CN115460921A - Fungicidal halomethyl ketones and hydrates and mixtures thereof - Google Patents

Fungicidal halomethyl ketones and hydrates and mixtures thereof Download PDF

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Publication number
CN115460921A
CN115460921A CN202180031728.9A CN202180031728A CN115460921A CN 115460921 A CN115460921 A CN 115460921A CN 202180031728 A CN202180031728 A CN 202180031728A CN 115460921 A CN115460921 A CN 115460921A
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Prior art keywords
radical
group
independently
methyl
alkyl
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Inventor
R·J·帕斯特里斯
T·C·麦克马洪
王恒斌
A·D·小克鲁斯
L·希埃
E·W·里德
S·吉塔博伊纳
R·P·雷迪
S·R·乌帕拉帕蒂
陈羽仲
B·维加-希门尼斯
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FMC Corp
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FMC Corp
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    • 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
    • A—HUMAN NECESSITIES
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    • 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
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    • A01N37/40—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • 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
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A—HUMAN NECESSITIES
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
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    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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Abstract

Disclosed is a fungicidal composition comprising: (a) At least one compound selected from the group consisting of compounds having formula 1, including all geometric and stereoisomers, tautomers, a-oxides, and salts thereof, wherein E, L, J, aAnd T is as defined in the disclosure; and (b) at least one additional fungicidal compound. Also disclosed is a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or plant seed, a fungicidally effective amount of a compound of formula 1, an a-oxide or salt thereof (e.g., as a component of the aforementioned composition). Also disclosed is a composition comprising: (a) At least one compound selected from the group consisting of compounds having formula 1 described above, a-oxides, and salts thereof; and at least one invertebrate pest control compound or agent.

Description

Fungicidal halomethyl ketones and hydrates and mixtures thereof
Technical Field
This invention relates to certain halomethyl ketone and hydrate derivatives, N-oxides, and salts thereof, and to mixtures and compositions comprising such halomethyl ketone and hydrate derivatives and methods of using such derivatives and mixtures and compositions thereof as fungicides.
Background
Control of plant diseases caused by fungal plant pathogens is extremely important to achieve high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal and fruit crops can cause significant yield losses and thereby result in increased consumer costs. In addition to often being highly destructive, plant diseases can be difficult to control and can develop resistance to commercial fungicides. Many products are commercially available for these purposes, but there is a continuing need for new fungicidal compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action. In addition to the introduction of new fungicides, combinations of fungicides are often used to promote disease control, broaden the spectrum of control and delay the development of resistance. In addition, certain rare fungicide combinations exhibit a greater than additive (i.e., synergistic) effect to provide a commercially important level of plant disease control. The advantages of a particular combination of fungicides are recognized in the art as being different, depending on factors such as: the particular plant species and plant disease to be treated, and whether the plant is treated before or after infection with a fungal plant pathogen. Thus, there is a need for new advantageous combinations to provide various options to best meet specific plant disease control needs. Such combinations have now been found.
Disclosure of Invention
The present invention relates to a fungicidal composition (i.e. combination, mixture) comprising
(a) At least one compound selected from the group consisting of compounds having formula 1 (including all stereoisomers), tautomers, N-oxides, and salts thereof:
Figure BDA0003913878900000021
wherein
T is selected from the group consisting of:
Figure BDA0003913878900000022
wherein the key extending to the left is attached to a;
R 1 is CF 3 、CHF 2 、CCl 3 、CHCl 2 、CF 2 Cl、CFCl 2 Or CHFCl;
w is O, S or NR 3 ；
R 3 Is H, cyano, nitro, C (= O) OH, benzyl, C 1 -C 4 Alkyl radical, C 2 -C 4 Alkylcarbonyl group, C 2 -C 4 Halogenated alkylcarbonyl, OR 3a Or NR 3b R 3c ；
R 3a Is H, benzyl, C 1 -C 4 Alkyl radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 A haloalkylcarbonyl group;
R 3b is H, C 1 -C 4 Alkyl radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 A haloalkylcarbonyl group;
R 3c is H or C 1 -C 4 An alkyl group; or
R 3b And R 3c Together form a 4-to 6-membered fully saturated heterocyclic ring, each ring containing, in addition to the linking nitrogen atom, ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, each ring optionally substituted with up to 2 methyl groups;
x is O, S or NR 5a ；
Y is O, S or NR 5b ；
R 5a And R 5b Each independently is H, hydroxy or C 1 -C 4 An alkyl group;
R 2a and R 2b Each independently is H, C 1 -C 4 Alkyl radical, C 2 -C 4 Alkenyl radical, C 3 -C 15 Trialkylsilyl group, C 3 -C 15 Halogenotrialkylsilyl, (CR) 4a R 4b ) p -OH、(CR 4a R 4b ) p -SH、(CR 4a R 4b ) p -Cl or (CR) 4a R 4b ) p -Br; or alternatively
R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-to 7-membered saturated ring containing, in addition to these atoms X and Y, a ring member selected from carbon atoms, wherein up to 2 carbon atom ring members are independently selected from C (= O) and C (= S), the ring being optionally substituted on a carbon atom ring member with up to 2 atoms independently selected from halogen, cyano, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy and C 1 -C 2 Substituted with a halo alkoxy group;
R 2c is C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Halogenated alkenyl group, C 2 -C 4 Alkynyl, C 2 -C 4 Haloalkynyl or trifluoromethylsulfonyl, each of which is optionally substituted by up to 2 substituents independently selected from cyano, hydroxy, SC ≡ N and C 1 -C 2 Substituent of alkoxy;
R 2d is H, cyano, halogen or C 1 -C 4 An alkyl group;
each R 4a And R 4b Independently is H or C 1 -C 4 An alkyl group;
p is 2 or 3;
when T is T-1 or T-2, then A is A 1 -A 2 -CR 6a R 6b Wherein A is 1 Is linked to J, and CR 6a R 6b Is linked to T;
when T is T-3, then A is A 1 -A 2 Wherein A is 1 Is connected to J, and A 2 Is linked to T;
A 1 is CR 6c R 6d 、N(R 7a ) O or S;
A 2 is a direct bond, CR 6e R 6f 、N(R 7b ) O or S;
R 6a 、R 6b 、R 6c 、R 6d 、R 6e and R 6f Each independently is H, cyano, hydroxy, halogen, C (= O) OCH 3 Or C 1 -C 4 An alkyl group;
R 7a and R 7b Each independently is H, C (= O) H, cyano, C 1 -C 4 Alkyl or C 2 -C 4 An alkylcarbonyl group;
j is selected from the group consisting of:
Figure BDA0003913878900000031
Figure BDA0003913878900000041
wherein the key extending to the left is attached to L and the key extending to the right is attached to a;
each R 8 Independently is F, cl, I, br, cyano, methyl, trifluoromethyl or methoxy;
q is 0, 1, 2, 3 or 4;
l is (CR) 9a R 9b ) n ；
Each R 9a And R 9b Independently H, halogen, cyano, hydroxy, nitro, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy or C 1 -C 3 A haloalkoxy group;
n is 0, 1, 2 or 3;
e is C 1 -C 6 Alkyl or C 1 -C 6 A haloalkyl group; or alternatively
E is E 1 Or E 2 ；
E 1 Is amino, cyano, hydroxyl, nitro, CH (= O), C (= O) OH, C (= O) NH 2 、C(＝S)NH 2 、OC(＝O)NH 2 、OC(＝S)NH 2 、NHC(＝O)NH 2 、NHC(＝S)NH 2 、SC≡N、-CH＝NNHC(＝O)OC 1 -C 6 Alkyl or-N (OCH) 3 )C(＝O)C 1 -C 6 An alkyl group; or alternatively
E 1 Is C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkylthio radical, C 2 -C 6 Alkenylthio radical, C 2 -C 6 Alkynylthio, C 1 -C 6 Alkylsulfinyl radical, C 2 -C 6 Alkenylsulfinyl, C 2 -C 6 Alkynylsulfinyl group, C 1 -C 6 Alkylsulfonyl radical, C 2 -C 6 Alkenylsulfonyl radical, C 2 -C 6 Alkynylsulfonyl, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkenylsulfonylamino group, C 2 -C 6 Alkynylsulfonylamino, C 1 -C 6 Alkylaminosulfonyl radical, C 2 -C 6 Dialkylaminosulfonyl radical, C 2 -C 6 Alkenylaminosulfonyl radical, C 2 -C 6 Alkynylaminosulfonyl radical, C 1 -C 6 Alkylamino sulfonylamino group, C 2 -C 6 Alkenylaminosulfonylamino group, C 2 -C 6 Alkynyl aminosulfonylamino, C 2 -C 6 Alkylcarbonyl group, C 3 -C 6 Alkenylcarbonyl group, C 3 -C 6 Alkynyl carbonyl group, C 2 -C 6 Alkylaminocarbonyl radical, C 3 -C 6 Alkenylaminocarbonyl group, C 3 -C 6 Alkynyl aminocarbonyl, C 2 -C 6 Alkylcarbonylamino, C 3 -C 6 Alkenylcarbonylamino group, C 3 -C 6 Alkynyl carbonylamino group, C 2 -C 6 Alkylamino carbonylamino group, C 3 -C 6 Alkenylaminocarbonylamino group, C 3 -C 6 Alkynyl aminocarbonylamino, C 2 -C 6 Alkylcarbonyloxy, C 3 -C 6 Alkenylcarbonyloxy, C 3 -C 6 Alkynyl carbonyloxy, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl, C 2 -C 6 Alkylamino carbonyloxy radical, C 3 -C 6 Alkenylaminocarbonyloxy, C 3 -C 6 Alkynyl aminocarbonyloxy, C 2 -C 6 Alkoxycarbonylamino group, C 3 -C 6 Alkenyloxycarbonylamino, C 3 -C 6 Alkynyloxycarbonylamino group, C 2 -C 6 Alkylamino (thiocarbonyl) oxy, C 3 -C 6 Alkenylamino (thiocarbonyl) oxy, C 3 -C 6 Alkynylamino (thiocarbonyl) oxy, C 2 -C 6 Alkoxy (thiocarbonyl) amino, C 3 -C 6 Alkenyloxy (thiocarbonyl) amino, C 3 -C 6 Alkynyloxy (thiocarbonyl) amino, C 2 -C 6 Alkyl (thiocarbonyl), C 2 -C 6 (alkylthio) carbonyl, C 3 -C 6 Alkenyl (thiocarbonyl), C 3 -C 6 (alkenylthio) carbonyl, C 3 -C 6 Alkynyl (thiocarbonyl), C 3 -C 6 (alkynylthio) carbonyl, C 2 -C 6 Alkylamino (thiocarbonyl), C 3 -C 6 Alkenylamino (thiocarbonyl), C 3 -C 6 Alkynylamino (thiocarbonyl), C 2 -C 6 Alkyl (thiocarbonyl) amino, C 2 -C 6 (alkylthio) carbonylamino, C 3 -C 6 Alkenyl (thiocarbonyl) amino, C 3 -C 6 (alkenylthio) carbonylamino group, C 3 -C 6 Alkynyl (thiocarbonyl) amino, C 3 -C 6 (alkynylthio) carbonylamino group, C 2 -C 6 Alkylamino (thiocarbonyl) amino, C 3 -C 6 Alkenylamino (thiocarbonyl) amino or C 3 -C 6 Alkynylamino (thiocarbonyl) amino wherein each carbon atom is optionally substituted by up to 1R 10a And up to 3 substituents independently selected from R 10b Substituted with the substituent(s);
R 10a is optionally selected from R by up to 3 11a Phenyl substituted with the substituent of (1); or a 5-to 6-membered heterocyclic ring containing a substituent selected from the group consisting ofRing members of carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, wherein up to 3 carbon atom ring members are independently selected from C (= O) and C (= S), and sulfur atom ring members are independently S (= O) u (＝NR 12 ) v Each ring is optionally substituted with up to 3 substituents independently selected from R on a carbon atom ring member 11a And independently selected from R on a nitrogen ring member 11b ；
Each R 10b Independently amino, cyano, halogen, hydroxy, nitro, SC ≡ N, -SH, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Halogenocycloalkyl, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 1 -C 4 Alkylthio radical, C 1 -C 4 Alkylsulfinyl radical, C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Haloalkylsulfonyl group, C 1 -C 4 Alkylamino radical, C 2 -C 4 Dialkylamino radical, C 2 -C 4 Alkylcarbonyl group, C 2 -C 4 Halogenoalkylcarbonyl group, C 2 -C 5 Alkoxycarbonyl group, C 2 -C 5 Halogenoalkoxycarbonyl, C 2 -C 5 Alkylaminocarbonyl or C 3 -C 5 A dialkylaminocarbonyl group;
each R 11a Independently halogen, hydroxy, cyano, amino, nitro, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, C 1 -C 4 Hydroxyalkyl, C 3 -C 6 Cycloalkyl, C 4 -C 7 Cycloalkylalkyl radical, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkynyloxy, C 2 -C 4 Alkoxyalkyl group, C 2 -C 6 Alkylcarbonyloxy, C 1 -C 4 Alkylthio radical, C 1 -C 4 Halogenoalkylthio, C 2 -C 6 Alkylcarbonylthio, C 1 -C 4 Alkylsulfinyl radical, C 1 -C 4 Halogenoalkylsulfinyl, C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Haloalkylsulfonyl, C 1 -C 4 Alkylsulfonyloxy, C 1 -C 4 Alkylamino radical, C 2 -C 8 Dialkylamino, C 3 -C 6 Cycloalkylamino, C 2 -C 4 Alkyl carbonyl, C 3 -C 5 Alkenyl carbonyl group, C 3 -C 5 Alkynyl carbonyl, C 4 -C 7 Cycloalkyl carbonyl, C 5 -C 8 Cycloalkylalkylcarbonyl, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 7 Alkenyloxycarbonyl radical, C 3 -C 7 Alkynyloxycarbonyl, C 4 -C 7 Cycloalkoxycarbonyl radical, C 5 -C 8 Cycloalkyl alkoxycarbonyl, C 2 -C 6 Alkylaminocarbonyl radical, C 3 -C 6 Alkenylaminocarbonyl group, C 3 -C 6 Alkynyl aminocarbonyl group, C 4 -C 7 Cycloalkylaminocarbonyl group, C 5 -C 8 Cycloalkylalkylaminocarbonyl radical, C 3 -C 8 Dialkylaminocarbonyl or C 3 -C 6 A trialkylsilyl group;
each R 11b Independently C (= O) H, C 1 -C 3 Alkyl radical, C 1 -C 3 Alkoxy radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 An alkoxycarbonyl group;
each R 12 Independently of one another H, cyano, C 1 -C 3 Alkyl or C 1 -C 3 A haloalkyl group;
each u and v is independently 0, 1 or 2, provided that the sum of u and v is 0, 1 or 2;
E 2 is G-Z, wherein Z is attached to L;
g is optionally selected from R by up to 3 13 Phenyl substituted with the substituent of (1); or
G is a 5-to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, each ring optionally substituted with up to 3 heteroatoms independently selected from R 13 Substituted with the substituent(s); or
G is a 3-to 7-membered non-aromatic ring or an 8-to 11-membered bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and optionally up to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, wherein up to 2 ring members are independently selected from C (= O), C (= S), S (= O), and S (= O) 2 Each ring or ring system is optionally substituted with up to 3 substituents independently selected from R 13 Substituted with a substituent of (1);
each R 13 Independently cyano, halogen, hydroxy, nitro, -SH, SF 5 、CH(＝O)、C(＝O)OH、NR 14a R 14b 、C(＝O)NR 14a R 14b 、C(＝O)C(＝O)NR 14a R 14b 、C(＝S)NR 14a R 14b 、C(R 15 )＝NR 16 、N＝CR 17 NR 18a R 18b or-U-V-Q; or C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 3 -C 7 Cycloalkyl radical, C 3 -C 7 Cycloalkenyl radical, C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, C 3 -C 7 Cycloalkoxy, C 1 -C 6 Alkylthio radical, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkyl amino sulfinyl, C 2 -C 6 Dialkylaminosulfinyl radical, C 1 -C 6 Alkylsulfonyloxy, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkyl carbonyl, C 4 -C 7 Cycloalkyl carbonyl group, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl, C 4 -C 7 Cycloalkoxycarbonyl radical, C 3 -C 6 Alkoxycarbonyl carbonyl group, C 2 -C 6 Alkylcarbonyloxy, C 4 -C 7 Cycloalkyl carbonyloxy, C 2 -C 6 Alkoxycarbonyloxy, C 4 -C 7 Cycloalkoxy-carbonyloxy, C 2 -C 6 Alkyl amino carbonyl oxygen radical, C 4 -C 7 Cycloalkyl aminocarbonyloxy, C 2 -C 6 Alkylcarbonylamino, C 4 -C 7 Cycloalkyl carbonylamino group, C 2 -C 6 Alkoxycarbonylamino group, C 4 -C 7 Cycloalkoxy-carbonylamino group, C 2 -C 6 Alkylamino carbonylamino group, C 4 -C 7 Cycloalkylaminocarbonylamino or C 2 -C 6 A dialkoxyphosphinyl group, each of which is optionally substituted by up to 3 radicals independently selected from R 19 Substituted with a substituent of (1);
Each R 14a Independently is H, cyano, hydroxy, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Haloalkenyl, C 2 -C 4 Alkynyl, C 2 -C 4 Halogenated alkynyl, C 1 -C 5 Alkoxy radical, C 2 -C 4 Alkoxyalkyl group, C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Haloalkylsulfonyl group, C 2 -C 4 Alkylthio alkyl, C 2 -C 4 Alkylsulfinylalkyl radical, C 2 -C 4 Alkylsulfonylalkyl group, C 2 -C 4 Alkylcarbonyl group, C 2 -C 4 Halogenoalkylcarbonyl group, C 4 -C 7 Cycloalkyl carbonyl group, C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkoxycarbonylalkyl, C 2 -C 5 Alkylaminocarbonyl or C 3 -C 5 A dialkylaminocarbonyl group;
each R 14b Independently of each other H, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl radical, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Halogenated alkynyl, C 1 -C 6 Hydroxyalkyl radical, C 2 -C 6 Cyanoalkyl, C 3 -C 8 Cycloalkyl radical, C 3 -C 8 Halogenocycloalkyl, C 3 -C 8 Cycloalkenyl radical, C 3 -C 8 Halogenated cycloalkenyl radical, C 4 -C 10 Alkyl cycloalkyl radical, C 4 -C 10 Cycloalkylalkyl radical, C 4 -C 10 Halocycloalkylalkyl radical, C 6 -C 14 Cycloalkyl, C 5 -C 10 Alkyl cycloalkyl alkyl, C 2 -C 6 Alkoxyalkyl group, C 2 -C 6 Haloalkoxyalkyl, C 4 -C 10 Cycloalkoxyalkyl radical, C 3 -C 8 Alkoxyalkoxyalkyl group, C 2 -C 6 Alkylthio alkyl, C 2 -C 6 Alkylsulfinylalkyl radical, C 2 -C 6 Alkylsulfonylalkyl, C 2 -C 6 Alkylaminoalkyl, C 2 -C 6 Haloalkyl aminoalkyl radical, C 3 -C 8 Dialkylaminoalkyl or C 4 -C 10 Cycloalkylaminoalkyl radicals, each optionally substituted by up to 1 substituent selected from the group consisting of cyano, hydroxy, nitro, C 2 -C 4 Alkylcarbonyl group, C 2 -C 4 Alkoxycarbonyl group, C 3 -C 15 Trialkylsilyl group, C 3 -C 15 Halo-trialkylsilyl and pyrimidinyl substituents; or alternatively
R 14a And R 14b Together form a 4-to 6-membered fully saturated heterocyclic ring containing, in addition to the linking nitrogen atom, ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, each ring optionally substituted with up to 3 heteroatoms independently selected from halogen and C 1 -C 3 Alkyl substituent substitution;
each R 15 Independently H, cyano, halogen, methyl, methoxy, methylthio or methoxycarbonylA group;
each R 16 Independently of the other is hydroxy or NR 20a R 20b (ii) a Or C 1 -C 4 Alkoxy radical, C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkynyloxy, C 2 -C 4 Alkylcarbonyloxy, C 2 -C 5 Alkoxycarbonyloxy, C 2 -C 5 Alkylamino carbonyloxy or C 3 -C 5 A dialkylaminocarbonyloxy group each optionally substituted with up to 1 substituent selected from cyano, halogen, hydroxy and C (= O) OH;
each R 17 Independently H, methyl, methoxy or methylthio;
each R 18a And R 18b Independently is H or C 1 -C 4 An alkyl group; or
R 18a And R 18b Together form a 5-to 6-membered fully saturated heterocyclic ring, each ring containing, in addition to the linking nitrogen atom, ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, each ring optionally substituted with up to 2 methyl groups;
Each R 19 Independently is amino, cyano, halogen, hydroxy, nitro, -SH, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Halogenocycloalkyl, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 2 -C 4 Alkoxyalkoxy radical, C 1 -C 4 Alkylthio radical, C 1 -C 4 Alkylsulfinyl radical, C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Haloalkylsulfonyl, C 2 -C 4 Alkylcarbonyl group, C 2 -C 4 Halogenoalkylcarbonyl group, C 2 -C 5 Alkoxycarbonyl group, C 1 -C 6 Alkylamino radical, C 2 -C 6 Dialkylamino, C 2 -C 5 Alkylaminocarbonyl radical, C 3 -C 5 Dialkylaminocarbonyl radicals、C 3 -C 5 Alkylthio alkylcarbonyl, C 3 -C 15 Trialkylsilyl group, C 3 -C 15 Halogenotrialkylsilyl, C (R) 21 )＝NOR 22 Or C (R) 23 )＝NR 24 ；
Each U is independently a direct bond, C (= O) O, C (= O) N (R) 25 ) Or C (= S) N (R) 26 ) Wherein the atom to the left is connected to G and the atom to the right is connected to V;
each V is independently a direct bond; or C 1 -C 6 Alkylene radical, C 2 -C 6 Alkenylene radical, C 3 -C 6 Alkynylene, C 3 -C 6 Cycloalkylene or C 3 -C 6 Cycloalkenylene, wherein up to 1 carbon atom is C (= O), each of which is optionally selected from halogen, cyano, nitro, hydroxy, C, independently, by up to 3 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy and C 1 -C 2 Substituted with a halo alkoxy group;
each Q is independently phenyl or phenoxy, each of which is optionally selected up to 2 independently from R 27 Substituted with the substituent(s); or
Each Q is independently a 5-to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, each ring optionally substituted with up to 2 heteroatoms independently selected from R 27 Substituted with the substituent(s); or
Each Q is independently a 3-to 7-membered non-aromatic heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, wherein up to 2 ring members are independently selected from C (= O), C (= S), S (= O), and S (= O) 2 Each ring is optionally substituted with up to 2 substituents independently selected from R 27 Substituted with a substituent of (1);
each R 20a Independently of each other H, C 1 -C 4 Alkyl or C 2 -C 4 An alkylcarbonyl group;
each R 20b Independently of one another H, cyano, C 1 -C 5 Alkyl radical, C 2 -C 5 Alkylcarbonyl group, C 2 -C 5 Halogenoalkylcarbonyl group, C 4 -C 7 Cycloalkyl carbonyl group, C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkoxycarbonylalkyl, C 2 -C 5 Alkylaminocarbonyl or C 3 -C 5 A dialkylaminocarbonyl group; or
R 20a And R 20b Together form a 5-to 6-membered fully saturated heterocyclic ring, each ring containing, in addition to the linking nitrogen atom, ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, each ring optionally substituted with up to 2 methyl groups;
Each R 21 And R 23 Independently of one another H, cyano, halogen, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 3 -C 6 Cycloalkyl or C 1 -C 3 An alkoxy group; or optionally up to 2 independently selected from halogen and C 1 -C 3 Phenyl substituted with a substituent of alkyl;
each R 22 Independently of each other H, C 1 -C 5 Alkyl radical, C 1 -C 5 Haloalkyl, C 2 -C 5 Alkenyl radical, C 2 -C 5 Haloalkenyl, C 2 -C 5 Alkynyl, C 3 -C 6 Cycloalkyl, C 3 -C 6 Halogenocycloalkyl, C 2 -C 5 Alkylcarbonyl or C 2 -C 5 An alkoxycarbonyl group; or
Each R 22 Is optionally selected from up to 2 independently selected from halogen and C 1 -C 3 Phenyl substituted with a substituent of alkyl; or a 5-to 6-membered fully saturated heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, each ring optionally substituted with up to 2 heteroatoms independently selected from up to 2Substituted with a substituent selected from the group consisting of halogen and C1-C3 alkyl;
each R 24 Independently of one another H, cyano, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 4 Alkoxy radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 An alkoxycarbonyl group;
each R 25 And R 26 Independently is H, cyano, hydroxy, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkylcarbonyl group, C 2 -C 4 Halogenoalkylcarbonyl group, C 2 -C 4 Alkoxycarbonyl or C 2 -C 4 A haloalkoxycarbonyl group;
each R 27 Independently halogen, cyano, hydroxy, nitro, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 1 -C 4 Alkoxy radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 An alkoxycarbonyl group;
z is a direct bond, O, S (= O) m 、N(R 28 )、C(＝O)、C(＝O)O、C(＝O)N(R 28 )、NR 28 C(＝O)、
N(R 28 )C(＝O)N(R 28 )、N(R 28 )C(＝S)N(R 28 )、OC(＝O)N(R 28 )、N(R 28 )C(＝O)O、S(O) 2 N(R 28 )、N(R 28 )S(＝O) 2 Or N (R) 28 )S(O) 2 N(R 28 ) Wherein the atom to the right is connected to L;
each R 28 Independently of each other H, C 1 -C 3 Alkyl radical, C 1 -C 3 Alkoxy radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 An alkoxycarbonyl group; and is provided with
m is 0, 1 or 2; and
(b) At least one additional fungicidal compound;
the premise is that:
(a) When A is 1 Is N (R) 7a ) O or S, then A 2 Is a direct bond or CR 6e R 6f (ii) a And is
(b) When A is 2 Is N (R) 7b ) O or S; then A is 1 Is CR 6c R 6d 。
The present invention also relates to a composition comprising: (a) At least one compound selected from the group consisting of the compounds having formula 1, N-oxides, and salts thereof described above; and at least one invertebrate pest control compound or agent.
The present invention also relates to a composition comprising one of the above-described compositions comprising component (a) and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
The present invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or plant seed, a fungicidally effective amount of one of the aforementioned compositions.
The above method may also be described as a method for protecting a plant or plant seed from a disease caused by a fungal pathogen, the method comprising applying to the plant (or portion thereof) or plant seed a fungicidally effective amount of one of the above compositions (either directly or through the environment of the plant or plant seed (e.g., the growth substrate)).
The invention also relates to a compound having the formula 1, a tautomer, an N-oxide, or a salt thereof, as described above.
Detailed Description
As used herein, the term "a" or "an" refers to a compound, the terms "comprising", "including", "having", "containing", "characterized by" or any other variant thereof, it is intended to cover non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.
The conjunctive phrase "consisting of \ 8230: \ 82305" excludes any unspecified elements, steps or components. If in the claims, this phrase will cause the claims to be closed, excluding materials other than those recited, except for impurities with which they are ordinarily associated. When the phrase "consisting of" \8230 ";" consists of "appears in a clause of the subject matter of the claims and not in the immediate preamble, this phrase limits only the elements set forth in this clause; the claims do not exclude other elements as a whole.
The conjunctive phrase "consisting essentially of 8230 \8230composition is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements in addition to those literally disclosed, provided that such additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of (8230); 8230consists of (intermediate) between (inclusive) and (consisting of (8230); 8230consists of (intermediate).
While applicants have defined the invention, or a portion thereof, in open-ended terms such as "comprising," it should be readily understood (unless otherwise indicated) that the specification should be interpreted to also describe the invention using the terms "consisting essentially of or" consisting of "\8230; composition of \8230;" 8230 ";" composition of \8230;.
Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, condition a or B is satisfied by any one of the following: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), and both a and B are true (or present).
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e., occurrences) of the element or component. Thus, "a" or "an" should be understood to include one or at least one and singular words of an element or component also include the plural unless the number clearly indicates the singular.
The term "agronomic" refers to the production of field crops such as those used for food and fiber, and includes the growth of maize (maize) or corn, soybean and other legumes, rice, cereals (e.g., wheat, oats, barley, rye, and rice), leafy vegetables (e.g., lettuce, cabbage, and other oilseed rape crops), fruit vegetables (e.g., tomatoes, peppers, eggplants, crucifers, and melon crops (cucurbits)), potatoes, sweet potatoes, grapes, cotton, fruits of trees (e.g., pome fruits (pomes), stone fruits (stones), and citrus fruits), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola (canola), sunflower, and olive).
The term "non-agronomic" refers to applications other than field crops, such as horticultural crops (e.g., greenhouses, nurseries, or ornamental plants not grown in the field), residential, agricultural, commercial, and industrial structures, turf (e.g., grasslands (sodfarm), rangelands, golf courses, lawns, sports fields, etc.), wood products, stored products, agriculture, forestry, and vegetation management, public health (i.e., human), and animal health (e.g., domestic animals such as pets, livestock, and poultry, non-domestic animals such as wildlife).
The term "crop vigor" refers to the growth rate or biomass accumulation of a crop plant. By "increase in vigor" is meant an increase in growth or biomass accumulation in a crop plant relative to an untreated control crop plant. The term "crop yield" refers to the return in quantity and quality of crop material obtained after harvesting a crop plant. By "increase in crop yield" is meant an increase in crop yield relative to an untreated control crop plant.
The term "biologically effective amount" refers to an amount of a biologically active compound (e.g., a compound having formula 1 or a mixture with at least one other fungicidal compound) sufficient to produce a desired biological effect when applied to (i.e., contacted with) the fungus to be controlled or its environment, or the plant, the seed from which the plant is growing, or the locus of the plant (e.g., a growth medium) to protect the plant from fungal disease or for other desired effects (e.g., increase plant vigor).
As referred to in the present disclosure and claims, a "plant" includes members of the kingdom plantae, in particular seed plants (normatopsid), in the full life stage, which includes young plants (e.g. germinating seeds developing into seedlings) and mature reproductive stages (e.g. plants that flower and bear seeds). A part of a plant includes geotropic members, such as roots, tubers, bulbs and corms, which typically grow below the surface of the growing medium (e.g., soil), and also members, such as leaves (including stems and leaves), flowers, fruits and seeds, which grow above the growing medium.
As referred to herein, the term "seedling", used alone or in combination of words, refers to a young plant developed from the embryo of a seed.
As referred to herein, the term "broadleaf," used alone or in words such as "broadleaf crop," refers to a dicot or dicot plant, a term used to describe a group of angiosperms characterized by an embryo having two cotyledons.
As referred to in this disclosure, the terms "fungal pathogen" and "fungal plant pathogen" include pathogens in the phyla Ascomycota (Ascomycota), basidiomycota (Basidiomycota) and Zygomycota (Zygomycota), and mycojust-like Oomycota (Oomycota) which are economically important pathogens of a broad spectrum of plant diseases affecting ornamental, turf, vegetable, field, cereal and fruit crops. In the context of the present disclosure, "protecting a plant from a disease" or "controlling a plant disease" includes prophylactic effects (interrupting the cycle of fungal infection, colonization, symptom development and spore production) and/or therapeutic effects (inhibiting colonization of plant host tissues).
As used herein, the term "mode of action" (MOA) is as defined by the Fungicide Resistance Action Committee (FRAC) and is used to differentiate fungicides according to their biochemical mode of action in the biosynthetic pathway of plant pathogens and their risk of resistance. The modes of action defined by FRAC include (a) nucleic acid metabolism, (B) cytoskeleton and motor proteins, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis or transport and membrane integrity or function, (G) sterol biosynthesis in the membrane, (H) cell wall biosynthesis, (I) melanin synthesis in the cell wall, (P) host plant defense induction, (U) unknown modes of action, (M) chemicals with multi-site activity and (BM) biologics with multiple modes of action. Each mode of action (i.e. letters a to BM) contains one or more subgroups (e.g. a includes subgroups A1, A2, A3 and A4) based on validated target sites of action alone, or in the case where the precise target site is unknown, on cross-resistance characteristics within or with other groups. Each of these subgroups (e.g., A1, A2, A3, and A4) is assigned an FRAC code as a number and/or letter. For example, subgroup A1 has a FRAC code of 4. Additional information about the target site and FRAC code may be obtained from a publicly available database maintained by FRAC, for example.
As used herein, the term "cross-resistance" refers to a phenomenon that occurs when a pathogen develops resistance to one fungicide and at the same time becomes resistant to one or more other fungicides. These other fungicides are typically, but not always, of the same chemical class or have the same target site of action, or can be detoxified by the same mechanism.
In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain and branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, and the different butyl, pentyl and hexyl isomers. "alkenyl" includes straight and branched chain olefins such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "alkenyl" also includes polyenes such as 1, 2-allenyl and 2, 4-hexadienyl. "alkynyl" includes straight and branched alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the different butynyl, pentynyl and hexynyl isomers. "alkynyl" may also include moieties made up of multiple triple bonds, such as 2, 5-hexadiynyl. "alkylene" means a straight or branched chain alkanediyl (alkenediyl). Examples of "alkylene" include CH 2 、CH 2 CH 2 、CH(CH 3 )、CH 2 CH 2 CH 2 、CH 2 CH(CH 3 ) And different butene isomers. "alkenylene" means a straight or branched chain alkenediyl group containing one ethylenic bond. Examples of "alkenylene" include CH = CH, CH 2 CH＝CH、CH＝C(CH 3 ) And different butenylene (butenylene) isomers. "Alkynylene" means a straight or branched alkynediyl group containing one triple bond. Examples of "alkynylene" include CH 2 C≡C、C≡CCH 2 And different butynylene, pentynylene or hexynylene isomers. The term "cycloalkylene" denotes a cycloalkyldiyl ring. Examples of "cycloalkylene" include cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl. The term "cycloalkenylene" denotes a cycloalkenediyl ring containing one olefinic bond. Examples of "cycloalkenylene" include cyclopropylenediyl and cyclopentenediyl.
"alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, and the different butoxy, pentoxy, and hexoxy isomers. "alkenyloxy" includes straight and branched chain alkenyl groups attached to and linked through an oxygen atom. Examples of "alkenyloxy" include H 2 C＝CHCH 2 O and CH 3 CH＝CHCH 2 And (O). "alkynyloxy" includes straight and branched chain alkynyl groups attached to and connected through an oxygen atom. Examples of "alkynyloxy" include HC ≡ CCH 2 O and CH 3 C≡CCH 2 O。
The term "alkylthio" includes straight and branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio and butylthio isomers. "Alkylsulfinyl" includes the two enantiomers of alkylsulfinyl. Examples of "alkylsulfinyl" include CH 3 S(＝O)、CH 3 CH 2 S(＝O)、CH 3 CH 2 CH 2 S(＝O)、(CH 3 ) 2 CHS (= O), and the different butylsulfinyl isomers. Examples of "alkylsulfonyl" include CH 3 S(＝O) 2 、CH 3 CH 2 S(＝O) 2 、CH 3 CH 2 CH 2 S(＝O) 2 、(CH 3 ) 2 CHS(＝O) 2 And different fromThe butylsulfonyl isomer of (a). "alkenylthio" includes straight and branched chain alkenyl groups attached to and linked through a sulfur atom. Examples of "alkenylthio" include H 2 C＝CHCH 2 S and CH 3 CH＝CHCH 2 And S. "Alkenylsulfinyl" includes both enantiomers of alkenylsulfinyl. Examples of "alkenylsulfinyl" include H 2 C＝CHCH 2 S(＝O)、CH 3 CH＝CHCH 2 S(＝O)、(CH 3 ) 2 C＝CHCH 2 S (= O). Examples of "alkenylsulfonyl" include CH 3 CH＝CHS(＝O) 2 、(CH 3 ) 2 C＝CHCH 2 S(＝O) 2 . "alkynylthio" includes straight and branched chain alkynyl groups attached to and linked through a sulfur atom. Examples of "alkynylthio" include HC ≡ CCH 2 S and CH 3 C≡CCH 2 And S. "Alkynylsulfinyl" includes both enantiomers of alkynylsulfinyl. Examples of "alkynylsulfinyl" include HC ≡ CCH 2 S(＝O)、CH 3 C≡CCH 2 S (= O). Examples of "alkynylsulfonyl" include CH 3 C≡CS(＝O) 2 、CH 3 C≡CCH 2 S(＝O) 2 。
"alkylthioalkyl" refers to an alkylthio substitution on an alkyl group. Examples of "alkylthioalkyl" include CH 3 SCH 2 、CH 3 SCH 2 CH 2 、CH 3 CH 2 SCH 2 、CH 3 CH 2 CH 2 SCH 2 And CH 3 CH 2 SCH 2 CH 2 (ii) a "Alkylsulfinylalkyl" and "alkylsulfonylalkyl" include the corresponding sulfoxides and sulfones, respectively.
"(alkylthio) carbonyl" represents a straight or branched alkylthio group bonded to a C (= O) moiety. Examples of "(alkylthio) carbonyl" include CH 3 SC(＝O)、CH 3 CH 2 CH 2 SC (= O) and (CH) 3 ) 2 CHSC (= O). The terms "(alkenylthio) carbonyl" and "(alkynylthio) carbonyl" are defined analogously. Examples of "(alkenylthio) carbonyl" include H 2 C＝CHCH 2 SC (= O) and CH 3 CH 2 CH = CHSC (= O). Examples of "(alkynylthio) carbonyl" include HC ≡ CCH 2 SC (= O) and CH 3 C≡CCH 2 SC(＝O)。
"alkyl (thiocarbonyl)" means a straight or branched alkyl group bonded to a C (= S) moiety. Examples of "alkyl (thiocarbonyl)" include CH 3 CH 2 C(＝S)、CH 3 CH 2 CH 2 C (= S) and (CH) 3 ) 2 CHCH 2 C (= S). The terms "alkenyl (thiocarbonyl)" and "alkynyl (thiocarbonyl)" are similarly defined. Examples of "alkenyl (thiocarbonyl)" include H 2 C＝CHCH 2 CH 2 C (= S) and CH 3 CH 2 CH = CHC (= S). Examples of "alkynyl (thiocarbonyl)" include HC ≡ CCH 2 CH 2 C (= S) and CH 3 C≡CCH 2 C(＝S)。
"alkylamino (thiocarbonyl)" means a straight or branched alkylamino group bonded to a C (= S) moiety. Examples of "alkylamino (thiocarbonyl)" include CH 3 NHC(＝S)、CH 3 CH 2 CH 2 NHC (= S) and (CH) 3 ) 2 CHNHC (= S). The terms "alkenylamino (thiocarbonyl)" and "alkynylamino (thiocarbonyl)" are defined similarly. Examples of "alkenylamino (thiocarbonyl)" include H 2 C＝CHCH 2 CH 2 NHC (= S) and CH 3 CH 2 CH = CHNHC (= S). Examples of "alkynylamino (thiocarbonyl)" include HC ≡ CCH 2 CH 2 NHC (= S) and CH 3 C≡CCH 2 NHC(＝S)。
"(alkylthio) carbonylamino" represents a straight or branched alkylthio group bonded to a C (= O) NH moiety. Examples of "(alkylthio) carbonylamino" include CH 3 CH 2 SC(＝O)NH、CH 3 CH 2 CH 2 SC (= O) NH and (CH) 3 ) 2 CHSC (= O) NH. The terms "(alkenylthio) carbonylamino" and "(alkynylthio) carbonylamino" are defined analogously. Examples of "(alkenylthio) carbonylamino" include H 2 C＝CHCH 2 SC (= O) NH and CH 3 CH = CHSC (= O) NH. Examples of "(alkynylthio) carbonylamino" includeIncluding HC ≡ CCH 2 CH 2 SC (= O) NH and CH 3 C≡CCH 2 CH 2 SC(＝O)NH。
"alkylamino" includes NH groups substituted with straight or branched chain alkyl groups. Examples of "alkylamino" include CH 3 CH 2 NH、CH 3 CH 2 CH 2 NH and (CH) 3 ) 2 CHCH 2 And (4) NH. Examples of "dialkylamino" include (CH) 3 ) 2 N、(CH 3 CH 2 CH 2 ) 2 N and CH 3 CH 2 (CH 3 ) And N is added. "alkylaminoalkyl" refers to alkylamino substitution on an alkyl group. Examples of "alkylaminoalkyl" include CH 3 NHCH 2 、CH 3 NHCH 2 CH 2 、CH 3 CH 2 NHCH 2 、CH 3 CH 2 CH 2 CH 2 NHCH 2 And CH 3 CH 2 NHCH 2 CH 2 。
"alkylcarbonyl" represents a straight or branched chain alkyl group bonded to a C (= O) moiety. Examples of "alkylcarbonyl" include CH 3 C(＝O)、CH 3 CH 2 CH 2 C (= O) and (CH) 3 ) 2 CHC (= O). The terms "alkenylcarbonyl" and "alkynylcarbonyl" are defined similarly. Examples of "alkenylcarbonyl" include H 2 C＝CHCH 2 C (= O) and CH 3 CH 2 CH = CHC (= O). Examples of "alkynylcarbonyl" include HC ≡ CCH 2 C (= O) and CH 3 C≡CCH 2 C (= O). "alkoxycarbonyl" includes a C (= O) moiety substituted with a straight or branched alkoxy group. Examples of "alkoxycarbonyl" include CH 3 OC(＝O)、CH 3 CH 2 OC(＝O)、CH 3 CH 2 CH 2 OC(＝O)、(CH 3 ) 2 CHOC (= O). The terms "alkenyloxycarbonyl" and "alkynyloxycarbonyl" are defined analogously. Examples of "alkenyloxycarbonyl" include H 2 C＝CHCH 2 OC (= O) and CH 3 CH 2 CH = CHOC (= O). Examples of "alkynyloxycarbonyl" include HC ≡ CCH 2 OC (= O) and CH 3 C≡CCH 2 OC(＝O)。
"alkylaminocarbonyl" represents a linear or branched alkyl group bonded to an NHC (= O) moiety. Examples of "alkylaminocarbonyl" include CH 3 NHC(＝O)、CH 3 CH 2 NHC(＝O)、CH 3 CH 2 CH 2 NHC(＝O)、(CH 3 ) 2 CHNHC (= O). The terms "alkenylaminocarbonyl" and "alkynylaminocarbonyl" are similarly defined. Examples of "alkenylaminocarbonyl" include H 2 C＝CHCH 2 NHC (= O) and (CH) 3 ) 2 C＝CHCH 2 NHC (= O). Examples of "alkynylaminocarbonyl" include CH 3 C ≡ CNHC (= O) and CH 3 C≡CCH 2 NHC (= O). Examples of "dialkylaminocarbonyl" include (CH) 3 ) 2 N(＝O)、(CH 3 CH 2 ) 2 NC(＝O)、CH 3 CH 2 (CH 3 )NC(＝O)、(CH 3 ) 2 CH(CH 3 ) NC (= O) and CH 3 CH 2 CH 2 (CH 3 )NC(＝O)。
The term "alkylcarbonylamino" denotes a straight or branched chain alkyl group bonded to a C (= O) NH moiety. Examples of "alkylcarbonylamino" include CH 3 CH 2 C (= O) NH and CH 3 CH 2 CH 2 C (= O) NH. The terms "alkenylcarbonylamino" and "alkynylcarbonylamino" are defined analogously. Examples of "alkenylcarbonylamino" include H 2 C＝CHCH 2 C (= O) NH and (CH) 3 ) 2 C＝CHCH 2 C (= O) NH. Examples of "alkynylcarbonylamino" include CH 3 C≡CCH(CH 3 ) C (= O) NH and HC ≡ CCH 2 CH 2 C (= O) NH. The term "alkoxycarbonylamino" denotes an alkoxy group bonded to a C (= O) NH moiety. Examples of "alkoxycarbonylamino" include CH 3 OC (= O) NH and CH 3 CH 2 OC(＝O)NH。
The term "alkylaminocarbonylamino" denotes a straight or branched alkyl group bonded to an NHC (= O) NH moiety. Examples of "alkylaminocarbonylamino" include CH 3 CH 2 NHC (= O) NH and (CH) 3 CH 2 ) 2 CH 2 NHC(＝O) NH. The terms "alkenylaminocarbonylamino" and "alkynylaminocarbonylamino" are defined analogously. Examples of "alkenylaminocarbonylamino" include H 2 C＝CHCH 2 NHC (= O) NH and (CH) 3 ) 2 C＝CHCH 2 NHC (= O) NH. Examples of "alkynylaminocarbonylamino" include CH 3 C≡CCH(CH 3 ) NHC (= O) NH and HC ≡ CCH 2 CH 2 NHC(＝O)NH。
"Alkylsulfonylamino" refers to an NH group substituted with an alkylsulfonyl group. Examples of "alkylsulfonylamino" include CH 3 CH 2 S(＝O) 2 NH and (CH) 3 ) 2 CHS(＝O) 2 And (4) NH. The terms "alkenylsulfonylamino" and "alkynylsulfonylamino" are defined analogously. Examples of "alkenylsulfonylamino" include H 2 C＝CHCH 2 CH 2 S(＝O) 2 NH and (CH) 3 ) 2 C＝CHCH 2 S(＝O) 2 And (4) NH. Examples of "alkynylsulfonylamino" include CH 3 C≡CCH(CH 3 )S(＝O) 2 NH and HC ≡ CCH 2 CH 2 S(＝O) 2 And (4) NH. The term "alkylsulfonyloxy" denotes an alkylsulfonyl group bonded to an oxygen atom. Examples of "alkylsulfonyloxy" include CH 3 S(＝O) 2 O、CH 3 CH 2 S(＝O) 2 O、CH 3 CH 2 CH 2 S(＝O) 2 O、(CH 3 ) 2 CHS(＝O) 2 O, and the different butylsulfonyloxy, pentylsulfonyloxy, and hexylsulfonyloxy isomers.
