JP2003073323A - Method for oxidizing organic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for oxidizing an organic compound by which a specific oxidizable functional group in the organic compound having a plurality of oxidizable functional groups having different intramolecular environments can suitably be selected and oxidized. SOLUTION: This method is to oxidize the organic compound having the plurality of oxidizable functional groups having the different intramolecular environments. The method for oxidizing the organic compound is carried out by oxidizing at least one of the plurality of oxidizable functional groups in the presence of a surfactant and an oxidation catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for oxidizing an organic compound having a plurality of oxidizable functional groups having different intramolecular environments.

[0002]

2. Description of the Related Art A method for oxidizing an organic compound having an oxidizable functional group in its molecule is used for producing various useful compounds. For example, epoxides, alcohols, aldehydes, ketones, carboxylic acids, sulfoxides, sulfones, amine oxides, aromatic compounds whose side chains and nuclei are oxidized, and the like can be synthesized by utilizing an oxidation reaction. In such an oxidation method of an organic compound, an organic compound having two or more oxidizable functional groups, and the oxidizable functional groups having different oxidizability due to a difference in structure in the periphery thereof, that is, a different intramolecular environment An organic compound having a plurality of oxidizable functional groups may be used.

J. Org. Chem.61[23] (1
996) (US) p. 8310-831, Bull. C
hem. Soc. Jpn.70[4] (1997) p.
905-915, J. Am. Chem. Soc.199
[50] (1997) (US) p. 12386-1238
7 and Bull. Chem. Soc. Jpn.72
[10] (1999) p. 2287-2306 (either
Also Noyori, R .; Other) is the raw in the reaction formula below.
As shown in the product yield, a phase transfer catalyst was used in a two-phase system.
When performing oxidation reaction by_TwoCH_TwoPO_ThreeH_TwoThe system
When added to the inside, it was discovered that an epoxy compound had formed.
It is shown. In the following reaction formula, H_TwoO_TwoIs an oxidizer
And Na_TwoWO_FourIs an oxidation catalyst, and [CH_Three(C
₈H₁₇) _ThreeN] HSO_FourIs a phase transfer catalyst.

[0004]

[Chemical 1]

Tetrahedron Lett. 25
[30] (1984) (US) p. 3231-3232
(Nakamura, M. et al.), 2,3-epoxy compound is preferentially synthesized in water in the presence of a surfactant (regioselective synthesis), as shown by the conversion of the product in the following reaction formula. What has been done is disclosed. In the following reaction formula, MCPBA is an abbreviation for m-chloroperbenzoic acid.

[0006]

[Chemical 2]

J. Org. Chem. 57 [4] (19
92) (US) p. 1198-1202 (Fringue)
Ili, F.L. In other), as shown by the yield of the product in the following reaction formula, by controlling the pH in water in the presence or absence of a surfactant, 2,3-
It is disclosed that an epoxy compound or a 6,7-epoxy compound was selectively synthesized (regioselective synthesis).
In the following reaction formula, CTAOH is an abbreviation for cetyltrimethylammonium hydroxide, and the number below the compound represents the ratio (selectivity) of the obtained compound.

[0008]

[Chemical 3]

Synth. Commun. 24 [18]
(1994) p. 2665-2673 (Pizzo,
F. Others), as shown in the following reaction formula, discloses that only aldehyde was selectively oxidized in the presence of a surfactant in water without producing sulfide or sulfone. In the following reaction formula, TBHP is t-
Butyl hydroperoxide, CTA is an abbreviation for cetyl trimethyl ammonium.

[0010]

[Chemical 4]

However, in these reaction methods, a specific oxidizable functional group is selectively oxidized with respect to an organic compound having a plurality of oxidizable functional groups having different intramolecular environments, and There was room for research so that it could be appropriately selected whether or not to oxidize the oxidizable functional group. For various organic compounds having different oxidizable functional groups with different intramolecular environments, if a specific oxidizable functional group can be appropriately selected and oxidized, various useful compounds can be selectively produced. Therefore, it is industrially expected to produce an organic compound by such an oxidation method.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and selects a specific oxidizable functional group in an organic compound having a plurality of oxidizable functional groups having different intramolecular environments. It is an object of the present invention to provide a method for oxidizing an organic compound that can be oxidized by the above method and a method for producing an oxidized organic compound.

[0013]

[Means for Solving the Problems] The inventors of the present invention have studied various methods of oxidizing an organic compound, and when oxidizing an organic compound having a plurality of oxidizable functional groups having different intramolecular environments, a surfactant is used. First, it was noted that a specific oxidizable functional group is oxidized when performed in the presence of an oxidation catalyst. In this case, it was found that when the kind of the surfactant is selected and used, the oxidizable functional group that is oxidized depending on the kind of the surfactant is selected, and it is conceived that the above problems can be solved satisfactorily. The present invention has been reached. According to such an organic compound oxidizing method, a specific oxidizable functional group in an organic compound having a plurality of oxidizable functional groups having different intramolecular environments is selected and oxidized by the type of surfactant. Therefore, it becomes possible to industrially efficiently and simply produce an organic compound in which a specific oxidizable functional group is oxidized.

That is, the present invention is a method of oxidizing an organic compound having a plurality of oxidizable functional groups having different intramolecular environments, wherein the method of oxidizing the organic compound is in the presence of a surfactant and an oxidation catalyst. It is a method for oxidizing an organic compound, which is carried out by oxidizing at least one of a plurality of oxidizable functional groups. The present invention also provides a compound represented by the general formula: R—C (R ′) ═CH—CH ₂ —OH (wherein R and R ′ are the same or different and each is a hydrogen atom or an alkyl group which may have a substituent). Or an aromatic ring) is used in the reaction system in the presence of an oxidation catalyst in the presence of an oxidation catalyst to produce an oxidized organic compound, which is anionic, nonionic. When at least one of the cationic and amphoteric surfactants is added to the reaction system, an organic compound in which the double bond is epoxidized is produced, and when a cationic surfactant is added, the hydroxyl group is It is also a method for producing an oxidized organic compound in which an oxidized carbonyl compound is produced. The present invention is described in detail below.

