2,5-di(tert-butyl)benzoic acid | 14034-95-8

• 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: 2,5-di(tert-butyl)benzoic acid
• 英文别名: 2,5-di-tert-butylbenzoic acid；2,5-di-tert-butyl-benzoic acid；2,5-Di-tert-butyl-benzoesaeure；2,5-Di-tert.-butyl-benzoesaeure；2,5-Ditert-butylbenzoic acid
• CAS: 14034-95-8
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: OHJGKKIIENYZIU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  2,5-di(tert-butyl)benzoic acid 在 lithium aluminium tetrahydride 作用下， 生成 (2,5-Di-tert-butyl-phenyl)-methanol
  参考文献：
  名称：

  Photocyclization of 2,4,6,2',4',6'-Hexaalkylbenzils

  摘要：

  Three of the title compounds-the hexamethyl-, hexaethyl-, and hexaisopropylbenzils-all photocyclize both in solution and as solids to 5,7-dialkyl-2-(2',4',6'-trialkylphenyl)-2-hyudroxy-1-indanones. At wavelengths <370 nm these primary photoproducts undergo secondary photocleavage to ketoaldehydes. The hexaethylbenzil produces only the (Z)-hydroxyindanone in the solid but a 2/1 Z/E ratio at low conversion in solution. The solid-state reactivity and the preference for formation of the (Z)-hydroxyindanone from the hexaethylbenzil suggest that much of the reaction involves delta-hydrogen abstraction followed by coupling of the 1,5-biradical. The formation of (E)-hydroxyindanones from o-ethylphenyl diketones had been attributed to stereospecific rearrangement of a photodienol formed by gamma-hydrogen abstraction. However, none of the H/D exchange of benzylic hydrogens expected of a photodienol occurs in methanol-d(4). Moreover, AM1-level semiempirical calculations suggest that a simple exothermic hydrogen transfer can convert the 1,4-biradical tripler dienol to the same 1,5-biradical formed by delta-hydrogen abstraction. The 1,5-biradical has two major conformations, one leading to Z product and an internally OH-O=C hydrogen bonded one leading to E product. The AM1 computations suggest that the two conformations are of comparable energy and thus implicate 1,5-biradicals as the major precursors to hydroxyindanone products. Stem-Volmer quenching studies indicate a triplet decay rate of 5 x 10(6) s(-1) for the hexaisopropylbenzil. The known behavior of structurally similar monoketones predicts such a rate for delta-hydrogen abstraction but a much slower rate for gamma-hydrogen abstraction. However, relative quantum efficiencies parallel those for benzocyclobutenol formation from 2,4,6-trialkylbenzophenones (iPr and Et similar to 0.3, Me similar to 0.03). The hexa-tert-butylbenzil undergoes very low quantum yield formation of 3,3-dimethyl-5,7-di-tert-butyl-1-indanone and 2,4,6-tri-tert-butylbenzaldehyde, presumably by delta-hydrogen abstraction and highly efficient radical cleavage of the resulting 1-aroyl-1-indanol.

  DOI：

  10.1021/ja00134a006
• 作为产物：
  描述：

  2,5-bis-tert-butylbenzaldehyde 在 吡啶 、 氢氧化钾 、 potassium permanganate 作用下， 生成 2,5-di(tert-butyl)benzoic acid
  参考文献：
  名称：

  Beets et al., Recueil des Travaux Chimiques des Pays-Bas, 1959, vol. 78, p. 570,582

  摘要：

  DOI：

文献信息

• Efficient Chemoselective Carboxylation of Aromatics to Arylcarboxylic Acids with a Superelectrophilically Activated Carbon Dioxide−Al₂Cl₆/Al System
  作者：George A. Olah、Béla Török、Jens P. Joschek、Imre Bucsi、Pierre M. Esteves、Golam Rasul、G. K. Surya Prakash

  DOI：10.1021/ja020787o

  日期：2002.9.1

  organoaluminum intermediates (PhAlCl(2) and PhAl(2)Cl(5)). The other proceeds through the formation of various complexes of CO(2) with aluminum chloride (AlCl(3))(n), n = 1-4. The calculations have shown that the organometallic pathway, leading eventually through the formation of phenylaluminum dichloride, is endothermic by 33 kcal/mol. In contrast, the preferred CO(2)-AlCl(3) complex forms in an exothermic

  通过在中等温度（20-80 摄氏度）下使用二氧化碳-Al(2)Cl(6)/Al 系统对芳烃进行羧化，可以获得基本上不含二芳基酮的芳香羧酸。为了优化反应条件和研究反应机理，研究了温度、Al(2)Cl(6)/Al 用量、各种路易斯酸、金属添加剂的作用、二氧化碳压力等实验变量。发现羧化反应是化学计量的而不是催化的，氯化铝形成羧酸的二氯铝酸盐。尽管使用 AlCl(3) 本身进行羧化，但金属添加剂（尤其是 Al）的存在增加了羧酸的产率和选择性。由于无法根据实验结果区分两种可能的反应机理途径，因此还进行了使用密度泛函理论 (DFT) 的理论计算。一种可能的途径涉及苯和 Al(2)Cl(6) 之间的初始复合物，随后形成有机铝中间体（PhAlCl(2) 和 PhAl(2)Cl(5)）。另一个通过 CO(2) 与氯化铝 (AlCl(3))(n) 形成各种配合物进行，n = 1-4。计算表明，最终形成苯基二氯化铝的有机金属途径吸热
• The rate retarding effect of alkyl groups on arene metalation quantified
  作者：Eckhard Baston、Qian Wang、Manfred Schlosser

