N-(p-toluenesulfonyl)pyrrolo diazene | 152940-78-8

• 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: N-(p-toluenesulfonyl)pyrrolo diazene
• 英文别名: 6-(4-Methylphenyl)sulfonyl-1,4-dihydropyrrolo[3,4-d]pyridazine
• CAS: 152940-78-8
• 化学式: C₁₃H₁₃N₃O₂S
• 分子量: 275.331
• InChiKey: ADLAJDFIWMRNTO-UHFFFAOYSA-N

物化性质

• 沸点：
  472.3±55.0 °C(Predicted)
• 密度：
  1.40±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  72.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(p-toluenesulfonyl)pyrrolo diazene 以 甲醇 为溶剂， 反应 0.83h， 生成 dimethyl 5-(4-methylphenyl)sulfonyl-4,6-dihydro-1H-pyrrolo[3,4-d]pyridazine-2,3-dicarboxylate
  参考文献：
  名称：

  Triplet Species from Dihydropyrrolo[3,4-d]pyridazines, the Diazene Precursors of N-Arenesulfonyl-3,4-dimethylenepyrroles

  摘要：

  In contrast to the photolyses of N-methyl- or N-pivaloylpyrrolo[3,4]dihydropyridazines in low-temperature matrices, which give the blue, ESR-inactive singlet 3,4-dimethylenepyrrole biradical at all wavelengths, the photolyses of the N-arenesulfonyl derivatives in this series are strongly wavelength-dependent. In three separate instances, both singlet and triplet N-arenesulfonyl-3,4-dimethylenepyrrole biradicals have been observed. In each case, one or two other triplets are seen by ESR spectroscopy after irradiation under special conditions, These are tentatively assigned conformationally isomeric diazenyl biradical structures. The possible origins of the slow intersystem crossing rates for singlet-triplet interconversions in N-arenesulfonyl-3,4-dimethylenepyrrole biradicals are examined. Near-zero ionic character of the singlet wave function is considered to be a less likely cause than conformational control of the spin state. The latter circumstance would require that intersystem crossing be coupled to conformational change, which can be very slow at low temperatures. The zero-field splittings determined from the ESR spectra of N-tosyl-3,4-dimethylenepyrrole biradical are found to be temperature-dependent, which could be caused by librations and/or internal rotational (conformational) motions of the biradical in the matrix.

  DOI：

  10.1021/ja963114c
• 作为产物：
  描述：

  3,4-吡咯二羧酸二乙酯 在 盐酸 、 氢氧化钾 、 四丁基硫酸氢铵 、 chlorotriphenylphosphonium chloride 、 sodium hydride 、 二异丁基氢化铝 、 dimethyl azodicarboxylate 作用下， 以 乙醚 、 二氯甲烷 、 二甲基亚砜 为溶剂， 生成 N-(p-toluenesulfonyl)pyrrolo diazene
  参考文献：
  名称：

  通过设计的结构变化调整非凯库勒系列中的单线态-三线态能隙。N-取代-3,4-二亚甲基吡咯双自由基的单线态

  摘要：

  半经验量子化学计算（AM1/CI 和 PM3/CI）证实了定性微扰预测，即 3,4-二亚甲基吡咯环氮上的吸电子基团应将单线态和三线态的能量分离降低到接近零。已经开发了此类双自由基的一系列前体的合成。对双自由基的化学和光谱研究表明，在取代基是甲基、异丁酰基和新戊酰基的情况下，它们具有持久的单线态。在 N-芳烃磺酰基-3,4-二亚甲基吡咯的情况下，可以观察到单线态和三线态两种形式作为持久性物种。在本文中，描述了该系列中的单线态的特性。

  DOI：

  10.1021/ja963113k

文献信息

• Absolute rates of heterocyclic singlet biradical reactions determined by nanosecond time-resolved absorption spectroscopy. Dimerizations and cycloadditions to alkenes and to dioxygen
  作者：Richard B. Heath、Linda C. Busch、Xu Wu Feng、Jerome A. Berson、J. C. Scaiano、Alain B. Berinstain

