CN1743304A - 一种2-(二取代)甲基丙烯酸酯类化合物及其应用 - Google Patents
一种2-(二取代)甲基丙烯酸酯类化合物及其应用 Download PDFInfo
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- CN1743304A CN1743304A CN 200510098960 CN200510098960A CN1743304A CN 1743304 A CN1743304 A CN 1743304A CN 200510098960 CN200510098960 CN 200510098960 CN 200510098960 A CN200510098960 A CN 200510098960A CN 1743304 A CN1743304 A CN 1743304A
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- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
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- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
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- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
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- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 14
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- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
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Abstract
本发明属于除草剂技术领域,涉及到一种2-(二取代)甲基丙烯酸酯类化合物及其应用。其特征是2-(二取代)甲基丙烯酸酯类化合物,如通式(I)所示,其中:R1选自苯基,取代苯基,C4-C6杂环;R2选自H,C1-C6烷基,C3-C6烯基或C3-C6炔基;R3选自C1-C4烷基;Q选自各种芳环基或取代芳环基;标*与*2的手性碳原子为R、S构型,或其不同比例的混合物。本发明的效果和益处是化合物具有除草活性,在苗后使用可有效控制单子叶杂草。对大豆、水稻、小麦安全。化合物对杂草具有很高的活性,而且对作物表现出优良的选择性。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。
Description
技术领域
本发明属于除草剂技术领域,涉及到一种2-(二取代)甲基丙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加强和对化学农药污染、农药对非靶标生物影响以及在农药生态环境中归宿问题的重视;世界耕地面积减少而人口增长对粮食需求量加大;农业生产技术的迅速发展与耕作制度的不断改进等原因,需要不断发明新型的和改进的除草化合物和组合物。
某些丙烯酸酯类化合物作为除草剂(EP149034A2,USP6251829,CN1626526)已有报道。但如本发明所示的2-(二取代)甲基丙烯酸酯类化合物未见公开。
发明内容
本发明提供了一种2-(二取代)甲基丙烯酸酯类化合物,如通式(I)所示:
其中:
R1选自苯基,取代苯基,C4-C6杂环;
R2选自H,C1-C6烷基,C3-C6烯基或C3-C6炔基;
R3选自C1-C4烷基;
Q选自如下所示基团之一:
标*与*2的手性碳原子为R、S构型,或其不同比例的混合物。
本发明中较为优选的化合物为通式(I)中:
R1选自苯基,取代苯基,C4-C6杂环;
R2选自H,C1-C6烷基,C3-C6烯基或C3-C6炔基;
R3选自H,C1-C4烷基;
Q选自Q1,Q2,Q3,Q4或Q5;
标*的手性碳原子为R构型。
标*2的手性碳原子为R、S构型,或其不同比例的混合物。
本发明中较为优选的化合物为通式(I)中:
R1选自苯基,取代苯基,C4-C6杂环;
R2选自H,C1-C6烷基,C3-C6烯基或C3-C6炔基;
R3选自甲基;
Q选自Q1,Q2,Q5;
标*与*2的手性碳原子为R、S构型,或其不同比例的混合物。
本发明中较为优选的化合物为通式(I)中:
R1选自苯基,取代苯基,C4-C6杂环;
R2选自H,C1-C6烷基,C3-C6烯基或C3-C6炔基;
R3选自甲基;
Q选自Q1,Q2,Q5;
标*的手性碳原子为R构型。
通式(I)中所指的烷基包括直链或支链烷基。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。杂环为含N,S,O等。
本发明的通式化合物I可由如下方法制备:
将原料(II,可由市场购得)溶于适宜的溶剂中,并加入到碱性水溶液中,温度为-10℃到沸点下反应0.5-48小时,再经盐酸或硫酸酸化,制得中间体酸即化合物(II-1)。适宜的溶剂选自氯仿,二氯甲烷,四氯化碳,正己烷,苯,甲苯,乙酸乙酯,THF或二氧六环等;适宜的碱选自氢氧化钠,氢氧化钾,碳酸钠,碳酸钾或碳酸氢钠等。
中间体酸(II-1)与SOCl2,草酰氯或PCl3溶于适宜的溶剂,例如氯仿,二氯甲烷,四氯化碳,正己烷,苯,甲苯,乙酸乙酯,THF或二氧六环等中,并以有机碱,如三乙胺,吡啶或DMF等作催化剂,温度为-10℃到沸点下反应0.5-48小时,制得中间体酰氯(II-2)。
中间体酰氯(II-2)与化合物III(可根据DE2155113、US3742669中所述方法,由相应的醛与丙烯酸酯通过Baylis-Hillman反应得到,标*2的手性碳原子为R、S构型,或其不同比例的混合物),在适宜的溶剂中,温度为-10℃到沸点下反应0.5-48小时制得产物(I)。溶剂选自氯仿,二氯甲烷,四氯化碳,己烷,苯,甲苯,乙酸乙酯,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,碳酸氢钠等对反应有利。
