KR20170109448A - METHOD OF PREPARING p-PHENYLENEDIAMINE - Google Patents

Abstract

The present invention relates to a method of preparing p-phenylenediamine, and more specifically, to a method of preparing p-phenylenediamine from 1,4-benzoquinone dioxime, and to a method for preparing p-phenylenediamine from para-nitroso phenol and hydroxylamine through a one-pot method.

Description

METHOD OF PREPARING P-PHENYLENEDIAMINE [0002]

More particularly, the present invention relates to a process for producing paraphenylenediamine from 1,4-benzoquinone dioxime and a process for producing para-phenylenediamine from para-nitroso phenol and hydroxylamine. One-pot. ≪ / RTI >

Para-phenylenediamine is used as a raw material for producing high heat-resistant aramid fibers and as a base material for producing polyurethane raw material p-phenylenediisocyanate. It is also used in dyes, cosmetics, antioxidant raw materials and fuel additives ≪ / RTI >

In general, as a conventional method for producing paraphenylenediamine, para-nitroaniline (PNA) is prepared by substituting ammonia for p-nitrochlorobenzene (PNCB) And then adding paraphenylenediamine through an addition process. However, a part of the ortho isomer is included in the process of preparing PNCB, which is a starting material, resulting in a small amount of ortho-isomer remaining in p-phenylenediamine, which makes it difficult to produce highly pure p-phenylenediamine. Further, it has a problem that it is difficult to treat a large amount of chlorine-containing wastewater generated in the process of substitution reaction with PNA in PNCB.

As another method, diazonium salt of diazonium salt is produced by diazonation of aniline, and then paraphenylenediamine and aniline are obtained through hydrogenation. US Patent No. 4,020,052 discloses a process for producing 1,3-diphenyltriazine by diazotizing aniline with nitrogen oxide and then reacting the diazotized compound with an excess of aniline to prepare 1,3-diphenyltriazine, which is rearranged under acidic conditions rearrangement, and hydrogenating to obtain paraphenylenediamine and aniline. However, according to this method, relatively high purity paraphenylenediamine can be produced, but the process is complicated and requires a multi-step reaction. In addition, since an excessive amount of aniline is used, effective recovery is not only a problem but also causes a large amount of organic wastewater to be generated, resulting in an economically costly problem.

In another method, benzamide (Benzamide), known as nucleophilic aromatic substitution of hydrogen (NASH) reaction, and tetravalent organic ammonium, a phase transfer catalyst, from nitrobenzene are used in U.S. Patent No. 5,436,371, N (4-Nitrophenyl) benzamide] is synthesized and hydrolyzed to prepare PNA and benzoic acid (or benzamide). According to this method, PNA can be produced very selectively, and a highly pure p-phenylenediamine can be produced by performing hydrogenation reaction thereon. However, this method has a disadvantage that it is difficult to obtain the product at a high yield due to the difficulty of adjusting the reaction conditions because the water must be controlled very strictly, and a phase transition catalyst having a relatively high cost is used.

Therefore, conventional methods for producing paraphenylenediamine have difficulty in producing highly pure paraphenylenediamine and generate a large amount of wastewater. Further, there is a disadvantage in that it is difficult to produce efficient paraphenylenediamine because the production process is complicated and the production cost is high.

U.S. Patent No. 4,020,052 U.S. Patent No. 5,436,371

As a result of many studies to solve the above problems, it has been found that parephenylenediamine can be directly produced by reducing 1,4-benzoquinone dioxime, and 1,4-benzoquinone dioxane can be prepared from para- Quinonedioxime can be prepared and para-phenylenediamine can be prepared as a one-pot through a simple reduction reaction. Thus, the present invention has been completed.

Accordingly, it is an object of the present invention to provide a process for producing paraphenylenediamine from 1,4-benzoquinone dioxime by a simple reduction reaction, by which para-phenylenediamine can be easily produced, And a method for producing phenylenediamine.

It is another object of the present invention to provide a method for preparing 1,4-benzoquinone dioxime from para-nitroso phenol and hydroxylamine, and producing para-phenylenediamine as a one-pot through a simple reduction reaction.

The present invention provides a method for producing a high yield and high purity paraphenylenediamine by a simple process.

The method for producing the paraphenylenediamine of the present invention comprises:

(a) preparing a 1,4-benzoquinonedioxime solution; And

(b) reducing the 1,4-benzoquinone dioxime of the solution to produce paraphenylenediamine.

