CN111302956B - Preparation method of 4-bromo-2-aminophenol - Google Patents
Preparation method of 4-bromo-2-aminophenol Download PDFInfo
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- CN111302956B CN111302956B CN202010289475.2A CN202010289475A CN111302956B CN 111302956 B CN111302956 B CN 111302956B CN 202010289475 A CN202010289475 A CN 202010289475A CN 111302956 B CN111302956 B CN 111302956B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
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Abstract
The invention belongs to the field of chemical synthesis, and in particular relates to a preparation method of 4-bromo-2-aminophenol, which comprises the following steps: (1) Adding Raney-Ni catalyst into water, then adding ferric nitrate and chromium nitrate, and stirring to obtain a mixed solution; (2) Adding an alkali solution into the mixed solution obtained in the step (1), continuously stirring, washing with water, and replacing water with methanol to obtain a Fe-Cr modified Raney-Ni catalyst; (3) Dissolving 2-nitro-4-bromophenol in an alcohol solvent, adding a Fe-Cr modified Raney-Ni catalyst, and carrying out hydrogenation reaction at normal pressure to obtain an alcohol solution of 4-bromo-2-aminophenol; (4) Filtering, desolventizing and refining to obtain 4-bromo-2-aminophenol. The Fe-Cr modified Raney-Ni catalyst has the advantages of high conversion rate, good selectivity, low debromination rate and good durability, and can inhibit debromination side reaction.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of 4-bromo-2-aminophenol.
Background
4-bromo-2-aminophenol is an important intermediate for the production of dyes, mainly for the production of pharmaceuticals, dyes and chemicals. In the prior art, most aromatic amine is obtained by reducing nitroaromatic hydrocarbon, wherein the iron powder reduction method is more common, but the post-treatment process of the iron powder reduction method is more complex, the energy consumption is high, and the pollution is serious. Catalytic hydrogenation belongs to a green reduction technology and is increasingly utilized, wherein the Raney-Ni catalyst has the advantages of higher activity, good sedimentation separation performance and the like for 4-bromo-2-aminophenol hydrogenation reaction, but has a plurality of defects. The direct use of commercial Raney-Ni catalyst for the reduction hydrogenation reaction also has the problems of high debromination rate (2-3%) and poor selectivity (about 97%).
Therefore, it is important to provide a method for preparing 4-bromo-2-aminophenol with high conversion rate of hydrogenation reduction nitro and good selectivity.
Disclosure of Invention
In order to solve the defects of low conversion rate and low selectivity in the preparation of 4-bromo-2-aminophenol in the prior art, the invention aims to provide a preparation method of 4-bromo-2-aminophenol. The method has the advantages of high conversion rate, low debromination rate and high yield of 4-bromo-2-aminophenol.
The invention is realized by the following technical scheme:
a preparation method of 4-bromo-2-aminophenol comprises the following steps:
(1) Adding Raney-Ni catalyst into water, then adding ferric nitrate and chromium nitrate, stirring and uniformly mixing to obtain a mixed solution;
(2) Adding an alkali solution into the mixed solution obtained in the step (1), continuously stirring for reaction, washing with water to be neutral, and replacing water with methanol to obtain a Fe-Cr modified Raney-Ni catalyst;
(3) Dissolving 2-nitro-4-bromophenol in an alcohol solvent, adding the Fe-Cr modified Raney-Ni catalyst obtained in the step (2), and carrying out hydrogenation reaction at normal pressure to obtain an alcohol solution of 4-bromo-2-aminophenol;
(4) Filtering, desolventizing and refining to obtain 4-bromo-2-aminophenol.
Preferably, in the step (1), the iron nitrate is added in an amount of 0.023 to 0.027mol and the chromium nitrate is added in an amount of 0.012 to 0.018mol based on the mole number of nickel. The iron auxiliary agent is adopted to modify the Raney-Ni catalyst so as to improve the activity of nitro hydrogenation, and the chromium auxiliary agent is adopted to modify the Raney-Ni catalyst so as to improve the selectivity of the catalyst in the process of hydrogenating the o-phenol nitro, so that the Fe-Cr modified Raney-Ni catalyst has the advantages of high conversion rate and good selectivity in the process of hydrogenation reduction of the nitro.
