The title compound（C25H16Cl2N3O3S）,as a thiopyran derivative,has been synthe-sized by the cyclization of an organic intermediate obtained from Baylis-Hillman adducts with a β-aroylthioamide using copper（I） salt a...The title compound（C25H16Cl2N3O3S）,as a thiopyran derivative,has been synthe-sized by the cyclization of an organic intermediate obtained from Baylis-Hillman adducts with a β-aroylthioamide using copper（I） salt as the catalyst.The crystal belongs to the monoclinic system,space group P21/c with a = 13.668（3）,b = 8.4803（17） c = 21.999（4） ,β = 113.57（3）°,V = 2337.2（10） 3,Z = 4,Mr = 510.38,Dc = 1.451 g/cm3,μ = 0.401 mm-1,F（000） = 1048,the final R = 0.0487 and wR = 0.1079 for 3678 observed reflections with I〉 2σ（I）.展开更多
A straightforward and efficient method for the synthesis of thiopyran derivatives via three-component reaction of alkyl propiolate, benzoylisothiocyanate or its derivatives and α-haloketones in the presence of triphe...A straightforward and efficient method for the synthesis of thiopyran derivatives via three-component reaction of alkyl propiolate, benzoylisothiocyanate or its derivatives and α-haloketones in the presence of triphenylphosphine under solvent-free conditions at 70℃ without using any catalyst is reported, The method offers several advantages including high yields of products and an easy work-up procedure.展开更多
The estrogen receptor is a target for therapeutic agents for hormone replacement in menopausal women,osteoporosis, reproductive cancers such as breast cancer,uterine cancer and prostate cancer.1,4-Dihydrothieno[3＇,2...The estrogen receptor is a target for therapeutic agents for hormone replacement in menopausal women,osteoporosis, reproductive cancers such as breast cancer,uterine cancer and prostate cancer.1,4-Dihydrothieno[3＇,2＇：5,6]thiopyrano[4,3- c]pyrazole-3-carboxylic amide derivatives were designed,synthesized and biological evaluated as potential estrogen receptor antagonists.展开更多
Ethylene trithiocarbonate reacted with dimethyl acetylenedicarboxylate to furnish tetramethyl thiopyran-4-spiro-2＇-（1,3- dithiolane）-2,3,5,6-tetracarboxylate,a new thiopyran-4-spiro-2＇-（1,3-dithiolane） heterocyc...Ethylene trithiocarbonate reacted with dimethyl acetylenedicarboxylate to furnish tetramethyl thiopyran-4-spiro-2＇-（1,3- dithiolane）-2,3,5,6-tetracarboxylate,a new thiopyran-4-spiro-2＇-（1,3-dithiolane） heterocyclic compound,as the minor product together with the major product dimethyl 2-thioxo-1,3-dithiole-4,5-dicarboxylate.The new heterocycle was probably formed through a[2 ＋ 2]cycloaddition between ethylene trithiocarbonate and dimethyl acetylenedicarboxylate followed by a 1,3-dipolar cycloaddition or[4 ＋ 2]cycloaddition.Crystal structure of the new compound revealed that the thiopyran ring and 1,3-dithiolane moiety were perpendicular to each other.展开更多
S-fused heterocycles have become popular building blocks to construct functional polycyclic compounds.In contrast to the abundant synthetic methodologies for thiophene-fused aromatics,the synthesis of S-heterocycles c...S-fused heterocycles have become popular building blocks to construct functional polycyclic compounds.In contrast to the abundant synthetic methodologies for thiophene-fused aromatics,the synthesis of S-heterocycles containing six-membered thiopyran and seven-membered thiepine rings is much less reported owing to their unfavorable synthetic protocols and the thermal instabilities.Herein,a series of thiepine-containing polycyclic S-heterocycles have been successfully synthesized via different synthetic routes which involve initial construction of sulfur bridges and final ring-closure reactions.Therefore,the dilithium intermediates are ex-cluded,which facilitates the fusion on the thiepine ring with different S-heterocycles,including thiophene and thiopyran derivatives.Typically,a S-fused multi-membered polycyclic compound simultaneously involving thiophen,thiopyran,and thiepine rings has been successfully prepared.Interestingly,nucleus-independent chemical shift calculations reveal that the incorporated thiopyran and thiepine rings demonstrate aromatic and nonaromatic characteristics,respectively.Moreover,the thermal stabilities of the thiepine derivatives have been tremendously improved after the fusion on the three vinyl groups in the thiepine unit,which is attributed to the enhancements of the activation energies for the S-extrusion reactions,as revealed by density functional theory calculations.Therefore,our findings not only provide a facile synthetic methodology for S-fused multi-membered polycyclic heterocycles,but also furnish a novel construction strategy towards thermally stable thiepine derivatives.展开更多
基金supported by the National Natural Science Foundation of China (No. 20872074 and 21072110)the Natural Science Foundation of Shandong Province (No. Z2008B03 and ZR2010BM007)the Doctoral Foundation of Qingdao University of Science and Technology
文摘The title compound（C25H16Cl2N3O3S）,as a thiopyran derivative,has been synthe-sized by the cyclization of an organic intermediate obtained from Baylis-Hillman adducts with a β-aroylthioamide using copper（I） salt as the catalyst.The crystal belongs to the monoclinic system,space group P21/c with a = 13.668（3）,b = 8.4803（17） c = 21.999（4） ,β = 113.57（3）°,V = 2337.2（10） 3,Z = 4,Mr = 510.38,Dc = 1.451 g/cm3,μ = 0.401 mm-1,F（000） = 1048,the final R = 0.0487 and wR = 0.1079 for 3678 observed reflections with I〉 2σ（I）.