The method for oxidizing an organic compound of the present invention is a method for oxidizing an organic compound having a plurality of oxidizable functional groups having different intramolecular environments. Examples of the organic compound having a plurality of oxidizable functional groups having different intramolecular environments include one or both of a form having different functional groups in the molecule and a form having the same functional group in the molecule. , For example,
Examples include those described below. (1) Compounds having different functional groups of unsaturated bond and hydroxyl group: allyl alcohol, crotyl alcohol, 3-buten-1-ol, 3-buten-2-ol, 2-methyl-3-penten-1-ol , 3-methyl-2-buten-1-ol, 3-penten-2-ol, 4-penten-1-ol, 3-methyl-1-penten-3-ol, 4-methyl-3-pentene-2 -Ol, cinnamic alcohol, 1- (1-hydroxyethyl) cyclohexene, 5-t-butyl-2-cyclohexen-1-ol, 2-cyclohexen-1-ol, 1-hexene-
3-ol, 3-cyclohexen-1-ol, 2-hexen-1-ol, 3-hexen-1-ol, 4-
Hexen-1-ol, 5-hexene-1-ol, 2
-Methyl-1-hepten-3-ol, 4-heptene-
2-ol, 3-octen-2-ol, 1-octen-3-ol, 1-nonen-3-ol, 2-nonene-
1-ol, 9-decen-1-ol, 2-methyl-2
-Undecen-4-ol, 2-undecen-1-ol, 10-undecen-1-ol, 1-dodecene-3
-Ol, 11-dodecen-2-ol, 5-cyclohexadecen-1-ol, ralpinen-4-ol, isopulegol, myrtenol, nopol, perylyl alcohol, citronellol and the like. (2) Compounds having two unsaturated bonds of the same functional group and different functional groups of hydroxyl groups: geraniol, nerol, linalool and the like. (3) Compounds having three unsaturated bonds of the same functional group and different functional groups of hydroxyl groups: farnesol and the like.

In the organic compounds shown above, allyl alcohol and crotyl alcohol have different functional groups with unsaturated bonds and hydroxyl groups, and geraniol has different functional groups with two unsaturated bonds and different functional groups. And a group. In this case, as a plurality of oxidizable functional groups having different intramolecular environments, allyl alcohol and crotyl alcohol have an unsaturated bond and a hydroxyl group, and geraniol has two unsaturated bonds and a hydroxyl group.

[0017]

[Chemical 5]

The oxidizable functional group is not particularly limited as long as it is a functional group capable of being oxidized in the molecule of the organic compound, and examples thereof include unsaturated bonds such as double bond, hydroxyl group, aldehyde group, sulfur atom, Examples thereof include a nitrogen atom, an alkyl group and an aromatic ring. Among these, easily oxidized,
Unsaturated bonds and / or hydroxyl groups are preferred because of their good selectivity. That is, the organic compound used in the present invention includes compounds having these oxidizable functional groups, and one kind or two or more kinds may be used. More preferably, the organic compound has a double bond as at least an oxidizable functional group.

The above-mentioned method for oxidizing an organic compound is carried out by oxidizing at least one of a plurality of oxidizable functional groups in the presence of a surfactant and an oxidation catalyst.
To oxidize at least one of a plurality of oxidizable functional groups means, for example, (1) selectively oxidizing a specific type of functional group in a different functional group having a different intramolecular environment,
(2) Examples include selective oxidation of functional groups in a specific intramolecular environment among functional groups of the same type having different intramolecular environments. In the case of the above (1), the specific functional group that is selectively oxidized may be one type or two or more types. In the case of the above (2), the functional group in a specific intramolecular environment that is selectively oxidized may be only a functional group in the same intramolecular environment, or two or more different intramolecular environments. It may be a functional group in. That is, when an organic compound has two oxidizable functional groups having different intramolecular environments in one molecule, one of the oxidizable functional groups is selectively oxidized. When one molecule has three or more oxidizable functional groups having different internal environments, one or two or more of the three or more oxidizable functional groups are selectively oxidized.

In a preferred embodiment of the present invention, the method of oxidizing the organic compound is carried out by oxidizing at least one of a plurality of oxidizable functional groups depending on the type of surfactant. In such a form, it becomes possible to change the oxidizable functional group to be oxidized by changing the kind of the surfactant. In this case, as the above-mentioned surfactant, it is preferable to use one or two selected from the group consisting of anionic, nonionic, cationic and amphoteric surfactants. More preferably, one of these is selected and used. When one or two kinds are selected from the group consisting of anionic, nonionic, cationic and amphoteric surfactants and the organic compound is oxidized in the presence of the surfactants and the oxidation catalyst, specific oxidizability is increased. It is possible to intentionally select and oxidize functional groups. This makes it possible to selectively produce various useful organic compounds using organic compounds having a plurality of oxidizable functional groups having different intramolecular environments as production raw materials. This makes it possible to easily select and produce a useful oxidized organic compound. For example, when carrying out the oxidation reaction of a compound having an unsaturated bond and a hydroxyl group by the oxidation method of the present invention,
When anionic, nonionic or amphoteric surfactants are used as the surfactant, unsaturated bonds are selectively oxidized, and when a cationic surfactant is used, the hydroxyl groups are selectively Will be oxidized to. In addition,
In the present invention, all of the plurality of oxidizable functional groups may be oxidized, and at least one of the plurality of oxidizable functional groups having different intramolecular environments may be different depending on the specific type of the surfactant. It suffices that relatively selective oxidation be performed as compared with the case of using the above types.

The above-mentioned surfactant and oxidation catalyst are distinguished from so-called phase transfer catalysts. A phase transfer catalyst is, for example, a nucleophilic anion existing in the aqueous phase and its anion exchanged in a reaction system of an aqueous phase containing a nucleophilic anion and a nonpolar organic phase containing an organic substrate that reacts with the aqueous phase. ,
It means a substance having a function of promoting a reaction by moving back and forth between an aqueous phase and an organic phase to transfer an nucleophilic anion to an organic substrate existing in the organic phase. In the present invention, the surfactant and the oxidation catalyst are not phase transfer catalysts but can promote the oxidation of the organic compound by themselves. The method for oxidizing an organic compound of the present invention does not exclude the use of a phase transfer catalyst together with a surfactant and an oxidation catalyst. You may use.

