CN104030925A - Method for catalytically synthesizing mononitrochlorobenzene - Google Patents
Method for catalytically synthesizing mononitrochlorobenzene Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- mononitrochlorobenzene
- carboxyl
- acidic ionic
- nitric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 39
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- 238000006396 nitration reaction Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- JCZMXVGQBBATMY-UHFFFAOYSA-N nitro acetate Chemical compound CC(=O)O[N+]([O-])=O JCZMXVGQBBATMY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 239000012074 organic phase Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001767 cationic compounds Chemical class 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 238000002390 rotary evaporation Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- -1 amino, hydroxyl Chemical group 0.000 description 8
- 238000004811 liquid chromatography Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000012044 organic layer Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000013517 stratification Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 2
- XRONOXONNCZNLI-UHFFFAOYSA-N hydrogen sulfate;2-pyridin-1-ium-1-ylacetic acid Chemical compound OS([O-])(=O)=O.OC(=O)C[N+]1=CC=CC=C1 XRONOXONNCZNLI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DTGKYEKXUPSPJH-UHFFFAOYSA-O 2-(1H-imidazol-3-ium-3-yl)acetic acid nitrate Chemical compound C1=C[N+](=CN1)CC(=O)O.[N+](=O)([O-])[O-] DTGKYEKXUPSPJH-UHFFFAOYSA-O 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- CAIZIGKCPQJNCW-UHFFFAOYSA-N nitric acid;pyridine Chemical compound O[N+]([O-])=O.C1=CC=NC=C1 CAIZIGKCPQJNCW-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种催化合成单硝基氯苯的方法，涉及化学合成工艺技术领域，本发明以羧基功能化酸性离子液体作为催化剂和溶剂，以硝酸-乙酸酐体系为硝化体系，对氯苯进行硝化反应；结束后，将上层有机相洗涤至近中性，经脱水干燥得到产物单硝基氯苯；本发明中含水的离子液体经旋转蒸发脱水并真空干燥后可循环使用。本发明采用高催化活性的羧基功能化酸性离子液体作为催化剂，取代硝硫混酸用于单硝基氯苯合成反应，不仅“三废”污染少，对环境友好，而且离子液体回收再生容易，可保持高活性重复使用。因此将羧基功能化酸性离子液体用于单硝基氯苯合成具有很好的工业应用前景，能够产生较高的经济效益和社会效益。A method for catalytically synthesizing mononitrochlorobenzene, which relates to the technical field of chemical synthesis technology. The present invention uses a carboxyl-functionalized acidic ionic liquid as a catalyst and a solvent, and uses a nitric acid-acetic anhydride system as a nitration system to carry out nitration reaction of p-chlorobenzene; After the end, the upper organic phase is washed to near neutrality, and the product mononitrochlorobenzene is obtained through dehydration and drying; the water-containing ionic liquid in the present invention can be recycled after being dehydrated by rotary evaporation and vacuum-dried. The present invention adopts carboxyl functionalized acidic ionic liquid with high catalytic activity as a catalyst to replace nitric acid mixed acid for the synthesis reaction of mononitrochlorobenzene, which not only has less pollution of "three wastes" and is environmentally friendly, but also easy to recycle and regenerate the ionic liquid, and can maintain Highly active for repeated use. Therefore, the use of carboxyl-functionalized acidic ionic liquids in the synthesis of mononitrochlorobenzene has a good industrial application prospect and can produce higher economic and social benefits.
Description
技术领域 technical field
本发明涉及化学合成工艺，特别涉及单硝基氯苯的合成技术领域。 The invention relates to a chemical synthesis process, in particular to the technical field of synthesis of mononitrochlorobenzene.
背景技术 Background technique
单硝基氯苯包括邻、对、间位硝基氯苯，由于硝基(间位定位基)的存在，与氯苯相比，硝基氯苯上的氯更容易被氨基、羟基、甲氧基所取代，生成的衍生物均是比较重要的染料、农药、医药中间体。 Mononitrochlorobenzene includes o-, p-, and meta-nitrochlorobenzenes. Due to the presence of nitro (meta-positioning group), compared with chlorobenzene, the chlorine on nitrochlorobenzene is more likely to be absorbed by amino, hydroxyl, formazan. Oxygen substituted, the generated derivatives are relatively important dyes, pesticides, and pharmaceutical intermediates.
