JPS6287536A - Chlorination of benzene and derivative thereof - Google Patents

Abstract

PURPOSE:To obtain a benzene derivative substituted by chlorine atom at its para position continuously in high selectivity and high conversion, by using L-type zeolite with a specific potassium content as a catalyst in chlorination of benzene and benzene derivative. CONSTITUTION:Benzene or benzene derivative, for example mono-chlorobenzene, with <=100ppm, preferably <=50ppm water content is chlorinated using L-type zeolite [0.1-0.2 molar ratio (Al2O3/SiO2) and about 8Angstrom effective pore diameter] containing 6-14wt% potassium expressed in terms of potassium oxide as a catalyst to obtain benzene derivative, substituted by chlorine atom at its para position and useful as a raw material for synthesizing various kinds of organic compound in as high as 84-88% selectivity and decrease of chlorine conversion caused by repeated use of catalyst can be suppressed by using said catalyst, which can be repeatedly used.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a chlorination ZJ method for producing benzene derivatives substituted with chlorine at the para position, which are useful as raw materials for the synthesis of various organic compounds. I'm concerned.

BACKGROUND ART Conventionally, as a method for converting benzene and benzene derivatives into salt water, a method using a Lewis acid such as ferric chloride or lj heptimony chloride as a catalyst has been known. In addition to the substituted product, the ortho-substituted product and the trichlorobenzene filter are also used, and the selectivity for the single substituted product is about 60% at most. Another method is to use an iron sulfide melting medium (Japanese Unexamined Patent Publication No. 5
0-Fi4231j'')) A method using selenium or U-lene compounds as a catalyst (JP-A No. 50-34010) has been proposed, but even in this method, the selection rR chamber for the production of rose substitution products is is about 70%.

Furthermore, a method for increasing the selectivity of loose counterfeits was described by JP-A-Sho,
59-1 (No. 13329 contains [, - desired pi A
A method using lights is disclosed. Here, the l-1'lzeA light used as a catalyst is used as an ion exchange intoxicant.
A case is exemplified in which a KL-type olide having a -1-one and C potassium r-Simion is used, and for example, the selectivity of valadichlorobenzene reaches 90% or more. However, when benzene and benzene derivatives are chlorinated using KL-type zeolite, newly prepared L-Kt-type zeolite 1- as a catalyst exhibits high reaction rate and high selectivity. However, when this catalyst is repeatedly used, the reaction rate and selectivity decrease, and at the same time, the formation ω of benzene and benzene derivative chloride adducts increases. . This disadvantage is further aggravated by the coexistence of water in the reaction system.

Invention 1] In view of the current situation as described above, the present invention aims at a method for chlorinating benzene and benzene derivatives that continuously produces a substituted substance with high selectivity and high reaction rate. , potassium j? lii is potassium oxide and 6・-+
4 i (i A base l- (-1 to 11ze Arai 1-) was completed by using.

Structure of the Invention The feature of the present invention is that when benzene and benzene derivatives are chlorinated, potassium-containing f? 1 is potassium oxide, 6-14 suspended base 1-, and 1-type zeolite is used to produce benzene derivatives in which the para position is substituted with chlorine. 3. The L-type zeolite used here Olide has an aluminum oxide/'silicon oxide molar ratio in the range of 0.1 to 0.2, and has an effective pore diameter of about 8.

All of the kabu-ons capable of ion exchange are replaced with potassium (
Then, potassium cum of 1G small Haversent will be included as potassium oxide. The performance of this product as a catalyst is as high as 9Ql'l (or more), but it is not practical because the activity decreases slowly with repeated use of the catalyst. Even if it is reduced to 90% or less, in order to put it to practical use and enable repeated use of 11 culms, it is necessary to adjust the potassium content to 6 to 14 weight percent as potassium oxide.