"alkylaminosulfonyl" means bonded to NHS (= O) 2 Some straight or branched chain alkyl. Examples of "alkylaminosulfonyl" include CH 3 CH 2 NHS(＝O) 2 And (CH) 3 ) 2 CHNHS(＝O) 2 . The terms "alkenylaminosulfonyl" and "alkynylaminosulfonyl" are defined analogously. Examples of "alkenylaminosulfonyl" include H 2 C＝CHCH 2 CH 2 NHS(＝O) 2 And (CH) 3 ) 2 C＝CHCH 2 NHS(＝O) 2 . Examples of "alkynylaminosulfonyl" include CH 3 C≡CCH(CH 3 )NHS(＝O) 2 And HC ≡ CCH 2 CH 2 NHS(＝O) 2 。
"alkylaminosulfonylamino" means bonded to NHS (= O) 2 Straight or branched chain alkyl of the NH moiety. Examples of "alkylaminosulfonylamino" include CH 3 CH 2 NHS(＝O) 2 NH and (CH) 3 ) 2 CHNHS(＝O) 2 And (4) NH. The terms "alkenylaminosulfonylamino" and "alkynylaminosulfonylamino" are defined analogously. Examples of "alkenylaminosulfonylamino" include H 2 C＝CHCH 2 CH 2 NHS(＝O) 2 NH and (CH) 3 ) 2 C＝CHCH 2 NHS(＝O) 2 And (4) NH. Examples of "alkynylaminosulfonylamino" include CH 3 C≡CCH(CH 3 )NHS(＝O) 2 NH and HC ≡ CCH 2 CH 2 NHS(＝O) 2 NH。
"alkoxyalkyl" refers to an alkoxy substitution on an alkyl group. Examples of "alkoxyalkyl" include CH 3 OCH 2 、CH 3 OCH 2 CH 2 、CH 3 CH 2 OCH 2 、CH 3 CH 2 CH 2 OCH 2 And CH 3 CH 2 OCH 2 CH 2 . "Alkoxyalkoxy" means an alkoxy substitution on another alkoxy moiety. "Alkoxyalkoxyalkyl" refers to an alkoxyalkoxy substitution on an alkyl group. Examples of "alkoxyalkoxyalkyl" include CH 3 OCH 2 OCH 2 、CH 3 OCH 2 OCH 2 CH 2 And CH 3 CH 2 OCH 2 OCH 2 。
The term "alkylcarbonyloxy" denotes a straight or branched chain alkyl group bonded to a C (= O) O moiety. Examples of "alkylcarbonyloxy" include CH 3 CH 2 C (= O) O and (CH) 3 ) 2 CHC (= O) O. The terms "alkenylcarbonyloxy" and "alkynylcarbonyloxy" are defined analogously. Examples of "alkenylcarbonyloxy" include H 2 C＝CHCH 2 CH 2 C (= O) O and (CH) 3 ) 2 C＝CHCH 2 C (= O) O. Examples of "alkynyl carbonyloxy" include CH 3 C≡CCH(CH 3 ) C (= O) O and HC ≡ CCH 2 CH 2 C (= O) O. The term "alkoxycarbonyloxy" denotes a linear or branched alkoxy group bonded to a C (= O) O moiety. Examples of "alkoxycarbonyloxy" include CH 3 CH 2 CH 2 OC (= O) O and (CH) 3 ) 2 CHOC (= O) O. The term "alkoxycarbonylalkyl" denotes an alkoxycarbonyl substitution on an alkyl group. Examples of "alkoxycarbonylalkyl" include CH 3 CH 2 OC(＝O)CH 2 、(CH 3 ) 2 CHOC(＝O)CH 2 And CH 3 OC(＝O)CH 2 CH 2 . The term "alkylaminocarbonyloxy" denotes a straight or branched chain alkylaminocarbonyl group attached to and linked through an oxygen atom. Examples of "alkylaminocarbonyloxy" include (CH) 3 ) 2 CHCH 2 NHC (= O) O and CH 3 CH 2 NHC (= O) O. The terms "alkenylaminocarbonyloxy" and "alkynylaminocarbonyloxy" are defined analogously.
The term "alkylcarbonylthio" denotes a straight or branched chain alkyl group bonded to a C (= O) S moiety. Examples of "alkylcarbonylthio" include CH 3 CH 2 C (= O) S and CH 3 CH 2 CH 2 C(＝O)S。
"cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "cycloalkylalkyl" denotes cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" groups include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight or branched chain alkyl groups. The term "alkylcycloalkyl" denotes alkyl substitution on the cycloalkyl moiety and includes, for example, ethylcyclopropyl, isopropylcyclobutyl, methylcyclopentyl and methylcyclohexyl. "Alkylcycloalkylalkyl" refers to an alkylcycloalkyl substitution on an alkyl group. Examples of "alkylcycloalkylalkyl" include methylcyclohexylmethyl and ethylcyclopropylmethyl. "cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl as well as groups having more than one double bond, such as 1, 3-cyclohexadienyl or 1, 4-cyclohexadienyl. The term "cycloalkylcycloalkyl" denotes a cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members. Examples of cycloalkylcycloalkyl groups include cyclopropylcyclopropyl (such as 1,1' -dicyclopropyl-1-yl, 1' -dicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4-cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as 1,1' -dicyclohexyl-1-yl) as well as the different cis-and trans-cycloalkylcycloalkyl isomers (such as (1r, 2s) -1,1' -dicyclopropyl-2-yl and (1r, 2r) -1,1' -dicyclopropyl-2-yl).
The term "cycloalkoxy" denotes a cycloalkyl group attached to and linked through an oxygen atom, including for example cyclopentoxy and cyclohexoxy. The term "cycloalkoxyalkyl" denotes cycloalkoxy substitution on the alkyl moiety. Examples of "cycloalkoxyalkyl" include cyclopropyloxymethyl, cyclopentyloxyethyl, and other cycloalkoxy groups bonded to straight or branched alkyl moieties.
The term "cycloalkylaminoalkyl" denotes a cycloalkylamino substitution on an alkyl group. Examples of "cycloalkylaminoalkyl" groups include cyclopropylaminomethyl, cyclopentylaminoethyl, and other cycloalkylamino moieties bonded to straight or branched chain alkyl groups.
"cycloalkylcarbonyl" denotes a cycloalkyl group bonded to a C (= O) group, and includes, for example, cyclopropylcarbonyl and cyclopentylcarbonyl. "cycloalkylcarbonyloxy" refers to a cycloalkylcarbonyl group attached to and linked through an oxygen atom. Examples of "cycloalkylcarbonyloxy" include cyclohexylcarbonyloxy and cyclopentylcarbonyloxy. The term "cycloalkoxycarbonyl" means a cycloalkoxy group bonded to a C (= O) group, for example, cyclopropyloxycarbonyl and cyclopentyloxycarbonyl. "cycloalkylaminocarbonylamino" denotes cycloalkylamino bonded to a C (= O) NH group, for example, cyclopentylaminocarbonylamino and cyclohexylaminocarbonylamino.
The term "halogen", alone or in compound words such as "haloalkyl", or when used in describing compounds such as "alkyl substituted with halogen", includes fluorine, chlorine, bromine or iodine. In addition to this, the present invention is,when used in compound words such as "haloalkyl", or when used in describing words such as "alkyl substituted with halogen", the alkyl may be partially or fully substituted with halogen atoms (which may be the same or different). Examples of "haloalkyl" or "alkyl substituted with halo" include CF 3 、ClCH 2 、CF 3 CH 2 And CF 3 CCl 2 . The terms "haloalkenyl," haloalkynyl, "" haloalkoxy, "" haloalkylsulfonyl, "" halocycloalkyl, "and the like are defined analogously to the term" haloalkyl. Examples of "haloalkenyl" include Cl 2 C＝CHCH 2 And CF 3 CH 2 CH＝CHCH 2 . Examples of "haloalkynyl" include HC ≡ CCHCl, CF 3 C≡C、CCl 3 C ≡ C and FCH 2 C≡CCH 2 . Examples of "haloalkoxy" include CF 3 O、CCl 3 CH 2 O、F 2 CHCH 2 CH 2 O and CF 3 CH 2 And O. Examples of "haloalkylsulfonyl" include CF 3 S(＝O) 2 、CCl 3 S(＝O) 2 、CF 3 CH 2 S(＝O) 2 And CF 3 CF 2 S(＝O) 2 . Examples of "halocycloalkyl" include 2-chlorocyclopropyl, 2-fluorocyclobutyl, 3-bromocyclopentyl and 4-chlorocyclohexyl.
"cyanoalkyl" refers to alkyl substituted with one cyano group. Examples of "cyanoalkyl" include NCCH 2 、NCCH 2 CH 2 And CH 3 CH(CN)CH 2 . "hydroxyalkyl" refers to an alkyl group substituted with one hydroxyl group. Examples of "hydroxyalkyl" include HOCH 2 CH 2 、CH 3 CH 2 (OH) CH and HOCH 2 CH 2 CH 2 CH 2 。
"trialkylsilyl" includes 3 branched and/or straight chain alkyl groups attached to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl. The term "halogenotrialkylsilyl" is defined analogously. Examples of the "halogenotrialkylsilyl group" include a trifluoromethylsilyl group and a trichloromethylsilyl group.
The total number of carbon atoms in the substituents being represented by "C i -C j "prefix" indicates where i and j are numbers from 1 to 15. E.g. C 1 -C 4 Alkylsulfonyl represents methylsulfonyl to butylsulfonyl; c 2 Alkoxyalkyl represents CH 3 OCH 2 ；C 3 Alkoxyalkyl denotes, for example, CH 3 CH(OCH 3 )、CH 3 OCH 2 CH 2 Or CH 3 CH 2 OCH 2 (ii) a And C 4 Alkoxyalkyl denotes various isomers of an alkyl group substituted with an alkoxy group having a total of four carbon atoms, and examples include CH 3 CH 2 CH 2 OCH 2 And CH 3 CH 2 OCH 2 CH 2 。
In general, when a molecular fragment (i.e., a free radical) is represented by a series of atomic symbols (e.g., C, H, N, O, and S), the implicit point or points of attachment will be readily identified by those skilled in the art. In some instances herein, one or more attachment points may be indicated by a hyphen ("-"), particularly where an alternative attachment point is possible.
The term "unsubstituted" in reference to a group such as a ring or ring system means that the group does not have any substituents other than its attachment to one or more of the remainder of formula 1. The term "optionally substituted" means that the number of substituents can be zero. Unless otherwise indicated, an optionally substituted group may be substituted with as many optional substituents as possible, which may be accommodated by replacing a hydrogen atom with a non-hydrogen substituent on any available carbon or nitrogen atom. Typically, the number of optional substituents (when present) ranges from 1 to 3. As used herein, the term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un) substituted.
The number of optional substituents may be constrained by specific limitations. For example, the phrase "optionally selected with up to 3 independently selected from R 13 By substitution ofBy substituted "is meant that 0, 1, 2 or 3 substituents may be present (if the number of potential attachment points permits). When the range specified for the number of substituents (e.g., x is an integer from 0 to 3 in EXAMPLE A) exceeds the number of available positions of the substituent on the ring (e.g., for (R) on G-7 in EXAMPLE A 13 ) x Is 1), the actual upper limit of the range is considered to be the number of available positions.
Unless otherwise indicated, when a compound is provided with a subscript (which indicates that the number of substituents can vary (e.g., (R) in example A 13 ) x Wherein x is 1 to 3)), then the substituents are independently selected from the group of defined substituents. When variable groups are shown to be optionally attached to one position (e.g., (R) in example A 13 ) x Where x may be 0), then hydrogen may be located at that position, even if not mentioned in the definition of variable groups.
The dotted lines in the rings depicted in this specification (e.g., rings G-44, G-45, G-48, and G-49 shown in example A) indicate that the indicated bonds can be single or double bonds.
The nomenclature of substituents in this disclosure uses recognized terminology to provide those skilled in the art with a concise understanding of the chemical structure. The bit order descriptor may be omitted for the sake of brevity.
Unless otherwise indicated, a "ring" or "ring system" (e.g., G) as a component having formula 1 is carbocyclic or heterocyclic. The term "ring system" denotes two or more linked rings. The term "spiro ring system" denotes a ring system consisting of two rings connected at a single atom (thus the rings share a single atom). The term "bicyclic ring system" denotes a ring system consisting of two rings sharing two or more common atoms. In a "fused bicyclic ring system," these common atoms are adjacent, and thus the rings share two adjacent atoms and the bond connecting them.
The term "ring member" refers to an atom (e.g., C, O, N, or S) or other moiety (e.g., C (= O), C (= S), S (= O) and forming the backbone of a ring or ring systemS(＝O) 2 ). The term "aromatic" means that each ring atom is substantially on the same plane and has a p-orbital perpendicular to the plane of the ring, and that (4 n + 2) pi electrons (where n is a positive integer) are associated with the ring to comply with Huckel's rule.
The term "carbocyclic ring" denotes a ring in which the atoms forming the ring backbone are selected from carbon only. Unless otherwise indicated, carbocycles may be saturated, partially unsaturated, or fully unsaturated rings. When a fully unsaturated carbocyclic ring satisfies the huckel rule, then the ring is also referred to as an "aromatic ring". "saturated carbocyclic ring" means a ring having a skeleton composed of carbon atoms connected to each other by single bonds; unless otherwise indicated, the remaining carbon valencies are occupied by hydrogen atoms.
As used herein, the term "partially unsaturated ring" or "partially unsaturated heterocyclic ring" refers to a ring that contains unsaturated ring atoms and one or more double bonds but is not aromatic.
The term "heterocyclic ring" or "heterocyclic" denotes a ring wherein at least one of the atoms forming the ring backbone is not carbon. Unless otherwise indicated, the heterocyclic ring may be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies the huckel rule, then the ring is also referred to as a "heteroaromatic ring" or an aromatic heterocyclic ring. "saturated heterocyclic ring" refers to a heterocyclic ring containing only single bonds between ring members.
Unless otherwise indicated, the heterocyclic rings and ring systems are attached to the remainder of formula 1 through any available carbon or nitrogen atom by replacement of a hydrogen on said carbon or nitrogen atom.
The compounds of the present invention may exist as one or more stereoisomers. Stereoisomers are isomers that are identical in constitution but differ in the arrangement of their atoms in space, and include enantiomers, diastereomers, cis and trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about a single bond, where the rotation barrier is high enough to allow separation of isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to one or more other stereoisomers, or when separated from one or more other stereoisomers. In addition, one skilled in the art would know how to isolate, enrich, and/or selectively prepare the stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest l.eliel and Samuel h.wilen, stereochemistry of Organic Compounds [ Organic Compounds Stereochemistry ], john Wiley & Sons [ John Wiley father company ],1994.
The compounds of the present invention may exist as a mixture of stereoisomers, as individual stereoisomers, or as optically active forms. For example, when T is T-3, then the compound of formula 1 contains at least one double bond and the configuration of the substituents around the double bond may be (Z) or (E) (cis or trans), or a mixture thereof. In the context of the present disclosure and claims, a wavy bond (e.g., as shown in the T-3 section of the summary) represents a single bond to an adjacent double bond, wherein the geometry around the adjacent double bond is either (Z) -configuration (cis-isomer (syn-isomer) or cis-isomer (cis-isomer)) or (E) -configuration (trans-isomer) or trans-isomer (trans-isomer)), or a mixture thereof. That is, the wavy bond means the unspecified (Z) -or (E) - (cis or trans) isomer, or a mixture thereof. Furthermore, the compounds of the present invention may contain one or more chiral centers and thus exist in enantiomeric and diastereomeric forms. Unless the structural formula or language of the present application clearly specifies the configuration of a particular cis or trans isomer or chiral center, the scope of the present invention is intended to encompass all such isomers per se as well as mixtures of cis and trans isomers, as well as mixtures of diastereomers and racemic mixtures of enantiomers (optical isomers).
The invention also includes compounds having formula 1 wherein one stereoisomer is enriched relative to the other stereoisomer or stereoisomers. Of note are compounds having formula 1 wherein T is T-3 and the substituents attached to the double bond in the T-3 moiety are predominantly in the (Z) -configuration, or predominantly in the (E) -configuration. The ratio of (Z) -to (E) -isomers in any compound having formula 1, whether stereoselective or non-stereoselective, can have a wide range of values. For example, the compound having formula 1 may comprise from about 10 to 90 weight percent of the (Z) -isomer and about 90 to 10 weight percent of the (E) -isomer. In other embodiments, the compound of formula 1 may contain from about 15 to 85 weight percent of the (Z) -isomer and about 85 to 15 weight percent of the (E) -isomer; in another embodiment, the mixture contains about 25 to 75 weight percent of the (Z) -isomer and about 75 to 25 weight percent of the (E) -isomer; in another embodiment, the mixture contains about 35 to 65 weight percent of the (Z) -isomer and about 65 to 35 weight percent of the (E) -isomer; in another embodiment, the mixture contains about 45 to 55 weight percent of the (Z) -isomer and about 55 to 45 weight percent of the (E) -isomer. These weight percentages are based on the total weight of the composition, and it is understood that the sum of the weight percentages of the (Z) -isomer and the (E) -isomer is 100 weight percentages. In other words, the compound having formula 1 may contain 65 weight percent of the (Z) -isomer and 35 weight percent of the (E) -isomer, or vice versa.
In addition, the present invention includes compounds that are enriched compared to the racemic mixture in the enantiomer having formula 1. Substantially pure enantiomers of the compound having formula 1 are also included. When enantiomerically enriched, one enantiomer is present in a greater amount than the other, and the degree of enrichment can be defined by expression of enantiomeric excess ("ee") defined as (2 x-1) · 100%, where x is the molar fraction of the predominate enantiomer in the mixture (e.g., 20% ee corresponds to a ratio of 60 of enantiomers.
Preferably, the compositions of the present invention have an enantiomeric excess of at least 50% of the more active isomer; more preferably at least 75% enantiomeric excess; still more preferably at least 90% enantiomeric excess; and most preferably at least a 94% enantiomeric excess. Of particular note are enantiomerically pure examples of the more active isomers.
The compounds of the present invention may exist as one or more conformational isomers due to limited rotation around an amide bond (e.g., C (= O) -N) in formula 1. The present invention includes mixtures of conformational isomers. In addition, the invention includes compounds enriched in one conformer relative to the other conformers.
The present invention includes all stereoisomers, conformational isomers and mixtures thereof in all ratios, as well as isotopic forms such as deuterated compounds.
Those skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides because the nitrogen requires an available lone pair to oxidize to the oxide; those skilled in the art will recognize those nitrogen-containing heterocycles that can form N-oxides. Those skilled in the art will also recognize that tertiary amines are capable of forming N-oxides. Synthetic methods for preparing N-oxides of heterocycles and tertiary amines are well known to those skilled in the art and include the oxidation of heterocycles and tertiary amines using peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for preparing N-oxides have been widely described and reviewed in the literature, see for example: gilchrist, comprehensive Organic Synthesis, vol.7, pp.748-750, edited by S.V.Ley, pergamon Press, pegman Press; tisler and b.stanovnik, comprehensive Heterocyclic Chemistry, volume 3, pages 18-20, editors a.j.boulton and a.mckillop, pegman press; m.r.grimett and b.r.t.keene, advances in Heterocyclic Chemistry [ Advances in Heterocyclic Chemistry ], volume 43, pages 149-161, editors of a.r.katitzky, academic Press [ Academic Press ]; tisler and b.stanovnik, advances in Heterocyclic Chemistry [ Advances in Heterocyclic Chemistry ], volume 9, pages 285-291, edited by a.r.katritzky and a.j.boulton, academic press; and g.w.h.cheeseman and e.s.g.werstink, advances in Heterocyclic Chemistry [ Advances in Heterocyclic Chemistry ], volume 22, pages 390-392, editions a.r.katritzky and a.j.boulton, academic press.
One skilled in the art recognizes that salts share the biological utility of non-salt forms, as salts of compounds are in equilibrium with their corresponding non-salt forms in the environment and under physiological conditions. Thus, a variety of salts of the compounds of formula 1 are useful in controlling plant diseases caused by fungal plant pathogens (i.e., are agriculturally suitable). Salts of the compounds having formula 1 include acid addition salts formed with inorganic or organic acids such as hydrobromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, tartaric acid, 4-toluenesulfonic acid, or valeric acid. When the compound having formula 1 contains an acidic moiety such as a carboxylic acid, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention includes compounds selected from formula 1, N-oxides and agriculturally suitable salts and solvates thereof.
A compound selected from formula 1, stereoisomers, tautomers, N-oxides, and salts thereof typically exist in more than one form, and thus formula 1 includes all crystalline and non-crystalline forms of the compound represented by formula 1. Non-crystalline forms include embodiments that are solids, such as waxes and gums, and embodiments that are liquids, such as solutions and melts. Crystalline forms include embodiments that represent substantially single crystal types and embodiments that represent mixtures of polymorphs (i.e., different crystalline types). The term "polymorph" refers to a particular crystalline form of a compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of molecules in a crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition by the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound within the crystal lattice. Polymorphs can differ in such chemical, physical, and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate, and bioavailability. One skilled in the art will appreciate that a polymorph of a compound represented by formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or mixture of polymorphs of the same compound represented by formula 1. The preparation and isolation of specific polymorphs of a compound represented by formula 1 can be achieved by methods known to those skilled in the art, including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of Polymorphism, see r.hilfiker editors, polymorphism in the Pharmaceutical Industry [ Polymorphism in the Pharmaceutical Industry ], wiley-VCH [ willi-VCH corporation ], weinheim [ wein heim ],2006.
One skilled in the art recognizes that the compounds having formula 1 can exist as a mixture of ketones and solvated forms (e.g., hemiketals, ketals and hydrates) and are each independently interconvertible and agriculturally active. For example, having formula 1 1 The ketone of (i.e., the compound of formula 1 wherein T is T-1) can correspond to the compound of formula 1 2 (i.e., wherein T is T-2, and R 2a X and R 2b Compounds having formula 1 wherein Y is OH) are present in equilibrium. In cases where the keto group is immediately adjacent to an electron withdrawing group, such as when R 1 With trifluoromethyl, this equilibrium is typically favored for the hydrate form.
Figure BDA0003913878900000251
The present invention includes all ketones and solvated forms of the compound of formula 1, as well as mixtures thereof in all ratios. Unless otherwise indicated, reference to a description of one tautomer should be taken to include all tautomers.
Furthermore, some of the unsaturated rings and ring systems depicted in example a may have arrangements of single and double bonds between ring members other than that depicted. Such different arrangements of bonds correspond to different tautomers, for specific arrangements of ring atoms. For these unsaturated rings and ring systems, the particular tautomers depicted should be considered as representing all possible tautomers of the ring atom arrangements shown.
As described in the summary, aspects of the present invention relate to a composition comprising (a) at least one compound selected from formula 1, N-oxides, and salts thereof, and (b) at least one additional fungicidal compound. More particularly, component (b) is selected from the group consisting of
(b1) Benzimidazole methyl carbamate (MBC) fungicides;
(b2) A dicarboximide fungicide;
(b3) Demethylation inhibitor (DMI) fungicides;
(b4) Phenylamide (PA) fungicides;
(b5) Amine/morpholine fungicides;
(b6) A phospholipid biosynthesis inhibitor fungicide;
(b7) Succinate dehydrogenase inhibitor (SDHI) fungicide;
(b8) Hydroxy (2-amino-) pyrimidine fungicides;
(b9) An Anilinopyrimidine (AP) fungicide;
(b10) N-phenyl carbamate fungicides;
(b11) Quinone outside inhibitor (QoI) fungicides;
(b12) Phenylpyrrole (PP) fungicides;
(b13) An azanaphthalene fungicide;
(b14) Cell peroxidation inhibitor fungicides;
(b15) Melanin biosynthesis inhibitor-reductase (MBI-R) fungicides;
(b 16 a) a melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicide;
(b 16 b) a melanin biosynthesis inhibitor-polyketide synthase (MBI-P) fungicide;
(b17) Ketoreductase inhibitor (KRI) fungicides;
(b18) Squalene epoxidase inhibitor fungicides;
(b19) Polyoxin fungicides;
(b20) Phenylurea fungicides;
(b21) Quinone Internal Inhibitor (QiI) fungicides;
(b22) Benzamide and thiazolecarboxamide fungicides;
(b23) An enol pyruronium (enopyranuronic acid) antibiotic fungicide;
(b24) A hexapyranosyl antibiotic fungicide;
(b25) Glucopyranosyl antibiotic: protein synthesis fungicides;
(b26) Glucopyranosyl antibiotic fungicides;
(b27) Cyanoacetamide oxime fungicides;
(b28) A carbamate fungicide;
(b29) Oxidative phosphorylation uncoupling fungicides;
(b30) An organotin fungicide;
(b31) A carboxylic acid fungicide;
(b32) A heteroaromatic fungicide;
(b33) Phosphonate fungicides;
(b34) O-carbamoylbenzoic acid fungicides;
(b35) A benzotriazine fungicide;
(b36) Benzene-sulfonamide fungicides;
(b37) A pyridazinone fungicide;
(b38) Thiophene-carboxamide fungicides;
(b39) Complex I NADH oxidoreductase inhibitor fungicide;
(b40) Carboxylic Acid Amide (CAA) fungicides;
(b41) A tetracycline antibiotic fungicide;
(b42) Thiocarbamate fungicides;
(b43) Benzamide fungicides;
(b44) A microbial fungicide;
(b45) Quinone external inhibitors, stakectin binding (QoSI) fungicides;
(b46) A plant extract fungicide;
(b47) Cyanoacrylate fungicides;
(b48) A polyene fungicide;
(b49) Oxysterol binding protein inhibitor (OSBPI) fungicide;
(b50) Aryl-phenyl-ketone fungicides;
(b51) Host plant defense inducing fungicides;
(b52) A multi-site active fungicide;
(b53) Biological agents with multiple modes of action;
(b54) A fungicide other than the fungicides of component (a) and components (b 1) to (b 53); and
(b1) Salts of the compounds of (a) to (b 54).
Of note are embodiments in which component (b) comprises at least one fungicidal compound from each of two different groups selected from (b 1) to (b 54).
"benzimidazole methyl carbamate (MBC) fungicide (b 1)" (FRAC code 1) inhibits mitosis by binding to β -tubulin during microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, intracellular trafficking, and cellular structure. Methyl benzimidazole carbamates fungicides include benzimidazole and thiophanate fungicides. Benzimidazoles include benomyl, carbendazim, fuberidazole and thiabendazole. The thiophanate group includes thiophanate and thiophanate methyl.
"dicarboximide fungicide (b 2)" (FRAC code 2) inhibits mitogen-activated protein (MAP)/histidine kinase in osmotic signal transduction. Examples include ethidium, dimethachlon, iprodione, procymidone and vinclozolin.
The "demethylation inhibitor (DMI) fungicide (b 3)" (FRAC code 3) (sterol biosynthesis inhibitor (SBI): category I) inhibits the C14-demethylase, which plays a role in sterol production. Sterols, such as ergosterol, are required for membrane structure and function, making them essential for the development of functional cell walls. Thus, exposure to these fungicides results in abnormal growth and eventual death of the susceptible fungus. DMI fungicides fall into several chemical classes: piperazine, pyridine, pyrimidine, imidazole, triazole and triazolethione. Piperazine includes azinam. Pyridine includes buthionine, pyribenzoxim, pyrisoxazole and (α S) - [3- (4-chloro-2-fluorophenyl) -5- (2, 4-difluorophenyl) -4-isoxazolyl ] -3-pyridinemethanol. Pyrimidines include fenarimol, fenarimol and pyriminol. The imidazole includes econazole, imazalil, oxpoconazole, pefurazoate, prochloraz and triflumizole. Triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, empenthnazole (ipfentrafluconazole), fluroxypyr, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole-P, alpha- (1-chlorocyclopropyl) -alpha- [2- (2, 2-dichlorocyclopropyl) ethyl ] -1H-1,2, 4-triazole-1-ethanol, rac-1- [ [ (2R, 3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) -2-oxiranyl ] methyl ] -1H-1,2, 4-triazole, rac-2- [ [ (2R, 3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) -2-oxiranyl ] methyl ] -1, 2-dihydro-3H-1, 2, 4-triazole-3-thione, and rac-1- [ [ (2R, 3S) -3- (2, 4-difluorophenyl) -2-oxiranyl ] methyl ] -1H-1,2, 4-triazole-1, 4-thion-1H-1, 4-triazole. Triazolethiones include prothioconazole. Biochemical studies have shown that all of the above Fungicides are DMI Fungicides, as described by k.h. kuck et al in Modern Selective Fungicides-Properties, applications and Mechanisms of Action, h.lyr (editors), gustav Fischer Verlag: new york, 1995, 205-258.
"Phenylamide (PA) fungicide (b 4)" (FRAC code 4) is a specific inhibitor of RNA polymerase in fungi of the class oomycetes. Sensitive fungi exposed to these fungicides show a reduced ability to incorporate uridine into rRNA. The growth and development of susceptible fungi is prevented by exposure to this class of fungicides. Phenylamide fungicides include acylalanine, oxazolidinone and butyrolactone fungicides. The acylalanines include benalaxyl, benalaxyl-M (also known as benalaxyl-M), furalaxyl, metalaxyl, and metalaxyl-M (also known as metalaxyl-M). The oxazolidinone includes oxadixyl. Butyrolactone includes furoamide.
"amine/morpholine fungicides (b 5)" (FRAC code 5) (SBI: categoryII) inhibition of two target sites within the sterol biosynthesis pathway, delta 8 →Δ 7 Isomerase and delta 14 A reductase. Sterols, such as ergosterol, are required for membrane structure and function, making them essential for the development of functional cell walls. Thus, exposure to these fungicides results in abnormal growth and eventual death of the susceptible fungi. Amine/morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholine, piperidine and spiroketal-amine fungicides. Morpholines include 4-dodecyl-2, 6-dimethylmorpholine (aldimorph), dodecamorpholine, fenpropimorph, tridemorph and trimorphamide (trimorphamide). The piperidine includes fenpropidin and propamocarb. The spiroketal alcohol-amine comprises spiroxamine.
"phospholipid biosynthesis inhibitor fungicide (b 6)" (FRAC code 6) inhibits fungal growth by affecting phospholipid biosynthesis. Phospholipid biosynthesis fungicides include phosphorothioate and dithiolane fungicides. The thiophosphate includes edifenphos, iprobenfos and pyriminophos. The dithiolane includes isoprothiolane.
The "succinate dehydrogenase inhibitor (SDHI) fungicide (b 7)" (FRAC code 7) inhibits complex II fungal respiration by disrupting a key enzyme called succinate dehydrogenase in the krebs cycle (TCA cycle). Inhibition of respiration prevents the fungus from producing ATP and thereby inhibits growth and reproduction. SDHI fungicides include phenylbenzamide, phenyloxoethylthiophenamide, pyridylethylbenzamide, furancarboxamide, oxathiazacyclodienecarboxamide, thiazolecarboxamide, pyrazole-4-carboxamide, N-cyclopropyl-N-benzyl-pyrazole carboxamide, N-methoxy- (phenyl-ethyl) -pyrazole carboxamide, picolinamide, and pyrazinecarboxamide fungicides. Phenylbenzamides include mexican, flutolanil and mefenapyr. The phenyloxoethyl thiophene amides include iprothioam. Pyridylethylbenzamides include fluopyram. Furancarboxamides include methylfuroamide. Oxathiane hexadienecarboxamides include carboxin and oxycarboxin. Thiazole carboxamides include thifluzamide. Pyrazole-4-carboxamides include benzoxazole, bixafen, flufen-ethyl (provisional common name, accession No. 1676101-39-5), thiabendazole, fluxapyroxad, furametpyr, imazalil (inpyrfluxam), isopyrazam, penflufen, penthiopyrad, propyne (pyrapropofol) (provisional common name, accession No. 1803108-03-3), sedaxane, and N- [2- (2, 4-dichlorophenyl) -2-methoxy-1-methylethyl ] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide. N-cyclopropyl-N-benzyl-pyrazole carboxamides include isofluram (isofluroxypram). N-methoxy- (phenyl-ethyl) -pyrazole carboxamide includes fluxapyroxad hydroxylamine. The picolinamide includes boscalid. Pyrazinecarboxamides include biphenylpyrazinecarboxamide.
The "hydroxy- (2-amino-) pyrimidine fungicide (b 8)" (FRAC code 8) inhibits nucleic acid synthesis by interfering with adenosine deaminase. Examples include brehmol (bupirimate), dimethirimol and ethirimol.
An "Anilinopyrimidine (AP) fungicide (b 9)" (FRAC code 9) was proposed to inhibit the biosynthesis of the amino acid methionine and to disrupt the secretion of hydrolytic enzymes that lyse plant cells during infection. Examples include cyprodinil, mepanipyrim and pyrimethanil.
The "N-phenyl carbamate fungicide (b 10)" (FRAC code 10) inhibits mitosis by binding to β -tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, intracellular trafficking, and cellular structure. Examples include diethofencarb.
The "quinone outside inhibitor (QoI) fungicide (b 11)" (FRAC code 11) inhibits complex III mitochondrial respiration in fungi by affecting panthenol oxidase. Oxidation of panthenol cytochrome bc located in the inner mitochondrial membrane of fungi 1 The "quinone outside" (Qo) sites of the complex are blocked. Inhibition of mitochondrial respiration prevents normal fungal growth and development. Quinone outside inhibitor fungicides include methoxyacrylate, methoxyacetamide, methoxycarbamate, hydroxyimino acetate, hydroxyimino acetamide, and dihydrodioxazine fungicides (collectively strobilurin fungicides) and oxazolidinedione, imidazolidinone, and benzyl carbamate fungicides. The methoxyacrylate includes azoxystrobin, coumoxystrobin, enostroburin (also known as enestroburin), and Dermatophagoides fluvialis Ester, picoxystrobin and pyraoxystrobin. The methoxyacetamide includes mandrostatin (mandrostatin). The methoxy carbamate includes pyraclostrobin, pyraclostrobin and nitrapyrin methyl. The trifloxystrobin acetate comprises kresoxim-methyl and trifloxystrobin. The oximinoacetamide includes dimoxystrobin, dimethomorph, metominostrobin and orysastrobin. Dihydrodioxazines include fluoxastrobin. Oxazolidinediones include famoxadone. Imidazolinones include fenamidone. The benzyl carbamate includes pyribencarb.
"phenylpyrrole (PP) fungicides (b 12)" (FRAC code 12) inhibit MAP/histidine kinases associated with osmotic signal transduction in fungi. Fenpiclonil and fludioxonil are examples of this class of fungicides.
The "azanaphthalene fungicide (b 13)" (FRAC code 13) was proposed to inhibit signal transduction by a mechanism as yet unknown. They have been shown to interfere with germination and/or outgrowth of the fungi causing powdery mildew disease. Azaphthalene fungicides include aryloxyquinoline and quinazolinone. The aryloxyquinoline comprises quinoxalin. Quinazolinones include propoxymoline.
"cell peroxidation inhibitor fungicides (b 14)" (FRAC code 14) are proposed for the inhibition of lipid peroxidation affecting membrane synthesis in fungi. Members of this class, such as hymexazol, can also affect other biological processes such as respiration and melanin biosynthesis. Cell peroxidation fungicides include aromatic and 1,2, 4-thiadiazole fungicides. Aromatic fungicides include biphenyl, dicyclopentadienyl, clonidine, pentachloronitrobenzene, tetrachloronitrobenzene, and tolclofos-methyl. The 1,2, 4-thiadiazole includes hymexazol.
"melanin biosynthesis inhibitor-reductase (MBI-R) fungicide (b 15)" (FRAC code 16.1) inhibits the naphthalene aldehyde condensation reduction step in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-reductase fungicides include isobenzofuranone, pyrroloquinolinone, and triazolobenzothiazole fungicides. Isobenzofuranones include tetrachlorophthalide. Pyrroloquinolinones include pyrroloquinolinones. The triazolobenzothiazole includes tricyclazole.
"melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicide (b 16 a)" (FRAC code 16.2) inhibits the pillared ketodehydratase enzyme in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitors-dehydratase fungicides include cyclopropanecarboxamide, carboxamide and propionamide fungicides. Cyclopropanecarboxamides include cyclopropyloamide. The formamide includes diclorocyanid. The propionamide comprises fenoxanil.
"polyketide synthase (MBI-P) fungicide (b 16 b), an inhibitor of melanin biosynthesis (FRAC code 16.3), inhibits polyketide synthase in melanin biosynthesis. Melanin is required for host plant infection by some fungi. The melanin biosynthesis inhibitor-polyketide synthase fungicides include trifluoroethylcarbamate fungicides. Trifluoroethylcarbamate includes tolprocarb (tolprocarb).
"ketoreductase inhibitor (KRI) fungicide (b 17)" (FRAC code 17) inhibits 3-ketoreductase during C4-demethylation in sterol production. Ketoreductase inhibitor fungicides (also known as Sterol Biosynthesis Inhibitors (SBIs)): class III) includes hydroxyanilines and amino-pyrazolones. The hydroxyanilides include fenhexamid. Amino-pyrazolones include fenpyrazamine. Quinofolin (Quinofumelin) (provisionally common name, accession number 861647-84-9) and fluoroquine (ipflufenoquin) (provisionally common name, accession number 1314008-27-9) are also known as ketoreductase inhibitor fungicides.
A "squalene epoxidase inhibitor fungicide (b 18)" (FRAC code 18) (SBI: class IV) inhibits squalene epoxidase in the sterol biosynthesis pathway. Sterols, such as ergosterol, are required for membrane structure and function, making them essential for the development of functional cell walls. Thus, exposure to these fungicides results in abnormal growth and eventual death of the susceptible fungus. Squalene epoxidase inhibitor fungicides include thiocarbamate and allylamine fungicides. Thiocarbamates include barnyard grass. Allylamines include naftifine and terbinafine.
The "polyoxin fungicide (b 19)" (FRAC code 19) inhibits chitin synthase. Examples include polyoxins.
The "phenylurea fungicide (b 20)" (FRAC code 20) was proposed to affect cell division. Examples include pencycuron.
The "Quinone Internal Inhibitor (QiI) fungicide (b 21)" (FRAC code 21) inhibits complex III mitochondrial respiration in fungi by affecting ubiquinone reductase. Reduction of ubiquinone cytochrome bc located in the inner mitochondrial membrane of fungi 1 The complex is blocked at the "quinone interior" (Qi) site. Inhibition of mitochondrial respiration prevents normal fungal growth and development. Quinone inside inhibitor fungicides include cyanoimidazole, sulfamoyl triazole, and picolinamide fungicides. The cyanoimidazole includes cyazofamid. Sulfamoyl triazoles include amisulbrom. Picolinamides include fenpicloram (fenpicoxamid) (accession number 517875-34-2).
"benzamide and thiazolecarboxamide fungicides (b 22)" (FRAC code 22) inhibit mitosis by binding to β -tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, intracellular trafficking, and cellular structure. Benzamides include toluamides, such as zoxamide. Thiazolecarboxamides include ethylaminothiazolecarboxamides, such as ethaboxam.
"Alenolpyruronan antibiotic fungicides (b 23)" (FRAC code 23) inhibit fungal growth by affecting protein biosynthesis. Examples include blasticidin-S.
The "hexopyranosyl antibiotic fungicide (b 24)" (FRAC code 24) inhibits fungal growth by affecting protein biosynthesis. Examples include kasugamycin.
"glucopyranosyl antibiotic: protein synthesis fungicides (b 25) "(FRAC code 25) inhibit fungal growth by affecting protein biosynthesis. Examples include streptomycin.
"Glucopyranosyl antibiotic fungicide (b 26)" (FRAC code U18, previously reclassified as U18 for FRAC code 26) was proposed for the inhibition of trehalase and inositol biosynthesis. Examples include validamycin.
"cyanoacetamide oxime fungicide (b 27)" (FRAC code 27) includes cymoxanil.
"carbamate fungicides (b 28)" (FRAC code 28) are considered to be multi-site inhibitors of fungal growth. They are proposed to interfere with fatty acid synthesis in cell membranes, which then disrupts cell membrane permeability. Iodopropynyl butyl carbamate (Iodocarb), propamocarb and thiocarb are examples of this group of fungicides.
The "oxidative phosphorylation uncoupling fungicide (b 29)" (FRAC code 29) inhibits fungal respiration by uncoupling oxidative phosphorylation. Inhibiting respiration prevents normal fungal growth and development. This class includes dinitrophenyl crotonates such as dicofos, dicofos and dinocap, and 2, 6-dinitroanilines such as fluazinam.
The "organotin fungicides (b 30)" (FRAC code 30) inhibit Adenosine Triphosphate (ATP) synthase in the oxidative phosphorylation pathway. Examples include triphenyltin acetate, triphenyltin chloride, and triphenyltin hydroxide.
The "carboxylic acid fungicide (b 31)" (FRAC code 31) inhibits fungal growth by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Examples include oxolinic acid.
The "heteroaromatic fungicide (b 32)" (FRAC code 32) was proposed to affect DNA/ribonucleic acid (RNA) synthesis. Heteroaromatic fungicides include isoxazoles and isothiazolones. Isoxazoles include hymexazol and isothiazolones include octhione.
"phosphonate fungicides (b 33)" (FRAC code P07, previously reclassified as P07 for FRAC code 33) include phosphorous acid and its various salts, including fosetyl aluminum.
"ortho-carbamoylbenzoic acid fungicide (b 34)" (FRAC code 34) includes biscumylphthalein.
"benzotriazine fungicides (b 35)" (FRAC code 35) include pyrazoxazines.
The "benzene-sulfonamide fungicide (b 36)" (FRAC code 36) includes flusulfamide.
The "pyridazinone fungicide (b 37)" (FRAC code 37) includes pyridazinone.
"thiophene-carboxamide fungicides (b 38)" (FRAC code 38) have been proposed for affecting ATP production. Examples include silthiopham.
"Complex I NADH oxidoreductase inhibitor fungicide (b 39)" (FRAC code 39) inhibits electron transport in mitochondria and includes pyrimidinamines such as fluopyram, pyrazole-5-carboxamides such as tolfenpyrad, and quinazolines such as fenazaquin.
The "Carboxylic Acid Amide (CAA) fungicide (b 40)" (FRAC code 40) inhibits cellulose synthase, which prevents growth and leads to death of the target fungus. Carboxylic acid amide fungicides include cinnamic acid amide, valinamide carbamate, and mandelic acid amide fungicides. Cinnamic acid amides include dimethomorph, flumorph and pyrimorph. Valinamide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tropicarb, and valienamine (also known as propamocarb). Mandelic acid amides include mandipropamid, N- [2- [4- [ [3- (4-chlorophenyl) -2-propyn-1-yl ] oxy ] -3-methoxyphenyl ] ethyl ] -3-methyl-2- [ (methylsulfonyl) amino ] butanamide and N- [2- [4- [ [3- (4-chlorophenyl) -2-propyn-1-yl ] oxy ] -3-methoxyphenyl ] ethyl ] -3-methyl-2- [ (ethylsulfonyl) amino ] butanamide.
"Tetracycline antibiotic fungicide (b 41)" (FRAC code 41) inhibits fungal growth by affecting protein synthesis. Examples include oxytetracycline.
"thiocarbamate fungicide (b 42)" (FRAC code M12, previously reclassified as M12) includes sulbencarb.
"benzamide fungicide (b 43)" (FRAC code 43) inhibits fungal growth by delocalization of spectrin-like proteins. Examples include pyridylmethyl benzamides such as fluopicolide and fluoetheramide.
"microbial fungicides (b 44)" (FRAC code BM02, previously reclassified as BM02 by FRAC code 44) disrupt fungal pathogen cell membranes. Microbial fungicides include Bacillus species, such as Bacillus amyloliquefaciens (Bacillus amyloliquefaciens) strain AP-136, AP-188, AP-218, AP-219, AP-295, QST713, FZB24, F727, MB1600, D747, TJ100 (also known as strain 1BE; known from EP 2962568), and the fungicidal lipopeptides that they produce.
"quinone outside inhibitors (quinone outside inhibitors)",the stakemectin-binding (QoSI) fungicide (b 45) "(FRAC code 45) is controlled by affecting the cytochrome bc 1 The "quinone outside" (Qo) site of the complex, the ubiquinone reductase at the peg-binding subsite, inhibits complex III mitochondrial respiration in fungi. Inhibition of mitochondrial respiration prevents normal fungal growth and development. QoSI fungicides include triazolopyrimethanil, such as ametoctradin.
The "plant extract fungicide (b 46)" (FRAC code 46) causes cell membrane disruption. Botanical extract fungicides include terpene hydrocarbons, terpene alcohols and terpene phenols such as extracts from Melaleuca alternifolia (tea tree) and vegetable oils (mixtures) such as eugenol, geraniol and thymol.
The "cyanoacrylate fungicide (b 47)" (FRAC code 47) binds to myosin motor domain and affects locomotor activity and actin assembly. Cyanoacrylates include fungicides, such as phenamacril.
The "polyene fungicide (b 48)" (FRAC code 48) causes the destruction of the fungal cell membrane by binding to the major sterol ergosterol in the membrane. Examples include natamycin (pimaricin).
An "oxysterol binding protein inhibitor (OSBPI) fungicide (b 49)" (FRAC code 49) binds to oxysterol binding protein in oomycetes, causing inhibition of zoospore release, zoospore motility, and sporangial germination. Fungicides which bind to oxysterol include piperidinyl thiazole isoxazolines such as fluorothiazolepyrietophenones (oxathiapirolin) and fluoxapride (fluoxaprirolin).
