CN109400526A

CN109400526A - Pyridine oxygroup thioes derivatives and preparation method thereof, Herbicidal combinations and application

Info

Publication number: CN109400526A
Application number: CN201811609358.9A
Authority: CN
Inventors: 连磊; 彭学岗; 华荣保; 张景远; 崔琦
Original assignee: Qingdao Qing Yuan Compound Co Ltd
Current assignee: Qingdao Qing Yuan Compound Co Ltd
Priority date: 2018-12-27
Filing date: 2018-12-27
Publication date: 2019-03-01
Anticipated expiration: 2038-12-27
Also published as: CN109400526B

Abstract

The invention belongs to technical field of pesticide, and in particular to a kind of pyridine oxygroup thioes derivatives and preparation method thereof, Herbicidal combinations and application.The pyridine oxygroup thioes derivatives as shown in formula I,Wherein, A, B separately represent halogen, contain or not contain the alkyl or cycloalkyl of halogen；C represents hydrogen, halogen, alkyl, halogenated alkyl；Q represents halogen, cyano, cyanoalkyl, hydroxy alkyl, amino, nitro, formoxyl, without or with the alkyl etc. of halogen；M represents alkyl, the alkenyl etc. without or with halogen；X represents nitro or NR₁R₂.The activity of weeding of the compound is excellent, and has higher crop safety, establishes good selectivity especially for critical harvests such as rice.

Description

Pyridine oxygroup thioes derivatives and preparation method thereof, Herbicidal combinations and application

Technical field

The invention belongs to technical field of pesticide, and in particular to a kind of pyridine oxygroup thioes derivatives and preparation method thereof remove Careless composition and application.

Background technique

The prevention and treatment of weeds is to realize a vital link during high-efficiency agriculture, although herbicide kind in the market A series of class multiplicity, for example, DE2335349A1, GB1418979A, US3761486 etc. disclose such as general formulas Compound represented and its application as herbicide.But due to the continuous expansion in market, the use longevity of the resistance of weeds, drug The problems such as life and the economy of drug and people are to the pay attention to day by day of environment, especially with five fluorine of ALS inhibiting mechanism Sulphur grass amine, bispyribac-sodium, pyribenzoxim, the cyhalofop-butyl of ACCe class inhibiting mechanism, the market mainstreams such as metamifop rice field standing grain The serious generation of undergraduate course weeds herbicide resistance, paddy field are prevented and kill off the gramineous grasses such as barnyard grass, herba digitariae, herba setariae viridis, semen euphorbiae and are encountered Severe challenge lacks the medicament for effectively preventing and kill off resistant weed, this just needs scientists constantly to study and then develops new height Effect, safety, economy and the herbicide kind with different role mode.

Summary of the invention

It is described the present invention provides a kind of pyridine oxygroup thioes derivatives and preparation method thereof, Herbicidal combinations and application The activity of weeding of compound is excellent, and has higher crop safety, establishes especially for critical harvests such as rice Good selectivity.

The technical solution adopted by the invention is as follows:

One kind pyridine oxygroup thioes derivatives as shown in formula I,

Wherein, A, B separately represent halogen, contain or not contain the alkyl or cycloalkyl of halogen；

C represents hydrogen, halogen, alkyl, halogenated alkyl；

Q represents halogen, cyano, cyanoalkyl, hydroxy alkyl, amino, nitro, formoxyl, without or with the alkane of halogen Base, alkenyl, alkynyl, naphthenic base, alkoxy, alkylthio group, alkyl-carbonyl, alkoxy carbonyl, alkylaminoalkyl group or alkoxy alkane Base, unsubstituted or substituted aryl, heteroaryl, aryl alkyl, heteroaryl alkyl；

M represent without or with the alkyl of halogen, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl ,-alkyl-R, And unsubstituted or substituted heterocycle Base, aryl, heteroaryl；

R is representedCyano, Nitro；

R₃Separately represent alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl and unsubstituted or substituted miscellaneous Ring group, aryl, heteroaryl, heterocyclylalkyl group, aryl alkyl, heteroaryl alkyl；

R₄、R₅、R₆Separately represent hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, alkoxy carbonyl with And unsubstituted or substituted heterocycle, aryl, heteroaryl, heterocyclylalkyl group, aryl alkyl, heteroaryl alkyl；

X represents nitro or NR₁R₂, wherein R₁H is represented, it optionally can be by 1-2 R₁₁Substituted alkyl, alkenyl or alkynyl ,- COR₁₂, nitro, OR₁₃, SO₂R₁₄, NR₁₅R₁₆, N=CR₁₇R₁₈, alkyl-carbamoyl, dialkyl carbamoyl, trialkyl first Silylation or dialkylphosphono；R₂H is represented, it optionally can be by 1-2 R₁₁Substituted alkyl or-COR₁₂；Or NR₁R₂It represents N=CR₂₁NR₂₂R₂₃, N=CR₂₄OR₂₅, unsubstituted or halogen, alkyl, alkoxy, halogenated alkoxy, alkane are independently selected from by 1-2 Sulfenyl, amino, alkyl amino, dialkyl amido, does not contain or contains replaced the group in alkoxy carbonyl halogenated alkylthio There are 5- the or 6- member saturation or unsaturated ring of oxygen atom, sulphur atom or other nitrogen-atoms；

Wherein R₁₁Independently represent halogen, hydroxyl, alkoxy, halogenated alkoxy, alkylthio group, halogenated alkylthio, amino, alkane Base amino, dialkyl amido, alkoxy carbonyl, unsubstituted or substituted aryl, heteroaryl；

R₁₂Represent H, alkyl, halogenated alkyl, alkoxy, phenyl, phenoxy group or benzyloxy；

R₁₃Represent H, alkyl, halogenated alkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represent H, alkyl or alkoxy； R₃₂Represent H, alkyl or benzyl；

R₁₄Represent alkyl, halogenated alkyl；

R₁₅Represent H, alkyl, formoxyl, alkyl acyl, halogenated alkyl acyl group, alkoxy carbonyl, phenylcarbonyl group, phenoxy group Carbonyl or benzyloxycarbonyl；R₁₆Represent H, alkyl；

R₁₇Represent H, alkyl, the unsubstituted or phenyl replaced 1-3 group in halogen, alkyl, alkoxy；R₁₈ Represent H, alkyl；Or N=CR₁₇R₁₈It represents

R₂₁、R₂₄Separately represent H or alkyl；

R₂₂、R₂₃Separately represent H or alkyl；Or NR₂₂R₂₃Representative do not contain or containing oxygen atom, sulphur atom or 5- the or 6- member of other nitrogen-atoms is saturated or unsaturated ring；

R₂₅Represent alkyl.

Preferably, A, B separately represent halogen, contain or not contain the C1-C8 alkyl or C3-C8 cycloalkanes of halogen Base；

C represents hydrogen, halogen, C1-C8 alkyl, halogenated C1-C8 alkyl；

Q represents halogen, cyano, cyano C1-C8 alkyl, hydroxyl C1-C8 alkyl, amino, nitro, and formoxyl is free of or contains There are C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C1-C8 alkoxyl, the C1-C8 alkylthio group, C1- of halogen C8 alkyl-carbonyl, C1-C8 alkoxyl carbonyl, C1-C8 alkyl amino C1-C8 alkyl or C1-C8 alkoxyl C1-C8 alkyl, do not take Generation or the aryl replaced, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl；

M is represented without or with the C1-C18 alkyl of halogen, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C3-C8 Naphthenic base C1-C8 alkyl ,-(C1-C8 alkyl)-R, And unsubstituted or substituted heterocycle, aryl, heteroaryl；

R is representedCyano, Nitro；

R₃Separately represent C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C3-C8 naphthenic base C1-C8 alkyl and unsubstituted or substituted heterocycle, aryl, heteroaryl, heterocycle C1-C8 alkyl, aryl C1-C8 alkyl, Heteroaryl C1-C8 alkyl；

R₄、R₅、R₆Separately represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C3- C8 naphthenic base C1-C8 alkyl, C1-C8 alkoxyl carbonyl and unsubstituted or substituted heterocycle C1-C8 alkyl, aryl C1-C8 Alkyl, heteroaryl C1-C8 alkyl；

X represents nitro or NR₁R₂, wherein R₁H is represented, it optionally can be by 1-2 R₁₁Substituted C1-C8 alkyl, C2-C8 alkene Base or C2-C8 alkynyl ,-COR₁₂, nitro, OR₁₃, SO₂R₁₄, NR₁₅R₁₆, N=CR₁₇R₁₈, C1-C8 alkyl-carbamoyl, two C1- C8 alkyl-carbamoyl, three C1-C8 aIkylsilyl groups or two C1-C8 alkyl phosphonos；R₂H is represented, it optionally can be by 1-2 A R₁₁Substituted C1-C8 alkyl or-COR₁₂；Or NR₁R₂Represent N=CR₂₁NR₂₂R₂₃, N=CR₂₄OR₂₅, unsubstituted or by 1-2 It is a to be independently selected from halogen, C1-C8 alkyl, C1-C8 alkoxyl, halogenated C1-C8 alkoxyl, C1-C8 alkylthio group, halogenated C1-C8 alkane Sulfenyl, amino, C1-C8 alkyl amino, two C1-C8 alkyl aminos, replaced the group in C1-C8 alkoxyl carbonyl

Wherein R₁₁Independently represent halogen, hydroxyl, C1-C8 alkoxyl, halogenated C1-C8 alkoxyl, C1-C8 alkylthio group, halogen For C1-C8 alkylthio group, amino, C1-C8 alkyl amino, two C1-C8 alkyl aminos, C1-C8 alkoxyl carbonyl is unsubstituted or by halogen Element, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxyl, phenyl, naphthalene replaced 1-3 group in nitro,

R₁₂Represent H, C1-C18 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxyl, phenyl, phenoxy group or benzyloxy；

R₁₃Represent H, C1-C8 alkyl, halogenated C1-C8 alkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represent H, C1-C8 Alkyl or C1-C8 alkoxyl；R₃₂Represent H, C1-C8 alkyl or benzyl；

R₁₄Represent C1-C8 alkyl, halogenated C1-C8 alkyl；

R₁₅Represent H, C1-C8 alkyl, formoxyl, C1-C8 alkyl acyl, halogenated C1-C8 alkyl acyl, C1-C8 alkoxyl Carbonyl, phenylcarbonyl group, phenyloxycarbonyl or benzyloxycarbonyl；R₁₆Represent H, C1-C8 alkyl；

R₁₇Represent H, C1-C8 alkyl, unsubstituted or by 1-3 group institute in halogen, C1-C8 alkyl, C1-C8 alkoxyl Substituted phenyl；R₁₈Represent H, C1-C8 alkyl；Or N=CR₁₇R₁₈It represents

