N,N-dimethylthioacrylamide | 61796-17-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代酰胺
• 英文名称: N,N-dimethylthioacrylamide
• 英文别名: N,N-dimethyl-α-methacrylothioamide；α-Methyl-thioacrylsaeure-dimethylamid；N,N,2-trimethylprop-2-enethioamide；N,N-dimethylthiomethacrylamide；2-Propenethioamide, N,N,2-trimethyl-
• CAS: 61796-17-6
• 化学式: C₆H₁₁NS
• 分子量: 129.226
• InChiKey: DEZABSITHPYRDN-UHFFFAOYSA-N

物化性质

• 沸点：
  130 °C(Press: 10 Torr)
• 密度：
  0.959±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  35.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,N-dimethylthioacrylamide 生成 dichloropalladium;N,N,2-trimethylprop-2-enethioamide
  参考文献：
  名称：

  TAMARU YOSHINAO; KAGOTANI MASAHIRO; YOSHIDA ZEN-ICHI, J. ORG. CHEM., 1979, 44, NO 15, 2816-2818

  摘要：

  DOI：
• 作为产物：
  描述：

  2-Hydroxy-2,N,N-trimethylthiopropionamid 在 2,6-二甲基吡啶 、 溶剂黄146 作用下， 以 乙醚 为溶剂， 反应 0.08h， 生成 N,N-dimethylthioacrylamide
  参考文献：
  名称：

  Solvolytic elimination reactions of tertiary .alpha.-CSNMe2-substituted systems

  摘要：

  The tertiary benzylic alpha-CSNMe2-substituted p-nitrobenzoates and trifluoroacetates of general structure Ar(CH3)C(CSNMe2)(OCOR), 7 and 8, solvolyze to give exclusively elimination products H2C = C(CSNMe2)Ar. A Hammett study gave a nonlinear correlation. Variation in rate with solvent ionizing power was small for the unsubstituted trifluoroacetate derivative of 8, and the beta-CD3 isotope effect on rate was negligible. There is, however, a large isotope effect (2.5-2.8) in formation of the elimination product when Ph(CH2D)C(CSNMe2)(OCOCF3) solvolyzes. It is concluded that an intermediate must be involved since the product-determining step and the rate-determining step have differing isotope effects. The likely intermediate is an alpha-CSNMe2-substituted cation (as an ion pair), despite the fact that the reaction has few characteristics of a typical E1 reaction. Tertiary norbornyl, cyclohexyl, and 2-propyl alpha-CSNMe2-substituted systems also react to give exclusively elimination products at rates far in excess of alpha-CONMe2 analogues. It is suggested that alpha-CSNMe2 cations are also intermediates and that these cations undergo proton loss at an early ion pair stage. These cations are proposed to derive substantial stabilization by charge delocalization onto sulfur of the thiocarbonyl group. By way of contrast, the secondary system CH3CH(CSNMe2)(OCOCF3), 25, solvolyzes to give mainly a rearranged product CH3CH(CONMe2)(SCOCH3) via a k(DELTA) mechanism involving neighboring thiocarbonyl participation leading to a cyclized ion.

  DOI：

  10.1021/jo00032a051

文献信息

• Herstellung und Reaktionen der valenzpolaromeren Verbindung (4,4-Dimethyl-2-thiazolin-5-dimethyliminium)-2-thiolat ⇌ (1-Dimethylthiocarbamoyl-1-methyl-äthyl)-isothiocyanat aus 3-Dimethyl-amino-2,2-dimethyl-2<i>H</i>-azirin und Schwefelkohlenstoff
  作者：Stanislav Chaloupka、Heinz Heimgartner、Hans Schmid、Helmut Link、Peter Schönholzer、Karl Bernauer

  DOI：10.1002/hlca.19760590733

  日期：1976.11.3

  Synthesis and reactions of the valence polaromeric compound (4,4-dimethyl-2-thiazoline-5-dimethyliminium)-2-thiolate ⇌ 1-dimethylthiocarbamoyl-1-methyl-ethyl isothiocyanate from 3-dimethylamino-2,2-dimethyl-2H-azirine and carbon disulfide.

  由3-二甲基氨基-2,2-二甲基-2合成四价价电子化合物（4,4-二甲基-2-噻唑啉-5-二甲基亚氨基）-2-硫醇盐⇌1-二甲基硫代氨基甲酰基-1-甲基-乙基异硫氰酸酯H-叠氮基和二硫化碳。
• Cooperative Activation of Alkyne and Thioamide Functionalities; Direct Catalytic Asymmetric Conjugate Addition of Terminal Alkynes to α,β-Unsaturated Thioamides
  作者：Ryo Yazaki、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1002/asia.201100050

  日期：2011.7.4

  revealed that the intermediate copper‐thioamide enolate functioned as a Brønsted base to generate copper alkynylide from the terminal alkyne, thus driving the catalytic cycle through an efficient proton transfer between substrates. These findings led to the identification of a more convenient catalyst using potassium hexamethyldisilazane (KHMDS) as the Brønsted base, which was particularly effective for

  详细描述了将末端炔烃直接催化不对称共轭加成至α，β-不饱和硫代酰胺的详细研究。一种柔软的路易斯酸/硬布朗斯台德碱协同催化剂，包含[Cu（CH 3 CN）4 ] PF 6，双膦配体和Li（OC 6 H 4 - p‐OMe）同时激活两种底物以补偿炔烃铜的低反应性。一系列控制实验表明，中间体铜硫代酰胺醇烯酸酯起布朗斯台德碱的作用，从末端炔烃生成炔烃铜，从而通过底物之间的有效质子转移驱动催化循环。这些发现导致鉴定了使用六甲基二硅氮烷钾（KHMDS）作为布朗斯台德碱的更方便的催化剂，该催化剂对于甲硅烷基乙炔的反应特别有效。硫酰胺官能团的不同转化以及GPR40受体激动剂AMG-837的简洁对映选择性合成突出了本催化方法的合成用途。
• Regiocontrolled 1,2-, 1,4-, and 1,6-additions of organometallics to unsaturated thioamides
  作者：Y. Tamaru、T. Harada、S. Nishi、Z. Yoshida

  DOI：10.1016/s0040-4039(00)87348-7

  日期：——

  1,4-Addition of allyllithiums to α,β-unsaturated thioamides and 1,4-(kinetic) and 1,6-(thermodynamic)regiocontrolled additions of lithium enolates to thiosorbamide are reported.

  据报道有1,4-烯丙基锂加到α，β-不饱和硫代酰胺上，以及1,4-（动力学）和1,6-（热力学）区域控制的烯醇锂加到硫代山梨糖酰胺上。
• Copper(I)‐Catalyzed Conjugate Addition/Enantioselective Protonation with Selenols and α‐Substituted α,β‐Unsaturated Thioamides
  作者：Hu Tian、Hong‐Ming Zhang、Liang Yin

  DOI：10.1002/anie.202301422

  日期：2023.6.12

  A copper(I)-catalyzed conjugate addition/enantioselective protonation with selenols and α-substituted α,β-unsaturated thioamides is disclosed, which affords a series of chiral selenides in high to excellent enantioselectivity.

  公开了铜 (I) 催化的与硒醇和 α-取代的 α,β-不饱和硫代酰胺的共轭加成/对映选择性质子化，它提供了一系列具有高对映选择性的手性硒化物。
• 1,4-Addition reactions of lithium enolates to .alpha.,.beta.-unsaturated thioamides
  作者：Yoshinao Tamaru、Toshiro Harada、Zenichi Yoshida

  DOI：10.1021/ja00499a062

  日期：1979.2