| On reviewing of the synthesis of water-soluble phosphine ligands and the developments in the hydroformylation of higher olefins,based on the concept of Thermoregulated Phase-transfer Catalysis(TRPTC)',a novel water-soluble bidentate ligand PEO-DPPPA containing P N atoms has been prepared via the ethoxylation of 2-(diphenylphosphino)phenylamine with ethylene oxide at the starting material of 2-chlorobenzoamine. Another amino-substituted nonionic water-soluble ligand PEO-DPPSA has also been prepared by the ethoxylation of 4-(diphenylphosphino)phenylsulfamide with ethylene oxide. The structures of PEO-DPPPA and PEO-DPPSA are following:The catalytic system of PEO-DPPPA/Rh complex formed in situ by PEO-DPPPA and RhCl3 has been successfully applied to the aqueous-organic two-phase hydroformylation of 1-decene. The effects of solvents,temperature,total pressure,P/Rh in mol ratio and 1-decene/Rh in mol ratio are investigated and discussed in detail. Under the reaction conditions of 120,5.0MPa(CO/H2=l),P/Rh=4,l-decene/Rh=1000 and reacted for 5h,the conversion of 1-decene and the yield of aldehyde are 99.5% and 99.0% respectively. The average turnover frequency(TOF) are up to 198h~',the ratio normal to iso-aldehyde is 0.62. Recycling text shows that the conversion of olefin and the yield of aldehyde remain higher than 94% when the catalyst is used for 20 times.The catalytic properties of PEO-DPPSA/Rh have been tested in the reaction system of aqueous-organic two-phase hydroformylation of 1-decene. Under the reaction conditions of 100,5.0MPa(CO/H2=l),P/Rh=12,l-decene/Rh=1000and reacted for 5h,the conversion of 1-decene and the yield of aldehyde are 98.3% and 97.0% respectively. The average turnover frequency(TOF) are up to 194h-1,the ratio normal to iso-aldehyde is 0.66. Recycling text shows that the conversion of olefin and the yield of aldehyde remain higher than 90% when the catalyst is used for 3 times. From the forth time of catalyst recycling the yield of aldehyde starts to descend to 83.0%.For the first time,the process of the aqueous/organic two-phase catalytic system has been developed in the hydroformylation of higher branched olefins. The main study is on the aqueous/organic two-phase hydroformylation of tripropene over PEO-DPPPA/Rh complex catalyst,and the effects of several conditions on the reaction have been discussed. Under the reaction conditions of 130,6.0MPa(CO/H2=l),P/Rh=8,l-decene/Rh=300 and reacted for lOh,the conversion of tripropene and the yield of aldehyde are 83.1% and 81.5% respectively. The average turnover frequency(TOF) are up to 194h'',the ratio normal to iso-aldehyde is 0.66. Recycling text under above conditions shows that the effect is not so good as that in the reaction of 1-decene. Instead of PEO-DPPPA,several other nonionic water-soluble ligands have been utilized in this process under the same condictions. The results show that the activity of PEO-DPPPA is the highest.A bidentate ligand containing P,N,named as 2-(2-diphenylphosphino)phenyl-oxazoline DPPPO,has been synthesized via two routes different from the method reported. The total yield of DPPPO amount to 31% in one route via a intermediate of 2-(2-bromophenyl)oxazoline is higher than that of reported. The structures of main products have been confirmed by IR,'H-NMR,31P-NMR and MS.The one-pot condensation reaction of amino alcohol with the different groups(-H,-Br,-PPh2) substituted benzonitrile on the ortho-position under catalysis with ZnCl2 has been investigated. The results show that the steric effect of the substituted groups has an important influence on the yield of this reaction,that is,the more strong the steric effect is,the lower the yield gets.The one-pot condensation of N-( {3 -hydroxyethyl)-o-bromobenzamide to corresponding oxaozoline performed by using SOC12 has been studied in detail. The experimental results show that the reaction temperature has a great influenceon the oxazoline yield. The oxazoline yield drop obviously with the rising of the reaction temperature and at room temperature...
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