CN105130883A - 2,2'-bipyridine, catalytic coupling synthesis method and applications thereof - Google Patents
2,2'-bipyridine, catalytic coupling synthesis method and applications thereof Download PDFInfo
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- CN105130883A CN105130883A CN201510494721.7A CN201510494721A CN105130883A CN 105130883 A CN105130883 A CN 105130883A CN 201510494721 A CN201510494721 A CN 201510494721A CN 105130883 A CN105130883 A CN 105130883A
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- pyridine
- bipyridine
- dmac
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- C—CHEMISTRY; METALLURGY
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/14—Ortho-condensed systems
Abstract
The present invention discloses 2,2'-bipyridine, a catalytic coupling synthesis method and applications thereof. According to the method, Raney nickel is adopted as a catalyst and a reaction aid is added to an autoclave to catalyze pyridine to be subjected to dehydrogenation so as to directly couple to synthesize 2,2'-bipyridine, wherein the chemical formula of the reaction aid is represented by R-X, R represents alkyl or alkoxy or amino, and X represents an alkali metal or third main group element. According to the present invention, the pyridine is adopted as the raw material and the dehydrogenation coupling is performed to obtain the 2,2'-bipyridine, such that the raw material is easy to obtain, the pyridine chlorination process is eliminated, the process is simple, the production cost is substantially reduced, the use of halogenated pyridine is avoided, the production pollution is reduced, and the environmental protection is provided; the used catalyst has the cheap price and effectively replaces the expensive precious metal so as to reduce the catalyst cost; and the reaction aid is added during the reaction process so as to effectively improve the pyridine raw material conversion rate and improve the 2,2'-bipyridine yield, and the method is suitable for factory scale production.
Description
Technical field
The invention belongs to fine chemistry industry to produce and technical field of pesticide, particularly relate to a kind of preparation method of 2,2'-dipyridyl.
Background technology
2,2'-dipyridyl is a kind of important fine chemistry industry and medicinal intermediates, and meanwhile, it or a kind of sequestrant of uniqueness, be used as to detect the part etc. of the indicator of metal ion, photosensitizers, orgnometallic catalyst.Therefore, the exploitation of this product to pyridine derived product has very important social effect and industrial applications prospect.
At present, the major industrialized production method of domestic and international 2,2'-dipyridyls has pyridine coupler method and Ullmann method.Syngenta Co., Ltd as diquat pioneer adopts pyridine coupler method synthesis 2,2'-dipyridyl, take pyridine as raw material, pyridine is direct dehydrogenation coupling synthesis 2 under metal catalyst effect, 2'-dipyridyl, wherein foreign patent US981353, GB1000656, GB1014077, GB1377213 etc. respectively with noble metal composite such as rhodium, osmium, iridium, platinum and rutheniums for catalyzer catalytic pyridine dehydrogenation coupling at high temperature under high pressure, precious metal is expensive, considerably increases production cost; Foreign patent US3053846, GB960176, GB899015, GB3152137 etc. take pyridine as raw material, adopt Soxhelt extraction agent device, investigate raney ni catalysis performance, and by adding toluene in solvent, methylcyclohexane is beneficial to product separation as mixed solvent, but can produce a large amount of waste water in production process, the man power and material of process waste water at substantial, significant cost increases, and is unfavorable for environment protection; In US4966972, GeraldL.Geo take pyridine as raw material high temperature raney ni catalysis dehydrogenation keep a part of pyridine to be in liquid state reacting in autoclave; but generate product 2; 2'-dipyridyl easily and Raney's nickel generation sequestering action and passivation occurs; transformation efficiency on average only has 20%; raw material pyridine low conversion rate; the productive rate of 2,2'-dipyridyl on average only has 17%, cannot meet the requirement of large-scale production.
Domestic manufacturer mainly adopts Ullmann method to produce 2,2'-dipyridyl, and namely 2-haloperidid dehalogenation linked reaction under metal catalytic effect generates 2,2'-dipyridyl.Although improve the productive rate of 2,2'-dipyridyl, the raw material 2-haloperidid source difficulty that this technique uses, technical process is complicated, and metal catalyst cost recovery is high, also has certain pollution to environment.
Summary of the invention
Problem to be solved by this invention is to provide a kind of 2,2'-dipyridyl catalytic coupling synthetic method, and raw material sources are convenient, and production cost is low; simple to operation, generate without waste water in production process, environmental friendliness, improve the transformation efficiency of raw material; the productive rate of 2,2'-dipyridyl is high, is applicable to large-scale production.
One 2 of the present invention, 2'-dipyridyl catalytic coupling synthetic method, take Raney's nickel as catalyzer, reaction promoter is added in autoclave, the direct coupling synthesis 2 of catalytic pyridine dehydrogenation, 2'-dipyridyl, the chemical formulation of described reaction promoter is: R-X, R represents alkyl or alkoxyl group or amino, X represents basic metal or the 3rd main group element, be specifically as follows sec.-propyl aluminium, sodium ethylate, aluminum isopropylate and sodium amide a kind of or two or more arbitrarily mixture wherein, with sec.-propyl aluminium or sodium ethylate or aluminum isopropylate or sodium amide or their mixture for nucleophilic reagent attack pyridine 2 C-H bond, reduce the activation energy of pyridine 2 C-H bond, thus improve the yield of pyridine, reduce temperature of reaction.
