JPH09262479A - Lewis acid catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high activity Lewis acid catalyst usable even under coexistence of water. SOLUTION: A resin complex consisting of a metallic halide represented by the formula and a quat. salt type anion exchange resin is synthesized. In the formula, M is at least one kind of metal selected from among groups IIIa-Vb elements of the periodic Table, X1 is halogen and (q) is an integer equal to the valance of M.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a complex catalyst composed of a metal halide used in a Lewis acid-catalyzed reaction and a quaternary salt type anion exchange resin.

[0002]

2. Description of the Related Art Up to now, a quaternary ammonium salt type anion exchange resin (Dowex-1: an ion exchange resin manufactured by Dow Chemical Co., USA) has been used in a hydrochloric acid rich in chlorides of iron, molybdenum, tungsten and uranium. Known to be adsorbed (J. Amer. Chem. Soc., 77, 3972 (1955), Journal of the American Chemical Society)
reference). It is also known that iron chloride (FeCl ₃ ) forms a complex with a quaternary ammonium salt type anion exchange resin in concentrated hydrochloric acid (Bulletin of the Chemical Society of Japan). of the Che
mical Society of Japan), 42, p. 1760 (1969)). Further, it is known that various metal chlorides form a chlorine-containing negative charge complex in concentrated hydrochloric acid and the complex is adsorbed by anion exchange resin, but this adsorption occurs only in concentrated hydrochloric acid. Observed and described as not adsorbed in dilute hydrochloric acid or water (Proceeding of the International Conference on the Peaceful Uses of Atomic Energy, Geneva). Ene
rgy, Geneva), 1955, 11: p / 837, 113-125). However, a complex composed of a metal halide other than iron chloride and a quaternary salt type anion exchange resin has not been known so far.

On the other hand, specific metal halides, for example, so-called Lewis acids such as aluminum halides, iron halides, zinc halides, tin halides, etc. are used in Friedel-Crafts alkylation reaction (synthesis of alkylbenzene derivative, etc.), Diels Industrially useful catalysts used for Alder reaction (addition reaction of conjugated diene compound and olefinic compound), ene reaction (addition reaction of olefinic compound and aldehyde compound or olefinic compound), cationic polymerization reaction, etc. Known as. However, a complex composed of a metal halide and a quaternary salt type anion exchange resin is a substance having a structure and physical properties different from those of the metal halide, and an example in which the complex is used as a catalyst has not been known so far.

[0004]

In a catalytic reaction using a general Lewis acid such as a metal halide, the catalyst is uniformly dissolved in the reaction solution or a part thereof is dissolved.
It was difficult to separate and collect the catalyst component from the reaction liquid component after the reaction. For this reason, the catalyst is often used as a disposable product, and after the reaction, it was separated from the reaction solution by a method such as washing with neutralized water or removal by adsorption, and was discarded. When the catalyst is reused, it was reused in a state that it contained a high-boiling-point by-product remaining after the product or the solvent was distilled off from the reaction solution. This method has a problem that the decomposition of the product is easily promoted because the catalyst component coexists during the distillation separation. Further, since the recovered catalyst contains a high boiling by-product, the catalyst performance may be lowered depending on the reaction. When carrying out the distillation operation in the coexistence of a halogen-containing catalyst, the corrosion of the device due to the elimination of halogen was also a big problem. In a reaction system containing water or a reaction system in which water is by-produced, there is a problem that decomposition of the catalyst is promoted by heat treatment during distillation. Further, a general Lewis acid such as a metal halide is usually hydrolyzed in the presence of water,
It is known to lose catalytic activity. That is, it has not been possible to use these Lewis acids in the presence of water or in a reaction in which water is by-produced.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors, a catalyst for a Lewis acid catalytic reaction that can be used in the presence of water and can be easily separated and recovered from the reaction solution after the reaction
Surprisingly, it was found that a complex composed of a specific metal halide and a quaternary salt type ion exchange resin exhibits high catalytic activity in a method for producing an unsaturated alcohol (ene reaction) by reacting an olefin with an aqueous formaldehyde solution. . In addition, the complex consisting of various metal halides, Diels Alder reaction, Friedel-Crafts alkylation reaction,
They have found that they can be used for Lewis acid catalyzed reactions such as cationic polymerization reactions. That is, the present invention provides a compound represented by the general formula (I):

[0006]

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(In the formula, M represents at least one metal selected from the group consisting of elements of Group A to Group VB of Periodic Table III, X ₁ represents a halogen atom, and q represents the valence of M. It was completed by finding a Lewis acid catalyst consisting of a metal halide represented by the same integer) and a quaternary salt type anion exchange resin. .

