3-<1-<3,8-dimethyl-5-(1-methylethyl)azulenyl>>-2-propenenitrile | 146431-75-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 3-<1-<3,8-dimethyl-5-(1-methylethyl)azulenyl>>-2-propenenitrile
• 英文别名: (E)-1-cyano-2-(3-guaiazulenyl)ethylene；(E)-3-(3,8-dimethyl-5-propan-2-ylazulen-1-yl)prop-2-enenitrile
• CAS: 146431-75-6
• 化学式: C₁₈H₁₉N
• 分子量: 249.356
• InChiKey: LJFQIZMNSFZQGX-AATRIKPKSA-N

物化性质

• 沸点：
  417.2±14.0 °C(Predicted)
• 密度：
  1.036±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-<1-<3,8-dimethyl-5-(1-methylethyl)azulenyl>>-2-propenenitrile 在 氢氧化钾 、 18-冠醚-6 、 二异丁基氢化铝 、 lithium diisopropyl amide 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 水 、 正戊烷 为溶剂， 反应 5.5h， 生成 7-<1-<3,8-dimethyl-5-(1-methylethyl)azulenyl>>-3-methyl-2,4,6-heptatrienoic acid
  参考文献：
  名称：

  Azulenic retinoids: novel nonbenzenoid aromatic retinoids with anticancer activity

  摘要：

  Several novel azulene-containing retinoids were prepared and evaluated for their ability to suppress carcinogen-induced neoplastic transformation and to concomitantly up-regulate gap junctional communication in the in vitro mouse fibroblast C3H/10T1/2 cell bioassay. The azulenic retinoids were divided into two groups: compounds 1-6 were modeled after retinoic acid with flexible polyenic side chain whereas retinoids 7-13 featured a benzoic acid moiety analogous to the prototypic retinobenzoate (E)-4-[2-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl)-1-propenyl]benzoic acid (TTNPB). Within this latter group the side chains for compounds 7, 10, and 11 were attached at the 1-, 2-, and 8-positions of the azulenic terminus, respectively. Biological activities were determined for all the new compounds. Two of these novel retinoids, azulenic retinobenzoic acid derivatives 7 and 11, were completely effective inhibitors of transformation at 10(-6) M. The most active azulenic retinoids also enhanced gap junctional communication in untransformed cells; this was associated with up-regulated expression of connexin 43, a structural protein of the gap junction. Two fluorinated analogs were also tested. The azulenic fluoro acid 5 was found to be more potent than the trifluoromethyl analog 6. Azulenic analogs with hydroxyl or carboxaldehyde side chain functional groups were ineffective transformation inhibitors. In general, azulenic retinobenzoic acid analogs structurally akin to TTNPB were more effective than flexible side chain analogs related to retinoic acid.

  DOI：

  10.1021/jm00073a013
• 作为产物：
  描述：

  愈创奥 在 potassium tert-butylate 、 三氯氧磷 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 生成 、 3-<1-<3,8-dimethyl-5-(1-methylethyl)azulenyl>>-2-propenenitrile
  参考文献：
  名称：

  刺激响应的环戊二烯[ef]庚烯：合成和光学特性

  摘要：

  我们报告了一系列环戊二烯[ef]庚烯4a-c的一锅合成、一维和二维核磁共振表征以及紫外/可见研究，这些环戊烯[ef]庚烯4a-c表现出强烈的刺激响应行为，由于使用 TFA/Et3N 掺杂/去掺杂后的 HOMO、LUMO 和 LUMO+1 能量。所采用的方法允许将环戊二烯骨架的 C-4 处的共轭从 X = H (4a) 扩展到 X = CN (4b) 和 X = 2-噻吩 (4c)，从而导致更长的吸收最大值环戊二烯鎓阳离子 4a-c+ 的光能隙更小。此外，在紫外线激活（< 300 nm）光酸产生剂 (PAG) 的存在下，4c 的质子化可以通过从 4c 的激发态到 PAG 的分子间光致电子转移 (PeT) 间接实现，后者发生光分解，产生酸。这种现象促进了使用环戊二烯 [ef] 庚烯 4a-c 作为商业 PAG 的可见敏化剂。

  DOI：

  10.1002/ejoc.201500059

文献信息

• Preparation, crystal structure, and spectroscopic, chemical, and electrochemical properties of (2E,4E)-1,4-di(3-guaiazulenyl)-1,3-butadiene compared with those of (E)-1,2-di(3-guaiazulenyl)ethylene
  作者：Shin-ichi Takekuma、Manami Yamamoto、Aki Nakagawa、Tomohiro Iwata、Toshie Minematsu、Hideko Takekuma

