4-tert-butylcyclohexan-1-ol,4-methylbenzenesulfonic acid | 7453-04-5

• 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: 4-tert-butylcyclohexan-1-ol,4-methylbenzenesulfonic acid
• 英文别名: cis-4-tert-butylcyclohexyl tosylate；(1s,4s)-4-(tert-butyl)cyclohexyl 4-methylbenzenesulfonate；cis-4-tert-butylcyclohexyl p-toluenesulfonate；cis-4-t-butylcyclohexyl toluene-p-sulphonate；cis-4-t-butylcyclohexyl tosylate；toluene-4-sulfonic acid-(cis-4-tert-butyl-cyclohexyl ester)；Toluol-4-sulfonsaeure-(cis-4-tert-butyl-cyclohexylester)
• CAS: 7453-04-5
• 化学式: C₁₇H₂₆O₃S
• 分子量: 310.458
• InChiKey: JGDVVPFUYCFCOV-GASCZTMLSA-N

物化性质

• 沸点：
  415.8±14.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.31
• 重原子数：
  21.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-tert-butylcyclohexan-1-ol,4-methylbenzenesulfonic acid 在 六氟异丙醇 、 水 作用下， 生成 3-(TERT-BUTYL)-1-(MESITYLMETHYL)-1H-PYRAZOLE-5-CARBOXYLIC ACID
  参考文献：
  名称：

  Alicyclic reaction mechanisms. 7. The predominance and quantification of steric effects in the solvolysis of secondary aliphatic esters

  摘要：

  DOI：

  10.1021/jo00369a010
• 作为产物：
  描述：

  4-叔丁基环己酮 在 盐酸 、 溶剂黄146 、 铂 作用下， 生成 4-tert-butylcyclohexan-1-ol,4-methylbenzenesulfonic acid
  参考文献：
  名称：

  Neighboring Carbon and Hydrogen. XIX. t-Butylcyclohexyl Derivatives. Quantitative Conformational Analysis

  摘要：

  DOI：

  10.1021/ja01626a037

文献信息

• Epimerization of Tertiary Carbon Centers via Reversible Radical Cleavage of Unactivated C(sp³)–H Bonds
  作者：Yaxin Wang、Xiafei Hu、Cristian A. Morales-Rivera、Guo-Xing Li、Xin Huang、Gang He、Peng Liu、Gong Chen

  DOI：10.1021/jacs.8b05753

  日期：2018.8.1

  cleavage of C(sp3)-H bonds can enable racemization or epimerization, offering a valuable tool to edit the stereochemistry of organic compounds. While epimerization reactions operating via cleavage of acidic C(sp3)-H bonds, such as the Cα-H of carbonyl compounds, have been widely used in organic synthesis and enzyme-catalyzed biosynthesis, epimerization of tertiary carbons bearing a nonacidic C(sp3)-H bond

  C(sp3)-H 键的可逆断裂可以实现外消旋化或差向异构化，为编辑有机化合物的立体化学提供了宝贵的工具。虽然通过裂解酸性 C(sp3)-H 键（例如羰基化合物的 Cα-H）进行的差向异构化反应已广泛用于有机合成和酶催化生物合成，但带有非酸性 C(sp3) 的叔碳的差向异构化-H 键更具挑战性，可用的实用方法很少。在这里，我们报告了第一个合成有用的协议，用于在温和条件下通过未活化的 C(sp3)-H 键与高价碘试剂苯并恶唑叠氮化物和 H2O 的可逆自由基裂解来进行叔碳差向异构化。这些反应对各种环烷烃的未活化 3° CH 键表现出优异的反应性和选择性，并为编辑传统方法难以处理的碳支架的立体化学构型提供了强大的策略。机理研究表明，N3• 作为催化氢原子穿梭的独特能力对于以高效率和选择性可逆地破坏和重组 3° CH 键至关重要。
• Stereospecific Nickel-Catalyzed Reductive Cross-Coupling of Alkyl Tosylate and Allyl Alcohol Electrophiles
  作者：Quentin D. Tercenio、Erik J. Alexanian

  DOI：10.1021/acs.orglett.1c02616

  日期：2021.9.17

  The stereospecific cross-coupling of easily accessed electrophiles holds significant promise in the construction of C–C bonds. Herein, we report a nickel-catalyzed reductive coupling of allyl alcohols with chiral, nonracemic alkyl tosylates. This cross-coupling delivers valuable allylation products with high levels of stereospecificity across a range of substrates. The catalytic system consists of

  易于获得的亲电子试剂的立体定向交叉偶联在 C-C 键的构建中具有重要的前景。在此，我们报道了烯丙醇与手性非外消旋烷基甲苯磺酸盐的镍催化还原偶联。这种交叉偶联可在一系列底物上提供具有高立体特异性的有价值的烯丙基化产物。该催化系统由简单的镍盐和市售的还原剂组成，重要的是代表了涉及两个亲电试剂的 C-O 键的交叉偶联的罕见例子。
• Reaction of magnesium iodide with tosylates
  作者：J. Gore、P. Place、M. L. Roumestant

  DOI：10.1039/c3973000821b

  日期：——

  Alkyl iodides are obtained in good yield from the reaction of MgI2 with tosylates; depending on the structure of the starting material the mechanism is SN1 or SN2; in several cases, elimination products are observed.

