4-(4',5'-dimethoxy-α'-methyl-2'-nitrobenzyloxycarbonyloxy)-3,5-dimethylbenzyl chloride | 250292-79-6

• 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: 4-(4',5'-dimethoxy-α'-methyl-2'-nitrobenzyloxycarbonyloxy)-3,5-dimethylbenzyl chloride
• 英文别名: 4-(a'-methyl-2'-nitro-4'-5'-dimethoxybenzyloxycarbonyloxy)-3,5-dimethylbenzyl chloride；[4-(Chloromethyl)-2,6-dimethylphenyl] 1-(4,5-dimethoxy-2-nitrophenyl)ethyl carbonate
• CAS: 250292-79-6
• 化学式: C₂₀H₂₂ClNO₇
• 分子量: 423.85
• InChiKey: QJMLYJXGFLPMLW-UHFFFAOYSA-N

物化性质

• 沸点：
  583.6±50.0 °C(Predicted)
• 密度：
  1.278±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  99.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  4-(4',5'-dimethoxy-α'-methyl-2'-nitrobenzyloxycarbonyloxy)-3,5-dimethylbenzyl chloride 在 水 作用下， 以 乙腈 为溶剂， 生成 4-(4',5'-dimethoxy-α'-methyl-2'-nitrobenzyloxycarbonyloxy)-3,5-dimethylbenzyl alcohol
  参考文献：
  名称：

  Hydrolytic Stabilization of Protected p-Hydroxybenzyl Halides Designed as Latent Quinone Methide Precursors

  摘要：

  The hydrolysis rates of a series of protected p-hydroxybenzyl halides designed to generate a p-quinone methide through 1,6-elimination following photolytic deprotection have been investigated in order to optimize hydrolytic stability. A number of p-hydroxybenzyl halides containing an ether-or carbonate-linked photolabile hydroxy protecting group and a fluoride, chloride, or bromide benzylic leaving group have been synthesized. The hydrolysis rates of these derivatives in different water/acetonitrile mixtures and temperatures have been determined. The hydrolysis half-life of the benzyl bromide with the p-hydroxy protected as the carbonate-linked alpha-methylnitroveratryl (18c) is more than 750 times that of the ether-linked analogue (16c). These studies afford a Hammett sigma(p)(+) of +0.28 for the carbonate-linked derivatives compared to a sigma(p)(+) of -0.39 for the ether-linked derivatives. The theoretical hydrolysis half-life of the most stable benzyl fluoride in 100% water was sufficiently long so as to preclude extrapolation, while the chloride was approximately 50 h, and even the bromide was estimated to be nearly 5 h.

  DOI：

  10.1021/jo991085t
• 作为产物：
  描述：

  1-(4,5-二甲氧基-2-硝基苯基)乙酮 在 吡啶 、 sodium tetrahydroborate 、 三光气 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 20.75h， 生成 4-(4',5'-dimethoxy-α'-methyl-2'-nitrobenzyloxycarbonyloxy)-3,5-dimethylbenzyl chloride
  参考文献：
  名称：

  Hydrolytic Stabilization of Protected p-Hydroxybenzyl Halides Designed as Latent Quinone Methide Precursors

  摘要：

  The hydrolysis rates of a series of protected p-hydroxybenzyl halides designed to generate a p-quinone methide through 1,6-elimination following photolytic deprotection have been investigated in order to optimize hydrolytic stability. A number of p-hydroxybenzyl halides containing an ether-or carbonate-linked photolabile hydroxy protecting group and a fluoride, chloride, or bromide benzylic leaving group have been synthesized. The hydrolysis rates of these derivatives in different water/acetonitrile mixtures and temperatures have been determined. The hydrolysis half-life of the benzyl bromide with the p-hydroxy protected as the carbonate-linked alpha-methylnitroveratryl (18c) is more than 750 times that of the ether-linked analogue (16c). These studies afford a Hammett sigma(p)(+) of +0.28 for the carbonate-linked derivatives compared to a sigma(p)(+) of -0.39 for the ether-linked derivatives. The theoretical hydrolysis half-life of the most stable benzyl fluoride in 100% water was sufficiently long so as to preclude extrapolation, while the chloride was approximately 50 h, and even the bromide was estimated to be nearly 5 h.