  DOI：10.1016/j.tet.2012.07.022

  日期：2012.9

  (two-electron) oxidation product (E)-ethylene-1,2-bis(3-guaiazulenylmethylium) bis(hexafluorophosphate) (14), quantitatively, and further, zinc-reduction of 14 in trifluoroacetic acid (=CF3COOH) at 0 °C for 1 h under argon reverts 4, quantitatively. Along with the above interesting results, our discovered another preparation method, spectroscopic properties, crystal structure, and electrochemical behavior

  （E）-3-（3-愈创木烯基）丙烯醛（11）与（3-愈创木烯基甲基）三苯基溴化（（9）在含有NaOEt的乙醇中在氩气下于25°C进行Wittig反应24小时，得到新标题（2 E， 4 E）-1,3-丁二烯衍生物4，分离出的产率为33％，在有氧条件下，在六氢磷酸（即65％HPF 6水溶液）中于四氢呋喃（= THF）中于25°C处理1 h提供了一种新的空气（两电子）氧化产物（E）-乙烯-1,2-双（3-愈创氮烯基甲基）双（六氟磷酸酯）（14），定量地还原了锌，还原了14在氩气下于0°C下于三氟乙酸（= CF 3 COOH）中还原1 h还原4。随着上述有趣的结果，我们发现了另一种制备方法中，光谱性质，晶体结构，和电化学行为4，其用作一个强大的双电子供体和受体，与先前报道的（相比ë）-1，详细记录了2-二（3-愈创氮烯基）乙烯（3）。
• Stimuli-Responsive Cyclopenta[<i>ef</i>]heptalenes: Synthesis and Optical Properties
  作者：Ebrahim H. Ghazvini Zadeh、Adam W. Woodward、David Richardson、Mykhailo. V. Bondar、Kevin D. Belfield

  DOI：10.1002/ejoc.201500059

  日期：2015.4

  characterization, and UV/Vis study of a series of cyclopenta[ef]heptalenes 4a–c that exhibit strong stimuli-responsive behavior, with a tunable energy gap as a result of perturbation of HOMO, LUMO, and LUMO+1 energies upon doping/dedoping with TFA/Et3N. The approach employed allows for the extension of conjugation at C-4 of the cyclopenta[ef]heptalene skeleton from X = H (4a) to X = CN (4b) and X = 2-thiophenyl

  我们报告了一系列环戊二烯[ef]庚烯4a-c的一锅合成、一维和二维核磁共振表征以及紫外/可见研究，这些环戊烯[ef]庚烯4a-c表现出强烈的刺激响应行为，由于使用 TFA/Et3N 掺杂/去掺杂后的 HOMO、LUMO 和 LUMO+1 能量。所采用的方法允许将环戊二烯骨架的 C-4 处的共轭从 X = H (4a) 扩展到 X = CN (4b) 和 X = 2-噻吩 (4c)，从而导致更长的吸收最大值环戊二烯鎓阳离子 4a-c+ 的光能隙更小。此外，在紫外线激活（< 300 nm）光酸产生剂 (PAG) 的存在下，4c 的质子化可以通过从 4c 的激发态到 PAG 的分子间光致电子转移 (PeT) 间接实现，后者发生光分解，产生酸。这种现象促进了使用环戊二烯 [ef] 庚烯 4a-c 作为商业 PAG 的可见敏化剂。
• Azulenic retinoids: novel nonbenzenoid aromatic retinoids with anticancer activity
  作者：Alfred E. Asato、Ao Peng、Mohammad Z. Hossain、Taraneh Mirzadegan、John S. Bertram

  DOI：10.1021/jm00073a013

  日期：1993.10

  Several novel azulene-containing retinoids were prepared and evaluated for their ability to suppress carcinogen-induced neoplastic transformation and to concomitantly up-regulate gap junctional communication in the in vitro mouse fibroblast C3H/10T1/2 cell bioassay. The azulenic retinoids were divided into two groups: compounds 1-6 were modeled after retinoic acid with flexible polyenic side chain whereas retinoids 7-13 featured a benzoic acid moiety analogous to the prototypic retinobenzoate (E)-4-[2-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl)-1-propenyl]benzoic acid (TTNPB). Within this latter group the side chains for compounds 7, 10, and 11 were attached at the 1-, 2-, and 8-positions of the azulenic terminus, respectively. Biological activities were determined for all the new compounds. Two of these novel retinoids, azulenic retinobenzoic acid derivatives 7 and 11, were completely effective inhibitors of transformation at 10(-6) M. The most active azulenic retinoids also enhanced gap junctional communication in untransformed cells; this was associated with up-regulated expression of connexin 43, a structural protein of the gap junction. Two fluorinated analogs were also tested. The azulenic fluoro acid 5 was found to be more potent than the trifluoromethyl analog 6. Azulenic analogs with hydroxyl or carboxaldehyde side chain functional groups were ineffective transformation inhibitors. In general, azulenic retinobenzoic acid analogs structurally akin to TTNPB were more effective than flexible side chain analogs related to retinoic acid.