(1α,4α,4aα,7aα)-4,4a,7,7a-tetrahydro-8,8-dimethyl-1,4-bis(3'-nitrophenyl)-1,4-methano-1H-cyclopentapyridazine

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: (1α,4α,4aα,7aα)-4,4a,7,7a-tetrahydro-8,8-dimethyl-1,4-bis(3'-nitrophenyl)-1,4-methano-1H-cyclopentapyridazine
• 英文别名: (1S,2R,6S,7R)-10,10-dimethyl-1,7-bis(3-nitrophenyl)-8,9-diazatricyclo[5.2.1.02,6]deca-3,8-diene
• 化学式: C₂₂H₂₀N₄O₄
• 分子量: 404.425
• InChiKey: CPXUHCGPWHBWAF-KIZRIRGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  30
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  116
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1α,4α,4aα,7aα)-4,4a,7,7a-tetrahydro-8,8-dimethyl-1,4-bis(3'-nitrophenyl)-1,4-methano-1H-cyclopentapyridazine 以 甲苯 为溶剂， 反应 8.0h， 以97%的产率得到2,4-bis(3'-nitrophenyl)-3,3-dimethyl-endo-tricyclo<3.3.0.0^2,4>oct-6-ene
  参考文献：
  名称：

  Radical Stabilization and Ground State Polar Substituent Effects in the Thermal Decomposition of Azoalkanes

  摘要：

  The thermolysis rates of a series of the 1,4-diaryl-2,3-diaza[2.2.1]bicyclohept-2 derivatives 1 with a large variety of aryl substituents (p-NH2, p-OMe, p-Me, H, p-F, p-Cl, p-Br, m-I, p-I, Nt-CN, p-CN, m-NO2, p-NOz, and p-CO(2)Me) have been determined to probe the electronic substituent effects in the thermal decomposition of azoalkanes. The correlation of the logarithmic relative rate constants versus the Creary substituent constants for radical stabilization (cf. Creary, X.; et al. J. Org. Chem. 1987, 52, 3254) improved considerably when polar effects (positive rho value) were included in the form of a two-parameter Hammett treatment. The importance of polar effects was also established in the reported thermolysis rate data for aryl-substituted azopropanes 2, azoethanes 3, azomethanes 4, azoneopentanes 5, and 3,5-diaryl-1-pyrazolines 6. The two-parameter analysis reveals that the thermal decomposition rates of azoalkanes are enhanced by radical- as well as anion-stabilizing substituents. On one hand, the ratio of the radical and polar reaction constants (rho(rad)+rho(pol)) serves as useful parameter to diagnose the radical nature in the decompositions of azoalkanes; thus, in general, radical effects dominate within the azoalkane 1-6 series. On the other hand, the overall sensitivity of the thermal decompositions toward substituent effects is reflected by the sum of the reaction constants (rho(rad)+rho(pol)) The polar effect is attributed to polar destabilization in the ground states of the azoalkanes, for which the polarized C-N bond is weakened by aryl substituents with electron accepters at the positively charged benzylic carbon atom. Semiempirical (AM1) calculations corroborate such polar effects for the azoalkanes 1-6 versus their corresponding diaryl-substituted alkanes 7-12.

  DOI：

  10.1021/ja00103a012
• 作为产物：
  描述：

  1,3-bis(3'-nitrophenyl)-2,2-dimethyl-1,3-propanedione 在 一水合肼 、 三氟乙酸 作用下， 以 二氯甲烷 、 氯仿 为溶剂， 反应 26.0h， 生成 (1α,4α,4aα,7aα)-4,4a,7,7a-tetrahydro-8,8-dimethyl-1,4-bis(3'-nitrophenyl)-1,4-methano-1H-cyclopentapyridazine
  参考文献：
  名称：

  Radical Stabilization and Ground State Polar Substituent Effects in the Thermal Decomposition of Azoalkanes

  摘要：

  The thermolysis rates of a series of the 1,4-diaryl-2,3-diaza[2.2.1]bicyclohept-2 derivatives 1 with a large variety of aryl substituents (p-NH2, p-OMe, p-Me, H, p-F, p-Cl, p-Br, m-I, p-I, Nt-CN, p-CN, m-NO2, p-NOz, and p-CO(2)Me) have been determined to probe the electronic substituent effects in the thermal decomposition of azoalkanes. The correlation of the logarithmic relative rate constants versus the Creary substituent constants for radical stabilization (cf. Creary, X.; et al. J. Org. Chem. 1987, 52, 3254) improved considerably when polar effects (positive rho value) were included in the form of a two-parameter Hammett treatment. The importance of polar effects was also established in the reported thermolysis rate data for aryl-substituted azopropanes 2, azoethanes 3, azomethanes 4, azoneopentanes 5, and 3,5-diaryl-1-pyrazolines 6. The two-parameter analysis reveals that the thermal decomposition rates of azoalkanes are enhanced by radical- as well as anion-stabilizing substituents. On one hand, the ratio of the radical and polar reaction constants (rho(rad)+rho(pol)) serves as useful parameter to diagnose the radical nature in the decompositions of azoalkanes; thus, in general, radical effects dominate within the azoalkane 1-6 series. On the other hand, the overall sensitivity of the thermal decompositions toward substituent effects is reflected by the sum of the reaction constants (rho(rad)+rho(pol)) The polar effect is attributed to polar destabilization in the ground states of the azoalkanes, for which the polarized C-N bond is weakened by aryl substituents with electron accepters at the positively charged benzylic carbon atom. Semiempirical (AM1) calculations corroborate such polar effects for the azoalkanes 1-6 versus their corresponding diaryl-substituted alkanes 7-12.