  DOI：10.1021/j100152a047

  日期：1993.12

  Singlet biradicals of the 3,4-dimethyleneheterocycle series, where the heterocycle is furan, thiophene, or N-substituted pyrrole, with chromophores in the UV-vis region (560-640 nm), are generated by nanosecond laser flash photolysis of diazene precursors in fluid solution. The rate constants for disappearance of these transients are determined by time-resolved absorption spectroscopy using the long-wavelength band. The rate constants for dimerization are near the encounter-controlled rate. Rates of trapping by alkenes are well described by a frontier orbital model. Oxygen trapping rate constants range between 10(7) and 10(9) M-1 s-1. The ratios of rate constants for trapping of 3,4-dimethylene-N-(p-toluenesulfonyl)pyrrole by pairs of alkenes in preparative competition experiments are in good agreement with those determined by the flash photolytic method. This confirms assignments of the 3,4-dimethyleneheterocycle structure to the chromophore of the biradical transients.
• Tuning the Singlet−Triplet Energy Gap in a Non-Kekulé Series by Designed Structural Variation. The Singlet States of <i>N</i>-Substituted-3,4-dimethylenepyrrole Biradicals
  作者：Linda C. Bush、Richard B. Heath、Xu Wu Feng、Patricia A. Wang、Ljiljana Maksimovic、Anne In Song、Wen-Sheng Chung、Alain B. Berinstain、J. C. Scaiano、Jerome A. Berson

  DOI：10.1021/ja963113k

  日期：1997.2.1

  that electron-withdrawing groups on the ring nitrogen of a 3,4-dimethylenepyrrole should diminish the energy separation of the singlet and triplet states to near zero. Syntheses of a series of precursors of such biradicals have been developed. Study of the chemistry and spectroscopy of the biradicals has revealed persistent singlet states for the cases where the substituent is methyl, isobutyryl, and

  半经验量子化学计算（AM1/CI 和 PM3/CI）证实了定性微扰预测，即 3,4-二亚甲基吡咯环氮上的吸电子基团应将单线态和三线态的能量分离降低到接近零。已经开发了此类双自由基的一系列前体的合成。对双自由基的化学和光谱研究表明，在取代基是甲基、异丁酰基和新戊酰基的情况下，它们具有持久的单线态。在 N-芳烃磺酰基-3,4-二亚甲基吡咯的情况下，可以观察到单线态和三线态两种形式作为持久性物种。在本文中，描述了该系列中的单线态的特性。
• Triplet Species from Dihydropyrrolo[3,4-<i>d</i>]pyridazines, the Diazene Precursors of <i>N</i>-Arenesulfonyl-3,4-dimethylenepyrroles
  作者：Linda C. Bush、Ljiljana Maksimovic、Xu Wu Feng、Helen S. M. Lu、Jerome A. Berson

  DOI：10.1021/ja963114c

  日期：1997.2.1

  In contrast to the photolyses of N-methyl- or N-pivaloylpyrrolo[3,4]dihydropyridazines in low-temperature matrices, which give the blue, ESR-inactive singlet 3,4-dimethylenepyrrole biradical at all wavelengths, the photolyses of the N-arenesulfonyl derivatives in this series are strongly wavelength-dependent. In three separate instances, both singlet and triplet N-arenesulfonyl-3,4-dimethylenepyrrole biradicals have been observed. In each case, one or two other triplets are seen by ESR spectroscopy after irradiation under special conditions, These are tentatively assigned conformationally isomeric diazenyl biradical structures. The possible origins of the slow intersystem crossing rates for singlet-triplet interconversions in N-arenesulfonyl-3,4-dimethylenepyrrole biradicals are examined. Near-zero ionic character of the singlet wave function is considered to be a less likely cause than conformational control of the spin state. The latter circumstance would require that intersystem crossing be coupled to conformational change, which can be very slow at low temperatures. The zero-field splittings determined from the ESR spectra of N-tosyl-3,4-dimethylenepyrrole biradical are found to be temperature-dependent, which could be caused by librations and/or internal rotational (conformational) motions of the biradical in the matrix.