CN107266324A - A kind of synthetic method of the chloro benzoic ether of 2 amino 3 - Google Patents
A kind of synthetic method of the chloro benzoic ether of 2 amino 3 Download PDFInfo
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- CN107266324A CN107266324A CN201710579820.4A CN201710579820A CN107266324A CN 107266324 A CN107266324 A CN 107266324A CN 201710579820 A CN201710579820 A CN 201710579820A CN 107266324 A CN107266324 A CN 107266324A
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- amino
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
Abstract
The present invention discloses a kind of synthetic method of the chloro benzoic ether of 2 amino 3, mixed by raw material, centrifuge, precipitation is crystallized, decolorization four-stage carries out reaction synthesis, methyl anthranilate and two chlordantoins are mainly used to carry out No. 3 position chlorine atom growths of phenyl ring in tetrachloro-ethylene environment, realize the increase of chlorine element needed for target product on phenyl ring, realize that simple reaction thing synthesizes polyfunctional group compared with high level goal product, reaction is easy to operate, efficiency high, high income, raw material availability is big, product purity is considerable, route can scale application, the product of synthesis can meet industrial agricultural production use demand.
Description
Technical field
The method of the present invention belongs to pharmaceutical synthesis field, and in particular to a kind of herbicide intermediate 2- amino -3- chlorobenzene first
The synthesis of sour methyl esters and its purification.
Background technology
2- amino -3- chloro benzoic ethers are played an important role in medication chemistry synthesis, and it is triazolo pyrimidine sulphonyl
An important intermediate in amine herbicide building-up process, in addition other many pesticide synthesis processes fall within it should
Use category.Current cloransulammethyl is, using a kind of relatively more extensive herbicide, its weeding to be the reason for extensive efficiently, to drought
Field crop weeds especially broad leaved weed herbicidal effect is notable.Agricultural modernization development improves weeding requirement, and then expands effect
Really excellent herbicide use demand, demand promotion production, herbicide industry needs further development, herbicide synthetic intermediate
2- amino -3- chloro benzoic ethers certainly will need to carry out the improvement of synthetic technology route.
At present, all there is the exploration in certain methods path, feelings in the preparation both at home and abroad on 2- amino -3- chloro benzoic ethers
Condition is mainly：Peter Tonne etc. (United States Patent (USP) US 4306074A) disclose a kind of 2- amino -3- chloro benzoic ethers
Preparation method, it be by 3- chloro-phthalic anhydrides through first amination then carry out Hofmann degradation obtain 3- chloroisatoic anhydrides and
6- chloroisatoic anhydrides, carry out being esterified afterwards and obtain 2- amino -3- chloro benzoic ethers and 2- amino -6- chloro benzoic ethers again.
It is low to there is obvious shortcoming, i.e. atom utilization in this method, and accessory substance is unfavorable for industrialized production with the generation of target product equivalent,
Other 3- chloro-phthalic anhydrides easily cause breathing problem, and not meeting safety in production as raw material in synthesis requires.
Norman R.Pearson etc. (United States Patent (USP) US 5118832A) disclose a kind of 2- amino -3- chlorobenzoic acid first
The preparation method of ester, embodiment is by 2- Methyl anthranilates and 1,3- bis- in the organic solvents such as carbon tetrachloride
The reaction of chloro- 5,5- dimethyl hydantoins, obtain target product 2- amino -3- chloro benzoic ethers and accessory substance 2- amino -
5- chloro benzoic ethers, 2- amino -3,5- methyl p-dichlorobenzenes, two kinds of accessory substances can cause target product 2- amino -3- chlorine
Methyl benzoate yield is greatly lowered, while influenceing the purity of 2- amino -3- chloro benzoic ethers.In addition 2- aminobenzoic acids
Methyl esters and chloro- 5, the 5- dimethyl hydantoins of 1,3- bis- are all important chemical industry synthesis products, and 2- amino -3- chlorine is carried out with the two
The synthesis of methyl benzoate is without production reasonability.
