3-methyl-cis-2,7-diphenyl-1,2,3,4,6,7-hexahydro-1,4-diazepin-5-one | 66110-31-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 3-methyl-cis-2,7-diphenyl-1,2,3,4,6,7-hexahydro-1,4-diazepin-5-one
• 英文别名: t-3-methyl-r-2,c-7-diphenylhexahydro-1,4-diazepin-5-one；(2R,3R,7R)-3-methyl-2,7-diphenyl-1,4-diazepan-5-one
• CAS: 66110-31-4；143900-77-0
• 化学式: C₁₈H₂₀N₂O
• 分子量: 280.37
• InChiKey: RVDBJQXNFKPNRX-QBIMZIAESA-N

物化性质

• 熔点：
  183-185 °C
• 沸点：
  496.0±45.0 °C(Predicted)
• 密度：
  1.073±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  41.1
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-methyl-cis-2,7-diphenyl-1,2,3,4,6,7-hexahydro-1,4-diazepin-5-one 在 盐酸 、 sodium nitrite 作用下， 生成 t-3-methyl-1-nitroso-r-2,c-7-diphenylhexahydro-1,4-diazepin-5-one
  参考文献：
  名称：

  Chemistry of N-nitroso compounds. 3. Synthesis and conformational analysis of N-nitrosohexahydro-1,4-diazepin-5-ones

  摘要：

  A comparison of the barrier to N-X rotation in a series of compounds with various N-X=Y systems has shown that the N-nitrosamines, some of which have been found to be highly carcinogenic, exhibit the highest rotation barrier. All the other systems which, to date, have not been found to be carcinogenic have lower barriers. With a view to studying the influence of the N-nitroso group on the conformations of N-nitrosodiazepinones, several 1-nitroso-r-2,c-7-diphenylhexahydro-1,4-diazepin-5-ones 16-20 were synthesized from the corresponding r-2,c-7-diphenylhexahydro-1,4-diazepin-5-ones 11-15 and their conformations in deuterated solvents were studied. The N-nitrosodiazepinones 16-20 were found to prefer boat conformations, with some flattening at the nitroso end of the ring and with quasi-axial phenyl groups. As shown earlier, N-nitroso-r-2,c-6-diphenylpiperidines prefer partially twisted chair conformations with equatorial phenyl groups and r-2,c-6-dimethyl-N-nitrosopiperidine prefers a chair conformation with 1,3-diaxial methyl groups. The title compounds 16-20 exist in conformational equilibria involving syn and anti orientations of the coplanar nitroso group in an approximate syn-anti ratio of 60:40 (observed from H-1 NMR spectroscopic studies). The C-13 NMR spectra of these compounds show that the carbons syn to the nitroso group are shifted upfield by about 11-15 ppm compared to the precursor compounds 11-15, while the anti carbons were shifted by less than 1 ppm in either direction. It was observed that all of the syn alpha-protons are more deshielded than the anti alpha-protons while for the beta-protons the reverse is true. The N-N=O rotational barriers for these compounds could not be determined precisely since they start decomposing above 150-degrees-C in DMSO-d6 Solutions. A rough estimate of the energy barrier for the isopropyl derivative 19 shows that the barrier is at least 21.5 kcal mol-1.

  DOI：

  10.1021/jo00048a041
• 作为产物：
  描述：

  3-methyl-2,6-diphenylpiperidin-4-one hydrochloride 在 sodium azide 、 硫酸 作用下， 生成 3-methyl-cis-2,7-diphenyl-1,2,3,4,6,7-hexahydro-1,4-diazepin-5-one
  参考文献：
  名称：

  Chemistry of N-nitroso compounds. 3. Synthesis and conformational analysis of N-nitrosohexahydro-1,4-diazepin-5-ones

