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CN102408339B - Clean nitration reaction of aromatic hydrocarbon of heteropolyacid pyridinium ionic liquid catalyst - Google Patents

Clean nitration reaction of aromatic hydrocarbon of heteropolyacid pyridinium ionic liquid catalyst Download PDF

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CN102408339B
CN102408339B CN201110250186.2A CN201110250186A CN102408339B CN 102408339 B CN102408339 B CN 102408339B CN 201110250186 A CN201110250186 A CN 201110250186A CN 102408339 B CN102408339 B CN 102408339B
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ionic liquid
heteropolyacid
pyridinium salt
nitration reaction
aromatic
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CN102408339A (en
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方东
张根成
郑龙洲
谢毅
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Yancheng Teachers University
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Abstract

本发明公开了一种杂多酸吡啶盐离子液体催化芳香烃清洁硝化反应的新方法。所用催化剂是阴离子为杂多酸根、阳离子为吡啶盐结构的离子液体，原料为芳烃化合物和硝酸，在催化剂作用下进行硝化反应得到芳烃的硝化产物。本发明与现有技术相比，其优点为：(1)采用杂多酸阴离子结构的离子液体，原料来源广泛，制备方便；对水稳定，催化剂不失活，可循环使用；(2)杂多酸吡啶盐型离子液体催化活性高、用量少，回收方便；(3)用离子液体代替硝/硫混酸工艺中使用的浓硫酸，安全可靠、环境友好，具有工业化应用前景。

The invention discloses a new method for catalyzing the clean nitration reaction of aromatic hydrocarbons by a heteropolyacid pyridinium salt ionic liquid. The catalyst used is an ionic liquid in which the anion is a heteropolyacid radical and the cation is a pyridinium salt structure. The raw materials are aromatic compound and nitric acid, and the nitration reaction is carried out under the action of the catalyst to obtain a nitrated product of aromatic hydrocarbon. Compared with the prior art, the present invention has the following advantages: (1) adopts the ionic liquid of heteropolyacid anion structure, has a wide range of raw material sources, and is convenient to prepare; it is stable to water, the catalyst is not deactivated, and can be recycled; (2) the heteropolyacid anion structure The multi-acid pyridinium salt-type ionic liquid has high catalytic activity, less dosage, and is easy to recycle; (3) the use of ionic liquid to replace the concentrated sulfuric acid used in the nitric/sulfur mixed acid process is safe, reliable, environmentally friendly, and has industrial application prospects.

