potassium (2,2-dicyano-1-methylsulfanylethen-1-yl)thiolate | 20602-68-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: potassium (2,2-dicyano-1-methylsulfanylethen-1-yl)thiolate
• 英文别名: potassium-(2,2-dicyano-1-methyl-thioethen-1-yl)thiolate；potassium (2,2-dicyano-1-methylthioethen-1-yl)thiolate；potassium-(2,2-dicyan-1-methylthioethen-1-yl)-thiolate；3-mercapto-3-methylthio-2-cyano-acrylonitrile potassium salt；3-Mercapto-3-methylmercapto-2-cyan-acrylnitril-Kaliumsalz；Potassium;2,2-dicyano-1-methylsulfanylethenethiolate
• CAS: 20602-68-0
• 化学式: C₅H₃N₂S₂*K
• 分子量: 194.323
• InChiKey: KXVOXOVKNVZWEE-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.84
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  73.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  potassium (2,2-dicyano-1-methylsulfanylethen-1-yl)thiolate 在 一水合肼 作用下， 反应 0.03h， 以72%的产率得到3-amino-5-thioxo-pyrazol-4-carbonitrile
  参考文献：
  名称：

  Amino-thieno[2,3-c]pyrazole und Amino-thieno[2,3-b]pyrrole

  摘要：

  The synthesis of thieno[2,3-c]pyrazoles and thieno [2,3-b]pyrroles is described. From the dithioliumsalt (1) and potassium hydroxide the potassium-(2,2-dicyan-1-methylthio-ethen-1-yl)-thiolate (2) is formed. This reacts with hydrazine hydrate to form the 3-amino-5-thioxo-pyrazol-4-carbonitrile (3). S-Alkylation with alpha-chlorocarbonyl compounds yielding (6a-c) leads via Thorpe-Ziegler-cyclization to 3,4-diamino-thieno[2,3-c]pyrazoles (9) if the position 1 is alkylated (8). Acetyl acetone yields 2-mercapto-pyrazolo[1,5-a]pyrimidine (5). After S-alkylation (10a-d) are immediately cyclized to thieno [2',3':3,4]pyrazolo[1,5-a]pyrimidine (11a-d). The ketone (6a) can be cyclized to the pyrazolo [5,1-b]thiazole (12). 3 reacts with oxalyl chloride to form the 2,3-dioxo-6-thioxo-imidazo[1,2-b]pyrazole (13) of which S-phenacyl derivative (14) because the NH-proton cannot be cyclized. The 5-amino-3,4-dicyano-pyrrol-2-thiolate (16) shows the analogous behaviour. The S-alkylation is followed by cyclization, and 3,5-diamino-thieno[2,3-b]pyrroles (18a-b) arise. Reaction of 5-amino-2-alkylthio-pyrrol-3,5-dicarbonitrile (17) with acetyl acetone provides pyrrolo[1,2-a]pyrimidine (20a-c) which can be cyclized to form thieno[3',2':4,6]pyrimidines (21a-c) very easily.

  DOI：

  10.1002/prac.199533701101
• 作为产物：
  描述：

  3-Amino-4-cyan-5-methylthio-(1,2)-dithioliumiodid 在 氢氧化钾 作用下， 反应 0.17h， 以81%的产率得到potassium (2,2-dicyano-1-methylsulfanylethen-1-yl)thiolate
  参考文献：
  名称：

  Amino-thieno[2,3-c]pyrazole und Amino-thieno[2,3-b]pyrrole

  摘要：

  The synthesis of thieno[2,3-c]pyrazoles and thieno [2,3-b]pyrroles is described. From the dithioliumsalt (1) and potassium hydroxide the potassium-(2,2-dicyan-1-methylthio-ethen-1-yl)-thiolate (2) is formed. This reacts with hydrazine hydrate to form the 3-amino-5-thioxo-pyrazol-4-carbonitrile (3). S-Alkylation with alpha-chlorocarbonyl compounds yielding (6a-c) leads via Thorpe-Ziegler-cyclization to 3,4-diamino-thieno[2,3-c]pyrazoles (9) if the position 1 is alkylated (8). Acetyl acetone yields 2-mercapto-pyrazolo[1,5-a]pyrimidine (5). After S-alkylation (10a-d) are immediately cyclized to thieno [2',3':3,4]pyrazolo[1,5-a]pyrimidine (11a-d). The ketone (6a) can be cyclized to the pyrazolo [5,1-b]thiazole (12). 3 reacts with oxalyl chloride to form the 2,3-dioxo-6-thioxo-imidazo[1,2-b]pyrazole (13) of which S-phenacyl derivative (14) because the NH-proton cannot be cyclized. The 5-amino-3,4-dicyano-pyrrol-2-thiolate (16) shows the analogous behaviour. The S-alkylation is followed by cyclization, and 3,5-diamino-thieno[2,3-b]pyrroles (18a-b) arise. Reaction of 5-amino-2-alkylthio-pyrrol-3,5-dicarbonitrile (17) with acetyl acetone provides pyrrolo[1,2-a]pyrimidine (20a-c) which can be cyclized to form thieno[3',2':4,6]pyrimidines (21a-c) very easily.

