JPS6032619B2 - Method for producing aminophenols - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides catalytic reduction of nitrophenols, nitrosophenols, or their salts under hydrogen pressure in the presence of a Raney nickel catalyst treated with acidic sulfite in the liquid phase. This invention relates to a method for producing phenols.

More details: '1} A method for producing aminophenols, which comprises catalytically reducing nitrophenols, nitrosophenols, or their salts in the presence of an acidic sulfite-poisoned Raney nickel catalyst in a liquid phase under hydrogen pressure. .

■ Production of aminophenols according to claim 1, characterized in that the acidic sulfite-poisoned Raney nickel is treated with acidic sulfite in a liquid separate from the reaction solution prior to the reaction. Method.

{31 Acidic sulfite poison Raney nickel is poisoned with an acidic sulfite in a reaction solution in which catalytic reduction is carried out, The method for producing aminophenols according to claim 1 It is related to.

Aminophenols are used as intermediates for dyes and as stabilizers or antioxidants for various chemicals.

Demand for para-aminophenol is increasing as a raw material for acetaminphenol, a symptomatic treatment for colds. Regarding the production method of aminophenols, a method of catalytically reducing nitrophenols in the presence of a catalyst under pressure of hydrogen can be found in patents or literature. However, there are very few examples of catalytic reduction in the presence of a nickel-based catalyst, and only the following patents have been disclosed. ■ U.S. Pat. A method is described in which p-aminophenol separated, cooled, and precipitated is separated in a furnace, and the furnace liquid is reused for reduction.

(2) US Pat. No. 2,183, 01, describes a method for hydrogen reduction of p-nitrophenol, -nitrophenol, or p-nitrophenol soda salt in an aqueous system in the presence of a nickel catalyst. ■Special Public Service 1977-
No. 27318 is a method characterized by reacting a nitro-substituted phenol compound with hydrogen in an aqueous alkaline soot in the presence of a hydrogenation catalyst, and Example 4 thereof describes an example in which a Raney nickel catalyst was used. There is.

(2) Japanese Patent Publication No. 43-30294 is characterized in that a rapid reaction rate, which is industrially advantageous, is obtained by a method in which catalytic reduction is carried out in the presence of a nickel-based catalyst using a mixed solvent of water and methanol. None of the above patents provide detailed descriptions of the quality of the reduction product.

In particular, p-aminophenol is required to have extremely high purity when used as a raw material for pharmaceuticals. In addition, products that do not discolor for a long period of time are required. The present inventors have investigated the characteristics of hydrogen reduction using a Raney-nickel catalyst, focusing on evaluating the quality of the reduction product. As a result, p-nitrophenol is produced in the presence of a Raney-nickel catalyst, and the product is p-aminophenol. I learned that not only aminocyclohexanol is produced, but also aminocyclohexanol. (For this, see Tatsumi et al., Osaka University Technical Report, Vol. 5, 205-210 (1955 Wang))
Shinichiro Komatsu et al., Kyoto Imperial University Kuwaho A, 13326-33
6 (1930) reported that the by-product of p-aminocyclohexanol becomes noticeable at 16,000 or higher.

The present inventors have studied the catalytic reduction of nitrophenols, nitrosophenols, or their salts under various conditions using a Raney nickel catalyst with reference to the above-mentioned patents and literature. In the case of hydrogen reduction of the same species, it was observed that even under mild reduction conditions there is a characteristic that involves hydrogenation of aromatic rings.

In other words, it is possible to catalytically reduce nitrophenols or their salts under hydrogen pressure, but if a Raney nickel catalyst developed by a conventional method is used as is,
In addition to the target aminophenols, the reduction products include products resulting from many side reactions, such as hydrogenated aromatic rings, catalytic hydrogenolysis products described below, and hydrogenated aromatic rings. . It was found that some of these created organisms were highly susceptible to oxidation and were easily colored. More specifically, the reduction products were examined and identified by gas chromatography, and in addition to aminophenol, which is the main product and target product, aminocyclohexanol,
It was found that aniline, phenol, cyclohexylamine, cyclohexanol, etc. were created. The production rates of these creations were characteristic for each nitrophenol to be reduced. For example, in the reduction of p-nitrophenol, p-aminocyclohexanol is
- In the hydrogenation of nitrophenol, aniline and phenol produced by decomposition and their hydrogenated forms, cyclohexanol and cyclohexylamine, were recognized as the main by-products. When carrying out catalytic reduction of aromatic nitro compounds on a large scale, the catalytic reduction is carried out while gradually feeding the raw material nitro compound into the reactor in order to smoothly support the radish side.

In this case, reaction conditions are adjusted so that the raw nitro compound is virtually undetectable in the reactor. In this way, when nitrophenols come into contact with the catalyst surface at extremely dilute concentrations, in addition to the main reaction of reducing nitro groups to amino groups, hydrogen reduction to aromatic rings and catalytic decomposition are also promoted. It was recognized that Based on these experimental results, the present inventors conducted research on how to complete a technology that can produce aminophenols in a liquid phase using Raney-nickel catalysts, and as a result, the results will be detailed later. The production of aminocyclohexanols, the above-mentioned aminobenzenes and phenols, and their aromatic ring hydrogenation can be achieved by using Funehnickel catalysts poisoned with acidic sulfites under various conditions. We discovered that it is possible to suppress the production of substances extremely effectively.

The "poisoned" Raney nickel used to carry out the present invention can be obtained in the following manner.

