CN1923810A - Chemical synthesis method of 4-amino-3,5,6-trichloropyridine-2-formic acid - Google Patents
Chemical synthesis method of 4-amino-3,5,6-trichloropyridine-2-formic acid Download PDFInfo
- Publication number
- CN1923810A CN1923810A CN 200610021917 CN200610021917A CN1923810A CN 1923810 A CN1923810 A CN 1923810A CN 200610021917 CN200610021917 CN 200610021917 CN 200610021917 A CN200610021917 A CN 200610021917A CN 1923810 A CN1923810 A CN 1923810A
- Authority
- CN
- China
- Prior art keywords
- formic acid
- ammonia
- chloro pyridine
- water
- ammoniacal liquor
- 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.)
- Granted
Links
Landscapes
- Pyridine Compounds (AREA)
Abstract
The invention discloses a synthesizing method of new-typed herbicide 4-amino-3, 5, 6-trichloropyridine-2-aminic acid, which is characterized by the following: adopting 3, 4, 5, 6-tetrachloropyridine formate or tetrachloropyridine formic acid as original raw material; ammonifying; acidifying; making the total receiving rate at 75-91%.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound weedicide, 4-amino-3,5 particularly, the chemical synthesis process of 6-trichloropyridine-2-formic acid.
Background technology
4-amino-3,5,6-trichloropyridine-2-formic acid is a kind of new herbicides.Document has been reported respectively with heptachlor picoline (SU445662) and 3,4,5,6-4 chloro pyridine nitrile (US4666384, AU8344982) be raw material synthetic method, because the solvability of these two kinds of raw materials in water is poor, so in building-up process, need to add a large amount of water as solvent, and temperature of reaction and pressure are also than higher, also need react under the ammoniation agent effect of vast scale simultaneously, the ratio of ammoniation agent that has and tetrachloro cyanopyridine will reach 62.85 times can obtain 75% ammonification yield.If the ratio of ammoniation agent reduces, the yield of product just reduces significantly.The wastewater flow rate that this reaction produced simultaneously is bigger, and product cost is higher.From safety, environment protection and synthetic manufacturing cost aspect, improved necessity is arranged all.
Summary of the invention
The present invention is intended to overcome the defective of aforesaid method, provide a kind of yield higher, the operation safer, production cost is lower, wastewater discharge is less, environment amenable 4-amino-3,5, the synthetic method of 6-trichloropyridine-2-formic acid.
For achieving the above object, the technical solution used in the present invention is as follows:
4-amino-3,5, the synthetic method of 6-trichloropyridine-2-formic acid is characterized in that with 3,4,5, and 6-4 chloro pyridine formate or 4 chloro pyridine formic acid are starting raw material, separate out product after aminating reaction and acidification, and concrete processing step is:
Adding 4 chloro pyridine formic acid and water in withstand voltage reactor, is that the pH that sodium hydroxide, potassium hydroxide, bicarbonate of ammonia or the volatile salt of 10～30% (W/V) is adjusted to solution is neutrality with concentration, and 4 chloro pyridine formic acid all is converted into corresponding salt; And then add ammoniation agent and closed reactor, and be heated to 100～140 ℃ of reactions 0.5～10. hour, discharge the intact ammonia of unreacted while hot, after ammonia has discharged in the question response liquid, add the mineral acid acidification to pH 1～2, promptly get product behind the filtering drying, yield is 75～91%.
Chemical reaction process of the present invention is as follows:
The intact ammonia water of unreacted of the present invention absorbs the back and supplies recycle next time as ammoniacal liquor, i.e. utilization is reclaimed ammoniacal liquor all 4 chloro pyridine formic acid is converted into ammonium salt, and the liquefied ammonia of excess of ammonia water and follow-up adding continues reaction as ammoniation agent together and makes product.
The weight ratio of the water in described 4 chloro pyridine formic acid and water or the ammoniacal liquor is 1: 3～15.
Described ammoniation agent is ammoniacal liquor, liquefied ammonia, volatile salt or bicarbonate of ammonia, preferred liquefied ammonia.
The mol ratio of described 4 chloro pyridine formic acid and ammoniation agent is 1: 5～49.
Described mineral acid is hydrochloric acid, rare nitric acid or dilute sulphuric acid.
