JPH07223989A - Method for producing acyl group-substituted aromatic compound - Google Patents

Abstract

PURPOSE:To efficiently perform the acylation reaction of an aromatic hydrocarbon with an aliphatic carboxylic acid or its derivative in a high conversion and in a high position selectivity. CONSTITUTION:A method for producing an acyl group-substituted aromatic compound of formula, R1-CO-Ar-(R3)m (R1 is alkyl; R3 is H, alkyl, when m is >=2, R3 may be mutually different alkyl groups; Ar is single cyclic, polycyclic or condensed cyclic aromatic residue, the polycyclic aromatic residue being directly bound; m is an integer of 1-5, when Ar is the single cyclic, and m is 1 to the largest binding number of R3, when the polycyclic or the condensed cyclic) comprises reacting an aromatic compound of formula, H-Ar-(R3), (H is hydrogen atom) with an acylating agent of formula, R1-CO-X (X is Cl, Br, OH, alkoxy or -OCOR2 (R2 is alkyl which is same as R. or different from R1) in the presence of a zeolite having a 12-membered fine hole structure subjected to an ion exchange with metal ions in a gaseous phase.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the reaction of an aromatic hydrocarbon compound with an aliphatic carboxylic acid and its derivative in a gas phase in the presence of a zeolite having a 12-membered ring pore structure ion-exchanged with a metal cation. By producing an acyl group-substituted aromatic compound.

Acyl group-substituted aromatic compounds such as acetophenone or p-isobutylacetophenone are very useful as raw materials for perfumes, pharmaceuticals and agricultural chemicals.

[0003]

2. Description of the Related Art Conventional methods for producing an acyl group-substituted aromatic compound generally include aluminum chloride as a catalyst,
A method in which a Lewis acid such as iron chloride or boron trifluoride or a protic acid such as hydrofluoric acid is used to carry out a Friedel-Crafts type acylation reaction between an aromatic compound and a carboxylic acid chloride or a carboxylic acid anhydride. It has been known. These catalysts are generally required in a stoichiometric amount or more, and when they are carried out industrially, they are highly corrosive to the equipment and during the treatment after the acylation reaction, the catalysts are hydrolyzed. It is well known that it has many operational and environmental problems to be solved, such as decomposition and generation of a large amount of waste including hydrochloric acid.

It has therefore been a long-standing research object to find non-corrosive, inexpensive solid acid catalysts that replace these catalysts. Various types of zeolite catalysts have been proposed to achieve this end. In general, many methods relating to acylation of aromatic ether compounds and phenol compounds, which are apt to undergo Friedel-Crafts type acylation reaction, have been disclosed (Japanese Patent Laid-Open No. 4-2359).
41, European Patent No. 334096, No. 31613
3, German Patent Nos. 3809260, 3704810
Nos. 4,668,826 and 4,652,683). High regioselectivity has been reported for zeolite catalysts. On the other hand, the following examples are disclosed as a method for acylation of an aromatic hydrocarbon compound which is generally less reactive than an aromatic ether compound and a phenol compound.

European Patent No. 455332 describes 1
In the presence of zeolite beta having a two-membered ring pore structure,
It has been shown to acylate aromatic compounds with aromatic carboxylic acids or their esters or anhydrides.

European Patent No. 239383 shows an acylation method in which a lower alkyl- or phenyl-substituted benzene is reacted with a lower alkanoic acid using a pentasil-type zeolite as a catalyst. As the alkanoic acid, only the lower one reacts, and a conversion rate of about 5% is obtained.

French Patent No. 2592039, or J. Org. Chem. , 51, 2128 to 2130
(1986) shows that Ce ion-exchanged zeolite, particularly Y-type zeolite, is effective in the method of liquid-phase acylation of aromatic hydrocarbons with carboxylic acids or acid chlorides or anhydrides thereof. Has been done. Only when using long-chain carboxylic acids such as octanoic acid,
It has been shown that high conversion is obtained and acetic acid and the like do not react.

In Japanese Patent Laid-Open No. 4-279545, there is 10
A method of gas phase acylating benzene with a carboxylic acid in the presence of a pentasil-type zeolite having a membered ring pore structure has been shown. In the reaction of benzene and acetic acid, acetophenone in the product was obtained at about 3% by weight. Has been.

[0009]

Thus, in the method of acylating an aromatic hydrocarbon compound using a zeolite catalyst, the conversion rate is not limited, although the non-corrosiveness is a recognized advantage. There has been a strong demand for the appearance of a catalyst that is industrially practical and has drawbacks such as a low level.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that in the presence of a zeolite having a 12-membered ring pore structure ion-exchanged with a metal cation They have found that an acyl group-substituted aromatic compound can be produced by reacting an aromatic hydrocarbon compound with an aliphatic carboxylic acid and its derivative, and reached the present invention.

