AU2018430945B2

AU2018430945B2 - Substituted pyrimidinyl formyl oxime derivative, preparation method therefor, herbicidal composition and use thereof

Info

Publication number: AU2018430945B2
Application number: AU2018430945A
Authority: AU
Inventors: Chuanbin CHENG; Qi CUI; Lei Lian; Peng Liu; Liaoning ZHANG
Original assignee: Qingdao Kingagroot Chemical Compound Co Ltd
Current assignee: Qingdao Kingagroot Chemical Compound Co Ltd
Priority date: 2018-07-05
Filing date: 2018-09-14
Publication date: 2023-07-13
Anticipated expiration: 2038-09-14
Also published as: AU2018430945A1; WO2020006869A1; CN108586357A; CN108586357B

Abstract

The present invention relates to the technical field of pesticides, and particularly relates to a substituted pyrimidinyl formyl oxime derivative represented by general formula I, a preparation method therefor, a herbicidal composition and use thereof. R

Description

Substituted pyrimidinyl formyl oxime derivative, preparation method therefor, herbicidal composition and use thereof

Technical Field The invention relates to the field of pesticide technology, and in particular a type of substituted pyrimidinyl formyl oxime derivative, preparation method therefor, herbicidal composition and use thereof.

Technical background Weed control is one of the most important links in the course of achieving high-efficiency agriculture. At present, various pyrimidinyl formic acid herbicides are available in the market, for example, W02005/063721A1, W02007/082076A1, US7863220B2, US7300907B2, US7642220B2 and US7786044B2 disclose some 6-amino-2-substituted pyrimidine-4-formic acids and derivatives thereof, as well as their use as herbicides. However, scientists still need to do continuously research and develop new herbicides with high efficacy, safety, economics and different modes of action due to problems such as the growing market, weed resistance, the service life and economics of pesticides as well as people's increasing concern on environment. Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field. Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to".

Content of the invention The present invention provides a substituted pyrimidinyl formyl oxime derivative, preparation method therefor, herbicidal composition and use thereof. Said compound has excellent herbicidal activity and higher crop safety, with especially good selectivity for key crops such as corn and rice. The technical solution adopted by the invention is as follows: A type of substituted pyrimidinyl formyl oxime derivative, as shown in general formula I: Y x 0 R,. CN 0N R2 0 0 C A B

wherein,

Ri and R2 independently represent H, halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, acyloxy, alkylthio, unsubstituted or substituted aryl, unsubstituted or substituted benzyl, unsubstituted or substituted heteroaryl, unsubstituted or substituted aryloxy, unsubstituted or substituted arylthio, unsubstituted or substituted heteroaryloxy, unsubstituted or substituted heteroarylthio or the group represented by the formula of -COR, wherein, R5 represents alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, alkenoxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio,

1n unsubstituted or substituted benzyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted aryloxy, unsubstituted or substituted heteroaryloxy, unsubstituted or substituted aryl methoxy, unsubstituted or substituted heteroaryl methoxy, unsubstituted or substituted benzylthio, unsubstituted or substituted arylthio, unsubstituted or substituted heteroarylthio, or amino which is optionally substituted by alkyl, acyl, acyloxy, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted arylalkyl or unsubstituted or substituted heteroarylalkyl; or RIand R2 are linked to form a 5- or 6-member saturated or unsaturated ring; X represents alkyl, alkoxy, alkylthio, halogen, alkenyl or alkynyl; Y represents nitro or NR 3 R4 , wherein, R 3 represents H, alkyl, alkenyl, alkynyl, -COR 12, nitro, OR 13 , S0 2 R 4 , NRi 5Ri, N=CR 17Ri, alkyl carbamoyl, dialkyl carbamoyl, trialkyl silyl or dialkyl phosphono, wherein the alkyl, alkenyl and alkynyl are independently optionally substituted by one or two Rii; R4 represents H, alkyl or -COR1 2 , the alkyl is optionally substituted by one or two Rii; or NR 3R4 represents N=CR 2 1NR 22R23, N=CR240R 25 or 5- or 6-member saturated or unsaturated ring which is unsubstituted or substituted by one or two groups selected from halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino and alkoxy carbonyl, and contains or does not contain oxygen atom, sulfur atom or other nitrogen atom; wherein, Rii independently represents halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxy carbonyl, unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl; R12 represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy;

R13 represents H, alkyl, haloalkyl, phenyl, benzyl or CHR 3 1C(O)OR 32; R 3 1 represents H, alkyl

or alkoxy; R3 2 represents H, alkyl or benzyl; R14 represents alkyl or haloalkyl;

Ris represents H, alkyl, formyl, alkylacyl, haloalkylacyl, alkoxy carbonyl, phenyl carbonyl, phenoxy carbonyl or benzyloxy carbonyl; Ri6 represents H or alkyl; R17 represents H, alkyl or phenyl, said phenyl is unsubstituted or substituted by 1-3 groups

selected from halogen, alkyl and alkoxy; Ris represents H or alkyl; or N=CR1 7Ris represents

or -0 ; R21 and R 24 each independently represent H or alkyl; R22 and R 2 3 each independently represent H or alkyl; or NR 2 2 R 2 3 represents 5- or 6-member

saturated or unsaturated ring not containing or containing oxygen atom, sulfur atom or other nitrogen atom; R2 5 represents alkyl; A represents halogen or amino;

B represents hydrogen, halogen, alkoxy, alkylthio, alkylamino or dialkylamino, the alkoxy, alkylthio, alkylamino and dialkylamino are independently unsubstituted or substituted by halogen; C represents halogen or haloalkyl. Preferably, Ri and R2 independently represent H, cyano, Cl-C8 alkyl, halo Cl-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, Cl-C8 alkoxy, Cl-C8 acyloxy, Cl-C8 alkylthio, unsubstituted or substituted aryl, unsubstituted or substituted benzyl, unsubstituted or substituted heteroaryl, unsubstituted or substituted aryloxy, unsubstituted or substituted arylthio, unsubstituted or substituted heteroaryloxy, unsubstituted or substituted heteroarylthio or the group represented by the formula of -COR 5 , wherein, R 5 represents Cl-C8 alkyl, halo Cl-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, Cl-C8 alkoxy, C2-C8 alkenoxy, C3-C8 cycloalkoxy, Cl-C8 alkylthio, C2-C8 alkenylthio, C3-C8 cycloalkylthio, unsubstituted or substituted benzyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted aryloxy, unsubstituted or substituted heteroaryloxy, unsubstituted or substituted aryl methoxy, unsubstituted or substituted heteroaryl methoxy, unsubstituted or substituted benzylthio, unsubstituted or substituted arylthio, unsubstituted or substituted heteroarylthio or amino which is optionally substituted by Cl-C8 alkyl, Cl-C8 acyl, Cl-C8 acyloxy, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted aryl Cl-C8 alkyl or unsubstituted or substituted heteroaryl Cl-C8 alkyl; wherein, said "substituted" refers to being substituted by one or more groups selected from halogen, cyano, nitro, Cl-C8 alkyl, halo Cl-C8 alkyl, C3-C8 cycloalkyl, Cl-C8 alkoxy, C2-C8 alkenoxy, Cl-C8 alkylthio, aryl, aryloxy, benzyl, benzyloxy, Cl-C8 acyl, Cl-C8 acyloxy, C2-C8 alkenyl andamino which is optionally substituted by Cl-C8 alkyl, aryl, aryloxy, Cl-C8 acyl, Cl-C8 acyloxy or C2-C8 alkenyl; X represents Cl-C8 alkyl, Cl-C8 alkoxy, Cl-C8 alkylthio, halogen, C2-C8 alkenyl or C2-C8 alkynyl; Y represents nitro or NR 3R4, wherein, R3 represents H, Cl-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, -COR 12, nitro, OR 13 , S0 2 R1 4 , NRi 5 Ri 6 , N=CR 17Ri, Cl-C8 alkyl carbamoyl, diCl-C8 alkyl carbamoyl, triCl-C8 alkyl silyl or diCl-C8 alkyl phosphono, the Cl-C8 alkyl, C2-C8 alkenyl and C2-C8 alkynyl are independently optionally substituted by one or two Rii; R4 represents H, Cl-C8 alkyl or -COR12, the Cl-C8 alkyl is optionally substituted by one or two Rii; or NR 3R4 represents

N=CR2 1NR 22 R 23 , N=CR 24 0R 25 , or the

N N) /, N and 0 are independently unsubstituted or substituted by 1-2 groups selected

from halogen, Cl-C8 alkyl, Cl-C8 alkoxy, halo Cl-C8 alkoxy, Cl-C8 alkylthio, halo Cl-C8 alkylthio, amino, Cl-C8 alkyl amino, diCl-C8 alkyl amino and Cl-C8 alkoxy carbonyl; wherein, Rii independently represents halogen, hydroxy, Cl-C8 alkoxy, halo Cl-C8 alkoxy, Cl-C8 alkylthio, halo Cl-C8 alkylthio, amino, Cl-C8 alkyl amino, diC1-C8 alkyl amino, Cl-C8

0 S NN alkoxy carbonyl, phenyl, naphthylNN o the ~~rN ~ N< or'

phenyl, naphthyl, , N and N are independently

unsubstituted or substituted by 1-3 groups selected from halogen, Cl-C8 alkyl, Cl-C8 alkoxy and nitro; R12 represents H, C1-C18 alkyl, halo Cl-C8 alkyl, Cl-C8 alkoxy, phenyl, phenoxy or

benzyloxy; R13 represents H, Cl-C8 alkyl, halo Cl-C8 alkyl, phenyl, benzyl or CHR 3 1C(O)OR 32 ; R 3

represents H, Cl-C8 alkyl orCl-C8 alkoxy; R3 2 represents H, Cl-C8 alkyl orbenzyl; R 14 represents Cl-C8 alkyl or halo Cl-C8 alkyl; R 1 5 represents H, Cl-C8 alkyl, formyl, Cl-C8 alkyl acyl, halo Cl-C8 alkyl acyl, Cl-C8 alkoxy

carbonyl, phenyl carbonyl, phenoxy carbonyl or benzyloxy carbonyl; R1 6 represents H or Cl-C8 alkyl; R 17 represents H, Cl-C8 alkyl or phenyl, said phenyl is unsubstituted or substituted by 1-3 groups selected from halogen, Cl-C8 alkyl and Cl-C8 alkoxy; R18 represents H or Cl-C8 alkyl; or

N N-O N=CR 17Ris represents or; R21 and R 24 each independently represent H or Cl-C8 alkyl;

R22 and R 2 3 each independently represent H or Cl-C8 alkyl; or NR 2 2 R 2 3 represents No, NNN N C / , or 0.

R2 5 represents Cl-C8 alkyl; A represents halogen or amino; B represents hydrogen, halogen, Cl-C8 alkoxy, Cl-C8 alkylthio, Cl-C8 alkyl amino or diC1-C8 alkyl amino, the Cl-C8 alkoxy, Cl-C8 alkylthio, Cl-C8 alkyl amino and diC1-C8 alkyl amino are independently unsubstituted or substituted by halogen; C represents halogen or halo Cl-C8 alkyl. In the definition of the general formula of compound presented above, the terms used are defined as follows: the aryl in said R and R2 groups preferably comprises phenyl, 2,3-dihydroindenyl and naphthyl, etc; said heteroaryl comprises 5-10 membered heteroaryl containing 1-3 heteroatoms selected from oxygen, sulfur and nitrogen, such as pyridyl, pyrimidyl, pyrazinyl, furanyl, thienyl, pyrryl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, pyridazinyl, triazinyl, quinolyl, quinoxalinyl, indolyl, benzotriazolyl, benzothienyl, benzofuranyl, isoquinolyl, tetrahydroquinolyl, etc. More preferably, Ri and R2 independently represent hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, cyano, C1-C6 alkoxy carbonyl or phenyl, said phenyl is unsubstituted or substituted by one or more groups selected from halogen, halo C1-C6 alkyl, C1-C6 alkyl, C1-C6 alkoxy and C2-C6 alkenyl; X represents C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogen, C2-C6 alkenyl or C2-C6 alkynyl; Y represents nitro or NR 3R4, wherein, R3 represents H, Cl-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, -COR 12, nitro, OR 13 , S0 2 R1 4 , NRi 5 Ri 6 , N=CR 17Ri, Cl-C6 alkyl carbamoyl, diCl-C6 alkyl carbamoyl, triC1-C6 alkyl silyl or diC1-C6 alkyl phosphono, the C1-C6 alkyl, C2-C6 alkenyl and C2-C6 alkynyl are independently optionally substituted by one or two RiI; R4 represents H, Cl-C6 alkyl or -COR12, the C1-C6 alkyl is optionally substituted by one or two Rii; or NR 3R4 represents

N=CR2 1NR 22 R 23 , N=CR 24 0R 25 , 0 or , the >N N

N 'NN N and 0 are independently unsubstituted or substituted by 1-2 groups selected

from halogen, C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkyl amino, diC1-C6 alkyl amino and C1-C6 alkoxy carbonyl; wherein, Ri Iindependently represents halogen, hydroxy, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkyl amino, diC1-C6 alkyl amino, C1-C6 HN 0 s - N N alkoxy carbonyl, phenyl, naphthyl, N , N or N , the

0 S N phenyl, naphthyl,N N and N are independently

unsubstituted or substituted by 1-3 groups selected from halogen, C1-C6 alkyl, C1-C6 alkoxy and nitro; R12 represents H, C1-C14 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or

benzyloxy; R13 represents H, Cl-C6 alkyl, halo C1-C6 alkyl, phenyl, benzyl or CHR 3 1C(O)OR 32 ; R 3 1

represents H, Cl-C6 alkyl or Cl-C6 alkoxy; R3 2 represents H, Cl-C6 alkyl or benzyl; R14 represents Cl-C6 alkyl or halo C1-C6 alkyl;

