(+/-)-2,2-dimethyl-3,4-decadiene | 84718-85-4

• 分子结构分类: 有机化合物 - 叠烯 - 无环联烯
• 英文名称: (+/-)-2,2-dimethyl-3,4-decadiene
• 英文别名: 2,2-dimethyl-3,4-decadiene；2,2-dimethyldeca-3,4-diene；2,2-dimethyl-deca-3,4-diene；2,2-Dimethyl-decadien-(3,4)
• CAS: 84718-85-4
• 化学式: C₁₂H₂₂
• 分子量: 166.307
• InChiKey: RLYOJWAFNPKWRK-UHFFFAOYSA-N

物化性质

• 沸点：
  86-87 °C(Press: 20 Torr)
• 密度：
  0.7643 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  (+/-)-2,2-dimethyl-3,4-decadiene 在 Lindlar's catalyst 氢气 作用下， 生成 2,2-二甲基癸烷
  参考文献：
  名称：

  Petrov,A.A. et al., Journal of general chemistry of the USSR, 1963, vol. 33, p. 407 - 409

  摘要：

  DOI：
• 作为产物：
  描述：

  (+/-)-2,2-dimethyl-3-decyn-5-ol 在 chromium dichloride 、 溶剂黄146 、 magnesium bromide 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 2.0h， 生成 (+/-)-2,2-dimethyl-3,4-decadiene
  参考文献：
  名称：

  1 H NMR手性识别烯丙基烃

  摘要：

  描述了烯丙基（±）-1，（±）-4和（±）-6以及富集样品（-）-1，（-）-4和（-）-6的合成。给出了由非手性盐Ag（fod）和旋光络合物（+）-Yb（hfbc）3的混合物引起的1 H NMR位移和分裂。这种分离的程度推荐该方法作为确定1，3-二取代的烯丙基烃的对映体纯度的手段。（-）-1和（-）-5的结果代表了该绝对方法的首次应用。

  DOI：

  10.1016/s0040-4020(01)87439-1

文献信息

• Pd‐Catalyzed Heck‐Type Reactions of Allenes for Stereoselective Syntheses of Substituted 1,3‐Dienes
  作者：Logan E. Vine、Jennifer M. Schomaker

  DOI：10.1002/chem.202103507

  日期：2022.1.3

  A stereoselective synthesis of (Z,E)-dienes from allenes is described. The method employs a Heck-type reaction catalyzed by tris(dibenzylideneacetone) dipalladium, Pd2dba3 and a CyJohnPhos ligand and does not require a leaving or directing group on the allene. The stereochemistry of both olefins of the diene is set simultaneously using both A1,3 strain and eclipsing interactions during the β-hydride

  描述了从丙二烯立体选择性合成( Z,E )-二烯。该方法采用由三(二亚苄基丙酮)二钯、Pd 2 dba 3和CyJohnPhos配体催化的Heck型反应，并且不需要丙二烯上的离去基团或导向基团。在β-氢化物消除过程中，使用 A 1,3应变和遮蔽相互作用同时设定二烯的两种烯烃的立体化学，以良好的选择性得到 ( Z,E ) : ( E,E ) 二烯。该方法还提供了对 2,4-二烯酸酯和二酰胺的区域控制访问。
• Mechanistic aspects of the formation of chiral allenes from propargylic ethers and organocopper reagents
  作者：A. Alexakis、I. Marek、P. Mangeney、J. F. Normant

  DOI：10.1021/ja00178a029

  日期：1990.10

  Propargylic ethers react with organocopper reagents to afford allenes by a syn addition to the triple bond followed by a β-elimination of the resulting alkenyl copper species. With use of chiral propargylic ethers and stoichiometric organocopper reagent, it was shown that the β-elimination step is purely anti, resulting in the formation of a chiral allene with 96% optical yield. The same reaction,

  炔丙醚与有机铜试剂反应，通过对三键进行顺式加成，然后β-消除生成的烯基铜物质来提供丙二烯。使用手性炔丙醚和化学计量有机铜试剂，表明 β-消除步骤是纯反的，导致形成具有 96% 光学产率的手性丙二烯。使用格氏试剂 RMgX 和催化量的 Cu I 盐进行相同的反应，通过反或顺整个过程提供丙二烯。关键的步骤是β-消除中间体烯基有机金属物种，它是反型与 RMgI 和顺型与 RMgCl。丙炔乙酸酯，在该反应中也提供丙二烯，但通过 Cu III 中间体，对这种“卤素效应”不敏感
• Mecanismes de la protonolyse des organo-chromiques issus de bromures propargyliques.
  作者：Bernard Cazes、Catherine Verniere、Jacques Gore

  DOI：10.1016/s0040-4039(00)87652-2

  日期：1982.1

  The reaction of CrCl2 with propargylic bromides leads to an allenic organo—chromic derivative protonated without rearrangement by carboxylic acids. Alcohols like methol transform this metallic to its propargylic isomer and then protonate it with rearrngement (SEi′ type mechanism).

  CrCl 2与炔丙基溴的反应会导致烯丙基有机-铬衍生物质子化，而不会被羧酸重排。像methol醇变换该金属至其炔异构体，然后用rearrngement（S质子化它Ë I'型机制）。
• 1,4-Dioxaspiro[2.2]pentanes. Synthesis, spectroscopic properties, and reactions with nucleophiles
  作者：Jack K. Crandall、David J. Batal、David P. Sebesta、Feng Lin

  DOI：10.1021/jo00003a044

  日期：1991.2

  A number of simple allenes have been converted cleanly to the corresponding 1,4-dioxaspiro[2.2]pentanes in good yields by oxidation with dimethyldioxirane. Mono- and trisubstituted allenes give the anti diastereomers with good stereoselectivity, whereas 1,3-disubstituted allenes show only a slight preference for the anti,anti isomers, unless steric effects are extreme. Stereochemical assignments are based on steric considerations and a consistent set of NMR characteristics that permit structural attributions. The addition of a range of nucleophiles (water, alcohols, amines, thiophenol, acetate, chloride, and fluoride) to these intermediates proceeded smoothly under buffered conditions to give highly functionalized products of general type 5. These reactions were shown to take place with the appropriate selectivities for S(N)2 substitutions in instances where these features were observable, namely, regioselective attack at the less-substituted epoxide carbon and inversion of configuration at the site of substitution. Under acidic conditions dioxaspiropentanes gave mixtures of other types of products, which appear to arise from carbocationic processes.
• Synthesis and stereochemistry of allenes. Part 3. Highly stereoselective synthesis of chiral alkyl allenes by organocopper(I)-induced anti 1,3-substitution of chiral propynyl esters
  作者：Cornelis J. Elsevier、Peter Vermeer

  DOI：10.1021/jo00276a040

  日期：1989.7