CN109156471A - 一种1，3-二甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用 - Google Patents
一种1，3-二甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon 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
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
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- Agronomy & Crop Science (AREA)
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Abstract
本发明涉及一种1,3‑二甲基‑1H‑吡唑‑4‑酰胺衍生物在制备除草剂中的应用。它以生菜和剪股颖种子为试验对象，在生物测定之前，种子均使用5‑10%的Chlorox溶液进行10分钟的表面灭菌，随后用Millipore系统的去离子水进行彻底冲洗，随后在无菌环境中风干，样品处理：所有的样品均使用丙酮作为溶剂，配置浓度为1 mM的溶液，最后进行生物测定，得到的化合物对生菜，剪股颖表现出了较好的抑制性；本发明所述化合物为具有除草活性的新化合物，为新农药的研发提供了基础。
Description
技术领域
本发明涉及一种新型含酰胺的吡唑类化合物即1,3-二甲基-1H-吡唑-4-酰胺衍生物在制备除草剂中的应用。
背景技术
如今，吡唑酰胺和脲类化合物由于含有吡唑、酰胺和脲桥等高活性结构基团，通常具有低毒、高效等优良且广泛的生物活性，硫脲类化合物同样也具有广泛的生物活性，如抗过敏、消炎、抗菌、杀虫和除草等，上世纪60年代末硫脲类化合物托布津和甲基托布津的高效、低毒杀菌剂的广泛使用将硫脲类衍生物的杀菌活性研究更加推向高潮，到目前为止，国外的一些药物公司相继成功地开发了数十个硫脲类的杀菌剂、杀虫剂、植物生长调节剂和杀鼠剂等新品种，如杀菌剂代菌灵、杀虫剂螟蛉畏、杀螨剂杀螨隆、植物生长调节剂呋苯硫脲、杀鼠剂安妥等。该类化合物具有对植物的残留低、药害小、对哺乳动物的急性毒性低等优点。
发明内容
本发明的目的在于提供一种1,3-二甲基-1H-吡唑-4-酰胺衍生物在制备除草剂中的应用，所述除草剂用于抑制生菜和剪股颖的生长。
所述的一种1,3-二甲基-1H-吡唑-4-酰胺衍生物在制备除草剂中的应用，其特征在于其结构式如式(Ⅰ)所示：
式(Ⅰ)中：R0为氢或甲基，R1为苯基或取代苯基，所述取代苯基的取代基为卤素、甲氧基、硝基、甲基、乙基、丁基。
所述的一种1,3-二甲基-1H-吡唑-4-酰胺衍生物在制备抵制生菜和剪股颖的除草剂中的应用，其特征在于其结构式如式(Ⅰ)所示：
式(Ⅰ)中：R0为氢或甲基，R1为苯基或取代苯基，所述取代苯基的取代基为卤素、甲氧基、硝基、甲基、乙基、丁基。
所述的应用，其特征在于式(Ⅰ)中R1为下列之一：(S)-N-(1-苯乙基)、(R)-N-(1-苯乙基)、N-(4-氯苄)、N-苯乙基、N-(1-(2-甲氧基-5硝基苄基)乙基)、N-(萘-1-亚甲基)、N-(3,4,5-三甲氧基苄基)、N-(吡啶-4-亚甲基)、(R)-N-(1-(4-氯苯基)乙基)。
与现有技术相比，本发明的有益效果主要体现在：本发明提供了一种1,3-二甲基-1H-吡唑-4-酰胺衍生物在制备除草剂中的应用，所给出的化合物对生菜、剪股颖表现出了较好的抑制性；本发明所述化合物为具有除草活性的新化合物，为新农药的研发提供了基础。
具体实施方式
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此：
实施例1(R)-1,3-二甲基-N-(1-苯乙基)-1H-吡唑-4-甲酰胺的制备
(1)1,3-二甲基-1H-吡唑-4-甲酸乙酯(Ⅱ)的合成：
将乙酰乙酸乙酯(7.36g,40mmol)，原甲酸三乙酯(8.88g,60mmol)在乙酸酐(12.24g,0.12mol)中回流反应8小时，气相追踪反应物至反应完全，反应结束后减压蒸馏，去除多余原甲酸三乙酯，得粗产品式1；冰浴下，逐滴将式1(9.6g,40mmol)滴入到40％甲基肼(6.9g,60mmol)与乙醇(20ml)混合液中，回流反应6小时，TLC(EA/PE＝1/1(V))跟踪反应，待反应结束后减压蒸馏，加入乙酸乙酯(20ml)与饱和食盐水萃取三次，有机层用无水硫酸钠除水后悬蒸，制得式(Ⅱ)所示的1,3-二甲基-1H-吡唑-4-甲酸乙酯；
