3,4,9-triaza-9-methoxycarbonyl-2,2-dimethyl-1,6-dioxaspiro[4.4]non-3-ene | 198777-99-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: 3,4,9-triaza-9-methoxycarbonyl-2,2-dimethyl-1,6-dioxaspiro[4.4]non-3-ene
• 英文别名: Methyl 2,2-dimethyl-1,6-dioxa-3,4,9-triazaspiro[4.4]non-3-ene-9-carboxylate
• CAS: 198777-99-0
• 化学式: C₈H₁₃N₃O₄
• 分子量: 215.209
• InChiKey: DQIAEKJMXCTCNM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  72.7
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,4,9-triaza-9-methoxycarbonyl-2,2-dimethyl-1,6-dioxaspiro[4.4]non-3-ene 、 苯酚 以 苯 为溶剂， 反应 24.0h， 以90%的产率得到3-methoxycarbonyl-2-phenoxyoxazolidine
  参考文献：
  名称：

  环状氨基氧卡宾的化学

  摘要：

  Δ3-1,3,4-恶二唑啉在苯中在 90°C 下热解产生的一系列恶唑烷-2-亚基和一个四氢-1,3-恶嗪-2-亚基通过插入 OH 键被截获酚类。在两种情况下，初始产物重排为 N-(2-芳氧基乙基)-N-甲基甲酰胺。围绕这些最终产物的酰胺 CN 键旋转的活化能测量为 20.4 kcal/mol。氨基氧卡宾与两当量的异氰酸甲酯或苯基酯反应生成螺合乙内酰脲。N-羰基卡宾与乙炔二甲酸二甲酯或丙炔酸甲酯反应的主要产物是 2-恶唑啉，这是由拟议的偶极中间体中从 N 到 C 的明显酰基转移产生的；还观察到 1:2（卡宾：陷阱）化学计量的次要产物。关键词：亲核卡宾，

  DOI：

  10.1139/v97-154
• 作为产物：
  描述：

  acetone 4-(2-hydroxyethyl)semicarbazone 在 碘苯二乙酸 、 potassium carbonate 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 48.0h， 生成 3,4,9-triaza-9-methoxycarbonyl-2,2-dimethyl-1,6-dioxaspiro[4.4]non-3-ene
  参考文献：
  名称：

  螺稠合的 2-烷氧基-2-氨基-Δ3-1,3,4-恶二唑啉。合成并热解为相应的氨基氧卡宾

  摘要：

  合成了在 C2 至 C2 处与恶唑烷 (12) 或四氢-1,3-恶嗪 (13) 的 C2 螺环稠合的 Δ3-1,3,4-恶二唑啉。恶二唑啉在苯中在 90 °C 下热解，一级速率常数为 (1.6–50) × 10−5 s−1。这些速率常数对恶二唑啉环上存在的取代基性质的依赖性与涉及羰基叶立德中间体的机制一致。恶唑烷或四氢-1,3-恶嗪部分的 N 上的取代基在确定碎裂途径中起主要作用。具有 N-羰基 (12c-j, 13d,e) 的恶二唑啉提供相应氨基氧卡宾的基本定量收率，而在恶二唑啉与 N-甲基 (12b, 13c) 或 N-磺酰基的情况下，其他断裂反应与卡宾的生成竞争(12k) 组。关键词：

  DOI：

  10.1139/v97-153

文献信息

• A reinterpretation of the substituent effect on the amide barrier. An experimental and theoretical study
  作者：Alex D. Bain、P. Hazendonk、P. Couture

  DOI：10.1139/cjc-77-8-1340

  日期：——

  Recent theoretical work on amide systems has brought into question the application of the concept of resonance. In particular, the role of the oxygen atom was questioned, since the calculations showed little change in its properties when the amide bond was rotated. This paper investigates, both experimentally and computationally, the effect of a substituent on the carbonyl carbon on the amide barrier, in order to test this view. The barriers to the amide rotation in seven spiro-fused oxazolidines were measured by NMR, to within 1 kJ mol(-1). A subset of three of them was modelled to the 6-31G** level. For all three substituents the computed and measured barriers corresponded to within 7 kJ mol(-1). The electron densities were analyzed using the Atoms in Molecules (AIM) theory. The AIM analysis revealed that the oxazolidines behaved similarly to formamide. The substituent effect was described in terms of the atomic populations and energies of the amide C, O, and N. A substituent on the carbonyl carbon caused electron redistributions between N and C, changing their basin attractive energies. Neither the population nor the energy of oxygen changed significantly. When interactions outside the basin of interest were considered, the energy of C was seen to be more sensitive to changing the substituent than the energy of N. However, the atomic parameters from the AIM analysis did not fully reflect the substituent effects observed. For these molecules, the barrier includes contributions from several sources - there is no single, dominant contribution.