2-bromo-2-methyl-N-(p-chlorophenyl)propanamide | 1970-52-1

• 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: 2-bromo-2-methyl-N-(p-chlorophenyl)propanamide
• 英文别名: 2-bromo-4'-chloro-2-methylpropananilide；2-bromo-N-p-chlorophenylisobutyramide；p-chloro-α-bromoisobutyranilide；4-chlorophenyl-2-bromo-2-methylpropanamide；2-bromo-N-(4-chlorophenyl)-2-methylpropanamide
• CAS: 1970-52-1
• 化学式: C₁₀H₁₁BrClNO
• 分子量: 276.56
• InChiKey: TYQQFFYDEIZSMZ-UHFFFAOYSA-N

物化性质

• 熔点：
  110-111 °C
• 沸点：
  383.7±27.0 °C(Predicted)
• 密度：
  1.530±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-bromo-2-methyl-N-(p-chlorophenyl)propanamide 以 N,N-二甲基甲酰胺 为溶剂， 生成 N-(4-氯苯基)-2-甲基-丙酰胺
  参考文献：
  名称：

  Electrochemical determination of the pKa of weak acids in N,N-dimethylformamide

  摘要：

  The electroreduction of NH-protic alpha-bromo amides in DMF generates an enolate-type base which undergoes a fast proton transfer from the parent compound (self-protonation), affording the corresponding reduced amide together with the conjugate base of the bromo amide. When an acid weaker than the bromo amide is added to the solution, a current increase in a potential region more negative than the main voltammetric reduction peak is observed under suitable conditions. The voltammetric pattern is in agreement with an unfavored protonation of the conjugate base of the starting compound by the added proton donor with regeneration of the electroactive bromo amide. The theoretical analysis of this reduction sequence has been carried out, and the voltammetric profiles have been simulated. Comparison of the experimental and simulated voltammetries led to the determination of the acidity difference, DELTA-pK(a), between the a-bromo amide and the added acid. For each alpha-bromo amide it was possible to obtain DELTA-pK(a) data ranging from 1.4 to 4.2. The use of a-bromo amides of different acidity with the same exogenous acids provided the link between the different sets of relative acidities. In this way, using six alpha-bromo amides, a relative acidity scale encompassing an overall pK(a) variation in DMF of about 10 units could be established. The relative scale was then anchored to the low pK(a) scale in DMF through both the determination of the acidity of selected acids and using a correlation between literature pK(a) data obtained in both DMF and DMSO. The application of this original electrochemical mechanism provided absolute pK(a) data in DMF ranging from about 16 to 26, i.e., a pK(a) region that is practically unexplored in this solvent.

  DOI：

  10.1021/ja00024a041
• 作为产物：
  描述：

  N-(4-氯苯基)-2-甲基-丙酰胺 以 N,N-二甲基甲酰胺 为溶剂， 生成 2-bromo-2-methyl-N-(p-chlorophenyl)propanamide
  参考文献：
  名称：

  Electrochemical determination of the pKa of weak acids in N,N-dimethylformamide

  摘要：

  The electroreduction of NH-protic alpha-bromo amides in DMF generates an enolate-type base which undergoes a fast proton transfer from the parent compound (self-protonation), affording the corresponding reduced amide together with the conjugate base of the bromo amide. When an acid weaker than the bromo amide is added to the solution, a current increase in a potential region more negative than the main voltammetric reduction peak is observed under suitable conditions. The voltammetric pattern is in agreement with an unfavored protonation of the conjugate base of the starting compound by the added proton donor with regeneration of the electroactive bromo amide. The theoretical analysis of this reduction sequence has been carried out, and the voltammetric profiles have been simulated. Comparison of the experimental and simulated voltammetries led to the determination of the acidity difference, DELTA-pK(a), between the a-bromo amide and the added acid. For each alpha-bromo amide it was possible to obtain DELTA-pK(a) data ranging from 1.4 to 4.2. The use of a-bromo amides of different acidity with the same exogenous acids provided the link between the different sets of relative acidities. In this way, using six alpha-bromo amides, a relative acidity scale encompassing an overall pK(a) variation in DMF of about 10 units could be established. The relative scale was then anchored to the low pK(a) scale in DMF through both the determination of the acidity of selected acids and using a correlation between literature pK(a) data obtained in both DMF and DMSO. The application of this original electrochemical mechanism provided absolute pK(a) data in DMF ranging from about 16 to 26, i.e., a pK(a) region that is practically unexplored in this solvent.

