甲基苯甲酸-α-¹³C | 110625-18-8

• 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: 甲基苯甲酸-α-¹³C
• 英文名称: -p-toluic acid
• 英文别名: p-toluic-carboxy-13C acid；4-Methylbenzoic-carboxy-13C acid；4-methylbenzoic acid
• CAS: 110625-18-8
• 化学式: C₈H₈O₂
• 分子量: 137.139
• InChiKey: LPNBBFKOUUSUDB-VJJZLTLGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  甲基苯甲酸-α-¹³C 在 乙基溴化镁 、 三苯基膦 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 为溶剂， 反应 18.17h， 生成 10-(dibutylboryl)-5-mesityl-1-(4-methylbenzoyl-carbonyl-13C)-9-[4-[2-(trimethylsilyl)ethynyl]benzoyl]dipyrromethane
  参考文献：
  名称：

  Meso-¹³C-Labeled Porphyrins for Studies of Ground-State Hole Transfer in Multiporphyrin Arrays

  摘要：

  Understanding electronic communication among interacting chromophores provides the foundation for a variety of applications. The ground-state electronic communication in diphenylethyne-linked zinc-porphyrin dyads has been investigated by a novel molecular design strategy that entails introduction of a C-13-atom (*) at specific sites of the porphyrins where there is substantial electron density in the relevant frontier (highest occupied) molecular orbital. The site of C-13 substitution is at a meso-position, either the site of attachment of the linker (proximal, "P") or the site trans to the linker (distal, "D"). The substituents (R) at the non-linking meso-positions are mesityl, tridec-7-yl ("swallowtail"), or p-tolyl groups. Altogether five isotopically labeled porphyrin dyads have been prepared. The hole/electron-transfer properties of one-electron oxidized dyads have been examined by electron paramagnetic resonance (EPR) spectroscopy. The introduction of the meso-C-13 label provides a "clock" (via the hyperfine interactions) that allows investigation of a time scale for hole transfer that is 3-4 times shorter than that provided by the natural abundance N-14 nuclei of the pyrrole nitrogen atoms. The EPR studies indicate that the hole transfer, which has been previously shown to be fast on the time scale of the N-14 hyperfine clock (similar to 220 ns), remains fast on the time scale of the C-13 hyperfine clock (similar to 50 ns).

  DOI：

  10.1021/jo070593x
• 作为产物：
  描述：

  C₇⁽¹³⁾CH₇N 在 硫酸 、 水 作用下， 反应 2.0h， 以1.41 g的产率得到甲基苯甲酸-α-¹³C
  参考文献：
  名称：

  Meso-¹³C-Labeled Porphyrins for Studies of Ground-State Hole Transfer in Multiporphyrin Arrays

  摘要：

  Understanding electronic communication among interacting chromophores provides the foundation for a variety of applications. The ground-state electronic communication in diphenylethyne-linked zinc-porphyrin dyads has been investigated by a novel molecular design strategy that entails introduction of a C-13-atom (*) at specific sites of the porphyrins where there is substantial electron density in the relevant frontier (highest occupied) molecular orbital. The site of C-13 substitution is at a meso-position, either the site of attachment of the linker (proximal, "P") or the site trans to the linker (distal, "D"). The substituents (R) at the non-linking meso-positions are mesityl, tridec-7-yl ("swallowtail"), or p-tolyl groups. Altogether five isotopically labeled porphyrin dyads have been prepared. The hole/electron-transfer properties of one-electron oxidized dyads have been examined by electron paramagnetic resonance (EPR) spectroscopy. The introduction of the meso-C-13 label provides a "clock" (via the hyperfine interactions) that allows investigation of a time scale for hole transfer that is 3-4 times shorter than that provided by the natural abundance N-14 nuclei of the pyrrole nitrogen atoms. The EPR studies indicate that the hole transfer, which has been previously shown to be fast on the time scale of the N-14 hyperfine clock (similar to 220 ns), remains fast on the time scale of the C-13 hyperfine clock (similar to 50 ns).

  DOI：

  10.1021/jo070593x

文献信息

• Palladium-Catalyzed Hydroxycarbonylation of Aryl and Vinyl Halides or Triflates by Acetic Anhydride and Formate Anions
  作者：Sandro Cacchi、Giancarlo Fabrizi、Antonella Goggiamani

  DOI：10.1021/ol0354371

  日期：2003.11.1

  [reaction: see text] The palladium-catalyzed reaction of aryl and vinyl halides or triflates in the presence of acetic anhydride and lithium formate as a condensed source of carbon monoxide provides an efficient simple route to the synthesis of the corresponding carboxylic acids. The reaction proceeds very smoothly under mild conditions and tolerates a wide range of functional groups, including ether

  [反应：参见正文]在乙酸酐和甲酸锂作为一氧化碳的缩合来源的情况下，芳基和乙烯基卤化物或三氟甲磺酸酯的钯催化反应为合成相应的羧酸提供了一条有效的简单途径。该反应在温和条件下进行得非常顺利，并且可以耐受各种官能团，包括醚，酮，酯和硝基。邻位取代基的存在不妨碍反应。可以通过使用H（13）COONa轻松制备标记的羰基产品。
• Dynamics for Reaction of an Ion Pair in Aqueous Solution:  Reactivity of Carboxylate Anions in Bimolecular Carbocation−Nucleophile Addition and Unimolecular Ion Pair Collapse
  作者：Yutaka Tsuji、Tetsuo Mori、John P. Richard、Tina L. Amyes、Mizue Fujio、Yuho Tsuno

  DOI：10.1021/ol015706s

  日期：2001.4.1

  [reaction: see text]. The sum of the rate constants for solvolysis and 18O-scrambling of 4-MeC6H4(13)CH(Me)18OC(O)C6F5 in 50/50 (v/v) trifluoroethanol/water, k(solv) + k(iso) = 1.22 x 10(-5) s(-1), is larger than k(solv) = 1.06 x 10(-5) s(-1) for solvolysis of the unlabeled ester. This shows that the ion pair intermediate undergoes significant internal return. The data give k(-1) = 7 x 10(9) s(-1)

  [反应：请参见文字]。在50/50（v / v）三氟乙醇/水中（k（solv）+ k（iso））中4-MeC6H4（13）CH（Me）18OC（O）C6F5的溶剂分解和18O加扰速率常数的总和对于未标记的酯而言，= 1.22 x 10（-5）s（-1）大于k（solv）= 1.06 x 10（-5）s（-1）。这表明离子对中间体经历显着的内部返回。数据给出了k（-1）= 7 x 10（9）s（-1）通过离子对的单分子塌陷进行内部返回的结果，该值显着大于k（Nu）= 5 x 10（8）M（- 1）xs（-1），用于将羧酸根阴离子双分子亲核加成到4-MeC6H4CH（Me）+。
• Thermal isomerization of benzocyclobutene
  作者：Orville L. Chapman、Uh Po Eric Tsou、Jeffery W. Johnson

  DOI：10.1021/ja00236a038

  日期：1987.1
• Structural Isomers of Aryl-Substituted <i>η</i>³-Propargyl Complexes:  <i>η</i>²-1-Metalla(methylene)cyclopropene and <i>η</i>³-Benzyl Complexes
  作者：Charles P. Casey、Timothy M. Boller、Stefan Kraft、Ilia A. Guzei

  DOI：10.1021/ja020439m

  日期：2002.11.1

  Hydride abstraction from C5Me5(CO)(2)Re(eta(2)-PhCequivalent toCCH(2)Ph) (1) gave a 3:1 mixture of eta(3)-propargyl complex [C5Me5(CO)(2)Re(eta(3)-PhCH-Cequivalent toCPh)][BF4] (5) and eta(2)-1 -metalla(methylene)cyclopropene complex [C5Me5(CO)(2)Re(eta(2)-PhC-C=CHPh)][BF4] (6). Observation of the eta(2)-isomer requires 1,3-diaryl substitution and is favored by electron-donating substituents on the C-3-aryl ring. Interconversion of eta(3)-propargyl and eta(2)-1-metalla(methylene)cyclopropene complexes is very rapid and results in coalescence of Cp-* H-1 NMR resonances at about -50 degreesC. Protonation of the alkynyl carbene complex C5Me5(CO)(2)Re=C(Ph)Cequivalent toCPh (22) gave a third isomer, the eta(3)-benzyl complex C5Me5(CO)(2)Re[eta(3)(alpha,1,2)-endo,syn-C6H5CH(Cequivalent toCC(6)H(5))]}-[BF4] (23) along with small amounts of the isomeric complexes 5 and 6. While 5 and 6 are in rapid equilibrium, there is no equilibration of the eta(3)-benzyl isomer 23 with 5 and 6.