JPS6045864B2 - Method for producing 1,4,4a,9a-tetrahydroanthraquinone compound - Google Patents

Description

Detailed Description of the Invention The present invention produces a 1,4,4a,93-tetrahydroanthraquinone compound, which is an important raw material for organic chemicals such as dyes, by reacting 1,4-naphthoquinone with 1,3-butadiene or isoprene. Relating to a method of manufacturing.

More specifically, a 1,4,4a,9a-tetrahydroanthraquinone compound is used as the reaction medium;
The present invention relates to a method for producing a 1,4,4a,9a-tetrahydroanthraquinone compound by reacting naphthoquinone with 1,3-butadiene or isoprene. 1, 4
- In the case of manufacturing a 1,4,4a,9a-tetrahydroanthraquinone (hereinafter simply abbreviated as THAQ) compound by subjecting naphthoquinone (hereinafter simply abbreviated as NQ) and 1,3-butadiene or isoprene to a so-called Diels-Alder reaction. , the reaction has traditionally been carried out in an inert solvent such as an aromatic hydrocarbon such as benzene, xylene or naphthalene.

However, in order to complete the reaction, it is generally necessary to use at least the same mole of 1,3-butadiene or isoprene based on NQ, and to recover excess 1,3-butadiene or isoprene after the reaction is completed. In the method using an organic solvent, it was difficult to recover 1,3-butadiene or isoprene because of its affinity for the solvent.Also, when obtaining the product directly as a THAQ compound, the solvent The solvent must be separated from the reaction mixture containing THAQ, which requires a separation and recovery process such as distillation, and even when distilled under vacuum, the solvent does not easily separate from the THAQ compound and remains. It was extremely difficult to substantially completely remove NQ.The present inventors discovered that under the Diers-Alder reaction conditions of NQ and 1,3-butadiene or isoprene, the reaction product THAQ compound is liquid. In particular, NQ is dissolved in liquid THAQ compound, and when 1,3-butadiene or isoprene is introduced in gaseous or liquid form to dissolved NQ under the reaction conditions, THA
They found that compound Q can be obtained in high yield and high quality, arrived at a new method other than the conventionally known method using an organic solvent, and completed the present invention.

The method of the present invention is a method for producing a THAQ compound by a Diers-Alder reaction between NQ and 1,3-butadiene or isoprene, which is characterized in that the THAQ compound is essentially used as a reaction medium. It is a manufacturing method, and further includes reacting NQ with 1,3-butadiene or isoprene in a corresponding liquid THAQ compound, and converting a portion of the resulting reaction product consisting essentially of the THAQ compound into a liquid or THAQ compounds are extracted in solid form, recycled as a medium for the next reaction, and the remainder is obtained as intermediate raw materials for products, such as bulb cooking aids, dyes and pesticides, and raw materials for the production of anthraquinone and dihydroanthraquinone derivatives. It depends on the manufacturing method.

The conjugated diolefin used in the method of the invention is 1,
The THAQ compounds obtained by the Diels-Alder reaction of 3-butadiene and isoprene with NQ are THAQ and 2-methyl THAQ, respectively, which have melting points of about 120° C. or less and are suitable as reaction media in the method of the present invention. used for.

In the method of the present invention, when NQ and 1,3-butadiene or isoprene are subjected to a Diels-Alder reaction,
The reaction temperature is determined by the type of conjugated diolefin, the amount used, the melting point of the THAQ compound corresponding to it, and the concentration of NQ, but a temperature higher than the melting point of the crude THAQ compound to be produced is adopted, and is generally 80-80°C. 250℃, preferably 100~1800C1, more preferably 110~
The optimum temperature is appropriately selected from the range of 150°C depending on the conditions of the reaction process.

If the reaction temperature is too high, the rate of side reactions will increase; if the reaction temperature is too low, the reaction rate will drop sharply. The reaction pressure depends on the temperature, the type of conjugated diolefin used, that is, the type and concentration of 1,3-butadiene or isoprene, etc.
,3-butadiene, it is 120 k9 no CltG or less, usually 1 to 30 kg IdG, preferably 3 to 20 kg IdG.
k91cItG range. As for the amount of 1,3-butadiene or isoprene used, the reaction will be completed more quickly if it is in excess of NQ, but if it is too much, it is not economical in terms of equipment, and it is usually 1 to 20 times the amount by mole. 1.1~
10 moles are taken.

The reaction time is limited by constraints such as the type, concentration, and reaction temperature of 1,3-butadiene or isoprene, and the optimum reaction time is selected for each, but it is generally carried out for 0.1 to 5 hours.

The method of the present invention can be adopted as either a batch method, a semi-continuous method using conventional batch reaction vessels in series, or a continuous method using a vireactor.

