3-allyltetrahydrothiopyran-4-one | 97694-65-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻烷
• 英文名称: 3-allyltetrahydrothiopyran-4-one
• 英文别名: 2-allyl tetrahydrothiopyranone；3-allyl-4-thianone；3-allylthian-4-one；3-prop-2-enylthian-4-one
• CAS: 97694-65-0；145213-38-3；91791-03-6
• 化学式: C₈H₁₂OS
• 分子量: 156.249
• InChiKey: RUXWMVYOIAFFDD-UHFFFAOYSA-N

物化性质

• 熔点：
  79-80 °C
• 沸点：
  78-80 °C(Press: 1.5 Torr)
• 密度：
  1.030±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  3-allyltetrahydrothiopyran-4-one 在 platinum(IV) oxide 氢气 作用下， 以 乙醇 为溶剂， 以100%的产率得到3-propyltetrahydro-2H-thiopyran-4-one
  参考文献：
  名称：

  从光学活性 3,3-二烷基-4-噻酮合成光学活性内酯和 3-环戊烯酮

  摘要：

  光学活性 3,3-二烷基-4-硫酮 3 和 4 以中等收率和约 90% 的对映体纯度使用不对称方法制备，该方法涉及手性 3-烷基-4-硫亚胺与甲基乙烯基酮的迈克尔型烷基化或丙烯酸甲酯。然后通过碱基诱导的环化将二酮 3 转化为新的杂环 5。3-甲基-和3-烯丙基-3-(2-甲氧基羰基乙基)-4-噻酮((+)-4a和(+)-4b)被转化为双环内酯(-)-6和(-)-7 ， 分别。衍生自内酯 (-)-6a 的砜 (+)-8 的立体化学通过 X 射线晶体结构分析确定。使用硼化镍对内酯 (-)-6b 进行脱硫得到相应的内酯 (+)-9。

  DOI：

  10.1246/bcsj.66.1743
• 作为产物：
  描述：

  3-allyl-3-methoxycarbonylthian-4-one 在 lithium iodide 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以87%的产率得到3-allyltetrahydrothiopyran-4-one
  参考文献：
  名称：

  Lane, Simon; Quick, Stephen J.; Taylor, Richard J.K., Journal of the Chemical Society. Perkin transactions I, 1985, p. 893 - 898

  摘要：

  DOI：

文献信息

• Developing the Saegusa–Ito Cyclisation for the Synthesis of Difluorinated Cyclohexenones
  作者：Jonathan M. Percy、Adam W. McCarter、Alan L. Sewell、Nikki Sloan、Alan R. Kennedy、David J. Hirst

  DOI：10.1002/chem.201503653

  日期：2015.12.21

  the turnover of the initial palladium(II) salt, whereas the provision of an oxygen atmosphere ensured more rapid reaction. Annulations required a minimum level of substitution on the chain, but failed when the alkene was substituted. Annelations allowed a range of n,6‐bicyclic systems to be prepared and afforded three products, in which heterocycles were fused to the new cyclohexenone. The least substituted

  钯（II）催化的环烯基化反应（Saegusa–Ito环化）首次用于在温和条件下将二氟甲硅烷基醚转化为二氟环烯酮。甲硅烷基醚前体是从三氟乙醇分两个高产步骤制备的，并以中等至良好的收率环化。空气和氯化铜（I）在乙腈中的混合产生了初始钯（II）盐的周转，而提供氧气气氛则确保了更快速的反应。必须在链上进行最低限度的取代，但是当烯烃被取代时，失败了。退火允许制备一系列n，6-双环系统，并提供三种产物，其中杂环与新的环己烯酮稠合。
• A new access to β-methyl substituted secondary alcohols. Application to the synthesis of 4-methylheptan-3-ol
  作者：Josef Růžička、Bohumı́r Koutek、Ludvı́k Streinz、David Šaman、Ladislav Lešetický

  DOI：10.1016/s0957-4166(99)00372-9

  日期：1999.9

  starting from 4-thianones. Key steps in the synthesis include: (a) reduction of 3-propyl-4-thianone to yield an easily separable isomeric mixture of cis- and trans-3-propyl-4-thianols; and (b) a highly efficient resolution of the particular cis/trans-isomers through a chromatographic separation of their respective esters with (S)-chlorofluoroacetic acid. Subsequent hydrolysis and desulfurization gave