Weigh a predetermined amount of the developed aqueous paste of Raney nickel, suspend it in a predetermined amount of distilled water (water that does not contain harmful heavy metal ions or sulfides), and pour a predetermined amount of acidic sulfite into a small amount using a rope. In addition, it is treated at a predetermined temperature for a predetermined time. After processing, remove the top solution, add freshly distilled water (same as above) and wash the rice bran. This washing operation is repeated several times, and the supernatant liquid is removed by decanting to obtain a "poisoned" Raney nickel aqueous paste. Using the poisoned Raney nickel aqueous paste thus produced, nitrophenols, nitrosophenols, or their salts are catalytically reduced under hydrogen pressure. When carrying out the reaction with a lower alcohol, an aqueous paste can be used after several substitution operations with the lower alcohol used. Alternatively, aminophenols can also be produced by catalytic reduction of nitrophenols, nitrosophenols, or salts thereof in the liquid phase under hydrogen pressure in the presence of acidic sulfite and a Raney nickel catalyst.

This method is preferably carried out as follows. That is, a predetermined amount of the developed Raney nickel aqueous paste is weighed, a portion of the water used for the reduction reaction is transferred to a reactor, a predetermined amount of acidic sulfite is added, and nitrophenols, nitrosophenols, or the like are added under hydrogen pressure. catalytic reduction of salts.

The acidic sulfite used in the present invention may be a salt having a chemical structure that is industrially easily available, such as acidic sodium sulfite, acidic ammonium sulfite, and the like. The amount of acidic sulfite to cause "sulfur" is 1/100 mole to 1/3 mole per 1 mole of nickel metal in Raney nickel, or in the case of acidic sodium sulfite per 100 g of nickel metal, from You can choose from a range.

The conditions under which it is appropriate to use the poisoned catalyst should be selected within a range that is industrially advantageous, depending on the type of nitrophenols, nitrosophenols, or their salts to be reduced. can be determined. Regarding the treatment method, if the amount of water used during poisoning, method of adding acidic sulfite, temperature, treatment time, number of times of washing after treatment, etc. are kept constant, there will be no noticeable difference in the poisoning effect. Since it does not appear, the method of reproducing the he table effect is high. The modified catalyst can be used repeatedly in the neutral to strong alkaline range.
Neither the activity nor the poisoning effect of the modified catalyst is significantly reduced by repeated use. Since the catalyst poisoned by the method of the present invention has lower activity than the non-poisoned catalyst, the amount used is, for example, 1. Sealing to 3. There is a need to do more than that. The relationship between the treatment conditions during poisoning and the degree of poisoning is as follows.

First, the amount of water used is related to the concentration of acidic sulfite, which is a poisoning agent, relative to the catalyst metal. The coverage effect will be greater. Any amount of water can be determined to suit the purpose of the present invention within an industrially manageable range. The method of adding acidic sulfite is usually to inject a concentrated aqueous solution into the solution, but the method is not limited thereto. The temperature at which poisoning occurs is usually room temperature or low temperature, and under heating, for example,
1000 to 4000, but is not necessarily limited thereto. The time required to hydrogenate a certain amount of nitrophenols, nitrosophenols, or their salts using the resulting catalyst is slightly longer when a catalyst treated at a higher temperature is used. Water rinsing after poisoning treatment is not performed when the reactor is poisoned by acidic sulfites.

Surprisingly, the effect of the treated catalyst does not diminish at all no matter how many times it is washed with water, and the poisoning effect persists even if the hydrogenation reaction is repeated with the same catalyst. was revealed as a result of the experiment.

As the method of catalytic reduction of nitrophenols, nitrosophenols, or their salts using the poisoned catalyst in the method of the present invention, several methods can be shown as follows.

However, the method of the present invention is not limited to these operating methods. ○ - Using water or a lower alcohol solvent, nitrophenols, nitrosophenols, or their salts are gradually introduced under pressure in the presence of a predetermined amount of catalyst for reduction. A method to obtain aminophenols produced by separating the catalyst under conditions such that all substances are dissolved, followed by crystallization by cooling, concentration, etc.

{2) A method of reducing the alkali metal salts of nitrophenols, nitrosophenols, or their salts, then separating the catalyst and neutralizing it to liberate the target aminophenols.

'3' In the presence of a predetermined amount of catalyst, a predetermined amount of alkali metal hydroxide is present in water or a lower alcohol solvent, and the alkali metal salt of aminophenols can be obtained by reduction under hydrogen pressure. .

It is generally more soluble than aminophenols, especially when heated. This method is used to reduce, separate and neutralize soot to obtain the desired product. {4) In '1}, at the same time as nitrophenols, nitrosophenols or their salts are injected, a predetermined amount of aqueous solution of alkali metal hydroxide is injected for reduction, and in the same manner as in [2', {3} How to get what you want.

■ Replenish the specified amount of catalyst, specified amount of solvent (water or lower alcohol), specified amount of nitrophenols, nitrosophenols, or their salts, and specified amount of aqueous alkali hydroxide solution to maintain hydrogen under constant pressure. A method in which aminophenols, which are the target products, are obtained from the reaction product liquid by continuously performing catalytic reduction by simultaneously pressurizing the reaction mixture into a reactor and removing the catalyst.

etc. The poisoned catalyst used in the present invention can be used for both batch reduction and continuous reduction, and can catalytically reduce nitrophenols at a practically rapid reaction rate.

The industrially valuable nitrophenols, nitrosophenols, or their salts to be reduced in the method of the present invention include p-nitrophenol m-nitrophenol o nitrophenol or their sodium salts p-nitrophenol Nitrophenol Examples include 4-nitroso-3-methylphenol or their ammonium salts, 2-nitro-p-cresol, 2-nitro-o-cresol, 2,4-dinitrophenol, and their sodium salts.