Beneficial effect of the present invention shows:
1, the present invention adopts water miscible 4 chloro pyridine formate or 4 chloro pyridine formic acid as raw material, has reduced temperature of reaction, and is lower to the requirement of equipment, the security that has improved building-up process.
2, the present invention adopts water miscible 4 chloro pyridine formate or 4 chloro pyridine formic acid as raw material, and the solvability of its product in water improves, and the add-on of reaction water consumption and ammoniation agent all significantly reduces.
3, the present invention adopts water miscible 4 chloro pyridine formate or 4 chloro pyridine formic acid as raw material, makes the reaction times reduce, and has improved combined coefficient.
4, the present invention adopts water miscible 4 chloro pyridine formate or 4 chloro pyridine formic acid as raw material, and reaction yield has obtained effective raising, and the product cost is reduced.
Embodiment
Embodiment 1
In the withstand voltage reactor of 1000ml, add sodium hydroxide 12.8g (0.3mol) and 750ml water, stirring and dissolving adds 4 chloro pyridine formic acid 83.1g (0.32mol then, 94.2%), adding 150g liquefied ammonia (8.82mol) again, is under the airtight condition of 110～125 ℃, reactor in temperature, stirring reaction 2.0 hours, after finishing, reaction emits unnecessary ammonia, add hcl acidifying again and handle to pH 1～2, filter dry by the fire in after the 70.6g product, yield is 91.3%.
Embodiment 2
In the autoclave of 1000ml, add potassium hydroxide 13.8g (0.3mol) and 750ml water, stirring and dissolving adds 4 chloro pyridine formic acid 83.1g (0.32mol then, 94.2%), adding 150g liquefied ammonia (8.82mol) again, is under the airtight condition of 110～120 ℃, reactor in temperature, stirring reaction 2.5 hours, after finishing, reaction emits unnecessary ammonia, add hcl acidifying again and handle, get 68.8g product, yield 89% behind the filtering drying to pH 1～2.
Embodiment 3
In the autoclave of 1000ml, add 750ml water, add 4 chloro pyridine formic acid 83.1g (0.32mol, 94.2%) then, add 320g volatile salt (3.3mol) again, in temperature is under the airtight condition of 120～130 ℃, reactor, stirring reaction 3.0 hours after reaction is finished, adds hcl acidifying again and handles to pH 1～2, promptly get the 67.2g product behind the filtering drying, yield is 87%.
Embodiment 4
In the autoclave of 1000ml, adding absorbs the ammoniacal liquor 750ml (17%) behind the unnecessary ammonia, add 4 chloro pyridine formic acid 83.1g (0.3mol, 94.2%) then, add 120g liquefied ammonia (7.06mol) again, in temperature is under the airtight condition of 125～130 ℃, reactor, stirring reaction 2 hours is emitted unnecessary ammonia after reaction is finished, and adds the dilute sulphuric acid acidification again to pH 1～2, promptly get the 69.1g product behind the filtering drying, yield is 89.4%.
Claims (5)
1,4-amino-3,5, the synthetic method of 6-trichloropyridine-2-formic acid is characterized in that with 3,4,5, and 6-4 chloro pyridine formate or 4 chloro pyridine formic acid are starting raw material, get product after aminating reaction and acidifying neutralizing treatment, and concrete processing step is:
Adding 4 chloro pyridine formic acid and water in withstand voltage reactor, is that the pH that 10～30% sodium hydroxide, potassium hydroxide, bicarbonate of ammonia or volatile salt are adjusted to solution is neutrality with concentration, and 4 chloro pyridine formic acid all is converted into corresponding salt; And then add ammoniation agent and closed reactor, and be heated to 100～140 ℃ of reactions 0.5～10 hour, discharge the intact ammonia of unreacted while hot, after ammonia has discharged in the question response liquid, add the mineral acid acidification to pH1～2, promptly get product behind the filtering drying, yield is 75～91%.
2, synthetic method as claimed in claim 1, it is characterized in that the intact ammonia water of described unreacted absorbs the back and supplies recycle next time as ammoniacal liquor, promptly utilize recovery ammoniacal liquor that all 4 chloro pyridine formic acid is converted into ammonium salt, the liquefied ammonia of excess of ammonia water and follow-up adding continues reaction as ammoniation agent together and makes product.