Reduction of 1,4-benzoquinone dioxime according to an embodiment of the present invention can be performed by adding hydrogen in the presence of a metal supported catalyst.

The metal supporting catalyst according to an embodiment of the present invention may be a catalyst in which a metal active material is supported on a carbon or alumina support.

The metal active material according to an embodiment of the present invention may be one or more selected from the group consisting of palladium, platinum, ruthenium, osmium, nickel, iridium, rhodium, and alloys thereof.

The effect of the present invention can be further achieved when the metal active material according to an embodiment of the present invention is palladium or platinum, which is preferable.

The metal supporting catalyst according to an embodiment of the present invention may be a catalyst carrying palladium or platinum on a carbon support.

The metal-supported catalyst according to one embodiment of the present invention may be added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of 1,4-benzoquinonedioxime.

Reduction of 1,4-benzoquinone dioxime according to an embodiment of the present invention may be performed at 10 to 200 ° C.

The pressure of hydrogen according to one embodiment of the present invention may be between 5 and 25 atmospheres.

Reduction of 1,4-benzoquinone dioxime according to an embodiment of the present invention can be performed by adding a reducing agent.

Reduction of 1,4-benzoquinone dioxime according to one embodiment of the present invention may be performed under acidic conditions.

The reducing agent according to an embodiment of the present invention may be one or more selected from the group consisting of metal, metal or boron hydride, sulfur, hydrogen sulfide, sulfite and hydrogen sulfite.

The metal according to an embodiment of the present invention may be one or more selected from zinc, magnesium, iron, tin, calcium and aluminum.

It is preferred because the effect of the present invention can be achieved when the metal according to one embodiment of the present invention is zinc or magnesium.

Metal or a hydride of boron, in accordance with an embodiment of the present invention, _{NaBH 4 (sodium borohydride), LiAlH} 4 (lithium aluminium hydride), B 2 H 6, AlH 3, NaH, 1 more selected from KH, CaH _2, and MgH ₂ Or two or more.

The effect of the present invention can be further achieved when the metal or boron hydride according to an embodiment of the present invention is NaBH ₄ (sodium borohydride), which is preferable.

The sulfur flame, the hydrogen sulfide salt, the sulfurous acid salt, and the hydrogen sulfurous acid salt according to an embodiment of the present invention may include one or more cations selected from an alkali metal cation, an ammonium cation, and an alkaline earth metal cation.

The reducing agent according to one embodiment of the present invention may be added in an amount of 40 to 200 parts by weight based on 100 parts by weight of 1,4-benzoquinonedioxime.

The acidic condition according to one embodiment of the present invention may be formed using at least one selected from hydrochloric acid, sulfuric acid, ammonium formate (HCO ₂ NH ₄ ), acetic acid, and formic acid.

Reduction of 1,4-benzoquinone dioxime according to an embodiment of the present invention may be performed at 20 to 150 ° C.

The 1,4-benzoquinone dioxime solution according to an embodiment of the present invention may be prepared by reacting a lower alcohol having 1 to 7 carbon atoms such as methanol, ethanol, and isopropanol, a lower alcohol such as dimethylsolventoxide (DMSO), dimethylformamide (DMF) Benzoquinone dioxime may be prepared by dissolving 1,4-benzoquinone dioxime in one or two polar solvents selected from acetamide and N-methylpyrrolidone (NMP).

After step (b) according to an embodiment of the present invention, the step of condensing the result of step (b), precipitating to produce a precipitate (step c) and recrystallizing the precipitate (step d) .

The present invention also relates to a process for producing p-phenylenediamine by reacting p-nitrosophenol with hydroxylamine in a polar solvent, adding a metal-supported catalyst and adding hydrogen to produce p-phenylenediamine ≪ / RTI >

The present invention also provides a method for producing p-phenylenediamine by reacting p-nitrosophenol with hydroxylamine in a polar solvent and then adding a reducing agent thereto.

The process for producing paraphenylenediamine according to the present invention is a process for producing paraphenylenediamine of high purity from 1,4-benzoquinone dioxime through a simple reduction reaction, which is easy to produce, has a relatively low production cost, Can be minimized.

In addition, the process for preparing paraphenylenediamine of the present invention is a process for preparing 1,4-benzoquinone dioxime from para-nitroso phenol and hydroxylamine, and simultaneously producing a high-purity paraphenylenediamine by a simple reduction reaction, .

