RU2791978C2 - R-pyridyloxycarboxylic acid and salt, composite ester derivative, production method, herbicidal composition and their use - Google Patents

Abstract

FIELD: agriculture; chemistry.

SUBSTANCE: invention relates to R-pyridyloxycarboxylic acids represented by the formula I

,

their salts, composite ester derivatives, where salt is metal salt, amine salt, sulfonium salt, or phosphonium salt; composite ester is

,

where X is O or S; M is alkyl, alkenyl, alkynyl, and the like with or without halogen.

EFFECT: new compounds are obtained, having excellent herbicidal activity and higher safety for plants, especially good selectivity relatively to such vital cultures as rice, or where weed is cereal weed (such as Echinochloa crusgalli, Digitaria sanguinalis, Semen Euphorbiae Lathyridis) or deciduous weed (such as Monochoria Vaginalis, Abutilon theophrasti Medic., Galium aparine).

9 cl, 6 tbl

Description

The field of technology to which the invention belongs

The invention relates to the field of pesticide technology and, in particular, the type of R-pyridyloxycarboxylic acid and salt, ester derivative, production method, herbicidal composition and their use.

State of the art invention

, и их применение в качестве гербицидов, но энантиомеры соединений не упоминаются. Ученым по-прежнему необходимо проводить постоянные исследования и разрабатывать новые гербициды, имеющие высокую эффективность, безопасность, экономичность и различные принципы действия из-за таких проблем, как растущий рынок, устойчивость к сорнякам, срок годности и рентабельность пестицидов, а также в связи с растущей обеспокоенностью людей об окружающей среде.Weed control is one of the most important links in the process of achieving highly efficient agriculture. Various herbicides are available on the market, for example, DE2335349A1, GB1418979A, US 3761486 and the like describe a number of compounds represented by the general formula

, and their use as herbicides, but the enantiomers of the compounds are not mentioned. Scientists still need to conduct continuous research and develop new herbicides that are highly effective, safe, economical and have various modes of action due to issues such as a growing market, weed resistance, shelf life and profitability of pesticides, as well as in connection with the growing people's concerns about the environment.

Content of the invention

The present invention provides a type of R-pyridyloxycarboxylic acid and a salt, an ester derivative thereof, a preparation method, a herbicidal composition and their use. The compound has excellent herbicidal activity and higher plant safety, especially good selectivity for key crops such as rice.

The technical solution adopted in the present invention is as follows:

The present invention provides an R-pyridyloxycarboxylic acid represented by formula I and its salt, an ester derivative,

where each A, B is independently a halogen; or alkyl or cycloalkyl with or without halogen;

C represents hydrogen, halogen, alkyl or haloalkyl;

Q is halogen, cyano, cyanoalkyl, hydroxyalkyl, amino, nitro, formyl; alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylaminoalkyl or alkoxyalkyl with or without halogen; or unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl;

Y is nitro or NR ₁ R ₂ where R ₁ is H; alkyl, alkenyl or alkynyl optionally substituted with 1-2 R ₁₁ ; -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N=CR ₁₇ R ₁₈ , alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl or dialkylphosphono; R ₂ is H; alkyl optionally substituted with 1-2 R ₁₁ ; or -COR ₁₂ ; or NR ₁ R ₂ is N=CR ₂₁ NR ₂₂ R ₂₃ , N=CR ₂₄ OR ₂₅ ; or a 5- or 6-membered saturated or unsaturated ring with or without an oxygen atom, a sulfur atom, or another nitrogen atom that is unsubstituted or substituted with 1-2 groups independently selected from the group consisting of halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl;

where R ₁₁ independently represents halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl; or unsubstituted or substituted aryl, heteroaryl;

R ₁₂ is H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;

R ₁₃ is H, alkyl, haloalkyl, phenyl, benzyl or CHR ₃₁ C(O)OR ₃₂ ; R ₃₁ is H, alkyl or alkoxy; R ₃₂ is H, alkyl or benzyl;

R ₁₄ is alkyl or haloalkyl;

R ₁₅ is H, alkyl, formyl, alkylacyl, haloalkylacyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R ₁₆ is H or alkyl;

;R ₁₇ is H, alkyl; or phenyl which is unsubstituted or substituted with 1-3 groups selected from the group consisting of halo, alkyl, alkoxy, R ₁₈ is H or alkyl; or N=CR ₁₇ R ₁₈ is

;

each R ₂₁ , R ₂₄ independently represents H or alkyl;

each R ₂₂ , R ₂₃ independently represents H or alkyl; or NR ₂₂ R ₂₃ is a 5- or 6-membered saturated or unsaturated ring with or without an oxygen atom, a sulfur atom, or another nitrogen atom;

R ₂₅ is alkyl;

the salt is a metal salt, an amine salt, a sulfonium salt, or a phosphonium salt;

где X представляет собой O или S;ester is

where X is O or S;

с галогеном или без него; или незамещенный или замещенный гетероциклил, арил, гетероарил;M is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, -alkyl-Z,

with or without halogen; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

циано, нитро, или незамещенный или замещенный гетероциклил, арил, гетероарил;Z represents

cyano, nitro, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

each R ₃ is independently alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, heteroarylalkyl;

each R ₄ , R ₅ , R ₆ is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxycarbonyl, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, heteroarylalkyl.

Preferably each A, B is independently halogen; or C1-C8 alkyl or C3-C8 cycloalkyl with or without halogen;

C is hydrogen, halo, C1-C8 alkyl or halo C1-C8 alkyl;

Q is halo, cyano, cyano C1-C8 alkyl, hydroxy C1-C8 alkyl, amino, nitro, formyl; C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylcarbonyl, C1-C8 alkoxycarbonyl, C1-C8 alkylamino C1-C8 alkyl or C1 -C8 alkoxy C1-C8 alkyl with or without halogen; or unsubstituted or substituted aryl, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl;

который не замещен или замещен 1-2 группами, независимо выбранными из группы, состоящей из галогена, C1-C8 алкила, C1-C8 алкокси, галогена C1-C8 алкокси, C1-C8 алкилтио, галогена C1-C8 алкилтио, амино, C1-C8 алкиламино, ди-C1-C8 алкиламино, C1-C8 алкоксикарбонила;Y is nitro or NR ₁ R ₂ where R ₁ is H; C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl optionally substituted with 1-2 R ₁₁ ; -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N=CR ₁₇ R ₁₈ , C1-C8 alkylcarbamoyl, di-C1-C8 alkylcarbamoyl, tri-C1-C8 alkylsilyl, or di-C1-C8 alkylphosphono; R ₂ is H; C1-C8 alkyl optionally substituted with 1-2 R ₁₁ ; or -COR ₁₂ ; or NR ₁ R ₂ is N=CR ₂₁ NR ₂₂ R ₂₃ , N=CR ₂₄ OR ₂₅ ; or

which is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halo, C1-C8 alkyl, C1-C8 alkoxy, halo C1-C8 alkoxy, C1-C8 alkylthio, halo C1-C8 alkylthio, amino, C1- C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl;

который является незамещенным или замещенным 1-3 группами, выбранными из группы, состоящей из галогена, C1-C8 алкила, галогена C1-C8 алкила, C1-C8 алкокси, нитро;where R ₁₁ is independently halo, hydroxy, C1-C8 alkoxy, halo C1-C8 alkoxy, C1-C8 alkylthio, halo C1-C8 alkylthio, amino, C1-C8 alkylamino, di-C1-C8 alkylamino, C1-C8 alkoxycarbonyl ; or phenyl, naphthyl,

which is unsubstituted or substituted with 1-3 groups selected from the group consisting of halo, C1-C8 alkyl, halo C1-C8 alkyl, C1-C8 alkoxy, nitro;

R ₁₂ is H, C1-C18 alkyl, halo C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;

R ₁₃ is H, C1-C8 alkyl, halo C1-C8 alkyl, phenyl, benzyl or CHR ₃₁ C(O)OR ₃₂ ; R ₃₁ is H, C1-C8 alkyl or C1-C8 alkoxy; R ₃₂ is H, C1-C8 alkyl or benzyl;

R ₁₄ is C1-C8 alkyl or halo C1-C8 alkyl;

R ₁₅ is H, C1-C8 alkyl, formyl, C1-C8 alkylacyl, halo C1-C8 alkylacyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R ₁₆ is H or C1-C8 alkyl;

R ₁₇ is H, C1-C8 alkyl; or phenyl which is unsubstituted or substituted with 1-3 groups selected from the group consisting of halo, C1-C8 alkyl, C1-C8 alkoxy; R ₁₈ is H or C1-C8 alkyl; or N=CR ₁₇ R ₁₈ is

each R ₂₁ , R ₂₄ is independently H or C1-C8 alkyl;

или

each R ₂₂ , R ₂₃ is independently H or C1-C8 alkyl; or NR ₂₂ R ₂₃ is

or

R ₂₅ is C1-C8 alkyl;

salt is a metal salt, ammonium salt NH₄ ⁺, salt of primary amine RNH₂, secondary amine salt (R)₂NH, tertiary amine salt (R)₃N, quaternary amine salt (R)₄N⁺, morpholine salt, piperidine salt, pyridine salt, aminopropylmorpholine salt, jeffamine D-230 salt, 2,4,6-tri(dimethylaminomethyl)phenol sodium hydroxide salt, alkylsulfonium salt, alkylsulfoxonium salt, alkylphosphonium salt, or alkanolphosphonium salt;

where each R is independently unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl or phenyl, and the above groups are optionally substituted with one or more of the following groups: halogen, hydroxy, alkoxy, alkylthio, hydroxyalkoxy, amino, alkylamino, aminoalkylamino, phenyl;

in formula I-1 X is O or S;

с галогеном или без него, или незамещенный или замещенный гетероциклил, арил, гетероарил;M is C1-C18 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, -(C1-C8 alkyl)-Z,

with or without halogen, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

циано, нитро, или незамещенный или замещенный гетероциклил, арил, гетероарил;Z represents

cyano, nitro, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

each R ₃ is independently C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl C1-C8 alkyl, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclyl C1-C8 alkyl , aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl;

each R ₄ , R ₅ , R ₆ is independently hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl, C1-C8 alkyl, C1-C8 alkoxycarbonyl, or unsubstituted or substituted heterocyclyl C1-C8 alkyl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl;

the term "heterocyclyl" refers to

который необязательно замещен, по меньшей мере, одной группой, выбранной из группы, состоящей из галогена, нитро, циано, тиоциано, гидрокси, карбокси, меркапто, формила; фенила, бензила, бензилокси, фенокси, который является незамещенным или замещенным по меньшей мере одной группой из группы, состоящей из галогена, алкила, алкокси, алкила, алкенила, алкинила, циклоалкила, циклоалкилалкила, OR”, SR”, -алкил-OR”, -алкил-SR”, COR”, COOR”, COSR”, SOR”, SO₂R”, OCOR”, SCOR” с галогеном или без него; и амино или аминокарбонила, замещенного одной или двумя группами, выбранными из группы, состоящей из водорода, алкила, алкенила, алкинила, циклоалкила, циклоалкилалкила, фенила, бензила, бензилокси, фенокси, COR”, COOR”, SO₂R”, OR”;with 0, 1 or 2 oxo groups; the term "aryl" refers to phenyl or naphthyl; the term "heteroaryl" refers to an aromatic ring group containing 3-6 ring atoms, and optionally fused through a benzene ring, 1-4 heteroatoms in the ring atoms are selected from oxygen, nitrogen and sulfur, e.g.,

which is optionally substituted with at least one group selected from the group consisting of halo, nitro, cyano, thiocyano, hydroxy, carboxy, mercapto, formyl; phenyl, benzyl, benzyloxy, phenoxy which is unsubstituted or substituted by at least one group from the group consisting of halogen, alkyl, alkoxy, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, OR”, SR”, -alkyl-OR” , -alkyl-SR”, COR”, COOR”, COSR”, SOR”, SO ₂ R”, OCOR”, SCOR” with or without halogen; and amino or aminocarbonyl substituted with one or two groups selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, benzyl, benzyloxy, phenoxy, COR”, COOR”, SO ₂ R”, OR” ;

each R' is independently hydrogen, nitro, hydroxy, amino; или алкил, алкенил, алкинил, циклоалкил, циклоалкенил, циклоалкилалкил, алкокси, алкенилокси, алкинилокси, циклоалкилокси, алкоксиалкил, алкоксикарбонил, алкилтиокарбонил, алкилсульфонил, алкилсульфонилалкил, алкилкарбонил, алкилкарбонилалкил, алкилацилокси, алкиламино, алкиламинокарбонил, алкоксиаминокарбонил, алкоксикарбонилалкил, алкиламинокарбонилалкил, триалкилсилил, диалкилфосфоно with or without halogen;

each R" is independently hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl.

More preferably, each A, B is independently halogen; or C1-C6 alkyl or C3-C6 cycloalkyl with or without halogen;

C is hydrogen, halo, C1-C6 alkyl or halo C1-C6 alkyl;

Q is halo, cyano, cyano C1-C6 alkyl, hydroxy C1-C6 alkyl, amino, nitro, formyl; C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylamino C1-C6 alkyl or C1 -C6 alkoxy C1-C6 alkyl with or without halogen; or unsubstituted or substituted aryl, heteroaryl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl;

который не замещен или замещен 1-2 группами, независимо выбранными из группы, состоящей из галогена, C1-C6 алкила, C1-C6 алкокси, галоген C1-C6 алкокси, C1-C6 алкилтио, галоген C1-C6 алкилтио, амино, C1-C6 алкиламино, ди-C1-C6 алкиламино, C1-C6 алкоксикарбонила;Y is nitro or NR ₁ R ₂ where R ₁ is H; C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl optionally substituted with 1-2 R ₁₁ ; -COR ₁₂ , nitro, OR ₁₃ , SO ₂ R ₁₄ , NR ₁₅ R ₁₆ , N=CR ₁₇ R ₁₈ , C1-C6 alkylcarbamoyl, di-C1-C6 alkylcarbamoyl, tri-C1-C6 alkylsilyl, or di-C1-C6 alkylphosphono; R ₂ is H; C1-C6 alkyl optionally substituted with 1-2 R ₁₁ ; or -COR ₁₂ ; or NR ₁ R ₂ is N=CR ₂₁ NR ₂₂ R ₂₃ , N=CR ₂₄ OR ₂₅ ; or

which is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halo, C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1- C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl;

который является незамещенным или замещенным 1-3 группами, выбранными из группы, состоящей из галогена, C1-C6 алкила, галоген C1-C6 алкила, C1-C6 алкокси, нитро;where R ₁₁ is independently halo, hydroxy, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkylamino, di-C1-C6 alkylamino, C1-C6 alkoxycarbonyl ; or phenyl, naphthyl,

which is unsubstituted or substituted with 1-3 groups selected from the group consisting of halo, C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy, nitro;

R ₁₂ is H, C1-C14 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;

R ₁₃ is H, C1-C6 alkyl, halo C1-C6 alkyl, phenyl, benzyl or CHR ₃₁ C(O)OR ₃₂ ; R ₃₁ is H, C1-C6 alkyl or C1-C6 alkoxy; R ₃₂ is H, C1-C6 alkyl or benzyl;

R ₁₄ is C1-C6 alkyl or halo C1-C6 alkyl;

R ₁₅ is H, C1-C6 alkyl, formyl, C1-C6 alkylacyl, halo C1-C6 alkylacyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R ₁₆ is H or C1-C6 alkyl;

R ₁₇ is H, C1-C6 alkyl; or phenyl which is unsubstituted or substituted with 1-3 groups selected from the group consisting of halo, C1-C6 alkyl, C1-C6 alkoxy; R ₁₈ is H or C1-C6 alkyl; or N=CR ₁₇ R ₁₈ is

each R ₂₁ , R ₂₄ is independently H or C1-C6 alkyl;

или

each R ₂₂ , R ₂₃ is independently H or C1-C6 alkyl; or NR ₂₂ R ₂₃ is

or

R ₂₅ is C1-C6 alkyl;

salt is a metal salt, ammonium salt NH₄ ⁺, salt of primary amine RNH₂, secondary amine salt (R)₂NH, tertiary amine salt (R)₃N, quaternary amine salt (R)₄N⁺, morpholine salt, piperidine salt, pyridine salt, aminopropylmorpholine salt, jeffamine D-230 salt, 2,4,6-tri(dimethylaminomethyl)phenol sodium hydroxide salt, C1-C18 alkylsulfonium salt, C1-C18 alkylsulfoxonium salt, C1- C18 alkylphosphonium or C1-C18 alkanolphosphonium salt;

where each R is independently unsubstituted C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C3-C18 cycloalkyl, or phenyl, and the above groups are optionally substituted with one or more of the following groups: halogen, hydroxy, C1-C8 alkoxy , C1-C8 alkylthio, hydroxy C1-C8 alkoxy, amino, C1-C8 alkylamino, amino C1-C8 alkylamino, phenyl;

in formula I-1 X is O or S;

с галогеном или без него, или незамещенный или замещенный гетероциклил, арил, гетероарил;M is C1-C18 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, -(C1-C6 alkyl)-Z,

with or without halogen, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

циано, нитро, или незамещенный или замещенный гетероциклил, арил, гетероарил;Z represents

cyano, nitro, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

each R ₃ is independently C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclyl C1-C6 alkyl , aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl;

each R ₄ , R ₅ , R ₆ is independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxycarbonyl, or unsubstituted or substituted heterocyclyl C1-C6 alkyl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl;

с 0, 1 или 2 оксогруппами; термин «арил» относится к фенилу или нафтилу; термин «гетероарил» относится к

который замещен 0, 1, 2 или 3 группами, выбранными из группы, состоящей из галогена, нитро, циано, тиоциано, гидрокси, карбокси, меркапто, формила; фенила, бензила, бензилокси, фенокси, который является незамещенным или замещенным по меньшей мере одной группой из группы, состоящей из галогена, C1-C6 алкила, C1-C6 алкокси; C1-C6 алкилу, C2-C6 алкенилу, C2-C6 алкинилу, C3-C6 циклоалкилу, C3-C6 циклоалкилу C1-C6 алкилу, OR”, SR”, -(C1-C6)алкил-OR”, -(C1-C6)алкил-SR”, COR”, COOR”, COSR”, SOR”, SO₂R”, OCOR”, SCOR” с галогеном или без него; и амино или аминокарбонилу, замещенному одной или двумя группами, выбранными из группы, состоящей из водорода, C1-C6 алкила, C2-C6 алкенила, C2-C6 алкинила, C3-C6 циклоалкила, C3-C6 циклоалкила C1-C6 алкила, фенила, бензила, бензилокси, фенокси, COR”, COOR”, SO₂R”, OR”;the term "heterocyclyl" refers to

with 0, 1 or 2 oxo groups; the term "aryl" refers to phenyl or naphthyl; the term "heteroaryl" refers to

which is substituted with 0, 1, 2 or 3 groups selected from the group consisting of halo, nitro, cyano, thiocyano, hydroxy, carboxy, mercapto, formyl; phenyl, benzyl, benzyloxy, phenoxy which is unsubstituted or substituted with at least one group from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy; C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, OR”, SR”, -(C1-C6)alkyl-OR”, -(C1- C6)alkyl-SR”, COR”, COOR”, COSR”, SOR”, SO ₂ R”, OCOR”, SCOR” with or without halogen; and amino or aminocarbonyl substituted with one or two groups selected from the group consisting of hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C6 alkyl, phenyl, benzyl, benzyloxy, phenoxy, COR”, COOR”, SO ₂ R”, OR”;

each R' is independently hydrogen, nitro, hydroxy, amino; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, C3-C6 cycloalkyl C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C6 cycloalkyloxy, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonyl C1-C6 alkyl, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyl C1-C6 alkyl, C1-C6 alkylacyloxy, C1-C6 alkylamino, C1-C6 alkylaminocarbonyl, C1-C6 alkoxyaminocarbonyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, C1-C6 alkylaminocarbonyl C1-C6 alkyl, tri-C1-C6 alkylsilyl, di-C1 -C6 alkylphosphono with or without fluorine, chlorine or bromine;

each R" is independently hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl or C3-C6 cycloalkyl C1-C6 alkyl.