Preferably, the alkali solution in the step (2) is sodium hydroxide solution, and the alkali solution is added in an amount such that the pH of the mixed solution is 8+ -0.5.
Preferably, the mass concentration of the sodium hydroxide solution is 5wt% to 10wt%.
Preferably, the reaction in step (2) takes from 30 to 60 minutes.
Preferably, the Fe-Cr modified Raney-Ni catalyst in step (3) is added in an amount of 0.8mol% to 1.2mol% of the 2-nitro-4-bromophenol.
Preferably, the alcoholic solvent in step (3) is methanol.
In the hydrogenation reaction process in the step (3), after detecting the disappearance of the reaction of the central control raw material 2-nitro-4-bromophenol, the hydrogenation reaction is required to be continued for 30-45min.
Preferably, the refining in the step (4) is refining by vacuum rectification.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the iron auxiliary agent is adopted to modify the Raney-Ni catalyst so as to improve the activity of nitro hydrogenation, and the chromium auxiliary agent is adopted to modify the Raney-Ni catalyst so as to improve the selectivity of the catalyst in the process of hydrogenating the o-phenol nitro, so that the hydrogenation reduction of the nitro by the Fe-Cr modified Raney-Ni catalyst has the advantages of high conversion rate, higher selectivity, capability of inhibiting the occurrence of debromination side reaction and lower debromination rate (0.3 mol%).
(2) Compared with the problems of complex post-treatment, high energy consumption and serious pollution of the preparation of 4-bromo-2-aminophenol by the method for reducing iron powder in the prior art, the Fe-Cr modified Raney-Ni catalyst has good durability, can be recycled for more than 10 times, does not need complex post-treatment, is environment-friendly and has low cost.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The numerical values set forth in these examples do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
Example 1
A preparation method of 4-bromo-2-aminophenol comprises the following steps:
(1) Adding 5.0g of Raney-Ni catalyst into water, then adding ferric nitrate and chromium nitrate, and stirring and uniformly mixing to obtain a mixed solution;
the addition amount of the ferric nitrate is 0.023mol based on the mole number of nickel, and the addition amount of the chromium nitrate is 0.015mol;
(2) Adding a sodium hydroxide solution with the mass concentration of 5wt% into the mixed solution obtained in the step (1), regulating the pH value of the mixed solution to 8+/-0.5, continuously stirring for reaction for 30min, washing with water to be neutral, and replacing water with methanol to obtain the Fe-Cr modified Raney-Ni catalyst;
(3) 1mol of 2-nitro-4-bromophenol is dissolved in 500mL of methanol, 0.8mol of Fe-Cr modified Raney-Ni catalyst obtained in the step (2) is added, hydrogen is introduced into the mixture for hydrogenation reaction under normal pressure, after the disappearance of the reaction of the central control raw material 2-nitro-4-bromophenol is detected, hydrogenation reaction is continued for 30min, and a methanol solution of 4-bromo-2-aminophenol is obtained;
(4) Filtering, desolventizing and refining by adopting vacuum rectification to obtain the 4-bromo-2-aminophenol.
The content of 4-bromo-2-aminophenol obtained in this example was 99.5%, and the yield was 89.5%; the nitro conversion was 100% and the debromination was 0.3mol%.
Example 2
A preparation method of 4-bromo-2-aminophenol comprises the following steps:
(1) Adding 5.0g of Raney-Ni catalyst into water, then adding ferric nitrate and chromium nitrate, and stirring and uniformly mixing to obtain a mixed solution;
the addition amount of the ferric nitrate is 0.025mol based on the mole number of nickel, and the addition amount of the chromium nitrate is 0.012mol;
(2) Adding 10wt% sodium hydroxide solution into the mixed solution obtained in the step (1), regulating the pH value of the mixed solution to 8+/-0.5, continuously stirring for reaction for 30min, washing with water to be neutral, and replacing water with methanol to obtain the Fe-Cr modified Raney-Ni catalyst;
(3) 1mol of 2-nitro-4-bromophenol is dissolved in 500mL of methanol, 1.0mol of Fe-Cr modified Raney-Ni catalyst obtained in the step (2) is added, hydrogen is introduced into the mixture for hydrogenation reaction under normal pressure, after the disappearance of the reaction of the central control raw material 2-nitro-4-bromophenol is detected, hydrogenation reaction is continued for 40min, and a methanol solution of 4-bromo-2-aminophenol is obtained;
(4) Filtering, desolventizing and refining by adopting vacuum rectification to obtain the 4-bromo-2-aminophenol.
