JPH11100356A - Purification of bis(3-amino-4-hydroxyphenyl)s - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain bis(3-amino-4-hydroxyphenyl)s in high purity and high yield by treating crude bis(3-amino-4-hydroxyphenyl)s with a solvent containing lower alcohols. SOLUTION: Crude bis(3-amino-4-hydroxyphenyl)s are treated with a solvent containing lower alcohols (e.g. a mixed solvent of the lower alcohol with water or hydrocarbons) according to a recrystallizing method, a washing method or the like to afford the objective compounds [e.g. bis(3-amino-4-hydroxyphenyl) methanes]. For example, in the recrystallizing method, the treatment is carried out by a method for dissolving the crude bis(3-amino-4-hydroxyphenyl)s in the solvent at normal temperatures or under heating, then cooling the resultant solution, distilling away the solvent, adding a poor solvent such as water or hydrocarbons or the like or combining the methods and depositing a crystal. Thereby, the compounds especially useful as a raw material for heat-resistant polymers or the like are obtained in high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bis (3-amino-
4-hydroxyphenyl).

[0002]

2. Description of the Related Art Bis (3-amino-4-hydroxyphenyl), especially 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, is an important compound as a raw material for heat-resistant polymers and the like. . Methods for producing 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane include the following methods, which have the following problems. JP-A-6
According to 211752, 2,2-bis (3-nitro-4
-Hydroxyphenyl) hexafluoropropane is subjected to catalytic hydrogen reduction under hydrogen pressure using palladium-carbon as a catalyst, and the catalyst is filtered, drained and crystallized to obtain a black-grey product. The crude product was further recrystallized three times with a mixture of ethyl acetate and n-hexane to give 2,2-bis (3
-Amino-4-hydroxyphenyl) hexafluoropropane. In this method, a mixed solvent of ethyl acetate and n-hexane is used. These have a low boiling point and pose a problem for the working environment, have a low decolorizing efficiency for coloring components, and have a high solvent recovery cost, and are not industrially advantageous production methods.

[0003]

SUMMARY OF THE INVENTION The above-mentioned conventional 2,2
The method for purifying -bis (3-amino-4-hydroxyphenyl) hexafluoropropane has problems such as low purification yield, influence on the working environment, high solvent recovery cost, and difficulty in removing impurities such as coloring components. Having.

[0004]

The present inventors have conducted intensive studies to solve the problems of the conventional method, and as a result,
Crude bis (3-amino-) represented by 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
The present inventors have found that bis (3-amino-4-hydroxyphenyl) s can be obtained with high purity and high yield by treating 4-hydroxyphenyl) with a solvent containing a lower alcohol. Things.

That is, the present invention provides (1) bis (3-amino-4-hydroxyphenyl) characterized by treating crude bis (3-amino-4-hydroxyphenyl) with a solvent containing lower alcohols. (2) bis (3-amino-4-hydroxyphenyl) is a compound of the formula (1)

[0006]

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[0007] (Wherein X represents a bond or a direct bond between phenyl groups, and R ₁ and R ₂ are substituents). (3) X Is a substituted or unsubstituted alkylene, aralkylene, -O
-, -S-, -SO-, -SO2-, -CO-, a substituted or unsubstituted amino, the purification method according to (2), (4).
(2) or (3) wherein the substituents of R ₁ and R ₂ are each a hydrogen atom, a lower alkyl group, a lower alkoxy group, a hydroxyl group, an alkyloxycarbonyl group, a carbamoyl group, an amino group, an acyloxy group or a halogen atom. (5) when the compound represented by the formula (1) is 2,
2- (bis- (3-amino-4-hydroxyphenyl) hexafluoropropane) (2), a method for purifying bis (3-amino-4-hydroxyphenyl) s, and (6) a solvent containing a lower alcohol. Is carried out by dissolving a crude bis (3-amino-4-hydroxyphenyl) in a lower alcohol and then adding water or a hydrocarbon. 3-
Amino-4-hydroxyphenyl) s. (7) Crystallization by distilling off a predetermined amount of a solvent containing a lower alcohol from a mixed solution containing a lower alcohol containing a crude bis (3-amino-4-hydroxyphenyl). A method for purifying bis (3-amino-4-hydroxyphenyl) s according to (1).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The production method of the present invention will be described below in detail. In the present invention, the bis (3-amino-4-hydroxyphenyl) s may be those obtained by isolating bis (3-amino-4-hydroxyphenyl) s precipitated from the reaction solution, and may remain in the reaction solution. You may. It is colored grayish white or pale red (the hue differs depending on the synthesis method), and its purity is about 98% or less (analytical value of liquid chromatography (area value%)).

