CN104030925A - Method for catalytically synthesizing mononitrochlorobenzene - Google Patents
Method for catalytically synthesizing mononitrochlorobenzene Download PDFInfo
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- CN104030925A CN104030925A CN201410289956.8A CN201410289956A CN104030925A CN 104030925 A CN104030925 A CN 104030925A CN 201410289956 A CN201410289956 A CN 201410289956A CN 104030925 A CN104030925 A CN 104030925A
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- chlorobenzene
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- acidic ion
- nitric acid
- mononitrochlorobenzene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a method for catalytically synthesizing mononitrochlorobenzene and relates to the technical field of chemical synthesis processes. According to the method, chlorobenzene is nitrified under the condition that a carboxyl functional acidic ionic liquid is used as a catalyst and a solvent and a nitric acid-acetic anhydride is used as a nitrifying system; and after reaction, the upper-layer organic phase is washed to be close to neutral, and is dehydrated and dried to obtain the product mononitrochlorobenzene. The water-containing ionic liquid provided by the invention can be circularly used through rotary evaporation and dehydration and vacuum drying. The carboxyl functional acidic ionic liquid with high catalytic activity is used as a catalyst to replace nitro-sulfuric acid to carry out synthetic reaction of mononitrochlorobenzene, so that the method can produce less three-waste pollution and is friendly to the environment; in addition, the ionic liquid is easy to recover and regenerate and can be repeatedly used with high activity. Therefore, the carboxyl functional acidic ionic liquid for synthesis of mononitrochlorobenzene has a very good industrial application prospect and can create high economic and social benefits.
Description
Technical field
The present invention relates to chemical synthesis process, particularly the synthesis technical field of single nitro-chlorobenzene.
Background technology
Single nitro-chlorobenzene comprises neighbour, to, a position nitro-chlorobenzene, due to the existence of nitro (meta-orienting group), compared with chlorobenzene, the chlorine on nitro-chlorobenzene is more easily replaced by amino, hydroxyl, methoxyl group, and the derivative of generation is all important dyestuff, agricultural chemicals, medicine intermediates.
The single nitro-chlorobenzene of current industrial preparation generally still adopts the traditional technology that is formed nitration mixture and carried out Chlorobenzene Nitration by nitric acid, sulfuric acid, this technique is mainly deposited problem both ways: the one, and nitration reaction regioselectivity is poor, in the single nitro-chlorobenzene generating, be 2.0 left and right to neighbour than only, in the time that on market, p-Nitrophenyl chloride demand is greater than o-Nitrochlorobenzene demand, cause o-Nitrochlorobenzene often to occur relative surplus, cause the wasting of resources; The 2nd, spent acid recycling difficulty after reaction, produces a large amount of acid-bearing wastewaters, not only etching apparatus, and serious environment pollution.Therefore find novel green technique for Chlorobenzene Nitration and control nitro-chlorobenzene neighbour's ratio is seemed to particularly important.
Ionic liquid has excellent chemistry, thermodynamic stability and good solubility because of it, almost without vapour pressure, pollution-free under room temperature, is applied and is more and more paid close attention to therefore set it as green solvent and green high-efficient catalyzer.Functionalized ion liquid refers to that ionic liquid zwitterion itself has specific structure or in zwitterion, introduces one or more functional groups and make ionic liquid have certain specific function or characteristic.Functionalization acidic ionic liquid body, owing to having the plurality of advantages of ionic liquid, liquid acid and solid acid concurrently, makes it not only in reaction, can be used as green solvent, and be mostly to affect whole reaction as acid catalyst, demonstrate high catalytic activity.
Although ionic liquid is a lot of for the research report of nitration reaction, the research of synthesizing single nitro-chlorobenzene with carboxyl-functional presence of acidic ionic liquid catalyst has no report.Therefore, the synthetic single nitro-chlorobenzene of carboxyl-functional presence of acidic ionic liquid catalyst is significant to " green chemical industry " future development for its suitability for industrialized production.
Summary of the invention
The object of the invention is to propose a kind of eco-friendly single nitro-chlorobenzene green synthesis method with industrialization development prospect.
Technical solution of the present invention is: using carboxyl-functional acidic ion liquid as catalysts and solvents, taking nitric acid-diacetyl oxide system as nitrated system, under 50～70 DEG C of temperature condition, carry out Chlorobenzene Nitration reaction; After reaction finishes, separate the moisture ionic liquid layer of lower floor, upper organic phase washing, near neutral, is obtained to product list nitro-chlorobenzene through dehydrating; In described carboxyl-functional acidic ion liquid, cation compound is N-Methylimidazole or pyridine, and described carboxyl-functional acidic ion liquid is bisulfate ion or nitrate anion class acidic ion liquid.
