein, R ² , R ³ and R ⁴ represent the same meaning as described above.)
A compound represented by the formula:
Equation (7)

(Wherein, R ² , R ³ and R ⁴ represent the same meaning as described above.)
A compound represented by the formula:
At least one compound selected from the group consisting of More specifically, a compound will be described. For example, when isophorone is used as the olefin, 3-hydroxymethyl-5,5-dimethyl-2-cyclohexen-1-one and / or formylisophorone and / or 5,5-Dimethyl-3-oxo-1-cyclohexene-1-carboxylic acid is obtained.

  Examples of the selenium compound include divalent, tetravalent or hexavalent selenium compounds such as selenium dioxide, selenium disulfide, selenyl chloride, selenic acid, selenous acid, selenium tetrachloride, selenocystine, selenourea, and dimethylselenourea. And preferably selenium dioxide, selenic acid and selenious acid. These selenium compounds may be used alone or as a mixture. The amount of the selenium compound to be used is usually 0.001 to 0.95 mol times based on the olefins.

  Examples of the organic hydroperoxide include tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumene hydroperoxide, cymene hydroperoxide and the like. The organic hydroperoxide is usually used as an aqueous solution or an organic solvent solution. The concentration of the organic hydroperoxide in the aqueous solution or the organic solvent solution is not particularly limited, but is practically about 1 to 90% by weight in consideration of volume efficiency, safety and the like.

  In the present invention, since the type and the production ratio of the oxygen-containing compound to be produced vary depending on the amount of the organic hydroperoxide used, the amount to be used may be appropriately determined according to the target oxygen-containing compound. For example, the amount of the organic hydroperoxide used for the purpose of alcohols is usually about 1 to 2 mole times the amount of the olefin, and the amount of the organic hydroperoxide used for the purpose of aldehydes is The amount is usually about 2 to 3 mole times, and the amount of the organic hydroperoxide used for the purpose of ketones is usually 2 mole times or more, and there is no particular upper limit, but considering the economic aspect, Practically, it is 50 mole times or less. The amount of the organic hydroperoxide used for the purpose of carboxylic acids is usually 3 mol times or more, and there is no particular upper limit. However, considering the economic aspect, it is practically 50 mol times or less. .

  Examples of the ionic liquid include a compound that is a salt composed of an organic cationic species and an anionic species, has a melting point of 100 ° C. or less, and maintains a stable and liquid state up to a high temperature of about 300 ° C. Such ionic liquids include, for example, alkyl-substituted imidazolium salts, alkyl-substituted pyridinium salts, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts and the like, with alkyl-substituted imidazolium salts being preferred.

  Examples of the alkyl-substituted imidazolium salt include an imidazolium cation in which at least one nitrogen atom on the imidazoline ring is bonded to an alkyl group which may be substituted, for example, a tetrafluoroborate anion, a chloride anion, a bromine anion, and an iodine anion. Salts composed of anion species such as hexafluorophosphate anion, bis (perfluoroalkanesulfonyl) amide anion, alkylcarboxylate anion, and alkanesulfonate anion are exemplified. Here, examples of the alkyl group which may be substituted include lower alkyl groups having 1 to 8 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and an n-pentyl group. Alkyl groups and lower alkoxy groups having 1 to 8 carbon atoms such as methoxy group and ethoxy group; halogen atoms such as fluorine atom, chlorine atom and bromine atom; Examples include a methyl group, a trifluoromethyl group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, and a methoxycarbonylmethyl group. Such an optionally substituted alkyl group may also be attached to a carbon atom on the imidazoline ring.

  Such alkyl-substituted imidazolium salts include, for example, 1-methyl-3-methylimidazolium tetrafluoroborate, 1-methyl-3-ethylimidazolium tetrafluoroborate, 1-methyl-3-butylimidazolium tetrafluoroborate, -Methyl-3-isobutylimidazolium tetrafluoroborate, 1-methyl-3-methoxyethylimidazolium tetrafluoroborate, 1-ethyl-3-ethylimidazolium tetrafluoroborate, 1-ethyl-3-butylimidazolium tetrafluoroborate Borate, 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-ethyl-3,5-dimethylimidazolium tetrafluoroborate, 1,3-diethyl-5-methylimidazolium tetrafluroate Alkyl-substituted imidazolium tetrafluoroborate such as roborate and 1-ethylimidazolium tetrafluoroborate, and alkyl-substituted imidazolium chloride in which the tetrafluoroborate anion of each of the above compounds is replaced by chlorine anion; and the tetrafluoroborate anion of each of the above compounds is bromine. Alkyl-substituted imidazolium bromide in place of an anion; alkyl-substituted imidazolium iodide in which the tetrafluoroborate anion of each compound is replaced by iodine anion; alkyl-substituted imidazolium in which tetrafluoroborate anion of each compound is replaced by hexafluorophosphate anion Lithium hexafluorophosphate; the tetrafluoroborate anion of each of the above compounds is bis (perfluoroalkanesulfonyl) amido; An alkyl-substituted imidazolium bis (perfluoroalkanesulfonyl) amide substituted for an anion; an alkyl-substituted imidazolium alkylcarboxylate in which the tetrafluoroborate anion of each of the compounds is replaced with an alkylcarboxylate anion; Alkyl-substituted imidazolium alkane sulfonates in place of alkane sulfonate anions;