文摘A straightforward and efficient method for the synthesis of thiopyran derivatives via three-component reaction of alkyl propiolate, benzoylisothiocyanate or its derivatives and α-haloketones in the presence of triphenylphosphine under solvent-free conditions at 70℃ without using any catalyst is reported, The method offers several advantages including high yields of products and an easy work-up procedure.
基金supported by the National Natural Science Foundation of China(NSFC)(No20474053)
文摘The estrogen receptor is a target for therapeutic agents for hormone replacement in menopausal women,osteoporosis, reproductive cancers such as breast cancer,uterine cancer and prostate cancer.1,4-Dihydrothieno[3＇,2＇：5,6]thiopyrano[4,3- c]pyrazole-3-carboxylic amide derivatives were designed,synthesized and biological evaluated as potential estrogen receptor antagonists.
基金Financial support of the project by Shanghai Municipal Natural Science Foundation(No06ZR14001)
文摘Ethylene trithiocarbonate reacted with dimethyl acetylenedicarboxylate to furnish tetramethyl thiopyran-4-spiro-2＇-（1,3- dithiolane）-2,3,5,6-tetracarboxylate,a new thiopyran-4-spiro-2＇-（1,3-dithiolane） heterocyclic compound,as the minor product together with the major product dimethyl 2-thioxo-1,3-dithiole-4,5-dicarboxylate.The new heterocycle was probably formed through a[2 ＋ 2]cycloaddition between ethylene trithiocarbonate and dimethyl acetylenedicarboxylate followed by a 1,3-dipolar cycloaddition or[4 ＋ 2]cycloaddition.Crystal structure of the new compound revealed that the thiopyran ring and 1,3-dithiolane moiety were perpendicular to each other.
基金supported by the National Key Research and Development Program of China(2018YFA0209401)the National Natural Science Foundation of China(22171053,21733003)the Natural Science Foundation of Shanghai(21zR1409600)。
文摘S-fused heterocycles have become popular building blocks to construct functional polycyclic compounds.In contrast to the abundant synthetic methodologies for thiophene-fused aromatics,the synthesis of S-heterocycles containing six-membered thiopyran and seven-membered thiepine rings is much less reported owing to their unfavorable synthetic protocols and the thermal instabilities.Herein,a series of thiepine-containing polycyclic S-heterocycles have been successfully synthesized via different synthetic routes which involve initial construction of sulfur bridges and final ring-closure reactions.Therefore,the dilithium intermediates are ex-cluded,which facilitates the fusion on the thiepine ring with different S-heterocycles,including thiophene and thiopyran derivatives.Typically,a S-fused multi-membered polycyclic compound simultaneously involving thiophen,thiopyran,and thiepine rings has been successfully prepared.Interestingly,nucleus-independent chemical shift calculations reveal that the incorporated thiopyran and thiepine rings demonstrate aromatic and nonaromatic characteristics,respectively.Moreover,the thermal stabilities of the thiepine derivatives have been tremendously improved after the fusion on the three vinyl groups in the thiepine unit,which is attributed to the enhancements of the activation energies for the S-extrusion reactions,as revealed by density functional theory calculations.Therefore,our findings not only provide a facile synthetic methodology for S-fused multi-membered polycyclic heterocycles,but also furnish a novel construction strategy towards thermally stable thiepine derivatives.