The surfactant used in the present invention is a compound having a structure in which a hydrophilic portion and a lipophilic portion are shared in one molecule, and one kind or two or more kinds can be used. As for such a surfactant, for example, a representative editor: Takao Karimei "New Edition Surfactant Analysis Method" (SHO 62-3-).
10) Koshobo p. As described in 1-3, the property is that it dissolves or disperses colloidally in water or oils, and is adsorbed or oriented on the surface or interface to lower the surface or interfacial tension, Then, it is possible to form micelles.

Among the above surfactants, for example, the following (1) to (9) are used as the anionic surfactant and the following (10) to (13) are used as the nonionic surfactant.
However, as the cationic surfactant, the following (14) to
(16) and the like include the following (17) as the amphoteric surfactant.
(21) and the like.

[0024]Anionic surfactant (1) Carboxylic acid and its salt: Aliphatic monocarboxylic acid
Salt, N-acryloyl sarcosine salt, N-acylloyl-β
-Fat such as alanine salt and N-acylloylglutamate
Group compounds; cyclic compounds such as abietic acid salts. (2) Sulfonic acid and its salt: Dialkylsulfo amber
Acid salt, alkane sulfonate, hydroxyalkane sulphate
Aliphatic compounds such as phonates; linear alkylbenzenesulfur
Phonate, alkyl (branched) benzene sulfonate,
Alkylnaphthalene sulfonate, alkylphenoxy
Polyoxyethylene propyl sulfonate, polyoxy
Ethylene alkylphenol sulfonate, naphthalene
Cyclic compound such as sulfonate-formaldehyde condensate
Product; N-methyl-N-oleyl taurine sodium, N
-Alkylsulfosuccinic acid monoamide disodium salt, etc.
Nitrogen-containing compounds; Other compounds such as petroleum sulfonates
Stuff.

(3) Sulfate ester salt and sulfite ester salt: Sulfated castor oil, sulfated beef leg oil, fatty acid alkyl ester sulfate ester salt, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, fatty acid monoglyceride sulfate ester Aliphatic compounds such as salts and polyoxyethylene alkyloylamide sulfates; cyclic compounds such as polyoxyethylene alkylphenyl ether sulfates and polyoxyethylene styrylphenyl ether sulfates. (4) Phosphoric acid esters and salts thereof: Aliphatic compounds such as alkyl phosphoric acid ester salts and polyoxyethylene alkyl ether phosphoric acid ester salts; cyclic compounds such as polyoxyethylene alkylphenyl ether phosphoric acid ester salts. (5) Polymerizable polymer compounds: styrene compounds such as partially saponified products of styrene-maleic anhydride copolymers; olefin compounds such as partially saponified products of olefin-maleic anhydride copolymers. (6) Polycondensation type polymer compound: naphthalene compound such as naphthalene sulfonate-formalin condensate.

(7) Phosphorous acid and phosphonic acid ester (8) Thiophosphoric acid compound (9) Boric acid-containing compound

[0027]Nonionic surfactant (10) Ether compound: polyoxyethylene alk
Aliphatic compounds such as ether; polyoxyethylene al
Kill phenyl ether, polyoxyethylene polystyril
Cyclic compounds such as ruphenyl ether; polyoxyethylene
Polyether such as polyoxypropylene glycol
Compound (11) Ester compound: Glycerin fatty acid partial ester
Tellur, sorbitan fatty acid partial ester, pentaerythri
Tall fatty acid partial ester, propylene glycol mono
Polyhydric esters such as fatty acid esters and sucrose fatty acid partial esters
Rucol partial ester. (12) Ester ether compound: polyoxyethylene
N-sorbitan fatty acid partial ester, polyoxyethylene
Sorbitol fatty acid partial ester, polyoxyethylene
Glycerin fatty acid partial ester, polyethylene glycol
Fatty acid ester, polyglycerin fatty acid partial ester
And polyoxyethylene such as polyoxyethylenated castor oil
Renated polyhydric alcohol fatty acid ester. (13) Nitrogen-containing compound: fatty acid diethanolamide,
N, N-bis-2-hydroxyalkylamine, Polio
Xyethylenealkylamine, triethanolamine fat
Fatty acid ester, trialkylamine oxide, etc.

[0028]Cationic surfactant (14) Primary to tertiary amine salt: alkylamine salt, dia
Aliphatic compounds such as rutile amine salts. (15) Quaternary ammonium salt: tetraalkyl ammonium
Aliphatic compounds such as aluminum salts; trialkylbenzylan
Monium salt, alkylpyridinium salt, 2-alkyl-
1-alkyl-1-hydroxyethyl imidazolinium
Cyclization of salts, N, N-dialkylmorpholinium salts, etc.
Stuff. (16) Polyethylene polyamine derivative: polyethylene
Polyamine fatty acid amide salt, polyethylene polyamine fat
Urea condensate of fatty acid amide, polyethylene polyamine
Quaternary ammonium salts of fatty acid amide urea condensation products, etc.

[0029]Amphoteric surfactant (17) Carboxybetaine type compound: N, N-dimethyl
Ru-N-alkyl-N-carboxyalkylene ammonium
Umbetaine etc. (18) Aminocarboxylic acid: N, N-dialkylamino
Alkylene carboxylates and the like. (19) Sulfobetaine type compound: N, N, N-tria
Rutile-N-sulfoalkylene ammonium betaine,
N, N-dimethyl-N-tetradecyl-N-sulfotri
Methylene ammonium betaine, etc. (20) Aminosulfate type compound: N-alkyl-
N, N-bispolyoxyethylene sulfate ester salt and the like. (21) Imidazoline type compound: 2-alkyl-1-hi
Droxyethyl-1-carboxymethyl imidazolinium
Mu salt etc.

