CN101602673A - The method that in ionic liquid, prepares oil of mirbane - Google Patents
The method that in ionic liquid, prepares oil of mirbane Download PDFInfo
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- CN101602673A CN101602673A CNA2009100233195A CN200910023319A CN101602673A CN 101602673 A CN101602673 A CN 101602673A CN A2009100233195 A CNA2009100233195 A CN A2009100233195A CN 200910023319 A CN200910023319 A CN 200910023319A CN 101602673 A CN101602673 A CN 101602673A
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Abstract
A kind of method for preparing oil of mirbane in ionic liquid comprises catalyst pre-treatment, preparation oil of mirbane, separates purification step.The present invention is in ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate, and the employing mass concentration is 30% H
2O
2As oxygenant, ammonium molybdate prepares oil of mirbane as catalyzer with the aniline oxidation, has avoided in the nitrated preparation oil of mirbane of the benzene process, and a large amount of acid solutions are to the corrosion of equipment and the pollution of environment; Also avoided in the aniline oxidising process simultaneously, adopt shortcomings such as expensive oxygenant or complicated easily loss catalyzer and productive rate are low, in chemical reaction process, with the ionic liquid replace organic solvent, ionic liquid has played the effect of solvent and promotor, reduced the harm of human body and the pollution of environment, enlarged the condition of reaction, shortened the reaction times, improved the productive rate of oil of mirbane, after reaction was finished, ionic liquid and catalyzer were still reusable, have reduced production cost.
Description
Technical field
The invention belongs to the nitro-compound technical field, be specifically related to substitute the method that organic solvent prepares oil of mirbane with ionic liquid.
Technical background
Oil of mirbane is a kind of important Organic Chemicals, is the intermediate of medicine, dyestuff, has been widely used industrial.Preparation about oil of mirbane at present mainly contains two kinds of methods, i.e. nitrated the and aniline oxidation of benzene.
The nitrated preparation oil of mirbane of benzene is directly to be used for obtaining oil of mirbane with nitric acid and vitriolic mixture and benzene.Benzene and nitric acid and vitriolic mixture unmixing in this process, reaction must be carried out under violent stirring, and the reaction times is longer, and productivity ratio is lower, and by product is many.Especially adopted a large amount of nitric acid and sulfuric acid in this reaction process, etching apparatus, and reacted acid solution contaminate environment does not easily meet modern green synthetic theory.
The aniline oxidation prepares in the process of oil of mirbane, has avoided the nitrated above-mentioned shortcoming of benzene.Originally, adopt tertbutyl peroxide as oxygenant, synthetic silicochromium molecular sieve is as catalyzer, the oxidation aromatic amino compound is corresponding nitro-compound in organic solvent (chloro thing), the productive rate of the oil of mirbane of this method preparation is than with the direct nitrated productive rate height of benzene, but this process has adopted comparatively expensive oxygenant tertbutyl peroxide and silicochromium molecular sieve catalyst, and catalyst loss is serious, and this reaction is to carry out in organic solvent, to human body worked the mischief and severe contamination environment.Afterwards, under the phase-transfer catalyst condition, with peroxide oxidation aniline synthesizing nitryl benzene, as Peracetic Acid.This method has been avoided the loss of catalyzer, but productive rate is too low, only has about 11%.Recently, the someone reports and adopts 90%H
2O
2Prepare oil of mirbane as oxygenant and heteropolyacid salt catalyst oxidation aniline, selected the H of high density in this method for use
2O
2, aniline oxidation gained by product is more, bring many technical problems for the separation and the purification of subsequent products, and the oil of mirbane productive rate is low.
In recent years, a kind of emerging green solvent---ionic liquid (ionic liquids is called for short IL) has become the focus of research.Ionic liquid is compared with conventional organic solvents, does not almost have vapour pressure, non-volatile, nontoxic; Equilibrium temperature scope and electrochemical stability potential window that better chemical stability, broad are arranged; Many inorganic salt and organism had good solubility; Be easy to and other separating substances; Advantage such as reusable makes it in catalyzed reaction, fields such as the organic synthesis potentiality that have a wide range of applications.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned oil of mirbane preparation method's shortcoming, and the method that a kind of environmental pollution is little, the reaction times is short, productive rate is high, product cost is low, catalyst recovery simply prepares oil of mirbane in ionic liquid is provided.