It is possible to produce the corresponding aminophenols by appropriately selecting the above-mentioned production methods using the poisoned catalyst of the method of the present invention and a similar method. The details of the present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 Into a beaker filled with Noobinko, we weighed and poured Raney nickel catalyst aqueous paste (manufactured by JII Ken Fine Chemical Co., Ltd.) equivalent to a predetermined amount in terms of alloy and water, and poured a predetermined amount of acidic sodium sulfite (Kanto Kagaku Co., Ltd.) while praying with a candle. (manufactured by the company) was added little by little and kept at room temperature for a predetermined period of time.

After that, I tilted it, threw away the supernatant water, added 100 ml of fresh water, and let it shine for 5 minutes. Once again, I tilted my head and threw away the water. This operation was repeated three times. Finally, the catalyst adhering to Yoko Haji was washed off, the water was thoroughly drained using a slant, and the mixture was used for the reaction. Put the covered catalyst, 200 g of water, and 1 p-nitrophenol in an autoclave with a 300 g. The temperature rose to 9500 while worshiping the lanterns.

When it reached 9500, increase the speed and increase the internal pressure to 10k9.
/ and started catalytic reduction.

During the reaction, the reaction temperature was maintained at 97-10 and 0, hydrogen was replenished, and the reaction pressure was maintained at 8-10 k9/gauge. After the reaction is carried out until the reduction of the nitro compound is completed (referred to as reaction termination), the reaction solution is maintained at the same temperature at 8 to 10 k9/Sakaki gauge, and after a certain period of time (referred to as the holding time after reaction termination). was taken out and analyzed by gas chromatography.

Table 1 shows the results.

Table 1 Reference Example 1 The same log equivalent Raney nickel catalyst aqueous paste alloy used in Example 1, 300 g of water, and 1 g of p-nitrophenol were placed in a 500 g autoclave equipped with a rope strainer.
The lid was closed, hydrogen was replaced, the pressure was increased to 5k9' gauge, and the temperature was raised to 9yo while slowly moving.

When the temperature reached 95 dC, the rope was tightened quickly to bring the internal pressure to 10k9/lump gauge, and catalytic reduction was started.

During the reaction, the reaction temperature was maintained at 97-100 pm, hydrogen was replenished, and the reaction pressure was maintained at 8-10 k9/gauge. Although the reduction of the nitro compound was completed in 3 minutes, hydrogen absorption continued. 8 to 10k at the same temperature while replenishing hydrogen
The gauge was maintained at g/g/. The reaction solution was sampled at regular intervals and analyzed by gas chromatography.
Table 2 shows the results. Table 2 Misty Trout Flea Worker Riko Yuhaya
p-Fuminofco [36 minutes later 6.85 20.95 69.477
0 〃 33.70 48.13 18.1
7120 〃 24.38 72.88 2.
73 Example 2 In the same manner as in Example 1, a Raney nickel catalyst paste equivalent to the specified amount of the alloy shown in Table 3 was poured into 100 g of water, kept at the temperature shown in Table 3 while holding a light, and a specified amount of acidic sodium sulfite was added. was added to the sardine in a small amount, and the sardines were incubated at a predetermined temperature for 30 minutes.

Washing of the catalyst after poisoning and reduction of p-nitrophenol were carried out in the same manner as in Example 1, and after completion of the reduction of the nitro compound, the composition of the reaction solution obtained was examined by maintaining the same temperature and pressure for a predetermined period of time. Ta.

Table 3 Fune 1110 ta 7 groups 25 minutes + time 〇, 9 poor 998, preliminary 2
″ ″ 55 18 ″ 011 99
．． 893″ 2 arc 85 knowledge ~ 13.5
046 99 Oni 4 ″″ 75~
051 9949 arc 12 ″5″
″ 15~sha 9 〃 500
9500 Fune Ichigumo Married Maizuru Habit Raiden Ryoshi Tsutomu Mi 61 o Yu 125 Abbreviation ``Solution 9 Minutes Rumor Time 5, 9 Minato 948, Mai 7
* 5 - - 6 1 18.57
81. *Reference Example Example 3 In the same manner as in Example 1, catalysts poisoned at the following proportions were prepared.

The poisoned catalyst was washed three times with 100 parts of water.

In a 500 skin autoclave equipped with a takazu, add a well-drained poisoned catalyst, 300 ml of water, and 30 ml of p-nitrophenol.
g, and then closed the lid, replaced with hydrogen, pressurized to 5k9/average gauge, and slowly raised the temperature to 125o0. When the pressure reaches 125qo, the internal pressure is increased to 10k.
9/lump gauge, and the reduction reaction was started.

When the reaction was carried out at 130:00, maintaining the gauge at 10 kg/kg, the reduction of the nitro compound was completed in 24.5 minutes.

Thereafter, it was maintained for 2 hours under the conditions used for the reaction. As a result of analysis, the composition of the reaction solution after 2 hours was found to be 0.55% low boiling point, 0.06% aminocyclohexanol, and 99.39% p-aminophenol.

Example 4 In the same manner as in Example 1, 15 g of Raney nickel catalyst aqueous paste alloy was used for poisoning at the proportions shown in Table 4.

The treatment temperature was room temperature. After treatment, it was thoroughly washed in the same manner as in Example 1. 500 ml of catalyst with a thickener, 300 ml of water, and 2 ml of p-nitrophenol soda salt.
Prepare 25.5g of hydrate, close the lid, replace with hydrogen,
Pressurize the 5k9′ ground gauge and slowly bow to 95.
The temperature was raised to qC.

