CN101279951A - 2-嘧啶氧(硫)基苯甲酸基烯酸酯类化合物及其应用 - Google Patents
2-嘧啶氧(硫)基苯甲酸基烯酸酯类化合物及其应用 Download PDFInfo
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- CN101279951A CN101279951A CNA2007100108586A CN200710010858A CN101279951A CN 101279951 A CN101279951 A CN 101279951A CN A2007100108586 A CNA2007100108586 A CN A2007100108586A CN 200710010858 A CN200710010858 A CN 200710010858A CN 101279951 A CN101279951 A CN 101279951A
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- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 238000009333 weeding Methods 0.000 claims abstract description 7
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- 239000005711 Benzoic acid Substances 0.000 claims description 7
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Landscapes
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Abstract
本发明公开了2－嘧啶氧(硫)基苯甲酸基烯酸酯类化合物，如通式(I，II)所示：式中：X选自氧或硫；R1选自H、卤素、4，6－二甲氧基嘧啶－2－基或者下列基团：其中，氮氧键与双键上的甲基为顺式或反式；R2、R3、R4、R6、R7分别选自H或C1－C6烷基；R5选自C1－C6烷基、C2－C6烷氧烷基、C3－C6烯基或C3－C6炔基；R6与R7基团为顺式或反式；R8选自C1－C6烷基、C3－C6烯基或C3－C6炔基。化合物(I，II)具有除草活性，对大豆、棉花、花生、油菜、玉米等作物安全。
Description
技术领域
本发明属于除草剂领域，具体涉及一种2-嘧啶氧(硫)基苯甲酸基烯酸酯类化合物及其应用。
背景技术
由于杂草种群的演替、变迁以及对化学农药抗药性的产生和迅速发展，人们对生态环境保护意识的不断加强，对化学农药污染、农药对非靶标生物影响的认识以及在农药生态环境中归宿问题的重视不断提高。随着世界耕地面积的逐渐减少、人口的不断增长及对粮食需求量的增加，迫使人们迅速发展农业生产技术、改进完善耕作制度，并需要不断发明新型的和改进的除草化合物和组合物。
EP223406报道了某些2-嘧啶氧(硫)基苯甲酸酯类化合物具有除草活性，并对花生、向日葵安全。CN1749236A和CN1927811A公开了某些3-苯氧基苯甲酸基烯酸酯类化合物具有除草活性。现有技术中未涉及如本发明所示的2-嘧啶氧(硫)基苯甲酸基烯酸酯类化合物的制备及其应用。
发明内容
本发明的目的是提供一种结构新颖、具有很好除草活性且对作物安全的2-嘧啶氧(硫)基苯甲酸基烯酸酯类化合物及其以该类化合物为活性组分的除草组合物，以满足农业生产迅速发展的需要。
本发明的技术方案如下：
本发明提供了一种结构新颖的2-嘧啶氧(硫)基苯甲酸基烯酸酯类化合物，如通式(I，II)所示：
式中：
X选自氧或硫；
R1选自氢、卤素、4，6-二甲氧基嘧啶-2-基或者下述基团：
其中，氮氧键与双键上的甲基为顺式或反式；
R2、R3、R4、R6、R7分别选自氢或C1-C6烷基；
R5选自C1-C6烷基、C2-C6烷氧烷基、C3-C6烯基或C3-C6炔基；
R6与R7基团为顺式或反式；
R8选自C1-C6烷基、C3-C6烯基或C3-C6炔基。
本发明中较为优选的化合物为，通式(I，II)中：
X选自氧或硫；
