WO2017181514A1 - Procédé de synthèse pour de la 2,2'-dipyridine utilisant un nanocatalyseur bimétallique à support - Google Patents

Procédé de synthèse pour de la 2,2'-dipyridine utilisant un nanocatalyseur bimétallique à support Download PDF

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WO2017181514A1
WO2017181514A1 PCT/CN2016/086353 CN2016086353W WO2017181514A1 WO 2017181514 A1 WO2017181514 A1 WO 2017181514A1 CN 2016086353 W CN2016086353 W CN 2016086353W WO 2017181514 A1 WO2017181514 A1 WO 2017181514A1
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reaction
catalyst
pyridine
autoclave
bipyridine
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Chinese (zh)
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冯乙巳
刘善和
韦永飞
王红伟
方红新
谷顺明
胡玉兵
杨红兵
周浩
吴德清
王光宇
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Anhui Costar Biochemical Co Ltd
Hefei University of Technology
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Anhui Costar Biochemical Co Ltd
Hefei University of Technology
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Definitions

  • the present invention relates to a method for synthesizing 2,2'-bipyridine, and more particularly to a method for directly synthesizing 2,2'-bipyridine by a pyridine direct coupling with a supported bimetallic nanocatalyst.
  • 2,2'-bipyridyl is one of the isomers of bipyridyl, and can be used as a ligand, a photosensitizer, an indicator for detecting metal ions, etc.; 2,2'-bipyridine is also an important intermediate in organic chemical production. Such as a key intermediate for the rapid production of herbicide diquat. Due to its acute toxicity, the widely used low-cost herbicide paraquat has limited application due to no specific antidote after poisoning humans and animals. Diquat herbicide is the best alternative to paraquat, and its production of 2,2'-bipyridine, the main raw material, determines its production cost. Therefore, research and development of high yield, low cost, good safety and low pollution of 2,2' bipyridyl green production technology will have important application prospects and market value.
  • bipyridyl synthetic routes have been reported at home and abroad, including pyridine carbonyl compound cyclization synthesis, halopyridine Ullmann coupling synthesis, Raney nickel catalyzed pyridine direct oxidative coupling synthesis and noble metal complex catalysis.
  • the earliest synthetic method of bipyridine was prepared by cyclization of a pyridine carbonyl compound. Beschke found in the experiment that the pyridine carbonyl compound and the ⁇ - ⁇ -unsaturated carbonyl compound can be cyclized to synthesize 2,2'-bipyridine under the action of a catalyst. Mixing 2-acetylpyridine, acrolein and ammonia in a molar ratio of 1:2:6 at 440 ° C, and producing 2,2'-bipyridine under the action of a catalyst, based on 2-acetylpyridine Up to 69%.
  • the method has high yield, the reaction temperature is too high, and the reaction is carried out under gas phase conditions, and there is a production safety hazard; the stability and catalytic efficiency of the reaction are unstable; and the pyridine carbonyl compound is expensive and difficult to obtain, so the method is Does not have industrial production value.
  • Ullmann coupling of halopyridine to synthesize 2,2'-bipyridine has matured Industrial applications.
  • the synthesis process is: pyridine is used as a raw material to convert to chloropyridine by chlorination, and then coupled to synthesize 2,2'-bipyridine.
  • the technology and process of the method are relatively mature, but the reaction synthesis route is relatively long and the production efficiency is low; the hydrogen atom on the pyridine ring is first replaced by a halogen atom, and the halogen atom is removed when the 2,2'-bipyridine is synthesized. .
  • ICI has used Raney nickel-catalyzed Ullmann coupling to synthesize 2,2'-bipyridine, which is heated under high pressure, but at a lower yield.
  • Ullmann coupling method will cause great pollution in the production process, and the product cost is relatively high, which is inconsistent with the production requirements of atomic economy and modern green chemical industry.
  • the industrially produced Raney nickel catalyst is usually stored in the aqueous phase system, and the pyridine direct coupling reaction is catalyzed. It is necessary to carry out under anhydrous conditions, and the preparation and use of the anhydrous Raney nickel catalyst is cumbersome, and there is a certain safety risk.
  • the present invention is to provide a method for efficiently synthesizing 2,2'-bipyridine by pyridine with a supported bimetallic nanocatalyst M 1 -M 2 @Al 2 O 3 in order to avoid the deficiencies of the prior art. It aims to reduce production costs and improve operational safety to suit large-scale industrial production.
  • the invention adopts a method for synthesizing 2,2'-bipyridine using a supported bimetallic nanocatalyst, which is characterized in that a supported bimetallic nanocatalyst M 1 -M 2 @Al 2 O 3 is used as a catalyst to catalyze direct coupling of pyridine.