The crude bis (3-amino-4) used in the present invention
-Hydroxyphenyl) includes, for example, a compound represented by the above formula (1). In the above formula (1), X represents a bonding chain or a direct bond between phenyl groups, and R ₁ and R ₂ are substituents. As the binding chain of X, for example,
Substituted or unsubstituted alkylene, aralkylene, -O-,-
S-, -SO-, -SO2-, -CO-, substituted or unsubstituted amino and the like. Examples of the substituted or unsubstituted alkylene include methylene, ethylene, trimethylene,
1,1,1,3,3,3-hexafluoropropane and the like; aralkylene includes, for example, benzylidene; and substituted or unsubstituted amino includes, for example, amino, methylamino, ethylamino, anilino and the like. No.

The substituent represented by R ₁ or R ₂ in the formula (1) is, for example, a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an alkyloxycarbonyl group, a carbamoyl group, an amino group, an acyloxy group or a halogen atom. And the like.

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl and 2-
Ethylhexyl, 2-ethyldecyl, n-decyl, n-
Examples thereof include C1-C12 alkyl groups such as dodecyl, and alkoxy groups include, for example, methoxy, ethoxy, n-
C1-C12 such as propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, and hydroxyl groups
Examples of the acyl group include C1 to C10 acyl groups such as formyl, acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, and octanoyl.Examples of the alkyloxycarbonyl group include methyl carboxy. Ray
Carboxylate, ethyl carboxylate, propyl carboxylate, butyl carboxylate, pentyl carboxylate, hexyl carboxylate, 2-ethylhexyl carboxylate and the like.Examples of the carbamoyl group include carboxamide and carboxylic dimethylamide. And carboxylic acid diethylamide, carboxylic acid methylamide, and carboxylic acid ethylamide. Examples of the amino group include amino, N-methylamino, N-ethylamino, N, N-dimethylamino, N, N-diethylamino, N-methylethylamino, N, N-dipropylamino, N, N-dibutylamino, N-morpholino and the like are mentioned. As the acyloxy group, for example, acetoxy, propionyloxy, butyryloxy group and the like are mentioned. Te is, for example fluorine, chlorine, bromine, and iodine.

The bis (3-amino-4-hydroxyphenyl) represented by the formula (1) used in the present invention includes:
For example, bis (3-amino-4-hydroxyphenyl) methanes, 2,2-bis (3-amino-4-hydroxyphenyl) propanes, 2,2-bis (3-amino-4-)
Hydroxyphenyl) hexafluoropropanes, 3,3
-Bis (3-amino-4-hydroxyphenyl) pentanes, 2,2'-diamino-4,4'-benzylidenebisphenols, bis (3-amino-4-hydroxyphenyl) ethers, bis (3-amino -4-hydroxyphenyl) sulfides, bis (3-amino-4-hydroxyphenyl) sulfones, bis (3-amino-4
-Hydroxyphenyl) sulfoxides, bis (3-amino-4-hydroxyphenyl) ketones, bis (3-
Amino-4-hydroxyphenyl) amines, 3,3 ′
-Diamino-4,4'-dihydroxybiphenyls and the like.

