Bipyridine derivative with substituted multiple functional groups and method for preparing bipyridine derivative

Abstract

The invention belongs to the field of organic chemistry, and particularly relates to a method for preparing a bipyridine derivative with substituted multiple functional groups. The method includes mixing halogenated pyridine derivatives and activated copper powder with one another to obtain first mixtures, carrying out reflux cooling, adding ammonia water into the first mixtures to obtain second mixtures, filtering, abstracting and extracting the second mixtures, combining organic phases with one another, drying the organic phases, and carrying out chromatographic purification by the aid of silica columns to obtain the bipyridine derivative (shown as a formula I) with the substituted multiple functional groups; dissolving products shown as the formula I in methanol, sequentially adding ferric trichloride and activated carbon into the methanol to obtain third mixtures and carrying out heating reflux for 10 minutes; adding hydrazine hydrate into the third mixtures to obtain fourth mixtures, carrying out reflux, filtering the fourth mixtures while the fourth mixtures are hot, washing the fourth mixtures, combining organic phases with one another, drying the organic phases and carrying out chromatographic purification by the aid of silica columns to obtain products shown as a formula II. The method has the advantages that coupling reaction is carried out under the catalytic effect of copper, and accordingly the bipyridine derivative with the substituted multiple functional groups can be efficiently synthesized; the method is simple and is important supplement to existing pyridine coupling reaction, and the obtained bipyridine derivative with substituted electron withdrawing groups further can be converted into a bipyridine derivative with substituted electron donating group amino.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and in particular relates to a preparation method of bipyridyl derivatives substituted by multifunctional groups. Background technique [0002] 2,2'-bipyridine and 3,3'-bipyridine are important intermediates in organic synthesis, and are widely used in the synthesis of dyes, pesticides and spices. The synthesis reaction of bipyridine is the same as the coupling reaction for forming C-C bonds, and these coupling reactions mainly include: Suzuki coupling reaction, Stille coupling reaction, Nigishi coupling reaction, etc. [0003] (1) Suzuki coupling reaction [0004] Suzuki coupling reaction refers to the reaction of aryl or alkenyl boronic acid or boronic acid ester with aryl or alkenyl halide under the catalysis of zero-valent palladium complex to form biaryl [Miyaura, N.; Suzuki, A. Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem. Rev. 1995, 95 , 2457-2483.]. 2,2...

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Problems solved by technology

The yield of synthesizing 3,3'-bipyridine by this method is relatively low, and the yield of synthesizing 2,2'-bipyridine is relatively high, especially when the 3-position of pyridine is substituted by nitro, even if it is chlorinated pyridine, the yield The rate has also been greatly improved [Goshaev, M.; Otroshchenko, O. S.; Sadykov, A. S. The UllmannReaction. Russian Chem. Rev. 1972. 41 , 1046-1059; Flatt, A. L.; Dirk, S. M.;Henderson, J. C.; Shen, D. E.; Su, J.; Reed, M. A.; Tour, J. M. Synthesis and testing of new end-functionalized oligomers for molecular electronics. Tetrahedron 2003, 59 , 8555-8570.]

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