JP2002047253A - Method for producing 2,2-bis(3-nitro-4-hydroxyphenyl) propane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable production of high-purity dinitro substance and reduce load to waste water by carrying out nitration reaction without using acetic acid. SOLUTION: Nitric acid is dropped into a solution of monochlorobenzene suspension of bisphenol A within the range of 0 deg.C to 20 deg.C and an organic layer is washed with an alkali within the range of 60 deg.C to 100 deg.C and successively washed with water and a poor solvent is charged thereinto to produce 2,2-bis(3- nitro-4-hydroxyphenyl)propane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a 2,2-bis (3
-Nitro-4-hydroxyphenyl) propane.

[0002]

2. Description of the Related Art 2,2-bis (3-nitro-4-hydroxyphenyl) propane (hereinafter abbreviated as dinitro compound) is
2,2 which are raw materials for polyhydroxyamide and polybenzoxazole used in the field of electric materials and heat-resistant materials
-Bis (3-amino-4-hydroxyphenyl) propane (hereinafter abbreviated as diamine) is a compound useful as an intermediate in the production. As a production method, a method of nitrating bisphenol A with nitric acid is known.

[0003] In general, it is known that a nitration reaction does not use an organic solvent and is carried out in sulfuric acid and nitric acid. As a method using a solvent, there is known an example in which alizarin, p-toluenesulfone-o-toluidine, acenaphthene, or the like is nitrated using acetic acid, monochlorobenzene, orthodichlorobenzene, or the like. However, depending on the reaction substrate, there are many parts to be examined, such as regioselectivity and reactivity, and it is not easy to determine reaction conditions in a straightforward manner.

For example, when monochlorobenzene is used as a solvent, the reaction product is converted into a homogeneous solution by referring to the method for nitrating p-toluenesulfone-o-toluidine described in US Pat. No. 2,459,002. If the reaction temperature at the time of nitration is kept at 50 ° C. or higher so that the nitration reaction of bisphenol A is performed, the yield of the target dinitro compound decreases.

On the other hand, when acetic acid is used as a solvent,
Since a homogeneous solution of bisphenol A can be obtained without raising the temperature to 50 ° C. or more, the conventionally known 2,2
Most of the methods for producing -bis (3-nitro-4-hydroxyphenyl) propane use acetic acid or a mixture of acetic acid and another organic solvent as a solvent.

For example, Polymer Letters, vol. 7, 185-191
(1969) describes a method of dropping concentrated nitric acid at 0 to 5 ° C. into a solution of bisphenol A dissolved in a mixed solution of acetic acid and benzene. In a similar way,
Macromolecules, vol. 27, 1147-1153 (1994). Describes a method in which bisphenol A is dissolved in a mixed solution of acetic acid and toluene, and nitric acid is added dropwise under ice-cooling. I have. Japanese Patent No. 420617 discloses a method in which concentrated nitric acid is dropped into an acetic acid solution of bisphenol A under ice-cooling to remove a deposited dinitro compound.
No. 1-60545 discloses that a required amount or less of concentrated nitric acid is dropped into an acetic acid solution of bisphenol A at 21 to 100 ° C., and then the remaining concentrated nitric acid is dropped at 0 to 20 ° C. Methods for obtaining the corresponding dinitro forms are described. However, in any of the methods, the purity of the dinitro compound in the obtained reaction product is low, and there is a problem that the purification step is burdensome when industrialized. In addition, there is a problem that a load is imposed on wastewater treatment containing acetic acid used as a solvent.

In addition, as a method not using acetic acid, JP-A-1-299262 describes a method in which phenols are supported on a support and brought into contact with a gas containing NOx. Bisphenol A
On the other hand, only about 0.5% of the desired dinitro compound is produced, which is not suitable for industrial production.

SUMMARY OF THE INVENTION The present inventors have found that in nitration using acetic acid, the purification step for increasing the purity of the obtained reaction product becomes complicated, and a load is imposed on the treatment of wastewater containing acetic acid. As a result of intensive studies in view of the problem of the prior art, using monochlorobenzene and controlling the reaction temperature, acetic acid is not used easily and economically,
The inventors have found that a dinitro compound can be produced, and have reached the present invention.

[0008]

That is, the present invention provides a nitration reaction by dropping nitric acid in a suspension of bisphenol A in monochlorobenzene at a temperature in the range of 0 ° C to 20 ° C, and allowing the nitrating reaction to proceed. After the organic layer is washed with alkaline water and then with water in the temperature range described above, a poor solvent is charged.
-Bis (3-nitro-4-hydroxyphenyl) propane.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, the nitration reaction is carried out while dropping nitric acid into a suspension of bisphenol A in monochlorobenzene. The reaction temperature at this time is from 0 ° C to 20 ° C, preferably 1 ° C.
0 to 20 ° C is good. If the reaction is carried out within this range, a special cooling device is not required, and it is economical. Nitric acid stays in the initial stage of the reaction, the induction period until the start of the reaction is lengthened, and there is little possibility that the control of the reaction becomes difficult. If the temperature is 20 ° C. or lower, the yield of the target dinitro compound is less likely to decrease.

