WO1991016284A1

WO1991016284A1 - Process for producing alkenylbenzene and derivative thereof

Info

Publication number: WO1991016284A1
Application number: PCT/JP1991/000542
Authority: WO
Inventors: Keizo Shimada; Koji Sumitani; Seiji Itoh
Original assignee: Teijin Limited
Priority date: 1990-04-25
Filing date: 1991-04-23
Publication date: 1991-10-31

Abstract

A process for producing efficiently alkenylbenzene, which comprises reacting alkylbenzene with 1,3-butadiene in the presence of a catalyst prepared by the dispersion treatment of an alkali metal with an inorganic potassium salt in the substantial absence of oxygen and water.

Description

m Itoda »

《Title of Invention》

Process for producing alkenylbenzene and derivatives thereof

"Technical field"

The present invention relates to a method for safely and efficiently producing alkenylbenzene by reacting alkylbenzene and butadiene in the presence of a recovery metal; more specifically, for example, the reaction of o-xylene with 1,3-butadiene. Reaction: ^5-- , o- ^¾ -ryl, which is alkenylbenzene obtained by this-', 1-benthene cyclizes it to dimethyltetralin, which is dehydrogenated, and This is a high industrial value chemical compound that can be converted into valuable 10-phthalene dicarboxylic acid as a polymer material by oxidation, and the present invention is a method for producing such valuable material. It is a measure

《Background technology》

Conventionally, a method for producing monoalkenyl benzene by reacting an alkylbenzene with i, 3-butadiene in the presence of an alkali metal is known (see US Pat. No. 3,247,47).

However, the above-mentioned method has a disadvantage that an expensive metal-based reactor must be used for 1 in order to obtain monoa with high yield; In order to solve the problem, when 1,3-butadiene is blown into alkylbenzene to cause a reaction, the use of expensive metal power lumps with the use of metal lumps and metal thotrium as catalysts is small. (See Japanese Patent Publication No. 34-34, U.S. Pat. No. 3, U.S. Pat. No. 3):

However, all of these methods use metal reams directly, so they are highly reactive to air, oxygen, water, etc., and ignite just by contacting these compounds, which is dangerous for disaster safety. particularly ten thorium over potassium © beam <-ヽa - _K: ten, '/ click> alloy oxygen, high activity to water, even ignited in contact with 〇 _2, H ₂ O and the like of trace,阇Extremely dangerous in the presence of near-flammables (petroleum)-a catalyst system that does not use metal powder is described in British Patent 126928G (April 6, 1972). Gen is said to have an inhibitory effect on the side-chain alkylation of aromatics with olefins using sodium and anhydrous magnesium compounds such as potassium carbonate as catalysts.

《Object of the invention》

The present invention solves the above-mentioned problems, and aims to produce alkenylbenzene in high yield without directly using an expensive metal rim having a high risk of ignition. Highly active and highly selective catalyst for reaction By reacting alkylbenzene with 1,3-butadiene, the production of by-products which is difficult and difficult to separate from the target product is suppressed, and the high-purity target product, i.e. A method for producing benzylbenzene in a high yield. A method for cyclizing the alkenylbenzene to produce alkyltetralin and a method for producing an alkyldephthalene by dehydrogenating the alkyltetralin. The purpose is to provide

《Disclosure of the invention》

The present invention relates to a catalyst obtained by reacting an alkylbenzene with 1,3-butadiene in the presence of a catalyst to produce alkenylbenzene, in which an alkali metal is dispersed as a catalyst and an inorganic lithium salt is dispersed. A process for producing alkene benzene, comprising reacting alkylbenzene with 1, butadiene in an environment in which oxygen and water do not substantially exist.

That is, in the production of alkenylbenzene by reacting alkylbenzene with 1,3-butadiene, Alkali metal is used as a catalyst without the substantial presence of oxygen and water, and high-temperature calcination dehydration is performed. By reacting alkylbenzene and 1,3-butadiene in the presence of a dried fine carbonic anhydride powder and a supported catalyst dispersed at a specific ratio, it is difficult and cumbersome to separate it from the target product. High by-products A method for producing alkenylbenzene, characterized by producing lukenylbenzene in high yield. Hereinafter, the present invention will be described in detail:

The starting material used in the method of the present invention is an alkylbenzene having 1 to 2 methyl or ethyl groups in the alkylbenzene benzene nucleus. Specific examples of the compound include toluene, ethylene pentene, o-xylene, m-xylene, p-xylene. Each of these alkylbenzenes is preferably used alone, and if a mixture is used, it becomes difficult to separate the target product from the reaction product, alkenylbenzene, with good purity:

For example, in the reaction of o-xylene and 1,3-butadiene, the purity of the target product can be reduced if alkylbenzenes such as toluene, p-xylene, m-xylene, and ethyl / benzene are mixed as impurities. Therefore, the purity of o-xylene is 95% or more, preferably 98. The above is preferable. However, a small amount of hydrocarbons having no alkyl group such as benzene-cyclohexane may be mixed:

Similarly, in the case of using tonolen, ethylene benzene, m-xylene.-xylene, the purity of each single product is 95 or more, preferably 9 S ° o or more. The incorporation of V-free hydrocarbons is possible: The starting material alk / lebenzene is preferably dehydrated and used in the reaction. As a dehydration method, for example, adsorption separation using a suitable drying agent (eg, activated aluminum, silica gel, molecular sieves, activated carbon, etc.) There is a method of dewatering by pre-contacting with cryogenic, cryogenic metal, or metallic lithium or metal power rim. The lower the amount of water in the raw material, the better, and the curl which is the usual method for measuring water content It is particularly preferable that the sensitivity is less than the measurement sensitivity of the social method, for example, several PPm or less.

In the present invention, 1,3-butadiene may be produced by any method, and 1,3-butadiene may be of any purity; for example, crude obtained by dehydrogenation of butane or butene. Butadiene can be used as it is, or 1,3-butadiene purified by a method such as extraction of the crude butadiene can be used. Also, 1,3-butadiene is dehydrated and reacted. Dehydration methods include a suitable drying agent such as activated aluminum, silica gel, molecular sieves, charcoal, etc., or cryogenic separation.] 3- The lower the water content in 'butadiene', the better, especially less than a few PP in

: *: The catalyst used in the invention for the reaction between alkylbenzene and i, 3-butadiene is a catalyst obtained by dispersing an alkali metal with inorganic powder ^: 'pium salt fine powder. The metal / recovery metal is preferably 10% metal, and the higher the purity, the better, but a trace amount of calcium.A purity that is acceptable even if it contains magnesium, preferably 99.0% or more. Is preferred

Potassium oxide, potassium hydroxide, potassium carbonate, chloride chloride, and mixtures thereof can be used as inorganic powders used as dispersants. Particularly preferred are potassium acid and potassium chloride. In some cases, a mixture of the two may produce a favorable effect. These charcoal it-lium and potassium chloride may contain about 10 equivalents or less of sodium carbonate, sodium chloride and potassium chloride. The average particle size of the inorganic potassium salt as the dispersant is preferably 100 μm or less, particularly preferably 10 to 0 μm. The particle size can be adjusted by a sieve or the like.

Carbonate in calcium carbonate. Lithium chloride. In some cases, the function of the catalyst may be improved. When acidium is used as a mixture of sodium carbonate and calcium, 10: 1 to 1: Used in a weight ratio of 10, preferably to 10: 1 :: 1 weight ratio:.

The ratio of the alkali metal and the inorganic salt of the dispersant may be dispersed and supported at the following ratio, but the final ratio of the metal 10 ^k "is i to 30 o by weight, preferably: 2ΰ ο, more preferably: ~ 10 c

The inorganic potassium salts used, for example KCO; i, K 2 CO 3-a.2 CO 3, KCO-:-\ a. C: K 2 CO 3-KC 等, etc. needs to be dried to T minutes and also improves the activity as a supported catalyst In this case, it is preferable to bake and dry at a high temperature of 500 ° C to 20C.

For the preparation of the supported catalyst comprising an alkali metal and an inorganic lithium salt used in the method of the present invention, for example, a method of dispersing and supporting 10 km of metal in fine particles of an inorganic lithium salt is adopted.

