701. Conjugated cyclic hydrocarbons and their heterocyclic analogues. Part VI. The condensation of azulenes with aliphatic aldehydes in the presence of perchloric acid
701. Conjugated cyclic hydrocarbons and their heterocyclic analogues. Part VI. The condensation of azulenes with aliphatic aldehydes in the presence of perchloric acid
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701. 共轭环烃及其杂环类似物。
DOI：
10.1039/jr9610003579
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发表时间：
1961
期刊：
影响因子：
--
通讯作者：
D. Reid
中科院分区：
文献类型：
--
作者：
E. C. Kirby;D. Reid
本文报道了在高氯酸存在下，甘菊环烃与以下几类脂肪醛的缩合反应：简单的α-不饱和醛、α-羰基醛、二醛、对羰基醛、α-氰基醛和α-硝基醛。产物的性质取决于甘菊环的烷基化程度和醛的类型。各种类型的产品的可能途径进行了讨论。在首次报道的甘菊环与醛的缩合反应中，愈创甘菊环（5-异丙基-3，8-二甲基甘菊环）与苯甲醛及其衍生物在氯化氢存在下反应生成3-芳基亚甲基愈创甘菊环氯化物2，这些盐不稳定，但可以转化为更稳定的苦味酸盐。虽然杂环芳香族和许多脂肪族醛也缩合，但不能分离出不稳定的产物。然后，在改进的工艺中，用70%（w/w）高氯酸代替无水氯化氢，与碳环和杂环芳香醛发生缩合反应，得到热稳定的结晶高氯酸盐。我们现在描述的应用程序，我们的修改程序的缩合的甘菊环烃与简单的和多官能的脂肪族醛。
Condensation of azulene hydrocarbons with the following classes of aliphatic aldehydes in the presence of perchloric acid is reported: simple aP-unsaturated aldehydes; a-oxo-aldehydes; dialdehydes; P-oxo-aldehydes; a-cyano-and a-nitro-aldehydes. The nature of the products depends on the degree of alkylation of the azulene and on the type of the aldehyde. Possible pathways to the various types of products are discussed. Spectral data for the products are recorded.IN the first reported condensations of azulenes with aldehydes, guaiazulene (5-isopropyl-3, 8-dimethylazulene) reacted with benzaldehyde and its derivatives in the presence of hydrogen chloride to form 3-arylmethyleneguaiazulenium chlorides2 These salts were unstable but could be converted into the somewhat more stable picrates. Although heterocyclic aromatic, and many aliphatic, aldehydes also condensed the unstable products could not be isolated. Subsequently, in an improved proced~ re,~ with 70%(w/w) perchloric acid in place of anhydrous hydrogen chloride, ready condensation occurred with carbocyclic and heterocyclic aromatic aldehydes to give the thermally stable, crystalline perchlorates. We now describe the application of our modified procedure to the condensation of azulene hydrocarbons with simple and multifunctional aliphatic aldehydes.