Preferably, the temperature of described high-pressure catalytic reaction controls at 160 DEG C-260 DEG C, and the transformation efficiency of raw material pyridine reaches 30% substantially, is far longer than the transformation efficiency of prior art, and the selectivity of 2,2'-dipyridyl reaches more than 90% substantially.
Preferably, the mass ratio of described pyridine and Raney's nickel is 2-10:1, and the effect of pyridine, Raney's nickel selection percentage is transformation efficiency and the yield of guaranteeing pyridine.
Preferably, the manufacture craft of described catalyzer Raney's nickel is: the Raney's nickel of preparation directly adds in ready solvent DMAC, adopts Rotary Evaporators dehydration and fluid-tight preservation, to guarantee that reaction is in anhydrous state.
Preferably, described high-pressure catalytic reaction is synthesized, to guarantee that reaction is in anhydrous and oxygen-free state under nitrogen or inert gas atmosphere.
Preferably, the mol ratio of described sec.-propyl aluminium, pyridine, DMAC is: 0.1-0.4:1:1-3; The mol ratio of described sodium ethylate, pyridine, DMAC is: 0.3-1.2:1:1-3; The mol ratio of described aluminum isopropylate, pyridine, DMAC is: 0.1-0.4:1:1-3; Described sodium amide or, the mol ratio of pyridine, DMAC is: 0.3-1.2:1:1-3.
Another object of the present invention is to provide the application as diquat intermediate of 2,2'-dipyridyls that a kind of aforesaid method obtains and this product.
The invention has the beneficial effects as follows: take pyridine as raw material dehydrogenation coupling synthesis 2,2'-dipyridyl, its raw material is easy to get, eliminate pyridine chlorination process, technical process is simple, and production cost reduces greatly, avoid using 2-haloperidid simultaneously, produce to pollute and reduce, environmentally friendly; The catalyzer low price used, effectively instead of expensive noble metal, catalyzer cost has fallen; Add reaction promoter in reaction process, effectively improve the transformation efficiency of pyridine raw material, improve the productive rate of 2,2'-dipyridyl, be applicable to plant sizeization and produce.
Embodiment
In embodiment of the present invention method, the dehydrogenation coupling effect of pyridine adopts high-pressure stirring autoclave reactor to carry out catalytic performance test, and raw material and product adopt gas-chromatography to analyze.Be described in detail below in conjunction with specific embodiment.
Embodiment 1-3
522.8gDMAC, 59.3g Raney's nickel, 102.1g sodium ethylate (58.5g sodium amide or 102.1g aluminum isopropylate) is taken respectively under room temperature, 237.3g raw material pyridine adds in autoclave successively, in autoclave, pass into nitrogen for some time with air in replacement reaction kettle with the speed of 100ml/min.After being replaced, reactor is warming up to 220 DEG C, and controlling reacting kettle inner pressure is that after 0.8-1.0MPa, 12h, cooling sampling adopts gas chromatographic analysis, and data see the following form:
Embodiment 4-9
Take 522.8gDMAC respectively under room temperature, 59.3g Raney's nickel, 58.5g sodium amide, 237.3g raw material pyridine adds in autoclave successively, in autoclave, pass into nitrogen for some time with air in replacement reaction kettle with the speed of 100ml/min.After being replaced, reactor is warming up to 160 DEG C respectively, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, 260 DEG C, and controlling reacting kettle inner pressure is that after 0.8-1.0MPa, 12h, cooling sampling adopts gas chromatographic analysis, and data see the following form:
Embodiment 10-18
522.8gDMAC, 59.3g Raney's nickel, a certain amount of sodium ethylate (sodium amide or aluminum isopropylate) is taken respectively under room temperature, 237.3g raw material pyridine adds in autoclave successively, in autoclave, pass into nitrogen for some time with air in replacement reaction kettle with the speed of 100ml/min.After being replaced, reactor is warming up to 220 DEG C, and controlling reacting kettle inner pressure is that after 1.0MPa, 12h, cooling sampling adopts gas chromatographic analysis, and data see the following form:
From above three tables, data can draw, add reaction promoter in reaction process, the productive rate that the transformation efficiency of pyridine raw material improves about 10%, 2,2'-dipyridyl is increased to more than 30%, are applicable to plant sizeization completely and produce.
2, the 2'-dipyridyls that embodiments of the invention 1-18 obtains and the application of this product as diquat intermediate.
Claims (9)
1. one kind 2,2'-dipyridyl catalytic coupling synthetic method, it is characterized in that, take Raney's nickel as catalyzer, in autoclave, add reaction promoter, the direct coupling synthesis of catalytic pyridine dehydrogenation 2,2'-dipyridyl, the chemical formulation of described reaction promoter is: R-X, R represents alkyl or alkoxyl group or amino, and X represents basic metal or the 3rd main group element.
