CN111670182A - Quinoline derivatives, preparation method and application thereof - Google Patents

Quinoline derivatives, preparation method and application thereof Download PDF

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Publication number
CN111670182A
CN111670182A CN201880087384.1A CN201880087384A CN111670182A CN 111670182 A CN111670182 A CN 111670182A CN 201880087384 A CN201880087384 A CN 201880087384A CN 111670182 A CN111670182 A CN 111670182A
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radical
alkyl
hydrogen
halo
independently
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李义涛
张虎
刘鹏飞
刘倩
林健
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Dongguan Hec Pesticides R&d Co ltd
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Dongguan Hec Pesticides R&d Co ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Abstract

Quinoline derivatives of formula (I) and processes for their preparation, compositions and formulations containing them and their use as herbicides; wherein R is hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, or the like; cy is optionally substituted pyrazolyl, etc.

Description

Quinoline derivatives, preparation method and application thereof Technical Field
The invention provides a new quinoline derivative and a preparation method thereof, a composition containing the compounds and application thereof in agriculture.
Background
WO 9812180, WO 9812192, WO 2000014069, CN 102249996 disclose that quinoline compounds have certain herbicidal activity, however, the compounds of the present invention described in detail hereinafter are not described in these documents.
The active ingredients known from the documents cited above have disadvantages in use, for example, (a) no or only insufficient herbicidal action on the weed plants, (b) too narrow a spectrum of weed plants to be controlled or (c) too low a selectivity in crops of useful plants.
Accordingly, there is a need to provide chemically active ingredients that can be advantageously used as herbicides or plant growth regulators.
Disclosure of Invention
The present invention provides a novel quinoline compound having excellent herbicidal action and excellent selectivity between crops and weeds.
In one aspect, the invention provides a compound of formula (I) or a stereoisomer, a nitroxide or a salt thereof:
Figure PCTCN2018122505-APPB-000001
wherein:
r is hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylaminoalkyl, alkylthioalkyl, haloalkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, arylalkyl, or heteroarylalkyl; r is optionally selected from R by 1,2,3, 4, 5 or 6xSubstituted with the substituent(s);
cy is the following subformula:
Figure PCTCN2018122505-APPB-000002
or
Figure PCTCN2018122505-APPB-000003
R1And R22Each independently hydrogen, -C (═ O) - (CH)2)n-R8、-(CH2)m-C(＝O)-R8a、-C(＝O)-O-R9、-C(＝O)-NR10R11、-S(＝O)2-R12、-S(＝O)2-NR13R14；
n is 0, 1,2 or 3;
m is 1,2 or 3;
wherein R is8、R8a、R9、R10、R11、R12、R13And R14Each independently is hydrogen, alkyl, alkoxyalkyl, aryl, or heteroaryl; r8、R8a、R9、R10、R11、R12、R13And R14Each independently is optionally selected from R by 1,2,3, 4, 5 or 6ySubstituted with the substituent(s);
R2、R3、R4、R5、R6and R7Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, alkoxy, alkylthio, or alkylcarbonyl;
R33is hydrogen, alkyl, alkenyl, alkynyl or cycloalkyl;
R44is hydrogen, cyano, fluorine, chlorine, bromine, iodine, alkyl, alkenyl, alkynyl, alkoxy, alkylthio or cycloalkyl;
Rxand RyEach independently is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-8Alkyl, halo C1-8Alkyl radical, C2-8Alkenyl, halo C2-8Alkenyl radical, C2-8Alkynyl, halo C2-8Alkynyl, C1-8Alkoxy, halo C1-8Alkoxy radical, C1-8Alkylamino radical, C1-8Alkylthio, halo C1-8Alkylamino, halogeno C1-8Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-9Heteroaryl or C1-9A heteroaryloxy group.
In some of these embodiments, the invention provides a compound of formula (IIa) or a stereoisomer, a nitrogen oxide, or a salt thereof, of a compound of formula (IIa):
Figure PCTCN2018122505-APPB-000004
wherein: r1、R2、R3、R4、R5、R6、R7And R has the meaning as described in the present invention.
In some of these embodiments, the present invention provides a compound of formula (IIb) or a stereoisomer, nitroxide, or salt thereof of a compound of formula (IIb):
Figure PCTCN2018122505-APPB-000005
wherein: r22、R33、R44And R has the meaning as described in the present invention.
In still other embodiments, the invention provides a compound of formula (IIIa) or a stereoisomer, nitroxide or salt thereof of a compound of formula (IIIa):
Figure PCTCN2018122505-APPB-000006
wherein: r22、R33And R44Have the meaning as described in the present invention.
In still other embodiments, the invention provides a compound of formula (IIIb) or a stereoisomer, nitroxide, or salt thereof, of a compound of formula (IIIb):
Figure PCTCN2018122505-APPB-000007
wherein: r22、R33And R44Have the meaning as described herein;
Rm、Rn、Rv、Rwand RzEach independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C2-6Alkenyl, halo C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkynyl, C1-6Alkoxy, halo C1-6Alkoxy radical, C1-6Alkylamino radical, C1-6Alkylthio, halo C1-6Alkylamino, halogeno C1-6Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-5Heteroaryl or C1-5A heteroaryloxy group.
In some of these embodiments, R is hydrogen, C1-8Alkyl radical, C2-8Alkenyl radical, C2-8Alkynyl, C1-8Alkoxy radical C1-8Alkyl radical, C1-8Alkylamino radical C1-8Alkyl radical, C1-8Alkylthio group C1-8Alkyl, halo C1-8Alkyl radical, C3-8Cycloalkyl radical, C2-10Heterocyclic group, C6-10Aryl radical, C1-9Heteroaryl group, C3-8Cycloalkyl radical C1-6Alkyl radical, C2-10Heterocyclyl radical C1-6Alkyl radical, C6-10Aryl radical C1-6Alkyl or C1-9Heteroaryl C1-6An alkyl group; r is optionally selected from R by 1,2,3, 4, 5 or 6xSubstituted with the substituent(s); wherein each RxHave the meaning as described in the present invention.
In other embodiments, R is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy radical C1-6Alkyl radical, C1-6Alkylamino radical C1-6Alkyl radical, C1-6Alkylthio group C1-6Alkyl, halo C1-6Alkyl radical, C3-8Cycloalkyl radical, C2-8Heterocyclic group, C6-10Aryl radical, C1-9Heteroaryl group, C3-8Cycloalkyl radical C1-6Alkyl radical, C2-8Heterocyclyl radical C1-6Alkyl radical, C6-10Aryl radical C1-6Alkyl or C1-9Heteroaryl C1-6An alkyl group; r is optionally selected from R by 1,2,3, 4, 5 or 6xSubstituted with the substituent(s); wherein each RxHave the meaning as described in the present invention.
In other embodiments, R is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C1-3Alkoxy radical C1-3Alkyl radical, C1-3Alkylamino radical C1-3Alkyl radical, C1-3Alkylthio group C1-3Alkyl, halo C1-4Alkyl radical, C3-6Cycloalkyl radical, C2-6Heterocyclic group, C6-10Aryl radical, C1-5Heteroaryl group, C3-6Cycloalkyl radical C1-3Alkyl radical, C2-6Heterocyclyl radical C1-4Alkyl radical, C6-10Aryl radical C1-3Alkyl or C1-5Heteroaryl C1-3An alkyl group; r is optionally selected from R by 1,2,3, 4, 5 or 6xSubstituted with the substituent(s); wherein each RxHave the meaning as described in the present invention.
In other embodiments, R is C1-3Alkyl radical, C2-3Alkenyl radical, C2-3Alkynyl, C1-3Alkoxy radical C1-3Alkyl, halo C1-3Alkyl, phenyl or C2-4Heterocyclyl radical C1-3An alkyl group; r is optionally selected from R by 1,2,3, 4, 5 or 6xSubstituted with the substituent(s); wherein each RxHave the meaning as described in the present invention.
In some of these embodiments, each R isxIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C2-6Alkenyl, halo C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkynyl, C1-6Alkoxy, halo C1-6Alkoxy radical, C1-6Alkylamino radical, C1-6Alkylthio, halo C1-6Alkylamino, halogeno C1-6Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-5Heteroaryl or C1-5A heteroaryloxy group.
In other embodiments, each R isxIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl, halo C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkoxy radical, C1-4Alkylamino radical, C1-4Alkylthio, halo C1-4Alkylamino, halogeno C1-4Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-5Heteroaryl or C1-5A heteroaryloxy group.
In other embodiments, each R isxIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, methoxy or trifluoromethoxy.
In still other embodiments, R is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CF3、-CH2CHF2、-CH2CF3、-CH2OCH3、-CH2CH2OCH3or-CH2OCH2CH3(ii) a Or R is the following subformula:
Figure PCTCN2018122505-APPB-000008
in some of these embodiments, R2、R3、R4、R5、R6And R7Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-6Alkyl radical, C1-6Alkoxy radical, C1-6Alkylthio or C1-6An alkylcarbonyl group.
