JP3232025B2 - Aluminum compound and acid catalyst containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aluminum compound useful as an acid catalyst and a method for producing esters, acetals, ketals and ethers using the compound as an acid catalyst.

[0002]

2. Description of the Related Art As aluminum-based acid catalysts, for example, aluminum chloride and alumina have been known. Among them, aluminum chloride is a metal chloride, and therefore, when alcohol is used as a reaction substrate, a problem of alcoholysis occurs. On the other hand, in the case of a solid acid catalyst such as alumina, there is a problem that the activity itself is low, a high temperature is required to obtain sufficient reactivity, and the type of reaction itself is limited.

[0003] As the acid-catalyzed reaction of alcohol, reactions with carbonyl compounds such as esterification, transesterification, acetalization, and ketalization, etherification reactions, and ring-opening reactions of epoxy compounds are known. Among them, in the reaction between alcohol and carbonyl compound or in the etherification reaction, a Bronsted acid such as sulfuric acid or p-toluenesulfonic acid is mainly used as an acid catalyst. On the other hand, in a ring opening reaction between an alcohol and an epoxy compound, a Lewis acid catalyst is mainly used because a Bronsted acid catalyst has low reactivity. However, among these Lewis acid catalysts, metal chlorides such as aluminum chloride, tin chloride and iron chloride cause catalyst deactivation and generation of free chlorine due to alcoholysis as described above. In particular, when a highly active Lewis acid such as boron trifluoride is used, it is difficult to control the reaction, and a side reaction such as polymerization of an epoxy compound tends to occur.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a Lewis acid catalyst which does not cause alcoholysis in a reaction using an alcohol as a raw material, has sufficient activity, and has few side reactions.

[0005]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the aluminum compound represented by the following general formula (1) does not cause alcoholysis of alcohol and uses alcohol as a substrate. Various reactions,
In particular, they have found that there is little side reaction in the reaction between the alcohol and the epoxy compound and the catalytic activity is high, and have completed the present invention.

That is, the present invention provides the following general formula (1)

[0007]

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(Wherein, R ¹ represents an optionally substituted hydrocarbon group, and R ² represents an oxygen atom, a chlorine atom, an optionally substituted hydrocarbon group or a substituent. Represents a hydrocarbon oxy group which may be possessed, wherein m and n are m = 1 to 1
3, where n = 0 to 2 and m + n = 3)
An acid catalyst comprising an aluminum compound represented by the formula:

[0009]

Further, the present invention provides an ester characterized in that an alcohol is reacted with a carbonyl compound, an alcohol, an olefin or an epoxy compound in the presence of an acid catalyst containing an aluminum compound represented by the general formula (1). , Acetals, ketals or ethers.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), the optionally substituted hydrocarbon group represented by R ¹ and R ² may be a hydroxyl group, an alkoxyl group or a halogen atom. An alkyl group (provided that R ¹ is not a halogenated alkyl group); a hydroxyl group, an alkoxyl group or an alkenyl group which may be substituted by a halogen atom; an alkyl group, a hydroxyl group, an alkoxyl group or a halogen atom which may be substituted. And an optionally substituted aryl group. Here, the alkyl group has 1 to 3 carbon atoms.
6 linear or branched alkyl groups, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecyl. Group, dodecyl group,
Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, 2-ethylhexyl, 3,5
-Dimethylhexyl group and the like. Examples of the alkenyl group include a linear or branched alkenyl group having 2 to 36 carbon atoms, and specific examples thereof include a vinyl group, a propenyl group, an oleyl group, and a linole group. Examples of the aryl group include a phenyl group and a naphthyl group. The alkoxyl group may have 1 to 3 carbon atoms.
And straight-chain or branched-chain alkoxyl groups such as methoxy, ethoxy, propoxy, isopropoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and nonyloxy groups. , Decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group,
Examples include a heptadecyloxy group, an octadecyloxy group, a nonadecyloxy group, an eicosyloxy group, a 2-ethylhexyloxy group, and a 3,5-dimethylhexyloxy group. Examples of the halogen atom include chlorine, bromine, fluorine and iodine.

The hydrocarbon oxy group which may have a substituent represented by R ² includes a hydroxyl group, an alkoxyl group or an alkoxyl group which may be substituted by a halogen atom; a hydroxyl group, an alkoxyl group or a halogen atom Is an alkenyloxy group which may be substituted; an alkyl group, a hydroxyl group, an alkoxyl group or an aryloxy group which may be substituted by a halogen atom. Here, the alkoxyl group, the alkyl group, and the halogen atom include the same as described above. Examples of the alkenyloxy group include a linear or branched alkenyloxy group having 2 to 36 carbon atoms, and specific examples thereof include a propenyloxy group, an oleyloxy group, and a linoloxy group. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group.

