高效除草剂环酯草醚的合成工艺优化
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摘要
目标化合物是高效水稻苗后广谱除草剂,为解决生产过程中环境污染问题,以硫代乙酸钾为硫代试剂,以2-乙酰基-6-硝基苯甲酸为原料,经硼氢化钠还原、硫代、双硫键还原和亲核取代合成目标化合物。考察了各步反应溶剂、反应温度、反应时间和原料配比等因素对反应收率的影响,并通过合成工艺优化和正交试验得到目标化合物最佳合成工艺条件。反应总收率达71. 3%,产品纯度为99. 1%,其结构经1HNMR、13CNMR、熔点和HR-MS(ESI)确证。该工艺路线安全、简便,适合工业化生产。
The target compound is high-efficiency rice seedling broad-spectrum herbicide.Potassium thioacetate was used as a thio reagent to solve the environmental pollution in the production process.Using 2-acetyl-6-nitrobenzoic acid as a raw material,the target compound was obtained via the successive reaction of borohydride reduction,thio reaction,disulfide bond reduction,nucleophilic substitution.The effect of yield for each step was investigated such as the reaction solvent,reaction temperature,reaction time and the ratio of raw materials and other factors.Synthetic process optimization and orthogonal experiments were used to screen the optimal synthesis conditions of the target compound.The total reaction yield and the product purity were 71. 3% and 99. 1%respectively.The structure of the target compound was confirmed by1 HNMR,13 CNMR,melting point and HR-MS(ESI).The new technology is safe,simple and suitable for industrial production.
The target compound is high-efficiency rice seedling broad-spectrum herbicide.Potassium thioacetate was used as a thio reagent to solve the environmental pollution in the production process.Using 2-acetyl-6-nitrobenzoic acid as a raw material,the target compound was obtained via the successive reaction of borohydride reduction,thio reaction,disulfide bond reduction,nucleophilic substitution.The effect of yield for each step was investigated such as the reaction solvent,reaction temperature,reaction time and the ratio of raw materials and other factors.Synthetic process optimization and orthogonal experiments were used to screen the optimal synthesis conditions of the target compound.The total reaction yield and the product purity were 71. 3% and 99. 1%respectively.The structure of the target compound was confirmed by1 HNMR,13 CNMR,melting point and HR-MS(ESI).The new technology is safe,simple and suitable for industrial production.
引文
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[8]LI Z H,YANG A J,XIA W T,et al. An innovative andconcise approach to synthesize pyriftalid[J]. Org. Prep.Proced.Int.,2017,49(4):382-388.
[9]KYTE A B,JONES-PARRY R,WHITTAKER D. Acetylnitrite:a useful nitrosating reagent[J].J.Chem.Soc.Chem.Commun.,1982,(1):74-75.
[10]苗丽,蔡鹏,来虎钦,等. 3-甲基-7-硝基苯酞的合成[J].浙江工业大学学报,2013,41(2):195-198.
[11]刘安昌,李高峰,夏强,等.新型除草剂环酯草醚的合成研究[J].世界农药,2010,32(5):19-21.
[2]SCHEIBLICH S,GERINGER M,KIND B. Bis-pyrimi-dylpyrazolinones-a new class of acetohydroxy-acid syn-thase(AHAS)inhibitor[J]. Pest Manag. Sci.,1999,55(6):636-638.
[3]LI K J,QU R Y,LIU Y C,et al. Design,synthesis,andherbicidal activity of pyrimidine-biphenyl hybrids as novelacetohydroxyacid synthase inhibitors[J]. J. Agr. FoodChem.,2018,66(15):3 773-3 782.
[4]付启明,欧晓明.巴斯夫除草剂嘧啶肟草醚拟在美国上市[J].农药研究与应用,2009,13(3):52.
[5]LTHY C,ZONDLER H,RAPOLD T,et al.7-(4,6-Dim-ethoxypyrimidinyl)oxy-and-thiophthalides as novel herbi-cides:Part 1 CGA 279 233:a new grass-killer for rice[J].Pest Manag.Sci.,2001,57(3):205-224.
[6]程志明.除草剂嘧草醚的开发[J].世界农药,2003,25(1):1-6.
[7]SCHNYDER A,PASSAFARO M,RAPOLD T.Process forthe preparation of 7-substituted 3-alkyl-3H-isobenzofuran-1-one derivatives:WO 2002EP05 572[P].2001-05-22.
[8]LI Z H,YANG A J,XIA W T,et al. An innovative andconcise approach to synthesize pyriftalid[J]. Org. Prep.Proced.Int.,2017,49(4):382-388.
[9]KYTE A B,JONES-PARRY R,WHITTAKER D. Acetylnitrite:a useful nitrosating reagent[J].J.Chem.Soc.Chem.Commun.,1982,(1):74-75.
[10]苗丽,蔡鹏,来虎钦,等. 3-甲基-7-硝基苯酞的合成[J].浙江工业大学学报,2013,41(2):195-198.
[11]刘安昌,李高峰,夏强,等.新型除草剂环酯草醚的合成研究[J].世界农药,2010,32(5):19-21.
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