JPH0645001B2 - Friedel Crafts Reaction Catalyst - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel Friedel-Crafts reaction catalyst, and more particularly to a reusable Friedel-Crafts catalyst having sufficient catalytic activity. It relates to a reaction catalyst.

[Problems to be solved by conventional techniques and reactions] The Friedel-Crafts reaction is a useful reaction as an alkylation reaction or an acylation reaction of aromatic hydrocarbons. Various Lewis acids are known as catalysts for such Friedel-Crafts reaction, and among them, anhydrous aluminum chloride has a high catalytic activity and is widely used as a typical Friedel-Crafts reaction catalyst.

However, this catalyst is
There is a problem that it cannot be reused because it is decomposed and deactivated by water.

The present invention solves the conventional problems described above, has a sufficient activity as a Friedel-Crafts reaction catalyst, and can be recovered and reused without being deactivated in the treatment step after the reaction is completed. The purpose is to provide a catalyst for use.

[Means for Solving the Problems] In the course of earnest research to achieve the above object, the present inventors focused on the Lewis acid property of chloride of the lanthanoid group element, -The present invention has been completed by confirming an excellent effect when used as a catalyst for crafts reaction.

That is, the catalyst for Friedel-Crafts reaction of the present invention is characterized by comprising a chloride of a lanthanoid group element.

[Detailed Description] The Friedel-Crafts catalyst of the present invention is composed of a chloride of a lanthanoid group element as described above, and particularly has the formula: LnCl ₃ (where Ln is a trivalent lanthanoid group element). The same shall apply hereinafter). The trivalent lanthanide group element chloride is preferable because of its high catalytic activity. Any lanthanoid group element Ln may be used, and heavy rare earth elements Dy, Ho, Tm, Yb and Lu are particularly preferable. These catalysts may be prepared by applying a conventional method, or commercially available products may be used as they are.
In addition, since the activity of these catalysts decreases due to the presence of water, it is preferable to use them as anhydrides.

The catalyst of the present invention can be applied to any reaction in the ordinary Friedel-Crafts reaction. That is, specifically, as the alkylation reaction, for example, (1) a reaction for producing diphenylmethane from benzyl chloride and benzene: (2) Reaction to produce p-tert-butylphenol from phenol and isovitylene: (3) Reaction of forming p-tert-butylphenol from phenol and tert-butyl chloride: Etc., and as an acylation reaction,
For example, the reaction that produces 4-methoxybenzophenone from (4) benzoyl chloride and anisole: (5) Reaction to produce 4-methoxyacetophenone from acetyl chloride and anisole: (6) Reaction to produce 4-methoxyphenylethylketone from propionyl chloride and anisole: And so on.

These reactions do not necessarily require a solvent.

Moreover, when a solvent is used, the type of the solvent used is not particularly limited. The reaction temperature is 0 to 200 ° C,
Preferably, the temperature is set to 70 to 150 ° C, respectively. In any reaction, the reaction time can be set to 0.5 to 20 hours, preferably 2 to 10 hours, and the pressure can be set appropriately.

Then, after the reaction product is treated with water after the completion of the alkylation or acylation reaction, the catalyst, that is, LnCl ₃
Can be easily recovered. This recovered LnCl ₃
Still has sufficient catalytic activity,
It can be reused.

[Examples] Examples 1 to 18 and Comparative Examples 1 to 3 using the various catalysts shown in Table 1, the above-mentioned formula (I)
The reaction indicated by All reagents were commercially available.

First, put 2 m of benzene in a flask and add 0.
Disperse 5 mmol into which benzyl chloride 1.3
75 ° C while dropping 4 mmol (only in Comparative Example 3 from 0 ° C to 2 ° C).
The temperature was raised to 5 ° C.) and the reaction was carried out while stirring for the indicated time. After completion of the reaction, the mixture was cooled to room temperature, the reaction product was put into 2N hydrochloric acid for hydrolysis, and ether was further added and stirred. The ether layer was subjected to gas chromatography analysis after distilling off the ether, and the yield of diphenylmethane at that time was calculated based on benzyl chloride and shown in the table. However, in the table, the value in parentheses indicates the yield expressed on the basis of the catalyst.

In Example 4, the catalyst recovered by heating and removing water from the aqueous phase remaining after the ether phase separation in Example 3, and then recovering it, that is, PrCl _3, was reused. Similarly, Example 11 was the catalyst recovered from Example 10, that is, DyCl ₃ was reused.
No. 2 is a reuse of DyCl ₃ recovered from Example 11. In addition, Example 17 was recovered after the reaction of Example 16 was completed.
It is a recycled version of YbCl ₃ .