Ri 5 represents H, Cl-C6 alkyl, formyl, Cl-C6 alkyl acyl, halo C1-C6 alkyl acyl, C1-C6 alkoxy carbonyl, phenyl carbonyl, phenoxy carbonyl or benzyloxy carbonyl; R 1 6 represents H or Cl-C6 alkyl; R 17 represents H, Cl-C6 alkyl or phenyl, said phenyl is unsubstituted or substituted by 1-3 groups selected from halogen, C1-C6 alkyl and C1-C6 alkoxy; Ri r epresents H or Cl-C6 alkyl; or

N=CR 17Ris represents or N ; R21 and R 24 independently represent H or Cl-C6 alkyl;

N -N R22 and R2 3 independently represent H or Cl-C6 alkyl; orNR22 R2 3 represents

N N

, or 0; R2 5 represents Cl-C6 alkyl; A represents halogen or amino; B represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkyl amino or diC1-C6 alkyl amino, the C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkyl amino and diC1-C6 alkyl amino are independently unsubstituted or substituted by halogen; C represents halogen or halo C1-C6 alkyl. More preferably, R 1 and R2 independently represent hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, cyano, C1-C4 alkoxy carbonyl or phenyl, said phenyl is unsubstituted or substituted by one or more groups selected from halogen, halo C1-C4 alkyl, C1-C4 alkyl, C1-C4 alkoxy and C2-C4 alkenyl; X represents C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, halogen, C2-C4 alkenyl or C2-C4 alkynyl; Y represents nitro or NR 3R4, wherein, R3 represents H, Cl-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, -COR 12, nitro, OR 13 , S0 2 R1 4 , NRi 5 Ri 6 , N=CR 17Ri, Cl-C4 alkyl carbamoyl, diC1-C4 alkyl carbamoyl, triC1-C4 alkyl silyl or diC1-C4 alkyl phosphono, the C1-C4 alkyl, C2-C4 alkenyl and C2-C4 alkynyl are independently optionally substituted by 1-2 Rii; R4 represents H, Cl-C4 alkyl or -COR 12, the C1-C4 alkyl is optionally substituted by one or two Rii; or NR 3R4 represents

NN N or- th N>-N/ N=CR2 1NR 22 R 23 , N=CR 24 0R 25 , or the

N NN , and 0 are independently unsubstituted or substituted by 1-2 groups selected

from halogen, C1-C4 alkyl, C1-C4 alkoxy, halo C1-C4 alkoxy, C1-C4 alkylthio, halo C1-C4 alkylthio, amino, C1-C4 alkyl amino, diC1-C4 alkyl amino and C1-C4 alkoxy carbonyl; wherein, RiI independently represents halogen, hydroxy, C1-C4 alkoxy, halo C1-C4 alkoxy, C1-C4 alkylthio, halo C1-C4 alkylthio, amino, C1-C4 alkyl amino, diC1-C4 alkyl amino, C1-C4

0 S NN alkoxy carbonyl, phenyl, naphthylNNo the ~~rN ~ N< or'

phenyl, naphthyl, , N and N are independently

unsubstituted or substituted by 1-3 groups selected from halogen, C1-C4 alkyl, C1-C4 alkoxy and nitro; R12 represents H, Cl-C8 alkyl, halo C1-C4 alkyl, C1-C4 alkoxy, phenyl, phenoxy or

benzyloxy; R13 represents H, Cl-C4 alkyl, halo C1-C4 alkyl, phenyl, benzyl or CHR 3 1C(O)OR 32 ; R 3

represents H, Cl-C4 alkyl or Cl-C4 alkoxy; R3 2 represents H, Cl-C4 alkyl or benzyl; R 14 represents Cl-C4 alkyl or halo C1-C4 alkyl; Ri r epresents H, Cl-C4 alkyl, formyl, Cl-C4 alkyl acyl, halo C1-C4 alkyl acyl, C1-C4 alkoxy carbonyl, phenyl carbonyl, phenoxy carbonyl or benzyloxy carbonyl; R1 6 represents H or Cl-C4 alkyl; R 17 represents H, Cl-C4 alkyl or phenyl, said phenyl is unsubstituted or substituted by 1-3 groups selected from halogen, C1-C4 alkyl and C1-C4 alkoxy; Ri r epresents H or Cl-C4 alkyl; or

N N-O N=CR 17Ris represents or; R21 and R 24 independently represent H or Cl-C4 alkyl;

R22 and R 2 3 independently represent H or Cl-C4 alkyl; or NR2 2 R2 3 represents

N N , N or 0.

R2 5 represents Cl-C4 alkyl; A represents halogen or amino; B represents hydrogen, halogen, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkyl amino or diC1-C4 alkyl amino, the C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkyl amino and diC1-C4 alkyl amino are independently unsubstituted or substituted by halogen; C represents halogen or halo C1-C4 alkyl. Further preferably, R1 and R2 independently represent hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, methylthio, ethylthio, cyano, methoxycarbonyl, ethoxycarbonyl or phenyl, said phenyl is unsubstituted or substituted by one or more groups selected from halogen, CF3 , methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, methoxy and ethoxy;

X represents chlorine, bromine, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl;

H H N' H _N, ' H N~' N NN Y represents NH 2 , NHMe, N(Me)2, COCH 3 , 3N 'OH,

0 0

' OH 'Nr - -HN

A represents fluorine, chlorine or amino; B represents hydrogen, fluorine, chlorine, methoxy, ethoxy or methylthio, the methoxy, ethoxy and methylthio independently contain or don't contain fluorine; C represents fluorine, chlorine or trifluoromethyl. A method for preparing the substituted pyrimidinyl formyl oxime derivative, which comprises the following steps: subjecting the compound of the general formula II and the compound of the general formula III to reaction to obtain the compound of the general formula I, the chemical reaction scheme is as follows: Y Y

-N OH 0o'.1 C N R2 C + HON -R2 C A 0 N -(C A A B B

The reaction is performed under the action of base and condensation agent and in aprotic solvent. The temperature of said reaction is from 0 °C to 90 °C, further preferably, from 25 °C to 30 °C. The solvent is one solvent or more mixed solvents selected from dichloromethane, dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, toluene and xylene. The base is one or more selected from organic bases such as triethylamine, trimethylamine, DIPEA and DBU. The condensation agent is PyBop, HATU or HOBt-EDCI. A herbicidal composition, comprising a herbicidally effective amount of at least one of the substituted pyrimidinyl formyl oxime derivative. The herbicidal composition further comprising formulation auxiliary. A method for controlling a harmful plant, comprising applying a herbicidally effective amount of at least one of the substituted pyrimidinyl formyl oxime derivative, or the herbicidal composition to the harmful plant or an area with the harmful plant. Use of at least one of the substituted pyrimidinyl formyl oxime derivative, or the herbicidal composition for controlling a harmful plant. Preferably, the substituted pyrimidinyl formyl oxime derivative is used to control a harmful plant in a useful crop. More preferably, the useful crop is a genetically modified crop or a crop treated by genome editing technique. The compounds of Formula I according to the invention have 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 representatives 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, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Sida, Matricaria and Abutilon from amongst the annuals, 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 specific 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 have reached the cotyledon stage but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely. In particular, the compounds according to the invention exhibit excellent activity against Apera spica venti, Chenopodium album, Lamium purpureum, Polygonum convulvulus, Stellaria media, Veronica hederifolia, Veronica persica, Viola tricolor and against Amaranthus, Galium and Kochia species. Although the compounds according to the invention have an excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops such as, for example, wheat, barley, rye, rice, corn, sugarbeet, cotton and soya, are not damaged at all, or only to a negligible extent. In particular, they have excellent compatibility in cereals, such as wheat, barley and corn, in particular wheat. For these reasons, the present compounds are highly suitable for selectively controlling undesired plant growth in plantings for agricultural use or in plantings of ornamentals. 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 have particularly advantageous properties, for example resistance to certain pesticides, in particular certain herbicides, resistance 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 specific ingredients 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 Formula I according to the invention or their salts in economically important transgenic crops of useful and ornamental plants, for example of cereal, such as wheat, barley, rye, oats, millet, rice, maniok and corn, or else in crops of sugarbeet, cotton, soya, rapeseed, potato, tomato, pea and other vegetable species is preferred. The compounds of Formula I can preferably be used as herbicides in crops of useful plants which are resistant or which have been made resistant by genetic engineering toward the phytotoxic effects of the herbicides. Conventional ways for preparing novel plants which have modified properties compared to known plants comprise, for example, traditional breeding methods and the generation of mutants. Alternatively, 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 have been described several cases: - 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 resistant to certain herbicides, for example, glufosinate (EP-A 0 242 236, EP-A 0 242 246), glyphosate-type (WO 92/00377), or sulfonylurea-type (EP-A 0 257 993, U.S. Pat. No. 5,013,659); - transgenic crop plants, for example cotton, having the ability to produce Bacillus thuringiensis toxins (Bt toxins) which impart resistance 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 preparation 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 Weinheim, 2nd edition 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 molecules 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 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 cleaves transcripts of the abovementioned gene product.

To this end it ispossible to employ both DNA molecules which comprise the entire coding sequence of a gene product including any flanking sequences that may be present, and DNA molecules 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 which have a high degree of homology to the coding sequences of a gene product but which are not entirely identical. When expressing nucleic acid molecules 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 region with DNA sequences which 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 have 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 specific 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 resistant, 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 have 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 vegetative growth, without destroying the plants in the process. Inhibition of vegetative growth plays an important role 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, emulsifiable concentrates, sprayable solutions, dusts or granules. The invention therefore also provides herbicidal compositions comprising compounds of Formula I. The compounds of Formula I can be formulated in various 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 concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, dusts (DP), capsule suspensions (CS), seed-dressing compositions, granules for broadcasting 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-Kuhler, "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 Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H. v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzflchenaktive thylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, "Chemische Technologie"

[Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th Edition 1986. Wettable powders are preparations 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 phenols, 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 prepare 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 Formulation auxiliaries. Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example 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 concentrates 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 emulsions (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 concentrates 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 mineral oils. Suitable active compounds can also be granulated in the manner which is customary for the preparation 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 preparation 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, "Agglomeration", Chemical and Engineering 1967, pages 147 ff.; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57. For 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 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 concentrates 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 depends partly on whether the active compound is in liquid or solid form and on the granulation auxiliaries, fillers, etc. that are used. In water-dispersible granules the content of active compound, for example, is between 1 and 95% by weight, preferably between 10 and 80% by weight. In addition, the formulations of active compound may comprise the tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation 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, cinosulfuron, 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, chlornitrofen, 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-1, 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, vernolate, 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 salt, 2,4-D dimethyla mine salt, MCPA-thioethyl, MCPA, 2,4-D propionic acid, high 2,4-D propionic acid salt, 2,4-D butyric acid, MCPA propionic acid, MCPA propionic acid salt, MCPA butyric acid, 2,4,5-D, 2,4,5-D propionic acid, 2,4,5-D butyric acid, MCPA amine salt, dicamba, erbon, chlorfenac, saison, TBA, chloramben, methoxy-TBA, diclofop-methyl, fluazifop-butyl, fluazifop-p-butyl, haloxyfop-methyl, haloxyfop-P, quizalofop-ethyl, quizalofop-p-ethyl, fenoxaprop-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, chlornidine, methalpropalin, dinoprop, glyphosate, anilofos, glufosinate ammonium, amiprophos-methyl, sulphosate, piperophos, bialaphos-sodium, bensulide, butamifos, phocarb, 2,4-DEP, H-9201, zytron, imazapyr, imazethapyr, imazaquin, imazamox, imazamox ammonium salt, 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-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023.

For use, Formulations which are present in commercially available form are, if appropriate, diluted in the customary manner, for example using water in the case of wettable powders, emulsifiable concentrates, 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 Formula I required varies with the external conditions, such as temperature, 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/ha or more of active substance, but it is preferably between 0.005 and 750 g/ha, in particular between 0.005 and 250 g/ha.

