(+)-(R)-ethyl p-tolyl sulfoxide | 1519-40-0

• 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: (+)-(R)-ethyl p-tolyl sulfoxide
• 英文别名: (R)-1-(ethylsulfinyl)-4-methylbenzene；ethyl (p-tolyl) sulfoxide；(r)-4-Tolylethyl sulfoxide；1-[(R)-ethylsulfinyl]-4-methylbenzene
• CAS: 1519-40-0
• 化学式: C₉H₁₂OS
• 分子量: 168.26
• InChiKey: OHXBXXWDEOXULA-LLVKDONJSA-N

物化性质

• 沸点：
  296.2±19.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-(R)-ethyl p-tolyl sulfoxide 在 三氟乙酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 27.5h， 生成 (1S,2S,R_s)-1-methyl-1-phenyl-2-(p-tolylsulfinyl)propylamine
  参考文献：
  名称：

  α -亚磺酰基碳负离子，以立体选择性加成ñ - p -tolylsulfinylketimines：光学纯的合成1,2,2'-三烷基-2-氨基乙醇

  摘要：

  衍生自甲基（1）和对甲苯基亚砜乙基（2）的对映异构体的锂碳负离子与（S）-N-芳基亚磺酰基酮亚胺3和4的反应以高度立体选择性的方式进行，且分离得率良好。与氮键合的碳的构型仅依赖于N-亚磺酰亚胺的构型。当将对甲苯基亚砜乙基（2）用作亲核试剂时，会同时创建两个手性中心，其中键合到硫上的碳的构型主要受2控制。。不对称的感应随着温度的升高而增加，在配对反应物的情况下，这种不对称的感应通常在室温下发生。对所获得的氨基亚砜进行非氧化的Pummerer反应，可以直接合成具有一个或两个手性中心的光学纯的1,2-乙醇胺，包括具有与胺基键合的庞大季碳的氨基醇。

  DOI：

  10.1021/jo049666s
• 作为产物：
  描述：

  4-甲基苯基亚硫酰氯 在 吡啶 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.0h， 生成 (+)-(R)-ethyl p-tolyl sulfoxide
  参考文献：
  名称：

  Asymmetric synthesis of alkane- and arenesulfinates of diacetone-D-glucose (DAG): an improved and general route to both enantiomerically pure sulfoxides

  摘要：

  Diacetone-D-glucose (DAG), a commercially available, sugar-derived secondary alcohol, was found to react with alkane- and arenesulfinyl chlorides in the presence of a tertiary amine in a very useful manner. When i-Pr2Net is used as the base, (-)-(S)-alkane- and arenesulfinates are obtained in 50-90% yield with 89-greater-than-or-equal-to 95% de. Simply changing the base from i-Pr2NEt to Py affords (+)-(R)-alkane- and arenesulfinates in 56-87% yield with 70-greater-than-or-equal-to 95% de. The de's were determined by H-1 NMR. Optically pure alkane- and arenesulfinates are obtained either by recrystallization or by column chromatography. These sulfinates were transformed into various enantiomerically pure sulfoxides (alkyl alkyl and alkyl aryl) by reaction with different Grignard reagents. This new methodology is cheap, quick, and very convenient when both enantiomers of a given sulfoxide are needed enantiomerically pure. The influence of the solvent, as well as the effect of other types of bases, on the stereochemical course of the reaction has been evaluated, and a possible origin of the diastereoselectivity is discussed. Other optically pure secondary alcohols are used m the same reaction, and the comparison of their behavior with that of DAG is also reported.

  DOI：

  10.1021/jo00051a022

文献信息

• Asymmetric Sulfinylations of<i>N</i>-Methylephedrine-Modified Tri- or Tetraalkyl Zincates by Symmetric Diaryl Sulfoxides
  作者：Simon Ruppenthal、Reinhard Brückner

  DOI：10.1002/ejoc.201701603

  日期：2018.6.7

  Diethylzinc was treated with 1 or 2 equiv. of AlkMgCl or PhMgBr (preferably) or with 1 equiv. of nBuLi (less efficiently) for forming species – plausibly zincates – which were sulfinylated by diaryl sulfoxides to give racemic alkyl aryl sulfoxides in yields reaching 100 %. Dialkylzinc reagents were also activated by treatments with 1 or 2 equiv. of an enantiomerically pure alkylmagnesium β‐aminoalkoxide

