1-(2,2-Bis-ethylsulfanyl-ethenesulfonyl)-4-methyl-benzene | 158752-57-9

• 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: 1-(2,2-Bis-ethylsulfanyl-ethenesulfonyl)-4-methyl-benzene
• 英文别名: 1-[2,2-Bis(ethylsulfanyl)ethenylsulfonyl]-4-methylbenzene
• CAS: 158752-57-9
• 化学式: C₁₃H₁₈O₂S₃
• 分子量: 302.483
• InChiKey: DBMMLPWICSFKJP-UHFFFAOYSA-N

物化性质

• 熔点：
  68-70 °C(Solv: hexane (110-54-3))
• 沸点：
  456.1±45.0 °C(Predicted)
• 密度：
  1.203±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  93.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  甲醇 、 1-(2,2-Bis-ethylsulfanyl-ethenesulfonyl)-4-methyl-benzene 在 盐酸 、 硫酸 、 mercury dichloride 作用下， 生成 对甲苯磺酰乙酸甲酯
  参考文献：
  名称：

  Additions of Organocopper Reagents and Heteroatom Nucleophiles to 1-Phenylseleno-2-(p-toluenesulfonyl)ethyne. Preparation of Vinyl and Allenic Sulfones and Formation of Michael, Anti-Michael, and Rearrangement Products

  摘要：

  1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (4) was produced nearly quantitatively from p-(toluenesulfonyl)ethyne and benzeneselenenyl chloride. It underwent stereo- and regioselective syn-additions of organocopper reagents RCu(CN)Li to the beta-position of the sulfone moiety to afford adducts 5. Further reaction of the products with reagents RCu(SePh)Li resulted in substitution of the phenylseleno group with retention of configuration. Control of E,Z-stereochemistry in the product beta,beta-disubstituted vinyl sulfones is therefore achieved by the order of addition of the reagents. Selenoxide syn-elimination of adducts 5 afforded the corresponding allenic sulfones. The additions of amines and alkoxides to 4 produced the corresponding anti-Michael regioisomers (where attack occurred a to the sulfone group) as the major or sole products. The additions were highly stereoselective, proceeding by anti-addition in the anti-Michael series and by syn-addition in the corresponding Michael regioisomers. The reactions of 4 with thiolates and selenolates were more complex, affording rearranged adducts and Michael adducts as the major and minor products, respectively. The formation of the rearranged products can be rationalized by a series of addition-elimination processes. Phenylselenoethyne (43) underwent conjugate additions of pyrrolidine, sodium methoxide, sodium ethanethiolate, and benzeneselenolate anion, affording the corresponding cis isomers via anti-addition. The experiments with heteroatom nucleophiles and acetylenes 4 and 43 show that the phenylseleno group has a surprisingly large activating effect upon conjugate additions.

  DOI：

  10.1021/jo981224r
• 作为产物：
  描述：

  乙炔基对甲苯基砜 在 sodium hydride 、 三乙胺 作用下， 反应 5.83h， 生成 1-(2,2-Bis-ethylsulfanyl-ethenesulfonyl)-4-methyl-benzene
  参考文献：
  名称：

  Additions of Organocopper Reagents and Heteroatom Nucleophiles to 1-Phenylseleno-2-(p-toluenesulfonyl)ethyne. Preparation of Vinyl and Allenic Sulfones and Formation of Michael, Anti-Michael, and Rearrangement Products

  摘要：

  1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (4) was produced nearly quantitatively from p-(toluenesulfonyl)ethyne and benzeneselenenyl chloride. It underwent stereo- and regioselective syn-additions of organocopper reagents RCu(CN)Li to the beta-position of the sulfone moiety to afford adducts 5. Further reaction of the products with reagents RCu(SePh)Li resulted in substitution of the phenylseleno group with retention of configuration. Control of E,Z-stereochemistry in the product beta,beta-disubstituted vinyl sulfones is therefore achieved by the order of addition of the reagents. Selenoxide syn-elimination of adducts 5 afforded the corresponding allenic sulfones. The additions of amines and alkoxides to 4 produced the corresponding anti-Michael regioisomers (where attack occurred a to the sulfone group) as the major or sole products. The additions were highly stereoselective, proceeding by anti-addition in the anti-Michael series and by syn-addition in the corresponding Michael regioisomers. The reactions of 4 with thiolates and selenolates were more complex, affording rearranged adducts and Michael adducts as the major and minor products, respectively. The formation of the rearranged products can be rationalized by a series of addition-elimination processes. Phenylselenoethyne (43) underwent conjugate additions of pyrrolidine, sodium methoxide, sodium ethanethiolate, and benzeneselenolate anion, affording the corresponding cis isomers via anti-addition. The experiments with heteroatom nucleophiles and acetylenes 4 and 43 show that the phenylseleno group has a surprisingly large activating effect upon conjugate additions.

