N-Ethyl-o-deuterobenzamide | 87768-57-8

• 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: N-Ethyl-o-deuterobenzamide
• 英文别名: 2-deuterio-N-ethylbenzamide
• CAS: 87768-57-8
• 化学式: C₉H₁₁NO
• 分子量: 150.184
• InChiKey: SDIDYFBTIZOPLA-RAMDWTOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.44
• 重原子数：
  11.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  29.1
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  N-ethyl-2-iodobenzamide 在 正丁基锂 、 重水 作用下， 以 四氢呋喃 、 吡啶 、 二氯甲烷 为溶剂， 反应 24.5h， 生成 N-Ethyl-o-deuterobenzamide
  参考文献：
  名称：

  酸性氘到卤素-锂交换位点的正式分子内转移是否表明锂-卤素交换比失去酸性氘更快？支持替代机制的证据

  摘要：

  酸性氘正式分子内转移到卤素-锂交换位点的反应可以解释为表明最初的卤素-锂交换发生得比酸性氘的损失更快。然而，对 N-deuterio-N-烷基-o、-m-和-p-卤代苯甲酰亚胺的卤素-金属-氘损失之间的竞争的研究与该机制不一致。他们提出了一种替代方案，其中酸性氘的初始损失随后是卤素-锂交换以得到二锂化的中间体。然后通过二锂化物质与未反应的 N-氘化酰胺发生分子间反应，将氘转移到卤素-锂交换位点。卤素-锂交换比反应物的完全混合更快，并且可以在最初形成的去质子化络合物中或在有机锂试剂的瞬时高局部浓度中发生。提供了两种可能性的证据。已经重新研究了文献中卤素-锂交换似乎比酸性氢的转移更快的两个反应，并发现它们可以用相似的序列来解释。

  DOI：

  10.1021/ja00219a031

文献信息

• A comparison of secondary and tertiary amides as directors of ortho and adjacent benzylic lithiation and of asymmetric induction in ortho lithiated benzamides
  作者：Peter Beak、Anthony Tse、Joel Haawkins、Chin-Wen Chen、Sander Mills

  DOI：10.1016/s0040-4020(01)91916-7

  日期：1983.1

  Comparisons are made between the influence of secondary and tertiary amides on ortho and adjacent benzylic metallations of benzamides. In the intramolecular competition offered by N,N-diethyl-N-ethylterephthalamide (1) the tertiary amide is the more effective director of ortho lithiation, while the secondary amide is better in the intermolecular competitions offered by the pairs N-ethyl-(9): N,N-diethylbenzamide(10)

  比较仲酰胺和叔酰胺对苯甲酰胺的邻位和邻位苄基金属化的影响。在N，N-二乙基-N-乙基对苯二甲酰胺（1）提供的分子内竞争中，叔酰胺是邻位锂化的更有效导向器，而仲酰胺在N-乙基-（9 ）：N，N-二乙基苯甲酰胺（10）和N-异丙基-（11）：N，N-二异丙基苯甲酰胺（12）。在2-异丙基苯甲酰胺25和26中，仲酰胺和叔酰胺都可以直接金属化到酰胺上; 然而，在仲2-乙基和2-甲基苯甲酰胺中发现苄基金属化21和22以及叔2-乙基苯甲酰胺19。注意到19的抗-N-亚甲基的磁性不等价。内硫基（S）-O-甲基-N-苯甲酰亮氨醇（34）与1-萘甲醛-1-d的反应在内酯化后得到3-（1-萘-1-d）-邻苯二甲酸酯与10％对映异构体过量的。通过在环化之前分离非对映异构体，可以以高对映体纯度获得邻苯二甲酰亚胺。对照实验确定观察到的不对称诱导归因于非对映异构过渡态。相应的叔苯甲酰胺在诱导不对称方面无效。为这些观察提供了结构和机械原理。
• Relative rates of deprotonation and of bromine-lithium exchange by organolithium reagents: interpretation of some deceptive results
  作者：Peter Beak、Chin-Wen Chen

  DOI：10.1016/s0040-4039(01)80830-3

  日期：1985.1

  Two reactions in which bromine-lithium exchange might be considered to be faster than deprotonation of an acidic deuterium on the basis of carbon deuterium labelling in the products, are suggested to involve initial dedeuteration followed by rapid bromine-lithium exchange and subsequent deuteration by a second molecule of deuterio acid.

  根据产品中的碳氘标记，建议考虑两个反应，其中溴-锂交换比酸性氘的去质子化更快，建议先进行氘化，然后快速进行溴-锂交换，再进行第二次氘化。氘酸分子。
• Selectivities in reactions of organolithium reagents with aryl bromides which bear proton-donating groups
  作者：Peter Beak、Timothy J. Musick、Chao Liu、Thomas Cooper、Donald J. Gallagher

  DOI：10.1021/jo00078a007

  日期：1993.12

  Studies of substrates which offer an acidic hydrogen and an aryl bromide for reaction with an organolithium reagent have been carried out with a series of benzene bromo amides and bromo anilides as well as selected benzene bromo carboxylic acids, bromoanilines, and bromobenzylamines. A representative example is the reaction of N-ethyl-N-deutero-o-bromobenzamide (6-d) with 1-lithio-3-phenylpropane to give N-ethyl-o-deuterobenzamide (46%, 94%-d) (7-d), N-ethyl-o-bromobenzamide (6)(49%), 3-deutero-1-phenylpropane(51%, 92%-d), and 1-bromo-3-phenylpropane (48%). Product formation in this and related cases is explained by the operation of a two step sequence in which an initial deprotonation is followed by a bromine-lithium exchange which is accelerated with respect to mixing. Such a sequence is consistent with the results of deuterium labeling and with changes in product ratios on different mixing and with differently aggregated organolithium reagents. Support is provided for the operation of two pathways for the expedited bromine-lithium exchange reactions. In one pathway a high local concentration of the organolithium reagent promotes rapid reaction and in the second the exchange reaction occurs within an initially formed complex. The selectivity for removal of a bromine ortho to a lithiated carboxamide is found to be 5-8 with n-butyllithium, and satisfactory synthetic ortho selectivity is obtained for N-ethyl-2,5-dibromobenzamide with phenyllithium.
• Beak Peter, Musick Timothy J., Liu Chao, Cooper Thomas, Gallagher Donald +, J. URG. Chem, 58 (1993) N 26, S 7330-7335
  作者：Beak Peter, Musick Timothy J., Liu Chao, Cooper Thomas, Gallagher Donald +

  DOI：——

  日期：——
• BEAK, P.;TSE, A.;HAWKINS, J.;CHEN, CHIN-WEN;MILLS, S., TETRAHEDRON, 1983, 39, N 12, 1983-1989
  作者：BEAK, P.、TSE, A.、HAWKINS, J.、CHEN, CHIN-WEN、MILLS, S.

  DOI：——

  日期：——