CN102850342B - 一种含噻二唑的噁二唑类化合物及其制备与应用 - Google Patents
一种含噻二唑的噁二唑类化合物及其制备与应用 Download PDFInfo
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
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Abstract
本发明涉及一种含噻二唑的噁二唑类化合物及其制备方法，所述的噻二唑类化合物，其结构如式（I）所示：
Description
技术领域
本发明涉及一种含噻二唑的噁二唑类化合物即2-(4-甲基-1,2,3-噻二唑-5-基)-5-(取代苄硫基)-1,3,4-噁二唑衍生物及其制备与应用。
背景技术
杂环化合物已是新农药发展的主流，而在杂环化合物中，又以含氮杂环为主。1,3,4-噁二唑类化合物也有很重要的生物活性，包括抗炎、抗癌、抗病毒、抑菌和除草等活性。如合成的2-取代吡唑-5-甲硫基-1,3,4-噁二唑，在100 mg/L时对水稻纹枯病菌表现出良好的抑制活性；2-甲基-5-取代苄硫基-1,3,4-噁二唑在100ppm下对油菜具有较好的抑制效果。1,2,3噻二唑类化合物是近年来发展比较迅速的一类，许多商品化的杀虫、杀菌、除草剂，植物诱抗剂属于该类。例如，日本农药公司开发的具有内吸性的杀菌剂噻酰菌胺（thiadinal）主要用于水稻稻瘟病的防治，对其他病害如褐斑病、白叶枯病、纹枯病及芝麻叶枯病等也有较好的防治效果。以及诺华公司开发的植物诱导抗病激活剂Bion（BTH）。
然而，尚未见有关2-(4-甲基-1,2,3-噻二唑-5-基)-5-(取代苄硫基)-1,3,4-噁二唑衍生物的合成及其生物活性研究的文献报道。
发明内容
本发明目的是提供一种具有杀菌活性的2-(4-甲基-1,2,3-噻二唑-5-基)-5-(取代苄硫基)-1,3,4-噁二唑衍生物及其制备方法与应用。
本发明的目的是这样实现的：
式（I）所示的含噻二唑的噁二唑类化合物：
（I）
式（I）中：R为取代苯基，所述取代选自氢、C1-C4烷基、C1-C4烷氧基和卤素。
本发明所述式（I）化合物可由如下方法制得：将式（II）化合物和式（III）化合物与有机溶剂混合，在碱性物质的存在下，0~25℃（优选25℃）搅拌反应，TLC跟踪反应（以体积比1:1~5的石油醚和乙酸乙酯混合溶液为展开剂，跟踪原料点消失为反应完全），反应完全后，将反应液置于冰水中，析出固体，过滤，滤液进行硅胶柱层析（以体积比为5:1的石油醚和乙酸乙酯混合溶液为洗脱剂，收集含目标组分的洗脱液，干燥）或用重结晶溶剂进行重结晶，获得式（I）所示的含噻二唑的噁二唑类化合物；
重结晶溶剂为石油醚、乙酸乙酯、正己烷或乙醇中的一种或多种，优选石油醚与乙酸乙酯的混合溶液；
有机溶剂为N,N-二甲基甲酰胺、四氢呋喃、1,4-二氧六环或丙酮中的一种或多种，优选为N,N-二甲基甲酰胺（DMF）；
碱性物质为碳酸钾、碳酸氢钠、氢氧化钠、氢氧化钾或氢化钠中的一种或多种，优选为碳酸钾；
式（II）化合物、式（III）化合物和碱性物质的物质的量之比为1:1.0~1.5:1.0~1.5，优选为1:1.0:1.2；有机溶剂体积用量以式（II）化合物物质的量计为2-10ml/mmol，优选4ml/mmol。
式（I）和式（III）中：R的定义如前所述，X为卤素或对甲苯磺酸酯基。
本发明还提供式（I）所示的含噻二唑的噁二唑化合物在防治黄瓜褐斑病、黄瓜细菌性角斑病、黄瓜蔓枯病、黄瓜霜霉病、黄瓜菌核病中的应用。
本发明还提供含有式（I）所示的含噻二唑的噁二唑化合物的杀菌剂，其还包含至少一种农药上可接受的助剂。
与现有技术相比，本发明的有益效果主要体现在：本发明提供了一种含噻二唑的噁二唑类化合物及中间体的其制备方法及应用，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。
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：
本发明的含噻二唑的噁二唑类化合物（I）可以如下方法合成：
25 mL圆底烧瓶中加入2 mmol化合物II、2 mmol取代氯苄、8mL DMF和2.4mmol的K2CO3，室温搅拌，TLC检测反应进度。反应完毕后，反应液倾入30mL冰水中，析出固体，过滤，脱溶，硅胶柱层析，得固体产物。
实施例1
2-(4-甲基-1,2,3-噻二唑-5-基)-5-(2,4-二氯苄硫基)-1,3,4-噁二唑（Ia）：白色晶体，产率 84%，熔点85-86℃; 1H
NMR (CDCl3, 400 MHz), δ:3.06(s,
3H, Het-Me), 4.60(s, 2H, SCH2), 7.22(d, J=8.49Hz, 1H, ArH),
7.44(s, 1H, ArH), 7.61(d, J=8.27Hz, 1H, ArH). MS (ESI), m/z: 360 (M+1).
