JPS63154632A - Production of halogenated benzene derivative - Google Patents

Abstract

PURPOSE:To selectively obtain a para-substituted halogenated benzene derivative in halogenating a benzene derivative by the use of faujasite type zeolite and/or L-type zeolite as a catalyst, by adding an organic phosphorus compound to a reaction system. CONSTITUTION:In producing a halogenated benzene derivative by halogenating reaction of a benzene derivative by the use of faujasite type zeolite and/or L-type zeolite as a catalyst, an organic phosphorus compound shown by formula I-formula V [R1-R3 are 1-20C hydrocarbon residue which may contain substituted group (OH, halogen, ester group or COOH); X and Y are halogen) in a ratio of 1X10<-5>-0.1g/g-zeolite, preferably 1X10<-4>-5X10<-2>g/g-zeolite calculated as phosphorus atom is added to the reaction system to give a para- substituted halogenated benzene derivative having abundant industrial demands in high selectivity while suppressing by-products of ortho-substituted halogenated benzene derivatives.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a halogenated benzene derivative by halogenating a benzene derivative. More specifically, unmodified or metal salt modified faujasite type zeolite and/or L type zeolite is used as a catalyst, an organic phosphorus compound is present in the reaction system, and benzene derivative is halogenated to ortho-substituted halogenation. The present invention relates to a method for selectively producing para-substituted halogenated benzene derivatives while reducing by-products such as benzene derivatives.

[Conventional technology]

Halogenated benzene derivatives are industrially important raw material intermediates in the field of organic synthetic chemistry, including pharmaceuticals and agricultural chemicals.

In the production of di-substituted benzene derivatives by halogenation of mono-substituted benzene derivatives, the products are 1,2-disubstituted (ortho), 1,3-disubstituted (meta), and 1.
．． Three types of 4-disubstituted (para) isomers are obtained, and the proportion of each isomer produced is determined by the type of substituent in the monosubstituted benzene derivative, the type of catalyst, etc. This is well known. For example, during the production of dichlorobenzene (hereinafter referred to as DCB) by the conventional liquid phase chlorination reaction of monochlorobenzene (hereinafter referred to as MOB) in the presence of ferric chloride, three types of The production ratio of isomers is as follows.

Orthodichlorobenzene: 30-40 Thimetadichlorobenzene: 0-5 Thibaracychlorobenzene: 60-70% Among these three types of isomers, industrially, the rose-substituted halogenated benzene derivatives are in great demand and are the most important. In such cases, it is possible to produce more of the target substance by performing an isomerization reaction, but the isomerization reaction from an ortho-substituted halogenated benzene derivative to a rose-substituted halogenated benzene derivative is extremely difficult. Yes, but not normally done.

Therefore, many methods have been proposed to more selectively produce halogenated benzene derivatives substituted with halogenated derivatives.

As one such method, a method has been proposed in which benzene derivatives are halogenated using zeolite as a catalyst to selectively produce rose-substituted halogenated benzene derivatives.

For example, Journal of Catalysis (, Tour
nal of C! analysis) ii, 1
10 (1979) reports the use of zeolite as a bromination catalyst for halogenated benzene.

In this cited example, various ion-exchange zeolites, ie, X-type and Y-type zeolites, are used as halogenation catalysts, and it has been shown that para-substituted bromobenzene derivatives are produced with high selectivity.

Also, Tetrahedron Letters (Tetrahear)
on Letters) L Yu, 3089 (1980) reports a benzene chlorination reaction using ZSM-5, ZSM-11, mordenite, L-type zeolite, Y-type zeolite, etc. as catalysts, and in particular, L-type zeolite. It is stated that a high selectivity to baladichlorobenzene (hereinafter abbreviated as PDCB) can be obtained in the case of Furthermore, for example, JP-A-59-130227, JP-A-59-144
No. 722, No. 59-165529, etc. disclose methods for producing halogens of benzene and alkylbenzene using L-type zeolite and Y-type zeolite as catalysts.

