6,6-dimethyl4-methylidenebicyclo[3.1.1]hept-2-ene | 190715-28-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 6,6-dimethyl4-methylidenebicyclo[3.1.1]hept-2-ene
• 英文别名: (1S:5S)-pinadiene-(2(10).3)；(1S:5S)-Pinadien-(2(10).3)；(1S)-Pina-2(10),3-dien; (-)-Verbenen；(-)-Verbenene；(1S,5S)-6,6-dimethyl-4-methylidenebicyclo[3.1.1]hept-2-ene
• CAS: 190715-28-7
• 化学式: C₁₀H₁₄
• 分子量: 134.221
• InChiKey: YOQFOABVDRBYCG-RKDXNWHRSA-N

物化性质

• 沸点：
  162.3±7.0 °C(Predicted)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• 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：

  6,6-dimethyl4-methylidenebicyclo[3.1.1]hept-2-ene 生成 trans-pin-3-en-2-ol
  参考文献：
  名称：

  绝对授权书

  摘要：

  芳樟醇的绝对构型的新的独立证明是由非对映体pin烷-2-醇的热解形成提供的。

  DOI：

  10.1016/0040-4020(62)80021-0
• 作为产物：
  描述：

  马鞭烯醇 在 sodium acetate 、 乙酸酐 作用下， 生成 6,6-dimethyl4-methylidenebicyclo[3.1.1]hept-2-ene
  参考文献：
  名称：

  Blumann; Zeitschel, Chemische Berichte, 1913, vol. 46, p. 1192

  摘要：

  DOI：

文献信息

• Incorporation of an Allene Unit intoα-Pinenevia β-Elimination
  作者：Benan Kilbas、Akin Azizoglu、Metin Balci

  DOI：10.1002/hlca.200690145

  日期：2006.7

  6-trimethylbicyclo[3.1.1]hept-2-ene (11) were synthesized by reacting 2,6,6-trimethylbicyclo[3.1.1]heptan-3-one (9) with hydrazine, followed by treatment with I2 in the presence of Et3N. Treatment of 11 with t-BuOK as base in diglyme at 220° resulted in the formation of 9 and 6,6-dimethyl-4-methylidenebicyclo[3.1.1]hept-2-ene (12). For the formation of 9, the cyclic allene 7 is proposed as an intermediate. Treatment

  两种双键异构体3-iodo-2,6,6-trimethylbicyclo [3.1.1] hept-2-ene（6b）和3-iodo-4,6,6-trimethylbicyclo [3.1.1] hept-2烯（11）由2,6,6-三甲基反应合成[3.1.1]庚烷-3-酮（9）与肼，随后用我2的Et的存在3 N.治疗11与在220°的二甘醇二甲醚中，以t- BuOK为碱，形成9和6,6-二甲基-4-亚甲基双环[3.1.1]庚-2-烯（12）。为了形成9，提出了环状丙二烯7作为中间体。第二种异构体6b的处理用170℃的t- BuOK，生成二烯12和二聚产物17。讨论了这种转换的潜在机制。基于对丙二烯7和炔烃15的密度泛函理论（DFT）计算，排除了后者作为中间体的形成。
• Electron transfer induced deprotonation of α- and β-pinene: Evidence for ring-closed vinylcyclobutane radical cations
  作者：Dahui Zhou、Mohsin Sheik、Heinz D. Roth

  DOI：10.1016/0040-4039(96)00332-2

  日期：1996.4

  Electron transfer from α- (1) or β-pinene (2), to 2,3,5,6-tetrachlorobenzoquinone generates radical cations, which are rapidly deprotonated by the semiquinone radical anion. (1S,5S)-2 is converted to (1S,5S)-1 and (1R,5R)-1 yields a dehydrogenation product, verbenene, (1R,5R)-9 with essentially quantitative retention of optical activity. The results support chiral, “ring-closed” radical cation structures

  电子从α-（1）或β-pine烯（2）转移到2,3,5,6-四氯苯醌产生自由基阳离子，该阳离子被半醌自由基阴离子迅速去质子化。（1S，5S）-2被转化为（1S，5S）-1，并且（1R，5R）-1产生具有基本上定量保留的光学活性的脱氢产物马鞭草烯（1R，5R）-9。结果支持了手性，“环封闭”的自由基阳离子结构，其中烯丙基-季环丁烷CC键保留了很大程度的键合。
• Bessiere-Chretien,Y.; Grison,C., Bulletin de la Societe Chimique de France, 1970, p. 3103 - 3111
  作者：Bessiere-Chretien,Y.、Grison,C.

  DOI：——

  日期：——
• Uzarewicz; Dresler, Polish Journal of Chemistry, 1997, vol. 71, # 2, p. 181 - 195
  作者：Uzarewicz、Dresler

  DOI：——

  日期：——
• Oxidation of α-pinene by atmospheric oxygen in the supercritical CO2—ethyl acetate system in the presence of Co(II) complexes
  作者：V. I. Anikeev、I. V. Il’ina、S. Yu. Kurbakova、A. A. Nefedov、K. P. Volcho、N. F. Salakhutdinov

  DOI：10.1134/s0036024412010049

  日期：2012.2

  The reactivity of monoterpene alpha-pinene in a flow reactor in the presence of cobalt catalyst in a complex supercritical solvent consisting of CO2 and ethyl acetate is studied over the temperature range of 190-320A degrees C and a pressure range of 110-125 atm. It was found that the main isomerization products include compounds with bicyclo[2.2.1]heptane and p-menthane backbones; the reaction is accompanied by partial racemization. The formation of oxidation products is observed in the presence of air, with epoxydation rather than allylic oxidation being the predominant process at the first stage. The oxidized products (campholenic aldehyde, verbenone, pinocamphone) are shown to be formed with a high enantioselectivity; the formation of acetoxylation products is observed at temperatures above 200A degrees C.

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