Description

The ionic liquid-catalyzed Aromatic Nitration of heteropolyacid pyridinium salt
One technical field
The present invention relates to the novel method of the ionic liquid-catalyzed Aromatic Nitration of a kind of heteropolyacid pyridinium salt, belong to chemical material preparing technical field.Present method is applicable to take aromatic hydroxy compound, nitric acid as raw material, the occasion of the nitration product of the synthetic aromatic hydrocarbons of heated and stirred under normal pressure.
Two background technologies
The nitration reaction of aromatic hydroxy compound is important organic synthesis unit process, substituted arene itrated compound is the very important Chemicals of a class, the research that all Method and process of the nitration reaction to aromatics has carried out of academia and industry member, nitre-sulphur mixed acid nitrifying that existing process using was used till today before 100 years carries out nitration reaction, there is seriously corroded in this method, the shortcoming such as the more and three-waste pollution of by product is serious.In recent years, because environmental pollution is day by day serious and energy scarcity, energy-saving and emission-reduction become the important topic of facing mankind, one of nitrated focus that becomes people's research of aromatics.
Heteropolyacid has the advantages that composition is simple, component is easily adjusted, and has acidity and oxidisability simultaneously, and can regulate and control its acidity by changing component; Because heteropolyacid anions is bulky, symmetry is high and electric density is low, no matter be therefore in solid-state or liquid, be all strong protonic acid, its strength of acid is more much better than than the mineral acid being comprised of respective center atom or ligating atom.These features make heteropolyacid show good catalytic activity in a lot of organic reactions, in recent years, in catalyticing research field, come into one's own.In recent years, the application of ionic liquid in organic synthesis is very active, the existing research of application as green solvent/catalyzer in nitrating aromatic compound reaction, the researchists such as Britain, the U.S., Japan have reported that the ionic liquid of trifluoromethanesulfonic acid based on glyoxaline cation, trifluoroacetic acid, nitrate is as solvent/catalyst successively, the application in the electric nitration reaction of aromatic hydrocarbon parent.
The method of open report is generally used imidazoles for positively charged ion, organic acid or common mineral acid are for anion ion liquid is as catalyzer, has frequent use diacetyl oxide or trifluoroacetic anhydride as promotor in nitrifying process.Due to imidazole type ion liquid cost costliness, be unfavorable for large-scale promotion application.In addition, a series of research shows (Garcia M T, Gathergood N, Scammells P J.Biodegradable ionic liquids Part II.Effect of the anion and toxicology.Green Chem.2005, 7:9-14), the biological degradability of the ionic liquid based on glyoxaline cation type is very poor, be difficult for by current most popular biological treatment or biological self-purification degraded, environment is had to potential harm, and diacetyl oxide, the use of trifluoroacetic anhydride not only cost is high, and be difficult to separating-purifying from product, be difficult for recycling use, thereby increased aftertreatment, the difficulty of product separation, can not meet environment, economical effects.
Three summary of the invention
The object of the present invention is to provide a kind of vitriol oil generally using at present that substitutes using the heteropolyacid ionic liquid that can be recycled as catalyzer, product and catalyzer are easily separated, product purity is high, make in the positively charged ion of ionic liquid of catalyzer the not method of the nitration product of the synthetic aromatic hydrocarbons of imidazole ring-containing.
The technical solution that realizes the object of the invention is: the novel method of the ionic liquid-catalyzed Aromatic Nitration of heteropolyacid quaternary ammonium salt, take negatively charged ion as heteropolyacid root, positively charged ion is as the ionic liquid of quaternary ammonium salt structure is as catalyzer, aromatic hydroxy compound, nitric acid are raw material, and under normal pressure, heating realizes the nitration reaction of aromatic hydroxy compound.
The present invention's ionic-liquid catalyst structure used is as follows:
Figure GSB0000117817260000021
Wherein heteropolyacid anions can be H 2pMo 12o 40 -, H 2pW 12o 40 -, H 2siW 12o 40 -in any.
The mol ratio of the present invention's material used is n (aromatic hydroxy compound): n (nitric acid)=1:1～3, and catalyst levels is 1～10% of aromatic hydroxy compound mole number, described material, the ionic liquid mix and blend that proportionally feeds intake.
The temperature of reaction of the present invention is 40～80 ℃.
The time of reaction of the present invention is 1～10 hour.
The concentration of nitric acid of the present invention is 65～70%.
The ionic liquid-catalyzed Aromatic Nitration of heteropolyacid pyridinium salt of the present invention, it is characterized in that: standing after completion of the reaction, reaction system is divided into liquid-liquid two-phase, upper strata is the nitration product of aromatic hydroxy compound, lower floor is the mixture of heteropolyacid pyridine ion liquid catalyzer and water, by being separated, shift out upper strata product, after washing, neutralization, vaccum dewatering, obtain purified product.The catalyzer that contains moisture content regeneration after dehydrating, feeds intake and carries out next batch building-up reactions in the ratio of the n of last batch (aromatic hydroxy compound): n (nitric acid).