Among the above surfactants, the following surfactants are more preferable. (Anionic surfactant) Aliphatic monocarboxylic acid salt, alkane sulfonate, linear alkylbenzene sulfonate, alkyl sulfate ester salt. (Nonionic surfactant) Polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid partial ester, trialkylamine oxide. (Cationic surfactant) Tetraalkylammonium salt, alkylpyridinium salt. (Amphoteric surfactant) N, N-dimethyl-N-alkyl-
N-carboxyalkylene ammonium betaine, N,
N, N-trialkyl-N-sulfoalkylene ammonium betaine.

In the present invention, an anionic, nonionic, cationic or amphoteric surfactant may be supported on a carrier and used as a carrier. The carrier is not particularly limited, and for example, an inorganic carrier such as silica, alumina, titania, zirconia; an ion exchange resin; a polymer or the like can be used.

The amount of the above surfactant used is not particularly limited and may be appropriately set depending on the types of the surfactant and the substrate, reaction conditions and the like. As an example of the preferred embodiment of the present invention, the amount of the surfactant used when crotyl alcohol is used as a substrate and the reaction is carried out under the following reaction conditions will be described. Substrate: 1000 μmol of crotyl alcohol Solvent: 6 mL Oxidation catalyst: 30 mg Reaction temperature: 32 ° C. Reaction time: 24 hours Aqueous hydrogen peroxide (H ₂ O ₂ ) solution: 200 μmol The preferred amount of surfactant used in the above reaction is, for example, Sodium as anionic surfactant
When dodecyl sulphate (SDS) is used, it is 0.005-5.0 g, and polyoxyethylene (20) c is used as a nonionic surfactant.
When using etylether (Brij58),
0.01-1.0 g, and as a cationic surfactant, cetyltrimethylammonium h
When using hydrogen sulphate (CTA), it is 0.01 to 0.5 g, and Zwittergent 3-14 Detergent as an amphoteric surfactant is used.
When using (N, N-dimethyl-tetradecyl-N-sulfotrimethylene ammonium betaine), 0.00
It is 5 to 5.0 g.

The oxidation catalyst used in the present invention is in the liquid phase.
Oxidation catalysts that can be used, i.e.
Is a substance that exhibits catalytic activity by using one or more
Inorganic compounds may be used, organometallization
Compounds and organic compounds may be used. Such an oxidation catalyst
Is, for example, a Group 2 compound such as BeO; Y_TwoO_Three,
La_TwoO_ThreeGroup 3 compounds such as; TiO_Two, ZrO_TwoEtc. 4
Group compounds; NaVO_Three, VO (acac)_Two5 groups of etc.
Compound; CrO_Three, (NH_Four)₆Mo₇O₂₄・ 4H
_TwoO, Na_TwoWO_4,Na_TwoMoO_FourGroup 6 compounds such as
NaReO₇, Salen Mn complex, CH_ThreeReO_ThreeSuch as 7
Group compounds; Fe_TwoO_Three, RuCl_Two(PPh_Two)_Three, F
eCl_3,n-Pr_FourN (RuO_Four), K_TwoOsO
_Two(OH)_Four, Fe (NH_Four)_Two(SO_Four)_Two・ FeO
Group 8 compounds such as Co (acac)_Two, RhCl_ThreeEtc.
Group 9 compound; Pd (OAc)_TwoGroup 10 compounds such as Cu; Cu
O, CuO_TwoGroup 11 compounds such as Hg (OAc)_TwoEtc.
Group 12 compound; B_TwoO_Three, LiBO_Two, NaBO_TwoEtc.
Group 13 compounds; GeO_TwoGroup 14 compounds such as As;
_TwoO_Three, NaAsO_Two, BiCl_ThreeGroup 15 compounds such as
SeO_Two, C₆H₅SeO_TwoH, Na _TwoSeO_Four, Na
_TwoTeO_ThreeGroup 16 compounds such as; I_TwoO₅17 group compound such as
Thing; H _FourSiW₁₂O₄₀, H_FourSiMo₁₂O₄₀,
H_ThreePW₁₂O₄₀, H_ThreePMo₁₂O₄₀, H₉PM
o₆V₆O₄₀And other polyoxometalates and the like.
It Among them, as the polyoxometallate, [SiW₉
O₃₄], [SiW₁₀O₃₆], [SiW
₁₁O₃₉], [PW₉O₃₄], [PW
₁₀O₃₆], [PW₁₁O₃₉], [P_TwoW₁₇O
₆₁], [P_TwoW₁₅O₅₆], [ZnW₉O₃₄],
[PMo₁₀O₃₆], [PMo₁₁O₃₉], Etc.
Those having a type skeleton are preferable, and these may be formed by other elements.
May be used in modified form, or in unmodified form
You may stay. More preferred are those with a 2-deficient skeleton
In addition, [γ-SiW modified with La, Zn, etc.
₁₀O₃₆] Two-defective polyoxometallate having skeleton
Is more preferred. Among these oxidation catalysts, poly
Oxo metallate and sodium tungstate, which is a Group 6 compound
Thorium (Na_TwoWO_Four), Sodium molybdate
(Na_TwoMoO _Four) Etc. are preferably used, and they are defective
A polyoxometallate having a skeleton is more preferable.

The form of use of the above-mentioned oxidation catalyst is not particularly limited, and it may be used in a homogeneous system or a heterogeneous system. Specifically, examples include a form in which the oxidation catalyst is dissolved in a solvent and used, and a form in which the oxidation catalyst is suspended in the solvent and used when the oxidation catalyst itself is solid. Further, the oxidation catalyst may be supported on a carrier and used as a carrier. The carrier is not particularly limited, for example, various ion exchange resins, silica,
A carrier such as alumina or another oxide generally used in a heterogeneous catalytic reaction can be used.

