1,1,1-trideutero-2-(1,1,1-trideuteromethyl)-2-butene | 1787-45-7

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1,1,1-trideutero-2-(1,1,1-trideuteromethyl)-2-butene
• 英文别名: 2-(methyl-d3)-2-butene-1,1,1-d3；2-(methyl-d3)-2-buten-1,1,1-d3；1,1,1-trideuterio-2-trideuteriomethyl-but-2-ene；1,1,1-Trideutero-2-(trideutero-methyl)-but-2-en；Trimethylethylen-d6；1,1,1-Trideuterio-2-(trideuteriomethyl)but-2-ene；1,1,1-trideuterio-2-(trideuteriomethyl)but-2-ene
• CAS: 1787-45-7
• 化学式: C₅H₁₀
• 分子量: 76.0868
• InChiKey: BKOOMYPCSUNDGP-XERRXZQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  二碘甲烷 、 1,1,1-trideutero-2-(1,1,1-trideuteromethyl)-2-butene 在 diethylzinc 作用下， 以 甲苯 为溶剂， 生成 1,1-(dimethyl-d6)-2-methylcyclopropane
  参考文献：
  名称：

  Cyclopropane intermediates in the rearrangement and fragmentation of olefinic molecular ions

  摘要：

  AbstractMethyl loss from deuterium‐labelled molecular ions of 4‐methyl‐2‐pentene, 2‐methyl‐2‐pentene and 1,1,2‐trimethylcyclopropane has been investigated for metastable molecular ions and for molecular ions formed by charge exchange with COS+˙, XE+˙ and CO+˙. For metastable ion fragmentation reactions all three compounds exhibit very similar behavior and show specific and essentially equal loss of each of the original methyl groups as well as specific loss of a methyl where the hydrogens derive exclusively from the non‐methyl hydrogens of the original molecules. The former results are interpreted in terms of interconversion of the three molecular ions through a ring‐opened form of the trimethylcyclopropane molecular ion. The loss of the non‐methyl hydrogens as CH3 is interpreted in terms of isomerization to the 2,3‐dimethyl‐2‐butene structure. With increasing internal energy direct allylic cleavage of the unrearranged methylpentene molecular ions increases in importance while the trimethylcyclopropane molecular ion shows an increased preference for loss of the C(2) methyl group. With increasing internal energy loss of the original non‐methyl hydrogens as CH3 decreases markedly in importance.

  DOI：

  10.1002/oms.1210201007
• 作为产物：
  描述：

  2-(Methyl-d₃)-2-butanol-1,1,1-d₃ 在 硫酸 作用下， 生成 1,1,1-trideutero-2-(1,1,1-trideuteromethyl)-2-butene
  参考文献：
  名称：

  β-氢同位素对不饱和系统中碳 13 NMR 化学位移的影响与超共轭相互作用强度之间的相关性

  摘要：

  ..β..-氢同位素对 CL/sub 3/C(R)=X（L = H 或 D）中三角碳的碳 13 NMR 化学位移的影响报告了 15 种物质，其中正电荷三方碳的密度通过 R 和 X 的系统变化来调节。在这些同位素效应和三方碳的化学位移之间发现了线性关系，这被视为这些同位素效应的大小依赖于CL/sub 3/ 和 C(R)=X 之间超共轭相互作用的强度。提出了根据非谐碳氢键弯曲振动对超共轭 NMR 同位素效应的解释。

  DOI：

  10.1021/ja00285a006

文献信息

• Electrophilic aromatic prenylation via cascade cyclization
  作者：John G. Kodet、Joseph J. Topczewski、Kevyn D. Gardner、David F. Wiemer

  DOI：10.1016/j.tet.2013.08.056

  日期：2013.11

  To gain access to prenylated hexahydroxanthenes, tandem cascade cyclization-electrophilic aromatic substitution reactions have been studied on substrates bearing allylic and propargylic substituents. Both BF3 center dot OEt2 and TMSOTf can be used to initiate this reaction sequence, resulting in different ratios of the C-2 and C-6 substitution products. Even though allylic transposition is observed in some cases, the results of a crossover experiment are consistent with an intramolecular reaction sequence. Taken together, these studies now allow preparation of either the C-2 or C-6 prenylated hexahydroxanthene products. (C) 2013 Elsevier Ltd. All rights reserved.
• Cyclopropane intermediates in the rearrangement and fragmentation of olefinic molecular ions
  作者：Keith R. Laderoute、Alex. G. Harrison

  DOI：10.1002/oms.1210201007

  日期：1985.10

  AbstractMethyl loss from deuterium‐labelled molecular ions of 4‐methyl‐2‐pentene, 2‐methyl‐2‐pentene and 1,1,2‐trimethylcyclopropane has been investigated for metastable molecular ions and for molecular ions formed by charge exchange with COS+˙, XE+˙ and CO+˙. For metastable ion fragmentation reactions all three compounds exhibit very similar behavior and show specific and essentially equal loss of each of the original methyl groups as well as specific loss of a methyl where the hydrogens derive exclusively from the non‐methyl hydrogens of the original molecules. The former results are interpreted in terms of interconversion of the three molecular ions through a ring‐opened form of the trimethylcyclopropane molecular ion. The loss of the non‐methyl hydrogens as CH3 is interpreted in terms of isomerization to the 2,3‐dimethyl‐2‐butene structure. With increasing internal energy direct allylic cleavage of the unrearranged methylpentene molecular ions increases in importance while the trimethylcyclopropane molecular ion shows an increased preference for loss of the C(2) methyl group. With increasing internal energy loss of the original non‐methyl hydrogens as CH3 decreases markedly in importance.
• A correlation between .beta.-hydrogen isotope effects on carbon-13 NMR chemical shifts in unsaturated systems and the strength of hyperconjugative interactions
  作者：Cheryl H. Arrowsmith、A. Jerry. Kresge

  DOI：10.1021/ja00285a006

  日期：1986.12

  ..beta..-Hydrogen isotope effects on the carbon-13 NMR chemical shifts of the trigonal carbon in CL/sub 3/C(R)=X (L = H or D) are reported for 15 substances in which the positive charge density at the trigonal carbon is regulated through systematic variation of R and X. A linear relationship is found between these isotope effects and the chemical shifts of the trigonal carbons, and this is taken as

  ..β..-氢同位素对 CL/sub 3/C(R)=X（L = H 或 D）中三角碳的碳 13 NMR 化学位移的影响报告了 15 种物质，其中正电荷三方碳的密度通过 R 和 X 的系统变化来调节。在这些同位素效应和三方碳的化学位移之间发现了线性关系，这被视为这些同位素效应的大小依赖于CL/sub 3/ 和 C(R)=X 之间超共轭相互作用的强度。提出了根据非谐碳氢键弯曲振动对超共轭 NMR 同位素效应的解释。