In other embodiments, R2、R3、R4、R5、R6And R7Each independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-4Alkyl radical, C1-4Alkoxy radical, C1-4Alkylthio or C1-4An alkylcarbonyl group.
In other embodiments, R2、R3、R4、R5、R6And R7Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, methyl, ethyl, n-propyl, isopropyl, or methoxy.
In some of these embodiments, R1And R22Each independently hydrogen, -C (═ O) - (CH)2)n-R8、-(CH2)m-C(＝O)-R8a、-C(＝O)-O-R9、-C(＝O)-NR10R11、-S(＝O)2-R12、-S(＝O)2-NR13R14；
n is 0, 1,2 or 3;
m is 1,2 or 3;
wherein R is8、R8a、R9、R10、R11、R12、R13And R14Each independently is hydrogen, C1-6Alkyl radical, C1-6Alkoxy radical C1-6Alkyl radical, C6-10Aryl or C1-9A heteroaryl group; r8、R8a、R9、R10、R11、R12、R13And R14Each independently is optionally selected from R by 1,2,3, 4, 5 or 6ySubstituted with the substituent(s); wherein each RyHave the meaning as described in the present invention.
In some of these embodiments, R33Is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-6A cycloalkyl group.
In some of these embodiments, R44Is hydrogen, cyano, fluorine, chlorine, bromine, iodine, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, alkynyl,C1-6Alkoxy radical, C1-6Alkylthio or C3-6A cycloalkyl group.
In other embodiments, R1And R22Each independently hydrogen, -C (═ O) - (CH)2)n-R8Or- (CH)2)m-C(＝O)-R8a；
n is 0, 1,2 or 3;
m is 1,2 or 3;
wherein R is8And R8aEach independently is hydrogen, C1-4Alkyl radical, C1-4Alkoxy radical C1-4Alkyl, phenyl or C2-3A heteroaryl group; r8And R8aEach independently is optionally selected from R by 1,2,3, 4, 5 or 6ySubstituted with the substituent(s); wherein each RyHave the meaning as described in the present invention.
In other embodiments, R8And R8aEach independently is phenyl or pyrazolyl; r8And R8aEach independently is optionally selected from R by 1,2,3, 4, 5 or 6ySubstituted with the substituent(s); wherein each RyHave the meaning as described in the present invention.
In other embodiments, R33Is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6A cycloalkyl group.
In other embodiments, R44Is hydrogen, cyano, fluorine, chlorine, bromine, iodine, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C1-4Alkoxy radical, C1-4Alkylthio or C3-6A cycloalkyl group.
In some of these embodiments, each R isyIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-6Alkyl, halo C1-6Alkyl radical, C2-6Alkenyl, halo C2-6Alkenyl radical, C2-6Alkynyl, halo C2-6Alkynyl, C1-6Alkoxy, halo C1-6Alkoxy radical, C1-6Alkylamino radical, C1-6Alkylthio, halo C1-6An alkylamino group,Halogen substituted C1-6Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-5Heteroaryl or C1-5A heteroaryloxy group.
In other embodiments, each R isyIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl, halo C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkoxy radical, C1-4Alkylamino radical, C1-4Alkylthio, halo C1-4Alkylamino, halogeno C1-4Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-5Heteroaryl or C1-5A heteroaryloxy group.
In other embodiments, each R isyIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, methoxy or trifluoromethoxy.
In other embodiments, R22Is hydrogen,
Figure PCTCN2018122505-APPB-000009
In other embodiments, R33Hydrogen, methyl, ethyl, n-propyl or isopropyl.
In other embodiments, R44Hydrogen, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl or cyclopropyl.
In other embodiments, Rm、Rn、Rv、RwAnd RzEach independently is hydrogen, fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl, halo C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkoxy radical、C1-4Alkylamino radical, C1-4Alkylthio, halo C1-4Alkylamino, halogeno C1-4Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-5Heteroaryl or C1-5A heteroaryloxy group.
In other embodiments, Rm、Rn、Rv、RwAnd RzEach independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, methoxy, or trifluoromethoxy.
In other embodiments, the invention provides a compound that is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of a compound having one of the following structures:
Figure PCTCN2018122505-APPB-000010
Figure PCTCN2018122505-APPB-000011
Figure PCTCN2018122505-APPB-000012
Figure PCTCN2018122505-APPB-000013
Figure PCTCN2018122505-APPB-000014
or
Figure PCTCN2018122505-APPB-000015
In another aspect, the present invention provides a composition comprising a compound described herein, optionally further comprising at least one adjuvant.
In another aspect, the invention provides the use of a compound or composition according to the invention in agriculture.
In some of these embodiments, the present invention provides the use of a compound or composition described herein for controlling unwanted vegetation.
In some of these embodiments, the present invention provides the use of a compound or composition described herein as a herbicide.
In another aspect, the present invention provides a method for controlling unwanted vegetation, characterized in that an effective amount of a compound according to the invention is applied to the plants, to the plant seeds, to the soil in or on which the plants are grown, or to the cultivation area.
The compound provided by the invention is a novel compound which is more effective to weeds, lower in cost, lower in toxicity and safe to environment.
The compounds of formula (I), formula (IIa), formula (IIb), formula (IIIa) or formula (IIIb) may exist in different stereoisomeric or optical isomeric or tautomeric forms. The invention encompasses all such isomers and tautomers and mixtures thereof in various ratios, as well as isotopic forms such as heavy hydrogen-containing compounds.
Isotopically enriched compounds have the structure depicted by the formulae given herein, except that one or more atoms are replaced by an atom having a selected atomic mass or mass number. Exemplary isotopes that can be incorporated into compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine and chlorine, such as2H，3H，11C，13C，14C，15N，17O，18O，18F，31P，32P，35S，36Cl and125I。
any asymmetric atom (e.g., carbon, etc.) of a compound disclosed herein can exist in racemic or enantiomerically enriched forms, such as the (R) -, (S) -or (R, S) -configuration.
The foregoing has outlined only certain aspects of the present invention and is not intended to be limited in these or other respects to the details described herein.
Detailed description of the invention
Definitions and general terms
Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated by the accompanying structural and chemical formulas. The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. One skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.
It will be further appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety.
The following definitions, as used herein, should be applied unless otherwise indicated. For the purposes of the present invention, the chemical elements are in accordance with the CAS version of the periodic Table of the elements, and the handbook of chemistry and Physics, 75 th edition, 1994. In addition, general principles of Organic Chemistry can be referred to as described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry" by Michael B.Smith and Jerry March, John Wiley & Sons, New York:2007, the entire contents of which are incorporated herein by reference.
The articles "a," "an," and "the" as used herein are intended to include "at least one" or "one or more" unless otherwise indicated or clearly contradicted by context. Thus, as used herein, the articles refer to articles of one or more than one (i.e., at least one) object. For example, "a component" refers to one or more components, i.e., there may be more than one component contemplated for use or use in embodiments of the described embodiments.
The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.
"stereoisomers" refers to compounds having the same chemical structure but differing in the arrangement of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"enantiomer" refers to two isomers of a compound that are not overlapping but are in mirror image relationship to each other.
"diastereomer" refers to a stereoisomer that has two or more chiral neutrals and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting points, boiling points, spectral properties, and reactivities. Mixtures of diastereomers may be separated by high resolution analytical procedures such as electrophoresis and chromatography, for example, by HPLC.
The stereochemical definitions and rules used in the present invention generally follow the general definitions of S.P. Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; stereochemical definitions and rules as described in and Eliel, e.and Wilen, s, "Stereochemistry of Organic Compounds", John Wiley & Sons, inc, New York, 1994.
Many organic compounds exist in an optically active form, i.e., they have the ability to rotate the plane of plane polarized light. In describing optically active compounds, the prefixes D and L or R and S are used to denote the absolute configuration of a molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are the symbols used to specify the rotation of plane polarized light by the compound, where (-) or l indicates that the compound is left-handed. Compounds prefixed with (+) or d are dextrorotatory. A particular stereoisomer is an enantiomer and a mixture of such isomers is referred to as an enantiomeric mixture. A50: 50 mixture of enantiomers is referred to as a racemic mixture or racemate, which may occur when there is no stereoselectivity or stereospecificity in the chemical reaction or process.
The compounds of the invention may be optionally substituted with one or more substituents, as described herein, in compounds of the general formula above, or as specifically exemplified, sub-classes, and classes of compounds encompassed by the invention. It is understood that the term "optionally substituted" may be used interchangeably with the term "substituted or unsubstituted". In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced with a particular substituent. Unless otherwise indicated, an optional substituent group may be substituted at each substitutable position of the group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position, identically or differently. Wherein said substituent may be, but is not limited to, deuterium, fluorine, chlorine, bromine, iodine, cyano, hydroxyl, nitro, amino, carboxyl, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkoxyalkylamino, aryloxy, heteroaryloxy, heterocyclyloxy, arylalkoxy, heteroarylalkoxy, heterocyclylalkoxy, cycloalkylalkoxy, alkylamino, alkylaminoalkyl, alkylaminoalkylamino, cycloalkylamino, cycloalkylalkylamino, alkylthio, haloalkyl, haloalkoxy, hydroxyl-substituted alkyl, hydroxyl-substituted alkylamino, cyano-substituted alkyl, cyano-substituted alkoxy, cyano-substituted alkylamino, amino-substituted alkyl, alkanoyl, heteroalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, heterocyclyl, heterocyclylalkyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.
