2-bromo-2-methyldecane | 502760-08-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 英文名称: 2-bromo-2-methyldecane
• CAS: 502760-08-9
• 化学式: C₁₁H₂₃Br
• 分子量: 235.208
• InChiKey: VPHRQYBYTFDBOA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  12
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  2-bromo-2-methyldecane 在 lithium aluminium tetrahydride 、 正丁基锂 、 zinc sulfide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 14.5h， 生成 2-methyl-2-(methylthio)decane
  参考文献：
  名称：

  Structure–Odor Correlations in Homologous Series of Alkanethiols and Attempts To Predict Odor Thresholds by 3D-QSAR Studies

  摘要：

  Homologous series of alkane-1-thiols, alkane-2-thiols, alkane-3-thiols, 2-methylalkane-1-thiols, 2-methylalkane-3-thiols, 2-methylalkane-2-thiols, and alkane-1,?-dithiols were synthesized to study the influence of structural changes on odor qualities and odor thresholds. In particular, the odor thresholds were strongly influenced by steric effects: In all homologous series a minimum was observed for thiols with five to seven carbon atoms, whereas increasing the chain length led to an exponential increase in the odor threshold. Tertiary alkanethiols revealed clearly lower odor thresholds than found for primary or secondary thiols, whereas neither a second mercapto group in the molecule nor an additional methyl substitution lowered the threshold. To investigate the impact of the SH group, odor thresholds and odor qualities of thiols were compared to those of the corresponding alcohols and (methylthio)alkanes. Replacement of the SH group by an OH group as well as S-methylation of the thiols significantly increased the odor thresholds. By using comparative molecular field analysis, a 3D quantitative structureactivity relationship model was created, which was able to simulate the odor thresholds of alkanethiols in good agreement with the experimental results. NMR and mass spectrometric data for 46 sulfur-containing compounds are additionally supplied.

  DOI：

  10.1021/jf506135c
• 作为产物：
  描述：

  2-癸酮 在 氢溴酸 、 lithium bromide 作用下， 以 乙醚 、 水 为溶剂， 反应 2.0h， 生成 2-bromo-2-methyldecane
  参考文献：
  名称：

  Structure–Odor Correlations in Homologous Series of Alkanethiols and Attempts To Predict Odor Thresholds by 3D-QSAR Studies

  摘要：

  Homologous series of alkane-1-thiols, alkane-2-thiols, alkane-3-thiols, 2-methylalkane-1-thiols, 2-methylalkane-3-thiols, 2-methylalkane-2-thiols, and alkane-1,?-dithiols were synthesized to study the influence of structural changes on odor qualities and odor thresholds. In particular, the odor thresholds were strongly influenced by steric effects: In all homologous series a minimum was observed for thiols with five to seven carbon atoms, whereas increasing the chain length led to an exponential increase in the odor threshold. Tertiary alkanethiols revealed clearly lower odor thresholds than found for primary or secondary thiols, whereas neither a second mercapto group in the molecule nor an additional methyl substitution lowered the threshold. To investigate the impact of the SH group, odor thresholds and odor qualities of thiols were compared to those of the corresponding alcohols and (methylthio)alkanes. Replacement of the SH group by an OH group as well as S-methylation of the thiols significantly increased the odor thresholds. By using comparative molecular field analysis, a 3D quantitative structureactivity relationship model was created, which was able to simulate the odor thresholds of alkanethiols in good agreement with the experimental results. NMR and mass spectrometric data for 46 sulfur-containing compounds are additionally supplied.

  DOI：

  10.1021/jf506135c

文献信息

• Silver-Catalyzed Benzylation and Allylation of Tertiary Alkyl Bromides with Organozinc Reagents
  作者：Yukihiro Mitamura、Yoshihiro Asada、Kei Murakami、Hidenori Someya、Hideki Yorimitsu、Koichiro Oshima

  DOI：10.1002/asia.201000068

  日期：2010.5.5

  Silver salts catalyze the benzylation and allylation of tertiary alkyl bromides with organozinc reagents. The reactions create quaternary carbon centers efficiently. Treatment of gem‐dibromoalkanes with benzylic or allylic zinc reagents under silver catalysis leads to dibenzylation or diallylation. The functional‐group compatibility of the present reactions is wider than that of the previous reactions

  银盐用有机锌试剂催化叔烷基溴化物的苄基化和烯丙基化。该反应有效地产生季碳中心。在银催化下用苄基或烯丙基锌试剂处理宝石二溴代烷烃会导致二苄基化或二烯丙基化。当前反应的官能团相容性比以前使用格氏试剂的反应要宽。
• Silver-catalyzed coupling reactions of alkyl halides with indenyllithiums
  作者：Hidenori Someya、Hideki Yorimitsu、Koichiro Oshima

  DOI：10.1016/j.tet.2010.06.030

  日期：2010.8

  Coupling reactions of tertiary and secondary alkyl halides with indenyllithiums proceeded effectively in the presence of a catalytic amount of silver bromide to provide tertiary- and secondary-alkyl-substituted indene derivatives in good yields.

