ethyl 2-bismethylthiomethylidene butanoate | 124658-66-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 2-bismethylthiomethylidene butanoate
• 英文别名: ethyl 3,3-bis(methylthio)-2-ethylacrylate；ethyl 3,3-(dimethylthio)-2-ethylacrylate；Ethyl 2-[bis(methylsulfanyl)methylidene]butanoate
• CAS: 124658-66-8
• 化学式: C₉H₁₆O₂S₂
• 分子量: 220.357
• InChiKey: KTFPKDXCLPXCJS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  76.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 2-bismethylthiomethylidene butanoate 在 六甲基磷酰三胺 、 samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 以90%的产率得到ethyl (2E)-2-(methylsulfanylmethylidene)butanoate
  参考文献：
  名称：

  Samarium diiodide-promoted reductive cleavage of carbon-sulfur bonds: a novel stereoselective generation of functionalized vinylsamarium species and synthesis of .beta.-thiobutenolides

  摘要：

  （烷氧基羰基）酮二硫代乙酸酯在SmI2的作用下被干净地还原，提供了一種新的、高效的立體選擇性方法，生成相應的高官能化烯基釸化合物。這些烯基釸化合物分別與質子、烯丙基溴和醛反應，生成相應的還原产物、烯丙基化产物和β-硫丁内酯。

  DOI：

  10.1021/jo00076a004
• 作为产物：
  描述：

  methyl-2-carboethoxy dithiobutanoate 、 碘甲烷 在 potassium carbonate 作用下， 以 丁酮 为溶剂， 以98%的产率得到ethyl 2-bismethylthiomethylidene butanoate
  参考文献：
  名称：

  硫代羰基化合物的Reformatsky反应：新的CC键形成反应

  摘要：

  Reformatsky regants被证明可以通过消除硫或烷硫基形成的亲碳性额外生成物，在三硫代碳酸酯，黄原酸酯，硫酮和二硫代酯上轻松形成CC键。

  DOI：

  10.1016/0040-4039(93)85065-5

文献信息

• Synthesis and anti-HIV-1 activity of 1,5-dialkyl-6-(arylselenenyl)uracils and -2-thiouracils
  作者：Dae-Kee Kim、Hun-Taek Kim、Jinsoo Lim、Jongsik Gam、Young-Woo Kim、Key H. Kim、Young Oh Shin

  DOI：10.1002/jhet.5570330356

  日期：1996.5

  6e-h in acetic acid either containing a catalytic amount of methanesulfonic acid at 80°or containing 1 equivalent of methanesulfonic acid at room temperature afforded 1,5-dialkyl-6-(methylthio)uracils 7a-d in 84–96% yields and 1,5-dialkyl-5,6-dihydro-6,6-di(methylthio)-2-thiouracils 11a-d in 88–99% yields, respectively. Oxidation of 7a-d and 11a-d with either 3-chloroperoxybenzoic acid in benzene or aqueous

  已经合成了1，5-二烷基-6-（芳基硒烯基）尿嘧啶10a-h和-2-硫尿嘧啶10i-p作为潜在的抗HIV-1试剂。的环化Ñ -烷基- N” - [3,3-二（甲硫基）-2- alkylacryloyl]脲图6a-d和-thioureas 6E-H在乙酸或者含有甲磺酸催化量在80℃或含有1室温下当量的甲磺酸得到84,96％产率的1,5-二烷基-6-（甲硫基）尿嘧啶7a-d和1,5-二烷基-5,6-二氢-6,6-二甲硫基-2-硫尿嘧啶11a-d的产率分别为88-99％。7a-d和11a-d的氧化用苯中的3-氯过氧苯甲酸或高碘酸钠水溶液的甲醇溶液制得1,5-二烷基-6-（甲基磺酰基）尿嘧啶8a-d，产率为88-98 ％，而1,5-二烷基-6-（甲基磺酰基）- 2-硫尿嘧啶12a-d的收率分别为57-73％，随后将其用芳基硒醇9a-b在氢氧化钠乙醇溶液中处理，以6099％的收率得到10a-p。这些化合物中，6-[[（3
• Pyrimidine acyclonucleoside derivatives
  申请人：Sunkyong Industries Co., Inc.

  公开号：US05889013A1

  公开（公告）日：1999-03-30

  The present invention relates to novel pyrimidine acyclonucleoside derivatives represented by the following general formula (I), antiviral agents containing the derivatives as the active ingredients and processes of preparation thereof. ##STR1## wherein R.sup.1 is ethyl or isopropyl; R.sup.2 is (3,5 dimethylphenyl)selenenyl; R.sup.3 is phenyl or methyl; X is oxygen; and Y is oxygen.