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention.

However, the following description does not limit the present invention to specific embodiments. In the following description of the present invention, detailed description of related arts will be omitted if it is determined that the gist of the present invention may be blurred .

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.

Hereinafter, the production method of the paraphenylenediamine of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

The present invention provides a method for producing a high yield and high purity paraphenylenediamine by a simple process.

The method for producing the paraphenylenediamine of the present invention comprises:

(a) preparing a 1,4-benzoquinonedioxime solution; And

(b) reducing the 1,4-benzoquinone dioxime of the solution to produce paraphenylenediamine.

First, 1,4-benzoquinone dioxime is dissolved in a polar solvent to prepare a 1,4-benzoquinone dioxime solution (step a).

The 1,4-benzoquinone dioxime may be represented by the following general formula (1).

[Chemical Formula 1]

Examples of the polar solvent include lower alcohols having 1 to 7 carbon atoms such as methanol, ethanol and isopropanol, dimethylsolventoxide (DMSO), dimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone (NMP) It is possible.

The 1,4-benzoquinone dioxime can be prepared by reacting p-nitrosophenol with hydroxylamine, but is not limited thereto. Commercial 1,4-benzoquinonedioxime can be purchased and used, and can be prepared by various known methods. When 1,4-benzoquinone dioxime is prepared by reacting para-nitroso phenol with hydroxylamine, the following steps are carried out in a single pot without separate separation or purification steps to give paraphenylenediamine Can be prepared.

Next, 1,4-benzoquinone dioxime of the solution is reduced to produce paraphenylenediamine (step b).

The para-phenylenediamine may be represented by the following general formula (2).

(2)

Reduction of 1,4-benzoquinone dioxime in step (b) is performed by adding hydrogen (Method A) or adding a reducing agent to the solution (Method B) in the presence of a metal-supported catalyst in the solution.

In the method A according to an embodiment of the present invention, the metal supporting catalyst may be a catalyst in which a metal active material is supported on a carbon or alumina support.

The metal active material according to an embodiment of the present invention may be one or more selected from the group consisting of palladium, platinum, ruthenium, osmium, nickel, iridium, rhodium and alloys thereof. In some respects, it may preferably be palladium or platinum.

The metal supported catalyst according to an embodiment of the present invention may more preferably be a catalyst carrying palladium or platinum on a carbon support.

In the method A according to an embodiment of the present invention, the metal-supported catalyst may be added in an amount of 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, per 100 parts by weight of 1,4-benzoquinonedioxime, More preferably 0.1 to 10 parts by weight, still more preferably 0.1 to 5 parts by weight. If the amount of the metal supported catalyst is out of the above range, the yield and economical efficiency may be lowered.

In Method A according to one embodiment of the present invention, the reduction of 1,4-benzoquinone dioxime can be performed at 10 to 200 ° C, preferably 10 to 150 ° C, more preferably 10 to 100 ° C , And even more preferably under reflux conditions.

In the method A according to an embodiment of the present invention, the pressure of the hydrogen may be 5 to 25 atm, preferably 5 to 20 atm, more preferably 10 to 15 atm.

In the method B according to an embodiment of the present invention, the reducing agent may be one or more selected from the group consisting of a metal, a metal or a boron hydride, a sulfur flame, a hydrogen sulfide salt, a sulfite, and a hydrogen sulfite.

The metal according to an embodiment of the present invention may be zinc, magnesium, iron, tin, calcium, aluminum, or the like, preferably zinc or magnesium.

The metal or a hydride of boron, in accordance with an embodiment of the present invention, _{NaBH 4 (sodium borohydride), LiAlH} 4 (lithium aluminium hydride), B 2 H 6, AlH 3, NaH, KH, CaH 2, MgH 2 , etc. is possible It will be, and preferably may be a NaBH ₄ (sodium borohydride).

The sulfur, hydrogen sulfide, sulfite and hydrogen sulfite salts according to an embodiment of the present invention may include alkali metal cations, ammonium cations or alkaline earth metal cations, preferably Na ⁺ , NH ₄ ⁺ , K ⁺ Ca ^{2 +} , Mg ^{2 +} , Ba ^{2 +,} and the like, and more preferably Na ⁺ or NH ₄ ⁺ .