Elemental anal. (%), calculated: C, 40.12; H, 2.24; N, 15.60; found: C, 39.88;
H, 2.55; N,15.79。
实施例2
2-(4-甲基-1,2,3-噻二唑-5-基)-5-(3-氯苄硫基)-1,3,4-噁二唑（Ib）：白色晶体，产率 88%，熔点88-89℃; 1H
NMR (CDCl3, 400 MHz), δ:3.06(s,
3H, Het-Me), 4.51(s, 2H, SCH2), 7.30(s, 2H, ArH), 7.34-7.39(m, 1H,
ArH), 7.47(s, 1H, ArH). MS (ESI), m/z: 326 (M+1). Elemental anal. (%),
calculated: C, 44.37; H, 2.79; N, 17.25; found: C, 44.67; H, 2.85; N,17.43。
实施例3
2-(4-甲基-1,2,3-噻二唑-5-基)-5-(3-氟苄硫基)-1,3,4-噁二唑（Ic）：白色晶体，产率 79%，熔点63-64◦C; 1H NMR (CDCl3,
400 MHz), δ:3.06(s, 3H, Het-Me), 4.53(s, 2H, SCH2),
7.04(t, J=7.46Hz, 1H, ArH), 7.19(d, J=9.27Hz, 1H, ArH),
7.29-7.35(m, 2H, ArH). MS (ESI), m/z: 309 (M+1). Elemental anal. (%),
calculated: C, 46.74; H, 2.94; N, 18.17; found: C, 46.45; H, 3.12; N, 18.44。
实施例4
2-(4-甲基-1,2,3-噻二唑-5-基)-5-(2-氯苄硫基)-1,3,4-噁二唑（Id）：白色晶体，产率 81%，熔点98-99℃; 1H
NMR (CDCl3, 400 MHz), δ:3.06(s,
3H, Het-Me), 4.65(s, 2H, SCH2), 7.26-7.30(m, 2H, ArH), 7.41(d, J=7.45Hz,
1H, ArH), 7.63(d, J=7.14Hz, 1H, ArH). MS (ESI), m/z: 326 (M+1).
Elemental anal. (%), calculated: C, 44.37; H, 2.79; N, 17.25; found: C, 44.64;
H, 2.99; N, 17.01。
实施例5
2-(4-甲基-1,2,3-噻二唑-5-基)-5-(2-氟苄硫基)-1,3,4-噁二唑（Ie）：白色晶体，产率 85%，熔点78-79℃; 1H
NMR (CDCl3, 400 MHz), δ:3.06(s,
3H, Het-Me), 4.58(s, 2H, SCH2), 7.07-7.14(m, 2H, ArH), 7.29-7.33(m,
1H, ArH), 7.55(t, J=8.20Hz, 1H, ArH). MS (ESI), m/z: 309 (M+1).
Elemental anal. (%), calculated: C, 46.74; H, 2.94; N, 18.17; found: C, 46.88;
H, 3.12; N, 18.43。
实施例6
2-(4-甲基-1,2,3-噻二唑-5-基)-5-(2-甲基苄硫基)-1,3,4-噁二唑（If）：白色晶体，产率 83%，熔点79-80℃; 1H
NMR (CDCl3, 400 MHz), δ:2.45(s,
3H, Ar-Me), 3.06(s, 3H, Het-Me), 4.59(s, 2H, SCH2), 7.8-7.23(m, 2H,
ArH), 7.29-7.34(m, 1H, ArH), 7.42(d, J=6.11Hz, 1H, ArH). MS (ESI), m/z:
305 (M+1). Elemental anal. (%), calculated: C, 51.30; H, 3.97; N, 18.41; found:
C, 51.55; H, 3.87; N, 18.49。
实施例7
2-(4-甲基-1,2,3-噻二唑-5-基)-5-(4-氟苄硫基)-1,3,4-噁二唑（Ig）：白色晶体，产率 77%，熔点84-85℃; 1H
NMR (CDCl3, 400 MHz), δ:2.45(s,
3H, Ar-Me), 3.06(s, 3H, Het-Me), 4.52(s, 2H, SCH2), 7.06(t, J=8.55Hz,
2H, ArH), 7.46(d, J=5.76Hz, 2H, ArH). MS (ESI), m/z: 305 (M+1).