Specific Mode for Carrying out the Invention The following embodiments are used to illustrate the present invention in detail and should not be taken as any limit to the present invention. The scope of the invention would be explained through the Claims. In view of economics, variety and biological activity of a compound, we preferably synthesized several compounds, part of which are listed in the following Table 1. The structure and information of a certain compound are shown in Table 1-2. The compounds in Table 1 are listed for further explication of the present invention, other than any limit therefor. The subject of the present invention should not be interpreted by those skilled in the art as being limited to the following compounds. Table 1. Structure of Compounds Y x

CN N R2

CJ A 0 B No.R 1 R2YC A I

No. Ri R2 X Y AI

1 Me Ph Br NH 2 CI F OMe

2 Me Ph OMe NH 2 CI F OMe

3 Me Ph Cl NH 2 CI F OMe

4 Ph Ph Cl NH 2 CI F ____ ___ ___ ______ ____ ____ ___ __ ____ ___ ___OMe

4-CF 3 , Ph Ph Cl NH 2 CI

6 Me Ph Cl NHCOCH 3 CI

7 3-F, Ph 4-Cl, Ph Cl NH 2 CI ' F

8 Me Ph SMe NH 2 CI F*

9 Me Et Cl NH 2 CI ' F

Ph Br NH 2 CI )::F

11 Me Ph Cl NH 2 C

12 Me Me Cl NH 2 CI

13 n-Bu QEt Cl NH 2 CI

14 H H Cl NH 2 l I

CH2CH 2CH 3 Cl Cl NH 2 OCF

16 H H Cl NH 2 Cl )::F

17 Me Me Cl NH 2 0

(Cl

18 Me CH 2CH 2Cl Cl NH 2 "" "'3

Me Ph OMe NH 2 0H ___ __ __ ___ __ __ ___ __ __ __ ___ __ _ ___ __ __ __Cl

Br

21 Ph 3-Cl, Ph Cl NH 2 0, CHF2 I!::

22 H Et Cl NHCOCH 3 S, '~CF 3 -X&F

23 CN 4-Cl, Ph Me NH 2 0, CF 3 CF 3 CI 24 F 2- OMe NHMe Nl OMe, Ph F

25clEt, 3-Ph Me NH 2 N 11c

FH

26 Br 4- MeNH CN, Ph M H CF 3

27 Me NO 2 Ph NH 2 0, CF3

4 28 QEt NHCOMe, Me NH 2 Ph & CF 3

29 SMe 4-e P Me NHCOCH 3 S~e, Ph l 1

NO 2 4-N(Me) 2 , Ph Me NH 2 CI

31 Ac 4 NHCOCH 3 NHOPh, Ph CI

32 Ph -<Ph Me c FH

4 33 COQEt Me N CI - 2 F PhOe

34B NH 22-, Ph Nc ID/I

CONHBn Me N(Et)2 CI ' F

"N~ 36 Me C

37 OPh COOPh ci ~

38 SPh COEt Me NH 2 CI

39 CONHPr 4- OMe NH 2 NMePh, Ph CI - F

CON(Me) 2 Ph Et NH 2 CI

CONH - I IEt

" 41 YNNM)2 CI " Me

42 CON H Ph kNH 2 0

CINII"'aI 43 N ~ H SO~

44COS-*a e Me F~ NH 2 0~".

tC CONH 0 44 Me Fr NH 2

' 47 ON~~h S~t NH 0,Ce

00 48H Ph Cl NH 2 + N NH

49 Et ~ t NH2ClNH 2

46 CNHe PhtB NH 2 CF 3

47 EtON-eB SEt NH 2 Cl

52 H3- e NH SCF3

48 - N02 Ph C H

Br

53 Me Ph Cl NH 2 0, "CHF 2

54 Et Et Cl NH 2 CI F*

Ph Ph OMe NH 2 CI ' F

56 Me 4- P Br NH 2 0' "CHF 2

57 Me Me Cl _N F

H 58 Me Ph Cl ~ N~ I

59 Me Ph Br H

H Me Ph OMe NI

61 Me Ph Cl N, N

0I 62PhPh 6Ph"OH Cl 0o CI HN'~ H

63 4-CF 3 9 Ph Ph Cl N ,K- c H

64 Me Ph Cl ~N Ao , Cl Cl

H 3-F, Ph 4-Cl, Ph Cl ,

0 CO I H -N 66 Me Ph SMe ~ 0 N'"I

H 67 Me Me Br IzNlo 0 Cl - F

H 68 Me Ph OMe ,N N Cl

69 Me Ph Cl CI FN 00 C e H Me Ph Br yN 0l 0 e

H 71 Me Ph OMe N SO 2Me CI ' F

H 72 Me Ph Cl N ~NH 2 c CI

H 73 Ph Ph Cl 1,N - N02 CI ' F

0 H 74 4-CF 3 , Ph Ph Cl ~N,,,, CI )::F

H Me Ph Cl ~N.--'OH CI

76 3-F, Ph 4-Cl, Ph Cl NO 2 CI

77 Me Ph Cl H

N 0l

78 Me Me Br H 0N1 c

H 79 Et Ph SMe

H 4-CF 3 , Ph Ph Cl *NC CI F

81 Et -CH(CH 3) 2 OMe H llaCI CI

82 Ph Ph Cl - -HN 0l' C

0 83 4-CF 3 , Ph Ph Cl H IjN)N0

s 84 Me Ph Cl HN/_i c 4.'

S 3-F, Ph 4-Cl, Ph ci H 1

H N 0l

Me Ph Cl ; _'N 0N 86 1 _ _ CF 3

HN NH 87 Me Ph Cl NN NH

~N H s 88 Me Ph Cl Z 1N'_

89 Me Ph Cl N ):;:CF H

Me Et Br H ICI Fj N

91 Et Et OMe HI N Nc

92 Me -CH 2 CH2CH 3 QEt H

93 Me Et Cl H I N CI N

HN'5 94 Me -CH(CH 3)2 Cl Cl - F

H N,

96 Ph Ph Cl NCl F OMe

97 Me QEt Cl NH 2 Cl )::F

98 H Ph Cl NH 2 Cl F

99 Me -C(CH3) 3 Cl NH 2 Cl F

100 Me Me Cl NH 2 c

101 H Ph Cl NH 2 CI Cl

102 Me Me Cl NH 2 CI F F

103 N R2 represents NCl NH 2 CI F OMe 104 Cl NH2

N R2 represents NNHCI F

Table 2. 1 H NMR data of compounds

No. 'HNMR

1 'H NMR (500 MHz, Chloroform-d) 6 7.53 - 7.43 (m, 5H), 7.31- 7.22 (m, 2H), 3.91 (s, 3H), 3.16 (s, 3H), 3.00 (s, 2H). J= 2 'H NMR (500 MHz, Chloroform-d) 6 7.53 - 7.43 (m, 5H), 7.28 (d, J= 7.4 Hz, 1H), 7.21 (dd, 7.4,5.6 Hz, 1H), 5.80 (s, 2H), 3.93 (s, 3H), 3.81 (s, 3H), 3.19 (s, 3H). 3 IH NMR (500 MHz, Chloroform-d) 6 7.53 - 7.43 (m, 5H), 7.31 - 7.22 (m, 2H), 5.80 (s, 2H), 3.91 (s, 3H), 3.17 (s, 3H). 4 'H NMR (500 MHz, Chloroform-d) 67.48 (tq, J= 7.1, 4.2, 3.6 Hz, 1H), 7.41 - 7.32 (m, 4H), 7.30 - 7.19 (m, 1H), 5.80 (s, 2H), 3.89 (s, 3H). Hz,1H), 7.30 IH NMR (500 MHz, Chloroform-d) 67.61 (q, J= 7.7 Hz, 4H), 7.46 (tt, J= 7.4, 2.0 - 7.22 (m, 3H), 7.25 - 7.15 (m, 3H), 5.80 (s, 2H), 3.88 (s, 3H). 6 IH NMR (500 MHz, Chloroform-d) 67.71 (s, 1H), 7.53 - 7.47 (m, 3H), 7.42 (dh, J= 5.4, 2.0, 1.6 Hz, 2H), 7.34 - 7.24 (m, 2H), 3.91 (s, 3H), 3.02 (s, 3H), 2.16 (s, 3H). 1H), 7.35 7 'H NMR (500 MHz, Chloroform-d) 6 7.55 - 7.49 (m, 2H), 7.46 (dt, J= 9.7, 1.6 Hz, 7.24 (m, 6H), 7.25 (dd, J= 7.5, 5.5 Hz, 1H), 5.80 (s, 2H), 3.91 (s, 3H). 8 IH NMR (500 MHz, Chloroform-d) 6 7.53 - 7.42 (m, 5H), 7.32 - 7.25 (m, 2H), 5.80 (s, 2H), 3.92 (s, 3H), 3.14 (s, 3H), 2.39 (s, 3H). 9 ' H NMR (500 MHz, DMSO-d 6 ) 7.62 (td, J = 8.3, 7.6, 1.8 Hz, 1H), 7.41 (dd, J = 8.6, 1.5 Hz, 1H), 3.89 (s, 3H) 2.44 - 2.30 (m, 2H), 2.0 (s, 3H), 1.05 (q, J= 7.8 Hz, 3H). IH NMR (500 MHz, Chloroform-d) 6 7.58 - 7.51 (m, 2H), 7.55 - 7.46 (m, 3H), 7.30 - 7.20 (m, 2H), 6.05 (ddt, J= 14.1, 12.3, 6.2 Hz, 1H), 5.12 (dt, J= 14.3, 1.3 Hz, 2H), 3.95 (s, 3H), 3.39 (dt, J= 6.3, 1.1 Hz, 2H), 2.66 (s, 2H). 7.27 (d, J= 11 IH NMR (500 MHz, Chloroform-d) 6 7.53 - 7.42 (m, 5H), 7.42 (d, J= 7.5 Hz, 1H), 7.3 Hz, 1H), 5.80 (s, 2H), 3.85 (s, 3H), 3.04 (s, 3H). 1 H NMR (500 MHz, Chloroform-d) 6 7.68 (dd, J = 8.7, 7.4 Hz, 1H), 7.24 - 7.17 (m, 1H), 5.80 12 (s, 2H), 3.99 (s, 3H), 2.12 (s, 3H), 2.04 (s, 3H). 'H NMR (500 MHz, Chloroform-d) 67.39 (dd, J= 7.5, 5.7 Hz, 1H), 7.28 (d, J= 7.5 Hz, 1H), 13 5.80 (s, 2H), 3.87 (s, 3H), 3.64 (q, J= 8.0 Hz, 2H), 2.11 (t, J= 8.0 Hz, 2H), 1.60 - 1.50 (m, 2H), 1.40 (dtd, J= 13.4, 8.0, 5.4 Hz, 2H), 1.28 (t, J= 8.0 Hz, 3H), 0.95 (t, J= 8.0 Hz, 3H). 14 'H NMR (500 MHz, Chloroform-d) 67.48 (d, J= 7.5 Hz, 1H), 7.43 (d, J= 7.5 Hz, 1H), 5.80 (s, 2H), 3.82 (s, 3H). IH NMR (500 MHz, Chloroform-d) 6 7.33 - 7.23 (m, 2H), 5.80 (s, 2H), 4.46 (q, J= 9.1 Hz, 2H), 2.11 (t, J= 5.4 Hz, 2H), 1.54 (dtd, J= 10.7, 8.0, 5.4 Hz, 2H), 0.91 (t, J= 8.0 Hz, 3H). 16 'H NMR (500 MHz, Chloroform-d) 67.40 (dd, J= 7.5, 5.7 Hz, 1H), 7.30 (d, J= 7.5 Hz, 1H), 5.80 (s, 2H), 3.86 (s, 3H). 17 IH NMR (500 MHz, Chlorofor-d) 67.38 (d, J= 7.5 Hz, 1H), 7.29 (d, J= 7.5 Hz, 1H), 5.80 (s, 2H), 3.86 (s, 3H), 2.63 (s, 6H). 18 IH NMR (500 MHz, Chlorofor-d) 67.49 (d, J= 7.5 Hz, 1H), 7.08 (d, J= 7.5 Hz, 1H), 5.80 (s, 2H), 4.51 (s, 2H), 3.79 (s, 3H), 3.60 (t, J= 7.9 Hz, 2H), 2.51 (s, 3H), 2.41 (t, J= 7.9 Hz, 2H). 7.32 19 IH NMR (500 MHz, Chloroforn-d) 6 7.46 (tt, J= 6.8, 2.6 Hz, 1H), 7.43 - 7.35 (m, 3H), 7.21 (m, 6H), 6.92 (d, J= 7.5 Hz, 1H), 4.51 (s, 2H), 2.72 (s, 2H), 2.33 (s, 3H). 'H NMR (500 MHz, Chloroforn-d) 6 7.54 - 7.47 (m, 3H), 7.45 (dtt, J= 5.4, 3.5, 1.5 Hz, 2H),