By using zeolite as a catalyst in this way,
Para-substituted I-logenated benzene derivatives have been produced with good selectivity, but in order to produce them with even better selectivity,
Research is underway on additives for the zeolite catalyst modification 1 reaction system. For example, JP-A-60-188333, JP-A-60-197652, JP-A-60-248651.
No. 3, etc., states that when zeolite treated with a lower acylating agent, an aliphatic carboxylic acid, a metal salt thereof, etc. is used as a catalyst in a liquid-phase 10-genation reaction of toluene, etc., para-substituted halogenated benzene derivatives can be selected. It has been reported that the rate is improved.

Chemistry Letters (C!chemistry Le
tters), p. 2007 (1984), in the bromination reaction of aniline using type A zeolite adsorbed with bromine, the addition of pyridine or 2,6-lutidine increases the bromination activity and selectivity of bromoaniline. It has been reported that it improves.

[Problem that the invention seeks to solve]

In the halogenation reaction of benzene derivatives, using zeolite as a catalyst is an effective means for selectively producing rose-substituted halogenated benzene derivatives;
The amount of by-products such as ortho-substituted halogenated benzene derivatives is preferably as small as possible from the standpoint of separation and purification of the target substance.

Therefore, there is a strong need for the development of a method for producing halogenated benzene derivatives with higher selectivity by further suppressing the production of by-products.

[Means for solving problems]

In view of this current situation, the present inventors conducted a detailed study on a method for selectively producing a rose-substituted halogenated benzene derivative by a halogenation reaction of a benzene derivative, particularly a reaction using a zeolite catalyst.

As a result, the present inventors found that when faujasite-type zeolite and/or L-type zeolite is used as a catalyst, the regioselectivity of halogenation is surprisingly reduced when an organic phosphorus compound is coexisting in the reaction system. The present inventors have discovered that the production of by-products such as ortho-substituted halogenated benzenes is suppressed, and the selectivity of para-substituted halogenated benzene derivatives is improved, leading to the completion of the present invention.

That is, the present invention is characterized in that when a halogenated benzene derivative is produced by a halogenation reaction of a benzene derivative using faujasite-type zeolite and/or L-type zeolite as a catalyst, an organic phosphorus compound is allowed to coexist in the reaction system. The present invention provides a method for producing a halogenated benzene derivative.

The present invention will be explained in more detail.

Zeolite is used as a catalyst in the method of the present invention, and zeolite is usually called crystalline aluminosilicate. Zeolite is S10. Although it is composed of tetrahedrons, Ato, and tetrahedra, many types are known due to the differences in the bonding styles of each tetrahedron. The zeolites used as catalysts in the process of the invention are faujasite-type zeolites and/or L-type zeolites.

Faujasite-type zeolite exists naturally, but it can also be synthesized by known methods, and Synthesized 7-Oujasite-type zeolite is widely known as X-type zeolite and Y-type zeolite. In the method of the present invention, synthetic Y-type zeolite, which has fewer impurities (and has a higher degree of crystallinity) among faujasite-type zeolites, is preferred. Faujasite-type zeolite has a characteristic crystal structure, so powder X-ray diffraction is difficult. It is possible to distinguish it from other zeolites by measuring it.The chemical composition of faujasite-type zeolite is expressed as a molar ratio of oxides, and is shown as a M, , O A403-b S i 02.

L-type zeolite also has a characteristic crystal structure, so powder
It is possible to distinguish it from other zeolites by measuring line diffraction. L-type zeolite is a type of synthetic zeolite, and can be synthesized by a known method. A typical composition of L-type zeolite, expressed in molar ratios of oxides, is: a M, 0, -b SiO.

It is indicated by.

