目的研究利可君的4个非对映异构体及其有关物质的结构。方法利用液相色谱-二极管阵列检测、液相色谱-串联质谱和液相色谱-核磁共振等联用技术研究利可君及有关物质的结构。采用Phenomnex Luna C18色谱柱(250 mm×4.60 mm ID,5μm),...目的研究利可君的4个非对映异构体及其有关物质的结构。方法利用液相色谱-二极管阵列检测、液相色谱-串联质谱和液相色谱-核磁共振等联用技术研究利可君及有关物质的结构。采用Phenomnex Luna C18色谱柱(250 mm×4.60 mm ID,5μm),水-乙腈-冰醋酸(58∶42∶0.3)为流动相。结果确定了在溶液状态下利可君及其有关物质的结构,发现其均有4个非对映异构体;还对利可君的4个非对映异构体在溶液中互变与稳定性进行比较与量子化学计算,证明其稳定构型为3R4S5R。结论利可君在溶液中非对映异构体相互转化,有一种优势构型。展开更多
A facile 7-step procedure for the synthesis of enantiomerically pure 1-（5-bromo-2-chlorophenyl）-1-（4-ethoxyphenyl）ethanes[（R）-2 and（S）-2] that started from （5-bromo-2-chlorophenyl）（4-ethoxyphenyl）methanone...A facile 7-step procedure for the synthesis of enantiomerically pure 1-（5-bromo-2-chlorophenyl）-1-（4-ethoxyphenyl）ethanes[（R）-2 and（S）-2] that started from （5-bromo-2-chlorophenyl）（4-ethoxyphenyl）methanone 3 was developed.The key step was the resolution of 2-（5-bromo-2-chlorophenyl）-2-（4-ethoxyphenyl）acetic acid 6 by crystallizations of its L-and D-menthyl esters 7 and 8 from petroleum ether to give optically pure enantiomers 9 and 10,respectively.The absolute configurations of the products were unambiguously determined by single-crystal X-ray diffractions of four key intermediates,9,10,13 and 14.This procedure is characterized by inexpensiveness,scalability and ability to produce two individual enantiomers of a diarylethane with unambiguously determined absolute configurations and high enantiomeric purities.展开更多
<正> A new series of dextrorotatory derivatives of 1R,3RS,5S-1,8,8-trimethyl-2,4,3-diazaphosphabicyclo [3.2.1] octane with a newly formed chiral phosphorus atom has been prepared by an asymmetric reaction of (+)...<正> A new series of dextrorotatory derivatives of 1R,3RS,5S-1,8,8-trimethyl-2,4,3-diazaphosphabicyclo [3.2.1] octane with a newly formed chiral phosphorus atom has been prepared by an asymmetric reaction of (+)-cis-1R,3S-1,2,2-trimethyl-1,3-cyclopentadiamine with some thiophosphoryl dichlorides. The optically active products consisted of two unequal amounts of diastereomers,(1R, 3R, 5S) isomers and(1R, 3S, 5S) isomers. Two regioselective reactions took place when phenoxy thiophosphoryl dichloride and N,N-dialkylamino thiophosphoryl dichlorides were chosen as the reagents for the reaction. The content of (1R, 3R, 5S) isomers in the product was over 90% for the former and there were only (1R, 3S, 5S) isomers obtained for the latter.展开更多
Asymmetric 6-substituted-2-methoxy-4-(2,4-dichlorophenyl)-4H-1,3,2-benzodioxaphosphorin a-sulfides were prepared from intramolecular cyclization. The diastereomers were separated by column chromatography and fractiona...Asymmetric 6-substituted-2-methoxy-4-(2,4-dichlorophenyl)-4H-1,3,2-benzodioxaphosphorin a-sulfides were prepared from intramolecular cyclization. The diastereomers were separated by column chromatography and fractional crystallization. Their structures were characterized on the basis of H-1 NMR, P-31 NMR and x-ray diffraction analysis.展开更多
the acetate of a novel phenolic glycoside, 1-O-beta-D-glucopyranosyl-( 1-->6)-beta-D-glucopyranosyloxy-3-hydroxy-5-methylbenzene anacardoside, from the fruits of Semecarpus anacardium, and its diastereomer were fir...the acetate of a novel phenolic glycoside, 1-O-beta-D-glucopyranosyl-( 1-->6)-beta-D-glucopyranosyloxy-3-hydroxy-5-methylbenzene anacardoside, from the fruits of Semecarpus anacardium, and its diastereomer were first synthesized using Koenigs-Knorr method from D-glucose through six steps with total yields 33% and 16% respectively.展开更多
Morpholine fungcides have certain antibacterial side effect, dodemorph being the most active among them. The diequatorial (cis-)?form of dodemorph expressed higher antibacterial activity than the axial-equatorial (tra...Morpholine fungcides have certain antibacterial side effect, dodemorph being the most active among them. The diequatorial (cis-)?form of dodemorph expressed higher antibacterial activity than the axial-equatorial (trans-)?form, and no synergy in their joint action could be revealed in this respect. Moreover, the partition of diastereomers between cells and medium strictly correlated to their toxicity.?Considerable differences were detected among degradation rates in various bacteria, and the?meso-(RS)-diastereomer was deteriorated more intensively, then the?trans-(SS?and?RR)-forms in?Corynebacterium?betae,?Erwinia uredovora?and?Pseudomonasfluorescens. As a result, the stereospecific degradation of diastereomers changed their ratio in the medium, thus this metabolic step could?influence the antifungal performance of dodemorph based preparations against filamentous fungi. It was demonstrated that due to synergic joint action,?the fungistatic effect of morpholine derivatives noticeably increased against?Botrytis cinerea?by changing the ratio of diastereomers.展开更多