7.33 (d,J= 7.5 Hz, 1H), 6.98 (d,J= 7.5 Hz,1H), 5.80 (s, 2H), 4.51 (s, 2H), 3.94 (s, 3H), 3.80 (s, 3H), 2.97 (s, 3H). - 7.21 21 'H NMR (500 MHz, Chloroform-d) 67.50 (d, J= 7.5 Hz, 1H), 7.51 - 7.39 (m, 3H), 7.35 (m, 6H), 7.20 - 7.11 (m, 1H), 5.80 (s, 2H). IH NMR (500 MHz, Chloroform-d) 7.71 (s, 1H), 7.58 (dt, J= 7.5, 5.7 Hz, 1H), 6.91 (dd, J 22 9.0, 7.5 Hz, 1H), 6.46 (t, J= 7.1 Hz, 1H), 2.22 - 2.12 (m, 2H), 2.16 (s, 3H), 0.96 (t, J= 8.0 Hz, 3H). (dd, J= 23 IH NMR (500 MHz, Chloroform-d) 6 7.53 - 7.43 (m, 4H), 7.41 (d, J= 7.5 Hz, 1H), 7.34 7.5, 5.7 Hz, 1H), 5.80 (s, 2H), 2.46 (s, 3H). 'H NMR (500 MHz, Chloroform-d) 6 7.52 - 7.41 (m, 2H), 7.11 (td, J= 7.5, 2.0 Hz, 1H), 7.00 24 (dd, J= 7.4, 5.8 Hz, 1H), 6.98 - 6.90 (m, 2H), 3.91 (s, 3H), 3.81 (s, 3H), 3.11 (s, 3H), 2.96 (s, 6H), 1.50 (s, 1H). 'H NMR (500 MHz, Chloroform-d) 67.58 (dt, J= 7.1, 2.1 Hz, 1H), 7.32 - 7.22 (m, 2H), 7.20 (d, J= 7.5 Hz, 1H), 7.12 (dd, J= 7.5, 5.7 Hz, 1H), 7.05 (tt, J= 2.1, 1.1 Hz,1H), 5.80 (s, 2H), 5.44 (s, 2H), 2.92 (s, 3H), 2.47 (s, 3H), 2.33 - 2.23 (m, 2H), 1.27 (t, J= 8.0 Hz, 3H). 7.5 26 'H NMR (500 MHz, Chloroform-d) 6 7.86 - 7.80 (m, 2H), 7.64 - 7.58 (m, 2H), 7.36 (d, J= Hz, 1H), 7.25 (dd, J= 7.5, 5.7 Hz, 1H), 5.80 (s, 2H), 2.77 (s, 3H), 2.51 (s, 3H), 2.06 (s, 1H). 7.5 27 IH NMR (500 MHz, Chloroform-d) 6 8.31 - 8.24 (m, 2H), 7.62 - 7.55 (m, 2H), 7.30 (d, J= Hz, 1H), 7.21 (dd, J= 7.5, 5.7 Hz, 1H), 5.80 (s, 2H), 3.12 (s, 3H). 'H NMR (500 MHz, Chloroform-d) 6 7.48 (s, 1H), 7.40 - 7.31 (m, 3H), 7.34 - 7.26 (m, 2H), 28 7.03 (dd, J= 7.5, 5.9 Hz, 1H), 5.80 (s, 2H), 3.97 (s, 3H), 3.62 (q, J= 8.0 Hz, 2H), 2.48 (s, 3H), 2.10 (s, 3H), 1.24 (t, J= 8.0 Hz, 3H). 29 'H NMR (500 MHz, Chloroform-d) 67.71 (s, 1H), 7.40 (s, 5H), 7.34 (d, J= 7.5 Hz, 1H), 3.85 (s, 3H), 2.46 (d, J= 14.8 Hz, 6H), 2.34 (s, 3H), 2.16 (s, 3H). IH NMR (500 MHz, Chloroform-d) 6 7.36 - 7.27 (m, 2H), 7.21 - 7.15 (m, 2H), 6.78 - 6.72 (m, 2H), 5.80 (s, 2H), 3.74 (s, 3H), 3.02 (s, 6H), 2.48 (s, 3H). 'H NMR (500 MHz, Chloroform-d) 67.71 (s, 1H), 7.30 (d, J= 7.5 Hz, 1H), 7.27 - 7.16 (m, 3H), 31 7.19 - 7.13 (m, 2H), 6.93 - 6.86 (m, 2H), 6.82 - 6.74 (m, 1H), 6.78 - 6.68 (m, 2H), 4.77 (s, 1H), 3.93 (s, 3Hs), 2.15 (d, J= 6.4 Hz, 6H). 32 'H NMR (500 MHz, Chloroform-d) 6 7.40 - 7.35 (m, 2H), 7.33 - 7.20 (m, 8H), 5.80 (s, 2H), 3.92 (s, 3H), 2.42 (s, 3H), 1.91 - 1.82 (m, 1H), 1.18 - 1.10 (m, 2H), 0.91 - 0.83 (m, 2H). IH NMR (500 MHz, Chloroform-d) 6 7.32 - 7.20 (m, 4H), 7.04 - 6.99 (m, 2H), 6.37 - 6.31 (m, 33 1H), 5.80 (s, 2H), 4.97 (dq, J= 11.0, 6.4 Hz, 1H), 4.23 (q, J= 8.0 Hz, 2H), 3.93 (s, 3H), 2.59 (s, 3H), 1.70 (dd, J= 6.4, 1.1 Hz, 3H), 1.31 (t, J= 8.0 Hz, 3H). IH NMR (500 MHz, Chloroform-d) 6 7.52 - 7.45 (m, 1H), 7.38 (dt, J= 6.1, 2.0 Hz, 3H), 7.32 (td, J= 34 (tdd, J= 10.2, 4.5, 2.7 Hz, 5H), 7.28 - 7.20 (m, 1H), 7.07 (td, J= 7.5, 2.0 Hz, 1H), 6.73 7.4, 1.9 Hz, 1H), 6.62 (dd, J= 7.4, 2.0 Hz, 1H), 6.41 - 6.32 (m, 2H), 5.17 (s, 2H), 4.93 (s, 1H), 4.93 (d, J= 2.1 Hz, 1H), 3.94 (s, 3H). IH NMR (500 MHz, Chloroform-d) 6 7.36 - 7.29 (m, 4H), 7.32 - 7.19 (m, 3H), 4.46 (s, 2H), 4.24 (q, J= 8.0 Hz, 4H), 3.83 (s, 3H), 2.49 (s, 3H), 1.40 (p, J= 7.0 Hz, 1H), 1.12 (t, J= 8.0 Hz, 6H), 0.29 - 0.21 (m, 2H), 0.10 - 0.02 (m, 2H). IH NMR (500 MHz, Chloroform-d) 6 7.46 - 7.38 (m, 2H), 5.85 (ddt, J= 14.7, 12.5, 6.2 Hz, 1H), 36 5.06 - 4.99 (m, 2H), 3.80 (s, 3H), 3.66 (ddt, J= 7.1, 5.6, 1.8 Hz, 4H), 2.80 (dt, J= 6.2, 1.0 Hz, 2H), 2.54 (s, 3H), 2.03 - 1.93 (m, 4H), 0.27 (ddd, J= 7.0, 4.2, 2.9 Hz, 2H), 0.12 (tt, J= 7.2, 4.3 Hz, 2H). 37 'H NMR (500 MHz, Chloroform-d) 6 7.43 - 7.24 (m, 7H), 7.26 - 7.16 (m, 3H), 7.08 - 6.97 (m, 3H), 3.90 (s, 3H), 3.66 (t, J= 5.2 Hz, 4H), 1.65 - 1.54 (m, 6H). 38 IH NMR (500 MHz, Chloroform-d) 6 7.51 - 7.41 (m, 3H), 7.35 - 7.20 (m, 4H), 5.80 (s, 2H), 3.87 (s, 3H), 2.58 (s, 3H), 2.44 (q, J= 8.0 Hz, 2H), 1.11 (t, J= 8.0 Hz, 3H). 'H NMR (500 MHz, Chloroform-d) 6 7.33 - 7.17 (m, 6H), 7.06 - 6.97 (m, 3H), 6.89 - 6.83 (m, 39 2H), 5.80 (s, 2H), 3.90 (s, 3H), 3.78 (s, 3H), 3.34 (s, 3H), 3.22 (t, J= 7.6 Hz, 2H), 1.52 (h, J= 7.9 Hz, 2H), 0.86 (t, J= 8.0 Hz, 3H). 'H NMR (500 MHz, Chloroform-d) 6 7.48 - 7.40 (m, 4H), 7.28 (d, J= 4.6 Hz, 2H), 5.80 (s, 2H), 3.90 (s, 3H), 2.94 (s, 6H), 2.66 (q, J= 8.0 Hz, 2H), 1.18 (t, J= 8.0 Hz, 3H). 'H NMR (500 MHz, Chloroform-d) 6 7.29 - 7.21 (m, 2H), 7.22 - 7.16 (m, 2H), 7.15 - 7.09 (m, 41 2H), 5.73 (ddt, J= 16.5, 10.1, 6.2 Hz, 1H), 5.29 (s, 1H), 5.31 - 5.22 (m, 1H), 5.18 - 5.07 (m, 1H), 4.46 (d, J= 1.2 Hz, 2H), 3.93 (s, 3H), 3.60 (dt, J= 6.2, 1.1 Hz, 2H), 3.33 (s, 6H), 2.23 2.13 (m, 5H), 0.99 (t, J= 8.0 Hz, 3H).

IH NMR (500 MHz, Chloroform-d) 6 7.58 - 7.49 (m, 3H), 7.48 - 7.37 (m, 3H), 7.36 - 7.22 (m, 42 5H), 7.00 (d, J= 7.5 Hz, 1H), 6.19 (s, 1H), 5.80 (s, 2H), 4.51 (s, 2H), 4.46 (s, 2H), 3.76 (s, 3H), 3.03 (s, 1H). (d, J 43 'H NMR (500 MHz, Chloroform-d) 67.47 (d, J= 7.5 Hz, 1H), 7.42 - 7.33 (m, 4H), 6.96 7.5 Hz, 1H), 6.11 (s, 1H), 5.80 (s, 2H), 4.68 (s, 1H), 4.51 (s, 2H), 2.46 - 2.37 (m, 9H). 'H NMR (500 MHz, Chloroform-d) 7.45 (d, J= 7.5 Hz, 1H), 7.38 (d, J= 7.5 Hz, 1H), 7.13 44 7.06 (m, 4H), 6.83 - 6.77 (m, 2H), 5.98 (s, 1H), 4.46 (d, J= 1.2 Hz, 2H), 3.93 (s, 3H), 3.80 (s, 3H), 2.82 (s, 3H). IH NMR (500 MHz, Chloroform-d) 6 7.63 - 7.49 (m, 3H), 7.47 (s, 3H), 7.52 - 7.41 (m, 3H), 7.34 - 7.25 (m, 2H), 6.41 (t, J= 7.5 Hz, 1H), 6.25 (dd, J= 7.5,1.5 Hz,1H), 6.21 (s, 1H), 5.80 (s, 2H), 4.07 (s, 2H). IH NMR (500 MHz, Chloroform-d) 67.58 - 7.48 (m, 3H), 7.50 - 7.42 (m, 3H), 7.31 - 7.16 (m, 46 5H), 7.11 (d, J= 7.5 Hz, 1H), 6.13 (s, 1H), 4.51 (s, 2H), 3.79 (s, 3H), 3.44 (t, J= 7.6 Hz, 2H), 2.76 - 2.68 (m, 4H). IH NMR (500 MHz, Chloroform-d) 6 7.63 - 7.56 (m, 2H), 7.44 - 7.38 (m, 1H), 7.32 (s, 1H), 47 7.37 - 7.17 (m, 4H), 5.80 (s, 2H), 4.81 (dd, J= 10.0, 1.5 Hz, 1H), 4.58 (dd, J= 16.7, 1.5 Hz, 1H), 3.71 (s, 3H), 2.97 (q, J= 8.0 Hz, 2H), 1.28 (t, J= 8.0 Hz, 3H). - 7.35 48 IH NMR (500 MHz, Chloroform-d) 6 7.58 - 7.50 (m, 1H), 7.45 (t, J= 7.5 Hz, 2H), 7.44 (m, 4H), 7.34 (d, J= 4.6 Hz, 4H), 5.80 (s, 2H), 5.25 (s, 2H), 3.82 (s, 3H). 'H NMR (500 MHz, Chloroform-d) 67.74 (s, 1H), 7.30 - 7.20 (m, 2H), 6.63 (dd, J= 7.5, 1.5 2H), 4.34 49 Hz, 1H), 6.15 (t, J= 7.5 Hz, 1H), 6.00 (dd, J= 7.4, 1.5 Hz,1H), 5.80 (s, 2H), 5.46 (s, (q, J= 8.0 Hz, 2H), 3.89 (s, 3H), 2.17 (q, J= 8.0 Hz, 2H), 1.61 (t, J= 8.0 Hz, 3H), 1.04 (t, J= 8.0 Hz, 3H). 'H NMR (500 MHz, Chloroform-d) 67.97 (t, J= 1.4 Hz, 1H), 7.86 - 7.78 (m, 2H), 7.75 (dd, J= 7.5, 1.6 Hz, 1H), 7.68 (dt, J= 7.7, 2.0 Hz, 1H), 7.54 - 7.44 (m, 2H), 7.28 (d, J= 7.4 Hz, 1H), 7.23 (dd, J= 7.4, 5.6 Hz, 1H), 5.80 (s, 2H), 3.96 (s, 3H), 3.80 (s, 3H), 2.66 (q, J= 8.0 Hz, 2H), 1.23 (t, J= 8.0 Hz, 3H). IH NMR (500 MHz, Chloroform-d) 6 7.26 - 7.17 (m, 2H), 5.80 (s, 2H), 4.34 (q, J= 8.0 Hz, 2H), 51 3.92 (s, 3H), 2.21 - 2.07 (m, 4H), 1.65 - 1.50 (m, 5H), 1.40 (dtd, J= 13.4, 8.0, 5.5 Hz, 2H), 0.91 (dt, J= 35.2, 8.0 Hz, 6H). 'H NMR (500 MHz, Chloroform-d) 68.09 (dt, J= 7.5, 2.0 Hz, 1H), 7.93 (q, J= 1.8 Hz, 1H), 52 7.70 - 7.64 (m, 1H), 7.59 - 7.50 (m, 2H), 7.40 (dt, J= 7.5, 5.7 Hz, 1H), 6.91 (dd, J= 8.8, 7.5 Hz, 1H), 5.80 (s, 2H), 2.37 (s, 3H). 53 'H NMR (500 MHz, Chloroform-d) 6 7.53 - 7.43 (m, 6H), 7.23 - 7.17 (m, 1H), 5.80 (s, 2H), 3.11 (s, 3H). 54 IH NMR (500 MHz, Chloroform-d) 67.48 (ddd, J= 8.1, 6.3, 3.0 Hz, 2H), 7.40 - 7.32 (m, 8H), 7.30 - 7.17 (m, 2H), 5.80 (s, 2H), 3.95 (s, 3H), 3.81 (s, 3H). IH NMR (500 MHz, Chloroform-d) 67.48 (ddd, J= 8.1, 6.3, 3.0 Hz, 2H), 7.40 - 7.32 (m, 8H), 7.30 - 7.17 (m, 2H), 5.80 (s, 2H), 3.95 (s, 3H), 3.81 (s, 3H). 56 'H NMR (500 MHz, Chloroform-d) 6 7.52 - 7.45 (m, 3H), 7.40 - 7.31 (m, 2H), 7.22 - 7.13 (m, 1H), 3.16 (s, 3H), 2.72 (s, 2H). (d, J= 7.4 57 IH NMR (500 MHz, Chloroform-d) 67.83 (s, 1H), 7.33 (dd, J= 7.5,5.7 Hz, 1H), 7.25 Hz, 1H), 3.91 (s, 3H), 2.85 (s, 6H), 2.65 (s, 6H). 7.27 (d, J= 58 'H NMR (500 MHz, Chloroform-d) 6 7.53 - 7.45 (m, 5H), 7.42 (d, J= 7.5 Hz, 1H), 7.5 Hz, 1H), 3.86 (s, 3H), 3.07 (s, 3H), 2.89 (d, J= 14.3 Hz, 2H). 59 'H NMR (500 MHz, Chloroform-d) 6 7.53 - 7.47 (m, 3H), 7.51 - 7.41 (m, 2H), 7.30 - 7.19 (m, 2H), 3.89 (s, 3H), 3.75 (t, J= 4.4 Hz, 2H), 3.15 (s, 3H), 2.72 (t, J= 4.4 Hz, 2H), 2.32 (s, 6H). IH NMR (500 MHz, Chloroform-d) 67.50 (s, 5H), 7.27 (t, J= 2.4 Hz, 3H), 3.78 (d, J= 13.0 Hz, 6H), 3.71 (t, J= 4.2 Hz, 2H), 3.49 (t, J= 4.2 Hz, 2H), 3.37 (s, 3H), 3.08 (s, 3H). 61 'H NMR (500 MHz, Chloroform-d) 68.02 (s, 1H), 7.53 - 7.43 (m, 5H), 7.29 (d, J= 4.9 Hz, 2H), 3.92 (s, 3H), 3.08 (s, 3H), 2.85 (s, 6H). 62 IH NMR (500 MHz, Chloroform-d) 67.48 (ddd, J= 9.5, 6.2, 2.8 Hz, 2H), 7.41 - 7.32 (m, 8H), 7.27 (d, J= 7.4 Hz, 1H), 7.19 (dd, J= 7.5, 5.5 Hz,1H), 4.47 (s, 2H), 3.90 (s, 3H), 3.34 (s, 1H). 'H NMR (500 MHz, Chloroform-d) 6 7.64 - 7.58 (m, 2H), 7.46 (tt, J= 7.3, 2.1 Hz, 1H), 7.42 63 7.35 (m, 2H), 7.34 - 7.21 (m, 5H), 7.18 (dd, J= 7.5, 5.7 Hz, 1H), 7.08 (s, 1H), 4.79 (s, 1H), 3.89 (s, 3H), 2.02 (s, 3H). 7.20 (d, J= 64 IH NMR (500 MHz, Chloroform-d) 6 7.54 - 7.43 (m, 5H), 7.39 (d, J= 7.5 Hz, 1H), 7.5 Hz, 1H), 4.13 (s, 2H), 3.84 (s, 3H), 3.65 (s, 3H), 3.15 (s, 3H), 2.12 (s, 1H).

