Carboxylate compound and application thereof
阅读说明：本技术 一种羧酸酯类化合物及其应用 (Carboxylate compound and application thereof ) 是由 杨辉斌 秦博 马宏娟 英君伍 商璐 王明欣 孙冰 王刚 陈霖 梁爽 张帆 李斌 于 2019-10-08 设计创作，主要内容包括：本发明公开一种羧酸酯类化合物及其应用,所述化合物如通式(I)所示：通式I中各取代基定义见说明书。本发明通式I化合物具有优异的除草活性,可用于防治农业杂草。(The invention discloses a carboxylate compound and application thereof, wherein the compound is shown as a general formula (I):)
1. A carboxylic acid ester compound characterized by: the compound is shown as a general formula I:
in the formula:
R1、R2each independently selected from H, C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C1-C6Haloalkyl, phenyl unsubstituted or substituted with at least one substituent selected from: halogen, cyano, nitro, C1-C6Alkyl radical, C3-C6Cycloalkyl or C1-C6A haloalkyl group;
R3、R4each independently selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Alkenyl or C3-C6Alkynyl.
X1、X2、X3、X4Each independently selected from cyano, nitro, halogen, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl group, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, or phenyl unsubstituted or substituted with 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 heteroatoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl or halophenyl;
W1selected from N or CX5；
W2Selected from N or CX6；
X5、X6Each independently selected from hydrogen, cyano, nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Halogenocycloalkyl C1-C6Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfoxide group, Y1Sulfone group, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfoxide group C1-C6Alkyl radical, Y1Sulfone group C1-C6Alkyl, COY1、COOY1、OCOOY1、NY1COOY2、C(O)NY1Y2、NY1C(O)NY1Y2、OC(O)N Y1Y2、C(O)N(Y1)OY2、NY1SO2Y2、NY1COY2、OSO2Y1、CH＝NOY1、C1-C6alkyl-CH-NOY1、C1-C6alkyl-O-N-C Y1Y2Or phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
Y1、Y2each independently selected from hydrogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
when W is1Is selected from CH, W2Selected from CH, X1And X3When selected from chlorine, X2Is not nitro or chlorine;
l is selected from the following:
R5、R7each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl or C2-C6Alkynyl C1-C6An alkyl group;
R6is selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl radical, C2-C6Alkynyl C1-C6Alkyl, or benzene unsubstituted or substituted with 1 to 5 substituents selected from halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C2-C6Alkenyl or C2-C6An alkynyl group;
m1、m2n is independently selected from 0-10;
Z1、Z2each independently selected from the group consisting of a bond, CH2O, S or NH.
2. A compound according to claim 1, wherein in formula I:
R1、R2each independently selected from H, C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C1-C6Haloalkyl, phenyl unsubstituted or substituted with at least one substituent selected from: halogen, cyano, nitro, C1-C6Alkyl radical, C3-C6Cycloalkyl or C1-C6A haloalkyl group;
R3、R4each independently selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Alkenyl or C3-C6Alkynyl.
X1、X2、X3、X4Each independently selected from cyano, nitro, halogen, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl group, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, or phenyl unsubstituted or substituted with 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 heteroatoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl or halophenyl;
W1selected from N or CX5；
W2Selected from N or CX6；
X5、X6Each independently selected from hydrogen, cyano, nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Halogenocycloalkyl C1-C6Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfoxide group, Y1Sulfone group, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfoxide group C1-C6Alkyl radical, Y1Sulfone group C1-C6Alkyl, COY1、COOY1、OCOOY1、CH＝NOY1、C1-C6alkyl-CH-NOY1、C1-C6alkyl-O-N-C Y1Y2Or phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
Y1、Y2each independently selected from hydrogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, unsubstituted or substituted by 1 to 5 substituentsSubstituted phenyl, 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aromatic heterocyclic ring containing 1-4 heteroatoms, 5-7 membered aliphatic heterocyclic ring containing 1-4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
when W is1Is selected from CH, W2Selected from CH, X1And X3When selected from chlorine, X2Is not nitro or chlorine;
l is selected from the following:
R5、R7each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl or C2-C6Alkynyl C1-C6An alkyl group;
R6is selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl radical, C2-C6Alkynyl C1-C6Alkyl, or benzene unsubstituted or substituted with 1 to 5 substituents selected from halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C2-C6Alkenyl or C2-C6An alkynyl group;
m1、m2n is independently selected from 0-10;
Z1、Z2each independently selected from the group consisting of a bond, CH2O, S or NH.
