JPS59144722A - Preparation of alkylbenzene nucleus halide - Google Patents

Abstract

PURPOSE:To obtain a p-halogenated alkylbenzene useful as a raw material for drugs, agricultural chemicals, various kinds of organic syntheses in high selectivity in high yield, by subjecting an alkylbenzene to nucleus halogenation using Y type zeolite as a catalyst. CONSTITUTION:An alkylbenzene especially preferably 1-4C alkylbenzene is subjected to nucleus halogenation with a halogenating agent such as a Cl2 gas, Br2 gas in the presence of a Y type zeolite catalyst optionally in a solvent in an inert gas such as N2, etc. at 0 deg.C- <= the boiling point of the solvent at normal pressure, to give the desired compound. The Y type zeolite is crystalline aluminosilicate having a molar ratio of SiO2/Al2O3 of 3-7, and aluminosilicate replaced with a metal of I A group except K, IIA group, IIIA group, IVA group, VA group and proton as a cation exchangeable with an ion is preferably used. EFFECT:Reaction and post-treatment operations are simple and catalyst can be reused.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an alkylbenzene halide. More specifically, alkylbenzene 7 is produced using a specific catalyst: Nuclear halogenation Lm selectivity J:<
1) - A method for producing halogenated trichlorbenzene.

Alkylbenzene nuclear halides are useful as raw materials for pharmaceuticals, agricultural products, and various organic synthetic chemicals.
-Chloroalkylbenzenes, such as tbp-chlorotoluene, are in high demand.

However, in the method of chlorine gaste chlorination using a Lewis acid such as antimony chloride, ferric chloride, or uruminium chloride as a catalyst, which is a nuclear salt conversion reaction that has conventionally been generally performed as a method for producing alkylbenzene nuclear halides. , 0-chloroalkylbenzene were mainly produced, and m-chloro and polychlorine derivatives were also produced as by-products, making it impossible to produce p-chloroalkylbenzene in a yield of 40 or more.

Therefore, in order to produce p-chloroalkylbenzene in good yield, a catalyst was developed.

For example, in a method using a Lewis acid and selenium or selenium as a catalyst, the p-chloro form is obtained in a yield of 45 to 52%, and in a method using a Lewis acid and a selenium as a catalyst, a p-chloro form is obtained. was obtained in a yield of 55 to 60 qb (Japanese Unexamined Patent Publication No. 19630/1983).

In a method using a Lewis acid and a phenoxatene compound as a catalyst, the p~chloro compound was obtained in a yield of 52 to 60% (Japanese Patent Application Laid-Open No. 175155/1982).

However, in both methods, the selectivity <p-
It was not yet sufficient to produce chloroalkylbenzene.

In view of the current situation, the present inventors have conducted intensive research and have surprisingly found that by using Y-type zeolite as a catalyst, not only can the conventional problems be solved, but also The present inventors discovered that p-halogenated trichlorbenzene can be produced with excellent selectivity, and based on this knowledge, they completed the present invention.

In other words, in the present invention, in the presence of a catalyst, the alkylbenzene nucleus is halogenated and the alkylbenzene nucleus is halogenated. I
This is a method for producing an alkylbenzene-nucleated halide, which is characterized in that C uses a Y-type zeolite as a catalyst.

In the present invention, the alkylbenzenes to be halogenated include chained and branched alkylbenzenes, but in particular, the γ-alkyl group has 1 to 4 carbon atoms (::). things are appropriate.

Further, the Y-type zeolite used in the method of the present invention may be a synthetic olide or a natural zeolite having a '@-layered aluminum AJzOi)/oxide vector. As the ion-exchangeable cation, Y-type zeolite, which is usually sodium, is available. In this case, it is also possible to ion-exchange sodium with potassium. For this ion exchange, a known ion exchange method is appropriately employed. Usually, ion exchange is easily carried out by treating the sodium 11iumium-containing 1jY type zeolite with a water bath solution containing potassium nitrate or chloride. The Y-type zeolite of the present invention may of course contain other cation components in addition to potassium ions; for example, potassium is preferably used. Also, these cations.

It may be one yuzu or two or more yuzu. For example, Y-type zeolite is synthetic zeolite manufactured by Union Carbide in the United States]
LZ-Y52. LZ-Y62. LZ-Y72 and LZ-
YB2 is well known.

