CN106135228B - 一种含甲基吡唑的三唑类化合物在制备杀菌剂中的应用 - Google Patents
一种含甲基吡唑的三唑类化合物在制备杀菌剂中的应用 Download PDFInfo
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- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 claims abstract description 6
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- RAGOYPUPXAKGKH-XAKZXMRKSA-N posaconazole Chemical compound O=C1N([C@H]([C@H](C)O)CC)N=CN1C1=CC=C(N2CCN(CC2)C=2C=CC(OC[C@H]3C[C@@](CN4N=CN=C4)(OC3)C=3C(=CC(F)=CC=3)F)=CC=2)C=C1 RAGOYPUPXAKGKH-XAKZXMRKSA-N 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明涉及一种含甲基吡唑的三唑类化合物在制备杀菌剂中的应用，该含甲基吡唑的三唑类化合物5‑(1‑甲基‑3‑甲基‑1H‑吡唑‑4‑基)‑4‑苯基‑4H‑1,2,4‑三唑‑3‑硫醚类化合物在制备杀菌剂中的应用，具体为该类化合物制得的杀菌剂在防治水稻纹枯病菌、番茄早疫病、瓜类炭疽病、黄瓜灰霉病菌中均有明显的效果，该化合物为具有杀菌活性的新化合物，为新农药的研发提供了基础。
Description
技术领域
本发明涉及一种含甲基吡唑的三唑类化合物即5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑-3-硫醚类化合物在制备杀菌剂中的应用。
背景技术
上世纪安替比林的发现使得吡唑类化合物以药物的身份进入了人们的视野，由于吡唑类化合物表现出的高效、低毒和结构多样性的特点，许多新型、高效、对环境友好的吡唑类衍生物的农药品种也应运而生，自此以来农药工业进入了快速发展时期，新药物中杂环化合物占据了主导地位，吡唑类衍生物作为杂环化合物中一个重要类别在新药研发领域更是具有重要地位。目前市场上此类农药应用范围极其广泛，包括除草、杀虫/杀螨、杀菌和植物生长调节等多个领域。已成功开发出多个抗菌剂品种有：绿叶宁、安种宁、茂叶宁、唑菌胺酯等。另一方面，三唑是咪唑环中的一个碳原子被氮取代得到的五元杂环，作为药效团三唑比咪唑具有更低的毒性，且其表现出的抗真菌、抗病毒、抗肿瘤、抗惊厥等特性广泛应用于临床和农业。例如特康唑，伊曲康唑，泊沙康唑，和氟康唑等三唑类抗真菌药物；病毒唑等用于抗病毒的三唑类药物。三唑类农药经过数十年的发展，应用范围和防治对象由过去主要用作杀菌剂到现在已开发出多种高效、低毒的除草剂、杀虫剂、植物生长调节剂。在除草剂方面例如唑草胺、氟胺草唑、唑酮草酯、五氟磺草胺等一系列含三唑类除草剂被相继开发，并得到广泛应用。综上可见，三唑的特殊结构使其三唑类化合物在医药、农药、化学化工等领域得到了异常广泛的应用,其研究与开发日益活跃，引起越来越多的科学工作者的关注。本发明专利即提供了新颖的具有除草活性的三唑连吡唑类化合物。
发明内容
针对现有技术中存在的上述问题，本发明目的是提供一种含甲基吡唑的三唑类化合物在制备杀菌剂中的应用。
所述的一种含甲基吡唑的三唑类化合物在制备杀菌剂中的应用，其特征在于含甲基吡唑的三唑类化合物为5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑-3-硫醚类化合物，其结构式如式(I)所示：
式(I)中：R选自氰基，4-氰基苯基，2,4-二氯苯基，2-氯苯基，4-氯苯基，2-氟苯基，4-溴苯基，2-氯-5-吡啶基。
所述的应用，其特征在于杀菌剂用于防治水稻纹枯病菌、番茄早疫病、瓜类炭疽病、黄瓜灰霉病菌。
所述的含甲基吡唑的三唑类化合物的制备方法，其特征在于具体步骤如下：