(2)1,3-二甲基-1H-吡唑-4-羧酸式(Ⅲ)的合成：
将式(Ⅱ)所示的1,3-二甲基-1H-吡唑-4-甲酸乙酯(8.88g,40mmol)加入到5％的氢氧化钠水溶液(100ml)中，60℃反应3小时，至反应体系透明，然后加入盐酸中和将pH调至弱酸性，析出固体，反应停止，抽滤得式(Ⅲ)所示的1,3-二甲基-1H-吡唑-4-羧酸；
(3)(R)-1,3-二甲基-N-(1-苯乙基)-1H-吡唑-4-甲酰胺式(K19)的合成：
式(Ⅲ)所示的1,3-二甲基-1H-吡唑-4-羧酸(7.76g,40mmol)与二氯亚砜(47.6g,0.4mol)回流4小时，待反应体系变为淡黄色透明液体时，继续反应30min，反应停止，冷却至室温后减压蒸馏得1,3-二甲基-1H-吡唑-4-酰氯，将1,3-二甲基-1H-吡唑-4-酰氯(2mmol)加入15ml二氯甲烷中，加入(R)-1-苯乙基-1-胺(2.1mmol)，随后缓慢滴加三乙胺(0.3g,3mmol)室温过夜搅拌；TLC(EA:PE＝2:1(V))追踪，待反应完全后用二氯甲烷/水＝1:1(V)体系萃取三次，浓缩有机层，甲苯或75％乙醇萃取，柱层析(EA:PE＝2:1(V))，得(K19)所示的(R)-1,3-二甲基-N-(1-苯乙基)-1H-吡唑-4-甲酰胺；
式(K19)所示的(R)-1,3-二甲基-N-(1-苯乙基)-1H-吡唑-4-甲酰胺结构式如下：
(R)-1,3-二甲基-N-(1-苯乙基)-1H-吡唑-4-甲酰胺：白色固体产率：35.5％，熔点：119～120℃，1H NMR(500MHz,CDCl3)δ:1.58(d,J＝7.0Hz,3H,CH3),2.47(s,3H,CH3),3.83(s,3H,CH3),5.25～5.32(m,1H,CH),5.86(d,J＝7.0Hz,1H,NH),7.29～7.30(m,1H,Ph),7.36～7.37(m,4H,Ph),7.68(s,1H,CH).HRMS(ESI)m/z:Calculated,244.1444,Found,244.14340[M+H]+。
实施例2(S)-1,3-二甲基-N-(1-苯乙基)-1H-吡唑-4-甲酰胺的制备
将实施例1步骤3)中的(R)-1-苯乙基-1-胺改为(S)-1-苯乙基-1-胺，乙酰乙酸乙酯与原甲酸三乙酯物质的量之比为1:2，1,3-二甲基-1H-吡唑-4-羧酸与氯化亚砜物质的量之比为1:1，1,3-二甲基-1H-吡唑-4-羧酸与(S)-1-苯乙基-1-胺物质的量之比为1:1，有机溶剂用二氧六环，其他操作同实施例1，制得目标化合物式(K20)所示的(S)-1,3-二甲基-N-(1-苯乙基)-1H-吡唑-4-甲酰胺
(S)-1,3-二甲基-N-(1-苯乙基)-1H-吡唑-4-甲酰胺：白色固体产率：45.2％，熔点：121～122℃，1H NMR(500MHz,CDCl3)δ:1.58(d,J＝7.0Hz,3H,CH3),2.47(s,3H,CH3),3.83(s,3H,CH3),5.27～5.30(m,1H,CH),5.86(d,J＝7.0Hz,1H,NH),7.28～7.30(m,2H,Ph),7.35～7.38(m,3H,Ph),7.68(s,1H,CH).HRMS(ESI)m/z:Calculated,244.1444,Found,244.14307[M+H]+.
实施例3N-(4-氯苄基)-1,3-二甲基-1H-吡唑-4-甲酰胺的制备
将实施例1步骤3)中的(R)-1-苯乙基-1-胺改为((4-氯苯基)甲胺，其他操作同实施例1，获得如式(K21)所示的N-(4-氯苄基)-1,3-二甲基-1H-吡唑-4-甲酰胺
N-(4-氯苄基)-1,3-二甲基-1H-吡唑-4-甲酰胺：淡黄色固体产率：93.9％，熔点：101～103℃，1H NMR(500MHz,CDCl3)δ:2.46(s,3H,CH3),3.84(s,3H,CH3),5.25(d,J＝7.0Hz,2H,CH2),5.86(d,J＝7.5Hz,1H,NH),7.29～7.33(m,4H,Ph),7.70(s,1H,CH).HRMS(ESI)m/z:Calculated,278.1055,Found,278.10645[M+H]+.
