CN101270117B - 一种除草剂及其制备方法 - Google Patents
一种除草剂及其制备方法 Download PDFInfo
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- CN101270117B CN101270117B CN2008100113381A CN200810011338A CN101270117B CN 101270117 B CN101270117 B CN 101270117B CN 2008100113381 A CN2008100113381 A CN 2008100113381A CN 200810011338 A CN200810011338 A CN 200810011338A CN 101270117 B CN101270117 B CN 101270117B
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
具有除草活性的苯并噁唑啉酮类化合物及其制备方法,属于除草剂技术及其制备方法领域。含有活性的苯并噁唑啉酮类化合物具有以下化学分子结构通式:式中的X为氯或溴等卤原子;R为甲基或烯丙基等;具有除草活性的苯并噁唑啉酮类化合物的制备方法是以取代苯乙酮为原料,经过缩合、闭环、烷基化等步骤合成中间体3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑;该中间体再经过卤代、硝化、脱甲基、硝基还原、闭环反应,最后进行不同的烷基化反应,即可得到系列具有除草活性的苯并噁唑啉酮类化合物。尤其化合物A8、A9采用150g/hm2或600g/hm2剂量,对狗尾草的除草率为50~80%,对马唐的除草率为45~80%,对苘麻的除草率为75~100%。
Description
技术领域
本发明涉及一种除草剂及其制备方法,也就是说,它主要含有一类具有除草活性的苯并噁唑啉酮类化合物及其制备方法,属于除草剂技术及其制备方法领域。
背景技术
由于人类对环保问题的重视,对农药的毒性及其对环境的影响提出了更高的要求,因此,化学农药的开发研制将进入“超高效、无毒、无污染”的新时期。近几十年来,研究开发了许多新型高效、低毒的除草剂以替代高毒有机磷农药,原卟啉原氧化酶抑制剂类除草剂便是其中的一类。其作用机理是除草剂分子和底物(原卟啉原IX)竞争原卟啉原氧化酶(protox)的活性位点,从而抑制protox的作用使叶绿体中的原卟啉原IX不能被氧化成原卟啉IX,从而会大量积累,从质体中泄漏出来。在细胞质中,原卟啉原IX同样会转化为原卟啉IX,它与氧气和光作用,形成单线态氧,导致脂质过氧化,使细胞死亡。许多公司对这类化合物进行了大量的研究,开发出了很多高效除草剂。例如:
该类除草剂的分子结构中,在苯环上的苯1,2,4-位上均有取代基,2,4-位为卤索,1-位与杂环相连。研究表明,苯环上的2-位为氟,4-位为氯取代的化合物,活性较高。
发明内容
本发明的目的就是在保留化合物活性部分的基础上,改变其它基团,开发一种具有除草活性的除草剂及其制备方法。这种除草剂具有取代吡唑基苯并噁唑酮结构,为取代吡唑基苯并噁唑酮构成的化合物,苯环上1-位连接的五元氮杂环是吡唑环,2,4-位碳原子上的氢原子分别被氟原子、氯原子取代,5,6-位上并上具有不同取代基的噁唑酮环。
一种除草剂,该除草剂具有以下化学分子结构通式:
其中:X为卤素;
R为C1-3的烷烃基或烯丙基。
当X为氯或溴原子时,R=CH3或-CH2-CH=CH2。
除草剂主要含有一类具有除草活性的苯并噁唑啉酮类化合物制备方法是以取代苯乙酮为原料,经过缩合反应、闭环反应、烷基化反应、卤代反应、苯环硝化反应、脱烷基反应、硝基还原反应、再闭环反应等步骤完成的,具体合成路线如下所示:
所合成除草剂A1~A4、A7~A9的具体结构见表1所示。
表1A1~A4、A7~A9的结构
化合物 | X | R |
