本发明涉及化学领域,具体的,本发明涉及化合物及其制备方法和应用,更具体的,本发明涉及式Ι所示化合物以及衍生物及其制备方法和应用。
背景技术:
膦酸酯衍生物是一类生物活性显著的化合物,并且已有许多膦酸酯衍生物被开发成除草剂或植物生长调节剂。近十年来,本发明人研制了A类型(贺红武等,中国发明专利,专利号为ZL 97109095.5;CN1274697C)的膦酸酯(盐)衍生物,它们均显示了不同程度的除草活性及植物生长调节活性。
而对此结构的进一步的研究具有重要的意义。
技术实现要素:
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此,本发明的目的在于提出一类具有除草活性的化合物。
在本发明的第一方面,提供了一种化合物。根据本发明的实施例,该化合物为式I所示化合物或式I所示化合物的对映异构体、非对映异构体、外消旋体、结晶水合物或溶剂合物,
其中,
R1为H,呋喃基或任选取代的烷基;
R2,R3和R4分别独立地为H或任选取代的烷基。
发明人惊奇地发现,根据本发明实施例的化合物具有有效地除草活性。
根据本发明的实施例,上述化合物还可以具有下列附加技术特征:
根据本发明的一个实施例中,所述烷基分别独立地含有1~10个碳原子。
根据本发明的一个实施例中,所述R1为H,呋喃基或含有1~3个碳原子的烷基,任选地,所述R1为H,呋喃基或甲基。
根据本发明的一个实施例中,所述R2,R3和R4分别独立地为H或含有1~5个碳原子的烷基,任选地,所述R2,R3和R4分别独立地为H或选自含有1~4个碳原子的直链或支链烷基。
根据本发明的一个实施例中,所述化合物为下列化合物或者所述下列化合物的对映异构体、非对映异构体、外消旋体、结晶水合物或溶剂合物:
在本发明的第二方面,本发明提供了一种制备前面所述化合物的方法,根据本发明的实施例,该方法包括:
使式II所示化合物与式III所示化合物式进行接触,以便获得式I所示化合物,
其中R1、R2、R3、R4是前面所定义的。
根据本发明的实施例,所述接触是通过将所述式II所示化合物、所述接触是通过将所述式II所示化合物与式III所示化合物溶于第一有机溶剂中,并且在-10-83℃条件下,搅拌1-24小时,
任选地,所述第一有机溶剂为苯、乙腈、1,2-二氯乙烷、氯仿、二氯甲烷、甲醇、乙醇或乙酸乙酯中的至少一种。
根据本发明的实施例,式II所示化合物、式III所示化合物摩尔比为1:1-2。
由此,根据本发明的实施例,本发明提出了一条合成路线,可以用于制备式I所示化合物:
根据发明实施例,其特征是式II所示化合物与式III所示化合物反应配比为1:1-2的摩尔比,反应溶剂采用有机溶剂苯、乙腈、1,2-二氯乙烷、氯仿、二氯甲烷、甲醇、乙醇或乙酸乙酯,在-10℃至83℃条件下,反应1-24小时,即可获得较好的收率。
本发明的第三方面,本发明提供了一种农药,其包括前面所描述的化合物。发明人发现该农药能够有效地用于除草。
在本发明的第四方面,本发明提供了前面所述的化合物或农药除杂草的方法,所述杂草为单子叶或双子叶植物;任选地,所述杂草为苘麻、刺苋或者藜。
本发明以高效高收率的方法合成的有机铵盐衍生物,此类化合物在除杂草的同时可以为经济作物提供所需要的氮盐,以促使作物的生长。
具体实施方式
下面详细描述本发明的实施例。下面的实施例是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。
实施例1
化合物1的制备
将2mmol O-甲基-2,4-二氯苯氧乙酰氧基烃基膦酸加入2mmol氨水的5mL 苯溶液中,电磁搅拌,TLC跟踪反应,83℃反应1小时;脱溶后,得白色固体粗品。直接用硅胶(G型)柱层析梯度淋洗,(洗脱剂丙酮:石油醚体积比=1:8)得纯品。
所得纯品为白色固体,收率为89%;m.p.140~141℃。
元素分析/%:计算值:C,36.69;H,4.48;N,3.89;实测值:C,36.33;H,4.14;N,3.74.
1H NMR(400MHz,CDCl3):δ1.34(d,3H,CH3,J=7.2Hz),3.53(d,3H,OCH3,J=9.4Hz),4.71(dd,2H,COCH2,J=16.316.2Hz),5.17(s,1H,PCH),,5.81(s,4H,NH4),6.75(d,1H,Ar-H,J=8.7Hz),7.09(dd,1H,Ar-H,J=8.62.2Hz),7.27(dd,1H,Ar-H,J=4.9,2.5Hz);
13C NMR(100MHz,CDCl3):δ167.86,151.82,129.97,127.57,126.90,123.39,114.44,68.32,66.73,66.13,52.91,15.45;
31P NMR(160MHz,CDCl3):12.26;
化合物2-16按化合物1类似方法制得,其结构鉴定数据如下:
化合物2
所得纯品为白色固体,收率为89%;m.p.52~53℃。
元素分析/%:计算值:C,38.52;H,4.85;N,3.74;实测值:C,38.74;H,5.06;N,3.70.