Specific examples of the compound of the formula (1) include, for example, bis (3-amino-4-hydroxyphenyl) methane, bis (3-amino-4-hydroxy-5-ethoxyphenyl) methane, bis (3 -Amino-4-hydroxy-5-acetoxyphenyl) methane, bis (3-amino-4-hydroxy-5- (N, N-diethylcarboxamido) phenyl) methane, bis (3-amino-4-hydroxy-6- Fluorophenyl) methane, bis (3-amino-4,5-dihydroxyphenyl) methane, 2,2-
Bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-methylphenyl) hexafluoropropane,
2,2-bis (3-amino-4-hydroxy-6-propanoylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5- (N, N-diethylamino) phenyl) hexa Fluoropropane, 2, 2
-Bis (3-amino-4,5-dihydroxyphenyl)
Hexafluoropropane, 2,2-bis (3-amino-4
-Hydroxy-5-butoxycarbonylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-6-chlorophenyl) hexafluoropropane, 3,3-bis (3-amino-4-hydroxyphenyl) Pentane, 3,3-bis (3-amino-4-hydroxy-5-methylphenyl) pentane, 3,3-bis (3-amino-4-hydroxy-5-chlorophenyl)
Pentane, 2,2'-diamino-4,4'-benzylidene-bisphenol, 2,2'-diamino-4,4 '
Benzylidene-5,5′-dimethylbisphenol,
2,2'-diamino-4,4'-benzylidene-5
5'-dichlorobisphenol, 2,2'-diamino-
4,4'-benzylidene-5,5'-diethoxybisphenol, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy-5
-Methylphenyl) ether, bis (3-amino-4-
Hydroxy-5- (N, N-diethylamino) phenyl) ether, bis (3-amino-4-hydroxy-5)
-Butyroxycarbonylphenyl) ether, bis (3
-Amino-4-hydroxy-6-chlorophenyl) ether, bis (3-amino-4-hydroxyphenyl) sulfide, bis (3-amino-4-hydroxy-5-methylphenyl) sulfide, bis (3-amino-4) , 5
-Dihydroxyphenyl) sulfide, bis (3-amino-4-hydroxy-5- (N-methylamino) phenyl) sulfide, bis (3-amino-4-hydroxy-
5-bromophenyl) sulfide, bis (3-amino-
4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxy-5-isobutylphenyl) sulfone, bis (3-amino-4-hydroxy-6-propanoylphenyl) sulfone, bis (3-amino-4- Hydroxy-5- (N, N-dipropylamino) phenyl)
Sulfone, bis (3-amino-4-hydroxy-6-methylphenyl) ketone, bis (3-amino-4-hydroxy-5-ethoxyphenyl) ketone, bis (3-amino-4-hydroxy-5-methylphenyl) ) Ketone, bis (3-amino-4-hydroxy-6-methylphenyl) ketone, bis (3-amino-4-hydroxy-5-
(N, N-dipropylamino) phenyl) ketone, bis (3-amino-4-hydroxy-5-methoxyphenyl) amine, bis (3-amino-4-hydroxy-5-
Methylphenyl) amine, N, N-di (3-amino-4
-Hydroxyphenyl) aniline, 3,3'-diamino-4,4'-dihydroxydiphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-dimethyldiphenyl, 3,3'-diamino- 4,4'-dihydroxy-5,5'-dichlorodiphenyl and the like.

[0014] The purification method of the present invention provides a crude bis (3-amino-
4-hydroxyphenyl) is purified with a solvent containing lower alcohols. The solvent containing a lower alcohol used here may contain water and hydrocarbons in addition to the lower alcohol. Specific examples of lower alcohols used in the present invention include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-
C1-C6 lower alcohols such as butanol and cyclohexanol are exemplified, and a mixed solvent thereof with water and hydrocarbons is exemplified. As the hydrocarbons, aromatic hydrocarbons such as toluene, xylene and mesitylene, n-
Examples thereof include aliphatic hydrocarbons such as hexane, cyclohexane, n-heptane and n-octane, and mixtures thereof.

In the case of a mixed solvent with water, the concentration of the lower alcohol is 30 to 95% by volume, preferably 40 to 80% by volume.
%, More preferably 50-60% by volume. Below that, colored matter cannot be removed. On the other hand, if it exceeds 95% by volume, the purification yield will be low, which is not economical. The amount of the solvent used is 0.3 to 10 times (v / w), preferably 0.5 to 5 times (v / w) the crude bis (3-amino-4-hydroxyphenyl). Preferably, 1.0
-3.0 times (v / w). If it is less than 0.5, the fluidity becomes poor, and stirring and filtration become difficult. If it exceeds 10 times, the yield becomes low and it is not economical. In some cases, a surfactant may be added to enhance the fluidity. The surfactant is 0.00001 to 1.0 times (w / w) the crude bis (3-amino-4-hydroxyphenyl),
Preferably 0.0001 to 0.1 times (w / w), particularly preferably 0.001 to 0.01 times (w / w) is used. Surfactants that can be used for this include alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonate,
Anionic surfactants such as naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ether,
Examples include nonionic surfactants such as polyoxyethylene alkylphenyl ether and polyoxyethylene sorbitan fatty acid ester, but are not limited thereto. Note that, in addition to water-alcohol, a water-soluble organic solvent such as tetrahydrofuran, acetonitrile, methyl ethyl ketone, and methyl isobutyl ketone may be included. Further, it may contain an antioxidant such as hydrazine, sodium sulfide, hydrosulfite, hydroquinone, and methoquinone.