3. A compound according to claim 2, wherein in formula I:
R1、R2each independently selected from C1-C3Alkyl or C3-C6A cycloalkyl group;
R3、R4each independently selected from C1-C3An alkyl group;
X1、X2、X3、X4each independently selected from cyano, halogen, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl group, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyloxy, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl group, the followingThe substituent is selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl or halophenyl;
W1selected from N or CX5；
W2Selected from N or CX6；
X5、X6Each independently selected from hydrogen, cyano, nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Halogenocycloalkyl C1-C6Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfone group, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfone group C1-C6Alkyl, COY1、COOY1Or phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
Y1、Y2each independently selected from hydrogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl or C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
when W is1Is selected from CH, W2Selected from CH, X1And X3When selected from chlorine, X2Is not chlorine;
l is selected from the following:
R5、R7each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl or C1-C6Alkoxy radical C1-C6An alkane;
R6is selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl radical, C2-C6Alkynyl C1-C6Alkyl or phenyl; the hydrogen on the phenyl ring may be substituted by one or more substituents selected fromThe substituent is selected from halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C2-C6Alkenyl or C2-C6An alkynyl group;
m1、m2n is independently selected from 0-10;
Z1、Z2each independently selected from the group consisting of a bond, CH2O, S or NH.
4. A compound according to claim 3, wherein in formula I:
R1、R2each independently selected from C1-C3Alkyl or C3-C6A cycloalkyl group;
R3、R4each independently selected from C1-C3An alkyl group;
X1、X2、X3、X4each independently selected from halogen, C1-C3Alkylsulfonyl radical, C1-C3Haloalkylsulfonyl group, C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Haloalkoxy, C1-C3Alkoxy radical C1-C3Alkyl radical, C1-C3Alkoxy radical C1-C3Alkoxy radical, C1-C3Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyloxy, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents being selected from nitroHalogen, C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Haloalkoxy, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
W1selected from N or CX5；
W2Selected from N or CX6；
X5、X6Each independently selected from hydrogen, halogen, C1-C3Alkyl radical, C1-C3Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Halogenocycloalkyl C1-C3Alkyl radical, Y1Oxy radical, Y1Sulfone group, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfone group C1-C6Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
Y1、Y2each independently selected from hydrogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, or phenyl which is unsubstituted or substituted by 1 to 5 substituents containing 1 to 4 hetero atoms5-7 membered aliphatic heterocyclic ring of the seed, 5-7 membered aromatic heterocyclic ring containing 1-4 hetero atoms, 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
when W is1Is selected from CH, W2Selected from CH, X1And X3When selected from chlorine, X2Is not chlorine;
l is selected from the following:
R5、R7each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl or C1-C6Alkoxy radical C1-C6An alkane;
R6is selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl radical, C2-C6Alkynyl C1-C6Alkyl, or benzene unsubstituted or substituted with 1 to 5 substituents selected from halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C2-C6Alkenyl or C2-C6An alkynyl group;
m1、m2n is independently selected from 0-8;
Z1、Z2each independently selected from the group consisting of a bond, CH2O, S or NH.
5. Use of a compound of formula I according to claim 1 for controlling weeds.
6. A herbicidal composition characterized by: the herbicidal composition is an active substance and an agriculturally acceptable carrier, the active ingredient is a compound of the general formula I as claimed in claim 1, and the weight percentage of the active ingredient in the composition is 1-99%.
7. A method of controlling weeds with a herbicidal composition according to claim 6, characterized in that: applying a herbicidally effective dose of the herbicidal composition of claim 6 to the weeds or to a growth medium or locus of the weeds.
Technical Field
The invention belongs to the field of herbicides. In particular to a carboxylic ester compound and application thereof.
Background
Due to succession and transition of weed populations and generation and rapid development of chemical pesticide resistance, people continuously strengthen the awareness of ecological environment protection, and continuously increase the attention to chemical pesticide pollution, understanding of the influence of pesticides on non-target organisms and problems of lodging in the pesticide ecological environment. With the diminishing area of cultivated land in the world, the increasing population and the increasing demand for food, people are forced to rapidly develop agricultural production techniques, improve the complete cultivation system, and need to continuously invent novel and improved herbicidal compounds and compositions.
JPS55363A reports that certain carboxylate compounds have herbicidal activity.
The dicarboxylate compounds according to the present invention are not disclosed.
Disclosure of Invention
The invention aims to provide a dicarboxylic ester compound which is novel in structure and safe to crops and an application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a carboxylic ester compound is shown as a general formula I:
in the formula:
R1、R2each independently selected from H, C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C1-C6Haloalkyl, phenyl unsubstituted or substituted with at least one substituent selected from: halogen, cyano, nitro, C1-C6Alkyl radical, C3-C6Cycloalkyl or C1-C6A haloalkyl group;
R3、R4each independently selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Alkenyl or C3-C6Alkynyl.
