trimethylsilyl enol ether of 1-acetylcyclohepta-1,3,5-triene | 287114-82-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: trimethylsilyl enol ether of 1-acetylcyclohepta-1,3,5-triene
• 英文别名: 1-Cyclohepta-1,3,5-trien-1-ylethenoxy(trimethyl)silane
• CAS: 287114-82-3
• 化学式: C₁₂H₁₈OSi
• 分子量: 206.36
• InChiKey: NJAQLWANQCZFOR-UHFFFAOYSA-N

物化性质

• 熔点：
  126-128 °C
• 沸点：
  254.8±9.0 °C(Predicted)
• 密度：
  0.926±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.79
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trimethylsilyl enol ether of 1-acetylcyclohepta-1,3,5-triene 在 三氟甲磺酸三甲基硅酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 23.0h， 生成
  参考文献：
  名称：

  Synthesis and stability of 1,1-dialkyl-1H-azulenium cations

  摘要：

  Starting from trimethylsilyl enol ether of 1-acetyl-1,3,5-cycloheptatriene, the title 1,1-dimethyl-, 1,1-diethyl-, and 1,1-dipropyl-1H-azulenium cations 6-8 were synthesized in five steps. The order of pK(R)+ values of these cations was found to be 7 > 8 > 6. A comparison of the values between 1, 1-dialkyl- and 1, 1-spiroalkylated 1H-azulenium cations with the same number of carbon atoms at the I-position provided the results of 7 > 1 and 8 < 3. The cation 8 shows a relatively lower pKR+ value to those of 3 and 7 probably due to its slightly bulkier propyl groups from which solvation stabilization of 8 under the conditions suffers. An intermolecular charge-transfer interaction between the cations and dibenzo-24-crown-8 was also studied. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2006.05.084
• 作为产物：
  描述：

  三甲基氯硅烷 、 1-(1,3,5-环庚三烯-1-基)乙酮 在 三乙胺 、 sodium iodide 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以94%的产率得到trimethylsilyl enol ether of 1-acetylcyclohepta-1,3,5-triene
  参考文献：
  名称：

  一种制备3,3-二烷基-1,2,3,8-四氢azulen-1-one的合成方法

  摘要：

  摘要 L-乙酰环庚-1,3,5-三烯的三甲基甲硅烷基烯醇醚通过Mukaiyama羟醛反应的两步序列转化为3,3-二烷基-1,2,3,8-四氢azulen-1-one与酮和随后的纳扎罗夫环化。

  DOI：

  10.1080/00397910008086874

文献信息

• Synthesis, Stability, and Crystal Structure of an Azulenium Cation Containing an Adamantyl Group
  作者：Mitsunori Oda、Nobue Nakajima、Nguyen Chung Thanh、Kazuhiro Kitahara、Ryuta Miyatake、Shigeyasu Kuroda

  DOI：10.1002/ejoc.200800700

  日期：2008.11

  been obtained in similar reactions forming tetrahydroazulenones. The pKR+ value of the title cation was found to be 9.8, which is less than that expected by inductive stabilization from the number of carbons at the 1-position. The X-ray crystal structure of the title cation (ClO4– salt) reveals CH–O interactions and deformation of the azulenyl ion part.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

  从 1-乙酰基-1,3,5-环庚三烯的三甲基甲硅烷基烯醇醚开始，通过五步序列合成标题 1H-azulenium 阳离子，包括 Noyori-Mukaiyama 羟醛反应、Nazarov 环化、Shapiro 反应、和氢化物抽象。羟醛型加合物的纳扎罗夫反应导致形成了一种不寻常的双键位置异构体，这在形成四氢芴酮的类似反应中从未获得过。发现标题阳离子的 pKR+ 值为 9.8，这低于通过 1 位碳数诱导稳定所预期的值。标题阳离子 (ClO4– 盐) 的 X 射线晶体结构揭示了薁基离子部分的 CH–O 相互作用和变形。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Synthesis, Stability, and X-Ray Crystallographic Structure Analysis of Spiro[1H-azulenium-1,1′-cycloalkane] Ions
  作者：Mitsunori Oda、Aya Fukuta (née Sakamoto)、Takanori Kajioka、Takuya Uchiyama、Hitoshi Kainuma、Ryuta Miyatake、Shigeyasu Kuroda

