guaiazulene-2-carboxaldehyde | 57440-48-9

• 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: guaiazulene-2-carboxaldehyde
• 英文别名: 2-Formylguaiazulen；1,4-Dimethyl-7-propan-2-ylazulene-2-carbaldehyde
• CAS: 57440-48-9
• 化学式: C₁₆H₁₈O
• 分子量: 226.318
• InChiKey: XYZGAIJEPCTOQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  guaiazulene-2-carboxaldehyde 在 氢氧化钾 、 lithium diisopropyl amide 作用下， 以 甲醇 为溶剂， 反应 4.0h， 生成 4-<2-<2-<3,8-dimethyl-5-(1-methylethyl)azulenyl>>ethenyl>benzoic 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：

  3,6-Dihydro-7-isopropyl-6-[(7-isopropyl-1-methyl-4-azulenyl)methyl]-1,4-dimethyl-2-azulenecarbaldehyde 以5%的产率得到
  参考文献：
  名称：

  KUROKAWA S., BULL. CHEM. SOC. JAP., 1979, 52, NO 6, 1748-1751

  摘要：

  DOI：

文献信息

• Azulene Functionalization by Iron-Mediated Addition to a Cyclohexadiene Scaffold
  作者：Petter Dunås、Lloyd C. Murfin、Oscar J. Nilsson、Nicolas Jame、Simon E. Lewis、Nina Kann

  DOI：10.1021/acs.joc.0c01412

  日期：2020.11.6

  The functionalization of azulenes via reaction with cationic η5-iron carbonyl diene complexes under mild reaction conditions is demonstrated. A range of azulenes, including derivatives of naturally occurring guaiazulene, were investigated in reactions with three electrophilic iron complexes of varying electronic properties, affording the desired coupling products in 43–98% yield. The products were

  经由反应薁的官能化与阳离子η 5 -铁羰二烯络合物温和的反应条件下是证明。在与三种具有不同电子性质的亲电子铁配合物的反应中，研究了各种天青石，包括天然愈创木酚的衍生物，以43–98％的收率提供了所需的偶联产物。用紫外-可见/荧光光谱法检查了产品，并显示出有趣的盐致变色性质。产物的分解和进一步衍生化提供了接近几种不同类别的1-取代的zu烯的途径，包括共轭酮和稠合四环。
• The Thermal Reaction of 3-Formylguaiazulene
  作者：Shinji Kurokawa、Teruyo Safo、Toru Noguchi、Katsumi Yano

  DOI：10.1246/bcsj.48.1559

  日期：1975.5

  When 3-formxlguaiazulene was heated at 200 °C for 1 hr, three new compounds were isolated in addition to S-guaiazulene (formed by loss of the formyl group). They were shown to be 2-formylguaiazulene, produced by migration of the formyl group, and dimers produced from two molecules of the starting material through dehydration between the formyl and the aromatic methyl groups. The observed elimination or migration of the formyl group was analogous to the behavior of 3-acylguaiazulenes which had been studied earlier. On the other hand, the extent of the loss of the acyl group and the formation of the dimers was peculiar to this substance. Moreover, migration of the formyl group was not reversible at 200 °C, but was at 250 °C.

  将 3-formxl-guaiazulene（3-甲酰基guaiazulene）在 200 °C 下加热 1 小时，除了 S-guaiazulene（甲酰基脱落形成）外，还分离出三种新化合物。它们分别是甲酰基迁移生成的 2-甲酰基guaiazulene，以及甲酰基和芳香甲基脱水生成的二聚物。观察到的甲酰基消除或迁移与早先研究过的 3-酰基胍唑烯的行为类似。另一方面，酰基消失的程度和二聚物的形成是这种物质所特有的。此外，甲酰基的迁移在 200 °C 时不可逆，但在 250 °C 时可逆。