  二乙基锌用1或2当量处理。最好是AlkMgCl或PhMgBr或1当量的AlkMgCl或PhMgBr。的Ñ振振有词锌酸盐- -丁基锂（效率较低），用于形成物种这是由二芳基sulfinylated亚砜，得到外消旋烷基芳基亚砜中的产率达到100％。二烷基锌试剂也可以通过用1或2当量的处理来活化。对映体纯的烷基镁β-氨基醇盐。当醇盐来自二烷基镁试剂和等摩尔量的N-甲基-（-）-麻黄碱时，这种方法最有效。该第二活化模式允许用二芳基亚砜将本来是二烷基锌试剂的亚磺酰基化。这样生成对映体比例高达93：7的烷基芳基亚砜，产率高达100％。
• Organocatalytic Asymmetric Synthesis of Sulfoxides from Sulfenic Acid Anions Mediated by a <i>Cinchona</i>-Derived Phase-Transfer Reagent
  作者：Fabien Gelat、Jayadevan Jayashankaran、Jean-François Lohier、Annie-Claude Gaumont、Stéphane Perrio

  DOI：10.1021/ol2010962

  日期：2011.6.17

  Preliminary results concerning a conceptually novel route to chiral sulfoxides based on the asymmetric alkylation of sulfenate salts with alkyl halides mediated by a chiral phase-transfer catalyst are described. As a representative example, o-anisyl methyl sulfoxide was produced in 96% yield and with an enantiomeric excess of 58% using commercial cinchonidinium derivative 2a.

  本文描述了有关手性亚砜在手性相转移催化剂介导的亚磺酸盐与烷基卤化物的不对称烷基化的基础上获得手性亚砜的新颖方法的初步结果。作为代表性的例子，ö -anisyl甲基亚砜，96％收率和58％对映体过量使用商业金鸡尼丁衍生物制备2A。
• Diastereoselective Radical Hydrogenation of α-(1-Hydroxyalkyl)vinyl Sulfoxides and Sulfones Controlled by Intramolecular Hydrogen Bonding
  作者：Nobuyuki Mase、Yoshihiko Watanabe、Takeshi Toru、Terumitsu Kakumoto、Tsuneo Hagiwara

  DOI：10.1021/jo005525o

  日期：2000.10.1

  (S)-alpha-(1-hydroxyalkyl)vinyl sulfoxides (S)-5 with alkyl radicals and tributyltin hydride gave the addition-hydrogenation products with high diastereoselectivity, whereas the reaction with (R)-alpha-(1-hydroxyalkyl)vinyl sulfoxides (R)-5 resulted in complete recovery of the starting sulfoxides. Stereoselective intramolecular hydrogen bonding between the hydroxy group and the diastereotopic sulfonyl oxygen led to high

  （S）-α-（1-羟烷基）乙烯基亚砜（S）-5与烷基和氢化三丁基锡的反应可得到高非对映选择性的加成氢化产物，而与（R）-α-（1-羟烷基）乙烯基亚砜（R）-5导致原料亚砜的完全回收。羟基和非对映体磺酰氧之间的立体选择性分子内氢键导致α-（1-羟乙基）乙烯基砜12自由基反应中的高非对映选择性。分子内氢键对非对映选择性以及对烷基的反应性具有重要作用。讨论了部首。
• An efficient asymmetric oxidation of sulfides to sulfoxides
  作者：P. Pitchen、E. Dunach、M. N. Deshmukh、H. B. Kagan

  DOI：10.1021/ja00338a030

  日期：1984.12

  Mise au point d'un nouveau reactif: Ti(O-i-C 3 H 7 ) 4 /tartrate de diethyle/eau/t-C 4 H 9 OOH dans les proportions (1:2:1:1). Ce reactif oxyde les sulfures fonctionnalises prochiraux en sulfoxydes optiquement actifs

  Mise au point d'un nouveau 反应：Ti(OiC 3 H 7 ) 4 /二乙基酒石酸盐/eau/tC 4 H 9 OOH dans les 比例（1:2:1:1）。氧化硫反应功能
• Novel Synthesis of Optically Active 2‐Ethylhexanoic Acid, 2‐Ethylhexanol, and 2‐Ethylhexylamine via the Asymmetric Favorskii Rearrangement
  作者：Motofumi Miura、Masaharu Toriyama、Shigeyasu Motohashi

  DOI：10.1080/00397910500374740

  日期：2006.1

  Abstract The asymmetric Favorskii rearrangement of optically active α‐haloketones, which are easily prepared from chiral menthyl‐4‐toluenesulfoxide in several steps using primary or secondary amines, yields their corresponding secondary or tertiary chiral amides. The secondary chiral amides were converted to acids or amines using acylation followed by hydrolysis or reduction. In addition, the tertiary

  摘要 旋光性 α-卤代酮的不对称 Favorskii 重排很容易从手性薄荷基-4-甲苯亚砜中使用伯胺或仲胺通过几个步骤制备，产生相应的仲或叔手性酰胺。使用酰化随后水解或还原将仲手性酰胺转化为酸或胺。此外，叔酰胺用 Super-Hydride® 直接还原为醇。