目前工业上制备单硝基氯苯一般仍采用由硝酸、硫酸组成混酸进行氯苯硝化的传统工艺，该工艺主要存在两方面问题：一是硝化反应区域选择性较差，生成的单硝基氯苯中对邻比仅为2.0左右，当市场上对硝基氯苯需求量大于邻硝基氯苯需求量时，致使邻硝基氯苯往往出现相对过剩，造成资源浪费；二是反应后废酸回收再利用困难，产生大量含酸废水，不仅腐蚀设备，而且严重污染环境。因此寻找新型绿色工艺用于氯苯硝化并控制硝基氯苯对邻比显得尤为重要。 At present, the traditional process of nitrating chlorobenzene with mixed acid composed of nitric acid and sulfuric acid is generally still used in the industrial preparation of mononitrochlorobenzene. There are two main problems in this process: one is that the nitration reaction regioselectivity is poor, and the produced mononitrochlorobenzene The p-ortho ratio in benzene is only about 2.0. When the demand for p-nitrochlorobenzene is greater than the demand for o-nitrochlorobenzene on the market, there will often be a relative surplus of o-nitrochlorobenzene, resulting in waste of resources; It is difficult to recover and reuse acid, and a large amount of acid-containing wastewater is produced, which not only corrodes equipment, but also seriously pollutes the environment. Therefore, it is particularly important to find a new green process for the nitration of chlorobenzene and control the para-ortho ratio of nitrochlorobenzene.
离子液体因其具有优异的化学、热力学稳定性和良好的溶解性，室温下几乎无蒸汽压，无污染，故将其作为绿色溶剂和绿色高效催化剂加以应用已得到越来越多的关注。功能化离子液体是指离子液体阴阳离子本身具有特定的结构或者在阴阳离子中引入一个或多个官能团而使得离子液体具有某种特殊功能或特性。功能化酸性离子液体由于兼具离子液体、液体酸及固体酸的诸多优点，使其不仅在反应中可作为绿色溶剂，而且更多是作为酸催化剂影响着整个反应，显示出极高的催化活性。 Due to their excellent chemical and thermodynamic stability, good solubility, almost no vapor pressure at room temperature, and no pollution, ionic liquids have attracted more and more attention as green solvents and green efficient catalysts. Functionalized ionic liquid means that the anion and cation of the ionic liquid itself has a specific structure or one or more functional groups are introduced into the anion and cation so that the ionic liquid has a certain special function or characteristic. Functionalized acidic ionic liquid has many advantages of ionic liquid, liquid acid and solid acid, so it can not only be used as a green solvent in the reaction, but also affect the whole reaction as an acid catalyst, showing extremely high catalytic activity .
离子液体用于硝化反应的研究报道虽然很多，但用羧基功能化酸性离子液体催化合成单硝基氯苯的研究却未见报道。因此，羧基功能化酸性离子液体催化合成单硝基氯苯对于其工业化生产向“绿色化工”方向发展具有重要意义。 Although there are many research reports on the use of ionic liquids in nitration reactions, there is no report on the synthesis of mononitrochlorobenzene catalyzed by carboxyl-functionalized acidic ionic liquids. Therefore, the synthesis of mononitrochlorobenzene catalyzed by carboxyl-functionalized acidic ionic liquids is of great significance for the development of its industrial production in the direction of "green chemical industry".
发明内容 Contents of the invention
本发明目的在于提出一种具有工业化发展前景的环境友好的单硝基氯苯绿色合成方法。 The purpose of the present invention is to propose an environmentally friendly mononitrochlorobenzene green synthesis method with industrialized development prospects.
