tert-butyl vinyl sulfoxide | 42779-15-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 亚砜
• 英文名称: tert-butyl vinyl sulfoxide
• 英文别名: 2-Ethenylsulfinyl-2-methylpropane
• CAS: 42779-15-7
• 化学式: C₆H₁₂OS
• 分子量: 132.227
• InChiKey: RKIAVFMRPCYSHY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  tert-butyl vinyl sulfoxide 400.0 ℃ 、1.33 Pa 条件下， 生成 (E)-ethanethial S-oxide
  参考文献：
  名称：

  Allium Chemistry:  Microwave Spectroscopic Identification, Mechanism of Formation, Synthesis, and Reactions of (E,Z)-Propanethial S-Oxide, the Lachrymatory Factor of the Onion (Allium cepa)

  摘要：

  Flow pyrolysis of 2-methyl-2-propyl 1'-propenyl sulfoxide (9b) affords a 98:2 mixture of (Z)- and (E)-propanethial S-oxide ((Z)- and (E)-5b), both characterized by Fourier transform microwave (FT-MW) spectroscopy, Sulfines (Z)- and (E)-5b are also identified by FT-MW in chopped onion volatiles and by NMR spectroscopy in onion extracts. Similarly, flow pyrolysis of 2-methyl-2-propyl vinyl sulfoxide (9c) affords (Z)- and (E)-isomers of ethanethial S-oxide (5a), identified by FT-MW methods. Pyrolysis in the presence of D2O affords (Z)-5a-d(1) and (Z)-5a-d(2) from 99 and (Z)-5b-d(1) from 9b; (Z)-5b-d(1) is also produced when an onion is homogenized in D2O. Pyrolysis of 9c with ethyl propiolate gives ethyl (E)-3-(vinylsulfinyl)acrylate (10). Neat 59 at 100 degrees C gives acetaldehyde. On standing, 5b dimerizes to trans-3,3-diethyl-1,2-dithietane 1,1-dioxide (12a); Me(3)SiCH=S+-O- (5f) undergoes an analogous dimerization. Compound 5b shows moderate potency as an anticarcinogen in inducing the enzyme quinone reductase.

  DOI：

  10.1021/ja960722j
• 作为产物：
  描述：

  叔丁基亚磺酰氯 、 乙烯基溴化镁 以 四氢呋喃 为溶剂， 以35%的产率得到tert-butyl vinyl sulfoxide
  参考文献：
  名称：

  Allium Chemistry:  Microwave Spectroscopic Identification, Mechanism of Formation, Synthesis, and Reactions of (E,Z)-Propanethial S-Oxide, the Lachrymatory Factor of the Onion (Allium cepa)

  摘要：

  Flow pyrolysis of 2-methyl-2-propyl 1'-propenyl sulfoxide (9b) affords a 98:2 mixture of (Z)- and (E)-propanethial S-oxide ((Z)- and (E)-5b), both characterized by Fourier transform microwave (FT-MW) spectroscopy, Sulfines (Z)- and (E)-5b are also identified by FT-MW in chopped onion volatiles and by NMR spectroscopy in onion extracts. Similarly, flow pyrolysis of 2-methyl-2-propyl vinyl sulfoxide (9c) affords (Z)- and (E)-isomers of ethanethial S-oxide (5a), identified by FT-MW methods. Pyrolysis in the presence of D2O affords (Z)-5a-d(1) and (Z)-5a-d(2) from 99 and (Z)-5b-d(1) from 9b; (Z)-5b-d(1) is also produced when an onion is homogenized in D2O. Pyrolysis of 9c with ethyl propiolate gives ethyl (E)-3-(vinylsulfinyl)acrylate (10). Neat 59 at 100 degrees C gives acetaldehyde. On standing, 5b dimerizes to trans-3,3-diethyl-1,2-dithietane 1,1-dioxide (12a); Me(3)SiCH=S+-O- (5f) undergoes an analogous dimerization. Compound 5b shows moderate potency as an anticarcinogen in inducing the enzyme quinone reductase.

  DOI：

  10.1021/ja960722j

文献信息

• HCV PROTEASE INHIBITORS AND USES THEREOF
  申请人：Niu Deqiang

  公开号：US20090176858A1

  公开（公告）日：2009-07-09

  The present invention provides compounds, pharmaceutically acceptable compositions thereof, and methods of using the same.

