CN113845449B - 一种制备硝磺草酮类除草剂的方法 - Google Patents
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Abstract
本发明属于化工领域,具体涉及一种制备硝磺草酮类除草剂的方法。将1,3‑环己二酮和酰氯A在路易斯酸和有机溶剂存在下反应,制得目标产物硝磺草酮。本发明反应温和,操作简单,无含氰废水产生,且收率高,产品纯度好。
Description
技术领域
本发明属于化工领域,具体涉及一种制备硝磺草酮类除草剂的方法。
背景技术
硝磺草酮是对羟基苯基丙酮酸双氧化酶(HPPD)抑制剂类除草剂,主要用于防除玉米田杂草,具有除草谱广、环境相容性好、对哺乳动物和水生生物毒性低等特点,市场需求量大,应用前景广阔。
专利CN106565556、US4780127等报道了制备硝磺草酮的方法,其中均有含氰化合物的参与。专利CN1272837、CN101735119、CN105712912、CN110818601、CN110256308等公开的方法中,用三氮唑、嘌呤或四甲基胍等作为转位剂,但经实验验证这些方法存在烯醇酯水解、收率不高等问题。
专利CN105693569公开了在路易斯酸存在下制备3-[4-(甲基磺酰基)-2-氯苯甲酰基]双环[3.2.1]-辛烷-2,4-二酮的方法,但按照该专利方法制备硝磺草酮时发现反应放出酸性气体、出现大量粘稠物、不易搅拌,后处理时需要加入大量盐酸来溶解反应中产生的粘稠固体,并且有黑色难溶物质影响收率和纯度,同时会伴随副反应产生。
进而需要一种反应温和,容易操作,且副产少,转化率、收率和产品纯度高的硝磺草酮的制备方法。
发明内容
本发明目的在于提供一种合成工艺简单、收率高,不使用高毒转位剂的硝磺草酮的制备方法。
为实现上述目的,本发明采用技术方案为:
一种制备硝磺草酮类除草剂的方法,将1,3-环己二酮及其类似物和A1-A9所示的酰氯,在路易斯酸和有机溶剂存在下反应,制得目标产物。
所述1,3-环己二酮的类似物为A1-A9所示的任意一个酰氯,
进一步的说,将2-硝基-4-甲基磺酰基苯甲酰氯加入到路易斯酸和溶剂的悬浮液中,溶解后得溶解液,将1,3-环己二酮及其类似物溶于溶剂中滴入上述溶解液中,滴完后在0℃至室温下反应0.5-5小时,再于室温-60℃下反应2-8小时,即得目标产物硝磺草酮类除草剂。
所述溶解液为:在零下10℃至室温下,将2-硝基-4-甲基磺酰基苯甲酰氯加入到路易斯酸和溶剂的悬浮液中,酰氯溶解后,即得溶解液,待用。
所述1,3-环己二酮溶液滴完之前反应体系的温度为0-20℃;滴完1,3-环己二酮溶液后于10℃至室温下反应1-2小时,再于35-45℃下反应2-5小时。
所述反应完成后滴加水,然后于室温至溶剂回流温度下搅拌至固体全部溶解,冷却至室温后经分液、萃取、有机相脱溶得粗产品,最后经纯化得到硝磺草酮类除草剂。
所述的溶剂选自二氯甲烷、1,2-二氯乙烷或氯仿;所述的路易斯酸选自三氯化铝,三氯化铝的用量(摩尔数)为1,3-环己二酮的3-5倍;2-硝基-4-甲基磺酰基苯甲酰氯、1,3-环己二酮、路易斯酸的摩尔比为1:1-1.2:3-5。
所述的溶剂选自1,2-二氯乙烷;2-硝基-4-甲基磺酰基苯甲酰氯、1,3-环己二酮、路易斯酸的摩尔比为1:1-1.2:3-3.5。
