N-benzoyl-β-lactam | 69689-45-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: N-benzoyl-β-lactam
• 英文别名: 1-benzoyl-azetidin-2-one；N-benzoyl-2-azetidinone；1-Benzoyl-2-azetidinon；2-Azetidinone, 1-benzoyl-；1-benzoylazetidin-2-one
• CAS: 69689-45-8
• 化学式: C₁₀H₉NO₂
• mdl: MFCD03788400
• 分子量: 175.187
• InChiKey: PIWYBAZOWRPLAK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-benzoyl-β-lactam 在 sodium hydroxide 作用下， 生成 N-苯甲酰基-beta-丙氨酸
  参考文献：
  名称：

  Different Transition-State Structures for the Reactions of β-Lactams and Analogous β-Sultams with Serine β-Lactamases

  摘要：

  beta-Sultams are the sulfonyl analogues of beta-lactams, and N-acyl beta-sultams are novel inactivators of the class C beta-lactamase of Enterobacter cloacae P99. They sulfonylate the active site serine residue to form a sulfonate ester which subsequently undergoes C-O bond fission and formation of a dehydroalanine residue by elimination of the sulfonate anion as shown by electrospray ionization mass spectroscopy. The analogous N-acyl beta-lactams are substrates for beta-lactamase and undergo enzyme-catalyzed hydrolysis presumably by the normal acylation-deacylation process. The rates of acylation of the enzyme by the beta-lactams, measured by the second-order rate constant for hydrolysis, k(cat)/K-m, and those of sulfonylation by the beta-sultams, measured by the second-order rate constant for inactivation, k(i), both show a similar pH dependence to that exhibited by the beta-lactamase-catalyzed hydrolysis of beta-lactam antibiotics. Electron-withdrawing groups in the aryl residue of the leaving group of N-aroyl beta-lactams increase the rate of alkaline hydrolysis and give a Bronsted beta(Ig) of -0.55, indicative of a late transition state for rate-limiting formation of the tetrahedral intermediate. Interestingly, the corresponding Bronsted beta(Ig) for the beta-lactamase-catalyzed hydrolysis of the same substrates is -0.06, indicative of an earlier transition state for the enzyme-catalyzed reaction. By contrast, although the Bronsted beta(Ig) for the alkaline hydrolysis of N-aroyl beta-sultams is -0.73, similar to that for the beta-lactams, that for the sulfonylation of beta-lactamase by these compounds is -1.46, compatible with significant amide anion expulsion/S-N fission in the transition state. In this case, the enzyme reaction displays a later transition state compared with hydroxide-ion-catalyzed hydrolysis of the beta-sultam.

  DOI：

  10.1021/ja056124z
• 作为产物：
  描述：

  1-苄基氮杂啶-2-酮 在 triethylamine tris(hydrogen fluoride) 作用下， 以 乙腈 为溶剂， 以58%的产率得到N-benzoyl-β-lactam
  参考文献：
  名称：

  Suda, Kohji; Hotoda, Katsumi; Aoyagi, Mitsuaki, Journal of the Chemical Society. Perkin transactions I, 1995, # 11, p. 1327 - 1330

  摘要：

  DOI：

文献信息

• Competitive endo- and exo-cyclic C–N fission in the hydrolysis of <i>N</i>-aroyl β-lactams
  作者：Wing Y Tsang、Naveed Ahmed、Karl Hemming、Michael I Page

  DOI：10.1139/v05-153

  日期：2005.9.1

  The balance between endo- and exo-cyclic C–N fission in the hydrolysis of N-aroyl β-lactams shows that the difference in reactivity between strained β-lactams and their acyclic analogues is minimal. Attack of hydroxide ion occurs preferentially at the exocyclic acyl centre rather than that of the β-lactam during the hydrolysis of N-p-nitrobenzoyl β-lactam. In general, both endo- and exo-cyclic C–N bond fission occurs in the alkaline hydrolysis of N-aroyl β-lactams, the ratio of which varies with the aryl substituent. Hence, the Brønsted β-values differ for the two processes: –0.55 for the ring-opening reaction and –1.54 for the exocyclic C–N bond fission reaction. For the pH-independent and acid-catalysed hydrolysis of N-benzoyl β-lactam, less than 3% of products are derived from exocyclic C–N bond fission. Key words: β-lactams, hydrolysis, linear free energy relationships, strain.

