THE STRUCTURE OF CERTAIN POLYAZAINDENES .2. THE PRODUCT FROM ETHYL ACETOACETATE AND 3-AMINO-1,2,4-TRIAZOLE
THE STRUCTURE OF CERTAIN POLYAZAINDENES .2. THE PRODUCT FROM ETHYL ACETOACETATE AND 3-AMINO-1,2,4-TRIAZOLE
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DOI：
10.1021/jo01088a014
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发表时间：
1959-01-01
影响因子：
3.6
通讯作者：
VANALLAN, JA
中科院分区：
文献类型：
--
作者：
ALLEN, CFH;BEILFUSS, HR;VANALLAN, JA
Birr和Walther [4]设计了一种他们认为是明确的合成方法;通过用甲酸环化2-肼基-4-羟基-6-甲基嘧啶（V），得到了与氨基三唑和乙酰乙酸乙酯相同的物质。因此，得出结论，氮原子具有1，2，3a，7-排列，如（IIa）中所示。重复比尔和瓦尔特的工作在这些实验室导致的发现，性质的产品取决于酸性的反应溶液。在比Birr和Walther的条件温和的条件下，得到了一种异构体，令人惊奇的是，在沸腾的甲酸中，它被异构化成了早已为人所知的1，3，3a，7-异构体！因此，Birr和Walther的综合并不明确。在稍微改变的实验条件下以类似的方式获得同源物。(3)德国作者使用的名称是“6-met，hyl-1，3-triazo-7，0 '-pyridazine-4-hydroxylic acid”。Beilstoin（主要作品，第4版，第XXVI卷，第433页）已将氧代形式I重命名为“7-氧代-5-甲基-6，7-二氢-1，3，4-三氮杂中氮茚”，在结构Ia中所示的互变异构体的情况下删除“6，7-二氢”。本文的作者继续使用前面使用的“a”系统，
Birr and Walther4 devised what appeared to them to be an unequivocal synthesis; by cyclizing 2-hydrazino-4-hydroxy-6-methylpyrimidine (V) with formic acid, the same substance was obtained as resulted from aminotriazole and ethyl acetoacetate. Hence, it was concluded that the nitrogen atoms had the 1, 2, 3a, 7-arrangement, as shown in (Ila). Repetition of Birr and Walther’s work in these Laboratories led to the discovery that the nature of the product depended on the acidity of the reacting solution. Under conditions milder than Birr and Walther’s, an isomer was obtained, which, amazingly, in boiling formic acid, was isomerized to thelong-known 1, 3, 3a, 7-isomer! Thus, Birr and Walther’s synthesis is not unambiguous. Homologs were obtained in a similar manner under slightly altered experimental conditions.(3) The German authors used the name“6-met, hyl-1, 3-triazo-7, 0'-pyridazine-4-hy droxylic acid.” Beilstoin (main work, 4th ed., Vol. XXVI, p. 433) has renamed the oxo form I,“7-oxo-5-methyl-6, 7-dihydro-l, 3, 4-triazaindolizine,” dropping the “6, 7-dihydro-” in the case of the tautomer shown in structure la. The authors of this paper have continued to use the “a” system, used in the preceding