Solving the problems of the technologies described above the scheme that is adopted is that this method comprises the steps:
1, catalyst pre-treatment
Under normal pressure, in flask, add aniline, ionic liquid and catalyzer ammonium molybdate, the mol ratio of aniline and ionic liquid, ammonium molybdate is 1: 0.6～4.0: 0.007～0.020,25～60 ℃ reactions 0.5～2 hour.
Above-mentioned ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate or chlorination N-butyl-pyridinium, and 1-butyl-3-methyl imidazolium tetrafluoroborate and chlorination N-butyl-pyridinium are produced by the prompt chemical company limited of last marine origin.
2, preparation oil of mirbane
The adding mass concentration is 30% H in step 1
2O
2, aniline and H
2O
2Mol ratio be 1: 4.4～10.6,60～80 ℃ the reaction 5～10 hours, the reaction finish after, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, obtain the oil of mirbane crude product.
3, separate purification
The oil of mirbane crude product of step 2 preparation is separated with the column chromatography chromatogram partition method, obtain oil of mirbane, after water dewatered, the ionic liquid of recovery and catalyst recirculation were used.
In step 1 of the present invention, the preferred molar ratio of aniline and ionic liquid, ammonium molybdate is 1: 1.2～4.0: 0.011～0.020,25～50 ℃ of reactions of preferable reaction temperature 1～2 hour.In step 2 of the present invention, aniline and H
2O
2Preferred molar ratio be 1: 5.7～10.6,65～80 ℃ of preferable reaction temperature reaction 5～8 hours after reaction is finished, is used CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, obtain the oil of mirbane crude product.
In step 1 of the present invention, the optimum mole ratio of aniline and ionic liquid, ammonium molybdate is 1: 1.8: 0.015,30 ℃ of reactions of optimal reaction temperature 1 hour.In step 2 of the present invention, aniline and H
2O
2Optimum mole ratio be 1: 7.1,75 ℃ of optimal reaction temperatures reaction 6 hours after reaction is finished, is used CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, obtain the oil of mirbane crude product.
Prepared oil of mirbane characterizes with gas chromatograph, Fourier transformation infrared spectrometer, superconduction fourier numeralization nuclear magnetic resonance spectrometer.
The present invention is in ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate, and the employing mass concentration is 30% H
2O
2As oxygenant, ammonium molybdate prepares oil of mirbane as catalyzer with the aniline oxidation, has avoided in the nitrated preparation oil of mirbane of the benzene process, and a large amount of acid solutions are to the corrosion of equipment and the pollution of environment; Also avoided in the aniline oxidising process simultaneously, adopt shortcomings such as expensive oxygenant or complicated easily loss catalyzer and productive rate are low, in chemical reaction process, with the ionic liquid replace organic solvent, ionic liquid has played the effect of solvent and promotor, reduced the harm of human body and the pollution of environment, enlarged reaction conditions, shortened the reaction times, improved the productive rate of oil of mirbane, after reaction was finished, ionic liquid and catalyzer were still reusable, have reduced production cost.
Description of drawings
Fig. 1 is the Fourier transform infrared spectroscopy figure that adopts the prepared oil of mirbane of the present invention.
Fig. 2 is the superconduction fourier numeralization nmr spectrum that adopts the prepared oil of mirbane of the present invention.
Embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
With the raw materials used 10mmol aniline of preparation product oil of mirbane of the present invention is example, and other used raw material and preparation method thereof step is as follows:
1, catalyst pre-treatment
Under normal pressure, in flask, add 0.93g aniline, 4.00g 1-butyl-3-methyl imidazolium tetrafluoroborate, 0.19g catalyzer ammonium molybdate, the mol ratio of aniline and 1-butyl-3-methyl imidazolium tetrafluoroborate, ammonium molybdate is 1: 1.8: 0.015, and 30 ℃ were reacted 1 hour.
2, preparation oil of mirbane
Adding 8.00g mass concentration is 30% H in step 1
2O
2, aniline and H
2O
2Mol ratio be 1: 7.1,75 ℃ the reaction 6 hours, the reaction finish after, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, obtain the oil of mirbane crude product.
