tert-butyl-aminyl | 41084-93-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: tert-butyl-aminyl
• CAS: 41084-93-9
• 化学式: C₄H₁₀N
• 分子量: 72.1301
• InChiKey: CQGVXQATBDGYNF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  1
• 氢给体数：
  1
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  tert-butyl-aminyl 在 氨 作用下， 生成 3-(4-nitrophenyl)-3H-diazirine
  参考文献：
  名称：

  NOVEL PATHWAY FOR THE SYNTHESIS OF DIAZIRINES, THAT MAY OR MAY NOT BE ENRICHED IN NITROGEN-15

  摘要：

  本发明涉及一种新型的合成重氮环化合物的方法，可以从氨基酸或亚胺中合成，可能富集于氮-15，采用一锅法合成方法，包括将起始氨基酸或亚胺与氨反应，可能富集于氮-15，并与高价碘氧化剂反应。本发明还涉及一种合成富集于氮-15的氨的方法。本发明还涉及某些可能通过所述合成方法获得的公式（I）的重氮环化合物，并且还涉及公式（I'）的15N2-重氮环化合物。所述的重氮环化合物可用于光亲和标记。15N2-重氮环化合物也可用于超极化，特别是在医学成像领域。

  公开号：

  US20220098155A1
• 作为产物：
  描述：

  叔丁胺 在 二苯甲酮 作用下， 以 乙腈 为溶剂， 生成 tert-butyl-aminyl
  参考文献：
  名称：

  N−H and α(C−H) Bond Dissociation Enthalpies of Aliphatic Amines

  摘要：

  Bond dissociation enthalpies (BIDES) of a large series of aliphatic amines (21) were measured by means of photoacoustic calorimetry. Despite the different structures studied in the primary, secondary, and tertiary amine series, the a(C-H) BIDES were found to be very similar for unconstrained amines with values very close to 91 kcal/mol. alphaC- and N-alkylation or introduction of an hydroxy group only slightly affect the BDEs, a fact in perfect agreement with calculations performed at different CBS levels. This demonstrates the predominance of the two-orbital-three-electron interaction involving the N and alphaC(.) orbitals. On the other hand, the N-H BIDE decreases when going from primary to secondary amines. This result is interpreted in term of a hyperconjugation in sigmaC-C bonds, which leads to a stabilization of the aminyl radical. For cyclized amines, the BIDES depend on the relative geometry of the singly occupied alphaC(.) orbital with respect to that of the N atom, disfavoring the two-orbital-three-electron interaction. However, such structures can exhibit through-bond interaction. For a crowded structure such as triisopropylamine, for which the alphaC(.) orbital is not coplanar with the nitrogen one, the relaxation of a strain energy allows the BIDE to be comparable to flexible structures.

  DOI：

  10.1021/ja0204168

文献信息

• Primary quantum yields of ketyl radicals in photoreduction by amines. Abstraction of hydrogen from nitrogen
  作者：Shai Inbar、Henry Linschitz、Saul G. Cohen

  DOI：10.1021/ja00524a034

  日期：1980.2

  photolysis studies of the primary reaction of benzophenone triplet with aliphatic amines in benzene solution are reported. Quantum yield of formation of benzophenone ketyl radical was 0.9 - 1.0. Quantum yields for reduction of ketone also were determined for various amines, and the effects of tert-butyl alcohol on radical formation was investigated. Data indicated that H is not abstracted from -CH/sub

  报告了二苯甲酮三联体与脂肪胺在苯溶液中的主要反应的激光闪光光解研究结果。二苯甲酮羰基自由基形成的量子产率为0.9-1.0。还测定了各种胺的酮还原的量子产率，并研究了叔丁醇对自由基形成的影响。数据表明 H 不是从 -CH/sub 3/ 中提取的，而是从 -NH/sub 2/ 中有效提取的。使用叔胺和仲胺观察到的非常高的量子产率被认为暗示了激基复合物的形成，但伯胺的较低量子产率有条件地归因于较高的电离电位。(BLM)
• Radiolytic reductions and oxidations in dimethyl sulfoxide solutions: solvent effects on reactivity of halogen atom complexes
  作者：M. Kumar、P. Neta

  DOI：10.1021/j100187a032

  日期：1992.4

  Radiolysis of dimethyl sulfoxide (DMSO) solutions containing various additives was used to achieve clean one-electron reduction of oxidation of solutes. Pulse radiolysis of benzoquinone in DMSO solutions containing acetone and triethylamine permitted conversion of all primary radicals into reducing species. The total yield of reduction in the gamma-radiolysis of methyl viologen solutions was found to be 0.37-mu-mol/J. In the pulse radiolysis of TMPD and triphenylamine in aerated DMSO containing LiCl and/or CCl4, all the primary radicals were converted into oxidizing species and gave a maximum yield of 0.39-mu-mol/J. In the latter systems, oxidation was partly by halogen atom complexes. The reactivity of complexes of DMSO (DMSO.Cl, DMSO.Br) and of halide ions (Br2.-,I2.-) was examined for several organic compounds. DMSO.Cl oxidizes chlorpromazine, triphenylamine, and zinc porphyrin with rate constants of the order of 10(7)-10(8) M-1 s-1, and the rates increase upon addition of CH2Cl2 as well as upon addition of water and formamide. DMSO.Cl also reacts with olefins by addition of Cl to the double bond; the rate constants increase upon increasing the electron-donating properties of the substituents on the double bond. The rate constants for oxidation of chlorpromazine by Br2.- and I2.- increase by more than 2 orders of magnitude upon changing the solvent from DMSO gradually to water. The change was less with acetonitrile/water mixtures, and the difference is probably due to differences in ion solvation.
• Absolute rate constants for the reactions of tert-butoxyl, tert-butylperoxyl, and benzophenone triplet with amines: the importance of a stereoelectronic effect
  作者：D. Griller、J. A. Howard、P. R. Marriott、J. C. Scaiano

  DOI：10.1021/ja00393a020

  日期：1981.2
• Hydrogen abstraction from amines: formation of aminyl vs. .alpha.-aminoalkyl radicals
  作者：A. S. Nazran、D. Griller

  DOI：10.1021/ja00345a051

  日期：1983.4
• N−H and α(C−H) Bond Dissociation Enthalpies of Aliphatic Amines
  作者：Jacques Lalevée、Xavier Allonas、Jean-Pierre Fouassier

  DOI：10.1021/ja0204168

  日期：2002.8.1

  Bond dissociation enthalpies (BIDES) of a large series of aliphatic amines (21) were measured by means of photoacoustic calorimetry. Despite the different structures studied in the primary, secondary, and tertiary amine series, the a(C-H) BIDES were found to be very similar for unconstrained amines with values very close to 91 kcal/mol. alphaC- and N-alkylation or introduction of an hydroxy group only slightly affect the BDEs, a fact in perfect agreement with calculations performed at different CBS levels. This demonstrates the predominance of the two-orbital-three-electron interaction involving the N and alphaC(.) orbitals. On the other hand, the N-H BIDE decreases when going from primary to secondary amines. This result is interpreted in term of a hyperconjugation in sigmaC-C bonds, which leads to a stabilization of the aminyl radical. For cyclized amines, the BIDES depend on the relative geometry of the singly occupied alphaC(.) orbital with respect to that of the N atom, disfavoring the two-orbital-three-electron interaction. However, such structures can exhibit through-bond interaction. For a crowded structure such as triisopropylamine, for which the alphaC(.) orbital is not coplanar with the nitrogen one, the relaxation of a strain energy allows the BIDE to be comparable to flexible structures.