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Study on the Reaction Mechanism and Synthesis of Derivatives of CF3CCl3

Author: LiuZhiZheng
Tutor: ChenZhiRong
School: Zhejiang University
Course: Applied Chemistry
Keywords: CF3COCl CF3COOH CHCl2C（OCH2CH3）3 synthesis density functional theory reaction mechanism
CLC: TQ222.2
Type: Master's thesis
Year: 2012
Downloads: 22
Quote: 0
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Abstract


Trifluoro acetyl chloride (CF3COCl. TFAC) and trifluoro acetic acid (CF3COOH, TFA) are a kind of important aliphatic fluorine-containing intermediates. They are mainly used to synthesize surfactants, material aids, new medicine, pesticides and so on. Orthodichloroacetic acid triethyl ester (CHCl2C(OCH2CH3)3) is an ortho halogenated acetic acid ester which can be used as a chemical intermediate of medicine, dye and organic synthesis. The purpose of this paper is to prepare them with1,1,1-trifluoro-2,2,2-trichloroethane (CF3CCl3) by new process and shed light on the reaction mechanism by experiments and theoretical calculations.Firstly, CF3COCI was prepared by the reaction of CF3CCl3with SO3. The optimal operation conditions of preparing CF3COCI were confirmed as the following:the reaction temperature was65℃, the mole ratio of SO3and CF3CCl3was1.1:1, the concentration of catalyst and sulfuric acid was1%and2%respectively. Then we studied the hydrolysis process of CF3COCI to make CF3COOH.Secondly, CHCl2C(OCH2CH3)3was prepared by the reaction of CF3CCl3and CH3CH2ONa/CH3CH2OH solution in the autocave. The optimistic reaction conditions were as follows:the molar ratio of CH3CH2ONa to CF3CCl3was5.5:1, the reaction temperature and time were140℃and9h respectively. This novel synthetic method is characterized by simple operation and mild reaction conditions that is suitable for industrial production.Lastly, the reaction mechanism of preparation of CF3COCI and CHCl2C(OCH2CH3)3were studied with the density functional theory (DFT) at the (u)B3LYP level. The results showed that the reaction mechanism of preparing CF3COCl was the free radical chain reaction path as the following: O2S(OHg·)2was generated under heat condition, causing CF3CCl3to produce CF3CCl2free radical which reacted with SO3leading to the formation of CF3CCl2OSO2decomposing into CF3COCI and·SO2Cl.Then the·SO2Cl free radical triggered CF3CCl3to regenerate CF3CCl2which recycled the free radical chain growth reaction. Mercury salts were initiators in this reaction. The reaction mechanism of preparing CHCl2C(OCH2CH3)3was as follows:CF3CCl3reacted with ethoxy anion to produce CF3CHCl2firstly. Then CF3CHCl2reacted with ethoxy anion to form different substituted products of ortho-dichloroacetic acid. The details of this procedure were show as following:the hydrogen atom of CF3CHCl2was seized by ethoxy anion to produce CF3CCl2which occurred defl-uorination reaction leading to the formation of CF2=CCl2. Then it reacted with ethoxy anion to form carbon anion which got hydrogen from CH3CH2OH to produce CF2OCH2CH3CHCl2. Different substituted products of ortho-dichloroacetic acid would take similar reactions as the above way. The current calculations confirm the conclusions of experimental observations well.

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CLC: > Industrial Technology > Chemical Industry > Basic Organic Chemistry Industry > The production of aliphatic compounds ( acyclic compounds) > Halogenated derivatives of aliphatic hydrocarbons > Saturated lipid hydrocarbon halogenated derivatives
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