R₂₁、R₂₄Separately represent H or C1-C8 alkyl；

R₂₂、R₂₃Separately represent H or C1-C8 alkyl；Or NR₂₂R₂₃It represents

R₂₅Represent C1-C8 alkyl；

" heterocycle " refers to 0,1 or 2 oxo group " aryl " refers to phenyl, naphthalene；It is described " miscellaneous The aromatic cyclic group that aryl " " heteroaryl " refers to containing 3 to 6 annular atoms and can also be condensed by benzo ring, it is described 1 to 4 hetero atom in annular atom is selected from oxygen, nitrogen and sulphur, for example, Wherein, halogen, nitro, cyano, thiocyano, hydroxyl, carboxylic are selected from Base, sulfydryl, formoxyl, unsubstituted or phenyl, benzyl replaced at least one group in halogen, alkyl, alkoxy Base, benzyloxy, phenoxy group, contain or not contain the alkyl of halogen, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, OR ", SR " ,- Alkyl-OR " ,-alkyl-SR ", COR ", COOR ", COSR ", SOR ", SO₂R ", OCOR ", SCOR ", and by selected from hydrogen, alkyl, Alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, phenyl, benzyl, benzyloxy, phenoxy group, COR ", COOR ", SO₂In R ", OR " Replaced at least one group in amino replaced one or two group or amino carbonyl；

R ' separately represents hydrogen, nitro, hydroxyl, and amino contains or not contain alkyl, alkenyl, alkynyl, the ring of halogen Alkyl, cycloalkenyl, cycloalkyl-alkyl, alkoxy, alkenyl oxygroup, alkynyl oxygroup, cycloalkyl oxy, alkoxyalkyl, alkoxy Carbonyl, alkylthiocarbonyl, alkyl sulphonyl, Alkylsulfonylalkyl, alkyl-carbonyl, Alkylcarbonylalkyl, alkyl acyloxy, alkane Base amino, alkyl amino-carbonyl, alkoxy amino carbonyl, alkoxy carbonyl alkyl, alkyl amino-carbonyl alkyl, trialkylsilyl Base, dialkylphosphono；

R " separately represents hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl.

It is highly preferred that A, B separately represent halogen, the C1-C6 alkyl or C3-C6 cycloalkanes of halogen are contained or not contain Base；

C represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl；

Q represents halogen, cyano, cyano C1-C6 alkyl, hydroxyl C1-C6 alkyl, amino, nitro, and formoxyl is free of or contains There are C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C1-C6 alkoxy, the C1-C6 alkylthio group, C1- of halogen C6 alkyl-carbonyl, C1-C6 alkoxy carbonyl, C1-C6 alkyl amino C1-C6 alkyl or C1-C6 alkoxy C 1-C6 alkyl, do not take Generation or the aryl replaced, heteroaryl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl；

M is represented without or with the C1-C12 alkyl of halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 Naphthenic base C1-C6 alkyl ,-(C1-C6 alkyl)-R, And unsubstituted or substituted heterocycle, aryl, heteroaryl；

R is representedCyano, Nitro；

R₃Separately represent C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base C1-C6 alkyl and unsubstituted or substituted heterocycle, aryl, heteroaryl, heterocycle C1-C6 alkyl, aryl C1-C6 alkyl, Heteroaryl C1-C6 alkyl；

R₄、R₅、R₆Separately represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3- C6 naphthenic base C1-C6 alkyl, C1-C6 alkoxy carbonyl and unsubstituted or substituted heterocycle C1-C6 alkyl, aryl C1-C6 Alkyl, heteroaryl C1-C6 alkyl；

X represents nitro or NR₁R₂, wherein R₁H is represented, it optionally can be by 1-2 R₁₁Substituted C1-C6 alkyl, C2-C6 alkene Base or C2-C6 alkynyl ,-COR₁₂, nitro, OR₁₃, SO₂R₁₄, NR₁₅R₁₆, N=CR₁₇R₁₈, C1-C6 alkyl-carbamoyl, two C1- C6 alkyl-carbamoyl, three C1-C6 aIkylsilyl groups or two C1-C6 alkyl phosphonos；R₂H is represented, it optionally can be by 1-2 A R₁₁Substituted C1-C6 alkyl or-COR₁₂；Or NR₁R₂Represent N=CR₂₁NR₂₂R₂₃, N=CR₂₄OR₂₅, unsubstituted or by 1-2 It is a to be independently selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio group, halogenated C1-C6 alkane Sulfenyl, amino, C1-C6 alkyl amino, two C1-C6 alkyl aminos, replaced the group in C1-C6 alkoxy carbonyl

Wherein R₁₁Independently represent halogen, hydroxyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio group, halogen For C1-C6 alkylthio group, amino, C1-C6 alkyl amino, two C1-C6 alkyl aminos, C1-C6 alkoxy carbonyl is unsubstituted or by halogen Element, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, naphthalene replaced 1-3 group in nitro,

R₁₂Represent H, C1-C14 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy group or benzyloxy；

R₁₃Represent H, C1-C6 alkyl, halogenated C1-C6 alkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represent H, C1-C6 Alkyl or C1-C6 alkoxy；R₃₂Represent H, C1-C6 alkyl or benzyl；

R₁₄Represent C1-C6 alkyl, halogenated C1-C6 alkyl；

R₁₅Represent H, C1-C6 alkyl, formoxyl, C1-C6 alkyl acyl, halogenated C1-C6 alkyl acyl, C1-C6 alkoxy Carbonyl, phenylcarbonyl group, phenyloxycarbonyl or benzyloxycarbonyl；R₁₆Represent H, C1-C6 alkyl；

R₁₇Represent H, C1-C6 alkyl, unsubstituted or by 1-3 group institute in halogen, C1-C6 alkyl, C1-C6 alkoxy Substituted phenyl；R₁₈Represent H, C1-C6 alkyl；Or N=CR₁₇R₁₈It represents

R₂₁、R₂₄Separately represent H or C1-C6 alkyl；

R₂₂、R₂₃Separately represent H or C1-C6 alkyl；Or NR₂₂R₂₃It represents

R₂₅Represent C1-C6 alkyl；

" heterocycle " refers to 0,1 or 2 oxo group " aryl " refers to phenyl, naphthalene；It is described " miscellaneous Aryl " refers to Wherein, by be selected from halogen, nitro, cyano, thiocyano, hydroxyl, carboxyl, sulfydryl, formoxyl, it is unsubstituted or by selected from halogen, Phenyl, benzyl, benzyloxy, phenoxy group replaced at least one group in C1-C6 alkyl, C1-C6 alkoxy, contain or not C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base C1-C6 alkyl, OR " containing halogen, SR " ,-(C1-C6) alkyl-OR " ,-(C1-C6) alkyl-SR ", COR ", COOR ", COSR ", SOR ", SO₂R”、OCOR”、 SCOR ", and it is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base C1-C6 Alkyl, phenyl, benzyl, benzyloxy, phenoxy group, COR ", COOR ", SO₂Ammonia replaced one or two of R ", OR " group Replaced 0,1,2 or 3 group in base or amino carbonyl；

R ' separately represents hydrogen, nitro, hydroxyl, and amino contains or not contain C1-C6 alkyl, the C2- of fluorine, chlorine, bromine C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 cycloalkenyl, C3-C6 naphthenic base C1-C6 alkyl, C1-C6 alkoxy, C2- C6 alkenyl oxygroup, C2-C6 alkynyl oxygroup, C3-C6 cycloalkyl oxy, C1-C6 alkoxy C 1-C6 alkyl, C1-C6 alkoxy carbonyl Base, C1-C6 alkylthiocarbonyl, C1-C6 alkyl sulphonyl, C1-C6 alkyl sulphonyl C1-C6 alkyl, C1-C6 alkyl-carbonyl, C1- C6 alkyl-carbonyl C1-C6 alkyl, C1-C6 alkyl acyloxy, C1-C6 alkyl amino, C1-C6 alkyl amino-carbonyl, C1-C6 alcoxyl Base amino carbonyl, C1-C6 alkoxy carbonyl C1-C6 alkyl, C1-C6 alkyl amino-carbonyl C1-C6 alkyl, three C1-C6 alkyl first silicon Alkyl, two C1-C6 alkyl phosphonos；

R " separately represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 ring Alkyl C1-C6 alkyl.

It is further preferred that A, B separately represent halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 cycloalkanes Base；

C represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl；

Q represents C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 naphthenic base, C2-C6 alkenyl, C2-C6 alkynyl, halogen, cyanogen Base, amino, nitro, formoxyl, C1-C6 alkoxy, C1-C6 alkylthio group, C1-C6 alkoxy carbonyl group, hydroxyl C1-C6 alkyl, C1-C6 Alkoxy C 1-C2 alkyl, cyano C1-C2 alkyl, C1-C6 alkylamino C1-C2 alkyl, benzyl, naphthalene, furyl, thienyl, thiophene Oxazolyl, pyridyl group, pyrimidine radicals and unsubstituted or alkyl-substituted by C1-C6It is unsubstituted or by C1-C6 alkyl, halogen For phenyl replaced at least one group in C1-C6 alkyl, halogen and C1-C6 alkoxy；

M represents C1-C12 alkyl (preferably C1-C8 alkyl, more preferable C1-C6 alkyl), halogenated C1-C8 alkyl, C3-C6 ring Alkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkoxy carbonyl group, C1-C6 alkyl sulphur Acyl group, cyano C1-C6 alkyl, nitro C1-C6 alkyl, C1-C6 alkoxy C 1-C6 alkyl, C1-C6 alkoxy carbonyl group C1-C6 alkyl, C2-C6 allyloxycarbonyl C1-C6 alkyl ,-(C1-C6 alkyl)-R,Tetrahydrofuran base, Pyridyl group, naphthalene, furyl, thienyl,And unsubstituted or C1-C6 is alkyl-substitutedIt is unsubstituted Or the phenyl replaced by C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkyl amino, halogen or C1-C6 alkoxy；

R is represented

R₃Separately represent C1-C6 alkyl；

R₄、R₅、R₆Separately represent hydrogen, C1-C6 alkyl, C1-C6 alkoxy carbonyl；

R ' represents C1-C6 alkyl, halogenated C1-C6 alkyl；

X represents amino, C1-C6 alkyl amino, C1-C6 alkyl-carbonyl-amino, benzylcarbonylamino, benzylamino, does not take Generation or the alkyl-substituted furanylmethylenyl amino of halogenated C1-C6.