X1、X2、X3、X4Each independently selected from cyano, nitro, halogen, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl group, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, or phenyl unsubstituted or substituted with 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 heteroatoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl or halophenyl;
W1selected from N or CX5；
W2Selected from N or CX6；
X5、X6Each independently selected from hydrogen, cyano, nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Halogenocycloalkyl C1-C6Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfoxide group, Y1Sulfone group, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfoxide group C1-C6Alkyl radical, Y1Sulfone group C1-C6Alkyl, COY1、COOY1、OCOOY1、NY1COOY2、C(O)NY1Y2、NY1C(O)NY1Y2、OC(O)N Y1Y2、C(O)N(Y1)OY2、NY1SO2Y2、NY1COY2、OSO2Y1、CH＝NOY1、C1-C6alkyl-CH-NOY1、C1-C6alkyl-O-N-C Y1Y2Or phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
Y1、Y2each independently selected from hydrogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
when W is1Is selected from CH, W2Selected from CH, X1And X3When selected from chlorine, X2Is not nitro or chlorine;
l is selected from the following:
R5、R7each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl or C2-C6Alkynyl C1-C6An alkyl group;
R6is selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl radical, C2-C6Alkynyl C1-C6Alkyl, or benzene unsubstituted or substituted with 1 to 5 substituents selected from halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C2-C6Alkenyl or C2-C6An alkynyl group;
m1、m2n is independently selected from 0-10;
Z1、Z2each independently selected from the group consisting of a bond, CH2O, S or NH.
The preferred compounds are characterized by the general formula I:
R1、R2each independently selected from H, C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C1-C6Haloalkyl, phenyl unsubstituted or substituted with at least one substituent selected from: halogen, cyano, nitro, C1-C6Alkyl radical, C3-C6Cycloalkyl or C1-C6A haloalkyl group;
R3、R4each independently selected from C1-C6Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Alkenyl or C3-C6Alkynyl.
X1、X2、X3、X4Each independently selected from cyano, nitro, halogen, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl group, C1-C6Alkylsulfinyl radical, C1-C6Haloalkylsulfinyl radical, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyl oxy, C2-C6Alkenyl radical, C2-C6Alkynyl, or phenyl unsubstituted or substituted with 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 heteroatoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6HaloalkoxyBase, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl or halophenyl;
W1selected from N or CX5；
W2Selected from N or CX6；
X5、X6Each independently selected from hydrogen, cyano, nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Halogenocycloalkyl C1-C6Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfoxide group, Y1Sulfone group, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfoxide group C1-C6Alkyl radical, Y1Sulfone group C1-C6Alkyl, COY1、COOY1、OCOOY1、CH＝NOY1、C1-C6alkyl-CH-NOY1、C1-C6alkyl-O-N-C Y1Y2Or phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
Y1、Y2each independently selected from hydrogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
when W is1Is selected from CH, W2Selected from CH, X1And X3When selected from chlorine, X2Is not nitro or chlorine;
l is selected from the following:
R5、R7each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl or C2-C6Alkynyl C1-C6An alkyl group;
R6is selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical、C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl radical, C2-C6Alkynyl C1-C6Alkyl, or benzene unsubstituted or substituted with 1 to 5 substituents selected from halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C2-C6Alkenyl or C2-C6An alkynyl group;
m1、m2n is independently selected from 0-10;
Z1、Z2each independently selected from the group consisting of a bond, CH2O, S or NH.
Further preferred are compounds of formula I:
R1、R2each independently selected from C1-C3Alkyl or C3-C6A cycloalkyl group;
R3、R4each independently selected from C1-C3An alkyl group;
X1、X2、X3、X4each independently selected from cyano, halogen, C1-C6Alkylsulfonyl radical, C1-C6Haloalkylsulfonyl group, C1-C6Alkylthio radical, C1-C6Haloalkylthio, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C1-C6Alkoxy radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C3Alkoxy radical, C1-C6Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyloxy, or unsubstituted or substituted by 1-Phenyl substituted with 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl or halophenyl;
W1selected from N or CX5；
W2Selected from N or CX6；
X5、X6Each independently selected from hydrogen, cyano, nitro, halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C3-C6Halogenocycloalkyl C1-C6Alkyl radical, Y1Oxy radical, Y1Thio radical, Y1Y2Amino group, Y1Sulfone group, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfone group C1-C6Alkyl, COY1、COOY1Or phenyl which is unsubstituted or substituted by 1 to 5 substituents, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 heteroatoms, a 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 heteroatoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6A halogenated alkoxy group,C3-C6Cycloalkyl radical, C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
Y1、Y2each independently selected from hydrogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl or C3-C6Cycloalkoxy, C2-C6Alkenyl radical, C2-C6Alkynyl, phenyl and halophenyl;
when W is1Is selected from CH, W2Selected from CH, X1And X3When selected from chlorine, X2Is not chlorine;
l is selected from the following:
R5、R7each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl or C1-C6Alkoxy radical C1-C6An alkane;
R6is selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl radical, C2-C6Alkynyl C1-C6Alkyl or phenyl; the hydrogen on the phenyl ring may be substituted by one or more substituents selected from halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C2-C6Alkenyl or C2-C6An alkynyl group;
m1、m2n is independently selected from 0-10;
Z1、Z2each independently selected from the group consisting of a bond, CH2O, S or NH.