When the temperature reaches 95o0, increase the speed and increase the internal pressure to 10k9.
/I increased the enemy gauge and started a reaction.

During the reaction, the reaction temperature was maintained at 10,000 ℃, and the reaction pressure was maintained at 8 to 10 k9/gauge while replenishing hydrogen. After the reduction of the nitro compound was completed, the reaction temperature and reaction pressure were maintained.

1. After 1 to 2 hours, the reaction solution was taken out and its composition was examined by gas chromatography.

The results are shown in Table 4. Table 4 Washing 6 times after treatment Reference example 2 Add 5 g of Fune Nickel ND alloy (manufactured by Kawaken Fine Chemicals Co., Ltd.) to 20% NaOH 80' at a concentration of 5000 or less and then warm it in a wound bath for 90 to 9500030 minutes. It was developed.

The developed Raney nickel catalyst aqueous paste was washed until the washing water became neutral.

500ml of bottle with strainer [Developed catalyst with water drained in an autoclave, 200ml of water and 39.9ml of p-nitrophenol dihydrate. The procedure was repeated in the same manner as in Reference Example 1, with the lid closed and hydrogen replaced.

In this example, the reaction temperature was kept at 80°C. Although the reduction of the nitro compound was completed in 22 minutes, hydrogen absorption continued. The reaction solution was sampled at regular intervals and its composition was investigated.

Table 5 shows the results. *；・
Table 5 Urabo Eel Cod Low Boil P-Puff Enore After 40 minutes 〇. 21% 6.74 omitted 93. o4 many 60 〃 0.29 10.55 89.1
6120 〃 2.01 15.27 82.
72 Example 5 An experiment similar to Example 4 was conducted using 15 g of the Raney nickel catalyst aqueous paste alloy used in the continuous hydrogenation reaction of different aromatic nitro compounds.

The results are shown in Table 6. In the fifth example in Table 6, the reaction temperature was 130°C. Table 6* Reaction temperature: 130° C. Others: 100° C. Example 6 7.5 g of Fune nickel catalyst aqueous paste alloy was treated at the following poisoning rate.

The treated catalyst was washed three times with 100' of water.

Furthermore, it was washed three times with 100 methanol each. With rope pestle 5
00 [Pour the poisoned catalyst paste from which methanol was removed by tilting, 300 methanol and 17 g of p-nitrophenol into an autoclave, close the lid, replace with hydrogen, and
Pressurize the k9/enemy gauge and slowly raise the temperature to 75o.
The temperature was raised to o.

When reaching 75qo, increase the frame speed and reduce the internal pressure to 10k9/
He became an enemy gauge and began to return.

Hydrogen was replenished according to hydrogen absorption. Internal pressure is 8 to 10k
9/Kept it on the ground. The reaction temperature was kept at 8'C. Reduction of the nitro form required 7 nights. 3 under the reaction conditions after the completion of the reaction.
Saved time. Table 7 shows the composition of the reaction solution immediately after the completion of the reaction and after 3 hours. Table 7 Aminocyclo p-amino low boiling point Hexyl phenol After 3 hours 0.09% Not observed 99.
91 Reference Examples 3 In Example 6, when a non-poisoning catalyst was used, the reduction of the nitro compound was completed in 26 minutes.

Table 8 shows the composition of the reaction solution immediately after the completion of the reaction and after 3 hours. Table 8 Low boiling point 2 sneak peeks ≧3 hours after forecast
0.06 foundation 2.47 large 97.47$ example
7 Example 4 Table 4 In the first example, acidic sodium sulfite 7
50-55% acidic ammonium sulfite instead of 50mo
When an aqueous solution (manufactured by Kanto Kagaku Co., Ltd.) at 1400 o was used, the reduction of the nitro compound was completed in 14 minutes.

After the reaction was completed, the reaction conditions were maintained for 3 hours. Table 9 shows the composition of the reaction solution immediately after the completion of the reaction and after 3 hours. Table 9
Amino Socro p-amino low boiling point Marinol Phenol 3 hours later 0.21 high 0
．． 02 omitted 99.77 *Example 8 Fune nickel catalyst aqueous paste alloy equivalent 1 female was treated at the following poisoning rate.

The poisoned catalyst was washed three times with 100M water each.

Put the coated catalyst from which the water had been removed by diagonally removing water, 200 M of water, and 1 g of p-nitrophenol into a 300' autoclave equipped with a rope strainer, close the lid, replace with hydrogen, and pressurize to a gauge of 5k9'. The temperature was raised to 95 oo while slowly heating up.
When it reaches 95oo, speed up the speed and reduce the internal pressure to 10k9/
I gave it to my enemy Gage and started the return. During the reaction, the reaction pressure was maintained at 8 to 10 kg/gauge depending on hydrogen absorption, and the reaction temperature was maintained at 95 to 10,000 ℃. After completion of the reduction of the nitro compound, the mixture was aged for 10 minutes under the reaction conditions. 100o after aging
While maintaining the temperature at 0, the foundation was stopped and the catalyst was allowed to settle.
Approximately 165 cc of top light containing no catalyst was extracted from the autoclave. The extracted reaction solution was cooled under a nitrogen stream,
The precipitated p-aminophenol crystals were separated by furnace. The furnace liquid was adjusted to 165 cc, and p-nitrophenol 1 was returned to the autoclave in which the catalyst and about 35 cc of the reaction liquid remained, and hydrogen reduction was repeated. Table 10 shows the results of three repetitions.