That is, the present invention has the following general formula (I) R1 --CO--X (I) (wherein R1 is an alkyl group; X is Cl, Br, O).
H, an alkoxy group or --OCOR2, where R
2 is an alkyl group, which may be the same as or different from R1. And an acylating agent represented by the following general formula (II) H-Ar- (R3) m (II) (wherein H is a hydrogen atom; Ar is a monocyclic, polycyclic or condensed ring). R3 is a hydrogen atom or an alkyl group, and when m is 2 or more, they are different from each other. M may represent an integer between 1 and 5 when Ar is a monocyclic ring, and 1 to R when it is a polycyclic or condensed ring system.
3 represents an integer between which maximum bonding is possible. ) Is reacted with an aromatic compound represented by the formula (1) in the presence of a zeolite having a 12-membered ring pore structure ion-exchanged with a metal cation. Ar- (R3) m (III) (wherein R1, R3, Ar, and m are the same as above), and is a method for producing an acyl group-substituted aromatic compound.

The process according to the invention is characterized by the use of zeolites with a 12-membered ring pore structure. 12
Examples of the zeolite having a member ring pore structure include zeolite beta (described in US Pat. No. 3,308,069) and faujasite (DW Breck, “Mo”).
(Leural Sieves ", 1974, etc.) and the like. Some zeolites, for example, faujasite type Y zeolite, are commercially available from PQ.

The zeolite can be produced by hydrothermal synthesis according to the method described in the above document. After crystallization, it is filtered, washed with water, dried and then calcined to remove the organic template. Then, ion exchange is performed with a metal cation by ion exchange. The metal cation is preferably a divalent or trivalent metal cation, and more preferably a divalent or trivalent ion of an alkaline earth metal, a transition metal or a rare earth metal. The type of metal is, for example, Ca, Mg, Cu, Z
Suitable examples include n, Ni, and Fe. And, a zeolite in which 50% or more, and more preferably 75% or more of substantially useful cation sites are substituted with metal cations is preferable.

In the method of the present invention, the zeolite may be used as a catalyst mixed with other zeolite, if necessary. Furthermore, the zeolite can be used after being appropriately treated with a substance such as acid, alkali, heat, steam, ammonia, halogen, or other non-metal compound.

As the catalyst used in the method of the present invention, pure zeolite may be used as it is or may be used as a molded body. The molding method is not particularly limited, and known methods such as an extrusion method and a compression method can be applied. If necessary during molding, silica, alumina,
A binder such as silica-alumina, magnesia or clay mineral may be used.

In the present invention, when the catalyst activity is lowered by the reaction, the catalyst is regenerated at appropriate intervals. As the method of the regeneration treatment, for example, the method such as washing, acid treatment and baking can be used.

The aromatic compound used in the method of the present invention has the following general formula (II) H-Ar- (R3) m (II) (wherein H is a hydrogen atom; Ar is a monocyclic ring). , A polycyclic or fused ring aromatic residue, wherein the polycyclic aromatic residue is bonded by a direct bond; R3 is a hydrogen atom or an alkyl group, and when m is 2 or more, they are different from each other. It may be an alkyl group; m represents an integer between 1 and 5 when Ar is a monocycle, and 1 to R when it is a polycycle or a condensed ring system.
3 represents an integer between which maximum bonding is possible). Especially an alkyl group having C ₁ -C ₁₀ preferably a R3.

Specific examples of the aromatic compound include benzene, toluene, ethylbenzene, o-, m- or p-xylene, n-propylbenzene, isopropylbenzene, n-butylbenzene, sec-butylbenzene and isobutylbenzene. , Tert-butylbenzene, o-, m- or p-cymene, mesitylene, pseudocumene, durene, o-, m- or p-ethyltoluene, o-, m- or p-diethylbenzene, n-pentylbenzene, n- Hexylbenzene, cyclohexylbenzene, diphenylmethane, tetralin, indane, benzylacetone, 1-phenyl-2-butanone,
Benzyl methyl ketone, benzyl ethyl ketone, dibenzyl ketone, biphenyl, 4-ethylbiphenyl, 2
-, 3- or 4-phenyltoluene, naphthalene, 1
Examples include-methylnaphthalene and 2-methylnaphthalene.

The acylating agent used in the present invention has the following general formula (I) R1 --CO--X (I) (wherein R1 is an alkyl group; X is Cl, Br, O).
H, an alkoxy group or --OCOR2, where R
2 is an alkyl group, which may be the same as or different from R1. ). Especially an alkyl group having C ₁ -C ₁₂ preferably a R1 and R2.

