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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 27, Number 2
JKCSEZ 27(2)
April 20, 1983 

Reaction of Thianthrene Cation Radical Perchlorate with Cumene Hydroperoxides

티안트렌 양이온 자유라디칼 과염소산염과 큐멘과산화수소의 반응
Jongheon Shin, Kyongtae Kim

신종헌, 김경태
아세토니트릴용액중의 티안트렌 양이온 라디칼 과염소산 염(1)은 Cumene hydroperoxide(4), p-chlorocumene hydroperoxide(2), p-nitrocumene hydroperoxide(3)와 상온에서 반응한다. 이 반응의 공통 생성물로서 티안트렌을 얻었으며 4로 부터 5-(4'-hydroxyphenyl) thianthrenium perchlorate (5), 2로부터 5-(5'-chloro-2'-hydroxyphenyl) thianthrenium perchlorate (7)와 5-acetonylthianthrenium perchlorate (6), 그리고 3으로부터 6만을 얻었다. 이 반응의 양관계는 1의 2몰이 티안트렌 1몰과 티안트렌이움 염(또는 염들) 1몰을 생성한다. 1에 대한 친핵성 활성도는 페놀 ≫ p-클로로페놀 ∼아세톤 ≫ p-니트로페놀 순서임이 밝혀졌다. Hydroperoxide의 산촉매 불균일 분해반응외에도 소량의 균일분해 반응생성물이 3과 4로부터 생성됨을 알았다.

Reaction of thianthrene cation radical perchlorate (1) with cumene (4), p-chlorocumene (2), and p-nitrocumene (3) hydroperoxides in acetonitrile at room temperature afforded, inter alia, thianthrene as a common product and 5-(4'-hydroxyphenyl) thianthrenium perchlorate (5) for 4, 5-(5'-chloro-2'-hydroxyphenyl) thianthrenium perchlorate (7) and 5-acetonylthianthrenium perchlorate (6) for 2 and 6 for 3, respectively. Stoichiometry of these reactions showed that 2 moles of 1 gave rise to 1mole of thianthrene and 1 mole of thianthrenium salt (or salts). Nucleophilic reactivity to 1 was found to be in the order of phenol ≫ p-chlorophenol ∼ acetone ≫ p-nitrophenol. Apart from acid-catalyzed heterolytic decomposition of hydroperoxides, small amount of homolytic decomposition products were found from 3 and 4.

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