CN108892636A - 一种羧酸苄酯类化合物及其用于防治农作物真菌病害的用途 - Google Patents

一种羧酸苄酯类化合物及其用于防治农作物真菌病害的用途 Download PDF

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CN108892636A
CN108892636A CN201810661824.1A CN201810661824A CN108892636A CN 108892636 A CN108892636 A CN 108892636A CN 201810661824 A CN201810661824 A CN 201810661824A CN 108892636 A CN108892636 A CN 108892636A
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benzyl carboxylate
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曹秀芳
鲍龙珠
王双双
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Huazhong Agricultural University
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Abstract

本发明公开了一种羧酸苄酯类化合物，具有式(Ⅰ)所示的结构。本发明通过对现有的化合物进行结构改造，提高了杀菌剂对作物病原真菌的抑制效果和广谱性，能更好地应用于防治农作物真菌病害，能克服传统甲氧基丙烯酸酯类杀菌剂产生的抗药性。

Description

一种羧酸苄酯类化合物及其用于防治农作物真菌病害的用途
技术领域
本发明属于农药领域，具体涉及一种羧酸苄酯类化合物及其用于防治农作物真菌病害的用途。
背景技术
甲氧基丙烯酸酯类杀菌剂是上世纪八十年代开发的一类广谱高效环境友好型杀菌剂，人们基于其特征结构单元β-甲氧基丙烯酸酯进行衍生并开发了大量杀菌剂新品种，该类杀菌剂目前在市场仍占有重要份额。
随着这类杀菌剂的广泛使用，植物本身复发性突变会产生抗药性个体，而抗性个体的迁移与繁殖会导致抗性亚种群的抗性个体也越来越多，使得这类杀菌剂的作用效果随着时间的推移变得越发不明显，为了解决植物病原真菌产生抗性的问题，必须研发新的化合物作为真菌杀菌剂候选物。
利用已知的具有生物活性的化合物作为中间体，通过化学衍生反应设计合成新化合物，经筛选、优化，从而发现高活性的先导化合物，提高发现新型先导化合物的效率，缩短研究阶段的时间以满足不断变化的市场需求，在农用化学品开发领域非常重要。
发明内容
本发明的目的在于提供一种可以抑制多种植物真菌病菌的含丙烯酸酯结构的羧酸苄酯类化合物，及其在农业领域中用于防治农作物真菌病害的用途。
本发明提供的羧酸苄酯类化合物，具有式(Ⅰ)所示的结构：
式(Ⅰ)中：X为N或CH，R为苯环上的常规取代基，G为结构如下的羧酸结构片段：
优选地，R为H、2-F、2-Cl、2-Br、2-MeO、2-CF3、4-F、4-Cl、4-Br、4-MeO、4-CF3。
式中的波浪线代表的是与分子骨架的连接位点。
试验表明，具有结构通式Ⅰ表示的化合物对茶树上的拟盘多毛孢病菌、拟茎点病菌、链格孢病菌、轮斑病菌、茎点病菌；油菜核盘病菌、菌核病菌；桃褐腐病菌；小麦赤霉病菌；水稻稻瘟病菌；辣椒炭疽病菌；棉花立枯病菌等具有良好的抑菌活性，可用作杀菌剂的有效成分。
本发明扩展了具有医药活性的羧酸类物质在农用杀菌剂领域内的应用，克服了传统甲氧基丙烯酸酯类杀菌剂产生的抗药性。
具体实施方式
本发明通过系统的合成及活性初筛研究，构建了一类羧酸苄酯类化合物，该类化合物具有良好的杀菌活性，能广泛应用于植物真菌病害的防治，是一类具有应用前景的杀菌活性物质。下面用实施例对本发明进行详细说明，本发明并不限于以下实施例。
实施例1
以下为本发明所述的一类羧酸苄酯类化合物的部分代表性化合物
化合物I-1的制备，合成制备路线如下：
在100mL三口圆底烧瓶中加入中间体I(1.5mmol)，然后加入10mL的DMF搅拌使其溶解，再加入无水碳酸钾(2.0mmol)，搅拌反应0.5h后，加入6-氯烟酸(1.5mmol)，在室温条件下搅拌反应，反应完全后，将15mL冰水倒入反应液中，室温搅拌10-15min，乙酸乙酯萃取，有机相用饱和食盐水洗涤，无水硫酸钠干燥，减压脱溶，经硅胶柱层析纯化得化合物I-1。
化合物I-1的结构表征数据如下：浅黄色固体.1H NMR(600MHz,Chloroform-d)δ8.97(s,1H),8.22(d,J＝8.3,2.5,1.0Hz,1H),7.58(s,1H),7.53–7.47(m,1H),7.42–7.32(m,3H),7.23–7.16(m,1H),5.28(s,2H),3.81(s,3H),3.63(s,3H).MS(ESI)m/z 384.3(M+Na)+,calcd.for C18H16ClNO5m/z＝361.07.
选用不同的常规化工原料，参照化合物I-1的合成方法，便可制备实施例1中的其它化合物，部分化合物的结构表征数据如下：
化合物I-2：
黄色半固体.1H NMR(600MHz,Chloroform-d)δ8.51(dd,J＝11.5,4.8,2.0Hz,1H),8.16(dd,J＝7.7,2.0Hz,1H),7.60(s,1H),7.57–7.49(m,1H),7.39–7.34(m,2H),7.30(dd,J＝7.7,4.7Hz,1H),7.21–7.18(m,1H),5.29(s,2H),3.81(s,3H),3.64(s,3H).MS(ESI)m/z384.3(M+Na)+,calcd.for C18H16ClNO5m/z＝361.07.
化合物I-3：