G unther Semler etc. (United States Patent (USP) US 5557005A) disclose a kind of 2- amino -3- chloro benzoic ethers
Preparation method, by 2- amino -3- chlorobenzoic acids first with phosgene reaction obtain 3- chloroisatoic anhydrides, then again with methanol carry out ester
Change reaction and obtain 2- amino -3- chloro benzoic ethers.This synthetic method make use of the esterification effect of classics, but prepare
What is taken during acid anhydrides is gas liquid reaction, is unfavorable for controlling the extent of reaction；Other phosgene is industrially using few, because it is acute
Poison, there is intense irritation, and very unsuitable pharmaceutical synthesis process is used.
Sun Yonghui etc. (the preparation method CN 103193666A of 2- amino -3- chloro benzoic ethers) takes more direct
Mode is synthesized:In organic solvent so that 2- amino -3- chlorobenzoic acids react with inorganic base, while using methylating reagent
Say that inorganic base is changed into methyl esters end.This method is simple to operation, but with only esterification, is not directed to span larger
Element increases and decreases process on phenyl ring, and 2- amino -3- chlorobenzoic acids have been sufficiently close to target product, and its price and 2- amino -
3- chloro benzoic ethers are closer to, and are not suitable for carrying out industrialized production.
(new synthetic method University Of Xiangtan natural science journal June the 29th in 2007 of 2 3,dichloro benzoic acid 99 such as Lin Yuanbin
Volume) using o-chloraniline as raw material, adjacent chloro aniline is first made and is given birth to concentrated sulfuric acid cyclization with chloral hydrate, hydroxylamine hydrochloride reaction
Use hydrogen peroxide oxidation again into 3- chlorisatides, 2- amino -3- chlorobenzoic acids be made, esterification is carried out afterwards, by 2- amino -
2- amino -3- chloro benzoic ethers are made with methanol reaction in 3- chlorobenzoic acids.This method is related to a variety of chemical reagent, and reaction seems
It is more complicated, and multi-step is not fully and completely to be reacted, and a variety of reactants easily cause remaining influence target product
Purity.
The content of the invention
Goal of the invention：The purpose of the present invention is that the prior art in terms of 2- amino -3- chloro benzoic ether preparations is explored
Learn from other's strong points to offset one's weaknesses in content, develop a kind of new operation it is relatively simple, reaction easily realize, yield meet production requirement and demand
2- amino -3- chloro benzoic ether synthetic routes.
Technical scheme：Synthetic schemes of the present invention mainly has raw material mixing, centrifugation, precipitation crystallization, decolorization four
Stage, the reactant being related to is less, and physico operation accounts for larger specific gravity in synthesis, convieniently synthesized easy, is specially：
1. tetrachloro-ethylene suction reactor is stirred heating, then adds methyl anthranilate, raise temperature
To 93 DEG C, two chlordantoins are added afterwards, two chlordantoins should be noted that temperature of reaction kettle changes when adding, if temperature is higher than 100 DEG C
Charging waiting temperature need to be stopped and be reduced to 93 DEG C or so, be further continued for adding two chlordantoins.Temperature is controlled after adding all reaction materials
At 110 DEG C, 6h is persistently stirred, chilling temperature is to 40 DEG C afterwards.
2. synthetic material is loaded centrifuge and carries out separation of solid and liquid, mother liquor input mother liquor tank, solid carries out defective material and returned
Bag.
3. mother liquor injection precipitation kettle is warming up to 105-115 DEG C.Observe discharging situation, reclaim abjection tetrachloro-ethylene in case
After use, residue is target product crude product, crude product is squeezed into high temperature precipitation kettle is warming up to 130-145 DEG C and steam product, is discharged
Mother liquor rectifying after residue, carrying out precipitation treatment obtains product of the content 98% or so, is transferred into crystallization kettle by 1：2 ratios
Add isoparaffin solvent oil and cool to 1-5 DEG C, crystallization 12h obtains product.
4. it is last to carry out activated carbon decolorizing processing, obtain white clear fluid product.
The reaction equation of this synthetic route is as follows：
The synthetic route of the present invention has certain advantage:1. it is simple to operate, easily carry out industrial-scale production；2. close
Three kinds of materials are only related into step, the organic solvent thing that wherein tetrachloro-ethylene is carried out as reaction creates reaction advantage,
On the one hand the efficiency requirements that reaction process meets industrialized production are accelerated, another aspect solvent is recyclable, saves reaction cost；③
Comprising precipitation crystallization and decolorization in synthetic schemes, meet the high-quality demand of product, the product of different levels can be met
Demand.