本发明技术方案是：以羧基功能化酸性离子液体作为催化剂和溶剂，以硝酸-乙酸酐体系为硝化体系，在50～70℃温度条件下进行氯苯硝化反应；反应结束后，分出下层含水的离子液体层，将上层有机相洗涤至近中性，经脱水干燥得到产物单硝基氯苯；所述羧基功能化酸性离子液体中阳离子化合物为N-甲基咪唑或吡啶，所述羧基功能化酸性离子液体为硫酸氢根或硝酸根阴离子类酸性离子液体。 The technical scheme of the present invention is: use carboxyl-functionalized acidic ionic liquid as catalyst and solvent, use nitric acid-acetic anhydride system as nitration system, and carry out chlorobenzene nitration reaction at a temperature of 50-70°C; after the reaction, separate the lower layer containing water The ionic liquid layer of the upper organic phase is washed to near neutrality, and the product mononitrochlorobenzene is obtained through dehydration and drying; the cationic compound in the carboxyl functionalized acidic ionic liquid is N-methylimidazole or pyridine, and the carboxyl functionalized The acidic ionic liquid is an acidic ionic liquid of hydrogen sulfate or nitrate anion.
本发明中含水的离子液体经旋转蒸发脱水并真空干燥后可循环使用。本发明采用高催化活性的羧基功能化酸性离子液体作为催化剂，取代硝硫混酸用于单硝基氯苯合成反应，不仅“三废”污染少，对环境友好，而且离子液体回收再生容易，可保持高活性重复使用。因此将羧基功能化酸性离子液体用于单硝基氯苯合成具有很好的工业应用前景，能够产生较高的经济效益和社会效益。 The water-containing ionic liquid in the present invention can be recycled after dehydration by rotary evaporation and vacuum drying. The present invention adopts carboxyl functionalized acidic ionic liquid with high catalytic activity as a catalyst to replace nitric acid mixed acid for the synthesis reaction of mononitrochlorobenzene, which not only has less pollution of "three wastes" and is environmentally friendly, but also easy to recycle and regenerate the ionic liquid, and can maintain Highly active for repeated use. Therefore, the use of carboxyl-functionalized acidic ionic liquids in the synthesis of mononitrochlorobenzene has a good industrial application prospect and can produce higher economic and social benefits.
本发明所述硝酸-乙酸酐硝化体系中硝酸的重量百分比为65.0 %～68.0%，硝化反应时，硝化体系与氯苯的投料摩尔比为1.0～2.5∶1。回收再生催化剂用量与新鲜催化剂用量相同。 The weight percent of nitric acid in the nitric acid-acetic anhydride nitration system of the present invention is 65.0% to 68.0%, and during the nitration reaction, the molar ratio of the nitration system to chlorobenzene is 1.0 to 2.5:1. The amount of regenerated catalyst recovered is the same as that of fresh catalyst.
本发明所述羧基功能化酸性离子液体中阳离子化合物为N-甲基咪唑或吡啶。在羧基功能化酸性离子液体中阳离子上引入羧酸功能化基团是将氯乙酸溶于二氯甲烷，滴加等摩尔目标阳离子化合物，缓慢升温反应后制得羧基功能化酸性离子液体中间体。 The cationic compound in the carboxyl-functionalized acidic ionic liquid of the present invention is N-methylimidazole or pyridine. The introduction of carboxylic acid functional groups into cations in carboxyl functional acidic ionic liquids is to dissolve chloroacetic acid in dichloromethane, add an equimolar target cationic compound dropwise, and slowly raise the temperature to prepare a carboxyl functional acidic ionic liquid intermediate.
本发明所述羧基功能化酸性离子液体为硫酸氢根或硝酸根阴离子类酸性离子液体，将羧基功能化酸性离子液体中间体溶于二氯甲烷中，滴加等摩尔浓硫酸或浓硝酸，缓慢升温反应后制得。 The carboxyl-functionalized acidic ionic liquid of the present invention is a bisulfate or nitrate anion acidic ionic liquid, and the carboxyl-functionalized acidic ionic liquid intermediate is dissolved in dichloromethane, and equimolar concentrated sulfuric acid or concentrated nitric acid is added dropwise, slowly Prepared after heating reaction.
