1-(phenylseleno)tricyclo<3.3.1.1^3,7>decane | 75480-69-2

• 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-(phenylseleno)tricyclo<3.3.1.1^3,7>decane
• 英文别名: 1-Adamantyl phenyl selenide；1-adamantylphenylselenide；1-phenylseleno-adamantane；1-phenylselenyladamantane；1-Phenylselanyladamantane
• CAS: 75480-69-2
• 化学式: C₁₆H₂₀Se
• 分子量: 291.295
• InChiKey: VMSZDCNMYTURST-UHFFFAOYSA-N

物化性质

• 熔点：
  35 °C
• 沸点：
  363.2±15.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-(phenylseleno)tricyclo<3.3.1.1^3,7>decane 在 偶氮二异丁腈 、 1,1,2,2-tetraphenyldisilane 作用下， 以 乙酸乙酯 为溶剂， 反应 14.0h， 以100%的产率得到金刚烷
  参考文献：
  名称：

  1,1,2,2-四芳基乙硅烷的合成用途：烷基苯基硫属元素化物的自由基还原

  摘要：

  研究了由Et 3 B或AIBN引发的四芳基乙硅烷作为烷基苯基硫族化物自由基还原剂的反应性。在此，烷基硫化物的反应性差。但是，用1,1,2,2-四苯基乙硅烷可将各种烷基苯基硒化物和碲化物以良好的收率还原为相应的烃类。

  DOI：

  10.1039/a905937g
• 作为产物：
  描述：

  1-金刚烷醇 在 三氟乙酸 、 锌 作用下， 以 二氯甲烷 为溶剂， 反应 36.25h， 生成 1-(phenylseleno)tricyclo<3.3.1.1^3,7>decane
  参考文献：
  名称：

  Photochemistry of phenyl thioethers and phenyl selenoethers. Radical vs. ionic behavior

  摘要：

  In analogy with alkyl iodides and bromides, the phenyl thio- and selenoethers 2a,b, 13a, 21b,c and 35 displayed competing radical and ionic photobehavior on irradiation in solution, via a mechanism thought to involve initial homolytic cleavage of the alkyl C-S or C-Se bond followed by electron transfer within the resulting radical pair cage (Scheme I). These are the first examples of ionic photobehavior to be recognized for the C-SAr and C-SeAr chromophores. The electronegatively substituted pentafluorophenyl analogues 2c, 13b, and 21d displayed enhanced ionic photobehavior. By contrast, the 4-methoxyphenyl derivative 21a exhibited almost exclusively radical behavior. The sulfoxide (2R*,R*S)-21f displayed principally radical behavior, accompanied by epimerization at sulfur. The quantum yields for the disappearance of the 2-norbornyl ethers 21b and 21c were 0.53-0.64 in solution and rose to 0.89-0.95 in the presence of suspended fumed silica. Irradiation of the phenyl thioether 21b on silica gel resulted in nucleophilic trapping by surface silanol groups to afford covalently bound material (33), which afforded chloride 34 on treatment with SOCl2. Irradiation of phenyl thioethers 2a and 35, phenyl selenoether 2b, or C6H5SH in allyl alcohol solutionafforded acetal 11, apparently via isomerization of some of the solvent to propanal (44) followed by acetalization. Irradiation of alcoholic solutions of aldehydes containing C6H5SH is a useful means of generating acetals under neutral conditions.

  DOI：

  10.1021/ja00019a030

文献信息

• The invention of radical reactions. Part XXXI. Diphenylsilane: a reagent for deoxygenation of alcohols via their thiocarbonyl derivatives, deamination via isonitriles, and dehalogenation of bromo- and iodo- compounds by radical chain chemistry
  作者：Derek H.R. Barton、Doo Ok Jang、Joseph Cs. Jaszberenyi

  DOI：10.1016/s0040-4020(01)87198-2

  日期：1993.8

  Various thionocarbonates and xanthates of alcohols and bis-xanthates of vic-diols are readily deoxygenated to the corresponding hydrocarbons or olefins, while bromides and iodides are dehalogenated with diphenylphenylsilane in good yield.

