OA20640A

OA20640A - R-type Pyridyloxycarboxylic acid, salt and ester derivative thereof, and preparation method therefor, and herbicidal composition and application thereof.

Info

Publication number: OA20640A
Application number: OA1202100303
Authority: OA
Inventors: Lei Lian; Xuegang PENG; Rongbao HUA; Jingyuan Zhang; Qi CUI
Original assignee: Qingdao Kingagroot Chemical Compound Co., Ltd.
Priority date: 2018-12-27
Filing date: 2019-12-20
Publication date: 2022-12-28

Abstract

The invention relates to the field of pesticide technology, and in particular to a type of Rpyridyloxycarboxylic acid and salt, ester derivative, preparation method, herbicidal composition and application thereof The Rpyridyloxycarboxylic acid is represented by formula wherein, A, B each independently represent halogen, alkyl or cycloalkyl with or without halogen; C represents hydrogen, halogen, alkyl, haloalkyl; Q represents halogen, cyano, cyanoalkyl and the like; Y represents nitro or NR1R2; the salt is metal salt, amine salt,

Description

The invention relates to the field of pesticide technology, and in particular to a type of Rpyridyloxycarboxylic acid and sait, ester dérivative, préparation method, herbicidal composition and application thereof The R-pyridyloxycarboxylic acid is represented by formula

wherein, A, B each independently represent halogen, alkyl or cycloalkyl with or without halogen;

C represents hydrogen, halogen, alkyl, haloalkyl; Q represents halogen, cyano, cyanoalkyl and the like; Y represents nitro or NR1R2; the sait is métal sait, amine sait, sulfonium sait, phosphonium sait; the ester is 1-1 , wherein, X represents O or S; M represents alkyl, alkenyl, alkynyl and the like with or without halogen. The compound has excellent herbicidal activity and higher crop safety, especially good selectivity for key crops such as rice.

O.A.P.I. - B.P. 887, YAOUNDE (Cameroun) - Tel. (237) 222 20 57 00-Site web: http:/www.oapi.int- Email: oapi@oapi.int

R-pyridyloxycarboxylic acid and sait, ester dérivative, préparation method, herbicidal composition and application thereof

Technical Field

The invention relates to the field of pesticide technology, and in particular a type of R-pyridyloxycarboxylic acid and sait, ester dérivative, préparation method, herbicidal composition and application thereof.

Technical background

Weed control is one of the most important links in the course of achieving high-efficiency agriculture. Varions herbicides are available in the market, for example, DE2335349A1, GB1418979A, US3761486 and the like disclose a sériés of compounds represented by the

Ri ^X-Z-/^X FM Jl JC CC general formula R₂ n o R and application thereof as herbicides, but enantiomers of the compounds are not mentioned. Scientists still need to do continuously research and develop new herbicides with high efficacy, safety, économies and different modes of action due to problems such as the growing market, weed résistance, the service life and économies of pesticides as well as people’s increasing concem on environment.

Invention contents

The présent invention provides a type of R-pyridyloxycarboxylic acid and sait, ester dérivative, préparation method, herbicidal composition and application thereof. The compound has excellent herbicidal activity and higher crop safety, especially good selectivity for key crops such as rice.

The technical solution adopted by the invention is as foliows:

The présent invention provides an R-pyridyloxycarboxylic acid represented by formula I and sait, ester dérivative thereof,

wherein, A, B each independently represent halogen; or alkyl or cycloalkyl with or without halogen;

C represents hydrogen, halogen, alkyl or haloalkyl;

Q represents halogen, cyano, cyanoalkyl, hydroxyalkyl, amino, nitro, formyl; alkyl, alkenyl, i

alkynyl, cycloalkyl, alkoxy, alkylthio, alkyl carbonyl, alkoxycarbonyl, alkylaminoalkyl or alkoxyalkyl with or without halogen; or unsubstituted or substituted aryl, heteroaryl, arylalkyl, heteroarylalkyl;

Y represents nitro or NRiR₂, wherein Ri représente H; alkyl, alkenyl or alkynyl optionally substituted by 1-2 Ru; -COR12, nitro, ORu, SO₂Ri4, NR15R16, N=CRiyRi8, alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl or dialkylphosphono; R₂ represents H; alkyl optionally substituted by 1-2 Ru; or -CORi₂; or NR1R2 represents N=CR_2iNR₂₂R₂3, N=CR₂4OR₂₅; or a 5- or 6-membered saturated or unsaturated ring with or without oxygen atom, sulfiir atom, or other nitrogen atom, which is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl;

wherein Ru independently represents halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl; or unsubstituted or substituted aryl, heteroaryl;

R12 represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;

R13 represents H, alkyl, haloalkyl, phenyl, benzyl or CHR3iC(O)OR₃₂; R31 represents H, alkyl or alkoxy; R₃₂ represents H, alkyl or benzyl;

R14 represents alkyl or haloalkyl;

R15 represents H, alkyl, formyl, alkylacyl, haloalkylacyl, alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R_i6 represents H or alkyl;

R17 represents H, alkyl; or phenyl that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, alkyl, alkoxy; Ri_S represents H or alkyl; or N=CRi₇R₁₈ ,^N=\ J \ represents or \__/ ;

R₂i, R₂4 each independently represent H or alkyl;

R22, R23 each independently represent H or alkyl; or NR₂₂R₂3 represents a 5- or 6-membered saturated or unsaturated ring with or without oxygen atom, sulfiir atom, or other nitrogen atom;

R₂5 represents alkyl;

the sait is métal sait, amine sait, sulfonium sait or phosphonium sait;

Y

O the ester is □ -1 , wherein, X represents O or S;

Ο

II . Ο

Μ represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, -alkyl-Z, Y ^R3, < ô ,

O ^R4>j'^R5 i_R3 Y^r< γ ⁰ , ^r5 , ^r5 , O with or without halogen; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

₇ 7% vV V⁴

Z represents * Ύ y o _; q , ^Rs , Rs , ^Rs , cyano, nitro, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

R₃ each independently represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, heteroarylalkyl;

R4, R5, Rô each independently represent hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxycarbonyl or unsubstituted or substituted heterocyclyl, aryl, heteroaryl, heterocyclylalkyl, arylalkyl, heteroarylalkyl.

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

C represents hydrogen, halogen, C1-C8 alkyl or halo C1-C8 alkyl;

Q represents halogen, 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 C l -C8 alkyl;

Y represents nitro or NRiR₂, wherein Ri represents H; C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl optionally substituted by 1-2 Ru; -COR12, nitro, OR₁₃, SO₂R₁₄, NR₁₅R₁₆, N=CR₁₇R₁₈, C1-C8 alkylcarbamoyl, di-Cl-C8 alkylcarbamoyl, tri-Cl-C8 alkylsilyl or di-Cl-C8 alkylphosphono; R₂ represents H; C1-C8 alkyl optionally substituted by 1-2 Ru; or -COR12; or > Ύ -¾ Y /n'Y /n'Y

NRiR₂ represents N=CR₂iNR₂₂R₂₃, N=CR₂₄OR₂5; or ^NV-J, ^N\Y La , or that is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halogen, C1-C8 alkyl, C1-C8 alkoxy, halo C1-C8 alkoxy, C1-C8 alkylthio, halo C1-C8 alkylthio, amino, C1-C8 alkylamino, di-Cl-C8 alkylamino, C1-C8 alkoxycarbonyl;

wherein Ru independently represents halogen, hydroxy, C1-C8 alkoxy, halo C1-C8 alkoxy, C1-C8 alkylthio, halo C1-C8 alkylthio, amino, C1-C8 alkylamino, di-Cl-C8 alkylamino, C1-C8 alkoxycarbonyl; or phenyl, naphthyl,

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

R12 represents H, C1-C18 alkyl, halo C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;

R13 represents H, C1-C8 alkyl, halo C1-C8 alkyl, phenyl, benzyl or CHR₃iC(O)OR₃₂; R31 represents H, C1-C8 alkyl or C1-C8 alkoxy; R₃₂ represents H, C1-C8 alkyl or benzyl;

Ru represents C1-C8 alkyl or halo C1-C8 alkyl;

R15 represents H, C1-C8 alkyl, formyl, C1-C8 alkylacyl, halo C1-C8 alkylacyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R₁₆ represents H or C1-C8 alkyl;

Rn represents H, C1-C8 alkyl; or phenyl that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, C1-C8 alkyl, C1-C8 alkoxy; R₁₈ represents H or

Cl-C8 alkyl; or N=CRi₇R_ts represents or

R21, R24 each independently represent H or C1-C8 alkyl;

R22, R23 each independently represent H or C1-C8 alkyl; or NR22R23 represents ^NO,

R25 represents C1-C8 alkyl;

the sait is métal sait, ammonium sait NH₄ ⁺, primary amine RNH₂ sait, secondary amine (R)₂NH sait, tertiary amine (R)₃N sait, quatemary amine sait (R)₄N⁺, morpholine sait, piperidine sait, pyridine sait, aminopropyl morpholine sait, Jeff amine D-230 sait, the sait of 2,4,6-tri(dimethylaminomethyl) phénol and sodium hydroxide, alkylsulfonium sait, alkylsulfoxonium sait, alkylphosphonium sait or alkanolphosphonium sait;

wherein, R each independently represents unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl or phenyl, and the foregoing groups are optionally substituted by one or more of the following groups: halogen, hydroxy, alkoxy, alkylthio, hydroxyalkoxy, amino, alkylamino, amino alkylamino, phenyl;

in formula 1-1, X represents O or S;

M represents Cl-Cl 8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8

O ο Λ JL R Ύ”⁴ .\ⁿY^r-> cycloalkyl C1-C8 alkyl, -(C1-C8 alkyl)-Z, V Ύ * 6 A ΑΌ , R5 , r_{5 ;} ·,Α

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

_t0 A r *>'V⁴ A'”⁴ ‘V¹’⁴

Z represents 1 ^R3, Λ O _; o , ^Rs , ^R5 , Rs , cyano, nitro, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

R₃ each independently represents 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;

R4, R₅, Rô each independently represent 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;

R' i rA _t <o_{v s} . M aî

Ύύ⁰ M? ' r / -l— 5 hN 7 4— h |—N the term “heterocyclyl” refers to v h—I ^; « </ I I

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 to 6 ring atoms and is optionally fused via benzo ring, 1 to 4 heteroatoms in the ring atoms being

selected from oxygen, nitrogen and sulfur, for example,

group selected from the group consisting of halogen, nitro, cyano, thiocyano, hydroxy, carboxy, mercapto, formyl; phenyl, benzyl, benzyloxy, phenoxy that 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”, SO2R”, OCOR”, SCOR” with or without halogen; and amino or aminocarbonyl substituted by one or two groups selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, benzyl, benzyloxy, phenoxy, COR”, COOR”, SO₂R”, OR”;

R’ each independently represents hydrogen, nitro, hydroxy, amino; or alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkoxyalkyl, alkoxycarbonyl, alkylthiocarbonyl, alkylsulfonyl, alkylsulfonylalkyl, alkylcarbonyl, alkylcarbonylalkyl, alkylacyloxy, alkylamino, alkylaminocarbonyl, alkoxyaminocarbonyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, trialkylsilyl, dialkylphosphono with or without halogen;

R” each independently represents hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl.

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

C represents hydrogen, halogen, C1-C6 alkyl or halo C1-C6 alkyl;

Q represents halogen, cyano, cyano C1-C6 alkyl, hydroxy CT-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;

Y represents nitro or NRiR₂, wherein Ri represents H; C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl optionally substituted by 1-2 R_H; -CORi₂, nitro, OR_]3, SO₂R₁₄, NRi₅R₁₆, N=CR₁₇Ri₈, C1-C6 alkylcarbamoyl, di-Cl-C6 alkylcarbamoyl, tri-Cl-C6 alkylsilyl or di-Cl-C6 alkylphosphono; R₂ represents H; C1-C6 alkyl optionally substituted by 1-2 Ru; or -COR₁₂; or

NR]R₂ represents N=CR₂iNR₂2R₂₃, N=CR₂4OR₂5; or \-k, k/, kk or k^O that is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkylamino, di-Cl-C6 alkylamino, C1-C6 alkoxycarbonyl;

wherein Ru independently represents halogen, hydroxy, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkylamino, di-Cl-C6 alkylamino, C1-C6 alkoxycarbonyl; or phenyl, naphthyl

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

R12 représente H, Cl-Cl 4 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;

Ri3 represents H, C1-C6 alkyl, halo C1-C6 alkyl, phenyl, benzyl or CHR3iC(O)OR₃2; R₃i represents H, C1-C6 alkyl or C1-C6 alkoxy; R₃₂ represents H, C1-C6 alkyl or benzyl;

Ru represents C1-C6 alkyl or halo C1-C6 alkyl;

Ris represents H, C1-C6 alkyl, formyl, C1-C6 alkylacyl, halo C1-C6 alkylacyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; R₁₆ represents H or C1-C6 alkyl;

Ri7 represents H, C1-C6 alkyl; or phenyl that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy; R_Ig represents H or C1-C6 alkyl; or N=CRi7Ris represents _or CZ/*;

R21, R24 each independently represent H or C1-C6 alkyl;

R22, R23 each independently represent H or C1-C6 alkyl; or NR22R23 represents ^NO,

XJ Q L J L o v—^J, ta , x/ or ---%

R₂5 represents C1-C6 alkyl;

the sait is métal sait, ammonium sait NH/, primary amine RNH₂ sait, secondary amine (R)₂NH sait, tertiary amine (R)₃N sait, quatemary amine sait (R)₄N⁺, morpholine sait, piperidine sait, pyridine sait, aminopropyl morpholine sait, Jeff amine D-230 sait, the sait of 2,4,6-tri(dimethylaminomethyl) phénol and sodium hydroxide, Cl-Cl 8 alkylsulfonium sait, Cl-Cl 8 alkylsulfoxonium sait, Cl-Cl 8 alkylphosphonium sait or Cl-Cl 8 alkanolphosphonium sait;

wherein, R each independently represents unsubstituted Cl-Cl 8 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C3-C18 cycloalkyl or phenyl, and the foregoing groups are optionally substituted by 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 1-1, X represents O or S;

M represents Cl-Cl 8 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6

O ,0 X A r X·⁴ Va⁴cycloalkyl C1-C6 alkyl, -(C1-C6 alkyl)-Z, V A * 6 ³, VO' \ R_{5 ;} R₅ ,

R4-_n.R₅ ./γ^οκ6

O _{7 v}o._R j_n._R, m ^v*⁴ A-*⁴ Δ⁴

Z represents 1 ^K3, A O _; o , Rs , R5 , Rs , cyano, nitro, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

R₃ each independently represents 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;

R4, R₅, Rê each independently represent 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;

R' i o rA . _t ,, T / 4— > an 1 4τ- b 1— n the term heterocyclyl” refers to V 11—I A/ \ ' ⁵ AA ।

R'

1Ej , LA, A^O _or A-⁰ with 0, 1 or 2 oxo groups; the term “aryl”

refers to phenyl or naphthyl; the term “heteroaryl” refers to

selected from the group consisting of halogen, nitro, cyano, thiocyano, hydroxy, carboxy, mercapto, formyl; phenyl, benzyl, benzyloxy, phenoxy that is unsubstituted or substituted by 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”, -(Cl-C6)alkyl-OR”, -(Cl-C6)alkyl-SR”, COR”, COOR”, COSR”, SOR”, SO₂R”, OCOR”,

SCOR” with or without halogen; and amino or aminocarbonyl substituted by 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”, SO₂R”, OR”;

R’ each independently represents hydrogen, nitro, hydroxy, amino; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 cyclo alkenyl, 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 CbC6 alkyl, C1-C6 alkylacyloxy, C1-C6 alkylamino, C1-C6 alkylaminocarbonyl, C1-C6 alkoxyaminocarbonyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, C1-C6 alkylaminocarbonyl C1-C6 alkÿl, tri-Cl-C6 alkylsilyl, di-C 1-C6 alkylphosphono with or without fluoro, chloro or bromo;

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

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

C represents hydrogen, halogen, C1-C6 alkyl or halo C1-C6 alkyl;

Q represents 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 . t) alkylamino C1-C2 alkyl, benzyl, naphthyl, furyl, thienyl, thiazolyl, pyridyl, pyrimidinyl; R¹' that is unsubstituted or substituted by C1-C6 alkyl; or phenyl that is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, halo C1-C6 alkyl, halogen and C1-C6 alkoxy;

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

the sait is métal sait, ammonium sait NH₄ ⁺, primary amine RNH₂ sait, secondary amine (R)₂NH sait, tertiary amine (R)₃N sait, quatemary amine sait (R)₄N⁺, morpholine sait, piperidine sait, pyridine sait, aminopropyl morpholine sait, Jeff amine D-230 sait, the sait of 2,4,6-tri(dimethylaminomethyl) phénol and sodium hydroxide, Cl-Cl 4 alkylsulfonium sait, C1-C14 alkylsulfoxonium sait, C1-C14 alkylphosphonium sait or C1-C14 alkanolphosphonium sait;

wherein, R each independently represents unsubstituted C1-C14 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C3-C12 cycloalkyl or phenyl; or C1-C14 alkyl optionally substituted by 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 1-1, X represents O or S;

M represents C1-C18 alkyl (preferably C1-C12 alkyl, more preferably C1-C8 alkyl, further 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 cycno 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 -(Cl-C2 o ^R<_NRs .

X n'”⁴ ^γ”⁴ Αγθ^ alkyl)-Z), ^Rs , ^Rs , O , tetrahydrofuryl, pyridyl, naphthyl, furyl, thienyl,

Y \ Il Y N-N _

Y that is unsubstituted or substituted by C1-C6 alkyl; or phenyl that is unsubstituted or substituted by C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkylamino, halogen or C1-C6 alkoxy;

o •<⁰ _Y%₃ ΑΛγ⁴ A'’⁴ /'N'*⁴ Tl ⁴¹ II ³ I l i N^—N

Z represents O , ^R ₅ , ^Rs , ^Rs , tetrahydrofuryl, pyridyl, r·' , thienyl, furyl, naphthyl; or phenyl that is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkyl, cyano and halogen;

R₃ each independently represents C1-C6 alkyl;

R4, R₅, Rô each independently represent hydrogen, C1-C6 alkyl or C1-C6 alkoxycarbonyl;

R’ represents hydrogen, C1-C6 alkyl or halo C1-C6 alkyl.

More further preferably, A, B each independently represent fluoro, chloro, bromo, iodo, methyl, ethyl, propyl, isopropyl, trifluoromethyl or cyclopropyl;

C represents hydrogen, fluoro, chloro, bromo, iodo, methyl or trifluoromethyl;

Q represents methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, fluoro, chloro, bromo, cyano, amino, nitro, formyl, methoxy, methylthio, methoxycarbonyl, monochloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloro ethyl, 2,2,2-trifluoroethyl, hydroxymethyl, \ \ Υή | , NC Y Y A benzyl, naphthyl, furyl, thiazolyl, pyridyl, pyrimidinyl; thiazolyl that is unsubstituted or substituted by chloro; thienyl that is

X

N-N unsubstituted or substituted by fluoro; R^,z that is unsubstituted or substituted by methyl or fluoro; or phenyl that is unsubstituted or substituted by at least one group selected from the group consisting of methyl, trifluoromethyl, chloro and methoxy;

O

H H H ÇA ₅ M 5 N X HN q Μ Λν /

Y represents NH₂, Y ''Ύ τ , A _; ^H

P^F3 h '' V o or the sait is métal sait, ammonium sait NH₄ ⁺, primary amine RNH₂ sait, secondary amine (R)₂NH sait, tertiary amine (R)₃N sait, quatemary amine sait (R)₄N⁺, morpholine sait, piperidine sait, pyridine sait, aminopropyl morpholine sait, Jeff amine D-230 sait, the sait of

2,4,6-tri(dimethylaminomethyl) phénol and sodium hydroxide, C1-C6 alkylsulfonium sait, C1-C6 alkylsulfoxonium sait, C1-C6 alkylphosphonium sait, or C1-C6 alkanolphosphonium sait;

wherein, R each independently represents unsubstituted Cl-Cl 4 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C12 cycloalkyl, phenyl or benzyl; or C1-C14 alkyl optionally substituted by 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;

the sait is preferably alkali métal (such as sodium, lithium, potassium, césium or rubidium) sait, alkaline earth métal (such as calcium, magnésium, barium or strontium) sait, heavy métal (such as antimony, zinc, bismuth, cadmium, cérium, chromium, cobalt, copper, iron or other metals with a density greater than 4) sait, aluminum sait, amine sait such as ammonium sait, tétraméthylammonium sait, tetraethylammonium sait, tetrapropyl ammonium sait, tetraisopropylammonium sait, tetrabutylammonium sait, benzyltrimethylammonium sait, benzyltriéthylammonium sait, choline amine sait, monomethylamine sait, dimethylamine sait, trimethylamine sait, monoethylamine sait, diethylamine sait, triethylamine sait, monoisopropylamine sait, diisopropylamine sait, triisopropylamine sait, monoisobutylamine sait, pentylamine sait, hexylamine sait, heptylamine sait, dodecylamine sait, tetradecyl amine sait, diallylamine sait, cyclododecylamine sait, benzylamine sait, monoethanolamine sait, diethanolamine sait, triethanolamine sait, tripropanolamine sait, triisopropanolamine sait, tri(2-hydroxypropyl)amine sait, methylmonoethanolamine sait, dimethylmonoethanolamine sait, methyldiethanolamine sait, diethylethanolamine sait, diglycolamine sait, sait of polyamine (for example, diethylenetriamine sait, dimethylaminopropylamine sait, 1,2-propyldiamine sait, triethylenetetramine sait, N,N-bis[aminopropyl]methylamine sait), 2-methylthiopropylamine sait,

HO. ! HO OH _ H₂N

2-butoxyethylamine sait, AEPD ( oh) sait, tri(methylol) aminomethane ( oh) sait,

O /N—\ morpholine sait, piperidine sait, pyridine sait, aminopropyl morpholine ( nh₂) sait,

T rc H₂b‘'''-X .

