o-nitrobenzyl diazomethane | 5385-87-5

• 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: o-nitrobenzyl diazomethane
• 英文别名: 2-nitrophenyl diazomethane；1-diazomethyl-2-nitro-benzene；2-Nitrophenyldiazomethane；1-(diazomethyl)-2-nitrobenzene
• CAS: 5385-87-5
• 化学式: C₇H₅N₃O₂
• 分子量: 163.136
• InChiKey: PWKYTHJKEZEJNG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  47.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  o-nitrobenzyl diazomethane 在 水 作用下， 以 乙腈 为溶剂， 生成 邻硝基苯甲醇
  参考文献：
  名称：

  布朗斯台德酸的pKa控制它们与重氮化合物的反应性

  摘要：

  我们研究了一系列小分子和生物聚合物中烷基重氮化合物对磷酸基团的O-烷基化作用。

  DOI：

  10.1039/c6cc03561b
• 作为产物：
  描述：

  2-nitro-benzaldehyde hydrazone 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 1.0h， 生成 o-nitrobenzyl diazomethane
  参考文献：
  名称：

  布朗斯台德酸的pKa控制它们与重氮化合物的反应性

  摘要：

  我们研究了一系列小分子和生物聚合物中烷基重氮化合物对磷酸基团的O-烷基化作用。

  DOI：

  10.1039/c6cc03561b

文献信息

• Studies on tRNA and related compounds. XXXVII. Synthesis and physical properties of 2'- or 3'-O-(o-nitrobenzyl)nucleosides: the use of o-nitrophenyldiazomethane as a synthetic reagent.
  作者：EIKO OHTSUKA、TOSHIAKI WAKABAYASHI、SHOJI TANAKA、TOSHIKI TANAKA、KAZUYUKI OSHIE、AKIRA HASEGAWA、MORIO IKEHARA

  DOI：10.1248/cpb.29.318

  日期：——

  2'-and 3'-O-(o-Nitrobenzyl) derivatives of uridine, cytidine, adenosine and guanosine were synthesized by treatment of uridine, N-benzoylcytidine, N-benzoyladenosine and N-isobutyrylguanosine, respectively, with o-nitrophenyldiazomethane followed by isolation and deblocking. 3'-O-(o-Nitrobenzyl) guanosine is a novel compound. By using N-acylated nucleosides, separation of the 2'-and 3'-substituted isomers on silica gel became feasible and these compounds were useful intermediates for the synthesis of oligoribonucleotides. Some physical properties of these compounds were studied by ultraviolet, nuclear magnetic resonance, circular dichroism and the 2'-substituted isomers were found to have more stacked structures than the 3'-isomers.

  通过将尿苷、N-苯甲酰胞苷、N-苯甲酰腺苷和N-异丁酰鸟苷分别与邻硝基苯基二氮甲烷处理，然后进行分离和去阻断，合成了尿苷、胞苷、腺苷和鸟苷的2'-和3'-O-(邻硝基苯甲基)衍生物。3'-O-(邻硝基苯甲基)鸟苷是一种新型化合物。通过使用N-酰化核苷，使在硅胶上分离2'-和3'-取代异构体成为可能，这些化合物是合成寡核糖核苷酸的有用中间体。通过紫外线、核磁共振、圆二色性等方法研究了这些化合物的一些物理性质，发现2'-取代异构体比3'-异构体具有更紧密的堆积结构。
• Syntheses of Phospholipids Containing 2-Nitrobenzyl Ester Moieties at the Terminals of Alkyl Chains and Properties of Photodegradable Liposomes from the Lipids
  作者：Kazuo Yamaguchi、Yoshihiro Tsuda、Taka-aki Shimakage、Akihiro Kusumi

  DOI：10.1246/bcsj.71.1923

  日期：1998.8

  Phospholipid 1a bearing 2-nitrobenzyl ester moieties as a photocleavable group at the terminal of alkyl chains was synthesized from the corresponding terminal carboxy-bearing phospholipid 2 by the reaction with 2-nitrophenyl-substituted diazomethane. Phospholipid, 1b bearing α-methyl-2-nitrobenzyl group, 1c bearing 4,5-dimethoxy-2-nitrobenzyl group, and 1d bearing α-methyl-4,5-dimethoxy-2-nitrobenzyl group were similarly synthesized by the use of the respective diazo compounds. The order of photolysis rates of 2-nitrobenzyl ester linkage of phospholipids by ultrahigh-pressure mercury lamp is 1b ≥ 1d > 1a > 1c. Liposomes of 1a—1d containing calcein in the inner aqueous layer were prepared by vortexing, sonication, and gel-filtration. UV irradiation resulted in fast release of the entrapped fluorescence dye. The order of release rates : 1b ≥ 1d > 1c > 1a is consistent with that of photolysis rates except for 1c, which has poor retention of the dye.

