CN105175269A - Synthesis method of 4-nitro m-xylene by selective nitration of bismuth nitrate - Google Patents
Synthesis method of 4-nitro m-xylene by selective nitration of bismuth nitrate Download PDFInfo
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Abstract
A synthesis method of 4-nitro m-xylene by selective nitration of bismuth nitrate comprises the following steps: adding 3-7ml of petroleum ether to a round bottom flask under magnetic stirring, successively adding 2.0-4.0mmol of m-xylene, 2.0-10.0mmol of acetic anhydride, 2.0-4.0mmol of Bi(NO3)3.5H2O and 0.4-1.2g of a zeolite molecular sieve catalyst Hbeta (500); heating with refluxing for 2-6 h and terminating the reaction; filtering for removing the catalyst; and conducting liquid washing, dewatering and drying. The method can greatly improve the yield of 4-nitro m-xylene in a nitration product, and the nitration selectivity of m-xylene is significantly enhanced; and under the optimum conditions, the yield and selectivity of 4-nitro m-xylene reach 89.9% and 8.26. The method has the advantages of easy control of reaction conditions, short time consumption, simple process, low production cost, less pollution, and convenience for industrial production.
Description
Technical field
The invention belongs to fine-chemical intermediate meta-xylene synthesis field, be specifically related to the method for a kind of Bismuth trinitrate selective nitration synthesis 4-Nitro-m-xylene.
Background technology
The nitrated main generation 4-Nitro-m-xylene of m-xylene one and 2-meta-xylene, they are important organic intermediates, are widely used in dyestuff, medicine, plastics, rubber ingredients, rust cleaning, sterilization and plant-growth regulator etc.Wherein, 4-Nitro-m-xylene is mainly used in pesticide industry, as the production of the organic nitrogen pesticides such as amitraz, single carbonamidine, medimeform, also can be used for the intermediate, acetyl waste water etc. of synthetic dyestuff, pigment, therefore developing 4-Nitro-m-xylene has important practical to be worth.At present, still using with m-xylene in industrial production is that raw material prepares 4-Nitro-m-xylene through nitric-sulfuric acid nitrofication process, but along with the development in epoch, the shortcoming of the method becomes increasingly conspicuous, and is mainly manifested in: strong acid is serious to equipment corrosion; The waste water serious environment pollution produced; Reaction preference is not high, and produce organic waste, productive rate is low, causes the wasting of resources; The side reactions such as easy generation polynitration and oxidation, have potential safety hazard.A large amount of research work has been done in recent years for addressing these problems many investigators, such as, the people such as Olah (Olah, G.A., etal., JournalofOrganicChemistry, 1981.46 (17): p.3533-3537.) have studied and use Silver Nitrate as the nitration reaction of nitrating agent to m-xylene under boron trifluoride catalysis in acetonitrile solution, this reaction vigorous stirring need react 18h at 25 DEG C, obtain 4-Nitro-m-xylene in nitration product and account for 87%, 2-meta-xylene accounts for 13%, 4-/2-ratio is 6.69, the method selectivity still can, but utilize acetonitrile as solvents, strong toxicity, use this Lewis acid of boron trifluoride to need nitrogen protection and anhydrous condition to carry out as catalyzer simultaneously, long reaction time, and it is expensive to use Silver Nitrate to make nitrating agent, the people such as Waller (Waller, F.J., etal., ChemicalCommunications, 1997 (6): p.613-614.) use the nitration reaction of the trifluoromethanesulfonic acid salt pair m-xylene of lanthanon to be studied, when use Ytterbiumtriflate (III) needs stirring and refluxing 12h as catalyzer, in nitration product, 4-Nitro-m-xylene accounts for 85%, 2-meta-xylene accounts for 15%, 4-/2-ratio is 5.67, the nitrated poor selectivity of the method, long reaction time, frequent use rare earth metal salt, not only add production cost, but also can be detrimental to health, therefore, although the preparation method of above-mentioned 4-Nitro-m-xylene avoids seriously polluted, security hidden trouble that traditional industry middle strong acidity reaction conditions brings to a certain extent, still exist produce that 4-Nitro-m-xylene cost is high, the nitrated poor selectivity of long reaction time, m-xylene and nitration product 4-Nitro-m-xylene productive rate problem on the low side.