It is further preferred that A, B separately represent fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, three Methyl fluoride, cyclopropyl；

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

Q represents methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, acetenyl, fluorine, chlorine, bromine, cyano, amino, nitre Base, formoxyl, methoxyl group, methyl mercapto, methoxycarbonyl group, chloromethyl, a methyl fluoride, difluoromethyl, trifluoromethyl, 2- chloroethene Base, 2,2,2- trifluoroethyl, hydroxymethyl,Benzyl, naphthalene, furan It mutters base, thienyl, thiazolyl, pyridyl group, pyrimidine radicals and unsubstituted or methyl substitutedIt is unsubstituted or by first Phenyl replaced at least one group in base, trifluoromethyl, chlorine and methoxyl group；

R ' represents methyl, ethyl, difluoromethyl；

M represents methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, amyl, hexyl, heptan Base, octyl, nonyl, decyl, undecyl, dodecyl, trifluoromethyl, pentafluoroethyl group, 3- chlorobutyl, 2- fluoro ethyl, 2- chlorine Ethyl, 2- bromoethyl, 2,2- bis-fluoro ethyls, 2,2,2- trifluoroethyl, 4,4,4- triRuorobutyl, 2,2,3,3,3- pentafluoropropyl group, Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, allyl, 2-propynyl, methoxyl group, carbethoxyl group, methyl sulphonyl, Tetrahydrofuran base, pyridyl group, naphthalene, furans Base, thienyl,And it is unsubstituted or methyl substitutedIt is unsubstituted or by methyl, dimethylamino, The phenyl that chlorine, methoxyl group, trifluoromethyl or isopropyl replace；

X represents NH₂、

In the definition of the compound shown in above-mentioned general formula I and following all structural formulas, no matter technical term used individually makes With or use in compound word, represent following substituent group: can be straight chain or branch with the alkyl group of more than two carbon atom Chain.Such as compound word "-alkyl-OR " " in alkyl can be-CH₂-、-CH₂CH₂-、-CH(CH₃)-、-C(CH₃)₂Etc..Alkyl group For for example, methyl；Ethyl；N-propyl or isopropyl；Normal-butyl, isobutyl group, tert-butyl or 2- butyl；Amyl；Hexyl, such as N-hexyl, isohesyl and 1,3- dimethylbutyl.Halogen is fluorine, chlorine, bromine or iodine.

If a group, replaced group, this is understood to mean that the group by one or more identical or different The group selected from those of mentioned group replace.In addition, what is contained in identical or different substituent group identical or different takes It is selected independently, may be the same or different for character.

According to the property of substituent group and its connected mode, compounds of formula I can be used as stereoisomer presence.Example Such as, if there is one or more asymmetric carbon atoms, then enantiomter and diastereoisomer be may occur in which.Stereoisomer It is obtained in the mixture that can be obtained from preparation by conventional separation methods, for example by chromatography.Can equally it pass through Stereoisomer is selectively prepared using Stereoselective reaction and using optically active starting material and/or auxiliary agent. The invention further relates to comprising in general formula I but all stereoisomers and its mixture that are not specifically defined.

The preparation method of the pyridine oxygroup thioes derivatives, comprising the following steps:

General formula III compound represented is carried out to react chemical combination shown in obtained general formula I with II compound represented of general formula Object；Its reaction equation is as follows:

Wherein, W represents alkali metal, preferably K, Na；Hal represents halogen, preferably Br, Cl；The reaction is in catalyst and molten It is carried out in the presence of agent, it is preferable that the catalyst is TBAB, and the solvent is one of DCM, DCE, ACN, THF, DMF Or multiple combinations.

Or when X represents NR₁R₂(R₁、R₂Simultaneously it is not hydrogen) when, by general formula I-1 compound representedReact with corresponding halides and be made；

Wherein, the preferred chloro thing of halides or bromo-derivative；The reaction carries out in the presence of alkali and solvent, the alkali choosing From one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate；Solvent is selected from In THF, 1,4- dioxane, toluene, 1,2- dichloroethanes, ethyl acetate, acetonitrile, DMF, acetone, methylene chloride and chloroform One or more combinations；Catalyst, preferably DMAP can also be added in the reaction process.

A kind of Herbicidal combinations, including (i) at least one of pyridine oxygroup thioes derivatives shown in formula I；It is preferred that Ground further includes (ii) one or more other herbicides and/or safener；It is highly preferred that further including on (iii) agriculture chemistry Acceptable formulation auxiliary agents.

A method of control weeds, including in the pyridine oxygroup thioes derivatives by herbicidally effective amount at least A kind of or described herbicidal composition use is on plant or weed regions, it is preferable that the plant is rice (such as round-grained rice Rice, long-grained nonglutinous rice), the weeds be grass family (such as barnyard grass, herba digitariae, semen euphorbiae, herba setariae viridis), broadleaved herb (such as piemarker, Monochoria vaginalis) and Sedge weed (such as cyperus iria).

At least one of described pyridine oxygroup thioes derivatives or the herbicidal composition are on control weeds Purposes, it is preferable that the pyridine oxygroup thioes derivatives are used to prevent and kill off the weeds in useful crop, the useful crop For genetically modified crops or the processed crop of genome editing technique, it is highly preferred that the crop is rice (such as japonica rice, Xian Rice), the weeds are grass family (such as barnyard grass, herba digitariae, semen euphorbiae, herba setariae viridis), broadleaved herb (such as piemarker, Monochoria vaginalis) and Cyperaceae Weeds (such as cyperus iria).

For many economically important unifacial leaves and dicotyledonous harmful plants, compound of formula I of the invention, which has, to be protruded Activity of herbicide.Active material of the invention is effective also for perennial weeds, these weeds are from rhizome, rhizomes or other Perennial organ on grow out, be difficult to control.In this regard, if prior to seeding, sprout before or sprout after using should Substance is generally inessential.The representative example of unifacial leaf and broadleaf weed group that specifically mentioned the compounds of this invention can control, The species for the determination being not limited to.The example of the weed species of active material useful effect includes monocotyledon: annual In Avena, rye, careless category, amur foxtail category, farad this, barnyard grass, knotgrass, setaria and Cyperus and perennial wheatgrass Category, Cynodon, cogon and sorghum and perennial Cyperus.

About dicotyldenous weed species, act on for example annual Bedstraw of species that can extend to, Viola, Veronica, lamium, Stellaria, Amaranthus, sinapsis alba category, Ipomoea, chrysanthemum harvest spp, Matricaria and abutilon and perennial Weeds japanese bearbind genus, Cirsium, Rumex and artemisia.Effectively control has active material of the present invention under the conditions of rice growing is this undetermined Evil plant, such as barnyard grass, Sagittaria, Waterplantain, Eleocharis, sugarcane grass and Cyperus.If the compounds of this invention applied before rudiment For soil surface, the rice shoot of weeds can be prevented completely before weeds grow, or just stopped growing when weeds grow cotyledon, It is finally completely dead after three to four weeks.The compounds of this invention especially resists the good activity of following plants, and A Pila is careless, small White dead nettle, volume stem smartweed, herba stellariae mediae, Changchun cane leaves Veronica, Veronica persica, heartsease and amaranth, Bedstraw and summer cypress.

Although the compounds of this invention has excellent activity of herbicide for unifacial leaf and dicots weeds, for important Economy class crop plants, such as wheat, barley, rye, rice, corn, beet, cotton and soybean do not damage but at all, Either damage is inappreciable.It is especially compatible very well with cereal crops, such as wheat, barley and corn, especially Wheat.Therefore, the compounds of this invention is very suitable for the useless plant being selectively controlled in agricultural crop or ornamental plant.

Due to their deweeding property, in the plant cultivation of genetic engineering that is known or will occurring, these active matters Matter can be used for controlling noxious plant.Genetically modified plants usually have superior character, such as especially special to specific insecticide The resistance for determining herbicide, to the resistance of the pathogenic microorganisms of plant disease or plant disease, such as specific insect or true The microorganism of bacterium, bacterium or virus.Other especially characters are related with following conditions of product, for example, quantity, quality, storage Stability, component and special ingredient.So, it is known that the transgenic plant product of acquisition have increased content of starch or Improved starch quality or different Fatty acid components.

Compound of formula I of the invention or its salt are preferred for, the crop and ornamental plant of economically important transgenosis, example Such as cereal, such as wheat, barley, rye, oat, grain, rice, cassava and corn or it is used for beet, cotton, soybean, rape The cultivation of seed, potato, tomato, pea and other vegetable plants.Compound of formula I is preferred for the weeding of useful plant cultivation Agent, these plants have drug resistance to the toxic action of herbicide with drug resistance or by genetic engineering.

Traditional breeding includes with the method than known plants with improvement shape plant, such as traditional mating method It is bred with mutant strain.It in other words, can be by means of the method for genetic engineering (see, e.g. EP-0221044 A, EP- 0131624 A) come obtain with improve character new plant.Such as, it has been described that several methods:

In order to improve the Starch synthesis in plant, change crop plants (such as WO 92/11376, WO using genetic engineering 92/14827, WO 91/19806)；

The transgenic crop plant resistant to specific herbicide, to glufosinate herbicide (such as EP-0242236 A, EP-0242246 A) or to glyphosate-class herbicides (WO 92/00377), or to sulfonylurea herbicide (EP-0257993 A, US-5013659 A)；

Such as the transgenic crop plant of cotton, it can generate bacillus thuringiensis toxin (Bt toxin), and this toxin can To defend the infringement (EP-0142924 A, EP-0193259 A) of specific pests on plants；

Transgenic crop plant (WO91/13972) with improved Fatty acid component.

Known many can prepare have improve character genetically modified plants molecular biotechnology (see, e.g. Sambrook etc., 1989, molecule amplification, the laboratory manual second edition, Cold Spring Harbor Laboratory publication, Cold SpringHarbor, New York；Or Winnacker " Gene und Klone " [gene and clone], VCH Weinheim, the second edition 1996 or Christou, " plant 1 (1996) 423-431 of the trend of science ")).In order to realize the operation of genetic engineering, nucleic acid molecules may be introduced plasmid, led to The recombination of DNA sequence dna is crossed, mutates or sequence changes.Using above-mentioned standard method, such as substrate, removing unit can be exchanged Sub-sequence increases the sequence naturally or synthesized.In order to which DNA fragmentation is interconnected, it is possible to be accompanied with combination in segment Body or connector.

The plant cell for reducing active gene prod can be prepared with following methods, such as at least one suitable by expression When antisense-RNA, justice-RNA achieve the effect that co-suppression, or ribozyme by expressing at least one appropriate structuring, it The transcription product of specific cleavage said gene product.

For this purpose, it is possible to use the DNA molecular comprising gene product whole coded sequence, includes that may be present Any flanking sequence, and use the DNA molecular comprising only only a part coded sequence, these parts must long enough to reach The effect of antisense in cell.Also can be used with gene product coded sequence has high homology but not exactly the same sequence Column.