An "aryl-phenyl-ketone fungicide (b 50)" (FRAC code 50, previously reclassified as 50 with FRAC code U8) inhibits growth of mycelium in fungi. Aryl-phenyl ketone fungicides include benzophenones such as metrafenone, and benzoylpyridines such as pyridinone.
The "host plant defense-inducing fungicide (b 51)" induces host plant defense mechanisms. Host plant defense inducing fungicides include benzothiadiazole (FRAC code P01), benzisothiazole (FRAC code P02), thiadiazole carboxamide (FRAC code P03), polysaccharide (FRAC code P04), plant extract (FRAC code P05), microorganism (FRAC code P06), and phosphonate fungicide (FRAC code P07, see (b 33) above). Benzothiadiazoles include acibenzolar-S-methyl. Benzisothiazoles include thiabendazole. The thiadiazolecarboxamide includes tiadinil and isotianil. The polysaccharide comprises laminarin. The plant extract comprises an extract from Polygonum cuspidatum (Polygonum cuspidatum). The microorganisms include cell walls of Bacillus mycoides (Bacillus mycoides) isolate J and Saccharomyces cerevisiae (Saccharomyces cerevisiae) strain LAS 117.
The "multi-site active fungicide (b 52)" inhibits fungal growth through multiple sites of action and has contact/preventive activity. Multisite active fungicides include copper fungicides (FRAC code M01), sulfur fungicides (FRAC code M02), dithiocarbamate fungicides (FRAC code M03), phthalimide fungicides (FRAC code M04), chloronitrile fungicides (FRAC code M05), sulfonamide fungicides (FRAC code M06), multisite contact guanidine fungicides (FRAC code M07), triazine fungicides (FRAC code M08), quinone fungicides (FRAC code M09), quinoxaline fungicides (FRAC code M10), maleimide fungicides (FRAC code M11) and thiocarbamate fungicides (FRAC code M12, see (b 42) above). Copper fungicides are inorganic compounds containing copper, typically in the copper (II) oxidation state; examples include copper oxychloride, copper sulfate, and copper hydroxide (e.g., including compositions such as bordeaux mixture (tribasic copper sulfate)). Sulphur fungicides are inorganic chemicals containing a ring or chain of sulphur atoms; examples include elemental sulfur. Dithiocarbamate fungicides contain a dithiocarbamate molecular moiety; examples include ferbam, mancozeb, maneb, metiram, propineb, thiram, zizyl, zineb and ziram. Phthalimide fungicides contain a phthalimide molecular moiety; examples include folpet, captan and captafol. Chloronitrile fungicides contain an aromatic ring substituted with chlorine and cyano; examples include chlorothalonil. Sulfonamide fungicides include benfuramide and tolylfluanide. Multi-site contact guanidine fungicides include biguanide salts, iminoctadine benzenesulfonates and iminoctadine triacetates. Triazine fungicides include trichlofone. Quinone fungicides include dithianon. Quinoxaline fungicides include mefenmanate (also known as chinomethionate). The maleimide fungicides include fentrazamide.
"biological agent with multiple modes of action (b 53)" includes agents from biological sources that show multiple mechanisms of action without evidence of a major mode of action. This category of fungicides includes polypeptides (lectins), phenols, sesquiterpenes, triterpenoids and coumarin fungicides (FRAC code BM 01), such as extracts from lupin plantlet cotyledons. This category also includes microbial fungicides (FRAC code BM02, see (b 44) above).
"a fungicide other than the fungicides of component (a) and components (b 1) to (b 53); (b 54) "; including certain fungicides whose mode of action may not be known. These include: (b 54.1) "phenyl-acetamide fungicide" (FRAC code U06), (b 54.2) "guanidine fungicide" (FRAC code U12), (b 54.3) "thiazolidine fungicide" (FRAC code U13), (b 54.4) "pyrimidone-hydrazone fungicide" (FRAC code U14), (b 54.5) "4-quinolinylacetate fungicide" (FRAC code U16), (54.6) "tetrazolyloxime fungicide" (FRAC code U17) and "glucopyranosyl antibiotic fungicide" (FRAC code U18, see (b 26) above). Phenyl-acetamides include cyflufenamid. The guanidine comprises dodine. Thiazolidines include fluthiacet (flutianil). Pyrimidinone hydrazones include cyprodinil. The 4-quinolinylacetate comprises tefloquin (tebufloquin). Tetrazoloxime includes tetrazolyl pyritinol (picarbtrazox).
(b54) Classes also include besoxazine (betaxazin), dichlorophenylazo (dichlobeniazox) (provisionally common name, accession No. 957144-77-3), dipyridamole (dipyridamole) (provisionally common name, accession No. 16114-35-5), flumetoquin (flometoquin), tianan (ferric methylarsenate), nitropyrrolidin, thiophanate (accession No. 304911-98-6), N' - [4- [ 4-chloro-3- (trifluoromethyl) phenoxy ] -2, 5-dimethylphenyl ] -N-ethyl-N-methylmethamidine, 5-fluoro-2- [ (4-fluorophenyl) methoxy ] -4-pyrimidinamine, and 4-fluorophenyl N- [1- [ [ [1- (4-cyanophenyl) ethyl ] sulfonyl ] methyl ] propyl ] carbamate.
Additional "fungicides other than the fungicides of classes (1) to (54)" whose mode of action may not be known or may not have been classified, include fungicidal compounds selected from components (b 54.7) to (b 54.13) as described below.
Component (54.7) relates to N- [ [3- (acetoxy) -4-methoxy-2-pyridinyl ] carbonyl ] -L-alanine (1S) -2, 2-bis (4-fluorophenyl) -1-methylethyl ester (provisionally common name picolinamide, accession number 1961312-55-9), which is considered a Quinone Internal Inhibitor (QiI) fungicide (FRAC code 21) that inhibits complex III mitochondrial respiration in fungi.
Component (54.8) relates to 1- [2- [ [ [1- (4-chlorophenyl) -1H-pyrazol-3-yl ] oxy ] methyl ] -3-methylphenyl ] -1, 4-dihydro-4-methyl-5H-tetrazol-5-one (temporary common name methyltetraproline, accession No. 1472649-01-6), which is considered a quinone outside inhibitor (QoI) fungicide (FRAC code 45) that inhibits mitochondrial respiration of complex III in fungi and is effective against QoI resistant strains.
Component (54.9) relates to 3-chloro-4- (2, 6-difluorophenyl) -6-methyl-5-phenylpyridazine (pyridine chloromethyl, provisionally common name, accession number 1358061-55-8), which is considered an accelerator for tubulin polymerization, producing antifungal activity against fungal species belonging to the phyla ascomycota and basidiomycota.
Component (54.10) relates to 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester (extemporaneous general name aminopyrine (accession No. 1531626-08-0), which is believed to inhibit GWT-1 protein in glycosylphosphatidylinositol-anchor biosynthesis in neurospora crassa.
Component (b 54.11) relates to compounds of the formula b54.11
Figure BDA0003913878900000381
Wherein
R b1 And R b3 Each independently is halogen; and is
R b2 Is H, halogen, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl or C 3 -C 6 A cycloalkyl group.
Examples of compounds having formula b54.11 include (b54.11a) methyl N- [ [5- [1- (2, 6-difluoro-4-formylphenyl) -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, (b54.11b) methyl N- [ [5- [1- (4-cyclopropyl-2, 6-dichlorophenyl) -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, (b54.11c) methyl N- [ [5- [1- (4-chloro-2, 6-difluorophenyl) -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, (b54.11d) methyl N- [ [5- [1- (4-cyclopropyl-2, 6-difluorophenyl) -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, (b54.11e) methyl N- [ [5- [1- [2, 6-difluoro-4- (1-methylethyl) phenyl ] -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, and (b54.11f) methyl N- [ [5- [1- [2, 6-difluoro-4- (trifluoromethyl) phenyl ] -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate. Compounds having the formula b54.11, their use as fungicides and methods of preparation are generally known; see, for example, PCT patent publications WO2008/124092, WO 2014/066120, and WO 2020/097012.
Component (b 54.12) relates to compounds of the formula b54.12
Figure BDA0003913878900000382
Wherein
R b4 Is that
Figure BDA0003913878900000383
R b6 Is C 2 -C 4 Alkoxycarbonyl or C 2 -C 4 A haloalkylaminocarbonyl group;
l is CH 2 Or CH 2 O, wherein the right atom is attached to the benzene ring in formula b 54.12; and is
R b5 Is that
Figure BDA0003913878900000391
Examples of compounds having formula b54.12 include (b54.12a) N- (2, 2-trifluoroethyl) -2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] -4-oxazolecarboxamide and ethyl (b54.12b) 1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenoxy ] methyl ] -1H-pyrazole-4-carboxylate. Compounds having the formula b54.11, their use as fungicides and methods for their preparation are generally known; see, for example, PCT patent publication WO 2020/056090.
Component (b 54.13) relates to compounds of the formula b54.13
Figure BDA0003913878900000392
Wherein
R b7 、R b8 And R b9 Each independently is H, halogen or cyano; and is
R b10 And R b11 Each independently of the others being H, halogen, C 1 -C 3 Alkyl or C 1 -C 3 And (3) methoxy.
Examples of compounds having the formula b54.13 include (b54.13a) 4- (2-chloro-4-fluorophenyl) -N- (2-fluoro-4-methyl-6-nitrophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (b54.13b) 4- (2-chloro-4-fluorophenyl) -N- (2-fluoro-6-nitrophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, (b54.13c) 3, 5-difluoro-4- [5- [ (4-methoxy-2-nitrophenyl) amino ] -1, 3-dimethyl-1H-pyrazol-4-yl ] -benzonitrile and (b54.13d) N- (2-chloro-4-fluoro-6-nitrophenyl) -4- (2-chloro-4-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine. Compounds having the formula b54.11, their use as fungicides and methods for their preparation are generally known; see, for example, PCT patent publication WO2020051402.
Embodiments of the present invention as described in the summary of the invention include those described below. In the following examples, formula 1 includes stereoisomers, N-oxides and salts thereof, unless further defined in the examples, and reference to "a compound having formula 1" includes the definition of the substituents specified in the summary.
Example 1. Compositions as described in the summary of the invention comprising components (a) and (b), wherein in formula 1, T is T-1.
Example 2. Compositions described in the summary of the invention comprising components (a) and (b), wherein in formula 1, T is T-2.
Example 3. Compositions described in the summary comprising components (a) and (b), wherein in formula 1, T is T-3.
Example 3a. Compositions as described in the summary of the invention comprising components (a) and (b), wherein in formula 1, T is T-2 or T-3.
Example 4. Compositions as described in the summary of the invention comprising components (a) and (b), wherein in formula 1, R 1 Is CF 3 。
Embodiment 5. The composition of the summary of the invention as described in any one of embodiments 1 to 4 comprising components (a) and (b), wherein in formula 1, W is O or S.
Embodiment 6. The composition of embodiment 5, wherein W is O.
Embodiment 7. The composition of the summary of the invention as described in any one of embodiments 1 to 4, comprising components (a) and (b), wherein in formula 1, W is NR 3 。
Embodiment 8. The composition of the summary of the invention as described in any one of embodiments 1 to 7 comprising components (a) and (b), wherein in formula 1, R 3 Is H, cyano, C (= O) OH, C 1 -C 2 Alkyl radical, C 2 -C 3 Alkylcarbonyl group, C 2 -C 3 Halogenated alkylcarbonyl, OR 3a Or NR 3b R 3c 。
Embodiment 9. The composition of embodiment 8, wherein R 3 Is H, cyano, C 1 -C 2 Alkyl OR OR 3a 。
Embodiment 10. The composition of embodiment 9, wherein R 3 Is H, cyano OR OR 3a 。
Embodiment 11. A composition as described in the summary of the invention of any one of embodiments 1 to 10 comprising components (a) and (b), wherein in formula 1, R 3a Is H、C 1 -C 2 Alkyl radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 A haloalkylcarbonyl group.
Embodiment 12. The composition of embodiment 11, wherein R 3a Is H.
Embodiment 13. The composition of the summary of the invention as described in any one of embodiments 1 to 12 comprising components (a) and (b), wherein in formula 1, when R is 3b Is isolated (i.e. not bound to R) 3c Together form a ring), then R 3b Is H, C 1 -C 3 Alkyl radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 A haloalkylcarbonyl group.
Embodiment 14. The composition of embodiment 13, wherein R 3b Is H or methyl.
Embodiment 15. The composition of the summary of the invention as described in any one of embodiments 1 to 14 comprising components (a) and (b), wherein in formula 1, when R is 3c Is isolated (i.e. not bound to R) 3b Together form a ring), then R 3c Is H or C 1 -C 2 An alkyl group.
Embodiment 16. The composition of embodiment 15, wherein R 3c Is H or methyl.
Embodiment 17. The composition of the summary of the invention as described in any one of embodiments 1 to 16, comprising components (a) and (b), wherein in formula 1, X is O or NR 5a 。
Embodiment 18. The composition of the summary of the invention as described in any one of embodiments 1 to 16 comprising components (a) and (b), wherein in formula 1, X is O, S, NH, or NOH.
Embodiment 19. The composition of embodiment 18, wherein X is O or NOH.
Embodiment 20. The composition of embodiment 20, wherein X is O.
Embodiment 21. The composition of the summary of the invention as described in any one of embodiments 1 to 20 comprising components (a) and (b), wherein in formula 1, Y is O or NR 5b 。
Embodiment 22. A composition as described in the summary of the invention of any one of embodiments 1 to 20 comprising components (a) and (b), wherein in formula 1, Y is O, S, NH, or NOH.
Embodiment 23. The composition of embodiment 22, wherein Y is O or NOH.
Embodiment 24. The composition of embodiment 23, wherein Y is O.
Embodiment 25. The composition of the summary of the invention as described in any one of embodiments 1 to 24 comprising components (a) and (b), wherein in formula 1, R 5a And R 5b Each independently is H, hydroxy or C 1 -C 2 An alkyl group.
Embodiment 26. The composition of embodiment 25, wherein R 5a And R 5b Each independently is H, hydroxy or methyl.
Embodiment 27. The composition of the summary of the invention as described in any one of embodiments 1 to 26 comprising components (a) and (b), wherein in formula 1, when R is 2a And R 2b When they are separate (i.e. do not form a ring together), then R 2a And R 2b Each independently is H, C 1 -C 3 Alkyl radical, C 2 -C 3 Alkenyl, (CR) 4a R 4b ) p -OH、(CR 4a R 4b ) p -Cl or (CR) 4a R 4b ) p -Br。
Embodiment 27a. The composition of the summary of the invention as described in any one of embodiments 1 to 26 comprising components (a) and (b), wherein in formula 1, when R is 2a And R 2b When they are separate (i.e. do not form a ring together), then R 2a And R 2b Each independently is H, C 1 -C 3 Alkyl radical, C 3 -C 15 Trialkylsilyl or C 3 -C 15 A halogenotrialkylsilyl group.
Embodiment 27b. The composition of embodiment 27a, wherein R 2a And R 2b Each independently is H, methyl, trimethylsilyl or halotrimethylsilyl.
Embodiment 27c. The composition of embodiment 27b, wherein R 2a And R 2b Each independently of the other is H, methyl, trimethylsilyl orA trifluoromethyl silyl group.
Embodiment 27d. The composition of embodiment 27c, wherein R 2a And R 2b Each independently is H, methyl or trimethylsilyl.
Embodiment 27e. The composition of embodiment 27d, wherein R 2a Is H and R 2b Is a trimethylsilyl group.
Embodiment 27f. The composition of embodiment 27d, wherein R 2a Is methyl and R 2b Is a trimethylsilyl group.
Embodiment 28. The composition of embodiment 27, wherein R 2a And R 2b Each independently is H, C 1 -C 3 Alkyl group, (CR) 4a R 4b ) p -Cl or (CR) 4a R 4b ) p -Br。
Embodiment 29. The composition of embodiment 28, wherein R 2a And R 2b Each independently of the others is H, methyl, (CR) 4a R 4b ) p -Cl or (CR) 4a R 4b ) p -Br。
Embodiment 30. The composition of embodiment 28, wherein R 2a And R 2b Each independently is H or C 1 -C 3 An alkyl group.
Embodiment 31. The composition of embodiment 30, wherein R 2a And R 2b Each independently is H or C 1 -C 2 An alkyl group.
Embodiment 32. The composition of embodiment 31, wherein R 2a And R 2b Each independently is H or methyl.
Embodiment 33. The composition of embodiment 32, wherein R 2a And R 2b Each is H.
Embodiment 34. The composition of the summary of the invention as described in any one of embodiments 1 to 33 comprising components (a) and (b), wherein in formula 1, when R is 2a And R 2b When they are separate (i.e. do not form a ring together), then R 2a And R 2b One is (CR) 4a R 4b ) p -OH、(CR 4a R 4b ) p -SH、(CR 4a R 4b ) p -Cl or (CR) 4a R 4b ) p -Br and the other is H.
Embodiment 35. The composition of embodiment 34, wherein R 2a And R 2b One is (CR) 4a R 4b ) p -Cl or (CR) 4a R 4b ) p -Br and the other is H.
Embodiment 36. The composition of the summary of the invention as described in any one of embodiments 1 to 35, comprising components (a) and (b), wherein in formula 1, R 2a And R 2b Each independently of the other is H, methyl, (CR) 4a R 4b ) p -OH、(CR 4a R 4b ) p -Cl or (CR) 4a R 4b ) p -Br; or R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-to 6-membered saturated ring containing, in addition to these atoms X and Y, ring members selected from carbon atoms, with up to 2 carbon atom ring members independently selected from C (= O) and C (= S), the ring being optionally selected on a carbon atom ring member from up to 2 independently selected from halogen, cyano, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy and C 1 -C 2 A substituent of a haloalkoxy group.
Embodiment 37. The composition of embodiment 36, wherein R 2a And R 2b Each independently is H or methyl; or R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-to 6-membered saturated ring containing, in addition to these atoms X and Y, a ring member selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C (= O), the ring being optionally substituted on a carbon atom ring member with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy.
Embodiment 38. The composition of embodiment 37, wherein R 2a And R 2b Each independently is H or methyl; or R 2a And R 2b With the atoms to which they are attachedThe atoms X and Y together form a 5-membered saturated ring which, in addition to the atoms X and Y, contains a ring member selected from carbon atoms, the ring being optionally substituted on the carbon atom ring member with up to 1 substituent selected from halogen, cyano and methyl.
Embodiment 39. The composition of embodiment 38, wherein R 2a And R 2b Each is H; or R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-membered saturated ring containing, in addition to these atoms X and Y, a ring member selected from carbon atoms, the ring being optionally substituted on the carbon atom ring member with up to 1 substituent selected from methyl.
Embodiment 40. The composition of embodiment 39, wherein R 2a And R 2b Each is H; or R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-membered saturated ring which, in addition to these atoms X and Y, contains a ring member selected from carbon atoms.
Embodiment 41. The composition of the summary of the invention as described in any one of embodiments 1 to 40 comprising components (a) and (b), wherein in formula 1, when R is 2a And R 2b When taken together to form a ring (i.e. not separated), then R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-to 6-membered saturated ring containing, in addition to these atoms X and Y, a ring member selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C (= O), the ring being optionally substituted on a carbon atom ring member with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy.
Embodiment 42. The composition of embodiment 41, wherein R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-membered saturated ring containing, in addition to these atoms X and Y, a ring member selected from carbon atoms, which ring is optionally substituted on the carbon atom ring member with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl and methoxy.
Embodiment 43. The composition of embodiment 42, whereinR 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-membered saturated ring containing, in addition to these atoms X and Y, a ring member selected from carbon atoms, the ring being optionally substituted on the carbon atom ring member with up to 1 substituent selected from halogen, methyl and halomethyl.
Embodiment 44. The composition of embodiment 43, wherein R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-membered saturated ring which, in addition to these atoms X and Y, contains a ring member selected from carbon atoms.
Embodiment 45. The composition of the summary of the invention as described in any one of embodiments 1 to 44 comprising components (a) and (b), wherein in formula 1, R 2c Is C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 2 -C 3 Alkenyl radical, C 2 -C 3 Halogenated alkenyl group, C 2 -C 3 Alkynyl or C 2 -C 3 Haloalkynyl groups, each of which is optionally substituted by up to 1 substituent selected from cyano, hydroxy, SC ≡ N and C 1 -C 2 Substituent of alkoxy.
Example 46. The composition of example 45, wherein R 2c Is C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 2 -C 3 Alkenyl radical, C 2 -C 3 Haloalkenyl, C 2 -C 3 Alkynyl or C 2 -C 3 Haloalkynyl groups, each of which is optionally substituted with up to 1 substituent selected from cyano and methoxy.
Embodiment 46a the composition of embodiment 46, wherein R 2c Is C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 2 -C 3 Alkenyl radical, C 2 -C 3 Haloalkenyl or C 2 -C 3 Alkynyl.
Embodiment 47. The composition of embodiment 46a, wherein R 2c Is C 1 -C 2 Alkyl radical, C 2 -C 3 Alkenyl or C 2 -C 3 Alkynyl.
Embodiment 48. The composition of embodiment 47, wherein R 2c Is methyl or ethyl.
Embodiment 48a. The composition of embodiment 48, wherein R 2c Is ethyl.
Embodiment 49. The composition of the summary of the invention as described in any one of embodiments 1 to 48a, comprising components (a) and (b), wherein in formula 1, R 2d Is H, cyano, halogen or C 1 -C 2 An alkyl group.
Embodiment 49a. The composition of embodiment 49, wherein R 2d Is H, cyano, cl, F or methyl.
Embodiment 50. The composition of embodiment 49a, wherein R 2d Is H or methyl.
Embodiment 51. The composition of embodiment 50, wherein R 2d Is H.
Embodiment 52. The composition of the summary of the invention as described in any one of embodiments 1 to 51 comprising components (a) and (b), wherein in formula 1, each R 4a And R 4b Independently is H or C 1 -C 2 An alkyl group.
Embodiment 53. The composition of embodiment 52, wherein each R 4a And R 4b Independently is H or methyl.
Embodiment 54. The composition of embodiment 53, wherein each R 4a And R 4b Is H.
Embodiment 55. A composition as described in the summary of the invention of any one of embodiments 1 to 54 comprising components (a) and (b), wherein in formula 1, p is 2.
Embodiment 56. A composition as described in the summary of the invention of any of embodiments 1 to 54 comprising components (a) and (b), wherein in formula 1, p is 3.
Embodiment 57. The composition of the summary of the invention as described in any one of embodiments 1 to 56 comprising components (a) and (b), wherein in formula 1, wherein A is 1 Is CR 6c R 6d O or S.
Embodiment 58. The composition of embodiment 57, wherein A 1 Is CR 6c R 6d Or O.
Embodiment 59. The composition of embodiment 58, wherein A 1 Is CR 6c R 6d 。
Embodiment 60. The composition of embodiment 58, wherein A 1 Is O.
Embodiment 61. The composition of the summary of the invention as described in any one of embodiments 1 to 60 comprising components (a) and (b), wherein in formula 1, a 1 Is CH 2 NH, O or S.
Embodiment 62. The composition of the summary of the invention as described in any one of embodiments 1 to 61, comprising components (a) and (b), wherein in formula 1, a 1 Is N (R) 7a )。
Embodiment 63. A composition as described in the summary of the invention of any one of embodiments 1 to 63 comprising components (a) and (b), wherein in formula 1, A 2 Is a direct bond, CR 6e R 6f O or S.
Embodiment 64. The composition of embodiment 63, wherein A 2 Is a direct bond, CR 6e R 6f Or O.
Embodiment 65. The composition of embodiment 64, wherein A 2 Is a direct bond or O.
Embodiment 66. The composition of embodiment 65, wherein A 2 Is a direct bond.
Embodiment 67. The composition of the summary of the invention as described in any one of embodiments 1 to 62, comprising components (a) and (b), wherein in formula 1, a 2 Is a direct bond, CH 2 NH, O or S.
Embodiment 67a the composition of embodiment 67, wherein A 2 Is a direct bond, CH 2 Or O.
Embodiment 68. The composition of embodiment 67a, wherein A 2 Is a direct bond or O.
Embodiment 69. The composition of the summary of the invention as described in any one of embodiments 1 to 62 comprising components (a) and (b), wherein in formula 1, A 2 Is N (R) 7b )。
Example 70A composition as described in the summary of any one of embodiments 1 to 69 comprising components (a) and (b), wherein in formula 1, when a is a 1 -A 2 -CR 6a R 6b When it is, then A 1 -A 2 -CR 6a R 6b Is selected from OCH 2 、OCH(Me)、CH(OH)CH 2 、CH 2 CH 2 、SCH 2 、OCF 2 And CH 2 OCH 2 。
Embodiment 71. The composition of embodiment 70, wherein A 1 -A 2 -CR 6a R 6b Is selected from OCH 2 OCH (Me) and CH 2 CH 2 。
Embodiment 72. The composition of embodiment 71, wherein A 1 -A 2 -CR 6a R 6b Is selected from OCH 2 And CH 2 CH 2 。
Embodiment 73. The composition of embodiment 72, wherein A 1 -A 2 -CR 6a R 6b Is OCH 2 。
Embodiment 74. A composition as described in the summary of the invention of any one of embodiments 1 to 74, comprising components (a) and (b), wherein in formula 1, when A is A 1 -A 2 When it is, then A 1 -A 2 Selected from O and CH 2 、OCH 2 And CH 2 O。
Embodiment 75. The composition of embodiment 74, wherein A 1 -A 2 Selected from O and CH 2 And CH 2 O。
Embodiment 76. The composition of embodiment 75, wherein A 1 -A 2 Is selected from O and CH 2 。
Embodiment 77. The composition of embodiment 76, wherein A 1 -A 2 Is O.
Embodiment 78. A composition as described in the summary of the invention of any one of embodiments 1 to 77 comprising components (a) and (b), wherein in formula 1, R 6a 、R 6b 、R 6c 、R 6d 、R 6e And R 6f Each independently is H, cyano, hydroxy, br, cl, F or methyl.
Embodiment 79 the composition of embodiment 78, wherein R 6a 、R 6b 、R 6c 、R 6d 、R 6e And R 6f Each independently is H, cyanohydroxy or methyl.
Embodiment 80. The composition of embodiment 79, wherein R 6a 、R 6b 、R 6c 、R 6d 、R 6e And R 6f Each independently is H or methyl.
Embodiment 81. The composition of embodiment 80, wherein R 6a 、R 6b 、R 6c 、R 6d 、R 6e And R 6f Each is H.
Embodiment 82. The composition of the summary of the invention as described in any one of embodiments 1 to 81, comprising components (a) and (b), wherein in formula 1, R 7a And R 7b Each independently is H, C 1 -C 2 Alkyl or C 2 -C 3 An alkylcarbonyl group.
Embodiment 83. The composition of embodiment 82, wherein R 7a And R 7b Each independently is H or C 1 -C 2 An alkyl group.
Embodiment 84. The composition of embodiment 83, wherein R 7a And R 7b Each is H.
Embodiment 85. The composition of the summary of the invention as described in any one of embodiments 1 to 84, comprising components (a) and (b), wherein in formula 1, when T is T-1 or T-2, then A is A 1 -A 2 -CH 2 。
Embodiment 86. The composition of the summary of any of embodiments 1 to 85, comprising components (a) and (b), wherein in formula 1, when T is T-1 or T-2, then A is OCH 2 、SCH 2 、NHCH 2 、CH 2 CH 2 、OCH 2 CH 2 、SCH 2 CH 2 、NHCH 2 CH 2 、CH 2 OCH 2 、CH 2 SCH 2 Or CH 2 NHCH 2 。
Example 87. The composition of example 86,wherein when T is T-1 or T-2, then A is OCH 2 、SCH 2 、CH 2 CH 2 、OCH 2 CH 2 、SCH 2 CH 2 、CH 2 OCH 2 Or CH 2 SCH 2 。
Embodiment 88. The composition of embodiment 87, wherein when T is T-1 or T-2, then A is OCH 2 Or CH 2 CH 2 。
Embodiment 89 the composition of embodiment 88, wherein when T is T-1 or T-2, then A is OCH 2 。
Embodiment 90. The composition of matter of any of embodiments 1 to 89 including components (a) and (b), wherein in formula 1, when T is T-3, then A is O, OCH 2 、SCH 2 、NHCH 2 、CH 2 、CH 2 CH 2 、CH 2 O、CH 2 S or CH 2 NH。
Embodiment 91. The composition of embodiment 82, wherein when T is T-3, then A is O, CH 2 Or OCH 2 。
Embodiment 92. The composition of embodiment 91, wherein when T is T-3, then A is O or CH 2 。
Embodiment 93. The composition of embodiment 92, wherein when T is T-3, then A is O.
Embodiment 94. The composition of matter described in the summary of any of embodiments 1 to 93, comprising components (a) and (b), wherein in formula 1, J is J-1 to J-3, J-6 to J-10, or J-14.
Embodiment 95. The composition of embodiment 94, wherein J is J-1, J-2, J-3, J-6, or J-14.
Embodiment 96. The composition of embodiment 95, wherein J is J-1, J-6, or J-14.
The composition of embodiment 97, wherein J is J-1 or J-6.
The composition of embodiment 97a, wherein J is J-14.
Embodiment 98. The composition of embodiment 97, wherein J is J-1.
Embodiment 99. The composition of embodiment 97, wherein J is J-6.
Embodiment 100. The composition of the summary of the invention as described in any of embodiments 1 to 99 comprising components (a) and (b), wherein in formula 1, each R 8 Independently F, cl or methyl.
Embodiment 100a. The composition of embodiment 100, wherein each R 8 Independently F or Cl.
Example 101. The composition of example 100, wherein each R 8 Independently F or methyl.
Embodiment 101a the composition of embodiment 101, wherein each R 8 Is F.
Embodiment 102. A composition as described in the summary of the invention of any one of embodiments 1 to 101a comprising components (a) and (b), wherein in formula 1, q is 0 or 1.
Embodiment 102a. A composition as described in the summary of the invention of any one of embodiments 1 to 101a comprising components (a) and (b), wherein in formula 1, q is 3 or 4.
Embodiment 102b. The composition of embodiment 102a, wherein in formula 1, q is 4.
Embodiment 103. The composition of embodiment 102, wherein q is 0.
Embodiment 103a the composition of embodiment 102, wherein q is 1.
Embodiment 104. The composition of the summary of the invention as described in any one of embodiments 1 to 103a comprising components (a) and (b), wherein in formula 1, each R 9a And R 9b Independently of each other H, halogen, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy or C 1 -C 3 A haloalkoxy group.
Embodiment 105. The composition of embodiment 104, wherein each R 9a And R 9b Independently of each other is H, halogen, C 1 -C 2 Alkyl or C 1 -C 2 A haloalkyl group.
Example 106 As described in example 105Wherein each R is 9a And R 9b Independently H, halogen or methyl.
Embodiment 107. The composition of embodiment 106, wherein each R 9a And R 9b Independently is H or methyl.
Embodiment 108. The composition of embodiment 107, wherein each R 9a And R 9b Is H.
Embodiment 109. A composition as described in the summary of the invention of any one of embodiments 1 to 108 comprising components (a) and (b), wherein in formula 1, n is 0, 1, or 2.
Embodiment 109a the composition of embodiment 109, wherein n is 1 or 2.
Embodiment 110. A composition as described in the summary of the invention of any one of embodiments 1 to 109a comprising components (a) and (b), wherein in formula 1, n is 0 or 1.
Embodiment 111. The composition of embodiments 109, 109a, or 110, wherein n is 1.
Embodiment 112. The composition of embodiment 109 or 110, wherein n is 0.
Embodiment 113. The composition of the summary of the invention as described in any one of embodiments 1 to 112, comprising components (a) and (b), wherein in formula 1, L is a direct bond, CH 2 CH (Me) or CH 2 CH 2 。
Embodiment 113a the composition of embodiment 113, wherein L is a direct bond, CH 2 Or CH 2 CH 2 。
Embodiment 114. The composition of embodiment 113a, wherein L is a direct bond or CH 2 。
Embodiment 115. The composition of embodiment 114, wherein L is CH 2 。
Embodiment 115a the composition of embodiment 114, wherein L is a direct bond.
Embodiment 116. The composition of the summary of the invention as described in any one of embodiments 1 to 115a, comprising components (a) and (b), wherein in formula 1, E is E 1 。
Example 116aThe composition of the summary of the invention of any one of embodiments 1 to 116 comprising components (a) and (b), wherein in formula 1, when L is a direct bond, then E is E 1 。
Embodiment 117. The composition of the summary of the invention as described in any one of embodiments 1 to 116a, comprising components (a) and (b), wherein in formula 1, E 1 Is cyano, nitro, C (= O) H, C (= O) OH or SC ≡ N; or C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 1 -C 6 Alkylsulfonyl radical, C 2 -C 6 Alkenylsulfonyl radical, C 2 -C 6 Alkynylsulfonyl, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkenylsulfonylamino group, C 2 -C 6 Alkynylsulfonylamino, C 1 -C 6 Alkylaminosulfonyl radical, C 2 -C 6 Dialkylaminosulfonyl radical, C 2 -C 6 Alkenylaminosulfonyl radical, C 2 -C 6 Alkylcarbonyl group, C 2 -C 6 Alkylaminocarbonyl radical, C 3 -C 6 Alkenylaminocarbonyl group, C 3 -C 6 Alkynyl aminocarbonyl group, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl or C 2 -C 6 Alkoxycarbonylamino wherein each carbon atom is optionally substituted by up to 1 atom selected from R 10a And up to 3 substituents independently selected from R 10b Is substituted.
Embodiment 118. The composition of embodiment 117, wherein E 1 Is cyano, nitro, C (= O) H, C (= O) OH or SC ≡ N; or C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkenylsulfonylamino group, C 2 -C 6 Alkylcarbonyl group, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical or C 3 -C 6 Alkynyloxycarbonyl, in which each carbon atom is optionally substituted by up to 1 From R 10a And up to 3 substituents independently selected from R 10b Is substituted.
Embodiment 119. The composition of embodiment 118, wherein E 1 Is C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylsulfonyl radical, C 2 -C 6 Alkylcarbonyl or C 2 -C 6 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1 atom selected from R 10a And up to 3 substituents independently selected from R 10b Is substituted with the substituent(s).
Embodiment 120 the composition of embodiment 119, wherein E 1 Is C 1 -C 3 Alkoxy radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1R 10a And up to 3 substituents independently selected from R 10b Is substituted with the substituent(s).
Embodiment 120a the composition of embodiment 120, wherein E 1 Is C 1 -C 3 Alkoxy or C 2 -C 3 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1 atom selected from R 10a Is substituted with the substituent(s).
Embodiment 121. The composition of embodiment 120, wherein E 1 Is C 1 -C 2 Alkoxy, wherein each carbon atom is optionally substituted by up to 1 atom selected from R 10a And up to 3 substituents independently selected from R 10b Is substituted with the substituent(s).
Embodiment 121a the composition of embodiment 120, wherein E 1 Is C 1 -C 2 Alkoxy, wherein each carbon atom is optionally substituted by up to 1 atom selected from R 10a Is substituted with the substituent(s).
Embodiment 121b. The composition of embodiment 121a, wherein E 1 Is optionally selected from R by up to 1 10a A substituent of (2) is substituted methoxy.
Embodiment 121c the composition of embodiment 121a, wherein E 1 Is selected from 1R 10a Substituted by a substituent ofA methoxy group of (1).
Embodiment 122. A composition as described in the summary of any of embodiments 1 to 121c, comprising components (a) and (b), wherein in formula 1, R 10a Is optionally selected from R by up to 3 11a Phenyl substituted with the substituent of (1); or a 5-to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, each ring optionally substituted with up to 3 substituents independently selected from R on carbon atom ring members 11a And is independently selected from R on a nitrogen atom ring member 11b 。
Embodiment 123. The composition of embodiment 122, wherein R 10a Is optionally selected from R by up to 2 11a Phenyl substituted with the substituent of (1); or a 5-to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, each ring optionally substituted with up to 2 substituents independently selected from R on the carbon atom ring members 11a And independently selected from R on a nitrogen ring member 11b 。
Embodiment 123a the composition of embodiment 123, wherein R 10a Is a 5-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms and up to 3N atoms, each ring optionally substituted on the carbon atom ring members with up to 2 heteroatoms independently selected from R 11a Is substituted with the substituent(s).
Embodiment 123b. The composition of embodiment 123a, wherein R 10a Is pyrazolyl, imidazolyl or triazolyl, each of which is optionally substituted by up to 2 independently selected R on a carbon atom ring member 11a Is substituted.
Embodiment 123c. The composition of embodiment 123b, wherein R 10a Is pyrazolyl or imidazolyl, each of which is optionally up to 2 independently selected from R on a carbon atom ring member 11a Is substituted.
Embodiment 123d. The composition of embodiment 123c, wherein R 10a Is optionally substituted on a carbon atom ring member by up to 1R 11a Substituted pyrazolyl, or pyrazolyl.
Embodiment 124. The composition of the summary of the invention as described in any one of embodiments 1 to 123c comprising components (a) and (b), wherein in formula 1, each R 10b Independently of one another is cyano, halogen, hydroxy, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 3 -C 6 Cycloalkyl radical, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Haloalkylsulfonyl, C 1 -C 4 Alkylamino radical, C 2 -C 4 Dialkylamino, C 2 -C 4 Alkylcarbonyl or C 2 -C 5 An alkoxycarbonyl group.
The composition of embodiment 124, wherein each R 10b Independently of one another is halogen, hydroxy, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 1 -C 4 Alkylsulfonyl radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 5 An alkoxycarbonyl group.
Embodiment 125a. The composition of embodiment 125 wherein each R 10b Independently of one another is halogen, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy or C 2 -C 4 An alkoxycarbonyl group.
Embodiment 126. The composition of the summary of the invention as described in any one of embodiments 1 to 125a comprising components (a) and (b), wherein in formula 1, each R 11a Independently of one another is halogen, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkynyloxy, C 2 -C 4 Alkoxyalkyl group, C 2 -C 6 Alkylcarbonyloxy, C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Haloalkylsulfonyl, C 1 -C 4 Alkylsulfonyloxy, C 2 -C 4 Alkyl carbonyl, C 3 -C 5 Alkenyl carbonyl group, C 3 -C 5 Alkynyl carbonyl group, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 7 Alkenyloxycarbonyl radical, C 3 -C 7 Alkynyloxycarbonyl group, C 2 -C 6 Alkylaminocarbonyl radical, C 3 -C 6 Alkenylaminocarbonyl group, C 3 -C 6 Alkynylaminocarbonyl or C 3 -C 8 A dialkylaminocarbonyl group.
Embodiment 127. The composition of embodiment 126, wherein each R 11a Independently of one another is halogen, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkoxyalkyl group, C 2 -C 4 Alkylcarbonyl group, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 7 Alkenyloxycarbonyl radical or C 2 -C 6 An alkylaminocarbonyl group.
Embodiment 128. The composition of embodiment 127, wherein each R 11a Independently of one another is halogen, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkylcarbonyl group, C 2 -C 4 Alkoxycarbonyl or C 3 -C 5 An alkenyloxycarbonyl group.
Embodiment 128a the composition of embodiment 128, wherein each R 11a Independently of one another is halogen, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy or C 2 -C 3 An alkoxycarbonyl group.
Embodiment 128b. The composition of embodiment 128a, wherein each R 11a Independently a methoxycarbonyl group or an ethoxycarbonyl group.
Embodiment 128c. The composition of embodiment 128b, wherein each R 11a Is an ethoxycarbonyl group.
Embodiment 129. The composition of matter described in any of embodiments 1 to 128c comprising components (a) and (b), wherein in formula 1, each R 11b Independently is C 1 -C 2 Alkyl radical, C 1 -C 2 Alkoxy radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 An alkoxycarbonyl group.
Embodiment 130. The composition of embodiment 129, wherein each R 11b Independently methyl, methoxy, methylcarbonyl or methoxycarbonyl.
Embodiment 131. The composition of embodiment 130, wherein each R 11b Independently methyl or methoxy.
Embodiment 132. The composition of the summary of any of embodiments 1 to 131, comprising components (a) and (b), wherein in formula 1, E is E 2 。
Embodiment 133. The composition of matter of any of embodiments 1 to 132 comprising components (a) and (b), wherein in formula 1, G is optionally selected independently from R by up to 3 13 Phenyl substituted with the substituent of (1); or 5-to 6-membered heteroaromatic rings, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, each ring optionally substituted with up to 3 heteroatoms independently selected from R 13 Substituted with the substituent(s); or a 3-to 7-membered non-aromatic ring or an 8-to 11-membered bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and optionally up to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms and up to 4N atoms Wherein up to 2 ring members are independently selected from C (= O), S (= O) and S (= O) 2 Each ring or ring system is optionally substituted with up to 3 independently selected R 13 Is substituted with the substituent(s).
Embodiment 134. The composition of embodiment 133, wherein G is selected from G-1 through G-118 as shown in example a.
Example A
Figure BDA0003913878900000531
Figure BDA0003913878900000541
Figure BDA0003913878900000551
Figure BDA0003913878900000561
Figure BDA0003913878900000571
Wherein the floating bond is attached to Z in formula 1 through any available carbon or nitrogen atom of the depicted ring or ring system; and x is 0, 1, 2 or 3.
Embodiment 135 the composition of embodiment 134, wherein G is G-1 to G-16, G-20, G-22 to G-30, G-36 to G-42, G-54 to G-60, G-85, G-86, G-108, G-110, or G-111.
Embodiment 136 the composition of embodiment 135, wherein G is G-1 to G-16, G-22, G-24, G-25, G-26, G-28, G-29, G-30, G-36, G-37, G-38, G-41, G-42, G-54, G-57, G-58, G-59, G-60, G-85, G-86, G-108, G-110, or G-111.
Embodiment 137. The composition of embodiment 136, wherein G is G-1 to G-13, G-22, G-24, G-25, G-26, G-28, G-29, G-41, G-42, G-54, G-57, G-58, G-59, or G-60.
Embodiment 138. The composition of embodiment 137, wherein G is G-1, G-2, G-3, G-7, G-8, G-9, G-10, G-12, G-13, G-22, G-29, G-42, G-54, or G-58.
Embodiment 139. The composition of embodiment 138, wherein G is G-1, G-3, G-12, G-13, G-22, or G-42.
Embodiment 140 the composition of embodiment 139, wherein G is G-1, G-3, G-12, G-13, or G-22.
Embodiment 141. The composition of embodiment 140, wherein G is G-1, G-3, G-12, or G-22.
Embodiment 142. The composition of embodiment 141, wherein G is G-1 or G-12.
Embodiment 143. The composition of embodiment 142 wherein G is G-1.
The composition of embodiment 144, wherein G is G-12.
Embodiment 145 the composition of embodiment 140, wherein G is G-3.
Embodiment 146. The composition of embodiment 140, wherein G is G-22.
Embodiment 147. The composition of embodiment 143, wherein position 2 of G-1 is attached to Z and position 4 is attached to R 13 。
Embodiment 148. The composition of embodiment 143, wherein position 2 of G-1 is attached to Z and position 5 is attached to R 13 。
Embodiment 149. The composition of embodiment 144, wherein the 1-position of G-12 is attached to Z and the 4-position is attached to R 13 。
Embodiment 150 the composition of embodiment 144, wherein position 1 of G-12 is attached to Z and position 3 is attached to R 13 。
Embodiment 151. The composition of embodiment 144, wherein position 1 of G-12 is attached to Z and positions 3 and 5 are attached to R 13 。
Embodiment 152. The composition of embodiment 144, wherein G-12With 1 to Z and 5 to R 13 。
Embodiment 153. The composition of embodiment 145, wherein position 1 of G-3 is attached to Z and position 4 is attached to R 13 。
Embodiment 154 the composition of embodiment 146, wherein the 4-position of G-22 is attached to Z and the 2-position is attached to R 13 。
The composition of any one of embodiments 147 to 154, wherein Z is a direct bond.
Embodiment 156 the composition of any one of embodiments 147 to 155, wherein x is 1 and R 13 Is methoxycarbonyl or ethoxycarbonyl.
The composition of any one of embodiments 134 to 155, wherein x is 1 or 2.
Embodiment 158. The composition of embodiment 157, wherein x is 1.
Embodiment 159. The composition of embodiment 157, wherein x is 2.
Embodiment 160. A composition as described in the summary of the invention of any of embodiments 134 to 155 comprising components (a) and (b), wherein in formula 1, x is 0.
Embodiment 161. The composition of the summary of the invention of any one of embodiments 1 to 159, including components (a) and (b), wherein in formula 1, each R is 13 Independently of one another cyano, halogen, NR 14a R 14b 、C(＝O)NR 14a R 14b 、C(R 15 )＝NR 16 、N＝CR 17 NR 18a R 18b or-U-V-Q; or C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylsulfonyloxy, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkylcarbonyl group, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl, C 4 -C 7 Cycloalkoxycarbonyl radical, C 2 -C 6 Alkylcarbonyloxy, C 2 -C 6 Alkoxycarbonyloxy, C 4 -C 7 Cycloalkoxy-carbonyloxy, C 2 -C 6 Alkylamino carbonyloxy radical, C 2 -C 6 Alkylcarbonylamino, C 2 -C 6 Alkoxycarbonylamino group or C 2 -C 6 (ii) alkylaminocarbonylamino, each of which is optionally substituted with up to 3 independently selected from R 19 Is substituted with the substituent(s).