As the method, an inert solvent dispersion-supporting method is preferred. The inert solvent dispersion-supporting method is used to uniformly prepare sodium metal in an amount of 0.1 to 30% by weight based on the inorganic lithium salt. For this purpose, it is preferable to adopt the masterbatch method or the method of mixing individual dispersion liquids. That is, for example, when 3 weight 5 of metal is dispersed and supported, 3 parts of metal A method is adopted in which 97 parts of carbonic acid lime is simultaneously added to 1000 parts of solvent o-xylene and stirred at a high speed of 110 to 13 G, but a dispersion is prepared in advance by dispersing at an appropriate dispersion ratio, and the dispersion is prepared. Further, a method of dispersing in a solvent by a carbon dioxide beam can also be carried out. Also, a solution obtained by emulsifying and dispersing 3 parts of metal sodium with 300 parts of o-xylene and 97 parts of potassium carbonate ( ) Mix the liquid dispersed in 700 parts of xylene. . And Ru can also perform the method of dispersing the supported metal Juto helium 3 parts of carbonate force Riumu 4 parts c '- alkoxy;.

500 parts of liquid emulsified and dispersed and 50 parts of carbon dioxide A method of mixing and dispersing a liquid dispersed in 500 parts of ren can be performed: Even when a solvent is not used, the dispersion is carried out by a master basin and a multi-layer method, and further, an inert solvent dispersion is carried out. This makes it possible to prepare a uniform catalyst having excellent activity and selectivity. As an inert solvent, it is industrially preferable to use alkylbenzene used as a reaction raw material.

The dispersed catalyst uniformly dispersed and supported as described above is prepared by pretreating a mixture with an α / lekilbenzene catalyst with O to 20 GC for 1 to 5 hours before introducing 3-butadiene and reacting. This can improve activity :.

In the method of the present invention, the reaction between alkylbenzene and 1,3-butadiene is carried out in the absence of water and oxygen. Therefore, the raw materials introduced into the reaction system from outside the system, namely, alkylbenzene and i, 3-butadiene are used. It is desirable to dehydrate as described above. Further, in order to make the space of the reaction system substantially free of oxygen and moisture, it is necessary to fill the space with a dry inert gas such as dry nitrogen or dry argon. Or under pressurized reaction conditions above the boiling point of alkylbenzene, it is desirable to fill the space with vapor such as alkylbenzene.

In the present invention, the reaction is preferably carried out at a temperature in the range of 5 to 2 G. When the reaction temperature is lower than 200, the reaction time is longer, and when the reaction temperature is higher than 200, more by-products are produced. Not: Preferred reaction temperature is 80 iSG. The reaction ratio of 1,3-butadiene to alkylbenzene can be selected appropriately under normal conditions-for example, alkylbenzene: 13-butadiene i: It can be carried out in the range 0.001 0., preferably 1: 0.G1 0.3, particularly preferably 1: 0.0: G.2.

The reaction time is in the range of 0.05 to 10 hours. The reaction time is as follows: catalyst amount <g—catalyst '.' G-alkylbenzene, catalyst composition (g—deuterium g—inorganic power. Lithium salt) : '.', Which is related to the reaction temperature (in) and the ratio of alkylbenzene to 1,1-butane-diene (g-alkylbenzene 'g-1,3-butadiene). An appropriate time is selected depending on the usage pattern of, for example, the presence or absence of circulating use. In general, if the value of the above factors decreases, the reaction time will be longer, but the preferred reaction time is 0.2 to S hours. Preferably G.5 4 hours

In the reaction, starting from the beginning, alkylbenzene, i.3 monobutadiene and a catalyst are simultaneously charged and reacted. 'Be -'-' reaction, alkylbenzene and catalyst are charged first, and then 1,3-butadiene is reacted for a short time. Semi-batch reaction to introduce quantitatively as the process progresses, continuous reaction to continuously introduce alkylbenzene,:-phthalene and catalyst into the reactor ぃ It is possible to adopt the above reaction method, or to combine them in the same way. Good, but Semiba ,, 'Ji reaction or Ren ^ Reaction is preferred

In the continuous reaction, two types are adopted. (Cimoto's method) In the method, the catalyst is a solid fine powder catalyst obtained by dispersing a metal stream of 10 to an inorganic porous salt. There are two methods: a method in which benzene is fed and 1,3-butadiene is introduced into α / rekirbensen to carry out a continuous reaction, and a method in which a catalyst is dispersed in a reaction system and stirred.