深棕色固体.1H NMR(600MHz,Chloroform-d)δ9.20(s,1H),8.76(d,J＝4.9,1.7Hz,1H),8.29(d,J＝8.0,2.0Hz,1H),7.58(s,1H),7.53(t,1H),7.41–7.35(m,3H),7.22–7.17(m,1H),5.29(s,2H),3.80(s,3H),3.63(s,3H).MS(ESI)m/z 328.4(M+H)+,calcd.forC18H17NO5m/z＝327.11.
化合物I-4：
黄色固体.1H NMR(600MHz,Chloroform-d)δ7.93(s,1H),7.57(s,1H),7.48(dd,J＝5.6,3.5Hz,1H),7.35(dd,J＝5.7,3.4Hz,2H),7.18(dd,J＝5.6,3.4Hz,1H),5.20(s,2H),3.94(s,3H),3.81(s,3H),3.64(s,3H).MS(ESI)m/z 321.4(M+Na)+,calcd.forC18H17F3N2O5m/z＝398.11.
化合物I-5：
白色固体.1H NMR(600MHz,Chloroform-d)δ7.88(s,1H),7.57(s,1H),7.49–7.44(m,1H),7.38–7.33(m,2H),7.21–7.15(m,1H),5.18(s,2H),3.94(s,3H),3.80(s,3H),3.63(s,3H),0.06(s,1H).MS(ESI)m/z 403.4(M+Na)+,calcd.for C18H18F2N2O5m/z＝380.12.
化合物I-6：
白色固体.1H NMR(600MHz,Chloroform-d)δ8.48(d,J＝4.6Hz,1H),7.87(d,J＝8.1Hz,1H),7.54(s,1H),7.40(dd,J＝8.0,4.7Hz,1H),7.31(d,J＝6.2Hz,3H),7.16(d,J＝7.2Hz,1H),7.00(s,1H),5.10(s,2H),3.77(s,3H),3.65(s,3H).MS(ESI)m/z 528.3(M+Na)+,calcd.for C21H17BrClN3O5m/z＝505.00.
化合物I-7：
白色固体.1H NMR(600MHz,Chloroform-d)δ9.60(s,1H),7.99(d,J＝8.0Hz,1H),7.60(s,1H),7.57–7.52(m,1H),7.47(s,1H),7.45–7.33(m,5H),7.29(t,J＝7.3Hz,2H),7.23–7.18(m,1H),6.79(t,1H),5.25(s,2H),3.81–3.78(m,3H),3.67–3.63(m,3H).MS(ESI)m/z 508.4(M+Na)+,calcd.for C26H22F3NO5m/z＝485.15.
化合物I-8：
黄色固体.1H NMR(600MHz,Chloroform-d)δ8.40(dd,J＝4.7,2.0Hz,1H),8.25(dd,J＝7.8,2.0Hz,1H),8.06(s,1H),7.87(d,J＝8.1Hz,1H),7.60(s,1H),7.52(t,1H),7.44–7.38(m,3H),7.27(t,J＝7.7Hz,1H),7.22(t,1H),6.76(dd,J＝7.8,4.7Hz,1H),5.27(s,2H),3.80(s,3H),3.64(s,3H).MS(ESI)m/z 487.4(M+H)+,calcd.for C25H21F3N2O5m/z＝486.14.
化合物I-9：
黄色固体.1H NMR(600MHz,Chloroform-d)δ8.86(d,J＝2.4Hz,1H),8.13(d,J＝2.4Hz,1H),7.73(d,J＝8.8Hz,1H),7.63(d,J＝8.5Hz,2H),7.55(d,J＝8.8Hz,1H),7.38–7.28(m,2H),7.20–7.15(m,1H),5.45(s,2H),3.80(s,3H),3.64(s,3H).MS(ESI)m/z 468.2(M+Na)+,calcd.for C22H17Cl2NO5m/z＝445.05.
化合物I-10：
棕色油状物.1H NMR(600MHz,Chloroform-d)δ7.58(s,1H),7.52–7.46(m,1H),7.39–7.31(m,3H),7.20–7.15(m,1H),7.01–6.97(m,2H),6.80(d,J＝8.0Hz,1H),6.26(d,J＝15.9Hz,1H),5.99(s,2H),5.12(s,2H),3.81(s,3H),3.66(s,3H).MS(ESI)m/z 419.4(M+Na)+,calcd.forC22H20O7m/z＝396.12.
化合物I-11：
棕色油状物.1H NMR(600MHz,Chloroform-d)δ7.64(dd,J＝8.2,1.7Hz,1H),7.57(s,1H),7.54–7.47(m,1H),7.44(d,J＝1.6Hz,1H),7.37–7.34(m,2H),7.20–7.15(m,1H),6.81(d,J＝8.2Hz,1H),6.02(s,2H),5.20(s,2H),3.79(s,3H),3.63(s,3H).MS(ESI)m/z393.3(M+Na)+,calcd.forC20H18O7m/z＝370.11.
化合物I-12：
白色固体.1H NMR(600MHz,Chloroform-d)δ7.56(s,1H),7.41–7.35(m,1H),7.34–7.31(m,2H),7.18–7.13(m,1H),6.85–6.61(m,3H),5.93(s,2H),5.03(s,2H),3.80(s,3H),3.68(s,3H),3.53(s,2H).MS(ESI)m/z 407.39(M+Na)+,calcd.for C21H20O7m/z＝384.12.
化合物I-13：
