Ⅰ. One-pot α-Fluorination Of Acetop-henones With Et₃N·3HFⅡ. Selective Oxidations Of Benzyl Alcohols With1,3-Dibromo-5,5-Dimethylhydantoin

Part IThe first chapter of this paper relates to the research on one-pot α-fluori nation of acetophenones with EtsN3HF.a-FI uoroacetophenones are i mportant kind of fluorine-containing building blocks, which are wildly used in the synthesis of medicines and pesticides. Tri ethyl amine trihydrofluoride(Et3N·3HF) as a kind of safe, cheap nucleophilic fluori nation reagent, is easily prepared and used with good activity. In this chapter, we researched on the one-pot α-fluori nation of acetophenones with Et3N·3HF as fluori nation reagent. Firstly, we i mproved the reaction-condi ti on of a-bromi nati ons of1,3-di bromo-5,5-di methyl hy dantoin and acetophenones, which are catalytic by silica gel. The new reactions used less amount of DBDMH, hanppened at lower temperature, and got a little higher yields Then the products of these a-bromi nati ons were directly fluorinated used Et3N·3HF without separation and purification, and we got a-f I uoroacetophenones in good yields.This reaction is a new synthesis method of a-f I uoroacetophenones in one-pot, which is easy to operate and used safe, cheap fluori nati on reagent.Part ⅡThe second chapter of thi s paper relates to the research on selective oxi dati ons of benzyl alcohols with1,3-di bromo-5,5-di methyl hydantoin.1,3-dibromo-5,5-dimethylhydantoin(DBDMH) which is wildly used as sanitizers and bromide reagent in industry, has some oxi dative. In this chapter, we firstly researched the oxidative of DBDMH using benzyl alcohols as substrate to research. From the research we found that DBDMH could directly oxide benzyl alcohol to methyl benzoate in methanol in room temperature without catalysts. Then we researched the selectivity of the oxidations with DBDMH. We found that benzal dehyde coul d be selective got as the oxidation products i n aproti c solvent. Thi s reaction has fast rate and also happens in room temperature without catalysts By using different solvents, we found the methods of selective oxidations of benzyl aloohols with1,3-dibromo-5,5-dimethylhydantoin, which have mild reaction-conditions, good selectivity and high yields. Furthermore, the experimental operations are easy and convenient, so we think the method will have a good application prospect...