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以1,1,2,3-四氯丙烯(1)为原料,合成了多种具有工业价值的氟氯化合物。首先,以叔胺-2HF为氟化试剂,亲核取代1得到3-氟-1,1,2-三氯丙烯(2);随后在AlCl3催化下异构2得到3-氟-2,3,3-三氯丙烯(3),在FeCl3或KCl催化下异构3得到1-氟-1,2,3-三氯丙烯(4);最后在铬基氟化催化剂催化下,气相氟化2高转化地得到2-氯-3,3,3-三氟丙烯(5),在SbCl5催化下,液相氟化3一步得到2-氯-1,1,1,2-四氟丙烷(6)。本文所合成的化合物5和6均是合成新一代环保型制冷剂HFO-1234yf的重要中间体。
A variety of industrially valuable chlorofluorocarbons were synthesized from 1,1,2,3-tetrachloropropene (1). First, 3-fluoro-1,1,2-trichloropropene (2) is obtained by nucleophilic substitution of tertiary amine-2HF as a fluorinating reagent to isomerize 2 under the catalysis of AlCl 3 to obtain 3-fluoro-2,3 , 3-trichloropropene (3), isomerization 3 under FeCl3 or KCl catalysis to obtain 1-fluoro-1,2,3-trichloropropene (4); finally catalyzed by a chromium-based fluorination catalyst, 2 obtained by high conversion of 2-chloro-3,3,3-trifluoropropene (5), SbCl5 catalysis, the liquid phase fluorination 3 to give 2-chloro-1,1,1,2-tetrafluoropropane 6). Compounds 5 and 6 synthesized in this paper are both important intermediates in the synthesis of a new generation of environmentally friendly refrigerants HFO-1234yf.