Zeolite molecular sieve is a kind of porousness silicon aluminate crystal, its elementary cell is Si-O tetrahedron and Al-O tetrahedron, these tetrahedrons are linked to be ring mutually by the Sauerstoffatom of drift angle, on ring, tetrahedron connects into orderly three dimensional skeletal structure by oxo bridge with certain rule again, there is the bug hole of marshalling, geode and duct, surface-area is large, and therefore zeolite molecular sieve has good catalytic performance, can be used as effective catalyzer and support of the catalyst.The catalytic activity of molecular sieve depends on surface acidity OH group (B acid) and dewaters and the L acid site of generation, these acid site overwhelming majority are positioned at the vestibule of molecular sieve, due to the combined action in pore passage structure and acid site, thus define shape selective catalysis ability specific to molecular sieve ordered structure.Nitrate carries out nitration reaction because the nitrate ion contained can be used as nitrating agent to simple aromatic hydrocarbons, and the acid avoiding the severe corrosive in traditional industry, as the use of nitric acid and sulfuric acid, has a good application prospect, receives the extensive concern of investigator.The shape selective catalysis ability utilizing zeolite molecular sieve good and nitrate as nitrating agent there is the advantage of Environmental Safety, both are used for jointly nitrated m-xylene and improve its reaction preference, the productive rate improving 4-Nitro-m-xylene has important actual heavy justice.
Summary of the invention
In order to overcome, prior art m-xylene is nitrated prepares too low, the nitrated poor selectivity of 4-Nitro-m-xylene productive rate, length consuming time, problem that production cost is high, and the present invention will provide the method for the Bismuth trinitrate selective nitration synthesis 4-Nitro-m-xylene that a kind of selectivity is strong, productive rate is desirable.
For realizing above-mentioned technical problem, the technical solution used in the present invention is:
A kind of method of Bismuth trinitrate selective nitration synthesis 4-Nitro-m-xylene, comprise the following steps: under (1) magnetic agitation, to round-bottomed flask PetroChina Company Limited. ether 3 ~ 7mL, then add m-xylene 2.0 ~ 4.0mmol, diacetyl oxide 2.0 ~ 10.0mmol, Bi (NO successively
3)
35H
2o2.0 ~ 4.0mmol and zeolite [molecular sieve H β (500) 0.4 ~ 1.2g;
(2) stopped reaction after reflux 2 ~ 6h;
(3) Filtration of catalyst, liquid phase washs the dry rear gas chromatographic analysis that dewaters.
Preferably, sherwood oil described in step (1) is that chloroform replaces.
Preferably, zeolite [molecular sieve H β (500) described in step (1) is H β (25), any one in H β (280) or SAPO-34 replace.
Preferably, Bi (NO described in step (1)
3)
35H
2the consumption of O is 2.4mmol ~ 3.2mmol.
Preferably, described in step (1), the consumption of diacetyl oxide is 5mmol ~ 7mmol.
Preferably, described in step (1), zeolite [molecular sieve H β (500) is 0.6 ~ 1.0g.
Preferably, described in step (2), return time is 3h ~ 5h.
Preferably, the washing of liquid phase described in step (3) is the NaHCO of 5% with water, massfraction successively
3solution and water washing.
The present invention compared with prior art, has following beneficial effect:
(1) the present invention is that nitrating agent avoids strong acid such as using nitric acid to the severe corrosive of equipment with Bismuth trinitrate, simultaneously bismuth ion wherein has certain catalytic effect, act synergistically with zeolite [molecular sieve H β (500) catalyzer, reaction is carried out fast, shorten the reaction times widely, improve production efficiency;
(2) the present invention is due to the pore passage structure of zeolite [molecular sieve H β (500) uniqueness, the 4-Nitro-m-xylene making molecular diameter close with its channel diameter more easily by, and other molecules due to steric hindrance not by, thus greatly improve the ratio of 4-Nitro-m-xylene in nitration product, the nitrated selectivity of m-xylene significantly strengthens, productive rate also obviously increases, and under top condition, productive rate reaches 89.9%, 4-/2-ratio and reaches 8.26.
(3) this invention easily-controlled reaction conditions, operating process is simple, the economic environmental protection of raw materials for production, and production cost is low.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described in detail.
Embodiment 1
In 25mL round-bottomed flask, add sherwood oil 3mL, under magnetic stirring, add m-xylene 2.0mmol, diacetyl oxide 2.0mmol, Bi (NO successively
3)
35H
2o2.0mmol and zeolite [molecular sieve H β (500) 0.4g, 4mL water stopped reaction is added after reflux 2h, filtering separation removing zeolite [molecular sieve H β (500), catalyzer can give over to and reuse, and gained liquid phase is the NaHCO of 5% by the water of 10mL, mass percent successively
3solution and water washing, then adding a small amount of magnesium sulfate and to dewater drying, is that internal standard substance carries out gas chromatographic analysis with para-nitrotoluene after above-mentioned steps completes.Result shows, productive rate is 85.5%, and wherein 4-Nitro-m-xylene accounts for 89.1%, 2-meta-xylene and accounts for 10.9%, 4-/2-ratio and reach 8.17.Zeolite [molecular sieve H β (500) in above step can be any one replacement in catalyzer H β (25), H β (280) or SAPO-34.