  各种thionocarbonates和醇的黄原酸盐和二的-xanthates VIC -diols容易脱氧成相应的烃或烯烃，而溴化物和碘化物与以良好的收率diphenylphenylsilane脱卤。
• Redox-Mediated Decarboxylative Photo-Phenylselenenylation of N-Acyloxyphthalimides
  作者：Keiji Okada、Katsura Okubo、Naoto Morita、Masaji Oda

  DOI：10.1246/cl.1993.2021

  日期：1993.12

  Decarboxylative phenylselenenylation of N-acyloxyphthalimides by visible light irradiation in aqueous solvents using catalytic amount of Ru(bpy)3Cl2 as a sensitizer in the presence of one equivalent of BNAH and 0.5 equivalent of diphenyl diselenide efficiently proceeds via redox-mediated radical chain mechanism. The AIBN-induced thermal reaction is also described.

  通过在含水溶剂中使用催化量的Ru(bpy)3Cl2作为敏化剂，在1当量的BNAH和0.5当量的二苯基二硒化合物存在下，利用可见光辐照，N-酰氧基邻苯二甲酰亚胺类化合物的脱羧基苯基硒醚化反应能高效进行，其反应途径涉及氧化还原介导的自由基链机制。此外，还描述了AIBN引发的热反应过程。
• S H2 reactions of diphenyl diselenide; preparation and reactions of bridgehead selenides
  作者：M. John Perkins、Eric S. Turner

  DOI：10.1039/c39810000139

  日期：——

  benzene when R is primary alkyl; with 1-adamantyl radicals this SH2 displacement affords a route to 1-adamantyl phenyl selenide which, on oxidation and pyrolysis of the resultant selenoxide, gives adamantan-1-ol; in contrast the selenoxide from bicyclo[3.3.1]nonan-1-yl phenyl selenide decomposes via bicyclo[3.3.1]non-l-ene.

  对于S H 2过程，R·+ PhSeSePh→PhSeR + PhSe·，k = ca。当R为伯烷基时，在苯中80°C，5×10 7 mol –1 s –1；具有1-金刚烷基的该S H 2置换提供了通往1-金刚烷基苯基硒化物的途径，其在所得硒氧化物的氧化和热解后，产生了金刚烷-1-醇。与此相反，从双环的氧化硒[3.3.1]壬烷-1-基苯基硒化物分解经由二环[3.3.1]壬-1-烯。
• Syntheses of Sulfides and Selenides through Direct Oxidative Functionalization of C(sp³)–H Bond
  作者：Bingnan Du、Bo Jin、Peipei Sun

  DOI：10.1021/ol5011449

  日期：2014.6.6

  functionalization of the C(sp3)–H bond of alkanes under metal-free conditions was developed. Using tBuOOtBu as the oxidant, the reaction of disulfides or diselenides with alkanes gave sulfides or selenides in moderate to good yields. The method was very simple and atom-economical.

  通过在无金属条件下对烷烃的C（sp 3）-H键进行直接官能化，开发了一种C-S和C-Se键形成的新方案。使用t BuOO t Bu作为氧化剂，二硫化物或二硒化物与烷烃的反应以中等至良好的收率得到硫化物或硒化物。该方法非常简单且原子经济。
• General synthesis of alkyl phenyl selenides from organic halides mediated by zinc in aqueous medium
  作者：Lothar W Bieber、Ana C.P.F de Sá、Paulo H Menezes、Simone M.C Gonçalves

  DOI：10.1016/s0040-4039(01)00820-6

  日期：2001.7

  halides of different structural types react with diphenyl diselenide and zinc dust in aqueous medium to give alkyl phenyl selenides. Benzylic and allylic bromides, α-bromoesters, acids and ketones and some primary alkyl iodides produce high yields even under acidic conditions. Less reactive halides need basic medium. The reaction proceeds equally well in the presence of various unprotected functional

  不同结构类型的有机卤化物与二苯基二硒化物和锌粉在水性介质中反应，生成烷基苯基硒化物。苄基和烯丙基溴化物，α-溴代酸酯，酸和酮以及某些伯烷基碘化物即使在酸性条件下也能产生高收率。反应性较低的卤化物需要基本介质。在各种未保护的官能团的存在下，反应同样良好地进行。对照实验通过烷基支持S H 2机理。