7-(phenoxyacetyl)-3-chloro-3-cephem-4-carboxylic acid p-nitrobenzyl ester | 65404-46-8

• 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: 7-(phenoxyacetyl)-3-chloro-3-cephem-4-carboxylic acid p-nitrobenzyl ester
• 英文别名: (4-nitrophenyl)methyl (6R,7R)-3-chloro-8-oxo-7-[(2-phenoxyacetyl)amino]-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate
• CAS: 65404-46-8
• 化学式: C₂₂H₁₈ClN₃O₇S
• 分子量: 503.92
• InChiKey: BJYNEWYPMMYDKH-WIYYLYMNSA-N

物化性质

• 沸点：
  802.4±65.0 °C(Predicted)
• 密度：
  1.56±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  156
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  7-(phenoxyacetyl)-3-chloro-3-cephem-4-carboxylic acid p-nitrobenzyl ester 在 palladium on activated charcoal 甲酸铵 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 6.0h， 以97%的产率得到(6R)-3-chloro-8-oxo-7t-(2-phenoxy-acetylamino)-(6rH)-5-thia-1-aza-bicyclo[4.2.0]oct-2-ene-2-carboxylic acid
  参考文献：
  名称：

  头孢菌素的4-硝基苄基酯的催化转移氢解

  摘要：

  使用无水甲酸铵或次膦酸作为催化转移剂，在10％的存在下，将头孢菌素1a-d选择性地氢解为相应的酸2a-d，而没有头孢烯双键的异构化。

  DOI：

  10.1016/s0040-4039(98)00210-x
• 作为产物：
  描述：

  7beta-Phenoxyacetamido-3-hydroxy-3-cephem-4-carboxylic acid p-nitrobenzyl ester 在 (PhO)3P⁽¹⁺⁾*Cl^(1-) 、 水 作用下， 生成 7-(phenoxyacetyl)-3-chloro-3-cephem-4-carboxylic acid p-nitrobenzyl ester
  参考文献：
  名称：

  Kinetic Differences in the Chlorination of Cephalosporin versus Carbacephalosporin Enols: Evidence of Sulfur Neighboring Group Participation

  摘要：

  Intermediates in the chlorination of carbacephalosporin and cephalosporin enols with chlorotriph-enoxyphosphonium chloride, (PHO)(3)P+Cl Cl-, have been characterized at low temperatures by NMR. P-31 NMR has been used to determine the rate constants and Arrhenius activation energies for the chlorination of the cephalosporin enol 1b and the carbacephalosporin enol 1c. The results show a 3.7 kcal/mol lower activation energy for the chlorination of the cephalosporin enol. Semiempirical and ab initio calculations have been employed to evaluate chloride attack and phosphate departure for model cephalosporin and carbacephalosporin enols. The experimental and computational results are consistent with a chlorination mechanism that involves rapid, reversible chloride addition to an intermediate enol phosphonium species followed by rate-limiting phosphate departure. The lower activation energy for phosphate departure in the cephalosporin case is attributed to sulfur neighboring group participation.

  DOI：

  10.1021/jo00098a034

文献信息

• Oral absorption of cephalosporin antibiotics. 3. Synthesis and biological properties of 7.alpha.-methoxy-7.beta.-arylacetamido-3-chloro-3-cephem-4-carboxylic acids
  作者：Janice Pfeil-Doyle、Stjepan Kukolja

  DOI：10.1021/jm00118a024

  日期：1988.10

  A series of 7 alpha-methoxy-7 beta-amido-3-chloro-3-cephem-4-carboxylic acids was prepared and evaluated for biological activity. When compared with the parent 7-non-methoxy analogues, these new 7 alpha-methoxy-3-chloro cephalosporins displayed diminished antimicrobial activity.

  制备了一系列的7种α-甲氧基-7β-氨基-3-氯-3-cephem-4-羧酸，并对其生物学活性进行了评估。当与母体7-非甲氧基类似物相比时，这些新的7α-甲氧基-3-氯头孢菌素显示出降低的抗菌活性。
• An Efficient Method for the Reduction of Cephalosporin Sulfoxides
  作者：Neera Tewari、Yatendra Kumar、Rajesh Kumar Thaper、Jag Mohan Khanna

  DOI：10.1080/00397919608003725

  日期：1996.3

  An efficient and convenient method for the reduction of cephalosporin sulfoxides to their corresponding sulfides by Lawesson reagent is reported.
• Catalytic transfer hydrogenolysis of 4-nitrobenzyl esters of cephalosporins
  作者：Domenico Albanese、Mario Leone、Michele Penso、Monica Seminati、Maurizio Zenoni

  DOI：10.1016/s0040-4039(98)00210-x

  日期：1998.4

  Cephalosporins 1a-d have been selectively hydrogenolysed to their corresponding acids 2a-d without isomerisation of the cephem double-bond using anhydrous ammonium formate or phosphinic acid as catalytic transfer agents in the presence of 10% .

  使用无水甲酸铵或次膦酸作为催化转移剂，在10％的存在下，将头孢菌素1a-d选择性地氢解为相应的酸2a-d，而没有头孢烯双键的异构化。
• Kinetic Differences in the Chlorination of Cephalosporin versus Carbacephalosporin Enols: Evidence of Sulfur Neighboring Group Participation
  作者：John E. Burks、Erik C. Chelius、Ross A. Johnson

  DOI：10.1021/jo00098a034

  日期：1994.9

  Intermediates in the chlorination of carbacephalosporin and cephalosporin enols with chlorotriph-enoxyphosphonium chloride, (PHO)(3)P+Cl Cl-, have been characterized at low temperatures by NMR. P-31 NMR has been used to determine the rate constants and Arrhenius activation energies for the chlorination of the cephalosporin enol 1b and the carbacephalosporin enol 1c. The results show a 3.7 kcal/mol lower activation energy for the chlorination of the cephalosporin enol. Semiempirical and ab initio calculations have been employed to evaluate chloride attack and phosphate departure for model cephalosporin and carbacephalosporin enols. The experimental and computational results are consistent with a chlorination mechanism that involves rapid, reversible chloride addition to an intermediate enol phosphonium species followed by rate-limiting phosphate departure. The lower activation energy for phosphate departure in the cephalosporin case is attributed to sulfur neighboring group participation.