CN104592101A - New synthesis method of sodium 3,5,6-trichloropyridyl-2-alkoxide - Google Patents
New synthesis method of sodium 3,5,6-trichloropyridyl-2-alkoxide Download PDFInfo
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- CN104592101A CN104592101A CN201510014543.3A CN201510014543A CN104592101A CN 104592101 A CN104592101 A CN 104592101A CN 201510014543 A CN201510014543 A CN 201510014543A CN 104592101 A CN104592101 A CN 104592101A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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Abstract
The invention relates to the field of fine chemical engineering, and particularly provides a new synthesis technique of sodium 3,5,6-trichloropyridyl-2-alkoxide, which comprises the following steps: by using trichloro-acetic chloride and acrylonitrile as raw materials, carrying out one-step addition cyclization under the actions of a specific solvent and a specific catalyst to obtain 3,3,5,6-tetrachloro-4,4-dihydropyridyl-2-one, filtering, desolventizing, crystallizing, and carrying out alkali resolution to obtain the sodium 3,5,6-trichloropyridyl-2-alkoxide. The method has the characteristics of low production cost, short process, small wastewater amount, higher reaction yield and the like, and is suitable for industrial production.
Description
Technical field
The present invention relates to field of fine chemical, a kind of synthetic method of 3,5,6-trichloropyridine-2-sodium alkoxide newly is specifically provided
Background technology
3,5,6-trichloropyridine-2-sodium alkoxide, molecular formula C5HONCl3Na, molecular weight 220.5, sterling is white solid, be a kind of important industrial chemicals, be mainly used in the main intermediate of the kind synthesis such as low toxicity, wide spectrum, the organic insecticidal miticide Chlorpyrifos 94 of low residue and chlorpyrifos_methyl.
The synthetic method of 3,5,6-trichloropyridine-2-sodium alkoxide, divides according to adopted starting raw material, mainly contains pyridine method and the large route of cyclization method two.Pyridine method comprises pyridine liquid phase chlorination method and pyridine gas-phase chlorination, and the sodium alkoxide yield of pyridine liquid phase chlorination method is low, consumes a large amount of solvent, is not suitable for industrialized production.The sodium alkoxide yield of pyridine gas-phase chlorination is high, and up to more than 80%, but pyroreaction operation easier is comparatively large, and fixed bed reaction technology domestic is at present immature.Cyclization method is divided by raw material and is mainly divided into trichoroacetic chloride method, trichoroacetic acid(TCA) phenyl ester method and propylene acid system.First propylene acid system will prepare acrylate chloride, and synthesis step is many, and route is long, and reaction process also will add valuable catalyst organophosphorus, organotin, is not suitable for the large production of industry.Trichoroacetic acid(TCA) phenyl ester method needs a large amount of valuable solvent sulfolanes, and by product not easily reclaims, and productive rate is lower, also not easily scale operation.Trichoroacetic chloride method raw material is easy to get, and low price, does not have particular requirement to processing condition, simple to operate, is convenient to scale operation.But adopt the yield of trichoroacetic chloride method synthesis trichloro pyridyl sodium alcoholate lower at present.
Technical problem to be solved by this invention there is provided a kind of trichoroacetic chloride single stage method and prepares 3,5,6-trichloropyridine-2-sodium phenolate, this method not only production cost is low, flow process is short, and efficiently solve the problem that addition cyclization single stage method by-product is many, wastewater flow rate is large, environmental pollution is large, simultaneously the selectivity of trichloro pyridyl sodium alcoholate and yield are all effectively improved.
Summary of the invention
The object of this invention is to provide a kind of trichoroacetic chloride single stage method and prepare 3,5,6-trichloropyridine-2-sodium phenolate, can efficiently solve the problem that addition cyclization single stage method by-product is many, wastewater flow rate is large, environmental pollution is large, and simultaneously the selectivity of trichloro pyridyl sodium alcoholate and yield are all effectively improved.