A1 | H | H |
A2 | Cl | H |
A3 | Br | H |
A4 | H | CH3 |
A7 | H | -CH2CH=CH2 |
A8 | Cl | -CH2CH=CH2 |
A9 | Br | -CH2CH=CH2 |
根据上述的反应式,为获得该除草剂的制备方法,其包括以下步骤:
(1)缩合反应:将原料4-氯-2-氟-5-甲氧基苯乙酮与三氟乙酸乙酯按摩尔比1∶1.1~1∶2.0在质量百分数为25%的甲醇钠存在下,于甲醇、乙醇、乙醚或异丙醚中在室温至回流条件下,反应45分钟~20小时,把所得产物倒入冰盐酸中,过滤、洗涤、干燥,制得缩合产物。
(2)闭环反应:将缩合产物与水合肼按摩尔比1∶2~1∶3在苯、甲苯或乙酸溶剂中,于回流条件下反应30~60分钟,降温,倒入水中、过滤、水洗、干燥,得到闭环产物。
(3)烷基化反应:将闭环产物溶于苯、甲苯或丙酮中,与硫酸二甲酯或碘甲烷按摩尔比1∶1.5~1∶2.5在室温至回流温度下,反应为0.5~8.0小时,反应结束后,反应液用1mol/L氢氧化钠溶液洗涤,水洗、干燥、过滤,蒸出溶剂,得到烷基化产物。
(4)卤代反应:将上述烷基化产物与卤代琥珀酰亚胺按摩尔比为1∶2~1∶3在乙酸或N,N-二甲基甲酰胺溶剂中,于70~110℃反应2~6小时,反应液倒入水中,用乙酸乙酯萃取,有机层水洗、干燥、过滤,蒸出乙酸乙酯,得到固体用乙醇重结晶,得卤代产物。
(5)硝化反应:将上述的烷基化产物或卤代产物溶于溶剂中,在冰水浴下滴加硝化试剂,按摩尔比1∶3~1∶5,0℃至回流温度下反应0.5~5.0小时,将反应液倒入冰水中,过滤、水洗、干燥,将得到固体用乙醇重结晶,制得硝化产物。
(6)脱烷基反应:将硝化产物溶于有机溶剂中,与脱烷基化试剂按摩尔比1∶1.5~1∶3.5,在室温至回流温度下反应0.5~2.0小时,反应液倒入冰盐酸中,分液,水相用有机溶剂萃取,有机相水洗、干燥、过滤,蒸出溶剂,制得脱烷基产物。
(7)硝基还原反应:将脱烷基产物溶于有机溶剂中,加入饱和氯化铵水溶液,再加入还原剂,脱烷基产物与还原剂的摩尔比为1∶4~1∶6,在室温至回流温度下反应2.0~10.0小时,蒸出有机溶剂,过滤,滤液用乙酸乙酯萃取,有机相水洗、干燥、过滤,蒸出乙酸乙酯,得到硝基还原产物。
(8)再闭环反应:将还原产物加到有机溶剂中,与固体光气按摩尔比3∶1在室温至回流温度下,反应1.0~10.0小时,再滴加三乙胺,继续反应0.5h后,反应液倒入水中,分液,有机相用5%碳酸氢钠溶液和水洗涤,干燥、过滤,蒸出有机溶剂,制得再闭环产物。
(9)再烷基化反应:将制得的再闭环产物与烷基化试剂按摩尔比1∶1.1~1∶2,在碳酸钾存在下,在丙酮中室温至回流温度下,反应1.0~4.0小时,制得所述除草剂。
在所述脱烷基反应时,所用的有机溶剂选自二氯甲烷、氯仿或N,二N-二甲基甲酰胺;脱烷基化试剂选自三氟化硼、三溴化硼、无水三氯化铝或浓硫酸。
在所述硝基还原反应时,所用的有机溶剂选自甲苯、甲醇或乙醇;还原剂选自硫化钠、铁粉、锌粉或氯化亚锡。
在所述再闭环合成R=H的除草剂A1~A3反应时,所用的有机溶剂选自甲苯、二氯甲烷、二氯乙烷或N,N-二甲基甲酰胺。
在所述再烷基化反应时,所用的再烷基化试剂选自碘甲烷、硫酸二甲酯或烯丙基溴。
产物的分离提纯既可以采用重结晶的方法(溶剂为甲醇、乙醇、丙醇、乙酸乙酯、乙酸甲酯、石油醚、苯、甲苯、二甲苯、氯仿、二氯甲烷等,或其混合物),也可以采用柱色谱分离的方法。
按照上述方法,合成的除草剂,分析数据如表2所示。
表2A1~A9的物性及分析数据
本发明的有益效果是:这种除草剂及其制备方法,含有活性的除草剂具有以下结构通式:
式中的X为氢、氯或溴等卤原子;R为氢原子、甲基或烯丙基等;除草剂的制备方法是以取代苯乙酮为原料,经过缩合、闭环、烷基化等步骤合成中间体3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑;该中间体再经过卤代、硝化、脱甲基、硝基还原、闭环反应,最后进行不同的烷基化反应,即可得到系列除草剂。尤其除草剂A2、A5、A6、A8、A9采用150g/hm2或600g/hm2剂量,对狗尾草的除草率为50~80%,对马唐的除草率为45~80%,对苘麻的除草率为75~100%。
