α-deuterio-benzaldehyde (E)-oxime | 14702-03-5

• 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: α-deuterio-benzaldehyde (E)-oxime
• 英文别名: (NE)-N-[deuterio(phenyl)methylidene]hydroxylamine
• CAS: 14702-03-5
• 化学式: C₇H₇NO
• 分子量: 122.131
• InChiKey: VTWKXBJHBHYJBI-KXZQRBKYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  甲烷亚磺酰氯化物 、 α-deuterio-benzaldehyde (E)-oxime 以95%的产率得到
  参考文献：
  名称：

  BANKS M. R.; BROWN C.; HUDSON R. F.; RECORD K. A. F., J. CHEM. SOC. PERKIN TRANS., 1986, PT 2, N 10, 1501-1507

  摘要：

  DOI：
• 作为产物：
  描述：

  苯甲醇-Alpha,Alpha-d2 生成 α-deuterio-benzaldehyde (E)-oxime
  参考文献：
  名称：

  Adams, Gregory W.; Bowie, John H.; Hayes, Roger N., Journal of the Chemical Society. Perkin transactions II, 1989, p. 2159 - 2168

  摘要：

  DOI：

文献信息

• Thermal Isomerization of 7,8-Diazabicyclo[4.2.2]deca-2,4,7,9-tetraeneN-oxide to Benzaldehyde Oxime
  作者：Henrik Olsen

  DOI：10.1002/hlca.19820650625

  日期：1982.9.22

  Thermal transformation of 7,8-diazabicyclo[4.2.2]deca-2,4,7,9-tetraene N-oxide (3) was observed, (Z)-benzaldehyde oxime being the major product, with (E)-benzaldehyde oxime as a minor product. N-Oxide 3 was labeled with deuterium α to the oxidized N-atom. The location of the deuterium label in the thermolysis products fitted one of two reasonable mechanisms.

  观察到7,8-二氮杂双环[4.2.2] deca-2,4,7,9-四烯N-氧化物的热转化（3），（Z）-苯甲醛肟为主要产物，（E）-苯甲醛肟为次要产品。N-氧化物3用氘α标记到氧化的N原子上。氘标记在热解产物中的位置符合两种合理机制之一。
• Elimination Reactions of (<i>E</i>)- and (<i>Z</i>)-Benzaldehyde <i>O</i>-Benzoyloximes. Transition State Differences for the Syn- and Anti-Eliminations Forming Nitriles
  作者：Bong Rae Cho、Hak Suk Chung、Nam Soon Cho

  DOI：10.1021/jo980264s

  日期：1998.7.1

  Elimination reactions of (E)- and (Z)-benzaldehyde O-benzoyloximes 1 and 2 with DBU in MeCN have been investigated kinetically. The reactions are second order and exhibit Substantial Values of Hammett rho and k(H)/k(D) values, and an E2 mechanism is evident. The rate of elimination from 2 is approximately 36000 fold faster than that from 1. For reactions of 1 with DBU in MeCN, k(H)/k(D) = 3.3 +/- 0.2, Hammett rho value of 2.19 +/- 0.05, beta(1g) = -0.49 +/- 0.02, Delta H-double dagger = 10.4 +/- 0.6 kcal/mol, and Delta S-double dagger = -34.3 +/- 2.6 eu have been determined. The corresponding values for 2 are k(H)/k(D) = 7.3 +/- 0.2, rho = 1.21 +/- 0.05, beta(1g) = -0.40 +/- 0.01, Delta H-double dagger = 6.8 +/- 0.5 kcal/mol, and Delta S-double dagger = -25.8 +/- 1.9 eu, respectively. The results indicate that the anti-eliminations from 2 proceed via more symmetrical transition states with smaller degrees of proton transfer and N-alpha-OC(O)Ar bond cleavage, less negative charge development at the beta-carbon, and a greater extent of triple bond formation than that for the syn-elimination.
• Elimination reactions of (E)-O-pivaloylbenzaldoximes
  作者：Bong Rae Cho、Wan Jin Jang、Jong Tae Je、Richard A. Bartsch

  DOI：10.1021/jo00067a022

  日期：1993.7

  Elimination reactions of (E)-O-pivaloylbenzaldoximes promoted by Et3N-MeCN, t-BuOK-t-BuOH, and t-BuOK-DMSO have been studied kinetically. The reactions produce benzonitrile quantitatively. The reactions are second-order and exhibit substantial values of rho,beta, and k(H)/k(D) and an E2 mechanism is evident. The rate of elimination from (E)-O-pivaloylbenzaldoxime increased with base-solvent system variation and gave relative rates of 1, 14.8, and 4.31 X 10(4) for Et3N-MeCN, t-BuOK-t-BuOH, t-BuOK-DMSO, respectively. The k(H)/k(D) value increased, but the Hammett rho value increased and then decreased, with this change in the base-solvent system. These results are compared with the predictions of the More O'Ferrall-Jencks reaction coordinate diagram to assess its scope and limitations in the interpretation of the elimination reactions.
• OLSEN, H., HELV. CHIM. ACTA, 1982, 65, N 6, 1921-1926
  作者：OLSEN, H.

  DOI：——

  日期：——