CN102417457A - P-chlorobenzotrifluoride clean nitration reaction catalyzed by heteropoly acid ionic liquid - Google Patents
P-chlorobenzotrifluoride clean nitration reaction catalyzed by heteropoly acid ionic liquid Download PDFInfo
- Publication number
- CN102417457A CN102417457A CN2011102501877A CN201110250187A CN102417457A CN 102417457 A CN102417457 A CN 102417457A CN 2011102501877 A CN2011102501877 A CN 2011102501877A CN 201110250187 A CN201110250187 A CN 201110250187A CN 102417457 A CN102417457 A CN 102417457A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- heteropolyacid
- nitration reaction
- chloro
- benzo trifluoride
- 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
Images
Abstract
The invention discloses a novel method for carrying out p-chlorobenzotrifluoride clean nitration reaction catalyzed by a heteropoly acid ionic liquid. The used catalyst is an ionic liquid having a heteropoly acid anionic structure, and p-chlorobenzotrifluoride and nitric acid used as raw materials are subjected to nitration reaction under the action of the catalyst, thus obtaining 4-chloro-3-nitrobenzotrifluoride. Compared with the prior art, the invention has the following advantages: (1) the used ionic liquid having a heteropoly acid anionic structure has a wide source of raw materials and is convenient to prepare; and the catalyst is stable in water, can not be inactivated and can be used circularly; (2) compared with corresponding inorganic acid, the heteropoly acid forming the anionic structure has higher strength, higher catalytic activity, less consumption and better environment friendliness; and (3) by using the ionic liquid instead of concentrated sulfuric acid, the nitration process is environment-friendly and has industrial application prospects.
Description
One technical field
The present invention relates to the novel method of the ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of a kind of heteropolyacid, belong to the chemical material preparing technical field.Present method is applicable to that with p-chloro benzo trifluoride-99, nitric acid be raw material, the occasion of the synthetic 4-chloro-3-nitro-trifluoromethyl toluene of heated and stirred under normal pressure.
Two background technologies
Nitration reaction is important organic synthesis unit process, and the substituted arene itrated compound is one type of very important Chemicals, the research that academia and industry member have all been carried out the method for the nitration reaction of aromatics and technology.Energy-saving and emission-reduction are important topics of face of mankind, and the clean nitration of aromatics becomes one of focus of people's research.
The nitration product 4-chloro-3-nitro-trifluoromethyl toluene of p-chloro benzo trifluoride-99 is widely used in industrial circles such as medicine, agricultural chemicals, fine-chemical intermediate.Shortcomings such as nitration reaction is carried out with nitre-sulphur mixed acid nitrifying so far in 100 years forward positions of existing process using, and there is seriously corroded in this method, and the more and three-waste pollution of by product is serious.
Heteropolyacid has forms characteristics simple, that component is prone to accent, has acidity and oxidisability simultaneously, and can be through changing its acidity of component regulation and control; Because heteropolyacid anions is bulky, symmetry is high and electric density is low, therefore no matter be in solid-state or liquid state, all be strong protonic acid, its strength of acid is more much better than than the mineral acid of being made up of respective center atom or ligating atom.These characteristics make heteropolyacid in a lot of organic reactions, show good catalytic activity, in recent years, come into one's own in the catalyticing research field.In recent years; The application of ionic liquid in organic synthesis is very active; As the existing research of the application of green solvent/catalyzer in the reaction of aromatics clean nitration; Researchists such as Britain, the U.S., Japan have reported the ionic liquid of trifluoromethanesulfonic acid based on glyoxaline cation, trifluoroacetic acid, nitrate salt successively as solvent, the application in the electric nitration reaction of aromatic hydrocarbon parent.
The method of public reported generally use imidazoles, pyridylium, organic acid or common mineral acid as anion ion liquid as catalyzer, frequent use diacetyl oxide or trifluoroacetic anhydride are arranged as promotor in the nitrifying process.Because the imidazole type ion liquid cost is expensive, is 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), very poor based on the ion liquid biological degradability of imidazoles, pyridylium type, be difficult for through present most popular biological treatment or biological self-purification degraded; Environment there is potential harm; And the use of diacetyl oxide, trifluoroacetic anhydride not only cost is high, and be difficult to from product, separate and purify, be difficult for recycling use; Thereby increased aftertreatment, the isolating difficulty of product, can not satisfy environment, economical effects.
