JPH0372435A - Production of alkylated naphthalenes - Google Patents

Abstract

PURPOSE:To readily obtain the title compound useful as a raw material for polymer in high selectivity and in high yield by reacting a naphthalene with an alkylating agent such as alcohol by the use of an ion exchange type lamellar compound having excellent heat resistance as a catalyst. CONSTITUTION:A naphthalene shown by formula I (R is alkyl, cycloalkyl or phenyl; (n) is 0 or 1) is reacted with an alcohol or olefin as alkylating agent preferably in a solvent in the presence of an ion exchange type lamellar compound catalyst to give the objective compound shown by formula II (R' is alkyl or cycloalkyl; (m) is 2 when (n) is 0; (m) is 1 when (m) is 2). The catalytic compound usually has a configuration of having a great number of accumulated lamellar clay and containing ion components between the layers of the lamellar clay and tetrasilicic mica, taeniolite, montmorilonite, etc., wherein ions are exchanged with aluminum ion, gallium ion, etc., are used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing alkylated naphthalenes by alkylating naphthalenes.

Alkylated naphthalenes obtained by alkylating naphthalenes, especially dialkylnaphthalenes obtained by alkylating alkylnaphthalenes, are important as precursors for polymer raw materials and intermediates in the production of pharmaceuticals. .

Conventionally, such dialkylnaphthalenes have been produced by the Friedel-Krach reaction in which naphthalene or alkylnaphthalenes are reacted with an alkyl halide or an olefin as an alkylating agent using aluminum chloride as a catalyst.

However, according to such a method, the selectivity to dialkylnaphthalenes is low, usually 40% or less.

In order to solve this problem, for example, Japanese Patent Application Laid-Open No. 1-102034 proposes a method of using water together with aluminum halide, but the selectivity of dialkylnaphthalenes is still low. In addition to being low,
There are problems with post-reaction neutralization, oil/water separation, and treatment of generated wastewater.

The present invention is aimed at solving the above-mentioned problems in the conventional production of alkylated naphthalenes by alkylation of naphthalenes, particularly in the production of dialkylnaphthalenes by alkylation of alkylnaphthalenes. The alkylation reaction is carried out on naphthalenes, preferably alkylnaphthalenes, in the presence of a solid acid catalyst,
It is an object of the present invention to provide a method for producing target alkylated naphthalenes, particularly dialkylnaphthalenes, with high selectivity.

According to the present invention, in the presence of an ion-exchange layered compound, a compound of the general formula (wherein R is an alkyl group, cycloalkyl group X is a phenyl group, and n is O or 1) A general formula (wherein R and n are the same as above, and R' represents an alkyl group or a cycloalkyl group) is characterized by reacting naphthalenes represented by and when n is 0, m represents 2; and when n is 1, m represents 1).

The starting materials used in the method of the present invention are naphthalenes represented by the general formula (wherein R represents an alkyl group, a cycloalkyl group, or a phenyl group, and n represents O or 1).

In the above general formula, R is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a phenyl group; In some cases, these may have substituents such as alkyl groups or halogen atoms. n is O
Or 1.

Therefore, as naphthalenes that can be used in the present invention,
Examples include alkylnaphthalenes such as naphthalene, methylnaphthalene, ethylnaphthalene, propylnaphthalene, butylnaphthalene and pentylnaphthalene, cycloalkylnaphthalenes such as cyclohexylnaphthalene and methylcyclohexylnaphthalene, and phenylnaphthalene. In particular, alkylnaphthalenes are preferably used in the present invention.

The alkylating agent used in the present invention is an alcohol or an olefin, and examples of the alcohol include linear or branched aliphatic alcohols having 1 to 6 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, and hexanol. Examples include alcohol and alicyclic alcohols such as cyclopentanol and cyclohexanol.

The alicyclic alcohol may have a substituent such as an alkyl group or a halogen atom on the ring. Therefore, for example, methylcyclohexanol and the like can also be used as alkylating agents. Moreover, as an olefin, carbon number 2-5
Preferably, ethylene, propylene, butene, pentene, etc. are used. These olefins are
It may be linear or branched.

In the present invention, these alkylating agents are usually used in a molar ratio of from 0.1 to the naphthalene starting material.
150, preferably in the range of 0.2 to 100.