  DOI：

  10.1002/prac.199533701101

文献信息

• NBS-mediated sequential one-pot synthesis of multifunctionalized thiazoles and thiophenes from 1,3-dicarbonyl compounds and mercaptonitrile salts
  作者：Laichun Luo、Lanlan Meng、Qi Sun、Zemei Ge、Runtao Li

  DOI：10.1016/j.tetlet.2013.11.014

  日期：2014.1

  A NBS-mediated sequential one-pot synthesis of multifunctionalized thiazoles and thiophenes from 1,3-dicarbonyl compounds and mercaptonitrile salts has been developed under mild conditions. This transformation involves sequential bromination/SN2 alkylation/Thorpe–Ziegler cyclization/regio-selective elimination of a –COR group, affording the desired products in moderate to good yields. The sequence

  由NBS介导的从1,3-二羰基化合物和硫醇腈盐开始的多官能噻唑和噻吩的顺序一锅法合成已经在温和的条件下进行。该转化涉及顺序溴化/ S N 2烷基化/索普-齐格勒环化/ -COR基团的区域选择性消除，以中等至良好的收率提供所需的产物。确定了-COR基团离去反应的顺序，并提出了可能的机制。
• Thioacylierung von Malonsäurederivaten mit Dithio- und Thionestern
  作者：K. Hartke、L. Peshkar

  DOI：10.1002/ardp.19683010810

  日期：——

  Malondinitril kondensieren mit Dithio‐ und Thionestern aliphatischer und aromatischer Carbonsäuren sowie mit Trithio‐ und Thionestern der Kohlensäure in Gegenwart von Alkalialkoholat zu den Alkalisalzen in 2‐Stellung substituierter 2‐Mercapto‐1‐cyan‐acrylnitrile 3, die durch Alkylierung entsprechend substituierte 2‐Alkylmercapto‐1‐cyan‐acryl‐nitrile 6 liefern. Die analoge Kondensation mit diversen Malonsäurederivaten

  等摩尔量的丙二腈与脂肪族和芳香族羧酸的二硫代和硫酮酯以及碳酸的三硫代和硫酮酯在碱金属醇化物存在下缩合形成碱金属盐 2-巯基-1-氰基-丙烯腈 3 被烷基化取代 -得到烷基巯基-1-氰基-丙烯腈6。与各种丙二酸衍生物而不是丙二腈的类似缩合产生碱金属盐8，其在酸化时分离游离巯基化合物9并与甲基碘形成甲基巯基化合物10。使用光谱数据讨论了 3、6、8、9 和 10 的结构。
• Novel synthesis of thiazolo/thienoazepine-5,8-diones from dihalo cyclic 1,3-diketones and mercaptonitrile salts
  作者：Laichun Luo、Lanlan Meng、Qi Sun、Zemei Ge、Runtao Li

  DOI：10.1039/c3ra46606j

  日期：——

  An efficient approach to thiazolo[4,5-b]azepine-5,8-diones and thieno[3,2-b]azepine-5,8-diones has been developed via a domino synthesis of multifunctionalized thiazoles/thiophenes and further intramolecular cyclization. This transformation proceeded rapidly under mild conditions without use of metal catalyst.

  通过多官能团噻唑/噻吩的多米诺合成以及进一步的分子内合成，已开发出一种有效的方法来处理噻唑并[4,5 - b ]氮杂5,8-二酮和噻吩并[3,2 - b ]氮杂5,8-二酮环化。在不使用金属催化剂的情况下，该转化在温和条件下迅速进行。
• Heterocondensed thiophenes and thiazoles by THORPE-ZIEGLER cyclization
  作者：Margit Gruner、Gesine Böttcher、Karl Gewald

  DOI：10.1002/jhet.5570450419

  日期：2008.7

  The syntheses of novel thieno-pyridones, thiazolo-pyridones, thiazolo-pyridines and amino- and diamino-dieno-pyridines were described. Simultaneously, it was demonstrated that in these compounds and in the related 3-aminothiophenes the replacement of the methylthio by the morpholino group is possible. The structures were characterized using 1H-, 13C-NMR, IR and elemental analysis.

  描述了新颖的噻吩并吡啶酮，噻唑并吡啶酮，噻唑并吡啶以及氨基和二氨基二酮基吡啶的合成。同时证明，在这些化合物和相关的3-氨基噻吩中，可以用吗啉代基团代替甲硫基。使用1 H-，13 C-NMR，IR和元素分析对结构进行表征。
• [EN] THIOPHENE DERIVATIVES AS MICROBICIDES AND HERBICIDES<br/>[FR] DERIVES DE THIOPHENE COMME MICROBICIDES ET HERBICIDES
  申请人：BAYER CROPSCIENCE AG

  公开号：WO2004067527A1

  公开（公告）日：2004-08-12

  Novel thiophene derivatives of the formula (I) wherein R1, R2, R3 and n have the meanings given in the specification, several processes for the preparation of the new compounds and their use as microbicides and herbicides.

  本发明涉及一种新的噻吩衍生物，其化学式为（I），其中R1，R2，R3和n的含义如规范中所述，还涉及制备这些新化合物的几种方法以及它们作为微生物杀菌剂和除草剂的用途。