IH NMR (500 MHz, Chloroform-d) 6 7.63 - 7.56 (m, 2H), 7.47 - 7.36 (m, 4H), 7.34 - 7.23 (m, 3H), 7.14 (dt, J= 8.9, 2.0 Hz, 1H), 3.87 (s, 3H), 3.66 (s, 3H), 2.58 (s, 1H). - 7.24 66 'H NMR (500 MHz, Chloroform-d) 67.50 (s, 4H), 7.50 (s, 1H), 7.53 - 7.41 (m, 2H), 7.38 (m, 5H), 4.79 (s, 1H), 3.91 (s, 3H), 3.10 (s, 3H), 2.80 (s, 1H), 2.38 (s, 3H). 67 IH NMR (500 MHz, Chloroform-d) 6 7.30 - 7.20 (m, 1H), 3.94 (s, 1H), 2.67 (s, 2H), 1.34 (s, 3H). 68 'H NMR (500 MHz, Chloroform-d) 6 7.54 - 7.46 (m, 2H), 7.50 (s, 4H), 7.35 - 7.26 (m, 2H), 3.89 (s, 3H), 3.81 (s, 3H), 3.10 (s, 3H), 2.14 (d, J= 6.8 Hz, 3H). 69 IH NMR (500 MHz, Chloroform-d) 6 7.53 - 7.41 (m, 5H), 7.31 - 7.21 (m, 2H), 3.92 (s, 3H), 3.77 (t, J= 4.6 Hz, 4H), 3.57 (t, J= 4.6 Hz, 4H), 3.11 (s, 3H). IH NMR (500 MHz, Chloroform-d) 6 7.56 - 7.43 (m, 8H), 3.86 (s, 3H), 3.65 (s, 3H), 3.02 (s, 3H). 7.5, 5.5 71 'H NMR (500 MHz, Chloroform-d) 67.50 (s, 5H), 7.28 (d, J= 7.5 Hz, 1H), 7.21 (dd, J= Hz, 1H), 5.61 (s, 1H), 3.85 (d, J= 18.1 Hz, 6H), 3.07 (s, 3H), 2.73 (s, 3H). 72 IH NMR (500 MHz, Chloroform-d) 67.50 (s, 5H), 7.41 (d, J= 7.5 Hz, 1H), 7.26 (d, J= 7.5 Hz, 1H), 3.81 (s, 3H), 3.07 (s, 1H), 3.03 (s, 3H), 2.09 (s, 2H). 73 'H NMR (500 MHz, Chloroform-d) 6 7.52 - 7.43 (m, 2H), 7.42 - 7.33 (m, 4H), 7.37 (s, 4H), 7.26 (d, J= 7.5 Hz, 1H), 7.14 (dd, J= 7.5, 5.7 Hz, 1H), 3.90 (s, 3H), 3.54 (s, 1H). 'H NMR (500 MHz, Chloroform-d) 6 7.65 - 7.57 (m, 4H), 7.46 (tt, J= 7.4, 2.0 Hz, 1H), 7.31 74 7.21 (m, 3H), 7.20 - 7.13 (m, 3H), 4.22 - 4.11 (m, 4H), 3.91 (s, 3H), 2.53 (s, 1H), 1.24 (t, J= 8.0 Hz, 3H). IH NMR (500 MHz, Chloroform-d) 67.50 (d, J= 1.3 Hz, 5H), 7.31 - 7.22 (m, 3H), 3.83 (s, 3H), 3.74 (t, J= 4.5 Hz, 2H), 3.62 (q, J= 4.7 Hz, 2H), 3.08 (s, 3H). 76 IH NMR (500 MHz, Chloroform-d) 6 7.60 - 7.48 (m, 3H), 7.43 (ddd, J= 8.8, 6.8, 2.0 Hz, 2H), 7.34 - 7.24 (m, 4H), 7.20 (dd, J= 7.5, 5.5 Hz, 1H), 3.93 (s, 3H). 77 'H NMR (500 MHz, Chloroform-d) 6 7.53 - 7.43 (m, 5H), 7.39 - 7.29 (m, 4H), 7.30 - 7.20 (m, 3H), 6.46 (s, 1H), 4.79 (s, 1H), 3.93 (s, 3H), 3.15 (s, 3H). (d, J= 1.0 78 IH NMR (500 MHz, Chloroform-d) 6 7.34 - 7.26 (m, 2H), 6.48 - 6.40 (m, 3H), 4.51 Hz, 2H), 3.93 (s, 3H), 3.84 (s, 3H), 3.78 (s, 3H), 2.63 (s, 6H). 'H NMR (500 MHz, Chloroform-d) 67.88 (dd, J= 6.6, 2.8 Hz, 1H), 7.69 - 7.62 (m, 2H), 7.66 79 7.55 (m, 1H), 7.54 - 7.47 (m, 3H), 7.46 - 7.38 (m, 3H), 7.29 (d, J= 7.5 Hz, 1H), 6.46 (s, 1H), 4.65 (d, J= 1.1 Hz, 2H), 3.86 (s, 3H), 2.76 (q, J= 8.0 Hz, 2H), 2.26 (s, 3H), 1.03 (t, J= 8.0 Hz, 3H). IH NMR (500 MHz, Chloroform-d) 6 7.68 - 7.58 (m, 4H), 7.46 (tt, J= 7.4, 2.0 Hz, 1H), 7.39 (tdd, J= 5.7, 1.9, 1.0 Hz, 1H), 7.34 - 7.22 (m, 5H), 7.25 - 7.15 (m, 3H), 7.11 (td, J= 7.5, 2.1 Hz, 1H), 6.46 (s, 1H), 4.65 (d, J= 1.1 Hz, 2H), 3.92 (s, 3H). IH NMR (500 MHz, Chloroform-d) 67.44 (d, J= 7.5 Hz, 1H), 7.26 (d, J= 7.5 Hz, 1H), 7.19 (td, 81 J= 5.8, 1.2 Hz, 2H), 7.02 - 6.94 (m, 2H), 6.46 (s, 1H), 4.79 (d, J= 1.2 Hz, 2H), 3.85 (d, J= 11.0 Hz, 6H), 2.21 - 2.06 (m, 3H), 1.04 (d, J= 6.8 Hz, 6H), 0.84 (t, J= 8.0 Hz, 3H). 'H NMR (500 MHz, Chloroform-d) 67.64 (dd, J= 7.4, 1.6 Hz, 1H), 7.52 - 7.44 (m, 2H), 7.42 82 7.30 (m, 8H), 7.32 - 7.25 (m, 2H), 6.48 - 6.40 (m, 2H), 6.34 (dd, J= 7.5, 1.6 Hz, 1H), 5.09 (s, 2H), 3.91 (s, 3H). 'H NMR (500 MHz, Chloroform-d) 67.69 (d, J= 7.5 Hz, 2H), 7.58 - 7.41 (m, 6H), 7.29 - 7.21 83 (m, 2H), 7.20 - 7.13 (m, 3H), 6.46 (s, 1H), 6.39 (dd, J= 7.5, 1.5 Hz, 1H), 4.65 (s, 2H), 3.85 (s, 3H). (t, J= 84 'H NMR (500 MHz, Chloroform-d) 6 7.54 - 7.41 (m, 7H), 7.34 (d, J= 7.5 Hz, 1H), 7.01 7.4 Hz, 1H), 6.90 (dd, J= 7.5, 1.7 Hz, 1H), 6.46 (s, 1H), 4.85 (s, 2H), 3.88 (s, 3H), 3.12 (s, 3H). IH NMR (500 MHz, Chloroform-d) 6 7.57 - 7.51 (m, 2H), 7.47 - 7.37 (m, 4H), 7.40 - 7.27 (m, 4H), 7.15 (dd, J= 7.5, 1.5 Hz, 1H), 7.03 - 6.94 (m, 2H), 6.46 (s, 1H), 4.70 (s, 2H), 3.95 (s, 3H). 7.5 86 'H NMR (500 MHz, Chloroform-d) 67.51 (h, J= 3.8, 3.3 Hz, 6H), 7.22 (s, 2H), 7.12 (d, J= Hz, 1H), 6.46 (s, 1H), 4.65 (s, 2H), 4.51 (s, 2H), 3.74 (s, 3H), 3.03 (s, 3H). 'H NMR (500 MHz, Chloroform-d) 67.50 (dp, J= 3.9, 1.9 Hz, 3H), 7.47 - 7.38 (m, 3H), 7.25 87 (d, J= 7.5 Hz, 1H), 7.01 (d, J= 7.5 Hz, 1H), 6.46 (s, 1H), 6.19 (d, J= 7.5 Hz,1H), 4.58 (s, 2H), 4.51 (s, 2H), 3.80 (s, 3H), 2.98 (s, 3H). 'H NMR (500 MHz, Chloroform-d) 67.55 - 7.47 (m, 5H), 7.46 - 7.40 (m, 2H), 7.17 (dd, J= 7.5, 88 1.6 Hz, 1H), 6.94 (d, J= 7.5 Hz, 1H), 6.57 (t, J= 7.5 Hz,1H), 5.76 (s, 2H), 4.51 (s, 2H), 3.00 (d, J= 16.1 Hz, 4H), 2.30 (s, 3H). 89 'H NMR (500 MHz, Chloroform-d) 6 7.55 - 7.44 (m, 6H), 7.31 - 7.21 (m, 2H), 6.46 (s, 1H), 6.08 (d, J= 7.5 Hz, 1H), 4.58 (s, 2H), 3.93 (s, 3H), 3.12 (s, 3H).

IH NMR (500 MHz, Chloroform-d) 68.69 (d, J= 1.2 Hz, 1H), 8.50 (dd, J= 5.0, 1.3 Hz, 1H), 90 7.66 (dt, J= 8.1, 1.3 Hz, 1H), 7.35 - 7.27 (m, 2H), 7.23 (dd, J= 8.0, 5.0 Hz, 1H), 6.46 (s, 1H), 4.65 (s, 2H), 3.91 (s, 3H), 2.62 (s, 3H), 2.17 (q, J= 8.0 Hz, 2H), 1.04 (t, J= 8.0 Hz, 3H). 'H NMR (500 MHz, Chloroform-d) 8.62 (dd, J= 4.9, 1.3 Hz, 1H), 7.57 (td, J= 8.0, 1.2 Hz, 91 1H), 7.41 (dd, J= 8.0, 1.1 Hz, 1H), 7.30 - 7.22 (m, 2H), 7.20 (dd, J= 7.5, 5.5 Hz, 1H), 6.46 (s, 1H), 4.91 (s, 2H), 3.90 (s, 3H), 3.68 (s, 3H), 2.17 (q, J= 8.0 Hz, 4H), 1.01 (t, J= 8.0 Hz, 6H). 'H NMR (500 MHz, Chloroform-d) 8.56 (d, J= 5.1 Hz, 2H), 7.33 (d, J= 5.2 Hz, 2H), 7.26 (d, 92 J= 7.5 Hz, 1H), 7.17 (dd, J= 7.5, 5.7 Hz, 1H), 6.46 (s, 1H), 5.57 (s, 2H), 4.34 (q, J= 8.0 Hz, 2H), 3.92 (s, 3H), 2.63 (s, 3H), 2.11 (t, J= 8.0 Hz, 2H), 1.65 - 1.54 (m, 3H), 1.57 - 1.48 (m, 2H), 0.92 (t, J= 8.1 Hz, 3H). 'H NMR (500 MHz, Chloroform-d) 68.49 (dd, J= 5.0, 1.2 Hz, 1H), 7.32 - 7.22 (m, 2H), 7.23 93 7.16 (m, 2H), 6.46 (s, 1H), 4.91 (s, 2H), 3.93 (s, 3H), 2.62 (s, 3H), 2.28 (s, 3H), 2.17 (q, J= 8.0 Hz, 2H), 1.04 (t, J= 8.0 Hz, 3H). 'H NMR (500 MHz, Chloroform-d) 6 7.82 - 7.73 (m, 2H), 7.72 (dt, J= 7.5, 1.6 Hz, 1H), 7.68 (t, - 7.26 94 J= 1.5 Hz, 1H), 7.58 (dd, J= 7.4, 1.5 Hz, 1H), 7.41 (dtd, J= 26.1, 7.4, 1.6 Hz, 2H), 7.33 (m, 2H), 6.46 (s, 1H), 4.90 (s, 2H), 3.94 (s, 3H), 2.59 (s, 3H), 1.69 (hept, J= 6.9 Hz, 1H), 1.07 (d, J= 6.8 Hz, 6H). IH NMR (500 MHz, Chloroform-d) 68.83 (dd, J= 7.5, 1.5 Hz, 1H), 8.35 (dd, J= 7.5, 1.4 Hz, 95 1H), 8.01 (dd, J= 7.4, 1.5 Hz, 1H), 7.71 - 7.63 (m, 3H), 7.66 - 7.57 (m, 2H), 7.56 - 7.48 (m, 2H), 7.39 - 7.31 (m, 2H), 7.28 (d, J= 7.5 Hz, 1H), 7.25 - 7.14 (m, 5H), 6.46 (s, 1H), 4.80 (s, 2H), 3.96 (s, 3H). IH NMR (500 MHz, Chloroform-d) 68.78 (s, 2H), 8.14 (d, J= 7.5 Hz, 1H), 7.92 (d, J= 1.5 Hz, 96 1H), 7.75 (dd, J= 7.5,1.5 Hz, 1H), 7.65 - 7.53 (m, 3H), 7.45 (t, J= 7.5 Hz, 2H), 7.35 (tt, J= 7.3, 2.2 Hz, 1H), 7.28 (d, J= 7.5 Hz, 1H), 7.28 - 7.18 (m, 3H), 7.18 (dd, J= 7.8, 2.1 Hz, 2H), 6.46 (s, 1H), 4.79 (s, 2H), 3.92 (s, 3H). = 8.7,1.6 Hz, 1H), 4.12 (t, J 97 i1H NMR (500 MHz, DMSO-d 6) 6 7.65 - 7.59 (m, 1H), 7.41 (dd, J = 7.2 Hz, 2H), 3.89 (s, 3H), 2.08 - 2.01 (m, 3H), 1.29 - 1.22 (m, 3H).