In the method of the present invention, the aforementioned naphthalenes are reacted with an alcohol or an olefin as an alkylating agent in the presence of an ion-exchange type layered compound as a catalyst.

Ion-exchange type layered compounds usually have a form in which a large number of layered clays are accumulated, and the glabella of such layered clays contains ionic components. The layered clay material is mainly composed of silicon and oxygen, and may further contain crustal elements such as aluminum, magnesium, and iron. These have a layered structure in which many non-uniform layers are laminated, and the catalyst surface is wide.Furthermore, some of these have a layered crystal structure itself, such as tetrasilycin mica. Sometimes, like mica, it has cleavage.

Examples of such ion-exchange type M-type compounds include:
montmorillonite, bentonite, vermiculite,
Examples include taeniolite, hectorite, saponite, and tetrasilicic mica.

In the present invention, among these, those with a developed layered structure are preferred, and tetrasilic mica, montmorillonite, bentonite, hectorite, and teniolite are particularly preferably used.

It is preferable that the ionic component between the eyebrows is a cationic component, and in particular, tjA'l from a proton or a trivalent or higher valent element.
Preferably, it is a cation that undergoes L.

In particular, 5 mol% or more of the ionic components, preferably
It is desirable that such cations account for 30 mol% or more. Examples of cations derived from trivalent or higher valence elements include aluminum ions, iron ions,
Zirconium ion, titanium ion, gallium ion,
Elemental ions such as indium ions, cerium ions, and lanthanum ions; fluoride ions such as aluminum fluoride, iron fluoride, zirconium fluoride, titanium fluoride, gallium fluoride, indium fluoride, cerium fluoride, and lanthanum fluoride; Chloride ions such as aluminum chloride, iron chloride, zirconium chloride, titanium chloride, gallium chloride, indium chloride, cerium chloride, lanthanum chloride, aluminum bromide, iron bromide, zirconium bromide, titanium bromide, gallium bromide, odor Bromide ions such as indium chloride, cerium bromide, and lanthanum bromide; iodides such as aluminum iodide, iron iodide, zirconium iodide, titanium iodide, gallium iodide, indium iodide, cerium iodide, and lanthanum iodide. ion, aluminum hydroxide, iron hydroxide,
Zirconium hydroxide, titanium hydroxide, gallium hydroxide,
Examples include trivalent or higher ions such as hydroxide ions such as indium hydroxide, cerium hydroxide, and lanthanum hydroxide, or mono to trivalent or higher valent ions containing elements that can induce trivalent or higher ions.

In particular, among the above-mentioned ionic components, protons, aluminium ions, gallium ions, zirconium ions, iron ions, titanium ions, or indium ions are preferable. These ionic components may be contained alone or in combination of two or more. When such an ionic component exists between the layers, the ion-exchange type layered compound has particularly high monoalkylation selectivity and high reaction activity, so it is suitable for producing dialkylnaphthalenes from monoalkylnaphthalenes. It can be used for.

Furthermore, the ion exchange type layered compound used in the present invention usually contains sodium ions, potassium ions,
Alkyl metal ions such as rubidium ions, cesium ions and francium ions and/or alkaline earth metal ions such as beryllium ions, magnesium ions, calcium ions, strontium ions, barium ions, radium ions, preferably less than 95 mol%. is contained in an amount of 70 mol% or less.

In the present invention, such an ion exchange type layered compound is used in an amount of usually 1 to 400 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the naphthalene as a starting material.

According to the present invention, by using an ion-exchange type layered compound as a catalyst, the alkylation of naphthacines, particularly the monoalkylation of alkylnaphthalenes, can be carried out with high selectivity and high yield. The target dialkylnaphthalenes can be obtained at a certain rate. Moreover, since the ion exchange type layered compound has excellent heat resistance, the method according to the present invention is industrially advantageous.

The reaction is generally carried out at a temperature in the range of 40 to 300°C, preferably in the range of 80 to 250°C, for 1 minute to 24 hours, preferably 30 minutes to 10 hours. The reaction is usually carried out under normal pressure, but can also be carried out under increased pressure if necessary.

