7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-甲醛 | 29915-83-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-甲醛
• 英文名称: 4,4-ethylenedioxy-2-methyl-1-cyclohexenecarbaldehyde
• 英文别名: 7-Methyl-1,4-dioxaspiro[4.5]dec-7-ene-8-carbaldehyde
• CAS: 29915-83-1
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: NOQHSCBTBLIRGQ-UHFFFAOYSA-N

物化性质

• 沸点：
  298.2±40.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2932999099

反应信息

• 作为反应物：
  描述：

  7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-甲醛 在 吡啶 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 正丁基锂 、 三氯化铝 、 草酰氯 、 L-(+)-酒石酸二乙酯 、 dimethyl sulfide borane 、 4 A molecular sieve 、 双氧水 、 sodium hydride 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 异辛烷 、 乙醚 、 二氯甲烷 为溶剂， 反应 16.0h， 生成 Toluene-4-sulfonic acid (2S,3S)-3-(7-methyl-1,4-dioxa-spiro[4.5]dec-7-en-8-ylmethyl)-oxiranylmethyl ester
  参考文献：
  名称：

  Oxyanion Orientation in Anionic Oxy-Cope Rearrangements

  摘要：

  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.

  DOI：

  10.1021/jo00085a037
• 作为产物：
  描述：

  (7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-基)甲醇 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 生成 7-甲基-1,4-二氧杂螺[4.5]癸-7-烯-8-甲醛
  参考文献：
  名称：

  Oxyanion Orientation in Anionic Oxy-Cope Rearrangements

  摘要：

  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.

  DOI：

  10.1021/jo00085a037

文献信息

• Studies on abscisic acid. Part XIV. Synthesis and physiological activity of methyl 6',6'-didemethyl abscisate and new chiral analogs.
  作者：Eiki NAGANO、Takayuki ORITANI、Kyohei YAMASHITA

  DOI：10.1271/bbb1961.44.2095

  日期：——

  Methyl 6', 6'-didemethyl abscisate (5) was synthesized and assayed to elucidate the physiological activity of methyl substituents on the cyclohexene ring of abscisic acid (ABA). During this study two new chiral stereoisomeric analogs 6 and 7 were synthesized from l- and d-carvone. The rice seedling assay and germination assay of garden radish showed that 6'-methyl groups of ABA were not important in biological activity and that 5'-isopropenyl analogs 6 and 7 were inactive.

  为了阐明脱落酸（ABA）环己烯环上甲基取代基的生理活性，我们合成并检测了 6'，6'-二去甲基脱落酸甲酯（5）。在这项研究中，从 l-和 d-香芹酮合成了两种新的手性立体异构体类似物 6 和 7。水稻育苗试验和萝卜发芽试验表明，ABA 的 6'-甲基对生物活性并不重要，5'-异丙烯基类似物 6 和 7 没有活性。
• Lee Eun, Lee Yong Rok, Moon Bongjin, Kwon Ohyun, Shim Mi Seong, Yun Jae S+, J. Org. Chem, 59 (1994) N 6, S 1444-1456
  作者：Lee Eun, Lee Yong Rok, Moon Bongjin, Kwon Ohyun, Shim Mi Seong, Yun Jae S+

  DOI：——

  日期：——
• SCHUBERT U., SYNTHESIS, 1978, NO 5, 364-365
  作者：SCHUBERT U.

  DOI：——

  日期：——
• 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.