Even further preferred are compounds of formula I wherein:
R1、R2each independently selected from C1-C3Alkyl or C3-C6A cycloalkyl group;
R3、R4each independently selected from C1-C3An alkyl group;
X1、X2、X3、X4each independently selected from halogen, C1-C3Alkylsulfonyl radical, C1-C3Haloalkylsulfonyl group, C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Haloalkoxy, C1-C3Alkoxy radical C1-C3Alkyl radical, C1-C3Alkoxy radical C1-C3Alkoxy radical, C1-C3Alkoxy radical C1-C3Alkoxy radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Cycloalkyl radical C1-C3Alkoxy radical, C3-C6Cycloalkyloxy, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered lipoheterocyclic ring containing 1 to 4 hetero atoms, containing 1 to 4 hetero atomsAtomic 5-7 membered aromatic heterocycle, 5-7 membered aliphatic heterocycle C containing 1-4 hetero atoms1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C3Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy radical, C1-C3Haloalkoxy, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
W1selected from N or CX5；
W2Selected from N or CX6；
X5、X6Each independently selected from hydrogen, halogen, C1-C3Alkyl radical, C1-C3Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C3Alkyl radical, C3-C6Halogenocycloalkyl C1-C3Alkyl radical, Y1Oxy radical, Y1Sulfone group, Y1Oxy radical C1-C6Alkyl radical, Y1Thio radical C1-C6Alkyl radical, Y1Y2Amino group C1-C6Alkyl radical, Y1Sulfone group C1-C6Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
Y1、Y2each independently selected from hydrogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C3-C6Cycloalkyl radical, C3-C6Cycloalkyl radical C1-C6Alkyl radical, C1-C6Alkoxy radical C1-C6Alkyl, or phenyl unsubstituted or substituted by 1 to 5 substituents, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aromatic heterocyclic ring containing 1 to 4 hetero atoms, 5-to 7-membered aliphatic heterocyclic ring containing 1 to 4 hetero atoms C1-C6Alkyl or 5-to 7-membered heteroaromatic ring C containing 1 to 4 heteroatoms1-C6Alkyl, the following substituents are selected from nitro, halogen and C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C1-C6Haloalkoxy, C3-C6Cycloalkyl or C3-C6A cycloalkoxy group;
when W is1Is selected from CH, W2Selected from CH, X1And X3When selected from chlorine, X2Is not chlorine;
l is selected from the following:
R5、R7each independently selected from C1-C6Alkyl radical, C1-C6Haloalkyl or C1-C6Alkoxy radical C1-C6An alkane;
R6is selected from C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C2-C6Alkenyl radical C1-C6Alkyl radical, C2-C6Alkynyl C1-C6Alkyl, or benzene unsubstituted or substituted with 1 to 5 substituents selected from halogen, C1-C6Alkyl radical, C1-C6Haloalkyl, C1-C6Alkoxy radical, C2-C6Alkenyl or C2-C6An alkynyl group;
m1、m2n is independently selected from 0-8;
Z1、Z2each independently selected from the group consisting of a bond, CH2O, S or NH.
In the definitions of the compounds of the general formula I given above, the terms used are collectively defined as follows:
alkyl means straight or branched chain forms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and the like. Cycloalkyl is meant to include cyclic chain forms such as cyclopropyl, methylcyclopropyl, cyclopropylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Alkoxy means a group having an oxygen atom attached to the terminal of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, and the like. The 5-7 membered aliphatic heterocyclic ring containing 1-4 hetero atoms means a 5-7 membered heterocyclic compound containing 1-4 hetero atoms and having no aromatic character, such as ethylene oxide, tetrahydrofuran, imidazolidinone, caprolactam, etc. The 5-7 membered aromatic heterocyclic ring containing 1-4 hetero atoms refers to a 5-7 membered heterocyclic compound containing 1-4 hetero atoms and having aromatic characteristics, such as furan, thiophene, pyrazole, pyridine and the like.
The compound I with the general formula can be prepared by the following method:
the compound of the general formula II, the compound of the general formula III and the compound of the general formula IV react in a proper solvent at the temperature of-10 ℃ to the boiling point of the proper solvent for 0.5 to 48 hours to prepare the target compound I.
Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide, and the like.
The addition of suitable alkali substances in the reaction system can be beneficial to the reaction. Suitable bases are selected from organic bases such as triethylamine, N-dimethylaniline or pyridine, etc., or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide, etc.
Compounds of formula IV are commercially available.
The preparation of the compounds of formula II is as follows:
the general formula V in the formula is reacted in a proper solvent at the temperature of minus 10 ℃ to boiling point for 0.5 to 48 hours under the action of alkali and a catalyst to prepare the compound of the general formula II. Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide, and the like. Suitable bases are selected from sodium carbonate, potassium carbonate or triethylamine and the like. Suitable catalysts are selected from sodium carbonate, potassium carbonate, acetone cyanohydrin, azide, quaternary ammonium azide, metal cyanide or DMAP, and the like.