Jeff amine D-230 ( n , _n is 2 or 3) sait, the sait of 2,4,6-tri(dimethylaminomethyl) phénol and sodium hydroxide, sulfonium sait such as alkylsulfonium sait (such as trimethylsulfonium sait, triethylsulfonium sait), alkylsulfoxonium sait, phosphonium sait such as alkylphosphonium sait or alkanolphosphonium sait;

in formula 1-1, X represents O or S;

M represents 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-fluoroethyI, 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, >%^CN ₅

/ or / )that is unsubstituted or substituted by methyl; phenyl that is unsubstituted or substituted by methyl, dimethylamino, chloro, methoxy, trifluoromethyl or isopropyl; or benzyl that is unsubstituted or substituted by trifluoromethyl, bromo, chloro, fluoro, methoxy, cyano or methyl;

R’ represents hydrogen, methyl, ethyl or difluoromethyl.

In the définition of the compound represented by the above general formula I and in ail the structural formula below, the term, whether used alone or in a compound name, 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 -CH₂-, -CH₂CH₂-, -CH(CH3)-, -C(CH₃)₂- and the like. The alkyl group is, for example, Cl alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6-alkyl-hexyl such as n-hexyl, isohexyl or 1,3-dimethylbutyl. Similarly, alkenyl includes, for example, allyl, l-methylprop-2-en-l-yl, 2-methylprop-2-en-l-yl, but-2-en-l-yl, but-3-en-l-yl, l-methylbut-3-en-l-yl and l-methylbut-2-en-l-yl. Alkynyl includes, for example, propargyl, but-2-yn-l-yl, but-3-yn-l-yl, l-methylbut-3-yn-l-yl. Multiple bond can be at 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 members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl, wherein double bond can be at any position. Halogen is fluorine, chlorine, bromine or iodine.

If a group is substituted by a group, it is understood to mean that the group is substituted by one or more identical or different groups selected from those mentioned above. Further, the same or different substitution characters contained in the same or different substituents are independently selected, and may be the same or different.

In addition, unless specifically indicated, the term occurring before or after multiple juxtaposed substituents (separated by or “or”) in the présent invention has a limiting effect on each of the subséquent 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 subséquent groups “aryl”, “heteroaryl”, “arylalkyl” and “heteroarylalkyl”.

The préparation method of the R-pyridyloxycarboxylic acid and sait, ester dérivative thereof comprises the following steps.

A compound of formula III is reacted with a compound of formula II to obtain a compound of formula I-1 -1 ; the reaction scheme is as follows:

wherein, W represents an alkali métal, preferably K, Na; Hal represents 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 1-1-1 is reacted in the presence of a lithium hydroxide aqueous solution and a solvent to obtain a compound of formula I; the reaction scheme is as follows:

□ -1-1 preferably, the solvent is one or more selected from the group consisting of methanol, éthanol, and isopropanol.

The compound of formula I is reacted with M-SH to obtain a compound of formula 1-1-2; the reaction scheme is as follows:

wherein, the reaction is carried out in the presence of a dehydrant and a solvent, preferably the dehydrant is DCC, and the solvent is one or more selected from the group consisting of dichloromethane, dichloroethane, acetonitrile, Ν,Ν-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, toluene, xylene;

or, when Y represents NRiR₂ (Ri, R₂ are not hydrogen at the same time), it is obtained by nh₂

C^rAo^°^HO reacting a compound of formula 1-2 Q-2 or a compound of formula 1-1-3 nh₂

[ ( ^Q*

C N^X O'^^X'M

O ^α -^1-3 with a corresponding halide;

wherein, the halide is preferably chloride or bromide; the reaction is carried out in the presence of a base and a solvent, wherein the base is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and césium 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 sait is an agrochemically acceptable sait, which is preferably prepared by reacting the R-pyridyloxycarboxylic acid compound of the présent invention with a chemically acceptable basic compound.

For example, in the présent application, the diethylamine sait is prepared by reacting the R-pyridyloxycarboxylic acid compound of the présent invention with diethylamine.

For another example, the sait of 2,4,6-tri(dimethylaminomethyl) phénol and sodium hydroxide refers to the sait obtained by reacting the R-pyridyloxycarboxylic acid compound of the présent invention with 2,4,6-tri(dimethylaminomethyl) phénol and sodium hydroxide

OH (CH, Xh-CH,-<q^- CH₂-H(CH, )_a

7^ 4-HaOH

CH₂-H(CH₃ X _

The aforesaid agrochemically acceptable sait can be easily separated and can be purified by conventional séparation methods such as solvent extraction, dilution, recrystallization, column chromatography, and préparative thin layer chromatography.

The présent invention provides a herbicidal composition comprising (i) at least one of an R-type pyridyloxycarboxylic acid of the formula I and sait, ester dérivative thereof; preferably, further comprising (ii) one or more further herbicides and/or safeners; more preferably, further comprising (iii) agrochemically acceptable formulation auxiliaries.

The présent invention provides a method for controlling a weed comprising applying a herbicidally effective amount of at least one of the R-type pyridyloxycarboxylic acid and sait, ester dérivative thereof or the herbicidal composition on a plant or in a weed area. Preferably, the plant is rice, or the weed is a gramineous weed (such as Echinochloa crusgalli, Digitaria sanguinalis, Semen Euphorbiae Lathyridis) or a broad-leaved weed (such as Monochorîa Vaginalis, Abutilon theophrasti Medic., Galium aparine).

Use of at least one of the R-pyridyloxycarboxylic acid and sait, ester dérivative thereof or the herbicidal composition for controlling a weed, preferably, the R-pyridyloxycarboxylic acid and sait, ester dérivative thereof being used to control a weed in a useful crop, wherein the useful crop is a genetically modified crop or a crop treated by gene editing technology. Preferably, the crop is rice, or the weed is a gramineous weed (such as Echinochloa crusgalli, Digitaria sanguinalis, Semen Euphorbiae Lathyridis) or a broad-leaved weed (such as Monochorîa Vaginalis, Abutilon theophrasti Medic., Galium aparine).

The compounds of the formula I according to the invention hâve an outstanding herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. The active compounds also act efficiently on perennial weeds which produce shoots from rhizomes, root stocks or other perennial organs and which are difficult to control. In this context, it is generally immaterial whether the substances are applied pre-sowing, pre-emergence or post-emergence. Specifically, examples may be mentioned of some représentatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds according to the invention, without these being a restriction to certain species. Examples of weed species on which the active compounds act efficiently are, from amongst the monocotyledons, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and also Cyperus species from the annual sector and from amongst the perennial species Agropyron, Cynodon, Imperata and Sorghum, and also perennial Cyperus species.

In the case of the dicotyledonous weed species, the spectrum of action extends to species such as, for example, Gcdium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Sida, Matricaria and Abutilon from amongst the armuals, and Convolvulus, Cirsium, Rumex and Artemisia in the case of the perennial weeds. The active compounds according to the invention also effect outstanding control of harmful plants which occur under the spécifie conditions of rice growing such as, for example, Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus. If the compounds according to the invention are applied to the soil surface prior to germination, then the weed seedlings are either prevented completely from emerging, or the weeds grow until they hâve reached the cotylédon stage but then their growth stops, and, eventually, after three to four weeks hâve elapsed, they die completely. In particular, the compounds according to the invention exhibit excellent activity against Apera spica vend, Chenopodium album, Lamium purpureum, Polygonum convulvulus, Stellaria media, Veronica hederifolia, Veronica persica, Viola tricoter and against Amaranthus, Galium and Kochia species.

Although the compounds according to the invention hâve an excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops such as, for example, wheat, barley, rye, rice, com, sugarbeet, cotton and soya, are not damaged at ail, or only to a negligible extent. In particular, they hâve excellent compatibility in cereals, such as wheat, barley and com, in particular wheat. For these reasons, the présent compounds are highly suitable for selectively controlling undesired plant growth in plantings for agricultural use or in plantings of ornamcntals.

Owing to their herbicidal properties, these active compounds can also be employed for controlling harmful plants in crops of known or still to be developed genetically engineered plants. The transgenic plants generally hâve particularly advantageous properties, for example résistance to certain pesticides, in particular certain herbicides, résistance to plant diseases or causative organisms of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate, for example, to the quantity, quality, storage-stability, composition and to spécifie ingrédients of the harvested product. Thus, transgenic plants having an increased starch content or a modified quality of the starch or those having a different fatty acid composition of the harvested produce are known.

The use of the compounds of the formula I according to the invention or their salts in economically important transgenic crops of useful and omamental plants, for example of cereal, such as wheat, barley, rye, oats, millet, rice, maniok and com, or else in crops of sugarbeet, cotton, soya, rapeseed, potato, tomato, pea and other vegetable species is preferred. The compounds of the formula I can preferably be used as herbicides in crops of useful plants which are résistant or which hâve been made résistant by genetic engineering toward the phytotoxic effects of the herbicides.

Conventional ways for preparing novel plants which hâve modified properties compared to known plants comprise, for example, traditional breeding methods and the génération of mutants. Altematively, novel plants having modified properties can be generated with the aid of genetic engineering methods (see, for example, EP-A 0 221 044, EP-A 0 131 624). For example, there hâve been described several cases of genetically engineered changes in crop plants in order to modify the starch synthesized in the plants (for example WO 92/11376, WO 92/14827, WO 91/19806), transgenic crop plants which are résistant to certain herbicides of the glufosinate (Glufosinate ammonium)- (cf., for example, EP-A 0 242 236, EP-A 0 242 246) or 5 glyphosate-type (WO 92/00377), or of the sulfonylurea-type (EP-A 0 257 993, U. S. Pat. No. 5,013,659 A), transgenic crop plants, for example cotton, having the ability to produce Bacillus thuringiensis toxins (Bt toxins) which impart résistance to certain pests to the plants (EP-A 0 142 924, EP-A 0 193 259), transgenic crop plants having a modified fatty acid composition (WO 91/13972).

Numerous molecular biological techniques which allow the préparation of novel transgenic plants having modified properties are known in principle; 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 15 Weinheim, 2nd édition 1996, or Christou, Trends in Plant Science 1 (1996) 423-431). In order to carry out such genetic engineering manipulations, it is possible to introduce nucleic acid molécules into plasmids which allow a mutagenesis or a change in the sequence to occur by recombination of DNA sequences. Using the abovementioned standard processes it is possible, for example, to exchange bases, to remove partial sequences or to add natural or synthetic 20 sequences. To link the DNA fragments with each other, it is possible to attach adaptors or linkers to the fragments.

Plant cells having a reduced activity of a gene product can be prepared, for example, by expressing at least one appropriate antisense-RNA, a sense-RNA to achieve a cosuppression effect, or by expressing at least one appropriately constructed ribozyme which specifically 25 cleaves transcripts of the abovementioned gene product.

To this end it is possible to employ both DNA molécules which comprise the entire coding sequence of a gene product including any flanking sequences that may be présent, and DNA molécules which comprise only parts of the coding sequence, it being necessary for these parts to be long enough to cause an antisense effect in the cells. It is also possible to use DNA sequences 30 which hâve a high degree of homology to the coding sequences of a gene product but which are not entîrely identical.

When expressing nucleic acid molécules in plants, the synthesized protein can be localized in any desired compartment of the plant cells. However, to achieve localization in a certain compartment, it is, for example, possible to link the coding région with DNA sequences which 35 ensure localization in a certain compartment. 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).

The transgenic plant cells can be regenerated to whole plants using known techniques. The transgenic plants can in principle be plants of any desired plant species, i, e. both monocotyledonous and dicotyledonous plants. In this manner, it is possible to obtain transgenic plants which hâve modified properties by overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or by expression of heterologous (=foreign) genes or gene sequences.

When using the active compounds according to the invention in transgenic crops, in addition to the effects against harmful plants which can be observed in other crops, there are frequently effects which are spécifie for the application in the respective transgenic crop, for example a modified or specifically broadened spectrum of weeds which can be controlled, modified application rates which can be used for the application, preferably good combinability with the herbicides to which the transgenic crops are résistant, and an effect on the growth and the yield of the transgenic crop plants. The invention therefore also provides for the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

In addition, the substances according to the invention hâve outstanding growth-regulating properties in crop plants. They engage in the plant metabolism in a regulating manner and can this be employed for the targeted control of plant constituents and for facilitating harvesting, for example by provoking desiccation and stunted growth. Furthermore, they are also suitable for generally regulating and inhibiting undesirable végétative growth, without destroying the plants in the process. Inhibition of végétative growth plays an important rôle in many monocotyledon and dicotyledon crops because lodging can be reduced hereby, or prevented completely.

The compounds according to the invention can be applied in the customary formulations in the form of wettable powders, emulsifïable concentrâtes, sprayable solutions, dusts or granules. The invention therefore also provides herbicidal compositions comprising compounds of the formula I. The compounds of the formula I can be formulated in varions ways depending on the prevailing biological and/or chemico-physical parameters. Examples of suitable formulation options are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrâtes, emulsifïable concentrâtes (EC), émulsions (EW), such as oil-in-water and water-in-oil émulsions, sprayable solutions, suspension concentrâtes (SC), oil dispersions (OD), oil- or water-based dispersions, oil-miscible solutions, dusts (DP), capsule suspensions (CS), seed-dressing compositions, granules for broadeasting and soil application, granules (GR) in the form of microgranules, spray granules, coating granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in 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 likewise known and are described, for example, in Watkîns, 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 Détergents and Emulsifiers Annual, MC Publ. Corp. , Ridgewood N. J. ; Sisley and Wood, Encyclopedia of Surface Active Agents, Chem. Publ. Co. Inc. , N. Y. 1964; Schonfeldt, Grenzflüchenaktive Âthylenoxidaddkte [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 préparations which are uniformly dispersible in water and which contain, in addition to the active compound and as well as a diluent or inert substance, surfactants of ionic and/or nonionic type (wetting agents, dispersants), for example polyethoxylated alkyl phénols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol ethersulfates, alkanesulfonates, alkylbenzenesulfonates, sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutyinaphthalenesulfona-te or else sodium oleoylmethyltaurinate. To préparé the wettable powders, the herbicidally active compounds are finely ground, for example in customary apparatus such as hammer mills, fan mills and air-jet mills, and are mixed simultaneously or subsequently with the formulation auxiliaries.

Emulsifiable concentrâtes are prepared by dissolving the active compound in an organic solvent, for examplc butanol, cyclohexanone, dimethylformamide, xylene or else relatively high-boiling aromatic compounds or hydrocarbons or mixtures of the solvents, with the addition of one or more surfactants of ionic and/or nonionic type (emulsifiers). Examples of emulsifiers which can be used are calcium alkylarylsulfonates, such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.

Dusts are obtained by grinding the active compound with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspension concentrâtes can be water- or oil-based. They can be prepared, for example, by wet milling using commercially customary bead mills, with or without the addition of surfactants as already mentioned above, for example, in the case of the other formulation types.

Emulsions, for example oil-in-water émulsions (EW), can be prepared for example by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and, if desired, surfactants as already mentioned above, for example, in the case of the other formulation types.

Granules can be prepared either by spraying the active compound onto adsorptive, granulated inert material or by applying active-compound concentrâtes to the surface of carriers such as sand, kaolinites or granulated inert material, by means of adhesive binders, for example polyvinyl alcohol, sodium polyacrylate or else minerai oils. Suitable active compounds can also be granulated in the manner which is customary for the préparation of fertilizer granules, if desired as a mixture with fertilizers. Water-dispersible granules are generally prepared by the customary processes, such as spray-drying, fluidized-bed granulation, disk granulation, mixing using high-speed mixers, and extrusion without solid inert material.

For the préparation of disk, fluidized-bed, extruder and spray granules, see for example processes in Spray-Drying Handbook 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, Agglomération, Chemical and Engineering 1967, pages 147 ff. ; Perry’s Chemical Engineer's Handbook, 5th Ed. , McGraw-Hill, New York 1973, pp. 8-57. For further details on the formulation of crop protection products, 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.

The agrochemical formulations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula I. In wettable powders the concentration of active compound is, for example, from about 10 to 99% by weight, the remainder to 100% by weight consisting of customary formulation constituents. In emulsifiable concentrâtes the concentration of active compound can be from about 1 to 90%, preferably from 5 to 80%, by weight. Formulations in the form of dusts contain from 1 to 30% by weight of active compound, preferably most commonly from 5 to 20% by weight of active compound, while sprayable solutions contain from about 0. 05 to 80%, preferably from 2 to 50%, by weight of active compound. In the case of water-dispersible granules the content of active compound dépends partly on whether the active compound is in liquid or solid form and on the granulation auxiliaries, fillers, etc. that are used. In water-dispersiblc granules the content of active compound, for example, is between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, said formulations of active compound may comprise the tackifiers, wetting agents, dispersants, emulsifiers, pénétrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, évaporation inhibitors and pH and viscosity regulators which are customary in each case.

Based on these formulations it is also possible to produce combinations with other pesticidally active substances, for example insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and/or growth regulators, for example in the form of a ready-mix or tank mix.

Suitable active compounds which can be combined with the active compounds according to the invention in mixed formulations or in a tank mix are, for example, known active compounds as described in for example World Herbicide New Product Technology Handbook, China Agricultural Science and Farming Techniques Press, 2010. 9 and in the literature cited therein. For example the following active compounds may be mentioned as herbicides which can be combined with the compounds of the formula I (note: the compounds are either named by the common name in accordance with the International Organization for Standardization (ISO) or by the Chemical names, if appropriate together with a customary code number): acetochlor, butachlor, alachlor, propisochlor, metolachlor, s-metolachlor, pretilachlor, propachlor, ethachlor, napropamide, R-left handed napropamide, propanil, mefenacet, diphenamid, diflufenican, ethaprochlor, beflubutamid, bromobutide, dimethenamid, dimethenamid-P, etobenzanid, flufenacet, thenylchlor, metazachlor, isoxaben, flamprop-M-methyl, flamprop-M-propyl, allidochlor, pethoxamid, chloranocryl, cyprazine, mefluidide, monalide, delachlor, prynachlor, terbuchlor, xylachlor, dimethachlor, cisanilide, trimexachlor, clomeprop, propyzamide, pentanochlor, carbetamide, benzoylprop-ethyl, cyprazole, butenachlor, tebutam, benzipram, mogrton, dichlofluanid, naproanilide, diethatyl-ethyl, naptalam, flufenacet, benzadox, chlorthiamid, chlorophthalimide, isocarbamide, picolinafen, atrazine, simazine, prometryn, cyanatryn, simetryn, ametryn, propazine, dipropetryn, SSH-108, terbutryn, terbuthylazine, triaziflam, cyprazine, proglinazine, trietazine, prometon, simetone, aziprotryne, desmetryn, dimethametryn, procyazine, mesoprazine, sebuthylazine, secbumeton, terbumeton, methoprotryne, cyanatryn, ipazine, chlorazine, atraton, pendimethalin, eglinazine, cyanuric acid, indaziflam, chlorsulfuron, metsulfuron-methyl, bensulfuron methyl, chlorimuron-ethyl, tribenuron-methyl, thifensulfuron-methyl, pyrazosulfuron-ethyl, mesosulfuron, iodosulfuron-methyl sodium, foramsulfuron, cinosuhuron, triasulfuron, sulfometuron methyl, nicosulfuron, ethametsulfuron-methyl, amidosulfuron, ethoxysulfuron, cyclosulfamuron, rimsulfuron, azimsulfuron, flazasulfuron, monosulfuron, monosulfuron-ester, flucarbazone-sodium, flupyrsulfuron-methyl, halosulfuron-methyl, oxasulfuron, imazosulfuron, primisulfuron, propoxycarbazone, prosulfuron, sulfosulfuron, trifloxysulfuron, triflusulfuron-methyl, tritosulfuron, sodium metsulfuron methyl, flucetosulfuron, HNPC-C, orthosulfamuron, propyrisulfuron, metazosulfuron, acifluorfen, fomesafen, lactofen, fluoroglycofen, oxyfluorfen, chlomitrofen, aclonifen, ethoxyfen-ethyl, bifenox, nitrofluorfen, chlomethoxyfen, fluorodifen, fluoronitrofen, furyloxyfen, nitrofen, TOPE, DMNP, PPG1013, AKH-7088, halosafen, chlortoluron, isoproturon, linuron, diuron, dymron, fluometuron, benzthiazuron, methabenzthiazuron, cumyluron, ethidimuron, isouron, tebuthiuron, buturon, chlorbromuron, methyldymron, phenobenzuron, SK-85, metobromuron, metoxuron, afesin, monuron, siduron, fenuron, fluothiuron, neburon, chloroxuron, noruron, isonoruron, 3-cyclooctyl-l, thiazfluron, tebuthiuron, difenoxuron, parafluron, methylamine tribunil, karbutilate, trimeturon, dimefuron, monisouron, anisuron, methiuron, chloreturon, tetrafluron, phenmedipham, phenmedipham-ethyl, desmedipham, asulam, terbucarb, barban, propham, chlorpropham, rowmate, swep, chlorbufam, carboxazole, chlorprocarb, fenasulam, BCPC, CPPC, carbasulam, butylate, benthiocarb, vemolate, molinate, triallate, dimepiperate, esprocarb, pyributicarb, cycloate, avadex, EPTC, ethiolate, orbencarb, pebulate, prosulfocarb, tiocarbazil, CDEC, dimexano, isopolinate, methiobencarb, 2,4-D butyl ester, MCPA-Na, 2,4-D isooctyl ester, MCPA isooctyl ester, 2,4-D sodium sait, 2,4-D dimethyla mine sait, MCPA-thioethyl, MCPA, 2,4-D propionic acid, high 2,4-D propionic acid sait, 2,4-D butyric acid, MCPA propionic acid, MCPA propionic acid sait, MCPA butyric acid, 2,4,5-D, 2,4,5-D propionic acid, 2,4,5-D butyric acid, MCPA amine sait, dicamba, erbon, chlorfenac, saison, TBA, chloramben, methoxy-TBA, diclofop-methyl, fluazifop-butyl, fhiazifop-p-butyl, haloxyfop-methyl, haloxyfop-P, quizalofop-ethyl, quizalofop-p-ethyl, fenoxaprop-ethy, fenoxaprop-p-ethyl, propaquizafop, cyhalofop-butyl, metamifop, clodinafop-propargyl, fenthiaprop-ethyl, chloroazifop-propynyl, poppenate-methyl, trifopsime, isoxapyrifop, paraquat, diquat, oryzalin, ethalfluralin, isopropalin, nitralin, profluralin, prodinamine, benfluralin, fluchloraline, dinitramina, dipropalin, chlomidine, methalpropalin, dinoprop, glyphosate, anilofos, glufosinate ammonium, amiprophos-methyl, sulphosate, piperophos, bialaphos-sodium, bensulide, butamîfos, phocarb, 2,4-DEP, H-9201, zytron, imazapyr, imazethapyr, imazaquin, imazamox, imazamox ammonium sait, imazapic, imazamethabenz-methyl, fluroxypyr, fluroxypyr isooctyl ester, clopyralid, picloram, trichlopyr, dithiopyr, haloxydine, 3,5,6-trichloro-2-pyridinol, thiazopyr, fluridone, aminopyralid, diflufenzopyr, triclopyr-butotyl, Cliodinate, sethoxydim, clethodim, cycloxydim, alloxydim, clefoxydim, butroxydim, tralkoxydim, tepraloxydim, buthidazole, metribuzin, hexazinone, metamitron, ethiozin, ametridione, amibuzin, bromoxynil, bromoxynil octanoate, ioxynil octanoate, ioxynil, dichlobenil, diphenatrile, pyraclonil, chloroxynil, iodobonil, flumetsulam, florasulam, penoxsulam, metosulam, cloransulam-methyl, diclosulam, pyroxsulam, benfuresate, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, benzobicylon, mesotrione, sulcotrione, tembotrione, tefuryltrione, bicyclopyrone, ketodpiradox, isoxaflutole, clomazone, fenoxasulfone, methiozolin, fluazolate, pyraflufen-ethyl, pyrazolynate, difenzoquat, pyrazoxyfen, benzofenap, nipyraclofen, pyrasulfotole, topramezone, pyroxasulfone, cafenstrole, flupoxam, aminotriazole, amicarbazone, azafenidin, carfentrazone-ethyl, sulfentrazone, bencarbazone, benzfendizone, butafenacil, bromacil, isocil, lenacil, terbacil, flupropacil, cinidon-ethyl, flumiclorac-pentyl, flumioxazin, propyzamide, MK-129, flumezin, pentachlorophenol, dinoseb, dinoterb, dinoterb acetate, dinosam, DNOC, chloronitrophene, medinoterb acetate, dinofenate, oxadiargyl, oxadiazon, pentoxazone, Flufenacet, fluthiacet-methyl, fentrazamide, flufenpyr-ethyl, pyrazon, brompyrazon, metflurazon, kusakira, dimidazon, oxapyrazon, norflurazon, pyridafol, quinclorac, quinmerac, bentazone, pyridate, oxaziclomefone, benazolin, clomazone, cinmethylin, ZJ0702, pyribambenz-propyl, indanofan, sodium chlorate, dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, flupropanate, cyperquat, bromofenoxim, epronaz, methazole, flurtamone, benfuresate, ethofumesate, tioclorim, chlorthal, fluorochloridone, tavron, acrolein, bentranil, tridiphane, chlorfenpropmethyl, thidiarizonaimin, phenisopham, busoxinone, methoxyphenone, saflufenacil, clacyfos, chloropon, alorac, diethamquat, etnipromid, iprymidam, ipfencarbazone, thiencarbazone-methyl, pyrimisulfan, chlorflurazole, tripropindan, sulglycapin, prosulfalin, cambendichlor, aminocyclopyrachlor, rodethanil, benoxacor, fenclorim, flurazole, fenchlorazole-ethyl, cloquintocet-mexyl, oxabetrinil, MG/91, cyometrinil, DKA-24, mefenpyr-diethyl, furilazole, fluxofenim, isoxadifen-ethyl, dichlormid, halauxifen-methyl, DOW florpyrauxifen, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, DK-8910, V-53482, PP-60O, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.