Three summary of the invention
The object of the present invention is to provide a kind ofly to substitute the vitriol oil that generally uses at present with the heteropolyacid ionic liquid that can be recycled as catalyzer, product and catalyzer are easily separated, product purity is high, make in the ion liquid positively charged ion of catalyzer the not method of the synthetic 4-chloro-3-nitro-trifluoromethyl toluene of imidazole ring-containing.
The technical solution that realizes the object of the invention is: the novel method of the ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of heteropolyacid; Promptly the ionic liquid with the heteropolyacid anions structure is a catalyzer; P-chloro benzo trifluoride-99, nitric acid are raw material, and heating realizes the nitration reaction to the chlorine trifluoromethyl under normal pressure.
The used ionic-liquid catalyst structure of the present invention is following:
Wherein heteropolyacid anions can be H
2PMo
12O
40 -, H
2PW
12O
40 -, H
2SiW
12O
40 -In any.
The mol ratio of the used material of the present invention is n (p-chloro benzo trifluoride-99): n (nitric acid)=1: 1～3, and catalyst levels is 1～10% of a p-chloro benzo trifluoride-99 mole number, and described material, ionic liquid proportionally feed intake to mix and stir.
The temperature of reaction according to the invention is 20～80 ℃.
The time of reaction according to the invention is 1～10 hour.
The concentration of nitric acid of the present invention is 65～100%.
The ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of a kind of heteropolyacid of the present invention; It is characterized in that: leave standstill after reaction finishes; Reaction system is divided into liquid-liquid two phases, and the upper strata is the nitration product to chloro-trifluoromethyl benzene, and lower floor is the mixture of heteropolyacid ionic-liquid catalyst and water; Shift out the upper strata product through being separated, behind washing, neutralization, vaccum dewatering, obtain refined prod.Contain catalyzer regenerated using after dehydrating of moisture content, feed intake in the ratio of last batch n (p-chloro benzo trifluoride-99): n (nitric acid) and carry out the next batch building-up reactions.
The chemical principle of institute of the present invention foundation is following:
According to the method for the ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration of heteropolyacid provided by the invention reaction, its key problem in technology is that to adopt negatively charged ion be that heteropolyacid root, positively charged ion are that the ionic liquid-catalyzed raw material of quaternary ammonium salt structure carries out nitration reaction to chloro-trifluoromethyl benzene and nitric acid and obtains 4-chloro-3-nitro-trifluoromethyl toluene compound.The present invention compared with prior art, its advantage is: the ionic liquid of heteropolyacid anions structure is adopted in (1), and raw material sources are extensive, preparation is convenient; Stable to water, the catalyzer non-inactivation can be recycled; (2) the corresponding mineral acid of the anionic heteropolyacid strength ratio of formation is strong, and catalytic activity is high, consumption is few, and environmental friendliness; (3) replacing the vitriol oil with ionic liquid, is eco-friendly nitration processes, has the industrial applications prospect.
Four description of drawings
Accompanying drawing is the schema of the ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of heteropolyacid of the present invention.
Five embodiments
Below through embodiment the present invention is detailed, these embodiment are only for clear open the present invention, not as limitation of the present invention.
Embodiment 1
In the 25mL round-bottomed flask, add 10mmol (1.81g) p-chloro benzo trifluoride-99 successively, 30mmol (2.8g) 65% nitric acid, (negatively charged ion is H to the catalyzer of 1.0mmol
2PMo
12O
40 -), mix down in 80 ℃ and to stir 10 hours, to cool off, leave standstill and be separated, upper strata thick product washing neutralization obtains straight product 4-chloro-3-nitro-trifluoromethyl toluene through vacuum-drying, productive rate 80%.
Embodiment 2
In the 25mL round-bottomed flask, add 10mmol (1.81g) p-chloro benzo trifluoride-99 successively, 20mmol (1.26g) 100% nitric acid, (negatively charged ion is H to the catalyzer of 0.5mmol
2PMo
12O
40 -), mix down in 20 ℃ and to stir 1 hour, to cool off, leave standstill and be separated, upper strata thick product washing neutralization obtains straight product 4-chloro-3-nitro-trifluoromethyl toluene through vacuum-drying, productive rate 83%.
