1-propylisoquinoline | 7661-37-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 英文名称: 1-propylisoquinoline
• 英文别名: 1-propyl-isoquinoline；1-Propyl-isochinolin；Isoquinoline, 1-propyl-
• CAS: 7661-37-2
• 化学式: C₁₂H₁₃N
• mdl: MFCD18448923
• 分子量: 171.242
• InChiKey: WGBFAILGFRYCLA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-propylisoquinoline 在 lithium carbonate 、 N-氟代双苯磺酰胺 作用下， 以 乙腈 为溶剂， 以78%的产率得到
  参考文献：
  名称：

  与二苯磺酰胺衍生物直接进行杂苄基氟化，二氟化和三氟甲硫基化†

  摘要：

  具有单或二氟烷基的杂环支架的功能化提供了调节药物p K a，影响效价和膜通透性以及减弱新陈代谢的独特机会。尽管已经取得了在杂环上添加氟代烷基自由基的进展，但是相对而言，尚没有直接进行C（sp 3）–H杂苄基氟化反应的研究。在这里，我们证明了使用便利方法的一系列烷基杂环的单氟化和二氟化反应，该方法依赖于亲电氟化剂N-氟苯磺酰亚胺的瞬时磺酰化作用。我们还报告了杂苄基三氟甲基硫醇化和18 F-氟化，为后期C（sp 3）–药物线索的H功能化和放射性示踪剂的发现。

  DOI：

  10.1039/c8sc01221k
• 作为产物：
  描述：

  N-phenethylbutyramide 在 1,2,3,4-四氢萘 、 phosphorus pentoxide 、 钯 作用下， 生成 1-propylisoquinoline
  参考文献：
  名称：

  Spaeth et al., Chemische Berichte, 1930, vol. 63, p. 134,136

  摘要：

  DOI：

文献信息

• Dioxygen-Mediated Decarbonylative CH Alkylation of Heteroaromatic Bases with Aldehydes
  作者：Subhasis Paul、Joyram Guin

  DOI：10.1002/chem.201503809

  日期：2015.12.1

  An operationally simple and economical method for the direct alkylation of heteroaromatic bases employing readily available aldehydes as alkyl radical precursors and molecular oxygen as a reagent is presented. This simple transformation demonstrates a broad substrate scope with respect to aldehydes and nitrogen heterocycles, enabling the introduction of several medicinally important yet challenging

  提出了一种操作简单且经济的方法，用于将杂芳族碱直接烷基化，该方法使用容易获得的醛作为烷基前体，并使用分子氧作为试剂。这种简单的转化展示了针对醛和氮杂环的广泛底物范围，从而能够将几种具有医学重要性但极具挑战性的烷基部分（例如乙基，异丙基，叔丁基和环己基）引入到不同类别的杂环碱中，优异的产量。
• Alcohols as alkylating agents in heteroarene C–H functionalization
  作者：Jian Jin、David W. C. MacMillan

  DOI：10.1038/nature14885

  日期：2015.9

  The biochemical process of spin-centre shift is used to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors; this represents the first broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. A central reaction in DNA biosynthesis is ribonucleotide deoxygenation via the radical-mediated elimination of H2O, which is an example of 'spin-centre shift' (SCS), during which an alcohol C–O bond is cleaved to produce in a carbon-centred radical intermediate. Although SCS is a well-understood biochemical process, it is underutilized by the synthetic organic chemistry community. Here Jian Jin and David MacMillan show that it is possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylations using alcohols as radical precursors. This method represents the first broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the merger of photoredox and hydrogen atom transfer catalysis. Redox processes and radical intermediates are found in many biochemical processes, including deoxyribonucleotide synthesis and oxidative DNA damage1. One of the core principles underlying DNA biosynthesis is the radical-mediated elimination of H2O to deoxygenate ribonucleotides, an example of ‘spin-centre shift’2, during which an alcohol C–O bond is cleaved, resulting in a carbon-centred radical intermediate. Although spin-centre shift is a well-understood biochemical process, it is underused by the synthetic organic chemistry community. We wondered whether it would be possible to take advantage of this naturally occurring process to accomplish mild, non-traditional alkylation reactions using alcohols as radical precursors. Because conventional radical-based alkylation methods require the use of stoichiometric oxidants, increased temperatures or peroxides3,4,5,6,7, a mild protocol using simple and abundant alkylating agents would have considerable use in the synthesis of diversely functionalized pharmacophores. Here we describe the development of a dual catalytic alkylation of heteroarenes, using alcohols as mild alkylating reagents. This method represents the first, to our knowledge, broadly applicable use of unactivated alcohols as latent alkylating reagents, achieved via the successful merger of photoredox and hydrogen atom transfer catalysis. The value of this multi-catalytic protocol has been demonstrated through the late-stage functionalization of the medicinal agents, fasudil and milrinone.

