CN103030594A - Synthesis method of 2,2'-dipyridyl - Google Patents
Synthesis method of 2,2'-dipyridyl Download PDFInfo
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- CN103030594A CN103030594A CN2012105289288A CN201210528928A CN103030594A CN 103030594 A CN103030594 A CN 103030594A CN 2012105289288 A CN2012105289288 A CN 2012105289288A CN 201210528928 A CN201210528928 A CN 201210528928A CN 103030594 A CN103030594 A CN 103030594A
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- dipyridyl
- alkaline hydrolysis
- toluene
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- chloropyridine
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Abstract
The invention discloses a synthesis method of 2,2'-dipyridyl, mainly comprising the following steps of: coupling 2-chloropyridine as a raw material under the catalysis effect of a catalyst to obtain 2,2'-dipyridyl; screening an alkaline hydrolysis reagent and an auxiliary agent, which have the better advantage, by selecting the alkaline hydrolysis reagent and the auxiliary agent, to carry out alkaline hydrolysis; and finally, carrying out steps of extraction, acid washing, second time of alkaline hydrolysis, second time of acid washing, alkaline hydrolysis and the like to obtain refined 2,2'-dipyridyl. The method disclosed by the invention is simple; the production cost is greatly reduced and the reaction yield is improved; and meanwhile, a process flow is further optimized.
Description
Technical field
The invention belongs to chemical industry and pesticide field, be specifically related to a kind of 2, the novel process that the 2'-dipyridyl is synthetic.
Background technology
2,2'-dipyridyl is one of dipyridyl isomer, is a kind of important organic synthesis intermediate, is mainly used in medicine intermediate, organic synthesis etc.Simultaneously, it also is a kind of widely used sequestrant, paint additive, is widely used in the aspects such as DYE PRODUCTION, pesticide producing and spices.Therefore, it is synthesized and the research of industrialization aspect will have great importance.
The traditional method Raney's nickel of synthetic 2,2'-dipyridyl is that catalyzer is synthetic take pyridine as raw material.The catalyst life of this method is shorter, should not recycle, and also can't satisfy the requirement in the production.
Take the dihalo-pyridine as raw material, synthesizing 2,2'-dipyridyl with composite catalyst becomes the main method of producing at present 2,2'-dipyridyl both at home and abroad.Therefore, seem particularly important for the optimization of whole technical process and the control of cost.
Summary of the invention
The present invention from optimization technological process, reduce production costs, the energy-conserving and environment-protective equal angles, proposed a kind of 2,2'-dipyridyl synthetic method.
To achieve these goals, the present invention adopts following technical scheme:
A kind of 2, the synthetic method of 2'-dipyridyl is characterized in that: concrete steps are:
(1) coupling: add successively 2-chloropyridine, solvent DMAC, catalyzer triphenylphosphine, zinc powder, nickelous chloride, Varion CDG-K in the reactor, be warming up to 60-100 ℃, insulation reaction 2-3h, then sampling analysis, wherein 2-chloropyridine: solvent DMAC: catalyzer triphenylphosphine: zinc powder: the mass ratio of nickelous chloride, Varion CDG-K is=125-130:250-300:70-75:60-70:5-10:3-4;
(2) precipitation: step (1) is through sampling analysis, and when 2-chloropyridine content＜0.5%, reaction finishes, and the control temperature is 100-130 ℃, and solvent DMAC is deviate from decompression, gets solid matter;
(3) alkaline hydrolysis: the sodium hydroxide solution and the bicarbonate of ammonia that add 10-12% in step (2) the gained solid matter are warming up to 65-70 ℃, alkaline hydrolysis 3-4h, adding dimethylbenzene, toluene obtained alkali solution liquid after alkaline hydrolysis was finished, and wherein the mass ratio of 2-chloropyridine is 900-1000:150-250:900-1000:125-130:50-60 in sodium hydroxide solution, bicarbonate of ammonia, dimethylbenzene, toluene and the step (1);
(4) extraction: with the press filtration of step (3) gained alkali solution liquid, filtrate is through the extraction of separatory, toluene, separatory obtains water and toluene mutually again;
(5) pickling: step (4) gained toluene is added to 10-12% chlorohydric acid pickling, separatory that 2-3 doubly measures obtains water and toluene mutually;
(6), absorption: add the modification infusorial earth that is equivalent to water weight 3-4% to aqueous phase, leave standstill after 2-3 hour and leach water; Described modification infusorial earth adopt diatomite through 500-560 ℃ lower sintering 3-4 hour, then, soak 1-2 hour through the 10-15% aqueous hydrochloric acid after, washing, oven dry obtain;
(7) acidolysis, alkaline hydrolysis: step (6) gained water is added appropriate hydrochloric acid solution regulate pH=3-4, left standstill 10-15 minute, add again an amount of sodium hydroxide solution and regulate pH=10-11, get secondary 2,2 '-dipyridyl crude product through press filtration;
(8) refining: with step (7) gained 2,2 '-dipyridyl crude product adds an amount of washing, press filtration, it is refining 2 to be drying to obtain, 2 '-dipyridyl.