  Examples of the alkyl-substituted pyridinium salt include a salt composed of a pyridinium cation in which a nitrogen atom on a pyridine ring is bonded to the alkyl group which may be substituted and the anion species, for example, N-methylpyridinium tetra Fluoroborate, N-ethylpyridinium tetrafluoroborate, N-propylpyridinium tetrafluoroborate, N-butylpyridinium tetrafluoroborate, N-butyl-4-methylpyridinium tetrafluoroborate, N-isobutylpyridinium tetrafluoroborate, N-pentyl Alkyl substituted pyridinium tetrafluoroborate such as pyridinium tetrafluoroborate and the like Um chloride; an alkyl-substituted pyridinium bromide in which the tetrafluoroborate anion of each of the compounds is replaced by a bromine anion; an alkyl-substituted pyridinium iodide in which the tetrafluoroborate anion of each of the compounds is replaced by an iodine anion; Alkyl-substituted pyridinium bis (perfluoroalkanesulfonyl) amide in which the tetrafluoroborate anion of each of the above compounds is replaced by bis (perfluoroalkanesulfonyl) amide anion; alkyl-substituted pyridinium bis (perfluoroalkanesulfonyl) amide in which each of the above compounds is substituted Substituted pyridinium alkyl carboxy substituted for alkyl carboxylate by tetrafluoroborate anion Over preparative; like; the tetrafluoroborate anion of the compound is an alkyl-substituted pyridinium alkane sulfonates behalf alkane sulfonate anions.

  Examples of the quaternary ammonium salt include, for example, a salt composed of an ammonium cation composed of the same or different four alkyl groups which may be substituted and a nitrogen atom, and the aforementioned anionic species. Quaternary ammonium tetrafluoroborate such as trimethylpentylammonium tetrafluoroborate, trimethylhexylammonium tetrafluoroborate, trimethylheptylammonium tetrafluoroborate, trimethyloctylammonium tetrafluoroborate, triethylpentylammonium tetrafluoroborate and the like, A quaternary ammonium hexafluorophosphate in which the borate anion replaces the hexafluorophosphate anion; A quaternary ammonium bis (perfluoroalkanesulfonyl) amide in which the fluoroborate anion is replaced by a bis (perfluoroalkanesulfonyl) amide anion; a quaternary ammonium alkyl in which the tetrafluoroborate anion of each of the above compounds is replaced by an alkylcarboxylate anion Carboxylate; a quaternary ammonium alkane sulfonate in which the tetrafluoroborate anion of each compound is replaced with an alkane sulfonate anion;

  Examples of the quaternary phosphonium salt include salts composed of a phosphonium cation composed of the same or different four optionally substituted alkyl groups and a phosphorus atom, and the aforementioned anionic species. For example, quaternary phosphonium tetrafluoroborate of trimethylpentylphosphonium tetrafluoroborate, tetrabutylphosphonium tetrafluoroborate, and quaternary phos- phos in which the tetrafluoroborate anion of each of the above compounds is replaced with hexafluorophosphate anion Phonium hexafluorophosphate; a quaternary phosphonium bis (perfluoroalkanesulfonyl) amide in which the tetrafluoroborate anion of each compound is replaced with a bis (perfluoroalkanesulfonyl) amide anion; A quaternary phosphonium alkyl carboxylate in which the tetrafluoroborate anion of each compound is replaced by an alkyl carboxylate anion; a quaternary phosphonium alkane sulfonate in which the tetrafluoroborate anion of each compound is replaced by an alkane sulfonate anion; Is mentioned.

  Examples of the tertiary sulfonium salt include, for example, a salt composed of a sulfonium cation composed of the same or different three alkyl groups which may be substituted and a sulfur atom, and the above-mentioned anionic species. Tertiary sulfonium tetrafluoroborate such as triethylsulfonium tetrafluoroborate, tributylsulfonium tetrafluoroborate and tertiary sulfonium tetrafluoroborate in which the tetrafluoroborate anion of each compound is replaced with hexafluorophosphate anion Phosphate; tertiary sulfonium bis (perfluoroa) in which the tetrafluoroborate anion of each compound is replaced with a bis (perfluoroalkanesulfonyl) amide anion Cansulfonyl) amide; tertiary sulfonium alkyl carboxylate in which the tetrafluoroborate anion of each compound is replaced with an alkyl carboxylate anion; tertiary sulfonium alkane sulfonate in which the tetrafluoroborate anion of each compound is replaced with an alkane sulfonate anion And the like.

