2,6-stelladione | 82431-27-4

• 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: 2,6-stelladione
• 英文别名: Stella-2,6-dione；tricyclo[3.3.0.03,7]octane-2,6-dione
• CAS: 82431-27-4
• 化学式: C₈H₈O₂
• 分子量: 136.15
• InChiKey: PUVOOUPCYNBSPQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,6-stelladione 在 吡啶 、 lithium diisopropyl amide 、 三氯氧磷 作用下， 反应 92.0h， 生成 6-(9H-xanthen-9-ylidene)tricyclo[3.3.0.0^3,7]octane-2-one
  参考文献：
  名称：

  Syntheses of Donor–Acceptor-Substituted 2,6-Stellanes

  摘要：

  A number of condensations could be carried out using tricyclo[3.3.0.0(3.7)]octane-2-one (stellanone, 4) and tricyclo[3.3.0.0(3.7)]octane-2,6-dione (2,6-stelladione, 5) as starting materials. The components for condensations were 2-trimethylsilyl-1,3-dithiane (6), 1,1-bis(trimethylsilyl)-1H-cyclopropa[b]naphthalene (7), its 3,6-dimethoxy-substituted analogue 8, fluorene (12), xanthene (13), diethyl malonate (14), and malononitrile (15). The condensation reactions with 5 yielded mono- and disubstituted products, among them were the donor-acceptor-substituted 2,6-stellanes 33-35. The structures of 18 (prepared from stellanone and fluorene), 19, 24, 27, 31 and 32 (synthesized by condensation of 2,6-stelladione and 2-trimethylsilyl-1,3-dithiane and malononitrile, respectively) were determined by X-ray crystallography.

  DOI：

  10.1002/(sici)1099-0690(199901)1999:1<73::aid-ejoc73>3.0.co;2-b
• 作为产物：
  描述：

  endo-2-methylene-3-[[(p-toluenesulfonyl)oxy]methyl]bicyclo[2.2.1]hept-5-ene 在 氢氧化钾 、 sodium periodate 、 四氧化锇 、 lithium aluminium tetrahydride 、 氯化亚砜 、 potassium tert-butylate 、 水 、 双氧水 、 氧气 、 臭氧 、 溶剂黄146 、 三乙胺 、 pyridinium chlorochromate 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 氯仿 、 水 、 乙二醇 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 263.17h， 生成 2,6-stelladione
  参考文献：
  名称：

  Synthesis of the D2d-dinoradamantane derivatives having two coaxially oriented unsaturated centers. 6-Methylene-D2d-dinoradamantan-2-one and D2d-dinoradamantane-2,6-dione

  摘要：

  DOI：

  10.1021/jo00139a017

文献信息

• Syntheses and Properties of Donor−Acceptor-Substituted Molecules with a Bicyclo[2.2.1]heptane, a Bicyclo[2.2.2]octane, and a Tricyclo[3.3.0.03,7]octane Spacer
  作者：Marco Altmayer、Bettina Gaa、Rolf Gleiter、Frank Rominger、Jana Kurzawa、Siegfried Schneider

  DOI：10.1002/1099-0690(200108)2001:16<3045::aid-ejoc3045>3.0.co;2-g

  日期：2001.8

  and 39 confirmed the (E) configuration at the exo double bond and yielded the molecular parameters. Fluorescence spectra provided evidence for efficient photoinduced electron transfer in only the naphthalene and pyrene derivatives 22 and 26, but not in the analogous anthracene derivative 24 in accordance with estimates for ΔGet.

  从双环[2.2.1]庚烷-2,5-二酮、双环[2.2.2]辛烷-2,5-二酮和三环[3.3.0.03,7]辛烷-2,6-二酮开始，我们能够合成通过缩合反应的供体-受体取代衍生物。缩合的组分是受体部分的丙二腈 (21) 和[(萘-1-基)甲基]膦酸二乙酯(12)、[(蒽-9-基)甲基]膦酸二乙酯(13)和二乙基[(芘-1-基)甲基]膦酸酯(14)。为了缩合丙二腈，我们使用了 Knoevenagel 缩合，对于膦酸酯，我们使用了 Wittig-Horner-Emmons 程序。通过 NOESY NMR 实验，可以建立供体 - 受体取代的自行车的外双键处的（E）构型。22、24、27、和 39 证实了外双键的 (E) 构型并得出了分子参数。根据对ΔGet的估计，荧光光谱仅在萘和芘衍生物22和26中提供了有效光致电子转移的证据，但在类似的蒽衍生物24中则没有。
• Preparation and Properties of Stelladiones
  作者：Rolf Gleiter、Bettina Gaa、Christoph Sigwart、Holger Lange、Oliver Borzyk、Frank Rominger、Hermann Irngartinger、Thomas Oeser

