FIVE-MEMBERED RING-SUBSTITUTED PYRIDAZINOL COMPOUNDS AND DERIVATIVES, PREPARATION METHODS, HERBICIDAL COMPOSITIONS AND APPLICATIONS THEREOF

Abstract

The invention belongs to the technical field of agricultural chemicals, and in particular relates to a five-membered ring-substituted pyridazinol compound and a derivatives thereof, preparation method, herbicidal composition and application thereof. The compound is as shown in Formula I:

##STR00001## wherein, X is halogen, cyano, alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, R.sub.1R.sub.2N(CO), or R.sub.1R.sub.2N, etc.; Ar is

##STR00002##

Het is a 5-membered unsaturated ring, the ring contains, besides the 1-C atom, 0 to 4 atoms or radicals follows to form the ring: O, NR.sub.b, S; R.sub.a is one or more groups selected from: hydrogen, halogen, RO(CH.sub.2).sub.n, and R.sub.1R.sub.2R.sub.3SiO, etc.; m is 0 or 1, n and q are independently an integer from 0 to 8, p is an integer from 1 to 8; R is hydrogen, or a halogen-containing or not containing group selected from alkyl, and alkenyl, etc.; R.sub.b, R.sub.1, R.sub.2, R.sub.3 are each independently hydrogen, nitro, hydroxy, or amino, etc. The compound and the derivative, as well as the composition thereof have very high herbicidal activity and good selectivity, and are safe for crops.

Claims

1. A five-membered ring-substituted pyridazinol compound of Formula I or a derivative thereof: ##STR00661## wherein, X is halogen, cyano, alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, R.sub.1R.sub.2N(CO), R.sub.1R.sub.2N, hydroxy, or unsubstituted or substituted aryl; Ar is ##STR00662## Het is a 5-membered unsaturated ring, the ring contains, besides the 1-C atom, 0 to 4 atoms or radicals follows to form the ring: O, NR.sub.b, S; R.sub.a is one or more groups selected from: hydrogen, halogen, cyano, nitro, azido, a halogen-containing or not containing group selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkylalkyl, a group selected from aryl, arylalkyl, heteroaryl, and heteroarylalkyl, which is unsubstituted or substituted, RO(CH.sub.2).sub.n, RO(CH.sub.2).sub.pO(CH.sub.2).sub.q, RO(CH.sub.2).sub.pS(CH.sub.2).sub.q, RS(CH.sub.2).sub.n, RS(CH.sub.2).sub.pO(CH.sub.2).sub.q, RS(CH.sub.2).sub.pS(CH.sub.2).sub.q, RO(CH.sub.2).sub.n(CO)(CH.sub.2).sub.q(O).sub.m, RS(CH.sub.2).sub.n(CS)(CH.sub.2).sub.q(S).sub.m, RO(CH.sub.2).sub.n(CO)(CH.sub.2).sub.q(S).sub.m, RO(CH.sub.2).sub.n(CS)(CH.sub.2).sub.q(O).sub.m, RS(CH.sub.2).sub.n(CO)(CH.sub.2).sub.q(O).sub.m, RO(CH.sub.2).sub.n(CS)(CH.sub.2).sub.q(S).sub.m, RS(CH.sub.2).sub.n(CO)(CH.sub.2).sub.q(S).sub.m, RS(CH.sub.2).sub.n(CS)(CH.sub.2).sub.q(O).sub.m, R(CO)(CH.sub.2).sub.n, R(CS)(CH.sub.2).sub.n, R(CO)(CH.sub.2).sub.nO(CH.sub.2).sub.q, R(CS)(CH.sub.2).sub.nS(CH.sub.2).sub.q, R(CO)(CH.sub.2).sub.nS(CH.sub.2).sub.q, R(CS)(CH.sub.2)O(CH.sub.2).sub.q, RSO(CH.sub.2)(O).sub.m, RSO(CH.sub.2)(S).sub.m, RSO(CH.sub.2).sub.n(NR.sub.3).sub.m, RSO.sub.2(CH.sub.2).sub.n(O).sub.m, RSO.sub.2(CH.sub.2).sub.n(S).sub.m, RSO.sub.2(CH.sub.2).sub.n(NR.sub.3).