Embodiment 162. The composition of embodiment 161, wherein each R 13 Independently is cyano, halogen, C (= O) NR 14a R 14b or-U-V-Q; or C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylsulfonyloxy, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkylcarbonyl group, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl or C 2 -C 6 Alkoxycarbonyloxy, each of which is optionally selected up to 3 independently from R 19 Is substituted with the substituent(s).
The composition of embodiment 162, wherein each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylsulfonyloxy, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkylcarbonyl group, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl group, C 4 -C 6 Cycloalkoxycarbonyl radical or C 2 -C 6 Alkoxycarbonyloxy, each of which is optionally selected up to 3 independently from R 19 Is substituted.
Embodiment 163a the composition of embodiment 162, wherein each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkenyloxycarbonyl radical, C 3 -C 5 Alkynyloxycarbonyl or C 4 -C 6 Cycloalkoxycarbonyl groups, each of which is optionally selected by up to 3 independently from R 19 Is substituted with the substituent(s).
Embodiment 163b the composition of embodiment 163a, wherein each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkynyloxycarbonyl or C 4 -C 6 Cycloalkoxycarbonyl, each of which is optionally substituted by up to 1R 19 Is substituted.
Embodiment 164. The composition of embodiment 163a, wherein each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl or C 2 -C 6 Alkoxycarbonyloxy, each of which is optionally selected up to 3 independently from R 19 Is substituted with the substituent(s).
Embodiment 164a the composition of embodiment 164 wherein each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, or C 3 -C 6 Alkynyloxycarbonyl, each of which is optionally up to 3 independently selected from R 19 Is substituted with the substituent(s).
The composition of embodiment 165, wherein each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkenyloxycarbonyl radical, or C 3 -C 5 Alkynyloxycarbonyl, each of which is optionally substituted with up to 3 independently selected from R 19 Is substituted with the substituent(s).
Embodiment 165a the composition of embodiment 165, wherein each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 5 Alkoxycarbonyl or C 3 -C 5 Alkenyloxycarbonyl, each of which is optionally substituted with up to 3 substituents independently selected from R 19 Is substituted with the substituent(s).
Embodiment 166. The composition of embodiment 165, wherein each R 13 Independently is C 2 -C 5 Alkoxycarbonyl or C 3 -C 5 Alkenyloxycarbonyl groups, each of which is optionally selected by up to 3 independently from R 19 Is substituted with the substituent(s).
Embodiment 167. The composition of embodiment 166, wherein each R 13 Independently is C 2 -C 5 Alkoxycarbonyl, each of which is optionally substituted with up to 3 substituents independently selected from R 19 Is substituted with the substituent(s).
Embodiment 168. The composition of embodiment 167, wherein each R 13 Independently is methoxycarbonyl or ethoxycarbonyl, each of which is optionally selected up to 3 independently from R 19 Is substituted with the substituent(s).
The composition of embodiment 169. The composition of embodiment 168, wherein each R 13 Independently is methoxycarbonyl or ethoxycarbonyl, each of which is optionally substituted by up to 1 selected from R 19 Is substituted with the substituent(s).
Embodiment 170. The composition of embodiment 169, wherein each R 13 Independently by up to 1 selected from R 19 Substituted ethoxycarbonyl group of (2).
The composition of embodiment 169, wherein each R 13 Independently methoxycarbonyl or ethoxycarbonyl.
Embodiment 172. The composition of embodiment 171, wherein each R 13 Is an ethoxycarbonyl group.
Embodiment 173. The composition of matter described in this summary of any one of embodiments 1 to 172 comprising components (a) and (b), wherein in formula 1, when each R is 14a Is isolated (i.e. not bound to R) 14b Together form a ring), then each R 14a Independently is H, cyano, hydroxy, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Haloalkenyl, C 2 -C 4 Alkynyl, C 2 -C 4 Halogenated alkynyl, C 2 -C 4 Alkyl carbonyl, C 2 -C 5 Alkoxycarbonyl or C 3 -C 5 A dialkylaminocarbonyl group.
Embodiment 174. The composition of embodiment 173, wherein each R 14a Independently of one another H, cyano, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, C 2 -C 4 Alkyl carbonyl, C 2 -C 5 Alkoxycarbonyl or C 3 -C 5 A dialkylaminocarbonyl group.
Embodiment 175. The composition of embodiment 174, wherein each R 14a Independently of each other H, C 1 -C 2 Alkyl radical, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 An alkoxycarbonyl group.
Embodiment 176. The composition of embodiment 175, wherein each R 14a Independently is H or C 1 -C 2 An alkyl group.
Embodiment 177. The composition of embodiment 176, wherein each R 14a Independently is H or methyl.
Embodiment 177a the composition of embodiment 177, wherein each R 14a Is H.
Embodiment 178. Any one of embodiments 1 to 177aThe composition comprising components (a) and (b) described in the summary of the invention, wherein in formula 1, when each R is 14b Is isolated (i.e. not bound to R) 14a Together form a ring), then each R 14b Independently of each other H, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl radical, C 2 -C 6 Haloalkenyl, C 2 -C 6 Alkynyl, C 2 -C 6 Halogenated alkynyl, C 2 -C 6 Cyanoalkyl, C 3 -C 8 Cycloalkyl radical, C 3 -C 8 Halogenocycloalkyl, C 3 -C 8 Cycloalkenyl radical, C 3 -C 8 Halogenated cycloalkenyl, C 4 -C 10 Alkyl cycloalkyl radical, C 4 -C 10 Cycloalkylalkyl radical, C 4 -C 10 Halocycloalkylalkyl radical, C 2 -C 6 Alkoxyalkyl group, C 2 -C 6 Haloalkoxyalkyl, C 2 -C 6 Alkylthioalkyl, C 2 -C 6 Alkylsulfonylalkyl group, C 2 -C 6 Alkylaminoalkyl or C 3 -C 8 Dialkylaminoalkyl, each optionally substituted by up to 1 substituent selected from cyano, hydroxy, nitro, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 Substituent of alkoxycarbonyl.
Example 179. The composition of example 178, wherein each R 14b Independently of each other H, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Halogenated alkenyl group, C 2 -C 4 Alkynyl, C 3 -C 5 Cycloalkyl radical, C 4 -C 6 Cycloalkylalkyl radical, C 2 -C 4 Alkoxyalkyl group, C 2 -C 4 Haloalkoxyalkyl, C 2 -C 4 Alkylaminoalkyl or C 3 -C 5 A dialkylaminoalkyl group.
Example 180. The composition of example 179, wherein each R 14b Independently of each other H, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Haloalkenyl, C 3 -C 5 Cycloalkyl, C 4 -C 6 Cycloalkylalkyl or C 2 -C 4 An alkoxyalkyl group.
Embodiment 181. The composition of embodiment 180, wherein each R 14b Independently of each other H, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, cyclopropylmethyl or C 2 -C 4 An alkoxyalkyl group.
The composition of embodiment 181a, wherein each R 14b Independently of each other H, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl or cyclopropylmethyl.
Embodiment 181b. The composition of embodiment 181a, wherein each R 14b Independently H, methyl or cyclopropylmethyl.
Embodiment 182. The composition of the summary of the invention as described in any of embodiments 1 to 181b comprising components (a) and (b), wherein in formula 1, when R is 14a And R 14b Together form a 4-to 6-membered fully saturated heterocyclic ring, then in addition to the linking nitrogen atom, said ring contains ring members selected from carbon atoms and up to 1 heteroatom selected from up to 1O atom, up to 1S atom and up to 1N atom, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.
Embodiment 183 the composition of embodiment 182, wherein R 14a And R 14b Together form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.
The composition of embodiment 184, wherein R 14a And R 14b Together form an azetidinyl or pyrrolidinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.
Embodiment 185 as in any of embodiments 1-184The composition comprising the components (a) and (b) described in the summary of the invention, wherein in formula 1, each R 15 Independently H, cyano, halogen, methyl or methoxy.
The composition of embodiment 185, wherein each R 15 Independently is H or methyl.
Embodiment 187. The composition of the summary of the invention as described in any one of embodiments 1 to 186, comprising components (a) and (b), wherein in formula 1, each R is 16 Independently of one another is hydroxy, NR 20a R 20b 、C 1 -C 2 Alkoxy radical, C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkylcarbonyloxy or C 2 -C 4 An alkoxycarbonyloxy group.
Embodiment 188. The composition of embodiment 187, wherein each R 16 Independently of one another is hydroxy, NR 20a R 20b Or C 1 -C 4 An alkoxy group.
Embodiment 189. The composition of embodiment 188, wherein each R 16 Independently of one another is hydroxy, NR 20a R 20b Or a methoxy group.
The composition of embodiment 190, wherein each R 16 Is a hydroxyl group.
Embodiment 191. The composition of the summary of the invention as described in any one of embodiments 1 to 190 comprising components (a) and (b), wherein in formula 1, each R 17 Independently is H or methyl.
Embodiment 192. The composition of embodiment 191, wherein each R 17 Is H.
Embodiment 193. Composition as described in the summary of the invention of any one of embodiments 1 to 192, including components (a) and (b), wherein in formula 1, when each R is 18a And R 18b When they are separate (i.e. do not form a ring together), then each R is 18a And R 18b Independently H, methyl or ethyl.
Embodiment 194. The composition of embodiment 193, wherein each R 18a And R 18b Independently is H or methyl.
Embodiment 195. The composition of the summary of the invention as described in any of embodiments 1 to 194, comprising components (a) and (b), wherein in formula 1, when R is 18a And R 18b Taken together to form a 5-to 6-membered fully saturated heterocyclic ring, then in addition to the linking nitrogen atom, the ring contains ring members selected from carbon atoms and up to 1 heteroatom selected from up to 1O atom, up to 1S atom and up to 1N atom, each ring optionally substituted with up to 2 methyl groups.
Embodiment 196 the composition of embodiment 195, wherein R 18a And R 18b Together form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl, or thiomorpholinyl ring, each ring optionally substituted with up to 2 methyl groups.
Embodiment 197. A composition as described in the summary of any of embodiments 1 to 196 comprising components (a) and (b), wherein in formula 1, each R 19 Independently cyano, halogen, hydroxy, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 3 -C 6 Cycloalkyl, C 1 -C 3 Alkoxy radical, C 1 -C 3 Haloalkoxy, C 2 -C 3 Alkoxyalkoxy radical, C 1 -C 3 Alkylthio radical, C 1 -C 3 Alkylsulfinyl radical, C 1 -C 3 Alkylsulfonyl radical, C 1 -C 3 Haloalkylsulfonyl group, C 2 -C 3 Alkylcarbonyl group, C 2 -C 3 Halogenoalkylcarbonyl group, C 2 -C 3 Alkoxycarbonyl group, C 2 -C 3 Alkylaminocarbonyl or C 3 -C 5 A dialkylaminocarbonyl group.
The composition of embodiment 198, wherein each R 19 Independently cyano, halogen, hydroxy, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 3 -C 6 Cycloalkyl radical, C 1 -C 2 Alkoxy radical, C 1 -C 2 Haloalkoxy, C 1 -C 2 Alkylthio radical, C 1 -C 2 Alkylsulfonyl radical, C 1 -C 2 Haloalkylsulfonyl group, C 2 -C 3 Alkyl carbonyl, C 2 -C 3 Halogenoalkylcarbonyl group, C 2 -C 3 Alkoxycarbonyl or C 2 -C 3 An alkylaminocarbonyl group.
Embodiment 199. The composition of embodiment 197, wherein each R 19 Independently of one another is cyano, halogen, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 3 -C 6 Cycloalkyl radical, C 1 -C 2 Alkoxy radical, C 1 -C 2 Haloalkoxy, C 2 -C 3 Alkylcarbonyl group, C 2 -C 3 Halogenoalkylcarbonyl or C 2 -C 3 An alkoxycarbonyl group.
Embodiment 200 the composition of embodiment 199, wherein each R 19 Independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl.
Embodiment 200a the composition of embodiment 200, wherein each R 19 Independently cyano, halogen, cyclopropyl or methoxy.
Embodiment 200b the composition of embodiment 200a, wherein each R 19 Independently cyano, cl, F, cyclopropyl or methoxy.
Embodiment 201. A composition as described in the summary of the invention of any of embodiments 1 to 200b, comprising components (a) and (b), wherein in formula 1, each U is independently a direct bond, C (= O) O, or C (= O) N (R) 25 )。
The composition of embodiment 202. The composition of embodiment 201, wherein each U is independently a direct bond or C (= O) O.
The composition of embodiment 203. The composition of embodiment 202, wherein each U is C (= O) O.
Embodiment 204. A composition as described in the summary of the invention of any one of embodiments 1 to 203 comprising components (a) and (b), wherein in formula 1, each V is independently a direct bond; or C 1 -C 6 Alkylene radical, C 2 -C 6 Alkenylene or C 3 -C 6 Alkynylene, each optionally substituted with up to 2 substituents independently selected from halogen, cyano, nitro, hydroxy, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy and C 1 -C 2 A substituent of a haloalkoxy group.
The composition of embodiment 205, wherein each V is independently a direct bond; or C 1 -C 3 Alkylene each optionally substituted by up to 2 independently selected from halogen, hydroxy, C 1 -C 2 Alkyl radical, C 1 -C 2 Alkoxy and C 1 -C 2 A substituent of a haloalkoxy group.
Embodiment 206. The composition of embodiment 205, wherein each V is independently a direct bond or C 1 -C 3 An alkylene group.
Embodiment 207. The composition of embodiment 206, wherein each V is independently a direct bond or CH 2 。
The composition of embodiment 208. The composition of embodiment 207, wherein each V is a direct bond.
Embodiment 209 the composition of embodiment 207, wherein each V is independently C 1 -C 2 An alkylene group.
Embodiment 210. The composition of embodiment 209, wherein each V is CH 2 。
Embodiment 211. The composition of matter of any one of embodiments 1 to 210 comprising components (a) and (b), wherein in formula 1, each Q is independently optionally selected from R independently by up to 2 27 Phenyl substituted with the substituent of (1); or 5-to 6-membered heteroaromatic rings, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, each ring optionally substituted with up to 2 heteroatoms independently selected from R 27 Substituted with the substituent(s); or a 3-to 6-membered non-aromatic heterocyclic ring, each ring containing carbon atoms and 1 to 4 atoms independently selected from up to 2O atoms, up to 2S atoms and up to 4N atoms Wherein up to 2 ring members are independently selected from the group consisting of C (= O), C (= S), S (= O) and S (= O) 2 Each ring is optionally substituted with up to 2 substituents independently selected from R 27 Is substituted with the substituent(s).
Embodiment 212. The composition of embodiment 210, wherein each Q is independently optionally selected from R by up to 2 27 Phenyl substituted with the substituent of (1); or pyridyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isoxazolyl, thienyl, isoxazolinyl, piperidinyl, morpholinyl or piperazinyl, each of which is optionally up to 2 independently selected from R 27 Is substituted with the substituent(s).
Embodiment 213 the composition of embodiment 212, wherein each Q is independently optionally selected from R independently by up to 2 27 Phenyl substituted with the substituent of (1); or pyridyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl or oxazolyl, each of which is optionally up to 2 independently selected from R 27 Is substituted.
Embodiment 214 the composition of embodiment 213, wherein each Q is independently optionally selected from R independently by up to 2 27 Phenyl substituted with the substituent of (1); or pyridyl or pyrazolyl, each of which is optionally substituted by up to 2 substituents independently selected from R 27 Is substituted.
Embodiment 214a the composition of embodiment 214, wherein each Q is independently phenyl or pyridyl, each of which is optionally selected with up to 2 independently selected from R 27 Is substituted with the substituent(s).
Embodiment 214b the composition of embodiment 214a, wherein each Q is independently optionally selected up to 2 independently from R 27 Phenyl substituted with the substituent(s) of (1).
Embodiment 215. The composition of matter described in this summary of any one of embodiments 1 to 214b, including components (a) and (b), wherein in formula 1, when each R is 20a Is isolated (i.e. not bound to R) 20b Together form a ring), then each R 20a Independently H, methyl or methylcarbonyl.
Embodiment 216. The composition of matter as described in any one of embodiments 1 to 215 comprising components (a) and (b), wherein in formula 1, when each R is 20b Is isolated (i.e. not bound to R) 20a Together form a ring), then each R 20b Independently H, cyano, methyl, methylcarbonyl, methoxycarbonyl, methoxycarbonylmethyl, methylaminocarbonyl or dimethylaminocarbonyl.
Embodiment 217. The composition of the summary of the invention as described in any one of embodiments 1 to 216 comprising components (a) and (b), wherein in formula 1, when R is 20a And R 20b Taken together to form a 5-to 6-membered fully saturated heterocyclic ring, then in addition to the linking nitrogen atom, the ring contains ring members selected from carbon atoms and up to 1 heteroatom selected from up to 1O atom, up to 1S atom and up to 1N atom, each ring optionally substituted with up to 2 methyl groups.
Embodiment 218. The composition of embodiment 217, wherein R 20a And R 20b Together form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl, or thiomorpholinyl ring, each ring optionally substituted with up to 2 methyl groups.
Embodiment 219. The composition of the summary of the invention as described in any one of embodiments 1 to 218, comprising components (a) and (b), wherein in formula 1, each R 21 And R 23 Independently H, cyano, halogen, methyl or methoxy.
Embodiment 220. The composition of matter as described in the summary of the invention of any one of embodiments 1 to 219, comprising components (a) and (b), wherein in formula 1, each R 22 Independently of each other H, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 An alkoxycarbonyl group; or phenyl optionally substituted with up to 2 substituents independently selected from halogen and methyl; or a 5-to 6-membered fully saturated heterocyclic ring, each ring containing up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, and carbon atoms Ring members, each ring optionally substituted with up to 2 substituents independently selected from halogen and methyl.
Embodiment 221. The composition of embodiment 220, wherein each R 22 Independently is H or C 1 -C 2 An alkyl group.
Embodiment 222. The composition of the summary of the invention as described in any one of embodiments 1 to 221 comprising components (a) and (b), wherein in formula 1, each R 24 Independently is H, cyano or C 1 -C 2 An alkyl group.
Embodiment 223. The composition of the summary of the invention as described in any of embodiments 1 to 222, comprising components (a) and (b), wherein in formula 1, each R is 25 And R 26 Independently is H, cyano, hydroxy, C 1 -C 4 Alkyl or C 1 -C 4 A haloalkyl group.
The composition of embodiment 224, wherein each R 25 And R 26 Independently is H, cyano, hydroxy or C 1 -C 2 An alkyl group.
Embodiment 225. The composition of matter described in this summary of any one of embodiments 1 to 224 including components (a) and (b), wherein in formula 1, each R 27 Independently of one another is halogen, cyano, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl or C 1 -C 4 An alkoxy group.
Embodiment 226. The composition of embodiment 225, wherein each R 27 Independently of one another is halogen, cyano, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl or C 1 -C 2 An alkoxy group.
Embodiment 227 the composition of embodiment 226, wherein each R 27 Independently halogen, methyl or methoxy.
Embodiment 228. The composition of embodiment 227, wherein each R 27 Independently a halogen.
Embodiment 229. Composition comprising components (a) and (b) as described in the summary of the invention of any one of embodiments 1 to 228Wherein in formula 1, Z is a direct bond, O, NH, C (= O) NH, NHC (= O) NH, OC (= O) NH, NHC (= O) O, S (= O) 2 NH、NHS(＝O) 2 Or NHS (= O) 2 NH。
The composition of embodiment 230, wherein Z is a direct bond, O, NH, C (= O) NH, or NHC (= O).
The composition of embodiment 231. Wherein Z is a direct bond, O, NH, or C (= O).
The composition of embodiment 232. The composition of embodiment 231, wherein Z is a direct bond.
Embodiment 233. The composition of formula 1 as described in any one of embodiments 1 to 232, wherein each R is 28 Independently is H or C 1 -C 3 An alkyl group.
Embodiment 234 the composition of embodiment 233, wherein each R 28 Independently H or methyl.
Embodiment 235. A composition as described in the summary of the invention of any one of embodiments 1 to 234, comprising components (a) and (b), wherein in formula 1, m is 0 or 2.
Embodiment 236. The composition of embodiment 235, wherein m is 2.
Embodiment 237. The composition of matter described in the summary of any of embodiments 1 to 236 comprising components (a) and (b), wherein component (a) does not comprise an N-oxide of the compound having formula 1.
Embodiment 238. A composition as described in the summary of the invention of any of embodiments 1 to 236 comprising components (a) and (b), wherein component (a) comprises a compound selected from the group consisting of
1- [ [4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester (compound 1);
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester (compound 32);
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester (compound 64);
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-3-carboxylic acid ethyl ester (compound 231);
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] -3-fluorophenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester (compound 262);
1- [ [3- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester (compound 265);
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenoxy ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester (compound 364);
n- (cyclopropylmethyl) -2- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] thiazole-4-carboxamide (compound 71);
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid 2-methylpropyl ester (compound 126);
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid cyclopropylmethyl ester (compound 127);
1- [2- [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] ethyl ] -1H-pyrazole-4-carboxylic acid ethyl ester (compound 132);
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid 2-methoxyethyl ester (compound 162);
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid 2-butyn-1-yl ester (compound 163);
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid 3-cyanopropyl ester (compound 171);
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid phenylmethyl ester (compound 186);
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid butyl ester (compound 218);
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid 3-chloropropyl ester (compound 221);
methyl 4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) benzoate (compound 229);
ethyl 1- [ [ 3-fluoro-4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate (compound 263);
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenylmethoxy ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester (compound 297);
1- [ [3- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid methyl ester (compound 330); and
1- [ [3- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid propyl ester (compound 331).
The composition of embodiment 239, wherein component (a) comprises a compound selected from the group consisting of: compounds 32, 64, 71, 126, 127, 132, 162, 163, 171, 186, 218, 229, 263, 297, 330 and 331.
Embodiment 240 the composition of embodiment 239, wherein component (a) comprises a compound selected from the group consisting of: compounds 32, 64, 71, 126, 127, 132, 162, 163, 171, 218, 229 and 263.
Embodiment 241. The composition of embodiment 240, wherein component (a) comprises a compound selected from the group consisting of: compounds 32, 64, 126, 127, 132, 162, 163, 171 and 263.
Embodiment 242 the composition of embodiment 241, wherein component (a) comprises a compound selected from the group consisting of: compounds 32, 64, 126, 132, 163 and 263.
The composition of embodiment 243, wherein component (a) comprises a compound selected from the group consisting of: compounds 32 and 64.
Embodiment 243a. The composition of embodiment 243, wherein component (a) is compound 32.
Embodiment 243b. The composition of embodiment 243, wherein component (a) is compound 64.
Embodiment 244. The composition of matter as described in any one of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is ethyl 1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate, an (E) -isomer thereof, or a mixture thereof.
Embodiment 245 a composition as described in the summary of the invention of any one of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is ethyl 1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate, its (E) -isomer, or a mixture thereof.
Embodiment 246. The composition of matter described in the summary of the invention of any of embodiments 1 to 243, comprising components (a) and (b), wherein component (a) is ethyl 1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] -3-fluorophenyl ] methyl ] -1H-pyrazole-4-carboxylate, an (E) -isomer thereof, or a mixture thereof.
Embodiment 247 a composition as described in the summary of the invention of any of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is ethyl 1- [ [3- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate, its (E) -isomer, or a mixture thereof.
Embodiment 248. The composition of matter as described in any of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is ethyl 1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenoxy ] methyl ] -1H-pyrazole-4-carboxylate, its (E) -isomer, or a mixture thereof.
Embodiment 249. A composition as described in the summary of the invention of any of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is ethyl 1- [2- [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] ethyl ] -1H-pyrazole-4-carboxylate, its (E) -isomer, or a mixture thereof.
Embodiment 250. A composition as described in the summary of the invention of any one of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is phenylmethyl 1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate, its (E) -isomer, or a mixture thereof.
Embodiment 251. A composition as described in the summary of any one of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is butyl 1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate, its (E) -isomer, or a mixture thereof.
Embodiment 252. The composition of matter as described in the summary of any one of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is 3-chloropropyl 1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate, its (E) -isomer, or a mixture thereof.
Embodiment 253. The composition of matter as described in any one of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is ethyl 1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenylmethoxy ] methyl ] -1H-pyrazole-4-carboxylate, its (E) -isomer, or a mixture thereof.
Embodiment 254 the composition as described in the summary of any one of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is methyl 1- [ [3- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate, its (E) -isomer, or a mixture thereof.
Embodiment 255. A composition as described in the summary of the invention of any one of embodiments 1 to 243 comprising components (a) and (b), wherein component (a) is propyl 1- [ [3- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate, its (E) -isomer, or a mixture thereof.
Embodiment 256. The composition of embodiments 238 to 255, wherein when component (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenoconazole, epoxiconazole, flutriafol, metconazole, prothioconazole or tebuconazole, then the other fungicidal compound is not azoxystrobin, benzovindiflupyr, bixafen, boscalid, fluopyram, fluindazoxamide, fluxapyroxad, isopyrazam, kresoxim-methyl, penthiopyrad, picoxystrobin, proquinclorac-ethyl, pyraclostrobin, quinoxyfen, epoxiconazole or trifloxystrobin.
Embodiment 257 the composition of embodiments 238-256, wherein when component (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenoconazole, epoxiconazole, flutriafol, prothioconazole or tebuconazole, the other fungicidal compound is not azoxystrobin, benzovindiflupyr, bixafen, indazoxamine, fluxapyroxad, isopyrazam, picoxystrobin, pyraclostrobin, or trifloxystrobin.
Embodiment 258. The composition of embodiment 257 wherein (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenoconazole, epoxiconazole, flutriafol, prothioconazole or tebuconazole, the other fungicidal compound is not azoxystrobin, benzovindiflupyr, bixafen, thiabendazole, fluxapyroxad, flutolanil, picoxystrobin, pyraclostrobin or trifloxystrobin.
Embodiments of the invention (including examples 1-258 above and any other embodiments described herein) may be combined in any manner, and the description of variables in the embodiments is directed not only to compositions comprising a compound having formula 1 and at least one other fungicidal compound, but also to compositions comprising a compound having formula 1 and at least one invertebrate pest control compound or agent, and also to compounds having formula 1 and compositions thereof, and also to starting compounds and intermediate compounds useful for preparing compounds having formula 1. Further, embodiments of the present invention (including embodiments 1-258 above as well as any other embodiments described herein) and any combination thereof relate to methods of the present invention. Thus, as another embodiment, of note is a composition as disclosed above comprising (a) at least one compound selected from the group consisting of compounds having formula 1, N-oxides, and salts thereof described above; and at least one invertebrate pest control compound or agent.
The combination of examples 1-258 is shown below:
example a. The composition described in this summary comprising components (a) and (b), wherein component (a) comprises a compound having formula 1 or a salt thereof, wherein in formula 1,
R 1 is CF 3 、CCl 3 Or CF 2 Cl；
W is O;
R 5a and R 5b Each independently is H, hydroxy or methyl;
R 2a and R 2b Each independently is H or methyl; or
R 2a And R 2b Form, together with the atoms X and Y to which they are attached, a 5-to 6-membered saturated ring containing, in addition to these atoms X and Y, a ring member selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C (= O), the ring being optionally substituted on a carbon atom ring member with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy;
R 2c is C 1 -C 2 Alkyl radical, C 2 -C 3 Alkenyl or C 2 -C 3 Alkynyl;
R 2d is H or methyl;
A 1 is CR 6c R 6d Or O;
A 2 is a direct bond, CR 6e R 6f Or O;
R 6a 、R 6b 、R 6c 、R 6d 、R 6e and R 6f Each independently is H, cyano, hydroxy, br, cl, F, or methyl;
j is J-1, J-6 or J-14;
each R 8 Independently F, cl or methyl;
each R 9a And R 9b Independently is H, halogen or methyl;
n is 0, 1 or 2;
E 1 is C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylsulfonyl radical, C 2 -C 6 Alkylcarbonyl or C 2 -C 6 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1 atom selected from R 10a And up to 3 substituents independently selected from R 10b Substituted with the substituent(s);
R 10a is optionally selected from R by up to 2 11a Phenyl substituted with the substituent of (1); or a 5-to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, each ring optionally substituted with up to 2 substituents independently selected from R on the carbon atom ring members 11a And independently selected from R on a nitrogen ring member 11b ；
Each R 10b Independently of one another is halogen, hydroxy, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 1 -C 4 Alkylsulfonyl radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 5 An alkoxycarbonyl group;
each R 11a Independently of one another is halogen, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy or C 2 -C 3 An alkoxycarbonyl group;
each R 11b Independently is methyl, methoxy, methylcarbonyl or methoxycarbonyl;
g is selected from the group consisting of:
Figure BDA0003913878900000741
Figure BDA0003913878900000751
Figure BDA0003913878900000761
Figure BDA0003913878900000771
Figure BDA0003913878900000781
wherein the floating bond is attached to Z in formula 1 through any available carbon or nitrogen atom of the depicted ring or ring system; and x is 0, 1, 2 or 3;
each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylsulfonyloxy, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkyl carbonyl, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl group, C 4 -C 6 Cycloalkoxycarbonyl radical or C 2 -C 6 Alkoxycarbonyloxy, each of which is optionally substituted with up to 3 independently selected from R 19 Substituted with the substituent(s);
each R 14a Independently of each other H, C 1 -C 2 Alkyl radical, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 An alkoxycarbonyl group;
each R 14b Independently of each other H, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Halogenated alkenyl group, C 2 -C 4 Alkynyl, C 3 -C 5 Cycloalkyl, C 4 -C 6 Cycloalkylalkyl radical, C 2 -C 4 Alkoxyalkyl group, C 2 -C 4 Haloalkoxyalkyl, C 2 -C 4 Alkylaminoalkyl or C 3 -C 5 A dialkylaminoalkyl group; or
R 14a And R 14b Together form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl, or thiomorpholinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl;
each R 19 Independently of one another is cyano, halogen, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 3 -C 6 Cycloalkyl radical, C 1 -C 2 Alkoxy radical, C 1 -C 2 Haloalkoxy, C 2 -C 3 Alkylcarbonyl group, C 2 -C 3 Halogenoalkylcarbonyl or C 2 -C 3 An alkoxycarbonyl group;
each U is independently a direct bond, C (= O) O, or C (= O) N (R) 25 )；
Each V is independently a direct bond; or C 1 -C 3 Alkylene each optionally substituted by up to 2 independently selected from halogen, hydroxy, C 1 -C 2 Alkyl radical, C 1 -C 2 Alkoxy and C 1 -C 2 Substituted with a halo alkoxy group;
each Q is independently optionally selected from R by up to 2 27 Phenyl substituted with the substituent of (1); or pyridyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl or oxazolyl, each of which is optionally up to 2 independently selected from R 27 Substituted with the substituent(s);
each R 25 Independently H, cyano, hydroxy or C 1 -C 2 An alkyl group;
each R 27 Independently of one another is halogen, cyano, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl or C 1 -C 2 An alkoxy group; and is
Z is a direct bond, O, NH, C (= O) NH, NHC (= O) NH, OC (= O) NH, NHC (= O) O, S (= O) 2 NH、NHS(＝O) 2 Or NHS (= O) 2 NH。
The composition of example a, wherein in formula 1,
R 1 is CF 3 ；
X is O;
y is O;
l is a direct bond or CH 2 (ii) a And is
Z is a direct bond.
The composition as in example a, wherein in formula 1,
R 1 is CF 3 ；
Z is a direct bond.
The composition of embodiment a, wherein in formula 1,
t is T-2 or T-3;
R 1 is CF 3 ；
X is O;
y is O;
R 2a and R 2b Each independently is H or methyl; or
R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-membered saturated ring containing, in addition to these atoms X and Y, a ring member selected from carbon atoms, which ring is optionally substituted on the carbon atom ring member with up to 1 substituent selected from halogen, methyl and halomethyl;
R 2c is methyl or ethyl;
R 2d is H;
A 1 is O;
A 2 is a direct bond or CH 2 ；
R 6a And R 6b Each independently is H, cyanohydroxy or methyl;
j is J-1 or J-6;
q is 0 or 1;
each R 9a And R 9b Independently is H or methyl;
E 1 is C 1 -C 3 Alkoxy radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1R 10a And up to 3 substituents independently selected from R 10b Substituted with a substituent of (1);
R 10a is pyrazolyl, imidazolyl or triazolyl, each of which is optionally substituted by up to 2 independently selected R on a carbon atom ring member 11a Substituted with the substituent(s);
each R 10b Independently of one another is halogen, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy or C 2 -C 4 An alkoxycarbonyl group;
g is G-1, G-3, G-12 or G-22;
x is 1 or 2;
each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkenyloxycarbonyl radical, C 3 -C 5 Alkynyloxycarbonyl or C 4 -C 6 Cycloalkoxycarbonyl groups, each of which is optionally selected by up to 3 independently from R 19 Substituted with the substituent(s);
each R 14a Independently is H or C 1 -C 2 An alkyl group;
each R 14b Independently of each other H, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, cyclopropylmethyl or C 2 -C 4 An alkoxyalkyl group;
each R 19 Independently cyano, halogen, cyclopropyl, cyclobutylMethoxy, halomethoxy or methoxycarbonyl;
each U is independently a direct bond or C (= O) O;
each V is independently a direct bond or CH 2 ；
Each Q is independently phenyl or pyridyl, each of which is optionally substituted with up to 2 substituents independently selected from R 27 Substituted with the substituent(s);
each R 27 Independently is halogen, methyl or methoxy; and is provided with
Z is a direct bond, O, NH, C (= O) NH, or NHC (= O).
The composition of embodiment B, wherein in formula 1,
l is a direct bond or CH 2 ；
G is G-1 or G-12; and is
Z is a direct bond.
The composition of example B, wherein in formula 1,
z is a direct bond.
The composition of embodiment B, wherein in formula 1,
R 2a and R 2b Each is H; or
R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-membered saturated ring which, in addition to these atoms X and Y, contains a ring member selected from carbon atoms;
A 2 is a direct bond;
R 6a And R 6b Each is H;
R 8 is F or Cl;
l is a direct bond, CH 2 Or CH 2 CH 2 ；
E 1 Is C 1 -C 2 Alkoxy or C 2 -C 3 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1R 10a Substituted with the substituent(s);
R 10a is pyrazolyl or imidazolyl, each of which is optionally on a carbon atom ring memberIs selected from up to 2 independently from R 11a Substituted with the substituent(s);
each R 11a Independently is methoxycarbonyl or ethoxycarbonyl;
g is G-1 and the 2-position of G-1 is linked to Z and the 4-position is linked to R 13 (ii) a Or G is G-12 and G-12 is attached at position 1 to Z and at position 4 to R 13 (ii) a Or G is G-12 and G-12 is attached to Z in position 1 and to R in position 3 13 ；
x is 1;
R 13 is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkynyloxycarbonyl or C 4 -C 6 Cycloalkoxycarbonyl, each of which is optionally substituted by up to 1R 19 Substituted with the substituent(s);
R 14a is H;
R 14b is H, methyl or cyclopropylmethyl;
R 19 is cyano, halogen, cyclopropyl or methoxy;
u is C (= O) O;
v is CH 2 ；
Q is optionally selected from R by up to 2 27 Phenyl substituted with the substituent of (1); and is
Z is a direct bond, O, NH or C (= O).
The composition of embodiment C, wherein in formula 1,
l is a direct bond or CH 2 (ii) a And is
Z is a direct bond.
The composition of embodiment d, wherein in formula 1,
R 8 is F;
l is a direct bond or CH 2 ；
E 1 Is selected from 1R 10a Methoxy substituted with the substituent of (1);
R 10a is optionally substituted on a carbon atom ring member by up to 1R 11a Substituted pyridine ofAn azole group;
g is G-12 and the 1-position of G-12 is linked to Z and the 4-position is linked to R 13 (ii) a Or G is G-12 and G-12 is attached at position 1 to Z and at position 3 to R 13 (ii) a And is
R 13 Is optionally selected from R by up to 1 19 C substituted by a substituent of 2 -C 5 An alkoxycarbonyl group;
R 19 is cyano, cl, F, cyclopropyl or methoxy; and is
Z is a direct bond.
The composition of embodiment D, wherein in formula 1,
l is a direct bond or CH 2 Provided that when L is a direct bond, then E is E 1 And when L is CH 2 When E is E 2 。
The composition of embodiment e, wherein in formula 1,
j is J-1;
q is 0;
l is CH 2 ；
E is E 2 ；
G is G-12 and the 1-position of G-12 is linked to Z and the 4-position is linked to R 13 (ii) a And is
R 13 Is methoxycarbonyl or ethoxycarbonyl.
The composition as in example E, wherein in formula 1,
R 2a and R 2b Together with the atoms X and Y to which they are attached form a 5-membered saturated ring which, in addition to these atoms X and Y, contains a ring member selected from carbon atoms.
The composition of any one of embodiments a through EE, wherein in formula 1,
t is T-2; and is provided with
R 13 Is an ethoxycarbonyl group.
The composition of any one of embodiments a-E, wherein in formula 1,
t is T-3; and is
R 13 Is an ethoxycarbonyl group.
The composition of any one of embodiments a-G, wherein component (a) comprises a compound selected from the group consisting of: compound 1, compound 32, compound 64, compound 71, compound 126, compound 127, compound 132, compound 162, compound 163, compound 171, compound 186, compound 218, compound 221, compound 229, compound 231, compound 262, compound 263, compound 265, compound 297, compound 330, compound 331 and compound 364.
The composition of embodiment i.e., wherein component (a) comprises a compound selected from the group consisting of: compound 32, compound 64, compound 71, compound 126, compound 127, compound 132, compound 162, compound 163, compound 171, compound 186, compound 218, compound 229, compound 263, compound 297, compound 330 and compound 331.
The composition of example I wherein component (a) comprises compound 32.
The composition of embodiment I wherein component (a) comprises compound 64.
Example b1. The compositions described in this summary (including but not limited to the compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 1) benzimidazole methyl carbamate fungicides such as benomyl, carbendazim, furylbenzimidazole thiabendazole, thiophanate, and thiophanate-methyl.
An embodiment b2. The composition described in the summary of the invention (including but not limited to the composition as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 2) dicarboximide fungicides such as ethiprole, dimethachlon, iprodione, procymidone and vinclozolin.
Example b3. The compositions described in this summary (including, but not limited to, the compositions described in any of examples 1-258 and a-K), wherein component (b) comprises at least one compound selected from (b 3) demethylation inhibitor fungicides such as triforine, butithidine, pyribenzoxim, pyrisoxazole fenarimol, fluoropyrimidinol, pyrimethanil, imazalil, oxpoconazole, pefurazoate, prochloraz, triflumizole, bitertazole, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, clofadroconazole, metconazole, myclobutanil, penconazole, propiconazole, imazalil, quinconazole, simeconazole, tebuconazole, triadimefon, tetraconazole, triadimenol, diniconazole, uniconazole, and P-triticonazole.
An embodiment b4. The composition described in this summary (including, but not limited to, the composition as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 4) phenylamide fungicides such as metalaxyl, metalaxyl-M, benalaxyl-M, furalaxyl, furalamide, and oxadixyl.
Example b5. The compositions described in this summary (including, but not limited to, the compositions described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 5) an amine/morpholine fungicide such as 4-dodecyl-2, 6-dimethylmorpholine, dodecacyclomorpholine, fenpropimorph, tridemorph, plumbing, fenpropidin, fenfluralin, and spiroxamine.
Example b6. Compositions described in the summary of the invention (including but not limited to compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 6) phospholipid biosynthesis inhibitor fungicides such as blasticidin, iprobenfos, pyrifos and isoprothiolane.
Example b7. The compositions described in this summary (including, but not limited to, the compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 7) succinate dehydrogenase inhibitor fungicides such as mefenoxam, flutolanil, mefuramide, mefuramethon, carboxin thifluzamide, benzovindiflupyr, bixafen, sulfenamide, fluxapyroxapyroxad, furametpyr, diflufenpyrad, isopyrazam, penthiopyrad, propyne, epoxiconazole, flufen, isoflurazofamide, fluxapyroxastrobin, boscalid and bixapyroxafen.
Embodiment b8. The compositions described in this summary (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 8) hydroxy (2-amino-) pyrimidine fungicides such as brehmol, metrafenone, and ethidium.
Embodiment b9. The compositions described in this summary (including, but not limited to, the compositions described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 9) an anilinopyrimidine fungicide such as cyprodinil, mepanipyrim, and pyrimethanil.
Embodiment b10. The compositions described in this summary (including but not limited to the compositions described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 10) N-phenyl carbamate fungicides such as diethofencarb.
Example b11. The compositions described in this summary (including, but not limited to, the compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 11) a fungicide quinone outside inhibitor fungicide such as azoxystrobin, coumoxystrobin, enestrobin, fluxastrobin, picoxystrobin, pyraclostrobin, mandipropal, pyraclostrobin, triclopyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, enestroburin, metominostrobin, fluoxastrobin, famoxadone, fenamidone, and pyrazocarb.
An embodiment b12. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 12) phenylpyrrole fungicide compounds such as fenpiclonil and fludioxonil.
An embodiment b13. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 13) azanaphthalene fungicides such as quinoxalin and propoxymine.
Example b14. A composition as described in the summary of the invention (including but not limited to a composition as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 14) a cell peroxidation inhibitor fungicide such as biphenyl, diclomethamine, clonitrobenzene, tetrachloronitrobenzene, tolclofos-methyl, and hymexazol.
Example b15. The compositions described in the summary of the invention (including, but not limited to, the compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 15) melanin biosynthesis inhibitor-reductase fungicides such as tetrachlorophthalide, pyroquilon, and tricyclazole.
Example b16a. The composition described in the summary (including but not limited to the composition as described in any one of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 16 a) a melanin biosynthesis inhibitor-dehydratase fungicide such as cyclopropylamide, diclorocyanide and fenoxanil.
An embodiment b16b. of the disclosure (including but not limited to the compositions of any one of embodiments 1-258 and a-K), wherein component (b) comprises at least one compound selected from (b 16 b) a melanin biosynthesis inhibitor-polyketide synthase fungicide such as topiramate.
An embodiment b17. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 17) ketoreductase inhibitor fungicides such as fenhexamid, fenpyrazamine, quinofolin, and fluquindox.
An embodiment b18. The composition described in the summary of the invention (including but not limited to the composition as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 18) squalene-epoxidase inhibitor fungicides such as barnyard grass, naftifine and terbinafine.
An embodiment b19. The composition described in the summary of the invention (including but not limited to the composition as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 19) polyoxin fungicides such as polyoxin.
Embodiment b20. The compositions described in the summary of the invention (including, but not limited to, the compositions as described in any of embodiments 1 to 243 and a to K), wherein component (b) comprises at least one compound selected from (b 20) phenylurea fungicides such as pencycuron.
An embodiment b21. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 21) quinone inside inhibitor fungicides such as cyazofamid, amisulbrom and fenofenap (accession number 517875-34-2).
Example b22. The compositions described in this summary (including but not limited to the compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 22) benzamide and thiazolecarboxamide fungicides such as zoxamide and ethaboxam.
Example b23. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 23) enol pyranouronic acid antibiotic fungicides such as blasticidin-S.
An embodiment b24. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 24) a hexopyranosyl antibiotic fungicide such as kasugamycin.
Embodiment b25. The composition described in the summary of the invention (including but not limited to the composition as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 25) glucopyranosyl antibiotics: protein synthesis fungicides such as streptomycin.
Embodiment b26. The composition described in this summary (including but not limited to the composition described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 26) a glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides such as validamycin.
An embodiment b27. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 27) cyanoacetamide oxime fungicides such as cymoxanil.
Example b28. Compositions described in the summary of the invention (including, but not limited to, compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 28) a carbamate fungicide such as propamocarb, thiolcarb, and iodopropynyl butyl carbamate.
An embodiment b29. The compositions described in the summary of the invention (including, but not limited to, the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 29) oxidative phosphorylation uncoupling fungicides such as fluazinam, binapacryl, mepiquat chloride and dinocap.
Embodiment b30. The compositions described in this summary (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 30) organotin fungicides such as triphenyltin acetate, triphenyltin chloride, and triphenyltin hydroxide.
Embodiment b31. The compositions described in this summary (including but not limited to the compositions described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 31) carboxylic acid fungicides such as oxolinic acid.
Embodiment b32. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 32) heteroaromatic fungicides such as hymexazol and octhio-none.
An embodiment b33. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 33) phosphonate fungicides such as phosphorous acid and various salts thereof, including fosetyl aluminum.
Embodiment b34. The compositions described in this summary (including, but not limited to, the compositions described in any of embodiments 1-258 and a-K), wherein component (b) comprises at least one compound selected from (b 34) an o-carbamoylbenzoic acid fungicide, such as, for example, phyllo-cumylphthalide.
Embodiment b35. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 35) benzotriazine fungicides such as pyrazoxazine.
An embodiment b36. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 36) benzene-sulfonamide fungicides such as flusulfamide.
An embodiment b37. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 37) pyridazinone fungicides such as pyridazinclear.
An embodiment b38. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 38) thiophene-carboxamide fungicides such as silthiopham.
An embodiment b39. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 39) complex I NADH oxidoreductase inhibitor fungicides such as fluoxamid, tolfenpyrad and fenazaquin.
Embodiment b40. The compositions described in this summary (including, but not limited to, the compositions described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 40) a carboxylic acid amide fungicide such as dimethomorph, benthiavalicarb-isopropyl, iprovalicarb, valienamine, mandipropamid, flumorph, dimethomorph, flumorph, pyrimorph, benthiavalicarb-isopropyl, iprovalicarb, iprocapium, valienamine, and mandipropamid.
A composition as described in the summary of the invention (including but not limited to compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 41) tetracycline antibiotic fungicides such as oxytetracycline.