具体实施方式 Detailed ways
一、制备羧基功能化硫酸氢根或硝酸根阴离子类酸性离子液体： 1. Preparation of carboxyl functionalized bisulfate or nitrate anion acidic ionic liquid:
将氯乙酸溶于二氯甲烷，滴加与氯乙酸等摩尔量的目标阳离子化合物，缓慢升温反应后制得羧基功能化酸性离子液体中间体；将上述羧基功能化酸性离子液体中间体再溶于二氯甲烷中，滴加与羧基功能化酸性离子液体中间体等摩尔量的浓硫酸或浓硝酸，缓慢升温反应后分别制得N-羧甲基吡啶硫酸氢根酸性离子液体、N-羧甲基吡啶硝酸根酸性离子液体、N-羧甲基咪唑硫酸氢根酸性离子液体和N-羧甲基咪唑硝酸根酸性离子液体，待用。 Dissolve chloroacetic acid in dichloromethane, add dropwise the target cationic compound in an equimolar amount to chloroacetic acid, and slowly heat up the reaction to obtain a carboxyl-functionalized acidic ionic liquid intermediate; redissolve the above-mentioned carboxyl-functionalized acidic ionic liquid intermediate in In dichloromethane, dropwise add concentrated sulfuric acid or concentrated nitric acid in an equimolar amount to the carboxyl functionalized acidic ionic liquid intermediate, and slowly heat up the reaction to prepare N-carboxymethylpyridine hydrogensulfate acidic ionic liquid, N-carboxymethyl Base pyridine nitrate acidic ionic liquid, N-carboxymethylimidazolium bisulfate acidic ionic liquid and N-carboxymethylimidazolium nitrate acidic ionic liquid, ready for use.
二、合成单硝基氯苯： 2. Synthesis of mononitrochlorobenzene:
实施例1：在装有回流冷凝管的反应容器中加入2.03gN-羧甲基吡啶硫酸氢根酸性离子液体，并依次加入6.2g(7.5mL)氯苯、7.7g(7.4mL)乙酸酐和7.1g(5.3mL)浓硝酸，加热至50～70℃温度条件下进行氯苯硝化反应。 Embodiment 1: add 2.03gN-carboxymethylpyridinium bisulfate acidic ionic liquid in the reaction vessel that reflux condenser is housed, and add successively 6.2g (7.5mL) chlorobenzene, 7.7g (7.4mL) acetic anhydride and 7.1g (5.3mL) of concentrated nitric acid was heated to 50-70°C for nitration of chlorobenzene.
反应结束后冷却至室温，静置分层，分出下层含水的离子液体层，将上层有机层相继采用5%NaHCO3水溶液和去离子水洗涤至近中性，真空干燥，得到淡黄色固体，即为单硝基氯苯，产率为87.94%。产物用液相色谱分析，对邻比为18.78。 After the reaction was finished, it was cooled to room temperature, allowed to stand for stratification, and the lower water-containing ionic liquid layer was separated, and the upper organic layer was successively washed with 5% NaHCO aqueous solution and deionized water until nearly neutral, and dried in vacuum to obtain a light yellow solid, namely It is mononitrochlorobenzene with a yield of 87.94%. The product was analyzed by liquid chromatography, and the pair ratio was 18.78.
含水的离子液体层经旋转蒸发除水，在70℃下真空干燥后可重复使用。 The aqueous ionic liquid layer was dehydrated by rotary evaporation and dried under vacuum at 70 °C for repeated use.
实施例2：在装有回流冷凝管的三口烧瓶中加入1.52gN-羧甲基吡啶硫酸氢根酸性离子液体，并依次加入6.2g（7.5mL）氯苯、7.7g（7.4mL）乙酸酐和7.1g（5.3mL）硝酸，加热至50～70℃温度条件下进行氯苯硝化反应。 Example 2: 1.52g of N-carboxymethylpyridine bisulfate acidic ionic liquid was added to a three-necked flask equipped with a reflux condenser, and 6.2g (7.5mL) of chlorobenzene, 7.7g (7.4mL) of acetic anhydride and 7.1g (5.3mL) of nitric acid was heated to 50-70°C for nitration reaction of chlorobenzene.
反应结束后冷却至室温，静置分层，分出下层含水的离子液体层，将上层有机层相继采用5%NaHCO3水溶液和去离子水洗涤至近中性，真空干燥，得到淡黄色固体，即为单硝基氯苯，产率为79.31%。产物用液相色谱分析，对邻比为9.58。 After the reaction was finished, it was cooled to room temperature, allowed to stand for stratification, and the lower water-containing ionic liquid layer was separated, and the upper organic layer was successively washed with 5% NaHCO aqueous solution and deionized water until nearly neutral, and dried in vacuum to obtain a light yellow solid, namely It is mononitrochlorobenzene with a yield of 79.31%. The product was analyzed by liquid chromatography, and the pair ratio was 9.58.
