trans-4-tert-butylcyclohexyl 4-toluenesulfonate | 7453-05-6

• 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: trans-4-tert-butylcyclohexyl 4-toluenesulfonate
• 英文别名: toluene-4-sulfonic acid-(trans-4-tert-butyl-cyclohexyl ester)；Toluol-4-sulfonsaeure-(trans-4-tert-butyl-cyclohexylester)；trans-4-tert-butyl-cyclohexyl-toluenesulfonate
• CAS: 7453-05-6
• 化学式: C₁₇H₂₆O₃S
• 分子量: 310.458
• InChiKey: JGDVVPFUYCFCOV-SHTZXODSSA-N

物化性质

• 熔点：
  89.4-90.0 °C(Solv: pentane (109-66-0); ethyl acetate (141-78-6))
• 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：

  trans-4-tert-butylcyclohexyl 4-toluenesulfonate 在 氢氧化钾 作用下， 生成 顺式-4-叔丁基环己烷-1-乙酸
  参考文献：
  名称：

  The Stereochemistry of the SN2' Reaction. I. Preparation of Pure trans-6-Alkyl-2-cyclohexen-1-ols

  摘要：

  DOI：

  10.1021/ja01599a024
• 作为产物：
  描述：

  4-tert-butylcyclohexan-1-ol,4-methylbenzenesulfonic acid 在 1-叠氮基-1,2-苯并氧代-3(1h)-酮 作用下， 以 水 、 氯苯 为溶剂， 反应 72.0h， 以50%的产率得到trans-4-tert-butylcyclohexyl 4-toluenesulfonate
  参考文献：
  名称：

  通过未活化的 C(sp3)-H 键的可逆自由基裂解使叔碳中心差向异构化

  摘要：

  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。

  DOI：

  10.1021/jacs.8b05753

文献信息

• Low-temperature X-ray structural studies of the ester and ether derivatives of cis- and trans-4-tert-butyl cyclohexanol and 2-adamantanol: application of the variable oxygen probe to determine the relative σ-donor ability of C–H and C–C bonds
  作者：Marisa Spiniello、Jonathan M. White

  DOI：10.1039/b303453d

  日期：——

  Results of low-temperature X-ray structural studies for five cis-, and three trans-4-tert-butyl cyclohexanol, and six 2-adamantanol ester and ether derivatives are reported. Plots of C–OR bond distance against pKa(ROH) for derivatives of axial alcohol (5), equatorial alcohol (6) and 2-adamantanol derivatives (7) give slopes of −2.77 × 10−3, −2.86 × 10−3 and −3.05 × 10−3, respectively. Given that the relative differences in the slopes are modest, no clear distinction can be made about the relative σ-donor ability of a C–H bond and a C–C bond.

  本文报道了五个顺式和三个反式4-叔丁基环己醇以及六个2-金刚烷醇酯和醚衍生物的低温X射线结构研究结果。对于轴向醇（5）、赤道醇（6）和2-金刚烷醇衍生物（7）的衍生物，C─OR键距离与pKa(ROH)的关系图分别给出了斜率为-2.77×10^-3、-2.86×10^-3和-3.05×10^-3。鉴于斜率之间的相对差异较小，无法明确区分C─H键和C─C键的相对σ-供体能力。
• Selective reduction of tertiary alkyl, benzyl, and allyl halides to hydrocarbons using lithium 9,9-di-n-butyl-9-borabicyclo[3.3.1]nonanate
  作者：Hiroo Toi、Yoshinori Yamamoto、Akio Sonoda、Shun-Ichi Murahashi

  DOI：10.1016/s0040-4020(01)97982-7

  日期：——

  The title 9-borabicyclo[3.3.1]nonane(9-BBN) ate complex (1) brings about selective removal of tertiary alkyl, benzyl and allyl halides to give the corresponding hydrocarbons in excellent yields without concomitant attack on secondary, primary and aryl derivatives. The reduction of cis- and trans - 4 - t - butyl - 1 - methylcyclohexyl chlorides (2) with 1 gives 4 - t - butyl - 1 - methylcyclohexanes

  标题9-borabicyclo [3.3.1]壬烷（9-BBN）配合物（1）可以选择性地除去叔烷基，苄基和烯丙基卤，从而以优异的收率得到相应的烃，而不会伴随着对仲，伯和芳基的攻击衍生品。的还原顺式-和反式- 4 -吨-丁基- 1 -甲基环己基氯化物（2）与1给出4 -吨-丁基- 1 - methylcyclohexanes（3），在环己烷的配置的局部反转，而在苯给出热力学稳定的反式- 3为主。1,1-二甲基-5-己烯基氯化物的反应（4）和1,7,7- -三甲基二环[2.2.1]庚- 2 -基磺酰氯（8）配有1继续进行到碳离子中间特性的重排。要求1所述的还原-乙基- 1 -甲基戊基氯与1如下二阶速率方程。
• Iron-Catalyzed Directed Alkylation of Aromatic and Olefinic Carboxamides with Primary and Secondary Alkyl Tosylates, Mesylates, and Halides
  作者：Laurean Ilies、Tatsuaki Matsubara、Saki Ichikawa、Sobi Asako、Eiichi Nakamura

  DOI：10.1021/ja5066015

  日期：2014.9.24

  Alkenes, arenes, and heteroarenes possessing an 8-quinolylamide group as the directing group are alkylated with primary and secondary alkyl tosylates, mesylate, and halides in the presence of Fe(acac)3/diphosphine as a catalyst and ArZnBr as a base. The reaction proceeds stereospecifically for alkene substrates and takes place without loss of regiochemical integrity of the starting secondary tosylate

  在作为催化剂的 Fe(acac)3/二膦和作为碱的 ArZnBr 存在下，具有 8-喹啉酰胺基团作为导向基团的烯烃、芳烃和杂芳烃与伯和仲烷基甲苯磺酸盐、甲磺酸盐和卤化物烷基化。该反应对烯烃底物立体特异性地进行，并且在不损失起始二级甲苯磺酸酯的区域化学完整性的情况下发生，但会损失手性中心的立体化学。
• 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。