6-methyl-6-(1-ethyl-2-hydroxy)fulvene | 93915-27-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-methyl-6-(1-ethyl-2-hydroxy)fulvene
• 英文别名: 6-(2-hydroxyethyl)-6-methylfulvene；1-Butanol, 3-(2,4-cyclopentadien-1-ylidene)-；3-cyclopenta-2,4-dien-1-ylidenebutan-1-ol
• CAS: 93915-27-6
• 化学式: C₉H₁₂O
• 分子量: 136.194
• InChiKey: FPKMZOODFCXJKN-UHFFFAOYSA-N

物化性质

• 沸点：
  252.9±9.0 °C(Predicted)
• 密度：
  1.038±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6-methyl-6-(1-ethyl-2-hydroxy)fulvene 在 N,N'-二异丙基碳二亚胺 作用下， 以 氘代氯仿 为溶剂， 生成
  参考文献：
  名称：

  Reversible Diels−Alder Reactions for the Generation of Dynamic Combinatorial Libraries

  摘要：

  Condensation reactions between various dienes and dienophiles have been screened for reversibility. Functionalized fulvenes, bearing in particular biological groups, and cyanolefins have been found to react rapidly and reversibly, in the temperature range from -10 to +50 degreesC. These results pave the way for the development of dynamic combinatorial libraries based on reversible Diels-Alder chemistry.

  DOI：

  10.1021/ol048065k
• 作为产物：
  描述：

  6-methyl-6-oxiranyl fulvene 在 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 以35%的产率得到6-methyl-6-(1-ethyl-2-hydroxy)fulvene
  参考文献：
  名称：

  Antczak, Kazimierz; Kingston, John F.; Fallis, Alex G., Canadian Journal of Chemistry, 1984, vol. 62, p. 2451 - 2455

  摘要：

  DOI：

文献信息

• Lewis Acid Promoted Regioselective Double Hydro(hetero)arylation of 6,6′-Dialkyl-Substituted Pentafulvenes: A Facile Approach to Bisindole Derivatives
  作者：Parameswaran Sasikumar、Bernard Prabha、Sarngadharan Sarath Chand、Maniyamma Aswathy、Murali Madhukrishnan、Preethalayam Preethanuj、Eringathodi Suresh、Florian Jaroschik、Kokkuvayil Vasu Radhakrishnan

  DOI：10.1002/ejoc.201700742

  日期：2017.8.17

  A Lewis acid catalysed double hydro(hetero)arylation of alkyl substituted pentafulvene towards the synthesis of bisindole substituted cyclopentenoids has been developed. The scope of the reaction was explored with a wide range of indoles and pentafulvenes and mechanistic insights were obtained. In addition, we also have demonstrated a hydro(hetero)arylation-dehydroxylation reaction of 2-hydroxy substituted

  已经开发了路易斯酸催化的烷基取代的五氟戊烯的双加氢（杂）芳基化反应，以合成双吲哚取代的环戊烯。用各种各样的吲哚和五烯酮对反应的范围进行了探索，并获得了机理上的见解。另外，我们还证明了2-羟基取代的五烯丙基戊烯的加氢（杂）芳基化-脱羟基反应，其提供了具有异戊二烯基取代的环戊烯的双吲哚衍生物。
• Unusual hydroxyl effect on fulvene endoperoxide decompositions
  作者：Ihsan Erden、John Basada、Daniela Poli、Gabriel Cabrera、Fupei Xu、Scott Gronert

  DOI：10.1016/j.tetlet.2016.04.024

  日期：2016.5

  The thermal decomposition of fulvene endoperoxides ordinarily proceeds via an allene oxide intermediate affording oxepin-2(3H)-one derivatives. We have now uncovered new, unusual pathways in these decompositions where the presence of a hydroxyl group on the alkyl or aryl attached to the fulvene exocyclic double bond has a profound effect on the fate of the reactive intermediates derived from the unstable

