1-Phenyl-1H-2-benzothiopyran-3,4-dicarbonsaeure-dimethylester | 75784-96-2

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1-Phenyl-1H-2-benzothiopyran-3,4-dicarbonsaeure-dimethylester
• 英文别名: dimethyl 1H-2-benzothiopyran-3,4-dicarboxylate；dimethyl 1-phenyl-1H-2-benzothiopyrane-3,4-dicarboxylate；dimethyl 1-phenyl-1H-2-benzothiopyran-4,5-dicarboxylate；1-phenyl-1H-isothiochromene-3,4-dicarboxylic acid dimethyl ester；dimethyl 1-phenyl-1H-isothiochromene-3,4-dicarboxylate
• CAS: 75784-96-2
• 化学式: C₁₉H₁₆O₄S
• 分子量: 340.4
• InChiKey: NYDXTXAIAYHVCC-UHFFFAOYSA-N

物化性质

• 熔点：
  91-92 °C(Solv: methanol (67-56-1))
• 沸点：
  513.3±50.0 °C(Predicted)
• 密度：
  1.287±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  77.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-Phenyl-1H-2-benzothiopyran-3,4-dicarbonsaeure-dimethylester 在 Pummerer 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 生成 Dimethyl 1-hydroxy-1-phenylisothiochromene-3,4-dicarboxylate
  参考文献：
  名称：

  Oxidation of 1H-2-Benzoselenopyrans. Generation of Benzoselenophenes, Benzaldehydes, and Benzophenones

  摘要：

  Oxidation of 1H-2-benzoselenopyrans bearing electron-withdrawing substituents gave benzoselenophenes, benzaldehydes, and benzophenone derivatives via the corresponding selenoxides followed by Pummerer and [3,3]sigmatropic rearrangements.

  DOI：

  10.3987/com-99-s118
• 作为产物：
  描述：

  二苯基甲烷硫酮 在 sodium thiophenolate 、 sulfur 、 丁炔二酸二甲酯 作用下， 以 丙酮 、 均三甲苯 为溶剂， 反应 140.0h， 生成 1-Phenyl-1H-2-benzothiopyran-3,4-dicarbonsaeure-dimethylester
  参考文献：
  名称：

  The Conversion of Thioketones to 1,2,4,5-Tetrathianes and Its Mechanism

  摘要：

  Thiobenzophenone and adamantanethione react with sulfur (1:1) under catalysis by sodium thiophenoxide in acetone at rt furnishing 1,2,4,5-tetrathianes (9 and 43) in high yields. An attack of the oligothiolate (R-S-x(-)) on the C-atom of drop C=S is proposed as initiating step. Thione S-sulfides (R2C=S+-S-, thiosulfines) cannot be intermediates, since they combine fast with thiones affording 1,2,4-trithiolanes. With more sulfur, adamantanethione produces the 1,2,3,5,6-pentathiepane-bis(spiroadamantane) (44) which interconverts with the tetrathiane, but not with the 1,2,4-trithiolane, in an equilibrium catalyzed by R-S-x(-). According to C-13 NMR evidence, the tetrathianebis(spiroadamantane) occurs in a twist conformation which inverts with Delta G not equal 16.0 kcal mol(-1).

  DOI：

  10.3987/com-96-7706

文献信息

• 1,3-Dipolar Activity in Cycloadditions of an Aliphatic Sulfine^,¹
  作者：Rolf Huisgen、Grzegorz Mloston、Kurt Polborn

  DOI：10.1021/jo9607424

  日期：1996.1.1

  4-Tetramethyl-3-thioxocyclobutanone S-oxide (4) combines with diaryl thioketones at room temperature furnishing spiro-1,2,4-oxadithiolanes 6 in equilibrium reactions. Compound 6a was oxidized to the cis-S,S-dioxide 9, the structure of which was established by X-ray analysis. These are the first unequivocal 1,3-cycloadditions of thione S-oxides (sulfines) which possess an allyl anion type MO; cycloadditions to

