CN108484416A - A kind of preparation method synthesizing Pendimethalin using nitrification process - Google Patents
A kind of preparation method synthesizing Pendimethalin using nitrification process Download PDFInfo
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- CN108484416A CN108484416A CN201810511465.1A CN201810511465A CN108484416A CN 108484416 A CN108484416 A CN 108484416A CN 201810511465 A CN201810511465 A CN 201810511465A CN 108484416 A CN108484416 A CN 108484416A
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- reaction
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- pendimethalin
- ethyl propyls
- acidolysis
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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
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of Pendimethalin preparation method, especially a kind of preparation method synthesizing Pendimethalin using nitrification process belongs to pharmaceutical preparation field.Its preparation principle is first amidation to be used to protect amino; it nitrifies again; then the technology path of acidolysis; method and step is with N- (1- ethyl propyls) -3; 4- dimethylanilines are starting material; using dichloroethanes as solvent; with aceticanhydride amidation; it is nitrified again with concentrated nitric acid; then acidolysis prepares Pendimethalin under dilute sulfuric acid effect again, and its purpose is to provide a kind of yield and high, the environmentally protective herbicide pendimethalin synthetic method of purity; process stabilizing is reliable compared with prior art, more environmentally protective.
Description
Technical field
The present invention relates to field of medicine preparing technology, specifically provide a kind of preparation side of pesticide herbicide Pendimethalin
Method, the nitrification Pendimethalin method of especially a kind of green.
Background technology
Pendimethalin is the common name of N- (1- ethyl propyls) -2,6- dinitro base -3,4- dimethylanilines, is by former beautiful
A kind of phenyl amines herbicide of cyanamide company of state research and development, is a kind of selective herbicide, prevents and kill off annual gramineae and certain one
Year life broad leaved weed.Preemergence application after cereal plants, corn and rice growing, or before broad bean, cotton, peanut and big bean sprout
Shallow mixed soil application.In vegetable fields tobacco sucker can be also prevented and kill off before seedling or application before transplanting.China 2002 starts to introduce life
Production, production level has reached Foreign Advanced Lerel at present, now mostly with N- (1- ethyl propyls) -3,4- dimethylanilines for raw material
Directly nitrification synthesis, but will produce by-product N- nitroso compounds in nitrifying process.Since N nitroso compounds are to big
Most mammals have carcinogenesis, therefore Environmental Protection Agency of various countries has done sternly to obtaining N- nitroso compounds in all kinds of chemicals
The regulation of lattice, all products that compound is obtained containing N- nitrosos must be reduced to its content before listing defined standard content
Once, the content of the N- nitroso compounds wherein in Pendimethalin (N- nitrosos Pendimethalin) be limited in 135ppm with
Under.Therefore after conventional method nitrification, N- nitrous product assay directly limits Pendimethalin city generally in 15%-20% or so
Access, needs further to take off N- nitroso compounds, at present de- N- nitroso compounds mainly use hydrochloric acid and sulfamic acid,
Two methods of frerrous chloride, and de- N- nitroso compounds will produce a large amount of waste water, synthesis active compound yield only has 90%, and active compound contains
Amount only 95%.
Invention content
The present invention in order to overcome the disadvantages and deficiencies of the prior art, provides and a kind of synthesizing Pendimethalin using nitrification process
Preparation method, this method yield and purity are high, environmentally protective.
For the goal of the invention for realizing above-mentioned, technical scheme is as follows：With N- (1- ethyl propyls) -3,4- dimethyl
Aniline is starting material, and aceticanhydride is added and carries out amidation, protects amino, reaction to finish decompression and slough acetic anhydride and acetic acid, then
Dichloroethanes is added as solvent, 95% concentrated nitric acid is added dropwise, is nitrified, nitrification finishes, and after neutralized washing, 50% sulphur is added
Acid is hydrolyzed, the neutralized washing of hydrolyzation material, and active compound Pendimethalin is obtained after then depressurizing precipitation.Its reaction principle is as follows：
(1) amidation process
(2) nitration reaction
(3) acidolysis reaction
The amidation process carries out according to the following steps：N- (1- ethyl propyls) -3,4- is added in 500ml reaction flasks
Dimethylaniline, acetic anhydride are warming up to 80-110 DEG C, and back flow reaction 5 hours is controlled in sampling, test N- (1- ethyl propyls) -3,
The reaction of 4- dimethylanilines finishes, qualified for reaction, and acetic anhydride and acetic acid are sloughed in decompression, obtain N- (1- ethyl propyls) -3,4- bis-
Methylbenzeneacetamide, content >=99%, yield >=99.5%；
The nitration reaction carries out according to the following steps：In N- (1- the ethyl propyls) -3,4- dimethyl for sloughing acetic anhydride acetic acid
In phenyl acetamide, dichloroethanes is added, is warming up to 30-40 DEG C, 95% concentrated nitric acid is then added dropwise, time for adding 1.5-2 hours adds
Finish, continue insulation reaction 5 hours, sample detection N- (1- ethyl propyls) -3,4- dimethyl benzene acetyl amine content≤1%, to close
Lattice, N- (1- ethyl propyls) -2,6- dinitro -3,4- dimethyl benzene acetyl amine content >=98%.Reaction finishes stratification, oil
It mutually neutralizes washing and enters hydrolysis step afterwards twice.