  The amount of the ionic liquid is not particularly limited, but is usually about 0.1 to 100 times by weight based on the selenium compound.

  This reaction is generally performed without a solvent, but may be performed in the presence of a solvent. Examples of the solvent include ether solvents such as diethyl ether, methyl tert-butyl ether and tetrahydrofuran; ester solvents such as ethyl acetate; alcohol solvents such as methanol, ethanol and tert-butanol; nitrile solvents such as acetonitrile and propionitrile A single or mixed solvent such as water; and the amount thereof is not particularly limited.

  In this reaction, an oxygen-containing compound can be obtained with higher yield by coexisting with an aromatic carboxylic acid. Examples of the aromatic carboxylic acid include benzoic acid, salicylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, picolinic acid, nicotinic acid, There is no particular limitation on the amount of isonicotinic acid and the like, but it is practically 0.1 to 10 times the molar amount of the selenium compound.

  In this reaction, an olefin, an ionic liquid, an organic hydroperoxide, a selenium compound and, if necessary, a solvent or an aromatic carboxylic acid may be mixed, and the mixing order is not particularly limited. It is shown below. First, an ionic liquid, a selenium compound, and a part of an organic hydroperoxide are mixed. At this time, an aromatic carboxylic acid may be mixed if necessary. Then, after adding the olefins, the remaining organic hydroperoxide is added, and the mixture is stirred at the reaction temperature, whereby the oxygen-containing compound can be obtained in good yield.

  When the reaction temperature is too low, the reaction does not easily proceed, and when the reaction temperature is too high, a side reaction such as polymerization of the raw material olefins may proceed. Therefore, a practical reaction temperature is 0 to 200 ° C. Range.

  This reaction may be performed under normal pressure conditions or may be performed under pressurized conditions. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR and IR.

  After completion of the reaction, the reaction liquid is decomposed as it is or, if necessary, the remaining organic hydroperoxide is decomposed with a reducing agent such as sodium sulfite. The oxygen-containing organic layer can be separated. When an aqueous solution is used at the time of reaction or post-treatment with a reducing agent, the aqueous solution may be separated into three layers: an ionic liquid layer, an oxygen-containing compound-containing organic layer, and an aqueous layer. Thus, an oxygen-containing compound-containing organic layer and an ionic liquid layer may be obtained. The oxygen-containing compound can be taken out by concentrating the organic layer thus obtained. The removed oxygen-containing compound may be further purified by a conventional purification means such as, for example, distillation or column chromatography.

  Examples of the organic solvent that does not mix with the ionic liquid include aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane, and aromatic hydrocarbon solvents such as toluene and xylene. Is not particularly limited.

  The ionic liquid layer usually contains a selenium compound or an oxide of the selenium compound, and the ionic liquid containing the selenium compound or the oxide of the selenium compound may be used as it is or as needed. After performing concentration treatment or the like, it can be used again in the present reaction. When such an ionic liquid layer is reused, a new selenium compound may not be used, but a selenium compound may be additionally used as necessary.

  Among the oxygenated compounds thus obtained, examples of the alcohols include E, E-2,6-dimethyl-2,6-octadien-8-acetoxy-1-ol and E, E-2,6-dimethyl-2. , 6-Octadien-8-benzoyloxy-1-ol, E, E-2,6-dimethyl-2,6-octadien-8-methoxy-1-ol, E, E-2,6-dimethyl-2, 6-octadien-8-benzyloxy-1-ol, E, E-2,6-dimethyl-2,6-octadien-1-ol-8-phenylsulfone, E, E-11-hydroxy-6,10- Dimethyl-5,9-undecadien-2-one, E-2-methyl-4-acetate-2-butene-1,4-diol, 6-hydroxy-7-octenoic acid methyl ester, 1-hexen-3-o 1-hepten-3-ol, 1-octen-3-ol, 1-dodecene-3-ol, 1-hydroxy-2-cyclopentene, 1-hydroxy-2-cyclohexene, 1-hydroxy-2-cycloheptene, 1-hydroxy-2-cyclooctene, 1-hydroxy-4-methyl-2-cyclopentene, 1-hydroxy-5-methyl-2-cyclopentene, 1-hydroxy-4,5-dimethyl-2-cyclopentene, 1-hydroxy -4-chloro-2-cyclopentene, 2-methyl-2-cyclohexen-1-ol, 2,5-dimethyl-2-cyclohexen-1-ol, 1-hydroxy-4-methyl-2-cyclohexene, 4-hydroxy -2-hexene, 3-hydroxy-1,7-octadiene, 3-hydroxy-1,2,3,6 Tetrahydrophthalic anhydride, 1-inden-1-ol, 3-phenyl-2-propen-1-ol, 1,3-diphenyl-2-propen-1-ol, 6- (hydroxymethyl) -4-methoxy- 2H-pyran-2-one, 2-phenyl-2-propen-1-ol, 2-methylenecyclobutanol, 2-methylenecyclopentanol, pinocarberol, dihydro-4-hydroxy-3-methylene-2-furanone 2-cyclohexylidenecyclohexanol, 2- (2-hydroxy-1-methylmethylidene) -5-methylcyclohexanone, 3-hydroxymethyl-5,5-dimethyl-2-cyclohexen-1-one, 2-carene-10 -Ol, isocamol, myrtenol and the like.

