1-(cyclohexylidenemethyl)pyrrolidine | 6815-55-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 1-(cyclohexylidenemethyl)pyrrolidine
• 英文别名: (Pyrrolidinylmethylene)cyclohexane；1-cyclohexylidenemethyl-pyrrolidine；1-(cyclohexylidenemethyl)-pyrrolidine；pyrrolidinomethylenecyclohexane；Pyrrolidinomethylen-cyclohexan
• CAS: 6815-55-0
• 化学式: C₁₁H₁₉N
• 分子量: 165.279
• InChiKey: YMFVUVMIQQNRRO-UHFFFAOYSA-N

物化性质

• 沸点：
  112 °C(Press: 13 Torr)
• 密度：
  1.036±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(cyclohexylidenemethyl)pyrrolidine 在 9-borabicyclo[3.3.1]nonane dimer 作用下， 生成 亚甲基环己烷
  参考文献：
  名称：

  Unusual directive effects in the hydroboration of .beta.,.beta.-disubstituted enamines. Conversion of .alpha.-substituted aldehydes to the corresponding alkenes and .beta.-amino alcohols

  摘要：

  A comprehensive study of the conversion of beta,beta-disubstituted enamines into the corresponding alkenes and beta-amino alcohols by hydroboration-elimination and hydroboration-oxidation, respectively, has been carried out. The amine moiety of beta,beta-disubstituted enamines was found to exert a decisive influence on the regioselectivity of the hydroboration reaction involving borane methyl sulfide (BMS). Thus, in the hydroboration of morpholino and piperidino enamines, the boron atom is initially placed predominantly in the alpha-position. Conversely, the pyrrolidino enamines direct the boron atom exclusively to the beta-position. Three oxidizing agents, trimethylamine N-oxide, sodium perborate, and 30% hydrogen peroxide-solid sodium hydroxide, were tried in order to optimize the oxidation of the intermediate organoborane derivatives to the corresponding amino alcohols. Our results clearly indicated that 30% hydrogen peroxide-solid sodium hydroxide is best suited for this transformation. The yield of amino alcohol ranged from good to essentially quantitative. Enamines derived from beta-aryl aldehydes, upon hydroboration with BMS followed by methanolysis and oxidation with neutral hydrogen peroxide, gave the corresponding 1,1-disubstituted alkenes. Contrary to the regioselectivity observed in the hydroboration reactions involving BMS, the hydroboration of beta,beta-disubstituted enamines using 9-borabicyclo[3.3.1]nonane (9-BBN) gave the trialkylborane intermediates in which the boron atom was placed exclusively at the beta-position regardless of the amine moiety of the enamine. These trialkylborane derivatives were very stable and did not undergo the usual elimination reaction with either methanol or sodium hydroxide. However, on thermal decomposition, these afforded the corresponding 1,1-disubstituted alkenes in high yields.

  DOI：

  10.1021/jo00019a043
• 作为产物：
  描述：

  cyclohexyl(pyrrolidin-1-yl)methanone 在 bis(triphenylphosphine)carbonyliridium(I) chloride 作用下， 以 甲苯 为溶剂， 反应 0.25h， 生成 1-(cyclohexylidenemethyl)pyrrolidine
  参考文献：
  名称：

  仲酰胺与叔酰胺的交叉偶联：使用叔酰胺作为烷基碳负离子的替代物进行酮合成

  摘要：

  近年来，在酰胺的直接转化领域取得了令人兴奋的进展，尽管如此，两种酰胺之间的缩合仍然很少，并且仅限于均偶联反应。本文中，我们报道了仲酰胺与叔酰胺的交叉偶联，这可在温和条件下提供酮的合成，并具有使用叔酰胺作为烷基碳负离子的替代物的功能。该方法依赖于由叔酰胺通过用Vaska催化剂催化部分还原叔酰胺而产生的烯胺与由仲酰胺通过三氟甲磺酸酐活化而原位形成的腈离子的偶联，以及随后的甲酰化作用。

  DOI：

  10.1002/cjoc.201900215

文献信息

• A novel route to aldehydic enol ethers and enamines
  作者：J.C. Gilbert、U. Weerasooriya

  DOI：10.1016/s0040-4039(00)71480-8

  日期：1980.1

  Base-promoted reaction of dimethyl diazomethylphosphonate () with dialkyl and cyclic ketones in the presence of alcohols and of amines affords aldehydic enol ethers and enamines, respectively.

