2,2-二甲基-1,6-二氧杂-3,4,9-三氮杂螺[4.4]壬-3-烯 | 143023-00-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 中文名称: 2,2-二甲基-1,6-二氧杂-3,4,9-三氮杂螺[4.4]壬-3-烯
• 英文名称: 3,4,9-triaza-2,2-dimethyl-1,6-dioxaspiro[4.4]non-3-ene
• 英文别名: 3,3-Dimethyl-4,6-dioxa-1,2,9-triazaspiro[4.4]non-1-ene；2,2-dimethyl-1,6-dioxa-3,4,9-triazaspiro[4.4]non-3-ene
• CAS: 143023-00-1
• 化学式: C₆H₁₁N₃O₂
• 分子量: 157.172
• InChiKey: HUOQWYDNWZZPID-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  甲酸对硝基苯酯 、 2,2-二甲基-1,6-二氧杂-3,4,9-三氮杂螺[4.4]壬-3-烯 以 二氯甲烷 为溶剂， 反应 72.0h， 以41%的产率得到3,4,9-triaza-9-formyl-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
• 作为产物：
  描述：

  acetone 4-(2-hydroxyethyl)semicarbazone 在 碘苯二乙酸 作用下， 以 二氯甲烷 为溶剂， 生成 2,2-二甲基-1,6-二氧杂-3,4,9-三氮杂螺[4.4]壬-3-烯
  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

• Reactions of nucleophilic carbenes with enols
  作者：Philippe Couture、David L. Pole、John Warkentin

  DOI：10.1039/a700169j

  日期：——

  The formal insertion of dimethoxycarbene (1a) into the acidic C–H bond of pentane-2,4-dione (9a), methyl acetoacetate (9b), 3-methylpentane-2,4-dione (9c) and 1,3-diphenylpropane-1,3-dione (9d) is reported as well as the insertion of 3-benzoyloxazolidin-2-ylidene (1b) into 9c. The β-dicarbonyl compounds 9 are known to be equilibrated with their corresponding enols in benzene solution and the insertions appear to proceed by proton abstraction from the enol tautomers of 9 to generate enolate anions and either a dimethoxymethyl cation (from 1a) or a 3-benzoyloxazolidin-2-ium cation (from 1b). Collapse of these ion pairs at the carbon atom of the enolate yields the major product. Formal insertion of 1a into the O–H bond of the enol tautomer of anthrone (12) is also reported.

  据报道，二甲氧基羰基（1a）正式插入戊烷-2,4-二酮（9a）、乙酰乙酸甲酯（9b）、3-甲基戊烷-2,4-二酮（9c）和 1,3-二苯基丙烷-1,3-二酮（9d）的酸性 C-H 键，以及 3-苯甲酰恶唑烷-2-亚基（1b）插入 9c。β-二羰基化合物 9 与相应的烯醇在苯溶液中处于平衡状态，插入似乎是通过从 9 的烯醇同系物中抽取质子来生成烯醇阴离子和二甲氧基甲基阳离子（来自 1a）或 3-苯甲酰恶唑啉-2-鎓阳离子（来自 1b）。 这些离子对在烯醇的碳原子上塌缩产生主要产物。此外，还报道了 1a 正式插入蒽酮 (12) 的烯醇同系物的 O-H 键的情况。
• 2-Alkoxy-2-amino-Δ³-1,3,4-oxadiazolines as Novel Sources of Alkoxyaminocarbenes
  作者：Philippe Couture、Johan K. Terlouw、John Warkentin

  DOI：10.1021/ja953813+

  日期：1996.1.1
• Spiro-fused 2-alkoxy-2-amino-Δ³-1,3,4-oxadiazolines. Synthesis and thermolysis to corresponding aminooxycarbenes
  作者：Philippe Couture、John Warkentin

  DOI：10.1139/v97-153

  日期：1997.9.1

  undergo thermolysis in benzene at 90 °C with first-order rate constants of (1.6–50) × 10−5 s−1. The dependence of these rate constants on the nature of the substituents present on the oxadiazoline ring is consistent with a mechanism involving a carbonyl ylide intermediate. Substituents on N of the oxazolidine or tetrahydro-1,3-oxazine moieties play a major role in determining the fragmentation pathways

  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：
• 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.