N-(3-hydroxynaphthalen-2-yl)-4-methylbenzenesulfonamide

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: N-(3-hydroxynaphthalen-2-yl)-4-methylbenzenesulfonamide
• 化学式: C₁₇H₁₅NO₃S
• 分子量: 313.377
• InChiKey: SRZMZHDSUAYHMA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 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-(3-hydroxynaphthalen-2-yl)-4-methylbenzenesulfonamide 在 磺酰氯 、 三乙胺 作用下， 生成 3-(Toluene-4-sulfonyl)-3H-1-oxa-2-thia-3-aza-cyclopenta[b]naphthalene 2,2-dioxide
  参考文献：
  名称：

  Acidity of Cyclic Sulfamates: Study of Substituted 1,2,3-Benzoxathiazole 2,2-Dioxides and Theoretical Investigation of the Effect of Conformation on Acidity

  摘要：

  Sulfamate 1b, 5-nitro-3-(4-toluenesulfonyl)-1,2,3-benzoxathiazole 2,2- dioxide, was treated with various nucleophiles: imidazole, benzylamine, tert-butylamine, sodium azide, potassium fluoride, pyridine, and sodium hydroxide. The first five attacked the exocyclic (tosyl) sulfur atom. No reaction was observed with the pyridine. The hydroxide ion attacked the endocyclic sulfur atom leading to opening of the benzoxathiazole ring. Several N-unsubstituted cyclic sulfamates, X-3H-1,2,3-benzoxathiazole 2,2-dioxides (2a, X = 5-H; 2b, X = 5-NO2; 2c, X = 5-Me; 2d, X = 5-Br; 2e, X = 5-Cl; 2f, X = 6-NO2; 2g, X = 5,6-Cl,Cl) and the naphtho-fused cyclic sulfamate (2h), were prepared by treatment of the respective N-tosyl compounds (1a-h) with sodium azide or potassium fluoride. The pK(a) values for these compounds were determined by potentiometric titration in 60% v/v EtOH/H2O. A Hammett plot using sigma(m) for 2a-e, sigma(p) for 2f, and both sigma(m) and sigma(p) for 2g gave a rho = 2.74. Ab initio calculations were done using sulfamic acid as a simple sulfamate model to test the effect of the geometry changes on pK(a). The calculations showed that the sulfamate with the ringlike geometry should be 3.6 pK(a) units more acidic than the acyclic sulfamate. This overall change was broken down into three factors affecting the pK(a). The N-S bond rotation accounted for a change of 0.22 units, O-S bond rotation for 2.03 units, and ring strain for 1.36 units.

  DOI：

  10.1021/jo00112a022
• 作为产物：
  描述：

  3-氨基-2-萘酚 在 吡啶 、 magnesium 作用下， 以 甲醇 为溶剂， 反应 36.0h， 生成 N-(3-hydroxynaphthalen-2-yl)-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

• 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。
• US6921740B1
  申请人：——

  公开号：US6921740B1

  公开（公告）日：2005-07-26
• 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。
• Acidity of Cyclic Sulfamates: Study of Substituted 1,2,3-Benzoxathiazole 2,2-Dioxides and Theoretical Investigation of the Effect of Conformation on Acidity
  作者：Kenneth K. Andersen、Martin G. Kociolek

  DOI：10.1021/jo00112a022

  日期：1995.4

  Sulfamate 1b, 5-nitro-3-(4-toluenesulfonyl)-1,2,3-benzoxathiazole 2,2- dioxide, was treated with various nucleophiles: imidazole, benzylamine, tert-butylamine, sodium azide, potassium fluoride, pyridine, and sodium hydroxide. The first five attacked the exocyclic (tosyl) sulfur atom. No reaction was observed with the pyridine. The hydroxide ion attacked the endocyclic sulfur atom leading to opening of the benzoxathiazole ring. Several N-unsubstituted cyclic sulfamates, X-3H-1,2,3-benzoxathiazole 2,2-dioxides (2a, X = 5-H; 2b, X = 5-NO2; 2c, X = 5-Me; 2d, X = 5-Br; 2e, X = 5-Cl; 2f, X = 6-NO2; 2g, X = 5,6-Cl,Cl) and the naphtho-fused cyclic sulfamate (2h), were prepared by treatment of the respective N-tosyl compounds (1a-h) with sodium azide or potassium fluoride. The pK(a) values for these compounds were determined by potentiometric titration in 60% v/v EtOH/H2O. A Hammett plot using sigma(m) for 2a-e, sigma(p) for 2f, and both sigma(m) and sigma(p) for 2g gave a rho = 2.74. Ab initio calculations were done using sulfamic acid as a simple sulfamate model to test the effect of the geometry changes on pK(a). The calculations showed that the sulfamate with the ringlike geometry should be 3.6 pK(a) units more acidic than the acyclic sulfamate. This overall change was broken down into three factors affecting the pK(a). The N-S bond rotation accounted for a change of 0.22 units, O-S bond rotation for 2.03 units, and ring strain for 1.36 units.