Oxidation Of Alcohols Catalyzed By Iron Complexes

The thesis consists of four parts as followings:Part I: ReviewsThis part reviewed the progress in the catalytic oxidation of alcohols including homogeneous oxidation, inorganic/organic biphase catalytic oxidation and liquid/solid heterogeneous catalytic oxidation systems. Then the thesis reviewed the metal-catalyzed oxidation particularly from the following eleven subsections, such as (i) ruthenium complex catalyzed system; (ii) palladium complex catalyzed system; (iii) copper (I) complex catalyzed system; (iv) iron complex catalyzed system; (v) cobalt complex catalyzed system; (vi) vanadium catalyzed system; (vii) osmium and the co-metal catalyzed system; (viii) chromium and its oxides system; (ix) aluminium oxides system; (x) multiple-metal catalyzed system and (xi) other transition metal catalyzed system, and a short conclusion was also proposed based on all of the reviews.Part II: The catalytic properties of FeCl₃ in the oxidation of alcoholsThe catalytic activities of FeCl₃ for the oxidation of 4-methoxybenzyl alcohol were investigated and the optimum conditions for the oxidation were proposed respectively. Then the oxidation of other alcohols with FeCl₃ and 30%H₂O₂ under the optimum conditions was carried out according to the former reaction conditions. The results show that FeCl₃ is a promising catalyst for the oxidation of alcohols. With the catalysis of FeCl₃, most of the benzalcohol derivatives as well as long-chained aliphatic alcohols can be oxidized to the corresponding carbonyl compounds with high conversion (about 100% for most of the alcohols) and selectivity (ca. 100%) at 80°C. The results also reveal that the catalysts shows better catalytic activity for the oxidation of aromatic alcohols which contain smaller and electron-attracting groups in the benzene rings. Otherwise, the catalytic activity decreases with the increasing of the chain length of the alcohols for the oxidation of aliphatic alcohols. And a short discussion was carried out according to the oxidation results.Part III: The catalytic properties of the low molecular weight complex TNTD-Fe(III) in the oxidation of alcoholsThe catalytic activities of iron-containing complex named TNTD-Fe(III) for the oxidation of 4-nitrobenzyl alcohol were investigated and the optimum conditions for the oxidation were proposed respectively. Then the oxidation of other alcohols with TNTD-Fe(III) and 30%H₂O₂ under the optimum conditions was carried out according to the former reaction conditions. The results show that iron-containing complex TNTD-Fe(III) is a good catalyst for the oxidation of alcohols. In this oxidation system, most of the benzalcohol derivatives as well as long-chained aliphatic alcohols can be oxidized to the corresponding carbonyl compounds with high conversion (about 100% for most of the alcohols) and selectivity (ca. 100%).Part IV: The catalytic properties of the dendrimer supported PAMAMSA(1G-6G) -Fe(III) complexes in the oxidation of alcoholsThe catalytic activities of dendrtic complexes named PAMAMSA(lG-6G)-Fe(III) (where G=generation) for the oxidation of benzyl alcohols were investigated and the optimum conditions for the oxidation were proposed respectively. Then the oxidation of other alcohols with PAMAMSA(2G)-Fe(III) and 3G%H₂O₂ under the optimum conditions was carried out according to the former reaction conditions. The results show that PAMAMSA(2G)-Fe(III) is also an excellent catalyst for the oxidation of alcohols. With the catalysis of the complex PAMAMSA(2G)-Fe(III), most of the benzalcohol derivatives as well as long- chained aliphatic alcohols can be oxidized to the corresponding carbonyl compounds with high conversion (about 100% for most of the alcohols) and selectivity (ca. 100%) at room temperature.