1,1,3-三乙氧基-2,3-二甲基丁烷 | 105901-36-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1,1,3-三乙氧基-2,3-二甲基丁烷
• 英文名称: 1,1,3-triethoxy-2,3-dimethylbutane
• 英文别名: 1,1,3-triethoxy-2,3-dimethyl-butane；3-ethoxy-2,3-dimethyl-butyraldehyde diethyl acetal；3-Aethoxy-2,3-dimethyl-butyraldehyd-diaethylacetal；1,1,3-Triaethoxy-2,3-dimethyl-butan；(+/-)-1,1,3-Triaethoxy-2,3-dimethyl-butan
• CAS: 105901-36-8
• 化学式: C₁₂H₂₆O₃
• 分子量: 218.337
• InChiKey: IXFKUMHTJBFCGN-UHFFFAOYSA-N

物化性质

• 沸点：
  88-89 °C(Press: 10 Torr)
• 密度：
  0.8908 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,1,3-三乙氧基-2,3-二甲基丁烷 在 甲酸 、 potassium tert-butylate 、 水 、 sodium formate 作用下， 以 乙醚 为溶剂， 反应 13.0h， 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：

  (E)-1-ethoxyprop-1-ene 、 2,2-二乙氧基丙烷 在 三氟化硼乙醚 作用下， 以52%的产率得到1,1,3-三乙氧基-2,3-二甲基丁烷
  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

• Nasarow et al., Zhurnal Obshchei Khimii, 1959, vol. 29, p. 3683,3686;engl.Ausg.S.3641,3644
  作者：Nasarow et al.

  DOI：——

  日期：——
• Normant,H.; Martin,G., Bulletin de la Societe Chimique de France, 1963, p. 1646 - 1650
  作者：Normant,H.、Martin,G.

  DOI：——

  日期：——
• 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.