JP3177666B2 - Oxidation reaction of olefins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for epoxidizing olefins.

[0002] Epoxy compounds are very important industrial chemical products. It can be used not only as a raw material for general epoxy resins and intermediates for organic chemicals and agricultural chemicals, but also as a curing agent for various resins. Further, by using a photocationic catalyst, it can be used as a photocuring agent for a transparent resin. Specific examples include uses as components such as inks, paints, photoresists, and hard coating agents for various substrates.

[0003]

2. Description of the Related Art Olefins are prepared in the presence of a transition metal catalyst.
Methods for obtaining the corresponding epoxy compounds using an organic peracid such as peracetic acid or an oxidizing agent such as hydrogen peroxide are known. Methods for producing the corresponding epoxy compounds by oxygen oxidation are known. In addition, there is a production method using a so-called co-oxidation reaction in which a peroxide is generated in the system by oxygen in the presence of a co-oxidizing agent such as an alkane or an aldehyde to oxidize olefins.

[0004] These methods have problems such as a high cost of the oxidizing agent and severe reaction conditions. Much catalytic research has been conducted on epoxidation reactions using molecular oxygen.However, only a few types of catalysts, such as metal porphyrin complex catalysts of iron, manganese, and ruthenium, have been found to be effective. is there. For example,
Tetrahedron Lett. 1011 (197
4) reports an oxygen oxidation reaction using a cyclopentadienyl-vanadium-carbonyl complex.

[0005] Org. Chem. , 45 , 3004
(1980) reports oxygen oxidation of olefins catalyzed by an oxovanadium acetylacetonate complex in the presence of azobisisobutyronitrile. J.
Chem. Soc. Chem. Commun. , 18
6 (1974), tetraphenylporphyrinatoiron chloride complex was prepared according to J. Am. Am. Chem. Soc. , 107 ,
5790 (1985) reports an oxidation reaction using a dioxo (tetramesitylporphyrinato) ruthenium complex as a catalyst. JP-A-3-246238 reports an oxygen oxidation method using a halogenated porphyrin complex catalyst.

However, the above-mentioned reaction method using a catalyst has problems such as the fact that the catalyst is expensive, has low activity, and requires a large amount of catalyst for the reaction to proceed sufficiently.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to oxidize an olefin compound with molecular oxygen using an onium salt of a heteropolyacid having a polyatom of tungsten or a derivative thereof as a catalyst to obtain a high selectivity and a high selectivity. An object of the present invention is to provide a method for obtaining an epoxy compound at a conversion rate.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a method for obtaining an epoxy compound by oxidizing an olefin compound with molecular oxygen using an onium salt of a heteropolyacid having a polyatom of tungsten or a derivative thereof as a catalyst.

Hereinafter, the present invention will be described in detail.

[0010] The catalyst used in the process of the present invention comprises:
An onium salt or a derivative of heteropolyacid poly atom is tungsten, the general formula _{(I) Q n XW 11 MO} 39 (I) ( wherein, M is in the periodic table 3A~7A Group, Group 8,. 1B- 5B
Group oxo or its oxo compound, n
Represents an integer of n = 12- (valence of X + valence of M), and X represents an element belonging to Group 3B to 5B in the periodic table. Also,
Q is a general formula (II) R ₁ R ₂ R ₃ R ₄ L ⁺ (II) (wherein, R _{1 to} R ₄ in the formula (II) each independently represent an alkyl group having 1 to 30 carbon atoms) And one of them may be hydrogen. L represents a nitrogen or phosphorus atom.) Represents a cation portion of an onium salt represented by the following formula: A compound represented by or general _{formula) (III) Q m X 2} W 17 MO 61 (III) ( wherein, m valence of m = 20-2 × (X) - Table with (valence of M) Wherein Q, M and X are as defined above, or a compound of the general formula (IV) Q ₁ (XW ₁₁ O ₃₉ ) ₂ M (IV) (where 1 is 9 or 10) And M represents any one of lanthanoid elements, and Q and X are the same as those described above.).

In the compound represented by the general formula (I) or (III), M is a group of 3A to 7A, 8 or 1 in the periodic table.
Represents any of the elements of groups B to 5B or an oxo compound thereof, and includes Cu, Fe, Ni, Cr, Co, Mn, Zn, S
n, Pb, Bi, Sb, NbO, or VO, particularly Cu, Co, Fe, Mn, Ni,
Preferably, it is either VO or Sn.

In the compound represented by the general formula (VI), M represents a lanthanoid element, and La, Ce, N
d and Sm can be exemplified.

In the compounds represented by formulas (I) or (III) and (IV), X represents 3 in the periodic table.
Represents any of the elements of groups B to 5B, for example, P, As,
Preferably, it is either Si or Ge.