当中间体酰氯(II-2)标*的手性碳原子构型确定,为R型(或S型),而化合物III标*2的手性碳原子为R、S构型不同比例的混合物时,得到一对不同比例非对映体Ia(标C*2手性碳原子构型为R或S)和Ib(标C*2手性碳原子构型为S或R)的混合物。异构体Ia、Ib可以通过重结晶、柱层析、不对称合成等方法而分别得到。(Ia、Ib的绝对构型没有确定)。
表1:部分如通式(I)所示的本发明化合物(标*的手性碳原子为R构型,R3为甲基)
表1:
化合物 | Ia/Ib | Q | R1 | R2 | m.p.(℃) |
1 | 1.0 | Q1 | 4-NO2Ph | CH3 | 粘稠物 |
2 | 1.6 | Q1 | 4-NO2Ph | C2H5 | 粘稠物 |
3 | 1.0 | Q1 | 4-FPh | CH3 | 粘稠物 |
4 | 0.2 | Q1 | 2,4-Cl2Ph | CH3 | 143~146 |
5 | 1.0 | Q1 | 2-thiophen | C2H5 | 粘稠物 |
6 | 1.0 | Q1 | 4-ClPh | C2H5 | 粘稠物 |
7 | 6.5 | Q1 | 2,4-Cl2Ph | C2H5 | 149~150 |
8 | 1.0 | Q1 | 2-furan | C2H5 | 粘稠物 |
9 | 只含Ia构型 | Q1 | 2-ClPh | CH3 | 144~145 |
10 | 只含Ia构型 | Q1 | 3-ClPh | CH3 | 121~122 |
11 | 1.0 | Q1 | 2-CH3OPh | CH3 | 98~103 |
12 | 1.0 | Q1 | 4-CH3OPh | CH3 | 111~125 |
13 | 1.0 | Q1 | 4-MePh | CH3 | 粘稠物 |
14-1 | 1.0 | Q1 | Ph | CH3 | 粘稠物 |
14-2 | 只含Ia构型 | Q1 | Ph | CH3 | 124~126 |
15-1 | 只含Ia构型 | Q2 | 2,4-Cl2Ph | CH3 | 117~119 |
15-2 | 0.3 | Q2 | 2,4-Cl2Ph | CH3 | 粘稠物 |
16 | 只含Ia构型 | Q2 | 4-FPh | CH3 | 105~106 |
17 | 1.0 | Q2 | 2,4-Cl2Ph | C2H5 | 88~92 |
18 | 1.0 | Q2 | 2-thiophen | C2H5 | 粘稠物 |
19 | 1.0 | Q2 | 4-ClPh | C2H5 | 粘稠物 |
20 | 1.0 | Q2 | 2-furan | CH3 | 粘稠物 |
21 | 1.0 | Q2 | 2-furan | C2H5 | 粘稠物 |
22 | 1.0 | Q2 | 2-thiophen | CH3 | 粘稠物 |
23 | 1.0 | Q2 | 4-NO2Ph | CH3 | 粘稠物 |
24 | 1.5 | Q2 | 4-NO2Ph | C2H5 | 粘稠物 |
25 | 1.0 | Q5 | 4-NO2Ph | CH3 | 粘稠物 |
26 | 1.0 | Q5 | 2,4-Cl2Ph | CH3 | 粘稠物 |
27 | 1.0 | Q5 | 4-FPh | CH3 | 粘稠物 |
28 | 1.0 | Q5 | 2,4-Cl2Ph | C2H5 | 粘稠物 |
29 | 1.0 | Q5 | 2-thiophen | C2H5 | 粘稠物 |
30 | 1.0 | Q5 | 4-ClPh | C2H5 | 粘稠物 |
注:Ia/Ib为通式(I)所示的C*2构型(R/S或S/R)比例,可由1H NMR分析得到,但不能判断出绝对构型。
表1中部分化合物的1H NMR(CDCl3,300MHz)、IR数据如下:化合物1:(异构体1a).1H NMR(CDCl3,300MHz)8.70(s,1H),8.12(d,J=8.7Hz,2H),8.07-8.05(m,1H),7.67-7.60(m,2H),7.35(d,J=8.7Hz,2H),7.17-7.12(m,2H),6.93-6.87(m,2H),6.76(s,1H),6.49(s,1H),5.90(s,1H),4.91-4.83(m,1H),3.69(s,3H),1.68-1.64(m,3H)。IRυmax(cm-1)3080,2950,1740,1500,1300,1210。
(异构体1b).1H NMR(CDCl3,300MHz)8.68(s,1H),8.22(d,J=8.7Hz,2H),8.07-8.05(m,1H),7.67-7.60(m,2H),7.57(d,J=8.7Hz,2H),7.17-7.12(m,2H),6.93-6.87(m,2H),6.80(s,1H),6.40(s,1H),5.69(s,1H),4.91-4.83(m,1H),3.74(s,3H),1.68-1.64(m,3H)。
化合物2:(异构体2a).1H NMR(CDCl3,300MHz)8.70(s,1H),8.11(d,J=8.7Hz,2H),8.06(m,1H),7.64-7.57(m,2H),7.36(d,J=8.7Hz,2H),7.17-7.12(m,2H),6.93-6.87(m,2H),6.76(s,1H),6.49(s,1H),5.90(s,1H),4.91-4.83(m,1H),4.21-4.15(m,2H),1.68-1.64(m,3H),1.28-1.20(m,3H)。IRυmax(cm-1)3070,2980,1720,1525,1350。
(异构体2b).1H NMR(CDCl3,300MHz)8.68(s,1H),8.21(d,J=8.7Hz,2H),8.06(m,1H),7.64-7.57(m,4H),7.17-7.12(m,2H),6.93-6.87(m,2H),6.80(s,1H),6.40(s,1H),5.69(s,1H),4.91-4.83(m,1H),4.21-4.15(m,2H),1.68-1.64(m,3H),1.28-1.20(m,3H)。
