JPH0466547A - Production of alpha,alpha.alpha'-trialkoxyxylene - Google Patents

Abstract

PURPOSE:To industrially and readily obtain the subject compound by placing an alkaline substance and a lower alcohol in a reaction system of a batch reactor, then adding and reacting alpha,alpha,alpha'-trichloroxylene therewith in the presence of the alkaline substance both during and after the reaction. CONSTITUTION:alpha,alpha,alpha'-Trichloroxylene is reacted with a lower alcohol to provide alpha,alpha,alpha'-trialkoxyxylene. In the process, an alkaline substance (especially a compound selected from hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals) and the lower alcohol are initially added into the reaction system of a batch reactor. The alpha,alpha,alpha'-trichloroxylene is then added and reacted therewith to carry out the reaction always in the presence of the alkaline substance both during and after the reaction. Apparatus materials made of inexpensive stainless steel can be employed by using the aforementioned method and equipment cost can be advantageously reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing α, α, α'-trialkoxyxylene. More specifically, when reacting α1αα′-trichloroxylene with a lower alcohol, an alkaline substance is always present in the reaction system during and after the reaction. This relates to a manufacturing method.

α,α,α'-Trialcoquinokylene is a characteristic compound having an alkoxymethyl group and an acetal in one molecule, and is very useful as a raw material for phenol resin and a crosslinking agent, for example.

[Conventional technology]

Conventionally, when producing α, α, α'-trialcoquinokilne by reacting α, α, α'-trichlorogysolene with a lower alcohol, expensive nonmetallic materials with strong α, α, α eating properties were used. equipment costs are always high.)
-There was a problem.

[Problems to be solved by the invention] The purpose of the present invention is to solve the problems of α, α,
The object of the present invention is to provide an industrial method for producing α' trichloroxylene. That is, it is desirable to provide an industrial production method that can use α, α, α1-lichlorquine and a lower alcohol with low equipment costs.

A Step to Solve Problem C The present inventors have made extensive studies to achieve the above object and published the present invention in '9.

That is, the present invention provides a method for producing α,αα"I-realcoquinokydylene by reacting α,α,α'-trichloroxolene with a lower alcohol. Adding an alkaline substance (1] u, 1] ico, α, αtr'Jlichlorki>L'7)l and an alkaline substance (1) to react, 1υ, anti-λ( ] - A method for producing αα,α'-1 realkoxyxylene, characterized in that the alkali-11 substance is constantly present in the reaction system during and after the reaction is completed.

The present invention will be explained in more detail below.

α,α,α'-1□LichlorxoI/7 used in the method of the present invention is α,α,α'-trichloro-0-
xylene, α, α, α-trichlor-m-xylene, α
, α,α'-trichloro-p-quinolene.

α, α, α'-4 Lichloroxylene is produced by a chlorination reaction of 0-xylene, m-xylene, or p-xylene. For example, by applying molecular chlorine to 0-xylene, m-xylene or p-xylene in the presence of light or in the presence of a peroxide radical initiator or an azyl radical initiator. Can be manufactured. The chlorination reaction of xylene is a sequential reaction, and the molar ratio t of chlorinated xylene determines the control of the four components. It is generally known that +11 can be formed.
1. Contained in the largest amount in the mass, α, α, α“−1
・In order to increase the yield of lichlorquine L・N, the molar ratio was increased to 3.
It is often done to reduce the amount of low boiling components to below 4J/J. In addition to such chlorination reaction mass, a large amount of α1α1α"-1 lyxolone remains in the residual pot during the production of α,α'-dichloro-L1-luxolene, which is extremely useful as an intermediate. It is possible to use the present invention by purifying the 2 liters using the method described below.Chlorination reaction mass α,α'-dichloride:α,α,o - Distillation is the most suitable method for extracting “-l lychlorquine I/n.In the case of crystallization, α, α, α
'-trichloroxy-n and α, α'-dichlor) L
/n forms a eutectic compound, so it is preferable L<no.