When expressing nucleic acid molecules in plant, the protein of synthesis can be determined in any desired plant cell room Position.However in order to be positioned in specific room, it is possible to for example code area is connected with DNA sequence dna, it is fixed in specific position to ensure Position.These sequences be known to those skilled in the art (see, e.g. Braun etc., EMBO J.11 (1992) 3219- 3227；Wolter etc., Proc.Natl.Acad.Sci.USA 85 (1988), 846-850；The Plant such as Sonnewald are J.1 (1991), 95-106).

Transgenic plant cells can be recombinated onto entire plant using known technology.Genetically modified plants can be to appoint What desired plant variety, i.e. unifacial leaf and dicotyledon.In such a way, by overexpressing, forbidding or inhibit homologous (=naturally) gene or gene order, or pass through (=external) gene or the expression of gene order of xenogenesis, it is possible to Obtain the genetically modified plants for improving character.

When using active material of the invention on the crop in transgenosis, can be observed on other crops in addition to having Inhibition noxious plant effect outside, special effect is often had on corresponding genetically modified crops, for example, can improve or Expand the range of control weeds, improves amount of application when application, the preferably drug resistance of genetically modified crops and the performance of herbicide very Good combination, and the growth of the crop plants of transgenosis and the influence of yield.Therefore present invention provides the compounds Purposes, as herbicide control transgenic crop plant in noxious plant.

In addition the compounds of this invention can obviously adjust the growth of crop plants.Plant metabolism is participated in by adjusting, is used The component and promotion harvest of these compound oriented control plants, such as make plant desiccation and stunted growth.And they are also fitted Growth in adjusting and inhibiting undesirable plant growth, without destroying crop.Many unifacial leaves that are grown in of plant are inhibited to plant Play very important effect in object and dicotyledon crop because can reduce in this way or completely pre- lodging-prevention.

General preparation can be used to apply the compound of the present invention, wettable powder can be used, emulsifiable concentrates, can spray Solution, powder or the particle spilt.Present invention provides the herbicidal compositions including compound of formula I in this way.According to common The physical parameter of biology and/or chemistry can prepare compound of formula I with various ways.Suitable preparation selects example are as follows: can Wet powder (WP), water-soluble powder (SP), water-soluble concentrate, emulsifiable concentrates (EC), for example oil in water dispersion and Emulsion (EW) that water disperses in the oil, sprayable solution, suspending agent concentrate (SC), dispersible oil-suspending agent (OD), with oil or Water is the suspension of diluent, the solution of miscible oil, powder (DP), capsule suspension liquid (CS), packet core (seeddressing) Composition, for broadcasting sowing with the particle of soil pesticide, injection particle, coated particle and absorbing particles, dispersible particle in water (WG), water-soluble particle (SG), ULV (ultra-low volume) formula, micro-capsule and wax work.These single preparation types are known , it is described in the following references, such as Winnacker-K ü chler, " Chemische Techonologie " [chemical work Skill], volume 7, C.Hauser Verlag Munich, the 4th edition 1986；Wade van Valkenburg, " Pesticide Formulations ", Marcel Dekker, N.Y., 1973；K.Martens, " Spray Drying " handbook, the 3rd edition 1979, G.Goodwin Ltd.London。

Necessary formulation auxiliary agents, such as inert substance, surfactant, solvent and other additives are similarly known, And it is described in following files, such as " powder diluent insecticide and the carrier handbook " of Watkins, the second edition, Darland book Caldwell N.J.；H.v.01phen " introduction of Clay Colloids chemistry ", the second edition, J.Wiley and Sons, N.Y.； " solvent guide " second edition of C.Marsden, Interscience, N.Y.1963；" detergent and the emulsifier of McCutcheon Annual report ", MC distributing and releasing corporation, Ridgewood N.J.；Sisley and Wood, " surfactant encyclopedia ", chemistry is published public Department, N.Y.1964；'s[ethylene oxide adduct surface Activating agent], Wiss.Verlagagesell.Stuttgart 1976；" the Chemische of Winnacker-K ü chler Technologie " [chemical technology], volume 7, C.Hauser Verlag Munich, the 4th edition 1986.

Wettable powder can equably can be dispersed in water, in addition to active material, further include diluent or inert substance, from Son and nonionic surface active agent (wetting agent, dispersing agent), such as polyethoxy alkylphenol, polyethoxy fatty alcohol, polyoxy Ethyl fatty race amine, poly alkyl alcohol ether sulfates, alkylsulfonate, alkyl benzene sulfonate, wooden sodium sulfonate, 2,2 '- Dinaphthyl methane -6,6 '-sodium disulfonate, nekal or oleoyl N-methyltaurine sodium.It, will in order to prepare wettable powder The active material fine grinding of herbicide, such as using common instrument, hammer-mill, fan grater and jet-propelled grater are such as used, Simultaneously or sequentially it is mixed into auxiliary agent.

Active material dissolution is prepared into emulsifiable concentrates, solvent such as butanol, cyclohexanone, dimethyl formyl in organic solvent The mixture of amine, the aromatic compounds of dimethylbenzene or higher or hydrocarbon or solvent, and add one or more Ion and/or nonionic surface active agent (emulsifier).The example for the emulsifier that can be used is such as detergent alkylate The alkyl aryl sulphonic acid calcium or nonionic emulsifier of sulfoacid calcium, for example, fatty acid polyglycol diol ester, alkylaryl polyglycol ether, The mountain of poly alkyl alcohol glycol ethers, propylene oxide-oxirane condensation product, alkyl, polyether, such as sorbitan fatty acid ester Pears glycan ester, or the polyoxyethylene sorbitan ester of such as Polyoxyethylene sorbitan fatty ester.

Active material and solid matter fine crushing are ground to obtain powder, solid matter such as talcum, such as kaolin, bentonite With the natural clay or diatomite of pyrophyllite.It can be prepared by following methods with water or oil for the suspension of substrate, such as benefit Wet-milling is carried out with commercially general bead mill, is added or is added without the surfactant of another above-mentioned preparation type.

The emulsion for preparing such as oil-water emulsifiers (EW), can be used aqueous organic solvent, uses blender, colloid Dismembyator and/or static mixer, if it is desired, the surfactant of another preparation type as described above is added.

Granule is prepared with following methods, active material is sprayed on adsorbate, using inert material particle, or will be lived Property substance be concentrated to for example husky, kaolinite carrier surface, inert material is granulated by adhesive, adhesive such as polyethylene Alcohol, Sodium Polyacrylate or mineral oil.Suitable active material can be granulated with the method for preparing fertiliser granulates agent, if necessary Fertilizer can be mixed with.Aqueous suspension granule is prepared using usual way, such as sprinkling-drying, fluidized bed prilling, mill are made Grain is mixed using high-speed mixer, and squeezed in the case where no solid, inert material.

About the preparation method for using mill, fluidized bed, extruder and sprayed particle agent, referring to following techniques, such as " Spray Drying handbook " third edition 1979, G.Goodwin Co., Ltd, London；J.E.Browning, " Agglomeration ", chemistry and engineering 1967,147ff pages；" engineer's handbook of Perry ' s chemistry ", the 5th edition, McGraw-Hill, New York 1973,8-57 pages.If it is to be understood that the preparation about crop protection products, see, for example, G.C.Klingman, " Weed Control as a Science ", John Wiley and Sons company, New York, 1961 81-96 Page and J.D.Freyer, S.A.Evans " weed control handbook ", the 5th edition, Blackwell Scientific Rublications, Oxford University 1968,101-103 pages.

Agrochemical formulation generally comprises the active material Formulas I of by weight 0.1 to 99%, especially 0.1 to 95%. The concentration of active material is in wettable powder, and by weight for example from about 10 to 99%, common formulation components composition is pressed Poidometer surplus is to 100%.Concentration by weight of the active material in emulsifiable concentrates can be about 1 to 90%, preferably 5 To 80%.Powder formulation includes by weight 1 to 30% active material, it is usually preferred to by weight 5 to 20% active matter Matter, however sprayable solution includes by weight about 0.05 to 80%, preferably 2 to 50% active material.It is outstanding about water The content of active material in floating particles agent, mainly according to active material be liquid or solid-state, and be granulated when use auxiliary agent, fill out Material etc..The content of active material is for example by weight between 1 to 95% in aqueous suspension granule, preferably by weight 10 To between 80%.

In addition the preparation of the active material may include tackifier, wetting agent, dispersing agent, emulsifier, bleeding agent, prevent Rotten agent, antifreezing agent, solvent, filler, carrier, colorant, defoaming agent, evaporation suppressor and usually all common in all cases PH and viscosity modifier.

Based on these preparations, it is also possible to and other biocidal activity substances for example insecticide, acaricide, herbicide and Fungicide mixing, can also mix, hybrid mode can be to be pre-mixed with safener, fertilizer and/or plant growth regulator Good or filling mixing.