In the context of the présent spécification, if an abbreviation of a generic name of an active compound is used, it includes in each case ail customary dérivatives, such as esters and salts, as well as isomers, in particular optical isomers, especially one or more commercially available forms. If the generic name dénotés an ester or a sait, it also includes in each case ail other conventional dérivatives, such as other esters and salts, free acids and neutral compounds, as well as isomers, in particular optical isomers, especially one or more commercially available forms. The Chemical name given to a compound means at least one compound encompassed by the generic name, and generally the preferred compound.

For use, the formulations which are présent in commercially available form are, if appropriate, diluted in the customary manner, for example using water in the case of wettable powders, emulsifiable concentrâtes, dispersions and water-dispersible granules. Products in the form of dusts, granules for soil application or broadcasting and sprayable solutions are usually not further diluted with other inert substances prior to use. The application rate of the compounds of the formula I required varies with the extemal conditions, such as température, humidity, the nature of the herbicide used and the like. It can vary within wide limits, for example between 0. 001 and 1. 0 kg a.i./ha or more of active substance, but it is preferably between 0. 005 and 750 g a.i./ha, in particular between 0. 005 and 500 g a.i./ha.

Spécifie Mode for Carrying out the Invention

The following examples are intended to illustrate the présent invention and should not be construed as limiting the présent invention in any way. The scope for which protection is sought in the présent invention is intended to be defined by the daims.

In view of économies and variety of a compound, we preferably synthesized several compounds, part of which are listed in the following Tables 1-2. The structure and information of a certain compound are shown in Tables 1-3. The compounds in Tables 1-2 are listed for fùrther explication of the présent invention, other than any limit therefor. The subject of the présent invention should not be interpreted by those skilled in the art as being limited to the following compounds.

Table 1 : The structure of compounds (7? configuration)

O

No.	A	B	c	Q	Y
1-1	F	F	F	p	nh₂
1-2	Cl	Cl	Cl	ch₃	nh₂
1-3	Cl	Cl	H		nh₂
1-4	Cl	Cl	F		nh₂
1-5	Cl	Cl	ch₃	ch₃	nh₂
1-6	Cl	Cl	cf₃	P	nh₂
1-7	ch₃	ch₃	F	ch₃	nh₂
1-8	Et	Et	cf₃	ch₃	nh₂
1-9		CI	H	ch₃	nh₂


1-10	-H	Cl	Cl	ch₃	nh₂
1-11	F		CF₃	ch₃	nh₂
1-12	Br	Br	F	ch₃	nh₇
1-13	I	I	H	ch₃	nh₂
1-14		-M	F	Ύ	nh₂
1-15	cf₃	Cl	F	ch₃	nh₂
1-16	Cl	cf₃	H	Y	nh₂
1-17	Cl	Cl	I	ch₃	nh₂
1-18	Cl		Br	0	nh₂
1-19	ch₃	ch₃	ch₃	ch₃	nh₂
1-20	Cl	ch₃	F	ch₃	nh₂
1-21	Cl	ch₃	H	ch₃	nh₂
1-22	Cl	40	F	ch₃	nh₂
1-23	F	F	cf₃	ch₃	nh₂
1-24	ch₃	40	F	ch₃	nh₂
1-25	Cl	ch₃	Br	ch₃	nh₂
1-26	Cl	Cl	F	ch₃	nh₂
1-27	Cl	Cl	F	Et	nh₂
1-28	Cl	Cl	F		nh₂
1-29	Cl	Cl	F		nh₂
1-30	Cl	Cl	F	40	nh₂
1-31	Cl	Cl	F	-Oc/	nh₂
1-32	Cl	Cl	F		nh₂
1-33	Cl	Cl	F		nh₂
1-34	Cl	Cl	F		nh₂
1-35	Cl	Cl	F		nh₂

1-36	Cl	Cl	F	F	nh₂
1-37	Cl	Cl	F	Cl	nh₂
1-38	Cl	CI	F	Br	nh₂
1-39	CI	Cl	F	Υόι	nh₂
1-40	Cl	Cl	F	Y F	nh₂
1-41	Cl	Cl	F	F A F	nh₂
1-42	Cl	Cl	F		νή₂
1-43	Cl	Cl	F	CF₃	nh₂
1-44	Cl	Cl	F	Vcf₃	nh₂
1-45	Cl	Cl	F	CN	nh₂
1-46	Cl	Cl	F	NcY	nh₂
1-47	Cl	Cl	F	nh₂	nh₂
1-48	Cl	CI	F		nh₂
1-49	Cl	Cl	F	Y'-	nh₂
1-50	Cl	Cl	F	VOH	nh₂
1-51	Cl	Cl	F	no₂	nh₂
1-52	Cl	Cl	F		nh₂
1-53	Cl	Cl	F	'Yto	nh₂
1-54	Cl	Cl	F	0 Va	nh₂
1-55	Cl	Cl	F	X	nh₂
1-56	Cl	Cl	F		nh₂
1-57	Cl	Cl	F		nh₂
1-58 _	Cl	Cl	F		nh₂

1-59	Cl	Cl	F	7PP N-N	nh₂
1-60	Cl	Cl	F	N-N /	nh₂
1-61	Cl	Cl	F	CF N-N F- / F	nh₂
1-62	Cl	Cl	F	'-''cf₃	nh₂
1-63	Cl	Cl	F	O P	nh₂
1-64	Cl	Cl	F		nh₂
1-65	Cl	Cl	F		nh₂
1-66	Cl	Cl	F	P	nh₂
1-67	Cl	Cl	F	N	nh₂
1-6S	Cl	Cl	F	ch₃	H AS
1-69	Cl	Cl	F	P	H
1-70	Cl	Cl	F	ch₃	0 A* H
1-71	Cl	Cl	F	ch₃	W H
1-72	Cl	Cl	F	ch₃	vO HN._rJ__

Table 2: The structure of dérivatives (7? configuration)

Y

O □ -1

No.	A	B	c	Q	X	Y	salt/M
2-1	CI	Cl	F		0	nh₂	sodium sait
2-2	Cl	Cl	F	ch₃	s	nh₂	calcium sait
2-3	Cl	Cl	F	ch₃	0	nh₂	ammonium sait
2-4	Cl	Cl	F	ch₃	s	nh₂	tétraméthylammonium sait
2-5	Cl	Cl	F	Et	0	nh₂	benzyltrimethylammonium sait
2-6	Cl	Cl	F		0	nh₂	choline amine sait
2-7	Cl	Cl	F	ch₃	0	nh₂	dimethylamine sait
2-8	Cl	Cl	F	yx	0	nh₂	monoisopropylamine sait
2-9	Cl	Cl	F	Et	s	nh₂	benzylamine sait
2-10	Cl	Cl	F	Et	0	nh₂	monoethanolamine sait
2-11	Cl	Cl	F		0	nh₂	diglycolamine sait
2-12	Cl	Cl	F	Et	s	nh₂	diallylamine sait
2-13	Cl	Cl	F	Ύ	0	nh₂	cyclododecylamine sait
2-14	Cl	CI	F	ch₃	0	nh₂	dimethylmonoethanolamine sait
2-15	Cl	Cl	F		0	nh₂	diethylenetriamine sait
2-16	Cl	Cl	F	(7	0	nh₂	dimethylaminopropylamine sait
2-17	Cl	Cl	F	ch₃	s	nh₂	1,2-propyldiamine sait
2-18	Cl	Cl	F	Et	s	nh₂	triethylenetetramine sait
2-19	Cl	Cl	F		0	nh₂	N,N-bis[aminopropyl]methyla mine sait___________
2-20	Cl	Cl	F		s	nh₂	2-methylthiopropylamine sait
2-21	Cl	Cl	F	—\| y]	0	nh₂	2-butoxyethylamine sait

2-22	Cl	Cl	F	Γ ch₃	0	nh₂	AEPD sait
2-23	Cl	Cl	F		O	nh₂	tri(methylol) aminomethane sait
2-24	Cl	Cl	F	ch₃	O	nh₂	morpholine sait
2-25	Cl	Cl	F	Et	s	nh₂	aminopropyl morpholine sait
2-26	Cl	Cl	F	ch₃	s	nh₂	Jeff amine D-230 sait
2-27	Cl	Cl	F	Et	0	nh₂	the sait of 2,4,6-tri(dimethylaminomethy 1) phénol and sodium hydroxide
2-28	Cl	ch₃	H	ch₃	0	nh₂	ch₃
2-29	Cl	ch₃	F	ch₃	0	nh₂	ch₃
2-30	Cl	Cl	H	ch₃	0	nh₂	ch₃
2-31	Cl	Cl	Cl	ch₃	O	nh₂	ch₃
2-32	Cl	Cl	ch₃	ch₃	O	nh₂	ch₃
2-33	Cl	Cl	F	Et	s	nh₂	ch₃
2-34	Cl	Cl	F	Et	O	nh₂	ch₃
2-35	Cl	Cl	F		O	nh₂	ch₃
2-36	Cl	Cl	F	A	s	nh₂	ch₃
2-37	Cl	Cl	F		O	nh₂	ch₃
2-38	Cl	Cl	F		O	nh₂	ch₃
2-39	Cl	Cl	F	cf₃	O	nh₂	ch₃
2-40	Cl	Cl	F	^cf₃	O	nh₂	ch₃
2-41	Cl	Cl	F	V'CI	O	nh₂	ch₃
2-42	Cl	Cl	F		O	nh₂	ch₃
2-43	Cl	Cl	F	yt	O	nh₂	ch₃
2-44	Cl	Cl	F	F Xf	O	nh₂	ch₃
2-45	Cl	Cl	F		O	nh₂	ch₃
246	Cl	Cl	F		O	nh₂	ch₃
2-47	Cl	Cl	F	0 Va	O	nh₂	ch₃
2-48	Cl	Cl	F	'Yq	O	nh₂	__________ch₃__________
2-49	Cl	Cl	F	Y^OH	O	nh₂	__ch₃

2-50	Cl	Cl	F	no₂	O	nh₂	ch₃
2-51	Cl	Cl	F	F	0	nh₂	ch₃
2-52	Cl	Cl	F	Br	0	nh₂	ch₃
2-53	Cl	Cl	F	Cl	0	nh₂	ch₃
2-54	Cl	Cl	F	Y'O^Z		nh₂	ch₃
2-55	Cl	Cl	F	^;Υ'ό^ζ		nh₂	ch₃
2-56	Cl	Cl	F	nh₂	0	nh₂	ch₃
2-57	Cl	Cl	F		0	nh₂	ch₃
2-58	Cl	Cl	F	γγ	0	nh₂	ch₃
2-59	Cl	Cl	F		0	nh₂	ch₃
2-60	Cl	Cl	F	νοΆ	0	nh₂	ch₃
2-61	Cl	Cl	F	CN	0	nh₂	ch₃
2-62	Cl	Cl	F	VG	O	nh₂	ch₃
2-63	Cl	Cl	F		0	nh₂	ch₃
2-64	Cl	Cl	F	Q	0	nh₂	ch₃
2-65	Cl	Cl	F		0	nh₂	ch₃
2-66	Cl	Cl	F	V	0	nh₂	ch₃
2-67	Cl	Cl	F	Ύ n-# Cl	0	nh₂	ch₃
2-68	Cl	Cl	F	. H Υγ-Κ F^Z	0	nh₂	ch₃
2-69	Cl	Cl	F	CH₃	O	nh₂	ch₃
2-70	Cl	Cl	F	ch₃	s	nh₂	ch₃
2-71	Cl	Cl	F	ch₃	0	nh₂	Et
2-72	Cl	Cl	F	ch₃	s	nh₂	Et
2-73	Cl	Cl	F	ch₃	0	_______nh₂_______

—
2-74	Cl	Cl	F	ch₃	s	nh₂
2-75	Cl	Cl	F	CH₃	0	nh₂
2-76	Cl	Cl	F	ch₃	s	nh₂	V
2-77	Cl	Cl	F	ch₃	0	nh₂	y./v/
2-78	Cl	Cl	F	ch₃	s	nh₂	XxXXX
2-79	Cl	Cl	F	ch₃	0	nh₂
2-80	Cl	Cl	F	ch₃	s	nh₂
2-81	Cl	Cl	F	ch₃	0	nh₂
2-82	Cl	Cl	F	ch₃	s	nh₂	'/γΧ
2-83	Cl	Cl	F	ch₃	0	nh₂	“T
2-84	Cl	Cl	F	ch₃	s	nh₂	V
2-85	Cl	Cl	F	ch₃	0	nh₂
2-86	Cl	Cl	F	ch₃	s	nh₂
2-87	Cl	Cl	F	ch₃	0	nh₂
2-88	Cl	Cl	F	ch₃	s	nh₂
2-89	Cl	Cl	F	ch₃	0	nh₂


2-90	Cl	Cl	F	CH₃	s	nh₂
2-91	Cl	Cl	F	ch₃	0	nh₂
2-92	Cl	Cl	F	ch₃	s	nh₂	Ά
2-93	Cl	Cl	F	ch₃	0	nh₂
2-94	Cl	CI	F	ch₃	s	nh₂
2-95	Cl	Cl	F	ch₃	0	nh₂
2-96	Cl	Cl	F	ch₃	s	nh₂	ηΛ
2-97	Cl	Cl	F	ch₃	0	nh₂
2-98	Cl	Cl	F	ch₃	s	nh₂
2-99	Cl	Cl	F	ch₃	0	nh₂	Τ
2-100	Cl	Cl	F	ch₃	s	nh₂	Τ
2-101	Cl	Cl	F	ch₃	0	nh₂
2-102	Cl	Cl	F	ch₃	s	nh₂
2-103	Cl	Cl	F	ch₃	0	nh₂	_


2-104	Cl	Cl	F	ch₃	s	nh₂	—
2-105	Cl	Cl	F	ch₃	0	nh₂
2-106	Cl	Cl	F	ch₃	s	nh₂
2-107	Cl	Cl	F	ch₃	0	nh₂
2-108	Cl	Cl	F	ch₃	s	nh₂
2-109	Cl	Cl	F	ch₃	0	nh₂
2-110	Cl	Cl	F	ch₃	s	νή₂
2-111	Cl	CI	F	ch₃	0	nh₂
2-112	CI	Cl	F	ch₃	s	nh₂
2-113	Cl	Cl	F	ch₃	0	nh₂
2-114	Cl	Cl	F	ch₃	s	nh₂
2-115	Cl	Cl	F	ch₃	0	nh₂
2-116	Cl	Cl	F	ch₃	s	nh₂
2-117	Cl	Cl	F	ch₃	0	nh₂
2-118	Cl	Cl	F	ch₃	s	_______nh₂_______


2-119	Cl	Cl	F	ch₃	0	nh₂
2-120	Cl	Cl	F	ch₃	s	nh₂
2-121	Cl	Cl	F	ch₃	0	nh₂
2-122	Cl	Cl	F	ch₃	s	nh₂
2-123	Cl	Cl	F	ch₃	0	nh₂
2-124	Cl	Cl	F	ch₃	s	nh₂
2-125	Cl	Cl	F	ch₃	0	nh₂
2-126	Cl	Cl	F	ch₃	s	nh₂
2-127	Cl	Cl	F	ch₃	O	nh₂
2-128	Cl	Cl	F	ch₃	s	nh₂
2-129	Cl	Cl	F	ch₃	0	nh₂
2-130	Cl	Cl	F	ch₃	s	nh₂
2-131	Cl	Cl	F	ch₃	0	nh₂ .
2-132	Cl	Cl	F	ch₃	s	nh₂

2-133	Cl	Cl	F	ch₃	0	nh₂
2-134	Cl	Cl	F	ch₃	s	nh₂
2-135	Cl	Cl	F	ch₃	O	nh₃
2-136	Cl	Cl	F	ch₃	s	nh₂
2-137	Cl	Cl	F	ch₃	0	nh₂
2-138	Cl	Cl	F	ch₃	s	nh₂
2-139	Cl	Cl	F	ch₃	0	nh₂
2-140	Cl	Cl	F	ch₃	s	nh₂
2-141	Cl	Cl	F	ch₃	0	nh₂
2-142	Cl	Cl	F	ch₃	s	nh₂
2-143	Cl	Cl	F	ch₃	O	nh₂
2-144	Cl	Cl	F	ch₃	s	nh₂
2-145	Cl	Cl	F	ch₃	O	nh₂	XX
2-146	Cl	Cl	F	ch₃	s	nh₂	_X_

2-147	Cl	Cl	F	ch₃	0	nh₂
2-148	Cl	Cl	F	CH₃	s	nh₂	ίγ
2-149	Cl	Cl	F	ch₃	0	nh₂
2-150	Cl	Cl	F	ch₃	s	nh₂
2-151	Cl	Cl	F	ch₃	0	nh₂	AA
2-152	Cl	Cl	F	ch₃	s	nh₂
2-153	CI	Cl	F	ch₃	0	nh₂
2-154	Cl	Cl	F	ch₃	s	nh₂
2-155	Cl	Cl	F	ch₃	0	nh₂
2-156	Cl	Cl	F	ch₃	s	nh₂
2-157	Cl	Cl	F	ch₃	0	nh₂
2-158	Cl	Cl	F	ch₃	s	nh₂
2-159	Cl	Cl	F	ch₃	0	•Ü nh₂
2-160	Cl	Cl	F	ch₃	s	nh₂
2-161	Cl	Cl	F	ch₃	0	nh₂


2-162	Cl	Cl	F	ch₃	s	nh₂
2-163	Cl	Cl	F	ch₃	0	nh₂
2-164	Cl	Cl	F	ch₃	s	nh₂
2-165	Cl	Cl	F	ch₃	0	nh₂
2-166	Cl	Cl	F	ch₃	s	nh₂
2-167	Cl	Cl	F	ch₃	0	nh₂
2-168	Cl	Cl	F	ch₃	s	nh₂
2-169	Cl	Cl	F	ch₃	0	nh₂	' La,-·-'
2-170	Cl	CI	F	ch₃	s	nh₂
2-171	Cl	Cl	F	ch₃	0	nh₂
2-172	Cl	Cl	F	ch₃	s	nh₂
2-173	Cl	Cl	F	ch₃	O	nh₂


