endo-5-aminomethylbicyclo[2.2.1]hept-2-ene

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: endo-5-aminomethylbicyclo[2.2.1]hept-2-ene
• 英文别名: bicyclo[2.2.1]hept-5-en-endo-2-ylmethylamine；[(1S,2S,4S)-2-bicyclo[2.2.1]hept-5-enyl]methanamine
• 化学式: C₈H₁₃N
• 分子量: 123.198
• InChiKey: XLBALIGLOMYEKN-XLPZGREQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  endo-5-aminomethylbicyclo[2.2.1]hept-2-ene 以78%的产率得到
  参考文献：
  名称：

  Markow W. I., Kasjan A. O., Seljutin O. B., Ukr. khim. zh, 60 (1994) N 7-8, S 575-581

  摘要：

  DOI：
• 作为产物：
  描述：

  5-norbornene-2-carbonitrile 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 endo-5-aminomethylbicyclo[2.2.1]hept-2-ene
  参考文献：
  名称：

  笼状胺在樟脑10磺酸酰胺的合成和氧化中的作用

  摘要：

  双环反应[2.2.1]庚-5-烯外切-和-内-2- ylmethanamines，外切-5,6-epoxybicyclo- [2.2.1]庚外型-2-基甲胺，1-（二环[在三乙胺存在下，在氯仿中，将2.2.1]庚-2-基）乙胺和1-（1-金刚烷基）乙胺与樟脑-10-磺酰氯一起得到具有两个笼状片段的相应磺酰胺。用由邻苯二甲酸酐和50％过氧化氢原位生成的过氧邻苯二甲酸氧化立体异构的N-（双环[2.2.1]庚-5-烯-2-基甲基）樟脑-10-磺酰胺。因此，外立体异构体被转化为相应的5,6-环氧衍生物，而内异构体产生4-（7,7-二甲基-2-氧代双环[2.2.1]庚-1-基甲基）-4-氮杂三环[4.2.1.0 3,7 ]-壬基-外-2--2-醇（取代的氮杂布伦丹）。合成的樟脑-10-磺酰胺的结构通过IR，1 H和13 C NMR光谱确认，采用了同位（COSY）和异核1 H- 13 C相关技术（HM

  DOI：

  10.1134/s1070428009070057

文献信息

• Synthesis and Reactivity of Amines Containing Several Cage-like Fragments
  作者：L. I. Kas’yan、D. V. Karpenko、A. O. Kas’yan、A. K. Isaev

  DOI：10.1007/s11178-005-0226-7

  日期：2005.5

  By reaction of bicyclo[2.2.1]hept-5-en-exo- and endo-2-ylmethylamine, exo-5,6-epoxybicyclo[2.2.1]hept-exo-2-ylmethylamine and benzylamine with 1-adamantanecarbonyl chloride, 1,3-adamantanedicarbonyl dichloride, and 1,3-adamantanediacetyl dichloride amides were obtained with one, two, and three cage-like fragments that were reduced to amines by lithium aluminum hydride. The reactivity of the amines was evaluated with the use of semiempirical quantum-chemical method PM3. Derivatives of the amines were prepared by reactions with arene-sulfonyl chlorides, p-nitrobenzoyl chloride, succinic and endic anhydrides, p-toluenesulfonyl and m-tolyl isocyanates, phenyl isothiocyanate, and p-nitrophenyloxirane. The structure of the new compounds was supported by analysis of their IR and 1H NMR spectra. The dependence of some reaction conditions was observed on the number and remoteness of the cage-like fragments from the reaction centers of the amines.

  通过双环[2.2.1]庚-5-烯-外-和内-2-基甲胺与外-5,6-环氧双环[2.2.1]庚-外-2-基甲胺和苄胺与1-金刚烷酰氯、1,3-金刚烷二酰二氯和1,3-金刚烷二乙酰二氯的反应，制得具有一个、两个和三个笼状片段的酰胺，这些酰胺经氢化锂铝还原为胺。使用半经验的量子化学方法PM3评估了这些胺的反应性。通过与芳烃磺酰氯、对硝基苯甲酰氯、琥珀酸和恩氏酐、对甲苯磺酰和间甲苯基异氰酸酯、苯基异硫氰酸酯和对硝基苯环氧化物的反应，制备了这些胺的衍生物。新化合物的结构得到了其红外和1H核磁共振光谱分析的支持。观察到某些反应条件依赖于笼状片段的数量及其与胺反应中心的距离。
• Amine-Containing Acetylene Compounds of the Norbornene Series—Promising Biocides for Use in Petroleum Production
  作者：M. I. Shatirova、M. M. Movsumzade、U. Sh. Dzhafarova、Ya. G. Avdeev

  DOI：10.1134/s0965544119020166

  日期：2019.2

  norbornene with propargyl bromide, corresponding adducts of the norbornene series which contain a terminal acetylene bond and an amino group in the side chain are formed depending on the molar ratio. Synthesized N-propargylbicyclo[2.2.1]hept-5-ene-2-yl-methylamine is a very reactive compound and can participate in various reactions, in particular, by the amino group or the double bond, to form new