化合物3:(异构体3a).1H NMR(CDCl3,300MHz)8.69(s,1H),8.05(s,1H),7.66(d,J=8.7Hz,1H),7.59(d,J=8.7Hz,1H),7.40-6.87(m,8H),6.70(s,1H),6.43(s,1H),5.81(s,1H),4.82(q,J=6.6Hz,1H),3.73(s,3H),1.63(d,J=6.6Hz,3H)。IRυmax(cm-1)3060,2950,1740,1500,1300,1200。
(异构体3b).1H NMR(CDCl3,300MHz)8.67(s,1H),8.05(s,1H),7.66(d,J=8.7Hz,1H),7.59(d,J=8.7Hz,1H),7.40-6.87(m,8H),6.74(s,1H),6.35(s,1H),5.64(s,1H),4.82(q,J=6.6Hz,1H),3.68(s,3H),1.63(d,J=6.6Hz,3H)。
化合物4:(异构体4a).1H NMR(CDCl3,300MHz)8.70(s,1H),8.06(d,J=1.8Hz,1H),7.69(d,J=8.7Hz,1H),7.61(dd,J=1.8,8.7Hz,1H),7.44-7.25(m,3H),7.16(d,J=8.7Hz,2H),7.04(s,1H),.95-6.91(m,2H),6.49(s,1H),5.57(s,1H),4.85(q,J=6.6Hz,1H),3.77(s,3H),1.67(d,J=6.6Hz,3H)。IRυmax(cm-1)1750,1710,1500,1305,1140。
(异构体4b).1H NMR(CDCl3,300MHz)8.69(s,1H),8.06(d,J=1.8Hz,1H),7.69(d,J=8.7Hz,1H),7.6 1(dd,J=1.8,8.7Hz,1H),7.44-7.25(m,3H),7.16(d,J=8.7Hz,2H),7.04(s,1H),6.95-6.91(m,2H),6.45(s,1H),5.48(s,1H),4.85(q,J=6.6Hz,1H),3.69(s,3H),1.67(d,J=6.6Hz,3H)
化合物5:(异构体5a).1H NMR(CDCl3,300MHz)8.67(s,1H),8.05(d,J=2.1Hz,1H),7.68(d,J=9.0Hz,1H),7.60(dd,J=2.1,9.0Hz,1H),7.31-7.23(m,1H),7.14-6.87(m,7H),6.46(s,1H),5.96(s,1H),4.82(q,J=6.6Hz,1H),4.25-4.11(m,2H),1.67-1.63(m,3H),1.27-1.20(m,3H)。IRυmax(cm-1)3070,2980,1720,1500,1300,1210。
(异构体5b).1H NMR(CDCl3,300MHz)8.67(s,1H),8.05(d,J=2.1Hz,1H),7.68(d,J=9.0Hz,1H),7.60(dd,J=2.1,9.0Hz,1H),7.31-7.23(m,1H),7.14-6.87(m,7H),6.39(s,1H),5.76(s,1H),4.82(q,J=6.6Hz,1H),4.25-4.11(m,2H),1.67-1.63(m,3H),1.27-1.20(m,3H)。
化合物6:(异构体6a).1H NMR(CDCl3,300MHz)8.69(s,1H),8.06-8.05(m,1H),7.67(d,J=8.7Hz,1H),7.60(dd,J=2.1,8.7Hz,1H),7.32-7.12(m,6H),6.88(dd,J=1.5,9.0Hz,2H),6.68(s,1H),6.43(s,1H),5.81(s,1H),4.82(q,J=6.6Hz,1H),4.23-4.07(m,2H),1.64(d,J=6.6Hz,3H),1.27-1.19(m,3H)。IRυmax(cm-1)3040,2980,1720,1500,1300。
(异构体6b).1H NMR(CDCl3,300MHz)8.67(s,1H),8.06-8.05(m,1H),7.67(d,J=8.7Hz,1H),7.60(dd,J=2.1-8.7Hz,1H),7.32-7.12(m,6H),6.88(dd,J=1.5,9.0Hz,2H),6.72(s,1H),6.35(s,1H),5.64(s,1H),4.82(q,J=6.9Hz,1H),4.23-4.07(m,2H),1.64(d,J=6.6Hz,3H),1.27-1.19(m,3H)。
化合物7:(异构体7a).1H NMR(CDCl3,300MHz)8.70(s,1H),8.07(d,J=2.1Hz,1H),7.68(d,J=8.7Hz,1H),7.61(dd,J=2.1,8.7Hz,1H),7.43-6.90(m,8H),6.48(s,1H),5.58(s,1H),4.84(q,J=6.9Hz,1H),4.27-4.13(m,2H),1.67(d,J=6.9Hz,3H),1.29-1.19(m,3H)。
(异构体7b).1H NMR(CDCl3,300MHz)8.68(s,1H),8.07(d,J=2.1Hz,1H),7.68(d,J=8.7Hz,1H),7.61(dd,J=2.1,8.7Hz,1H),7.43-6.90(m,8H),6.45(s,1H),5.49(s,1H),4.84(q,J=6.9Hz,1H),4.27-4.13(m,2H),1.67(d,J=6.9Hz,3H),1.29-1.19(m,3H)。
化合物8:(异构体8a).1H NMR(CDCl3,300MHz)8.67(s,1H),8.05(d,J=2.1Hz,1H),7.69(d,J=9.0Hz,1H),7.60(dd,J=2.1,9.0Hz,1H),7.42-7.36(m,1H),7.14(d,J=9.0Hz,,2H),6.93-6.83(m,3H),6.50(s,1H),6.35(s,1H),6.31-6.26(m,1H),5.96(s,1H),4.86-4.79(m,1H),4.26-4.11(m,2H),1.68-1.63(m,3H),1.27-1.21(m,3H)。
(异构体8b).1H NMR(CDCl3,300MHz)8.67(s,1H),8.05(d,J=2.1Hz,1H),7.69(d,J=9.0Hz,1H),7.60(dd,J=2.1,9.0Hz,1H),7.42-7.36(m,1H),7.14(d J=9.0Hz,,2H),6.93-6.83(m,3H),6.43(s,1H),6.35(s,1H),6.31-6.26(m,1H),5.75(s,1H),4.86-4.79(m,1H),4.26-4.11(m,2H),1.68-1.63(m,3H),1.27-1.21(m,3H)。