The content of 4-bromo-2-aminophenol obtained in this example was 99.5%, and the yield was 89.8%; the nitro conversion was 100% and the debromination was 0.3mol%.
Example 3
A preparation method of 4-bromo-2-aminophenol comprises the following steps:
(1) Adding 5.0g of Raney-Ni catalyst into water, then adding ferric nitrate and chromium nitrate, and stirring and uniformly mixing to obtain a mixed solution;
the addition amount of the ferric nitrate is 0.027mol based on the mole number of nickel, and the addition amount of the chromium nitrate is 0.018mol;
(2) Adding a sodium hydroxide solution with the mass concentration of 5wt% into the mixed solution obtained in the step (1), regulating the pH value of the mixed solution to 8+/-0.5, continuously stirring for reaction for 30min, washing with water to be neutral, and replacing water with methanol to obtain the Fe-Cr modified Raney-Ni catalyst;
(3) 1mol of 2-nitro-4-bromophenol is dissolved in 500mL of methanol, 1.2mol of Fe-Cr modified Raney-Ni catalyst obtained in the step (2) is added, hydrogen is introduced into the mixture for hydrogenation reaction under normal pressure, after the disappearance of the reaction of the central control raw material 2-nitro-4-bromophenol is detected, hydrogenation reaction is continued for 45min, and a methanol solution of 4-bromo-2-aminophenol is obtained;
(4) Filtering, desolventizing and refining by adopting vacuum rectification to obtain the 4-bromo-2-aminophenol.
The content of 4-bromo-2-aminophenol obtained in this example was 99.5%, and the yield was 90.0%; the nitro conversion was 100% and the debromination was 0.3mol%.
Comparative example 1
A preparation method of 4-bromo-2-aminophenol comprises the following steps:
(1) Adding 5.0g of Raney-Ni catalyst into water, then adding ferric nitrate, stirring and uniformly mixing to obtain a mixed solution;
the addition amount of the ferric nitrate is 0.023mol based on the mole number of nickel;
(2) Adding a sodium hydroxide solution with the mass concentration of 5wt% into the mixed solution obtained in the step (1), regulating the pH value of the mixed solution to 8+/-0.5, continuously stirring for reaction for 30min, washing with water to be neutral, and replacing water with methanol to obtain the Fe-modified Raney-Ni catalyst;
(3) 1mol of 2-nitro-4-bromophenol is dissolved in 500mL of methanol, 0.8mol of Fe modified Raney-Ni catalyst obtained in the step (2) is added, hydrogen is introduced into the mixture for hydrogenation reaction under normal pressure, after the disappearance of the reaction of the central control raw material 2-nitro-4-bromophenol is detected, hydrogenation reaction is continued for 30min, and a methanol solution of 4-bromo-2-aminophenol is obtained;
(4) Filtering, desolventizing and refining by adopting vacuum rectification to obtain the 4-bromo-2-aminophenol.
The content of 4-bromo-2-aminophenol obtained in this example was 98.2% and the yield was 81.5%; the nitro conversion was 98% and the debromination was 1.5mol%.
