Ru(PPh_3)Cl_2催化的苄醇氧化反应研究
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摘要
以Ru(PPh_3)Cl_2为催化剂,取代苄醇为原料,在O_2氛围中利用分子氧进行选择性氧化,合成了12个芳香醛衍生物(2a~2l),其结构经~1H NMR,~(13)C NMR和IR确证。以4-甲氧基苯甲醛(2b)的合成为例,研究了催化剂、反应温度、溶剂和催化剂用量对2产率的影响。结果表明:在最优反应条件[1 1 mmol,5 mmol%Ru(PPh_3)Cl_2,1,2-二氯乙烷2 m L,于90℃反应6 h]下,2a~2l产率75%~97%。
Twelve aromatic aldehyde derivatives( 2 a ~ 2 l) were synthesized from substituted benzyl alcohols,using Ru( PPh_3)Cl_2 as catalyst in the O_2 atmosphere. The structures were confirmed by ~1 H NMR,~(13) C NMR and IR. Taking 2 b as an example,the effects of catalyst,temperature,solvent and the equivalent of catalyst on the yield of 2 were studied. The results showed that under the optimum conditions[1 1 mmol,5 mmol% Ru( PPh_3)Cl_2,1,2-dichloroethane 2 mL,reaction at 90 ℃ for6 h],2 a ~ 2 l were achieved with the yield of 75% ~ 97%.
Twelve aromatic aldehyde derivatives( 2 a ~ 2 l) were synthesized from substituted benzyl alcohols,using Ru( PPh_3)Cl_2 as catalyst in the O_2 atmosphere. The structures were confirmed by ~1 H NMR,~(13) C NMR and IR. Taking 2 b as an example,the effects of catalyst,temperature,solvent and the equivalent of catalyst on the yield of 2 were studied. The results showed that under the optimum conditions[1 1 mmol,5 mmol% Ru( PPh_3)Cl_2,1,2-dichloroethane 2 mL,reaction at 90 ℃ for6 h],2 a ~ 2 l were achieved with the yield of 75% ~ 97%.
引文
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[3]ENACHE D I,EDWARDS J K,LANDON P,et al.Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/Ti O2catalysts[J].Catalysis Letters,2005,311(1):362-365.
[4]BACKVALL J E.Modern oxidation methods[M].Weinheim:Wiley-VCH,2010.
[5]TOJO G,FERNANDEZ M.Oxidation of alcohols to aldehydes and ketones[J].Chinese Chemical Letters,2006,23(7):801-804.
[6]LUZZIO A F,GUZIEC JR S F.Recent applications of oxochromiumamine complexes as oxidants in organic synthesis.A review[J].Organic Preparations and Procedures International,1988,20(6):533-584.
[7]TAYLOR R J K,REID M,FOOT J,et al.Tandem oxidation processes using manganese dioxide:Discovery,applications,and current studies[J].Accounts of Chemical Research,2005,38(11):851-869.
[8]UYANIK M,ISHIHARA K.Hypervalent iodine-mediated oxidation of alcohols[J].Chemical Communications,2009,16(16):2086-2099.
[9]MAAYAN G,WARD M D,KIRSHENBAUM K.Folded biomimetic oligomers for enantioselective catalysis[J].Proceedings of the National Academy of Sciences of the United States of America,2009,106(33):13679-13684.
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[11]GIAGOU T,MEYER M P.Mechanism of the Swern oxidation:Significant deviations from transition state theory[J].Journal of Organic Chemistry,2010,75(23):8088-8099.
[12]YIN J,GALLIS C E,CHISHOLM J D.Tandem oxidation/halogenation of aryl allylic alcohols under Moffatt-Swern conditions[J].Journal of Organic Chemistry,2007,72(18):7054-7057.
[13]TSUCHIYA D,TABATA M,MORIYAMA K,et al.Efficient Swern oxidation and Corey-Kim oxidation with ion-supported methyl sulfoxides and methyl sulfides[J].Tetrahedron,2012,68(34):6849-6855.
[14]JUDY-AZAR A R,MOHEBBI S.A novel magnetic hybrid nanomaterial as a highly efficient and selective catalyst for alcohol oxidation based on new Schiff base complexes of transition metal ions[J].Journal of Molecular Catalysis A:Chemical,2015,397:158-165.
[15]LIU Y,XIE A,LI J,et al.Heterocycle-substituted tetrazole ligands for copper-catalysed aerobic oxidation of alcohols[J].Tetrahedron,2014,70(52):9791-9796.
[16]AZIZI S N,TILAMI S E.Cu-modified analcime as a catalyst for oxidation of benzyl alcohol:Experimental and theoretical[J].Microporous&Mesoporous Materials,2013,167(5):89-93.
[17]FARSANI M R,YADOLLAHI B.Synthesis,characterization and catalytic performance of a Fe polyoxometalate/silica composite in the oxidation of alcohols with hydrogen peroxide[J].Journal of Molecular Catalysis A:Chemical,2014,392(15):8-15.
[18]HEIDARNEZHAD A,ZAMANI F.Chromium containing Fe3O4/polyacrylonitrile-ethylenediamine as a magnetically recoverable catalyst for alcohol oxidation[J].Catalysis Communications,2015,60:105-109.
[19]BESSON M,GALLEZOT P.Selective oxidation of alcohols and aldehydes on metal catalysts[J].Catalysis Today,2000,57(1):127-141.
[20]ISHII Y,SAKAGUCHI S,IWAHAMA T.Innovation of hydrocarbon oxidation with molecular oxygen and related reactions[J].Advanced Synthesis&Catalysis,2001,343(5):393-427.
[21]MORI K,HARA T,MIZUGAKI T,et al.Hydroxyapatite-supported palladium nanoclusters:A highly active heterogeneous catalyst for selective oxidation of alcohols by use of molecular oxygen[J].Journal of the American Chemical Society,2004,126(34):10657-10666.
[22]MA H,XU J,ZHANG Q,et al.Selective oxidation of ethylbenzene by a biomimetic combination:Hemin and N-hydroxyphthalimide(NHPI)[J].Catalysis Communications,2007,8(1):27-30.