3, synthetic method as claimed in claim 1 or 2, the weight ratio that it is characterized in that the water in described 4 chloro pyridine formic acid and water or the ammoniacal liquor is 1: 5～15.
4, the method for claim 1 is characterized in that described ammoniation agent is ammoniacal liquor, liquefied ammonia, volatile salt or bicarbonate of ammonia.
5, synthetic method as claimed in claim 1, the mol ratio that it is characterized in that described 4 chloro pyridine formic acid and ammoniation agent is 1: 5～49.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100219175A CN100443471C (en) | 2006-09-22 | 2006-09-22 | Chemical synthesis method of 4-amino-3,5,6-trichloropyridine-2-formic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100219175A CN100443471C (en) | 2006-09-22 | 2006-09-22 | Chemical synthesis method of 4-amino-3,5,6-trichloropyridine-2-formic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1923810A true CN1923810A (en) | 2007-03-07 |
| CN100443471C CN100443471C (en) | 2008-12-17 |
Family
ID=37816653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100219175A Withdrawn - After Issue CN100443471C (en) | 2006-09-22 | 2006-09-22 | Chemical synthesis method of 4-amino-3,5,6-trichloropyridine-2-formic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100443471C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173994A (en) * | 2011-03-21 | 2011-09-07 | 上海帝埃碧化学科技有限公司 | Preparation method of 3,3',4,4'-tetraamino biphenyl |
| CN103497151A (en) * | 2013-10-30 | 2014-01-08 | 山东铂源药业有限公司 | Synthetic method of 4-amidogen-6-methylnicotinicacid |
| CN104628635A (en) * | 2015-02-10 | 2015-05-20 | 湖南比德生化科技有限公司 | Method for separating and purifying high-content picloram from picloram production waste residues |
| CN104649965A (en) * | 2015-02-10 | 2015-05-27 | 湖南比德生化科技有限公司 | Preparation method of 3,4,5,6-tetrachloropyridine-2-carboxylic acid |
| CN106146393A (en) * | 2015-04-14 | 2016-11-23 | 利尔化学股份有限公司 | Prepare 3,4,6-trichloropyridine-2-formic acid and the method for corresponding esters thereof |
| CN113045485A (en) * | 2021-03-22 | 2021-06-29 | 山东潍坊润丰化工股份有限公司 | Continuous production method of picloram |
| CN114702440A (en) * | 2022-04-26 | 2022-07-05 | 永农生物科学有限公司 | Preparation method of picloram and picloram prepared by same |
| CN117019069A (en) * | 2023-08-11 | 2023-11-10 | 北京弗莱明科技有限公司 | Pipeline reactor and continuous production method of 4-amino-3, 5, 6-trichloropyridine carboxylic acid |
| CN117466810A (en) * | 2023-12-26 | 2024-01-30 | 北京弗莱明科技有限公司 | Industrial continuous production method of picloram |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3285925A (en) * | 1962-03-06 | 1966-11-15 | Dow Chemical Co | Amino-trichloropicolinic acid compounds |
| SU445662A1 (en) * | 1972-12-22 | 1974-10-05 | Предприятие П/Я Г-4684 | Method for producing 4-amino-3,5,6trichloropicolinic acid |
| US4087431A (en) * | 1976-05-17 | 1978-05-02 | The Dow Chemical Company | Preparation of 3,6-dichloropicolinic acid |
| US4336384A (en) * | 1981-04-23 | 1982-06-22 | The Dow Chemical Company | Preparation of 4-amino-3,5,6-trichloropicolinic acid |
-
2006
- 2006-09-22 CN CNB2006100219175A patent/CN100443471C/en not_active Withdrawn - After Issue
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173994A (en) * | 2011-03-21 | 2011-09-07 | 上海帝埃碧化学科技有限公司 | Preparation method of 3,3',4,4'-tetraamino biphenyl |
| CN103497151A (en) * | 2013-10-30 | 2014-01-08 | 山东铂源药业有限公司 | Synthetic method of 4-amidogen-6-methylnicotinicacid |
| CN103497151B (en) * | 2013-10-30 | 2015-07-15 | 山东铂源药业有限公司 | Synthetic method of 4-amidogen-6-methylnicotinicacid |
| CN104628635A (en) * | 2015-02-10 | 2015-05-20 | 湖南比德生化科技有限公司 | Method for separating and purifying high-content picloram from picloram production waste residues |