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.n, R.sub.1R.sub.2N(CH.sub.2).sub.nO(CH.sub.2).sub.q(O).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.nO(CH.sub.2).sub.q(S).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.nO(CH.sub.2).sub.q(NR.sub.3).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.n(CO)(CH.sub.2).sub.q(O).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.n(CO)(CH.sub.2).sub.q(S).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.n(CO)(CH.sub.2).sub.q(NR.sub.3).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.nSO.sub.2(CH.sub.2).sub.q(O).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.nSO.sub.2(CH.sub.2).sub.q(S).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.nSO.sub.2(CH.sub.2).sub.q(NR.sub.3).sub.m, R.sub.1R.sub.2PO.sub.3(O).sub.m(CH.sub.2).sub.q, R.sub.1R.sub.2R.sub.3SiO(CH.sub.2).sub.q, R.sub.1R.sub.2R.sub.3Si(CHCH).sub.m(CH.sub.2).sub.q, R.sub.1R.sub.2CN(O).sub.m(CH.sub.2).sub.n, and R.sub.1R.sub.2CNNH(CH.sub.2).sub.n; or two adjacent R.sub.a form OCH.sub.2O, CH.sub.2CH.sub.2O, OCH.sub.2CH.sub.2O, OCH(CH.sub.3)O, OC(CH.sub.3).sub.2O, OCF.sub.2O, CF.sub.2CF.sub.2O, OCF.sub.2CF.sub.2O, or CHCHCHCH; m is 0 or 1, n and q are independently an integer from 0 to 8, p is an integer from 1 to 8; R is hydrogen, a halogen-containing or not containing group selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkylalkyl, or a group selected from aryl, arylalkyl, heteroaryl, and heteroarylalkyl, which is unsubstituted or substituted; R.sub.b, R.sub.1, R.sub.2, R.sub.3 are each independently hydrogen, nitro, hydroxy, amino, a halogen-containing or not containing group selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkoxyalkyl, alkoxycarbonyl, alkylsulfanylcarbonyl, alkylsulfonyl, alkylsulfonylalkyl, alkylcarbonyl, alkylcarbonylalkyl, alkylcarbonyloxy, alkylamino, alkylaminocarbonyl, alkoxyaminocarbonyl, alkoxycarbonylalkyl, alkylaminocarbonylalkyl, trialkylsilyl, and dialkylphosphonyl, or a group selected from 6-membered heterocyclyl, aryl, arylalkyl, aryloxy, arylalkyloxy, aryloxyalkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroarylalkyl, heteroaryloxy, heteroarylalkyloxy, heteroaryloxyalkyl, heteroarylcarbonyl, and heteroarylsulfonyl, which is unsubstituted or substituted; or R.sub.1R.sub.2N forms a 6-membered heterocyclyl; or adjacent R.sub.a and R.sub.b form CH.sub.2CH.sub.2NR.sub.3CH.sub.2.

2. The five-membered ring-substituted pyridazinol compound or a derivative thereof according to claim 1, wherein, X is halogen, cyano, C.sub.1-8alkyl, halogenated C.sub.1-8alkyl, C.sub.1-8alkoxy, halogenated C.sub.1-8alkoxy, R.sub.1R.sub.2N(CO), R.sub.1R.sub.2N, hydroxy, or aryl, said aryl is unsubstituted or substituted with 15 substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, carboxyl, sulfhydryl, amino, and a halogen-containing or not containing group selected from