Further, Table 11 shows the compositions of the first, fifth, and eighth reaction solutions.

Table 10 Catalyst Water used Reaction completion time
Oven-dried cod, reusable, and dried.

Evening 200 14 minutes 69 Evening 2 ″ Residual catalyst
Last time residual liquid 35cC 28 8
．． 5th time furnace liquid 165cc3 〃 〃
″ 32 9
．． 04 〃 ″ ″
37 9.35 〃
〃 ″ 4
0 9.16 〃 ″
″ 4 7
10.37 〃 ″
″ 52 9.78
〃 〃 ″
57 9.1* There was some fluctuation in the amount of reaction liquid extracted.

Table 11 Low boiling point Aminosocro p-aminohexanol Phenol 1st time 0.17% Not recognized 99.83 high 5″ 0.33
″ 99.668 〃 0.18
99.82 Example 9 Fune nickel catalyst aqueous paste alloy equivalent 1 female was treated at the following poisoning rate.

Processing temperature Room temperature processing time
The catalyst which had been poisoned by 3 parts was washed 3 times with 100 parts of water each.

Put the oxidized catalyst, which had been strained to remove water, and 285 ml of water into a 500' autoclave with Nada Azusa equipment, close the lid, replace the hydrogen, pressurize to 5 kg/gauge, and slowly evaporate. The temperature was raised to 95 oo. When it reached 95 qo, increase the speed of the fly frame and add 10 qo of water, p-nit, using a metering pump that kept the introduction route and cylinder section warm.

Phenol water melt (purity 70%) 51.1g, water 20
Catalytic reduction was performed while press-fitting the samples into the autoclave in the order shown on the desk. The aqueous p-nitrophenol melt was injected under pressure over a period of 60 minutes. The reaction temperature was maintained at 95 to 10,000℃, hydrogen was replenished during the reaction, and the pressure was maintained at 8 to 10k9'C. Shortly after the injection was completed, no hydrogen absorption was observed. After keeping the same temperature as the reaction temperature for 1 minute, the feeding was stopped and the catalyst was allowed to settle.

Approximately 300' of supernatant, substantially free of catalyst, was withdrawn. Approximately 5 portions of reaction solution and catalyst remained in the autoclave. The extracted reaction solution was cooled under a nitrogen stream, and the precipitated p-aminophenol crystals were separated in a furnace. Approximately 210 ml of the furnace liquid was returned to the autoclave, and the same procedure as in the first step was carried out to prepare 10 parts of water and 3 parts of the p-nitrophenol melt.
Catalytic reduction was carried out by pressurizing 9.1 g of water and 20 g of water. p
The nitrophenol-water melt was injected for 60 minutes. After the reaction, about 250 ml of reaction solution was extracted. This reaction operation was repeated 1q times. The catalyst was left in the autoclave and no covering operation was performed during the repeating process. The compositions of the reaction liquids extracted from the first, third, fifth, seventh, and 1qth times were investigated by gas chromatography. The results are shown in Table 12. Table 12 Low boiling point RU; Shozo Z Miku 1st o. 15 omitted Not accepted 99.85*
3rd 0.20 trace 99.80
5th 0.32 0.09 99.60
7th 0.18 0.05 99.77
10th 0.18 0.05 99.78
Reference Example Put 200% of water and 200% of water into an autoclave, close the lid, replace with hydrogen, pressurize to 5k9/2 gauge, and while slowly bowing, The temperature was raised to 95 qo.

When it reached 95qo, the lighting speed was increased and the internal pressure was raised to 10k9/average gauge.

Using a metering pump keeping the cylinder part of the introduction route warm, add 10% water, p-nitrophenol-water melt (purity 7
0%)57. Catalytic reduction was performed while pressurizing 300ml of water and 30ml of water into an autoclave in that order. p-nitrophenol-
The water melt was press-fitted in two cases, one requiring 60 minutes and the other requiring 90 minutes. After the reaction, the contents of the autoclave were washed out with water, heated to dissolve the precipitated substances, passed through a hot oven to remove the catalyst, and the oven liquid was evaporated to dryness under vacuum. The product contained a hulk-like substance and quickly turned black in the air. The composition of the product was investigated by gas chromatography. The results were examined in Table 13. Table 13 Injection time of p-nitrophenol aqueous solvent Low boiling point Aminocyclobetanol p-aminophenol 60 minutes o. 34 turtle lo. 95 omitted 88.71 Blind p-nitophenol Low boiling point x Aminosic.

Yakenol p-aminopheno-nole water solvent injection time 90 minutes t 30.28
69.72x It is thought that the low boiling point components were scattered during evaporation to dryness.

Example 10 A rudder made of nickel catalyst aqueous paste alloy equivalent was treated at the following degree of poisoning.

Water 150 °C Sodium sulfite 750 °C Treatment temperature Room temperature Treatment time 3 minutes The washed catalyst was washed three times with 100 grams of water each.

The poisoned catalyst and water 255.9 and p-nitrophenol soda salt dihydrate 108. Put in the umbrella, close the lid, replace the hydrogen, pressurize to 5k9/ground, and slowly raise the temperature to 80o.
The temperature was raised to o. When the temperature reached 80q C, the speed of evacuation was increased, the internal pressure was set to 10k9' gauge, and hydrogen reduction was started.

The reduction of the nitro compound was completed in 126.5 minutes.