Some specific examples of the onium salt of the compounds represented by the general formulas (I), (III) and (IV) except for the cation portion are shown below, but are not limited thereto. is not.

Specific examples of the compound represented by the general formula (I) include (PW ₁₁ NiO ₃₉ ) ^5- and (PW ₁₁ CuO
₃₉ ) ^5- , (PW ₁₁ FeO ₃₉ ) ^4- , (PW ₁₁
MnO ₃₉ ) ^5- , (PW ₁₁ MnO ₃₉ ) ^4- , (P
W ₁₁ ZnO ₃₉ ) ^5- , (PW ₁₁ Bi
O ₃₉ ) ^4- , (PW ₁₁ CrO ₃₉ ) ^4- , (PW
^{_{11 CoO 3 9) 5-, (}} PW 11 SnO 39) 5-,
(PW ₁₁ SnO ₃₉ ) ^3- , (PW ₁₁ VO ₄₀ )
^{_{4-, (SiW 11 NiO 39)}} 6-, (SiW 11 F
^{_{eO 3 9) 5-, (GeW}} 11 NiO 39) 6-, (G
Compounds represented by a composition formula such as eW ₁₁ FeO ₃₉ ) ^5- may be mentioned.

Specific examples of the compound represented by the general formula (III) include (P ₂ W ₁₇ NiO ₆₁ ) ^8- and (P ₂ W
₁₇ CuO ₆₁ ) ^8- , (P ₂ W ₁₇ Fe
O ₆₁ ) ^7- , (P ₂ W ₁₇ CoO ₆₁ ) ^8- , (P ₂
W ₁₇ VO ₆₂ ) ⁷⁻ , (P _2W17 Sn
O ₆₁ ) ^8- , (P ₂ W ₁₇ SnO ₆₁ ) ^6- , (Si
^{_{2 W 17 NiO 61) 10 -}} , (Ge 2 W 17 NiO
₆₁ ) Compounds represented by a composition formula such as ^10- can be exemplified.

Specific examples of the compound represented by the general formula (IV) include ((PW ¹¹ O ³⁹ ) ² Ce) ¹⁰⁻ , ((P
W ¹¹ O ³⁹ ) ² Ce) ^9- , ((PW ¹¹ O ³⁹ ) ²
Nd) ^10- , ((PW ¹¹ O ³⁹ ) ² Nd) ^9- ,
^{((PW 11 O 39) 2} Sm) 10-, ((PW 11 O
³⁹ ) ² Sm) ^{9- and the} like.

The cation part of the onium salt represented by the general formula (II) is a quaternary ammonium or a quaternary phosphonium, and specific examples thereof include tetraethylammonium, tetranormal propyl ammonium, tetraisopropyl ammonium, tetra normal butyl ammonium, Tetranormalhexyl ammonium, tetracyclohexylammonium, trioctylmethyl ammonium,
Tetradodecyl ammonium, cetyl pyridinium, ethyl picolinium, normal butyl picolinium, ethyl imidazoline, tetra normal butyl phosphonium,
Examples include, but are not limited to, tetracyclohexylphosphonium, trioctylethylphosphonium, and the like.

The above-mentioned compound may contain an arbitrary amount of bound water. Usually, a compound containing 5 or less bound water per molecule of the compound is obtained. Therefore, if necessary, it may be used after dehydration under reduced pressure or heating.

Formulas (I) or (III) and (I)
The compound represented by V) may be obtained by any method, and is not particularly limited. Moreover, you may use a commercial item as it is.

The heteropolyacid onium salt having a polyatom of tungsten or a derivative thereof is, for example, a compound represented by the above general formula (I) ((C ₈ H ₁₇ ) ₃ CH)
For _{3 N) 5 PW 11 NiO 39} , can be obtained by the following procedures. 12-Tungsulic acid was reacted with nickel nitrate in an aqueous solution at 90 ° C., and a solution of potassium acetate / acetic acid was added to keep the pH at 7, and after further reacting for 30 minutes, the mixture was cooled to obtain K ₅ PW ₁₁ NiO _39.・ NH ₂
O crystals are obtained. This in aqueous solution, the stoichiometric amount of _{(C 8 H 17) 3 CH} 3 N + Cl - can be obtained as a yellow solid by allowing the reaction. The resulting compound can be extracted and extracted with an organic agent such as dichloroethane, dried, and used for the reaction.

The amount of the catalyst used depends on the olefin used.
The molar ratio can be in the range of 0.001 to 0.5 mol, particularly preferably in the range of 0.01 to 0.1 mol.
These catalysts may be used alone or in combination of two or more.

