季膦盐和钨酸钠催化下双氧水溶液清洁氧化醇和烯烃的研究

Oxidation of alcohol and olefins using hydrogen peroxide solution as oxidant under the catalysis of quaternary phosphonium and sodium tungstate

首先合成1-羟甲基苯并三唑、1-氯甲基苯并三唑、1,4-二溴丁烷单季膦盐等几种中间体,通过熔点、红外谱图等手段对其进行了结构表征;进而合成1-三苯基膦甲基苯并三唑、双季膦盐和ω-苯并三唑基丁基季膦盐等3种催化剂.其次,对自制的3种催化剂辅助过氧化氢氧化环己醇、苯甲醇、环己烯的性能进行了评价.即利用各季膦盐与钨酸钠构成三种催化体系,在无有机溶剂条件下,实现了30%过氧化氢水溶液清洁催化环己醇、苯甲醇、环己烯为环己酮、苯甲醛(或苯甲酸)、己二酸;考察了3种催化剂分别在3种体系下的催化性能.结果表明:对于环己醇的氧化1-三苯基膦甲基苯并三唑催化剂的效果最好;对于环己烯的氧化仍是1-三苯基膦甲基苯并三唑催化剂的效果最好;对于苯甲醇的氧化ω-苯并三唑基丁基季膦盐的催化效果最好.研究发现:在苯甲醇氧化时,随催化剂种类、体系和过氧化氢加入量的不同,可以选择性地氧化成苯甲醛或苯甲酸.在环己烯氧化时,随催化剂加量、过氧化氢加入量的不同和实验室的条件等的限制选择性很大.

several kinds of intermediates:1-hydroxymethyl benzotriazole,1-chloromethyl benzotriazole and 1,4-dibromo butane phosphonium salts are synthesized.Their structure is characterized by their melting point and infrared spectrometry.Then 1-benzotriazolyl methyl phosphonium salts,biquaternary phosphonium salts and omega-benzotriazolyl butyl phosphonium salts are synthesized too.Without organic solvent,cyclohexanol,benzyl alcohol and cyclohexene are oxidized into cyclohexanone,benzaldehyde(or benzoic acid) and adipic acids separately using the hydrogen peroxide solution of 30% under three catalysis systems composed of sodium tungstate and quaternary phosphonium salts.It is shown that the maximum yields of adipic acids,benzoic acid,benzaldehyde and cyclohexanone are 32.4%,28.96%,62.3%,and 62.45% respectively.The catalysis performance of the three catalysts in the three catalysis systems are studied,and it is shown that 1-benzotriazolyl methyl phosphonium salts have the best catalysis result to the oxidation of cyclohexanol and cyclohexene,and omega-benzotriazolyl butyl phosphonium salts have the best catalysis result to the oxidation of benzyl alcohol.It is also shown that benzyl alcohol can be oxidized into benzaldehyde or benzoic acid according to different kind of catalysts,different catalysis systems and different dosage of hydrogen peroxide,and the oxidization of cyclohexene varies a lot with the dosage of the catalysts and hydrogen peroxide and experimental conditions.