[2-Chloro-2-methyl-prop-(E)-ylidene]-cyclohexyl-amine | 62134-57-0

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [2-Chloro-2-methyl-prop-(E)-ylidene]-cyclohexyl-amine
• CAS: 62134-57-0
• 化学式: C₁₀H₁₈ClN
• 分子量: 187.713
• InChiKey: SZAAPJXIDZNSPP-XYOKQWHBSA-N

物化性质

• 沸点：
  259.2±32.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.41
• 重原子数：
  12.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  12.36
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [2-Chloro-2-methyl-prop-(E)-ylidene]-cyclohexyl-amine 以81%的产率得到
  参考文献：
  名称：

  KIMPE N. DE; VERHE R.; BUYCK L. DE; SCHAMP N., BULL. SOC. CHIM. BELG. , 1977, 86, NO 9, 663-673

  摘要：

  DOI：
• 作为产物：
  描述：

  2-氯-2-甲基丙醛 、 环己胺 在 magnesium sulfate 作用下， 生成 [2-Chloro-2-methyl-prop-(E)-ylidene]-cyclohexyl-amine
  参考文献：
  名称：

  Rearrangement of 4-(1-Haloalkyl)- and 4-(2-Haloalkyl)-2-azetidinones into Methyl ω-Alkylaminopentenoates via Transient Aziridines and Azetidines

  摘要：

  The synthesis of 4-(1-haloalkyl)-2-azetidinones and 4-(2-haloalkyl)-2-azetidinones was investigated with use of the Staudinger reaction between in situ generated ketenes and alpha-haloimines or beta-haloimines. This new class of functionalized 2-azetidinones was further evaluated for its potential use as intermediates in the synthesis of highly functionalized compounds. The reaction of 4-(1-haloalkyl)-2-azetidinones and 4-(2-haloalkyl)-2-azetidinones with sodium methoxide in methanol yielded ring-opened products, i.e., methyl 2-alkoxy-4-(alkylamino)pentenoate and methyl 5-(alkylamino)pentenoate, respectively. Further attention was paid in detail to the reaction mechanism involved in this peculiar transformation. It was proven that these reactions proceeded via intermediate aziridines or azetidines.

  DOI：

  10.1021/jo040161b

文献信息

• Synthesis, fragmentations and rearrangements of 3-(1-haloalkyl)oxaziridines
  作者：Norbert de Kimpe、Bart de Corte

  DOI：10.1016/s0040-4020(01)88271-5

  日期：1992.1

  variety of new 3-(1-haloalkyl)oxaziridines was synthesized by oxidation of α-chloro-, α-bromo-, α,α-dichloro-, α,α-dibromo- and α,α,α-trichloroaldimines with meta-chloroperbenzoic acid. Attempts to induce dehydrohalogenation into the elusive methyleneoxaziridines were unsuccessful. However, presumptive evidence is presented that 2-t-butyl-3-(trichloromethyl)oxaziridine is dehydrochlorinated into a transient

  通过将α-氯代，α-溴代，α，α-二氯-，α，α-二溴代和α，α-α-三氯代亚胺与间氧化反应合成了多种新的3-（1-卤代烷基）恶唑烷-氯过苯甲酸。试图将脱氢卤化作用引入难以捉摸的亚甲基恶唑烷中的尝试没有成功。然而，提供了推定证据，即2-叔丁基-3-（三氯甲基）恶唑烷被脱氯化氢成瞬时的亚甲基恶唑烷，后者经化合价异构化成中间体亚氨基环氧乙烷，后者被片段化成叔丁基异氰化物。报告了标题化合物的各种类型的反应。其中，2-烷基-3-（1-氯-1-甲基）乙基恶唑烷与甲基锂重排成2-（N-烷基）氨基异丁醛。
• Organometallic reactions of α-haloimines as a useful tool in organic synthesis
  作者：Norbert de Kimpe、Bart de Corte、Roland Verhe、Laurent de Buyck、Niceas Schamp

  DOI：10.1016/s0040-4039(01)80111-8

  日期：1984.1

  The reaction of organometallic reagents, e.g. alkyllithiums, cuprates and alkylcoppers, with α-haloimines gave selectively a variety of synthetically useful reactions, including coupling to 1,4-diimines, homologation, and production of heterocycles.