98 '1H NMR (500 MHz, DMSO-d 6 ) 6 8.91 (s, 1H), 7.80 - 7.75 (m, 2H), 7.64 (t, J = 8.1 Hz, 1H), 7.60 - 7.54 (m, 1H), 7.52 (dd, J= 8.2, 6.6 Hz, 2H), 7.42 (dd, J= 8.7, 1.6 Hz, 1H), 3.90 (s, 3H). Hz, 1H), 3.89 99 1 H NMR (500 MHz, DMSO-d 6 ) 6 7.61 (t, J= 8.0 Hz, 1H), 7.41 (dd, J= 8.6, 1.6 (s, 3H), 1.98 (d, J= 1.5 Hz, 3H), 1.11 (d, J = 1.5 Hz, 9H). 100 IH NMR (500 MHz, Chloroform-d) 6 7.60 (dd, J = 7.5, 5.7 Hz, 1H), 7.41 (dd, J = 8.9, 2.0 Hz, 1H), 7.13 (dd, J = 7.5, 2.0 Hz, 1H), 5.80 (s, 2H), 2.60 (s, 6H). 101 'H NMR (500 MHz, Chloroform-d) 6 7.84 (s, 1H), 7.58 - 7.50 (m, 1H), 7.47 - 7.39 (m, 2H), 7.36 - 7.30 (m, 2H), 7.27 (dd, J= 7.5, 5.7 Hz, 1H), 7.12 (d, J= 7.5 Hz, 1H), 5.80 (s, 2H). 102 IH NMR (500 MHz, Chloroform-d) 6 7.36 (dd, J = 7.5, 5.7 Hz, 1H), 7.28 (dd, J= 7.5, 5.7 Hz, 1H), 5.80 (s, 2H), 2.66 (s, 6H). 103 'H NMR (500 MHz, Chloroform-d) 6 7.43 (dd, J= 7.5, 5.7 Hz, 1H), 7.34 (d, J= 7.5 Hz, 1H), 5.80 (s, 2H), 3.89 (s, 3H), 2.11 (t, J= 5.6 Hz, 4H), 1.72 - 1.56 (m, 6H). 104 1 H NMR (500 MHz, DMSO-d 6 ) 6 7.61 (t, J= 8.1 Hz, 1H), 7.41 (d, J = 8.6 Hz, 1H), 3.89 (s, 3H), 2.49-2.47 (m, 4H), 1.76-1.71 (m, 4H). Examples of representative compounds are as follows: 1.Preparation of compound 98: NH2 NH 2 C N F H PyBOP N' N HO 0 0 0"N_ ! N" &I "I _ TEADOM _ N' N N" K 0 01

a b 98

Construction of device: a 50 mL single-necked flask with round bottom, a stirring bar, and a constant temperature stirrer.

Compound a (0.4 g, 1.2 mmol, 1.0 eq), PyBOP (0.69 g, 1.32mmol, 1.leq) and Et 3 N (0.16 g, 1.6mmol, 1.3eq) were added sequentially to 8 mL of DCM, and the reaction solution was stirred at room temperature for 30 min followed by the addition of Compound b (0.16 g, 1.3mmol, 1.leq). Then, the reaction solution was stirred for 12 hours. TLC test showed that the reaction was completed. The reaction solution was poured into 10 ml of water, and the mixture was separated, and the aqueous phase was extracted with 10 ml of DCM for three times, and the organic phase was dried, evaporated to dryness under reduced pressure and separated by column chromatography to obtain Compound 98 (0.35 g, 67% yield) (white solid). 2.Preparation of compound 99: NH2 NH 2 CI N/ C

H'N F HATU N N

NC N'A DBU, ACN C1 F 0 CI F a c

Construction of device: a 50 mL single-necked flask with round bottom, a stirring bar, and a constant temperature magnetic stirrer. Compound a (0.4 g, 1.2 mmol, 1.0 eq), HATU (0.50 g, 1.32mmol, 1.leq), DBU (0.24 g, 1.6mmol, 1.3eq) were added sequentially to 10 mL of ACN, and the reaction solution was stirred at room temperature for 30 min followed by the addition of Compound c (0.15 g, 1.3mmol, 1.leq). Then, the reaction solution was stirred for 12 hours. TLC test showed that the reaction was completed. The reaction solution was poured into 10 ml of water, and the mixture was separated, and the aqueous phase was extracted with 10 ml of ethyl acetate for three times, and the organic phase was dried, evaporated to dryness under reduced pressure and separated by column chromatography to obtain Compound 99 (0.38 g, 74% yield) (white solid). The method for preparing the compound of the invention will be explained in detail in the following program and embodiment. The material is commercial available or prepared through known method reported in the literature or shown in the route. Those skilled in the art should understand that the compound of the invention can also be synthesized by other synthetic route. Although the detailed material and reaction condition in the synthetic route have been explicated in the following text, it is still easy to be replaced by other similar material and condition. Isomer of the compound, for example, that produced with the variation of the preparation method of the present invention is included in the scope of the present invention. In addition, the following preparation method can be further modified according to the disclosures of the present invention by using common chemical method known to those skilled in the art, for example, protection of suitable group in the process of the reaction, etc. The following method of application can be used to improve further understanding of the preparation method of the present invention. The specific material, class and condition have been determined to be further explication of the present invention, not to be any limit of the reasonable scope thereof. Reagents of the following synthetic compound showed in the table can either be purchased from the market or easily prepared by those skilled in the art.

Examples of representative compounds are as follows. Evaluation of biological activity: The activity level standard of harmful plant destruction (i.e. growth inhibition rate) is as follows: Level 10: completely dead; Level 9: above 95% growth inhibition rate; Level 8: above 90% growth inhibition rate; Level 7: above 80% growth inhibition rate; Level 6: above 70% growth inhibition rate; Level 5: above 60% growth inhibition rate; Level 4: above 50% growth inhibition rate; Level 3: above 20% growth inhibition rate; Level 2: 5-20% growth inhibition rate; Level 1: below 5% growth inhibition rate; Level 0: no effect. The above described growth inhibition rates are fresh weight inhibition rates. Experiment of post-emergence test: monocotyledonous and dicotyledonous weed seeds as well as main crop seeds (i.e., wheat, corn, rice, soybean, cotton, oilseed rape, millet and sorghum) were put into a plastic pot loaded with soil, then covered with 0.5-2 cm of soil, and the seeds were allowed to grow in good greenhouse environment. The test plants were treated at 4-5 leaf stage 2-3 weeks after sowing. The test compounds of the invention were dissolved in acetone respectively, then added with Tween-80 and diluted by a certain amount of water to give solutions with certain concentrations. The solution was sprayed to the plants with a sprayer. The plants were cultured for 3 weeks in the greenhouse. The experiment results of weed controlling effect after 3 weeks were listed in Table 3 and Table 4. Table 3. Experiment on weed control effect in Post-emergence stage Descurainia Galium aparine Abutilon Sagittaria Monochoria Compound No. sophia L. theophrasti trifolia L. vaginalis 1 10 10 10 10 10

2 10 10 10 10 10

3 10 10 10 10 10

4 10 10 10 10 10

5 10 10 10 10 10

6 10 10 10 10 10

7 10 10 10 10 10

8 10 10 10 10 10

9 10 10 10 10 10

10 10 10 10 10 10

I1 10 10 10 10 10

12 10 10 10 10 10

13 10 10 10 10 10

14 10 10 10 10 10

10 10 10 10 10

16 10 10 10 10 10

17 10 10 10 10 10

18 10 10 10 10 10

19 10 10 10 10 10

10 10 10 10 10

21 10 10 10 10 10

22 10 10 10 10 10

23 10 10 10 10 10

24 10 10 10 10 10

10 10 10 10 10

26 10 10 10 10 10

27 10 10 10 10 10

28 10 10 10 10 10

29 10 10 10 10 10

10 10 10 10 10

31 10 10 10 10 10

32 10 10 10 10 10

33 10 10 10 10 10

34 10 10 10 10 10

10 10 10 10 10

36 10 10 10 10 10

37 10 10 10 10 10

38 10 10 10 10 10

39 10 10 10 10 10

10 10 10 10 10

41 10 10 10 10 10

42 10 10 10 10 10

43 10 10 10 10 10

44 10 10 10 10 10

10 10 10 10 10

46 10 10 10 10 10

47 10 10 10 10 10

48 10 10 10 10 10

49 10 10 10 10 10

10 10 10 10 10

51 10 10 10 10 10

52 10 10 10 10 10

53 10 10 10 10 10

54 10 10 10 10 10

10 10 10 10 10

56 10 10 10 10 10

57 10 10 10 10 10

58 10 10 10 10 10

59 10 10 10 10 10

10 10 10 10 10

61 10 10 10 10 10

62 10 10 10 10 10

63 10 10 10 10 10

64 10 10 10 10 10

10 10 10 10 10

66 10 10 10 10 10

67 10 10 10 10 10

68 10 10 10 10 10

69 10 10 10 10 10

10 10 10 10 10

71 10 10 10 10 10

72 10 10 10 10 10

73 10 10 10 10 10

74 10 10 10 10 10

10 10 10 10 10

76 10 10 10 10 10

77 10 10 10 10 10

78 10 10 10 10 10

79 10 10 10 10 10

10 10 10 10 10

81 10 10 10 10 10

82 10 10 10 10 10

83 10 10 10 10 10

84 10 10 10 10 10

10 10 10 10 10

86 10 10 10 10 10

87 10 10 10 10 10

88 10 10 10 10 10

89 10 10 10 10 10

10 10 10 10 10

91 10 10 10 10 10

92 10 10 10 10 10

93 10 10 10 10 10

94 10 10 10 10 10

10 10 10 10 10

96 10 10 10 10 10

97 10 10 10 10 10

98 10 10 10 10 10

99 10 10 10 10 10

100 10 10 10 10 10

101 10 10 10 10 10

102 10 10 10 10 10

103 10 10 10 10 10

104 10 10 10 10 10 Control 6 4 5 5 6 Compound A Note: The application rate was 45g/ha of active ingredient, with 450kg/ha of adding water. 0 N 'N ;-- 'N I

Control Compound A: NH2 (CN102675218B). Table 4. Experiment on weed control effect in Post-emergence stage

Sagittaria Veronica Rorippa Leptochloa Echinochloa No. Corn Rice trifolia L. didya indica chinensis crusgalli 9 1 1 10 10 6 7 10 99 1 1 10 10 7 8 10 Control 3 2 5 3 6 2 3 Compound A Control 8 5 10 9 3 5 8 Compound B Control 7 5 10 2 2 3 8 Compound C Note: The application rate was 30g/ha of active ingredient, with 450kg/ha of adding water. NH 2

N CI

N COOH C1 Control Compound B: OMe ;Control Compound C: halauxifen-methyl. According to Table 3 and Table 4, compared with the control compounds, the crop safety and herbicidal activity of the compounds of the present invention are significantly improved by changing the mother ring structure, the substituent, as well as the type of the carboxyl derivative, especially the compounds of the present invention have good selectivity for important crops such as corn, rice, and the like, while the control compounds have poor selectivity for major crops. It demonstrates that the present invention has excellent technical effects. Experiment of pre-emergence test: Seeds of monocotyledonous and dicotyledonous weeds and main crops (e.g. wheat, corn, rice, soybean, cotton, oilseed rape, millet and sorghum) were put into a plastic pot loaded with soil and covered with 0.5-2cm of soil. The test compounds of the present 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 sowing. The obtained seeds were incubated for 4 weeks in the greenhouse after spraying. The test results were observed 3 weeks later. It was observed that the herbicides of the present invention mostly had excellent effect at dose of 250g/ha, especially to weeds such as Echinochloa crusgalli, Digitariasanguinalis and Abutilon theophrasti, etc., and many compounds had good selectivity for corn, wheat, rice, soybean, oilseed rape, etc. It is indicated from the experiment that the compound of the present invention generally have good weed control efficacy, especially for major grass weeds such as Echinochloa crusgalli,