The complex of metal halide and quaternary salt type ion exchange resin found by the present invention, which has never been used for catalytic purposes, acts as a highly active catalyst for Lewis acid catalyzed reaction. To do. Further, the complex catalyst can be used as a catalyst even in the presence of water.
Further, since the complex catalyst is a solid substance, it can be separated from the reaction solution after the reaction by a simple method such as filtration or decantation and can be reused.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The quaternary salt type anion exchange resin used in the present invention may be any resin as long as it is an anion exchange resin containing a quaternary salt type substituent. The quaternary salt-type anion exchange resin is composed of an ion exchange resin polymer substrate, a quaternary salt-type substituent, and a linker connecting both of them. The ion-exchange resin polymer substrate has the general formula (II)

[0010]

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(In the formula, R _a is a hydrogen atom or an optionally substituted lower alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group. R _b and R _c each represent a hydrogen atom, an optionally substituted lower alkyl group, an optionally substituted aryl group, an ester group or an amide group, and m and n represent the degree of polymerization of the ion exchange resin. Represents an integer corresponding to the ratio of 1: 9
It is in the range of 9 to 99: 1. ) Is a copolymer of substituted ethylene and divinylbenzene. The quaternary salt type substituent is usually represented by the general formula (III)

[0012]

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(In the formula, K represents a nitrogen atom or a phosphorus atom, and R ¹ , R ² and R ³ are each a lower alkyl group which may be substituted, a cycloalkyl group which may be substituted, or a substituted alkyl group. Which represents an optionally substituted aryl group or an optionally substituted aralkyl group, and X ₂ represents a halogen atom or a hydroxyl group, and an ammonium salt-type or phosphonium salt-type substituent represented by the general formula (IV)

[0014]

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(In the formula, Py represents a portion obtained by removing a nitrogen atom from the pyridine ring, N represents a nitrogen atom in the pyridine ring, R ⁴ is an optionally substituted lower alkyl group, or an optionally substituted lower alkyl group. Which represents a good cycloalkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, and X ₂ is as defined above.) Is a pyridinium salt type substituent. The linker varies depending on the component of the monomer that is the constituent raw material of the ion exchange resin,

[0016]

[Chemical 6]

Or the general formula (VI-1, VI-2)

[0018]

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(In the formula, r represents an integer other than zero). Therefore, the quaternary salt type anion exchange resin has the general formula (VII)

[0020]

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(Wherein R _a , R _b , R _c , m and n are as defined above, L represents a linker, and Q represents a quaternary salt type substituent).

R ⁴ , R ⁵ and R ⁶ in the general formula (III) and R ⁷ in the general formula (IV) are each a lower alkyl group which may be substituted, a cycloalkyl group which may be substituted, and a substituted alkyl group. Represents an optionally substituted aryl group and an optionally substituted aralkyl group, and these lower alkyl group, cycloalkyl group and aryl group may each be substituted with, for example, a lower alkyl group or a hydroxyl group. The aromatic ring portion of the aralkyl group may be substituted with a lower alkyl group or a halogen atom. Specific examples of the ammonium salt-type or phosphonium salt-type substituent represented by the general formula (III) include, for example, trimethylammonium chloride chloride group, triethylammonium chloride chloride group, tributylammonium chloride chloride group, and dimethylbutylammonium chloride chloride group. Trimethylammonium bromide group, dimethyl (hydroxyethyl) ammonium chloride methyl group, dimethylbenzylammonium bromide group,
Examples thereof include tributylphosphonium methyl chloride group, triphenylphosphonium methyl bromide group, tricyclohexylphosphonium methyl bromide group, but are not limited thereto. The pyridinium salt-type substituent of the general formula (IV) is, for example, a substituent of the nitrogen atom in the pyridine ring, such as N-methyl chloride, N-ethyl chloride, N-butyl chloride, N-benzyl chloride. , N-methyl bromide, and the like, but are not limited thereto.

The metal halide used in the present invention is
It is a halide of at least one metal selected from the group consisting of elements of Group A to Group VB of the periodic table III, preferably Sn, Ga, In, Sc, Fe, Al, B, Zn, T.
It is a halide of at least one metal selected from i, Zr, Sb, Cd, Y and lanthanoid metals.
The type of metal depends on the type of reaction and is appropriately selected.

