CN108689860A - A kind of synthetic method preparing 4- butyl benzene -1,2- diamines - Google Patents
A kind of synthetic method preparing 4- butyl benzene -1,2- diamines Download PDFInfo
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- CN108689860A CN108689860A CN201810789465.8A CN201810789465A CN108689860A CN 108689860 A CN108689860 A CN 108689860A CN 201810789465 A CN201810789465 A CN 201810789465A CN 108689860 A CN108689860 A CN 108689860A
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- Prior art keywords
- diamines
- sodium
- weight
- synthetic method
- butyl benzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Abstract
The invention discloses a kind of synthetic methods preparing 4- butyl benzene -1,2- diamines, it includes the following steps:4- butyl -2- nitroanilines are dissolved in solvent, the aqueous solution containing vulcanized sodium, sodium thiosulfate and sodium dithionite is then added and heat reaction, TLC detections, after reaction, it filters, organic solvent extraction, organic solvent extract liquor is evaporated to get 4- butyl benzene -1,2- diamines.The method of the present invention is not high to equipment requirement, easy to operate, of low cost, is suitable for industrialized production, and reaction yield reaches 89.2%, and crude product purity reaches 97% or more.
Description
Technical field
The technical field of medicine intermediate preparation method of the present invention, and in particular to a kind of to prepare 4- butyl benzene -1,2- diamines
Synthetic method.
Background technology
About the chemical synthesis of 4- butyl benzene -1,2- diamines, domestic and foreign literature report is few, can be used as introduced in document
4- butyl -2- nitroanilines are restored in alkalinity or acid medium and are made by zinc powder;Or as patent US, 3413227 is used
Hydrogenating reduction is made under Raney's nickel high temperature and pressure;Or the reduction of palladium carbon high-pressure hydrogenation is used to be made in neutral conditions.Wherein adopt
With zinc powder alkalinity or acid medium in reduction method, a large amount of zinc mud are generated although cost is relatively low, in reaction process, are caused
Post-processing filtering is difficult, and environmental protection pressure is big;Using Raney's nickel hydrogenating reduction method, the requirement to equipment is very high, operational danger compared with
Greatly, cost is higher;Palladium carbon hydrogenating reduction method is used in neutral conditions, although dangerous without Raney's nickel height, equipment is wanted
Ask high, and palladium carbon price, it is of high cost, it is also unsuitable for large-scale industrial production.Therefore, it is necessary to develop one it is new low
The route for being easy to industrialized synthesis 4- butyl benzene -1,2- diamines of cost, to meet the market demand.
Invention content
It is environmental-friendly the purpose of the present invention is to provide a kind of easy to operate, mild condition, it is low-cost to be suitable for industry
The method that metaplasia produces 4- butyl benzene -1,2- diamines, has especially used cheap vulcanized sodium, thiosulfuric acid in preparation process
As reducing agent, single step reaction obtains 4- butyl benzene -1,2- diamines for sodium, sodium dithionite.Compared to technique in existing literature, originally
Preparation process is simple, and equipment requirement is not high, used in organic solvent can recovery, cost is greatly reduced, and to ring
Border pollution is small, is easy to industrialize, overall yield of reaction reaches 89.2%, and crude product purity reaches 97% or more.For this purpose, the present invention by with
Lower reaction step is realized:
1. 4- butyl -2- nitroanilines are dissolved in solvent, stir evenly spare;
2. vulcanized sodium, sodium thiosulfate and sodium dithionite are dissolved in aqueous solution, clear solution is obtained, then by this solution
It is added drop-wise in 1. solvent, continues to stir, temperature control reaction, TLC monitorings stop after the completion of reaction, and reaction solution is let cool to room temperature;
3. taking step, 2. reaction solution filters, merging filtrate, filtrate is extracted with organic solvent, merges extraction organic phase, dry, mistake
Filter, filtrate be evaporated to get.
The solvent is any one in water, methanol, ethyl alcohol, DMF, acetone, DMA, DMSO, fourth sulfone, dioxane, THF
Kind.
The solvent by water, methanol, ethyl alcohol, THF, DMF, acetone, DMA, DMSO, dioxane any two or two
Kind or more mixture composition.
The temperature of heating reaction is controlled at 20-120 DEG C.