  在催化量的溴化银存在下，叔烷基卤化物和仲烷基卤化物与茚基锂的偶联反应有效地进行，从而以高收率提供了叔烷基和仲烷基取代的茚衍生物。
• Cobalt-Catalyzed Cross-Coupling Reactions of Alkyl Halides with Allylic and Benzylic Grignard Reagents and Their Application to Tandem Radical Cyclization/Cross-Coupling Reactions
  作者：Hirohisa Ohmiya、Takashi Tsuji、Hideki Yorimitsu、Koichiro Oshima

  DOI：10.1002/chem.200400545

  日期：2004.11.19

  Details of cobalt-catalyzed cross-coupling reactions of alkyl halides with allylic Grignard reagents are disclosed. A combination of cobalt(II) chloride and 1,2-bis(diphenylphosphino)ethane (DPPE) or 1,3-bis(diphenylphosphino)propane (DPPP) is suitable as a precatalyst and allows secondary and tertiary alkyl halides--as well as primary ones--to be employed as coupling partners for allyl Grignard reagents

  公开了烷基卤化物与烯丙基格利雅试剂的钴催化的交叉偶联反应的细节。氯化钴（II）和1,2-双（二苯基膦基）乙烷（DPPE）或1,3-双（二苯基膦基）丙烷（DPPP）的组合适合作为预催化剂，并允许使用仲和叔烷基卤化物作为主要试剂-可用作烯丙基格氏试剂的偶联伙伴。该反应提供了季碳中心的简便合成，而钯，镍和铜催化剂几乎是不可能的。苄基，甲基烯丙基和巴豆基格氏试剂均可以与卤代烷偶联。苄基化肯定需要DPPE或DPPP作为配体。反应机理应包括由母体烷基卤生成烷基。可以根据串联自由基环化/交叉偶联反应来解释该机理。此外，还描述了5-烷氧基-6-卤代-4-氧杂-1-氧杂-1-己烯衍生物的偶发串联自由基环化/环丙烷化/羰基烯丙基化。以碳为中心的自由基的中间体导致母体烷基卤化物的原始立体化学丧失，从而产生了外消旋烷基卤化物不对称交叉偶联的可能性。
• Silver-Catalyzed Benzylation and Allylation Reactions of Tertiary and Secondary Alkyl Halides with Grignard Reagents
  作者：Hidenori Someya、Hirohisa Ohmiya、Hideki Yorimitsu、Koichiro Oshima

  DOI：10.1021/ol800038a

  日期：2008.3.1

  Treatment of alkyl halides, including tertiary alkyl bromides, with benzylic or allylic Grignard reagent in the presence of a catalytic amount of silver nitrate in ether yielded the corresponding cross-coupling products in high yields. The coupling reactions of tertiary alkyl halides provide efficient access to quaternary carbon centers.

  在醚中催化量的硝酸银存在下，用苄基或烯丙基格氏试剂处理卤代烷，包括叔烷基溴化物，可以高产率得到相应的交叉偶联产物。叔烷基卤化物的偶联反应提供了到季碳中心的有效通道。
• Silver-catalyzed cross-coupling reactions of alkyl bromides with alkyl or aryl Grignard reagents
  作者：Hidenori Someya、Hideki Yorimitsu、Koichiro Oshima

  DOI：10.1016/j.tetlet.2009.02.040

  日期：2009.7

  Treatment of secondary or tertiary alkyl bromides with alkyl Grignard reagents in the presence of catalytic amounts of silver bromide and potassium fluoride in CH2Cl2 afforded the corresponding cross-coupling products in reasonable yields. Moreover, silver showed catalytic activity for the cross-coupling reactions of alkyl bromides with aryl Grignard reagents.

  在催化量的溴化银和氟化钾在CH 2 Cl 2中的存在下，用烷基格氏试剂处理仲或叔烷基溴化物，可以合理的收率得到相应的交叉偶联产物。此外，银对于烷基溴与芳基格氏试剂的交叉偶联反应显示出催化活性。