C.sub.1-8alkyl, C.sub.3-8cycloalkyl, C.sub.3-8cycloalkyl-C.sub.1-8alkyl, C.sub.2-8alkenyl, C.sub.2-8alkynyl, C.sub.1-8alkoxy, C.sub.1-8alkylcarbonyl, C.sub.1-8alkoxycarbonyl, C.sub.1-8alkylsulfonyl, C.sub.1-8alkylamino, and C.sub.1-8alkylcarbonyloxy; Ar is ##STR00663## Het is a 5-membered unsaturated heterocycle, the heterocycle contains, besides the 1-C atom, 1 to 4 atoms or radicals follows to form the ring: O, NR.sub.b, S; R.sub.a is one or more substituents selected from: hydrogen, halogen, cyano, nitro, azido, a halogen-containing or not containing group selected from C.sub.1-8alkyl, C.sub.2-8alkenyl, C.sub.2-8alkynyl, C.sub.3-8cycloalkyl, C.sub.5-8cycloalkenyl, and C.sub.3-8cycloalkyl-C.sub.1-8alkyl, aryl, aryl-C.sub.1-8alkyl, heteroaryl, heteroaryl-C.sub.1-8alkyl, each of said aryl, aryl-C.sub.1-8alkyl, heteroaryl, or heteroaryl-C.sub.1-8alkyl is unsubstituted or substituted with 15 groups independently selected from halogen, cyano, nitro, hydroxy, carboxyl, sulfhydryl, amino, and a halogen-containing or not containing group selected from C.sub.1-8alkyl, C.sub.3-8cycloalkyl, C.sub.3-8cycloalkyl-C.sub.1-8alkyl, C.sub.2-8alkenyl, C.sub.2-8alkynyl, C.sub.1-8alkoxy, C.sub.1-8alkylcarbonyl, C.sub.1-8alkoxycarbonyl, C.sub.1-8alkylsulfonyl, C.sub.1-8alkylamino, and C.sub.1-8alkylcarbonyloxy, RO(CH.sub.2).sub.n, RO(CH.sub.2).sub.pO(CH.sub.2).sub.q, RO(CH.sub.2).sub.pS(CH.sub.2).sub.q, RS(CH.sub.2).sub.n, RS(CH.sub.2).sub.pO(CH.sub.2).sub.q, RS(CH.sub.2).sub.pS(CH.sub.2).sub.q, RO(CH.sub.2).sub.n(CO)(CH.sub.2).sub.q, RS(CH.sub.2).sub.n(CS)(CH.sub.2).sub.q, RO(CH.sub.2).sub.n(CS)(CH.sub.2).sub.q, RS(CH.sub.2).sub.n(CO)(CH.sub.2).sub.q, RO(CO)(CH.sub.2).sub.q(O).sub.m, RS(CS)(CH.sub.2).sub.q(S).sub.m, RO(CO)(CH.sub.2).sub.q(S).sub.m, RO(CS)(CH.sub.2).sub.q(O).sub.m, RS(CO)(CH.sub.2).sub.q(O).sub.m, RO(CS)(CH.sub.2).sub.q(S).sub.m, RS(CO)(CH.sub.2).sub.q(S).sub.m, RS(CS)(CH.sub.2).sub.q(O).sub.m, RO(CH.sub.2).sub.n(CO)(O).sub.m, RS(CH.sub.2).sub.n(CS)(S).sub.m, RO(CH.sub.2).sub.n(CO)(S).sub.m, RO(CH.sub.2).sub.n(CS)(O).sub.m, RS(CH.sub.2).sub.n(CO)(O).sub.m, RO(CH.sub.2).sub.n(CS)(S).sub.m, RS(CH.sub.2).sub.n(CO)(S).sub.m, RS(CH.sub.2).sub.n(CS)(O).sub.m, R(CO), R(CS), R(CO)(CH.sub.2)O, R(CS)(CH.sub.2)S, R(CO)(CH.sub.2)S, R(CS)(CH.sub.2)O, R(CO)O(CH.sub.2).sub.q, R(CS)S(CH.sub.2).sub.q, R(CO)S(CH.sub.2).sub.q, R(CS)O(CH.sub.2).sub.q, RSO(O).sub.m, RSO(S).sub.m, RSO(NR.sub.3).sub.m, RSO.sub.2(O).sub.m, RSO.sub.2(S).sub.m, RSO.sub.2(NR.sub.3).sub.m, RSO(CH.sub.2).sub.n, RSO.sub.2(CH.sub.2).sub.n, R.sub.1R.sub.2N, R.sub.1R.sub.2N(CH.sub.2).sub.nO(CH.sub.2).sub.q, R.sub.1R.sub.2N(CH.sub.2).sub.n(CO)(CH.sub.2).sub.q, R.sub.1R.sub.2N(CH.sub.2).sub.nSO.sub.2(CH.sub.2).sub.q, R.sub.1R.sub.2N(CH.sub.2).sub.n(CO)(O).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.n(CO)(S).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.n(CO)(NR.sub.3).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.nSO.sub.2(O).