4-Methylenespiro<2.7>decane | 119489-88-2

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 4-Methylenespiro<2.7>decane
• 英文别名: 4-methylenespiro[2,2]decane；4-methylenespiro[2.7]decane；4-Methylidenespiro[2.7]decane；10-methylidenespiro[2.7]decane
• CAS: 119489-88-2
• 化学式: C₁₁H₁₈
• 分子量: 150.264
• InChiKey: QOQIEULYFLBOBV-UHFFFAOYSA-N

物化性质

• 沸点：
  213.1±7.0 °C(Predicted)
• 密度：
  0.89±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  4-Methylenespiro<2.7>decane 在 氢氧化钾 、 乙醇 、 苄基三乙基氯化铵 、 sodium 作用下， 以 苯 为溶剂， 反应 38.0h， 生成 dispiro<2.0.2.6>dodecane
  参考文献：
  名称：

  Electronic and molecular structure of simple bicyclopropyls. Photoelectron spectroscopy and model calculations

  摘要：

  DOI：

  10.1021/jo00137a011
• 作为产物：
  描述：

  2,2-dichloro-10-methylidenespiro[2.7]decane 在 乙醇 、 sodium 作用下， 生成 4-Methylenespiro<2.7>decane
  参考文献：
  名称：

  Electronic and molecular structure of simple bicyclopropyls. Photoelectron spectroscopy and model calculations

  摘要：

  DOI：

  10.1021/jo00137a011

文献信息

• (-)-(9<i>R</i>,10<i>S</i>)-10-Acetyl-9,10-dimethylbicyclo[6.4.0]dodec-1(8)-ene: Optical Resolution, Catalyst Systems, Derivatives and Olfactory Properties
  作者：Philip Kraft、Sofia Gallo

  DOI：10.1055/s-2004-815943

  日期：——

  By separation of the enantiomers of the woody-ambery odorant 10-acetyl-9,10-dimethylbicyclo[6.4.0]dodec-1(8)-ene (rac-12) via their diastereomeric (-)-camphanoates, the (-)-(9R,10S)-isomer (9R,10S)-12 was determined to be the most powerful enantiomer. With an odor threshold of 0.19 ng/L it is about one hundred times stronger than its antipode. Racemic 10-acetyl-9,10-dimethylbicyclo[6.4.0]dodec-1(8)-ene (rac-12) was synthesized by an unusual [4+2]-cycloaddition of 4-methylenespiro[2.7]decane (10) and 3-methylbut-3-en-2-one (11) in the presence of Wilkinson’s catalyst. However, attempts to induce optical activity with chiral rhodium(I) catalysts proved futile. Platinum(II)-DIOP catalysts furnished traces (0.05% GC yield) of (-)-(9R,10S)-10-acetyl-9,10-dimethylbicyclo[6.4.0]dodec-1(8)-ene [(9R,10S)-12] with an enantiomeric excess of around 40% ee. For further studies on the structure-odor correlation of woody odorants, two new tricyclic analogs of rac-12, (±)-(2R*,3S*,7S*)-2-methyltricyclo[7.6.0.03,7]pentadec-1(9)-en-4-one (18) and (±)-(2R*,3S*,7S*)-2,3-dimethyl-tricyclo[7.6.0.03,7]pentadec-1(9)-en-4-one (20) were synthesized and characterized.

  通过将木质-琥珀香型香料10-乙酰基-9,10-二甲基二环[6.4.0]十二碳-1(8)-烯（外消旋体12）的非对映异构体(-)-樟脑酸盐分离，确定(-)-(9R,10S)异构体（9R,10S）-12为最强手性异构体。其嗅觉阈值为0.19 ng/L，约为其对映体的100倍。10-乙酰基-9,10-二甲基二环[6.4.0]十二碳-1(8)-烯（外消旋体12）是通过4-甲亚基螺[2.7]癸烷（10）和3-甲基丁-3-烯-2-酮（11）在Wilkinson催化剂存在下不寻常的[4+2]环加成合成的。然而，尝试用 chiral rhodium(I) 催化剂诱导光学活性证明是徒劳的。铂(II)-DIOP 催化剂提供了痕量（0.05% GC 产率）的(-)-(9R,10S)-10-乙酰基-9,10-二甲基二环[6.4.0]十二碳-1(8)-烯[(9R,10S)-12]，具有约40%的ee值。为了进一步研究木质香料的结构-嗅觉相关性，合成了外消旋体12的两个新的三环类似物，(±)-(2R*,3S*,7S*)-2-甲基三环[7.6.0.03,7]十五碳-1(9)-烯-4-酮（18）和(±)-(2R*,3S*,7S*)-2,3-二甲基-三环[7.6.0.03,7]十五碳-1(9)-烯-4-酮（20），并进行了表征。
• Design and Synthesis of Violet Odorants with Bicyclo[6.4.0]dodecene and Bicyclo[5.4.0]undecene Skeletons
  作者：Philip Kraft

  DOI：10.1055/s-1999-3444

  日期：1999.4

  The Diels-Alder reaction of 1,2-bis(methylene)cyclooctane (13), 4-methylenespiro[2,7]decane (29), 4-methylene-spiro[2.6]nonane (40) and 4-methylenespiro[2,7]dec-8-ene (46) with different α,β-unsaturated carbonyl compounds afforded various derivatives 16, 18, 20, 22, 24, 26, 32, 36, 38, 41, 42 and 47 of a molecular-modeled lead compound 9. These less flexible β-ionone-mimics with bicyclo[6.4]dodecene and bicyclo[5.4.0]undecene skeletons possess interesting fruity-woody-floral odor notes and provide insight into the structure-odor correlation of violet odorants. 5-(2-Methylcycloalk-1-en-1-yl)hex-3-en-2-ones (e. g. 35) were identified as byproducts of the Rh(I)-catalyzed reactions of the vinylcyclopropanes 29 and 40.

