2,6-dichloro-N,N-diethylbenzamide | 10345-78-5

• 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: 2,6-dichloro-N,N-diethylbenzamide
• 英文别名: N,N-diethyl-2,6-dichlorobenzamide；3-deutero-N,N-diethyl-2,6-dichlorobenzamide；2,6-Dichlorbenzoesaeure-diethylamid；2.6-Dichlor-N.N-aethylbenzamid；Benzamide, 2,6-dichloro-N,N-diethyl-
• CAS: 10345-78-5
• 化学式: C₁₁H₁₃Cl₂NO
• 分子量: 246.136
• InChiKey: AAVLZXHEADHXKR-UHFFFAOYSA-N

物化性质

• 沸点：
  370.1±32.0 °C(Predicted)
• 密度：
  1.220±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,6-dichloro-N,N-diethylbenzamide 在 Schwartz's reagent 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 以17%的产率得到2,6-二氯苯甲醛
  参考文献：
  名称：

  Mild and Selective Hydrozirconation of Amides to Aldehydes Using Cp₂Zr(H)Cl:  Scope and Mechanistic Insight

  摘要：

  An investigation of the use of Cp2Zr(H)Cl (Schwartz's reagent) to reduce a variety of amides to the corresponding aldehydes under very mild reaction conditions and in high yields is reported. A range of tertiary amides, including Weinreb's amides, can be converted directly to the corresponding aldehydes with remarkable chemoselectivity. Primary and secondary amides proved to be viable substrates for reduction as well, although the yields were somewhat diminished as compared to the corresponding tertiary amides. Results from NMR experiments suggested the presence of a stable, 18-electron zirconacycle intermediate that presumably affords the aldehyde upon water or silica gel workup. A series of competition experiments revealed a preference of the reagent for substrates in which the lone pair of the nitrogen is electron releasing and thus more delocalized across the amide bond by resonance. This trend accounts for the observed excellent selectivity for tertiary amides versus esters. Experiments regarding the solvent dependence of the reaction suggested a kinetic profile similar to that postulated for the hydrozirconation of alkenes and alkynes. Addition of p-anisidine to the reaction intermediate resulted in the formation of the corresponding imine mimicking the addition of water that forms the aldehyde.

  DOI：

  10.1021/ja066362+

文献信息

• The tertiary amide as an effective director of ortho lithiation
  作者：Peter Beak、Roger A. Brown

  DOI：10.1021/jo00340a008

  日期：1982.1
• Aminoborohydrides as reducing agents. 1. Sodium (dimethylamino)- and (tert-butylamino)borohydrides as selective reducing agents
  作者：Robert O. Hutchins、Keith Learn、Farag El-Telbany、Yurly P. Stercho

  DOI：10.1021/jo00187a028

  日期：1984.6
• BEAK, P.;BROWN, R. A., J. ORG. CHEM., 1982, 47, N 1, 34-36
  作者：BEAK, P.、BROWN, R. A.

  DOI：——

  日期：——
• HUTCHINS, R. O.;LEARN, K.;EL-TELBANY, F.;STERCHO, Y. P., J. ORG. CHEM., 1984, 49, N 13, 2438-2443
  作者：HUTCHINS, R. O.、LEARN, K.、EL-TELBANY, F.、STERCHO, Y. P.

  DOI：——

  日期：——
• Mild and Selective Hydrozirconation of Amides to Aldehydes Using Cp₂Zr(H)Cl:  Scope and Mechanistic Insight
  作者：Jared T. Spletstoser、Jonathan M. White、Ashok Rao Tunoori、Gunda I. Georg

  DOI：10.1021/ja066362+

  日期：2007.3.1

  An investigation of the use of Cp2Zr(H)Cl (Schwartz's reagent) to reduce a variety of amides to the corresponding aldehydes under very mild reaction conditions and in high yields is reported. A range of tertiary amides, including Weinreb's amides, can be converted directly to the corresponding aldehydes with remarkable chemoselectivity. Primary and secondary amides proved to be viable substrates for reduction as well, although the yields were somewhat diminished as compared to the corresponding tertiary amides. Results from NMR experiments suggested the presence of a stable, 18-electron zirconacycle intermediate that presumably affords the aldehyde upon water or silica gel workup. A series of competition experiments revealed a preference of the reagent for substrates in which the lone pair of the nitrogen is electron releasing and thus more delocalized across the amide bond by resonance. This trend accounts for the observed excellent selectivity for tertiary amides versus esters. Experiments regarding the solvent dependence of the reaction suggested a kinetic profile similar to that postulated for the hydrozirconation of alkenes and alkynes. Addition of p-anisidine to the reaction intermediate resulted in the formation of the corresponding imine mimicking the addition of water that forms the aldehyde.