p-nitrobenzyl glyoxylate monohydrate | 83654-96-0

• 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: p-nitrobenzyl glyoxylate monohydrate
• 英文别名: p-nitrobenzyl glyoxylate hydrate；4-nitrobenzyl glyoxylate monohydrate；4-nitrobenzyl-1,1-dihydroxyacetate；p-nitrobenzyl glyoxalate (hydrate)；4-Nitrobenzyl 2,2-dihydroxyacetate；(4-nitrophenyl)methyl 2,2-dihydroxyacetate
• CAS: 83654-96-0
• 化学式: C₉H₉NO₆
• 分子量: 227.174
• InChiKey: JESMSJZDKNVWNX-UHFFFAOYSA-N

物化性质

• 熔点：
  103-105 °C
• 沸点：
  413.0±35.0 °C(Predicted)
• 密度：
  1.519±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  113
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  p-nitrobenzyl glyoxylate monohydrate 在 吡啶 、 二甲基硫 、 4 A molecular sieve 、 四氯化锡 、 臭氧 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 14.5h， 生成 p-nitrobenzyl 7β-[(phenoxyacetyl)amino]-3-hydroxy-1-carba-1-dethia-3-cephem-4-carboxylate
  参考文献：
  名称：

  Halide-Terminated N-Acyliminium Ion−Alkyne Cyclizations:  A New Construction of Carbacephem Antibiotics

  摘要：

  A series of 4-(3-alkynyl)azetidinones 13 was prepared from 4-(phenylsulfonyl)azetidine-2-one (9) and isopropyl glyoxylate hydrate. The 3-pentynyl (13a) and 4-phenyl-3-butynyl (13b) azetidinone acetates underwent 6-exo cyclization when treated with 3 equiv of SnCl4 at 0 degrees C to provide 3-(1-chloroalkylidene)carbacephems 15a (65%) and 15b (33%) respectively. In contrast, the 5-butynyl (13d) and 4-(trimethylsilyl)-3-butynyl (13c) azetidinone acetates under ent 7-endo cyclization under similar conditions to give 1-azabicyclo[5.2.0]nonenes 14a (11%) and 14b (71%), respectively. Beginning with penicillin degradation product 18, the more elaborate 3-pentynyl azetidinone cyclization substrate 27 was prepared in seven steps. Exposure to 27 to 3 equiv of SnCl4 in CH2Cl2 at 0 degrees C for 6 h, followed by allowing the reaction mixture to warm to rt, provided the desired 3-(1-chloroethylidene)carbacephem 28 in 60% yield and high (>99%) enantiometric purity. Cleavage of the chloroethylidene group of 28 with ozone gave 3-hydroxy carbacephem 29 in 77% yield. Since this intermediate has been converted in three steps to loracarbef (3), a new formal total synthesis of this carbacephem antiboitic was concluded.

  DOI：

  10.1021/jo971433w
• 作为产物：
  描述：

  bis-p-nitrobenzyl tartrate 在 过碘酸 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以74%的产率得到p-nitrobenzyl glyoxylate monohydrate
  参考文献：
  名称：

  Process Improved Preparation of a Versatile α-Ketoester Acyl Anion Synthon

  摘要：

  An improved scalable procedure for preparation of an alpha-ketoester acyl anion synthon is described.

  DOI：

  10.1080/00397919408011714

文献信息

• Indium mediated allylation of glyoxylate oxime ethers, esters and cyanoformates
  作者：Dougal J. Ritson、Russell J. Cox、John Berge

  DOI：10.1039/b402764g

  日期：——

  An indium mediated procedure has been developed for the allylation of activated O-functionalised oximes and nitriles as exemplified by a variety of glyoxylate derivatives. This method gives the corresponding free (or protected) amine in a one pot-process. The method is regiospecific and is carried out under remarkably mild conditions so that even oxime esters can be subjected to the typical reaction conditions.

  已开发出一种铟介导的方法，用于活化的O-官能化肟和腈的烯丙基化，如多种甘油酸衍生物的实例所示。该方法可在一步反应中获得相应的自由（或保护）胺。该方法具有区域选择性，并在非常温和的条件下进行，因此即使是肟酯也可以承受典型的反应条件。
• 2-(Alkylthio)penem-3-carboxylic acids. III. Synthesis of 6-ethylpenems.
  作者：AKIRA YOSHIDA、TERUO HAYASHI、NORIKO TAKEDA、SADAO OIDA、EIJI OHKI

  DOI：10.1248/cpb.29.1854

  日期：——

  An N-protected derivative of 4-phenylthio-2-azetidinone (3b) was ethylated to give 3c, which was converted into the phosphorane 5d by the standard procedure. Intramolecular Wittig reaction of 5d afforded 6-ethylpenem esters 8a and 9a which were transformed via manipulation of the side chain to the amino acids 8d and 9d and subsequently to the acetamido derivatives 8e and 9e, which are 1-thia analogs of the antibiotic PS-5.

