4-methyl-4-phenylcyclohexanone | 18932-33-7

• 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-methyl-4-phenylcyclohexanone
• 英文别名: 4-Methyl-4-phenyl-cyclohexanon；4-methyl-4-phenylcyclohexan-1-one
• CAS: 18932-33-7
• 化学式: C₁₃H₁₆O
• mdl: MFCD10569281
• 分子量: 188.269
• InChiKey: XPRFFLCYHYODMZ-UHFFFAOYSA-N

物化性质

• 沸点：
  295.6±29.0 °C(Predicted)
• 密度：
  1.014±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.461
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2914399090

反应信息

• 作为反应物：
  描述：

  4-methyl-4-phenylcyclohexanone 在 氢氧化钾 、 一水合肼 作用下， 以86%的产率得到1beta-甲基-1-苯基环己烷
  参考文献：
  名称：

  Conformational analysis. 40. Conformation of 1-methyl-1-phenylcyclohexane and conformational energies of the phenyl and vinyl groups

  摘要：

  DOI：

  10.1021/jo00322a056
• 作为产物：
  描述：

  4-甲基-4-苯基-2-环己烯-1-酮 在 palladium 10% on activated carbon 、 氢气 作用下， 以 乙酸乙酯 为溶剂， 20.0 ℃ 、800.01 kPa 条件下， 反应 5.0h， 生成 4-methyl-4-phenylcyclohexanone
  参考文献：
  名称：

  硅氢交换反应：一种对映选择性合成烯醇硅烷的催化 σ-键复分解方法

  摘要：

  手性烯醇硅烷在 Mukaiyama aldol、Michael 和 Mannich 反应以及 Saegusa-Ito 脱氢等基本转化中的使用使对映纯天然产物和有价值的药物的化学合成成为可能。然而，以高对映体纯度获取这些中间体通常需要使用化学计量的手性前体或化学计量的手性试剂。我们现在描述一种催化方法，其中强酸性和受限的亚胺二磷酰亚胺 (IDPi) 催化酮和烯醇硅烷的高度对映选择性互变。这些“硅 - 氢交换反应”能够通过互变异构化 σ 键复分解反应获得对映纯烯醇硅烷，

  DOI：

  10.1021/jacs.0c06677

文献信息

• Efficient methods for enol phosphate synthesis using carbon-centred magnesium bases
  作者：William J. Kerr、David M. Lindsay、Vipulkumar K. Patel、Muralikrishnan Rajamanickam

  DOI：10.1039/c5ob01849h

  日期：——

  Efficient conversion of ketones into kinetic enol phosphates under mild and accessible conditions has been realised using the developed methods with di-tert-butylmagnesium and bismesitylmagnesium. Optimisation of the quench protocol resulted in high yields of enol phosphates from a range of cyclohexanones and aryl methyl ketones, with tolerance of a range of additional functional units.

  使用已开发的二叔丁基镁和双金属镁的方法，已在温和且易接近的条件下将酮有效地转化为动力学烯醇式磷酸酯。淬灭方案的优化导致从一系列环己酮和芳基甲基酮中获得高收率的烯醇磷酸酯，并具有一定范围的附加功能单元。
• Desymmetrisation of 4,4-disubstituted cyclohexanones by enzyme-catalysed resolution of their enol acetates
  作者：Graham Allan、Andrew J. Carnell、Maria Luisa Escudero Hernandez、Alan Pettman

  DOI：10.1039/b005466f

  日期：——

  Enol acetates 3–10 derived from prochiral 4,4-disubstituted cyclohexanones can be resolved with Pseudomonas fluorescens lipase to give enantiomerically pure (>99% ee) enol esters by transesterification with n-BuOH. The product ketones are prochiral and can easily be recycled giving an overall desymmetrisation of the ketone. Highest selectivity was obtained for substrates containing a 4-cyano and 4-aryl or a 4-benzyloxy substituent. The methodology was compared to asymmetric deprotonation–enolate trapping using the chiral base (S,S)-bis(α-methylbenzyl)amide which gave low (54–64%) ee’s for this class of ketones.

  来自对称的4,4-二取代环己酮的醇乙酸酯3-10可以通过荧光假单胞菌脂肪酶进行分离，以转酯化反应与正丁醇生成对映体纯度>99% ee的醇酯。生成的酮是对称的，可以很容易地循环利用，从而实现酮的整体去对称化。对于含有4-氰基和4-芳基或4-苄氧基取代基的底物，获得了最高的选择性。该方法与使用手性碱(S,S)-双(α-甲基苯甲酰)胺的非对称去质子化-烯醇捕获进行了比较，该方法在这一类酮中获得了较低的对映体纯度(54-64% ee)。
• Stereoselective Desymmetrizations by Recombinant Whole Cells Expressing the Baeyer–Villiger Monooxygenase fromXanthobacter sp. ZL5: A New Biocatalyst Accepting Structurally Demanding Substrates
  作者：Daniela V. Rial、Dario A. Bianchi、Petra Kapitanova、Alenka Lengar、Jan B. van Beilen、Marko D. Mihovilovic