In the continuous reaction mode, any of a tubular reactor, a column reactor, and a tank reactor may be used. A preferable continuous reaction method is to provide a plurality of reaction zones and to use 13-butadiene. It is a contract cross-flow type continuous reaction system in which a fixed amount is introduced into each reaction zone;

The reaction operation may be carried out as long as the alkylbenzene and:.: Butadiene can be sufficiently contacted and mixed in the presence of the catalyst, and there is no particular limitation. 1,3-butadiene is likely to adhere to a resinous or gum-like substance presumed to be a 1,3-butadiene polymer near the inlet of butadiene, causing a clogging phenomenon. 1,3-butadiene mixed with alkynylene benzene, for example, liquid phase mixture of liquid butadiene here / rexbenzene, gaseous 1,3—butadiene and liquid α / lekybenzene and ku) gas-liquid mixture The method of introducing 1, 3-butadiene and alkirbensen 1,3-butadiene can be supplied to the reaction space or the reaction zone space, and the absorption reaction can be performed on the surface of the reaction solution where the catalyst is present to prevent the clogging phenomenon. An inert gas from which oxygen and moisture have been removed, such as nitrogen, argon, and hydrogen, is suitable as the carrier gas, which can be blown together with the carrier gas and increase the stirring effect at the same time.

The reaction can be preferably carried out by providing appropriate stirring. However, 1,3-butadiene ′ can be introduced into the reaction system in a gaseous phase, and the gas can have a stirring effect. The agitation should be of a strength necessary to uniformly disperse the catalyst in the reaction system and to uniformly mix the reaction material and the reaction product. In the liquid phase dispersion reaction system In the case of reaction, after the reaction, the used catalyst can be separated from the reaction product system by a known means, for example, centrifugal sedimentation, gravity sedimentation, or a liquid-solid phase at a lower temperature. Any known means such as solid phase separation from water, eg filtration, centrifugation, etc. may be used: The separated catalyst can be recycled and reused in the reaction system

When the catalyst deactivates and loses its catalytic function, the phase of lithium carbonate and chloride is partly dehydrated due to the deactivation of the metal trim. Oxidized and baked with glutin adhered, converted to carbonates, it can be produced and reused. * According to the inventive method, 5-toluene-benthene is synthesized in the reaction of toluene with i, 3-butadiene, and in the reaction of o-xylene with 1,3-butadiene,

(o-trible) 1-pentenka p-xylene and 丄, 3—phthalene reaction 5— (p—tolyl) 1 benchin is in—xylene and 1,3-butadiene 5— (m-trinole) Penten is synthesized, and 5- (phenyl) -hexene is synthesized in the reaction between ethylbenzene and butadiene.

The alkenylbenzene, which is the target product of the present invention, is subjected to a cyclization reaction and then dehydrogenation as described above, whereby a compound useful as a raw material for a pharmaceutical or a polymer material, that is, mosoalkylnaphthalene ′, In this case, the purity of benzene and hexene in cyclizing fluoropentene and ethanol liubenzone is a problem. The position of the so-called arylalkenorefinous double bond of phenylenebenzene, phenylhexene, and triphenylene is 1 or 2, but In the conventionally known method, isomers having different positions of the olefinic double bond, for example, in the reaction of o-xylene with butadiene, 5— (o-lithre) 1 pen 'ampine (1). — R-ril ' ― 丁丁、） τ> — \ —! , Ri /, ichibencho no '.>', 5-(o-tori) ichi pen dry 4) etc. By-products and contaminants: other toluene, ethylbenzene.

Phenylpentene and phenylhexene synthesized by the reaction of P-xylene, m-xylene and butadiene. Also in lylhthene, isomers with different olefinic double bond positions are by-produced. Among these isomers, those in which the olefinic double bond is in the 1 or 2 position can be cyclized to be converted to alkyltetralin, while others are converted to alkyltetralin. Not only does it not react with the target product, alkyltetralin, but also as a high-boiling product, reducing the yield of the target product. '

Moreover, it is extremely difficult to remove the isomer in which the above-mentioned olefinic double bond is located at positions 3, 4, and 5 from alkenylbenzene as the target product of the method of the present invention. For example, o-xylene and I, 3 Reaction mixture with 1-butadiene, ': The target products are 5-(o-tolyl) 1-pentene-one (2) and 5-- <o-tolyl) 1-pentene-one (1)) The crude distillation was performed using a rectification column with 50 theoretical plates and a reflux ratio of 2 [! On the other hand, the isomers can hardly be separated even by rectification in the reaction. On the other hand, in the reactants obtained by the method of the present invention, there are very few such difficult-to-separate by-products. Is very high

Alkenylbenzene 'is known per se in the known manner, by contacting acid catalysts such as silica and solid phosphoric acid. By contacting with an acid catalyst such as silica aluminum at a temperature of ~ 25 ° C for 10 seconds to 10 hours. ring Can be converted to alkyltetralin

