CN109438287A - A kind of preparation method of afesin - Google Patents
A kind of preparation method of afesin Download PDFInfo
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- CN109438287A CN109438287A CN201811504509.4A CN201811504509A CN109438287A CN 109438287 A CN109438287 A CN 109438287A CN 201811504509 A CN201811504509 A CN 201811504509A CN 109438287 A CN109438287 A CN 109438287A
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- Prior art keywords
- afesin
- preparation
- alkali
- product
- dimethyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1854—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety
- C07C273/1863—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas by reactions not involving the formation of the N-C(O)-N- moiety from urea
Abstract
The invention belongs to pesticide synthesis technology fields, more particularly, to a kind of preparation method of afesin.Its structure and chemically synthesized steric hindrance by analyzing afesin, it is main material using cheap and easily-available chlorophenyl isocyanate and dimethyl azanol hydrochloride, it is reacted in polar solvent, product afesin can be made in single step reaction, and product purity is up to 98% or more, thus product yield solves that complex process existing for prior art afesin preparation process, by-product are more, pollute the technical issues of environment close to 80%.
Description
Technical field
The invention belongs to pesticide synthesis technology fields, more particularly, to a kind of preparation method of afesin.
Background technique
Afesin also known as 3- (rubigan) -1- methoxyl group -1- methylurea are a kind of important organochlorine insecticides, extensively
It is general to be applied to veterinary drug and pesticide field.But up to the present there are no the effective industrialized preparing process for preparing this product.
Once a kind of method (Journal of Chromatography, 554 (1- for preparing afesin was reported in document
2),233-50；1991；Angewandte Chemie,75(18),851-4；1963), specific synthetic route is as follows:
This method needs multistep to synthesize since raw material needs the used time to prepare, and synthesis technology is complicated；In addition dimethyl suflfate has
Poison, reaction generate the sodium salt of many waste water and by-product methyl sulfate, there is very big pollution to environment.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of preparation method of afesin,
By analyzing the structure and chemically synthesized steric hindrance of afesin, cheap and easily-available chlorophenyl isocyanate and diformazan are utilized
Hydroxylamine hydrochloride is main material, is reacted in polar solvent, and one-step method can be made product afesin, and product purity is up to 98%
More than, product yield close to 80%, thus solve complex process existing for prior art afesin preparation process, by-product it is more,
The technical issues of polluting environment.
To achieve the above object, according to one aspect of the present invention, a kind of preparation method of afesin is provided, to chlorine
Phenylisocyanate and dimethyl azanol hydrochloride are main material, under polar solvent and alkali existence condition, sufficiently separate and mention after reaction
It is pure to obtain product afesin；Wherein, the alkali is used to neutralize the hydrochloric acid in dimethyl azanol hydrochloride, it is made to be converted into free two
First azanol.
As a preferred option, the alkali is organic base or inorganic base.
As further preferred scheme, the alkali be one of sodium carbonate, potassium carbonate, sodium bicarbonate and triethylamine or
It is a variety of.
As further preferred scheme, the solvent is dioxane, methylene chloride, tetrahydrofuran, toluene, N, N- bis-
One of methylformamide (DMF) and water are a variety of.
As further preferred scheme, reaction temperature is minus 30 DEG C above freezing between 100 DEG C.
As further preferred scheme, reaction temperature is subzero 10 DEG C to 50 DEG C above freezing.
As further preferred scheme, the preparation method includes the following steps:
(1) under agitation, alkali is added in batches into the mixed solution of dimethyl azanol hydrochloride and polar solvent, controls
Solution heating processed is not higher than 20 DEG C, and the alkali is used to neutralize the hydrochloric acid in dimethyl azanol hydrochloride, it is made to be converted into free two
First azanol；
(2) it between 15 DEG C, is slowly added to above freezing into system obtained by step (1) to chlorobenzene isocyanic acid at subzero 30 DEG C
Ester, control temperature are warming up to 50-100 DEG C, react 5-12 hours, product afesin is obtained after separating-purifying.