浅黄色固体.1H NMR(600MHz,Chloroform-d)δ7.58(s,1H),7.51–7.45(m,1H),7.41(dd,J＝15.2,11.0Hz,1H),7.37–7.31(m,2H),7.20–7.15(m,1H),6.99(d,J＝1.7Hz,1H),6.91(dd,J＝8.1,1.7Hz,1H),6.83(t,1H),6.79(s,1H),6.72–6.66(m,1H),5.98(d,2H),5.95(d,J＝15.2Hz,1H),5.11(s,2H),3.82(s,3H),3.68(s,3H).MS(ESI)m/z 445.38(M+Na)+,calcd.for C24H22O7m/z＝422.14.
化合物I-14：
白色固体.1H NMR(600MHz,Chloroform-d)δ7.56(s,1H),7.51–7.39(m,1H),7.38–7.28(m,2H),7.21–7.13(m,1H),6.95(d,J＝9.5Hz,1H),5.02(q,2H),3.82(s,3H),3.69(s,3H),2.16(t,J＝8.9Hz,1H),1.99(d,J＝8.4Hz,1H),1.29(d,J＝4.9Hz,6H).MS(ESI)m/z469.42(M+Na)+,calcd.for C21H22ClF3O5m/z＝446.11.
化合物I-15：
浅绿色油状物.1H NMR(600MHz,Chloroform-d)δ7.52(s,1H),7.32–7.28(m,3H),7.27(s,4H),7.15(d,J＝6.3Hz,1H),5.03(d,J＝13.0Hz,1H),4.94(d,J＝13.0Hz,1H),3.77(s,3H),3.67(s,3H),3.17(d,J＝10.5Hz,1H),2.30(m,1H),1.02(d,J＝6.5Hz,3H),0.70(d,J＝6.7Hz,3H).MS(ESI)m/z 439.35(M+Na)+,calcd.for C23H25ClO5m/z＝416.14.
化合物I-16：
浅绿色油状物.1H NMR(600MHz,Chloroform-d)δ7.58(s,1H),7.52(d,J＝1.8Hz,1H),7.37–7.29(m,4H),7.18(d,J＝7.6Hz,1H),6.59(d,J＝8.6Hz,1H),5.17–5.00(m,3H),3.95(d,J＝5.6Hz,1H),3.81(s,3H),3.69(s,3H),2.23(m,1H),1.06(d,J＝6.9Hz,3H),1.02(d,J＝6.8Hz,3H).MS(ESI)m/z 522.5(M+Na)+,calcd.for C24H25ClF3NO5m/z＝499.14.
实施例3抑制病原真菌菌丝生长试验
供试靶标：茶树拟盘多毛孢病菌(Pestalotiopsis theae)、拟茎点病菌(Phomopsis adianticola)、链格孢病菌(Altermaria alternata)、轮斑病菌(Pestallozzia theae)、茎点病菌(Phoma adianticola)；油菜核盘病菌(Sclerotiniasclerotiorum)、菌核病菌(Rap Sclerotinia stem rot)；桃褐腐病菌(Moniliniafructicola)；小麦赤霉病菌(Gibberella zeae)；水稻稻瘟病菌(Magnapothe grisea)；辣椒炭疽病菌(Colletotrichum gloeosporioides)；棉花立枯病菌(Rhizoctonia solani)。
试验方法：平皿法抑制病原真菌菌丝生长试验
药剂配制：用分析天平(0.01mg)称取一定质量的化合物I-1～I-16，中间体I，加丙酮溶解配制成1×104ppm的均相溶液，现配现用。
将以上配制的药液加入一定量的PDA，制成浓度为100ppm的带药PDA培养基平板，以加丙酮的PDA为空白对照。取活化的以上12种病菌菌块(用Ф＝0.50cm的打孔器制备菌块)，接种于上述PDA平板中，每个菌种和空白对照都重复两次，保鲜膜封口后置于29士1℃培养箱中培养。空白对照组病菌培养长至约为培养皿的三分之二后，用十字交叉法测量菌落直径，计算每种化合物在该浓度下对该菌的抑菌率。
药剂处理：在无菌操作条件下，将预先融化的灭菌培养基定量加入无菌锥形瓶中，将以上配制的药液加入上述锥形瓶中，充分摇匀。制成浓度为100ppm的带药PDA培养基平板，试验设不含药剂的处理作空白对照。
接种：将培养好的以上12种病原菌，在无菌条件下用直径5mm的灭菌打孔器，自菌落边缘切取菌饼，用接种器将菌饼接种于含药平板中央，菌丝面朝上，盖上皿盖，保鲜膜封口后置于29士1℃培养箱中培养。
试验统计：空白对照组病菌培养长至约为培养皿的三分之二后，用十字交叉法测量菌落直径，单位为毫米(mm)。每个菌落用十字交又法垂直测量直径各一次，取其平均值。计算每种化合物在该浓度下对该菌的抑菌率。测定结果如下表1及表2.
表1
表2
从表中的数据可以看出：中间体I对茶树拟盘多毛孢病菌、茶树拟茎点病菌、茶树轮斑病菌、油菜菌核病菌、桃褐腐病菌、小麦赤霉病菌、水稻稻瘟病菌具有一定的抑制活性，而对茶树链格孢病菌、油菜核盘病菌、辣椒炭疽病菌、茶树茎点病菌、棉花立枯病菌的抑制活性很低甚至没有活性，可见中间体I对病原真菌抑制的广谱性较差且抑菌能力较弱。
而本发明中的化合物对12种病原真菌都具有抑制活性，说明通过结构改造提高了抑菌剂的广谱性，而且抑菌效果普遍优于中间体I，其中化合物I-4、I-10、I-12、I-14抑菌谱最广，抑菌效果最强。
以上仅列举了本发明化合物对12种真菌的抑制率，需要强调的是，本发明实施例1中的化合物作为杀菌剂所能防治的作物病原真菌并没有特别限制，代表性作物病害的例子包括但不限于：霜霉病、叶霉病、灰霉病、疫霉病、赤霉病、稻瘟病、稻曲病、黑星病、赤星病、叶斑病、褐斑病、疫病、颖枯病、立枯病、叶枯病、纹枯病、网斑病、黑斑病、斑点落叶病、红腐病、腐烂病、根腐病、褐腐病、恶苗病、轮纹病、炭疽病、菌核病、白粉病、锈病、疫病、黄萎病、小斑病、全蚀病、枝枯病、松赤枯病等。