Embodiment 3
In the 25mL round-bottomed flask, add 10mmol (1.81g) p-chloro benzo trifluoride-99 successively, 10mmol (0.63g) 100% nitric acid, (negatively charged ion is H to the catalyzer of 0.5mmol
2PMo
12O
40 -), mix down in 50 ℃ and to stir 5 hours, to cool off, leave standstill and be separated, upper strata thick product washing neutralization obtains straight product 4-chloro-3-nitro-trifluoromethyl toluene through vacuum-drying, productive rate 95%.
Embodiment 4
In the 25mL round-bottomed flask, add 10mmol (1.81g) p-chloro benzo trifluoride-99 successively, 10mmol (0.63g) 100% nitric acid, (negatively charged ion is H to the catalyzer of 0.5mmol
2PW
12O
40 -), mix down in 50 ℃ and to stir 5 hours, to cool off, leave standstill and be separated, upper strata thick product washing neutralization obtains straight product 4-chloro-3-nitro-trifluoromethyl toluene through vacuum-drying, productive rate 95%.
Embodiment 5
In the 25mL round-bottomed flask, add 10mmol (1.81g) p-chloro benzo trifluoride-99 successively, 10mmol (0.63g) 100% nitric acid, (negatively charged ion is H to the catalyzer of 1mmol
2SiW
12O
40 -), mix down in 50 ℃ and to stir 5 hours, to cool off, leave standstill and be separated, upper strata thick product washing neutralization obtains straight product 4-chloro-3-nitro-trifluoromethyl toluene through vacuum-drying, productive rate 90%.
Embodiment 6
In the 25mL round-bottomed flask, add 10mmol (1.81g) p-chloro benzo trifluoride-99 successively, 20mmol (1.4g) 90% nitric acid, (negatively charged ion is H to the catalyzer of 0.5mmol
2PMo
12O
40 -), mix down in 80 ℃ and to stir 2 hours, to cool off, leave standstill and be separated, upper strata thick product washing neutralization obtains straight product 4-chloro-3-nitro-trifluoromethyl toluene through vacuum-drying, productive rate 82%.
Embodiment 7
In the 25mL round-bottomed flask, add 10mmol (1.81g) p-chloro benzo trifluoride-99 successively, 10mmol (0.63g) 100% nitric acid, (negatively charged ion is H to the catalyzer of 0.8mmol
2PMo
12O
40 -), mix down in 40 ℃ and to stir 6 hours, to cool off, leave standstill and be separated, upper strata thick product washing neutralization obtains straight product 4-chloro-3-nitro-trifluoromethyl toluene through vacuum-drying, productive rate 88%.
Embodiment 8
In the 25mL round-bottomed flask, add 10mmol (1.81g) p-chloro benzo trifluoride-99 successively, 10mmol (0.63g) 100% nitric acid, (negatively charged ion is H to the catalyzer of 1mmol
2PMo
12O
40 -), mix down in 50 ℃ and to stir 5 hours, to cool off, leave standstill and be separated, upper strata thick product washing neutralization obtains straight product 4-chloro-3-nitro-trifluoromethyl toluene through vacuum-drying, productive rate 96%.
Embodiment 9
After the thick product in embodiment 8 upper stratas was separated, the catalyzer that water byproduct is contained in lower floor can regenerated using after dehydrating, and adds 10mmol (1.81g) p-chloro benzo trifluoride-99 successively, 10mmol (0.63g) 100% nitric acid, and (negatively charged ion is H to the catalyzer of 1mmol
2PMo
12O
40 -), mix down in 50 ℃ and to stir 5 hours, to cool off, leave standstill and be separated, upper strata thick product washing neutralization obtains straight product 4-chloro-3-nitro-trifluoromethyl toluene through vacuum-drying, productive rate 95%.
Claims (7)
1. ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of heteropolyacid; It is characterized in that: be that heteropolyacid root, positively charged ion are that the ionic liquid of quaternary ammonium salt structure is a catalyzer with the negatively charged ion; P-chloro benzo trifluoride-99, nitric acid are raw material, and heating realizes the nitration reaction to the chlorine trifluoromethyl under normal pressure.
