潘飞,张伟,鲁墨弘,李明时

• 1:常州大学石油化工学院江苏省绿色催化材料与技术重点实验室

摘要(Abstract)：

以对二氯苯为起始原料,经过氧化氢氧化羟基化反应、二氧化碳羧基化反应,绿色合成了麦草畏中间体3,6-二氯水杨酸。重点研究了以V_2O_5为催化剂,过氧化氢为氧化剂,催化对二氯苯羟基化合成2,5-二氯苯酚的反应,考察了不同溶剂、主催化剂用量、助催化剂用量、氧化剂用量、反应温度、以及反应时间对羟基化反应收率的影响,确定了羟基化适宜反应条件为:n(对二氯苯):n(五氧化二钒):n(草酸):n(磷酸):n(过氧化氢)=0.1:0.00125:0.01:0.25:0.5,于30℃下反应10 h。2,5-二氯苯酚收率达39.3%,反应的总收率为31.3%。产物结构经过了1H-NMR,13C-NMR和GC-MS确定。所用方法原料廉价易得、反应条件温和、操作简便。

关键词(KeyWords)： 对二氯苯;羟基化反应;2,5-二氯苯酚;3,6-二氯水杨酸

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金(21307009);; 江苏高校优势学科建设工程资助项目

作者(Author): 潘飞,张伟,鲁墨弘,李明时

参考文献(References)：

• [1]ZHANG Si-gui(章思规).Practical manual of fine chemicals(实用精细化学品手册)[M].Beijing(北京):Chemical Industry Press(化学工业出版社),1996.
• [2]TIAN Lin(田琳),TAN Hai-jun(谭海军).Synthetic reviews on Dicamba and its intermediates(麦草畏及其中间体的合成评述)[J].Modern Agrochemicals(现代农药).2011,5(10):12-15.
• [3]CAO Guang-hong(曹广宏).Research advances in 2,5-dichlorophenol synthesis technology(2,5-二氯苯酚生产工艺述评)[J].Hubei Chemical Industry(湖北化工),1991(2):30-32.
• [4]Sandoz L T D.Preparation of 2,5-dichlorophenol:US,4,670,610[P].1987-06-02.
• [5]Sidney B R.2-methoxy-3,6-dichlorobenzoates:US,3,013,054[P].1961-12-12.
• [6]ZHANG Xiao-bo(章小波),JIANG Yong-xiang(蒋永祥),TANG Miao-rong(汤淼荣).The synthesis of herbicides Dicamba(安息香酸系除草剂--麦草畏的合成)[J].Agrochemicals(农药),2002,41(11):13-14.
• [7]JIANG Yong-xiang(蒋永祥).The synthetic technology of antidepressant nefazodone intermediate-2-phenoxy-ethanamine and herbicides Dicamba(抗抑郁药奈法唑酮中间体及麦草畏的合成)[D].Hangzhou(杭州):Zhejiang University(浙江大学),2003.
• [8]Pittsburgh Plate Glass Company.Trichlorophenoxy alkanoic acid free of chlorinated diben-zo-p-dioxins:US,4,326,882[P].1982-04-27.
• [9]Noelting E,Kopp E.Zur kenntniss des amido-p-dichlorbenzols[J].Berichte der Deutschen Chemischen Gesellschaft,1905,38(3):3506-3515.
• [10]Jiangsu Shenghua pesticide Co Ltd(江苏生花农药有限公司).Improved Dicamba process for diazotizat-ion reaction(改进的麦草畏生产的重氮化工艺):CN,1830943[P].2006-09-13.
• [11]ZHANG Yong(张咏),LU Min(陆敏).Study on the synthesis of Dicamba(麦草畏合成工艺的究)[J].Agrochemicals(农药),2002,41(7):15-17.
• [12]Novartis A G.Process for the hydroxylation of 1,4-dichlorobenzene:WO,9,847,843[P].1998-10-29.
• [13]Sandoz L T D.Oxidation process:US,5,648,562[P].1997-07-15.
• [14]Syngenta Participations Ag.Oxidation process:US,6,274,776[P].2001-08-14.
• [15]Syngenta Participations Ag.Oxidation process:US,6,323,377[P].2001-11-27.
• [16]Syngenta Participations Ag.Oxidation process:US,6,586,624[P].2003-07-01.
• [17]XU Wen-jun(徐文俊),JING Li(景丽),ZHANG Fu-min(张富民),et al.Kinetics of hydroxylation of benzene to phenol with hydrogen peroxide over organic molybdovanadophosphoric heteropolyacid salt catalysts(钼钒磷杂多酸有机盐催化下苯与过氧化氢羟基化制苯酚的动力学)[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2012,26(4):624-628.
• [18]ZHANG Jing-chang(张敬畅),ZHANG Xin-fang(张信芳),CAO Wei-liang(曹维良),et al.Study on hydroxylation of phenol using iron-based composite oxides as catalysts(负载型铁基复合氧化物催化苯酚羟基化的研究)[J].Molecule Catalysis(分子催化),2003,17(1):40-45.
• [19]Hussain S,Swaroop P A,Kifayatulla M.Process for the preparation of 2,5-dichlorophenol of 99%purity:IN,150341[P].1982-09-18.
• [20]JANG Yi-wen(蒋亦文).Study on Kolbc-Schmitt reaction mechanism of dichlorophenol in carbonation(二氯苯酚羧化的Kolbe-Schmitt反应机理研究)[D].Shanghai(上海):East China University of Science and Technology(华东理工大学),2011.
• [21]Kolbe H.On the synthesis of salieylic acid[J].Liebigs Alln,1860,113:125-127.
• [22]Galat Alexander.The preparation of 2,4,5-trichlorophenoxyacetic acid(2,4,5-T)[J].Journal of the American Chemical Society,1952,74(15):3890-3891.
• [23]ZHANG Yong(张咏).Study on the preparation of 3,6-dichlorosalicylic acid(3,6-二氯水杨酸合成工艺的研究)[J].Technology and Testing(化工时刊),2001,15(9):27-31.