CN102174014B - Preparation method of 3-chloropyridine - Google Patents
Preparation method of 3-chloropyridine Download PDFInfo
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- CN102174014B CN102174014B CN2011100596872A CN201110059687A CN102174014B CN 102174014 B CN102174014 B CN 102174014B CN 2011100596872 A CN2011100596872 A CN 2011100596872A CN 201110059687 A CN201110059687 A CN 201110059687A CN 102174014 B CN102174014 B CN 102174014B
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Abstract
The invention discloses a preparation method of 3-chloropyridine. 3-chloropyridine is a fine chemical engineering intermediate extensively used in the fields of medicine and pesticides. The preparation method comprises the following steps of: taking 2,6-dichloropyridine as a raw material and performing chlorination reaction to obtain 2,3,6-trichloropyridine; putting the 2,3,6-trichloropyridine, an acid-binding agent, a metal catalyst and an organic solvent into a reactor for performing hydrogenation reaction, wherein the mol ratio of the 2,3,6-trichloropyridine to the acid-binding agent is 1:(0.5-1.0); cooling the hydrogenation reaction liquid, adding water to dissolve the hydrochlorate of the acid-binding agent, filtering and standing to separate the water layer; extracting the organic solvent layer by aqueous acid at least more than three times; combining the extracted aqueous acid layers, thinning up with water, alkalizing for adjusting the pH value of the filtrate to be 7; and layering the filtrate to obtain the liquid product of 3-chloropyridine. The preparation method of 3-chloropyridine has a novel process route, short reaction steps, simplicity of operation, high yield, low production cost and environmental friendliness, and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of chemical synthesis process, relate in particular to a kind of preparation method who is widely used in the important fine-chemical intermediate 3-chloropyridine of medicine and pesticide field.
Background technology
The 3-chloropyridine is a kind of important fine-chemical intermediate, and it is widely used in medicine and pesticide field.
Synthetic method about the 3-chloropyridine:
Ciamician.Dennstedt is at Chemische Berichte, and 1882, vol.15 discloses a series of synthetic methods with preparation 3-chloropyridines such as pyrroles, carbon trichloride or tetracol phenixin in p.1179.
Wibaut.Nicolai is at Recueil des Travaux Chimiques des Pays-Bas, and 1939, vol.58 adopts the synthetic 3-chloropyridine of method of pyridine direct chlorination in p.709-721, and still, this preparation method's by product is more.
Raeth is at Justus Liebigs Annalen der Chemie, and 1931, vol.486 has introduced take the 3-aminopyridine as raw material in p.95, and the synthetic 3-chloropyridine of method that diazotization is hydrolyzed chloro again occurs in hydrochloric acid, copper powder, Sodium Nitrite.
But the preparation of 3-chloropyridine is mainly all that to be hydrolyzed the method for chloro take the 3-aminopyridine as starting raw material through chloro, diazotization synthetic again in above-mentioned prior art, and the synthetic method step is more; Production cost take the 3-aminopyridine as starting raw material is also higher; A large amount of waste liquid environmental pollutions that diazotization, chlorination operation produce are serious, restricted the suitability for industrialized production scale of 3-chloropyridine.
Summary of the invention
In view of this, for the cost of material that exists in the preparation method who solves above-mentioned existing 3-chloropyridine high, synthesis step is more, the problems such as reaction type complexity, the invention provides a kind of raw material cheap and easy to get, simple process, yield is high and environmentally friendly, is suitable for the new preparation method of the 3-chloropyridine of suitability for industrialized production.
The preparation method of a kind of 3-chloropyridine of the present invention comprises the steps
A, chlorination reaction: be raw material with 2,6-dichloropyridine, and heat up after catalyst mix, pass into chlorine and carry out chlorination reaction, question response fully after, cooling, rectification under vacuum namely get 2,3,6-trichloropyridine;
Further,
Catalyzer in described chlorination reaction is selected from a kind of common Lewis acid: sulphur trioxide, boron trifluoride, iron trichloride or aluminum chloride, the consumption of this catalyzer are 0.01～1.00 times of 2,6-dichloropyridine mole dosage, preferred 0.01～0.50 times.
Normally 50～300 ℃ of temperature in described chlorination reaction, preferred 100～200 ℃.
The lower concentration distillate that produces in rectifying in described chlorination reaction also can be applied mechanically to lower batch and again react or apply mechanically to lower batch of rectification and purification again.
B, hydrogenation: with gained 2,3,6-trichloropyridine and acid binding agent, metal catalyst, organic solvent are thrown to reactor, are under 0～10MPa in pressure range, pass into hydrogen after intensification and carry out hydrogenation, and recording reaction solution pH is 4～8 o'clock, stop logical hydrogen.The mol ratio of 2,3,6-trichloropyridine and acid binding agent is 1: 0.5～1.0, preferred 1: 0.7～1.0.Preferred 0～the 5MPa of the pressure range of hydrogenation.Normally 20～200 ℃ of temperature of reaction in hydrogenation, preferred 20～150 ℃.
