CN1182104C - Chemical synthesizing method for 5-chlorine-2-nitroaniline - Google Patents
Chemical synthesizing method for 5-chlorine-2-nitroaniline Download PDFInfo
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- CN1182104C CN1182104C CNB021434816A CN02143481A CN1182104C CN 1182104 C CN1182104 C CN 1182104C CN B021434816 A CNB021434816 A CN B021434816A CN 02143481 A CN02143481 A CN 02143481A CN 1182104 C CN1182104 C CN 1182104C
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Abstract
The present invention belongs to a new method for synthesizing 5-chloro-2-nitroaniline, which takes 3-chloroaniline as initial raw materials which are reacted by formylating, nitrating and hydrolyzing to synthesize the 5-chloro-2-nitroaniline which is target compounds. The total yield is more than 60 %, and product purity is above 98%. The present invention has the characteristics of easy raw material obtaining, easy operation, low productive cost, no environmental pollution, etc.
Description
Technical field:
The present invention relates to a kind of novel method of synthetic 5-chloro-2-N-methyl-p-nitroaniline.This method is to be starting raw material with the 3-chloroaniline, through formylation, nitrated and hydrolysis three-step reaction synthesising target compound 5-chloro-2-N-methyl-p-nitroaniline.
Background technology:
5-chloro-2-N-methyl-p-nitroaniline is a kind of important medicine and pesticide intermediate.The method for preparing 5-chloro-2-N-methyl-p-nitroaniline of bibliographical information is to be starting raw material with the 3-chloroaniline, make the 3-chloroacetanilide with acetic anhydride earlier, then in the mixed solvent of acetate and diacetyl oxide with the nitrated 5-chloro-2-nitracetanilide that makes of nitrosonitric acid, back flow reaction 24h synthesising target compound 5-chloro-2-N-methyl-p-nitroaniline (GB2018766) in sodium methylate/methanol solution at last.This method adopts diacetyl oxide as protecting group, and cost is higher; Except generating 5-chloro-2-nitracetanilide, also generated a certain proportion of by product 3-chloro-4-nitracetanilide simultaneously when the 3-chloroacetanilide is nitrated; With sodium methylate/methanol solution 5-chloro-2-nitracetanilide being carried out alcoholysis, to prepare the 5-chloro-2-N-methyl-p-nitroaniline reaction times very long, and cost is higher.
Summary of the invention:
The objective of the invention is to overcome the shortcoming of existing method, the synthetic method of a kind of economy and 5-chloro-2-N-methyl-p-nitroaniline easy and simple to handle is provided.
Feature of the present invention is: with the 3-chloroaniline is starting raw material, through formylation, nitrated and hydrolysis three-step reaction synthesising target compound 5-chloro-2-N-methyl-p-nitroaniline.The formylation reaction of 3-chloroaniline is that azeotropic dehydration in inert organic solvents prepares 3-chloroformyl aniline with formic acid and 3-chloroaniline; the mol ratio of 3-chloroaniline and formic acid is 1: 1.4～1.5; feeding mode be earlier with 1.1 times formic acid in the inert organic solvents solution that joins the 3-chloroaniline below 70 ℃; heating azeotropic dehydration 1～1.5h; be cooled to then below 70 ℃; add remaining formic acid; reheat azeotropic dehydration 1～1.5h; used inert organic solvents comprises: isopropyl ether, positive propyl ether, n-butyl ether; benzene; toluene, dimethylbenzene, chlorobenzene.
The nitrifying method of 3-chloroformyl aniline is that the drips of solution with the preparation of 95% nitrosonitric acid and diacetyl oxide is added in the 3-chloroformyl aniline, molar ratio is: 3-chloroformyl aniline: nitric acid: diacetyl oxide=1.0: 1.3～1.5: 1.3～2.5, wherein with 1.0: 1.4: 1.8 the bests, temperature of reaction is-5～10 ℃, wherein with 0～5 ℃ of the best, reaction times 2.0～2.5h, with gas-chromatography reaction is monitored, after reaction finishes, do not need to carry out separating treatment, directly carry out next step hydrolysis reaction.
With above nitration reaction liquid in 20～25%NaOH aqueous solution in 100～110 ℃ of back flow reaction 1～1.5h, be cooled to room temperature, filtration under diminished pressure, cold water washing in 60～80 ℃ of oven dry, promptly obtains 5-chloro-2-N-methyl-p-nitroaniline, purity is more than 98%.
Reaction formula of the present invention is as follows:
The present invention compared with prior art has the following advantages:
1. usefulness formic acid than using diacetyl oxide economy, helps protecting environment as the amido protective material.Formic acid not only price is more easy than diacetyl oxide, and the atom utilization height, and molecular weight is not as good as 1/2 of diacetyl oxide, and therefore, with the 3-chloroaniline reaction of equal amts, the consumption of formic acid will be so that many, and consequent by product is also just few, has fewer environmental impacts.And the by product that formic acid and the reaction of 3-chloroaniline produce is a water, need not reclaim, and a small amount of wastewater treatment is more convenient.
2.3-chloroformyl aniline is compared with the 3-chloroacetanilide, because the volume ratio ethanoyl of formyl radical is little, nitrated sterically hindered littler at the amido ortho position, selectivity is higher.The primary product that the inventive method obtains is a 5-chloro-2-nitro formylaniline, by product seldom, the 5-chloro-2-N-methyl-p-nitroaniline purity that obtains after the direct hydrolysis is more than 98%.
3. the nitration product of the inventive method need not separate, and directly is hydrolyzed, and has simplified operation steps, has improved reaction yield.Compare with the alcoholysis method of bibliographical information, present method has shortened the reaction times greatly.