In mixture preparation or bucket mix formulation, can be with the suitable active material of active material of the invention mixing, Such as " world pesticide new varieties technology complete works of ", Scientia Agricultura Sinica technology publishing house, 2010.9 and document incorporated herein in Known substance.Such as herbicidal activity substance mentioned below can be mixed with Formulas I mixture, (remarks: the name of compound Title is perhaps the common name according to International Organization for standardization (ISO) or is chemical name, there is code name when appropriate): Acetochlor, butachlor, alachlor, propisochlor, isopropyl methoxalamine, S-metolachlor, pretilachlor, propachlor, kecaoan, naphthalene Propionyl grass amine, the left-handed naphthalene propionyl grass amine of R-, propanil, mefenacet, diphenamide, diflufenican, N-alpha-chloroacetyl-N-isopropyl-o ethylaniline, fluorine butyryl Careless amine, bromobutide, dimethenamid, dimethenamidP, ethobenzanid, flufenacet, thenylchlor, pyrrole grass Amine, isoxaben, flampropMmethyl, flampropMisopropyl, allidochlor, pethoxamid, chloranocryl, cyclopropyl grass Amine, mefluidide, monalide, delachlor, prynachlor, terbuchlor, xylachlor, dimethachlor, amine of taking to the greenwood, Front three ring grass amine, propyzamide, valeryl benzene grass amine, blocks careless amine, suffer, the careless amine of tricyclic match, butylene grass at clomeprop Amine, tebutam, benzyl grass amine, quinone duckweed amine, dichlofluanid, naproanilide, acetyl alachlor, quinclorac, fenacet, pyrrole cyanogen grass amine, benzene More grams of grass is dead, chlorothiamid, chlorine phthalimide, fourth amidine amine, fluorine metazachlor, atrazine, Simanex, prometryn, cyanatryn, symetryne, Ametryn, dipropetryn, flur, terbutryn, Garagard, triaziflam, cyprazine, proglinazine, trietazine, is flutterred propazine Going out, logical, Gesadrual, nitrine be net, desmetryn, dimethametryn, cyclopropyl blueness saliva, green bristlegrass of going out saliva, another Ding Jin, Zhong Dingtong, Te Dingtong, methoxy Third net, cyanatryn, ipazine, chlorazine, atraton, weed eradication be logical, Radix Glycyrrhizae saliva, cyanuric acid, Indaziflam, green sulphur are grand, first Sulphur is grand, bensulfuron-methyl, chlorimuron, tribenuron-methyl, thifensulfuron methyl, pyrazosulfuron, mesosulfuron, iodosulfuron-methyl-sodium, formyl Amino Sulfometuron Methyl, cinosulfuron, triasulfuron, sulfometuronmethyl, nicosulfuron, ethametsulfuron, amidosulfuron, ethoxysulfuron, ring Third Sulfometuron Methyl, rimsulfuron, azimsulfuron, pyridine ethyl methyl, monosulfmeturon, single phonetic sulphur ester, flucarbazone, flupyrsulfuron-methyl-sodium, Fluorine pyrazosulfuron, oxasulfuron, imazosulfuron, primisulfuronmethyl, procarbazone, prosulfuron, Sulfosulfuron, trifluoro pyridine Sulphur is grand, triflusulfuronmethyl, tritosulfuron, metsulfuron-methyl sodium salt, flucetosulfuron, Sulfonylurea, orthosulfamuron, Propyrisulfuron (proxazuron-methyl), piperazine pyrazosulfuron, acifluorfen, fomesafen, lactofen, second carboxylic Fluofazone, Oxyfluorfen, Mo 9 granular, aclonifen, ethoxyfen-ethyl, bifenox, fluoroform grass ether, methoxy weeding Ether, fluorodifen, fluorination nitrofen, fluorine furan grass ether, nitrofen, first grass ether, diformazan grass ether, fluorine lactazone grass ether, fluofazone ester, Halosafen, chlortoluron, isoproturon, linuron, diuron, Sha flutter grand, fluometuron, benzthiazuron, methabenzthiazuron, cumyluron, Ethidimuron, isouron, terbufos benzthiazuron, buturon, bromax, methyldymron, phenobenzuron, methoxy daimuron, metobromuron, first Oxygen is grand, afesin, telvar, Tupersan, fenuron, fluorine sulphur are grand, neburea, chloroxifenidium, herban, isonoruron, Alipur-O, Thiazfluron, tebuthiuron, difenoxuron, to fluon, methylamine methabenz thiazuron, Long Caote, front three isourea, dimefuron, Monisouron, Anisuron, Methiuron, Chloreturon, four fluon, phenmedipham, phenmedipham-ethyl ester, desmedipham, the spirit of sulphur grass, special grass Spirit, oatax, Chem hoe, chlorpropham, benzyl dichloride grass ester, swep, chlorbufam, Carboxazole, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Ding Caote, benthiocarb, vernolate, molinate, tri-allate, dimepiperate, dogstail Fear, pyributicarb, cycloate, Avadex, bactericide, the careless spy of second sulphur, orbencarb, pebulate, prosulfocarb, tiocarbazil, sulfuric acid, Dimexan, Isopolinate, Methiobencarb, 2,4- d butyl ester, 2 first, 4 chlorine sodium, the different monooctyl ester of 2,4- drop, 2 first, 4 chlorine are different pungent Ester, 2,4- drop sodium salt, 2,4- drop dimethylamine salt, 2 first, 4 chloroethene thioesters, 2 first, 4 chlorine, 2,4- drop propionic acid, high 2,4- drop propionate, 2, 4- Embutox, Vi par, Vi par salt, Thistrol, 2,4,5- tears, 2,4,5- tears propionic acid, 2,4,5- tears fourth Acid, 2 first, 4 chloramines salt, dicamba, erbon, Fenac, match pine, trichlorobenzoic acid, chloramben, methoxy trichlorobenzoic acid, dogstail Spirit, fluazifop, efficient fluazifop, haloxyfop-P-methyl, efficient haloxyfop, quizalofop-ethyl, Quizalotop-ethyl, oxazole dogstail Spirit, fenoxapropPethyl, propaquizafop, cyhalofop-butyl, metamifop, clodinafop-propargyl, diclofop-methyl thiazole, chloroazifoppropynyl, the spirit of hydroxyl penta standing grain, Trifluoro dogstail oxime, isoxapyrifop, paraquat, diquat dibromide, oryzalin, ethalfluralin, isopropalin, nitralin, cyclopropyl fluorine Spirit, prodiamine, benfluralin, fluchloraline, the spirit of amino second fluorine, dipropalin, chloroethene dipropalin, Methalpropalin, Third nitre phenol, glyphosate, Sha barnyard grass phosphine, glufosinate-ammonium, amiprophos-methyl, sulphosate, piperazine grass phosphine, bialaphos, bensulide, butamifos, Creeping weed phosphorus cuts down ridge phosphorus, double first amiprophos, dow crabgrass killer, imazapyr, imazethapyr, imazaquin, imazamox, first Oxygen Imazethapyr ammonium salt, AC 263222, miaow grass ester, fluroxypyr, the different monooctyl ester of fluroxypyr, clopyralid, ammonia Chloropyridine acid, trichlopyr, dithiopyr, halogen grass be fixed, phenolate trichloropyridine, thiazopyr, fluridone, chlorine Fampridine acid, Diflufenzopyr, triclopyr butoxyethyl ester, Cliodinate, sethoxydim, clethodim, cycloxydim, alloxydimsodium, ring benzene grass Ketone, butroxydim, tralkoxydim, tepraloxydim, Buthidazole, metribuzin, hexazinone, metamitron, ethiozin, Ametridione, Amibuzin, Brominal, bromoxynil octanoate, ioxynil octanoate, ioxynil, dichlobenil, diphenatril, polybenzobisoxazole Oxalic acid dinitrile, chloroxynil, Iodobonil, Flumetsulam, florasulam, penoxsuam, metosulam, cloransulammethyl, Diclosulam, pyroxsulam, fluorine straw colour, bispyribac-sodium, pyribenzoxim, pyriftalid, KIH 6127, pyrithiobacsodium, bicyclic sulphur It is humulone, mesotrione, sulphur humulone, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, different Oxazole humulone, isoxachlorotole, Fenoxasulfone, Methiozolin, fluazolate, pyraflufen-ethyl, pyrazolate, wild swallow Withered, pyrazoxyfen, benzofenap, pyrrole chlorine grass amine, Pyrasulfotole, topramezone, Pyroxasulfone, cafenstrole, fluorine amine grass Azoles, Amrol, amicarbazone, azafenidin, profluazone, sulfentrazone, Bencarbazone, benzfendizone, fluorine third are phonetic Careless ester, bromacil, isoprocil, lenacil, terbacil, Flupropacil, cinidon-ethyl, Flumiclorac pentyl, flumioxazin, Alkynes grass amine, phthalein benzyl oxide, Flumezin, pentachlorophenol (sodium), dinoseb, dinoterb, dinoterb acetate, dinosam, Chemox PE, chlorine nitre phenol, Medinoterb acetate, Di Lete, oxadiargyl, oxadiazon, pentoxazone, profluazol, fluthiacet, fentrazamide, fluorine Pyridazine grass ester, pyrazon, brompyrazon, diformazan reach careless volt, Kusakira, grass pyridazone, grass and rattle away pine, norflurazon, Pyridafol, dichloro Quinolinic acid, quinmerac, Bentazon, pyridate, oxaziclomefone, benazolin, clomazone, cinmethylin, iso-propyl-ester nitrofen, Propyl-ester nitorfen, indanofan, sodium chlorate, Dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoro propionic acid, herbage is fast, bromine phenol Oxime, triazole sulphur, kill azoles, flurtamone, benfuresate, ethofumesate, phonetic careless amine, chlorine phthalandione, fluorochloridone, barnyard grass, methacrylaldehyde, Bentranil, tridiphane, Bidisin, thiadiazoles grass amine, phenisopham, hydroxyl humulone, dioxybenzone, benzene flumetsulam, chlorine acyl grass phosphine, three Chloropropionic acid, Alorac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone- Methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, first sulphur nitralin, Cambendichlor, cyclopropyl pyrimidine acid, rodethanii, benoxacor, fenclorim, flurazole, fenchlorazole, solve careless quinoline, oxabetrinil, Oxalane, cyometrinil, desorpenic, mefenpyrdiethyl, furilazole, fluxofenim, isoxadifen, allyl dichloride amine, fluorine Chloropyridine ester, DOW chlorine fluorine pyridine ester, UBH-509, D489, LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189、SC-0744、DOWCO535、DK-8910、V-53482、PP-600、MBH-001、KIH-9201、ET-751、 KIH-6127 and KIH-2023.

In the context of the present specification, if the abbreviated form of the adopted name using reactive compound, at every kind In the case of include all conventional derivatives, such as ester and salt and isomers, especially optical isomer are especially a kind of Or a variety of commercial forms.It in each case further include every other conventional derivatisation if adopted name indicates ester or salt Object, such as other esters and salt, free acid and neutral compound and isomers, especially optical isomer, it is especially a kind of Or a variety of commercial forms.The chemical name of the compound provided indicates at least one compound covered by adopted name, usually It is preferred compound.

When in use, if desired, commercially available preparation is diluted in common mode, such as in wettable powder, concentration When emulsion, suspension and the particle to suspend in water, make to be diluted with water.Granule used in powder, soil pesticide or broadcast sowing and The solution of sprinkling does not need generally further to be diluted with inert substance before use.With the variation of external condition, it is desirable that formula The usage amount of Compound I is also different, and external condition is, such as temperature, humidity, the property of herbicide used etc..It can be with Have a big amplitude of variation, such as 0.001 between 1.0kg/ha, or more active material, but preferably arrived 0.005 Between 750g/ha, especially 0.005 between 500g/ha.

Specific embodiment

Following embodiment should not be regarded it as limiting the invention in any way for illustrating the present invention.The present invention Claimed interest field is illustrated by claims.

In view of the economy and diversity of compound, we are preferably synthetic some compounds, in many chemical combination of synthesis In object, selected part is listed in the table below in 1.Specific compound structure and corresponding compound information are as shown in Tables 1 and 2.In table 1 Compound be intended merely to better illustrate the present invention, but limit the present invention, for a person skilled in the art, no The range that this should be interpreted as to the above-mentioned theme of the present invention is only limitted to following compound.

