CN101565400A - Preparation method of 4-amino-3, 5, 6-chloropyridine-2-methanoic acid - Google Patents
Preparation method of 4-amino-3, 5, 6-chloropyridine-2-methanoic acid Download PDFInfo
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- CN101565400A CN101565400A CNA2009100842526A CN200910084252A CN101565400A CN 101565400 A CN101565400 A CN 101565400A CN A2009100842526 A CNA2009100842526 A CN A2009100842526A CN 200910084252 A CN200910084252 A CN 200910084252A CN 101565400 A CN101565400 A CN 101565400A
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Abstract
The invention provides a preparation method of 4-amino-3, 5, 6-chloropyridine-2-methanoic acid, which adopts 3, 4, 5, 6-tetrachloropyridine carbonitrile as a starting material, and obtains 4-amino-3, 5, 6-chloropyridine-2-carbonitrile by adding ammonia gas or liquid ammonia for ammonolysis reaction under the action of a catalyst; and then obtains the 4-amino-3, 5, 6-chloropyridine-2-methanoic acid by hydrolysis reaction, with the total yield of 70 to 80 percent. The preparation method has the advantages of safe and simple operation, less discharge of the three wastes, being environment-friendly and the like. Particularly, the ammonolysis reaction is conducted at normal temperature and normal pressure, the adopted solvents are safe and low in toxicity, excess ammonia and solvents after full reaction can be recycled for application; and the post-treatment operation is simple, thus being easy for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of organic compound weedicide, specifically, relate to a kind of 4-amino-3,5, the preparation method of 6-trichloropyridine-2-formic acid.
Background technology
4-amino-3,5,6-trichloropyridine-2-formic acid (Picloram, poison is elegant fixed) is the weedicide of a kind of new type of safe, high-efficiency low-toxicity.
According to the literature, 4-amino-3,5, the preparation method of 6-trichloropyridine-2-formic acid mainly contains following three kinds:
1, as among the SU445662, be starting raw material with the heptachlor picoline, through ammonia separate, the synthetic target product that obtains of hydrolysis two-step reaction; Because the heptachlor picoline is difficult to obtain, cause that raw materials cost is too high, product market competitiveness is poor.
2, as US4336384, BR8202369, among the AU8344982, with 3,4,5,6-4 chloro pyridine formonitrile HCN is a starting raw material, through ammonia separate, the synthetic target product that obtains of hydrolysis two-step reaction; Wherein, use ammoniacal liquor during ammonolysis reaction, when the consumption of ammoniacal liquor was more than 60 times of starting raw material, ammonia hydrolysis products yield only was 70%; Thereby produce a large amount of waste water, run counter to the production theory of energy-saving and emission-reduction.
3, as among the CN100443471C, with 3,4,5,6-4 chloro pyridine formic acid is the synthetic target product that obtains of starting raw material; Owing to be under condition of high voltage, to react, there is certain potential safety hazard.
Because at aspects such as safety in production, environment protection and production costs, there is certain deficiency in prior art in varying degrees, is necessary to carry out Technology and improves.
Summary of the invention
The objective of the invention is to overcome the deficiency of aforesaid method, a kind of preparation 4-amino-3,5 is provided, the method for 6-trichloropyridine-2-formic acid, advantage such as it has reaction yield height, operational safety, production cost is low, wastewater discharge is few, environmentally friendly.
For realizing the object of the invention, 4-amino-3,5 of the present invention, the preparation method of 6-trichloropyridine-2-formic acid, it adopts with 3,4,5, and 6-4 chloro pyridine formonitrile HCN (hereinafter to be referred as: the 4 chloro pyridine nitrile) be starting raw material, under catalyst action, add ammonia or liquefied ammonia and carry out ammonolysis reaction and obtain 4-amino-3,5, and 6-trichloropyridine-2-formonitrile HCN (hereinafter to be referred as: the aminopyridine nitrile); Obtain target product 4-amino-3,5 through hydrolysis reaction then, 6-trichloropyridine-2-formic acid.
Chemical reaction process of the present invention is as follows:
Wherein: the mol ratio of 4 chloro pyridine nitrile and liquefied ammonia/ammonia is 1: 5～30, preferred 1: 10～15.Described catalyzer is cuprous chloride, cupric chloride, copper 8-quinolinolate or its mixture, and the mass ratio of 4 chloro pyridine nitrile and catalyzer is 1: 0.001～0.005, preferred 1: 0.002～0.004.
