2-methoxycarbonyl-5-(4'-nitrophenyloxy)tetrazole | 320603-23-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methoxycarbonyl-5-(4'-nitrophenyloxy)tetrazole
• 英文别名: methyl 5-(4-nitrophenoxy)tetrazole-2-carboxylate；2-methoxycarbonyl-5-(p-nitrophenoxy)tetrazole
• CAS: 320603-23-4
• 化学式: C₉H₇N₅O₅
• 分子量: 265.185
• InChiKey: DPZPONPNSMISDB-UHFFFAOYSA-N

物化性质

• 沸点：
  453.1±47.0 °C(Predicted)
• 密度：
  1.65±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  125
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-methoxycarbonyl-5-(4'-nitrophenyloxy)tetrazole 反应 72.0h， 生成 1-methyl-5-(4-nitrophenoxy)tetrazole 、 2-methyl-5-(4-nitrophenoxy)tetrazole
  参考文献：
  名称：

  Dabbagh; Mansoori; Jafary, Journal of Chemical Research - Part S, 2000, # 9, p. 442 - 445

  摘要：

  DOI：
• 作为产物：
  描述：

  氯甲酸甲酯 、 5-p-nitrophenoxytetrazole 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以72%的产率得到2-methoxycarbonyl-5-(4'-nitrophenyloxy)tetrazole
  参考文献：
  名称：

  摘要：

  The kinetics and mechanism of the N-2-N-1-isomerization of 2-methoxycarbonyl-5-(p-X-phenoxy)tetrazoles (X = H, CH3, NHCOCH3, Cl, Br, NO,) were studied by H-1 NMR spectroscopy in a DMSO-d(6)-CDCl3 mixture (25: 75). The rate of isomerization of the N-2-isomer into N-1-isomer fit the first-order equation (after three half-conversion periods). The isomerization is accompanied by hydrolysis and decarboxylation. The Hammett plot of ln(k(x)/k(H)) for the isomerization showed a good correlation with sigma(-) values (p(-) = 1.33, r = 0.965). A poor correlation with sigma values was obtained. The kinetic data, the effect of solvent polarity, the substituent effects, and the results of AMI quantum-chemical calculations suggest an ionic mechanism of the isomerization in polar solvents and a concerted mechanism in nonpolar solvents.

  DOI：

  10.1023/a:1013947228772

文献信息

• Reaction of 5-Aryloxytetrazoles with Dimethyl Sulfoxide and DMSO-Acetic Anhydride. Structure and Quantum-Chemical Calculations of 1-Methylsulfanylmethyl-5-(4-nitrophenoxy)tetrazole
  作者：H. A. Dabbagh、N. Noroozi Pesyan、A. Bagheri、S. Takemo、H. Hayashi

  DOI：10.1007/s11178-005-0293-9

  日期：2005.7

  Decomposition of methyl 5-(4-nitrophenoxy)tetrazole-2-carboxylate in dimethyl sulfoxide at room temperature yields a mixture of 1-methylsulfanylmethyl-5-(4-nitrophenoxy)tetrazole, 1- and 2-methyl-5-(4-nitrophenoxy)tetrazoles, and 5-(4-nitrophenoxy)tetrazole. Methyl 5-aryloxytetrazole-2-carboxylates containing electron-donor substituents in the aryloxy group do not give rise to the corresponding products under analogous conditions. The reactions of 5-aryloxytetrazoles [Ar = 4-O2NC6H4, C6H5, 2,6-(MeO)2C6H3] with dimethyl sulfoxide in the presence of acetic anhydride lead to mixtures of 1- and 2-methylsulfanylmethyl-5-aryloxytetrazoles whose yield and ratio depend on the substituent in the aryloxy group. The structure of 1-methylsulfanylmethyl-5-(4-nitrophenoxy)tetrazole was studied by X-ray analysis, two-dimensional NMR spectroscopy (HSQC, HMBC, NOESY), and quantum-chemical methods (ab initio, AM1, PM3). A highly selective procedure was developed for the synthesis of 5-(4-nitrophenoxy)tetrazole.

