4-bromo-N,N-dibutylbenzamide

• 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: 4-bromo-N,N-dibutylbenzamide
• 英文别名: N,N-dibutyl-4-bromobenzamide；4-(Bu2NC(O))C6H4Br；Benzamide, N,N-dibutyl-4-bromo-
• 化学式: C₁₅H₂₂BrNO
• mdl: MFCD01014841
• 分子量: 312.25
• InChiKey: WQPWOINOXVZQKN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.533
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-bromo-N,N-dibutylbenzamide 生成 N,N,N',N'-tetra-n-butyl-p,p'-butadiynylenedibenzamide
  参考文献：
  名称：

  UV-Irradiated Formation of Diradicals of Diphenylbutadiyne and Some of Itsp,p′-Disubstituted Derivatives

  摘要：

  首次发现芳香二炔在紫外光照射下，在溶液或固态中生成稳定的碳自由基物种，产生强烈的电子自旋共振（ESR）信号。自由基的数量达到了每摩尔二炔约10^20个，自溶液由于其重组形成聚合物而变成红色。在惰性气氛下，这些自由基几乎无限稳定。这些自由基的不寻常稳定性归因于与丁二炔相连的芳香环的共振效应。在黑暗中非常缓慢的湮灭似乎是由于它们之间的重组。理论计算表明，在1-和4-碳上的单体双自由基以sp构型形成，这些自由基结合形成通过ESR光谱检测到的二聚体或更高物种。

  DOI：

  10.1246/bcsj.78.1986
• 作为产物：
  描述：

  4-溴苯甲酸 、 二正丁胺 在 草酰氯 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 以94%的产率得到4-bromo-N,N-dibutylbenzamide
  参考文献：
  名称：

  Efficient Modulation of γ-Aminobutyric Acid Type A Receptors by Piperine Derivatives

  摘要：

  Piperine activates TRPV1 (transient receptor potential vanilloid type 1 receptor) receptors and modulates gamma-aminobutyric acid type A receptors (GABA(A)R). We have synthesized a library of 76 piperine analogues and analyzed their effects on GABA(A)R by means of a two-microelectrode voltage-clamp technique. GABA(A)R were expressed in Xenopus laevis oocytes. Structure-activity relationships (SARs) were established to identify structural elements essential for efficiency and potency. Efficiency of piperine derivatives was significantly increased by exchanging the piperidine moiety with either N,N-dipropyl, N,N-diisopropyl, N,N-dibutyl, p-methylpiperidine, or N,N-bis(trifluoroethyl) groups. Potency was enhanced by replacing the piperidine moiety by N,N-dibutyl, N,N-diisobutyl, or N,N-bistrifluoroethyl groups. Linker modifications did not substantially enhance the effect on GABA(A)R. Compound 23 [(2E,4E)-5-(1,3-benzodioxol-5-yl)-N,N-dipropyl-2,4-pentadienamide] induced the strongest modulation of GABA(A) (maximal GABA-induced chloride current modulation (IGABA-max = 1673% +/- 146%, EC50 = 51.7 +/- 9.5 mu M), while 25 [(2E,4E)-5-(1,3-benzodioxol-5-yl)-N,N-dibutyl-2,4-pentadienamide] displayed the highest potency (EC50 = 13.8 +/- 1.8 mu M, IGABA-max = 760% +/- 47%). Compound 23 induced significantly stronger anxiolysis in mice than piperine and thus may serve as a starting point for developing novel GABA(A)R modulators.

  DOI：

  10.1021/jm5002277

文献信息

• Carbonylative Tertiary Amide Synthesis from Aryl Iodides and Tertiary Amines <i>via</i> Oxidant-Free C−N Bond Cleavage Catalyzed by Palladium(II) Chloride in Polyethylene Glycol/Water
  作者：Rajendra S. Mane、Bhalchandra M. Bhanage

  DOI：10.1002/adsc.201700317

  日期：2017.8.7

  the C−N bond cleavage. The developed protocol offers the selective N‐dealkylation of tertiary amines in a polyethylene glycol/water solvent system. Numerous symmetrical and unsymmetrical aliphatic, alicyclic, benzyl, as well as aromatic tertiary amines with aryl iodides were well tolerated and afforded the desired products in good yields. Furthermore, the in situ generation of palladium(0) nanoparticles

