CN108164421A - The preparation method of o-nitrobenzaldehyde - Google Patents
The preparation method of o-nitrobenzaldehyde Download PDFInfo
- Publication number
- CN108164421A CN108164421A CN201711251648.6A CN201711251648A CN108164421A CN 108164421 A CN108164421 A CN 108164421A CN 201711251648 A CN201711251648 A CN 201711251648A CN 108164421 A CN108164421 A CN 108164421A
- Authority
- CN
- China
- Prior art keywords
- nitrobenzaldehyde
- initiator
- hydrogen peroxide
- reaction
- preparation
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to medicine intermediate fields, disclose a kind of preparation method of o-nitrobenzaldehyde, including being 35 by mass ratio：26 ~ 28 ortho-methylnitrobenzene and bromine are dissolved in the in the mixed solvent of water and organic solvent, are heated to 55 ~ 65 DEG C, add in initiator and are reacted to color fade, generate one bromobenzyl of adjacent nitro and adjacent nitro cyclite；70 ~ 75 DEG C are heated to, adding hydrogen peroxide and initiator, the reaction was continued to color fade；Keep temperature-resistant, adding hydrogen peroxide and initiator, the reaction was continued to color fade；Keep temperature-resistant, adding hydrogen peroxide and initiator, the reaction was continued to color fade；It keeps temperature-resistant, hydrogen peroxide and initiator is added to keep the temperature 1.5 ~ 2.5h；Aqueous sodium carbonate is added in, one bromobenzyl of adjacent nitro is hydrolyzed into nitro alcohol；Add dust technology, nitro alcohol is oxidized to o-nitrobenzaldehyde.This method yield is higher, reduces the generation of organic matter by-product and the discharge capacity of inorganic salts (acid) waste water.
Description
Technical field
The present invention relates to the preparation field of medicine intermediate, more particularly to a kind of preparation method of o-nitrobenzaldehyde.
Background technology
In the preparation process of medicine intermediate o-nitrobenzaldehyde, bromine and ortho-methylnitrobenzene are used as former
Material, under the initiation of initiator, the bromide ion that bromine decomposites reacts generation adjacent nitro bromobenzyl with ortho-methylnitrobenzene, herein
In the process, if it is desired to the reaction was complete as possible for ortho-methylnitrobenzene, then can increase the amount of the bromine of addition, but when reaction reaches
Certain balance, the amount of increases bromine simply can't promote reaction to positive direction progress again, and the yield of reaction does not have bright
Aobvious promotion.
Invention content
Goal of the invention：For problems of the prior art, the present invention provides a kind of preparation side of o-nitrobenzaldehyde
Method, this method yield is higher, reduces the generation of organic matter by-product and the discharge capacity of inorganic salts (acid) waste water.
Technical solution：The present invention provides a kind of preparation methods of o-nitrobenzaldehyde, include the following steps：S1：By matter
Amount is than being 35：26 ~ 28 ortho-methylnitrobenzene and bromine is dissolved in the in the mixed solvent of water and organic solvent and adds in mixed solution
Into reaction kettle, 55 ~ 65 DEG C are heated to, initiator is added in and is reacted to color fade, generation one bromobenzyl of adjacent nitro and adjacent nitre
Base cyclite；S2：70 ~ 75 DEG C are heated to, adding hydrogen peroxide and initiator, the reaction was continued to color fade；S3：Keep temperature-resistant,
Adding hydrogen peroxide and initiator, the reaction was continued to color fade；S4：It keeps temperature-resistant, adds hydrogen peroxide and initiator the reaction was continued extremely
Color fade；S5：It keeps temperature-resistant, hydrogen peroxide and initiator is added to keep the temperature 1.5 ~ 2.5h；S6：Aqueous sodium carbonate is added in, it will
System temperature is controlled at 90 ~ 100 DEG C, and one bromobenzyl of adjacent nitro is hydrolyzed into nitro alcohol；S7：Add in dust technology, body
It is that temperature is controlled at 65 ~ 70 DEG C, the nitro alcohol is oxidized to o-nitrobenzaldehyde.
Further, after the S7, S8 is further included：The o-nitrobenzaldehyde is extracted, is remained after extraction
Under mother liquor in add in sodium hydrate aqueous solution, the adjacent nitro cyclite is hydrolyzed into o-nitrobenzaldehyde.Extract adjacent nitro
Adjacent nitro cyclite after benzaldehyde in remaining mother liquor hydrolyzes generation product o-nitrobenzaldehyde by sodium hydrate aqueous solution, carries
High W-response yield.
Preferably, in the S8, a concentration of the 50% of the sodium hydrate aqueous solution.
