1-(1-deuterioethyl)-9-diazofluorene | 166985-80-4

• 英文名称: 1-(1-deuterioethyl)-9-diazofluorene
• CAS: 166985-80-4
• 化学式: C₁₅H₁₂N₂
• 分子量: 221.266
• InChiKey: GYQXVEJMEVAHMM-VMNATFBRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  36.4
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1-(1-deuterioethyl)-9-diazofluorene 在 silica gel 作用下， 以 正戊烷 为溶剂， 350.0~450.0 ℃ 、0.01 Pa 条件下， 生成 、
  参考文献：
  名称：

  Chemistry of 1-Alkylfluorenylidenes. Steric Effects on Arylcarbene Reactivities

  摘要：

  9-Diazofluorenes (RDAF, 1) having a series of alkyl (R) groups from Me to tBu at the 1-position were prepared and decomposed to generate the corresponding fluorenylidenes (RFL, 2) under various conditions in order to examine steric effects on the reactivities of carbenes. Thus, in cyclohexane, singlet fluorenylidenes ((1)RFLs) gave 9-cyclohexylfluorenes while triplet states ((3)RFLs) underwent H abstraction to give 9-fluorenyl (RFLH(.)), which eventually led to fluorene (4, RFLH(2)) and 9,9'bifluorenyl (5), and the ratio of the triplet products to the singlet was increased as more bulky R groups were introduced at the 1-position. These results are interpreted in terms of the steric effects on singlet reactivity, which requires formation of two bonds simultaneously. Generation of tBuFL resulted in the almost exclusive formation of intramolecular reaction products which involved not only insertion of carbene into the delta-C-H bonds of the tert-butyl group but also insertion of the 1,5-biradical, followed by neophyl-type rearrangement. The results are understood as indicating that abstraction of the delta-H by (3)tBuFL gains over the concerted intramolecular C-H insertion in (1)tBuFL. Generation of 1-RFL (R = Et, iPr, tBu) in the gas phase at high temperature gave intramolecular reaction products both in singlet and in triplet states, but the ratio of the singlet to the triplet product increased in going from Et to iPr to tBu presumably due to the increased opportunities of (1)FL to be trapped by delta-C-H bonds. Spectroscopic studies using matrix isolation techniques as well as laser flash photolysis were also carried out to gain information on the intermediates.

  DOI：

  10.1021/ja00121a007
• 作为产物：
  描述：

  1-ethyl-9H-fluoren-9-one 在 chromium(VI) oxide 、 manganese(IV) oxide 、 氢氧化钾 、 硼氘化钠 、 盐酸肼 、 硫酸 、 溴 、 silica gel 、 一水合肼 、 sodium sulfate 作用下， 以 四氯化碳 、 乙醇 、 二甲基亚砜 、 丙酮 为溶剂， 反应 16.5h， 生成 1-(1-deuterioethyl)-9-diazofluorene
  参考文献：
  名称：

  Chemistry of 1-Alkylfluorenylidenes. Steric Effects on Arylcarbene Reactivities

  摘要：

  9-Diazofluorenes (RDAF, 1) having a series of alkyl (R) groups from Me to tBu at the 1-position were prepared and decomposed to generate the corresponding fluorenylidenes (RFL, 2) under various conditions in order to examine steric effects on the reactivities of carbenes. Thus, in cyclohexane, singlet fluorenylidenes ((1)RFLs) gave 9-cyclohexylfluorenes while triplet states ((3)RFLs) underwent H abstraction to give 9-fluorenyl (RFLH(.)), which eventually led to fluorene (4, RFLH(2)) and 9,9'bifluorenyl (5), and the ratio of the triplet products to the singlet was increased as more bulky R groups were introduced at the 1-position. These results are interpreted in terms of the steric effects on singlet reactivity, which requires formation of two bonds simultaneously. Generation of tBuFL resulted in the almost exclusive formation of intramolecular reaction products which involved not only insertion of carbene into the delta-C-H bonds of the tert-butyl group but also insertion of the 1,5-biradical, followed by neophyl-type rearrangement. The results are understood as indicating that abstraction of the delta-H by (3)tBuFL gains over the concerted intramolecular C-H insertion in (1)tBuFL. Generation of 1-RFL (R = Et, iPr, tBu) in the gas phase at high temperature gave intramolecular reaction products both in singlet and in triplet states, but the ratio of the singlet to the triplet product increased in going from Et to iPr to tBu presumably due to the increased opportunities of (1)FL to be trapped by delta-C-H bonds. Spectroscopic studies using matrix isolation techniques as well as laser flash photolysis were also carried out to gain information on the intermediates.

  DOI：

  10.1021/ja00121a007