2,4-二氯-5-氟嘧啶的合成及废液回收处理利用

doi:10.11949/j.issn.0438-1157.20141261

化工学报 ›› 2015, Vol. 66 ›› Issue (5): 1723-1729.DOI: 10.11949/j.issn.0438-1157.20141261

• 催化、动力学与反应器 • 上一篇下一篇

2,4-二氯-5-氟嘧啶的合成及废液回收处理利用

付永丰¹, 郭宁², 云志¹, 孙珊珊²

1 南京工业大学化学化工学院, 江苏南京 210009;
2 齐鲁工业大学化学与制药工程学院, 山东济南 250353

收稿日期:2014-08-20 修回日期:2014-12-31 出版日期:2015-05-05 发布日期:2015-05-05
通讯作者: 云志

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

FU Yongfeng¹, GUO Ning², YUN Zhi¹, SUN Shanshan²

1 School of Chemistry and Chemical Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, China;
2 School of Chemistry and Pharmaceutical Engineering, Qilu University of Technology, Jinan 250353, Shandong, China

Received:2014-08-20 Revised:2014-12-31 Online:2015-05-05 Published:2015-05-05

摘要/Abstract

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

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

中图分类号:

TQ254.1

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.

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.

参考文献 22

[1]	Moon B S, Skim A Y, Lee K C, Lee H J, An J I. Synthesis of F-18 labeled capecitabine using [18F] F2 gas as a tumor imaging agent [J]. Bull. Korean Chem. Soc., 2005, 26 (11): 1865-1868
[2]	Ray S J, Richardson K. Triazole antifungal agents [P]. EP 0440372. 1991-08-07
[3]	John C H, Ben C G, Timothy C J. Herbicidal alkoxy-1,2,4-triazolo [1,5-c]pyrimidine-2-sulfonamides [P]. US 5163995. 1992-11-17
[4]	Prystas M, Sorm F. Nucleic acids components and their analogues. (LⅫ):Synthesis of anomeric 1-(2-deoxy-D-ribofuranosyl) derivatives of 5-fluorouracil and 5-nitrouracil [J]. Collect. Collect. Czech. Chem. Commun., 1965, 30 (6): 1900-1912
[5]	Undheim K, Gacek M. Some derivatives of 5-fluoropyrimidine [J]. Acta Chemica Scandinavica, 1969, 23: 294-299
[6]	Gershon H, Grefig A T. A study of the chlorination of pyrimidines with phosphorus oxychloride in the presence of N,N-dimethylaniline [J]. J. Heterocyclic Chem., 1984, 21:1161-1167
[7]	Robert D, Essex F. Processes and intermediates for deoxyfluorocytidine [P]. US 3040026. 1962-06-19
[8]	Paegle R A, Plata M G, Lidak M Y, Popel Y Y. Synthesis and properties of N-(2-chloro-5-fluoro-4-pyrimidyl)-and N-(2-ethylthio-5-fluoro-4-pyridmidyl)-substituted amino acids [J]. Chemistry of Heterocyclic Compounds, 1971, 7: 237-239
[9]	Fu Aiqing. Method for preparing 2,4-dichloro-5-fluoropyrimidine compound [P]. CN 102070536. 2011-05-25
[10]	Hashimoto A, Iwasaki K, Nakasugi N, Nakajima M, Yagi O. Degradation pathways of trichloroethylene and 1,1,1-trichloroethane by Mycobacterium sp. TA27 [J]. Bioscience, Biotechnology and Biochemistry, 2002, 66 (2): 385-390
[11]	Yang Yiyan (杨义燕), Su Haijia (苏海佳), Qin Wei (秦炜), Li Ruili (李芮丽), Dai Youyuan (戴猷元). Study on extraction of aniline from industrial effluents by chemical complexation [J]. Chemical Industry and Engineering Progress (化工进展), 1995, (2): 24-27
[12]	Ren Nanqi (任南琪), Zhou Xianjiao (周显娇), Guo Wanqian (郭婉茜), Yang Shanshan (杨姗姗). A review on treatment methods of dye wastewater [J]. CIESC Journal (化工学报), 2013, 64 (1): 84-94
[13]	Pyne A, Chatterjee K, Suryanarayanan R. Crystalline to amorphous transition of disodium hydrogen phosphate during primary drying [J]. Pharmaceutical Research, 2003, 20 (5): 802-803
[14]	Herman G, Anthony T G. Pyrimidines. 7. A study of the chlorination of pyrimidines with phosphorus of pyrimidines with phosphorus oxychloride in the presence of N,N-dimethylaniline [J]. J. Heterocyclic Chem., 1984, 21 (4): 1161-1167
[15]	Renzo D, Senkichi N, Yoshiaki T, Nobuhiko N, Yasuo O, Takeo N. Activity of fluorine containing pyrimidinylsulfanilamide derivatives [J]. Yakugaku Zasshi, 1967, 87: 419-429
[16]	Armarego W L F, Christina L L C. Purification of Laboratory Chemicals [M]. 5th ed. Amsterdam: Elsevier, 2003: 213
[17]	Zhang Yang (张洋), Shen Yuhui (沈裕辉). Research on the mechanism of POCl3 in the Niementowski reaction [J]. Chemical Reagents (化学试剂), 2009, 31 (1): 69-70
[18]	Jie J L. Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications [M]. Rong Guobin (荣国斌), trans. 4th ed. Beijing: Science Press, 2011: 48-49, 558-559
[19]	Manfred M, Hans B, Bahman S, Matthias K. Erzeugung und Ionisationsmuster der iso (valenz)elektronischen Verbindungen ClP (=O)2 und ClP (=S)2 [J]. Angew. Chem., 1989, 101 (10): 1378-1381
[20]	Willeams D H, Fleming L. Spectroscopic Methods in Orgnic Chemistry [M]. Wang Jianbo (王建波), Shi Weifeng (施卫峰), trans. 5th ed. Beijing: Beijing University Press, 2001:23-48, 49-134
[21]	Anderson R J, Bendell D J, Groundwater P W. Organic Spectroscopic Analysis [M]. Tang Chuanjiang (唐川江), trans. Beijing: China Textile & Apparel Press, 2004: 24-111
[22]	Jiang Chuanhai (姜传海), Yang Chuanzheng (杨传铮). Technology and Application of X-ray Diffraction (X射线衍射技术及其应用)[M]. Shanghai: East China University of Science and Technology Press, 2010: 62-75

2,4-二氯-5-氟嘧啶的合成及废液回收处理利用

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

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