JPH03153639A - Production of allyl group-containing aromatic compound - Google Patents

Abstract

PURPOSE:To obtain the title substance under a mild condition in high selectivity and in high yield by subjecting a 1-allyl-2-butene and ethylene to metathesis reaction in the presence of a metathesis catalyst selected from rhenium, tungsten and Mo. CONSTITUTION:A compound shown by formula I (R<1> to R<3> are H, lower alkyl or R<1> and R<2> are mutually bonded to form ring) and ethylene are subjected to metathesis reaction in the presence of a metathesis catalyst to give a compound shown by formula II. The reaction is carried out by liquid-phase reaction using Re2O7 supported on Al2O3 as the catalyst in n-hexane as a solvent at 0-70 deg.C or by a vapor phase reaction (50-200 deg.C) by fixed bed reaction method of circulation system using the same catalyst, having 1,000-200,000 hours contact time of raw material mixed gas. The metathesis catalyst is pretreated, packed into a fixed bed reactor of circulation system and an inert gas is circulated under normal pressure at 300-600 deg.C. The compound shown by formula II is useful as a monomer or an intermediate for drugs.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing an aromatic compound having an allyl group, and more specifically, in the presence of a specific metathesis catalyst, 1-aryl-2-butenes and ethylene are produced. The present invention relates to a method for producing an aromatic compound having an allyl group by metathesis reaction with.

BACKGROUND OF THE INVENTION Aromatic compounds having allyl groups are useful compounds that can be used as monomers for various olefin copolymers or synthetic intermediates for pharmaceuticals, fragrances, and the like. Therefore, it is strongly desired to develop an inexpensive and efficient method for producing aromatic compounds having an allyl group.

Heretofore, the following methods have been disclosed as methods for producing aromatic compounds having an allyl group, particularly allylbenzene.

(a) Diallyl ether and phenylmercury chloride are L
A method for producing allylbenzene at a yield of 18.7% by reacting at 24° C. for 16 hours in the presence of i2PdC1 (US Pat. No. 3,658,917).

1. Method for Producing Reaction Product Mixtures (U.S. Pat. No. 4,489)
212 Specification) PhH+ C112=CI(-C112CI(b)benzene and chloride in the presence of cupric chloride, 1
Method for producing allylbenzene by reacting at 50°C and 70 atm for 4 hours (US Pat. No. 3,678,122) (iii) Benzene and allyl chloride are brought to room temperature in the presence of a tantalum (V) chloride catalyst supported on silica. te1
By reacting for a time, allylbenzene, 2-chloropropylbenzene 1:(d)allyl bromide and phenylmagnesium bromide were combined in the presence of iodide IN (I) and nitrobenzene at a conversion rate of allyl chloride of 30%. By reacting in tetrahydrofuran solvent at reflux temperature for 30 minutes, the yield was 82.
% method for producing allylbenzene (Journal of Organometallic Chemistry (J, Org.
anomet.

Chem, ), Vol. 329, pp. 133-138, 1987
year) 1'L=CH-CLBr + PhMgBrTI(
F etc.

Problems to be Solved by the Invention However, in the production methods (a) to (c) disclosed above, the selectivity and/or yield of allylbenzene is low and the industrial applicability of diallyl ether etc. is low. It has problems such as using low-quality compounds as raw materials or having severe reaction conditions, and cannot be said to provide an industrially usable production technology. In addition, although the production method (2) disclosed above has a high yield,
The problem is that it is difficult to implement industrially because it uses a Grignard reagent that is expensive and difficult to handle.

Moreover, conventionally, there has been no known method for producing an aromatic compound having an allyl group by subjecting 1-aryl-2-butenes and ethylene to a metathesis reaction in the presence of a metathesis catalyst.

The present invention aims to solve problems associated with conventional techniques such as low yield and low industrial feasibility when producing aromatic compounds having an allyl group. The purpose of this invention is to provide an inexpensive and efficient method for producing aromatic compounds.

Means for Solving the Problems Summary of the Invention The present inventors, while investigating various methods for producing aromatic compounds having an allyl group, discovered that 1-aryl-2-butenes were produced in the presence of a specific metathesis catalyst. The present inventors have discovered that it is possible to produce aromatic compounds having allyl groups with high selectivity, high yield, and under mild conditions by conducting a metathesis reaction between ethylene and ethylene, and have completed the present invention.

