CN112194583A - Preparation method of o-phenylenediamine - Google Patents
Preparation method of o-phenylenediamine Download PDFInfo
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- CN112194583A CN112194583A CN202010983133.0A CN202010983133A CN112194583A CN 112194583 A CN112194583 A CN 112194583A CN 202010983133 A CN202010983133 A CN 202010983133A CN 112194583 A CN112194583 A CN 112194583A
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- ammonia
- phenylenediamine
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- cupric
- dichlorobenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
Abstract
The invention discloses a preparation method of o-phenylenediamine, which comprises the following steps: in the presence of a copper catalyst and a ligand, o-dichlorobenzene reacts with ammonia to obtain o-phenylenediamine. The method improves the activity of the catalyst by adding the catalyst ligand into the reaction system, so that the reaction condition is milder, the reaction efficiency is high, and the method is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for synthesizing o-phenylenediamine from o-dichlorobenzene as a raw material.
Background
The o-phenylenediamine is mainly used as a pesticide intermediate and is a raw material of carbendazim and thiophanate-methyl; also dye intermediates for the production of cationic and vat dyes; in addition, rubber anti-aging agents, fur dyes, developers and surfactants can also be produced.
At present, the synthesis methods of o-phenylenediamine are many, and the important synthesis methods are mainly three.
One method is to take ortho-nitrochlorobenzene as a starting material to carry out an ammoniation reaction with strong ammonia water to obtain ortho-nitroaniline, and then to reduce the ortho-nitroaniline by adopting sodium sulfide to obtain the o-phenylenediamine (see Rev. Chim.,1976,27(5): 394-401). The method adopts sodium sulfide for reduction, the reduction yield is not high, and harmful gas is emitted during reaction, thereby polluting the environment.
And secondly, taking p-dichlorobenzene as a starting material, carrying out nitration under mixed acid to obtain 2, 5-dichloronitrobenzene, and then carrying out ammonolysis reaction with strong ammonia water to obtain the 4-chloro-2-nitroaniline. 4-chloro-2-nitroaniline is then catalytically hydrogenated and dechlorinated to give o-phenylenediamine (see US 4207261). The method uses mixed acid in the nitration process, can generate a large amount of waste water and waste residue, and has great pollution to the environment.
Thirdly, ortho-dichlorobenzene is subjected to ammonolysis reaction under the action of a copper catalyst to obtain o-phenylenediamine (see GB440697, JP 57027133). The method needs to be carried out under the conditions of high temperature and high pressure, has high requirements on equipment and has long reaction time.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides o-phenylenediamine obtained by the reaction of o-dichlorobenzene and ammonia in the presence of a copper catalyst, and the catalyst ligand is added into a reaction system, so that the catalyst activity is improved, the reaction conditions are mild, the reaction efficiency is high, and the method is suitable for industrial production.
In order to solve the above problems, the present invention provides the following technical solutions.
The invention provides a preparation method of o-phenylenediamine, which comprises the following steps: in the presence of a copper catalyst and a ligand, o-dichlorobenzene reacts with ammonia to obtain o-phenylenediamine.
The ammonia is ammonia water or liquid ammonia. If the ammonia is ammonia water, the concentration of the ammonia water is 25 to 45 percent.
The copper catalyst is selected from one or the combination of cuprous chloride, cuprous bromide, cuprous iodide, cupric oxide, cupric nitrate, cupric acetate, cupric sulfate, cuprous cyanide, cupric acetylacetonate, cupric trifluoroacetate and cuprous oxide.
The ligand includes but is not limited to one or a combination of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,2 ' -bipyridine, 4,4 ' -di-tert-butyl-2, 2 ' -bipyridine, 1, 10-phenanthroline, 3,4,7, 8-tetramethyl-1, 10-phenanthroline, N, N, -dimethylglycine, 8-hydroxyquinoline and L-proline.
In the invention, the molar ratio of o-dichlorobenzene to ammonia is preferably 1: 3-8, and more preferably 1: 3-5.
The molar ratio of the p-dichlorobenzene to the catalyst is 1: 0.1-0.5, preferably 1: 0.2-0.4. The molar ratio of the ligand to the catalyst is preferably 0.1-0.3: 1.
The reaction temperature is 130-180 ℃, preferably 130-150 ℃, but not limited to 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ or any two values.
The reaction pressure is 2-10 MPa, preferably 2-6 MPa, but can be 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa or any two values.
The time of the ammoniation reaction is 2-12 h, but not limited to 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h or any two of the above values.
Compared with the prior art, the invention has the beneficial effects that: because the ligand is added into the reaction system, the catalytic activity of the copper catalyst is greatly improved, the reaction efficiency is improved, the selectivity is good, and the reaction yield is high; and the reaction temperature and pressure are reduced, so that the reaction condition is milder, the safety risk is reduced, and the method is suitable for industrial production.
Detailed Description
Example 1
29.4 g (0.2mol) of o-dichlorobenzene, 40.8 g (0.6mol) of 25% aqueous ammonia, 1.98 g (0.02mol) of cuprous chloride and 0.54 g (0.002mol) of 4,4 '-di-tert-butyl-2, 2' -bipyridine were charged into the autoclave. Heating to 130 ℃, reacting for 1h under the pressure of 10 MPa. After the reaction is finished, cooling, decompressing and recovering ammonia, extracting o-phenylenediamine with toluene, layering, recovering the catalyst in the water phase, removing toluene from the organic phase, and then distilling under reduced pressure to obtain o-phenylenediamine with the yield of 86.3%.