Alkyl titraline is contacted for 5 seconds to 10 minutes at a temperature of 350 to 45 GC with a deoxidizing catalyst such as aluminum chromia, PtAi0--, etc. By dehydration, it can be reduced to alkyl 10-phthalene

Alkyl phthalene can be prepared by a method known per se, that is, by using a solid acid catalyst such as silica-aluminum, ZSM-5, Y-type zeolite, or H-type morphite at a temperature of 2Gi to 4 ° C for 5 seconds to 5 seconds. Can be isomerized by contacting for 10 hours, for example, 1,5-dimethylnaphthalene can be converted to 2,6-dimethyl10-phthalene

<< Best mode for carrying out the invention >>

In the present invention, the catalyst used for reacting α / lekybenzene with 1,3-butane is a catalyst obtained by dispersing a metal of sodium using carbon dioxide and alkylbenzene as a solvent. It is preferable to use

ADVANTAGE OF THE INVENTION According to the present invention, it is possible to produce dimethyl-10-phthalene, a compound useful as a raw material for a polymer material, from alkylbenzene as follows.

That is, o-xylene and 1,3-butadiene are reacted with a catalyst obtained by dispersing an alkali metal with an inorganic lithium salt to produce 5-o-trile> bentenene, and: 5 ”,“ Koiyai 5 — (o — Trinole) To produce 1,5-dimethyltetralin, and then dehydrogenate the 1,5-dimethyltetralin in a manner known per se to give 1,5-dimethyltetralin. After producing phthalene, the 1,5-dimethyl-10-phthalene can be isomerized to produce 2,6-dimethyl-10-phthalene.

Further, by oxidizing the 2,6-dimethyl-10-phthalene, ten-phthalene-2,6-dicarboxylic acid can be produced.

"The invention's effect" . '- '

The reaction product obtained by the method of the present invention has very few by-products which are difficult to separate, and therefore the yield of the cyclization reaction product is extremely high.

According to the method of the present invention, a metal decadmium is calcined at a high temperature and dehydrated at a specific ratio with a fine powder of an inorganic potassium salt which is dehydrated by heating at a high temperature without substantially allowing oxygen and moisture to be present. According to the method of the present invention, it is possible to produce alkenylbenzene by reacting alkylbenzene with 1,3-butadiene in the presence of a catalyst which has been prepared, and it is expensive and has a high risk of ignition. Na—K: Ten times, it is difficult to separate the target product from the target product without directly using a nockey alloy, with high activity and high selectivity for the alkenylation reaction. The production of complicated by-products was suppressed, and it was possible to produce high-purity target products in high yields. The catalyst used in the method of the present invention has an advantage that the catalyst can be easily separated without troublesome and troublesome work when preparing the catalyst, but the cost is low.

"Example"

Hereinafter, the present invention will be described in detail with reference to examples.

Needless to say, the present invention is not limited to these examples. In the following examples and comparative examples, the yield and purity of the target compound are defined as follows. Simply "parts" means parts by weight.- (Yield and purity)

After filtering the entire reaction mixture at room temperature, about 5 G 0 g was distilled under a reduced pressure of 22 mm Hg <abs :! in a Widmer rectification column, and a fraction with a rectification column top temperature of 75 C or less,? A fraction of 5 to 170 and a residue were separated: and a fraction of above: was collected as alkenylate of quinylene alkenylated with i.3-butadiene: in a sample of this alkenylate fraction The yield of alkenyl / leuide in the total reaction mixture was calculated from the proportions determined in:

Further, the fraction of the alkenyl compound was analyzed by gas chromatography and the duff method, and the content of 5- (tolyl) pentene ';2:' and 匸 ': 5— (tolyl) benten <1) was determined. Unreacted xylene was less than or not present in the α / refractionated fraction, i: weight or less. Similarly, for the reaction product of toluene and butadiene, the contents of 5-phenylene retentene <1> and 5-phenylene / lenene (2) are determined, and the yield of the desired product is calculated. The yield when using xylenes' ゼンへへへンゼンゼン、は、、ンンン、、、ンンンンンンン

Yield =

Butadiene usage; '

54 (1, 3 — molecular weight of butadiene. ''

160 (Molecular weight of target product) '' The calculation of the reaction product of toluene and butadiene was calculated by the following formula: Yield of target product)

Yield two

1, 3 Amount of butadiene (g ¹ '

