N,N-dimethylbenzylamine-d8 | 143958-59-2

• 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,N-dimethylbenzylamine-d8
• 英文别名: dimethylbenzylamine-d8
• CAS: 143958-59-2
• 化学式: C₉H₁₃N
• 分子量: 143.145
• InChiKey: XXBDWLFCJWSEKW-MUESUBCOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.75
• 重原子数：
  10.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  3.24
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  N,N-bis(trideuteriomethyl)benzamide 在 lithium aluminium deuteride 作用下， 以 乙醚 为溶剂， 生成 N,N-dimethylbenzylamine-d8
  参考文献：
  名称：

  Kinetics and mechanism of aliphatic amine oxidation by aqueous (batho)2CuII

  摘要：

  The kinetics of oxidation of a large series of aliphatic amines by the 'high-potential'' oxidant (batho)2Cu(II) (batho = 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolinedisulfonate) was studied under pseudo-first-order conditions (excess amine) in water or in 30% aqueous methanol (v/v) at 25-degrees-C over the pH range 7-11. The oxidations follow bell-shaped pH-rate profiles, with the low-pH leg reflecting the fact that only the free amine base is subject to oxidation and the high-pH leg representing conversion of (batho)2Cu(II) to an ineffective oxidant at high pH. The latter is thought to be (batho)Cu(II)(OH2)OH on the basis of the observed effect of [batho] on rate at high pH, and curve fitting of the rate data yielded estimates of the unitless K(eq) values governing this conversion. The variation in rate with degree of N-substitution and other structure-reactivity trends (such as the effect of ring size and the non-rate-retarding effect of 2,4,6-trimethyl substitution on PhCH2NR2) support a mechanism involving initial outer-sphere one-electron transfer, followed by proton transfer to the solvent, and then a rapid second one-electron oxidation to give imine/iminium product. Inner-sphere coordination of chelating amines shuts down the redox reaction, presumably as a consequence of displacement of the batho ligand(s) needed for high oxidant strength. Deuterium kinetic isotope effect (DKIE) measurements (i) comparing PhCD2N(CD3)2 vs PhCH2N(CH3)2 (intermolecular DKIE) and (ii) determining N-dealkylation preference in the case of PhCH2N(CH3)CD2Ph (intramolecular DKIE) suggest that the initial electron transfer is mainly rate-limiting. A rate comparison between erythro and three diastereomers of 1,2-diphenyl-2-piperidinoethanol indicates a stereoelectronic preference for one-electron oxidation at nitrogen when held antiperiplanar to a beta-hydroxyl. Stoichiometry studies using an excess of the Cu(II) oxidant reveal regioselective and chemoselective factors governing the overall amine-to-iminium oxidations.

  DOI：

  10.1021/ja00027a032

文献信息

• Direct Synthesis of N,N-Dimethylated and β-Methyl N,N-Dimethylated Amines from Nitriles Using Methanol: Experimental and Computational Studies
  作者：Bhaskar Paul、Sujan Shee、Dibyajyoti Panja、Kaushik Chakrabarti、Sabuj Kundu

  DOI：10.1021/acscatal.8b00021

  日期：2018.4.6

  Direct and selective synthesis of N,N-dimethylated amines from nitriles using methanol as C1 building blocks is reported using an air- and moisture-stable ruthenium complex. Following this process, various aromatic as well as aliphatic nitriles were converted to the corresponding N-methylated amines. Interestingly, tandem C-methylation as well as N-methylation was achieved by introducing multiple methyl

  据报道，使用空气和水分稳定的钌络合物，可以使用甲醇作为C1结构单元，从腈直接和选择性地合成N，N-二甲基胺。在该过程之后，将各种芳族腈和脂族腈转化为相应的N-甲基化胺。有趣的是，串联C-甲基化和N-甲基化是通过引入多个甲基实现的。通过与不同腈的制备规模反应以及抗过敏药“铁砧”的合成，揭示了该方法的实用方面。进行了几次动力学实验和详细的DFT计算，以了解该过程的机理。
• Selective synthesis of mono- and di-methylated amines using methanol and sodium azide as C1 and N1 sources
  作者：Kaushik Chakrabarti、Anju Mishra、Dibyajyoti Panja、Bhaskar Paul、Sabuj Kundu

  DOI：10.1039/c8gc00863a

  日期：——

  A Ru(II) complex mediated synthesis of various N,N-dimethyl and N-monomethyl amines from organic azides using methanol as a methylating agent is reported. This methodology was successfully applied for a one-pot reaction of bromide derivatives and sodium azide in methanol. Notably, by controlling the reaction time several N-monomethylated and N,N-dimethylated amines were synthesized selectively. The

  报道了使用甲醇作为甲基化剂，由有机叠氮化物介导的Ru（II）络合物介导的各种N，N-二甲基和N-单甲基胺的合成。该方法已成功应用于溴化物衍生物和叠氮化钠在甲醇中的一锅法反应。明显地，通过控制反应时间，几个N-单甲基化和N，N选择性合成-二甲基化胺。通过与不同有机叠氮化物的制备规模反应以及抗眩晕药倍他司汀的合成，揭示了该串联过程的实际适用性。进行了一些动力学实验和DFT研究，以了解这种转化的机理。
• A Novel Route to Synthesize <i>N,</i> <scp> <i>N</i> ‐Dimethyl </scp> Arylmethylamines from Aryl Aldehydes, Hexamethylenetetramine and Hydrogen ^†
  作者：Zhengang Ke、Bo Yu、Yunyan Wu、Yanfei Zhao、Peng Yang、Shien Guo、Zhimin Liu

  DOI：10.1002/cjoc.202000004

  日期：2020.8

  green routes to access valuable chemicals is of significance. Herein, we present a green and novel route to synthesize N,N‐ dimethyl arylmethylamines (DAMAs) from hexamethylenetetramine (HMTA) and aryl aldehydes in the presence of hydrogen, and a series of DAMAs can be obtained in good yields. This approach opens the precedent for HMTA as N,N ‐dimethylamine source to synthesize chemicals with N,N ‐dimethylamine

  开发简单而绿色的途径来获取有价值的化学品具有重要意义。在本文中，我们提出了一条绿色新颖的路线，​​可以在氢气存在下由六亚甲基四胺（HMTA）和芳基醛合成N，N-二甲基芳基甲胺（DAMA），并且可以高收率获得一系列DAMA。这种方法为HMTA作为N，N-二甲胺源合成具有N，N-二甲胺基团的化学品开辟了先例，在含N的化学品合成中具有广阔的应用前景。