Embodiment:
In order to be easy to further understand the present invention, the following example has been set forth more specific details.
Embodiment 1
3-chloroformyl aniline: in the 250ml there-necked flask of water trap is housed, add 51.5g (0.41mol) 3-chloroaniline and 150ml toluene, stirring and dissolving, slowly add 23.5g (0.45mol) 88% formic acid then, temperature rising reflux 1h is cooled to 65～70 ℃, add 6.4g (0.12mol) 88% formic acid, temperature rising reflux 1h is cooled to room temperature once more, takes off most toluene and excessive formic acid on rotatory evaporator, cooling, white solid 3-chloroformyl aniline 61.7g, yield 97%, m.p.51～53 ℃.
Embodiment 2
3-chloroformyl aniline: except replacing toluene with benzene, other operational condition is all identical with embodiment 1, white solid 3-chloroformyl aniline 53.8g, yield 84%, m.p.50～53 ℃.
Embodiment 3
3-chloroformyl aniline: except replacing toluene with n-butyl ether, other operational condition is all identical with embodiment 1, white solid 3-chloroformyl aniline 58.2g, yield 91%, m.p.51～53 ℃.
Embodiment 4
5-chloro-2-N-methyl-p-nitroaniline: in the 50ml there-necked flask, the 3-chloroformyl aniline that adds 10.0g (64mmol) grinding powder, ice-water bath is cooled to 0～5 ℃, slowly drip solution by 6.0g (90mmol) 95% nitric acid and the preparation of 8.6g (84mmol) acetic anhydride, keep 0～5 ℃ of temperature, continue at stirring reaction 2h under this temperature after adding, reaction joins reaction solution in the 110ml 25%NaOH aqueous solution after finishing, stirring and refluxing 2h, be cooled to room temperature, filtration under diminished pressure, cold water washing, get yellow solid 5-chloro-2-N-methyl-p-nitroaniline 8.0g, yield 62%, m.p.128～129 ℃, purity 98.8%.
Embodiment 5
5-chloro-2-N-methyl-p-nitroaniline: except the acetic anhydride consumption was 11.8g (116mmol), other operational condition was all identical with embodiment 4, got 5-chloro-2-N-methyl-p-nitroaniline 9.2g, yield 72%, purity 98.4%.
Embodiment 6
5-chloro-2-N-methyl-p-nitroaniline: except the acetic anhydride consumption was 16.3g (160mmol), other operational condition was all identical with embodiment 4, got 5-chloro-2-N-methyl-p-nitroaniline 7.7g, yield 60%, purity 98.2%.
Embodiment 7
5-chloro-2-N-methyl-p-nitroaniline: except dropping temperature and temperature of reaction are controlled at-5～0 ℃, other operational condition is all identical with embodiment 5,5-chloro-2-N-methyl-p-nitroaniline 8.2g, yield 64%, purity 98.8%.
Embodiment 8
5-chloro-2-N-methyl-p-nitroaniline: except dropping temperature and temperature of reaction are controlled at 5～10 ℃, other operational condition is all identical with embodiment 5,5-chloro-2-N-methyl-p-nitroaniline 8.5g, yield 66%, purity 98.0%.
Claims (4)
1.5-the chemical synthesis process of chloro-2-N-methyl-p-nitroaniline is characterized in that: with the 3-chloroaniline is starting raw material, through formylation, nitrated and hydrolysis three-step reaction synthesising target compound 5-chloro-2-N-methyl-p-nitroaniline.
2. synthetic method according to claim 1; it is characterized in that: the formylation reaction of 3-chloroaniline is that azeotropic dehydration in inert organic solvents prepares 3-chloroformyl aniline with formic acid and 3-chloroaniline; the mol ratio of 3-chloroaniline and formic acid is 1: 1.4～1.5; feeding mode be earlier with 1.1 times of formic acid in the inert organic solvents solution that joins the 3-chloroaniline below 70 ℃; heating azeotropic dehydration 1～1.5h; be cooled to then below 70 ℃; add remaining formic acid; reheat azeotropic dehydration 1～1.5h, above-mentioned inert organic solvents is meant isopropyl ether; positive propyl ether; n-butyl ether; benzene; toluene; a kind of in dimethylbenzene and the chlorobenzene.
3. synthetic method according to claim 1, it is characterized in that: the nitration reaction of 3-chloroformyl aniline is that the drips of solution with the preparation of 95% nitrosonitric acid and diacetyl oxide is added to and carries out the nitrated 5-of preparation chloro-2-nitro formylaniline in the 3-chloroformyl aniline, molar ratio is: 3-chloroformyl aniline: nitric acid: diacetyl oxide=1.0: 1.3～1.5: 1.3～2.5, temperature of reaction is-5～10 ℃, reaction times 2.0～2.5h obtains 5-chloro-2-nitro formylaniline solution.
4. synthetic method according to claim 3, it is characterized in that: the hydrolysis reaction of 5-chloro-2-nitro formylaniline is that above-mentioned 5-chloro-2-nitro formylaniline solution is joined in 20～25%NaOH aqueous solution in 100～110 ℃ of back flow reaction 1～1.5h, be cooled to room temperature, filtration under diminished pressure, cold water washing, in 60～80 ℃ of oven dry, promptly obtain 5-chloro-2-N-methyl-p-nitroaniline then.
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| CNB021434816A CN1182104C (en) | 2002-09-30 | 2002-09-30 | Chemical synthesizing method for 5-chlorine-2-nitroaniline |
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| CN103965122B (en) * | 2014-03-18 | 2016-03-30 | 浙江工业大学 | A kind of nitrifying method of quinoxaline alkane substitute |
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