N,N-dimethyl-2-(2-propenyl)benzenamine | 41652-86-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N-dimethyl-2-(2-propenyl)benzenamine
• 英文别名: o-(2-propenyl)-N,N-dimethylaniline；2-allyl-N,N-dimethylaniline；2-Allyl-N,N-dimethylanilin；N,N-dimethyl-2-prop-2-enylaniline
• CAS: 41652-86-2
• 化学式: C₁₁H₁₅N
• mdl: MFCD11111039
• 分子量: 161.247
• InChiKey: AMVODJHPDRXHEK-UHFFFAOYSA-N

物化性质

• 沸点：
  85 °C(Press: 9 Torr)
• 密度：
  0.938±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.272
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,N-dimethyl-2-(2-propenyl)benzenamine 在 双(乙腈)氯化钯(II) 、 sodium acetate 作用下， 以 乙腈 为溶剂， 反应 6.0h， 以89%的产率得到2H-N,N-dimethylquinolinium chloride
  参考文献：
  名称：

  Palladium-Mediated Intramolecular C-N Bond Formation between Tertiary Amines and Alkenes

  摘要：

  The reaction of terminal alkenylarenes having either o-(dimethylamino) or o-[(dimethylamino)methyl] substituents with PdCl2(MeCN)(2) in MeOH in the presence of NaOAc and PPh(3) has been studied. This reaction affords allylic phosphonium compounds for those substrates having more than six carbon atoms between the alkene function and the tertiary amine nitrogen atom, In those cases where the alkene is closer to the NMe(2) unit, this reaction leads, via allylic metalation, to intramolecular cyclization that involves generation of a new C-N bond and results in the formation of cationic 5-, 6-, or 7-membered heterocyclic ammonium compounds. For example, C6H4(CH2CH=CH2)-1-(CHMeNMe(2))-2 can be converted to the endo-cyclization product [C6H4{CH=CHCH(2)NMe(2)CH(Me)}-1,2]Cl in 86% yield with this Pd(II)-based system. The cyclization reaction is highly selective and occurs either at the terminal, less substituted olefinic carbon atom (C-gamma), affording ende-cyclization, or at the allylic C-alpha carbon atom, resulting in the formation of exo-cyclic products. The cyclization reaction is thought to proceed via a palladium-assisted C-H activation route: in most cases it was possible to isolate and characterize an eta(3)-allylpalladium complex as a key intermediate and then allow it to react further with PPh(3) to afford a cyclized end product. The X-ray crystal structures of a palladium-allyl complex, i.e., 2i(syn), and a quinolinium derivative, 3a, are described. Crystal data for 2i(syn): monoclinic, space group P2(1)/c, with a = 8.902(1), b = 20.587(1), and c = 9.702(1) Angstrom, beta = 95.52(1)degrees, Z = 4, R = 0.038. Crystal data for 3a: monoclinic, space group P2(1)/n with a = 13.032(1), b = 6.544(1), and c 13.415(1) Angstrom, beta = 114.72(1)degrees, Z = 4, R = 0.042,

  DOI：

  10.1021/ja00091a016
• 作为产物：
  描述：

  sodium 1,1-dimethyl-1-(2-propen-1-yl)silanolate 、 2-溴-N,N-二甲基苯胺 在 bis(η3-allyl-μ-chloropalladium(II)) 作用下， 以 乙二醇二甲醚 为溶剂， 反应 12.0h， 以84%的产率得到N,N-dimethyl-2-(2-propenyl)benzenamine
  参考文献：
  名称：

  Cross-Coupling of Aromatic Bromides with Allylic Silanolate Salts

  摘要：

  The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85 degrees C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (gamma-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher gamma-selectivity than the pure (2)-silanolates. A unified mechanistic picture involving initial gamma-transmetalation followed by direct reductive elimination or sigma-pi isomerization can rationalize all of the observed trends.

  DOI：

  10.1021/ja805951j

文献信息

• Dynamic Covalent Chemistry of Nucleophilic Substitution Component Exchange of Quaternary Ammonium Salts
  作者：Sirinan Kulchat、Jean-Marie Lehn

  DOI：10.1002/asia.201500604

  日期：2015.11

  catalyst. Microwave irradiation was used to assist the exchange reaction between the pyridinium salts and pyridine derivatives. Finally, experiments towards the generation of dynamic ionic liquids were performed. The results of this study pave the way for the extension of dynamic combinatorial chemistry to nucleophilic substitution reactions.