Of the above R ¹ , an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, The optionally substituted naphthyl group is preferable, and among these, the alkyl group optionally having a substituent is more preferably a methyl group, and the phenyl or naphthyl group optionally having a substituent is a phenyl group. , Chlorophenyl group, methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group is more preferable. And a hydroxyphenyl group are particularly preferred.

Among R ² , an alkoxyl group, an alkenyloxy group and an aryloxy group which may have a substituent are preferable, and an aryloxy group which may have a substituent is particularly preferable. The alkoxyl group is particularly preferably an isopropoxy group, and the optionally substituted aryloxy group is particularly preferably a phenoxy group, a chlorophenoxy group, a dichlorophenoxy group, a trichlorophenoxy group, or a naphthyloxy group.

Specific examples of the aluminum compound (1) include the following compounds.

[0016]

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The aluminum compound (1) is obtained, for example, by reacting a sulfonic acid with a trialkylaluminum or trialkoxyaluminum, and partially or entirely substituting the alkyl or alkoxyl group of the trialkylaluminum or trialkoxyaluminum with the sulfonic acid. After that, it is produced by further substituting the remaining alkyl or alkoxy group with an appropriate alcohol or phenol.

The aluminum compound (1) is useful as an acid catalyst, particularly as an acid catalyst in various reactions using alcohol as a raw material.

In the reaction of an alcohol with a carbonyl compound, an alcohol, an olefin or an epoxy compound,
When the aluminum compound (1) is used as the acid catalyst, an ester, an acetal, a ketal, an olefin or an ether can be obtained in a high yield without deactivation of the catalyst or side reaction due to alcoholysis. Further, the aluminum compound (1) is particularly useful in the reaction of reacting an alcohol with an epoxy compound to obtain an ether (epoxy ring opening reaction).
That is, in this reaction, catalyst deactivation and generation of free chlorine due to alcoholysis such as aluminum chloride do not occur, and there are few side reactions such as polymerization of epoxy compounds.

The reaction between the alcohol and the carbonyl compound, alcohol, olefin or epoxy compound is carried out in the same manner as in the ordinary esterification, acetalization, ketalization or etherification reaction, except that the aluminum compound (1) is used as the acid catalyst. Just do it. For example, the reaction between the alcohol and the epoxy compound is carried out in an amount of 0.5 to 1.5 mole times, preferably 1.0 to 1.
The aluminum compound (1) is used in an amount of 0.001 to 0.1 times, preferably 0.01 to 0.05 times the molar amount of the alcohol, and the reaction temperature is 10 to 12 times.
The heat treatment may be performed at 0 ° C., preferably 70 to 110 ° C., for 1 to 5 hours. Here, as the epoxy compound, epihalohydrin can be used in addition to a normal epoxy compound.

[0021]

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

Example 1 50 ml of toluene, 3.60 g (1.76 mmol) of aluminum triisopropoxide and 9.21 g (5.28 mmol) of p-phenolsulfonic acid were placed in a 100 ml four-necked flask, and a Dean-Stark trap was used. The mixture was refluxed for 3 hours while stirring under nitrogen. The solvent was distilled off and 9.6 was collected.
g of the present compound (a) was obtained as a pale yellow-white solid.
(Mp = 300 ° C. (dec.)). As shown in FIG.
Identified by solid state FT-IR.

Ν _OH = 3281 cm ⁻¹ (phenolic hydroxyl group) [ _CH stretching derived from isopropyl group of aluminum triisopropoxide ν _CH = 2800 to 3000 cm ⁻¹ disappearance]

Octyl alcohol 11.7 g (0.09
mol), 0.98 g (1.80 mmol) of the present compound (a)
l) was placed in a 100 ml four-necked flask, and heated to 95 ° C. while stirring under nitrogen. Next, 10.0 g (0.108 mol) of epichlorohydrin was added dropwise over 10 minutes.
The mixture was stirred for 3 hours. The yield of halohydrin ether determined by GLC was 87%. The residual amount of unreacted octyl alcohol was determined by GLC and found to be 5% or less.