R1选自氢、卤素、4，6-二甲氧基嘧啶-2-基或者下述基团：
其中，氮氧键与双键上的甲基为顺式；
R2、R3、R4、R6、R7分别选自氢；R6与R7基团为反式；
R5选自C1-C6烷基、C3-C6烯基或C3-C6炔基；
R8选自甲基。
本发明中进一步优选的化合物为，通式(I，II)中：
X选自氧或硫；
R1选自氢或卤素；
R2、R3、R4、R6、R7分别选自氢；R6与R7基团为反式；
R5选自C1-C6烷基、C3-C6烯基或C3-C6炔基。
通式(I，II)中所指的烷基包括直链或支链烷基。烷氧烷基是指直链或支链形式，含烷氧基团的烷基，例如甲氧甲基、异丙氧乙基等。烯基是指直链或支链形式，有1到2个碳碳双键的基团，例如，丙烯基、烯丙基等。炔基是指直链或支链形式，有1到2个碳碳三键的基团，例如，丙炔基、炔丙基等。卤素包括氟，氯，溴，碘。
本发明的通式(I，II)化合物可由如下方法制备：
将化合物(III)(有市售，也可自制、制备方法参见Pestic.Sci.1996，47，115-124)与化合物(IV)(制备方法参见J.Org.Chem.32：3229(1967))溶于适宜的溶剂中，在温度为-10℃到沸点之间反应0.5-48小时制得化合物(V)。适宜的溶剂可选自例如甲苯、丙酮、DMF、THF或二氧六环等。加入碱类物质，如三乙胺、吡啶、氢氧化钠、氢氧化钾、碳酸钠、碳酸钾等对反应有利。
将化合物(V)与适宜的碱加入到适宜的有机溶剂和水形成的混合溶剂中，在温度为-10℃到沸点之间反应0.5-48小时，反应液经盐酸或硫酸酸化，制得中间体酸即化合物(VI)。适宜的有机溶剂选自氯仿、二氯甲烷、四氯化碳、正己烷、苯、甲苯、乙酸乙酯、甲醇、乙醇、THF或二氧六环等；适宜的碱选自氢氧化钠、氢氧化钾、碳酸钠或碳酸钾等。
化合物(VI)与化合物(VII)(VII的制备方法参见合成化学，13(3)，315-316，(2005))溶于适宜的溶剂例如甲苯、丙酮、DMF、THF或二氧六环等，在温度为-10℃到沸点之间反应0.5-48小时，制得化合物(I)。加入碱类物质如三乙胺、吡啶、氢氧化钠、氢氧化钾、碳酸钠、碳酸钾等对反应有利。化合物(VII)中，Y可为氯、溴或碘。
由于起始原料或者反应条件的差异，可得到R6与R7基团为顺式或反式的化合物(VIII)，或同时含有不同比例的顺式和反式化合物(VIII)的混合物(VIII的制备参见CN1927811A)。化合物(VIII)中，Y可为氯、溴或碘。
化合物(VI)与化合物(VIII)溶于适宜的溶剂例如甲苯、丙酮、DMF、THF或二氧六环等，在温度为-10℃到沸点之间反应0.5-48小时，制得R6与R7基团为顺式或反式的化合物(II)，或同时含有不同比例的顺式和反式化合物(II)的混合物。加入碱类物质如三乙胺、吡啶、氢氧化钠、氢氧化钾、碳酸钠或碳酸钾等对反应有利。
表1：部分如通式(I)所示的本发明化合物
表2：部分如通式(II)所示的本发明化合物
部分化合物的1H NMR(CDCl3，300MHz)δ(ppm)数据如下：
化合物1
3.807(s，9H，CH3)，4.857(s，2H，CH2)，5.736(s，1H)，5.857(s，1H，＝CH)，6.332(s，1H，＝CH)，7.328(m，2H，Ar-H)，7.569(m，1H，Ar-H)，8.040(q，1H，J＝1.8Hz，Ar-H).
化合物2
0.947(t，3H，J＝7.3Hz，CH3)，1.693(m，2H，CH2)，3.804(s，6H，OCH3)，4.110(t，2H，J＝6.6Hz，CH2)，4.867(s，2H，CH2)，5.736(s，1H)，5.834(d，1H，J＝1.2Hz，＝CH)，6.331(d，1H，J＝0.9Hz，＝CH)，7.352(m，2H，Ar-H)，7.594(m，1H，Ar-H)，8.040(q，1H，J＝1.8Hz，Ar-H).
化合物3
2.492(t，1H，J＝2.4Hz，1H)，3.784(s，6H，OCH3)，4.765(s，2H，CH2)，4.878(s，2H，CH2)，5.740(s，1H)，5.929(d，1H，J＝0.9Hz，＝CH)，6.402(d，1H，J＝0.9Hz，＝CH)，7.327(m，2H，Ar-H)，7.601(m，1H，Ar-H)，8.044(q，1H，J＝1.8Hz，Ar-H).
