The intermolecular reductive coupling of nitrites with azobenzene induced by SmI2 was studied. Amidine derivatives were prepared in good yields under neutral and mild conditions.
The reduction of disulfides by samarium diiodide led to sa arium thiolates (ArSSml2).This new thiolate anion species reacted smoothly with α, β -unsaturated esters (nitriles) to give 1,4-addition products β -thioes...The reduction of disulfides by samarium diiodide led to sa arium thiolates (ArSSml2).This new thiolate anion species reacted smoothly with α, β -unsaturated esters (nitriles) to give 1,4-addition products β -thioesters and β -thionitriles in good yields under mild and neutralcondition.展开更多
The sorption behavior and mechanism of a novel chelate resin, diglycolamidic acid resin (DAAR), for Sm(III) were investigated. The optimal sorption condition of DAAR for Sm(III) is pH=6.0 in HAc-NaAc medium. The stati...The sorption behavior and mechanism of a novel chelate resin, diglycolamidic acid resin (DAAR), for Sm(III) were investigated. The optimal sorption condition of DAAR for Sm(III) is pH=6.0 in HAc-NaAc medium. The statically saturated sorption capacity is 190mg/g resin at 298K. The Sm(III) adsorbed on DAAR can be eluted reaching 100% by 0.5~2.0mol/L HCl used as eluant. The resin can be regenerated and reused without apparent decrease of sorption capacity. The apparent sorption rate constant is k298= 1.96×10-5s-1. The apparent activation energy is 26kJ/mol. The sorption behavior of DAAR for Sm(III) obeys the Freundlich isotherm. The thermodynamic sorption parameters, enthalpy change 腍 of DAAR for Sm(III) is 16.9kJ/mol. The molar coordination ratio of the functional group of DAAR to Sm (III) is 3. The sorption mechanism of DAAR for Sm(III) was examined by using chemical method and IR spectrometry. The coordination bond was formed between oxygen atoms in the functional group of DAAR and Sm(III).展开更多
Sm(III) was quantitatively adsorbed by amino methylene phosphonic acid resin (APAR) in the medium of pH=5.0. The statically saturated sorption capacity is 251mg/g·resin. Sm(III) adsorbed on APAR can be reductivel...Sm(III) was quantitatively adsorbed by amino methylene phosphonic acid resin (APAR) in the medium of pH=5.0. The statically saturated sorption capacity is 251mg/g·resin. Sm(III) adsorbed on APAR can be reductively eluted by 2.0mol/L HCl. The sorption rate constant is k298= 1.35×10-5s-1. The sorption behavior of APAR for Sm(III) obeys the Freundlich isotherm. The enthalpy change △H of sorption is 24.9kJ/mol. The apparent activation energy is Ea=11.7kJ/mol. The sorption mechanism shows that the nitrogen and oxygen atoms of the functional group of APAR coordinated with Sm(III) to form coordination bond.展开更多
Nitrodisulfides were reduced by SmI2/HMPA in anhydrous THF at room temperature to produce active intermediates (samarium thiolates and amides), which were 'living' double-anions and reacted smoothly with aldeh...Nitrodisulfides were reduced by SmI2/HMPA in anhydrous THF at room temperature to produce active intermediates (samarium thiolates and amides), which were 'living' double-anions and reacted smoothly with aldehydes or ketones to afford benzothiazolines in good yields under mild and neutral conditions.展开更多
The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se-2(2-) and Se2-), these nucleophilic species reacted readily with sodium alkyl thiosulfates to afford ...The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se-2(2-) and Se2-), these nucleophilic species reacted readily with sodium alkyl thiosulfates to afford dithiodiselenides and dithioselenides in moderate to good yield under mild conditions.展开更多
The Se-St bond in arylselenotrimethylsilane was reduced by samarium diiodide to produce samarium arylselenolate, which reacted with a,β-unsaturated esters or α,β-unsaturated nitriles to give β-selenoesters and β-...The Se-St bond in arylselenotrimethylsilane was reduced by samarium diiodide to produce samarium arylselenolate, which reacted with a,β-unsaturated esters or α,β-unsaturated nitriles to give β-selenoesters and β-selenonitriles, respectively.展开更多
o-Nitrophenylazide was reduced by SmI2 in anhydrous THF at room temperature to produce active intermediate 2 (samarium amide), "living" double-anion in situ which reacted smoothly with α，β-unsaturated ket...o-Nitrophenylazide was reduced by SmI2 in anhydrous THF at room temperature to produce active intermediate 2 (samarium amide), "living" double-anion in situ which reacted smoothly with α，β-unsaturated ketones to afford 2,3-dihydro-1H-1,5-benzodiazepines in good yields under mild and neutral conditions.展开更多
1-（β-Hydroxyalkyl）-l,3,4-oxadiazole derivatives were synthesized via reductive addition reactions of 2-chloromethyl-l,3,4-oxadiazole with carbonyl compounds under mild conditions promoted by SmI2.
Dihydro-(2H)-1 .2.4-benzothiadizine-1. 1-dioixdes were prepared in good yields via reductive cyclization of o-nitrobenzenesulfonamidcs with aldchydes promoted by Sml2 under mild and neutral condition.