Preferably, in the S6, a concentration of the 14% of the aqueous sodium carbonate.
Preferably, in the S7, a concentration of the 60% of the dust technology.
Preferably, the organic solvent is dichloroethanes.
Preferably, the initiator is EHP.
Advantageous effect：In the present invention, with excessive bromine under the initiation of initiator bromination occurs for ortho-methylnitrobenzene
It reacts to the color fade of bromine（Illustrate that bromine reacts away completely）, generate one bromobenzyl of adjacent nitro and adjacent nitro cyclite and pair
Then product hydrobromic acid adds in hydrogen peroxide and initiator for the first time, with byproduct hydrobromic acid oxidation reaction can occur for hydrogen peroxide,
Bromide ion in hydrobromic acid is oxidized to bromine, bromine can continue to that substitution reaction occurs up to bromine with ortho-methylnitrobenzene again
Color fade；Similarly, second, third time, the 4th addition hydrogen peroxide and initiator, due to the use of hydrogen peroxide so that most
Whole ortho-methylnitrobenzene can react completely, while promote substitution reaction and carried out to positive direction；When ortho-methylnitrobenzene reacts completely
Fall and then add in aqueous sodium carbonate, one bromobenzyl of adjacent nitro therein is carbonated sodium water solution hydrolysis generation product adjacent nitro
Benzyl alcohol and by-product sodium bromide, nitro alcohol are oxidized to required product o-nitrobenzaldehyde by dust technology again, then
O-nitrobenzaldehyde is extracted.
This method improves product yield and purity, and relatively industrial conventional method improves nearly 1.5 times to yield at present, and this method is total
Yield reaches 65 ~ 75%, and product purity is more than 99.5%；
This method oxidation technology can carry out under low pressure, and the reaction time shortens, the mild conditions such as reaction temperature；
The method reduces the generation of organic matter by-product and inorganic salts (acid) wastewater discharges；
This method can efficiently use molecular bromine, reduce the consumption of bromine；
Bromination and hydrolysis are completed in same reactor in this method, easy to operate；
This method can preparative separation go out high-purity medicine intermediate o-nitrobenzaldehyde.
Specific embodiment
The present invention is described in detail With reference to embodiment.
Embodiment 1：
Ortho-methylnitrobenzene 350 ㎏ and bromine 260kg are dissolved in the solvent of 700 ㎏ of water and 900 ㎏ of dichloroethanes compositions, and are fallen
Enter in 3000 liters of reaction kettle, be heated to 55 ~ 65 DEG C, add in 10 ㎏ of initiator and reacted to color fade, generate adjacent nitro
One bromobenzyl and adjacent nitro cyclite；70 ~ 75 DEG C are heated to, adding hydrogen peroxide 100 ㎏ and initiator 5kg for the first time, the reaction was continued to face
Color takes off；Keep temperature-resistant, adding hydrogen peroxide 100 ㎏ and initiator 5kg for the second time, the reaction was continued to color fade；Keep temperature
Constant, third time adds hydrogen peroxide 80kg and initiator 3kg to color fade；Keep temperature-resistant, the 4th time plus hydrogen peroxide 60kg
2h is kept the temperature with after 2 ㎏ of initiator；Then add in the aqueous sodium carbonate of 1800kg a concentration of 14%, system temperature control 90 ~
100 DEG C, one bromobenzyl of adjacent nitro is hydrolyzed into nitro alcohol；Then the dust technology of 400kg a concentration of 60%, system temperature are added in
Nitro alcohol is oxidized to o-nitrobenzaldehyde by degree control at 65 ~ 70 DEG C；Finally the o-nitrobenzaldehyde of generation is extracted
Out, and after extraction the sodium hydrate aqueous solution of 100kg a concentration of 50% is added in remaining mother liquor, by adjacent nitro therein
Cyclite is hydrolyzed into o-nitrobenzaldehyde.Finally it there are product o-nitrobenzaldehyde 227.5kg.Reaction yield is 65%.
