methyl 1-methyl-1H-indole-3-carbodithioate | 30082-24-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: methyl 1-methyl-1H-indole-3-carbodithioate
• 英文别名: methyl 1-N-methyl-1H-indole-3-carbodithioate；methyl (1-N-methyl-3-indolyl)-3-carbodithioate；methyl (1-N-methyl-1H-3-indolyl)carbodithioate；1-methyl-indole-3-carbodithioic acid methyl ester；1-Methyl-indol-3-dithiocarbonsaeure-methylester；Methyl 1-methylindole-3-carbodithioate
• CAS: 30082-24-7
• 化学式: C₁₁H₁₁NS₂
• 分子量: 221.347
• InChiKey: OLYSXCBHAVELSB-UHFFFAOYSA-N

物化性质

• 沸点：
  380.6±34.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  62.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 1-methyl-1H-indole-3-carbodithioate 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 1-(furan-2-yl)-3-(1-methyl-1H-indol-3-yl)-3-(methylthio)-prop-2-en-1-one
  参考文献：
  名称：

  Cyclocondensation of Arylhydrazines with 1,3-Bis(het)arylmonothio-1,3-diketones and 1,3-Bis(het)aryl-3-(methylthio)-2-propenones: Synthesis of 1-Aryl-3,5-bis(het)arylpyrazoles with Complementary Regioselectivity

  摘要：

  Two efficient highly regioselective routes for the synthesis of unsymmetrically substituted 1-aryl-3,5-bis(het)arylpyrazoles with complementary regioselectivity starting from active methylene ketones have been reported. In the first protocol, the newly synthesized 1,3-bis(het)aryl-monothio-1,3-diketone precursors (prepared by condensation of active methylene ketones with het(aryl) dithioesters in the presence of sodium hydride) were reacted with arylhydrazines in refluxing ethanol under neutral conditions, furnishing 1-aryl-3,5-bis(het)arylpyrazoles 7, in which the het(aryl) moiety attached to the thiocarbonyl group of monothio-1,3-diketones is installed at the 3-position. In the second method, the corresponding 3-(methylthio)-1,3-bis(het)aryl-2-propenones (prepared in situ by base-induced alkylation of 1,3-monothiodiketones) were condensed with arylhydrazines in the presence of potassium tert-butoxide in. refluxing tert-butyl alcohol, yielding 1-aryl-3,5-bis(het)arylpyrazoles 9 with complementary regioselectivity (method A). The efficiency of this protocol was further improved by developing a one-pot, three-component procedure for the synthesis of pyrazoles 9, directly from active methylene ketones, by reacting in situ generated 3-(methylthio)-1,3-bis(het)aryl-2-propenones with arylhydrazines in the presence of sodium hydride (instead of potassium tert-butoxide as base). The structures and regiochemistry of newly synthesized pyrazoles were confirmed from their spectral and analytical data along with X-ray crystallographic data of three pairs of regioisomers.

  DOI：

  10.1021/jo400599e
• 作为产物：
  描述：

  indole-3-carbodithioic acid 、 硫酸二甲酯 在 氢氧化钾 作用下， 生成 methyl 1-methyl-1H-indole-3-carbodithioate
  参考文献：
  名称：

  Doyle et al., Journal of the Chemical Society, 1956, p. 2853,2856

  摘要：

  DOI：

文献信息

• Synthesis of 2,4,5-Trisubstituted Oxazoles with Complementary Regioselectivity from α-Oxoketene Dithioacetals and β-(Methylthio)-β-(het)aryl-2-propenones
  作者：Siripuram Vijay Kumar、Anand Acharya、Hiriyakkanavar Ila

  DOI：10.1021/acs.joc.8b00900

  日期：2018.6.15

  An efficient protocol for the synthesis of 2,5-substituted 4-acyloxazoles and the related 2,4-substituted 5-acyloxazoles with complementary regioselectivity from the corresponding α-oxoketene dithioacetals or β-(het)aryl/(methylthio)enone precursors has been reported. In the first protocol, the α-oxoketene dithioacetals or β-(methylthio)enones were converted to the corresponding α-bromo-β-(methylthio)enones

