2-Azaspiro[5.5]undec-1-ene | 67625-76-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-Azaspiro[5.5]undec-1-ene
• 英文别名: 2-azaspiro<5,5>undec-1-ene
• CAS: 67625-76-7
• 化学式: C₁₀H₁₇N
• 分子量: 151.252
• InChiKey: FPJLJNVIQKKKCL-UHFFFAOYSA-N

物化性质

• 沸点：
  60-63 °C(Press: 0.6 Torr)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-Azaspiro[5.5]undec-1-ene 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 、 甲苯 为溶剂， 25.0 ℃ 、310.27 kPa 条件下， 反应 5.0h， 生成 2-Aza-spiro[5.5]undecane-2-carboxylic acid methylamide
  参考文献：
  名称：

  Liebowitz; Belair; Witiak, European Journal of Medicinal Chemistry, 1986, vol. 21, # 5, p. 439 - 444

  摘要：

  DOI：
• 作为产物：
  描述：

  环己甲腈 在 二异丁基氢化铝 、 lithium diisopropyl amide 作用下， 以 甲苯 为溶剂， 反应 15.25h， 生成 2-Azaspiro[5.5]undec-1-ene
  参考文献：
  名称：

  Burk, Robert M.; Overman, Larry E., Heterocycles, 1993, vol. 35, # 1, p. 205 - 225

  摘要：

  DOI：

文献信息

• Synthesis of novel pipecolic acid derivatives: a multicomponent approach from 3,4,5,6-tetrahydropyridines
  作者：Wolfgang Maison、Arne Lützen、Marc Kosten、Imre Schlemminger、Ole Westerhoff、Jürgen Martens

  DOI：10.1039/a905119h

  日期：——

  A simple approach to several derivatives of pipecolic acid is via a multicomponent reaction starting from cyclic imines 2, which are synthesized on a large scale and with different substitution patterns. The protected amino acids 3 are formed in high yields. In cases where chiral imines are used the target compounds are obtained with remarkable diastereoselectivity. Bisamides 3 serve as versatile precursors for the preparation of a wide range of amino acid derivatives. Different methods of hydrolysis of 3 lead to the free pipecolic acids or its derivatives. Employment of methanol or ethanethiol as a nucleophile in the acid-mediated conversion of enamides 3 results in N-acylated amino acid esters 5. Furthermore a method for the resolution of the obtained racemic α-amino acids via diastereomeric salt formation is described.

  一种简单的方法用于多种派克酸衍生物的合成，是通过从环状亚胺2开始的多组分反应，这些环状亚胺可以大规模合成并具有不同的取代模式。保护的氨基酸3以高产率生成。当使用手性亚胺时，目标化合物以显著的非对映体选择性获得。双酰胺3作为多功能的前体，用于制备多种氨基酸衍生物。对3的不同水解方法可以生成游离的派克酸或其衍生物。在酸介导下，使用甲醇或乙硫醇作为亲核试剂对烯酰胺3进行转化，得到N-酰基氨基酸酯5。此外，还描述了一种通过非对映体盐形成来分离获得的外消旋α-氨基酸的方法。
• Synthesis of novel pipecolic acid derivatives. Part 2. Addition of trimethylsilyl cyanide to 3,4,5,6-tetrahydropyridines
  作者：Ole Westerhoff、Arne Lützen、Wolfgang Maison、Marc Kosten、Jürgen Martens

  DOI：10.1039/b009112j

  日期：——

  The synthesis of alkyl- and aryl-substituted derivatives of pipecolic acid (piperidine-2-carboxylic acid) by a modified Strecker protocol is described. Addition of trimethylsilyl cyanide (TMSCN) to various tetrahydropyridines 1 and subsequent hydrolysis of the obtained α-amino nitriles 2 yielded pipecolic acid derivatives 3. Addition of TMSCN to cyclic imines 1 proceeded rapidly and led to α-amino nitriles in excellent yields without any necessary further purification. Almost quantitative diastereoselectivity for the formation of 2,6-trans-substituted amino nitrile 2g was observed at low temperature, when chiral imine 1g was used as reactant. Acidic hydrolysis of α-amino nitriles 2 yielded the corresponding amino acids 3 in good to excellent yields. Furthermore, an efficient protocol for the optical resolution of N-formylated derivatives of pipecolic acid by separation of diastereomeric norephedrinium salts is described.

  描述了一种通过改进的斯特雷克合成法合成烷基-和芳基取代的哌啶-2-羧酸（皮啶酸）衍生物。将三甲基硅基氰化物（TMSCN）添加到各种四氢吡啶1中，经过水解得到的α-氨基腈2生成了哌啶酸衍生物3。TMSCN与环状亚胺1的反应迅速进行，生成了α-氨基腈，产率极佳，无需进一步净化。在低温下，当使用手性亚胺1g作为反应物时，观察到2,6-反式取代的氨基腈2g的绝对立体选择性几乎是定量的。α-氨基腈2的酸性水解得到相应的氨基酸3，产率良好到优秀。此外，还描述了一种有效的光学分辨法，用于通过分离二醇异构体盐来分离N-甲酰化的哌啶酸衍生物。
• The Synthesis of Novel Cyclic β-Amino Acids as Intermediates for the Preparation of Bicyclic β-Lactams
  作者：Wolfgang Maison、Marc Kosten、Audrey Charpy、Jürgen Kintscher-Langenhagen、Imre Schlemminger、Arne Lützen、Ole Westerhoff、Jürgen Martens