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.nSO.sub.2(S).sub.m, R.sub.1R.sub.2N(CH.sub.2).sub.nSO.sub.2(NR.sub.3).sub.m, R.sub.1R.sub.2N(CO)(CH.sub.2).sub.n(O).sub.m, R.sub.1R.sub.2N(CO)(CH.sub.2)(S).sub.m, R.sub.1R.sub.2N(CO)(CH.sub.2)(NR.sub.3).sub.m, R.sub.1R.sub.2NSO.sub.2(CH.sub.2).sub.q(O).sub.m, R.sub.1R.sub.2NSO.sub.2(CH.sub.2).sub.q(S).sub.m, R.sub.1R.sub.2NSO.sub.2(CH.sub.2).sub.q(NR.sub.3).sub.m, R.sub.1R.sub.2N(CH.sub.2)O, R.sub.1R.sub.2NO(CH.sub.2).sub.q, R.sub.1R.sub.2PO.sub.3(O).sub.m, R.sub.1R.sub.2R.sub.3SiO, R.sub.1R.sub.2R.sub.3Si(CHCH).sub.m, R.sub.1R.sub.2CN(O).sub.m, and R.sub.1R.sub.2CNNH; or two adjacent R.sub.a form OCH.sub.2O, CH.sub.2CH.sub.2O, OCH.sub.2CH.sub.2O, OCH(CH.sub.3)O, OC(CH.sub.3).sub.2O, OCF.sub.2O, CF.sub.2CF.sub.2O, OCF.sub.2CF.sub.2O, or CHCHCHCH; m is 0 or 1, n and q are independently an integer from 0 to 6, p is an integer from 1 to 6; R is hydrogen, a halogen-containing or not containing group selected from C.sub.1-8alkyl, C.sub.2-8alkenyl, C.sub.2-8alkynyl, C.sub.3-8cycloalkyl, C.sub.5-8cycloalkenyl, and C.sub.3-8cycloalkyl-C.sub.1-8alkyl, aryl, aryl-C.sub.1-8alkyl, heteroaryl, or heteroaryl-C.sub.1-8alkyl, each of said aryl, aryl-C.sub.1-8alkyl, heteroaryl, or heteroaryl-C.sub.1-8alkyl is unsubstituted or substituted with 15 groups substituents independently selected from halogen, cyano, nitro, hydroxy, carboxyl, sulfhydryl, amino, and a halogen-containing or not containing group selected from C.sub.1-8alkyl, C.sub.3-8cycloalkyl, C.sub.3-8cycloalkyl-C.sub.1-8alkyl, C.sub.2-8alkenyl, C.sub.2-8alkynyl, C.sub.1-8alkoxy, C.sub.1-8alkylcarbonyl, C.sub.1-8alkoxycarbonyl, C.sub.1-8alkylsulfonyl, C.sub.1-8alkylamino, and C.sub.1-8alkylcarbonyloxy; R.sub.b, R.sub.1, R.sub.2, R.sub.3 are each independently hydrogen, nitro, hydroxy, amino, a halogen-containing or not containing group selected from C.sub.1-8alkyl, C.sub.2-8alkenyl, C.sub.2-8alkynyl, C.sub.3-8cycloalkyl, C.sub.5-8cycloalkenyl, C.sub.3-8cycloalkyl-C.sub.1-8alkyl, C.sub.1-8alkoxy, C.sub.2-8alkenyloxy, C.sub.2-8alkynyloxy, C.sub.3-8cycloalkyloxy, C.sub.1-8alkoxy-C.sub.1-8alkyl, C.sub.1-8alkoxycarbonyl, C.sub.1-8alkylcarbonyl-C.sub.1-8alkyl, C.sub.1-8alkylsulfanylcarbonyl, C.sub.1-8alkylsulfonyl, C.sub.1-8alkylsulfonyl-C.sub.1-8alkyl, C.sub.1-8alkylcarbonyl, C.sub.1-8alkylcarbonyloxy, C.sub.1-8alkylamino, C.sub.1-8alkylaminocarbonyl, C.sub.1-8alkoxyaminocarbonyl, C.sub.1-8alkoxycarbonyl-C.sub.1-8alkyl, C.sub.1-8alkylaminocarbonyl-C.sub.1-8alkyl, triC.sub.1-8alkylsilyl, and diC.sub.1-8alkylphosphonyl, 6-membered heterocyclyl, aryl, aryl-C.sub.1-8alkyl, aryloxy, aryl-C.sub.1-8alkyloxy, aryloxy-C.sub.1-8alkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroaryl-C.sub.1-8alkyl, heteroaryloxy, heteroaryl-C.sub.1-8alkyloxy, heteroaryloxy-C.sub.1-8alkyl, heteroarylcarbonyl, or heteroarylsulfonyl, each of said 6-membered