Steps are as follows for the acidolysis reaction：N- (1- ethyl propyls) -2,6- dinitro -3,4- dimethyl is obtained after neutralizing washing
Phenyl acetamide dichloroethane solution is added in 50% sulfuric acid solution, and stirring is warming up to 80-85 DEG C, and reaction is hydrolyzed, and is kept the temperature
Hydrolysis 4 hours, sampling and testing N- (1- ethyl propyls) -2,6- dinitro -3,4- dimethyl benzene acetyl amine content≤0.5% are
Reaction is qualified, and reaction finishes, stratification, in oil reservoir and washes twice, then depressurizes precipitation, precipitation finishes, and obtains peony two
First penta is found pleasure in clever active compound, content >=98%, and test nitrous product assay is 0%.
The present invention has following advantage compared with prior art：The present invention protects amino using amidation, then is nitrified, and has
Effect prevents the generation of N- nitroso compounds, more environmentally-friendly, obtains product feed purity and yield higher, process recovery ratio carries after change
5 percentage points high, active compound content improves 3 percentage points and reaches 98%, and the present invention uses this route, saves de- nitrous step, produces
The reduction 80% relatively of raw waste water, it is more environmentally friendly.
Specific implementation mode
Embodiment 1
For the present embodiment using amidation, nitrification, three step synthetic technology route of acidolysis, reaction principle equation is as follows：
(1) amidation process
(2) nitration reaction
(3) acidolysis reaction
Amidation process carries out according to the following steps：N- (1- ethyl propyls) -3,4- diformazans are added in 500ml reaction flasks
Base aniline, acetic anhydride are warming up to 110 DEG C, and back flow reaction 5 hours is controlled in sampling, test N- (1- ethyl propyls) -3,4- diformazans
Base aniline reaction finishes, qualified for reaction, and acetic anhydride and acetic acid are sloughed in decompression, obtain N- (1- ethyl propyls) -3,4- dimethyl benzenes
Acetamide.
Pilot run is as follows：
| Batch | 1 | 2 | 3 | 4 | 5 | 6 | It is average |
| Yield (g) | 133.5 | 133.1 | 133.4 | 133.7 | 133.7 | 133.6 | 133.5 |
| Content (%) | 99.1 | 99.4 | 99.3 | 99.0 | 99.1 | 99.0 | 99.2 |
| Yield (%) | 99.1 | 99.1 | 99.2 | 99.1 | 99.2 | 99.1 | 99.1 |
Remarks:Six batch experiment conditions are identical
Nitration reaction carries out according to the following steps：In N- (1- the ethyl propyls) -3,4- dimethyl benzene second for sloughing acetic anhydride acetic acid
In amide, dichloroethanes is added, is warming up to 40 DEG C, 95% concentrated nitric acid is then added dropwise, time for adding 2 hours finishes, continues to keep the temperature
Reaction 5 hours, sample detection N- (1- ethyl propyls) -3,4- dimethyl benzene acetyl amine content≤1%, for qualification, N- (1- ethyls
Propyl) -2,6- dinitro -3,4- dimethyl benzene acetyl amine content >=98%.Reaction finishes stratification, in oil phase and washing two
Enter hydrolysis step after secondary.
Pilot run is as follows：
| Batch | 1 | 2 | 3 | 4 | 5 | 6 | It is average |
| Yield (g) | 176.1 | 176.3 | 176.5 | 176.4 | 176.3 | 176.1 | 176.3 |
| Content (%) | 99.2 | 99.0 | 98.9 | 98.9 | 99.0 | 99.1 | 99.0 |
| Yield (%) | 98.7 | 98.6 | 98.6 | 98.6 | 98.6 | 98.6 | 98.6 |
Steps are as follows for acidolysis reaction：N- (1- ethyl propyls) -2,6- dinitro -3,4- dimethyl benzene second is obtained after neutralizing washing
Amide dichloroethane solution is added in 50% sulfuric acid solution, and stirring is warming up to 85 DEG C, and reaction is hydrolyzed, and heat preservation hydrolysis 4 is small
When, sampling and testing N- (1- ethyl propyls) -2,6- dinitro -3,4- dimethyl benzene acetyl amine content≤0.5% closes for reaction
Lattice, reaction finish, stratification, in oil reservoir and wash twice, then depressurize precipitation, precipitation finishes, and obtains peony pendimethalin
Clever active compound, content >=98%, test nitrous product assay are 0%.
