N-(2-hydroxy-5-methylphenyl)-4-methylbenzenesulfonamide | 81256-11-3

• 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-(2-hydroxy-5-methylphenyl)-4-methylbenzenesulfonamide
• CAS: 81256-11-3
• 化学式: C₁₄H₁₅NO₃S
• 分子量: 277.344
• InChiKey: GPUGAPONHYNNRQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 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-(2-hydroxy-5-methylphenyl)-4-methylbenzenesulfonamide 在 磺酰氯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 5-Methyl-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-amino-4-methylphenyl 4-methylbenzene sulfonate 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 1.0h， 以50%的产率得到N-(2-hydroxy-5-methylphenyl)-4-methylbenzenesulfonamide
  参考文献：
  名称：

  Substitution at tetracoordinate sulfur(VI). Rearrangement of 2-aminoaryl arenesulfonates to N-(2-hydroxyaryl)arenesulfonamides

  摘要：

  DOI：

  10.1021/jo00349a013

文献信息

• A one-pot hypoiodite catalysed oxidative cycloetherification approach to benzoxazoles
  作者：Siva Senthil Kumar Boominathan、Wan-Ping Hu、Gopal Chandru Senadi、Jaya Kishore Vandavasi、Jeh-Jeng Wang

  DOI：10.1039/c4cc02425g

  日期：——

  A practical one-pot hypoiodite catalysed oxidative cyclization approach to synthesize alpha-ketobenzoxazole derivatives was successfully developed. This operationally simple protocol utilizes easily-accessible starting materials and has a broad substrate scope with excellent yields.

  成功开发了一种实用的一锅式次碘酸盐催化氧化环化方法，用于合成α-酮基苯并恶唑衍生物。该操作简单的方案使用易于获得的起始原料，具有广泛的底物范围，且产率高。
• Hexafluoroisopropanol (HFIP)-prompted rearrangement of N-phenoxysulfonamides for the direct assembly of ortho-sulfonamide phenols: A combined experimental and computational study
  作者：Yi Wang、Xiaoli Chen、Shuang Lin、Hui Gao、Fu-Xiaomin Liu、Zhi Zhou、Wei Yi

  DOI：10.1016/j.tetlet.2021.153601

  日期：2022.1

  chemistry. Herein an efficient metal-free rearrangement reaction has been developed for the construction of ortho-sulfonamide phenols via HFIP-prompted intramolecular sulfonamide group 1,3-migration. This protocol features mild reaction conditions, broad functional group compatibility and good regioselectivity. Combined experimental mechanistic study and detailed DFT calculations clarified the crucial

  邻磺酰胺酚代表了药物和合成化学中一类有吸引力的结构基序。本文开发了一种有效的无金属重排反应，用于通过 HFIP 促进的分子内磺酰胺基团 1,3-迁移构建邻磺酰胺酚。该方案具有反应条件温和、官能团兼容性广、区域选择性好等特点。结合实验机理研究和详细的 DFT 计算，阐明了 HFIP 分子在促进该反应中的关键作用，并且推导出了独特的氢键网络来解释观察到的反应性。
• 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。
• Switchable Oxidative Reactions of <i>N</i>-allyl-2-Aminophenols: Palladium-Catalyzed Alkoxyacyloxylation vs an Intramolecular Diels–Alder Reaction
  作者：Sabrina Giofrè、Manfred Keller、Leonardo Lo Presti、Egle M. Beccalli、Letizia Molteni

  DOI：10.1021/acs.orglett.1c02539

  日期：2021.10.15

  The Pd(II)-catalyzed reaction of N-allyl-2-aminophenols in the presence of PhI(OCOR)2 as the oxidant resulted in an alkoxyacyloxylation process, with the formation of functionalized dihydro-1,4-benzoxazines. The reaction performed in the absence of palladium catalyst switched to an intramolecular Diels–Alder reaction (IMDA) pathway, which was the result of an oxidative dearomatization of the 2-aminophenol

  在 PhI(OCOR) 2作为氧化剂的存在下，Pd(II) 催化的N-烯丙基-2-氨基苯酚反应导致烷氧基酰氧基化过程，形成官能化的二氢-1,4-苯并恶嗪。在没有钯催化剂的情况下进行的反应切换到分子内 Diels-Alder 反应 (IMDA) 途径，这是 2-氨基苯酚的氧化脱芳构化、亲核加成和 Diels-Alder 反应级联的结果，突出了氧化剂既是亲核供体又是氧化剂。
• Solvent-Controlled Pd(II)-Catalyzed Aerobic Chemoselective Intermolecular 1,2-Aminooxygenation and 1,2-Oxyamination of Conjugated Dienes for the Synthesis of Functionalized 1,4-Benzoxazines
  作者：Ke Wen、Zhengxing Wu、Banruo Huang、Zheng Ling、Ilya D. Gridnev、Wanbin Zhang

  DOI：10.1021/acs.orglett.8b00352

  日期：2018.3.16

  Pd(II)-catalyzed intermolecular 1,2-aminooxygenation and 1,2-oxyamination of conjugated dienes have been developed. The chemoselective preparation of a variety of 2-functionalized and 3-functionalized 1,4-benzoxazine derivatives was accomplished via the adjustment of a coordinating solvent. Oxygen was successfully used in this oxidative difunctionalization of alkenes. Good yields and selectivities

  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。