heterocyclyl, aryl, aryl-C.sub.1-8alkyl, aryloxy, aryl-C.sub.1-8alkyloxy, aryloxy-C.sub.1-8alkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroaryl-C.sub.1-8alkyl, heteroaryloxy, heteroaryl-C.sub.1-8alkyloxy, heteroaryloxy-C.sub.1-8alkyl, heteroarylcarbonyl, or heteroarylsulfonyl is unsubstituted or substituted with 15 groups independently selected from halogen, cyano, nitro, hydroxy, carboxyl, sulfhydryl, amino, and a halogen-containing or not containing group selected from C.sub.1-8alkyl, C.sub.3-8cycloalkyl, C.sub.3-8cycloalkyl-C.sub.1-8alkyl, C.sub.2-8alkenyl, C.sub.2-8alkynyl, C.sub.1-8alkoxy, C.sub.1-8alkylcarbonyl, C.sub.1-8alkoxycarbonyl, C.sub.1-8alkylsulfonyl, C.sub.1-8alkylamino, and C.sub.1-8alkylcarbonyloxy; or R.sub.1R.sub.2N forms a 6-membered heterocyclyl containing or not containing other hetero atoms; or adjacent R.sub.a and R.sub.b form CH.sub.2CH.sub.2NR.sub.3CH.sub.2; the derivative refers to an agriculturally acceptable derivative of the 4-hydroxy of the pyridazine ring of Formula I.

3. The five-membered ring-substituted pyridazinol compound or a derivative thereof according to claim 1 or 2, wherein, X is fluorine, chlorine, bromine, iodine, cyano, C.sub.1-6alkyl, halogenated C.sub.1-6alkyl, C.sub.1-6alkoxy, halogenated C.sub.1-6alkoxy, R.sub.1R.sub.2N(CO), R.sub.1R.sub.2N, hydroxy, or phenyl, said phenyl is unsubstituted or substituted with 15 substituents independently selected from the group consisting of halogen, cyano, nitro, hydroxy, carboxyl, sulfhydryl, amino, and a halogen-containing or not containing group selected from C.sub.1-6alkyl, C.sub.3-6cycloalkyl, C.sub.3-6cycloalkyl-C.sub.1-6alkyl, C.sub.2-6alkenyl, C.sub.2-6alkynyl, C.sub.1-6alkoxy, C.sub.1-6alkylcarbonyl, C.sub.1-6alkoxycarbonyl, C.sub.1-6alkylsulfonyl, C.sub.1-6alkylamino, and C.sub.1-6alkylcarbonyloxy; Ar is ##STR00664## Het is a 5-membered unsaturated heterocycle, the heterocycle contains, besides the 1-C atom, 2, 3, or 4 atoms or radicals follows to form the ring: O, NR.sub.b, S; R.sub.a is one or more substituents selected from: hydrogen, fluorine, chlorine, bromine, cyano, nitro, azido, a fluoro-, chloro-, or bromo-containing or not containing group selected from C.sub.1-6alkyl, C.sub.2-6alkenyl, C.sub.2-6alkynyl, C.sub.3-6cycloalkyl, C.sub.5-6cycloalkenyl, and C.sub.3-6cycloalkyl-C.sub.1-6alkyl, aryl, aryl-C.sub.1-6alkyl, heteroaryl, heteroaryl-C.sub.1-6alkyl, each of said aryl, aryl-C.sub.1-6alkyl, heteroaryl, or heteroaryl-C.sub.1-6alkyl is unsubstituted or substituted with 13 groups independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxy, carboxyl, sulfhydryl, amino, and a fluoro-, chloro-, or bromo-containing or not containing group selected from C.sub.1-6alkyl, C.sub.3-6cycloalkyl, C.sub.3-6cycloalkyl-C.sub.1-6alkyl, C.sub.2-6alkenyl, C.sub.2-6alkynyl, C.sub.1-6alkoxy, C.sub.1-6alkylcarbonyl, C.sub.1-6alkoxycarbonyl, C.sub.1-6alkylsulfonyl, C.sub.1-6alkylamino, and