In the case of a mixed solvent with hydrocarbons, the concentration of the lower alcohol is 2 to 95% by volume, preferably 10 to 95% by volume.
It is -70% by volume, more preferably 15-50% by volume, particularly preferably 20-40% by volume. If it is less than 2%, the colored matter cannot be removed. If it exceeds 95%, the purification yield is low, and it is not economical. The amount of the solvent used is based on crude bis (3-amino-4-hydroxyphenyl).
0.3-10 times (v / w), preferably 0.5-5.
It is 0 times (v / w), particularly preferably 1.0-3.0 times (v / w). If it is less than 0.5 (v / w), the fluidity becomes poor, and stirring and filtration become difficult. If it exceeds 10.0 times, the yield becomes low and it is not economical. Incidentally, it may contain an antioxidant such as hydrazines, sodium sulfide, hydrosulfite, hydroquinone and methoquinone.

The method of treating the crude bis (3-amino-4-hydroxyphenyl) with a solvent containing a lower alcohol includes, for example, a recrystallization method and a washing method. The washing method is performed, for example, by contacting a crude bis (3-amino-4-hydroxyphenyl) crystal with a mixed solvent containing a lower alcohol. Examples of the contacting method include a method of passing the mixed solvent through the crystal cake and a method of dispersing the crystals in the mixed solvent. Examples of the mixed solvent used here include the above-mentioned mixed solvent of water and lower alcohol and the mixed solvent of hydrocarbons and lower alcohol.

In the recrystallization method, for example, a crude bis (3-amino-4-hydroxyphenyl) is dissolved in a lower alcohol under heating or at room temperature, and then cooled, the solvent is distilled off, and water or hydrocarbons are removed. It is carried out by a method such as addition of a poor solvent or by combining these methods to precipitate crystals.

The recrystallization method will be described more specifically.
The method using water as the poor solvent may be performed, for example, as follows. That is, crude bis (3-amino-4-hydroxyphenyl) which may be anhydrous or water-containing
To the crude bis (3-amino-4)
After dissolving or dispersing the (-hydroxyphenyl) compound, water is added or the solution is sufficiently stirred. Further, after adding and dispersing the crude bis (3-amino-4-hydroxyphenyl) in water, a small amount of lower alcohol may be added. Further, the crude bis (3-amino-4-hydroxyphenyl) may be added to a purified solvent composed of water-lower alcohol. The order of adding the crude bis (3-amino-4-hydroxyphenyl), water, and lower alcohol is not particularly limited. The precipitated crystals are filtered off and dried,
High purity bis (3-amino-4-hydroxyphenyl)
Get the kind. Lower alcohols are initially in excess,
The crude bis (3-amino-4-hydroxyphenyl) is
Disperse or dissolve, heat, reduce pressure or normal pressure,
A part of the lower alcohols is distilled off to adjust the amount of the lower alcohols so that the alcohol ratio becomes 50 to 60% by weight. Then, hot water is added to reduce the amount of the mixed solvent containing the lower alcohols. It may be 1.0-3.0 times (v / w) that of bis (3-amino-4-hydroxyphenyl) s. After depositing the crystal, the crystal may be grown by cooling slowly. The amount of water to be added depends on the crude bis (3-amino-4
-Hydroxyphenyl) 0.3-5.0 times (v
/ W), preferably 0.5-3.0 times (v / w), particularly preferably 1.0-2.0 times (v / w). Crystals may be collected by filtering the crystals after hot precipitation, or by filtering them under cooling with ice. The filter cake may be further washed with a water-containing lower alcohol.