1 compound structure of table and its¹HNMR data

2 compound of table¹HNMR data

The several methods detailed annotation for preparing the compounds of this invention is illustrated in following scheme and embodiment.Raw material can be through market It buys or can be prepared by known in the literature method or as shown in detailed annotation.Those skilled in the art should manage Solution, also can use other synthetic routes and synthesizes the compound of the present invention.Although hereinafter to the tool in synthetic route Body raw material and condition are illustrated, however, it is possible to easily be replaced with other similar raw materials and condition, these are right Modification or the variant of preparation method of the present invention and the various isomeries of compound etc. generated are included in the scope of the invention It is interior.In addition, preparation method as described below can routinize according to the disclosure of invention, using well known to those skilled in the art Method is further modified.For example, during the reaction group appropriate protect etc..

For embodiment of the method presented below for promoting further appreciating that preparation method of the invention, what is used is specific Substance, type and condition are determined as not being the limitation to its zone of reasonableness to further explanation of the invention.In the following table Reagent used in the synthesis compound shown can perhaps be bought with market or can be light by those of ordinary skill in the art Easily it is prepared.

The embodiment of representative compound is as follows:

1, the synthesis of compound 50

(1) by compound 50-1 (500mg, 4.16mmol), NBS (741mg, 4.16mmol), catalytic amount AIBN (10mg), carbon tetrachloride (20mL) are placed in 100mL single port bottle, and 60 DEG C are stirred 12 hours, and high performance liquid chromatography detects raw material It has been reacted that, reaction solution is down to room temperature, filtered out solid, carbon tetrachloride is mutually concentrated, compound 50-2 (800mg, crude product) is obtained, It does not purify, is directly used in next step.

(2) by compound a (400mg, 1.7mmol), the compound 50-2 (800mg, crude product) that upper step obtains, catalytic amount TBAB (10mg), DMF (10mL) are placed in 50mL round-bottomed flask, are heated to 85 DEG C and are reacted 12 hours.The reaction of liquid quality detection raw material It is complete, room temperature, water (100mL) and methyl tertiary butyl ether(MTBE) (50mL x 2) extraction are down in reaction, organic phase is dry, is concentrated, through column Compound 50 (180mg, yield 33%) is obtained after separation.

2, the synthesis of compound 66

(1) compound 66-1 (300mg, 4.83mmol), TEA (586mg, 5.79mmol) are dissolved in anhydrous methylene chloride In (20mL), it is cooled to 0 DEG C, compound b (1.15g, 5.31mmol) is slowly added dropwise.It is slowly raised to room temperature, it is 12 small that the reaction was continued When.Reaction solution to be poured into quenching reaction in ice water, is extracted, organic phase is washed once with saturated sodium bicarbonate 50mL, and organic phase is dry, Concentration, obtains compound 66-2 (1.2g, crude product), does not have to purifying, is directly used in next step.

(2) by compound a (400mg, 2.13mmol), the compound 66-2 (1.2g, crude product) that (1) step obtains, catalysis The TBAB (10mg) of amount, DMF (10mL) are placed in 50mL round-bottomed flask, are heated to 85 DEG C and are reacted 12 hours.Liquid quality detection raw material It has been reacted that, room temperature, water (100mL) and methyl tertiary butyl ether(MTBE) (50mL x 2) extraction are down in reaction, organic phase is dry, is concentrated, It is obtained after post separation compound 66 (300mg, yield 56%), compound 66 is white solid.

3, the synthesis of compound 97

(1) compound 97-1 (300mg, 4.1mmol) is dissolved in anhydrous methanol (20mL), is cooled to 0 DEG C, in batches plus Enter solid sodium methylate (244mg, 4.51mmol).10min is stirred at 0 DEG C, and compound 97-2 is slowly added dropwise at such a temperature (271mg, 4.51mmol).It is slowly raised to room temperature, the reaction was continued 12 hours.High performance liquid chromatography detects raw material fundamental reaction It is complete, a small amount of acetum is added dropwise to neutrality.Methanol is removed into reaction solution concentration, with water (100mL) and ethyl acetate (100mL x 2) it extracts, organic phase is dry, is concentrated, and obtains compound 97-3 (500mg, crude product), does not have to purifying, is directly used in anti-in next step It answers.

(2) by compound 97-3 (500mg, crude product), TEA (518mg, 5.12mmol) is dissolved in anhydrous methylene chloride In (20mL), it is cooled to 0 DEG C, compound b (1.01g, 4.69mmol) is slowly added dropwise.It is slowly raised to room temperature, it is 12 small that the reaction was continued When.Reaction solution to be poured into quenching reaction in ice water, is extracted, organic phase is washed once with saturated sodium bicarbonate 50mL, and organic phase is dry, Concentration, obtains compound 97-4 (1g, crude product), does not have to purifying, is directly used in next step.

(3) by compound a (400mg, 1.7mmol), the compound 97-4 (1g, crude product) that upper step obtains, catalytic amount TBAB (10mg), DMF (10mL) are placed in 50mL round-bottomed flask, are heated to 85 DEG C and are reacted 12 hours.The reaction of liquid quality detection raw material It is complete, room temperature, water (100mL) and methyl tertiary butyl ether(MTBE) (50mL x 2) extraction are down in reaction, organic phase is dry, is concentrated, through column It is obtained after separation compound 97 (240mg, yield 38%), compound 10 is white solid.

4, the synthesis of compound 130

Compound 4 is made in the preparation method of reference compound 66, then by compound 4 (200mg, 0.67mmol), carbonic acid Potassium (185mg, 1.34mmol), compound 130-1 (161mg, 1.00mmol), the DMAP (10mg) of catalytic amount, acetonitrile (20mL) It is placed in 50mL round-bottomed flask, is heated to 80 DEG C and reacts 12 hours.Liquid quality detection raw material has reacted, and room temperature is down in reaction, dense Contracting, obtains compound 130 (150mg, yield 59%) through column chromatography for separation, and compound 130 is colorless oil.

Biological evaluation:

The active class criteria that noxious plant destroys (i.e. growth control rate) is as follows:

5 grades: growth control rate is 85% or more；

4 grades: growth control rate is more than or equal to 60% and less than 85%；

3 grades: growth control rate is more than or equal to 40% and less than 60%；

2 grades: growth control rate is more than or equal to 20% and less than 40%；

1 grade: growth control rate is more than or equal to 5% and less than 20%；

0 grade: growth control rate is less than 5%.

The above growth control rate is fresh weight control rate.

Test experiments after seedling: by unifacial leaf and broadleaf weed seed and chief crop seed (wheat, corn, rice, Soybean, cotton, rape, millet, sorghum) it is placed in the plastic tub equipped with soil, 0.5-2 centimetres of soil is then covered, it is made It is grown in good greenhouse, handles test plants in the 2-3 leaf phase after sowing 2 weeks, it respectively will be for the chemical combination of the present invention of examination Object acetone solution, is then added Tween 80, dilute with certain water using the missible oil of 1.5 liter/hectare methyl oleates as synergist It is interpreted into certain density solution, is sprayed application on plant with spray tower.It is cultivated in the greenhouse after application 3 weeks, the experiment of weeds after 3 weeks Effect is listed in table 3-4.

3 compound activity test result of table (1000 grams/ha)

Weeds test result after 4 seedling of table

Note: administration dosage is 600 grams/ha of effective component, and the amount of being watered is 450 kilograms/hectare.Barnyard grass and cyperus iria are adopted From Ningxia, China, resistance is produced to ALS class herbicide.

Control compound A:

Control compound A is known compound, poor to Security of rice, selects index low, it is difficult to commercially use. Making us unexpected is that the compound of the present invention is high to rice selection index, and safety is good, there is good commercial value.And Barnyard grass, the cyperus iria excellent of ALS class anti-to paddy field, are able to solve the weeds of resistance.

Test experiments before seedling:

By unifacial leaf and broadleaf weed seed and chief crop seed (wheat, corn, rice, soybean, cotton, oil Dish, millet, sorghum) it is placed in the plastic tub equipped with soil, 0.5-2 centimetres of soil is then covered, it respectively will be for this hair of examination Bright compound acetone solution, is then added Tween 80, is diluted to certain density solution with certain water, after planting sprays immediately It applies.It is cultivated in the greenhouse after application 4 weeks, observation experiment after 3 weeks is as a result, find that medicament majority of the invention is counted at 250 grams/ha Lower superior is measured, especially to weeds such as barnyard grass, Ma Tang, piemarkers, and many compounds are to corn, wheat, rice, soybean, oil Dish has good selectivity.

By testing we have found that compound of the present invention generally has preferable Weed-control effect, particularly with corn The main gramineae weed such as weeds barnyard grass, herba digitariae, herba setariae viridis that field, paddy field, wheat paddock occur extensively and piemarker, indian rorippa herb, The main broadleaf weeds such as beggar-ticks has good effect, has good commercial value.Especially it was noted that for ALS The broadleaf weeds such as the resistant indian rorippa herb of inhibitor, Descurainia sophia, shepherd's purse, corn gromwell, clearvers, herba stellariae mediae have high activity.

Transplanting rice safety evaluatio and paddy land weed preventive effect are evaluated:

After being packed into paddy field soil in 1/1,000,000 hectare of tank, the seed of Monochoria vaginalis is sowed, is lightly covered on it Soil is statically placed in greenhouse with 0.5-1 centimetres of state of water storage depth.Thereafter 3-4 centimetres of water storage depth is kept, reaches 0.5 in Monochoria vaginalis Leaf will modulate the water diluent of wettable powder made of the compounds of this invention or suspending agent according to common formulation method, Uniformly drip processing with pipette to reach defined active ingredient amount.

In addition, after being packed into paddy field soil in 000,000 hectare of tank, progress is smooth 1/1, make 3-4 centimetres of water storage depth, the The rice (japonica rice) of 3 leaf phases is transplanted within two days with 3 centimetres of transplanting depth.The present invention is handled as described above within the 5th day after transplanting Compound.

The fertility status of 14th day Monochoria vaginalis after the chemicals treatment that detects by an unaided eye respectively, the 21st day rice after chemicals treatment Fertility status, with above-mentioned 0-5 grades of activity criteria's level evaluation herbicidal effect, many compounds show excellent activity and Selectivity.

5 assay activity of table and security test result (1000 grams/ha)

Compound numbers	Rice	Monochoria vaginalis
			3	0	5
4	0	5
			7	0	5
66	0	5
			74	0	5
77	0	5
			79	0	5
82	0	5
			87	0	5
88	0	5
			97	0	5
98	0	5
			130	0	5
50 grams/ha of penoxsuam	1	1

Note: Monochoria vaginalis seed is acquired from Chinese Heilungkiang, after testing to the pyrazosulfuron of routine dose, penoxsulam Amine has drug resistance.

The compounds of this invention is to the anti-ALS Inhibitory Mechanism to face severe challenge in production it can be seen from this experiment Weeds have outstanding activity, be able to solve the resistance problem got worse.

