N-(2-fluoroethyl)-N-methyl-aniline | 120977-75-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-(2-fluoroethyl)-N-methyl-aniline
• 英文别名: N-(2-Fluoroethyl)-N-methylaniline
• CAS: 120977-75-5
• 化学式: C₉H₁₂FN
• 分子量: 153.199
• InChiKey: QXVOKNXEWIVGLN-UHFFFAOYSA-N

物化性质

• 沸点：
  212.4±15.0 °C(Predicted)
• 密度：
  1.025±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  甲醇 、 N-(2-fluoroethyl)-N-methyl-aniline 在 氢氧化钾 作用下， 以84%的产率得到N-(2-Fluoroethyl)-N-(methoxymethyl)aniline
  参考文献：
  名称：

  Electrolytic Reactions of Fluoroorganic Compounds. 14. Regioselective Anodic Methoxylation of N-(Fluoroethyl)amines. Preparation of Highly Useful Fluoroalkylated Building Blocks

  摘要：

  Anodic methoxylation of various types of N-(fluoroethyl)amines, ArRNCH(2)R(f) (R(f) = CF3, CHF2, CH2F, etc.) has been systematically studied and it was found that a methoxy group was exclusively or preferentially introduced into the position a to the fluoromethyl (R(f)) group, depending on the R(f) and R groups. The effect of the R(f) group on the promotion of the anodic alpha-methoxylation decreased in the order CF3, CHF2, and CH2F. This remarkable promotion effect and unique regioselectivity can be explained mainly in terms of the alpha-CH kinetic acidities of the cation radicals formed by one-electron oxidation of the amines. The alpha-methoxylated products are highly useful precursors for the construction of carbon-carbon bonds alpha to the trifluoromethyl and difluoromethyl groups, which is difficult by other methods.

  DOI：

  10.1021/jo00082a018
• 作为产物：
  描述：

  2-(N-methylanilino)ethyl methanesulfonate 在 potassium fluoride 、 2C₁₆H₃₆N⁽¹⁺⁾*C₂H₄O₆S₂^(2-) 作用下， 以 水 、 叔丁醇 为溶剂， 反应 4.0h， 以93%的产率得到N-(2-fluoroethyl)-N-methyl-aniline
  参考文献：
  名称：

  使用氟化钾进行不平衡离子对催化的亲核氟化

  摘要：

  不平衡的离子对促进剂（例如，四丁基硫酸铵）由大体积的电荷离域阳离子和小电荷局部阴离子组成，使用易于处理的 KF 极大地加速了亲核氟化。我们还成功地将廉价且市售的离子交换树脂转化为聚合物负载的离子对促进剂 (A26–SO 4 2– )，过滤后可重复使用。此外，A26–SO 4 2–可用于连续流动条件。在我们的条件下，水的耐受性良好。

  DOI：

  10.1021/acs.orglett.1c03887

文献信息

• Substitution-reduction: an alternative process for the[18F]N-(2-fluoroethylation) of anilines
  作者：Emmanuelle Briard、Victor W. Pike

  DOI：10.1002/jlcr.816

  日期：2004.3.30

  Substitution of a halo atom (chloro or bromo) in easily prepared N-haloacetyl-anilines with no-carrier added (NCA) cyclotron-produced [18F]fluoride ion (18F, t1/2= 109.8 min; β+=96.9%), followed by reduction with borane–tetrahydrofuran (BH3–THF), provides an alternative route to NCA [18F]N-(2-fluoroethyl)-anilines. This two-step and one-pot process is rapid (∼50 min) and moderately high yielding (∼40% decay-corrected radiochemical yield (RCY) overall). In the nucleophilic substitution reaction, 18-crown-6 is preferred to Kryptofix® 222 as complexing agent for the solubilization of the counter-ion (K+), derived from an added metal salt, in acetonitrile. Weakly basic potassium bicarbonate is preferred as the added metal salt. Inclusion of a small amount of water, equating to 4–5 molar equivalents relative to 18-crown-6, base or precursor (held in equimolar ratio), is beneficial in preventing the adsorption of radioactivity onto the wall of the glass reaction vessel and for achieving high RCY in the nucleophilic substitution reaction. BH3–THF is effective for the rapid reduction of the generated [18F]N-fluoroacetyl-aniline to the [18F]N-(2-fluoroethyl)-aniline. Copyright © 2004 John Wiley & Sons, Ltd.

