JPH1149764A - Production of epoxy compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing the subject compound by reacting a compound having a non-aromatic, ethylenic double bond with oxygen in the presence of an oxidation catalyst to form the corresponding epoxy compound. SOLUTION: This epoxy compound is obtained by reacting a compound having a non-aromatic, ethylenic double bond, e.g. an alkene or cycloalkene compound, with oxygen in the presence of an oxidation catalyst composed of an imide compound shown by the formula [R<1> and R<2> are each H, a halogen, alkyl, aryl, cycloalkyl, hydroxyl, alkoxy, carboxyl, alkoxycarbonyl or acyl, wherein R<1> and R<2> are bound to each other to form a double bond or ring; X is O or hydroxyl; and (n) is 1 to 3]. The oxidation catalyst may be composed of a cocatalyst, e.g. a metallic compound containing a IV to VIII group element, together with the imide compound shown by the formula. The method gives an epoxy compound in high yield by a simple procedure, The epoxy compound can be obtained efficiently by the action of oxygen even under mild conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a corresponding epoxy compound from a compound having a non-aromatic ethylene bond such as an alkene and a cycloalkene.

[0002]

2. Description of the Related Art Chain or cyclic epoxy compounds are important compounds as medicines, fragrances, dyes, organic synthetic intermediates and polymer resin raw materials. Epoxy compounds are produced by reacting a compound having a non-aromatic ethylene bond such as an alkene or a cycloalkene with a peracid such as peracetic acid or perbenzoic acid. However, peracids are unstable and require special care in handling. There is also known a method of obtaining an epoxy compound by treating a halohydrin obtained by reacting a hypohalous acid on an unsaturated compound with an alkali. However, this method is difficult to apply to olefins having a complicated structure. Furthermore, a method of producing a corresponding epoxy compound by allowing a microorganism to act on an unsaturated compound in the presence of oxygen is also known. However, the method using a microorganism is disadvantageous in terms of productivity since the substrate concentration cannot generally be increased.

[0003] Among epoxy compounds, 2,3-hydroxyl groups having a hydroxyl group bonded to a carbon atom adjacent to an epoxy group are known.
Epoxy alcohol (α-hydroxy epoxy compound)
Is especially useful as a synthetic intermediate for high value-added products such as pharmaceuticals. As a method for producing such 2,3-epoxy alcohol, Lions, J. et al. E. [Lyons, JE], Tetrahedron Letters [Te
trahedoron Letters], the pages 2737 (1974), and cyclohexene and oxygen, vanadium complexes [C ₅ H ₅ V (C
O) ₄ ] to synthesize 2,3-epoxycyclohexanol. In addition, Kaneda, K. and other journals of the organic chemistry [J. Org.
m.], Vol. 45, p. 3004 (1980), corresponding to the reaction of cycloalkene and oxygen with vanadium complex [VO (acac) ₂ ] in the presence of azobisisobutyronitrile. Methods for obtaining 2,3-epoxycycloalkanols are disclosed. However, in these methods, the conversion of the reaction components is low, and it is not possible to produce 2,3-epoxy alcohol with a high yield. Adam, W [Ad
am, W.], etc., Tetrahedoron Letters
Letters], p. 2839 (1986), describes the reaction of alkene with singlet oxygen in the presence of titanium tetraisopropoxide Ti (Oi-Pr) ₄ to produce the corresponding 2,3-epoxy alcohol. There is disclosed a method for causing this to occur. However, this method requires a singlet oxygen generator.

[0004] JP-A-8-38909 describes that when a hydrocarbon is oxidized in the presence of an imide compound, a corresponding hydroxy compound, aldehyde compound, ketone compound or organic acid is produced. However, this document does not describe the production of a corresponding epoxy compound from a compound having a non-aromatic ethylene double bond.

[0005]

Accordingly, an object of the present invention is to provide a compound having a non-aromatic ethylene double bond and a corresponding epoxy compound, particularly 2,3-epoxy alcohol (α-hydroxy epoxy compound). Is to provide a method and a catalyst which can be produced with a simple operation in a high yield. Another object of the present invention is to provide a method and a catalyst capable of efficiently producing an epoxy compound from a compound having a non-aromatic ethylene double bond with oxygen under mild conditions.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that an imide compound such as an N-hydroxyphthalimide compound or an oxidation catalyst composed of the imide compound and a cocatalyst is used. It has been found that when used, a corresponding epoxy compound is produced with high yield from a compound having a non-aromatic ethylene double bond by oxygen, and the present invention has been completed. That is, in the production method of the present invention, the general formula (1)

