N-methyl-N-[4-(pyridine-3-carbonyl)phenyl]benzenesulfonamide | 160694-17-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-methyl-N-[4-(pyridine-3-carbonyl)phenyl]benzenesulfonamide
• CAS: 160694-17-7
• 化学式: C₁₉H₁₆N₂O₃S
• 分子量: 352.414
• InChiKey: WOGLJQFDNYKFMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  75.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (5-羧基戊基)三苯基溴化磷 、 N-methyl-N-[4-(pyridine-3-carbonyl)phenyl]benzenesulfonamide 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 生成 、 (Z)-7-[4-[benzenesulfonyl(methyl)amino]phenyl]-7-pyridin-3-ylhept-6-enoic acid
  参考文献：
  名称：

  苯基3-吡啶基酮的Wittig反应中的立体选择性：酰胺取代基对优先（E）-烯烃形成的影响

  摘要：

  酰胺取代的苯基3-吡啶基酮与含有羧基末端的“不稳定的”磷酰化物的维蒂希反应优选形成（E）-烯烃。对于这种立体选择性的偏爱是由于在氧杂膦烷中间体的形成过程中，酰胺基团与羧基末端之间的氢键键合或盐桥形成。

  DOI：

  10.1016/s0040-4039(98)01194-0
• 作为产物：
  描述：

  N-(4-溴苯基)甲磺酰胺 在 manganese(IV) oxide 、 sodium hydroxide 、 正丁基锂 、 四丁基硫酸氢铵 、 potassium carbonate 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 反应 3.92h， 生成 N-methyl-N-[4-(pyridine-3-carbonyl)phenyl]benzenesulfonamide
  参考文献：
  名称：

  Stereoselectivity in the Wittig Reaction of Aromatic Ketones: Origin of Preference for the Olefin Geometry

  摘要：

  Investigation of the stereoselectivity observed in the Wittig reaction of aromatic ketones with ''nonstabilized'' phosphonium ylides revealed that the nature of the substituent on the phenyl ring of phenyl S-pyridyl ketone determined the stereoselectivity. Generally the Wittig reaction of such ketones with carboxy phosphonium ylides proceeded preferentially to yield (Z)-olefin, albeit with modest selectivity. However, the reaction with aryl sulfonamido-substituted aromatic ketones resulted in high (E)-stereoselectivity. In order to understand the origin of this high (E)-selectivity, a semiempirical conformational analysis of the four uncharged diastereomeric oxaphosphetane intermediates was performed with a cumulatively modified sampling procedure to generate initial conformations, followed by full energy optimization. Computational studies of the unsubstituted and 4-nitrophenyl-substituted oxaphosphetane intermediates were consistent with the low (Z)stereoselectivity observed. The results in the calculations of the aryl sulfonamido-substituted intermediate likewise were consistent with the high (E)-stereoselectivity observed. Calculations of the potassium-coordinated acid anion of the latter species were also performed. All calculations supported interaction of the sulfonamido and carboxylate groups by either hydrogen bonding or salt bridge formation which appears to effect the final stereochemical outcome. Furthermore, we investigated the stereoselectivity of Wittig reactions in which the sulfonamido NH or the carboxylate were removed. In both cases, the (Z)-olefin was formed preferentially, thereby supporting the existence of intramolecular hydrogen bonding or salt bridge formation.

  DOI：

  10.1021/jo00106a029

文献信息

• Stereoselectivity in the Wittig Reaction of Aromatic Ketones: Origin of Preference for the Olefin Geometry
  作者：Kumiko Takeuchi、Jonathan W. Paschal、Richard J. Loncharich

  DOI：10.1021/jo00106a029

  日期：1995.1

  Investigation of the stereoselectivity observed in the Wittig reaction of aromatic ketones with ''nonstabilized'' phosphonium ylides revealed that the nature of the substituent on the phenyl ring of phenyl S-pyridyl ketone determined the stereoselectivity. Generally the Wittig reaction of such ketones with carboxy phosphonium ylides proceeded preferentially to yield (Z)-olefin, albeit with modest selectivity. However, the reaction with aryl sulfonamido-substituted aromatic ketones resulted in high (E)-stereoselectivity. In order to understand the origin of this high (E)-selectivity, a semiempirical conformational analysis of the four uncharged diastereomeric oxaphosphetane intermediates was performed with a cumulatively modified sampling procedure to generate initial conformations, followed by full energy optimization. Computational studies of the unsubstituted and 4-nitrophenyl-substituted oxaphosphetane intermediates were consistent with the low (Z)stereoselectivity observed. The results in the calculations of the aryl sulfonamido-substituted intermediate likewise were consistent with the high (E)-stereoselectivity observed. Calculations of the potassium-coordinated acid anion of the latter species were also performed. All calculations supported interaction of the sulfonamido and carboxylate groups by either hydrogen bonding or salt bridge formation which appears to effect the final stereochemical outcome. Furthermore, we investigated the stereoselectivity of Wittig reactions in which the sulfonamido NH or the carboxylate were removed. In both cases, the (Z)-olefin was formed preferentially, thereby supporting the existence of intramolecular hydrogen bonding or salt bridge formation.
• Stereoselectivity in the Wittig reaction of phenyl 3-pyridyl ketones: Amide substituent effect on the preferential (E)-ollefin formation
  作者：Kumiko Takeuchi、Todd J. Kohn

  DOI：10.1016/s0040-4039(98)01194-0

  日期：1998.8

  A Wittig reaction of amide substituted phenyl 3-pyridyl ketones with “nonstabilized” phosphorus ylides which contain a carboxyl terminus preferentially forms (E)-olefin. The preference for this stereoselectivity stems from either hydrogen bonding or salt-bridge formation between the amide group and the carboxyl terminus during the oxaphosphetane intermediate formation.

  酰胺取代的苯基3-吡啶基酮与含有羧基末端的“不稳定的”磷酰化物的维蒂希反应优选形成（E）-烯烃。对于这种立体选择性的偏爱是由于在氧杂膦烷中间体的形成过程中，酰胺基团与羧基末端之间的氢键键合或盐桥形成。