In the present invention, the method for carrying out the oxidation reaction is not particularly limited, and examples thereof include an oxidation catalyst, a surfactant,
It is possible to apply a method in which an oxidizing agent and a substrate, which is an organic compound having a plurality of oxidizable functional groups having different intramolecular environments, and the like are added to a solvent and stirred to carry out an oxidation reaction. The order of addition and the stirring method are not particularly limited as long as the effects of the present invention are exhibited.

The oxidizing agent is not particularly limited, and compounds and substances capable of forming oxygen ions, oxygen radicals, peroxides and superperoxides, such as hydrogen peroxide, organic peroxides, inorganic peroxides, oxygen and oxygen. And a mixed gas of hydrogen, nitrous oxide, iodosylbenzene and the like can be mentioned, and one kind or two or more kinds can be used. Among these, it is preferable to use hydrogen peroxide because the effects of the present invention can be more sufficiently exhibited. In this case, as a usage form of hydrogen peroxide, it is practically preferable to use a 0.01 to 70% by weight aqueous solution or a solution of alcohols. The amount of the oxidizing agent to be used may be appropriately set according to the type of the oxidizing compound or the organic compound having a plurality of oxidizable functional groups having different intramolecular environments as substrates, and is not particularly limited.

The above-mentioned solvent is not particularly limited, and water and / or an organic solvent can be used, and it is appropriately selected depending on the kind of the surfactant and the kind of the desired oxidation reaction. When forming two phases using water etc., you may use a phase transfer catalyst. As the organic solvent, it is preferable to use one that does not react with an organic compound that is a substrate, an oxidizing agent, a product, etc., and examples thereof include 1 to 6 carbon atoms such as methanol, ethanol, normal propanol, isopropanol, and tertiary butanol. Primary, secondary, and tertiary monohydric alcohols; polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; ethylene oxide such as diethylene glycol and triethylene glycol;
Oligomer of propylene oxide; Ethers such as ethyl ether, isopropyl ether, dioxane, tetrahydrofuran; Esters such as ethyl acetate, formic acid ester of polyhydric alcohol, acetic acid ester; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone; Dimethyl sulfoxide (DMS
O) and other sulfur-containing compounds; dimethylformamide (DM
F), nitrogen compounds such as nitromethane and nitriles; phosphorus compounds such as phosphoric acid esters such as triethyl phosphate and diethylhexyl phosphate; chloroform, dichloromethane,
Examples thereof include halogenated hydrocarbons such as ethylene dichloride; aliphatic hydrocarbons such as normal hexane and normal heptane; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane. These may be used alone or in combination of two or more.
Among these, preferred solvents are water and carbon number 1
~ 4 alcohols, 1,2-dichloroethane, heptane, toluene, xylene, chlorobenzene, acetonitrile, DMSO, DMF, etc., and mixtures thereof.

The pH of the reaction system in the present invention is not particularly limited and may be appropriately set according to the kind of the oxidizable functional group to be oxidized. For example, in the case of selectively oxidizing an unsaturated bond (epoxidation), it is preferably neutral or acidic, and thereby the selectivity can be further improved. When it is made acidic, usually one or more acidic substances are appropriately added to the reaction system. As the acidic substance, for example, Bronsted acid, Lewis acid and the like can be used, and as the Bronsted acid, for example, mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; acetic acid, benzoic acid, formic acid. , Organic acids such as trichloroacetic acid, trifluoromethanesulfonic acid, and sulfonic acid; inorganic acids such as zeolites and mixed oxides as Lewis acids, for example, aluminum chloride, ferric chloride, boron chloride compound, antimony chloride Examples thereof include compounds, stannic chloride, antimony fluoride, compounds of zinc and titanium, zeolites, mixed oxides and the like. Inorganic or organic acid salts can also be used. Furthermore, the reaction can be carried out in the presence of a buffer such as sodium acetate, tetrabutylammonium acetate, trimethylamine N-oxide.

The reaction conditions in the present invention are not particularly limited as long as the effects of the present invention are exhibited, and may be appropriately set depending on the type of production raw material, the usage ratio of the surfactant and the oxidation catalyst, and the like. For example, the reaction temperature is 0 to 2
The temperature is preferably 50 ° C., more preferably room temperature to
It is 180 ° C. The reaction time is preferably several minutes to 150 hours, more preferably several minutes to 48 hours. The reaction pressure is preferably atmospheric pressure to 2 × 10 ⁷ Pa, more preferably atmospheric pressure to 5 × 10 7.
It is ⁶ Pa. Moreover, you may perform a pressure reduction reaction. As an organic compound having a plurality of oxidizable functional groups having different intramolecular environments, for example, when the organic compound represented by the above general formula is used as a substrate to carry out an oxidation reaction, 10 mL of a solvent is used for 1 mol of the substrate. In 10 L (when the substrate is a liquid or when it is dissolved in water, it is possible to use no solvent), the oxidation catalyst is 10 ^{−5 to} 0.2 mol, the hydrogen peroxide is 0.01 to 10 mol, and the surfactant is It is preferable to add 5 to 400 g, the reaction temperature is room temperature to 120 ° C., the reaction time is several minutes to 24 hours, and the reaction pressure is atmospheric pressure to 5 × 10 ⁶ Pa. More preferably, the oxidation catalyst is 10 ^{−4 to} 0.1 mol, the hydrogen peroxide is 0.1 mol to 2 mol, and the surfactant is 10 to 30 with respect to 1 mol of the substrate in 100 mL to 5 L of the solvent.
0 g was added, the reaction temperature was room temperature to 100 ° C., the reaction time was 1 to 12 hours, and the reaction pressure was normal pressure to 2 × 1.
The reaction is performed at 0 ⁶ Pa.

The present invention can be applied to a method for producing an oxidized organic compound. For example, an organic compound represented by the above general formula is oxidized with hydrogen peroxide in the presence of an oxidation catalyst in a reaction system. In the method for producing an oxidized organic compound, the double bond is epoxidized when at least one of anionic, nonionic and amphoteric surfactant is added to the reaction system. When an organic compound is produced and a cationic surfactant is added, it can be suitably applied to a method for producing an oxidized organic compound in which a carbonyl compound having an oxidized hydroxyl group is produced.
The method for producing such an oxidized organic compound is also one aspect of the present invention.

