CN105461567A - Synthesis method of 2,4,6-trimethyl-m-phenylenediamine - Google Patents
Synthesis method of 2,4,6-trimethyl-m-phenylenediamine Download PDFInfo
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- CN105461567A CN105461567A CN201510780888.XA CN201510780888A CN105461567A CN 105461567 A CN105461567 A CN 105461567A CN 201510780888 A CN201510780888 A CN 201510780888A CN 105461567 A CN105461567 A CN 105461567A
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- trimethylammonium
- mphenylenediamine
- trimethyl
- dinitrobenzene
- synthesis
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- 0 CCc1c([*+])c(C)cc(C*)c1C#N Chemical compound CCc1c([*+])c(C)cc(C*)c1C#N 0.000 description 2
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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
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a synthesis method of 2,4,6-trimethyl-m-phenylenediamine. The method is characterized by comprising the steps of: (1) dropwise adding mixed acid into mesitylene for nitration and generation of 2,4,6-trimethyl-m-dinitrobenzene; after the reaction, standing for layering; neutralizing and washing an obtained organic layer to obtain 2,4,6-trimethyl-m-dinitrobenzene; (2) adding the 2,4,6-trimethyl-m-dinitrobenzene the obtained the step (1) to an autoclave, then adding a catalyst and a solvent, replacing the air in the autoclave with nitrogen gas, introducing hydrogen gas and conducting hydrogenation reduction to form 2,4,6-trimethyl-m-phenylenediamine, wherein the hydrogenation temperature is 50-120 DEG C, and the catalyst is a nickel catalyst; discharging hydrogen after the hydrogenation reduction, discharging the materials, removing methanol, cooling, crystallizing, and filtering to obtain the 2,4,6-trimethyl-m-phenylenediamine. The method has the advantages of short synthetic route, high product purity, high yield, few reaction steps, and long usage period of a hydrogenation reduction catalyst.
Description
Technical field
The present invention relates to the method for a kind of synthesis 2,4,6-trimethylammonium mphenylenediamine, belong to technical field of organic synthesis.
Background technology
2,4,6-trimethylammonium mphenylenediamine is the intermediate of a kind of acidity, reactive dyestuffs, medicine, sensitive materials.Be widely used in dyestuff and medicine industry.
In the prior art, 2,4, the synthetic method of 6-trimethylammonium mphenylenediamine is generally adopt mesitylene to be raw material, first bromination generates 2,4,6-trimethylammonium bromination benzene, 2 are generated again with mixed acid nitrification, dinitrobenzene bromination benzene between 4,6-trimethylammonium, finally sloughs bromine through hydrogenating reduction and generates 2 under catalyst action, 4,6-trimethylammonium mphenylenediamine.This synthetic route is adopted to there is following problem: (1) reactions steps is many; (2) hydrogenating reduction pressure is up to 5 ~ 7.5MPa; (3) hydrogenating reduction catalyzer easy in inactivation, catalyzer life cycle is short; (4) yield low (total recovery only has 65%), production cost is high; (5) environmental pollution is large, product purity low (only having 97%), and unstable.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide the method for a kind of synthesis 2,4,6-trimethylammonium mphenylenediamine, this synthetic method production cost is low, and synthetic route is short, and 2,4, the 6-trimethylammonium mphenylenediamine product purities obtained are high.
According to technical scheme provided by the invention, the method for described synthesis 2,4,6-trimethylammonium mphenylenediamine, is characterized in that, comprise the following steps:
(1) in mesitylene, nitration mixture is dripped by formula I nitrated generation 2,4,6-trimethylammonium Meta-dinitrobenzene,
described nitrated temperature is 20 ~ 100 DEG C, and nitration mixture is added dropwise to complete rear reaction 30 ~ 35 minutes, is warming up to 90 ~ 95 DEG C, and be incubated 30 ~ 35 minutes, stratification, the organic layer obtained obtains 2,4,6-trimethylammonium Meta-dinitrobenzene through neutralization &washing;
(2) step (1) is obtained 2,4,6-trimethylammonium Meta-dinitrobenzene adds in autoclave, then adds catalysts and solvents, with the air in nitrogen, hydrogen exchange autoclave, open stirring and be warming up to 60 ~ 65 DEG C, start logical hydrogen, hydrogen pressure is 1 ~ 4MPa, 2 are generated by (II) hydrogenating reduction, 4,6-trimethylammonium mphenylenediamine
the temperature of described hydrogenating reduction is 50 ~ 120 DEG C, and catalyzer is nickel catalyzator; Hydrogenation terminates maintenance 1 ~ 1.2 hour, discharges hydrogen, sloughs methyl alcohol, crystallisation by cooling, filtration obtain 2,4,6-described trimethylammonium mphenylenediamines after discharging.
In an embodiment, described nitration mixture is H
2sO
4and HNO
3mixing acid, H
2sO
4and HNO
3weight ratio be 75 ~ 87:13 ~ 25.
In an embodiment, described solvent is methyl alcohol, ethanol or Virahol.
