3-diazo-3-phenylpropyne | 157022-41-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-diazo-3-phenylpropyne
• 英文别名: 1-Diazoprop-2-ynylbenzene；1-diazoprop-2-ynylbenzene
• CAS: 157022-41-8
• 化学式: C₉H₆N₂
• 分子量: 142.16
• InChiKey: LTSYDCKDVVPHLP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-diazo-3-phenylpropyne 生成
  参考文献：
  名称：

  Reactions of Ethynylcarbenes Related to Solid-State Polymerization of 1-Phenyl-1,3-butadiyne

  摘要：

  制备1,8-二苯基-1,8-双(重氮)-辛-4-烯-2,6-二炔并光解以高产率得到1-苯基-1,3-丁二炔。 6 K 下在 MTHF 中光解产生的乙炔基苯基卡宾和 β-苯基乙炔基卡宾处于平衡状态，其中后者在 90 K 下占主导地位。

  DOI：

  10.1246/cl.1991.1357
• 作为产物：
  描述：

  N-(1-phenyl-2-propynyl)acetamide 在 吡啶 、 sodium hydroxide 、 nitrosonium tetrafluoroborate 作用下， 以 乙醚 、 乙醇 为溶剂， 生成 3-diazo-3-phenylpropyne
  参考文献：
  名称：

  Carbene-Carbene Interconversion between 1- and 3-Phenyl-2-propynylidenes

  摘要：

  1-Phenyl-3-diazopropyne (Id) and 3-phenyl-3-diazopropyne (2d) were prepared and photolyzed under various conditions. In ethanol at ambient temperatures, both 1d and 2d gave a 1:10 +/- 1 mixture of 1-phenyl-3-ethoxypropyne (3) and 3-phenyl-3-ethoxypropyne (4). The photolyses of matrix-isolated 1d and 2d at cryogenic temperatures were followed by EPR, IR, and UV-visible spectroscopy. EPR experiments in 2-methyltetrahydrofuran (MTHF), isopentane, and ethanol-d(6) matrices at 9 K showed spectra due to a mixture of the corresponding triplet carbenes 1c (\D/hc\ = 0.543 and \E/hc\ = 0.003 cm(-1)) and 2c (\D/hc\ = 0.526 and \E/hc\ = 0.010 cm(-1)). The ratio of the generated carbenes carried the memory of the starting diazo compounds; 1c and 2c were produced mainly from 1d and 2d, respectively. Carbene 2c isomerized to 1c at 70-90 K in MTHF and ethanol-d(6) and at 44-68 K in isopentane, indicating that 1c was thermodynamically more stable than 2c on the triplet ground-state potential energy surface. IR and UV-visible absorption experiments employing various media (argon, isopentane, N-2, CO/Ar, O-2/N-2, and O-2/Ar) revealed that the photolysis of 2d afforded mostly absorptions due to 2c. Photolysis of 1d produced similar spectra, due mainly to 2c, together with weak absorptions due to 1c. The different results observed in EPR and IR experiments were explained by the difference in the matrices in which the diazo groups were photolyzed. Calculations at the ab initio MP2/DZV(d) level of theory showed that the triplet ground state of 1c was more thermodynamically stable than 2c by 1.41 kcal/mol, in agreement with the experimental results. The situation is reversed in the singlet manifold, where 2c was computed to be much lower in energy than 1c. The energy differences (Delta E(ST)) between the singlet and triplet states were computed to be 15.7 and 11.0 kcal/mol for 1c and 2c, respectively, with the DZV(d) basis set.

  DOI：

  10.1021/ja00093a017

文献信息

• Carbene-Carbene Interconversion between 1- and 3-Phenyl-2-propynylidenes
  作者：Masaki Noro、Takeshi Masuda、Andrew S. Ichimura、Noboru Koga、Hiizu Iwamura

  DOI：10.1021/ja00093a017

  日期：1994.7

  1-Phenyl-3-diazopropyne (Id) and 3-phenyl-3-diazopropyne (2d) were prepared and photolyzed under various conditions. In ethanol at ambient temperatures, both 1d and 2d gave a 1:10 +/- 1 mixture of 1-phenyl-3-ethoxypropyne (3) and 3-phenyl-3-ethoxypropyne (4). The photolyses of matrix-isolated 1d and 2d at cryogenic temperatures were followed by EPR, IR, and UV-visible spectroscopy. EPR experiments in 2-methyltetrahydrofuran (MTHF), isopentane, and ethanol-d(6) matrices at 9 K showed spectra due to a mixture of the corresponding triplet carbenes 1c (\D/hc\ = 0.543 and \E/hc\ = 0.003 cm(-1)) and 2c (\D/hc\ = 0.526 and \E/hc\ = 0.010 cm(-1)). The ratio of the generated carbenes carried the memory of the starting diazo compounds; 1c and 2c were produced mainly from 1d and 2d, respectively. Carbene 2c isomerized to 1c at 70-90 K in MTHF and ethanol-d(6) and at 44-68 K in isopentane, indicating that 1c was thermodynamically more stable than 2c on the triplet ground-state potential energy surface. IR and UV-visible absorption experiments employing various media (argon, isopentane, N-2, CO/Ar, O-2/N-2, and O-2/Ar) revealed that the photolysis of 2d afforded mostly absorptions due to 2c. Photolysis of 1d produced similar spectra, due mainly to 2c, together with weak absorptions due to 1c. The different results observed in EPR and IR experiments were explained by the difference in the matrices in which the diazo groups were photolyzed. Calculations at the ab initio MP2/DZV(d) level of theory showed that the triplet ground state of 1c was more thermodynamically stable than 2c by 1.41 kcal/mol, in agreement with the experimental results. The situation is reversed in the singlet manifold, where 2c was computed to be much lower in energy than 1c. The energy differences (Delta E(ST)) between the singlet and triplet states were computed to be 15.7 and 11.0 kcal/mol for 1c and 2c, respectively, with the DZV(d) basis set.
• Reactions of Ethynylcarbenes Related to Solid-State Polymerization of 1-Phenyl-1,3-butadiyne
  作者：Noboru Koga、Masahiro Matsumura、Masaki Noro、Hiizu Iwamura

  DOI：10.1246/cl.1991.1357

  日期：1991.8

  1,8-Diphenyl-1,8-bis(diazo)-octa-4-ene-2,6-diyne was prepared and photolyzed to give 1-phenyl-1,3-butadiyne in high yield. Ethynylphenylcarbene and β-phenylethynylcarbene generated by photolysis in MTHF at 6 K are in equilibrium in which the latter predominates at 90 K.

  制备1,8-二苯基-1,8-双(重氮)-辛-4-烯-2,6-二炔并光解以高产率得到1-苯基-1,3-丁二炔。 6 K 下在 MTHF 中光解产生的乙炔基苯基卡宾和 β-苯基乙炔基卡宾处于平衡状态，其中后者在 90 K 下占主导地位。