实施例4 1,3-二甲基-N-苯乙基-1H-吡唑-4-甲酰胺的制备
将实施例1步骤3)中的(R)-1-苯乙基-1-胺改为2-苯基-1-胺，乙酰乙酸乙酯与原甲酸三乙酯物质的量之比为1:5，1,3-二甲基-1H-吡唑-4-羧酸与氯化亚砜物质的量之比为1:190，1,3-二甲基-1H-吡唑-4-羧酸与2-苯基-1-胺物质的量之比为1:3，有机溶剂用二甲苯，其他操作同实施例1，获得如式(K22)所示的1,3-二甲基-N-苯乙基-1H-吡唑-4-甲酰胺
1,3-二甲基-N-苯乙基-1H-吡唑-4-甲酰胺：淡黄色固体产率：41.9％，熔点：65～66℃，1H NMR(500MHz,CDCl3)δ:2.32(s,3H,CH3),2.91(t,J＝7.0Hz,2H,CH2),3.66～3.70(m,2H,CH2),3.82(s,3H,CH3),5.63(s,1H,NH),7.23～7.26(m,3H,Ph),7.33～7.35(m,2H,Ph),7.63(s,1H,CH).
实施例5N-(1-(2-甲氧基-5-硝基苯基)乙基)-1,3-二甲基-1H-吡唑-4-甲酰胺的制备
将实施例1步骤3)中的(R)-1-苯乙基-1-胺改为1-(2-甲氧基-5-硝基苯基)乙基-1-胺，乙酰乙酸乙酯与原甲酸三乙酯物质的量之比为1:4，1,3-二甲基-1H-吡唑-4-羧酸与氯化亚砜物质的量之比为1:100，1,3-二甲基-1H-吡唑-4-羧酸与1-(2-甲氧基-5-硝基苯基)乙基-1-胺物质的量之比为1:2，有机溶剂用二甲苯，其他操作同实施例1，获得如式(K23)所示的N-(1-(2-甲氧基-5-硝基苯基)乙基)-1,3-二甲基-1H-吡唑-4-甲酰胺
N-(1-(2-甲氧基-5-硝基苯基)乙基)-1,3-二甲基-1H-吡唑-4-甲酰胺：白色固体产率：65.0％，熔点：63～64℃，1H NMR(500MHz,CDCl3)δ:2.39(s,3H,CH3),3.08(s,3H,CH3),3.85(s,3H,CH3),3.97(s,3H,CH3),4.72(s,1H,CH),6.97(d,J＝9.0Hz,1H,Ph),7.48(s,1H,CH),8.06(d,J＝2.5Hz,1H,Ph),8.22～8.24(m,1H,Ph).HRMS(ESI)m/z:Calculated,319.1401,Found,319.14190[M+H]+.
实施例6N,1,3-三甲基-N-(萘-1-亚甲基)-1H-吡唑-4-甲酰胺的制备
将实施例1步骤3)中的(R)-1-苯乙基-1-胺改为萘-1-亚甲基胺，其他操作同实施例1，获得如式(K24)所示的N,1,3-三甲基-N-(萘-1-亚甲基)-1H-吡唑-4-甲酰胺
N,1,3-三甲基-N-(萘-1-亚甲基)-1H-吡唑-4-甲酰胺：白色固体产率：32.4％，熔点：45～46℃，1H NMR(500MHz,CDCl3)δ:2.36(s,3H,CH3),2.99(s,3H,CH3),3.77(s,3H,CH3),5.17(s,2H,CH2),7.13～7.25(m,1H,Ph),7.43(d,J＝7.0Hz,1H,Ph),7.49(s,1H,CH),7.53～7.55(m,2H,Ph),7.85(d,J＝8.5Hz,1H,Ph),7.91-7.92(m,1H,Ph),8.09(s,1H,Ph).