Ionic liquid moisture in the present invention can be recycled after rotary evaporation dehydration vacuum-drying.The present invention adopts the carboxyl-functional acidic ion liquid of high catalytic activity as catalyzer, replace nitric-sulfuric acid for single nitro-chlorobenzene building-up reactions, not only " three wastes " pollute few, environmentally friendly, and ionic liquid reclaiming is easy, can keep high reactivity to reuse.Therefore carboxyl-functional acidic ion liquid is had to good prospects for commercial application for single nitro-chlorobenzene is synthetic, can produce higher economic benefit and social benefit.
In the nitrated system of nitric acid-diacetyl oxide of the present invention, the weight percent of nitric acid is 65.0 %～68.0%, and when nitration reaction, the molar ratio of nitrated system and chlorobenzene is 1.0～2.5: 1.Reclaiming catalyst levels is identical with live catalyst consumption.
In carboxyl-functional acidic ion liquid of the present invention, cation compound is N-Methylimidazole or pyridine.In carboxyl-functional acidic ion liquid, introducing carboxylic acid functional group on positively charged ion is that Mono Chloro Acetic Acid is dissolved in to methylene dichloride, and mole target cation compounds such as dropping slowly make carboxyl-functional acidic ion liquid intermediate after temperature reaction.
Carboxyl-functional acidic ion liquid of the present invention is bisulfate ion or nitrate anion class acidic ion liquid, carboxyl-functional acidic ion liquid intermediate is dissolved in methylene dichloride, mole vitriol oils such as dropping or concentrated nitric acid, slowly make after temperature reaction.
Embodiment
One, prepare carboxyl-functional bisulfate ion or nitrate anion class acidic ion liquid:
Mono Chloro Acetic Acid is dissolved in to methylene dichloride, and the target cation compound of dropping and Mono Chloro Acetic Acid equimolar amount, slowly makes carboxyl-functional acidic ion liquid intermediate after temperature reaction; Above-mentioned carboxyl-functional acidic ion liquid intermediate is dissolved in methylene dichloride again, drip the vitriol oil or concentrated nitric acid with carboxyl-functional acidic ion liquid intermediate equimolar amount, slowly after temperature reaction, make respectively N-carboxymethyl pyridine bisulfate ion acidic ion liquid, N-carboxymethyl pyridine nitrate radical acidic ion liquid, N-carboxymethyl imidazoles bisulfate ion acidic ion liquid and N-carboxymethyl imidazoles nitrate radical acidic ion liquid, stand-by.
Two, synthetic single nitro-chlorobenzene:
embodiment 1:in the reaction vessel that reflux condensing tube is housed, add 2.03gN-carboxymethyl pyridine bisulfate ion acidic ion liquid, and add successively 6.2g (7.5mL) chlorobenzene, 7.7g (7.4mL) diacetyl oxide and 7.1g (5.3mL) concentrated nitric acid, be heated to carry out Chlorobenzene Nitration reaction under 50～70 DEG C of temperature condition.
After reaction finishes, be cooled to room temperature, stratification, separates the moisture ionic liquid layer of lower floor, and upper strata organic layer is adopted to 5%NaHCO in succession
3the aqueous solution and deionized water wash are near neutral, and vacuum-drying, obtains faint yellow solid, is single nitro-chlorobenzene, and productive rate is 87.94%.Product liquid-phase chromatographic analysis is 18.78 to neighbour's ratio.
Moisture ionic liquid layer dewaters through rotary evaporation, reusable after vacuum-drying at 70 DEG C.
embodiment 2:in the there-necked flask that reflux condensing tube is housed, add 1.52gN-carboxymethyl pyridine bisulfate ion acidic ion liquid, and add successively 6.2g(7.5mL) chlorobenzene, 7.7g(7.4mL) diacetyl oxide and 7.1g(5.3mL) nitric acid, be heated to carry out Chlorobenzene Nitration reaction under 50～70 DEG C of temperature condition.
After reaction finishes, be cooled to room temperature, stratification, separates the moisture ionic liquid layer of lower floor, and upper strata organic layer is adopted to 5%NaHCO in succession
3the aqueous solution and deionized water wash are near neutral, and vacuum-drying, obtains faint yellow solid, is single nitro-chlorobenzene, and productive rate is 79.31%.Product liquid-phase chromatographic analysis is 9.58 to neighbour's ratio.
Moisture ionic liquid layer dewaters through rotary evaporation, reusable after vacuum-drying at 70 DEG C.
embodiment 3:in the there-necked flask that reflux condensing tube is housed, add 2.03gN-carboxymethyl pyridine bisulfate ion acidic ion liquid, and add successively 6.2g(7.5mL) chlorobenzene, 7.7g(7.4mL) diacetyl oxide and 5.8g(4.3mL) nitric acid, be heated to carry out Chlorobenzene Nitration reaction under 50～70 DEG C of temperature condition.
