2-(phenylthio)cyclopent-2-en-1-one | 34780-08-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-(phenylthio)cyclopent-2-en-1-one
• 英文别名: 2-(phenylthio)-2-cyclopentenone；2-phenylthiocyclopentenone；2-Cyclopenten-1-one, 2-(phenylthio)-；2-phenylsulfanylcyclopent-2-en-1-one
• CAS: 34780-08-0
• 化学式: C₁₁H₁₀OS
• 分子量: 190.266
• InChiKey: ICPWBZQTTNZFGD-UHFFFAOYSA-N

物化性质

• 熔点：
  64-65 °C(Solv: hexane (110-54-3))
• 沸点：
  344.6±42.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(phenylthio)cyclopent-2-en-1-one 在 对苯二酚 、 氢化铝 、 mercury dichloride 作用下， 以 四氢呋喃 、 水 、 甲苯 为溶剂， 反应 32.0h， 生成 cis-bicyclo<4.3.0>non-3-en-7-one
  参考文献：
  名称：

  Diels-Alder reactions of 2-(phenylthio)cyclopentenone. Synthesis of dihydro-1-indanones

  摘要：

  DOI：

  10.1021/jo00316a028
• 作为产物：
  描述：

  2-氧代环戊烷-1-甲醛 在 对甲苯磺酰叠氮 、 三乙胺 作用下， 以 乙醚 为溶剂， 反应 0.5h， 生成 2-(phenylthio)cyclopent-2-en-1-one
  参考文献：
  名称：

  通过苯磺酰氯与α-二氮酮的αα-加成反应，合成α-（苯硫基）环烯酮和α-苯基-α-（苯硫基）酮的区域特异性合成

  摘要：

  在室温下，环状α-二氮酮与苯磺酰氯反应生成α-氯-α-（苯硫基）环链烷酮，当用三乙胺处理时，α-氯代-α-（苯硫基）环烯酮易于脱氯化氢成α-（苯硫基）环烯酮。无环末端α-二氮酮还提供α-氯代-α-（苯硫基）加合物，它们在合成α-苯基-α-（苯硫基）酮中是有用的亲电子试剂。

  DOI：

  10.1016/s0040-4039(00)81343-x

文献信息

• NaOH-Catalyzed Thiolysis of α,β-Epoxyketones in Water. A Key Step in the Synthesis of Target Molecules Starting from α,β-Unsaturated Ketones
  作者：Francesco Fringuelli、Ferdinando Pizzo、Luigi Vaccaro

  DOI：10.1021/jo035804m

  日期：2004.4.1

  high yields (90−96%). The reactions of calchone oxide (10) with thiols 2b−d have exclusively resulted in the formation of β-carbonylsulfides 10b−d (82−93% yield), coming from the nucleophilic attack at the α-position and retroaldol condensation. To highlight the synthetic utility of this procedure, one-pot multisteps preparation of vinyl sulfides 7b and 7c, vinyl sulfoxides 12 and 13, and 1,5,6,7-tetrahydro-4H-1

  NaOH（0.02-0.3摩尔当量）是α，β-环氧酮与烷基和芳基硫醇在水中硫解反应的有效催化剂。在温和的条件下（30°C和pH 6或9），具有完全的C-α-区域选择性和抗立体选择性，并完成了3,4-环氧庚烷-2-酮（1）与硫醇2a - d的硫解反应。抗-β-羰基-β-羟基硫化物3a - d的制备产率很高（95-98％）。化合物3a - d取决于其性质和pH条件，已发生脱水，C-3差向异构化反应和逆醛醇缩合。脱水抗-通过在70°C下进行原位酸性处理，化学选择性地进行了3a - d的反应，立体选择性地获得了相关的（Z）-乙烯基硫化物4，总产率为89-94％。下的NaOH催化硫解条件，环状α，β-环氧酮6 - 9只和自发脱水所示的C-α攻击，得到相应的乙烯基硫化物以高产率（90-96％）。氧化钙（10）与硫醇2b - d的反应仅导致β-羰基硫的形成10b - d（82-93％的收率）来自于α位的
• A Significant Substituent Effect on the Stereochemistry of the Trityl Salt-Catalyzed Michael Reaction
  作者：Teruaki Mukaiyama、Masanori Tamura、Shu Kobayashi

  DOI：10.1246/cl.1987.743

  日期：1987.4.5

  In the presence of a catalytic amount of trityl salts, silyl enol ethers of thioesters react with α-substituted α,β-unsaturated cyclic ketones to afford the corresponding Michael adducts in good yields with excellent lk diastereoselectivities.