In addition, unless otherwise explicitly indicated, the descriptions of the terms "… independently" and "… independently" and "… independently" used in the present invention are interchangeable and should be understood in a broad sense to mean that the specific items expressed between the same symbols do not affect each other in different groups or that the specific items expressed between the same symbols in the same groups do not affect each other.
In the various parts of this specification, substituents of the disclosed compounds are disclosed in terms of group type or range. It is specifically intended that the invention includes each and every independent subcombination of the various members of these groups and ranges. For example, the term "C1-C6Alkyl "or" C1-6Alkyl "means in particular independently disclosed methyl, ethyl, C3Alkyl radical, C4Alkyl radical, C5Alkyl and C6An alkyl group.
The term "alkyl" or "alkyl group" as used herein, denotes a saturated, straight or branched chain, monovalent hydrocarbon group containing from 1 to 20 carbon atoms; wherein the alkyl group is optionally substituted with one or more substituents described herein. Unless otherwise specified, alkyl groups contain 1-20 carbon atoms. In one embodiment, the alkyl group contains 1 to 12 carbon atoms; in one embodiment, the alkyl group contains 1 to 10 carbon atoms; in one embodiment, the alkyl group contains 1 to 8 carbon atoms; in another embodiment, the alkyl group contains 1 to 6 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 4 carbon atoms; in yet another embodiment, the alkyl group contains 1 to 3 carbon atoms.
Examples of alkyl groups include, but are not limited to, methyl (Me, -CH)3) Ethyl group (Et, -CH)2CH3) N-propyl (n-Pr, -CH)2CH2CH3) Isopropyl group (i-Pr, -CH (CH)3)2) N-butyl (n-Bu, -CH)2CH2CH2CH3) Isobutyl (i-Bu, -CH)2CH(CH3)2) Sec-butyl (s-Bu, -CH (CH)3)CH2CH3) Tert-butyl (t-Bu, -C (CH)3)3) N-pentyl (-CH)2CH2CH2CH2CH3) 2-pentyl (-CH (CH)3)CH2CH2CH3) 3-pentyl (-CH (CH)2CH3)2) 2-methyl-2-butyl (-C (CH)3)2CH2CH3) 3-methyl-2-butyl (-CH (CH)3)CH(CH3)2) 3-methyl-1-butyl (-CH)2CH2CH(CH3)2) 2-methyl-1-butyl (-CH)2CH(CH3)CH2CH3) N-hexyl (-CH)2CH2CH2CH2CH2CH3) 2-hexyl (-CH (CH)3)CH2CH2CH2CH3) 3-hexyl (-CH (CH)2CH3)(CH2CH2CH3) 2-methyl-2-pentyl (-C (CH))3)2CH2CH2CH3) 3-methyl-2-pentyl (-CH (CH)3)CH(CH3)CH2CH3) 4-methyl-2-pentyl (-CH (CH)3)CH2CH(CH3)2) 3-methyl-3-pentyl (-C (CH)3)(CH2CH3)2) 2-methyl-3-pentyl (-CH (CH)2CH3)CH(CH3)2) 2, 3-dimethyl-2-butyl (-C (CH)3)2CH(CH3)2) 3, 3-dimethyl-2-butyl (-CH (CH)3)C(CH3)3) N-heptyl, n-octyl, and the like.
The term "alkenyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one site of unsaturation, i.e. one carbon-carbon sp 2A double bond, wherein said alkenyl group may be optionally substituted with one or more substituents described herein, including the positioning of "cis" and "tans", or "E" and "And Z' is positioned. In one embodiment, the alkenyl group contains 2 to 10 carbon atoms; in one embodiment, the alkenyl group contains 2 to 8 carbon atoms; in another embodiment, the alkenyl group contains 2 to 6 carbon atoms; in yet another embodiment, the alkenyl group contains 2 to 4 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl (-CH ═ CH)2) Allyl (-CH)2CH＝CH2) Allyl (CH)3-CH＝CH-)，-CH2CH2CH＝CH2、-CH2CH＝CHCH3、-CH2CH2CH2CH＝CH2、-CH2CH2CH＝CHCH3、-CH2CH2CH2CH＝CHCH3And so on.
The term "alkynyl" denotes a straight or branched chain monovalent hydrocarbon radical containing 2 to 12 carbon atoms, wherein there is at least one carbon-carbon sp triple bond, wherein the alkynyl radical may be optionally substituted with one or more substituents as described herein. In one embodiment, alkynyl groups contain 2-10 carbon atoms; in one embodiment, alkynyl groups contain 2-8 carbon atoms; in another embodiment, alkynyl groups contain 2-6 carbon atoms; in yet another embodiment, alkynyl groups contain 2-4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C.ident.CH, -C.ident.CCH3、-CH2-C≡CH、-CH2-C≡CCH3、-CH2CH2-C≡CH、-CH2-C≡CCH2CH3、-CH2CH2-C≡CH2CH3And so on.
The term "alkoxy" means an alkyl group attached to the rest of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy group contains 1 to 12 carbon atoms. In one embodiment, the alkoxy group contains 1 to 10 carbon atoms; in one embodiment, the alkoxy group contains 1 to 8 carbon atoms; in one embodiment, the alkoxy group contains 1 to 6 carbon atoms; in another embodiment, the alkoxy group contains 1 to 4 carbon atoms; in yet another embodiment, the alkoxy group contains 1 to 3 carbon atoms. The alkoxy group may be optionally substituted with one or more substituents described herein.
Examples of alkoxy groups include, but are not limited to, methoxy (MeO, -OCH)3) Ethoxy (EtO, -OCH)2CH3) 1-propoxy (n-PrO, n-propoxy, -OCH)2CH2CH3) 2-propoxy (i-PrO, i-propoxy, -OCH (CH)3)2) 1-butoxy (n-BuO, n-butoxy, -OCH)2CH2CH2CH3) 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH)2CH(CH3)2) 2-butoxy (s-BuO, s-butoxy, -OCH (CH)3)CH2CH3) 2-methyl-2-propoxy (t-BuO, t-butoxy, -OC (CH)3)3) 1-pentyloxy (n-pentyloxy, -OCH)2CH2CH2CH2CH3) 2-pentyloxy (-OCH (CH)3)CH2CH2CH3) 3-pentyloxy (-OCH (CH))2CH3)2) 2-methyl-2-butoxy (-OC (CH))3)2CH2CH3) 3-methyl-2-butoxy (-OCH (CH)3)CH(CH3)2) 3-methyl-l-butoxy (-OCH)2CH2CH(CH3)2) 2-methyl-l-butoxy (-OCH)2CH(CH3)CH2CH3) And so on.
The term "alkylamino" or "alkylamino" includes "N-alkylamino" and "N, N-dialkylamino" in which the amino groups are each independently substituted with one or two alkyl groups. In some of these embodiments, the alkylamino group is one or two C1-6Lower alkylamino groups in which the alkyl group is attached to the nitrogen atom. In other embodiments, the alkylamino group is C1-3Lower alkylamino groups of (a). Suitable alkylamino groups can be monoalkylamino or dialkylamino, and such examples include, but are not limited to, N-methylamino, N-ethylamino, N-dimethylamino, N-diethylamino, and the like.
The term "alkylthio" refers to a straight or branched chain alkyl group attached to a divalent sulfur atom, wherein the alkyl group has the meaning as described herein. Examples of alkylthio groups include, but are not limited to, -SCH3、-SCH2CH3、-SCH2CH2CH3And so on.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "haloalkyl" denotes an alkyl group substituted with one or more halogen atoms. Examples of haloalkyl include, but are not limited to, -CH2F，-CHF2，-CH2Cl，-CH2Br，-CF3，-CH2CF3，-CH2CH2F，-CH2CH2Cl，-CH2CH2Br，-CH2CHF2，-CH2CH2CF3，-CH2CH2CH2F，-CH2CH2CH2Cl，-CH2CH2CH2Br，-CHFCH2CH3，-CHClCH2CH3And so on.
The term "haloalkenyl" denotes an alkenyl group substituted with one or more halogen atoms.
The term "haloalkynyl" denotes an alkynyl group substituted by one or more halogen atoms.
The term "haloalkoxy" denotes an alkoxy group substituted with one or more halogen atoms. Examples of haloalkoxy include, but are not limited to, -OCH2F，-OCHF2，-OCH2Cl，-OCH2Br，-OCF3，-OCH2CF3，-OCH2CH2F，-OCH2CH2Cl，-OCH2CH2Br，-OCH2CHF2，-OCH2CH2CF3，-OCH2CH2CH2F，-OCH2CH2CH2Cl，-OCH2CH2CH2Br，-OCHFCH2CH3，-OCHClCH2CH3And so on.