  DOI：10.1002/(sici)1099-0690(199801)1998:1<171::aid-ejoc171>3.0.co;2-m

  日期：1998.1

  Tricyclo[3.3.0.03,7]octane-2,4-dione (2,4-stelladione, 3), tricyclo[3.3.0.03,7]octane-2,6-dione (2,6-stelladione, 4), and 2-oxotricyclo[3.3.0.03,7]octane-6-thione (5) were synthesized. Key steps in the procedures were a Paterno-Buchi reaction followed by an oxetane splitting with a strong base. Structure analysis on single crystals of 4 and 5 revealed long central C−C bonds (1.59 A) of the stellane

  三环[3.3.0.03,7]辛烷-2,4-二酮(2,4-stelladione, 3)、三环[3.3.0.03,7]辛烷-2,6-二酮(2,6-stelladione, 4),合成了2-氧代三环[3.3.0.03,7]辛烷-6-硫酮(5)。程序中的关键步骤是 Paterno-Buchi 反应，然后是用强碱裂解氧杂环丁烷。对 4 和 5 单晶的结构分析揭示了星烷骨架的长中心 C-C 键 (1.59 A)。基于量子力学计算 (HF-SCF, 6) 记录和解释了 3、5 和 4-亚甲基三环-[3.3.0.03,7]octan-2-one (9) 的 He(I) 光电子光谱-31G* 基础）。3 (0.8 eV) 的第一个 PE 带之间的巨大能量差异是由于氧原子上的孤对与 σ 框架之间的强相互作用。
• Syntheses and Structural Properties of Distellenes
  作者：Rolf Gleiter、Gerd Fritzsche、Oliver Borzyk、Thomas Oeser、Frank Rominger、Hermann Irngartinger

  DOI：10.1021/jo971938m

  日期：1998.5.1

  The syntheses of a mixture of the racemic (a) and the meso form (b) of several derivatives of 2,2'-bi(tricyclo[3.3.0.0(3,7)]octylidene) are described: The 6,6'-diisopropylidene- (4), 6,6'-dimethylidene- (5), 6,6'-dione- (6), syn-4,4'-dione- (7), anti-4,4'-dione- (8), syn-4-methylidene-4'-one- (9), anti-4-methylidene-4'-one- (10), syn-4,4'-dimethylidene- (11), and anti-4,4'-dimethylidene- (12) derivatives. Starting materials for all compounds were tricyclo[3.3.0.0(3,7)]octane-2,4-diol (19) and its 2,6-isomer 20. Key reaction was the McMurry coupling of 6-isopropylidenetricyclo[3.3.0.0(3,7)]octa (23) or 6-methylidenetricyclo[3.3.0.0(3,7)]octan-2-one (24) to yield 4 or 5, respectively. The McMurry coupling of the ketone 26 yielded 7 and 8. From the latter, species 9-12 could be generated via the Wittig reaction. In most cases only the racemates could be isolated. X-ray investigations on 4a revealed a separation of the isopropylidene groups by 10.3 Angstrom. The central C-C bridging bonds of the stellane units in 4a, 7a, 8a, 12a, and 30 C(1)-C(5), C(3)-C(7), C(1)-C(5'), C(3')-C(7') were found to be between 1.596(2) and 1.616(3) Angstrom. In 4a we found a twisting between the terminal isopropylidene groups by a torsion ((CH3)(2)C=C ... C=C(CH3)(2)) of 74 degrees and 83 degrees, respectively, in both independent molecules. The twist angle between the CO groups in 7a amounts to 53 degrees, and in 8a to 118 degrees. The same twist angle was found between the exo-methylidene groups in 12a.
• Gleiter, Rolf; Borzyk, Oliver, Angewandte Chemie, 1995, vol. 107, # 9, p. 1094 - 1095
  作者：Gleiter, Rolf、Borzyk, Oliver

  DOI：——

  日期：——
• Synthesis of the D2d-dinoradamantane derivatives having two coaxially oriented unsaturated centers. 6-Methylene-D2d-dinoradamantan-2-one and D2d-dinoradamantane-2,6-dione
  作者：Masao Nakazaki、Koichiro Naemura、Hiroshi Harada、Hideya Narutaki

  DOI：10.1021/jo00139a017

  日期：1982.8