CN115322159B - (r)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物及其应用 - Google Patents
(r)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物及其应用 Download PDFInfo
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 title claims abstract description 17
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 6
- 239000001301 oxygen Substances 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
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- 239000004009 herbicide Substances 0.000 claims abstract description 12
- QMNUDYFKZYBWQX-UHFFFAOYSA-N 1H-quinazolin-4-one Chemical compound C1=CC=C2C(=O)N=CNC2=C1 QMNUDYFKZYBWQX-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims description 7
- 235000001602 Digitaria X umfolozi Nutrition 0.000 claims description 5
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 3
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
- C07D239/96—Two oxygen atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P13/00—Herbicides; Algicides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
本发明涉及一种(R)‑2‑[4‑((喹唑啉‑4‑酮)‑2‑氧基)苯氧基]丙酸酯衍生物的合成及应用。该类化合物的结构通式为(I),R和R1如权利要求所定义。以各种取代的邻氨基苯甲酸和甲基异硫氰酸酯为原料,通过环化、氯化反应得到各种取代的2‑氯代喹诺啉‑4‑酮衍生物,然后通过与(R)‑2‑(4‑羟基苯氧基)丙酸酯进行亲核反应得到目标化合物(R)‑2‑[4‑((喹唑啉‑4‑酮)‑2‑氧基)苯氧基]丙酸酯衍生物。本发明还涉及(R)‑2‑[4‑((喹唑啉‑4‑酮)‑2‑氧基)苯氧基]丙酸酯衍生物在除草方面的应用。测试结果显示这类化合物对于稗草和马唐具有良好的除草活性,是一类结构新颖、应用前景广阔的选择性除草剂
Description
技术领域
本发明涉及一种(R)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物及其用途,尤其在农业除草方面的用途。
背景技术
对天然产物进行结构改造,从而发现新的具有农用生物活性的先导化合物,是绿色农药研究与开发的一条有效途径。目前,国外各大农化公司在该方面做了大量的研究工作,并且取得了丰硕的成果。例如:德国拜耳公司以天然产物双丙氨酰膦为先导开发出具有谷氨酰胺合成酶(GS)抑制作用的高效除草剂-草铵膦;国际壳牌公司以天然产物桉树脑为先导开发出了具有天冬酰胺酸合成酶(AS)抑制作用的高效广谱除草剂-环庚草醚;美国先正达公司以天然产物纤精酮为先导开发出了具有对羟基苯丙酮酸双加氧酶(HPPD)抑制作用的三酮类除草剂-硝磺草酮;法国安万特公司和美国罗门哈斯公司以天然产物莎草茵为先导同时开发出了具有原卟啉原氧化酶(PPO)抑制作用的二苯醚类除草剂-三氟羧草醚。然而,我国在以天然产物为先导开发除草剂的方面相对于发达国家起步较晚,拥有自主知识产权的产品为数不多。本文利用组合化学原理,将喹唑啉-4-酮类天然产物的母核结构与具有除草活性的芳氧苯氧丙酸酯类除草分子进行结构杂合,设计合成(R)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物,并对其除草活性进行测试,以期获得具有良好除草活性的先导化合物。目前,关于(R)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物的合成及其在农药除草剂方面的用途未见报道。
发明内容
本发明的目的是提供一种(R)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物的合成及其在农用除草剂方面的应用。以各种取代的邻氨基苯甲酸和甲基异硫氰酸酯为原料,通过环化、氯化反应得到各种取代的2-氯代喹诺啉-4-酮衍生物,然后通过与(R)-2-(4-羟基苯氧基)丙酸酯进行亲核反应得到目标化合物(R)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物。测试该类化合物对油菜、稗草、苋菜和马唐等杂草的抑制效果,其结果显示该类化合物在苗前1500克/公顷处理情况下,对稗草和马唐具有很好的除草活性,是一类结构新颖、应用前景广阔的选择性除草剂。
本发明提供的一种(R)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物的合成及在除草剂方面的应用,其特征在于其结构通式为(I):
其中,R代表H、5-Cl、6-Cl、7-Cl、8-Cl、5-F、6-F、7-F、8-F、5-Me、6-Me、7-Me、8-Me、6-Me-7-Me、6-F-7-F;R1代表Me、Et、Pr、i-Pr、n-Bu、n-Pentyl、Propargyl、Allyl、(Tetrahydrofuran-2-yl)methanyl、Ph、Benzyl。
本发明提供的(R)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物合成方法包括的步骤:
反应条件:a三乙胺,乙醇,80℃,3h;b磺酰氯,氯仿,90℃,2h;c碳酸钾,乙腈,90℃,2h.