  DOI：10.1016/s0040-4039(99)02160-7

  日期：2000.1

  tert-alkyl substituent effects on the metalation rates at aromatic ortho, meta and para positions. Unlike alkyl groups, hetero elements generally accelerate metalation reactions. 1,1,3,3-Tetramethyl-1,3-dihydroisobenzofuran undergoes the hydrogen/metal exchange 3–6 times faster than the indanes mentioned above, the reaction occurring at both the 5- and at the 4-position.

  除非试剂以高浓度使用，否则施加于相对惰性的叔烷基取代的芳烃的金属化/捕获顺序往往会产生不良的收率。在优化的条件下，甚至1,4-双（叔丁基）苯，1,1,3,3-四甲基茚满和1,1,2,2,3,3-六甲基茚满也可以平稳地转化为衍生物。通过竞争实验，可以定量评估叔烷基取代基对芳族邻位，间位和对位金属化速率的影响职位。与烷基不同，杂元素通常会加速金属化反应。1,1,3,3-四甲基-1,3-二氢异苯并呋喃的氢/金属交换速度是上述茚满的3-6倍，反应发生在5位和4位。
• THE TERTIARYBUTYLBENZENES: III. THE SYNTHESIS OF 2,4,6-TRI-<i>t</i>-BUTYLBENZOIC ACID AND THE DISSOCIATION OF DI- AND TRI-<i>t</i>-BUTYLBENZOIC ACIDS
  作者：Eileen E. Betts、L. Ross C. Barclay

  DOI：10.1139/v55-219

  日期：1955.12.1

  4-di-t-butylbenzene with bromine gave 2,5-di-t-butylbromobenzene, which on reaction with n-butyllithium and subsequent carbonation gave 2,5-di-t-butylbenzoic acid. The reaction of 1,3,5-tri-t-butylbenzene with acetyl chloride in the presence of aluminum chloride gave a liquid ketone, and hypohalide oxidation of this ketone yielded 3,5-tri-t-butylbenzoic acid. The ultraviolet absorption spectra of the two bromo

  2,4,6-三叔丁基溴苯，熔点 177–177.5°，是通过在硝酸银存在下溴化 1,3,5-三叔丁基苯制备的。2,4,6-三叔丁基溴苯和正丁基锂反应生成2,4,6-三叔丁基苯基锂，碳酸化生成2,4,6-三叔丁基苯甲酸， mp 297°。将该酸在发烟硫酸中的溶液倒入无水甲醇中时，会生成一种甲基酯，熔点 96-98°。用溴对 1,4-二叔丁基苯进行类似处理得到 2,5-二叔丁基溴苯，其与正丁基锂反应并随后碳酸化得到 2,5-二叔丁基苯甲酸。在氯化铝存在下，1,3,5-三叔丁基苯与乙酰氯反应得到液体酮，该酮的次卤氧化得到3,5-三叔丁基苯甲酸。测量并讨论了两种溴化合物和三种酸的紫外吸收光谱。2,4,6-三叔丁基苯甲酸的显着弱酸作用是...
• Method for oxidising hydrocarbons into acids
  申请人：——

  公开号：US20030166967A1

  公开（公告）日：2003-09-04

  The present invention relates to a process for oxidizing hydrocarbons, in particular branched or unbranched saturated aliphatic hydrocarbons, cycloaliphatic or alkylaromatic hydrocarbons to acidic or polyacidic compounds. The invention relates more particularly to the oxidation, with an oxidizing agent containing molecular oxygen, of cyclohexane to adipic acid, in the presence of organic acid of lipophilic nature and in the absence of adipic acid. The separation and recycling of the unoxidized cyclohexane, the oxidation intermediates and the catalysts are easier than in the presence of acetic acid.

  本发明涉及一种将碳氢化合物，特别是支链或非支链饱和脂肪烃、环脂烃或烷芳烃氧化成酸性或多酸性化合物的工艺。 本发明尤其涉及在有亲脂性有机酸存在和没有己二酸的情况下，用含分子氧的氧化剂将环己烷氧化成己二酸。与有乙酸存在时相比，未氧化的环己烷、氧化中间产物和催化剂更容易分离和回收。
• Dimetalation: The Acidity of Monometalated Arenes Towards Superbasic Reagents
  作者：Eckhard Baston、Raimondo Maggi、Kirstin Friedrich、Manfred Schlosser

  DOI：10.1002/1099-0690(200111)2001:21<3985::aid-ejoc3985>3.0.co;2-y

  日期：2001.11