化合物9:1H NMR(CDCl3,300MHz)8.69(s,1H),8.06(d,J=2.1Hz,1H),7.68(d,J=9.0Hz,1H),7.60(dd,J=2.1,9.0Hz,1H),7.38-7.01(m,7H),6.93(d,J=9.0Hz,2H),6.49(s,1H),5.52(s,1H),4.84(q,J=6.6,1H),3.78(s,3H),1.68(d,J=6.6,3H)。
化合物10:1H NMR(CDCl3,300MHz)8.68(s,1H),8.06(s,1H),7.67(d,J=9.0Hz,1H),7.60(d,J=9.0Hz,1H),7.37-7.21(m,4H),7.13(d,J=9.0Hz,2H),6.90(d,J=9.0Hz,2H),6.73(s,1H),6.43(s,1H),5.78(s,1H),4.82(q,J=6.6,1H),3.73(s,3H),1.64(d,J=6.6,3H)。
化合物11:(异构体11a).1H NMR(CDCl3,300MHz)8.69(s,1H),8.05(d,J=2.1Hz,1H),7.69(d,J=8.7Hz,1H),7.61(dd,J=2.1,8.7Hz,1H),7.37-7.12(m,5H),6.98-6.84(m,4H),6.43(s,1H),5.56(s,1H),4.81(q,J=6.6,1H),3.83-3.68(m,6H),1.66(d,J=6.6,3H)
(异构体11b).1H NMR(CDCl3,300MHz)8.68(s,1H),8.05(d,J=2.1Hz,1H),7.69(d,J=8.7Hz,1H),7.61(dd,J=2.1,8.7Hz,1H),7.37-7.12(m,5H),6.98-6.84(m,4H),6.40(s,1H),5.47(s,1H),4.81(q,J=6.6,1H),3.83-3.68(m,6H),1.66(d,J=6.6,3H)
化合物12:(异构体12a).1H NMR(CDCl3,300MHz)8.69(s,1H),8.06-8.05(m,1H),7.68(d,J=8.7Hz,1H),7.60(dd,J=2.1,8.7Hz,1H),7.35-6.84(m,9H),6.43(s,1H),5.55(s,1H),4.81(q,J=6.9,1H),3.83-3.68(m,6H),1.66(d,J=6.9,3H)
(异构体12b).1H NMR(CDCl3,300MHz)8.67(s,1H),8.06-8.05(m,1H),7.68(d,J=8.7Hz,1H),7.60(dd,J=2.1,8.7Hz,1H),7.35-6.84(m,9H),6.40(s,1H),5.48(s,1H),4.81(q,J=6.9,1H),3.83-3.68(m,6H),1.66(d,J=6.9,3H)
化合物13:(异构体13a).1H NMR(CDCl3,300MHz)8.69(s,1H),8.06(s,1H),7.68(d,J=8.7Hz,1H),7.60(d,J=8.7Hz,1H),7.29-7.10(m,6H),6.92-6.86(m,2H),6.70(s,1H),6.41(s,1H),5.78(s,1H),4.80(q,J=6.9,1H),3.73(s,3H),2.28(s,3H),1.65-1.62(m,3H)。
(异构体13b).1H NMR(CDCl3,300MHz)8.68(s,1H),8.06(s,1H),7.68(d,J=8.7Hz,1H),7.60(d,J=8.7Hz,1H),7.29-7.10(m,6H),6.92-6.86(m,2H),6.73(s,1H),6.34(s,1H),5.62(s,1H),4.80(q,J=6.9,1H),3.67(s,3H),2.32(s,3H),1.65-1.62(m,3H)。
化合物14-2:(异构体14a).1H NMR(CDCl3,300MHz)8.68(s,1H),8.06(d,J=2.1Hz,1H),7.67(d,J=8.7Hz,1H),7.60(dd,J=2.1,8.7Hz,1H),7.38-7.20(m,5H),7.13(d,J=9.0Hz,2H),6.90(d,J=9.0Hz,2H),6.73(s,1H),6.43(s,1H),5.78(s,1H),4.82(q,J=6.6Hz,1H),3.73(s,3H),1.64(d,J=6.6Hz,3H)。
化合物14-1:(异构体14b).1H NMR(CDCl3,300MHz)8.67(s,1H),8.04(d,J=2.1Hz,1H),7.67(d,J=8.7Hz,1H),7.60(dd,J=2.1,8.7Hz,1H),7.38-7.20(m,5H),7.11(d,J=9.0Hz,2H),6.88(d,J=9.0Hz,2H),6.77(s,1H),6.36(s,1H),5.86(s,1H),4.82(q,J=6.6Hz,1H),3.68(s,3H),1.65(d,J=6.6Hz,3H)。
化合物15-1:(异构体15a).1H NMR(CDCl3,300MHz)7.45-7.42(m,2H),7.38(d,J=2.1Hz,1H),7.31-7.24(m,3H),7.21(dd,J=2.1,8.7Hz 1H),7.01(s,1H),6.92-6.88(m,3H),6.47(s,1H),5.54(s,1H),4.81(q,J=6.6Hz,1H),3.77(s,3H),1.66(d,J=6.6Hz,3H)。
化合物15-2:(异构体15b).1H NMR(CDCl3,300MHz)7.43-7.38(m,3H),7.31-7.22(m,4H),7.03(s,1H),6.94-6.88(m,3H),6.44(s,1H),5.50(s,1H),4.82(q,J=6.6Hz,1H),3.69(s,3H),1.65(d,J=6.6Hz,3H)。
化合物16:(异构体16a).1H NMR(CDCl3,300MHz)7.45(d,2.1Hz 1H),7.42(d,J=8.4Hz,1H),7.28-7.24(m,3H),7.17-7.13(m,2H),7.01-6.95(m,2H),6.87(d,J=8.7Hz,2H),6.68(s,1H),6.42(s,1H),5.79(s,1H),4.78(q,J=6.6Hz,1H),3.73(s,3H),1.61(d,J=6.6Hz,3H)。