  • the reaction synthesizes 2,2'-bipyridyl, and the reaction equation is as shown in formula (1):
  • R 1 , R 2 , R 3 and R 4 are each independently selected from H, methyl, ethyl, propyl, butyl, pentyl or hexyl;
  • the obtained reaction mixture was subjected to solid-liquid separation, and the obtained solid was used as a catalyst, which was recycled; and the obtained filtrate was subjected to fractional distillation under reduced pressure to obtain an unreacted pyridine and a desired product 2,2'-bipyridine.
  • the mass ratio of M 1 -M 2 @Al 2 O 3 to pyridine is from 1:1 to 10,000, preferably from 1:4 to 50.
  • the reaction temperature is preferably 400 ° C, and the reaction time is preferably 8 h.
  • the supported bimetallic nanocatalyst M 1 -M 2 @Al 2 O 3 is supported by Al 2 O 3 , and any two different metals M 1 and M 2 are active components; wherein M 1 and M 2 are independent It is selected from the noble metals Pd, Pt, Ru, Au, Ag, Rh, or non-precious metals such as Ni, Cu, Fe, Zn, Co.
  • the noble metal is preferably Pd, Pt or Ru; the non-precious metal is preferably Cu or Ni;
  • the support of the catalyst may be such that various crystal forms of Al 2 O 3 , such as ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 and amorphous Al 2 O 3 , preferably ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 ;
  • the molar ratio of the two components of the active component M 1 , M 2 is 1:0.01-100; the ratio of the active component mass to the total mass of the catalyst is 5-60%, preferably 30-50%;
  • the corresponding noble metal active component is converted by using a mineral acid or an organic acid salt of a corresponding ion, or a metal organic compound or the like as a precursor; for example, RuCl 3 ⁇ 3H 2 O, RuO 2 , (NH 4 ) 2 RuCl 6 , [(C 6 H 5 ) 3 P] 3 RuCl 2 , acetylacetonate hydrazine, H 2 PtCl 6 ⁇ 6H 2 O, PtCl 4 , PtCl 3 , PtCl 2 , [Pt(NH 3 ) 4 ](NO 3 ) 2 , (NH 4 ) 2 PtCl 6 , Pt(NO 3 ) 2 , (NH 4 ) 2 PtCl 4 , acetylacetonate platinum, Pd(NO 3 ) 2 , Pd (OAc) 2 , PdCl 2 , Pd(
  • the corresponding non-noble metal active component is converted by using a mineral acid or an organic acid salt of a corresponding ion, or a metal organic compound or the like as a precursor; for example, Cu ( NO 3 ) 2 ⁇ 3H 2 O, CuCl 2 ⁇ 2H 2 O, CuO, Cu 2 O, Cu(OAc) 2 , Cu 2 (OH) 2 CO 3 , copper acetylacetonate, copper trimethoxylate, C 4 H 6 O 4 Co, CoCO 3 , CoCl 2 , CoSO 4 ⁇ 7H 2 O, Co(OH) 2 , Co(NO 3 ) 2 , CoF 2 , CoCl 2 (NH 3 ) 4 , cobalt naphthenate, cobalt acetylacetonate, FeCl 3 , FeS, Fe 2 (C 2 O 4 ) 3 ⁇ 5H 2 O, Fe(NO 3 ) 3 ,
  • the preparation method of the supported bimetallic nanocatalyst of the invention may be a nanoparticle loading method or an in situ loading method.
  • the step of the nanoparticle loading method is: purchasing commercially available or self-made alloy nanoparticles M 1 -M 2 , and selecting a suitable solvent according to the type and nature of the coating agent outside the alloy nanoparticles (such as deionized water, alcohol, ether, preferably Water and alcohol), to prepare a uniform and stable dispersion of the alloy nanoparticle dispersion solution.
  • a suitable solvent such as deionized water, alcohol, ether, preferably Water and alcohol
  • the appropriate amount of the above solution is added, and then a certain mass fraction of the carrier is added, and the mixture is continuously stirred and mixed, and then the solvent is removed by drying at a suitable temperature, and then calcined, reduced, and annealed at a high temperature to obtain a supported bimetal.
  • Nanoalloy catalyst is: purchasing commercially available or self-made alloy nanoparticles M 1 -M 2 , and selecting a suitable solvent according to the type and nature of the coating agent outside the alloy nanoparticles (such as de
  • the step of preparing the catalyst by the in-situ loading method is as follows: the precursor raw material is weighed according to the ratio of the active components, dissolved or stirred with water or a suitable solvent, and the carrier is added to the above solution according to the ratio, and stirred for a period of time until uniform. It is viscous, and then dried under appropriate temperature conditions to remove the solvent. After grinding, it is calcined, reduced, and annealed at a high temperature to obtain the supported bimetallic nanoalloy catalyst.
  • the present invention applies a supported bimetallic nanocatalyst to a direct coupling of pyridine to produce 2,2'-bipyridine, which has high production efficiency, conforms to the atomic economic principle in chemical production, does not produce environmentally harmful pollution, and is a green chemical industry. Intermediate production technology.
  • the pyridine is recovered by distillation under reduced pressure, the recovery rate is up to 90-98%, the purity of pyridine is 98-99.5%, and the pyridine can be directly recycled after distillation; and after the catalyst is recovered, according to the specific situation, Direct re-use or simple drying regeneration is repeated, still maintaining high catalytic activity and product selectivity.