[0007]

Embedded image (Wherein R ¹ and R ² are the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. X represents an oxygen atom or a hydroxyl group, and n represents an integer of 1 to 3) in the presence of an oxidation catalyst composed of an imide compound represented by the following formula: To form a corresponding epoxy compound. The oxidation catalyst may be composed of an imide compound represented by the general formula (1) and a co-catalyst. The co-catalyst can be composed of a metal compound containing a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, or a Group 8 element of the periodic table. Examples of the compound having a non-aromatic ethylene bond include a compound having a chain hydrocarbon having 2 to 20 carbon atoms having an ethylene bond and a compound having a 3 to 30-membered cycloalkene ring. In the above method, a compound having a carbon-hydrogen bond at a site adjacent to an ethylene bond is contacted with oxygen to form a corresponding 2,3-
An epoxy alcohol may be formed. The oxidation catalyst of the present invention is a catalyst for producing a corresponding epoxy compound by bringing a compound having a non-aromatic ethylene bond into contact with oxygen, and comprises an imide compound represented by the general formula (1). It is composed of In the present specification, the “compound having a non-aromatic ethylene double bond” may be simply referred to as “substrate”.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

[Imide compound] In the compound represented by the general formula (1), a halogen atom among the substituents R ¹ and R ² includes:
Includes iodine, bromine, chlorine and fluorine. Examples of the alkyl group include a linear or branched chain having about C _1-10 such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Includes chain alkyl groups. Preferred alkyl groups include, for example, C
_{About 1-6} , especially about C _1-4 alkyl groups are exemplified.

The aryl group includes a phenyl group, a naphthyl group and the like, and the cycloalkyl group includes a cyclopentyl, cyclohexyl, cyclooctyl group and the like. Alkoxy groups include, for example, methoxy, ethoxy,
Propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy groups and the like, about C _1-10 , preferably about C _1-6 , especially C _1-4
A degree of alkoxy groups are included.

The alkoxycarbonyl group includes, for example, an alkoxy moiety such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, etc. _It contains about _1-10 alkoxycarbonyl groups. Preferred alkoxycarbonyl groups include those having an alkoxy moiety of about C _1-6 , especially about C _1-4 .

Examples of the acyl group include C _1-6 acyl groups such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and pivaloyl groups.

The substituents R ¹ and R ² may be the same or different. In the general formula (1),
R ¹ and R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. Preferred aromatic or non-aromatic rings are 5 to 12 membered rings, especially 6 to 1
It is about a zero-membered ring, and may be a heterocyclic ring or a fused heterocyclic ring, but is often a hydrocarbon ring. Examples of such a ring include a non-aromatic alicyclic ring (a cycloalkene ring which may have a substituent such as a cyclohexane ring and a cycloalkene which may have a substituent such as a cyclohexene ring). Ring), a non-aromatic bridged ring (eg, a bridged hydrocarbon ring which may have a substituent such as a 5-norbornene ring), a benzene ring, a naphthalene ring or the like. And aromatic rings. The ring is often composed of an aromatic ring.

Preferred imide compounds include those represented by the following formula:

[0014]

Embedded image (Wherein, R ^{3 to} R ⁶ are the same or different and are each a hydrogen atom,
It represents an alkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a nitro group, a cyano group, an amino group, and a halogen atom. R ¹ ,
R ² and n are the same as described above. In the substituents R ^{3 to} R ⁶ , the alkyl group includes the same alkyl group as the above-described alkyl group, particularly an alkyl group having about _1-6 carbon atoms. Is the same alkoxy group as described above, particularly an alkoxy group having about C _1-4 , and the alkoxycarbonyl group includes the same alkoxycarbonyl group as described above, particularly an alkoxycarbonyl group having an alkoxy moiety of about C _1-4 . Examples of the acyl group include the same acyl groups as described above, particularly, an acyl group of about C _{1-6, and} examples of the halogen atom include fluorine, chlorine, and bromine atoms. The substituents R ^{3 to} R ⁶ are usually a hydrogen atom, C
_It is often about _1-4 alkyl groups, carboxyl groups, nitro groups, and halogen atoms.

In the general formula (1), X represents an oxygen atom or a hydroxyl group, and n is usually about 1 to 3,
Preferably it is 1 or 2. One or more compounds represented by the general formula (1) can be used in the epoxidation reaction.