In the method B according to an embodiment of the present invention, the reducing agent may be added in an amount of 40 to 200 parts by weight, preferably 40 to 150 parts by weight, and more preferably 40 to 150 parts by weight based on 100 parts by weight of 1,4-benzoquinonedioxime May be added in an amount of 45 to 120 parts by weight. If the amount of the reducing agent used is out of the above range, the yield and economical efficiency may be lowered.

In the method B according to an embodiment of the present invention, the reduction of the 1,4-benzoquinone dioxime can be carried out under acidic conditions. To the 1,4-benzoquinone dioxime solution, hydrochloric acid, sulfuric acid, Acidic conditions can be formed by adding mate (ammonia formate, HCO ₂ NH ₄ ), acetic acid, formic acid, or the like. In this case, it may be preferable to use a metal as a reducing agent.

In Method B according to one embodiment of the present invention, the reduction of 1,4-benzoquinone dioxime can be carried out at a temperature of from 20 캜 to the temperature at which the polar solvent is refluxed, preferably from 20 to 150 캜, Lt; RTI ID = 0.0 > 80 C < / RTI >

After step (b) according to an embodiment of the present invention, the step of condensing the result of step (b), precipitating to produce a precipitate (step c) and recrystallizing the precipitate (step d) And the purity of the paraphenylenediamine can be improved by the recrystallization.

The method of preparing paraphenylenediamine of the present invention can be carried out by reacting p-nitrosophenol and hydroxylamine in a polar solvent, adding a metal-supported catalyst, adding hydrogen, or adding a reducing agent To prepare p-phenylenediamine as a one-pot.

That is, when 1,4-benzoquinone dioxime is prepared by reacting para-nitroso phenol with hydroxylamine, the above-described steps are carried out in a single pot without separate separation or purification, It is possible to prepare a lendiamine.

[Example]

Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.

The product prepared through the following examples was analyzed and analyzed using a gas chromatography-mass spectrometry detector (GC-MS). Quantitative analysis was performed using paraphenylenediamine of Sigma-Aldrich as a standard reagent Respectively. Test conditions for gas chromatography are as follows.

1) Capillary column: ULTRA2 (Crosslinked 5% Ph Me Silicone) 50 mm x 0.2 mm x 0.33 m

2) Carrier gas: Nitrogen

3) Head pressure: 20psi

4) Oven: 100 ° C (2min) to 200 ° C, β = 10 ° C / min

5) Detector and Temperature: FID (280 ° C)

6) Split ratio: 30: 1

7) Make-up gas flow rate: 30ml / min

The yield of the product was calculated on the basis of the 1,4-benzoquinone dioxime used.

[Production of paraphenylenediamine]

Example  One

A solution of 13.8 g (0.1 mole) of 1,4-benzoquinonedioxime (BQO, Sigma-Adrich) in 50 ml of methanol was added to 1 g of 5% Pd / C catalyst (5% palladium on activated carbon, Sigma-Aldrich) The mixture was placed in an autoclave reactor, and hydrogen gas was slowly injected into the tube through the tube while stirring at 80 ° C. The reaction was continued for 2 hours while maintaining the pressure at 10 atm. After the reaction was completed, the reaction mixture was cooled to room temperature, the catalyst was removed by a filter, and the solvent was removed by distillation under reduced pressure to obtain 11 g of a solid.

The solids were dissolved in 100 ml of ethanol, treated with 5 g of activated carbon at 50 ° C, and then concentrated under reduced pressure with 30 ml of a solution to prepare a concentrate. The resultant precipitate was filtered and vacuum dried to obtain 8.4 g of paraphenylenediamine (yield: 78%, GC analysis purity: 99.0%, GC / Mass [M] < + >: 108).

^{1 H NMR (300 MHz, DMSO} -d 6) δ 6.51 (s, 4H), 3.3 (brs, 4H); ¹³ C NMR (100 MHz, DMSO-d ₆ )? 139.5, 116.1

Example  2

(Yield: 81%, GC analysis purity: 98.5%, GC / Mass [M] +) was obtained in the same manner as in Example 1, except that DMSO (dimethyl sulfoxide) was used instead of methanol to obtain 8.7 g of paraphenylenediamine. : 108).

Example  3

Except that 8% Pt / C (8% platinum on activated carbon) catalyst was used in place of 5% Pd / C catalyst (yield: 70% GC purity 98.0%, GC / Mass [M] +: 108).