The chemical principle of institute of the present invention foundation is as follows:
Figure GSB0000117817260000022
According to heteropolyacid pyridinium salt provided by the invention ionic liquid-catalyzed Aromatic Nitration, its key problem in technology is to adopt the ionic liquid-catalyzed raw material of heteropolyacid pyridinium salt aromatic hydroxy compound and nitric acid to be carried out nitration reaction and obtained the nitration product of aromatic hydrocarbons.Compared with prior art, its advantage is in the present invention: (1) adopts negatively charged ion is that heteropolyacid root, positively charged ion are the ionic liquid of pyridinium salt structure, and raw material sources are extensive, easy to prepare; Moisture-stable, catalyzer non-inactivation, can be recycled; (2) the ionic liquid-catalyzed activity of heteropolyacid pyridine salt type is high, consumption is few, and it is convenient to reclaim; (3) with ionic liquid, replace the vitriol oil using in nitre/sulphur nitration mixture technique, safe and reliable, environmental friendliness, has industrial applications prospect.
Four accompanying drawing explanations
Accompanying drawing is the schema of the ionic liquid-catalyzed Aromatic Nitration of heteropolyacid pyridinium salt of the present invention.
Five embodiments
The present invention is described in detail in detail by the following examples, and these embodiment are only for clear open the present invention, not as limitation of the present invention.
Embodiment 1
In 25mL round-bottomed flask, add successively 10mmol (1.81g) p-chloro benzo trifluoride-99,30mmol (2.8g) 68% nitric acid, (negatively charged ion is H to the catalyzer of 1mmol 2pMo 12o 40 -), mix and blend 5 hours at 80 ℃, cooling, standing being separated, upper strata thick product washing neutralization obtains the chloro-3-nitro-trifluoromethyl toluene of straight product 4-, productive rate 85% through vacuum-drying.
Embodiment 2
In 25mL round-bottomed flask, add successively 10mmol (1.81g) p-chloro benzo trifluoride-99,30mmol (2.8g) 68% nitric acid, (negatively charged ion is H to the catalyzer of 1mmol 2pW 12o 40 -), mix and blend 5 hours at 80 ℃, cooling, standing being separated, upper strata thick product washing neutralization obtains the chloro-3-nitro-trifluoromethyl toluene of straight product 4-, productive rate 83% through vacuum-drying.
Embodiment 3
In 25mL round-bottomed flask, add successively 10mmol (1.81g) p-chloro benzo trifluoride-99,30mmol (2.8g) 68% nitric acid, (negatively charged ion is H to the catalyzer of 1mmol 2siW 12o 40 -), mix and blend 5 hours at 80 ℃, cooling, standing being separated, upper strata thick product washing neutralization obtains the chloro-3-nitro-trifluoromethyl toluene of straight product 4-, productive rate 84% through vacuum-drying.
Embodiment 4
In 25mL round-bottomed flask, add successively 10mmol (0.92g) toluene, 10mmol (0.9g) 65% nitric acid, (negatively charged ion is H to the catalyzer of 1mmol 2pMo 12o 40 -), mix and blend 10 hours at 80 ℃, cooling, standing being separated, upper strata thick product washing neutralization obtains mononitrotoluene through vacuum-drying, productive rate 85%.
Embodiment 5
In 25mL round-bottomed flask, add successively 10mmol (0.92g) toluene, 20mmol (1.8g) 70% nitric acid, (negatively charged ion is H to the catalyzer of 0.5mmol 2pMo 12o 40 -), mix and blend 1 hour at 80 ℃, cooling, standing being separated, upper strata thick product washing neutralization obtains mononitrotoluene through vacuum-drying, productive rate 70%.
Embodiment 6
In 25mL round-bottomed flask, add successively 10mmol (0.92g) toluene, 30mmol (2.8g) 68% nitric acid, (negatively charged ion is H to the catalyzer of 0.5mmol 2pMo 12o 40 -), mix and blend 10 hours at 40 ℃, cooling, standing being separated, upper strata thick product washing neutralization obtains mononitrotoluene through vacuum-drying, productive rate 85%.
Embodiment 7
In 25mL round-bottomed flask, add successively 10mmol (1.13g) chlorobenzene, 20mmol (1.8g) 70% nitric acid, (negatively charged ion is H to the catalyzer of 0.5mmol 2pMo 12o 40 -), mix and blend 4 hours at 75 ℃, cooling, standing being separated, upper strata thick product washing neutralization obtains a nitro-chlorobenzene through vacuum-drying, productive rate 82%.
Embodiment 8
In 25mL round-bottomed flask, add successively 10mmol (0.96g) fluorobenzene, 20mmol (1.8g) 70% nitric acid, (negatively charged ion is H to the catalyzer of 0.5mmol 2pMo 12o 40 -), mix and blend 5 hours at 70 ℃, cooling, standing being separated, upper strata thick product washing neutralization obtains a fluoronitrobenzene through vacuum-drying, productive rate 80%.
Embodiment 9
After the embodiment 1 thick product in upper strata is separated, the catalyzer that water byproduct is contained in lower floor can regeneration after dehydrating, add successively 10mmol (1.81g) p-chloro benzo trifluoride-99,30mmol (2.8g) 100% nitric acid, (negatively charged ion is H to the catalyzer of 1mmol 2pMo 12o 40 -), mix and blend 5 hours at 80 ℃, cooling, standing being separated, upper strata thick product washing neutralization obtains the chloro-3-nitro-trifluoromethyl toluene of straight product 4-, productive rate 85% through vacuum-drying.

