dimethyl 1',3'-dibenzyl-5-[(Z)-1,4-dimethoxy-1,4-dioxobut-2-en-2-yl]sulfanyl-7,7-dimethylspiro[8H-thiochromene-4,2'-imidazolidine]-2,3-dicarboxylate | 135192-57-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl 1',3'-dibenzyl-5-[(Z)-1,4-dimethoxy-1,4-dioxobut-2-en-2-yl]sulfanyl-7,7-dimethylspiro[8H-thiochromene-4,2'-imidazolidine]-2,3-dicarboxylate
• CAS: 135192-57-3
• 化学式: C₃₇H₄₀N₂O₈S₂
• 分子量: 704.865
• InChiKey: ACUJEIGBAMIXGC-XHPQRKPJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  49
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  162
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  dimethyl 1',3'-dibenzyl-5-[(Z)-1,4-dimethoxy-1,4-dioxobut-2-en-2-yl]sulfanyl-7,7-dimethylspiro[8H-thiochromene-4,2'-imidazolidine]-2,3-dicarboxylate 在 盐酸 作用下， 以 乙腈 为溶剂， 以82%的产率得到4-[Benzyl-(2-benzylamino-ethyl)-amino]-5-((Z)-1,2-bis-methoxycarbonyl-vinylsulfanyl)-7,7-dimethyl-7H-thiochromene-2,3-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Addition of twisted 1,1-bis(thioacyl)-2,2-diaminoethylenes to dimethyl acetylenedicarboxylate. 2. Structure determination of two isomeric spiro adducts by x-ray crystallography and of a rearrangement product by the 2D INADEQUATE technique

  摘要：

  1,3-Dialkyl-2-(4,4-dimethyl-2,6-dithioxocyclohexylidene)imidazolidines (twisted push-pull ethylenes) react smoothly with dimethyl acetylenedicarboxylate (DMAD) but require at least 3 equiv of DMAD for complete consumption. Chromatography of the complex reaction mixture gave two isomeric 1:2 adducts, shown by X-ray crystallography to be (E)- and (Z)-[1,2-bis(methoxycarbonyl)vinyl]thio-susbstituted thiopyran-4-spiro-2'-imidazolidines. Treatment of the spior compounds with dilute nonaqueous acid led to isomers in which the imidazolidine ring had opened, and acid hydrolysis gave a thiopyrone and its enol tautomer. Continued chromatography of the original reaction mixture gave three new compounds, a thiopyran-4-thione, a tetrakis-(methoxycarbonyl)-1,4-dithiaphenalene, and a precursor to this with the same ring system. The formation of these compounds requires migration of a sulfur atom from the cyclohexene ring to the annelated thiopyran ring, and a possible mechanism is discussed. The dithiaphenalene structure was firmly established by the 2D INADEQUATE technique.

  DOI：

  10.1021/jo00016a021
• 作为产物：
  描述：

  2-(1,3-Dibenzyl-imidazolidin-2-yl)-3-mercapto-5,5-dimethyl-cyclohex-2-enethione 、 丁炔二酸二甲酯 以 甲苯 为溶剂， 以19%的产率得到2,3-bis(methoxycarbonyl)-5(E)-<<1,2-bis(methoxycarbonyl)vinyl>thio>-7,7-dimethyl-7,8-dihydro-1',3'-dibenzylbenzothiopyran-4-spiro-2'-imidazolidine
  参考文献：
  名称：

  Addition of twisted 1,1-bis(thioacyl)-2,2-diaminoethylenes to dimethyl acetylenedicarboxylate. 2. Structure determination of two isomeric spiro adducts by x-ray crystallography and of a rearrangement product by the 2D INADEQUATE technique

  摘要：

  1,3-Dialkyl-2-(4,4-dimethyl-2,6-dithioxocyclohexylidene)imidazolidines (twisted push-pull ethylenes) react smoothly with dimethyl acetylenedicarboxylate (DMAD) but require at least 3 equiv of DMAD for complete consumption. Chromatography of the complex reaction mixture gave two isomeric 1:2 adducts, shown by X-ray crystallography to be (E)- and (Z)-[1,2-bis(methoxycarbonyl)vinyl]thio-susbstituted thiopyran-4-spiro-2'-imidazolidines. Treatment of the spior compounds with dilute nonaqueous acid led to isomers in which the imidazolidine ring had opened, and acid hydrolysis gave a thiopyrone and its enol tautomer. Continued chromatography of the original reaction mixture gave three new compounds, a thiopyran-4-thione, a tetrakis-(methoxycarbonyl)-1,4-dithiaphenalene, and a precursor to this with the same ring system. The formation of these compounds requires migration of a sulfur atom from the cyclohexene ring to the annelated thiopyran ring, and a possible mechanism is discussed. The dithiaphenalene structure was firmly established by the 2D INADEQUATE technique.

  DOI：

  10.1021/jo00016a021

文献信息

• Addition of twisted 1,1-bis(thioacyl)-2,2-diaminoethylenes to dimethyl acetylenedicarboxylate. 2. Structure determination of two isomeric spiro adducts by x-ray crystallography and of a rearrangement product by the 2D INADEQUATE technique
  作者：Agha Zul Qarnain Khan、Jan Sandstroem、Karl Eric Bergquist、Chih Yi Cheng、Sue Lein Wang

  DOI：10.1021/jo00016a021

  日期：1991.8

  1,3-Dialkyl-2-(4,4-dimethyl-2,6-dithioxocyclohexylidene)imidazolidines (twisted push-pull ethylenes) react smoothly with dimethyl acetylenedicarboxylate (DMAD) but require at least 3 equiv of DMAD for complete consumption. Chromatography of the complex reaction mixture gave two isomeric 1:2 adducts, shown by X-ray crystallography to be (E)- and (Z)-[1,2-bis(methoxycarbonyl)vinyl]thio-susbstituted thiopyran-4-spiro-2'-imidazolidines. Treatment of the spior compounds with dilute nonaqueous acid led to isomers in which the imidazolidine ring had opened, and acid hydrolysis gave a thiopyrone and its enol tautomer. Continued chromatography of the original reaction mixture gave three new compounds, a thiopyran-4-thione, a tetrakis-(methoxycarbonyl)-1,4-dithiaphenalene, and a precursor to this with the same ring system. The formation of these compounds requires migration of a sulfur atom from the cyclohexene ring to the annelated thiopyran ring, and a possible mechanism is discussed. The dithiaphenalene structure was firmly established by the 2D INADEQUATE technique.