2-(phenylsulfanyl)-2-cycloheptenone | 85808-24-8

• 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-(phenylsulfanyl)-2-cycloheptenone
• 英文别名: 2-(phenylsulfanyl)cyclohept-2-enone；2-(Phenylthio)-2-cycloheptenone；2-Phenylthio-2-cycloheptenon；2-Phenylsulfanylcyclohept-2-en-1-one
• CAS: 85808-24-8
• 化学式: C₁₃H₁₄OS
• 分子量: 218.32
• InChiKey: KVQGNFKGQWMKLW-UHFFFAOYSA-N

物化性质

• 沸点：
  372.9±42.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 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-(phenylsulfanyl)-2-cycloheptenone 在 sodium periodate 作用下， 以 甲醇 为溶剂， 反应 16.0h， 以98%的产率得到2-(phenylsulfinyl)cyclohept-2-en-1-one
  参考文献：
  名称：

  Cyclopentannulations leading to the synthesis of bicyclic conjugated enediones.

  摘要：

  Base-induced reactions of 1-(phenylsulfonyl)-2-methylene-3-bromopropane (4) with 2-(phenylsulfonyl)-2-cycloalkenones 8a-d were investigated with the ultimate purpose to develop a route leading to bicyclic conjugated enediones. Low-temperature, fast-quenched reactions led generally to open-chain adducts, while increase of temperature and addition of HMPA resulted in subsequent ring closure by a tandem Michael-S(N)2 process. The stereochemical features of the bicyclo[3.3.0]octanes 11 and 12, bicyclo[4.3.0]nonanes 18 and 19, bicyclo[5.3.0]decanes 22 and 23, and bicyclo[6.3.0]-undecanes 26-28 thus obtained have been determined. Ozonolysis and silica-induced elimination of the tertiary phenylsulfonyl group converted stereoselectively the above products into the desired enediones: pentalenedione 29, indenedione 30, azulenedione 32 and cyclopentacyclooctenedione 33, respectively.

  DOI：

  10.1021/jo00121a035
• 作为产物：
  描述：

  2-(phenylsulfinyl)cycloheptanone 在 甲烷磺酸 、 乙酸酐 作用下， 以86%的产率得到2-(phenylsulfanyl)-2-cycloheptenone
  参考文献：
  名称：

  Cyclopentannulations leading to the synthesis of bicyclic conjugated enediones.

  摘要：

  Base-induced reactions of 1-(phenylsulfonyl)-2-methylene-3-bromopropane (4) with 2-(phenylsulfonyl)-2-cycloalkenones 8a-d were investigated with the ultimate purpose to develop a route leading to bicyclic conjugated enediones. Low-temperature, fast-quenched reactions led generally to open-chain adducts, while increase of temperature and addition of HMPA resulted in subsequent ring closure by a tandem Michael-S(N)2 process. The stereochemical features of the bicyclo[3.3.0]octanes 11 and 12, bicyclo[4.3.0]nonanes 18 and 19, bicyclo[5.3.0]decanes 22 and 23, and bicyclo[6.3.0]-undecanes 26-28 thus obtained have been determined. Ozonolysis and silica-induced elimination of the tertiary phenylsulfonyl group converted stereoselectively the above products into the desired enediones: pentalenedione 29, indenedione 30, azulenedione 32 and cyclopentacyclooctenedione 33, respectively.

  DOI：

  10.1021/jo00121a035

文献信息

• Carbenoid type base induced ring expansion of the adducts of cyclic ketones with bis(phenylthio)methyllithium
  作者：William D. Abraham、M. Bhupathy、Theodore Cohen

  DOI：10.1016/s0040-4039(00)96080-5

  日期：1987.1

  In another application of the principle that metallo derivatives of bis(phenylthio)acetals behave as carbenoids when present in the same molecule with another anionic group, the adducts of cyclic ketones with bis(phenylthio)methyllithium react with an alkyllithium to yield the ring expanded α-(phenylthio) ketones.

  在双（苯硫基）缩醛的金属衍生物与另一个阴离子基团存在于同一分子中时，双（苯硫基）乙缩醛的金属衍生物表现为类胡萝卜素的原理的另一个应用中，环酮与双（苯硫基）甲基锂的加合物与烷基锂反应生成扩环的α -（苯硫基）酮。
• Regiospecific synthesis of α-(phenylthio)cycloalkenones and of α-phenyl-α-(phenylthio) ketones VIA αα-addition of phenylsulphenyl chloride to ∢-diazoketones
  作者：M.Anthony McKervey、Pinit Ratananukul

  DOI：10.1016/s0040-4039(00)81343-x

  日期：1983.1

  phenylsulphenyl chloride at room temperature to furnish α-chloro-α-(phenylthio)cycloalkanones which undergo ready dehydrochlorination to α-(phenylthio)cycloalkenones when treated with triethylamine; acyclic, terminal α-diazoketones also furnish α-chloro-α-(phenylthio)adducts which are useful electrophiles in the synthesis of α-phenyl-α-(phenylthio)ketones.

  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。
• Cinchona alkaloids in the asymmetric synthesis of 2-(phenylsulfanyl)aziridines
  作者：Stefania Fioravanti、M. Gabriella Mascia、Lucio Pellacani、Paolo A. Tardella

  DOI：10.1016/j.tet.2004.06.119

  日期：2004.9

  Enantioselective aza-Michael initiated ring closure (MIRC) additions of ethyl nosyloxycarbamate to 2-(phenylsulfanyl)-2-cycloalkenones catalysed by Cinchona alkaloids were studied. The results suggest that the enantioselectivity obtained is influenced by the structure of the catalyst and the different amination conditions. Substrate ring size also plays an important role.

  研究了金鸡纳生物碱催化的对映选择性氮杂-迈克尔引发的闭环（MIRC）加成的壬基氧基氨基甲酸乙酯与2-（苯基硫烷基）-2-环烯酮的反应。结果表明，所获得的对映选择性受催化剂结构和不同胺化条件的影响。基材环的尺寸也起着重要作用。
• Iodine-Catalyzed Selective Synthesis of 2-Sulfanylphenols<i>via</i>Oxidative Aromatization of Cyclohexanones and Disulfides
  作者：Wenlei Ge、Xun Zhu、Yunyang Wei

  DOI：10.1002/adsc.201300493

  日期：2013.10.11

  AbstractIodine‐catalyzed intermolecular dehydrogenative aromatizations of six‐membered cyclohexanones for the selective synthesis of 2‐sulfanylphenols have been developed. Both aryl and alkyl disulfides can be used as sulfanylation reagents to give the desired products in good yields under the optimized reaction conditions. The catalytic reaction uses dimethyl sulfoxide or oxygen as the terminal oxidant and avoids the use of transition metal catalysts. In addition, α‐sulfanyl enones could also be obtained via an iodine‐catalyzed oxidative system from simple cyclic ketones using dimethyl sulfoxide as the oxidant.magnified image
• MCKERVEY, M. A.;RATANANUKUL, P., TETRAHEDRON LETT., 1983, 24, N 1, 117-120
  作者：MCKERVEY, M. A.、RATANANUKUL, P.

  DOI：——

  日期：——