  利用自旋中心转移的生化过程，通过醇作为自由基前体，可以实现温和的、非传统的烷基化反应。这在合成有机化学领域尚未得到充分应用。本文中Jin Jian和David MacMillan展示了一种方法，即利用这一自然发生的自旋中心转移过程，以醇作为自由基前体，实现温和、非传统的烷基化反应。这种方法首次实现了在广泛应用上将非活化醇作为潜在烷基化试剂，其核心是通过光氧化还原与氢原子转移催化的结合来实现。氧化还原过程和自由基中间体在很多生化过程中都存在，包括脱氧核糖核酸的合成和氧化性DNA损伤。DNA生物合成的关键原理之一就是通过自由基介导的水分子消除反应来脱氧核糖核苷酸，这也是"自旋中心转移"的一个例子。在这个过程中，醇的C-O键断裂，形成碳中心的自由基中间产物。虽然自旋中心转移是一个广为人知的生化过程，但在合成有机化学领域，这一方法尚未得到广泛应用。我们想知道是否有可能利用这个自然发生的自旋中心转移过程，以醇作为自由基前体，实现温和、非传统的烷基化反应。传统的基于自由基的烷基化方法通常需要使用化学计量的氧化剂、提高温度或使用过氧化物，因此一个使用简单且丰富的烷基化试剂的温和协议在合成多样功能化的药物分子上具有很大的应用价值。在这里，我们描述了一种使用醇作为温和烷基化试剂的双催化烷基化杂芳烃的方法。据我们所知，这代表了首次在广泛应用上将非活化醇作为潜在烷基化试剂，其成功在于实现了光氧化还原与氢原子转移催化的结合。该多催化协议的价值已通过药物分子法舒地尔和米力农的后期功能化得到展示。
• Radical C−H Acylation of Nitrogen Heterocycles Induced by an Aerobic Oxidation of Aldehydes
  作者：Subhasis Paul、Manotosh Bhakat、Joyram Guin

  DOI：10.1002/asia.201900857

  日期：2019.9.16

  ketones is described herein. The reaction involves cross-dehydrogenative coupling between aldehydes and heteroaromatic bases with molecular oxygen (O2 ). The key aspect of the method is the generation of reactive acyl radical via homolytic activation of aldehyde C-H bond using O2 as the sole oxidant. The reaction has a good substrate scope with respect to aldehydes and functionalized nitrogen heterocycles

  本文描述了用于合成不对称杂芳基酮的需氧自由基方法。该反应涉及醛和杂芳族碱与分子氧（O2）之间的交叉脱氢偶联。该方法的关键方面是使用O2作为唯一氧化剂，通过醛CH键的均质活化来生成反应性酰基基团。关于醛和官能化的氮杂环，该反应具有良好的底物范围。根据我们的机理研究，建议该反应采用自由基链途径。该方法的合成应用在天然生物碱（±）安格西汀的形式合成中得到了证明。
• PROCESS FOR PRODUCTION OF BIS-QUATERNARY AMMONIUM SALT, AND NOVEL INTERMEDIATE
  申请人：Okamoto Kuniaki

  公开号：US20120130107A1

  公开（公告）日：2012-05-24

  Object To provide a method for producing a bis-quaternary ammonium salt efficiently and a novel synthetic intermediate thereof. Solution The present invention relates to a method for producing a bis-quaternary ammonium salt represented by a general formula [3] which comprises reacting a disulfonic acid ester represented by a general formula [1] (in the formula, definitions of two R 1 's and T are as described in claim 1 ) with a tertiary amine represented by a general formula [2] (in the formula, definitions of R 3 to R 5 are as described in claim 1 ), and a disulfonic acid ester represented by a general formula [1′] (in the formula, two R 16 's represent independently a halogen atom or a C1-C3 fluoroalkyl group, and two m's represent independently an integer of 1 to 5).

  提供一种高效生产双季铵盐和其新型合成中间体的方法。本发明涉及一种生产由通用式[3]表示的双季铵盐的方法，包括将由通用式[1]表示的二磺酸酯（在该式中，两个R1和T的定义如权利要求1中所述）与由通用式[2]表示的三级胺（在该式中，R3到R5的定义如权利要求1中所述）以及由通用式[1']表示的二磺酸酯（在该式中，两个R16独立表示卤原子或C1-C3氟烷基，两个m独立表示1至5的整数）反应。
• Trimethyl borate/magnesium halide complex-induced one-pot homologation reactions of isoquinoline with dialkyl-TMP-zincate
  作者：Hye Ji Seo、Sung Keon Namgoong

  DOI：10.1016/j.tetlet.2012.05.002

  日期：2012.7

  one-pot homologation reactions of isoquinoline with lithium dialkyl-TMP-zincate⋅2MgBrCl/trimethyl borate are described. 1-Alkylisoquinolines (2, 3A, 4A, 5A, 6, and 7) and 1-alkyl-3,4-dihydroisoquinolines (3B, 4B, and 5B) are easily prepared under the presented reaction conditions. The role of the B(OMe)3/MgBrCl complex is examined in these homologation reactions. The specific reaction mechanisms, including

  描述了异喹啉与二烷基锂-TMP-锌酸酯·2MgBrCl /硼酸三甲酯的新型一锅同源反应。1-Alkylisoquinolines（2，3A，4A，5A，6和7）和1-烷基-3,4-二氢异喹啉（3B，4B，和5B）很容易呈现的反应条件下制备。在这些同源反应中检查了B（OMe）3 / MgBrCl复合物的作用。提出了具体的反应机理，包括从1-异喹啉基锌酸酯的烷基配体的1，2-迁移。还讨论了1-异喹啉基锌酸酯的配体的迁移能力。