  合成了具有2-硝基苯甲酯基团的磷脂1a，该基团作为光分解基团位于烷基链的末端，通过与2-硝基苯基取代的叠氮甲烷反应，从对应的末端羧基含量磷脂2合成。磷脂1b（具有α-甲基-2-硝基苯甲基基团）、1c（具有4,5-二甲氧基-2-硝基苯甲基基团）和1d（具有α-甲基-4,5-二甲氧基-2-硝基苯甲基基团）也同样通过相应的叠氮化合物合成。通过超高压汞灯光分解的磷脂中2-硝基苯甲酯键的光解速率顺序为1b ≥ 1d > 1a > 1c。通过涡旋、超声波和凝胶过滤法制备了含有钙黄绿素的磷脂1a—1d的内水相的脂质体。紫外照射导致被捕获的荧光染料快速释放。释放速率的顺序为：1b ≥ 1d > 1c > 1a，这与光解速率的顺序一致，除了1c，其染料的保持效果较差。
• Studies on transfer ribonucleic acids and related compounds. XLI. Synthesis of tRNA fragments containing modified nucleosides.
  作者：EIKO OHTSUKA、JITSUHIRO MATSUGI、HIDEAKI TAKASHIMA、SHOICHI AOKI、TOSHIAKI WAKABAYASHI、TETSUO MIYAKE、MORIO IKEHARA

  DOI：10.1248/cpb.31.513

  日期：——

  tRNA fragments containing modified nucleosides have been synthesized either by condensation of nucleotides containing a modified base or by modification of oligonucleotides. Ribothymidine 3'-phosphate was prepared by condensation of the silylated base with protected D-ribose followed by phosphorylation. Ribothymidine-containing trimer, T-Ψ-C, was synthesized by the phosphodiester method. A ribothymidine-containing hexamer T-U-C-A-A-A and a 2'-O-methylcytidine containing hexamer C-G-G-G-Cm-Up were synthesized by the phosphotriester method. A dihydrouridine-containing trimer D-A-G and a 7-methylguanosine-containing trimer m7G-U-C were obtained by modification of the trimers by reduction and methylation, respectively.

  含有修饰核苷的 tRNA 片段是通过缩合含有修饰碱基的核苷酸或修饰寡核苷酸合成的。3'- 磷酸核苷酸是通过硅烷化碱基与受保护的 D-核糖缩合，然后进行磷酸化而制备的。含核糖胸苷的三聚体 T-Ψ-C 是用磷酸二酯法合成的。用磷酸二酯法合成了含核糖胸苷的六聚体 T-U-C-A-A-A 和含 2'-O- 甲基胞苷的六聚体 C-G-G-G-Cm-Up。通过还原和甲基化修饰三聚体，分别得到了含二氢尿苷的三聚体 D-A-G 和含 7-甲基鸟苷的三聚体 m7G-U-C。
• Photo-labile protecting agents and method
  申请人：MEDICAL RESEARCH COUNCIL

  公开号：EP0233403A1

  公开（公告）日：1987-08-26

  The invention provides diazo compounds having the formula XYCNN and their parent hydrazones, where X is an ortho-nitro aromatic group such as o-nitrophenyl and Y is a hydrocarbon group such as methyl. The hydrazones may be prepared by reacting the corresponding ketone with hydrazine and the diazo compounds by hydrazone oxidation. The diazo compound may be reacted with an organic compound having a reactive hydrogen atom such as phosphate, thiophosphate, phosphonate, carboxyl and phenol, to form a caged compound from which the original organic compound can be released by photolysis, eg in situ in a biological system. Preferred organic compounds are ATP and other nucleotides.

  本发明提供了具有式 XYCNN 的重氮化合物及其母体肼酮，其中 X 为邻硝基苯基等正硝基芳香基团，Y 为甲基等烃基团。肼酮可通过相应的酮与肼反应制备，重氮化合物可通过腙氧化反应制备。重氮化合物可与具有活性氢原子（如磷酸盐、硫代磷酸盐、膦酸盐、羧基和苯酚）的有机化合物反应，形成笼状化合物，原有机化合物可通过光解（如在生物系统中的原位光解）从中释放出来。首选的有机化合物是 ATP 和其他核苷酸。
• Tomioka, Hideo; Ichikawa, Naoki; Komatsu, Kazunori, Journal of the American Chemical Society, 1992, vol. 114, # 21, p. 8045 - 8053
  作者：Tomioka, Hideo、Ichikawa, Naoki、Komatsu, Kazunori

  DOI：——

  日期：——