  DOI：10.1016/s0040-4020(00)00964-9

  日期：2000.12

  subsequent hydride abstraction with a trityl salt gave spiro[1H-azulenium-1,1′-cyclopentane and -1,1′-cyclohexane] ions (3 and 4). On the other hand, spiro[1H-azulenium-1,1′-cycloheptane] ion (5) was synthesized from 1-acetylcyclohepta-1,3,5-triene by a sequence involving the Mukaiyama aldol reaction, the Nazarov cyclization, the Shapiro reaction, and hydride abstraction. These cations showed greater

  1，6-二氢杂氮烯直接环烷基化，然后用三苯甲基盐提取氢化物，得到螺[1 H -azulenium-1,1'-环戊烷和-1,1'-环己烷]离子（3和4）。另一方面，由1-乙酰基环庚-1,3,5-三烯通过涉及Mukaiyama aldol反应，Nazarov环化的序列合成了螺[1 H -azulenium-1,1'-cycloheptane]离子（5）， Shapiro反应和氢化物提取。这些阳离子显示出比三元和四元环同系物更大的动力学稳定性。他们的p K R+值与已知的二取代的对位阳离子相比要大得多，并且处于1位碳原子数的顺序，这表明除π共轭和σ共轭作用外，螺烷基的诱导作用。 ，控制热力学稳定性。还描述了这些阳离子的X射线晶体结构分析。
• Spiro[1H-azulenium-1,9′-fluorene] perchlorate. Intramolecular charge-transfer interaction between orthogonally arranged units of the azulenium cation and fluorene
  作者：Mitsunori Oda、Nobue Nakajima、Nguyen Chung Thanh、Shigeyasu Kuroda

  DOI：10.1016/j.tetlet.2008.09.142

  日期：2008.12

  9′-fluorene] (3) perchlorate was synthesized in five steps starting from fluorenone and trimethylsilyl enol ether of 1-acetylcycloheptatriene. The pKR+ value of 3 was determined to be 7.8. A characteristic absorption band of 3 in acetonitrile was observed at 430 nm, which shows a bathochromic shift in dichloromethane, indicating the first example of the intramolecular charge-transfer interaction between orthogonally

  从芴酮和1-乙酰基环庚三烯的三甲基甲硅烷基烯醇醚开始，分五个步骤合成了螺[1 H -azulenium-1,9'-芴]（3）高氯酸盐。测定的p K R +值为3。在430 nm处观察到乙腈中3的特征吸收带，表明在二氯甲烷中发生了红移，表明具有对yl离子环的z离子和具有两个氟原子的芴的正交排列单元之间分子内电荷转移相互作用的第一个例子苯环。
• Synthesis and stability of 1,1-dialkyl-1H-azulenium cations
  作者：Mitsunori Oda、Nobue Nakajima、Nguyen Chung Thanh、Takanori Kajioka、Shigeyasu Kuroda

  DOI：10.1016/j.tet.2006.05.084

  日期：2006.8

  Starting from trimethylsilyl enol ether of 1-acetyl-1,3,5-cycloheptatriene, the title 1,1-dimethyl-, 1,1-diethyl-, and 1,1-dipropyl-1H-azulenium cations 6-8 were synthesized in five steps. The order of pK(R)+ values of these cations was found to be 7 > 8 > 6. A comparison of the values between 1, 1-dialkyl- and 1, 1-spiroalkylated 1H-azulenium cations with the same number of carbon atoms at the I-position provided the results of 7 > 1 and 8 < 3. The cation 8 shows a relatively lower pKR+ value to those of 3 and 7 probably due to its slightly bulkier propyl groups from which solvation stabilization of 8 under the conditions suffers. An intermolecular charge-transfer interaction between the cations and dibenzo-24-crown-8 was also studied. (c) 2006 Elsevier Ltd. All rights reserved.
• A Synthetic Method for Preparing 3,3-Dialkyl-1,2,3,8-tetrahydroazulen-1-one
  作者：Mitsunori Oda、Takanori Kajioka、Kazuya Ikeshima、Ryuta Miyatake、Shigeyasu Kuroda

  DOI：10.1080/00397910008086874

  日期：2000.7

  Abstract The trimethylsilyl enol ether of l-acetylcyclohepta-1,3,5-triene was transformed to 3,3-dialkyl-1,2,3,8-tetrahydroazulen-1-one by a two-step sequence involving the Mukaiyama aldol reaction with ketones and the subsequent Nazarov cyclization.

  摘要 L-乙酰环庚-1,3,5-三烯的三甲基甲硅烷基烯醇醚通过Mukaiyama羟醛反应的两步序列转化为3,3-二烷基-1,2,3,8-四氢azulen-1-one与酮和随后的纳扎罗夫环化。