  Examples of the aldehydes include E, E-2-formyl-8-acetoxy-6-methyl-2,6-octadiene and E, E-2-formyl-8-benzoyloxy-6-methyl-2,6-octadiene. E, E-2-formyl-8-methoxy-6-methyl-2,6-octadiene, E, E-2-formyl-8-benzyloxy-6-methyl-2,6-octadiene, E, E- 2-formyl-8-phenylsulfone-6-methyl-2,6-octadiene, E, E-2,6-dimethyl-10-oxo-2,6-undecadienal, E-4- (acetyloxy)- 2-methyl-2-butenal, α-formylstyrene, 3-phenyl-2-propenal, 4-methoxy-2-oxo-2H-pyran-6-carboxyaldehyde, 2- (4-methyl-2 Cyclohexylidene) propanal, formyl isophorone, 7,7-dimethyl-2-Norukaren 3-carboxaldehyde, 7,7-dimethyl-3-Norukaren 3-carboxaldehyde, Mirutenonaru and the like.

  Examples of ketones include methyl 6-oxo-7-octenoate, 3-oxo-1-hexene, 3-oxo-1-heptene, 3-oxo-1-octene, 3-oxo-1-dodecene, -Cyclopentenone, 2-methyl-2-cyclohexen-1-one, 2,5-dimethyl-2-cyclohexen-1-one, 2-cyclohexenone, 2-cycloheptenone, 2-cyclooctenone, 4-methyl- 2-cyclopentenone, 5-methyl-2-cyclopentenone, 4,5-dimethyl-2-cyclopentenone, 4-chloro-2-cyclopentenone, 4-methyl-2-cyclohexenone, 4-oxo -2-hexene, 3-oxo-1,7-octadiene, 3-oxo-1,2,3,6-tetrahydrophthalic anhydride, inden-1-one, 1,3- Phenyl-2-propen-1-one, 2-methylene-cyclobutanone, 2-methylene cyclopentanone, Pinokarubon, dihydro-4-oxo-3-methylene-2-furanone, 2-cyclohexylidene cyclohexanone.

  Examples of the carboxylic acids include E, E-2-carboxy-8-acetoxy-6-methyl-2,6-octadiene and E, E-2-carboxy-8-benzoyloxy-6-methyl-2,6-octadiene. , E, E-2-carboxy-8-methoxy-6-methyl-2,6-octadiene, E, E-2-carboxy-8-benzyloxy-6-methyl-2,6-octadiene, E, E- 2-carboxy-8-phenylsulfone-6-methyl-2,6-octadiene, E, E-2,6-dimethyl-10-oxo-2,6-undecadienoic acid, E-4- (acetyloxy) -2- Methyl-2-butenoic acid, α-carboxystyrene, 2- (4-methyl-2-cyclohexylidene) propanoic acid, 5,5-dimethyl-3-oxo-1-cyclohexene-1 Carboxylic acid, 7,7-dimethyl - bicyclo [4.1.0] hept-2-ene-3-carboxylic acid, Kaminikku acid and Mirutenikku acid.

  Next, the application of the present invention will be described with reference to specific examples, but the present invention is not limited thereto.

（式中、Ｒ^５は置換されていてもよいアルキル基、置換されていてもよいアリール基または置換されていてもよいアラルキル基を表わす。）
で示される化合物（以下、菊酸エステル（８）と略記する。）を用いれば、含酸素化合物として、式（９）

（式中、Ｒ^５は上記と同一の意味を表わす。）
で示される化合物（以下、アルコール（９）と略記する。）；
式（１０）

（式中、Ｒ^５は上記と同一の意味を表わす。）
で示される化合物（以下、アルデヒド（１０）と略記する。）；
式（１１）

（式中、Ｒ^５は上記と同一の意味を表わす。）
で示される化合物（以下、カルボン酸（１１）と略記する。）；
からなる群から選ばれる少なくとも１つの化合物を得ることができる。 As the olefins in the present invention, for example, a compound represented by the formula (8)

(In the formula, R ⁵ represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group.)
(Hereinafter abbreviated as chrysanthemic acid ester (8)), an oxygen-containing compound represented by the formula (9)

(Wherein, R ⁵ has the same meaning as described above.)
(Hereinafter abbreviated as alcohol (9));
Equation (10)

(Wherein, R ⁵ has the same meaning as described above.)
(Hereinafter abbreviated as aldehyde (10));
Equation (11)

(Wherein, R ⁵ has the same meaning as described above.)
(Hereinafter abbreviated as carboxylic acid (11));
At least one compound selected from the group consisting of

Optionally substituted alkyl group, an aralkyl group which may be also substituted aryl groups and substituted substituted include the same ones as exemplified for the R ^1.