1)将乙酰乙酸乙酯和原甲酸三乙酯在乙酸酐中回流反应，反应结束后减压蒸馏得粗产品，即式(Ⅱ)所示的化合物(E)-2-乙氧基亚甲基-3-乙酰乙酸甲酯；
2)将式(Ⅱ)所示的化合物与甲基肼在有机溶剂中55-65℃反应，反应结束后减压蒸馏、萃取，得式(Ⅲ)所示的化合物；
3)将式(Ⅲ)所示的化合物与水合肼在有机溶剂中回流反应，得式(IV)所示的化合物；
4)将式(IV)所示的化合物与异硫氰酸苯酯在有机溶剂中回流反应，得式(V)所示的化合物；
5)将式(V)所示的化合物在碱性物质的水溶液中回流反应，反应结束加入酸中和，析出固体，抽滤、重结晶得式(Ⅵ)所示的化合物；
6)将式(Ⅵ)所示的化合物加入到有机溶剂中，在碱性物质存在下与卤代物RCH2X室温过夜反应，反应结束后倒入碎冰中，析出固体后抽滤、重结晶得目标产物式(I)所示的含甲基吡唑的三唑类化合物，卤代物RCH2X中的R为氰基，4-氰基苯基，2,4-二氯苯基，2-氯苯基，4-氯苯基，2-氟苯基，4-溴苯基，2-氯-5-吡啶基；
所述的一种含甲基吡唑的三唑类化合物的制备方法，其特征在于步骤1)中乙酰乙酸乙酯、原甲酸三乙酯与乙酸酐的物质的量之比为1:1.0～2.0:2.0～3.0。
所述的一种含甲基吡唑的三唑类化合物的制备方法，其特征在于步骤2)中所述有机溶剂为甲醇、乙醇、甲苯中的一种或几种混合物，有机溶剂体积用量以式(Ⅱ)所示的化合物的物质的量计为0.5～1.0mmol/ml，式(Ⅱ)所示的化合物与甲基肼的物质的量之比为1:1.5～2.0。
所述的一种含甲基吡唑的三唑类化合物的制备方法，其特征在于步骤3)中所述有机溶剂为甲醇或乙醇，有机溶剂体积用量以式(Ⅲ)所示的化合物的物质的量计为0.5～1.0mmol/ml；式(Ⅲ)所示的化合物与水合肼的物质的量之比为1:1.5～3.0。
所述的一种含甲基吡唑的三唑类化合物的制备方法，其特征在于步骤4)中所述有机溶剂为甲醇，乙醇，甲苯中的一种或几种混合物，式(IV)所示的化合物与异硫氰酸苯酯的物质的量之比为1:1.0～1.5。
所述的一种含甲基吡唑的三唑类化合物的制备方法，其特征在于步骤5)中所述碱性物质为碳酸钠，碳酸钾，氢氧化铵，氢氧化钠，氢氧化钾中的一种，碱溶液的浓度为2％～10％；酸为盐酸、硫酸或硝酸；重结晶溶剂为乙醇，乙酸乙酯，石油醚中的一种或几种混合物。
所述的一种含甲基吡唑的三唑类化合物的制备方法，其特征在于步骤6)中所述有机溶剂为丙酮，乙腈，二甲基甲酰胺中的一种或几种混合物；有机溶剂体积用量以式(V)所示的化合物的物质的量计为0.1～0.3mmol/ml；所述碱性物质为碳酸钠，碳酸钾，氢氧化钠，氢氧化钾中的一种或几种混合物。
所述的一种含甲基吡唑的三唑类化合物的制备方法，其特征在于步骤6)中式(Ⅵ)所示的与卤代物的物质的量之比为1:1.0～1.5，重结晶溶剂为乙醇，乙酸乙酯，石油醚中的一种或几种的混合物。
本发明的合成过程如下：
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5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑-3-硫醚类化合物的应用，该类化合物为具有杀菌活性的新化合物，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：
本发明的含吡唑的甲酰胺类化合物(I)可以如下方法合成：
1)1-甲基-3-甲基-1H-吡唑-4-甲酸乙酯,式(Ⅲ)的合成
将乙酰乙酸乙酯(40mmol)，原甲酸三乙酯(60mmol)在乙酸酐(0.12mol)中回流反应8小时,反应结束后减压蒸馏，得粗产品式(Ⅱ)；冰浴下，逐滴将式(Ⅱ)(40mmol)滴入到甲基肼(60mmol)与乙醇(20mL)混合液中，60℃反应8小时，反应结束后减压蒸馏，加入乙酸乙酯(20mL)与饱和食盐水萃取，有机层用无水硫酸钠除水后悬蒸，得式(Ⅲ)1-甲基-3-甲基-1H-吡唑-4-甲酸乙酯；
2)1-甲基-3-甲基-1H-吡唑-4-碳酰肼，式(IV)的合成
将式(Ⅲ)化合物5mmol加入到10mL乙醇中，搅拌下加入80％水合肼10mmol，回流反应10小时，反应结束后加压蒸馏，析出固体，用水冲洗抽滤，得式(IV)化合物。
