4-甲基苯磺酸2-氟苯酯 | 4416-66-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 4-甲基苯磺酸2-氟苯酯
• 英文名称: 2-fluorophenyl 4-methylbenzenesulfonate
• 英文别名: (2-fluorophenyl) 4-methylbenzenesulfonate
• CAS: 4416-66-4
• 化学式: C₁₃H₁₁FO₃S
• mdl: MFCD10168450
• 分子量: 266.293
• InChiKey: MRHDJDZJOOZLDD-UHFFFAOYSA-N

物化性质

• 沸点：
  386.3±42.0 °C(Predicted)
• 密度：
  1.308±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.076
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2906299090

反应信息

• 作为反应物：
  描述：

  4-甲基苯磺酸2-氟苯酯 在 锰 、 NiBr₂bipy 、 三氟乙酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以69%的产率得到2,2-二氟联苯
  参考文献：
  名称：

  Dimerization of Aryl Sulfonates by in situ Generated Nickel(0)

  摘要：

  A mild and user-friendly nickel-catalyzed method for the reductive homocoupling of aromatic tosylates is presented. The reaction proceeds between room temperature and 60 degrees C, with stable substrates (ArOTs) easily prepared from inexpensive and commercially available phenols or naphthols. It relies on a catalytic amount (10 mol%) of a robust catalyst (NiBr(2)bipy) that does not require the preparation of sensitive organometallic intermediates. Yields are good to excellent.

  DOI：

  10.1055/s-0035-1560712
• 作为产物：
  描述：

  2-氟苯酚 、 对甲苯磺酰氯 在 三乙烯二胺 作用下， 以 二氯甲烷 为溶剂， 生成 4-甲基苯磺酸2-氟苯酯
  参考文献：
  名称：

  Copper-catalysed Coupling of Aryl Tosylates with Sodium Arylsulfinates

  摘要：

  以[Cu(CH3CN)4]PF6 为催化剂，可以轻松地从芳基对甲苯磺酸盐和芳基磺酸钠中高产合成二甲基砜衍生物。该转化过程高效、简单，且起始材料容易获得。

  DOI：

  10.3184/174751914x14117977782502

文献信息

• Direct Carboxylation of Aryl Tosylates by CO₂Catalyzed by In situ-Generated Ni⁰
  作者：Fatima Rebih、Manuel Andreini、Aurélien Moncomble、Anne Harrison-Marchand、Jacques Maddaluno、Muriel Durandetti

  DOI：10.1002/chem.201503926

  日期：2016.3.7

  A novel Ni0‐catalyzed carboxylation of aryl tosylates with carbon dioxide has been achieved under moderate temperatures and atmospheric pressure. In this procedure, the active Ni0 species is generated in situ by simply mixing the Ni0 precatalyst [NiBr2(bipy)] with an excess of manganese metal. This approach requires neither a glove‐box nor the tedious preparation of sophisticated intermediate organometallic

  在中等温度和大气压下，已经实现了新的Ni 0催化的甲苯磺酸芳基酯的羧化反应。在此过程中，只需将Ni 0预催化剂[NiBr 2（bipy）]与过量的锰金属混合即可就地生成活性Ni 0物质。这种方法既不需要手套箱，也不需要繁琐的复杂中间体有机金属衍生物的制备。这种温和，方便，用户友好的方法已成功应用于二氧化碳的增值和具有广泛取代基耐受性的通用反应物的合成。
• Enantioselective Intermolecular Heck and Reductive Heck Reactions of Aryl Triflates, Mesylates, and Tosylates Catalyzed by Nickel
  作者：Xiaolei Huang、Shenghan Teng、Yonggui Robin Chi、Wenqiang Xu、Maoping Pu、Yun‐Dong Wu、Jianrong Steve Zhou

  DOI：10.1002/anie.202011036

  日期：2021.2.8

  Nickel‐catalyzed intermolecular Heck reaction of cycloalkenes proceeds well with aryl triflates, mesylates and tosylates in excellent enantiomeric ratios. The asymmetric reductive Heck reaction also works with a 2‐cyclopentenone ketal, which is equivalent to conjugate arylation of the enone itself.

  镍催化的环烯烃的分子间Heck反应与芳基三氟甲磺酸酯，甲磺酸酯和甲苯磺酸酯的对映体比率极好。不对称的还原性Heck反应也适用于2-环戊烯酮缩酮，这相当于烯酮本身的共轭芳基化。
• Kinetic Study of Alkaline Hydrolysis of Substituted Phenyl Tosylates. XXII. Variation of Ortho Substituent Effect with Solvent
  作者：Vilve Nummert、Mare Piirsalu、Marika Lepp、Vahur Mäemets、Ilmar Koppel

  DOI：10.1135/cccc20050198

  日期：——

  The second-order rate constants k (dm³ mol^-1 s^-1) for the alkaline hydrolysis of meta-, para-, and ortho-substituted phenyl tosylates 4-CH₃C₆H₄SO₂OC₆H₄-X in aqueous 0.5 M Bu₄NBr have been measured spectrophotometrically in a wide temperature range. The log k values for ortho-substituted derivatives at various temperatures together with meta- and para-substituted derivatives were analyzed using the modified Fujita-Nishioka equation log k_m,p,ortho = c₀ + c_1(m,p,ortho)σ° + c_2(ortho)σ_I + c₃(1/T) + c_4(m,p,ortho)(1/T)σ° + c_5(ortho)(1/T)σ_I. In order to study the dependence of substituent effects, especially ortho inductive and resonance terms on different solvent parameters, the following equation was used: ∆log k_m,p,ortho = c₀ + c_1(m,p,ortho)σ° + c_2(ortho)σ_I + c₃∆E + c₄∆Y + c₅∆P + c_6(m,p,ortho)∆Eσ° + + c_7(m,p,ortho)∆Yσ° + c_8(m,p,ortho)∆Pσ° + c_9(ortho)∆Eσ_I + c_10(ortho)∆Yσ_I + c_11(ortho)∆Pσ_I. ∆log k = log k^X - log k^H, σ° and σ_I, are the Taft polar and inductive substituent constants, E, Y and P, are the solvent electrophilicity, polarity and polarizability parameters, respectively. In data treatment ∆E = E_S - E_H2O, ∆Y = Y_S - Y_H2O, ∆P = P_S - P_H2O were used. The solvent electrophilicity was found to be the main factor responsible for changes in the ortho, para, and meta polar substituent effects with medium. The variation of the ortho inductive term with the solvent electrophilicity E_S was found to be twice smaller than that for para substituents, while the ortho resonance term appeared to vary with solvent nearly similarly to that for para substituents. The ortho effect caused by the supplementary inductive effect from ortho position was found to disappear in a solvent whose electrophilic solvating power is comparable to pure DMSO (E ≈ 4).

  对于在水性0.5 M Bu4NBr中对4-CH3C6H4SO2OC6H4-X进行的邻位、间位和对位取代苯甲基对磺酸酯碱性水解的二阶速率常数k（dm3 mol-1 s-1）已经在广泛的温度范围内通过光谱法测量。各种温度下邻位取代衍生物的对数k值以及间位和对位取代衍生物已经使用改进的Fujita-Nishioka方程log km,p,ortho = c0 + c1(m,p,ortho)σ° + c2(ortho)σI + c3(1/T) + c4(m,p,ortho)(1/T)σ° + c5(ortho)(1/T)σI 进行分析。为了研究取代基效应的依赖性，尤其是对不同溶剂参数上的对位感应和共振项的依赖性，使用了以下方程：Δlog km,p,ortho = c0 + c1(m,p,ortho)σ° + c2(ortho)σI + c3ΔE + c4ΔY + c5ΔP + c6(m,p,ortho)ΔEσ° + c7(m,p,ortho)ΔYσ° + c8(m,p,ortho)ΔPσ° + c9(ortho)ΔEσI + c10(ortho)ΔYσI + c11(ortho)ΔPσI。Δlog k = log kX - log kH，σ°和σI，是Taft极性和归纳取代基常数，E，Y和P，是溶剂亲电性、极性和极化率参数，分别。在数据处理中ΔE = ES - EH2O，ΔY = YS - YH2O，ΔP = PS - PH2O。发现溶剂亲电性是导致对位、邻位和间位极性取代基效应变化的主要因素。随着溶剂亲电性ES的变化，对位感应项的变化比邻位取代基小了一倍，而对位共振项的变化似乎与邻位取代基几乎相似。由于来自对位位置的补充感应效应引起的对位效应被发现在其亲电性溶剂的溶剂化能力与纯DMSO相当时消失（E≈4）。
• Buchwald–Hartwig Amination of (Hetero)Aryl Tosylates Using a Well-Defined N-Heterocyclic Carbene/Palladium(II) Precatalyst
  作者：Yin Zhang、Guy Lavigne、Vincent César

  DOI：10.1021/acs.joc.5b01272

  日期：2015.8.7

  The cross-coupling of aryl tosylates with amines and anilines was achieved by using for the first time a Pd-NHC system based on the popular Pd-PEPPSI precatalyst platform in which the anchoring imidazol-2-ylidene ligand IPr(Nme2)2 incorporates two dimethylamino groups as backbone substituents enhancing both the electronic and steric properties of the carbene. The system optimization and its application scope are disclosed.
• Copper-catalysed Coupling of Aryl Tosylates with Sodium Arylsulfinates
  作者：Chunjie Wang、Hui Zhang、Zhiwei Li、Ziyun Wang

  DOI：10.3184/174751914x14117977782502

  日期：2014.11

  Diaryl sulfones derivatives were easily synthesised from aryl tosylates and sodium arylsulfinates in high yields using [Cu(CH₃CN)₄]PF₆ as catalyst. The transformation is efficient, simple and the starting materials are readily available.

  以[Cu(CH3CN)4]PF6 为催化剂，可以轻松地从芳基对甲苯磺酸盐和芳基磺酸钠中高产合成二甲基砜衍生物。该转化过程高效、简单，且起始材料容易获得。