CN102329236B - Technology for producing o-nitrobenzaldehyde - Google Patents
Technology for producing o-nitrobenzaldehyde Download PDFInfo
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- CN102329236B CN102329236B CN 201110173088 CN201110173088A CN102329236B CN 102329236 B CN102329236 B CN 102329236B CN 201110173088 CN201110173088 CN 201110173088 CN 201110173088 A CN201110173088 A CN 201110173088A CN 102329236 B CN102329236 B CN 102329236B
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Abstract
The invention relates to a technology for producing o-nitrobenzaldehyde. The technology is characterized in that: o-nitrotoluene which is a raw material is subjected to steps of bromination, hydrolysis, oxidation, addition, alkali precipitation and the like to prepare o-nitrobenzaldehyde. Dichloroethane which is used in the bromination of the technology and is environmentally friendly allows a problem of carbon tetrachloride forbidding to be solved, and the unreacted raw material is adopted as a solvent in the oxidation step. Cheap hydrogen peroxide which is added in bromination allows the bromine utilization rate to be effectively improved and unfavorable influences of a large amount of a hydrogen bromide gas to environment and workers to be avoided.
Description
Technical field
The present invention relates to a kind of production technique of organic synthesis intermediate, particularly a kind of technology for producing o-nitrobenzaldehyde.
Background technology
In prior art, what the Ortho Nitro Benzaldehyde production method adopted is a kind of bromination method of three steps, is to be adjacent nitro bromobenzyl with Ortho Nitro Toluene bromination under the existence of initiator, then is hydrolyzed to corresponding benzylalcohol, reoxidizes to be aldehyde.This Ortho Nitro Benzaldehyde production method is that major defect is: the one, and bromination, oxidation have adopted the tetracol phenixin of having forbidden in the world at present as solvent, and the 2nd, it is unfavorable that a large amount of bromize hydrogen gas of producing during bromination operate environment and workman, need be processed.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, a kind of new more environmental protection, safety is provided, also can improves the technology for producing o-nitrobenzaldehyde of the utilization ratio of raw material.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of technology for producing o-nitrobenzaldehyde, is characterized in, its step is as follows:
(1) bromination: the water, ethylene dichloride, Ortho Nitro Toluene, the bromine that measure are dropped into closed bromination reaction still, pass into the chilled brine cooling toward condenser, under whipped state, reactor is warming up to 40 ℃, add initiator peroxy dicarbonate (2-ethylhexyl) ester, continue to heat up 50～55 ℃ fade after, minute 2-3 batch adds hydrogen peroxide and initiator, adds after the question response thing fades at every turn all again; Hydrogen peroxide and initiator finish, the reaction mixture standing demix after rear insulation 2～3 h that fades, and organic layer enters next hydrolyzing process; The weight ratio of each raw material is Ortho Nitro Toluene: bromine: water: ethylene dichloride: hydrogen peroxide: initiator=1: 0.4-0.6: 2.0-3.0: 2.0-3.0: 0.4-0.6: 0.04-0.06;
(2) hydrolysis: adding the mass percent concentration for preparing in hydrolysis kettle is the 8-12% aqueous sodium carbonate, bromination operation gained organic layer is put into hydrolysis kettle stir, and CO is arranged
2Gas generates; Heat up, hydrolysis, while Distillation recovery ethylene dichloride, the ethylene dichloride cover under reclaiming is used for the bromo chemical order; Layering after insulation 2～3 h after distillation finishes, the gained organic layer enters next oxidation operation;
(3) oxidation: the dilute nitric acid solution that is 55-65% with the mass percent concentration for preparing adds scale tank, hydrolysis reaction gained organic layer is put into oxidizing reactor, add the catalyzer Sodium Nitrite, start stirring, slowly drip dilute nitric acid solution when being warming up to 45 ± 5 ℃, the reaction nature is warming up to 55～60 ℃; Dropwise standing demix after rear insulation 2～5h, the gained organic layer enters in next and operation;
(4) neutralization: the liquid caustic soda that is 25-35% with mass percent concentration adds scale tank, oxidation gained organic layer put into and still, and after the dropping liquid caustic soda is neutralized to pH=7～8, standing demix; The gained organic layer enters next addition operation;
(5) refining: that the aqueous solution that mass percent concentration is the Sodium Pyrosulfite of 10-14% is put into the addition still, neutralization reaction gained organic layer is added in the addition still, after stirring, standing, divide the organic layer that goes to the bottom, after the water layer on upper strata added liquid caustic soda to be adjusted to pH=13～14, centrifugation got the Ortho Nitro Benzaldehyde crude product; Crude product is put into refining decolouring still, add appropriate toluene and gac, be warming up to 50 ± 5 ℃, enter in crystallization kettle after filtration to lower the temperature, temperature is centrifugal after reducing, dry to get finished product.