  在催化量的三苯甲基盐的存在下，硫酯的甲硅烷基烯醇醚与 α-取代的 α,β-不饱和环酮反应，以良好的收率和优异的 lk 非对映选择性提供相应的迈克尔加合物。
• 1,2- versus 1,4-Addition to α-donor-cyclopenten-1-ones; a comparison of calculated and experimental data †
  作者：Hanna S. H. Gautun、Rolf Carlson、Per N. Skancke

  DOI：10.1039/a905444h

  日期：——

  A series of α-donor-cyclopenten-1-ones, 1 (α-donor; X = H, Cl, Br, OMe, pyrrolidin-1-yl, SPh and SePh) were treated with methyllithium, lithium dimethylcuprate and cyanomethyllithium in tetrahydrofuran at –78 °C. The reactions between 1 and methyllithium gave 1,2-adducts in 28–75% yield. No trace of the corresponding 1,4-adduct was observed. By treatment of 1 with lithium dimethylcuprate only 1,4-addition was obtained in 51–76% yield, except for X = OMe or pyrrolidin-1-yl, which gave no reaction at all. In the reactions between 1 and cyanomethyllithium the 1,2-adducts were the main products (43–60%), but varying amounts of 1,4-adducts (8–30%) were also formed. The products formed have been fully characterized. Net atomic charges obtained by density functional theory (DFT) calculations of the lithiated cations of 1 with X = H, Cl, Br or OMe showed very small differences between the substituted and unsubstituted systems for all X, except for X = OMe. In this case the C2 position was positive rather than negative. The C3 position was found to be significantly more negative. The calculated relative energies of the methylated and cyanomethylated 1,2- and 1,4-adducts with X = H, Cl, Br and OMe indicated that the 1,4-adducts were thermodynamically favoured by 8 to 12 kcal mol–1 for all but one case. In the cyanomethylation of 1 with X = OMe the 1,2-adduct was predicted to be favoured by 12 kcal mol–1. Thus, the predominance of 1,2-attack in the reactions involving methyllithium and cyanomethyllithium cannot be explained by the relative thermodynamic stabilities of the products.

  一系列α-给体-环戊烯-1-酮，1（α-给体；X = H、Cl、Br、OMe、吡咯烷-1-基、SPh和SePh）在-78°C下与甲基锂、二甲基铜锂和氰基甲基锂在四氢呋喃中进行反应。1与甲基锂的反应生成1,2-加合物，产率为28-75%。未观察到相应的1,4-加合物。1与二甲基铜锂的反应仅得到1,4-加成产物，产率为51-76%，除了X = OMe或吡咯烷-1-基，这些情况下根本不发生反应。1与氰基甲基锂的反应中，1,2-加合物是主要产物（43-60%），但也形成了不同数量的1,4-加合物（8-30%）。形成的产物已完全表征。通过密度泛函理论（DFT）计算得到的1的锂化阳离子（X = H、Cl、Br或OMe）的净原子电荷显示，所有X的取代和未取代体系之间的差异非常小，除了X = OMe的情况。在这种情况下，C2位置是正的而不是负的。C3位置显著更加负电。计算得到的甲基化和氰基甲基化的1,2-和1,4-加合物（X = H、Cl、Br和OMe）的相对能量表明，除了一个情况外，1,4-加合物在热力学上更优，优于8到12 kcal/mol。在X = OMe的1的氰基甲基化中，预测1,2-加合物更优，优于12 kcal/mol。因此，涉及甲基锂和氰基甲基锂的反应中1,2-攻击的主导地位不能通过产物的相对热力学稳定性来解释。
• Extracyclic Stereocontrol in Addition Reaction of Crotylsilanes with 2-Substituted 2-Cyclopentenones. Stereodivergent Synthesis of (+)-Neonepetalactone and (+)-Isoneoneptalactone
  作者：Li-Rui Pan、Takashi Tokoroyama

  DOI：10.1246/cl.1990.1999

  日期：1990.11

  The addition reaction of E- and Z-crotylsilanes with 2-substituted 2-cyclopentenones showed the preference of erythro and threo products respectively. The refinement of the selectivity was investigated and the result was utilized for efficient syntheses of the title natural products.

  E-和Z-巴豆基硅烷与2-取代的2-环戊烯酮的加成反应分别显示出赤型和苏型产物的优先性。研究了选择性的改进，并将结果用于标题天然产物的有效合成。
• Reactions of 2-phenylthio-2-cycloalkenones and 2-[phenyl(thiomethyl)]-2-cycloalkenones: Synthesis of some useful chiral and achiral intermediates
  作者：Yashwant D. Vankar、G. Kumaravel、Indrani Bhattacharya、Padma S. Vankar、Kamaljit Kaur

  DOI：10.1016/0040-4020(95)00168-8

  日期：1995.4

  diethyl malonate have been found to take place with the allyl acetates having a vinyl sulfide moiety whereas 2-phenylthio-2-cyclopentenone and 2-[phenylthio(methyl)]-2-cyclohexenone are transformed into some highly functionalised sulfur containing intermediates.

  猪水解了2-苯硫基-2-环戊烯酮，2-苯硫基-2-环己烯酮，2-苯硫基（甲基）]-2-环戊烯酮和2- [苯硫基（甲基）]-2-环己烯酮的乙酸烯丙酯肝丙酮粉以获得光学纯形式的相应醇。已发现丙二酸二乙酯与具有烯丙基硫醚部分的乙酸烯丙酯发生钯催化的烷基化反应，而2-苯硫基-2-环戊烯酮和2- [苯硫基（甲基）]-2-环己烯酮被转化为一些高度官能化的含硫化合物。中间体。