N-Ethoxycarbonyl-2-allyl-anilin | 67902-35-6

• 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: N-Ethoxycarbonyl-2-allyl-anilin
• 英文别名: N-Ethoxycarbonyl-2-allylaniline；ethyl 2-allylphenylcarbamate；N-Carbethoxy-2-allylaniline；Carbamic acid, [2-(2-propenyl)phenyl]-, ethyl ester；ethyl N-(2-prop-2-enylphenyl)carbamate
• CAS: 67902-35-6
• 化学式: C₁₂H₁₅NO₂
• 分子量: 205.257
• InChiKey: OHXKBKSOFDRCSU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-Ethoxycarbonyl-2-allyl-anilin 在 三氟化硼乙醚 、 一水合肼 、 三氟乙酸 作用下， 以 乙醇 为溶剂， 反应 1.17h， 生成 1-(ethoxycarbonyl)-2,3-dihydro-2-<(phenyltelluro)methyl>indole
  参考文献：
  名称：

  Organotelluriums. 20. Aminotellurinylation of olefins and its utilization for synthesis of 2-oxazolidinones

  摘要：

  DOI：

  10.1021/jo00279a031
• 作为产物：
  描述：

  乙醇 、 2-烯丙基苯甲酰胺 在 碘苯二乙酸 、 platinum(II) chloride 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 2.0h， 以86%的产率得到N-Ethoxycarbonyl-2-allyl-anilin
  参考文献：
  名称：

  通过酰胺顺序重排和氨基环化反应，铂催化一锅串联合成吲哚和异喹啉

  摘要：

  通过使用氯化铂（II）作为路易斯酸催化剂，已通过串联的2的霍夫曼型重排实现了简明高效的吲哚氨基甲酸酯，1，2-二氢异喹啉氨基甲酸酯，大环吲哚氨基甲酸酯，吲哚脲和吲哚环烷的合成。炔基苯甲酰胺和2-炔基苄基酰胺，醇和胺向异氰酸酯中间体的亲核加成，以及由此形成的氨基甲酸酯和脲的分子内氨基环化成2-炔基官能团。可以将各种亲核试剂（例如醇，胺和稳定的Wittig试剂）引入衍生自酰胺的异氰酸酯中间体的高度亲电性碳中。当反应在微波辐射下进行时，我们观察到反应速率的提高。

  DOI：

  10.1021/jo101347f

文献信息

• The use of chiral diferrocenyl diselenides for highly selective asymmetric intramolecular selenocyclisation
  作者：Hiroya Takada、Yoshiaki Nishibayashi、Sakae Uemura

  DOI：10.1039/a901087d

  日期：——

  Asymmetric intramolecular selenocyclisation of alkenoic acids, alkenols and alkenyl urethanes using chiral 2-[1-(dimethylamino)ethyl]ferrocenylselenenyl cations proceeds smoothly to give the corresponding organoselenenyl moiety-containing lactones, cyclic ethers and N-heterocycles, respectively, in good to excellent chemical yields (up to 97%) with very high diastereoselectivities (up to 98% de). The nature of the counter anions of the selenenylating agents affected remarkably the diastereoselectivity of the cyclisation, PF6– and BF4– being revealed to be the best for alkenoic acids and alkenols, and alkenyl urethanes, respectively. A plausible reaction scheme for the cyclisation is presented where a chiral selenenylating agent approaches the carbon–carbon double bond of the substrate from the less sterically-congested direction to afford a chiral episelenonium ion followed by an intramolecular back side attack of a nucleophile.

