(E)-2-methyl-1,5-heptadien-4-ol | 107791-76-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-2-methyl-1,5-heptadien-4-ol
• 英文别名: 1,5-dimethyl-1,5-hexadiene-3-ol；2-Methyl-1,5-heptadien-4-ol；2-methyl-hepta-1,5t-dien-4-ol；2-Methyl-hepta-1,5-dien-4-ol；(5E)-2-methylhepta-1,5-dien-4-ol
• CAS: 107791-76-4
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: MDTLRZIDFDKYHS-SNAWJCMRSA-N

物化性质

• 沸点：
  185.3±9.0 °C(Predicted)
• 密度：
  0.858±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-2-methyl-1,5-heptadien-4-ol 在 palladium on activated charcoal 氢气 作用下， 生成 2-甲基-4-庚醇
  参考文献：
  名称：

  Vapor-phase thermolyses of 3-hydroxy-1,5-hexadienes. II. Effects of methyl substitution

  摘要：

  DOI：

  10.1021/ja00990a019
• 作为产物：
  描述：

  6-chloro-2-methyl-4,5-epoxy-1-heptene 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 以74%的产率得到(E)-2-methyl-1,5-heptadien-4-ol
  参考文献：
  名称：

  摘要：

  Substituted 1,5-hexadien-3-ols were synthesized by the [2,3]-Wittig rearrangement of unsymmetrical bis-allyl ethers, as well as by reactions of 1-(2-alkenyl)-2-chloromethyloxiranes with Mg/THF. The products were oxidized with pyridinium chlorochromate (PCC), zinc chlorochromate (ZCC), tert-butyl hydroperoxide in the presence of OsO4, and tent-butyl hydroperoxide alone. The oxidation of substituted 1,5-hexadien-3-ols with PCC and ZCC gave the corresponding carbonyl compounds. In the reaction with tertbutyl hydroperoxide catalyzed by OsO4 the internal double bond in the substrate was regioselectively converted into epoxy group, whereas allylic oxidation was prevented.

  DOI：

  10.1023/a:1013843700623

文献信息

• An Investigation of the Reactions of Substituted Homoallylic Alcohols with Various Oxidation Reagents
  作者：S. Servi、A. Acar

  DOI：10.3390/70200104

  日期：——

  Substituted homoallylic alcohols have been synthesised both by [2,3]-Wittig rearrangement of unsymmetrical bis-allylic ethers and reaction of alkenyl chloromethyl oxiranes with Mg/THF. These substrates were then oxidized using four different oxidants. When the substituted homoallylic alcohols were oxidized with pyridinium chlorochromate or zinc chlorochromate nonahydrate the corresponding carbonyl

  取代的高烯丙醇已通过不对称双烯丙基醚的 [2,3]-Wittig 重排和烯基氯甲基环氧乙烷与 Mg/THF 的反应合成。然后使用四种不同的氧化剂氧化这些底物。当取代的高烯丙醇被氯铬酸吡啶鎓或氯铬酸锌九水合物氧化时，产生相应的羰基化合物。当用 t-BuOOH 氧化时，相同的底物与环氧化产物一起形成相应的烯丙基氧化产物。当使用 t-BuOOH 和催化量的 OsO4 时，烯丙基氧化反应被阻止，形成的唯一产物是那些取代双键被环氧化的产物。
• Selective epoxidation of allylic alcohols with dibutyltin oxyperoxide
  作者：Shigekazu Kanemoto、Tsuyoshi Nonaka、Koichiro Oshima、Kiltiro Utimoto、Hitosi Nozaki

  DOI：10.1016/s0040-4039(00)84803-0

  日期：——

  Dibutyltin oxyperoxide derived from Bu2SnO and tBuOOH epoxidize allylic alcohols with high stereo- and regioselectivities.

  衍生自Bu 2 SnO和t BuOOH的过氧化二丁基氧化锡以高的立体选择性和区域选择性环氧化烯丙醇。
• Oxyanion Orientation in Anionic Oxy-Cope Rearrangements
  作者：Eun Lee、Yong Rok Lee、Bongjin Moon、Ohyun Kwon、Mi Seong Shim、Jae Sook Yun

  DOI：10.1021/jo00085a037

  日期：1994.3

  Efficiency of chirality transfer in anionic oxy-Cope rearrangement depends solely on the orientational preference of the oxyanionic bond in the substrates with a single carbinol carbon chiral center. In chairlike transition-state conformations for the rearrangement of simplest substrates like anions generated from (E)-1-phenyl-1,5-hexadien-3-ol and (E)-1,5-heptadien-4-ol, the oxyanionic bond is more prone to adopt the pseudoaxial orientation. On the other hand, anions generated from (E)-2-methyl-1,5-heptadien-4-ol, (E)-5-tert-butyl-1-phenyl-1,5-hexadien-3-ol, and 4-(2'-methyl-1'-cyclohexenyl)-1-buten-3-ol undergo rearrangement via chairlike transition states in which the pseudoequatorial oxyanionic bond is favored. It can thus be surmized that there is a slight stereoelectronic preference for the pseudoaxial oxyanionic bond in the chairlike transition states for the rearrangement of substrates without steric constraints. Substitution at C5 of the basic 1,5-hexadien-3-ol framework of substrates, however, leads to 1,3-diaxial steric interaction in the chairlike transition states with pseudoaxial oxyanionic bond, and pseudoequatorial disposition of oxyanionic bond becomes more favorable.
• Asymmetric Synthesis of 2°- and 3°-Carbinols via <i>B</i>-Methallyl-10-(TMS and Ph)-9-borabicyclo[3.3.2]decanes
  作者：José G. Román、John A. Soderquist

  DOI：10.1021/jo701633k

  日期：2007.12.1

  [GRAPHICS]Simple Grignard procedures provide methallylboranes la and 1b in enantiomerically pure form from air-stable precursors in 98% and 95% yields, respectively. These reagents add smoothly to aldehydes and methyl ketones, respectively, providing branched 2 degrees- (6, 69-89%, 94-99% ee) and 3 degrees-(10, 71-87%, 74-96% ee) homoallylic alcohols.
• Use of Hine's D Values To Predict the Position of the Equilibrium in the Cope Rearrangement of Multiply Substituted 1,5-Dienes
  作者：James P. Hagen、Kemberly D. Lewis、Scott W. Lovell、Paolo Rossi、Ayse Z. Tezcan

  DOI：10.1021/jo00128a019

  日期：1995.11

  A series of 1,5-dienes (1a-f) were employed to test whether Hine's D values can predict the position of equilibrium in Cope rearrangements. In the cases of the substituent pairs [OCH3, H], [OCH3, CH3], [N(CH3)(2), H], [N(CH3)(2), CH3], and [N(CH3)(2), OCH3], equilibrium constants calculated with Hine's D values gave reasonable agreement with those obtained experimentally. Dienes 1g-i were prepared to test whether reduction of the pi-donating character of a nitrogen substituent (carbamoyl vs dimethylamino) would change the directing ability of the nitrogen group. The aggregate order of directing ability was N(CH3)(2) > OCH3 > EtO(2)CN(CH3) > CH3 > A. Diene 15a, with a more complicated substitution pattern (OCH3 and CH3 versus CH3 and H) not directly amenable to analysis with D values, can be considered to reduce to the case of [OCH3, H]. The experimental K-eq obtained agreed with that expected for the [OCH3, H] pair. Dienes 15c and 16b, designed to test the pairs [CH3, SPh] and [OCH3, SPh], respectively, decomposed under the gas phase conditions of the rearrangement. Attempts to effect rearrangement with Pd(II) catalysis failed.

表征谱图