Difuran-2-ylmethanthion | 389130-79-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: Difuran-2-ylmethanthion
• 英文别名: bis(2-furyl)methanethione；di(furan-2-yl)methanethione；bis(furan-2-yl)methanethione
• CAS: 389130-79-4
• 化学式: C₉H₆O₂S
• 分子量: 178.211
• InChiKey: BXIKDGKQEQRLMD-UHFFFAOYSA-N

物化性质

• 沸点：
  261.0±38.0 °C(Predicted)
• 密度：
  1.263±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  58.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Difuran-2-ylmethanthion 在 三苯基膦 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 2-[Bis(5-formylfuran-2-yl)methylen]-1,3-dithiol-4,5-dicarbonitril
  参考文献：
  名称：

  Annulenoide Tetrathiafulvalene:, 5,16-Bis(1,3-benzodithiol-2-yliden)-5,16-dihydrotetraepoxy- und 5,16-Bis(1,3-benzodithiol-2-yliden)-5,16-dihydrotetraepithio[22]annulene(2.1.2.1)

  摘要：

  The title compounds are among the first tetrathiafulvalenes with annulene spacers, here with tetraepoxy-[22]annulene(2.1.2.1) (see 3a), tetraepithio[22]annulene(2.1.2.1) (see 3b), and diepithiodiepoxy[22]annulene(2.1.2.1) (see 23) units. The annulenoid tetrathiafulvalenes 3a and 3b are prepared by cyclizing McMurry coupling of the 5,5'-(1,3-benzodithiol-2-ylidenemethylene)bis[furan- or thiophene-2-carbaldehydes] (8a or 8b, resp.) or by Wittig reaction of (1,3-benzodithiol-2-yl)tributylphosphonium tetra fluoroborate (13b) with tetraepoxy[22]annulene(2.1.2.1)-1,12-dione 20 (formation of 3a) or diepithiodiepoxy[22]annulene(2.1.2.1)1,12-dione 22 (formation of 23). The annulenoide tetrathiafulvalene 3a is obtained as a mixture of the isomers (E,E)- and (Z,Z)-3a. At 130 degrees, (Z,Z)-3a rearranges quantitatively into the (E,E)-isomer. Isomer (E,E)-3a is a dynamic molecule, where the (E)-ethene-1,2-diyl bridges rotate around the adjacent sigma -bonds, The tetraepithioannulene derivative 3b as well as 23 only exist in the (Z,Z) -configuration. The oxidation of (E,E/Z,Z)-3a with Br-2 yields the annulene -bridged tetrathiafulvalene dication (E,E)-3a(Ox), while with 4,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile (DDQ) obviously only the radical cation 3a(Sem) is formed, which belongs to the class of cyanine-like violenes. The annulenoide tetrathiafulvalenes 3b and 23, which exist only in the (Z,Z) -configuration, obviously for steric reasons, cannot be oxidized by DDQ. Electrochemical studies are in agreement with these results.

  DOI：

  10.1002/1522-2675(20010815)84:8<2220::aid-hlca2220>3.0.co;2-1
• 作为产物：
  描述：

  di-furan-2-yl-methanone 在 劳森试剂 作用下， 以 甲苯 为溶剂， 反应 0.03h， 生成 Difuran-2-ylmethanthion
  参考文献：
  名称：

  Thia-Diels-杂芳基硫酮与未活化的1,3-二烯导致3,6-dihydro-2 H -pyrans的Alder反应：一种双自由基机理的证据

  摘要：

  具有噻吩-2-基和硒代苯-2-基环的二杂芳基硫酮作为“超二亲”试剂与未活化的1,3-二烯，例如2,3-二甲基丁-1,3-二烯，环戊二烯和异构六-己基混合物2,4-二烯以中等至优异的产率产生预期的2 H-硫吡喃。在后一种情况下，相应的顺式-2,2-二杂芳基-3,6-二甲基-3,6-二氢-2 H-硫代吡喃形成了立体收敛的硫-狄尔斯-阿尔德反应的唯一产物。假定通过离域双基中间体的逐步机理来合理化所观察到的反应过程。m过量处理4,5-二甲基-2,2-二（噻吩-2-基）-3,6-二氢-2 H-噻喃室温下的-CPBA导致六元环中C = C键和硫原子的氧化。