1H NMR(400MHz,CDCl3):δ1.40(dd,3H,CH3,J=14.5,7.1Hz),2.49(s,3H,NCH3),3.58(d,3H,OCH3,J=10.1Hz),4.74(q,2H,COCH2,J=16.2Hz),5.20-5.24(m,1H,PCH),6.22(s,3H,NH3),6.81(d,1H,Ar-H,J=8.9Hz),7.16(dd,1H,Ar-H,J=8.92.5Hz),7.34(dd,1H,Ar-H,J=14.5,2.5Hz);
13C NMR(100MHz,CDCl3):δ167.80,152.11,130.08,127.57,126.88,123.67,114.60,68.12,66.81,66.24,52.75,24.83,15.66;
31P NMR(160MHz,CDCl3):14.16;
化合物3
所得纯品为白色固体,收率为88%;m.p.53~55℃。
元素分析/%:计算值:C,40.22;H,5.19;N,3.61;实测值:C,40.30;H,5.24;N,3.78.
1H NMR(400MHz,CDCl3):δ1.26(t,3H,CH3,J=7.2Hz),1.41(dd,3H,CH3,J=14.5,7.0Hz),2.90(dd,2H,CH2,J=14.5,7.2Hz),3.59(d,3H,OCH3,J=10.1Hz),4.73(q,2H,COCH2,J=16.3Hz),5.21-5.25(m,1H,PCH),5.56(s,3H,NH3),6.82(d,1H,Ar-H,J=8.8Hz),7.16(dd,1H,Ar-H,J=8.82.5Hz),7.36(dd,1H,Ar-H,J=11.2,2.5Hz);
13C NMR(100MHz,DMSO-d6):δ167.62,152.09,130.01,127.49,126.77,123.65,114.53,68.29,66.72,66.17,52.67,34.67,15.64,12.60;
31P NMR(160MHz,DMSO-d6):13.89;
化合物4
所得纯品为白色固体,收率为90%;m.p.52~53℃。
元素分析/%:计算值:C,41.81;H,5.51;N,3.48;实测值:C,41.55;H,5.68;N,3.62.
1H NMR(400MHz,CDCl3):δ0.94(t,3H,CH3,J=6.8Hz),1.41(dd,3H,CH3,J=14.3,6.8Hz),1.66(s,2H,CH2),2.79(s,2H,CH2),3.59(d,3H,OCH3,J=9.9Hz),4.73(q,2H,COCH2,J=16.2Hz),5.00(s,3H,NH3),5.22(s,1H,PCH),5.56(s,3H,NH3),6.83(d,1H,Ar-H,J=8.9Hz),7.17(dd,1H,Ar-H,J=8.82.2Hz),7.36(dd,1H,Ar-H,J=11.2,2.5Hz);
13C NMR(100MHz,DMSO-d6):δ167.67,152.11,129.99,127.48,126.75,123.66,114.56,68.32,66.73,66.16,52.65,41.07,20.82,15.62,10.87;
31P NMR(160MHz,DMSO-d6):12.08;
化合物5
所得纯品为白色固体,收率为95%;m.p.42~44℃。
元素分析/%:计算值:C,41.81;H,5.51;N,3.48;实测值:C,41.59;H,5.49;N,3.67.
1H NMR(400MHz,CDCl3):δ1.28(d,6H,2CH3,J=4.2Hz),1.43(dd,3H,CH3,J=14.4,6.9Hz),3.33(s,1H,CH),3.60(d,3H,OCH3,J=10.0Hz),4.73(q,2H,COCH2,J= 16.4Hz),5.00(s,3H,NH3),5.23(s,1H,PCH),6.82(d,1H,Ar-H,J=8.8Hz),7.16(dd,1H,Ar-H,J=8.82.4Hz),7.36(dd,1H,Ar-H,J=12.1,2.4Hz);
13C NMR(100MHz,DMSO-d6):δ167.65,152.07,130.00,127.47,126.69,123.62,114.46,68.23,66.62,66.10,52.73,43.49,20.59,15.65;
31P NMR(160MHz,DMSO-d6):13.51;
化合物6
所得纯品为白色固体,收率为89%;m.p.45~46℃。
元素分析/%:计算值:C,43.28;H,5.81;N,3.37;实测值:C,43.21;H,5.63;N,3.58.
1H NMR(400MHz,CDCl3):δ0.90(d,3H,CH3,J=7.3Hz),1.32(dd,2H,CH2,J=14.7,7.4Hz),1.42(dd,3H,CH3,J=14.5,6.9Hz),1.60(d,2H,CH2,J=7.0Hz),2.80(d,2H,CH2,J=7.2Hz),3.59(d,3H,OCH3,J=10.0Hz),4.73(q,2H,COCH2,J=16.2Hz),5.21-5.23(m,1H,PCH),5.55(s,3H,NH3),6.83(d,1H,Ar-H,J=8.9Hz),7.15(t,1H,Ar-H,J=8.6Hz),7.36(d,1H,Ar-H,J=10.8Hz);
13C NMR(100MHz,DMSO-d6):δ167.61,152.15,129.99,127.45,126.75,123.72,114.60,68.29,66.75,66.18,52.64,39.20,29.45,19.64,15.63,13.39;
31P NMR(160MHz,DMSO-d6):12.23;
化合物7
所得纯品为黄色油状,收率为86%;折射率为1.5310。
元素分析/%:计算值:C,40.22;H,5.19;N,3.61;实测值:C,40.47;H,5.27;N,3.32.