In carrying out the present invention, 0.19 or more, preferably 0.5 to 0.19 per mole of raw material benzene or benzene derivative
10g of zeolide was used, and the reaction temperature was 20-110℃.
°C1 preferably 50 to 70 °C.

Furthermore, when carrying out the present invention, the catalyst activity is
In order to suppress 1W11+ of I, l polychloride,
The moisture in the raw material benzene or benzene derivative is reduced to 110%.
It is necessary to adjust the content to 0 ppm or less, preferably 50 ppm or less. Of course, even when handling the catalyst, care must be taken to avoid adsorption of moisture, etc. in the air.

The D;1 rice used in the present invention includes benzene, U-nochlorobenzene, Mop[]L-benzene, monofluorobenzene, 1-luene, nibblebenzene, 1n-benzyl, anisole, and the like.

Effect of the invention By adjusting the potassium content as described above as a catalyst, 1'
Knee L-'S'! When benzene and benzene derivatives are chlorinated using zeolites 1 to 1, the selectivity of products with chlorine substitution at the para position is 84 to 88.
%, which is lower than 90% or more of KL-type UA Lii, but the decrease in the reaction rate of chlorine when the catalyst is used repeatedly is small. For example, when chlorinating benzene using the catalyst of the present invention, if the water in benzene is controlled to 10 ppm, the selectivity for producing benzene is about 85%. However, after repeating the reaction 25 times, the reaction rate for r = elementary was as high as 90% or more. On the other hand, K
When L-type t-<light is used, the selectivity of paradichlorobenzene is 90%, but the reaction rate of chlorine already drops to below 90% after repeated use.

In addition, the selectivity of the product substituted at the para position means that when the Ili material is benzene, the selectivity of the product substituted at the para position is
It is the proportion of colbenzene, and when the raw material is a monosubstituted benzene such as Toluene, it means the proportion of the para-substituted product in the monochloro-substituted product.

Next, non-limiting embodiments of the invention will be described.

Example 1 In a brown four-bottle flask equipped with a reflux condenser, a temperature δl, a stirrer and a gas blowing tube, L-type zeolite 1 having a potassium content Φ of 11.1 weight percent as potassium oxide was added.
Monochlorobenzene 25 with 2.5g and 10ppm water content
0 J was added, and while stirring at 70°C, chlorine was blown in at a rate of 0.6 mol per hour. The reaction was completed after 3 hours, and the catalyst was filtered off under a nitrogen atmosphere. Wash the reaction solution with water (crotch, gask []
Seven samples were analyzed.

The filtered catalyst was washed with an appropriate number of benzene, and then washed with 250 g of benzene.
¥1! ' was used for reaction.

At the end of the reaction of repeated anti-17δ carried out as in l1, at time Y, add +3 to l! The reaction rate and selectivity of benzene and polychloride are shown in Table-1. The results are shown in Table-2. Note that the force per unit weight is the potassium oxide equivalent value.

Table 2 Example 3 Example 1 was repeated. However, Table 3 shows the results when the water content in benzene is changed using 61Φ1 percent 1-1) lizeolite as potassium oxide as a catalyst and changing the water content in benzene. Table 3 Example 4 Table 4 shows the results obtained by repeating Example 1 and changing the reaction temperature.

Table 4 Example 5 Table 4 shows the results when Example 1 was repeated and the display medium was changed.
1J, shown in 5.

Table 5 Example 6 The results of chlorination of benzene and benzene derivatives under the same reaction conditions as in Example 1 are shown in Table 6. Japan License Agency Officer Uga Michibu Tonka 1, Incident Indication Patent Application No. 228150 of 1985
Tan ≧ 8 Title of the invention Method for chlorinating benzene and benzene derivatives 3, Relationship with famous case for amendment Patent applicant name (110) Kureha Kagaku 2 [Gyo Co., Ltd. 1,
Agent 1-1-14 Shinjuku, Shinjuku-ku, Tokyo
Yamada Building (zip code 160) Telephone <03> 34
M-86235, Date of amendment order Invention Specification 1, Name of invention Benzene and benzene derivatives j! Chemicalization method 2, Claims (1) Potassium, ＼containing potassium oxide is 6~
14 A method for chlorinating benzene and benzene derivatives characterized by using 1-type zeolite 1-, which is a small hanging perhint, as a catalyst.
The method according to claim 1, wherein the amount is 00 pp or less.