Claims (6)

1.一种杂多酸吡啶盐离子液体催化芳香烃硝化反应，其特征在于：以杂阴离子为杂多酸根、阳离子为季铵盐结构的离子液体为催化剂，芳烃化合物、硝酸为原料，在常压下加热实现芳烃化合物的硝化反应；芳香烃化合物是指甲苯、对氯三氟甲苯、氯苯、或氟苯；作为催化剂的离子液体具有如下结构：1. A heteropolyacid pyridinium salt ionic liquid catalyzes aromatic hydrocarbon nitration reaction, is characterized in that: take heteroanion as heteropolyacid radical, cation as the ionic liquid of quaternary ammonium salt structure as catalyst, aromatic hydrocarbon compound, nitric acid as raw material, in normal Press down and heat to realize the nitration reaction of the aromatic compound; the aromatic compound is toluene, p-chlorotrifluorotoluene, chlorobenzene, or fluorobenzene; the ionic liquid as a catalyst has the following structure: 其中杂多酸阴离子可以是H2PMo12O40 -、H2PW12O40 -、H2SiW12O40 -中的任一种。Wherein the heteropolyacid anion can be any one of H 2 PMo 12 O 40 - , H 2 PW 12 O 40 - , H 2 SiW 12 O 40 - . 2.根据权利要求1所述的一种杂多酸吡啶盐离子液体催化芳香烃硝化反应，其特征在于：所用物料的摩尔比为n(芳烃化合物)：n(硝酸)＝1：1～3，催化剂用量为芳烃化合物摩尔数的1～10％，所述的物料与离子液体按照比例投料混合搅拌。2. A heteropolyacid pyridinium salt ionic liquid according to claim 1 catalyzes the nitration reaction of aromatic hydrocarbons, characterized in that: the molar ratio of the materials used is n (aromatic compound): n (nitric acid)=1:1～3 The dosage of the catalyst is 1-10% of the number of moles of the aromatic compound, and the materials and the ionic liquid are mixed and stirred according to the proportion. 3.根据权利要求1所述的一种杂多酸吡啶盐离子液体催化芳香烃硝化反应，其特征在于：反应的温度为40～80℃。3. A heteropoly acid pyridinium salt ionic liquid according to claim 1 catalyzes the nitration reaction of aromatic hydrocarbons, characterized in that: the reaction temperature is 40-80°C. 4.根据权利要求1所述的一种杂多酸吡啶盐离子液体催化芳香烃硝化反应，其特征在于：反应的时间为1～10小时。4. A heteropoly acid pyridinium salt ionic liquid according to claim 1 catalyzes the nitration reaction of aromatic hydrocarbons, characterized in that: the reaction time is 1 to 10 hours. 5.根据权利要求1所述的一种杂多酸吡啶盐离子液体催化芳香烃硝化反应，其特征在于：硝酸的浓度为65～70％。5. A heteropolyacid pyridinium salt ionic liquid according to claim 1 catalyzes the nitration reaction of aromatic hydrocarbons, characterized in that: the concentration of nitric acid is 65-70%. 6.根据权利要求1所述的一种杂多酸吡啶盐离子液体催化芳香烃硝化反应，其特征在于：反应完毕后静置，反应体系分为液-液两相，上层为芳烃化合物的硝化产物，下层为含有杂多酸吡啶盐离子液体催化剂的混合物，通过相分离移出上层产品，经洗涤、中和、真空除水后得到精制产品，含有水份的催化剂经脱水干燥后再生利用，按前一批次的n(芳烃化合物)：n(硝酸)的比例投料进行下一批合成反应。6. a kind of heteropolyacid pyridinium salt ionic liquid catalyzed aromatic hydrocarbon nitration reaction according to claim 1, is characterized in that: leave standstill after finishing the reaction, reaction system is divided into liquid-liquid two-phase, and the upper strata is the nitration of aromatic hydrocarbon compound The product, the lower layer is a mixture containing the heteropolyacid pyridinium salt ionic liquid catalyst, the upper layer product is removed by phase separation, and the refined product is obtained after washing, neutralization, and vacuum dehydration, and the catalyst containing water is recycled after dehydration and drying. The ratio of n (aromatic compound): n (nitric acid) in the previous batch is fed to carry out the next batch of synthetic reactions.
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CN106622364A (en) * 2016-12-21 2017-05-10 新疆大学 Solid phase preparation method of ionic liquid polyoxometallate nano electrocatalyst
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CN109574851B (en) * 2018-11-27 2021-08-06 浙江工业大学上虞研究院有限公司 Method for preparing 2, 4-dinitrochlorobenzene by nitrifying chlorobenzene under catalysis of ionic liquid

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