3-((二甲氨基)亚甲基)樟脑 | 473929-46-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: 3-((二甲氨基)亚甲基)樟脑
• 英文名称: 3-((dimethylamino)methylene)camphor
• 英文别名: (1R,4R)-3-[(E)-(dimethylamino)methylidene]-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one；(1R,4S)-3-[(E)-(dimethylamino)methylidene]-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one；(1R,3E,4S)-3-[(dimethylamino)methylidene]-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one；(1R,4S,3E)-3-((dimethylamino)methylene)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one；(1R,4S,E)-3-((dimethylamino)methylene)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one
• CAS: 473929-46-3
• 化学式: C₁₃H₂₁NO
• 分子量: 207.316
• InChiKey: UGOSHQIMOIGOEZ-HWWWMWNKSA-N

物化性质

• 沸点：
  277.7±19.0 °C(Predicted)
• 密度：
  1.058±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.46
• 重原子数：
  15.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  20.31
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3-((二甲氨基)亚甲基)樟脑 在 盐酸肼 作用下， 以 甲醇 为溶剂， 反应 24.0h， 以81%的产率得到(4S,7R)-4,7-甲桥-1H-吲唑
  参考文献：
  名称：

  Cyclocondensations of (+)-camphor derived enaminones with hydrazine derivatives

  摘要：

  Reactions of 3-[(E)-(dimethylamino)methylidene]-(+)-camphor and (1R,5S)-4-[(E)-(dimethylamino)methylidene]-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-one with hydrazine derivatives were studied. Treatment of 3-[(E)-(dimethylamino)methylidene]-(+)camphor with hydrazines afforded the corresponding fused pyrazoles. Similarly, fused pyrazoles were obtained upon reaction of (1R,5S)-4-[(E)-(dimethylamino)methylidene]-1,8,8-tritnethyl-2-oxabicyclo[3.2.1]octan-3-one with ortho-unsubstituted phenylhydrazines, while reactions with ortho-substituted phenylhydrazines and with hydrazine hydrochloride resulted in 'ring switching' type of transformation to furnish 2-aryl-4-[(1S, 3R)-3-hydroxy-2,2,3-trimethylcyclopentyl]-1,2-dihydro-3H-pyrazol-3-ones. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.02.048
• 作为产物：
  描述：

  Bredereck 试剂 、 白樟油 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以77%的产率得到3-((二甲氨基)亚甲基)樟脑
  参考文献：
  名称：

  新型樟脑硫脲的合成及结构解析

  摘要：

  制备了九种新颖的（+）-樟脑胶衍生的硫脲。3 - （（二甲基氨基）亚甲基）樟脑（2）作为两个的制备中的共同的前体，2-硫脲15，16，17，18，19，20和3 -硫脲官能樟脑衍生物6，7 / 7'， 分别。从2开始，后者分两步或三步准备，而前者分五步准备。所有新化合物的构型都是使用NMR技术和/或单晶X射线晶体学方法精心确定的。手性，2012年。©2012 Wiley Periodicals，Inc.。

  DOI：

  10.1002/chir.21999

文献信息

• Selective α-Methylation of Ketones
  作者：Andriy I. Frolov、Eugeniy N. Ostapchuk、Alexander E. Pashenko、Yaroslav O. Chuchvera、Eduard B. Rusanov、Dmitriy M. Volochnyuk、Sergey V. Ryabukhin

  DOI：10.1021/acs.joc.1c00148

  日期：2021.6.4

  The convenient and scalable preparative approach for the two-step α-methylation of ketones is described. The optimized protocols for regioselective preparation of enaminones with further diastereoselective and functional groups tolerant hydrogenation to α-methylketones are developed. The scope and limitations of the proposed methodology are discussed. The advantages compared to known procedures are

  描述了用于酮的两步 α-甲基化的方便且可扩展的制备方法。开发了区域选择性制备烯胺酮的优化方案，具有进一步的非对映选择性和官能团耐受氢化成 α-甲基酮。讨论了所提议方法的范围和局限性。证明了与已知程序相比的优点。暗示了丙酮在氢化中的意想不到的作用。显示了对早期构建块合成和后期 CH 功能化方法的评估。复杂程序的可制备性和可扩展性通过合成高达 100 g 的几种 α-甲基酮来证明。
• Synthesis of 2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-3-((dimethylamino)methyl)camphor organocatalysts
  作者：Uroš Grošelj、Sebastjan Ričko、Jurij Svete、Branko Stanovnik

  DOI：10.1002/chir.22035

  日期：2012.5

  In a stereo‐divergent synthesis, three novel camphor‐derived bifunctional thiourea organocatalysts 7, 8, 9 have been prepared in five steps starting from (+)‐camphor. In addition, borneol‐derived bifunctional thiourea organocatalysts 19/19’ have been prepared in three steps from (1S)‐(+)‐camphorquinone. Novel organocatalysts 7, 8, 9, 19/19’ have been evaluated in a model reaction of Michael addition

