2-carbethoxy-1,1,3-trimethyl-1,3-butadiene | 17773-75-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-carbethoxy-1,1,3-trimethyl-1,3-butadiene
• 英文别名: ethyl 2-isopropenyl-3-methyl-2-butenoate；2-Butenoic acid, 3-methyl-2-(1-methylethenyl)-, ethyl ester；ethyl 3-methyl-2-prop-1-en-2-ylbut-2-enoate
• CAS: 17773-75-0
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: MTYLEFXCVKHMFY-UHFFFAOYSA-N

物化性质

• 沸点：
  55 °C(Press: 10 Torr)
• 密度：
  0.908±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-carbethoxy-1,1,3-trimethyl-1,3-butadiene 在 咪唑 、 4-二甲氨基吡啶 、 氢氧化钾 、 二异丁基氢化铝 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 115.5h， 生成 2-(tert-butyldimethylsiloxymethyl)-4-(2,4,6-triisoporpyl-benzenesulfonyl-hydrazono)-1,3,3-trimethyl-cyclohex-1-ene
  参考文献：
  名称：

  Total Synthesis of taxol. 2. Construction of A and C ring intermediates and initial attempts to construct the ABC ring system

  摘要：

  A method for the formation of Taxol's ABC ring system has been developed. General methods for the synthesis of versatile synthons for Taxol's A ring (8) and C ring (55) are presented. A model study using a simplified C ring synthon (17) confirmed the viability of the sequential Shapiro-McMurry strategy for formation of Taxol's B ring. Careful exploration of the chemistry of various A-B ring conjugates allowed the development of a successful method for formation of the B ring in a more functionalized system.

  DOI：

  10.1021/ja00107a007
• 作为产物：
  描述：

  1-Brom-1-aethoxycarbonyl-2,2,3,3-tetramethyl-cyclopropan 在 铜 作用下， 300.0 ℃ 、40.0 Pa 条件下， 生成 2-carbethoxy-1,1,3-trimethyl-1,3-butadiene
  参考文献：
  名称：

  Warner, Philip M.; Le, Diem, Synthetic Communications, 1984, vol. 14, # 14, p. 1341 - 1348

  摘要：

  DOI：

文献信息

• Diastereoselective triple radical cyclization of a bromomethyldimethylsilyl allyl ether
  作者：Andrew S. Kende、Michel Journet、Richard G. Ball、Nancy N. Tsou

  DOI：10.1016/0040-4039(96)01383-4

  日期：1996.8

  A convergent strategy to construct the B-ring in an AC → ABC cyclization to the taxane framework was tested. The bicyclic bromomethyldimethylsilyl ether 2 was efficiently synthesized by a sequence proceeding through the alkylation of the C-ring malonate 4 by the hindered A-ring bromide 3. The desired tandem 5-exo-trig/8-exo-dig cyclization of 2 to diol 1 was not observed. An alternative pathway was

  测试了在AC→ABC环化中建立紫杉烷骨架的B环的收敛策略。通过经受阻的A环溴化物3使C环丙二酸酯4烷基化而进行的序列有效地合成了双环溴甲基二甲基甲硅烷基醚2。没有观察到期望的串联的2-exo-trig / 8-exo-dig 2到二醇1的环化反应。通过分离结晶的四环非对映异构体12a和12b指示了另一种途径，该结晶四环非对映异构体由三个自由基环化的非对映选择性序列得到。
• Reactivity of hindered 1,1-dimethylbutadienes towards α,β-unsaturated enones
  作者：Kirsten A. Granum、Glenn Merkel、Jason A. Mulder、Stefan A. Debbins、Richard P. Hsung

  DOI：10.1016/s0040-4039(98)02333-8

  日期：1998.12

  The reactivity of several hindered 1,1-dimethylbutadienes towards alpha,beta-unsaturated enones were studied and compared. Computational and experimental results suggest that substituents at C-2 and C-3 of the dienes significantly effect the reactivities. A synthetic application of this reaction is also described. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Furuhata, Akimichi; Hirano, Masachika; Fujimoto, Izumi, Agricultural and Biological Chemistry, 1987, vol. 51, # 6, p. 1633 - 1640
  作者：Furuhata, Akimichi、Hirano, Masachika、Fujimoto, Izumi、Matsui, Masano

  DOI：——

  日期：——
• WARNER, P. M.;LE, D., SYNTH. COMMUN., 1984, 14, N 14, 1341-1347
  作者：WARNER, P. M.、LE, D.

  DOI：——

  日期：——
• FURUHATA, AKIMICHI;HIRANO, MASACHIKA;FUJIMOTO, IZUMI;MATSUI, MASANAO, AGR. AND BIOL. CHEM., 51,(1987) N 6, 1633-1640
  作者：FURUHATA, AKIMICHI、HIRANO, MASACHIKA、FUJIMOTO, IZUMI、MATSUI, MASANAO

  DOI：——

  日期：——