具体实施方式
实施例1:
(1)缩合反应
(4-氯-2-氟-5-甲氧基苯基)-4,4,4-三氟-1,3-丁二酮的合成:
在250ml三口烧瓶中加入13g4-氯-2-氟-5-甲氧基苯乙酮,60ml甲醇,13.5g三氟乙酸乙酯和26ml质量百分数为25%的甲醇钠/甲醇溶液。升温至回流,反应45min。反应结束后,将反应物倒入含有盐酸的冰水中,抽滤,水洗,干燥,得白色固体18.6g,产率97.2%。m.p.122~123℃;1H NMR(400MHz,CDCl3),δ:3.96(s,3H,OCH3),6.73(s,1H,=CH-),7.27(d,1H,J=10.8Hz,Ph-3-H),7.50(d,1H,J=6.4Hz,Ph-6-H)。
(2)闭环反应
(5)-(4-氯-2-氟-5-甲氧基苯基)-5(3)-三氟甲基吡唑的合成:
在100ml三口烧瓶中加入2g l-(4-氯-2-氟-5-甲氧基苯基)-4,4,4-三氟-1,3-丁二酮,20ml乙酸和1ml质量百分数为80%的水合肼,升温至110℃反应1h。降温,有固体析出,将反应物倒入水中,过滤,水洗,干燥,得淡黄色固体2g,产率100%。m.p.194~198℃;1H NMR(400MHz,CDCl3),δ:3.94(s,3H,OCH3),6.90(s,1H,Pyr-H),7.22(d,1H,J=10.0Hz,Ph-3-H),7.41(d,1H,J=6.0Hz,Ph-6-H)。
(3)甲基化反应
3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑的合成:
在100ml三口烧瓶中加入2g 3(5)-(4-氯-2-氟-5-甲氧基苯基)-5(3)-三氟甲基吡唑,20ml甲苯和2ml硫酸二甲酯。升温至回流反应6h。反应结束后,反应液用1mol/L氢氧化钠溶液10ml洗,水洗,无水硫酸镁干燥,过滤,蒸出甲苯。加入少量乙醇重结晶,得到了白色固体1.9g,产率90.5%。m.p.115.5-116℃;1HNMR(400MHz,CDCl3),δ:3.94(s,3H,OCH3),4.04(s,3H,Pyr-CH3),7.02(d,1H,J=3.0Hz,Pyr-H),7.17(d,1H,J=8.8Hz,Ph-3-H),7.55(d,1H,J=5.8Hz,Ph-6-H)。
(4)卤代反应
4-氯-3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑的合成:
在250ml三口烧瓶中加入3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑15g、N-氯代琥珀酰亚胺20g和N,N-二甲基甲酰胺125ml,升温至80℃反应2h,将反应液倒入水中,30ml乙酸乙酯萃取两遍。合并有机层,15ml水洗两遍,无水硫酸镁干燥,过滤,蒸出乙酸乙酯,得白色固体。乙醇重结晶,得到了白色晶体14.0g,产率83.2%。m.p.72-72.5℃;1H NMR(400MHz,CDCl3),δ:3.91(s,3H,OCH3),4.07(s,3H,Pyr-CH3),7.03(d,1H,J=6.4Hz,Ph-6-H),7.26(d,1H,J=9.2Hz,Ph-3-H)。
(5)硝化反应
3-(4-氯-6-氟-3-甲氧基-2-硝基苯基)-1-甲基-5-三氟甲基-1H-吡唑的合成:
在100mL三口烧瓶中,加入8g 3-(4-氯-2-氟-5-甲氧基苯基)-1-甲基-5-三氟甲基-1H-吡唑,25mL冰乙酸,冰水浴下滴加27mL混酸(V(乙酐)∶V(硝酸)=2∶1)。保持温度继续反应2h,然后将反应液倒入冰水中,过滤,水洗,干燥,得红棕色固体。少量乙醇中重结晶,得淡黄色固体3.7g,收率83%,m.p.94~96℃。