Example 2
29.4 g (0.2mol) of o-dichlorobenzene, 48.6 g of 35% aqueous ammonia, 5.94 g (0.06mol) of cuprous chloride and 3.22 g (0.012mol) of 4,4 '-di-tert-butyl-2, 2' -bipyridine were charged into the autoclave. Heating to 150 ℃, and reacting for 1h under the pressure of 6 MPa. After the reaction is finished, cooling, decompressing and recovering ammonia, extracting o-phenylenediamine with toluene, layering, recovering the catalyst in the water phase, removing toluene from the organic phase, and then carrying out reduced pressure distillation to obtain the o-phenylenediamine with the yield of 88.5%.
Example 3
29.4 g (0.2mol) of o-dichlorobenzene, 60.4 g of 45% aqueous ammonia, 9.9 g (0.1mol) of cuprous chloride, and 8.04 g (0.03mol) of 4,4 '-di-t-butyl-2, 2' -bipyridine were charged into the autoclave. Heating to 180 ℃, and reacting for 1h under the pressure of 2 MPa. After the reaction is finished, cooling, decompressing and recovering ammonia, extracting o-phenylenediamine with toluene, layering, recovering the catalyst in the water phase, removing toluene from the organic phase, and then carrying out reduced pressure distillation to obtain the o-phenylenediamine with the yield of 87.8%.
Example 4
29.4 g (0.2mol) of o-dichlorobenzene, 13.6 g of liquid ammonia, 30 g of water, 5.94 g (0.06mol) of cuprous chloride and 3.22 g (0.012mol) of 4,4 '-di-tert-butyl-2, 2' -bipyridine were charged into the autoclave. Heating to 150 ℃, and reacting for 1h under the pressure of 6 MPa. After the reaction is finished, cooling, decompressing and recovering ammonia, extracting o-phenylenediamine with toluene, layering, recovering the catalyst from the water phase, removing toluene from the organic phase, and then distilling under reduced pressure to obtain the o-phenylenediamine with the yield of 86.5%.
Examples 5 to 15
The same raw materials and process conditions as in example 2, except for the catalyst and ligand, and the ratio of catalyst to ligand. The method comprises the following specific steps:
the foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the invention is not limited to the embodiments described above, which are described in the specification only to illustrate the principles of the invention. The invention also includes various insubstantial changes and modifications within the spirit of the invention, as claimed by those skilled in the art.
Claims (8)
1. A method for preparing o-phenylenediamine comprising: in the presence of a copper catalyst and a ligand, o-dichlorobenzene reacts with ammonia to obtain o-phenylenediamine.
2. The method according to claim 1, characterized in that the ammonia is liquid ammonia or aqueous ammonia.
3. The method according to claim 2, characterized in that the concentration of the aqueous ammonia is between 25% and 45%.
4. The process of claim 1, wherein the copper catalyst is selected from the group consisting of cuprous chloride, cuprous bromide, cuprous iodide, cupric oxide, cupric nitrate, cupric acetate, cupric sulfate, cuprous cyanide, cupric acetylacetonate, cupric trifluoroacetate, and cuprous oxide, and combinations thereof.
5. The method of claim 1, wherein the ligand is selected from the group consisting of pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,2 ' -bipyridine, 4,4 ' -di-tert-butyl-2, 2 ' -bipyridine, 1, 10-phenanthroline, 3,4,7, 8-tetramethyl-1, 10-phenanthroline, N, N-dimethylglycine, 8-hydroxyquinoline, and L-proline, or a combination thereof.
6. The process according to any one of claims 1 to 5, wherein the molar ratio of o-dichlorobenzene to ammonia is preferably 1:3 to 8, more preferably 1:3 to 5.
7. The process according to any one of claims 1 to 5, characterized in that the molar ratio of ortho-dichlorobenzene to catalyst is 1: 0.1-0.5, preferably 1: 0.2-0.4; the molar ratio of the ligand to the catalyst is 0.1-0.3: 1.
8. A process according to any one of claims 1 to 5, characterized in that the reaction temperature is 130 to 180 ℃, preferably 130 to 150 ℃; the reaction pressure is 2-10 MPa, preferably 2-6 MPa.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010983133.0A CN112194583A (en) | 2020-09-18 | 2020-09-18 | Preparation method of o-phenylenediamine |
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| CN202010983133.0A CN112194583A (en) | 2020-09-18 | 2020-09-18 | Preparation method of o-phenylenediamine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149327A (en) * | 2021-11-04 | 2022-03-08 | 安徽东至广信农化有限公司 | Method for synthesizing o-phenylenediamine through continuous ammoniation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120018949A (en) * | 2010-08-24 | 2012-03-06 | 에스케이케미칼주식회사 | Preparation method for phenylene diamine |
| KR20140131817A (en) * | 2013-05-06 | 2014-11-14 | 한국화학연구원 | Manufacturing process of phenylenediamine having recyclability of iodine |
| CN105037171A (en) * | 2015-06-08 | 2015-11-11 | 江阴市华亚化工有限公司 | Method for synthesizing and preparing o-phenylenediamine from orthodichlorobenzene |
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2020
- 2020-09-18 CN CN202010983133.0A patent/CN112194583A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120018949A (en) * | 2010-08-24 | 2012-03-06 | 에스케이케미칼주식회사 | Preparation method for phenylene diamine |
| KR20140131817A (en) * | 2013-05-06 | 2014-11-14 | 한국화학연구원 | Manufacturing process of phenylenediamine having recyclability of iodine |
| CN105037171A (en) * | 2015-06-08 | 2015-11-11 | 江阴市华亚化工有限公司 | Method for synthesizing and preparing o-phenylenediamine from orthodichlorobenzene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149327A (en) * | 2021-11-04 | 2022-03-08 | 安徽东至广信农化有限公司 | Method for synthesizing o-phenylenediamine through continuous ammoniation |
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