  DOI：

  10.1021/jo981224r

文献信息

• Generation of Sulfonyl Radicals from Sodium Sulfinates by Oxidation with Metallic Oxidants and Their Addition Reaction with Olefins
  作者：Koichi Narasaka、Takashi Mochizuki、Satoshi Hayakawa

  DOI：10.1246/cl.1994.1705

  日期：1994.9

  Sodium arylsulfinates are treated with manganese(III) 2-pyridinecarboxylate or cerium(IV) tetrabutylammonium nitrate to generate sulfonyl radicals, which react with various olefins giving the addition products.

  芳基亚磺酸钠用锰 (III) 2-吡啶羧酸盐或铈 (IV) 四丁基硝酸铵处理生成磺酰基自由基，磺酰基自由基与各​​种烯烃反应生成加成产物。
• Sulfonylation and Phosphinylation of Olefinic Compounds with Radical Species Generated by the Oxidation of Sodium Sulfinates and Diphenylphosphine Oxide
  作者：Takashi Mochizuki、Satoshi Hayakawa、Koichi Narasaka

  DOI：10.1246/bcsj.69.2317

  日期：1996.8

  Sodium arenesulfinates are oxidized with manganese(III) 2-pyridinecarboxylate or ammonium cerium(IV) nitrates to generate sulfonyl radicals, which add to olefinic compounds to afford sulfonylated products in good yield. When 1-vinyl cyclic alcohols are used as sulfonyl radical acceptors, sulfonylation proceeds with ring-enlargement. Diphenylphosphinyl radical can also be generated by treating diphenylphosphine

  芳烃亚磺酸钠与 2-吡啶羧酸锰 (III) 或硝酸铈 (IV) 铵氧化生成磺酰基自由基，磺酰基自由基添加到烯烃化合物中，以良好的收率提供磺酰化产物。当 1-乙烯基环醇用作磺酰基自由基受体时，磺酰化会随着环扩大而进行。二苯基膦基也可以通过用 2-吡啶羧酸锰 (III) 处理氧化二苯基膦并与烯烃化合物反应生成次膦酰化产物而产生。
• 1-(Phenylseleno)-2-(p-toluenesulfonyl)ethyne. A Novel Acetylenic Sulfone That Undergoes Normal and Anti-Michael Nucleophilic Additions
  作者：T Back

  DOI：10.1016/00404-0399(50)09253-

  日期：1995.7.3
• Narasaka Koichi, Mochizuki Takashi, Hayakawa Satoshi, Chem. Lett, (1994) N 9, S 1705-1708
  作者：Narasaka Koichi, Mochizuki Takashi, Hayakawa Satoshi

  DOI：——

  日期：——
• Additions of Organocopper Reagents and Heteroatom Nucleophiles to 1-Phenylseleno-2-(<i>p</i>-toluenesulfonyl)ethyne. Preparation of Vinyl and Allenic Sulfones and Formation of Michael, Anti-Michael, and Rearrangement Products
  作者：Thomas G. Back、Richard J. Bethell、Masood Parvez、Daniel Wehrli

  DOI：10.1021/jo981224r

  日期：1998.10.1

  1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (4) was produced nearly quantitatively from p-(toluenesulfonyl)ethyne and benzeneselenenyl chloride. It underwent stereo- and regioselective syn-additions of organocopper reagents RCu(CN)Li to the beta-position of the sulfone moiety to afford adducts 5. Further reaction of the products with reagents RCu(SePh)Li resulted in substitution of the phenylseleno group with retention of configuration. Control of E,Z-stereochemistry in the product beta,beta-disubstituted vinyl sulfones is therefore achieved by the order of addition of the reagents. Selenoxide syn-elimination of adducts 5 afforded the corresponding allenic sulfones. The additions of amines and alkoxides to 4 produced the corresponding anti-Michael regioisomers (where attack occurred a to the sulfone group) as the major or sole products. The additions were highly stereoselective, proceeding by anti-addition in the anti-Michael series and by syn-addition in the corresponding Michael regioisomers. The reactions of 4 with thiolates and selenolates were more complex, affording rearranged adducts and Michael adducts as the major and minor products, respectively. The formation of the rearranged products can be rationalized by a series of addition-elimination processes. Phenylselenoethyne (43) underwent conjugate additions of pyrrolidine, sodium methoxide, sodium ethanethiolate, and benzeneselenolate anion, affording the corresponding cis isomers via anti-addition. The experiments with heteroatom nucleophiles and acetylenes 4 and 43 show that the phenylseleno group has a surprisingly large activating effect upon conjugate additions.