2-((4-溴苯基)(甲基)氨基)乙腈 | 157671-45-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 2-((4-溴苯基)(甲基)氨基)乙腈
• 英文名称: 2-[(4-bromophenyl)(methyl)amino]acetonitrile
• 英文别名: N-methyl-N-(4-bromophenyl)aminoacetonitrile；2-((4-Bromophenyl)(methyl)amino)acetonitrile；2-(4-bromo-N-methylanilino)acetonitrile
• CAS: 157671-45-9
• 化学式: C₉H₉BrN₂
• 分子量: 225.088
• InChiKey: RLEAQLVWFCWOOF-UHFFFAOYSA-N

物化性质

• 熔点：
  40℃
• 沸点：
  205-206 °C
• 密度：
  1.466±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  27
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2926909090

反应信息

• 作为反应物：
  描述：

  2-((4-溴苯基)(甲基)氨基)乙腈 以 solid 为溶剂， 生成 1,3-bis(N-methyl-4-bromoanilino)-2,4-bis(2-phenylethenyl)cyclobutane-1,3-dicarbonitrile
  参考文献：
  名称：

  Solution and Solid-State Photochemistry of 2-Anilino-5-phenyl-2,4-pentadienenitriles

  摘要：

  2-(N-Methylanilino)-5-phenyl-2,4-pentadienenitrile (3) undergoes either isomerization or oxidative cleavage at the 2,3-double bond upon irradiation in solution, whereas it dimerizes in a regiospecific manner to give the [2 + 2] cycloaddition product 12 upon irradiation in the solid state. From the fluorescence spectra and semiempirical calculation, the excited state of 3 is proposed to be a twist intramolecular charge transfer species. The X-ray analysis indicates that molecules 3b orient appropriately with a reasonable distance for the [2 + 2] cycloaddition in the solid state. The distance between C2 and C3' is 525 pm, the longest distance known in solid-state [2 + 2] cycloadditions. 2-(N-Methyl-p-bromoanilino)-5-phenyl-2,4-pentadienenitrile (4) shows behavior similar to that of 3 in the solution and solid-state photochemistry, whereas analogs 7-10 having nitro substituents on the 5-phenyl rings do not dimerize upon irradiation in the solid state. Semiempirical calculation of the electronic structures is used to interprete the discrepancy of reactivity.

  DOI：

  10.1021/jo00098a037
• 作为产物：
  描述：

  2-(甲基(苯基)氨基)乙腈 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 为溶剂， 反应 2.0h， 生成 2-((4-溴苯基)(甲基)氨基)乙腈
  参考文献：
  名称：

  Solution and Solid-State Photochemistry of 2-Anilino-5-phenyl-2,4-pentadienenitriles

  摘要：

  2-(N-Methylanilino)-5-phenyl-2,4-pentadienenitrile (3) undergoes either isomerization or oxidative cleavage at the 2,3-double bond upon irradiation in solution, whereas it dimerizes in a regiospecific manner to give the [2 + 2] cycloaddition product 12 upon irradiation in the solid state. From the fluorescence spectra and semiempirical calculation, the excited state of 3 is proposed to be a twist intramolecular charge transfer species. The X-ray analysis indicates that molecules 3b orient appropriately with a reasonable distance for the [2 + 2] cycloaddition in the solid state. The distance between C2 and C3' is 525 pm, the longest distance known in solid-state [2 + 2] cycloadditions. 2-(N-Methyl-p-bromoanilino)-5-phenyl-2,4-pentadienenitrile (4) shows behavior similar to that of 3 in the solution and solid-state photochemistry, whereas analogs 7-10 having nitro substituents on the 5-phenyl rings do not dimerize upon irradiation in the solid state. Semiempirical calculation of the electronic structures is used to interprete the discrepancy of reactivity.

  DOI：

  10.1021/jo00098a037

文献信息

• Photoredox-Catalyzed C_α–H Cyanation of Unactivated Secondary and Tertiary Aliphatic Amines: Late-Stage Functionalization and Mechanistic Studies
  作者：Ozgur Yilmaz、Martins S. Oderinde、Marion H. Emmert

  DOI：10.1021/acs.joc.8b01700

  日期：2018.9.21

  general, high-yielding amine Cα–H cyanation protocol via photoredox catalysis. Inexpensive NaCN is employed as the cyanide source and air is the external oxidant, resulting in mild and highly functional group tolerant conditions. Notably, efficient Cα–H cyanations of secondary and tertiary aliphatic amines and of complex, biologically active compounds (drugs) can be performed using the established methodology