The specific example of the oxidation reaction in the present invention is not particularly limited. For example, (1) oxidation of an unsaturated double bond of an alkene, specifically, for example, oxidation of propylene to propylene oxide (formula) (1)), etc., (2) oxidation of unsaturated triple bond of alkyne, (3) oxidation of hydroxyl group,
(4) Oxidation of sulfur atom, (5) Oxidation of nitrogen atom, (6)
Examples include oxidation of alkanes, (7) oxidation of aromatics, (8) oxidation reactions other than these (1) to (7). By such an oxidation reaction, the oxidizable functional group is oxidized to produce an oxidized organic compound.

Examples of the above-mentioned (1) oxidation of unsaturated double bond of alkene include epoxidation, reaction of alkene to produce ketone (Wacker oxidation), reaction of alkene to produce dihydroxy compound, and alkene to α-hydroxy. Examples thereof include reactions for forming ketones, alkene cleavage, allylic oxidation, oxidative cleavage, ammoxidation and the like. Specifically, these oxidation reactions are represented by the following reaction formulas (1) to
It is shown by (9).

[0043]

[Chemical 6]

Examples of the above-mentioned (2) oxidation of the unsaturated triple bond of the alkyne include a reaction of forming an α, β-epoxyketone from an alkyne and a reaction of forming a diketone from an alkyne. These oxidation reactions are specifically shown by the following reaction formulas (10) and (11).

[0045]

[Chemical 7]

Examples of the above-mentioned (3) oxidation of hydroxyl group include a reaction of forming a carbonyl compound, and specifically, a reaction of forming an aldehyde from a primary alcohol, a reaction of forming a carboxylic acid from an aldehyde, Examples include a reaction in which a ketone is produced from a dialcohol. These oxidation reactions are specifically shown by the following reaction formulas (12) and (13).

[0047]

[Chemical 8]

Examples of the above (4) oxidation of sulfur atom include a reaction of sulfoxide to sulfide, a reaction of sulfoxide to sulfone, and a reaction of thiol to disulfide. Specifically, these oxidation reactions are represented by the following reaction formulas (14) and (1)
5).

[0049]

[Chemical 9]

The above-mentioned (5) oxidation of nitrogen atom is, for example, a reaction in which a hydroxyamine is produced from a primary amine,
Reaction of hydroxyamine to form nitroso compound or azoxy compound, reaction of nitroso compound to form oxime or nitro compound, reaction of secondary amine to form hydroxylamine, reaction of hydroxylamine to form nitrone, tertiary amine to amine Examples include a reaction in which oxide is generated. These oxidation reactions are
Specifically, the following reaction formulas (16), (17) and (1
8).

[0051]

[Chemical 10]

Examples of the above-mentioned (6) oxidation of alkane include a reaction in which a hydroxyl group, a hydroperoxy group, a carboxyl group and a carbonyl group are introduced into an alkane, an ammoxidation and the like. Such an oxidation reaction is specifically represented by the following reaction formula (19).

[0053]

[Chemical 11]

Examples of the above (7) aromatic oxidation include nuclear hydroxylation and side chain oxidation. Specifically, these oxidation reactions are represented by the following reaction formulas (20) and (21).
Indicated by.

[0055]

[Chemical 12]

Examples of the oxidation reaction other than the above (8) (1) to (7) include a reaction in which a lactone is produced from a ketone, Baeyer-Villinger oxidation, oxidative coupling and the like. Specifically, these oxidation reactions are represented by the following reaction formulas (22) and (23).

[0057]

[Chemical 13]

The above reaction formulas (1) to (23) exemplify each form of the oxidation reaction in the present invention. For example, a portion represented as a methyl group is a hydrogen atom or another group. Moreover, each compound may have a substituent and is not particularly limited thereto.

In the oxidation method of the present invention, it is possible to change the oxidizable functional group to be oxidized by changing the kind of the surfactant as described above. The oxidizable functional group can be appropriately selected and oxidized. It should be noted that which type of surfactant is used to determine which oxidizable functional group of a plurality of oxidizable functional groups having different internal environments will be oxidized in advance. It will be determined by changing the type of and examining. This makes it possible to understand which kind of surfactant is used to oxidize which oxidizable functional group, and to identify the organic compound having a plurality of oxidizable functional groups having different internal environments. By selectively oxidizing a specific oxidizable functional group, the present invention can be applied to the production of industrially useful organic compounds.

[0060]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

The oxidation catalyst used in the examples was prepared by the following method. Oxidation catalyst preparation method 1 2 deficient polyoxometalate having TBA (tetrabutylammonium) having a [γ-SiW ₁₀ O ₃₆ ] skeleton modified with La as a counter cation (hereinafter, referred to as La-PO
M-TBA) Inorg. Synth. Bi-defective Keggin-type K ₈ [γ-Si prepared by the method described in 1990, 127, 88].
W ₁₀ O ₃₆ ] 12H ₂ O ₁₀ g, deionized water 20 m
L was added and dissolved, and a nitric acid aqueous solution was added to adjust the pH to 3.8.
Adjusted to. 0.43 g of lanthanum nitrate hexahydrate dissolved in 3.5 mL of ion-exchanged water was added thereto, stirred for 5 minutes, and then tetrabutylammonium nitrate 6.9.
g was added as a solid and stirring was continued for 15 minutes. The produced precipitate was filtered and the filtrate was dried at room temperature for 3 hours, then the recovered solid was dissolved in 7.5 mL of acetonitrile, 150 mL of ion-exchanged water was gently added, and the mixture was stirred for 30 minutes in ice water. The resulting precipitate was collected by filtration and dried at room temperature for 3 hours. The above purification treatment was repeated once more to obtain 4.8 g of the desired compound.

Oxidation catalyst preparation method 2 2-defective polyoxometalate using TBA having a [γ-SiW ₁₀ O ₃₆ ] skeleton modified with Zn as a counter cation (hereinafter referred to as Zn-POM-TBA) lanthanum nitrate Zinc nitrate hexahydrate in place of hexahydrate 0.3
L except that an aqueous solution of g in ion-exchanged water is used
It was prepared according to the method for preparing a-POM-TBA to obtain 5.3 g of the target compound.