  季铵阳离子的动态共价库（DCL中）通过可逆亲核取代（S设置Ñ 2'和S Ñ 2）铵盐和叔胺的交换反应。反应在60°C下进行，以生成季铵化合物和叔胺的热力学和动力学控制混合物，并通过使用碘化物作为亲核催化剂来加速反应。微波辐射用于辅助吡啶鎓盐和吡啶衍生物之间的交换反应。最后，进行了产生动态离子液体的实验。这项研究的结果为将动态组合化学扩展到亲核取代反应铺平了道路。
• Palladium-catalyzed aerobic oxidative allylic C–H arylation of alkenes with polyfluorobenzenes
  作者：Huanfeng Jiang、Wanfei Yang、Huoji Chen、Jianxiao Li、Wanqing Wu

  DOI：10.1039/c4cc02023e

  日期：——

  An aerobic oxidative cross-coupling reaction of alkenes with polyfluorobenzenes, through palladium-catalyzed allylic C-H activation, is reported. This attractive route provides a new way to forge allylic C-C bonds of valuable products, in good yields, with high regioselectivity.

  据报道，通过钯催化的烯丙基CH活化，烯烃与多氟苯的需氧氧化交叉偶联反应。这一诱人的途径提供了一种新方法，可以以高收率和高区域选择性来锻造有价值产品的烯丙基CC键。
• Photochemische Cyclisierung von<i>o</i>-,<i>m</i>-,<i>P</i>-Allylanisolen und<i>o</i>-Allylanilinen. 52. Mitteilung über Photoreaktionen
  作者：Ursula Koch-Pomeranz、Hans Schmid、Hans-Jürgen Hansen

  DOI：10.1002/hlca.19770600309

  日期：1977.4.20

  Photochemical Cyclization of o-, m-, p-Allylanisoles and o-Allylanilines

  o-，m-，p-烯丙基苯甲醚和o-烯丙基苯胺的光化学环化
• Cyclizations via Frustrated Lewis Pairs: Lewis Acid Induced Intramolecular Additions of Amines to Olefins and Alkynes
  作者：Tanja Voss、Chao Chen、Gerald Kehr、Elisa Nauha、Gerhard Erker、Douglas W. Stephan

  DOI：10.1002/chem.200903483

  日期：2010.3.8

  Intramolecular additions of amines to olefinic and acetylenic residues in the presence of B(C6F5)3 affords a “frustrated Lewis Pair” strategy to five‐ and six‐membered‐ring heterocyclic ammonium borate derivatives (see picture).

  在B（C 6 F 5）3存在下，将胺分子内加成到烯属和炔属残基上，为五元和六元环杂环硼酸铵衍生物提供了“沮丧的路易斯对”策略（见图）。
• Polymers of carbon monoxide with olefinically unsaturated compounds
  申请人：SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

  公开号：EP0501586A2

  公开（公告）日：1992-09-02

  Polymers of carbon monoxide with one or more olefinically unsaturated compounds, which a) can be prepared by polymerization of carbon monoxide with one or more compounds of the general formula CH₂=CH-R⁶-R⁷ in which R⁷ represents an optionally substituted phenyl group which, with one of the carbon atoms of its aromatic ring, is connected to a divalent aliphatic hydrocarbylene bridging group R⁶ containing at least one carbon atom in the bridge, and, optionally, in addition with one or more olefinically unsaturated aliphatic compounds, b) possess a linear structure, and in which c) the units from carbon monoxide and the units from the olefinically unsaturated compounds are present in a substantially alternating arrangement.

  一氧化碳与一种或多种烯烃不饱和化合物的聚合物，其中 a) 可通过一氧化碳与一种或多种通式为 CH₂=CH-R⁶-R⁷ 的化合物聚合制备，其中 R⁷ 代表任选取代的苯基，该苯基与其芳香环的一个碳原子连接到二价脂肪族烃桥基 R⁶ 上，桥基中至少含有一个碳原子，此外还可任选与一种或多种烯烃不饱和脂肪族化合物聚合、 b) 具有线性结构，其中 c) 来自一氧化碳的单元和来自烯烃不饱和化合物的单元基本上交替排列。