The lower alcohols used in the method of the present invention include methanol, coatanol, 1-propanol, and 2-propanol.

α, α, α'-[・realkoxyxylene 2 which cannot be obtained by the method of the present invention using these raw material compounds is as follows:
α1α,α' lrimethoxy-0xyα,α α′-trime(quin-m-xylene, α1-trimethy-1-quinolxylene, αtriethoxy-0-kiln, α7α triethoxy-M-xylene, α, α, α Trietquin-p-xylene, α, α, α'-1-li(1-propogine)-0xolene, α1α, α1su(1-propoxy L
m-Kinren, α, α, α-tri (I-pu “” Bokin)-
p-xylene, α1α・tos(2-propoquino)-0-
xylene, α, αl・su(2-prol-lboxo)-mxylene, α,αtri(2-propoquino)-p-quino L/
It is.

Len', α α α α is 511S301.5115302, S1. I
S303.5llS3Q4.5US305.511
S308.5tlS321 5US347.5IIS3
04L, 5US316.5US317.5US316L
SSUS309.5US314.

The alkaline substances used in the method of the present invention include hydroxides, carbonates, and bicarbonates of alkali metals and alkaline earth metals, and representative examples thereof include lithium hydroxide, lithium carbonate, These include sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, calcium hydroxide, and calcium carbonate. These alkaline substances are usually used alone, but there is no problem even if they are used in a mixture of two or more types, and the alkaline substances can be used in the form of a highly pure solid or a low purity aqueous solution.

In the method of the present invention, the alkaline substance is constantly present in the reaction system both during and after the reaction, making it unusable.

The amounts of these alkaline substances used are as follows depending on their type. When the alkaline substances are alkali metal hydroxides and bicarbonates, these alkaline substances are
α used as raw material.

The number of moles of chlorine contained in α,α”-trichloroxylene or more may be used.If the alkaline substance is an alkali metal carbonate, alkaline earth metal hydroxide, or carbonate, α,α , α'-trichloroxylene may be 1/2 or more of the number of moles of chlorine contained in α'-trichloroxylene.Also, in the case of a mixture, the amount used may be calculated from the amount used above.Of course, during the progress of the reaction It is also possible to add such alkaline substances to α.

Even if it is in large excess compared to the chlorine contained in α,α'-trichloroxylene, there is no particular adverse effect on the reaction.

In the method of the present invention, the lower alcohol is charged in advance into the reaction system together with the alkaline substance, but of course it may be added sequentially during the progress of the reaction. The amount of lower alcohol added should be at least the number of moles of chlorine contained in α, α, α'-trichloroxylene, but industrially, The appropriate amount is 1.5 times or more the number of moles of chlorine used.

In addition, even if the lower alcohol is in large excess compared to α,α,α'-trichloroxylene, there is no particular adverse effect on the reaction.
It may be selected appropriately depending on the capacity, shape, etc. of the reactor used.

In the method of the present invention, α, α, α“-trichloroxylene is added to a reaction system in which alkaline substances and lower alcohols have been prepared. If , α, α
Since the reaction between α'-trichloroxylene and lower alcohol is an exothermic reaction, the reaction proceeds rapidly and reaction control is difficult, so a method of sequential addition is usually adopted.

In the method of the present invention, the reaction temperature can be arbitrarily selected within the range of 0 to 200°C, and the reaction pressure may be either normal pressure or elevated pressure. For example, it is industrially advantageous to use the heat of reaction between α, α, α′ trichloroxylene and a lower alcohol, and to reflux the lower alcohol to control the temperature to the boiling point of the lower alcohol at normal pressure. be.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Production Examples, Examples, and Comparative Examples.