  1,2-双(亚甲基)环辛烷(13)、4-亚甲基螺[2,7]癸烷(29)、4-亚甲基螺[2.6]壬烷(40)和4-亚甲基螺[2,7]癸-8-烯(46)与不同的α,β-不饱和羰基化合物进行Diels-Alder反应，得到了分子模型化合物的各种衍生物16、18、20、22、24、26、32、36、38、41、42和47。这些较不灵活的双环[6.4]十二碳烯和双环[5.4.0]十一碳烯骨架的β-紫罗兰酮类似物，具有有趣的果香-木香-花香气味特征，并为进一步了解紫罗兰酮类化合物的结构与气味相关性提供了见解。5-(2-甲基环烷-1-烯-1-基)己-3-烯-2-酮(例如35)被确认为乙烯基环丙烷29和40在Rh(I)催化反应中的副产物。
• Ring opening rections of vinyl cyclopropanes with para toluene sulphonyl iodide.
  作者：Maria C.M. de C. Alpoim、Angela D. Morris、William B. Motherwell、Dennis M. O'Shea

  DOI：10.1016/s0040-4039(00)80448-7

  日期：1988.1

  Substituted 1-iodo-5-para toluene sulphonyl pent-3-enes are readily prepared by regiospecific ring opening of vinyl cyclopropanes with para toluene sulphonyl iodide. Intramolecular carbanionic cyclisation of the cisoid isomers via α or γ alkylation is substrate dependent.

  通过乙烯基环丙烷与对甲苯磺酰碘的区域特异性开环，可以容易地制备取代的1-碘-5-对甲苯磺酰戊-3-烯。通过α或γ烷基化的顺式异构体的分子内碳负离子环化取决于底物。
• Synthesis and Olfactory Properties of Spirocyclic Georgywood^® Analogues
  作者：Philip Kraft、David Frech、Urs Müller、Georg Fráter

  DOI：10.1055/s-2006-942418

  日期：2006.7

  Spirocyclic analogues of Georgywood® (3) and unlike-10-acetyl-9,10-dimethylbicyclo[6.4.0]dodec-1(8)-ene (4), in which the acetyl moiety and the methyl substituent of C-10 are part of a cyclopentyl or cyclohexyl ring, were synthesized from 8a-homomyrcene (6) and 4-methylenespiro[2.7]decane (13), respectively. 2-(Dimethylaminomethyl)cyclopentanone (7) or the allyl 1-(acetoxymethyl)-2-oxocycloalkanecarboxylates

  Georgywood® (3) 的螺环类似物和不同于-10-acetyl-9,10-dimethylbicyclo[6.4.0]dodec-1(8)-ene (4)，其中乙酰基部分和 C-10 的甲基取代基是环戊基或环己基环的一部分，分别由 8a-高月桂烯 (6) 和 4-亚甲基螺[2.7]癸烷 (13) 合成。2-(二甲氨基甲基)环戊酮 (7) 或烯丙基 1-(乙酰氧基甲基)-2-氧代环烷烃羧酸酯 14 和 18 在普通 Diels-Alder 反应或乙烯基环丙烷系统上的 [4+2] 环加成反应中用作亚甲基环烷酮前体13 在威尔金森的催化剂存在下。通过用甲基碘对所得螺环进行简单的 LDA 介导烷基化，制备了更多类似物，为 Iso E Super® (1) 的典型木质-琥珀气味特征的结构和立体化学要求提供了额外的见解，这对 Hong 和 Corey 提出的结合模型提出了质疑。本研究中发现的最佳气味剂是
• Bicyclic aldehyde and ketone odorants
  申请人：Givaudan Roure (International) S.A.

  公开号：US06242413B1

  公开（公告）日：2001-06-05

  The invention relates to bicyclic aldehydes and ketones of formula (I): wherein n is 1 or 2; R1 and R4 are independently H or CH3; and R2 and R3 are independently H, CH3 or CH2CH3 The invention also provides odorant compositions containing at least one compound of formula (I). A process for the manufacture of R1-methyl substituted compounds of formula (I) having a bridgehead-positioned double bond, as well as intermediates thereof is also provided.

  本发明涉及公式（I）的双环醛和酮：其中n为1或2；R1和R4独立地为H或CH3；R2和R3独立地为H，CH3或CH2CH3。本发明还提供含有至少一种公式（I）化合物的香料组合物。本发明还提供制备具有桥头位置双键的R1-甲基取代化合物的方法，以及其中间体。