  DOI：

  10.1021/jo991085t

文献信息

• Biomolecular labeling
  申请人：University of Arkansas

  公开号：US06657052B1

  公开（公告）日：2003-12-02

  A method for using an organic compound to label polynucleotides is described. The method utilizes an organic compound including an oligonucleotide, and electrophilic active site, an active complex, and a phosphate binding site. The oligonucleotide has a sequence that is complimentary to a specific region of a polynucleotide. This facilitates labeling of DNA or RNA at a specific site in its sequence. The active site consists of a stable precursor, and only becomes reactive upon activation. Leaving and protecting functional groups may be attached to the active site in order to facilitate the formation of a stable precursor and subsequent activation. The active complex may be a drug, polypeptide or a reporter molecule such as an isotope or fluorescing compound. The phosphate binding sites may be any functional group capable of forming ionic bonds with phosphate oxygens. Nucleotide labeling using this compound does not interfere with a polynucleotide sequence. The described method for utilizing this compound may be performed in situ. Latent reactivity is utilized to make the reaction chemically specific, alkylating only phosphodiester groups on the polynucleotide. A lactonization reaction traps the trialkylphosphate in a stable form.

  描述了一种使用有机化合物标记多聚核苷酸的方法。该方法利用包括寡核苷酸、亲电活性位点、活性复合物和磷酸结合位点的有机化合物。寡核苷酸具有与多聚核苷酸特定区域互补的序列。这有助于在其序列中特定位置标记DNA或RNA。活性位点由稳定的前体组成，在激活后才变得活性。为了促进稳定前体的形成和随后的激活，可以连接离去和保护性功能基团到活性位点。活性复合物可以是药物、多肽或报告分子，如同位素或荧光化合物。磷酸结合位点可以是任何能够与磷酸氧形成离子键的功能基团。使用这种化合物进行核苷酸标记不会干扰多聚核苷酸序列。描述的利用该化合物的方法可以在原位进行。潜在的反应性用于使反应在化学上具有特异性，仅烷化多聚核苷酸上的磷酸二酯基团。内酯化反应将三烷基磷酸酯固定在稳定形式中。
• US6657052B1
  申请人：——

  公开号：US6657052B1

  公开（公告）日：2003-12-02
• Hydrolytic Stabilization of Protected <i>p</i>-Hydroxybenzyl Halides Designed as Latent Quinone Methide Precursors
  作者：Robert G. Dyer、Kenneth D. Turnbull

  DOI：10.1021/jo991085t

  日期：1999.10.1

  The hydrolysis rates of a series of protected p-hydroxybenzyl halides designed to generate a p-quinone methide through 1,6-elimination following photolytic deprotection have been investigated in order to optimize hydrolytic stability. A number of p-hydroxybenzyl halides containing an ether-or carbonate-linked photolabile hydroxy protecting group and a fluoride, chloride, or bromide benzylic leaving group have been synthesized. The hydrolysis rates of these derivatives in different water/acetonitrile mixtures and temperatures have been determined. The hydrolysis half-life of the benzyl bromide with the p-hydroxy protected as the carbonate-linked alpha-methylnitroveratryl (18c) is more than 750 times that of the ether-linked analogue (16c). These studies afford a Hammett sigma(p)(+) of +0.28 for the carbonate-linked derivatives compared to a sigma(p)(+) of -0.39 for the ether-linked derivatives. The theoretical hydrolysis half-life of the most stable benzyl fluoride in 100% water was sufficiently long so as to preclude extrapolation, while the chloride was approximately 50 h, and even the bromide was estimated to be nearly 5 h.