An embodiment b42. The composition described in the summary of the invention (including but not limited to the composition as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 42) thiocarbamate fungicides such as sulbencarb.
Embodiment b43. The compositions described in the summary of the invention (including, but not limited to, the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 43) benzamide fungicides such as fluopicolide and fluoroether carboxamide.
Example b44. The compositions described in this summary (including but not limited to the compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 44) microbial fungicides such as bacillus amyloliquefaciens strain QST713, FZB24, MB1600, D747, F727, TJ100 (also referred to as strain 1BE; known from EP 2962568), and the fungicidal lipopeptides they produce.
Embodiment b45. The compositions described in the summary of the invention (including, but not limited to, the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 45) quinone external inhibitors, mepiquat chloride-binding fungicides such as ametoctradin.
Example b46. The compositions described in the summary of the invention (including, but not limited to, the compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 46) plant extract fungicides such as melaleuca alternifolia, eugenol, geraniol and thymol.
Embodiment b47. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 47) cyanoacrylate fungicides such as phenamacril.
Embodiment b48. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 48) polyene fungicides such as natamycin.
An embodiment b49. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 49) oxysterol binding protein inhibitor fungicides such as oxathiapiprolin and fosfalcon fluoride.
Embodiment b50. The compositions described in the summary of the invention (including, but not limited to, the compositions as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 50) aryl-phenyl-ketone fungicides such as metrafenone and metrafenone.
Example b51. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 51) host plant defense inducing fungicides such as acibenzolar-S-methyl, thiabendazole, tiadinil, isotianil, laminarin, extracts from polygonum cuspidatum, and cell walls of bacillus mycoides strain J and saccharomyces cerevisiae strain LAS 117.
Example b52. The composition described in the summary of the invention (including but not limited to the composition as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 52) multi-site active fungicides such as copper oxychloride, copper sulfate, copper hydroxide, boldo composition (tribasic copper sulfate), elemental sulfur, ferbam, mancozeb, maneb, metiram, propineb, thiram, fosthiazate, zineb, ziram, folpet, captan, captafol, chlorothalonil, benfluanid, mefonamide, biguanide salts, biguanide octenyl benzenesulfonate, biguanide octamine triacetate, dichlofluanid, dithianon, chlorfenapyr, and fenzopyr.
Example b53. A composition described in the summary of the invention (including but not limited to a composition as described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 53) a biologicai fungicide having multiple modes of action such as an extract from the cotyledon of a lupin plantlet.
Example b54. The compositions described in this summary (including but not limited to the compositions described in any of examples 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 54) fungicides other than the fungicides of component (a) and components (b 1) to (b 53), such as cyflufenamid, besoxazine, tianan, nitropyrrolidin, tefloquine, dodine, fluthiacet, cyprodinil, fenpyrazoxamethyl, dichlorophenazo (accession No. 957144-77-3), dipyridamole (accession No. 16114-35-5), flumetoquine, sulfentrazofam (accession No. 30498-6), N' - [4- [ 4-chloro-3- (trifluoromethyl) phenoxy ] -2, 5-dimethylphenyl ] -N-ethyl-N-methylmethamidine, 5-fluoro-2- [ (4-fluorophenyl) methoxy ] -4-pyrimidinamine and N- [1- (4-cyanophenyl) ethyl ] propyl ] amino ] propyl ] amino-benzoate (XR-XR 911-911).
Example b55. Compositions described in the summary of the invention (including, but not limited to, compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises N- [ [3- (acetoxy) -4-methoxy-2-pyridinyl ] carbonyl ] -L-alanine (1S) -2, 2-bis (4-fluorophenyl) -1-methylethyl ester (provisionally common name picolinamide).
Example b56. Compositions described in the summary of the invention (including but not limited to compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises 1- [2- [ [ [1- (4-chlorophenyl) -1H-pyrazol-3-yl ] oxy ] methyl ] -3-methylphenyl ] -1, 4-dihydro-4-methyl-5H-tetrazol-5-one (provisionally common name methyltetraproline).
Example b57. The compositions described in the summary of the invention (including but not limited to the compositions as described in any of examples 1 to 258 and a to K), wherein component (b) comprises 3-chloro-4- (2, 6-difluorophenyl) -6-methyl-5-phenylpyridazine (provisionally common name pyridine chloromethyl).
Embodiment b58. The compositions described in this summary (including, but not limited to, the compositions described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester (temporary common name aminopyrine).
Embodiment b59. The compositions described in the summary of the invention (including, but not limited to, the compositions described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 54.11) (i.e., formula b 54.11)
Figure BDA0003913878900000911
Wherein
R b10 And R b11 Each independently is halogen; and is
R 6 Is H, halogen, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl or C 3 -C 6 A cycloalkyl group.
The composition of embodiment B60. Wherein component (B) comprises at least one fungicidal compound selected from the group consisting of: methyl N- [ [5- [1- (2, 6-difluoro-4-formylphenyl) -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, methyl N- [ [5- [1- (4-cyclopropyl-2, 6-dichlorophenyl) -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, methyl N- [ [5- [1- (4-chloro-2, 6-difluorophenyl) -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, methyl N- [ [5- [1- (4-cyclopropyl-2, 6-difluorophenyl) -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, methyl N- [ [5- [1- [2, 6-difluoro-4- (1-methylethyl) phenyl ] -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, and methyl N- [ [5- [1- [2, 6-difluoro-4- (trifluoromethyl) phenyl ] -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate.
Embodiment b61. The compositions described in this summary (including but not limited to the compositions described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 54.12) (i.e., formula b 54.12)
Figure BDA0003913878900000921
Wherein
R b4 Is that
Figure BDA0003913878900000922
R b6 Is C 2 -C 4 Alkoxycarbonyl or C 2 -C 4 A haloalkylaminocarbonyl group;
l is CH 2 Or CH 2 O, wherein the right atom is attached to the benzene ring in formula b 54.12; and is provided with
R b5 Is that
Figure BDA0003913878900000923
Embodiment B62. The composition of embodiment B61, wherein component (B) comprises at least one fungicidal compound selected from the group consisting of: ethyl N- (2, 2-trifluoroethyl) -2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] -4-oxazolecarboxamide and 1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenoxy ] methyl ] -1H-pyrazole-4-carboxylate.
An embodiment b63. The compositions described in this summary (including, but not limited to, the compositions described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one compound selected from (b 54.13) (i.e., formula b 54.13)
Figure BDA0003913878900000931
Wherein
R b7 、R b8 And R b9 Each independently is H, halogen or cyano; and is provided with
R b10 And R b11 Each independently of the others being H, halogen, C 1 -C 3 Alkyl or C 1 -C 3 And (4) methoxy.
The composition of embodiment B64, wherein component (B) comprises at least one fungicidal compound selected from the group consisting of: 4- (2-chloro-4-fluorophenyl) -N- (2-fluoro-4-methyl-6-nitrophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, 4- (2-chloro-4-fluorophenyl) -N- (2-fluoro-6-nitrophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, 3, 5-difluoro-4- [5- [ (4-methoxy-2-nitrophenyl) amino ] -1, 3-dimethyl-1H-pyrazol-4-yl ] -benzonitrile and N- (2-chloro-4-fluoro-6-nitrophenyl) -4- (2-chloro-4-fluorophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine.
An embodiment b65. The composition described in the summary of the invention (including but not limited to the composition as described in any of embodiments 1 to 258 and a to K), wherein component (b) comprises at least one fungicidal compound (fungicide) selected from the group consisting of: azoxystrobin, benzovindiflupyr, boscalid (nicobifen), bixafen, bromuconazole, carbendazim, chlorothalonil, copper hydroxide, cyflufenamid, cyproconazole, difenoconazole, dimoxystrobin, epoxiconazole, famoxadone, fenbuconazole, fenpropidin, fenpropimorph, flurindazofam, flusilazole, flutriafol, fluxapyroxad, hexaconazole, ipconazole, maneb, metconazole, metominostrobin, metrafenone, myclobutanil, penconazole, penthiopyrad, picoxystrobin, prochloraz, propiconazole, proquinclorac, prothioconazole, trifloxystrobin, pyraclostrobin pyraoxystrobin, pyridinizolidone quinoxyfen, tebuconazole, trifloxystrobin, triticonazole, methyl N- [ [5- [1- [2, 6-difluoro-4- (1-methylethyl) phenyl ] -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, methyl N- [ [5- [1- [2, 6-difluoro-4- (trifluoromethyl) phenyl ] -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, ethyl N- (2, 2-trifluoroethyl) -2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] -4-oxazolecarboxamide, ethyl 1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenoxy ] methyl ] -1H-pyrazole-4-carboxylate, 4- (2-chloro-4-fluorophenyl) -N- (2-fluoro-4-methyl-6-nitrophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, 4- (2-chloro-4-fluorophenyl) -N- (2-fluoro-6-nitrophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine and 3, 5-difluoro-4- [5- [ (4-methoxy-2-nitrophenyl) amino ] -1, 3-dimethyl-1H-pyrazol-4-yl ] -benzonitrile.
The composition of embodiment B66. Wherein component (B) comprises at least one compound selected from the group consisting of: <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , N- [ [5- [1- [2,6- -4- (1- ) ] -1H- -3- ] -2- ] ] , N- [ [5- [1- [2,6- -4- ( ) ] -1H- -3- ] -2- ] ] , N- (2,2,2- ) -2- [ [4- [5- ( ) -1,2,4- -3- ] ] ] -4- , 1- [ [4- [5- ( ) -1,2,4- -3- ] ] ] -1H- -4- ,4- (2- -4- ) -N- (2- -4- -6- </xnotran> 1, 3-dimethyl-1H-pyrazol-5-amine, 4- (2-chloro-4-fluorophenyl) -N- (2-fluoro-6-nitrophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine and 3, 5-difluoro-4- [5- [ (4-methoxy-2-nitrophenyl) amino ] -1, 3-dimethyl-1H-pyrazol-4-yl ] -benzonitrile.
Embodiment B67. The composition of embodiment B66, wherein component (B) comprises at least one compound selected from the group consisting of: azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, difenoconazole, epoxiconazole, fenpropidin, fenpropimorph, flurindazofamid, flutriafol, fluxapyroxad, maneb, metominostrobin, picoxystrobin, prothioconazole, fluxapyroxad, pyraclostrobin, tebuconazole, trifloxystrobin, N- [ [5- [1- [2, 6-difluoro-4- (1-methylethyl) phenyl ] -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamic acid methyl ester methyl N- [ [5- [1- [2, 6-difluoro-4- (trifluoromethyl) phenyl ] -1H-pyrazol-3-yl ] -2-methylphenyl ] methyl ] carbamate, ethyl N- (2, 2-trifluoroethyl) -2- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] -4-oxazolecarboxamide, ethyl 1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenoxy ] methyl ] -1H-pyrazole-4-carboxylate, 4- (2-chloro-4-fluorophenyl) -N- (2-fluoro-4-methyl-6-nitrophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine, 4- (2-chloro-4-fluorophenyl) -N- (2-fluoro-4-fluorophenyl) -2-fluoro-pyrazol-5-amine -6-nitrophenyl) -1, 3-dimethyl-1H-pyrazol-5-amine and 3, 5-difluoro-4- [5- [ (4-methoxy-2-nitrophenyl) amino ] -1, 3-dimethyl-1H-pyrazol-4-yl ] -benzonitrile.
The composition of embodiment B68, wherein component (B) comprises at least one compound selected from the group consisting of: azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, epoxiconazole, fenpropidin, fenpropimorph, thiabendazole amine, flutriafol, fluxapyroxad, maneb, metominostrobin, picoxystrobin, prothioconazole, fluxapyroxad, pyraclostrobin, tebuconazole and trifloxystrobin.
Notably, the composition of any one of the embodiments described herein, including any of embodiments 1 through 258, a through K, and B1 through B68, wherein reference to formula 1 includes salts thereof, but not N-oxides thereof; thus, the phrase "compound having formula 1" may be replaced by the phrase "compound having formula 1 or a salt thereof". In this noteworthy composition, component (a) comprises a compound having formula 1 or a salt thereof.
Also of note as an example is a fungicidal composition of the present invention comprising a fungicidally effective amount of a composition as described in examples 1 through 258, a through K, and B1 through B68, and at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent.
Embodiments of the present invention further include methods for controlling plant diseases caused by fungal plant pathogens comprising applying to a plant or portion thereof, or plant seed or seedling, a fungicidally effective amount of a composition as described in any one of examples 1-258, a-K, and B1-B68 (e.g., as a composition comprising formulation ingredients as described herein). Embodiments of the present invention also include methods for protecting a plant or plant seed from a disease caused by a fungal pathogen, the method comprising applying to the plant or plant seed a fungicidally effective amount of a composition as described in any one of embodiments 1 through 258, a through K, and B1 through B68.
Some embodiments of the invention relate to controlling or protecting against plant diseases that primarily infest plant leaves and/or applying the compositions of the invention to plant leaves (i.e., the plant rather than the seed). Preferred methods of use include those relating to the above preferred compositions; and diseases that are particularly effective to control include plant diseases caused by fungal plant pathogens. The combination of fungicides used according to the invention promotes disease control and delays resistance development.
The method embodiment further comprises:
Embodiment c1. A method for protecting a plant from a disease selected from rust, powdery mildew and septoria, comprising applying to the plant a fungicidally effective amount of a composition comprising components (a) and (b) as described in the summary of any of embodiments 1 to 258.
Embodiment C2. The method of embodiment C1, wherein the disease is rust and component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of: (b3) A demethylation inhibitor (DMI) fungicide, (b 5) an amine/morpholine fungicide, (b 7) a succinate dehydrogenase inhibitor fungicide, (b 11) a quinone outside inhibitor (QoI) fungicide, (b 13) a benzimidazole methyl carbamate fungicide, and (b 52) a multi-site active fungicide.
Embodiment C3. The method of embodiment C2, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of: (b3) A demethylation inhibitor (DMI) fungicide, (b 7) a succinate dehydrogenase inhibitor fungicide, and (b 11) a quinone outside inhibitor (QoI) fungicide.
Embodiment C4. The method of embodiment C3, wherein component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of: azoxystrobin, cyproconazole, difenoconazole, epoxiconazole, sulfentrazone, flutriafol, fluxapyroxad, picoxystrobin, prothioconazole, pyraclostrobin, tebuconazole and trifloxystrobin.
Example C5. The method of examples C2 to C4, wherein the disease is asian soybean rust caused by Puccinia recondite (Puccinia recondite).
Example C6. The method of examples C2-C4, wherein the disease is wheat leaf rust caused by Phakopsora pachyrhizi (Phakopsora pachyrhizi).
Embodiment C7. The method of embodiment C1, wherein the disease is powdery mildew and component (b) of the composition comprises at least one fungicidal compound selected from: (b3) A demethylation inhibitor (DMI) fungicide, (b 11) a quinone outside inhibitor (QoI) fungicide, and (b 13) an azanaphthalene fungicide.
Example C8. The method of example C7, wherein the disease is wheat powdery mildew.
Example C9. The method of example C7, wherein the disease is botrytis.
The method of embodiments C10. The method of embodiments C7 to C9, wherein component (b) comprises at least one fungicidal compound selected from (b 3) DMI fungicides.
The method of embodiment C10, wherein component (b) comprises at least one fungicidal compound selected from the group consisting of: cyproconazole, difenoconazole, epoxiconazole, prothioconazole and tebuconazole.
Embodiment C12. The method of embodiment C11, wherein component (b) comprises at least one fungicidal compound selected from the group consisting of: cyproconazole, difenoconazole and prothioconazole.
The method of embodiments C8-C10, wherein component (b) comprises at least one fungicidal compound selected from (b 11) QoI fungicides.
Embodiment C14. The method of embodiment C12, wherein component (b) comprises at least one fungicidal compound selected from the group consisting of: azoxystrobin, picoxystrobin and pyraclostrobin.
Embodiment C15. The method of embodiment C1, wherein the disease is a septoria disease and component (b) of the composition comprises at least one fungicidal compound selected from the group consisting of: epoxiconazole, metalaxyl (including metalaxyl-M), iprovalicarb and fenpropimorph.
Example C16. The method of example C15, wherein the disease is wheat leaf blight.
Embodiment C17. The method of any one of embodiments C1 to C16, wherein components (a) and (b) are administered in synergistically effective amounts (and in synergistic ratios with respect to each other).
Of note are embodiments corresponding to embodiments C1 through C17, which relate to a method for controlling plant disease caused by a fungal plant pathogen comprising applying to the plant or part thereof a fungicidally effective amount of a fungicidal composition of the invention.
As indicated in the summary, the invention also relates to a compound having formula 1, or an N-oxide or salt thereof. It should also be noted that embodiments of the present invention (including embodiments 1 to 258) also relate to compounds having formula 1. Thus, the combination of examples 1-258 is further illustrated as follows:
embodiment d1. A compound having formula 1, or an N-oxide or salt thereof, wherein
T is T-2;
R 1 is CF 3 ；
X is O;
y is O;
R 2a is H or methyl;
R 2b is C 3 -C 15 Trialkylsilyl or C 3 -C 15 A halogenotrialkylsilyl group;
A 1 is O;
A 2 is a direct bond or CH 2 ；
R 6a And R 6b Each independently is H, cyanohydroxy or methyl;
j is J-1 or J-6;
q is 0 or 1;
l is a direct bond or CH 2 ；
E is E 1 Or E 2 ；
E 1 Is C 1 -C 3 Alkoxy radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1R 10a And up to 3 substituents independently selected from R 10b Substituted with the substituent(s);
R 10a is pyrazolyl, imidazolyl or triazolyl, each of which is optionally substituted by up to 2 independently selected R on a carbon atom ring member 11a Substituted with the substituent(s);
each R 10b Independently of one another is halogen, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy or C 2 -C 4 An alkoxycarbonyl group;
each R 11a Independently methoxycarbonyl or ethoxycarbonyl;
G is G-1, G-3, G-12 or G-22;
x is 1 or 2;
each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkenyloxycarbonyl radical, C 3 -C 5 Alkynyloxycarbonyl or C 4 -C 6 Cycloalkoxycarbonyl groups, each of which is optionally substituted with up to 3 substituents independently selected from R 19 Substituted with a substituent of (1);
each R 14a Independently is H or C 1 -C 2 An alkyl group;
each R 14b Independently of each other H, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, cyclopropylmethyl or C 2 -C 4 An alkoxyalkyl group;
each R 19 Independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl;
each U is independently a direct bond or C (= O) O;
each V is independently a direct bond or CH 2 ；
Each Q is independently phenyl or pyridyl, each of which is optionally substituted with up to 2 substituents independently selected from R 27 Substituted with the substituent(s);
each R 27 Independently halogen, methyl or methoxy; and is
Z is a direct bond, O, NH, C (= O) NH, or NHC (= O).
The compound of embodiment D1, wherein
R 2a Is H or methyl;
R 2b is trimethylsilyl or halotrimethylsilyl;
A 2 is a direct bond;
R 6a and R 6b Each is H;
R 8 is F or Cl;
E 1 is C 1 -C 2 Alkoxy or C 2 -C 3 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1 atom selected from R 10a Substituted with the substituent(s);
R 10a is pyrazolyl or imidazolyl, each of which is optionally selected up to 2 independently from R on a carbon atom ring member 11a Substituted with the substituent(s);
each R 11a Independently methoxycarbonyl or ethoxycarbonyl;
g is G-1 and the 2-position of G-1 is linked to Z and the 4-position is linked to R 13 (ii) a Or G is G-12 and G-12 is attached to Z at position 1 and to R at position 4 13 (ii) a Or G is G-12 and position 1 of G-12 is attached toZ and the 3 position is linked to R 13 ；
x is 1;
R 13 is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkynyloxycarbonyl or C 4 -C 6 Cycloalkoxycarbonyl, each of which is optionally substituted by up to 1R 19 Substituted with a substituent of (1);
R 14a is H;
R 14b is H, methyl or cyclopropylmethyl;
R 19 is cyano, halogen, cyclopropyl or methoxy;
u is C (= O) O;
v is CH 2 ；
Q is optionally selected from R by up to 2 27 Phenyl substituted with the substituent of (1); and is provided with
Z is a direct bond, O, NH or C (= O).
The compound of embodiment D2, wherein
R 2a Is H or methyl;
R 2b is a trimethylsilyl group;
R 8 is F;
E 1 is selected from 1R 10a Methoxy substituted with the substituent of (1);
R 10a is optionally substituted on a carbon atom ring member by up to 1R 11a Substituted pyrazolyl substituted with the substituents of (1);
G is G-12 and the 1-position of G-12 is linked to Z and the 4-position is linked to R 13 (ii) a Or G is G-12 and G-12 is attached at position 1 to Z and at position 3 to R 13 (ii) a And is provided with
R 13 Is optionally selected from R by up to 1 19 C substituted by a substituent of 2 -C 5 An alkoxycarbonyl group;
R 19 is cyano, cl, F, cyclopropyl or methoxy; and is provided with
Z is a direct bond.
Embodiment D3. The compound of embodiment D3, wherein
R 2a Is methyl;
j is J-1;
q is 0;
l is CH 2 ；
E is E 2 ；
G is G-12 and the 1-position of G-12 is linked to Z and the 4-position is linked to R 13 (ii) a And is provided with
R 13 Is methoxycarbonyl or ethoxycarbonyl.
Additional embodiments include a fungicidal composition comprising: (1) a compound as described in any one of examples D1 to D3; and (2) at least one additional component selected from the group consisting of a surfactant, a solid diluent, and a liquid diluent. Additional embodiments also include a method for protecting a plant or plant seed from a disease caused by a fungal pathogen, the method comprising applying to the plant (or portion thereof) or plant seed a fungicidally effective amount of a compound of any one of embodiments D1-D3 (directly or through the environment (e.g., growth substrate) of the plant or plant seed). Of note are embodiments directed to a method for controlling plant disease caused by a fungal plant pathogen comprising applying to a plant or portion thereof a fungicidally effective amount of a compound of any one of embodiments D1 through D3.
The present invention also provides a fungicidal composition comprising a compound having formula 1 (including all stereoisomers, N-oxides, and salts thereof) (i.e., in a fungicidally effective amount) and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. Notably, embodiments of such compositions are compositions comprising a compound corresponding to any of the compound embodiments described above.
One or more of the following methods and variations as described in schemes 1-17 can be used to prepare compounds having formula 1. Unless otherwise indicated, E, L, A in the following compounds having formulae 1-14 1 、A 2 、J、T、X、Y、R 1 、R 2a 、R 2b 、R 2c 、R 2d 、R 6a 、R 6b And R 29 Is as defined in the summary above. Unless otherwise indicated, have the formula 1a-1a 1 、1b-1b 6 And 1c-1c 1 Are a different subset of formula 1, and formulae 1a-1a 1 、1b-1b 6 And 1c-1c 1 All substituents of (a) are as defined above for formula 1. Since the synthetic literature includes many methods of forming halomethyl ketones and hydrates that can be readily adapted to prepare the compounds of the present invention, the following methods in schemes 1-17 are merely representative examples of the various procedures that can be used to prepare compounds having formula 1. For a review of methods for forming ketones and hydrates, see, e.g., tetrahedron ]1991,47,3207-3258 and chem]2013,49 (95), 11133-11148, and the references cited therein. See also the methods outlined in U.S. Pat. No. 6,350,892.
As shown in scheme 1, wherein R 1 Is CF 3 The compound of formula 1a (i.e., formula 1 wherein T is T-1 and W is O) can be prepared by trifluoroacetylation of the organometallic compound of formula 2. Typically, in this process, ethyl trifluoroacetate (i.e., ethyl trifluoroacetate) is used as the source of trifluoroacetyl groups, although trifluoroacetonitrile and various salts of trifluoroacetate can also be used. Depending on the reaction conditions, a double addition on the trifluoroacetyl compound may occur. Conducting the reaction at-65 deg.C or more preferably at-78 deg.C can reduce the occurrence of the bis-addition adduct to trace amounts, particularly when using organometallic species having formula 2 wherein M is Li or MgBr. Many other organometallic species produce similar results. For reaction conditions that can be used in the process of scheme 1, as well as other accepted routes for the synthesis of trifluoromethyl ketones, see, e.g., journal of Organic Chemistry [ Journal of Organic Chemistry ]]1987,52 (22), 5026-5030; chemical Communications [ Chemical Communications ] ]2013,49 (95), 11133-11148; and Journal of Fluorine Chemistry [ Journal of fluorochemical Chemistry]1981,18,117-129. The conditions described in these references can be readily varied to produce compounds in which R is 1 Other than CF 3 (e.g., a dihalo-or trichloro-moiety) of a compound having formula 1 a.
Scheme 1
Figure BDA0003913878900001021
Wherein R is 1 Is CF 3 The compound of formula 1a (i.e., formula 1 wherein T is T-1 and W is O) can also be prepared by reacting ethyl 4, 4-trifluoroacetoacetate (ETFAA) with a compound wherein L is a Is a leaving group such as a halogen (e.g., cl, br) or a sulfonate (e.g., mesylate) to produce. In this process, ETFAA is first treated with a base such as sodium hydride in a polar aprotic solvent such as Tetrahydrofuran (THF), THF/Hexamethylphosphoramide (HMPA), or acetone. The ETFAA anion then displaces a leaving group in the compound having formula 3 to give an intermediate ester, which is subjected to hydrolysis and decarboxylation in the presence of lithium chloride (LiCl) and N, N-Dimethylformamide (DMF) to give the ketone compound having formula 1 a. For the reaction conditions, see Journal Chemical Society, chemical Communications [ Journal of Chemical Society, chemical communication ]]1989, (2), 83-84; chemical Communications ]2013,49 (95), 11133-11148; and Journal of Fluorine Chemistry [ Journal of fluorochemical Chemistry]1989,44,377-394。
Scheme 2
Figure BDA0003913878900001022
As shown in scheme 3, wherein R 1 Is CF 3 The compound of formula 1a (i.e., formula 1 wherein T is T-1 and W is O) can also be prepared by reacting trifluoromethyltrimethylsilane (TMS-CF) 3 ) Prepared by trifluoromethylation of esters having formula 5. The reaction is carried out in the presence of a fluoride initiator such as tetrabutylammonium fluoride and in an anhydrous solvent such as toluene or dichloromethane at about-78 ℃ (see, for reaction conditions, see, e.g., angelw.chem., int.ed. [ international in applied chemistry ]Printing plate]1998,37 (6),820-821). Cesium fluoride can also be used as an initiator in solvents such as 1, 2-dimethoxyethane (glyme) at room temperature (see, for example, j],1999,64,2873). The reaction proceeds through a trimethyl silicate intermediate, which is hydrolyzed with aqueous acid to yield the desired trifluoromethyl ketone compound having formula 1 a. Weinreb amides can also be used in place of the starting esters (see, e.g., chem]2012,48,9610)。
Scheme 3
Figure BDA0003913878900001031
As shown in scheme 4, wherein R 1 Is CF 3 And R is 6a Or R 6b Is H has the formula 1a 1 (i.e. wherein A is A 1 -A 2 -CR 6a R 6b The compound of formula 1 a) of (a) can be prepared by reacting an acid chloride having formula 6 with trifluoroacetic anhydride (TFAA) and pyridine in a solvent such as dichloromethane or toluene at a temperature between about 0 ℃ and 80 ℃, followed by hydrolysis (see, for example, tetrahedron [ tetrahedral ] for reaction conditions]1995,51,2573-2584). The compound having formula 6 can be prepared from the compound having formula 5 by ester hydrolysis to the corresponding carboxylic acid and treatment with oxalyl chloride, as known to those skilled in the art.
Scheme 4
Figure BDA0003913878900001032
As shown in scheme 5, wherein R 2a X and R 2b Compounds having formula 1b wherein Y is OH (i.e., formula 1 wherein T is T-2) can be prepared by oxidizing an alcohol having formula 4 to the corresponding dihydroxy. The oxidation reaction can be carried out by a variety of means, such as by treating the alcohol having formula 4 with manganese dioxide, dess-martin periodinane, pyridinium chlorochromate, or pyridinium dichromate. Dictionary for recording mediaSee example 6, step F and example 8, step F, for reaction conditions for form i.
Scheme 5
Figure BDA0003913878900001041
Scheme 6 illustrates the preparation of a compound having formula 1b 1 (i.e., wherein L is CH 2 J is phenyl (i.e., J-1) and A is OCH 2 And R is 1 Is CF 3 A specific example of the general process of scheme 5 for the compound of formula 1 b). In this process, a compound having formula 4a (i.e., wherein L is CH) 2 J is phenyl (i.e., J-1), A is OCH 2 And R is 1 Is CF 3 With an oxidizing agent such as dess-martin periodinane in a solvent such as dichloromethane at a temperature between about 0 ℃ and 80 ℃. Inventive example 1, step C, illustrates the method of scheme 6.
Scheme 6
Figure BDA0003913878900001042
As shown in scheme 7, compounds having formula 4 can be prepared by reacting a compound having formula 2 with R 1 CHO reaction. For the reaction conditions see Tetrahedron Letters [ Tetrahedron Letters report]2007,48,6372-6376。
Scheme 7
Figure BDA0003913878900001043
As shown in scheme 8, having formula 4b (i.e., where A is OCR 6a R 6b The compound of formula 4) of (1) can be prepared by reacting a compound having formula 7 with an epoxide having formula 8. The reaction is typically carried out in a solvent such as acetonitrile with a catalytic amount of a base such as cesium carbonate or potassium carbonate at a temperature between about 20 ℃ and 80 ℃; or in a solvent such as dichloromethaneWith a catalytic amount of a lewis acid such as boron trifluoride etherate at a temperature between about 0 ℃ and 40 ℃. Inventive example 8 step E illustrates the method of scheme 8. Those skilled in the art will recognize that when A is SCR 6a R 6b Or N (R) 7a )CR 6a R 6b The method of scheme 8 may also be performed, thereby providing other compounds having formula 4 b.
The compounds having formulas 7 and 8 are available from commercial sources and can be readily prepared using commercial precursors and known methods. The present invention is illustrated by example 1, step a, example 6, step D and example 8, step D, the preparation of a compound having formula 7.
Scheme 8
Figure BDA0003913878900001051
Scheme 9 illustrates the preparation of compounds having formula 4b 1 (i.e., where L is CH 2 J is phenyl (i.e., J-1), R 6a And R 6b Is H and R 1 Is CF 3 A specific example of the general process of scheme 8 for compounds of formula 4 b). In this process, a compound having formula 7a (i.e., wherein L is CH) 2 And J is phenyl (i.e., J-1) with 2- (trifluoromethyl) oxirane (i.e., formula 8 a) in the presence of cesium carbonate in a solvent such as acetonitrile at a temperature between about 60 ℃ to 80 ℃. Inventive example 1, step B, illustrates the process of scheme 9.
Scheme 9
Figure BDA0003913878900001052
As shown in scheme 10, ketones having formula 1a (i.e., formula 1 wherein T is T-1 and W is O) can correspond to those wherein R 2a X and R 2b A ketone hydrate having formula 1b (i.e., formula 1 wherein T is T-2) wherein Y is OH (i.e., dihydroxy) is present in equilibrium. The advantage of equation 1a or equation 1b depends on several factors, such as environment and structure. For example, in an aqueous environment, havingThe ketone of formula 1a can be reacted with water to give a ketone hydrate (also known as a 1, 1-gem-diol) having formula 1 b. Conversion back to the keto form is typically accomplished by treatment with a dehydrating agent such as magnesium sulfate or molecular sieves. When the ketone moiety is in close proximity to an electron withdrawing group, such as when R 1 When trifluoromethyl, this equilibrium typically favors the dihydrate form. In these cases, conversion back to the keto form may require a strong dehydrating agent, such as phosphorus pentoxide (P) 2 O 5 ). See, e.g., eur.j.org.chem. [ european journal of organic chemistry ] for reaction conditions]2013,3658-3661; and Chemical Communications]2013,49 (95), 11133-11148, and references cited therein.
Scheme 10
Figure BDA0003913878900001061
As shown in scheme 11, ketones having formula 1a can also have formula 1b therewith 2 (i.e., wherein R is 2b Y is OH and R 2a Hemiketals, hemithioketals and hemiaminals of formula 1 b) other than H and their use in which R 2a And R 2b The ketal, thioketal aminal of formula 1b, other than H, is present in equilibrium. Having the formula 1b 2 By reacting a compound of formula 1a with a compound of formula R 2a X-H compounds (e.g. alcohols in which X is O, thiols in which X is S or NR 5a Amines) typically in the presence of a catalyst such as a bronsted (protic) acid or a lewis acid (e.g., BF) 3 ) Prepared by reaction in the presence of (see, e.g., master Organic Chemistry](online), for acetals and hemiacetals, 5.2010, 28 days, www. Masterorganic-chemistry. Com/2010/05/28/on-acetic-and-hemiacetals). In a subsequent step, having the formula 1b 2 Under dehydrating conditions or other water removal means to shift the equilibrium of the reaction to the right, using a compound of formula R 2b Compounds of Y-H (e.g. alcohols in which Y is O, thiols in which Y is S or NR in which Y is 5b Amine of (b) to provide wherein R is 2a And R 2b A compound having formula 1b other than H. Alternatively, ketones having formula 1a can be first treated with two equivalents (or an excess) of an alcohol, thiol, or amine, typically in the presence of a catalytic and dehydrating agent, to provide directly a compound having formula 1b (see, e.g., U.S. Pat. No. 6,350,892 for the preparation of dimethyl ketal using methanol and trimethyl orthoformate).
Scheme 11
Figure BDA0003913878900001062
As shown in scheme 12, having formula 1b 3 (i.e., wherein X and Y are O, and R 2a And R 2b The cyclic ketal of formula 1 b) which together form a 5-to 7-membered ring can be prepared by treating the corresponding ketone of formula 1a with a halohydrin (e.g., 2-chloroethanol or 2-bromopropanol) in the presence of a base such as potassium carbonate or potassium tert-butoxide and in a solvent such as acetonitrile or N, N-Dimethylformamide (DMF). For the reaction conditions, see Organic Letters]2006 8(17),3745-3748。
Scheme 12
Figure BDA0003913878900001071
The method of scheme 12 can also be used to prepare cyclic ketals starting from the corresponding ketone hydrate form. Scheme 13 illustrates a specific example, having formula 1b 4 (i.e., where L is CH 2 J is phenyl (i.e., J-1) and A is OCH 2 ，R 2a X and R 2b Y is OH and R 1 Is CF 3 With 2-chloroethanol in the presence of potassium carbonate in acetonitrile at a temperature between about 25 ℃ and 70 ℃ to provide a ketone hydrate of formula 1 b) having formula 1b 5 (i.e., wherein L is CH 2 J is phenyl (i.e., J-1) and A is OCH 2 X and Y are O, R 2a And R 2b Together form a 5-membered ring and R 1 Is CF 3 A compound of formula 1 b). The process of scheme 13 is illustrated in example 2 of the invention.
Scheme 13
Figure BDA0003913878900001072
As shown in scheme 14, wherein A 1 Is N (R) 7a ) O or S and A 2 Is a direct bond, or wherein A 1 Is CR 6c R 6d And A is 2 Is N (R) 7b ) Of O or S has the formula 1b 6 Of (i.e. wherein A is A) 1 -A 2 -CR 6a R 6b Of formula 1 b) can be prepared by reacting a compound of formula 1 b) wherein 1 Is O, S or N (R) 7a ) And A is 2 Is a direct bond, or wherein A 1 Is CR 6c R 6d And A is 2 Is O, S or N (R) 7b ) With a compound having formula 10. The reaction is typically carried out in a solvent such as N, N-Dimethylformamide (DMF) or dimethylsulfoxide and a base such as cesium carbonate or potassium carbonate or sodium hydride at a temperature between about 20 ℃ and 80 ℃. The method of scheme 14 is illustrated in example 4, step D.
Scheme 14
Figure BDA0003913878900001081
The compounds having formula 10 can be prepared using commercial precursors and known methods. For example, as shown in scheme 15, having formula 10a (i.e., wherein R 6a And R 6b Is H, X and Y are O and R 2a And R 2b Compound of formula 10) together forming a 5-membered ring may be prepared by reacting a compound of formula 11 with a halohydrin (e.g., 2-chloroethanol or 3-bromopropanol) under basic conditions (e.g., potassium tert-butoxide in a solvent such as N, N-dimethylformamide or tetrahydrofuran) to provide a compound of formula 12. Various methods for converting ketones to cyclic ketals are disclosed in the chemical literature and can be readily adapted to prepare compounds having formula 12 (see, e.g., g.hilgetag and a.martini editors, preparatory Organic C Chemistry [ preparative organic chemistry]Pages 381-387: wiley [ Wiley corporation]New york, 1972, and references cited therein; see also inventive example 4, step a). The resulting ester moiety of the cyclic ketal having formula 12 can be reduced to the corresponding alcohol having formula 13 by standard methods known to those skilled in the art (example 4, step B illustrates a typical procedure). The hydroxyl moiety in the compound having formula 13 can then be converted to a variety of R 29 To provide a compound having formula 10 a. For example, a mesylate or tosylate group may be disposed by treating the alcohol with methanesulfonyl chloride (methanesulfonyl chloride) or 4-toluenesulfonyl chloride (p-toluenesulfonyl chloride) in the presence of a base such as triethylamine at a temperature between about 0 ℃ and 40 ℃ and in a solvent such as dichloromethane. The triflate group can be prepared by using trifluoromethanesulfonic anhydride (CF) 3 SO 2 ) 2 The alcohol was treated with O to settle as illustrated in example 4, step C. Compounds having formula 11 are known and can be prepared by methods known to those skilled in the art.
Scheme 15
Figure BDA0003913878900001091
Compounds having formula 1c (i.e. formula 1 wherein T is T-3 and X is O) can be prepared by reacting a compound having formula 1c wherein R is 6a And R 6b Is H (i.e., formula 1 wherein T is T-1 and W is O) with a compound of formula 14 in the presence of a base, as illustrated in scheme 16. Suitable bases include cesium carbonate or potassium carbonate in a solvent such as N, N-Dimethylformamide (DMF) or dimethyl sulfoxide at a temperature of from about 20 ℃ to 80 ℃. In some cases, the process of scheme 16 produces a mixture of O-alkylated products (typically as a mixture of (E) -and (Z) -isomers), along with C-alkylated products. Purification can be achieved using standard techniques such as column chromatography (see Magnetic Resonance in Chemistry ]1991,29,675-678). Compounds having formula 14 are commercially available and can be readily prepared by general methods known to those skilled in the artAnd (4) synthesizing.
Scheme 16
Figure BDA0003913878900001092
The process of scheme 16 can also be used to prepare compounds having formula 1c starting from the corresponding ketone hydrates. Scheme 17 illustrates a specific example, wherein there is formula 1b 4 (i.e., where L is CH 2 J is phenyl (i.e., J-1), A is OCH 2 ，R 2a X and R 2b Y is OH and R 1 Is CF 3 With iodoethane in the presence of cesium carbonate in dimethyl sulfoxide at a temperature between about 25 ℃ and 75 ℃ to provide a ketone hydrate of formula 1 b) having formula 1c 1 (i.e., where L is CH 2 J is phenyl (i.e., J-1), A is O, R 2d Is H, XR 2c Is OCH 2 CH 3 And R is 1 Is CF 3 A compound of formula 1 c). The process of scheme 17 is illustrated in example 5 of the present invention.
Scheme 17
Figure BDA0003913878900001101
Compounds having formula 1 wherein T is T-1 and W is S can be prepared from the corresponding compounds wherein W is O by treatment with phosphorus pentasulfide or 2, 4-bis (4-methoxyphenyl) -1, 3-dithio-2, 4-diphosphetane-2, 4-disulfide (lawson' S reagent) in a solvent such as toluene, xylene or tetrahydrofuran. Those skilled in the art will also recognize that where T is T-1 and W is NR 3 The compound of formula 1 can be prepared from a compound of formula 1 wherein T is T-1 and W is O or S by reacting under dehydrating conditions with a compound of formula R 3 NH 2 By amine treatment.
The E-L-moieties present in the compounds of formula 1 and intermediate compounds of formulae 2 to 7 and 9 are common organic functional groups, the preparation of which is well documented in the literature. Those skilled in the art will recognize that these well-known chemical classes (esters, amides, sulfonamides, sulfones, ethers, carbamates, ureas, heterocycles) can be readily prepared by a variety of methods (see, e.g., WO 2018/080859, WO 2018/118781, WO 2018/187553, and WO 2019/010192).
It will be appreciated that certain of the reagents and reaction conditions described above for preparing compounds having formula 1 may not be compatible with certain functional groups present in the intermediates. In these cases, incorporating protection/deprotection sequences or functional group interconversions into the synthesis will help to obtain the desired product. The use and selection of protecting Groups will be apparent to those skilled in the art of chemical Synthesis (see, e.g., T.W.Greene and P.G.M.Wuts, protective Groups in Organic Synthesis, 2 nd edition; wiley [ Willey ]: new York, 1991). One skilled in the art will recognize that, in some cases, following the introduction of a given reagent as depicted in any individual scheme, it may be necessary to perform additional conventional synthetic steps not described in detail to complete the synthesis of the compound of formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps shown in the above schemes in a different order than the specific sequence presented to prepare the compound having formula 1.
One skilled in the art will also recognize that the compounds of formula 1 and intermediates described herein can undergo various electrophilic, nucleophilic, free radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. Accordingly, the following examples are to be construed as merely illustrative, and not limitative of the disclosure in any way whatsoever. The steps in the examples below illustrate the procedure for each step in the overall synthetic conversion, and the starting materials for each step do not have to be prepared by specific preparative trials whose procedures are described in other examples or steps. The percentages are by weight, except for chromatographic solvent mixtures or where otherwise indicated. Unless otherwise indicated herein, the term "a" or "an" is used,parts and percentages of the chromatographic solvent mixture are by volume. 1 H NMR spectra are reported in ppm at the low field of tetramethylsilane; "s" means singlet, "br s" means broad singlet, "d" means doublet, "dd" means doublet of doublets, "t" means triplet, "q" means quartet, and "m" means multiplet. 19 The F NMR spectrum is reported in ppm using trichlorofluoromethane as a reference.
Example 1
Preparation of ethyl 1- [ [4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate (Compound 1)
Step A: preparation of ethyl 1- [ (4-hydroxyphenyl) methyl ] -1H-pyrazole-4-carboxylate
---------------------------------------------------------
A mixture of ethyl 1H-pyrazole-4-carboxylate (1.40g, 10mmol), 4- (chloromethyl) phenyl acetate (2.0g, 11mmol) and potassium carbonate (1.6g, 11mmol) in N, N-dimethylformamide (10 mL) was stirred at room temperature for 16H. Ethanol (10 mL) was added and the reaction mixture was heated at 65 ℃ for 16h, cooled, and poured into ice water. The resulting precipitate was collected by filtration, washed with water and air dried. The resulting solid (2.0 g) was crystallized from acetonitrile to provide the title compound as a white solid which melted at 113 ℃ to 115 ℃.
1 H NMR(CDCl 3 ):δ1.32(t,3H),3.10(d,1H),4.10-4.40(m,5H),5.24(s,2H),6.91(d,2H),7.22(d,2H),7.83(s,1H),7.93(s,1H)。
And B, step B: preparation of ethyl 1- [ [4- (3, 3-trifluoro-2-hydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate
------------------------------------------------------------
A mixture of ethyl 1- [ (4-hydroxyphenyl) methyl ] -1H-pyrazole-4-carboxylate (i.e., the product of step A) (2.36g, 9.6 mmol), 2- (trifluoromethyl) oxirane (1.3g, 11.6 mmol) and cesium carbonate (50mg, 0.15mmol) in acetonitrile (20 mL) was heated at 65 ℃. After 3 days, the reaction mixture was cooled and concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0% to 50% ethyl acetate in hexanes) to provide the title compound as a white solid (2.46 g).
1 H NMR(CDCl 3 ):δ1.33(t,3H),4.29(q,2H),5.21(s,2H),5.95(br s,1H),6.76(d,2H),7.09(d,2H),7.84(s,1H),7.95(s,1H)。
19 F NMR(CDCl 3 ):δ-77.54。
Step C: preparation of ethyl 1- [ [4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenyl ] methyl ] 1H-pyrazole-4-carboxylate
----------------------------------------------------------------
A mixture of ethyl 1- [ [4- (3, 3-trifluoro-2-hydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate (i.e. the product of step B) (1.23g, 3.4 mmol) and Dess-Martin (Dess-Martin) periodinane (2.2 g,5.2 mmol) in dichloromethane (20 mL) was stirred at room temperature for 16H and then concentrated under reduced pressure. The resulting material was dissolved in ethyl acetate and washed with sodium bisulfite solution (2M aqueous solution) and then with saturated aqueous sodium bicarbonate solution. The organic layer was dried, filtered and the filtrate was concentrated under reduced pressure. The resulting tan solid (1.77 g) was crystallized from acetonitrile to provide the title compound (compound of the invention) as solid needles which melted at 120 ℃ to 123 ℃.
1 H NMR(CDCl 3 ):δ1.32(t,3H),3.80(br s,1.7H),4.18(s,2H),4.28(q,2H),5.25(s,2H),6.95(d,2H),7.22(d,2H),7.82(s,1H),7.95(s,1H)。
19 F NMR(CDCl 3 ):δ-84.92。
Example 2
Preparation of ethyl 1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate (Compound 32)
------------------------------------------------------------
A mixture of ethyl 1- [ [4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate (i.e. the product of example 1) (1.07g, 3.0 mmol), 2-chloroethanol (0.24g, 3.0 mmol) and potassium carbonate (0.5g, 3.6 mmol) in N, N-dimethylformamide (3.5 mL) was stirred at room temperature for 16H and then heated (briefly) at 65 ℃. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The resulting material was diluted with diethyl ether and washed with saturated aqueous sodium chloride. The organic layer was dried, filtered, and the filtrate was concentrated under reduced pressure to give the title compound (compound of the present invention) (1.06 g) as a colorless oil.