  • the double active component can effectively adjust the cleavage of the CH bond and the coupling of the CC bond, thereby improving the activity of the catalyst;
  • ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 and ⁇ -Al 2 O 3 are carriers, the specific surface area is large, and the interaction with each active component is strong, so that the active component is stable on the carrier, and is more convenient for recycling and repeated use.
  • Example 1 Preparation and catalytic reaction of Pd@ ⁇ -Al 2 O 3 metal nanocatalyst in situ loading method
  • Example 2 Preparation and catalytic reaction of Cu@ ⁇ Al 2 O 3 metal nanocatalyst in situ loading method
  • Example 3 Preparation and catalytic reaction of bimetallic nanocatalysts by in-situ loading method Pd-Ni@ ⁇ -Al 2 O 3 (Pd and Ni molar ratio is 2:1)
  • Example 4 Preparation of in-situ loading method Pd-Ni@ ⁇ -Al 2 O 3 (Pd and Ni molar ratio is 1:1) Preparation and catalytic reaction of bimetallic nanocatalyst:
  • Example 5 In-situ loading method Pd-Cu@ ⁇ -Al 2 O 3 (Pd and Cu molar ratio is 3:1) Preparation and catalytic reaction of bimetallic nanocatalyst:
  • Example 6 Preparation of in-situ loading method Pd-Cu@ ⁇ -Al 2 O 3 (Pd and Cu molar ratio is 1:1) Preparation and catalytic reaction of bimetallic nanocatalyst:
  • Example 8 Preparation of in-situ loading method Pt-Cu@ ⁇ -Al 2 O 3 (Pt and Cu molar ratio is 1.5:1) Preparation and catalytic reaction of bimetallic nanocatalyst:
  • Example 9 In-situ loading method Ru-Ni@ ⁇ -Al 2 O 3 (molar ratio of Ru to Ni is 2:1) Preparation and catalytic reaction of bimetallic nanocatalyst:
  • Example 10 Preparation and Catalytic Reaction of Pd-Ni@ ⁇ -Al 2 O 3 (3:1) Bimetallic Nanocatalyst by Nanoparticle Loading Method:
  • the reaction mixture is taken out from the autoclave, separated by filtration and recovered, and the catalyst can be directly recycled.
  • the filtrate was subjected to fractional distillation under reduced pressure to obtain 15.7 g of pyridine. The recovery was 93%, and the content was determined to be 96.3%; 22.9 g of 2,2'-bipyridine was obtained, and the yield was 43.1%.
  • Example 12 Preparation of in-situ loading method Pt-Pd@ ⁇ -Al 2 O 3 (Pt and Pd molar ratio is 1:1) Preparation and catalytic reaction of bimetallic nanocatalyst:
  • Example 13 In-situ loading method Pt-Pd@ ⁇ -Al 2 O 3 (molar ratio of Pt to Pd is 2:1) Preparation and catalytic reaction of bimetallic nanocatalyst:
  • Example 14 Preparation of in-situ loading method Cu-Ni@ ⁇ -Al 2 O 3 (molar ratio of Cu to Ni is 1:1) Preparation and catalytic reaction of bimetallic nanocatalyst:
  • the filtrate was subjected to fractional distillation under reduced pressure to obtain 52.7 g of pyridine, the recovery was 93%, and the content was found to be 95.0%; 2,2'-bipyridyl 3.48 g was obtained, and the yield was 5.8%.
  • Example 15 In-situ loading method Pd-Ni@ ⁇ -Al 2 O 3 (molar ratio of Pd to Ni is 2:1) Preparation and catalytic reaction of bimetallic nanocatalyst:
  • Example 16 In-situ loading method Pd-Ni@ ⁇ -Al 2 O 3 (molar ratio of Pd to Ni is 2:1) Preparation and catalytic reaction of bimetallic nanocatalyst:
  • Step (1) Preparation of catalyst and the recovered 2.5g of pyridine 20g (content of ⁇ 98.0%) added to the autoclave, which replaced with N 2 O 2, the sealed reactor; open autoclave was stirred and heated to a pot temperature 400 ° C; after 8 h of reaction, the heating was stopped, and the temperature of the kettle was lowered to room temperature, and the autoclave valve was opened to safely discharge the H 2 generated by the reaction.
  • the reaction mixture is taken out from the autoclave, separated by filtration and recovered, and the catalyst can be directly recycled.
  • the filtrate was subjected to fractional distillation under reduced pressure to obtain 9.25 g of pyridine. The recovery was 91%, and the content was found to be 94.6%.
  • the 2,2'-bipyridine was obtained in a yield of 50.1%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pyridine Compounds (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé pour la synthèse de 2,2'-dipyridine utilisant un nanocatalyseur bimétallique à support. Le nanocatalyseur bimétallique à support M1-M2@Al2O3 est utilisé en tant que catalyseur pour catalyser la réaction de couplage direct de pyridine pour la synthèse de 2,2'-dipyridine. Le nanocatalyseur bimétallique à support M1-M2@Al2O3 selon la présente invention est un catalyseur comprenant de l'Al2O3 en tant que support et deux métaux différents quelconques M1 et M2 en tant que constituants actifs, M1 et M2 étant chacun indépendamment choisis parmi les métaux nobles Pb, Pt, Ru, Au, Ag et Rh ou les métaux non nobles Ni, Cu, Fe, Zn et Co. Par l'application du nanocatalyseur bimétallique à support dans la production de 2,2'-dipyridine à partir de pyridine par couplage direct, le rendement de production est élevé et des polluants qui sont nocifs pour l'environnement ne sont pas produits.
PCT/CN2016/086353 2016-04-22 2016-06-20 Procédé de synthèse pour de la 2,2'-dipyridine utilisant un nanocatalyseur bimétallique à support Ceased WO2017181514A1 (fr)