Synthetic zeolite contains sodium cations, potassium cations, etc. as cations in its bifurcated state. In the method of the present invention, there are no particular limitations on the cations contained in the zeolite. That is, catalysts containing sodium cations, potassium cations, etc. contained during synthesis can be used as catalysts as they are, but catalysts that have been exchanged with other cations can also be used. In this case, the ion exchange treatment may be carried out using a known method, for example, by immersing the zeolite in an aqueous solution containing the cations to be exchanged.

In the method of the present invention, the various ion-exchanged zeolites described above may be used as catalysts as they are, but preferably zeolites further modified with metal salts are used.

Modification of zeolite with metal salts is described, for example, in JP-A-61-
This may be carried out according to the method described in Japanese Patent No. 189236.

That is, it is sufficient to bring the zeolite and the metal salt into intimate contact with each other, and specifically, the usual impregnation method or mixing method can be used.

Examples include the crosstalk method. Although there are no particular limitations on the method of modification with metal salts, it is possible to homogeneously modify the inside of the pores of the zeolite particles, not just the outer surface of the zeolite particles, and it is also simple. An impregnation method in which the zeolite is dissolved and impregnated with the zeolite is suitable.

There are no particular limitations on the metal salts used in these modification methods, and halides, carbonates, sulfates, etc. of alkali metals, alkaline earth metals, rare earth metals, etc. may be used. For example, sodium chloride, potassium chloride, strontium chloride, barium chloride, lanthanum chloride, sodium carbonate, potassium carbonate, strontium carbonate, barium carbonate, sodium sulfate.

Examples include potassium sulfate, strontium sulfate, barium sulfate, and the like. The amount of metal salt used for modification is 0.1N90 expressed as a weight percent relative to the catalyst.
It may be 10 to 80 inches, preferably 10 to 80 inches.

In the method of the present invention, there is no particular restriction on the shape of the catalyst, and it may be used as a catalyst by being normally shaped, but it may also be used as a powder in some cases. The molding method may be a conventional method, and examples thereof include extrusion molding, tablet molding, spray drying granulation, and the like. When molding,
For the purpose of increasing the mechanical strength, etc., a substance inert to this reaction may be added as a binder or molding aid. For example, 0 to 80% by weight of silica, clay, graphite, stearic acid, starch, polyvinyl alcohol, etc.
, preferably in a range of 2 to 30% by weight.

The catalyst thus obtained is dried if necessary, and then dried under air flow or nitrogen.

A calcination treatment is performed for 10 minutes to 24 hours under the flow of an inert gas such as helium, and used for the halogenation reaction. The firing temperature is 20
The temperature range may be from 0 to 900°C, preferably from 300 to 8
50℃ is good.

The method of the present invention is characterized in that the halogenation reaction of benzene derivatives is carried out in the presence of the above-mentioned zeolite catalyst and in the presence of an organic phosphorus compound in the reaction system. The organophosphorus compound as used in the present invention refers to a 6-carbon compound containing carbon atoms.
It is a valent or pentavalent phosphorus compound, and can be represented by the following general formulas (I) to (V).

R, -P -R3・Song・(I) ■ R, O-p -oRs -------(U)OR.

R,-P-0, , , , (IIQ ■ OR.

R, O-P -0... (M Rs s Here, R1+ R9+ RB each has 1 to 2 carbon atoms
0 represents a hydrocarbon residue containing or not containing a hydroxyl group, a halogeno group, an ester group, or a carboxyl group. However, this does not prevent part or all of R1 to R8 from being the same hydrocarbon residue. Furthermore, in the general formula (V), X and Y represent the same or different halogen atoms.

Examples of the organic phosphorus compound represented by the general formula (1) include phosphines such as diethylbutylphosphine, tributylphosphine, and butyldiphenylphosphine. Examples of the organic phosphorus compound represented by the general formula (11) include phosphites such as tripropyl phosphite and triphenyl phosphite, and examples of (m) include diethylpropylphosphine oxide and tributylphosphine oxide.