(3) The method according to claim 1 or 2, wherein the benzene derivative is monochrome [J benzene.

3. Detailed Description of the Invention Industrial Field of Application The present invention is directed to the production of bembin derivative I) in which the bara position is substituted with chlorine, which is useful as a raw material in the synthesis of various organic compounds. Concerning disguise method.

BACKGROUND ART Conventionally, as a method for hydrogenation of benzene and benzene derivatives, for example, a method using a Lewis acid such as ferric chloride or antimony pentachloride as a catalyst has been known. In addition to this, ortho-substituted products, tri[10-benzene, etc.] are produced as by-products, and the selectivity for the production of para-substituted products is about 60% at most. Other methods include a method using an iron sulfide catalyst (JP-A-50-64231 j'l';) a method using selenium or a selenium compound as a catalyst (JP-A-1, J-No. 50-34010)
) have been proposed, but even with these methods,
The selectivity for the production of para-substituted products (approximately 170%).

Furthermore, as a method to increase the selectivity of rose substituted products, JP-A No. 5
No. 9-163329 discloses a method using L-type pyaraite as a catalyst. Here, a case is exemplified in which Kl-type zeolite is used as a catalyst and Kl-type zeolite has potassium ion as an ion-exchangeable cation. ing. However, when benzine and benzene derivatives are chlorinated using KL-type biolide, when the newly prepared KL-type zeolite 1 is used as a catalyst, rose substituted products can be obtained with high reaction rate and high selectivity. 15
1, but when this catalyst is used repeatedly, the reaction is
At the same time as the selectivity decreases, there is the disadvantage that the production of benzene and chlorine adducts of benzene derivatives increases. This disadvantage is further aggravated by the coexistence of water in the reaction system.

Purpose of the Invention In view of the above-mentioned current situation, the present invention aims to provide a method for chlorinating benzene and benzene derivatives that continuously produces %AjΔ with high selectivity and high reaction rate using a substituted substance as a catalyst. , potassium-containing tij is 6 to 1 as potassium diluted
It was completed by using L-type zeolite, which is 4 small skewers and 1 to 1.

Structure of the Invention The present invention is characterized in that when benzene and benzene derivatives are chlorinated, an L-type zeolite having a potassium content of 6 to 14 fi [i percent 1-] as potassium oxide is used in the chlorination of benzene and benzene derivatives. The purpose is to convert a benzene derivative substituted with chlorine at the 51j i'i position.

The aluminum oxide/silicon oxide used here has a ratio of 01 to 02, and an effective pore diameter of about 8.

If all ion-exchangeable cations are replaced with lithium, then 1f3.7'[im percent of potassium will be included in the total as potassium oxide. The performance of B as a catalyst is as high as 90% or more for each of the 122 prefecture substitutions in the rose position, but for repeated use of the catalyst, filter-activated bamboo is extremely low, making it impractical. do not have. Even if we reduce the salt water replacement rate to over 90% ■ζ, there are concerns about practical use! In order to make it possible to repeatedly use the culm, it is necessary to adjust the potassium content to 6 to 14 Φ 1% (11% potassium).

In carrying out the present invention, 0.19 or more per mole of raw benzene or benzene derivative, preferably
Using zeolite 1-1, the reaction temperature was 20-1.
The temperature is 10°C, preferably 50 to 70°C.

