ethyl 3-methylamino-5-phenylthiophene-2-carboxylate | 92802-07-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻吩类
• 英文名称: ethyl 3-methylamino-5-phenylthiophene-2-carboxylate
• 英文别名: 2-Thiophenecarboxylic acid, 3-(methylamino)-5-phenyl-, ethyl ester；ethyl 3-(methylamino)-5-phenylthiophene-2-carboxylate
• CAS: 92802-07-8
• 化学式: C₁₄H₁₅NO₂S
• 分子量: 261.345
• InChiKey: RTFZGXMXUUYTRB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  66.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-methyl-5-phenyl-4-isothiazolin-3-thione 在 sodium tetrahydroborate 、 mercury(II) diacetate 作用下， 以 乙醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 48.33h， 生成 ethyl 3-methylamino-5-phenylthiophene-2-carboxylate
  参考文献：
  名称：

  C-2上具有各种取代基的3-烷基氨基-5-芳基噻吩的便捷合成及反应机理的研究

  摘要：

  在乙酸汞（II）的存在下，用活性亚甲基化合物（包括β-酮酸酯，硝基甲烷，氰基乙酸，对甲苯磺酰基丙酮，4-硝基苯乙酸和4-乙基苯基乙酸）处理亚硫酰芳基烯酮S，N-缩醛。 CH（2）Cl（2）在室温下。这些反应以良好的收率得到了含有各种取代基的3-烷基氨基-5-芳基噻吩，这些取代基分别在C-2上包含烷氧羰基，硝基，氰基，对甲苯磺酰基，4-硝基苯基和二乙基膦酰基。在相同条件下，使3-甲基氨基-3-甲基硫基-1-苯基硫代丙烯与丙二酸或Meldrum酸反应，得到3-甲基氨基-5-苯基噻吩。同样地，使用各种可烯丙基环酮（例如4-羟基-6-甲基-2-吡喃酮）处理3-甲基氨基-3-甲基硫基-1-苯基硫代丙烯，

  DOI：

  10.1021/jo991884b

文献信息

• Rhodium(<scp>ii</scp>)-mediated reactions of thiobenzoylketene S,N-acetals with α-diazo carbonyl compounds: synthesis of 2-substituted 3-alkylamino-5-phenylthiophenes
  作者：Hyun Min Song、Kyongtae Kim

  DOI：10.1039/b203931a

  日期：——

  Treatment of 3-methylamino-3-methylsulfanyl-1-phenylpropenethione 1 with excess (2.5 equiv.) α-diazo carbonyl compounds such as α-diazoketones and α-diazoesters in the presence of a catalytic amount of Rh(II) acetate in CH2Cl2 at rt gave 2-acyl- or 2-aroyl-3-methylamino-5-phenylthiophenes and alkyl 3-methylamino-5-phenylthiophene-2-carboxylates, respectively, as major products along with 1-phenyl-2-methylsulfanylethanones. The formation of the major products indicates that the carbenes or carbenoids generated interact initially with the thione sulfur of 1.

  3-甲基氨基-3-甲基硫醇-1-苯基丙烯硫酮1与多量（2.5倍当量）α-二氮烯羰基化合物（如α-二氮酮和α-二氮酯）在常温下的二氯甲烷中，存在催化量的铑(II)醋酸盐反应，主要生成2-酰基或2-芳酰基-3-甲基氨基-5-苯基噻吩和烷基3-甲基氨基-5-苯基噻吩-2-羧酸酯，以及1-苯基-2-甲基硫基乙酮。主要产品的形成表明，生成的卡宾或卡宾类化合物最初与1的硫酮硫发生相互作用。
• [4+1] Cycloaddition of Enaminothiones and Aldehyde <i>N</i> -Tosylhydrazones Toward 3-Aminothiophenes
  作者：Zhuqing Liu、Ping Wu、Yuan He、Ting Yang、Zhengkun Yu