2-174	Cl	Cl	F	ch₃	s	nh₂
2-175	Cl	Cl	F	ch₃	O	nh₂
2-176	Cl	Cl	F	ch₃	s	nh₂
2-177	Cl	Cl	F	ch₃	O	nh₂
2-178	Cl	Cl	F	ch₃	s	. nh₂
2-179	Cl	Cl	F	ch₃	0	nh₂
2-180	Cl	Cl	F	ch₃	s	nh₂
2-181	Cl	Cl	F	ch₃	0	nh₂
2-182	Cl	Cl	F	ch₃	s	nh₂
2-183	Cl	Cl	F	ch₃	0	nh₂
2-184	Cl	Cl	F	ch₃	s	nh₂
2-185	Cl	Cl	F	ch₃	0	nh₂
2-186	Cl	Cl	F	ch₃	s	nh₂
2-187	Cl	Cl	F	ch₃	⁰	______nh₂_______	____________________________________________________ \|


2-188	Cl	Cl	F	ch₃	s	nh₂
2-189	Cl	Cl	F	ch₃	0	nh₂
2-190	Cl	Cl	F	ch₃	s	nh₂
2-191	Cl	Cl	F	ch₃	0	nh₂
2-192	Cl	Cl	F	ch₃	s	nh₂
2-193	Cl	Cl	F	ch₃	0	nh₂	7™
2-194	Cl	Cl	F	ch₃	s	nh₂	Ύ“
2-195	Cl	Cl	F	ch₃	0	nh₂
2-196	Cl	Cl	F	ch₃	s	nh₂
2-197	Cl	Cl	F	ch₃	0	nh₂
2-198	Cl	Cl	F	ch₃	s	nh₂
2-199	Cl	Cl	F	ch₃	O	nh₂
2-200	Cl	Cl	F	ch₃	s	nh₂
2-201	Cl I Cl	F	ch₃	o \|________nh₂________


2-202	Cl	Cl	F	ch₃	s	nh₂
2-203	Cl	Cl	F	ch₃	0	nh₂
2-204	Cl	Cl	F	ch₃	s	nh₂
2-205	Cl	Cl	F	ch₃	0	nh₂
2-206	Cl	Cl	F	ch₃	s	nh₂
2-207	Cl	Cl	F	ch₃	0	nh₂	QCk
2-208	Cl	Cl	F	ch₃	s	nh₂
2-209	Cl	Cl	F	ch₃	0	nh₂	/ [AP
2-210	Cl	Cl	F	ch₃	s	nh₂
2-211	Cl	Cl	F	ch₃	0	nh₂	PL
2-212	Cl	Cl	F	ch₃	s	nh₂	PL

2-213	Cl	Cl	F	ch₃	0	nh₂
2-214	Cl	Cl	F	ch₃	s	nh₂	T
2-215	Cl	Cl	F	ch₃	0	nh₂
2-216	Cl	Cl	F	ch₃	s	nh₂
2-217	Cl	Cl	F	ch₃	0	nh₂	YyYzYzYzY
2-218	Cl	Cl	F	ch₃	s	nh₂	YyYzYzYY
2-219	Cl	Cl	F	ch₃	0	nh₂
2-220	Cl	Cl	F	ch₃	s	nh₂
2-221	Cl	Cl	F	ch₃	0	nh₂
2-222	Cl	Cl	F	ch₃	s	nh₂
2-223	Cl	Cl	F	ch₃	0	nh₂
2-224	Cl	Cl	F	ch₃	s	nh₂
2-225	Cl	Cl	F	ch₃	0	nh₂
2-226	Cl	Cl	F	ch₃	s	______nh₂_______


2-227	Cl	Cl	F	ch₃	0	nh₂
2-228	Cl	Cl	F	ch₃	s	nh₂	Oik
2-229	Cl	Cl	F	ch₃	0	nh₂
2-230	Cl	Cl	F	ch₃	s	nh₂
2-231	Cl	Cl	F	ch₃	0	nh₂	/	\
2-232	Cl	Cl	F	ch₃	s	nh₂	P	t<
2-233	Cl	Cl	F	ch₃	0	nh₂
2-234	Cl	Cl	F	ch₃	s	nh₂
2-235	Cl	Cl	F	ch₃	0	nh₂
2-236	Cl	Cl	F	ch₃	s	nh₂
2-237	Cl	Cl	F	ch₃	0	nh₂
2-238	Cl	Cl	F	ch₃	s	nh₂

						1
2-239	Cl	Cl	F	ch₃	0	nh₂
2-240	Cl	Cl	F	ch₃	s	nh₂
2-241	Cl	Cl	F	CH₃	0	nh₂	\ —/
2-242	Cl	Cl	F	ch₃	s	nh₂	Τ’- —/
2-243	Cl	Cl	F	ch₃	0	nh₂
2-244	Cl	Cl	F	ch₃	s	nh₂
2-245	Cl	Cl	F	ch₃	O	nh₂
2-246	Cl	Cl	F	ch₃	s	nh₂
2-247	Cl	Cl	F	ch₃	0	nh₂	yv
2-248	Cl	Cl	F	ch₃	s	nh₂
2-249	Cl	Cl	F	ch₃	0	nh₂	/
2-250	Cl	Cl	P 1	ch₃	s	nh₂


2-251	Cl	Cl	F	CH₃	0	nh₂		\
2-252	Cl	Cl	F	ch₃	s	nh₂	/	—
2-253	Cl	Cl	F	ch₃	0	nh₂
2-254	Cl	Cl	F	ch₃	s	nh₂
2-255	Cl	Cl	F	ch₃	0	nh₂	Y(ch₂)₁₇ch₃
2-256	Cl	CI	F	ch₃	S	nh₂	γ(ΟΗ₂)₁₇ΟΗ₃
2-257	Cl	Cl	F	ch₃	0	nh₂	Χ-γ-(ϋΗ₂)₁₂ΟΗ(ϋΗ₃)₂
2-258	Cl	Cl	F	ch₃	s	nh₂
2-259	Cl	Cl	F	ch₃	0	nh₂	^^CH₂)i₃CH₃
2-260	Cl	Cl	F	ch₃	s	nh₂	Î^(ch₂)₁₃ch₃
2-261	Cl	Cl	F	ch₃	0	nh₂	A ¹ (ch₂)₇ch₃
2-262	Cl	Cl	F	ch₃	s	nh₂	A ¹ (CH₂)₇CH₃
2-263	Cl	Cl	F	ch₃	O	______nh₂_______	I

2-264	Cl	Cl	F	ch₃	0	nh₂
2-265	Cl	Cl	F	ch₃	0	nh₂
2-266	Cl	Cl	F	ch₃	s	nh₂
2-267	Cl	Cl	F	ch₃	0	nh₂	γ,ΟΝ
2-268	Cl	Cl	F	ch₃	0	nh₂	Y,.no₂
2-269	Cl	Cl	F	ch₃	O	nh₂
2-270	Cl	Cl	ch₃	ch₃	0	nh₂
2-271	Cl	Cl	F	ch₃	O	nh₂
2-272	Cl	Cl	F	ch₃	s	nh₂	__ΥΧΧ__
2-273	Cl	Cl	F	ch₃	0	nh₂
2-274	Cl	Cl	F	ch₃	s	nh₂
2-275	Cl	CI	F	ch₃	0	nh₂	kk ___
2-276	Cl	Cl	F	ch₃	0	nh₂
2-277	CI	Cl	F	ch₃	0	nh₂	__
2-278	Cl	Cl	F	ch₃	0	nh₂	^^'Rr
2-279	Cl	Cl	F	ch₃	0	nh₂	-A
2-280	Cl	Cl	F	ch₃	O	nh₂
2-281	Cl	Cl	F	ch₃	0	nh₂	A'· cf_q
2-282	Cl	Cl	F	ch₃	0	nh₂	V Ο -Π Π ω
2-283	CI	Cl	F	ch₃	O	nh₂	1
2-284	Cl	Cl	F	ch₃	0	nh₂	_____X^NH?_____
2-285	Cl	Cl	F	ch₃	0	nh₂
2-286	Cl	Cl	F	ch₃	0	nh₂	Cl χΑγΟΙ Cl
2-287	Cl	Cl	F	ch₃	0	nh₂
2-288	Cl	Cl	F	ch₃	0	nh₂	(/X
2-289	Cl	Cl	F	ch₃	0	nh₂	o 1

2-290	Cl	CI	F	CH₃	s	nh₂	O
2-291	Cl	Cl	F	ch₃	0	nh₂	/ \__
2-292	Cl	Cl	F	ch₃	0	nh₂	ΑΧ
2-293	Cl	Cl	F	ch₃	0	nh₂	O t II - -s— ' II 0
2-294	Cl	Cl	F	ch₃	0	nh₂	0
2-295	Cl	Cl	F	ch₃	O	nh₂
2-296	Cl	Cl	F	ch₃	0	nh₂	JT _
2-297	Cl	Cl	F	ch₃	0	nh₂	Xk
2-298	Cl	CI	F	ch₃	0	nh₂
2-299	Cl	Cl	F	ch₃	0	nh₂	T
2-300	Cl	Cl	F	ch₃	0	nh₂	TJ
2-301	Cl	Cl	F	ch₃	s	nh₂
2-302	Cl	Cl	F	ch₃	O	nh₂
2-303	Cl	Cl	F	ch₃	s	nh₂	Tp¹
2-304	Cl	Cl	F	ch₃	0	nh₂	xXX
2-305	Cl	Cl	F	ch₃	s	nh₂	TT
2-306	Cl	Cl	F	ch₃	0	nh₂
2-307	CI	Cl	F	ch₃	s	nh₂


2-308	Cl	Cl	F	ch₃	0	nh₂
2-309	Cl	Cl	F	ch₃	s	nh₂	XJ3 F
2-310	Cl	Cl	F	ch₃	0	nh₂	xx
2-311	Cl	Cl	F	ch₃	^s	nh₂	. LL M
2-312	Cl	Cl	F	ch₃	0	nh₂	X
2-313	Cl	Cl	F	ch₃	s	nh₂	^i\.F
2-314	Cl	Cl	F	ch₃	o	nh₂	XJ) Cl
2-315	Cl	Cl	F	ch₃	s	nh₂	Xj) Cl
2-316	Cl	Cl	F	ch₃	0	nh₂	xx
2-317	Cl	Cl	F	ch₃	s	nh₂	XX
2-318	Cl	Cl	F	ch₃	0	nh₂	XA
2-319	Cl	CI	F	ch₃	s	nh₂	Xj
2-320	Cl	Cl	F	ch₃	0	nh₂
2-321	Cl	Cl	F	ch₃	s	nh₂	__ Xj) Br
2-322	Cl	Cl	F	ch₃	o	nh₂	XX
2-323	CI	Cl	F	ch₃	s	nh₂	R □□

2-324	Cl	Cl	F	ch₃	0	nh₂	b CD “T
2-325	Cl	Cl	F	ch₃	s	nh₂	^Br
2-326	Cl	Cl	F	Et	0	nh₂	/=\ / MW^-0
2-327	Cl	Cl	F	ch₃	O	nh₂	cf₃
2-328	Cl	Cl	F	ch₃	s	nh₂	yjQ cf₃
2-329	Cl	Cl	F	ch₃	O	nh₂	XxCX_CF3
2-330	Cl	Cl	F	ch₃	s	nh₂
2-331	Cl	Cl	F	ch₃	0	nh₂	b O “Π Cû
2-332	Cl	Cl	F	ch₃	s	nh₂	b O J¹
2-333	Cl	Cl	F	ch₃	O	nh₂
2-334	Cl	Cl	F	ch₃	s	nh₂	Ύ) CN
2-335	Cl	Cl	F	ch₃	0	nh₂	Z O X
2-336	Cl	Cl	F	ch₃	s	nh₂	yYY
2-337	Cl	Cl	F	ch₃	O	nh₂	,,χχ ,CN
2-338	Cl	Cl	F	ch₃	s	nh₂	b O z
2-339	Cl	Cl	F	ch₃	s	nh₂	^yoo

2-340	Cl	Cl	F	ch₃	O	nh₂
2-341	Cl	Cl	F	ch₃	0	nh₂	Y
2-342	Cl	Cl	F	ch₃	O	nh₂	γΥ	X 'n
2-343	Cl	Cl	F	ch₃	s	nh₂	Y	N
2-344	Cl	Cl	F	ch₃	0	nh₂	γχ	Yn L Jj
2-345	Cl	Cl	F	ch₃	s	nh₂	X	Yn L j
2-346	Cl	Cl	F	ch₃	0	nh₂	Y	XX
2-347	Cl	Cl	F	ch₃	s	nh₂	b
2-348	Cl	Cl	F	ch₃	0	nh₂	χχ	X)
2-349	Cl	Cl	F	ch₃	0	nh₂	vx	Lo
2-350	Cl	Cl	F	ch₃	0	nh₂	Y	y
2-351	Cl	Cl	F	ch₃	O	nh₂	ύΧ	Y
2-352	Cl	Cl	F	ch₃	0	nh₂	N-	b -N
2-353	Cl	Cl	F	ch₃	0	nh₂	-y.	A'N
2-354	Cl	Cl	F	ch₃	0	nh₂
2-355	Cl	Cl	F	ch₃	0	nh₂	Y
2-356	Cl	Cl	F	ch₃	0	nh₂	xp	Y
2-357	Cl	Cl	F	ch₃	s	nh₂		V<^CI

2-358	Cl	Cl	F	ch₃	s	nh₂	-κγν
2-359	Cl	Cl	F	ch₃	0	nh₂	tl
2-360	Cl	Cl	F	ch₃	s	nh₂	A
2-361	Cl	Cl	F	ch₃	0	nh₂	^y€0
2-362	Cl	Cl	F	ch₃	0	nh₂	LL
2-363	Cl	Cl	F	ch₃	s	nh₂	1 ô
2-364	Cl	Cl	F	ch₃	0	nh₂	/ Y
2-365	Cl	Cl	F	ch₃	s	nh₂	/ n-n yQ
2-366	Cl	Cl	F	ch₃	0	nh₂	Y Y
2-367	Cl	Cl	F	ch₃	0	nh₂
2-368	Cl	Cl	F	ch₃	s	nh₂	b
2-369	Cl	Cl __	F	ch₃	O	nh₂	-YY

2-370	Cl	Cl	F	ch₃	O	nh₂
2-371	Cl	Cl	F	ch₃	0	nh₂	O nh₂
2-372	Cl	Cl	F	ch₃	0	nh₂	0 γν HN, Boc
2-373	Cl	Cl	F	ch₃	s	nh₂	y^NH ₂o
2-374	Cl	Cl	F	ch₃	O	nh₂	0
2-375	Cl	Cl	F	ch₃	O	H AS	ch₃
2-376	Cl	Cl	F	ch₃	s	H	ch₃
2-377	Cl	Cl	F	ch₃	O	0 Pp H	ch₃
2-378	Cl	Cl	F	ch₃	0	/SV Vô ^H	ch₃
2-379	Cl	Cl	F	ch₃	O	vO ^HS	ch₃
2-380	Cl	Cl	F	ch₃	0	A	ch₃
2-381	Cl	Cl	F	ch₃	O	VO hn .	ch₃
2-382	Cl	Cl	F		0	nh₂	Et
2-383	Cl	Cl	F	-M	0	nh₂	Et
2-384	Cl	Cl	F	Et	O	nh₂
2-385	Cl	Cl	F		s	nh₂	ch₃
2-386	Cl	Cl	ch₃	ch₃	0	nh₂	'^V
2-387	Cl	Cl	F	ch₃	O	CF₃	ch₃
Table 3 ¹HNMR data of compounds
No.	_______________________________’HNMR ________________

1-2	H NMR (500 MHz, DMSO-d₆) δ 12.33 (s, 1H), 7.07 (s, 2H), 5.15 (q, J= 7.0 Hz, 1H) 1 50 (d _________ 7.0Hz, 3H). ’
1-4	H NMR (500 MHz, Chloroform-7) δ 7.63 - 7.61 (m, 2H), 7.45-7.38 (m, 3H), 6.13 (s, 1H) 5 18 (s 2H) ’ ‘ ’
1-26	H NMR (500 MHz, DMSO-7J δ 12.96 (s, 1H), 6.99 (s, 2H), 5.06 (q, J=7.0 Hz, 1H) 1 50 (d >7 0 ___________ Hz, 3H) ’
1-27	H NMR (500 MHz, DMSO-70 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	H NMR (500 MHz, DMSO-d₆) 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, 7= 7 0Hz 3H) ’
2-2S	Ή NMR (500 MHz, DMSO-7₆) δ 7.53 (s, 1H), 6.36 (s, 2H), 4.63 (q, 7.0 Hz, 1H), 3.72 (s, 3H) _________________________________2.08 (s, 3H), 1,50 (d, J= 7.0 Hz, 3H)._______________________ ’ ’
2-29	H NMR (500 MHz, DMSO-7₆) δ 6.36 (s, 2H), 4.66 (q, J= 7.0 Hz, 1H), 3.72 (s, 3H), 2.08 (s 3H) _____________________________________1.51 (d, 7= 7.0 Hz, 3H).______________________________ ’ ’
2-30	H NMR (500 MHz, DMSO-7₆) δ 7.61 (s, 1H), 6.80 (s, 2H), 4.63 (q, J= 7.0 Hz, 1H), 3.72 (s 3H) 1.51 (d, 7= 7.0Hz, 3H). ’ ’ ’
2-31	H NMR (500 MHz, DMSO-0) δ 6.81 (s, 2H), 4.66 (q, 7= 7.0 Hz, 1H), 3.72 (s, 3H), 1 52 (d 7= 7 0 Hz, 3H). ’
2-32	H NMR (500 MHz, DMSO-70 δ 6.81 (s, 2H), 4.65 (q, 7= 7.0 Hz, 1H), 3.72 (s, 3H), 2.53 (s 3H) _Ί__ 1.51 (d, 7= 7.0 Hz, 3H). ’ ’
2-33	H NMR (500 MHz, DMSÔ-7₆) δ 6.79 (s, 2H), 4.74 (dd, 7= 10.0, 2.5 Hz, 1H), 2.31 (s, 3H), 1.84 (dtd ___,__7= 8.0, 4.0, 2.0 Hz, 1H), 1.74-1.84 (m, 1H), 0.89 (t, 7= 8.0 Hz, 3H). ’ ’
2-34	H NMR (500 MHz, DMSO-7₆) 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	H NMR (500 MHz, Chloroform-7) δ 5.14 (s, 2H), 4.97 (d, 7= 4.5Hz, 1H), 3.75 (s, 3H), 2.31-2.37 (m 1H), 1.09 (dd, 7= 7.0,2.0 Hz, 6H). ’ ’
2-36	H NMR (500 MHz, DMSO-70 δ 6.79 (s, 2H), 4.83 (d, 7= 7.0 Hz, 1H), 2.31 (s, 3H), 2.27 (dt 7= _______________________13.5, 7.0 Hz, 1H), 0,88 (dd, 7= 25.0, 7.0 Hz, 6H).________________ ’
2-37	HNMR(500MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.32 (dd, 7= 11.0, 1.0Hz, 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	H NMR (500 MHz, DMSO-d₆) δ 6.77 (s, 2H), 4.63 (d, 7= 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	H NMR (500 MHz, Chloroform-7) δ 5.05 (q, 7= 7.0 Hz, 1H), 4.44 (s 2H) 3 85 (s 3H)
2-40	HNMR (500 MHz, Chloroform-7) δ 4.52 (dd, 7= 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	H NMR (500 MHz, Chlorofom-7) δ 4.74 (t, 7= 7.0 Hz, 1H), 4.44 (s, 2H), 4.35 (dd, 7=12 5 7 0 Hz 1H), 4.00 (dd, 7= 12.5, 7.0 Hz, 1H), 3.85 (s, 3H). ’ ’
2-42	H NMR (500 MHz, DMSO-7₆) 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	H NMR (500 MHz, DMSO-î/₆) δ 6.80 (s, 2H), 5.16- 5.25 (m, 1H), 5.11 (dd, 7= 10.5, 5.0 Hz, 1H) ______________________4.83 - 4.92 (m, 1H), 4.75 - 4.85 (m, 1H), 3.72 (s, 3H).________’ ’ ’
2-44	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 6.29 (d, 7= 7.0 Hz, 1H), 5.Ï6-5.25 (m, 1H) 3 72 (s 3H), ’ ’
2-45	H NMR (500 MHz, Chloroform-7) 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	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 5.67 (d, 7= 3.0 Hz, 1H), 3.68 (d, 7= 3.0 Hz 1H) 3 65 _______________ (s, 3H). ’
2-47	_________ H NMR (500 MHz, DMSO-7₆) δ 7.18 (s, 2H), 5.80 (s, 1H), 3.76 (s, 6H).
2-48	H NMR (500 MHz, DMSO-7,) δ 9.95 (d, 7= 6.0 Hz, 1H), 6.80 (s, 2H), 5.38 (d, 7= 6 0 Hz 1H) 3 63 _________________:______________________________________________(s, 3H).________________________________________________’ ’
2-49	H NMR (500 MHz, DMSO-7₆) δ 6.79 (s, 2H), 4.97 (t, 7= 5.5 Hz, 1H), 4.35 (t, 7= 7.0 Hz, 1H) __________________________4.21-4.26 (m, 1H), 3.91-3.96 (m, 1H), 3.72 (s, 3H)._________________’ ^?
2-50 2-51	_________H NMR (500 MHz, Chloroform-d) δ 7.27 (s, 1H), 4.45 (s, 2H), 3.71 (s, 3H).________ H NMR (500 MHz, Chlorofonn-7) δ 6.96 (s, 1H), 6,86 (d, 7= 47.0 Hz, 1H), 4.45 (s, 2H) 3 74 (s __________________________________________________________ 3H).__³ ’ ’
2-52 2-53	___________ H NMR (500 MHz, DMSO-7₆) δ 6.83 (s, 2H), 6,76 (s, 1H), 3.66 (s, 3H)._____________ _____________H NMR (500 MHz, Chlorofotm-7) δ 6.62 (s, 1H), 4.47 (s, 2H), 3,73 (s, 3H).__