1H NMR(400MHz,CDCl3):δ1.43(dd,3H,CH3,J=7.1,7.0Hz),2.56(s,6H,2CH3),3.62(d,3H,OCH3,J=10.1Hz),4.73(s,2H,COCH2),5.26(s,1H,PCH),6.83(d,1H,Ar-H,J=8.8Hz),7.17(dd,1H,Ar-H,J=8.82.6Hz),7.37(dd,1H,Ar-H,J=5.7,2.4Hz);
13C NMR(100MHz,DMSO-d6):δ167.67,152.11,130.07,127.52,126.75,123.64,114.45,68.34,66.75,66.14,52.79,34.63,15.70;
31P NMR(160MHz,DMSO-d6):15.91;
化合物8
所得纯品为白色油状,收率为87%;折射率为1.4978。
元素分析/%:计算值:C,43.28;H,5.81;N,3.37;实测值:C,43.54;H,5.71;N,3.56.
1H NMR(400MHz,CDCl3):δ1.32(s,6H,2CH3),1.45(dd,3H,CH3,J=6.9,7.0Hz),2.90(s,4H,2CH2),3.61(d,3H,OCH3,J=10.0Hz),4.72(s,2H,COCH2),5.24-5.27(m,1H,PCH),6.82(d,1H,Ar-H,J=8.8Hz),7.17(dd,1H,Ar-H,J=8.82.6Hz),7.38(d,1H,Ar-H,J=2.3Hz),9.65(s,2H,NH2);
13C NMR(100MHz,DMSO-d6):δ167.63,152.29,130.14,127.55,126.81,123.84,114.61,68.47,66.88,66.32,52.70,41.88,15.85,11.12;
31P NMR(160MHz,DMSO-d6):13.42;
化合物9
所得纯品为黄色油状,收率为89%;折射率为1.4942。
元素分析/%:计算值:C,45.96;H,6.35;N,3.15;实测值:C,45.56;H,6.32;N,3.03.
1H NMR(400MHz,CDCl3):δ0.95(t,6H,2CH3,J=7.4Hz),1.44(dd,3H,CH3,J=7.1,7.0Hz),1.75(dd,4H,2CH2,J=7.6,7.7Hz),2.73-2.77(m,4H,2CH2),3.59(d,3H,OCH3,J=10.1Hz),4.71(s,2H,COCH2),5.23(s,1H,PCH),6.82(d,1H,Ar-H,J=8.8Hz),7.16(dd,1H,Ar-H,J=8.82.5Hz),7.38(d,1H,Ar-H,J=2.5Hz);
13C NMR(100MHz,DMSO-d6):δ167.53,152.27,130.09,127.48,126.76,123.84,114.60,68.40,66.80,66.28,52.59,48.96,19.26,15.73,11.16;
31P NMR(160MHz,DMSO-d6):14.46;
化合物10
所得纯品为白色油状,收率为90%;折射率为1.4942。
元素分析/%:计算值:C,45.96;H,6.35;N,3.15;实测值:C,45.68;H,6.32;N,3.31.
1H NMR(400MHz,CDCl3):δ1.32(d,12H,4CH3,J=6.4Hz),1.45(dd,3H,CH3,J=7.0,7.0Hz),3.23-3.26(m,2H,2CH),3.60(d,3H,OCH3,J=10.0Hz),4.70(s,2H,COCH2),5.23-5.26(m,1H,PCH),6.82(d,1H,Ar-H,J=8.8Hz),7.15(dd,1H,Ar-H,J=8.81.7Hz),7.38(d,1H,Ar-H,J=2.2Hz);
13C NMR(100MHz,DMSO-d6):δ167.54,152.29,130.03,127.46,126.69,123.80,114.63,68.44,66.85,66.29,52.45,46.19,18.78,15.83;
31P NMR(160MHz,DMSO-d6):13.62;
化合物11
所得纯品为白色油状,收率为93%;折射率为1.4960。
元素分析/%:计算值:C,48.31;H,6.83;N,2.97;实测值:C,48.32;H,6.64;N,3.03
1H NMR(400MHz,CDCl3):δ0.92(t,6H,2CH3,J=7.3Hz),1.34-1.38(m,4H,2CH2),1.44(dd,3H,CH3,J=7.0,7.0Hz),1.69(s,4H,2CH2),2.79(s,4H,2CH2),3.60(d,3H,OCH3,J=10.1Hz),4.72(s,2H,COCH2),5.23-5.26(m,1H,PCH),6.82(d,1H,Ar-H,J=8.8Hz),7.16(dd,1H,Ar-H,J=8.82.5Hz),7.38(d,1H,Ar-H,J=2.5Hz);
13C NMR(100MHz,DMSO-d6):δ167.48,167.42,152.24,130.01,127.43,126.68,123.77,114.57,68.31,66.72,66.24,52.46,47.24,27.82,19.94,15.67,13.56;
31P NMR(160MHz,DMSO-d6):13.25;
化合物12
所得纯品为白色油状,收率为89%;折射率为1.4961。
元素分析/%:计算值:C,48.31;H,6.83;N,2.97;实测值:C,48.03;H,6.59;N,2.84.
