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Synthesis of 4,4í»disubstituted-2,2í»-dipyridine

A synthetic method and a secondary substitution technology, applied in 4 fields, can solve problems such as energy waste, waste of energy, and increase production costs, and achieve the effects of simplifying equipment and operating procedures, reducing energy loss, and improving reaction rates

Inactive Publication Date: 2008-07-16
WUXI RES INST OF APPLIED TECH TSINGHUA UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Above-mentioned method all is to carry out by the mode of reflux under normal pressure condition, though can obtain target product, there are following problems: (1) reaction time is long and productive rate is low
As everyone knows, appropriately increasing the reaction temperature can speed up the reaction rate, but the upper limit of the temperature of the reflux reaction system under normal pressure is the boiling point temperature of the reaction solution (made up of solvent, reactant, product, intermediate product, etc.), and the reaction temperature cannot be further improved; ( 2) Waste of energy
During the heating and reflux operation, on the one hand, it is necessary to provide heat to the reaction liquid to vaporize it, and on the other hand, it is necessary to use circulating water or other cooling methods to take away the heat to condense the vaporized reaction liquid, so a considerable amount of heat is consumed. In the vaporization process, resulting in a waste of energy; (3) high production costs
It is necessary to provide continuous nitrogen, argon and other inert gas protection to the reaction system, and a heating reflux device is required, which increases the production cost

Method used

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  • Synthesis of 4,4í»disubstituted-2,2í»-dipyridine
  • Synthesis of 4,4í»disubstituted-2,2í»-dipyridine
  • Synthesis of 4,4í»disubstituted-2,2í»-dipyridine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Synthesis of 4,4'-Dimethyl-2,2'-bipyridine

[0026] 4-methylpyridine 25.0g is mixed with 0.5g palladium / activated carbon catalyst (the palladium content of this catalyzer is 10wt.%), is packed in the stainless steel reaction kettle with polytetrafluoroethylene liner, with high-purity N 2 Bubble air for 15 minutes to remove dissolved oxygen therein, close the reactor, heat, and react at 180° C. for 15 hours while maintaining magnetic stirring; cool, filter the resulting mixture, and spin the filtrate to remove unreacted 4-picoline. 18.0 g of unreacted 4-methylpyridine was collected, and the white precipitate precipitated after rotary evaporation was recrystallized with ethyl acetate to obtain 5.2 g of 4,4'-dimethyl-2,2'-bipyridine, yield It was 74.3%, and the measured melting point was 175-179°C.

[0027] 1 H NMR (DMSO, 300MHz) δ: 2.41 (s, 6H, 2CH3), 7.27 (d, J=4.9Hz, 2H, H-5, H-5'), 8.23 ​​(s, 2H, H-3, H -3'), 8.52 (d, J=4.9 Hz, 2H, H-6, H-6').

[0028] Elemental an...

Embodiment 2

[0030] Synthesis of 4,4'-Dimethyl-2,2'-bipyridine

[0031] The 4-picoline of 100.0g is mixed with 5 platinum / activated carbon catalysts (the platinum content of this catalyzer is 5wt.%), is packed in the stainless steel reactor with polytetrafluoroethylene liner, with N 2 Bubble air for 20 minutes, close the reactor, heat, and react at 200°C for 48 hours while maintaining magnetic stirring; cool, filter the resulting mixture, spin the filtrate to remove unreacted 4-methylpyridine, and collect 4-methylpyridine 10.5 g of 4,4'-dimethyl-2,2'-bipyridine was obtained by recrystallizing the white precipitate separated out after rotary evaporation with ethyl acetate, and the yield was 80.1%. It is 175-179°C.

[0032] 1 H NMR (DMSO, 300MHz) δ: 2.41(s, 6H, 2CH 3 ), 7.27(d, J=4.9Hz, 2H, H-5, H-5'), 8.23(s, 2H, H-3, H-3'), 8.52(d, J=4.9Hz, 2H, H-6, H-6').

Embodiment 3

[0034] Synthesis of 4,4'-diethyl-2,2'-bipyridine

[0035] The 4-ethylpyridine of 50.0g is mixed with 5.0g palladium / activated carbon catalyst (the palladium content of this catalyzer is 10wt.%), is charged in the stainless steel reaction kettle with polytetrafluoroethylene liner, with Ar gas bubbling 20 Minutes, remove dissolved oxygen therein, close the reactor, heat, and react at 200°C for 30 hours, during which magnetic stirring is maintained; after cooling, the resulting mixture is filtered to obtain a filtrate, and the unreacted 4-ethylpyridine is removed by rotary distillation of the filtrate, collected 41.7g of 4-ethylpyridine was obtained, and the white precipitate precipitated after rotary evaporation was recrystallized with ethyl acetate to obtain 6.5g of 4,4'-diethyl-2,2'-bipyridine with a yield of 78.3% .

[0036] Elemental analysis calculated value (C 14 h 16 N 2): C 79.25, H 7.55, N 13.21; Measured value: C 79.10, H 7.76, N 13.14 (%).

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Abstract

The invention discloses a method for synthesizing 4, 4'-disubstituted-2, 2'-bipyridine, which mainly mixes a 4-substituent pyridine and a metal catalyst according to a weight ratio of 100: 0.2 to 40. The mixture is put in a closable reactor which can be heated and pressurized, which is bubbled for 5 to 30 minutes with inert gases; then the reactor is closed to be heated to a temperature of 140 to 300 DEG C, reacted for 2 to 350 hours under a condition of stirring; after cooling, filtering, rotating steaming and re-crystallization, a target product 4, 4'-disubstituted-2, 2'-bipyridine can be obtained. The method of the invention is simple with the advantages of high efficiency and low cost, thus being suitable for large-scale industrial production.

Description

technical field [0001] The invention belongs to the field of synthetic chemistry, in particular to a method for synthesizing 4,4'-disubstituent-2,2'-bipyridine. Background technique [0002] As an important chemical synthesis intermediate, 4,4'-disubstituent-2,2'-bipyridine compounds can react with various metal ions to form complexes, thereby becoming photosensitizers, detecting the presence and content of trace metal ions indicators, and metal catalysts. Taking 4,4'-dimethyl-2,2'-bipyridine as an example, it is an important raw material for the synthesis of sensitizers, the famous dye N3([Ru(dcbpy) used in dye-sensitized solar cells (DSSC) ) 2 (NCS) 2 ]), the ligand dcbpy, namely 4,4'-dicarboxy-2,2'-bipyridine is synthesized via 4,4'-dimethyl-2,2'-bipyridine, and the subsequent development The DSSC dyes such as K19, Z907, and K77 all need the ligand dcbpy as a ligand, so 4,4'-dimethyl-2,2'-bipyridine is an important raw material. Mohammad K et al. (Mohammad K et al. J...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/22
Inventor 陈崧哲徐盛明李林艳徐刚
Owner WUXI RES INST OF APPLIED TECH TSINGHUA UNIV
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