The acid anhydride corresponding to the imide compound represented by the general formula (1) includes, for example, a saturated or unsaturated aliphatic dicarboxylic anhydride such as succinic anhydride and maleic anhydride, and tetrahydrophthalic anhydride. And unsaturated non-aromatic cyclic polycarboxylic acids such as hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride) and 1,2,3,4-cyclohexanetetracarboxylic acid 1,2-anhydride Anhydrides (alicyclic polycarboxylic anhydrides), bridged cyclic polycarboxylic anhydrides such as hetic anhydride and hymic anhydride (alicyclic polycarboxylic anhydrides), phthalic anhydride, tetrabromo Phthalic anhydride, tetrachlorophthalic anhydride, nitrophthalic anhydride, trimellitic anhydride, methylcyclohexentricarboxylic anhydride, pyromellitic anhydride, none Mellitic acid, 1,8; 4,
Aromatic polycarboxylic anhydrides such as 5-naphthalenetetracarboxylic dianhydride are included. Preferred imide compounds include, for example, N-hydroxysuccinimide,
N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N'-dihydroxycyclohexanetetracarboxylic imide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalide Acid imide, N
-Hydroxyhetimide, N-hydroxyhymic imide, N-hydroxytrimellitic imide,
N, N'-dihydroxypyromellitic imide,
N'-dihydroxynaphthalenetetracarboxylic imide and the like. Particularly preferred compounds include N-hydroxyimide compounds derived from alicyclic polycarboxylic anhydrides, especially aromatic polycarboxylic anhydrides, such as N-hydroxyphthalimide.

The imide compound is prepared by a conventional imidation reaction, for example, by reacting a corresponding acid anhydride with hydroxylamine N
It can be prepared by reacting with H ₂ OH to open the acid anhydride group and then closing the ring to imidize the ring.

[Co-catalyst] The catalyst may comprise an imide compound represented by the above formula (1) and a co-catalyst. The co-catalyst includes a metal compound, for example, a periodic table group 2 element (magnesium, calcium, strontium, barium, etc.), a transition element, a periodic table group 13 element (boron B, aluminum A
l)). The cocatalyst can be used alone or in combination of two or more.

Examples of the element of the transition metal include elements belonging to Group 3 of the periodic table (for example, scandium Sc, yttrium Y, lanthanum La, cerium Ce, samarium S).
lanthanoid element such as m, actinoid element such as actinoid Ac), group 4 element (such as titanium Ti, zirconium Zr, hafnium Hf), group 5 element (such as vanadium V, niobium Nb, tantalum Ta), and group 6 element (chromium Cr , Molybdenum Mo, tungsten W, etc.), Group 7 elements (manganese Mn, technetium Tc, rhenium Re)
Group 8 element (iron Fe, ruthenium Ru, osmium Os), group 9 element (cobalt Co, rhodium Rh, iridium Ir), group 10 element (nickel Ni, palladium Pd, platinum Pt, etc.), group 11 element ( Copper Cu, silver A
g, gold Au, etc.) and Group 12 elements (zinc Zn, cadmium Cd, etc.).

Preferred co-catalysts include transition metal elements (for example, lanthanoid elements such as Ce, Group 3 elements of the periodic table such as actinoid elements, Ti, Zr, and H).
Group 4 element such as f, Group 5 element such as V, Nb, Ta, C
Group 6 elements such as r, Mo and W; Group 7 elements such as Mn, Tc and Re; Group 8 elements such as Fe, Ru and Os; Group 11 elements such as Cu); and Group 13 elements such as B. . Among them, a group 4 element, a group 5 element, a group 6 element, a group 7 element and a group 8 element of the periodic table are preferable. The oxidation number of the metal element constituting the co-catalyst is not particularly limited, and may be, for example, 0, +2, +3, +4, +5, +6, etc., depending on the type of the element.

The co-catalyst may be a simple metal, a hydroxide or the like, but is usually a metal oxide (including double oxides, oxyacids or salts thereof), an organic acid salt or an inorganic acid containing the above elements. salt,
Halide, coordination compound (complex) containing the metal element
Or a polyacid (heteropolyacid or isopolyacid) or a salt thereof in many cases.

Examples of the boron compound include hydrogenated hydrogen
Iodine (eg, borane, diborane, tetraborane, pen
Taborane, decaborane, etc.), boric acid (orthoboric acid,
Metaboric acid, tetraboric acid, etc.), borate (for example, borate
Nickel phosphate, magnesium borate, manganese borate
Etc.), B_TwoO_ThreeSuch as boron oxide, borazan, boraze
Nitrogen such as boron, borazine, boron amide and boron imide
Compound, BF_Three, BCl _Three, Tetrafluoroborate
Any halide, borate ester (for example, boric acid
Butyl, phenyl borate, etc.). Preferred
Boron compounds include borohydride, orthoboric acid, etc.
In particular, boric acid or a salt thereof is included.