Comparative example 2
A preparation method of 4-bromo-2-aminophenol comprises the following steps:
(1) Adding 5.0g of Raney-Ni catalyst into water, then adding chromium nitrate, and stirring and uniformly mixing to obtain a mixed solution;
the adding amount of the chromium nitrate is 0.015mol;
(2) Adding a sodium hydroxide solution with the mass concentration of 5wt% into the mixed solution obtained in the step (1), regulating the pH value of the mixed solution to 8+/-0.5, continuously stirring for reaction for 30min, washing with water to be neutral, and replacing water with methanol to obtain a Cr-modified Raney-Ni catalyst;
(3) Dissolving 1mol of 2-nitro-4-bromophenol in 500mL of methanol, adding 0.8mol% of Cr-modified Raney-Ni catalyst obtained in the step (2), introducing hydrogen to perform hydrogenation reaction under normal pressure, detecting the disappearance of the reaction of the central control raw material 2-nitro-4-bromophenol, and continuing the hydrogenation reaction for 30min to obtain a methanol solution of 4-bromo-2-aminophenol;
(4) Filtering, desolventizing and refining by adopting vacuum rectification to obtain the 4-bromo-2-aminophenol.
The content of 4-bromo-2-aminophenol obtained in this example was 98.5%, and the yield was 83.0%; the nitro conversion was 98% and the debromination was 2.0mol%.
The Fe-Cr modified Raney-Ni catalyst obtained in examples 1 to 3, the Fe modified Raney-Ni catalyst obtained in comparative example 1 and the Cr modified Raney-Ni catalyst obtained in comparative example 2 were repeatedly used, and the results show that the Fe-Cr modified Raney-Ni catalyst in examples 1 to 3 can be repeatedly used for more than 10 times and still has good activity, and the Fe modified Raney-Ni catalyst obtained in comparative example 1 and the Cr modified Raney-Ni catalyst obtained in comparative example 2 have more remarkable activity reduction after being repeatedly used for 5 times.
Therefore, the Raney-Ni catalyst modified by the Fe-Cr has high conversion rate and higher selectivity, can inhibit the occurrence of debromination side reaction, and has lower debromination rate (0.3 mol%).
Compared with the problems of complex post-treatment, high energy consumption and serious pollution of the preparation of 4-bromo-2-aminophenol by the method for reducing iron powder in the prior art, the Fe-Cr modified Raney-Ni catalyst has good durability, can be recycled for more than 10 times, does not need complex post-treatment, is environment-friendly and has low cost.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (6)
1. The preparation method of the 4-bromo-2-aminophenol is characterized by comprising the following steps:
(1) Adding Raney-Ni catalyst into water, then adding ferric nitrate and chromium nitrate, stirring and uniformly mixing to obtain a mixed solution;
(2) Adding an alkali solution into the mixed solution obtained in the step (1), continuously stirring for reaction, washing with water to be neutral, and replacing water with methanol to obtain a Fe-Cr modified Raney-Ni catalyst;
(3) Dissolving 2-nitro-4-bromophenol in an alcohol solvent, adding the Fe-Cr modified Raney-Ni catalyst obtained in the step (2), and carrying out hydrogenation reaction at normal pressure to obtain an alcohol solution of 4-bromo-2-aminophenol;
(4) Filtering, desolventizing and refining to obtain 4-bromo-2-aminophenol;
in the step (1), the addition amount of the ferric nitrate is 0.023 to 0.027mol based on the mole number of nickel, and the addition amount of the chromium nitrate is 0.012 to 0.018mol;
the alkali solution in the step (2) is sodium hydroxide solution, and the addition amount of the alkali solution is based on that the pH value of the mixed solution is 8+/-0.5;
the Fe-Cr modified Raney-Ni catalyst in the step (3) is added in an amount of 0.8mol% to 1.2mol% of the 2-nitro-4-bromophenol.
2. The method for preparing 4-bromo-2-aminophenol according to claim 1, characterized in that the sodium hydroxide solution has a mass concentration of 5% to 10% by weight.
3. The method for producing 4-bromo-2-aminophenol according to claim 1, wherein the reaction time in step (2) is 30 to 60 minutes.
4. The method for producing 4-bromo-2-aminophenol according to claim 1, wherein the alcoholic solvent in step (3) is methanol.
5. The method for preparing 4-bromo-2-aminophenol according to claim 1, wherein in the hydrogenation step (3), the hydrogenation is continued for 30 to 45 minutes after the reaction of the central control raw material 2-nitro-4-bromophenol is detected to be disappeared.
6. The method for producing 4-bromo-2-aminophenol according to claim 1, wherein the purification in the step (4) is carried out by vacuum distillation.
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