Simultaneously by many test discoveries, compound of the present invention and combinations thereof is much to Korea lawn grass, Bermuda grass, height The Gramineae lawns such as fescue grass, annual bluegrass, rye grass, seashore paspalum have good selectivity, and it is miscellaneous to prevent and kill off many crucial grass family Grass and broadleaf weeds.To the wheat under different insecticide-applying way, corn, rice, sugarcane, soybean, cotton, oily certain herbaceous plants with big flowers, potato, fruit The tests such as tree, vegetables also show that fabulous selectivity and commercial value.

Claims

1. a kind of pyridine oxygroup thioes derivatives as shown in formula I,

C represents hydrogen, halogen, alkyl, halogenated alkyl；

Q represents halogen, cyano, cyanoalkyl, hydroxy alkyl, amino, nitro, formoxyl, alkyl, alkene without or with halogen Base, alkynyl, naphthenic base, alkoxy, alkylthio group, alkyl-carbonyl, alkoxy carbonyl, alkylaminoalkyl group or alkoxyalkyl, not Aryl, the heteroaryl, aryl alkyl, heteroaryl alkyl for replacing or replacing；

R is representedCyano, nitro；

R₃Separately represent alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl and unsubstituted or substituted heterocycle, Aryl, heteroaryl, heterocyclylalkyl group, aryl alkyl, heteroaryl alkyl；

R₄、R₅、R₆Separately represent hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, alkoxy carbonyl and not Heterocycle, the aryl, heteroaryl, heterocyclylalkyl group, aryl alkyl, heteroaryl alkyl for replacing or replacing；

X represents nitro or NR₁R₂, wherein R₁H is represented, it optionally can be by 1-2 R₁₁Substituted alkyl, alkenyl or alkynyl ,-COR₁₂, Nitro, OR₁₃, SO₂R₁₄, NR₁₅R₁₆, N=CR₁₇R₁₈, alkyl-carbamoyl, dialkyl carbamoyl, trialkylsilyl Base or dialkylphosphono；R₂H is represented, it optionally can be by 1-2 R₁₁Substituted alkyl or-COR₁₂；Or NR₁R₂Represent N= CR₂₁NR₂₂R₂₃, N=CR₂₄OR₂₅, unsubstituted or halogen, alkyl, alkoxy, halogenated alkoxy, alkane sulphur are independently selected from by 1-2 Base, amino, alkyl amino, dialkyl amido, does not contain or contains replaced the group in alkoxy carbonyl halogenated alkylthio 5- the or 6- member of oxygen atom, sulphur atom or other nitrogen-atoms is saturated or unsaturated ring；

Wherein R₁₁Independently represent halogen, hydroxyl, alkoxy, halogenated alkoxy, alkylthio group, halogenated alkylthio, amino, alkyl ammonia Base, dialkyl amido, alkoxy carbonyl, unsubstituted or substituted aryl, heteroaryl；

R₁₃Represent H, alkyl, halogenated alkyl, phenyl, benzyl or CHR₃₁C(O)OR₃₂；R₃₁Represent H, alkyl or alkoxy；R₃₂It represents H, alkyl or benzyl；

R₁₄Represent alkyl, halogenated alkyl；

R₁₅Represent H, alkyl, formoxyl, alkyl acyl, halogenated alkyl acyl group, alkoxy carbonyl, phenylcarbonyl group, phenyloxycarbonyl Or benzyloxycarbonyl；R₁₆Represent H, alkyl；

R₁₇Represent H, alkyl, the unsubstituted or phenyl replaced 1-3 group in halogen, alkyl, alkoxy；R₁₈Represent H, Alkyl；Or N=CR₁₇R₁₈It represents

R₂₁、R₂₄Separately represent H or alkyl；

R₂₂、R₂₃Separately represent H or alkyl；Or NR₂₂R₂₃Representative does not contain or contains oxygen atom, sulphur atom or other 5- the or 6- member of nitrogen-atoms is saturated or unsaturated ring；

R₂₅Represent alkyl.

2. pyridine oxygroup thioes derivatives according to claim 1, which is characterized in that

A, B separately represents halogen, contains or not contain the C1-C8 alkyl or C3-C8 naphthenic base of halogen；

C represents hydrogen, halogen, C1-C8 alkyl, halogenated C1-C8 alkyl；

Q represents halogen, cyano, cyano C1-C8 alkyl, hydroxyl C1-C8 alkyl, amino, nitro, formoxyl, without or with halogen C1-C8 alkyl, the C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C1-C8 alkoxyl, C1-C8 alkylthio group, C1-C8 alkane of element Base carbonyl, C1-C8 alkoxyl carbonyl, C1-C8 alkyl amino C1-C8 alkyl or C1-C8 alkoxyl C1-C8 alkyl, it is unsubstituted or Substituted aryl, heteroaryl, aryl C1-C8 alkyl, heteroaryl C1-C8 alkyl；

M is represented without or with the C1-C18 alkyl of halogen, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C3-C8 cycloalkanes Base C1-C8 alkyl ,-(C1-C8 alkyl)-R, And unsubstituted or substituted heterocycle, aryl, heteroaryl；

R is representedCyano, nitre Base；

R₄、R₅、R₆Separately represent hydrogen, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 naphthenic base, C3-C8 ring Alkyl C1-C8 alkyl, C1-C8 alkoxyl carbonyl and unsubstituted or substituted heterocycle C1-C8 alkyl, aryl C1-C8 alkyl, Heteroaryl C1-C8 alkyl；

X represents nitro or NR₁R₂, wherein R₁H is represented, it optionally can be by 1-2 R₁₁Substituted C1-C8 alkyl, C2-C8 alkenyl or C2-C8 alkynyl ,-COR₁₂, nitro, OR₁₃, SO₂R₁₄, NR₁₅R₁₆, N=CR₁₇R₁₈, C1-C8 alkyl-carbamoyl, two C1-C8 alkane Base carbamoyl, three C1-C8 aIkylsilyl groups or two C1-C8 alkyl phosphonos；R₂H is represented, it optionally can be by 1-2 R₁₁ Substituted C1-C8 alkyl or-COR₁₂；Or NR₁R₂Represent N=CR₂₁NR₂₂R₂₃, N=CR₂₄OR₂₅, unsubstituted or only by 1-2 It is vertical selected from halogen, C1-C8 alkyl, C1-C8 alkoxyl, halogenated C1-C8 alkoxyl, C1-C8 alkylthio group, halogenated C1-C8 alkylthio group, Amino, C1-C8 alkyl amino, two C1-C8 alkyl aminos, replaced the group in C1-C8 alkoxyl carbonyl

Wherein R₁₁Independently represent halogen, hydroxyl, C1-C8 alkoxyl, halogenated C1-C8 alkoxyl, C1-C8 alkylthio group, halogenated C1- C8 alkylthio group, amino, C1-C8 alkyl amino, two C1-C8 alkyl aminos, C1-C8 alkoxyl carbonyl, it is unsubstituted or by halogen, C1-C8 alkyl, halogenated C1-C8 alkyl, C1-C8 alkoxyl, phenyl, naphthalene replaced 1-3 group in nitro,

R₁₄Represent C1-C8 alkyl, halogenated C1-C8 alkyl；

R₁₇Represent H, C1-C8 alkyl, unsubstituted or replaced 1-3 group in halogen, C1-C8 alkyl, C1-C8 alkoxyl Phenyl；R₁₈Represent H, C1-C8 alkyl；Or N=CR₁₇R₁₈It represents

R₂₁、R₂₄Separately represent H or C1-C8 alkyl；

R₂₅Represent C1-C8 alkyl；

" heterocycle " refers to 0,1 or 2 oxo group " aryl " refers to phenyl, naphthalene；It is described " miscellaneous Aryl " refers to

Wherein, by be selected from halogen, nitro, cyano, thiocyano, hydroxyl, carboxyl, sulfydryl, formoxyl, it is unsubstituted or by be selected from halogen Element, alkyl, phenyl, benzyl, benzyloxy, phenoxy group replaced at least one group in alkoxy, contain or not contain halogen Element alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, OR ", SR " ,-alkyl-OR " ,-alkyl-SR ", COR ", COOR ", COSR”、SOR”、SO₂R ", OCOR ", SCOR ", and it is selected from hydrogen, alkyl, alkenyl, alkynyl, naphthenic base, cycloalkyl-alkyl, benzene Base, benzyl, benzyloxy, phenoxy group, COR ", COOR ", SO₂Amino replaced one or two of R ", OR " group or ammonia Replaced at least one group in base carbonyl；

R ' separately represents hydrogen, nitro, hydroxyl, and amino contains or not contain alkyl, alkenyl, alkynyl, the cycloalkanes of halogen Base, cycloalkenyl, cycloalkyl-alkyl, alkoxy, alkenyl oxygroup, alkynyl oxygroup, cycloalkyl oxy, alkoxyalkyl, alkoxy carbonyl Base, alkylthiocarbonyl, alkyl sulphonyl, Alkylsulfonylalkyl, alkyl-carbonyl, Alkylcarbonylalkyl, alkyl acyloxy, alkyl Amino, alkyl amino-carbonyl, alkoxy amino carbonyl, alkoxy carbonyl alkyl, alkyl amino-carbonyl alkyl, trialkylsilyl Base, dialkylphosphono；

3. pyridine oxygroup thioes derivatives according to claim 2, which is characterized in that

A, B separately represents halogen, contains or not contain the C1-C6 alkyl or C3-C6 naphthenic base of halogen；

C represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl；

Q represents halogen, cyano, cyano C1-C6 alkyl, hydroxyl C1-C6 alkyl, amino, nitro, formoxyl, without or with halogen C1-C6 alkyl, the C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C1-C6 alkoxy, C1-C6 alkylthio group, C1-C6 alkane of element Base carbonyl, C1-C6 alkoxy carbonyl, C1-C6 alkyl amino C1-C6 alkyl or C1-C6 alkoxy C 1-C6 alkyl, it is unsubstituted or Substituted aryl, heteroaryl, aryl C1-C6 alkyl, heteroaryl C1-C6 alkyl；

M is represented without or with the C1-C12 alkyl of halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 cycloalkanes Base C1-C6 alkyl ,-(C1-C6 alkyl)-R, And unsubstituted or substituted heterocycle, aryl, heteroaryl；

R is representedCyano, nitro；

R₄、R₅、R₆Separately represent hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 ring Alkyl C1-C6 alkyl, C1-C6 alkoxy carbonyl and unsubstituted or substituted heterocycle C1-C6 alkyl, aryl C1-C6 alkyl, Heteroaryl C1-C6 alkyl；