  在醇和胺的存在下，重氮二甲基膦酸二甲酯（）与二烷基和环状酮的碱促进反应分别得到醛烯醇醚和烯胺。
• Enamines as Surrogates of Alkyl Carbanions for the Direct Conversion of Secondary Amides to α-Branched Ketones
  作者：Yong-Peng Liu、Shu-Ren Wang、Ting-Ting Chen、Cun-Cun Yu、Ai-E Wang、Pei-Qiang Huang

  DOI：10.1002/adsc.201801443

  日期：2019.3.5

  A direct transformation of secondary amides into α‐branched ketones with enamines as soft alkylation reagents was developed. In this reaction, enamines serve as surrogates of alkyl carbanions, rather than the conventional enolates equivalents in the Stork's reactions, which allowed for the easy introduction of alkyl groups with electrophilic functional groups. In the presence of 4 Å molecular sieves

  已开发了以烯胺作为软烷基化试剂将仲酰胺直接转化为α-支链酮的方法。在该反应中，烯胺充当烷基碳负离子的替代物，而不是Stork反应中的常规烯醇式等同物，从而可以轻松引入具有亲电官能团的烷基。在存在4Å分子筛的情况下，该方法可以扩展到仲酰胺与醛的单锅偶联以生成酮。
• Divergent and solvent dependent reactions of 4-ethoxycarbonyl-3-methyl-1-tert-butoxycarbonyl-1,2-diaza-1,3-diene with enamines
  作者：Elisabetta Rossi、Giorgio Abbiati、Orazio A. Attanasi、Silvia Rizzato、Stefania Santeusanio

  DOI：10.1016/j.tet.2007.08.039

  日期：2007.11

  temperatures allows the divergent synthesis of 5,6-dihydro-4H-pyridazines, 2-(1-N-boc-hydrazono-ethyl)-4-pyrrolidin-1-yl-but-3-enoic acid ethyl ester, and 1-amino-pyrroles. Moreover, some interesting conclusions about the mechanism(s) of the reaction have been drawn by careful analysis of products' structure and distribution. Thus, the reaction may proceed through a stereospecific [4+2] cycloaddition mechanism

  从1-叔丁氧基羰基-3-甲基-4-乙氧基羰基-1,2-二氮杂1,3-二烯和β，β，β以及α，β-取代的烯胺开始，谨慎选择溶剂，温度允许变化5,6-二氢-4 H-哒嗪，2-（1- N -boc-肼基-乙基）-4-吡咯烷-1-基-丁-3-烯酸乙酯和1-氨基吡咯的合成。此外，通过仔细分析产物的结构和分布，得出了一些有关反应机理的有趣结论。因此，反应可以通过立体特异性的[4 + 2]环加成机理进行，从而产生5,6-二氢-4 H-哒嗪，或者通过简单的加成或多米诺加成/环化途径分别提供2-（1- N-boc-肼基-乙基）-4-吡咯烷-1-基-丁-3-烯酸乙酯和1-氨基-吡咯（以前是[3 + 2]环加成产物）。
• Process of preparing proline derivatives
  申请人：Hoechst Aktiengesellschaft

  公开号：US04849524A1

  公开（公告）日：1989-07-18

  The invention relates to a process for preparing compounds of the formula I ##STR1## in which R stands for hydrogen, alkyl or aralkyl and R.sup.1 to R.sup.5 are identical or different radicals, (substituted) alkyl, cycloalkyl or (substituted) aryl or in which the pairs of radicals R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, and R.sup.4 and R.sup.5 together with the carbon atom(s) supporting them form a mono- or bicyclic ring system and the other radicals are hydrogen, by treating a compound of the formula II ##STR2## in which R and R.sup.1 and R.sup.5 have the abovementioned meaning and R.sup.6 and R.sup.7 denote alkyl or aralkyl or together with the nitrogen atom supporting them form a heterocycle which can additionally contain an oxygen atom, with a reducing agent.

  本发明涉及一种制备式I的化合物的过程：##STR1## 其中，R表示氢、烷基或芳基烷基，R1至R5是相同或不同的基团，（取代）烷基、环烷基或（取代）芳基，或者其中基团R1和R2、R2和R3，以及R4和R5与支持它们的碳原子一起形成单环或双环环系统，而其他基团为氢。该过程通过用还原剂处理式II的化合物实现：##STR2## 其中，R和R1和R5具有上述含义，而R6和R7表示烷基或芳基烷基，或者与支持它们的氮原子一起形成一个杂环，该杂环可以额外包含一个氧原子。
• Synthesis of New 4,4a-Dihydroxanthones via [4+2]-Cycloaddition Reaction
  作者：N. M. Chernov、T. V. Moroz、R. V. Shutov、N. N. Kuz’mich、A. E. Shchegolev、M. V. Sopova、I. P. Yakovlev

  DOI：10.1134/s1070363219120223

  日期：2019.12

  The effect of electronic properties of substituents in the reactants on the [4+2]-cycloaddition of 3-vinyl-chromen-4-ones (dienes) and N-vinylpyrrolidines (dienophiles) has been studied. The conditions determining the formation of 4,4a-dihydroxanthones or benzophenones as the major products have been found. The aromatization of 4,4a-dihydroxanthones via pyran ring opening has been interpreted by quantum

  已经研究了反应物中取代基的电子性质对3-乙烯基色烯-4-酮（二烯）和N-乙烯基吡咯烷酮（二亲亲烯）的[4 + 2]-环加成的影响。已经发现确定形成4,4a-二氢黄嘌呤或二苯甲酮作为主要产物的条件。通过吡喃开环将4,4a-二氢氧杂蒽芳构化已通过量子化学计算进行了解释。已分离出一系列新的4,4a-二氢黄酮和二苯甲酮衍生物。