As further preferred scheme, the charged molar ratio of the chlorobenzene isocyanates and dimethyl azanol hydrochloride is 1:
(1.1-1.5), the input amount of alkali are 1-2 times of dimethyl azanol hydrochloride mole.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect.
(1) the preparation method raw material of afesin provided by the invention is commercially available obtains, and raw material is easy to get, and solvent for use is cheap.
(2) synthetic reaction of afesin provided by the invention is one pot reaction, and single step reaction can be obtained target product
Afesin, easy to operate, convenient post-treatment, and yield are close to 80%, and purity is up to 98% or more.
(3) reaction time is short, consumes energy low.
(4) there is no by-product in technique, and there is no " three wastes " generation substantially.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of product made from the embodiment of the present invention 1；
Fig. 2 is the efficient liquid phase chromatographic analysis figure of product made from the embodiment of the present invention 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The preparation method of a kind of afesin provided by the invention, based on chlorophenyl isocyanate and dimethyl azanol hydrochloride
Raw material, under polar solvent and alkali existence condition, sufficiently separating-purifying obtains product afesin after reaction；Wherein, the alkali is used
In neutralizing the hydrochloric acid in dimethyl azanol hydrochloride, carried out instead after so that it is converted into free dimethylhydroxylamine with chlorophenyl isocyanate
It answers.
Specific synthesis technology of the invention is as follows:
The preparation of afesin can be realized by single step reaction for the technique.
Alkali of the present invention is organic base or inorganic base, and in some embodiments, the alkali is sodium carbonate, potassium carbonate, carbonic acid
One of hydrogen sodium and triethylamine are a variety of.
In some embodiments, the solvent is dioxane, methylene chloride, tetrahydrofuran, toluene, N, N- dimethyl formyl
One of amine (DMF) and water are a variety of.
In some embodiments, the present invention synthesize afesin reaction temperature be minus 30 DEG C it is above freezing between 100 DEG C.
In some preferred embodiments, it is subzero 10 DEG C to 50 DEG C above freezing that the present invention, which synthesizes afesin reaction temperature,.
Afesin preparation method of the present invention preferably carries out in accordance with the following steps:
(1) under agitation, at room temperature (10-30 DEG C) into the mixed solution of dimethyl azanol hydrochloride and polar solvent
Alkali is added in batches, control solution heating is not higher than 20 DEG C, and the alkali is used to neutralize the hydrochloric acid in dimethyl azanol hydrochloride, makes it
It is converted into free dimethylhydroxylamine；Alkali neutralization dimethyl azanol hydrochloride is exothermic reaction, thereby increases and it is possible to generate gas, for example use carbon
When hydrochlorate or bicarbonate, carbon dioxide gas can be generated；The purpose of alkali is added in batches first is that increasing width to control temperature
Degree should not be too big, second is that avoiding once addition from generating bulk gas leads to slug.
(2) it between 15 DEG C, is slowly added to above freezing into system obtained by step (1) to chlorobenzene isocyanic acid at subzero 30 DEG C
Ester can control temperature between 50-100 DEG C, react 5-12 hours by the way of addition is added dropwise.
(3) add water that solid is precipitated after reaction, be cooled to 0-10 DEG C, keep the temperature 3-4 hours, solid is collected in filtering, will
The solid is dissolved in methanol or methylene chloride, and with active carbon decoloring, then concentration removal solvent, is cooled to 0-10 DEG C, slowly analyses
White crystal out isolates solid, product afesin is obtained after drying.
In the synthesis of afesin of the present invention, the charged molar ratio of chlorobenzene isocyanates, dimethyl azanol hydrochloride and alkali is 1:
(1.1-1.5), wherein dimethyl azanol hydrochloride is dimethylhydroxylamine hydrochloric acid relative to the chlorobenzene isocyanates amount of skipping over, the input amount of alkali
1-2 times of salt mole.
The present invention passes through the structure and chemically synthesized steric hindrance of analysis afesin, using cheap and easily-available to chlorobenzene
Isocyanates and dimethyl azanol hydrochloride are main material, react at room temperature in polar solvent, product afesin can be prepared,
Product purity is up to 98% or more, and yield is close to 80%.