2. the ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of a kind of heteropolyacid according to claim 1 is characterized in that having following structure as the ionic liquid of catalyzer:
Wherein heteropolyacid anions can be H
2PMo
12O
40 -, H
2PW
12O
40 -, H
2SiW
12O
40 -In any.
3. the ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of a kind of heteropolyacid according to claim 1; It is characterized in that: the mol ratio of used material is n (p-chloro benzo trifluoride-99): n (nitric acid)=1: 1～3; Catalyst levels is 1～10% of a phenylfluoroform mole number, and described material proportionally feeds intake with ionic liquid and mixes stirring.
4. the ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of a kind of heteropolyacid according to claim 1, it is characterized in that: the temperature of reaction is 20～80 ℃.
5. the ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of a kind of heteropolyacid according to claim 1, it is characterized in that: the time of reaction is 1～10 hour.
6. the ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of a kind of heteropolyacid according to claim 1, it is characterized in that: the concentration of nitric acid is 65～100%.
7. the ionic liquid-catalyzed p-chloro benzo trifluoride-99 clean nitration reaction of a kind of heteropolyacid according to claim 1; It is characterized in that: leave standstill after reaction finishes; Reaction system is divided into liquid-liquid two phases, and the upper strata is the nitration product to chloro-trifluoromethyl benzene, and lower floor is the mixture that contains the heteropolyacid ionic-liquid catalyst; Shift out the upper strata product through being separated, behind washing, neutralization, vaccum dewatering, obtain refined prod.Contain catalyzer regenerated using after dehydrating of moisture content, feed intake in the ratio of last batch n (p-chloro benzo trifluoride-99): n (nitric acid) and carry out the next batch building-up reactions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102501877A CN102417457A (en) | 2011-08-22 | 2011-08-22 | P-chlorobenzotrifluoride clean nitration reaction catalyzed by heteropoly acid ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102501877A CN102417457A (en) | 2011-08-22 | 2011-08-22 | P-chlorobenzotrifluoride clean nitration reaction catalyzed by heteropoly acid ionic liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102417457A true CN102417457A (en) | 2012-04-18 |
Family
ID=45942127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102501877A Pending CN102417457A (en) | 2011-08-22 | 2011-08-22 | P-chlorobenzotrifluoride clean nitration reaction catalyzed by heteropoly acid ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102417457A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104032324A (en) * | 2014-06-04 | 2014-09-10 | 中国科学院过程工程研究所 | Method for electrocatalytic reduction of carbon dioxide using multi-metal oxygen cluster ionic liquid as electrocatalyst |
| CN105016975A (en) * | 2015-06-27 | 2015-11-04 | 青岛科技大学 | Method for preparation of terpineol by alpha-pinene hydration reaction |
| CN108911998A (en) * | 2018-08-06 | 2018-11-30 | 朱晓萍 | A kind of method of green syt 1- amino anthraquinones |
| CN109574851A (en) * | 2018-11-27 | 2019-04-05 | 浙江工业大学上虞研究院有限公司 | A kind of method that ionic liquid-catalyzed Chlorobenzene Nitration prepares dinitrofluorobenzene |
| CN111153802A (en) * | 2018-11-08 | 2020-05-15 | 中国石油化工股份有限公司 | Green nitration method based on strong acid proton type ionic liquid catalysis |
| CN111205187A (en) * | 2020-03-16 | 2020-05-29 | 内蒙古大中实业化工有限公司 | Preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602673A (en) * | 2009-07-14 | 2009-12-16 | 西安近代化学研究所 | The method that in ionic liquid, prepares oil of mirbane |
-
2011
- 2011-08-22 CN CN2011102501877A patent/CN102417457A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602673A (en) * | 2009-07-14 | 2009-12-16 | 西安近代化学研究所 | The method that in ionic liquid, prepares oil of mirbane |