The preparation of the compounds of formula V is as follows:
the compound of formula VI is reacted in a suitable solvent with a compound of formula VII (prepared as described in commercially available or reference EP 0240001) in a suitable solvent at a temperature of-10 deg.C to reflux temperature for 0.5-24 hours to produce the compound of formula IV. Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, acetic acid, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide, and the like.
The addition of suitable alkali substances is beneficial to the reaction. Suitable bases are selected from organic bases such as triethylamine, N-dimethylaniline or pyridine, etc., or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide or potassium tert-butoxide, etc.
The starting carboxylic acid (commercially available) corresponding to the compound of formula VI is reacted with an acid acylating agent in a solvent at a temperature of-10 deg.C to the boiling point for 0.5 to 48 hours to produce the compound of formula V. Suitable acid halogenating agents are selected from oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus trichloride or phosphorus pentachloride and the like. Suitable solvents are selected from dichloromethane, 1, 2-dichloroethane, hexane, benzene, toluene, acetonitrile, acetic acid, dioxane or liquid acid acylating agents and the like.
The preparation method of the compound in the general formula III is the same as that of the compound in the general formula II.
The compound of the general formula I has herbicidal activity and can be used for preventing and controlling various weeds in agriculture. Compared with the compounds disclosed in the prior art, the carboxylic ester compound disclosed by the invention not only has excellent herbicidal activity, but also is safe to crops.
The invention also comprises a weeding composition taking the compound in the general formula I as an active component. The weight percentage of the active components in the weeding composition is 1-99%. The herbicidal composition also includes an agriculturally acceptable carrier.
The herbicidal compositions of the present invention can be applied in the form of various formulations. The compounds of the present invention are typically formulated to be more easily dispersed for use as herbicides by dissolving or dispersing the compounds in a carrier. For example: the chemical preparation can be prepared into wettable powder or missible oil and the like. Thus, in these compositions, at least one liquid or solid carrier is added, and it is generally necessary to add a suitable surfactant.
The present invention also provides an implementation method for controlling weeds, which comprises applying a herbicidally effective amount of the herbicidal composition of the present invention to the weeds or to the locus where the weeds grow or to the surface of a growth medium thereof. Preferably, the effective dose is from 1 to 1000 grams per hectare, preferably from 10 to 500 grams per hectare. For certain applications, one or more additional herbicides may be added to the herbicidal compositions of the present invention, thereby providing additional advantages and benefits.
The compounds of the present invention can be used alone or in combination with other known insecticides, fungicides, plant growth regulators or fertilizers.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
The invention has the advantages that:
compared with the known carboxylic ester compounds, the compounds in the general formula contain two different benzoyl substitutions, the structure is novel, the carboxylic ester compounds have unexpected high herbicidal activity, and also have high herbicidal activity under a lower dosage, so that the efficiency is high, the use amount of pesticides is reduced, the cost is reduced, and the pollution to the environment is reduced.
Detailed Description
The following examples and biological test results are provided to further illustrate the invention and are not meant to limit the invention.
Synthesis examples
Example 1 Synthesis of Compounds 1-21
(1) Synthesis of 2-chloro-3-methoxymethyl-4-methylsulfonylbenzoyl chloride
2-methanesulfonyl-4-trifluoromethylbenzoic acid (4 g, 14.35 mmol), dichloromethane (30 ml) and DMF were added to the reaction flask one drop, oxalyl chloride (9.11 g, 71.8 mmol) was added slowly, the mixture was stirred at room temperature for 40 minutes, the solvent was evaporated under reduced pressure, toluene (15 ml) was added to the residue and after stirring for 3 minutes, the solvent was evaporated under reduced pressure to give 4.26 g of a yellow solid, which was taken directly to the next step.
(2) Synthesis of 2-chloro-3-methoxymethyl-4-methylsulfonylbenzoic acid (1, 3-dimethylpyrazol-5-yl) ester
To a reaction flask, 1, 3-dimethyl-5-hydroxypyrazole (1.77 g, 15.79 mmol), dichloromethane (100 ml), and triethylamine (2.9 g, 28.7 mmol) were added, and a dichloromethane solution (30 ml) of the above-obtained 2-chloro-3-methoxymethyl-4-methanesulfonylbenzoyl chloride was added dropwise. After stirring at room temperature for 1 hour, the solvent was evaporated under reduced pressure, ethyl acetate (100 ml) was added to the residue, water (100 ml) was added for liquid-phase extraction, the organic phase was washed successively with saturated brine (100 ml), dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was separated by column chromatography to give 3.4 g of an off-white solid, yield: and (3.5).
