Synthesis method of dipyridyl derivative or analogue

A synthesis method and derivative technology, applied in the field of bipyridine derivatives and analogues, can solve the problems of unsuitable industrial production, waste of reagents, environment, retention, etc., and achieve the effects of high selectivity, wide application range, and low cost

Inactive Publication Date: 2015-01-14
BEIJING NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This obviously brings great difficulties to the preparation of such compounds, and causes waste of reagents and environmental pollution
In addition, most of the current methods (2) are only suitable for the preparation of symmetrical products
The above two methods, due to the use of difficult-to-prepare metal reagents or the use of a large number of catalytic metals and ligands, make these methods generally stay in laboratory applications, and it is difficult or even impossible to be used in industrial production

Method used

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  • Synthesis method of dipyridyl derivative or analogue
  • Synthesis method of dipyridyl derivative or analogue
  • Synthesis method of dipyridyl derivative or analogue

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Embodiment 1, the synthesis of 2,2'-dipyridine-5,5'-methyl dicarboxylate

[0028]

[0029] Add nickel chloride hexahydrate (0.12g, 0.5mmol) into 20mL N,N-dimethylformamide, add 2-bromopyridine-5-carboxylic acid methyl ester (2.16g, 10mmol), anhydrous lithium chloride (0.43g, 10mmol) and zinc powder (0.78g, 12mmol). Heat the system at 40°C, add a grain of iodine to initiate the reaction, and then keep it warm at 55-60°C until the reaction is complete. The reaction mixture was neutralized to alkaline by adding concentrated ammonia water, the resulting mixture was extracted with dichloromethane, the organic layer was dried over anhydrous sodium carbonate, and the solvent was recovered, and the obtained crude product was purified by column chromatography to obtain the target product 2,2'-bipyridine- Methyl 5,5'-dicarboxylate, yield: 77%.

[0030] The product is a white solid, mp: 260.6-261.9°C.ν max (KBr) / cm -1 1727. 1 H NMR (400MHz, CDCl 3 ):δ9.23(s,2H),8.52(s,2H)...

Embodiment 2、2

[0031] The synthesis of embodiment 2,2,2'-quinoxaline

[0032]

[0033] Nickel chloride hexahydrate (0.12g, 0.5mmol) was added to 20mL N,N-dimethylformamide, followed by adding 2-chloroquinoxaline (1.65g, 10mmol), anhydrous lithium chloride (0.43g, 10mmol) and manganese powder (0.61g, 12mmol). Heat the system at 40°C, add a grain of iodine to initiate the reaction, and then keep it warm at 55-60°C until the reaction is complete. The reaction mixture was neutralized to alkaline by adding concentrated ammonia water, the resulting mixture was extracted with dichloromethane, the organic layer was dried over anhydrous sodium carbonate, and the solvent was recovered, and the obtained crude product was purified by column chromatography to obtain the target product 2,2'-quinoxaline , Yield: 72%.

[0034] The product is a white solid, mp193-195°C. 1 H NMR (400MHz, CDCl 3 ): δ8.81(d, J=8.6Hz, 2H), 8.28(d, J=8.6Hz, 2H), 8.20(d, J=8.3Hz, 2H), 7.83(d, J=8.1Hz, 2H ), 7.70(t, J=7.2Hz...

Embodiment 3

[0035] Embodiment 3, the synthesis of 2,2'-bipyridine-6,6'-dicarbonitrile

[0036]

[0037] Nickel chloride hexahydrate (0.05g, 0.2mmol) was added to 20mL N,N-dimethylformamide, followed by adding 2-chloro-6-cyanopyridine (1.39g, 10mmol), anhydrous lithium chloride (0.65 g, 15mmol) and zinc powder (0.56g, 11mmol). Heat the system at 40°C, add a grain of iodine to initiate the reaction, and then keep it warm at 55-60°C until the reaction is complete. The reaction mixture was neutralized to alkaline by adding concentrated ammonia water, the resulting mixture was extracted with dichloromethane, the organic layer was dried over anhydrous sodium carbonate, and the solvent was recovered, and the obtained crude product was purified by column chromatography to obtain the target product 2,2'-bipyridine- 6,6'-dicarbonitrile, yield: 83%.

[0038] The product is white solid, mp264.5-265.9℃.ν max (KBr) / cm -1 2236. 1 H NMR (400MHz, CDCl 3 ): δ8.73(d, J=8.1Hz, 2H), 8.02(t, J=7.8Hz, ...

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Abstract

The invention relates to a synthesis method of a dipyridyl derivative or an analogue without adding a ligand. The method comprises the steps of mixing and heating 2-halogenated pyridine, its derivative or analogue, nickel salt, zinc powder or manganese powder and halide salt in a solvent to form a coupled product. The method has the advantages that the catalyst ligand is not required to be added; particularly, the high-toxic organic phosphine ligand is not required to be added; the catalyst nickel salt is low in price and small in use amount; and the method is easy and simple to operate, mild in condition, easy to amplify, especially suitable for industrial production, wide in application scope, high in yield, low in cost and environment-friendly.

Description

technical field [0001] The invention relates to the field of organic compound preparation and catalytic synthesis, in particular to a method for bipyridyl derivatives and analogs. Background technique [0002] Bipyridine and its analogs are a very important class of nitrogen-containing bidentate ligands, which are widely used in coordination chemistry, analytical chemistry, supramolecular chemistry, nanochemistry, etc. [Hapke, M.; Brandt, L. ; Lützen, A.Chem.Soc.Rev.2008,37,2782]; In organic chemistry, bipyridine compounds are often excellent ligands for transition metal catalyzed reactions, and many optically active bipyridines are used in asymmetric catalytic reactions occupies an important position in [Fletcher, N.C.J.Chem.Soc., Perkin Trans.12002,1831]. At the same time, many bipyridyl compounds also occupy a very important position in natural product chemistry. For example, Caerulomycins and Collismycins series of bipyridine natural products show good biological activ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D213/80C07D213/803C07D241/42C07D213/84C07D213/64C07D213/38C07D213/68
CPCC07D213/38C07D213/64C07D213/68C07D213/80C07D213/803C07D213/84C07D241/42
Inventor 段新方廖连燕孔兴蕊
Owner BEIJING NORMAL UNIVERSITY
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