  摘要在双环[2.2.1]庚-5-烯-2-基-甲基胺的基础上，合成了一系列对硫酸盐还原菌具有杀菌活性的炔丙基胺衍生物。已经显示，在胺基降冰片烯与炔丙基溴相互作用的情况下，取决于摩尔比，形成了降冰片烯系列的相应加合物，其在末端链中包含末端乙炔键和氨基。合成的N-炔丙基双环[2.2.1]庚-5-烯-2-基-甲基胺是一种非常活泼的化合物，可以参与各种反应，特别是通过氨基或双键参与，以形成新的衍生物。已经发现，所有浓度为500mg / L的合成物质都完全抑制硫酸盐还原菌的生长。
• Epoxidation and Heterocyclization of Arenesulfonamides of the Norbornene Series
  作者：A. O. Kas'yan、D. V. Karpenko、L. I. Kas'yan

  DOI：10.1007/s11178-006-0035-7

  日期：2005.12

  Reactions of previously known and newly synthesized N-(bicyclo[2.2.1]hept-5-en-endo-2-ylmethyl)arenesulfonamides with monoperoxyphthalic acid generated in situ from phthalic anhydride and 30% hydrogen peroxide lead mostly to the corresponding N-arylsulfonyl-exo-2-hydroxy-4-azatricyclo[4.2.1.03,7]nonanes (azabrendanes). In some cases, N-(exo-5,6-epoxybicyclo[2.2.1]hept-5-en-exo-2-ylmethyl)arenesulfonamides were isolated as the only products or mixtures of alternative oxidation products were obtained. The presence of electron-acceptor nitro groups in the benzene ring and bulky substituents, primarily in the ortho position, is considered to be a structural factor preventing the primary oxidation products (epoxy derivatives) from undergoing heterocyclization.

  以前已知的和新合成的N-(bicyclo[2.2.1]hept-5-en-endo-2-ylmethyl)芳基磺酰胺与现场生成的单过氧邻苯二甲酸的反应，主要是通过邻苯二甲酸酐和30%的过氧化氢反应生成的，主要生成相应的N-芳基磺酰基-exo-2-羟基-4-氮杂三环[4.2.1.03,7]壬烷（氮杂布伦丹）。在某些情况下，N-(exo-5,6-环氧双环[2.2.1]庚-5-烯-exo-2-ylmethyl)芳基磺酰胺被分离为唯一产物，或获得了其他氧化产物的混合物。苯环中存在的电子受体硝基基团和主要位于邻位的笨重取代基被认为是阻止主要氧化产物（环氧衍生物）发生杂环化反应的结构因素。
• Generation of aminyl radicals using sulfenamides as synthetic precursors
  作者：W.Russell Bowman、David N. Clark、Robert J. Marmon

  DOI：10.1016/s0040-4020(01)80837-1

  日期：1994.1

  Sulfenamides are synthesised from reaction between amines and N-(benzenesulfenyl)-phthalimide or benzenesulfenyl chloride. The sulfenamides undergo reaction with tributyltin hydride to yield aminyl radicals which can be cyclised onto suitable alkenes.

  亚磺酰胺是由胺与N-（苯硫基）-邻苯二甲酰亚胺或苯硫基氯之间的反应合成的。所述亚磺酰胺与氢化三丁基锡反应以产生可被环化到合适的烯烃上的氨基自由基。
• Azabrendanes IV. Synthesis and characterization of N-(alkyl- and benzylsulfonyl)-exo-2-hydroxy-4-azatricyclo[4.2.1.03,7]nonanes
  作者：Lilija I. Kasyan、Igor N. Tarabara、Andrey O. Kasyan、Sergiy I. Okovytyy、Andrey V. Tokar、Svetlana V. Shishkina、Oleg V. Shishkin

  DOI：10.1016/j.tet.2006.12.039

  日期：2007.2

  exo- and endo-5-Aminomethylbicyclo[2.2.1]hept-2-enes have been obtained from stereoisomeric exo- and endo-5-cyanobicyclo[2.2.1]hept-2-enes and the corresponding sulfonamides were obtained through reaction of amines with methyl-, n-propyl-, n-butyl-, benzyl-, and cyclohexylsulfonyl chlorides. From the stereoisomeric sulfonamides with peroxy acids, various products were obtained: exo-sulfonamides were

  外-和内-5- Aminomethylbicyclo [2.2.1]庚-2-烯类已经从立体异构体得到的外-和内通过的反应制得-5- cyanobicyclo [2.2.1]庚-2-烯类与相应的磺酰胺与甲基，正丙基，正丁基，苄基和环己基磺酰氯的胺。从具有过氧酸的立体异构磺酰胺中，获得了各种产物：将外磺酰胺转化为环氧衍生物，相反，大多数内消旋异构体都进行了杂环化反应，从而生成了取代的-2--2-羟基-4-氮杂三环[4.2]。 1.0 3,7]壬烷。类型获得不依赖于所使用的过氧酸的种类的产品（过氧，peroxyphthalic，和中号氯过氧之一）。与其他内磺酰胺相反，N-（环己基磺酰基）-内-5-氨甲基双环[2.2.1]庚-2-烯与过氧乙酸反应未发生杂环化，这可能是由于空间因素引起的。通过光谱法证实了磺酰胺的结构和立体化学均一性以及它们被过氧酸氧化的产物的结构。N-（环己基磺酰基）-内-5-氨基