The method using hydrocarbons as a poor solvent can be carried out, for example, as follows. That is, crude bis (3-amino-4-, which may be anhydrous or water-containing,
A lower alcohol is added to the (hydroxyphenyl) s to dissolve or disperse the crude bis (3-amino-4-hydroxyphenyl) s. Further, hydrocarbons are added and the mixture is sufficiently stirred. After adding hydrocarbons first, lower alcohols may be added, or hydrocarbons adjusted in advance,
A purified solvent containing lower alcohols may be added.
Further, crude bis (3-amino-4-hydroxyphenyl)
May be added to the purification solvent. Crude bis (3-amino-4
-Hydroxyphenyl), hydrocarbons, and lower alcohols are added in any order. The precipitated crystals are separated by filtration, washed with a hydrocarbon containing a lower alcohol or a hydrocarbon, and, if necessary, washed with water and dried to obtain a high-purity bis (3-amino acid). -4-hydroxyphenyl). The lower alcohols are initially added in excess to the crude bis (3-amino-4-
Dispersing or dissolving hydroxyphenyl), heating and partially distilling the lower alcohol under reduced pressure or normal pressure to reduce the ratio of the lower alcohol to the crude bis (3-amino-4-hydroxyphenyl). May be adjusted to 40 to 60% by weight, and then hydrocarbons may be added during heating to precipitate crystals, followed by slow cooling to grow the crystals. The amount of hydrocarbons added was 0.3-1 based on the crude bis (3-amino-4-hydroxyphenyl).
0.0 times (v / w), preferably 0.5-5.0 times (v / w), particularly preferably 1.0-3.0 times (v / w).
w). The concentration of lower alcohols in the solvent is 2-
95% by volume, preferably 10-70% by volume, more preferably 15-50% by volume, particularly preferably 20-4% by volume
0% by volume. When the amount of the lower alcohol after the distillation is small, crystals are precipitated in the distillation step. Crystals may be collected by filtering the crystals after hot precipitation, or by filtering them under cooling with ice. After adding the hydrocarbons, the solvent may be further distilled off to adjust the concentration of the lower alcohols. Water may be contained, or hydrocarbons may be added, water may be azeotropically distilled to remove most of the water, and then lower alcohols may be added.

Alternatively, crystallization may be carried out from a water-containing reaction solution obtained by reducing a crude bis (3-nitro-4-hydroxyphenyl) using a lower alcohol as a reaction solvent. For example, the reaction solution is heated, and a predetermined amount of a solvent containing a lower alcohol is distilled off under reduced pressure or normal pressure. The end point temperature after the solvent was distilled off was 75-85 ° C., and the amount of the aqueous solvent containing lower alcohols remaining after the distillation was reduced with respect to the crude bis (3-amino-4-hydroxyphenyl). 0.3 to 10 times (v /
w), preferably 0.5-5 times (v / w), more preferably 1.0-3.0 times (v / w). The concentration of lower alcohols in the obtained water-containing solvent is 30 to 80% by volume, preferably 40 to 70% by volume, particularly preferably 50 to 70% by volume.
-60% by volume. After distilling off the solvent, crystallization was carried out by spontaneous crystallization or by adding seed crystals while cooling slowly. The liquid temperature during crystallization is particularly preferably 70-80 ° C. Crystals may be collected by filtering the crystals after hot precipitation, or by filtering them under cooling with ice. Preferably, it is better to slowly cool and sufficiently crystallize. The precipitated crystals are separated by filtration and washed with a solvent containing a lower alcohol, or thereafter, washed with water and dried to obtain a high-purity bis (3-amino-4-hydroxyphenyl). The concentration of the lower alcohol in the cleaning solvent containing the lower alcohol is 10-9.
0% by volume, preferably 30-70% by volume, particularly preferably 40-60% by volume. The amount of the washing solution is 0.3 to 10.0 times (w / w) the amount of bis (3-amino-4-hydroxyphenyl), preferably 0.5-fold.
5.0 times (w / w), particularly preferably 1.0-3.0 times (w / w).

The crude bis (3-amino-4) used in the present invention
-Hydroxyphenyl) is bis (3-nitro-4-
Hydroxyphenyls) can be obtained by reducing under hydrogen pressure and in the presence of a catalyst, or by reducing iron powder, reducing zinc, or reducing hydrazine. Specific examples of the reduction method are described below.

(1) Production method by hydrogenation using Raney nickel as a catalyst. Bis (3-nitro-4-hydroxyphenyl) s, a reaction solvent and Raney nickel are added to an autoclave, and hydrogen is introduced thereinto for reduction. Further, a reaction solvent, Raney nickel, is added to the autoclave, and bis (3-nitro-4-hydroxyphenyl) s are dissolved or dispersed in the reaction solvent under hydrogen pressure at a predetermined temperature, and continuously or intermittently. It may be charged and reacted. The amount of Raney nickel used is bis (3-nitro-4-
1 to 30% by weight, more preferably 5 to 10% by weight, based on the hydroxyphenyl). Examples of the reaction solvent include lower alcohols such as methanol, ethanol, n-propanol and isopropanol. The amount used is 0.5 to 20 times (v / w), more preferably 2 to 5 times (v / w) the amount of bis (3-nitro-4-hydroxyphenyl). The reaction temperature is 0-
The temperature is 150C, more preferably 40-80C. The hydrogen pressure is not particularly limited, but is usually 0-9 kg / cm.
² (gauge pressure).