1 H NMR(CDCl 3 ):δ1.32(t,3H),4.21(s,4H),4.23(s,2H),4.27(q,2H),5.24(s,2H),6.94(d,2H),7.20(d,2H),7.81(s,1H),7.93(s,1H)。
19 F NMR(CDCl 3 ):δ-81.39。
Example 3
Preparation of ethyl 1- [ [4, 4-dimethyl-2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate (Compound 12)
-----------------------------------------------------------
The title compound was prepared by a procedure similar to example 2.
1 H NMR(CDCl 3 ):δ1.32(t,3H),1.13(s,3H),1.45(s,3H),3.95(d,1H),4.00(d,1H),4.18(m,2H),4.27(q,2H),5.24(s,2H),6.94(d,2H),7.20(d,2H),7.81(s,1H),7.93(s,1H)。
19 F NMR(CDCl 3 ):δ-81.01。
Example 4
Alternative preparation of ethyl 1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate (Compound 32)
Step A: preparation of methyl 2- (trifluoromethyl) -1, 3-dioxolane-2-carboxylate
--------------------------------------------------------------
To a mixture of methyl 3, 3-trifluoro-2-oxopropanoate (31.2g, 200mmol) in petroleum ether (100 mL) was added 2-bromoethanol (25.0 g, 200mmol) over a period of 15 minutes. The reaction mixture was stirred at room temperature for 30 minutes, then cooled to 5 ℃ and potassium carbonate (28g, 200mmol) was added with vigorous stirring. Stirring was continued for another 4h at 5 ℃ and then the reaction mixture was allowed to warm to room temperature, diluted with diethyl ether (100 mL) and filtered. The filtrate was concentrated under reduced pressure, and the resulting material was dissolved in diethyl ether (200 mL) and washed with saturated aqueous sodium chloride (3 ×). The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give the title compound (29 g) as a colorless oil.
1 H NMR(CDCl 3 ):δ3.80(s,3H),4.30(m,4H)。
19 F NMR(CDCl 3 ):δ-80.52。
And B, step B: preparation of 2- (trifluoromethyl) -1, 3-dioxolane-2-methanol
---------------------------------------------------------------
To a mixture of methyl 2- (trifluoromethyl) -1, 3-dioxolane-2-carboxylate (i.e., the product of step A) (5g, 25mmol) in tetrahydrofuran (75 mL) was added sodium bis (2-methoxyethoxy) alaninate (60% in toluene) (12.2mL, 37.5 mmol). The reaction mixture was heated at 40 ℃ for 1.5h and then cooled to room temperature and a solution of ethyl acetate (3.30g, 37.5 mmol) in tetrahydrofuran (15 mL) was added dropwise over a period of 15 minutes. The reaction mixture was stirred for 45 minutes and then concentrated under reduced pressure. The resulting material was diluted with diethyl ether (400 mL), washed with saturated aqueous sodium chloride (2 ×), dried over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to give the title compound (3.8 g) as an oil.
1 H NMR(CDCl 3 ):δ2.59(t,1H),3.82(d,2H),4.19(m,4H)。
19 F NMR(CDCl 3 ):δ-81.50。
Step C: preparation of [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methyl 1, 1-triflate
--------------------------------------------------------------------
A mixture of 2- (trifluoromethyl) -1, 3-dioxolane-2-methanol (i.e., the product of step B) (1.67g, 9.70mmol) and triethylamine (1.5mL, 10.8mmol) in dichloromethane (50 mL) was cooled to-78 deg.C and then a solution of trifluoromethanesulfonic anhydride (1.81mL, 10.8mmol) in dichloromethane (50 mL) was added over a period of 30 minutes. The reaction mixture was stirred at-78 ℃ for 1.5h, and then water (50 mL) was added dropwise while the reaction was allowed to warm to room temperature. The resulting mixture was partitioned between dichloromethane-water and the organic layer was washed with water, dried over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to give the title compound (3.0 g) as a colorless solid.
1 H NMR(CDCl 3 ):δ4.24(m,4H),4.60(br s,2H)。
19 F NMR(CDCl 3 ):δ-74.84,-81.50。
Step D: preparation of ethyl 1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate
-------------------------------------------------------------------
To a mixture of ethyl 1- [ (4-hydroxyphenyl) methyl ] -1H-pyrazole-4-carboxylate (i.e., the product of step A of example 1) (16.85g, 68.0 mmol) and cesium carbonate (53.53g, 164.5 mmol) in N, N-dimethylformamide (100 mL) was added [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methyl 1, 1-triflate (i.e., the product of step C) (24.9g, 82.0 mmol). The reaction mixture was stirred at room temperature for 24h and then diluted with diethyl ether. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0% to 60% ethyl acetate in hexanes) to provide the title compound (compound of the invention) as a white solid, which melted at 59 ℃ -60 ℃ (23 g).
1 H NMR(CDCl 3 ):δ1.32(t,3H),4.21(s,4H),4.23(s,2H),4.27(q,2H),5.24(s,2H),6.94(d,2H),7.20(d,2H),7.81(s,1H),7.93(s,1H)。
19 F NMR(CDCl 3 ):δ-81.39。
Example 5
Preparation of ethyl 1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate (Compound 64)
--------------------------------------------------------------------
A mixture of ethyl 1- [ [4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate (i.e. the product of example 1) (1.0 g, 2.67mmol), iodoethane (2.5 g, 169mmol) and cesium carbonate (1.75g, 5.37mmol) in dimethyl sulfoxide (10 mL) was heated at 40 ℃ for 45 minutes. The reaction mixture was diluted with diethyl ether, washed with water and saturated aqueous sodium chloride solution, dried and filtered. The filtrate was concentrated under reduced pressure to give the title compound (compound of the present invention) as a white solid (0.80 g). A portion of the solid was further purified by silica gel chromatography (eluting with a gradient of 0% to 50% ethyl acetate in hexanes) to provide a solid that melted at 59 ℃ -60 ℃. A Nuclear Orvowegian Effect (NOE) was observed between the trifluoromethyl moiety and the vinyl proton, representing the cis configuration.
1 H NMR(CDCl 3 ):δ1.30-1.40(m,6H),4.17(q,2H),4.27(q,2H),5.28(s,2H),6.78(q,1H),7.05(m,2H),7.29(m,2H),7.86(s,1H),7.94(s,1H)。
19 F NMR(CDCl 3 ):δ-70.13。
Example 6
Preparation of ethyl 1- [ [3- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate (Compound 266)
Step A: preparation of 3- (bromomethyl) phenol
-----------------------------------------------------------------
A mixture of 1- (bromomethyl) -3-methoxybenzene (15.48g, 76.99mmol) in dichloromethane (150 mL) was cooled to-78 deg.C and then boron tribromide (1M solution in dichloromethane) was added dropwise. The reaction mixture was allowed to warm to room temperature, stirred for 2h, and then cooled to-20 ℃, and methanol (150 mL) was added dropwise. After warming to room temperature, the reaction mixture was concentrated under reduced pressure and the resulting material was diluted with dichloromethane and washed with saturated aqueous sodium bicarbonate. The organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0% to 100% ethyl acetate in hexanes) to provide the title compound as a white solid (14.16 g).
1 H NMR(CDCl 3 ):δ4.44(s,2H),4.89(s,1H),6.76(dd,1H),6.87(s,1H),6.95(d,1H),7.19-7.23(t,1H)。
And B, step B: preparation of 3- (bromomethyl) phenyl acetate
----------------------------------------------------------------
A solution of 3- (bromomethyl) phenol (i.e., the product of step A) (14.16g, 75.7mmol) in dichloromethane (130 mL) was cooled to 0 deg.C and acetic anhydride (12.96g, 12mL, 126.9mmol) was then added followed by concentrated sulfuric acid (5 drops). The reaction mixture was allowed to warm to room temperature, stirred for 1h, and then saturated aqueous sodium bicarbonate solution (300ml, 318mmol) was added. The organic layer was separated, washed with water, dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to give the title compound (16.68 g) as a solid.
1 H NMR(CDCl 3 ):δ4.47(s,2H),7.02-7.04(m,1H),7.14(s,1H),7.25(m,1H),7.35(t,1H)。
And C: preparation of ethyl 1- [ [3- (acetoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate
---------------------------------------------------------------------
To a mixture of 3- (bromomethyl) phenyl acetate (i.e., the product of step B) (16.68g, 72.8mmol) in acetonitrile (300 mL) was added ethyl 1H-pyrazole-4-carboxylate (10.61g, 75.7 mmol) followed by potassium carbonate (19.35g, 140mmol). The reaction mixture was heated at 70 ℃ overnight, cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure to give the title compound (20.5 g) as a yellow oil.
1 H NMR(CDCl 3 ):δ2.30(s,3H),4.47(s,2H),7.02(dd,1H),7.15(s,1H),7.25(m,1H)。
Step D: preparation of ethyl 1- [ (3-hydroxyphenyl) methyl ] -1H-pyrazole-4-carboxylate
-----------------------------------------------------------------
To a mixture of ethyl 1- [ [3- (acetoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate (i.e. the product of step C) (20.5g, 72.8mmol) in ethanol was added potassium carbonate (10.1g, 73mmol). The reaction mixture was heated at reflux for 3h, cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure and the resulting material was purified by MPLC silica gel chromatography (eluting with a gradient of 0% to 100% ethyl acetate in hexanes) to provide the title compound as a white solid (10.02 g).
1 H NMR(CDCl 3 ):δ1.33(t,3H)4.29(q,2H),5.20(br s,1H),5.25(s,2H),6.66(m,1H),6.78-6.81(m,2H),7.21-7.24(m,1H),7.87(s,1H),7.94(s,1H)。
And E, step E: preparation of ethyl 1- [ [3- (3, 3-trifluoro-2-hydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate
---------------------------------------------------------------
To a mixture of ethyl 1- [ (3-hydroxyphenyl) methyl ] -1H-pyrazole-4-carboxylate (i.e.the product of step D) (2.38g, 9.66mmol) in acetonitrile (100 mL) was added 3-bromo-1, 1-trifluoro-2-propanol (1.93g, 1.04mL, 10mmol), followed by potassium carbonate (2.86g, 20.7mmol). The reaction mixture was heated at reflux for 48h, cooled to room temperature, filtered and the filtrate concentrated under reduced pressure. The resulting material was purified by MPLC silica gel chromatography (eluting with a gradient of 0% to 100% ethyl acetate in hexanes) to provide the title compound as a solid (2.75 g).
1 H NMR(CDCl 3 ):δ1.33(q,3H),4.1-4.4(m,5H),5.27(s,2H),6.80(m,1H),6.87-6.89(m,2H),7.28-7.31(m,1H),7.88(s,1H),7.94(s,1H)。
19 F NMR(CDCl 3 ):δ-77.53。
Step F: preparation of ethyl 1- [ [3- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate
---------------------------------------------------------------------
To a mixture of ethyl 1- [ [3- (3, 3-trifluoro-2-hydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate (i.e. the product of step E) (5.7g, 14.9mmol) in dichloromethane (300 mL) was added dess-martin periodinane (9.13g, 20.3mmol) in one portion. After 3h, the reaction mixture was concentrated under reduced pressure, diluted with ethyl acetate and washed with sodium bisulfite solution (10% aqueous solution), saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The resulting material was triturated with 1-chlorobutane to give the title compound (compound of the present invention) as a white solid (4.89 g).
1 H NMR(DMSO-d 6 ):δ1.27(t,3H),4.01(s,2H),4.20(m,2H),5.33(s,2H),6.86-6.92(m,3H),7.26-7.29(m,1H),7.31(s,2H,),7.87(s,1H),8.48(s,1H)。
19 F NMR(DMSO-d 6 ):δ-81.82。
Example 7
Preparation of ethyl 1- [ [3- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylate (Compound 265)
---------------------------------------------------------------------
To a mixture of ethyl 1- [ [3- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylate (i.e. the product of example 6) (2.94g, 7.85mmol) in dimethyl sulfoxide (24 mL) was added iodoethane (2.39g, 15.3mmol). The reaction mixture was heated at 65 ℃ and cesium carbonate (4.21g, 12.92mmol) was then added. After 45 minutes, the reaction mixture was cooled to room temperature and poured into diethyl ether/water (400ml, 1. The organic layer was separated and washed with water, saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0% to 100% ethyl acetate in hexanes) to provide the title compound (compound of the invention) as a white solid (2.59 g) that melted at 41 ℃ -43 ℃.
1 H NMR(CDCl 3 ):δ1.32(m,6H),4.16(m,2H,),4.30(m,2H,),5.31(s,2H,),6.76(s,1H),6.93(m,1H),7.00-7.03(m,2H),7.34-7.37(m,1H),7.90(s,1H),7.95(s,1H)。
19 F NMR(CDCl 3 ):δ-70.09。
Example 8
Preparation of ethyl 1- [ [4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenoxy ] methyl ] -1H-pyrazole-4-carboxylate (compound 366)
Step A: preparation of 1- (hydroxymethyl) -1H-pyrazole-4-carboxylic acid ethyl ester
--------------------------------------------------------------------
A mixture of ethyl 1H-pyrazole-4-carboxylate (6.0 g, 43mmol), formaldehyde (37% aqueous solution, 12 mL) and ethanol (50 mL) was heated at reflux overnight. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The resulting material was triturated with 1-chlorobutane to give the title compound as a white solid (6.2 g).
1 H NMR(DMSO-d 6 ):δ1.27(t,3H)4.22(q,2H),5.41(s,2H),7.89(s,1H),8.36(s,1H)。
And B: preparation of 1- (chloromethyl) -1H-pyrazole-4-carboxylic acid ethyl ester
-------------------------------------------------------------------
To a mixture of ethyl 1- (hydroxymethyl) -1H-pyrazole-4-carboxylate (i.e., the product of step a) (6.2 g, 36mmol) in dichloroethane (100 mL) was added N, N-dimethylformamide (2 drops) followed by dropwise addition of thionyl chloride (5.3 mL, 73mmol). After 3h, the reaction mixture was concentrated under reduced pressure to give the title compound as a yellow solid (6.2 g).
1 H NMR(CDCl 3 ):δ1.35(t,3H),4.31(q,2H),5.85(s,2H),7.99(s,1H),8.11(s,1H)。
And C: preparation of 1- [ (4-methoxyphenoxy) methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester
----------------------------------------------------------------------
A mixture of ethyl 1- (chloromethyl) -1H-pyrazole-4-carboxylate (i.e., the product of step B) (2.0g, 11mmol), 4-methoxyphenol (1.24g, 10mmol), potassium carbonate (2.8g, 20mmol) and N, N-dimethylformamide (25 mL) was stirred at room temperature. After 3 days, the reaction mixture was poured into ice water (150 mL) and extracted with diethyl ether (2X 100 mL). The combined organic layers were washed with water (50 mL), saturated aqueous sodium chloride (25 mL), dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 10% to 100% ethyl acetate in hexanes) to provide the title compound as a colorless oil (2.7 g).
1 H NMR(CDCl 3 ):δ1.34(t,3H),3.78(s,3H),4.29(q,2H),5.90(s,2H),6.80-6.84(m,2H),6.88-6.91(m,2H),7.96(s,1H),8.05(s,1H)。
Step D: preparation of 1- [ (4-hydroxyphenoxy) methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester
----------------------------------------------------------------------
To a mixture of ethyl 1- [ (4-methoxyphenoxy) methyl ] -1H-pyrazole-4-carboxylate (i.e. the product of step C) (1.7 g,6.2 mmol) in dichloromethane (3 mL) was added a solution of boron tribromide (1m, 12.4mL,12.4mmol in dichloromethane). After 4h, saturated aqueous ammonium chloride (25 mL) was added to the reaction mixture and stirring was continued for a further 15 minutes. The reaction mixture was diluted with dichloromethane (25 mL) and saturated aqueous ammonium chloride (25 mL). The organic layer was separated and washed with saturated aqueous sodium bicarbonate (25 mL) and saturated aqueous sodium chloride (25 mL), dried over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to give the title compound (1.65 g) as a solid.
1 H NMR(DMSO-d 6 ):δ1.26(t,3H),4.21(q,2H),5.76(s,1H),5.96(s,2H),6.62-6.71(m,2H),6.82-6.88(m,2H),7.93(d,1H),8.48(d,1H)。
Step E: preparation of ethyl 1- [ [4- (3, 3-trifluoro-2-hydroxypropoxy) phenoxy ] methyl ] 1H-pyrazole-4-carboxylate
-----------------------------------------------------------------
To a mixture of ethyl 1- [ (4-hydroxyphenoxy) methyl ] -1H-pyrazole-4-carboxylate (i.e. the product of step D) (6.2 mmol) in acetonitrile (20 mL) was added 2- (trifluoromethyl) oxirane (0.62mL, 7.6 mmol) and cesium carbonate (approximately 10 mg). The reaction mixture was heated at 75 ℃ overnight, and then cooled to room temperature and concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 10% to 100% ethyl acetate in hexanes) to provide the title compound as a white solid (0.95 g).
1 H NMR(DMSO-d 6 ):δ1.26(t,3H),3.96-4.08(m,1H),4.12(dd,1H),4.22(q,2H),4.33-4.36(m,1H),6.04(s,2H),6.62(d,1H),6.88-6.97(m,2H),7.00-7.03(m,2H),7.95(s,1H),8.54(s,1H)。
Step F: preparation of ethyl 1- [ [4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenoxy ] methyl ] -1H-pyrazole-4-carboxylate
---------------------------------------------------------------------
To a mixture of ethyl 1- [ [4- (3, 3-trifluoro-2-hydroxypropoxy) phenoxy ] methyl ] -1H-pyrazole-4-carboxylate (i.e. the product of step E) (0.95g, 2.5 mmol) in dichloromethane (25 mL) was added dess-martin periodinane (1.5g, 3.5 mmol) in one portion. The reaction mixture was stirred for 2.5h, and then saturated aqueous sodium thiosulfate (30 mL) was added, and the mixture was concentrated under reduced pressure. The resulting mixture was extracted with ethyl acetate (150 mL), and the combined organic layers were washed with saturated aqueous sodium thiosulfate solution (50 mL), saturated aqueous sodium bicarbonate solution (50 mL), and saturated aqueous sodium chloride solution (25 mL), dried over magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure and the resulting material was triturated with dichloromethane to give the title compound (compound of the present invention) as a solid (0.65 g).
1 H NMR(DMSO-d 6 ):δ1.26(t,3H),3.98(s,2H),4.21(q,2H),6.03(s,2H),6.86-6.94(m,2H),6.95-7.06(m,2H),7.27(s,2H),7.94(s,1H),8.53(s,1H)。
Example 9
Preparation of ethyl 1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenoxy ] methyl ] -1H-pyrazole-4-carboxylate (Compound 364)
-------------------------------------------------------------------------
A mixture of iodoethane (2.7ml, 34mmol), potassium carbonate (0.84g, 6.1mmol) and dimethyl sulfoxide (7 mL) was stirred at room temperature for 20 minutes and then a solution of ethyl 1- [ [4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenoxy ] methyl ] -1H-pyrazole-4-carboxylate (i.e. the product of example 8) (0.64g, 1.6 mmol) in dimethyl sulfoxide (7 mL) was added portionwise over 20 minutes. After stirring at room temperature for 1.5 hours, the reaction mixture was poured into ice-water (150 mL) and extracted with ethyl acetate (125 mL). The organic layer was washed with water (2X 50 mL) and saturated aqueous sodium chloride (50 mL), dried over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and the resulting material was purified by silica gel chromatography (eluting with a gradient of 10% to 100% ethyl acetate in hexanes) to provide the title compound (compound of the invention) as a colorless oil (0.46 g).
1 H NMR(DMSO-d 6 ):δ1.23-1.27(m,6H),4.11(q,2H),4.22(q,2H),6.10(s,2H),7.07-7.24(m,4H)7.95(s,1H)8.58(s,1H)。
The following compounds in tables 1, 1A-48A, 2 and 1B-48B can be prepared by the procedures described herein and methods known in the art. The following abbreviations are used in the tables: t means tertiary, s means secondary, n means normal, i means iso, c means ring, me means methyl, et means ethyl, pr means propyl, i-Pr means isopropyl, c-Pr means cyclopropyl, bu means butyl, i-Bu means isobutyl, t-Bu means tertiary butyl, and Ph means phenyl.
TABLE 1
Figure BDA0003913878900001201
In the above formula, E is equal to E 2 ，E 2 Is equal to G-Z-, and G is optionally substituted by R 13 And (4) substitution. The definition of G is as defined in example a in the above embodiments. In column G, the number in parentheses refers to the attachment point of the G-ring to Z. (R) 13 ) x The columns refer to one or more substituents attached to the G-ring, as shown in example a above. (R) 13 ) x Dash "-" in the column means that R is absent 13 Substituents and remainders on the G-ringThe valency is occupied by a hydrogen atom.
Figure BDA0003913878900001211
Figure BDA0003913878900001221
Figure BDA0003913878900001231
Figure BDA0003913878900001241
Figure BDA0003913878900001251
Figure BDA0003913878900001261
Figure BDA0003913878900001271
Figure BDA0003913878900001281
The disclosure also includes tables 1A through 48A, except for the line title in Table 1 (i.e., "J is J-1, L is CH) 2 And Z is a direct key ") is replaced with a corresponding row header shown below, the construction of each table is the same as in table 1 above.
Figure BDA0003913878900001282
Figure BDA0003913878900001291
TABLE 2
Figure BDA0003913878900001292
In the above formula, E is equal to E 2 ，E 2 Is equal to G-Z-, and G is optionally substituted by R 13 And (4) substitution. The definition of G is as defined in example a in the above embodiments. In column G, the number in parentheses refers to the attachment point of the G-ring to Z. (R) 13 ) x The columns refer to one or more substituents attached to the G-ring, as shown in example a above. (R) 13 ) x Dash "-" in the column means that R is absent 13 Substituents and the remaining valencies on the G-ring are occupied by hydrogen atoms.
Figure BDA0003913878900001293
Figure BDA0003913878900001301
Figure BDA0003913878900001311
Figure BDA0003913878900001321
Figure BDA0003913878900001331
Figure BDA0003913878900001341
Figure BDA0003913878900001351
Figure BDA0003913878900001361
The disclosure also includes tables 1B through 48B, except for the line title in Table 2 (i.e., "J is J-1, L is CH) 2 And Z is a direct key ") is replaced with a corresponding row header shown below, the construction of each table is the same as in table 2 above.
Figure BDA0003913878900001371
Formulations/utilities
The compounds of formula 1 (including N-oxides and salts thereof) or mixtures (i.e., compositions) comprising the compounds with at least one additional fungicidal compound as described in the summary of the invention will generally be employed as the fungicidal active ingredient in a composition (i.e., formulation) in which at least one additional component is selected from the group consisting of surfactants, solid diluents and liquid diluents, employed as a carrier. The formulation or composition ingredients are selected to be consistent with the physical characteristics of the active ingredient, the mode of application, and environmental factors such as soil type, moisture, and temperature.
Mixtures of component (a) (i.e., at least one compound having formula 1, an N-oxide or salt thereof) with component (b) (e.g., selected from (b 1) to (b 54) and salts thereof as described above) and/or one or more other biologically active compounds or agents (i.e., insecticides, other fungicides, nematicides, acaricides, herbicides, and other biological agents) can be formulated in a variety of ways including:
(i) Component (a), component (b) and/or one or more other biologically active compounds or agents may be formulated separately and administered separately or simultaneously in appropriate weight ratios, for example as a tank mix; or
(ii) Component (a), component (b) and/or one or more other biologically active compounds or agents may be formulated together in appropriate weight ratios.
Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates, and/or suspoemulsions), and the like, which optionally can be thickened into gels. Common types of aqueous liquid compositions are soluble concentrates, suspension concentrates, capsule suspensions, concentrated emulsions, microemulsions, oil-in-water emulsions, flowable concentrates and suspoemulsions. Common types of non-aqueous liquid compositions are emulsifiable concentrates, micro-emulsifiable concentrates, dispersible concentrates and oil dispersions.
The general types of solid compositions are powders, granules, pellets, granules, 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 as seed treatment agents. The active ingredient may be (micro-) encapsulated and further formed into a suspension or solid formulation; alternatively, the entire formulation of active ingredient 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 granule formulations. The high strength compositions are mainly used as intermediates for further formulations.
Of note are composition embodiments wherein particles of a solid composition comprising a compound having formula 1 (or an N-oxide or salt thereof) are mixed with particles of a solid composition comprising component (b). These mixtures may be further mixed with granules comprising additional agricultural protection agents. Alternatively, two or more agricultural protectants (e.g., component (a) (formula 1) compound, component (b) compound, agricultural protectant other than component (a) or (b)) may be combined in a solid composition of a set of particles, which is then mixed with particles of one or more sets of solid compositions comprising one or more additional agricultural protectants. These particle mixtures may be in accordance with the general particle mixture disclosure of PCT patent publication WO 94/24861 or, more preferably, the homogeneous particle mixture teaching of U.S. Pat. No. 6,022,552.
Sprayable formulations are typically dispersed in a suitable medium prior to spraying. Such liquid and solid formulations are formulated to be readily dilutable in a spray medium, usually water, but occasionally another suitable medium like aromatic or paraffinic hydrocarbons or vegetable oils. The spray capacity can range from about one to several thousand liters per hectare, but more typically ranges from about ten to several hundred liters per hectare. The sprayable formulation may be tank mixed with water or another suitable medium for foliar treatment by air or ground application, or for application to the growing medium of the plant. The liquid and dry formulations can be metered directly into the drip irrigation system or into the furrow during planting. Liquid and solid formulations can be applied as seed treatments to the seeds of crops and other desired vegetation prior to planting to protect the developing roots and other plant parts and/or foliage below the ground through systemic absorption.
The formulation will typically contain an effective amount of active ingredient, diluent and surfactant, totaling up to 100 weight percent, within the following approximate ranges.
Figure BDA0003913878900001391
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 Watkins et al, handbook of Insecticide Dust Diluents and Carriers, 2 nd edition, dorland Books, caldwell, new Jersey [ Cowdwell, N.J. ].
The liquid diluent includes, for exampleSuch as water, N, N-dimethyl alkylamides (e.g., N, N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oil, N-paraffin, isoparaffin), alkylbenzenes, alkylnaphthalenes, glycerols, triacetic glycerol esters, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactic acid esters, dibasic esters, alkyl and aryl benzoates and gamma-butyrolactone, and alcohols which may be linear, branched, saturated or unsaturated, such as methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, N-hexanol, 2-ethylhexanol, N-octanol, decanol, isodecanol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, tridecanol, oily alcohols, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include 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 (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., beef tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated (e.g., methylated, ethylated, butylated) fatty acids, wherein the fatty acids may be obtained by hydrolysis of glycerides from plant and animal sources and may be purified by distillation. Typical liquid diluents are described in Marsden, solvents Guide [ solvent 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 referred to as "surface active agents") generally alter, most often reduce, the surface tension of liquids when added to liquids. 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. Nonionic surfactants useful in the compositions of the present invention include, but are not limited to: alcohol alkoxylates such as those based on natural and synthetic alcohols (which may be branched or straight chain) and prepared from alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides, and ethoxylated alkanolamides; alkoxylated triglycerides, such as ethoxylated soybean oil, castor oil, 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 trans-block polymers in which 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, 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, 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 polyglycosides; an alkyl polysaccharide; and glucamides such as octyl-N-methylglucamide and decyl-N-methylglucamide (e.g. from Clariant) and
Figure BDA0003913878900001411
Products available under GA name).
Useful anionic surfactants include, but are not limited to: alkyl aryl sulfonic acids and salts thereof; carboxylated alcohol 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 alcohol alkoxylate phosphate esters, alkylphenol alkoxylate phosphate esters, and styrylphenol ethoxylate phosphate esters; a protein-based surfactant; a sarcosine derivative; styryl phenol 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 the sulfonates of dodecylbenzene and tridecylbenzene; a sulfonate of condensed naphthalene; sulfonates of naphthalene and alkylnaphthalenes; petroleum fraction sulfonates; 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 ammonium acetate 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 recommended uses are disclosed in a number of published references, including The emulsifier and detergent compositions of McCutcheon, published by The Manufacturing conditioner Publishing Co [ candy manufacturer Publishing company ], mcutcheon division, annual American and International Editions [ U.S. and International year edition ]; sisely and Wood, encyclopedia of Surface Active Agents [ surfactant Encyclopedia ], chemical publication. And a.s.davidson and b.milwidsky, synthetic Detergents, seventh edition, john Wiley and Sons [ John Wiley father company ], new york, 1987.
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 auxiliaries and additives may control: pH (buffer), foaming during processing (antifoam agents such as polyorganosiloxanes), sedimentation of the active ingredient (suspending agents), viscosity (thixotropic thickeners), microbial growth in the container (antimicrobials), product freezing (antifreeze), color (dye/pigment dispersion), elution (film former or sticker), evaporation (evaporation retarder), 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 those listed in the following: mcCutcheon' sVolume 2, published by the McCutcheon division of Manufacturing Confector publishing company: functional materials ], annual and North American ages [ International and North American annual edition ]; and PCT publication WO03/024222.
The compound having formula 1 and any other active ingredients are typically incorporated into the compositions of the present invention by dissolving the active ingredients in a solvent or by grinding in a liquid or dry diluent. Solutions including emulsifiable concentrates can be prepared by simply mixing the ingredients. If the solvent of the liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the solvent containing the active ingredient upon dilution with water. Slurries of active ingredient having a particle size of up to 2,000 μm can be wet milled using a media mill to give particles having an average particle size of less than 3 μm. The aqueous slurry can be made into finished suspensions (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 process, resulting in an average particle size in the range of 2 to 10 μm. Powders and powders may be prepared by blending and typically by grinding (e.g. with a hammer mill or fluid energy mill). Granules and pellets can be prepared by spraying the active substance onto a preformed granule carrier or by agglomeration techniques. See, browning, "Agglomeration ]", chemical Engineering, 12.4.1967, pages 147-48; perry's Chemical Engineers ' Handbook [ Parry's Chemical Engineers Manual ], 4 th edition, mcGraw-Hill [ McGray Hill group ], new York, 1963, pages 8-57 and beyond, and WO 91/13546. Spheroids may be prepared as described in U.S.4,172,714. Water dispersible and water soluble granules may be prepared as taught in U.S.4,144,050, U.S.3,920,442 and DE 3,246,493. Tablets may be prepared as taught in U.S.5,180,587, U.S.5,232,701 and U.S.5,208,030. Membranes can be prepared as taught in GB 2,095,558 and u.s.3,299,566.
One embodiment of the present invention relates to a method for controlling a fungal pathogen, the method comprising diluting a fungicidal composition of the present invention (a compound of formula 1 formulated with a surfactant, a solid diluent, and a liquid diluent, or a formulated mixture of a compound of formula 1 and at least one other fungicide) with water, and optionally adding an adjuvant to form a diluted composition, and contacting the fungal pathogen or its environment with an effective amount of the diluted composition.
While spray compositions formed by diluting a sufficient concentration of the fungicidal composition of the present invention with water may provide sufficient efficacy in controlling fungal pathogens, separately formulated adjuvant products may also be added to the spray tank mix. These additional adjuvants are commonly referred to as "spray adjuvants" or "tank mix adjuvants" and include any substance that is mixed in the spray tank to improve the performance of the pesticide or to alter the physical characteristics of the spray mixture. The adjuvant may be an anionic or nonionic surfactant, emulsifier, petroleum-based crop oil, crop-derived seed oil, acidifying agent, buffer, thickener, or defoamer. Adjuvants are used to enhance efficacy (e.g., bioavailability, adhesion, permeability, coverage uniformity, and protection durability), or to minimize or eliminate spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization, and degradation. The adjuvants are chosen according to the nature of the active ingredient, the formulation and the target (e.g. crop, insect pest) in order to obtain optimum performance.
The amount of adjuvant added to the spray mixture is typically in the range of about 0.1% to 2.5% by volume. The application rate of the adjuvant added to the spray mixture is typically between about 1 and 5L per hectare. Representative examples of spray aids include:
Figure BDA0003913878900001441
(Syngenta) liquid hydrocarbons 47% methylated rapeseed oil,
Figure BDA0003913878900001442
(Helena Chemical Company) polyether-modified heptamethyltrisiloxane and
Figure BDA0003913878900001443
(BASF) 83% of a 17% surfactant blend in paraffin-based mineral oil.
One method of seed treatment is by spraying or dusting the seed with the compounds of the invention (i.e., as a formulated composition) prior to sowing the seed. Compositions formulated for seed treatment typically comprise a film former or binder. Thus, typically, the seed coating composition of the present invention comprises a biologically effective amount of a compound having formula 1 and a film-forming agent or binder. The seeds may be coated by spraying the flowable suspension agent directly into a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wet powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water may be sprayed on the seeds. The method is particularly useful for applying a film coating to seeds. Various coating machines and methods may be used by those skilled in the art. Suitable methods include those described in p.kosters et al, seed Treatment: progress and processes [ Seed Treatment: progression and prospects ],1994BCPC monograph No. 57 and those methods listed in the references listed therein.
For further information on The field of formulation, see "The formulations's Toolbox-Product Forms for model Agriculture analysis" in T.S. woods, pesticide Chemistry and Bioscience, the Food-environmental Challenge [ Pesticide Chemistry and Bioscience, food and environmental challenges ], editions of T.Brooks and T.R.Roberts, proceedings of The9th International conference on Pesticide Chemistry [ ninth International conference on Pesticide Chemistry ], the Royal Society of Chemistry [ British chemical Society of England ], cambridge, 1999, pages 120-133. 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 [ Weed Control Science ], john Wiley and Sons, inc. [ John Wiley father, new york, 1961, pages 81-96; hance et al, weed Control Handbook, 8 th edition, blackwell Scientific Publications Blackwell Scientific Press, oxford, 1989; and development in formulation technology [ Developments in formulation technology ], PJB Publications [ PJB publishing Co., ltd ], british, 2000.
In the following examples, all percentages are by weight and all formulations are prepared in a conventional manner. Active ingredient refers to the compounds in the index tables a-L disclosed herein. Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. Accordingly, the following examples are to be construed as merely illustrative, and not limitative of the disclosure in any way whatsoever.
Example A
High strength concentrate
Compound 263 98.5%
0.5 percent of silicon dioxide aerogel
Synthetic amorphous Fine silica 1.0%
Example B
Wettable powder
Figure BDA0003913878900001451
Example C
Granules
Compound 64.0%
Attapulgite granule (low volatile matter, 0.71/0.30mm; 90.0% U.S.S. No. 25-50 sieve)
Example D
Extrusion spheronization agent
Figure BDA0003913878900001452
Figure BDA0003913878900001461
Example E
Emulsifiable concentrate
Compound 64.0%
Polyoxyethylene sorbitol hexaoleate 20.0%
C 6 -C 10 Fatty acid methyl ester 70.0%
Example F
Microemulsion
Figure BDA0003913878900001462
Example G
Seed treatment agent
Figure BDA0003913878900001463
Example H
Fertilizer bar
Figure BDA0003913878900001464
Figure BDA0003913878900001471
Example I
Suspending agent
Figure BDA0003913878900001472
Example J
Emulsions in water
Figure BDA0003913878900001473
Figure BDA0003913878900001481
Example K
Oil dispersion
Figure BDA0003913878900001482
Example L
Suspoemulsion
Figure BDA0003913878900001483
Water-soluble and water-dispersible formulations are typically diluted with water to form an aqueous composition prior to application. Aqueous compositions (e.g., spray tank compositions) for direct application to plants or parts thereof typically contain at least about 1ppm or more (e.g., from 1ppm to 100 ppm) of one or more compounds of the invention.
The seed is typically treated at a rate of from about 0.001g (more typically about 0.1 g) to about 10g/kg of seed (i.e., from about 0.0001% to 1% by weight of seed prior to treatment). Flowable suspensions formulated for seed treatment typically contain from about 0.5% to about 70% active ingredient, from about 0.5% to about 30% film-forming binder, from about 0.5% to about 20% dispersant, from 0% to about 5% thickener, from 0% to about 5% pigment and/or dye, from 0% to about 2% defoamer, from 0% to about 1% preservative, and from 0% to about 75% volatile liquid diluent.
The composition of the present invention is useful as a plant disease control agent. Accordingly, the present invention further includes a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected or to the plant seed to be protected an effective amount of a compound of the present invention or a fungicidal composition containing said compound. The compounds and/or compositions of the present invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the phyla Ascomycota (Ascomycota), basidiomycota (Basidiomycota), zygomycota (Zygomycota), and fungi-like Oomycota (fungal-like Oomycota) classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal and fruit crops. These pathogens include, but are not limited to, those listed in tables 1-1. For ascomycetes (ascomycetes) and basidiomycetes (basidiomycetes), the names of sexual/sexually typed/sexual stages and of asexual/anormoid/asexual stages are listed under known conditions (in parentheses). Synonymous names for pathogens are indicated by equal numbers. For example, the sexual/sexual type/stage name Septoria nodorum (Phaeosphaeria nodorum) is followed by the corresponding asexual/anormoid/stage name Septoria nodorum (Stagnospora nodorum) and the synonymous, older name Septoria nodorum (Septoria nodorum).
TABLE 1-1
Figure BDA0003913878900001491
Figure BDA0003913878900001501
Figure BDA0003913878900001511
In addition to their fungicidal activity, the compositions or combinations also have activity against bacteria such as Erwinia amylovora (Erwinia amylovora), xanthomonas campestris (Xanthomonas campestris), pseudomonas syringae (Pseudomonas syringae) and other related species. By controlling harmful microorganisms, the compositions of the present invention can be used to increase (i.e., increase) the ratio of beneficial to harmful microorganisms in contact with a crop plant or its propagules (e.g., seed, bulb, tuber, cuttings) or in the agronomic environment of a crop plant or its propagules.
The compositions of the invention can be used to treat all plants, plant parts and seeds. Plant and seed varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which the heterologous gene (transgene) has been stably integrated into the plant or seed genome. A transgene defined by the specific location of the transgene in the plant genome is referred to as a transformation or transgene event.
Genetically modified plant cultivars that may be treated according to the invention include those that are resistant to one or more biotic stresses (pests, such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinization, etc.), or those that contain other desirable characteristics. Plants may be genetically modified to exhibit traits such as herbicide tolerance, insect resistance, modified oil characteristics, or drought tolerance.
Treatment of genetically modified plants and seeds with the compounds of the invention may result in superadditive or enhanced effects. For example, reducing application rates, broadening the spectrum of activity, increasing tolerance to biotic/abiotic stresses, or enhancing storage stability may be greater than would be expected from the simple additive effect of applying the compounds of the invention on genetically modified plants and seeds.
The compounds and compositions of the invention are useful in seed treatments to protect seeds from plant disease. In the context of the present disclosure and claims, treating seed means contacting the seed with a biologically effective amount of a compound of the present invention typically formulated as a composition of the present invention. The seed treatment protects the seed from soil-borne disease pathogens and may also generally protect the roots of seedlings developed from the germinating seed and other plant parts in contact with the soil. Seed treatment agents may also provide protection to the leaves by translocating a compound of the present invention or a second active ingredient in the developing plant. Seed treatments can be applied to all types of seeds, including those that will germinate to form plants genetically transformed to express a particular trait. Representative examples include those expressing proteins toxic to invertebrate pests, such as bacillus thuringiensis toxins, or those expressing herbicide resistance, such as glyphosate acetyltransferases that provide glyphosate resistance. Seed treatment agents using the compounds and compositions of the present invention may also increase the vigor of plants grown from seeds.
The compounds and compositions of the present invention are particularly useful in seed treatments for crops including, but not limited to, maize or corn, soybean, cotton, cereals (e.g., wheat, oats, barley, rye, and rice), potatoes, vegetables, and oilseed rape.
In addition, the compounds and compositions of the present invention are useful in treating postharvest disease of fruits and vegetables caused by fungi, oomycetes and bacteria. These infections can occur before, during and after harvest. For example, infection may occur prior to harvest and then remain dormant until some point during maturation (e.g., the host begins to organize changes in such a way that infection can progress or conditions become conducive to disease development); infection may also be caused by surface trauma resulting from mechanical or insect injury. In this regard, the compositions of the present invention can reduce losses (i.e., losses due to quantity and quality) due to postharvest diseases that may occur at any time from harvest to consumption. Treatment of post-harvest diseases with the compounds of the present invention may increase the period of time during which perishable edible plant parts (e.g., fruits, seeds, leaves, stems, bulbs, tubers) may be stored frozen or unfrozen after harvest and remain edible and free from significant or harmful degradation or contamination by fungi or other microorganisms. Treatment of edible plant parts before or after harvest with the compounds of the invention may also reduce the formation of toxic metabolites of fungi or other microorganisms, for example mycotoxins such as aflatoxin.
Plant disease control is typically achieved by applying an effective amount of a compound of the invention to parts of the plant to be protected, such as the roots, stems, leaves, fruits, seeds, tubers or bulbs, before or after infection, or to the medium (soil or sand) in which the plant to be protected is growing. These compounds may also be applied to seeds to protect the seeds and seedlings developing from the seeds. These compounds can also be applied by irrigation water to treat plants. Control of post-harvest pathogens that infect pre-harvest products is typically achieved by on-site application of the compounds of the invention, and in cases where infection occurs post-harvest, these compounds can be applied to harvested crops as impregnants, sprays, fumigants, treatment wraps, and box liners.
The compounds and compositions of the present invention may also be administered using an Unmanned Aerial Vehicle (UAV) to disperse the compositions disclosed herein over a planting area. In some embodiments, the planting area is an area containing a crop. In some embodiments, the crop is selected from monocots (monocots) or dicots (dicots). In some embodiments, the crop is selected from rice, corn, barley, soybean, wheat, vegetables, tobacco, tea, fruit trees, and sugarcane. In some embodiments, the compositions disclosed herein are formulated for spraying at ultra-low volumes. Products applied by drone may use water or oil as the spray carrier. Typical spray volumes (including products) for global drone applications. 5.0-100 liters per hectare (about 0.5-10 gpa). This includes the range of ultra low spray volumes (ULV) to low spray volumes (LV). Although not uncommon, there may be situations where even lower spray capacities as low as 1.0 liter per hectare (0.1 gpa) may be used.
Suitable application rates (e.g., fungicidally effective amounts) of component (a) (i.e., at least one compound selected from compounds having formula 1, N-oxides and salts thereof) and of mixtures and compositions comprising component (a) according to the present invention can be influenced by factors such as the plant disease to be controlled, the plant species to be protected, the population structure of the pathogen to be controlled, the ambient humidity and temperature, and should be determined under actual conditions of use. The fungicidally effective amount required for the desired level of plant disease control can be readily determined by one skilled in the art by simple experimentation. The leaves are generally protected when treated at a ratio of active ingredient from less than about 1g/ha to about 5,000g/ha. Seeds and seedlings can generally be protected when the seeds are treated at a rate of from about 0.001g (more typically about 0.1 g) to about 10g per kilogram of seed. The application rates of component (a) and mixtures thereof and compositions containing the particular combination of active ingredients according to the invention required to provide the desired spectrum of plant protection and control of plant diseases and optionally other plant pests can be readily determined by the skilled person by simple experimentation.
The compounds and compositions of the present invention may also be used to increase the vigor of crop plants. The method comprises contacting a crop plant (e.g., leaves, flowers, fruits or roots) or seeds from which the crop plant grows with a composition comprising a compound having formula 1 in an amount sufficient (i.e., a biologically effective amount) to achieve a desired plant vigor effect. Typically, the compound having formula 1 is administered in a formulated composition. Although the compounds of formula 1 are typically applied directly to the crop plant or to the seed thereof, these compounds may also be applied to the locus of the crop plant, i.e., to the environment of the crop plant, particularly to parts of the environment that are close enough for the compounds of formula 1 to migrate to the crop plant. The locus in connection with the method most often includes a growing medium (i.e., a medium that provides nutrients to the plant), typically soil in which the plant is grown. Thus, treatment of a crop plant to increase the vigor of the crop plant comprises contacting the crop plant, the seed from which the crop plant grows, or the locus of the crop plant with a biologically effective amount of a compound having formula 1.
Increasing crop vigor may result in one or more of the following observed effects: (a) Optimal crop cultivation (establistment) as demonstrated by excellent seed germination, crop emergence, and crop density (stand); (b) Enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., as measured by leaf area index), plant height, tiller number (e.g., for rice), root mass, and total dry weight of nutrients for the crop; (c) Improved crop yield as demonstrated by flowering time, duration of flowering, number of flowers, total biomass accumulation (i.e., yield), and/or product grade marketability (i.e., yield quality) of the fruit or grain; (d) Enhanced crop tolerance or prevention of plant disease infection and arthropod, nematode or mollusc pest infestation; and (e) increased ability of the crop to withstand environmental stresses such as exposure to extreme heat, suboptimal water, or phytotoxin chemicals.
The compounds and compositions of the present invention can increase the vigor of treated plants compared to untreated plants by preventing and/or treating plant diseases caused by fungal plant pathogens in the plant environment. In the absence of such control of plant disease, the disease reduces plant vigor by consuming plant tissue or juice, or transmitting plant pathogens such as viruses. The compounds of the present invention can increase plant vigor by altering the metabolism of the plant, even in the absence of fungal plant pathogens. Generally, if a plant is grown in a non-ideal environment, i.e., an environment that contains one or more aspects that are not conducive to the plant achieving its full genetic potential that should be exhibited in an ideal environment, then the vigor of the crop plant will be most significantly increased by treating the plant with a compound of the present invention.