1H NMR(400MHz,CDCl3):δ1.03(d,12H,4CH3,J=6.7Hz),1.43(dd,3H,CH3,J=7.0,7.0Hz),1.69(s,4H,2CH2),2.11-2.18(m,2H,2CH),2.68(d,4H,2CH2,J=7.1Hz),3.59(d,3H,OCH3,J=10.1Hz),4.71(s,2H,COCH2),5.21-5.24(m,1H,PCH),6.82(d,1H,Ar-H,J=8.8Hz),7.15(dd,1H,Ar-H,J=8.82.5Hz),7.37(d,1H,Ar-H,J=2.5Hz);
13C NMR(100MHz,DMSO-d6):δ167.35,152.23,129.93,127.38,126.56,123.72,114.55,68.49,66.91,66.20,55.09,52.38,25.28,20.45,15.69;
31P NMR(160MHz,DMSO-d6):13.42;
化合物13
所得纯品为白色油状,收率为88%;折射率为1.4978。
元素分析/%:计算值:C,41.81;H,5.51;N,3.48;实测值:C,41.68;H,5.54;N,3.38.
1H NMR(400MHz,CDCl3):δ1.49(dd,3H,CH3,J=7.1,7.1Hz),2.77(s,9H,3CH3),3.67(d,3H,OCH3,J=10.2Hz),4.75(s,2H,COCH2),4.98(s,1H,NH),5.27-5.34(m,1H,PCH),6.85(d,1H,Ar-H,J=8.8Hz),7.17(dd,1H,Ar-H,J=8.82.5Hz),7.37(d,1H,Ar-H,J=2.5Hz);
13C NMR(100MHz,DMSO-d6):δ167.57,152.10,129.85,127.49,126.49,123.45,114.53,68.29,66.68,66.04,52.56,44.66,15.55;
31P NMR(160MHz,DMSO-d6):14.45;
化合物14
所得纯品为白色油状,收率为97%;折射率为1.4945。
元素分析/%:计算值:C,45.96;H,6.35;N,3.15;实测值:C,46.08;H,6.57;N,3.04.
1H NMR(400MHz,CDCl3):δ1.30(t,9H,3CH3,J=7.3Hz),1.47(dd,3H,CH3,J=7.1,7.1Hz),3.06(q,6H,3CH2,J=7.3Hz),3.64(d,3H,OCH3,J=10.1Hz),4.74(d,2H,COCH2,J=3.8Hz),5.25-5.32(m,1H,PCH),6.85(d,1H,Ar-H,J=8.8Hz),7.16(dd,1H,Ar-H,J=8.82.5Hz),7.37(d,1H,Ar-H,J=2.5Hz);
13C NMR(100MHz,DMSO-d6):δ167.38,152.14,129.65,127.41,126.28,123.36,114.59,68.30,66.71,66.02,52.27,45.26,15.58,8.20;
31P NMR(160MHz,DMSO-d6):15.09;
化合物15
所得纯品为白色油状,收率为94%;折射率为1.4910。
元素分析/%:计算值:C,49.39;H,7.05;N,2.88;实测值:C,49.41;H,7.24;N,3.09.
1H NMR(400MHz,CDCl3):δ0.98(t,9H,3CH3,J=7.3Hz),1.47(dd,3H,CH3,J=7.1,7.1Hz),1.68-1.78(m,6H,3CH2),2.89-2.94(m,6H,3CH2),2.75(s,1H,NH),3.63(d,3H,OCH3,J=10.1Hz),4.70-4.79(m,2H,COCH2),5.26-5.30(m,1H,PCH),6.85(d,1H,Ar-H,J=8.9Hz),7.16(dd,1H,Ar-H,J=8.82.4Hz),7.37(d,1H,Ar-H,J=2.5Hz);
13C NMR(100MHz,DMSO-d6):δ167.59,152.31,129.97,127.51,126.58,123.71,114.65,68.45,66.86,66.24,53.23,52.60,16.58,15.74,11.08;
31P NMR(160MHz,DMSO-d6):15.21;
化合物16
所得纯品为黄色油状,收率为79%;折射率为1.4809。
元素分析/%:计算值:C,52.28;H,7.63;N,2.65;实测值:C,52.32;H,7.61;N,2.64.