(2) Production method by hydrazine reduction. Bis (3-nitro-4-hydroxyphenyl) is dissolved or dispersed in a reaction solvent and reduced by adding hydrazine in the presence of a catalyst. Alternatively, a reaction solvent, a catalyst and hydrazines are added, and the mixture is maintained at a predetermined temperature, and bis (3-nitro-4-hydroxyphenyl) is dissolved in a solid powder or after being dissolved or dispersed in the reaction solvent, or continuously or intermittently. And react. Examples of the hydrazines include hydrazine, hydrazine monohydrate, methylhydrazine, and hydrazinium salts such as hydrazinium chloride and hydrazinium sulfate. These reducing agents can be used as a solution, for example, an aqueous solution, an alcohol solution, or an ether solution, preferably 30 to 90% by weight, more preferably 60 to 80% by weight of an aqueous solution of hydrazine monohydrate. Good to use. The amount of the hydrazine used is 3.0 to 20.0 moles per mole of bis (3-nitro-4-hydroxyphenyl), preferably 3.0 to 5.0.
Used on a molar basis.

As the catalyst, iron halides / activated carbon,
Raney nickel, Pd / activated carbon, Ru / activated carbon and the like. Examples of the iron halide catalyst include ferrous chloride, ferric chloride, ferrous bromide, hydrates and anhydrides of ferric bromide, and the like. The amount of the iron halide to be used is 0.01 to 0.5 mol, preferably 0.02 to 0.5 mol, per 1 mol of bis (3-nitro-4-hydroxyphenyl) s.
1 mole. The activated carbon used in combination may be a hydrated product or a dried product, and 0.1 to 1000 parts by weight based on 100 parts by weight of bis (3-nitro-4-hydroxyphenyl) s.
Preferably it is 10 to 100 parts by weight.

The amount of Raney nickel used is 1-30% by weight, preferably 5-10% by weight, based on bis (3-nitro-4-hydroxyphenyl) s. Platinum and palladium may be used by being dispersed on a carrier such as activated carbon, silica gel, alumina, barium sulfate, calcium carbonate, pumice, porous diatomaceous earth, graphite, activated clay, magnesium oxide and / or aluminum oxide. In addition, it can be used as an oxide, and specific examples in which platinum oxide and palladium oxide can be used can be given.
For the weight ratio of noble metal to dinitroaromatic, the bis (3
-Nitro-4-hydroxyphenyl) based on 0.01
〜10.0% by weight, preferably 0.1-0.5% by weight. Examples of the reaction solvent include lower aliphatic alcohols such as methanol, ethanol, and isopropanol, and a mixed solvent thereof with water. Preferred solvents are methanol and isopropanol, more preferably methanol.

[0027]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these specific examples.

Example 1 NDT-9 was placed in a 500 cc autoclave equipped with a stirrer.
0 (trade name, Raney nickel catalyst, manufactured by Kawaken Fine Chemical Co., Ltd.) 24.4 g (in terms of alloy), methanol 30
0 cc and 100.0 g of 2,2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane were added, and the atmosphere was sufficiently replaced by nitrogen and hydrogen. Hydrogen pressure 3.0kg / c
pressurized to m ^2, and the reaction temperature was started from room temperature. The temperature was raised naturally to 60 ° C. upon the start of stirring, and hydrogen was continuously supplied during the reaction to maintain 3.0 kg / cm ^2. After the absorption of hydrogen was stopped, the mixture was further stirred for 30 minutes, cooled and allowed to stand. After filtering off the catalyst from the reaction solution, 80%
3.7 g of hydrazine monohydrate aqueous solution (Junsei Chemical Co., Ltd.)
And 10 minutes of Taiko Activated Carbon-SA (trade name, activated carbon, Nimura Chemical Co., Ltd.) was added.
After stirring for 20 minutes at 30C to 30C, the mixture is allowed to stand. After the activated carbon was filtered off from the reaction solution, the reaction solvent was recovered, concentrated and dried to dryness. As a result, 84.5 g of a crude product, a crude yield of 98.3%, and a liquid chromatographic analysis value of 98.1% (area%) were gray-white. Crude 2,2-
Bis (3-amino-4-hydroxyphenyl) hexafluoropropane was obtained.

