The Diazotization of 2-Aminoazulene Derivatives. The Formation of 2-Diazo-2,6-azulenoquinone Derivatives

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概要

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• The Diazotization of 2-amino-6-bromo (or alkoxy)-azulene, with alkoxycarbonyl or cyano groups at the 1 and 3-positions, by sodium nitrite in dioxane–sulfuric acid afforded mainly the corresponding 2-diazo-2,6-azulenoquinone derivatives (<B>2a</B>, <B>2b</B>, <B>16</B>). The catalytic hydrogenation of these compounds gave 1,3-disubstituted 6-hydroxyazulenes (<B>4a</B>, <B>4b</B>, <B>18</B>), from which 1,3-disubstituted 6-alkoxy- or 6-acetoxy-azulenes were obtained. The diazotization of diethyl 2-amino-6-bromoazulene-1,3-dicarboxylate (<B>1a</B>) in dry benzene with isoamyl nitrite in the presence of hydrogen chloride afforded the 2,6-dichloroazulene derivative (<B>20</B>) and the 5-bromo-2-diazo-2,6-azulenoquinone derivative (<B>21</B>); the latter, accompanied by a bromine addition product (<B>22</B>), was also obtained by the bromination of <B>2a</B>. The diazotization of diethyl 2-aminoazulene-1,3-dicarboxylate (<B>25</B>) afforded <B>2a</B> and a deamination product (<B>26</B>). The structure and mechanism of the formation of these diazoazulenoquinones are discussed.

• 公益社団法人 日本化学会の論文

著者

• Ando Masayoshi

  Department of Applied Chemistry, Niigata University

• Nozoe Tetsuo

  Department of Chemistry Faculty of Science Tohoku University

• Asao Toyonobu

  Department of Chemistry Faculty of Science Tohoku University

• Susumago Hiroshi

  Department of Chemistry, Faculty of Science, Tohoku University

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