The complex composed of the metal halide and the quaternary salt type ion exchange resin has a complex structure in which 0.1 to 1.0 unit of the metal halide is coordinated with 1 unit of the quaternary salt type substituent in the resin. I have. The complex is a complex formed by an ionic bond consisting of a quaternary cation of the resin and a metal salt anion, in which a halogen ion or a hydroxyl ion in the quaternary salt type ion exchange resin is coordinated with a metal halide. It is estimated that

The complex can be prepared by mixing a liquid in which a metal halide is dissolved in water or an organic solvent and a quaternary salt type ion exchange resin, then impregnating and adsorbing and supporting, and distilling off the solvent. When preparing a solution of a metal halide, a hydrogen halide solution may be added if necessary,
You may use a mixed solvent of 2 or more types as a solvent. Further, after the impregnation treatment, excess metal halide may be washed with a solvent, if necessary. The treatment temperature is not particularly limited, but when using a solvent containing water as a treatment solvent,
Since the metal halide may be hydrolyzed, 60
It is recommended to process at as low a temperature as possible, below ℃.

The complex catalyst comprising a metal halide and a quaternary salt type ion exchange resin should be used for various Lewis acid catalytic reactions such as ene reaction, Diels-Alder reaction, Friedel-Crafts alkylation reaction and cationic polymerization reaction. Can be done.

A complex catalyst composed of a metal halide and a quaternary salt type anion exchange resin has a general formula (VIII).

[0028]

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(Wherein R ^{5 to} R ⁹ each represent a hydrogen atom or an optionally substituted hydrocarbon group) and an olefin having the structure of general formula (IX)

[0030]

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From the aldehyde compound having the structure of the formula (wherein R ¹⁰ represents a hydrogen atom or an optionally substituted hydrocarbon group), a compound represented by the general formula (X):

[0032]

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(Wherein R ^{5 to} R ¹⁰ are as defined above), a process for producing an unsaturated alcohol having a structure of general formula (VIII) and a general formula (XI)

[0034]

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(In the formula, R ^{11 to} R ¹³ each represent a hydrogen atom or an optionally substituted hydrocarbon group, and R ¹⁴ represents a hydrogen atom, an optionally substituted hydrocarbon group, a cyano group or an ester group. , Which represents a substituent such as an aldehyde group or a carboxyl group) by the addition reaction of an olefinic compound having the structure (XII)

[0036]

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It can be used for the production (ene reaction) of an olefinic compound having the structure of the formula (R ^{5 to} R ⁹ and R ^{11 to} R ¹⁴ are as defined above).

The metal halide used in the ene reaction is preferably a halide of at least one metal selected from the group consisting of tin, gallium, indium and scandium. Examples of metal halides used include stannous (IV) chloride, stannous (IV) bromide, stannous (IV) iodide, gallium (III) chloride, gallium (III) bromide, indium chloride. (III), indium (III) bromide, scandium (III) chloride, scandium (III) bromide and hydrates thereof, and the like.
It is not limited to these. Also, a mixture of these or a metal halide other than these may be used.

Examples of the olefin represented by the structure of the general formula (VIII) include aliphatic olefins such as propylene, isobutene, 1-butene, 2-butene and 1-octene, and isopropenylbenzene, 3-methyl-3-. Examples thereof include aromatic olefins such as buten-1-ol and substituted olefins, but are not limited thereto.

Examples of the aldehyde represented by the structure of the general formula (IX) include formaldehyde, acetaldehyde,
Examples thereof include, but are not limited to, propionaldehyde, isobutyraldehyde, benzaldehyde and the like. Further, citronellal in which an olefin and an aldehyde are present in the same molecule can also be used.

Examples of the olefinic compound represented by the structure of the general formula (XI) include, but are not limited to, acrylonitrile, methyl acrylate, methyl methacrylate, methyl crotonate, acrolein, methacrolein and isobutene. Not something. In addition, olefin and olefinic compound exist in the same molecule 3,7
-Dimethyl-1,7-octadiene and the like can also be used.

A complex catalyst composed of a metal halide and a quaternary salt type ion exchange resin has the general formula (XIII)

[0043]

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(In the formula, R ^{15 to} R ²⁰ are each a hydrogen atom,
It represents an optionally substituted hydrocarbon group, an alkoxy group, a halogen or an acyloxy group. ) Conjugated diene compound represented by structure and general formula (XIV)

[0045]

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(Wherein R ^{21 to} R ²⁴ each represent a hydrogen atom, an optionally substituted hydrocarbon group, an aldehyde group, an ester group or a cyano group) by a reaction with an olefinic compound. It can be used for the production of cyclic olefins (Diels-Alder reaction).