  DOI：

  10.1007/s10593-017-2086-9

文献信息

• Hetaryl Thioketones: Synthesis and Selected Reactions
  作者：Grzegorz Mlostoń、Katarzyna Urbaniak、Krzysztof Gębicki、Paulina Grzelak、Heinz Heimgartner

  DOI：10.1002/hc.21191

  日期：2014.11

  lithiated heterocycles. Under typical conditions, selected examples of the hetaryl thioketones were oxidized selectively to give thiocarbonyl S-oxides (sulfines). Reactions with diazomethane at –65°C yielded 1,3-dithiolanes in a regioselective manner and hetero-Diels–Alder reactions of 2-thienyl substituted thioketones with dimethyl acetylenedicarboxylate yielded the corresponding 7H-thieno[2,3- c]thiopyran-4

  通过用劳森试剂处理相应酮的氧/硫交换，已经制备了一系列苯基/杂芳基和双杂四芳基硫酮。通过锂化呋喃、噻吩和硒吩分别与 N,N-二甲基苯甲酰胺和杂芳基甲酰胺反应，可以方便地获得非对称酮，而对称酮是通过用 2 当量的锂化杂环处理 N,N-二甲基氨基甲酸乙酯获得的。在典型条件下，选择的杂芳基硫酮实例被选择性氧化以得到硫代羰基 S-氧化物（亚砜）。在 –65°C 下与重氮甲烷反应以区域选择性方式产生 1,3-二硫杂环戊烷，2-噻吩基取代的硫酮与乙炔二甲酸二甲酯的杂-Diels-Alder 反应产生相应的 7H-噻吩并 [2,
• Hetero-Diels–Alder reactions of hetaryl and aryl thioketones with acetylenic dienophiles
  作者：Grzegorz Mlostoń、Paulina Grzelak、Maciej Mikina、Anthony Linden、Heinz Heimgartner

  DOI：10.3762/bjoc.11.63

  日期：——

  Selected hetaryl and aryl thioketones react with acetylenecarboxylates under thermal conditions in the presence of LiClO4 or, alternatively, under high-pressure conditions (5 kbar) at room temperature yielding thiopyran derivatives. The hetero-Diels-Alder reaction occurs in a chemo- and regioselective manner. The initially formed [4 + 2] cycloadducts rearrange via a 1,3-hydrogen shift sequence to give

  所选择的杂芳基和芳基硫代酮在热条件下，在LiClO4存在下或在室温下在高压条件下（5 kBAr）与乙炔羧酸酯反应，生成噻喃衍生物。杂Diels-Alder反应以化学和区域选择性方式发生。最初形成的[4 + 2]环加合物通过1，3-氢转移序列进行重排，得到最终产物。通过用mCPBA处理将后者平滑氧化为相应的砜。
• New Applications of Hetaryl Thioketones for the Synthesis of Hetaryl-Substituted Ethenes via ‘Two-Fold Extrusion Reaction’
  作者：Heinz Heimgartner、Grzegorz Mlostoń、Katarzyna Urbaniak、Aneta Pawlak

  DOI：10.3987/com-15-s(t)8

  日期：——

  A series of aryl/hetaryl thioketones was applied for the reactions with aryl/hetaryldiazomethanes yielding, after elimination of N-2, the corresponding thiiranes. The relatively unstable dihetaryldiazomethanes were generated in situ from the corresponding hydrazones by oxidation with DMSO. The obtained thiiranes were converted into tetraaryl/hetaryl-substituted ethenes in good yields by desulfurization performed with tris(diethylamino)phosphine ((Et2N)(3)P).