Examples include phosphine oxides such as butyl diphenylphosphine oxide, and phosphates such as trizolobyl phosphate, tributyl phosphate, and propyl butylphenyl phosphate. Examples of the compound include phosphine halides such as tributylphosphine dichloride and triphenylphosphine dichloride.

In the method of the present invention, it is necessary to use at least one type of the above-mentioned organic phosphorus compounds, but two
There is no problem even if more than one type is used in some cases.

Although various methods can be considered for making the organic phosphorus compound coexist in the reaction system of the halogenation reaction, any of the following methods may be used, and there are no particular limitations. That is, the organic phosphorus compound may be added to the reaction system separately from the raw materials and the catalyst, or it may be adsorbed or supported on the zeolite catalyst in advance and introduced into the reaction system together with the catalyst.

The amount of coexisting organic phosphorus compounds is affected by the addition method, the type of zeolite, the type of organic phosphorus compound, etc., so it is difficult to define it unambiguously, but it is determined by the weight of the phosphorus atoms contained in the organic phosphorus compound. It is possible to specify.

In other words, for the unit weight of zeolite, which is the catalyst,
I as the weight of phosphorus atoms contained in an organic phosphorus compound
A coexisting amount of X 10-'9/9-zeolite to α19/9-zeolite, preferably I X 10-4 g/9-zeolite to 5 X 10-''9/9-zeolite is required. The amount of coexistence is I x 10=
If the content is less than α19/9-zeolite, the effect of reducing the selectivity of by-products such as ortho-substituted halogenated benzene derivatives will be small, and if it exceeds α19/9-zeolite, it may have an adverse effect on the catalyst activity.

In the method of the present invention, benzene derivatives refer to benzene, halogenated benzenes, alkylbenzenes, etc., in which the hydrogen of benzene is substituted with a substituent such as a halogen or an alkyl group, such as benzene, benzene, monofluorobenzene, etc. .

Examples include MCB, monobromobenzene, monoiodobenzene, toluene, and ethylbenzene. Further, the halogenating agent may be a single halogen, and examples thereof include chlorine, bromine, and iodine.

In the method of the present invention, the reaction can be carried out in either a gas phase or a liquid phase, but a liquid phase is preferable in consideration of productivity and the like. In reactions in the liquid phase, the reactor.

There are no restrictions on the reaction method and reaction conditions as long as the benzene derivative is in a liquid state and comes into contact with the catalyst. For example, the reactor may be of a batch type, semi-batch type, or continuous type. The catalyst may be used in the form of, for example, a fixed bed or a suspended bed. The reaction is carried out using a liquid phase medium such as the liquid benzene derivative itself, or a solvent that does not participate in the halogenation reaction.
For example, it can be carried out in the presence of carbon tetrachloride or the like as a medium. When a solvent is used, the concentration of the benzene derivative is preferably 5 to 99% by weight, preferably 20 to 99% by weight. If it is less than 5% by weight, there will be fewer opportunities for the raw material to come into contact with the catalyst, making it impossible to obtain a sufficient conversion rate. When the halogenating agent is continuously supplied, an inert gas such as nitrogen or helium may be included. When using an accompanying gas, the concentration of the halogenating agent is preferably 5 to 99% by volume, and 20% by volume.
~99 capacity ratio is preferred. When using a batch type or semi-batch type reactor, the catalyst is mainly used in the form of suspension in the reaction liquid, but the amount of catalyst per unit reaction liquid volume is α001~19.
/l is good, and [9/l is preferable for 1005 to r1.1. If it is less than (1,001) cg/1, the load on the catalyst will be large and a sufficient conversion rate will not be obtained. Furthermore, when the ratio exceeds 1 to 9/l, the effect of increasing the amount of catalyst becomes small. The amount of halogenating agent supplied can be expressed as the amount of halogenating agent per unit time relative to the weight of the catalyst, and is 1 to 1500 moL.
/kg-cata'1yst-hr is good, 1o ~ a
o o mot/ni9-cata'1yst-h, r
is preferred. If it is less than 1 catalyst, a sufficient rate of production of the halogenated benzene derivative cannot be obtained, and if it exceeds 1500 catalysts, the amount of unreacted halogenating agent increases, which is not economical. When a continuous reactor is used, the amount of benzene derivative supplied can be expressed as the amount per unit time for the catalyst used, and is approximately 5 to 300 t/Q-ca.
tal-yst-hr is sufficient, and 9-yst-hr is sufficient for 2 to 100 t/
cata'lyst *hr is preferred. Other reaction conditions are the same as in the case of using a batch type or semi-batch type reactor.