The metal halide used in the Diels-Alder reaction is preferably a halide of at least one metal selected from the group consisting of iron, zinc, aluminum, titanium, zirconium, tin, gallium, indium and scandium. Examples of metal halides used are ferric chloride (III), zinc chloride, aluminum chloride, titanium chloride, zirconium chloride, stannic chloride (IV), stannic bromide (IV), stannic iodide. Tin (I
V), gallium chloride, gallium bromide, indium chloride,
Examples thereof include, but are not limited to, indium bromide, scandium chloride, scandium bromide and hydrates thereof. Further, a mixture thereof can be used, and a metal halide other than these may be used.

Examples of the conjugated diene represented by the structure of the general formula (XIII) include butadiene, isoprene, 1,3-pentadiene, cyclopentadiene and 1,3-dichlorohexadiene, but are not limited thereto. is not. Examples of the olefinic compound represented by the structure of the general formula (XIV) include acrylonitrile, methyl acrylate, methyl methacrylate, methyl crotonate, acrolein, methacrolein, dimethyl maleate, and maleic anhydride. It is not limited to.

A complex catalyst composed of a metal halide and a quaternary salt type ion exchange resin is an aromatic compound and a compound of the general formula (XV)

[0050]

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(In the formula, R ^{25 to} R ²⁸ each represent a hydrogen atom or an optionally substituted hydrocarbon group.) Or an olefinic compound represented by the formula (XVI)

[0052]

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(Wherein R ^{25 to} R ²⁸ are as defined above and Y represents a halogen or a hydroxyl group) to produce a substituted aromatic compound by reaction with a substituted hydrocarbon (Friedel). (Crafts alkylation reaction).

The metal halide used in the Friedel-Crafts alkylation reaction is iron, zinc, aluminum,
At least one selected from the group consisting of titanium, zirconium, tin, gallium, indium and scandium.
Preferred are metal halides. Examples of metal halides used are ferric chloride (III), zinc chloride, aluminum chloride, titanium chloride, zirconium chloride, stannic chloride (IV), stannic bromide (IV), stannic iodide. Examples include tin (IV), gallium chloride, gallium bromide, indium chloride, indium bromide, scandium chloride, scandium bromide and hydrates thereof.
It is not limited to these. Further, a mixture thereof can be used, and a metal halide other than these may be used.

Examples of aromatic compounds used in the present invention include benzene, toluene, ethylbenzene, xylene, mesitylene, anisole, phenetole, paramethylanisole, methyl salicylate, phenol, nalthalene, anthracene, 4-methylpyridine, 2 -Methoxyfuran, 2-methoxypyrrole, 2-methoxythiol and the like, but not limited thereto. Examples of the olefinic compound represented by the general formula (XV) include olefins such as ethylene, propylene, isobutylene, and 1-butene, and examples of the substituted hydrocarbon represented by the general formula (XVI) include methyl iodide and odor. Examples thereof include halogenated hydrocarbons such as ethyl chloride and -t-butyl chloride, alcohols such as t-butanol, t-amyl alcohol, and 2-phenyl-2-propanol, but are not limited thereto.

The complex catalyst composed of a metal halide and a quaternary salt type ion exchange resin can also be used in cationic polymerization reactions such as polymerization of unsaturated compounds and ring-opening polymerization of heterocyclic compounds. The metal halide used in the cationic polymerization reaction is preferably a halide of at least one metal selected from the group consisting of iron, aluminum, titanium, boron, zirconium, tin, gallium and antimony. Examples of metal halides used include ferric chloride (II
I), boron fluoride, aluminum chloride, aluminum bromide, titanium chloride, zirconium chloride, stannic (IV) chloride, stannic (IV) bromide, gallium chloride, antimony chloride, gallium bromide and their waters. Examples include, but are not limited to, Japanese products. Further, a mixture thereof can be used, and a metal halide other than these may be used.

Examples of unsaturated compounds used in the present invention include, but are not limited to, isobutene, styrene, α-methylstyrene, vinyl ether, butadiene, isoprene and the like. Examples of the heterocyclic compound include, but are not limited to, ethylene oxide, propylene oxide, oxetane, tetrahydrofuran, ethyleneimine, caprolactone and the like. Further, a cocatalyst such as water, alcohol, acid or acid anhydride may be added to these reactions, if necessary.