化合物4
1.287(t，3H，J＝7.1Hz，CH3)，3.780(s，6H，OCH3)，4.219(q，2H，J＝7.2Hz，CH2)，4.866(s，2H，CH2)，5.732(s，1H)，5.831(s，1H，＝CH)，6.321(s，1H，＝CH)，7.324(m，2H，Ar-H)，7.590(m，1H，Ar-H)，8.039(q，1H，J＝1.2Hz，Ar-H).
化合物5
1.305(t，3H，J＝7.1Hz，CH3)，3.711(s，6H，OCH3)，4.222(q，2H，J＝7.2Hz，CH2)，5.045(s，2H，CH2)，5.709(s，1H)，5,860(s，1H，＝CH)，6.339(s，1H，＝CH)，7.448(m，2H，Ar-H)，7.631(d，1H，Ar-H).
化合物12
3.761(s，3H，CO2CH3)，3.788(s，6H，OCH3)，4.786(q，2H，CH2)，5.739(s，1H)，6.020(m，1H，＝CH)，6.840(m，1H，CH＝)，7.340(m，2H，Ar-H)，7.616(m，1H，Ar-H)，8.162(m，1H，Ar-H).
化合物13
1.272(t，3H，CH3)，3.789(s，6H，OCH3)，4.189(q，2H，CH2)，4.786(q，2H，CH2)，5.740(s，1H)，6.006(m，1H，＝CH)，6.856(m，1H，CH＝)，7.282(m，2H，Ar-H)，7.616(m，1H，Ar-H)，8.031(m，1H，Ar-H).
化合物14
0.970(m，3H，CH3)，1.407(m，2H，CH2)，1.659(m，2H，CH2)，3.789(s，6H，CH3)，4.191(m，2H，CH2)，4.785(q，2H，CH2)，5.739(s，1H)，6.014(m，1H，＝CH)，6.804(m，1H，CH＝)，7.342(m，2H，Ar-H)，7.618(m，1H，Ar-H)，8.052(m，1H，Ar-H).
化合物15
0.960(m，3H，CH3)，1.678(m，2H，CH2)，3.790(s，6H，OCH3)，4.112(m，2H，CH2)，4.789(q，2H，CH2)，5.746(s，1H)，6.014(m，1H，＝CH)，6.810(m，1H，CH＝)，7.260(m，1H，Ar-H)，7.369(m，1H，Ar-H)，7.613(m，1H，Ar-H)，8.053(m，1H，Ar-H).
化合物16为两种构型的混合物，其中含顺式33％(通式II中，R6与R7基团在双键同侧)；
含反式67％(通式II中，R6与R7基团不在双键同侧)。
顺式：1.271(m，3H，CH3)，1.872(s，3H，CH3)，3.800(s，6H，OCH3)，4.172(q，2H，J＝6.9Hz，CH2)，5.266(s，2H，CH2)，5.735(s，1H，＝CH)，5.788(s，1H)，7.325(m，2H，Ar-H)，7.617(m，1H，Ar-H)，8.059(m，1H，Ar-H).
反式：1.271(m，3H，CH3)，2.105(s，3H，CH3)，3.800(s，6H，OCH3)，4.172(q，2H，J＝6.9Hz，CH2)，4.615(s，2H，CH2)，5.735(s，1H，＝CH)，5.788(s，1H)，7.325(m，2H，Ar-H)，7.617(m，1H，Ar-H)，8.059(m，1H，Ar-H).
化合物17
1.285(t，3H，CH3)，3.720(s，6H，OCH3)，4.199(q，2H，CH2)，4.955(m，2H，CH2)，5.717(s，1H)，6.012(m，1H，＝CH)，6.918(m，1H，CH＝)，7.469(m，2H，Ar-H)，7.635(d，1H，Ar-H).