In an embodiment, in the organic layer that described step (1) obtains, add water and sheet alkali, stratification after stirring.
In an embodiment, described step (1) reacted spent acid is used for the nitration reaction of lower batch of 2,4,6-trimethylammonium mphenylenediamine building-up processes.
The present invention generates 2,4,6-trimethylammonium Meta-dinitrobenzene with mesitylene and mixed acid nitrification, then is that under the effect of solvent, hydrogenating reduction becomes 2,4,6-trimethylammonium mphenylenediamine at catalyzer and alcohol.Synthetic route of the present invention is short, product purity high (99.5%), yield high (94%).With existing bromination, mixed acid nitrification, hydrogenating reduction debrominate technique (product purity 97%, yield 65%) compare, reactions steps is few, material cost obviously reduces, hydrogenating reduction catalyzer life cycle is long, non-inactivation, constant product quality, meets the needs of high-quality dye, pharmaceutical synthesis.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
The present invention first generates 2,4,6-trimethylammonium Meta-dinitrobenzene with mesitylene and mixed acid nitrification, be that under the effect of solvent, hydrogenating reduction becomes 2 at catalyzer and alcohol again, 4,6-trimethylammonium mphenylenediamine, its reactions steps is as shown in formula I, formula II.
Embodiment 1:
In the nitrating pot that 1000L has coil pipe to cool, add 114kg mesitylene, (nitration mixture is H to open agitation and dropping nitration mixture 700kg
2sO
4and HNO
3mixing acid, H
2sO
4and HNO
3weight ratio be 80.4:19.6), control temperature of reaction at 55 DEG C, drip off maintenance 30 minutes, be warming up to 95 DEG C, maintains 30 minutes, stratification, spent acid apply mechanically down criticize nitration reaction.Add water 500kg, sheet alkali 2kg in organic layer warp, stir 1 hour stratification, then add 500kg water, through washing to obtain 2,4,6-trimethylammonium Meta-dinitrobenzenes.
Above-mentioned 2,4,6-trimethylammonium Meta-dinitrobenzenes are added to 1000L and rise autoclave, then add Ni catalyzer 10kg, methyl alcohol 320kg, with nitrogen, hydrogen exchange.Open stirring and be warming up to 60 DEG C, start hydrogenation, control hydrogenation pressure 1 ~ 3MPa, temperature 80 DEG C, hydrogenation terminates maintenance 1.1 hours, and row's hydrogen, discharging, sloughs methyl alcohol, crystallisation by cooling, filters to obtain 2,4,6-trimethylammonium mphenylenediamines.
Embodiment 2:
In the nitrating pot that 1000L has coil pipe to cool, add 114kg mesitylene, (nitration mixture is H to open agitation and dropping nitration mixture 700kg
2sO
4and HNO
3mixing acid, H
2sO
4and HNO
3weight ratio be 75:25), control temperature of reaction at 20 DEG C, drip off maintenance 35 minutes, be warming up to 90 DEG C, maintains 35 minutes, stratification, spent acid apply mechanically down criticize nitration reaction.Add water 500kg, sheet alkali 2kg in organic layer warp, stir 1 hour stratification, then add 500kg water, through washing to obtain 2,4,6-trimethylammonium Meta-dinitrobenzenes.
Above-mentioned 2,4,6-trimethylammonium Meta-dinitrobenzenes are added to 1000L and rise autoclave, then add Ni catalyzer 10kg, methyl alcohol 320kg, with nitrogen, hydrogen exchange.Open stirring and be warming up to 65 DEG C, start hydrogenation, control hydrogenation pressure 4MPa, temperature 80 DEG C, hydrogenation terminates maintenance 1 hour, row hydrogen, discharging, sloughs methyl alcohol, crystallisation by cooling, filter 2,4,6-trimethylammonium mphenylenediamine, drying obtains 135kg, and purity is 99.7%, yield 94.7%.
Embodiment 3:
In the nitrating pot that 1000L has coil pipe to cool, add 114kg mesitylene, (nitration mixture is H to open agitation and dropping nitration mixture 700kg
2sO
4and HNO
3mixing acid, H
2sO
4and HNO
3weight ratio be 87:13), control temperature of reaction at 100 DEG C, drip off maintenance 30 minutes, be warming up to 90 DEG C, maintains 30 minutes, stratification, spent acid apply mechanically down criticize nitration reaction.Add water 500kg, sheet alkali 2kg in organic layer warp, stir 1 hour stratification, then add 500kg water, through washing to obtain 2,4,6-trimethylammonium Meta-dinitrobenzenes.
Above-mentioned 2,4,6-trimethylammonium Meta-dinitrobenzenes are added to 1000L and rise autoclave, then add Ni catalyzer 10kg, ethanol 320kg, with nitrogen, hydrogen exchange.Open stirring and be warming up to 65 DEG C, start hydrogenation, control hydrogenation pressure 2MPa, temperature 95 DEG C, hydrogenation terminates maintenance 1.2 hours, and row's hydrogen, discharging, sloughs methyl alcohol, crystallisation by cooling, filters to obtain 2,4,6-trimethylammonium mphenylenediamines.