  富烯内过氧化物的热分解通常是通过环氧乙烷中间体进行的，从而提供oxepin-2（3H）-one衍生物。现在，我们发现了这些分解中新的，不寻常的途径，其中连接在富烯外环双键上的烷基或芳基上的羟基的存在对衍生自不稳定内过氧化物的反应性中间体的命运产生了深远的影响。计算工作支持所提出的机械路径。
• Experimental and Theoretical Exploration of the Kinetics and Thermodynamics of the Nucleophile-Induced Fragmentation of Ylidenenorbornadiene Carboxylates
  作者：Abigail D. Richardson、Scott J. L’Heureux、Ava M. Henry、Elizabeth A. McDonough、Cameron J. Fleischer、Cameron C. McMullen、Trevor R. Reynafarje、Gisele P. Guerrero、Quinn E. Williams、Qingyang Zhou、David M. Malouf、Spencer E. Thurman、Julia E. Soeller、Jerry Y. Sheng、Erica A. Medhurst、Angel E. Canales、Ty B. Cecil、K. N. Houk、Philip J. Costanzo、Daniel A. Bercovici

  DOI：10.1021/acs.joc.3c00980

  日期：2023.8.18

  calculations were performed to investigate the mechanism of fragmentation and support an asynchronous retro-[4 + 2] cycloaddition transition state. The computations generally correlated well with the observed free energies of activation for four diastereomers of the model system as a whole, within 2.6 kcal/mol. However, the observed order of the fragmentation rates across the set of diastereomers deviated from

  亚叉冰片二烯 (YND) 通过富烯和乙炔羧酸盐之间的 [4 + 2] 环加成反应制备，与硫醇亲核试剂反应，根据 YND 底物的对称性产生 4 至 8 个非对映异构体的混合物。非对映异构体混合物通过逆[4 + 2]环加成发生片段化，速率变化很大，80°C 下半衰期为 16 至 11,000 分钟。丙硫醇加合物 [YND-丙硫醇 (PT)] 的非对映异构体富集样品通过核奥沃豪瑟效应光谱 (NOESY) 相关性进行分离和鉴定。使用模拟动力学从观察到的速率数据推断各个非对映异构体的速率常数，并且它与直接测量的速率常数以及从分离的非对映异构体富集样品中测量的速率常数密切相关。模型系统的各个非对映异构体以不同的速率断裂，在CDCl 3中的半衰期范围为5至44分钟。进行密度泛函理论计算来研究碎片机制并支持异步逆[4 + 2]环加成过渡态。计算结果总体上与观察到的模型系统的四种非对映异构体的活化自由能良好相关，在
• Scope and Limitations of Fulvene Syntheses. Preparation of 6-Vinyl-Substituted and -Functionalized Fulvenes. First Examples of Nucleophilic Substitution on a 6-(Chloromethyl)fulvene
  作者：Ihsan Erden、Fu-Pei Xu、Aladin Sadoun、Wyatt Smith、Greg Sheff、Madeleine Ossun

  DOI：10.1021/jo00109a010

  日期：1995.2

  Very few 6-vinylfulvenes have previously been reported in the Literature. In a few cases where Little's procedure (using pyrrolidine as base) has been employed, most enones undergo conjugate attack by the cyclopentadienyl anion followed by either a retroaldol reaction or dihydropentalene formation. In several cases, Diels-Alder reaction of the enone with cyclopentadiene occurs rather than condensation. We have found that in cases where the Little procedure fails to give the desired 6-vinylfulvenes, the Thiele method using NaOH (or NaOMe in some cases) as base gives satisfactory results. In the latter instances, Michael attack is completely suppressed in all but one example. By appropriate choice of base, a variety of fulvenes carrying functional groups on the 6-alkyl position can be prepared. Some of these fulvenes have been shown to undergo further functional group transformations (e.g., nucleophilic substitutions); giving rise to derivatives bearing SR, S(O)R, N-3 or SCN groups.
• An exceptionally simple and efficient synthesis of 6-methyl-6-vinylfulvene, and its oxidative transformations
  作者：Ihsan Erden、Christian Gärtner

  DOI：10.1016/j.tetlet.2009.02.221

  日期：2009.5

  A new efficient synthesis of 6-methyl-6-vinylfulvene was developed, starting from the 6-(2-hydroxyethyl)-6-methylfulvene. With larger quantities of the title compound in hand, its photooxygenation with singlet oxygen Was Studied. Cyclization of the cyclopropanone intermediate to both vinyl moieties in the unsaturated system was observed, whereas the saturated endoperoxide gave mostly the cyclopentenone derivative. m-CPBA attacks exclusively the endocyclic double bonds and gives the 3 -cyclopentenones via the unstable epoxides. (C) 2009 Elsevier Ltd. All rights reserved.