  Examples of the chrysanthemic acid ester (8) include, for example, methyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate and 3,3-dimethyl-2- (2-methyl-1-propenyl) Ethyl cyclopropanecarboxylate, isopropyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate, 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate tert-butyl, cyclohexyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate, menthyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate, Benzyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate, 3,3-dimethyl 2- (2-methyl-1-propenyl) cyclopropanecarboxylic acid (4-chlorobenzyl), 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylic acid (2,3,5, 6-tetrafluorobenzyl), 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylbenzyl), 3,3- Dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methoxybenzyl), 3,3-dimethyl-2- (2-methyl-1- Propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methoxymethylbenzyl), 3,3-dimethyl-2- (2-methyl-1-propenyl) cycl Propane carboxylic acid (3-phenoxybenzyl) and the like.

Such chrysanthemic acid ester (8), to the cyclopropane ring plane, -CO ₂ group and 2-methyl-1-propenyl group represented by R ⁵ is, trans-isomer in the cis form opposite on the same side Exists, but either one of them may be used in the present invention, or a mixture may be used. When a mixture is used, the mixing ratio of the cis form and the trans form is not particularly limited.

  Further, such chrysanthemic acid ester (8) has an asymmetric carbon atom in the molecule and has optical isomers. In the present invention, either of the optical isomers alone or a mixture thereof may be used. Good.

  Among the obtained oxygenated compounds, examples of the alcohol (9) include methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate, and 3,3-dimethyl-2- E-ethyl (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate, isopropyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate, 3,3-dimethyl- Tert-butyl 2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate, cyclohexyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate, 3, 3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylic acid Butyl, benzyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate, 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropane Carboxylic acid (4-chlorobenzyl), 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluorobenzyl), 3,3 -Dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methylbenzyl), 3,3-dimethyl-2-E- ( 2-hydroxymethyl-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methoxybenzyl), 3,3-dimethyl 2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methoxymethylbenzyl), 3,3-dimethyl-2-E- (2- (Hydroxymethyl-1-propenyl) cyclopropanecarboxylic acid (3-phenoxybenzyl) and the like.

  As the aldehyde (10), for example, methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate, 3,3-dimethyl-2-E- (2-formyl-1- Ethyl propenyl) cyclopropanecarboxylate, isopropyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate, 3,3-dimethyl-2-E- (2-formyl-1- Tert-butyl propenyl) cyclopropanecarboxylate, cyclohexyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate, 3,3-dimethyl-2-E- (2-formyl- Menthyl 1-propenyl) cyclopropanecarboxylate, 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropyl Benzyl pancarboxylate, 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate (4-chlorobenzyl), 3,3-dimethyl-2-E- (2-formyl- 1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluorobenzyl), 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylic acid (2,3 5,6-tetrafluoro-4-methylbenzyl), 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-) Methoxybenzyl), 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro-4-methoxymethyl) Rubenjiru), 3,3-dimethyl -2-E- (2-formyl-1-propenyl) cyclopropanecarboxylic acid (3-phenoxybenzyl) and the like.

  Examples of the carboxylic acid (11) include methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate and 3,3-dimethyl-2-E- (2-carboxy-1). -Propenyl) cyclopropanecarboxylate ethyl, 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate isopropyl, 3,3-dimethyl-2-E- (2-carboxy-1 Tert-butyl-propenyl) cyclopropanecarboxylate, cyclohexyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate, 3,3-dimethyl-2-E- (2-carboxy) Menthyl-1-propenyl) cyclopropanecarboxylate, 3,3-dimethyl-2-E- (2-carboxy-1-propene B) benzyl cyclopropanecarboxylate, 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate (4-chlorobenzyl), 3,3-dimethyl-2-E- (2 -Carboxy-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluorobenzyl), 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylic acid (2 , 3,5,6-tetrafluoro-4-methylbenzyl), 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetrafluoro) -4-methoxybenzyl), 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylic acid (2,3,5,6-tetra Ruoro-4-methoxy-methylbenzyl) 3,3-dimethyl -2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylic acid (3-phenoxybenzyl) and the like.