In general, any synthetic zeophyte or natural zeolite having the same X-ray diffraction spectrum as that of the synthetic zeophyte or natural zeolite may be used.

Faujaside is common among natural zeolites. Further, the catalyst may be unfired or fired (7).

In order to carry out the alkylbenzene /kullogenation by the method of the present invention, Y-type zeolite corresponding to 421 moles of alkylbenzene is mixed at a voltage of 0.011 V or more, preferably 0.1 V or more, to the extent that it can be stirred. The halogenating agent is introduced at a temperature below the liI point. The reaction solvent may be used as desired. Further, it is appropriate for the reaction humidity to be industrially carried out at a temperature of 0° C. to below the fluoro point. As the halogenating agent in this case, 9 halogenating agents which are usually avoided can be used, but chlorine gas or bromine is preferable.

Also, it is not acceptable to use an inert gas such as methane during the reaction. The above reaction may be carried out under reduced pressure or increased pressure, but is usually carried out at normal pressure.

According to the method of the present invention, the halogenation of the 〇-position of alkylbenzene can be suppressed, the p-position can be selectively and efficiently halogenated, and the alkylbenzene side chain such as benzyl chloride/halogenide and polynuclear) ＼It has advantages such as very little generation of rogides, etc.

Furthermore, it is suitable for producing p-no-logogenated alkylbenzene, as the 5 reactions and post-treatment operations are simple, and the catalyst can be used conveniently, and its effectiveness is extremely high.i) Ru.

Hereinafter, the method of the present invention will be specifically explained with reference to Examples.

Example 1 In a 2001 reaction flask equipped with a cooling tube, a turbidity meter, a stirrer, and a blowing tube, 5 f. Stir at 100°C for 60 minutes.

Subsequently, 0.29 mol of chlorine was blown into the solution for 7 hours to carry out a reaction. After the reaction was completed, the resulting reaction solution was analyzed by gas chromatography, and the toluene conversion rate was 8.
2.7, 2-chlorotoluene/4-chlorotoluene production ratio (0/Put) -0.85. Benzyl chloride's sub-number (it was α8).

The Y-type zeolite (manufactured by Union Carbide, LZ-Y52) used in the reaction had a secondary chemical composition (atomic absorption method).

EliO, (Wtll) Dry base 6
'6.8'lkAjmOshin (wtlg)
22.9'INa,O(Wt-)
13.016S i OH/ AJ+ Os molar ratio &
4.740aO (wtl)
Section 0.38 Example 2 The reaction was carried out in the same manner as in Example 1, and the catalyst was used repeatedly. As a result, 9 reactions proceeded normally and the 07P ratio was 0.
．． It was 82. Furthermore, it was possible to reuse the catalyst.

Example 3 50 equipped with cooling tube, temperature needle, stirrer, chlorine blowing tube
0 txl fi reaction flask, Y type theolite (manufactured by Union Carbide, LZ-Y52)5. Of, Torxton L6t (0,05 mol), carbon tetrachloride purple 2 as bath medium
501 and stirred at room temperature for 60 minutes under 1Nlz flow. Next, a reaction was carried out at room temperature by blowing chlorine at α17 mol/hour for 125 hours.

After the reaction was completed, the resulting reaction solution was analyzed by gas chromatography, and the toluene conversion rate was 82.7.

2-chlorotoluene/4-chlorotoluene production ratio (0/
P ratio) was -0.70. Furthermore, the amount of by-product of benzyl chloride was 0.35 yen.

Patent applicant Ihara Chemical Industry Co., Ltd. 8- Procedural amendment (self-imposed February 1982 IS date 1, case description 1982 patent application No. 017711 2, title of invention Process for producing alkylhenzene nuclear halides 3) , Person making the amendment 4, Date of amendment order Voluntary action 5, Number of inventions increased by the amendment 06, Subject of amendment 7, Contents of the amendment 1) Page 4 of the specification [Aluminum oxide (#z03)/Silicon oxide (SiO
□) ratio] [Silicon oxide (SiO□)/aluminum oxide (uzo3) molar ratio]

that's all

Claims (1)

[Claims] A method for producing an alkylbenzene nucleus halide, which comprises using Y-type theolite as a catalyst in the method of producing an alkylbenzene nucleus halide by halogenating an alkylbenzene in the presence of M K cv s.