During the reaction, the reaction temperature was maintained at 80:00, hydrogen was replenished according to hydrogen absorption, and the reaction pressure was maintained at 8 to 10 k9/gauge. After the reaction was completed, the autoclave was kept at the same temperature as the reaction temperature for 10 minutes, the heat exchanger was stopped, and the autoclave was externally cooled. The pressure was reduced, the lid was opened, the contents were taken out, and the catalyst was separated from the furnace. The mixture was neutralized with hydrochloric acid under a nitrogen stream, and the precipitated p-aminophenol was collected in a furnace. The yield was 96%. The composition of the reaction solution is: low boiling point 0.18% aminocyclohexanol 0
．． 003% p-aminophenol99. It was a pseudo%.

Example 11 One part of Fune nickel catalyst aqueous paste alloy equivalent, one part of water
Acidic sulfite soda 750 while hanging on [50] and worshiping the light
A poisoned catalyst was prepared by adding a sample and keeping it at room temperature for 3 minutes.

After the poisoning treatment, it was washed three times with 100ml of water. With rope comb 5
00 [Pour the poisoned catalyst from which water was removed by slanting into an autoclave and 135.1 g of a 16.3% caustic soda aqueous solution,
Close the lid, replace with hydrogen, apply pressure to a 5k9'c mustache gauge,
The temperature rose to 80 oo while slowly bowing. 8000
When the temperature was reached, the speed was increased, the internal pressure was set to 10k9/gauge, and a metering pump with the cylinder part of the introduction route kept warm was used to pump out 30 g of water and a p-nitrophenol aqueous melt (purity 7).
0%) and 30 g of water were press-fitted in this order.

The p-nitrophenol-water melt was injected over a period of 180 minutes. During the reaction, the reaction temperature was maintained at 80° C., hydrogen was replenished according to hydrogen absorption, and the reaction pressure was maintained at 8 to 10 k9/gauge. After 30% of water had been injected, the autoclave was kept at the same temperature as the reaction temperature for 10 minutes, and then cooled from the outside of the autoclave. After cooling, the feeding was stopped and the catalyst was allowed to settle. Alarmed, the supernatant reaction solution containing substantially no catalyst was extracted. Carbon dioxide gas was blown into the extracted reaction solution to precipitate p-aminophenol, and after cooling, the p-aminophenol was separated by furnace. From the second time onwards, since the reaction solution containing the catalyst remained in the autoclave, the same operation as shown above was repeated.

The experimental results of this example are shown in Table 14.

Table 14 Example 12 1 part of Fune nickel catalyst aqueous paste alloy equivalent to 1 part of water
5. Hanging on top of the object, drinking acidic soda 750 sulfite while worshiping.
A small amount of mo was added to the mixture, and the mixture was heated to room temperature for 30 minutes.

After treatment, it was refined three times with 100 g of water. 500 with damage device
Add the poisoned catalyst, which had been removed from the water in an autoclave, and 120ml of water, close the lid, replace the hydrogen, pressurize to 5k9/gauge, and slowly raise the temperature to 9000 while heating. did. When it reaches 9000, increase the fly speed and reduce the internal pressure by 1.
109.5 g of p-nitrophenol-water melt (purity 70%) was injected using a metering pump with a 0k9/gage and keeping the cylinder part of the introduction path warm.

At the same time, 5 dilutions of a 40% aqueous sodium hydroxide solution was injected in parallel using another metering pump. Both liquids were injected for 16 minutes. During the reaction, the reaction temperature was maintained at 90 q0, and hydrogen was replenished according to hydrogen absorption to maintain the internal pressure at 8 to 10 k9/g.
Immediately after the injection of the p-nitrophenol-water melt was finished, hydrogen absorption stopped, so the autoclave was kept at the same temperature for 10 minutes and then cooled from the outside of the autoclave. After cooling, the rope worship was stopped and the catalyst was allowed to settle. After a while, 233 g of a supernatant reaction solution containing substantially no catalyst was extracted. The composition of the extracted reaction solution was examined by gas chromatography, and the result was a low boiling point of 0.04%, no aminocyclohexanol, and 99.96% of p-aminophenol. The reaction solution was neutralized with concentrated hydrochloric acid under a nitrogen stream to precipitate p-aminophenol, and after cooling down, p-aminophenol was purified. It weighed 48g after vacuum drying. (Theoretical quantity is 4
8. Example 13 15 g of Raney nickel catalyst aqueous paste alloy equivalent to 15 g of Raney nickel catalyst aqueous paste alloy, 300 g of water, 750 g of acidic sodium sulfite, and 1 flower of p-nitrophenol were placed in a 500' autoclave with a cypress pot. Put it in, close the lid, check the hydrogen pupil, 5k9
Pressure was applied to the /me gauge, and the temperature was raised to 95 qo while stirring slowly.

When it reached 95oo, increase the fly speed and increase the internal pressure to 10k9/
We used Sakaki gauge and started catalytic reduction.

During the reaction, the temperature was maintained at 95 to 100 pm, and the reaction pressure was maintained at 8 to 10 k9' gauge while replenishing hydrogen according to hydrogen absorption. The reduction reaction of the nitro compound was completed in 3 minutes. After the reaction was completed, the temperature and pressure were kept the same as the reaction conditions.

In the same manner, a reaction was carried out using 200 parts of acidic sodium sulfite.

The reduction reaction of the nitro compound was completed in 5.5 minutes.

After the reaction was completed, the temperature and pressure were kept the same as the reaction conditions. After a certain period of time, the reaction solution was taken out and analyzed by gas chromatography. Table 15 shows the results. Table 15 Example 14 Put 15 g of Raney nickel catalyst aqueous paste, 300 g of water, 750 g of acidic sodium sulfite, and 1 g of p-nitrophenol into a 500 g autoclave equipped with a rice cooker, close the lid, and add hydrogen. The air was replaced, the pressure was increased to 5K9/Gauge, and the temperature was raised to 9500C.

