The α-acetyl ketene dithioacetals 2, which bear various alkylthio groups, are a kind of important intermediates in organic synthesis. In this paper, dithioacetals 2 were prepared in very high yields (90%—100%) via t...The α-acetyl ketene dithioacetals 2, which bear various alkylthio groups, are a kind of important intermediates in organic synthesis. In this paper, dithioacetals 2 were prepared in very high yields (90%—100%) via the deacetylation reaction of the corresponding α,α-diacetyl ketene dithioacetals 1 in the presence of concentrated sulfuric acid. This reaction involves an %in-situ% electrophilic addition-deacetylation mechanism and shows the nucleophilicity of the α-carbon atom in α-oxo ketenedithioacetals. Meanwhile, when the reaction time was prolonged to 22—25 h, the β-keto thiolesters 3a and 3c were produced in good yields.展开更多
As a novel collector, O-isopropyl-N,N-diethyl thionocarbamate(IPDTC) was designed and synthesized for copper-sulfur flotation separation. Density functional theory calculations were performed to investigate the electr...As a novel collector, O-isopropyl-N,N-diethyl thionocarbamate(IPDTC) was designed and synthesized for copper-sulfur flotation separation. Density functional theory calculations were performed to investigate the electronic structures of IPDTC. The results showed that IPDTC had higher energy of the highest occupied molecular orbital but lower electronegativity than O-isopropyl-N-ethyl thionocarbamate(Z-200). It was predicted that IPDTC had strong collection ability according to the reaction energy criteria. Flotation results demonstrated that the collecting ability of IPDTC to chalcopyrite and pyrite was stronger than that of Z-200. Then, the flotation mechanism was analyzed by measurements of surface tension, adsorption capacity, XPS, FTIR and zeta potential. These results indicated that IPDTC could reduce the solution surface tension. The adsorption capacity of IPDTC on chalcopyrite was higher than that on pyrite, consistent with the results of the flotation tests. FTIR, zeta potential and XPS results also demonstrated that IPDTC was strongly absorbed on the chalcopyrite surface by formation of Cu—S—C bonds, but showed a weak affinity on the pyrite surface.展开更多
The surface hydrophobization and flotation of a xanthate−hydroxamate collector toward copper oxide mineral were compared with the combined collectors of xanthate and hydroxamate through water contact angle(WCA)and mic...The surface hydrophobization and flotation of a xanthate−hydroxamate collector toward copper oxide mineral were compared with the combined collectors of xanthate and hydroxamate through water contact angle(WCA)and micro-flotation experiments.The results showed that S-[(2-hydroxyamino)-2-oxoethyl]-O-octyl-dithiocarbonate ester(HAOODE)exhibited stronger hydrophobization and better flotation performance to malachite(Cu2(OH)2CO3)than octyl-hydroxamic acid(OHA)and its combination with S-allyl-O-ethyl xanthate ester(AEXE).To understand the hydrophobic intensification mechanism of HAOODE to malachite,zeta potential,atomic force microscopy(AFM)and XPS measurements were carried out.The results recommended that malachite chemisorbed HAOODE to form Cu—HAOODE complexes in which the hydroxamate—(O,O)—Cu and—O—C(—S—Cu)—S—configurations co-existed.The co-adsorption of HAOODE’s hetero-difunctional groups was more stable than the single-functionalgroup adsorption of OHA and AEXE,which produced the“loop”structure and intensified the self-assembly alignment of HAOODE on malachite surfaces.In addition,the“h”shape steric orientation of the double hydrophobic groups in HAOODE facilitated stronger hydrophobization toward malachite than the“line”or“V”hydrophobic carbon chains of OHA or AEXE.Thus,HAOODE achieved the preferable flotation recovery of malachite particles in comparison with OHA and AEXE.展开更多
Various amino acid esters were reacted with different isothiocyanates in alkaline Al2O3 at room temperature for 1 h affording thiohydantoins in moderate to excellent yields.
文摘The α-acetyl ketene dithioacetals 2, which bear various alkylthio groups, are a kind of important intermediates in organic synthesis. In this paper, dithioacetals 2 were prepared in very high yields (90%—100%) via the deacetylation reaction of the corresponding α,α-diacetyl ketene dithioacetals 1 in the presence of concentrated sulfuric acid. This reaction involves an %in-situ% electrophilic addition-deacetylation mechanism and shows the nucleophilicity of the α-carbon atom in α-oxo ketenedithioacetals. Meanwhile, when the reaction time was prolonged to 22—25 h, the β-keto thiolesters 3a and 3c were produced in good yields.
基金financial supports from the Open Foundation of State Key Laboratory of Mineral Processing,China (Nos.BGRIMM-KJSKL-2019-06,BGRIMMKJSKL-2022-13)the Open Fund of State Key Laboratory of Comprehensive Utilization of Low-Grade,China (No.ZJKY2017(B)KFJJ003)。
文摘As a novel collector, O-isopropyl-N,N-diethyl thionocarbamate(IPDTC) was designed and synthesized for copper-sulfur flotation separation. Density functional theory calculations were performed to investigate the electronic structures of IPDTC. The results showed that IPDTC had higher energy of the highest occupied molecular orbital but lower electronegativity than O-isopropyl-N-ethyl thionocarbamate(Z-200). It was predicted that IPDTC had strong collection ability according to the reaction energy criteria. Flotation results demonstrated that the collecting ability of IPDTC to chalcopyrite and pyrite was stronger than that of Z-200. Then, the flotation mechanism was analyzed by measurements of surface tension, adsorption capacity, XPS, FTIR and zeta potential. These results indicated that IPDTC could reduce the solution surface tension. The adsorption capacity of IPDTC on chalcopyrite was higher than that on pyrite, consistent with the results of the flotation tests. FTIR, zeta potential and XPS results also demonstrated that IPDTC was strongly absorbed on the chalcopyrite surface by formation of Cu—S—C bonds, but showed a weak affinity on the pyrite surface.
基金Project(51474253)supported by the National Natural Science Foundation of China。
文摘The surface hydrophobization and flotation of a xanthate−hydroxamate collector toward copper oxide mineral were compared with the combined collectors of xanthate and hydroxamate through water contact angle(WCA)and micro-flotation experiments.The results showed that S-[(2-hydroxyamino)-2-oxoethyl]-O-octyl-dithiocarbonate ester(HAOODE)exhibited stronger hydrophobization and better flotation performance to malachite(Cu2(OH)2CO3)than octyl-hydroxamic acid(OHA)and its combination with S-allyl-O-ethyl xanthate ester(AEXE).To understand the hydrophobic intensification mechanism of HAOODE to malachite,zeta potential,atomic force microscopy(AFM)and XPS measurements were carried out.The results recommended that malachite chemisorbed HAOODE to form Cu—HAOODE complexes in which the hydroxamate—(O,O)—Cu and—O—C(—S—Cu)—S—configurations co-existed.The co-adsorption of HAOODE’s hetero-difunctional groups was more stable than the single-functionalgroup adsorption of OHA and AEXE,which produced the“loop”structure and intensified the self-assembly alignment of HAOODE on malachite surfaces.In addition,the“h”shape steric orientation of the double hydrophobic groups in HAOODE facilitated stronger hydrophobization toward malachite than the“line”or“V”hydrophobic carbon chains of OHA or AEXE.Thus,HAOODE achieved the preferable flotation recovery of malachite particles in comparison with OHA and AEXE.
基金National Natural Science Foundation of China(Grant No.20972005)
文摘Various amino acid esters were reacted with different isothiocyanates in alkaline Al2O3 at room temperature for 1 h affording thiohydantoins in moderate to excellent yields.
