5-<(allylamino)(methylthio)methylene>-2,2-dimethyl-1,3-dioxane-4,6-dione | 131297-20-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-<(allylamino)(methylthio)methylene>-2,2-dimethyl-1,3-dioxane-4,6-dione
• 英文别名: 2,2-Dimethyl-5-[methylsulfanyl-(prop-2-enylamino)methylidene]-1,3-dioxane-4,6-dione
• CAS: 131297-20-6
• 化学式: C₁₁H₁₅NO₄S
• 分子量: 257.31
• InChiKey: SAJIYKPZKNXMRI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  89.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-<(allylamino)(methylthio)methylene>-2,2-dimethyl-1,3-dioxane-4,6-dione 500.0 ℃ 、133.32 Pa 条件下， 以60%的产率得到S-methyl 2-cyanopent-4-enethioate
  参考文献：
  名称：

  Synthesis of .alpha.-cyano carbonyl compounds by flash vacuum thermolysis of (alkylamino)methylene derivatives of Meldrum's acid. Evidence for facile 1,3-shifts of alkylamino and alkylthio groups in imidoylketene intermediates

  摘要：

  The syntheses and flash vacuum thermolyses of 5-[(alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones (Meldrum's acid derivatives) 13a-i are described. Thermolysis of 13a as well as of ethyl 3-(tert-butylamino)acrylate (22) gives a tautomeric mixture of cyanoacetaldehyde (14) and 3-hydroxypropenenitrile (15). Thermolysis of 13b gives iminoacrolein 26 and not cyanoacetone (29). Thermolysis of 13c,d gives S-methyl cyanothioacetate (30), and 13f-h give cyanoacetamides 31 in high yields. 2-Cyanopent-4-enoic acid derivatives 32 are obtained from Meldrum's acids 13e,i. The results are discussed in terms of facile 1,3-shifts of methylthio and alkylamino groups in imidoylketenes, interconverting imidoylketenes and acylketene imines.

  DOI：

  10.1021/jo00003a014
• 作为产物：
  描述：

  丙二酸环(亚)异丙酯 在 二硫化碳 、 三乙胺 作用下， 以 乙醇 为溶剂， 反应 39.0h， 生成 5-<(allylamino)(methylthio)methylene>-2,2-dimethyl-1,3-dioxane-4,6-dione
  参考文献：
  名称：

  Synthesis of .alpha.-cyano carbonyl compounds by flash vacuum thermolysis of (alkylamino)methylene derivatives of Meldrum's acid. Evidence for facile 1,3-shifts of alkylamino and alkylthio groups in imidoylketene intermediates

  摘要：

  The syntheses and flash vacuum thermolyses of 5-[(alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones (Meldrum's acid derivatives) 13a-i are described. Thermolysis of 13a as well as of ethyl 3-(tert-butylamino)acrylate (22) gives a tautomeric mixture of cyanoacetaldehyde (14) and 3-hydroxypropenenitrile (15). Thermolysis of 13b gives iminoacrolein 26 and not cyanoacetone (29). Thermolysis of 13c,d gives S-methyl cyanothioacetate (30), and 13f-h give cyanoacetamides 31 in high yields. 2-Cyanopent-4-enoic acid derivatives 32 are obtained from Meldrum's acids 13e,i. The results are discussed in terms of facile 1,3-shifts of methylthio and alkylamino groups in imidoylketenes, interconverting imidoylketenes and acylketene imines.

  DOI：

  10.1021/jo00003a014

文献信息

• Next-Generation TLC: A Quantitative Platform for Parallel Spotting and Imaging
  作者：Alexander A. Boulgakov、Sarah R. Moor、Hyun Hwa Jo、Pedro Metola、Leo A. Joyce、Edward M. Marcotte、Christopher J. Welch、Eric V. Anslyn

  DOI：10.1021/acs.joc.0c00349

  日期：2020.8.7

  developed using a thin-layer chromatography (TLC) imaging method. As a test-bed reaction, we monitored 48 thiol conjugate additions to a Meldrum’s acid derivative (1) in parallel using TLC. The TLC elutions were imaged using a cell phone and a LEGO brick-constructed UV/vis light box. Further, a spotting device was constructed from LEGO bricks that allows simple transfer of the samples from a well-plate

  使用薄层色谱 (TLC) 成像方法开发了一种高通量筛选方法，用于同时分析和量化多达 48 个反应的转化百分比。作为试验台反应，我们使用 TLC 平行监测了 48 个硫醇缀合物添加到 Meldrum 酸衍生物 ( 1 )。使用手机和乐高积木结构的紫外/可见光箱对 TLC 洗脱液进行成像。此外，一个点样装置由乐高积木构成，可以将样品从孔板简单地转移到 TLC 板。使用专为检测“斑点”并报告其强度而开发的软件，我们能够通过一次分析定量确定 48 次反应的完成程度。
• CHEIKH, ABDELHAMID;BEN;CHUCHE, JOSSELIN;MANISSE, NOEL;POMMELET, JEAN CLAU+, J. ORG. CHEM., 56,(1991) N, C. 970-975
  作者：CHEIKH, ABDELHAMID、BEN、CHUCHE, JOSSELIN、MANISSE, NOEL、POMMELET, JEAN CLAU+

  DOI：——

  日期：——
• Synthesis of .alpha.-cyano carbonyl compounds by flash vacuum thermolysis of (alkylamino)methylene derivatives of Meldrum's acid. Evidence for facile 1,3-shifts of alkylamino and alkylthio groups in imidoylketene intermediates
  作者：Abdelhamid Ben Cheikh、Josselin Chuche、Noel Manisse、Jean Claude Pommelet、Klaus Peter Netsch、Primoz Lorencak、Curt Wentrup

  DOI：10.1021/jo00003a014

  日期：1991.2

  The syntheses and flash vacuum thermolyses of 5-[(alkylamino)methylene]-2,2-dimethyl-1,3-dioxane-4,6-diones (Meldrum's acid derivatives) 13a-i are described. Thermolysis of 13a as well as of ethyl 3-(tert-butylamino)acrylate (22) gives a tautomeric mixture of cyanoacetaldehyde (14) and 3-hydroxypropenenitrile (15). Thermolysis of 13b gives iminoacrolein 26 and not cyanoacetone (29). Thermolysis of 13c,d gives S-methyl cyanothioacetate (30), and 13f-h give cyanoacetamides 31 in high yields. 2-Cyanopent-4-enoic acid derivatives 32 are obtained from Meldrum's acids 13e,i. The results are discussed in terms of facile 1,3-shifts of methylthio and alkylamino groups in imidoylketenes, interconverting imidoylketenes and acylketene imines.