  When a trans-form is used as the chrysanthemic acid ester (8), the trans-form oxygen-containing compound (at least one compound selected from the group consisting of alcohol (9), aldehyde (10) and carboxylic acid (11)) Is obtained. When cis-form chrysanthemic acid ester (8) is used, a cis-form oxygen-containing compound is obtained. When the optically active chrysanthemic acid ester (8) is used, an optically active oxygen-containing compound is obtained.

  The alcohol (9), aldehyde (10) and carboxylic acid (11) thus obtained are all important compounds as synthetic intermediates such as pyrethroid-based home protection products and insecticides, and are used as industrial production methods for these compounds. This reaction can be applied.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate and 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate The yield of methyl acid was calculated from the results of analysis by a liquid chromatography internal standard method, and the yield of other products was calculated from the results of analysis by a gas chromatography internal standard method.

Example 1
In a 100 mL flask equipped with a magnetic rotor and a reflux condenser, 50 mg of selenium dioxide, 100 mg of 3,4-dihydroxybenzoic acid, 1 g of 1-butyl-3-methylimidazolium tetrafluoroborate and 70% by weight of tert-butyl hydroperoxide 1 g of water was added, and the mixture was stirred and maintained at an internal temperature of 40 ° C. for 30 minutes. Thereafter, 1.5 g of methyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate was charged, the temperature was raised to an internal temperature of 60 ° C, and 70% by weight of tert- 1.64 g of butyl hydroperoxide water was added dropwise over 1 hour, and the mixture was stirred and reacted at the same temperature for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.5 g of an ionic liquid layer containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 3%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 44%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 42%.

Example 2
1.5 g of the ionic liquid layer obtained in Example 1 and 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylic acid were placed in a 100 mL flask equipped with a magnetic rotor and a reflux condenser. After charging 1.5 g of methyl, the temperature was raised to an internal temperature of 60 ° C., and 2.6 g of 70% by weight tert-butyl hydroperoxide water was added dropwise with stirring at the same temperature over 1 hour. And the mixture was stirred and reacted at the same temperature for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.6 g of an ionic liquid layer containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 7%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 43%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 33%.

Example 3
A 100 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 50 mg of selenium dioxide, 100 mg of picoline, 1 g of 1-butyl-3-methylimidazolium tetrafluoroborate and 0.5 g of 70% by weight tert-butyl hydroperoxide water. The mixture was stirred and maintained at an internal temperature of 40 ° C. for 30 minutes. Thereafter, 1.5 g of methyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate was charged, the temperature was raised to an internal temperature of 60 ° C, and 70% by weight of tert- After 2.2 g of butyl hydroperoxide water was added dropwise over 1 hour, the internal temperature was raised to 80 ° C., and the mixture was stirred and reacted at the same temperature for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.5 g of an ionic liquid layer containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 8%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 54%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 8%.

Example 4
1.5 g of the ionic liquid layer obtained in Example 3 and 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylic acid were placed in a 100 mL flask equipped with a magnetic rotor and a reflux condenser. After charging 1.5 g of methyl, the internal temperature was raised to 60 ° C., 2.6 g of 70% by weight tert-butyl hydroperoxide water was added dropwise with stirring at the same temperature over 1 hour, and the mixture was stirred at the same temperature for 5 hours. And reacted. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.6 g of an ionic liquid layer containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 36%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 37%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 7%.

Example 5
A 100 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 50 mg of selenium dioxide, 1 g of 1-butyl-3-methylimidazolium tetrafluoroborate and 0.5 g of 70% by weight tert-butyl hydroperoxide water, and heated at an internal temperature. The mixture was stirred and maintained at 40 ° C. for 30 minutes. Thereafter, 1.5 g of methyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate was charged, the temperature was raised to an internal temperature of 70 ° C, and 70% by weight of tert- After 2.2 g of butyl hydroperoxide water was added dropwise over 1 hour, the mixture was stirred and reacted at the same temperature for 7 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.4 g of an ionic liquid layer containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 20%
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 44%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 16%.

Example 6
In a 100 mL flask equipped with a magnetic rotor and a reflux condenser, 1.4 g of the ionic liquid layer obtained in Example 5 and 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylic acid 1.5 g of methyl was charged, the internal temperature was raised to 70 ° C., 2.6 g of 70% by weight tert-butyl hydroperoxide water was added dropwise over 1 hour with stirring at the same temperature, and the mixture was stirred at the same temperature for 6 hours. And reacted. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.6 g of an ionic liquid layer containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 34%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 21%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 5%,
35% of the raw material remained.