Examples 19 to 22 Above Examples 1 to 18 except that benzyl bromide was used in place of benzyl chloride, and the reaction time was 18 hours except for Example 21 (reaction time 2 hours).
Diphenylmethane was produced in exactly the same manner as in, and the yield is shown in Table 2.

Examples 23-25 Using the catalysts shown in Table 3, the following formula: The reaction shown by was carried out to obtain benzyltoluene. The reaction was performed at room temperature for 18 hours, yield of benzyltoluene based on benzyl chloride, and ortho of each benzyltoluene (o-),
The ratios of meta (m-) and pyra (p-) are shown in the table.

Examples 26 to 30 Using various catalysts shown in Table 4, the above formula (II) was used.
The reaction indicated by All reagents were commercially available.

Autoclave labeled catalyst 0.2 mmol, phenol 4
0 mmol, isobutylene (C ₄ mixture: isobutylene, 1
-Butene, 2-butene, a mixture of n-butane and isobutane) (20 mmol) and tert-butyl chloride (0.6 mmol) as a cocatalyst were charged, and the mixture was stirred at a reaction temperature of 60 ° C for 3 hours. After the reaction was completed, the reaction solution was cooled to 25 ° C., filtered, and the obtained filtrate was subjected to gas chromatography analysis.
The yield of the produced p-tert-butylphenol was calculated based on isobutylene and shown in the table.

Examples 31 to 35 Using the various catalysts shown in Table 5, the above-mentioned formula (II
The reaction indicated by I) was performed. All reagents were commercially available.

Autoclave labeled catalyst 0.2 mmol, phenol 4
0 mmol and 20 mmol of tert-butyl chloride were charged, and the mixture was stirred at a reaction temperature of 80 ° C. for 3 hours, and p-tert-butylphenol was obtained in the same manner as in Examples 26 to 30. Then, the yield of p-tert-butylphenol produced by the same gas chromatography analysis was calculated based on tert-butyl chloride and shown in the table.

Note that pt manufactured by the above formula (II) or (III)
ert-Butylphenol is useful as, for example, a preservative, the formaldehyde condensate of this product is useful as an oil-soluble resin, and the acetaldehyde condensate thereof is useful as an adhesive.

Example 36 A flask was charged with 5 mmol of YbCl ₃ , 20 mmol of benzoyl chloride and 24 mmol of anisole as a catalyst, and the reaction represented by the above formula (IV) was carried out. The reaction conditions at this time were set to temperature: 150 ° C., pressure: 0 kg / cm ² G and reaction time: 5 hours, respectively. After the reaction,
When cooled to 25 ° C., the yield of 4-methoxybenzophenone produced by gas chromatography analysis was calculated based on benzoyl chloride, and it was 85 mol%.

Example 37 An autoclave was charged with 5 mmol of TmCl ₃ as catalyst, 20 mmol of acetyl chloride and 24 mmol of anisole, and the reaction represented by the above formula (V) was carried out. The reaction conditions at this time were set to temperature: 150 ° C., pressure: 2 kg / cm ² G and reaction time: 5 hours, respectively. After completion of the reaction, the yield of 4-methoxyacetophenone was calculated based on acetyl chloride in the same manner as in Example 36 and it was 63 mol%.

Example 38 A flask was charged with ₃ mmol of HoCl, 20 mmol of propionyl chloride and 24 mmol of anisole as a catalyst, and the reaction represented by the above formula (VI) was carried out. The reaction conditions for Kotokinoki were set to a temperature of 120 ° C., a pressure of 0 kg / cm ² G and a reaction time of 8 hours. After the reaction,
When the yield of 4-methoxyphenylethyl ether ketone was calculated based on propionyl chloride in the same manner as in Example 36, it was 68 mol%.

EFFECTS OF THE INVENTION As is clear from the above description, the Friedel
The catalyst for the Krafts reaction can be used in Friedel-Crafts reactions in various systems to obtain a desired product in a sufficient yield, and further, it can be recovered and reused after the completion of the reaction. Especially, in the field of synthetic organic chemistry, its industrial value is extremely large.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C07C 2/86 15/16 9280-4H 37/14 8930-4H 37/18 8930-4H 39/06 8930-4H 45/46 7457-4H 49/84 C 7457-4H

Claims (1)

[Claims] 1. A catalyst for Friedel-Crafts reaction, which comprises a chloride of a lanthanoid group element.