C-(3-fluorophenyl)-N-tert-butylnitrone | 139607-30-0

• 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: C-(3-fluorophenyl)-N-tert-butylnitrone
• 英文别名: (Z)-N-3-fluorobenzylidene-t-butanamine oxide；N-tert-butyl-1-(3-fluorophenyl)methanimine oxide
• CAS: 139607-30-0
• 化学式: C₁₁H₁₄FNO
• 分子量: 195.237
• InChiKey: IIUMYGRCEAEUFA-JYRVWZFOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  28.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  溴氟乙酸乙酯 、 C-(3-fluorophenyl)-N-tert-butylnitrone 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以43%的产率得到4-bromo-2-(t-butyl)-4-fluoro-3-(3-fluorophenyl)isoxazolidin-5-one
  参考文献：
  名称：

  氟代链烷酸酯和氟化异恶唑烷酮的立体选择性合成：控制亚硝基双反应性的N-取代基

  摘要：

  α-氟链烯酸酯和4-氟-5-异恶唑烷酮因其潜在的生物学应用而备受关注。现在，我们通过硝酮与α-氟代-α-溴乙酸酯之间的反应证明（E）-α-氟代链烯酸酯和4-氟代-5-异恶唑烷酮的合成。通过改变硝酮中的N-取代基，可以实现高化学选择性和立体选择性，分别获得（E）-α-氟代链烯酸酯和4-氟-5-异恶唑烷酮。已经进行了实验和计算研究以阐明反应机理。线性自由能关系研究进一步表明，N取代基效应主要是电子起源的。

  DOI：

  10.1002/chem.201303509
• 作为产物：
  描述：

  N-叔丁基羟胺盐酸盐 、 3-氟苯甲醛 以 吡啶 为溶剂， 反应 36.0h， 以89%的产率得到C-(3-fluorophenyl)-N-tert-butylnitrone
  参考文献：
  名称：

  Electronic properties of the nitrone substituent. Stabilization of benzylic carbocations

  摘要：

  The nitrone substituent CH=N(O) t-Bu is electron-withdrawing with a Taft sigma (1) value of 0.20. It also retards the solvolysis rate of a cumyl chloride when placed in the meta-position (sigma (+) = 0.20). However, CH=N(O) t-Bu becomes weakly cation stabilizing when placed in the para-position of a cumyl cation (sigma (+) = -0.04). This weak cation stabilization is a result of a conjugative interaction which delocalizes charge and offsets the inductive effect of the nitrone. When the nitrone is placed in the para-position, but then twisted out of conjugation with the aromatic ring by incorporation of flanking 3,5-dimethyl groups, it again retards solvolysis rates. Computational studies (B3LYP/6-31G*) show that the nitrone substituent stabilizes a para-substituted benzyl cation relative to the meta-substituted analog by a conjugative interaction. However, the calculated stabilization greatly overestimates the cation stabilization seen in solvolytic reactions. Copyright (C) 2001 John Wiley & Sons, Ltd.

  DOI：

  10.1002/1099-1395(200102)14:2<97::aid-poc340>3.0.co;2-2

文献信息

• COMPOSITIONS AND METHODS OF INHIBITING RETINAL DEGENERATION
  申请人：Anderson Robert E.

  公开号：US20130225694A1

  公开（公告）日：2013-08-29

  Nitrone-based compositions are disclosed that may be utilized for the prevention and treatment of a variety of ophthalmic diseases or conditions where RPE65 protein isomerohydrolase is implicated. Methods of production and use of said nitrone-based compositions, as well as pharmaceutical and ophthalmic compositions containing same, are disclosed.