  本文描述了开发和一个一般地，高产胺的C机理研究α -H氰化经由photoredox催化协议。廉价的NaCN用作氰化物源，空气是外部氧化剂，导致温和且高度官能团耐受的条件。值得注意的是，高效的C α -H的cyanations二级和三级可使用所建立的方法进行脂族胺和复杂的，生物活性化合物（药物）的。机理研究表明，该羧酸添加剂具有三种作用：形成稳定的半胱氨酸中间体，通过使底物质子化来防止催化剂分解以及调节光激发催化剂物种的荧光猝灭。
• [EN] PYRROLE AND PYRAZOLE DERIVATIVES AS POTENTIATORS OF GLUTAMATE RECEPTORS<br/>[FR] COMPOSES DE PYRROLE ET PYRAZOLE PRESENTANT UN EFFET POTENTIATEUR SUR LES RECEPTEURS DU GLUTAMATE
  申请人：LILLY CO ELI

  公开号：WO2005040110A1

  公开（公告）日：2005-05-06

  The present invention relates to pyrrole and pyrazole compounds of formula (I) and their pharmaceutically acceptable salts, and further relates to their use in treating schizophrenia, cognitive deficits associated with schizophrenia, Alzheimer's disease, dementia of the Alzheimer's type, mild cognitive impairment, or depression. The compounds act as potentiators on glutamate receptors, in particular AMPA and the GluR family.

  本发明涉及式(I)的吡咯和吡唑化合物及其药用可接受的盐，并且进一步涉及它们在治疗精神分裂症、与精神分裂症相关的认知缺陷、阿尔茨海默病、阿尔茨海默型痴呆、轻度认知障碍或抑郁症方面的应用。这些化合物作为谷氨酸受体的增强剂，特别是AMPA和GluR家族。
• A Widely Applicable Regioselective Aerobic α-Cyanation of Tertiary Amines Heterogeneously Catalyzed by Manganese Oxides
  作者：Kazuya Yamaguchi、Ye Wang、Noritaka Mizuno

  DOI：10.1002/cctc.201300477

  日期：2013.10

  A fit catalyst for some aerobic exercise: A manganese oxide‐based octahedral molecular sieve, OMS‐2, could act as an efficient heterogeneous catalyst for the regioselective α‐cyanation of various tertiary amines, including trialkyl, benzylic, and N,N‐dialkylaniline derivatives using trimethylsilyl cyanide (TMSCN) as the cyano source and molecular oxygen as the terminal oxidant.

  适合进行有氧运动的催化剂：基于氧化锰的八面体分子筛OMS-2可作为有效的非均相催化剂，用于多种叔胺的区域选择性α-氰化，包括三烷基，苄基和N，N-二烷基苯胺衍生物，使用三甲基甲硅烷基氰化物（TMSCN）作为氰基源，使用分子氧作为末端氧化剂。
• Iron-Catalyzed α-C–H Cyanation of Simple and Complex Tertiary Amines
  作者：Ozgur Yilmaz、Cagatay Dengiz、Marion H. Emmert

  DOI：10.1021/acs.joc.0c02642

  日期：2021.2.5

  cyanation of tertiary amines and its application in late-stage functionalization. Suitable substrates include tertiary aliphatic, benzylic, and aniline-type substrates and complex substrates. Functional groups tolerated under the reaction conditions include various heterocycles and ketones, amides, olefins, and alkynes. This broad substrate scope is remarkable, as comparable reaction protocols for

  该手稿详细介绍了叔胺α-C–H氰化的通用温和方法的开发及其在后期官能化中的应用。合适的底物包括叔脂族，苄基和苯胺型底物和复合物底物。在反应条件下容许的官能团包括各种杂环和酮，酰胺，烯烃和炔烃。这种宽泛的底物范围非常引人注目，因为类似的α-C–H氰化反应方案经常通过自由基机制发生，因此从根本上限制了它们的官能团耐受性。相反，所提出的催化剂体系可耐受通常与自由基反应的官能团，提示了另一种反应途径。所描述的催化剂体系的所有组分均易于获得，
• Acetone Cyanohydrin: A Convenient Alternative of Toxic Sodium Cyanide/Acetic Acid for Oxidative Cyanation of Tertiary Amines
  作者：Sanny Verma、Suman L. Jain、Bir Sain

  DOI：10.1007/s10562-011-0582-6

  日期：2011.6

  Acetone cyanohydrin was found to be a facile, convenient and comparatively safer alternative to toxic sodium cyanide/acetic acid system for generating in situ HCN for the oxidative cyanation of tertiary amines to α-aminonitriles in high yields with hydrogen peroxide using RuCl3 as catalyst. In addition organic nature of acetone cyanohydrin makes it more suitable for an organic transformation since

  发现丙酮氰醇是一种简便、方便且相对安全的有毒氰化钠/乙酸体系的替代品，用于原位生成 HCN，以使用 RuCl3 作为催化剂，使用过氧化氢以高产率将叔胺氧化氰化为 α-氨基腈。此外，丙酮氰醇的有机性质使其更适合于有机转化，因为它易溶于反应介质并且可以以受控方式添加。 图形摘要