The amount of monochlorobenzene to be used is usually 1.5 to 6 times the weight of bisphenol A, and preferably 2 to 4 times the weight of the reaction mass from the viewpoint of fluidity and economy.

The concentration of the nitric acid to be dropped is usually preferably 40% or more. Although a lower concentration may be used, 98%, 68% and 65%, which are industrially easily available, are preferred. In particular, 50
To 70% is preferable because the yield of the obtained dinitro compound is high and a less colored product is obtained.

The amount of nitric acid to be dropped is a theoretical amount, that is, a molar ratio of usually 2 to 3 mol, preferably 2 to 2.5 mol, based on bisphenol A.

After the nitration reaction, alkaline water is charged into the reaction product, and the reaction is carried out at 60 to 100 ° C, preferably 70 to 9 ° C.
At 0 ° C., the remaining nitric acid and the decomposition product of nitric acid are neutralized, and at the same time, the decomposition product of bisphenol A or dinitro compound generated during the reaction is extracted into the aqueous layer, followed by liquid separation. 100 ° C, preferably 70 ° C to 90 ° C
To obtain a solution of the dinitro compound in monochlorobenzene. If the reaction is carried out at 60 ° C. or higher, it is unlikely that the dinitro compound as the target substance is precipitated or the liquid separation between the organic layer and the aqueous layer is deteriorated. In addition, when only water washing is performed without alkaline water washing, the quality of the dinitro compound may be deteriorated due to remaining nitrate groups or insufficient extraction of the decomposition product of bisphenol A or dinitro compound generated during the reaction. May be adversely affected.

The term "nitrate" as used in the present invention refers to a trace amount of impurities derived from nitric acid, such as nitric acid and nitrogen oxides which are decomposition products of nitric acid.

In the present invention, examples of the alkali used for washing with alkaline water include inorganic bases such as sodium hydroxide, sodium carbonate, and sodium hydrogencarbonate. This is not the case if it can be adjusted to 8.5. Among them, sodium bicarbonate is preferred. There is no problem in the quality of the obtained dinitro compound even if the pH of the aqueous layer exceeds 8.5, but it is not preferable because the amount of the dinitro compound lost to the aqueous layer increases. On the other hand, when the pH of the aqueous layer is lower than 7.0, the purity of the obtained dinitro compound tends to decrease, which is not preferable.

The dinitro compound can be taken out by a well-known method such as charging a poor solvent into a solution of the dinitro compound in monochlorobenzene, and centrifuging or filtering the precipitated dinitro compound. The poor solvent referred to in the present invention is a solvent that dissolves in monochlorobenzene but hardly dissolves the dinitro compound. The dinitro compound can be removed from the monochlorobenzene solution of the dinitro compound by concentrating the solvent to dryness or by cooling after concentration.
There are problems such as coloring of the dinitro compound and reduction of the yield.

The amount of the poor solvent used in the present invention is usually 2 to 10 times the weight of monochlorobenzene.
When the amount of the poor solvent used is less than 2 times by weight, the amount of the dinitro compound lost in the filtrate tends to increase. on the other hand,
There is no problem even if the poor solvent is used 10 times by weight or more, but it is not very economical, for example, the kettle efficiency is lowered.

Examples of the poor solvent used in the present invention include aliphatic hydrocarbons such as pentane and hexane and those having 1 carbon atom.
To 5 alcohols, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, amyl alcohol and the like. Among them, alcohols are preferred, and isopropyl alcohol is more preferred.

When the poor solvent is charged, the dinitro compound may be directly charged into the monochlorobenzene solution, but the solution may be concentrated in advance to reduce the amount of monochlorobenzene. The monochlorobenzene recovered at that time can be recycled without any problem even if it is used again for the nitration reaction. Further, a monochlorobenzene solution of a dinitro compound may be dropped into a poor solvent previously charged.
Thereafter, the precipitated dinitro compound can be removed by a known method such as filtration or centrifugation.

By drying the reaction product obtained by the method described above, high purity dinitro-form yellow crystals free of nitrate groups are obtained. In addition, there is no problem if the reaction product is used in the next hydrogenation reduction step without drying.