化合物17:(异构体17a).1UH NMR(CDCl3,300MHz)7.46-7.37(m,3H),7.31-7.10(m,4H),7.02(s,1H),6.93-6.89(m,3H),6.47(s,1H),5.56(s,1H),4.84-4.77(m,1H),4.25-4.13(m,2H),1.67-1.64(m,3H),1.29-1.20(m,3H)。
(异构体17b).1H NMR(CDCl3,300MHz)7.46-7.37(m,3H),7.31-7.10(m,4H),7.04(s,1H),6.93-6.89(m,3H),6.43(s,1H),5.50(s,1H),4.84-4.77(m,1H),4.25-4.13(m,2H),1.67-1.64(m,3H),1.29-1.20(m,3H)。
化合物18:(异构体18a).1H NMR(CDCl3,300MHz)7.43(s,1H),7.40(d,J=9.0Hz,1H),7.32-7.23(m,4H),7.09-6.86(m,5H),6.46(s,1H),5.95(s,1H),4.82-4.74(m,1H),4.22-4.15(m,2H),1.65-1.61(m,3H),1.27-1.20(m,3H)。IRυmax(cm-1)3100,2980,1720,1630,1570,1500,1340。
(异构体18b).1H NMR(CDCl3,300MHz)7.43(s,1H),7.40(d,J=9.0Hz,1H),7.32-7.23(m,4H),7.09-6.86(m,5H),6.38(s,1H),5.78(s,1H),4.82-4.74(m,1H),4.22-4.15(m,2H),1.65-1.61(m,3H),1.27-1.20(m,3H)。
化合物19:(异构体19a).1H NMR(CDCl3,300MHz)7.45-7.44(m,1H),7.42(d,J=8.7Hz,1H),7.32-7.09(m,7H),6.87(m,2H),6.67(s,1H),6.42(s,1H),5.79(s,1H),4.82-4.75(m,1H),4.22-4.11(m,2H),1.62(d,J=6.6Hz,3H),1.28-1.18(m,3H)。IRυmax(cm-1)3080,2990,1720,1630,1510,1200。
(异构体19b).1H NMR(CDCl3,300MHz)7.45-7.44(m,1H),7.42(d,J=8.7Hz,1H),7.32-7.09(m,7H),6.87(m,2H),6.71(s,1H),6.34(s,1H),5.65(s,1H),4.82-4.75(m,1H),4.22-4.11(m,2H),1.62(d,J=6.6Hz,3H),1.28-1.18(m,3H)。
化合物20:(异构体20a).1H NMR(CDCl3,300MHz)7.44-7.36(m,3H),7.30-7.23(m,3H),6.90(dd,J=2.1,8.7Hz,2H),6.83-6.80(m,1H),6.50(s,1H),6.35(s,1H),6.32-6.25(m,1H),5.96(s,1H),4.79(q,J=6.6Hz,1H),3.76(s,3H),1.66-1.62(m,3H)。
(异构体20b).1H NMR(CDCl3,300MHz)7.44-7.36(m,3H),7.30-7.23(m,3H),6.90(dd,J=2.1,8.7Hz,2H),6.83-6.80(m,1H),6.43(s,1H),6.35(s,1H),6.32-6.25(m,1H),5.79(s,1H),4.79(q,J=6.6Hz,1H),3.73(s,3H),1.66-1.62(m,3H)。
化合物21:(异构体21a).1H NMR(CDCl3,300MHz)7.44(d,J=2.1Hz,1H),7.40(d,J=8.7Hz,1H),7.36-7.23(m,4H),6.90(dd,J=1.8,8.7Hz,2H),6.82(m,1H),6.42(s,1H),6.35(s,1H),6.31-6.25(m,1H),5.95(s,1H),4.79(q,J=6.6Hz,1H),4.26-4.16(m,2H),1.66-1.61(m,3H),1.27-1.21(3H)。
(异构体21b).1H NMR(CDCl3,300MHz)7.44(d,J=2.1Hz,1H),7.40(d,J=8.7Hz,1H),7.36-7.23(m,4H),6.90(dd,J=1.8,8.7Hz,2H),6.82(m,1H),6.49(s,1H),6.35(s,1H),6.31-6.25(m,1H),5.77(s,1H),4.79(q,J=6.6Hz,1H),4.26-4.16(m,2H),1.66-1.61(m,3H),1.27-1.21(3H)。
化合物22:(异构体22a).1H NMR(CDCl3,300MHz)7.44(d,J=1.8Hz,1H),7.41(d,J=8.4Hz,1H),7.32-7.31(m,1H),7.28-7.23(m,3H),7.09-6.93(m,3H),6.91-6.86(m,2H),6.47(s,1H),5.96(s,1H),4.82-4.74(m,1H),3.75(s,3H),1.65-1.61(m,3H)。
(异构体22b).1H NMR(CDCl3,300MHz)7.44(d,J=1.8Hz,1H),7.41(d,J=8.4Hz,1H),7.32-7.31(m,1H),7.28-7.23(m,3H),7.09-6.93(m,3H),6.91-6.86(m,2H),6.39(s,1H),5.79(s,1H),4.82-4.74(m,1H),3.72(s,3H),1.65-1.61(m,3H)。
化合物23:(异构体23a).1H NMR(CDCl3,300MHz)8.16(d,J=8.7Hz,2H),7.58-7.24(m,7H),6.89(d,J=8.7Hz,2H),6.74(s,1H),6.487(s,1H),5.87(s,1H),4.83(q,J=6.6Hz,1H),3.74(s,3H),1.65(d,J=6.6Hz,3H)。IRυmax(cm-1)3080,2950,1730,1570,1500,1350,1190。
