CN105601523A - Method for synthesizing 2,5-dimethoxy-4-chloroaniline - Google Patents
Method for synthesizing 2,5-dimethoxy-4-chloroaniline Download PDFInfo
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- CN105601523A CN105601523A CN201610154769.8A CN201610154769A CN105601523A CN 105601523 A CN105601523 A CN 105601523A CN 201610154769 A CN201610154769 A CN 201610154769A CN 105601523 A CN105601523 A CN 105601523A
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- dimethoxy
- chloroaniline
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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
Abstract
The invention relates to a method for synthesizing 2,5-dimethoxy-4-chloroaniline. The method comprises the steps: in the presence of carbon oxide and water, performing the reaction in an organic solvent under a high temperature and high pressure by adopting 2,5-dimethoxy-4-chloro-nitrobenzene as a raw material, selenium as a catalyst and organic alkali or inorganic alkali as an assistant catalyst, and reducing the nitro to amino to synthesize the 2,5-dimethoxy-4-chloroaniline. The method adopts high-pressure reaction and one-pot reaction, so that less equipment investment is needed, the operation is simple and convenient, and a product is relatively easy to separate and purify.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to 2,5-dimethoxy-4 '-chloronitrobenzene as raw material, selenium isCatalyst, organic base or inorganic base are co-catalyst, under the condition of carbon monoxide and water existence, in organic solvent, high temperatureThe method of synthetic 2,5-dimethoxy-4 '-chloroaniline under high pressure.
Background technology
2,5-dimethoxy-4 '-chloroaniline is the important intermediate of organic pigment and agricultural chemicals, be mainly used in coating, ink,The industries such as plastics, rubber, synthetic fibers, have good application performance. At present, in the process of nitroreduction, mainly contain withLower several method: iron powder reducing, catalytic hydrogenating reduction, hydrazine hydrate reduction, sodium sulfide reducing and electroreduction etc. Iron powder and sulphurAlthough choline reducing process is widely applicable, technique is simple, in reduction process, environment is produced to serious pollution, though catalytic hydrogenationSo the method for reducing that a kind of application surface is very wide, efficiency is higher, but in the time containing other reducible sensitive group in substrate, alsoFormer meeting is restricted, and this method cost is higher in addition, operates more complicated. Although electrolysis productive rate is high, free from environmental pollution, energy consumptionBe used for laboratory and half suitability for industrialized production greatly. Hydrazine hydrate due to application cost very high, the certain restriction being therefore subject to.
Summary of the invention
The object of the present invention is to provide a kind of in organic solvent, easy and simple to handle and with low cost 2, the 5-that catalyzes and synthesizesThe method of dimethoxy-4 '-chloroaniline.
For achieving the above object, the technical scheme that the present invention takes is as follows: a kind of synthetic 2,5-dimethoxy-4 '-chloroanilineMethod, method is as follows: taking nitro compound as substrate, under the condition existing at carbon monoxide and water, in organic solvent, seleniumFor catalyst, organic base or inorganic base are co-catalyst, at 120-170 DEG C, react 4-10 hour under 2-7MPa, are cooled to chamberTemperature, suction filtration with distilled water washing, vacuum drying, obtains product.
The method of above-mentioned synthetic 2,5-dimethoxy-4 '-chloroaniline, the 1%-that the mole dosage of selenium is nitro compound4%, the consumption of organic base or inorganic base is for making system pH remain on 7-9.
The method of above-mentioned synthetic 2,5-dimethoxy-4 '-chloroaniline, described nitro compound be 2,5-dimethoxy-4-chloronitrobenzene.
The method of above-mentioned synthetic 2,5-dimethoxy-4 '-chloroaniline, described inorganic base is sodium acid carbonate, Carbon DioxideThe mixing of one or more of sodium, potash, NaOH, calcium hydroxide or potassium hydroxide; Described organic base is threeEthamine, pyridine, 4-picoline, 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene, N, accelerine or N-methylThe mixing of one or more in pyrroles.
The method of above-mentioned synthetic 2,5-dimethoxy-4 '-chloroaniline, described organic solvent is cyclohexane.
The present invention, under the condition existing at carbon monoxide and water, with 2,5-dimethoxy-4 '-chloronitrobenzene for raw material, seleniumFor catalyst, organic base or inorganic base are co-catalyst, in organic solvent, under HTHP, react, and be ammonia by nitroreductionBase synthesizes 2,5-dimethoxy-4 '-chloroaniline. Reaction equation of the present invention is as follows:
Tool of the present invention has the following advantages:
1. be reaction under high pressure, one pot reaction, equipment investment is few, simple to operation.
2. be reaction dissolvent with cyclohexane give, be difficult for introducing other impurity, and the separating-purifying of product be comparatively easy.
3. with low cost, raw material is simple and easy to get, and with the lower nonmetal selenium of price as catalyst.