Main chemical reactions equation in the inventive method is:
H
2O
2+2HBr
Br
2+2H
2O
NaHSO
3 + NaOH
Na
2SO
3+H
2O
NNO
3 + NaOH
NaNO
3+H
2O
In the step of above-described technology for producing o-nitrobenzaldehyde technical scheme (5), after can applying mechanically 4～5 times, described toluene carries out again toluene recovery.
Compared with prior art, technique of the present invention mainly has the following advantages:
1, the solvent that uses during bromination is ethylene dichloride, and more environmental protection has also solved the problem of tetracol phenixin forbidding, and the solvent during oxidation has adopted unreacted raw material as solvent.
2, during bromination, to effectively to improve the utilization ratio of bromine, avoid again a large amount of bromize hydrogen gas to environment and workman's adverse effect by adding cheap hydrogen peroxide.
Embodiment
Below further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not consist of its Copyright law.
Embodiment 1, a kind of technology for producing o-nitrobenzaldehyde, and its step is as follows:
(1) bromination: the water, ethylene dichloride, Ortho Nitro Toluene, the bromine that measure are dropped into closed bromination reaction still, pass into the chilled brine cooling toward condenser, under whipped state, reactor is warming up to 40 ℃, add initiator peroxy dicarbonate (2-ethylhexyl) ester, continue to heat up 50 ℃ fade after, minutes 2 batches add hydrogen peroxide and initiator, add after the question response thing fades at every turn all again; Hydrogen peroxide and initiator finish, the reaction mixture standing demix after rear insulation 2 h that fades, and organic layer enters next hydrolyzing process; The weight ratio of each raw material is Ortho Nitro Toluene: bromine: water: ethylene dichloride: hydrogen peroxide: initiator=1: 0.4: 2.0: 2.0: 0.4: 0.04;
(2) hydrolysis: adding the mass percent concentration for preparing in hydrolysis kettle is 8% aqueous sodium carbonate, bromination operation gained organic layer is put into hydrolysis kettle stir, and CO is arranged
2Gas generates; Heat up, hydrolysis, while Distillation recovery ethylene dichloride, the ethylene dichloride cover under reclaiming is used for the bromo chemical order; Layering after insulation 2 h after distillation finishes, the gained organic layer enters next oxidation operation;
(3) oxidation: be that 55% dilute nitric acid solution adds scale tank with the mass percent concentration for preparing, hydrolysis reaction gained organic layer is put into oxidizing reactor, add the catalyzer Sodium Nitrite, start stirring, slowly drip dilute nitric acid solution when being warming up to 40 ℃, the reaction nature is warming up to 55 ℃; Dropwise standing demix after rear insulation 2h, the gained organic layer enters in next and operation;
(4) neutralization: be that 25% liquid caustic soda adds scale tank with mass percent concentration, oxidation gained organic layer is put into and still, after dripping liquid caustic soda and being neutralized to pH=7, standing demix; The gained organic layer enters next addition operation;
(5) refining: the aqueous solution that with mass percent concentration is 10% Sodium Pyrosulfite is put into the addition still, neutralization reaction gained organic layer is added in the addition still, after stirring, standing, divide the organic layer that goes to the bottom, after the water layer on upper strata added liquid caustic soda to be adjusted to pH=13, centrifugation got the Ortho Nitro Benzaldehyde crude product; Crude product is put into refining decolouring still, add appropriate toluene and gac, be warming up to 45 ℃, enter in crystallization kettle after filtration to lower the temperature, temperature is centrifugal after reducing, dry to get finished product.
