N,N-dimethyl-3,4-difluorobenzylamine | 1416982-27-8

• 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-dimethyl-3,4-difluorobenzylamine
• 英文别名: 1-(3,4-difluorophenyl)-N,N-dimethylmethanamine
• CAS: 1416982-27-8
• 化学式: C₉H₁₁F₂N
• 分子量: 171.19
• InChiKey: MRLKOQMKKILENK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.333
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N,N-dimethyl-3,4-difluorobenzylamine 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 sodium carbonate 、 三苯基膦 作用下， 以 乙醚 、 二甲基亚砜 、 甲苯 为溶剂， 100.0 ℃ 、101.33 kPa 条件下， 反应 8.5h， 生成 2-(3,4-difluorophenyl)-N-phenylacetamide
  参考文献：
  名称：

  钯通过C–N键活化将苄基铵盐羰基化为酰胺和酯†

  摘要：

  首次报道了一种有效的钯催化的季铵盐与CO的有效的羰基催化羰基化反应，可通过苄基的C–N键裂解产生芳基乙酰胺和芳基酸酯。该方案的特点是在CO的大气压下具有温和的反应条件，无需其他氧化剂即可进行的氧化还原中性工艺，以及适用于各种胺，醇和酚的广泛底物范围。

  DOI：

  10.1039/c8ob00488a
• 作为产物：
  描述：

  二甲胺 、 alkaline earth salt of/the/ methylsulfuric acid 以 乙醚 为溶剂， 反应 12.0h， 生成 N,N-dimethyl-3,4-difluorobenzylamine
  参考文献：
  名称：

  Electrochemical Dehydrogenative Imidation of N-Methyl-Substituted Benzylamines with Phthalimides for the Direct Synthesis of Phthalimide-Protected gem-Diamines

  摘要：

  A general and green electrochemical dehydrogenative method for the imidation of N-methyl benzylamines with phthalimides with excellent regioselectivities is reported for the first time. This operationally simple method offers a valuable tool to obtain structurally diverse phthalimide-protected gem-diamines.

  DOI：

  10.1021/acs.orglett.8b03624

文献信息

• Nickel-Catalyzed Cross Couplings of Benzylic Ammonium Salts and Boronic Acids: Stereospecific Formation of Diarylethanes via C–N Bond Activation
  作者：Prantik Maity、Danielle M. Shacklady-McAtee、Glenn P. A. Yap、Eric R. Sirianni、Mary P. Watson

  DOI：10.1021/ja3089422

  日期：2013.1.9

  We have developed a nickel-catalyzed cross coupling of benzylic ammonium triflates with aryl boronic acids to afford diarylmethanes and diarylethanes. This reaction proceeds under mild reaction conditions and with exceptional functional group tolerance. Further, it transforms branched benzylic ammonium salts to diarylethanes with excellent chirality transfer, offering a new strategy for the synthesis

  我们开发了一种镍催化的苄基三氟甲磺酸铵与芳基硼酸的交叉偶联，以提供二芳基甲烷和二芳基乙烷。该反应在温和的反应条件下进行，具有出色的官能团耐受性。此外，它以优异的手性转移将支化的苄基铵盐转化为二芳基乙烷，为从容易获得的手性苄基胺合成高度对映体富集的二芳基乙烷提供了一种新策略。
• Palladium-Catalyzed Reductive Aminocarbonylation of Benzylammonium Triflates with <i>o</i>-Nitrobenzaldehydes for the Synthesis of 3-Arylquinolin-2(1<i>H</i>)-ones
  作者：Yongzhu Liu、Xinxin Qi、Xiao-Feng Wu

  DOI：10.1021/acs.joc.1c01984

  日期：2021.10.1

  straightforward procedure for the synthesis of 3-arylquinolin-2(1H)-ones has been developed. The synthesis proceeds through a palladium-catalyzed reductive aminocarbonylation reaction of benzylic ammonium triflates with o-nitrobenzaldehydes, and a wide range of 3-arylquinolin-2(1H)-ones was obtained in moderate to good yields with very good functional group compatibility.

