Synthesis of 2,4-dichloro-5-fluoropyrimidine and recovery of DMA from waste water

doi:10.11949/j.issn.0438-1157.20141261

Abstract

Abstract: 2,4-Dichloro-5-fluoropyrimidine was prepared by reaction of 5-fluorouracil (5-FU) and phosphorus oxychloride in the presence of N,N-dimethylaniline (DMA) as acid acceptor. The effect of molar ratio of 5-FU to phosphorus oxychloride, molar ratio of 5-FU to N,N-dimethylaniline, reaction temperature and reaction time was investigated. Furthermore, reaction mechanism was discussed. 5-FU and POCl₃ ratio 1:10, 5-FU and DMA ratio 1:1.5, reaction temperature 114℃, reaction time 2 h were the optimum process parameters of synthesizing 2,4-dichloro-5-fluoropyrimidine. Under this process condition, maximum yield of 92.2% of 2,4-dichloro-5-fluoropyrimidine could be obtained. The pH of waste water was then adjusted by adding sodium hydroxide, and the effect of pH on recovery of DMA and yield of by-product disodium hydrogen phosphate was studied. When pH was adjusted to 7, maximum recovery of DMA and maximum yield of by-product disodium hydrogen phosphate could be obtained.

Key words: 5-fluorouracil, acid acceptor, synthesis, waste water, recovery, hydrate

摘要： 使用5-氟尿嘧啶(5-FU)和三氯氧磷(POCl₃)作为原料、N,N-二甲基苯胺(DMA)作为缚酸剂合成2,4-二氯-5-氟嘧啶,系统研究了5-FU与POCl₃的摩尔比、5-FU与DMA的摩尔比、反应温度和反应时间对反应收率的影响,简要阐述该反应机理。反应结束后,向废液中加入NaOH固体对废液进行处理,探讨DMA的回收率和副产物磷酸氢二钠的收率与pH的关系。结果表明,在工艺参数为5-FU与POCl₃的摩尔比为1:10、5-FU与DMA的摩尔比为1:1.5、回流温度114℃、回流时间2 h时,2,4-二氯-5-氟嘧啶的收率为92.2%;通过加入NaOH固体将废液pH调至7,DMA的回收率和副产物磷酸氢二钠的收率都为最大值。

关键词: 5-氟尿嘧啶, 缚酸剂, 合成, 废水, 回收, 水合物

CLC Number:

TQ254.1

FU Yongfeng, GUO Ning, YUN Zhi, SUN Shanshan. Synthesis of 2,4-dichloro-5-fluoropyrimidine and recovery of DMA from waste water[J]. CIESC Journal, 2015, 66(5): 1723-1729.

付永丰, 郭宁, 云志, 孙珊珊. 2,4-二氯-5-氟嘧啶的合成及废液回收处理利用[J]. 化工学报, 2015, 66(5): 1723-1729.

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