N-(5-bromo-2-hydroxyphenyl)-4-methylbenzenesulfonamide | 136061-89-7

• 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-(5-bromo-2-hydroxyphenyl)-4-methylbenzenesulfonamide
• CAS: 136061-89-7
• 化学式: C₁₃H₁₂BrNO₃S
• 分子量: 342.213
• InChiKey: XMBDNYHRHPDEGI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  74.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-(5-bromo-2-hydroxyphenyl)-4-methylbenzenesulfonamide 在 磺酰氯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 5-Bromo-3-(4-toluenesulfonyl)-1,2,3-benzoxathiazole 2,2-dioxide
  参考文献：
  名称：

  1,2,3-Benzoxathiazole 2,2-dioxides: synthesis, mechanism of hydrolysis, and reactions with nucleophiles

  摘要：

  The rates of base-induced hydrolysis of some five-membered cyclic sulfamates, X-3-(p-tolylsulfonyl)-1,2,3-benzoxathiazole 2,2-dioxides (1a, X = H; 1b, X = 5-Me; 1c, X = 5-t-Bu; 1d, X = 5-Br; 1e, X = 5-Cl; 1f, X = 5-Ac; 1g, X = 5-NO2; 8a, X = 6-NO2) were measured in aqueous acetonitrile. The hydrolyses occurred with cleavage of the endocyclic N-SO2 bond. A Hammett plot using sigma-m values for 1a-g and sigma-p for 8a had rho = +2.20. Activation enthalpies and entropies were measured for 1a and for 3-methyl-1,2,3-benzoxathiazole 2,2-dioxide (10). Volumes of activation were determined for 1g and for 8a. The mechanistic profile for hydrolysis resembled that for the saponification of the analogous sultones and cyclic sulfates. These first examples of 1,2,3-benzoxathiazole 2,2-dioxides (1a-g, 8a) were prepared by treating N-(2-hydroxyphenyl)-p-toluenesulfonamides with sulfuryl chloride and triethylamine or by oxidizing the monoxide precursors using m-chloroperbenzoic acid. Treatment of 1a with potassium fluoride gave 1,2,3-benzoxathiazole 2,2-dioxide (9), which was methylated to give 10. Sulfamate 1a was treated with various nucleophilic reagents: phenyllithium, methyllithium, potassium fluoride, methylamine, tert-butylamine, and sodium methoxide. The first three attacked the tosyl sulfur atom and cleaved the exocyclic N-SO2 bond. The amines attacked the endocyclic sulfonyl sulfur atom and cleaved the endocyclic N-SO2 bond. Sodium methoxide attacked both sulfonyl groups.

  DOI：

  10.1021/jo00023a012
• 作为产物：
  描述：

  2-氨基-4-溴苯酚 在 吡啶 、 magnesium 作用下， 以 甲醇 为溶剂， 反应 36.0h， 生成 N-(5-bromo-2-hydroxyphenyl)-4-methylbenzenesulfonamide
  参考文献：
  名称：

  溶剂控制的Pd（II）催化的需氧化学选择性分子间1,2-氨基氧化和共轭二烯的1,2-氧肟化反应，以合成功能化的1,4-苯并恶嗪

  摘要：

  已经开发了Pd（II）催化的共轭二烯的分子间1,2-氨基加氧和1,2-氧胺化。通过调节配位溶剂可以完成多种2官能化和3官能化的1,4-苯并恶嗪衍生物的化学选择性制备。氧气已成功用于烯烃的氧化双官能化。大多数产品都具有良好的收率和选择性。还从2，3-二取代的1，3-二烯获得带有螺线结构的产物。

  DOI：

  10.1021/acs.orglett.8b00352

文献信息

• Pd(II)-Catalyzed Enantioselective Ring-Contraction for the Construction of 1,4-Benzoxazines
  作者：Chenghao Ye、Feng Gao、Haipeng Wei、Jianzhong Chen、Guoqiang Yang、Qianjia Yuan、Wanbin Zhang

  DOI：10.1021/acs.joc.1c01874

  日期：2021.12.3

  Enantioselective ring-contraction reactions have not been widely reported. We have developed an enantioselective ring contraction of 5,6-dihydro-2H-benzo[b][1,4]oxazocines, affording enantiomerically enriched 3,4-dihydro-2H-1,4-benzoxazine derivatives as single regioisomers. An acidic additive is necessary in order to obtain the products with good yields and enantiomeric ratios (up to 93% yield, 98:2

  对映选择性环收缩反应尚未被广泛报道。我们开发了 5,6-dihydro-2 H -benzo [ b ][1,4]oxazocines 的对映选择性环收缩，提供对映体富集的 3,4-dihydro-2 H -1,4-benzoxazine衍生物作为单一区域异构体。为了获得具有良好产率和对映体比率（高达 93% 产率，98:2 er）的产品，酸性添加剂是必需的。该反应成功地进行了克级反应，产物易于衍生化。
• Palladium-catalyzed oxamidation of alkenes: A new approach to benzoxazolidines
  作者：Niranjan Panda、Sushree Arpitabala Yadav

  DOI：10.1016/j.tet.2018.02.012

  日期：2018.3

  A novel palladium catalyzed protocol for the synthesis of benzoxazolidine by the reaction sulfamidophenol and terminal alkene was developed. This oxamidation process is simple and does not require any ligand, base or inert atmosphere for the overall transformation. From control experiments, it is apparent that the cross-coupling reaction proceeds with initial formation of enesulfonamide which undergoes

  提出了一种新的钯催化方案，其通过磺酰胺基苯酚和末端烯烃的反应合成苯并恶唑烷。该乙酰胺化过程很简单，不需要任何配体，碱或惰性气氛即可进行整体转化。从对照实验中可以明显看出，交叉偶联反应是随着烯磺酰胺的初步形成而进行的，该烯磺酰胺通过分子内的环化反应而被核仁酸化，随后被TsOH进行原去palpalpalpal化，从而得到苯并恶唑烷。
• Palladium-Catalyzed Asymmetric Aminohydroxylation of 1,3-Dienes
  作者：Hong-Cheng Shen、Yu-Feng Wu、Ying Zhang、Lian-Feng Fan、Zhi-Yong Han、Liu-Zhu Gong

  DOI：10.1002/anie.201712350

  日期：2018.2.23

  A PdII‐catalyzed asymmetric aminohydroxylation of 1,3‐dienes with N‐tosyl‐2‐aminophenols was developed by making use of a chiral pyridinebis(oxazoline) ligand. The highly regioselective reaction provides direct and efficient access to chiral 3,4‐dihydro‐2H‐1,4‐benzoxazines in high yield and enantioselectivity (up to 96:4 e.r.). The reaction employs readily available N‐tosyl‐2‐aminophenols as a unique

  利用手性吡啶双（恶唑啉）配体开发了Pd II催化的1,3-二烯与N-甲苯磺酰基-2-氨基苯酚的不对称氨基羟基化反应。高度区域选择性反应可直接高效地获得手性3,4-二氢-2 H -1,4-苯并恶嗪，且产率高且对映选择性高（高达96：4 er）。该反应采用现成的N-甲苯磺酰基-2-氨基苯酚作为独特的氨基羟基化试剂，是已知不对称氨基羟基化方法的补充。