Furthermore, when carrying out the present invention, the catalytic activity is maintained at 11+1! , ; In order to suppress the by-product of accumulated products, the water content in the raw benzene or benzene derivative was reduced to 1100pp.
Hereinafter, it is necessary to adjust the pH to preferably 50 ppH or less. Needless to say, care must be taken to avoid absorbing moisture from the air while handling the catalyst.

In the present invention, the raw materials 11 used in 15 are benzene, U-nochlorobenzene, V-nobrobenzene, monochlorobenzene, 1-1-1 chlorobenzene, benzyl chloride, anisole, and the like.

When benzene and benzene derivatives are chlorinated using type 1 zeolite 1~ with the potassium content adjusted as described above as the effective catalyst of the invention, it is found that ``one position and one para position are substituted.'' Product selectivity L; t8-4 to 88%, KL-
Although the rate of 90% 1-J to type ZA is low, the decrease in t4 element in the reaction chamber when the melting medium is repeatedly used is small. For example, when colobenzene is chlorinated using the catalyst of the present invention, the water content in monochlorobenzene is reduced to 10 pp.
! The selectivity for the production of baladichlorobenzene is about 85% when controlled at 25%, but even if one reaction is repeated 25 times, the reaction rate of chlorine is as high as 90% or more. On the other hand, when KL-type zeolite is used, the selectivity of Balajik's lobenzene is approximately 90%, but the reaction rate of chlorine has already decreased to less than 90% after 6 repeated uses. The selectivity of a product substituted at a position is the proportion of bala-dichlorobenzene in the dichlorobenzene produced when the raw material is benzene, and when the raw material is a mono-substituted benzene such as toluene, it is the proportion of the monochloro-substituted product. It means the proportion of jackfruit substitutes in

Next, a northernmost embodiment of the present invention will be described.

Implementation 1A1 A four-liter flask equipped with a reflux condenser, a temperature gauge, a stirrer, and a gas blowing tube has a potassium content of 11.1 percent by weight as potassium oxide - JXl! v-s
Lie 1-12.5a and moisture is 1 opHm no E-/'
) D 250 J of Lobengen was added, and while stirring at 70°C, chlorine was blown in at a rate of 0.6 E per hour. 3
The reaction was completed within a certain period of time, and the catalyst was filtered off under a nitrogen atmosphere.

After washing the reaction solution with water, it was washed with Gas Chroma 1 to Graphie for minutes vi.
Shita.

The filtered catalyst was washed with an appropriate amount of monochlorobenzene, mixed in 250 g of monochlorobenzene, and subjected to reaction.

Table 1 shows the chlorine reaction rate, the selectivity of baladichlorobenzene, and the production variation [10 mole % of added chlorinated product with respect to ben U] at the end of the repeated reaction in which ↑j was achieved as described above.

Table 1 Example 2 Table 2 shows the results of the 'Q combination by repeating Example 1 and changing the potassium content t3 in the catalyst. Note that the force 1 is the σ value in terms of potassium oxide.

Table 2 Example 3 Example 1 was repeated. However, Table 3 shows the results when a 1-type zeolide with 61% by weight of 3% potassium as potassium oxide was used as a catalyst, and the water content in the raw material L-nocro[]benzene was changed.

Table 3 Length JL=4 Table 4 shows the results obtained by repeating Example 1 and changing the reaction temperature.

Table 4 Example 5 Example 1 was repeated and the results when i!m was changed are shown in Table 5.

Table 5 Example 6 Table 6 shows the results of salt hatching carried out on benzene and benzene derivatives in the same reaction column 1'10 as in Example 1.

Claims (3)

[Claims] (1) A method for chlorinating benzene and benzene derivatives, which is characterized by using L-type zeolite having a potassium content of 6 to 14 weight percent as potassium oxide as a catalyst. (2) The water content of benzene and benzene derivatives is 1
The method according to claim 1, wherein the amount is 00 ppm or less. (3) The method according to claim 1 or 2, wherein the benzene derivative is monochlorobenzene.