Comparative Example 1 11.7 g (0.09 mol) of octyl alcohol and 0.36 g (1.77 g) of aluminum triisopropoxide
mmol) into a 100 ml four-necked flask and introducing nitrogen,
The temperature was raised to 95 ° C. while stirring. Next, 10.0 g (0.108 mol) of epichlorohydrin was added dropwise over 10 minutes, and the mixture was stirred for 3 hours. The yield of halohydrin ether was 6%, and the remaining amount of unreacted octyl alcohol and epichlorohydrin was 90% or more.

Comparative Example 2 11.7 g (0.09 mol) of octyl alcohol and p
0.94 g of phenolsulfonic acid was placed in a 100 ml four-necked flask, and the temperature was raised to 95 ° C. while stirring under nitrogen. Next, epichlorohydrin 10.0 g (0.10
8 mol) was added dropwise over 10 minutes, and the mixture was stirred for 3 hours. The yield of halohydrin ether was 22%, and the remaining amount of unreacted octyl alcohol was 65% or more.

Comparative Example 3 11.7 g (0.09 mol) of octyl alcohol and B
0.25 g (1.77 mmol) of F ₃ OEt ₂ was placed in a 100 ml four-necked flask, and 10.0 g (0.108 mol) of epichlorohydrin was added dropwise with stirring under nitrogen for 30 minutes. Stirred. All epichlorohydrin was consumed, but the yield of halohydrin ether was 61%.

Example 2 21.8 g (0.09 mol) of hexadecyl alcohol,
1.00 g (1.83 mmol) of the present compound (a) was added to 10
The mixture was placed in a 0 ml four-necked flask and heated to 80 ° C. while stirring under nitrogen. Next, butyl glycidyl ether 1
1.7 g (0.09 mol) was added dropwise over 10 minutes, and the mixture was stirred for 4 hours. After the completion of the reaction, the mixture was washed with 40 ml of a 4N aqueous solution of sodium hydroxide, further washed twice with 40 ml of water, and then purified by distillation under reduced pressure.
3-Hexadecyl glyceryl ether was obtained as a colorless transparent oil (total yield: 80%), and identified by ¹ H-NMR (200 MHz). Purity is 95.0% by GLC and 5% of 1-
It contained butyl-2-hexadecyl glyceryl ether.

Example 3 100 ml of 11.7 g (0.09 mol) of octyl alcohol and 1.00 g (1.83 mmol) of the compound (a) of the present invention were obtained.
Put in a four-necked flask and stir under nitrogen while stirring.
The temperature was raised to 0 ° C. Next, 1,2-epoxydecane16.
6 g (0.09 mol) was added, and the mixture was stirred as it was for 3 hours. After the completion of the reaction, the reaction solution was washed with 40 ml of a 4N aqueous sodium hydroxide solution, further washed twice with 40 ml of water, and then purified by distillation under reduced pressure to obtain 21.3 g of 11-oxa-9-hydroxynonadecane as a colorless transparent oil. (Total yield 83
%) And ¹ H-NMR (200 MHz). Purity was 95.0% by GLC and contained 5% of 10-oxa-9-hydroxymethylnonadecane.

[0030]

The aluminum compound (1) does not cause alcoholysis and has a high catalytic activity, so that it is particularly useful as an acid catalyst in various reactions using alcohol as a raw material.

[Brief description of the drawings]

FIG. 1 is a view showing an IR spectrum of the compound (a) of the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 41/50 C07C 41/50 41/54 41/54 67/03 67/03 67/08 67/08 67/14 67/14 // C07B 61/00 300 C07B 61/00 300 (56) References JP-A-57-90643 (JP, A) JP-B-47-22649 (JP, B1) (58) Fields investigated (Int. Cl. ⁽⁷ , DB name) C07F 5/06 B01J 31/02 103 C07B 41/04 C07B 41/12 C07C 41/03 C07C 41/50 C07C 41/54 C07C 67/03 C07C 67/08 C07C 67/14

Claims (4)

(57) [Claims] 1. The following general formula (1): (Wherein R ¹ is a hydroxyphenyl group, having 1 to 36 carbon atoms)
An alkyl group or an alkyl-substituted phenyl group having 1 to 36 carbon atoms; R ² represents an isopropoxy group or a phenoxy group, m and n are m = 1 to 3, n = 0 to 2,
m + n = 3).) An acid catalyst comprising an aluminum compound represented by the formula: 2. A method for producing an ester, comprising reacting an alcohol with a carbonyl compound in the presence of the acid catalyst according to claim 1. 3. A method for producing an ether, comprising reacting an alcohol with an epoxy compound in the presence of the acid catalyst according to claim 1. 4. The method for producing an ether according to claim 3, wherein the epoxy compound is epihalohydrin.