3, separate purification
The oil of mirbane crude product of step 2 preparation is separated with the column chromatography chromatogram partition method, obtain oil of mirbane, after water dewatered, the ionic liquid of recovery and catalyst recirculation were used, and the productive rate of oil of mirbane is 77%.
Embodiment 2
With the raw materials used 10mmol aniline of preparation product oil of mirbane of the present invention is example, and other used raw material and preparation method thereof step is as follows:
In step 1 of the present invention, under normal pressure, in flask, add 0.93g aniline, 1.40g 1-butyl-3-methyl imidazolium tetrafluoroborate, 0.09g catalyzer ammonium molybdate, the mol ratio of aniline and 1-butyl-3-methyl imidazolium tetrafluoroborate, ammonium molybdate is 1: 0.6: 0.007, and 30 ℃ were reacted 1 hour.In step 2 of the present invention, adding 5.00g mass concentration is 30% H in step 1
2O
2, aniline and H
2O
2Mol ratio be 1: 4.4,75 ℃ of temperature of reaction reaction 6 hours, other step in this step is identical with embodiment 1, is prepared into the oil of mirbane crude product.Other step is identical with embodiment 1, is prepared into oil of mirbane.
Embodiment 3
With the raw materials used 10mmol aniline of preparation product oil of mirbane of the present invention is example, and other used raw material and preparation method thereof step is as follows:
In step 1 of the present invention, under normal pressure, in flask, add 0.93g aniline, 9.00g 1-butyl-3-methyl imidazolium tetrafluoroborate, 0.25g catalyzer ammonium molybdate, the mol ratio of aniline and 1-butyl-3-methyl imidazolium tetrafluoroborate, ammonium molybdate is 1: 4.0: 0.020, and 30 ℃ were reacted 1 hour.In step 2 of the present invention, adding 12.00g mass concentration is 30% H in step 1
2O
2, aniline and H
2O
2Mol ratio be 1: 10.6,75 ℃ of temperature of reaction reaction 6 hours, other step in this step is identical with embodiment 1, is prepared into the oil of mirbane crude product.Other step is identical with embodiment 1, is prepared into oil of mirbane.
Embodiment 4
With the raw materials used 10mmol aniline of preparation product oil of mirbane of the present invention is example, and other used raw material and preparation method thereof step is as follows:
In the step 1 of above embodiment 1～3, the chlorination N-butyl-pyridinium of used ionic liquid 1-butyl-mole numbers such as 3-methyl imidazolium tetrafluoroborate usefulness is replaced, and other step is identical with respective embodiments, is prepared into oil of mirbane.
Embodiment 5
With the raw materials used 10mmol aniline of preparation product oil of mirbane of the present invention is example, and other used raw material and preparation method thereof step is as follows:
In the step 1 of above embodiment 1～4, used raw material and proportion of raw materials are identical with respective embodiments, and 25 ℃ were reacted 2 hours.In step 2, the adding mass concentration is 30% H in step 1
2O
2Identical with respective embodiments, 60 ℃ of reactions 10 hours, other step in this step was identical with embodiment 1, is prepared into the oil of mirbane crude product.Other step is identical with embodiment 1, is prepared into oil of mirbane.
Embodiment 6
With the raw materials used 10mmol aniline of preparation product oil of mirbane of the present invention is example, and other used raw material and preparation method thereof step is as follows:
In the step 1 of above embodiment 1～4, used raw material and proportion of raw materials are identical with respective embodiments, and 60 ℃ were reacted 0.5 hour.In step 2, the adding mass concentration is 30% H in step 1
2O
2Identical with respective embodiments, 80 ℃ of reactions 5 hours, other step in this step was identical with embodiment 1, is prepared into the oil of mirbane crude product.Other step is identical with embodiment 1, is prepared into oil of mirbane.