The object of the invention is to be achieved through the following technical solutions:
A kind of synthetic method of 3,5,6-trichloropyridine-2-sodium alkoxide newly, its feature comprises following step:
(1) fresh trichoroacetic chloride, vinyl cyanide, solvent are mixed in certain proportion, stir 30-60 minute, under the effect of cuprous chloride, copper powder, and by addition reaction 12-30h under reflux conditions, addition reaction temperature is 100 DEG C ~ 140 DEG C, be cooled to 80 DEG C again and add special catalyst A, cyclization 4-8h is obtained by reacting pyridone dilute solution; Described trichoroacetic chloride, the mol ratio of vinyl cyanide are 1:1.05-1.5; The mass ratio of trichoroacetic chloride, solvent and cuprous chloride is 1:2.0-5.0:0.002-0.008; The mass ratio of cuprous chloride and copper powder is 1:0.5-1.5; Described special catalyst A is selected from the one in trialkylamine, pyridine, lutidine or metal chloride, and described cuprous chloride and the mol ratio of catalyst A are 1:0.5-1.5;
(2) pyridone dilute solution is filtered out catalyzer, then by underpressure distillation, reclaim unreacted raw material and partial solvent, mother liquor is pyridone strong solution;
(3) pyridone strong solution is mixed with a certain amount of solvent B, slowly drip liquid caustic soda to it after stirring and regulate PH=10-12, control temperature is at 20 DEG C-50 DEG C, and drip and terminate rear 38-42 DEG C of insulation 6h, the mass ratio of trichoroacetic chloride, solvent B is 1:2.0-2.5;
(4) alkali is analysed liquid and be down to 20 DEG C, obtain 3,5,6-trichloropyridine-2-sodium phenolate by press filtration.
In step (1), solvent used is selected from any one or the multiple arbitrary combination in Benzene Chloride, orthodichlorobenzene, butylacetate, o-Xylol, p-Xylol, dimethyl formamide.
Described solvent B in step (3) be selected from Benzene Chloride, orthodichlorobenzene, butylacetate, o-Xylol, p-Xylol, dimethyl formamide and their aqueous solution thereof, pure water any one.
Liquid caustic soda in step (3) is the NaOH solution of 10%-30% content.。
The step that the present invention adopts specifically can be carried out as follows:
(1) addition and cyclization: fresh tribromo-acetyl, vinyl cyanide, specific solvent are mixed in certain proportion, stir 30-60 minute, under the effect of CuCl, copper powder, and by addition reaction 12-30h under reflux conditions, be cooled to 80 DEG C again and add special catalyst A, cyclization 4-8h is obtained by reacting pyridone dilute solution;
(2) precipitation: pyridone dilute solution is filtered out catalyzer, then by underpressure distillation, reclaim unreacted raw material and partial solvent, mother liquor is pyridone strong solution;
(3) aromizing: mixed with a certain amount of solvent B by pyridone, slowly drips liquid caustic soda to it after stirring and regulates PH=10-12, and control temperature, at 20 DEG C-50, drips and terminates rear 40 DEG C of insulation 6h;
(4) alkali is analysed near 20 DEG C of liquid, obtain 3,5,6-trichloropyridine-2-sodium phenolate by press filtration.
Technical characteristics of the present invention:
The present invention increases a temperature-fall period and carries out ring-closure reaction again after addition reaction terminates, and under can avoiding high temperature like this, cyclisation product kinetics produces 4 chloro pyridine, and water and HCl form strong acid, accelerate the generation of side reaction, cause sodium alkoxide yield lower.Special catalyst A mainly trialkylamine, pyridine, lutidine or the metal chloride simultaneously introduced after addition terminates to lower the temperature.Can cause the generation of ring-closure reaction after special catalyst A adds system, the HCl that ring-closure reaction is produced simultaneously is the catalyzer of ring-closure reaction, impels thoroughly carrying out of ring-closure reaction.
Under normal pressure, addition cyclization single stage method adds temperature-fall period after addition reaction terminates, and introduce special catalyst, effectively reduces the generation of by-product, effectively improves the selectivity of trichoroacetic chloride, thus make the yield of trichloro pyridyl sodium alcoholate reach more than 75%.
Embodiment
embodiment 1:
In the enamel glass reactor of 3000L, add 546Kg trichoroacetic chloride, 190.8kg vinyl cyanide, 1638kg Benzene Chloride, 2.73Kg cuprous chloride, 5.46Kg copper powder, back flow reaction temperature controls at 100 DEG C-125 DEG C, and reaction 30h, after addition reaction terminates, cool to 80 DEG C, add 2.73g trialkylamine, react 4 hours, after reaction terminates, filter out catalyzer, filtrate takes off 3/4 under negative pressure-0.8 ~-0.9Mpa.Then residual solution being discharged to alkali analyses in still, analyses in still add 1000L water to alkali, stirs 30 minutes, drip the NaOH solution of 20%, control temperature of reaction and be no more than 50 DEG C, adjust PH=11,40 DEG C are incubated 6 hours, and be then cooled to 20 DEG C of filtrations and obtain trichloro pyridyl sodium alcoholate, yield is 78%.