The following are embodiments:
Embodiment 1
Dimethyl azanol hydrochloride (718.8 grams) is dissolved in inside 7 liters of DMF, be cooled to 0 DEG C or so (minus 5 DEG C of low temperature, high temperature
Positive 5 DEG C).The solution of above-mentioned stirring is added portionwise in sodium bicarbonate (1030 grams).Temperature control is less than 20 DEG C, chlorophenyl isocyanate (943
Gram) be slowly added into, it is added in about 2 hours.
After adding, being warming up to is room temperature, continues stirring 5-12 hours.
Above-mentioned reaction system is added in the water that 7-10 rises, and solid is slowly presented, and is cooled to 0-10 DEG C, keeps the temperature 3-4 hours, solid
It is precipitated, starts to filter, collect solid.
Above-mentioned solid is dissolved in methanol or methylene chloride, and with active carbon decoloring, then most of solvent is walked in concentration, is cooled to
0-10 DEG C, white crystal is slowly precipitated.
Solid is collected by centrifugation, drying obtains product, and nucleus magnetic hydrogen spectrum such as Fig. 1, liquid chromatogram HPLC analyze result such as Fig. 2 institute
Show, analysis knows that it is 3- (rubigan) -1- methoxyl group -1- methylurea, as 1120 grams of product afesin, yield 71%.
Embodiment 2
Dimethyl azanol hydrochloride (718.8 grams) is dissolved in inside 7 liters of toluene, be cooled to 0 DEG C or so (minus 5 DEG C of low temperature, high temperature
Positive 5 DEG C).The solution of above-mentioned stirring is added portionwise in triethylamine (1200 grams).Temperature control is less than 20 DEG C, chlorophenyl isocyanate (943
Gram) be slowly added into, it is added in about 2 hours.
After adding, being warming up to is room temperature, continues stirring 5-12 hours.
Reaction solution is cooled to 0-10 DEG C, keeps the temperature 3-4 hours, and solid is precipitated, and starts to filter, and collects solid.
Above-mentioned solid is dissolved in methanol or methylene chloride, and with active carbon decoloring, then most of solvent is walked in concentration, is cooled to
0-10 DEG C, white crystal is slowly precipitated.
Solid is collected by centrifugation, drying obtains product, as 1250 grams of product afesin, yield 79%.
Embodiment 3
Dimethyl azanol hydrochloride (718.8 grams) is dissolved in inside 7 liters of DMF, be cooled to 0 DEG C or so (minus 5 DEG C of low temperature, high temperature
Positive 5 DEG C).The solution of above-mentioned stirring is added portionwise in sodium bicarbonate (1030 grams).Temperature control is less than 20 DEG C, chlorophenyl isocyanate (943
Gram) be slowly added into, it is added in about 2 hours.
After adding, being warming up to is 80 DEG C, continues stirring 5 hours.
Above-mentioned reaction system is added in the water that 7-10 rises, and solid is slowly presented, and is cooled to 0-10 DEG C, keeps the temperature 3-4 hours, solid
It is precipitated, starts to filter, collect solid.
Above-mentioned solid is dissolved in methanol or methylene chloride, and with active carbon decoloring, then most of solvent is walked in concentration, is cooled to
0-10 DEG C, white crystal is slowly precipitated.
Solid is collected by centrifugation, drying is 984 grams of product afesin, yield 62%.
Embodiment 4
Dimethyl azanol hydrochloride (718.8 grams) is dissolved in inside 7 liters of DMF, be cooled to 0 DEG C or so (minus 5 DEG C of low temperature, high temperature
Positive 5 DEG C).The solution of above-mentioned stirring is added portionwise in sodium bicarbonate (1030 grams).Temperature control is less than 20 DEG C, chlorophenyl isocyanate (943
Gram) be slowly added into, it is added in about 2 hours.
After adding, being warming up to is 80 DEG C, continues stirring 5 hours.