C.sub.1-6alkylcarbonyloxy, RO, RO(CH.sub.2).sub.pO, RO(CH.sub.2).sub.pS, RS, RS(CH.sub.2).sub.pO, RS(CH.sub.2).sub.pS, RO(CO)(O).sub.m, RS(CS)(S).sub.m, RO(CO)(S).sub.m, RO(CS)(O).sub.m, RS(CO)(O).sub.m, RO(CS)(S).sub.m, RS(CO)(S).sub.m, RS(CS)(O).sub.m, RO(CO)(CH.sub.2).sub.q, RS(CS)(CH.sub.2).sub.q, RO(CS)(CH.sub.2).sub.q, RS(CO)(CH.sub.2).sub.q, RO(CH.sub.2).sub.n(CO), RS(CH.sub.2).sub.n(CS), RO(CH.sub.2).sub.n(CS), RS(CH.sub.2).sub.n(CO), R(CO), R(CS), R(CO)O, R(CS)S, R(CO)S, R(CS)O, RSO, RSO.sub.2, R.sub.1R.sub.2N, R.sub.1R.sub.2NO, R.sub.1R.sub.2N(CO)(CH.sub.2).sub.p, R.sub.1R.sub.2N(CO)(O).sub.m, R.sub.1R.sub.2N(CO)(S).sub.m, R.sub.1R.sub.2N(CO)(NR.sub.3).sub.m, R.sub.1R.sub.2NSO.sub.2(CH.sub.2).sub.p, R.sub.1R.sub.2NSO.sub.2, R.sub.1R.sub.2N(CH.sub.2).sub.p(CO), R.sub.1R.sub.2N(CH.sub.2).sub.pSO.sub.2, R.sub.1R.sub.2N(CH.sub.2).sub.pO, R.sub.1R.sub.2NO(CH.sub.2).sub.p, R.sub.1R.sub.2PO.sub.3, R.sub.1R.sub.2R.sub.3SiO, R.sub.1R.sub.2R.sub.3Si, R.sub.1R.sub.2R.sub.3SiCHCH, R.sub.1R.sub.2CN, R.sub.1R.sub.2CNO, and R.sub.1R.sub.2CNNH; or two adjacent R.sub.a form CHCHCHCH; m is 0 or 1, n and q are each independently 0, 1, 2, 3 or 4, p is 1, 2, 3 or 4; R is hydrogen, a fluoro-, chloro-, or bromo-containing or not containing group selected from C.sub.1-6alkyl, C.sub.2-6alkenyl, C.sub.2-6alkynyl, C.sub.3-6cycloalkyl, C.sub.5-6cycloalkenyl, and C.sub.3-6cycloalkyl-C.sub.1-6alkyl, aryl, aryl-C.sub.1-6alkyl, heteroaryl, or heteroaryl-C.sub.1-6alkyl, each of said aryl, aryl-C.sub.1-6alkyl, heteroaryl, or heteroaryl-C.sub.1-6alkyl is unsubstituted or substituted with 13 substituents independently selected from the group consisting of fluorine, chlorine, bromine, cyano, nitro, hydroxy, carboxyl, sulfhydryl, amino, and a fluoro-, chloro-, or bromo-containing or not containing group selected from C.sub.1-6alkyl, C.sub.3-6cycloalkyl, C.sub.3-6cycloalkyl-C.sub.1-6alkyl, C.sub.2-6alkenyl, C.sub.2-6alkynyl, C.sub.1-6alkoxy, C.sub.1-6alkylcarbonyl, C.sub.1-6alkoxycarbonyl, C.sub.1-6alkylsulfonyl, C.sub.1-6alkylamino, and C.sub.1-6alkylcarbonyloxy; R.sub.b, R.sub.1, R.sub.2, R.sub.3 are each independently hydrogen, nitro, hydroxy, amino, a fluoro-, chloro-, or bromo-containing or not containing group selected from C.sub.1-6alkyl, C.sub.2-6alkenyl, C.sub.2-6alkynyl, C.sub.3-6cycloalkyl, C.sub.5-6cycloalkenyl, C.sub.3-6cycloalkyl-C.sub.1-6alkyl, C.sub.1-6alkoxy, C.sub.2-6 alkenyloxy, C.sub.2-6 alkynyloxy, C.sub.3-6 cycloalkyloxy, C.sub.1-6 alkoxy-C.sub.1-6 alkyl, C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylsulfanylcarbonyl, C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkylsulfonyl-C.sub.1-6 alkyl, C.sub.1-6 alkylcarbonyl, C.sub.1-6 alkylcarbonyl-C.sub.1-6 alkyl, C.sub.1-6 alkylcarbonyloxy, C.sub.1-6 alkylamino, C.sub.1-6 alkylaminocarbonyl, C.sub.1-6 alkoxyaminocarbonyl, C.sub.1-6 alkoxycarbonyl-C.sub.1-6 alkyl, C.sub.1-6 alkylaminocarbonyl-C.sub.1-6 alkyl, triC.sub.1-6 alkylsilyl, and diCi.sub.1-6 alkylphosphonyl, ##STR00665## aryl, aryl-C.sub.1-6 alkyl, aryloxy, aryl-C.sub.1-8alkyloxy, aryloxy-C.sub.1-6 alkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroaryl-C.sub.1-6 