Elemental anal. (%), calculated: C, 46.74; H, 2.94; N, 18.17; found: C, 46.88;
H, 3.06; N, 17.99。
实施例8
2-(4-甲基-1,2,3-噻二唑-5-基)-5-(苄硫基)-1,3,4-噁二唑（Ih）：白色晶体，产率 88%，熔点72-73℃; 1H
NMR (CDCl3, 400 MHz), δ:3.05(s,
3H, Het-Me), 4.55(s, 2H, SCH2), 7.30-7.37(m, 3H, ArH), 7.46(d, J=7.21Hz,
2H, ArH). MS (ESI), m/z: 291 (M+1). Elemental anal. (%), calculated: C, 49.64;
H, 3.47; N, 19.30; found: C, 50.01; H, 3.78; N, 19.12。
实施例9
2-(4-甲基-1,2,3-噻二唑-5-基)-5-(4-甲氧基苄硫基)-1,3,4-噁二唑（Ii）：白色晶体，产率 79%，熔点56-57℃; 1H
NMR (CDCl3, 400 MHz), δ:3.05(s,
3H, Het-Me), 3.80(s, 3H, OMe), 4.52(s, 2H, SCH2), 6.87(d, J=8.41Hz,
2H, ArH), 7.41(d, J=8.46Hz, 2H, ArH). MS (ESI), m/z: 321 (M+1).
Elemental anal. (%), calculated: C, 48.73; H, 3.78; N, 17.49; found: C, 48.78;
H, 3.99; N, 17.54。
杀菌活性测试
供试作物：黄瓜(Cucumis sativus L.)，品种为：新泰密刺。
环境条件：黄瓜苗2片子叶期。
试验药剂及处理剂量：各样品均设一个试验浓度500mg/L。
供试菌株：黄瓜褐斑病菌，黄瓜细菌性角斑病菌，黄瓜蔓枯病菌，黄瓜霜霉病菌，黄瓜菌核病菌，上述菌株均来自中国农业科学院蔬菜花卉所。
所有处理均分别设3次重复，每次重复10株苗，温室内采用随机排列。
施药、接种方式：将供试药剂及对照药剂分别按试验浓度配好，于晴天上午将供试药剂及对照药剂均匀喷施于黄瓜子叶上，2小时后接种病原菌，保湿培养。
待对照充分发病后调查病情指数并计算防治效果，结果见表1。
表 1 目标化合物的活体杀菌活性
| 编号 | 黄瓜褐斑病 | 黄瓜细菌性角斑病 | 黄瓜蔓枯病 | 黄瓜霜霉病 | 黄瓜菌核病 |
| Ia | 77.66 | 68.08 | -2.73 | 41.78 | 36.93 |
| Ib | 53.68 | 38.02 | 19.13 | 35.97 | 12.98 |
| Ic | 84.55 | 53.30 | 59.52 | 68.43 | 21.16 |
| Id | 92.77 | 58.22 | 48.17 | 53.13 | -10.26 |
| Ie | 94.64 | 47.98 | 56.81 | 53.13 | -21.48 |
| If | 88.12 | 53.27 | 26.02 | 45.39 | 3.05 |
| Ig | 72.35 | 14.78 | 31.99 | 46.24 | 16.48 |
| Ih | 72.72 | 65.59 | 23.72 | 42.75 | 32.51 |
| Ii | 64.26 | 32.62 | -11.66 | 59.56 | 0.81 |
Claims (2)
1.一种式（I）所示的含噻二唑的噁二唑类化合物，
R为邻氯苯基，邻氟苯基，间氟苯基，对氟苯基，邻甲基苯基，苯基，2,4-二氯苯基。
2.一种如权利要求1所述的含噻二唑的噁二唑化合物在防治以下病害中的应用，其中防治黄瓜褐斑病，其中R为邻氯苯基，邻氟苯基，间氟苯基，对氟苯基，邻甲基苯基，苯基，2,4-二氯苯基；黄瓜细菌性角斑病，其中R为邻氯苯基，2,4-二氯苯基；黄瓜蔓枯病，R为邻氟苯基，间氟苯基，对氟苯基，邻甲基苯基，苯基；黄瓜菌核病，R为间氟苯基，对氟苯基，邻甲基苯基，苯基，2,4-二氯苯基。
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