An efficient and environmentally friendly procedure for the one-pot synthesis of 13-acetyl-9-methyl-ll-oxo-8-oxa-10,12-diazatricyclo[7.3.1.0^2,7]trideca-2,4,6-triene from salicylaldehyde, acetylacetone and urea via Bi...An efficient and environmentally friendly procedure for the one-pot synthesis of 13-acetyl-9-methyl-ll-oxo-8-oxa-10,12-diazatricyclo[7.3.1.0^2,7]trideca-2,4,6-triene from salicylaldehyde, acetylacetone and urea via Biginelli condensation and intramolecular Michael-addition by using magnesium bromide as an inexpensive and easily available catalyst in a solvent-free condition is described. The structural elucidation of the product is reported by ^1H- and ^13C NMR spectra. The product can also be identified by its EI TOF mass spectrometry based on the molecular ion at m/s 246（10%） and on the fragment ions in which two nitrogen atoms are remained. Three kinds of characteristic fragmentation pathways from the molecular ion were observed. One is the loss of the OH radical to form the dihydropyrimidinone cation at m/z 229（48%）, followed by elimination of a molecular methane forming the pyrimidinone cation at m/z 213（27%）. The second is the cleavage of the C6H4OH radical, and the formation of the dihydropyrimidinone cation at m/z 153（24%）. The third one is the loss of MeC-O radical to afford the oxygen-bridged fragment ion at m/z 203（33%）.展开更多
Two series monot ailed porphyrins, Cobalt-5- {4- [ω- （1-adamant aneamino） alkyloxy] phenyl }- 10,15,20-triphenyl porphyrinate （CoPCnA, n=4,5,6） and Nickel-5-{4-[ω-（1-adamantaneamino）alkyloxy]phenyl}-10,15.20- ...Two series monot ailed porphyrins, Cobalt-5- {4- [ω- （1-adamant aneamino） alkyloxy] phenyl }- 10,15,20-triphenyl porphyrinate （CoPCnA, n=4,5,6） and Nickel-5-{4-[ω-（1-adamantaneamino）alkyloxy]phenyl}-10,15.20- triphenyl porphyrinate （NiPCnA, n=4,5,6）, were synthesized, in which the porphyrin moiety was connected to l-adamantanamine via a flexible hydrocarbon chain. The fluorescence quenching between these donor substrates and mono-6-p-nitrobenzoyl-β-cyclodextrin （NBCD） was studied in detail. Distinct fluorescence quenching occured in these supramolecular systems. This quenching was attributed to the photoinduced electron transfer （PET） inside the supramolecular assembly between the porphyrin donors and cyclodextrin acceptors. Detailed Stern-Volmer constants were measured and they were partitioned into dynamic Stern- Volmer quenching constants and static binding constants. It was demonstrated that the PET interaction between the porphyrin subunits and NBCD is indeed effective.展开更多
1,3-Dipolar cycloaddition of DTE-azomethine ylides （DTE： dithienyl-ethene） to C60 in refluxed toluene was used to synthesize novel dumbbell-type fullerene dimer 1. For the sake of comparison, the monoadduct 2 were ...1,3-Dipolar cycloaddition of DTE-azomethine ylides （DTE： dithienyl-ethene） to C60 in refluxed toluene was used to synthesize novel dumbbell-type fullerene dimer 1. For the sake of comparison, the monoadduct 2 were also synthesized. The molecular geometries of these two compounds were determined by theoretical calculations with HF-3/21G method. UV-Vis and fluorescence experiments were carried out in solvents with different polarity at the room temperature. All the results indicated the existence of a photoinduced intramolecular electron transfer process between the donor and acceptor moieties.展开更多
With the depletion of fossil resources, there is a need to find alternative resources of fuels and chemicals. The use of renewable feedstock such as those from seed oil processing is one of the best available resource...With the depletion of fossil resources, there is a need to find alternative resources of fuels and chemicals. The use of renewable feedstock such as those from seed oil processing is one of the best available resources that have come to the fore-front recently. This paper critically analyzes and highlights major factors in the biodiesel industry, such as seeds oil composition, production methods, properties of biodiesel, problems and potential solutions of using vegetable seed oil, the composition, quality and effective utilization of crude glycerol, the catalytic conversion of glycerol into possible fuels and chemicals.展开更多
An iron（Ⅲ）-catalyzed selective oxidation of 5-HMF to 2,5-DFF in air at room temperature was developed.This approach gives 2,5-DFF with good selectivity and yields. Additionally, a two-step process was developed for...An iron（Ⅲ）-catalyzed selective oxidation of 5-HMF to 2,5-DFF in air at room temperature was developed.This approach gives 2,5-DFF with good selectivity and yields. Additionally, a two-step process was developed for the oxidation of 2,5-DFF to 2,5-FDCA at remarkably high substrate concentrations. This work demonstrates unequivocally the great potential of iron as a cheap and earth-abundant catalyst for the development of new protocols for the conversion of biomass to value-added chemicals.展开更多
基金This work was supported by the Natural Science Foundation of China （No.20425309）.