  本发明涉及以下一般式（I）所代表的新型嘧啶缺环核苷衍生物，包含该衍生物作为活性成分的抗病毒剂以及其制备方法。其中，R.sup.1为乙基或异丙基；R.sup.2为（3,5-二甲基苯基）硒基；R.sup.3为苯基或甲基；X为氧；Y为氧。
• A Novel and Efficient Generation of Functionalized Vinylcopper Reagents and their Reactions with Electrophiles. Synthesis of β-Methylthiobutenolides
  作者：Makoto Hojo、Hajime Harada、Akira Hosomi

  DOI：10.1246/cl.1994.437

  日期：1994.3

  amounts of dimethylcuprate derived from methyllithium and cuprous cyanide to yield the corresponding functionalized vinylcopper species. These organocopper species are efficiently trapped by carbon electrophiles. Formal substitution reactions of a methylthio group in ketene dithioacetals by electrophiles can be attained by one-pot operation. Synthesis of β-thiobutenolides was also achieved.

  在 2 位带有烷氧羰基的乙烯酮二硫缩醛被两个等摩尔量的甲基锂和氰化亚铜衍生的二甲基铜有效还原，得到相应的官能化乙烯基铜物质。这些有机铜物种被碳亲电子试剂有效地捕获。亲电试剂对乙烯酮二硫缩醛中甲硫基的正式取代反应可以通过一锅法进行。还实现了β-硫代丁烯内酯的合成。
• A convenient approach to the synthesis of 6-substituted 1,5-dialkyluracils and -2-thiouracils
  作者：Dae-Kee Kim、Young-Woo Kim、Jongsik Gam、Jinsoo Lim、Key H Kim

  DOI：10.1016/0040-4039(95)01238-d

  日期：1995.8

  A general and convenient approach to the synthesis of 6-substituted 1,5-dialkyluracils and 2-thiouracils via 1,5-dialkyl-6-(methylsulfonyl) uracils 1 and 1,5-dialkyl-6-(methylsulfinyl)-2-thiouracils 2, respectively, has been described. The compounds 1 and 2 were synthesized from ethyl 2-alkyl-3,3-di(methylthio)acrylates 3 in live steps in good yields.
• Synthesis and Anti-HIV-1 Activity of a Series of 1-Alkoxy-5-alkyl-6-(arylthio)uracils
  作者：Dae-Kee Kim、Jongsik Gam、Young-Woo Kim、Jinsoo Lim、Hun-Taek Kim、Key H. Kim

  DOI：10.1021/jm9607921

  日期：1997.7.1

  A series of 1-alkoxy-5-alkyl-6-(arylthio)uracils was synthesized and tested for their ability to inhibit HIV-1 replication. Treatment of 2-alkyl-3,3-bis(methylthio)acryloyl chlorides (5a-e) with AgOCN in benzene followed by reaction of the resulting isocyanates 6a-e with an appropriate alkoxyamine gave N-alkoxy-N'-((2-alkyl-3,3-bis(methylthio (10a-z) in good to excellent yields. Cyclization of 10a-z in AcOH containing st catalytic amount of p-TsOH produced 1-alkaxy-5-alkyl-6-(methylthio)uracils (11a-z). Oxidation of 11a-z with 3-chloroperoxybenzoic acid in CH2Cl2 resulted in high yields of 1-alkoxy-5-alkyl-6-(methylsulfonyl)uracils (12a-x and 12z) and 1-(benzyloxy)-6-(methylsulfinyl)thymine (12y), which were subsequently reacted with an appropriate arenethiol in ethanolic NaOH solution to afford 1-alkoxy-5-alkyl-6-(arylthio)uracils (14-49). Substitution at the 3- and 5-positions of the C-6-(phenylthio) ring by two methyl groups significantly increased its original anti-HIV-l activity (EC50: 6-((3,5-dimethylphenyl)thio)-5-isopropyl-1-propoxyuracil (18), 0.064 mu M; 6-((3,5-dimethylphenyl)thio)-1-(3-hydroxypropoxy)-5-isopropyluracil (23), 0.19 mu M). Among the various alkoxy substituents at the N-1, the propoxy group was the most beneficial for improving the anti-HIV-1 activity. The 1-propoxy derivative 18 proved to be the most potent inhibitor of HIV-1 replication, followed by the 1-(3-hydroxypropoxy) derivative 23. Introduction of an isopropyl group at C-5 of the uracil base also remarkably enhanced the activity. When compound 18 was incubated with a rat liver homogenate preparation, no metabolite was observed, thus confirming the metabolic stability of the N-O bond in these 1-alkoxyuracils.