Specific examples of the acylating agent are as follows. Acetic acid, acetic acid chloride, acetic acid bromide, acetic anhydride, methyl acetate, propionic acid, propionic acid chloride, propionic acid bromide, propionic anhydride, methyl propionate, n-butyric acid, n-butyric acid chloride, n-butyric acid anhydrous, isobutyric acid, Isobutyric acid chloride, isobutyric acid anhydride, pivalic acid, pivalic acid chloride, pivalic acid anhydride, valeric acid, valeric acid chloride, valeric acid anhydride, caproic acid, caproic acid chloride, caproic acid anhydride, heptanoic acid, heptanoic acid chloride, heptane anhydrous Acid, octanoic acid, octanoic acid chloride, octanoic acid anhydride, chloroacetyl chloride, dichloroacetyl chloride, acrylic acid, acrylic acid chloride, methacrylic acid, methacrylic acid chloride, cyclohexylcarboxylic acid chloride, phenylacetyl chloride Ride, malonic anhydride, and the like succinic anhydride can be exemplified.

In the method of the present invention, the reaction can be carried out by a known method, but it is preferably carried out in the gas phase.

In the present invention, the reaction is carried out by feeding the acylating agent and the aromatic compound to the reactor. When feeding, if necessary, a diluent which does not participate in the acylation reaction, such as carbon tetrachloride, is used. A diluent or an inert gas such as nitrogen or helium may be used as the diluent, or these may be supplied separately.

The optimum supply ratio of the acylating agent to the reaction system in the method of the present invention is determined by the reaction temperature, the supply ratio of the aromatic compound as a raw material, the reaction apparatus, the type of reaction, etc. The aromatic compound may be used in a proportion of 0.01 to 20 mol, preferably 0.01 to 5 mol, per mol of the aromatic compound. The optimum range of residence time of the reaction mixture in the reaction zone is determined by the reaction temperature and the like, but is usually 0.1 to 60 seconds.

The reaction temperature used in the present invention may be in the range of not higher than the decomposition temperature, but it is preferably 150 to 500 ° C., more preferably 20 to 400 ° C. in view of reaction efficiency and the like. Further, the reaction pressure may be any of reduced pressure, normal pressure and increased pressure, as required. Most conveniently, the reaction is carried out at normal pressure.

In the present invention, a reactor packed with a zeolite catalyst can be used and can be carried out by various operations using various types of devices. For example, a fixed bed type, a fluidized bed type, a moving bed type or the like can be used as a continuous operation or an intermittent operation.

Thus, according to the acylation reaction of the present invention, the following general formula (III) R1 --CO--Ar-(R3) m (III) (wherein R1, R3, Ar and m are the same as above) The aromatic group-substituted aromatic compound represented by

The product mixture after the reaction is usually obtained as an oily substance through a condenser, and the produced acyl group-substituted aromatic compound can be separated and purified by a conventional distillation method, crystallization method or chromatographic method. . The separated unreacted raw material can be reused for the acylation reaction.

[0028]

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

Example 1 96.2 g of a 20 wt% tetraethylammonium hydroxide aqueous solution, a sodium aluminate aqueous solution (Al ₂ O
₃ content 19.5%, Na ₂ O content 20.2%) 1
6.8 g was dissolved in 254.1 g of water. 52.6 g of silicic acid was added to this aqueous solution and stirred to prepare a mixture slurry. This mixture slurry was charged into an autoclave having a volume of 500 ml, and reacted at 160 ° C. for 11 days while stirring. After cooling, the contents were taken out, filtered and washed with water seven times, and then dried at 120 ° C. overnight.

The X-ray diffraction pattern of the obtained product is shown in Table 1.
It was shown to. The product obtained from this result was zeolite beta.

[0031]

[Table 1]

Alumina sol was added to the obtained zeolite beta powder in an amount of 15% by weight in terms of Al ₂ O ₃ , and the mixture was kneaded, and then extruded into 14 to 24 mesh and molded at 500 ° C.
And baked in air for 2 hours. This zeolite beta molded body was subjected to ion exchange (solid-liquid ratio 20 ml / 10 g) 7 times at 90 ° C. using a 10 wt% nickel nitrate aqueous solution.
Further, it was thoroughly washed with water, dried at 120 ° C. overnight, and then calcined in air at 540 ° C. for 2 hours to prepare a Ni cation exchange type catalyst.