(异构体23b).1H NMR(CDCl3,300MHz)8.22(d,J=8.7Hz,2H),7.58-7.24(m,7H),6.90(d,J=8.7Hz,2H),6.79(s,1H),6.400(s,1H),5.72(s,1H),4.83(q,J=6.6Hz,1H),3.70(s,3H),1.64(d,J=6.6Hz,3H)。
化合物24:(异构体24a).1H NMR(CDCl3,300MHz)8.16(d,J=8.4Hz,2H),7.52-7.06(m,7H),6.89-6.70(m,3H),6.48(s,1H),5.87(s,1H),4.83(q,J=6.6Hz,1H),4.24-4.14(m,2H),1.65(d,J=6.6Hz,3H),1.28-1.19(m,3H)。
(异构体24b).1H NMR(CDCl3,300MHz)8.26(d,J=8.4Hz,2H),7.52-7.06(m,7H),6.89-6.70(m,3H),6.56(s,1H),5.65(s,1H),4.83(q,J=6.6Hz,1H),4.24-4.14(m,2H),1.65(d,J=6.6Hz,3H),1.28-1.19(m,3H)。
化合物25:(异构体25a).1H NMR(CDCl3,300MHz)8.30-8.29(m,1H),8.13(d,J=8.7Hz,2H),7.99-7.97(m,1H),7.31(d,J=8.7Hz,2H),7.05(d,J=9.0Hz,2H),6.87(d,J=9.0Hz,2H),6.74(s,1H),6.47(s,1H),5.86(s,1H),4.84(q,J=6.6Hz,1H),3.74(s,3H),1.64(m,3H)。IRυmax(cm-1)3070,2950,1750,1610,1500,1325。
(异构体25b).1H NMR(CDCl3,300MHz)8.25-8.24(m,1H),8.22(d,J=8.7Hz,2H),7.99-7.97(m,1H),7.56(d,J=8.7Hz,2H),7.05(d,J=9.0Hz,2H),6.89(d,J=9.0Hz,2H),6.77(s,1H),6.37(s,1H),5.69(s,H),4.84(q,J=6.6Hz,1H),3.69(s,3H),1.64(m,3H)。
化合物26:(异构体26a).1H NMR(CDCl3,300MHz)8.30(s,1H),7.99-7.97(m,1H),7.44-7.37(m,1H),7.17(dd,J=2.1,8.7Hz,1H),7.07-7.01(m,3H),6.92-6.85(m,3H),6.48(s,1H),5.52(s,1H),4.82(q,J=6.6Hz,1H),3.78(s,3H),1.67-1.63(m,3H)。IRυmax(cm-1)3050,2950,1730,1500,1320。
(异构体26b).1H NMR(CDCl3,300MHz)8.25(s,1H),7.99-7.97(m,1H),7.44-7.37(m,1H),7.17(dd,J=2.1,8.7Hz,1H),7.07-7.01(m,3H),6.92-6.85(m,3H),6.43(s,1H),5.48(s,1H),4.82(q,J=6.6Hz,1H),3.69(s,3H),1.67-1.63(m,3H)。
化合物27:(异构体27a).1H NMR(CDCl3,300MHz)8.27-8.26(m,1H),7.98-7.96(m,1H),7.18-7.14(m,2H),7.06-6.93(m,4H),6.86(dd,J=1.8,9.0Hz,2H),6.69(s,1H),6.41(s,1H),5.79(s,1H),4.82-4.75(m,1H),3.72(s,3H),1.61(d,J=6.6Hz,3H)。IRυmax(cm-1)3060,2950,1730,1605,1505,1310。
(异构体27b).1H NMR(CDCl3,300MHz)8.25-8.24(m,1H),7.98-7.96(m,1H),7.38-7.33(m,2H),7.06-6.93(m,4H),6.86(dd,J=1.8,9.0Hz,2H),6.72(s,1H),6.33(s,1H),5.64(s,1H),4.82-4.75(m,1H),3.68(s,3H),1.61(d,J=6.6Hz,3H)。
化合物28:(异构体28a).1H NMR(CDCl3,300MHz)8.3 1-8.30(m,1H),7.99-7.96(m,1H),7.43-7.37(m,1H),7.27(s,1H),7.18-7.12(m,1H),7.09-7.03(m,3H),6.89(d,J=8.7Hz,2H),6.47(s,1H),5.54(s,1H),4.85-4.74(m,1H),4.24-4.12(m,2H),1.67-1.63(m,3H),1.29-1.19(m,3H)。IRυmax(cm-1)3060,2980,1730,1505,1325。
(异构体28b).1H NMR(CDCl3,300MHz)8.26-8.25(m,1H),7.99-7.96(m,1H),7.43-7.37(m,1H),7.26(s,1H),7.18-7.12(m,1H),7.09-7.03(m,3H),6.91(d,J=8.7Hz,2H),6.42(s,1H),5.49(s,1H),4.85-4.74(m,1H),4.24-4.12(m,2H),1.67-1.63(m,3H),1.29-1.19(m,3H)。
化合物29:(异构体29a).1H NMR(CDCl3,300MHz)8.31-8.30(m,1H),8.25(s,1H),7.96(s,1H),7.70-7.64(m,1H),7.56-7.463(m,1H),7.32-7.25(m,1H),7.09-6.85(m,5H),6.46(s,1H),5.95(s,1H),4.79(q,J=6.6Hz,1H),n4.18(q,J=6.6Hz,2H),1.65-1.61(m,3H),1.27-1.21(m,3H)。