Embodiment 2
In 25mL round-bottomed flask, add sherwood oil 7mL, under magnetic stirring, add m-xylene 4.0mmol, diacetyl oxide 10.0mmol, Bi (NO successively
3)
35H
2o4.0mmo and zeolite [molecular sieve H β (500) 1.2g, 6mL water stopped reaction is added after reflux 6h, filtering separation removing zeolite [molecular sieve H β (500), catalyzer can give over to and reuse, and gained liquid phase is the NaHCO of 5% by the water of 10mL, mass percent successively
3solution and water washing, then adding a small amount of magnesium sulfate and to dewater drying, is that internal standard substance carries out gas chromatographic analysis with para-nitrotoluene after above-mentioned steps completes.Result shows, productive rate is 86.4%, and wherein 4-Nitro-m-xylene accounts for 88.7%, 2-meta-xylene and accounts for 11.3%, 4-/2-ratio and reach 7.85.
Experiment 3
In 25mL round-bottomed flask, add sherwood oil 5mL, under magnetic stirring, add m-xylene 3.0mmol, diacetyl oxide 6.0mmol, Bi (NO successively
3)
35H
2o3.0mmol and zeolite [molecular sieve H β (500) 0.8g, 5mL water stopped reaction is added after reflux 4h, filtering separation removing zeolite [molecular sieve H β (500), catalyzer can give over to and reuse, and gained liquid phase is the NaHCO of 5% by the water of 10mL, mass percent successively
3solution and water washing, then adding a small amount of magnesium sulfate and to dewater drying, is that internal standard substance carries out gas chromatographic analysis with para-nitrotoluene after above-mentioned steps completes.Result shows, productive rate is 89.9%, and wherein 4-Nitro-m-xylene accounts for 89.2%, 2-meta-xylene and accounts for 10.8%, 4-/2-ratio and reach 8.26.
Embodiment 4
In 25mL round-bottomed flask, add chloroform 3mL, under magnetic stirring, add m-xylene 3.0mmol, diacetyl oxide 5.0mmol, Bi (NO successively
3)
35H
2o2.4mmol and zeolite [molecular sieve H β (500) 0.6g, 5mL water stopped reaction is added after reflux 3h, filtering separation removing zeolite [molecular sieve H β (500), catalyzer can give over to and reuse, and gained liquid phase is the NaHCO of 5% by the water of 10mL, mass percent successively
3solution and water washing, then adding a small amount of magnesium sulfate and to dewater drying, is that internal standard substance carries out gas chromatographic analysis with para-nitrotoluene after above-mentioned steps completes.Result shows, productive rate is 89.9%, and wherein 4-Nitro-m-xylene accounts for 88.9%, 2-meta-xylene and accounts for 11.1%, 4-/2-ratio and reach 8.01.
Embodiment 5
In 25mL round-bottomed flask, add chloroform 5mL, under magnetic stirring, add m-xylene 3.0mmol, diacetyl oxide 7.0mmol, Bi (NO successively
3)
35H
2o3.2mmol and zeolite [molecular sieve H β (500) 1.0g, 8mL water stopped reaction is added after reflux 5h, filtering separation removing zeolite [molecular sieve H β (500), catalyzer can give over to and reuse, and gained liquid phase is the NaHCO of 5% by the water of 10mL, mass percent successively
3solution and water washing, then adding a small amount of magnesium sulfate and to dewater drying, is that internal standard substance carries out gas chromatographic analysis with para-nitrotoluene after above-mentioned steps completes.Result shows, productive rate is 84.9%, and wherein 4-Nitro-m-xylene accounts for 89.1%, 2-meta-xylene and accounts for 10.9%, 4-/2-ratio and reach 8.17.
Embodiment 6
In 25mL round-bottomed flask, add chloroform 7mL, under magnetic stirring, add m-xylene 3.0mmol, diacetyl oxide 8.0mmol, Bi (NO successively
3)
35H
2o2.8mmol and zeolite [molecular sieve H β (500) 0.7g, 5mL water stopped reaction is added after reflux 4h, filtering separation removing zeolite [molecular sieve H β (500), gained liquid phase is the NaHCO of 5% by the water of 10mL, mass percent successively
3solution and water washing, then adding a small amount of water in a small amount of magnesium sulfate removing solution, is that internal standard substance carries out gas chromatographic analysis with para-nitrotoluene after above-mentioned steps completes.Result shows, productive rate is 80.3%, and wherein 4-Nitro-m-xylene accounts for 88.7%, 2-meta-xylene and accounts for 11.3%, 4-/2-ratio and reach 7.85.