  DOI：10.1002/(sici)1099-0690(199909)1999:9<2433::aid-ejoc2433>3.0.co;2-x

  日期：1999.9

  homopipecolic acid are prepared by α-amino alkylation of malonic acid with cyclic imines 6 and 7. These are prepared on a large scale and with different substitution patterns. The β-amino acids 8 and 9 were formed in high yield and with remarkable diastereoselectivity if chiral imines are used as starting materials. The diastereoselectivity of the amino alkylation leading to homopipecolic acid analogues

  通过丙二酸与环状亚胺 6 和 7 的 α-氨基烷基化制备了高哌啶酸的几种衍生物。这些是大规模制备的，具有不同的取代模式。如果使用手性亚胺作为起始原料，β-氨基酸 8 和 9 会以高产率和显着的非对映选择性形成。通过差向异构化实验将导致高哌啶酸类似物的氨基烷基化的非对映选择性与噻唑烷乙酸的非对映选择性进行比较。描述了通过形成非对映体盐来拆分获得的外消旋 β-氨基酸的方法。β-氨基酸 9 和 15 被转化为它们相应的碳酰苯丙胺类似物 14 和异戊烷 16。
• Azaspiro compounds
  申请人：Rohm and Haas Company

  公开号：US04400512A1

  公开（公告）日：1983-08-23

  This invention relates to a method of using compounds selected from those of the following formula : ##STR1## wherein R.sup.1 is hydrogen, alkyl or alkenyl; R.sup.2 is hydrogen, alkyl, cycloalkyl or mononuclear aryl or R.sup.1 and R.sup.2, taken together with the carbon atom to which they are attached, form a cycloalkyl or cycloalkoxyalkyl; R.sup.3 is hydroxy, alkyl, alkoxycarbonyl, hydroxy lower alkyl or a radical of the formula: --C(.dbd.Y)NR.sup.4 R.sup.5 wherein R.sup.4 is hydrogen, alkyl, or alkenyl, R.sup.5 is alkyl, alkenyl carbalkoxy, or mononuclear aryl, or R.sup.4 and R.sup.5 may be joined together with the nitrogen atom to which they are attached to form a 5- to 7- membered heterocyclic ring having from 1 to 3 hetero atoms; Y is O or S; X is alkyl, alkoxycarbonylalkyl or cyano; m is an integer of 0 to 2 and n and n' are integers each having a value of 1 to 2 and the dotted line indicates an optional carbon to carbon double bond, compositions containing said compounds as insect repellents and to novel compounds.

  这项发明涉及一种使用从以下式中选择的化合物的方法：其中R.sup.1是氢、烷基或烯基；R.sup.2是氢、烷基、环烷基或单核芳基或者R.sup.1和R.sup.2连同它们连接的碳原子形成环烷基或环烷氧基烷；R.sup.3是羟基、烷基、烷氧羰基、羟基较低烷基或者具有以下式的基团：--C(.dbd.Y)NR.sup.4 R.sup.5其中R.sup.4是氢、烷基或烯基，R.sup.5是烷基、烯基羰氧基烷或单核芳基，或者R.sup.4和R.sup.5可能与它们连接的氮原子结合形成具有1到3个杂原子的5到7成员杂环的环；Y是O或S；X是烷基、烷氧羰基烷或氰基；m是0到2的整数，n和n'是每个具有1到2值的整数，虚线表示可选的碳到碳双键，含有所述化合物作为防虫剂的组合物以及新化合物。
• Multicomponent synthesis of tripeptides containing pipecolic acid derivatives: selective induction of cis- and trans-imide bonds into peptide backbones
  作者：Wolfgang Maison、Arne Lützen、Marc Kosten、Imre Schlemminger、Ole Westerhoff、Wolfgang Saak、Jürgen Martens

  DOI：10.1039/b002258f

  日期：——

  A simple approach to several tripeptides consisting of two terminal glycine fragments and a central pipecolic acid derivative was found via a multicomponent reaction starting from tetrahydropyridines. The protected peptides 2a–g were formed in high yields and with different substitution patterns of the central heterocyclic amino acid. In cases where chiral imines were used the target compounds were obtained with remarkable diastereoselectivity. The influence of different substituents attached to the pipecolic acid fragment on N-terminal amide isomerism was investigated using X-ray crystallography and NMR spectroscopic methods.

  通过以四氢吡啶为起点的多组分反应，我们找到了一种简单的方法来制备由两个末端甘氨酸片段和一个中心哌啶醇酸衍生物组成的多种三肽。受保护的肽 2a-g 产量很高，而且中心杂环氨基酸的取代模式各不相同。在使用手性亚胺的情况下，获得的目标化合物具有显著的非对映选择性。利用 X 射线晶体学和核磁共振光谱法研究了连接在哌啶醇酸片段上的不同取代基对 N 端酰胺异构体的影响。