CN106187811A - The synthesis technique of pyraclostrobin intermediate p-hydrochloride - Google Patents
The synthesis technique of pyraclostrobin intermediate p-hydrochloride Download PDFInfo
- Publication number
- CN106187811A CN106187811A CN201610524996.5A CN201610524996A CN106187811A CN 106187811 A CN106187811 A CN 106187811A CN 201610524996 A CN201610524996 A CN 201610524996A CN 106187811 A CN106187811 A CN 106187811A
- Authority
- CN
- China
- Prior art keywords
- sodium nitrite
- temperature
- pressure
- reaction
- hydrochloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The synthesis technique of pyraclostrobin intermediate p-hydrochloride, its synthesis technique comprises the following steps: first prepares diazo liquid, then reacts with sodium nitrite solution, is acidified, i.e. can get p-hydrochloride.Compared with prior art, the technique that the present invention provides not only reduces production cost, and more environmentally friendly, it is easy to operates and is more beneficial for industrialized production, further synthesizing pyrazole kresoxim-methyl.
Description
Technical field
The present invention relates to pesticide synthesis field, be specifically related to the synthesis work of pyraclostrobin intermediate p-hydrochloride
Skill.
Background technology
Pyraclostrobin is the methoxy acrylic bactericide having pyrrazole structure concurrently, and 1993 public by Germany's BASF
Department finds, calendar year 2001 registers and lists, has been used at present in 100 various crop.2009, it is beautiful that its sales volume reaches 7.35 hundred million
Unit, is only second to Fluoxastrobin, becomes world's second largest antibacterial.Pyraclostrobin wide spectrum, efficiently, toxicity low, to non-target organism
Safety, to user and environment all safety close friends, is good market prospect in strobilurin series bactericidal agent, patent will mistake
The staple product of phase.
Sum up to get up to be divided into two to the synthetic route of pyraclostrobin the most both at home and abroad:
Article 1, route is by ortho-methylnitrobenzene, first obtains o-nitrobenzyl bromide, o-nitrobenzyl bromide through Benzylphosphonium Bromide
With 1-(4-chlorphenyl)-3-hydroxypyrazoles is condensed to yield 2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl] Nitrobenzol, then pass through
Reduction obtains N-hydroxy-n-2-[(N-4-chlorphenyl)-3-pyrazoles epoxide methyl]-aniline, then with methylchloroformate reaction obtains
N-hydroxy-n-2-[(N-rubigan)-3-pyrazoles epoxide methyl] carbanilate, last and dimethyl sulfate is reacted
To pyraclostrobin.
Article 2 route, by ortho-methylnitrobenzene, obtains o-methyl-phenyl-azanol through reduction, then with methylchloroformate
Reaction obtains N-hydroxy-n-toluidino methyl formate, then obtains N-methoxy-. N-methyl phenylamino with dimethyl sulfate reaction
Base methyl formate.N-methoxy-. N-methyl phenylcarbamate obtains pyrazoles with 1-(4-chlorphenyl)-3-hydroxypyrazoles again
Pyraclostrobin.
Above-mentioned 2 synthetic route reactions steps are essentially the same, all there are reduction and 2 committed steps of bromination.In circuit 2 also
Former fairly simple, method is relatively more and the highest to equipment requirements, than circuit 1 advantage.In bromination reaction also easy than circuit 1, but
Bromination there is impurity generate, be not readily separated, be directly brought in product, cause product to refine.
Summary of the invention
For the deficiencies in the prior art, the invention provides the synthesis work of pyraclostrobin intermediate p-hydrochloride
Skill.
The present invention can be achieved through the following technical solutions:
The synthesis technique of pyraclostrobin intermediate p-hydrochloride, it is characterised in that synthesis technique includes following
Step:
(1) be in glass lined diazotising still, to put into the parachloroanilinum of 1 weight portion to material, the hydrochloric acid of 2.5 weight portions and
The water of 1.5 weight portions, opens anchor formula agitating device, and the peripheral speed controlling anchor formula stirrer paddle outer rim is 0.5-1.5m/s, rises
High reaction temperature, continues stirring and makes solid all dissolve, and controls temperature and is less than 100 DEG C, and holding pressure is pressure-fired；
(2) it is in glass lined sodium nitrite dissolution kettle, to add sodium nitrite and 5 weight parts waters of 2 weight portions to material,
Opening anchor formula agitating device, rise high-temperature, control temperature and be less than 100 DEG C, holding pressure is pressure-fired, until sodium nitrite is complete
Portion dissolves；
(3) solution after dissolving in step 1 drips the sodium nitrite solution of step 2, sentences with starch potassium iodide paper
Disconnected terminal, when, after reagent paper variable color, stopping dropping sodium nitrite solution, continues stirring 1h, obtains diazo liquid standby after filtration；
(4) sodium nitrite solution remaining in step 3 is transferred in material is glass lined reduction kettle, slowly rises high temperature
Degree, to 80 DEG C, is opened third gear paddle agitating device, is dripped the diazo liquid in step 3 while stirring, protect in reduction kettle under normal pressure
Temperature reaction 2h, after reaction terminates, the activated carbon adding 0.1 weight portion while hot continues reaction 0.5h；
(5) being transferred to be acidified in still after continuing to filter, controlling temperature is 80 DEG C, and normal pressure bottom rotor type stirs, and adds while stirring
Enter the dilute hydrochloric acid of 5 weight portions, insulation reaction, until there being a large amount of white solid to produce.