Embodiment
Embodiment one：
Tetrachloro-ethylene 54kg suction reactors are stirred and heated and are heated up, 6kg o-amino benzoyls are then added
Sour methyl esters, continues rise temperature and is carried out to 93 DEG C, afterwards in the addition operation of two chlordantoins, this adition process it should be noted that temperature becomes
Change, if two chlordantoin feeding operations need to be stopped higher than 100 DEG C of phenomenons by temperature occur, waiting temperature is reduced to 90-93 DEG C, continues to add
Enter two chlordantoins, two chlordantoin additions are 4.5kg.After all reaction materials are installed additional and finished, temperature is maintained near 110 DEG C,
6h is persistently stirred, stirring carries out cooling down operation after terminating, reduction temperature is to 40 DEG C.
Centrifuge separation of solid and liquid operation is carried out, the mother liquor input mother liquor tank isolated, solid carries out scraps recycle pack.
Mother liquor enters precipitation kettle from mother liquor tank, is warming up to 105-115 DEG C, the tetrachloro-ethylene of abjection is reclaimed for future use, is remained
Excess is crude product.Crude product is squeezed into high temperature precipitation kettle and is warming up to 130-145 DEG C, product is steamed, residue, carrying out precipitation treatment is discharged.
Mother liquor progress rectifying is obtained into product afterwards, is then transferred into crystallization kettle by 1：2 ratios add isoparaffin solvent oil,
Temperature is reduced to 3 DEG C (2-5 DEG C), and crystallization 12h obtains product.
To product decolorization, obtain white clear fluid product, weigh quality is 9.86kg, purity detecting value is
98.06%, product homogenisation degree is preferable.
Embodiment two：
Material is carried out in a kettle. and adds operation, is added methyl anthranilate 6kg, is then carried out warming temperature,
Raise temperature to 93 DEG C, backward reactor add two chlordantoins, temperature change is noted during addition, if occur temperature be higher than 100
DEG C phenomenon need to stop two chlordantoin feeding operations, carry out cooling processing, and waiting temperature is reduced to 90-93 DEG C, continuously adds dichloro
Glycolylurea is until add the chlordantoin materials of 4.5kg bis-.All reaction materials are installed additional finish after, maintain temperature at 110 DEG C, persistently stirred
12h is mixed, stirring cools after terminating to be operated, and is cooled to 40 DEG C.
Centrifuge separation of solid and liquid operation is carried out, the mother liquor input mother liquor tank isolated, solid carries out scraps recycle pack.
Mother liquor is inputted into precipitation kettle, warming temperature to temperature in the range of 105-115 DEG C, the recovery of the tetrachloro-ethylene of abjection with
Standby rear use, is that crude product squeezes into high temperature precipitation kettle by residue, warming temperature to temperature reaches 130-145 DEG C, steams product, and discharge is surplus
Remaining residue, carries out preliminary purification by carrying out precipitation treatment operation afterwards.Mother liquor is subjected to distillation operation afterwards, product is obtained, then
It is transferred into crystallization kettle by 1：2 ratios add isoparaffin solvent oil, and temperature is reduced to 3 DEG C, and crystallization 24h obtains final production
Product.
To product decolorization, obtain white clear fluid product, weigh product quality is 9.75kg, purity detecting value
For 90.12%, product homogenisationization is general, slightly has suspension little particle compared to embodiment one.
The correlation circumstance of embodiment three, four, five is tabulated below：
Contrast embodiment one and embodiment two find that synthesis is carried out not under carbon tetrachloride solvent environment, even if turning over
Times reactant incorporation time and product crystallization time, yield are still reduced.Synthesized in carbon tetrachloride organic solvent, dichloro
Glycolylurea and methyl anthranilate reaction efficiency height, high income, raw material availability are big, can save production cost.
Inventory, mixing time, crystallization time can be carried out pure when being synthesized by embodiment three, four, five visible changes
Degree, yield regulation.
