1-methyl-4-(2-methylallylsulfonyl)benzene | 16192-04-4

• 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-methyl-4-(2-methylallylsulfonyl)benzene
• 英文别名: 2-methylprop-2-enyl p-tolyl sulphone；2-Methyl-2-propenyl p-tolyl sulphone；1-methyl-4-(2-methylprop-2-enylsulfonyl)benzene
• CAS: 16192-04-4
• 化学式: C₁₁H₁₄O₂S
• 分子量: 210.297
• InChiKey: KKSRFROTRSZRSD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  42.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-methyl-4-(2-methylallylsulfonyl)benzene 在 溴 作用下， 以 四氯化碳 为溶剂， 反应 4.0h， 以99%的产率得到1,2-dibromo-2-methyl-3-tosylpropane
  参考文献：
  名称：

  A simple method for the synthesis of γ-functionalized vinyl and allyl sulfones

  摘要：

  The synthesis of gamma-functionalized vinyl sulfones 3 have been carried out directly starting from dibromides 2 derived from allyl sulfones 1 by reaction with different nucleophiles. The process is stereoselective affording compounds 3 with E configuration except in the case of methallylic derivatives. The regioisomeric gamma-functionalized allyl sulfones 4 were obtained from dibromides 2 or from vinyl sulfones 3, with Z configuration, except when triphenylphosphine was used as nucleophile, in this case the corresponding (E)-vinylphosphonium bromide 4al was obtained.

  DOI：

  10.1016/s0040-4020(01)86563-7
• 作为产物：
  描述：

  1-甲基-4-(2-丙炔磺酰基)-苯 在 N-甲基吗啉 、 copper(l) iodide 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 为溶剂， 生成 1-methyl-4-(2-methylallylsulfonyl)benzene
  参考文献：
  名称：

  Koosha,K. et al., Bulletin de la Societe Chimique de France, 1975, p. 1284 - 1290

  摘要：

  DOI：

文献信息

• Radical-chain reactions of sulfonyl azides and of ethyl azidoformate with allylstannanes: homolytic allylation at nitrogen
  作者：Hai-Shan Dang、Brian P. Roberts

  DOI：10.1039/p19960001493

  日期：——

  amounts of allyl 4-methylphenyl sulfone were also formed. The reaction follows a free-radical chain mechanism which involves competitive addition of Ph3Sn˙ to Na and to Nc of the azido group in ArSO2NaNbNc. Addition to Na followed by loss of nitrogen gives ArSO2ṄSnPh3, the precursor of the N-allylarenesulfonamide, while addition to Nc leads to the formation of ArṠO2 and thence to the allyl aryl sulfone

  在2,2'-偶氮双（2-甲基丙腈）作为引发剂的存在下，4-甲基苯磺酰叠氮化物与烯丙基三苯基锡烷（ATPS）在回流的苯中反应，经过水解处理后以良好的收率得到N-烯丙基-4-甲基苯磺酰胺。也形成少量的烯丙基4-甲基苯基砜。该反应如下涉及竞争性加入pH的自由基链机构3 SN至N一个和至N ç叠氮基的在ARSO 2 Ñ一个Ñ b Ñ Ç。除了到N一个用氮气的损失给出ARSO 2 ṄSnPh 3，所述的前体Ñ-allylarenesulfonamide，而除了到N Ç导致ARFO的形成2和从此到烯丙基芳基砜。以类似的方式，以ATPS Allyltrimethylstannane的行为，但allyltributylstannane仅给出的低产率Ñ -allylarenesulfonamide和主要产物是未取代的磺酰胺的MeC 6 H ^ 4 SO 2 NH 2，其结果，因为自由基ARSO 2 ṄSnBu
• Efficient synthesis of bicyclo[2.2.1]heptane derivatives via stereoselective intramolecular Michael reactions of vinyl sulfones
  作者：Mark A. Collins、D. Neville Jones

  DOI：10.1016/0040-4020(96)00421-8

  日期：1996.6

  Efficient synthesis of 6-endo-methyl substituted bicyclo[2.2.1]heptane derivatives formed via completely diastereoselective intramolecular Michael addition reactions of vinyl sulfones, derived from allyl sulfones and cyclopentenones, are described.

  的有效合成6-内-甲基取代的二环[ 2.2.1形成]庚烷衍生物通过乙烯基砜，从烯丙基砜和环戊烯酮衍生的非对映选择性完全分子内迈克尔加成反应，进行说明。
• Palladium-catalyzed substitution of allylic alcohols with sulfinate salts: A synthesis of bicalutamide
  作者：Yin-Jia Jhang、Chieh-Yu Chang、Yu-Huan Lin、Chein-Chung Lee、Yen-Ku Wu

  DOI：10.1016/j.tetlet.2021.153060

  日期：2021.6

  A method is presented for the direct substitution of allylic alcohols with sodium arylsulfinates. The process involves a cooperative action of palladium catalysts, phenylboronic acid and titanium tetraisopropoxide. By taking advantage of this protocol, we achieved a concise synthesis of bicalutamide, an anti-androgen compound for treating prostate cancer.

  提出了一种用芳基亚磺酸钠直接取代烯丙醇的方法。该过程涉及钯催化剂、苯基硼酸和四异丙醇钛的协同作用。通过利用该协议，我们实现了比卡鲁胺的简洁合成，比卡鲁胺是一种用于治疗前列腺癌的抗雄激素化合物。
• SO₂ conversion to sulfones: development and mechanistic insights of a sulfonylative Hiyama cross-coupling
  作者：Aurélien Adenot、Joëlle Char、Niklas von Wolff、Guillaume Lefèvre、Lucile Anthore-Dalion、Thibault Cantat

  DOI：10.1039/c9cc06858a

  日期：——

  A Pd-catalyzed Hiyama cross-coupling reaction using SO₂ is described.

  一种使用二氧化硫的Pd催化Hiyama交叉偶联反应被描述。
• Synthesis of small ring-containing conjugated dienes via the coupling reaction of cyclopropyl- and cyclobutylmagnesium carbenoids with α-sulfonylallyllithiums
  作者：Tsutomu Kimura、Mio Inumaru、Takuma Migimatsu、Masashi Ishigaki、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2013.03.019

  日期：2013.5

  synthesized via the coupling reaction of cyclopropyl- and cyclobutylmagnesium carbenoids with α-sulfonylallyllithiums. Small ring cycloalkylmagnesium carbenoids were generated from aryl 1-chlorocycloalkyl sulfoxides and a Grignard reagent, and the resultant magnesium carbenoids were reacted with α-sulfonylallyllithiums, which were prepared via the deprotonation of p-tolyl vinyl sulfones or allyl p-tolyl

  通过环丙基和环丁基镁类胡萝卜素与α-磺酰基烯丙基锂的偶联反应，合成了各种烯丙基环丙烷和烯丙基环丁烷。由芳基1-氯环烷基亚砜和格利雅试剂生成小环环烷基镁类胡萝卜素，然​​后使生成的镁类胡萝卜素与α-磺酰基烯丙基锂反应，后者是通过对甲苯基乙烯基砜或烯丙基p的去质子化反应制得的。-甲苯基砜。亚芳基环烷烃的收率中等至良好，而亚芳基环烷烃与四氰基乙烯的Diels-Alder反应提供了螺环化合物。无环烷基镁类胡萝卜素与α-磺酰基烯丙基锂的偶联反应提供了作为几何异构体混合物的共轭二烯。DFT计算的结果表明，相对于相应的氯环烷烃，小环环烷基镁类胡萝卜素具有较长的C–Cl键，并且C–Cl键的背面具有扩展的键角。