2-54	H NMR (500 MHz, DMSO-d₆) δ 7.07 (s, 2H), 5.31-5.33 (m, 1H), 3.85-3.89 (m, 1H) 3 72-3 77 ___r (m, 1H), 3,66 (s, 3H), 3.34 (s, 3H). ’ '
2-55	H NMR (500 MHz, DMSOA₆j 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	_______^H NMR (500 MHz, Chloroform-J) δ 5.97 (s, 1H), 4.46 (s, 2H), 3.71 (s 3H) 1 97 (s 2H)
2-57	_______H NMR (500 MHz, Chloroform-J) δ 5.80 (s, 1H), 4.44 (s, 2H), 3.71 fs 3H1 2 23 fs 3H1
2-58
H NMR (500 MHz, Chloroform-J) δ 6.17 (s, 1H), 4.45 (s, 2H), 3.71 (s 3H) 3 42 (s 3H)
2-59 2-60	H NMR (500 MHz, DMSO-J0 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, 7= 12.5, 7.0 Hz, 1H), 2,25 (s, 6H).___________ ’ H NMR (500 MHz, Chloroform-J) 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	________ H NMR (500 MHz, Chloroformé) δ 5.76 (s, 1H), 4.45 (s, 2H) 3 75 fs 3H)
2-62
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 _Ί___ 2H), 3.73 (s, 3H). ’ ’ ' ’
2-63 2-64	H NMR (500 MHz, DMSO-d₆) 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). ’ ’ ' H NMR (500 MHz, Chloroform-J) 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	H NMR (500 MHz, DMSO-Aj δ 7.41 (dd, J = 7.5, 1.5 Hz, 1H), 7.17 (dd, 7.5, 1.5 Hz, 1H), 7.06 (t ________________________J= TA Hz, 1H), 6.82 (s, 2H), 6.22 (s, 1H), 3.66 (s, 3H).__________’ ’ ' ’
2-67	H NMR (500 MHz, DMSOé₆) δ 7.27 (s, 1H), 6.82 (s, 2H), 6.14 (s 1H) 3 66 (s 3H)
2-68
H NMR (500 MHz, DMSO-J₆) δ 7.50 (d, J= 8.0 Hz. 1H), 7.23 (s, 2H), 5.81 (s, 1H) 3 67 fs 3H)
2-69 2-70
H NMR (500 MHz, DMSOé_é) δ 7.04 (s, 2H), 5.15 (q, J= 7.0 Hz, 1H), 3.65 (s, 3H) 1 50 (d J= _____________________________________________7.0Hz, 3H)._____________________ ’
H NMR (500 MHz, HMSOé₆) 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 2-72	HNMR(500 MHz, Chloroform-i/) δ 5.24 (q, J= 7.0Hz, 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). ’ ’ '
H NMR (500 MHz, Chloroformé) δ 5.52 (q, J= 7.0 Hz, 1H), 5.19 (s, 2H), 2.84-2.92 (m 2H) 1 60 (d, 7.0 Hz, 3H), 1.25 (t, J= 7.5 Hz, 3H). ’ ’
2-73
H NMR (500 MHz, Chloroform-J) δ 5.25 (q, 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
H NMR (500 MHz, DMSOé₆) 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	H NMR (500 MHz, DMSÔé₆) 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 .7=6 5 Hz 3H) ’ ’
2-76
H NMR (500 MHz, DMSOé₆) 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= 7.0Hz, 3H), 1,30 (s, 6H). ’ ’
2-77
HNMR (500 MHz, Chloroform-i/) 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
HNMR (500 MHz, DMSOé₆) δ 6.80 (s, 2H), 4.99 (q, J= 7.0 Hz, 1H), 3.29 (td, J= 12.5, 3.5 Hz 1H), 3.04 (td, J= 12.5,2.5 Hz, 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	H NMR (500 MHz, DMSOé₆) δ 6.80 (s, 2H), 4.67 (q, 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	HNMR (500 MHz, DMSO-A) 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	H NMR (500 MHz, Chloroform-J) 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	‘H NMR (500 MHz, DMSOé₆) 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, 8.0 Hz 3H) ’
2-83 2-84 1
H NMR (500 MHz, Chloroformé) 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), ’ ’
	H NMR (500 MHz, DMSOéfi) δ 6.80 (s, 2H), 5,01 (q, J=7.0Hz, 1H), 1.53 (d, J= 7 0 Hz 3H) 1 32

	___ (s, 9H). '
2-85	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.67 (q, J= 7.0 Hz, 1H), 4.07 - 3.97 (m, 1H), 3.90 (td 7=12,5, 3.0 Hz, 1H), 1.52 (d, 7= 7.0 Hz, 3H), 1.32 - 1.13 (m, 6H), 0.90 (t, J= 7.0 Hz, 3H) ’
2-86	H NMR (500 MHz, DMSO-7_â) δ 6.80 (s, 2H), 4.97 (q, J= 7.0 Hz, 1H), 3.41 (td, 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, 7=6.5 Hz, 3H), 1.10- 1,38 (m, 4H) _______________ 0.84 - 0.92 (m,2H), 0.88 (s, 2H). ’ ’
2-87	H NMR (500 MHz, DMSO-7_fi) 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,7= 12.5, 7.0Hz, 1H), 1.72- 1.85 (m,7= 7.0 Hz, 1H), 1.51 (d,7= 7.0Hz, 3H), 1,23- ______________ l-35(m, 1H), 1.07- 1.20 (m,lH), 0.83-0.92 (m,6H). ’
2-88	Ή NMR (500 MHz, DMSO-7_fi) δ 6.80 (s, 2H), 5.00 (q, 7= 7. Hz, 1H), 3.28 (dd, 7= 12.5, 7.0 Hz 1H) 2.74 (dd,7= 12.5, 7.0 Hz, 1H), 1.61 -1.74 (m, 1H), 1.54 (d, 7= 7.0 Hz, 3H), 1.28-1.41 (m, 1H), ________________1.08-1.14 (m, 1H), 0.91 (d, 7= 7.0 Hz, 3H), 0.84 (t, 7= 8.0 Hz, 3H). ’ ’
2-89	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.67 (q, 7=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, 7=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	H NMR (500 MHz, DMSO-4₆) δ 6.80 (s, 2H), 4.99 (q, 7= 6.9 Hz, 1H), 3.51 (td,7= 12.2, 4.2 Hz 1H),2.89 (td, 7= 12.3,3.1 Hz, 1H), 1.68- 1.58 (m, 1H), 1.62- 1.44 (m, 5H), 0.85 (dd,7=25 0 6 7 ____________ Hz, 6H). ’
2-91	H NMR (500 MHz, DMSO-7₆) δ 6.81 (s, 2H), 4.68 (q, 7= 7.0 Hz, 1H), 3.50-3.61 (m, 2H) 1 53 (d __ 7= 7.0 Hz, 3H), 1.05 (s, 9H). ’ ’
2-92	Ή NMR (500 MHz, DMSO-7_é) δ 6.80 (s, 2H), 4.99-5.03 (m, 1H), 3.70 (d, 7= 12.5 Hz, 1H), 2.84 (d J __= 12.5 Hz, 1H), 1.54 (d,7= 7.0 Hz, 3H), 0.86 (s, 9H). ’ ’
2-93	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.68 (q, 7= 7.0 Hz, 2H), 1.52 (d, 7= 7.0 Hz, 3H), 1.34 __________~ t·⁴⁸ (m, 1H), 1.13- 1.25 (m, 5H), 1.03 - 1.16 (m, 1H), 0.81 (t,7= 8.0 Hz, 3H).’ ’
2-94	H NMR (500 MHz, DMSO-7₆) δ 6.79 (s, 2H), 5.02 (q,7= 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, 7= 7.0 Hz, 3H), 1.02 - 1.23 (m, 2H), 0.79 (t, 7= 8.0 Hz 3H1
2-95	H NMR (500 MHz, DMSOVj δ 6.80 (s, 2H), 4.66-4.75 (m, 2H), 1.92- 2.05 (m, 7= 7 0 Hz 1H) __1-52 (d,7= 7.0 Hz, 3H), 1.17 (d,7= 7.0 Hz, 3H), 0.79 (d, J=7.0Hz,6H). ’ ’
2-96	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 5.00 (q, 7= 7.0 Hz, 1H), 3.08-3.13 (m, 1H), 1.73-1.80 _________ (m, 1H), 1.54 (d, 7= 7.0 Hz, 3H), 1.34 (d, 7= 7.0Hz, 3H), 0.84-0.90 (m, 6H). ’
2-97	H NMR (500 MHz, DMSO-7₆) δ 6.8Ô (s, 2H), 4.64- 4.72 (m, 1H), 3.07-3.12 (m, 1H), 1.52 (d, 7= 7 0 __________ Hz, 3H), 1.25-1.32 (m,4H), 0.83 (t, 7= 8.0 Hz, 6H). ’ ’
2-98	H NMR (500 MHz, DMSO-7₆) 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,7= 7.0 Hz, 3H), 1.37- 1.45 (m, 2H), 0.82 (t,7= 8.0 Hz, 6H). ’
2-99	H NMR (500 MHz, DMSO-A) δ 6.80 (s, 2H), 4.68 (q, 7= 7.0Hz, 1H), 1.56-1.63 (m,ÎH), 1.52 (d,7= _________________ 7.0 Hz, 3H), 1.34 -1.45 (m, 7H), 0.84 (t, 7= 8.0 Hz, 3H). ’ ’
2-100	H NMR (500 MHz, DMSO-7₆) 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, 7= 8.0 Hz, 3H). ’
2-101	H NMR (500 MHz, DMSO-A) δ 6.81 (s, 2H), 4.67 (q, 7= 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	H NMR(500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 5.00 (q, 7= 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,7= 7.0Hz, 3H), 1.09- 1.41 (m, 6H), 1.00-1.12 (m 1H) 0 87 _______ (t, 7= 8.0 Hz, 3H). ’
2-103	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.67 (q, 7= 7.0 Hz, 1H), 4.23 (dd, 7= 12.5, 7.0Hz, 1H), 3.57 (dd,7= 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	H NMR (500 MHz, DMSO^₆) δ 6.80 (s, 2H), 4.99 (q, 7= 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	H NMR (500 MHz, DMSO-7₆) δ 6.81 (s, 2H), 4.67 (q, 7= 7.0 Hz, 1H), 4.10 - 4.20 (m 1H) 3 84 3.93 (m, 1H), 1.52 (d, 7= 7.0 Hz, 3H), 1.23 - 1.39 (m, 4H), 1.09 - 1.20 (m, 1H), 0.83 - 0.92 (m 6H)
2-106	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.99 (q, 7= 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, 7= 7.0 Hz, 3H), 1.19-1.46 (m, 3H), 1.08- 1.20 (m, 1H) 0 81__ 0.88(m, 6H). ’
2-107	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.68 (q, 7= 7.0 Hz, 1H), 4,42-4.48 (m, 1H) 3 49-3 45 (m, 1H), 1.53 (dd,7= 16.5, 7.0 Hz, 4H), 1.39-1.51 (m, 1H), 1.26-1.33 (m, 1H), 1.16-1.23 (m, 1H),
2-108	_______________1.03 - 1,16 (m, 1H), 0.92 (d, 7=7.0 Hz, 3H), 0,90 (d, 7=7.0 Hz, 3H)._________ H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.99 (q, 7= 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 9 4 _______________________ (m, 6H). ’ ’
2-113	H NMR (500 MHz, DMSO-^) 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, 7= 8.0 Hz, 3H). ’
2-114	H NMR (500 MHz, DMSO-d₆) 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, 7=7.0 Hz, 3H), 1,11 - 1.30 (m, 2H), 0.88 (t, 7= 7.5 Hz. 3ED ’
	H NMR (500 MHz, DMSO-d₆) δ 6.81 (s, 2H), 4.67 (q, 7= 7.0 Hz, 1H), 3.98-4.03 (m, 1H) 3 95 -
2-121	3.85 (m, 1H), 1.52 (d, 7= 7.0 Hz, 3H), 1.13-1.32 (m, 8H), 0.83-0.91 (m, 2H), 0.87(t 7= 7 5 Hz ______________ 3H). ’
2-122	HNMR (500 MHz, DMSO-d₆) δ 6.80 (s, 2H), 4.99 (q, 7=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	H NMR (500 MHz, DMSO-7₆) δ 6.81 (s, 2H),4.67 (q, 7= 7.0 Hz, 1H), 3.90-4.02 (m, 2H), 1.52 (d J ___ =7.0Hz,3H), 1.31-1.43 (m, 1H), 1.16-1.31 (m, 10H), 1.17 (s, 1H), 0.87 (t, 7= 7.5 Hz. 3H) ’
2-156	H NMR (500 MHz, DMSO-7,) δ 6.80 (s, 2H), 5.00 (q, 7=7.0 Hz, 1H), 3.26 (dd, 7= 12.5, 7.0 Hz 1H), 2.78 (dd, 7= 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	H NMR (500 MHz, DMSO-d₆) δ 6.80 (s, 2H), 4.68 (q, 7=7.0 Hz, 1H), 4.14 (dd, 7= 12.5, 7.0 Hz 1H), 3.82 (dd,7= 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 _____- l-29(m, 4H), 0.94-0.99 (m, 4H), 0.88 (t, 7= 8.0 Hz, 3H). ’
2-158	H NMR (500 MHz, DMSO-d₆) δ 6.80 (s, 2H), 5.00 (q, J- 7.0 Hz, 1H), 3.26 (dd, 7= 12.5, 7.0 Hz 1H), 2.78 (dd,7= 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	H NMR (500 MHz, DMSO-d₆) δ 6.81 (s, 2H), 4.67 (q, 7= 7.0 Hz, 1H), 3.89 - 4.02 (m, 2H) 1 52 (dd 7= 7.0, 3.0 Hz, 4H), 1.35 - 1.49 (m, 1H), 1.00- 1.34 (m, 7H), 0.93 (d,7= 7.0 Hz, 3H), 0.89 (d 7= ’ _t_________________ 7.0 Hz, 3H). ’
2-160	H NMR (500 MHz, DMSO-J₆) δ 6.80 (s, 2H), 4.99 (q,7= 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, 7= 25.0, 7.0 Hz, 6H).
2-163	H NMR (500 MHz, DMSO-7₆) δ 6.81 (s, 2H), 4.68 (qd, 7= 7.0, 2,0 Hz, 2H), 1.52 (d,7= 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	H NMR (500 MHz, DMSO-d₆) δ 6.80 (s, 2H), 5.00 (q, 7= 7.0 Hz, 1H), 3.09 - 3.20 (m 1H) 1 68 1.79 (m, 1H), 1.54 (d,7= 6.5 Hz, 3H), 1.32 - 1.45 (m, 2H), 1.29 (d, 7= 7.0 Hz, 3H), M6-l’19(m ________________ 6H), 1.13 (s, 1H), 0.86-0.88 (m, 3H). ’
2-175	H NMR (500 MHz, DMSO-d₆) δ 6.81 (s, 2H), 4.67 (q, 7= 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	H NMR (500 MHz, DMSO-7₆) δ 6.79 (s, 2H), 4.99 (q, 7= 7.0 Hz, 1H), 3.24 - 3.33 (m, 1H), 2,963.06 (m, 1H), 1.47-1.62 (m, 5H), 1.14- 1.31 (m, HH), 1.07- 1.17 (m, 1H), 0.85-0.89 (m’sH)
2-195	H NMR (500 MHz, DMSO-d₆) δ 6.80 (s, 2H), 4.67 (q,7= 7.0Hz, 1H), 3.89 - 4.01 (m, 2H), 1 52 (d J _______________ = 7.0Hz, 3H), 1.08- 1.33 (m, 16H), 0.84-0.90 (m,3H). ’ ’
2-196	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.99 (q, 7= 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	H NMR (500 MHz, DMSO-d₆) δ 6.81 (s, 2H), 4.67 (q, 7= 7.0 Hz, 1H), 3.91-4.01 (m, 2H), 1 52 (d 7 ____________=_7.0Hz,3H), 1.21 - 1.31 (m, 2H), 1.12- 1.24 (m, 16H), 0.83 -0.91 (m, 3H) ’ ’
2-216	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.99 (q, 7= 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	H NMR (500 MHz, DMSO-7₆) δ 6.81 (s, 2H), 4.67 (q, 7= 7.0 Hz, 1H), 4.00-4.05 (m, 1H), 3.83 ___ 3-92 (m, 1H), 1.52 (d, 7= 7.0 Hz, 3H), 109 - 1.32 (m, 20H), 0.82 - 0.92 (m, 3H). ’
2-236	H NMR (500 MHz, DMSO-d₆) δ 6.80 (s, 2H), 4.99 (q, 7= 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	H NMR (500 MHz, DMSO-d₆) δ 6.77 (s, 2H), 4.62 (q, 7= 7.0 Hz, 1H), 3.32 (p, 7= 7.0 Hz, 1H), 1,50 __(d, 7= 7.0 Hz, 3H), 0.44-0.48 (m, 2H), 0.23 -0.35 (m, 2H), ’ ’
2-264	H NMR (500 MHz, DMSO-d₆) δ 6.80 (s, 2H), 4.68 (q, 7= 7.0 Hz, 1H), 4.49 (p, 7= 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, 7= 7.0 Hz, 3H). ’
2-265	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.87 (p, 7= 7.0 Hz, 1H), 4.68 (q, 7= 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	H NMR (500 MHz, DMSO-7₆) 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	H NMR (500 MHz, DMSO-^) δ 6.80 (s, 2H), 5.40 (d, J= 12.5 Hz, 1H), 4.89 (d, J= 12.5 Hz 1H) “ __________ 4.67 (q, 7= 7.0 Hz, 1H), 1.53 (d, 7=7.0 Hz, 3H). ’ ’
2-268	H NMR (500 MHz, DMSO-7₆) δ 7.32 (d, 0= 12.5 Hz, 1H), 6.80 (s, 2H), 6.29 (d, J= 12.5 Hz, 1H) ’ .____________________4.66 (g, 0= 7.0 Hz, 1H), 1.56 (d, J= 7.0 Hz, 3H)._______________ ’ ’
2-270	H NMR (500 MHz, Chloroform-7) 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, 7=7.0 Hz, 3H) ’ ’ ' ’
2-271	H NMR (500 MHz, Chloroform-7) 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, 0= 6.5 Hz, 3H), 1.59-1.15 (m, 4H), 1.03 (t 0=7 5 Hz __________ 3H). ’
2-272	H NMR (500 MHz, DMSO-7₆) δ 6.79 (s, 2H), 4.99 (q, 0= 7.0 Hz, 1H), 3.37 (td, 0= 12 5 3 0 Hz 1H), 3.30 (td,7= 12.0, 1.5Hz, 1H),3.21 (dt,0= 12.5, 3.0Hz, 1H),3.18 (s, 3H),2.98 (td,0= 125 3 5 Hz, ÎH), 1,64- 1.74 (m, 1H), 1.60 (tt, 7= 12.0, 3.5 Hz, 1H), 1.54 (d, 0=7 0 Hz 3H) ’
2-273	H NMR (500 MHz, DMSO-d₆) 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, 7= 7.0 Hz, 3H)·_________’
2-274	H NMR (500 MHz, DMSO-0j δ 6.80 (s, 2H), 4.96 (q, 7= 7.0 Hz, IH), 4.14 (dd, 7= 12,5 3.0 Hz 1H), 3,53 (dd, 7= 12,5, 3.0 Hz, 1H), 3,09 (t, 7= 3.0 Hz, 1H), 1 61 (d 7= 7 0 Hz 3H1 ’

2-275	H NMR (500 MHz, DMSO-00 δ 6.80 (s, 2H), 4.71 (dd, 7= 12,5, 3.0 Hz, 1H), 4.59- 4.70 (m 2H) ________________________3.55 (t, 7= 3.0 Hz, 1H), 1,52 (d, 7=7.0 Hz, 3H).___________ ’ ’
2-276	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 4.50 - 4.83m, 3H), 4.25 - 4.48 (m, 2H) 1 50 (d 7= _____ 7.0 Hz, 3H). ’ ’
2-277	HNMR(500 MHz, DMSO-0Û δ 6.80 (s, 2H), 4.83 (dt, 7= 12.5, 1.5 Hz, 1H), 4.70 (q, 7= 7.0 Hz ________________1H), 3.78 - 3.89 (m, 2H), 3.46-3.51(m, 1H), 1,52 (d, 7= 7.0 Hz, 3H) ’ ’
2-278	H NMR (500 MHz, DMSO-0) δ 6.80 (s, 2H), 4.68 (q, 7= 7.0 Hz, 1H), 4.54 (dt, 7= 12.5 2.0 Hz 1H), 4.39-4.44 (m, 1H), 3.61 (dt,7= 12.5, 2.0 Hz, 1H), 3.29-3.34 (m, 1H), 1,48 (d,7= 7 0 Hz 3H)
2-279	H NMR (500 MHz, DMSO-7₆) δ 6.80 (s, 2H), 5.86 (t, 7= 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, 7= 7.0 Hz, 3H). ’ ’ ’
2-280	H NMR (500 MHz, DMSO-7₆) 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	H NMR (500 MHz, DMSO-00 δ 6.80 (s, 2H), 5.17-5.25 (m, 1H), 4.66 (q, 7= 7.0 Hz, 1H), 4 03-4 09 ___ (m, 1H), 1.53 (d, 7= 7.0 Hz, 3H). ’
2-282	H NMR (500 MHz, ChIoroform-7) δ 4.77-5.00 (m, 2H), 4.59 (q, 7= 7.0 Hz, 1H), 4.45 (s 2H) 1 69 _________________ (d, 7= 7.0Hz, 3H). ’ ’ ’ ‘
2-283	H NMR (500 MHz, DMSO-0.) δ 6.81 (s, 2H), 4.67 (q, 7= 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,7= 7.0 Hz 3H1 ’
2-284	H NMR (500 MHz, DMSO-0,) δ 6.80 (s, 2H), 4.66 (q, 7= 7.0Hz, 1H), 4.45-4.50 (m, 1H) 3 46-3 51 _Ί________________(m, 1H), 2.80 (s, 2H), 2.60-2.74 (m, 2H), 1.52 (d, 7= 7.0Hz, 3H) ’
2-285	H NMR(500 MHz, DMSO-7₆) δ 6.81 (s, 2H), 6.24-6.28 (m, 1 H), 6.01-6.07 (m, 1H),4.61 -472 (m _______________ 3H), 1.53 (d, 7= 7.0 Hz, 3H). ’ ' ’
2-286	H NMR (500 MHz, Chloroform-7) δ 6.07 (d, 7= 12.5 Hz, 1H), 4.57 (q, 7= 7.0 Hz, 1H), 4.43 (s 2H) ____________ 4.25 (d, 7= 12.5 Hz, 1H), 1.67 (d, 7= 7.0 Hz, 3H). ’ ’ ’ ’ ’
2-287	H NMR (500 MHz, DMSO-d₆) 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	H NMR (500 MHz, Chloroform-7) 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,7= 7.0 Hz, 3H), 1 62 (s 3H) 1 57 (s 3H1
2-289	H NMR (500 MHz, Chloroform-7) δ 5.32 (d, 7= 12.5 Hz, 1H), 5.03 (d, J= 12.5 Hz, 1H), 4.70 (q 7= —__________⁶·⁵ Hz, ÎH), 4.47 (s, 2H), 2.95 (s, 3H), 2.84 (s, 3H), 1.61 (d, 7= 6.5 Hz,3H) ’ ’
2-290	H NMR (500 MHz, DMSO-7₆) δ 6.82 (s, 2H), 5.13 (q, 7= 7.0 Hz, 1H), 4.26 (d, 7= 12.5 Hz 1H) __________________3-73 (d, 7= 12.5 Hz, 1H), 3.67 (s, 3H), 1.50 (d, 7= 7.0 Hz, 3H). ’ ’
2-291	H NMR (500 MHz, Chloroform-7) δ 6.00 (dd, 7= 10.0, 1.5 Hz, 1H), 4.59 (q, 7= 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	H NMR (500 MHz, DMSO-0) δ 6.79 (s, 2H), 4.73 (q, 7= 7.0 Hz, 1H), 2.47 (s, 3H) 2 41 (s 3H) _______________ 1.50 (d, 7= 7.0 Hz, 3H). ’ ’
2-294	H NMR (500 MHz, Chloroform-7) δ 5.04 (d, 7= 12.5 Hz, 1H), 4.89 (d, 7= 12.5 Hz, 1H), 4.60 (q 7= __LP Hz. 1H), 4.45 (s, 2H), 4.23-4.30 (m, 2H), 1,69 (d, 7= 7.0Hz, 3H), L22 (t, 7= 8 0 Hz 3H) ’
2-295	H NMR (500 MHz, Chloroform-d) δ 5.32 (q, 7= 7.0 Hz, 1H), 4.62 (q, 7= 7.0 Hz, 1H), 4.45 (_s 2H) __3.85 (s, 3H), L73 (d,7= 7.0 Hz, 3H), 1,59 (d 7=7 0 Hz 3H) ’ ’ ’
2-296	H NMR (500 MHz, Chloroform-7) δ 7.82 (q, 7= 6.5 Hz, 1H), 4.57 (q, 7= 6.5 Hz, 1H), 4 45 (s 2H) __4.01 (s, 3H), 1.69-1.52 (m, 6H).________________ ’ ’ ’

