(+/-)-(1S,2S)-2-(N-benzyl-N-methylamino)cyclohexanol | 109433-73-0

• 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,2S)-2-(N-benzyl-N-methylamino)cyclohexanol
• 英文别名: (+/-)-trans-2-(N-benzyl-N-methylamino)cyclohexanol；trans-2-(N-Benzyl-N-methylamino)cyclohexanol；trans-2-(benzylmethylamino)cyclohexanol；(+/-)-trans-2-(Benzyl-methyl-amino)-cyclohexanol；(1R,2R)-2-[benzyl(methyl)amino]cyclohexan-1-ol
• CAS: 109433-73-0
• 化学式: C₁₄H₂₁NO
• 分子量: 219.327
• InChiKey: JBKPJCRFOPWOGF-ZIAGYGMSSA-N

物化性质

• 沸点：
  165-170 °C(Press: 12 Torr)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

安全信息

• 危险等级：
  IRRITANT

反应信息

• 作为反应物：
  描述：

  (+/-)-(1S,2S)-2-(N-benzyl-N-methylamino)cyclohexanol 在 甲基磺酰氯 、 三乙胺 、 ammonium hydroxide 作用下， 以 乙醚 为溶剂， 反应 16.0h， 生成 (1R,2R)-N-benzyl-N-methylcyclohexane-1,2-diamine
  参考文献：
  名称：

  化学活性的光学活性反式环-环己烷-1，2-二胺衍生物的制备：镇痛药U-（-）-50,488的有效合成。

  摘要：

  （+/-）-反-N，N-环己烷-1,2-二胺（（+/-）-4 ag）的立体定向合成是从相应的（+/-）-反-N，N-通过连续用甲磺酰氯和氨水处理二烷基氨基环己醇。立体化学结果表明形成了中叠氮鎓离子中间体。二胺（+/-）-4的动力学拆分可有效地完成南极假丝酵母脂肪酶B催化的氨解反应，其中乙酸乙酯为溶剂和酰基供体。分离出的乙酰胺和其余的二胺作为苄氧羰基衍生物，具有很高的ee值（92-99％）。一种氨基甲酸酯用作镇痛剂U-（-）-50,488的前体。

  DOI：

  10.1002/chem.200400607
• 作为产物：
  描述：

  1-(N-Benzyl-N-methylamino)cyclohexene 生成 (+/-)-(1S,2S)-2-(N-benzyl-N-methylamino)cyclohexanol
  参考文献：
  名称：

  Boranes in Synthesis. 5. The Hydroboration of Enamines with Mono- and Dialkylboranes. Asymmetric Synthesis of .beta.-Amino Alcohols of Moderate Enantiomeric Purity from Aldehyde Enamines

  摘要：

  The hydroboration of both acyclic and cyclic aldehyde and ketone enamines with such representative mono- and dialkylboranes as thexylborane and dicyclohexylborane, followed by an oxidative workup, yields the corresponding beta-amino alcohols in good to excellent isolated yields. The hydroboration of ketone and aldehyde enamines with the asymmetric hydroboration reagents monoisopinocampheylborane ((d)IpcBH(2)) and diisopinocampheylborane ((d)Ipc(2)BH) was also investigated, (d)Ipc(2)BH is highly effective for the asymmetric hydroboration of acyclic aldehyde enamines, such as 1-(4-morpholino)-3-phenyl-1-propene and 1-(1-pyrrolidino)-1-octene. Oxidation of the intermediate trialkylborane furnishes the corresponding beta-amino alcohols in 50-86% ee. The stereogenic center of the carbinol carbon is consistently enriched in the R-enantiomer when (d)Ipc(2)BH prepared from (+)-alpha-pinene is used as the hydroboration reagent. The enantiomeric excesses of the beta-amino alcohols synthesized in this study were determined by HPLC using a chiral stationary phase. The absolute configurations of some of the beta-amino alcohols synthesized in this study were determined by chiral HPLC comparison with authentic beta-amino alcohols prepared from chiral epoxides of known absolute configuration.

  DOI：

  10.1021/jo00112a026

文献信息

• Asymmetric Azidation under Hydrogen Bonding Phase-Transfer Catalysis: A Combined Experimental and Computational Study
  作者：Jimmy Wang、Matthew A. Horwitz、Alexander B. Dürr、Francesco Ibba、Gabriele Pupo、Yuan Gao、Paolo Ricci、Kirsten E. Christensen、Tejas P. Pathak、Timothy D. W. Claridge、Guy C. Lloyd-Jones、Robert S. Paton、Véronique Gouverneur

  DOI：10.1021/jacs.1c13434

  日期：2022.3.16

  encouraged us to undertake a detailed study on the application of hydrogen bonding phase-transfer catalysis (HB-PTC) to enantioselective azidation with sodium azide. So far, this phase-transfer manifold has been applied exclusively to insoluble metal alkali fluorides for carbon–fluorine bond formation. Herein, we disclose the asymmetric ring opening of meso aziridinium electrophiles derived from β-chloroamines