(6)脱烷基反应
6-氯-4-氟-3-(1-甲基-5-三氟甲基-1H-吡唑-3-基)-2-硝基苯酚的合成:
在100mL三口烧瓶中加入3.7g 3-(4-氯-6-氟-3-甲氧基-2-硝基苯基)-1-甲基-5-三氟甲基-1H-吡唑和3.4g三氯化铝,再加入60mL二氯甲烷作为溶剂。常温下搅拌反应2h。反应完毕后将反应液倒入冰盐酸中,分液,水相用二氯甲烷萃取,合并有机相,有机相水洗后无水硫酸镁干燥,过滤,蒸出二氯甲烷,得黄色固体3.5g,产率~100%,m.p.94~97℃。
(7)硝基还原反应
2-氨基-6-氯-4-氟-3-(1-甲基-5-三氟甲基-1H-吡唑-3-基)苯酚的合成:
在氮气保护下,向100mL三口烧瓶中加入700mg 6-氯-4-氟-3-(1-甲基-5-三氟甲基-1H-吡唑-3-基)-2-硝基苯酚、25mL甲醇、20ml饱和氯化铵水溶液及720mg铁粉,机械搅拌50℃下反应6h,冷却,蒸出甲醇,过滤,滤液用乙酸乙酯萃取3次,合并有机相,有机相水洗后无水硫酸镁干燥,过滤,蒸出乙酸乙酯。得到棕色固体450mg,产率75%,m.p.87~89℃。
(8)再闭环反应
7-氯-5-氟-4-(1-甲基-5-三氟甲基-1H-吡唑-3-基)苯并噁唑-2(3H)-酮(化合物A1)的合成:
在50mL单口瓶中,加入210mg三光气,再加入3mL甲苯溶解。取500mg2-氨基-6-氯-4-氟-3-(5-三氟甲基-1-甲基-1H-吡唑-3-基)苯酚溶于18mL甲苯,然后在搅拌下滴加于单口瓶中。常温反应1h后,滴加0.5ml三乙胺后继续反应0.5h。反应完毕将反应液倒入水中,分液。有机相先后用5%碳酸氢钠溶液和水洗涤,无水硫酸镁干燥,过滤,蒸出甲苯,得灰色粉末320mg,产率60%。
类似方法合成除草剂A2、A3。
实施例2:7-氯-5-氟-4-(1-甲基-5-三氟甲基-1H-吡唑-3-基)-3-甲基苯并噁唑-2(3H)-酮(化合物A4)和3-烯丙基-7-氯-5-氟-4-(1-甲基-5-三氟甲基-1H-吡唑-3-基)苯并噁唑-2(3H)-酮(化合物A7)的合成:
在25mL小烧瓶中,加入7-氯-5-氟-4-(1-甲基-5-三氟甲基-1H-吡唑-3-基)苯并噁唑-2(3H)-酮150mg和10ml丙酮,再加入适量无水碳酸钾粉末,滴加1ml硫酸二甲脂或0.3ml烯丙基溴,常温下反应4h,反应完毕将反应液倒入水中,用10mL乙酸乙脂萃取三次,有机相合并后水洗,无水硫酸镁干燥,过滤,蒸出乙酸乙酯,得化合物A4为灰白色固体。得化合物A7为白色固体。
类似方法合成除草剂A5、A6、A8、A9。
实施例3:除草活性测试
用少量丙酮溶解A1~A9除草剂原药,按设计剂量,用含有0.1%吐温80的静置自来水稀释,制得待测化合物溶液。选取生长良好、叶期一致的杂草(马唐、狗尾草、苘麻,2-3叶期),用作物喷雾机进行喷雾处理,喷液量600L/hm2,处理后于通风处阴干,然后转移至温室进行正常培养。以清水处理为空白对照。处理后10天参比空白对照,目测调查各化合物对杂草的除草活性,100为全部杀死,0为无效。测试结果见表3所示。
表3除草活性测试结果
*.除草剂的使用剂量(g a.i./hm2)
Claims (8)
2.据权利要求1所述的除草剂,其特征在于:当X为氯或溴原子时,R=CH3或-CH2-CH=CHa。
3.如权利要求1所述的除草剂的制备方法,其特征在于:它包括以下步骤:
(1)缩合反应:将原料4-氯-2-氟-5-甲氧基苯乙酮与三氟乙酸乙酯按摩尔比1∶1.1~1∶2.0在质量百分数为25%的甲醇钠存在下,于甲醇、乙醇、乙醚或异丙醚中在室温至回流条件下,反应45分钟~20小时,把所得产物倒入冰盐酸中,过滤、洗涤、干燥,制得缩合产物;
(2)闭环反应:将缩合产物与水合肼按摩尔比1∶2~1∶3在苯、甲苯或乙酸溶剂中,于回流条件下反应30~60分钟,降温,倒入水中、过滤、水洗、干燥,得到闭环产物;