The reaction can be carried out by any method such as batch suspension type or fixed bed continuous type.

In the case of a batch suspension type reaction, separation and recovery of the complex after the reaction can be easily separated from the liquid phase component by filtration or decantation. Further, in the case of the fixed bed continuous system, since only the liquid phase component flows out from the outlet of the reaction tank, it is possible to continuously provide the reaction as it is without a recovery operation.

[0060]

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

Reference Example 1 (Trimethylammonium) Methyl Chloride Substituent (4.2
100 g of styrenedivinylbenzene copolymer resin having meq / g) was suspended in 1 liter of acetonitrile, and 70 g of tin tetrachloride (SnCl ₄ ) was added dropwise over 30 minutes under ice cooling, followed by stirring at room temperature for 2 hours. . After distilling off acetonitrile under reduced pressure, 500 ml of acetonitrile
The tin tetrachloride-impregnated resin was washed with 3 times and then dried under reduced pressure to obtain a resin complex containing 37.1% by weight of SnCl ₄ . When the Sn structure of the obtained resin was examined by solid-state NMR, a signal was observed at -730 ppm. This is the signal of SnCl ₄ itself (-680 pp
m) and SnCl ₄ supported on a polyvinylstyrene divinylbenzene copolymer copolymer (−6)
80 ppm: SnCl ₄ just adsorbed on the polymer
It is confirmed that the resin forms a resin complex because it is clearly different from the same signal as that of the resin alone. Moreover, SnCl ₄ is 0.5 for 1 unit of resin amino group.
It was calculated to be a 4-coordinated complex.

Example 1 Isobutene 56.1 was added to a 300 ml glass autoclave.
g (1.0 mol), 50% formaldehyde aqueous solution 6.
0 g (0.10 mol), acetonitrile 32.8 g
(0.80 mol) and the resin complex 7.0 obtained in Reference Example 1.
g (SnCl ₄ : 0.01 mol content) was added, and the mixture was stirred at 60 ° C. for 2 hours. The reaction pressure at this time is 8.0 kg / cm.
^{Was 2} . After cooling the reactor, isobutene was removed by pressure release and the resin complex was removed by decantation to obtain 43.2 g of a reaction solution. As a result of analyzing the obtained reaction liquid, formaldehyde remained 1.65 g (0.055 mol), 3-methyl-3-buten-1-ol 2.83 g (0.033 mol), 4,4 -Dimethyl-
0.03 g (0.27 mmol) of 1,3-dioxane
Had been generated. The conversion rate based on formaldehyde is 45
%, The selectivity to unsaturated alcohol is 73%, alkyl-
The selectivity to m-dioxane was 1.2%.

Example 2 Isobutene 56.1 was added to a 300 ml glass autoclave.
g (1.0 mol), 50% formaldehyde aqueous solution 6.
0 g (0.10 mol), acetonitrile 32.8 g
(0.80 mol) and 7.5 g of the resin complex recovered in Example 1 were added, and the mixture was stirred at 60 ° C. for 2 hours. Post-treatment was carried out in the same manner as in Example 1, and the obtained reaction solution was analyzed. As a result, the conversion rate based on formaldehyde was 43%, the selectivity to unsaturated alcohol was 72%, and the alkyl-m-dioxane was selected. The selectivity to was 1.5%, and the activity was retained even after repetition.

Example 3 6.3 g of the resin complex prepared in Reference Example 1 was filled in a stainless steel reaction tube (internal volume: 10 ml) having an inner diameter of 4 mm and a length of 80 cm and kept at 60 ° C. Isobutene 56.1g
(1.0 mol), 50% formaldehyde aqueous solution 6.0
g (0.10 mol), t-butanol 37.0 g (0.
A mixed solution of 50 mol) and 16 mg (0.16 mmol) of hydrochloric acid was sent to the reaction tube at a rate of 10 ml per hour. After 2 hours, the reaction liquid flowing out from the reaction tube was recovered, isobutene was released, and the components were analyzed. As a result, all the formaldehyde disappeared and 3-methyl-3-butene-
71% of 1-ol and 1.0% of 4,4-dimethyl-1,3-dioxane were produced. Subsequently, the reaction was continuously carried out, and the same analysis was carried out after 50 hours. As a result, all the formaldehyde disappeared, and 3-methyl-3-butene-1
-70% of ol and 1.2% of 4,4-dimethyl-1,3-dioxane were produced. No decrease in activity was observed by 50 hours.