Described ammonolysis reaction carries out at normal temperatures and pressures, and the reaction times is 8～40 hours.
Described ammonolysis reaction also needs to carry out under organic solvent, and described organic solvent is ethanol, acetonitrile, Virahol or N, dinethylformamide (DMF).Described hydrolysis reaction carries out under 95～100 ℃, and the reaction times is 6～8 hours.
Can add mineral acid or mineral alkali in the described hydrolytic process.
Described mineral acid is sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid, preferably sulfuric acid; The mol ratio of aminopyridine nitrile and mineral acid is 1: 5～15, preferred 1: 10.
Described mineral alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide or magnesium hydroxide, preferred sodium hydroxide; The mol ratio of described aminopyridine nitrile and mineral alkali is 1: 1～5, preferred 1: 3.
Postprocessing working procedures such as the present invention filters behind hydrolysis reaction, washing promptly get 4-amino-3,5,6-trichloropyridine-2-formic acid.
The concrete processing step of the present invention is: add 4 chloro pyridine nitrile, catalyzer and organic solvent in reactor (bottle), logical ammonia reacted about 30 hours to required amount in the room temperature downhill reaction liquid; It is reaction end less than 0.5% that sampling detects the 4 chloro pyridine nitrile; Intensification is carried out material filtering after reclaiming unreacted ammonia, obtains the aminopyridine nitrile; Then the aminopyridine nitrile is added in the reactor (bottle), adding mineral acid or mineral alkali were 95～100 ℃ of following hydrolysis reaction 6～8 hours; It is reaction end that sampling detects aminopyridine nitrile content＜0.2%, and after reaction was finished, filtration, washing, oven dry obtained product 4-amino-3,5,6-trichloropyridine-2-formic acid, and product content is more than 98%, and total recovery reaches 70～80%.
Advantages such as the present invention prepares 4-amino-3,5, and the method for 6-trichloropyridine-2-formic acid has operational safety, simple, and three wastes discharge amount is few, and is environmentally friendly.Below the concrete advantage:
1, the present invention adopts ammonia or liquefied ammonia and 4 chloro pyridine nitrile to react under catalyst action, and the ammonolysis reaction mild condition is carried out at normal temperatures and pressures, and the solvent for use safety and low toxicity are simple to operate, meet requirement of safe production.
2, the present invention adopt pure ammonia in organic solvent with 4 chloro pyridine nitrile reaction, excess of ammonia gas with solvent absorbing after recovery set usefulness, emit no waste water, reduced the exhaust gas discharging amount, reached cleaner production, energy saving purposes.
3, hydrolysis reaction mild condition among the present invention is difficult for producing impurity, product content height, reaction yield height.
4, after hydrolysis reaction was finished among the present invention, the aftertreatment of product was simple, directly reduces production costs.
Embodiment
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.In the embodiment explanation, symbol g=gram, the mL=milliliter, the mol=mole, ℃=degree centigrade.
Embodiment 1 4-amino-3,5, the preparation of 6-trichloropyridine-2-formonitrile HCN
In having the 500mL four-hole bottle of stirring, thermometer, dropping funnel, add 95% ethanol 250mL, stirring the slow ammonia 26g (1.5mol, 99.9%) of feeding under the cooling state.After logical ammonia finishes, add 4 chloro pyridine nitrile 25.47g (0.1mol, 95%) and catalyzer cuprous chloride 0.06g; Reaction is 30 hours under the room temperature.It is qualified that sampling detects 4 chloro pyridine nitrile content＜0.5%, filters out product; Obtain 18.3g 4-amino-3,5 after washing, oven dry, 6-trichloropyridine-2-formonitrile HCN, yield are 80.1%.
Embodiment 2 4-amino-3,5, the preparation of 6-trichloropyridine-2-formonitrile HCN
In having the 500mL four-hole bottle of stirring, thermometer, dropping funnel, add acetonitrile 250mL, stirring the slow ammonia 12g (0.7mol, 99.9%) of feeding under the cooling state.After logical ammonia finishes, add 4 chloro pyridine nitrile 25.47g (0.1mol, 95%) and catalyzer cuprous chloride 0.05g and copper 8-quinolinolate 0.05g; Reaction is 30 hours under the room temperature, and it is qualified that sampling detects 4 chloro pyridine nitrile content＜0.5%, filters out product; Obtain 17.2g4-amino-3,5 after washing, oven dry, 6-trichloropyridine-2-formonitrile HCN, yield are 75.1%.