(3)烷基化反应:将闭环产物溶于苯、甲苯或丙酮中,与硫酸二甲酯或碘甲烷按摩尔比1∶1.5~1∶2.5在室温至回流温度下,反应为0.5~8.0小时,反应结束后,反应液用1mol/L氢氧化钠溶液洗涤,水洗、干燥、过滤,蒸出溶剂,得到烷基化产物;
(4)卤代反应:将上述烷基化产物与卤代琥珀酰亚胺按摩尔比为1∶2~1∶3在乙酸或N,N-二甲基甲酰胺溶剂中,于70~110℃反应2~6小时,反应液倒入水中,用乙酸乙酯萃取,有机层水洗、干燥、过滤,蒸出乙酸乙酯,得到固体用乙醇重结晶,得卤代产物;
(5)硝化反应:将上述的卤代产物溶于溶剂中,在冰水浴下滴加硝化试剂,按摩尔比1∶3~1∶5,0℃至回流温度下反应0.5~5.0小时,将反应液倒入冰水中,过滤、水洗、干燥,将得到固体用乙醇重结晶,制得硝化产物;
(6)脱烷基反应:将硝化产物溶于有机溶剂中,与脱烷基化试剂按摩尔比1∶1.5~1∶3.5,在室温至回流温度下反应0.5~2.0小时,反应液倒入冰盐酸中,分液,水相用有机溶剂萃取,有机相水洗、干燥、过滤,蒸出溶剂,制得脱烷基产物;
(7)硝基还原反应:将脱烷基产物溶于有机溶剂中,加入饱和氯化铵水溶液,再加入还原剂,脱烷基产物与还原剂的摩尔比为1∶4~1∶6,在室温至回流温度下反应2.0~10.0小时,蒸出有机溶剂,过滤,滤液用乙酸乙酯萃取,有机相水洗、干燥、过滤,蒸出乙酸乙酯,得到硝基还原产物;
(8)再闭环反应:将还原产物加到有机溶剂中,与固体光气按摩尔比3∶1在室温至回流温度下,反应1.0~10.0小时,再滴加三乙胺,继续反应0.5h后,反应液倒入水中,分液,有机相用5%碳酸氢钠溶液和水洗涤,干燥、过滤,蒸出有机溶剂,制得再闭环产物;
(9)再烷基化反应:将制得的再闭环产物与烷基化试剂按摩尔比1∶1.1~1∶2,在碳酸钾存在下,在丙酮中室温至回流温度下,反应1.0~4.0小时,制得所述除草剂。
4.据权利要求3所述的制备方法,其特征在于:在所述硝化反应时,所用的溶剂选自浓硫酸、冰醋酸、二氯甲烷或硝基苯;硝化试剂选自浓硝酸、发烟硝酸、硝酸/浓硫酸或硝酸/乙酸酐。
5.据权利要求3所述的制备方法,其特征在于:在所述脱烷基反应时,所用的有机溶剂选自二氯甲烷、氯仿或N,N-二甲基甲酰胺;脱烷基化试剂选自三氟化硼、三溴化硼、无水三氯化铝或浓硫酸。
6.据权利要求3所述的制备方法,其特征在于:在所述硝基还原反应时,所用的有机溶剂选自甲苯、甲醇或乙醇;还原剂选自硫化钠、铁粉、锌粉或氯化亚锡。
7.据权利要求3所述的制备方法,其特征在于:在所述再闭环反应时,所用的有机溶剂选自甲苯、二氯甲烷、二氯乙烷或N,N-二甲基甲酰胺。
8.据权利要求3所述的制备方法,其特征在于:在所述再烷基化反应时,所用的烷基化试剂选自碘甲烷、硫酸二甲酯或烯丙基溴。
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CN-1302298A 2001.07.04 |
周宇涵,苗蔚荣,程侣柏.取代苯基吡唑类化合物合成及其除草活性.大连理工大学学报43 5.2003,43(5),582-585. |
周宇涵,苗蔚荣,程侣柏.取代苯基吡唑类化合物合成及其除草活性.大连理工大学学报43 5.2003,43(5),582-585. * |
朱聪伟等.三光气在羰基化环合反应中的研究.化学试剂28 7.2006,28(7),421-422. |
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李荣坡,周伟澄.噁唑烷酮类抗菌剂的合成.中国医药工业杂志34 6.2003,34(6),302-309. |
李荣坡,周伟澄.噁唑烷酮类抗菌剂的合成.中国医药工业杂志34 6.2003,34(6),302-309. * |
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