Example  4

15 g of zinc was added to a solution of 20.7 g (0.15 mole) of 1,4-benzoquinonedioxime (BQO) in 100 ml of methanol, and the mixture was introduced into a reactor equipped with a reflux condenser, and 50 ml of a 20% And the reaction was allowed to proceed slowly. After completion of the reaction, methanol was removed by distillation under reduced pressure, and the mixture was cooled to room temperature. The pH of the solution was adjusted to 12 with 10% caustic soda solution and extracted with 100 ml of toluene. Next, toluene was removed through vacuum distillation to obtain 15 g of a solid.

The solids were dissolved in 100 ml of ethanol, treated with 5 g of activated carbon at 50 ° C, and then concentrated under reduced pressure with 30 ml of a solution to prepare a concentrate. The resultant precipitate was filtered and vacuum dried to obtain 10.3 g of paraphenylenediamine (yield: 64%, GC analysis purity: 97.5%, GC / Mass [M] < + >: 108).

Example  5

Except that a solution obtained by dissolving 25 g of ammonium formate in 50 ml of water instead of the hydrochloric acid solution was used to prepare 10.9 g of paraphenylenediamine (yield: 67%, GC analysis Purity 98.0%, GC / Mass [M] < + >: 108).

Example  6

(Yield: 72%, GC analysis purity: 97.5%, GC / Mass [M] +: 108) was obtained in the same manner as in Example 4 except that 10 g of magnesium was used instead of zinc ).

Example  7

A solution in which 13.8 g of 1,4-benzoquinonedioxime (BQO) was dissolved in 50 ml of methanol was charged into a reactor equipped with a reflux apparatus, 8 g of NaBH ₄ powder was slowly added thereto under reflux for 2 hours, Further reaction. When the reaction was completed, the solid precipitate formed by cooling to room temperature was filtered off, and then 10 g of solid matter was obtained by distillation under reduced pressure.

The solids were dissolved in 100 ml of ethanol, treated with 5 g of activated carbon at 50 ° C, and then concentrated under reduced pressure with 30 ml of a solution to prepare a concentrate. The resultant precipitate was filtered and vacuum dried to obtain 8.2 g of paraphenylenediamine (yield: 76%, GC analysis purity: 98.5%, GC / Mass [M] < + >: 108).

Example  8

(Yield: 69%, GC analysis purity: 98.5) was prepared in the same manner as in Example 7, except that 50 ml of a 15% Na ₂ S (sodium sulfide) aqueous solution was used instead of 8 g of NaBH ₄ powder. %, GC / Mass [M] < + >: 108).

Example  9

5.7 g of paraphenylenediamine (yield: 53%, GC analysis purity: 97.6%) was obtained in the same manner as in Example 7, except that 50 ml of 25% NaHSO ₃ (sodium bisulfite) aqueous solution was used instead of 8 g of NaBH ₄ powder. , GC / Mass [M] < + >: 108).

Example  10

(Yield: 56%, GC analysis purity: 98.0%, GC / Mass (mass%)) was prepared in the same manner as in Example 7, except that 50 ml of a 15% aqueous solution of MgSO ₃ was used instead of 8 g of NaBH ₄ powder. [M] < + >: 108).

Example  11

A solution of 12.3 g (0.1 mole) of p-nitrosophenol in 50 ml of methanol was placed in an autoclave reactor, and 8 g of hydroxylamine hydrochloride (NH ₂ OH · HCl, hydroxylamine hydrochloride) was dissolved in 25 ml of water Solution was added to prepare a reaction solution. After the temperature of the reaction solution was lowered to 5 캜, 20% ammonia water was added slowly until the pH became 12, and further stirred for 2 hours while maintaining the temperature at not over 10 캜. Next, the temperature of the reaction solution was raised to room temperature, and then 1 g of a 5% Pd / C catalyst was added. The reaction solution was slowly injected with hydrogen gas through a tube pipe while stirring at 80 ° C, and the reaction was carried out for 2 hours while maintaining the pressure at 10 atm. After the reaction was completed, the reaction mixture was cooled to room temperature, the catalyst was removed by a filter, and the solvent was removed by distillation under reduced pressure to obtain 11 g of a solid.

The solids were dissolved in 100 ml of ethanol, treated with 5 g of activated carbon at 50 ° C, and then concentrated under reduced pressure with 30 ml of a solution to prepare a concentrate. The resultant precipitate was filtered and vacuum dried to obtain 7.7 g of paraphenylenediamine (yield: 71%, GC analysis purity: 98.0%, GC / Mass [M] < + >: 108).