That is, the present invention is based on the general formula [I] p+3 [wherein R1, R2 and R3 are hydrogen atoms or lower alkyl groups, preferably alkyl groups having 1 to 4 carbon atoms,
R1 and R2 may be bonded to each other to form a ring.

] General formula [II) 3 characterized by subjecting 1-allyl-2-butenes represented by 1-allyl-2-butenes and ethylene to a metathesis reaction in the presence of at least one metathesis catalyst selected from rhenium, tungsten and molybdenum. [In the formula, R1, R2 and R3 have the same meanings as above. The present invention relates to a method for producing an aromatic compound having an allyl group represented by the following formula.

Hereinafter, the method for producing an aromatic compound having an allyl group according to the present invention will be specifically explained.

Metathesis Reaction The metathesis reaction is a reaction represented by the following formula (i), which is also referred to as an olefin disproportionation reaction or metathesis reaction. The metathesis reaction is carried out in the presence of a metathesis catalyst.

R'-CII=C)I-R'(i>R5-CH=C11-R') In the production method according to the present invention, as shown in the following formula (ii), for example, 1-phenyl-2- By using butene and ethylene, allylbenzene and propylene are produced.

10H, C-C11=CR2 (ii) Also, from the following formula, allylbenzene is produced, and 1,4-diphenyl-2-butene and 2-butene are produced as by-products.

Manufacture.

1 10H,C-(1:H=CI-CH3 In the production method according to the present invention, in the presence of at least one metathesis catalyst selected from rhenium, tungsten and molybdenum, a compound represented by the following general formula [11] By subjecting 1-aryl-2-butenes to a metathesis reaction with ethylene, an aromatic compound 3 having an allyl group [wherein R1, R2 and R3 have the same meanings as above] is obtained. Butenes are, for example, produced by Brenns off-Chemie.
) 1963, Vol. 44, No. 6, p. 175, benzene and butadiene (4/1 molar ratio)
For example, by reacting with 95% phosphoric acid catalyst at 60 to 65°C,
Nauk Azerbaijanskoy Nisnisar (mouth o
kl, Akad, Nauk, Azerb, 5SR)
1965, Vol. 21, No. 2, p. 15, benzene, butadiene and 70%
It can be obtained in good yield by reacting sulfuric acid (4/1/1 molar ratio) at 55°C.

Specifically, the above-mentioned 1-aryl-2-butenes include 1-phenyl-2-butene, 1-tolyl-2-butene, 1-xylyl-2-butene, and l-natralyl-2-butene.
butene, 1-naphthyl-2-butene, etc. Among these, in the production method according to the present invention, 1-phenyl-2-butene, ■-trily-2-butene, and 1-xylyl-2-butene are used. is preferred.

Metathesis catalyst rhenium used in the production method according to the present invention,
The at least one metathesis catalyst selected from tungsten and molybdenum may be selected from known heterogeneous and homogeneous metathesis catalysts depending on the reaction type.

In the present invention, the metathesis catalyst used for reactions in a liquid phase heterogeneous system and gas phase is a catalyst in which Re2L is supported on A11 (hereinafter abbreviated as Re2L /Al2os).
, Re2L /VJs-Al1[1*, Re-07/
Mo[]=-AIJi, Re2L/5iOz M
O[)3/COO-81,03, WO,+/
5lOz Mo()+-3n(C)+3)a
/ 81203, W(0)s-8n(CH3)=/
5i02 is preferable, and as a metathesis catalyst for metathesis reaction in a homogeneous liquid phase system, WCla-BtO
H-EtAICl2,! JO(No)zc12[P([
"685)ff:] 2-BtAIC+2,
WOCl, −[EtAICl□, W(0)s−EtAI
Cl2-3n(CHa),,! JO(CD)s
-BtAl[1zSn(Cf13)4, ReC1s-I
EtAICI2 and the like are preferably used.

In addition, the metathesis catalysts used in the liquid phase heterogeneous system and the gas phase are pretreated before being subjected to the metathesis reaction. and inert gas such as dry smoke air and/or helium gas at normal pressure and 300 to 600°C to GIISV 1.000 to 100,00
This can be carried out by circulating the mixture for several hours at 0 hours (normal temperature and normal pressure).