Further preferably, each A, B is independently halo, C1-C6 alkyl, halo C1-C6 alkyl, or C3-C6 cycloalkyl;

C is hydrogen, halo, C1-C6 alkyl or halo C1-C6 alkyl;

который является незамещенным или замещенным C1-C6 алкилом; или фенил, который является незамещенным или замещенным по меньшей мере одной группой, выбранной из группы, состоящей из C1-C6 алкила, галоген C1-C6 алкила, галогена и C1-C6 алкокси;Q is C1-C6 alkyl, halo C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, cyano, amino, nitro, formyl, C1-C6 alkoxy, C1-C6 alkylthio, C1 -C6 alkoxycarbonyl, hydroxy C1-C6 alkyl, C1-C6 alkoxy C1-C2 alkyl, cyano C1-C2 alkyl, C1-C6 alkylamino C1-C2 alkyl, benzyl, naphthyl, furyl, thienyl, thiazolyl, pyridyl, pyrimidinyl;

which is unsubstituted or substituted C1-C6 alkyl; or phenyl which is unsubstituted or substituted with at least one group selected from the group consisting of C1-C6 alkyl, halo C1-C6 alkyl, halo and C1-C6 alkoxy;

Y is amino, C1-C6 alkylamino, C1-C6 alkylcarbonylamino, phenylcarbonylamino, benzylamino; or furylmethyleneamino which is unsubstituted or substituted halo C1-C6 alkyl;

salt is a metal salt, ammonium salt NH₄ ⁺, salt of primary amine RNH₂, secondary amine salt (R)₂NH, tertiary amine salt (R)₃N, quaternary amine salt (R)₄N⁺, morpholine salt, piperidine salt, pyridine salt, aminopropylmorpholine salt, jeffamine D-230 salt, 2,4,6-tri(dimethylaminomethyl)phenol sodium hydroxide salt, C1-C14 alkylsulfonium salt, C1-C14 alkylsulfoxonium salt, C1- C14 alkylphosphonium or C1-C14 alkanolphosphonium salt;

where each R is independently unsubstituted C1-C14 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C3-C12 cycloalkyl, or phenyl; or C1-C14 alkyl optionally substituted with one or more of the following groups: halogen, hydroxy, C1-C6 alkoxy, C1-C6 alkylthio, hydroxy C1-C6 alkoxy, amino, C1-C6 alkylamino, amino C1-C6 alkylamino, phenyl;

in formula I-1 X is O or S;

тетрагидрофурил, пиридил, нафтил, фурил, тиенил,

который является незамещенным или замещенным C1-C6 алкилом; или фенил, который является незамещенным или замещенным C1-C6 алкилом, галоген C1-C6 алкилом, C1-C6 алкиламино, галогеном или C1-C6 алкокси;M is C1-C18 alkyl (preferably C1-C12 alkyl, more preferably C1-C8 alkyl, even more preferably C1-C6 alkyl), halo C1-C8 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, halo C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, cyano C1-C6 alkyl (preferably cyano C1-C2 alkyl), nitro C1-C6 alkyl (preferably nitro C1-C2 alkyl), C1-C6 alkoxy C1-C6 alkyl (preferably C1-C6 alkoxy C1-C2 alkyl), C1-C6 alkoxycarbonyl C1-C6 alkyl (preferably C1-C6 alkoxycarbonyl C1-C2 alkyl), C2-C6 alkenyloxycarbonyl C1-C6 alkyl (preferably C2-C6 alkenyloxycarbonyl C1-C2 alkyl), -(C1-C6 alkyl)-Z (preferably -(C1-C2 alkyl)-Z),

tetrahydrofuryl, pyridyl, naphthyl, furyl, thienyl,

which is unsubstituted or substituted C1-C6 alkyl; or phenyl which is unsubstituted or substituted by C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkylamino, halo or C1-C6 alkoxy;

тетрагидрофурил, пиридил,

тиенил, фурил, нафтил; или фенил, который является незамещенным или замещенным по меньшей мере одной группой, выбранной из группы, состоящей из C1-C6 алкила, C1-C6 алкокси, галоген C1-C6 алкила, циано и галогена;Z represents

tetrahydrofuryl, pyridyl,

thienyl, furyl, naphthyl; or phenyl which is unsubstituted or substituted with at least one group selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkyl, cyano and halo;

each R ₃ is independently C1-C6 alkyl;

each R ₄ , R ₅ , R ₆ independently represents hydrogen, C1-C6 alkyl or C1-C6 alkoxycarbonyl;

R' is hydrogen, C1-C6 alkyl or halo C1-C6 alkyl.

Even more preferably, each A, B is independently fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, trifluoromethyl, or cyclopropyl;

C represents hydrogen, fluorine, chlorine, bromine, iodine, methyl or trifluoromethyl;

бензил, нафтил, фурил, тиазолил, пиридил, пиримидинил; тиазолил, который является незамещенным или замещенным хлором; тиенил, который является незамещенным или замещенным фтором;

который является незамещенным или замещенным метилом или фтором; или фенил, который является незамещенным или замещенным по меньшей мере одной группой, выбранной из группы, состоящей из метила, трифторметила, хлора и метокси;Q is methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, cyano, amino, nitro, formyl, methoxy, methylthio, methoxycarbonyl, monochloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2 ,2,2-trifluoroethyl, hydroxymethyl,

benzyl, naphthyl, furyl, thiazolyl, pyridyl, pyrimidinyl; thiazolyl which is unsubstituted or substituted with chlorine; thienyl which is unsubstituted or substituted with fluorine;

which is unsubstituted or substituted with methyl or fluorine; or phenyl which is unsubstituted or substituted with at least one group selected from the group consisting of methyl, trifluoromethyl, chlorine and methoxy;

Y is NH ₂ ,

salt is a metal salt, ammonium salt NH₄ ⁺, salt of primary amine RNH₂, secondary amine salt (R)₂NH, tertiary amine salt (R)₃N, quaternary amine salt (R)₄N⁺, morpholine salt, piperidine salt, pyridine salt, aminopropylmorpholine salt, jeffamine D-230 salt, 2,4,6-tri(dimethylaminomethyl)phenol sodium hydroxide salt, C1-C6 alkylsulfonium salt, C1-C6 alkylsulfoxonium salt, C1- C6 alkylphosphonium or C1-C6 alkanolphosphonium salt;

where each R is independently unsubstituted C1-C14 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C12 cycloalkyl, phenyl, or benzyl; or C1-C14 alkyl optionally substituted with one or more of the following groups: hydroxy, C1-C4 alkoxy, C1-C4 alkylthio, hydroxy C1-C4 alkoxy, amino, C1-C4 alkylamino, amino C1-C4 alkylamino;

), соль три(метилол)аминометана (

), соль морфолина, соль пиперидина, соль пиридина, соль аминопропилморфолина (

), соль джеффамина D-230 (

, n равно 2 или 3), соль 2,4,6-три(диметиламинометил)фенола и гидроксида натрия, соль сульфония, такая как соль алкилсульфония (как, например, соль триметилсульфония, соль триэтилсульфония), соль алкилсульфоксония, соль фосфония, такая как соль алкилфосфония или соль алканолфосфония;the salt is preferably an alkali metal salt (such as sodium, lithium, potassium, cesium or rubidium), an alkaline earth metal salt (such as calcium, magnesium, barium or strontium), a heavy metal salt (such as antimony, zinc, bismuth, cadmium, cerium, chromium, cobalt, copper, iron or other metals with a density greater than 4), aluminum salt, amine salt such as ammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetraisopropylammonium salt, tetrabutylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, Cholinamine Salt, Monomethylamine Salt, Dimethylamine Salt, Trimethylamine Salt, Monoethylamine Salt, Diethylamine Salt, Triethylamine Salt, Monoisopropylamine Salt, Diisopropylamine Salt, Triisopropylamine Salt, Monoisobutylamine Salt, Pentylamine Salt, Hexylamine Salt, Heptylamine Salt, Dodecylamine Salt, Tetradecylamine Salt, Diallylamine Salt , cyclododecylamine salt, benzylamine salt, monoethanolamine salt, diethanolamine salt, salt triethanolamine, tripropanolamine salt, triisopropanolamine salt, tri(2-hydroxypropyl)amine salt, methylmonoethanolamine salt, dimethylmonoethanolamine salt, methyldiethanolamine salt, diethylethanolamine salt, diglycolamine salt, polyamine salt (e.g. diethylenetriamine salt, dimethylaminopropylamine salt, 1,2-propyldiamine salt, triethylenetetramine salt, N,N-bis[aminopropyl]methylamine salt), 2-methylthiopropylamine salt, 2-butoxyethylamine salt, AEPD(

), tri(methylol)aminomethane salt (

), morpholine salt, piperidine salt, pyridine salt, aminopropylmorpholine salt (

), jeffamine salt D-230 (

, n is 2 or 3), 2,4,6-tri(dimethylaminomethyl)phenol sodium hydroxide salt, sulfonium salt such as alkylsulfonium salt (such as trimethylsulfonium salt, triethylsulfonium salt), alkylsulfoxonium salt, phosphonium salt, such as an alkylphosphonium salt or an alkanolphosphonium salt;

in formula I-1 X is O or S;

тетрагидрофурил (

), тетрагидрофурилметилен (

), пиридил (

или

), пиридилметилен (

), нафтил (

), нафтилметилен (

), фурил (

), фурилметилен (

), тиенил (

), тиенилметилен (

),

(

или

),

(

),

(

или

);

(

) который является незамещенным или замещенным метилом; фенил, который является незамещенным или замещенным метилом, диметиламино, хлором, метокси, трифторметилом или изопропилом; или бензил, который является незамещенным или замещенным трифторметилом, бромом, хлором, фтором, метокси, циано или метилом;M is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl, trifluoromethyl, pentafluoroethyl, 3-chlorobutyl , 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 4,4,4-trifluorobutyl, 2,2,3,3,3-pentafluoropropyl, cyclopropyl, cyclobutyl , cyclopentyl, cyclohexyl, allyl, 2-propynyl, methoxy, ethoxycarbonyl, methylsulfonyl,

tetrahydrofuryl (

), tetrahydrofurylmethylene (

), pyridyl (

or

), pyridylmethylene (

), naphthyl (

), naphthylmethylene (

), furyl (

), furylmethylene (

), thienyl (

), thienylmethylene (

),

(

or

),

(

),

(

or

);

(

) which is unsubstituted or substituted with methyl; phenyl which is unsubstituted or substituted with methyl, dimethylamino, chlorine, methoxy, trifluoromethyl or isopropyl; or benzyl which is unsubstituted or substituted with trifluoromethyl, bromine, chlorine, fluorine, methoxy, cyano or methyl;

R' is hydrogen, methyl, ethyl or difluoromethyl.

In the definition of a compound represented by general formula I above, and in all structural formulas below, the term, whether used alone or in the name of the compound, refers to the following substituent: an alkyl group having more than two carbon atoms may be straight or branched. For example, in the compound name “-alkyl-OR”, alkyl may be -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ and the like. The alkyl group is, for example, C1 alkylmethyl; C2 alkylethyl; C3 alkylpropyl such as n-propyl or isopropyl; C4 alkylbutyl such as n-butyl, isobutyl, t-butyl or 2-butyl; C5 alkylpentyl such as n-pentyl; C6-alkylhexyl such as n-hexyl, isohexyl or 1,3-dimethylbutyl. Similarly, alkenyl includes, for example, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en- 1-yl, 1-methylbut-3-en-1-yl and 1-methylbut-2-en-1-yl. Alkynyl includes, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. The multiple bond may be in any position of each unsaturated group. Cycloalkyl is a carbocyclic saturated ring system having, for example, three to six carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl is a monocyclic alkenyl having, for example, three to six carbocyclic elements such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, the double bond being in any position. Halogen is fluorine, chlorine, bromine or iodine.

When a group is substituted by a group, the group is meant to be substituted by one or more of the same or different groups selected from the groups indicated above. In addition, the same or different substitution symbols contained in the same or different substituents are independently selected and may be the same or different.

In addition, unless specifically indicated, a term occurring before or after several adjacent substituents (separated by "," or the union "or") in the present invention has a limiting effect on each of the subsequent substituents, for example, the term "unsubstituted or "substituted" in the expression "unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl" has a limiting effect on each of the following groups: "aryl", "heteroaryl", "arylalkyl" and "heteroarylalkyl".

The method for producing R-pyridyloxycarboxylic acid and its salt, ester derivative includes the following steps.

A compound of formula III is reacted with a compound of formula II to give a compound of formula I-1-1; the reaction scheme looks like this:

where W is an alkali metal, preferably K, Na; Hal is halogen, preferably Br, Cl; the reaction is carried out in the presence of a catalyst and a solvent. Preferably the catalyst is TBAB and the solvent is one or more selected from the group consisting of DCM, DCE, ACN, THF, DMF.

The compound of formula I-1-1 reacts in the presence of an aqueous solution of lithium hydroxide and a solvent to obtain a compound of formula I; the reaction scheme is as follows:

preferably the solvent is one or more selected from the group consisting of methanol, ethanol and isopropanol.

The compound of formula I is subjected to reaction with M-SH to obtain a compound of formula I-1-2; the reaction scheme looks like this:

where the reaction is carried out in the presence of a dehydrating agent and a solvent, preferably the dehydrating agent is DCC, and the solvent is one or more selected from the group consisting of dichloromethane, dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, toluene, xylene;

или соединения формулы I-1-3

с соответствующим галогенидом;or when Y is NR ₁ R ₂ (R ₁ , R ₂ are not hydrogen at the same time) it is obtained by reacting a compound of formula I-2

or compounds of formula I-1-3

with the corresponding halide;

where the halide is preferably chloride or bromide; the reaction is carried out in the presence of a base and a solvent, where the base is one or more of the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate; the solvent is one or more selected from the group consisting of THF, 1,4-dioxane, toluene, 1,2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane and chloroform; a catalyst, preferably DMAP, is optionally added during the reaction.

The salt is an agrochemically acceptable salt, which is preferably prepared by reacting an R-pyridyloxycarboxylic acid compound of the present invention with a chemically acceptable basic compound.

For example, in the present application, a diethylamine salt is prepared by reacting an R-pyridyloxycarboxylic acid compound of the present invention with diethylamine.

In another example, 2,4,6-tri(dimethylaminomethyl)phenol sodium hydroxide salt refers to a salt prepared by reacting an R-pyridyloxycarboxylic acid compound of the present invention with 2,4,6-tri(dimethylaminomethyl)phenol and sodium hydroxide

.

.

The agrochemically acceptable salt mentioned above can be easily separated and can be purified by conventional separation methods such as solvent extraction, dilution, recrystallization, column chromatography and preparative thin layer chromatography.

The present invention provides a herbicidal composition comprising (i) at least one R-type pyridyloxycarboxylic acid of formula I and a salt, an ester derivative thereof; preferably also containing (ii) one or more additional herbicides and/or safeners; more preferably, additionally containing (iii) agrochemically acceptable formulation auxiliaries.

The present invention relates to a weed control method comprising applying a herbicidally effective amount of at least one R-type pyridyloxycarboxylic acid and a salt, ester derivative or herbicidal composition thereof to a plant or weed site. Preferably the plant is rice or the weed is a grass weed (such as Echinochloa crusgalli, Digitaria sanguinalis, Semen Euphorbiae Lathyridis ) or a deciduous weed (such as Monochoria Vaginalis, Abutilon theophrasti Medic., Galium aparine ).

The use of at least one of R-pyridyloxycarboxylic acid and its salt, ester derivative or herbicidal composition for weed control, preferably R-pyridyloxycarboxylic acid and its salt, ester derivative, is used for weed control in a useful crop, where the useful crop is a genetically modified crop or a crop modified by genome editing technology. Preferably the crop is rice or the weed is a grass weed (such as Echinochloa crusgalli, Digitaria sanguinalis, Semen Euphorbiae Lathyridis ) or a deciduous weed (such as Monochoria Vaginalis, Abutilon theophrasti Medic., Galium aparine ).

The formula I compounds of the invention have outstanding herbicidal activity against a wide range of economically important monocot and dicot pests. The active compounds are also effective against perennial weeds that sprout from rhizomes, root crops or other perennial organs and are difficult to control. In this context, as a rule, it does not matter whether these substances are applied before sowing, before germination or after germination. In particular, examples can be given of certain representatives of the monocot and dicot weed flora that can be controlled by the compounds of the invention, without any limitation to certain species. Examples of weed species effectively affected by the active compounds are, among the monocotyledonous species, Avena , Lolium , Alopecurus , Phalaris , Echinochloa , Digitaria , Setaria , and the Cyperus species from the annual and perennial species of Agropyron , Cynodon , Imperata and Sorghum , as well as perennial species of Cyperus .

In the case of dicotyledonous weed species, the spectrum of activity extends to such species as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Sida, Matricaria and Abutilon among the annuals, and Convolvulus, Cirsium, Rumex and Artemisia in case of perennial weeds. The active compounds of the invention are also effective in controlling harmful plants that are found under specific rice growing conditions, such as, for example, Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus . If the compounds of the invention are applied to the soil surface before germination, then the emergence of weed seedlings is either completely prevented, or the weeds grow until they reach the cotyledon stage, but then their growth stops, and, ultimately, after three to four weeks they are completely dead. In particular, the compounds of the invention show excellent activity against the species Apera spica venti, Chenopodium album, Lamium purpureum, Polygonum convulvulus , Stellaria media, Veronica hederifolia, Veronica persica, Viola tricolor, and against Amaranthus, Galium and Kochia .

Although the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops such as, for example, wheat, barley, rye, rice, corn, sugar beet, cotton and soybeans are not affected at all or only slightly affected. degree. In particular, they have excellent compatibility with cereals such as wheat, barley and corn, especially wheat. Therefore, the present compounds are particularly suitable for selectively controlling unwanted plant growth in the agricultural production of useful crops or in ornamental crop production.

Due to their herbicidal properties, these active compounds can also be used to control harmful plants in cultures of known plants or genetically modified plants still being developed. Transgenic plants usually have particularly advantageous properties, for example resistance to certain pesticides, especially certain herbicides, resistance to plant diseases and plant pathogens such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties relate to the harvested crop, such as its quantity, quality, keeping quality, composition, and special ingredients. Thus, transgenic plants with an increased starch content or a modified starch quality, or plants with a different fatty acid composition in the harvested crop, are known.

Preferably the use of the compounds of formula I according to the invention or their salts for economically important transgenic crops of useful plants and ornamental plants, for example cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn, or in crops of sugar beet, cotton , soybeans, rapeseed, potatoes, tomatoes, peas and other types of vegetables. The compounds of formula I can preferably be used as herbicides in useful crops which are resistant or which have been genetically engineered to be resistant to the phytotoxic effects of herbicides.