3)5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑-3-硫醇，式(Ⅵ)的合成
将式(IV)化合物5mmol加入到10mL乙醇中，加入搅拌下加入异硫氰酸苯酯6mmol，回流反应3小时后冷却，析出固体，抽滤，得式(V)化合物。式(V)在5％氢氧化钠溶液中回流4小时后，加入1N盐酸中和，析出固体，抽滤，重结晶得式(Ⅵ)化合物。
4)5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑-3-硫醚类化合物，式(I)的合成
以3-苄硫基-5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑为例，将式(Ⅵ)化合物(1mmol)加入到10mLDMF中，加入氯苄(1.2mmol)，室温过夜反应，反应结束后减压蒸馏，重结晶得目标化合物3-苄硫基-5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑。其他5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑-3-硫醚类化合物同样方法制得。
实施例1
3-(4-氰基苄硫基)-5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑，白色针状晶体，熔点106-109℃，收率27.6％，1H NMR(500MHz,CDCl3)ppm7.60-7.50(m,7H,pyrazole H and Ar-H),7.14(d,J＝7.27Hz,2H,Ar-H),6.59(s,1H,Ar-H),4.49(s,2H,-CH2-),3.68(s,3H,N-CH3),2.42(s,3H,pyrazole CH3)
实施例2
3-(2-氯苄基硫基)-5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑，白色晶体，熔点108-109℃，收率59.1％，1H NMR(500MHz,CDCl3)ppm 7.59(dd,J＝7.16,1.89Hz,1H,Ar-H),7.54-7.47(m,3H,pyrazole H and Ar-H),7.36(dd,J＝7.54,1.57Hz,1H,Ar-H),7.25-7.19(m,2H,Ar-H),7.11(d,J＝7.45Hz,2H,Ar-H),6.60(s,1H,Ar-H),4.60(s,2H,-CH2-),3.68(s,3H,N-CH3),2.43(s,3H,pyrazole CH3)
实施例3
3-(4-氯苄基硫基)-5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑，白色晶体，熔点97-99℃，收率64.1％，1H NMR(500MHz,CDCl3)ppm 7.56-7.48(m,3H,pyrazole H and Ar-H),7.33(d,J＝8.36Hz,2H,Ar-H),7.30-7.25(m,2H,Ar-H),7.13(d,J＝7.21Hz,2H,Ar-H),6.61(s,1H,Ar-H),4.44(s,2H,-CH2-),3.69(s,3H,N-CH3),2.43(s,3H,pyrazole CH3)
实施例4
3-(2-氟苄基硫基)-5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑，白色晶体，熔点123-125℃，收率65.1％，1H NMR(500MHz,CDCl3)ppm 7.58-7.47(m,4H,pyrazole H and Ar-H),7.32-7.24(m,1H,Ar-H),7.13(d,J＝7.29Hz,2H,Ar-H),7.09-7.02(m,2H,Ar-H),6.61(s,1H,Ar-H),4.52(s,2H,-CH2-),3.69(s,3H,N-CH3),2.44(s,3H,pyrazole CH3)
实施例5