Above-mentioned reaction system is added in the water that 7-10 rises, and solid is slowly presented, and is cooled to 0-10 DEG C, keeps the temperature 3-4 hours, solid
It is precipitated, starts to filter, collect solid.
Above-mentioned solid is dissolved in methanol or methylene chloride, and with active carbon decoloring, then most of solvent is walked in concentration, is cooled to
0-10 DEG C, white crystal is slowly precipitated.
Solid is collected by centrifugation, drying is 984 grams of product afesin, yield 62%.
Embodiment 5
Dimethyl azanol hydrochloride (300 kilograms) is dissolved in inside 3000 liters of toluene, be cooled to 0 DEG C or so (minus 5 DEG C of low temperature,
Positive 5 DEG C of high temperature).The solution of above-mentioned stirring is added portionwise in sodium bicarbonate (400 kilograms).Temperature control is less than 20 DEG C, to chlorobenzene isocyanic acid
Ester (390 kilograms) is slowly added into.
After adding, being warming up to is room temperature, continues stirring 5-12 hours.
Reaction solution is cooled to 0-10 DEG C, keeps the temperature 3-4 hours, and solid is precipitated, and starts to filter, and collects solid.
Above-mentioned solid is dissolved in methanol or methylene chloride, and with active carbon decoloring, then most of solvent is walked in concentration, is cooled to
0-10 DEG C, white crystal is slowly precipitated.
Solid is collected by centrifugation, drying is 490 kilograms of product afesin, yield 74%.
Embodiment 6
Dimethyl azanol hydrochloride (300 kilograms) is dissolved in inside 2500 liters of toluene, be cooled to 0 DEG C or so (minus 5 DEG C of low temperature,
Positive 5 DEG C of high temperature).The solution of above-mentioned stirring is added portionwise in sodium carbonate (300 kilograms).Temperature control is less than 20 DEG C, chlorophenyl isocyanate
(390 kilograms) are slowly added into.
After adding, being warming up to is room temperature, continues stirring 5-12 hours.
Reaction solution is cooled to 0-10 DEG C, keeps the temperature 3-4 hours, and solid is precipitated, and starts to filter, and collects solid.
Above-mentioned solid is dissolved in methanol or methylene chloride, and with active carbon decoloring, then most of solvent is walked in concentration, is cooled to
0-10 DEG C, white crystal is slowly precipitated.
Solid is collected by centrifugation, drying is 473 kilograms of product afesin, yield 72%.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of afesin, which is characterized in that using chlorophenyl isocyanate and dimethyl azanol hydrochloride as raw material,
Under polar solvent and alkali existence condition, sufficiently separating-purifying obtains product afesin after reaction；Wherein, the alkali is for neutralizing
Hydrochloric acid in dimethyl azanol hydrochloride makes it be converted into free dimethylhydroxylamine.
2. preparation method as described in claim 1, which is characterized in that the alkali is organic base or inorganic base, preferably carbonic acid
One of sodium, potassium carbonate, sodium bicarbonate and triethylamine are a variety of.
3. preparation method as described in claim 1, which is characterized in that the solvent is dioxane, methylene chloride, tetrahydro furan
It mutters, one of toluene, N,N-dimethylformamide (DMF) and water or a variety of.
4. preparation method as described in claim 1, which is characterized in that the reaction temperature of the reaction is minus 30 DEG C above freezing
Between 100 DEG C.
5. preparation method as described in claim 1, which comprises the steps of:
(1) under agitation, alkali is added in batches into the mixed solution of dimethyl azanol hydrochloride and polar solvent, controls molten
Liquid heating is not higher than 20 DEG C, and the alkali is used to neutralize the hydrochloric acid in dimethyl azanol hydrochloride, it is made to be converted into free diformazan hydroxyl
Amine；
(2) between 15 DEG C, it is slowly added to chlorophenyl isocyanate into system obtained by step (1) to above freezing at subzero 30 DEG C, controlled
Temperature processed reacts 5-12 hours between 50-100 DEG C, product afesin is obtained after separating-purifying.
