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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 33, Number 4
JKCSEZ 33(4)
August 20, 1989 

 
Title
1,2,4-Triazine Ⅲ : Synthesis of 1-Methyl-1,2,4-triazinium Iodides and Their Ring Contraction Reaction to 1-Methyl-1,2,4-triazoles

1,2,4-Triazine Ⅲ : 1,2,4-Triazine 유도체의 Methiodide 염 합성과 이들 염의 고리 축소화반응에 의한 1,2,4-Triazole 유도체 합성
Author
Jae Keun Lee, Hyang Sun Ryu, W. W. Paudler

이재근, 유향선, W. W. Paudler
Keywords
Abstract
1,2,4-Triazine 유도체들을 acetone 용매하에서 methyl iodide와 반응시켜 다양한 1-methyl-1,2,4-triazinium iodide 염을 합성하였다. 또한 이들 염을 10% NaOH 수용액 내에서 K3Fe(CN)6로 산화시킨 결과 고리 축소화반응이 일어나 1-methyl-1,2,4-triazole 유도체를 주로 얻을 수 있었으나 C6에 치환기가 없을 경우는 미량이긴 하지만 1,6-dihydro-6-oxo-1,2,4-triazine 유도체도 동시에 얻을 수 있었다. 고리 축소화반응은 OH-에 의해 먼저 pseudo base를 형성하고 이 Pseudo base가 1-methyl-1,2,4-triazole과 1,6-dihydro-6-oxo-1,2,4-triazine으로 진행됨을 확인할 수 있었고 또한 1,2,4-triazine의 3개의 질소원자 중 N1 원자에 quaternization됨을 확인할 수 있었다.

Various 1-methyl-1,2,4-triazinium iodides were easily synthesized by the reaction of various 1,2,4-triazines and methyl iodide in acetone. When methyl iodide salts of 1,2,4-triazine derivatives were treated with K3Fd(CN)6 in 10% NaOH solution, 1-methyl-1,2,4-triazole derivatives as the main products were obtained by ring contraction. In addition to 1-methyl-1,2,4-triazole derivatives, 1,6-dihydro-6-oxo-1,2,4-triazine derivatives as the minor products were also obtained when there were no substitutents in C6-position of 1,2,4-triazines. The formation of pseudo base by OH- and then oxidation to either 1,6-dihydro-6-oxo-1,2,4-triazines or 1-methyl-1,2,4-triazoles were suggested as the mechanism of the ring contraction. This mechanism also verified that the position of quaternization was neither N2 nor N4 but 1-nitrogen of 1,2,4-triazine.

Page
419 - 425
Full Text
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