  从相应的α-氧杂环丁烯二硫缩醛或β-（杂）芳基/（甲硫基）烯酮前体合成具有互补区域选择性的2,5-取代的4-酰基恶唑和相关的2,4-取代的5-酰基恶唑的有效方案是被报道。在第一个方案中，将α-氧杂环丁烯二硫缩醛或β-（甲硫基）烯酮转化为相应的α-溴-β-（甲硫基）烯酮，然后用各种伯酰胺将这些中间体进行铜催化的中间/分子内环化，得到2- （杂）芳基/烷基-4-（杂）芳酰基-5-（甲硫基）/（杂）芳基恶唑是通过酰胺中间体同时形成C4-N和C5-O键。在第二种方法中 首先，将起始的α-氧杂环丁烯二硫缩醛或β-（甲硫基）-β-（杂）芳基酮与各种伯酰胺进行碱诱导的共轭加成消除反应，以提供β-芳烯酰胺，随后碘将其催化的分子内氧化C–H官能化/ CO键的形成，以优异的收率提供了相应的区域异构体2-（杂）芳基/烷基-4-（甲硫基）/（杂）芳基-5-（杂）芳酰基恶唑。该方法也已扩展到合成区域异构的4-或5-
• Single-Pot Preparation of 4-Amino-2-(het)aryl-5-Substituted Thiazoles Employing Functionalized Dithioesters as Thiocarbonyl Precursors
  作者：Anusha Avadhani、Pethaperumal Iniyavan、Yogendra Kumar、Hiriyakkanavar Ila

  DOI：10.1021/acs.joc.1c00616

  日期：2021.6.18

  4-amino-2-(het)aryl/alkyl-5-functionalized thiazoles has been disclosed, utilizing aryl/heteroaryl/alkyl dithioesters as thiocarbonyl coupling partners in a modified Thorpe–Ziegler type cyclization. The reaction proceeds at room temperature, under mild conditions, in excellent yields, displaying broad functional group compatibility at 2 and 5 positions of thiazoles. This synthetic strategy has been further

  已经公开了一种有效的、面向多样性的、4-氨基-2-（杂）芳基/烷基-5-官能化噻唑的一锅反应，利用芳基/杂芳基/烷基二硫酯作为改性索普-齐格勒型中的硫代羰基偶联伙伴环化。该反应在室温、温和条件下以优异的产率进行，在噻唑的 2 位和 5 位显示出广泛的官能团相容性。这种合成策略已进一步扩展用于高产率的一锅法构建两种高效微管蛋白聚合抑制剂，即 2-(het)aryl-4-amino-5-(3,4,5-trimethoxyaroyl) thiazoles .
• Reaction of 1,3-Bis(het)arylmonothio-1,3-diketones with Sodium Azide: Regioselective Synthesis of 3,5-Bis(het)arylisoxazoles via Intramolecular N–O Bond Formation
  作者：Mary Antony P、Gantala L. Balaji、Pethaperumal Iniyavan、Hiriyakkanavar Ila

  DOI：10.1021/acs.joc.0c02216

  日期：2020.12.4

  An efficient new synthesis of 3,5-bis(het)arylisoxazoles, involving the reaction of 1,3-bis(het)arylmonothio-1,3-diketones with sodium azide in the presence of IBX catalyst, has been reported. The reaction proceeds at room temperature in high yields and is applicable to a broad range of substrates including the synthesis of 5-methyl-3-arylisoxazoles, a key subunit present in several β-lactamase-resistant