Metathesis Reaction Conditions The metathesis reaction according to the present invention can be carried out in any of a liquid phase heterogeneous system, a liquid phase homogeneous system, or a gas phase system. The reaction method may be any conventionally known batch method, semi-batch method, or continuous method including fixed bed method, moving bed method, and fluidized bed method.

In the liquid phase reaction of the present invention, for example, Re2O7/A]2
When carrying out batchwise using a 03 catalyst, the reaction temperature is 0 to 0.
It may be carried out at 70°C and an ethylene partial pressure of 1-10 kg/cm2G. Further, a reaction time of 0.5 to 5 hours is sufficient.

Preferred solvents used in the liquid phase reaction include n-hexane, rhohebutane, cyclohexane, benzene, toluene, and chlorobenzene. Further, the amount of the catalyst to be used may be about 1.0×10 −′ to 0.1 mol of the metathesis catalyst per 1 mol of the 1-aryl-2-butenes.

In the gas phase reaction of the present invention, for example, Re20t/Al
When using a 2O3 catalyst in a fixed bed flow reaction system, the contact time of the mixed gas of 1-aryl-2-butenes and ethylene with the catalyst is GH3V at room temperature and pressure.
It is preferable to set the time at about 1,000 to 20,000 hours.

In addition, it is desirable that the reaction temperature is about 50 to 200°C; if it is less than 50°C, the reaction rate will be slow and the 1-
Because the vapor pressure of aryl-2-butenes is low, the supply amount decreases; on the other hand, if the temperature exceeds 200°C, the reactant 1-aryl-2-butene and the product aromatic product having an allyl group decrease. Both are unfavorable because side reactions occur due to isomerization of group compounds. The reaction pressure may be normal pressure or elevated pressure.

Effects of the Invention In the method of the present invention, an aromatic compound having an allyl group is produced using 1-aryl-2-butenes and ethylene as raw materials, so the raw materials have high industrial applicability and can be produced at low cost. Aromatic compounds having allyl groups can be produced.

In addition, in the method of the present invention, aromatic compounds having an allyl group are produced in a metathesis reaction in the presence of at least one metathesis catalyst selected from rhenium, tungsten, or molybdenum using ■-aryl-2-butenes and ethylene as raw materials. Since a compound is produced, an aromatic compound having an allyl group can be produced with high selectivity and high yield under mild conditions.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Note that the percentages in the examples are based on weight unless otherwise specified.

Example 1 A Re2L/^1203 catalyst (atomic ratio of Re/8 = 5/95) was prepared according to the method described in "Catalyst" Vol. 23, No. 2, p. 179, 1981. Rhenium heptoxide (1 g ampoule, manufactured by Mitsuwa Kagaku) was used as a reagent, and activated alumina calcined in air at 600° C. for 5 hours was used as a carrier. 2.5 g of the catalyst prepared with steam was charged into a fixed bed reactor with a flow system, and dry air was passed through it at 50 d/min (at normal temperature and normal pressure) at 510°C for 1 hour, and then 50 mj of helium gas was passed through the reactor. Distributed at normal temperature and pressure), 5
The catalyst was pretreated by calcining at 10° C. for 1 hour.

In a glass autoclave with an internal volume of 300 m1, the above pretreated catalyst and the dehydrated and purified n-
100 mf of hexane was charged, heated to 50°C, ethylene was introduced with stirring, and the system was pressurized to 5 kg/cm2G. Thereafter, 8.5 g of 1-phenyl-2-butene was introduced into the autoclave, and a metathesis reaction in a liquid phase heterogeneous system was carried out at 50° C. for 3 hours while stirring.

After the reaction was completed, the catalyst was filtered off from the reaction product, and the organic layer was analyzed by gas chromatography using ethylbenzene as an internal standard.

As a result, the conversion rate of 1-phenyl-2-butene was 32.
It was found that the yield of allylbenzene was 21.0%. In addition, the by-product 1,4-diphenyl-
The yield of 2-butene was 11.8%.

Example 2 1-phenyl-2-butene was replaced with 1-phenyl-2-butene as a reaction raw material.
Catalyst preparation, catalyst pretreatment, metathesis reaction, and gas chromatographic analysis were carried out in the same manner as in Example 1, except that tolyl-2-butene was used.