Further,
Acid binding agent in described hydrogenation is selected from organic bases or inorganic alkali compound.Described organo-alkali compound is selected from a kind of in alkaline metal salt, metal alkylide lithium compound or the amido lithium compound of pyridine, triethylamine, alcohol, preferred pyridine or triethylamine.
Wherein, the alkaline metal salt of alcohol is selected from a kind of in sodium methylate, potassium ethylate or potassium tert.-butoxide; The metal alkylide lithium compound is selected from a kind of in butyllithium or phenyl lithium; The amido lithium compound is selected from lithium diisopropyl amido or hexamethyldisilazane lithium; Described alkali-metal oxyhydroxide class is selected from sodium hydroxide or potassium hydroxide; Alkali-metal carbonate and bicarbonate salts are selected from a kind of in sodium carbonate, salt of wormwood, sodium bicarbonate or saleratus; Acetates is selected from sodium acetate or potassium acetate.Described inorganic alkali compound is selected from a kind of in alkali-metal oxyhydroxide class, alkali-metal carbonate and bicarbonate salts, Acetates.
Metal catalyst in described hydrogenation is selected from a kind of in single-metal reforming catalyst, multimetallic catalyst, loading type or non-loading type metal catalyst.Described single-metal reforming catalyst is selected from a kind of in platinum, palladium, cobalt or nickel; Described multimetallic catalyst is selected from a kind of in binary alloy catalyzer copper-nickel, copper-palladium, palladium-Yin, platinum-Jin or platinum-copper; Described load type metal catalyst is selected from platinum charcoal or palladium charcoal; Described non-loading type metal catalyst is selected from a kind of in Raney's nickel, Lei Nitong or thunder Buddhist nun cobalt, a kind of in preferred platinum charcoal, palladium charcoal, Raney's nickel or Lei Nitong.
Organic solvent in described hydrogenation is selected from a kind of in ester class, ethers, aromatic hydrocarbons, nitrile, perhaps several any mixture; Described ester class is selected from methyl acetate, ethyl acetate or butylacetate, described ethers is selected from ether, methyl tertiary butyl ether, tetrahydrofuran (THF) or Dui diox, described aromatic hydrocarbons is selected from benzene, toluene or chlorobenzene, and described nitrile is selected from acetonitrile or propionitrile, preferred toluene or ethyl acetate.
C, post-processing operation: above-mentioned reaction solution is down to room temperature, the acid binding agent hydrochloride is dissolved in water, filter, with the filtrate standing demix, after separating water layer, extract at least three time or more with aqueous acids organic solvent layer, aqueous acids is the laminated and thin up that gets up again filters, and adds alkali and regulates filtrate pH value=7 o'clock, with the filtrate layering, namely get 3-chloropyridine liquid product.
Further,
Recyclable the applying mechanically of catalyzer that described post-processing operation filters out in being dissolved in water after the acid binding agent hydrochloride.
Organic solvent layer in described post-processing operation is by adding the also lower batch raw material of recyclable conduct of 2,3,6-trichloropyridine and organic solvent.
Aqueous acids in described aftertreatment behaviour is selected from a kind of in water-soluble mineral acid or organic acid; Mineral acid is selected from a kind of in hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid or nitric acid; Organic acid is selected from the low-grade carboxylic acid: a kind of in formic acid, acetic acid, propionic acid, butanic acid or positive valeric acid.
Aqueous acids in described post-processing operation and 2,3,6-trichloropyridine mol ratio are 1～5: 1.
Further, the organic acid in described post-processing operation also can be selected from Whitfield's ointment or Phenylsulfonic acid.
(see Fig. 1) in reaction formula of the present invention: be starting raw material with 2,6-dichloropyridine, pass into chlorine generation chlorination reaction, obtain 2,3,6-trichloropyridine, then 2,3,6-trichloropyridine hydrogenating reduction is prepared the 3-chloropyridine.This shows, operational path of the present invention is novel simple, and adopts the high efficiency separation recovery technology, and is environmentally friendly when reducing production costs.It is a friendly process that adapts to suitability for industrialized production.
Description of drawings
Fig. 1 is reaction formula figure of the present invention.
The invention will be further described with way of example again for the below, provides implementation detail of the present invention, but be not to be intended to limit protection scope of the present invention.