Reference Example 2 100 g of a vinylpyridinedivinylbenzene copolymer resin having an N-propyl chloride substituent (3.8 meq / g) was suspended in 1 liter of acetonitrile, and tin tetrachloride (SnCl ₄ ) was cooled with ice. After 70 g was added dropwise over 30 minutes, the mixture was stirred at room temperature for 2 hours. After distilling off the acetonitrile under reduced pressure, the tin tetrachloride-impregnated resin was washed 3 times with 500 ml of acetonitrile and then dried under reduced pressure to give 3
A resin complex containing 2.1 wt% SnCl ₄ was obtained.
Solid-state NMR of Sn gave a signal at -728 ppm and confirmed that a complex was formed. In addition, it was determined by calculation that this was a complex in which 0.48 equivalent of SnCl ₄ was coordinated to 1 unit of the resin amino group.

Example 4 6.2 g of the resin complex prepared in Reference Example 2 was filled in a stainless steel reaction tube (internal volume: 10 ml) having an inner diameter of 4 mm and a length of 80 cm and kept at 60 ° C. Isobutene 56.1g
(1.0 mol), 50% formaldehyde aqueous solution 6.0
g (0.10 mol), t-butanol 37.0 g (0.
A mixed solution of 50 mol) and 16 mg (0.16 mmol) of hydrochloric acid was sent to the reaction tube at a rate of 10 ml per hour. After 2 hours, the reaction liquid flowing out from the reaction tube was recovered, the pressure of isobutene was released, and the components were analyzed. As a result, all the formaldehyde disappeared and 3-methyl-3-butene-
77% of 1-ol and 1.3% of 4,4-dimethyl-1,3-dioxane were produced. Subsequently, the reaction was continuously carried out, and the same analysis was carried out after 50 hours. As a result, all the formaldehyde disappeared, and 3-methyl-3-butene-1
-76% of ol and 1.3% of 4,4-dimethyl-1,3-dioxane were produced. No decrease in activity was observed by 50 hours.

Reference Example 3 (Trimethylammonium) Methyl Chloride Substituent (4.2
100 g of styrenedivinylbenzene copolymer resin having meq / g) was suspended in 800 ml of acetonitrile, and a solution of 45 g of scandium chloride (ScCl ₃ ) in 200 ml of acetonitrile was added dropwise over 30 minutes under ice-cooling, followed by room temperature. It was stirred for 2 hours. After the acetonitrile was distilled off under reduced pressure, the scandium chloride-impregnated resin was washed 3 times with 500 ml of acetonitrile and then dried under reduced pressure to obtain a resin complex containing 24.2% by weight of ScCl ₃ . ScC for 1 unit of resin amino group
It was determined by calculation that l ₃ was a 0.50 equivalent coordination complex.

Example 5 Isobutene 56.1 was added to a 300 ml glass autoclave.
g (1.0 mol), 50% formaldehyde aqueous solution 6.
0 g (0.10 mol), acetonitrile 32.8 g
(0.80 mol) and the resin complex 6.2 obtained in Reference Example 3.
Add 6 g (ScCl ₃ : 0.01 mol content), 60 ℃
For 2 hours. The reaction pressure at this time is 8.0 kg / c.
m ² . Post-treatment is carried out in the same manner as in Example 1,
As a result of analyzing the obtained reaction liquid, 1.71 g (0.057 mol) of formaldehyde remained, 2.35 g (0.027 mol) of 3-methyl-3-buten-1-ol, 4,4 -Dimethyl-1,3-dioxane 0.06
0 g (0.52 mmol) had formed. The conversion based on formaldehyde was 43%, the selectivity to unsaturated alcohol was 63.5%, and the selectivity to alkyl-m-dioxane was 2.4%.

Example 6 In a 300 ml glass autoclave, 126 g (1.0 mol) of 2-methyl-1-octene, 6.0 g (0.10 mol) of 50% aqueous formaldehyde solution, and t-butanol g were added.
37.0 g (0.50 mol) and 7.0 g of the resin complex prepared in Reference Example 1 (containing SnCl ₄ : 0.01 mol) were added, and the mixture was stirred at 60 ° C. for 2 hours. The reaction pressure at this time was 8.0 kg / cm ² . After cooling the reactor, the resin complex was removed from the reaction solution by decantation, and the obtained reaction solution was analyzed. As a result, formaldehyde was found to be 1.59.
g (0.053 mol) remaining, 3-methyl-3-nonen-1-ol and 2- (2-hydroxyethyl)
A mixture of 2-octene was produced in an amount of 4.60 g (0.029 mol) and 0.074 g (0.40 mmol) of 4-methyl-4-hexyl-1,3-dioxane. The conversion based on formaldehyde was 47%, the selectivity to unsaturated alcohol was 62.7%, and the selectivity to alkyl-m-dioxane was 1.7%.