Digitaria sanguinalis and Setaria viridis, etc. and major broad-leaved weeds such as Abutilon theophrasti, Rorippa indica and Bidens pilosa, which are widely occurred in corn, rice and wheat fields, and have excellent commercial value. Above all, it is noted that the compound of the invention have extremely high activity to broad-leaved weeds, which are resistant to ALS inhibitor, like Rorippa indica, Descurainiasophia, Capsella bursa-pastoris,Lithospermum arvense, Galium aparineand Stellaria media, etc.. Transplanted rice safety evaluation and weed control effect evaluation in rice field: Rice field soil was loaded into a 1/1,000,000 ha pot. The seeds of Echinochloa crusgalli, Scirpus juncoides, Bidens tripartiteand Sagittaria trifolia L. were sowed and gently covered with soil, then left to stand still in greenhouse in the state of 0.5-1cm of water storage. The tuber of Sagittaria trifolia L. was planted in the next day or 2 days later. 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 preparation method of the compounds of the present invention with pipette homogeneously to achieve specified effective amount when Echinochloa crusgalli, Scirpus juncoides and Bidens tripartite reached 0.5 leaf stage and Sagittaria trifolia L. reached the time point of primary 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 3cm of transplanting depth the next day. The compound of the present invention was treated by the same way after 5 days of transplantation. The fertility condition of Echinochloa crusgalli, Scirpus juncoides, Bidens tripartite and Sagittariatrifolia L. 14 days after the treatment of the compound of the invention and the fertility condition of rice 21 days after the treatment of the compound of the invention respectively with the naked eye. Evaluate the weed control effect with 1-10 activity standard level. It has been found that many of the compounds have excellent activity and selectivity, Note: The seeds of Echinochloa crusgalli, Scirpusjuncoides, Sagittaria trifolia L. and Bidens tripartitewere collected from Heilongjiang Province of China. Tests indicated that the weeds were resistant to common rate of pyrazosulfuron-ethyl. At the same time, it is found after several tests that the compound of the present invention have good selectivity to many gramineae grasses such as zoysia japonica, bermuda grass, tall fescue, bluegrass, ryegrass and seashore paspalum etc, and are able to control many important grass weeds and broadleaf weeds. The compounds also show excellent selectivity and commercial value in the tests on soybean, cotton, oil sunflower, potato, orchards and vegetables in different herbicide application methods.

Claims

Claims 1. A type of substituted pyrimidinyl formyl oxime derivative, as shown in general formula I: Y x CN N R2

Cj A 0 B

wherein, Ri and R2 independently represent H, halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, acyloxy, alkylthio, unsubstituted or substituted aryl, unsubstituted or substituted benzyl, unsubstituted or substituted heteroaryl, unsubstituted or substituted aryloxy, unsubstituted or substituted arylthio, unsubstituted or substituted heteroaryloxy, unsubstituted or substituted heteroarylthio or the group represented by the formula of -COR, wherein, R5 represents alkyl, haloalkyl, alkenyl, cycloalkyl, alkoxy, alkenoxy, cycloalkoxy, alkylthio, alkenylthio, cycloalkylthio, unsubstituted or substituted benzyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted aryloxy, unsubstituted or substituted heteroaryloxy, unsubstituted or substituted aryl methoxy, unsubstituted or substituted heteroaryl methoxy, unsubstituted or substituted benzylthio, unsubstituted or substituted arylthio, unsubstituted or substituted heteroarylthio, or amino which is optionally substituted by alkyl, acyl, acyloxy, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted arylalkyl or unsubstituted or substituted heteroarylalkyl; or Riand R2 are linked to form a 5- or 6-member saturated or unsaturated ring; X represents alkyl, alkoxy, alkylthio, halogen, alkenyl or alkynyl; Y represents nitro or NR3R4, wherein, R3 represents H, alkyl, alkenyl, alkynyl, -COR12, nitro, OR13, S02R14, NR15Ri, N=CR17Ri, alkyl carbamoyl, dialkyl carbamoyl, trialkyl silyl or dialkyl

phosphono, wherein the alkyl, alkenyl and alkynyl are independently optionally substituted by one or two Rii; R4 represents H, alkyl or -COR12, the alkyl is optionally substituted by one or two Rii; or NR3R4 represents N=CR21NR22R23, N=CR240R25or 5- or 6-member saturated or unsaturated ring which is unsubstituted or substituted by one or two groups selected from halogen, alkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino and alkoxy carbonyl, and contains or does not contain oxygen atom, sulfur atom or other nitrogen atom; wherein, Rii independently represents halogen, hydroxy, alkoxy, haloalkoxy, alkylthio, haloalkylthio, amino, alkylamino, dialkylamino, alkoxy carbonyl, unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl; R12 represents H, alkyl, haloalkyl, alkoxy, phenyl, phenoxy or benzyloxy; R13 represents H, alkyl, haloalkyl, phenyl, benzyl or CHR3C(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, alkoxy carbonyl, phenyl carbonyl, phenoxy carbonyl or benzyloxy carbonyl; R16 represents H or alkyl; R17 represents H, alkyl or phenyl, said phenyl is unsubstituted or substituted by 1-3 groups selected from halogen, alkyl and alkoxy; Ri8 represents H or alkyl; or N=CR17Ri8 represents or; R21 and R24 each independently represent H or alkyl; R22 and R23 each independently represent H or alkyl; or NR22R23 represents 5- or 6-member saturated or unsaturated ring not containing or containing oxygen atom, sulfur atom or other nitrogen atom; R25 represents alkyl; A represents halogen or amino; B represents hydrogen, halogen, alkoxy, alkylthio, alkylamino or dialkylamino, the alkoxy, alkylthio, alkylamino and dialkylamino are independently unsubstituted or substituted by halogen; C represents halogen or haloalkyl.
2. The substituted pyrimidinyl formyl oxime derivative according to claim 1, wherein, Ri and R2 independently represent H, cyano, Cl-C8 alkyl, halo Cl-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, Cl-C8 alkoxy, Cl-C8 acyloxy, Cl-C8 alkylthio, unsubstituted or substituted aryl, unsubstituted or substituted benzyl, unsubstituted or substituted heteroaryl, unsubstituted or substituted aryloxy, unsubstituted or substituted arylthio, unsubstituted or substituted heteroaryloxy, unsubstituted or substituted heteroarylthio or the group represented by the formula of -COR5, wherein, R5 represents Cl-C8 alkyl, halo Cl-C8 alkyl, C2-C8 alkenyl, C3-C8 cycloalkyl, Cl-C8 alkoxy, C2-C8 alkenoxy, C3-C8 cycloalkoxy, Cl-C8 alkylthio, C2-C8 alkenylthio, C3-C8 cycloalkylthio, unsubstituted or substituted benzyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted aryloxy, unsubstituted or substituted heteroaryloxy, unsubstituted or substituted aryl methoxy, unsubstituted or substituted heteroaryl methoxy, unsubstituted or substituted benzylthio, unsubstituted or substituted arylthio, unsubstituted or substituted heteroarylthio or amino which is optionally substituted by Cl-C8 alkyl, Cl-C8 acyl, Cl-C8 acyloxy, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted aryl Cl-C8 alkyl or unsubstituted or substituted heteroaryl Cl-C8 alkyl; wherein, said "substituted" refers to being substituted by one or more groups selected from halogen, cyano, nitro, Cl-C8 alkyl, halo Cl-C8 alkyl, C3-C8 cycloalkyl, Cl-C8 alkoxy, C2-C8 alkenoxy, Cl-C8 alkylthio, aryl, aryloxy, benzyl, benzyloxy, Cl-C8 acyl, Cl-C8 acyloxy, C2-C8 alkenyl and amino which is optionally substituted by Cl-C8 alkyl, aryl, aryloxy, Cl-C8 acyl, Cl-C8 acyloxy or

C2-C8 alkenyl; X represents Cl-C8 alkyl, Cl-C8 alkoxy, Cl-C8 alkylthio, halogen, C2-C8 alkenyl or C2-C8 alkynyl; Y represents nitro or NR3R4, wherein, R3 represents H, Cl-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, -COR12, nitro, OR13, S02R4, NR15Ri, N=CR17Ri, Cl-C8 alkyl carbamoyl, diCl-C8 alkyl carbamoyl, triCl-C8 alkyl silyl or diCl-C8 alkyl phosphono, the Cl-C8 alkyl, C2-C8 alkenyl and C2-C8 alkynyl are independently optionally substituted by one or two Rii; R4 represents H, Cl-C8 alkyl or -COR12, the Cl-C8 alkyl is optionally substituted by one or two Rii; or NR3R4 represents

N=CR21NR22R23, N=CR240R25, N2 N N or , the -N N

N N N /, and 0 are independently unsubstituted or substituted by 1-2 groups selected

from halogen, Cl-C8 alkyl, Cl-C8 alkoxy, halo Cl-C8 alkoxy, Cl-C8 alkylthio, halo Cl-C8 alkylthio, amino, Cl-C8 alkyl amino, diCl-C8 alkyl amino and Cl-C8 alkoxy carbonyl; wherein, Rii independently represents halogen, hydroxy, Cl-C8 alkoxy, halo Cl-C8 alkoxy, Cl-C8 alkylthio, halo Cl-C8 alkylthio, amino, Cl-C8 alkyl amino, diCl-C8 alkyl amino, Cl-C8

0 S HN N alkoxy carbonyl, phenyl, naphthyl , - , N, N or N ,the

0 S phenyl, naphthyl, '/ / - N , N and N are independently

unsubstituted or substituted by 1-3 groups selected from halogen, Cl-C8 alkyl, Cl-C8 alkoxy and nitro; R12 represents H, C1-C18 alkyl, halo Cl-C8 alkyl, Cl-C8 alkoxy, phenyl, phenoxy or benzyloxy; R13 represents H, Cl-C8 alkyl, halo Cl-C8 alkyl, phenyl, benzyl or CHR31C(O)OR32; R31 represents H, Cl-C8 alkyl or Cl-C8 alkoxy; R32 represents H, Cl-C8 alkyl or benzyl; R14 represents Cl-C8 alkyl or halo Cl-C8 alkyl; R15 represents H, Cl-C8 alkyl, formyl, Cl-C8 alkyl acyl, halo Cl-C8 alkyl acyl, Cl-C8 alkoxy carbonyl, phenyl carbonyl, phenoxy carbonyl or benzyloxy carbonyl; R16 represents H or Cl-C8 alkyl; R17 represents H, Cl-C8 alkyl or phenyl, said phenyl is unsubstituted or substituted by 1-3 groups selected from halogen, Cl-C8 alkyl and Cl-C8 alkoxy; Ris represents H or Cl-C8 alkyl; or

N N=CR17Ris represents - or 'A;N0 R21 and R24 each independently represent H or Cl-C8 alkyl;

R22 and R23 each independently represent H or Cl-C8 alkyl; or NR22R23 represents

Y-N-JN 7 N0o or 0.' R25 represents Cl-C8 alkyl; A represents halogen or amino; B represents hydrogen, halogen, Cl-C8 alkoxy, Cl-C8 alkylthio, Cl-C8 alkyl amino or diCl-C8 alkyl amino, the Cl-C8 alkoxy, Cl-C8 alkylthio, Cl-C8 alkyl amino and diCl-C8 alkyl amino are independently unsubstituted or substituted by halogen; C represents halogen or halo Cl-C8 alkyl.
3. The substituted pyrimidinyl formyl oxime derivative according to claim 1 or 2, wherein, Ri and R2 independently represent hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, cyano, C1-C6 alkoxy carbonyl or phenyl, said phenyl is unsubstituted or substituted by one or more groups selected from halogen, halo C1-C6 alkyl, C1-C6 alkyl, C1-C6 alkoxy and C2-C6 alkenyl; X represents C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, halogen, C2-C6 alkenyl or C2-C6 alkynyl; Y represents nitro or NR3R4, wherein, R3 represents H, Cl-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, -COR12, nitro, OR13, S02R4, NR15Ri, N=CR17Ri, Cl-C6 alkyl carbamoyl, diCl-C6 alkyl carbamoyl, triCl-C6 alkyl silyl or diCl-C6 alkyl phosphono, the C1-C6 alkyl, C2-C6 alkenyl and C2-C6 alkynyl are independently optionally substituted by one or two Rii; R4 represents H, Cl-C6 alkyl or -COR12, the C1-C6 alkyl is optionally substituted by one or two Rii; or NR3R4 represents

N=CR21NR22R23, N=CR240R25, N N N or , the FNc N

N ~N N,) and 0 are independently unsubstituted or substituted by 1-2 groups selected

from halogen, C1-C6 alkyl, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkyl amino, diC1-C6 alkyl amino and C1-C6 alkoxy carbonyl; wherein, Rii independently represents halogen, hydroxy, C1-C6 alkoxy, halo C1-C6 alkoxy, C1-C6 alkylthio, halo C1-C6 alkylthio, amino, C1-C6 alkyl amino, diCl-C6 alkyl amino, C1-C6

~ 0H N

alkoxy carbonyl, phenyl, naphthyl, Q--//N - N N or t Nthe

0 S H phenyl, naphthyl, N), N and are independently

unsubstituted or substituted by 1-3 groups selected from halogen, C1-C6 alkyl, C1-C6 alkoxy and nitro;