(3) Synthesis of 1, 3-dimethyl-4- (2-chloro-3-methoxymethyl-4-methanesulfonylbenzoyl) -5-hydroxypyrazole
To a reaction flask were added 2-chloro-3-methoxymethyl-4-methylsulfonylbenzoic acid (1, 3-dimethylpyrazol-5-yl) ester (3.4 g, 9.12 mmol), dichloromethane (100 ml), triethylamine (1.38 g, 13.68 mmol), and acetone cyanohydrin (1 ml), reacted at room temperature for 12 hours, water was added to the reaction solution to extract (50 ml × 3), the aqueous phase was collected and then adjusted to pH 2 to 3 with 20% hydrochloric acid, the aqueous phase was extracted twice with ethyl acetate (100 ml), the organic phase was washed with saturated saline (50 ml), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 3.26 g of a yellow solid, yield: 96 percent.
(4) Synthesis of Compounds 1 to 21
1, 3-dimethyl-4- (2-chloro-3-methoxymethyl-4-methanesulfonylbenzoyl) -5-hydroxypyrazole (1.8 g, 4.8 mmol) was added to a reaction flask, triethylamine (1 g, 10 mmol) and dichloromethane (20 ml) were added thereto, adipoyl chloride (0.75 g, 4 mmol) was added dropwise under ice bath, and the mixture was reacted at room temperature for 30 minutes. The reaction mixture was subjected to column chromatography directly to give 97 mg of a yellow oil with a purity of 82% and a yield of 2.3%.
Example 2 Synthesis of Compounds 1-31
(1) Synthesis of 2-chloro-3-methoxyethoxymethyl-4-methanesulfonyl chloride
2-chloro-3-methoxyethoxymethyl-4-methylsulfonylbenzoic acid (3.4 g, 10.5 mmol) and toluene (20 ml) were added to a reaction flask, thionyl chloride (7.52 g, 63.2 mmol) was slowly added thereto, and the mixture was heated under reflux for 4 hours, and the solvent was evaporated under reduced pressure to give 3.6 g of a yellow oil which was used directly in the next step.
(2) Synthesis of 1, 3-dimethyl-4- (2-chloro-3-methoxyethoxymethyl-4-methylsulfonylbenzoyl) -5-carboxylate
To a reaction flask, 1, 3-dimethyl-5-carboxylate (1.4 g, 12.6 mmol), dichloromethane (50 ml), triethylamine (2.1 g, 21 mmol) were added, and a dichloromethane solution (20 ml) of the above-obtained 2-chloro-3-methoxyethoxymethyl-4-methylsulfonylbenzoyl chloride was added dropwise. After stirring at room temperature for 1 hour, triethylamine (1.6 g, 15.8 mmol) and 2 drops of acetone cyanohydrin were added, the mixture was stirred at room temperature overnight, water (50 ml) was added and stirred for half an hour, the aqueous phase was adjusted to pH 2-3 with 10% diluted hydrochloric acid, ethyl acetate (50 ml × 2) was extracted 2 times, the combined organic phases were washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 4.1 g of yellow oil with purity of 98% and yield of 91%.
(3) Synthesis of Compounds 1 to 31
To a reaction flask, 1, 3-dimethyl-4- (2-chloro-3-methoxyethoxymethyl-4-methanesulfonylbenzoyl) -5-carboxylate (1.25 g, 3 mmol), triethylamine (0.36 g, 3.6 mmol) and dichloromethane (20 ml) were added, and adipoyl chloride (0.27 g, 1.5 mmol) was added dropwise under ice bath. After stirring at room temperature for 30 minutes, the solvent was evaporated off under reduced pressure, ethyl acetate (50 ml) was added to the residue to dissolve it, the residue was washed 3 times with saturated sodium bicarbonate solution (50 ml x 3), the organic phase was washed with saturated brine (50 ml), dried over anhydrous magnesium sulfate, the solvent was evaporated off under reduced pressure, and the residue was separated by column chromatography to give 0.35 g of a yellow oil, 89% pure, yield 11%.
The compounds represented by general formula I can be obtained by substituting the raw materials in the reaction process according to the above-mentioned preparation method, and the compounds are shown in table 1, table 2 and table 3. Wherein, in the compounds of the general formula I shown in Table 1, W1Is CX5、W2Is CX6(ii) a In the compounds of the general formula I, W is shown in Table 21Is CX5、W2Is N; in Table 3, W is shown as1Is N, W2Is N.
A compound of the general formula I, wherein W1Is CX5、W2Is CX6。
Table 1 structural and physical properties of some compounds of formula I
A compound of the general formula I, wherein W1Is N, W2Is N.
Table 2 structural and physical properties of part of compounds of formula I
A compound of the general formula I, wherein W1Is CX5、W2Is N.
Table 3 structural and physical properties of part of compounds of formula I
Of partial compounds1H NMR(600MHz,DMSO-d6) The data are as follows:
compounds 1-2: 8.21(s,2H),8.13-8.14(d,2H),7.67-7.68(d,2H),3.46(s,6H),3.35(s,6H),2.90(s,4H),2.16(s, 6H).