本发明的通式(I，II)化合物具有除草活性。与现有技术中公开的化合物相比，本发明的化合物在较低剂量下苗前、苗后使用可有效控制单双子叶杂草，尤其对禾本科杂草具有较高的防除活性。因此本发明的技术方案包括通式(I，II)化合物用于控制杂草的用途。
本发明的通式(I，II)化合物在苗前使用，对大豆、棉花、花生等作物安全；在苗后使用，对玉米、花生、油菜等作物安全，尤其对禾本科作物玉米的安全性具有令人出乎意料的满意效果，同时保持了对禾本科杂草稗草的高防除活性。
本发明还包括以通式(I，II)化合物作为活性组分的除草组合物。该除草组合物中活性组分的重量百分含量为5-90％。该除草组合物中还包括农业上可接受的载体。
本发明的除草组合物可以多种制剂的形式施用。通常将本发明的化合物溶解或分散于载体中配制成制剂以便作为除草剂使用时更易于分散。例如：这些化学制剂可被制成可湿性粉剂或乳油。因此，在这些组合物中，至少加入一种液体或固体载体，并且通常需要加入适当的表面活性剂。
本发明另外的实施方案为防治杂草的方法，该方法包括将本发明的除草组合物施于所述杂草或所述杂草生长的场所或其生长介质的表面上。通常选择的较为适宜有效量为每公顷10克到5000克，优选有效量为每公顷20克到2500克。对于某些应用，可在本发明的除草组合物中加入一种或多种其它的除草剂，由此可产生附加的优点和效果。
本发明的化合物既可以单独使用也可以和其它已知的杀虫剂、杀菌剂、植物生长调节剂或肥料等一起混合使用。
应明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动。
具体实施方式
下列实施例和生测试验结果可用来进一步说明本发明，但不意味着限制本发明。合成实例
化合物4的合成：
1.
向250毫升圆底烧瓶中加入4，6-二甲氧基-2-甲磺酰基嘧啶7克(0.036摩尔)，水杨酸甲酯6毫升(0.047摩尔)，碳酸钾6克(0.043摩尔)，N，N-二甲基甲酰胺100毫升。于110-130℃搅拌反应4小时后，冷却至室温。向反应液中加入乙酸乙酯200毫升和水180毫升，萃取。有机相依次用1％稀盐酸50毫升、50毫升饱和碳酸氢钠、3×50毫升饱和氯化钠水溶液洗涤，无水硫酸镁干燥，脱溶后得到的残余物经硅胶柱色谱(石油醚/乙酸乙酯＝5/1)纯化，得到2-(4，6-二甲氧基-2-嘧啶氧基)苯甲酸甲酯8.35克。
2.
向150毫升圆底烧瓶中依次加入2-(4，6-二甲氧基-2-嘧啶氧基)苯甲酸甲酯2.93克(0.01摩尔)、四氢呋喃50毫升、氢氧化钠0.4克(0.01摩尔)溶于50毫升水的溶液，常温搅拌反应过夜。反应完全后减压蒸出四氢呋喃。向残余物中加入200毫升乙酸乙酯、浓盐酸2毫升，50毫升水洗，3×50毫升饱和氯化钠水溶液洗涤有机相，无水硫酸镁干燥，脱溶后得2-(4，6-二甲氧基-2-嘧啶氧基)苯甲酸2.05克。
3.