R12 represents H, C1-C14 alkyl, halo C1-C6 alkyl, C1-C6 alkoxy, phenyl, phenoxy or benzyloxy; R13 represents H, Cl-C6 alkyl, halo C1-C6 alkyl, phenyl, benzyl or CHR31C(O)OR32; R31 represents H, Cl-C6 alkyl or Cl-C6 alkoxy; R32 represents H, Cl-C6 alkyl or benzyl; R14 represents Cl-C6 alkyl or halo C1-C6 alkyl; RI represents H, Cl-C6 alkyl, formyl, Cl-C6 alkyl acyl, halo C1-C6 alkyl acyl, C1-C6 alkoxy carbonyl, phenyl carbonyl, phenoxy carbonyl or benzyloxy carbonyl; R16 represents H or Cl-C6 alkyl; R17 represents H, Cl-C6 alkyl or phenyl, said phenyl is unsubstituted or substituted by 1-3 groups selected from halogen, C1-C6 alkyl and C1-C6 alkoxy; Ris represents H or Cl-C6 alkyl; or

N=CR17Ris represents . or -0 ; R21 and R24 independently represent H or Cl-C6 alkyl;

4N3N R22 and R23 independently represent H or Cl-C6 alkyl; orNR22R23 represents ,N

, N N N or N

R25 represents C1-C6 alkyl; A represents halogen or amino; B represents hydrogen, halogen, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkyl amino or diC1-C6 alkyl amino, the C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkyl amino and diC1-C6 alkyl amino are independently unsubstituted or substituted by halogen; C represents halogen or halo C1-C6 alkyl.
4. The substituted pyrimidinyl formyl oxime derivative according to any one of claims I to 3, wherein, Ri and R2 independently represent hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, cyano, C1-C4 alkoxy carbonyl or phenyl, said phenyl is unsubstituted or substituted by one or more groups selected from halogen, halo C1-C4 alkyl, C1-C4 alkyl, C1-C4 alkoxy and C2-C4 alkenyl; X represents C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, halogen, C2-C4 alkenyl or C2-C4 alkynyl; Y represents nitro or NR3R4, wherein, R3 represents H, Cl-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, -COR12, nitro, OR13, S02R14, NR15Ri, N=CR17Ri, Cl-C4 alkyl carbamoyl, diCl-C4 alkyl carbamoyl, triC1-C4 alkyl silyl or diC1-C4 alkyl phosphono, the C1-C4 alkyl, C2-C4 alkenyl and C2-C4 alkynyl are independently optionally substituted by 1-2 Rii; R4 represents H, Cl-C4 alkyl or -COR12, the C1-C4 alkyl is optionally substituted by one or two Rii; or NR3R4 represents

N=CR21NR22R23, N=CR240R25, N N/ N or ,the N' N

N 'N N /, and 0 are independently unsubstituted or substituted by 1-2 groups selected

from halogen, C1-C4 alkyl, C1-C4 alkoxy, halo C1-C4 alkoxy, C1-C4 alkylthio, halo C1-C4 alkylthio, amino, C1-C4 alkyl amino, diC1-C4 alkyl amino and C1-C4 alkoxy carbonyl; wherein, Rii independently represents halogen, hydroxy, C1-C4 alkoxy, halo C1-C4 alkoxy, C1-C4 alkylthio, halo C1-C4 alkylthio, amino, C1-C4 alkyl amino, diC1-C4 alkyl amino, C1-C4

0HN S -N N alkoxy carbonyl, phenyl, naphthyl,*,2- ,N , N or N ,the

H 0 S _ N phenyl, naphthyl, - /, "&, N , N and N are independently

unsubstituted or substituted by 1-3 groups selected from halogen, C1-C4 alkyl, C1-C4 alkoxy and nitro; R12 represents H, Cl-C8 alkyl, halo C1-C4 alkyl, C1-C4 alkoxy, phenyl, phenoxy or benzyloxy; R13 represents H, Cl-C4 alkyl, halo C1-C4 alkyl, phenyl, benzyl or CHR31C(O)OR32; R31 represents H, Cl-C4 alkyl or Cl-C4 alkoxy; R32 represents H, Cl-C4 alkyl or benzyl; R14 represents Cl-C4 alkyl or halo C1-C4 alkyl; RI represents H, Cl-C4 alkyl, formyl, Cl-C4 alkyl acyl, halo C1-C4 alkyl acyl, C1-C4 alkoxy carbonyl, phenyl carbonyl, phenoxy carbonyl or benzyloxy carbonyl; R16 represents H or Cl-C4 alkyl; R17 represents H, Cl-C4 alkyl or phenyl, said phenyl is unsubstituted or substituted by 1-3 groups selected from halogen, C1-C4 alkyl and C1-C4 alkoxy; Ris represents H or Cl-C4 alkyl; or N - N-0 N=CR17Ris represents or R21 and R24 independently represent H or Cl-C4 alkyl;

-GN N R22 and R23 independently represent H or Cl-C4 alkyl; orNR22R23 represents , 1,

N or 0.

R25 represents Cl-C4 alkyl; A represents halogen or amino;

B represents hydrogen, halogen, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkyl amino or diC1-C4 alkyl amino, the C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkyl amino and diC1-C4 alkyl amino are independently unsubstituted or substituted by halogen; C represents halogen or halo C1-C4 alkyl.
5. The substituted pyrimidinyl formyl oxime derivative according to claim 1, wherein, Ri and R2 independently represent hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, methylthio, ethylthio, cyano, methoxycarbonyl, ethoxycarbonyl or phenyl, said phenyl is unsubstituted or substituted by one or more groups selected from halogen, CF3, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, methoxy and ethoxy; X represents chlorine, bromine, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl;

SH H N'H N H 'H N' H Y represents NH2, NHMe, N(Me)2, COCH 3 , N N

0 H 00 O H 'OH or-

A represents fluorine, chlorine or amino; B represents hydrogen, fluorine, chlorine, methoxy, ethoxy or methylthio, the methoxy, ethoxy and methylthio independently contain or don't contain fluorine; C represents fluorine, chlorine or trifluoromethyl.
6. The substituted pyrimidinyl formyl oxime derivative according to claim 1, wherein, its structural formula is any of the following: NH 2 NH 2 NH2

NC N CN "'N 'NjI C #N 0 '' -N

CI F F 0'C OMe OMe OMe 1 2 3

F F F 0

NH 2 NH 2 HN

C NICI O CO

N '

C1 0 0 0-CI F F CI #

OMe OMe OMe 4 5 6

NH 2 N NH 2 NH 2 c 7 0 N7 S N N 'NN NN N N 0N cI F 0 ClC1) :F 0 7C F 0Me OMe OMe 7 8 9 NH 2 N NH 2 clNH c 2 N N 0, N, 'NN N 'N NN '-N 0 CIJ F 0 CI j70 0 70 F 0Me 0Me 0Me 10 11 12

NH 2 NH 2 N2c N CI7 N7 CI N7 0 N~ 0 N N O'N CI " 0,N 0--*"" Cl: N 0, N 0 0 CI 0CIJ;

OMeOe 13 14 CF 3 15

NH 2 NH 2 NH 2 c

N0 ' " 0N N , N'N C N N ' 0 CIF 0" FC NH 2 c OMe Fc l 03

16 17 18 F

NH 2 NNH 2 0-NH 2 Nl 7 7 7 N Br N "I N C 0 N N N 'N' N N N N NN 'N ci0 1710 C1Br c N H2 C NH 2 0c Is19 -0 20 F2HC' 21 C

0

NHN

0 'N,~ NC ~ N N ,N IN N Y N N F F 3C F 0 701 71 '

F3-22 F3C- 23 24

NH2 CI NH2NH 2 0~7 N --N N N N7 Br 0, 0 CI F 0cl F N~ 7 NN l-- F 0 N02 rN F 3C' F 0CN 0 F O cl25 IIH26 F 3C' 27

NH 2 o ANH NH 2

N 0 N 0 s N O zN2 'N N N '#N 0 O'N N N' N

' 0Ny -II 0 F 3 C' F N C CI S, CI N 0O8 e 29 C OMe F 30 0 A HNH 2 'NNH 2

CI 0 N" N" 5' ONN N' N N

CI ' F " N' 0 'NCI '[: F CIl F 0 *) W~e 31H OMe 32OMe 3

N N NCII 'N ~ ' N N' ~ 0N-'N

17 N0 HN 0 7N

' CI FH2 N Cl '? F' 0 l) :c 0Me 34OMe 35Me 36

N -'NH 2 "NH 2

0c - 00

' N -N -N O- N 'N N N CF'NCI F CI F 'N 'N'

' OMe OMe OMe 37 38 39

NH 2 NH2 'N

N I N 0' N' 0 N 70 N N 0 N 0 NCl N Cl F 0 C: Cl OMeCI#FC'N24 40 OMe 41 ,04

Cl0

NH 2 'NNH 2 'NNH 2 Cl HN 0 N- S 0 NH N- F 0 NH N-' 'N N 0 'N- 0 ' N 0 'N- 17 'N Br N 0,N N I'

l Ci l 0 B Cl NH 2 0'N 1 s43 1 0 44F 2 HC- 45

NH 2 NH 2 ( cr Br 0 NH N- N7 NH C 0 " N' N:r N9 2 N N N 0'N N 0 N F3 C0 N H2 0FC 'FF 3Cq I,, F 46 F3C0 47 7- 70 48

NH 2 N NH 2 NNH 2 H 7-1 0 N7 0 0 0 NN N N N 0,7 N N N 1 N 07 ' 0 N o, 0.9 'N

7 - - CI F 0 CI F' CI J:; OMe OMe OMe 49 50 51 NH 2 NH 2 NH 2

N N N l oxN 0- NN; 0 N NN 7 -

' F 7 0 0 2CI Br CI ' ]F - FC52 F2 HC- 53 OMe 5

N NH NH2 N2BrN c

N N 'N- N N N N a l N N N 'N 7 7 CI F 0 7Cl# B 0 7101- 0

OMe 55FHC- 0 56 OMe 5

H'OH H HN"N7 0 clN Br N' 0

I , N 0' 'Ny Nj'l NN07 N Olxl- e OMe Ol q e Me 58 59 Oe 60 0

N HO Oz CF 3 0 N LN ' NH NHN'NH

N Nl 07 N' 07 N0N N N N 'N0 N N N 'N0 N 7 - - X! F , - 0 7Cl % 0 7 OMe 61OMe 62OMe 6

HN 0 c F HN HN>T

Nl N N'N

701~ cCIe 011 ci cl 0 OMe 64 Oe 65 Me66

,0 NH ~'NHN N~ NN N1Br

--N y 0N 0 N 01 0 CI F cI F 7 Ci OMe 67 OMe 68 Oe 69

2 HN'NH2 0' "NH HN'

N 'Br N~ 0-- c

0, ". N N N N N W I~~C CII F 0 CIC

O2SN 0 N Fcl CF3

HN 0 H 02N N'3H O

N I l NN.c-0. c*,

N N y ,N "' 0N N NNy N N

CI F 0 ""IF 0 'CIF 0 OMe 73Me 74Me 7

0~'

'0

NO 2 clF NHN clHN B N I 'N' 7 N7 0 'N' NOz:

FN 0 Cl F 010 CI) OMe 76 OMe 77OMe 78

,F N02 'F CF 3I

HN HNHN CI 0 N cN C)-. 'N N N

7011 F N Oe 79 Oe 80 OMe 81

0 CF 3 '~

HN HN? H HN

''N YN"NC N'.N YN jN' 'N N YN CIF1 0 1 OMe 82 ~O83 OMe 84

sN-NH NH

HN NE HN clH N CI , N- N7

-- N 'N 0, N N N ON'N` ~r 0 'N -- x:_ F ~CiF ( NH2 C I ):NH OMe 85 86 O 8

NN

KNH HN HN cl N cl N Br

- N N N N "N 0, N N 0,N-' 0 0,0 0 CI NH 2 CI j::F F 88 OMe 89 OMe 90

N

y HN HN H

0 N N 'T NC N N 0 N C

cI F 0 ON N0N oi- 0Me OMe 11 CI F 91 92 OMe 93

NN

N HN HN CN C CO N I NN

0 NN N 0F 'N N 'N 0CI ' 0 70 CI ; 4 Fl 7 OMe 95 9 96

I CI C H2N H2 ' N NN N~ HN NN

F 0 F 'NF 'NF 7 N N NN N N N N N N0 CNI NH0N CNI o0 H2N O N H2N N H2 N C1 0 CI 0 CI 0 CI 0 '

97 98 99 100

IC

NH 2 C1NH 'N 2

N 0,7 0 N7 N ' N N N ' N Y N' 0 OU H H2 N 'N0 C1) F 01 '] F 0 0N 101 102 13or N N CI

H2 N N H CI 0 104
7. Amethod for preparing the substituted pyrimidinyl formyl oxime derivative according to any one of claims Ito 6,which comprises the following steps: subjecting the compound of the general formulaI11and the compound of the general formula III to reaction to obtain the compound of the general formula, the chemical reaction scheme is asfollows: Y Y

OH 0 ,l -N + HOK -- N N R2 C 0 N R2 A B B

preferably, said reaction is performed under the action of base and condensation agent and in aprotic solvent; preferably, the temperature of said reaction is from 0 °C to 90 °C, further preferably, from 25 °C to 30 °C; said solvent is one solvent or more mixed solvents selected from dichloromethane, dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, toluene and xylene; said base is one or more selected from triethylamine, trimethylamine, DIPEA and DBU; said condensation agent is PyBop, HATU or HOBt-EDCI.
8. A herbicidal composition, wherein, the composition comprises a herbicidally effective amount of at least one of the substituted pyrimidinyl formyl oxime derivative according to any one of claims 1 to 6, preferably, further comprises formulation auxiliary.
9. A method for controlling a harmful plant, comprising applying a herbicidally effective amount of at least one of the substituted pyrimidinyl formyl oxime derivative according to any one of claims 1 to 6, or the herbicidal composition according to claim 8 to the harmful plant or an area with the harmful plant.
10. Use of at least one of the substituted pyrimidinyl formyl oxime derivative according to any one of claims 1 to 6, or the herbicidal composition according to claim 8 for controlling a harmful plant, preferably, the substituted pyrimidinyl formyl oxime derivative is used to control a harmful plant in a useful crop, the useful crop is a genetically modified crop or a crop treated by genome editing technique.