Traditional ways of producing new plants that exhibit modified properties compared to those of known plants include, for example, conventional methods for growing and producing mutants. Alternatively, new plants with modified properties can be obtained using genetic engineering techniques (see, for example, EP-A 0 221 044, EP-A 0 131 624). For example, several cases of genetically modified changes in crop plants have been described in order to modify the starch synthesized in plants (for example, WO 92/11376, WO 92/14827, WO 91/19806),

transgenic crop plants resistant to certain glufosinate (ammonium glufosinate) herbicides (see e.g. EP-A 0 242 236, EP-A 0 242 246) or glyphosate herbicides (e.g. WO 92/00377) or sulfonylurea type (EP- A 0 257 993, US 5013659 A),

transgenic crop plants capable of producing Bacillus thuringiensis toxins (Bt toxins) that confer resistance to certain weeds (EP-A 0 142 924, EP-A 0 193 259),

transgenic crop plants having a modified fatty acid composition (WO 91/13972).

In principle, numerous methods of molecular biology are known that make it possible to create new transgenic plants with modified properties; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N. Y. ; or Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim, 2nd edition 1996, or Christou, "Trends in Plant Science" 1 (1996) 423-431). For this kind of genetic manipulation, nucleic acid molecules can be introduced into plasmids that cause mutagenesis or sequence change due to recombination of DNA sequences. Using the aforementioned standard methods, it is possible, for example, to exchange bases, remove part of a sequence, or add natural or synthetic sequences. To link DNA fragments to each other, adapters or linkers can be attached to the fragments.

The production of plant cells with reduced gene product activity can be achieved, for example, by expressing at least one appropriate antisense RNA, one sense RNA to achieve a co-suppression effect, or by expressing at least one appropriately designed ribozyme that cleaves a specific transcript of the above gene product.

For this, both DNA molecules that cover the entire coding sequence of the gene product, including any possibly present side fragments of the sequence, and DNA molecules that cover only part of the coding sequence, and these parts must be of sufficient length to cause an antisense effect in cells, can be used. . It is also possible to use DNA sequences that show a high degree of similarity with the coding sequences of the gene product, but are not completely identical.

In the case of the expression of nucleic acid molecules in plants, the synthesized protein can be localized at any desired location in plant cells. However, in order to achieve localization at a specific site, it is possible, for example, to link the coding region to DNA sequences that provide localization at a specific site. Such sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846 -850; Sonnewald et al., Plant J. 1 (1991), 95-106).

Transgenic plant cells can be regenerated into whole plants by known methods. Transgenic plants can in principle be plants of any kind, ie. both monocots and dicots. So, for example, transgenic plants can be obtained, the properties of which are changed by overexpression, suppression or inhibition of homologous (natural) genes or their sequences, or by expression of heterologous (foreign) genes or their sequences.

When the biologically active compounds of the invention are used in transgenic crops, in addition to the effects observed on weeds in other crops, there often appear effects that are specific when used in the corresponding transgenic crop, for example, a modified or specially extended range of weeds, with which it is possible to to fight, modified application rates of the drug that can be used in the treatment, mainly good compatibility with herbicides to which transgenic crops are resistant, as well as the effect on the growth and yield of transgenic crop plants. Therefore, the invention also provides for the use of the compounds according to the invention as herbicides for the control of harmful plants in transgenic crop plants.

In addition, the substances of this invention have excellent growth regulating properties in crop plants. They act as regulators in plant metabolism and can thus be used to target plant constituents and to facilitate harvesting, for example by promoting moisture loss and stunting. In addition, they are also suitable for general regulation and inhibition of unwanted vegetative growth without killing plants. The retardation of vegetative growth plays an important role in many monocots and dicots, as lodging can be reduced or completely prevented.

The compounds of this invention may be used in conventional formulations as wettable powders, emulsion concentrates, sprays, sprays or granules. Thus, the invention also relates to herbicidal compositions containing compounds of formula I. Compounds of formula I can be prepared in various ways depending on the prevailing biological and/or chemical-physical parameters. Examples of suitable formulation options are: wettable powders (WP), water soluble powders (SP), water soluble concentrates, emulsion concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, spray solutions , suspension concentrates (SC), oil dispersions (OD), oil-based or water-based dispersions, oil-miscible solutions, pollinators (DP), capsule suspensions (CS), seed dressing compositions, spreading and soil granules , granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULW compositions, microcapsules and waxes. These individual types of compositions are known in principle and are described, for example, in the following works: Winnacker-Küchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th. Edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N. Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and described in, for example, Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N. J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N. Y. ; C. Marsden, Solvents Guide; 2nd Ed., Interscience, N. Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N. J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N. Y. 1964; Schönfeldt, "Grenzflüchenaktive Äthylenoxidaddkte" [Surface-active ethylene oxide adducts], Wiss. Verlagagesell. Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Edition 1986.

Wettable powders are preparations which are evenly dispersed in water and which contain, in addition to the active compound and a diluent or inert agent, surfactants of the ionic and/or non-ionic type (wetting agents, dispersants), e.g. polyethoxylated alkylphenols , polyethoxylated fatty alcohols, polyethoxylated fatty amines, polyglycol ether sulfates of fatty alcohols, alkane sulfonates, alkylbenzenesulfonates, sodium lignin sulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurinate. For the preparation of wettable powders, the herbicidally active compounds are finely ground, for example, in conventional apparatus such as hammer mills, impeller mills and air jet mills, and simultaneously with or after milling are mixed with the auxiliaries of the formulations.

Emulsion concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene, or also in high boiling aromatic compounds or hydrocarbons, or mixtures of these solvents, with the addition of one or more ionic and/or non-ionic type surfactants. (emulsifiers). Examples of emulsifiers that can be used are: calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate or non-ionic emulsifiers such as polyglycol fatty acid esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide and ethylene oxide condensates, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.

Pollinators are prepared by grinding the active compound together with fine solids such as talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspension concentrates may be water or oil based. They can be obtained, for example, by wet grinding with commercially available bead mills, with or without the addition of surfactants, which are already mentioned above for other types of compositions.

Emulsions, such as oil-in-water (EW) type emulsions, can be prepared, for example, with stirrers, colloid mills and/or static mixers using aqueous organic solvents and, if appropriate, surfactants that are already above for other types of compositions.

Granules can be prepared either by spraying the active compound onto an adsorbent granular inert material or by applying active compound concentrates to the surface of carriers such as sand, kaolinite, or granular inert material using adhesives such as polyvinyl alcohol, sodium polyacrylate, or also mineral oils. Suitable active compounds can also be granulated in a manner which is customary for the preparation of fertilizer granules, optionally as a mixture with fertilizers. Water-dispersible granules are usually produced by conventional methods such as spray drying, fluid bed granulation, disk granulation, mixing using high speed mixers, and extrusion without solid inert material.

For granule production processes such as disk, fluidized bed, extrusion and spraying, see, for example, "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff. ; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57. For more detailed information on plant protection product compositions see, for example, G. C. Klingman, "Weed Control as a Science", John Wiley and Sons Inc., New York, 1961, pages 81-96, and J. D. Freyer, S. A. Evans , "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

Agrochemical compositions contain, as a rule, from 0.1 to 99 wt. -%, in particular from 0.1 to 95 wt. active compounds of formula I. In wettable powders, the concentration of the active compound is, for example, from about 10 to 99 wt. -%, and the rest up to 100% of the mass. consists of the usual components of the composition. In emulsion concentrates, the concentration of the active compound can be from about 1 to 90% by weight, preferably 5-80% by weight. Compositions in the form of means for pollination contain 1-30% of the mass. active compound, preferably most often 5-20% of the mass. active compound, while spray solutions contain from about 0.05 to 80% wt., preferably 2-50% wt. active connection. In the case of water-dispersible granules, the content of the active compound depends in part on whether the active compound is in liquid or solid form and also on which excipients, excipients, and the like. used in granulation. In water-dispersible granules, the content of the active compound, for example, is 1-95% by weight, preferably 10-80% by weight.

In addition, said active compound compositions may contain tackifiers, wetting agents, dispersants, emulsifiers, impregnating agents, preservatives, freezing point depressants, solvents, fillers, carriers, colorants, antifoams, evaporative retarders, and pH and viscosity adjusters that are commonly used in every case.

These compositions can also be combined with other pesticide-active substances, for example, insecticides, acaricides, herbicides and fungicides, as well as safeners, fertilizers and/or growth regulators, for example, in the form of a ready mix or tank mix.

Suitable active compounds that can be combined with the active compounds of the invention in mixed formulations or tank mix are, for example, known active compounds as described, for example, in World Herbicide New Product Technology Handbook , China Agricultural Science and Farming Techniques Press, 2010. 9 and in the literature cited there. For example, the following active compounds may be named as herbicides, which may be combined with compounds of formula I (Note: the compounds are either referred to by the "common name" in accordance with the requirements of the International Organization for Standardization (ISO), or chemical names, if necessary, together with conventional numerical code): acetochlor, butachlor, alachlor, propisochlor, metolachlor, c-metolachlor, pretilachlor, propachlor, ethachlor, napropamide, R-levorotatory napropamide, propanil, mefenacet, diphenamide, diflufenican, etaprochlor, beflubutamide, bromobutide, dimethenamid, dimethenamid -P, etobenzanide, fluphenacet, tenylchlor, metazachlor, isoxaben, flamprop-M-methyl, flamprop-M-propyl, allidochlor, petoxamide, chloranocryl, cyprazine, mefluidide, monalid, delachlor, prinachlor, terbuchlor, xylachlor, dimetachlor, cisanilide, trimexachlor , clomeprop, propizamide, pentanochlor, carbetamide, benzoylprop-ethyl, ciprazole, butenachlor, tebutam, benzipram, mogrton, dichlofluanid, naproanilide, d iethatyl-ethyl, naptalam, fluphenacet, benzadox, chlorthiamide, chlorphthalimide, isocarbamide, picolinafen, atrazine, simazine, promethrin, cyanathrine, symetrin, ametrin, propazine, dipropetrin, SSH-108, terbutrin, terbutylazine, triaziflam, ciprazine, proglinazine, trietazine, promethone, simeton, aziprotrin, desmetrin, dimethamethrin, procyazine, mesoprazine, sebutylazine, secbumeton, terbumeton, metoprotrin, cyanathrine, ipazine, chlorazine, atratone, pendimethalin, eglinazine, cyanuric acid, indaziflam, chlorsulfuron, metsulfuron-methyl, benchlorimuron-methyl, ethyl, tribenuron-methyl, triphensulfuron-methyl, pyrazosulfuron-ethyl, mesosulfuron, iodosulfuron-methyl sodium, foramsulfuron, cinosulfuron, triasulfuron, sulfometuron methyl, nicosulfuron, etametsulfuron-methyl, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, monosulfuron, monosulfuron ester, flucarbazone sodium, flupyrsulfuron methyl, halosulfuron methyl, oxasulfuron, imazosulfuron, primisulfuron, propoxybazone, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron-methyl, tritosulfuron, metsulfuron methyl sodium, flucetosulfuron, HNPC-C, orthosulfamuron, propyrisulfuron, metazosulfuron, acifluorfen, fomesafen, lactofen, fluoroglycofen, oxyfluorfen, biphenoxyphenol-clone, ethyl chloride , nitrofluorfen, chlomethoxifen, fluorodifen, fluoronitrofen, furyloxifene, nitrofen, TOPE, DMNP, PPG1013, AKH-7088, halosafen, chlortoluron, isoproturon, linuron, diuron, dimron, fluometuron, benzthiazuron, metabenzthiazuron, cumiluron, ethidimuron, isouron, tebuthiron , chlorbromuron, methyldymron, fenobenzuron, SK-85, metobromuron, methoxiron, afesin, monouron, siduron, fenuron, fluothiuron, neburon, chloroxuron, noruron, isonoruron, 3-cyclooctyl-1, thiazfluron, tebuthiuron, difenoxuron, parafluron, methylamine tribunil, carbutylate, trimeturon, dimefuron, monisouron, anisuron, methiuron, chloreturon, tetrafluron, phenmedipham, phenmedipham-ethyl, desmedipham, asulam, terbucarb, barban, profam, chlorpropham, roumate, swep, chlorbufam, carboxazole, chlorprocarb, fenasulam, BCPC, CPPC, carbasulam, butylate, bentiocarb, vernolate, molinate, triallate, dimepiperate, esprocarb, pyributicarb, cycloate, avadex, EPTC, etiolate, orbencarb, pebulate, prosulfocarb, thiocarbazyl, CDEC, dimexano, isopolynate, methiobencarb, 2,4-D butyl ester, MCPA-Na, 2,4-D isooctyl ether, MCPA isooctyl ether, 2,4-D sodium salt, salt 2,4-D dimethylamine, MCPA-thioethyl, MCPA, 2,4-D propionic acid, salt of higher 2,4-D propionic acid, 2,4-D butyric acid, MCPA propionic acid, MCPA salt of propionic acid, MCPA butyric acid, 2,4,5-D, 2,4,5-D propionic acid, 2,4,5-D butyric acid, MCPA amine salt, dicamba, erbon, chlorfenac, saison, TBA, chloramben, methoxy-TBA, diclofop-methyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-P, quizalofop-ethyl, quizalofop-p-ethyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, propaquizafop, cyhalofop-butyl, meth amifop, clodinafop-propargyl, fentiaprop-ethyl, chlorazifop-propynyl, propenate-methyl, triphopsime, isoxapirifop, paraquat, diquat, oryzalin, ethalfluralin, isopropalin, nitraline, profluralin, prodynamine, benfluralin, fluchloralin, dinitramine, dipropalin, chlornidine, metalpropalin, dinoprop, glyphosate, anilophos, ammonium glufosinate, amiprofos-methyl, sulfosate, piperophos, bialafos-sodium, bensulide, butamiphos, focarb, 2,4-DEP, H-9201, zitron, imazapir, imazethapyr, imazakquin, imazamox, imazamox ammonium salt , imazapic, imazamethabenz-methyl, fluroxypyr, fluroxypyr isooctyl ester, clopyralid, picloram, triclopyr, dithiopyr, haloxydin, 3,5,6-trichloro-2-pyridinol, thiazopyr, fluridone, aminopyralid, diflufenzopyr, triclopyr-butolyl, Cliodinate, Setoxydim, Cletodim, Cycloxydim, Allodim, Clefoxidim, Butroxydim, Tralkoxydim, Tepraloxydim, Butidazole, Metribuzin, Hexazinon, Metamitron, Ethiosin, Ametridione, Amibusin, Bromoxynil, Bromoxynil Octanoate, Ioxynyl Octanoate, Ioxynil, Dichlob enyl, diphenatril, pyraclonil, chloroxynil, iodobonil, flumetsulam, florasulam, penoxsulam, methosulam, cloransulam-methyl, diclosulam, pyroxsulam, benfuresate, bispyribac-sodium, pyribenzoxime, pyrifthalide, pyriminobac-methyl, pyrithiobac-sodium, benzobicillone, mesotrione, tembotrione, tefuryltrione, bicyclopyrone, ketopyradox, isoxaflutol, clomazone, phenoxasulfone, methiozolin, fluazolate, pyraflufen-ethyl, pyrazolinate, diphenzoquat, pyrazoxifene, benzofenap, nipyraclofen, pyrasulfotol, topramesone, pyroxasulfone, cafenstrol, fluroxam, aminophenitrazone, aminotrabadine, aminotrabadine ethyl, sulfentrazone, bencarbazone, benzfendison, butafenakil, bromacyl, isocyl, lenacil, terbacil, flupropacil, cynidone-ethyl, flumicrolac-pentyl, flumioxazine, propizamide, MK-129, flumezin, pentachlorophenol, dinoseb, dinoterb, dinoterb acetate, dinosam, DNOC , chlornitrofen, medinoterb acetate, dinofenate, oxadiargyl, oxadiazon, pentoxazone, flufenacet, fluthiacet-methyl, phentrazamide, flufenpyr-ethyl, pyrazo n, bromopyrazone, metflurazone, kusakira, dimidazone, oxapirazone, norflurazone, pyridafol, quinclorac, chinmerac, bentazone, pyridate, oxaziclomefone, benazoline, clomazone, cinmethylin, ZJ0702, pyribambenz-propyl, indanophane, sodium chlorate, dalapon, trichloroacetic acid, monochloroacetic acid , hexachloroacetone, flupropanate, cyperquat, bromophenoxime, epronase, metazol, flurtamone, benfuresate, etofumesate, thioclorim, chlorthal, fluorochloridone, tavron, acrolein, bentranil, tridiphan, chlorphenpropmethyl, thidiarizonaimine, fenizofam, busoxinone, methoxyponenone, chloracflufenacilos, alo , dietamquat, ethnipromide, iprimidam, ipfencarbazone, thiencarbazone-methyl, pyrimisulfan, chlorflurazol, tripropindan, sulglycapine, prosulfalin, cambendichlor, aminocyclopyrachlor, rodetanil, benoxacor, fenclorim, flurazol, fenchlorazole-ethyl, cloquintocet-mexyl, oxabetrinil, MG9 , DKA-24, mefenpyr-diethyl, furilazole, fluxofenim, isoxadifen-ethyl, dichlormide, halauxifen-methyl, DOW florbiroxifene, UBH-509 , D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.

In the context of the present description, if an abbreviation of the generic name of the active compound is used, it includes in each case all the usual derivatives such as esters and salts, as well as isomers, in particular optical isomers, especially one or more commercially available forms. When a generic name means an ester or salt, it also includes in each case all other conventional derivatives such as other esters and salts, free acids and neutral compounds, as well as isomers, in particular optical isomers, especially one or more of the commercially available forms . The chemical name given to a compound means at least one compound covered by the generic name, and generally the preferred compound.

For use, compositions which are present in commercially available form are diluted if necessary in the usual manner, for example using water in the case of wettable powders, emulsion concentrates, dispersions and water-dispersible granules. Products in the form of pollinators, granules for soil application or spreading, and spray solutions are generally not further diluted with other inert substances prior to use. The rate of application of the compounds of formula I varies depending on external conditions such as temperature, humidity, the nature of the herbicide used and the like. It can vary within wide limits, for example 0.001-1.0 kg a.i./ha or more active substance, but preferably 0.005-750 g a.i./ha, in particular 0.005-500 g a.i./ ha.

Specific way of carrying out the invention

The following examples are intended to illustrate the present invention and should not be construed as limiting the present invention in any way. The required scope of patent protection in the present invention is determined by the claims.

From the point of view of economy and variety of compounds, the authors preferably synthesized several compounds, some of which are listed in the following tables 1-2. Structure and information about a specific compound are shown in Tables 1-3. The compounds in Tables 1-2 are listed to further illustrate the present invention and not to limit it. The subject matter of the present invention should not be interpreted by those skilled in the art as being limited to the following compounds.