Example  12

Except that 10 g of hydroxylamine sulfate ((NH ₂ OH) ₂ SO ₄ , hydroxylamine sulfate) was used instead of 8 g of hydroxylamine hydrochloride (NH ₂ OH.HCl, hydroxylamine hydrochloride) To obtain 8.0 g of paraphenylenediamine (yield: 74%, purity of GC: 98.5%, GC / Mass [M] +: 108).

Example  13

A solution obtained by dissolving 12.3 g (0.1 mole) of p-nitrosophenol in 50 ml of methanol was placed in a reactor equipped with a reflux apparatus, and 10 g of hydroxylamine sulfate ((NH ₂ OH) ₂ SO ₄ , hydroxylamine sulfate) Was dissolved in 25 ml of water to prepare a reaction solution. After the temperature of the reaction solution was lowered to 5 캜, 20% ammonia water was added slowly until the pH became 12, and further stirred for 2 hours while maintaining the temperature at not over 10 캜. After the stirring, 50 ml of a 25% NH ₄ HSO ₃ (sodium bisulfite) aqueous solution was slowly added thereto at room temperature over 2 hours, and then reacted for 2 hours. When the reaction was completed, the resulting solid precipitate was filtered off and vacuum distilled to obtain a solid.

The solids were dissolved in 100 ml of ethanol, treated with 5 g of activated carbon at 50 ° C, and then concentrated under reduced pressure with 30 ml of a solution to prepare a concentrate. The resultant precipitate was filtered and vacuum dried to obtain 5.8 g of paraphenylenediamine (yield: 54%, GC analysis purity: 98.3%, GC / Mass [M] < + >: 108).

Comparative Example  One

Para-phenylenediamine purchased from Sigma-Aldrich was used as Comparative Example 1.

(GC / Mass [M] < + >: 108)

[Test Example]

Test Example  One: Paraphenylenediamine  Manufacturing Confirmation

Analysis of the GC-MS of the paraphenylenediamine according to Example 4 and Comparative Example 1 showed that the results were consistent.

Thus, it was confirmed that para-phenylenediamine conforming to the para-phenylenediamine standard reagent purchased from Sigma-Aldrich was produced in high purity according to Example 4.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Claims (9)

(a) preparing a 1,4-benzoquinonedioxime solution; And
(b) reducing the 1,4-benzoquinone dioxime of the solution to prepare paraphenylenediamine;
≪ / RTI > The method according to claim 1,
The reduction of 1,4-benzoquinone dioxime in the step (b) is carried out by adding hydrogen in the presence of a metal-supported catalyst on which a metal active material is supported on a carbon or alumina support. Way. 3. The method of claim 2,
Wherein the metal active material is at least one selected from the group consisting of palladium, platinum, ruthenium, osmium, nickel, iridium, rhodium and alloys thereof. The method according to claim 1,
Wherein the reduction of the 1,4-benzoquinone dioxime in the step (b) is carried out by adding a reducing agent. 5. The method of claim 4,
Wherein the reducing agent is at least one selected from the group consisting of a metal, a metal or a boron hydride, a sulfur flame, a hydrogen sulfide salt, a sulfite, and a hydrogen sulfite. 6. The method of claim 5,
Wherein the metal is zinc, magnesium, iron, tin, calcium and aluminum, one or two or more kinds selected from the metal or the hydride of boron is _{NaBH 4 (sodium borohydride), LiAlH} 4 (lithium aluminium hydride), B 2 H 6 , AlH ₃ , NaH, KH, CaH _2, and MgH _2. The sulfur, hydrogen sulfide, sulfite and hydrogen sulfite salts may be one or more selected from the group consisting of alkali metal cations, ammonium cations and alkaline earth metal cations Or at least two kinds of cations. The method according to claim 1,
Characterized in that after said step (b) further comprises the step of concentrating and precipitating the product of step (b) to produce a precipitate (step c) and recrystallizing said precipitate (step d) / RTI > P-nitrosophenol and hydroxylamine in a polar solvent, adding a metal-supported catalyst, and adding hydrogen to produce p-phenylenediamine as a one-pot. Reacting p-nitrosophenol with hydroxylamine in a polar solvent, and then adding a reducing agent to prepare p-phenylenediamine as a one-pot.