  不对称催化叠氮化对于获得对映体富集的含氮分子的重要性增加，但使用廉价叠氮化钠的方法仍然很少。这鼓励我们对氢键相转移催化（HB-PTC）在叠氮化钠对映选择性叠氮化中的应用进行详细研究。到目前为止，这种相转移歧管仅应用于不溶性金属碱金属氟化物以形成碳-氟键。在此，我们公开了在手性双脲催化剂存在下，由 β-氯胺与叠氮化钠衍生的内消旋氮丙啶鎓亲电子试剂的不对称开环。对新型氢键叠氮化物配合物的结构进行了计算分析，在固态通过 X 射线衍射，在溶液相通过1 H 和14 N/ 15 N NMR 光谱。与N-异丙基化的 BINAM 衍生的双脲，叠氮化物以三足方式与所有三个 NH 键末端结合在能量上是有利的，这种排列让人想起相应的动态更刚性的三叉氢键合氟化物络合物。计算分析表明，导致主要对映异构体的最稳定过渡态显示来自叠氮化物阴离子的氢键末端的攻击。所有三个氢键都保持在过渡态；然而，如在不对称 HB-PTC 氟化中所见，亲核试剂和单齿脲之间的
• Synthesis, in vitro acetylcholine-storage-blocking activities, and biological properties of derivatives and analogs of trans-2-(4-phenylpiperidino)cyclohexanol (vesamicol)
  作者：Gary A. Rogers、Stanley M. Parsons、D. C. Anderson、Lena M. Nilsson、Ben A. Bahr、Wayne D. Kornreich、Rose Kaufman、Robert S. Jacobs、Bernard Kirtman

  DOI：10.1021/jm00126a013

  日期：1989.6

  Eighty-four analogues and derivatives of the acetylcholine-storage-blocking drug trans-2-(4-phenylpiperidino)-cyclohexanol (vesamicol) were synthesized, and their potencies were evaluated with the acetylcholine active-transport assay utilizing purified synaptic vesicles from Torpedo electric organ. The parent drug exhibits enantioselectivity, with (-)-vesamicol being 25-fold more potent than (+)-vesamicol. The atomic structure and absolute configuration of (+)-vesamicol were determined by X-ray crystallography. The absolute configuration of (-)-vesamicol is 1R,2R. Structure-activity evidence indicates that (-)-vesamicol does not act as an acetylcholine analogue. Alterations to all three rings can have large effects on potency. Unexpectedly, analogues locking the alcohol and ammonium groups trans-diequatorial or trans-diaxial both exhibit good potency. A potent benzovesamicol family has been discovered that is suitable for facile elaboration of the sort useful in affinity labeling and affinity chromatography applications. A good correlation was found between potencies as assessed by the acetylcholine transport assay and LD50 values in mouse.
• Aminocyclohexyl Esters
  作者：Seymour L. Shapiro、Harold Soloway、Harris J. Shapiro、Louis Freedman

  DOI：10.1021/ja01524a043

  日期：1959.8
• Blaha; Kovar, Collection of Czechoslovak Chemical Communications, 1959, vol. 24, p. 152,156
  作者：Blaha、Kovar

  DOI：——

  日期：——
• Studies of reactions of dimethylphosphoramidic difluoride withtrans-2-(N,N-dialkylamino)cycloalkanols in the presence of various sulfur-containing nucleophiles
  作者：M. A. Kochetkov、V. S. Kuz'min、S. V. Sadovnikov、V. B. Sitnikov、A. V. Sosnov、E. A. Fokin

  DOI：10.1007/bf02495700

  日期：1998.9

  The reactions of dimethylphosphoramidic difluoride (I) with trans-2-(N,N-dialkylamino)cycloalkanols were studied in the presence of various sulfur-containing nucleophiles and Et3N. When O,O-diisopropyl thiophosphoric acid was used as a nucleophile, the corresponding O, O-diisopropyl S-[2-(N,N-dialkylamino)cycloalkyl] thiophosphates were obtained in satisfactory yields. The direction of this reaction in the presence of O-isopropyl toluenephosphonothioic acid depends on the pK(a) of aminoalcohol, namely, the amount of O-isopropyl tolylphosphonofluoridate that was formed along with O-isopropyl S-[2-(N,N-dialkylamino)cycloalkyl] tolylphosphonothioates was increased as the pK(a) increased. The reactions of compound 1 with trans-2-(N, N-dialkylamino)cycloalkanols and thioacetic acid afforded 2-(N,N-dialkylamino)cycloalkanethiols, certain of which were readily oxidized to the corresponding disulfides. In the case of potassium ethyl xanthate, the composition of the reaction products depends on the nature of aminoalcohol. X-ray diffraction analysis of S-(2-piperidinocyclohexyl) N,N-dimethyldithiocarbamate demonstrated that this compound exists as the trans isomer. This fact supports the reaction mechanism, which we have suggested previously and which involves the formation of aziridinium cations followed by their opening under the action of nucleophilic agents.