[15,16-Bis(2-methylprop-1-enyl)-6-tricyclo[9.3.1.14,8]hexadeca-1(15),2,4,6,8(16),9,11,13-octaenyl]-naphthalen-1-ylmethanone | 1266185-52-7

• 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: [15,16-Bis(2-methylprop-1-enyl)-6-tricyclo[9.3.1.14,8]hexadeca-1(15),2,4,6,8(16),9,11,13-octaenyl]-naphthalen-1-ylmethanone
• 英文别名: [15,16-bis(2-methylprop-1-enyl)-6-tricyclo[9.3.1.14,8]hexadeca-1(15),2,4,6,8(16),9,11,13-octaenyl]-naphthalen-1-ylmethanone
• CAS: 1266185-52-7
• 化学式: C₃₅H₃₀O
• 分子量: 466.623
• InChiKey: LKXOEAYQUKTIIZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.7
• 重原子数：
  36
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [15,16-Bis(2-methylprop-1-enyl)-6-tricyclo[9.3.1.14,8]hexadeca-1(15),2,4,6,8(16),9,11,13-octaenyl]-naphthalen-1-ylmethanone 生成 10b,10c-bis(2-methyl-1-propenyl)-2-(1-naphthoyl)-trans-10b,10c-dihydropyrene
  参考文献：
  名称：

  Calculation Driven Synthesis of an Excellent Dihydropyrene Negative Photochrome and its Photochemical Properties

  摘要：

  The photochromic properties of dihydropyrenes have been substantially improved by making use of density functional theory (DFT) activation barrier calculations, which suggested that the di-isobutenylcyclophanediene 15' should have a significant barrier to thermal isomerization to the dihydropyrene (DHP) 15, which itself should resist isomerization involving migration of the internal groups to the rearranged dihydropyrene 9 (X = -CH=C(Me)(2)). As a result of these calculations, the synthesis of the colorless cyclophanediene (CPD) 15' was undertaken and achieved from the dinitrile 28 in four steps in 37% overall yield %. The cyclophanediene 15' thermally isomerized to the dihydropyrene 15 at 100 degrees C with t(1/2) = 4.5 h, giving an extrapolated 20 degrees C t(1/2) of similar to 16 y, consistent with the DFT calculations. No evidence for [1,5]-sigmatropic rearrangement in to 9 (X = -CH=C(Me)(2)) was observed on heating to 130 degrees C. The ring-opening isomerization quantum yields (phi(open)) for DHP 15 in to CPD 15' were determined in cyclohexane to be 0.12 +/- 0.01, which is three times greater than for the benzoDHP 1. Friedel-Crafts naphthoylation of 15 gave 70% of purple 32, which in toluene showed the largest photochemical ring-opening isomerization quantum yields (phi(open)) of 0.66 +/- 0.02 for any known dihydropyrene, similar to nine times greater than 1 in toluene. The thermal closing of 32' to 32, although faster than for 15', gave a useful extrapolated t(1/2) of similar to 2 y at 20 degrees C.

  DOI：

  10.1021/ja1100596
• 作为产物：
  描述：

  10b,10c-bis(2-methyl-1-propenyl)-2-(1-naphthoyl)-trans-10b,10c-dihydropyrene 以 氘代甲苯 为溶剂， 生成 [15,16-Bis(2-methylprop-1-enyl)-6-tricyclo[9.3.1.14,8]hexadeca-1(15),2,4,6,8(16),9,11,13-octaenyl]-naphthalen-1-ylmethanone
  参考文献：
  名称：

  Calculation Driven Synthesis of an Excellent Dihydropyrene Negative Photochrome and its Photochemical Properties

  摘要：

  The photochromic properties of dihydropyrenes have been substantially improved by making use of density functional theory (DFT) activation barrier calculations, which suggested that the di-isobutenylcyclophanediene 15' should have a significant barrier to thermal isomerization to the dihydropyrene (DHP) 15, which itself should resist isomerization involving migration of the internal groups to the rearranged dihydropyrene 9 (X = -CH=C(Me)(2)). As a result of these calculations, the synthesis of the colorless cyclophanediene (CPD) 15' was undertaken and achieved from the dinitrile 28 in four steps in 37% overall yield %. The cyclophanediene 15' thermally isomerized to the dihydropyrene 15 at 100 degrees C with t(1/2) = 4.5 h, giving an extrapolated 20 degrees C t(1/2) of similar to 16 y, consistent with the DFT calculations. No evidence for [1,5]-sigmatropic rearrangement in to 9 (X = -CH=C(Me)(2)) was observed on heating to 130 degrees C. The ring-opening isomerization quantum yields (phi(open)) for DHP 15 in to CPD 15' were determined in cyclohexane to be 0.12 +/- 0.01, which is three times greater than for the benzoDHP 1. Friedel-Crafts naphthoylation of 15 gave 70% of purple 32, which in toluene showed the largest photochemical ring-opening isomerization quantum yields (phi(open)) of 0.66 +/- 0.02 for any known dihydropyrene, similar to nine times greater than 1 in toluene. The thermal closing of 32' to 32, although faster than for 15', gave a useful extrapolated t(1/2) of similar to 2 y at 20 degrees C.

  DOI：

  10.1021/ja1100596

文献信息

• Calculation Driven Synthesis of an Excellent Dihydropyrene Negative Photochrome and its Photochemical Properties
  作者：Khurshid Ayub、Rui Li、Cornelia Bohne、Richard Vaughan Williams、Reginald H. Mitchell

  DOI：10.1021/ja1100596

  日期：2011.3.23

  The photochromic properties of dihydropyrenes have been substantially improved by making use of density functional theory (DFT) activation barrier calculations, which suggested that the di-isobutenylcyclophanediene 15' should have a significant barrier to thermal isomerization to the dihydropyrene (DHP) 15, which itself should resist isomerization involving migration of the internal groups to the rearranged dihydropyrene 9 (X = -CH=C(Me)(2)). As a result of these calculations, the synthesis of the colorless cyclophanediene (CPD) 15' was undertaken and achieved from the dinitrile 28 in four steps in 37% overall yield %. The cyclophanediene 15' thermally isomerized to the dihydropyrene 15 at 100 degrees C with t(1/2) = 4.5 h, giving an extrapolated 20 degrees C t(1/2) of similar to 16 y, consistent with the DFT calculations. No evidence for [1,5]-sigmatropic rearrangement in to 9 (X = -CH=C(Me)(2)) was observed on heating to 130 degrees C. The ring-opening isomerization quantum yields (phi(open)) for DHP 15 in to CPD 15' were determined in cyclohexane to be 0.12 +/- 0.01, which is three times greater than for the benzoDHP 1. Friedel-Crafts naphthoylation of 15 gave 70% of purple 32, which in toluene showed the largest photochemical ring-opening isomerization quantum yields (phi(open)) of 0.66 +/- 0.02 for any known dihydropyrene, similar to nine times greater than 1 in toluene. The thermal closing of 32' to 32, although faster than for 15', gave a useful extrapolated t(1/2) of similar to 2 y at 20 degrees C.