Claims (7)
1. a kind of synthetic method of 2- amino -3- chloro benzoic ethers, it synthesizes particular content and is：Mixed by 1. raw material；②
Centrifuge；3. precipitation is crystallized；4. four steps of decolorization, cause in tetrachloro-ethylene environment methyl anthranilate with
Two chlordantoins carry out reaction to obtain target product.
2. a kind of Material synthesis method of 2- amino -3- chloro benzoic ethers according to claim 1, it is characterised in that
Tetrachloro-ethylene suction reactor is stirred heating, methyl anthranilate is then added, rise temperature is to 93 DEG C, afterwards
Two chlordantoins are added, two chlordantoins should be noted that temperature of reaction kettle changes when adding, if temperature need to stop charging etc. higher than 100 DEG C
Treat that temperature is reduced to 93 DEG C or so, be further continued for adding two chlordantoins up to material addition is finished, add and controlled after all reaction materials
Temperature persistently stirs 6h near 110 DEG C, and cooling down operation makes temperature maintain 40 DEG C afterwards.
3. mixing time according to claim 2, it is characterised in that can suitably increase to 8h.
4. a kind of centrifugal separation method of 2- amino -3- chloro benzoic ethers according to claim 1, it is characterised in that
Synthetic material is loaded centrifuge and carries out separation of solid and liquid, mother liquor input mother liquor tank, solid carry out scraps recycle pack in case
Processing.
5. a kind of precipitation method for crystallising of 2- amino -3- chloro benzoic ethers according to claim 1, it is characterised in that
Mother liquor injection precipitation kettle is warming up to 105-115 DEG C.Discharging situation is observed, the tetrachloro-ethylene deviate from is reclaimed for future use, it is remaining
Thing is target product crude product, crude product is squeezed into high temperature precipitation kettle is warming up to 130-145 DEG C and steam product, discharges residue, precipitation
Mother liquor rectifying after processing obtains product of the content 98% or so, is transferred into crystallization kettle by 1：2 ratios add isomery
Alkane solvent oil cools to 1-5 DEG C, and crystallization 12h obtains product.
6. addition isoparaffin solvent oil operation according to claim 5, it is characterised in that 13-16 carbon isomeries can be used
Alkane is used as isoparaffin solvent oil.
7. a kind of decoloration treatment method of 2- amino -3- chloro benzoic ethers according to claim 1, it is characterised in that
Product decolorization is carried out using activated carbon as decolorising agent.
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| CN201710579820.4A CN107266324A (en) | 2017-07-17 | 2017-07-17 | A kind of synthetic method of the chloro benzoic ether of 2 amino 3 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047069A (en) * | 2017-12-29 | 2018-05-18 | 南通泰禾化工股份有限公司 | A kind of preparation method of 2- amino -3- chloro benzoic ethers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118832A (en) * | 1991-06-14 | 1992-06-02 | Dowelanco | Process for the preparation of alkyl 3-chloroanthranilates |
| US5557005A (en) * | 1993-04-22 | 1996-09-17 | Hoechst Aktiengesellschaft | Process for preparing 3-chloroanthranilic alkyl esters of high purity from 3-chloroanthranilic acid |
| CN103193666A (en) * | 2013-04-09 | 2013-07-10 | 江苏省农用激素工程技术研究中心有限公司 | Preparation method of 2-amino-3-chlorobenzoic methyl ester |
-
2017
- 2017-07-17 CN CN201710579820.4A patent/CN107266324A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118832A (en) * | 1991-06-14 | 1992-06-02 | Dowelanco | Process for the preparation of alkyl 3-chloroanthranilates |
| US5557005A (en) * | 1993-04-22 | 1996-09-17 | Hoechst Aktiengesellschaft | Process for preparing 3-chloroanthranilic alkyl esters of high purity from 3-chloroanthranilic acid |
| CN103193666A (en) * | 2013-04-09 | 2013-07-10 | 江苏省农用激素工程技术研究中心有限公司 | Preparation method of 2-amino-3-chlorobenzoic methyl ester |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047069A (en) * | 2017-12-29 | 2018-05-18 | 南通泰禾化工股份有限公司 | A kind of preparation method of 2- amino -3- chloro benzoic ethers |
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Application publication date: 20171020 |