In the present invention, the obtained dinitro compound is converted to a diamine compound useful in the field of electric materials and heat-resistant materials by a generally known reduction reaction. For example, it is a method of charging a reactor together with a polar solvent and performing a hydrogenation reduction reaction in the presence of a Pd catalyst. In particular N, N- dimethylformamide was used as a solvent, the use of Pd / _Al 2 _{O 3,} raise the pot efficiency preferable.

[0022]

The present invention is not limited to the following examples.

Example 1 500 ml of 4 equipped with a stirrer, thermometer and dropping funnel
Bisphenol A13 in a flask with a bottom opening cock
0.9 g (0.57 mol) and 382.3 g of monochlorobenzene were charged and stirred, and the internal temperature was reduced to 15 ° C. in an ice water bath.
I lowered it. 113.0 g of 65% nitric acid (1.17 m
ol) was added dropwise over 1 hour, then the ice-water bath was removed and stirring was continued at room temperature for 1 hour. Next, 382.3 g of a 5% aqueous solution of sodium hydrogencarbonate was charged, the temperature was raised to 80 ° C., and the mixture was stirred for 1 hour.
g, and the mixture was stirred at 80 ° C. for 1 hour and allowed to stand still for liquid separation. The obtained organic layer was concentrated at 80 ° C. under reduced pressure to recover 300 g of monochlorobenzene.
5 g was charged dropwise over 30 minutes. Thereafter, the mixture was cooled to room temperature, and the precipitated yellow solid was filtered, dried with a ventilation dryer at 70 ° C. until a constant weight was reached, and 144.3 g of 2,2-bis (3-nitro-4-hydroxyphenyl) propane was obtained.
(79.1% yield). The purity by HPLC analysis was 98.7 Area%.

Comparative Example 1 110.0 g of 2,2-bis (3-nitro-4-hydroxyphenyl) propane was obtained in the same manner as in Example 1 except that the reaction temperature during nitration was changed to 50 ° C. 60.3%)
I got The purity by HPLC analysis is 96.0 Area%.
was.

Comparative Example 2 500 ml of 4 equipped with a stirrer, thermometer and dropping funnel
20.64 g of bisphenol A (0.
(086 mol) and 100 ml of glacial acetic acid, and the mixture was stirred, and the internal temperature was raised to 50 ° C. in a hot water bath. 2 ml of concentrated nitric acid
(0.026 mol) was added dropwise over 1 hour, and then cooled with ice to lower the internal temperature to 13 ° C., and 13.3 ml of concentrated nitric acid was further added.
(0.149 mol) was added dropwise over 1 hour. Thereafter, stirring was continued for 3 hours, and the precipitated yellow crystals were filtered, washed sequentially with 40 ml of glacial acetic acid and 80 ml of water, and dried under reduced pressure.
2,2-bis (3-nitro-4-hydroxyphenyl)
12.8 g (yield 46.5%) of propane were obtained. HPL
The purity by C analysis was 45.2 Area%, and contained 23.2% of mononitro compound and 29.4% of trinitro compound. 10.2 g (37.1% yield) from the filtrate
Was recovered, and the purity by HPLC analysis was 37.8 Ar
In ea%, the mononitro compound was 5.1 Area% and the trinitro compound was 47.8%.

[0026]

According to the present invention, a high-purity dinitro compound can be produced by nitration without using acetic acid, the purification process is simplified, and the load on wastewater is reduced. Was done.

Claims (4)

[Claims] 1. A 2,2-bis (3-nitric acid solution, wherein nitric acid is added dropwise to a suspension of bisphenol A in monochlorobenzene in a temperature range of 0 ° C. to 20 ° C. and nitrated.
A method for producing (nitro-4-hydroxyphenyl) propane. 2. Nitric acid is added dropwise to a suspension of bisphenol A in monochlorobenzene at a temperature of 0 ° C. to 20 ° C. to cause a nitration reaction, and then the organic layer is alkalized at a temperature of 60 ° C. to 100 ° C. After a water wash followed by a water wash,
A method for producing 2,2-bis (3-nitro-4-hydroxyphenyl) propane, which comprises obtaining the dinitro compound. 3. Nitric acid is added dropwise to a suspension of bisphenol A in monochlorobenzene at a temperature in the range of 0 ° C. to 20 ° C. to cause a nitration reaction. Then, the organic layer is alkalized at a temperature in the range of 60 ° C. to 100 ° C. After a water wash followed by a water wash,
2,2-bis (3-nitro-4) characterized in that the dinitro compound is obtained from a monochlorobenzene solution of 2,2-bis (3-nitro-4-hydroxyphenyl) propane by charging a poor solvent. -Hydroxyphenyl) propane. 4. The method for producing 2,2-bis (3-nitro-4-hydroxyphenyl) propane according to claim 3, wherein the poor solvent is an alcohol.