Oxidation catalyst preparation method 3 2-defective polyoxometalate (hereinafter referred to as Zn-POM-Cs) using Cs having a [γ-SiW ₁₀ O ₃₆ ] skeleton modified with Zn as a counter cation Inorg. Synth. Bi-defective Keggin-type K ₈ [γ-Si prepared by the method described in 1990, 127, 88].
W ₁₀ O ₃₆ ] 12H ₂ O ₁₀ g, deionized water 20 m
L was added and dissolved, and a nitric acid aqueous solution was added to adjust the pH to 3.8.
Adjusted to. 0.3 g of zinc nitrate hexahydrate dissolved in 3.5 mL of ion-exchanged water was added thereto and stirred for 5 minutes, then 3.8 g of CsCl was added as a solid and stirring was continued for 15 minutes. The formed precipitate was filtered and the filtrate was dried for 3 hours at room temperature to obtain 10 g of the target compound.

Examples 1 to 15 and Comparative Examples 1 to 4 As a substrate, oxidation catalyst, surfactant and oxidizer in water solvent
Hydrogen peroxide is added, and allyl alcohol is added with stirring.
Was carried out at atmospheric pressure. Oxidation catalyst used for reaction, dissolution
The media, surfactants and reaction conditions are shown in Tables 1 and 2. Was
However, in Example 15 and Comparative Example 4, H was used instead of the water solvent.
_TwoA mixed solvent of O / MeCN = 3 mL / 3 mL was used. Substrate: Allyl alcohol 1000 μmol Solvent: 6 mL Oxidation catalyst: 30 m when using polyoxometallate
g, Na_TwoWO_Four・ 2H _TwoO or Na_TwoMoO_Four・
2H_Two8 mg if O is used Reaction temperature: 32 ° C Reaction time: 24 hours Hydrogen peroxide (H_TwoO_Two) 35% aqueous solution: H_TwoO_TwoThe mole
200 μmol as a number

Examples 16 to 18 and Comparative Example 5 In the above Examples and Comparative Examples, the pH was set to 3.5 in the solvent.
The oxidation reaction of allyl alcohol was carried out in the same manner except that a buffering agent was added to adjust to ˜6.0. Table 3 shows the oxidation catalyst, solvent, surfactant, buffer and reaction conditions used in the reaction.

The reaction yield (mol%) and reaction selectivity (mol%) of the above oxidation reaction are shown in Tables 1, 2 and 3. The reaction yield (mol%) is obtained by calculating the number of moles of the product by gas chromatography: {(number of moles of H ₂ O ₂ consumed to form the product) / (added H ₂ O ₂ The number of moles)} × 100. The reaction selectivity (mol%) is the ratio of glycidol and acrolein with the total of glycidol and acrolein in the product being 100. The reaction formula of this reaction is shown below.

[0067]

[Chemical 14]

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

Tables 1, 2 and 3 will be described. Among surfactants, SDS is an abbreviation for anionic surfactant sodium dodecyl sulphate, and Brij58 (trademark of ICI) is a nonionic surfactant polyoxyethylene.
e (20) cetylether, and CTA is a cationic surfactant cetyltrime.
thylammoniumhydrogensulfa
Abbreviation for te, ZWD (“Zwittergent
3-14 Detergent "is Calbiochem
(Trademark) is an abbreviation for N, N-dimethyl-tetradecyl-N-sulfotrimethylene ammonium betaine which is an amphoteric surfactant.

From Table 1, Table 2 and Table 3, when an anionic surfactant, a nonionic surfactant or an amphoteric surfactant is used, unsaturated bonds are selectively oxidized and glycidol is mainly contained. It can be seen that the formation of impurities and the generation of impurities are suppressed and the yield is increased. It can be seen that when a cationic surfactant is used, the hydroxyl group is selectively oxidized to produce acrolein.

Examples 19 to 26 Substrates, an oxidation catalyst, a surfactant and hydrogen peroxide as an oxidant were added to a water solvent, and crotyl alcohol was oxidized with stirring. Oxidation catalyst used in the reaction, solvent,
Table 4 shows the surfactants and reaction conditions. The results of the oxidation reaction of crotyl alcohol are shown in Table 4. The charged amount and reaction conditions are the same as in the case of allyl alcohol. In addition, crotyl alcohol is a mixture of cis- and trans-forms.

Table 4 shows the reaction yield (mol%) and reaction selectivity (mol%) of the above oxidation reaction. The reaction yield (mol%) is the same as the case of Table 1, and the reaction selectivity (mol%) is the case where the total of 2,3-epoxybutanol and 2-butenal in the product is 100. It is a ratio of 2,3-epoxybutanol and 2-butenal. The reaction formula of this reaction is shown below.

[0075]

[Chemical 15]

[0076]

[Table 4]

Abbreviations and the like in Table 4 are the same as above. From Table 4, when an anionic surfactant, a nonionic surfactant or an amphoteric surfactant is used, the unsaturated bond is selectively oxidized to form mainly 2,3-epoxybutanol, and the cation. In the case of using anionic surfactant, the selectivity for hydroxyl group becomes higher than that in the case of using anionic surfactant, nonionic surfactant or amphoteric surfactant, and thus, with 2,3-epoxybutanol. It can be seen that 2-butenal is produced.

Examples 27 to 33 and Comparative Example 6 Substrate, oxidation catalyst, surfactant and hydrogen peroxide as an oxidant were added to a water solvent and stirred with 3-butene-1-.
Oxidation reaction of all was performed. Table 5 shows the oxidation catalyst, solvent, surfactant and reaction conditions used in the reaction. The results of the oxidation reaction of 3-buten-1-ol are shown in Table 5. The charging amount and the reaction conditions are the same as in the case of allyl alcohol except that the reaction time is 24 hours to 48 hours.