  本发明提供了化合物、药学上可接受的组合物以及使用它们的方法。
• Divergent Method to <i>trans</i>-5-Hydroxy-6-alkynyl/alkenyl-2-piperidinones: Syntheses of (−)-Epiquinamide and (+)-Swainsonine
  作者：Chang-Mei Si、Zhuo-Ya Mao、Han-Qing Dong、Zhen-Ting Du、Bang-Guo Wei、Guo-Qiang Lin

  DOI：10.1021/acs.joc.5b00803

  日期：2015.6.5

  An efficient diastereoselective approach to access trans-5-hydroxy-6-alkynyl/alkenyl-2-piperidinones has been developed through nucleophilic addition of α-chiral aldimines using alkynyl/alkenyl Grignard reagents. The diastereoselectivity of alkenyl in C-6 position of 2-piperidinone was controlled by α-alkoxy substitution, while the alkynyl was controlled by the coordination of the α-alkoxy substitution

  通过使用炔基/烯基格利雅试剂试剂亲核加成α-手性醛亚胺，已经开发了一种有效的非对映选择性方法，可用于反式-5-羟基-6-炔基/烯基-2-哌啶酮。α-烷氧基取代控制2-哌啶酮C-6位置链烯基的非对映选择性，而α-烷氧基取代和亚磺酰胺的立体化学则控制炔基。（-）-表喹酰胺和（+）-swainsonine的不对称合成证明了这种简单的级联过程的实用性。
• Asymmetric Intermolecular Pauson−Khand Reactions of Unstrained Olefins:  The (<i>o</i>-Dimethylamino)phenylsulfinyl Group as an Efficient Chiral Auxiliary
  作者：Marta Rodríguez Rivero、Juan Carlos de la Rosa、Juan Carlos Carretero

  DOI：10.1021/ja038491l

  日期：2003.12.1

  The first asymmetric version of intermolecular Pauson-Khand reactions of unstrained alkenes is described. Generally simple acyclic alkenes exhibit low reactivity and regioselectivity in intermolecular Pauson-Khand reactions; however, o-(dimethylamino)phenyl vinyl sulfoxide reacts under very mild conditions with a wide variety of terminal alkynes in a completely regioselective and highly stereoselective

  描述了无应变烯烃的分子间 Pauson-Khand 反应的第一个不对称版本。通常，简单的无环烯烃在分子间 Pauson-Khand 反应中表现出低反应性和区域选择性；然而，邻（二甲氨基）苯基乙烯基亚砜在非常温和的条件下以完全区域选择性和高度立体选择性的方式与多种末端炔烃反应。抗生素 (-)-戊烯霉素 I 的非常短的对映选择性合成说明了所得 5-亚磺酰基-2-环戊烯酮在不对称合成中的应用。
• Vinyl Sulfoxides as Stereochemical Controllers in Intermolecular Pauson-Khand Reactions: Applications to the Enantioselective Synthesis of Natural Cyclopentanoids
  作者：Marta Rodríguez Rivero、Inés Alonso、Juan C. Carretero

  DOI：10.1002/chem.200400443

  日期：2004.11.5

  diastereoselectivity (de=86->96 %, (S,R(S)) diastereomer). Experimental studies suggest that the high reactivity exhibited by the vinyl sulfoxide 1 i relies on the ability of the amine group to act as a soft ligand on the alkyne dicobalt complex prior to the generation of the cobaltacycle intermediate. On the other hand, both theoretical and experimental studies show that the high stereoselectivity of the process is

  描述了亚砜在不对称分子间Pauson-Khand反应中作为手性助剂的用途。在α，β-不饱和亚砜中筛选了硫原子上的各种取代基后，事实证明，现成的邻-（N，N-二甲基氨基）苯基乙烯基亚砜（1i）在氮气氛下可与取代的末端炔烃高度反应-氧化促进条件（CH3CN，0摄氏度）。另外，这些Pauson-Khand反应以完全的区域选择性和非常高的非对映选择性（de ＝ 86-＞ 96％，（S，R（S））非对映异构体）发生。实验研究表明，乙烯基亚砜1 i表现出的高反应性取决于在生成钴环中间体之前，胺基团充当炔烃二钴配合物上的软配体的能力。另一方面，理论和实验研究均表明，该方法的高立体选择性是由于所得的5-亚磺酰基-2-环戊烯酮加合物在C5中心容易发生热力学差向异构。当考虑到已知的不对称分子间Pauson-Khand反应仅限​​于使用高反应性的双环烯烃，主要是降冰片烯和降冰片二烯时，该新颖的方法构成了具有未应
• Novel cellulose derivative, process for preparing the same and sulfur dioxide gas permselective membrane comprising the same
  申请人：Shin-Etsu Chemical Co., Ltd.

  公开号：EP0213944A2

  公开（公告）日：1987-03-11

  Hydrocarbylsulfinylethyl cellulose represented by the formula (1): wherein. X may be the same or different and represents hydrogen atom or hydrocarbylsulfinylethyl group represented by the formula (II): wherein, R may be the same or different and represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, with the average substitution degree with the hydrocarbylsulfinylethyl group of the formula (II) per glucose unit being at least 0.05 is provided together with a process for preparing the same and a sulfur dioxide gas permeation membrane comprising said cellulose derivative. This membrane is excellent in sulfur dioxide gas permselectivity.

  由式(1)代表的烃基亚磺酰基乙基纤维素： 其中X可以相同或不同，代表氢原子或由式(II)代表的烃基亚磺酰基乙基： 其中，R 可以相同或不同，代表具有 1 至 6 个碳原子的烷基或苯基，每个葡萄糖单位与式 (II) 中的烃基亚磺酰基的平均取代度至少为 0.05。这种膜具有优异的二氧化硫气体渗透性。

表征谱图