ethyl benzylidine carbamate | 51608-63-0

• 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: ethyl benzylidine carbamate
• 英文别名: ethyl (NE)-N-benzylidenecarbamate
• CAS: 51608-63-0
• 化学式: C₁₀H₁₁NO₂
• 分子量: 177.203
• InChiKey: MVXGXMUYIXDLQP-DHZHZOJOSA-N

物化性质

• 沸点：
  263.9±23.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl benzylidine carbamate 在 六甲基磷酰三胺 、 potassium carbonate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.0h， 生成 ethyl 4-methyl-2-phenyl-3-(phenylsulfonyl)-2,5-dihydropyrrole-1-carboxylate
  参考文献：
  名称：

  将砜碳负离子立体选择性添加到 C=N：对 MIRC 反应中酰胺阴离子稳定性和反应性的关键依赖

  摘要：

  通过在添加烯丙基砜碳负离子过程中调节与受体亚胺氮原子相连的吸电子基团（ArSO2、COOEt、ArSO），开发了一种选择性合成功能化 4-亚甲基吡咯烷的方法。还检查了添加到 2H-氮杂环中的砜碳负离子。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejoc.200300781
• 作为产物：
  描述：

  ethyl [phenyl(phenylsulfonyl)methyl]carbamate 在 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以97%的产率得到ethyl benzylidine carbamate
  参考文献：
  名称：

  A Novel [3+2] Cycloaddition Approach to Nitrogen Heterocycles via Phosphine-Catalyzed Reactions of 2,3-Butadienoates or 2-Butynoates and Dimethyl Acetylenedicarboxylate with Imines:  A Convenient Synthesis of Pentabromopseudilin

  摘要：

  The reactivity of a new three carbon synthon, generated in situ from the reaction of 2,3-butadienoates or 2-butynoates with an appropriate phosphine as the catalyst, toward the electron deficient imines is described. Triphenylphosphine-catalyzed reaction of-methyl a,3-butadienoate with N-sulfonylimines gave the single [3+2] cycloadduct in excellent yield; tributylphosphine-catalyzed reaction of methyl 2,3-butadienoate or 2-butynoate with N-tosylimines afforded the corresponding [3+2] cycloadduct as the major product along with a small amount of the three components adduct. Aliphatic N-tosylimines gave moderate yield for this reaction. In addition, a new phosphine-catalyzed cyclization reaction of dimethyl acetylenedicarboxylate with N-tosylimines is also described. A:reaction mechanism is proposed. Further elaborations of the cycloaddition products and the synthesis of pentabromopseudilin using this method are exemplified.

  DOI：

  10.1021/jo9723063

文献信息

• Sulfonylimidates as Nucleophiles in Catalytic Addition Reactions
  作者：Ryosuke Matsubara、Florian Berthiol、Shū Kobayashi

  DOI：10.1021/ja077054u

  日期：2008.2.1

  first catalytic addition reactions of sulfonylimidates have been accomplished. In the presence of a catalytic amount of DBU (normally 5−10 mol %), sulfonylimidates reacted with several N-protected imines, methyl acrylate, and azodicarboxylate to afford the corresponding addition adducts, sulfonylimidates, in excellent yields. In the addition reactions to imines, high anti-selectivity was observed. A

  磺酰亚胺酯的第一次催化加成反应已经完成。在催化量的 DBU（通常为 5-10 mol%）存在下，磺酰亚胺酯与几种 N 保护的亚胺、丙烯酸甲酯和偶氮二羧酸酯反应，以极好的收率提供相应的加合物磺酰亚胺酯。在与亚胺的加成反应中，观察到高抗选择性。还描述了从醛和磺酰亚胺酸酯直接形成 β-氨基酸衍生物的新方法。
• Asymmetric Aza-Morita-Baylis-Hillman Reactions of Alkyl Vinyl Ketones with N-Protected Imines or In Situ Generated N-Protected Imines
  作者：Xiao-Yang Guan、Yin Wei、Min Shi