The term "haloalkylamino" denotes an alkylamino group substituted with one or more halogen atoms.
The term "haloalkylthio" denotes an alkylthio group substituted by one or more halogen atoms.
The term "alkoxyalkyl" denotes an alkyl group substituted by one or more alkoxy groups, wherein alkyl groups and alkoxy groups have the meaning as described herein. Examples of alkoxyalkyl groups include, but are not limited to, -CH2OCH3、-CH2CH2OCH3、-CH2OCH2CH3or-CH2CH2OCH2CH3。
The term "alkylaminoalkyl" denotes an alkyl group substituted with one or more alkylamino groups, wherein alkyl and alkylamino groups have the meaning as described herein.
The term "alkylthioalkyl" means that the alkyl group is substituted with one or more alkylthio groups, wherein the alkyl group and the alkylthio group have the meaning as described herein.
The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing from 3 to 15 carbon atoms. In one embodiment, the cycloalkyl group contains 3 to 12 carbon atoms; in one embodiment, the cycloalkyl group contains 3 to 10 carbon atoms; in another embodiment, cycloalkyl contains 3 to 8 carbon atoms; in yet another embodiment, the cycloalkyl group contains 3 to 6 carbon atoms. The cycloalkyl group is optionally substituted with one or more substituents described herein. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, adamantyl, and the like.
The term "cycloalkylalkyl" denotes an alkyl group substituted by a cycloalkyl group, wherein the alkyl group and the cycloalkyl group have the meaning as described herein.
The terms "heterocyclyl" and "heterocycle" are used interchangeably herein and are bothRefers to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3 to 15 ring atoms, wherein no aromatic ring is contained in the monocyclic, bicyclic or tricyclic ring, and at least one ring atom is selected from nitrogen, sulfur and oxygen atoms. Unless otherwise specified, heterocyclyl may be carbon-or nitrogen-based, and-CH2-the group may optionally be replaced by-C (═ O) -. The sulfur atom of the ring may optionally be oxidized to the S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxygen compound. Examples of heterocyclyl groups include, but are not limited to, oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl (e.g., 2-pyrrolidinyl), 2-pyrrolinyl, 3-pyrrolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, 1, 3-dioxocyclopentyl, dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl, 3-piperidinyl, 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo) -thiomorpholinyl, (1, 1-dioxo) -thiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thioxanyl, homopiperazinyl, homopiperidinyl, oxepanyl, thiepanyl, 2-oxa-5-azabicyclo [2.2.1]Hept-5-yl, tetrahydropyridinyl. In heterocyclic radicals of-CH2Examples of-groups substituted by-C (═ O) -include, but are not limited to, 2-oxopyrrolidinyl, oxo-1, 3-thiazolidinyl, 2-piperidinonyl, 3, 5-dioxopiperidinyl. Examples of sulfur atoms in heterocyclic groups that are oxidized include, but are not limited to, sulfolane, 1, 1-dioxothiomorpholinyl. The heterocyclyl group is optionally substituted with one or more substituents described herein.
The term "heterocyclylalkyl" refers to a heterocyclyl-substituted alkyl group; wherein heterocyclyl and alkyl groups have the meaning as indicated in the present invention.
The term "ring of x atoms", where x is an integer, typically describes the number of ring-forming atoms in a molecule in which the number of ring-forming atoms is x. For example, piperidinyl is a heterocyclic group consisting of 6 atoms.
The term "unsaturated" as used herein means that the group contains one or more unsaturations.
The term "heteroatom" refers to O, S, N, P and Si, including N, S and any oxidation state form of P; primary, secondary, tertiary amines and quaternary ammonium salt forms; or a form in which a hydrogen on a nitrogen atom in the heterocycle is substituted, for example, N (like N in 3, 4-dihydro-2H-pyrrolyl), NH (like NH in pyrrolidinyl) or NR (like NR in N-substituted pyrrolidinyl).
The term "aryl" denotes monocyclic, bicyclic and tricyclic carbon ring systems containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring system is aromatic, wherein each ring system comprises a ring of 3 to 7 atoms with one or more attachment points to the rest of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of the aryl group may include phenyl, indenyl, naphthyl and anthryl. The aryl group is optionally substituted with one or more substituents described herein.
The term "arylalkyl" or "aralkyl" means that an alkyl group is substituted with one or more aryl groups, wherein the alkyl and aryl groups have the meanings as described herein. Examples of arylalkyl groups can include phenylmethyl (i.e., benzyl), phenylethyl, and the like.
The term "aryloxy" or "aryloxy" includes optionally substituted aryl groups, as defined herein, attached to and linked from an oxygen atom to the rest of the molecule, wherein the aryl group has the meaning as described herein.
The term "heteroaryl" denotes monocyclic, bicyclic and tricyclic ring systems containing 5 to 12 ring atoms, or 5 to 10 ring atoms, or 5 to 6 ring atoms, wherein at least one ring system is aromatic and at least one ring system contains one or more heteroatoms, wherein each ring system contains a ring of 5 to 7 atoms with one or more attachment points to the rest of the molecule. The term "heteroaryl" may be used interchangeably with the terms "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein.
In one embodiment, a heteroaryl group of 5-10 atoms contains 1,2,3, or 4 heteroatoms independently selected from O, S, and N.
In another embodiment, the ring atoms of the heteroaryl group comprise 1 to 9 carbon atoms and 1 to 4 heteroatoms selected from N, O or S; in another embodiment, the ring atoms of the heteroaryl group comprise 1 to 5 carbon atoms and 1 to 4 heteroatoms selected from N, O or S.
In yet another embodiment, heteroaryl represents a 5-or 6-membered heteroaryl group containing 1-4N heteroatoms; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group containing 1-3 heteroatoms selected from N, O or S; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group containing 1-3 heteroatoms selected from N or O; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl group containing 1-3 heteroatoms selected from N or S.
Examples of heteroaryl groups include, but are not limited to, 2-furyl, 3-furyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyridazinyl (e.g., 3-pyridazinyl), 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, tetrazolyl (e.g., 5-tetrazolyl), triazolyl (e.g., 2-triazolyl and 5-triazolyl), 2-thienyl, 3-thienyl, pyrazolyl, isothiazolyl, 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 3-triazolyl, 1,2, 3-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, pyrazinyl, 1,3, 5-triazinyl, pyrimidinonyl, pyridonyl; the following bicyclic rings are also included, but are in no way limited to these: benzimidazolyl, benzofuranyl, benzotetrahydrofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), and the like.
The term "heteroarylalkyl" means that an alkyl group is substituted with one or more heteroaryl groups, wherein the alkyl group and heteroaryl groups have the meaning as set forth herein.
The term "heteroaryloxy" or "heteroaryloxy" includes optionally substituted heteroaryl groups, as defined herein, attached to and linked by an oxygen atom to the rest of the molecule, wherein the heteroaryl group has the meaning as set forth herein.
When the compounds of the present invention contain an acid moiety, salts of the compounds of the present invention include those derived from alkali or alkaline earth metals as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and those of formula N+(RaRbRcRd) Ammonium cation of (2), wherein R isa、Rb、RcAnd RdIndependently selected from hydrogen, C1-C6Alkyl and C1-C6A hydroxyalkyl group. Salts of the compound of formula (I) can be prepared by treating the compound of formula (I) with a metal hydroxide (e.g., sodium hydroxide) or an amine (e.g., ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine).
When a compound of the invention comprises a base moiety, acceptable salts can be formed from organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, napthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids.
Compositions and formulations of the compounds of the invention
The compounds of the present invention are generally useful as herbicidal active ingredients in compositions or formulations further comprising at least one adjuvant selected from the group consisting of surfactants, solid diluents and liquid diluents. The formulation or composition ingredients are selected to be compatible with the physical characteristics of the active ingredient, the mode of application, and environmental factors such as soil type, moisture and temperature.
Useful formulations include liquid compositions and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions), and the like, which may optionally be thickened into gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspoemulsions. Common types of non-aqueous liquid compositions are emulsifiable concentrates, microemulsifiable concentrates, dispersible concentrates and oil dispersions.
The general types of solid compositions are powders, granules, pellets, prills, lozenges, tablets, filled films (including seed coatings), and the like, which may be water dispersible ("wettable") or water soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. The active ingredient may be (micro) encapsulated and further formed into a suspension or solid formulation; alternatively, the entire active ingredient formulation may be encapsulated (or "coated"). Encapsulation may control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granular formulations. The high concentration compositions are mainly used as intermediates for other formulations.