alkyl, heteroaryloxy, heteroaryl-C.sub.1-6 alkyloxy, heteroaryloxy-C.sub.1-6 alkyl, heteroarylcarbonyl, or heteroarylsulfonyl, each of said ##STR00666## aryl, aryl-C.sub.1-6 alkyl, aryloxy, aryl-C.sub.1-6 alkyloxy, aryloxy-C.sub.1-8alkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroaryl-C.sub.1-6 alkyl, heteroaryloxy, heteroaryl-C.sub.1-6 alkyloxy, heteroaryloxy-C.sub.1-6 alkyl, heteroarylcarbonyl, or heteroarylsulfonyl is unsubstituted or substituted with 13 groups independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxy, carboxyl, sulfhydryl, amino, and a fluoro-, chloro-, or bromo-containing or not containing group selected from C.sub.1-6 alkyl, C.sub.3-6 cycloalkyl, C.sub.3-6 cycloalkyl-C.sub.1-6 alkyl, C.sub.2-6 alkenyl, C.sub.2-6 alkynyl, C.sub.1-6 alkoxy, C.sub.1-6 alkylcarbonyl, C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkylamino, and C.sub.1-6 alkylcarbonyloxy; or R.sub.1R.sub.2N is ##STR00667## or adjacent R.sub.a and R.sub.b form CH.sub.2CH.sub.2N(Boc)CH.sub.2; the aryl is selected from ##STR00668## the heteroaryl is selected from ##STR00669## ##STR00670## R is hydrogen, nitro, hydroxy, amino, a fluoro-, chloro-, or bromo-containing or not containing group selected from C.sub.1-6 alkyl, C.sub.2-6 alkenyl, C.sub.2-6 alkynyl, C.sub.3-6 cycloalkyl, C.sub.5-6 cycloalkenyl, C.sub.3-6 cycloalkyl-C.sub.1-6 alkyl, C.sub.1-6 alkoxy, C.sub.2-6 alkenyloxy, C.sub.2-6 alkynyloxy, C.sub.3-6 cycloalkyloxy, C.sub.1-6 alkoxy-C.sub.1-6 alkyl, C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylsulfanylcarbonyl, C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkylsulfonyl-C.sub.1-6 alkyl, C.sub.1-6 alkylcarbonyl, C.sub.1-6 alkylcarbonyl-C.sub.1-6 alkyl, C.sub.1-6 alkylcarbonyloxy, C.sub.1-6 alkylamino, C.sub.1-6 alkylaminocarbonyl, C.sub.1-6 alkoxyaminocarbonyl, C.sub.1-6 alkoxycarbonyl-C.sub.1-6 alkyl, C.sub.1-6 alkylaminocarbonyl-C.sub.1-6 alkyl, triC.sub.1-6 alkylsilyl, and diCi.sub.1-6 alkylphosphonyl, ##STR00671## aryl, aryl-C.sub.1-8alkyl, aryloxy, aryl-C.sub.1-6 alkyloxy, aryloxy-C.sub.1-6 alkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroaryl-C.sub.1-6 alkyl, heteroaryloxy, heteroaryl-C.sub.1-6 alkyloxy, heteroaryloxy-C.sub.1-6 alkyl, heteroarylcarbonyl, or heteroarylsulfonyl, each of said ##STR00672## aryl, aryl-C.sub.1-6 alkyl, aryloxy, aryl-C6 alkyloxy, aryloxy-C.sub.1-6 alkyl, arylcarbonyl, arylsulfonyl, heteroaryl, heteroaryl-C.sub.1-6 alkyl, heteroaryloxy, heteroaryl-C.sub.1-6 alkyloxy, heteroaryloxy-C.sub.1-6 alkyl, heteroarylcarbonyl, or heteroarylsulfonyl is unsubstituted or substituted with 13 groups independently selected from fluorine, chlorine, bromine, cyano, nitro, hydroxy, carboxyl, sulfhydryl, amino, and a fluoro-, chloro-, or bromo-containing or not containing group selected from C.sub.1-6 alkyl, C.sub.3-6 cycloalkyl, C.sub.3-6 cycloalkyl-C.sub.1-6 alkyl, C.sub.2-6 alkenyl, C.sub.2-6 alkynyl, C.sub.1-6 alkoxy, C.sub.1-6 alkylcarbonyl, C.sub.1-6 alkoxycarbonyl, C.sub.1-6 alkylsulfonyl, C.sub.1-6 alkylamino, and C.sub.1-6 alkylcarbonyloxy; the derivative refers to an agriculturally acceptable derivative of the 4-hydroxy of the pyridazine ring of Formula I, including a salt, an ester, a hydrazine, a hydroxylamine, an ether thereof, and the like.