  通过从4-噻吩酮开始的五步路线合成了4-甲基庚烷-3-醇的所有四个立体异构体。合成的关键步骤包括：（a）还原3-丙基-4-噻吩酮，以生成易于分离的顺式和反式-3-丙基-4-噻吩醇异构体混合物；（b）通过用（S）-氯氟乙酸色谱分离其各自的酯，对特定的顺式/反式异构体进行高效拆分。随后的水解和脱硫以18％的总收率得到了所需的化合物。获得的所有立体异构体的纯度均优于90％。
• Preparation of 3-Substituted 4-Thianones and Their 1,1-Dioxides via Palladium Mediated Deallyloxycarbonylation
  作者：Guy Casy、Alan G. Sutherland、Richard J. K. Taylor、Peter G. Urben

  DOI：10.1055/s-1989-27389

  日期：——

  3-Alkyl-4-thianones 4 (3-alkyl-thiacyclohexan-4-ones) can be conveniently prepared by the alkylation of 3-allyloxycarbonyl-4-thianone (1b) followed by deallyloxycarbonylation mediated by tetrakis (triphenylphosphine)palladium in the presence of morpholine. The corresponding sulphones 9, as well as 2,3-dialkyl 4-thianone derivatives 12 and 13 can be prepared by analogous procedures.

  3- 烷基-4-噻酮 4（3-烷基-硫杂环己烷-4-酮）可以通过 3-烯丙氧羰基-4-噻酮（1b）的烷基化，然后在吗啉存在下，由四（三苯基膦）钯介导的脱烯丙氧羰基化反应方便地制备。相应的砜类化合物 9 以及 2,3-二烷基 4-噻酮衍生物 12 和 13 可通过类似的方法制备。
• TETRAHYDROTHIOPYRAN-4-ONE. A USEFUL 5 C SYNTHON FOR THE SYNTHESIS OF 3-CYCLOPENTENONES
  作者：Haruo Matsuyama、Yasuyuki Miyazawa、Yuji Takei、Michio Kobayashi

  DOI：10.1246/cl.1984.833

  日期：1984.5.5

  2-Alkyl-3-cyclopentenones were prepared in moderate yields starting from tetrahydrothiopyran-4-one by the one-pot Ramberg–Bäcklund reaction of 6-alkyl-1,4-dioxa-8-thiaspiro[4.5]decane 8,8-dioxides, followed by acid catalyzed de-dioxolanation.

  通过 6-烷基-1,4-二氧杂-8-硫杂螺[4.5]癸烷 8,8-二氧化合物的 Ramberg-Bäcklund 一锅反应，以四氢噻喃-4-酮为起点，制备了 2-烷基-3-环戊烯酮，收率适中，随后在酸催化下进行了去二氧戊环化反应。
• A Comparison of Cyclohexanone and Tetrahydro-4<i>H</i>-thiopyran-4-one 1,1-Dioxide as Pharmacophores for the Design of Peptide-Based Inhibitors of the Serine Protease Plasmin
  作者：Fengtian Xue、Christopher T. Seto

  DOI：10.1021/jo0508954

  日期：2005.10.1

  The plasminogen system is important in the proteolytic cascade that facilitates angiogenesis, a process that is essential for tumor growth and metastasis. The serine protease plasmin has a central role in the plasminogen system. This protease acts by degrading several components of the basement membrane and by activating other proteases. Therefore, inhibition of plasmin may be an effective method for blocking angiogenesis and, as a result, inhibiting the growth of primary tumors and secondary metastases. Three pairs of plasmin inhibitors were synthesized to compare the relative potency of inhibitors that are based upon a cyclohexanone or a tetrahydro-4H-thiopyran-4-one 1,1-dioxide nucleus. Compounds 1, 3, and 5 were cyclohexanone-based inhibitors, whereas compounds 2, 4, and 6 were tetrahydro-4H-thiopyran-4-one 1,1-dioxide-based inhibitors. Compounds 5 and 6 are reasonable inhibitors with IC50 values of 25 and 5.5 mu M, respectively. Comparisons of the IC50 values of the three pairs show that the electron-withdrawing sulfone functional group is a beneficial element for the design of plasmin inhibitors. The presence of the sulfone increases inhibitor potency by a factor of 3-5 when compared to inhibitors that are based upon a simple cyclohexanone core.