Compounds 1-3: 8.27(d,2H),8.23-8.22(m,2H),7.68(d,2H),3.55(s,6H),3.33(s,6H),2.17-2.16(m,4H),2.12(s,6H),1.29-1.27(m, 2H).
Compounds 1-4: 8.35(d,2H),8.31-8.27(m,2H),7.75(d,2H),3.60(s,6H),3.41(s,6H),2.29(s,6H),2.24-2.22(m,4H),1.29-1.27(m, 4H).
Compounds 1-5: 8.28(d,2H),8.23-8.21(m,2H),7.68(d,2H),3.54(s,6H),3.34(s,6H),2.20(s,6H),2.07-2.06(m,4H),1.25-1.22(m,4H),1.11-1.09(m, 2H).
Compounds 1-6: 8.30(d,2H),8.26-8.24(m,2H),7.70(d,2H),3.55(s,6H),3.35(s,6H),2.25(s,6H),2.03-2.00(m,4H),1.29-1.24(m,4H),1.10-1.08(m, 4H).
Compounds 1-7: 8.21(s,2H),8.13-8.14(d,2H),7.68-7.69(d,2H),3.54(s,6H),3.35(s,6H),2.24(s,6H),2.17-2.20(t,4H),1.44-1.49(m,4H),1.25-1.30(m, 6H).
Compounds 1-13: 8.28(d,2H),8.26-8.24(m,2H),7.73(d,2H),3.64(s,6H),3.34(s,6H),2.25(s,6H),2.19-2.18(m,4H),1.53-1.52(m, 4H).
Compounds 1-15: 8.28(s,2H),8.22-8.24(m,2H),7.67-7.68(d,2H),3.53(s,6H),3.35(s,6H),2.50(s,6H),2.07-2.09(m,2H),2.00-2.03(m,1H),1.82-1.85(m,1H),1.62-1.66(m,1H),1.32-1.40(m,2H),1.16-1.19(m, 6H).
Compounds 1-19: 8.01(d,2H),7.43(d,2H),3.55(s,6H),3.34(s,6H),2.72(s,6H),2.25(s,6H), 2.19(s,4H),1.49(s, 4H).
Compounds 1-21: 8.12(d,2H),7.38(d,2H),5.08(s,4H),3.58(s,6H),3.49(s,6H),3.25(s,6H),2.26(s,6H),2.17(s,4H),1.61(s, 4H).
Compounds 1-31: 8.12(d,2H),7.37(d,2H),5.19(s,4H),3.75-3.59(m,4H),3.58(s,6H),3.55-3.57(m,4H),3.33(s,6H),3.31(s,6H),2.26(s,6H),2.15(s,4H),1.48(s, 4H).
Compounds 1-32: 8.12(d,2H),7.37(d,2H),5.20(s,4H),4.01-4.09(m,2H),3.76-3.83(m,2H),3.68-3.75(m,4H),3.62-3.67(m,2H),3.58(s,6H),3.32(s,6H),2.26(s,6H),2.16(s,4H),1.78-2.01(m,6H),1.56(m,2H),1.49(s, 4H).
Compounds 1-68: 8.06-8.07(d,2H),7.58-7.60(d,2H),4.94(s,4H),3.54(s,6H),3.35(s,6H),3.33(s,6H),2.28(s,6H),2.02-2.05(t,4H),1.42-1.45(m,4H),1.25-1.27(m, 2H).
Compounds 1-69: 8.07-8.08(d,2H),7.59-7.61(d,2H),4.95(s,4H),3.55(s,6H),3.41(s,6H),3.34(s,6H),2.29(s,6H),2.02-2.04(t,4H),1.47-1.48(m,4H),1.30-1.32(m, 4H).
Compounds 1-108: 8.04(s,2H),7.92(d,2H),7.45(d,2H),3.55(s,6H),3.31(s,6H),2.15-2.17(m,10H),1.36(s, 4H).
Compounds 1-127: 8.07(d,2H),7.95-7.97(dd,2H),7.69-7.71(dd,4H),3.53(s,6H),3.35(s,6H),2.19-2.21(m,4H),1.49-1.51(m, 4H).
Compound 1-193: 8.60(s,2H),8.34-8.36(d,2H),8.85-8.87(d,2H),7.62(s,2H),3.49(s,6H),3.40(s,6H),2.19-2.20(m,4H),1.50-1.51(m, 4H).
Compound I-521: 8.07-8.08(d,2H),7.95-7.97(m,2H),7.69-7.70(d,2H),7.38(s,2H),3.53(s,6H),3.33(s,6H),2.90(s, 4H).
Compound I-522: 8.07(d,2H),7.95-7.96(d,2H),7.68-7.70(d,2H),7.37(s,2H),3.53(s,6H),3.33(s,6H),2.69-2.72(m,4H),1.85-1.90(m, 2H).