含水的离子液体层经旋转蒸发除水，在70℃下真空干燥后可重复使用。 The aqueous ionic liquid layer was dehydrated by rotary evaporation and dried under vacuum at 70 °C for repeated use.
实施例3：在装有回流冷凝管的三口烧瓶中加入2.03gN-羧甲基吡啶硫酸氢根酸性离子液体，并依次加入6.2g（7.5mL）氯苯、7.7g（7.4mL）乙酸酐和5.8g（4.3mL）硝酸，加热至50～70℃温度条件下进行氯苯硝化反应。 Example 3: 2.03g of N-carboxymethylpyridine bisulfate acidic ionic liquid was added to a three-necked flask equipped with a reflux condenser, and 6.2g (7.5mL) of chlorobenzene, 7.7g (7.4mL) of acetic anhydride and 5.8g (4.3mL) of nitric acid was heated to 50-70°C for the nitration reaction of chlorobenzene.
反应结束后冷却至室温，静置分层，分出下层含水的离子液体层，将上层有机层相继采用5%NaHCO3水溶液和去离子水洗涤至近中性，真空干燥，得到淡黄色固体，即为单硝基氯苯，产率为79.95%。产物用液相色谱分析，对邻比为15.07。 After the reaction was finished, it was cooled to room temperature, allowed to stand for stratification, and the lower water-containing ionic liquid layer was separated, and the upper organic layer was successively washed with 5% NaHCO aqueous solution and deionized water until nearly neutral, and dried in vacuum to obtain a light yellow solid, namely It is mononitrochlorobenzene with a yield of 79.95%. The product was analyzed by liquid chromatography, and the pair ratio was 15.07.
含水的离子液体层经旋转蒸发除水，在70℃下真空干燥后可重复使用。 The aqueous ionic liquid layer was dehydrated by rotary evaporation and dried under vacuum at 70 °C for repeated use.
实施例4：在装有回流冷凝管的三口烧瓶中加入回收再生的2.03gN-羧甲基吡啶硫酸氢根酸性离子液体，并依次加入6.2g（7.5mL）氯苯、7.7g（7.4mL）乙酸酐和7.1g（5.3mL）硝酸，加热至50~70℃温度条件下进行氯苯硝化反应。 Example 4: Add recovered and regenerated 2.03g of N-carboxymethylpyridinium bisulfate acidic ionic liquid into a three-necked flask equipped with a reflux condenser, and add 6.2g (7.5mL) chlorobenzene, 7.7g (7.4mL) in sequence Acetic anhydride and 7.1g (5.3mL) of nitric acid were heated to 50~70°C for nitration of chlorobenzene.
反应结束后冷却至室温，静置分层，分出下层含水的离子液体层，将上层有机层相继采用5%NaHCO3水溶液和去离子水洗涤至近中性，真空干燥，得到淡黄色固体，即为单硝基氯苯，产率为87.85%。产物用液相色谱分析，对邻比为18.69。 After the reaction was finished, it was cooled to room temperature, allowed to stand for stratification, and the lower water-containing ionic liquid layer was separated, and the upper organic layer was successively washed with 5% NaHCO aqueous solution and deionized water until nearly neutral, and dried in vacuum to obtain a light yellow solid, namely It is mononitrochlorobenzene with a yield of 87.85%. The product was analyzed by liquid chromatography, and the pair ratio was 18.69.
含水的离子液体层经旋转蒸发除水，在70℃下真空干燥后可重复使用。 The aqueous ionic liquid layer was dehydrated by rotary evaporation and dried under vacuum at 70 °C for repeated use.
对比实例1：在装有回流冷凝管的三口烧瓶中加入1.73gN-羧甲基吡啶硝酸根酸性离子液体，并依次加入6.2g（7.5mL）氯苯、7.7g（7.4mL）乙酸酐和7.1g（5.3mL）硝酸，加热至50～70℃温度条件下进行氯苯硝化反应。 Comparative Example 1: 1.73g of N-carboxymethylpyridine nitrate acidic ionic liquid was added to a three-necked flask equipped with a reflux condenser, and 6.2g (7.5mL) of chlorobenzene, 7.7g (7.4mL) of acetic anhydride and 7.1 g (5.3mL) of nitric acid, heated to 50-70°C for nitration of chlorobenzene.