4- butyl -2- nitroaniline dosage 0.1-20 parts by weight, amount of sodium sulfide 0.1-20 parts by weight, sodium thiosulfate are used
Measure 0.1-20 parts by weight, sodium dithionite dosage 0.1-20 parts by weight.
4- butyl -2- nitroaniline dosage 4-10 parts by weight, amount of sodium sulfide 4-10 parts by weight, sodium thiosulfate dosage 7-
15 parts by weight, sodium dithionite dosage 2-15 parts by weight.
Extraction organic solvent is by any one in dichloromethane, ethyl acetate, solvent naphtha, n-hexane, normal heptane, toluene
It plants or two kinds or more of mixture replaces.
It is an advantage of the invention that it provides a kind of easy to operate, mild condition, equipment requirement is not high, environmental-friendly cost
The cheap method suitable for industrialized production 4- butyl benzene -1,2- diamines.In preparation process, present invention employs cheap
Vulcanized sodium and sodium thiosulfate, sodium dithionite as reducing agent, and subsequent processing is simply easy, and organic solvent used is equal
It is recyclable to apply mechanically, document synthetic method is compared, this method is not high to equipment requirement, easy to operate, of low cost, is suitable for industrialization
Production, reaction yield reach 89.2%, and crude product purity reaches 97% or more.
Description of the drawings
Fig. 1 is that the HPLC of sample 4- butyl benzene -1,2- diamines analyzes collection of illustrative plates.
Fig. 2 is the nuclear magnetic resonance spectroscopy collection of illustrative plates of sample 4- butyl benzene -1,2- diamines.
Specific implementation mode
Below with specific embodiment, the present invention is further explained.These examples of implementation be merely to illustrate the present invention without
For limiting the scope of the invention.
Embodiment 1
1. 4g4- butyl -2- nitroanilines are dissolved in 50mlDMF, stir evenly, be warming up to 85 degree;
2. separately taking 6 grams of vulcanized sodium, 12 grams of sodium thiosulfate, 10 grams of sodium dithionite, 50ml water dissolutions are added, by this water drop
It is added in 1. solution, opens agitating device stirring, 85 degree of temperature, TLC monitorings is kept after reaction, to be extracted with dichloromethane,
Combining extraction liquid, revolving, obtains 4- butyl-neighbour's aniline.
Embodiment 2
1. 6g4- butyl -2- nitroanilines are dissolved in 40ml THF, stir evenly, be warming up to 75 degree;
2. separately taking 4 grams of vulcanized sodium, 8 grams of sodium thiosulfate, 7 grams of sodium dithionite, 40ml water dissolutions are added, this aqueous is added dropwise
Enter in 1. solution, open agitating device stirring, 75 degree of temperature, TLC monitorings is kept after reaction, to be extracted with toluene, merge extraction
Liquid is taken, revolving is dry, obtains 4- butyl-neighbour's aniline.
Embodiment 3
1. 2.4g4- butyl -2- nitroanilines are dissolved in 80ml DMSO, stir evenly, be warming up to 95 degree;
2. separately taking 8 grams of vulcanized sodium, 12 grams of sodium thiosulfate, 6 grams of sodium dithionite, 80ml water dissolutions are added, by this water drop
It is added in 1. solution, opens agitating device stirring, 95 degree of temperature, TLC monitorings is kept after reaction, to be extracted with dichloromethane,
Combining extraction liquid, revolving, obtains 4- butyl-neighbour's aniline.
Claims (7)
1. a kind of synthetic method preparing 4- butyl benzene -1,2- diamines, it is characterised in that it includes the following steps:By 4- butyl-
2- nitroanilines are dissolved in solvent, and the aqueous solution containing vulcanized sodium, sodium thiosulfate and sodium dithionite is then added and adds
Thermal response, TLC detections, after reaction, filtering, organic solvent extracts, and organic solvent extract liquor is evaporated to get 4- butyl benzenes-
1,2- diamines.
2. a kind of synthetic method preparing 4- butyl benzene -1,2- diamines according to claim 1, it is characterised in that described molten
Agent is any one in water, methanol, ethyl alcohol, DMF, acetone, DMA, DMSO, fourth sulfone, dioxane, THF.