所述反应完成后在冰浴条件下滴加水,滴加完于30-60℃下搅拌至固体全部溶解。
进一步的说,反应完成后滴加水,然后于室温至回流温度下搅拌至固体全部溶解,冷却至室温后分液、水相用有机溶剂萃取2次,有机相合并、水洗、干燥、脱溶得粗产品,将粗产品溶于氢氧化钾水溶液中,可适量地加入一种或几种有机溶剂,再用盐酸调至酸性,析出的固体经过滤、水洗、干燥得硝磺草酮产品。溶有三氯化铝的水相可加入碱,生成氢氧化铝沉淀,回收利用。
硝磺草酮类除草剂包括硝磺草酮(mesotrione)、磺草酮(sulcotrione)、环磺酮(tembotrione)、磺苯呋草酮(tefuryltrione)、fenquinotrione、lancotrione、喹草酮、甲基喹草酮和二氯喹啉草酮等
反应所用的2-硝基-4-甲基磺酰基苯甲酰氯可按照CN105712912等文献提供的方法制备,其他原料或试剂均有市售。
本发明所具有的优点:
本发明通过路易斯酸在温和条件下使1,3-环己二酮和2-硝基-4-甲基磺酰基苯甲酰氯反应合成硝磺草酮,反应过程中不会生成大量深色粘稠固体,无大量酸性气体放出;并且后处理不用加入大量酸,也不需要含氰转位剂、不用处理烯醇酯的中间过程;同时,本发明反应温和,容易操作,且副产少,转化率、收率和产品纯度高。
具体实施方式
以下结合实例对本发明的具体实施方式做进一步说明,应当指出的是,此处所描述的具体实施方式只是为了说明和解释本发明,并不局限于本发明。
实施例1
将8.3g三氯化铝(0.062mol)加入到250mL三口瓶中(带搅拌、温度计和冷凝管),加入80mL1,2-二氯乙烷搅拌,冰浴下加入2-硝基-4-甲基磺酰基苯甲酰氯5.27g(0.02mol),约10分钟后酰氯全部溶解,滴加2.24g1,3-环己二酮(0.02mol)的70mL1,2-二氯乙烷溶液,约15分钟滴完,撤去冰浴,室温下反应1小时,再于40℃下保温反应4小时。HPLC检测反应完成,将反应液降至室温,并在冰浴下滴加50mL水,滴完50℃下搅拌至固体全部溶解,冷却、分层,分出水相用80mL1,2-二氯乙烷分两次萃取,有机相合并,用30mL冷水洗涤,用无水硫酸镁干燥,脱溶得粗产品。将粗品溶于2.24g氢氧化钾的50mL水溶液中,再用盐酸调节pH值至1.5左右,55±2℃搅拌1小时,冷却,过滤固体,用冷水洗涤,干燥,得硝磺草酮产品6.35g,纯度98.1%,收率约为91.9%。
实施例2
将8.3g三氯化铝(0.062mol)加入到250mL三口瓶中(带搅拌、温度计和冷凝管),加入80mL二氯甲烷搅拌,冰浴下加入2-硝基-4-甲基磺酰基苯甲酰氯5.27g(0.02mol),约10分钟后酰氯全部溶解,滴加2.24g1,3-环己二酮(0.02mol)的70mL二氯甲烷溶液,约15分钟滴完,撤去冰浴,室温下反应1小时,再于35-40℃下保温反应4小时。HPLC检测反应完成,将反应液降至室温,并在冰浴下滴加50mL水,滴完50℃下搅拌至固体全部溶解,冷却、分层,分出水相用80mL二氯甲烷分两次萃取,有机相合并,用30mL冷水洗涤,用无水硫酸镁干燥,脱溶得粗产品。将粗品溶于2.24g氢氧化钾的50mL水溶液中,再用盐酸调节pH值至1.5左右,55±3℃搅拌1小时,冷却,过滤固体,用冷水洗涤,干燥,得硝磺草酮产品6.45g,纯度97.8%,收率约为93.0%。