反应结束后冷却至室温，静置分层，分出下层含水的离子液体层，将上层有机层相继采用5%NaHCO3水溶液和去离子水洗涤至近中性，真空干燥，得到淡黄色固体，即为单硝基氯苯，产率为69.40%。产物用液相色谱分析，对邻比为10.47。 After the reaction was finished, it was cooled to room temperature, allowed to stand for stratification, and the lower water-containing ionic liquid layer was separated, and the upper organic layer was successively washed with 5% NaHCO aqueous solution and deionized water until nearly neutral, and dried in vacuum to obtain a light yellow solid, namely It is mononitrochlorobenzene with a yield of 69.40%. The product was analyzed by liquid chromatography, and the pair ratio was 10.47.
含水的离子液体层经旋转蒸发除水，在70℃下真空干燥后可重复使用。 The aqueous ionic liquid layer was dehydrated by rotary evaporation and dried under vacuum at 70 °C for repeated use.
对比实例2：在装有回流冷凝管的三口烧瓶中加入2.06gN-羧甲基咪唑硫酸氢根酸性离子液体，并依次加入6.2g（7.5mL）氯苯、7.7g（7.4mL）乙酸酐和7.1g（5.3mL）硝酸，加热至50～70℃温度条件下进行氯苯硝化反应。 Comparative Example 2: Add 2.06g of N-carboxymethylimidazolium bisulfate acidic ionic liquid to a three-necked flask equipped with a reflux condenser, and add 6.2g (7.5mL) of chlorobenzene, 7.7g (7.4mL) of acetic anhydride and 7.1g (5.3mL) of nitric acid was heated to 50-70°C for nitration reaction of chlorobenzene.
反应结束后冷却至室温，静置分层，分出下层含水的离子液体层，将上层有机层相继采用5%NaHCO3水溶液和去离子水洗涤至近中性，真空干燥，得到淡黄色固体，即为单硝基氯苯，产率为78.25%。产物用液相色谱分析，对邻比为16.52。 After the reaction was finished, it was cooled to room temperature, allowed to stand for stratification, and the lower water-containing ionic liquid layer was separated, and the upper organic layer was successively washed with 5% NaHCO aqueous solution and deionized water until nearly neutral, and dried in vacuum to obtain a light yellow solid, namely It is mononitrochlorobenzene with a yield of 78.25%. The product was analyzed by liquid chromatography, and the pair ratio was 16.52.
含水的离子液体层经旋转蒸发除水，在70℃下真空干燥后可重复使用。 The aqueous ionic liquid layer was dehydrated by rotary evaporation and dried under vacuum at 70 °C for repeated use.
对比实例3：在装有回流冷凝管的三口烧瓶中加入1.75gN-羧甲基咪唑硝酸根酸性离子液体，并依次加入6.2g（7.5mL）氯苯、7.7g（7.4mL）乙酸酐和7.1g（5.3mL）硝酸，加热至50～70℃温度条件下进行氯苯硝化反应。 Comparative Example 3: 1.75g of N-carboxymethylimidazole nitrate acidic ionic liquid was added to a three-necked flask equipped with a reflux condenser, and 6.2g (7.5mL) of chlorobenzene, 7.7g (7.4mL) of acetic anhydride and 7.1 g (5.3mL) of nitric acid, heated to 50-70°C for nitration of chlorobenzene.
反应结束后冷却至室温，静置分层，分出下层含水的离子液体层，将上层有机层相继采用5%NaHCO3水溶液和去离子水洗涤至近中性，真空干燥，得到淡黄色固体，即为单硝基氯苯，产率为58.12%。产物用液相色谱分析，对邻比为6.03。 After the reaction was finished, it was cooled to room temperature, allowed to stand for stratification, and the lower water-containing ionic liquid layer was separated, and the upper organic layer was successively washed with 5% NaHCO aqueous solution and deionized water until nearly neutral, and dried in vacuum to obtain a light yellow solid, namely It is mononitrochlorobenzene with a yield of 58.12%. The product was analyzed by liquid chromatography, and the pair ratio was 6.03.
