(+)-(1S,2R,5R)-2-isopropyl-5-methylcyclohexyl p-toluenesulfonate | 2230-91-3

• 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: (+)-(1S,2R,5R)-2-isopropyl-5-methylcyclohexyl p-toluenesulfonate
• 英文别名: (+)-(1S,2R,5R)-isomenthyl tosylate；toluene-4-sulfonic acid-((1R)isomenthyl ester)；Toluol-4-sulfonsaeure-((1R)isomenthylester)；Toluol-sulfonsaeure-(4)-((1R)-isomenthylester)；p-Toluolsulfonsaeure-isomenthylester；[(1S,2R,5R)-5-methyl-2-propan-2-ylcyclohexyl] 4-methylbenzenesulfonate
• CAS: 2230-91-3
• 化学式: C₁₇H₂₆O₃S
• 分子量: 310.458
• InChiKey: XVOCEKOSQBFFHW-OIISXLGYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-(1S,2R,5R)-2-isopropyl-5-methylcyclohexyl p-toluenesulfonate 在 甲基锂 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 74.0h， 生成 Lithium,[1-[(1R,2R,5R)-5-methyl-2-(1-methylethyl)cyclohexyl]-1H-inden-1-yl]-
  参考文献：
  名称：

  The role of torsional isomers of planarly chiral nonbridged bis(indenyl)metal type complexes in stereoselective propene polymerization

  摘要：

  Reaction of enantiomerically pure (1-neomenthylindenyl)lithium with ZrCl4(THF)2 gave the three diastereomeric bis(1-neomenthylindenyl)zirconium dichloride complexes 4a-A,-B,and -C, in a 93:2:5 ratio. Similarly, a 82:7:11 mixture of the three bis(1-neoisomenthylindenyl)zirconium dichloride diastereoisomers (4b-A,B,C) was obtained from (1-neoisomenthylindenyl)lithium and the zirconium tetrachloride-bis(tetrahydrofuran) adduct. Recrystallization from methylene chloride furnished the (optically active) pure diastereomers 4a-A and 4b-A, respectively. Catalytic hydrogenation (PtO2, 50-60 bar of H-2, CH2Cl2) converted them into the pure (p-S, p-S)-bis(1-neomenthyl-4,5,6,7-tetrahydroindenyl)zirconium dichloride (5a-A) and (p-R,p-R)-bis(1-neoisomenthyl-4,5,6,7-tetrahydroindenyl)zirconium dichloride (5b-A) complexes. All four metallocenes were characterized by X-ray crystal structure analyses. Complex 4a-A crystallizes in space group P2 with cell parameters a = 10.510(1) angstrom, b = 6.975(1) angstrom, c = 12.421(1) angstrom, beta = 108.18(1)degrees, Z = 1, R = 0.037, R(w) = 0.041; 4b-A P2(1), a = 7.559(2) angstrom, b = 9.046(2) angstrom, c = 25.015(3) angstrom, beta = 96.72(1)degrees, Z = 2, R = 0.037, R(w) = 0.040; 5a-A P2(1)2(1)2, a = 15.422(1) angstrom, b = 18.716(1) angstrom, c = 7.118(1) angstrom, Z = 2, R = 0.062, R(w) = 0.074; 5b-A P2(1)2(1)2, a = 10.103(1) angstrom, b = 26.626(5) angstrom, c = 6.762(1) angstrom, Z = 2, R = 0.030, R(w) = 0.037. Complexes 4a-A, 5a-A, and 5b-A exhibit C2-symmetric bent metallocene conformations in the crystal which are characterized as having the bulky terpenyl substituents oriented antiperiplanarly toward the lateral sectors of the bent metallocene wedge (''bis-lateral:anti'' conformation). In contrast, the bis(neoisomenthylindenyl)zirconium dichloride complex 4b-A has only one hydrocarbyl substituent arranged laterally whereas the other is oriented to the open front side of the metallocene backbone (C1-symmetric ''central,lateral:gauche'' conformation). In solution the conformational behavior of these complexes is different. By dynamic temperature-dependent H-1 and C-13 NMR spectroscopy both neoisomenthyl-substituted complexes 4b-A and 5b-A appear as single C2-symmetric species in solution. In contrast, the neomenthyl-substituted complexes 4a-A and 5a-A exhibit equilibrating conformational mixtures. In the case of the (p-S,p-S)-bis(1-neomenthyl-4,5,6,7-tetrahydroindenyl)zirconium dichloride system (5a-A) it was shown that two conformational isomers are present in a ca. 80:20 ratio. These are C2- (major isomer) and C1-symmetric (minor isomer) and probably correspond to the ''bis-lateral:anti'' and ''central,lateral:gauche'' conformational types, respectively, that were identified by X-ray diffraction in the crystal. These conformational properties seem to determine the outcome of the stereoselective propene polymerization to a considerable extent, which was carried out at homogeneous bent metallocene/methylalumoxane Ziegler-type catalysts derived from the complexes 4 and 5. Both neoisomenthyl-substituted systems produce isotactic high molecular weight polypropylene with purely enantiomorphic site control at low temperature. The isomeric neomenthyl-substituted systems are much less stereoselective.It is assumed that the bis(1-neomenthyltetrahydroindenyl)zirconium catalyst switches back and forth between the C2- and C1-symmetric conformations of the bent metallocene backbone during the catalytic process, thereby probably giving rise to the formation of alternating isotactic and near to atactic sequences along the growing polymer chain.