2-297	H NMR (500 MHz, Chloroform-7) δ 6.29 (t, 7= 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 IH) ’
2-298	HNMR (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,7= 7.0 Hz, 3H), 1.59-1.54 (m, 1H). ’ ’
2-299	H NMR (500 MHz, Chlore form-7) δ 7.47 - 7.39 (m, 1H), 7.41 - 7.33 (m, 2H), 7.04 - 6.98 (m, 2H) 4.60 (q, 7= 7.0 Hz, 1H), 4.42 (s, 2H), 1.76 (d, 7= 7.0 Hz, 3H). ’ ’
2-300	H NMR (500 MHz, DMSO-7₆) 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	H NMR (500 MHz, Chloroform-7) 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, 7= 7.0 Hz, 3H). ’ ’ '
2-302	H NMR (500 MHz, Chloroform-7) δ 7.31 - 7.17 (m, 4H), 5.77-5.79 (m, 1H), 4.68-4,71 (m, 1H), 4.55 __ (q, 7= 7.0 Hz, IH), 4.42 (s, 2H), 2.25 (s, 3H), 1.67 (d, 7= 7.0 Hz, 3H). ’ ’ '
2-303	H NMR (500 MHz, DMSO-7₆) 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 (q, 7=7.0 Hz, 1H), 4.49 (dt, 7= 12.0, 1.0 Hz, 1H), 4.30-4.40 (m, 1H), 2.23 (d, 7= 1.5 Hz’ !__ 3H), 1.31 (d, 7= 7.0Hz, 3H). ’ ' ’
2-304	H NMR (500 MHz, DMSO-7₆) δ 7.38 (t, 7= 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, 7= 7.0 Hz, 1H), 2.22 (d, 7= 2.0 Hz, 1H), 2,22 (s, 2H) 1 51 (d 7= ____ 7.0 Hz, 3H). ’
2-305	H NMR (500 MHz, DMSO-7₆) 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 (q, 7= 7.0 Hz, 1H), 4.41-4.51 (m, IH), 4.10 - 4.17 (m, 1H), 2.22 (d, 7= 2.0 Hz 1H) 2.22 (s, 2H), 1.53 (d, 7= 7.0 Hz, 3H). ’ ’
2-306	Ή NMR (500 MHz, DMSO-d₆) δ 7.39-7.46 (m, 2H), 7.17 - 7.23(m, 2H), 6.78 (s, 2H), 5.10 (dt 7= 12.5, 1.0 Hz, 1H), 5.04 (d,7= 12.5 Hz, 1H), 4.65 (q, 7=7.0 Hz, 1H), 2.21 (d,7= 2.0 Hz, IH), 2 21 (s ___________ 2H), 1.51 (d, 7= 7.0 Hz, 3H). ’
2-307	HNMR (500 MHz, DMSO-7₆) δ 7.31 (dt,7=7.5,1.0 Hz, 2H), 7.09 (dd, 7= 7.5, 1.5Hz,2H) 6 77 (s 2H), 4.99 (q, 7= 7.0 Hz, 1H), 4.47 (dt,7= 12.5, 1.0 Hz, 1H), 4.10 (dt,7= 12.5, 1.0 Hz, 1H), 2.21 (d,7 _ ⁼ 2.0 Hz, 1H), 2.21 (s, 2H), 1.54 (d, 7= 7.0 Hz, 3H). ’
2-308	H NMR (500 MHz, DMSO-7₆) 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, 7= 12.5, 1.0 Hz, 1H), 5.07 (d, 7= 12.5 Hz, 1H), 4.66 (q, 7= 7.0 Hz, 1H) 1 52’(d 7= __ 7.0 Hz, 3H). ’
2-309	H NMR (500 MHz, DMSO-7₆) δ 7.23-7.31 (m, 3H), 7.07 (td, 7= 7.5,2.0 Hz, 1H), 6.77 (s, 2H), 4.99 (g, 7= 7.0 Hz, 1H),4.52 (d, 7= 12.5 Hz, 1H), 4.35 (dd, 7= 12.5,1.0 Hz, 1H), 1.54 (d, 7= 7Ό Hz. 3H)
2-310	HNMR (500 MHz, DMSO-7₆) 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,7= 12.5, 1.0 Hz, 1H), 4.87 (d,7= 12.5 Hz, 1H), 4.64 (q, 7= 7 0Hz ___ 1H), 1.50 (d, 7= 7.0 Hz, 3H). ’
2-311	H NMR (500 MHz, DMSO-d₆) δ 7.33 (td, 7= 7.5, 5.5 Hz, 1H),7.21 (dq, 7= 7.5, 2.0 Hz, 1H),7.1O (dq,7= 9.0,2.0 Hz, 1H), 6.93-6.97 (m, 1H), 6.76 (s, 2H), 4.74 (dt, 7= 12,5, 1.0 Hz, 1H), 4.52 (q,7= _________ 6.5 Hz, 1H), 4.19 (d, 7= 12.5 Hz, 1H), 1.51 (d, 7= 7.0Hz, 3H). ’
2-312 —	Ή NMR (500 MHz, DMSO-7₆) 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, 7= 7.0 Hz, 3H).
2-313	Ή NMR (500 MHz, DMSO-7₆) δ 7.41-7.45 (m, 2H), 7.08- 7.16 (m, 2H), 6.76 (s, 2H), 4.64 (dt, 7= 12.0, 1.0 Hz, 1H), 4.58 (q, 7= 7.0 Hz, 1H), 4.11 (d,7= 12.5 Hz, 1H), 1.51 (d, 7= 7.0 Hz 3H)
2-314	H NMR (500 MHz, DMSO-7₆) δ 7.39 - 7.49 (m, 2H), 7.24 (td, 7= 7.5, 2.0 Hz, 1H), 7.10 (td, 7= 7.5, 2.0 Hz, 1H), 6.77 (s, 2H), 5.56 (d, 7= 12.5 Hz, 1H), 4.85 (dd, 7= 12.5, 1.0 Hz, 1H), 4.64 (q, 7= 7.0 ’ . ₁___________________ Hz, 1H), 1.52 (d, 7= 7.0 Hz, 3H).
2-315	H NMR (500 MHz, OMSO-t/j δ 7.39 (dd, 7=7.5, 2.0 Hz, 1H), 7.24-7.28 (m, 1H), 7.18 (td 7= 7 5 2.0 Hz, 1H), 7.03 (td, 7= 7.5, 2.0 Hz, 1H), 6.77 (s, 2H), 5.00 (q, 7= 7.0 Hz, 1H), 4.64 (dd, 7= ’ _____ 12.5,1.0Hz, 1H), 4.37 (dd, 7= 12.5, 1.0 Hz, 1H), 1.54 (d, 7= 7.0 Hz, 3H). ’
2-316	H NMR (500 MHz, DMSO-7₆) δ 7.51 (q, 7= 1.5 Hz, 1H), 7.27- 7.34(m, 3H), 6.80 (s, 2H), 5.82 (d, 7 = 12.5 Hz, 1H), 4.64 (q, 7= 7.0 Hz, 1H), 4.52 (d, 7= 12.5 Hz, 1H), 1.47 (d, 7= 6.5 Hz 3H) ’
2-317	H NMR (500 MHz, DMSO-7₆) δ 7.54 (q, 7= 1.5 Hz, 1H), 7.25- 7.37(m, 3H), 6.79 (s, 2H), 4.72 (dt, 7 = 12-5, 1.0 Hz, 1H), 4.49 (q, 7= 7.0Hz, 1H), 4.19 (d, 7= 12.5 Hz, 1H), 1.51 (d, 7=7.0 Hz 3H) ’
2-318	H NMR (500 MHz, DMSO-7₆) δ 7.40 - 7.47 (m, 2H), 7.31 - 7.37 (m, 2H), 6.75 (s, 2H), 5.73 (dt, 7= 12.5, 1.0 Hz, 1H), 4.65 (q, 7= 6.5 Hz, 1H), 4.56 (d, 7= 12.5 Hz, 1H), 1.48 (d, 7= 7.0 Hz 3H1’
2-319	H NMR (500 MHz, DMSO-7₆) δ 7.37 - 7.44 (m, 2H), 7.31 - 7.37 (m, 2H), 6.75 (s, 2H), 5.03 (q 7= 7-0 Hz, 1H), 4.68 (d,7=12.5Hz, 1H), 4.15 (dt, 7= 12,5, 1.2 Hz, 1H), 1.50 (d, 7= 7.0 Hz, 3H)
2-320	H NMR (500 MHz, DMSO-7₆) δ 7.65 (dd, 7= 7.5, 2.0 Hz, 1H), 7.40-7.42 (m, 1H), 7.32 (td, 7= 7.5 ^2.0 Hz, 1H), 7,25 (td, J= 7.5, 2,0 Hz, 1H), 6.77 (s, 2H), 5.58 (d, 7= 12,5 Hz, IH), 4.88 (dd,7= 12^5,’

_	__________________1-0 Hz, IH), 4,66 (g, J= 7.0Hz, 1H), 1.54 (d, J~- 7.0 Hz, 3H).
2-321	H NMR (500 MHz, DMSO-2_fi) δ 7.50 (dd, J= 7.5, 1.5 Hz, 1H), 7.26 - 7.35 (m, 2H), 7 13 - 7 22 (m 1 H), 6.77 (s, 2H), 5.22 (d, J= 12.5 Hz, IH), 5.04 (q, 2= 7.0 Hz, 1H), 4.05 - 4.12(m, 1H) 1 50 (d J= ______________ 7.0 Hz, 3H). ’ ’
2-322	H NMR (500 MHz, DMSO-2₆) δ 7.61 (q, J= 2.0 Hz, 1H), 7.51 (dt, 7.5, 2.0 Hz, 1H), 7.45 (dq J= 7.5,2.0Hz, 1H), 7.28 (t, 2= 7.5 Hz, 1H), 6.83 (s,2H), 5.81 (dt, J= 12.5, 1.0Hz, 1H), 4.64 (q, J=7 0 ____Hz, IH), 4.49 (d, J= 12.5 Hz, 1H), 1.47 (d, J= 7.0 Hz, 3H). ’
2-323	H NMR (500 MHz, DMSO-d₆) δ 7.39-7.49 (m, 3H), 7.22 (t, J= 7.5 Hz, 1H), 6.83 (s, 2H), 4.71 (dt . A 12-5, 1.0 Hz, 1H), 4.48 (q, 2=7.0 Hz, 1H),4.16 (d, J= 12.5 Hz, 1H), 1.51 (d, J= 7 0 Hz 3141
2-324	H NMR (500 MHz, DMSO-2,) 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, IH),4.65 (g, J= 7.0Hz, 1H),4.54 (d. J= 12.5 Hz, 1H), 1.48 (d 7=7 0Hz 3H1’
2-325	‘H NMR (500 MHz, DMSO-2₆) δ 7.52 - 7.59 (m, 2H), 7.22 (dt, J= 7.5, 1.0 Hz’, 2H) 6 77 (s 2H) 4.99 (q, 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	H NMR (500 MHz, DMSO-2₆) δ 7.56 - 7.62 (m, 1H), 7.49 (td, 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	H NMR (500 MHz, ΌΜ8Ο-2_ή) δ 7.52 (dd, J= 7.0,2.0Hz, 1H), 7.40 (td, J= 7.5, 2.0 Hz, 1H) 7.29 (t /= 7.2 Hz, 2H), 6.77 (s, 2H), 5.01 (q, 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	H NMR (500 MHz, DMSO-2₆) δ 7.65 (dd, J= 2.5, 1.5 Hz, 1H), 7.58 (dq, J= 5.5, 3.0 Hz, 1H) 7.50 (s, IH), 7.49 (d, 2= 3.0 Hz, 1H), 6.77 (s, 2H), 5.09 - 5.18 (m, 2H), 4.64 (q, 2= 7.0 Hz, 1H), 1.51 (d J ___________ — 6.5 Hz, 3H).
2-330	H NMR (500 MHz, DMSO-2_â) 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 (g, 7.0 Hz, 1H), 4.59 (dt, 2= 12.5, 1.0 Hz, IH), 4.18 (dd, 2= 12.5 1 5Hz’ 1H)’ ____________ 1-55 (d, 2= 7.0 Hz, 3H). ’ ’ ’
2-331	H NMR (500 MHz, DMSO-2₆) δ 7.69 (d, 2= 7.0 Hz, 2H), 7.52 - 7.58 (m, 2H), 6.78 (s, 2H) 5.18 (dt 2- 12.5, 1,0 Hz, 1H), 5,10 (d,2= 12,5 Hz, 1H), 4.65 (q, 2= 7 0 Hz 1H) 151 td Ί OHz 3H1 ’

2-332	H NMR (500 MHz, DMSO-2₆) δ 7.59 - 7.65 (m, 2H), 7.40 - 7.46 (m, 2H), 6.78 (s, 2H), 5.02 (q 2= 7.0 Hz, 1H), 4.73 (d,2= 12.5 Hz, 1H), 4.19 (dt, 2= 12.5, 1.0 Hz, 1H), 1.50 (d,2= 7.0 Hz 3H1
2-333	H NMR (500 MHz, DMSO-Y δ 7.71 - 7.78 (m, 1H), 7.60-7.66 (m, 3H), 6.77 (s, 2H), 5,59 (d 2= _,_____12.5 Hz, 1H), 5.10 (d, 2= 12.5 Hz, 1H), 4.63 (q, 2= 7.0 Hz, 1H), 1.55 (d, 2= 7.0 Hz 3H) ’
2-334	H NMR (500 MHz, DMSO-4) δ 7.64 (dd, 2= 7.0,2.0 Hz, 1H), 7.46 - 7.58 (m, 2H), 7,42 - 7 48 (m 1H), 6.76 (s, 2H), 5.05 (q, 2=7.0 Hz, 1H), 4.76 (dd,2= 12.5, 1.0 Hz, 1H), 4.50 (dd,2= 12 5 1 0 Hz’ _,___________ 1H), 1.52 (d, 2= 7.0 Hz, 3H). ’ ’
2-335	H NMR (500 MHz, DMSO-2₆) δ 7.96 (q, 2= 1.5 Hz, 1H), 7.86 (dt, 2= 7.5, 2.0 Hz, 1H), 7.64-7.67 (m, 1H), 7.49 (t, 2= 7.5 Hz, 1H), 6.77 (s, 2H), 5.69 (d, 2= 12.5 Hz, 1H), 4.60 - 4.69 (m 2H) 1 48 (d ___________ 2= 7.0 Hz, 3H). ’ ’
2-336	H NMR (500 MHz, DMSO-2₆) δ 7.76 - 7.84 (m, 2H), 7.62 - 7.69 (m, 1H), 7.45 (t, 2= 7 5 Hz 1H) 6.81 (s, 2H), 5.00 (q, 2= 7.0 Hz, 1H),4.75 (d,2= 12.5 Hz, 1H),4.23 (dt,2= 12.5, 1.0 Hz, 1H) 1 52 _τ_________________ (d, 2 = 7.0 Hz, 3H). ’
2-337	H NMR (500 MHz, DMSO-2₆) δ 7.84 - 7.90 (m, 2H), 7.66 - 7.73 (m, 2H), 6.76 (s, 2H), 5.79 (dt 2= ___12.5, 1,0 Hz, IH), 4.62 - 4.70 (m,2H), 1.49 (d, 2= 7.0 Hz, 3H). ’ ’
2-338	H NMR (500 MHz, DMSO-2₆) δ 7.61 - 7.68 (m, 2H), 7.46 - 7.52 (m, 2H), 6.77 (s, 2H) 4.99 (q 2= 7.0 Hz, 1H), 4.75 (d, 2= 12.5 Hz, 1H), 4.23 (dt, 2= 12.5, 1.0 Hz, 1H), 1.52 (d, 2= 7.0 Hz 3ΗΊ
2-339	H NMR (500 MHz, DMSO-2₆) Ô7.95- 8.02 (m, 2H), 7.82 - 7.90 (m, 2H), 7.81 (dd, 2= 7.5 1.5 Hz ______IH), ⁷·⁴⁷ - ⁷·56 (m, 2H), 6.11 (s, 2H), 5.07 (q, 2= 7.0 Hz, 1H), 1.46 (d, 2= 7.0 Hz. 3H) ’
2-340	H NMR (500 MHz, DMSO-2₆) δ 8.01-8.04 (m, 1H), 7.90-7.99 (m, 3H), 7.66 (6ζ2= 7.5, 1.0 Hz 1H), 7.57 (dd, 2= 5.5, 3.5 Hz, 2H), 5.92 (s, 2H), 5.53 (dt, 2= 12.5, 1.0 Hz, IH), 5.00 (d, J= 12.5 Hz _,_______________ 1H), 4.69 (q, 2= 7.0 Hz, 1H), 1.50 (d, 2= 6.5 Hz, 3H). ’
2-341	H NMR (500 MHz, DMSO-2₆) δ 8.02 (dt, 2= 7.5, 1.5 Hz, IH), 7.95 (dq,2= 7.0, 1.5 Hz 2H) 7 66 (dt,2= 7.5, 1.5 Hz, IH), 7.55 - 7.66 (m, 2H), 7.38 (td, 2= 7.5, 1.5 Hz, 1H), 5.92 (s, 2H), 5.62 (d 2= 12.5 Hz, 1H), 5.14 (dd, 2= 12.5, 1.0 Hz, IH), 4.69 (q, 2= 7.0 Hz, IH), 1.55 (d, 2= 7.0 Hz 3H1
2-342	HNMR(500 MHz, DMSO-2g) δ 8.53 (dd, 2= 5.0,1.5 Hz, IH), 7.75 (td, 2= 8.0, 1.5 Hz, IH) 7.51 (dt, 2=8.0, 1.5 Hz, IH), 7.28-7.30 (m, IH), 6.78 (s, 2H), 5.44 (dd, 2= 12.5, 1.5 Hz, IH), 5.18 (d 2= ____12-5 Hz, IH), 4.65 (q, 2= 7.0 Hz, IH), 1.51 (d, 2= 7.0 Hz, 3H). ’
2-343	H NMR (500 MHz, DMSO-2₆) δ 8.40 (dd, 2=5.0, 1.0 Hz, 1 H), 7.67 (td, 2= 8.0, 1.5 Hz, IH) 7.49 (dt,2= 8.0, 1.5 Hz, IH), 7.28-7.31 (m, IH), 6,76 (s, 2H), 5.05 (d,2= 12.5 Hz, IH), 5.00 (q, 2= 7.0