向100毫升三口圆底烧瓶中依次加入2-(4，6-二甲氧基-2-嘧啶氧基)苯甲酸1.0克(3.6毫摩尔)、N，N-二甲基甲酰胺30毫升、碳酸钾0.50克(3.6毫摩尔)、2-溴甲基丙烯酸乙酯0.69克(3.6毫摩尔)。于40-60℃搅拌反应8小时后，向反应液中加入乙酸乙酯200毫升和水180毫升，萃取，用180毫升的饱和氯化钠水溶液洗涤有机相，再用无水硫酸镁干燥，脱溶后得到的残余物经硅胶柱色谱(石油醚/乙酸乙酯＝3/1)纯化，得到2-(乙氧羰基)烯丙基-2-(4，6-二甲氧基-2-嘧啶氧基)苯甲酸酯1.05克。
化合物17的合成：
向100毫升三口圆底烧瓶中依次加入6-氯-2-(4，6-二甲氧基-2-嘧啶硫基)苯甲酸0.32克(0.9毫摩尔)、N，N-二甲基甲酰胺10毫升、碳酸钾0.17克(1.2毫摩尔)、反式4-溴丁烯酸乙酯0.34克(1.5毫摩尔)。于80℃搅拌反应4小时后，向反应液中加入乙酸乙酯200毫升和水180毫升，萃取，用200毫升的饱和氯化钠水溶液洗涤有机相，再用无水硫酸镁干燥，脱溶后得到的残余物经硅胶柱色谱(石油醚/乙酸乙酯＝3/1)纯化，得到4-(6-氯-2-(4，6-二甲氧基-2-嘧啶硫基)苯甲酸基)反式丁烯酸乙酯0.28克。
表1和表2中的其他化合物可通过以上类似的方法制得。
生测实例
原药用丙酮溶解后，按试验要求用1‰的吐温80静置自来水配制所需浓度的待测液。用履带式作物喷雾机(英国Engineer Research Ltd.设计生产)进行喷雾处理(喷雾压力1.95kg/cm2，喷液量50ml/m2，履带速度30cm/s，喷嘴为扇形喷嘴)。
苗前试验：将定量的杂草(苘麻、稗草、狗尾草)和作物(水稻、小麦、玉米、棉花、花生、大豆)种子分别播于截面积为100cm2的培养钵中，播后覆土1cm，供试化合物喷雾于土壤表面，处理后置于温室，然后浇水，以1‰的吐温80静置自来水处理作为对照。
苗后试验：将定量的杂草(苘麻、稗草、狗尾草)和作物(玉米、棉花、花生、油菜、大豆)种子分别播于截面积为100cm2的培养钵中，播后覆土1cm，在温室按常规方法培养。待杂草长至1.5叶期，水稻、小麦、玉米、棉花、花生、油菜和大豆2-3叶期，选取生长均匀一致的试材进行苗后茎叶喷雾处理，以1‰的吐温80静置自来水处理作为对照。试材处理后放在干燥通风处，待药液自然风干后，置于温室内按常规方法管理，处理后48小时内采用从底部灌水的方法，避免药液被冲刷。
处理后4周进行目测调查，抑制率为与对照相比的各种损伤程度，包括杀死、失绿、枯斑、扭曲、畸形、生长抑制或叶片灼烧等。部分测试结果见表3、4。
表3：部分通式(I，II)化合物的除草活性(苗前/苗后，抑制率％)
表4：部分通式(I，II)化合物对作物的安全性(苗前/苗后，抑制率％)
注*：表3和表4中，“-”表示未测。
Claims (6)
1. 2-嘧啶氧(硫)基苯甲酸基烯酸酯类化合物，如通式(I，II)所示：
式中：
X选自氧或硫；
R1选自氢、卤素、4，6-二甲氧基嘧啶-2-基或者下列基团：
其中，氮氧键与双键上的甲基为顺式或反式；
R2、R3、R4、R6、R7分别选自氢或C1-C6烷基；
R5选自C1-C6烷基、C2-C6烷氧烷基、C3-C6烯基或C3-C6炔基；
R6与R7基团为顺式或反式；
R8选自C1-C6烷基、C3-C6烯基或C3-C6炔基。
2. 按照权利要求1所述的化合物，其特征在于，通式(I，II)中：
X选自氧或硫；
R1选自氢、卤素、4，6-二甲氧基嘧啶-2-基或者下述基团：
其中，氮氧键与双键上的甲基为顺式；
R2、R3、R4、R6、R7分别选自氢；R6与R7基团为反式；
R5选自C1-C6烷基、C3-C6烯基或C3-C6炔基；
R8选自甲基。
3. 按照权利要求2所述的化合物，其特征在于，通式(I，II)中：
X选自氧或硫；
R1选自氢或卤素；
R2、R3、R4、R6、R7分别选自氢；R6与R7基团为反式；
R5选自C1-C6烷基、C3-C6烯基或C3-C6炔基。
4. 权利要求1所述的通式(I，II)化合物用于控制杂草的用途。
5. 一种除草组合物，含有如权利要求1所述的作为活性组分的通式(I，II)化合物和农业上可接受的载体，组合物中活性组分的重量百分含量为5-90％。
6. 一种控制杂草的方法，其特征在于：向杂草或杂草的生长介质或地点上施用除草有效剂量的如权利要求5所述的除草组合物。
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