2-Neopentyl-3-furyl tert-butyl ketone | 153626-04-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-Neopentyl-3-furyl tert-butyl ketone
• 英文别名: 1-[2-(2,2-Dimethylpropyl)furan-3-yl]-2,2-dimethylpropan-1-one
• CAS: 153626-04-1
• 化学式: C₁₄H₂₂O₂
• 分子量: 222.327
• InChiKey: AFBPLXKABJXNSZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  30.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-Neopentyl-3-furyl tert-butyl ketone 在 lithium aluminium tetrahydride 、 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 生成 2,3-Bis(tert-butylmethylene)-2,3-dihydrofuran
  参考文献：
  名称：

  Effects of .alpha.-tert-butyl group substitution on the reactivity and dimerization products of furan-based o-quinodimethanes

  摘要：

  Flash vacuum pyrolysis (FVP) of 2-neopentyl-3-furylmethyl benzoate (8) produces 3-methylene-2-(tert-butylmethylene)-2,3-dihydrofuran (5), the major product as shown by low-temperature H-1 NMR spectroscopy. Upon warming to room temperature, 5 dimerizes giving mostly two stereoisomeric [4 + 2] dimers 11a and 11b in addition to a small amount of the [4 + 4] dimer 12. FVP of a mixture of the two [4 + 2] dimers 11a and 11b gives the thermodynamically more stable [4 + 4] dimer 12. The rate constants for the dimerization of 5 in solution at temperatures from -29 to +5 OC were determined by H-1 NMR spectroscopy The rate constants and activation parameters (Delta H-double dagger = 10.8 kcal/mol, Delta S-double dagger = -28.8 eu) are very similar to those reported for the unsubstituted furan-based o-quinodimethane. FVP of (2-methyl-3-furyl)(tert-butyl)methyl benzoate (13) and (2-neopentyl-3-furyl)(tert-butyl)methyl benzoate (18) give as the major product, 2-methylene-3-(tert-butylmethylene)-2,3-dihydrofuran (6) and 2,3-bis(tert-butylmethylene)-2,3-dihydro (7), respectively. Compounds 6 and 7, in contrast to 5, are stable at room temperature apparently because for each of these compounds a bulky tert-butyl group is on the more reactive methylene, the S-methylene. These results offer further support for the mechanism for the dimerization of furan-based o-quinodimethanes which proceeds in two steps via a transient diradical intermediate.

  DOI：

  10.1021/jo00088a050
• 作为产物：
  描述：

  3,3-二甲基丁酰氯 在 吡啶 、 sodium hydroxide 、 copper(l) iodide 、 氯化亚砜 、 lithium cyclohexylisopropylamide 作用下， 以 乙醚 为溶剂， 反应 26.0h， 生成 2-Neopentyl-3-furyl tert-butyl ketone
  参考文献：
  名称：

  Effects of .alpha.-tert-butyl group substitution on the reactivity and dimerization products of furan-based o-quinodimethanes

  摘要：

  Flash vacuum pyrolysis (FVP) of 2-neopentyl-3-furylmethyl benzoate (8) produces 3-methylene-2-(tert-butylmethylene)-2,3-dihydrofuran (5), the major product as shown by low-temperature H-1 NMR spectroscopy. Upon warming to room temperature, 5 dimerizes giving mostly two stereoisomeric [4 + 2] dimers 11a and 11b in addition to a small amount of the [4 + 4] dimer 12. FVP of a mixture of the two [4 + 2] dimers 11a and 11b gives the thermodynamically more stable [4 + 4] dimer 12. The rate constants for the dimerization of 5 in solution at temperatures from -29 to +5 OC were determined by H-1 NMR spectroscopy The rate constants and activation parameters (Delta H-double dagger = 10.8 kcal/mol, Delta S-double dagger = -28.8 eu) are very similar to those reported for the unsubstituted furan-based o-quinodimethane. FVP of (2-methyl-3-furyl)(tert-butyl)methyl benzoate (13) and (2-neopentyl-3-furyl)(tert-butyl)methyl benzoate (18) give as the major product, 2-methylene-3-(tert-butylmethylene)-2,3-dihydrofuran (6) and 2,3-bis(tert-butylmethylene)-2,3-dihydro (7), respectively. Compounds 6 and 7, in contrast to 5, are stable at room temperature apparently because for each of these compounds a bulky tert-butyl group is on the more reactive methylene, the S-methylene. These results offer further support for the mechanism for the dimerization of furan-based o-quinodimethanes which proceeds in two steps via a transient diradical intermediate.

  DOI：

  10.1021/jo00088a050

文献信息

• Trahanovsky Walter S., Huang Yih-chuan Jason, Leung Man-kit, J. Org. Chem, 59 (1994) N 9, S 2594-2598
  作者：Trahanovsky Walter S., Huang Yih-chuan Jason, Leung Man-kit

  DOI：——

  日期：——
• Effects of .alpha.-tert-butyl group substitution on the reactivity and dimerization products of furan-based o-quinodimethanes
  作者：Walter S. Trahanovsky、Yihchuan Jason Huang、Mankit Leung

  DOI：10.1021/jo00088a050

  日期：1994.5

  Flash vacuum pyrolysis (FVP) of 2-neopentyl-3-furylmethyl benzoate (8) produces 3-methylene-2-(tert-butylmethylene)-2,3-dihydrofuran (5), the major product as shown by low-temperature H-1 NMR spectroscopy. Upon warming to room temperature, 5 dimerizes giving mostly two stereoisomeric [4 + 2] dimers 11a and 11b in addition to a small amount of the [4 + 4] dimer 12. FVP of a mixture of the two [4 + 2] dimers 11a and 11b gives the thermodynamically more stable [4 + 4] dimer 12. The rate constants for the dimerization of 5 in solution at temperatures from -29 to +5 OC were determined by H-1 NMR spectroscopy The rate constants and activation parameters (Delta H-double dagger = 10.8 kcal/mol, Delta S-double dagger = -28.8 eu) are very similar to those reported for the unsubstituted furan-based o-quinodimethane. FVP of (2-methyl-3-furyl)(tert-butyl)methyl benzoate (13) and (2-neopentyl-3-furyl)(tert-butyl)methyl benzoate (18) give as the major product, 2-methylene-3-(tert-butylmethylene)-2,3-dihydrofuran (6) and 2,3-bis(tert-butylmethylene)-2,3-dihydro (7), respectively. Compounds 6 and 7, in contrast to 5, are stable at room temperature apparently because for each of these compounds a bulky tert-butyl group is on the more reactive methylene, the S-methylene. These results offer further support for the mechanism for the dimerization of furan-based o-quinodimethanes which proceeds in two steps via a transient diradical intermediate.