Table 3
H-NMR data of compounds No. ¹ H-NMR 1-2 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 12.33 (s, 1H), 7.07 (s, 2H), 5.15 (q, J=7.0 Hz, 1H), 1.50 (d, J=7.0 Hz, 3H). 1-4 ¹ H NMR (500 MHz, Chloroform-d) δ 7.63-7.61 (m, 2H), 7.45-7.38 (m, 3H), 6.13 (s, 1H), 5.18 (s, 2H) 1-26 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 12.96 (s, 1H), 6.99 (s, 2H), 5.06 (q, J=7.0 Hz, 1H), 1.50 (d, J=7.0 Hz, 3H) 1-27 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.82 (s, 2H), 4.18 (dd, J=11.0, 2.0 Hz, 1H), 2.05-2.27 ( m, 2H), 0.93 (t, J=8.0 Hz, 3H). 1-71 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 12.42 (s, 1H), 8.21 (d, J=2.5 Hz, 1H), 7.76 (t, J=5.5 Hz , 1H), 7.21-7.11 (m, 2H), 5.15 (q, J=7.0 Hz, 1H), 4.98 (d, J=5.5 Hz, 2H), 1 .50 (d, J=7.0 Hz, 3H). 2-28 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.53 (s, 1H), 6.36 (s, 2H), 4.63 (q, J=7.0 Hz, 1H), 3.72 (s, 3H), 2.08 (s, 3H), 1.50 (d, J=7.0 Hz, 3H). 2-29 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.36 (s, 2H), 4.66 (q, J=7.0 Hz, 1H), 3.72 (s, 3H), 2.08 (s, 3H), 1.51 (d, J=7.0 Hz, 3H). 2-30 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.61 (s, 1H), 6.80 (s, 2H), 4.63 (q, J=7.0 Hz, 1H), 3.72 (s, 3H), 1.51 (d, J=7.0 Hz, 3H). 2-31 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.66 (q, J=7.0 Hz, 1H), 3.72 (s, 3H), 1.52 (d, J=7.0 Hz, 3H). 2-32 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.65 (q, J=7.0 Hz, 1H), 3.72 (s, 3H), 2.53 (s, 3H), 1.51 (d, J=7.0 Hz, 3H). 2-33 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.79 (s, 2H), 4.74 (dd, J=10.0, 2.5 Hz, 1H), 2.31 (s, 3H) , 1.84 (dtd, J=8.0, 4.0, 2.0 Hz, 1H), 1.74-1.84 (m, 1H), 0.89 (t, J=8.0 Hz , 3H). 2-34 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.04 (s, 2H), 5.00-5.03 (m, 1H), 3.66 (s, 3H), 1.84-1, 94 (m, 2H), 0.96-1.0 (m, 3H). 2-35 ¹ H NMR (500 MHz, Chloroform-d) δ 5.14 (s, 2H), 4.97 (d, J=4.5 Hz, 1H), 3.75 (s, 3H), 2.31- 2.37 (m, 1H), 1.09 (dd, J=7.0, 2.0 Hz, 6H). 2-36 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.79 (s, 2H), 4.83 (d, J=7.0 Hz, 1H), 2.31 (s, 3H), 2.27 (dt, J=13.5, 7.0 Hz, 1H), 0.88 (dd, J=25.0, 7.0 Hz, 6H). 2-37 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.32 (dd, J=11.0, 1.0 Hz, 1H), 3.72 (s, 3H) , 1.81-1.92 (m, 1H), 1.54-1.69 (m, 2H), 1.35-1.49 (m, 1H), 0.77-0.85 (m, 3H). 2-38 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.77 (s, 2H), 4.63 (d, J=7.0 Hz, 1H), 3.72 (s, 3H), 0.79 -0.86 (m, 1H), 0.37-0.49 (m, 2H), 0.28-0.33 (m, 2H). 2-39 ¹ H NMR (500 MHz, Chloroform-d) δ 5.05 (q, J=7.0 Hz, 1H), 4.44 (s, 2H), 3.85 (s, 3H). 2-40 ¹ H NMR (500 MHz, Chloroform-d) δ 4.52 (dd, J=11.0, 2.0 Hz, 1H), 4.44 (s, 2H), 3.85 (s, 3H), 2.77-2.87 (m, 1H), 2.65-2.73 (m, 1H). 2-41 ¹ H NMR (500 MHz, Chloroform-d) δ 4.74 (t, J=7.0 Hz, 1H), 4.44 (s, 2H), 4.35 (dd, J=12.5.7 .0 Hz, 1H), 4.00 (dd, J=12.5, 7.0 Hz, 1H), 3.85 (s, 3H). 2-42 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.58-4.61 (m, 1H), 3.78-3.86 (m, 1H), 3, 72 (s, 3H), 3.63-3.69 (m, 1H), 2.24-2.29 (m, 1H), 2.07-2.13 (m, 1H). 2-43 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.16-5.25 (m, 1H), 5.11 (dd, J=10.5, 5.0 Hz, 1H), 4.83-4.92 (m, 1H), 4.75-4.85 (m, 1H), 3.72 (s, 3H). 2-44 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 6.29 (d, J=7.0 Hz, 1H), 5.16-5.25 (m, 1H) , 3.72 (s, 3H). 2-45 ¹ H NMR (500 MHz, Chloroform-d) δ 6.12-6.19 (m, 1H), 5.43-5.45 (m, 1H), 5.32-5.37 (m, 1H) , 5.15-5.21 (m, 1H), 4.45 (s, 2H), 3.70 (s, 3H). 2-46 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.67 (d, J=3.0 Hz, 1H), 3.68 (d, J=3.0 Hz , 1H), 3.65 (s, 3H). 2-47 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.18 (s, 2H), 5.80 (s, 1H), 3.76 (s, 6H). 2-48 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 9.95 (d, J=6.0 Hz, 1H), 6.80 (s, 2H), 5.38 (d, J=6.0 Hz , 1H), 3.63 (s, 3H). 2-49 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.79 (s, 2H), 4.97 (t, J=5.5 Hz, 1H), 4.35 (t, J=7.0 Hz , 1H), 4.21-4.26 (m, 1H), 3.91-3.96 (m, 1H), 3.72 (s, 3H). 2-50 ¹ H NMR (500 MHz, Chloroform-d) δ 7.27 (s, 1H), 4.45 (s, 2H), 3.71 (s, 3H). 2-51 ¹ H NMR (500 MHz, Chloroform-d) δ 6.96 (s, 1H), 6.86 (d, J=47.0 Hz, 1H), 4.45 (s, 2H), 3.74 ( s, 3H). 2-52 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.83 (s, 2H), 6.76 (s, 1H), 3.66 (s, 3H). 2-53 ¹ H NMR (500 MHz, Chloroform-d) δ 6.62 (s, 1H), 4.47 (s, 2H), 3.73 (s, 3H). 2-54 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.07 (s, 2H), 5.31-5.33 (m, 1H), 3.85-3.89 (m, 1H), 3, 72-3.77 (m, 1H), 3.66 (s, 3H), 3.34 (s, 3H). 2-55 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.43 (t, J=7.0 Hz, 1H), 4.02 (dd, J=12.5, 7.0 Hz, 1H), 3.87 (dd, J=12.5, 7.0 Hz, 1H), 3.19 (s, 3H), 2.31 (s, 3H). 2-56 ¹ H NMR (500 MHz, Chloroform-d) δ 5.97 (s, 1H), 4.46 (s, 2H), 3.71 (s, 3H), 1.97 (s, 2H). 2-57 ¹ H NMR (500 MHz, Chloroform-d) δ 5.80 (s, 1H), 4.44 (s, 2H), 3.71 (s, 3H), 2.23 (s, 3H). 2-58 ¹ H NMR (500 MHz, Chloroform-d) δ 6.17 (s, 1H), 4.45 (s, 2H), 3.71 (s, 3H), 3.42 (s, 3H). 2-59 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.49 (t, J=7.0 Hz, 1H), 3.72 (s, 3H), 3.14 (dd, J=12.5, 7.1 Hz, 1H), 2.62 (dd, J=12.5, 7.0 Hz, 1H), 2.25 (s, 6H). 2-60 ¹ H NMR (500 MHz, Chloroform-d) δ 4.91 (t, J=7.0 Hz, 1H), 4.45 (s, 2H), 3.85 (s, 3H), 3.33- 3.37 (m, 1H), 2.95-3.00 (m, 1H). 2-61 ¹ H NMR (500 MHz, Chloroform-d) δ 5.76 (s, 1H), 4.45 (s, 2H), 3.75 (s, 3H). 2-62 ¹ H NMR (500 MHz, Chloroform-d) δ 7.61-7.63 (m, 2H), 7.38-7.45 (m, 3H), 6.13 (s, 1H), 5.18 (s, 2H), 3.73 (s, 3H). 2-63 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.33-7.40 (m, 2H), 7.20-7.28 (m, 2H), 7.15-7.23 (m, 1H ), 6.76 (s, 2H), 5.22 (t, J=7.0 Hz, 1H), 3.72 (s, 3H), 3.31-2.98 (m, 2H). 2-64 ¹ H NMR (500 MHz, Chloroform-d) δ 7.61-7.63 (m, 2H), 7.38-7.45 (m, 2H), 6.13 (s, 1H), 5.18 (s, 2H), 3.73 (s, 3H). 2-65 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.41 (dd, J=7.5, 1.5 Hz, 1H), 7.17 (dd, J=7.5, 1.5 Hz, 1H), 7.06 (t, J=7.5 Hz, 1H), 6.82 (s, 2H), 6.22 (s, 1H), 3.66 (s, 3H). 2-67 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.27 (s, 1H), 6.82 (s, 2H), 6.14 (s, 1H), 3.66 (s, 3H). 2-68 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.50 (d, J=8.0 Hz, 1H), 7.23 (s, 2H), 5.81 (s, 1H), 3.67 (s, 3H). 2-69 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.04 (s, 2H), 5.15 (q, J=7.0 Hz, 1H), 3.65 (s, 3H), 1.50 (d, J=7.0 Hz, 3H). 2-70 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 2.31 (s, 3H), 1.54 (d, J=7.0 Hz, 3H). 2-71 ¹ H NMR (500 MHz, Chloroform-d) δ 5.24 (q, J=7.0 Hz, 1H), 5.15 (s, 2H), 4.19-4.25 (m, 2H), 1.64 (d, J=7.5 Hz, 3H), 1.27 (t, J=7.5 Hz, 3H). 2-72 ¹ H NMR (500 MHz, Chloroform-d) δ 5.52 (q, J=7.0 Hz, 1H), 5.19 (s, 2H), 2.84-2.92 (m, 2H), 1.60 (d, J=7.0 Hz, 3H), 1.25 (t, J=7.5 Hz, 3H). 2-73 ¹ H NMR (500 MHz, Chloroform-d) δ 5.25 (q, J=7.0 Hz, 1H), 5.14 (s, 2H), 4.09-4.15 (m, 2H), 1.55-1.68 (m, 5H), 0.92 (t, J=7.5 Hz, 3H). 2-74 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.97 (q, J=7.0 Hz, 1H), 3.42 (td, J=12.5, 3.0 Hz, 1H), 2.90 (td, J=12.5, 2.5 Hz, 1H), 1.71-1.86 (m, 1H), 1.54 (d, J=7 .0 Hz, 3H), 1.34-1.44 (m, 1H), 0.98 (t, J=8.0 Hz, 3H). 2-75 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.03 (s, 2H), 5.03 (q, J=7.0 Hz, 1H), 4.89-4.94 (m, 1H) , 1.49 (d, J=7.0 Hz, 3H), 1.19 (d, J=6.5 Hz, 3H), 1.14 (d, J=6.5 Hz, 3H). 2-76 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.00 (q, J=7.0 Hz, 1H), 3.36 (dq, J=13.5, 7.0 Hz, 1H), 1.54 (d, J=7.0 Hz, 3H), 1.30 (s, 6H). 2-77 ¹ H NMR (500 MHz, Chloroform-d) δ 5.24 (q, J=7.0 Hz, 1H), 5.15 (s, 2H), 4.12-4.20 (m, 2H), 1.59-1.64 (m, 5H), 1.31-1.38 (m, 2H), 0.89-0.93 (m, 3H). 2-78 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.29 (td, J=12.5, 3.5Hz, 1H), 3.04(td, J=12.5, 2.5Hz, 1H), 1.62-1.75(m, 1H), 1.44-1.57(m , 4H), 1.33-1.41 (m, 1H), 1.14-1.27 (m, 1H), 0.92 (t, J=8.0 Hz, 3H). 2-79 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 4.23 (dd, J=12.5, 7.0 Hz, 1H), 3.12 (dd, J=12.5, 7.0 Hz, 1H), 1.93-2.01 (m, 1H), 1.51 (d, J=7 .0 Hz, 3H), 0.88 (d, J=7.0 Hz, 6H). 2-80 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.01 (q, J=7.0 Hz, 1H), 3.56 (dd, J=12.5, 7.0 Hz, 1H), 2.89 (dd, J=12.5, 7.0 Hz, 1H), 1.73 (dp, J=13.5, 7.0 Hz, 1H), 1, 54 (d, J=7.0 Hz, 3H), 0.92 (dd, J=25.7.0 Hz, 6H). 2-81 ¹ H NMR (500 MHz, Chloroform-d) δ 5.17-5.20 (m, 1H), 5.14 (s, 2H), 4.86-4.94 (m, 1H), 1.51 -1.66 (m, 5H), 1.18-1.28 (m, 3H), 0.83-0.95 (m, 3H) 2-82 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.79 (s, 2H), 5.00 (q, J=7.0 Hz, 1H), 2.88-2.95 (m, 1H) , 2.21-2.27 (m, 1H), 1.51-1.62 (m, 4H), 1.32 (d, J=7.0 Hz, 3H), 0.88 (t, J =8.0 Hz, 3H). 2-83 ¹ H NMR (500 MHz, Chloroform-d) δ 5.14 (s, 2H), 5.09 (q, J=7.0 Hz, 1H), 1.60 (d, J=7.0 Hz, 3H), 1.46 (s, 9H). 2-84 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.01 (q, J=7.0 Hz, 1H), 1.53 (d, J=7.0 Hz , 3H), 1.32 (s, 9H). 2-85 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 4.07-3.97 (m, 1H) , 3.90 (td, J=12.5, 3.0 Hz, 1H), 1.52 (d, J=7.0 Hz, 3H), 1.32-1.13 (m, 6H), 0.90 (t, J=7.0 Hz, 3H). 2-86 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.97 (q, J=7.0 Hz, 1H), 3.41 (td, J=12.5, 3.5 Hz, 1H), 2.89 (td, J=12.5, 2.5 Hz, 1H), 1.69-1.75 (m, 1H), 1.54 (d, J=6 .5 Hz, 3H), 1.10-1.38 (m, 4H), 0.84-0.92 (m, 2H), 0.88 (s, 2H). 2-87 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 4.15 (dd, J=12.5, 7.0 Hz, 1H), 3.67 (dd, J=12.5, 7.0 Hz, 1H), 1.72-1.85 (m, J=7.0 Hz, 1H), 1, 51 (d, J=7.0 Hz, 3H), 1.23-1.35 (m, 1H), 1.07-1.20 (m, 1H), 0.83-0.92 (m, 6H). 2-88 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.00 (q, J=7.Hz, 1H), 3.28 (dd, J=12.5.7 .0 Hz, 1H), 2.74 (dd, J=12.5, 7.0 Hz, 1H), 1.61-1.74 (m, 1H), 1.54 (d, J=7, 0 Hz, 3H), 1.28-1.41 (m, 1H), 1.08-1.14 (m, 1H), 0.91 (d, J=7.0 Hz, 3H), 0, 84 (t, J=8.0 Hz, 3H). 2-89 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 4.43-4.47 (m, 1H) , 3.44-3.50 (m, 1H), 1.77-1.85 (m, 1H), 1.51 (d, J=7.0 Hz, 3H), 1.42-1.47 (m, 1H), 1.24-1.31 (3, 1H), 0.97 (d, J=7.0 Hz, 6H). 2-90 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=6.9 Hz, 1H), 3.51 (td, J=12.2, 4.2Hz, 1H), 2.89(td, J=12.3, 3.1Hz, 1H), 1.68-1.58(m, 1H), 1.62-1.44(m , 5H), 0.85 (dd, J=25.0, 6.7 Hz, 6H). 2-91 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.68 (q, J=7.0 Hz, 1H), 3.50-3.61 (m, 2H) , 1.53 (d, J=7.0 Hz, 3H), 1.05 (s, 9H). 2-92 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99-5.03 (m, 1H), 3.70 (d, J=12.5 Hz, 1H) , 2.84 (d, J=12.5 Hz, 1H), 1.54 (d, J=7.0 Hz, 3H), 0.86 (s, 9H). 2-93 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.68 (q, J=7.0 Hz, 2H), 1.52 (d, J=7.0 Hz , 3H), 1.34-1.48 (m, 1H), 1.13-1.25 (m, 5H), 1.03-1.16 (m, 1H), 0.81 (t, J =8.0 Hz, 3H). 2-94 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.79 (s, 2H), 5.02 (q, J=7.0 Hz, 1H), 3.27-3.34 (m, 1H) , 2.15-2.22 (m, 1H), 1.45-1.57 (m, 4H), 1.29 (d, J=7.0 Hz, 3H), 1.02-1.23 (m, 2H), 0.79 (t, J=8.0 Hz, 3H). 2-95 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.66-4.75 (m, 2H), 1.92-2.05 (m, J=7.0 Hz, 1H), 1.52 (d, J=7.0 Hz, 3H), 1.17 (d, J=7.0 Hz, 3H), 0.79 (d, J=7.0 Hz, 6H). 2-96 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.00 (q, J=7.0 Hz, 1H), 3.08-3.13 (m, 1H) , 1.73-1.80 (m, 1H), 1.54 (d, J=7.0 Hz, 3H), 1.34 (d, J=7.0 Hz, 3H), 0.84- 0.90 (m, 6H). 2-97 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.64-4.72 (m, 1H), 3.07-3.12 (m, 1H), 1, 52 (d, J=7.0 Hz, 3H), 1.25-1.32 (m, 4H), 0.83 (t, J=8.0 Hz, 6H). 2-98 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99-5.03 (m, 1H), 2.89-2.94 (m, 1H), 1, 94 -2.08 (m, 2H), 1.54 (d, J=7.0 Hz, 3H), 1.37-1.45 (m, 2H), 0.82 (t, J=8, 0 Hz, 6H). 2-99 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.68 (q, J=7.0 Hz, 1H), 1.56-1.63 (m, 1H) , 1.52 (d, J=7.0 Hz, 3H), 1.34-1.45 (m, 7H), 0.84 (t, J=8.0 Hz, 3H). 2-100 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99-5.03 (m, 1H), 2.20-2.27 (m, 1H), 1, 44-1.56 (m, 4H), 1.35 (s, 3H), 1.30 (s, 3H), 0.82 (t, J=8.0 Hz, 3H). 2-101 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 3.89-4.02 (m, 2H) , 1.52 (d, J=6.5 Hz, 3H), 1.11-1.31 (m, 8H), 0.85-0.89 (m, 3H). 2-102 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.00 (q, J=7.0 Hz, 1H), 3.41-3.47 (m, 1H) , 2.86-2.92 (m, 1H), 1.54-1.65 (m, 1H), 1.54 (d, J=7.0 Hz, 3H), 1.09-1.41 (m, 6H), 1.00-1.12 (m, 1H), 0.87 (t, J=8.0 Hz, 3H). 2-103 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 4.23 (dd, J=12.5, 7.0 Hz, 1H), 3.57 (dd, J=12.5, 7.0 Hz, 1H), 1.67-1.81 (m, 1H), 1.40-1.54 (m , 4H), 1.25-1.30 (m, 1H), 1.14-1.22 (m, 1H), 1.00-1.10 (m, 1H), 0.79-0.89 (m, 6H). 2-104 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.15-3.19 (m, 1H) , 2.82-2.90 (m, 1H), 1.63-1.70 (m, 1H), 1.49-1.60 (m, 4H), 1.35-1.40 (m, 1H), 1.12-1.26 (m, 2H), 0.79-0.91 (m, 6H). 2-105 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 4.10-4.20 (m, 1H) , 3.84-3.93 (m, 1H), 1.52 (d, J=7.0 Hz, 3H), 1.23-1.39 (m, 4H), 1.09-1.20 (m, 1H), 0.83-0.92 (m, 6H). 2-106 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.50-3.56 (m, 1H) , 2.86-2.92 (m, 1H), 1.85-1.92 (m, 1H), 1.54 (d, J=7.0 Hz, 3H), 1.19-1.46 (m, 3H), 1.08-1.20 (m, 1H), 0.81-0.88 (m, 6H). 2-107 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.68 (q, J=7.0 Hz, 1H), 4.42-4.48 (m, 1H) , 3.49-3.45 (m, 1H), 1.53 (dd, J=16.5, 7.0 Hz, 4H), 1.39-1.51 (m, 1H), 1.26 -1.33(m, 1H), 1.16-1.23(m, 1H), 1.03-1.16(m, 1H), 0.92(d, J=7.0Hz, 3H ), 0.90 (d, J=7.0 Hz, 3H). 