The hydroxide includes, for example, Mn (OH)_Two,
MnO (OH), Fe (OH)_Two, Fe (OH)_ThreeSuch
Is included. Metal oxides include, for example, TiO_Two, Zr
O_Two, V_TwoO_Three, V_TwoO_Five, CrO, Cr_TwoO_Three, Mo
O_Three, W_TwoO_Three, MnO, Mn_ThreeO_Four, Mn_TwoO_Three, M
nO_Two, Mn_TwoO₇, FeO, Fe_TwoO_Three, Fe
_ThreeO _Four, RuO_Two, RuO_FourAnd so on. Double oxide
Or, as the oxyacid (or a salt thereof), for example, MnA
l_TwoO_Four, MnTiO_Three, LaMnO_Three, K_TwoMn_TwoO
_Five, CaO.xMnO_Two(X = 0.5, 1, 2, 3,
5); Manganese acid or a salt thereof [for example, Na_ThreeMn
O_Four, Ba_Three(MnO_Four)_TwoManganese (V) acid salts, such as
K_TwoMnO_Four, Na_TwoMnO_Four, BaMnO_FourMa
Ganganate (VI), KMnO_Four, NaMnO_Four, LiMn
O_Four, NH_FourMnO_Four, CsMnO_Four, AgMnO_Four,
Ca (MnO_Four)_Two, Zn (MnO_Four)_Two, Ba (Mn
O_Four)_Two, Mg (MnO_Four)_Two, Cd (MnO_Four)_TwoWhat
Which permanganate]; vanadate, niobate, tantalum
Lulic acid, molybdic acid, tungstic acid or their oxygen
Acid salts and the like.

As the organic acid salt, for example, manganese acetate
Manganese propionate, manganese naphthenate,
C such as manganese alate_2-20Fatty acids (or cycloaliphatic
Boronic acid) salts, manganese thiocyanate and the corresponding Ti salts,
Zr salt, V salt, Cr salt, Mo salt, Fe salt, Ru salt, etc.
Examples of the inorganic acid salt include, for example, iron nitrate,
Nitrates such as gangan, and corresponding sulfates and phosphoric acids
Salts and carbonates (eg, iron sulfate, manganese sulfate, phosphorus
Iron acid, manganese phosphate, iron carbonate, manganese carbonate, perchlorine
Iron oxide and the like). Also, as halide
Is, for example, TiCl_Two, ZrCl_Two, ZrOCl_Two,
VCl_Three, VOCl_Two, MnCl_Two, MnCl_Three, Fe
Cl_Two, FeCl_Three, RuCl_ThreeSuch as chloride or this
Fluoride, bromide and iodide (e.g.,
MnF_Two, MnBr_Two, MnF_Three, FeF_Two, Fe
F_Three, FeBr_Two, FeBr_Three, FeI_Two, CuBr,
CuBr_TwoEtc.), M¹MnC
l_Three, M¹ _TwoMnCl_Four , M¹ _TwoMnCl_Five , M¹ _TwoMnCl
₆(M¹Indicates a monovalent metal)
Is mentioned.

The ligand forming a complex includes an alkoxy group such as OH (hydroxo), methoxy, ethoxy, propoxy and butoxy groups, an acyl group such as acetyl (OAc) and propionyl, methoxycarbonyl (acetato), ethoxycarbonyl and the like. Alkoxycarbonyl group, acetylacetonato (AA), cyclopentadienyl group, halogen atom such as chlorine, bromine, CO, CN, oxygen atom, H ₂ O (aquo), phosphine (eg, triphenylphosphine, etc.) Phosphorus compounds such as triarylphosphine); and nitrogen-containing compounds such as NH ₃ (ammine), NO, NO ₂ (nitro), NO ₃ (nitrat), ethylenediamine, diethylenetriamine, pyridine, and phenanthroline. In the complex or complex salt, the same or different ligands may be coordinated by one kind or two or more kinds. Preferred ligands include, for example, phosphorus compounds such as OH, alkoxy group, acyl group, alkoxycarbonyl group, acetylacetonate, halogen atom, CO, CN, H ₂ O (aquo) and triphenylphosphine;
Nitrogen-containing compounds are included, including H ₃ , NO ₂ , and NO ₃ .