In the present invention, a reaction solvent may or may not be used. When using a solvent, any solvent can be used as long as it is inert to the starting materials, alkylating agent and catalyst, but organic solvents that can dissolve well the naphthalenes and reaction products used are particularly preferred. For example, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, and dibromobenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and decane, and halogenated fats such as dichloromethane and 1,2-dichloroethane. group hydrocarbons, diethyl ether,
Ethers such as tetrahydrofuran and dioxane are used. In particular, halogenated aromatic hydrocarbons such as dichlorobenzene and dibromobenzene are preferably used.

The amount of solvent used is not particularly limited, but is usually used in a weight ratio of 0.2 to 500 relative to the naphthalene starting material.

After the reaction is completed, the catalyst can be removed from the reaction mixture by an appropriate means such as filtration, and then a reaction product can be obtained by an appropriate means such as distillation.

According to the invention, corresponding to the starting materials mentioned above, -formula (wherein R and n are the same as above, R' represents an alkyl group or a cycloalkyl group, and when n is O, (m represents 2, and when n is 1, m represents 1.) Alkylated naphthalenes represented by: can be obtained. In addition, in the above-mentioned format, the substituents R and R
' may be on any aromatic ring. Therefore, according to the present invention, the dialkylnaphthalenes include, for example,
Dimethylnaphthalene, ethylmethylnaphthalene, diethylnaphthalene, isopropylmethylnaphthalene, isopropylethylnaphthalene, cyclohexylmethylnaphthalene, cyclohexylethylnaphthalene, dicyclohexylnaphthalene, etc. can be obtained.

In the present invention, when naphthalenes are cycloalkylated, the resulting compound is not, strictly speaking, an alkylated naphthalene, but herein, such cycloalkylated naphthalenes are also included in the alkylated naphthalenes. .

According to the method of the present invention, naphthalenes, preferably alkylnaphthalenes, are reacted with an alcohol or an olefin as an alkylating agent in the presence of an ion-exchange layered compound, resulting in high selectivity and high The desired dialkylnaphthalenes can be obtained in high yield.

The present invention will be explained below with reference to examples, but the present invention is not limited to these examples in any way.

Example 1 2-methylnaphthalene 725cm, methanol 0°5ml
A mixture of 200 ml of tetrasilicic mica ion-exchanged with aluminum ions and 2 ml of chlorobenzef was charged into a 50 ml autoclave.
The mixture was stirred at 20°C for 2 hours and 30 minutes.

The reaction results were 2-methylnaphthalene conversion rate of 33.6%,
The dimethylnaphthalene selectivity was 90.0%.

Example 2 The reaction was carried out in the same manner as in Example 1, except that montmorillonite 200cm, which had been ion-exchanged with protons, was used instead of tetrasilicic mica, which had been ion-exchanged with aluminum ions. I did this.

The reaction results were 2-methylnaphthalene conversion rate of 28.3%,
The dimethylnaphthalene selectivity was 91.2%.

Example 3 The reaction was carried out in the same manner as in Example 1, except that Taeniolite 200■ which had been ion-exchanged with gallium ions was used instead of tetrasilicic mica which had been ion-exchanged with aluminum ions. I did this.

The reaction results were 2-methylnaphthalene conversion rate of 38.5%,
The dimethylnaphthalene selectivity was 87.6%.

Example 4 In the same manner as in Example 1, except that Hectorite 200■ which had been ion-exchanged with iron ions was used instead of tetrasilicic mica which had been ion-exchanged with aluminum ions, The reaction was carried out.

The reaction results were 2-methylnaphthalene conversion rate of 32.6%,
The dimethylnaphthalene selectivity was 93.1%.

Comparative Example 1 In Example 1, except that 200 μm of silica-alumina (8-volatile N-632L) was used instead of tetrasilicic mica that had been ion-exchanged with aluminum ions.
A reaction was attempted in the same manner as in Example 1, but the reaction did not proceed at all.

Comparative Example 2 A procedure was carried out in the same manner as in Example 1, except that 200 tg of Y-type zeola 4) (TSZ-320) was used in place of the tetrasilicic mica ion-exchanged with alkium ions in Example 1. , conducted the reaction.

Reaction t41 had a 2-methylnaphthalene conversion rate of 16°0%.
, the dimethylnaphthalene selectivity was 77.0%.