  DOI：10.1002/adsc.201801028

  日期：2018.11.16

  An efficient protocol toward trisubstituted 3‐aminothiophenes has been developed through a [4+1] cycloaddition of enaminothiones and aldehyde N‐tosylhydrazones under transition‐metal‐free conditions. 3‐Aminothiophene derivatives as well as their chiral analogs were obtained in good to excellent yields. Direct interaction of the enaminothiones with the diazo compounds of α‐carbonyl or ester group‐functionalized

  通过在无过渡金属条件下烯胺硫酮和醛N-甲苯磺酰s的[4 + 1]环加成反应，已开发出一种有效的三取代3-氨基噻吩方案。3-氨基噻吩衍生物及其手性类似物的收率良好。烯氨基硫酮与α-羰基或酯基官能化醛的重氮化合物的直接相互作用也有效地提供了相同类型的3-氨基噻吩。合成方法的多样性已通过广泛的底物范围和对烯胺硫酮的C-S，C-O和C-N键裂解的出色化学选择性证明。
• The conversions of isothiazolium salts into thiophenecarboxylic ester derivatives
  作者：David M. McKinnon、K. Ann Duncan、Lesley M. Millar

  DOI：10.1139/v84-271

  日期：1984.8.1

  Several 3-aminothiophene-2-carboxylic ester derivatives are made by reaction of potassium 3-ethoxy-3-oxopropanoate with isothiazolium salts or by reaction with 2-ethoxy-2-oxoethylidenedimethylsulfurane. In the latter case deaminated products are also isolated. These products are consistent with initial nucleophilic attack on the sulfur atom of the isothiazolium salt. In one case a pyrrole derivative is formed by a novel rearrangement of an intermediate aziridine derivative. Some further derivatives of 3-benzylaminobenzo[b]thiophene are described.

  通过将钾3-乙氧基-3-氧代丙酸酯与异噻唑盐反应或与2-乙氧基-2-氧代乙基亚甲基二甲基硫烷反应，制备了几种3-氨基噻吩-2-羧酸酯衍生物。在后一种情况下，还分离出去氨基产物。这些产物与异噻唑盐的硫原子的初始亲核攻击一致。在一个案例中，通过中间环氮烷衍生物的新颖重排形成吡咯衍生物。还描述了一些3-苄基氨基苯并[b]噻吩的进一步衍生物。
• Reactions of Thioaroylketene <i>S,N</i>-Acetals with 1,3-Dicarbonyl Compounds in the Presence of Mercury(II) Acetate:  A General Route to 2-Acyl- and 2-Aroyl-3-(alkylamino)-5- arylthiophenes and 2-(Ethoxycarbonyl)-3- (methylamino)-5-arylthiophenes
  作者：Bo Sung Kim、Kyung Seok Choi、Kyongtae Kim

  DOI：10.1021/jo981043p

  日期：1998.9.1
• Novel Synthesis of 5,6-Dihydro-4<i>H</i>-thieno[3,2-<i>b</i>]pyrrol-5-ones via the Rhodium(II)-Mediated Wolff Rearrangement of 3-(Thieno-2-yl)-3-oxo-2-diazopropanoates
  作者：Dong Joon Lee、Kyongtae Kim、Yung Ja Park

  DOI：10.1021/ol016995n

  日期：2002.3.1

  [GRAPHICS]Treatment of thioaryolketene S,N-acetals 12 with Hg(OAc)(2) followed by addition of 2-diazo-3-trimethylsilyloxy-3-butenoic acid alkyl esters 15 in CH2Cl2 at room temperature gave 3-(3-alkylamino-5-arylthieno-2-yl)-3-oxo-2-diazopropanoates 16 in good yields. Subsequent reactions of 16 with a catalytic amount of Rh-2(OAc)(4).2H(2)O in benzene at reflux afforded a mixture of 5,6-dihydro-4H-thieno[3,2-b]pyrrol-5-ones 18 and the corresponding enols 19 in excellent yields.