2-108 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.25-3.31 (m, 1H) , 2.99-3.04 (m, 1H), 1.72-1.85 (m, 1H), 1.48-1.56 (m, 4H), 1.37-1.46 (m, 1H), 1.14-1.31 (m, 2H), 0.88-0.94 (m, 6H). 2-113 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.64-4.78 (m, 1H), 1.52 (d, J=7.0 Hz, 3H) , 1.33-1.47 (m, 4H), 1.05-1.26 (m, 6H), 0.88 (t, J=8.0 Hz, 3H). 2-114 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.79 (s, 2H), 4.99-5.03 (m, 1H), 3.00-3.10 (m, 1H), 2, 13-2.22 (m, 1H), 1.42-1.57 (m, 6H), 1.31 (d, J=7.0 Hz, 3H), 1.11-1.30 (m, 2H), 0.88 (t, J=7.5 Hz, 3H). 2-121 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 3.98-4.03 (m, 1H) , 3.95-3.85 (m, 1H), 1.52 (d, J=7.0 Hz, 3H), 1.13-1.32 (m, 8H), 0.83-0.91 (m, 2H), 0.87 (t, J=7.5 Hz, 3H). 2-122 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.23-3.33 (m, 1H) , 2.96-3.06(m, 1H), 1.48-1.63(m, 6H), 1.09-1.30(m, 7H), 0.85-.88(m, 3H ). 2-155 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 3.90 -4.02 (m, 2H) , 1.52 (d, J = 7.0 Hz, 3H), 1.31-1.43 (m, 1H), 1.16-1.31 (m, 10H), 1.17 (s, 1H ), 0.87 (t, J=7.5 Hz, 3H). 2-156 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.00 (q, J=7.0 Hz, 1H), 3.26 (dd, J=12.5, 7.0 Hz, 1H), 2.78 (dd, J=12.5.7.0 Hz, 1H), 1.36-1.71 (m, 8H), 1.09-1.25 (m , 2H), 0.99-1.12 (m, 2H), 0.82-0.90 (m, 6H). 2-157 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.68 (q, J=7.0 Hz, 1H), 4.14 (dd, J=12.5, 7.0 Hz, 1H), 3.82 (dd, J=12.5, 7.0 Hz, 1H), 1.66-1.68 (m, 1H), 1.49-1.62 (m , 4H), 1.36-1.52 (m, 2H), 1.03-1.29 (m, 4H), 0.94-0.99 (m, 4H), 0.88 (t, J =8.0 Hz, 3H). 2-158 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.00 (q, J=7.0 Hz, 1H), 3.26 (dd, J=12.5, 7.0 Hz, 1H), 2.78 (dd, J=12.5, 7.0 Hz, 1H), 1.71-1.36 (m, 8H), 1.25-1.09 (m , 2H), 1.12-0.99 (m, 2H), 0.90-0.80 (m, 6H). 2-159 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 3.89-4.02 (m, 2H) , 1.52 (dd, J=7.0, 3.0 Hz, 4H), 1.35-1.49 (m, 1H), 1.00-1.34 (m, 7H), 0.93 (d, J=7.0 Hz, 3H), 0.89 (d, J=7.0 Hz, 3H). 2-160 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.23-3.45 (m, 1H) , 2.95-3.06 (m, 1H), 1.47-1.63 (m, 7H), 1.34-1.50 (m, 1H), 1.19-1.31 (m, 1H), 1.15-1.18 (m, 2H), 1.00-1.15 (m, 1H), 0.91 (dd, J=25.0, 7.0 Hz, 6H). 2-163 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.68 (q.d., J=7.0, 2.0 Hz, 2H), 1.52 (d, J=7.0 Hz, 3H), 1.46-1.35(m, 1H), 1.28(s, 1H), 1.20-1.29(m, 1H), 1.12-1 .24 (m, 9H), 1.00-1.10 (m, 1H), 0.86-0.88 (m, 3H). 2-164 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.00 (q, J=7.0 Hz, 1H), 3.09-3.20 (m, 1H) , 1.68-1.79 (m, 1H), 1.54 (d, J=6.5 Hz, 3H), 1.32-1.45 (m, 2H), 1.29 (d, J =7.0 Hz, 3H), 1.16-1.19 (m, 6H), 1.13 (s, 1H), 0.86-0.88 (m, 3H). 2-175 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 3.86 -4.04 (m, 2H) , 1.52 (d, J = 7.0 Hz, 3H), 1.12-1.31 (m, 14H), 0.86-0.89 (m, 3H). 2-176 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.79 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.24-3.33 (m, 1H) , 2.96-3.06 (m, 1H), 1.47-1.62 (m, 5H), 1.14-1.31 (m, 11H), 1.07-1.17 (m, 1H), 0.85-0.89 (m, 3H). 2-195 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 3.89-4.01 (m, 2H) , 1.52 (d, J=7.0 Hz, 3H), 1.08-1.33 (m, 16H), 0.84-0.90 (m, 3H). 2-196 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.23-3.33 (m, 1H) , 2.96-3.06 (m, 1H), 1.49-1.62 (m, 5H), 1.11-1.26 (m, 14H), 0.82-0.93 (m, 3H). 2-215 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 3.91-4.01 (m, 2H) , 1.52 (d, J=7.0 Hz, 3H), 1.21-1.31 (m, 2H), 1.12-1.24 (m, 16H), 0.83-0.91 (m, 3H) 2-216 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.23-3.33 (m, 1H) , 2.96-3.06 (m, 1H), 1.48-1.62 (m, 5H), 1.11-1.27 (m, 16H), 0.82-0.92 (m, 3H). 2-235 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 4.00-4.05 (m, 1H) , 3.83-3.92 (m, 1H), 1.52 (d, J=7.0 Hz, 3H), 109-1.32 (m, 20H), 0.82-0.92 (m , 3H). 2-236 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.23-3.33 (m, 1H) , 2.96-3.06 (m, 1H), 1.48-1.26 (m, 15H), 0.81-0.91 (m, 11H). 2-263 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.77 (s, 2H), 4.62 (q, J=7.0 Hz, 1H), 3.32 (p, J=7.0 Hz , 1H), 1.50 (d, J=7.0 Hz, 3H), 0.44-0.48 (m, 2H), 0.23-0.35 (m, 2H). 2-264 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.68 (q, J=7.0 Hz, 1H), 4.49 (p, J=7.0 Hz , 1H), 2.09-2.20 (m, 2H), 1.78-1.92 (m, 3H), 1.63-1.76 (m, 1H), 1.52 (d, J =7.0 Hz, 3H). 2-265 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.87 (p, J=7.0 Hz, 1H), 4.68 (q, J=7.0 Hz , 1H), 1.73-1.80 (m, 2H), 1.58-1.67 (m, 2H), 1.42-1.56 (m, 6H), 1.40-1.45 (m, 1H). 2-266 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.76 (s, 2H), 4.96 (s, 1H), 2.95 (s, 1H), 1.49-1.70 (m, 4H), 1.52 (s, 4H), 1.32-1.38 (m, 3H), 1.04-1.09 (m, 2H). 2-267 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.40 (d, J=12.5 Hz, 1H), 4.89 (d, J=12.5 Hz , 1H), 4.67 (q, J=7.0 Hz, 1H), 1.53 (d, J=7.0 Hz, 3H). 2-268 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.32 (d, J=12.5 Hz, 1H), 6.80 (s, 2H), 6.29 (d, J=12.5 Hz , 1H), 4.66 (q, J=7.0 Hz, 1H), 1.56 (d, J=7.0 Hz, 3H). 2-270 ¹ H NMR (500 MHz, Chloroform-d) δ 4.49-4.58 (m, 2H), 4.45 (s, 2H), 3.72-3.62 (m, 1H), 3.60 -3.50 (m, 2H), 3.37 (s, 3H), 2.51 (s, 3H), 1.68 (d, J=7.0 Hz, 3H). 2-271 ¹ H NMR (500 MHz, Chloroform-d) δ 4.67 (q, J=6.5 Hz, 1H), 4.45 (s, 2H), 4.20-4.09 (m, 2H), 3.38-3.12 (m, 3H), 3.04-2.95 (m, 1H), 1.61 (d, J=6.5 Hz, 3H), 1.59 -1.15 ( m, 4H), 1.03 (t, J=7.5 Hz, 3H). 2-272 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.79 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 3.37 (td, J=12.5, 3.0Hz, 1H), 3.30 (td, J=12.0, 1.5Hz, 1H), 3.21 (dt, J=12.5, 3.0Hz, 1H), 3, 18 (s, 3H), 2.98 (td, J=12.5, 3.5 Hz, 1H), 1.64-1.74 (m, 1H), 1.60 (tt, J=12, 0, 3.5 Hz, 1H), 1.54 (d, J=7.0 Hz, 3H). 2-273 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 5.94-6.02 (m, 1H), 5.28-5.37 (m, 1H), 5, 20-5.31 (m, 1H), 4.55-4.70 (m, 3H), 1.53 (d, J=7.0 Hz, 3H). 2-274 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.96 (q, J=7.0 Hz, 1H), 4.14 (dd, J=12.5, 3.0 Hz, 1H), 3.53 (dd, J=12.5, 3.0 Hz, 1H), 3.09 (t, J=3.0 Hz, 1H), 1.61 (d, J=7.0 Hz, 3H). 2-275 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.71 (dd, J=12.5, 3.0 Hz, 1H), 4.59-4.70 ( m, 2H), 3.55 (t, J=3.0 Hz, 1H), 1.52 (d, J=7.0 Hz, 3H). 2-276 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.50-4.83m, 3H), 4.25-4.48 (m, 2H), 1.50 ( e, J=7.0 Hz, 3H). 2-277 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.83 (dt, J=12.5, 1.5 Hz, 1H), 4.70 (q, J= 7.0 Hz, 1H), 3.78-3.89 (m, 2H), 3.46-3.51 (m, 1H), 1.52 (d, J=7.0 Hz, 3H). 2-278 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.68 (q, J=7.0 Hz, 1H), 4.54 (dt, J=12.5, 2.0 Hz, 1H), 4.39-4.44 (m, 1H), 3.61 (dt, J=12.5, 2.0 Hz, 1H), 3.29-3.34 (m , 1H), 1.48 (d, J=7.0 Hz, 3H). 2-279 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.86 (t, J=7.0 Hz, 1H), 4.68-4.78 (m, 1H) , 4.62-4.72 (m, 1H), 3.74-3.87 (m, 1H), 1.52 (d, J=7.0 Hz, 3H). 2-280 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.06 (s, 2H), 5.13-5.14 (m, 1H), 4.15-4.17 (m, 2H), 2, 12-2.26(m, 2H), 1.74-1.77(m, 2H), 1.43-1.52(m, 3H). 2-281 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 5.17-5.25 (m, 1H), 4.66 (q, J=7.0 Hz, 1H) , 4.03-4.09 (m, 1H), 1.53 (d, J=7.0 Hz, 3H). 2-282 ¹ H NMR (500 MHz, Chloroform-d) δ 4.77-5.00 (m, 2H), 4.59 (q, J=7.0 Hz, 1H), 4.45 (s, 2H), 1.69 (d, J=7.0 Hz, 3H). 2-283 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 4.67 (q, J=7.0 Hz, 1H), 4.37-4.42 (m, 1H) , 4.02-4.08 (m, 1H), 2.75 (s, 6H), 2.59-2.62 (m, 1H), 1.79-1.89 (m, 1H), 1 .52 (d, J=7.0 Hz, 3H). 2-284 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.66 (q, J=7.0 Hz, 1H), 4.45-4.50 (m, 1H) , 3.46-3.51 (m, 1H), 2.80 (s, 2H), 2.60-2.74 (m, 2H), 1.52 (d, J=7.0 Hz, 3H ). 2-285 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.81 (s, 2H), 6.24-6.28 (m, 1H), 6.01-6.07 (m, 1H), 4, 61-4.72 (m, 3H), 1.53 (d, J=7.0 Hz, 3H). 2-286 ¹ H NMR (500 MHz, Chloroform-d) δ 6.07 (d, J=12.5 Hz, 1H), 4.57 (q, J=7.0 Hz, 1H), 4.43 (s, 2H), 4.25 (d, J=12.5 Hz, 1H), 1.67 (d, J=7.0 Hz, 3H). 2-287 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.00 (s, 2H), 5.11 (q, J=7.0 Hz, 1H), 4.31-4.27 (m, 1H) , 4.20-4.15 (m, 1H), 4.08-4.00 (m, 2H), 1.75 (s, 3H), 1.66 (s, 3H), 1.48 (d , J=7.0 Hz, 3H). 2-288 ¹ H NMR (500 MHz, Chloroform-d) δ 5.90-5.98 (m, 1H), 5.13-5.26 (m, 1H), 5.22-5.11 (m, 1H) , 4.94-4.86 (m, 1H), 4.68-4.59 (m, 2H), 4.45 (s, 2H), 1.69 (d, J=7.0 Hz, 3H ), 1.62 (s, 3H), 1.57 (s, 3H). 2-289 ¹ H NMR (500 MHz, Chloroform-d) δ 5.32 (d, J=12.5 Hz, 1H), 5.03 (d, J=12.5 Hz, 1H), 4.70 (q, J=6.5Hz, 1H), 4.47(s, 2H), 2.95(s, 3H), 2.84(s, 3H), 1.61(d, J=6.5Hz, 3H). 2-290 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.82 (s, 2H), 5.13 (q, J=7.0 Hz, 1H), 4.26 (d, J=12.5 Hz , 1H), 3.73 (d, J=12.5 Hz, 1H), 3.67 (s, 3H), 1.50 (d, J=7.0 Hz, 3H). 2-291 ¹ H NMR (500 MHz, Chloroform-d) δ 6.00 (dd, J=10.0, 1.5 Hz, 1H), 4.59 (q, J=6.5 Hz, 1H), 4, 45 (s, 2H), 3.27 (s, 3H), 1.77-1.68 (m, 4H), 1.23-0.87 (m, 4H). 2-292 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.79 (s, 2H), 4.73 (q, J=7.0 Hz, 1H), 2.47 (s, 3H), 2.41 (s, 3H), 1.50 (d, J=7.0 Hz, 3H). 2-294 ¹ H NMR (500 MHz, Chloroform-d) δ 5.04 (d, J=12.5 Hz, 1H), 4.89 (d, J=12.5 Hz, 1H), 4.60 (q, J=7.0 Hz, 1H), 4.45 (s, 2H), 4.23-4.30 (m, 2H), 1.69 (d, J=7.0 Hz, 3H), 1, 22 (t, J=8.0 Hz, 3H). 2-295 ¹ H NMR (500 MHz, Chloroform-d) δ 5.32 (q, J=7.0 Hz, 1H), 4.62 (q, J=7.0 Hz, 1H), 4.45 (s, 2H), 3.85 (s, 3H), 1.73 (d, J=7.0 Hz, 3H), 1.59 (d, J=7.0 Hz, 3H). 2-296 ¹ H NMR (500 MHz, Chloroform-d) δ 7.82 (q, J=6.5 Hz, 1H), 4.57 (q, J=6.5 Hz, 1H), 4.45 (s, 2H), 4.01 (s, 3H), 1.69-1.52 (m, 6H). 2-297 ¹ H NMR (500 MHz, Chloroform-d) δ 6.29 (t, J=7.0 Hz, 1H), 4.57 (q, J=7.0 Hz, 1H), 4.45 (s, 2H), 3.93-3.97(m, 1H), 3.81-3.85(m, 1H), 2.09-1.89(m, 2H), 1.65-1.72( m, 4H), 1.53-1.59 (m, 1H). 2-298 ¹ H NMR (500 MHz, Chloroform-d) δ 5.28 (q, J=7.0 Hz, 1H), 5.15 (s, 2H), 4.27-4.07 (m, 3H), 3.91-3.73 (m, 2H), 2.04-1.82 (m, 3H), 1.66 (d, J=7.0 Hz, 3H), 1.59-1.54 ( m, 1H). 2-299 ¹ H NMR (500 MHz, Chloroform-d) δ 7.47-7.39 (m, 1H), 7.41-7.33 (m, 2H), 7.04-6.98 (m, 2H) , 4.60 (q, J=7.0 Hz, 1H), 4.42 (s, 2H), 1.76 (d, J=7.0 Hz, 3H). 2-300 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.34-7.27 (m, 5H), 7.05 (s, 2H), 5.20-5.17 (m, 3H), 1, 53 (d, J=7.0 Hz, 3H). 2-301 ¹ H NMR (500 MHz, Chloroform-d) δ 7.25-7.34 (m, 5H), 5.59 (q, J=7.0 Hz, 1H), 5.21 (s, 2H), 4.15 (s, 2H), 1.65 (d, J=7.0 Hz, 3H). 2-302 ¹ H NMR (500 MHz, Chloroform-d) δ 7.31-7.17 (m, 4H), 5.77-5.79 (m, 1H), 4.68-4.71 (m, 1H) , 4.55 (q, J=7.0 Hz, 1H), 4.42 (s, 2H), 2.25 (s, 3H), 1.67 (d, J=7.0 Hz, 3H) . 2-303 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.17-7.20 (m, 1H), 7.10-7.19 (m, 2H), 7.02-7.06 (m, 1H ), 6.76 (s, 2H), 4.92 (kv, J=7.0 Hz, 1H), 4.49 (dt, J=12.0, 1.0 Hz, 1H), 4.30 -4.40 (m, 1H), 2.23 (d, J=1.5 Hz, 3H), 1.31 (d, J=7.0 Hz, 3H). 2-304 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.38 (t, J=7.5 Hz, 1H), 7.31-7.33 (m, 2H), 7.02-7.04 ( m, 1H), 6.78 (s, 2H), 5.04-5.16 (m, 2H), 4.65 (q, J=7.0 Hz, 1H), 2.22 (d, J =2.0 Hz, 1H), 2.22 (s, 2H), 1.51 (d, J=7.0 Hz, 3H). 2-305 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.25-7.34 (m, 2H), 7.22-7.29 (m, 1H), 6.93-6.99 (m, 1H ), 6.77 (s, 2H), 4.99 (kv, J=7.0 Hz, 1H), 4.41-4.51 (m, 1H), 4.10-4.17 (m, 1H), 2.22 (d, J=2.0 Hz, 1H), 2.22 (s, 2H), 1.53 (d, J=7.0 Hz, 3H). 2-306 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.39-7.46 (m, 2H), 7.17-7.23 (m, 2H), 6.78 (s, 2H), 5, 10 (dt, J=12.5, 1.0 Hz, 1H), 5.04 (d, J=12.5 Hz, 1H), 4.65 (kv, J=7.0 Hz, 1H), 2.21 (d, J=2.0 Hz, 1H), 2.21 (s, 2H), 1.51 (d, J=7.0 Hz, 3H). 2-307 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.31 (dt, J=7.5, 1.0 Hz, 2H), 7.09 (dd, J=7.5, 1.5 Hz, 2H), 6.77 (s, 2H), 4.99 (q, J=7.0 Hz, 1H), 4.47 (dt, J=12.5, 1.0 Hz, 1H), 4, 10 (dt, J=12.5, 1.0 Hz, 1H), 2.21 (d, J=2.0 Hz, 1H), 2.21 (s, 2H), 1.54 (d, J =7.0 Hz, 3H). 2-308 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.39-7.46 (m, 1H), 7.28-7.40 (m, 2H), 7.14-7.48 (m, 1H ), 6.78 (s, 2H), 5.43 (dd, J=12.5, 1.0 Hz, 1H), 5.07 (d, J=12.5 Hz, 1H), 4.66 (q, J=7.0 Hz, 1H), 1.52 (d, J=7.0 Hz, 3H). 2-309 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.23-7.31 (m, 3H), 7.07 (td, J=7.5, 2.0 Hz, 1H), 6.77 ( s, 2H), 4.99 (q, J=7.0 Hz, 1H), 4.52 (d, J=12.5 Hz, 1H), 4.35 (dd, J=12.5.1 .0 Hz, 1H), 1.54 (d, J=7.0 Hz, 3H). 2-310 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.37-7.41 (m, 1H), 7.28-7.30 (m, 1H), 7.22-7.24 (m, 1H ), 7.00-7.04 (m, 1H), 6.77 (s, 2H), 5.40 (dt, J=12.5, 1.0 Hz, 1H), 4.87 (d, J=12.5Hz, 1H), 4.64(q, J=7.0Hz, 1H), 1.50(d, J=7.0Hz, 3H). 2-311 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.33 (td, J=7.5, 5.5 Hz, 1H), 7.21 (dkv, J=7.5, 2.0 Hz, 1H), 7.10 (dkv, J=9.0, 2.0 Hz, 1H), 6.93-6.97 (m, 1H), 6.76 (s, 2H), 4.74 (dt , J=12.5, 1.0 Hz, 1H), 4.52 (q, J=6.5 Hz, 1H), 4.19 (d, J=12.5 Hz, 1H), 1.51 (d, J=7.0 Hz, 3H). 2-312 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.37-7.41 (m, 2H), 7.17-7.25 (m, 2H), 6.75 (s, 2H), 5, 58-5.65 (m, 1H), 4.58-4.69 (m, 2H), 1.49 (d, J=7.0 Hz, 3H). 2-313 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.41-7.45 (m, 2H), 7.08-7.16 (m, 2H), 6.76 (s, 2H), 4, 64 (dt, J=12.0, 1.0 Hz, 1H), 4.58 (kv, J=7.0 Hz, 1H), 4.11 (d, J=12.5 Hz, 1H), 1.51 (d, J=7.0 Hz, 3H). 