  有机金属试剂（例如烷基锂，铜酸盐和烷基铜）与α-卤代亚胺的反应选择性地产生了多种合成上有用的反应，包括与1,4-二亚胺的偶联，同系物和杂环的产生。
• Synthesis of 1,2-Diamines, 2-Imidazolidinones and 2-Imidazolidinethiones from α-Haloimines
  作者：Norbert De Kimpe、Luc D'Hondt

  DOI：10.1055/s-1993-25989

  日期：——

  α-Bromo- and α-chloroaldimines 1 are easily converted into α-azidoaldimines 2 which are reduced by lithium aluminum hydride to afford N-monoalkylated 1,2-diamines 3. In a similar way, aromatic α-bromoketimines 7 are transformed into the corresponding α-azidoketimines 8 and α-monoalkylated 1,2-diamines 9. The 1,2-diamines, thus obtained, are converted into 2-imidazolidinones 4, 10 and 2-imidazolidinethiones 5, 11.

  δ-溴和δ-氯醛酸亚胺 1 很容易转化成δ-叠氮醛酸亚胺 2，后者经氢化铝锂还原后得到 N-单烷基化的 1,2-二胺 3。同样，芳香族 δ±-溴酮亚胺 7 也可转化为相应的δ-叠氮酮亚胺 8 和δ-单烷基化 1,2-二胺 9。由此得到的 1,2-二胺可转化为 2-咪唑烷酮 4、10 和 2-咪唑烷硫酮 5、11。
• Reactivity of α-chloro-aldimines
  作者：Norbert De Kimpe、Roland Verhé、Laurent De Buyck、Hashim Hasma、Niceas Schamp

  DOI：10.1016/0040-4020(76)87034-2

  日期：1976.1

  intermediate. On the other hand, α-phenyl-substituted α-chloro aldimines on treatment with methoxide in methanol underwent α-substitution, consistent with an SN1 mechanism. Powerful nucleophiles such as sodium thiophenolate in methanol and sodium azide in acetone caused α-substitution. Reaction of α-chloro aldimines with Grignard reagents produced coupling of two aldimine units or α-alkylation. Finally

  通过将二取代的乙醛与伯胺缩合，然后在四氯化碳中用N-氯代琥珀酰亚胺氯化来制备一系列的仲N-1-（2-氯亚烷基）胺。描述了对这些α-氯醛的N-同源物的反应性的研究。在甲醇中用甲醇钠处理标题化合物得到高产率的α，β-不饱和醛亚胺。然而，N-1-（2-氯-2-甲基亚丙基）胺提供了消除和重排产物的混合物，其通过氮丙啶中间体进行。另一方面，在甲醇中用甲醇盐处理的α-苯基取代的α-氯醛亚胺经历了α取代，这与S N相一致。1机制。强大的亲核试剂，例如甲醇中的硫酚钠和丙酮中的叠氮化钠会引起α取代。α-氯醛亚胺与格氏试剂的反应产生两个醛亚胺单元的偶联或α-烷基化。最后，将α-氯醛亚胺的反应性与相应的氧类似物，即α-氯醛的反应性进行了比较。
• Electrophile-Induced Ring Expansions of <i>β</i>-Lactams toward γ-Lactams
  作者：Willem Van Brabandt、Norbert De Kimpe

  DOI：10.1021/jo0509556

  日期：2005.10.1

  was developed from 4-(1-chloroalkyl)azetidin-2-ones. Starting from the latter β-lactams, a new synthesis of pyrrolidin-2-ones was achieved. When 4-isopropenylazetidin-2-ones were treated with bromine in dichloromethane, diastereoselective electrophile-induced ring expansions toward 5-bromopyrrolidin-2-ones were performed. Further oxidation of 3-benzyloxypyrrolidin-2-ones with bromine toward 3-bromopyrrolidin-2-ones

  从4-（1-氯烷基）氮杂环丁烷-2-酮开发了一种有效而直接的向3,4-顺-4-异丙烯基氮杂环丁烷-2-酮的途径。从后者的β-内酰胺开始，实现了吡咯烷-2-酮的新合成。当将4-异丙烯基氮杂环丁烷-2-酮用溴在二氯甲烷中处理时，进行了非对映选择性亲电试剂诱导的向5-溴吡咯烷酮-2-酮的环扩展。还确定了3-苄氧基吡咯烷-2-酮进一步被溴氧化成3-溴吡咯烷-2-酮。当将4-异丙烯基-β-内酰胺添加到NBS和TMSN 3的混合物中时，以中等至高收率获得了5-叠氮基吡咯烷酮-2-酮。