Embodiment 7
In 25mL round-bottomed flask, add sherwood oil 4mL, under magnetic stirring, add m-xylene 3.0mmol, diacetyl oxide 8.0mmol, Bi (NO successively
3)
35H
2o3.6mmol and zeolite [molecular sieve H β (500) 1.1g, 5mL water stopped reaction is added after reflux 4h, filtering separation removing zeolite [molecular sieve H β (500), gained liquid phase is the NaHCO of 5% by the water of 10mL, mass percent successively
3solution and water washing, then adding a small amount of water in a small amount of magnesium sulfate or calcium chloride removing solution, is that internal standard substance carries out gas chromatographic analysis with para-nitrotoluene after above-mentioned steps completes.Result shows, productive rate is 81.5%, and wherein 4-Nitro-m-xylene accounts for 88.4%, 2-meta-xylene and accounts for 11.6%, 4-/2-ratio and reach 7.62.
It should be noted last that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (8)
1. a method for Bismuth trinitrate selective nitration synthesis 4-Nitro-m-xylene, is characterized in that comprising the following steps:
(1) under magnetic agitation, in round-bottomed flask, add sherwood oil 3 ~ 7mL, then add m-xylene 2.0 ~ 4.0mmol, diacetyl oxide 2.0 ~ 10.0mmol, Bi (NO successively
3)
35H
2o2.0 ~ 4.0mmol and zeolite [molecular sieve H β (500) 0.4 ~ 1.2g;
(2) stopped reaction after reflux 2 ~ 6h;
(2) Filtration of catalyst, liquid phase washs the dry rear gas chromatographic analysis that dewaters.
2. the method for Bismuth trinitrate selective nitration synthesis 4-Nitro-m-xylene according to claim 1, is characterized in that: sherwood oil described in step (1) is that chloroform replaces.
3. the method for Bismuth trinitrate selective nitration according to claim 1 synthesis 4-Nitro-m-xylene, is characterized in that: zeolite [molecular sieve H β (500) described in step (1) is H β (25), any one in H β (280) or SAPO-34 replaces.
4. the method for Bismuth trinitrate selective nitration synthesis 4-Nitro-m-xylene according to claim 1, is characterized in that: Bi (NO described in step (1)
3)
35H
2the consumption of O is 2.4mmol ~ 3.2mmol.
5. the method for Bismuth trinitrate selective nitration synthesis 4-Nitro-m-xylene according to claim 1, is characterized in that: described in step (1), the consumption of diacetyl oxide is 5mmol ~ 7mmol.
6. the method for Bismuth trinitrate selective nitration synthesis 4-Nitro-m-xylene according to claim 1, is characterized in that: described in step (1), zeolite [molecular sieve H β (500) is 0.6 ~ 1.0g.
7. the method for Bismuth trinitrate selective nitration synthesis 4-Nitro-m-xylene according to claim 1, is characterized in that: described in step (2), return time is 3h ~ 5h.
8. the method for Bismuth trinitrate selective nitration according to claim 1 synthesis 4-Nitro-m-xylene, is characterized in that: the washing of liquid phase described in step (3) is the NaHCO of 5% with water, massfraction successively
3and water washing.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565604A (en) * | 2016-10-31 | 2017-04-19 | 河南师范大学 | Synthetic method of 5-nitro-8-carboxamidoquinoline compound |
| CN110577470A (en) * | 2019-10-09 | 2019-12-17 | 蚌埠学院 | method for catalyzing selective nitration of 2-naphthyl methyl ether by zeolite molecular sieve |
| CN110590558A (en) * | 2019-10-09 | 2019-12-20 | 蚌埠学院 | Method for catalyzing selective nitration of 1-methoxynaphthalene by using zeolite molecular sieve |
| CN113563196A (en) * | 2021-07-27 | 2021-10-29 | 安徽江泰新材料科技有限公司 | Preparation method of 2,4(2,6) -dimethyl nitrobenzene |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565604A (en) * | 2016-10-31 | 2017-04-19 | 河南师范大学 | Synthetic method of 5-nitro-8-carboxamidoquinoline compound |
| CN106565604B (en) * | 2016-10-31 | 2019-01-01 | 河南师范大学 | A kind of synthetic method of 5- nitro -8- amide groups quinolines |
| CN110577470A (en) * | 2019-10-09 | 2019-12-17 | 蚌埠学院 | method for catalyzing selective nitration of 2-naphthyl methyl ether by zeolite molecular sieve |
| CN110590558A (en) * | 2019-10-09 | 2019-12-20 | 蚌埠学院 | Method for catalyzing selective nitration of 1-methoxynaphthalene by using zeolite molecular sieve |
| CN110577470B (en) * | 2019-10-09 | 2022-12-27 | 蚌埠学院 | Method for catalyzing selective nitration of 2-naphthyl methyl ether by using zeolite molecular sieve |
| CN113563196A (en) * | 2021-07-27 | 2021-10-29 | 安徽江泰新材料科技有限公司 | Preparation method of 2,4(2,6) -dimethyl nitrobenzene |
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