  用无载体添加（NCA）回旋加速器产生的[18F]氟离子（18F，t1/2= 109.8 分钟；β+=96.9%）取代容易制备的 N-卤乙酰基苯胺中的卤原子（氯或溴），然后用硼烷-四氢呋喃（BH3-THF）还原，为 NCA [18F]N-(2-fluoroethyl)-anilines 提供了另一条途径。这种两步一锅的工艺快速（∼50 分钟），产率适中（总体衰变校正放射化学产率（RCY）∼40%）。在亲核取代反应中，18-crown-6 比 Kryptofix® 222 更适合作为络合剂，用于在乙腈中溶解由添加的金属盐产生的反离子（K+）。添加的金属盐以弱碱性碳酸氢钾为佳。加入少量水（相当于 18-冠醚-6、碱或前体（以等摩尔比保持）的 4-5 摩尔当量）有利于防止放射性吸附到玻璃反应容器壁上，并在亲核取代反应中获得高 RCY。BH3-THF 能有效地将生成的[18F]N-氟乙酰基苯胺快速还原为[18F]N-（2-氟乙基）苯胺。Copyright © 2004 John Wiley & Sons, Ltd. All Rights Reserved.
• Unbalanced-Ion-Pair-Catalyzed Nucleophilic Fluorination Using Potassium Fluoride
  作者：Wangbing Li、Zhichao Lu、Gerald B. Hammond、Bo Xu

  DOI：10.1021/acs.orglett.1c03887

  日期：2021.12.17

  An unbalanced ion pair promoter (e.g., tetrabutylammonium sulfate), consisting of a bulky and charge-delocalized cation and a small and charge-localized anion, greatly accelerates nucleophilic fluorinations using easy handling KF. We also successfully converted an inexpensive and commercially available ion-exchange resin to the polymer-supported ion pair promoter (A26–SO42–), which could be reused

  不平衡的离子对促进剂（例如，四丁基硫酸铵）由大体积的电荷离域阳离子和小电荷局部阴离子组成，使用易于处理的 KF 极大地加速了亲核氟化。我们还成功地将廉价且市售的离子交换树脂转化为聚合物负载的离子对促进剂 (A26–SO 4 2– )，过滤后可重复使用。此外，A26–SO 4 2–可用于连续流动条件。在我们的条件下，水的耐受性良好。
• Electrolytic Reactions of Fluoroorganic Compounds. 14. Regioselective Anodic Methoxylation of N-(Fluoroethyl)amines. Preparation of Highly Useful Fluoroalkylated Building Blocks
  作者：Toshio Fuchigami、Shinji Ichikawa

  DOI：10.1021/jo00082a018

  日期：1994.2

  Anodic methoxylation of various types of N-(fluoroethyl)amines, ArRNCH(2)R(f) (R(f) = CF3, CHF2, CH2F, etc.) has been systematically studied and it was found that a methoxy group was exclusively or preferentially introduced into the position a to the fluoromethyl (R(f)) group, depending on the R(f) and R groups. The effect of the R(f) group on the promotion of the anodic alpha-methoxylation decreased in the order CF3, CHF2, and CH2F. This remarkable promotion effect and unique regioselectivity can be explained mainly in terms of the alpha-CH kinetic acidities of the cation radicals formed by one-electron oxidation of the amines. The alpha-methoxylated products are highly useful precursors for the construction of carbon-carbon bonds alpha to the trifluoromethyl and difluoromethyl groups, which is difficult by other methods.