Of note are methods for increasing the vigor of crop plants, wherein the crop plants are grown in an environment that includes plant diseases caused by fungal plant pathogens. Also of note are methods for increasing the vigor of a crop plant, wherein the crop plant is grown in an environment that does not include plant diseases caused by fungal plant pathogens. Also of note are methods for increasing the vigor of a crop plant, wherein the crop plant is grown in an environment that includes an amount of moisture that is less than the ideal amount of moisture to support the growth of the crop plant.
The compounds and compositions of the present invention may also be mixed with one or more other biologically active compounds or agents, including fungicides, insecticides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and root growth stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, viruses or fungi to form multi-component pesticides to impart an even broader spectrum of agricultural protection. Thus, the present invention also relates to a composition comprising a compound having formula 1 (in a fungicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount), and the composition may further comprise at least one of a surfactant, a solid diluent or a liquid diluent. Other biologically active compounds or agents may be formulated into compositions comprising at least one of a surfactant, a solid or a liquid diluent. For the mixtures of the invention, one or more other biologically active compounds or agents may be formulated together with the compound having formula 1 to form a premix, or one or more other biologically active compounds or agents may be formulated separately from the compound having formula 1, and the formulations are combined together prior to administration (e.g., in a spray tank), or alternatively, administered sequentially.
As mentioned in the summary, one aspect of the present invention is a fungicidal composition comprising a compound having formula 1, an N-oxide or a salt thereof (i.e., component (a)) and at least one other fungicide (i.e., component (b)) (i.e., a mixture or combination thereof). Of note is such a combination wherein the other fungicidally active ingredient has a different site of action than the compound of formula 1. In certain cases, a combination with at least one other fungicidal active ingredient having a similar control spectrum but different sites of action would be particularly advantageous for resistance management. Thus, the compositions of the present invention may further comprise a fungicidally effective amount of at least one additional fungicidal active ingredient having a similar spectrum of control but a different site of action.
<xnotran> (b) -S- ,4- -2,6- , , , , , , ( -M), , , ( - ), , , , , , , -S, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ( -M), , , , , , , , , (enoxastrobin) ( (enestroburin)), , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , (mandepropamid), , , , , , ( -M/ ), , , , , , , , , , , , , , , , , , , , , , , , , , ( , , ), , , , , , , , , , , , , , , , , , , , , , </xnotran> <xnotran> , , , , , quinofumelin ( 861647-84-9), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , -P, , ( ), , , , , N- [2- (1S,2R) - [1,1' - ] -2- ] -3- ( ) -1- -1H- -4- , α - (1- ) - α - [2- (2,2- ) ] -1H-1,2,4- -1- , (α S) - [3- (4- -2- ) -5- (2,4- ) -4- ] -3- , -1- [ [ (2R,3S) -3- (2- ) -2- (</xnotran> 2, 4-difluorophenyl) -2-oxocyclopropyl ] methyl ] -1H-1,2, 4-triazole, meso-2- [ [ (2R, 3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) -2-oxocyclopropyl ] methyl ] -1, 2-dihydro-3H-1, 2, 4-triazole-3-thione, meso-1- [ [ (2R, 3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) -2-oxocyclopropyl ] methyl ] -5- (2-propen-1-ylthio) -1H-1,2, 4-triazole, N- [2- [4- [ [3- (4-chlorophenyl) -2-propyn-1-yl ] oxy ] -3-methoxyphenyl ] ethyl ] -3-methyl-2- [ (methylsulfonyl) amino ] butanamide, N- [2- [4- [ [3- (4-chlorophenyl) -2-propyn-1-yl ] oxy ] -3-methoxyphenyl ] ethyl ] -3-methyl-2- [ (methylsulfonyl) amino ] ethyl ] -4-methyl ] -butanamide, N- [4- [ [ -yl ] methyl ] oxy ] -3-amino ] ethyl ] -4-2- [4- (4-chloro-methyl ] butanamide, n- [ [ (cyclopropylmethoxy) amino ] [6- (difluoromethoxy) -2, 3-difluorophenyl ] methylene ] phenylacetamide, N- [2- (2, 4-dichlorophenyl) -2-methoxy-1-methylethyl ] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, N- (3 ',4' -difluoro [1,1' -biphenyl ] -2-yl) -3- (trifluoromethyl) -2-pyrazinecarboxamide, 3- (difluoromethyl) -N- (2, 3-dihydro-1, 3-trimethyl-1H-inden-4-yl) -1-methyl-1H-pyrazole-4-carboxamide, 5, 8-difluoro-N- [2- [ 3-methoxy-4- [ [4- (trifluoromethyl) -2-pyridinyl ] oxy ] phenyl ] ethyl ] -4-quinazolinamine, 1- [4- [4- [5R- [ (2, 6-difluorophenoxy) methyl ] -4, 5-dihydro-3-isoxazolyl ] -2-thiazolyl ] -2-piperidinyl ] -2- [ 5-methyl-3- (trifluoromethyl) -1H-pyrazol-yl ] ethanone, 1- [4- (cyanopropyl ] amino ] methyl ] propyl ] methyl ] ethanone, 1- [1- (1H-cyanopropyl ] amino ] phenyl ] ethyl ] methyl ] ethyl ] phenyl ] ethanone 4-fluorophenyl acid ester, 5-fluoro-2- [ (4-fluorophenyl) methoxy ] -4-pyrimidinamine, α - (methoxyimino) -N-methyl-2- [ [ [1- [3- (trifluoromethyl) phenyl ] ethoxy ] imino ] methyl ] phenylacetamide, and [ [ 4-methoxy-2- [ [ [ (3S, 7R,8R, 9S) -9-methyl-8- (2-methyl-1-oxopropoxy) -2, 6-dioxo-7- (phenylmethyl) -1, 5-dioxononan-3-yl ] amino ] carbonyl ] -3-pyridyl ] oxy ] methyl 2-methylpropionate. Thus, of note are fungicidal compositions comprising as component (a) a compound having formula 1 (or an N-oxide or salt thereof) and as component (b) at least one fungicide selected from the foregoing lists.
Of particular note is the combination of a compound having formula 1 (or an N-oxide or salt thereof), i.e., component (a) in the composition, with a component (b) compound selected from the group consisting of: <xnotran> ( 1531626-08-0), , , , , , , , , , , , , ( 957144-77-3), , , , , , , , , , , , , , , , , , ( 1314008-27-9), , , , , , , , , ( -M/ ), , , , ( 1472649-01-6), , , , , ( , , - ), , , , , ( 1358061-55-8), , ( 1803108-03-3), , , , , , , , , α - (1- ) - α - [2- (2,2- ) ] -1H-1,2,4- -1- , </xnotran> N- [2- (2, 4-dichlorophenyl) -2-methoxy-1-methylethyl ] -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, 3- (difluoromethyl) -N- (2, 3-dihydro-1, 3-trimethyl-1H-inden-4-yl) -1-methyl-1H-pyrazole-4-carboxamide, 1- [4- [4- [5R- (2, 6-difluorophenyl) -4, 5-dihydro-3-isoxazolyl ] -2-thiazolyl ] -1-piperidinyl ] -2- [ 5-methyl-3- (trifluoromethyl) -1H-pyrazol-1-yl ] ethanone, a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable carrier 1, 1-dimethylethyl N- [6- [ [ [ [ (1-methyl-1H-tetrazol-5-yl) phenylmethylene ] amino ] oxy ] methyl ] -2-pyridinyl ] carbamate, 5-fluoro-2- [ (4-fluorophenyl) methoxy ] -4-pyrimidinamine, (α S) - [3- (4-chloro-2-fluorophenyl) -5- (2, 4-difluorophenyl) -4-isoxazolyl ] -3-pyridinemethanol, meso-1- [ [ (2R, 3S) -3- (2-chlorophenyl) -2- (2, 4- Difluorophenyl) -2-oxiranyl ] methyl ] -1H-1,2, 4-triazole, meso-2- [ [ (2R, 3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) -2-oxocyclopropyl ] methyl ] -1, 2-dihydro-3H-1, 2, 4-triazole-3-thione, and meso-1- [ [ (2R, 3S) -3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) -2-oxocyclopropyl ] methyl ] -5- (2-propen-1-ylthio) -1H-1,2, 4-triazole (i.e., as component (b) in the composition).
Generally preferred for better control of plant diseases caused by fungal plant pathogens (e.g., lower use rates or a broader spectrum of controlled plant pathogens) or resistance management are mixtures of compounds having formula 1, an N-oxide or salt thereof, and a fungicidal compound selected from the group consisting of: <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , . </xnotran>
In the fungicidal compositions of the present invention, component (a) (i.e., at least one compound selected from the group consisting of compounds having formula 1, N-oxides, and salts thereof) and component (b) are present in a fungicidally effective amount. The weight ratio of component (a) to component (b) (i.e., the one or more additional fungicidal compound (s)) is generally between about 1. Of note are compositions wherein the weight ratio of component (a) to component (b) is from about 125. In the case of many fungicidal compounds of component (b), these compositions are particularly effective for controlling plant diseases caused by fungal plant pathogens. Of particular note are compositions wherein the weight ratio of component (a) to component (b) is from about 25 to about 1. The weight ratio and application rate of the fungicidal compounds required for the desired fungicidal protection and control profile can be readily determined by one skilled in the art by simple experimentation. It will be apparent that the inclusion of an additional fungicidal compound in component (b) can extend the spectrum of plant diseases controlled beyond that controlled by component (a) alone. Furthermore, tables A1 to a21 and C1 to C21 illustrate the weight ratios of the combinations of fungicidal compounds of the present invention. Table B1 lists typical, more typical and most typical ratio ranges for specific fungicidal compounds relating to component (B).
The specific mixtures (compound numbers refer to the compounds in the index tables a to L) are listed in tables A1 to a 21. In table A1, each row under the column headings "component (a)" and "component (b)" specifically discloses a mixture of component (a) (i.e., compound 32) and component (b) a fungicidal compound. The entry under the heading "illustrative ratio" discloses three specific weight ratios of component (a) to component (b) of the disclosed mixtures. For example, the first row of table A1 discloses a mixture of compound 32 with acibenzolar-S-methyl and lists a weight ratio of compound 32 to acibenzolar-S-methyl of 1.
TABLE A1
Figure BDA0003913878900001601
Figure BDA0003913878900001611
Figure BDA0003913878900001621
Figure BDA0003913878900001631
Figure BDA0003913878900001641
Figure BDA0003913878900001651
Figure BDA0003913878900001661
Figure BDA0003913878900001671
(a) weight ratio of component (a) to component (b).
Tables A2 to a21 are each constructed identically to table A1 above, except that the entries under the column heading "component (a)" are replaced by the corresponding component (a) column entries shown below. Thus, for example, in table A2, the entries below the column heading "component (a)" all list "compound 64" and the first row below the column heading in table A2 specifically discloses a mixture of compound 64 and acibenzolar-S-methyl. Tables A3 to a21 are similarly constructed.
Figure BDA0003913878900001672
Figure BDA0003913878900001681
Table B1 lists specific combinations of component (B) compounds with component (a), illustrating the mixtures, compositions, and methods of the present invention. The first column of table B1 lists the specific component (B) compounds (e.g., "acibenzolar-S-methyl" in the first row). The second, third and fourth columns of table B1 list weight ratio ranges relative to the rate at which component (B) compounds are typically applied to field-grown crops. Thus, for example, the first row of table B1 discloses that the combination of component (a) compound and acibenzolar-S-methyl is typically applied in a weight ratio of component (a) to component (B) of between 2. The remaining rows of table B1 will be similarly constructed. Of particular note are compositions comprising any of the compounds listed in example 238 as a mixture of component (a) with the compounds listed in the column for component (B) of table B1, in the weight ratios disclosed in table B1. Table B1 therefore complements the specific ratios disclosed in tables A1 to a21 with the ratio ranges of these combinations.
TABLE B1
Figure BDA0003913878900001682
Figure BDA0003913878900001691
Figure BDA0003913878900001701
Figure BDA0003913878900001711
Figure BDA0003913878900001721
Figure BDA0003913878900001731
Figure BDA0003913878900001741
Figure BDA0003913878900001751
As already indicated, the present invention includes embodiments wherein in the composition comprising components (a) and (b), component (b) comprises at least one fungicidal compound from each of the two groups selected from (b 1) to (b 54). Tables C1 to C21 list specific mixtures (compound numbers refer to the compounds in the index tables a to L) to illustrate examples where component (b) comprises at least one fungicidal compound from each of the two groups selected from (b 1) to (b 54). In table C1, each row under the column headings "component (a)" and "component (b)" discloses in particular a mixture of component (a), which is compound 32, and at least two component (b) fungicidal compounds. The entry under the heading "illustrative ratio" discloses three specific weight ratios of component (a) to each component (b) fungicidal compound of the disclosed mixtures in order. For example, the first row discloses a mixture of compound 32 with cyproconazole and azoxystrobin and lists the weight ratio of compound 32 to cyproconazole and azoxystrobin as 1.
TABLE C1
Figure BDA0003913878900001761
Figure BDA0003913878900001771
Figure BDA0003913878900001781
Figure BDA0003913878900001791
Figure BDA0003913878900001801
(a) component (a) to component (b) in sequential weight ratios.
Tables C2 through C21 are each constructed identically to table C1 above, except that the entries under the "component (a)" column heading are replaced with the corresponding component (a) column entries shown below. Thus, for example, in table C2, the following entry under the column heading "component (a)" all recites "compound 64", and the first row under the column heading in table C2 specifically discloses compound 64 in admixture with cyproconazole and azoxystrobin, and an illustrative weight ratio of compound 64: cyproconazole: azoxystrobin is 1, 2. Tables C3 through C21 are similarly constructed.
Figure BDA0003913878900001811
Of note are compositions of the present invention comprising a compound having formula 1 (or an N-oxide or salt thereof) and at least one other fungicidal compound having a different site of action than the compound having formula 1. In certain cases, combination with at least one other fungicidal compound having a similar spectrum of control but different sites of action would be particularly advantageous for resistance management. Thus, the compositions of the present invention may advantageously comprise at least one fungicidally active compound selected from the group consisting of (b 1) to (b 54) as described above, having a similar spectrum of control but different sites of action.
Component (a), or the combination of components (a) and (b), may be further mixed with one or more other biologically active compounds or agents including insecticides, nematicides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as molting and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, phytonutrients, other biologically active compounds or entomopathogenic bacteria, viruses or fungi to form a multi-component pesticide to impart an even broader spectrum of agricultural protection. Thus, the present invention also relates to a composition comprising a fungicidally effective amount of component (a), or a mixture of component (a) and component (b), and a biologically effective amount of at least one additional biologically active compound or agent, and may further comprise at least one of a surfactant, a solid diluent or a liquid diluent. Other biologically active compounds or agents may also be formulated separately into compositions comprising at least one of a surfactant, a solid or a liquid diluent. For the compositions of the present invention, one or more additional biologically active compounds or agents may be formulated together with one or both of components (a) and (b) to form a premix, or one or more additional biologically active compounds or agents may be formulated separately from components (a) and (b) and the formulations combined together prior to administration (e.g., in a spray tank), or alternatively, administered sequentially.
Examples of such biologically active compounds or agents that may be formulated with component (a), or a combination of component (a) and component (b), are: insecticides, such as abamectin, acephate, norgestimate, acetamiprid, fluthrin, acribo (acytonapyr), diproprionate ([ (3S, 4R,4aR,6S,6aS,12R,12aS, 12bS) -3- [ (cyclopropylcarbonyl) oxy]1,3, 4a,5, 6a,12,12a, 12b-decahydro-6, 12-dihydroxy-4, 6a, 12b-trimethyl-11-oxo-9- (3-pyridyl) -2H, 11H-naphtho [2,1-b ]]Pyrano [3,4-e ]]Pyran-4-yl]Methyl cyclopropane formate), sulfadiazine, amitraz, abamectin, azadirachtin, baprofos, benfuracarb, benfurazone, pyriproxyfen (benzpyrimoxan), bifenthrin, kappa-bifenthrin, bifenazate, bistrifluron, borate, brofenamide (broflanilide), buprofezin, cadusate, carbaryl, carbofuran, cartap, vampire, chlorantraniliprole, chlorfenapyr, chlorfluazuron, d-trans-chlorpromazine (chloroprallethrin), chlorpyrifos-e (chloropyridios-e), chlorpyrifos-methyl, chromafenozide, clofentezine, d-trans-chlorpromazine, clothianidin, cyantraniliprolide (3-bromo-1- (3-chloro-2-pyridyl) -N- [ 4-cyano-2-methyl-6- [ (methylamino) carbonyl ]Phenyl radical]-1H-pyrazole-5-carboxamide), cyclobromamid (3-bromo-N- [ 2-bromo-4-chloro-6- [ [ (1-cyclopropylethyl) amino group]Carbonyl radical]Phenyl radical]-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxamide), cycloprothrin, cycloxaprid ((5S, 8R) -1- [ (6-chloro-3-pyridyl) methyl group]-2,3,5,6,7, 8-hexahydro-9-nitro-5, 8-epoxy-1H-imidazo [1,2-a ]]Azepine), cyenopyrafen, cyflumetofen, cyfluthrin, lambda-cyhalothrin, cyhalodiamide, cyhalothrin, lambda-cyhalothrin, cypermethrin, cis-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, diclomethaz, dieldrin, diflubenzuron, tetramethrin, dimehypo, dimethoate, metrizamide, dinotefuran, bendiofen, emamectin, methylamino-methylAbamectin benzoate, endosulfan, esfenvalerate, ethiprole, ethofenprox, epsilon-methoxybenzylfluthrin, etoxazole, fenbutatin oxide, fenitrothion, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flumetoquinone (2-ethyl-3, 7-dimethyl-6- [4- (trifluoromethoxy) phenoxy)]-4-quinolinylmethyl carbonate), flonicamid, triflumidinamide, flubendiamide, flucythrinate, pyrimethanil, flufenoxuron, flubendiamide ((alpha E) -2- [ [ 2-chloro-4- (trifluoromethyl) phenoxy ] phenacyl ]Methyl radical]-alpha- (methoxymethylene) phenylacetic acid methyl ester), flusufene (5-chloro-2- [ (3, 4-trifluoro-3-buten-1-yl) sulfonyl group]Thiazole), flurohexyl, fluopyram, butachlor (flupirole) (1- [2, 6-dichloro-4- (trifluoromethyl) phenyl group]-5- [ (2-methyl-2-propen-1-yl) amino]-4- [ (trifluoromethyl) sulfinyl group]-1H-pyrazole-3-carbonitrile), fluoropyrafuranone (4- [ [ (6-chloro-3-pyridinyl) methyl group](2, 2-Difluoroethyl) amino]-2 (5H) -furanone), flubiprofen (flupyrimin), cyfluthrin, fenvalerate, fluxaflutolide, disulfoton, varroan, fosthiazate, lambda-cyhalothrin, chlorfenapyr, heptaflumethrin ([ 2,3,5, 6-tetrafluoro-4- (methoxymethyl) phenyl) methothrin]Methyl 2, 2-dimethyl-3- [ (1Z) -3, 3-trifluoro-1-propen-1-yl]Cyclopropane carboxylic acid ester), hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soap, isopropylaminophen, isoxazolide, kappa-tefluthrin, lambda-cyhalothrin, lufenuron, malathion, cyhalothrin ([ 2,3,5,6-tetrafluoro-4- (methoxymethyl) phenyl group)]Methyl (1R, 3S) -3- (2, 2-dichlorovinyl) -2, 2-dimethylcyclopropanecarboxylate), metaflumizone, metaldehyde, methamidophos, methiocarb, methomyl, methoprene, methoxychlor, metocloprid, methoxyfenozide, epsilon-methoxybenzyl-fluthrin, epsilon-cyfluthrin (momfluorothrin), monocrotophos, monofluthrin ([ 2,3,5, 6-tetrafluoro-4- (methoxymethyl) phenyl group ]Methyl 3- (2-cyano-1-propen-1-yl) -2, 2-dimethylcyclopropanecarboxylate), nicotine, nitenpyram, nithiazine, novaluron, noviflu-uron, oxamyl, benzoxazole (oxazosulfyl), parathion, methyl parathion, permethrin, phorate, vothion, phosmet, phosphamidon, pirimicarb, profenofos, proffluthrin, propargitePropylbenzene hydrocarbon chrysanthemate and diflufenican (1, 3, 5-trimethyl-N- (2-methyl-1-oxopropyl) -N- [3- (2-methylpropyl) -4- [2, 2-trifluoro-1-methoxy-1- (trifluoromethyl) ethyl)]Phenyl radical]-1H-pyrazole-4-carboxamide), pymetrozine, pyriminostrobin, pyrethrin, pyridaben, pyridalyl, fluquinconazole, pyriminostrobin ((alpha E) -2- [ [ [2- [ (2, 4-dichlorophenyl) amino group]-6- (trifluoromethyl) -4-pyrimidinyl]Oxy radical]Methyl radical]-methyl alpha- (methoxymethylene) phenylacetate), pyraclodin, pyriproxyfen, rotenone, lanoline, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, meperidine ethyl (spiroperipridine), spirotetramat, thioprofenofos, sulfoxaflor (N- [ methyl oxide [1- [6- (trifluoromethyl) -3-pyridyl) pyrimethanil]Ethyl radical]-λ 4 -sulfinylamino]Cyanamide), tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, kappa-tefluthrin, terbufos, tetrachlorfenpyrad, fenpropathrin, tetramethrin, and tefluthrin ([ 2,3,5,6-tetrafluoro-4- (methoxymethyl) phenyl ] phenothrin ]Methyl 2,2,3,3-tetramethyl cyclopropanecarboxylate), tebuconazole, thiacloprid, thiamethoxam, thiodicarb, dimehypo, thiazafen (3-phenyl-5- (2-thienyl) -1,2,4-oxadiazole), tolfenpyrad, tetrabromoethrin, triazamate, trichlorfon, trifluoropyrimidine (2,4-dioxo-1- (5-pyrimidinylmethyl) -3- [3- (trifluoromethyl) phenyl ] pyrimidine]-2H-pyrido [1,2-a]Pyriminostrobin), triflumuron, thifenpyr (tylcyclopyrazoflor), beta-cypermethrin, bacillus thuringiensis delta-endotoxin, entomopathogenic bacteria, entomopathogenic viruses or entomopathogenic fungi.
One example of a biological agent for mixing with a compound of the present disclosure includes entomopathogenic bacteria, such as bacillus thuringiensis, and by
Figure BDA0003913878900001841
Encapsulated delta-endotoxins of bacillus thuringiensis prepared by processes such as
Figure BDA0003913878900001842
And
Figure BDA0003913878900001843
biocideInsect agent (A)
Figure BDA0003913878900001844
And
Figure BDA0003913878900001845
is Mycogen Corporation, indianapolis, indiana, USA [ Macken, indianapolis, ind. Napolis, ind., USA]Trademark of (d); entomopathogenic fungi, such as green muscardine fungi (green muscardine fungus); and entomopathogenic (naturally occurring and genetically modified) viruses, including baculovirus, nucleopolyhedrovirus (NPV), such as spodoptera frugiperda nucleopolyhedrovirus (hznnpv), spodoptera apiacea nucleopolyhedrovirus (AfNPV); and Granulosis Virus (GV), such as codling moth granulosis virus (CpGV).
General references to such agricultural protectants (i.e., insecticides, fungicides, nematicides, acaricides, herbicides and biological agents) include The Pesticide Manual, 13 th edition, c.d. s.tomlin editions, british Crop Protection Council, farnham, surrey, u.k. [ samadem of British ],2003 and The BioPesticide Manual, 2 nd edition, l.g. copping editions, british Crop Protection committee, farnham, surrey, u.k. [ samadem of British ],2001.
For embodiments in which one or more of these different mixing partners are used, the weight ratio of these different mixing partners (total) to component (a), or mixture of component (a) and component (b), is typically between about 1. Of note is a weight ratio between about 1. It will be apparent that the inclusion of these additional components can extend the spectrum of disease controlled beyond that controlled by component (a), or a mixture of component (a) and component (b).
The component (a) compound and/or combinations thereof with the component (b) compound and/or one or more other biologically active compounds or agents may be administered to plants genetically transformed to express proteins toxic to invertebrate pests, such as bacillus thuringiensis delta-endotoxin. The action of component (a) alone or in combination with component (b) of the present invention applied exogenously may act synergistically with the expressed toxin protein.
Of note is a combination or composition comprising component (a) or components (a) and (b) as described in the summary of the invention, which further comprises at least one invertebrate pest control compound or agent (e.g., insecticide, acaricide). Of particular note are compositions comprising component (a) and at least one (i.e., one or more) invertebrate pest control compound or agent, which may then be subsequently combined with component (b) to provide a composition comprising components (a) and (b) and the one or more invertebrate pest control compound or agent. Alternatively, without first being mixed with component (b), a biologically effective amount of a composition comprising component (a) and at least one invertebrate pest control agent may be applied to a plant or plant seed (directly or through the environment of the plant or plant seed) to protect the plant or plant seed from disease caused by fungal pathogens and damage caused by invertebrate pests.
For embodiments in which one or more of the invertebrate pest control compounds are used, the weight ratio of these compounds (total) to the compound of component (a) is typically between about 1. Of note is a weight ratio between about 1. The biologically effective amount of the active ingredient required for the desired spectrum of biological activity can be readily determined by one skilled in the art by simple experimentation.
Of note are compositions of the present invention that, in addition to the component (a) compound (alone or in combination with component (b)), further comprise at least one invertebrate pest control compound or agent selected from the group consisting of: <xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ζ - , , , , , , , , ε - , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , κ - , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> Sulfoxaflor, tebufenozide, tetramethrin, transfluthrin, thiacloprid, thiamethoxam, thiodicarb, dimehypo, tetrabromthrin, triazamate, triflumuron, fentrazazole, zeta-cypermethrin, bacillus thuringiensis delta-endotoxin, all strains of Bacillus thuringiensis and all strains of nuclear polyhedrosis virus.
In certain cases, the combination of the component (a) compounds of the present invention (alone or in admixture with component (b)) with other biologically active, in particular fungicidal, compounds or agents (i.e. active ingredients) may produce a more than additive (i.e. synergistic) effect. It has been desirable to reduce the amount of active ingredient released in the environment while ensuring effective pest control. Such combinations may be advantageously used to reduce crop production costs and reduce environmental loads when the fungicidal active ingredients produce an enhanced effect at application rates that achieve agronomically satisfactory levels of fungal control.
Table D1 lists specific combinations of invertebrate pest control agents with compound 32 as component (a) compound (compound number refers to the compound in index tables a to L), illustrating mixtures and compositions comprising these active ingredients and methods of using them according to the present invention. The second column of table D1 lists specific invertebrate pest control agents (e.g., "abamectin" in the first row). The third column of table D1 lists the mode of action (if known) or chemical class of the invertebrate pest control agent. The fourth column of table D1 lists one or more examples of weight ratio ranges for typical application rates of the invertebrate pest control agent relative to compound 32 alone or in combination with component (b) (e.g., abamectin is "50 to 1. Thus, for example, the first row of table D1 specifically discloses that the combination of compound 32 and abamectin is typically administered in a weight ratio between 50. The remaining rows of table D1 will be similarly constructed. Thus, for example, the first row of table D1 specifically discloses that the combination of compound 32 and abamectin is typically administered in a weight ratio between 50. The remaining rows of table D1 will be similarly constructed.
TABLE D1
Figure BDA0003913878900001871
Figure BDA0003913878900001881
Figure BDA0003913878900001891
Tables D2 through D21 are each constructed identically to table D1 above, except that the entries under the "component (a)" column heading are replaced with the corresponding component (a) column entries shown below. Thus, for example, in table D2, the entries under the column heading "component (a)" all list "compound 64", and the first row under the column heading in table D2 specifically discloses a mixture of compound 64 and abamectin. Tables D3 to D21 are similarly constructed.
Figure BDA0003913878900001892
Compositions comprising compounds having formula 1 useful for seed treatment agents may further comprise bacteria and fungi having the ability to provide protection from phytopathogenic fungi or the harmful effects of bacteria and/or earthy animals such as nematodes. Bacteria exhibiting nematicidal properties may include, but are not limited to, bacillus firmus, bacillus cereus, bacillus subtilis, and bacillus pasteurii. A suitable Bacillus firmus strain is as BioNem TM The commercially available strain CNCM I-1582 (GB-126). A suitable strain of Bacillus cereus is strain NCMM I-1592. Both strains of bacillus are disclosed in US 6,406,690. Other suitable bacteria exhibiting nematicidal activity are bacillus amyloliquefaciens IN937a and bacillus subtilis strain GB03. Bacteria exhibiting fungicidal properties may include, but are not limited to, bacillus pumilus strain GB34. Fungal species exhibiting nematicidal properties may include, but are not limited to, myrothecium verrucaria, paecilomyces lilacinus and Purpureocillium lilacinum.
The seed treatment may also comprise one or more nematicides of natural origin, such as elicitor proteins known as hypersensitive proteins (harpins), isolated from certain bacterial plant pathogens, such as erysiphe pyricularis (Erwinia amylovora). Examples are as N-Hibit TM Harpin-N-Tek seed treatment technology available from Gold CST.
The seed treatment may also comprise one or more species of leguminous plant root nodule bacteria, such as the micro symbiotic nitrogen fixing bacteria bradyrhizobium japonicum. These inoculants may optionally comprise one or more Lipid Chitooligosaccharides (LCO), which areIs a nodulation (Nod) factor produced during the initiation of nodulation on the roots of leguminous plants by rhizobia bacteria. For example,
Figure BDA0003913878900001901
brand seed treatment Technology combined with LCO promoter Technology in combination with inoculant TM 。
The seed treatment may further comprise one or more isoflavones, which may increase the level of root colonization by the mycorrhizal fungi. Mycorrhizal fungi improve plant growth by enhancing the uptake of nutrients such as water, sulfate, nitrate, phosphate and metals by the roots. Examples of isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperetin, naringenin, and pratensein. Formononetin as mycorrhizal inoculant product such as PHC
Figure BDA0003913878900001902
The active ingredient in AG is available.
The seed treatment may further comprise one or more plant activators that cause systemic acquired resistance in plants upon contact by a pathogen. An example of a plant activator that causes such a protective mechanism is acibenzolar-S-methyl.
In the fungicidal compositions of the present invention, the compound of formula 1 of component (a) may act synergistically with the additional fungicidal compound of component (b) to provide such beneficial results as extending the spectrum of plant diseases controlled, extending the duration of prophylactic and therapeutic protection, and inhibiting the proliferation of resistant fungal pathogens. In a particular embodiment, there is provided according to the present invention a composition comprising the proportions of component (a) and component (b) that are particularly useful for controlling specific fungal diseases such as early blight of tomato, powdery mildew of wheat, botrytis cinerea, puccinia triticina, rhizoctonia solani, septoria nodorum, septoria tritici.
Mixtures of fungicides can also provide significantly better disease control than might be expected based on the activity of the individual components. This synergy has been described as "the cooperation of two components of a mixture such that the total effect is greater than or exceeds the sum of the two (or more) individual effects" (see p.m.l.tames, neth.j.plant Pathology [ J.Phytopathology of the Netherlands ]1964,70, 73-80). In a method of providing plant disease control, wherein a synergistic effect is exhibited from a combination of active ingredients (e.g., fungicidal compounds) applied to a plant or seed, the active ingredients are applied in a synergistically effective weight ratio and in synergistically effective (i.e., synergistically effective) amounts. The disease control, inhibition and prevention measures cannot exceed 100%. Thus, expression of substantial synergy typically requires the use of an application rate of the active ingredients where the active ingredients alone provide far less than 100% of the effect such that their additive effect is substantially less than 100% to allow for increased likelihood of effect due to synergy. On the other hand, too low an application rate of the active ingredient may show not much activity in the mixture, even though there is a synergistic benefit. The weight ratio and application rate (i.e. amount) of the fungicidal compound providing the synergistic effect can be easily determined and optimized by the person skilled in the art by simple experiments.
The existence of Synergistic effects between the two active ingredients was determined by means of the Kolbe's ratio (Colby) equation (see Colby, S.R. "marketing Synergistic and Antagonistic Responses of Herbicide Combinations [ calculate Synergistic and Antagonistic Responses of Herbicide Combinations ]", weeds [ Weeds ], (1967), 15, 20-22):
Figure BDA0003913878900001911
using the korbi method, it was determined that there was a synergistic interaction between the two active ingredients by first calculating the expected activity p of the mixture based on the activities of the two components applied separately. If p is below the experimentally determined effect, a synergistic effect occurs. In the above formula, a is the fungicidal activity controlled as a percentage of one component applied alone at a ratio x. Item B is the fungicidal activity controlled as a percentage of the second component applied at the ratio y. This formula estimates the expected fungicidal activity of p, i.e. a mixture of a in a ratio x and B in a ratio y, if their effect is strictly additive and no interaction occurs.
The following tests demonstrate the control efficacy of the compounds of the invention against specific pathogens. However, the pathogen control protection provided by the compounds is not limited to these species. Compound descriptions are found in the following index tables a to L. The following abbreviations are used in the index tables: me means methyl, et means ethyl, n-Pr means n-propyl, i-Pr means isopropyl, c-Pr means cyclopropyl, n-Bu means n-butyl, i-Bu means isobutyl, c-Bu means cyclobutyl, c-hexyl means cyclohexyl, ph means phenyl, meO means methoxy and EtO means ethoxy. The abbreviation "cmpd.no." stands for "mixture number" and the abbreviation "Ex" stands for "example" and is followed by a number indicating in which example the compound was prepared. The abbreviation "m.p." stands for melting point. The values reported in the "MS" column are obtained by adding H to the molecule with the highest isotopic abundance + (molecular weight 1) the highest isotopically abundant positively charged parent ion (M + 1) formed, or by loss of H + (molecular weight 1) the highest isotopically abundant negatively charged ion (M-1) formed has a molecular weight. No higher atomic weight isotopes containing one or more lower abundances are reported (e.g., 37 Cl、 81 br) is present. The reported MS peaks were observed by mass spectrometry using electrospray ionization (ESI) or Atmospheric Pressure Chemical Ionization (APCI).
Index Table A
Figure BDA0003913878900001921
Figure BDA0003913878900001922
Figure BDA0003913878900001931
* 19 F NMR data see index table M.
Index Table A1
Figure BDA0003913878900001932
Figure BDA0003913878900001933
* 19 The F NMR data are referred to index Table M.
Index Table A2
Figure BDA0003913878900001941
Figure BDA0003913878900001942
Index table B
Figure BDA0003913878900001943
A dash "-" in column L means that L is a direct bond.
Figure BDA0003913878900001944
Figure BDA0003913878900001951
* 19 F NMR data see index table M.
** 1 See index table N for H NMR data.
Index table C
Figure BDA0003913878900001952
Figure BDA0003913878900001953
Figure BDA0003913878900001961
Figure BDA0003913878900001971
* 19 The F NMR data are referred to index Table M.
Note 1: a mixture of diastereomers of 87.
Note 2: a 33.
Note 4: 60 of the cis-trans isomer.
Index table D
Figure BDA0003913878900001972
Figure BDA0003913878900001973
Figure BDA0003913878900001981
* 19 The F NMR data are referred to index Table M.
Index table E
Figure BDA0003913878900001982
A dash "-" in column L means that L is a direct bond.
Figure BDA0003913878900001983
Figure BDA0003913878900001991
Figure BDA0003913878900002001
* 19 F NMR data see index table M.
Index table E1
Figure BDA0003913878900002002
Figure BDA0003913878900002003
Figure BDA0003913878900002011
Index table F
Figure BDA0003913878900002012
R 13 Dash "-" in the column means that R is absent 13 The substituents and the remaining carbon valencies are occupied by hydrogen atoms. A dash "-" in column L means that L is a direct bond. Unless otherwise indicated, the configuration of the substituents around the double bond in the above structure is as shown in the structure.
Figure BDA0003913878900002013
Figure BDA0003913878900002021
Figure BDA0003913878900002031
* 19 F NMR data see index table M.
Index Table F1
Figure BDA0003913878900002032
Unless otherwise indicated, the configuration of the substituents around the double bond in the above structures is as shown in the structures.
Figure BDA0003913878900002033
* 19 F NMR data see index table M.
Index table G
Figure BDA0003913878900002041
A dash "-" in column L means that L is a direct bond. Unless otherwise indicated, the configuration of the substituents around the double bond in the above structure is as shown in the structure.
Figure BDA0003913878900002042
Figure BDA0003913878900002051
Figure BDA0003913878900002061
Figure BDA0003913878900002071
Figure BDA0003913878900002081
Figure BDA0003913878900002091
* 19 F NMR data see index table M.
** 1 See index table N for H NMR data.
Note 7: HBr salt.
Index table H
Figure BDA0003913878900002092
Unless otherwise indicated, the configuration of the substituents around the double bond in the above structures is as shown in the structures.
Figure BDA0003913878900002093
Figure BDA0003913878900002101
* 19 F NMR data see index table M.
Index Table I
Figure BDA0003913878900002102
R 13 Dash "-" in the column means that R is absent 13 The substituents and the remaining carbon valencies are occupied by hydrogen atoms. Unless otherwise indicated, the configuration of the substituents around the double bond in the above structures is as shown in the structures.
Figure BDA0003913878900002103
* 19 The F NMR data are referred to index Table M.
Index table J
Figure BDA0003913878900002111
Unless otherwise indicated, the configuration of the substituents around the double bond in the above structure is as shown in the structure.
Figure BDA0003913878900002112
* 19 F NMR data see index table M.
Index table K
Figure BDA0003913878900002113
A dash "-" in column L means that L is a direct bond. Unless otherwise indicated, the configuration of the substituents around the double bond in the above structures is as shown in the structures.
Figure BDA0003913878900002114
Figure BDA0003913878900002121
* 19 The F NMR data are referred to index Table M.
Index Table K1
Figure BDA0003913878900002131
R 8 Dash "-" in the column means that R is absent 8 The substituents and the remaining carbon valencies are occupied by hydrogen atoms. Unless otherwise indicated, the configuration of the substituents around the double bond in the above structures is as shown in the structures.
Figure BDA0003913878900002132
Index table L
Figure BDA0003913878900002133
Figure BDA0003913878900002141
Figure BDA0003913878900002151
Figure BDA0003913878900002161
Figure BDA0003913878900002171
Figure BDA0003913878900002181
Figure BDA0003913878900002191
Note 6: 3 of the geometric isomer.
* 19 F NMR data see index table M.
** 1 See index table N for H NMR data.
Index table M
Figure BDA0003913878900002192
Figure BDA0003913878900002201
Figure BDA0003913878900002211
Figure BDA0003913878900002221
Figure BDA0003913878900002231
Figure BDA0003913878900002241
a Unless otherwise indicated, all references to FIGS 19 F NMR spectra in CDCl 3 In solution, relative to CF 3 CCl 3 Reported in ppm. Coupling is specified by(s) -singlet, (t) -triplet and (m) -multiplet.
Index table N
Figure BDA0003913878900002242
a 1 H NMR data is reported in ppm at low field of tetramethylsilane. Coupling is specified by(s) -singlet, (t) -triplet, (q) -quartet.
Biological examples of the invention
General protocol for preparing test suspensions for tests a-E: the test compound was first dissolved in acetone in an amount equal to 3% of the final volume and then suspended in acetone and purified water (50/50 mix by volume) containing 250ppm of the surfactant PEG400 (polyol ester) at the desired concentration (in ppm). The resulting test suspensions were then used for tests a-E.
Test A
The test solution was sprayed onto soybean seedlings to the point of run-off. The following day, seedlings were inoculated with a spore suspension of soybean rust (Phakopsora pachyrhizi) (the causative agent of asian soybean rust) and incubated for 24h in a saturated atmosphere at 22 ℃, and then moved to a growth chamber at 22 ℃ for 8 days, after which visual disease rating was performed.
Test B
The test solution was sprayed to the point of run-off on wheat seedlings. The following day, seedlings were inoculated with a spore suspension of Puccinia recondita f.sp.tritici (a pathogen of wheat leaf rust) and incubated in a saturated atmosphere at 20 ℃ for 24h, and then moved to a growth chamber at 20 ℃ for 6 days, after which disease rating was performed.
Test C
The test solution was sprayed to the point of run-off on grape seedlings. The following day, seedlings were inoculated with a spore suspension of grape powdery mildew (Uncinula necator), the causative agent of grape powdery mildew, and incubated in a growth chamber at 20 ℃ for 12 days, after which disease ratings were performed.
Test D
The test solution was sprayed to the point of run-off on wheat seedlings. The next day, seedlings were inoculated with a spore suspension of wheat leaf blight (zymophytotia tritici) (the causative agent of wheat leaf spot disease) and incubated in a saturated atmosphere at 24 ℃ for 48h, and then moved to a growth chamber at 20 ℃ for 17 days, after which disease rating was performed.
Test E
The test suspension was sprayed to the point of run-off on wheat seedlings. The next day, seedlings were inoculated with spore powder of Erysiphe graminis f.sp.tritici (also known as Erysiphe graminis f.sp.tritici), the causative agent of wheat powdery mildew, and incubated in a growth chamber at 20 ℃ for 8 days, after which visual disease ratings were performed.
The results of tests a-E are given in table a. In the table, a rating of 100 indicates disease control of 100% and a rating of 0 indicates no disease control (relative to control). The asterisks "+" or double asterisks "+" or triple asterisks "+" next to the rank values indicate that 50ppm, 10ppm and 250ppm of test suspension were used, respectively. Dash (-) indicates compound not tested.
TABLE A
Figure BDA0003913878900002261
Figure BDA0003913878900002271
Figure BDA0003913878900002281
Figure BDA0003913878900002291
Figure BDA0003913878900002301
Figure BDA0003913878900002311
Figure BDA0003913878900002321
Figure BDA0003913878900002331
Figure BDA0003913878900002341
Figure BDA0003913878900002351
Figure BDA0003913878900002361
Figure BDA0003913878900002371
Figure BDA0003913878900002381
Figure BDA0003913878900002391
Figure BDA0003913878900002401
The test results presented in table a above for compounds having formula 1 illustrate the fungicidal activity of component (a), which contributes to the plant disease control efficacy of compositions comprising a combination of component (a) with component (b) and optionally at least one additional fungicidal compound according to the present invention.
Test F below demonstrates the control efficacy of the compositions of the present invention against asian soybean rust. The general protocol for preparing the test compositions for test F is as follows: compound 32, compound 64, azoxystrobin, propiconazole, bixafen, chlorothalonil, cyproconazole, epoxiconazole, fenpropidin, fenpropimorph, thiabendazole, flutriafol, fluxapyroxad, metominostrobin, picoxystrobin, prothioconazole, fluxapyroxad, pyraclostrobin, tebuconazole and trifloxystrobin were obtained as unformulated, technical grade materials. Copper hydroxide and mancozeb are available as formulated products sold under the trademarks KOCIDE 3000 and MANZATE, respectively. The unformulated material was first dissolved in acetone and then suspended in acetone at the desired concentration (in ppm) and containing 250ppm of surfactant
Figure BDA0003913878900002411
014 (polyol ester) in purified water (50/50 mix by volume). The formulated material is dispersed in sufficient water to achieve the desired concentration and neither organic solvents nor surfactants are added to the suspension. The resulting test mixture was then used in test F. The tests were performed on four individual plants and the results are reported as the average of four plants.
The existence of a Synergistic effect between the two active ingredients was determined by means of the formula of the Korl ratio (Colby, S.R. "stabilizing Synergistic and Antagonistic Responses of Herbicide Combinations [ calculate Synergistic and Antagonistic Responses of Herbicide Combinations ]", seeds [ Weeds ], (1967), 15, 20-22):
Figure BDA0003913878900002412
using the kor ratio method, it was determined that there was a synergistic interaction between the two active ingredients by first calculating the expected activity p of the mixture based on the activities of the two components administered separately. If p is below the experimentally determined effect, a synergistic effect occurs. In the above formula, a is the fungicidal activity controlled as a percentage of one component applied alone at a ratio x. Item B is the fungicidal activity controlled as a percentage of the second component applied at the rate y. This formula estimates the expected fungicidal activity of p, i.e. a mixture of a in a ratio x and B in a ratio y, if their effect is strictly additive and no interaction occurs.
Test F
The test mixture was sprayed to the point of run-off on soybean seedlings. The following day, seedlings were inoculated with a spore suspension of soybean rust (Phakopsora pachyrhizi), a causative agent of asian soybean rust, and incubated in a saturated atmosphere at 22 ℃ for 24h and then moved to a growth chamber at 22 ℃ for 8 days, after which visual disease rating was performed.
The results of test F are given for compound 32 in tables B-1 to I-1 and for compound 64 in tables B-2 to I-2. Each table corresponds to a set of evaluations that are performed together at the same time. In each table, a rating of 100 indicates disease control of 100% and a rating of 0 indicates no disease control (relative to control). The column labeled "Obsd" indicates the average of the results observed from tests performed on four individual plants. The column labeled "Exp" indicates the expected value of each treatment mixture using the kerr's ratio formula.