Example 7 In a 300 ml glass autoclave, 86.1 g (1.0 mol) of 3-methyl-3-buten-1-ol, 6.0 g (0.10 mol) of 50% aqueous formaldehyde solution, t-
Butanol g37.0g (0.50 mol) and resin complexes 7.0g, prepared in Reference Example 1 (SnCl _4: 0.01
(Containing mol) and stirred at 60 ° C. for 2 hours. The reaction pressure at this time was 8.0 kg / cm ² . After cooling the reactor, the resin complex was removed from the reaction solution by decantation, and the obtained reaction solution was analyzed. As a result, formaldehyde remained 1.46 g (0.049 mol), and 3-methylene-1, 5-pentanediol and 3-methyl-2
3.59 g of a mixture of pentene-1,5-diol
(0.031 mol), 4-methyl-4- (β-hydroxyethyl) -1,3-dioxane 0.075 g (0.5
1 mmol) had formed. The conversion rate based on formaldehyde is 51.2%, and the selectivity to unsaturated alcohol is 6
0.3%, selectivity to alkyl-m-dioxane is 2.
It was 0%.

Example 8 Acetonitrile 3 was placed in a 200 ml glass autoclave.
2.8 g (0.8 mol), resin complexes 14.0g prepared in Reference Example 1 (SnCl _4: 20 mmol) and citronellal put Le 15.4g (0.10 mol) was 2hr reaction at 60 ° C.. After the reaction, the resin complex was separated by filtration, and the obtained reaction solution was analyzed. As a result, 2.26 g (14.7 mmol) of citronellal remained and 11.55 g (75.0 mmol) of isopulegol was produced. It was The conversion based on citronellal was 85.3%, and the selectivity for isopulegol was 87.9%.

Example 9 In a 200 ml glass autoclave, acetonitrile 3 was added.
2.8 g (0.8 mol), Reference Example 1 resin complex 28.0g prepared in (SnCl _4: 40 mmol), methyl vinyl ketone 14.0 g (0.20 mol) and isoprene 27.2 g (0.40 Mol) was added and the reaction was carried out at 60 ° C. for 2 hours. After the reaction, the resin complex was separated by filtration, and the obtained reaction solution was analyzed.
88 g (12.6 mmol) remained, 11.0 g of 1-acetoxy-4-methyl-3-cyclohexene (1
(52 mmol) was produced. The conversion of methyl vinyl ketone is 93.7%, 1-acetoxy-4-methyl-3-
The selectivity for cyclohexene was 81.2%.

Example 10 Acetonitrile 3 was placed in a 200 ml glass autoclave.
2.8 g (0.8 mol), resin complexes 14.0g prepared in Reference Example 1 (SnCl _4: 20 mmol), methacrolein 14.0g (0.20 mol) and butadiene 2
1.6 g (0.40 mol) was added and the reaction was carried out at 80 ° C. for 1 hr. After the reaction, the resin complex was separated by filtration, and the obtained reaction solution was analyzed. As a result, methacrolein disappeared and 1-methyl-3-cyclohexenyl aldehyde was found
2.3 g (179.6 mmol) had been produced. The conversion of methacrolein was 100% and the selectivity of 1-methyl-3-cyclohexenyl aldehyde was 89.8%.

Example 11 In a 200 ml glass autoclave, 28.0 g (SnCl ₄ : 40 mmol) of the resin complex prepared in Reference Example 1, 15.4 g (0.40 mol) of anisole, 18.5 g (0 of t-butyl chloride) were added. 0.2 mol) and put at 100 ° C for 3
The reaction was carried out for hr. After the reaction, the resin complex was separated by filtration, and the obtained reaction solution was analyzed. As a result, 1.26 g (14 mmol) of t-butyl chloride remained and 15.3 g (93.0 g of 9-3.0 g) of 4-t-butylanisole. Mmol), 2-
2.8 g (16.8 mmol) of t-butylanisole and 5.8 g of 2,4-di-t-butylanisole.
(26.2 mmol) had been produced. The conversion of t-butyl chloride was 93.2%, and the selectivity of alkylated anisole was 87.0%.