Preferred complexes include those containing the preferred transition metal elements. The transition metal element and the ligand can be appropriately combined to form a complex, for example, an acetylacetonato complex (eg, Ce, Sm, Ti, Z
acetylacetonato complexes such as r, V, Cr, Mo, Mn, Fe, Ru, Cu, Zn, titanylacetylacetonato complex TiO (AA) ₂ , zirconylacetylacetonato complex ZrO (AA) ₂ , vanadylacetylacetate such as diisocyanato complex VO (AA) _2, carbonyl complexes or cyclopentadienyl complexes (e.g., tricarbonyl cyclopentadienyl manganese (I), bis cyclopentadienyl manganese (II), bis-cyclopentadienyl iron (I
I), Fe (CO) ₅ , Fe ₂ (CO) ₉ , Fe ₃ (C
O) ₁₂ ), nitrosyl compounds (eg, Fe (N
O) ₄ , Fe (CO) ₂ (NO) ₂ ), thiocyanato complex (eg, cobalt thiocyanate, manganese thiocyanate, iron thiocyanate, etc.), acetyl complex (eg, cobalt acetate, manganese acetate, iron acetate, Copper acetate, zirconyl acetate ZrO (OAc) ₂ , titanyl acetate TiO
(OAc) ₂ , vanadyl acetate VO (OAc) _2, etc.).

The polyacid is, for example, an element belonging to Group 5 or 6 of the periodic table, for example, V (vanadic acid), Mo (molybdic acid).
And W (tungstic acid) in many cases, and the central atom is not particularly limited. For example, Be,
B, Al, Si, Ge, Sn, Ti, Zr, Th, N,
P, As, Sb, V, Nb, Ta, Cr, Mo, W,
S, Se, Te, Mn, I, Fe, Co, Ni, Rh,
Os, Ir, Pt, Cu or the like may be used. Specific examples of the heteropolyacid include, for example, cobalt molybdate, cobalt tungstate, molybdenum tungstate, manganese molybdate, manganese tungstate,
Manganese molybdenum tungstic acid, vanad molybdophosphoric acid, manganese vanadium molybdic acid, manganese vanadomolybdophosphoric acid, vanadium molybdic acid, vanadium tungstic acid, silicomolybdic acid, silicotungstic acid, phosphomolybdic acid, phosphotungstic acid, lyvanadomolybdenum Acid, phosphorus vanadotungstic acid and the like.

The imide compound represented by the formula (1), or the catalyst composed of the imide compound and the cocatalyst, may be a homogeneous system or a heterogeneous system.
Further, the catalyst may be a solid catalyst in which a catalyst component is supported on a carrier. As the carrier, a porous carrier such as activated carbon, zeolite, silica, silica-alumina and bentonite is often used. The supported amount of the catalyst component in the solid catalyst is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the carrier. It is about 1 to 20 parts by weight. The amount of the cocatalyst supported is 0.1 to 30 parts by weight, preferably 0.5 to 30 parts by weight, per 100 parts by weight of the carrier.
It is about 25 parts by weight, more preferably about 1 to 20 parts by weight.

The amount of the imide compound represented by the general formula (1) can be selected from a wide range, for example, from 0.001 mol (0.1 mol%) to 1 mol (1 mol) relative to 1 mol of the substrate.
00 mol%), preferably about 0.001 mol (0.1 mol%) to 0.5 mol (50 mol%), more preferably about 0.01 to 0.30 mol, and 0.01 to 0.1 mol. 2
It is often about 5 moles. The amount of the co-catalyst (co-oxidizing agent) to be used can be appropriately selected within a range that does not decrease the reactivity and the selectivity.
00001 mol (0.001 mol%) to 1 mol (100
Mol%), preferably about 0.00005 to 0.7 mol, more preferably about 0.0001 to 0.5 mol,
0.0002 to 0.1 mol (for example, 0.0002 to
0.01 mol) in many cases. The activity of the imide compound may decrease as the amount of the cocatalyst increases. Therefore, in order to maintain the high activity of the oxidation catalyst system, the ratio of the cocatalyst is not less than 0.1 mol (for example,
0.001 to 0.1 mol, preferably 0.005 to 0.
08 mol, more preferably about 0.007 to 0.07 mol).