  DOI：

  10.1021/ja00064a022
• 作为产物：
  描述：

  (+)-异薄荷醇 生成 (+)-(1S,2R,5R)-2-isopropyl-5-methylcyclohexyl p-toluenesulfonate
  参考文献：
  名称：

  Hueckel; Niggemeyer, Chemische Berichte, 1939, vol. 72, p. 1354,1357

  摘要：

  DOI：

文献信息

• Structure–Odor Activity Studies on Monoterpenoid Mercaptans Synthesized by Changing the Structural Motifs of the Key Food Odorant 1-<i>p</i>-Menthene-8-thiol
  作者：Sebastian Schoenauer、Peter Schieberle

  DOI：10.1021/acs.jafc.6b01645

  日期：2016.5.18

  ring always resulted in higher odor thresholds compared to thiols with a mercapto group in the side chains. Although all tertiary thiols always exhibited low odor thresholds, none of the 31 compounds reached the extremely low threshold of 1. Also, none of the synthesized mercapto monoterpenoids showed a similar odor quality resembling grapefruit. Although the saturated and aromatic analogues exhibited

  1- p-甲基-Nenthene-8-硫醇（1）几十年前被发现是柚子汁中的主要气味物质，它对水果的整体气味有贡献，在空气中的气味阈值极低，仅为0.000034 ng / L。该值是有史以来针对食品气味剂报告的最低气味阈值之一。为了检查结构1的修饰是否会导致气味阈值和气味质量的变化，使用了34个含巯基的对薄荷烷和1- p合成了薄荷烯衍生物以及几种芳族和开链巯基单萜。文献中首次报道了其中的18种，并提供了它们的气味阈值和气味质量以及分析数据。感官数据与1的感官数据比较表明，双键的氢化导致气味阈值明显增加。此外，与在侧链中具有巯基的硫醇相比，将巯基移入环中总是导致较高的气味阈值。尽管所有叔硫醇始终表现出较低的气味阈值，但31种化合物均未达到极低的阈值1。同样，没有合成的巯基单萜类化合物具有类似于葡萄柚的类似气味质量。尽管饱和和芳香族类似物的香气与1类似，但大多数其他化合物的香气被描述为含硫，橡胶
• Instantaneous Deprotection of Tosylamides and Esters with SmI₂/Amine/Water
  作者：Tobias Ankner、Göran Hilmersson

  DOI：10.1021/ol802243d

  日期：2009.2.5

  SmI2/amine/water mediates instantaneous cleavage of tosyl amides and tosyl esters. Highly hindered, sensitive and functionalized substrates were successfully deprotected in near quantitative yield.

  SmI 2 /胺/水介导甲苯磺酰胺和甲苯磺酯的瞬时裂解。高度受阻，敏感和功能化的底物以接近定量的收率成功脱保护。
• Hueckel; Wagner, Chemische Berichte, 1941, vol. 74, p. 657,660
  作者：Hueckel、Wagner

  DOI：——

  日期：——
• Hueckel et al., Justus Liebigs Annalen der Chemie, 1959, vol. 624, p. 142,202
  作者：Hueckel et al.

  DOI：——

  日期：——
• Synthesis and reactions of enantiomerically pure dialkyl diselenides from the p-menthane group
  作者：Zbigniew Rafiński、Jacek Ścianowski

  DOI：10.1016/j.tetasy.2008.04.027

  日期：2008.5

  A convenient route for the synthesis of optically active dialkyl diselenides from the p-menthane system utilizing a reaction of alkyl tosylates and chlorides with sodium diselenide is reported. The diselenides obtained have been used for asymmetric methoxyselenenylation of styrene. Quantum chemical calculations of the chair conformers stability of the terpeneselenenyl bromides from the p-menthane group have also been carried out using density functional theory (DFF, at the B3LYP/6-311G(d) level). The influence of the diselenides structure on the stereoselectivity in the methoxyselenenylation reaction is also discussed. (C) 2008 Elsevier Ltd. All rights reserved.