The invention have the benefit that 1) in diazotising still, use anchor formula agitating device, the blade of this agitating device exists
The reactant in agitator tank can be removed during rotation, maintain the mixing effect of agitator；2) the enamel material of diazotising still is prevented
Rotten effect is more preferable than general reactor, reacts, the pressure in still can be made to be slightly above external pressure in the case of pressure-fired
Dry draught head, force the moisture in external environment, dust, salt fog etc. can not invade in the shell of diazotising still, make absolutely
Edge, the working environment of shell remain clean, drying regime, extend the service life of diazotising still.
Detailed description of the invention:
By embodiment, the detailed description of the invention of the present invention is made an explanation below.
Embodiment
The synthesis technique of pyraclostrobin intermediate p-hydrochloride, its synthesis technique comprises the following steps: (1) to
Material is the interior parachloroanilinum putting into 1 weight portion of glass lined diazotising still, the hydrochloric acid of 2.5 weight portions and the water of 1.5 weight portions,
Opening anchor formula agitating device, the peripheral speed controlling anchor formula stirrer paddle outer rim is 1.5m/s, rises high reaction temperature, continues stirring
Making solid all dissolve, controlling temperature is 60 DEG C, and holding pressure is pressure-fired；(2) it is that glass lined sodium nitrite is molten to material
Add sodium nitrite and 5 weight parts waters of 2 weight portions in solving still, open anchor formula agitating device, rise high-temperature, control temperature 60
DEG C, holding pressure is pressure-fired, until sodium nitrite is all dissolved；(3) solution after dissolving in step 1 drips step 2
Sodium nitrite solution, judge terminal with starch potassium iodide paper, when after reagent paper variable color, stop dropping sodium nitrite solution, continue
Continuous stirring 1h, obtains diazo liquid standby after filtration；(4) sodium nitrite solution remaining in step 3 is transferred to material for warding off glass
In the reduction kettle of glass, slowly liter high-temperature is to 80 DEG C, opens third gear paddle agitating device, under normal pressure while stirring in reduction kettle
Diazo liquid in dropping step 3, insulation reaction 2h, after reaction terminates, the activated carbon adding 0.1 weight portion while hot continues reaction
0.5h；(5) being transferred to be acidified in still after continuing to filter, controlling temperature is 80 DEG C, and normal pressure bottom rotor type stirs, and adds 5 while stirring
The dilute hydrochloric acid of weight portion, insulation reaction, until there being a large amount of white solid to produce, it is p-hydrochloride.By above-mentioned side
The yield of the p-hydrochloride that method obtains is 92%.