1a R=H;1b R=6-Me;1c R=5-Me;1d R=4-Me;1e R=3-Me;1f R=6-F;1g R=5-F;1h R=4-F;1i R=3-F;1j R=6-Cl;1k R=5-Cl;1l R=4-Cl;1m R=3-Cl;1n R=4,5-2Me;1o R=4,5-2F;2a/3a R=H;2b/3b R=5-Me;2c/3c R=6-Me;2d/3d R=7-Me;2e/3eR=8-Me;2f/3f R=5-F;2g/3g R=6-F;2h/3h R=7-F;2i/3i R=8-F;2j/3j R=5-Cl;2k/3k R=6-Cl;2l/3l R=7-Cl;2m/3m R=8-Cl;2n/3n R=6,7-2Me;2o/3o R=6,7-2F;QPP-1R=H R1=Et;QPP-2 R=5-Me R1=Et;QPP-3 R=6-Me R1=Et;QPP-4 R=7-Me R1=Et;QPP-5 R=8-Me R1=Et;QPP-6 R=5-F R1=Et;QPP-7 R=6-F R1=Et;QPP-8 R=7-F R1=Et;QPP-9 R=8-F R1=Et;QPP-10 R=5-Cl R1=Et;QPP-11 R=6-Cl R1=Et;QPP-12 R=7-Cl R1=Et;QPP-13 R=8-Cl R1=Et;QPP-14 R=6,7-2Me R1=Et;QPP-15 R=6,7-2F R1=Et;QPP-16 R=6-F R1=Me QPP-17 R=6-F R1=Pr;QPP-18 R=6-F R1=i-Pr;QPP-19 R=6-F R1=n-Bu;QPP-20 R=6-F R1=n-Pentyl;QPP-21 R=6-F R1=Propargyl;QPP-22 R=6-F R1=Allyl;QPP-23 R=6-F R1=(Tetrahydrofuran-2-yl)methanyl;QPP-24 R=6-FR1=Ph;QPP-25 R=6-F R1=Benzyl.
以取代邻氨基苯甲酸1为原料,在80℃下,与甲基异硫氰酸酯(1.0eq)反应3小时得到中间体2。
将化合物2溶于氯仿,加入磺酰氯(1.0eq)反应2小时得到2-氯代喹唑啉-4-酮3。
将化合物3溶于乙腈中,加入(R)-2-(4-羟基苯氧基)丙酸酯4(1.0eq),加热回流反应2小时,得到目标化合物(R)-2-[4-((喹唑啉-4(3H)-酮)-2-氧基)苯氧基]丙酸酯衍生物I。
本发明还提供了(R)-2-[4-((喹唑啉-4(3H)-酮)-2-氧基)苯氧基]丙酸酯衍生物在农业上用作除草剂。所述杂草为单子叶植物或双子叶植物。
进一步的,所述的杂草为油菜、苋菜、稗草和马唐。
本发明进一步提供了上述化合物及其在农业上可以接受的盐作为有效成分与其他成分混合作为农药组合物,用做除草剂。
与现有技术相比,本发明具有如下有益效果:本发明提供的(R)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物在苗前处理的条件下,对稗草和马唐等杂草具有十分显著的抑制效果,其结果显示该类化合物具有广谱除草活性,是一类结构新颖、应用前景广阔的选择性除草剂。
具体实施方式
以下结合实施例进一步说明本发明,所举之例不应视为对本发明保护范围的限制。实施例中未注明具体条件的实验方法,通常按照常规条件以及手册中所述的条件,或按照制造厂商所建议的条件;所用的设备、材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1
将5.48g的2-氨基苯甲酸1a溶于30mL乙醇中,分别加入2.92g异硫氰酸甲酯和4.04g的三乙胺。反应体系升温至80℃搅拌3h,TLC跟踪反应,反应结束后,抽滤,先后用乙醇和正庚烷洗涤固体部分,晾干并收集固体,得到6.29g白色固体2a。收率82.0%。
将4.00g的化合物2a溶于30mL三氯甲烷中,加入2.70g的磺酰氯。反应体系升温至90℃,搅拌2h,TLC跟踪反应,反应结束后,将反应体系中加入水和二氯甲烷萃取,水相用二氯甲烷萃取2次,合并有机相。有机相用饱和食盐水洗涤3次,再用无水硫酸钠干燥。减压旋干溶剂后,将残余物经过硅胶柱层析分离(石油醚:乙酸乙酯=20:1)得到2.4g白色固体3a。收率63.0%。
将0.97g的化合物3a溶于10mL的乙腈中,加入1.00g的(R)-(+)-2-(4-羟基苯氧基)丙酸乙酯及1.04g的碳酸钾,反应体系升温至90℃,搅拌2h,TLC跟踪反应,反应结束后,减压旋干溶剂,将残余物经过硅胶柱层析分离(石油醚:乙酸乙酯=10:1)得到0.85g白色固体I-1。熔点:77.9~80.4℃;收率46.2%。1H NMR(500MHz,CDCl3)δ:8.21(dd,J=8.0,1.3Hz,1H),7.62–7.58(m,1H),7.38–7.30(m,2H),7.20–7.12(m,2H),6.98–6.88(m,2H),4.76(q,J=6.8Hz,1H),4.31–4.20(m,2H),3.70(s,3H),1.65(d,J=6.8Hz,3H),1.28(t,J=7.1Hz,3H);13C NMR(125MHz,CDCl3)δ:172.1,163.1,155.4,152.6,146.6,145.9,134.3,127.1,126.0,124.9,122.7,118.9,115.9,73.2,61.4,28.8,18.6,14.2.