3. a kind of synthetic method preparing 4- butyl benzene -1,2- diamines according to claim 1, it is characterised in that described molten
Agent by any two or two kinds or more in water, methanol, ethyl alcohol, THF, DMF, acetone, DMA, DMSO, dioxane mixture
Composition.
4. a kind of synthetic method preparing 4- butyl benzene -1,2- diamines according to claim 1, it is characterised in that heating is anti-
The temperature answered is controlled at 20-120 DEG C.
5. a kind of synthetic method preparing 4- butyl benzene -1,2- diamines according to claim 1, it is characterised in that 4- fourths
Base -2- nitroaniline dosage 0.1-20 parts by weight, amount of sodium sulfide 0.1-20 parts by weight, sodium thiosulfate dosage 0.1-20 weight
Part, sodium dithionite dosage 0.1-20 parts by weight.
6. a kind of synthetic method preparing 4- butyl benzene -1,2- diamines according to claim 5, it is characterised in that 4- fourths
Base -2- nitroaniline dosage 4-10 parts by weight, amount of sodium sulfide 4-10 parts by weight, sodium thiosulfate dosage 7-15 parts by weight, even
Sodium sulfite dosage 2-15 parts by weight.
7. a kind of synthetic method preparing 4- butyl benzene -1,2- diamines according to claim 1, it is characterised in that extraction is used
Organic solvent is by any one or two kinds or more in dichloromethane, ethyl acetate, solvent naphtha, n-hexane, normal heptane, toluene
Mixture replaces.
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| CN201810789465.8A CN108689860A (en) | 2018-07-18 | 2018-07-18 | A kind of synthetic method preparing 4- butyl benzene -1,2- diamines |
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| CN201810789465.8A CN108689860A (en) | 2018-07-18 | 2018-07-18 | A kind of synthetic method preparing 4- butyl benzene -1,2- diamines |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413227A (en) * | 1963-12-06 | 1968-11-26 | Geigy Chem Corp | Compositions containing substituted benzotriazoles |
| US5512209A (en) * | 1993-04-27 | 1996-04-30 | Canon Kabushiki Kaisha | Quinoxaline compound, liquid crystal composition containing the compound, liquid crystal device using the composition, display apparatus and display method |
| CN101245049A (en) * | 2008-03-10 | 2008-08-20 | 江苏工业学院 | Method for producing 5-n-butyl-2-benzoglioxaline methyl carbamate |
| CN103450104A (en) * | 2013-05-08 | 2013-12-18 | 如皋市金陵化工有限公司 | Synthesis process of 5-n-butyl-1H-benzotriazole |
| CN106316863A (en) * | 2016-08-13 | 2017-01-11 | 安徽东至广信农化有限公司 | Efficient o-phenylenediamine recovery method |
-
2018
- 2018-07-18 CN CN201810789465.8A patent/CN108689860A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413227A (en) * | 1963-12-06 | 1968-11-26 | Geigy Chem Corp | Compositions containing substituted benzotriazoles |
| US5512209A (en) * | 1993-04-27 | 1996-04-30 | Canon Kabushiki Kaisha | Quinoxaline compound, liquid crystal composition containing the compound, liquid crystal device using the composition, display apparatus and display method |
| CN101245049A (en) * | 2008-03-10 | 2008-08-20 | 江苏工业学院 | Method for producing 5-n-butyl-2-benzoglioxaline methyl carbamate |
| CN103450104A (en) * | 2013-05-08 | 2013-12-18 | 如皋市金陵化工有限公司 | Synthesis process of 5-n-butyl-1H-benzotriazole |
| CN106316863A (en) * | 2016-08-13 | 2017-01-11 | 安徽东至广信农化有限公司 | Efficient o-phenylenediamine recovery method |
Non-Patent Citations (4)
| Title |
|---|
| C. JOHN DICUOLLO等: "Metabolic and Tissue Residue Studies on Parbendazole in Sheep", 《J.AGR.FOOD CHEM.》 * |
| 吕永梅: "邻苯二胺生产技术进展与市场分析", 《现代农药》 * |
| 周亚利 等: "还原法制备芳香胺的研究进展", 《应用化工》 * |
| 章思规，辛忠: "《精细有机化工制备手册》", 30 April 1994, 科学技术文献出版社 * |
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