Next, the obtained crude 2,2-bis (3-amino-4-hydroxyphenyl) was placed in a 300 cc four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer.
Hexafluoropropane (84.5 g) and isopropyl alcohol (120 cc) were added, and the mixture was refluxed for crude 2,2-bis (3
-Amino-4-hydroxyphenyl) hexafluoropropane dissolves. After making a red-brown homogeneous solution, 80 cc of isopropyl alcohol was distilled off from the system. While maintaining the reflux state while crystallization, 125 cc of toluene was gradually added, and after dropping of toluene was completed, stirring was continued at the reflux temperature for 15 minutes. Thereafter, the mixture was gradually cooled to room temperature over 1 hour, and further stirred at 0 to 5 ° C. for 30 minutes under ice water cooling. After sufficient precipitation of the crystals, the crystals and the purified solvent were separated on a Nutsche, and the crystals were filtered and washed with 500 cc of a mixed solution of 10% isopropyl alcohol and toluene. The cake was air dried thoroughly. High purity white crystals, purification yield 9
0.0%, yield 77.3 g, liquid chromatographic analysis 99.
9% (area%) was obtained.

Example 2 200 equipped with a thermometer, a Dimroth condenser and a stirrer
In a 0 cc four-necked flask, 2,2-bis (3-nitro-
4-hydroxyphenyl) hexafluoropropane 40
0.0 g and 1200 cc of methanol were added and stirred for 20 minutes, and then E196R / W 5% Pd (trade name, 5% palladium-carbon catalyst, manufactured by Degussa Japan Co., Ltd.) 2
0.0 g (dry equivalent) was added, and the mixture was heated with stirring and kept at a liquid temperature of 60 ° C. to 65 ° C., and 313.2 g of an aqueous solution of 60% hydrazine monohydrate was added dropwise over 4 hours. After the completion of the hydrazine charge, the reaction was continued for 30 minutes, the temperature was gradually cooled to room temperature, the catalyst was filtered off, the solvent was recovered from the reaction solution by an evaporator, concentrated, and dried to obtain a crude yield of 336.8 g.
A light red crude 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was obtained with a crude yield of 98% and a liquid chromatographic analysis of 97.9% (area%).

Next, the obtained crude 2,2-bis (3-amino-4-hydroxyphenyl) was placed in a 2000 cc four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer.
336 g of hexafluoropropane, 415 cc of methanol
And the mixture is refluxed to give crude 2,2-bis (3-amino-4-
Heat until (hydroxyphenyl) hexafluoropropane dissolves. After making a reddish brown homogeneous solution, water 255c
c was gradually added, and after dropping was completed, stirring was continued at reflux temperature for 15 minutes. Then, slowly cool to room temperature over 1 hour,
The mixture was further stirred at 0 to 5 ° C. for 30 minutes under ice water cooling. After sufficient precipitation of the crystals, the crystals and the purified solvent were separated on a Nutsche, and the crystals remaining on the Nutsche were sufficiently washed with 500 cc of water previously cooled to 5 ° C, and the filtrate was replaced. Air dried. High-purity white crystals, a yield of 89.3%, a yield of 306.9 g, and a liquid chromatographic analysis value of 99.9% (area%) were obtained.

Example 3 200 equipped with a thermometer, a Dimroth condenser and a stirrer
2,2-bis (3% containing 35% water in a cc four-necked flask
-Nitro-4-hydroxyphenyl) hexafluoropropane (39.4 g) and methanol (77 cc) were added, stirred for 20 minutes, and then E106B / W 5% Pd (trade name, 5% palladium-carbon catalyst, manufactured by Degussa Japan Co., Ltd.)
0.51 g (in dry terms) was added, and the mixture was heated under reflux with stirring, and kept at an initial liquid temperature of 69 ° C. to 73 ° C., and 20.0 g of an aqueous solution of 60% hydrazine monohydrate was added dropwise over 4 hours.
After the completion of the hydrazine charge, the reaction was continued for 30 minutes, the reaction was gradually cooled to room temperature, and the reaction was completed.
% (Area%) to give crude 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.