4. environmentally friendly, be green reaction without the three wastes substantially, reach the requirement of cleaner production, be conducive to large-scale industryChange and produce.
5. good economy performance, reaction selectivity is high, and with nonmetal selenium be catalyst to the catalytic selectivity of nitro up toMore than 99%.
6. reaction process difficulty is low, easy and simple to handle, and product separates with catalyst is easy.
7. catalyst selenium has phase transfer catalysis (PTC) function, and before reaction, solid selenium powder is that catalyst is insoluble to reaction system,In course of reaction, the selenium of solid phase changes the active specy that dissolves in reaction system into and carries out homogeneous catalytic reaction, at reaction knotShu Hou, catalyst is separated out with solid phase selenium form again, easy and product separation. Therefore, the present invention combines homogeneous catalysis and heterogeneousThe advantage of catalysis.
Detailed description of the invention
Example is below to detailed description of the present invention, instead of limitation of the present invention.
Embodiment 12,5-dimethoxy-4 '-chloroaniline synthetic
In the 100ml autoclave that stirrer is housed, add 2,5-dimethoxy-4 '-chloronitrobenzene (10mmol), selenium powder(0.0158g)，H2O(2ml)，C6H12(40ml)，NaHCO3(0.42g), pass into carbon monoxide to 6MPa, be then heated to 150 DEG CStirring reaction 8 hours, is put into autoclave in air naturally coolingly, product is stirred in air to oxidation and takes out after a period of timeFilter, and with distilled water washing 2 to 3 times, after suction filtration, obtain white solid, being target product, lucifuge is dried.
White solid is after testing: mp117～118 DEG C.
1HNMR(300MHz,CDCl3)δ7.26(s,2H,NH2), 6.79 (s, 1H, ArH skeletons), 6.37 (s, 1H, ArH bonesFrame), 3.80 (s, J=3.5Hz, 6H, CH3)。
It is 98.38% that product detects its purity by high performance liquid chromatography.
Embodiment 22,5-dimethoxy-4 '-chloroaniline synthetic
Other experimental techniques and condition, with embodiment 1, only change reaction temperature, record 2,5-dimethoxy-4 '-chloroanilineYield as table 1.
Table 1
| Temperature (DEG C) | 120 | 130 | 140 | 150 | 160 | 170 |
| Productive rate (%) | 31.86 | 50.52 | 66.01 | 82.89 | 74.86 | 67.59 |
Embodiment 32,5-dimethoxy-4 '-chloroaniline synthetic
Other experimental techniques and condition, with embodiment 1, only change CO pressure, records 2,5-dimethoxy-4 '-chloroanilineYield is as table 2.
Table 2
| Pressure (MPa) | 2 | 3 | 4 | 5 | 6 | 7 |
| Productive rate (%) | 30.06 | 40.34 | 50.39 | 68.74 | 82.89 | 73.53 |
Embodiment 42,5-dimethoxy-4 '-chloroaniline synthetic
Other experimental techniques and condition, with embodiment 1, only change the reaction time, record 2,5-dimethoxy-4 '-chloroanilineYield as table 3.
Table 3
| Time (h) | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Productive rate (%) | 48.59 | 60.36 | 70.84 | 77.52 | 82.89 | 78.02 | 77.51 |
Embodiment 52,5-dimethoxy-4 '-chloroaniline synthetic
Other experimental techniques and condition, with embodiment 1, only change co-catalyst kind, record 2,5-dimethoxy-4 '-chlorineThe yield of aniline is as table 4.
Table 4
Embodiment 62,5-dimethoxy-4 '-chloroaniline synthetic
Other experimental techniques and condition, with embodiment 1, only change selenium powder consumption, record 2,5-dimethoxy-4 '-chloroanilineYield as table 5.
Table 5
| Selenium (mmol) | 0 | 0.1 | 0.2 | 0.3 | 0.4 | 0.5 |
| Productive rate (%) | 13.92 | 61.36 | 82.89 | 72.95 | 72.81 | 58.83 |
Embodiment 72,5-dimethoxy-4 '-chloroaniline synthetic
Other experimental techniques and condition, with embodiment 1, only change co-catalyst NaHCO3Consumption, record 2,5-dimethoxyThe yield of base-4-chloroaniline is as table 6.
Table 6
| NaHCO3(mmol) | 0 | 3 | 5 | 7 | 9 |
| Productive rate (%) | 7.57 | 68.30 | 82.89 | 74.00 | 58.40 |
Claims (5)
1. the method for synthetic 2, a 5-dimethoxy-4 '-chloroaniline, is characterized in that method is as follows: taking nitro compound the end of asThing, under the condition of carbon monoxide and water existence, in organic solvent, selenium is catalyst, organic base or inorganic base are for helping catalysisAgent, at 120-170 DEG C, reacts under 2-7MPa 4-10 hour, cool to room temperature, and suction filtration with distilled water washing, vacuum drying,Obtain product.