  MgI 2与甲苯磺酸酯的反应可得到高产率的烷基碘。取决于原料的结构，机理是S N 1或S N 2；在某些情况下，观察到消除产物。
• Kinetic Studies of Solvolysis. XVI. Phenolysis of<i>cis</i>- and<i>trans</i>-4-<i>t</i>-Butylcyclohexy<i>p</i>-Toluenesulfonates. Rates and Product Distribution
  作者：Kunio Okamoto、Seiki Saitô、Haruo Shingu

  DOI：10.1246/bcsj.42.3288

  日期：1969.11

  The rates of the phenolysis of cis- and trans-4-t-butylcyclohexyl p-toluenesulfonates have been measured in the presence of equimolar amounts of triethylamine in phenol, phenol-benzene (3 : 1 by wt), and phenol-benzene (1 : 1 by wt) solvents. At 75°C, the axial isomer, i.e., the cis tosylate, phenolyzes more rapidly in the phenol-benzene mixture (1 : 1 by wt) than the equatorial isomer, i.e., the trans tosylate, by a factor of 3.08; this factor is not far from the axial-equatorial rate ratios observed in other hydroxylic solvents, indicating that phenol is a typical solvolytic solvent. Under the same reaction conditions as the rate measurements, the equatorial tosylate yields t-butylcyclo-hexene (72.5%), t-butylcyclohexyl phenyl ether (9.4%), predominantly inverted (cis-4-t-butylcyclo-hexyl) phenyl ether, and t-butylcyclohexylphenol (4.4%), whereas the axial tosylate yields t-butyl-cyclohexene (87%) and the phenyl ether (8.7%), largely inverted (trans-4-t-butylcyclohexyl) phenyl ether, but containing increasing amounts of retained (cis-4-t-butylcyclohexyl) and and rearranged (trans-3-t-butylcyclohexyl) ethers; the rest is a mixture of t-butylcyclohexylphenols (1.6%). The composition percentages of the retained phenyl ether obtained from the two tosylates, i.e., 20.4% for the cis tosylate and 12.9% for the trans tosylate, indicate the highest extents of retention for phenol among those known for any other hydroxylic solvents. The initially added t-butylcyclohexenes exert no influence on the olefin or on the phenyl ether composition, whereas triethylammonium and diethylammonium p-toluenesulfonates, when added initially, enhance the phenolysis rate and exert a small but definite influence on the composition of the phenyl ether. The hypothesis of the hydrogen-bridged cation, proposed in order to explain the enhanced rate of the cis isomer and in order to elucidate the retained solvolysis product, has been questioned by a consideration of the mechanism on the basis of the results of this phenolysis.

  在苯酚、苯-苯酚（重量比3:1）和苯-苯酚（重量比1:1）溶剂中，测量了对苯磺酸酯的顺式和反式4-t-丁基环己基对苯磺酸酯的酚解速率。在75°C时，轴向异构体，即顺式磺酸酯，在苯-苯酚混合物（重量比1:1）中的酚解速率比赤道异构体，即反式磺酸酯快3.08倍；这一因子与在其他羟基溶剂中观察到的轴向-赤道速率比相差不远，表明苯酚是一种典型的溶剂。在与速率测量相同的反应条件下，赤道磺酸酯产生72.5%的t-丁基环己烯、9.4%的t-丁基环己基苯醚（主要是反转的顺式4-t-丁基环己基苯醚）和4.4%的t-丁基环己基酚，而轴向磺酸酯产生87%的t-丁基环己烯和8.7%的苯醚，主要是反转的反式4-t-丁基环己基苯醚，但含有越来越多的保留的（顺式4-t-丁基环己基）和重排的（反式3-t-丁基环己基）苯醚，其余是1.6%的t-丁基环己基酚混合物。从两个磺酸酯得到的保留苯醚的组成百分比，即顺式磺酸酯为20.4%，反式磺酸酯为12.9%，表明苯酚在已知的任何其他羟基溶剂中具有最高的保留程度。最初添加的t-丁基环己烯对烯烃或苯醚的组成没有影响，而初始添加的三乙铵盐和二乙铵盐对苯酚解速率的增强和对苯醚组成的轻微但明确的影响则显著。为了解释顺式异构体速率的提高和阐明保留的溶解产物，提出了氢桥阳离子的假说，但通过对这一酚解反应结果的机制进行考虑，对该假说提出了质疑。
• PROCESS FOR PRODUCING ESTER OR ALCOHOL
  申请人：Mitsui Chemicals, Inc.

  公开号：EP2039680A1

  公开（公告）日：2009-03-25

  Provided is a process for producing an ester or alcohol using a fluoroimidinium sulfonate derivative represented by the general formula (9) or a fluoroimidinium carboxylate derivative represented by the general formula (6) and using as a raw material alcohol involving inversion of steric configuration. Further provided are a fluoroimidinium sulfonate derivative represented by the general formula (9), and a process for producing the same.

  本发明提供了一种使用通式（9）代表的氟亚氨基磺酸酯衍生物或通式（6）代表的氟亚氨基羧酸酯衍生物并以涉及立体构型反转的醇为原料生产酯或醇的工艺。进一步提供了通式（9）代表的氟亚氨基磺酸鎓衍生物及其生产工艺。