2. method according to claim 1, is characterized in that, described reaction promoter is sec.-propyl aluminium, sodium ethylate, aluminum isopropylate and sodium amide a kind of or two or more arbitrarily mixture wherein.
3. method according to claim 1, is characterized in that, the temperature of described high-pressure catalytic reaction controls at 160 DEG C-260 DEG C.
4. method according to claim 1, is characterized in that, the mass ratio of described pyridine and Raney's nickel is 2-10:1.
5. method according to claim 1, is characterized in that, the treatment process of described Raney's nickel catalyst is: the Raney's nickel of preparation directly adds in ready solvent DMAC, adopts Rotary Evaporators dehydration and fluid-tight preservation.
6. method according to claim 1, is characterized in that, the mol ratio of described sec.-propyl aluminium, pyridine, DMAC is: 0.1-0.4:1:1-3; The mol ratio of described sodium ethylate, pyridine, DMAC is: 0.3-1.2:1:1-3; The mol ratio of described aluminum isopropylate, pyridine, DMAC is: 0.1-0.4:1:1-3; Described sodium amide or, the mol ratio of pyridine, DMAC is: 0.3-1.2:1:1-3.
7. method according to claim 1, is characterized in that, described high-pressure catalytic reaction is synthesized under dry nitrogen atmosphere.
8. 2, the 2'-dipyridyls that method obtains according to any one of claim 1-7.
9. 2,2'-dipyridyls according to claim 8 are as the application of diquat intermediate.
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| CN201510494721.7A CN105130883A (en) | 2015-08-10 | 2015-08-10 | 2,2'-bipyridine, catalytic coupling synthesis method and applications thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380444A (en) * | 2016-08-17 | 2017-02-08 | 南京红太阳生物化学有限责任公司 | A method of preparing 2,2'-bipyridine |
| CN106699642A (en) * | 2017-01-16 | 2017-05-24 | 南京红太阳生物化学有限责任公司 | Method for gas phase continuous production of 2,2'-dipyridyl |
| CN106986817A (en) * | 2016-01-20 | 2017-07-28 | 张燕梅 | A kind of synthetic method of 2,2 '-bipyridyl |
| GB202106814D0 (en) | 2020-05-14 | 2021-06-30 | Johnson Matthey Plc | Catalyst for biaryl production |
| CN113385219A (en) * | 2021-06-17 | 2021-09-14 | 东南大学 | Hierarchical pore molecular sieve packaged platinum-nickel bimetallic nano catalytic material and preparation method and application thereof |
| CN114014799A (en) * | 2021-12-08 | 2022-02-08 | 安徽国星生物化学有限公司 | Production process of 2, 2-bipyridine |
| CN115245841A (en) * | 2022-08-22 | 2022-10-28 | 山东明化新材料有限公司 | Application of nickel-cobalt metal framework catalyst in preparation of 2,2' -bipyridyl |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986817A (en) * | 2016-01-20 | 2017-07-28 | 张燕梅 | A kind of synthetic method of 2,2 '-bipyridyl |
| CN106380444A (en) * | 2016-08-17 | 2017-02-08 | 南京红太阳生物化学有限责任公司 | A method of preparing 2,2'-bipyridine |
| CN106380444B (en) * | 2016-08-17 | 2018-08-28 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of 2,2 '-bipyridyls |
| CN106699642A (en) * | 2017-01-16 | 2017-05-24 | 南京红太阳生物化学有限责任公司 | Method for gas phase continuous production of 2,2'-dipyridyl |
| GB202106814D0 (en) | 2020-05-14 | 2021-06-30 | Johnson Matthey Plc | Catalyst for biaryl production |
| WO2021229227A1 (en) | 2020-05-14 | 2021-11-18 | Johnson Matthey Public Limited Company | Catalyst for biaryl production |
| GB2599981A (en) | 2020-05-14 | 2022-04-20 | Johnson Matthey Plc | Catalyst for biaryl production |
| CN113385219A (en) * | 2021-06-17 | 2021-09-14 | 东南大学 | Hierarchical pore molecular sieve packaged platinum-nickel bimetallic nano catalytic material and preparation method and application thereof |
| CN113385219B (en) * | 2021-06-17 | 2022-03-08 | 东南大学 | Hierarchical pore molecular sieve packaged platinum-nickel bimetallic nano catalytic material and preparation method and application thereof |
| CN114014799A (en) * | 2021-12-08 | 2022-02-08 | 安徽国星生物化学有限公司 | Production process of 2, 2-bipyridine |
| CN115245841A (en) * | 2022-08-22 | 2022-10-28 | 山东明化新材料有限公司 | Application of nickel-cobalt metal framework catalyst in preparation of 2,2' -bipyridyl |
| CN115245841B (en) * | 2022-08-22 | 2024-01-26 | 山东明化新材料有限公司 | Application of nickel-cobalt metal framework catalyst in preparation of 2,2' -bipyridine |
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Application publication date: 20151209 |