After reaction finishes, be cooled to room temperature, stratification, separates the moisture ionic liquid layer of lower floor, and upper strata organic layer is adopted to 5%NaHCO in succession
3the aqueous solution and deionized water wash are near neutral, and vacuum-drying, obtains faint yellow solid, is single nitro-chlorobenzene, and productive rate is 79.95%.Product liquid-phase chromatographic analysis is 15.07 to neighbour's ratio.
Moisture ionic liquid layer dewaters through rotary evaporation, reusable after vacuum-drying at 70 DEG C.
embodiment 4:in the there-necked flask that reflux condensing tube is housed, add the 2.03gN-carboxymethyl pyridine bisulfate ion acidic ion liquid of reclaiming, and add successively 6.2g(7.5mL) chlorobenzene, 7.7g(7.4mL) diacetyl oxide and 7.1g(5.3mL) nitric acid, be heated to carry out Chlorobenzene Nitration reaction under 50 ~ 70 DEG C of temperature condition.
After reaction finishes, be cooled to room temperature, stratification, separates the moisture ionic liquid layer of lower floor, and upper strata organic layer is adopted to 5%NaHCO in succession
3the aqueous solution and deionized water wash are near neutral, and vacuum-drying, obtains faint yellow solid, is single nitro-chlorobenzene, and productive rate is 87.85%.Product liquid-phase chromatographic analysis is 18.69 to neighbour's ratio.
Moisture ionic liquid layer dewaters through rotary evaporation, reusable after vacuum-drying at 70 DEG C.
comparison example 1:in the there-necked flask that reflux condensing tube is housed, add 1.73gN-carboxymethyl pyridine nitrate radical acidic ion liquid, and add successively 6.2g(7.5mL) chlorobenzene, 7.7g(7.4mL) diacetyl oxide and 7.1g(5.3mL) nitric acid, be heated to carry out Chlorobenzene Nitration reaction under 50～70 DEG C of temperature condition.
After reaction finishes, be cooled to room temperature, stratification, separates the moisture ionic liquid layer of lower floor, and upper strata organic layer is adopted to 5%NaHCO in succession
3the aqueous solution and deionized water wash are near neutral, and vacuum-drying, obtains faint yellow solid, is single nitro-chlorobenzene, and productive rate is 69.40%.Product liquid-phase chromatographic analysis is 10.47 to neighbour's ratio.
Moisture ionic liquid layer dewaters through rotary evaporation, reusable after vacuum-drying at 70 DEG C.
comparison example 2:in the there-necked flask that reflux condensing tube is housed, add 2.06gN-carboxymethyl imidazoles bisulfate ion acidic ion liquid, and add successively 6.2g(7.5mL) chlorobenzene, 7.7g(7.4mL) diacetyl oxide and 7.1g(5.3mL) nitric acid, be heated to carry out Chlorobenzene Nitration reaction under 50～70 DEG C of temperature condition.
After reaction finishes, be cooled to room temperature, stratification, separates the moisture ionic liquid layer of lower floor, and upper strata organic layer is adopted to 5%NaHCO in succession
3the aqueous solution and deionized water wash are near neutral, and vacuum-drying, obtains faint yellow solid, is single nitro-chlorobenzene, and productive rate is 78.25%.Product liquid-phase chromatographic analysis is 16.52 to neighbour's ratio.
Moisture ionic liquid layer dewaters through rotary evaporation, reusable after vacuum-drying at 70 DEG C.
comparison example 3:in the there-necked flask that reflux condensing tube is housed, add 1.75gN-carboxymethyl imidazoles nitrate radical acidic ion liquid, and add successively 6.2g(7.5mL) chlorobenzene, 7.7g(7.4mL) diacetyl oxide and 7.1g(5.3mL) nitric acid, be heated to carry out Chlorobenzene Nitration reaction under 50～70 DEG C of temperature condition.
After reaction finishes, be cooled to room temperature, stratification, separates the moisture ionic liquid layer of lower floor, and upper strata organic layer is adopted to 5%NaHCO in succession
3the aqueous solution and deionized water wash are near neutral, and vacuum-drying, obtains faint yellow solid, is single nitro-chlorobenzene, and productive rate is 58.12%.Product liquid-phase chromatographic analysis is 6.03 to neighbour's ratio.
Moisture ionic liquid layer dewaters through rotary evaporation, reusable after vacuum-drying at 70 DEG C.