Example 7
In a 100 mL flask equipped with a magnetic rotor and a reflux condenser, 50 mg of selenium dioxide, 100 mg of 3,4-dihydroxybenzoic acid, 1 g of 1-butyl-3-methylimidazolium tetrafluoroborate and 70% by weight of tert-butyl hydroperoxide 0.5 g of water was charged, and the mixture was stirred and maintained at an internal temperature of 40 ° C. for 30 minutes. Thereafter, 1.58 g of geranyl acetate was charged, the temperature was raised to an internal temperature of 50 ° C., and 2.2 g of 70% by weight tert-butyl hydroperoxide water was added dropwise with stirring at the same temperature over 1 hour. The mixture was stirred and reacted for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.5 g of an ionic liquid layer containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.

Yield of each component E, E-2,6-dimethyl-2,6-octadiene-1,8-diol-8-acetate: 35%,
E, E-2-formyl-8-acetoxy-6-methyl-2,6-octadiene: 25%,
33% of the raw material remained.

Example 8
A 100 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 60 mg of selenyl chloride, 1 g of 1-butyl-3-methylimidazolium tetrafluoroborate and 0.5 g of 70% by weight tert-butyl hydroperoxide water. The mixture was stirred and maintained at a temperature of 40 ° C. for 30 minutes. Thereafter, 1.5 g of methyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate was charged, the temperature was raised to an internal temperature of 60 ° C, and 70% by weight of tert- After 2.2 g of butyl hydroperoxide water was added dropwise over 1 hour, the temperature was raised to 80 ° C., and the mixture was stirred and reacted at the same temperature for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.4 g of an ionic liquid layer containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 3%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 32%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 8%.

Example 9
In a 100 mL flask equipped with a magnetic rotor and a reflux condenser, 1.4 g of the ionic liquid layer obtained in Example 8 and 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylic acid After charging 1.5 g of methyl, the temperature was raised to an internal temperature of 60 ° C., 2.6 g of 70% by weight tert-butyl hydroperoxide water was added dropwise over 1 hour with stirring at the same temperature, and the temperature was raised to 80 ° C. The mixture was stirred and reacted at the temperature for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.6 g of an ionic liquid layer containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 22%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 44%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 7%.

Example 10
A 100 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 50 mg of selenium dioxide, 1 g of N-butyl-4-methylpyridinium tetrafluoroborate and 0.5 g of 70% by weight tert-butyl hydroperoxide water, and the internal temperature was set at 40%. The mixture was stirred and maintained at 30 ° C for 30 minutes. Thereafter, 1.5 g of methyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate was charged, the temperature was raised to an internal temperature of 60 ° C, and 70% by weight of tert- After 2.2 g of butyl hydroperoxide water was added dropwise over 1 hour, the temperature was raised to 80 ° C., and the mixture was stirred and reacted at the same temperature for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.5 g of an ionic liquid layer containing N-butyl-4-methylpyridinium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 6%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 35%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 11%.

Example 11
1.5 g of the ionic liquid layer obtained in Example 10 and 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylic acid were placed in a 100 mL flask equipped with a magnetic rotor and a reflux condenser. After charging 1.5 g of methyl, the internal temperature was raised to 60 ° C., 2.6 g of 70% by weight tert-butyl hydroperoxide water was added dropwise over 1 hour with stirring at the same temperature, and then the temperature was raised to 80 ° C. The mixture was stirred and reacted at the same temperature for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.6 g of an ionic liquid layer containing N-butyl-4-methylpyridinium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 24%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 35%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 8%,
6% of the raw material remained.

Example 12
In a 100 mL flask equipped with a magnetic rotor and a reflux condenser, 80 mg of selenocystine, 1 g of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, 40 mg of 98% sulfuric acid and 70% by weight of tert-butyl hydroperoxide 0.5 g of water was charged, and the mixture was stirred and maintained at an internal temperature of 40 ° C. for 30 minutes. Thereafter, 1.5 g of methyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate was charged, the temperature was raised to an internal temperature of 60 ° C, and 70% by weight of tert- After 2.2 g of butyl hydroperoxide water was added dropwise over 1 hour, the temperature was raised to 80 ° C., and the mixture was stirred and reacted at the same temperature for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer, an ionic liquid layer, and an aqueous layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.4 g of an ionic liquid layer containing 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfone) amide was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 26%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 39%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 7%,
20% of the raw material remained.