Sprayable formulations are typically dispersed in a suitable medium prior to spraying. Such liquid and solid formulations are formulated to be readily diluted in a spray medium, typically water. The spray volume may be in the range of about one to several thousand liters per hectare, but more typically in the range of about ten to several hundred liters per hectare. The sprayable formulation may be mixed with water or another suitable medium in a water tank for treatment of the foliage by air or ground application, or applied to the growing medium of the plant. The liquid and dry formulations can be dosed directly into the drip irrigation system or into the furrow during planting.
The formulation will typically comprise effective amounts of active ingredient, diluent and surfactant, the sum being 100% by weight.
Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starches, dextrins, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate and sodium sulfate. Typical solid Diluents are described in Handbook of Instrument Dust Diluents and Cariers, 2 nd edition, Dorland Books, Caldwell, N.J. by Watkins et al.
Liquid diluents include, for example, water, N-dimethyl alkanamides (e.g., N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, N-paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones (e.g., cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone), acetates (e.g., isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate, and isobornyl acetate), Other esters (such as alkylated lactates, dibasic esters and gamma-butyrolactones) and may be straight chain, branched chain, saturated or unsaturated alcohols (such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecanol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol). Liquid diluents also include saturated and unsaturated fatty acids (typically C)6-C22) Such as vegetable seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grapeseed oil, safflower oil, cottonseed oil, soybean oil, rapeseed oil, coconut oil, and palm kernel oil), animal-derived fats (e.g., tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, which can be obtained by hydrolysis of vegetable and animal derived glycerides and can be purified by distillation. Typical liquid diluents are described in Marsden's Solvents Guide, 2 nd edition, Interscience, New York, 1950.
The solid and liquid compositions of the present invention typically comprise one or more surfactants. Surfactants (also known as "surface active agents") generally change when added to a liquid, most often lowering the surface tension of the liquid. Surfactants can be used as wetting agents, dispersing agents, emulsifying agents, or defoaming agents, depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule.
Surfactants can be classified as nonionic, anionic, or cationic surfactants. Nonionic surfactants useful as compositions of the present invention include, but are not limited to: alcohol alkoxylates, such as alcohol alkoxylates based on natural and synthetic alcohols (which are branched or linear) and prepared from alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylation, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean, castor and rapeseed oil; alkylphenol alkoxylates such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers, wherein the end blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenols (including those prepared from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); fatty acid esters, glycerides, lanolin-based derivatives, polyethoxylated esters, such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters, and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives, such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd PEG (polyethylene glycol) resins, graft or comb polymers, and star polymers; polyethylene glycol (PEG); polyethylene glycol fatty acid esters; a silicone-based surfactant; and sugar derivatives such as sucrose esters, alkyl polyglucosides, and alkyl polysaccharides.
Useful anionic surfactants include, but are not limited to: alkyl aryl sulfonic acids and their salts; carboxylated alcohols or alkylphenol ethoxylates; a diphenyl sulfonate derivative; lignin and lignin derivatives, such as lignosulfonates; maleic or succinic acid or anhydrides thereof; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; a protein-based surfactant; a sarcosine derivative; styrylphenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; amine and amide sulfonates, such as N, N-alkyl taurates; benzene, cumene, toluene, xylene, and sulfonates of dodecylbenzene and tridecylbenzene; a sulfonate of condensed polynaphthalene; sulfonates of naphthalene and alkylnaphthalenes; sulfonates of petroleum fractions; sulfosuccinamates; and sulfosuccinates and their derivatives, such as dialkyl sulfosuccinates.
Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propylene diamine, tripropylene triamine and dipropylene tetramine, and ethoxylated, ethoxylated and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts, such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxide and bis- (2-hydroxyethyl) -alkylamine oxide.
Also useful in the compositions of the present invention are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their proposed uses are disclosed in a number of published references, including McCutcheon's Emulsifiers and Detergents, north american and international yearbook versions, published by McCutcheon's Division, The Manufacturing conditioner Publishing co; the Encyclopdia of Surface Active Agents by Sisely and Wood, Chemical Publ.Co., Inc., New York, 1964; and Synthetic Detergents, seventh edition, John Wiley and Sons, New York, 1987, by a.s.davidson and b.milwidsky.
The compositions of the present invention may also contain formulation adjuvants and additives known to those skilled in the art as co-formulations (some of which may also be considered to act as solid diluents, liquid diluents or surfactants). Such formulation aids and additives may control: pH (buffer), foaming during processing (antifoam such as polyorganosiloxane), sedimentation of the active ingredient (suspending agent), viscosity (thixotropic thickener), microbial growth in the container (biocide), product freezing (antifreeze), color (dye/pigment dispersion), elution (film former or binder), evaporation (anti-evaporation agent), and other formulation attributes. Film formers include, for example, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymers, polyvinyl alcohol copolymers, and waxes. Examples of formulation aids and additives include McCutcheon's Volume 2 published by McCutcheon's Division, The Manufacturing conditioner Publishing co: functional Materials, north american and international yearbook versions; and those listed in PCT publication WO 03/024222.
The compounds of the present invention and any other active ingredients are typically incorporated into the compositions of the present invention by dissolving the active ingredient in a solvent or by grinding the active ingredient in a liquid diluent or a dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of the liquid composition used as an emulsifiable concentrate is water-immiscible, an emulsifier is usually added to emulsify the solvent containing the active ingredient upon dilution with water. A media mill may be used to wet grind an active ingredient slurry having a particle size of up to 2,000 μm to obtain particles having an average diameter of less than 3 μm. The aqueous slurry can be prepared as a finished suspension concentrate (see, e.g., U.S.3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations typically require a dry milling step, which results in an average particle size in the range of 2 to 10 μm. Powders and dusts can be prepared by mixing, and usually by grinding (e.g., with a hammer mill or fluid energy mill). Particles and granules can be prepared by spraying the active substance onto preformed particle carriers or by agglomeration techniques. See Browning "agglomerization" (Chemical Engineering, 12.4.1967, pages 147-48; Perry's Chemical Engineering' Handbook, 4 th edition, McGraw-Hill, New York, 1963, pages 8-57 and later and WO 91/13546. the pellets can be prepared as described in u.s.4,172,714. the water dispersible and water soluble particles can be prepared as set forth in u.s.4,144,050, u.s.3,920,442 and de.3,246,493. the tablets can be prepared as set forth in u.s.5,180,587, u.s.5,232,701 and u.s.5,208,030. the films can be prepared as set forth in GB2,095,558 and u.s.3,299,566.
For additional information regarding The field of formulation, see "The formulations's Toolbox-Product Forms for model Agriculture" by T.S. woods, The Food-Environment Challenge, T.Brooks and T.R. Roberts eds, Proceedings of The 9th International conformation on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, p.120. 133. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S. Pat. No. 3,309,192, column 5, column 43 to column 7, column 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138, 162, 164, 166, 167 and 169, 182; U.S.2,891,855 at column 3, line 66 to column 5, line 17 and examples 1-4; wed Control as a Science by Klingman, John Wiley and Sons, Inc., New York, 1961, pages 81-96; weed Control Handbook, 8 th edition, Blackwell Scientific Publications, Oxford, 1989, by Hance et al; and Developments in simulation technology, PJB Publications, Richmond, UK, 2000.
Use of the Compounds of the invention
The herbicides of the present invention can be used by spraying plants, applying to soil, applying to the surface of water. The amount of the active ingredient is appropriately determined to meet the purpose of use. The content of the active ingredient is appropriately determined depending on the purpose.
The amount of the compound of the present invention to be used is determined depending on the kind of the compound to be used, the target weed, the tendency of weed to appear, environmental conditions, the kind of herbicide, and the like. When the herbicides of the invention are used as such, for example in the form of powders or granules, the amount is suitably selected to be from 1g to 50kg per 1 hectare of active ingredient, preferably from 10g to 10kg per 1 hectare. When the herbicide of the present invention is used in a liquid form, for example, in the form of an emulsifiable concentrate, a wettable powder or a flowable formulation, the amount thereof is suitably selected from 0.1 to 50,000ppm, preferably from 10 to 10,000 ppm.
The present invention provides a method for controlling weeds in a crop of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful plants or to the locus of said useful plants, a compound or composition of the invention.
The invention also provides a method of selectively controlling grasses and/or weeds in crops of useful plants, which comprises applying to the useful plants or to the locus thereof or to the area of cultivation a herbicidally effective amount of a compound of formula (I), formula (IIa), formula (IIb), formula (IIIa) or formula (IIIb).
The term "herbicide" means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means the amount of such a compound or combination of such compounds that is capable of producing a control or modification of the growth of plants. The effects of control or modification include all deviations from natural development, e.g., kills, delays, leaf burns, albinism, dwarfing, etc. The term "plant" refers to all tangible parts of a plant, including seeds, seedlings, plantlets, roots, tubers, stems, stalks, leaves, and fruits. The term "locus" is intended to include soil, seeds and seedlings, as well as established plants (grassed habitat) and includes not only areas where weeds may have grown, but also areas where weeds have not yet emerged, and also areas for the planting of crops of useful plants. "planted area" includes the land on which crop plants have grown, as well as the land intended for planting such crop plants. The term "weeds" as used herein means any undesirable vegetation and thus includes not only important agronomic weeds as described below, but also volunteer crop plants.