	_t_______________ Hz, 1H), 4.13 (dd, 7= 12.5,1.5 Hz, 1H), 1.51 (d,7= 7.0 Hz, 3H). '
2-344	H NMR (500 MHz, DMSO-d₆) δ 8.58 (d, J= 5.0 Hz, 2H), 7.51 -7.56 (m, 2H), 6.77 (s, 2H) 5 07 (dt 7=12,5, 1.0 Hz, 1H), 4.94 (d, 12.5 Hz, 1 H), 4.65 (q, J= 7.0 Hz, 1H), 1.51 (d, 7= 7.0 Hz 3H) ’
2-345	^lH NMR (500 MHz, DMSO-%) δ 8.40 (d, J= 5.0 Hz, 2H), 7.38 (d, J= 5.0 Hz, 2H), 6.77 (s, 2H), 4.95 (g, 7= 7.0 Hz, 1H), 4.48 (d, J= 12.5 Hz, 1H), 4.11 (d, 7= 12.5 Hz, 1H), 1.54 (d,7= 7.0 Hz, 3H).
2-346	H NMR (500 MHz, DMSO-7₆) δ 8.59 (dd, 7= 5.0, 1.5 Hz, 1H),8.43 (d,7= 1.0 Hz, 1H), 8.01 (dd,7= 8.0, 5.0 Hz, 1H), 7.53 (dt, 7= 8.0, 1.5 Hz, 1H), 6.77 (s, 2H), 4.99 (d, 7= 12.5 Hz, 1H), 4.93 (d, 7=
__	___________ 12.5 Hz, 1H), 4.64 (q, 7= 7.0 Hz, 1H), 1.51 (d, 7= 7.0 Hz, 3H).
2-347	Ή NMR (500 MHz, DMSO-7,) δ 8.39 - 8.49 (m, 2H), 7.59 (dt, 7= 8.0, 1.5 Hz, 1H), 7.36 (dd, 7= 8 0 5.0 Hz, 1H), 6.77 (s, 2H), 4.96 (q, 7= 7.0Hz, 1H), 4.46 (d, 7= 12.5 Hz, 1H), 4.10 (d, 7= 12.5 Hz 1H)’ __ 1.54 (d, 7= 7.0 Hz, 3H). ’ ’
2-348	H NMR (500 MHz, Chloroform-7) δ 7.41 (d, 7= 2.0 Hz, 1H), 6.41 (d, 7=3.5 Hz, 1H), 6.36 (dd, 7= 3.5,2.0 Hz, 1H), 5.25 (q, 7= 7.0 Hz, 1H), 5.20 - 5.08 (m, 4H), 1.63 (d, J= 7.0 Hz, 3H). ’
2-349	Ή NMR (500 MHz, DMSO-7₆) δ 7.46 (d, 7= 7.5 Hz, 1H), 7.25 (d, 7= 1.5 Hz, 1H), 6.81 (s, 2H), 6.37 (dd, 7=7.5,1.5 Hz, 1H),5.47 (d,7= 12.5 Hz, 1H), 4.99 (d, 7= 12.5 Hz, 1H), 4.69 (g, 7=7.0 Hz, 1H) __________ 1.53 (d, 7= 7.0 Hz, 3H). ’
2-350	^lH NMR (500 MHz, DMSO-%) δ 7.35 (dd, 7=6.5, 2.0 Hz, 1H), 7.00 - 7.09 (m, 2H), 6.81 (s, 2H), 5.71 (d,7= 12,5 Hz, 1H), 5.20 (d, 7=12,5 Hz, 1H), 4.69 (q, 7= 7.0 Hz, 1H), 1.54 (d, 7= 7.0 Hz, 3H).
2-351	H NMR (500 MHz, DMSO-7₆) δ 7.33 (d,7= 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, 7= 12.5 Hz, 1H), 4.71 (q, 7= 7.0 Hz, 1H), 1.52 (d, 7= 7.0 Hz, 3H) ’
2-352	ΉNMR(500 MHz, DMSO-7₆) 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, 7= 7.0 Hz, 3H). ’ ’
2-353	Ή NMR (500 MHz, DMSO-7₆) δ 7.53 (d, 7= 7.5 Hz, 1H), 6.81 (s, 2H), 6.37 (dd, 7= 7.5, 1.0 Hz, 1H), 5.40 - 5.47 (m, 1H), 5.03 (d, 7= 12.5 Hz, 1H), 4.70 (q, 7=7.0 Hz, 1H), 3.75 (s, 3H), 1.55 (d, 7= ’ ____________ 7.0Hz, 3H).
2-354	H NMR (500 MHz, DMSO-7_Ê) δ 7.70 (t,7= 1.5 Hz, 1H), 7.01 (t, 7= 1.0 Hz, 1H), 6.81 (s, 2H), 5.00____________5-07 (m, 2H), 4,69 (q, 7=7.0 Hz, 1H), 3.89 (s, 3H), 1,54 (d, 7= 7.0 Hz, 3H). ’ ’
2-355	'HNMR(500MHz, DMSO-7₆) 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, 7= 7.0 Hz, 1H), 2,10 (d, 7= l.OHz,3H), 1.61 (d, 7= 7.0 Hz, 3H). ’
2-357	H NMR (500 MHz, DMSO-7₆) δ 7.71 (t, 7= 2.0 Hz, 1H), 7.52 (dt, 7= 7.5, 2.0 Hz, 1H), 7.36 (dt, 7= 7.5, 2.0 Hz, 1H), 7.25 (t, 7= 7.5 Hz, 1H), 6.74 (s, 2H), 5.04 (q, 7= 7.0 Hz, 1H), 1.52 (d, 7= 7.0 Hz ____ 3H). ’
2-358	H NMR (500 MHz, DMSO-7₆) δ 7.61 - 7.67 (m, 2H), 6.93-7.00 (m, 2H), 6.73 (s, 2H), 5.06 (q, 7=7.0 ___ Hz, 1H), 3.79 (s, 3H), 1.51 (d, 7= 7.0 Hz, 3H). ’
2-360	H NMR (500 MHz, DMSO-<4) δ 7.46 - 7.53 (m, 2H), 7.28 (t, 7= 7.5 Hz, 1H), 7.15-7.18 (Μ, 1H), 6.77 (s, 2H), 4.98 (q,7= 7.0 Hz, 1H), 2.89 (tt, 7= 8,0, 6.0 Hz, 1H), 1,45 (d, 7= 7.0Hz, 3H), 1.17-1.23 __ (m, 6H).
2-363	H NMR (500 MHz, DMSO-Tj δ 8.50 (d, 7= 5.0 Hz, 2H), 7.76 (d,7= 5.0 Hz, 2H), 6.74 (s, 2H), 5.03 , _ (q, 7= 7.0Hz, 1H), 1.51 (d, 7= 7.0 Hz, 3H). ’ ’
2-365	H NMR (500 MHz, DMSO-7₆) 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, 7= 7.0 Hz, 3H). ’ ’
2-368	Ή NMR (500 MHz, DMSO-%) δ 6.80 (s, 2H), 6.66 (dd,7= 7.5, 1.5 Hz, 1H), 6.29 (dd, 7= 7.5, 1.5 Hz, 1H), 6.12 (t, 7= 7.5 Hz, 1H), 5.07 (q, 7= 7.0 Hz, 1H), 3.62 (s, 3H), 1,56 (d, 7= 7.0 Hz, 3H).
2-370	H NMR (500 MHz, DMS0-7₆) δ 6.80 (s, 2H), 4.98 (d, 7= 12.5 Hz, 1H), 4.93 (d, 7= 12.5 Hz, 1H), 4.66 (q, 7= 6.5 Hz, 1H), 3.44-3.51 (m, 1H), 3.16-3.24 (m, 1H), 1.51 (d,7= 7.0 Hz, 3H), 1.05 (t 7= __ 8.0 Hz, 3H). ’
2-371	H NMR (500 MHz, Chloroform-7) δ 6.76 (s, 1H), 4.61 (q, 7 = 6.5 Hz, 1H), 4.44 (s, 2H), 1 73 (d 7= 6.5 Hz, 3H), 1.66 (s, 2H). ’ ’
2-372	H NMR (500 MHz, Chloroform-7) δ 8.09 (s, 1H), 4.93 (s, 1H), 4.71 (q, 7= 6.5 Hz, 1H), 4.47 (s, 2H), _______ 3.63 (s, 3H), 1.71 (d, 7= 6.5 Hz, 3H), 1.44 (s, 9H). ’ ’ ’
2-373	H NMR (500 MHz, DMSO-7₆) δ 7.46 (s, 2H), 6.79 (s, 2H), 5.02 (q, 7= 7.0 Hz, 1H), 1.59 (d, 7=7 0 _।______ Hz, 3H).
2-376	H NMR (500 MHz, DMSO-7₆) δ 6.12 (s, 1H), 4.99 (q, 7=7.0 Hz, 1H), 3.66 (dq, 7= 12.5, 8.0 Hz, !H), 3.28 (dq,7= 12.5, 8.0 Hz, 1H),2.31 (s, 3H), 1.54 (d, 7= 7.0 Hz, 3H), 1.26 (t, 7= 8.0 Hz, 3H).
2-377	H NMR (500 MHz, Chloroform-7) δ 9.90 (s, 1 H), 4.64 (q, 7= 7.0 Hz, 1H), 3.85 (s, 3H), 2.20 (s 3H) ,__ 1.70 (d, 7= 7.0 Hz, 3H). ’ ’
2-378	H NMR (500 MHz, DMSO-%) δ 7.55 (dd, 7= 7.0, 2.0 Hz, 1H), 6.34 - 6.43 (m, 2H), 6.22 (s, 1H), 5,14 (d, 7= 12.5 Hz, 1H), 4.67 (q, 7= 7.0 Hz, 1H), 4.43 (d, 7=12.5 Hz, 1H), 3.72 (s, 3H), 1.53 (d, 7=

	, _ 7.0 Hz, 3H).
2-379	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= 7.0Hz, 3H). ’ ’
2-381	Ή NMR (500 MHz, DMSO-d₆) 57.93- 8.00 (m, 2H), 7.55 7.63 (m, 1H), 7.50 - 7.58 (m_r 2H), 4.63 (q, .7=7.0 Hz, 1H), 3.72(s, 3H), 1.53 (d,J= 7.0 Hz, 3H). ’
2-383	H NMR (500 MHz, DMSO-î/₆) δ 7.04 (s, 2H), 4.41 (d, J=8.5Hz, 1H), 4.11-4.18 (m, 2H), 1.14-1 31 (m, 5H), 0.48-0.66 (m, 3H)
2-385	H NMR (500 MHz, DMSO-J,) 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	H NMR (500 MHz, DMSO-d₆) 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. 3H1
2-387	‘H NMR (500 MHz, DMSO-d₆) 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 présent invention are detailedly illustrated in the following schemes and examples. The starting materials can be purchased commercially or can be prepared by methods known in the literature or according to the detailed illustrations. Those skilled in the art will appreciate that other synthetic routes can also be utilized to synthesize the compounds of the présent invention. Although spécifie starting materials and conditions in the synthetic route hâve been described below, they can be easily replaced with other similar starting materials and conditions, and various isomers of compounds and the like produced by variations or variants of the préparation methods of the présent invention are included in the scope of the présent invention. Additionally, the préparation methods described below can be further modified in accordance with the présent disclosure, using conventional Chemical methods well known to those skilled in the art. For example, appropriate groups are protected during the reaction, and the like.

The method examples are provided below to facilitate a further understanding of the préparation method of the présent invention, and the spécifie materials, types and conditions used are determined to be further description of the présent invention and are not intended to limit its rational scope. The reagents used for synthesizing the following compounds indicated in the table below are either commercially available or can be readily prepared by those skilled in the art.

The examples of représentative compounds are as follows, the synthetic methods 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 (300mg, 1.27mmol), compound b (255mg, 1.53mmol), a catalytic amount of TBAB (lOmg), and DMF (20mL) were added to a 50 mL round-bottom flask, heated to 85 C and reacted for 12 hr. After completed reaction of the starting materials according to LC-MS détection, the reaction solution was cooled to room température, concentrated, and separated by column chromatography to obtain compound 2-31 (180mg, yield 47%).

2-31-1

2-31 (2) Compound 2-31 (0.5g, 1.77mmol), methanol (20mL) were added to a 100 mL single-port flask, lithium hydroxide (74mg, 1.77mmol) was dissolved in 2 mL of water, and slowly added dropwise to the single-port flask at room température, followed by stirring at room température for 12 hr. After completed reaction of the starting materials according to LC-MS détection, the reaction solution was adjusted with 0.5M dilute HCl to pH = 5-6, concentrated, and then extracted with water and ethyl acetate. The organic phase was dried, and concentrated to obtain compound 1-2 (400mg) as a white solid.

2. Synthesis of compound 2-45 (1) Compound 2-45-1 (1g, 8.61mmol), phosphorus oxybromide (3.7g, 12.9mmol) were added to a 50 mL round-bottom flask, heated to 60°C and reacted for 5 hr. After completed reaction of the starting materials according to HPLC détection, the reaction solution was cooled to room température, and slowly poured into an ice-water bath, with the température being controlled at 0-10°C during quenching. The aqueous phase was extracted with ethyl acetate (lOOmL x 2). The organic phase was dried and concentrated to obtain compound 2-45-2 (1.5g, crude product). Without further purification, the compound was directly used in the next step.

o o

2-45-1 2-45-2 (2) Compound a (400mg, 2.13mmol), compound 2-45-2 (700mg), a catalytic amount of TBAB (lOmg), and DMF (lOmL) were added to a 50 mL round-bottom flask, heated to 85°C and reacted for 12 hr. After completed reaction of the starting materials according to LC-MS détection, the reaction solution was cooled to room température, and extracted with water (lOOmL) and methyl tert-butyl ether (50mLx 2). The organic phase was dried, concentrated, and separated by column chromatography to obtain compound 2-45 (200mg, yield 35%), as a white solid.

a

Ο 2-45-2

NH₂

CI^A^CI TBAB _> J T DMF Ρ^Ν^Ο^γ⁰'

O 2-45

3. Synthesis of compound 2-69

Compound a (0.5g, 2.13mmol), compound b (313mg, 2.55mmol), a catalytic amount of TBAB (lOmg), and DMF (lOmL) were added to a round-bottom flask, and stirred at room température 15 °C for 24 hr. When there was a small amount of starting materials remained according to LC-MS détection, a further treatment was made. The reaction solution was poured into 50mL of water, and extracted with methyl tert-butyl ether twice (50mL x 2). The organic phase was dried, concentrated, and separated by column chromatography, to obtain compound 2-69 (300mg, yield 50%), as a white solid.

o ^a b 2-69

4. Synthesis of compound 2-319

With a reference to the synthesis method of compound 1-2, compound 1-26 was prepared, then compound 1-26 (400mg, 1.49mmol), compound 2-319-1 (219mg, 1.49mmol), DCC (459mg, 2.24mmol), and anhydrous DCM (20mL) were added to a 100 mL round-bottom flask, and reacted at room température for 12 hr. After completed reaction of the starting materials according to LC-MS détection, the reaction solution was concentrated, and separated by column chromatography to obtain compound 2-319 (250mg, yield 41%), as a white solid.

5. Synthesis of compounds 2-378 and 1-71 (1) Compound 2-69 (200mg, 0.71mmol), compound c (145mg, 0.85mmol), potassium carbonate (leq), a catalytic amount of DMAP (lOmg), and acetonitrile (20mL) were added to a 50 mL round-bottom flask, heated to 80°C and reacted for 12 hr. After completed reaction of the starting materials according to LC-MS détection, the reaction solution was cooled to room température, concentrated, and separated b y column chromatography to obtain compound 2-378 (150mg, yield 50%), as a colorless oil.

Ο

2-69

B

K₂CO₃ DMAP^

MeCN

(2) Compound 2-378 (0,15g, 0.43mmol), methanol (20mL) were added to a 100 mL single-port flask, lithium hydroxide (48mg, 2mmol) was dissolved in 2 mL water, and slowly added dropwise to the single-port flask at room température, foliowed by stirring at room température for 12 hr. After completed reaction of the starting materials according to LC-MS détection, the reaction solution was adjusted with 0.5M dilute HCl to pH = 5-6, concentrated, and then extracted with water and ethyl acetate. The organic phase was dried and concentrated to obtain compound 1-71 (lOOmg), as a white solid.

Biological activity évaluation:

The activity level standard of plants destruction (i. e. growth inhibition rate) is as follows:

Level 5: the growth inhibition rate is greater than 85%;

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

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

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

Level 1 : the growth inhibition rate is equal to or greater than 5% and less than 20%;

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

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

Post-emergence test experiment: Monocotyledonous and dicotyledonous weed seeds and main crop seeds (i. e. wheat, com, rice, soybean, cotton, oilseed, millet and sorghum. ) were put into a plastic pot loaded with soil. Then covered with 0.5-2 cm soil, the seeds were allowed to grow in good greenhouse environment. The test plants were treated at 2-3 leaf stage 2 weeks after sowing. The test compounds of the invention were dissolved with acetone respectively, then added with tween-80, and using 1.5 liters per hectare of an emulsible concentrate of methyl oleate as a synergist, and diluted by certain amount of water to certain concentration. The solution was sprayed to the plants with a sprayer. Then the plants were cultured for 3 weeks in the greenhouse, and the experiment resuit of weed controlling effect was listed in tables 4-5.

Table 4 Activity test results of compounds (1000 g a.i./ha)

No.	Echinochloa crusgalli	Digitaria sanguinalis	Monochorîa 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	Γ 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

Table 5 Post-emergence comparative activity test

No.	Echinochloa crusgalli	Digitaria sanguinalis	Semen Euphorbiae Lathyridis	rice
_____________________1-2___________________________	5	5	5	N
nh₂ ^ciX^ci _ _ ·. 0	2	3	3	N
nh₂ Clx^-Yci cXnX>Jy⁰'h _____________________0 CS configuration)	1	1	1	N
_________________________1-26	5	5	5	0
_________________1-26 (400 g a.i./ha)	5	5	5	3
Y ! ---------------=---------Cl_______Q______________________	2	3	3	2
h₂n VoV ______________Cl_______O (N configuration)	1	1	1	N
___________________________1-71___________________________	5	5	5	0
_____________________ 2-30	4	5	4	N
nh₂ OyCci Η^γΧγ⁰'''' --Q_________________	2	3	2	N

NH2 CI^J^CI H O (S configuration )	0	0	0	N
2-69	5	5	5	0
2-70	5	5	5	0
2-71	5	5	5	0
2-71 (400 g a.i./ha)	5	5	5	2
Cl O	2	2	3	1
X,- Cl O (S configuration)	1	1	1	N
2-72	5	5	5	0
2-86	5	5	5	0
2-103	5	5	5	0
2-113	5	5	5	0
2-121	5	5	5	0
2-195	4	5	5	0
2-215	4	5	5	0
2-235	5	5	5	0
2-271	5	5	5	0
2-280	5	5	5	0
2-283	5	5	5	0
2-287	5	5	5	0
2-292	5	5	5	N
2-294	5	5	5	0
2-298	5	5	5	0
2-298 (400 g a.i./ha)	5	5	5	1
2-298 ( 100 g a.i./ha)	4	5	5	0
0 0 0 b	3	N	N	0
nh₂ en .X γι O (S configuration)	1	N	N	N
2-300	5	5	5	0
2-319	5	5	5	0
2-343	5	5	5	0
2-348	5	5	5	0
bispyribac-sodium ( 100 g a.i./ha)	1	1	0	N
cyhalofop-butyl (300 g a.i./ha)	1	1	1	0

Notes: An average value was obtained through three répétitive experiments, N represented missing of some data; if not clearly indicated, the application dose was active ingrédient 200 g/ha, plus water 450 kg/ha. Echinochloa crusgalli collected from Jiangsu, China, was résistant to ALS inhibitor herbicides and ACCe herbicides, and Digitaria sanguinalis and Semen

Euphorbiae Lathyridis also collected from Jiangsu were résistant to the ACCe herbicide cyhalofop-butyl.

Unexpectedly, although the compounds of the présent invention were similar in structure to the control compounds, they had good effects and better selectivity for major gramineous weeds, broad-leaved weeds, and Cyperus rotundus in rice fields, and had excellent commercial value. In particular, they were still outstanding to control key weeds that were résistant 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 présent invention had significantly improved activity against gramineous weeds such as Echinochloa crusgalli, Digitaria sanguinalis and Semen Euphorbiae Lathyridis, and had good selectivity for rice.

Experiment on weed effcct in pre-emergence stage

Seeds of monocotyledonous and dicotyledonous weeds and main crops (e. g. wheat, corn, rice, soybean, cotton, oilseed, millet and sorghum) were put into a plastic pot loaded with soil and covered with 0. 5-2cm soil. The test compounds of the présent invention was dissolved with acetone, then added with tween-80, diluted by a certain amount of water to reach a certain concentration, and sprayed immediately after sowîng. The obtained seeds were incubated for 4 weeks in the greenhouse after spraying and the test results were observed. It was observed that the herbicide mostly had excellent effect at the application rate of 250 g a.i./ha, especially to weeds such as Echinochloa crusgalli, Digitaria sanguinalis and Abutilon theophrasti, etc. Many compounds had good selectivity for corn, wheat, rice, soybean, oilseed râpe, etc.

Through experiments, we found that the compounds of the présent invention generally had better weed control effects, especially for major gramineous weeds such as Echinochloa crusgalli, Digitaria sanguinalis, and Setaria viridis, which are widely occurring in corn fields, rice fields and wheat fields, and major broad-leaved weeds such as Abutilon theophrasti, Rorippa indica and Bidens pilosa, and had excellent commercial value. In particular, we noticed that they had extremely high activity against broad-leaved weeds, such as Rorippa indica, Descurainia sophia, Capsella bursa-pastoris, Lithospermum arvense, Galium aparine and Stellaria media, which were résistant to ALS inhibitors.

Transplanted rice safety évaluation and weed control effect évaluation in rice field:

Rice field soil was loaded into a 1/1,000,000 ha pot. The seeds of Monochoria vaginalis were sowed and gently covered with soil, then left to stand still in greenhouse in the State of 0.5-lcm of water storage. It was kept at 3-4cm of water storage thereafter. The weeds were treated by dripping the WP or SC water diluents prepared according to the common préparation method of the compounds of the présent invention with pipette homogeneously to achieve specified effective amount when Monochoria vaginalis reached 0. 5 leaf stage.

In addition, the rice field soil that loaded into the 1/1,000,000 ha pot was leveled to keep water storage at 3-4cm depth. The 3-leaf stage rice (japonica rice) was transplanted at 3 cm of transplanting depth the next day. The compound of the présent invention was treated by the same way after 5 days of transplantation.

The fertility condition of Monochoria vaginalis 14 days and rice 21 days after the treatment of the compound of the invention with the naked eye. Evaluate the weed control effect with the aforementioned activity standard level of 0-5, many compounds exhibited excellent activity and selectivity.

Table 6 Test results of activity and safety (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: The seeds of Monochoria vaginalis were collected from Heilongjing Province of China. Tests indicated that the weeds were résistant to common rate of pyrazosulfuron-ethyl and penoxsulam.

It can be seen from the experiments that the compounds of the présent invention had excellent activity against weeds having an anti-ALS inhibiting activity which cause a serions challenge in production, and can solve the increasingly serions problem of résistance.