Example 13
A 100 mL flask equipped with a magnetic rotor and a reflux condenser was charged with 70 mg of dimethylselenourea, 1 g of 1-butyl-3-methylimidazolium tetrafluoroborate, and 0.5 g of 70% by weight tert-butyl hydroperoxide water. The mixture was stirred and maintained at a temperature of 40 ° C. for 30 minutes. Thereafter, 1.5 g of methyl 3,3-dimethyl-2- (2-methyl-1-propenyl) cyclopropanecarboxylate was charged, the temperature was raised to an internal temperature of 60 ° C, and 70% by weight of tert- After 2.2 g of butyl hydroperoxide water was added dropwise over 1 hour, the temperature was raised to 80 ° C., and the mixture was stirred and reacted at the same temperature for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, 10 g of n-hexane was added, and the mixture was subjected to liquid separation treatment to obtain an n-hexane layer and an ionic liquid layer. The ionic liquid layer was further extracted twice with n-hexane, and the obtained n-hexane layer was mixed with the previously obtained n-hexane layer to obtain an organic layer containing an oxygen-containing compound. In addition, 1.4 g of an ionic liquid layer containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.

Yield of each component Methyl 3,3-dimethyl-2-E- (2-hydroxymethyl-1-propenyl) cyclopropanecarboxylate: 12%,
Methyl 3,3-dimethyl-2-E- (2-formyl-1-propenyl) cyclopropanecarboxylate: 44%,
Methyl 3,3-dimethyl-2-E- (2-carboxy-1-propenyl) cyclopropanecarboxylate: 8%.

Claims (9)

A process for producing an oxygen-containing compound, comprising reacting an olefin having a carbon-carbon double bond bonded to a methyl group or a methylene group with an organic hydroperoxide in the presence of an ionic liquid and a selenium compound. The method for producing an oxygen-containing compound according to claim 1, wherein the oxygen-containing compound is at least one selected from the group consisting of alcohols, aldehydes, ketones, and carboxylic acids. An olefin having a carbon-carbon double bond bonded to a methyl group or a methylene group is represented by the formula (1)

(In the formula, R ¹ represents an alkyl group which may be substituted, an aryl group which may be substituted, or an aralkyl group which may be substituted. R ² , R ³ and R ⁴ are the same or different. An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted aralkyl group, Optionally substituted aralkyloxy group, optionally substituted alkylcarbonyl group, optionally substituted arylcarbonyl group, optionally substituted aralkylcarbonyl group, optionally substituted alkoxycarbonyl group, substituted An optionally substituted aryloxycarbonyl group, an optionally substituted aralkyloxycarbonyl group, Sill group, a halogen atom or a hydrogen atom. Here, with ^{R 1} and ^R 3, ^{R 2} and ^R 4, at least one pair of ^{R 1} and ^{R 2} and ^{R 3} and ^{R 4} are bonded, the bond A ring may be formed together with the carbon atom.)
Wherein the oxygen-containing compound is represented by the formula (2)

(Wherein, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above.)
And / or formula (3)

(Wherein, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above.)
The method for producing an oxygen-containing compound according to claim 1, which is a compound represented by the formula: An olefin having a carbon-carbon double bond bonded to a methyl group or a methylene group is represented by the formula (4)

(Wherein, R ² , R ³ and R ⁴ each have the same meaning as described above. Here, R ² and R ⁴ or R ³ and R ⁴ are bonded to form a ring together with the bonded carbon atom. May be.)
Wherein the oxygen-containing compound is represented by the formula (5)

(Wherein, R ² , R ³ and R ⁴ represent the same meaning as described above.)
A compound represented by the formula:
Equation (6)

(Wherein, R ² , R ³ and R ⁴ represent the same meaning as described above.)
A compound represented by the formula:
Equation (7)

(Wherein, R ² , R ³ and R ⁴ represent the same meaning as described above.)
A compound represented by the formula:
The method for producing an oxygen-containing compound according to claim 1, wherein the method is at least one compound selected from the group consisting of: An olefin having a carbon-carbon double bond bonded to a methyl group or a methylene group is represented by the formula (8)

(In the formula, R ⁵ represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group.)
Wherein the oxygen-containing compound is represented by the formula (9)

(Wherein, R ⁵ has the same meaning as described above.)
A compound represented by the formula:
Equation (10)

(Wherein, R ⁵ has the same meaning as described above.)
A compound represented by the formula:
Equation (11)

(Wherein, R ⁵ has the same meaning as described above.)
A compound represented by the formula:
The method for producing an oxygen-containing compound according to claim 1, wherein the method is at least one compound selected from the group consisting of: The method for producing an oxygen-containing compound according to claim 1, wherein the ionic liquid is at least one selected from the group consisting of an alkyl-substituted imidazolium salt, an alkyl-substituted pyridinium salt, and a quaternary ammonium salt. The method for producing an oxygen-containing compound according to claim 1, wherein the selenium compound is at least one selected from the group consisting of selenium dioxide, selenic acid, and selenous acid. The method for producing an oxygen-containing compound according to claim 1, wherein the reaction is carried out in the presence of an aromatic carboxylic acid. The method according to claim 1, wherein the ionic liquid containing the selenium compound is recovered after the production of the oxygen-containing compound, and the ionic liquid containing the selenium compound is recycled.