Crops of useful plants in which the compositions according to the invention may be used include, but are not limited to, perennial crops such as citrus fruits, grapevines, nuts, oil palms, olives, pome fruits, stone fruits and rubber, and annual arable crops such as cereals (such as barley and wheat), cotton, oilseed rape, maize, rice, soya, sugar beet, sugar cane, sunflowers, ornamentals, switchgrass, turf and vegetables, especially cereals, maize and soya.
The grasses and weeds to be controlled can be both monocotyledonous species, such as agrostis, alopecurus, avena, brachiaria, bromus, tribulus, cyperus, digitaria, barnyard grass, kojima, lolium, monocrotonia, panicum, poa, cylindron, arrowhead, scirpus, setaria, sida and sorghum, and dicotyledonous species, such as kenaf, amaranthus, chenopodium, chrysanthemum, euphorbia, labra, ipomoea, kochia, eclipta, polygonum, rhodomyrtus, sinapis, solanum, chickweed, veronica, viola and xanthium.
The compounds of the invention may show tolerance to important crops including, but not limited to, alfalfa, barley, cotton, wheat, canola, sugar beet, corn (maize), sorghum, soybean, rice, oats, peanut, vegetables, tomato, potato, perennial crop plants including coffee, cocoa, oil palm, rubber, sugar cane, citrus, grapes, fruit trees, nut trees, bananas, plantains, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf varieties (e.g., prairie grass, san augustine grass (st. augustine grass), Kentucky hair and bermudagrass).
If desired, the compounds of the formula (I), formula (IIa), formula (IIb), formula (IIIa) or formula (IIIb) according to the invention can also be used in combination with other active ingredients, for example other herbicides and/or insecticides and/or acaricides and/or nematicides and/or molluscicides and/or fungicides and/or plant growth regulators. These mixtures, and the use of these mixtures for controlling the growth of weeds and/or undesired vegetation, form yet further aspects of the invention. For the avoidance of doubt, mixtures of the invention also include mixtures of two or more different compounds of formula (I), formula (IIa), formula (IIb), formula (IIIa) or formula (IIIb). In particular, the invention also relates to a composition according to the invention which, in addition to the compound of formula (I), formula (IIa), formula (IIb), formula (IIIa) or formula (IIIb), comprises at least one further herbicide.
General synthetic procedure
In this specification, a structure is dominant if there is any difference between the chemical name and the chemical structure. In general, the compounds of the invention may be prepared by the methods described herein, unless otherwise indicated. The starting materials, reagents and the like used in the preparation of the compounds of the present invention are commercially available or can be prepared by methods conventional in the art.
The test conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: brookfield (Bruker) nuclear magnetic instrument at 400MHz or 600MHz in CDC1 at room temperature3，d6-DMSO，CD3OD or d6Acetone as solvent (reported in ppm) with TMS (0ppm) or chloroform (7.26ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (singleton), d (doublet), t (triplet), q (quatet, quartet), m (multiplet ), br (broadpeded, broad), dd (doublet of doublets), dt (doublet of triplets). Coupling constants are expressed in hertz (Hz).
The mass spectrometry method used in the invention comprises the following steps: the conditions for low resolution Mass Spectrometry (MS) data determination were: agilent 6120Quadrupole HPLC-MS (column model: Zorbax SB-C18,2.1X 30mm,3.5 μm,6min, flow rate 0.6mL/min, mobile phase 5% -95% (CH with 0.1% formic acid)3CN) in (containing 0.1% formic acid)H of (A) to (B)2Proportion in O)), at 210/254nm with UV detection, using electrospray ionization mode (ESI).
The following abbreviations are used throughout the present invention:
DCM: methylene dichloride
DMF: n, N-dimethylformamide, dimethylformamide
Et3N: triethylamine
THF: tetrahydrofuran (THF)
NaH: sodium hydride
NaHCO3: sodium bicarbonate
TLC: thin Layer Chromatography, Thin Layer Chromatography
The following synthetic schemes and examples serve to further illustrate the context of the invention.
Synthesis scheme I
Figure PCTCN2018122505-APPB-000016
The compounds E can be prepared by the first synthesis scheme, wherein R has the meaning as described in the present invention. 4-chloroquinoline-6-carboxylic acid methyl ester and alcohol R-OH are subjected to nucleophilic substitution reaction at the temperature of 80-150 ℃ under the alkaline condition (such as sodium hydride, potassium carbonate, triethylamine, pyridine and the like) to obtain a compound A; hydrolyzing the compound A under alkaline condition (such as lithium hydroxide, potassium hydroxide, sodium hydroxide, etc.) to obtain a compound B; performing halogenation reaction on the compound B and thionyl chloride at the temperature of 60-100 ℃ to obtain a compound C; carrying out esterification reaction on the compound C and 1,3 cyclohexanedione at 0-35 ℃ to obtain a compound D; the compound D and trimethylsilyl cyanide undergo Fries rearrangement reaction at 10-40 ℃ to obtain a target compound E.
Synthesis scheme two
Figure PCTCN2018122505-APPB-000017
Compound G can be prepared by synthesis scheme two, wherein R, R33And R44Have the meaning as described in the present invention. Carrying out esterification reaction on the compound C and optionally substituted hydroxypyrazole at 0-35 ℃ to obtain a compound F; the compound F and trimethylsilyl cyanide undergo Fries rearrangement reaction at 10-40 ℃ to obtain a target compound G.
Synthesis scheme three
Figure PCTCN2018122505-APPB-000018
Compound (IIb') can be prepared by synthesis scheme three, wherein X is halogen; r22' is-C (═ O) - (CH)2)n-R8Or- (CH)2)m-C(＝O)-R8a；R、R33、R44、n、m、R8And R8aHave the meaning as described in the present invention. Compound G and compound R22' -X under alkaline conditions (e.g., Cs)2CO3、K2CO3Etc.) to perform nucleophilic substitution reaction at 25-50 ℃ to obtain the target compound (IIb').
Examples
Example 12- ((4- (4- (2, 2-Difluoroethoxy) quinoline-6-carbonyl) -1, 3-dimethyl-1H-pyrazol-5-yl) oxy) -1-acetophenone
Figure PCTCN2018122505-APPB-000019
Step 1: synthesis of methyl 4- (((4, 4-dimethyl-2, 6-dioxocyclohexylidene) methyl) amino) benzoate
Figure PCTCN2018122505-APPB-000020
Methyl p-aminobenzoate (500mg,3.3mmol), Meldrum's acid (572mg,3.97mmol) and absolute ethanol (10mL) were added in sequence to a single-neck flask, then triethyl orthoformate (586mg,3.97mmol) was slowly added dropwise, the temperature was slowly raised to 78 ℃ and reaction was carried out for 2h, a large amount of white solid precipitated. TLC monitored the reaction complete and stopped the reaction. Cooling to room temperature, suction filtering, washing the filter cake with cooled ethanol, and drying to obtain 990mg of white solid with yield of 98%.
Step 2: synthesis of methyl 4-oxo-1, 4-dihydroquinoline-6-carboxylate
Figure PCTCN2018122505-APPB-000021
Methyl 4- (((4, 4-dimethyl-2, 6-dioxocyclohexylidene) methyl) amino) benzoate (10g,33.9mmol) and o-dichlorobenzene (50mL) were added to a single-neck flask, and then the system was put into a 180 ℃ oil bath to be heated and reacted for 7h, TLC followed the reaction progress, the system was from insoluble to colorless transparent, the color was further deepened to dark brown, and when the reaction was completed, a solid was generated in the system. After cooling to room temperature, suction filtration was carried out to obtain 2.5g of a yellowish solid in a yield of 38%.
MS(ES-API,pos.ion)m/z:204.1[M+H]+。
And step 3: synthesis of 4-chloroquinoline-6-carboxylic acid methyl ester
Figure PCTCN2018122505-APPB-000022
To a single neck flask was added methyl 4-oxo-1, 4-dihydroquinoline-6-carboxylate (150mg,0.738mmol), toluene (3mL) and phosphorus oxychloride (125mg,0.812mmol), added to a 120 ℃ oil bath, stirred for 3h and monitored by TLC for reaction completion. Ethyl acetate (10mL) was added for dilution, washed with saturated sodium bicarbonate solution (5mL), the organic phase was concentrated, and column chromatography (petroleum ether/ethyl acetate (V/V) ═ 5/1) gave 141mg of a white solid in 86% yield.