2-314 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.39-7.49 (m, 2H), 7.24 (td, J=7.5, 2.0 Hz, 1H), 7.10 ( td, J=7.5, 2.0 Hz, 1H), 6.77 (s, 2H), 5.56 (d, J=12.5 Hz, 1H), 4.85 (dd, J=12 .5, 1.0 Hz, 1H), 4.64 (q, J=7.0 Hz, 1H), 1.52 (d, J=7.0 Hz, 3H). 2-315 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.39 (dd, J=7.5, 2.0 Hz, 1H), 7.24-7.28 (m, 1H), 7.18 ( td, J=7.5, 2.0 Hz, 1H), 7.03 (td, J=7.5, 2.0 Hz, 1H), 6.77 (s, 2H), 5.00 (kv , J=7.0 Hz, 1H), 4.64 (dd, J=12.5,1.0 Hz, 1H), 4.37 (dd, J=12.5, 1.0 Hz, 1H) , 1.54 (d, J=7.0 Hz, 3H). 2-316 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.51 (q, J=1.5 Hz, 1H), 7.27-7.34 (m, 3H), 6.80 (s, 2H) , 5.82 (d, J=12.5 Hz, 1H), 4.64 (q, J=7.0 Hz, 1H), 4.52 (d, J=12.5 Hz, 1H), 1 .47 (d, J=6.5 Hz, 3H). 2-317 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.54 (q, J=1.5 Hz, 1H), 7.25-7.37 (m, 3H), 6.79 (s, 2H) , 4.72 (dt, J=12.5, 1.0 Hz, 1H), 4.49 (q, J=7.0 Hz, 1H), 4.19 (d, J=12.5 Hz, 1H), 1.51 (d, J=7.0 Hz, 3H). 2-318 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.40-7.47 (m, 2H), 7.31-7.37 (m, 2H), 6.75 (s, 2H), 5, 73 (dt, J=12.5, 1.0Hz, 1H), 4.65 (q, J=6.5Hz, 1H), 4.56 (d, J=12.5Hz, 1H), 1.48 (d, J=7.0 Hz, 3H). 2-319 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.37-7.44 (m, 2H), 7.31-7.37 (m, 2H), 6.75 (s, 2H), 5, 03 (kv, J=7.0Hz, 1H), 4.68 (d, J=12.5Hz, 1H), 4.15 (dt, J=12.5, 1.2Hz, 1H), 1.50 (d, J=7.0 Hz, 3H). 2-320 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.65 (dd, J=7.5, 2.0 Hz, 1H), 7.40-7.42 (m, 1H), 7.32 ( td, J=7.5, 2.0 Hz, 1H), 7.25 (td, J=7.5, 2.0 Hz, 1H), 6.77 (s, 2H), 5.58 (d , J=12.5 Hz, 1H), 4.88 (dd, J=12.5, 1.0 Hz, 1H), 4.66 (kv, J=7.0 Hz, 1H), 1.54 (d, J=7.0 Hz, 3H). 2-321 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.50 (dd, J=7.5, 1.5 Hz, 1H), 7.26-7.35 (m, 2H), 7.13- 7.22 (m, 1H), 6.77 (s, 2H), 5.22 (d, J=12.5 Hz, 1H), 5.04 (q, J=7.0 Hz, 1H), 4.05-4.12 (m, 1H), 1.50 (d, J=7.0 Hz, 3H). 2-322 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.61 (q, J=2.0 Hz, 1H), 7.51 (dt, J=7.5, 2.0 Hz, 1H), 7 .45 (dkv, J=7.5, 2.0 Hz, 1H), 7.28 (t, J=7.5 Hz, 1H), 6.83 (s, 2H), 5.81 (dt, J=12.5, 1.0Hz, 1H), 4.64(q, J=7.0Hz, 1H), 4.49(d, J=12.5Hz, 1H), 1.47( e, J=7.0 Hz, 3H). 2-323 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.39-7.49 (m, 3H), 7.22 (t, J=7.5 Hz, 1H), 6.83 (s, 2H) , 4.71 (dt, J=12.5, 1.0 Hz, 1H), 4.48 (q, J=7.0 Hz, 1H), 4.16 (d, J=12.5 Hz, 1H), 1.51 (d, J=7.0 Hz, 3H). 2-324 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.59-7.66 (m, 2H), 7.26-7.33 (m, 2H), 6.77 (s, 2H), 5, 77 (dt, J=12.5, 1.0Hz, 1H), 4.65 (q, J=7.0Hz, 1H), 4.54 (d, J=12.5Hz, 1H), 1.48 (d, J=7.0 Hz, 3H). 2-325 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.52-7.59 (m, 2H), 7.22 (dt, J=7.5, 1.0 Hz, 2H), 6.77 ( s, 2H), 4.99 (kv, J=7.0 Hz, 1H), 4.48 (dt, J=12.5, 1.0 Hz, 1H), 4.13 (dt, J=12 .5, 1.0 Hz, 1H), 1.53 (d, J=7.0 Hz, 3H). 2-327 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.56-7.62 (m, 1H), 7.49 (td, J=7.5, 2.0 Hz, 1H), 7.37- 7.46 (m, 2H), 6.77 (s, 2H), 5.55 (dd, J=12.5, 1.0 Hz, 1H), 5.14 (dd, J=12.5, 1.0 Hz, 1H), 4.63 (q, J=7.0 Hz, 1H), 1.55 (d, J=7.0 Hz, 3H). 2-328 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.52 (dd, J=7.0, 2.0 Hz, 1H), 7.40 (td, J=7.5, 2.0 Hz, 1H), 7.29 (t, J=7.2 Hz, 2H), 6.77 (s, 2H), 5.01 (q, J=7.0 Hz, 1H), 4.66 (d, J=12.5 Hz, 1H), 4.55 (dd, J=12.5, 1.0 Hz, 1H), 1.54 (d, J=7.0 Hz, 3H). 2-329 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.65 (dd, J=2.5, 1.5 Hz, 1H), 7.58 (dkv, J=5.5, 3.0 Hz, 1H), 7.50 (s, 1H), 7.49 (d, J=3.0 Hz, 1H), 6.77 (s, 2H), 5.09-5.18 (m, 2H), 4.64 (q, J=7.0 Hz, 1H), 1.51 (d, J=6.5 Hz, 3H). 2-330 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.60 (d, J=2.0 Hz, 1H), 7.50-7.57 (m, 1H), 7.38-7.46 ( m, 2H), 6.77 (s, 2H), 4.90 (kv, J=7.0 Hz, 1H), 4.59 (dt, J=12.5, 1.0 Hz, 1H), 4.18 (dd, J=12.5, 1.5 Hz, 1H), 1.55 (d, J=7.0 Hz, 3H). 2-331 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.69 (d, J=7.0 Hz, 2H), 7.52-7.58 (m, 2H), 6.78 (s, 2H) , 5.18 (dt, J=12.5, 1.0 Hz, 1H), 5.10 (d, J=12.5 Hz, 1H), 4.65 (kv, J=7.0 Hz, 1H), 1.51 (d, J=7.0 Hz, 3H). 2-332 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.59-7.65 (m, 2H), 7.40-7.46 (m, 2H), 6.78 (s, 2H), 5, 02 (q, J=7.0Hz, 1H), 4.73 (d, J=12.5Hz, 1H), 4.19 (dt, J=12.5, 1.0Hz, 1H), 1.50 (d, J=7.0 Hz, 3H). 2-333 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.71-7.78 (m, 1H), 7.60-7.66 (m, 3H), 6.77 (s, 2H), 5, 59 (d, J=12.5 Hz, 1H), 5.10 (d, J=12.5 Hz, 1H), 4.63 (q, J=7.0 Hz, 1H), 1.55 ( e, J=7.0 Hz, 3H). 2-334 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.64 (dd, J=7.0, 2.0 Hz, 1H), 7.46-7.58 (m, 2H), 7.42- 7.48(m, 1H), 6.76(s, 2H), 5.05(kv, J=7.0Hz, 1H), 4.76(dd, J=12.5, 1.0Hz , 1H), 4.50 (dd, J=12.5, 1.0 Hz, 1H), 1.52 (d, J=7.0 Hz, 3H). 2-335 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.96 (q, J=1.5 Hz, 1H), 7.86 (dt, J=7.5, 2.0 Hz, 1H), 7 .64-7.67 (m, 1H), 7.49 (t, J=7.5 Hz, 1H), 6.77 (s, 2H), 5.69 (d, J=12.5 Hz, 1H), 4.60-4.69 (m, 2H), 1.48 (d, J=7.0 Hz, 3H). 2-336 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.76-7.84 (m, 2H), 7.62-7.69 (m, 1H), 7.45 (t, J=7.5 Hz, 1H), 6.81 (s, 2H), 5.00 (q, J=7.0 Hz, 1H), 4.75 (d, J=12.5 Hz, 1H), 4.23 ( dt, J=12.5, 1.0 Hz, 1H), 1.52 (d, J=7.0 Hz, 3H). 2-337 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.84-7.90 (m, 2H), 7.66-7.73 (m, 2H), 6.76 (s, 2H), 5, 79 (dt, J=12.5, 1.0 Hz, 1H), 4.62-4.70 (m, 2H), 1.49 (d, J=7.0 Hz, 3H). 2-338 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.61-7.68 (m, 2H), 7.46-7.52 (m, 2H), 6.77 (s, 2H), 4, 99 (q, J=7.0 Hz, 1H), 4.75 (d, J=12.5 Hz, 1H), 4.23 (dt, J=12.5, 1.0 Hz, 1H), 1.52 (d, J=7.0 Hz, 3H). 2-339 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.95-8.02 (m, 2H), 7.82-7.90 (m, 2H), 7.81 (dd, J=7.5 , 1.5 Hz, 1H), 7.47-7.56 (m, 2H), 6.11 (s, 2H), 5.07 (kv, J=7.0 Hz, 1H), 1.46 (d, J=7.0 Hz, 3H). 2-340 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.01-8.04 (m, 1H), 7.90-7.99 (m, 3H), 7.66 (dt, J=7.5 , 1.0 Hz, 1H), 7.57 (dd, J=5.5, 3.5 Hz, 2H), 5.92 (s, 2H), 5.53 (dt, J=12.5, 1.0Hz, 1H), 5.00(d, J=12.5Hz, 1H), 4.69(kv, J=7.0Hz, 1H), 1.50(d, J=6, 5 Hz, 3H). 2-341 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.02 (dt, J=7.5, 1.5 Hz, 1H), 7.95 (dkv, J=7.0, 1.5 Hz, 2H), 7.66 (dt, J=7.5, 1.5 Hz, 1H), 7.55-7.66 (m, 2H), 7.38 (td, J=7.5, 1, 5 Hz, 1H), 5.92 (s, 2H), 5.62 (d, J=12.5 Hz, 1H), 5.14 (dd, J=12.5, 1.0 Hz, 1H) , 4.69 (q, J=7.0 Hz, 1H), 1.55 (d, J=7.0 Hz, 3H). 2-342 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.53 (dd, J=5.0, 1.5 Hz, 1H), 7.75 (td, J=8.0, 1.5 Hz, 1H), 7.51 (dt, J=8.0, 1.5 Hz, 1H), 7.28-7.30 (m, 1H), 6.78 (s, 2H), 5.44 (dd , J=12.5, 1.5 Hz, 1H), 5.18 (d, J=12.5 Hz, 1H), 4.65 (kv, J=7.0 Hz, 1H), 1.51 (d, J=7.0 Hz, 3H). 2-343 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.40 (dd, J=5.0, 1.0 Hz, 1H), 7.67 (td, J=8.0, 1.5 Hz, 1H), 7.49 (dt, J=8.0, 1.5 Hz, 1H), 7.28-7.31 (m, 1H), 6.76 (s, 2H), 5.05 (d , J=12.5 Hz, 1H), 5.00 (kv, J=7.0 Hz, 1H), 4.13 (dd, J=12.5, 1.5 Hz, 1H), 1.51 (d, J=7.0 Hz, 3H). 2-344 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.58 (d, J=5.0 Hz, 2H), 7.51-7.56 (m, 2H), 6.77 (s, 2H) , 5.07 (dt, J=12.5, 1.0 Hz, 1H), 4.94 (d, J=12.5 Hz, 1H), 4.65 (kv, J=7.0 Hz, 1H), 1.51 (d, J=7.0 Hz, 3H). 2-345 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.40 (d, J=5.0 Hz, 2H), 7.38 (d, J=5.0 Hz, 2H), 6.77 (s , 2H), 4.95 (q, J=7.0 Hz, 1H), 4.48 (d, J=12.5 Hz, 1H), 4.11 (d, J=12.5 Hz, 1H ), 1.54 (d, J=7.0 Hz, 3H). 2-346 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.59 (dd, J=5.0, 1.5 Hz, 1H), 8.43 (d, J=1.0 Hz, 1H), 8 .01 (dd, J=8.0, 5.0 Hz, 1H), 7.53 (dt, J=8.0, 1.5 Hz, 1H), 6.77 (s, 2H), 4, 99 (d, J=12.5 Hz, 1H), 4.93 (d, J=12.5 Hz, 1H), 4.64 (q, J=7.0 Hz, 1H), 1.51 ( e, J=7.0 Hz, 3H). 2-347 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.39-8.49 (m, 2H), 7.59 (dt, J=8.0, 1.5 Hz, 1H), 7.36 ( dd, J=8.0, 5.0 Hz, 1H), 6.77 (s, 2H), 4.96 (q, J=7.0 Hz, 1H), 4.46 (d, J=12 .5 Hz, 1H), 4.10 (d, J=12.5 Hz, 1H), 1.54 (d, J=7.0 Hz, 3H). 2-348 ¹ H NMR (500 MHz, Chloroform-d) δ 7.41 (d, J=2.0 Hz, 1H), 6.41 (d, J=3.5 Hz, 1H), 6.36 (dd, J=3.5, 2.0Hz, 1H), 5.25(q, J=7.0Hz, 1H), 5.20-5.08(m, 4H), 1.63(d, J =7.0 Hz, 3H). 2-349 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.46 (d, J=7.5 Hz, 1H), 7.25 (d, J=1.5 Hz, 1H), 6.81 (s , 2H), 6.37 (dd, J=7.5, 1.5 Hz, 1H), 5.47 (d, J=12.5 Hz, 1H), 4.99 (d, J=12, 5 Hz, 1H), 4.69 (q, J=7.0 Hz, 1H), 1.53 (d, J=7.0 Hz, 3H). 2-350 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.35 (dd, J=6.5, 2.0 Hz, 1H), 7.00-7.09 (m, 2H), 6.81 ( s, 2H), 5.71 (d, J=12.5 Hz, 1H), 5.20 (d, J=12.5 Hz, 1H), 4.69 (q, J=7.0 Hz, 1H), 1.54 (d, J=7.0 Hz, 3H). 2-351 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.33 (d, J=7.5 Hz, 1H), 7.05-7.12 (m, 2H), 6.81 (s, 2H) , 5.51 (d, J=12.5 Hz, 1H), 4.87 (d, J=12.5 Hz, 1H), 4.71 (q, J=7.0 Hz, 1H), 1 .52 (d, J=7.0 Hz, 3H). 2-352 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.82 (s, 2H), 5.84 (s, 1H), 4.69 (q, J=7.0 Hz, 1H), 3.72 (s, 3H), 2.32 (s, 3H), 1.44 (d, J=7.0 Hz, 3H). 2-353 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.53 (d, J=7.5 Hz, 1H), 6.81 (s, 2H), 6.37 (dd, J=7.5, 1.0Hz, 1H), 5.40-5.47(m, 1H), 5.03(d, J=12.5Hz, 1H), 4.70(kv, J=7.0Hz, 1H), 3.75 (s, 3H), 1.55 (d, J=7.0 Hz, 3H). 2-354 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.70 (t, J=1.5 Hz, 1H), 7.01 (t, J=1.0 Hz, 1H), 6.81 (s , 2H), 5.00-5.07 (m, 2H), 4.69 (q, J=7.0 Hz, 1H), 3.89 (s, 3H), 1.54 (d, J= 7.0 Hz, 3H). 2-355 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.19-7.28 (m, 2H), 7.15-7.21 (m, 1H), 7.09-7.29 (m, 1H ), 6.77 (s, 2H), 4.71 (q, J=7.0 Hz, 1H), 2.10 (d, J=1.0 Hz, 3H), 1.61 (d, J =7.0 Hz, 3H). 2-357 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.71 (t, J=2.0 Hz, 1H), 7.52 (dt, J=7.5, 2.0 Hz, 1H), 7 .36 (dt, J=7.5, 2.0 Hz, 1H), 7.25 (t, J=7.5 Hz, 1H), 6.74 (s, 2H), 5.04 (kv, J=7.0 Hz, 1H), 1.52 (d, J=7.0 Hz, 3H). 2-358 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.61-7.67 (m, 2H), 6.93-7.00 (m, 2H), 6.73 (s, 2H), 5, 06 (q, J=7.0 Hz, 1H), 3.79 (s, 3H), 1.51 (d, J=7.0 Hz, 3H). 2-360 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.46-7.53 (m, 2H), 7.28 (t, J=7.5 Hz, 1H), 7.15-7.18 ( m, 1H), 6.77 (s, 2H), 4.98 (kv, J=7.0 Hz, 1H), 2.89 (tt, J=8.0, 6.0 Hz, 1H), 1.45 (d, J=7.0 Hz, 3H), 1.17-1.23 (m, 6H). 2-363 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.50 (d, J=5.0 Hz, 2H), 7.76 (d, J=5.0 Hz, 2H), 6.74 (s , 2H), 5.03 (q, J=7.0 Hz, 1H), 1.51 (d, J=7.0 Hz, 3H). 2-365 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.97 (s, 1H), 6.82 (s, 2H), 5.06 (q, J=7.0 Hz, 1H), 3.90 (s, 3H), 2.14 (s, 3H), 1.53 (d, J=7.0 Hz, 3H). 2-368 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 6.66 (dd, J=7.5, 1.5 Hz, 1H), 6.29 (dd, J= 7.5, 1.5 Hz, 1H), 6.12 (t, J=7.5 Hz, 1H), 5.07 (kv, J=7.0 Hz, 1H), 3.62 (s, 3H), 1.56 (d, J=7.0 Hz, 3H). 2-370 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.80 (s, 2H), 4.98 (d, J=12.5 Hz, 1H), 4.93 (d, J=12.5 Hz , 1H), 4.66 (q, J=6.5 Hz, 1H), 3.44-3.51 (m, 1H), 3.16-3.24 (m, 1H), 1.51 ( e, J=7.0 Hz, 3H), 1.05 (t, J=8.0 Hz, 3H). 2-371 ¹ H NMR (500 MHz, Chloroform-d) δ 6.76 (s, 1H), 4.61 (q, J=6.5 Hz, 1H), 4.44 (s, 2H), 1.73 ( d, J=6.5 Hz, 3H), 1.66 (s, 2H). 2-372 ¹ H NMR (500 MHz, Chloroform-d) δ 8.09 (s, 1H), 4.93 (s, 1H), 4.71 (q, J=6.5 Hz, 1H), 4.47 ( s, 2H), 3.63 (s, 3H), 1.71 (d, J=6.5 Hz, 3H), 1.44 (s, 9H). 2-373 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.46 (s, 2H), 6.79 (s, 2H), 5.02 (q, J=7.0 Hz, 1H), 1.59 (d, J=7.0 Hz, 3H). 2-376 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.12 (s, 1H), 4.99 (q, J=7.0 Hz, 1H), 3.66 (dq, J=12.5, 8.0 Hz, 1H), 3.28 (dkv, J=12.5, 8.0 Hz, 1H), 2.31 (s, 3H), 1.54 (d, J=7.0 Hz, 3H), 1.26 (t, J=8.0 Hz, 3H). 2-377 ¹ H NMR (500 MHz, Chloroform-d) δ 9.90 (s, 1H), 4.64 (q, J=7.0 Hz, 1H), 3.85 (s, 3H), 2.20 ( s, 3H), 1.70 (d, J=7.0 Hz, 3H). 2-378 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.55 (dd, J=7.0, 2.0 Hz, 1H), 6.34-6.43 (m, 2H), 6.22 ( s, 1H), 5.14 (d, J=12.5 Hz, 1H), 4.67 (q, J=7.0 Hz, 1H), 4.43 (d, J=12.5 Hz, 1H), 3.72 (s, 3H), 1.53 (d, J=7.0 Hz, 3H). 2-379 ¹ H NMR (500 MHz, Chloroform-d) δ 7.95-7.98 (m, 3H), 7.52-7.56 (m, 2H), 7.29-7.33 (m, 1H) , 4.56 (q, J=7.0 Hz, 1H), 3.85 (s, 3H), 1.69 (d, J=7.0 Hz, 3H). 2-381 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.93-8.00 (m, 2H), 7.55-7.63 (m, 1H), 7.50-7.58 (m, 2H ), 4.63 (q, J=7.0 Hz, 1H), 3.72 (s, 3H), 1.53 (d, J=7.0 Hz, 3H). 2-383 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.04 (s, 2H), 4.41 (d, J=8.5 Hz, 1H), 4.11-4.18 (m, 2H) , 1.14-1.31 (m, 5H), 0.48-0.66 (m, 3H) 2-385 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.59-7.62 (m, 2H), 7.32-7.34 (m, 3H), 6.77 (s, 2H), 6, 27 (d, J=1.0 Hz, 1H), 2.31 (s, 3H). 2-386 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.96 (s, 2H), 5.10 (q, J=7.0 Hz, 1H), 4.30-4.26 (m, 1H) , 4.19-4.14 (m, 1H), 4.07-4.00 (m, 2H), 2.23 (s, 3H), 1.75 (s, 3H), 1.66 (s , 3H), 1.48 (d, J=7.0 Hz, 3H). 2-387 ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 6.43-6.34 (m, 2H), 6.22 (s, 1H), 4.84 (d, J=7.0 Hz, 1H) , 4.70-4.62 (m, 2H), 3.26 (s, 3H), 1.51 (d, J=7.0 Hz, 3H).