  2,2,4,4-四甲基-3-硫代氧杂环丁酮S-氧化物（4）在室温下与二芳基硫代酮结合，在平衡反应中提供螺1,1,2,4-恶二硫杂环戊烷6。化合物6a被氧化为顺式S，S-二氧化物9，其结构通过X射线分析确定。这些是具有烯丙基阴离子MO的硫酮S-氧化物（亚砜）的第一个明确的1，3-环加成；以前已经描述了将硫的C ＝ S键的环加成为亲二亲性和亲二亲性。
• 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。
• Generation of Thiosulfines by Dithiation of Diarylmethylenetriphenylphosphoranes
  作者：Kentaro Okuma、Masashi Shimasaki、Kazuki Kojima、Hiroshi Ohta、Renji Okazaki

  DOI：10.1246/cl.1993.1599

  日期：1993.9

  Reaction of phosphonium ylides with excess sulfur afforded the corresponding thiosulfines, which were trapped with maleic anhydride to give the corresponding cycloadducts (1,2-dithiolanes) in good yields. Intermediary thiosulfines were also formed by sulfurization of thiobenzophenones with elemental sulfur to give the 1,2-dithiolanes in moderate yields.

  磷阳离子与过量硫反应生成相应的硫代亚磺酸盐，这些硫代亚磺酸盐与马来酸酐反应生成相应的环加成物（1,2-二噁烷）且收率良好。通过与元素硫反应使硫苯基酮硫化，同样也形成了中间体硫代亚磺酸盐，从而以中等收率得到1,2-二噁烷。
• The first stable 1,2-thiastannete and 1,2-selenastannete: their syntheses and crystal structures
  作者：Norihiro Tokitoh、Yasusuke Matsuhashi、Renji Okazaki

  DOI：10.1039/c39930000407

  日期：——

  Thermal decomposition of overcrowded 1,2,4,3-trichalcogenastannolanes 1 resulted in the formation of the first stable 1,2-chalcogenastannete derivatives 3via[2 + 2]cycloaddition of intermediary stannanethione and stannanselone 2; the molecular structures of 3 were determined by X-ray crystallographic analysis.

  过度拥挤的 1,2,4,3-三钙原石杉烷 1 受热分解后，通过中间体石杉硫酮和石杉硒酮 2 的[2 + 2]环加成，形成了首个稳定的 1,2-三钙原石杉烷衍生物 3；通过 X 射线晶体分析法确定了 3 的分子结构。
• Reaction of Selenobenzophenones with Olefins. Formation of 1<i>H</i>-2-Benzoselenopyrans. Reaction of 1<i>H</i>-2-Benzoselenopyrans with Diazoalkanes
  作者：Kentaro Okuma、Yuji Koga、Kazuki Kojima、Kosei Shioji、Haruo Matsuyama、Yoshinobu Yokomori

  DOI：10.1021/jo991679w

  日期：2000.4.1

  Selenobenzophenone reacts as a diene with dimethyl acetylenedicarboxylate (DMAD) to lead to dimethyl 1H-1-diphenylmethyl-1-phenyl-2-benzoselenopyran-3,4-dicarboxylate (5c) in moderate yield; the initial [4 + 2] cycloaddition is followed by the addition of another 1 mol equiv of selenobenzophenone. The reaction might proceed through carbene insertion of the primary cycloadduct. On the other hand, 4

  硒代二苯甲酮作为二烯与乙酰二羧酸二甲酯（DMAD）反应，以中等收率生成1H-1-二苯基甲基-1-苯基-2-苯并硒基吡喃-3,4-二羧酸二甲酯（5c）; 最初的[4 + 2]环加成反应之后，再加入另外1摩尔当量的硒代二苯甲酮。该反应可以通过伯环加合物的卡宾插入而进行。另一方面，4,4'-二甲氧基硒代二苯甲酮与二烯结合，与DMAD一起提供1H-1-对甲氧基苯基-6-甲氧基-2-苯并硒喃-3,4-二羧酸二甲酯（4a）。苯并硒基吡喃衍生物（4）与二芳基重氮甲烷的反应提供了另一种类型的卡宾插入产物。

表征谱图