(异构体29b).1H NMR(CDCl3,300MHz)8.31-8.30(m,1H),8.25(s,1H),7.96(s,1H),7.70-7.64(m,1H),7.56-7.463(m,1H),7.32-7.25(m,1H),7.09-6.85(m,5H),6.37(s,1H),5.76(s,1H),4.79(q,J=6.6Hz,1H),4.18(q,J=6.6Hz,2H),1.65-1.61(m,3H),1.27-1.21(m,3H)。
化合物30:(异构体30a).1H NMR(CDCl3,300MHz)8.29-8.28(m,1H),7.98-7.96(m,1H),7.32-7.10(m,4H),7.03(dd,J=1.8,9.0Hz,2H),6.86(dd,J=1.8,9.0Hz,2H),6.70(s,1H),6.41(s,1H),5.78(s,1H),4.83-4.75(m,1H),4.19-4.10(m,2H),1.63(s,3H),1.26-1.19(m,3H)。
(异构体30b).1H NMR(CDCl3,300MHz)8.26-8.25(m,1H),7.98-7.96(m,1H),7.32-7.10(m,4H),7.03(dd,J=1.8,9.0Hz,2H),6.86(dd,J=1.8,9.0Hz,2H),6.69(s,1H),6.33(s,1H),5.64(s,1H),4.83-4.75(m,1H),4.19-4.10(m,2H),1.60(s,3H),1.26-1.19(m,3H)。
本发明的效果和益处,本发明的通式(I)化合物具有除草活性,在苗后使用可有效控制单子叶杂草。对大豆、水稻、小麦安全。
本发明还包括以通式(I)化合物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1-99%。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等。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剂量为每公顷1克到1000克,优选有效剂量为每公顷5克到500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
下列结合实施例和生测试验结果详细叙述本发明的实施方式,但不意味着限制本发明。
合成实例:化合物1的合成:
向500毫升的反应瓶中加入精喹禾灵(30.00克,80.40毫摩尔,购于江苏丰山集团有限公司,标*的手性碳原子为R构型,下同)和80毫升四氢呋喃,搅拌至全溶,加入氢氧化钠(3.26克,80.68毫摩尔)和水(80毫升)形成的溶液,室温搅拌反应5小时,停止反应,加入100毫升乙酸乙酯萃取,水相用浓盐酸酸化,过滤,虑饼干燥得白色固体,即中间体酸25.00克。
向250毫升的反应瓶中加入上述中间体酸(20.00克,58.00毫摩尔)和150毫升二氯甲烷,搅拌下缓慢加入草酰氯(11.00克,85.74毫摩尔),再加入3滴DMF,室温搅拌反应4小时,之后,减压脱出二氯甲烷和过量的草酰氯得23.00克黄色液体,即中间体酰氯。
向50毫升的反应瓶中加入2-(羟基(4-硝基苯基)甲基)丙烯酸甲酯(0.71克,3.0毫摩尔),三乙胺(0.35克,3.43毫摩尔)和5毫升二氯甲烷,冰水浴下滴加入上述中间体酰氯(1.25克,3.40毫摩尔)和10毫升二氯甲烷形成的溶液,约半小时滴加完,室温下反应5小时,之后,向反应液中加入100毫升乙酸乙酯和20毫升水,分液,乙酸乙酯层依次用饱和碳酸氢钠水溶液、饱和氯化钠水溶液各20毫升洗涤,无水硫酸镁干燥,减压脱溶,经硅胶柱层析分离(乙酸乙酯/石油醚=1/10),得1.06克棕色粘稠物,为化合物1。由1H NMR分析其C*2构型为R型和S型的混合物(R/S或S/R=1),为一对非对映体。
化合物14-1、14-2的合成:
向50毫升的反应瓶中加入2-(羟基(苯基)甲基)丙烯酸甲酯(0.58克,3.00毫摩尔),三乙胺(0.35克,3.43毫摩尔)和5毫升二氯甲烷溶液中,冰水浴下滴加入上述中间体酰氯(1.25克,3.40毫摩尔)和10毫升二氯甲烷形成的溶液,约半小时滴加完,室温下反应8小时,之后,向反应液中加入100毫升乙酸乙酯和20毫升水,乙酸乙酯层依次用饱和碳酸氢钠水溶液、饱和氯化钠水溶液各20毫升洗涤,无水硫酸镁干燥,减压脱溶,经硅胶柱层析分离(乙酸乙酯/石油醚=1/5),得0.91克浅黄色粘稠物,为化合物14-1。由1H NMR分析其C*2构型为R型和S型的混合物(R/S或S/R=1),为一对非对映体。
将上面所得到的等比例非对映体化合物14-1用苯重结晶,先析出白色固体,为化合物14-2(C*2构型为R型或S型),m.p.124~126℃。
化合物15-1、15-2的合成:
向500毫升的反应瓶中加入精噁唑禾草灵(19.04克,50.0毫摩尔,购于沈阳化工研究院,标*的手性碳原子为R构型,下同)和100毫升四氢呋喃。室温下,用30分种滴加入氢氧化钠(2.30克,55.0毫摩尔)和水(100毫升)形成的溶液,室温搅拌反应6小时,停止反应。用盐酸酸化,加入乙酸乙酯萃取,无水硫酸镁干燥,脱溶得浅棕色固体,即中间体酸17.00克。
向250毫升的反应瓶中加入上述中间体酸(2.67克,8.00毫摩尔)和40毫升二氯甲烷,搅拌下缓慢加入草酰氯(1.54克,12.00毫摩尔),再加入2滴DMF,室温搅拌反应4小时,之后,减压脱出二氯甲烷和过量的草酰氯得2.79克黄色液体,即中间体酰氯。
向50毫升的反应瓶中加入2-(羟基(2,4-二氯苯基)甲基)丙烯酸甲酯(0.78克,3.00毫摩尔),三乙胺(0.35克,3.43毫摩尔)和5毫升二氯甲烷,冰水浴下滴加入上述中间体酰氯(1.19克,3.40毫摩尔)和10毫升二氯甲烷形成的溶液,约半小时滴加完,室温下反应5小时,之后,向反应液中加入100毫升乙酸乙酯和20毫升水,分液,乙酸乙酯层依次用饱和碳酸氢钠水溶液、饱和氯化钠水溶液各20毫升洗涤,无水硫酸镁干燥,减压脱溶,经硅胶柱层析分离(乙酸乙酯/石油醚=1/20),分别得到两个化合物。化合物15-1与15-2。其中化合物15-1(C*2构型为R型或S型)为白色固体(0.32克),m.p.117~119℃。化合物15-2为白色粘稠物(0.61克),由1H NMR分析其C*2构型为R型和S型的混合物(R/S或S/R=0.3)。
化合物30的合成:
向250毫升的反应瓶中加入高效盖草能(15.00克,40.0毫摩尔,购于沈阳化工研究院,标*的手性碳原子为R构型,下同)和60毫升2N氢氧化钠水溶液,升温至70℃,搅拌反应2小时,停止反应。降至室温,用浓盐酸酸化,加入二氯甲烷萃取,脱溶得棕色固体,即中间体酸13.04克。
向250毫升的反应瓶中加入上述中间体酸(2.89克,8.00毫摩尔)和40毫升二氯甲烷,搅拌下缓慢加入草酰氯(1.54克,12.00毫摩尔),再加入2滴DMF,室温搅拌反应4小时,之后,减压脱出二氯甲烷和过量的草酰氯得2.84克黄色液体,即中间体酰氯。
向50毫升的反应瓶中加入2-(羟基(4-氯苯基)甲基)丙烯酸乙酯(0.72克,3.00毫摩尔),三乙胺(0.35克,3.43毫摩尔)和5毫升二氯甲烷,冰水浴下滴加入上述中间体酰氯(1.29克,3.40毫摩尔)和10毫升二氯甲烷形成的溶液,约半小时滴加完,室温下反应5小时,之后,向反应液中加入100毫升乙酸乙酯和20毫升水,分液,乙酸乙酯层依次用饱和碳酸氢钠水溶液、饱和氯化钠水溶液各20毫升洗涤,无水硫酸镁干燥,减压脱溶,经硅胶柱层析分离(乙酸乙酯/石油醚=1/10),得0.92克无色透明粘稠物,为化合物30。由1H NMR分析其C*2构型为R型和S型的混合物(R/S或S/R=1),为一对非对映体。
表1中的其他化合物可通过以上类似的方法制得。
生测实例
用丙酮溶解原药,按设计剂量,加入到含表面活性剂的一定量水中,制得一定浓度的制剂。用移动带式喷雾器进行喷雾。试材放于喷雾橱内的滚带上,移动喷头经过试材上部,以扇面喷雾形式将药剂喷到试材上,喷嘴与通常田间喷雾器上的相同。滚带将试材移出橱外,置于干燥箱中干燥。
苗后试验,种子发芽并生长10~21天,使处理前具有一系列生育阶段的试材,然后选择大小、生育阶段一致的试材,进行处理,处理后置于温室并浇水。未用化合物处理的试材作对照。试材为单子叶杂草稗草和马唐。
喷雾干燥后的试材置于温室中。苗后试验从底部灌水并保持48小时以使水不接触到叶面。
处理后4周进行调查。抑制率为各种损害如失绿、枯斑、生长阻滞或叶角灼烧的总效果,与空白对照比较后得到结果。部分测试结果见表2。
表2:通式(I)中化合物的除草活性(苗后,抑制率%)
化合物 | 剂量ga.i./ha | 稗草 | 马唐 |
1 | 200 | 100 | 100 |
40 | 100 | 98 | |
5 | 100 | * | |
2 | 200 | 100 | 98 |
40 | 100 | 98 | |
5 | 100 | ||
3 | 200 | 100 | 100 |
40 | 100 | 98 | |
5 | 40 | ||
5 | 1000 | 100 | 100 |
200 | 98 | 90 |
40 | 95 | 80 | |
8 | 200 | 100 | 98 |
40 | 100 | 98 | |
10 | 100 | ||
9 | 1000 | 100 | 98 |
200 | 100 | 95 | |
40 | 100 | 90 | |
10 | 1000 | 100 | 100 |
200 | 100 | 100 | |
40 | 100 | 98 | |
14-2 | 1000 | 100 | 100 |
200 | 100 | 100 | |
40 | 100 | 95 | |
18 | 200 | 100 | 100 |
40 | 100 | 98 | |
5 | 80 | ||
19 | 1000 | 100 | 100 |
200 | 95 | 95 | |
40 | 90 | 45 | |
20 | 1000 | 100 | 100 |
200 | 100 | 98 | |
40 | 100 | 85 |
25 | 200 | 100 | 100 |
40 | 100 | 98 | |
5 | 50 | ||
27 | 200 | 100 | 100 |
40 | 100 | 100 | |
20 | 98 | 100 | |
30 | 1000 | 100 | 100 |
200 | 98 | 85 | |
40 | 25 | 50 |
*:空格表示未测
本发明进行了作物安全性试验,部分结果见表3。
表3部分通式(I)中化合物的安全性测定结果(苗后)
化合物 | 剂量ga.i./ha | 抑制或杀死% | |||
小麦 | 玉米 | 水稻 | 大豆 | ||
2 | 40 | 0 | 10 | 0 | 0 |
200 | 0 | 30 | 5 | 0 | |
1000 | 15 | 80 | 40 | 0 | |
18 | 40 | 0 | 0 | 0 | 0 |
200 | 2 | 20 | 0 | 0 | |
1000 | 4 | 95 | 0 | 0 | |
19 | 40 | 0 | 15 | 0 | 0 |
200 | 0 | 55 | 0 | 0 | |
1000 | 5 | 95 | 0 | 0 |
Claims (6)
2、根据权利要求1所述的化合物,其特征在于,通式(I)中:
R1选自苯基,取代苯基,C4-C6杂环;
R2选自H,C1-C6烷基,C3-C6烯基或C3-C6炔基;
R3选自C1-C4烷基;
Q选自Q1,Q2,Q3,Q4或Q5;
标*的手性碳原子为R构型;
标*2的手性碳原子为R、S构型,或其不同比例的混合物。
3、根据权利要求1所述的化合物,其特征在于,通式(I)中:
R1选自苯基,取代苯基,C4-C6杂环;
R2选自H,C1-C6烷基,C3-C6烯基或C3-C6炔基;
R3选自甲基;
Q选自Q1,Q2,Q5;
标*与*2的手性碳原子为R、S构型,或其不同比例的混合物。
4、根据权利要求1所述的化合物,其特征在于,通式(I)中:
R1选自苯基,取代苯基,C4-C6杂环;
R2选自H,C1-C6烷基,C3-C6烯基或C3-C6炔基;
R3选自甲基;
Q选自Q1,Q2,Q5;
标*的手性碳原子为R构型;
标*2的手性碳原子为R、S构型,或其不同比例的混合物。
5、根据权利要求1所述的化合物及其应用,其特征在于化合物或其组合物用于控制杂草的用途;组合物含有权利要求1所述的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1-99%。
6、根据权利要求1所述的化合物及其应用,其特征在于向杂草或杂草的生长介质或地点上施用如权利要求5所述的组合物。
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