Reference Example 4 (Trimethylammonium) Methyl Chloride Substituent (4.2
100 g of styrene-divinylbenzene copolymer resin having meq / g) was suspended in 0.5 L of acetonitrile,
Under ice cooling, 65 g of iron (III) chloride was added to 0.5 g of acetonitrile.
After dropping the solution dissolved in liter over 30 minutes,
Stirred at room temperature for 2 hours. After distilling off acetonitrile under reduced pressure, the iron chloride-impregnated resin was washed 3 times with 500 ml of acetonitrile, and subsequently dried under reduced pressure to obtain a resin complex containing 40.9% by weight of FeCl ₃ .

Example 12 In a 200 ml glass autoclave, 15.9 g (FeCl ₃ : 40 mmol) of the resin complex prepared in Reference Example 4, 15.4 g (0.40 mol) of anisole and 1 of isobutene were used.
1.2 g (0.2 mol) was added and the reaction was carried out at 120 ° C. for 3 hours. After the reaction, the pressure of isobutene was released, and the resin complex was separated by filtration.
-Butylanisole was 3.94 g (24.0 mmol) and 2-t-butylanisole was 0.46 g (2.8).
(Mmol) had been produced. The yield of alkylated anisole was 13.4%.

Example 13 To a 200 ml glass autoclave was added 5.0 g (SnCl ₄ : 7.1 mmol) of the resin complex prepared in Reference Example 1 and 104 g (1.0 mol) of styrene, and the reaction was carried out at 100 ° C. for 3 hours. went. The obtained polymer was dissolved in THF, the resin complex was collected by filtration, and then GPC measurement was performed. As a result, it was found that polystyrene having a number average molecular weight of 7800 was obtained.

Example 14 To a 200 ml glass autoclave, 5.0 g (SnCl ₄ : 7.1 mmol) of the resin complex prepared in Reference Example 1 and 114 g (1.0 mol) of caprolactone were added, and 60
The reaction was performed at 4 ° C. for 4 hours. The obtained polymer was dissolved in THF, the resin complex was collected by filtration, and GPC measurement was performed. As a result, it was found that polycaprolactone having a number average molecular weight of 2800 was obtained.

[0079]

INDUSTRIAL APPLICABILITY The complex consisting of a metal halide and a quaternary salt type ion exchange resin, which has not been used for catalytic purposes until now, has been found by the present invention. Acts as. The complex catalyst can be used as a catalyst even in the presence of water. further,
Since the complex catalyst is a solid substance, it can be separated from the reaction solution after the reaction by a simple method such as filtration or decantation and can be reused.

Claims (10)

[Claims] 1. A compound of the general formula (I) (In the formula, M represents at least one metal selected from the group consisting of elements from Group A to Group VB of the periodic table, X ₁ represents a halogen atom, and q is an integer equal to the valence number of M. A Lewis acid catalyst comprising a metal halide represented by: and a quaternary salt type anion exchange resin. 2. The metal halide is Sn, Ga, In,
Sc, Fe, Al, B, Zn, Ti, Zr, Sb, C
The catalyst according to claim 1, which is a halide of at least one metal selected from the group consisting of d, Y and lanthanoid metals. 3. The catalyst according to claim 1, which is used for an ene reaction. 4. The catalyst for ene reaction according to claim 1, wherein the metal halide is a halide of at least one metal selected from the group consisting of Sn, Ga, In and Sc. 5. The catalyst according to claim 1, which is used for a Diels-Alder reaction. 6. The metal halide is Fe, Zn, Al,
The catalyst for Diels-Alder reaction according to claim 1, which is a halide of at least one metal selected from the group consisting of Ti, Zr, Sn, Ga, In and Sc. 7. The catalyst according to claim 1, which is used for Friedel-Crafts alkylation reaction. 8. The metal halide is Fe, Zn, Al,
The catalyst for Friedel-Crafts alkylation reaction according to claim 1, which is a halide of at least one metal selected from the group consisting of Ti, Zr, Sn, Ga, In and Sc. 9. The catalyst according to claim 1, which is used for a cationic polymerization reaction. 10. The metal halide is Fe, Al, T.
The catalyst for cationic polymerization reaction according to claim 1, which is a halide of at least one metal selected from the group consisting of i, B, Zr, Sn, Ga and Sb.