2. according to the method for synthetic 2,5-dimethoxy-4 '-chloroaniline claimed in claim 1, it is characterized in that: selenium moleConsumption is the 1%-4% of nitro compound, and the consumption of organic base or inorganic base is for making system pH remain on 7-9.
3. the method that requires described synthetic 2,5-dimethoxy-4 '-chloroaniline according to claim 1 or 2, is characterized in that: instituteThe nitro compound of stating is 2,5-dimethoxy-4 '-chloronitrobenzene.
4. according to the method for synthetic 2, the 5-dimethoxy-4 '-chloroaniline described in claim 1 or 2, it is characterized in that: describedInorganic base be sodium acid carbonate, natrium carbonicum calcinatum, potash, NaOH, calcium hydroxide or potassium hydroxide one or both withOn mixing; Described organic base is triethylamine, pyridine, 4-picoline, 1,8-diazabicylo [5.4.0] 11 carbon-7-The mixing of one or more in alkene, N, accelerine or N-methylpyrrole.
5. according to the method for synthetic 2, the 5-dimethoxy-4 '-chloroaniline described in claim 1 or 2, it is characterized in that: describedOrganic solvent is cyclohexane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437111A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis C acid |
| CN110437110A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis M acid |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041671A (en) * | 1988-06-22 | 1991-08-20 | Hoechst Aktiengesellschaft | Process for the preparation 4-chloro-2,5-dimethoxy-aniline |
| CN101445459A (en) * | 2008-12-29 | 2009-06-03 | 辽宁大学 | Method for synthesizing 2, 4-dichloroaniline |
| CN102344382A (en) * | 2011-07-29 | 2012-02-08 | 河北华戈染料化学股份有限公司 | Method for preparing 2,5-dimethoxy-4-chloroaniline by hydrogenation reduction |
| CN102344380A (en) * | 2011-07-29 | 2012-02-08 | 江苏力达宁化工有限公司 | Method for preparing 2,5-dimethoxy-4-chloroaniline by using liquid-phase catalytic hydrogenation method |
| CN103113245A (en) * | 2013-02-18 | 2013-05-22 | 辽宁大学 | Method for synthesizing 1-aminoanthraquinone |
| CN103265441A (en) * | 2013-05-16 | 2013-08-28 | 响水恒利达科技化工有限公司 | Preparation method of 2,5-dimethoxyl-4-chloroaniline |
| CN104557574A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing 2,5-dimethoxy-4-chloroaniline |
-
2016
- 2016-03-15 CN CN201610154769.8A patent/CN105601523B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041671A (en) * | 1988-06-22 | 1991-08-20 | Hoechst Aktiengesellschaft | Process for the preparation 4-chloro-2,5-dimethoxy-aniline |
| CN101445459A (en) * | 2008-12-29 | 2009-06-03 | 辽宁大学 | Method for synthesizing 2, 4-dichloroaniline |
| CN102344382A (en) * | 2011-07-29 | 2012-02-08 | 河北华戈染料化学股份有限公司 | Method for preparing 2,5-dimethoxy-4-chloroaniline by hydrogenation reduction |
| CN102344380A (en) * | 2011-07-29 | 2012-02-08 | 江苏力达宁化工有限公司 | Method for preparing 2,5-dimethoxy-4-chloroaniline by using liquid-phase catalytic hydrogenation method |
| CN103113245A (en) * | 2013-02-18 | 2013-05-22 | 辽宁大学 | Method for synthesizing 1-aminoanthraquinone |
| CN103265441A (en) * | 2013-05-16 | 2013-08-28 | 响水恒利达科技化工有限公司 | Preparation method of 2,5-dimethoxyl-4-chloroaniline |
| CN104557574A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing 2,5-dimethoxy-4-chloroaniline |
Non-Patent Citations (7)
| Title |
|---|
| 何庆 等: "2,5-二甲氧基-4-氯硝基苯用水合肼还原的研究", 《精细与专用化学品》 * |
| 刘晓智 等: "硒催化CO/H2O还原1-硝基萘制1-萘胺", 《催化学报》 * |
| 刘晓智 等: "硒催化CO/H2O还原芳烃硝化物制苯胺及其衍生物的反应", 《化学进展》 * |
| 宋园园 等: "2,5-二甲氧基-4-氯苯胺的合成", 《染料与染色》 * |
| 王东田 等: "2,5-二甲氧基-4-氯苯胺的制备研究", 《哈尔滨建筑大学学报》 * |
| 王东田 等: "锌粉还原法制备2,5-二甲氧基-4-氯苯胺的研究", 《材料科学与工艺》 * |
| 高扬 等: "硒催化CO/H2O体系水相还原1-硝基蒽醌制1-氨基蒽醌", 《染料与染色》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437111A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis C acid |
| CN110437110A (en) * | 2019-08-26 | 2019-11-12 | 辽宁大学 | A method of synthesis M acid |
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