ethyl diexo 3-isothiocyanobicyclo[2.2.1]hept-5-ene-2-carboxylate

• 分子结构分类: 有机化合物 - 有机硫化合物 - 异硫氰酸盐
• 英文名称: ethyl diexo 3-isothiocyanobicyclo[2.2.1]hept-5-ene-2-carboxylate
• 英文别名: ethyl (1R,2R,3S,4S)-3-isothiocyanatobicyclo[2.2.1]hept-5-ene-2-carboxylate
• 化学式: C₁₁H₁₃NO₂S
• 分子量: 223.296
• InChiKey: GEQOGKVWHKACSV-JLIMGVALSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  70.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl diexo 3-isothiocyanobicyclo[2.2.1]hept-5-ene-2-carboxylate 在 氨 作用下， 以 甲醇 为溶剂， 以87%的产率得到diexo 5,8-methano-2-thioxo-1,4,4a,5,8,8a-hexahydroquinazolin-4-one
  参考文献：
  名称：

  Synthesis and Structure of Norbornane/ene-fused Thiouracils and Thiazino[3,2-a]pyrimidinones

  摘要：

  Ethyl diexo-3-aminobicyclo [2.2.1]heptane- and -hept-5-ene-2-carboxylates (la,b) and the diendo derivatives were transformed with thiophosgene to the isothiocyanates (2a,b and 3a,b) and then cyclized to the norbornane/enecondensed 2-thioxopyrimidin-4-ones (4a,b and 5a,b). On heating, the norbornene compounds (4b and 5b) furnished thiouracil (6) via cyclopentadiene elimination. With dimethyl acetylenedicarboxylate, the thioxopyrimidinones (4a,b) and (5a,b) form angularly-fused [1,3]thiazino[3,2-a]pyrimidinones (7a,b and 8a,b). On heating, 7b decomposes to give 3-methyl-2,3-dihydro-2-thioxo-4(1H)-pyrimidinone (9) in a retro Diels-Alder process by methyl migration and splitting-off of cyclopentadiene. The structures were elucidated by IR and NMR spectroscopies, with DNOE, DEFT and 2D-HSC techniques.

  DOI：

  10.3987/com-99-8560
• 作为产物：
  描述：

  硫光气 、 ethyl exo-3-aminobicyclo<2.2.1>hept-5-ene-2-exo-carboxylate hydrochloride 在 碳酸氢钠 作用下， 以 水 、 丙酮 为溶剂， 反应 3.0h， 生成 ethyl diexo 3-isothiocyanobicyclo[2.2.1]hept-5-ene-2-carboxylate
  参考文献：
  名称：

  Bernath, G., Bulletin des Societes Chimiques Belges, 1994, vol. 103, # 9-10, p. 509 - 530

  摘要：

  DOI：

文献信息

• Synthesis of Alicyclic 2-Methylenethiazolo[2,3-b]quinazolinone Derivatives via Base-Promoted Cascade Reactions
  作者：Márta Palkó、Mohamed El Haimer、Tünde Faragó、Zsuzsanna Schelz、István Zupkó

  DOI：10.1055/s-0040-1720028

  日期：2022.9

  The synthesis of alicyclic 2-methylenethiazolo[2,3-b]quinazo­l­inones is performed via base-promoted cascade reactions, starting from either alicyclic β-amino propargylamides using carbon disulfide, or from alicyclic ethyl 2-isothiocyanatocarboxylates by addition of propargylamine. In both cases the cascade reaction proceeds by way of a favoured 5-exo-dig process during the second ring closure, as

  脂环族 2-亚甲基噻唑并 [2,3-b] 喹唑啉酮的合成是通过碱促进的级联反应进行的，从使用二硫化碳的脂环族 β-氨基炔丙酰胺开始，或从添加炔丙胺的脂环族 2-异硫氰酸基羧酸乙酯开始。在这两种情况下，级联反应在第二次闭环期间通过有利的 5-exo-dig 过程进行，如完整的 NMR 光谱分配所证实的那样。此外，对降冰片烯衍生物进行了高产率的逆狄尔斯-阿尔德 (RDA) 反应，生成 2-亚甲基-2H-噻唑并[3,2-a]嘧啶-5(3H)-酮。获得的化合物对一组人类妇科癌细胞系具有适度的抗增殖活性。
• Bernath, G., Bulletin des Societes Chimiques Belges, 1994, vol. 103, # 9-10, p. 509 - 530
  作者：Bernath, G.

  DOI：——

  日期：——
• Synthesis and Structure of Norbornane/ene-fused Thiouracils and Thiazino[3,2-a]pyrimidinones
  作者：Géza Stájer、Angela E. Szabó、Pál Sohár

  DOI：10.3987/com-99-8560

  日期：——

  Ethyl diexo-3-aminobicyclo [2.2.1]heptane- and -hept-5-ene-2-carboxylates (la,b) and the diendo derivatives were transformed with thiophosgene to the isothiocyanates (2a,b and 3a,b) and then cyclized to the norbornane/enecondensed 2-thioxopyrimidin-4-ones (4a,b and 5a,b). On heating, the norbornene compounds (4b and 5b) furnished thiouracil (6) via cyclopentadiene elimination. With dimethyl acetylenedicarboxylate, the thioxopyrimidinones (4a,b) and (5a,b) form angularly-fused [1,3]thiazino[3,2-a]pyrimidinones (7a,b and 8a,b). On heating, 7b decomposes to give 3-methyl-2,3-dihydro-2-thioxo-4(1H)-pyrimidinone (9) in a retro Diels-Alder process by methyl migration and splitting-off of cyclopentadiene. The structures were elucidated by IR and NMR spectroscopies, with DNOE, DEFT and 2D-HSC techniques.