Embodiment
Embodiment 1
Chlorination reaction
Take 2,6-dichloropyridine 1480.0g and anhydrous FeCl
3Heat up after the four-hole boiling flask of 2000ml mixes 89.2g be placed in, when reaching 120～140 ℃, temperature passes into chlorine, after question response is abundant, be cooled to 100 ℃, rectification under vacuum, in-0.1MPa, collect product cut under 118～124 ℃ of top temperature, the lower concentration distillate that produces in rectifying also can be applied mechanically to lower batch and again react or apply mechanically to lower batch of rectification and purification again.Apply mechanically rear 2,3, the 6-trichloropyridine 1715.0g that finally obtains, applying mechanically rear total recovery is 94.0%, purity 〉=99.5%.
Hydrogenation
With make in chlorination reaction 2,3,6-trichloropyridine 557.8g, triethylamine 232.0g, palladium charcoal 8.5g, toluene 1675g are disposable throws to reactor, be warming up to 60～80 ℃, pass into hydrogen and carry out hydrogenation, the pH that records reaction solution is 4～8 o'clock, stop logical hydrogen, hydrogenation finishes.
Post-processing operation
Above-mentioned reaction solution is down to room temperature, adds water 790g dissolving triethylamine hydrochloride, filter, add entry 30g and toluene 30g washing leaching cake, filter cake is the palladium charcoal.The filtrate standing demix is removed water layer; With layering after 200g hcl as extraction agent three times, solution after extraction is by adding 2,3,6-trichloropyridine and toluene, capable of circulation applying mechanically to lower batch reaction, add entry 1630g dilution in hydrochloric acid after the extraction, filter, then water 100g washing (recyclable the applying mechanically to extraction stages of waste water that produces after washing), add alkali and regulate filtrate pH for neutral, layering obtains the 3-chloropyridine.Applying mechanically rear product total mass is 297.2g, and yield is 85.6%, purity 〉=99.5%.
Embodiment 2
Chlorination reaction
Take the cut liquid 533.7g (wherein 2, the 6-dichloropyridine accounts for 86.1%, 2,3,6-trichloropyridine and accounts for 9%) of 2,6-dichloropyridine 299.2g and recovery, with anhydrous AlCl
336.5g being placed in reactor mixes, pass into chlorine when being warmed up to 120～140 ℃, after question response is complete, be cooled to 100 ℃, rectification under vacuum, in-0.1MPa, collect product cut under 118～124 ℃ of top temperature, the lower concentration product that steams can be applied mechanically to lower batch and again react or apply mechanically to lower batch of rectification and purification again; Apply mechanically rear 2,3, the 6-trichloropyridine 890.7g that finally obtains, applying mechanically rear total recovery is 95.2%, purity 〉=99.5%.
Hydrogenation
Can be with the toluene solution 1340g that contains 2,3,6-trichloropyridine that reclaims in embodiment 1, add again 2,3,6-trichloropyridine 410.5g, and toluene 348g, amount to 2,3,6-trichloropyridine 562.7g, the palladium charcoal 5.6g of pyridine 195.0g, recovery, the disposable throwing to reactor, be warming up to 60～80 ℃, logical hydrogen reaction, survey pH are 4～8 and stop logical hydrogen, the hydrogenation end.
Post-processing operation
Above-mentioned reaction solution is down to room temperature, adds water 800g dissolving pyridine hydrochloride, filter, add entry 30g and toluene 30g washing leaching cake, filter cake is the palladium charcoal.The filtrate standing demix is removed water layer; With layering after 200g hcl as extraction agent three times, toluene after extraction is by adding 2,3,6-trichloropyridine and toluene, capable of circulation applying mechanically to lower batch reaction, add entry 1650g dilution in hydrochloric acid after the extraction, filter, then water 120g washing (recyclable the applying mechanically to extraction stages of waste water that produces after washing), add alkali and regulate filtrate pH for neutral, layering obtains the 3-chloropyridine.Applying mechanically rear product total mass is 290.9g, and yield is 83.2%, purity 〉=99.5%.
Claims (8)
1. the preparation method of a 3-chloropyridine, is characterized in that: comprise the steps
(1) chlorination reaction: be raw material with 2,6-dichloropyridine, and heat up after catalyst mix, pass into chlorine and carry out chlorination reaction, question response fully after, cooling, rectification under vacuum namely get 2,3,6-trichloropyridine; Catalyzer in described chlorination reaction is selected from sulphur trioxide, boron trifluoride, iron trichloride or aluminum chloride;
(2) hydrogenation: with gained 2,3,6-trichloropyridine and acid binding agent, metal catalyst, organic solvent are thrown to reactor, be under 0-l0MPa in pressure range, pass into hydrogen after intensification and carry out hydrogenation, recording reaction solution pH is 4～8 o'clock, stops logical hydrogen; Described 2,3, the mol ratio of 6-trichloropyridine and acid binding agent is 1:0.5～1.0; Described acid binding agent is selected from pyridine, triethylamine, alkali-metal oxyhydroxide class, a kind of in alkali-metal carbonate and bicarbonate salts; Described metal catalyst is selected from platinum charcoal, palladium charcoal, Raney's nickel or thunder Buddhist nun cobalt; Described organic solvent is selected from a kind of in ethyl acetate, butylacetate, methyl tertiary butyl ether, Dui diox and toluene, perhaps several any mixture; Temperature of reaction in described hydrogenation is 20-150 ℃;
(3) post-processing operation: above-mentioned reaction solution is down to room temperature, the acid binding agent hydrochloride is dissolved in water, filter, with the filtrate standing demix, after separating water layer, extract at least three time or more with aqueous acids organic solvent layer, laminated and the thin up that gets up of aqueous acids after extracting again, filter, add alkali and regulate filtrate pH value=7 o'clock, will namely get 3-chloropyridine liquid product after the filtrate layering.