As a result, the conversion rate of ■-trily-2-butene was 25.6.
%, and the yield of allyltoluene was found to be 17.3%. In addition, the by-product 1,4-ditolyl-2
-The yield of butene was 8.3%.

Example 3 A ReJt/A12[1z catalyst (Re/AI atomic ratio -1/99) was prepared in the same manner as in Example 1, and 0.3 g of the prepared catalyst was pretreated in the same manner as in Example 1.

After that, the internal temperature of the fixed bed reactor was maintained at 100°C, and helium gas was passed through at atmospheric pressure at 100 d/min (normal temperature, normal pressure) and ethylene gas for 4°-7 min (normal temperature, normal pressure). Helium gas was supplied to the system fixed bed reactor, and further helium gas was introduced into the vaporizer filled with 1-phenyl-2-butene by cocking, and 1-phenyl-2-butene vapor of 0.8
Metathesis reaction in the gas phase was carried out by supplying 9 ml for 1.7 minutes (at normal temperature and normal pressure) together with helium gas to a fixed bed reactor with a flow system. At this time, the molar ratio of 1-phenyl-2-butene vapor and ethylene gas to the fixed bed reactor was I/45. The gas after passing through the catalyst layer was collected in a trap using methanol as a solvent, and gas chromatographic analysis was performed using ethylbenzene as an internal standard.

As a result, the conversion rate of 1-phenyl-2-butene was 31.
It was found that the selectivity of allylbenzene was 96.0%, and the yield of allylbenzene was 29.8%.

Example 4 In a glass autoclave with an internal volume of 300 mf, 100 ml of dried and purified benzene was added as a solvent.
10 g of 2-butene and 0.05 mol/each as catalyst
Il concentration of WC+s-ethanol (WC+,/ethanol-
15 ml of funnel solution and 0. 2 mol/l-a degrees of BtA
A metathesis reaction was carried out in a liquid phase heterogeneous system by charging 15 rd benzene solution of I (Iz), introducing ethylene under stirring and pressurizing the system to 5 kg/cm2G.The reaction was carried out at room temperature under stirring. The reaction was continued for 1 hour at 100 ml of water, and the reaction was stopped by adding methanol to the autoclave.

After the reaction was completed, gas chromatography analysis was performed.

As a result, the conversion rate of 1-phenyl-2-butene was 18.
5%, and the yield of allylbenzene was found to be 13.7%. The by-product is 61.4-diphenyl-
The yield of 2-butene was 4.8%.

Example 5 Mo(NO) at a concentration of 0.05 mol/l as catalyst
2CIz CP (CsHs) 3] Benzene solution of 2 15mj! and 0.2-11-rule/j”a1 degree no B
A metathesis reaction in a liquid phase heterogeneous system was carried out in the same manner as in Example 9, except that tAIC1z (D Hensen's solution 15d) was used.

As a result, the conversion rate of 1-phenyl-2-butene was 36.
4%, and the yield of allylbenzene was found to be 26.9%. In addition, the by-product 1,4-diphenyl-
The yield of 2-butene was 9.5%.

Comparative Example 1 A catalyst pretreatment and a metathesis reaction in a liquid phase heterogeneous system were performed under the same conditions as in Example 1 except that a Nb2O5/3102 catalyst was used as a catalyst, but the reaction did not proceed at all. Therefore, when the reaction temperature was increased from 50°C to 150°C and the reaction was continued for an additional 3 hours, only the isomerization reaction of the raw material 1-phenyl-2-butene occurred, and no production of allylbenzene was observed. .

Comparative Example 2 A metathesis reaction in a liquid phase heterogeneous system was carried out under the same conditions as in Example 4 except that SmC1:+-BtAICI2 catalyst was used as a catalyst, but no production of allylbenzene was observed.

Claims (1)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] [In the formula, R^1, R^2 and R^3 are hydrogen atoms or lower alkyl groups, and R ^1 and R^2 may be bonded to each other to form a ring. ] A general formula characterized by subjecting 1-allyl-2-butenes represented by the formula and ethylene to a metasense reaction in the presence of at least one metasense catalyst selected from the group consisting of rhenium, tungsten, and molybdenum. II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] [In the formula, R^1, R^2 and R^3 have the same meanings as above. ]
A method for producing an aromatic compound having an allyl group represented by