文摘目的研究利可君的4个非对映异构体及其有关物质的结构。方法利用液相色谱-二极管阵列检测、液相色谱-串联质谱和液相色谱-核磁共振等联用技术研究利可君及有关物质的结构。采用Phenomnex Luna C18色谱柱(250 mm×4.60 mm ID,5μm),水-乙腈-冰醋酸(58∶42∶0.3)为流动相。结果确定了在溶液状态下利可君及其有关物质的结构,发现其均有4个非对映异构体;还对利可君的4个非对映异构体在溶液中互变与稳定性进行比较与量子化学计算,证明其稳定构型为3R4S5R。结论利可君在溶液中非对映异构体相互转化,有一种优势构型。
基金Supported by the National Natural Science Foundation of China（No.21302141） and the Key Projects of Tianjin Science and Technology Support Plan,China（No.10ZCKFSH01300）.
文摘A facile 7-step procedure for the synthesis of enantiomerically pure 1-（5-bromo-2-chlorophenyl）-1-（4-ethoxyphenyl）ethanes[（R）-2 and（S）-2] that started from （5-bromo-2-chlorophenyl）（4-ethoxyphenyl）methanone 3 was developed.The key step was the resolution of 2-（5-bromo-2-chlorophenyl）-2-（4-ethoxyphenyl）acetic acid 6 by crystallizations of its L-and D-menthyl esters 7 and 8 from petroleum ether to give optically pure enantiomers 9 and 10,respectively.The absolute configurations of the products were unambiguously determined by single-crystal X-ray diffractions of four key intermediates,9,10,13 and 14.This procedure is characterized by inexpensiveness,scalability and ability to produce two individual enantiomers of a diarylethane with unambiguously determined absolute configurations and high enantiomeric purities.
文摘<正> A new series of dextrorotatory derivatives of 1R,3RS,5S-1,8,8-trimethyl-2,4,3-diazaphosphabicyclo [3.2.1] octane with a newly formed chiral phosphorus atom has been prepared by an asymmetric reaction of (+)-cis-1R,3S-1,2,2-trimethyl-1,3-cyclopentadiamine with some thiophosphoryl dichlorides. The optically active products consisted of two unequal amounts of diastereomers,(1R, 3R, 5S) isomers and(1R, 3S, 5S) isomers. Two regioselective reactions took place when phenoxy thiophosphoryl dichloride and N,N-dialkylamino thiophosphoryl dichlorides were chosen as the reagents for the reaction. The content of (1R, 3R, 5S) isomers in the product was over 90% for the former and there were only (1R, 3S, 5S) isomers obtained for the latter.
文摘Asymmetric 6-substituted-2-methoxy-4-(2,4-dichlorophenyl)-4H-1,3,2-benzodioxaphosphorin a-sulfides were prepared from intramolecular cyclization. The diastereomers were separated by column chromatography and fractional crystallization. Their structures were characterized on the basis of H-1 NMR, P-31 NMR and x-ray diffraction analysis.
文摘the acetate of a novel phenolic glycoside, 1-O-beta-D-glucopyranosyl-( 1-->6)-beta-D-glucopyranosyloxy-3-hydroxy-5-methylbenzene anacardoside, from the fruits of Semecarpus anacardium, and its diastereomer were first synthesized using Koenigs-Knorr method from D-glucose through six steps with total yields 33% and 16% respectively.
文摘Morpholine fungcides have certain antibacterial side effect, dodemorph being the most active among them. The diequatorial (cis-)?form of dodemorph expressed higher antibacterial activity than the axial-equatorial (trans-)?form, and no synergy in their joint action could be revealed in this respect. Moreover, the partition of diastereomers between cells and medium strictly correlated to their toxicity.?Considerable differences were detected among degradation rates in various bacteria, and the?meso-(RS)-diastereomer was deteriorated more intensively, then the?trans-(SS?and?RR)-forms in?Corynebacterium?betae,?Erwinia uredovora?and?Pseudomonasfluorescens. As a result, the stereospecific degradation of diastereomers changed their ratio in the medium, thus this metabolic step could?influence the antifungal performance of dodemorph based preparations against filamentous fungi. It was demonstrated that due to synergic joint action,?the fungistatic effect of morpholine derivatives noticeably increased against?Botrytis cinerea?by changing the ratio of diastereomers.