2. preparation method described according to claim l is characterized in that:
The consumption of the catalyzer in described chlorination reaction is 0.01-1.00 times of 2,6-dichloropyridine mole dosage;
Temperature in described chlorination reaction is 100-200 ℃;
The lower concentration distillate that produces in rectifying in described chlorination reaction also can be applied mechanically to lower batch and again react or apply mechanically to lower batch of rectification and purification again.
3. preparation method according to claim 2 is characterized in that:
The consumption of the catalyzer in described chlorination reaction is 0.01-0.50 times of 2,6-dichloropyridine mole dosage.
4. preparation method according to claim 1, it is characterized in that: described alkali-metal oxyhydroxide class is selected from sodium hydroxide or potassium hydroxide; Described alkali-metal carbonate and bicarbonate salts are selected from a kind of in sodium carbonate, salt of wormwood, sodium bicarbonate or saleratus.
5. according to claim 1 or 4 described preparation methods is characterized in that:
Described acid binding agent is selected from pyridine or triethylamine;
Described metal catalyst is selected from a kind of in platinum charcoal, palladium charcoal or Raney's nickel;
Described organic solvent is selected from toluene or ethyl acetate.
6. preparation method according to claim 1 is characterized in that:
Pressure range in described hydrogenation is 0-5MPa;
In described hydrogenation 2,3, the mol ratio of 6-trichloropyridine and acid binding agent are 1:0.7-1.0.
7. preparation method described according to claim l is characterized in that:
Be dissolved in water in described post-processing operation after the acid binding agent hydrochloride, the catalyzer that filters out is recyclable to be applied mechanically;
Organic solvent layer in described post-processing operation is by adding the also lower batch raw material of recyclable conduct of 2,3,6-trichloropyridine and organic solvent;
Aqueous acids in described post-processing operation is selected from a kind of in water-soluble mineral acid or organic acid; Mineral acid is selected from a kind of in hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid or nitric acid; Organic acid is selected from a kind of in formic acid, acetic acid, propionic acid, butanic acid or positive valeric acid;
Described aqueous acids and 2,3,6-trichloropyridine mol ratio are l～5:1.
8. preparation method according to claim 7, it is characterized in that: described organic acid also is selected from Whitfield's ointment or Phenylsulfonic acid.
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| CN103145609B (en) * | 2013-03-05 | 2015-08-05 | 衢州恒顺化工有限公司 | A kind of preparation method of 2,3-dichloropyridine |
| CN108484492A (en) * | 2018-05-23 | 2018-09-04 | 安徽国星生物化学有限公司 | Niacinamide synthesizes the technical study of 2,3,6- trichloropyridines |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515953A (en) * | 1983-04-22 | 1985-05-07 | Kalama Chemical, Inc. | Production of polychlorinated pyridine mixtures by liquid phase chlorination of pyridine or pyridine hydrochloride |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515953A (en) * | 1983-04-22 | 1985-05-07 | Kalama Chemical, Inc. | Production of polychlorinated pyridine mixtures by liquid phase chlorination of pyridine or pyridine hydrochloride |
Non-Patent Citations (5)
| Title |
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| Jacqueline E.，等.An Extremely Active Catalyst for the Negishi Cross-Coupling Reaction.《J. AM. CHEM. SOC.》.2004,第126卷(第40期),第13028-13032页. * |
| 吡啶衍生物及其催化闭环法合成;魏优昌;《精细与专用化学品》;20060906;第14卷(第17期);第1-9页，具体参见第6页图7 * |
| 蒋德超,等.氯代吡啶化合物的研究应用与展望.《精细化工中间体》.2010,第40卷(第5期),第13-16页,具体参见第14页第14页第二栏. * |
| 陈煦，等.2,3,6-三氯吡啶的合成.《精细石油化工》.2000,(第3期),第38-40页. * |
| 魏优昌.吡啶衍生物及其催化闭环法合成.《精细与专用化学品》.2006,第14卷(第17期),第1-9页，具体参见第6页图7. |
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