2,3-Dihydroperimidine-2-spiro-1'(3,5-di-tert-butyl-2,5-cyclohexadien-4-one) | 120570-49-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2,3-Dihydroperimidine-2-spiro-1'(3,5-di-tert-butyl-2,5-cyclohexadien-4-one)
• 英文别名: 2,3-Dihydro-2-spiro-(4-2,6-di-tert-butyl-2,5-cyclohexadienone)perimidine；2,3-dihydro-2-spiro-(4-2,6-di-tert-butylcyclohexadien-2,5-one)permidine；3,5-di-tert-butyl-1'H,3'H,4H-spiro[cyclohexa-2,5-diene-1,2'-perimidin]-4-one；2',6'-ditert-butylspiro[1,3-dihydroperimidine-2,4'-cyclohexa-2,5-diene]-1'-one
• CAS: 120570-49-2
• 化学式: C₂₄H₂₈N₂O
• 分子量: 360.499
• InChiKey: AUNBJSSHPOVQPI-UHFFFAOYSA-N

物化性质

• 熔点：
  163-165 °C(Solv: heptane (142-82-5))
• 沸点：
  565.2±50.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  41.1
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,3-Dihydroperimidine-2-spiro-1'(3,5-di-tert-butyl-2,5-cyclohexadien-4-one) 以 乙腈 为溶剂， 生成 4-(8-Amino-naphthalen-1-ylimino)-2,6-di-tert-butyl-cyclohexa-2,5-dienone
  参考文献：
  名称：

  喹唑啉螺己二烯酮分子开关的实验和计算电化学–电致变色与光致变色行为的差异

  摘要：

  我们的本科研究小组长期致力于光致变色分子开关的perimidinespirohexadienone（PSHD）系列的缺电子类似物的制备和研究，有可能用作“光致变色光氧化剂”，以提高对光感应电荷转移的门控敏感性。我们先前曾报道过两种紧密相关且还原性更高的喹唑啉螺己二酮（QSHD）的光化学，其中PSHD的萘被喹啉取代。在目前的工作中，我们报告了我们对这些不对称QSHDs的电化学研究。除了短波长和光致变色长波长异构体之外，我们还发现，第二种独特的长波长异构体是​​通过电化学方法生产的。这种不同的长波长异构体是​​由螺环开环的区域化学差异引起的。通过循环伏安法确定了两种长波异构体的结构，1 H NMR分析与计算模型相结合。将这些结果与对称母体PSHD的结果进行比较，后者由于对称性在电化学或光化学开环时仅具有单一可能的区域异构体。键长，键序和分子轨道的密度泛函理论计算可合理化QSHD的这种光致变色与电致变色行为。

  DOI：

  10.3762/bjoc.15.240
• 作为产物：
  描述：

  4-(8-Amino-naphthalen-1-ylimino)-2,6-di-tert-butyl-cyclohexa-2,5-dienone 生成 2,3-Dihydroperimidine-2-spiro-1'(3,5-di-tert-butyl-2,5-cyclohexadien-4-one)
  参考文献：
  名称：

  KOMISSAROV, V. N.;XARLANOV, V. A.;UXIN, L. YU.;MINKIN, V. I., DOKL. AN CCCP, 301,(1988) N 4, S. 902-905

  摘要：

  DOI：

文献信息

• Synthesis, structure and properties of perimidine spirans
  作者：S. M. Aldoshin、M. A. Novozhilova、L. O. Atovmyan、V. N. Komissarov、V. A. Kharlanov、L. Yu. Ukhin、V. I. Minkin

  DOI：10.1007/bf00958007

  日期：1991.3

  A study was carried out on a new class of photo- and thermochromic spirocyclic cyclohexadienoneperimidines and 4H-naphtholinoneperimidines. The structures of two of these compounds were determined. The lengths of the C(spiro)-N bonds were found to be unequivalent; one of these bonds is cleaved in the photo- and thermochromic transformations. The nitrogen atom of the perimidine ring in both compounds was found to have pyramidal configuration with cis arrangement of the unshared electron pairs, while the cyclohexadienone fragments are strongly distorted toward the boat conformation. The nature of the dependence of the photo- and thermochromic properties on their structure and solvent was established.
• Kharlanov, V. A.; Knyazhanskii, M. I.; Kuznetsov, V. E., Journal of Organic Chemistry USSR (English Translation), 1992, vol. 28, # 5.2, p. 855 - 858
  作者：Kharlanov, V. A.、Knyazhanskii, M. I.、Kuznetsov, V. E.

  DOI：——

  日期：——
• ——
  作者：V. A. Kharlanov

  DOI：10.1023/a:1012405229637

  日期：——

  Thermodynamic equilibrium between the spirane and quinonimine structures of photochromic perimidine derivatives was studied by electron absorption spectroscopy and semiempirical quantum-chemical methods (AM1 and PM3). The experimental data showed that the reaction entropy DeltaS(0) in octane weakly depends on the substituent structure (0.015-0.024 kJ mol(-1) K-1) and that the enthalpy of the reaction for the compound with bulky isobutyl substituent (DeltaH(0) = 7.1 kJ/mol) is lower than for those containing hydrogen and methyl group (12.9 and 13.1 kJ/mol, respectively). According to the calculations, in the spirane structure the orientation of lone electron pairs on the perimidine nitrogen atoms may be both cisoid or transoid for different orientations of the cyclohexadiene fragment which adopts a boat conformation. The quinonimine isomer can also exist in different stable conformations.
• Kharlamov, V. A.; Komissarov, V. N.; Ukhin, L. Yu., Journal of Organic Chemistry USSR (English Translation), 1991, vol. 27, # 8, p. 1550 - 1554
  作者：Kharlamov, V. A.、Komissarov, V. N.、Ukhin, L. Yu.、Osipova, M. L.、Knyazhanskii, M. I.

  DOI：——

  日期：——
• Synthesis and structure of 2,6-di-tert-butyl-1,4-benzoquinone-4N-(8-tosylamino-1-naphthyl) imine
  作者：S. M. Aldoshin、M. A. Novozhilova、L. O. Atovmyan、V. N. Komissarov、L. Yu. Ukhin、V. A. Kharlanov

  DOI：10.1007/bf01172258

  日期：1991.8

  The structure of 2,6-di-tert-butyl-1,4-benzoquinone-4-N-(8-tosylamino-1-naphthyl)imine (IId) has been studied as a model for the open form of thermo- and photochromic compounds in the cyclohexadienoneperimidine series (I), in which rearrangement occurs due to C(spiro)-N bond cleavage and N --> N proton transfer upon thermal or photoexcitation. Introduction of a bulky, electron-withdrawing tosyl substituent to the nitrogen atom stabilizes the open quinoneimine form, both in the crystalline state and in solution. The cyclohexadienone fragment is nonplanar and exists in a "boat" configuration. The open quinoneimine structure is retained upon replacement of the tosyl substituent by a less bulky electron-withdrawing acetyl substituent, suggesting that electronic factors are decisive in formation of the open structure.