6-(Chloromethyl)-6-methylfulvene | 162143-85-3

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: 6-(Chloromethyl)-6-methylfulvene
• 英文别名: 6-chloromethyl-6-methylfulvene；5-(1-Chloropropan-2-ylidene)cyclopenta-1,3-diene
• CAS: 162143-85-3
• 化学式: C₈H₉Cl
• mdl: MFCD19235906
• 分子量: 140.612
• InChiKey: PNPXJYPACQITES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  6-(Chloromethyl)-6-methylfulvene 在 silver nitrate 作用下， 以 水 、 丙酮 为溶剂， 反应 5.5h， 以5%的产率得到
  参考文献：
  名称：

  烯丙基对 SN2 反应性的影响

  摘要：

  苄基和在S烯丙基的激活作用Ñ 2反应是公知的。6-氯甲基-6-甲基富烯，也是一种主要的烯丙基卤化物，在室温下与 KI/丙酮的反应速度是苄基氯的 30 倍。后一个结果以及新的实验观察表明，富烯基是 S N 2 反应中特别活化的烯丙基。对恒等 S N 2 反应的计算工作，例如氯化物-置换氯化物-和氨置换氨，表明带负电荷的 S N根据 Galabov-Allen-Wu 静电模型，2 个过渡态 (tss) 被烯丙基激活，但由于过渡态 (ts) 中的某些环戊二烯化物特征，富烯基在帮助离域负电荷方面特别有效。相反，三富烯基正在失活。然而，氨反应的带正电荷的 S N 2 过渡态被三富烯基显着稳定，它直接与具有 S N的反应中心结合ts 中的 1 个字符。对各种烯丙醇和羧酸的酸度进行的实验和计算支持富烯基在稳定附近负电荷方面的特殊性质，并突出了富烯物质即使在没有直接共轭的情况下也能显着改变过程能量的能力。

  DOI：

  10.1021/jo501157s
• 作为产物：
  描述：

  环戊二烯 、 一氯丙酮 在 四氢吡咯 作用下， 以66%的产率得到6-(Chloromethyl)-6-methylfulvene
  参考文献：
  名称：

  Scope and Limitations of Fulvene Syntheses. Preparation of 6-Vinyl-Substituted and -Functionalized Fulvenes. First Examples of Nucleophilic Substitution on a 6-(Chloromethyl)fulvene

  摘要：

  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.

  DOI：

  10.1021/jo00109a010

文献信息

• Diverse Modes of Reactivity of 6‐(Chloromethyl)‐6‐methylfulvene
  作者：Ihsan Erden、Scott Gronert、Gabriel Cabrera、Necdet Coskun、Marco Tapken

  DOI：10.1002/ejoc.201700442

  日期：2017.5.26

  compound exhibits a number of modes of reactivity toward nucleophiles/bases owing to the presence of several electrophilic and potentially nucleophilic sites in the molecule. We explored the reactions of 6-(chloromethyl)-6-methylfulvene with oxygen and nitrogen nucleophiles and bases as well as a carbon-based nucleophile (an enamine) and realized all possible reactivity modes predicted on the basis of electrophilic

  由于分子中存在几个亲电和潜在的亲核位点，标题化合物对亲核试剂/碱基表现出多种反应模式。我们探索了6-（氯甲基）-6-甲基富烯与氧和氮亲核试剂和碱以及碳基亲核试剂（烯胺）的反应，并实现了在此亲电和亲核位置的基础上预测的所有可能的反应模式化合物。
• 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.
• Effect of Allylic Groups on S_N2 Reactivity
  作者：Ihsan Erden、Scott Gronert、James R. Keeffe、Jingxiang Ma、Nuket Ocal、Christian Gärtner、Leah L. Soukup

  DOI：10.1021/jo501157s

  日期：2014.7.18

  allyl groups on SN2 reactivity are well-known. 6-Chloromethyl-6-methylfulvene, also a primary, allylic halide, reacts 30 times faster with KI/acetone than does benzyl chloride at room temperature. The latter result, as well as new experimental observations, suggests that the fulvenyl group is a particularly activating allylic group in SN2 reactions. Computational work on identity SN2 reactions, e.g

  苄基和在S烯丙基的激活作用Ñ 2反应是公知的。6-氯甲基-6-甲基富烯，也是一种主要的烯丙基卤化物，在室温下与 KI/丙酮的反应速度是苄基氯的 30 倍。后一个结果以及新的实验观察表明，富烯基是 S N 2 反应中特别活化的烯丙基。对恒等 S N 2 反应的计算工作，例如氯化物-置换氯化物-和氨置换氨，表明带负电荷的 S N根据 Galabov-Allen-Wu 静电模型，2 个过渡态 (tss) 被烯丙基激活，但由于过渡态 (ts) 中的某些环戊二烯化物特征，富烯基在帮助离域负电荷方面特别有效。相反，三富烯基正在失活。然而，氨反应的带正电荷的 S N 2 过渡态被三富烯基显着稳定，它直接与具有 S N的反应中心结合ts 中的 1 个字符。对各种烯丙醇和羧酸的酸度进行的实验和计算支持富烯基在稳定附近负电荷方面的特殊性质，并突出了富烯物质即使在没有直接共轭的情况下也能显着改变过程能量的能力。