Several methods for preparing the compounds of the present invention are illustrated in detail in the following Schemes and Examples. Starting materials may be commercially purchased or may be prepared by methods known in the literature or in accordance with detailed illustrations. Those skilled in the art will appreciate that other synthetic methods may be used to synthesize the compounds of the present invention. Although specific starting materials and synthesis conditions are described below, they can be easily replaced by other similar starting materials and conditions, and various isomers of compounds and the like obtained by variations or variants of the production methods of the present invention are included in the scope of the present invention. In addition, the preparation methods described below can be further modified in accordance with the present invention using conventional chemical methods well known to those skilled in the art. For example, appropriate groups are protected during the reaction, and the like.

Method examples are given below to facilitate further understanding of the method of obtaining the present invention, and the specific materials, types and conditions used are defined as a further description of the present invention and are not intended to limit its conceptual scope. The reagents used to synthesize the following compounds listed in the table below are either commercially available or readily available to those skilled in the art.

Examples of representative compounds follow below, methods for the synthesis of other compounds are similar and will not be described in detail here.

1. Synthesis of compounds 2-31 and 1-2

(1) Compound 2-31-1 (300 mg, 1.27 mmol), compound b (255 mg, 1.53 mmol), a catalytic amount of TBAB (10 mg) and DMF (20 ml) were added to a 50 ml round bottom flask. ml, heated to 85°C and allowed to react for 12 hours. After completion of the reaction of the starting materials according to the determination of LC-MS, the reaction solution was cooled to room temperature, concentrated and separated by column chromatography to obtain compound 2-31 (180 mg, yield 47%).

(2) Compound 2-31 (0.5 g, 1.77 mmol), methanol (20 ml) was added to a 100 ml single neck flask, lithium hydroxide (74 mg, 1.77 mmol) was dissolved in 2 ml of water, and slowly was added dropwise to a one-necked flask at room temperature, followed by stirring at room temperature for 12 hours. After completion of the reaction of the starting materials as determined by LCMS, the reaction solution was adjusted with 0.5 M dilute HCl to pH 5-6, concentrated, and then extracted with water and ethyl acetate. The organic phase was dried and concentrated to give Compound 1-2 (400 mg) as a white solid.

2. Synthesis of compound 2-45

(1) Compound 2-45-1 (1 g, 8.61 mmol), phosphorus oxybromide (3.7 g, 12.9 mmol) was added to a 50 ml round bottom flask, heated to 60°C, and allowed to react for 5 hours After completion of the reaction of the starting materials according to HPLC determination, the reaction solution was cooled to room temperature, and slowly poured into an ice water bath, while the temperature was controlled at 0-10 °C during quenching. The aqueous phase was extracted with ethyl acetate (100 ml x 2). The organic phase was dried and concentrated to give compound 2-45-2 (1.5 g, crude product). Without further purification, the compound was used directly in the next step.

(2) Compound a (400 mg, 2.13 mmol), compound 2-45-2 (700 mg), a catalytic amount of TBAB (10 mg) and DMF (10 ml) were added to a 50 ml round bottom flask, heated to 85 °C and allowed to react for 12 hours. After completion of the reaction of the starting materials according to the definition of LCMS, the reaction solution was cooled to room temperature, and was extracted with water (100 ml) and simple methyl tert-butyl ether (50 ml × 2). The organic phase was dried, concentrated and separated by column chromatography to give compound 2-45 (200 mg, 35% yield) as a white solid.

3. Synthesis of compound 2-69

Compound a (0.5 g, 2.13 mmol), compound b (313 mg, 2.55 mmol), a catalytic amount of TBAB (10 mg) and DMF (10 ml) were added to a round bottom flask and stirred at room temperature 15° C within 24 hours. When a small amount of starting materials remained, as determined by LCMS, further processing was carried out. The reaction solution was poured into 50 ml of water and extracted twice with methyl tert-butyl ether (50 ml×2). The organic phase was dried, concentrated and separated by column chromatography to give compound 2-69 (300 mg, 50% yield) as a white solid.

4. Synthesis of compound 2-319

According to the method of synthesis of compound 1-2, compound 1-26 was obtained, then compound 1-26 (400 mg, 1.49 mmol), compound 2-319-1 (219 mg, 1.49 mmol), DCC (459 mg , 2.24 mmol) and anhydrous DCM (20 ml) were added to a 100 ml round bottom flask and reacted at room temperature for 12 hours. obtaining compound 2-319 (250 mg, 41% yield) as a white solid.

5. Synthesis of compounds 2-378 and 1-71

(1) Compound 2-69 (200 mg, 0.71 mmol), compound c (145 mg, 0.85 mmol), potassium carbonate (1 eq.), catalytic amount of DMAP (10 mg) and acetonitrile (20 ml) was added to a 50 ml round-bottom flask, heated to 80° C., and reacted for 12 hours. After completion of the reaction of the starting materials according to the LC-MS determination, the reaction solution was cooled to room temperature, concentrated, and separated by column chromatography to obtain compound 2- 378 (150 mg, 50% yield) as a colorless oil.

(2) Compound 2-378 (0.15 g, 0.43 mmol), methanol (20 ml) was added to a 100 ml single-necked flask, lithium hydroxide (48 mg, 2 mmol) was dissolved in 2 ml of water and added slowly drops into a single-necked flask at room temperature, followed by stirring at room temperature for 12 hours. After completion of the reaction of the starting materials as determined by LCMS, the reaction solution was adjusted to pH 5-6 with 0.5 M dilute HCl, concentrated, and then extracted with water and ethyl acetate . The organic phase was dried and concentrated to give compound 1-71 (100 mg) as a white solid.

Assessment of biological activity:

The activity level standard for plant killing (i.e., the degree of growth inhibition) is as follows:

Level 5: the degree of growth inhibition exceeds 85%;

Level 4: the degree of growth inhibition is equal to or greater than 60% and less than 85%;

Level 3: the degree of growth inhibition is equal to or greater than 40% and less than 60%;

Level 2: the degree of growth inhibition is equal to or greater than 20% and less than 40%;

Level 1: the degree of growth inhibition is equal to or more than 5% and less than 20%;

Level 0: the degree of growth inhibition is less than 5%;

The growth inhibition rate described above is the fresh weight inhibition rate.

Post-emergence test experiment: Monocots and dicots weed seeds and main crop seeds (eg wheat, corn, rice, soybean, cotton, oilseed, millet and sorghum) were placed in a plastic pot filled with soil. Then, covered with soil by 0.5-2 cm, the seeds were left to grow in good greenhouse conditions. The test plants were treated at the 2-3 leaf stage 2 weeks after sowing. The test compounds of the present invention were dissolved in acetone, respectively, then Tween-80 was added and 1.5 liters per hectare of methyl oleate emulsion concentrate was used as a synergist, and diluted with some water to a certain concentration. The solution was sprayed onto the plants using a sprayer. The plants were then cultivated in a greenhouse for 3 weeks, and the result of the weed control experiment is shown in Tables 4-5.

Table 4 Results of Compound Activity Tests (1000 g a.i./ha)

No. Echinochloa crusgalli Digitaria sanguinalis Monochoria Vaginalis Abutilon theophrasti Medic. Galium aparine 1-2 5 5 5 5 5 1-4 5 5 5 1-26 5 5 5 5 5 1-27 5 5 5 1-71 5 5 5 5 5 2-1 5 5 5 2-2 5 5 5 5 5 2-3 5 5 5 5 5 2-4 5 5 5 5 5 2-5 5 5 5 2-6 5 5 5 2-7 5 5 5 5 5 2-8 5 5 5 2-9 5 5 5 2-10 5 5 5 2-11 5 5 5 2-12 5 5 5 2-13 5 5 5 2-14 5 5 5 5 5 2-15 5 5 5 2-16 5 5 5 2-17 5 5 5 5 5 2-18 5 5 5 2-19 5 5 5 2-20 5 5 5 2-21 5 5 5 2-22 5 5 5 5 5 2-23 5 5 5 2-24 5 5 5 5 5 2-25 5 5 5 2-26 5 5 5 5 5 2-27 5 5 5 2-28 5 5 5 5 5 2-29 5 5 5 5 5 2-30 5 5 5 5 5 2-31 5 5 5 5 5 2-32 5 5 5 5 5 2-33 5 5 5 2-34 5 5 5 2-35 5 5 5 2-36 5 5 5 2-37 5 5 5 2-38 5 5 5 2-39 5 5 5 2-40 5 5 5 2-41 5 5 5 2-42 5 5 5 2-43 5 5 5 2-44 5 5 5 2-45 5 5 5 2-46 5 5 5 2-47 5 5 5 2-48 5 5 5 2-49 5 5 5 2-50 5 5 5 2-51 5 5 5 2-52 5 5 5 2-53 5 5 5 2-54 5 5 5 2-55 5 5 5 2-56 5 5 5 2-57 5 5 5 2-58 5 5 5 2-59 5 5 5 2-60 5 5 5 2-61 5 5 5 2-62 5 5 5 2-63 5 5 5 2-64 5 5 5 2-65 5 5 5 2-67 5 5 5 2-68 5 5 5 2-69 5 5 5 5 5 2-70 5 5 5 5 5 2-71 5 5 5 5 5 2-72 5 5 5 5 5 2-73 5 5 5 5 5 2-74 5 5 5 5 5 2-75 5 5 5 5 5 2-76 5 5 5 5 5 2-77 5 5 5 5 5 2-78 5 5 5 5 5 2-79 5 5 5 5 5 2-80 5 5 5 5 5 2-81 5 5 5 5 5 2-82 5 5 5 5 5 2-83 5 5 5 5 5 2-84 5 5 5 5 5 2-85 5 5 5 5 5 2-86 5 5 5 5 5 2-87 5 5 5 5 5 2-88 5 5 5 5 5 2-89 5 5 5 5 5 2-90 5 5 5 5 5 2-91 5 5 5 5 5 2-92 5 5 5 5 5 2-93 5 5 5 5 5 2-94 5 5 5 5 5 2-95 5 5 5 5 5 2-96 5 5 5 5 5 2-97 5 5 5 5 5 2-98 5 5 5 5 5 2-99 5 5 5 5 5 2-100 5 5 5 5 5 2-101 5 5 5 5 5 2-102 5 5 5 5 5 2-103 5 5 5 5 5 2-104 5 5 5 5 5 2-105 5 5 5 5 5 2-106 5 5 5 5 5 2-107 5 5 5 5 5 2-108 5 5 5 5 5 2-113 5 5 5 5 5 2-114 5 5 5 5 5 2-121 5 5 5 5 5 2-122 5 5 5 5 5 2-155 5 5 5 5 5 2-156 5 5 5 5 5 2-157 5 5 5 5 5 2-158 5 5 5 5 5 2-159 5 5 5 5 5 2-160 5 5 5 5 5 2-163 5 5 5 5 5 2-164 5 5 5 5 5 2-175 5 5 5 5 5 2-176 5 5 5 5 5 2-195 5 5 5 5 5 2-196 5 5 5 5 5 2-215 5 5 5 5 5 2-216 5 5 5 5 5 2-235 5 5 5 5 5 2-236 5 5 5 5 5 2-263 5 5 5 5 5 2-264 5 5 5 5 5 2-265 5 5 5 5 5 2-266 5 5 5 5 5 2-267 5 5 5 5 5 2-268 5 5 5 5 5 2-270 5 5 5 5 5 2-271 5 5 5 5 5 2-272 5 5 5 5 5 2-273 5 5 5 5 5 2-274 5 5 5 5 5 2-275 5 5 5 5 5 2-276 5 5 5 5 5 2-277 5 5 5 5 5 2-278 5 5 5 5 5 2-279 5 5 5 5 5 2-280 5 5 5 5 5 2-281 5 5 5 5 5 2-282 5 5 5 5 5 2-283 5 5 5 5 5 2-284 5 5 5 5 5 2-285 5 5 5 5 5 2-286 5 5 5 5 5 2-287 5 5 5 5 5 2-288 5 5 5 5 5 2-289 5 5 5 5 5 2-290 5 5 5 5 5 2-291 5 5 5 5 5 2-292 5 5 5 5 5 2-294 5 5 5 5 5 2-295 5 5 5 5 5 2-296 5 5 5 5 5 2-297 5 5 5 5 5 2-298 5 5 5 5 5 2-299 5 5 5 5 5 2-300 5 5 5 5 5 2-301 5 5 5 5 5 2-302 5 5 5 5 5 2-303 5 5 5 5 5 2-304 5 5 5 5 5 2-305 5 5 5 5 5 2-306 5 5 5 5 5 2-307 5 5 5 5 5 2-308 5 5 5 5 5 2-309 5 5 5 5 5 2-310 5 5 5 5 5 2-311 5 5 5 5 5 2-312 5 5 5 5 5 2-313 5 5 5 5 5 2-314 5 5 5 5 5 2-315 5 5 5 5 5 2-316 5 5 5 5 5 2-317 5 5 5 5 5 2-318 5 5 5 5 5 2-319 5 5 5 5 5 2-320 5 5 5 5 5 2-321 5 5 5 5 5 2-322 5 5 5 5 5 2-323 5 5 5 5 5 2-324 5 5 5 5 5 2-325 5 5 5 5 5 2-327 5 5 5 5 5 2-328 5 5 5 5 5 2-329 5 5 5 5 5 2-330 5 5 5 5 5 2-331 5 5 5 5 5 2-332 5 5 5 5 5 2-333 5 5 5 5 5 2-334 5 5 5 5 5 2-335 5 5 5 5 5 2-336 5 5 5 5 5 2-337 5 5 5 5 5 2-338 5 5 5 5 5 2-339 5 5 5 5 5 2-340 5 5 5 5 5 2-341 5 5 5 5 5 2-342 5 5 5 5 5 2-343 5 5 5 5 5 2-344 5 5 5 5 5 2-345 5 5 5 5 5 2-346 5 5 5 5 5 2-347 5 5 5 5 5 2-348 5 5 5 5 5 2-349 5 5 5 5 5 2-350 5 5 5 5 5 2-351 5 5 5 5 5 2-352 5 5 5 5 5 2-353 5 5 5 5 5 2-354 5 5 5 5 5 2-355 5 5 5 5 5 2-357 5 5 5 5 5 2-358 5 5 5 5 5 2-360 5 5 5 5 5 2-363 5 5 5 5 5 2-365 5 5 5 5 5 2-368 5 5 5 5 5 2-370 5 5 5 5 5 2-371 5 5 5 5 5 2-372 5 5 5 5 5 2-373 5 5 5 5 5 2-376 5 5 5 5 5 2-377 5 5 5 5 5 2-378 5 5 5 5 5 2-379 5 5 5 5 5 2-381 5 5 5 5 5 2-383 5 5 5 2-385 5 5 5 2-386 5 5 5 5 5 2-387 5 5 5 5 5

Notes: The mean was obtained from three replicate experiments, N means missing some data; unless explicitly stated, the application rate was 200 g/ha of active ingredient plus 450 kg/ha of water. Echinochloa crusgalli , collected in Jiangsu, China, was resistant to ALS inhibitor herbicides and ACCe herbicides, Digitaria sanguinalis and Semen Euphorbiae Lathyridis , also collected in Jiangsu, were resistant to the ACCe herbicide cyhalofop-butyl.

