Synthesis of Novel Acetal Thia-Cage Compounds
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- 作者：Chung-Yi Wu ; Hui-Chang Lin ; Zhongyi Wang ; and Hsien-Jen Wu
- 刊名：Journal of Organic Chemistry
- 出版年：2001
- 出版时间：June 29, 2001
- 年：2001
- 卷：66
- 期：13
- 页码：4610 - 4618
- 全文大小：122K
- 年卷期：v.66,no.13(June 29, 2001)
- ISSN：1520-6904
文摘
The synthesis of novel acetal thia-cage compounds has been accomplished by the direct substitutionfor the oxygen atom by the sulfur atom in the reaction of the acetal groups of oxa-cages withLawesson reagent (LR). Reaction of the tetraoxa-cage compound 2 with LR in dichloromethane at25 
C sequentially gave the monothia-, dithia-, trithia-, and tetrathia-cage compounds 3, 6, 7, and9. The reaction mechanism for the conversion from oxa-cages into thia-cages was proposed. Thediacetal trioxa-cages 18-20 and 24-26 were also transformed into the thia-cages 21-23 and 27-29, respectively. Reaction of the trioxa-cages 34 and 35 with LR under the same reaction conditionsgave the thia-cages 36 and 37 with the carbonyl group intact. Treatment of the pentaoxa[5]peristylane 40 with LR in chloroform under supersonic shaking at refluxing temperature gave themonothia[5]peristylane 41 and the dithia[5]peristylane 42. Attempts to synthesize the thia[5]peristylanes from the tetraoxa-cage 51 and the transformation from the parent (unsubstituted)pentaoxa[5]peristylane 46 to the thia-cages have been made. Reaction of the pentaoxa[5]-peristylane40 with P2S5 in refluxing toluene gave 41, 42, and a rearrangement product 47. The synthesis ofnew heterocyclic cage compounds 59 and 60, which contain oxygen, nitrogen, and sulfur atoms inthe same molecule, was also accomplished.
C sequentially gave the monothia-, dithia-, trithia-, and tetrathia-cage compounds 3, 6, 7, and9. The reaction mechanism for the conversion from oxa-cages into thia-cages was proposed. Thediacetal trioxa-cages 18-20 and 24-26 were also transformed into the thia-cages 21-23 and 27-29, respectively. Reaction of the trioxa-cages 34 and 35 with LR under the same reaction conditionsgave the thia-cages 36 and 37 with the carbonyl group intact. Treatment of the pentaoxa[5]peristylane 40 with LR in chloroform under supersonic shaking at refluxing temperature gave themonothia[5]peristylane 41 and the dithia[5]peristylane 42. Attempts to synthesize the thia[5]peristylanes from the tetraoxa-cage 51 and the transformation from the parent (unsubstituted)pentaoxa[5]peristylane 46 to the thia-cages have been made. Reaction of the pentaoxa[5]-peristylane40 with P2S5 in refluxing toluene gave 41, 42, and a rearrangement product 47. The synthesis ofnew heterocyclic cage compounds 59 and 60, which contain oxygen, nitrogen, and sulfur atoms inthe same molecule, was also accomplished.