5 g of the above-prepared catalyst was charged into a reaction tube having a quartz tube having a length of 18 mmφ and a length of 530 mm, and a gentle nitrogen gas flow (2.4 l / Hr). Under toluene 46.1 g / Hr
(0.5 mol / Hr) and n-valeric anhydride 9.3 g /
Hr (0.05 mol / Hr) was flushed. At this time, the temperature in the catalyst layer was 240 ° C.

The reaction gas flowing out from the reaction tube was introduced into a container equipped with a condenser and condensed. After reacting for 1 hour, 54.1 g of a reaction product was obtained. A small amount of this reaction solution was taken, and p-methyl-n-valerophenone was quantified by an internal standard correction percentage method using a gas chromatogram.
-Production yield based on valeric acid was 6.3%.

Example 2 Y-type zeolite having a silica / alumina ratio of 30 (“CBV-720” manufactured by PQ) was molded in the same manner as in Example 1,
Ion exchange was performed by treating with a 10 wt% nickel nitrate aqueous solution at 90 ° C. seven times (solid-liquid ratio 20 ml / 10 g). It was washed 6 times with water at 90 ° C and then dried at 120 ° C overnight. This was calcined in air at 540 ° C. for 2 hours to prepare a Ni cation exchange type catalyst.

The n-valeric anhydride in Example 1 was replaced by n-valeric acid chloride, and 80 g of the catalyst prepared above was used.
After reacting for minutes, p-methyl-n-valerophenone was produced in a yield of 3.6% based on n-valeric acid chloride.

Example 3 Zeolite beta molded in the same manner as in Example 1 was treated with 10w.
Ion exchange was performed by treating with an aqueous t% ferric nitrate solution at 90 ° C. seven times (solid-liquid ratio 20 ml / 10 g). It was washed 6 times with water at 90 ° C and then dried at 120 ° C overnight. This was calcined in air at 540 ° C. for 2 hours to prepare an Fe cation exchange type catalyst.

The same reaction was carried out using 3.0 g / Hr of acetic acid (0.05 mol / Hr) in place of the anhydrous n-valeric acid of Example 1. Gas chromatogram analysis revealed that p-methylacetophenone was produced in a yield of 5% based on acetic acid. The p-form selectivity was 98.3%.

[0039]

According to the present invention, there is an effect that an acylation reaction of an aromatic hydrocarbon with an aliphatic or aromatic carboxylic acid and a derivative thereof can be efficiently performed with a high conversion rate and a high regioselectivity.

Claims (8)

[Claims] 1. The following general formula (I) R1 --CO--X (I) (wherein R1 is an alkyl group; X is Cl, Br, O).
H, an alkoxy group or --OCOR2, where R
2 is an alkyl group, which may be the same as or different from R1. And an acylating agent represented by the following general formula (II) H-Ar- (R3) m (II) (wherein H is a hydrogen atom; Ar is a monocyclic, polycyclic or condensed ring). R3 is a hydrogen atom or an alkyl group, and when m is 2 or more, they are different from each other. M may represent an integer between 1 and 5 when Ar is a monocyclic ring, and 1 to R when it is a polycyclic or condensed ring system.
3 represents an integer between which maximum bonding is possible. ) Is reacted with an aromatic compound represented by the formula (1) in the presence of a zeolite having a 12-membered ring pore structure ion-exchanged with a metal cation, the following general formula (III) R1 --CO-- Ar- (R3) m (III) (wherein R1, R3, Ar and m are the same as above), and a method for producing an acyl group-substituted aromatic compound. 2. The method for producing an acyl group-substituted aromatic compound according to claim 1, wherein the reaction is carried out in a gas phase. 3. The method for producing an acyl group-substituted aromatic compound according to claim 1, wherein the zeolite having a 12-membered ring pore structure is selected from beta and faujasite. 4. The method for producing an acyl group-substituted aromatic compound according to claim 1, wherein the metal cation is a divalent or trivalent metal cation. 5. The divalent or trivalent metal cation is at least one metal cation selected from alkaline earth metal cations, transition metal cations and rare earth metal cations. A method for producing an acyl group-substituted aromatic compound. 6. The acyl group-substituted aroma according to claim 4, wherein the divalent or trivalent metal cation is at least one metal cation selected from alkaline earth metal cations and transition metal cations. Method for producing group compound. 7. The acyl group-substituted aromatic compound according to claim 1, wherein R ₁ and R 2 in the acylating agent represented by the general formula (I) are C _{1 to} C ₁₂ alkyl groups. Method. 8. The method for producing an acyl group-substituted aromatic compound according to claim ₁ , wherein R 3 in the aromatic compound represented by the general formula (II) is a C _{1 to} C ₁₀ alkyl group.