When it reached 95 qo, the reduction rate was increased and the internal pressure was increased to 10 k9/qo gauge to start the catalytic reduction reaction.

During the reaction, the temperature was maintained at 95 to 10 psi, and the internal pressure was maintained at 8 to 10 k9/average gauge by replenishing hydrogen according to hydrogen absorption. The reduction reaction of the nitro compound was completed in 38 minutes. Thereafter, the reaction temperature was maintained for 5 minutes, and then the waste gas was stopped and the catalyst was allowed to settle, and the supernatant reaction liquid containing substantially no catalyst was extracted. During the autoclave, about 50% of the catalyst and reaction liquid are
[was left. After the autoclave has cooled down, reduce the pressure, lift the lid and add 250 g of water and 14 g of p-nitrophenol. Then, the lid was closed again and catalytic reduction was carried out in the same manner. The reduction reaction of the nitro compound required 59 minutes. The reaction solution was extracted in the same manner. Table 16 shows the analysis results of the composition of the reaction solution each time. Table 16 p-amino low boiling point Z-shizueshi Kunor 1st o. o5* Not accepted 99.95 second
The reaction solution extracted at 0.02 99.98 times was cooled and precipitated p-aminophenol was separated in a furnace.

Example 15 One piece of Fune nickel catalyst aqueous paste alloy equivalent was treated at a poisoning rate.

Processing temperature Room temperature processing time
The poisoned catalyst was purified three times using 100% water each.

Put the poisoned catalyst and 215' of water into a 500 autoclave with a frame loss device, close the lid, replace the hydrogen, pressurize to 5k9/gauge, and slowly cook the sea bream. The temperature was raised to 9,500 degrees. When the temperature reached 95oC, the speed of the pestle was increased and the internal pressure was adjusted to 10k9c.

Water 10 skin-p-nitrophenol ammonia aqueous solution (p
- A mixture of 1 head of nitrosophenol, 28% NH3, and 15 parts of water) - 30 parts of water were injected in this order using a metering pump. The p-nitrosoammonia aqueous solution was added over a period of 80 minutes. During the reaction, the temperature was maintained at 100° C., and the internal pressure was maintained at 8 to 9/c fin gauge while supplying hydrogen according to hydrogen absorption. By the time 30 minutes of washing water had been injected, almost no hydrogen had been absorbed.

After the reaction was completed, the temperature and pressure were kept the same as the reaction conditions. The reaction solution was sampled at regular intervals and its composition was examined using gas chromatography. The results are shown in Table 17. *One hour after Omotemachi Gunshio Nephew Hire Shoiri stopped 0.66ゑ o. oo8 reward 99.33
3 hours after stopping Tashoiri 0.56 0.05 99
．． Example 38 A covered catalyst was prepared with a weight ratio of 16th order.

The poisoned catalyst was washed three times with 100 g of water each.

A poisoned catalyst with a 500-liter autoclave to remove water, 250 grams of water, an aqueous solution of o-nitrophenol and caustic soda (17 g of o-nitrophenol, 4 grams of caustic soda, and 50 grams of water) (I made it myself) and close the lid.
The autoclave was replaced with hydrogen, pressurized to 5K9/Gauge, and heated to 95OO while slowly turning on the light. When the temperature reached 9,500, the speed was increased, the internal pressure was set to 10k9/lump gauge, and catalytic reduction was started.

During the reaction, the reaction temperature was maintained at 95 to 10,030 degrees Celsius, and the reaction pressure was increased to 80 degrees Celsius while replenishing hydrogen as it was absorbed.
I kept it at 10k9/gage. The reduction of nitro body is 1
Completed in 0 minutes. After the reaction was completed, the reaction conditions were maintained for 3 hours and the composition of the reaction solution was examined by gas chromatography. In the reaction solution, the catalyst was first separated in a furnace, neutralized with an aqueous HCI solution, and the precipitated o-aminophenol was collected after cooling down. On the other hand, Raney nickel catalyst aqueous paste alloy conversion 1o
g was used in the same reaction without poisoning.

The compositions of the reaction solutions for these two reactions were investigated using gas chromatography. The results are shown in Table 18. Table 18 Reference Example Example 17 Two poisoned catalysts were prepared at the following weight ratios.

Fune nickel catalyst aqueous base East alloy conversion None of them screamed for 100 minutes after being exposed. The rice bran was washed three times using two different types of rice bran.

Each has 500 [auto] with a fly pestle. Tilt the water into the crepe Removed poisoned catalyst and water 300 Scream and m-nitrophenol Insert the log and close the lid. Hydrogen replacement, 5k9/enemy game Pressurize it and slowly worship the light While doing so, the temperature was raised to 95℃.

When it reaches 9500, the loss number Gauge for internal pressure of 10kg/ As a result, contact reduction was started. Ta.

During the reaction, the temperature was maintained at 95 to 10,000℃ and the pressure was Replenishes hydrogen according to elementary absorption While playing 8-10k9/engagement game I kept it on the same page.

Reduction of nitro body is that Finished in 13.5 minutes and 24.8 minutes, respectively. did.

After the reaction is completed, change the reaction conditions. After holding for 3 hours, reduce the pressure, Take out the reaction solution and add the catalyst to the furnace. Separate the furnace liquid into an evaporator. Vacuum evaporate with m-a Minophenol was obtained.