Embodiment 2：
Ortho-methylnitrobenzene 350 ㎏ and bromine 270kg are dissolved in the solvent of 700 ㎏ of water and 900 ㎏ of dichloroethanes compositions, and are fallen
Enter in 3000 liters of reaction kettle, be heated to 55 ~ 65 DEG C, add in 10 ㎏ of initiator and reacted to color fade, generate adjacent nitro
One bromobenzyl and adjacent nitro cyclite；70 ~ 75 DEG C are heated to, adding hydrogen peroxide 100 ㎏ and initiator 5kg for the first time, the reaction was continued to face
Color takes off；Keep temperature-resistant, adding hydrogen peroxide 100 ㎏ and initiator 5kg for the second time, the reaction was continued to color fade；Keep temperature
Constant, third time adds hydrogen peroxide 80kg and initiator 3kg to color fade；Keep temperature-resistant, the 4th time plus hydrogen peroxide 60kg
2h is kept the temperature with after 2 ㎏ of initiator；Then add in the aqueous sodium carbonate of 1600kg a concentration of 14%, system temperature control 90 ~
100 DEG C, one bromobenzyl of adjacent nitro is hydrolyzed into nitro alcohol；Then the dust technology of 350kg a concentration of 60%, system temperature are added in
Nitro alcohol is oxidized to o-nitrobenzaldehyde by degree control at 65 ~ 70 DEG C；Finally the o-nitrobenzaldehyde of generation is extracted
Out, and after extraction the sodium hydrate aqueous solution of 120kg a concentration of 50% is added in remaining mother liquor, by adjacent nitro therein
Cyclite is hydrolyzed into o-nitrobenzaldehyde.Finally it there are product o-nitrobenzaldehyde 245kg.Reaction yield is 70%.
Embodiment 3：
Ortho-methylnitrobenzene 350 ㎏ and bromine 280kg are dissolved in the solvent of 700 ㎏ of water and 900 ㎏ of dichloroethanes compositions, and are fallen
Enter in 3000 liters of reaction kettle, be heated to 55 ~ 65 DEG C, add in 10 ㎏ of initiator and reacted to color fade, generate adjacent nitro
One bromobenzyl and adjacent nitro cyclite；70 ~ 75 DEG C are heated to, adding hydrogen peroxide 100 ㎏ and initiator 5kg for the first time, the reaction was continued to face
Color takes off；Keep temperature-resistant, adding hydrogen peroxide 100 ㎏ and initiator 5kg for the second time, the reaction was continued to color fade；Keep temperature
Constant, third time adds hydrogen peroxide 80kg and initiator 3kg to color fade；Keep temperature-resistant, the 4th time plus hydrogen peroxide 60kg
2h is kept the temperature with after 2 ㎏ of initiator；Then add in the aqueous sodium carbonate of 1500kg a concentration of 14%, system temperature control 90 ~
100 DEG C, one bromobenzyl of adjacent nitro is hydrolyzed into nitro alcohol；Then the dust technology of 330kg a concentration of 60%, system temperature are added in
Nitro alcohol is oxidized to o-nitrobenzaldehyde by degree control at 65 ~ 70 DEG C；Finally the o-nitrobenzaldehyde of generation is extracted
Out, and after extraction the sodium hydrate aqueous solution of 150kg a concentration of 50% is added in remaining mother liquor, by adjacent nitro therein
Cyclite is hydrolyzed into o-nitrobenzaldehyde.Finally it there are product o-nitrobenzaldehyde 262.5kg.Reaction yield is 75%.
The technical concepts and features of the above embodiment only to illustrate the invention, its object is to allow be familiar with technique
People can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent transformation or modification that Spirit Essence is done, should be covered by the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of o-nitrobenzaldehyde, which is characterized in that include the following steps：
S1：It is 35 by mass ratio：26 ~ 28 ortho-methylnitrobenzene and bromine is dissolved in the in the mixed solvent of water and organic solvent and will be mixed
It closes solution to be added in reaction kettle, is heated to 55 ~ 65 DEG C, add in initiator and reacted to color fade, generate adjacent nitro one
Bromobenzyl and adjacent nitro cyclite；
S2：70 ~ 75 DEG C are heated to, adding hydrogen peroxide and initiator, the reaction was continued to color fade；
S3：Keep temperature-resistant, adding hydrogen peroxide and initiator, the reaction was continued to color fade；
S4：Keep temperature-resistant, adding hydrogen peroxide and initiator, the reaction was continued to color fade；
S5：It keeps temperature-resistant, hydrogen peroxide and initiator is added to keep the temperature 1.5 ~ 2.5h；
S6：Aqueous sodium carbonate is added in, system temperature is controlled at 90 ~ 100 DEG C, and one bromobenzyl of adjacent nitro is hydrolyzed into adjacent nitro
Benzyl alcohol；
S7：Dust technology is added in, system temperature is controlled at 65 ~ 70 DEG C, and the nitro alcohol is oxidized to o-nitrobenzaldehyde.
2. the preparation method of o-nitrobenzaldehyde according to claim 1, which is characterized in that after the S7, also wrap
Include S8：The o-nitrobenzaldehyde is extracted, adds in sodium hydrate aqueous solution in remaining mother liquor after extraction, by described in
Adjacent nitro cyclite is hydrolyzed into o-nitrobenzaldehyde.
