The reaction mechanism of o-aminophenol, acetic acid and phosphorus oxytrichloride in one-pot to form 2-methyl benzoxazole was studied by density functional theory. The geometries of the reactants, transition states, ...The reaction mechanism of o-aminophenol, acetic acid and phosphorus oxytrichloride in one-pot to form 2-methyl benzoxazole was studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the GGA/PW91/DNP level. Vibration analysis was carried out to confirm the transition state structure. Two possible reaction pathways were investigated in this study. The result indicates that the reaction Re→TS1→IM1→TSA2→IMA2→TSA3→IMA3→TSA4→IMA4→TSA5→P2 is the main pathway, the activation energy of which is the lowest. Re→TS1→IM1 is the rate-limiting step, with the activation energy being 221.54 kJ·mol^(-1) and the reaction heat being 10.06 kJ·mol^(-1). The dominant product predicted theoretically is in agreement with the experiment results.展开更多
An environmental benign procedure for synthesis of 2-(N-formyl)-5-aryl/aryloxymethyl-1,3,4-thiadiazoles has been developed by reaction of 2-amino-5-aryl/aryloxymethyl-1,3,4-thiadiazoles with formic acid in PEG-400.The...An environmental benign procedure for synthesis of 2-(N-formyl)-5-aryl/aryloxymethyl-1,3,4-thiadiazoles has been developed by reaction of 2-amino-5-aryl/aryloxymethyl-1,3,4-thiadiazoles with formic acid in PEG-400.The key advantages of this protocol are the shorter reaction time,higher yields,lower cost,simple workup,and environment-friendly compared to conventional organic solvent reaction.The present method does not involve any hazardous organic solvent or catalyst.展开更多
Two 2-aryl imidazo [2,1-a] isoquinolines were synthesized and tested for pregnancy terminating activities. Both of them are new compounds and their structures were confirmed by IR, (HNMR)-H-1, MS and elemental analysi...Two 2-aryl imidazo [2,1-a] isoquinolines were synthesized and tested for pregnancy terminating activities. Both of them are new compounds and their structures were confirmed by IR, (HNMR)-H-1, MS and elemental analysis. They both showed high activities in NIH mice.展开更多
Triphenylamine(TPA)-containing 2-(2-hydroxyphenyl)benzoxazoles(2a-2c)have been synthesized via a highly efficient rhodium-catalyzed C–H/C–H cross-coupling reaction.Compound 2a is a novel mechanofluorochromic materia...Triphenylamine(TPA)-containing 2-(2-hydroxyphenyl)benzoxazoles(2a-2c)have been synthesized via a highly efficient rhodium-catalyzed C–H/C–H cross-coupling reaction.Compound 2a is a novel mechanofluorochromic material with blue-shifted mechanochromic properties.Compounds 2b and 2c presented opposite mechanochromic trends.For 2b,the enol-form emission enhanced,and the ketoform emission blue-shift after grinding.In contrast,2c exhibited the weak enol-form emission disappeared and the keto-form emission slightly red-shift after grinding treatments.The estrone-containing2b-based water-dispersed nanoparticles(NPs)exhibit apparent dual-emission and were applied for fluorescence images.In addition,bis(TPA)-containing 2c-based devices exhibit dual-emission with good performance and a singlet exciton yield of 92%,which breaks through the theoretical upper limit of 25%in conventional fluorescent OLEDs.This is one of the highest exciton utilization values recorded for the ESIPT molecules with a dual emission system.展开更多
基金Supported by the Scientific and Technological Research Program of Chongqing Municipal Education Commission(KJ1601215)the Ministry of Education "Chunhui Plan"(Z2016177)
文摘The reaction mechanism of o-aminophenol, acetic acid and phosphorus oxytrichloride in one-pot to form 2-methyl benzoxazole was studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the GGA/PW91/DNP level. Vibration analysis was carried out to confirm the transition state structure. Two possible reaction pathways were investigated in this study. The result indicates that the reaction Re→TS1→IM1→TSA2→IMA2→TSA3→IMA3→TSA4→IMA4→TSA5→P2 is the main pathway, the activation energy of which is the lowest. Re→TS1→IM1 is the rate-limiting step, with the activation energy being 221.54 kJ·mol^(-1) and the reaction heat being 10.06 kJ·mol^(-1). The dominant product predicted theoretically is in agreement with the experiment results.
基金support from the Natural Science Foundation of Gansu Province(No.3ZS061- A25-019)the Scientific Research fund of Gansu Provincial Education Department(No.0601-25)
文摘An environmental benign procedure for synthesis of 2-(N-formyl)-5-aryl/aryloxymethyl-1,3,4-thiadiazoles has been developed by reaction of 2-amino-5-aryl/aryloxymethyl-1,3,4-thiadiazoles with formic acid in PEG-400.The key advantages of this protocol are the shorter reaction time,higher yields,lower cost,simple workup,and environment-friendly compared to conventional organic solvent reaction.The present method does not involve any hazardous organic solvent or catalyst.
文摘Two 2-aryl imidazo [2,1-a] isoquinolines were synthesized and tested for pregnancy terminating activities. Both of them are new compounds and their structures were confirmed by IR, (HNMR)-H-1, MS and elemental analysis. They both showed high activities in NIH mice.
基金Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology(No.BM2012110)the fundamental research funds for the central universities(No.2023CDJYGRH-YB17)+4 种基金the Venture&Innovation Support Program for Chongqing Overseas Returnees(No.cx2022061)the Natural Science Foundation of Chongqing(No.CSTB2022NSCQ-MSX1123)the Chongqing Talents:Exceptional Young Talents Project(No.cstc2021ycjh-bgzxm0067)Changzhou University,Advanced Catalysis and Green Manufacturing Collaborative Innovation Center(No.ACGM2022–10–10)National Natural Science Foundation of China(Nos.21702019,62174160)for financial support。
文摘Triphenylamine(TPA)-containing 2-(2-hydroxyphenyl)benzoxazoles(2a-2c)have been synthesized via a highly efficient rhodium-catalyzed C–H/C–H cross-coupling reaction.Compound 2a is a novel mechanofluorochromic material with blue-shifted mechanochromic properties.Compounds 2b and 2c presented opposite mechanochromic trends.For 2b,the enol-form emission enhanced,and the ketoform emission blue-shift after grinding.In contrast,2c exhibited the weak enol-form emission disappeared and the keto-form emission slightly red-shift after grinding treatments.The estrone-containing2b-based water-dispersed nanoparticles(NPs)exhibit apparent dual-emission and were applied for fluorescence images.In addition,bis(TPA)-containing 2c-based devices exhibit dual-emission with good performance and a singlet exciton yield of 92%,which breaks through the theoretical upper limit of 25%in conventional fluorescent OLEDs.This is one of the highest exciton utilization values recorded for the ESIPT molecules with a dual emission system.