Non-Patent Citations (2)
| Title |
|---|
| 方东: "《南京理工大学博士论文》", 17 October 2008 * |
| 陈学玺 等: "4_氯_3_5_二硝基三氟甲苯硝化工艺研究进展[1]", 《现 代 农 药》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104032324A (en) * | 2014-06-04 | 2014-09-10 | 中国科学院过程工程研究所 | Method for electrocatalytic reduction of carbon dioxide using multi-metal oxygen cluster ionic liquid as electrocatalyst |
| CN104032324B (en) * | 2014-06-04 | 2016-08-17 | 中国科学院过程工程研究所 | A kind of with multi-metal oxygen cluster ionic liquid be eelctro-catalyst electro-catalysis reduction carbon dioxide method |
| CN105016975A (en) * | 2015-06-27 | 2015-11-04 | 青岛科技大学 | Method for preparation of terpineol by alpha-pinene hydration reaction |
| CN105016975B (en) * | 2015-06-27 | 2016-08-24 | 青岛科技大学 | A kind of method that australene hydration reaction prepares terpineol |
| CN108911998A (en) * | 2018-08-06 | 2018-11-30 | 朱晓萍 | A kind of method of green syt 1- amino anthraquinones |
| CN111153802A (en) * | 2018-11-08 | 2020-05-15 | 中国石油化工股份有限公司 | Green nitration method based on strong acid proton type ionic liquid catalysis |
| CN109574851A (en) * | 2018-11-27 | 2019-04-05 | 浙江工业大学上虞研究院有限公司 | A kind of method that ionic liquid-catalyzed Chlorobenzene Nitration prepares dinitrofluorobenzene |
| CN111205187A (en) * | 2020-03-16 | 2020-05-29 | 内蒙古大中实业化工有限公司 | Preparation method of 4-chloro-3, 5-dinitrobenzotrifluoride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102417457A (en) | P-chlorobenzotrifluoride clean nitration reaction catalyzed by heteropoly acid ionic liquid | |
| CN101486639B (en) | Novel method for synthesizing mixed glucose derivative | |
| CN103965045B (en) | Preparation process and device for glycerol triacetate | |
| CN105001027A (en) | Fluorne compound preparing method | |
| CN101475473A (en) | Method for preparing oxalate by coupling reaction of CO | |
| CN103242154B (en) | A kind of preparation method of 2,2-dimethylol propionic acid | |
| CN103212437A (en) | Method for preparing titanium-based catalyst and synthesizing epoxypropane and dicumyl peroxide | |
| CN102408339B (en) | Clean nitration reaction of aromatic hydrocarbon of heteropolyacid pyridinium ionic liquid catalyst | |
| CN101585771B (en) | Method of comprehensively use of chloronitrobenzene mixture by fluoro-reaction | |
| CN105461515A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN102731333B (en) | Method for preparing tetracaine | |
| CN102786499A (en) | Method for preparing cyclohexene oxide | |
| CN101914060B (en) | Synthesis of polyhydroacridine derivatives by clean catalysis of degradable ionic liquid | |
| CN103864618A (en) | Synthetic process of 1, 1-cyclopropane dicarboxylic acid dimethyl ester | |
| CN101773851B (en) | Dichloropropanol catalyst prepared by glycerol method | |
| CN106892823A (en) | The method for synthesizing the chloro- 3,5- dinitro-p-trifluorotoluenes of 2,4- bis- in microreactor | |
| CN101633620A (en) | Normal-temperature continuous production technology for cetane number improver | |
| CN102872911A (en) | Ion liquid catalyst and fatty acid preparation method | |
| CN102249927B (en) | Clean nitration reaction of p-chlorobenzotrifluoride under catalysis of degradable functional ionic liquid | |
| CN104030925A (en) | Method for catalytically synthesizing mononitrochlorobenzene | |
| CN102702043A (en) | Method for preparing CLT acid (6-chloro-3-nitrotoluene-4-sulfonic acid) by continuous hydrogenation reduction of 6-chloro-3-nitrotoluene-4-sulfonicacid liquid phase | |
| CN1730463A (en) | The green nitration method of perfluoro alkyl sulfonic acid salt catalysis sym-trimethylbenzene | |
| CN102702035B (en) | Method for continuously preparing fluorinated vinyl ether | |
| CN102069010A (en) | Montmorillonite catalyst used in preparation of cyclic carbonate | |
| CN110357826B (en) | Process for coproducing tetrahydroxymethyl melamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120418 |
|
| WD01 | Invention patent application deemed withdrawn after publication |