实施例7N,1,3-三甲基-N-(3,4,5-三甲氧基苄基)-1H-吡唑-4-甲酰胺的制备
将实施例1步骤3)中的(R)-1-苯乙基-1-胺改为(3,4,5-三甲氧基苯基)甲胺，有机溶剂用四氢呋喃，其他操作同实施例1，获得如式(K25)所示的N,1,3-三甲基-N-(3,4,5-三甲氧基苄基)-1H-吡唑-4-甲酰胺
N,1,3-三甲基-N-(3,4,5-三甲氧基苄基)-1H-吡唑-4-甲酰胺：白色固体产率：35.6％，熔点：97～98℃，1H NMR(500MHz,CDCl3)δ:2.37(s,3H,CH3),3.01(s,3H,CH3),3.81(s,3H,CH3),3.84(s,9H,3CH3),4.61(s,2H,CH2),6.38～6.58(m,2H,Ph),7.43(s,1H,CH).
实施例8(R)-N-(1-(4-氯苯基)乙基)-N,1,3-三甲基-1H-吡唑-4-甲酰胺的制备
将实施例1步骤3)中的(R)-1-苯乙基-1-胺改为(R)-1-(4-氯苯基)乙基-1-胺，其他操作同实施例1，获得如式(K26)所示的(R)-N-(1-(4-氯苯基)乙基)-N,1,3-三甲基-1H-吡唑-4-甲酰胺
(R)-N-(1-(4-氯苯基)乙基)-N,1,3-三甲基-1H-吡唑-4-甲酰胺：淡黄色固体产率：82.9％，熔点：107～108℃，1H NMR(500MHz,CDCl3)δ:1.55(d,J＝6.5Hz,3H,CH3),2.46(s,3H,CH3),3.83(s,3H,CH3),5.22～5.25(m,1H,CH),5.88(d,J＝7.0Hz,1H,NH),7.28～7.33(m,4H,Ph),7.70(s,1H,CH).
实施例9除草活性测试
试验对象：生菜(Lettuce)、剪股颖(Agrostis)的种子。
试验处理：种子处理：在生物测定之前，种子均使用5-10％的Chlorox溶液进行10分钟的表面灭菌，随后用Millipore系统的去离子水进行彻底冲洗，随后在无菌环境中风干。样品处理：所有的样品均使用丙酮作为溶剂，配置浓度为1mM的溶液，放置待用。
生物测定：所有生物测定均分为一式两份测定，均在无菌无热原聚苯乙烯24孔细胞培养板(CoStar 3524,Corning Incorporated)中进行。将一个滤纸盘(Whatman Grade1,1.5cm)置于每个待使用的孔中。所有对照孔中均有200μL水，对照+溶剂的孔中含有180μL水和20μL溶剂，而所有的样品孔中均有180μL水和20μL适当稀释的样品。在加入样品之前，先将180μL水吸入孔中。所有的平板均放置在无菌的环境中，并且尽可能的减少污染的机会。在所有的孔中均放入5颗种子，用盖子密封。将板放在CU-36L5的培养箱中，温度为26℃，光照强度为120.1umol s-1m-2的条件下孵育，将平板至少孵育7天，得到相对主观的植物排名。排名共分为5个等级：0-5。等级为0的表示没有明显的抑制作用(样品孔植物与对照+溶剂孔植物相同)，等级5表示为完全抑制，即孔中所有的种子完全没有发芽。
除草活性测试结果如表1所示。
表1 1mm下各化合物的除草活性
从表1得出，本发明所采用的化合物1mm下对生菜表现出了较好的抑制性，尤其是(K-26)化合物；对剪股颖表现出了较好的抑制性，尤其是(K-26)化合物；其他化合物也都表现出了良好的对生菜、剪股颖的抑制性。
Claims (3)
1.一种1,3-二甲基-1H-吡唑-4-酰胺衍生物在制备除草剂中的应用，其特征在于其结构式如式（Ⅰ）所示：
式（Ⅰ）中：R0为氢或甲基，R1为苯基或取代苯基，所述取代苯基的取代基为卤素、甲氧基、硝基、甲基、乙基、丁基。
2.一种1,3-二甲基-1H-吡唑-4-酰胺衍生物在制备抵制生菜和剪股颖的除草剂中的应用，其特征在于其结构式如式（Ⅰ）所示：
式（Ⅰ）中：R0为氢或甲基，R1为苯基或取代苯基，所述取代苯基的取代基为卤素、甲氧基、硝基、甲基、乙基、丁基。
3.根据权利要求1或2所述的应用，其特征在于式（Ⅰ）中R1为下列之一：（S）-N-（1-苯乙基）、（R）-N-（1-苯乙基）、N-(4-氯苄）、N-苯乙基、N-（1-（2-甲氧基-5硝基苄基）乙基）、N-（萘-1-亚甲基）、N-（3,4,5-三甲氧基苄基）、N-（吡啶-4-亚甲基）、（R）-N-（1-(4-氯苯基）乙基）。
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