1H NMR(400MHz,CDCl3):δ0.96(t,9H,3CH3,J=7.3Hz),1.35-1.40(m,6H,3CH2), 1.47(dd,3H,CH3,J=7.1,7.1Hz),1.63-1.69(m,6H,3CH2),2.92-2.96(m,6H,3CH2),3.62(d,3H,OCH3,J=10.1Hz),4.73(s,2H,COCH2),5.25-5.29(m,1H,PCH),6.85(d,1H,Ar-H,J=8.8Hz),7.16(dd,1H,Ar-H,J=8.82.5Hz),7.36(d,1H,Ar-H,J=2.5Hz);
13C NMR(100MHz,DMSO-d6):δ167.07,151.92,129.33,127.09,125.98,125.10,123.14,114.38,66.79,66.37,65.78,51.92,51.06,24.53,19.49,15.24,13.02;
31P NMR(160MHz,DMSO-d6):15.07;
实施例2
化合物17的制备
将2mmol O-甲基-2,4-二氯苯氧乙酰氧基烃基膦酸加入4mmol氨水的5mL甲醇溶液中,电磁搅拌,TLC跟踪反应,0℃以下反应24小时;脱溶后,得白色固体粗品。直接用硅胶(G型)柱层析梯度淋洗,(洗脱剂丙酮:石油醚体积比=1:8)得纯品。
所得纯品为棕红色油状,收率为94%;折射率为1.4981。
元素分析/%:计算值:C,40.80;H,3.91;N,3.40;实测值:C,40.77;H,4.07;N,3.56.
1H NMR(400MHz,DMSO-d6):δ3.56(d,3H,OCH3,J=10.1Hz),4.99(s,2H,COCH2),6.03(s,1H,PCH),6.41(s,1H,furan-H),6.55(s,1H,furan-H),7.05(d,1H,Ar-H,J=8.9Hz),7.32(dd,1H,Ar-H,J=8.92.3Hz),7.58(d,1H,Ar-H,J=2.3Hz),7.61(s,1H,furan-H),8.90(s,4H,NH4);
13C NMR(100MHz,DMSO-d6):δ167.60,152.26,150.15,142.97,129.54,128.08,125.31,122.50,115.27,110.76,110.33,79.39,66.96,65.58,52.22;
31P NMR(160MHz,DMSO-d6):δ6.53;
化合物18-32按化合物17类似方法制得,其结构鉴定数据如下:
化合物18
所得纯品为棕红色油状,收率为90%;折射率为1.5033。
元素分析/%:计算值:C,42.27;H,4.26;N,3.29;实测值:C,42.42;H,4.13;N,3.34.
1H NMR(400MHz,DMSO-d6):δ2.49(s,3H,CH3),3.45(d,3H,OCH3,J=10.1Hz),4.90(dd,2H,COCH2,J=16.416.4Hz),5.96(d,1H,PCH,J=13.3Hz),6.41(s,1H,furan-H),6.55(s,1H,furan-H),7.05(d,1H,Ar-H,J=8.9Hz),7.32(dd,1H,Ar-H,J=8.92.3Hz),7.58(d,1H,Ar-H,J=2.3Hz),7.61(s,1H,furan-H),8.10(s,3H,NH3);
13C NMR(100MHz,DMSO-d6):δ167.16,152.31,149.99,142.94,129.65,127.55,125.92,122.83,115.13,110.57,110.13,66.85,65.50,65.31,52.12,34.05;
31P NMR(160MHz,DMSO-d6):6.63;
化合物19
所得纯品为棕红色油状,收率为89%;折射率为1.5302。
元素分析/%:计算值:C,43.65;H,4.58;N,3.18;实测值:C,43.41;H,4.52;N,3.22.
1H NMR(400MHz,DMSO-d6):δ1.12(t,3H,CH3,J=7.2Hz),2.73(dd,2H,CH2,J=14.37.1Hz),3.40(d,3H,OCH3,J=10.0Hz),4.95(dd,2H,COCH2,J=16.716.7Hz),5.93(d,1H,PCH,J=13.3Hz),6.41(s,1H,furan-H),6.55(s,1H,furan-H),7.05(d,1H,Ar-H,J=8.9Hz),7.32(dd,1H,Ar-H,J=8.92.3Hz),7.58(d,1H,Ar-H,J=2.3Hz),7.61(s,1H,furan-H),8.10(s,3H,NH3);
13C NMR(100MHz,DMSO-d6):δ167.36,152.11,149.93,142.84,129.35,127.85,125.22,122.43,115.13,110.57,110.13,66.85,65.50,65.31,52.12,34.05,12.42;
31P NMR(160MHz,DMSO-d6):6.73;
化合物20
所得纯品为白色固体,收率为89%;m.p.153~154℃。
元素分析/%:计算值:C,44.95;H,4.88;N,3.08;实测值:C,44.75;H,4.54;N,3.22.
1H NMR(400MHz,DMSO-d6):δ0.87(t,3H,CH3,J=7.4Hz),1.53(dd,2H,CH2, J=14.87.4Hz),2.76-2.57(m,2H,CH2),3.39(d,3H,OCH3,J=10.0Hz),4.94(dd,2H,COCH2,J=16.716.7Hz),5.92(d,1H,PCH,J=13.2Hz),6.41(s,1H,furan-H),6.54(s,1H,furan-H),7.04(d,1H,Ar-H,J=8.9Hz),7.32(d,1H,Ar-H,J=8.8Hz),7.58(s,1H,Ar-H),7.60(s,1H,furan-H),8.08(s,3H,NH3);
13C NMR(100MHz,DMSO-d6):δ167.49,152.23,150.24,142.92,129.49,128.00,125.28,122.49,115.25,110.68,110.26,67.02,65.59,52.18,40.50,20.52,11.09;
31P NMR(160MHz,DMSO-d6):6.66;
化合物21
所得纯品为棕红色油状,收率为92%;折射率为1.4966。
元素分析/%:计算值:C,44.95;H,4.88;N,3.08;实测值:C,45.03;H,4.61;N,3.21.