When a heteropolyacid or a salt thereof is used as a cocatalyst, 0.1 to 25 parts by weight, preferably 0.5 to 10 parts by weight, more preferably about 1 to 5 parts by weight, per 100 parts by weight of the substrate. It is. By using such an oxidation catalyst, the epoxidation reaction of a non-aromatic ethylene bond can be catalytically promoted even under mild conditions with high oxidation activity, and the corresponding epoxy compound can be produced with high yield. Can be. In particular, when the imide compound is used in combination with a metal compound containing a Group 4 element, a Group 5 element, a Group 6 element, a Group 7 element, or a Group 8 element, an epoxy compound can be obtained with high selectivity. it can. In particular, as a substrate,
When a compound having a carbon-hydrogen bond at a position adjacent to an ethylene bond is used, the corresponding 2,3-epoxy alcohol can be produced in high yield.

[Substrate] The compound having a non-aromatic ethylene bond as a substrate includes (A) a chain hydrocarbon having an ethylene bond, and (B) a compound having a cycloalkene ring. It may have a plurality of non-aromatic ethylene bonds.

A chain hydrocarbon having an ethylene bond (A)
As a linear or branched hydrocarbon such as ethene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 2,
3-dimethyl-2-butene, 3-hexene, 1-heptene, 2-heptene, 1-octene, 2-octene, 3-
Octene, 2-methyl-2-butene, 1-nonene, 2-
Alkenes such as nonene, decene, undecene, dodecene, tetradecene, hexadecene, and octadecene; for example, butadiene, isoprene, 1,5-hexanediene, 1,6-heptadiene, 1,7-octadiene,
2,6-octadiene, decadiene, undecadiene,
Alkadienes such as dodecadiene; and alkatrienes such as undecatriene and dodecatriene. These chain hydrocarbons include, for example, hydroxyl group, mercapto group, carboxyl group, substituted oxy group (alkoxy group, aryloxy group, etc.), substituted thio group (alkylthio group, arylthio group, etc.), substituted oxycarbonyl group (alkoxy group) Carbonyl group, aryloxycarbonyl group, etc.), oxo group, carbamoyl group, substituted carbamoyl group, cyano group, nitro group, amino group, substituted amino group, sulfo group, aromatic hydrocarbon group, heterocyclic group,
It may have a substituent such as a halogen atom. The chain hydrocarbon (A) has, for example, about 2 to 20, preferably about 2 to 12 carbon atoms.

Examples of the compound (B) having a cycloalkene ring include cycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene and cyclododecene;
Cyclopentadiene, 1,3-cyclohexadiene,
Cycloalkadienes such as 1,4-cyclohexadiene, 1,3-cycloheptadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene, cyclodecadiene and cyclododecadiene; for example, cyclooctatriene; For example, cycloalkatetraenes such as cyclooctatetraene and the like. These compounds include, for example, an alkyl group (for example, a C _1-4 alkyl group), a hydroxyl group, a mercapto group, a hydroxyalkyl group,
Carboxyl group, substituted oxy group (alkoxy group, aryloxy group, etc.), substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, etc.),
Substituted thio group (alkylthio group, arylthio group, etc.),
Oxo group, carbamoyl group, substituted carbamoyl group, cyano group, amino group, substituted amino group, nitro group, sulfo group,
It may have a substituent such as an aromatic hydrocarbon group, a heterocyclic group or a halogen atom. Preferred compound (B) includes 3
~ 30 membered ring (e.g. 3-20 membered ring), preferably 3 ~
16-membered ring, especially a 5- to 12-membered ring (for example, a 5- to 10-membered ring)
And compounds having the formula:

When these compounds having a non-aromatic ethylene bond are oxidized by the method of the present invention, even under mild conditions, the ethylene bond is epoxidized and a carbon-hydrogen bond is formed at a site adjacent to the ethylene bond. In the compound having (1), a hydroxyl group is introduced into a carbon atom at a position adjacent to the ethylene bond, and the corresponding epoxide and / or 2,3-epoxy alcohol can be efficiently produced. In particular, when a compound having a cycloalkene ring is used,
3-Epoxy alcohol can be easily produced.

[Epoxylation Reaction] The oxygen used for epoxidation of the compound having a non-aromatic ethylene bond may be active oxygen, but it is economically advantageous to use molecular oxygen. . The molecular oxygen is not particularly limited, and pure oxygen may be used, or oxygen diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide may be used. It is preferable to use air from the viewpoint of economy as well as operability and safety. The amount of oxygen used can be selected according to the type of the substrate, and is usually 0.5 mol or more (for example, 1 mol or more), preferably 1 to 100 mol, more preferably 2 to 50 mol per mol of the substrate. It is about a mole. In many cases, an excess molar amount of oxygen relative to the substrate is used, and it is particularly advantageous to carry out the reaction under an atmosphere containing molecular oxygen such as air or oxygen.