  在立体发散合成，三新颖樟脑衍生的双官能硫脲有机催化剂7，8，9已在五个步骤，用（+）起始-樟脑。此外，冰片衍生的双官能硫脲有机催化剂19 / 19 '已在由式（1三个步骤制备小号（+） - -樟脑醌）。新颖有机催化剂7，8，9，19 / 19 '已在模型反应评价迈克尔加成丙二酸二甲酯向反-β-硝基苯乙烯，具有低至中等对映选择性（20％–60％ee）。已经使用核磁共振（NMR）技术精心确定了所有新化合物的构型。手性24：412–419，2012。分级为4 +©2012 Wiley Periodicals，Inc.
• Stereoselective additions to the exocyclic CC bond of some α-alkylidene-(+)-camphor derivatives
  作者：Uroš Grošelj、David Bevk、Renata Jakše、Anton Meden、Branko Stanovnik、Jurij Svete

  DOI：10.1016/j.tetasy.2006.04.014

  日期：2006.4

  Stereoselective additions to the exocyclic CC double bond of some (1R,3E,4S)-3-alkylidene-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones and (1R,4E,5S)-4-alkylidene-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-ones were studied. All additions took place predominantly from the less hindered endo-face of the methylidene compounds to give the corresponding exo-adducts as the major isomers. Thus, catalytic hydrogenations

  一些（1 R，3 E，4 S）-3-亚烷基-1,7,7-三甲基双环[2.2.1]庚-2--2-和（1 R，4 E，研究了5 S）-4-亚烷基-1,8,8-三甲基-2-氧杂双环[3.2.1] octan-3-one。所有添加发生主要来自较少阻碍内的亚甲基化合物的-面，得到相应的外-adducts为主要异构体。因此，催化氢化提供了α-烷基化的（1 R，3 R，4 R）-1,7,7-三甲基双环[2.2.1]庚基-2-酮和（1 R，4 R，5R）-1,8,8-三甲基-2-氧杂双环[3.2.1] octan-3-ones in 28-100％de。同样，2,4,6-三取代的苄腈氧化物的1,3-偶极环加成反应生成相应的螺环加合物，其取代度为66-100％。通过2D NMR技术，NOESY光谱和X射线衍射确定了结构。
• Stereoselective synthesis of (1R,3R,4R)-3-(1,2,4-triazolo[4,3-x]azin-3-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones
  作者：Uroš Grošelj、Simon Rečnik、Jurij Svete、Anton Meden、Branko Stanovnik

  DOI：10.1016/s0957-4166(02)00208-2

  日期：2002.5

  (1R,3R,4R)-3-(1,2,4-Triazolo[4,3-x]azin-3-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ones were prepared in 68-94% d.e. in three steps from (IR)-(+)-camphor via coupling of (1R,4R)-3-[(E)-(dimethylamino)methylidene]-1 17,7-trimethylbicyclo[2.2.1]heptan-2-one with hydrazinoazines followed by oxidative cyclisation of the intermediate hydrazones with methanolic bromine. The structures were determined by 2D NMR techniques and NOESY spectroscopy as well as by X-ray diffraction. (C) 2002 Elsevier Science Ltd. All rights reserved.

  (1R,3R,4R)-3-(1,2,4-三唑并[4,3-x]嗪-3-基)-1,7,7-三甲基双环[2.2.1]庚烷-2-酮是从 (IR)-(+)-樟脑出发，通过 (1R,4R)-3-[(E)-(二甲基氨基)甲亚基]-1,17,7-三甲基双环[2.2.1]庚烷-2-酮与杂环氨基化合物的缩合反应，随后对中间体的腙进行甲醇溴的氧化环化反应，在三步反应中以 68-94% 的d.e.值成功制备。通过二维核磁共振技术、NOESY 谱和 X 射线衍射对化合物的结构进行了表征。 (C) 2002 Elsevier Science Ltd. 保留所有权利。
• Synthesis and Structural Characterization of Novel Camphor-derived Amines
  作者：Uroš Grošelj、Alen Sevšek、Sebastijan Ričko、Amalija Golobič、Jurij Svete、Branko Stanovnik

  DOI：10.1002/chir.22069

  日期：2012.10

  Two novel 4‐substituted camphidine derivatives 10a,b have been prepared from (+)‐camphor (1) in five steps, the Beckmann rearrangement being the bottleneck of the synthesis. Isoborneol derivative 5b, formed as a side product during the hydrogenation of arylidene ketone 3b, under Beckmann rearrangement conditions yielded interesting novel rearrangement products 11 and 12. (1S)‐(+)‐Camphorquinone (13)

  由（+）-樟脑（1）分五个步骤制备了两个新颖的4-取代的樟脑定衍生物10a，b，贝克曼重排是合成的瓶颈。在贝克曼重排条件下，亚芳基酮3b加氢过程中作为副产物形成的异冰片衍生物5b产生了有趣的新重排产物11和12。（1 S）-（+）-樟脑醌（13）分两步转化为二胺15和16，前者被环化成咪唑啉盐17是N杂环卡宾的前体。所有新化合物的结构均已使用NMR技术和/或单晶X射线分析进行了精细表征。手性24：778–788，2012。分级为4 +©2012 Wiley Periodicals，Inc.