4--amino>-5-(methylthio)-7H-7,7-dimethylbenzothiopyran-2,3-dicarboxylate | 115094-79-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4--amino>-5-(methylthio)-7H-7,7-dimethylbenzothiopyran-2,3-dicarboxylate
• 英文别名: Dimethyl 4-[benzyl-[2-(benzylamino)ethyl]amino]-7,7-dimethyl-5-methylsulfanylthiochromene-2,3-dicarboxylate
• CAS: 115094-79-6
• 化学式: C₃₂H₃₆N₂O₄S₂
• 分子量: 576.781
• InChiKey: LCHFPAQQHUJJAD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  40
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  119
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4--amino>-5-(methylthio)-7H-7,7-dimethylbenzothiopyran-2,3-dicarboxylate 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 0.33h， 以0.0053 g的产率得到Dimethyl 5-(methylthio)-7,7-dimethyl-4-oxo-7,8-dihydro-benzothiopyran-2,3-dicarboxylate
  参考文献：
  名称：

  Addition of twisted 1-thioacyl-2,2-diaminoethylenes to dimethyl acetylenedicarboxylate. Formation and ring opening of thiopyran-4-spiro-2'-(1',3'-diazacyclanes)

  摘要：

  Reaction of 1,3-dialkyl-2-(4,4-dimethyl-2,6-dithioxocyclohexylidene)imidazolidines and -hexahydropyrimidines (twisted push-pull ethylenes, 3) with methyl iodide followed by treatment with base leads smoothly to S-methyl derivatives, which are betaines with a 1,4-dipole and an electron-rich 1,3-butadiene system (5). These compounds react with DMAD to give dihydrobenzothiopyranspiroimidazolidine and -hexahydropyrimidine derivatives 7 in high yields. The spiro compounds rearrange in acid medium or on chromatography on silica gel to compounds, which we previously incorrectly described as ''folded ethylenes'' A but which are now shown to be 4-(2-aminoethyl)amino-ethyl)amino- or 4-(3-aminopropyl)aminothiopyran derivatives 11. The 4-amino groups of 11 are twisted out of the thiopyran plane by the flanking substituents, and the barrier to rotation through the plane was found by NMR bandshape analysis to be 17.8 kcal/mol for the (2-aminoethyl)amino and 16.9 kcal/mol for the (3-aminopropyl)amino group. A 1:2 adduct of 5 and DMAD which we also previously incorrectly described as a folded ethylene (B), was shown to be an aminomaleic ester derivative 12 formed by addition of the NH group of 11 to DMAD.

  DOI：

  10.1021/jo00005a043
• 作为产物：
  描述：

  1,3-Dibenzyl-2-(4,4-dimethyl-2-methylsulfanyl-6-thioxo-cyclohex-1-enyl)-4,5-dihydro-3H-imidazol-1-ium; iodide 在 silica gel 碳酸氢钠 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 生成 4--amino>-5-(methylthio)-7H-7,7-dimethylbenzothiopyran-2,3-dicarboxylate
  参考文献：
  名称：

  Addition of twisted 1-thioacyl-2,2-diaminoethylenes to dimethyl acetylenedicarboxylate. Formation and ring opening of thiopyran-4-spiro-2'-(1',3'-diazacyclanes)

  摘要：

  Reaction of 1,3-dialkyl-2-(4,4-dimethyl-2,6-dithioxocyclohexylidene)imidazolidines and -hexahydropyrimidines (twisted push-pull ethylenes, 3) with methyl iodide followed by treatment with base leads smoothly to S-methyl derivatives, which are betaines with a 1,4-dipole and an electron-rich 1,3-butadiene system (5). These compounds react with DMAD to give dihydrobenzothiopyranspiroimidazolidine and -hexahydropyrimidine derivatives 7 in high yields. The spiro compounds rearrange in acid medium or on chromatography on silica gel to compounds, which we previously incorrectly described as ''folded ethylenes'' A but which are now shown to be 4-(2-aminoethyl)amino-ethyl)amino- or 4-(3-aminopropyl)aminothiopyran derivatives 11. The 4-amino groups of 11 are twisted out of the thiopyran plane by the flanking substituents, and the barrier to rotation through the plane was found by NMR bandshape analysis to be 17.8 kcal/mol for the (2-aminoethyl)amino and 16.9 kcal/mol for the (3-aminopropyl)amino group. A 1:2 adduct of 5 and DMAD which we also previously incorrectly described as a folded ethylene (B), was shown to be an aminomaleic ester derivative 12 formed by addition of the NH group of 11 to DMAD.

  DOI：

  10.1021/jo00005a043

文献信息

• KHAN, AGHA ZUL-QARNAIN;SANDSTROM, J. ORG. CHEM., 56,(1991) N, C. 1902-1907
  作者：KHAN, AGHA ZUL-QARNAIN、SANDSTROM

  DOI：——

  日期：——