Embodiment 2, a kind of technology for producing o-nitrobenzaldehyde, and its step is as follows:
(1) bromination: the water, ethylene dichloride, Ortho Nitro Toluene, the bromine that measure are dropped into closed bromination reaction still, pass into the chilled brine cooling toward condenser, under whipped state, reactor is warming up to 40 ℃, add initiator peroxy dicarbonate (2-ethylhexyl) ester, continue to heat up 55 ℃ fade after, minutes 3 batches add hydrogen peroxide and initiator, add after the question response thing fades at every turn all again; Hydrogen peroxide and initiator finish, the reaction mixture standing demix after rear insulation 3 h that fades, and organic layer enters next hydrolyzing process; The weight ratio of each raw material is Ortho Nitro Toluene: bromine: water: ethylene dichloride: hydrogen peroxide: initiator=1: 0.6: 3.0: 3.0: 0.6: 0.06;
(2) hydrolysis: adding the mass percent concentration for preparing in hydrolysis kettle is 12% aqueous sodium carbonate, bromination operation gained organic layer is put into hydrolysis kettle stir, and CO is arranged
2Gas generates; Heat up, hydrolysis, while Distillation recovery ethylene dichloride, the ethylene dichloride cover under reclaiming is used for the bromo chemical order; Layering after insulation 3 h after distillation finishes, the gained organic layer enters next oxidation operation;
(3) oxidation: be that 65% dilute nitric acid solution adds scale tank with the mass percent concentration for preparing, hydrolysis reaction gained organic layer is put into oxidizing reactor, add the catalyzer Sodium Nitrite, start stirring, slowly drip dilute nitric acid solution when being warming up to 50 ℃, the reaction nature is warming up to 60 ℃; Dropwise standing demix after rear insulation 5h, the gained organic layer enters in next and operation;
(4) neutralization: be that 35% liquid caustic soda adds scale tank with mass percent concentration, oxidation gained organic layer is put into and still, after dripping liquid caustic soda and being neutralized to pH=8, standing demix; The gained organic layer enters next addition operation;
(5) refining: the aqueous solution that with mass percent concentration is 14% Sodium Pyrosulfite is put into the addition still, neutralization reaction gained organic layer is added in the addition still, after stirring, standing, divide the organic layer that goes to the bottom, after the water layer on upper strata added liquid caustic soda to be adjusted to pH=14, centrifugation got the Ortho Nitro Benzaldehyde crude product; Crude product is put into refining decolouring still, add appropriate toluene and gac, be warming up to 55 ℃, enter in crystallization kettle after filtration to lower the temperature, temperature is centrifugal after reducing, dry to get finished product.After applying mechanically 5 times, described toluene carries out toluene recovery.Yield is about 46%.
Embodiment 3, a kind of technology for producing o-nitrobenzaldehyde, and its step is as follows:
(1) bromination: the water, ethylene dichloride, Ortho Nitro Toluene, the bromine that measure are dropped into closed bromination reaction still, pass into the chilled brine cooling toward condenser, under whipped state, reactor is warming up to 40 ℃, add initiator peroxy dicarbonate (2-ethylhexyl) ester, continue to heat up 52 ℃ fade after, minutes 2 batches add hydrogen peroxide and initiator, add after the question response thing fades at every turn all again; Hydrogen peroxide and initiator finish, the reaction mixture standing demix after rear insulation 2.5 h that fades, and organic layer enters next hydrolyzing process; The weight ratio of each raw material is Ortho Nitro Toluene: bromine: water: ethylene dichloride: hydrogen peroxide: initiator=1: 0.5: 2.5: 2.5: 0.5: 0.05;
(2) hydrolysis: adding the mass percent concentration for preparing in hydrolysis kettle is 10% aqueous sodium carbonate, bromination operation gained organic layer is put into hydrolysis kettle stir, and CO is arranged
2Gas generates; Heat up, hydrolysis, while Distillation recovery ethylene dichloride, the ethylene dichloride cover under reclaiming is used for the bromo chemical order; Layering after insulation 2.5 h after distillation finishes, the gained organic layer enters next oxidation operation;
(3) oxidation: be that 60% dilute nitric acid solution adds scale tank with the mass percent concentration for preparing, hydrolysis reaction gained organic layer is put into oxidizing reactor, add the catalyzer Sodium Nitrite, start stirring, slowly drip dilute nitric acid solution when being warming up to 45 ℃, the reaction nature is warming up to 58 ℃; Dropwise standing demix after rear insulation 4h, the gained organic layer enters in next and operation;
(4) neutralization: be that 30% liquid caustic soda adds scale tank with mass percent concentration, oxidation gained organic layer is put into and still, after dripping liquid caustic soda and being neutralized to pH=7.5, standing demix; The gained organic layer enters next addition operation;
(5) refining: the aqueous solution that with mass percent concentration is 12% Sodium Pyrosulfite is put into the addition still, neutralization reaction gained organic layer is added in the addition still, after stirring, standing, divide the organic layer that goes to the bottom, after the water layer on upper strata added liquid caustic soda to be adjusted to pH=13.5, centrifugation got the Ortho Nitro Benzaldehyde crude product; Crude product is put into refining decolouring still, add appropriate toluene and gac, be warming up to 50 ℃, enter in crystallization kettle after filtration to lower the temperature, temperature is centrifugal after reducing, dry to get finished product.After applying mechanically 4 times, described toluene carries out toluene recovery.Yield is about 45%.
