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CN112409226B - Substituted benzoyl compounds and application thereof - Google Patents

Substituted benzoyl compounds and application thereof Download PDF

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Publication number
CN112409226B
CN112409226B CN201910785500.3A CN201910785500A CN112409226B CN 112409226 B CN112409226 B CN 112409226B CN 201910785500 A CN201910785500 A CN 201910785500A CN 112409226 B CN112409226 B CN 112409226B
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compound
methyl
mmol
alkyl
chloro
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CN112409226A (en
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李义涛
林健
黄敏
吴庆国
刘鹏飞
张虎
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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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/38—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atom of at least one amino group being part of any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylaminosulfones
    • C07C317/40—Y being a hydrogen or a carbon atom
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/76—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur 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
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention provides a substituted benzoyl compound and application thereof; specifically, the invention provides a compound shown in a formula (I) and a preparation method thereof; compositions containing these compounds and their use as herbicides; wherein Q is optionally substituted oxycyclohexenyl or substituted pyrazolyl, and the like; r is R 1 Is hydrogen, C 1‑6 Alkyl, halogenated C 1‑6 Alkyl, C 3‑8 Cycloalkyl groups, and the like; r is R 2 is-C (=O) -C 6‑10 Aryl, -C (=o) -C 1‑9 Heteroaryl, -C (=o) -C 3‑8 Cycloalkyl, -SO 2 ‑C 6‑10 Aryl, -SO 2 ‑C 1‑9 Heteroaryl, and the like; x is chlorine or-SO 2 CH 3 。

Description

Substituted benzoyl compounds and application thereof
Technical Field
The invention provides a novel substituted benzoyl compound and a preparation method thereof; compositions containing these compounds and their use in agriculture.
Background
Substituted benzoyl compounds are a class of compounds with excellent biological activity, the herbicidal activity of which is reported, for example, in CN1524075A, CN1649830a, etc. However, the compounds of the present invention described in detail below are not described in these documents.
The active ingredients known from the above-cited documents have disadvantages in use, for example (a) have no or only inadequate herbicidal action on the weed plants, (b) have a too narrow spectrum of weed plants to be controlled or (c) have too low a selectivity in crops of useful plants.
Thus, 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 substituted benzoyl compound having an excellent herbicidal effect, a broad weed control spectrum and excellent selectivity between crops and weeds.
In one aspect, the present invention provides a compound of formula (I) or a stereoisomer, tautomer, nitroxide, or salt thereof of a compound of formula (I):
wherein:
R 1 is hydrogen, C 1-6 Alkyl, halogenated C 1-6 Alkyl, C 1-6 Alkoxy C 1-6 Alkyl, C 2-8 Alkenyl, C 2-6 Alkynyl, C 3-8 Cycloalkyl, C 3-8 Cycloalkyl C 1-6 Alkyl, C 2-8 Heterocyclyl or C 2-8 Heterocyclyl C 1-6 An alkyl group;
R 2 is-C (=O) -C 6-10 Aryl, -C (=o) -C 1-9 Heteroaryl, -C (=o) -C 3-8 Cycloalkyl, -SO 2 -C 6-10 Aryl, -SO 2 -C 1-9 Heteroaryl, -SO 2 -C 3-8 Cycloalkyl or-SO 2 -C 2-8 A heterocyclic group; wherein R is 2 Optionally by 1, 2 or 3 members selected from halogen or C 1-6 Substituted by alkyl;
x is chlorine or-SO 2 CH 3 ；
Q is the following sub-structural formula:
R 3 is hydrogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl or C 3-8 Cycloalkyl;
R 4 is hydrogen or-CH 2 -CO-C 6-10 An aryl group; wherein the-CH 2 -CO-C 6-10 Aryl is optionally substituted with 1, 2 or 3 groups selected from halogen or C 1-6 Substituted by alkyl;
R 5 is C 1-6 An alkyl group;
R 6 and R is 7 Each independently is hydrogen or C 1-6 An alkyl group.
In some embodiments, R 1 Is hydrogen, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 1-3 Alkoxy C 1-4 Alkyl, C 2-6 Alkenyl, C 2-4 Alkynyl, C 3-6 Cycloalkyl, C 3-6 Cycloalkyl C 1-4 Alkyl, C 2-6 Heterocyclyl or C 2-6 Heterocyclyl C 1-4 An alkyl group.
In other embodiments, R 1 Is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Wherein the method comprises the steps ofIn some embodiments, R 2 is-C (=O) -C 6-10 Aryl, -C (=o) -C 1-5 Heteroaryl, -C (=o) -C 3-6 Cycloalkyl, -SO 2 -C 6-10 Aryl, -SO 2 -C 1-5 Heteroaryl, -SO 2 -C 3-6 Cycloalkyl or-SO 2 -C 2-6 A heterocyclic group; wherein R is 2 Optionally by 1, 2 or 3 members selected from halogen or C 1-4 The substituent of the alkyl group is substituted.
In other embodiments, R 2 is-C (=o) -phenyl, -C (=o) -thienyl, -C (=o) -furyl, -C (=o) -cyclopropyl, -C (=o) -cyclobutyl, -C (=o) -cyclopentyl, -C (=o) -cyclohexyl, -SO 2 -phenyl, -SO 2 -thienyl, -SO 2 -furyl, -SO 2 -cyclopropyl, -SO 2 -cyclobutyl, -SO 2 Cyclopentyl or-SO 2 -a cyclohexyl group; wherein R is 2 Optionally by 1, 2 or 3 members selected from halogen or C 1-3 The substituent of the alkyl group is substituted.
In some embodiments, R 3 Is hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl or C 3-6 Cycloalkyl groups.
In other embodiments, R 3 Is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
In some embodiments, R 4 Is hydrogen or-CH 2 -CO-phenyl; wherein the-CH 2 -CO-phenyl optionally substituted with 1, 2 or 3 groups selected from halogen or C 1-4 The substituent of the alkyl group is substituted.
In other embodiments, R 4 Is hydrogen.
In some embodiments, R 5 Is C 1-4 An alkyl group.
In other embodiments, R 5 Is methyl or ethyl.
In some embodiments, R 6 And R is 7 Each independently is hydrogen or C 1-4 An alkyl group.
In other embodiments, R 6 And R is 7 Each independently is hydrogen or methyl.
In some embodiments, the present invention provides a compound that is a compound of formula (Ia) or a stereoisomer, tautomer, nitroxide, or salt of a compound of formula (Ia):
wherein:
Ay 1 is C 6-10 Aryl, C 3-6 Cycloalkyl or C 1-5 Heteroaryl; wherein Ay is 1 Optionally by 1, 2 or 3 members selected from halogen or C 1-4 Substituted by alkyl;
R 1 x and Q have the meanings as described in the present invention.
In some embodiments, the present invention provides a compound that is a compound of formula (Ib) or a stereoisomer, tautomer, oxynitride or salt of a compound of formula (Ib):
Wherein:
Ay 2 is C 6-10 Aryl, C 3-6 Cycloalkyl or C 1-5 Heteroaryl; wherein Ay is 2 Optionally by 1, 2 or 3 members selected from halogen or C 1-4 Substituted by alkyl;
R 1 x and Q have the meanings as described in the present invention.
In other embodiments, ay 1 Is cyclopropyl, cyclobutyl, phenyl, thiophen-2-yl or furan-2-yl; wherein Ay is 1 Optionally by 1, 2 or 3 members selected from halogen or C 1-3 The substituent of the alkyl group is substituted.
In other embodiments, ay 1 Is cyclopropyl or cyclobutyl; or Ay 1 Optionally substituted by 1, 2 or 3 groups selected from halogen or C 1-3 Phenyl, thiophen-2-yl or furan-2-yl substituted by substituents of alkyl.
In other embodiments, ay 1 Is cyclopropyl or cyclobutyl; or Ay 1 Phenyl, thiophen-2-yl or furan-2-yl optionally substituted with 1, 2 or 3 substituents selected from fluorine, chlorine, bromine, iodine or methyl.