  DOI：

  10.1021/ja00103a012

文献信息

• Electronic Effects of <i>para</i>- and <i>meta</i>-Substituents on the EPR <i>D</i> Parameter in 1,3-Arylcyclopentane-1,3-diyl Triplet Diradicals. A New Spectroscopic Measure of α Spin Densities and Radical Stabilization Energies in Benzyl-Type Monoradicals
  作者：Waldemar Adam、Heinrich M. Harrer、Fumio Kita、Hans-Gert Korth、Werner M. Nau

  DOI：10.1021/jo9622035

  日期：1997.3.1

  The zero-field splitting D parameter was determined in a 2-MTHF glass matrix at 77 K for a large set (35 derivatives) of para- and meta-substituted 1,3-arylcyclopentane-1,3-diyl triplet diradicals 6. The D values are a sensitive function of electronic substituent effects; for convenience, the Delta D scale was defined as the difference D-H - D-X. Spin accepters decrease while spin donors increase the D value relative to the unsubstituted reference system (D-H) Theoretical (PM3-AUHF) alpha spin densities (rho alpha) for the corresponding cumyl monoradicals 7 display a good linear dependence (r(2) = 0.963) when plotted against the D parameters of the triplet diradicals 6. The radical stabilization energies (RSE) of the cumyl radicals 7 were semiempirically calculated as the energy difference between in-plane (full conjugation) and perpendicular (no conjugation) conformations of the aryl groups and shown to correlate linearly (r(2) = 0.947) against the experimental D parameter for the corresponding triplet diradicals 6. These linear correlations, i.e., D versus rho alpha and versus RSE, demonstrate that the D parameter of the localized triplet diradicals 6 reflects reliably electronic substituent effects in benzyl-type monoradicals. The spectroscopic Delta D scale correlates poorly with the reported chemical sigma(rad) scales, unless polar corrections (Hammett sigma(pol) values) are made by means of a two-parameter Hammett treatment. Then a good linear correlation (r(2) = 0.921) of the Delta D values versus the Creary sigma(rad) scale applies; as expected, the radical effects dominate(rho(rad) = 1.00 versus rho(pol) = 0.41). The advantages of the new EPR-spectroscopic Delta D scale are that polar effects are nominal and the D parameter can be measured experimentally with sufficient accuracy to probe even small and subtle electronic effects through changes in the a spin densities.
• Radical Stabilization and Ground State Polar Substituent Effects in the Thermal Decomposition of Azoalkanes
  作者：Werner M. Nau、Heinrich M. Harrer、Waldemar Adam

  DOI：10.1021/ja00103a012

  日期：1994.11

  The thermolysis rates of a series of the 1,4-diaryl-2,3-diaza[2.2.1]bicyclohept-2 derivatives 1 with a large variety of aryl substituents (p-NH2, p-OMe, p-Me, H, p-F, p-Cl, p-Br, m-I, p-I, Nt-CN, p-CN, m-NO2, p-NOz, and p-CO(2)Me) have been determined to probe the electronic substituent effects in the thermal decomposition of azoalkanes. The correlation of the logarithmic relative rate constants versus the Creary substituent constants for radical stabilization (cf. Creary, X.; et al. J. Org. Chem. 1987, 52, 3254) improved considerably when polar effects (positive rho value) were included in the form of a two-parameter Hammett treatment. The importance of polar effects was also established in the reported thermolysis rate data for aryl-substituted azopropanes 2, azoethanes 3, azomethanes 4, azoneopentanes 5, and 3,5-diaryl-1-pyrazolines 6. The two-parameter analysis reveals that the thermal decomposition rates of azoalkanes are enhanced by radical- as well as anion-stabilizing substituents. On one hand, the ratio of the radical and polar reaction constants (rho(rad)+rho(pol)) serves as useful parameter to diagnose the radical nature in the decompositions of azoalkanes; thus, in general, radical effects dominate within the azoalkane 1-6 series. On the other hand, the overall sensitivity of the thermal decompositions toward substituent effects is reflected by the sum of the reaction constants (rho(rad)+rho(pol)) The polar effect is attributed to polar destabilization in the ground states of the azoalkanes, for which the polarized C-N bond is weakened by aryl substituents with electron accepters at the positively charged benzylic carbon atom. Semiempirical (AM1) calculations corroborate such polar effects for the azoalkanes 1-6 versus their corresponding diaryl-substituted alkanes 7-12.