Table 5 shows the reaction yield (mol%) and reaction selectivity (mol%) of the above oxidation reaction. The reaction yield (mol%) is the same as the case of Table 1, and the reaction selectivity (mol%) is the case where the total of 3,4-epoxybutanol and 3-butenal in the product is 100. It is a ratio of 3,4-epoxybutanol and 3-butenal. The reaction formula of this reaction is shown below.

[0080]

[Chemical 16]

[0081]

[Table 5]

Abbreviations and the like in Table 5 are the same as above. From Table 5, when an anionic surfactant, a nonionic surfactant or an amphoteric surfactant is used, the unsaturated bond is selectively oxidized to produce mainly 3,4-epoxybutanol, and the cation When a hydrophilic surfactant is used, the hydroxyl group is selectively oxidized to form 3-butenal.

Examples 34 to 37 and Comparative Examples 7 to 8 Hydrogen peroxide was added as a substrate, an oxidation catalyst, a surfactant and an oxidizing agent in a water solvent, and the nerol oxidation reaction was carried out with stirring. Table 6 shows the oxidation catalyst, solvent, surfactant and reaction conditions used in the reaction. The results of the nerol oxidation reaction are shown in Table 6. The charged amount and reaction conditions are the same as in the case of allyl alcohol.

Table 6 shows the reaction yield (mol%) and reaction selectivity (mol%) of the above oxidation reaction. The reaction yield (mol%) is the same as in the case of Table 1, and the reaction selectivity (mol%) is 2 when the total of 2,3-epoxynerol and neral in the product is 100. , 3-epoxynerol and neral. The reaction formula of this reaction is shown below.

[0085]

[Chemical 17]

[0086]

[Table 6]

Abbreviations and the like in Table 6 are the same as above. From Table 6, when an anionic surfactant or a nonionic surfactant is used, one of the unsaturated bonds is selectively oxidized to mainly form 2,3-epoxynerol, and the cationic interface is used. When an activator is used, the hydroxyl group is selectively oxidized to produce neral. In these cases a few
-Epoxynerol and neral were the products, 6,7-epoxynerol was not obtained in any case.

To summarize the above Examples and Comparative Examples, for example, when an oxidation reaction of a compound having an unsaturated bond and a hydroxyl group is carried out by the oxidation method of the present invention, an anionic or nonionic surfactant is used as the surfactant. If an amphoteric surfactant is used, the unsaturated bond will be selectively oxidized, and if a cationic surfactant is used, the hydroxyl group will be selectively oxidized.

That is, in the case of carrying out the oxidation reaction of allyl alcohol according to the present invention, the use of anionic, nonionic or amphoteric surfactants produces mainly glycidol selectively, and the use of cationic surfactants. , Acrolein is selectively produced. Further, in the case of carrying out the oxidation reaction of crotyl alcohol, when an anionic, nonionic or amphoteric surfactant is used, mainly 2,3-epoxybutanol is selectively produced to form a cationic surfactant. When used, it also produces 2-butenal together with 2,3-epoxybutanol. In this case, the selectivity of 2-butenal is relatively improved when the cationic surfactant is used as compared with when the anionic, nonionic or amphoteric surfactant is used. Therefore, when producing 2,3-epoxybutanol using crotyl alcohol as a raw material, an anionic, nonionic surfactant or amphoteric surfactant is selected, and when producing 2-butenal, a cationic surfactant is used. Can be industrially produced by selecting and purifying. Furthermore, 3-butene-1-
When an all-oxidation reaction is performed, the use of anionic or nonionic surfactants or amphoteric surfactants leads mainly to 3,4-
Epoxy butanol is selectively produced, and when a cationic surfactant is used, 3-butenal is selectively produced. When an anionic or nonionic surfactant is used for the oxidation reaction of nerol having two double bonds and a hydroxyl group in the molecule, mainly 2,3-epoxynerol is selectively produced, and cation is used. When the organic surfactant is used, neral is selectively produced.

[0090]

The method for oxidizing an organic compound according to the present invention has the above-mentioned constitution, whereby a specific oxidizable functional group in an organic compound having a plurality of oxidizable functional groups having different intramolecular environments is provided. Since it can be selectively oxidized depending on the kind of the surfactant, various industrially useful organic compounds can be efficiently and simply produced.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 303/14 C07D 303/14 (72) Inventor Masahiro Wada 5-8 Nishimitabicho Suita City Osaka Prefecture Stock Company NIPPON SHOKUBAI (72) Inventor Tetsutaka Mizuno 3-3-6-501 F-term, Nerima-ku, Tokyo F-Term (reference) 4C048 AA01 BB02 BB07 CC01 UU03 XX02 4H006 AA02 AC45 BA14 BA30 BA33 BA35 BA51 BE32 4H039 CA62 CC20

Claims (4)

[Claims] 1. A method of oxidizing an organic compound having a plurality of oxidizable functional groups having different intramolecular environments, the method comprising oxidizing a plurality of oxidizable compounds in the presence of a surfactant and an oxidation catalyst. A method for oxidizing an organic compound, which is carried out by oxidizing at least one of the oxidizing functional groups. 2. The oxidation of an organic compound according to claim 1, wherein the method of oxidizing the organic compound is performed by oxidizing at least one of a plurality of oxidizable functional groups depending on the kind of the surfactant. Method. 3. The method for oxidizing an organic compound according to claim 1 or 2, wherein the organic compound has a double bond as at least an oxidizable functional group. 4. General formula: R—C (R ′) ═CH—CH ₂ —OH (In the formula, R and R ′ are the same or different, and are a hydrogen atom or an alkyl group which may have a substituent. Or an aromatic ring) is used in the reaction system in the presence of an oxidation catalyst in the presence of an oxidation catalyst to produce an oxidized organic compound, which is anionic, nonionic. When at least one of the cationic and amphoteric surfactants is added to the reaction system, an organic compound in which the double bond is epoxidized is produced, and when a cationic surfactant is added, the hydroxyl group is A method for producing an oxidized organic compound, which comprises producing an oxidized carbonyl compound.