化合物I-2~I-25按照与I-1相似的方法合成,相关数据列于表1中。
表1化合物I-2~I-25的物理性质
实施例2
用油菜平皿法、稗草小杯法对I-1~I-25化合物进行了除草活性测试。
油菜平皿法:直径6cm的培养皿中铺好一张直径5.6cm的滤纸,加入2mL一定浓度的供试化合物溶液,设置一个只加蒸馏水的空白对照,播种浸种4~6h的油菜种子粒10粒,28℃下,黑箱培养了72小时后测定胚根长度。通过黑暗条件下化合物对油菜胚根的生长抑制来检测化合物的除草活性。
稗草小杯法:通过光照条件下化合物对稗草幼苗株高的生长抑制来检测化合物的除草活性。在25mL的烧杯底部铺满一层大小一致的玻璃球,然后放一张与杯底大小一致的滤纸,加入配置好的一定浓度的待测化合物溶液5.5mL,并设置一个只加蒸馏水的空白对照。播种出芽一致的稗草种子10粒,在28℃的光室内培养72小时,测定稗草幼苗地上长度,通过与空白对照计算出对稗草地上部分的抑制率。
化合物I-1~I-25的除草活性列于表2中。由生物活性测试结果可以看出,在100μg/mL的剂量下,大部分目标化合物对单子叶植物稗草具有很好的抑制效果。其中,目标化合物I-7~I-9、I-11~I-13和I-15~I-25在10μg/mL的剂量下,对稗草的抑制率达到70%以上,但是对双子叶植物油菜的抑制效果不理想。由此可以看出,该类化合物可选择性的抑制单子叶植物。
表2目标化合物I-1~I-25的小杯平皿除草活性
实施例3
苗前盆栽法:塑料盒中装入(11×7.5×6)中装入100g沙土,用水湿润后,播种15颗发芽的种子于泥土下0.5cm深,喷洒待测化合物的溶液(1500克/公顷),设置一个不喷晒药剂的空白对照。温室下(温度25±1℃,12小时光照条件),生长15天。幼苗收割后,从根苗分界处剪切后称重,与空白对照对比,计算抑制百分数。每个浓度设置三个重复,取平均值。
苗后盆栽法:把发芽的种子改成出苗后的种子,其他操作同苗前盆栽法。
化合物I-1~I-25的盆栽除草活性列于表3中。由生物活性测试结果可以看出,在1500克/公顷的剂量下,目标化合物对稗草和马唐均具有很好的抑制效果,对油菜和苋菜的效果不理想。并且通过比较可以看出,目标化合物的苗前处理效果要优于苗后处理活性。其中,目标化合物I-6~I-9,I-12~I-13、I-15~I-25在苗前1500克/公顷的剂量下处理,对稗草和马唐的抑制率均达到100%。由此可以看出,该类化合物可以在苗前处理的条件下作为对单子叶植物稗草和马唐潜在的除草剂。
表3目标化合物I-1~I-25的盆栽除草活性(剂量=1500克/公顷)
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Claims (4)
1.一种(R)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸酯衍生物,其特征在于,其结构通式为(I):
;其中R代表H、5-Cl、6-Cl、7-Cl、8-Cl、5-F、6-F、7-F、8-F、5-Me、6-Me、7-Me、8-Me、6-Me-7-Me、6-F-7-F;R1代表Me、Et、n-Pr、i-Pr、n-Bu、n-Pentyl、Propargyl、Allyl、(Tetrahydrofuran-2-yl)methyl、Ph、Benzyl。
2.一种权利要求1所述的(R)-2-[4-((喹唑啉-4-酮)-2-氧基)苯氧基]丙酸乙酯衍生物或其可接受的盐的应用,其特征在于,用作农用除草剂,所述的杂草为单子叶植物。
3.按照权利要求2所述的应用,其特征在于:所述的杂草为稗草和马唐。
4.一种用于农业上除草方面的农药组合物,其特征在于含有权利要求1所述的化合物,或者含有其在农业上可接受的盐。
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