1H NMR(400MHz,CDCl3):δ1.16(t,6H,2CH3),3.15(s,1H,CH),3.63(d,3H,OCH3,J=9.8Hz),4.72(q,2H,COCH2,J=16.4Hz),6.25(d,1H,PCH,J=13.7Hz),6.33(s,1H,furan-H),6.53(s,1H,furan-H),6.73(d,1H,Ar-H,J=8.3Hz),7.10(d,1H,Ar-H,J=8.0Hz),7.36(s,1H,Ar-H),7.43(s,1H,furan-H),8.11(s,3H,NH3);
13C NMR(100MHz,CDCl3):δ167.30,152.20,148.46,143.41,130.21,127.56,126.96,123.93,114.68,111.50,110.72,66.33,66.14,64.75,53.37,43.51,20.57;
31P NMR(160MHz,CDCl3):8.58,8.72;
化合物22
所得纯品为白色固体,收率为90%;m.p.149~150℃。
元素分析/%:计算值:C,46.17;H,5.17;N,2.99;实测值:C,46.26;H,5.36;N,3.02.
1H NMR(400MHz,DMSO-d6):δ0.84(s,3H,CH3),1.27(d,2H,CH2,J=6.1Hz),1.49(s,2H,CH2),2.64(s,2H,CH2),3.41(d,3H,OCH3,J=9.8Hz),4.96(dd,2H, COCH2,J=16.716.7Hz),5.95(d,1H,PCH,J=13.1Hz),6.40(s,1H,furan-H),6.55(s,1H,furan-H),7.04(d,1H,Ar-H,J=8.6Hz),7.31(d,1H,Ar-H,J=6.7Hz),7.55(s,1H,Ar-H),7.60(s,1H,furan-H),8.18(s,3H,NH3);
13C NMR(100MHz,DMSO-d6):δ167.52,152.26,150.26,142.94,129.52,128.06,125.31,122.51,115.30,110.72,110.28,67.07,65.61,52.26,38.65,29.19,19.42,13.67;
31P NMR(160MHz,DMSO-d6):6.23;
化合物23
所得纯品为黄色固体,收率为91%;m.p.117~119℃。
元素分析/%:计算值:C,43.65;H,4.58;N,3.18;实测值:C,43.49;H,4.70;N,3.42.
1H NMR(400MHz,DMSO-d6):δ2.45(s,6H,2CH3),2.73(dd,2H,CH2,J=14.37.1Hz),3.63(d,3H,OCH3,J=10.3Hz),4.76(q,2H,COCH2,J=16.5Hz),6.26(d,1H,PCH,J=13.6Hz),6.37(s,1H,furan-H),6.55(s,1H,furan-H),6.76(d,1H,Ar-H,J=8.6Hz),7.12(d,1H,Ar-H,J=8.5Hz),7.37(s,1H,Ar-H),7.44(s,1H,furan-H),9.55(s,2H,NH2);
13C NMR(100MHz,DMSO-d6):δ167.35,152.07,148.74,143.09,130.08,127.53,126.81,123.69,114.55,111.07,110.75,66.51,66.08,64.92,53.21,34.57;
31P NMR(160MHz,DMSO-d6):9.89;
化合物24
所得纯品为棕红色油状,收率为94%;折射率为1.5103。
元素分析/%:计算值:C,46.17;H,5.17;N,2.99;实测值:C,46.24;H,5.38;N,2.97.
1H NMR(400MHz,CDCl3):δ1.21(s,6H,2CH3),2.77(s,4H,2CH2),3.61(d,3H,OCH3,J=10.3Hz),4.68-4.78(m,2H,COCH2),6.21(d,1H,PCH,J=13.6Hz),6.34(s,1H,furan-H),6.53(s,1H,furan-H),6.74(d,1H,Ar-H,J=8.7Hz),7.10(d,1H,Ar-H, J=8.7Hz),7.35(s,1H,Ar-H),7.38(s,1H,furan-H),9.50(s,2H,NH2);
13C NMR(100MHz,CDCl3):δ166.14,150.99,147.95,141.64,128.89,126.32,125.61,122.60,113.45,109.63,109.47,65.59,64.95,64.00,51.91,51.85,40.59,9.73;
31P NMR(160MHz,CDCl3):8.67;
化合物25
所得纯品为棕红色油状,收率为92%;折射率为1.4884。
元素分析/%:计算值:C,48.40;H,5.69;N,2.82;实测值:C,48.46;H,5.70;N,2.88.
1H NMR(400MHz,CDCl3):δ0.90(s,6H,2CH3),1.65(s,4H,2CH2),2.64(s,4H,2CH2),3.61(d,3H,OCH3,J=9.7Hz),4.59-4.97(m,2H,COCH2),6.20(d,1H,PCH,J=13.5Hz),6.35(s,1H,furan-H),6.53(s,1H,furan-H),6.74(d,1H,Ar-H,J=8.0Hz),7.11(d,1H,Ar-H,J=8.5Hz),7.36(s,1H,Ar-H),7.38(s,1H,furan-H),9.52(s,2H,NH2);
13C NMR(100MHz,CDCl3):δ167.20,152.17,149.23,142.74,130.04,127.46,126.76,123.80,114.63,110.74,110.56,66.75,66.12,65.17,52.96,48.84,19.08,11.17;
31P NMR(160MHz,CDCl3):8.53;
化合物26
所得纯品为棕红色油状,收率为89%;折射率为1.5081。
元素分析/%:计算值:C,48.40;H,5.69;N,2.82;实测值:C,48.41;H,5.89;N,2.71.