α,α,α'-Trichloroxylene production example jacket,
After charging 200 g of ρ-xylene and 300 g of carbon tetrachloride as a solvent into a glass photoreactor with a volume of 1 j2 and equipped with a reflux condenser, a stirrer, and a chlorine gas inlet, and equipped with an internally illuminated 100-mercury lamp. , while stirring, 10
400 g of chlorine was blown in at a rate of g/min. The reaction temperature was adjusted to 70°C by feeding cold water into the jacket. Analysis of various chlorinated substances in the reaction mass by gas chromatography revealed that α,α,α1-trichloro-p-xylene was 48% by weight, α,α-dichloro-p-xylene was 20% by weight.
%, α, α.

, α', α, α-tetrachloro-p-xylene 23% and others 9wt%. In addition, almost no chlorine was detected in the gas discharged from the reactor.

300 g of the above reaction solution was taken out and subjected to batch karate distillation in a -40-stage old show type Fujitome vessel (made of glass, tray type). The top vacuum was set to 10ff10ff1 at a reflux ratio of 3, and the fraction up to the top temperature of 135°C was 1.155°C.
Fraction 2 was collected, and its composition was analyzed by gas chromatography. As a result, fraction 1 weighed 73 g, and its composition was 72 wt% of α,α'-dichloro-p-xylene,
α,α1,α'-trichloro-ρ-xylene 14wt%
, and others were 14-t%. Fraction 2 weighs 138g, and its composition is α,α'-dichloro-p-xylene 5wt.
%, α, α, α'-Trichloro-p-xylene 90-t
%, α, α, α', α'-tetrachloro-p-xylene 3-t%, and others 2 wt%.

Since fraction 1 contains a large amount of α,α'-dichloro-p-xylene, it can be donated to the reaction again. Further, in fraction 2, α,α,α'-trichloro-p-xylene with a purity of 90% was obtained.

Example 1 500mj equipped with stirrer, reflux condenser and dropping funnel! A test piece made of 5US304 (
After charging 320.4 g of methanol and 13.6 g of 97% caustic soda, 20.0 g of α, α, α' - trichlor p-xylene obtained in the production example was added. 95 g was added dropwise to react. The reaction temperature was controlled by immersing the reactor in an oil path and refluxing methanol. After completion of the dropwise addition, post-reaction was carried out for 5 hours to complete the reaction. The material test piece was taken out, lightly washed with water and acetone, then dried, weight loss was measured, and the degree of corrosion (mm/y) was determined to be 0, indicating complete corrosion resistance. The corrosion degree was calculated according to the following formula.

Corrosion degree-((Wi-Wf)X 365)/(SxdX
day) Furthermore, as a result of gas chromatography analysis of the reaction solution, α,α,α′-trichloro-p-xylene was not detected, and α,αα″-trimethoxy-p-xylene with a purity of 89% was detected.
-Xylene was produced. The results are shown in Table 1.

Examples 2 to 5, Comparative Example 1 Reacted in the same manner as in Example 1 under the conditions shown in Table 1,
The degree of corrosion was determined. The results are shown in Table 1.

Comparative Example 2 Into the reactor used in Example 1, test pieces made of the materials shown in Table 1, methanol, α, α, α-1・Lichlorop-
After charging xylene, 50% caustic soda was added dropwise from the dropping funnel over 5 hours to cause a reaction.

The results are shown in Table 1.

〔Effect of the invention〕

As is clear from the above examples, the production method of the present invention can be used in the reactor from before the start of the reaction to during the reaction, is highly safe, and has α, α.

, α'-trimethoxyxylene This is an excellent method for producing α, α, α1-trimethoxyxylene with high purity.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. In a method for producing α,α,α'-trialkoxyxylene by reacting α,α,α'-trichloroxylene with a lower alcohol, in the reaction system of a batch reactor. Add an alkaline substance and lower alcohol to
α, α, α' characterized in that α, α, α'-trichloroxylene is added and reacted, and the alkaline substance is constantly present in the reaction system during and after the reaction.
- A method for producing trialkoxyxylene. 2. α according to claim 1, wherein the alkaline substance is selected from the group of hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, either alone or in a mixture of two or more.
, α,α'-Trialkoxyxylene manufacturing method.