MS(ES-API,pos.ion)m/z:222.0[M+H]+。
And 4, step 4: synthesis of methyl 4- (2, 2-difluoroethoxy) quinoline-6-carboxylate
Figure PCTCN2018122505-APPB-000023
To a two-necked flask was added NaH (1.0g,24.82mmol, Wt ═ 60%) under nitrogen, followed by ultra-dry DMF (45mL), and 2, 2-difluoroethanol (2.04g,24.82mmol) was slowly added dropwise and stirred at room temperature for 30 min. Then 4-chloroquinoline-6-carboxylic acid methyl ester (5.0g,22.56mmol) was added rapidly, the temperature was raised to 80 ℃ for 12h reaction, and the completion of the reaction was monitored by TLC. The system was poured into water (200mL) and a large amount of solid precipitated, which was filtered off with suction and the filter cake was washed with water (20mL) to give 4g of a yellow solid in 66% yield.
MS(ES-API,pos.ion)m/z:268.0[M+H]+。
And 5: synthesis of 4- (2, 2-difluoroethoxy) quinoline-6-carboxylic acid
Figure PCTCN2018122505-APPB-000024
To a single neck flask was added methyl 4- (2, 2-difluoroethoxy) quinoline-6-carboxylate (5.0g,18.71mmol), THF (35mL), ethanol (35mL), water (35mL) and lithium hydroxide monohydrate (1.5g,37.42mmol), stirred at room temperature, and reacted for 2 h. TLC monitored the reaction complete. The THF and ethanol were removed by distillation under reduced pressure, dissolved in water, extracted with ethyl acetate (20 mL. times.2), the aqueous phase collected, acidified with concentrated hydrochloric acid (2M,30mL) and a large amount of solid precipitated, filtered off with suction to give 2.2g of a white solid in 46% yield.
MS(ES-API,pos.ion)m/z:254.1[M+H]+。
Step 6: synthesis of 4- (2, 2-difluoroethoxy) quinoline-6-acyl chloride
Figure PCTCN2018122505-APPB-000025
4- (2, 2-Difluoroethoxy) quinoline-6-carboxylic acid (500mg,1.97mmol) and thionyl chloride (4mL) were added to a single-neck flask, stirred at room temperature, then catalyzed by 2 drops of DMF, reacted under reflux for 3h, and the starting material was dissolved. The system was drained and dried DCM (5mL) was added to give a suspension of 4- (2, 2-difluoroethoxy) quinoline-6-carbonyl chloride.
And 7: synthesis of 1, 3-dimethyl-1H-pyrazol-5-yl 4- (2, 2-difluoroethoxy) quinoline-6-carboxylic acid ester
Figure PCTCN2018122505-APPB-000026
To a single-necked flask was added 1, 3-dimethyl-1H-pyrazol-5-ol (265mg,2.39mmol), dried dichloromethane (20mL) and Et3N (372mg,3.68mmol), stirring at 0 deg.C, then adding the suspension of 4- (2, 2-difluoroethoxy) quinoline-6-carbonyl chloride in step 6. The temperature is raised to room temperature, the reaction is carried out overnight, and the reaction is detected to be complete by TLC. The reaction mixture was washed with saturated sodium hydrogencarbonate solution (10mL) and saturated brine (10mL), and the mixture was concentrated and recrystallized to give 600mg of a yellow solid.
MS(ES-API,pos.ion)m/z:348.0[M+H]+。
And 8: synthesis of (4- (2, 2-difluoroethoxy) quinolin-6-yl) (5-hydroxy-1, 3-dimethyl-1H-pyrazol-4-yl) methanone
Figure PCTCN2018122505-APPB-000027
To a single-necked flask was added 1, 3-dimethyl-1H-pyrazol-5-yl 4- (2, 2-difluoroethoxy) quinoline-6-carboxylic acid ester (600mg,1.73mmol), acetonitrile (25mL) and triethylamine (350mg,3.46mmol), stirred at room temperature, and then trimethylsilyl cyanide (25mg,0.26mmol) was added. The reaction was carried out at room temperature for 24h and the completion of the reaction was monitored by TLC. The reaction mixture was acidified with glacial acetic acid (1mL), stirred at room temperature for 30min, the organic solvent was removed from the reaction mixture, dissolved in water (15mL), extracted with dichloromethane (20mL × 2), and purified by column chromatography (dichloromethane/methanol (V/V) ═ 20/1) to give 300mg of a yellow solid with a yield of 50%.
MS(ES-API,pos.ion)m/z:348.1[M+H]+；
1H NMR(400MHz,DMSO-d6)8.85(d,J＝5.2Hz,1H),8.43(s,1H),8.03–7.95(m,2H),7.20(d,J＝5.2Hz,1H),6.57(tt,J＝54.0,3.2Hz,1H),4.67(td,J＝14.6,3.2Hz,2H),3.46(s,3H),2.15(s,3H).
And step 9: synthesis of 2- ((4- (4- (2, 2-difluoroethoxy) quinoline-6-carbonyl) -1, 3-dimethyl-1H-pyrazol-5-yl) oxy) -1-acetophenone
Figure PCTCN2018122505-APPB-000028
(4- (2, 2-Difluoroethoxy) quinolin-6-yl) (5-hydroxy-1, 3-dimethyl-1H-pyrazol-4-yl) methanone (95mg,0.274mmol), dry DMF (10mL) and potassium carbonate (57mg,0.411mmol) were added to a single-neck flask, dissolved with stirring, and then α -bromoacetophenone (60mg,0.301mmol) was added thereto, the reaction was allowed to react overnight at room temperature, the reaction was monitored by TLC for completion, ethyl acetate (20mL) was added to the system, and the mixture was diluted with saturated NaHCO3The solution was washed, and the organic phase was concentrated and subjected to column chromatography (dichloromethane/methanol (V/V) ═ 50/1) to give a yellowish brown solid 90mg with a yield of 70%.
MS(ES-API,pos.ion)m/z:466.1[M+H]+；
1H NMR(600MHz,CDCl3)8.85(d,J＝5.1Hz,1H),8.56(d,J＝1.8Hz,1H),8.11(d,J＝8.7Hz,1H),8.03(dd,J＝8.7,1.8Hz,1H),7.72(d,J＝7.2Hz,2H),7.55(t,J＝7.5Hz,1H),7.41(t,J＝7.8Hz,2H),6.79(d,J＝5.1Hz,1H),6.27(tt,J＝54.6,4.2Hz,1H),5.48(s,2H),4.44(td,J＝12.6,4.2Hz,2H),3.88(s,3H),2.02(s,3H).
The target compounds of table 1 can be obtained by referring to the synthesis schemes of the present invention or the synthesis of specific examples, using the corresponding raw materials and conditions.
TABLE 1
Figure PCTCN2018122505-APPB-000029
Figure PCTCN2018122505-APPB-000030
Figure PCTCN2018122505-APPB-000031
Figure PCTCN2018122505-APPB-000032
Figure PCTCN2018122505-APPB-000033
Figure PCTCN2018122505-APPB-000034
Figure PCTCN2018122505-APPB-000035
Figure PCTCN2018122505-APPB-000036
Figure PCTCN2018122505-APPB-000037
Figure PCTCN2018122505-APPB-000038
Biological examples
Compound preparation: weighing a certain mass of original medicine by an analytical balance (0.0001g), dissolving the original medicine by a proper amount of DMF (dimethyl formamide), and then diluting the original medicine by a certain volume of distilled water containing 1 per mill of Tween-80 emulsifier for later use.
The test method comprises the following steps: the test targets are piemarker, purslane, cockspur grass and green bristlegrass.
Stem and leaf spraying method: and (3) loading soil in a flowerpot with the length and the width of 7.0cm to 3/4 positions, directly sowing the pretreated weed target seeds, covering soil with the soil for about 1.0cm, and performing spray treatment when the seedlings grow to be of a proper age. After the compounds were applied at the set dose, the mixture was transferred to the outside for cultivation, and the activity (%) against weeds was examined 21 days later.
The test results are shown in Table A.
TABLE A dose of 1000g a.i./ha, control of purslane by the compounds of the invention
Examples Control effect (%)
Compound (M) 80
Example 1 95
Example 2 95
Example 3 100
Example 4 90
Example 5 88
Example 6 100
Example 16 95
Example 33 80
Example 34 90
Example 37 80
The results in table a show that the control effect of the compounds of the invention on purslane at 1000g of a.i./ha can reach 80-100%. In addition, the compound has good control effect on broadleaf weeds (such as piemarker, amaranthus retroflexus and snakehead gut) and grassy weeds (such as crab grass, cockspur grass and green bristlegrass), is safe to crops and has good application prospect.