In the method of the present invention, when the reaction is carried out in a liquid phase, there are no restrictions on the reaction temperature and reaction pressure as long as the benzene derivative or its solution is in a liquid phase.

When the reaction temperature is higher than the boiling point of benzene derivatives, etc.
Although the halogenation reaction can be carried out in a liquid phase by increasing the reaction pressure, the reaction temperature is preferably 0 to 200°C, more preferably 20 to 150°C. Below 0℃,
A sufficient reaction rate cannot be obtained, and if the temperature exceeds 200°C, the selectivity of para-substituted halogenated benzene derivatives decreases. When the reaction is carried out in the gas phase, the benzene derivative and the organic phosphorus compound are brought into contact with the catalyst in a vaporized state.
A range of 00°C is good. In the case of a reaction temperature lower than this temperature range, a sufficient reaction rate cannot be obtained, and in the case of a reaction temperature higher than this temperature range, the selectivity of para-substituted halogenated benzene derivatives etc. is reduced.

〔Effect of the invention〕

According to the method of the present invention, by-products such as ortho-substituted halogenated benzene derivatives are reduced in the benzene derivative nohalogenation reaction, and para-substituted halogenated benzene derivatives, which are industrially valuable, are selected more highly than in conventional methods. can be manufactured at a high rate. In the method for producing a substituted halogenated benzene derivative, the isomerization reaction from an ortho-substituted halogenated benzene derivative to a para-substituted halogenated benzene derivative is very difficult and is therefore not usually carried out industrially. Therefore, if the selectivity of para-substituted halogenated benzene derivatives increases even slightly, the amount of by-product ortho-substituted halogenated benzene derivatives with low industrial value can be greatly reduced, and Separation and purification becomes easy, and as a result, manufacturing costs can be reduced. For example, the selectivity of para-substituted halogenated benzene derivatives in Comparative Example 10 by the method of the present invention
The improvement from 85% to 86% or more in Examples 1 to 4086 means that the amount of by-products such as ortho-substituted halogenated benzene derivatives was reduced by 7% or more.

Therefore, the present invention is extremely significant from an industrial perspective.

〔Example〕

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

Note that the conversion rate and selectivity shown in the examples represent numerical values calculated by the following formula.

Sum of production amounts of all products (mot) Example 1 12.87G+ sodium chloride (NaCt) was placed in a 1t porcelain beaker and dissolved in 300d distilled water. Keep this solution at 95°C using a hot bath, and add 5iOy'A to it while stirring thoroughly with a glass stirring blade.
30 liters of sodium cation-containing Y-type zeolite (manufactured by Toyo Soda Kogyo ■) with a 40s ratio of 5.5 was added. Evaporate to dryness on a hot water bath until all moisture is gone, dry in a dryer kept at 130°C for 15 hours, and then dry at 540°C under air circulation for 5 hours.
After firing for a period of time, a sodium cation-containing Y-type zeolite containing 30% by weight of MaCl was obtained.

Liquid phase chlorination of monochlorobenzene (MCB) was carried out using this catalyst and tributylphosphine as an organic phosphorus compound. The reaction was carried out using a conventional semi-batch reactor. gas blowing pipe.

