STABILITY, DECOMPOSITION, AND REACTIVITY OF A 1,2-DIAZACYCLOPENTENE-3,5-DIONE - 4,4-DIETHYLPYRAZOLINE-3,5-DIONE
STABILITY, DECOMPOSITION, AND REACTIVITY OF A 1,2-DIAZACYCLOPENTENE-3,5-DIONE - 4,4-DIETHYLPYRAZOLINE-3,5-DIONE
复制标题
DOI：
10.1021/jo01262a080
复制
发表时间：
1969-01-01
影响因子：
3.6
通讯作者：
IZYDORE, RA
中科院分区：
文献类型：
--
作者：
GILLIS, BT;IZYDORE, RA
二氮杂环戊烯-3, 5-二酮, 4, 4-二乙基吡唑啉-3, 5-二酮 (2) 通过用四氧化二氮或四乙酸铅 (LTA) 氧化 4, 4-二乙基吡唑烷-3, 5-二酮 (1) 来制备。当使用四氧化二氮氧化1时，2的稀溶液被证明更稳定，并且可以在—15下无限期储存。升温至室温后，2 很容易分解，生成取决于氧化剂性质和分解条件的产物。用四氧化二氮氧化1并分解得到氮、2,2,6,6-四乙基吡唑并[1,2-a]吡唑-1,3,5,7-四酮(3),1-(二乙基羧基乙酰基)-4,4-二乙基-吡唑烷-3,5-二酮(4)和二乙基丙二酸(5)作为产物。用 LTA 氧化 1 并分解，得到氮、3、二乙基丙二酸铅 (9)、3-乙酰氧基-4, 4-二乙基-2-吡唑啉-5-酮 (10)、3, 5-二乙酰氧基-4, 4-二乙基吡唑 (11) 和二乙酰氧基二乙基丙二酸 (13) 作为产物。 2与二烯的原位反应产生了一系列狄尔斯-阿尔德加合物。通过2与2, 3-二甲基-1, 3-丁二烯、异戊二烯、1, 4-二苯基-1, 3-丁二烯、环戊二烯、1, 3-环己二烯、α-水芹烯、1, 3-环辛二烯和蒽反应得到加合物。当使用 LTA 氧化 1 时，加合物的产率更高。加合物的核磁共振和紫外光谱提供了大量有关其几何结构的信息。通过缺电子 cfs-偶氮亲二烯体和共轭二烯在 1, 4 环加成反应制备二氮杂双环体系已有报道。 2-8 这些 cfs-偶氮亲二烯体通常比反式偶氮亲二烯体更具反应性。 2-8 本研究的目的是开发和研究新的 cfs-偶氮化合物，这些化合物可用作 1, 4-环加成反应中的亲二烯体。发现酰肼 4, 4-二乙基吡唑烷-3, 5-二酮 (1) 的氧化生成 1, 2-二氮杂环戊烯-3, 5-二酮 2.9
The diazacyclopentene-3, 5-dione, 4, 4-diethylpyrazoline-3, 5-dione (2), was prepared by the oxidation of 4, 4-diethylpyrazolidine-3, 5-dione (1) with either nitrogen tetroxide or lead tetraacetate (LTA). Dilute solutions of 2 proved to be more stable when nitrogen tetroxide was used to oxidize 1 and could be stored for indefinite periods at—15. On warming to room temperature, 2 decomposed readily to give products which depended on the nature of the oxidant and decomposition conditions. Oxidation of 1 with nitrogen tetroxide and decomposition gave nitrogen, 2, 2, 6, 6-tetraethylpyrazolo [l, 2-a] pyrazole-l, 3, 5, 7-tetraone (3), l-(diethylcarboxyacetyl)-4, 4-diethyl-pyrazolidine-3, 5-dione (4), and diethylmalonic acid (5) as products. Oxidation of 1 with LTA and decomposition gave nitrogen, 3, lead diethylmalonate (9), 3-acetoxy-4, 4-diethyl-2-pyrazolin-5-one (10), 3, 5-diacetoxy-4, 4-diethylpyrazole (11), and diacetoxydiethylmalonate (13) as products. The in situ reaction of 2 with dienes yielded a series of Diels-Alder adducts. Adducts were obtained by the reaction of 2 with 2, 3-dimethyl-l, 3-butadiene, isoprene, 1, 4-diphenyl-l, 3-butadiene, cyclopentadiene, 1, 3-cyclohexadiene, a-phellandrene, 1, 3-cyclooctadiene, and anthracene. Higher yields of the adducts resulted when LTA was used to oxidize 1. The nmr and uv spectra of the adducts gave a considerable amount of information about their geometry.The preparation of diazabicyclic systems by the re-action of electron-deficient cfs-azo dienophiles and conjugated dienes in 1, 4 cycloaddition has been re-ported. 2-8 These cfs-azo dienophiles were found to be generally more reactive than trans-azo dienophiles. 2-8 The purpose of this investigation was to develop and study new cfs-azo compounds which may be useful as dienophiles in 1, 4-cycloaddition reactions. Oxidation of the hydrazide, 4, 4-diethylpyrazolidine-3, 5-dione (1), was found to yield the 1, 2-diazacyclopentene-3, 5-dione 2.9