On the other hand, Raney nickel contact Hydrophilic paste alloy conversion One female was exposed to the same reaction without being poisoned. It was used accordingly.

The reaction completion time in this case was 18.8 minutes. Ta.

The same reaction conditions were maintained for 3 hours.

These experimental results are shown in Table 19. It was shown to.

Table 19 Concubine reference example Example 18 poisoned touch in the following weight ratio: I created a medium.

The poisoned catalyst was purified three times using 100 parts of water.

In a 500' autoclave equipped with a takazu, put the Qin catalyst from which the water was removed, 300 M of water, and 7.6 g of 5-nitro-o-cresol, close the lid, replace with hydrogen, and add 5k9/
Pressure was applied to the lump gauge, and the temperature was raised to 100 oo while slowly turning on the light.

When the temperature reaches 100o0, increase the fly frame speed and increase the internal pressure to 10k.
9/1, and catalytic reduction was started.

During the reaction, the temperature was maintained at 10 to 105 qo, and the pressure was increased to 8 to 10 qo while replenishing hydrogen according to hydrogen absorption.
I kept it in the enemy gauge. 7. Reduction of nitro form. It was already over. After the completion of the reaction, the reaction conditions were maintained for 2 hours, the pressure was reduced, the reaction liquid was taken out, the catalyst was separated from the furnace, and the furnace liquid was cooled.
Table 20 shows the results of the experiment in which amino-o-cresol was obtained.

The composition of the taken out reaction solution was investigated by gas chromatography.

On the other hand, one female (equivalent to Raney nickel catalyst aqueous paste alloy) was used in the same reaction without being mixed.

The reaction termination time in this case was 6 minutes. The same reaction conditions were maintained for 2 hours.

These two actual tables 20 Concubines Reference Example Example 19 A catalyst was made with the following weight ratio.

The poisoned catalyst was washed three times with 100 parts of water.

The poisoned catalyst, which had been removed by autoclaving with a rope strainer, 250 g of water, and an aqueous solution of 2,4-dinitrophenol and caustic soda (2,4-dinitrophenol, 22 g.
．． 5g, caustic soda 4. The tank was heated to 10,000 ℃ while stirring slowly.

When reaching 100qo, increase the pseudo-Azusa speed and reduce the internal pressure to 10k9.
/ Became an enemy gauge and started contact reduction.

During the reaction, the temperature was maintained at 10 to 10 degrees Celsius, and the pressure was kept at 8 to 10 k9/lump gauge with hydrogen replenishment depending on hydrogen uptake.

Reduction of the nitro form required 37.5 minutes. Thereafter, the reaction conditions were maintained for 3 hours, but no hydrogen absorption occurred. The autoclave was cooled from the outside, the pressure was reduced, the lid was opened, the reaction solution was taken out under a nitrogen stream, the catalyst was separated, the autoclave was neutralized with HCl, and the water was evaporated in vacuo to obtain 2,4-diaminophenol. The yield was 96.8%. On the other hand, the same operation as above was performed using 1 og of Raney nickel catalyst aqueous paste alloy equivalent.

Reduction of the nitro form required 17.5 minutes. After the reaction was completed, the mixture was held for 3 hours. The yield was 96.5%. When each reaction solution was acidified with hydrochloric acid and spotted on a thin layer of silica gel and developed with ethanol, the one that had been reduced with hydrogen using a poisoning catalyst showed a single spot with an Rf value of 0.5, whereas it was not poisoned. Hydrogen reduction using a catalyst*
In addition to the Rf value 0.5 spot, Rf value 0.55 0. Spots were also shown on the stain, indicating that low molecular weight compounds were being produced.

*Reference Example Example 20 A catalyst was made with the following weight ratio.

The poisoned catalyst was thoroughly washed three times using 100 volumes of water each.

In a 500-core autoclave with a rope strainer, add the strained catalyst to remove water, 250 g of water, and 2 nitro-p-cresol caustic soda solution (2 nitro-p-cresol 1 ml).
5. Pour in warm NaOH and 50 ml of water, close the lid, replace with hydrogen, pressurize to 5 kg/gage,
The temperature was raised to 9yC while slowly worshiping the candles.

When reaching 95qo, increase the speed and increase the internal pressure to 10k9
/ Became an enemy gauge and started contact reduction.

During the reaction, the temperature was maintained at 95-100 q C and the pressure was maintained at 8-10 k9/gauge, supplemented according to hydrogen absorption. The reduction of the nitro compound was completed in 7.5 minutes.

After the reaction was completed, the reaction conditions were maintained for 3 hours, but no hydrogen was absorbed. The autoclave was cooled externally, the pressure was reduced, the lid was opened, and the reaction solution was taken out. After the catalyst was removed from the furnace, the furnace solution was neutralized with concentrated hydrochloric acid to precipitate cresamine (2-nitro-p-cresol). After cooling down, the crystals were taken up in a furnace and dried in vacuum. The yield was 9%.

Claims (1)

[Scope of Claims] 1. Production of aminophenols, characterized by catalytic reduction of nitrophenols, nitrosophenols, or their salts in the presence of an acidic sulfite-poisoned Raney-nickel catalyst in a liquid phase under hydrogen pressure. Method. 2. Production of aminophenols according to claim 1, wherein the acidic sulfite-poisoned Raney nickel is treated with acidic sulfite in a liquid separate from the reaction solution prior to the reaction. Method. 3. The method for producing aminophenols according to claim 1, wherein the acidic sulfite-poisoned Raney nickel is poisoned with an acidic sulfite in a reaction solution in which catalytic reduction is carried out.