THE CHEMISTRY OF SIMPLE HETEROCYCLIC SYSTEMS .3. BASIC CENTRES OF 4-SUBSTITUTED QUINAZOLINE DERIVATIVES
THE CHEMISTRY OF SIMPLE HETEROCYCLIC SYSTEMS .3. BASIC CENTRES OF 4-SUBSTITUTED QUINAZOLINE DERIVATIVES
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DOI：
10.1039/jr9490001354
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发表时间：
1949-01-01
期刊：
影响因子：
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通讯作者：
SIMPSON, JCE
中科院分区：
文献类型：
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作者：
MORLEY, JS;SIMPSON, JCE
4-苯氧基喹唑啉与对甲苯磺酸甲酯稠合，通过不稳定的季盐生成1-甲基-4-喹唑啉酮，从而揭示了N(l)作为苯氧基化合物中的碱性中心；然而，4-甲氧基喹唑啉的类似处理会攻击N(1)和N(3)，形成季盐(IV)或(IVa)。尝试将肉桂啉甲碘化物转化为 1-甲基-kcinnolone，导致脱烷基化并以 50% 的产率形成肉桂啉。最近表明（Morley 和 Simpson, J., 1948, 360）6-和 7-硝基-4-乙酰氨基-和-4-联氧基-喹唑啉通过季盐形成和随后的裂变转化为6-和7-硝基-1-甲基-4-喹唑啉酮，因此N(!)是这些喹唑啉中的质子接受中心。另一方面，根据季盐的形成和降解推论，喹唑啉本身的碱度中心是 N1 (Gabriel 和 Colman, Ber., 1904, 37, 3643)。因此，需要确定 N,,, 或 N,,, 是否是其他 4-取代喹唑啉的基本中心，我们现在用 4-PhsnoxyquinazoZine (I; R= Ph) 和 4-methoxyquinazoline (I; R= Me) 记录我们的结果。
Fusion of 4-phenoxyquinazoline with methyl toluene-p-sulphonate yields 1-methyl-4-quinazolone via an unstable quaternary salt, thus disclosing N (l) as the basic centre in the phenoxy-compound; however, similar treatment of 4-methoxyquinazoline attacks both N (l) and N (3) with formation of the quaternary salt (IV) or (IVa). Attempted conversion of cinnoline methiodide into 1-methyl-kcinnolone results in dealkylation and formation of cinnoline in 50% yield.IT has recently been shown (Morley and Simpson, J., 1948, 360) that 6-and 7-nitro-4-acetamido-and-4-plienoxy-quinazoline are converted by quaternary-salt formation and subsequent fission into 6-and 7-nitro-l-methyl-4-quinazolone, and therefore that N (!) is the proton-accepting centre in these quinazolines. On the other hand, the centre of basicity, as deduced from quaternary-salt formation and degradation, is N,, in quinazoline itself (Gabriel and Colman, Ber., 1904, 37, 3643). It was therefore desirable to ascertain whether N,,, or N,,, is the basic centre in other 4-substituted quinazolines, and we now record our results with 4-PhsnoxyquinazoZine (I; R= Ph) and 4-methoxyquinazoline (I; R= Me).