54 (ί, 3 Molecular weight of butadiene: '

..146 (Molecular weight of target substance)

<Example 1

(A) Preparation of fine metal particle dispersion

After heating and refluxing in the presence of a metal stream in advance, distillation and dehydration with a molecular sieve, 1000 parts of substantially water-free o-xylene, dry high-purity nitrogen (containing oxygen: pm or less, Content G. 以下 pm or less), removes and removes dissolved Ifi, and then removes the metal 99.95 ° o) 9.0 parts were added, and emulsified and dispersed using an emulsifying and dispersing machine under the above nitrogen atmosphere for 30 minutes to prepare an emulsified dispersion of metallic sodium.

On the other hand, high-purity potassium carbonate (purity 99 or more: 30 U part was calcined and dehydrated at 200 to 400 C for 2 hours, cooled, and then turned into fine particles having a particle size of 45 m. The dehydrated o-xylene was charged into 1000 parts, and the mixture was dispersed in an emulsifying and dispersing machine for 10 minutes to form a carbon dioxide-containing dispersion.

(B) Mixture of metal sodium carbonate and carbon dioxide spheres.Preparation of dispersion The above sodium carbonate fine particle dispersion is stirred at high speed, the above potassium carbonate dispersion is added, heated to 14G, and heated at 140 for 1 hour. Heat treatment to form catalyst dispersion

(C) 5-(o-trile) Benthene synthesis reaction

2,000 parts of o-xylene dehydrated and purified as described above is added to the catalyst preparation solution prepared in <B) above with stirring in a nitrogen atmosphere (total 4000 parts of o-xylene> 14 G to 0: After stirring for a while, 20 g of 1,3-butadiene 2. were introduced over a period of time and allowed to react:

After completion of the reaction, immediately cool to 11 ° C, stop stirring and keep for 30 minutes while maintaining at iiG, to separate the reaction product solution into the catalyst and the target product liquid phase. — Io--Lil) Bentene is distilled under reduced pressure of 22 删 Hg abs to obtain 5-o-

K ') Vv) Bentenc) Yield and Purity

Shown in 1: Examples 2 to S, Comparative Examples 1 to 5>

Examples 2 to 8 and Comparative Examples 1 to 5 were obtained by carrying out the reaction under the same conditions as in Example 1 except that the composition, ratio, amount, reaction temperature, and reaction time of the catalyst were variously changed. Are shown in Tables 1 and 2 below.

See Table 1! Thus, according to the method of the present invention, it is possible to obtain high-yield and high-purity 5— (o-tolyl) pentene.

Every time

'·, »).) 8.0 .3 .1

C Example 9 16 and Comparative Example)

In Example 1, O-xylene was replaced with p-xinine, and the reaction of 1,3-butadiene was performed.

The preparation and reaction of the catalyst were carried out in the same manner as in Example '].

The results are shown in Tables 3 and 4.

Tsu Roh was also, ^ off Ά) off Shikabane ο: Bruno 4ゝψί ^u n ^'1 to Li, one

High yield and high purity 5- (p-tolyl) ben

Ru Rukoto or 'Wa force ^s..

1,. "

i

>

c,

m then i

One;

;

• ■;

¾ ■ 1-!

z

I =! ; X (: Example 17>

(A) Preparation of catalyst

In the present embodiment, a catalyst was used in which a 10-millimeter metal was melted, supported on solid-free fine-particle carbonic acid rim, and further dispersed in ethylbenzene. That is, high-purity lithium carbonate (purity: 99. '%) 400 parts (weight) was baked and dehydrated for 5 hours at 400 to 5C'G, and after cooling, finely divided to an average particle size of 45> urn, 15 parts of metallic deuterium was added, and the mixture was added under a high-purity nitrogen atmosphere. 110. After dispersion treatment with C for 60 minutes, the catalyst was further treated with 13G for 60 minutes in the presence of

(Β) δ-(Phenyl) monohexene synthesis

To the catalyst prepared in (Α) above, 4,000 parts of ethylenebenzene dehydrated and purified as in Example 1 was added, and 135 to 145 parts were added. 205 parts of 1-butadiene was introduced and reacted over a period of time.