A 100-volume Pyrex reactor (inner diameter 40 fi, height 100 mm) equipped with a cooling tube was filled with 409 MOB and [10829 tributylphosphine, and further,
1.439% of the above zeolite catalyst was added to form a suspension.

In this case, the amount of coexisting tributylphosphine per unit weight of zeolite is 1.5
10-2 g/9-zeolite.

While stirring the reaction mixture well with a magnetic stirrer, chlorine gas (accompanied by an equal amount of nitrogen gas) was bubbled in at a feed rate of 30 dl min. The reaction temperature was controlled at 100° C. by using an oil bath around the reactor. Three hours after starting to blow chlorine gas,
The product was analyzed by gas chromatography. The results are shown in Table 1.

Examples 2 to 6 Using sodium cation-containing Y-type zeolite modified with NaO4 prepared in the same manner as in Example 1 as a catalyst,
As an organic phosphorus compound, instead of tributylphosphine, trioctylphosphine 0.159. ) liptyl phosphite 0.10 g,) butyl phosphite) (Lll
g,) Riphenylphosphine 0.529. ) A liquid phase chlorination reaction of MCB was carried out in exactly the same manner as in Example 1, except that Riphenylphosphine dichloride 11159 was used in each case. The results are shown in Table 1.

Comparative Example 1 A liquid phase chlorination reaction of MCB was carried out in exactly the same manner as in Example 1, except that tributylphosphine was not allowed to coexist. The results are shown in Table 1.

From Table 1, it is understood that when the organic phosphorus compound is co-present in the reaction system, the production of by-products is significantly suppressed.

Example 7 As a catalyst, a potassium cation-containing zeolite with a ZO 5iOt/A403 ratio (manufactured by Toyo Soda Kogyo ■) of 1.09
using tributylphosphine α033,
A liquid phase chlorination reaction of MOB was carried out in the same manner as in Example 1 except that the reaction temperature was 70°C. In this case, the coexisting amount of tributylphosphine is 5.5% by weight of phosphorus atom per unit weight of zeolite. IXl 0''-''9/9-zeolite.

The MOB conversion rate 3 hours after starting to blow chlorine gas is as follows:
6α1%, by-product selectivity such as 0DOB 4.1ch, FD
The OB selection rate was 95.9ch.

Comparative Example 2 A liquid phase chlorination reaction of MCB was carried out in the same manner as in Example 7 except that tributylphosphine was not allowed to coexist. The MCB conversion rate 3 hours after starting the reaction was 6α3
H, by-product selectivity such as 0DCB, 9.4, PDC:B
The selection rate was 9Q, 6Q.

From Example 7 and Comparative Example 2, it is understood that the effect of the coexistence of organic phosphorus compounds is remarkable even in L-type zeolite.

Example 8 A liquid phase chlorination reaction of toluene was carried out in the same manner as in Example 1 except that MoB was replaced with toluene. The toluene conversion rate 3 hours after starting to blow chlorine gas was 5.59 cm,
The selectivity for by-products such as orthochlorotoluene was 315%, and the selectivity for parachlorotoluene was 6 & 7%. Small amounts of methachlorotoluene and dichlorotoluenes were confirmed as by-products other than orthochlorotoluene.

Comparative Example 3 A liquid phase chlorination reaction of toluene was carried out in exactly the same manner as in Example 8 except that tributylphosphine was not present. 3 hours after starting the reaction) /l/ :L 7
The conversion rate was 54.6%, the selectivity for by-products such as orthochlorotoluene was 57.6 tl, and the selectivity for parachlorotoluene was 62.4%.

Claims (1)

[Claims] A halogenated benzene derivative characterized in that an organic phosphorus compound is allowed to coexist in the reaction system when the halogenated benzene derivative is produced by a halogenation reaction of a benzene derivative using faujasite type zeolite and/or L type zeolite as a catalyst. Production method.