In order to determine optimised process step of the present invention, the contriver has carried out a large amount of laboratory study tests, and various experiment situations are as follows:
1, ion liquid selection
Under the normal pressure, in 5 flasks, add 0.93g aniline respectively, 0.17g ammonium molybdate, add 4.00g1-butyl-3-methyl imidazolium tetrafluoroborate respectively, 4.25g 1-butyl-3-Methylimidazole hydrosulfate, 3.90g bromination 1-butyl-3-Methylimidazole, 3.10g chlorination N-butyl-pyridinium, 0.60g a kind of in the methyl alcohol, be aniline and ammonium molybdate, the mol ratio of 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-butyl-3-Methylimidazole hydrosulfate or bromination 1-butyl-3-Methylimidazole or chlorination N-butyl-pyridinium or methyl alcohol is 1: 0.014: 1.8,30 ℃ were reacted respectively 1 hour, added 6.5g oxygenant H more respectively
2O
2, i.e. aniline and H
2O
2Mol ratio be 1: 5.7,60 ℃ were reacted respectively 6 hours, had investigated different ionic liquid and methyl alcohol as reaction medium, to the influence of prepared oil of mirbane productive rate.After reaction is finished, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, separate through the column chromatography chromatogram partition method, obtain oil of mirbane.Experimental result sees Table 1.
[bmim] BF in the table
4, [bmim] HSO
4, [bmim] Br, [bPy] Cl be respectively writing a Chinese character in simplified form of ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-Methylimidazole hydrosulfate, bromination 1-butyl-3-Methylimidazole, chlorination N-butyl-pyridinium.
The oil of mirbane productivity ratio in the various media of table 1
By table 1 as seen, under the same conditions, with ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate and chlorination N-butyl-pyridinium is solvent prepares oil of mirbane than aniline oxidation in methanol solvate productive rate height, and the productive rate in ionic liquid 1-butyl-3-Methylimidazole hydrosulfate and bromination 1-butyl-3-Methylimidazole is more much lower than the productive rate at methanol solvate on the contrary, and the productive rate in chlorination N-butyl-pyridinium is the highest.The present invention selects for use 1-butyl-3-methyl imidazolium tetrafluoroborate or chlorination N-butyl-pyridinium as reaction medium, and has carried out the investigation of optimum experimental condition.
2, the selection of ionic liquid consumption
Under the normal pressure, in 6 flasks, add 0.93g (10mmol) aniline, 0.17g (0.14mmol) ammonium molybdate respectively, add 1.40,2.70,4.00,5.50,6.80 respectively, 9.00g 1-butyl-3-methyl imidazolium tetrafluoroborate (being abbreviated as IL in the table), be that mole number corresponds to 6,12,18,24,30,40mmol, 30 ℃ were reacted respectively 1 hour, added 6.5g oxygenant H more respectively
2O
2, i.e. aniline and H
2O
2Mol ratio be 1: 5.7,60 ℃ were reacted respectively 6 hours, had investigated the influence of the consumption p-nitrophenyl productive rate of ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate.After reaction is finished, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, separate through the column chromatography chromatogram partition method, obtain oil of mirbane.
Experimental result sees Table 2.
The influence of the ion liquid consumption p-nitrophenyl of table 2 productive rate
| IL(mmol) | 6 | 12 | 18 | 24 | 30 | 40 |
| Productive rate (%) | 63 | 65 | 68 | 67 | 66 | 65 |
By table 2 as seen, under the same reaction conditions, the productive rate of oil of mirbane all has raising after adding ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate, the productive rate influence of the consumption p-nitrophenyl of ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate is little, ionic liquid 1-butyl-productive rate was the highest when 3-methyl imidazolium tetrafluoroborate consumption was 18mmol, had reached 68%.It is 1: 0.6～4.0 that the present invention selects aniline and ion liquid mol ratio, and optimum mole ratio is 1: 1.8.
3, the selection of oxygenant consumption
Under the normal pressure, in 9 flasks, add 0.93g (10mmol) aniline, 4.00g 1-butyl-3-methyl imidazolium tetrafluoroborate, 0.17g catalyzer ammonium molybdate respectively, the mol ratio that is aniline and 1-butyl-3-methyl imidazolium tetrafluoroborate, ammonium molybdate is 1: 1.8: 0.014,30 ℃ were reacted respectively 1 hour, added 3.00,4.00,5.00,6.00,6.50,7.00,8.00,8.50 more respectively, 12.00g oxygenant H
2O
2, promptly mole number correspond to 26,35,44,53,57,62,71,75,106mmol, 60 ℃ were reacted respectively 6 hours, and had investigated oxygenant H
2O
2The influence of consumption p-nitrophenyl productive rate.After reaction is finished, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, separate through the column chromatography chromatogram partition method, obtain oil of mirbane.
