ethyl N-[(phenyl)(tosyl)methyl]carbamate | 3696-52-4

• 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 N-[(phenyl)(tosyl)methyl]carbamate
• 英文别名: Ethyl N-[[(4-methylphenyl)sulfonyl]phenylmethyl]carbamate；ethyl N-[(4-methylphenyl)sulfonyl-phenylmethyl]carbamate
• CAS: 3696-52-4
• 化学式: C₁₇H₁₉NO₄S
• 分子量: 333.408
• InChiKey: ONAOZAKSCOTEBC-UHFFFAOYSA-N

物化性质

• 熔点：
  132-135 °C
• 沸点：
  542.5±50.0 °C(Predicted)
• 密度：
  1.231±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  80.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl N-[(phenyl)(tosyl)methyl]carbamate 在 potassium fluoride on basic alumina 、 对甲苯磺酸 作用下， 以 甲醇 、 氯仿 、 乙酸乙酯 为溶剂， 反应 42.0h， 生成 ethyl 2-methyl-5-phenyl-1H-pyrrole-1-carboxylate
  参考文献：
  名称：

  α-酰胺基砜与官能化硝基化合物的反应：N-烷氧基羰基-2,5-二取代吡咯的新两步合成†

  摘要：

  由KF在氧化铝上促进的α-酰胺基砜与硝基缩酮的反应提供了相应的加合物，其在用对甲苯磺酸处理后产生相应的N-烷氧基羰基-2，5-二取代的吡咯。后一种转化涉及级联过程，包括缩酮切割，闭环和通过亚硝酸消除而最终的芳构化。

  DOI：

  10.1039/c4ra08112a
• 作为产物：
  描述：

  sodium 4-methylbenzenesulfinate 在 盐酸 作用下， 以 水 为溶剂， 反应 1.33h， 生成 ethyl N-[(phenyl)(tosyl)methyl]carbamate
  参考文献：
  名称：

  Different modes of acid-catalyzed cyclization of 4-(γ-oxoalkyl)semicarbazide hydrazones: 7-membered versus 14-membered cyclic semicarbazones formation

  摘要：

  Acid-catalyzed cyclization of 4-(gamma-oxoalkyl)semicarbazide hydrazones has been studied. 7-Membered cyclic semicarbazones, 2,4,5,6-tetrahydro-3H-1,2,4-triazepin-3-ones, were obtained from the gamma-phenyl-substituted semicarbazides, while the cyclization of the gamma-methyl-substituted semicarbazides involved two molecules of the starting material to result in 14-membered cyclic bis-semicarbazones, 1,2,4,8,9,11-hexaazacyclotetradeca-7,14-diene-3,10-diones. The 4-(gamma-oxoalkyl)semicarbazide hydrazones were prepared according to a four-step synthesis based on amidoallcylation of the sodium enolates of 1,3-diketones with ethyl N-(1-tosylallc-1-yl)carbamates followed by base-promoted retro-Claisen reaction and treatment of the obtained ethyl N-(gamma-oxoalkyl)carbamates with hydrazine. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.10.079

文献信息

• Highly Enantioselective Monofluoromethylation of C2-Arylindoles Using FBSM under Chiral Phase-Transfer Catalysis
  作者：Kohei Matsuzaki、Tatsuya Furukawa、Etsuko Tokunaga、Takashi Matsumoto、Motoo Shiro、Norio Shibata

  DOI：10.1021/ol4013102

  日期：2013.7.5

  The highly enantioselective addition of 1-fluoro-1,1-bis(phenylsulfonyl)methane (FBSM) to vinylogous imines generated in situ from 2-aryl-3-(1-arylsulfonylmethyl)indoles was achieved using chiral ammonium salts derived from cinchona alkaloids. One-pot conversion from 2-arylindoles with FBSM was also adaptable under the same reaction conditions. The key for this transformation is the effective use of

  使用衍生自金鸡纳生物碱的手性铵盐可将1-氟-1,1-双（苯磺酰基）甲烷（FBSM）高度对映选择性地添加到由2-芳基-3-（1-芳基磺酰基甲基）吲哚原位生成的乙烯基亚胺中。 。在相同的反应条件下，2-芳基吲哚与FBSM的一锅转化也适用。该转化的关键是芳基磺酰基的有效利用。
• InBr₃: A Versatile Catalyst for the Different Types of Friedel−Crafts Reactions
  作者：Ponnaboina Thirupathi、Sung Soo Kim