Next, 22 g of crude 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane obtained after filtering the catalyst was placed in a 200 cc four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer. , Heating under normal pressure, recovering a predetermined amount of solvent from the reaction solution, concentrating,
57 g of solvent was recovered from 28 g, and the temperature at which the solvent was distilled off was 79 ° C
After that, the distillation was terminated, and seeds were added for crystallization.
The solution temperature was kept at 79 ° C. for 30 minutes. Thereafter, the mixture was gradually cooled to room temperature over 1 hour, and further stirred at 0 to 5 ° C. for 30 minutes under ice water cooling. After sufficient precipitation of crystals, the crystals and the purified solvent are separated on Nutsche, and the crystals remaining on
Wash thoroughly with 45 g of 50% aqueous methanol solution cooled to 100 ° C. and 100 g of ion-exchanged water.
Time, more thoroughly dried. High purity white crystals, yield 8
8.3%, yield 19.4 g, liquid chromatographic analysis 99.
9% (area%) white 2,2-bis (3-amino-4)
-Hydroxyphenyl) hexafluoropropane was obtained.

Example 4 500 equipped with a thermometer, a Dimroth condenser and a stirrer
2,2-bis (3
-Nitro-4-hydroxyphenyl) hexafluoropropane (120.9 g) and methanol (250 cc) were added.
Stir for 1 minute, then 1.67 g of E106B / W 5% Pd
Then, 66.8 g of an aqueous solution of 60% hydrazine monohydrate was added dropwise over 4 hours while maintaining the initial liquid temperature at 69 ° C. to 73 ° C. while stirring. After the hydrazine was charged, the reaction was continued for 30 minutes, the reaction was gradually cooled to room temperature, and the reaction was completed. The liquid chromatographic analysis value was 97.3% (area%), and the crude 2,2-bis (3-amino-4-hydroxyphenyl) was obtained. ) Hexafluoropropane was obtained.

Next, 365 g of crude 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane obtained after filtration of the catalyst was placed in a 500 cc four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer. A predetermined amount of the solvent was recovered from the reaction solution by heating under normal pressure, concentrated, and 190 g of the solvent was recovered from the initial liquid amount of 365 g.
When the temperature reached 9 ° C., the distillation was terminated, seeds were added for crystallization, and the liquid temperature was kept at 79 ° C. for 30 minutes. Thereafter, the mixture was gradually cooled to room temperature over 1 hour, and further stirred at 0 to 5 ° C. for 30 minutes under ice water cooling. After sufficient precipitation of the crystals, the crystals and the purified solvent were separated on the Nutsche, and the crystals remaining on the Nutsche were cooled to 5 ° C. in advance with a 50% aqueous methanol solution.
g, and further thoroughly washed with 300 g of ion-exchanged water, and dried for 1 hour. High-purity white crystals,
87% yield, 63.3 g yield, liquid chromatographic analysis 9
9.9% (area%) of white 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was obtained.

[0036]

According to the present invention, bis (3-amino-4)
-Hydroxyphenyl) s, in particular, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, a compound useful as a raw material for heat-resistant polymers and the like, particularly a heat-resistant polymer for electronic materials and the like. This has the effect that purification can be performed efficiently with high yield. Also, the content of inorganic ions such as halogen ions and metal ions can be reduced.

Claims (7)

[Claims] 1. A method for purifying bis (3-amino-4-hydroxyphenyl), which comprises treating a crude bis (3-amino-4-hydroxyphenyl) with a solvent containing a lower alcohol. 2. Bis (3-amino-4-hydroxyphenyl) is represented by the formula (1) The method according to claim 1, wherein X is a bond or a direct bond between phenyl groups, and R ₁ and R ₂ are substituents. 3. The bonding chain for X is a substituted or unsubstituted alkylene, aralkylene, -O-, -S-, -SO-, -SO
3. A 2-, -CO-, substituted or unsubstituted amino.
Purification method described in 1. 4. The substituent of R ₁ and R ₂ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a hydroxyl group, an alkyloxycarbonyl group, a carbamoyl group, an amino group, an acyloxy group or a halogen atom.
Or the purification method according to 3. 5. The bis (3-amino-amino) according to claim 2, wherein the compound represented by the formula (1) is 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
4-hydroxyphenyl) purification method. 6. The treatment with a solvent containing lower alcohols is performed by dissolving crude bis (3-amino-4-hydroxyphenyl) in lower alcohols and then adding water or hydrocarbons. The method for purifying bis (3-amino-4-hydroxyphenyl) s according to claim 1, characterized in that: 7. Crystallization by distilling off a predetermined amount of a solvent containing a lower alcohol from a mixed solution containing a lower alcohol containing a crude bis (3-amino-4-hydroxyphenyl). The method for purifying bis (3-amino-4-hydroxyphenyl) s according to claim 1.