Experimental result sees Table 3.
Table 3H
2O
2The influence of consumption p-nitrophenyl productive rate
| H 2O 2(mmol) | 26 | 35 | 44 | 53 | 57 | 62 | 71 | 75 | 106 |
| Productive rate (%) | 45 | 52 | 58 | 61 | 68 | 71 | 73 | 72 | 64 |
By table 3 as seen, oxygenant H
2O
2When consumption was 44～106mmol, the oil of mirbane productive rate was higher, wherein, and H
2O
2Consumption when being 71mmol the productive rate of oil of mirbane the highest, reach 73%.The present invention adopts aniline and H
2O
2Mol ratio be 1: 4.4～10.6, optimum mole ratio is 1: 7.1.
4, the selection of catalyst levels
Under the normal pressure, in 7 flasks, add 0.93g (10mmol) aniline, 4.00g 1-butyl-3-methyl imidazolium tetrafluoroborate respectively, the mol ratio that is aniline and 1-butyl-3-methyl imidazolium tetrafluoroborate is 1: 1.8, add 0.09,0.13,0.15,0.17,0.19,0.20 respectively, 0.25g catalyzer ammonium molybdate, be that mole number corresponds to 0.07,0.11,0.12,0.14,0.15,0.16,0.20mmol, 30 ℃ were reacted respectively 1 hour, added 8.00g oxygenant H more respectively
2O
2, i.e. aniline and H
2O
2Mol ratio be 1: 7.1, reacted respectively 6 hours under 60 ℃, investigated the influence of catalyst levels p-nitrophenyl productive rate.After reaction is finished, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, separate through the column chromatography chromatogram partition method, obtain oil of mirbane.Experimental result sees Table 4.
The influence of table 4 ammonium molybdate consumption p-nitrophenyl productive rate
| Ammonium molybdate (mmol) | 0.07 | 0.11 | 0.12 | 0.14 | 0.15 | 0.16 | 0.20 |
| Productive rate (%) | 64 | 69 | 71 | 73 | 75 | 71 | 68 |
By table 4 as seen, catalyzer ammonium molybdate consumption is when 0.07～0.20mmol, and the oil of mirbane productivity ratio is higher, and when the ammonium molybdate consumption was 0.15mmol, the oil of mirbane productive rate reached and is up to 75%.It is 1: 0.007～0.020 that the present invention adopts the mol ratio of aniline and ammonium molybdate, and optimum mole ratio is 1: 0.015.
5, the selection of catalyst pre-treatment temperature of reaction
Under the normal pressure, in 8 flasks, add 0.93g aniline, 4.00g 1-butyl-3-methyl imidazolium tetrafluoroborate, 0.19g catalyzer ammonium molybdate respectively, the mol ratio that is aniline and 1-butyl-3-methyl imidazolium tetrafluoroborate, ammonium molybdate is 1: 1.8: 0.015, identical down in other condition, 20,25,30,35,40,50,60,70 ℃ of reactions 1 hour, add 8.00g oxygenant H more respectively respectively
2O
2, i.e. aniline and H
2O
2Mol ratio be 1: 7.1,60 ℃ were reacted respectively 6 hours.Investigated the influence of under differing temps, carrying out catalyst pre-treatment p-nitrophenyl productive rate.After reaction is finished, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, separate through the column chromatography chromatogram partition method, obtain oil of mirbane.Experimental result sees Table 5.
The influence of table 5 differential responses temperature catalyst pre-treatment p-nitrophenyl productive rate
| Temperature (℃) | 20 | 25 | 30 | 35 | 40 | 50 | 60 | 70 |
| Productive rate (%) | 56 | 66 | 75 | 69 | 70 | 68 | 65 | 32 |
By table 5 as seen, under same reaction conditions, ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate and catalyzer ammonium molybdate are except lower at 20 and 70 ℃ of prepared in reaction oil of mirbane productive rates, the productive rate of oil of mirbane all increases under other temperature, and the productive rate at 30 ℃ is the highest, reaches about 75%.It is 25～60 ℃ that the present invention adopts the catalyst pre-treatment temperature of reaction, and wherein optimal reaction temperature is 30 ℃.