TABLE B-1
Observed and expected effects of compound 32 alone and in mixture with picoxystrobin in controlling asian soybean rust
Figure BDA0003913878900002421
TABLE B-2
Observed and expected effects of compound 64 alone and in mixture with picoxystrobin in controlling asian soybean rust
Figure BDA0003913878900002422
Figure BDA0003913878900002431
TABLE C-1
Observed and expected effects of Compound 32 alone and in mixtures with Bixafen, fluxapyroxad and Fluindazinam in the control of Asian Soybean rust
Figure BDA0003913878900002432
Figure BDA0003913878900002441
TABLE C-2
Observed and expected effects of Compound 64 alone and in admixture with Bixafen, fluxapyroxad and Fluindazinam in the control of Asian Soybean rust
Figure BDA0003913878900002442
Figure BDA0003913878900002451
TABLE D-1
Observed and expected effects of compound 32 alone and in admixture with mancozeb, fenpropimorph and tebuconazole in the control of asian soybean rust
Figure BDA0003913878900002452
Figure BDA0003913878900002461
TABLE D-2
Observed and expected effects of compound 64 alone and in admixture with mancozeb, fenpropimorph and tebuconazole in the control of asian soybean rust
Figure BDA0003913878900002462
Figure BDA0003913878900002471
TABLE E-1
Observed and expected effects of Compound 32 alone and in admixture with cyproconazole, azoxystrobin and trifloxystrobin in controlling Asian Soybean rust
Figure BDA0003913878900002472
Figure BDA0003913878900002481
TABLE E-2
Observed and expected effects of Compound 64 alone and in admixture with cyproconazole, azoxystrobin and trifloxystrobin in controlling Asian soybean rust
Figure BDA0003913878900002482
Figure BDA0003913878900002491
TABLE F-1
Observed and expected effects of compound 32 alone and in admixture with epoxiconazole and fluxapyroxad in controlling asian soybean rust
Figure BDA0003913878900002492
Figure BDA0003913878900002501
TABLE F-2
Observed and expected effects of Compound 64 alone and in mixtures with epoxiconazole and Fluxapyroxad in the control of Asian Soybean Rust
Figure BDA0003913878900002502
TABLE G-1
Observed and expected effects of Compound 32 alone and in admixture with Benzovindiflupyr, prothioconazole and chlorothalonil in the control of Asian Soybean Rust
Figure BDA0003913878900002511
TABLE G-2
Observed and expected effects of Compound 64 alone and in admixture with Benzovindiflupyr, prothioconazole, and chlorothalonil in controlling Asian Soybean Rust
Figure BDA0003913878900002521
TABLE H-1
Observed and expected effects of compound 32 alone and in admixture with fluxapyroxad, pyraclostrobin and metominostrobin in controlling asian soybean rust
Figure BDA0003913878900002522
Figure BDA0003913878900002531
TABLE H-2
Observed and expected effects of compound 64 alone and in admixture with fluxapyroxad, pyraclostrobin and metominostrobin in controlling asian soybean rust
Figure BDA0003913878900002532
Figure BDA0003913878900002541
TABLE I-1
Observed and expected effects of Compound 32 alone and in mixtures with copper hydroxide, flutriafol, and fenpropidin in the control of Asian Soybean rust
Figure BDA0003913878900002542
Figure BDA0003913878900002551
TABLE I-2
Observed and expected effects of Compound 64 alone and in mixture with copper hydroxide, flutriafol, and fenpropidin in the control of Asian Soybean rust
Figure BDA0003913878900002552
Figure BDA0003913878900002561

Claims (15)

1. A fungicidal composition comprising:
(a) At least one compound selected from compounds having formula 1, N-oxides, and salts thereof:
Figure FDA0003913878890000011
wherein
T is selected from the group consisting of:
Figure FDA0003913878890000012
wherein the key extending to the left is attached to a;
R 1 is CF 3 、CHF 2 、CCl 3 、CHCl 2 、CF 2 Cl、CFCl 2 Or CHFCl;
w is O, S or NR 3 ；
R 3 Is H, cyano, nitro, C (= O) OH, benzyl, C 1 -C 4 Alkyl radical, C 2 -C 4 Alkylcarbonyl group, C 2 -C 4 Halogenated alkylcarbonyl, OR 3a Or NR 3b R 3c ；
R 3a Is H, benzyl, C 1 -C 4 Alkyl radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 A haloalkylcarbonyl group;
R 3b is H, C 1 -C 4 Alkyl radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 A haloalkylcarbonyl group;
R 3c is H or C 1 -C 4 An alkyl group; or
R 3b And R 3c Together form a 4-to 6-membered fully saturated heterocyclic ring, each ring containing, in addition to the linking nitrogen atom, ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, each ring optionally substituted with up to 2 methyl groups;
x is O, S or NR 5a ；
Y is O, S or NR 5b ；
R 5a And R 5b Each independently is H, hydroxy or C 1 -C 4 An alkyl group;
R 2a and R 2b Each independently is H, C 1 -C 4 Alkyl radical, C 2 -C 4 Alkenyl radical, C 3 -C 15 Trialkylsilyl group, C 3 -C 15 Halogenotrialkylsilyl group, (CR) 4a R 4b ) p -OH、(CR 4a R 4b ) p -SH、(CR 4a R 4b ) p -Cl or (CR) 4a R 4b ) p -Br; or
R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-to 7-membered saturated ring containing, in addition to these atoms X and Y, a ring member selected from carbon atoms, wherein up to 2 carbon atom ring members are independently selected from C (= O) and C (= S), the ring being optionally substituted on a carbon atom ring member with up to 2 atoms independently selected from halogen, cyano, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy and C 1 -C 2 Substituted with a halo alkoxy group;
R 2c is C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Haloalkenyl, C 2 -C 4 Alkynyl, C 2 -C 4 Haloalkynyl or trifluoromethylsulfonyl, each of which is optionally substituted with up to 2 substituents independently selected from cyano, hydroxyGroup, SC ≡ N and C 1 -C 2 Substituent substitution of alkoxy;
R 2d is H, cyano, halogen or C 1 -C 4 An alkyl group;
each R 4a And R 4b Independently is H or C 1 -C 4 An alkyl group;
p is 2 or 3;
when T is T-1 or T-2, then A is A 1 -A 2 -CR 6a R 6b Wherein A is 1 Is linked to J, and CR 6a R 6b Is linked to T;
when T is T-3, then A is A 1 -A 2 Wherein A is 1 Is connected to J, and A 2 Is linked to T;
A 1 is CR 6c R 6d 、N(R 7a ) O or S;
A 2 is a direct bond, CR 6e R 6f 、N(R 7b ) O or S;
R 6a 、R 6b 、R 6c 、R 6d 、R 6e and R 6f Each independently is H, cyano, hydroxy, halogen, C (= O) OCH 3 Or C 1 -C 4 An alkyl group;
R 7a and R 7b Each independently is H, C (= O) H, cyano, C 1 -C 4 Alkyl or C 2 -C 4 An alkylcarbonyl group;
j is selected from the group consisting of:
Figure FDA0003913878890000021
Figure FDA0003913878890000031
wherein the key extending to the left is attached to L and the key extending to the right is attached to a;
each R 8 Independently F, cl, I, br, cyanoMethyl, trifluoromethyl or methoxy;
q is 0, 1, 2, 3 or 4;
l is (CR) 9a R 9b ) n ；
Each R 9a And R 9b Independently H, halogen, cyano, hydroxy, nitro, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 3 Alkoxy or C 1 -C 3 A haloalkoxy group;
n is 0, 1, 2 or 3;
e is C 1 -C 6 Alkyl or C 1 -C 6 A haloalkyl group; or alternatively
E is E 1 Or E 2 ；
E 1 Is amino, cyano, hydroxyl, nitro, CH (= O), C (= O) OH, C (= O) NH 2 、C(＝S)NH 2 、OC(＝O)NH 2 、OC(＝S)NH 2 、NHC(＝O)NH 2 、NHC(＝S)NH 2 、SC≡N、-CH＝NNHC(＝O)OC 1 -C 6 Alkyl or-N (OCH) 3 )C(＝O)C 1 -C 6 An alkyl group; or
E 1 Is C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkylthio radical, C 2 -C 6 Alkenylthio radical, C 2 -C 6 Alkynylthio, C 1 -C 6 Alkylsulfinyl radical, C 2 -C 6 Alkenylsulfinyl, C 2 -C 6 Alkynylsulfinyl group, C 1 -C 6 Alkylsulfonyl radical, C 2 -C 6 Alkenylsulfonyl radical, C 2 -C 6 Alkynylsulfonyl radical, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkenylsulfonylamino group, C 2 -C 6 Alkynylsulfonylamino, C 1 -C 6 Alkylaminosulfonyl radical, C 2 -C 6 Dialkylaminosulfonyl radical, C 2 -C 6 Alkenylaminosulfonyl radical, C 2 -C 6 Alkynylaminosulfonyl radical, C 1 -C 6 Alkylamino sulfonylamino group, C 2 -C 6 Alkenylaminosulfonylamino group, C 2 -C 6 Alkynyl aminosulfonylamino, C 2 -C 6 Alkylcarbonyl group, C 3 -C 6 Alkenylcarbonyl group, C 3 -C 6 Alkynyl carbonyl group, C 2 -C 6 Alkylaminocarbonyl radical, C 3 -C 6 Alkenylaminocarbonyl group, C 3 -C 6 Alkynyl aminocarbonyl group, C 2 -C 6 Alkylcarbonylamino, C 3 -C 6 Alkenylcarbonylamino group, C 3 -C 6 Alkynyl carbonylamino group, C 2 -C 6 Alkylamino carbonylamino group, C 3 -C 6 Alkenylaminocarbonylamino group, C 3 -C 6 Alkynyl aminocarbonylamino, C 2 -C 6 Alkylcarbonyloxy, C 3 -C 6 Alkenylcarbonyloxy, C 3 -C 6 Alkynyl carbonyloxy, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl, C 2 -C 6 Alkyl amino carbonyl oxygen radical, C 3 -C 6 Alkenylaminocarbonyloxy radical, C 3 -C 6 Alkynyl aminocarbonyloxy, C 2 -C 6 Alkoxycarbonylamino group, C 3 -C 6 Alkenyloxycarbonylamino, C 3 -C 6 Alkynyloxycarbonylamino group, C 2 -C 6 Alkylamino (thiocarbonyl) oxy, C 3 -C 6 Alkenylamino (thiocarbonyl) oxy, C 3 -C 6 Alkynylamino (thiocarbonyl) oxy, C 2 -C 6 Alkoxy (thiocarbonyl) amino, C 3 -C 6 Alkenyloxy (thiocarbonyl) amino, C 3 -C 6 Alkynyloxy (thiocarbonyl) amino, C 2 -C 6 Alkyl (thiocarbonyl), C 2 -C 6 (alkylthio) carbonyl, C 3 -C 6 Alkenyl (thiocarbonyl), C 3 -C 6 (alkenylthio) carbonyl, C 3 -C 6 Alkynyl (thiocarbonyl), C 3 -C 6 (alkynylthio) carbonyl, C 2 -C 6 Alkylamino (thiocarbonyl), C 3 -C 6 Alkenylamino (thiocarbonyl), C 3 -C 6 Alkynylamino (thiocarbonyl), C 2 -C 6 Alkyl (thiocarbonyl) amino, C 2 -C 6 (alkylthio) carbonylamino, C 3 -C 6 Alkenyl (thiocarbonyl) amino, C 3 -C 6 (alkenylthio) carbonylamino group, C 3 -C 6 Alkynyl (thiocarbonyl) amino, C 3 -C 6 (alkynylthio) carbonylamino group, C 2 -C 6 Alkylamino (thiocarbonyl) amino, C 3 -C 6 Alkenylamino (thiocarbonyl) amino or C 3 -C 6 Alkynylamino (thiocarbonyl) amino wherein each carbon atom is optionally substituted with up to 1 substituent selected from R 10a And up to 3 substituents independently selected from R 10b Substituted with the substituent(s);
R 10a is optionally selected from R by up to 3 11a Phenyl substituted with the substituent of (1); or a 5-to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, wherein up to 3 carbon atom ring members are independently selected from C (= O) and C (= S), and sulfur atom ring members are independently S (= O) u (＝NR 12 ) v Each ring is optionally substituted with up to 3 substituents independently selected from R on a carbon atom ring member 11a And independently selected from R on a nitrogen ring member 11b ；
Each R 10b Independently amino, cyano, halogen, hydroxy, nitro, SC ≡ N, -SH, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Halocycloalkyl radical, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 1 -C 4 Alkylthio radical, C 1 -C 4 Alkylsulfinyl radical, C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Haloalkylsulfonyl group, C 1 -C 4 Alkylamino radical, C 2 -C 4 Dialkylamino radical, C 2 -C 4 Alkyl carbonyl, C 2 -C 4 Halogenoalkylcarbonyl group, C 2 -C 5 Alkoxycarbonyl group, C 2 -C 5 Halogenoalkoxycarbonyl, C 2 -C 5 Alkylaminocarbonyl or C 3 -C 5 A dialkylaminocarbonyl group;
each R 11a Independently halogen, hydroxy, cyano, amino, nitro, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, C 1 -C 4 Hydroxyalkyl, C 3 -C 6 Cycloalkyl radical, C 4 -C 7 Cycloalkylalkyl radical, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkynyloxy, C 2 -C 4 Alkoxyalkyl group, C 2 -C 6 Alkylcarbonyloxy, C 1 -C 4 Alkylthio radical, C 1 -C 4 Halogenoalkylthio, C 2 -C 6 Alkylcarbonylthio, C 1 -C 4 Alkylsulfinyl radical, C 1 -C 4 Haloalkylsulfinyl radical, C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Haloalkylsulfonyl group, C 1 -C 4 Alkylsulfonyloxy, C 1 -C 4 Alkylamino radical, C 2 -C 8 Dialkylamino radical, C 3 -C 6 Cycloalkylamino, C 2 -C 4 Alkylcarbonyl group, C 3 -C 5 Alkenylcarbonyl group, C 3 -C 5 Alkynyl carbonyl group, C 4 -C 7 Cycloalkyl carbonyl group, C 5 -C 8 Cycloalkylalkylcarbonyl, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 7 Alkenyloxycarbonyl radical, C 3 -C 7 Alkynyloxycarbonyl group, C 4 -C 7 Cycloalkoxycarbonyl radical, C 5 -C 8 Cycloalkyl alkoxycarbonyl, C 2 -C 6 Alkylaminocarbonyl radical, C 3 -C 6 Alkenylaminocarbonyl group, C 3 -C 6 Alkynyl aminocarbonyl group, C 4 -C 7 Cycloalkylaminocarbonyl group, C 5 -C 8 Cycloalkylalkylaminocarbonyl radical, C 3 -C 8 Dialkylaminocarbonyl or C 3 -C 6 A trialkylsilyl group;
each R 11b Independently C (= O) H, C 1 -C 3 Alkyl radical, C 1 -C 3 Alkoxy radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 An alkoxycarbonyl group;
each R 12 Independently of one another H, cyano, C 1 -C 3 Alkyl or C 1 -C 3 A haloalkyl group;
each u and v is independently 0, 1 or 2, provided that the sum of u and v is 0, 1 or 2;
E 2 is G-Z, wherein Z is attached to L;
g is optionally selected from R by up to 3 13 Phenyl substituted with the substituent of (1); or
G is a 5-to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, each ring optionally substituted with up to 3 heteroatoms independently selected from R 13 Substituted with the substituent(s); or
G is a 3-to 7-membered non-aromatic ring or an 8-to 11-membered bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and optionally up to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, wherein up to 2 ring members are independently selected from C (= O), C (= S), S (= O), and S (= O) 2 Each ring or ring system is optionally substituted with up to 3 substituents independently selected from R 13 Substituted with the substituent(s);
each R 13 Independently cyano, halogen, hydroxy, nitro, -SH, SF 5 、CH(＝O)、C(＝O)OH、NR 14a R 14b 、C(＝O)NR 14a R 14b 、C(＝O)C(＝O)NR 14a R 14b 、C(＝S)NR 14a R 14b 、C(R 15 )＝NR 16 、N＝CR 17 NR 18a R 18b or-U-V-Q; or C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 3 -C 7 Cycloalkyl radical, C 3 -C 7 Cycloalkenyl radical, C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, C 3 -C 7 Cycloalkoxy, C 1 -C 6 Alkylthio radical, C 1 -C 6 Alkylsulfinyl radical, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylaminosulphinyl radical, C 2 -C 6 Dialkylaminosulfinyl radical, C 1 -C 6 Alkylsulfonyloxy, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkylcarbonyl group, C 4 -C 7 Cycloalkyl carbonyl, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl, C 4 -C 7 Cycloalkoxycarbonyl radical, C 3 -C 6 Alkoxycarbonyl carbonyl, C 2 -C 6 Alkylcarbonyloxy, C 4 -C 7 Cycloalkyl carbonyloxy, C 2 -C 6 Alkoxycarbonyloxy, C 4 -C 7 Cycloalkoxycarbonyloxy, C 2 -C 6 Alkyl amino carbonyl oxygen radical, C 4 -C 7 Cycloalkyl aminocarbonyloxy, C 2 -C 6 Alkylcarbonylamino, C 4 -C 7 Cycloalkyl carbonylamino group, C 2 -C 6 Alkoxycarbonylamino group, C 4 -C 7 Cycloalkoxy-carbonylamino group, C 2 -C 6 Alkylamino carbonylamino group, C 4 -C 7 Cycloalkylaminocarbonylamino or C 2 -C 6 A dialkoxyphosphinyl group, each of which is optionally substituted by up to 3 radicals independently selected from R 19 Substituted with a substituent of (1);
each R 14a Independently of each other H, cyano, hydroxy, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Halogenated alkenyl group, C 2 -C 4 Alkynyl, C 2 -C 4 Halogenated alkynyl, C 1 -C 5 Alkoxy radical, C 2 -C 4 Alkoxyalkyl group, C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Haloalkylsulfonyl, C 2 -C 4 Alkylthioalkyl, C 2 -C 4 Alkylsulfinylalkyl radical, C 2 -C 4 Alkylsulfonylalkyl group, C 2 -C 4 Alkyl carbonyl, C 2 -C 4 Halogenoalkylcarbonyl group, C 4 -C 7 Cycloalkyl carbonyl group, C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkoxycarbonylalkyl, C 2 -C 5 Alkylaminocarbonyl or C 3 -C 5 A dialkylaminocarbonyl group;
each R 14b Independently of each other H, C 1 -C 6 Alkyl radical, C 1 -C 6 Haloalkyl, C 2 -C 6 Alkenyl radical, C 2 -C 6 Halogenated alkenyl group, C 2 -C 6 Alkynyl, C 2 -C 6 Halogenated alkynyl, C 1 -C 6 Hydroxyalkyl, C 2 -C 6 Cyanoalkyl, C 3 -C 8 Cycloalkyl radical, C 3 -C 8 Halocycloalkyl radical, C 3 -C 8 Cycloalkenyl radical, C 3 -C 8 Halogenated cycloalkenyl radical, C 4 -C 10 Alkyl cycloalkyl, C 4 -C 10 Cycloalkylalkyl radical, C 4 -C 10 Halocycloalkylalkyl radical, C 6 -C 14 Cycloalkyl, C 5 -C 10 Alkyl cycloalkyl alkyl, C 2 -C 6 Alkoxyalkyl group, C 2 -C 6 Haloalkoxyalkyl, C 4 -C 10 Cycloalkoxyalkyl, C 3 -C 8 Alkoxyalkoxyalkyl group, C 2 -C 6 Alkylthio alkyl, C 2 -C 6 Alkylsulfinylalkyl, C 2 -C 6 Alkylsulfonylalkyl, C 2 -C 6 Alkylaminoalkyl, C 2 -C 6 Haloalkyl aminoalkyl, C 3 -C 8 Dialkylaminoalkyl radicalOr C 4 -C 10 Cycloalkylaminoalkyl radicals, each of which is optionally substituted by up to 1 radical selected from the group consisting of cyano, hydroxy, nitro, C 2 -C 4 Alkyl carbonyl, C 2 -C 4 Alkoxycarbonyl group, C 3 -C 15 Trialkylsilyl group, C 3 -C 15 Halo-trialkylsilyl and pyrimidinyl substituents; or alternatively
R 14a And R 14b Together form a 4-to 6-membered fully saturated heterocyclic ring containing, in addition to the linking nitrogen atom, ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, each ring optionally substituted with up to 3 heteroatoms independently selected from halogen and C 1 -C 3 Alkyl substituent;
each R 15 Independently H, cyano, halogen, methyl, methoxy, methylthio, or methoxycarbonyl;
each R 16 Independently of the other is hydroxy or NR 20a R 20b (ii) a Or C 1 -C 4 Alkoxy radical, C 2 -C 4 Alkenyloxy radical, C 2 -C 4 Alkynyloxy, C 2 -C 4 Alkylcarbonyloxy, C 2 -C 5 Alkoxycarbonyloxy, C 2 -C 5 Alkylamino carbonyloxy or C 3 -C 5 A dialkylaminocarbonyloxy group, each of which is optionally substituted with up to 1 substituent selected from cyano, halogen, hydroxy, and C (= O) OH;
each R 17 Independently H, methyl, methoxy or methylthio;
each R 18a And R 18b Independently is H or C 1 -C 4 An alkyl group; or
R 18a And R 18b Together form a 5-to 6-membered fully saturated heterocyclic ring, each ring containing, in addition to the linking nitrogen atom, ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, each ring optionally substituted with up to 2 methyl groups;
each R 19 Independently is amino, cyano, halogen, hydroxy, nitro, -SH, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Halocycloalkyl radical, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 2 -C 4 Alkoxyalkoxy radical, C 1 -C 4 Alkylthio radical, C 1 -C 4 Alkylsulfinyl radical, C 1 -C 4 Alkylsulfonyl radical, C 1 -C 4 Haloalkylsulfonyl group, C 2 -C 4 Alkyl carbonyl, C 2 -C 4 Halogenoalkylcarbonyl group, C 2 -C 5 Alkoxycarbonyl group, C 1 -C 6 Alkylamino radical, C 2 -C 6 Dialkylamino radical, C 2 -C 5 Alkylaminocarbonyl radical, C 3 -C 5 Dialkylaminocarbonyl group, C 3 -C 5 Alkylthio alkylcarbonyl, C 3 -C 15 Trialkylsilyl group, C 3 -C 15 Halogenotrialkylsilyl, C (R) 21 )＝NOR 22 Or C (R) 23 )＝NR 24 ；
Each U is independently a direct bond, C (= O) O, C (= O) N (R) 25 ) Or C (= S) N (R) 26 ) Wherein the atom to the left is connected to G and the atom to the right is connected to V;
each V is independently a direct bond; or C 1 -C 6 Alkylene radical, C 2 -C 6 Alkenylene radical, C 3 -C 6 Alkynylene radical, C 3 -C 6 Cycloalkylene or C 3 -C 6 Cycloalkenylene, wherein up to 1 carbon atom is C (= O), each of which is optionally selected from up to 3 independently selected from halogen, cyano, nitro, hydroxy, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy and C 1 -C 2 Substituted with a halo alkoxy group;
each Q is independently phenyl or phenoxy, each optionally substituted with up to 2 substituents independently selected from R 27 By substitution ofSubstituted by radicals; or
Each Q is independently a 5-to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, each ring optionally substituted with up to 2 heteroatoms independently selected from R 27 Substituted with a substituent of (1); or
Each Q is independently a 3-to 7-membered non-aromatic heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, wherein up to 2 ring members are independently selected from C (= O), C (= S), S (= O), and S (= O) 2 Each ring is optionally substituted with up to 2 substituents independently selected from R 27 Substituted with the substituent(s);
each R 20a Independently of each other H, C 1 -C 4 Alkyl or C 2 -C 4 An alkylcarbonyl group;
each R 20b Independently of one another H, cyano, C 1 -C 5 Alkyl radical, C 2 -C 5 Alkyl carbonyl, C 2 -C 5 Halogenoalkylcarbonyl group, C 4 -C 7 Cycloalkyl carbonyl group, C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkoxycarbonylalkyl, C 2 -C 5 Alkylaminocarbonyl or C 3 -C 5 A dialkylaminocarbonyl group; or
R 20a And R 20b Together form a 5-to 6-membered fully saturated heterocyclic ring, each ring containing, in addition to the linking nitrogen atom, ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, each ring optionally substituted with up to 2 methyl groups;
each R 21 And R 23 Independently of one another H, cyano, halogen, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 3 -C 6 Cycloalkyl or C 1 -C 3 An alkoxy group; or optionally up to 2 independently selected from halogen and C 1 -C 3 Taking of alkyl groupsPhenyl substituted by substituents;
each R 22 Independently of each other H, C 1 -C 5 Alkyl radical, C 1 -C 5 Haloalkyl, C 2 -C 5 Alkenyl radical, C 2 -C 5 Haloalkenyl, C 2 -C 5 Alkynyl, C 3 -C 6 Cycloalkyl radical, C 3 -C 6 Halogenocycloalkyl, C 2 -C 5 Alkylcarbonyl or C 2 -C 5 An alkoxycarbonyl group; or
Each R 22 Is optionally selected from up to 2 independently selected from halogen and C 1 -C 3 Phenyl substituted with a substituent of alkyl; or a 5-to 6-membered fully saturated heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 2N atoms, each ring optionally substituted with up to 2 heteroatoms independently selected from halogen and C 1 -C 3 Alkyl substituent substitution;
each R 24 Independently of one another H, cyano, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, C 1 -C 4 Alkoxy radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 An alkoxycarbonyl group;
each R 25 And R 26 Independently of each other H, cyano, hydroxy, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkylcarbonyl group, C 2 -C 4 Halogenoalkylcarbonyl group, C 2 -C 4 Alkoxycarbonyl or C 2 -C 4 A haloalkoxycarbonyl group;
each R 27 Independently halogen, cyano, hydroxy, nitro, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 1 -C 4 Alkoxy radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 An alkoxycarbonyl group;
z is a direct bond, O, S (= O) m 、N(R 28 )、C(＝O)、C(＝O)O、C(＝O)N(R 28 )、NR 28 C(＝O)、N(R 28 )C(＝O)N(R 28 )、N(R 28 )C(＝S)N(R 28 )、OC(＝O)N(R 28 )、N(R 28 )C(＝O)O、S(O) 2 N(R 28 )、N(R 28 )S(＝O) 2 Or N (R) 28 )S(O) 2 N(R 28 ) Wherein the right atom is attached to L;
each R 28 Independently of each other H, C 1 -C 3 Alkyl radical, C 1 -C 3 Alkoxy radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 An alkoxycarbonyl group; and is
m is 0, 1 or 2; and
(b) At least one additional fungicidal compound;
the premise is that:
(c) When A is 1 Is N (R) 7a ) When, O or S, then A 2 Is a direct bond or CR 6e R 6f (ii) a And is
When A is 2 Is N (R) 7b ) O or S; then A is 1 Is CR 6c R 6d 。
2. The composition of claim 1, wherein component (a) comprises a compound having formula 1 or a salt thereof, wherein
R 1 Is CF 3 、CCl 3 Or CF 2 Cl；
W is O;
R 5a and R 5b Each independently is H, hydroxy or methyl;
R 2a and R 2b Each independently is H or methyl; or
R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-to 6-membered saturated ring containing, in addition to these atoms X and Y, a ring member selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C (= O), the ring being optionally substituted on a carbon atom ring member with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy;
R 2c is C 1 -C 2 Alkyl radical, C 2 -C 3 Alkenyl or C 2 -C 3 An alkynyl group;
R 2d is H or methyl;
A 1 is CR 6c R 6d Or O;
A 2 is a direct bond, CR 6e R 6f Or O;
R 6a 、R 6b 、R 6c 、R 6d 、R 6e and R 6f Each independently is H, cyano, hydroxy, br, cl, F or methyl;
J is J-1, J-6 or J-14;
each R 8 Independently F, cl or methyl;
each R 9a And R 9b Independently H, halogen or methyl;
n is 0, 1 or 2;
E 1 is C 1 -C 6 Alkoxy radical, C 1 -C 6 Alkylsulfonyl radical, C 2 -C 6 Alkylcarbonyl or C 2 -C 6 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1R 10a And up to 3 substituents independently selected from R 10b Substituted with the substituent(s);
R 10a is optionally selected from R by up to 2 11a Phenyl substituted with the substituent of (1); or a 5-to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2O atoms, up to 2S atoms, and up to 4N atoms, each ring optionally substituted with up to 2 substituents independently selected from R on the carbon atom ring members 11a And independently selected from R on a nitrogen ring member 11b ；
Each R 10b Independently of one another is halogen, hydroxy, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 1 -C 4 Alkoxy radical, C 1 -C 4 Haloalkoxy, C 1 -C 4 Alkylsulfonyl radical, C 2 -C 4 Alkylcarbonyl or C 2 -C 5 An alkoxycarbonyl group;
each R 11a Independently of one another is halogen, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy or C 2 -C 3 An alkoxycarbonyl group;
each R 11b Independently is methyl, methoxy, methylcarbonyl or methoxycarbonyl;
G is selected from the group consisting of:
Figure FDA0003913878890000101
Figure FDA0003913878890000111
Figure FDA0003913878890000121
Figure FDA0003913878890000131
Figure FDA0003913878890000141
Figure FDA0003913878890000151
wherein the floating bond is attached to Z in formula 1 through any available carbon or nitrogen atom of the depicted ring or ring system; and x is 0, 1, 2 or 3;
each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 1 -C 6 Alkyl radical, C 2 -C 6 Alkenyl radical, C 2 -C 6 Alkynyl, C 1 -C 6 Alkoxy radical, C 2 -C 6 Alkenyloxy radical, C 2 -C 6 Alkynyloxy, C 1 -C 6 Alkylsulfonyl radical, C 1 -C 6 Alkylsulfonyloxy, C 1 -C 6 Alkylsulfonylamino group, C 2 -C 6 Alkylcarbonyl group, C 2 -C 6 Alkoxycarbonyl group, C 3 -C 6 Alkenyloxycarbonyl radical, C 3 -C 6 Alkynyloxycarbonyl group, C 4 -C 6 Cycloalkoxycarbonyl radical or C 2 -C 6 Alkoxycarbonyloxy, each of which is optionally substituted with up to 3 independently selected from R 19 Substituted with the substituent(s);
each R 14a Independently of each other H, C 1 -C 2 Alkyl radical, C 2 -C 4 Alkenyl radical, C 2 -C 4 Alkynyl, C 2 -C 4 Alkylcarbonyl or C 2 -C 4 An alkoxycarbonyl group;
each R 14b Independently of each other H, C 1 -C 4 Alkyl radical, C 1 -C 4 Haloalkyl, C 2 -C 4 Alkenyl radical, C 2 -C 4 Halogenated alkenyl group, C 2 -C 4 Alkynyl, C 3 -C 5 Cycloalkyl, C 4 -C 6 Cycloalkylalkyl radical, C 2 -C 4 Alkoxyalkyl group, C 2 -C 4 Haloalkoxyalkyl, C 2 -C 4 Alkylaminoalkyl or C 3 -C 5 A dialkylaminoalkyl group; or
R 14a And R 14b Together form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl, or thiomorpholinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl;
Each R 19 Independently of one another is cyano, halogen, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 3 -C 6 Cycloalkyl, C 1 -C 2 Alkoxy radical, C 1 -C 2 Haloalkoxy, C 2 -C 3 Alkylcarbonyl group, C 2 -C 3 Halogenoalkylcarbonyl or C 2 -C 3 An alkoxycarbonyl group;
each U is independently a direct bond, C (= O) O, or C (= O) N (R) 25 )；
Each V is independently a direct bond; or C 1 -C 3 Alkylene each optionally substituted by up to 2 independently selected from halogen, hydroxy, C 1 -C 2 Alkyl radical, C 1 -C 2 Alkoxy and C 1 -C 2 Substituted with a halo alkoxy group;
each Q is independently optionally selected from R by up to 2 27 Phenyl substituted with the substituent of (1); or pyridyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl or oxazolyl, each of which is optionally up to 2 independently selected from R 27 Substituted with the substituent(s);
each R 25 Independently is H, cyano, hydroxy or C 1 -C 2 An alkyl group;
each R 27 Independently of one another is halogen, cyano, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl or C 1 -C 2 An alkoxy group; and is
Z is a direct bond, O, NH, C (= O) NH, NHC (= O) NH, OC (= O) NH, NHC (= O) O, S (= O) 2 NH、NHS(＝O) 2 Or NHS (= O) 2 NH。
3. The composition of claim 2, wherein component (a) comprises a compound having formula 1 or a salt thereof, wherein
T is T-2 or T-3;
R 1 Is CF 3 ；
X is O;
y is O;
R 2a and R 2b Each independently is H or methyl; or
R 2a And R 2b Form a 5-membered saturated ring together with the atoms X and Y to which they are attached, except for these atoms XAnd Y, the ring containing a ring member selected from carbon atoms, the ring being optionally substituted on the carbon atom ring member with up to 1 substituent selected from halogen, methyl and halomethyl;
R 2c is methyl or ethyl;
R 2d is H;
A 1 is O;
A 2 is a direct bond or CH 2 ；
R 6a And R 6b Each independently is H, cyanohydroxy or methyl;
j is J-1 or J-6;
q is 0 or 1;
each R 9a And R 9b Independently is H or methyl;
E 1 is C 1 -C 3 Alkoxy radical, C 2 -C 3 Alkylcarbonyl or C 2 -C 3 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1R 10a And up to 3 substituents independently selected from R 10b Substituted with a substituent of (1);
R 10a is pyrazolyl, imidazolyl or triazolyl, each of which is optionally selected up to 2 independently from R on a carbon atom ring member 11a Substituted with the substituent(s);
each R 10b Independently of one another is halogen, C 1 -C 2 Alkyl radical, C 1 -C 2 Haloalkyl, C 1 -C 2 Alkoxy or C 2 -C 4 An alkoxycarbonyl group;
g is G-1, G-3, G-12 or G-22;
x is 1 or 2;
each R 13 Independently is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkenyloxycarbonyl radical, C 3 -C 5 Alkynyloxycarbonyl or C 4 -C 6 Cycloalkoxycarbonyl groups, each of which is optionally selected by up to 3 independently from R 19 Substituted with the substituent(s);
each R 14a Independently isH or C 1 -C 2 An alkyl group;
each R 14b Independently of each other H, C 1 -C 3 Alkyl radical, C 1 -C 3 Haloalkyl, cyclopropylmethyl or C 2 -C 4 An alkoxyalkyl group;
each R 19 Independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl;
each U is independently a direct bond or C (= O) O;
each V is independently a direct bond or CH 2 ；
Each Q is independently phenyl or pyridyl, each of which is optionally substituted with up to 2 substituents independently selected from R 27 Substituted with a substituent of (1);
each R 27 Independently halogen, methyl or methoxy; and is provided with
Z is a direct bond, O, NH, C (= O) NH, or NHC (= O).
4. The composition of claim 3, wherein component (a) comprises a compound having formula 1 or a salt thereof, wherein
R 2a And R 2b Each is H; or alternatively
R 2a And R 2b Together with the atoms X and Y to which they are attached form a 5-membered saturated ring which, in addition to these atoms X and Y, contains a ring member selected from carbon atoms;
A 2 is a direct bond;
R 6a and R 6b Each is H;
R 8 is F or Cl;
l is a direct bond, CH 2 Or CH 2 CH 2 ；
E 1 Is C 1 -C 2 Alkoxy or C 2 -C 3 Alkoxycarbonyl wherein each carbon atom is optionally substituted by up to 1 atom selected from R 10a Substituted with the substituent(s);
R 10a is pyrazolyl or imidazolyl, each of which is optionally substituted by up to 2 on carbon atom ring membersIndependently selected from R 11a Substituted with the substituent(s);
each R 11a Independently is methoxycarbonyl or ethoxycarbonyl;
g is G-1 and the 2-position of G-1 is linked to Z and the 4-position is linked to R 13 (ii) a Or G is G-12 and G-12 is attached to Z at position 1 and to R at position 4 13 (ii) a Or G is G-12 and G-12 is attached at position 1 to Z and at position 3 to R 13 ；
x is 1;
R 13 is C (= O) NR 14a R 14b or-U-V-Q; or C 2 -C 5 Alkoxycarbonyl group, C 3 -C 5 Alkynyloxycarbonyl or C 4 -C 6 Cycloalkoxycarbonyl, each of which is optionally substituted by up to 1 selected from R 19 Substituted with the substituent(s);
R 14a is H;
R 14b is H, methyl or cyclopropylmethyl;
R 19 is cyano, halogen, cyclopropyl or methoxy;
u is C (= O) O;
v is CH 2 ；
Q is optionally selected from R by up to 2 27 Phenyl substituted with the substituent of (1); and is provided with
Z is a direct bond, O, NH or C (= O).
5. The composition of claim 4, wherein component (a) comprises a compound having formula 1 or a salt thereof, wherein
R 8 Is F;
l is a direct bond or CH 2 ；
E 1 Is selected from 1R 10a Methoxy substituted with the substituent of (1);
R 10a Is optionally substituted on a carbon atom ring member by up to 1R 11a Substituted pyrazolyl substituted with the substituents of (1);
g is G-12 and the 1-position of G-12 is linked to Z and the 4-position is linked to R 13 (ii) a Or G is G-12 and G-12 is attached at position 1 to Z and at position 3 to R 13 (ii) a And is
R 13 Is optionally selected from R by up to 1 19 C substituted by a substituent of 2 -C 5 An alkoxycarbonyl group;
R 19 is cyano, cl, F, cyclopropyl or methoxy; and is
Z is a direct bond.
6. The composition of claim 5, wherein component (a) comprises a compound having formula 1 or a salt thereof, wherein
J is J-1;
q is 0;
l is CH 2 ；
E is E 2 ；
G is G-12 and the 1-position of G-12 is linked to Z and the 4-position is linked to R 13 (ii) a And is
R 13 Is methoxycarbonyl or ethoxycarbonyl.
7. The composition of claim 1, wherein component (a) comprises a compound selected from the group consisting of:
1- [ [4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester;
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester;
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester;
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-3-carboxylic acid ethyl ester;
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] -3-fluorophenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester;
1- [ [3- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester;
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenoxy ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester;
n- (cyclopropylmethyl) -2- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] thiazole-4-carboxamide;
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid 2-methylpropyl ester;
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid cyclopropylmethyl ester;
1- [2- [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] ethyl ] -1H-pyrazole-4-carboxylic acid ethyl ester;
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid 2-methoxyethyl ester;
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid 2-butyn-1-yl ester;
1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid 3-cyanopropyl ester;
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid phenylmethyl ester;
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid butyl ester;
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid 3-chloropropyl ester;
4- (3, 3-trifluoro-2, 2-dihydroxypropoxy) phenyl carboxylic acid methyl ester;
1- [ [ 3-fluoro-4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester;
1- [ [4- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenylmethoxy ] methyl ] -1H-pyrazole-4-carboxylic acid ethyl ester;
1- [ [3- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid methyl ester; and
1- [ [3- [ [ (1Z) -2-ethoxy-3, 3-trifluoro-1-propen-1-yl ] oxy ] phenyl ] methyl ] -1H-pyrazole-4-carboxylic acid propyl ester.
8. The composition of any one of claims 1 to 7, wherein component (b) comprises at least one fungicidal compound selected from the group consisting of:
(b1) Benzimidazole methyl carbamate (MBC) fungicides;
(b2) A dicarboximide fungicide;
(b3) Demethylation inhibitor (DMI) fungicides;
(b4) Phenylamide (PA) fungicides;
(b5) Amine/morpholine fungicides;
(b6) A phospholipid biosynthesis inhibitor fungicide;
(b7) Succinate dehydrogenase inhibitor (SDHI) fungicide;
(b8) Hydroxy (2-amino-) pyrimidine fungicides;
(b9) An Anilinopyrimidine (AP) fungicide;
(b10) N-phenyl carbamate fungicides;
(b11) Quinone outside inhibitor (QoI) fungicides;
(b12) Phenylpyrrole (PP) fungicides;
(b13) An azanaphthalene fungicide;
(b14) Cell peroxidation inhibitor fungicides;
(b15) Melanin biosynthesis inhibitor-reductase (MBI-R) fungicides;
(b 16 a) a melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicide;
(b 16 b) polyketide synthase (MBI-P) fungicides that are inhibitors of melanin biosynthesis;
(b17) Ketoreductase inhibitor (KRI) fungicides;
(b18) A squalene epoxidase inhibitor fungicide;
(b19) Polyoxin fungicides;
(b20) Phenylurea fungicides;
(b21) Quinone Internal Inhibitor (QiI) fungicides;
(b22) Benzamide and thiazolecarboxamide fungicides;
(b23) An enol pyranouronic acid antibiotic fungicide;
(b24) A hexapyranosyl antibiotic fungicide;
(b25) Glucopyranosyl antibiotics: protein synthesis fungicides;
(b26) A glucopyranosyl antibiotic fungicide;
(b27) Cyanoacetamide oxime fungicides;
(b28) A carbamate fungicide;
(b29) Oxidative phosphorylation uncoupling fungicides;
(b30) An organotin fungicide;
(b31) A carboxylic acid fungicide;
(b32) A heteroaromatic fungicide;
(b33) Phosphonate fungicides;
(b34) Anthranilic acid fungicides;
(b35) A benzotriazine fungicide;
(b36) Benzene-sulfonamide fungicides;
(b37) A pyridazinone fungicide;
(b38) Thiophene-carboxamide fungicides;
(b39) Complex I NADH oxidoreductase inhibitor fungicide;
(b40) Carboxylic Acid Amide (CAA) fungicides;
(b41) A tetracycline antibiotic fungicide;
(b42) Thiocarbamate fungicides;
(b43) Benzamide fungicides;
(b44) A microbial fungicide;
(b45) Quinone external inhibitors, stakectin binding (QoSI) fungicides;
(b46) A plant extract fungicide;
(b47) Cyanoacrylate fungicides;
(b48) A polyene fungicide;
(b49) Oxysterol binding protein inhibitor (OSBPI) fungicide;
(b50) Aryl-phenyl-ketone fungicides;
(b51) Host plant defense inducing fungicides;
(b52) A multi-site active fungicide;
(b53) Biological agents with multiple modes of action;
(b54) A fungicide other than the fungicides of component (a) and components (b 1) to (b 53); and salts of the compounds of (b 1) to (b 54).
9. The composition of claim 8, wherein component (b) comprises at least one fungicidal compound from each of two different groups selected from (b 1) to (b 54).
10. The composition of any one of claims 1 to 7, wherein component (b) comprises at least one compound selected from the group consisting of: <xnotran> -S- , 4- -2,6- , , , , , , , -M, , , , - , , , , , , , -S, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , -M, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> <xnotran> , , , , , , , , , , , , , , , , , , , , -M, , , , , , , , , ( ), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> Uniconazole, validamycin, valinamide, vinclozolin, zineb, ziram, zoxamide, N' - [4- [ 4-chloro-3- (trifluoromethyl) phenoxy ] -2, 5-dimethylphenyl ] -N-ethyl-N-methylmercapto-amidine, 5-chloro-6- (2, 4, 6-trifluorophenyl) -7- (4-methylpiperidin-1-yl) [1,2,4] triazolo [1,5a ] pyrimidine (DPX-BAS 600F), N- [2- [4- [ [3- (4-chlorophenyl) -2-propyn-1-yl ] oxy ] -3-methoxyphenyl ] ethyl ] -3-methyl-2- [ (methylsulfonyl) amino ] butanamide, N- [2- [4- [ [3- (4-chlorophenyl) -2-propyn-1-yl ] oxy ] -3-methoxyphenyl ] ethyl ] -3-methyl-2- [ (ethylsulfonyl) amino ] butanamide, N- [1- (4-cyanophenyl) ethyl ] amino ] propyl ] amino ] phenyl ] benzoate, N- [3- (4-difluoromethoxy ] propyl ] phenyl ] amino ] phenyl ] -3- [1- (4- [ [ -difluoromethoxy ] phenyl ] acetamide Phenyl ] ethoxy ] imino ] methyl ] phenylacetamide, N' - [4- [ 4-chloro-3- (trifluoromethyl) phenoxy ] -2, 5-dimethylphenyl ] -N-ethyl-N-methylcarboxamidine, 2- [ [ [ [3- (2, 6-dichlorophenyl) -1-methyl-2-propen-1-ylidene ] amino ] oxy ] methyl ] -a- (methoxyimino) -N-methylbenzacetamide and 1- [ (2-propenylthio) carbonyl ] -2- (1-methylethyl) -4- (2-methylphenyl) -5-amino-1H-pyrazol-3-one, 5-ethyl-6-octyl- [1,2,4] triazolo [1,5-a ] pyrimidin-7-ylamine.
11. The composition of claim 10, wherein component (b) comprises at least one compound selected from the group consisting of: azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, epoxiconazole, fenpropidin, fenpropimorph, flurindazofamid, flutriafol, fluxapyroxad, mancozeb, metominostrobin, picoxystrobin, prothioconazole, fluxapyroxad, pyraclostrobin, tebuconazole and trifloxystrobin.
12. A composition, comprising: (a) At least one compound selected from the group consisting of compounds having formula 1, N-oxides and salts thereof as defined in claim 1; and at least one invertebrate pest control compound or agent.
13. A composition comprising the composition of any one of claims 1 to 12 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
14. A method for protecting a plant or plant seed from a disease caused by a fungal pathogen, the method comprising applying to the plant or plant seed a fungicidally effective amount of the composition of any one of claims 1 to 13.
15. A method for protecting a plant from rust comprising applying to the plant a fungicidally effective amount of the composition of any one of claims 1 to 13, wherein component (b) comprises at least one fungicidal compound selected from: (b11) A quinone outside inhibitor fungicide, (b 3) a demethylation inhibitor fungicide, (b 5) an amine/morpholine fungicide, (b 7) a succinate dehydrogenase inhibitor fungicide, (b 11) a quinone outside inhibitor (QoI) fungicide, (b 13) a benzimidazole methyl carbamate fungicide, and (b 52) a multi-site active fungicide.
CN202180031728.9A 2020-03-11 2021-03-11 Fungicidal halomethyl ketones and hydrates and mixtures thereof Pending CN115460921A (en)

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