  一个N-保护的4-苯硫基-2-氮杂环丁酮衍生物(3b)经过乙基化得到3c，后者通过标准程序转化为膦叶立德5d。5d的内酰胺Wittig反应产生了6-乙基青霉烯酯8a和9a，通过侧链操作转变为氨基酸8d和9d，接着转化为乙酰胺衍生物8e和9e，它们是抗生素PS-5的1-硫类似物。
• From Penicillin to Penem and Carbapenem. IX. C₁-Unit Introduction and the Carbapenam Synthesis from the Penicillin Molecule
  作者：Katsumi Fujimoto、Yuji Iwano、Koichi Hirai

  DOI：10.1246/bcsj.59.1887

  日期：1986.6

  An effective method for (R)-1-hydroxyethylation of benzyl bis(phenylseleno)penicillanate is described. The hydroxyethylated product was transformed into the 4-methylsulfonyl- and 4-phenylsulfonyl-2-azetidinone derivatives. These monocyclic compounds were reacted with potassium cyanide under two-phase conditions to give the 4-cyano-2-azetidinone derivative (C1-unit introduction) in high yield. The cyano group was then converted into the iodomethyl group. Using the 4-iodomethyl-2-azetidinone derivative an isopenam derivative was synthesized. Furthermore, carbapenam derivative were also constructed by a novel [3+2] cyclization reaction between 4-iodomethyl-2-azetidinone and dimethyl 2-methylthio- and 2-phenylthiofumarate.

  本研究描述了一种有效的方法，用于(R)-1-羟乙基化双(苯基硒)青霉烷酸苄酯。羟乙基化产物转化为 4-甲磺酰基和 4-苯磺酰基-2-氮杂环丁酮衍生物。在两相条件下，这些单环化合物与氰化钾反应，得到高产率的 4-氰基-2-氮杂环丁酮衍生物（C1-单位引入）。氰基随后转化为碘甲基。利用 4-碘甲基-2-氮杂环丁酮衍生物合成了异培南衍生物。此外，通过 4-iodomethyl-2-azetidinone 与 2-甲硫基和 2-苯硫基富马酸二甲酯之间的新型 [3+2] 环化反应，还合成了碳青霉烯类衍生物。
• Synthesis of 3-aminoalkyl substituted carbapenems via a phosphorane intermediate
  作者：Johannes G. de Vries、Gerhard Sigmund

  DOI：10.1016/s0040-4039(00)94906-2

  日期：1985.1

  Reaction of azetidinone phosphoranes with aldehyde gave the olefins , which were converted into carbapenem esters 6 in 4 steps. Hydrogenation of gave the title compounds.

  氮杂环丁酮膦烷与醛的反应得到烯烃，将其分四步转化为碳青霉烯酯6。氢化得到标题化合物。
• Nuclear analogs of β-lactam antibiotics. Synthesis of 6,6-disubstituted acylaminopenems
  作者：Jacques Banville、Philippe Lapointe、Bernard Belleau、Marcel Menard

  DOI：10.1139/v88-225

  日期：1988.6.1

  The preparation of 6α-methyl-2-methyl-6β-phenoxyacetamidopenem-3-carboxylate, 6α-methoxy-2-methyl-6β-phenoxyacetamidopenem-3-carboxylate, and 6α-methoxy-2-methyl-6β-phenylmalonylamidopenem-3-carboxylate from penicillin V and 6-aminopenicillanic acid is described. These penems have been isolated and characterized as their sodium or potassium salt. The chemical stability of the above compounds was determined as their half-life in aqueous buffer. In this way, it was found that the 6α-methyl analog was more stable than the parent 6-monosubstituted acylaminopenem while the remaining analogs were of comparable stability.

  描述了从青霉素V和6-氨基青霉烷酸制备6α-甲基-2-甲基-6β-苯氧乙酰胺基青霉烷-3-羧酸酯、6α-甲氧基-2-甲基-6β-苯氧乙酰胺基青霉烷-3-羧酸酯和6α-甲氧基-2-甲基-6β-苯基丙酰胺基青霉烷-3-羧酸酯的方法。这些青霉烷类化合物已被分离并表征为其钠盐或钾盐。通过在水溶液中测定它们的半衰期，确定了上述化合物的化学稳定性。通过这种方法，发现6α-甲基类似物比亲代6-单取代酰胺基青霉烷更稳定，而其余类似物的稳定性相当。