1H NMR(400MHz,CDCl3):δ1.23(s,12H,4CH3),3.15(s,2H,CH),3.61(d,3H,OCH3,J=10.2Hz),4.73(s,2H,COCH2),6.19(d,1H,PCH,J=13.1Hz),6.33(s,1H,furan-H),6.52(s,1H,furan-H),6.74(d,1H,Ar-H,J=8.7Hz),7.10(d,1H,Ar-H,J=7.6Hz),7.36(s,1H,Ar-H),7.36(s,1H,furan-H),9.17(s,2H,NH2);
13C NMR(100MHz,CDCl3):δ167.28,152.22,149.33,142.55,130.03,127.45,126.73,123.82,114.69,110.64,110.51,67.02,66.16,65.43,52.88,46.11,18.59;
31P NMR(160MHz,CDCl3):7.53;
化合物27
所得纯品为棕红色油状,收率为98%;折射率为1.5321。
元素分析/%:计算值:C,50.39;H,6.15;N,2.67;实测值:C,50.29;H,6.27;N,2.59.
1H NMR(400MHz,CDCl3):δ0.90(t,6H,2CH3),1.30(d,4H,2CH2,J=7.1Hz),1.61(s,4H,2CH2),2.68(s,4H,2CH2),3.62(d,3H,OCH3,J=10.3Hz),4.73(q,2H,COCH2,J=16.5Hz),6.21(d,1H,PCH,J=13.6Hz),6.35(s,1H,furan-H),6.55(s,1H,furan-H),6.75(d,1H,Ar-H,J=8.8Hz),7.11(d,1H,Ar-H,J=8.6Hz),7.36(s,1H,Ar-H),7.39(s,1H,furan-H),9.55(s,2H,NH2);
13C NMR(100MHz,CDCl3):δ167.23,152.18,149.31,142.72,130.05,127.44,126.76,123.82,114.64,110.70,110.57,66.76,66.13,65.17,52.93,47.13,27.64,19.97,13.58;
31P NMR(160MHz,CDCl3):8.57;
化合物28
所得纯品为棕红色油状,收率为98%;折射率为1.5183。
元素分析/%:计算值:C,50.39;H,6.15;N,2.67;实测值:C,50.58;H,6.29;N,2.74.
1H NMR(400MHz,CDCl3):δ0.96(d,12H,4CH3,J=6.0Hz),2.03-2.06(m,2H,CH),2.56(d,4H,2CH2,J=6.5Hz),3.60(d,3H,OCH3,J=10.1Hz),4.68-4.78(m,2H,COCH2),6.19(d,1H,PCH,J=13.8Hz),6.34(s,1H,furan-H),6.54(s,1H,furan-H),6.75(d,1H,Ar-H,J=8.7Hz),7.11(d,1H,Ar-H,J=8.6Hz),7.37(s,1H,Ar-H),7.37(s,1H,furan-H),9.32(s,2H,NH2);
13C NMR(100MHz,CDCl3):δ167.24,152.20,149.43,142.57,130.01,127.44, 126.68,123.79,114.66,110.70,110.53,66.92,66.12,65.33,54.88,52.89,25.18,20.41;
31P NMR(160MHz,CDCl3):7.87;
化合物29
所得纯品为棕红色油状,收率为91%;折射率为1.5381。
元素分析/%:计算值:C,44.95;H,4.88;N,3.08;实测值:C,44.71;H,4.93;N,3.30.
1H NMR(400MHz,CDCl3):δ2.72(s,9H,3CH3),3.65(d,3H,OCH3,J=10.5Hz),4.78(q,2H,COCH2,J=16.4Hz),6.30(d,1H,PCH,J=13.5Hz),6.37(s,1H,furan-H),6.60(s,1H,furan-H),6.79(d,1H,Ar-H,J=8.7Hz),7.13(d,1H,Ar-H,J=8.0Hz),7.36(s,1H,Ar-H),7.42(s,1H,furan-H),12.61(s,1H,NH);
13C NMR(100MHz,CDCl3):δ167.39,152.20,148.71,142.96,130.09,127.64,126.77,123.71,114.64,111.05,110.82,66.75,66.07,65.15,53.26,44.90;
31P NMR(160MHz,CDCl3):9.18;
化合物30
所得纯品为棕红色油状,收率为90%;折射率为1.5161。
元素分析/%:计算值:C,48.40;H,5.69;N,2.82;实测值:C,48.59;H,5.51;N,2.76.