6, the selection of temperature of reaction
Under the normal pressure, in 6 flasks, add 0.93g aniline, 4.00g 1-butyl-3-methyl imidazolium tetrafluoroborate, 0.19g catalyzer ammonium molybdate respectively, the mol ratio that is aniline and 1-butyl-3-methyl imidazolium tetrafluoroborate, ammonium molybdate is 1: 1.8: 0.015,30 ℃ were reacted respectively 1 hour, added 8.00g oxygenant H more respectively
2O
2, i.e. aniline and H
2O
2Mol ratio be 1: 7.1,50,60,65,70,75,80 ℃ of down reactions 6 hours, investigated the productive rate influence of different temperature of reaction p-nitrophenyls respectively.After reaction is finished, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, separate through the column chromatography chromatogram partition method, obtain oil of mirbane.Experimental result sees Table 6.
The influence of table 6 temperature of reaction p-nitrophenyl productive rate
| Temperature (℃) | 50 | 60 | 65 | 70 | 75 | 80 |
| Productive rate (%) | 46 | 68 | 72 | 75 | 77 | 71 |
By table 6 as seen, under the same reaction conditions, along with the raising of temperature of reaction, the productive rate of oil of mirbane increases gradually, reaches 77% in the time of 75 ℃, elevated temperature again, and productive rate will descend to some extent.It is 60～80 ℃ that the present invention adopts temperature of reaction, and wherein optimal reaction temperature is 75 ℃.
7, the selection in reaction times
Under the normal pressure, in 6 flasks, add 0.93g aniline, 4.00g 1-butyl-3-methyl imidazolium tetrafluoroborate, 0.19g catalyzer ammonium molybdate respectively, the mol ratio that is aniline and 1-butyl-3-methyl imidazolium tetrafluoroborate, ammonium molybdate is 1: 1.8: 0.015,30 ℃ were reacted respectively 1 hour, added 8.00g oxygenant H more respectively
2O
2, i.e. aniline and H
2O
2Mol ratio be 1: 7.1, reacted respectively 2,5,6,7,8,10 hours under 75 ℃, investigated the influence of differential responses time p-nitrophenyl productive rate.After reaction is finished, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, separate through the column chromatography chromatogram partition method, obtain oil of mirbane.Experimental result sees Table 7.
The influence of table 7 reaction times p-nitrophenyl productive rate
| Time (hour) | 2 | 5 | 6 | 7 | 8 | 10 |
| Productive rate (%) | 59 | 71 | 77 | 74 | 67 | 68 |
By table 7 as seen, under the same reaction conditions, in 5～10 hours reaction times, the oil of mirbane productive rate is higher, wherein reaches the highest in 6 hours, is 77%.It is 5～10 hours that the present invention selects the reaction times for use, and optimum reacting time is 6 hours.
8, round-robin test
In flask, add 0.93g aniline, 4.00g 1-butyl-3-methyl imidazolium tetrafluoroborate, 0.19g catalyzer ammonium molybdate, the mol ratio that is aniline and 1-butyl-3-methyl imidazolium tetrafluoroborate, ammonium molybdate is 1: 1.8: 0.015,30 ℃ were reacted 1 hour, and added 8.00g oxygenant H again
2O
2, i.e. aniline and H
2O
2Mol ratio be 1: 7.1,75 ℃ the reaction 6 hours.After reaction is finished, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, separate through the column chromatography chromatogram partition method, obtain oil of mirbane, after water dewaters, add again and above-mentioned reacting phase raw material and proportioning thereof together, repeat 2 secondary responses, obtain oil of mirbane.3 times the prepared oil of mirbane productive rate of chemical reaction sees Table 8.
The oil of mirbane productive rate that table 8 catalyzer and ionic liquid circulation are 3 times
| |
1 | 2 | 3 |
| Productive rate (%) | 77 | 72 | 65 |
By table 8 as seen, 3 employed ammonium molybdate catalyzer of cyclic chemical reaction still have catalytic activity, and ammonium molybdate and ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate can be recycled.
In order to verify beneficial effect of the present invention, the contriver adopts the oil of mirbane of the embodiment of the invention 1 preparation to test, and various experiment situations are as follows:
Testing tool: Fourier transformation infrared spectrometer, model are Avatar360E.S.P.FTIR, are produced by Buddhist nun's high-tensile strength instrument company; Superconduction fourier numeralization nuclear magnetic resonance spectrometer, model is AVANCF300MHZ, is produced by Bruker company.