3-(2,4-二氯苄基硫基)-5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑，白色固体，熔点133-135℃，收率83.9％，1H NMR(500MHz,CDCl3)ppm7.62-7.47(m,4H,pyrazole H and Ar-H),7.37(d,J＝2.07Hz,1H,Ar-H),7.19(dd,J＝8.24,2.02Hz,1H,Ar-H),7.13(d,J＝7.03Hz,2H,Ar-H),6.59(s,1H,Ar-H),4.54(s,2H,-CH2-),3.68(s,3H,N-CH3),2.42(s,3H,pyrazole CH3)
实施例6
3-(4-溴苄基硫基)-5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑，黄色固体，熔点105-108℃，收率57.7％，1H NMR(500MHz,CDCl3)ppm 7.58-7.49(m,3H,pyrazole H and Ar-H),7.42(d,J＝8.37Hz,2H,Ar-H),7.30-7.25(m,2H,Ar-H),7.12(d,J＝7.43Hz,2H,Ar-H),6.61(s,1H,Ar-H),4.42(s,2H,-CH2-),3.69(s,3H,N-CH3),2.43(s,3H,pyrazole CH3)
实施例7
2-((5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑-3-基)硫基)乙腈，黄色固体，熔点117-118℃，收率32.3％，1H NMR(500MHz,CDCl3)ppm 7.65-7.58(m,3H,pyrazole H and Ar-H),7.32(s,2H,Ar-H),6.68(s,1H,Ar-H),4.09(s,2H,-CH2-),3.71(s,3H,N-CH3),2.44(s,3H,pyrazole CH3)
实施例8
2-氯-5-(((5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑-3-基)硫基)甲基)吡啶，淡黄色固体，熔点102-103℃，收率70.7％，1H NMR(500MHz,CDCl3)ppm 8.40(d,J＝2.31Hz,1H,吡啶环H),7.83(dd,J＝8.24,2.49Hz,1H,吡啶环H),7.60-7.52(m,3H,pyrazole H and Ar-H),7.27(d,J＝8.29Hz,1H,吡啶环H),7.17(d,J＝7.20Hz,2H,Ar-H),6.62(s,1H,Ar-H),4.44(s,,2H,-CH2-),3.70(s,3H,N-CH3),2.43(s,3H,pyrazole CH3)。
实施例1-8中步骤4的反应条件如表1所示。
表1各实施例具体反应条件
实施例9
杀菌活性测试
试验对象：水稻纹枯病菌、番茄早疫病、瓜类炭疽病、黄瓜灰霉病菌。
试验处理：式(I)化合物用DMF溶解成1％EC备用。采用菌丝生长抑制法，评价这些化合物在20mg/L剂量下对4种试验靶标的室内杀菌活性。
试验方法：创制农药生物活性评价SOP(杀菌剂卷)。
水稻纹枯病菌、番茄早疫病、瓜类炭疽病、黄瓜灰霉病菌杀菌活性测试试验结果如表1所示。
表1 20mg/L下各化合物的杀菌活性(％防效)
本发明的式(Ⅰ)所示的5-(1-甲基-3-甲基-1H-吡唑-4-基)-1,3,4-噻二唑-2-硫醚类化合物及其制备方法与在防治水稻纹枯病菌、番茄早疫病、瓜类炭疽病、黄瓜灰霉病菌中的应用，本发明化合物为具有杀菌活性的新化合物，为新农药的研发提供了基础。
Claims (1)
1.一种含甲基吡唑的三唑类化合物在制备用于防治水稻纹枯病菌、番茄早疫病、瓜类炭疽病、黄瓜灰霉病菌的杀菌剂中的应用，其特征在于含甲基吡唑的三唑类化合物为5-(1-甲基-3-甲基-1H-吡唑-4-基)-4-苯基-4H-1,2,4-三唑-3-硫醚类化合物，其结构式如式（I）所示：
式（I）中：R选自氰基，4-氰基苯基，2,4-二氯苯基，2-氯苯基，4-氯苯基，2-氟苯基，4-溴苯基， 2-氯-5-吡啶基。
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