Embodiment 3 4-amino-3,5, the preparation of 6-trichloropyridine-2-formonitrile HCN
In having the 500mL four-hole bottle of stirring, thermometer, dropping funnel, add Virahol 250mL, stirring the slow liquefied ammonia 26g (1.5mol, 99.9%) of feeding under the cooling state.After logical ammonia finishes, add 4 chloro pyridine nitrile 25.47g (0.1mol, 95%) and catalyzer cupric chloride 0.05g; Reaction is 30 hours under the room temperature, and it is qualified that sampling detects 4 chloro pyridine nitrile content＜0.5%, filters out product; Obtain 17.5g 4-amino-3,5 after washing, oven dry, 6-trichloropyridine-2-formonitrile HCN, yield are 77.4%.
Embodiment 4 4-amino-3,5, the preparation of 6-trichloropyridine-2-formonitrile HCN
In having the 500mL four-hole bottle of stirring, thermometer, dropping funnel, add DMF150mL, stirring the slow ammonia 17g (1mol, 99.9%) of feeding under the cooling state.After logical ammonia finishes, add 4 chloro pyridine nitrile 25.47g (0.1mol, 95%) and catalyzer copper 8-quinolinolate 0.05g, reaction is 30 hours under the room temperature; It is qualified that sampling detects 4 chloro pyridine nitrile content＜0.5%, filters out product; Obtain 16.4g 4-amino-3,5 after washing, oven dry, 6-trichloropyridine-2-formonitrile HCN, yield are 71.5%.
Embodiment 5 4-amino-3,5, the preparation of 6-trichloropyridine-2-formic acid
In having the 500mL four-hole bottle of stirring, thermometer, dropping funnel, add entry 51mL, under whipped state, slowly be added dropwise to sulfuric acid 100g (1mol, 98%); Add the back and add 4-amino-3,5,6-trichloropyridine-2-formonitrile HCN 23.3g (0.1mol, 95%) is warming up to 95 ℃, is incubated in 95～100 ℃ and reacts 6 hours down.It is qualified that sampling detects aminopyridine nitrile content＜0.2%; Be cooled to 40 ℃, be added dropwise to 200mL water, restir 15 minutes obtains 22.8g 4-amino-3,5 after filtering, wash, drying, and 6-trichloropyridine-2-formic acid, yield are 94.0%.
Embodiment 6 4-amino-3,5, the preparation of 6-trichloropyridine-2-formic acid
In having the 500mL four-hole bottle of stirring, thermometer, dropping funnel, add entry 16mL, under whipped state, slowly be added dropwise to sulfuric acid 100g (1mol, 98%); Add the back and add 4-amino-3,5,6-trichloropyridine-2-formonitrile HCN 23.3g (0.1mol, 95%) is warming up to 95 ℃, is incubated in 95～100 ℃ and reacts 8 hours down.It is qualified that sampling detects aminopyridine nitrile content＜0.2%, is cooled to 40 ℃, is added dropwise to 250mL water, and restir 15 minutes obtains 23.2g 4-amino-3,5 after filtering, wash, drying, and 6-trichloropyridine-2-formic acid, yield are 94.8%.
Embodiment 7 4-amino-3,5, the preparation of 6-trichloropyridine-2-formic acid
In having the 500mL four-hole bottle of stirring, thermometer, dropping funnel, add entry 120mL, whipped state adds liquid caustic soda 40g (0.3mol, 30% aqueous sodium hydroxide solution) down; Add the back and add 4-amino-3,5,6-trichloropyridine-2-formonitrile HCN 23.3g (0.1mol, 95%) is warming up to 95 ℃, is incubated in 95～100 ℃ and reacts 8 hours down.It is qualified that sampling detects aminopyridine nitrile content＜0.2%, is cooled to 30 ℃, be added dropwise to the dilute hydrochloric acid acidifying after, stirred 15 minutes, obtain 23.5g 4-amino-3,5 after filtering, wash, drying, 6-trichloropyridine-2-formic acid, yield are 96.5%.