  摘要：

  A comparison of the barrier to N-X rotation in a series of compounds with various N-X=Y systems has shown that the N-nitrosamines, some of which have been found to be highly carcinogenic, exhibit the highest rotation barrier. All the other systems which, to date, have not been found to be carcinogenic have lower barriers. With a view to studying the influence of the N-nitroso group on the conformations of N-nitrosodiazepinones, several 1-nitroso-r-2,c-7-diphenylhexahydro-1,4-diazepin-5-ones 16-20 were synthesized from the corresponding r-2,c-7-diphenylhexahydro-1,4-diazepin-5-ones 11-15 and their conformations in deuterated solvents were studied. The N-nitrosodiazepinones 16-20 were found to prefer boat conformations, with some flattening at the nitroso end of the ring and with quasi-axial phenyl groups. As shown earlier, N-nitroso-r-2,c-6-diphenylpiperidines prefer partially twisted chair conformations with equatorial phenyl groups and r-2,c-6-dimethyl-N-nitrosopiperidine prefers a chair conformation with 1,3-diaxial methyl groups. The title compounds 16-20 exist in conformational equilibria involving syn and anti orientations of the coplanar nitroso group in an approximate syn-anti ratio of 60:40 (observed from H-1 NMR spectroscopic studies). The C-13 NMR spectra of these compounds show that the carbons syn to the nitroso group are shifted upfield by about 11-15 ppm compared to the precursor compounds 11-15, while the anti carbons were shifted by less than 1 ppm in either direction. It was observed that all of the syn alpha-protons are more deshielded than the anti alpha-protons while for the beta-protons the reverse is true. The N-N=O rotational barriers for these compounds could not be determined precisely since they start decomposing above 150-degrees-C in DMSO-d6 Solutions. A rough estimate of the energy barrier for the isopropyl derivative 19 shows that the barrier is at least 21.5 kcal mol-1.

  DOI：

  10.1021/jo00048a041

文献信息

• Fast Equilibrium in <i>N</i>-(Ethoxycarbonyl)-<i>r</i>-2,<i>c</i>-7-diphenylhexahydro-1,4-diazepin-5-ones in Flattened Boat Conformations
  作者：Ramasubbu Jeyaraman、Subbu Ponnuswamy

  DOI：10.1021/jo9704265

  日期：1997.11.1

  N(1),N(4)-bis(ethoxycarbonyl) derivatives 9 and 10, and the barriers for the N-CO rotation were found to be 49.9 and 58.0 kJ mol(-1), respectively. These barriers are much lower than those observed for N-nitroso- and N-formyl-r-2,c-7-diphenylhexahydro-1,4-diazepin-5-ones (90.0 and 84.4 kJ mol(-1), respectively), indicating a fast equilibrium in 9 and 10 at room temperature.

  已经使用NMR光谱技术研究了r-2，c-7-二苯基六氢-1，4-二氮杂庚基-5-酮9-11的三种N-乙氧基羰基衍生物的优选构象。发现N（1），N（4）-双（乙氧羰基）-r-2，c-7-二苯基六氢-1,4-二氮杂-5--5-酮9和10偏爱扁平的船形，且两者之间具有快速平衡发现N-CO旋转异构体，而发现4-（乙氧基羰基）-t-3-异丙基-r-2，c-7-二苯基六氢-1,4-二氮杂潘-5-酮（11）更喜欢N-CO异构体COOEt组锁定在一种旋转状态。对N（1），N（4）-双（乙氧基羰基）衍生物9和10进行了动态（1）H NMR研究，发现N-CO旋转的障碍为49.9和58.0 kJ mol （-1）。这些势垒远低于N-亚硝基和N-甲酰基-r-2，c-7-二苯基六氢-1，
• Chemistry of N-Nitroso Compounds. 7. Conformational Preferences of Hexahydro-N1,N4- dinitroso-r-2,c-7-diphenyl-1H-1,4-diazepines: Use of Modified 1D HOHAHA and NOE Techniques
  作者：Ramasubbu Jeyaraman、Udayampalayam P. Senthilkumar、Peter Bigler

  DOI：10.1021/jo00128a018

  日期：1995.11

  Modified HOHAHA and NOE experiments on three N,N'-dinitrosohexahydrodiazepines, at temperatures ranging from -50 degrees C to +120 degrees C, indicated that each of the title compounds exists as an equilibrium mixture of two families of conformations, the major family consisting of four rotamers and the minor consisting of, possibly, four rotamers resulting from two parallel dynamic processes viz., the restricted N-N rotation at two N-NO bonds and the pseudorotation of the seven-membered ring. The 3-isopropyl derivative 10, at +50 degrees C, exhibited only four resonances for each kind of proton/carbon, indicating that the rate of pseudorotation is fast compared to the NMR time scale. The H-1 resonances, broad at room temperature, became decoalesced at -50 degrees C as a result of the slow pseudorotation process. In all the three dinitroso compounds, of the two sets of twist-chair conformers, the major rotamers (similar to 95%) have the alkyl group (at C3) axially disposed while the minor rotamers have quasiequatorial alkyl groups. On the other hand, the alkyl group at C6 of the 3,6-dimethyl derivative 11 adopts equatorial orientation in all its conformers.
• Bhaskar Reddy; Somasekhar Reddy; Padmavathi, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1999, vol. 38, # 2, p. 141 - 147
  作者：Bhaskar Reddy、Somasekhar Reddy、Padmavathi

  DOI：——

  日期：——