(Methylenedicyclohexane-1,4-diyl)bis(2-methoxyethyl carbamate)

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (Methylenedicyclohexane-1,4-diyl)bis(2-methoxyethyl carbamate)
• 英文别名: 2-methoxyethyl N-[4-[[4-(2-methoxyethoxycarbonylamino)cyclohexyl]methyl]cyclohexyl]carbamate
• 化学式: C₂₁H₃₈N₂O₆
• 分子量: 414.543
• InChiKey: QFNRVQAZUAWYAQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  29
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  95.1
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2-氯乙基甲基醚 、 二氧化碳 、 4,4'-二氨基二环己基甲烷 在 cyclohexyl tetraethyl guanidine 作用下， 生成 (Methylenedicyclohexane-1,4-diyl)bis(2-methoxyethyl carbamate)
  参考文献：
  名称：

  Carbon Dioxide as a Phosgene Replacement: Synthesis and Mechanistic Studies of Urethanes from Amines, CO2, and Alkyl Chlorides

  摘要：

  Several carbamate esters were synthesized from amines, carbon dioxide, and alkyl chlorides. The effect of added base on the yield and selectivity of carbamate ester formation was found to be highly important with the use of sterically hindered guanidine bases giving the best results. Relative rate studies were carried out giving the following order of reactivity between carbamate anions in acetonitrile with benzyl chloride giving carbamate esters: Et(2)NCO(2)(-) = Bu(2)NCO(2)(-) > t-BuNHCO(2)(-) CyNHCO(2)(-) = s-BuNHCO(2)(-) > PhNHCO(2)(-) > CyCH(2)NHCO(2) = n-octylNHCO(2)(-) = n-BuNHCO(2)(-). Rate studies were carried out with the diethyl, s-butyl, phenyl, and n-butyl carbamates and activation parameters were determined to be Et(2)NCO(2)(-), Delta H-double dagger = 11.8 kcal/mol, Delta S-double dagger = -33 eu; s-BuNHCO(2)(-), Delta H-double dagger = 12.8 kcal/mol, Delta S-double dagger = -33 eu; PhNHCO(2)(-), Delta H-double dagger = 14.3 kcal/mol, Delta S-double dagger = -28 eu; n-BuNHCO(2)(-), Delta H-double dagger: = 23.4 kcal/mol, Delta S-double dagger = -3 eu. The unusual results obtained from the use of n-BuNHCO(2)(-) prompted further studies which showed that the rate of reaction was inversely dependent on carbon dioxide pressure (20 psig CO2, k = 4.84 x 10(-4) M(-1) s(-1); 120 psig CO2, k = 1.83 x 10(-4) M(-1) s(-1)). Nitrogen NMR spectroscopy indicated, via a labeling study with N-15 amines and C-13 enriched carbon dioxide, the formation of a doubly inserted product from the addition of two carbon dioxides to ethylamine in acetonitrile.

  DOI：

  10.1021/jo00114a035

文献信息

• Carbon Dioxide as a Phosgene Replacement: Synthesis and Mechanistic Studies of Urethanes from Amines, CO2, and Alkyl Chlorides
  作者：William McGhee、Dennis Riley、Kevin Christ、Yi Pan、Barry Parnas

  DOI：10.1021/jo00114a035

  日期：1995.5

  Several carbamate esters were synthesized from amines, carbon dioxide, and alkyl chlorides. The effect of added base on the yield and selectivity of carbamate ester formation was found to be highly important with the use of sterically hindered guanidine bases giving the best results. Relative rate studies were carried out giving the following order of reactivity between carbamate anions in acetonitrile with benzyl chloride giving carbamate esters: Et(2)NCO(2)(-) = Bu(2)NCO(2)(-) > t-BuNHCO(2)(-) CyNHCO(2)(-) = s-BuNHCO(2)(-) > PhNHCO(2)(-) > CyCH(2)NHCO(2) = n-octylNHCO(2)(-) = n-BuNHCO(2)(-). Rate studies were carried out with the diethyl, s-butyl, phenyl, and n-butyl carbamates and activation parameters were determined to be Et(2)NCO(2)(-), Delta H-double dagger = 11.8 kcal/mol, Delta S-double dagger = -33 eu; s-BuNHCO(2)(-), Delta H-double dagger = 12.8 kcal/mol, Delta S-double dagger = -33 eu; PhNHCO(2)(-), Delta H-double dagger = 14.3 kcal/mol, Delta S-double dagger = -28 eu; n-BuNHCO(2)(-), Delta H-double dagger: = 23.4 kcal/mol, Delta S-double dagger = -3 eu. The unusual results obtained from the use of n-BuNHCO(2)(-) prompted further studies which showed that the rate of reaction was inversely dependent on carbon dioxide pressure (20 psig CO2, k = 4.84 x 10(-4) M(-1) s(-1); 120 psig CO2, k = 1.83 x 10(-4) M(-1) s(-1)). Nitrogen NMR spectroscopy indicated, via a labeling study with N-15 amines and C-13 enriched carbon dioxide, the formation of a doubly inserted product from the addition of two carbon dioxides to ethylamine in acetonitrile.