In other embodiments, ay 2 Is cyclopropyl, cyclobutyl, phenyl, thiophen-2-yl or furan-2-yl; wherein Ay is 2 Optionally by 1, 2 or 3 members selected from halogen or C 1-3 The substituent of the alkyl group is substituted.
In other embodiments, ay 2 Is cyclopropyl or cyclobutyl; or Ay 2 Optionally substituted by 1, 2 or 3 groups selected from halogen or C 1-3 Phenyl, thiophen-2-yl or furan-2-yl substituted by substituents of alkyl.
In other embodiments, ay 2 Is cyclopropyl or cyclobutyl; or Ay 2 Phenyl, thiophen-2-yl or furan-2-yl optionally substituted by 1, 2 or 3 substituents selected from fluorine, chlorine, bromine, iodine or methyl.
In other embodiments, ay 1 Is thatWherein Ay is 1 Optionally substituted with 1, 2 or 3 substituents selected from fluorine, chlorine, bromine, iodine, methyl or ethyl.
In other embodiments, ay 2 Is thatWherein Ay is 2 Optionally substituted with 1, 2 or 3 substituents selected from fluorine, chlorine, bromine, iodine, methyl or ethyl.
In other embodiments, ay 1 The following sub-structural formula is shown as follows:
in other embodiments, ay 2 The following sub-structural formula is shown as follows:
in other embodiments, Q is of the formula:
in some embodiments, the invention provides a compound that is a stereoisomer, tautomer, nitroxide, or salt thereof, of a compound having one of the following structures:
in another aspect, the invention provides a composition comprising a compound of the invention.
In some of these embodiments, the compositions of the present invention further optionally comprise at least one additional component.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention in agriculture.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention for controlling grassy weeds.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention for controlling broadleaf weeds.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention for the control of abutilon, purslane, barnyard grass or zinnia.
In some of these embodiments, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention for controlling unwanted vegetation.
In a further aspect, the present invention provides the use of a compound of the invention or a composition comprising a compound of the invention as a herbicide.
In another aspect, the invention provides the use of a compound of the invention or a composition comprising a compound of the invention as a post-emergent herbicide.
In another aspect, the present invention provides a method for controlling unwanted plants, characterized in that an effective amount of a compound of the present invention is applied to the plants, plant seeds, soil in or on which the plants are grown, or the cultivation area.
In a further aspect, the present invention provides a method of controlling weed growth in a useful plant comprising applying to the locus of the weed an effective amount of a compound of the invention or a composition comprising a compound of the invention.
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 (Ia) or formula (Ib) may exist in different stereoisomers or optical isomers or tautomeric forms. The present invention encompasses all such isomers and tautomers and mixtures thereof in various proportions, as well as isotopic forms such as heavy hydrogen-containing compounds.
Isotopically enriched compounds have structures depicted by the formulae given herein except that one or more atoms are replaced by an atom having a selected atomic 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 as 2 H， 3 H， 11 C， 13 C， 14 C， 15 N， 17 O， 18 O， 18 F， 31 P， 32 P， 35 S， 36 Cl and Cl 125 I。
Any asymmetric atom (e.g., carbon, etc.) of the disclosed compounds may exist in racemic or enantiomerically enriched form, such as in the (R) -, (S) -or (R, S) -configuration.
The foregoing merely outlines certain aspects of the invention and is not limited to these and other aspects, which are described more fully below.
Detailed description definitions and general terms of the invention
Reference will now be made in detail to certain embodiments of the invention, examples of which are illustrated in the accompanying structural and chemical formulas. The invention is intended to cover all alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. Those 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 of one or more of the incorporated references, patents and similar materials differing from or contradictory to the present application (including but not limited to defined terms, term application, described techniques, etc.), the present application controls.
It should further be 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 sub-combination.
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, chemical elements are in accordance with CAS version of the periodic Table of the elements, and handbook of chemistry and physics, 75 th edition, 1994. In addition, general principles of organic chemistry may be referenced to the descriptions in "Organic Chemistry", thomas Sorrell, university Science Books, sausalato: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" are intended to include "at least one" or "one or more" unless the context clearly dictates otherwise or otherwise. Thus, as used herein, these articles refer to one or to more than one (i.e., to at least one) object. For example, "a component" refers to one or more components, i.e., more than one component is contemplated as being employed or used in embodiments of the described embodiments.
The term "comprising" is an open-ended expression, i.e., including what is indicated by the invention, but not excluding other aspects.
"stereoisomers" refer to compounds having the same chemical structure but different arrangements of atoms or groups in space. Stereoisomers include enantiomers, diastereomers, conformational isomers (rotamers), geometric isomers (cis/trans), atropisomers, and the like.
"enantiomer" refers to two isomers of a compound that do not overlap but are in mirror image relationship to each other.
"diastereoisomers" refers to stereoisomers which have two or more chiralities and whose molecules are not mirror images of each other. Diastereomers have different physical properties, such as melting point, boiling point, spectral properties, and reactivity. The diastereomeric mixture may be separated by high resolution analytical procedures such as electrophoresis and chromatography, e.g., HPLC.
The stereochemical definitions and rules used in the present invention generally follow S.P. Parker, ed., mcGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, new York; and Eliel, e.and Wilen, s., "Stereochemistry of Organic Compounds", john Wiley & Sons, inc., new York, 1994.
Many organic compounds exist in 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 represent the absolute configuration of the molecule with respect to one or more of its chiral centers. The prefixes d and l or (+) and (-) are symbols for specifying the rotation of plane polarized light by a compound, where (-) or l indicates that the compound is left-handed. The compound prefixed with (+) or d is dextrorotatory. One 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 can occur when there is no stereoselectivity or stereospecificity in a chemical reaction or process.
The term "tautomer" or "tautomeric form" refers to structural isomers having different energies that can be interconverted by a low energy barrier (low energy barrier). If tautomerism is possible (e.g., in solution), chemical equilibrium of the tautomers can be achieved. For example, proton tautomers (also known as proton transfer tautomers (prototropic tautomer)) include interconversions by proton transfer, such as keto-enol isomerisation and imine-enamine isomerisation. Valence tautomers (valance tautomers) include interconversions by recombination of some of the bond-forming electrons. Specific examples of keto-enol tautomerism are tautomerism of pentane-2, 4-dione, hexane-1, 3-dione and 4-hydroxypent-3-en-2-one tautomer. Another example of tautomerism is phenol-ketone tautomerism. One specific example of phenol-ketone tautomerism is the interconversion of pyridin-4-ol and pyridin-4 (1H) -one tautomers. Unless otherwise indicated, all tautomeric forms of the compounds of the invention are within the scope of the invention.
In the present invention, depending on external conditions (such as solvent, pH, etc.), there is a tautomerism of keto-enol:
the compounds of the invention may be optionally substituted with one or more substituents, as described in the present invention, such as the compounds of the general formula above, or as specific examples within the examples, subclasses, and classes of compounds encompassed by the invention. It is to be 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 specific substituent. An optional substituent group may be substituted at each substitutable position of the group unless otherwise indicated. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, then the substituents may be the same or different at each position. Wherein the substituents may be, but are 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 alkyl, alkylamino, 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, heterocyclylacyl, aryl, arylalkyl, arylamino, heteroaryl, heteroarylalkyl, heteroarylamino, amido, sulfonyl, aminosulfonyl, and the like.
In addition, unless explicitly indicated otherwise, the descriptions used in this disclosure of the manner in which each … is independently "and" … is independently "and" … is independently "are to be construed broadly as meaning that particular items expressed between the same symbols in different groups do not affect each other, or that particular items expressed between the same symbols in the same groups do not affect each other.
In the various parts of the specification, the substituents of the compounds disclosed in this invention are as per the type or scope of the groupsOpening. It is specifically noted that the present invention includes each individual subcombination of the individual members of these group classes and ranges. For example, the term "C 1 -C 6 Alkyl "or" C 1-6 Alkyl "means in particular methyl, ethyl, C independently disclosed 3 Alkyl, C 4 Alkyl, C 5 Alkyl and C 6 An alkyl group.
The term "alkyl" or "alkyl group" as used herein, means a saturated straight or branched monovalent hydrocarbon group containing 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 to 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 (Et, -CH) 2 CH 3 ) N-propyl (n-Pr, -CH) 2 CH 2 CH 3 ) Isopropyl (i-Pr, -CH (CH) 3 ) 2 ) N-butyl (n-Bu, -CH) 2 CH 2 CH 2 CH 3 ) Isobutyl (i-Bu, -CH) 2 CH(CH 3 ) 2 ) Sec-butyl (s-Bu, -CH (CH) 3 )CH 2 CH 3 ) Tert-butyl (t-Bu, -C (CH) 3 ) 3 ) N-pentyl (-CH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH) 3 )CH 2 CH 2 CH 3 ) 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) N-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-hexyl (-CH (CH) 3 )CH 2 CH 2 CH 2 CH 3 ) 3-hexyl (-CH (CH) 2 CH 3 )(CH 2 CH 2 CH 3 ) 2-methyl-2-pentyl (-C (CH) 3 ) 2 CH 2 CH 2 CH 3 ) 3-methyl-2-pentyl (-CH (CH) 3 )CH(CH 3 )CH 2 CH 3 ) 4-methyl-2-pentyl (-CH (CH) 3 )CH 2 CH(CH 3 ) 2 ) 3-methyl-3-pentyl (-C (CH) 3 )(CH 2 CH 3 ) 2 ) 2-methyl-3-pentyl (-CH (CH) 2 CH 3 )CH(CH 3 ) 2 ) 2, 3-dimethyl-2-butyl (-C (CH) 3 ) 2 CH(CH 3 ) 2 ) 3, 3-dimethyl-2-butyl (-CH (CH) 3 )C(CH 3 ) 3 ) N-heptyl, n-octyl, and the like.
The term "alkenyl" denotes a straight-chain or branched monovalent hydrocarbon radical containing 2 to 12 carbon atoms, in which there is at least one site of unsaturation, i.e. one carbon-carbon sp 2 A double bond, wherein the alkenyl group may be optionally substituted with one or more substituents described herein, including the positioning of "cis" and "tans", or the positioning of "E" and "Z". 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 comprises 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) 2 CH＝CH 2 ) Propenyl (CH) 3 -CH＝CH-)，-CH 2 CH 2 CH＝CH 2 、-CH 2 CH＝CHCH 3 、-CH 2 CH 2 CH 2 CH＝CH 2 、-CH 2 CH 2 CH＝CHCH 3 、-CH 2 CH 2 CH 2 CH＝CHCH 3 Etc.
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 group may be optionally substituted with one or more substituents described herein. In one embodiment, the alkynyl group contains 2 to 10 carbon atoms; in one embodiment, the alkynyl group contains 2 to 8 carbon atoms; in another embodiment, the alkynyl group contains 2 to 6 carbon atoms; in yet another embodiment, the alkynyl group contains 2 to 4 carbon atoms. Examples of alkynyl groups include, but are not limited to, -C.ident.CH, -C.ident.CCH 3 、-CH 2 -C≡CH、-CH 2 -C≡CCH 3 、-CH 2 CH 2 -C≡CH、-CH 2 -C≡CCH 2 CH 3 、-CH 2 CH 2 -C≡CH 2 CH 3 Etc.
The term "alkoxy" means that the alkyl group is attached to the remainder of the molecule through an oxygen atom, wherein the alkyl group has the meaning as described herein. Unless otherwise specified, the alkoxy groups contain 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) 2 CH 3 ) 1-propoxy (n-PrO, n-propoxy, -OCH) 2 CH 2 CH 3 ) 2-propoxy (i-PrO, i-propoxy, -OCH (CH) 3 ) 2 ) 1-butoxy (n-BuO, n-butoxy, -OCH) 2 CH 2 CH 2 CH 3 ) 2-methyl-l-propoxy (i-BuO, i-butoxy, -OCH) 2 CH(CH 3 ) 2 ) 2-butoxy (s-BuO, s-butoxy, -OCH (CH) 3 )CH 2 CH 3 )，2-methyl-2-propoxy (t-BuO, t-butoxy, -OC (CH) 3 ) 3 ) 1-pentoxy (n-pentoxy, -OCH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentoxy (-OCH (CH) 3 )CH 2 CH 2 CH 3 ) 3-pentoxy (-OCH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butoxy (-OC (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butoxy (-OCH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-l-butoxy (-OCH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-l-butoxy (-OCH) 2 CH(CH 3 )CH 2 CH 3 ) And so on.
The term "alkoxyalkyl" means an alkyl group substituted with one or more alkoxy groups, where alkyl and alkoxy groups have the meaning as described herein. Examples of alkoxyalkyl groups include, but are not limited to, -CH 2 OCH 3 、-CH 2 OCH 2 CH 3 、-CH 2 OCH 2 CH 2 CH 3 、-CH 2 CH 2 OCH 3 、-CH 2 CH 2 OCH 2 CH 3 、-CH 2 CH 2 CH 2 OCH 3 And so on.
The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
The term "haloalkyl" means an alkyl group substituted with one or more halogen atoms. Examples of haloalkyl groups include, but are not limited to, -CH 2 F，-CHF 2 ，-CH 2 Cl，-CH 2 Br，-CF 3 ，-CH 2 CF 3 ，-CH 2 CH 2 F，-CH 2 CH 2 Cl，-CH 2 CH 2 Br，-CH 2 CHF 2 ，-CH 2 CH 2 CF 3 ，-CH 2 CH 2 CH 2 F，-CH 2 CH 2 CH 2 Cl，-CH 2 CH 2 CH 2 Br，-CHFCH 2 CH 3 ，-CHClCH 2 CH 3 And so on.
The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic ring system containing 3 to 12 carbon atoms. In one embodiment, cycloalkyl groups contain 3 to 12 carbon atoms; in one embodiment, cycloalkyl groups contain 3 to 10 carbon atoms; in another embodiment, cycloalkyl groups contain 3 to 8 carbon atoms; in yet another embodiment, cycloalkyl groups contain 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" means that the alkyl group is substituted with a cycloalkyl group, where the alkyl group and cycloalkyl group have the meanings as described herein. Examples include, but are not limited to, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, and the like.
The term "unsaturated" as used in the present invention means that the group contains one or more unsaturations.
The terms "heterocyclyl" and "heterocycle" are used interchangeably herein to refer to a saturated or partially unsaturated monocyclic, bicyclic or tricyclic ring containing 3 to 15 ring atoms, wherein the monocyclic, bicyclic or tricyclic ring contains no aromatic rings and at least one ring atom is selected from the group consisting of nitrogen, sulfur and oxygen atoms. Unless otherwise indicated, a heterocyclic group may be a carbon or nitrogen group, and-CH 2 The group may optionally be replaced by-C (=o) -. The sulfur atom of the ring may optionally be oxidized to an S-oxide. The nitrogen atom of the ring may optionally be oxidized to an N-oxide. 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-dioxacyclopentyl, dithiocyclopentyl, tetrahydropyranyl, dihydropyranyl, 2H-pyranyl, 4H-pyranyl, tetrahydrothiopyranyl, piperidinyl (2-piperidinyl)Group, 3-piperidinyl, 4-piperidinyl), morpholinyl, thiomorpholinyl, (1-oxo) -thiomorpholinyl, (1, 1-dioxo) -thiomorpholinyl, piperazinyl, dioxanyl, dithianyl, thiazanyl, homopiperazinyl, homopiperidinyl, oxacycloheptyl, thiacycloheptyl, 2-oxa-5-azabicyclo [2.2.1]Hept-5-yl, tetrahydropyridinyl. In heterocyclic groups-CH 2 Examples of the substitution of the-group by-C (=o) -include, but are not limited to, 2-oxopyrrolidinyl, oxo-1, 3-thiazolidinyl, 2-piperidonyl, 3, 5-dioxopiperidyl. Examples of sulfur atoms in the heterocyclic group that are oxidized include, but are not limited to, sulfolane, 1-dioxothiomorpholino. 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 described herein. Examples include, but are not limited to, tetrahydrofuranylmethyl, and the like.
The term "heteroatom" refers to O, S, N, P and Si, including N, S and any oxidation state forms of P; primary, secondary, tertiary and quaternary ammonium salt forms; or a form in which the hydrogen on the 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" means a monocyclic, bicyclic and tricyclic carbocyclic ring system 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 contains a ring of 3 to 7 atoms, and wherein one or more attachment points are attached to the remainder of the molecule. The term "aryl" may be used interchangeably with the term "aromatic ring". Examples of aryl groups may include phenyl, indenyl, naphthyl and anthracenyl. The aryl group is optionally substituted with one or more substituents described herein.
The term "heteroaryl" means 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 and has one or more attachment points attached to the remainder of the molecule. The term "heteroaryl" may be used interchangeably with the term "heteroaromatic ring" or "heteroaromatic compound". The heteroaryl group is optionally substituted with one or more substituents described herein.
In one embodiment, the heteroaryl group of 5 to 10 atoms comprises 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 containing 1-3 heteroatoms selected from N, O or S; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl containing 1-3 heteroatoms selected from N or O; in yet another embodiment, heteroaryl represents a 5 membered heteroaryl containing 1-3 heteroatoms selected from N or S.
In one embodiment, C 1-9 Heteroaryl means heteroaryl containing 1 to 9 carbon atoms as ring atoms. In another embodiment, C 1-6 Heteroaryl means heteroaryl containing 1 to 6 carbon atoms as ring atoms. In yet another embodiment, C 1-5 Heteroaryl means heteroaryl containing 1 to 5 carbon atoms as ring atoms.
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-triazolyl, 3-triazolyl, 1, 3-triazolyl, 3-thiotriazinyl, 1, 2-thiotriazinyl, 1-thiotriazinyl; the following bicyclic rings are also included, but are in no way limited to: benzimidazolyl, benzofuranyl, benzothienyl, indolyl (e.g., 2-indolyl), and the like.
When the compounds of the present invention contain one acid moiety, salts of the compounds of the present invention include those derived from alkali metals or alkaline earth metals, as well as those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium and have the formula N + (R 19 R 20 R 21 R 22 ) Wherein R is an ammonium cation of 19 、R 20 、R 21 And R is 22 Independently selected from hydrogen, C 1 -C 6 Alkyl and C 1 -C 6 A hydroxyalkyl group. Salts of the compounds of formula (I), formula (Ia) or formula (Ib) may be prepared by treating a compound of formula (I), formula (Ia) or formula (Ib) with a metal hydroxide (e.g. sodium hydroxide) or an amine (e.g. ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecamine or benzylamine).
When the compounds of the present invention contain a base moiety, acceptable salts may be formed with organic and inorganic acids, such as acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, 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 herbicide active ingredients in compositions or formulations having at least one additional component selected from the group consisting of surfactants, solid diluents, liquid diluents, and the like, which meet the pesticide use requirements, are within the scope of the present invention. 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, humidity 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 to a gel. General types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions and suspoemulsions. The general 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, 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 form a suspension or solid formulation; alternatively, the entire active ingredient formulation may be encapsulated (or "coated"). Encapsulation can control or delay the release of the active ingredient. Emulsifiable granules combine the advantages of both emulsifiable concentrate formulations and dry granule 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 as formulations that are readily diluted in a spray medium (typically water). The spray volume may be in the range of about one to several thousand litres per hectare, but more typically in the range of about ten to several hundred litres per hectare. The sprayable formulation may be mixed with water or another suitable medium in a sink for treatment of the foliage by air or ground application or into the growing medium of the plant. The liquid and dry formulations may be dosed directly into the drip irrigation system or into the furrow during planting.
The formulation will typically comprise an effective amount of the 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, starch, dextrin, sugar (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and sodium bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al, handbook of Insecticide Dust Diluents and Carriers, 2 nd edition, dorland Books, caldwell, new Jersey.
Liquid diluents include, for example, water, N-dimethylalkanamide (e.g., N, N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidone (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, glyceryl 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., isopentyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate), other esters (e.g., alkylated lactate, dibasic esters and gamma-butyrolactone), and alcohols which may be linear, branched, saturated or unsaturated (e.g., methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, N-hexanol, 2-ethylhexanol, N-octanol, decanol, isodecanol, stearyl alcohol, lauryl alcohol, benzyl alcohol, and benzyl alcohol. The liquid diluent also includes saturated and unsaturated fatty acids (typically C 6 -C 22 ) Such as vegetable seed and fruit oils (e.g., olive oil, castor oil, linseed oil, sesame oil, corn oil, peanut oil, sunflower oil, grape seed 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, where the fatty acids can be obtained by hydrolysis of glycerides derived from plants and animals, and can be purified by distillation. Typical liquid diluents are described in solvent guides, 2 nd edition, interscience, new York,1950, of Marsden.
The solid and liquid compositions of the present invention generally comprise one or more surfactants. When added to a liquid, surfactants (also referred to as "surface-active agents") typically change, most typically lowering the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in the surfactant molecule, the surfactant may act as a wetting agent, dispersant, emulsifier or defoamer.
Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful as the 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 ethoxylated, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybeans, castor and rapeseed oils; alkylphenol ethoxylates, such as octylphenol ethoxylate, nonylphenol ethoxylate, dinonylphenol ethoxylate, and dodecylphenol ethoxylate (prepared from phenol and ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof); a block polymer prepared from ethylene oxide or propylene oxide and a reverse block polymer, wherein the end block is 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, glycerol esters, 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, grafted 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: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives, such as lignin sulfonates; maleic acid or succinic acid or their anhydrides; olefin sulfonate; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates, and phosphate esters of styrylphenol ethoxylates; protein-based surfactants; sarcosine derivatives; styrylphenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfate of alcohol; a sulfate salt of an ethoxylated alcohol; sulfonates of amines and amides, such as N, N-alkyl taurates; sulfonates of benzene, cumene, toluene, xylene, dodecylbenzene and tridecylbenzene; sulfonate of condensed naphthalene; sulfonates of naphthalene and alkyl naphthalenes; sulfonate of petroleum fraction; 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, as well as ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetate and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and di-quaternary salts; and amine oxides such as alkyl dimethyl amine oxide and di- (2-hydroxyethyl) -alkyl amine oxide.
Mixtures of nonionic and anionic surfactants, or mixtures of nonionic and cationic surfactants, may also be used in the compositions of the present invention. Nonionic, anionic and cationic surfactants and their proposed uses are disclosed in a number of published references, including McCutcheon's Division, the Manufacturing Confectioner Publishing co. Encyclopedia of Surface Active Agents by sisey and Wood, chemical publication.co., inc., new York,1964; and Synthetic Detergents by A.S. Davidson and B.Milwidsky, seventh edition, john Wiley and Sons, new York,1987.
The compositions of the present invention may also contain formulation aids 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 can be controlled: pH (buffer), foaming during processing (defoamer such as polyorganosiloxane), sedimentation of active ingredient (suspending agent), viscosity (thixotropic thickener), microbial growth in the container (antimicrobial agent), 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 Confectioner Publishing co: functional Materials, north America and International yearbook edition; and those listed in PCT publication WO 03/024322.
The compounds of the invention and any other active ingredients are typically incorporated into the compositions of the invention by dissolving the active ingredient in a solvent or by grinding the active ingredient in a liquid diluent or in a dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent used as the liquid composition of the emulsifiable concentrate is water-immiscible, an emulsifier is typically 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 may 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 that produces an average particle size in the range of 2 μm to 10 μm. Powders and powders may be prepared by mixing, and typically by grinding (e.g., with a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active material onto preformed particulate carriers or by agglomeration techniques. See Browning, "Agglomeration" (Chemical Engineering, 12/month 4/1967, pages 147-48; chemical Engineer's Handbook of Perry, 4 th edition, mcGraw-Hill, new York,1963, pages 8-57 and thereafter and WO91/13546. Pellets may be prepared as described in U.S.4,172,714. Water-dispersible and water-soluble granules may be prepared as set forth in U.S.4,144,050, U.S.3,920,442 and DE.3,246,493. Tablets may be prepared as set forth in U.S.5,180,587, U.S.5,232,701 and U.S.5,208,030. Films may 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 Formulator's Toolbox-Product Forms for Modern Agriculture", pesticide Chemistry and Bioscience, the Food-Environment Challenge, edited by t.s. Brooks and t.r. roberts, proceedings of The 9th International Congress on Pesticide Chemistry,The Royal Society of Chemistry,Cambridge,1999, pages 120-133, of t.s. woods. See also U.S.3,235,361, column 6, line 16 to column 7, line 19 and examples 10-41; U.S.3,309,192, column 5, line 43 to column 7, line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S.2,891,855, column 3, line 66 to column 5, line 17 and examples 1-4; klingman Weed Control as a Science, john Wiley and Sons, inc., new York,1961, pages 81-96; hance et al Weed Control Handbook, 8 th edition, blackwell Scientific Publications, oxford,1989; and Developments in formulation technology, PJB Publications, richmond, UK,2000.
Use of the compounds of the invention
The herbicides of the invention can be used by spraying plants, applying to the soil, applying to the water surface. The amount of the active ingredient is appropriately determined to meet the purpose of use. The content of the active ingredient is appropriately determined according to the purpose.
The amount of the compound of the present invention to be used depends on the kind of the compound used, the target weeds, the tendency of the weeds to appear, the environmental conditions, the kind of herbicide, etc. When the herbicide according to the invention is used by itself, for example in the form of a powder or granules, its amount is suitably chosen to be from 1g to 50kg, preferably from 10g to 10kg, of active ingredient per 1 hectare. When the herbicide of the present invention is used in liquid form, for example, in the form of emulsifiable concentrate, wettable powder or flowable formulation, its amount is suitably selected to be 0.1 to 50,000ppm, preferably 10 to 10,000ppm.
The present invention provides a method for controlling weeds in crops of useful plants, which method comprises 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 present 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 cultivation area a herbicidally effective amount of a compound of formula (I), formula (Ia) or formula (Ib).
The term "herbicide" means a compound that controls or alters plant growth. The term "effective amount" means the amount of such a compound or a composition of such compounds that is capable of producing a controlled or altered plant growth effect. The effects of control or alteration include all naturally occurring deviations, e.g., killing, delay, leaf burn, albinism, dwarfing, etc. The term "plant" refers to all tangible parts of a plant, including seeds, seedlings, young plants, roots, tubers, stems, stalks, leaves, and fruits. The term "locus" is intended to include soil, seeds and seedlings, together with established plants (established vegetation) and includes not only areas where weeds may have grown, but also areas where weeds have not yet appeared, and also areas where crops of useful plants are grown. "area of planting" includes the land on which crop plants have grown, as well as the land intended for planting such crop plants. The term "weed" as used herein means any undesired plant and thus includes not only the important agronomic weeds as described below, but also volunteer crop plants.
Useful plant crops in which the compositions according to the invention may be used include, but are not limited to, perennial crops such as citrus fruits, vines, nuts, oil palm, olives, pomes, stone fruits and rubber, and annual cultivars such as cereals (e.g. barley and wheat), cotton, oilseed rape, maize, rice, soybean, sugar beet, sugarcane, sunflower, ornamental plants, switchgrass, turf and vegetables, especially cereals, maize and soybean.
The grass and weeds to be controlled may be monocotyledonous species such as, for example, agrimonia, myrtaria, avena, alternaria, bromus, tribulus, cyperus, crabgrass, barnyard, wild millet, lolium, july, panicum, poa, legionella, scirpus, setaria, sida and sorghum, or dicotyledonous species such as, for example, cannabis, amaranthus, chenopodium, chrysanthemum, euphorbia, lala, ipomoea, kochia, apocynum, polygonum, sida, sinapis, solanum, barbary, pogostemon, 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, oat, peanut, vegetable, tomato, potato, perennial crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grape, fruit tree, nut tree, banana, plantain, pineapple, hops, tea and forests such as in-tree and needle-leaved trees (e.g., loblolly pine), and turf species (e.g., bluegrass, st. Augustine grass), kentucky, and bermudagrass).
The compounds according to the invention of the formula (I), formula (Ia) or formula (Ib) can also be used, if desired, 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 to control weeds and/or unwanted plant growth, form further aspects of the invention. For the avoidance of doubt, the mixtures of the present invention also include mixtures of two or more different compounds of formula (I), formula (Ia) or formula (Ib). In particular, the invention also relates to a composition according to the invention comprising at least one further herbicide in addition to the compounds of formula (I), formula (Ia) or formula (Ib).
General synthetic procedure
In this specification, a structure is dominant if there is any difference between a chemical name and a chemical structure. In general, the compounds of the invention may be prepared by the methods described herein unless otherwise indicated.
The testing conditions of the nuclear magnetic resonance hydrogen spectrum of the invention are as follows: nuclear magnetic instrument of 400MHz or 600MHz of Bruker (Bruker) under room temperature condition, CDC1 3 ，d 6 -DMSO，CD 3 OD or d 6 Acetone as solvent (reported in ppm) with TMS (0 ppm) or chloroform (7.26 ppm) as reference standard. When multiple peaks occur, the following abbreviations will be used: s (single, singlet), d (doublet ), t (triplet, quartet), q (quartet), m (multiplet ), br (broadened, broad), dd (doublet of doublets, doublet), dt (doublet of triplets, doublet). Coupling constants are expressed in hertz (Hz).
The mass spectrometry method used in the invention comprises the following steps: agilent 1260HPLC was used; agilent 6120ESI.
Phase A: water (0.1% formic acid); and B phase: acetonitrile (containing 0.1% formic acid).
Gradient elution: 0-3min,5-100% B;3-6min,100% B.
Flow rate: 0.6mL/min.
Detection wavelength: 254nm.
MS parameters: ESI is scanning, collision induced ionization: 70V.
And (3) drying nitrogen: 12L/min, atomization gas pressure: 40psi, gas temperature: 350 ℃.
Taking a proper amount of sample, dissolving in 0.5mL of methanol, sampling, and performing primary MS full scanning under a positive ESI mode to obtain an excimer ion peak [ M+H ]] + And (5) reading.
The following abbreviations are used throughout the present invention:
AIBN: azobisisobutyronitrile
DMF: n, N-dimethylformamide, dimethylformamide
NBS: n-bromosuccinimide
EtOAc: acetic acid ethyl ester
PE or Petroleum ether: petroleum ether
TLC: thin layer chromatography
SOCl 2 : thionyl chloride
DMSO: dimethyl sulfoxide
CCl 4 : carbon tetrachloride
The following synthetic schemes and examples 1-17 are provided to further illustrate the teachings of the present invention.
Synthetic scheme
Synthesis scheme one
The compound (E) can be prepared by the synthesis of scheme one, wherein R 1 、R 2 、R 6 、R 7 And X has the meaning as described in the present invention; y is halogen. Reacting the compound (A1) with the compound (M1) under alkaline conditions (such as sodium carbonate and potassium carbonate) at 0-35 ℃ to obtain a compound (A); the compound (A) and the compound (M2) are reacted under alkaline conditions (e.g. carbonSodium acid and potassium carbonate) and reacting at 0-35 ℃ to obtain a compound (B1); hydrolyzing the compound (B1) under alkaline conditions (such as lithium hydroxide) to obtain a compound (B); the compound (B) and acyl chloride (such as oxalyl chloride) react in a halogenating way at 0-100 ℃ to obtain a compound (C); the compound (C) and the compound (M3) are subjected to esterification reaction at the temperature of 0-35 ℃ to obtain a compound (D); the compound (D) and the trimethylcyano silane undergo Fries rearrangement reaction at the temperature of 10-40 ℃ to obtain the target compound (E).
Synthesis scheme II
The compound (G) can be prepared by the synthesis scheme II, wherein R 1 、R 2 、X、R 3 And R is 5 Has the meaning as described in the present invention. The compound (C) and the substituted pyrazole (F1) are subjected to esterification reaction at the temperature of 0-35 ℃ to obtain a compound (F); the compound (F) and the trimethylcyano silane undergo Fries rearrangement reaction at the temperature of 10-40 ℃ to obtain the target compound (G).
Intermediate 1: preparation of methyl 2, 4-dichloro-3- (bromomethyl) benzoate
Step 1: preparation of 2, 4-dichloro-3-methylacetophenone
To a single flask was added aluminum chloride (49.68 g,372.6 mmol) and 2, 6-dichlorotoluene (50 g,310.5 mmol), stirred at room temperature, then acetyl chloride (26.81 g,341.6 mmol) was slowly added dropwise, heated to 40℃and reacted for 2h, and TLC monitored the completion of the starting material reaction. The system was slowly poured into ice water (500 mL), acidified with dilute hydrochloric acid (1 m,30 mL), extracted with dichloromethane (150 mL x 3), dried over anhydrous sodium sulfate and concentrated to give 60g of a colorless oil in 95% yield.
Step 2: preparation of 2, 4-dichloro-3-methylbenzoic acid
To a single-necked flask, 2, 4-dichloro-3-methylacetophenone (30 g,147.7 mmol) and 1, 4-dioxane (100 mL) were added, the temperature was raised to 80℃and sodium hypochlorite solution (5% available chlorine 300 mL) was added dropwise, the temperature was maintained under stirring for 5h, and TLC monitoring of the completion of the reaction of the starting materials. After returning to room temperature, the phases were separated, the lower solution was separated, acidified to ph=2 with concentrated hydrochloric acid, suction filtered, the filter cake was washed with water (100 ml x 3) and dried at 50 ℃ to give 22g of a white solid with a yield of 74%.
Step 3: preparation of methyl 2, 4-dichloro-3-methylbenzoate
To a single-necked flask, 2, 4-dichloro-3-methylbenzoic acid (20 g,97.54 mmol) and methanol (80 mL) were added, the temperature was lowered to 0℃and SOCl was slowly added dropwise 2 (13.85 mL,195.0 mmol) was added dropwise, and the mixture was reacted at 60℃for 10 hours. The vast majority of methanol was removed by distillation under reduced pressure, the remaining mass was slowly added to ice water (200 mL) and ph=8 was adjusted with saturated sodium bicarbonate, extracted with dichloromethane (50 mL x 3), dried over anhydrous sodium sulfate, concentrated organic phase, recrystallized to give 16.3g of white solid in 76% yield.
Step 4: preparation of methyl 2, 4-dichloro-3- (bromomethyl) benzoate
To a single flask was added methyl 2, 4-dichloro-3-methylbenzoate (12 g,54.78 mmol), NBS (13.65 g,76.69 mmol), carbon tetrachloride (60 mL) and AIBN (1.8 g,10.92 mmol), nitrogen blanket, stirring at 78℃for 3.5h and TLC monitoring was complete. Cooling, suction filtration, washing the filter cake with carbon tetrachloride (20 mL x 3), vacuum distillation to remove carbon tetrachloride, and recrystallization to obtain 15g of white solid with 92% yield.
Intermediate 2: preparation of methyl 2-chloro-3-bromomethyl-4-methylsulfonylbenzoate
Step 1: preparation of 2-methyl-3-chloroanisole
To a single vial was added sodium methyl mercaptan solid (10.05 g,143.46 mmol) and DMSO (50 mL), then 2, 4-dichlorotoluene (21.00 g,130.41 mmol) was added, the temperature was raised to 100deg.C, the temperature was maintained under stirring overnight, and TLC monitored for reaction completion. The system was poured into water (300 mL), extracted with ethyl acetate (100 ml×3), the organic phases were combined, washed with saturated brine (200 mL), dried over anhydrous sodium sulfate, and concentrated to give 20g of oil in 88% yield.
Step 2: preparation of 2-chloro-3-acetyl-6-methylthiotoluene
To a single flask was added aluminum chloride (18.53 g,138.98 mmol), 1, 2-dichloroethane (80 mL) and 2-methyl-3-chloroanisole (20 g,115.83 mmol), kept stirring at 0deg.C, then acetyl chloride (10.09 g,128.54 mmol) was added dropwise, the reaction was resumed at room temperature overnight after the addition, and TLC was monitored to be complete. The system was slowly poured into ice water (400 mL), extracted with dichloromethane (200 mL x 2), dried over anhydrous sodium sulfate, and concentrated to give 20g of oily substance, which was used in the next reaction without purification in 80.4% yield.
Step 3: preparation of 2-chloro-3-acetyl-6-methylsulfonylmethylbenzene
To a single-necked flask, 2-chloro-3-acetyl-6-methylthiotoluene (20 g,93.15 mmol), sodium tungstate (2 g,5.32 mmol) and isopropyl alcohol (100 mL) were added, the temperature was raised to 50℃and hydrogen peroxide (100 mL, wt=30%) was slowly added dropwise, the temperature was maintained for reaction for 6 hours, and the reaction was completed by TLC. The isopropanol was distilled off under reduced pressure, water (200 mL) was added, suction filtration, water washing (50 mL. Times.2) and drying gave 18g of a white solid in 79% yield.
Step 4: preparation of 2-chloro-3-methyl-4-methylsulfonylbenzoic acid
To a single-necked flask, 2-chloro-3-acetyl-6-methylsulfonylmethyltoluene (60 g,243.02 mmol) and 1, 4-dioxane (200 mL) were added, the temperature was raised to 80℃and sodium hypochlorite solution (500 mL, available chlorine: 6% -14%) was slowly added dropwise, the temperature was maintained for 6 hours, and the TLC detection reaction was complete. Cooled to room temperature, the lower solution was separated, extracted with ethyl acetate (100 mL), the aqueous phase was acidified to ph=3 with concentrated hydrochloric acid, a white solid precipitated, filtered off with suction, washed with water (50 mL x 2), dried to give 48g of a white solid in 80% yield.
Step 5: preparation of methyl 2-chloro-3-methyl-4-methylsulfonylbenzoate
To a single-necked flask, 2-chloro-3-methyl-4-methylsulfonylbenzoic acid (30.0 g,120.64 mmol) and methanol (200 mL) were added, followed by stirring at 0℃and then dropwise addition of thionyl chloride (28.70 g,241.23 mmol). After the completion of the dripping, the temperature is raised to 60 ℃ for reaction for 5 hours. Excess thionyl chloride was quenched by dropwise addition of water (20 mL), methanol was distilled off under reduced pressure, water (200 mL) was added, suction filtration was performed, and the filter cakes were washed with saturated sodium bicarbonate solution (50 mL. Times.2), water (100 mL) and dried, to give 27.5g of a white solid in 90% yield.
Step 6: preparation of methyl 2-chloro-3-bromomethyl-4-methylsulfonylbenzoate
To a single vial was added methyl 2-chloro-3-methyl-4-methylsulfonylbenzoate (27.5 g,104.68 mmol), NBS (26.08 g,146.53 mmol), AIBN (3.44 g,20.95 mmol) and CCl 4 (140 mL), nitrogen, and the reaction was warmed to 78deg.C for 5h, and TLC monitored for completion. Filtering to remove insoluble substances in the system, and using CCl 4 The filter cake was washed (30 ml x 2), the organic phase was concentrated and recrystallized (PE/EtOAc (V/V) =5/1) to give 25g of white solid in 70% yield.
Examples
Example 1: 4-chloro-N- (2-chloro-3- (2-hydroxy-6-oxocyclohex-1-enecarbonyl) -6- (methylsulfonyl) benzyl) -N-cyclopropylbenzamide
Step 1: synthesis of methyl 2-chloro-3- ((cyclopropylamino) methyl) -4- (methylsulfonyl) benzoate
To a single-necked flask, cyclopropylamine (1.34 g,23.4 mmol), potassium carbonate (1.62 g,11.7 mmol) and N, N-dimethylformamide (30 mL) were successively added, followed by stirring for 30 minutes and then adding methyl 2-chloro-3-bromomethyl-4-methylsulfonylbenzoate (2.00 g,5.9 mmol) to react at room temperature for 24 hours. TLC monitored the reaction was complete and stopped. Water (100 mL) was added to the system for dilution, and ethyl acetate was used for extraction (100 mL. Times.3), and the organic phases were combined and washed with saturated brine (50 mL. Times.2). The organic phase was dried over anhydrous sodium sulfate and concentrated, and subjected to column chromatography (eluent: n-hexane/ethyl acetate (v/v) =4/1) to obtain 1.69g of a white solid in 90% yield.
MS(ES-API,pos.ion)m/z:318.0[M+H] + .
Step 2: synthesis of methyl 2-chloro-3- ((4-chloro-N-cyclopropylbenzamido) methyl) -4- (methylsulfonyl) benzoate
To a single-necked flask was added methyl 2-chloro-3- ((cyclopropylamino) methyl) -4- (methylsulfonyl) benzoate (2.00 g,6.3 mmol), triethylamine (1.27 g,12.6 mmol) and methylene chloride (30 mL), followed by slowly dropwise addition of p-chlorobenzoyl chloride (1.32 g,7.6 mmol) and reaction at room temperature for 3 hours. The reaction was stopped after TLC monitoring complete reaction. The reaction was quenched with water (30 mL), then the organic phase was separated, recovered, concentrated, and column chromatographed (eluent: n-hexane/ethyl acetate (v/v) =6/1) to give 2.44g of a white solid in 85% yield.
Step 3: synthesis of 2-chloro-3- ((4-chloro-N-cyclopropylbenzamido) methyl) -4- (methylsulfonyl) benzoic acid
In a single-necked flask was added methyl 2-chloro-3- ((4-chloro-N-cyclopropylbenzamido) methyl) -4- (methylsulfonyl) benzoate (2.5 g,5.48 mmol), tetrahydrofuran (10 mL), ethanol (10 mL), water (10 mL) and lithium hydroxide monohydrate (0.28 g,6.57 mmol) and the reaction was stirred at room temperature until the starting materials were fully reacted. After stopping the reaction, the solvent was stripped off, the residue was dissolved with water (20 mL) and extracted with dichloromethane (20 mL. Times.2), and the aqueous phase was acidified to pH about 4 with hydrochloric acid (1 mol/L). A white solid precipitated, and after standing, suction filtration was performed, and the cake was washed with water (20 mL. Times.2) and dried to give 1.99g of a white solid, with a yield of 82%.
MS(ES-API,pos.ion)m/z:442.0[M+H] + .
Step 4: synthesis of 2-chloro-3- ((4-chloro-N-cyclopropylbenzamido) methyl) -4- (methylsulfonyl) benzoyl chloride
To a single flask was added 2-chloro-3- ((4-chloro-N-cyclopropylbenzamido) methyl) -4- (methylsulfonyl) benzoic acid (800 mg,1.8 mmol) and super-dry dichloromethane (30 mL), oxalyl chloride (689 mg,5.44 mmol) and DMF (12 mg,0.17 mmol) were added under ice bath and reacted at room temperature for 3 hours. The system was dried and ultra-dry dichloromethane (10 mL) was added to give 2-chloro-3- ((4-chloro-N-cyclopropylbenzamide) methyl) -4- (methylsulfonyl) benzoyl chloride solution.
Step 5: synthesis of 3-oxocyclohex-1-en-1-yl 2-chloro-3- ((4-chloro-N-cyclopropylbenzamido) methyl) -4- (methylsulfonyl) benzoate
To a single vial was added 1, 3-cyclohexanedione (234 mg,5.1 mmol), dried dichloromethane (20 mL) and triethylamine (351 mg,3.5 mmol), stirred at 0deg.C, then the 2-chloro-3- ((4-chloro-N-cyclopropylbenzamide) methyl) -4- (methylsulfonyl) benzoyl chloride solution obtained in step 4. After the reaction was completed by TLC monitoring, the reaction was warmed to room temperature for 3 hours, and then washed with a saturated sodium hydrogen carbonate solution (20 mL), a saturated brine (20 mL), and the organic phase was concentrated and subjected to column chromatography (eluent: n-hexane/ethyl acetate (v/v) =5/2) to give 700mg of a white solid.
Step 6: synthesis of 4-chloro-N- (2-chloro-3- (2-hydroxy-6-oxocyclohex-1-enecarbonyl) -6- (methylsulfonyl) benzyl) -N-cyclopropylbenzamide
To a single vial was added 3-oxocyclohex-1-en-1-yl 2-chloro-3- ((4-chloro-N-cyclopropylbenzamido) methyl) -4- (methylsulfonyl) benzoate (700 mg,1.30 mmol), acetonitrile (30 mL) and triethylamine (264 mg,2.61 mmol), stirred at room temperature, followed by trimethylcyanosilane (25 mg,0.26 mmol). The reaction was carried out at room temperature for 24h, and tlc monitored the reaction was complete. The system was acidified with glacial acetic acid (1 mL), stirred at room temperature for 30min, the organic solvent was removed from the system, dissolved in water (20 mL), extracted with dichloromethane (20 mL x 2), and purified by column chromatography (eluent: dichloromethane/methanol (v/v) =50/1) to give 400mg of white solid in 57% yield.
MS(ES-API,pos.ion)m/z:536.1[M+H] + ；
1 H NMR(400MHz,CDCl 3 )δ8.16(d,J＝8.1Hz,1H),7.54(d,J＝8.3Hz,2H),7.42–7.22(m,4H),5.34(d,J＝30.8Hz,2H),3.26(s,3H),2.83(t,J＝6.0Hz,2H),2.69(s,1H),2.44(t,J＝6.1Hz,2H),2.11–2.04(m,2H),0.65–0.40(m,4H).
Example 2: synthesis of N- (2-chloro-3- (5-hydroxy-1, 3-dimethyl-1H-pyrazole-4-carbonyl) -6- (methylsulfonyl) benzyl) -N-cyclopropylcyclopropane carboxamide
Step 1: synthesis of methyl 2-chloro-3- ((N-cyclopropylcyclopropanecarboxamide) methyl) -4- (methylsulfonyl) benzoate
To a single vial was added methyl 2-chloro-3- ((cyclopropylamino) methyl) -4- (methylsulfonyl) benzoate (2.00 g,6.3 mmol), triethylamine (1.27 g,12.6 mmol) and dichloromethane (30 mL), followed by slow dropwise addition of p-cyclopropylcarboxychloride (0.79 g,7.6 mmol) for 3 hours at room temperature. The reaction was stopped after TLC monitoring complete reaction. The reaction was quenched with water (30 mL), then the organic phase was separated, recovered, concentrated, and column chromatographed (eluent: n-hexane/ethyl acetate (v/v) =6/1) to give 2.30g of a white solid in 94% yield.
Step 2: synthesis of 2-chloro-3- ((N-cyclopropylcyclopropanecarboxamide) methyl) -4- (methylsulfonyl) benzoic acid
In a single-necked flask was added methyl 2-chloro-3- ((N-cyclopropylcyclopropanecarboxamide) methyl) -4- (methylsulfonyl) benzoate (2.30 g,5.96 mmol), tetrahydrofuran (10 mL), ethanol (10 mL), water (10 mL) and lithium hydroxide monohydrate (0.30 g,7.15 mmol), and the reaction was stirred at room temperature until the starting materials were fully reacted. After stopping the reaction, the solvent was stripped off, the residue was dissolved with water (20 mL) and extracted with dichloromethane (20 mL. Times.2), and the aqueous phase was acidified to pH about 4 with hydrochloric acid (1 mol/L). A white solid precipitated, which was left standing, suction-filtered, and the cake was washed with water (20 mL. Times.2) and dried to give 1.50g of a white solid in 67% yield.
MS(ES-API,pos.ion)m/z:372.0[M+H] + .
Step 3: synthesis of 2-chloro-3- ((N-cyclopropylcyclopropanecarboxamide) methyl) -4- (methylsulfonyl) benzoyl chloride
To a single flask was added 2-chloro-3- ((N-cyclopropylcyclopropanecarboxamide) methyl) -4- (methylsulfonyl) benzoic acid (500 mg,1.34 mmol) and ultra-dry dichloromethane (30 mL), oxalyl chloride (512 mg,4.03 mmol) and DMF (12 mg,0.17 mmol) were added under ice bath and reacted at room temperature for 3 hours. The system was dried and ultra-dry dichloromethane (10 mL) was added to give 2-chloro-3- ((N-cyclopropylcyclopropanecarboxamide) methyl) -4- (methylsulfonyl) benzoyl chloride solution.
Step 4: synthesis of 1, 3-dimethyl-1H-pyrazol-5-yl 2-chloro-3- ((N-cyclopropylcyclopropanecarboxamide) methyl) -4- (methylsulfonyl) benzoate
1, 3-dimethyl-5-hydroxypyrazole (224 mg,2.00 mmol) was dissolved in ultra-dry dichloromethane (20 mL), then triethylamine (264 mg,2.66 mmol) was added to the reaction solution, cooled to 0℃and a 2-chloro-3- ((N-cyclopropylcyclopropanecarboxamide) methyl) -4- (methylsulfonyl) benzoyl chloride solution was added to the reaction solution, and reacted at room temperature for 3h, and TLC monitored the completion of the starting material reaction. To the reaction solutionSaturated sodium bicarbonate solution (50 mL), dichloromethane extraction (50 mL. Times.3), combined organic phases, anhydrous Na 2 SO 4 Drying, concentration, column chromatography (eluent: PE/EtOAc (v/v) =100/30) gave 500mg of white solid in 80% yield.
Step 5: synthesis of N- (2-chloro-3- (5-hydroxy-1, 3-dimethyl-1H-pyrazole-4-carbonyl) -6- (methylsulfonyl) benzyl) -N-cyclopropylcyclopropane carboxamide
To a single vial was added 1, 3-dimethyl-1H-pyrazol-5-yl 2-chloro-3- ((N-cyclopropylcyclopropanecarboxamide) methyl) -4- (methylsulfonyl) benzoate (500 mg,1.07 mmol), acetonitrile (30 mL) and triethylamine (217 mg,2.15 mmol), stirred at room temperature, and then trimethylcyanosilane (25 mg,0.26 mmol). The reaction was carried out at room temperature for 24h, and tlc monitored the reaction was complete. The system was acidified with glacial acetic acid (1 mL), stirred at room temperature for 30min, the organic solvent was removed from the system, dissolved in water (20 mL), extracted with dichloromethane (20 mL x 2), and purified by column chromatography (eluent: dichloromethane/methanol (v/v) =50/1) to give 330mg of a pale grey solid in 66% yield.
MS(ES-API,pos.ion)m/z:466.1[M+H] + ；
1 H NMR(400MHz,CDCl 3 )δ8.16(d,J＝8.1Hz,1H),7.36(d,J＝8.1Hz,1H),5.05(s,2H),3.64(s,3H),3.35(s,3H),3.05(m,1H),2.20–2.13(m,1H),1.69(s,3H),1.04–0.89(m,4H),0.79(m,4H).
The synthesis method of reference examples 1-2, in combination with the synthesis schemes one and two of the present invention, employed the corresponding starting materials and conditions, gave the target compounds of Table 1.
TABLE 1
Biological embodiment
The raw medicine with a certain mass is weighed by an analytical balance (0.0001 g), dissolved by a proper amount of DMF and then diluted by a certain volume of distilled water containing 1 permillage of Tween-80 emulsifier for standby. Taking a flowerpot with the length and the width of 7.0cm, filling soil to 3/4 parts, directly sowing pretreated weed target seeds, covering soil by about 0.5cm, spraying when seedlings grow to a proper age stage, naturally airing the pesticide liquid after the pesticide application, transferring the seedlings into a greenhouse for conventional culture, and checking the activity (%) of weeds after 21 days; wherein 0 indicates no injury or normal growth process and 100 indicates complete death of at least the aerial parts. The test results are shown in tables 2-4.
TABLE 2 Activity of the inventive Compounds against Abutilon at 300g/ha
Examples Abutilon (Abutilon) Examples Abutilon (Abutilon)
Example 2 87 Example 4 90
Example 7 90 Example 8 92
Example 9 82 Example 11 94
Example 13 96 Example 14 87
Example 17 96
TABLE 3 Activity of the inventive Compounds against Portulaca oleracea at 300g/ha
Examples Purslane (Portulaca oleracea L.) L Examples Purslane (Portulaca oleracea L.) L
Example 3 98 Example 8 98
Example 11 85 Example 12 95
Example 13 98 Example 14 98
Example 15 85
TABLE 4 Activity of the inventive Compounds against barnyard grass at 300g/ha
Examples Barnyard grass Examples Barnyard grass
Example 2 92 Example 7 80
Example 11 95 Example 17 80
The results in tables 2-4 show that the compound of the invention has good control effect on abutilon, purslane and barnyard grass at 300 g/ha.
The compound has good control effect on broadleaf weeds (such as abutilon, amaranthus retroflexus, zinnia, intestine and purslane) and grassy weeds (such as crabgrass, barnyard grass, ryegrass and green bristlegrass). The herbicide composition is safe to crops, quick in pesticide effect, better in weed control effect than commercial herbicides and benzoyl compounds with similar structures, and has good application prospects.

Claims (4)

1. A compound which is a compound having one of the following structures or a salt thereof:
2. A composition comprising the compound of claim 1.
3. Use of a compound according to claim 1 or a composition according to claim 2 for controlling abutilon, purslane and/or barnyard grass.
4. A method of controlling weed growth in a useful plant comprising applying to the locus of a weed an effective amount of a compound according to claim 1 or a composition according to claim 2, wherein the weed is abutilon, purslane and/or barnyard grass.
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Publication number Priority date Publication date Assignee Title
US6432881B1 (en) * 1997-08-07 2002-08-13 Basf Aktiengesellschaft 2-benzoylcyclohexane-1,3-dione as herbicides
CN1524075A (en) * 2001-05-09 2004-08-25 �ݶ�ũ�����ѧ�ɷݹ�˾ Substitued arylketones
CN1649830A (en) * 2002-03-05 2005-08-03 拜尔农作物科学股份公司 Substituted aryl ketones

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Publication number Priority date Publication date Assignee Title
US6432881B1 (en) * 1997-08-07 2002-08-13 Basf Aktiengesellschaft 2-benzoylcyclohexane-1,3-dione as herbicides
CN1524075A (en) * 2001-05-09 2004-08-25 �ݶ�ũ�����ѧ�ɷݹ�˾ Substitued arylketones
CN1649830A (en) * 2002-03-05 2005-08-03 拜尔农作物科学股份公司 Substituted aryl ketones

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