  已开发出一种钯催化的直接合成 3-芳基喹啉-2(1 H )-酮的方法。该合成通过苄基三氟甲磺酸铵与邻硝基苯甲醛的钯催化还原氨基羰基化反应进行，并以中等至良好的收率获得了范围广泛的 3-芳基喹啉-2（1 H）-酮，并具有非常好的官能团兼容性。
• Manganese-Mediated C–H Bond Activation of Fluorinated Aromatics and the <i>ortho</i>-Fluorine Effect: Kinetic Analysis by <i>In Situ</i> Infrared Spectroscopic Analysis and Time-Resolved Methods
  作者：L. Anders Hammarback、Amy L. Bishop、Christina Jordan、Gayathri Athavan、Jonathan B. Eastwood、Thomas J. Burden、Joshua T. W. Bray、Francis Clarke、Alan Robinson、Jean-Philippe Krieger、Adrian Whitwood、Ian P. Clark、Michael Towrie、Jason M. Lynam、Ian J. S. Fairlamb

  DOI：10.1021/acscatal.1c05477

  日期：2022.1.21

  successful implementation in the synthesis of complex target molecules. The introduction of fluorine atoms into substrates has the potential to deliver this selectivity. In this study, we employ spectroscopic and computational methods to demonstrate how the “ortho-fluorine effect” influences the kinetic and thermodynamic control of C–H bond activation in manganese(I)-mediated reactions. The C–H bond activation

  深入了解控制过渡金属催化的 C-H 键官能化反应的位点选择性的因素对于它们在复杂靶分子合成中的成功实施至关重要。将氟原子引入基板有可能提供这种选择性。在这项研究中，我们采用光谱和计算方法来证明“邻氟效应”如何影响锰 (I) 介导的反应中 C-H 键活化的动力学和热力学控制。苄基锰(I)五羰基BnMn(CO) 5对氟化N、N-二甲基苄胺和氟化2-苯基吡啶的C-H键活化导致形成环锰化四羰基配合物（2a-b和4a-e ），它们都表现出邻位C-H 键活化-对氟。用密度泛函理论方法证实了实验结果，证实了动力学控制的不可逆 σ-配合物辅助复分解机制在这些反应中是有效的。苯甲酸的添加导致机械转换，因此环锰化通过可逆的 AMLA-6 机制（动力学和热力学控制）进行。这些化学计量的发现对催化至关重要，特别是随后将合适的受体底物插入区域异构环锰化四羰基络合物中间体的 C-Mn 键中。使用时间分辨红外光谱分析可以将末端乙炔插入
• ALKYLAMINOPROLINE DERIVATIVES AS ALFA-2-DELTA-1 BLOCKERS
  申请人：ESTEVE PHARMACEUTICALS, S.A.

  公开号：EP3904339A1

  公开（公告）日：2021-11-03

  The present invention relates to compounds showing pharmacological activity towards the subunit α2δ of voltage-gated calcium channels (VGCC), especially the α2δ-1 subunit of voltage-gated calcium channels. More particularly, the invention relates to alkylaminoproline derivatives having this pharmacological activity, to processes of preparation of such compounds, to pharmaceutical compositions comprising them, and to their use in therapy, in particular for the treatment of pain and/or as neuroprotective agents.

  本发明涉及对电压门控钙通道（VGCC）亚基α2δ，特别是电压门控钙通道的α2δ-1亚基具有药理活性的化合物。 更具体地说，本发明涉及具有这种药理活性的烷基氨基脯氨酸衍生物、这种化合物的制备工艺、包含它们的药物组合物，以及它们在治疗中的用途，特别是用于治疗疼痛和/或作为神经保护剂。
• The Role of Fluorine Substituents in the Regioselectivity of Intramolecular C–H Bond Functionalization of Benzylamines at Palladium(II)
  作者：Jessica Milani、Natalie E. Pridmore、Adrian C. Whitwood、Ian J. S. Fairlamb、Robin N. Perutz

  DOI：10.1021/acs.organomet.5b00608

  日期：2015.9.14

  The effect of fluorine substituents on the regio-selectivity of intramolecular reactions of mono- and difluorinated N,N-dimethylbenzylamines (la-f) at palladium, to form palladacycles di-mu-acetatobis [o-dimethylaminomethyl-n-fluorophenyl-C,N)dipalladium(II) (2a-f) and dilt-chlorobis[o-dimethylaminomethyl-n-fluorophenyl-C,N)dipalladium(II) (3a-e), has been investigated. When fluorinated substrates with two sites available for the C-H functionalization (1c and le) undergo cyclopalladation via a CMD mechanism (acetate-bridged palladacydes), they do not exhibit regioselectivity. In contrast, the same substrates exhibit complete regioselectivity for the C-H functionalization para to fluorine in cydopalladation reactions that proceed via an SEAr mechanism (involving chloride-bridged palladacydes). X-ray crystal structures were obtained for all the palladacydes synthesized, and a structural analysis showed that the number and the position of the fluorine atoms on the aromatic ring have a marked effect on the "clamshell" structure of the acetate-bridged palladacydes. By contrast, there is no great variation in the structures of the planar chloride-bridged palladacydes.