  公开了基于亚硝基的组合物，可用于预防和治疗多种眼科疾病或条件，其中涉及RPE65蛋白异构酶。公开了生产和使用上述亚硝基组合物的方法，以及包含同样组合物的制药和眼科组合物。
• NITRONE DERIVATIVES
  申请人：SUMITOMO PHARMACEUTICALS COMPANY, LIMITED

  公开号：EP0945426A1

  公开（公告）日：1999-09-29

  A compound represented by the figure (1) or a pharmaceutically acceptable salt thereof is useful as a medicament for treating retinal degenerative disorders: wherein Ar is optionally substituted phenyl or optionally substituted heteroaryl;. n is 0, 1 or 2; W is -CH2NH- or -CH=N(O)-; R1, R2 and R3 are independently optionally substituted alkyl, carboxyl or alkoxycarbonyl; any two groups of R1, R2 and R3 may be taken together with the carbon atom to form optionally substituted cycloalkane; all of R1, R2 and R3 may be taken together with the adjusent carbon atom to form optionally substituted bicycloalkane or optionally substituted tricycloalkane; R4 and R5 are independently hydrogen atom or optionally substituted alkyl.

  图（1）所代表的化合物或其药学上可接受的盐可作为治疗视网膜变性疾病的药物： 其中 Ar 是任选取代的苯基或任选取代的杂芳基；. n 是 0、1 或 2； W是-CH2NH-或-CH=N(O)-； R1、R2 和 R3 独立地是任选取代的烷基、羧基或烷氧基羰基；R1、R2 和 R3 中的任意两个基团可与碳原子结合形成任选取代的环烷；所有 R1、R2 和 R3 可与相邻碳原子结合形成任选取代的双环烷或任选取代的三环烷； R4 和 R5 独立地为氢原子或任选取代的烷基。
• Electronic properties of the nitrone substituent. Stabilization of benzylic carbocations
  作者：Xavier Creary、Kresna Hartandi

  DOI：10.1002/1099-1395(200102)14:2<97::aid-poc340>3.0.co;2-2

  日期：2001.2

  The nitrone substituent CH=N(O) t-Bu is electron-withdrawing with a Taft sigma (1) value of 0.20. It also retards the solvolysis rate of a cumyl chloride when placed in the meta-position (sigma (+) = 0.20). However, CH=N(O) t-Bu becomes weakly cation stabilizing when placed in the para-position of a cumyl cation (sigma (+) = -0.04). This weak cation stabilization is a result of a conjugative interaction which delocalizes charge and offsets the inductive effect of the nitrone. When the nitrone is placed in the para-position, but then twisted out of conjugation with the aromatic ring by incorporation of flanking 3,5-dimethyl groups, it again retards solvolysis rates. Computational studies (B3LYP/6-31G*) show that the nitrone substituent stabilizes a para-substituted benzyl cation relative to the meta-substituted analog by a conjugative interaction. However, the calculated stabilization greatly overestimates the cation stabilization seen in solvolytic reactions. Copyright (C) 2001 John Wiley & Sons, Ltd.
• Synthesis and characterization of phenyl-substituted C-phenyl-N-tert-butylnitrones and some of their radical adducts
  作者：Randall D. Hinton、Edward G. Janzen

  DOI：10.1021/jo00035a020

  日期：1992.4

  Synthesis of C-phenyl-N-tert-butylnitrone (PBN) and several of its analogues with substituents in the 2-, 3-, or 4-position on the phenyl ring is described. While a one-pot reduction/condensation method proved suitable for most compounds, it was necessary to prepare some examples by direct condensation or through oxidation of the appropriate imine. The H-1 NMR data for the 3-X- and 4-X-PBN's can be correlated with the Hammett equation. For the 3-X series DELTA-delta for the alpha-proton correlates best with sigma(+) and has a correlation coefficient of 0.90. For the 4-X series a dual substituent parameter equation using sigma(R)0 gives the best correlation with r = 0.99. The hyperfine splitting constants (hfsc's) of the HO. and HOO. adducts of several substituted PBN's are also included and their correlation with the Hammett equation is discussed.
• US6194461B1
  申请人：——

  公开号：US6194461B1

  公开（公告）日：2001-02-27