Compound I-523: 8.12(s,2H),7.95-7.96(d,2H),7.81(s,2H),7.37(s,2H),3.53(s,6H),3.34(s,6H),2.41-2.45(m,4H),1.52-1.53(m,4H),1.32-1.35(m, 4H).
Compound I-524: 8.12(d,2H),7.99-8.00(m,2H),7.63-7.64(d,2H),4.34-4.38(m,2H),3.35(s,6H),2.27(s,6H),2.03-2.07(m,4H),1.35-1.36(m,4H),1.30-1.31(d, 12H).
Compound I-525: 8.12-8.13(d,2H),7.99-8.01(m,2H),7.65-7.66(d,2H),4.37-4.41(m,2H),3.36(s,6H),2.19-2.21(m,4H),2.18(s,6H),1.49-1.54(m,2H),1.29-1.30(d, 12H).
Compound I-526: 7.78(d,2H),7.75(s,2H),7.55-7.57(m,2H),7.48-7.49(d,2H),4.01-4.06(m,4H),2.69-2.74(m,4H),1.90-1.93(m,2H),1.26-1.29(t, 6H).
Compound I-527: 8.12(d,2H),7.99-8.00(m,2H),7.61-7.63(d,2H),3.57(s,6H),3.35(s,6H),2.73-2.77(m,4H),1.98-2.03(m,4H),1.25-1.29(m,4H),1.17-1.19(t, 6H).
Compound I-528: 8.28(d,2H),8.21-8.22(m,2H),7.64-7.65(d,2H),4.01-4.05(m,4H),3.52(s,6H),3.34(s,6H),2.19(s,4H),1.14-1.16(t, 6H).
Compound I-529: 8.28(s,2H),8.21-8.22(m,2H),7.65-7.66(d,2H),4.01-4.05(m,4H),3.55(s,6H),3.33(s,6H),2.02-2.06(m,4H),1.38-1.43(m,2H),1.14-1.16(t, 6H).
Compound I-530: 8.29-8.30(d,2H),8.25-8.26(d,2H),8.19-8.20(d,2H),4.01-4.05(m,4H),3.34(s,6H),2.49(s,6H),2.14-2.16(t,4H),1.36-1.39(m,4H),1.15-1.16(m,6H)
Compound I-531: 8.28-8.29(d,2H),8.23-8.25(m,2H),7.66-7.68(d,2H),4.01-4.05(m,4H),3.54(s,6H),3.34(s,6H),2.17-2.20(m,4H),1.44-1.49(m,4H),1.25-1.27(m,4H),1.17-1.19(m, 6H).
Compound I-532: 8.29(s,2H),8.24-8.25(m,2H),7.66-7.67(d,2H),4.01-4.05(m,4H),3.54(s,6H),3.34(s,6H),2.17-2.19(t,4H),1.45-1.49(m,4H),1.23-1.25(m,4H),1.17-1.19(m, 8H).
Compound I-533: 8.21(s,2H),8.13-8.14(d,2H),7.67-7.68(d,2H),6.63(s,2H),3.59(s,6H),3.35(s,6H),2.50(s, 6H).
Examples of bioassay
Example 3 determination of herbicidal Activity
Sowing seeds of broad-leaved weeds (zinnia elegans and abutilon) or grassy weeds (green bristlegrass and barnyard grass) in a paper cup with the diameter of 7cm and containing nutrient soil, covering soil for 1cm after sowing, compacting, spraying water, culturing in a greenhouse according to a conventional method, and spraying stems and leaves after 2-3 leaf periods of the weeds.
After the original drug is dissolved by acetone, the solution to be tested with the required concentration is prepared by using 1 per mill of Tween 80 to stand tap water according to the test requirements. The spray treatment (spray pressure 1.95 kg/cm) was carried out on a crawler-type crop sprayer (Engineer Research Ltd. in England) at the experimental design dose2The amount of the liquid spray is 500L/hm2And the track speed is 1.48 km/h). The experiment was repeated 3 times. After being treated, the test material is placed in an operation hall, after the liquid medicine is naturally dried in the shade, the test material is placed in a greenhouse for management according to a conventional method, the reaction condition of weeds to the agent is observed and recorded, the weed control effect of the test agent to weeds is regularly observed and visually observed after the treatment, the weed control effect is expressed by 0-100%, and the weed control effect is expressed by 0% to 100%, and the weed control effect is expressed by 100%.
Test results show that the compound of the general formula I has higher control effect on broad leaf weeds and grassy weeds generally. Some of the compounds tested, such as compounds 1-3, 1-4, 1-31, 1-32, 1-108, were administered at a dose of 600g a.i./hm2The composition has better control effect on zinnia elegans, piemarker, green bristlegrass or cockspur grass, and the control effect is more than 80 percent.
The compound with the general formula has herbicidal activity and can be used for controlling various weeds in agriculture. Meanwhile, the carboxylic ester compound has excellent herbicidal activity and is safe to crops.
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