1-Methyl-2,3-dihydro-2-spiro-(4-2,6-di-tert-butyl-2,5-cyclohexadienone)perimidine | 120608-41-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-Methyl-2,3-dihydro-2-spiro-(4-2,6-di-tert-butyl-2,5-cyclohexadienone)perimidine
• 英文别名: 1-methyl-2,3-dihydro-2-spiro-(4-2,6-di-tert-butylcyclohexadien-2,5-one)perimidine；2',6'-ditert-butyl-3-methylspiro[1H-perimidine-2,4'-cyclohexa-2,5-diene]-1'-one
• CAS: 120608-41-5
• 化学式: C₂₅H₃₀N₂O
• 分子量: 374.526
• InChiKey: OEXHCAAHNUMKRY-UHFFFAOYSA-N

物化性质

• 熔点：
  179-180 °C(Solv: heptane (142-82-5))
• 沸点：
  556.4±50.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  32.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-Methyl-2,3-dihydro-2-spiro-(4-2,6-di-tert-butyl-2,5-cyclohexadienone)perimidine 以 正辛烷 为溶剂， 生成 2,6-Di-tert-butyl-4-(8-methylamino-naphthalen-1-ylimino)-cyclohexa-2,5-dienone
  参考文献：
  名称：

  摘要：

  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.

  DOI：

  10.1023/a:1012405229637
• 作为产物：
  描述：

  2,6-二叔丁基苯醌 在 potassium carbonate 作用下， 以 丙醇 、 二甲基亚砜 为溶剂， 反应 15.0h， 生成 1-Methyl-2,3-dihydro-2-spiro-(4-2,6-di-tert-butyl-2,5-cyclohexadienone)perimidine
  参考文献：
  名称：

  Synthesis, structure and properties of perimidine spirans

  摘要：

  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.

  DOI：

  10.1007/bf00958007

文献信息

• 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：——
• 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.
• ALDOSHIN, S. M.;NOVOZHILOVA, M. A.;ATOVMYAN, L. O.;KOMISSAROV, V. N.;XARL+, IZV. AN CCCP. CEP. XIM.,(1991) N, S. 702-708
  作者：ALDOSHIN, S. M.、NOVOZHILOVA, M. A.、ATOVMYAN, L. O.、KOMISSAROV, V. N.、XARL+

  DOI：——

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

  DOI：——

  日期：——