Beneficial effect of the present invention:
Whole process flow process of the present invention is simple, reaction yield is higher, production cost is lower, environmental friendliness.Adopt gained 2 of the present invention, the yield of 2 '-dipyridyl can be brought up to by original 85% present more than 95%.
Embodiment
A kind of 2, the synthetic method of 2'-dipyridyl, concrete steps are:
(1) coupling: add successively 2-chloropyridine, solvent DMAC, catalyzer triphenylphosphine, zinc powder, nickelous chloride, Varion CDG-K in the reactor, be warming up to 60-70 ℃, insulation reaction 3h, then sampling analysis, wherein 2-chloropyridine: solvent DMAC: catalyzer triphenylphosphine: zinc powder: the mass ratio of nickelous chloride, Varion CDG-K is=125:300:70:60:5:3;
(2) precipitation: step (1) is through sampling analysis, and when 2-chloropyridine content＜0.5%, reaction finishes, and the control temperature is 100-130 ℃, and solvent DMAC is deviate from decompression, filters, and gets solid matter;
(3) alkaline hydrolysis: the sodium hydroxide solution and the bicarbonate of ammonia that add 10-12% in step (2) the gained solid matter are warming up to 65-70 ℃, alkaline hydrolysis 3-4h, adding dimethylbenzene, toluene obtained alkali solution liquid after alkaline hydrolysis was finished, and wherein the mass ratio of 2-chloropyridine is 1000:250:900:130:50 in sodium hydroxide solution, bicarbonate of ammonia, dimethylbenzene, toluene and the step (1);
(4) extraction: with the press filtration of step (3) gained alkali solution liquid, filtrate is through the extraction of separatory, toluene, separatory obtains water and toluene mutually again;
(5) pickling: 10-12% chlorohydric acid pickling, the separatory that step (4) gained toluene is added to 3 times of volumes obtains water and toluene mutually;
(6), absorption: add the modification infusorial earth that is equivalent to water weight 4% to aqueous phase, leave standstill after 2-3 hour and leach water; Described modification infusorial earth adopt diatomite through 500-560 ℃ lower sintering 3-4 hour, then, soak 1-2 hour through the 10-15% aqueous hydrochloric acid after, washing, oven dry obtain;
(7) acidolysis, alkaline hydrolysis: step (6) gained water is added appropriate hydrochloric acid solution regulate pH=3, left standstill 10-15 minute, add again an amount of sodium hydroxide solution and regulate pH=10-11, get secondary 2,2 '-dipyridyl crude product through press filtration;
(8) refining: with step (7) gained 2,2 '-dipyridyl crude product adds an amount of washing, press filtration, it is refining 2 to be drying to obtain, 2 '-dipyridyl.
Through measuring and calculating, gained 2 of the present invention, the yield of 2 '-dipyridyl can be brought up to by 85% of traditional technology present more than 95%.