The process of the present invention is usually carried out in an organic solvent inert to the reaction. Examples of the organic solvent include organic acids such as acetic acid and propionic acid, nitriles such as acetonitrile, propionitrile and benzonitrile, formamide, acetamide, dimethylformamide (DM
F), amides such as dimethylacetamide, aliphatic hydrocarbons such as hexane and octane, aromatic hydrocarbons such as benzene, halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride and chlorobenzene, nitrobenzene, nitromethane, Examples thereof include nitro compounds such as nitroethane, esters such as ethyl acetate and butyl acetate, and mixed solvents thereof.
The substrate may be used as a reaction solvent by using an excess amount of the substrate. As the solvent, an organic acid such as acetic acid, a nitrile such as acetonitrile, and a halogenated hydrocarbon such as dichloroethane are often used.

The method of the present invention is characterized in that the epoxidation reaction proceeds smoothly even under relatively mild conditions. The reaction temperature can be appropriately selected depending on the type of the substrate and the like, and is, for example, 0 to 300 ° C, preferably 30 to 250 ° C.
° C, more preferably about 40 to 200 ° C, and usually reacts at about 50 to 150 ° C (for example, about 50 to 90 ° C) in many cases. The reaction can be performed under normal pressure or under pressure. When the reaction is performed under pressure, it is usually 1 to 100 atm (for example, 1.5 to 80 atm).
m), preferably 2 to 70 atm, more preferably 5 atm.
It is often about 50 atm. The reaction time can be appropriately selected depending on the reaction temperature and pressure, for example, from a range of 30 minutes to 48 hours, preferably 1 to 36 hours, more preferably 2 to 24 hours. The type of substrate,
By controlling the reaction temperature and the reaction time according to the type of the catalyst and the co-catalyst, the generation of by-products (for example, ketones) can be suppressed, and the epoxy compound can be generated with high selectivity. The reaction is carried out in the presence of the catalyst.
The substrate may be brought into contact with oxygen, and the reaction can be carried out by a conventional method such as a batch system, a semi-batch system, or a continuous system in the presence of molecular oxygen or in the flow of molecular oxygen. After completion of the reaction, the reaction product is subjected to a conventional method, for example, filtration, concentration,
Separation means such as distillation, extraction, crystallization, recrystallization, and column chromatography, and separation means combining these,
It can be easily separated and purified.

In the method of the present invention, a compound having a non-aromatic ethylene bond such as an alkene or a cycloalkene is used as an intermediate compound for pharmaceuticals, fragrances, dyes, foods, organic synthetic intermediates, and raw materials for polymer resins. Can be obtained.

[0039]

According to the method of the present invention, the above-mentioned general formula (1)
In order to use an imide compound represented by or an oxidation catalyst composed of this imide compound and a cocatalyst, the corresponding epoxy compound is produced from the compound having a non-aromatic ethylene bond by a simple operation in a high yield. be able to. In addition, even under mild conditions, the epoxy compound can be produced with oxygen at a high production efficiency.

[0040]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. Example 1 3 mmol of cyclohexene, 1.25 mol% of N-hydroxyphthalimide based on cyclohexene, 0.05 mol% of vanadyl acetylacetonate VO (AA) ₂ , 1,2-dichloroethane 5 based on cyclohexene
The mixture was stirred at 70 ° C. for 4 hours under an oxygen atmosphere. When the product in the reaction solution was examined by gas chromatography analysis, the conversion of cyclohexene was 70%,
2,3-epoxycyclohexanol (selectivity 66%)
And cyclohexene oxide (selectivity 11%). In addition to the above compounds, 2-cyclohexen-1-one (selectivity 15%) and 2-cyclohexen-1-one
1-ol (selectivity 4%) was formed.

Example 2 A reaction was carried out in the same manner as in Example 1 except that N-hydroxyphthalimide was used in an amount of 5 mol% based on cyclohexene. As a result, the conversion of cyclohexene was 95%, and the conversion of 2,3-epoxycyclohexanol (selectivity was 95%). 56%) and cyclohexene oxide (selectivity 10%). In addition to the above compounds, 2-cyclohexen-1-one (selectivity 21%) and 2-cyclohexen-1-ol (selectivity 2%) were formed.

Example 3 N-Hydroxyphthalimide was 10 mol% based on cyclohexene, and vanadyl acetylacetonate VO (A
A) ₂ is used in an amount of 0.5 mol% based on cyclohexene;
The reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at 5 ° C. for 18 hours.
3-epoxycyclohexanol (selectivity 48%);
Cyclohexene oxide (selectivity 15%) was obtained. In addition to the above compounds, 2-cyclohexene-
1-one (selectivity 15%) and 2-cyclohexene-1
-All (selectivity 4%).