Interpretation of result:
As seen from the above-described embodiment, in single nitro-chlorobenzene building-up reactions, obtain target product productive rate using N-carboxymethyl pyridine bisulfate ion acidic ion liquid as catalyzer higher.
Claims (5)
1. catalyze and synthesize a method for single nitro-chlorobenzene, it is characterized in that using carboxyl-functional acidic ion liquid as catalysts and solvents, taking nitric acid-diacetyl oxide system as nitrated system, under 50～70 DEG C of temperature condition, carry out Chlorobenzene Nitration reaction; After reaction finishes, separate the moisture ionic liquid layer of lower floor, upper organic phase washing, near neutral, is obtained to product list nitro-chlorobenzene through dehydrating; In described carboxyl-functional acidic ion liquid, cation compound is N-Methylimidazole or pyridine, and described carboxyl-functional acidic ion liquid is bisulfate ion or nitrate anion class acidic ion liquid.
2. method according to claim 1, is characterized in that the weight percent of nitric acid in the nitrated system of described nitric acid-diacetyl oxide is 65.0 %～68.0%, and when nitration reaction, the molar ratio of nitrated system and chlorobenzene is 1.0～2.5: 1.
3. method according to claim 1, the molar ratio that it is characterized in that described carboxyl-functional acidic ion liquid and chlorobenzene is 1.0～2.5: 10.
4. method according to claim 1, is characterized in that in the nitrated system of described nitric acid-diacetyl oxide, diacetyl oxide is 1.0～1.5: 1 with the mol ratio of mixing of nitric acid.
5. method according to claim 1, is characterized in that to adopt weight percent when neutral be the NaHCO of 5.0 % near by described upper organic phase washing
3the aqueous solution and deionized water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646572A (en) * | 2015-12-16 | 2016-06-08 | 连云港市金囤农化有限公司 | Method for preparing tris (2,4-dichloro-5-nitrophenyl) phosphate |
| CN111116372A (en) * | 2019-12-30 | 2020-05-08 | 浙江本立科技股份有限公司 | 3,4 dichloronitrobenzene full-continuous flow synthesis process under action of catalyst |
| CN113563196A (en) * | 2021-07-27 | 2021-10-29 | 安徽江泰新材料科技有限公司 | Preparation method of 2,4(2,6) -dimethyl nitrobenzene |
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| WO2002030865A2 (en) * | 2000-10-10 | 2002-04-18 | The Queen's University Of Belfast | Aromatic nitration reactions |
| WO2005028446A1 (en) * | 2003-09-18 | 2005-03-31 | Sumitomo Chemical Company, Limited | Ionic liquid and method of reaction using the same |
| CN101412677A (en) * | 2008-11-12 | 2009-04-22 | 扬州大学 | Clean chlorobenzene liquid phase nitration method having superior para-selectivity |
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2014
- 2014-06-26 CN CN201410289956.8A patent/CN104030925A/en active Pending
Patent Citations (3)
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| WO2002030865A2 (en) * | 2000-10-10 | 2002-04-18 | The Queen's University Of Belfast | Aromatic nitration reactions |
| WO2005028446A1 (en) * | 2003-09-18 | 2005-03-31 | Sumitomo Chemical Company, Limited | Ionic liquid and method of reaction using the same |
| CN101412677A (en) * | 2008-11-12 | 2009-04-22 | 扬州大学 | Clean chlorobenzene liquid phase nitration method having superior para-selectivity |
Non-Patent Citations (4)
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| CUN ZHANG等: "Regioselective mononitration of chlorobenzene using caprolactam-based Brønsted acidic ionic liquids", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| CUN ZHANG等: "Regioselective mononitration of chlorobenzene using caprolactam-based Brønsted acidic ionic liquids", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》, vol. 383384, 2 December 2013 (2013-12-02), pages 101 - 105 * |
| 鲍少华: "新型酸功能化离子液体的制备及其在有机合成中的应用", 《华东师范大学博士学位论文》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646572A (en) * | 2015-12-16 | 2016-06-08 | 连云港市金囤农化有限公司 | Method for preparing tris (2,4-dichloro-5-nitrophenyl) phosphate |
| CN111116372A (en) * | 2019-12-30 | 2020-05-08 | 浙江本立科技股份有限公司 | 3,4 dichloronitrobenzene full-continuous flow synthesis process under action of catalyst |
| CN111116372B (en) * | 2019-12-30 | 2021-05-11 | 浙江本立科技股份有限公司 | 3,4 dichloronitrobenzene full-continuous flow synthesis process under action of catalyst |
| CN113563196A (en) * | 2021-07-27 | 2021-10-29 | 安徽江泰新材料科技有限公司 | Preparation method of 2,4(2,6) -dimethyl nitrobenzene |
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Application publication date: 20140910 |