Pilot run is as follows：
In summary known to result：Amidation average content：99.2%, average yield：99.1%；Nitrify average content
99%, average yield：98.6%；Acidolysis average content：99%, average yield：98.9%.With N- (1- ethyl propyls) -3,4-
Dimethylaniline is that raw material calculates Pendimethalin total recovery >=96%, and Pendimethalin active compound content >=98.9%, N- is sub-
Nitro content is 0.
The above disclosure is only the preferred embodiments of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, therefore equivalent changes made in accordance with the claims of the present invention, is still within the scope of the present invention.
Claims (4)
1. a kind of preparation method synthesizing Pendimethalin using nitrification process, which is characterized in that its preparation process is：Using amide
Change, nitrification, acidolysis three-step reaction synthetic technology route, with N- (1- ethyl propyls) -3,4- dimethylanilines for starting material, with
Dichloroethanes is solvent, and aceticanhydride amidation, then is nitrified with concentrated nitric acid, and then acidolysis prepares diformazan penta under dilute sulfuric acid effect again
Happy spirit, reaction principle are as follows：
(1) amidation process
(2) nitration reaction
(3) acidolysis reaction
2. preparation method according to claim 1, which is characterized in that the amidation process carries out according to the following steps：
N- (1- ethyl propyls) -3,4- dimethylanilines 0.7mol, acetic anhydride 0.75mol is added in 500ml reaction flasks, is warming up to
80-110 DEG C, acetic anhydride and acetic acid are sloughed in back flow reaction 5 hours, decompression, obtain N- (1- ethyl propyls) -3,4- dimethyl benzene acetyl
Amine.
3. preparation method according to claim 1, which is characterized in that the nitration reaction carries out according to the following steps：In N-
In (1- ethyl propyls) -3,4- dimethyl benzene acetamides, dichloroethanes 1.5mol is added, is warming up to 30-40 DEG C, is then added dropwise
95% concentrated nitric acid, nitric acid molal quantity are 1.5mol, and time for adding 1.5-2 hours finishes, and continue insulation reaction 5 hours, are obtained
N- (1- ethyl propyls) -2,6- dinitro -3,4- dimethyl benzene acetamides, reaction finish stratification, in oil phase and washing two
Enter hydrolysis step after secondary.
4. preparation method according to claim 1, which is characterized in that steps are as follows for the acidolysis reaction：After neutralizing washing
N- (1- ethyl propyls) -2,6- dinitro -3,4- dimethyl benzene acetamides are obtained, dichloroethanes 0.5mol is added, is added after mixing
Into 50% sulfuric acid solution, sulfuric acid molal quantity is 0.4mol, and stirring is warming up to 80-85 DEG C, and reaction, heat preservation hydrolysis is hydrolyzed
4 hours, reaction finished, stratification, in oil reservoir and washes twice, then depressurizes precipitation, precipitation finishes, and obtains peony diformazan penta
Happy spirit active compound.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5922913A (en) * | 1998-11-06 | 1999-07-13 | Srm Chemical, Ltd., Co. | Process for nitrating aromatic amines |
| CN101070287A (en) * | 2007-06-07 | 2007-11-14 | 吉化集团公司 | Process for removing N-nitroso-pendimethalin from pendimethialin |
| CN101891631A (en) * | 2010-07-08 | 2010-11-24 | 上海海事大学 | Method for preparing pendimethalin |
| CN107473974A (en) * | 2017-08-23 | 2017-12-15 | 山东华阳农药化工集团有限公司 | Application of the waste water caused by a kind of preparation method of Pendimethalin and the preparation method in chlopyrifos waste water is handled |
-
2018
- 2018-05-24 CN CN201810511465.1A patent/CN108484416A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5922913A (en) * | 1998-11-06 | 1999-07-13 | Srm Chemical, Ltd., Co. | Process for nitrating aromatic amines |
| CN101070287A (en) * | 2007-06-07 | 2007-11-14 | 吉化集团公司 | Process for removing N-nitroso-pendimethalin from pendimethialin |
| CN101891631A (en) * | 2010-07-08 | 2010-11-24 | 上海海事大学 | Method for preparing pendimethalin |
| CN107473974A (en) * | 2017-08-23 | 2017-12-15 | 山东华阳农药化工集团有限公司 | Application of the waste water caused by a kind of preparation method of Pendimethalin and the preparation method in chlopyrifos waste water is handled |
Non-Patent Citations (2)
| Title |
|---|
| 刘翠翠 等: "二甲戊乐灵的合成进展", 《化工中间体》 * |
| 滕裕翔: "微反应器中绿色硝化合成二甲戊乐灵的工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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