6-Oxa-7-aza-bicyclo[3.2.2]non-8-ene-7-carboxylic acid benzyl ester | 146309-04-8

• 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: 6-Oxa-7-aza-bicyclo[3.2.2]non-8-ene-7-carboxylic acid benzyl ester
• 英文别名: benzyl 6-oxa-7-azabicyclo[3.2.2]non-8-ene-7-carboxylate
• CAS: 146309-04-8
• 化学式: C₁₅H₁₇NO₃
• 分子量: 259.305
• InChiKey: ZIYCQZMHDUAAPY-UHFFFAOYSA-N

物化性质

• 沸点：
  387.2±32.0 °C(Predicted)
• 密度：
  1.209±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.05
• 重原子数：
  19.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  38.77
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  6-Oxa-7-aza-bicyclo[3.2.2]non-8-ene-7-carboxylic acid benzyl ester 在 palladium on activated charcoal 氯化亚砜 、 氢溴酸 、 氢气 、 溶剂黄146 、 锌 作用下， 以 甲醇 、 氘代氯仿 为溶剂， 25.0~60.0 ℃ 、101.33 kPa 条件下， 反应 48.5h， 生成 降莨菪鹼
  参考文献：
  名称：

  Synthetic approaches to nortropanes and nortrop-6-enes; intramolecular displacement by nitrogen in 7-membered rings

  摘要：

  The synthesis of simple nortropane and nortrop-6-ene derivatives from cyclohepta-1,3-diene is described. The key intermediates are trans-1-amino-4-chloro-cycloheptanes and -cyclohept-2-enes which are derived efficiently from the corresponding cis-amino-alcohols and undergo intramolecular cyclisation. Corresponding derivatisation of cyclohexa- and cycloocta-1,3-dienes is explored and attempts to achieve Pd-catalysed cyclisation of 1-amino-4-acetoxy-derivatives is described. Nitrogen inversion data for selected nortropane derivatives are included.

  DOI：

  10.1016/s0040-4020(01)80313-6
• 作为产物：
  描述：

  N-(苄羰氧基)羟基胺 、 1,3-环庚二烯 在 tetramethylammonium metaperiodate 作用下， 以 二氯甲烷 为溶剂， 以91%的产率得到6-Oxa-7-aza-bicyclo[3.2.2]non-8-ene-7-carboxylic acid benzyl ester
  参考文献：
  名称：

  降冰片烷和降冰片烯6烯衍生物的简单方法

  摘要：

  分子内环化的-1-（苄基氨基）-4- chlorocycloheptane和庚-2-烯分别得到相应的8-氮杂双环[3.2.1]辛烷（去甲莨菪烷）和-辛-6-烯（nortrop -6-烯）衍生物。在适当的条件下，环庚-1,3-二烯以75％的总收率转化为降冰片烷。

  DOI：

  10.1016/s0040-4039(01)81095-9

文献信息

• Synthesis of physoperuvine (8-methyl-8-azabicyclo[3.2.1]octan-1-ol), norphysoperuvine and dehydro-derivates
  作者：David E. Justice、John R. Malpass

  DOI：10.1039/p19940002559

  日期：——

  4-Aminocycloheptanones have been synthesised in high yield from cyclohepta-1,3-diene. These compounds exist mainly as the bicyclic tautomers (8-azabicyclo[3.2.1 ]octan-1-ol derivatives; the title compounds) as shown by 13C NMR spectroscopy at low temperatures. 4-Aminocyclohept-2enones are reactive but show a preference for the monocyclic tautomers; N-benzyloxycarbonyl derivatives of the saturated and

  已经从环庚-1，3-二烯高产率地合成了4-氨基环庚酮。这些化合物主要以双环互变异构体（8-氮杂双环[3.2.1]辛烷-1-醇衍生物；标题化合物）的形式存在，如低温下的13 C NMR光谱所示。4-Aminocyclohept-2enones具有反应性，但对单环互变异构体表现出偏爱；分离出饱和和不饱和体系的N-苄氧基羰基衍生物作为单环互变异构体。
• Manipulation of substituents at nitrogen in tropanes, homotropanes, and dehydro- derivatives
  作者：Nicola M. Howarth、John R. Malpass、Craig R. Smith

  DOI：10.1016/s0040-4020(98)00643-7

  日期：1998.9

  Trop-6-ene (8-methyl-8-azabicyclo[3.2.1]oct-6-ene) and substituted N-benzylnortrop-6-enes are synthesised. N-Debenzylation of tropanes fails using a wide variety of non-hydrogenolytic conditions despite effective application in model piperidine derivatives; debenzylation of homotropanes is more successful, giving norhomotropane and norhomotrop-7-ene. Bridged N-benzyl compounds react more slowly than N-methyl analogues with chloroformates; the resulting quaternary intermediates are more prone than the N-methyl analogues to suffer competitive reversion to the starting amine, especially in the tropanes, consistent with slower S(N)2 attack at the benzylic carbon during decomposition; the use of an N-p-methoxybenzyl group does allow partial debenzylation to nortrop-6-ene, suggesting greater SNI character in the decomposition step in this case. 'Equatorial' attack is preferred in methylation of N-benzyl-nortrop-6-ene and -homotrop-7-ene with CH3I; subsequent reductive debenzylation of the quaternary salt achieves overall replacement of N-benzyl by N-methyl in both cases. VT NMR studies show the presence of a single 'equatorial' invertomer (Cl syn- to the 2C-bridge) in N-chloro-norhomotropanes and -7-enes and, by analogy, in the N-alkyl compounds. (C) 1998 Elsevier Science Ltd. All rights reserved.
• BATHGATE, ANTOINETTE;MALPASS, JOHN R., TETRAHEDRON LETT., 28,(1987) N 47, 5937-5940
  作者：BATHGATE, ANTOINETTE、MALPASS, JOHN R.

  DOI：——

  日期：——