After completion of the reaction, the reaction mixture was immediately cooled to 8 (cooled to TC, kept at that temperature, stopped stirring, and allowed to stand for 30 minutes to separate the reaction product liquid into a catalyst and a liquid phase of the target substance. The desired product 5—Fluene hexene was distilled under reduced pressure of 25 niDiHg abs to determine the yield and purity. As a result, the purity was 98.5 98 and the yield was 88.5%. ,

For comparison, a similar reaction was carried out using a catalyst in which only metallic tantalum was melted and supported on solid fine-grain potassium carbonate, that is, high-purity lithium carbonate <pure Degree 99.9 c,) 400 parts (weight) baked for 5 hours at 40G 50G: After dehydration, after cooling, atomized to a particle size of about 30G 50 () bam, add 15 parts of metallic sodium to 15 parts and add high purity nitrogen When the reaction was carried out in the same manner as in Example 17 using a catalyst which had been subjected to a dispersion treatment at 11 G for 60 minutes in an atmosphere, the yield of the desired product was 0 ° 0.

The reaction between toluene and 3-butadiene was carried out at a reaction temperature of 130 to 14 ° C. using a metal sodium-potassium carbonate dispersion treatment catalyst prepared under the same conditions as in the operation method of Example 17.

Consequently .DELTA.5? ₀ yield purity 9δ. 5% of 5-Fuweniruben Ten were obtained.

This example describes the synthesis of 2,6-dimethyl'-dephthalene by cyclization, dehydrogenation, and isomerization of 5-<o-tolyl) monobenthene:

(A) Synthesis of 1,5-dimethyltetralin by cyclization of 5- (o_tolyl) -pentene

The cyclization reaction was carried out using a 10% solution of 5- (o-tolyl: 1-pentene in toluene obtained in Example 1 having a purity of 99.0%: using solid phosphoric acid as a catalyst, and the reaction temperature. 15G

As a result, the conversion rate of the raw material was 10ij <: The selectivity for the formation of the cyclized product, 15-dimethyltetralin, was ¾ or more. 2f

(Dehydrogenation of B i, 5 -dimethyltetralin: Synthesis of ό-dimethyldecaphthalene

Obtained by the method of the above (A); The dehydrogenation reaction was performed using a solution of 0.3-o P,, AiO 3 as the hydrogen catalyst, and 40G in a hydrogen atmosphere. 1.5-dimethyl 10-phthalene at conversion 99

, F.P, + Π O -r;> ι-) jh 1 'l ^ i. Β_.,-.

Hachisao 4 /; - _0,丄':. Over emissions - non-placement' Bruno Bruno Reno ΛΤ 1 cun, :)

(C) Synthesis of 2, π-Dimethylnaphthalene by Isomerization of 1,5-Dimethyl-10-phthalene

An experiment was performed to synthesize 2,6-dimethyl-10-phthalene by isomerizing 1,5-dimethylnaphthalene obtained by dehydrogenation according to the method (B) described above.

H-type morte 'Tith 3G ^: ' at a temperature of 350 ° C / 10 ° / leene solution of 1, -dimethyldecaphthalene at a temperature of 350 ° C. As a result of carrying out the isomerization reaction,-dimethyl dephthalene i0,

Dimethyl dephthalene '43 ?. , 1,0-dimethyl 10 tan 44% and other 10-phthalene compound 3ο were obtained as a compound. This was crystallized and purified to give a purity of 'c.-, -Dimethyl 10 50 ^ο ο of phthalene collected

Claims

The scope of the requiem

1. When alkylbenzene and 1,3-butadiene are reacted in the presence of a catalyst to produce alkenylbenzene, a catalyst obtained by dispersing an alkali metal salt with an inorganic lithium salt is used as a catalyst, and A method for producing alkenylbenzene, comprising reacting alkylbenzene with 1,3-butadiene in an environment substantially free of oxygen and water.

2. The method according to claim 1, wherein the alkylbenzene is at least one of toluene, ethylbenzene, 'o-xylene, p-xylene, and m-xylene.

3. The method according to claim 1, wherein the aluminum metal is sodium.

4. The production method according to claim 1, wherein the inorganic lithium salt is a carbonated lime and / or a chlorided lime.

5. The production method according to claim 1, wherein the dispersion treatment is performed by an inert solvent dispersion supporting method.

b. The method according to claim 5, wherein alkylbenzene is used as the inert solvent.

7. A method for producing alkyltetralin, comprising cyclizing alkenylbenzene obtained by the method according to claim 1.

8. Al obtained by the method described in claim 7 Process for producing alkyl tertalene by dehydrogenating quiltetralin