X represents nitro or NR₁R₂, wherein R₁H is represented, it optionally can be by 1-2 R₁₁Substituted C1-C6 alkyl, C2-C6 alkenyl or C2-C6 alkynyl ,-COR₁₂, nitro, OR₁₃, SO₂R₁₄, NR₁₅R₁₆, N=CR₁₇R₁₈, C1-C6 alkyl-carbamoyl, two C1-C6 alkane Base carbamoyl, three C1-C6 aIkylsilyl groups or two C1-C6 alkyl phosphonos；R₂H is represented, it optionally can be by 1-2 R₁₁ Substituted C1-C6 alkyl or-COR₁₂；Or NR₁R₂Represent N=CR₂₁NR₂₂R₂₃, N=CR₂₄OR₂₅, unsubstituted or only by 1-2 It is vertical selected from halogen, C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio group, halogenated C1-C6 alkylthio group, Amino, C1-C6 alkyl amino, two C1-C6 alkyl aminos, replaced the group in C1-C6 alkoxy carbonyl

Wherein R₁₁Independently represent halogen, hydroxyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, C1-C6 alkylthio group, halogenated C1- C6 alkylthio group, amino, C1-C6 alkyl amino, two C1-C6 alkyl aminos, C1-C6 alkoxy carbonyl, it is unsubstituted or by halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, phenyl, naphthalene replaced 1-3 group in nitro,

R₁₄Represent C1-C6 alkyl, halogenated C1-C6 alkyl；

R₁₇Represent H, C1-C6 alkyl, unsubstituted or replaced 1-3 group in halogen, C1-C6 alkyl, C1-C6 alkoxy Phenyl；R₁₈Represent H, C1-C6 alkyl；Or N=CR₁₇R₁₈It represents

R₂₁、R₂₄Separately represent H or C1-C6 alkyl；

R₂₅Represent C1-C6 alkyl；

Wherein, by be selected from halogen, nitro, cyano, thiocyano, hydroxyl, carboxyl, sulfydryl, formoxyl, it is unsubstituted or by be selected from halogen Phenyl, benzyl, benzyloxy, phenoxy group replaced at least one group in element, C1-C6 alkyl, C1-C6 alkoxy, contain Or C1-C6 alkyl without containing halogen, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base C1-C6 alkyl, OR ", SR " ,-(C1-C6) alkyl-OR " ,-(C1-C6) alkyl-SR ", COR ", COOR ", COSR ", SOR ", SO₂R”、OCOR”、 SCOR ", and it is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base C1-C6 Alkyl, phenyl, benzyl, benzyloxy, phenoxy group, COR ", COOR ", SO₂Ammonia replaced one or two of R ", OR " group Replaced 0,1,2 or 3 group in base or amino carbonyl；

R ' separately represents hydrogen, nitro, hydroxyl, and amino contains or not contain fluorine, chlorine, the C1-C6 alkyl of bromine, C2-C6 alkene Base, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 cycloalkenyl, C3-C6 naphthenic base C1-C6 alkyl, C1-C6 alkoxy, C2-C6 alkene Base oxygroup, C2-C6 alkynyl oxygroup, C3-C6 cycloalkyl oxy, C1-C6 alkoxy C 1-C6 alkyl, C1-C6 alkoxy carbonyl, C1- C6 alkylthiocarbonyl, C1-C6 alkyl sulphonyl, C1-C6 alkyl sulphonyl C1-C6 alkyl, C1-C6 alkyl-carbonyl, C1-C6 alkyl Carbonyl C1-C6 alkyl, C1-C6 alkyl acyloxy, C1-C6 alkyl amino, C1-C6 alkyl amino-carbonyl, C1-C6 alkoxy amino Carbonyl, C1-C6 alkoxy carbonyl C1-C6 alkyl, C1-C6 alkyl amino-carbonyl C1-C6 alkyl, three C1-C6 aIkylsilyl groups, two C1-C6 alkyl phosphono；

R " separately represents hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 naphthenic base, C3-C6 naphthenic base C1-C6 alkyl.

4. pyridine oxygroup thioes derivatives according to claim 3, which is characterized in that

A, B separately represents halogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 naphthenic base；

C represents hydrogen, halogen, C1-C6 alkyl, halogenated C1-C6 alkyl；

Q represents C1-C6 alkyl, halogenated C1-C6 alkyl, C3-C6 naphthenic base, C2-C6 alkenyl, C2-C6 alkynyl, halogen, cyano, ammonia Base, nitro, formoxyl, C1-C6 alkoxy, C1-C6 alkylthio group, C1-C6 alkoxy carbonyl group, hydroxyl C1-C6 alkyl, C1-C6 alcoxyl Base C1-C2 alkyl, cyano C1-C2 alkyl, C1-C6 alkylamino C1-C2 alkyl, benzyl, naphthalene, furyl, thienyl, thiazole Base, pyridyl group, pyrimidine radicals and unsubstituted or alkyl-substituted by C1-C6It is unsubstituted or by C1-C6 alkyl, halogenated Phenyl replaced at least one group in C1-C6 alkyl, halogen and C1-C6 alkoxy；

M represents C1-C12 alkyl, halogenated C1-C8 alkyl, C3-C6 naphthenic base, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C2-C6 alkynes Base, C1-C6 alkoxy, C1-C6 alkoxy carbonyl group, C1-C6 alkyl sulphonyl, cyano C1-C6 alkyl, nitro C1-C6 alkyl, C1- C6 alkoxy C 1-C6 alkyl, C1-C6 alkoxy carbonyl group C1-C6 alkyl, C2-C6 allyloxycarbonyl C1-C6 alkyl ,-(C1-C6 alkane Base)-R,Tetrahydrofuran base, pyridyl group, naphthalene, furyl, thienyl,And unsubstituted or C1-C6 is alkyl-substitutedIt is unsubstituted or by C1-C6 alkyl, halogenated C1-C6 alkane The phenyl that base, C1-C6 alkyl amino, halogen or C1-C6 alkoxy replace；

R is represented

R₃Separately represent C1-C6 alkyl；

R ' represents C1-C6 alkyl, halogenated C1-C6 alkyl；

X represent amino, C1-C6 alkyl amino, C1-C6 alkyl-carbonyl-amino, benzylcarbonylamino, benzylamino, it is unsubstituted or The halogenated alkyl-substituted furanylmethylenyl amino of C1-C6.

5. pyridine oxygroup thioes derivatives according to claim 4, which is characterized in that

A, B separately represents fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, trifluoromethyl, cyclopropyl；

Q represent methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, acetenyl, fluorine, chlorine, bromine, cyano, amino, nitro, Formoxyl, methoxyl group, methyl mercapto, methoxycarbonyl group, chloromethyl, a methyl fluoride, difluoromethyl, trifluoromethyl, 2- chloroethyl, 2, 2,2- trifluoroethyl, hydroxymethyl,Benzyl, naphthalene, furyl, Thienyl, thiazolyl, pyridyl group, pyrimidine radicals and unsubstituted or methyl substitutedIt is unsubstituted or by methyl, three Phenyl replaced at least one group in methyl fluoride, chlorine and methoxyl group；

R ' represents methyl, ethyl, difluoromethyl；

M represents methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, amyl, hexyl, heptyl, pungent Base, nonyl, decyl, undecyl, dodecyl, trifluoromethyl, pentafluoroethyl group, 3- chlorobutyl, 2- fluoro ethyl, 2- chloroethyl, 2- bromoethyl, 2,2- bis-fluoro ethyls, 2,2,2- trifluoroethyl, 4,4,4- triRuorobutyl, 2,2,3,3,3- pentafluoropropyl group, cyclopropyl Base, cyclobutyl, cyclopenta, cyclohexyl, allyl, 2-propynyl, methoxyl group, carbethoxyl group, methyl sulphonyl, Tetrahydrofuran base, pyridyl group, naphthalene, furans Base, thienyl,And it is unsubstituted or methyl substitutedIt is unsubstituted or by methyl, dimethylamino, The phenyl that chlorine, methoxyl group, trifluoromethyl or isopropyl replace；

X represents NH₂、

6. pyridine oxygroup thioes derivatives according to claim 5, which is characterized in that its any one in table 1.

7. a kind of preparation method of pyridine oxygroup thioes derivatives as claimed in any one of claims 1 to 6, which is characterized in that The following steps are included:

II compound represented of general formula is carried out to react obtained general formula I compound represented with general formula III compound represented；Its Reaction equation is as follows:

Wherein, W represents alkali metal, preferably K, Na；Hal represents halogen, preferably Br, Cl；The reaction is in catalysts and solvents In the presence of carry out, it is preferable that the catalyst is TBAB, and the solvent is one of DCM, DCE, ACN, THF, DMF or more Kind combination；

Or when X represents NR₁R₂(R₁、R₂Simultaneously it is not hydrogen) when, by general formula I-1 compound representedWith Corresponding halides carry out reaction and are made；

Wherein, the preferred chloro thing of halides or bromo-derivative；The reaction carries out in the presence of alkali and solvent, and the alkali is selected from hydrogen One or more of sodium oxide molybdena, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and cesium carbonate；Solvent be selected from THF, One of 1,4- dioxane, toluene, 1,2- dichloroethanes, ethyl acetate, acetonitrile, DMF, acetone, methylene chloride and chloroform Or multiple combinations；Catalyst, preferably DMAP can also be added in the reaction process.

8. a kind of Herbicidal combinations, which is characterized in that including (i) pyridine oxygroup thioesters as claimed in any one of claims 1 to 6 At least one of derivative；It preferably, further include (ii) one or more other herbicides and/or safener；More preferably Ground further includes acceptable formulation auxiliary agents on (iii) agriculture chemistry.

9. a kind of method for controlling weeds, which is characterized in that including described in the claim 1-6 any one by herbicidally effective amount At least one of pyridine oxygroup thioes derivatives or herbicidal composition use according to any one of claims 8 on plant or Weed regions, it is preferable that the plant is rice (such as japonica rice, long-grained nonglutinous rice), and the weeds are grass family (such as barnyard grass, herba digitariae, a thousand pieces of gold Son, herba setariae viridis), broadleaved herb (such as piemarker, Monochoria vaginalis) and sedge weed (such as cyperus iria).

10. at least one of pyridine oxygroup thioes derivatives as claimed in any one of claims 1 to 6 or claim 8 institute Purposes of the herbicidal composition stated on control weeds, it is preferable that be used to prevent and kill off by the pyridine oxygroup thioes derivatives Weeds in useful crop, the useful crop be genetically modified crops or the processed crop of genome editing technique, it is more excellent Selection of land, the crop be rice (such as japonica rice, long-grained nonglutinous rice), the weeds be grass family (such as barnyard grass, herba digitariae, semen euphorbiae, herba setariae viridis), Broadleaved herb (such as piemarker, Monochoria vaginalis) and sedge weed (such as cyperus iria).