Claims (5)
1. the method for synthesis 2,4, a 6-trimethylammonium mphenylenediamine, is characterized in that, comprise the following steps:
(1) in mesitylene, nitration mixture is dripped by formula I nitrated generation 2,4,6-trimethylammonium Meta-dinitrobenzene,
described nitrated temperature is 20 ~ 100 DEG C, and nitration mixture is added dropwise to complete rear reaction 30 ~ 35 minutes, is warming up to 90 ~ 95 DEG C, and be incubated 30 ~ 35 minutes, stratification, the organic layer obtained obtains 2,4,6-trimethylammonium Meta-dinitrobenzene through neutralization &washing;
(2) step (1) is obtained 2,4,6-trimethylammonium Meta-dinitrobenzene adds in autoclave, then adds catalysts and solvents, with the air in nitrogen, hydrogen exchange autoclave, open stirring and be warming up to 60 ~ 65 DEG C, start logical hydrogen, hydrogen pressure is 1 ~ 4MPa, 2 are generated by (II) hydrogenating reduction, 4,6-trimethylammonium mphenylenediamine
the temperature of described hydrogenating reduction is 50 ~ 120 DEG C, and catalyzer is nickel catalyzator; Hydrogenation terminates maintenance 1 ~ 1.2 hour, discharges hydrogen, sloughs methyl alcohol, crystallisation by cooling, filtration obtain 2,4,6-described trimethylammonium mphenylenediamines after discharging.
2. the method for synthesis as claimed in claim 12,4,6-trimethylammonium mphenylenediamine, is characterized in that: described nitration mixture is H
2sO
4and HNO
3mixing acid, H
2sO
4and HNO
3weight ratio be 75 ~ 87:13 ~ 25.
3. the method for synthesis as claimed in claim 12,4,6-trimethylammonium mphenylenediamine, is characterized in that: described solvent is methyl alcohol, ethanol or Virahol.
4. the method for synthesis as claimed in claim 12,4,6-trimethylammonium mphenylenediamine, is characterized in that: add water and sheet alkali in the organic layer that described step (1) obtains, stratification after stirring.
5. the method for synthesis as claimed in claim 12,4,6-trimethylammonium mphenylenediamine, is characterized in that: described step (1) reacted spent acid is used for the nitration reaction of lower batch of 2,4,6-trimethylammonium mphenylenediamine building-up processes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372518A (en) * | 2019-08-07 | 2019-10-25 | 江苏方圆芳纶研究院有限公司 | A kind of continuous preparation process and system of phenylenediamine |
| CN114573467A (en) * | 2022-03-21 | 2022-06-03 | 北京印刷学院 | Green synthesis process of 2, 4-dimethyl-3-aminobenzoic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801751A (en) * | 1986-09-30 | 1989-01-31 | Air Products And Chemicals, Inc. | Process for the disproportionation of alkylated aromatic primary amines |
| CN1730463A (en) * | 2005-07-15 | 2006-02-08 | 中国科学院上海有机化学研究所 | The green nitration method of perfluoro alkyl sulfonic acid salt catalysis sym-trimethylbenzene |
| CN1800143A (en) * | 2006-01-10 | 2006-07-12 | 江阴市倪家巷化工有限公司 | 2,4,6-trimethylaniline synthesis method |
-
2015
- 2015-11-13 CN CN201510780888.XA patent/CN105461567A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801751A (en) * | 1986-09-30 | 1989-01-31 | Air Products And Chemicals, Inc. | Process for the disproportionation of alkylated aromatic primary amines |
| CN1730463A (en) * | 2005-07-15 | 2006-02-08 | 中国科学院上海有机化学研究所 | The green nitration method of perfluoro alkyl sulfonic acid salt catalysis sym-trimethylbenzene |
| CN1800143A (en) * | 2006-01-10 | 2006-07-12 | 江阴市倪家巷化工有限公司 | 2,4,6-trimethylaniline synthesis method |
Non-Patent Citations (1)
| Title |
|---|
| 李汝贤等: "均三甲苯二硝化反应的研究", 《精细化工中间体》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372518A (en) * | 2019-08-07 | 2019-10-25 | 江苏方圆芳纶研究院有限公司 | A kind of continuous preparation process and system of phenylenediamine |
| CN110372518B (en) * | 2019-08-07 | 2020-06-02 | 江苏方圆芳纶研究院有限公司 | Continuous preparation process and system of phenylenediamine |
| CN114573467A (en) * | 2022-03-21 | 2022-06-03 | 北京印刷学院 | Green synthesis process of 2, 4-dimethyl-3-aminobenzoic acid |
| CN114573467B (en) * | 2022-03-21 | 2023-11-21 | 北京印刷学院 | Synthesis process of 2, 4-dimethyl-3-aminobenzoic acid |
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Application publication date: 20160406 |