Ethyl bis(phenylthio)-acetate | 20461-96-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: Ethyl bis(phenylthio)-acetate
• 英文别名: Acetic acid, bis(phenylthio)-, ethyl ester；ethyl 2,2-bis(phenylsulfanyl)acetate
• CAS: 20461-96-5
• 化学式: C₁₆H₁₆O₂S₂
• 分子量: 304.434
• InChiKey: XTRVHAAFWOCIRN-UHFFFAOYSA-N

物化性质

• 沸点：
  186-188 °C(Press: 0.3 Torr)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  76.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Ethyl bis(phenylthio)-acetate 在 二异丁基氢化铝 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 2.0h， 以80%的产率得到bis(phenylthio)acetaldehyde
  参考文献：
  名称：

  Sulfur-Directed Regioselective Radical Cyclization Leading to .beta.-Lactams: Formal Synthesis of (.+-.)-PS-5 and (+)-Thienamycin

  摘要：

  A new method for the synthesis of beta-lactams by tributyltin hydride (Bu(3)SnH)-mediated radical cyclizations of N-ethenyl-alpha-bromo amides bearing sulfur-substituent(s) at the terminus of the N-vinylic bond is described. N-[2-(Phenylthio)ethenyl]-alpha-bromoacetamide (11), upon treatment with Bu(3)SnH in the presence of azobis(isobutyronitrile) (AIBN) in boiling toluene, underwent radical cyclization in a 4-exo-trig manner to give beta-lactam 13, but in low yield (22%), whereas N-[2,2-bis(phenylthio)ethenyl] congener 23 cyclized with a high degree of efficiency to give beta-lactam 25 and a partially desulfurized lactam 13 in 70% combined yield. The effectiveness of the 4-exo cyclization of 23 can be explained in terms of the high stability of the intermediate of radical 19b. Similar treatment of alpha-bromobutanamide 24 with Bu(3)SnH afforded, in 58% yield, beta-lactam 26, which was transformed, via aldehyde 31, into the key intermediate 35 for the synthesis of(+/-)-PS-5 (36). 1,2-Asymmetric induction in radical cyclizations leading to beta-lactams was then examined. Cyclization of (2S,3R)-3-acetoxy-2-bromo-N-[2-(phenylthio)ethenyl]butanamide (38) proceeded with no diastereoselectivity to give beta-lactams 40a and 40b in approximately equal amounts. However, 2,2-bis(phenylthio) congener 39 provided (3R,4R)-2-azetidinone 41a and its (3S,4S)-isomer 41b in a ratio of ca. 2:1. Similarly, (2R,3S)-butanamide 47 afforded 48a as a major product. Saponification of 48a followed by partial desulfurization of 49 gave alcohol 50, which was then subjected to Mitsunobu inversion to afford 52. This compound was converted into the key intermediate 56 for the synthesis of (+)-thienamycin (58). Reversibility of the radical cyclization leading to the beta-lactams is discussed.

  DOI：

  10.1021/jo00110a035
• 作为产物：
  描述：

  (甲基硫代)醋酸乙酯 在 aluminum oxide 磺酰氯 作用下， 反应 24.0h， 生成 Ethyl bis(phenylthio)-acetate
  参考文献：
  名称：

  一种新颖且方便的双[芳硫基]甲烷的合成方法

  摘要：

  用中性氧化铝处理芳基氯甲基硫化物可以高产率生产双[芳硫基]甲烷。

  DOI：

  10.1016/s0040-4039(00)78674-6

文献信息

• Organic Syntheses without Solvent: Preparation of Sulfones and Dithioacetals
  作者：Georges Bram、André Loupy、Marie Claude Roux-Schmitt、Jean Sansoulet、Tekla Strzalko、Jacqueline Seyden-Penne

  DOI：10.1055/s-1987-27843

  日期：——

  Sulfones are prepared by alkylation of sulfinate salts under solid-liquid phase-transfer catalysis without solvent; dithioacetals are obtained by heterogeneous uncatalyzed reactions of potassium arenethiolates and gem-dihaloalkanes. In both cases, the yields are high and the reaction conditions are mild. Some limitations are given.