Embodiment 8 4-amino-3,5, the preparation of 6-trichloropyridine-2-formic acid
In having the 500mL four-hole bottle of stirring, thermometer, dropping funnel, add entry 200mL, whipped state adds potassium hydroxide 18.26g (0.3mol, 92%) down; Add the back and add 4-amino-3,5,6-trichloropyridine-2-formonitrile HCN 23.3g (0.1mol, 95%) is warming up to 95 ℃, is incubated in 95～100 ℃ and reacts 6 hours down.It is qualified that sampling detects aminopyridine nitrile content＜0.2%, is cooled to 30 ℃, be added dropwise to the dilute hydrochloric acid acidifying after, restir 15 minutes filters, washing, obtains 23.1g 4-amino-3,5 after drying, 6-trichloropyridine-2-formic acid, yield are 95.4%.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. 4-amino-3,5, the preparation method of 6-trichloropyridine-2-formic acid is characterized in that, it adopts with 3,4,5, and 6-4 chloro pyridine formonitrile HCN is a starting raw material, under catalyst action, add ammonia or liquefied ammonia and carry out ammonolysis reaction and obtain 4-amino-3,5,6-trichloropyridine-2-formonitrile HCN; Obtain target product 4-amino-3,5 through hydrolysis reaction then, 6-trichloropyridine-2-formic acid.
2. method according to claim 1 is characterized in that, and is described 3,4,5, and the mol ratio of 6-4 chloro pyridine formonitrile HCN and ammonia/liquefied ammonia is 1: 5～30, preferred 1: 10～15.
3. method according to claim 1 and 2, it is characterized in that, described catalyzer is the compound of copper-containing metal, be preferably cupric chloride, cuprous chloride, copper 8-quinolinolate or its mixture, 3,4,5, the mass ratio of 6-4 chloro pyridine formonitrile HCN and catalyzer is 1: 0.001～0.005, preferred 1: 0.002～0.004.
4. according to any described method of claim 1-3, it is characterized in that described ammonolysis reaction carries out at normal temperatures and pressures, the reaction times is 8～40 hours
5. according to any described method of claim 1-4, it is characterized in that described ammonolysis reaction also needs to carry out under organic solvent, described organic solvent is ethanol, acetonitrile, Virahol or N, dinethylformamide.
6. according to any described method of claim 1-5, it is characterized in that described hydrolysis reaction carries out under 95～100 ℃, the reaction times is 6～8 hours.
7. according to any described method of claim 1-6, it is characterized in that, add mineral acid or mineral alkali in the described hydrolytic process.
8. method according to claim 7 is characterized in that, described mineral acid is sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid, preferably sulfuric acid; 4-amino-3,5, the mol ratio of 6-trichloropyridine-2-formonitrile HCN and mineral acid is 1: 5～15, preferred 1: 10.
9. method according to claim 7 is characterized in that, described mineral alkali is sodium hydroxide, potassium hydroxide, calcium hydroxide or magnesium hydroxide, preferred sodium hydroxide; Described 4-amino-3,5, the mol ratio of 6-trichloropyridine-2-formonitrile HCN and mineral alkali is 1: 1～5, preferred 1: 3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106854178A (en) * | 2015-12-09 | 2017-06-16 | 湖南比德生化科技股份有限公司 | A kind of method that picloram is separated and recovered in the ammonium salt waste residue from picloram |
| CN113015721A (en) * | 2018-09-19 | 2021-06-22 | 科迪华农业科技有限责任公司 | Preparation of picloram halogen analogs |
| 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 |
-
2009
- 2009-05-15 CN CN2009100842526A patent/CN101565400B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN106854178A (en) * | 2015-12-09 | 2017-06-16 | 湖南比德生化科技股份有限公司 | A kind of method that picloram is separated and recovered in the ammonium salt waste residue from picloram |
| CN106854178B (en) * | 2015-12-09 | 2019-04-30 | 湖南比德生化科技股份有限公司 | A method of separating and recovering picloram from picloram ammonium salt waste residue |
| CN113015721A (en) * | 2018-09-19 | 2021-06-22 | 科迪华农业科技有限责任公司 | Preparation of picloram halogen analogs |
| 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 |
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