Example 5 In Example 1, instead of 2-methylnaphthalene, 1
- Example 1 except that methylnaphthalene 725■ was used
The reaction was carried out in the same manner.

The reaction results were 1-methylnaphthalene conversion rate of 34.6%,
The dimethylnaphthalene selectivity was 92.3%.

Example 6 In Example 2, instead of 2-methylnaphthalene, 1
- Example 1 except that methylnaphthalene 725■ was used
The reaction was carried out in the same manner.

The reaction results were 2-methylnaphthalene conversion rate of 28.3%,
The dimethylnaphthalene selectivity was 92.5%.

Example 7 In Example 1, instead of 2-methylnaphthalene, 2
- Example 1 except that ethylnaphthalene 725■ was used
The reaction was carried out in the same manner.

The reaction results were 2-ethylnaphthalene conversion rate of 36°2%,
The ethylmethylnaphthalene selectivity was 90.3%.

Example 8 A mixture of 4.44 g of 2-methylnaphthalene, 0.97 g of montmorillonite ion-exchanged with aluminum ions, and 15 ml of chlorobenzene was heated to reflux, and a mixture of 2.35 g of isopropanol and chlorobenzene 8a+1 was dropped into the mixture. The mixture was added dropwise over a period of 1 hour. During this time, the water produced by the reaction was removed from the reaction system using a Dean-Stark water trap. After the completion of the dropwise addition, heating and stirring were continued for an additional 20 minutes.

The reaction TC result was 2-methylnaphthalene conversion rate of 63.5%.
The selectivity for isopropylmethylnaphthalene was 86.4%.

Example 9 In Example 8, instead of montmorillonite ion-exchanged with aluminum ions, tetrasilycin mica 0.97 was ion-exchanged with titanium ions.
The reaction was carried out in the same manner as in Example 8, except that g was used.

The reaction results were 2-methylnaphthalene conversion rate of 51.9%,
The isopropylmethylnaphthalene selectivity was 90.6%.

Comparative Example 3 The reaction was carried out in the same manner as in Example 8, except that 0.97 g of silica alumina (JGC N~632L) was used instead of montmorillonite that had been ion-exchanged with aluminum ions. Ta.

The reaction results were 2-methylnaphthalene conversion rate of 26.5%,
The isopropylmethylnaphthalene selectivity was 63.2%.

Example IO A reaction was carried out in the same manner as in Example 8, except that 3.82 g of cyclohexanol was used instead of isopropanol.

The reaction results were 2-methylnaphthalene conversion rate of 81.4%,
The cyclohexylmethylnaphthalene selectivity was 82.6%.

Example 1) 4.44 g of 2-methylnaphthalene, 0.91 g of Taeniolite ion-exchanged with aluminum ions and
- A mixture consisting of 20 ml of dichlorobenzene is heated to reflux, and propylene is added thereto at a rate of 20 ml/min.
The time passed.

The reaction results were 2-methylnaphthalene conversion rate of 70°3%,
The isopropylmethylnaphthalene selectivity was 80.2%.

Example 12 In Example 1), 0.97 g of montmorillonite ion-exchanged with zirconium ions was used instead of taeniolite ion-exchanged with aluminum ions.
The reaction was carried out in the same manner as in Example 1) except that .

The reaction results were 2-methylnaphthalene conversion rate of 62.3%,
The isopropylmethylnaphthalene selectivity was 91.6%.

Example 13 In the same manner as in Example 1), except that in Example 1), 0.97 g of hectorai) which had been ion-exchanged with indium ions was used instead of Taeniolite which had been ion-exchanged with aluminum ions. The reaction was carried out.

The reaction results were 2-methylnaphthalene conversion rate of 58.2%,
The isopropylmethylnaphthalene selectivity was 86.5%.

Example 14 The reaction was carried out in the same manner as in Example 1), except that isobutyne was used instead of propylene.

The reaction results were 2-methylnaphthalene conversion rate of 74.6%,
The t-butylmethylnaphthalene selectivity was 80.2%.

Claims (1)

[Claims] (1) In the presence of an ion-exchange layered compound, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting naphthalenes represented by (.) with alcohol or olefin as an alkylating agent. ' represents an alkyl group or a cycloalkyl group, when n is 0, m represents 2, and when n is 1, m represents 1.) A method for producing an alkylated naphthalene represented by: