2-Methyl-2-butyl trifluoroacetate | 461-73-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-Methyl-2-butyl trifluoroacetate
• 英文别名: Acetic acid, trifluoro-, 1,1-dimethylpropyl ester；2-methylbutan-2-yl 2,2,2-trifluoroacetate
• CAS: 461-73-4
• 化学式: C₇H₁₁F₃O₂
• 分子量: 184.158
• InChiKey: BTOHAHVYNSIQLJ-UHFFFAOYSA-N

物化性质

• 沸点：
  31 °C(Press: 50 Torr)
• 密度：
  1.122±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  2-甲基-丁烯 、 三氟乙酸 生成 2-Methyl-2-butyl trifluoroacetate
  参考文献：
  名称：

  Secondary and tertiary 2-methylbutyl cations. 2. Addition of trifluoroacetic acid to methylbutene

  摘要：

  The reaction of 8-methyl-1-butene (4), 2-methyl-1-butene (5), and 2-methyl-2-butene (6) in trifluoroacetic acid (TFA), neat or buffered with potassium trifluoroacetate, and in 74:26 TFA-MeCN was studied. Alkenes 5 and 6, which form a tertiary carbocation (2) upon hydronation, react 6.6 x 10(4) and 5.8 X 10(4) times faster than 4 (TFA-MeCN, 25 degrees C). The rates in TFA-d gave KIEs of 6.8 (4, 26.5 degrees C), ca. 5 (5, -18 degrees C), and 3.9 (6, -18 degrees C). The esters 3-methyl-2-butyl trifluoroacetate (7) and 2-methyl-2-butyl trifluoroacetate (8) are formed from 4 in the same ratio in TFA and in TFA-d (ca. 53:47),thus proving that 4 reacts entirely by a carbocationic mechanism, with no measurable contribution from a molecular addition. In the presence of p-toluenesulfonic acid the reaction of 4 at 0 degrees C forms significant amounts of 3-methyl-2-butyl tosylate (3), and the final ratio of 7:8 was close to that observed in the solvolysis of 3. The different product distributions in solvolyses and alkene hydronations observed before are brought about most probably by the different anions present in the tight ion pairs rather than by differences in the nature of the intermediate carbocations. The reaction in TFA-d showed that the 3-methyl-2-butyl cation (1) undergoes methyl shift to an extent (32%) smaller than in the solvolysis of the tosylate 3 before being trapped by the solvent. Extensive H/D exchange between the solvent and ester 8 prevented us from ascertaining whether skeletal rearrangement had occurred in the latter as well. Formation of the 2-methyl-2-butyl cation (2) from 5 and 6 is reversible, leading to partial isomerization of 5 to 6 in the initial stages of the reaction. Therefore the quoted rate ratios of 5 to 6 to 4 are minimum values. Hydron loss from the ethyl group of 2 is 9.3 +/- 1.8 faster than hydron loss from a methyl group. In 74:26 TFA-MeCN, cation 2 is trapped by the two solvents in a 12.6:1 ratio at 25 degrees C.

  DOI：

  10.1021/jo00080a026

文献信息

• Hypervalent Iodine-Based Activation of Triphenylphosphine for the Functionalization of Alcohols
  作者：Jasmin Eljo、Myriam Carle、Graham Murphy

  DOI：10.1055/s-0036-1589069

  日期：2017.12

  The use of hypervalent iodine reagents as a general tool for the activation of PPh3 and its application to the functionalization of alcohols is reported. Combination of PPh3 with PhICl2 or TolIF2 gives dihalophosphoranes that are characterized by 31P NMR, however, with PhIOAc2, PhI(OTFA)2, or the cyclic chloro(benzoyloxy)iodane, no phosphoranes were observed. Reaction of these iodanes with PPh3 in the presence of primary, secondary, or tertiary alcohols results in either halogenation or acyl-transfer products in moderate to high yield.

  报道了使用高价碘试剂作为活化PPh3的通用工具，并将其应用于醇的官能化。将PPh3与PhICl2或TolIF2结合得到二卤代膦烷，通过31P NMR进行表征，然而，与PhIOAc2、PhI(OTFA)2或环状氯代苯甲酰氧碘烷结合时，未观察到膦烷的形成。这些碘烷与PPh3在一次、二次或三次醇的存在下反应，产物为卤代化合物或酰基转移产物，产率中等至高。
• 2-(phenyl or heterocyclic)-1H-phenantrho[9,10-d]imidazoles as mPGES-1 inhibitors
  申请人：Chau Anh

  公开号：US20090075998A1

  公开（公告）日：2009-03-19

  The invention encompasses novel compounds of Formula I or pharmaceutically acceptable salts thereof. These compounds are inhibitors of the microsomal prostaglandin E synthase-1 (mPGES-1) enzyme and are therefore useful to treat pain and/or inflammation from a variety of diseases or conditions, such as osteoarthritis, rheumatoid arthritis and acute or chronic pain. Methods of treating diseases or conditions mediated by the mPGES-1 enzyme and pharmaceutical compositions are also encompassed.

  该发明涵盖了式I的新化合物或其药学上可接受的盐。这些化合物是微粒体前列腺素E合酶-1（mPGES-1）酶的抑制剂，因此可用于治疗多种疾病或情况引起的疼痛和/或炎症，如骨关节炎，类风湿性关节炎和急性或慢性疼痛。还包括治疗由mPGES-1酶介导的疾病或情况的方法和制药组合物。
• 2-(Phenyl or heterocyclic)-1H-phenantrho[9,10-d]imidazoles as mPGES-1 inhibitors
  申请人：Chau Anh

  公开号：US20070208017A1

  公开（公告）日：2007-09-06

  The invention encompasses novel compounds of Formula I or pharmaceutically acceptable salts thereof. These compounds are inhibitors of the microsomal prostaglandin E synthase-1 (mPGES-1) enzyme and are therefore useful to treat pain and/or inflammation from a variety of diseases or conditions, such as osteoarthritis, rheumatoid arthritis and acute or chronic pain. Methods of treating diseases or conditions mediated by the mPGES-1 enzyme and pharmaceutical compositions are also encompassed.

  本发明涵盖了公式I的新化合物或其药学上可接受的盐。这些化合物是微粒体前列腺素E合成酶-1（mPGES-1）酶的抑制剂，因此可用于治疗各种疾病或病况引起的疼痛和/或炎症，如骨关节炎、类风湿性关节炎和急性或慢性疼痛。还包括治疗由mPGES-1酶介导的疾病或病况的方法和制药组合物。
• Phenanthrene derivatives as MPGES-1 inhibitors
  申请人：Cote Bernard

  公开号：US20090209571A1

  公开（公告）日：2009-08-20

  The invention encompasses novel compounds of Formula or pharmaceutically acceptable salts thereof. These compounds are inhibitors of the microsomal prostaglandin E synthase-1 (mPGES-1) enzyme and are therefore useful to treat pain and/or inflammation from a variety of diseases or conditions, such as osteoarthritis, rheumatoid arthritis and acute or chronic pain. Methods of treating diseases or conditions mediated by the mPGES-1 enzyme and pharmaceutical compositions are also encompassed.

  本发明涵盖了公式或其药学上可接受的盐的新型化合物。这些化合物是微粒体前列腺素E合成酶-1(mPGES-1)酶的抑制剂，因此可用于治疗各种疾病或病况引起的疼痛和/或炎症，例如骨关节炎、类风湿性关节炎和急性或慢性疼痛。本发明还涵盖了治疗由mPGES-1酶介导的疾病或病况的方法和制药组合物。
• Methods for Treating or Preventing Neoplasias
  申请人：Kargman Stacia

  公开号：US20090192158A1

  公开（公告）日：2009-07-30

  The present invention is directed to a method for treating or preventing a neoplasia in a human patient in need of such treatment comprising administering to the patient a compound that inhibits microsomal prostaglandin E synthase-1 in an amount that is effective for treating or preventing the neoplasia.

  本发明涉及一种治疗或预防人类患者肿瘤的方法，包括向患者施用一种抑制微粒体前列腺素E合酶-1的化合物，其剂量足以治疗或预防该肿瘤。