Shortcut Approach to 1,4-Diazepine from 3-Pyridylnitrene Intermedietes under Mild Condition

The Journal of Pure and Applied Chemistry Research

Hideki Okamoto¹  Siti Mariyah Ulfa²  Kyosuke Satake³ 

[1] Okayama University, Japan$$;Laboratory of Organic Chemistry, Chemistry Department, Brawijaya University$$;Okayama University$$

关键词: Goitrogenic;    Iodium;    Malondialdehyde;    KIO3;    KI salt;    therapy;   

DOI  :  

来源: University of Brawijaya

【 摘 要 】

The reaction of nitropyridine derivatives and tributylphosphine (Bu 3 P) with the existence of nucleophilic solvent gives ring expansion product as diazepines in medium yield. Reaction mechanism subjected the formation of phenylnitrene, followed by intramolecular electrophilic insertion reaction to pyridine ring and subsequent ring enlargement. The intermediate in the reaction confirmed by computational calculation using B3LYP/6-31G* level. The intramolecular insertion reaction of pyridylnitrene is considered suppressed by the low HOMO (-9.932 eV) energy level of pyridine ring compared to that of benzene (-9.653 eV), hence 1,4-diazepine is obtained when employed 3-nitro-2,6-lutidine as starting material. The formation of diazepines was confirmed by the analysis of 1 H NMR data. Separation of the product mixture using column chromatography on SiO 2 was carried out and found to give expected diazepine along with the reduction product.

【 授权许可】

Unknown