  DOI：10.1002/ejoc.200700872

  日期：2008.3

  Baeyer–Villiger monooxygenase from Xanthobacter sp. ZL5 with respect to biotransformations of prochiral substrates is characterized. This enzyme catalyzes the desymmetrization of cyclic ketones bearing different chemical features with stereoselectivity similar to that obtained with a related protein fromAcinetobacter as a prototype representative of the cyclohexanone monooxygenase enzyme cluster. Moreover

  在这项工作中，过表达来自黄杆菌属的 Baeyer-Villiger 单加氧酶的工程全细胞的底物谱和立体选择性。ZL5 关于前手性底物的生物转化的特征。该酶催化具有不同化学特征的环酮的去对称化，立体选择性类似于用来自不动杆菌的相关蛋白质作为环己酮单加氧酶酶簇的原型代表获得的。此外，这种生物催化剂能够以优异的对映选择性转化以前没有被其他酶转化的空间要求高的底物。这些结果扩展了全细胞生物转化过程可获得的光学纯内酯的所有成分，它们是合成天然和生物活性产品的有用中间体。此外，我们观察到由该单加氧酶催化的非活化 C=C 键发生显着的环氧化反应。（© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008）
• The Catalytic Asymmetric Fischer Indolization
  作者：Steffen Müller、Matthew J. Webber、Benjamin List

  DOI：10.1021/ja2092163

  日期：2011.11.23

  The first catalytic asymmetric Fischer indolization is reported. In the presence of a 5 mol % loading of a novel spirocyclic chiral phosphoric acid, 4-substituted cyclohexanone-derived phenylhydrazones undergo a highly enantioselective indolization. Efficient catalyst turnover was achieved by the addition of a weakly acidic cation exchange resin, which removes the generated ammonia. The reaction can

  报道了第一个催化不对称 Fischer 吲哚化反应。在 5 mol% 负载的新型螺环手性磷酸的存在下，4-取代的环己酮衍生的苯腙经历高度对映选择性的吲哚化。通过添加弱酸性阳离子交换树脂，去除产生的氨，实现了有效的催化剂周转。该反应可以在温和的条件下进行，并以通常高的收率得到各种 3-取代的四氢咔唑。
• 4-Arylcyclohexylamines
  申请人：The Upjohn Company

  公开号：US03979444A1

  公开（公告）日：1976-09-07

  The invention relates to novel 4-hydroxymethyl(acyloxymethyl and methyl)-4-arylcyclohexylamines embraced by the formula ##SPC1## Wherein Ar is an aromatic ring selected from the group consisting of phenyl and naphthyl, each of which has from zero through three substituents independently selected from the group consisting of fluorine, chlorine, bromine, lower alkyl of one through three carbon atoms, lower alkoxy of one through three carbon atoms, and lower alkylthio of one through three carbon atoms; Z is selected from the group consisting of hydrogen, hydroxy and lower acyloxy of one through four carbon atoms; .about. is a generic expression denoting cis and trans stereoconfiguration and mixtures thereof, with the proviso that when the stereoconfiguration of the linkage connecting the cyclohexane ring and CH.sub.2 Z is cis to the amino group, the linkage connecting the cyclohexane and Ar rings is trans, and vice versa; R.sup.1 is selected from the group consisting of hydrogen and lower alkyl of one through three carbon atoms; R.sup.2 is selected from the group consisting of hydrogen, lower alkyl of one through three carbon atoms, ##EQU1## WHEREIN N IS 2 THROUGH 5 AND Ar has the same meaning as above; R.sup.1 and R.sup.2 taken together with --N< is a saturated heterocyclic amino radical selected from the group consisting of unsubstituted and substituted pyrrolidino, piperidino, hexamethylenimino, morpholino and piperazino; and pharmacologically acceptable acid addition salts thereof. It also relates to intermediates and processes for the preparation of the aforesaid novel compounds (I) and novel derivatives thereof. The administration to humans and animals of the novel compounds (I) depresses their central nervous systems and lowers their blood pressures.

  该发明涉及一种新型4-羟甲基(酰氧甲基和甲基)-4-芳基环己胺，其化学式如下：其中Ar是从苯基和萘基中选择的芳香环，每个环上独立选择的取代基包括氟、氯、溴、1至3个碳原子的低烷基、1至3个碳原子的低烷氧基和1至3个碳原子的低烷基硫基；Z选择自氢、羟基和1至4个碳原子的低酰氧基；~表示顺式和反式立体构型及其混合物，但当连接环己烷环和CH2Z的立体构型为顺时，连接环己烷环和Ar环的连接是反式，反之亦然；R1选择自氢和1至3个碳原子的低烷基；R2选择自氢、1至3个碳原子的低烷基、其中N为2至5且Ar的含义与上述相同；R1和R2与-N<一起构成从未取代和取代的吡咯啉基、哌啶基、六亚甲基基、吗啉基和哌嗪基中选择的饱和杂环氨基基团；以及其药理学上可接受的酸盐。它还涉及中间体和用于制备上述新化合物(I)及其新衍生物的过程。将该新型化合物(I)用于人类和动物，可抑制其中枢神经系统并降低其血压。