diethyl(3,4-dimethylpent-3-enyl)amine | 259200-10-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: diethyl(3,4-dimethylpent-3-enyl)amine
• 英文别名: N,N-diethyl-3,4-dimethylpent-3-en-1-amine
• CAS: 259200-10-7
• 化学式: C₁₁H₂₃N
• 分子量: 169.31
• InChiKey: FMTXOJDYIWLZMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  diethyl(3,4-dimethylpent-3-enyl)amine 在 氢氧化钾 作用下， 以 水 、 乙二醇 、 丙酮 为溶剂， 生成 3,4-Dimethyl-1,3-pentadiene
  参考文献：
  名称：

  Regioselective Synthesis and Diels−Alder Reaction of 3,4-Dimethylpenta-1,3-diene. Conformational Study of Bicyclic Adducts Structures by ¹H NMR (NOESY, ASIS) and Molecular Modeling (MM2, AM1, RHF, and DFT)

  摘要：

  A three-step, regioselective synthesis of 3,4-dimethylpenta-1,3-diene 1 has been developed. The condensation of acetone diethylacetal with ethyl propenyl ether yielded, after hydrolysis of the resulting triethoxy adduct 10, 2,3-dimethyl-2-butenal 7. Wittig reaction of 7 with methylenetriphenylphosphorane afforded desired diene 1 in 31% overall yield, easily scalable to the 10 g level, Diels-Alder reaction of 1 with maleic anhydride in benzene was known to afford a 50:50 mixture of "normal" (2) and "rearranged" (3) adducts. In THF as solvent, 2 has been reproducibly obtained in over 90% yield as a 98:2 mixture with 3. H-1 NMR spectroscopy (NOESY, ASIS) and molecular modeling (MM2, AM1, ab initio) have been used jointly to determine the conformation of 2 and 3, All are consistent with a folded structure of "rearranged" 3. On the other hand, only RHF/6-31G* and B3LYP/6-31G* ab initio models were in agreement with NMR spectroscopy for an extended conformation of adduct 2. In this case, neither MM2 nor AM1 models gave results consistent with NMR: discrepancies as high as 30 degrees were noted for some dihedrals between these models and ab initio ones.

  DOI：

  10.1021/jo991173d
• 作为产物：
  描述：

  1-二乙基氨-3-丁酮 、 碘化异丙基三苯鏻 在 potassium tert-butylate 作用下， 以 二甲基亚砜 、 苯 为溶剂， 反应 0.5h， 以29.5%的产率得到diethyl(3,4-dimethylpent-3-enyl)amine
  参考文献：
  名称：

  Regioselective Synthesis and Diels−Alder Reaction of 3,4-Dimethylpenta-1,3-diene. Conformational Study of Bicyclic Adducts Structures by ¹H NMR (NOESY, ASIS) and Molecular Modeling (MM2, AM1, RHF, and DFT)

  摘要：

  A three-step, regioselective synthesis of 3,4-dimethylpenta-1,3-diene 1 has been developed. The condensation of acetone diethylacetal with ethyl propenyl ether yielded, after hydrolysis of the resulting triethoxy adduct 10, 2,3-dimethyl-2-butenal 7. Wittig reaction of 7 with methylenetriphenylphosphorane afforded desired diene 1 in 31% overall yield, easily scalable to the 10 g level, Diels-Alder reaction of 1 with maleic anhydride in benzene was known to afford a 50:50 mixture of "normal" (2) and "rearranged" (3) adducts. In THF as solvent, 2 has been reproducibly obtained in over 90% yield as a 98:2 mixture with 3. H-1 NMR spectroscopy (NOESY, ASIS) and molecular modeling (MM2, AM1, ab initio) have been used jointly to determine the conformation of 2 and 3, All are consistent with a folded structure of "rearranged" 3. On the other hand, only RHF/6-31G* and B3LYP/6-31G* ab initio models were in agreement with NMR spectroscopy for an extended conformation of adduct 2. In this case, neither MM2 nor AM1 models gave results consistent with NMR: discrepancies as high as 30 degrees were noted for some dihedrals between these models and ab initio ones.

  DOI：

  10.1021/jo991173d

文献信息

• Regioselective Synthesis and Diels−Alder Reaction of 3,4-Dimethylpenta-1,3-diene. Conformational Study of Bicyclic Adducts Structures by ¹H NMR (NOESY, ASIS) and Molecular Modeling (MM2, AM1, RHF, and DFT)
  作者：Pascal Gosselin、Christophe Bourdy、Stéphane Mille、Angélique Perrotin

  DOI：10.1021/jo991173d

  日期：1999.12.1

  A three-step, regioselective synthesis of 3,4-dimethylpenta-1,3-diene 1 has been developed. The condensation of acetone diethylacetal with ethyl propenyl ether yielded, after hydrolysis of the resulting triethoxy adduct 10, 2,3-dimethyl-2-butenal 7. Wittig reaction of 7 with methylenetriphenylphosphorane afforded desired diene 1 in 31% overall yield, easily scalable to the 10 g level, Diels-Alder reaction of 1 with maleic anhydride in benzene was known to afford a 50:50 mixture of "normal" (2) and "rearranged" (3) adducts. In THF as solvent, 2 has been reproducibly obtained in over 90% yield as a 98:2 mixture with 3. H-1 NMR spectroscopy (NOESY, ASIS) and molecular modeling (MM2, AM1, ab initio) have been used jointly to determine the conformation of 2 and 3, All are consistent with a folded structure of "rearranged" 3. On the other hand, only RHF/6-31G* and B3LYP/6-31G* ab initio models were in agreement with NMR spectroscopy for an extended conformation of adduct 2. In this case, neither MM2 nor AM1 models gave results consistent with NMR: discrepancies as high as 30 degrees were noted for some dihedrals between these models and ab initio ones.