1-adamantyl tert-butyl ketone imine | 100083-94-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-adamantyl tert-butyl ketone imine
• 英文别名: 1-(1-adamantyl)-2,2-dimethyl-1-propanimine；1-(1-Adamantyl)-2,2-dimethylpropan-1-imine
• CAS: 100083-94-1；100083-95-2
• 化学式: C₁₅H₂₅N
• 分子量: 219.37
• InChiKey: LCXLKUZISORNNX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  23.8
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-adamantyl tert-butyl ketone imine 在 盐酸羟胺 、 sodium acetate 作用下， 以 乙醇 为溶剂， 生成 1-adamantyl tert-butyl ketoxime
  参考文献：
  名称：

  Structural Effects on Stabilities of Iminoxy Radicals

  摘要：

  The equilibrium acidities for the O-H bonds of seven ketoximes in dimethyl sulfoxide and the oxidation potentials of their conjugate anions have been measured. The combination of the pK(HA) and E(OX)(A(-)) values using eq 1 has allowed estimates to be made of the ethalpies for homolytic cleavage of the O-H bonds (BDEs). The BDEs estimated for the O-H bonds in t-Bu(2)C=NOK-and t-Bu(1-Ad)C=NOH by our simple method using eq 1, BDE = 1.37pK(HA) + 23.1E(OX)(A(-)) + 73.3, were found to be within experimental error of those obtained by a direct calorimetric method. The BDEs of the O-H bonds become progressively weaker as the size of the alkyl groups R and R' in the RR'C=NOH oximes become larger. The BDEs cover a range of 14 kcal/mol from that of 95.8 kcal/mol for the BDE of the O-H bond in Me(2)C=NOH to 81.7 kcal/mol for the BDE of the O-H bond in t-Bu(Ad)C=NOH. The effects are rationalized in terms of increasing ground state energies and decreasing BDEs with increasing size of the alkyl groups, as the result of progressively larger relief of steric strain as the O-H bond is broken homolytically. These and other effects of structural changes in oximes on BDEs of their O-H bonds are consistent with delocalization of the odd electron in a p orbital on oxygen to carbon. The X-ray crystal structure of di-tert-butyl ketoxime has been measured and compared with that of dimethyl ketoxime.

  DOI：

  10.1021/ja00122a016
• 作为产物：
  描述：

  1-氰基金刚烷 、 叔丁基锂 以 乙醚 、 正戊烷 为溶剂， 反应 3.0h， 生成 1-adamantyl tert-butyl ketone imine
  参考文献：
  名称：

  Structural Effects on Stabilities of Iminoxy Radicals

  摘要：

  The equilibrium acidities for the O-H bonds of seven ketoximes in dimethyl sulfoxide and the oxidation potentials of their conjugate anions have been measured. The combination of the pK(HA) and E(OX)(A(-)) values using eq 1 has allowed estimates to be made of the ethalpies for homolytic cleavage of the O-H bonds (BDEs). The BDEs estimated for the O-H bonds in t-Bu(2)C=NOK-and t-Bu(1-Ad)C=NOH by our simple method using eq 1, BDE = 1.37pK(HA) + 23.1E(OX)(A(-)) + 73.3, were found to be within experimental error of those obtained by a direct calorimetric method. The BDEs of the O-H bonds become progressively weaker as the size of the alkyl groups R and R' in the RR'C=NOH oximes become larger. The BDEs cover a range of 14 kcal/mol from that of 95.8 kcal/mol for the BDE of the O-H bond in Me(2)C=NOH to 81.7 kcal/mol for the BDE of the O-H bond in t-Bu(Ad)C=NOH. The effects are rationalized in terms of increasing ground state energies and decreasing BDEs with increasing size of the alkyl groups, as the result of progressively larger relief of steric strain as the O-H bond is broken homolytically. These and other effects of structural changes in oximes on BDEs of their O-H bonds are consistent with delocalization of the odd electron in a p orbital on oxygen to carbon. The X-ray crystal structure of di-tert-butyl ketoxime has been measured and compared with that of dimethyl ketoxime.

  DOI：

  10.1021/ja00122a016

文献信息

• Thermal decomposition of O-benzyl ketoximes; role of reverse radical disproportionation
  作者：Jessie A. Blake、Keith U. Ingold、Shuqiong Lin、Peter Mulder、Derek A. Pratt、Brad Sheeller、John C. Walton

  DOI：10.1039/b313491a

  日期：——

  9,10-dihydrophenanthrene and 9,10-dihydroanthracene than in tetralin. These results indicated that a reverse radical disproportionation reaction in which a hydrogen atom was transferred from the solvent to the oxime ether, followed by [small beta]-scission of the resultant aminoalkyl radical, must be important in the latter two solvents. Benzaldehyde was found to be an additional product from thermolyses

  已在三个氢供体中研究了七个二烷基，两个烷基芳基和两个二芳基O-苄基酮肟醚R（1）R（2）C [双键，长度为m-破折号NOCH（2）Ph）的热解溶剂：四氢萘，9,10-二氢菲和9,10-二氢蒽。所有肟醚均给出了OC键（即，R（1）R（2）C [双键，长度为m-NOH和PhCH（3））均被裂解的预期产物，以及NO键（即，R（1）R（2）C [双键，长度为m-NH和PhCH（2）OH）。这些产物的产率取决于所使用的溶剂，并且在9，10-二氢菲和9，10-二氢蒽中的O-苄基肟醚的分解速率大于在四氢化萘中。这些结果表明，其中有一个氢原子从溶剂转移到肟醚上的逆自由基歧化反应，然后对所得的氨基烷基进行小β-断裂，在后两种溶剂中必须很重要。发现苯甲醛是在四氢化萘中进行热解的另一产物。该证据和其他证据表明，涉及一些苄基氢原子的另一种诱导的分解模式涉及提取苄基氢原子，然后对所得的苄基进行小β-断裂。通过比较不能产生烯胺互变异构体的双环[3
• Flamm-ter Meer, Manuela A.; Beckhaus, Hans-Dieter; Peters, Karl, Chemische Berichte, 1986, vol. 119, # 5, p. 1492 - 1510
  作者：Flamm-ter Meer, Manuela A.、Beckhaus, Hans-Dieter、Peters, Karl、von Schnering, Hans-Georg、Fritz, Hans、Ruechardt, Christoph

  DOI：——

  日期：——
• FLAMM-TER, MEER, M. A.;BECKHAUS, H. -D.;PETERS, K.;VON, SCHNERING, H. G.;+, CHEM. BER., 1986, 119, N 5, 1492-1510
  作者：FLAMM-TER, MEER, M. A.、BECKHAUS, H. -D.、PETERS, K.、VON, SCHNERING, H. G.、+

  DOI：——

  日期：——