  在这项工作中，我们描述了通过无氧化剂的C（sp 3）-N键裂解，使用原位形成钯（0）的钯（0）纳米粒子，从芳基碘化物和叔胺作为主要来源的酰胺基羰基合成羰基合成方法。聚乙二醇400 /水中的氯化物。值得注意的是，这些反应是在无碱，无配体的条件下进行的，不需要任何氧化剂即可裂解C-N键。开发的协议提供了选择性的N在聚乙二醇/水溶剂体系中对叔胺进行脱烷基。具有对称性和不对称性的脂肪族，脂环族，苄基以及芳族碘与芳族叔胺的耐受性很好，并以良好的收率提供了所需的产物。此外，通过TEM，FEG-SEM，EDS和XRD技术证实了聚乙二醇400中钯（0）纳米粒子的原位生成，这强烈表明钯纳米粒子是高活性物质，反应通过经典的钯进行（0）/钯（II）途径。另外，合成可以容易地按比例放大，并且催化体系可以循环多达五次，而不会损失其催化活性和选择性。
• Palladium-Catalyzed β-Selective Direct Arylation of Porphyrins
  作者：Yu Kawamata、Sumito Tokuji、Hideki Yorimitsu、Atsuhiro Osuka

  DOI：10.1002/anie.201102318

  日期：2011.9.12

  catalyst/potassium carbonate/pivalic acid system enables direct arylation of porphyrins by aryl bromides (see scheme; Ar′=3,5‐tBu2C6H3). The CH arylation shows excellent β selectivity and does not require porphyrin prefunctionalization, hence representing an extremely efficient method for rapidly providing a series of new β‐arylated porphyrins.

  四鸟一石：钯催化剂/碳酸钾/新戊酸体系可使卟啉被芳基溴直接芳基化（参见方案； Ar'= 3,5- t Bu 2 C 6 H 3）。与c  ħ芳基化显示出优异的选择性β并且不需要卟prefunctionalization，因此代表用于快速提供了一系列新的β-芳基化的卟啉的非常有效的方法。
• A novel Pd-catalyzed N-dealkylative carbonylation of tertiary amines for the preparation of amides
  作者：Tao Fang、Xu-Hong Gao、Ri-Yuan Tang、Xing-Guo Zhang、Chen-Liang Deng

  DOI：10.1039/c4cc07378a

  日期：——

  A novel and convenient protocol for the formation of amides via palladium-catalyzed N-dealkylative carbonylation of alkyl tertiary amines has been developed. In the presence of PdCl2(PhCN)2, CuO, PhCN and CO, a range of substituents on both aryl iodides and alkyl tertiary amines were compatible with the reaction to afford a series of N,N-disubstituted amides in moderate to excellent yields.

  开发了一种新颖方便的协议，通过钯催化的N-去烃基化羰基化反应形成酰胺。在PdCl2(PhCN)2、CuO、PhCN和CO的存在下，许多取代基的芳基碘化物和烷基三级胺均与该反应兼容，产出一系列N,N-二取代酰胺，产率中等至优良。
• Tunable Pd/C-catalyzed oxidative alkoxycarbonylation/aminocarbonylation of aryl hydrazines with alcohols/inert tertiary amines through C–N bond activation
  作者：Yuvraj A. Kolekar、Bhalchandra M. Bhanage

  DOI：10.1039/d2nj02172b

  日期：——

  sp2 C–N bond activation using molecular oxygen as an oxidant. The tertiary amine acts as both a nucleophile and a base. Advantageously, this process involves Pd/C as a heterogeneous and recyclable catalyst, and propylene carbonate as an environmentally benign solvent. This established protocol provides a promising, simple, and effective approach for preparing esters and tertiary amides under co-catalyst-free

  我们报告了 Pd/C 催化的未活化芳基肼的氧化氨基羰基化和烷氧基羰基化。该协议采用惰性叔胺作为胺源，并使用分子氧作为氧化剂通过氧化 sp 3和 sp 2 C-N 键活化芳基肼。叔胺既作为亲核试剂又作为碱。有利地，该方法涉及作为非均相和可回收催化剂的Pd/C，以及作为环境无害溶剂的碳酸亚丙酯。该已建立的协议为在无助催化剂和对水分敏感的无配体条件下制备酯和叔酰胺提供了一种有前途、简单且有效的方法。这种催化过程具有可持续、资源丰富、可回收且有价值的产品。
• Transition‐Metal‐Free Intermolecular Hydrocarbonation of Styrenes Mediated by NaH/1,10‐Phenanthroline
  作者：Kanako Nozawa‐Kumada、So Onuma、Kanako Ono、Tomohiro Kumagai、Yuki Iwakawa、Katsuhiko Sato、Masanori Shigeno、Yoshinori Kondo

  DOI：10.1002/chem.202203143

  日期：2023.3.28

  AbstractA transition‐metal‐free intermolecular coupling reaction of halocompounds with styrenes in the presence of NaH and 1,10‐phenanthroline was developed. This reaction afforded hydrocarbonated products with complete anti‐Markovnikov selectivity. The method allows the use of a wide range of halocompounds, including aryl and alkyl halides, and good functional group tolerance. Detailed mechanistic studies indicated that an anilide anion generated in situ by the NaH‐mediated reduction of 1,10‐phenanthroline works as an electron donor and a hydrogen source.