Claims (4)

1.一种羧酸苄酯类化合物，其特征在于具有式(Ⅰ)所示的结构：
其中：X为N或CH，R为苯环上的常规取代基，G为结构如下的羧酸结构片段：
2.如权利要求1所述的一种羧酸苄酯类化合物，其特征在于：R为H、2-F、2-Cl、2-Br、2-MeO、2-CF3、4-F、4-Cl、4-Br、4-MeO、4-CF3。
3.权利要求1或2所述的羧酸苄酯类化合物用于防治农作物真菌病害的用途。
4.一种用于防治农作物真菌病害的杀菌剂，其活性成分是权利要求1或2所述的羧酸苄酯类化合物。
CN201810661824.1A 2018-06-25 2018-06-25 一种羧酸苄酯类化合物及其用于防治农作物真菌病害的用途 Pending CN108892636A (zh)

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US5194438A (en) * 1988-07-15 1993-03-16 Basf Aktiengesellschaft α-arylacrylates substituted by a trifluoromethylpyrimidinyloxy radical, fungicidal compositions and methods
CN101921226A (zh) * 2009-06-15 2010-12-22 中国中化股份有限公司 取代羧酸酯类化合物及其用途
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Publication number Priority date Publication date Assignee Title
US4952720A (en) * 1987-10-07 1990-08-28 Basf Aktiengsellschaft Ortho-substituted benzyl carboxylates and fungicides which contain these compounds
US5194438A (en) * 1988-07-15 1993-03-16 Basf Aktiengesellschaft α-arylacrylates substituted by a trifluoromethylpyrimidinyloxy radical, fungicidal compositions and methods
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