OBJECTIVE To achieve a protected disaccharide galactopyranosyl(α1→2) glucopyranoside fragment with a 1,2-cis galactosyl linkage and protected groups easily selectively deprotected.METHODS Through multiple protecting and coupling protocol,methyl 3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-α-D-galactopyranosyl-(1→2)-3,4,6-tri-O-benzoyl-α-D-glucopyranoside(11) was synthesized with D-galactose and D-glucose as raw materials.RESULTS Methyl 3,4,6-tri-O-benzoyl-α-D-glucopyranoside was achieved via selective acetylation,benzoylation,debenzylidenation,benzoylation and selective deacetylation of methyl 4,6-O-benzylidene-α-D-glucopyranoside from D-glucose.A donor isopropyl 3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-1-thio-β-D-galactopyranoside from D-galactose and an acceptor methyl 3,4,6-tri-O-benzoyl-α-D-glucopyranoside were coupled to obtain methyl 3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-α-D-galactopyranosyl-(1→2)-3,4,6-tri-O-benzoyl-α-D-glucopyranoside and methyl 3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-β-D-galactopyranosyl-(1→2)-3,4,6-tri-O-benzoyl-α-D-glucopyranoside,and the stereoselective ratio of α-galactosyl linkage to β-galactosyl linkage was 3∶1.All products were characterized with NMR,MS etc.CONCLUSION The protected disaccharide Gal(α1→2) Glc fragment 3-O-allyl-2-O-benzoyl-4,6-O-benzylidene-α-D-galactopyranosyl-(1→2)-3,4,6-tri-O-benzoyl-α-D-glucopyranoside was stereoselectively synthesized for the first time.
A novel copper extractant 5-decylsalicylaldoxime is synthesized with the use of a cheap mixture by-product,5-decylsalicylaldoxime,from the petrochemical industry.The optimal condition is,n(decylphenol)∶n(magnesium)∶n(paraformaldehyde)=1∶0.65∶2.8,reaction time 5 h for the formylation reaction and n(decylphenol)∶n(hydroxylamine hydrochloride)=1∶1,reaction time 1 h for the oximation reaction.Under this condition,the yield of the desired product reaches to 75.9%(based on decylphenol) with 99.0% purity(determined by GC).The structure is elucidated by MS,NMR and EA analysis.It is indicated by the comparison with the M5640 and M5774 that the extraction performance of the product is of high copper load capability(6.36 g/L),good copper selectivity over iron(β=1 340),the extracting and stripping balance time are short,the extracting rate is more than 98% and the stripping extracting rate is more than 90% through only one stage.
以廉价的工业副产物混合癸烯和次膦酸钠反应,在常压下合成了二癸基次膦酸,分离产率达99.8%,产物纯度>98%.萃取实验表明,二癸基次膦酸对镍/钻分离的选择性要好于Cyanex 272,对镍和钻的萃取率和反萃率均大于96%;同时,对钻等金属离子,可实现对低pH浸出液的直接萃取.