The reduction of diacyl diselenides by samarium diiodide led to the production ofsamarium acylselenolates, which reacted with a,β-unsaturated esters or nitriles to give β-selenoesters or selenonitriles under mild an...The reduction of diacyl diselenides by samarium diiodide led to the production ofsamarium acylselenolates, which reacted with a,β-unsaturated esters or nitriles to give β-selenoesters or selenonitriles under mild and neutral conditions.展开更多
文摘The intermolecular reductive coupling of nitrites with azobenzene induced by SmI2 was studied. Amidine derivatives were prepared in good yields under neutral and mild conditions.
文摘The reduction of disulfides by samarium diiodide led to sa arium thiolates (ArSSml2).This new thiolate anion species reacted smoothly with α, β -unsaturated esters (nitriles) to give 1,4-addition products β -thioesters and β -thionitriles in good yields under mild and neutralcondition.
基金The Natural Science Foundation of Zhejiang Province (No.200072)
文摘The sorption behavior and mechanism of a novel chelate resin, diglycolamidic acid resin (DAAR), for Sm(III) were investigated. The optimal sorption condition of DAAR for Sm(III) is pH=6.0 in HAc-NaAc medium. The statically saturated sorption capacity is 190mg/g resin at 298K. The Sm(III) adsorbed on DAAR can be eluted reaching 100% by 0.5~2.0mol/L HCl used as eluant. The resin can be regenerated and reused without apparent decrease of sorption capacity. The apparent sorption rate constant is k298= 1.96×10-5s-1. The apparent activation energy is 26kJ/mol. The sorption behavior of DAAR for Sm(III) obeys the Freundlich isotherm. The thermodynamic sorption parameters, enthalpy change 腍 of DAAR for Sm(III) is 16.9kJ/mol. The molar coordination ratio of the functional group of DAAR to Sm (III) is 3. The sorption mechanism of DAAR for Sm(III) was examined by using chemical method and IR spectrometry. The coordination bond was formed between oxygen atoms in the functional group of DAAR and Sm(III).
基金Foundations of Zhejiang Provincial Education Ministry (No.20010677)
文摘Sm(III) was quantitatively adsorbed by amino methylene phosphonic acid resin (APAR) in the medium of pH=5.0. The statically saturated sorption capacity is 251mg/g·resin. Sm(III) adsorbed on APAR can be reductively eluted by 2.0mol/L HCl. The sorption rate constant is k298= 1.35×10-5s-1. The sorption behavior of APAR for Sm(III) obeys the Freundlich isotherm. The enthalpy change △H of sorption is 24.9kJ/mol. The apparent activation energy is Ea=11.7kJ/mol. The sorption mechanism shows that the nitrogen and oxygen atoms of the functional group of APAR coordinated with Sm(III) to form coordination bond.
基金We thank the National Natural Science Foundation of China (Project! No.29872010)the Laboratory of Organometallic Chemistry,
文摘Nitrodisulfides were reduced by SmI2/HMPA in anhydrous THF at room temperature to produce active intermediates (samarium thiolates and amides), which were 'living' double-anions and reacted smoothly with aldehydes or ketones to afford benzothiazolines in good yields under mild and neutral conditions.
基金We are grateful to the National Natural Science Foundation of China(Project No.29872010)NSF of Zhejiang Province,China for the financial support.
文摘The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se-2(2-) and Se2-), these nucleophilic species reacted readily with sodium alkyl thiosulfates to afford dithiodiselenides and dithioselenides in moderate to good yield under mild conditions.
文摘The Se-St bond in arylselenotrimethylsilane was reduced by samarium diiodide to produce samarium arylselenolate, which reacted with a,β-unsaturated esters or α,β-unsaturated nitriles to give β-selenoesters and β-selenonitriles, respectively.
基金We thank the National Natural Science Foundation of China (Project No.29872010) NSF of Zhejiang province for financial support.
文摘o-Nitrophenylazide was reduced by SmI2 in anhydrous THF at room temperature to produce active intermediate 2 (samarium amide), "living" double-anion in situ which reacted smoothly with α，β-unsaturated ketones to afford 2,3-dihydro-1H-1,5-benzodiazepines in good yields under mild and neutral conditions.
基金the National Natural Science Foundation of China(Project No.20072033)the NSF of Zhejiang Province for financial support.
文摘1-（β-Hydroxyalkyl）-l,3,4-oxadiazole derivatives were synthesized via reductive addition reactions of 2-chloromethyl-l,3,4-oxadiazole with carbonyl compounds under mild conditions promoted by SmI2.
文摘Dihydro-(2H)-1 .2.4-benzothiadizine-1. 1-dioixdes were prepared in good yields via reductive cyclization of o-nitrobenzenesulfonamidcs with aldchydes promoted by Sml2 under mild and neutral condition.
文摘The reduction of diacyl diselenides by samarium diiodide led to the production ofsamarium acylselenolates, which reacted with a,β-unsaturated esters or nitriles to give β-selenoesters or selenonitriles under mild and neutral conditions.