For a general method of carrying out the invention, as an example, 1,3-
This will be explained using butadiene. THAQ. 1,3-Butadiene was introduced in liquid or gaseous form into the mixture with 15NQ while maintaining the temperature at 120°C, and the reaction pressure was 6k91cItG.
and stir for 2.5 hours.

After the reaction is completed, excess 1,3-butadiene is recovered by releasing the pressure, and liquid THAQ is obtained as it is.

Generally, a portion of the product is used as the next reaction medium, and the remainder is either directly flaked or pulverized into a product, or used as a raw material in the manufacturing process of anthraquinone or dihydroanthraquinone. can. In the present invention, the amount of THAQ compound used as a reaction medium is not particularly limited, but it is generally selected from the range of 0.5 to 5 parts by weight based on NQ. The THAQ compound produced by the method of the present invention is mainly used as a raw material for anthraquinone derivatives, which are important as intermediates for dyes and pigments. High-quality anthraquinone derivatives can be produced in high yield.

In addition, it is noteworthy that THAQ compounds have attracted attention as direct intermediate raw materials for anthraquinone dyes and pigments, and new demand has expanded as a valve cooking aid.
Industrial production of I(AQ compound) is urgently needed.The method of the present invention can easily and quickly remove excess 1,3-butadiene or isoprene after the Diels-Alder reaction, and can also remove the organic solvent. Since high-quality THAQ compounds required for the above-mentioned various uses can be obtained extremely easily and in high yields through simple steps, this method has great industrial value.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the scope is not limited thereto.

In the examples, part J means 1 part by weight. Example 1 30.0 parts of THAQ and 31.0 parts of NQ. 6 parts were placed in an autoclave, heated to 120°C, and maintained at the same temperature.

A constant temperature and constant pressure reaction was carried out at a pressure of 6 kg and 1 dG while stirring the contents and adding liquid 1,3-butadiene under pressure below the liquid surface. After reacting for 3 hours, excess 1,3-butadiene is released from the autoclave while maintaining the same temperature until the pressure reaches normal pressure, and is then cooled and collected. 99% of the amount was recovered.

Thereafter, the product was cooled to room temperature to obtain 72.3 parts of product.

The content of THAQ in the product was 99.2% and the amount of 1,3-butadiene remaining was trace. The above TH
Similar results were obtained by reusing the nodule of the AQ compound as the reaction medium and carrying out the same procedure as in the above example.

Comparative example NQ3l. A 45% solution of ortho-xylene containing 6 parts was charged into an autoclave, heated to 120°C, and maintained at the same temperature.

While stirring the contents, liquid 1,3-butadiene was added below the liquid surface under pressure at a temperature of 120°C and a pressure of 6kg'C.
A constant temperature and constant pressure reaction of rlG was performed. After reacting for 3 hours, the pressure is released to normal pressure at the same temperature, and excess 1,3-butadiene is discharged from the autoclave. 80% was recovered as a solution containing 10% ortho-xylene.

Furthermore, water vapor is 0.45% relative to 1,3-butadiene.
By supplying double the amount of 1,3-butadiene and stripping 1, a total of 99% of 1,3-butadiene was recovered in about 8 minutes from the initial excess 1,3-butadiene.
The same result was obtained when isoprene was used instead of 1,3-butadiene.

Example 2 2-Methyl THAQ3O Nijibu and NQ3l. 6 parts were placed in an autoclave, heated to 115°C, and maintained at the same temperature.

A low-temperature, low-pressure reaction of 6k91c1iG was carried out under pressure while stirring the contents and adding liquid isoprene below the liquid surface. After reacting for 3.5 hours, the liquid temperature was raised to 120°C, and while maintaining the same temperature, excess isoprene was released.
It was cooled to room temperature to obtain 75.0 parts of product.

The 2-methyl THAQ content in the product was 98.5%, and the amount of remaining isoprene was only a trace. (9) parts of the above 2-methyl THAQ product were reused as the reaction medium and carried out as in the above example with similar results.

Claims (1)

[Claims] 1 1,4-naphthoquinone and 1,3-butadiene or isoprene are reacted by Diers-Alder reaction to produce 1,4-
A method for producing a 1,4,4a,9a-tetrahydroanthraquinone compound, characterized in that the 1,4,4a,9a-tetrahydroanthraquinone compound is essentially used as a reaction medium. manufacturing method. 2 A substantially 1,4,4a,9a-tetrahydroanthraquinone compound obtained by reacting 1,4-naphthoquinone and 1,3-butadiene or isoprene in a liquid 1,4,4a,9a-tetrahydroanthraquinone compound 2. The method according to claim 1, wherein a part of the reaction product is recycled as the next reaction medium, and the remainder is obtained as a product.