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1、会计学1工业有机合成工业有机合成22. can be made by the oxidation reactionsROHRCHORCOHOOCOHOCOHOROOHRCNEpoxy-compoundCyano-compound第1页/共21页33. The general features of the oxidation reactions1)The oxidizing agentsThe gas phase oxygen O2 cheaper, without the instrument damage, but lower oxidizing ability need catalyti
2、c.Oxygen atom O generated from the chemical oxidizing agents, high oxidizing-abilities, high selection, mild reaction conditions, but high cost.第2页/共21页42) Strong heat releasing reactions3) Unconverted reactionX4) Multi-reaction ways and with by-reactions In order to obtained the target oxidized com
3、pound, the suitable way must be selected第3页/共21页5The air is flowed into the organic compound in liquid phase under the action of catalytic, then the compound is oxidized, this kind of reaction has been called the air liquid phase oxidation reaction u 9.2 Air liquid phase oxidation reactionsDefinitio
4、n for the reactionrequirementA: special reactor:air-flowing-style reactorB: catalytic (soluble in the organic liquid)第4页/共21页6Some organic compounds O2Automatic reactThe reaction very slowIncreasing the reaction Catalytic or initiation agent 第5页/共21页7The automatic oxidationTypical free radical chain
5、-style reactionB: Chain transfer C: Chain terminationA: Chain initiation第6页/共21页81. The chain initiationRHheat or ray radiationR+HRHR+H+Mn+ M(n-1)+RHR+HX+X第7页/共21页92. The Chain transferR+O2ROOROO+RHROOH第8页/共21页103. The chain terminationROO+RROORR+RRR第9页/共21页11n 1. Initiation agents and catalytic1) +
6、 initiation agent the organic compound to be oxidized easy2) + catalytic ( the transitional metal ion, such as: Co2+ , Mn2+, Fe3+, V5+ etc.) the activation energy of the organic compound to be reduced 第10页/共21页122. The influence of the oxidized organic compounds structureThe organic compounds C-H bo
7、nds to be broken are relative to the energy of these bonds The energy order as follows:The third C-H the second C-H the first C-H, thus , the oxidation first occur at the third C atom.CHCH3CH3OCCH3CH3+H第11页/共21页133.The influence of the anti-reactive (阻化)agentsThe anti-reactive agents can react with
8、the free radicals to form the stable compounds, and to result the chain termination; and few quantity of the agents can also make the oxidation process slowing down. 第12页/共21页14The stronger anti-reactive agents including:RCHCH2OHRNH2OOROO+OHROOH+O a: phenolic; b: amine;c: quinone;d: alkenesuch as:第1
9、3页/共21页15 4. The influence of the degree of the oxidation (氧化深度)For most of the automatic oxidation, particularly to synthesize organic peroxides, aldehydes and ketones:In order to overcome this problem, the conversation rate should be kept at lower level, as the result the oxidation could be with a
10、 higher reaction speed and a higher selective.with the conversation rate (转化率) increasingthe by-products (containing the anti-reactive agents) increasedthe oxidation speeds slowed downthe by-reaction can also cause the oxidized compound to be decomposed further.第14页/共21页16Although the conversation r
11、ate on-one-way is unlikely higher, but the higher selective could be kept, and the unreacted raw material could also to be re-used circularly, therefore, the general productivity is higher. on special situation, for the oxidation with some stable oxidized products,such as: carboxylic acid (羧酸) 第15页/
12、共21页17Benzoic acid as the food additive, intermediate of dyes, drugs and perfumes etc pay a very important role in the fine chemical industry, the common way to synthesis this compound to employ toluene and air :+CH3COOH1.5 O2Co(Ac)21MPa, 150-1700C第16页/共21页18The industrial chemical process of synthesis benzoic acid 第17页/共21页191)CH31 The oxidation reactorpre-heated 2) AirTo be pressed3) Co(Ac)2from 7The o
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