  DOI：10.1002/ejoc.201000496

  日期：2010.7

  DABCO-catalyzed aza-MBH reactions of N-Boc imines with MVK and EVK have been thoroughly investigated in the paper. The asymmetric version of this aza-MBH reaction was also systematically investigated by using a chiral amine or a chiral phosphane catalyst. It was found that most of the N-protected imines are suitable substrates under the mild reaction conditions and are able to give the corresponding

  DABCO 催化的 N-Boc 亚胺与 MVK 和 EVK 的 aza-MBH 反应已在论文中进行了彻底的研究。还通过使用手性胺或手性磷烷催化剂系统地研究了这种 aza-MBH 反应的不对称形式。发现大多数 N 保护的亚胺在温和的反应条件下是合适的底物，并且能够以中等产率和高 ee 值得到相应的加合物。TQO-或LB1-催化的N-保护的α-酰氨基烷基苯砜或α-酰氨基烷基对甲苯基砜与MVK的氮杂-MBH反应可以很好地进行，这为获得高对映选择性氮杂-MBH加合物提供了一种简便直接的途径.
• Catalytic imino Diels–Alder reaction by triflic imide and its application to one-pot synthesis from three components
  作者：Kiyosei Takasu、Naoya Shindoh、Hidetoshi Tokuyama、Masataka Ihara

  DOI：10.1016/j.tet.2006.09.092

  日期：2006.12

  An imino Diels–Alder reaction of 2-siloxydienes with aldimines catalyzed by triflic imide (Tf2NH; 0.1∼10 mol % amount) has been developed leading to substituted piperidin-4-ones. Tf2NH catalyst is compatible with basic functions, such as pyridine and indole rings in the imino Diels–Alder reaction. Furthermore, X-ray crystallographic analysis indicates that trans-2,6-diphenyl-4-piperidinone 4a obtained

  已经开发了2-甲硅烷基二烯与三氟甲酰亚胺（Tf 2 NH； 0.1〜10 mol％的量）催化的醛亚胺的亚氨基Diels-Alder反应，从而产生了取代的哌啶-4-酮。Tf 2 NH催化剂与基本功能兼容，例如亚氨基Diels-Alder反应中的吡啶和吲哚环。此外，X射线晶体学分析表明，通过该反应获得的反式-2,6-二苯基-4-哌啶酮4a在固态具有独特的构象。
• Remote asymmetric induction in reactions between 4- and 5-benzyloxypent-2-enyl(tributyl)stannanes and chiral imines prepared from butyl glyoxylate
  作者：David J. Hallett、Eric J. Thomas

  DOI：10.1039/c39950000657

  日期：——

  Transmetallation of 4- and 5-benzyloxypent-2-enyl(tributyl)stannanes 13 and 18 with tin(IV) chloride generates intermediate allyltin trichlorides which react with imines 9 and ent-9, prepared from butyl glyoxylate and either (R)- or (S)-1-phenylethylamine, with effective 1,5-asymmetric induction.

  4- 和 5-苄氧基戊-2-烯基（三丁基）锡 13 和 18 与氯化锡（IV）发生反金属反应，生成中间体烯丙基三氯化锡，与乙醛酸丁酯和 (R)- 或 (S)-1- 苯乙胺制备的亚胺 9 和 ent-9 发生反应，产生有效的 1,5- 不对称诱导。
• Enantioselective Brønsted Acid Catalyzed Addition Reactions of ­Methyleneaminopyrrolidine to Imines
  作者：Darren J. Dixon、A. Louise Tillman

  DOI：10.1055/s-2005-917098

  日期：——

  A new series of BINOL-derived multidentate Bronsted acid catalysts has been developed for the enantioselective addition of the d 1 -synthon, methyleneaminopyrrolidine. to N-Boc imines, yielding the versatile, protected α-aminohydrazone intermediates in moderate to good ee.

  已经开发了一系列新的 BINOL 衍生的多齿布朗斯台德酸催化剂，用于对映选择性加成 d 1 -合成子，亚甲基氨基吡咯烷。到 N-Boc 亚胺，以中等至良好的 ee 产生多功能、受保护的 α-氨基腙中间体。