Claims (1)
1. a technology for producing o-nitrobenzaldehyde, is characterized in that, its step is as follows:
(1) bromination: the water, ethylene dichloride, Ortho Nitro Toluene, the bromine that measure are dropped into closed bromination reaction still, pass into the chilled brine cooling toward condenser, under whipped state, reactor is warming up to 40 ℃, add initiator peroxy dicarbonate (2-ethylhexyl) ester, continue to heat up 55 ℃ fade after, minutes 3 batches add hydrogen peroxide and initiator, add after the question response thing fades at every turn all again; Hydrogen peroxide and initiator finish, the reaction mixture standing demix after rear insulation 3 h that fades, and organic layer enters next hydrolyzing process; The weight ratio of each raw material is Ortho Nitro Toluene: bromine: water: ethylene dichloride: hydrogen peroxide: initiator=1: 0.6: 3.0: 3.0: 0.6: 0.06;
(2) hydrolysis: adding the mass percent concentration for preparing in hydrolysis kettle is 12% aqueous sodium carbonate, bromination operation gained organic layer is put into hydrolysis kettle stir, and CO is arranged
2Gas generates; Heat up, hydrolysis, while Distillation recovery ethylene dichloride, the ethylene dichloride cover under reclaiming is used for the bromo chemical order; Layering after insulation 3 h after distillation finishes, the gained organic layer enters next oxidation operation;
(3) oxidation: be that 65% dilute nitric acid solution adds scale tank with the mass percent concentration for preparing, hydrolysis reaction gained organic layer is put into oxidizing reactor, add the catalyzer Sodium Nitrite, start stirring, slowly drip dilute nitric acid solution when being warming up to 50 ℃, the reaction nature is warming up to 60 ℃; Dropwise standing demix after rear insulation 5h, the gained organic layer enters in next and operation;
(4) neutralization: be that 35% liquid caustic soda adds scale tank with mass percent concentration, oxidation gained organic layer is put into and still, after dripping liquid caustic soda and being neutralized to pH=8, standing demix; The gained organic layer enters next addition operation;
(5) refining: the aqueous solution that with mass percent concentration is 14% Sodium Pyrosulfite is put into the addition still, neutralization reaction gained organic layer is added in the addition still, after stirring, standing, divide the organic layer that goes to the bottom, after the water layer on upper strata added liquid caustic soda to be adjusted to pH=14, centrifugation got the Ortho Nitro Benzaldehyde crude product; Crude product is put into refining decolouring still, add appropriate toluene and gac, be warming up to 55 ℃, enter in crystallization kettle after filtration to lower the temperature, temperature is centrifugal after reducing, dry to get finished product; After applying mechanically 5 times, described toluene carries out toluene recovery.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323575A (en) * | 2007-06-15 | 2008-12-17 | 南京理工大学 | Synthetic method of nitrobenzene methyl aldehyde |
| CN101362697A (en) * | 2008-09-23 | 2009-02-11 | 浙江大学 | O-nitrobenzaldehyde and p-nitrobenzaldehyde and preparation method of halides thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1579383A (en) * | 1976-07-12 | 1980-11-19 | Ciba Geigy Ag | Process for the manufacture of substituted benzaldehydes |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323575A (en) * | 2007-06-15 | 2008-12-17 | 南京理工大学 | Synthetic method of nitrobenzene methyl aldehyde |
| CN101362697A (en) * | 2008-09-23 | 2009-02-11 | 浙江大学 | O-nitrobenzaldehyde and p-nitrobenzaldehyde and preparation method of halides thereof |
Non-Patent Citations (6)
| Title |
|---|
| Jing Cao 等.Protecting-group-free amination of halogenated nitrobenzaldehyde with palladium catalyst.《Chinese Chemical Letters》.2010,第21卷第935-938页. |
| Protecting-group-free amination of halogenated nitrobenzaldehyde with palladium catalyst;Jing Cao 等;《Chinese Chemical Letters》;20101231;第21卷;第935-938页 * |
| 刁春莉.间硝基苯甲醛的合成.《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2008,(第12期),第11,16,18页. |
| 刘长令 等.苯并呋喃药物及其中间体的制备.《精细与专用化学品》.2002,(第1期),第26页. |
| 苯并呋喃药物及其中间体的制备;刘长令 等;《精细与专用化学品》;20021231(第1期);第26页 * |
| 间硝基苯甲醛的合成;刁春莉;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20081215(第12期);第11,16,18页 * |
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