6. preparation method as described in claim 1, which is characterized in that the chlorobenzene isocyanates and dimethyl azanol hydrochloride
Charged molar ratio is 1:(1.1-1.5), the input amount of alkali is 1-2 times of dimethyl azanol hydrochloride mole.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB852422A (en) * | 1957-06-14 | 1960-10-26 | Hoechst Ag | New urea derivatives and process for their manufacture |
| US3198830A (en) * | 1958-04-17 | 1965-08-03 | Hoechst Ag | Process for preparing n-chlorophenyl-n'-methoxy-n'-methyl |
| CN1511143A (en) * | 2001-05-21 | 2004-07-07 | 拜尔农作物科学股份公司 | Herbicidal substituted benzoylpyrazoles |
| CN101781236A (en) * | 2010-02-11 | 2010-07-21 | 江苏快达农化股份有限公司 | Method for preparing 3-(3,4-dichlorophenyl)-1-methoxy-1-methyl urea |
| CN103910654A (en) * | 2014-04-22 | 2014-07-09 | 江苏快达农化股份有限公司 | Synthesis method of 1-methyl-1-methoxyl-3-phenylurea |
| CN105017085A (en) * | 2014-04-28 | 2015-11-04 | 中国科学院上海药物研究所 | Novel KCNQ potassium channel agonist and preparation method and application thereof |
| CN106831492A (en) * | 2017-03-28 | 2017-06-13 | 常州沃腾化工科技有限公司 | A kind of preparation method of phenylurea herbicide |
| CN110128301A (en) * | 2018-02-08 | 2019-08-16 | 上海裕兰生物科技有限公司 | A kind of blue-green alge remover and its environment-friendly preparation method thereof |
-
2018
- 2018-12-10 CN CN201811504509.4A patent/CN109438287A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB852422A (en) * | 1957-06-14 | 1960-10-26 | Hoechst Ag | New urea derivatives and process for their manufacture |
| US3198830A (en) * | 1958-04-17 | 1965-08-03 | Hoechst Ag | Process for preparing n-chlorophenyl-n'-methoxy-n'-methyl |
| CN1511143A (en) * | 2001-05-21 | 2004-07-07 | 拜尔农作物科学股份公司 | Herbicidal substituted benzoylpyrazoles |
| CN101781236A (en) * | 2010-02-11 | 2010-07-21 | 江苏快达农化股份有限公司 | Method for preparing 3-(3,4-dichlorophenyl)-1-methoxy-1-methyl urea |
| CN103910654A (en) * | 2014-04-22 | 2014-07-09 | 江苏快达农化股份有限公司 | Synthesis method of 1-methyl-1-methoxyl-3-phenylurea |
| CN105017085A (en) * | 2014-04-28 | 2015-11-04 | 中国科学院上海药物研究所 | Novel KCNQ potassium channel agonist and preparation method and application thereof |
| CN106831492A (en) * | 2017-03-28 | 2017-06-13 | 常州沃腾化工科技有限公司 | A kind of preparation method of phenylurea herbicide |
| CN110128301A (en) * | 2018-02-08 | 2019-08-16 | 上海裕兰生物科技有限公司 | A kind of blue-green alge remover and its environment-friendly preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| D. BARCELO ET AL: "Applications of thermospray liquid chromatography-mass spectrometry in photochemical studies of pesticides in water", 《JOURNAL OF CHROMATOGRAPHY》 * |
| ECKSTEIN ZYGMUNT ET AL: "Possibilities of using 4-chloro-2-methylphenoxyacetohydroxamic acid for synthesis of O-mono- and O,N-dimethylhydroxylamines", 《PRZEMYSL CHEMICZNY 》 * |
| K.HARTEL ET AL: "Darstellung von N-alkoxylierten Harnstoffen und ihr Einsatz als selektive Herbizide", 《ANGEWANDTE CHEMIE》 * |
| 冯玉冰等: "稳定同位素氘标记苯脲类除草剂的合成研究", 《化学试剂》 * |
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