1H NMR(400MHz,CDCl3):δ1.25(s,9H,3CH3),2.98(s,6H,3CH2),3.64(d,3H,OCH3,J=8.2Hz),4.71-4.82(m,2H,COCH2),6.26(d,1H,PCH,J=11.7Hz),6.35(s,1H,furan-H),6.59(s,1H,furan-H),6.79(d,1H,Ar-H,J=8.5Hz),7.11(s,1H,Ar-H),7.35(s,1H,Ar-H),7.39(s,1H,furan-H),12.20(s,1H,NH);
13C NMR(100MHz,CDCl3):δ167.34,152.18,149.35,142.55,129.90,127.52,126.56,123.60,114.66,110.59,66.96,66.07,65.38,52.98,52.92,45.26,8.29;
31P NMR(160MHz,CDCl3):9.00;
化合物31
所得纯品为棕红色油状,收率为88%;折射率为1.5191。
元素分析/%:计算值:C,51.31;H,6.37;N,2.60;实测值:C,51.19;H,6.13;N,2.65.
1H NMR(400MHz,CDCl3):δ0.95(t,9H,3CH3,J=7.3Hz),1.66-1.68(m,6H,3CH2),1.66-1.68(m,6H,3CH2),2.83(dd,6H,3CH2,J=10.3,6.1Hz),3.64(d,3H,OCH3,J=10.3Hz),4.77(q,2H,COCH2,J=16.4Hz),6.24(d,1H,PCH,J=13.5Hz),6.36(s,1H,furan-H),6.59(s,1H,furan-H),6.80(d,1H,Ar-H,J=8.8Hz),7.13(d,1H,Ar-H,J=8.8Hz),7.36(s,1H,Ar-H),7.39(s,1H,furan-H),12.20(s,1H,NH);
13C NMR(100MHz,CDCl3):δ167.29,152.20,149.50,142.47,129.88,127.49,126.52,123.61,114.67,110.53,66.96,66.07,65.38,53.25,16.49,11.07;
31P NMR(160MHz,CDCl3):8.92;
化合物32
所得纯品为黄色油状,收率为99%;折射率为1.4891。
元素分析/%:计算值:C,53.80;H,6.95;N,2.41;实测值:C,53.94;H,7.10;N,2.46.
1H NMR(400MHz,CDCl3):δ0.96(d,9H,3CH3,J=6.1Hz),1.34(d,6H,3CH2,J=6.5Hz),1.61(s,6H,3CH2),2.88(d,6H,3CH2,J=6.8Hz),3.64(d,3H,OCH3,J=9.6Hz),4.77(q,2H,COCH2,J=16.4Hz),6.25(d,1H,PCH,J=12.7Hz),6.35(s,1H,furan-H),6.60(s,1H,furan-H),6.80(d,1H,Ar-H,J=8.4Hz),7.12(d,1H,Ar-H,J=8.6Hz),7.35(s,1H,Ar-H),7.39(s,1H,furan-H),12.30(s,1H,NH);
13C NMR(100MHz,CDCl3):δ167.28,152.20,149.56,142.44,129.86,127.47,126.50,123.62,114.67,110.52,66.94,66.07,65.37,52.84,51.38,24.85,19.96,13.52.;
31P NMR(160MHz,CDCl3):8.99;
实施例3
盆栽法除草活性抑制实验
本专利采用苘麻、刺苋和藜为代表性双子叶植物靶标,采用温室盆栽法对本专利所合成的部分目标化合物进行了除草活性测试。
试验药剂:用分析天平称取原药,加乳化剂(吐温-80)和溶剂(DMF或DMSO或水),配制成1.0~5.0%的乳油小制剂或水剂。然后用蒸溜水稀释成10g/亩浓度备用。
试验方法:将供试杂草种子均匀播入内径9cm盆钵中,于温室中培养。待双子叶杂草真叶期时,在自动喷雾装置上进行芽后茎叶喷雾处理。每处理3次重复,设空白对照,处理后静置4~5小时,待叶片上药液干后,移入温室内培养。每天观察植株生长情况,定期记录受害症状,分别于药后25天目测调查综合除草活性。
评价标准:结果调查采用目测法,目测评价药剂对植株生长抑制、畸形、黄化、腐烂、坏死等影响程度,然后根据综合受害程度按0~100%分级法目测评价除草活性。评价标准具体见表1。
表1 除草活性目测法评价标准
衍生物对双子叶植物的盆栽除草活性数据详见以下表2:
表2 部分化合物I对双子叶植物的除草活性(盆栽法)
上述研究结果表明,在母体骨架中引入有机铵盐而得到的结构骨架I显示了高效的除草活性。例如化合物7、13、15、31其除草活性均高于相应的金属钾盐、钠盐、锂盐。特别是化合物7在150gai/ha剂量下对苘麻、刺苋和藜的防效为100%,而且当剂量降低8倍,在18.75g ai/ha剂量下对苘麻、刺苋和藜的抑制率也为60-80%,因此,具有通式I的化合物具有进一步研究和开发的价值。
本发明的化合物作为除草剂使用时,可将本发明的化合物与其它植保上允许的载体或稀释剂混合,借此将其调制成通常使用的各种剂型,如混剂、颗粒剂、水乳剂等来使用,也可以与其它农药如杀菌剂、杀虫剂、除草剂、植物生长调节剂等混合使用或同时并用。
在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外,在不相互矛盾的情况下,本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本发明的实施例,可以理解的是,上述实施例是示例性的,不能理解为对本发明的限制,本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。