  DOI：10.1021/jo9014613

  日期：2009.10.16

  Mild and efficient InBr3-catalyzed Friedel−Crafts alkylation of heteroaromatic or electron-rich aromatic compounds with α-amido sulfones at room temperature in CH2Cl2 has been developed. The products undergo further Friedel−Crafts alkylation with heteroaromatic or electron-rich aromatic compounds leading to unsymmetrical or bis-symmetrical triaryl methanes in good yield. α-Amido sulfones are employed

  在室温下，在CH 2 Cl 2中，已开发出温和有效的InBr 3催化的杂芳族或富电子芳族化合物与α-酰胺基砜的Friedel-Crafts烷基化反应。产物进一步与杂芳族或富电子芳族化合物进行弗里德-克拉夫特烷基化反应，从而以高收率得到不对称或双对称的三芳基甲烷。α-酰胺基砜被用于合成不对称和双对称的三芳基甲烷。使用温和的反应条件，低催化负荷和高收率是本方法的优点。
• Three-Component Synthesis of α-Aminoperoxides Using Primary and Secondary Dialkylzinc Reagents with O₂ and α-Amido Sulfones
  作者：Alicia Monleón、Marc Montesinos-Magraner、Amparo Sanz-Marco、Gonzalo Blay、José R. Pedro

  DOI：10.1021/acs.orglett.0c01692

  日期：2020.7.17

  synthesis of unprecedented α-aminoperoxides bearing primary and secondary alkylperoxide substituents is described. Commercially available dialkylzinc reagents are oxidized with molecular oxygen and the consequent peroxide species react with stable (hetero)aromatic and aliphatic α-amido sulfones in excellent yields (>90%). The now available α-aminoperoxides are of potential interest in medicinal chemistry

  描述了一种合成前所未有的带有伯和仲烷基过氧化物取代基的α-氨基过氧化物的直接策略。市售的二烷基锌试剂被分子氧氧化，其后的过氧化物与稳定的（杂）芳族和脂族α-酰胺基砜反应，收率极高（> 90％）。目前可用的α-氨基过氧化物在药物化学中具有潜在的意义，特别是用于合成抗疟疾化合物。而且，反应条件的改变选择性地以良好的产率产生N，O-缩醛。
• Synthesis of novel 14-membered cyclic bis-semicarbazones
  作者：Anatoly D. Shutalev、Anastasia A. Fesenko、Olesya M. Kuzmina、Alexander N. Volov、Dmitry V. Albov、Vladimir V. Chernyshev、Ilia A. Zamilatskov

  DOI：10.1016/j.tetlet.2014.08.016

  日期：2014.10

  An efficient method for the stereoselective synthesis of novel 14-membered cyclic bis-semicarbazones based on acid-catalyzed cyclization of the hydrazones of 3-(3-oxobutyl)semicarbazides has been developed. The starting semicarbazides were prepared according to a four-step strategy involving amidoalkylation of the sodium enolate of acetylacetone with N-(α-tosylbenzyl)carbamates followed by base-promoted

  开发了一种有效的立体选择性合成新型14元环状双-半-氨基脲的方法，该方法基于3-（3-氧代丁基）-氨基脲的carb的酸催化环化反应。根据四步策略制备起始氨基脲，该策略涉及乙酰丙酮的烯醇钠与N-（α-甲苯磺酰基苄基）氨基甲酸酯的酰胺烷基化，然后进行碱促进的逆克莱森反应和处理所得的N-（3-氧代丁基）氨基甲酸酯与肼。
• Metal-Free Synthesis of Imido Derivatives by Direct Oxidation of α-Amido Sulfones
  作者：Fabio Martinelli、Alessandro Palmieri、Marino Petrini

  DOI：10.1002/ejoc.201000634

  日期：2010.9

  Oxidation of α-amidoaryl sulfones with m-chloroperoxybenzoic acid under mild conditions readily provides the corresponding imides in satisfactory yields. The overall process probably involves formation of an N-acyliminium ion intermediate, which by attack of the peroxyacid anion generates the final imido derivatives.

  在温和条件下用间氯过氧苯甲酸氧化 α-酰氨基芳基砜很容易以令人满意的产率提供相应的酰亚胺。整个过程可能涉及 N-酰基胺离子中间体的形成，它通过过氧酸阴离子的攻击产生最终的亚胺衍生物。