The olefin used in the epoxidation reaction using the compound of the present invention as a catalyst has the general formula (V) R ₅ R ₆ C = CR ₇ R ₈ (V) (wherein R ₅ , R ₆ , R ₇ and R ₈ are each substituted with a functional group which is inactive in the epoxidation reaction, and each is a hydrogen atom or an alkyl and alkenyl having up to 20 carbon atoms, optionally a cycloalkyl or cycloalkyl having a branched shape. And alkenyl, aryl, alkylaryl, and alkenylaryl. Further, R _{5 to} R ₈ may form a ring with an adjacent group, respectively. R _{5 to} R
_The group represented by ₈ is, for example, a group such as a hydrogen atom, hydroxy, halogen, nitro, alkoxy, carbonyl, carboxylic acid, ester, and nitrile.

Specific examples of the olefins represented by the general formula (V) include, as alkenes, ethylene, propylene, butenes, butadiene, pentenes, 1-hexene, 3-hexene, 1-heptene, 1- Examples include octene, diisobutylene, 1-nonene, limonene, pinene, myrcene, 1-undecene, 1-pentadecene, 1-octadecene, 1-nonadecene, and trimers and tetramers of propylene. Chain terpenes as polyenes,
And polybutadiene. Examples of the aromatic olefinic hydrocarbon include styrene, methylstyrene, divinylbenzene, indene, and stilbene. In addition, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, cyclodecene, cyclododecatriene, dicyclopentadiene, methylenecyclopropane, as alicyclic olefinic hydrocarbons,
Examples include methylenecyclopentane, methylenecyclohexane, and vinylcyclohexane. Examples of substituted olefinic hydrocarbons include olefin ketones such as methyl allyl ketone, halogenated olefins such as allyl chloride, allyl bromide, crotyl chloride, methallyl chloride, and dichlorobutene, acrylic acid, methacrylic acid, crotonic acid, and the like. Olefin carboxylic acids, olefin alcohols such as allyl alcohol, and olefin esters such as allyl acetate, alkyl acrylate, alkyl methacrylate, diallyl maleate, and diallyl phthalate, but are not limited thereto.

The reaction temperature and pressure are determined by the reactivity, physical and chemical properties of the olefin. For example, it can be set to 0 to 150 ° C. The reaction may be carried out at normal pressure or in an autoclave under overpressure.

The reaction time can be 0.5 to 48 hours.

In this reaction, oxidation is carried out using molecular oxygen. Pure oxygen may be used, or an inert gas containing molecular oxygen may be used. The partial pressure of oxygen by oxygen or an inert gas containing oxygen is preferably 0.1%.
３０30 kg / cm ² , 0.5 to 10 kg / cm ²
Is more preferable. In addition, the reaction may be performed under pressure with oxygen or under an atmosphere, or may be performed by supplying oxygen to the reaction solution by bubbling.

A solvent may be used. Examples of the solvent used include aromatic hydrocarbons such as benzene and toluene;
Examples thereof include, but are not limited to, halogenated hydrocarbons such as dichloromethane, chloroform, and dichloroethane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and nitriles such as acetonitrile.

In the method of the present invention, hydroperoxides such as tertiary butyl hydroperoxide, and peracids such as acetic acid and peracetic acid may be added as a reaction accelerator. At that time, the accelerator may be added at the beginning of the reaction or may be added continuously as the reaction proceeds.

The reaction of the present invention may be carried out continuously in the liquid phase or batchwise.

The reaction mixture obtained by the above method comprises an epoxy compound and by-products, unreacted starting materials,
Since it contains a catalyst and the like, it can be obtained by separating and purifying the target epoxy compound from the reaction mixture. The separation method used is not particularly limited, for example, distillation,
A known separation method such as an adsorption method, extraction, or recrystallization may be used. Specifically, for example, a crude product can be recovered by dissolving the reaction solution in an organic solvent such as dichloromethane, washing with an aqueous sodium carbonate solution and pure water, and removing the solvent. By purifying the crude product by distillation,
The desired product can be obtained.

[0032]

The present invention will be described in detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 ((C ₈ H ₁₇ ) ₃ as a catalyst in a 100 ml reaction vessel
CH ₃ N) ₅ PW ₁₁ NiO ₃₉ (0.02 mmol)
After sufficiently replacing the inside of the reaction vessel with oxygen, cyclooctene (2.2 g, 20 mmol) and dichloroethane (20 ml) as a solvent were charged, and an oxygen partial pressure of 1 kg /
cm ² and reacted at 80 ° C. for 24 hours.

After completion of the reaction, the reaction mixture was analyzed by gas chromatography to find that the conversion of cyclooctene was
It was 25.0 mol% and the selectivity to epoxycyclooctane was 85.0 mol%.

