(2Z,6Z)-2,6-bis((1H-pyrrol-2-yl)methylene)cyclohexanone

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (2Z,6Z)-2,6-bis((1H-pyrrol-2-yl)methylene)cyclohexanone
• 英文别名: (2Z,6Z)-2,6-bis(1H-pyrrol-2-ylmethylidene)cyclohexan-1-one
• 化学式: C₁₆H₁₆N₂O
• 分子量: 252.316
• InChiKey: UKIUACHVRRQMGB-MIMPSMLTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  48.6
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-吡咯甲醛 在 potassium hydroxide 作用下， 以 氘代二甲亚砜 、 乙醇 、 二氯甲烷-D2 、 水 为溶剂， 反应 2.0h， 生成 (2Z,6Z)-2,6-bis((1H-pyrrol-2-yl)methylene)cyclohexanone
  参考文献：
  名称：

  Molecular Structure and Photoinduced Intramolecular Hydrogen Bonding in 2-Pyrrolylmethylidene Cycloalkanones

  摘要：

  The structures of pyrrolylmethylidene derivatives of 2,3-dihydro-1H-inden-1-one (3), 3,4-dihydro-naphthalen-1(2H)-one (4), and cycloalkanones (5-7) were studied for the first time in the solid state and solution by NMR, IR, and UV spectroscopies supported by DFT quantum mechanical calculations. It was shown that all studied compounds except cycloheptanone derivative 7 both in crystal and in solution exist in the form of dimers where single E or E,E configuration with respect to the exocyclic C=C bond is stabilized by intermolecular hydrogen bonds N-H center dot center dot center dot O=C. UV irradiation at a wavelength of 365 nm of MeCN or DMSO solutions of 3-6 results, depending on the exposition time and solvent, partial to complete isomerization to the Z or Z,E isomers (in the case of 6, also the Z,Z isomer). The NMR and IR spectroscopy data show the existence of a strong intramolecular hydrogen bond N-H center dot center dot center dot O=C in the Z moieties of isomerized compounds. The studied compounds are protonated by trifluoroacetic acid at the carbonyl oxygen, in spite of the reverse order of basicity and nucleophilicity of the carbonyl group and the pyrrole ring. Investigation of the behavior of compound 6 with respect to acetate and fluoride anions allows one to consider it as a potential fluoride sensor.

  DOI：

  10.1021/acs.joc.5b01604

文献信息

• Molecular Structure and Photoinduced Intramolecular Hydrogen Bonding in 2-Pyrrolylmethylidene Cycloalkanones
  作者：Mark Sigalov、Bagrat Shainyan、Nina Chipanina、Larisa Oznobikhina、Natalia Strashnikova、Irina Sterkhova

  DOI：10.1021/acs.joc.5b01604

  日期：2015.11.6

  The structures of pyrrolylmethylidene derivatives of 2,3-dihydro-1H-inden-1-one (3), 3,4-dihydro-naphthalen-1(2H)-one (4), and cycloalkanones (5-7) were studied for the first time in the solid state and solution by NMR, IR, and UV spectroscopies supported by DFT quantum mechanical calculations. It was shown that all studied compounds except cycloheptanone derivative 7 both in crystal and in solution exist in the form of dimers where single E or E,E configuration with respect to the exocyclic C=C bond is stabilized by intermolecular hydrogen bonds N-H center dot center dot center dot O=C. UV irradiation at a wavelength of 365 nm of MeCN or DMSO solutions of 3-6 results, depending on the exposition time and solvent, partial to complete isomerization to the Z or Z,E isomers (in the case of 6, also the Z,Z isomer). The NMR and IR spectroscopy data show the existence of a strong intramolecular hydrogen bond N-H center dot center dot center dot O=C in the Z moieties of isomerized compounds. The studied compounds are protonated by trifluoroacetic acid at the carbonyl oxygen, in spite of the reverse order of basicity and nucleophilicity of the carbonyl group and the pyrrole ring. Investigation of the behavior of compound 6 with respect to acetate and fluoride anions allows one to consider it as a potential fluoride sensor.