Claims (1)
1. one kind 2, the synthetic method of 2'-dipyridyl is characterized in that: concrete steps are:
(1) coupling: add successively 2-chloropyridine, solvent DMAC, catalyzer triphenylphosphine, zinc powder, nickelous chloride, Varion CDG-K in the reactor, be warming up to 60-100 ℃, insulation reaction 2-3h, then sampling analysis, wherein 2-chloropyridine: solvent DMAC: catalyzer triphenylphosphine: zinc powder: the mass ratio of nickelous chloride, Varion CDG-K is=125-130:250-300:70-75:60-70:5-10:3-4;
(2) precipitation: step (1) is through sampling analysis, and when 2-chloropyridine content＜0.5%, reaction finishes, and the control temperature is 100-130 ℃, and solvent DMAC is deviate from decompression, gets solid matter;
(3) alkaline hydrolysis: the sodium hydroxide solution and the bicarbonate of ammonia that add 10-12% in step (2) the gained solid matter are warming up to 65-70 ℃, alkaline hydrolysis 3-4h, adding dimethylbenzene, toluene obtained alkali solution liquid after alkaline hydrolysis was finished, and wherein the mass ratio of 2-chloropyridine is 900-1000:150-250:900-1000:125-130:50-60 in sodium hydroxide solution, bicarbonate of ammonia, dimethylbenzene, toluene and the step (1);
(4) extraction: with the press filtration of step (3) gained alkali solution liquid, filtrate is through the extraction of separatory, toluene, separatory obtains water and toluene mutually again;
(5) pickling: step (4) gained toluene is added to 10-12% chlorohydric acid pickling, separatory that 2-3 doubly measures obtains water and toluene mutually;
(6), absorption: add the modification infusorial earth that is equivalent to water weight 3-4% to aqueous phase, leave standstill after 2-3 hour and leach water; Described modification infusorial earth adopt diatomite through 500-560 ℃ lower sintering 3-4 hour, then, soak 1-2 hour through the 10-15% aqueous hydrochloric acid after, washing, oven dry obtain;
(7) acidolysis, alkaline hydrolysis: step (6) gained water is added appropriate hydrochloric acid solution regulate pH=3-4, left standstill 10-15 minute, add again an amount of sodium hydroxide solution and regulate pH=10-11, get secondary 2,2 '-dipyridyl crude product through press filtration;
(8) refining: with step (7) gained 2,2 '-dipyridyl crude product adds an amount of washing, press filtration, it is refining 2 to be drying to obtain, 2 '-dipyridyl.
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| CN2012105289288A CN103030594A (en) | 2012-12-11 | 2012-12-11 | Synthesis method of 2,2'-dipyridyl |
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| CN2012105289288A CN103030594A (en) | 2012-12-11 | 2012-12-11 | Synthesis method of 2,2'-dipyridyl |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151231A (en) * | 2014-09-11 | 2014-11-19 | 利尔化学股份有限公司 | Preparation method of 2, 2'-bipyridyl |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230950A (en) * | 1997-05-22 | 1999-10-06 | 三得利株式会社 | Method of production and method of separation of 2,4'-dipyridyl derivatives and methods of production of benzoxazepine derivatives and salts thereof |
| JP2006022012A (en) * | 2004-07-06 | 2006-01-26 | Koei Chem Co Ltd | Method for producing 4, 4'-dicarboxy-2, 2'-bipyridine |
| WO2009025160A1 (en) * | 2007-08-20 | 2009-02-26 | Sumitomo Chemical Company, Limited | Transition metal complex and process for producing conjugated aromatic compound with the transition metal complex |
| WO2012029411A1 (en) * | 2010-08-31 | 2012-03-08 | 住友化学株式会社 | Method for producing biaryl compound |
-
2012
- 2012-12-11 CN CN2012105289288A patent/CN103030594A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1230950A (en) * | 1997-05-22 | 1999-10-06 | 三得利株式会社 | Method of production and method of separation of 2,4'-dipyridyl derivatives and methods of production of benzoxazepine derivatives and salts thereof |
| JP2006022012A (en) * | 2004-07-06 | 2006-01-26 | Koei Chem Co Ltd | Method for producing 4, 4'-dicarboxy-2, 2'-bipyridine |
| WO2009025160A1 (en) * | 2007-08-20 | 2009-02-26 | Sumitomo Chemical Company, Limited | Transition metal complex and process for producing conjugated aromatic compound with the transition metal complex |
| WO2012029411A1 (en) * | 2010-08-31 | 2012-03-08 | 住友化学株式会社 | Method for producing biaryl compound |
Non-Patent Citations (4)
| Title |
|---|
| CHRISTOPH JANIAK,等: "Modified Bipyridines: 5,5’-Diamino-2,2’-bipyridine Metal Complexes Assembled in to Multidimensional Networks via Hydrogen Bonding andπ- π Stacking Interactions", 《EUROPEAN JOURNAL OF INORGANIC CHEMISTRY》 * |
| ISMAEL COLON,等: "Coupling of Aryl Chlorides by Nickel and Reducing Metals", 《J. ORG. CHEM.》 * |
| 吴梧桐: "《生物制药工艺学》", 28 February 2006 * |
| 陈玉岩,等: "2,2′,6,6′-四甲氧基-4,4′-二(二苯基氧膦)-3,3′-联吡啶的合成", 《精细化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151231A (en) * | 2014-09-11 | 2014-11-19 | 利尔化学股份有限公司 | Preparation method of 2, 2'-bipyridyl |
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