Surprisingly, although the compounds of the present invention were similar in structure to the control compounds, they had good effects and better selectivity against basic grass weeds, broadleaf weeds and Cyperus rotundus in paddy fields and excellent commercial value. In particular, they were still outstanding for controlling key weeds that were resistant to the ALS inhibitor bispyribac-sodium and the ACCe inhibitor cyhalofop-butyl. In addition, compared with the racemate and the S isomer, the R isomer of the present invention had significantly better activity against cereal weeds such as Echinochloa crusgalli, Digitaria sanguinalis and Semen Euphorbiae Lathyridis , and had good selectivity for rice.

Experiment on the action on weeds at the pre-emergence stage

Seeds of monocots and dicots and main crops (eg, wheat, corn, rice, soybeans, cotton, oilseeds, millet, and sorghum) were placed in a plastic pot filled with soil and covered with 0.5-2 cm of soil. The test compounds of the present invention were dissolved in acetone, then Tween-80 was added, diluted with some water to a certain concentration and sprayed immediately after inoculation. The resulting seeds were incubated for 4 weeks in a greenhouse after spraying and the test results were observed. It was noted that the herbicide generally showed excellent performance at a rate of 250 g ai/ha, especially against weeds such as Echinochloa crusgalli, Digitaria sanguinalis and Abutilon theophrasti , etc. Many compounds had good selectivity for corn, wheat , rice, soybeans, oilseed rape, etc.

Through experiments, the inventors have found that the compounds of the present invention generally have a better weed control effect, especially on major cereal weeds such as Echinochloa crusgalli, Digitaria sanguinalis , and Setaria viridis , which are widely distributed in corn fields, rice fields and wheat fields, as well as major deciduous weeds such as Abutilon theophrasti, Rorippa indica and Bidens pilosa , and have excellent commercial value. In particular, the inventors noted that they have extremely high activity against deciduous weeds such as Rorippa indica , Descurainia sophia, Capsella bursa-pastoris, Lithospermum arvense, Galium aparine and Stellaria media , which were resistant to ALS inhibitors.

Seedling rice safety assessment and weed control effect assessment in paddy field:

The rice field soil was loaded into a 1/1,000,000 hectare pot. Seeds of Monochoria vaginalis were sown and carefully covered with soil, then left to stand in the greenhouse in a state of water reserve of 0.5-1 cm. After that, they were kept at 3-4 cm of water reserve. Weeds were treated by dropping aqueous solutions of WP or SC prepared according to the general method for preparing the compounds of the present invention evenly with a pipette to reach the desired effective amount when Monochoria vaginalis had reached the 0.5 leaf stage.

In addition, the soil of the rice field placed in a 1/1,000,000 ha pot was leveled to keep the water reserve at a depth of 3-4 cm. . The compound of the present invention was applied in the same manner 5 days after transplantation.

The fertility status of Monochoria vaginalis 14 days later and rice 21 days after treatment with the compound of the invention was assessed with the naked eye. Based on the evaluation of the weed control effect according to the above standard of activity level 0-5, it was found that many compounds exhibit excellent activity and selectivity.

Table 6 Activity and safety test results (1000 g a.i./ha)

No. rice Monochoria Vaginalis 1-2 0 5 1-26 0 5 1-71 0 5 2-69 0 5 2-70 0 5 2-71 0 5 2-294 0 5 2-300 0 5 2-319 0 5 2-343 0 5 2-348 0 5 penoxsulam (50 g a.i./ha) 1 1

Note: Monochoria vaginalis seeds were collected from Heilongjiang Province, China. Tests showed that the weeds were resistant to the usual rate of pyrazosulfuron-ethyl and penoxsulam.

From experiments, it can be seen that the compounds of the present invention exhibit excellent activity against weeds having anti-ALS inhibitory activity, which are a serious problem in production conditions, and can solve the increasingly acute problem of resistance.

At the same time, after several tests, the compound and composition of the present invention were found to have good selectivity to many grass weeds such as Zoysia japonica , Cynodon dactylon , Festuca elata , Poa annua , Lolium perenne , and Paspalum vaginatum , etc., and able to control many major grass weeds and deciduous weeds. The compound also shows excellent selectivity and commercial value in tests on wheat, corn, rice, sugar cane, soybeans, cotton, sunflowers, potatoes, orchards and vegetables in various herbicide applications.

Claims (83)

1. R-pyridyloxycarboxylic acid represented by formula I, and its salt, ester derivative,

the salt is a metal salt, an amine salt, a sulfonium salt, or a phosphonium salt; ester is

; where each A, B is independently halo or C1-C8 alkyl; C is hydrogen, halo or C1-C8 alkyl; Q is halo, cyano, cyano C1-C8 alkyl, hydroxy C1-C8 alkyl, amino, nitro, formyl; C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkoxycarbonyl, C1-C8 alkylamino C1-C8 alkyl or C1-C8 alkoxy C1- C8 alkyl with or without halogen; or unsubstituted or substituted aryl, heteroaryl, aryl C1-C8 alkyl; Y is NR ₁ R ₂ where R ₁ is H; C1-C8 alkyl optionally substituted with 1-2 R ₁₁ ; or -COR ₁₂ ; R ₂ is H or C1-C8 alkyl; where R ₁₁ represents

, which is unsubstituted or substituted with 1-3 groups selected from the group consisting of halo C1-C8 alkyl; or R ₁₂ is H, C1-C18 alkyl or phenyl; in formula I-1 X is O or S; M is C1-C18 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, -(C1-C8 alkyl)-Z,

or

with or without halogen; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl; Z represents

,

,

,

,

,

, cyano, nitro or unsubstituted or substituted heterocyclyl, aryl, heteroaryl; each R ₃ is independently C1-C8 alkyl or C2-C8 alkenyl; each R ₄ , R ₅ , R ₆ independently represents hydrogen, C1-C8 alkyl or C1-C8 alkoxycarbonyl; the term "heterocyclyl" refers to

; the term "aryl" refers to phenyl or naphthyl; the term "heteroaryl" refers to

or

, which is optionally substituted with at least one group selected from the group consisting of halogen, cyano, C1-C6 alkyl, OR”, SR”, with or without halogen; each R' is independently hydrogen or C1-C6 alkyl with or without halogen; each R" is independently hydrogen or C1-C6 alkyl. 2. R-pyridyloxycarboxylic acid and its salt, ester derivative according to claim 1, where each A, B is independently halogen or C1-C6 alkyl; C is hydrogen, halo or C1-C6 alkyl; Q is halo, cyano, cyano C1-C6 alkyl, hydroxy C1-C6 alkyl, amino, nitro, formyl; C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkoxycarbonyl, C1-C6 alkylamino C1-C6 alkyl or C1-C6 alkoxy C1- C6 alkyl with or without halogen; or unsubstituted or substituted aryl, heteroaryl, aryl C1-C6 alkyl; Y is NR ₁ R ₂ where R ₁ is H; C1-C6 alkyl optionally substituted with 1-2 R ₁₁ ; or -COR ₁₂ ; R ₂ is H or C1-C6 alkyl; where R ₁₁ represents

, which is unsubstituted or substituted with 1-3 groups selected from the group consisting of halo C1-C6 alkyl; R ₁₂ is H, C1-C14 alkyl or phenyl; salt is a metal salt, ammonium salt NH ₄ ⁺ , primary amine salt RNH ₂ , secondary amine salt (R) ₂ NH, tertiary amine salt (R) ₃ N, quaternary amine salt (R) ₄ N ⁺ , morpholine salt, salt piperidine, pyridine salt, aminopropylmorpholine salt, jeffamine D-230 salt, 2,4,6-tri(dimethylaminomethyl)phenol sodium hydroxide salt, C1-C18 alkylsulfonium salt, C1-C18 alkylsulfoxonium salt, C1-C18 alkylphosphonium salt, or C1 salt -C18 alkanolphosphonium; where each R is independently unsubstituted C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C3-C18 cycloalkyl or phenyl and the above groups are optionally substituted with one or more of the following groups: halogen, hydroxy, C1-C8 alkoxy, C1-C8 alkylthio, hydroxy C1-C8 alkoxy, amino, C1-C8 alkylamino, amino C1-C8 alkylamino, phenyl; in formula I-1 X is O or S; M is C1-C18 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, -(C1-C6 alkyl)-Z,

or

with or without halogen; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl; Z represents

,

,

,

,

,

, cyano, nitro or unsubstituted or substituted heterocyclyl, aryl, heteroaryl; each R ₃ is independently C1-C6 alkyl or C2-C6 alkenyl; each R ₄ , R ₅ , R ₆ independently represents hydrogen, C1-C6 alkyl or C1-C6 alkoxycarbonyl; the term "heterocyclyl" refers to

; the term "aryl" refers to phenyl or naphthyl; the term "heteroaryl" refers to

or

, which is substituted with 0, 1, 2 or 3 groups selected from the group consisting of halogen, cyano, C1-C6 alkyl, OR”, SR”, with or without halogen; each R' is independently hydrogen or C1-C6 alkyl with or without fluorine, chlorine or bromine; each R" is independently hydrogen or C1-C6 alkyl. 3. R-pyridyloxycarboxylic acid and its salt, ester derivative according to claim 2, where each A, B is independently halogen or C1-C6 alkyl; C is hydrogen, halo or C1-C6 alkyl; Q is C1-C6 alkyl, halo C1-C6 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, C2-C6 alkynyl, halogen, cyano, amino, nitro, formyl, C1-C6 alkoxy, C1-C6 alkylthio, C1 -C6 alkoxycarbonyl, hydroxy C1-C6 alkyl, C1-C6 alkoxy C1-C2 alkyl, cyano C1-C2 alkyl, C1-C6 alkylamino C1-C2 alkyl, benzyl, thienyl, thiazolyl;

, which is unsubstituted or substituted with C1-C6 alkyl; or phenyl which is unsubstituted or substituted with at least one group selected from the group consisting of halogen; Y is amino, C1-C6 alkylamino, C1-C6 alkylcarbonylamino, phenylcarbonylamino, benzylamino or furylmethyleneamino which is unsubstituted or halo-substituted C1-C6 alkyl; salt is a metal salt, ammonium salt NH ₄ ⁺ , primary amine salt RNH ₂ , secondary amine salt (R) ₂ NH, tertiary amine salt (R) ₃ N, quaternary amine salt (R) ₄ N ⁺ , morpholine salt, salt piperidine, pyridine salt, aminopropylmorpholine salt, jeffamine D-230 salt, 2,4,6-tri(dimethylaminomethyl)phenol sodium hydroxide salt, C1-C14 alkylsulfonium salt, C1-C14 alkylsulfoxonium salt, C1-C14 alkylphosphonium salt, or C1 salt -C14 alkanolphosphonium; where each R is independently unsubstituted C1-C14 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C3-C12 cycloalkyl, or phenyl; or C1-C14 alkyl optionally substituted with one or more of the following groups: halogen, hydroxy, C1-C6 alkoxy, C1-C6 alkylthio, hydroxy C1-C6 alkoxy, amino, C1-C6 alkylamino, amino C1-C6 alkylamino, phenyl; in formula I-1 X is O or S; M is C1-C18 alkyl, halo C1-C8 alkyl, C3-C6 cycloalkyl, C2-C6 alkenyl, halo C2-C6 alkenyl, C2-C6 alkynyl, cyano C1-C2 alkyl, nitro C1-C2 alkyl, C1-C6 alkoxy C1-C2 alkyl, C1-C6 alkoxycarbonyl C1-C2 alkyl, C2-C6 alkenyloxycarbonyl C1-C2 alkyl, -(C1-C2 alkyl)-Z,

, tetrahydrofuryl, pyridyl, naphthyl,

which is unsubstituted or substituted C1-C6 alkyl; or phenyl which is unsubstituted or substituted with C1-C6 alkyl, halo or C1-C6 alkoxy; Z represents

tetrahydrofuryl, pyridyl,

thienyl, furyl, naphthyl or phenyl which is unsubstituted or substituted with at least one group selected from the group consisting of C1-C6 alkyl, halo C1-C6 alkyl, cyano and halo; each R ₃ is independently C1-C6 alkyl; each R ₄ , R ₅ , R ₆ independently represents hydrogen, C1-C6 alkyl or C1-C6 alkoxycarbonyl; R' is hydrogen or C1-C6 alkyl. 4. R-pyridyloxycarboxylic acid and its salt, ester derivative according to claim 3, where each A, B independently represents chlorine or methyl; C represents hydrogen, fluorine, chlorine or methyl; Q is methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, fluorine, chlorine, bromine, cyano, amino, nitro, formyl, methoxy, methylthio, methoxycarbonyl, monochloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2 ,2,2-trifluoroethyl, hydroxymethyl,

benzyl; thiazolyl which is unsubstituted or substituted with chlorine; thienyl;

, which is unsubstituted or substituted with methyl or fluorine; or phenyl which is unsubstituted or substituted with at least one chlorine; Y is NH ₂ ,

or

; salt is an alkali metal salt, alkaline earth metal salt, heavy metal salt, aluminum salt or ammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetraisopropylammonium salt, tetrabutylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, cholinamine salt, monomethylamine salt, dimethylamine salt , trimethylamine salt, monoethylamine salt, diethylamine salt, triethylamine salt, monoisopropylamine salt, diisopropylamine salt, triisopropylamine salt, monoisobutylamine salt, pentylamine salt, hexylamine salt, heptylamine salt, dodecylamine salt, tetradecylamine salt, diallylamine salt, cyclododecylamine salt, benzylamine salt, salt monoethanolamine, diethanolamine salt, triethanolamine salt, tripropanolamine salt, triisopropanolamine salt, tri(2-hydroxypropyl)amine salt, methylmonoethanolamine salt, dimethylmonoethanolamine salt, methyldiethanolamine salt, diethylethanolamine salt, diglycolamine salt, diethylenetriamine salt, e salt imethylaminopropylamine, 1,2-propyldiamine salt, triethylenetetramine salt, N,N-bis[aminopropyl]methylamine salt, 2-methylthiopropylamine salt, 2-butoxyethylamine salt, AEPD salt, tri(methylol)aminomethane salt, morpholine salt, aminopropylmorpholine salt, salt jeffamine D-230, 2,4,6-tri(dimethylaminomethyl)phenol sodium hydroxide salt; in formula I-1 X is O or S; M is methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, 2-fluoroethyl, 2-chloroethyl, 2 -bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 4,4,4-trifluorobutyl, 2,2,3,3,3-pentafluoropropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, allyl, 2-propynyl ,

tetrahydrofuryl, tetrahydrofurylmethylene, pyridyl, pyridylmethylene, naphthyl, naphthylmethylene, furylmethylene, thienylmethylene,

which is unsubstituted or substituted with methyl; phenyl which is unsubstituted or substituted with methyl, chlorine, methoxy or isopropyl; or benzyl which is unsubstituted or substituted with trifluoromethyl, bromine, chlorine, fluorine, cyano or methyl; R' is hydrogen or methyl. 5. R-pyridyloxycarboxylic acid and its salt, ester derivative according to claim 4, selected from the following compounds:

6. The method for producing R-pyridyloxycarboxylic acid and its salt, ester derivative according to any one of claims 1 to 5, which includes the following steps: a compound of formula III is reacted with a compound of formula II to give a compound of formula I-1-1; the reaction scheme is as follows:

where W is an alkali metal, preferably K, Na; Hal is halogen, preferably Br, Cl; the reaction is carried out in the presence of a catalyst and a solvent, preferably the catalyst is TBAB and the solvent is one or more selected from the group consisting of DCM, DCE, ACN, THF, DMF; a compound of formula I-1-1 is reacted in the presence of an aqueous solution of lithium hydroxide and a solvent to give a compound of formula I; the reaction scheme is as follows:

preferably the solvent is one or more selected from the group consisting of methanol, ethanol and isopropanol; the compound of formula I is subjected to reaction with M-SH to obtain a compound of formula I-1-2; the reaction scheme is as follows:

where the reaction is carried out in the presence of a dehydrating agent and a solvent, preferably the dehydrating agent is DCC and the solvent is one or more selected from the group consisting of dichloromethane, dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran , toluene, xylene; or when Y is NR ₁ R ₂ (R ₁ , R ₂ are not hydrogen at the same time), it is obtained by reacting a compound of formula I-2

or compounds of formula I-1-3

with the corresponding halide; where the halide is preferably chloride or bromide; the reaction is carried out in the presence of a base and a solvent, where the base is one or more of the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate; the solvent is one or more selected from the group consisting of THF, 1,4-dioxane, toluene, 1,2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane and chloroform; a catalyst, preferably DMAP, is optionally added during the reaction. 7. Herbicidal composition containing (i) at least one R-type pyridyloxycarboxylic acid and its salt, ester derivative according to any one of claims 1 to 5 in a herbicidally effective amount; preferably further comprising (ii) agrochemically acceptable formulation auxiliaries. 8. A weed control method comprising applying a herbicidally effective amount of at least one R-type pyridyloxycarboxylic acid and a salt thereof, an ester derivative according to any one of claims 1 to 5, or a herbicidal composition according to claim 7, to a plant or weed site, preferably the plant is a rice or the weed is a grass weed (such as Echinochloa crusgalli, Digitaria sanguinalis, Semen Euphorbiae Lathyridis ) or a deciduous weed (such as Monochoria Vaginalis, Abutilon theophrasti Medic., Galium aparine ). 9. The use of at least one of R-pyridyloxycarboxylic acid and its salt, ester derivative according to any one of claims 1 to 5 or the herbicidal composition according to claim 7 for weed control, preferably R-pyridyloxycarboxylic acid and its salt, ester derivative, used for weed control in a useful crop, where the beneficial crop is a genetically modified crop or a crop altered by genome editing technology, preferably the crop is rice or the weed is a grass weed (such as Echinochloa crusgalli, Digitaria sanguinalis, Semen Euphorbiae Lathyridis ) or deciduous weed (such as Monochoria Vaginalis, Abutilon theophrasti Medic., Galium aparine ).