embodiment 2:
In the enamel glass reactor of 3000L, add 546Kg trichoroacetic chloride, 190.8kg vinyl cyanide, 1965kg orthodichlorobenzene, 2.73Kg cuprous chloride, 5.46Kg copper powder, back flow reaction temperature controls at 100 DEG C-140 DEG C, reaction 15h, after addition reaction terminates, cool to 80 DEG C, add 4.65gZnCl
2, react 4 hours, after reaction terminates, filter out catalyzer, filtrate takes off 3/4 under negative pressure-0.8 ~-0.9Mpa.Then residual solution being discharged to alkali analyses in still, analyses in still add 1000L water to alkali, stirs 30 minutes, drip the NaOH solution of 30%, control temperature of reaction and be no more than 50 DEG C, adjust PH=11,40 DEG C are incubated 6 hours, and be then cooled to 20 DEG C of filtrations and obtain trichloro pyridyl sodium alcoholate, yield is 75%.
embodiment 3:
In the enamel glass reactor of 3000L, add 546Kg trichoroacetic chloride, 190.8kg vinyl cyanide, 1965kg orthodichlorobenzene, 2.73Kg cuprous chloride, 5.46Kg copper powder, back flow reaction temperature controls at 100 DEG C-140 DEG C, reaction 15h, after addition reaction terminates, cool to 80 DEG C, add 4.9gAlCl
3, react 4 hours, after reaction terminates, filter out catalyzer, filtrate takes off 3/4 under negative pressure-0.8 ~-0.9Mpa.Then residual solution being discharged to alkali analyses in still, analyses in still add 1000L water to alkali, stirs 30 minutes, drip the NaOH solution of 30%, control temperature of reaction and be no more than 50 DEG C, adjust PH=11,40 DEG C are incubated 6 hours, and be then cooled to 20 DEG C of filtrations and obtain trichloro pyridyl sodium alcoholate, yield is 77%.
embodiment 4:
In the enamel glass reactor of 3000L, add 546Kg trichoroacetic chloride, 190.8kg vinyl cyanide, 1965kg orthodichlorobenzene, 2.73Kg cuprous chloride, 5.46Kg copper powder, back flow reaction temperature controls at 100 DEG C-140 DEG C, reaction 15h, after addition reaction terminates, cool to 80 DEG C, add 4.9gAlCl
3, react 4 hours, after reaction terminates, filter out catalyzer, filtrate takes off 3/4 under negative pressure-0.8 ~-0.9Mpa.Then residual solution being discharged to alkali analyses in still, analyse in still to alkali and add 500L water and 500Kg orthodichlorobenzene, stir 30 minutes, drip the NaOH solution of 30%, control temperature of reaction and be no more than 50 DEG C, adjust PH=11,40 DEG C are incubated 6 hours, then be cooled to 20 DEG C of filtrations and obtain trichloro pyridyl sodium alcoholate, yield is 75.8%.
embodiment 5:
In the enamel glass reactor of 3000L, add 546Kg trichoroacetic chloride, 190.8kg vinyl cyanide, 1965kg orthodichlorobenzene, 2.73Kg cuprous chloride, 5.46Kg copper powder, back flow reaction temperature controls at 100 DEG C-140 DEG C, reaction 15h, after addition reaction terminates, cool to 80 DEG C, add 4.65gZnCl
2, react 4 hours, after reaction terminates, filter out catalyzer, filtrate takes off 3/4 under negative pressure-0.8 ~-0.9Mpa.Then residual solution being discharged to alkali analyses in still, analyses in still add 1000Kg orthodichlorobenzene to alkali, stirs 30 minutes, drip the NaOH solution of 30%, control temperature of reaction and be no more than 50 DEG C, adjust PH=11,40 DEG C are incubated 6 hours, and be then cooled to 20 DEG C of filtrations and obtain trichloro pyridyl sodium alcoholate, yield is 75.0%.
embodiment 6:
In the enamel glass reactor of 3000L, add 546Kg trichoroacetic chloride, 190.8kg vinyl cyanide, 1965kg dimethyl methyl acid amide, 2.73Kg cuprous chloride, 5.46Kg copper powder, back flow reaction temperature controls at 100 DEG C-140 DEG C, and reaction 15h, after addition reaction terminates, cool to 80 DEG C, add 4.65gZnCl
2, react 4 hours, after reaction terminates, filter out catalyzer, filtrate takes off 3/4 under negative pressure-0.8 ~-0.9Mpa.Then residual solution being discharged to alkali analyses in still, analyses in still add 1000Kg water to alkali, stirs 30 minutes, drip the NaOH solution of 30%, control temperature of reaction and be no more than 50 DEG C, adjust PH=11,40 DEG C are incubated 6 hours, and be then cooled to 20 DEG C of filtrations and obtain trichloro pyridyl sodium alcoholate, yield is 77%.