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CN117414835A (zh) * 2023-10-23 2024-01-19 常州大学 一种用于三丙酮胺制备2,2,6,6-四甲基-4-哌啶胺的催化剂及其应用

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CN107935919B (zh) 2017-11-17 2019-09-03 南京红太阳生物化学有限责任公司 一种2,2’-联吡啶及其衍生物的制备方法
CN108484486B (zh) * 2018-05-23 2021-04-27 安徽国星生物化学有限公司 一种2,2′-联吡啶的精制方法
CN110586102B (zh) * 2019-08-21 2022-09-27 中山大学 一种类杂原子催化剂的制备方法
CN110801841A (zh) * 2019-11-27 2020-02-18 中国科学院大连化学物理研究所 一种用于合成吡啶偶联制2,2’-联吡啶的催化剂及其制备方法和应用
CN114014799A (zh) * 2021-12-08 2022-02-08 安徽国星生物化学有限公司 一种2,2-联吡啶的生产工艺
CN115245841B (zh) * 2022-08-22 2024-01-26 山东明化新材料有限公司 一种镍钴金属骨架催化剂在2,2’-联吡啶制备中的应用
CN116482189B (zh) * 2023-05-16 2025-08-22 吉林大学 一种基于高导电双金属Co/Cu-HHTP敏感材料的NH3气体传感器及其制备方法
CN117105850A (zh) * 2023-08-08 2023-11-24 江苏诺恩作物科学股份有限公司 一种1,1-二甲基-4,4'-联吡啶二氯化物的制备方法

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CN117414835A (zh) * 2023-10-23 2024-01-19 常州大学 一种用于三丙酮胺制备2,2,6,6-四甲基-4-哌啶胺的催化剂及其应用

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