文摘An efficient and environmentally friendly procedure for the one-pot synthesis of 13-acetyl-9-methyl-ll-oxo-8-oxa-10,12-diazatricyclo[7.3.1.0^2,7]trideca-2,4,6-triene from salicylaldehyde, acetylacetone and urea via Biginelli condensation and intramolecular Michael-addition by using magnesium bromide as an inexpensive and easily available catalyst in a solvent-free condition is described. The structural elucidation of the product is reported by ^1H- and ^13C NMR spectra. The product can also be identified by its EI TOF mass spectrometry based on the molecular ion at m/s 246（10%） and on the fragment ions in which two nitrogen atoms are remained. Three kinds of characteristic fragmentation pathways from the molecular ion were observed. One is the loss of the OH radical to form the dihydropyrimidinone cation at m/z 229（48%）, followed by elimination of a molecular methane forming the pyrimidinone cation at m/z 213（27%）. The second is the cleavage of the C6H4OH radical, and the formation of the dihydropyrimidinone cation at m/z 153（24%）. The third one is the loss of MeC-O radical to afford the oxygen-bridged fragment ion at m/z 203（33%）.
基金V. ACKN0WLEDGMENT This work was supported Science Foundation of China by the National Natural （No.20472079）.
文摘Two series monot ailed porphyrins, Cobalt-5- {4- [ω- （1-adamant aneamino） alkyloxy] phenyl }- 10,15,20-triphenyl porphyrinate （CoPCnA, n=4,5,6） and Nickel-5-{4-[ω-（1-adamantaneamino）alkyloxy]phenyl}-10,15.20- triphenyl porphyrinate （NiPCnA, n=4,5,6）, were synthesized, in which the porphyrin moiety was connected to l-adamantanamine via a flexible hydrocarbon chain. The fluorescence quenching between these donor substrates and mono-6-p-nitrobenzoyl-β-cyclodextrin （NBCD） was studied in detail. Distinct fluorescence quenching occured in these supramolecular systems. This quenching was attributed to the photoinduced electron transfer （PET） inside the supramolecular assembly between the porphyrin donors and cyclodextrin acceptors. Detailed Stern-Volmer constants were measured and they were partitioned into dynamic Stern- Volmer quenching constants and static binding constants. It was demonstrated that the PET interaction between the porphyrin subunits and NBCD is indeed effective.
基金Ⅴ. ACKN0WLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.20332020 and No.20472079）.
文摘1,3-Dipolar cycloaddition of DTE-azomethine ylides （DTE： dithienyl-ethene） to C60 in refluxed toluene was used to synthesize novel dumbbell-type fullerene dimer 1. For the sake of comparison, the monoadduct 2 were also synthesized. The molecular geometries of these two compounds were determined by theoretical calculations with HF-3/21G method. UV-Vis and fluorescence experiments were carried out in solvents with different polarity at the room temperature. All the results indicated the existence of a photoinduced intramolecular electron transfer process between the donor and acceptor moieties.
基金supported by the National Natural Science Foundation of China(21325208,21172209,21272050)the Chinese Academy of Sciences(KJCX2-EW-J02)FRFCU(WK2060190025,WK2060190033)
文摘With the depletion of fossil resources, there is a need to find alternative resources of fuels and chemicals. The use of renewable feedstock such as those from seed oil processing is one of the best available resources that have come to the fore-front recently. This paper critically analyzes and highlights major factors in the biodiesel industry, such as seeds oil composition, production methods, properties of biodiesel, problems and potential solutions of using vegetable seed oil, the composition, quality and effective utilization of crude glycerol, the catalytic conversion of glycerol into possible fuels and chemicals.
基金the National Basic Research Program of China (Nos. 2013CB228103, 2012CB215306)NNSFC (Nos. 21472033, 21325208, 21172209)+3 种基金FRFCU (No. WK2060190025)SRFDP (No. 20123402130008)CAS (No. KJCX2-EW-J02)Fok Ying Tung Education Foundation for the financial support
文摘An iron（Ⅲ）-catalyzed selective oxidation of 5-HMF to 2,5-DFF in air at room temperature was developed.This approach gives 2,5-DFF with good selectivity and yields. Additionally, a two-step process was developed for the oxidation of 2,5-DFF to 2,5-FDCA at remarkably high substrate concentrations. This work demonstrates unequivocally the great potential of iron as a cheap and earth-abundant catalyst for the development of new protocols for the conversion of biomass to value-added chemicals.
