6-methyl-hepta-4,5-dienylamine | 42192-42-7

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 6-methyl-hepta-4,5-dienylamine
• 英文别名: 2-Methyl-2,3-octadiene；2-methyl-octa-2,3-diene；2-Methyl-octa-2,3-dien；2-Methyl-2,3-octadien
• CAS: 42192-42-7
• 化学式: C₉H₁₆
• 分子量: 124.226
• InChiKey: CYZFLEBJVHANSW-UHFFFAOYSA-N

物化性质

• 沸点：
  140-145 °C(Press: 744 Torr)
• 密度：
  0.7570 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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-methyl-hepta-4,5-dienylamine 在 二甲基二环氧乙烷 、 sodium hydride 、 potassium carbonate 作用下， 以 四氢呋喃 、 丙酮 、 paraffin 为溶剂， 反应 0.17h， 生成 2-methyl-4-hydroxy-2-(propyloxy)-3-octanone
  参考文献：
  名称：

  1,4-Dioxaspiro[2.2]pentanes. Synthesis, spectroscopic properties, and reactions with nucleophiles

  摘要：

  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.

  DOI：

  10.1021/jo00003a044
• 作为产物：
  描述：

  3-甲基-1,2-丁二烯 在 正丁基锂 、 三正丁基氢锡 作用下， 反应 5.0h， 生成 6-methyl-hepta-4,5-dienylamine
  参考文献：
  名称：

  Cyclizations of .omega.-allenyl radicals

  摘要：

  DOI：

  10.1021/jo00186a009

文献信息

• Insetion d'allenes
  作者：J.L Roustan、A Guinot、P Cadiot

  DOI：10.1016/s0022-328x(00)96194-1

  日期：1980.8

  ketones are generated in moderate yields (50–60%) from allene or a mono-, di- or tri-substituted allenic hydrocarbon, n alkyl halide and sodium tetracarbonylferrate. The first step is the formation of a complex anion which results from transfer of the alkyl group on a coordinated CO, then of the acyl ligand thus formed on the allenic sp carbon. Protonation with acetic acid yields a hydroxy-η4-trimethylenemethane

  α，β-不饱和酮的生成是中等程度的收率（50-60％），来自于烯丙基或单，二或三取代的烯丙基烃，正烷基卤化物和四羰基高铁酸钠。第一步是形成络合阴离子，这是由于烷基转移到配位的CO上，然后转移了在烯丙基sp碳上形成的酰基配体。质子化用乙酸产生一个羟基η 4 -trimethylenemethane，容易异构化为一个η 4 -heterodieneiron三羰基。最后，在用三甲胺氧化物氧化时释放出α，β-不饱和酮。最取代的酮为主。
• Reactions of 3-alkyl- and 3,3-dialkyl-1-bromoallenes with organocuprates: Effects of the nature of the cuprate reagent on the regio- and stereoselectivity
  作者：Anna Maria Caporusso、Carmela Polizzi、Luciano Lardicci

  DOI：10.1016/s0040-4039(00)96867-9

  日期：1987.1

  Organocuprates induce 1,3- and direct substitution in 3-alkyl- and 3,3-dialkyl-1-bromo-1,2-dienes leading respectively to either terminal acetylenes or allenic hydrocarbons. The nature of the cuprate exerts a prominent role in determining both the regio- and the stereochemistry of these reactions.

  有机酸盐诱导3-烷基-和3,3-二烷基-1-溴-1,2-二烯中的1,3-和直接取代，分别导致末端乙炔或烯丙烃。铜酸盐的性质在确定这些反应的区域化学和立体化学中起着重要作用。
• Allenes. Part XXVII. Reaction of dialkyl(lithio)copper reagents with 1-bromoallenes, 1-iodoallenes, and 3-chloroalk-1-ynes
  作者：Michael Kalli、Phyllis D. Landor、Stephen R. Landor

  DOI：10.1039/p19730001347

  日期：——

  Allenic hydrocarbons are obtained in high yield by the reaction of 1-halogenoallenes or 3-chloroalk-1-ynes with dialkyl(lithio)copper reagents at low temperature.

  通过使1-卤代Allenes或3-chloroalk-1-ynes与二烷基（硫代）铜试剂在低温下反应，可以高收率获得烯丙烃。
• Preparation of allenes and acetylenes from ethynylalkanol acetates via organoboranes
  作者：M. Mark Midland

  DOI：10.1021/jo00435a034

  日期：1977.7
• A Tunable Class of Chiral Cp Ligands for Enantioselective Rhodium(III)-Catalyzed C–H Allylations of Benzamides
  作者：Baihua Ye、Nicolai Cramer

  DOI：10.1021/ja311956k

  日期：2013.1.16

  The lack of robust and tunable chiral versions of cyclopentadienyl (Cp) ligands hampers progress in the development of catalytic asymmetric versions of a myriad of reactions catalyzed by this ubiquitous ligand. Herein, we describe of a class of chiral Cp ligands with tunable steric parameters. Coordinated to transition metals, the ligand creates a well-defined chiral pocket, able to imprint its chirality onto the metal. The corresponding Rh complexes are shown to be excellent catalysts for enantioselective allylation of N-methoxybenzamides via directed C-H functionalizations at very mild conditions. The obtained enantioselectivities are excellent and demonstrate the viability of chiral Cp complexes as selective transition metal catalysts.