At the same time, it is found after several tests that the compound and the composition of the présent invention hâve good selectivity to many gramineae weeds such as Zoysia japonica, Cynodon dactylon, Festuca data, Poa annua, Lolium perenne and Paspalum vaginatum etc, and is able to control many important gramineous weeds and broad-leaved weeds. The compound also shows excellent selectivity and commercial value in the tests on wheat, corn, rice, sugarcane, soybean, cotton, oil sunflower, potato, orchards and vegetables in different herbicide application methods.

Claims

1. An R-pyridyloxycarboxylic acid represented by formula I and sait, ester dérivative thereof,

V

C represents hydrogen, halogen, alkyl or haloalkyl;

Q represents 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 represents nitro or NRjR₂, wherein Ri represents H; alkyl, alkenyl or alkynyl optionally substituted by 1-2 Ru; -COR12, nitro, OR13, SO2R14, NR15R16, N=CRi₇Ri8, alkylcarbamoyl, dialkylcarbamoyl, trialkylsilyl or dialkylphosphono; R₂ represents H; alkyl optionally substituted by 1-2 Ru; or -COR12; or NR1R2 represents N=CR₂iNR2₂R23_; N=CR24OR₂5; or a 5- or 6-membered saturated or unsaturated ring with or without oxygen atom, sulfur atom, or other nitrogen atom, which is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halogen^ alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxycarbonyl;

Ri2 represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;

R13 represents H, alkyl, haloalkyl, phenyl, benzyl or CHR3iC(O)OR₃2; R31 represents H, alkyl or alkoxy; R32 represents H, alkyl or benzyl;

R|₄ represents alkyl or haloalkyl;

Ris represents H, alkyl, formyl, alkylacyl, haloalkylacyl, alkoxycarbonyl, phenylcarbonyl, phenoxy carbonyl or benzyloxycarbonyl; R]6 represents H or alkyl;

R17 represents H, alkyl; or phenyl that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, alkyl, alkoxy; R^ represents H or alkyl; or N=CRi₇Ri8 ^N=\ J n=/M represents or Ά X__/ ;

R21, R24 each independently represent H or alkyl;

R22, R23 each independently represent H or alkyl; or NR22R23 represents a 5- or 6-membered saturated or unsaturated ring with or without oxygen atom, sulfur atom, or other nitrogen atom;

R25 represents alkyl;

the sait is métal sait, amine sait, sulfonium sait or phosphonium sait;

Q

Jl J h v

O the ester is ¹ , wherein, X represents O or S;

O

5,0, Ah'R

M represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, -alkyl-Z, 1 ^R3, < ό ³,

O ^R4_N'^R5

O -A'^R4 -V^N—'^R4 àA^or6 । I ^e 11

A ⁰ , ^R5 , ^R5 , 0 with or without halogen; or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

O

J ._R, x°Y% Y Y /-Y

Z represents * ^R3, T O _; ό , ^Rs , ^R5 , ^Rs , cyano, nitro, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

2. The R-pyridyloxycarboxylic acid and sait, ester dérivative thereof according to claim 1, wherein A, B each independently represent halogen; or C1-C8 alkyl or C3-C8 cycloalkyl with or without halogen;

C represents hydrogen, halogen, C1-C8 alkyl or halo C1-C8 alkyl;

Q represents halogen, 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;

Y represents nitro or NRjR₂, wherein Ri represents H; C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl optionally substituted by 1-2 Ru; -CORi₂, nitro, ORi₃, SO₂Ri4, NRi₅Ri₆, N=CR_[7R_1S, C1-C8 alkylcarbamoyl, di-Cl-C8 alkylcarbamoyl, tri-Cl-C8 alkylsilyl or di-Cl-C8 alkylphosphono; R₂ represents H; C1-C8 alkyl optionally substituted by 1-2 Ru; or -COR]₂; or NRiR₂ represents

Y -7 χΧ Y xX_

J s Z-x V Y ί N Y

Yn i Yn h I Y i i ¹

N=CR₂iNR₂₂R₂3, N=CR₂4OR₂5; or \V, \—, -Y, YY or Y⁰ that is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halogen, C1-C8 alkyl, C1-C8 alkoxy, halo C1-C8 alkoxy, C1-C8 alkylthio, halo C1-C8 alkylthio, amino, C1-C8 alkylamino, di-Cl-C8 alkylamino, C1-C8 alkoxycarbonyl;

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

Ri₂ represents H, Cl-Cl 8 alkyl, halo C1-C8 alkyl, C1-C8 alkoxy, phenyl, phenoxy or benzyloxy;

Ri3 represents H, C1-C8 alkyl, halo C1-C8 alkyl, phenyl, benzyl or CHR₃iC(O)OR3₂; R₃i represents H, C1-C8 alkyl or C1-C8 alkoxy; R₃₂ represents H, C1-C8 alkyl or benzyl;

Ri4 represents C1-C8 alkyl or halo C1-C8 alkyl;

Ris represents H, C1-C8 alkyl, formyl, C1-C8 alkylacyl, halo C1-C8 alkylacyl, C1-C8 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; Rie represents H or C1-C8 alkyl;

Ri7 represents H, C1-C8 alkyl; or phenyl that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, C1-C8 alkyl, C1-C8 alkoxy; R₁₈ represents H or

N=b3 n=/ ?

C1-C8 alkyl; or N=CRi7Ri8 represents V or za \__/;

R₂i, R₂4 each independently represent H or C1-C8 alkyl;

β-Ν'Υ

R₂₂, R₂₃ each independently represent H or C1-C8 alkyl; or NR₂₂R₂₃ represents \-Y,

R₂₅ represents C1-C8 alkyl;

the sait is métal sait, ammonium sait NHY primary amine RNH₂ sait, secondary amine (R)₂NH sait, tertiary amine (R)₃N sait, quatemary amine sait (R)4N⁺, morpholine sait, piperidine sait, pyridine sait, aminopropyl morpholine sait, Jeff amine D-230 sait, the sait of 2,4,6-tri(dimethylammomethyl) phénol and sodium hydroxide, alkyl sulfonium sait, alkylsulfoxonium sait, alkylphosphonium sait or alkanolphosphonium sait;

wherein, R each independently represents unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl or phenyl, and the foregoing groups are optionally substituted by one or more of the following groups: halogen, hydroxy, alkoxy, alkylthio, hydroxyalkoxy, amino, alkylamino, aminoalkylamino, phenyl;

in formula 1-1, X represents O or S;

M represents C1-C18 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C3-C8

O

II

O cycloalkyl C1-C8 alkyl, -(C1-C8 alkyl)-Z, t ^₃, M ^R3

O

^R4_N'^R5

O n î » χ^ογ%₃ Ar^NY^R< Α·ν^λ

-^R3 k II 3 I I I

Z represents V ^R3, X O , o , ^R5 , ^Rs , ^Rs , cyano, nitro, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

R4, Rs, Ré each independently represent 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;

R' ,γΛ ύ ,R' ) An ] It^- b I—N ; _ N the term “heterocyclyl” refers to v , si—I, \ I ! , I

'ύ-'⁰ or with 0, 1 or 2 oxo groups; the term “aryl” refers to phenyl

or A ^N , which is optionally substituted by at least one group selected from the group consisting of halogen, nitro, cyano, thiocyano, hydroxy, carboxy, mercapto, formyl; phenyl, benzyl, benzyloxy, phenoxy that 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”, SO₂R”, OCOR”, SCOR” with or without halogen; and amino or aminocarbonyl substituted by one or two groups selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, benzyl, benzyloxy, phenoxy, COR”, COOR”, SO₂R”, OR”;

3. The R-pyridyloxycarboxylic acid and sait, ester dérivative thereof according to claim 2, wherein A, B each independently represent halogen; or C1-C6 alkyl or C3-C6 cycloalkyl with or without halogen;

C represents hydrogen, halogen, C1-C6 alkyl or halo C1-C6 alkyl;

Q represents halogen, 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;

Y represents nitro or NRjR₂, wherein Ri represents H; C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl optionally substituted by 1-2 Ru; -CORj₂, nitro, ORb, SO₂Ri4, NR_i5Ri₆, N=CRi7Ris, C1-C6 alkylcarbamoyl, di-Cl-C6 alkylcarbamoyl, tri-Cl-C6 alkylsilyl or di-Cl-C6 alkylphosphono; R₂ represents H; C1-C6 alkyl optionally substituted by 1-2 Ru; or -CORi₂; or NRjR₂ represents

N=CR₂iNR₂₂R₂3, N=CR₂4OR₂₅; or

or ⁰ that is unsubstituted or substituted by 1-2 groups independently selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkylamino, di-Cl-C6 alkylamino, C1-C6 alkoxycarbonyl;

wherein Ru independently represents halogen, hydroxy, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkylamino, di-Cl-C6 alkylamino, C1-C6 alkoxycarbonyl; or phenyl, naphthyl,

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

R12 represents H, Cl-Cl4 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy;

Ri3 represents H, C1-C6 alkyl, halo C1-C6 alkyl, phenyl, benzyl or CHR₃iC(O)OR₃₂; R₃i represents H, C1-C6 alkyl or C1-C6 alkoxy; R₃? represents H, C1-C6 alkyl or benzyl;

Ri4 represents C1-C6 alkyl or halo C1-C6 alkyl;

Ris represents H, C1-C6 alkyl, formyl, C1-C6 alkylacyl, halo C1-C6 alkylacyl, C1-C6 alkoxycarbonyl, phenylcarbonyl, phenoxycarbonyl or benzyloxycarbonyl; Ri₆ represents H or C1-C6 alkyl;

Ri7 represents H, C1-C6 alkyl; or phenyl that is unsubstituted or substituted by 1-3 groups selected from the group consisting of halogen, C1-C6 alkyl, C1-C6 alkoxy; R_lg represents H or ^N=\ J N=Z )

Cl-C6 alkyl; or N=CRi7Rjg represents or H

R21, R24 each independently represent H or C1-C6 alkyl;

R22, R23 each independently represent H or C1-C6 alkyl; or NR22R23 represents ^NCb,

W, O_or U;

R25 represents C1-C6 alkyl;

the sait is métal sait, ammonium sait NH₄ ⁺, primary amine RNH2 sait, secondary amine (R)₂NH sait, tertiary amine (R)₃N sait, quatemary amine sait (R)₄N⁺, morpholine sait, piperidine sait, pyridine sait, aminopropyl morpholine sait, Jeff amine D-230 sait, the sait of 2,4,6-tri(dimethylaminomethyl) phénol and sodium hydroxide, C1-C18 alkylsulfonium sait, Cl-Cl 8 alkylsulfoxonium sait, Cl-Cl 8 alkylphosphonium sait or Cl-Cl 8 alkanolphosphonium sait;

wherein, R each independently represents unsubstituted Cl-Cl 8 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C3-C18 cycloalkyl or phenyl, and the foregoing groups are optionally substituted by 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 1-1, X represents O or S;

M represents C1-C18 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 O

9 O '-o Y r₃ n a η cycloalkyl C1-C6 alkyl, -(C1-C6 alkyl)-Z, ^R3 J Ô ³, b θ' , ^Rs , ^Rs ,

O with or without halogen, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl; o ο λ _R \°y°'r₃ N^R<

Z represents V°^R3, Vo^³, O , ^Rs , ^Rs , ^Rs , cyano, nitro, or unsubstituted or substituted heterocyclyl, aryl, heteroaryl;

R4, R₅, Ré each independently represent 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;

R' ·' O “K -^R' _^O < ) U X f/η ·γ X _ΓΝ -N the term “heterocyclyl” refers to v , b—b o, ' , Χ-Ά ¹—¹ , ^Sl—¹ ,

Y'n^R' N Y ^Ν-γ M'Y or with 0, 1 or 2 oxo groups; the term “aryl” refers to phenyl

consisting of halogen, nitro, cyano, thiocyano, hydroxy, carboxy, mercapto, formyl; phenyl, benzyl, benzyloxy, phenoxy that is unsubstituted or substituted by 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”, -(Cl-C6)alkyl-OR”, -(Cl-C6)alkyl-SR”, COR”, COOR”, COSR”, SOR”, SO₂R”, OCOR”, SCOR” with or without 5 halogen; and amino or aminocarbonyl substituted by 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”, SO₂R”, OR”;

R each independently represents 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, 10 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-Cl-C6 alkylsilyl, di-Cl-C6 15 alkylphosphono with or without fhioro, chloro orbromo;

4. The R-pyridyloxycarboxylic acid and sait, ester dérivative thereof according to claim 3, wherein A, B each independently represent halogen, C1-C6 alkyl, halo C1-C6 alkyl or C3-C6 20 cycloalkyl;

C represents hydrogen, halogen, C1-C6 alkyl or halo C1-C6 alkyl;

Q represents 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

V

25 alkyl, benzyl, naphthyl, furyl, thienyl, thiazolyl, pyridyl, pyrimidinyl; R^,/ that is unsubstituted or substituted by C1-C6 alkyl; or phenyl that is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, halo C1-C6 alkyl, halogen and C1-C6 alkoxy;

30 the sait is métal sait, ammonium sait NH₄ ⁺, primaiy amine RNH₂ sait, secondary amine (R)₂NH sait, tertiary amine (R)₃N sait, quatemary amine sait (R)₄N⁺, morpholine sait, piperidine sait, pyridine sait, aminopropyl morpholine sait, Jeff amine D-230 sait, the sait of 2,4,6-tn(dimethylaminomethyl) phénol and sodium hydroxide, C1-C14 alkylsulfonium sait, C1-C14 alkylsulfoxonium sait, C1-C14 alkylphosphonium sait or C1-C14 alkanolphosphonium sait;

wherein, R each independently represents unsubstituted Cl-Cl4 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C3-C12 cycloalkyl or phenyl; or C1-C14 alkyl optionally substituted by 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 1-1, X represents O or S;

M represents Cl-Cl 8 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-C2 alkyl, nitro C1-C2 alkyl, C1-C6 alkoxy C1-C2 alkyl, C1-C6 alkoxycarbonyl C1-C2 alkyl, C2-C6

O ^R4-_N'^R5

Ύ*⁴ vⁿy^r4 alkenyloxycarbonyl C1-Ç2 alkyl, -(C1-C2 alkyl)-Z, ^Rs , ^Rs , o , R' ^R' Υγ > AY tetrahydrofuryl, pyridyl, naphthyl, furyl, thienyl, * YA, ^N Y; r'^z that is unsubstituted or substituted by C1-C6 alkyl; or phenyl that is unsubstituted or substituted by C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkylamino, halogen or C1-C6 alkoxy;

o ⁰ ArV⁴ AV -A'A

Z represents O , ^Rs , ^Rs , ^Rs , tetrahydrofuryl, pyridyl, R^,z , thienyl, furyl, naphthyl; or phenyl that is unsubstituted or substituted by at least one group selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkyl, cyano and halogen;

R₃ each independently represents C1-C6 alkyl;

R4, R5, Rs each independently represent hydrogen, C1-C6 alkyl or C1-C6 alkoxycarbonyl;

R’ represents hydrogen, C1-C6 alkyl or halo C1-C6 alkyl.

5. The R-pyridyloxycarboxylic acid and sait, ester dérivative thereof according to claim 4, wherein A, B each independently represent fluoro, chloro, bromo, iodo, methyl, ethyl, propyl, isopropyl, trifluoromethyl or cyclopropyl;

C represents hydrogen, fluoro, chloro, bromo, iodo, methyl or trifluoromethyl;

Q represents methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, fluoro, chloro, bromo, cyano, amino, nitro, formyl, methoxy, methylthio, methoxycarbonyl, monochloromethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl,

I hydroxymethyl, Ύ-'⁰', Vo^z, T , νοΎ Yⁿ\, benzyl, naphthyl, furyl, thiazolyl, pyridyl, pyrimidinyl; thiazolyl that is unsubstituted or substituted by chloro; thienyl that is

-h . . ^{N N} unsubstituted or substituted by fluoro; R’ that is unsubstituted or substituted by methyl or fluoro; or phenyl that is unsubstituted or substituted by at least one group selected from the group consisting of methyl, trifluoromethyl, chloro and methoxy;

the sait is métal sait, ammonium sait NH₄ ⁺, primary amine RNH₂ sait, secondary amine (R)₂NH sait, tertiary amine (R)jN sait, quaternary amine sait (R)₄N⁺, morpholine sait, piperidine sait, pyridine sait, aminopropyl morpholine sait, Jeff amine D-230 sait, the sait of 2,4,6-tri(dimethylaminomethyl) phénol and sodium hydroxide, C1-C6 alkylsulfonium sait, C1-C6 alkylsulfoxonium sait, C1-C6 alkylphosphonium sait or C1-C6 alkanolphosphonium sait;

wherein, R each independently represents unsubstituted C1-C14 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C12 cycloalkyl, phenyl or benzyl; or C1-C14 alkyl optionally substituted by 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;

or the sait is alkali métal sait, alkaline earth métal sait, heavy métal sait, aluminum sait, ammonium sait, tétraméthylammonium sait, tetraethylammonium sait, tetrapropylammonium sait, tetraisopropylammonium sait, tetrabutylammonium sait, benzyltrimethylammonium sait, benzyltriéthylammonium sait, choline amine sait, monomethylamine sait, dimethylamine sait, trimethylamine sait, monoethylamine sait, diethylamine sait, triethylamine sait, monoisopropylamine sait, diisopropylamine sait, triisopropylamine sait, monoisobutylamine sait, pentylamine sait, hexylamine sait, heptylamine sait, dodecylamine sait, tetradecylamine sait, diallylamine sait, cyclo dodecylamine sait, benzylamine sait, monoethanolamine sait, diethanolamine sait, triethanolamine sait, tripropanolamine sait, triisopropanolamine sait, tri(2-hydroxypropyl)amine sait, methylmonoethanolamine sait, dimethylmonoethano lamine sait, methyldiethanolamine sait, diethylethanolamine sait, diglycolamine sait, diethylenetriamine sait, dimethylaminopropylamine sait, 1,2-propyldiamine sait, triethylenetetramine sait, N,N-bis[aminopropyl]methylamine sait, 2-methylthiopropylamine sait, 2-butoxyethylamine sait, AEPD sait, tri(methylol) aminomethane sait, morpholine sait, aminopropyl morpholine sait, Jeff amine D-230 sait, the sait of 2,4,6-tri(dimethylaminomethyl) phénol and sodium hydroxide;

in formula I-1, X represents O or S;

M represents 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, yV^N°2₅ /° \__,

^γΛ'^/^^νη2 , tetrahydrofuryl, tetrahydrofurylmethylene, pyridyl, pyridylmethylene,

5 naphthyl, naphthylmethylene, furyl, furylmethylene, thienyl, thienylmethylene,

N-N _N-n

R' ; / that is unsubstituted or substituted by methyl; phenyl that is unsubstituted or substituted by methyl, dimethylamino, chloro, methoxy, trifluoromethyl or isopropyl; or benzyl that is unsubstituted or substituted by trifluoromethyl, bromo, chloro, fluoro, methoxy, cyano or methyl;

R’ represents hydrogen, methyl, ethyl or difluoromethyl.

10

6. The R-pyridyloxycarboxylic acid and sait, ester dérivative thereof according to claim 5, which is selected from: nh₂

1-26 ⁰

2-30

O

2-34

2-62

Ο

2-271

2-294

2-283

ο 2-300

7. A préparation method of the R-pyridyloxycarboxylic acid and sait, ester dérivative thereof according to any one of claims 1-6, which comprises the following steps:

5 a compound of formula III is reacted with a compound of formula II to obtain a compound of formula 1-1-1; the reaction scheme is as foliows:

wherein, W represents an alkali métal; Hal represents halogen; the reaction is carried out in the presence of a catalyst and a solvent, the catalyst is TBAB, and the solvent is one or more selected 10 from the group consisting of DCM, DCE, ACN, THF, DMF;

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

Y ¥

l -14 I the solvent is one or more selected from the group consisting of methanol, éthanol, and 15 isopropanol;

.1 Ί-2 wherein, the reaction is carried out in the presence of a dehydrant and a solvent, the dehydrant is DCC, and the solvent is one or more selected from the group consisting of dichloromethane, dichloroethane, acetonitrile, N,N-dimethylformamide, Ν,Ν-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, toluene, xylene;

or, when Y represents NR|R₂ (R_u R₂ are not hydrogen at the same time), it is obtained by

reacting a compound of formula 1-2 or a compound of formula 1-1-3

ï L3 _with a corresponding halide;

wherein, the reaction is carried out in the presence of a base and a solvent, wherein the base is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and césium 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 is optionally added during the reaction.

8. A herbicidal composition comprising (i) at least one of an R-type pyridyloxycarboxylic acid and sait, ester dérivative thereof according to any one of claims 1-6; optionally, comprising (ii) one or more further herbicides and/or safeners or (iii) agrochemically acceptable formulation auxiliaries.

9. A method for controlling a weed comprising applying a herbicidally effective amount of at least one of the R-type pyridyloxycarboxylic acid and sait, ester dérivative thereof according to any one of claims 1-6 or the herbicidal composition according to claim 8 on a plant or in a weed area.

10. Use of at least one of the R-type pyridyloxycarboxylic acid and sait, ester dérivative thereof according to any one of claims 1-6 or the herbicidal composition according to claim 8 for controlling a weed.

Abstract

The invention relates to the field of pesticide technology, and in particular to a type of R-pyridyloxycarboxylic acid and sait, ester dérivative, préparation method, herbicidal composition and application thereof. The R-pyridyloxycarboxylic acid is represented by formula

A

C

5 I,

H

O ^ü , wherein, A, B each independently represent halogen, alkyl or cycloalkyl with or without halogen; C represents hydrogen, halogen, alkyl, haloalkyl; Q represents halogen, cyano, cyanoalkyl and the like; Y represents nitro or NRiR₂; the sait is métal sait, amine sait, sulfonium sait, phosphonium sait; the ester is

A

^B Q

O ^0-1 , wherein, X represents O or

S; M represents alkyl, alkenyl, alkynyl and the like with or without halogen. The compound has 10 excellent herbicidal activity and hîgher crop safety, especially good selectivity for key crops such as rice.