Claims (10)

  1. A compound which is a compound of formula (I) or a stereoisomer, a nitroxide or a salt of a compound of formula (I):
    Figure PCTCN2018122505-APPB-100001
    wherein:
    r is hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, alkylaminoalkyl, alkylthioalkyl, haloalkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, cycloalkylalkyl, heterocyclylalkyl, arylalkyl, or heteroarylalkyl; r is optionally selected from R by 1,2,3, 4, 5 or 6xSubstituted with the substituent(s);
    cy is the following subformula:
    Figure PCTCN2018122505-APPB-100002
    or
    Figure PCTCN2018122505-APPB-100003
    R1And R22Each independently hydrogen, -C (═ O) - (CH)2)n-R8、-(CH2)m-C(＝O)-R8a、-C(＝O)-O-R9、-C(＝O)-NR10R11、-S(＝O)2-R12、-S(＝O)2-NR13R14；
    n is 0, 1,2 or 3;
    m is 1,2 or 3;
    wherein R is8、R8a、R9、R10、R11、R12、R13And R14Each independently is hydrogen, alkyl, alkoxyalkyl, aryl, or heteroaryl; r8、R8a、R9、R10、R11、R12、R13And R14Each independently is optionally selected from R by 1,2,3, 4, 5 or 6ySubstituted with the substituent(s);
    R2、R3、R4、R5、R6and R7Each independently is hydrogen, fluoro, chloro, bromo, iodo, amino, nitro, cyano, hydroxy, carboxy, alkyl, alkoxy, alkylthio, or alkylcarbonyl;
    R33is hydrogen, alkyl, alkenyl, alkynyl or cycloalkyl;
    R44is hydrogen, cyano, fluorine, chlorine, bromine, iodine, alkyl, alkenyl, alkynyl, alkoxy, alkylthio or cycloalkyl;
    Rxand RyEach independently is fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, C1-8Alkyl, halo C1-8Alkyl radical, C2-8Alkenyl, halo C2-8Alkenyl radical, C2-8Alkynyl, halo C2-8Alkynyl, C1-8Alkoxy, halo C1-8Alkoxy radical, C1-8Alkylamino radical, C1-8Alkylthio, halo C1-8Alkylamino, halogeno C1-8Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-9Heteroaryl or C1-9A heteroaryloxy group.
  2. The compound of claim 1, wherein
    R is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy radical C1-6Alkyl radical, C1-6Alkylamino radical C1-6Alkyl radical, C1-6Alkylthio group C1-6Alkyl, halo C1-6Alkyl radical, C3-8Cycloalkyl radical, C2-8Heterocyclic group, C6-10Aryl radical, C1-9Heteroaryl group, C3-8Cycloalkyl radical C1-6Alkyl radical, C2-8Heterocyclyl radical C1-6Alkyl radical, C6-10Aryl radical C1-6Alkyl or C1-9Heteroaryl C1-6An alkyl group; r is optionally selected from R by 1,2,3, 4, 5 or 6xSubstituted with the substituent(s);
    each RxIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl, halo C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkoxy radical, C1-4Alkylamino radical, C1-4Alkylthio, halo C1-4Alkylamino, halogeno C1-4Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-5Heteroaryl or C1-5A heteroaryloxy group.
  3. The compound of claim 2, wherein
    R is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C1-3Alkoxy radical C1-3Alkyl radical, C1-3Alkylamino radical C1-3Alkyl radical, C1-3Alkylthio group C1-3Alkyl, halo C1-4Alkyl radical, C3-6Cycloalkyl radical, C2-6Heterocyclic group, C6-10Aryl radical, C1-5Heteroaryl group, C3-6Cycloalkyl radical C1-3Alkyl radical, C2-6Heterocyclyl radical C1-4Alkyl radical, C6-10Aryl radical C1-3Alkyl radicalOr C1-5Heteroaryl C1-3An alkyl group; r is optionally selected from R by 1,2,3, 4, 5 or 6xSubstituted with the substituent(s);
    each RxIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, methoxy or trifluoromethoxy.
  4. The compound of claim 3, wherein
    R is hydrogen, -CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CF3、-CH2CHF2、-CH2CF3、-CH2OCH3、-CH2CH2OCH3or-CH2OCH2CH3；
    Or R is the following subformula:
    Figure PCTCN2018122505-APPB-100004
  5. the compound of claim 1, wherein
    R1And R22Each independently hydrogen, -C (═ O) - (CH)2)n-R8、-(CH2)m-C(＝O)-R8a、-C(＝O)-O-R9、-C(＝O)-NR10R11、-S(＝O)2-R12、-S(＝O)2-NR13R14；
    n is 0, 1,2 or 3;
    m is 1,2 or 3;
    wherein R is8、R8a、R9、R10、R11、R12、R13And R14Each independently is hydrogen, C1-6Alkyl radical, C1-6Alkoxy radical C1-6Alkyl radical, C6-10Aryl or C1-9A heteroaryl group; r8、R8a、R9、R10、R11、R12、R13And R14Each independently is optionally selected from R by 1,2,3, 4, 5 or 6ySubstituted with the substituent(s);
    R33is hydrogen, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl or C3-6A cycloalkyl group;
    R44is hydrogen, cyano, fluorine, chlorine, bromine, iodine, C1-6Alkyl radical, C2-6Alkenyl radical, C2-6Alkynyl, C1-6Alkoxy radical, C1-6Alkylthio or C3-6A cycloalkyl group;
    each RyIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxy, carboxyl, C1-4Alkyl, halo C1-4Alkyl radical, C2-4Alkenyl, halo C2-4Alkenyl radical, C2-4Alkynyl, halo C2-4Alkynyl, C1-4Alkoxy, halo C1-4Alkoxy radical, C1-4Alkylamino radical, C1-4Alkylthio, halo C1-4Alkylamino, halogeno C1-4Alkylthio radical, C6-10Aryl radical, C6-10Aryloxy radical, C1-5Heteroaryl or C1-5A heteroaryloxy group.
  6. The compound of claim 5, wherein
    R1And R22Each independently hydrogen, -C (═ O) - (CH)2)n-R8Or- (CH)2)m-C(＝O)-R8a；
    n is 0, 1,2 or 3;
    m is 1,2 or 3;
    R33is hydrogen, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl or C3-6A cycloalkyl group;
    R44is hydrogen, cyano, fluorine, chlorine, bromine, iodine, C1-4Alkyl radical, C2-4Alkenyl radical, C2-4Alkynyl, C1-4Alkoxy radical, C1-4Alkylthio or C3-6A cycloalkyl group;
    wherein R is8And R8aEach independently is hydrogen, C1-4Alkyl radical, C1-4Alkoxy radical C1-4Alkyl, phenyl or C2-3A heteroaryl group; r8And R8aEach independently is optionally selected from R by 1,2,3, 4, 5 or 6ySubstituted with the substituent(s);
    each RyIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, methoxy or trifluoromethoxy.
  7. The compound of claim 6, wherein
    R1And R22Each independently hydrogen, -C (═ O) - (CH)2)n-R8Or- (CH)2)m-C(＝O)-R8a；
    n is 0, 1,2 or 3;
    m is 1,2 or 3;
    R8and R8aEach independently is phenyl or pyrazolyl; r8And R8aEach independently is optionally selected from R by 1,2,3, 4, 5 or 6ySubstituted with the substituent(s);
    each RyIndependently fluorine, chlorine, bromine, iodine, amino, nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, trifluoromethyl, methoxy or trifluoromethoxy;
    R33is hydrogen, methyl, ethyl, n-propyl or isopropyl;
    R44hydrogen, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl or cyclopropyl.
  8. A compound which is a compound having one of the following structures or a stereoisomer, a nitroxide or a salt thereof of a compound having one of the following structures:
    Figure PCTCN2018122505-APPB-100005
    Figure PCTCN2018122505-APPB-100006
    Figure PCTCN2018122505-APPB-100007
    Figure PCTCN2018122505-APPB-100008
    Figure PCTCN2018122505-APPB-100009
    or
    Figure PCTCN2018122505-APPB-100010
  9. A composition comprising a compound of any one of claims 1-8; optionally comprising at least one adjuvant.
  10. Use of a compound according to any one of claims 1 to 8 or a composition according to claim 9 in agriculture.
CN201880087384.1A 2018-12-21 2018-12-21 Quinoline derivatives, preparation method and application thereof Pending CN111670182A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1230951A (en) * 1996-09-20 1999-10-06 巴斯福股份公司 Hetaroyl cyclohexanedione derivatives with herbicidal effect
CN1235600A (en) * 1996-09-20 1999-11-17 巴斯福股份公司 4-hetaroylpyrazol derivatives
CA2353572A1 (en) * 1998-12-04 2000-06-15 Basf Aktiengesellschaft Method for producing pyrazolylbenzoyl derivatives and novel pyrazolylbenzoyl derivatives
US7030063B1 (en) * 1998-09-08 2006-04-18 Basf Aktiengesellschaft Cyclohexenonquinolinoyl-derivatives as herbicidal agents

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1230951A (en) * 1996-09-20 1999-10-06 巴斯福股份公司 Hetaroyl cyclohexanedione derivatives with herbicidal effect
CN1235600A (en) * 1996-09-20 1999-11-17 巴斯福股份公司 4-hetaroylpyrazol derivatives
US7030063B1 (en) * 1998-09-08 2006-04-18 Basf Aktiengesellschaft Cyclohexenonquinolinoyl-derivatives as herbicidal agents
CA2353572A1 (en) * 1998-12-04 2000-06-15 Basf Aktiengesellschaft Method for producing pyrazolylbenzoyl derivatives and novel pyrazolylbenzoyl derivatives

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