N-methyl-5,5-diphenyl-4-pentenamine | 151888-93-6

• 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-methyl-5,5-diphenyl-4-pentenamine
• 英文别名: N-methyl-5,5-diphenylpent-4-en-1-amine
• CAS: 151888-93-6
• 化学式: C₁₈H₂₁N
• 分子量: 251.371
• InChiKey: JRGDYRNZAMFZDG-UHFFFAOYSA-N

物化性质

• 沸点：
  396.2±37.0 °C(Predicted)
• 密度：
  0.985±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-methyl-5,5-diphenyl-4-pentenamine 在 dipotassium hydrogenphosphate 、 potassium carbonate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 28.0h， 生成 O-(2,4-dinitrophenyl)-N-(5,5-diphenylpent-4-en-1-yl)-N-methylhydroxylamine
  参考文献：
  名称：

  Ni 催化下氮自由基与有机金属的反应：N-芳基化和氨基官能化级联

  摘要：

  在此，我们报告了一种通过有机基-Ni I物质的基态单电子转移产生氮自由基的策略。根据 N-自由基的亲和性，已经开发了两种类型的工艺。在亲核氨基自由基的情况下，可实现与芳基有机锌、有机硼和有机硅试剂的直接N-芳基化。对于亲电子酰胺基自由基，已经开发了涉及分子内环化，然后与芳基和烷基有机金属反应的级联过程。N-环化-烷基化级联引入了一种新颖的逆向合成断开方法，用于组装取代的内酰胺和吡咯烷，其潜力在四种毒液生物碱的简短全合成中得到了证明。

  DOI：

  10.1002/anie.201900510
• 作为产物：
  描述：

  5-溴戊酸 在 对甲苯磺酸 氯化亚砜 作用下， 生成 N-methyl-5,5-diphenyl-4-pentenamine
  参考文献：
  名称：

  Rate constants for aminyl radical reactions

  摘要：

  Rate constantS for cyclization of the N-methyl-5,5-diphenyl-4-pentenaminyl radical (4) and for reaction of this radical with t-BuSH were determined by direct methods.

  DOI：

  10.1016/s0040-4039(00)73871-8

文献信息

• A Kinetic Scale for Dialkylaminyl Radical Reactions
  作者：Osama M. Musa、John H. Horner、Haifa Shahin、Martin Newcomb

  DOI：10.1021/ja954268f

  日期：1996.4.24

  A kinetic scale for dialkylaminyl radicals was established by measuring unimolecular rate constants for a series of dialkylaminyl radical clocks that spans eight orders of magnitude and using clock reactions to measure the second order rate constants for reactions of several hydrogen atom donors. N-Hydroxypyridine-2-thione derivatives of carbamic acids (so-called PTOC carbamates) were used as radical

  通过测量跨越八个数量级的一系列二烷基胺自由基时钟的单分子速率常数并使用时钟反应测量几个氢原子供体反应的二级速率常数，建立了二烷基胺自由基的动力学标度。氨基甲酸的 N-羟基吡啶-2-硫酮衍生物（所谓的 PTOC 氨基甲酸酯）在直接、激光闪光动力学测量和间接、自由基链动力学研究中用作自由基前体。校准的自由基时钟是 N-methyl-6,6-diphenyl-5-hexenaminyl, N-methyl-trans-5-phenyl-4-pentenaminyl, N-methyl-5,5-diphenyl-4-pentenaminyl, N-methyl -反-2-苯基环丁胺基和N-甲基-反-2-苯基环丙胺基。校准的氢原子供体是 Bu3SnH、t-BuSH、PhSH 和 PhSeH。
• Kinetics of Dialkylaminium Cation Radical Reactions: Radical Clocks, Solvent Effects, Acidity Constants, and Rate Constants for Reactions with Hydrogen Atom Donors
  作者：John H. Horner、Felix N. Martinez、Osama M. Musa、Martin Newcomb、Haifa E. Shahin

  DOI：10.1021/ja00150a012

  日期：1995.11

  Dialkylaminium cation radical kinetics were studied directly by laser flash photolysis methods. Irradiation of N-hydroxypyridine-2-thione carbamates with 355-nm light gave dialkylaminyl radicals that were protonated to produce dialkylaminium cation radicals. Fragmentation of the N-ethyl-2,2-diphenylethylaminium cation radical (2A) and cyclizations of the N-methyl-5,5-diphenyl-4-pentenaminium cation radical (6A) and the N-methyl-6,6-diphenyl-5-hexenaminium cation radical (9A) were studied. In organic solvents, these reactions are several orders of magnitude faster than analogous reactions of their neutral dialkylaminyl radical precursors and faster than reactions of isostructural carbon radical analogs. In acetonitrile and in THF with carboxylic acids as proton sources, reactions of 2A and 9A displayed saturation kinetics from which rate constants for reaction and apparent equilibrium constants for protonation could be determined by regression analysis of observed rate constants as a function of acid normality. In ethanol with perchloric acid, 9A was completely protonated. In aqueous solutions, the observed kinetics for reactions of 2A and 9A were dependent on the pH of the solutions which permitted determinations of both the rate constants for the reactions and the pK(a) values for the dialkylaminium cation radicals. Large kinetic solvent effects and a counterion effect when oxalic acid was the proton source in acetonitrile were observed. Arrhenius functions for 2A in acetonitrile and in THF and for 9A in acetonitrile, THF, and ethanol were determined. A rate constant for the 5-exo cyclization of 6A in acetonitrile at 20 degrees C was estimated by comparing the apparent second-order rate constants for reactions of the aminyl radical precursors to 6A and 9A with various carboxylic acids; with strong carboxylic acids, rate limiting protonation for the precursor to 6A apparently occurred. Second-order rate constants at ambient temperature for reactions of octanethiol and triphenylstannane with radical 2A were determined directly, and that for reaction of thiophenol with radical 9A was determined by indirect methods; the stannane, with an electron rich hydrogen, reacts much more rapidly with the aminium cation radical than with carbon radicals, whereas the thiols react less rapidly.
• US3987201A
  申请人：——

  公开号：US3987201A

  公开（公告）日：1976-10-19
• US4098890A
  申请人：——

  公开号：US4098890A

  公开（公告）日：1978-07-04
• Reaction of Nitrogen‐Radicals with Organometallics Under Ni‐Catalysis: N‐Arylations and Amino‐Functionalization Cascades
  作者：Lucrezia Angelini、Jacob Davies、Marco Simonetti、Laia Malet Sanz、Nadeem S. Sheikh、Daniele Leonori

  DOI：10.1002/anie.201900510

  日期：2019.4

  the generation of nitrogen‐radicals by ground‐state single electron transfer with organyl–NiI species. Depending on the philicity of the N‐radical, two types of processes have been developed. In the case of nucleophilic aminyl radicals direct N‐arylation with aryl organozinc, organoboron, and organosilicon reagents was achieved. In the case of electrophilic amidyl radicals, cascade processes involving

  在此，我们报告了一种通过有机基-Ni I物质的基态单电子转移产生氮自由基的策略。根据 N-自由基的亲和性，已经开发了两种类型的工艺。在亲核氨基自由基的情况下，可实现与芳基有机锌、有机硼和有机硅试剂的直接N-芳基化。对于亲电子酰胺基自由基，已经开发了涉及分子内环化，然后与芳基和烷基有机金属反应的级联过程。N-环化-烷基化级联引入了一种新颖的逆向合成断开方法，用于组装取代的内酰胺和吡咯烷，其潜力在四种毒液生物碱的简短全合成中得到了证明。