Claims (4)
1. the synthetic method of new 3,5,6-trichloropyridine-2-sodium alkoxide, its feature comprises following step:
(1) fresh trichoroacetic chloride, vinyl cyanide, solvent are mixed in certain proportion, stir 30-60 minute, under the effect of cuprous chloride, copper powder, and by addition reaction 12-30h under reflux conditions, addition reaction temperature is 100 DEG C ~ 140 DEG C, be cooled to 80 DEG C again and add special catalyst A, cyclization 4-8h is obtained by reacting pyridone dilute solution; Described trichoroacetic chloride, the mol ratio of vinyl cyanide are 1:1.05-1.5; The mass ratio of trichoroacetic chloride, solvent and cuprous chloride is 1:2.0-5.0:0.002-0.008; The mass ratio of cuprous chloride and copper powder is 1:0.5-1.5; Described special catalyst A is selected from the one in trialkylamine, pyridine, lutidine or metal chloride, and described cuprous chloride and the mol ratio of catalyst A are 1:0.5-1.5;
(2) pyridone dilute solution is filtered out catalyzer, then by underpressure distillation, reclaim unreacted raw material and partial solvent, mother liquor is pyridone strong solution;
(3) pyridone strong solution is mixed with a certain amount of solvent B, slowly drip liquid caustic soda to it after stirring and regulate PH=10-12, control temperature is at 20 DEG C-50 DEG C, and drip and terminate rear 38-42 DEG C of insulation 6h, the mass ratio of trichoroacetic chloride, solvent B is 1:2.0-2.5;
(4) alkali is analysed liquid and be down to 20 DEG C, obtain 3,5,6-trichloropyridine-2-sodium phenolate by press filtration.
2. as claimed in claim 1 new 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that: in step (1), solvent used is selected from any one or the multiple arbitrary combination in Benzene Chloride, orthodichlorobenzene, butylacetate, o-Xylol, p-Xylol, dimethyl formamide.
3. as claimed in claim 1 new 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that: the described solvent B in step (3) be selected from Benzene Chloride, orthodichlorobenzene, butylacetate, o-Xylol, p-Xylol, dimethyl formamide and their aqueous solution thereof, pure water any one.
4. the synthetic method of 3,5,6-new as claimed in claim 1 trichloropyridine-2-sodium alkoxide, is characterized in that: the liquid caustic soda in step (3) is the NaOH solution of 10%-30% content.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330597A (en) * | 2015-10-27 | 2016-02-17 | 安徽国星生物化学有限公司 | Solvent-free method for synthesizing sodium 3,5,6-trichloropyridin-2-ol with one-pot method |
| CN106366127A (en) * | 2016-08-26 | 2017-02-01 | 湖北犇星农化有限责任公司 | One-pot method for synthesizing chlorpyrifos |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR8703983A (en) * | 1987-06-05 | 1989-02-14 | Martinuzzi Enzo Amadeo | PROCESS FOR THE SYNTHESIS OF 2-HYDROXY-3,5,6-TRYCHLOROPYRIDINE |
| CN102993237A (en) * | 2012-12-12 | 2013-03-27 | 江苏琦衡农化科技有限公司 | Aqueous-phase synthesis method of chlorpyrifos by using trichloro-acetic chloride as initial material |
| CN104177290A (en) * | 2014-07-23 | 2014-12-03 | 安徽国星生物化学有限公司 | New synthesis technique of 3,5,6-trichloropyridyl-2-sodium alkoxide |
-
2015
- 2015-01-13 CN CN201510014543.3A patent/CN104592101A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR8703983A (en) * | 1987-06-05 | 1989-02-14 | Martinuzzi Enzo Amadeo | PROCESS FOR THE SYNTHESIS OF 2-HYDROXY-3,5,6-TRYCHLOROPYRIDINE |
| CN102993237A (en) * | 2012-12-12 | 2013-03-27 | 江苏琦衡农化科技有限公司 | Aqueous-phase synthesis method of chlorpyrifos by using trichloro-acetic chloride as initial material |
| CN104177290A (en) * | 2014-07-23 | 2014-12-03 | 安徽国星生物化学有限公司 | New synthesis technique of 3,5,6-trichloropyridyl-2-sodium alkoxide |
Non-Patent Citations (1)
| Title |
|---|
| 金炼铁: "三氯吡啶酚及其钠盐的合成", 《精细化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330597A (en) * | 2015-10-27 | 2016-02-17 | 安徽国星生物化学有限公司 | Solvent-free method for synthesizing sodium 3,5,6-trichloropyridin-2-ol with one-pot method |
| CN106366127A (en) * | 2016-08-26 | 2017-02-01 | 湖北犇星农化有限责任公司 | One-pot method for synthesizing chlorpyrifos |
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