Adopt the Fourier transform infrared spectroscopy figure of the oil of mirbane of the embodiment of the invention 1 preparation to see Fig. 1, as seen from Figure 1,3075cm
-1Can belong to stretching vibration, 850,792 and 701cm for c h bond on the phenyl ring
-1The absorption frequency at place is a mono-substituted charateristic avsorption band on the phenyl ring, 1524 and 1347cm
-1The absorption frequency at place is on the phenyl ring-NO
2Charateristic avsorption band.This standard infrared spectrogram with oil of mirbane is consistent.
Adopt the superconduction fourier numeralization nmr spectrum of the oil of mirbane of the embodiment of the invention 1 preparation to see Fig. 2, as seen from Figure 2,8.2,7.7, the 7.5ppm place is respectively the chemical shift of oil of mirbane ortho position, contraposition, a position H.This standard nmr spectrum with oil of mirbane is consistent.
Claims (3)
1, a kind of method for preparing oil of mirbane in ionic liquid is characterized in that this method comprises the steps:
(1) catalyst pre-treatment
Under normal pressure, in flask, add aniline, ionic liquid and catalyzer ammonium molybdate, the mol ratio of aniline and ionic liquid, ammonium molybdate is 1: 0.6～4.0: 0.007～0.020,25～60 ℃ reactions 0.5～2 hour;
Above-mentioned ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate or chlorination N-butyl-pyridinium;
(2) preparation oil of mirbane
The adding mass concentration is 30% H in step 1
2O
2, aniline and H
2O
2Mol ratio be 1: 4.4～10.6,60～80 ℃ the reaction 5～10 hours, the reaction finish after, use CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, obtain the oil of mirbane crude product;
(3) separate purification
The oil of mirbane crude product of step 2 preparation is separated with the column chromatography chromatogram partition method, obtain oil of mirbane, after water dewatered, the ionic liquid of recovery and catalyst recirculation were used.
2, according to the described method that in ionic liquid, prepares oil of mirbane of claim 1, it is characterized in that: in step 1, the mol ratio of aniline and ionic liquid, ammonium molybdate is 1: 1.2～4.0: 0.011～0.020,25～50 ℃ of reactions of temperature of reaction 1～2 hour; In step 2, aniline and H
2O
2Mol ratio be 1: 5.7～10.6,65～80 ℃ of temperature of reaction reaction 5～8 hours after reaction is finished, is used CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, obtain the oil of mirbane crude product.
3, according to the described method for preparing oil of mirbane in ionic liquid of claim 1, it is characterized in that: in step 1, the mol ratio of aniline and ionic liquid, ammonium molybdate is 1: 1.8: 0.015,30 ℃ of reactions of temperature of reaction 1 hour; In step 2, aniline and H
2O
2Mol ratio be 1: 7.1,75 ℃ of temperature of reaction reaction 6 hours after reaction is finished, is used CH
2Cl
2From reaction solution, extract organic phase, boil off CH
2Cl
2, obtain the oil of mirbane crude product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417457A (en) * | 2011-08-22 | 2012-04-18 | 盐城师范学院 | P-chlorobenzotrifluoride clean nitration reaction catalyzed by heteropoly acid ionic liquid |
| CN108017089A (en) * | 2017-12-11 | 2018-05-11 | 宁夏共宣环保科技有限责任公司 | A kind of method that ammonium molybdate is recycled from useless molybdenum catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005028446A1 (en) * | 2003-09-18 | 2005-03-31 | Sumitomo Chemical Company, Limited | Ionic liquid and method of reaction using the same |
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2009
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417457A (en) * | 2011-08-22 | 2012-04-18 | 盐城师范学院 | P-chlorobenzotrifluoride clean nitration reaction catalyzed by heteropoly acid ionic liquid |
| CN108017089A (en) * | 2017-12-11 | 2018-05-11 | 宁夏共宣环保科技有限责任公司 | A kind of method that ammonium molybdate is recycled from useless molybdenum catalyst |
| CN108017089B (en) * | 2017-12-11 | 2019-08-02 | 宁夏共宣环保科技有限责任公司 | A method of recycling ammonium molybdate from useless molybdenum catalyst |
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