  在室温下，甲基5-(4-硝基苯氧基)四唑-2-羧酸酯在二甲基亚砜中的分解反应生成1-甲硫基甲基-5-(4-硝基苯氧基)四唑、1-和2-甲基-5-(4-硝基苯氧基)四唑以及5-(4-硝基苯氧基)四唑的混合物。含有供电子取代基的芳氧基团的甲基5-芳氧基四唑-2-羧酸酯在类似条件下不会生成相应的产物。在乙酸酐存在下，5-芳氧基四唑[Ar = 4-O2NC6H4, C6H5, 2,6-(MeO)2C6H3]与二甲基亚砜的反应生成1-和2-甲硫基甲基-5-芳氧基四唑的混合物，其产率和比例取决于芳氧基团上的取代基。通过X射线分析、二维核磁共振光谱（HSQC, HMBC, NOESY）和量子化学方法（从头计算法，AM1, PM3）研究了1-甲硫基甲基-5-(4-硝基苯氧基)四唑的结构。开发了一种高度选择性的5-(4-硝基苯氧基)四唑合成方法。
• A one-pot synthesis and X-ray crystallographic and computational analyses of methyl-2,4-dimethoxysalicylate — a potential anti-tumour agent
  作者：Hossein A Dabbagh、Nader Noroozi-Pesyan、Brian O Patrick、Brian R James

  DOI：10.1139/v04-113

  日期：2004.7.1

  The thermal decarboxylation of 2-methoxycarbonyl-5-(4′-nitrophen-oxy)tetrazole (1a) with the electron-rich, aromatic compounds (anisole, N,N-dimethylaniline, 1,4-dimethoxybenzene, and 1,3,5-trimethoxybenzene), neat or in polar solvents (DMSO, DMF, and CH₃CN), is investigated. The solid phase thermal decomposition of a mixture of 1a, 1,3,5-trimethoxybenzene, and a Lewis acid (AlCl₃) produces methyl-2,4-dimethoxysalicylate (8) in good yield, instead of the expected 2,4,6-trimethoxybenzoic acid. The X-ray structure of 8 shows intramolecular hydrogen bonds between the carbonyl oxygen and hydrogens of Me and OH groups. A measured pK_a value of 6.8 compares well with a value of 6.4 estimated using the [C=O···H···O] hydrogen bond distances.Key words: anti–tumor, novel synthesis, X-ray structure, hydrogen bonds, computational analysis.

  本文研究了2-甲氧羰基-5-(4'-硝基苯氧基)四唑（1a）与富电子芳香化合物（甲氧基苯、N,N-二甲基苯胺、1,4-二甲氧基苯和1,3,5-三甲氧基苯）在无溶剂或极性溶剂（DMSO、DMF和CH3CN）中的热脱羧反应。将1a、1,3,5-三甲氧基苯和Lewis酸（AlCl3）混合物的固相热分解产物为甲基-2,4-二甲氧基水杨酸酯（8），而不是预期的2,4,6-三甲氧基苯甲酸。8的X射线结构显示了羰基氧原子与Me和OH基团的氢键内部作用。实测pKa值为6.8，与使用[C=O···H···O]氢键距离估计的值6.4相符。关键词：抗肿瘤、新型合成、X射线结构、氢键、计算分析。
• ——
  作者：H. A. Dabbagh、Ya. Mansoori

  DOI：10.1023/a:1013947228772

  日期：——

  The kinetics and mechanism of the N-2-N-1-isomerization of 2-methoxycarbonyl-5-(p-X-phenoxy)tetrazoles (X = H, CH3, NHCOCH3, Cl, Br, NO,) were studied by H-1 NMR spectroscopy in a DMSO-d(6)-CDCl3 mixture (25: 75). The rate of isomerization of the N-2-isomer into N-1-isomer fit the first-order equation (after three half-conversion periods). The isomerization is accompanied by hydrolysis and decarboxylation. The Hammett plot of ln(k(x)/k(H)) for the isomerization showed a good correlation with sigma(-) values (p(-) = 1.33, r = 0.965). A poor correlation with sigma values was obtained. The kinetic data, the effect of solvent polarity, the substituent effects, and the results of AMI quantum-chemical calculations suggest an ionic mechanism of the isomerization in polar solvents and a concerted mechanism in nonpolar solvents.
• Dabbagh; Mansoori; Jafary, Journal of Chemical Research - Part S, 2000, # 9, p. 442 - 445
  作者：Dabbagh、Mansoori、Jafary、Rostami

  DOI：——

  日期：——