  在N-酰基β-内酰胺水解中，内环和外环C-N裂解之间的平衡表明，受应变β-内酰胺和它们的非环结构类似物之间的反应性差异是最小的。在N-p-硝基苯甲酰基β-内酰胺水解过程中，羟根离子的攻击优先发生在外环酰基中心而不是β-内酰胺中心。一般来说，在N-酰基β-内酰胺的碱性水解中，内环和外环C-N键裂解都会发生，其比例随芳基取代基而变化。因此，这两个过程的Brønsted β值不同：环开启反应为-0.55，外环C-N键裂解反应为-1.54。对于N-苯甲酰基β-内酰胺的pH无关和酸催化水解，少于3%的产物来自外环C-N键裂解。关键词：β-内酰胺，水解，线性自由能关系，应变。
• Trifluoromethanesulfonic acid catalyzed Friedel–Crafts acylation of aromatics with β-lactams
  作者：Kevin W. Anderson、Jetze J. Tepe

  DOI：10.1016/s0040-4020(02)01026-8

  日期：2002.10

  N-Protected and unprotected 2-azetidinones, protolytically activated by superacidic trifluoromethanesulfonic acid, react with aromatic compounds to give β-amino aromatic ketones in good to excellent yields (65–98%). Non-benzenoid aromatics (pyrrole and ferrocene) produced good yield (64–89%) of the corresponding ketones.

  被超酸性三氟甲磺酸经蛋白水解活化的N-保护的和未保护的2-氮杂环丁酮与芳族化合物反应生成β-氨基芳族酮，收率良好至优异（65-98％）。非苯类芳族化合物（吡咯和二茂铁）的相应酮收率良好（64-89％）。
• The aminolysis of N-aroyl β-lactams occurs by a concerted mechanism
  作者：Wing Y. Tsang、Naveed Ahmed、Michael I. Page

  DOI：10.1039/b616420j

  日期：——

  insignificant solvent kinetic isotope effect, kH2ORNH2/kD2ORNH2, of 1.01 for the aminolysis of N-benzoyl beta-lactam with 2-methoxyethylamine. The Bronsted betalg value decreases from -1.03 to -0.71 as the amine nucleophile is changed from 2-cyanoethylamine to propylamine. The Bronsted betanuc value is more invariant although it changes from +0.90 to +0.85 on changing the amide leaving group from p-methoxy

  N-芳酰基β-内酰胺是具有外和内环酰基中心的酰亚胺，其与水溶液中的胺反应以产生开环的β-内酰胺氨解产物。不同于β-内酰胺类抗生素（如青霉素和头孢啶）的强碱催化氨解反应，N-芳酰基β-内酰胺类酶解的速率定律主要由一阶术语决定，该术语对游离碱形式的胺浓度具有一级依赖性，表示未催化的氨解反应。Np-甲氧基苯甲酰基β-内酰胺与一系列取代胺的未催化氨解反应的二级速率常数产生+0.90的布朗斯台德甜菜碱值。这表明过渡态的胺亲核试剂上正有效电荷的大量发展。相似地，对于不同的酰胺离去基团，2-氰基乙胺与取代的N-芳酰基β-内酰胺反应的速率常数给出的布朗斯泰德β1g值为-1.03，表明过渡态的离去基团上的有效电荷有相当大的变化。这些观察结果与用于逐步机理的四面体中间体形成的晚期过渡态或同时形成键和裂变的协同机理一致，其中酰胺离去基团作为阴离子排出。对于N-苯甲酰基β-内酰胺与2-甲氧基乙胺的氨解，无意义的溶剂动力学同位素效应kH2ORNH2
• Acyl vs Sulfonyl Transfer in <i>N</i>-Acyl β-Sultams and 3-Oxo-β-sultams
  作者：Naveed Ahmed、Wing Y. Tsang、Michael I. Page

  DOI：10.1021/ol0361305

  日期：2004.1.1

  and C-N bond fission. However, the hydrolysis of N-acyl beta-sultams is a sulfonyl transfer reaction that occurs with S-N fission and opening of the four-membered ring. Similar to other beta-sultams, the N-acyl derivatives are at least 10(6)-fold more reactive than N-acyl sulfonamides. 3-Oxo-beta-sultams are both beta-lactams and beta-sultams but also hydrolyze with preferential S-N bond fission.

  [反应：见正文] N-酰基磺酰胺通常通过酰基转移和CN键裂变与亲核试剂反应。然而，N-酰基β-杜马酰胺的水解是随着SN裂变和四元环的打开而发生的磺酰基转移反应。与其他β-舒马酸相似，N-酰基衍生物的反应性比N-酰基磺酰胺至少高10（6）倍。3-Oxo-beta-sultams既是beta-内酰胺又是beta-sultams，但也具有优先的SN键裂变而水解。
• Verfahren zur Herstellung von Amidoperoxicarbonsäuren
  申请人：HOECHST AKTIENGESELLSCHAFT

  公开号：EP0739880A2

  公开（公告）日：1996-10-30

  Verfahren zur Herstellung von Amidoperoxicarbonsäuren umfassend die Verfahrensschritte: Ringöffnung des N-Acyllactams zu der entsprechenden Amidocarbonsäure und nachfolgend Oxidation der erhaltenen Amidocarbonsäure zur entsprechenden Amidoperoxicarbonsäure.

  制备脒基过氧羧酸的工艺，包括以下步骤：N-酰基内酰胺开环生成相应的脒基羧酸，然后将生成的脒基羧酸氧化成相应的脒基过氧羧酸。