Example 4 Manganese (II) acetylacetonate Mn (AA) in place of vanadyl acetylacetonate VO (AA) _{2
When the} reaction was carried out in the same manner as in Example 1 except that 0.05 mol% of ₂ was used relative to cyclohexene, 2,3-epoxycyclohexanol (yield: 60%) was obtained with a conversion of cyclohexene of 67%. .

Example 5 Instead of vanadyl acetylacetonate VO (AA) ₂ , manganese (III) acetylacetonate Mn (A
A) Reaction was carried out in the same manner as in Example 1 except that 0.05 mol% of ₃ was used with respect to cyclohexene. As a result, 2,3-epoxycyclohexanol (yield 62%) was obtained with a conversion of cyclohexene of 66%. Was done.

Example 6 The reaction was carried out in the same manner as in Example 1 except that H ₂ MoO ₄ molybdate was used in an amount of 0.05 mol% with respect to cyclohexene instead of vanadyl acetylacetonate VO (AA) _2. With a conversion of 58%
-Epoxycyclohexanol (52% yield) was obtained.

Example 7 A reaction was carried out in the same manner as in Example 1 except that vanadyl acetylacetonate VO (AA) ₂ was replaced by 0.05 mol% of iron acetylacetonate Fe (AA) ₃ with respect to cyclohexene. However, the conversion of cyclohexene is 52
%, 2,3-epoxycyclohexanol (yield 50
%)was gotten.

Example 8 A reaction was carried out in the same manner as in Example 1 except that manganese acetate Mn (OAc) ₂ was used in an amount of 0.05 mol% with respect to cyclohexene in place of vanadyl acetylacetonate VO (AA) ₂ . With a conversion of cyclohexene of 71%,
2,3-Epoxycyclohexanol (66% yield) was obtained.

Example 9 A reaction was carried out in the same manner as in Example 1 except that chromium acetylacetonate Cr (AA) ₃ was used in an amount of 0.05 mol% with respect to cyclohexene instead of vanadyl acetylacetonate VO (AA) ₂ . However, at a conversion of cyclohexene of 74%, 2,3-1-cyclohexanol (yield 71
%)was gotten.

Example 10 Vanadyl acetylacetonate VO (AA)_Two Instead of
And tungsten oxide W _TwoO_ThreeTo cyclohexene
In the same manner as in Example 1 except that
When the conversion of cyclohexene was 51%, 2,3
-Epoxycyclohexanol (47% yield) was obtained
Was.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that vanadyl acetylacetonate VO (AA) ₂ was used in an amount of 0.5 mol% based on cyclohexene without using N-hydroxyphthalimide. The conversion was less than 5%, only a small amount of cyclohexene oxide (less than 1% selectivity) was formed, and no 2,3-epoxycyclohexanol was formed.

Claims (6)

[Claims] 1. A compound of the general formula (1) (Wherein R ¹ and R ² are the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. X represents an oxygen atom or a hydroxyl group, and n represents an integer of 1 to 3) in the presence of an oxidation catalyst composed of an imide compound represented by the following formula: A method for producing an epoxy compound in which a corresponding epoxy compound is produced by contact. 2. A compound having a non-aromatic ethylene bond is brought into contact with oxygen in the presence of an oxidation catalyst comprising an imide compound represented by the general formula (1) and a cocatalyst,
A method for producing an epoxy compound that produces a corresponding epoxy compound. 3. The co-catalyst comprises a Group 4 element, a Group 5 element,
The method for producing an epoxy compound according to claim 2, which is a metal compound containing a Group 6 element, a Group 7 element, or a Group 8 element. 4. The compound having a non-aromatic ethylene bond is a compound having an ethylene bond and having a chain hydrocarbon having 2 to 20 carbon atoms or a cycloalkene ring having 3 to 30 members. A method for producing the epoxy compound as described above. 5. The method for producing an epoxy compound according to claim 1, wherein a compound having a carbon-hydrogen bond at a site adjacent to the ethylene bond is brought into contact with oxygen to produce a corresponding 2,3-epoxy alcohol. . 6. A catalyst for producing a corresponding epoxy compound by bringing a compound having a non-aromatic ethylene bond into contact with oxygen, wherein the catalyst has the general formula (1): (Wherein R ¹ and R ² are the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. X represents an oxygen atom or a hydroxyl group, and n represents an integer of 1 to 3).