2,6-Difluoropyridine

 

作者:

 

期刊: Nature  (Nature Available online 1961)
卷期: Volume 191, issue 4788  

页码: 595-595

 

ISSN:0028-0836

 

年代: 1961

 

DOI:10.1038/191595a0

 

出版商: Nature Publishing Group

 

数据来源: Nature

 

摘要:

The present report describes the synthesis of 2,6-difluoropyridine from starting materials readily obtainable by standard laboratory procedures. Conversion of methyl 6-fluoropicolinate4 (60-0 gm.) to 6-fluoropicolinic hydrazido (51-2 gm.), m.p. 120-5-121 (found: C, 46-7; H, 4-0; CeH6FN3O requires C, 46-5; H, 3-9 per cent), with hydrazine in methanol, followed by a modified Curtius-type degradation, gave 2-amino-6-fluoropyridine, m.p. 58-59 (found: C, 53-6; H, 4-3; N, 24-9; 05Η5ΕΝ2 requires C, 53-6; Η, 45; Ν, 25-0). As it is known that fluorine atoms adjacent to aromatic ring nitrogens undergo facile hydrolysis in acid solution5, it was found advisable to reverse the normal addition procedure of the Curtius degradation. Consequently, addition of Ν hydrochloric acid to a stirred slurry of sodium nitrite dissolved in water, 6-fluoropicolinic hydrazide (20-0 gm.), and ether gave 6-fluoropicolinic azide. This was decomposed in warm carbon tetrachloride to crude 6-fluoropicolinic m>cyanate, which was hydrolysed directly to 2-amino-6-fluoropyridine (7-2 gm.) with 50 per cent aqueous acetic acid. By use of Roe's modification of the Schiemann reaction6, 2-amino-6-fluoropyridine (10-0 gm.) was converted to 2,6-difluoropyridine (2-8 gm.), b.p. 124-5 (743 mm.), n% 1-4349 (found: C, 52-2; H, 2-6; N, 12-1; C5H3F2N requires C, 52-2; H, 2-6; N, 12-2). The infra-red spectrum of 2,6-difluoropyridine in carbon tetrachloride, obtained with a Perkin-Elmer model 21 spectrophometer equipped with sodium chloride optics, showed absorptions at 1,607, 1,592 and 1,493 cm.-1, providing evidence for a pyridine nucleus. Additional absorptions at 3,110 and 717 cm.-1 contribute support for the proposed structure of this compound.2,6-Difluoropyridine is exceptionally volatile and shows the same solubility characteristics as 2-fluoro-pyridine. In contrast to pentafluoropyridine, it does exhibit some basic properties in 50 per cent ethanol when titrated against 0-01 N hydrochloric acid. However, no hydrochloride was formed in ethereal hydrogen chloride and no picrate formed in ethanol. An attempt to prepare 2,3-difluoropyridine from methyl 2-fluoronicotinate (10-0 gm.), b.p. 101 (10 mm.), ny 1-4978 (found: C, 54-4; H, 3-9; N, 9-1; C7HeFNO2 requires C, 54-2; H, 3-9; 1ST, 9-0) by a similar route failed because hydrazine was found to react preferentially with the fluorine rather than the ester moiety giving methyl 2-hydrazinonicotinate (1-3 gm.), m.p. 106-106-5 (found: C, 50-4; H, 5-4; N, 25-4; C7H9N3O2 requires C, 50-3; H, 5-4; N, 25-1).A more detailed report of this and related work will be published else

 

点击下载:  PDF (141KB)



返 回