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
Cyclopropanedicarboxylic anhydride can be converted to 4-substituted (or 4-spiro-)3-oxabicyclo[3.1.0]hexan-2-one by addition of Grignard (or α,ω-di-Crignard) reagents in ether or tetrahydrofuran solution.
The spiro-calix[4]arenes 3a-b can he synthesized conveniently by the reaction of p-tert-butylcalix[4]arene (1a) or calix[4]arene (1b) with pentaerythritol tetrakis(2-chloroacetate) (2).
Results of oxidation 2-(N-acetylamine)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid oxygen depend on temperature. At 55℃?- 60℃, 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa i...Results of oxidation 2-(N-acetylamine)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid oxygen depend on temperature. At 55℃?- 60℃, 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa is formed. The constitution is based on dates of spectrums 1Н and 13С NMR. At 95℃?- 97℃, mixtures of 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa and of 6,8-di-tert-butyl-3-(N-acetylamine)spiro(4,5)deca-1-oxa-5,8-dien-2,7-dione are produced. Structures are calculated by the method of Hartrii-Foka. Values of enthalpies and of entropies allow to assume dynamic isomerism.展开更多
The double Michael reactions between benzofuran-3-one or 1-indone and symmetric dienones in the presence of catalytic ionic liquids were successfully developed and spiro[benzofuran-2, 1′-cyclohexane]-3-one or spiro[c...The double Michael reactions between benzofuran-3-one or 1-indone and symmetric dienones in the presence of catalytic ionic liquids were successfully developed and spiro[benzofuran-2, 1′-cyclohexane]-3-one or spiro[cyclo- hexane-1,2′-indene]-1′,4（3′H）-dione derivatives containing a spiro quaternary stereogenic center, which widely exist in biologically active products and building blocks in organic synthesis, were obtained in excellent yields （up to 99%）. This catalytic system was also extended to the double Michael reaction of less reactive 1-indone and the desired products were also obtained in 31%-62% yields. The catalytic system was highly active and efficient for a broad of substrates under mild conditions.展开更多
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.
文摘Cyclopropanedicarboxylic anhydride can be converted to 4-substituted (or 4-spiro-)3-oxabicyclo[3.1.0]hexan-2-one by addition of Grignard (or α,ω-di-Crignard) reagents in ether or tetrahydrofuran solution.
文摘The spiro-calix[4]arenes 3a-b can he synthesized conveniently by the reaction of p-tert-butylcalix[4]arene (1a) or calix[4]arene (1b) with pentaerythritol tetrakis(2-chloroacetate) (2).
文摘Results of oxidation 2-(N-acetylamine)-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid oxygen depend on temperature. At 55℃?- 60℃, 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa is formed. The constitution is based on dates of spectrums 1Н and 13С NMR. At 95℃?- 97℃, mixtures of 2,4-di-tert-butylbicyclo(4,3,1)deca-4,6-dien-8-(N-acetylamine)-3,9-dion-1-oxa and of 6,8-di-tert-butyl-3-(N-acetylamine)spiro(4,5)deca-1-oxa-5,8-dien-2,7-dione are produced. Structures are calculated by the method of Hartrii-Foka. Values of enthalpies and of entropies allow to assume dynamic isomerism.
基金supported by the National Basic Research Program of China (973 Program 2011CB808600)+4 种基金the National Natural Science Foundation of China (21172176 21372180)Hubei Province Natural Science Foundation (ZRZ0273)Fundamental Research Funds for the Central Universitiesan Academic Award for Excellent PhD Candidates Funded by the Ministry of Education of China (5052011203011)~~
文摘The double Michael reactions between benzofuran-3-one or 1-indone and symmetric dienones in the presence of catalytic ionic liquids were successfully developed and spiro[benzofuran-2, 1′-cyclohexane]-3-one or spiro[cyclo- hexane-1,2′-indene]-1′,4（3′H）-dione derivatives containing a spiro quaternary stereogenic center, which widely exist in biologically active products and building blocks in organic synthesis, were obtained in excellent yields （up to 99%）. This catalytic system was also extended to the double Michael reaction of less reactive 1-indone and the desired products were also obtained in 31%-62% yields. The catalytic system was highly active and efficient for a broad of substrates under mild conditions.