  DOI：

  10.1021/ja00024a041

文献信息

• Photochemical Reactions of N-(2-Halogenoalkanoyl) Derivatives of Anilines
  作者：Takehiko Nishio、Hidenori Asai、Takenori Miyazaki

  DOI：10.1002/1522-2675(20000705)83:7<1475::aid-hlca1475>3.0.co;2-y

  日期：2000.7.5

  The photochemical reactions of 2-substituted N-(2-halogenoalkanoyl) derivatives 1 of anilines and 5 of cyclic amines are described. Under irradiation, 2-bromo-2-methylpropananilides 1a – e undergo exclusively dehydrobromination to give N-aryl-2-methylprop-2-enamides (=methacrylanilides) 3a – e (Scheme 1 and Table 1). On irradiation of N-alkyl- and N-phenyl-substituted 2-bromo-2-methylpropananilides

  描述了苯胺的 2-取代的 N-(2-卤代烷酰基) 衍生物 1 和环胺的 5 的光化学反应。在辐照下，2-溴-2-甲基丙酰苯胺 1a – e 仅进行脱溴氢反应，得到 N-芳基-2-甲基丙酰苯胺（=甲基丙烯酰苯胺）3a – e（方案 1 和表 1）。在辐照 N-烷基和 N-苯基取代的 2-溴-2-甲基丙苯胺 1f – m 时，环化产物，即 1,3-二氢-2H-吲哚-2-酮 (=oxindoles) 2f – m 和 3 ,4-二氢喹啉-2(1H)-ones (=dihydrocarbostyrils) 4f – m, 除了 3f – m。另一方面，N-甲基取代的 2-氯-2-苯基乙酰苯胺 1o - q 和 2-氯乙酰苯胺 1r 的辐照产生了羟吲哚 2o - r 作为唯一的产物，但收率低（方案 3 和表 2）。相应的 N-苯基衍生物 1s - v 光环化为羟吲哚 2s - v 进行顺利。提出了形成光产物的合理机制（方案
• Bromo–nitro substitution on a tertiary α carbon—a previously uncharacterized facet of the Kornblum substitution
  作者：Matthew J. Leonard、Peter G. McKay、Anthony R. Lingham

  DOI：10.1039/c5ra14798k

  日期：——

  Sodium nitrite in dimethylformamide substitutes nitro for bromine alpha to an amide carbonyl in high yield at a tertiary site.

  在二甲基甲酰胺中，亚硝酸钠以高产率在三级位点将硝基取代溴原子结合到酰胺羰基上。
• Cu-catalyzed intermolecular oxyalkylation of styrenes under air: access to diverse iminolactones
  作者：Yunhe Lv、Weiya Pu、Shukuan Mao、Xiaoran Ren、Yingtao Wu、Hao Cui

  DOI：10.1039/c7ra07306b

  日期：——

  A practical, simple, and efficient copper-catalyzed oxyalkylation of styrenes with α-bromoacetamides for the synthesis of iminolactones was developed under air.

  一种实用、简单、高效的铜催化氧烷基化苯乙烯与α-溴乙酰胺合成亚胺内酯的方法在空气中开发。
• Trans-selective cyclizations of alpha-bromocarboxamides and <i>E</i>/<i>Z</i>-mixed internal olefins catalyzed by a Fe salt
  作者：Yusei Nakashima、Shinya Ishimaru、Takashi Nishikata

  DOI：10.1039/d2cc04796a

  日期：——

  There are several reports of lactam cyclizations, but most yield less-substituted lactam rings. Therefore, diastereoselective cyclization to yield highly substituted lactams is one of the challenges in this field. We therefore propose a strategy involving the reactions of α-halocarboxamides with E/Z-mixed internal olefins here. An Fe/triphos catalyst system is effective in reactions between α-bromocarboxamides

  有几篇关于内酰胺环化的报道，但大多数产生较少取代的内酰胺环。因此，非对映选择性环化产生高度取代的内酰胺是该领域的挑战之一。因此，我们在这里提出了一种涉及 α-卤代羧酰胺与E / Z混合内烯烃反应的策略。Fe/triphos 催化剂体系在 α-溴代羧酰胺和内烯烃之间的反应中有效，以形成具有季碳的反式内酰胺。对照实验表明该反应涉及一个激进的过程。该反应可用于药物领域，因为 γ-内酰胺部分构成了许多药物和天然生物碱的核心结构。
• Electro-carboxylation of 2-bromoisobutyramides. a useful synthetic way to ester-amides of 2,2-dimethylmalonic acid
  作者：Flavio Maran、Monica Fabrizio、Ferruccio D'Angeli、Elio Vianello

  DOI：10.1016/s0040-4020(01)81744-0

  日期：1988.1