  据报道，在IBX催化剂存在下，一种有效的新的3,5-双（杂）芳基异恶唑合成涉及1,3-双（杂）芳基单硫-1,3-二酮与叠氮化钠的反应。该反应在室温下以高收率进行，适用于多种底物，包括5-甲基-3-芳基异恶唑的合成，5-甲基-3-芳基异恶唑是几种抗β-内酰胺酶的抗生素中存在的关键亚基。已经提出了形成异恶唑的可能机理。还通过使相应的1-（杂）芳基-1-（甲硫基）-4-（杂）亚芳基-丁-1-烯-反应而合成了一些5-苯乙烯基/芳基丁二烯基-3-（杂）芳基异恶唑。在较高温度下与叠氮化钠共3个。β-酮二硫酯与叠氮化钠的反应显示出可提供高产率的β-酮腈。
• Sequential One-Pot Synthesis of Tri- and Tetrasubstituted Thiophenes and Fluorescent Push–Pull Thiophene Acrylates Involving (Het)aryl Dithioesters as Thiocarbonyl Precursors
  作者：Anand Acharya、G. Parameshwarappa、B. Saraiah、H. Ila

  DOI：10.1021/jo502429c

  日期：2015.1.2

  An efficient, one-pot three component synthesis of highly functionalized tri- and tetrasubstituted thiophenes has been reported involving (het)aryl dithioesters as thiocarbonyl precursors. Thus, sequential base mediated condensation of readily available (het)aryl active methylene ketones with (het)aryl dithioesters followed by S-alkylation of the resulting enethiolate salts with activated halomethylene

  已经报道了一种高效，一锅三组分的高度官能化的三和四取代噻吩的合成方法，其中涉及（杂）芳基二硫代酯作为硫代羰基前体。因此，容易获得的（杂）芳基活性亚甲基酮与（杂）芳基二硫代酯的顺序碱介导的缩合，然后用活化的卤代亚甲基化合物对所得的烯硫醇盐进行S-烷基化，同时S-烷基化的化合物的分子内醇醛缩合型提供了取代基。噻吩的收率极高。通过使用溴巴豆酸酯作为活化的亚甲基烷基化剂，该方法也已扩展到合成高荧光推挽式取代的噻吩-5-丙烯酸酯。
• Synthesis of 2-Phenyl-4,5-Substituted Oxazoles by Copper-Catalyzed Intramolecular Cyclization of Functionalized Enamides
  作者：S. Vijay Kumar、B. Saraiah、N. C. Misra、H. Ila

  DOI：10.1021/jo3021192

  日期：2012.12.7

  An efficient two-step synthesis of 2-phenyl-4,5-substituted oxazoles involving intramolecular copper-catalyzed cyclization of highly functionalized novel β-(methylthio)enamides as the key step has been reported. These enamides are obtained by nucleophilic ring-opening of newly synthesized 4-[(methylthio)hetero(aryl)methylene]-2-phenyl-5-oxazolone precursors by alkoxides, amines, amino acid esters and

  已经报道了2-苯基-4，5-取代的恶唑的有效两步合成，其中涉及高度功能化的新型β-（甲硫基）烯酰胺的分子内铜催化的环化作为关键步骤。这些酰胺是通过新合成的4-[（（甲硫基）杂（芳基）亚甲基] -2-苯基-5-恶唑烷酮前体的亲核开环反应，通过醇盐，胺，氨基酸酯和芳基/烷基格氏试剂进行亲核开环而获得的。在产物恶唑的4-位引入酯，N-取代的羧酰胺或酰基官能团。还描述了通过相应的2,5-二芳基恶唑-4-羧酸酯的两步水解-脱羧反应合成两种天然存在的2,5-二芳基恶唑，即texamine和uguenenazole。相似地，通过DAST / DBU介导的环脱水-脱卤化氢序列，将三种丝氨酸衍生的oxazole-4-carboxamides精制为新型三取代的4,2'-bisoxazoles。本协议是对我们先前报道的碳酸银诱导的β-双（甲硫基）烯酰胺成2-苯基-5-（甲硫基）-4-取代的恶唑环化的补充和改进。