| CN104649965A (en) * | 2015-02-10 | 2015-05-27 | 湖南比德生化科技有限公司 | Preparation method of 3,4,5,6-tetrachloropyridine-2-carboxylic acid |
| CN104628635B (en) * | 2015-02-10 | 2016-02-10 | 湖南比德生化科技有限公司 | A kind ofly produce separating-purifying waste residue from picloram and go out the method for high-content picloram |
| CN106146393A (en) * | 2015-04-14 | 2016-11-23 | 利尔化学股份有限公司 | Prepare 3,4,6-trichloropyridine-2-formic acid and the method for corresponding esters thereof |
| CN113045485A (en) * | 2021-03-22 | 2021-06-29 | 山东潍坊润丰化工股份有限公司 | Continuous production method of picloram |
| CN114702440A (en) * | 2022-04-26 | 2022-07-05 | 永农生物科学有限公司 | Preparation method of picloram and picloram prepared by same |
| CN114702440B (en) * | 2022-04-26 | 2024-06-18 | 永农生物科学有限公司 | Preparation method of picloram and picloram prepared by same |
| CN117019069A (en) * | 2023-08-11 | 2023-11-10 | 北京弗莱明科技有限公司 | Pipeline reactor and continuous production method of 4-amino-3, 5, 6-trichloropyridine carboxylic acid |
| CN117466810A (en) * | 2023-12-26 | 2024-01-30 | 北京弗莱明科技有限公司 | Industrial continuous production method of picloram |
| CN117466810B (en) * | 2023-12-26 | 2024-04-09 | 北京弗莱明科技有限公司 | Industrial continuous production method of picloram |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100443471C (en) | 2008-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1923810A (en) | Chemical synthesis method of 4-amino-3,5,6-trichloropyridine-2-formic acid | |
| CN1944408A (en) | Process for preparing symmetric tetrachloro pyridine | |
| CN102002015B (en) | Air-borne preparation method for isothiazolinone and derivants thereof | |
| CN103508938B (en) | Preparation method of N, N'-bis(2, 2, 6, 6-tetramethyl-4-piperidyl)-1, 3-benzenedicarboxamide | |
| CN105418493B (en) | A kind of synthetic method of 2 chloropyridine | |
| CN101735153A (en) | Production technology of carbendazim | |
| CN109232411B (en) | Method for preparing boscalid | |
| CN103588682B (en) | Preparation method of 1, 3-diamino guanidine hydrochloride | |
| CN101880262B (en) | Preparation method of 2-thiazolidine ketone | |
| CN108912043B (en) | Synthetic method of 2,3, 5-trichloropyridine | |
| CN101565400B (en) | Preparation method of 4-amino-3, 5, 6-chloropyridine-2-methanoic acid | |
| CN105418494A (en) | Preparation method of clodinafop propargyl | |
| CN106749071B (en) | A kind of preparation method of aromatics 1,2,4,5- tetrazine compound | |
| JP2019130468A (en) | Manufacturing method of platinum compound-containing composition, and manufacturing method of hexahydroxoplatinic acid (iv) as raw material therefor | |
| CN104513198A (en) | 2-chloronicotinic acid synthetic method | |
| CN109896942A (en) | A kind of preparation method of alpha-alcohol ketone photoinitiator | |
| CN108358835B (en) | Preparation method of 2,3, 5-trichloropyridine | |
| CN110818603A (en) | Preparation method of methomyl oxime | |
| CN1277811C (en) | Production process and use of chlorobromoisocyanuric acid | |
| CN112159349B (en) | Synthetic method of 2,3, 5-trichloropyridine | |
| CN101659605A (en) | Method for synthesizing o-hydroxy benzophenone-rare earth coordination compound | |
| CN106565532A (en) | Synthetic method of substituted phenyl diazene compound and application of synthetic method | |
| EP1902042A1 (en) | Process for preparing 3,4-dichloroisothiazolecarboxylic acid | |
| CN112142603A (en) | Preparation method of 2, 4, 6-trichloroaniline | |
| KR20040111675A (en) | Production process of aminomethyl group-containing benzamide compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| AV01 | Patent right actively abandoned | ||
| AV01 | Patent right actively abandoned |
Granted publication date: 20081217 Effective date of abandoning: 20200220 |