Example 2 As a catalyst, ((C ₈ H ₁₇ ) ₃ CH ₃ N) ₄ PW ₁₁
The reaction was carried out in the same manner as in Example 1, except that FeO ₃₉ (0.02 mmol) was used. As a result, the conversion of cyclooctene was 29.5 mol%, and the selectivity to epoxycyclooctane was 88.4 mol.
1%.

Example 3 As a catalyst, ((C ₈ H ₁₇ ) ₃ CH ₃ N) ₅ PW ₁₁
SnO ₃₉ and ((C ₈ H ₁₇ ) ₃ CH ₃ N) ₃ PW ₁₁
The reaction was carried out in the same manner as in Example 1, except that a mixture of Sn ₃₉ (0.02 mmol) was used.
As a result, the conversion of cyclooctene was 22.0 mol%.
And a selectivity to epoxycyclooctane of 88.3.
mol%.

Example 4 ((C ₈ H ₁₇ ) ₃ CH ₃ N) ₄ PW ₁₁ as a catalyst
Except that VO ₄₀ (0.02 mmol) was used,
The reaction was carried out in the same manner as in Example 1. As a result, the conversion of cyclooctene was 29.4 mol%, and the selectivity to epoxycyclooctane was 86.1 mol.
1%.

Example 5 ((C ₈ H ₁₇ ) ₃ CH ₃ N) ₇ P ₂ W was used as a catalyst.
_The reaction was performed in the same manner as in Example 1, except that ₁₇ FeO ₆₁ (0.08 mmol) was used. As a result, the conversion of cyclooctene was 40.2 mol%, and the selectivity to epoxycyclooctane was 81.4 mol.
1%.

Example 6 As a catalyst, ((C ₈ H ₁₇ ) ₃ CH ₃ N) ₈ P ₂ W
_The reaction was carried out in the same manner as in Example 1, except that ₁₇ NiO ₆₁ (0.08 mmol) was used. As a result, the conversion of cyclooctene was 38.0 mol%, and the selectivity to epoxycyclooctane was 86.3 mol.
1%.

Example 7 As a catalyst, ((C ₈ H ₁₇ ) ₃ CH ₃ N) ₁₀ (PW
_The reaction was performed in the same manner as in Example 1, except that ₁₁ O ₃₉ ) ₂ Nd (0.08 mmol) was used.
As a result, the conversion of cyclooctene was 16.1 mol%.
And a selectivity to epoxycyclooctane of 82.4 m.
ol%.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that no catalyst was used. As a result, the conversion of cyclooctene was 1.3 mol%, and only trace amounts of epoxycyclooctane were detected.

Comparative Example 2 As a catalyst, ((C ₈ H ₁₇ ) ₃ CH ₃ N) ₂ WO
Example 1 except that ₄ (0.15 mmol) was used.
The reaction was carried out in the same manner as described above. As a result, the conversion of cyclooctene was 1.7 mol%, and only trace amounts of epoxycyclooctane were detected.

[0043]

According to the method of the present invention, the epoxidation of olefins using molecular oxygen can be carried out by using an onium salt of a heteropolyacid having a polyatom of tungsten and / or a derivative thereof as a catalyst. It can be carried out.

Claims (2)

(57) [Claims] (1) When oxidizing an olefin compound with molecular oxygen to obtain an epoxide, the following general formula (I) or (II)
An oxygen oxidation method for an olefin compound, wherein at least one selected from I) and (IV) is used as a catalyst. _{Q n XW 11 MO 39 (I} ) ( wherein, M is in the periodic table 3A~7A Group, Group 8, wires 1 b to 5 b
Group oxo or its oxo compound, n
Represents an integer of n = 12- (valence of X + valence of M), and X represents an element belonging to Group 3B to 5B in the periodic table. Also,
Q is a general formula (II) R ₁ R ₂ R ₃ R ₄ L ⁺ (II) (wherein, R _{1 to} R ₄ in the formula (II) each independently represent an alkyl group having 1 to 30 carbon atoms) And one of them may be hydrogen. L represents a nitrogen or phosphorus atom.) Represents a cation portion of an onium salt represented by the following formula: _{) Q m X 2 W 17 MO} 61 (III) ( wherein, m is m = 20-2 × (valence of X) - represents an integer represented by (M valence of), Q, M, X Is the same as described above.) Q ₁ (XW ₁₁ O ₃₉ ) ₂ M (IV) (In the formula, 1 is 9 or 10, M represents any of lanthanoid elements, and Q and X are the same as described above.) ) 2. M is Cu, Fe, Ni, Co, Mn, S
2. The oxygen oxidation method according to claim 1, wherein the oxygen oxidation method is any one of n and VO.