  砜可通过无溶剂固-液相转移催化磺酸盐的烷基化来制备；二硫代缩醛则由无催化剂的非均相反应生成，该反应涉及钾芳硫醇盐与偕二卤代烷。两种情况下的产率均较高，反应条件也温和。此外，还提到了一些限制性因素。
• First Lewis Acid Catalyzed Generation and Reaction of α-Organylsulfanyl and α-Organylselanyl Carbenium Ions Using Ethyl α-Fluoroacetate Derivatives
  作者：Mitsuhiro Yoshimatsu、Masayo Kawamoto、Kohei Gotoh

  DOI：10.1002/ejoc.200500179

  日期：2005.7

  Lewis acid catalyzed generation and reactions of α-organylsulfanyl and α-organylselanyl carbenium ions with nucleophiles proceeded in high yields using α-fluoro-α-organylsulfanyl- and α-fluoro-α-organylselanylacetate and 5 mol-% scandium triflate. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  使用 α-氟-α-有机基硫基-和 α-氟-α-有机基硒基乙酸盐和 5 mol% 的三氟甲磺酸钪，路易斯酸催化 α-有机基硫基和 α-有机基硒基碳鎓离子与亲核试剂的生成和反应以高产率进行。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Highly selective electrochemical fluorination of dithioacetal derivatives bearing electron-withdrawing substituents at the position α to the sulfur atom using poly(HF) salts
  作者：Bin Yin、Shinsuke Inagi、Toshio Fuchigami

  DOI：10.3762/bjoc.11.12

  日期：——

  Anodic fluorination of dithioacetals bearing electron-withdrawing ester, acetyl, amide, and nitrile groups at their α-positions was comparatively studied using various supporting poly(HF) salts like Et₃N·nHF (n = 3–5) and Et₄NF·nHF (n = 3–5). In the former two cases, the corresponding α-fluorination products or fluorodesulfurization products were obtained selectively depending on supporting poly(HF) salts used. In sharp contrast, in the latter two cases, fluorination product selectivity was strongly affected by the electron-withdrawing ability of α-substituents: A dithioacetal bearing a relatively weak electron-withdrawing amide group provided a fluorodesulfurization product selectively while a dithioacetal having a strongly electron-withdrawing nitrile group gave the α-fluorination product predominantly regardless of the poly(HF) salts used.

  含有α位电子吸引酯、乙酰、酰胺和腈基团的二硫代缩醛的阳极氟化反应进行了比较研究，使用了各种支持性聚合物(HF)盐，如Et₃N·nHF (n = 3–5)和Et₄NF·nHF (n = 3–5)。在前两种情况下，根据使用的支持性聚合物(HF)盐，选择性地获得了相应的α-氟化产物或氟去硫化产物。与此形成鲜明对比的是，在后两种情况下，氟化产物的选择性受到α位取代基的电子吸引能力的强烈影响：含有相对较弱的电子吸引酰胺基团的二硫代缩醛选择性地提供氟去硫化产物，而具有强烈电子吸引腈基团的二硫代缩醛无论使用何种聚合物(HF)盐，主要产生α-氟化产物。
• Scandium-Catalyzed Carbon-Carbon Bond Formations Using .ALPHA.-Organosulfanyl and Organoselanyl-.ALPHA.-fluoroacetic Acid Derivatives
  作者：Kohei Gotoh、Teruhisa Yamamoto、Mitsuhiro Yoshimatsu

  DOI：10.1248/cpb.54.1611

  日期：——

  The scandium-catalyzed reactions of alpha-organosulfanyl and organoselanyl-alpha-fluoroacetates 1-2, acetamides 3-4 and acetonitrile 5 with soft nucleophiles proceeded to give the products 6a-b, 7a-c, 8a-c, 9a-e in good to high yields. We also successfully performed the scandium-catalyzed intramolecular cyclization reactions and obtained the unique 5-methylene-2-oxotetrahydropyrans 16-17.

  soft催化的α-有机硫烷基和有机糖基-α-氟乙酸酯1-2，乙酰胺3-4和乙腈5与柔软的亲核试剂的反应进行，得到的产物6a-b，7a-c，8a-c，9a-e好到高产。我们还成功地进行了dium催化的分子内环化反应，并获得了独特的5-亚甲基-2-氧代四氢吡喃16-17。
• Lissel, Manfred, Liebigs Annalen der Chemie, 1982, # 9, p. 1589 - 1601
  作者：Lissel, Manfred

  DOI：——

  日期：——