3. the preparation method of o-nitrobenzaldehyde according to claim 2, which is characterized in that in the S8, the hydrogen
A concentration of the 50% of aqueous solution of sodium oxide.
4. the preparation method of o-nitrobenzaldehyde according to claim 1, which is characterized in that in the S6, the carbon
A concentration of the 14% of acid sodium aqueous solution.
5. the preparation method of o-nitrobenzaldehyde according to claim 1, which is characterized in that described dilute in the S7
A concentration of the 60% of nitric acid.
6. the preparation method of o-nitrobenzaldehyde according to any one of claim 1 to 5, which is characterized in that described to have
Solvent is dichloroethanes.
7. the preparation method of o-nitrobenzaldehyde according to any one of claim 1 to 5, which is characterized in that described to draw
Hair agent is EHP.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711251648.6A CN108164421A (en) | 2017-12-01 | 2017-12-01 | The preparation method of o-nitrobenzaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711251648.6A CN108164421A (en) | 2017-12-01 | 2017-12-01 | The preparation method of o-nitrobenzaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108164421A true CN108164421A (en) | 2018-06-15 |
Family
ID=62524295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711251648.6A Pending CN108164421A (en) | 2017-12-01 | 2017-12-01 | The preparation method of o-nitrobenzaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108164421A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947848A (en) * | 2018-08-07 | 2018-12-07 | 安庆市长虹化工有限公司 | A kind of nitrification installation and nitration processes method of o-nitrobenzaldehyde preparation |
| CN109810002A (en) * | 2019-02-14 | 2019-05-28 | 安徽泰格生物技术股份有限公司 | A kind of method that useless bromobenzyl prepares benzylamine |
| CN110655457A (en) * | 2019-09-05 | 2020-01-07 | 门希国 | Novel method for preparing p-fluorobenzaldehyde by catalytic oxidation of hydrogen peroxide |
-
2017
- 2017-12-01 CN CN201711251648.6A patent/CN108164421A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947848A (en) * | 2018-08-07 | 2018-12-07 | 安庆市长虹化工有限公司 | A kind of nitrification installation and nitration processes method of o-nitrobenzaldehyde preparation |
| CN109810002A (en) * | 2019-02-14 | 2019-05-28 | 安徽泰格生物技术股份有限公司 | A kind of method that useless bromobenzyl prepares benzylamine |
| CN110655457A (en) * | 2019-09-05 | 2020-01-07 | 门希国 | Novel method for preparing p-fluorobenzaldehyde by catalytic oxidation of hydrogen peroxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108164421A (en) | The preparation method of o-nitrobenzaldehyde | |
| CA2232209C (en) | Method of producing chlorine dioxide | |
| CN109319827A (en) | A kind of preparation method of germanium dioxide | |
| CN108503531B (en) | Preparation method of 3, 3-dimethyl-2-oxobutyric acid | |
| KR100916974B1 (en) | A process for the production of chlorine dioxide | |
| CN107055477A (en) | The method and its device of hydrogen fluoride are prepared by fluosilicic acid | |
| CA2085682A1 (en) | Integrated procedure for high yield production of chlorine dioxide | |
| CN102249189A (en) | Method for recycling hydrochloric acid in chloroacetic acid production process | |
| JPH07300304A (en) | Continuous preparation of nitrosyl chloride | |
| CN111392732A (en) | Treatment process of organic byproduct potassium fluoride and potassium chloride mixture | |
| CN107311838A (en) | A kind of method of new synthesis Cyclopropyl Bromide | |
| CN108046332A (en) | The preparation method of high-valence state molysite | |
| CN112047849A (en) | Preparation method of aminomethylbenzoic acid | |
| CN115432679B (en) | Method for preparing polyphosphoric acid from wet phosphoric acid raffinate acid and application thereof | |
| JP5629776B2 (en) | Method for producing chlorine dioxide | |
| CN106865513B (en) | A kind of preparation method of hydrazine hydrate | |
| CN107108675A (en) | The method for preparing diosmin | |
| CN101993423A (en) | Method for producing epoxy chloropropane | |
| CN108164434A (en) | A kind of preparation method of inexpensive 4 '-bromomethyl -2- cyanobiphenyls | |
| EP0131378B2 (en) | Process for the production of chlorine dioxide | |
| CN206970204U (en) | The device of hydrogen fluoride is prepared for fluosilicic acid | |
| US6921521B2 (en) | Method of producing chlorine dioxide employs alkaline chlorate in a mineral acid medium and urea as a reducing agent | |
| CN104860843A (en) | Synthesis method of ketazine | |
| CN108658776A (en) | A kind of preparation method of o-nitrobenzaldehyde | |
| CN107935968A (en) | A kind of epoxychloropropane preparation method based on biomass glycerol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180615 |