对比实施例1
将8.3g三氯化铝(0.062mol)加入到250mL三口瓶中(带搅拌、温度计和冷凝管),加入150mL1,2-二氯乙烷搅拌,然后加入2-硝基-4-甲基磺酰基苯甲酰氯5.27g(0.02mol),继续搅拌30分钟。然后加入2.24g1,3-环己二酮(0.02mol),加热反应器,使内部反应温度为58℃,体系中有气体放出,并出现块状粘稠固体。继续搅拌3小时,反应完成,将反应液降至室温,并在冰浴下搅拌滴加28g浓盐酸和50mL水的溶液,分层,水相用50mL1,2-二氯乙烷萃取,有机相合并,脱溶得粗品。粗品中加入25毫升甲醇和4毫升6摩尔/升的盐酸,60±2℃下搅拌1小时,室温搅拌过夜,过滤固体,固体溶于2.24g氢氧化钾的50mL水溶液中,再用盐酸调节pH值至1.5左右,冷却,过滤固体,用冷水洗涤,干燥,得硝磺草酮产品4.30,纯度96.5%,收率约为60.0%。
对比实施例2
将5.34g三氯化铝(0.04mol)加入到250mL三口瓶中(带搅拌、温度计和冷凝管),加入150mL1,2-二氯乙烷搅拌,然后加入2-硝基-4-甲基磺酰基苯甲酰氯5.27g(0.02mol),继续搅拌30分钟。然后加入2.24g1,3-环己二酮(0.02mol),加热反应器,使内部反应温度为58℃,保温反应3小时,HPLC显示无产物生成。
Claims (5)
1.一种制备硝磺草酮的方法,其特征在于:将1,3-环己二酮和2-硝基-4-甲基磺酰基苯甲酰氯,在路易斯酸和有机溶剂存在下反应,制得目标产物;
具体为:将2-硝基-4-甲基磺酰基苯甲酰氯加入到路易斯酸和溶剂的悬浮液中,溶解后得溶解液,将1,3-环己二酮溶于溶剂中滴入上述溶解液中,滴完后在0℃至室温下反应0.5-5小时,再于室温-60℃下反应2-8小时,后处理并纯化即得目标产物硝磺草酮;
所述反应完成后滴加水,然后于室温至溶剂回流温度下搅拌至固体全部溶解,冷却至室温后经分液、萃取、有机相脱溶得粗产品,最后经纯化得到硝磺草酮;
所述的溶剂选自二氯甲烷、1,2-二氯乙烷或氯仿;所述的路易斯酸选自三氯化铝;2-硝基-4-甲基磺酰基苯甲酰氯、1,3-环己二酮、路易斯酸的摩尔比为1:1-1.2:3-5。
2.根据权利要求1所述的制备硝磺草酮的方法,其特征在于:所述溶解液为:在零下10℃至室温下,将2-硝基-4-甲基磺酰基苯甲酰氯加入到路易斯酸和溶剂的悬浮液中,酰氯溶解后,即得溶解液,待用。
3.根据权利要求1所述的制备硝磺草酮的方法,其特征在于:所述1,3-环己二酮溶液滴完之前反应体系的温度为0-20℃;滴完1,3-环己二酮溶液后于10℃至室温下反应1-2小时,再于35-45℃下反应2-5小时。
4.根据权利要求1所述的制备硝磺草酮的方法,其特征在于:所述的溶剂选自1,2-二氯乙烷;2-硝基-4-甲基磺酰基苯甲酰氯、1,3-环己二酮、路易斯酸的摩尔比为1:1-1.2:3-3.5。
5.根据权利要求1所述的制备硝磺草酮的方法,其特征在于:所述反应完成后在冰浴条件下滴加水,滴加完于30-60℃下搅拌至固体全部溶解。
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