含水的离子液体层经旋转蒸发除水，在70℃下真空干燥后可重复使用。 The aqueous ionic liquid layer was dehydrated by rotary evaporation and dried under vacuum at 70 °C for repeated use.
结果分析： Result analysis:
由上述实施例可见，在单硝基氯苯合成反应中，以N-羧甲基吡啶硫酸氢根酸性离子液体作为催化剂得到目标产物产率较高。 It can be seen from the above examples that in the synthesis reaction of mononitrochlorobenzene, the yield of the target product obtained by using N-carboxymethylpyridinium hydrogensulfate acidic ionic liquid as a catalyst is higher.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410289956.8A CN104030925A (en) | 2014-06-26 | 2014-06-26 | Method for catalytically synthesizing mononitrochlorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410289956.8A CN104030925A (en) | 2014-06-26 | 2014-06-26 | Method for catalytically synthesizing mononitrochlorobenzene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104030925A true CN104030925A (en) | 2014-09-10 |
Family
ID=51461950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410289956.8A Pending CN104030925A (en) | 2014-06-26 | 2014-06-26 | Method for catalytically synthesizing mononitrochlorobenzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104030925A (en) |
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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2014
- 2014-06-26 CN CN201410289956.8A patent/CN104030925A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
|---|
| 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》 * |
| 龚达: "咪唑型离子液体中一硝基氯苯的区域选择性研究", 《合肥工业大学硕士学位论文》 * |
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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yue et al. | Synthesis and application of task-specific ionic liquids used as catalysts and/or solvents in organic unit reactions | |
| Sun et al. | Lysine functional heteropolyacid nanospheres as bifunctional acid–base catalysts for cascade conversion of glucose to levulinic acid | |
| CN100513394C (en) | Ketopyrrolidine sulfurate in liquid and its prpearing method | |
| CN105152922A (en) | Method for synthesizing benzoic acid with thioxanthone catalyst under condition of illumination | |
| CN105061185A (en) | Method for catalytic synthesis of benzoic acid by use of anthraquinone under lighting condition | |
| CN105152905A (en) | Method for synthesizing benzoic acid through thioxanthene catalysis under condition of illumination | |
| CN103788034A (en) | Preparation method for 5-hydroxymethylfurfural | |
| CN104437637A (en) | Epoxy resin loaded phosphotungstic acid catalyst as well as preparation method and application thereof | |
| CN108047009A (en) | The preparation method of methyl substituted benzaldehyde | |
| CN104030925A (en) | Method for catalytically synthesizing mononitrochlorobenzene | |
| Wang et al. | Enhancing esterification of small molecular acids with alcohols by molten salt hydrates | |
| CN106946800B (en) | A kind of synthetic method of quinazoline-2,4(1H,3H)-dione and its derivatives | |
| CN102557946A (en) | Method for catalyzing to synthesize propyl gallate by acidic ionic liquid | |
| CN103880617B (en) | A kind of propargyl alcohol aoxidizes the method for acetylenic ketone processed | |
| CN105175269A (en) | Synthesis method of 4-nitro m-xylene by selective nitration of bismuth nitrate | |
| CN104275210A (en) | Catalytic system for preparing 2, 5-furan dicarboxaldehyde by using 5-hydroxymethyl furfural and application thereof | |
| CN103724320A (en) | Preparation method of 2-isopropyl thioxanthone | |
| CN103012203B (en) | Improved method for preparing 4-phenyl-cyanophenyl | |
| CN102408339B (en) | Clean nitration reaction of aromatic hydrocarbon of heteropolyacid pyridinium ionic liquid catalyst | |
| CN102675052B (en) | Method for preparing dihydroxybenzene through phenol hydroxylation reaction | |
| CN105801376B (en) | Silica gel supported imidazole ion liquid is catalyzed the production method of benzene direct oxidation phenol | |
| CN1332924C (en) | Method for esterifying organic acid | |
| CN103304419A (en) | Method for synthesizing trioctyl trimellate under catalysis of functionalized acidic ionic liquid | |
| CN102212048B (en) | Method for preparing hydroxymethyl furfural by catalytic dehydration reaction of hexose | |
| CN102627551A (en) | Method for isomerizing rosin resin acid promoted by solid super acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140910 |