bis(2,6-dimethoxyphenyl)amine | 372194-97-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(2,6-dimethoxyphenyl)amine
• 英文别名: N-(2,6-dimethoxyphenyl)-2,6-dimethoxyaniline
• CAS: 372194-97-3
• 化学式: C₁₆H₁₉NO₄
• 分子量: 289.331
• InChiKey: JBBXEBORVCYOLP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  49
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  bis(2,6-dimethoxyphenyl)amine 在 三氯化铝 作用下， 以 邻二氯苯 、 甲苯 为溶剂， 反应 24.0h， 生成 tris(2,6-dihydroxyphenyl)amine
  参考文献：
  名称：

  Bonding along a Linear B···N···B Triad

  摘要：

  The synthesis of tris(2,6-dihydroxyphenyl)amine diborate, 4, is reported. This compound contains a linear (BNB)-N-...-B-.... array for which a symmetrical three-center two-electron (3c-2e) bond is possible. The X-ray crystal structure of 4 shows that 3c-2e bonding is, in fact, absent. Rather, the B-N-B array of 4 is unsymmetrical, having a 2c-2e B-N dative bond with the remaining boron pyramidalized outward and bonded to the oxygen of THF, i.e., 4(.)THF. In THF solution, 4 displays temperature-dependent C-13 NMR spectra from which a DeltaG(double dagger) of 11.6 kcal/mol at 262 K may be calculated. The dynamic process observed in solution corresponds to a bond-switching equilibrium in which the B-N bond oscillates between the two borons ("bell clapper"). Ab initio calculations indicate that the most likely pathway for the bond switch does not involve a 3c-2e (BNB)-N-...-B-... bond, but rather occurs by nucleophilic attack of THF on the datively bonded boron to generate 4(.)(THF)(2), lacking any B-N interactions, followed by loss of one THF. The B-N-B system of 4 sans the perturbing effect of solvent was also investigated computationally. The form of 4 containing a 3c-2e bond is found to be a transition state in the solvent-free bond-switch reaction of 4, lying 2.66 kcal/mol above 4. The stability of three-center bonds to in-line distortion (viz., (XYX)-Y-...-X-...-->X-(YX)-X-.........) is discussed from the point of view of the second-order Jahn-Teller effect.

  DOI：

  10.1021/jo040199o
• 作为产物：
  描述：

  2-碘-1,3-二甲氧基苯 、 2,6-二甲氧基苯胺 在 18-冠醚-6 、 铜 、 potassium carbonate 作用下， 以 邻二氯苯 为溶剂， 反应 24.0h， 生成 bis(2,6-dimethoxyphenyl)amine
  参考文献：
  名称：

  Bonding along a Linear B···N···B Triad

  摘要：

  The synthesis of tris(2,6-dihydroxyphenyl)amine diborate, 4, is reported. This compound contains a linear (BNB)-N-...-B-.... array for which a symmetrical three-center two-electron (3c-2e) bond is possible. The X-ray crystal structure of 4 shows that 3c-2e bonding is, in fact, absent. Rather, the B-N-B array of 4 is unsymmetrical, having a 2c-2e B-N dative bond with the remaining boron pyramidalized outward and bonded to the oxygen of THF, i.e., 4(.)THF. In THF solution, 4 displays temperature-dependent C-13 NMR spectra from which a DeltaG(double dagger) of 11.6 kcal/mol at 262 K may be calculated. The dynamic process observed in solution corresponds to a bond-switching equilibrium in which the B-N bond oscillates between the two borons ("bell clapper"). Ab initio calculations indicate that the most likely pathway for the bond switch does not involve a 3c-2e (BNB)-N-...-B-... bond, but rather occurs by nucleophilic attack of THF on the datively bonded boron to generate 4(.)(THF)(2), lacking any B-N interactions, followed by loss of one THF. The B-N-B system of 4 sans the perturbing effect of solvent was also investigated computationally. The form of 4 containing a 3c-2e bond is found to be a transition state in the solvent-free bond-switch reaction of 4, lying 2.66 kcal/mol above 4. The stability of three-center bonds to in-line distortion (viz., (XYX)-Y-...-X-...-->X-(YX)-X-.........) is discussed from the point of view of the second-order Jahn-Teller effect.

  DOI：

  10.1021/jo040199o

文献信息

• A New Route To Hindered Tertiary Amines
  作者：Minmin Yang、Xing Wang、Hui Li、Peter Livant

  DOI：10.1021/jo010583a

  日期：2001.10.1

  dimethyl diazomalonate has been found to insert into the N-H bond of sterically hindered secondary aliphatic amines to afford hindered tertiary aliphatic amines in quite satisfactory yields. For example dimethyl 2-(dicyclohexylamino)propanedioate was formed in 85% yield from dicyclohexylamine, and the severely hindered dimethyl 2-(2,2,6,6-tetramethyl-1-piperidinyl)propanedioate was formed in 38% yield

  已发现衍生自重氮丙二酸二甲酯的Rh（2）（OAc）（4）稳定的类胡萝卜素可插入空间位阻仲脂肪族胺的NH键中，从而以令人满意的产率提供受阻叔脂肪族胺。例如，由二环己基胺以85％的收率形成2-（二环己基氨基）丙二酸二甲酯，而由2形成38％收率的严重受阻的2-（2,2,6,6-四甲基-1-哌啶基）丙二酸二甲酯。 2,6,6-四甲基哌啶。发现Rh（2）（OAc）（4）-重氮丙二酸二甲酯反应也可用于芳基烷基胺和二芳基胺。在这些情况下，检测到由类胡萝卜素正式插入芳族CH键而产生的少量产物。邻位取代导致CH插入产物的产率增加。其他重氮化合物，即。
• Bonding along a Linear B···N···B Triad
  作者：Peter D. Livant、D. John D. Northcott、Yiping Shen、Thomas R. Webb

  DOI：10.1021/jo040199o

  日期：2004.10.1

  The synthesis of tris(2,6-dihydroxyphenyl)amine diborate, 4, is reported. This compound contains a linear (BNB)-N-...-B-.... array for which a symmetrical three-center two-electron (3c-2e) bond is possible. The X-ray crystal structure of 4 shows that 3c-2e bonding is, in fact, absent. Rather, the B-N-B array of 4 is unsymmetrical, having a 2c-2e B-N dative bond with the remaining boron pyramidalized outward and bonded to the oxygen of THF, i.e., 4(.)THF. In THF solution, 4 displays temperature-dependent C-13 NMR spectra from which a DeltaG(double dagger) of 11.6 kcal/mol at 262 K may be calculated. The dynamic process observed in solution corresponds to a bond-switching equilibrium in which the B-N bond oscillates between the two borons ("bell clapper"). Ab initio calculations indicate that the most likely pathway for the bond switch does not involve a 3c-2e (BNB)-N-...-B-... bond, but rather occurs by nucleophilic attack of THF on the datively bonded boron to generate 4(.)(THF)(2), lacking any B-N interactions, followed by loss of one THF. The B-N-B system of 4 sans the perturbing effect of solvent was also investigated computationally. The form of 4 containing a 3c-2e bond is found to be a transition state in the solvent-free bond-switch reaction of 4, lying 2.66 kcal/mol above 4. The stability of three-center bonds to in-line distortion (viz., (XYX)-Y-...-X-...-->X-(YX)-X-.........) is discussed from the point of view of the second-order Jahn-Teller effect.