O-(6-benzyloxy-1-isopropyl-hexyl)-S-methyldithiocarbonate | 1043905-75-4

• 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: O-(6-benzyloxy-1-isopropyl-hexyl)-S-methyldithiocarbonate
• 英文别名: O-[(8-benzyloxy-2-methyl)oct-3-yl]-S-methylxanthate；O-(2-methyl-8-phenylmethoxyoctan-3-yl) methylsulfanylmethanethioate
• CAS: 1043905-75-4
• 化学式: C₁₈H₂₈O₂S₂
• 分子量: 340.551
• InChiKey: YZTNNRBDOXALCH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  22
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  75.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  O-(6-benzyloxy-1-isopropyl-hexyl)-S-methyldithiocarbonate 在 偶氮二异丁腈 、 (1-butyl-3-methyl-1H-imidazol-3-ium-2-yl) trihydroborate 作用下， 以 苯 为溶剂， 反应 2.0h， 以85%的产率得到((7-methyloctyloxy)methyl)benzene
  参考文献：
  名称：

  1-丁基-3-甲基咪唑-2-亚乙基硼烷：一种现成的液态N-杂环碳硼烷试剂

  摘要：

  1-丁基-3-甲基咪唑-2-亚烷基硼烷是直接由两种廉价的商业试剂合成的：溴化1-丁基-3-甲基咪唑鎓和硼氢化钠。这种NHC-硼烷试剂是一种稳定的，自由流动的液体，具有在自由基，离子和金属催化反应中使用的前景。

  DOI：

  10.1021/acs.joc.7b02730
• 作为产物：
  描述：

  、 碘甲烷 以 四氢呋喃 为溶剂， 以1.84 g的产率得到O-(6-benzyloxy-1-isopropyl-hexyl)-S-methyldithiocarbonate
  参考文献：
  名称：

  Complexes of Borane and N-Heterocyclic Carbenes: A New Class of Radical Hydrogen Atom Donor

  摘要：

  Calculations suggest that complexes of borane with N-heterocyclic carbenes (NHC) have B-H bond dissocation energies more then 20 Kcal/mol less than free borane, diborane, borane-THF, and related complexes. Values are in the range of popular radical hydrogen atom donors like tin hydrides (70-80 Kcal/mol). The resulting prediction that NHC borane complexes could be used as radical hydrogen atom donors was verified by radical deoxygenations of xanthates by using either AIBN or triethylborane as initiator.

  DOI：

  10.1021/ja804150k

文献信息

• <i>N</i>-Heterocyclic Carbene Boryl Radicals: A New Class of Boron-Centered Radical
  作者：Shau-Hua Ueng、Andrey Solovyev、Xinting Yuan、Steven J. Geib、Louis Fensterbank、Emmanuel Lacôte、Max Malacria、Martin Newcomb、John C. Walton、Dennis P. Curran

  DOI：10.1021/ja904103x

  日期：2009.8.12

  Reduction of xanthates by N-heterocyclic carbene boranes (NHC-boranes) has been suggested to occur by a radical chain mechanism involving heretofore unknown NHC-boryl radicals. In support of this suggestion, both the expected borane dithiocarbonate product and an unexpected borane xanthate product have now been isolated. These are the first NHC-boranes with boron-sulfur bonds, and their structures

  N-杂环卡宾硼烷 (NHC-硼烷) 对黄原酸酯的还原被认为是通过涉及迄今为止未知的 NHC-硼基自由基的自由基链机制发生的。为支持这一建议，预期的硼烷二硫代碳酸酯产品和意外的硼烷黄原酸盐产品现已分离出来。这些是第一个具有硼硫键的 NHC-硼烷，它们的结构已通过光谱和晶体学手段得到保证。通过使用取代的环丁基羰基自由基的开环作为时钟反应来确定从 NHC 硼烷络合物转移 H 原子的第一速率常数。NHC-硼烷与仲烷基在环境温度下反应的速率常数为 4 x 10(4) M(-1) s(-1)，并且 Arrhenius 函数显示了双分子反应的典型熵项（log A 项）。NHC-硼烷复合物的 BH 键解离能估计为 88 kcal/mol。EPR 光谱已检测到这些转化中假定的 NHC-硼基自由基。光谱分析表明它是一种π自由基，类似于苄基。
• Radical Deoxygenation of Xanthates and Related Functional Groups with New Minimalist N-Heterocyclic Carbene Boranes
  作者：Shau-Hua Ueng、Louis Fensterbank、Emmanuel Lacôte、Max Malacria、Dennis P. Curran

  DOI：10.1021/ol101015m

  日期：2010.7.2

  Minimalist N-heterocyclic carbene boranes 1,3-dimethylimidazol-2-ylideneborane and 2,4-dimethyl-1,2,4-triazol-3-ylideneborane are readily available and have low molecular weights. They exhibit superior performance to first-generation NHC−boranes, providing improved yields in reductions of xanthates and related functional groups.

  极简主义的N-杂环卡宾硼烷1,3-二甲基咪唑-2-亚基硼烷和2,4-二甲基-1,2,4-三唑-3-亚基硼烷很容易获得，并且分子量低。它们表现出优于第一代NHC-硼烷的性能，在减少黄药和相关官能团方面提供了更高的收率。
• 1-Butyl-3-methylimidazol-2-ylidene Borane: A Readily Available, Liquid N-Heterocyclic Carbene Borane Reagent
  作者：Daniel A. Bolt、Dennis P. Curran

  DOI：10.1021/acs.joc.7b02730

  日期：2017.12.15

  1-Butyl-3-methylimidazol-2-ylidene borane has been synthesized directly from two inexpensive commercial reagents: 1-butyl-3-methylimidazolium bromide and sodium borohydride. This NHC-borane reagent is a stable, free-flowing liquid that shows promise for use in radical, ionic, and metal-catalyzed reactions.

  1-丁基-3-甲基咪唑-2-亚烷基硼烷是直接由两种廉价的商业试剂合成的：溴化1-丁基-3-甲基咪唑鎓和硼氢化钠。这种NHC-硼烷试剂是一种稳定的，自由流动的液体，具有在自由基，离子和金属催化反应中使用的前景。
• Complexes of Borane and N-Heterocyclic Carbenes: A New Class of Radical Hydrogen Atom Donor
  作者：Shau-Hua Ueng、Malika Makhlouf Brahmi、Étienne Derat、Louis Fensterbank、Emmanuel Lacôte、Max Malacria、Dennis P. Curran

  DOI：10.1021/ja804150k

  日期：2008.8.1

  Calculations suggest that complexes of borane with N-heterocyclic carbenes (NHC) have B-H bond dissocation energies more then 20 Kcal/mol less than free borane, diborane, borane-THF, and related complexes. Values are in the range of popular radical hydrogen atom donors like tin hydrides (70-80 Kcal/mol). The resulting prediction that NHC borane complexes could be used as radical hydrogen atom donors was verified by radical deoxygenations of xanthates by using either AIBN or triethylborane as initiator.