  不对称的分子内硒环化反应针对烯酸、烯醇和烯基氨基甲酸酯，采用手性2-[1-(二甲基氨基)乙基]铁烯基硒正离子顺利进行，生成相应的含有有机硒基团的内酯、环醚和氮杂环，化学收率良好到优异（高达97%），且具有非常高的diastereoselectivity（高达98%去对映体选择性）。硒化试剂的反离子性质显著影响了环化反应的diastereoselectivity，PF6–和BF4–分别被证明是烯酸和烯醇、烯基氨基甲酸酯的最佳选择。提出了一个合理的反应机制，其中手性硒化试剂从立体空间上不拥挤的方向靠近底物的碳-碳双键，形成手性的episelenonium离子，随后发生亲核试剂的分子内背面攻击。
• Aminotellurinylation of Olefins with Benzenetellurinyl Acetate and Ethyl Carbamate
  作者：Nan Xing Hu、Yoshio Aso、Tetsuo Otsubo、Fumio Ogura

  DOI：10.1246/cl.1987.1327

  日期：1987.7.5

  Benzenetellurinyl acetate or trifluoroacetate in combination with ethyl carbamate effected aminotellurinylation of olefins in chloroform under reflux in the presence of boron trifluoride etherate to give ethyl [(2-phenyltelluro)alkyl]carbamates in high yields after reduction with hydrazine hydrate. This reaction was extended to cyclofunctionalization of olefinic carbamates into nitrogen heterocycles.

  乙酸苯碲酯或三氟乙酸酯与氨基甲酸乙酯组合，在三氟化硼乙醚存在下，在回流下，在氯仿中进行烯烃的氨基碲酰化，在用水合肼还原后，以高收率得到[(2-苯基碲)烷基]氨基甲酸乙酯。该反应扩展到烯属氨基甲酸酯环官能化成氮杂环。
• Cyclofunctionalization of olefinic urethanes using benzeneselenenyl chloride in the presence of silica gel: a general route to nitrogen heterocycles
  作者：D. L. J. Clive、Vittorio Farina、Alok Singh、Chi Kwong Wong、William A. Kiel、Steven M. Menchen

  DOI：10.1021/jo01299a019

  日期：1980.5
• Efficient Regio- and Stereoselective Formation of Azocan-2-ones via 8-<i>Endo</i> Cyclization of α-Carbamoyl Radicals
  作者：Xinqiang Fang、Kun Liu、Chaozhong Li

  DOI：10.1021/ja9082649

  日期：2010.2.24

  The iodine-atom-transfer 8-endo cyclization of alpha-carbamoyl radicals was investigated experimentally and theoretically. With the aid of Mg(ClO4)(2) and a bis(oxazoline) ligand, N-ethoxycarbonyl-substituted N-(pent-4-enyl)-2-iodoalkanamides underwent 8-endo cyclization leading to the formation of only the corresponding 3,5-trans-substituted azocan-2-ones in excellent yields Similarly, the BF3 center dot OEt2/H2O-promoted reactions of N-ethoxycarbonyl-N-(2-allylaryl)-2-iodoalkanamides afforded exclusively the benzazocanone products with a 3,5-cis configuration in high yields The bidentate chelation of substrate radicals not only significantly improved the efficiency of cyclization but also resulted in the change of stereochemistry of azocanone products from 3,8-trans to 3,8-cis Theoretical calculations at the UB3LYP/6-31G* level revealed that the cyclization of N-carbonyl-substituted alpha-carbamoyl radicals occurs via the E-conformational transition states without the presence of a Lewis acid. On the other hand, the cyclization proceeds via the Z-conformational transition states when the substrates form the bidentate chelation with a Lewis acid In both cases, the 8-endocyclization is always fundamentally preferred over the corresponding 7-exo cyclization The complexed radicals having the more rigid conformations also allow the better stereochemical control in the iodine-atom-abstraction step To further understand the reactivity of alpha-carbamoyl radicals, the competition between the 8-endo and 5-exo cyclization was also studied The results demonstrated that the 8-endo cyclization is of comparable rate to the corresponding 5-exo cyclization for alpha-carbamoyl radicals with fixed Z-conformational transition states As a comparison, the 8-endo mode is fundamentally preferred over the 5-exo mode in the cyclization of INIH-amide substrates because the latter requires the Z-conformational transition states, whereas the former proceeds via the more stable E-conformational transition states.
• Muehlstaedt, Manfred; Hollmann, Kerstin; Widera, Roland, Zeitschrift fur Chemie, 1988, vol. 28, # 12, p. 436
  作者：Muehlstaedt, Manfred、Hollmann, Kerstin、Widera, Roland

  DOI：——

  日期：——