Claims (1)
1. the synthesis technique of pyraclostrobin intermediate p-hydrochloride, it is characterised in that synthesis technique includes following step
Rapid:
(1) it is in glass lined diazotising still, to put into the parachloroanilinum of 1 weight portion, the hydrochloric acid of 2.5 weight portions and 1.5 weights to material
The water of amount part, opens anchor formula agitating device, and the peripheral speed controlling anchor formula stirrer paddle outer rim is 0.5-1.5m/s, raises reaction
Temperature, continues stirring and makes solid all dissolve, and controls temperature and is less than 100 DEG C, and holding pressure is pressure-fired；
(2) it is in glass lined sodium nitrite dissolution kettle, to add sodium nitrite and 5 weight parts waters of 2 weight portions to material, opens
Anchor formula agitating device, rises high-temperature, controls temperature and is less than 100 DEG C, and holding pressure is pressure-fired, until sodium nitrite is the most molten
Solve；
(3) solution after dissolving in step 1 drips the sodium nitrite solution of step 2, judges eventually with starch potassium iodide paper
Point, when, after reagent paper variable color, stopping dropping sodium nitrite solution, continues stirring 1h, obtains diazo liquid standby after filtration；
(4) sodium nitrite solution remaining in step 3 is transferred in material is glass lined reduction kettle, slowly rises high-temperature extremely
80 DEG C, opening third gear paddle agitating device, drip the diazo liquid in step 3 while stirring in reduction kettle under normal pressure, insulation is anti-
Answering 2h, after reaction terminates, the activated carbon adding 0.1 weight portion while hot continues reaction 0.5h；
(5) being transferred to be acidified in still after continuing to filter, controlling temperature is 80 DEG C, and normal pressure bottom rotor type stirs, and adds 5 weights while stirring
The dilute hydrochloric acid of amount part, insulation reaction, until there being a large amount of white solid to produce.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610524996.5A CN106187811A (en) | 2016-07-02 | 2016-07-02 | The synthesis technique of pyraclostrobin intermediate p-hydrochloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610524996.5A CN106187811A (en) | 2016-07-02 | 2016-07-02 | The synthesis technique of pyraclostrobin intermediate p-hydrochloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106187811A true CN106187811A (en) | 2016-12-07 |
Family
ID=57465292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610524996.5A Pending CN106187811A (en) | 2016-07-02 | 2016-07-02 | The synthesis technique of pyraclostrobin intermediate p-hydrochloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106187811A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573256A (en) * | 2017-09-26 | 2018-01-12 | 安徽国星生物化学有限公司 | A kind of p-hydrochloride continuous production method and its device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993044A (en) * | 2012-12-31 | 2013-03-27 | 天津市天川化工有限公司 | Preparation method of 4-chlorophenylhydrazine hydrochloride |
-
2016
- 2016-07-02 CN CN201610524996.5A patent/CN106187811A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993044A (en) * | 2012-12-31 | 2013-03-27 | 天津市天川化工有限公司 | Preparation method of 4-chlorophenylhydrazine hydrochloride |
Non-Patent Citations (1)
| Title |
|---|
| 钱盛超: "三氯苯肼的合成工艺", 《宁波化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573256A (en) * | 2017-09-26 | 2018-01-12 | 安徽国星生物化学有限公司 | A kind of p-hydrochloride continuous production method and its device |
| CN107573256B (en) * | 2017-09-26 | 2020-02-21 | 安徽国星生物化学有限公司 | Continuous production method and device for p-chlorophenylhydrazine hydrochloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102766050A (en) | Method for synthesizing dimethyl fumarate | |
| CN105541845A (en) | Folic-acid cleaning production technology | |
| CN103819375B (en) | A kind of synthetic method of high-purity solid Sodium Dimethyldithiocarbamate | |
| CN109320413A (en) | A kind of preparation method of phenylacetic acid class compound | |
| CN106187811A (en) | The synthesis technique of pyraclostrobin intermediate p-hydrochloride | |
| CN103193611B (en) | A kind of synthetic method of (TrifluoroMethyl)acetophenone | |
| CN102898328B (en) | Synthesis method of diethyl azodicarboxylate and intermediate of diethyl azodicarboxylate | |
| CN103717580A (en) | Method for preparing amino-triazolinone | |
| CN101391969B (en) | Method for preparing N-methyl-2-(2,4-dichlorophenoxy) acetamide | |
| CN105837452B (en) | 2- methyl-5-nitro phenol production process | |
| CN107793295A (en) | A kind of preparation method of 3,5 difluorophenol | |
| CN106496031B (en) | A method of improving dimethyl malenate yield | |
| CN101575301B (en) | Preparation method of 2-amino-5-chlorobenzamide | |
| CN106496068B (en) | The preparation method of dimethyl malenate | |
| CN101671281A (en) | Method for extracting oxime compounds from cymoxanil mother liquor wastewater to synthesize cymoxanil | |
| CN106957240A (en) | Hydroxypropyl azanol and its synthetic method | |
| CN103073520B (en) | Method for synthesizing 2-phenyl benzothiazole and derivative thereof | |
| CN104402837B (en) | A kind of preparation method of herbicide hexazinone | |
| CN103193724B (en) | A kind of UV light absorber 2, the preparation method of 2 '-methylene radical two [6-(2H-benzotriazole-2-the base)-4-tertiary butyl] phenol | |
| CN101570519A (en) | Preparation method of 1, 2-benzisothiazolin-3-ketone | |
| CN105859559A (en) | Production method of 3-ethoxy-4-nitrophenol | |
| CN102093291B (en) | Preparation method of N-[4-(triethyl aminomethyl) benzoyl] caprolactam bromide | |
| CN104672180A (en) | Chiral preparation method of [(1S)-3-methyl-1-[[(2R)-2-methylepoxyethyl]carbonyl]butyl]tert-butyl carbamate | |
| CN103739421B (en) | 1,1-diphenyl ethylene derivatives and preparation method thereof | |
| CN110305065A (en) | Bromochloroin continuous production equipment and production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161207 |
|
| RJ01 | Rejection of invention patent application after publication |