(Z)-2-methyl-3-(N-phenylamino)propenenitrile

• 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: (Z)-2-methyl-3-(N-phenylamino)propenenitrile
• 英文别名: 2-methyl-3-(N-phenylamino)propenenitrile；(Z)-3-anilino-2-methylprop-2-enenitrile
• 化学式: C₁₀H₁₀N₂
• 分子量: 158.203
• InChiKey: RYTXAYUCDBABIW-HJWRWDBZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  35.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  aniline hydrochloride 、 3-amino-2-methylamino-propenenitrile 以 甲醇 为溶剂， 反应 5.0h， 以65%的产率得到(Z)-2-methyl-3-(N-phenylamino)propenenitrile
  参考文献：
  名称：

  Phototransposition chemistry of 1-phenylpyrazole. Experimental and computational studies

  摘要：

  Photophysical and photochemical properties of 1-phenylpyrazole and 3-,4-, and 5-methyl-1-phenylpyrazoles have been investigated. INDO/S calculations agree with experimental measurements which show that the S1 and T1 states of these compounds are pi,pi* in character. Upon S0 --> S1(pi,pi*) excitation, these 1-phenylpyrazoles undergo phototransposition via a P4 permutation pathway. This process is consistent with a mechanism involving initial N-N bond cleavage followed by a 1,2-shift and cyclization to form the 1-phenylimidazole product. The 1,2-shift may occur via an undetected azirine intermediate. Whereas the regioselectivity of the reaction may be due to the stability of the N-phenyl radical, the quantum efficiencies of reaction and fluorescence are remarkably dependent on the location of the methyl group in the pyrazole ring. AM1 calculations provide energy-minimized structures for the more reactive 1-phenylpyrazole and 4-methyl- and 5-methyl-1-phenylpyrazoles in which the phenyl and pyrazole rings are perpendicular as required to stabilize the transition state for N-N bond cleavage. In contrast, such a perpendicular energy minimized S1 structure could not be obtained for the least reactive S1(pi,pi*) 3-methyl-1-phenylpyrazole which undergoes mainly radiative return to the ground state.

  DOI：

  10.1021/ja00070a008

文献信息

• Photochemistry of Phenyl-Substituted 1-Methylpyrazoles
  作者：James W. Pavlik、Naod Kebede

  DOI：10.1021/jo970897r

  日期：1997.11.1

  confirming the generality of this pathway in pyrazole photochemistry. Direct irradiation of 1-methyl-5-phenylpyrazole (3) resulted in the formation of 1-methyl-5-phenylimidazole (7), 1-methyl-2-phenylimidazole (8), and 1-methyl-4-phenylimidazole (4). Deuterium labeling revealed that these products were formed by P(4), P(6), and P(7) permutation pathways, respectively. (E)/(Z)-3-(N-methylamino)-3-phenylpropenenitrile

  1-甲基-4-苯基吡唑（2）在甲醇中的直接辐照导致区域特异性光变位成1-甲基-4-苯基咪唑（4）并光解为（E）/（Z）-3-（N-甲基氨基）- 2-苯基丙烯腈（5）和（E）/（Z）-2-（N-甲基氨基）-1-苯基乙烯基异氰酸酯（6）。氘标记确认通过P（4）排列途径发生的光移位。单独的实验表明5和6经历（Z）->（E）异构化和光环化成咪唑4。这些反应的量子产率表明，序列2-> 6-> 4是P（ 4）2-> 4的光子转移。也检测到异氰酸酯作为各种其他吡唑的P（4）光子转移的中间体，证实了该途径在吡唑光化学中的普遍性。1-甲基-5-苯基吡唑（3）的直接照射导致形成1-甲基-5-苯基咪唑（7），1-甲基-2-苯基咪唑（8）和1-甲基-4-苯基咪唑（4 ）。氘标记表明，这些产物分别由P（4），P（6）和P（7）排列途径形成。（E）/（Z）-3-（N-甲基氨基）-3-苯基丙烯腈（9）和（E）/（Z）-
• Colony stimulating factor-1 receptor (CSF-1R) inhibitors
  申请人：Genzyme Corporation

  公开号：US11274108B2

  公开（公告）日：2022-03-15

  Compounds of the formulas which are useful as colony stimulating factor-1 receptor inhibitors (“CSF-1R inhibitors”).

  下列式子的化合物 可用作集落刺激因子-1 受体抑制剂（"CSF-1R 抑制剂"）。
• COLONY STIMULATING FACTOR-1 RECEPTOR (CSF-1R) INHIBITORS
  申请人：Genzyme Corporation

  公开号：US20190016707A1

  公开（公告）日：2019-01-17

  Compounds of the formulas which are useful as colony stimulating factor-1 receptor inhibitors (“CSF-1R inhibitors”).
• Phototransposition chemistry of 1-phenylpyrazole. Experimental and computational studies
  作者：James W. Pavlik、Robert E. Connors、Douglas S. Burns、Edyth M. Kurzweil

  DOI：10.1021/ja00070a008

  日期：1993.8

  Photophysical and photochemical properties of 1-phenylpyrazole and 3-,4-, and 5-methyl-1-phenylpyrazoles have been investigated. INDO/S calculations agree with experimental measurements which show that the S1 and T1 states of these compounds are pi,pi* in character. Upon S0 --> S1(pi,pi*) excitation, these 1-phenylpyrazoles undergo phototransposition via a P4 permutation pathway. This process is consistent with a mechanism involving initial N-N bond cleavage followed by a 1,2-shift and cyclization to form the 1-phenylimidazole product. The 1,2-shift may occur via an undetected azirine intermediate. Whereas the regioselectivity of the reaction may be due to the stability of the N-phenyl radical, the quantum efficiencies of reaction and fluorescence are remarkably dependent on the location of the methyl group in the pyrazole ring. AM1 calculations provide energy-minimized structures for the more reactive 1-phenylpyrazole and 4-methyl- and 5-methyl-1-phenylpyrazoles in which the phenyl and pyrazole rings are perpendicular as required to stabilize the transition state for N-N bond cleavage. In contrast, such a perpendicular energy minimized S1 structure could not be obtained for the least reactive S1(pi,pi*) 3-methyl-1-phenylpyrazole which undergoes mainly radiative return to the ground state.