4. The five-membered ring-substituted pyridazinol compound or a derivative thereof according to claim 1 or 2, wherein, X represents fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, trifluoromethyl, pentafluoroethyl, difluoromethyl, monofluoromethyl, methoxy, ethoxy, trifluoromethoxy, or pentafluoroethoxy; Het is ##STR00673## R.sub.a is selected from one or more of the following groups: hydrogen, methyl, ethyl, cyano, cyclopropyl, phenyl, fluorine, chlorine, bromine, iodine, cyano, nitro, difluoromethyl, 2,2,2,-trifluoroethyl, trifluoromethyl, methoxy, ethoxy, benzyloxy, COOEt, amino, methylamino, dimethylamino, acetyl amino, ##STR00674## or Ar is ##STR00675## R.sub.b represents hydrogen, methyl, ethyl, n-propyl, isopropyl, difluoromethyl, 2,2,2-trifluoroethyl, acetyl, phenyl, benzyl, ##STR00676## or triphenylmethyl; the derivative refers to an agriculturally acceptable derivative of the 4-hydroxy of the pyridazine ring of Formula I, including a salt, an ester, a hydrazine, a hydroxylamine, an ether thereof, and the like.

5. A method for preparing a five-membered ring-substituted pyridazinol compound or derivative thereof according to any one of claims 1 to 4, comprising: the method for preparing the five-membered ring-substituted pyridazinol compound, comprising the steps of: (1) subjecting a compound of Formula II and a compound of Formula III to Suzuki reaction to obtain a compound of Formula IV; (2) subjecting a compound of Formula IV to halogenating reaction to obtain a compound of Formula V; (3) subjecting a compound of Formula V to hydrolysis reaction to obtain a compound of Formula I; wherein the reaction route is as follows: ##STR00677## L.sub.1, L.sub.2 each independently represent halogen, preferably chlorine, bromine, or iodine; the reaction route for preparing an ester or ether derivative is as follows: ##STR00678## wherein, Y.sub.1 is a halogen, preferably chlorine or bromine; the reaction route for preparing an oxime or hydroxylamine derivative is as follows: ##STR00679## wherein, Y.sub.2 is a halogen, preferably chlorine or fluorine.

6. The method for preparing a five-membered ring-substituted pyridazinol compound or derivative thereof according to claim 5, wherein, the reactions are carried out in the range of 20 to 150 C., preferably 50 to 130 C.; step (1) is carried out in the presence of a catalyst, a base and a solvent, wherein the catalyst is Pd(dppf)Cl.sub.2CH.sub.2Cl.sub.2, Pd(dba).sub.2, Pd.sub.2(dba).sub.3, Pd(PPh.sub.3).sub.4, PdCl.sub.2, Pd(OAc).sub.2, Pd(dppf)Cl.sub.2, Pd(PPh.sub.3).sub.2Cl.sub.2, or Ni(dppf)Cl.sub.2, the base is one or more selected from Et.sub.3N, NaHCO.sub.3, KOAc, K.sub.2CO.sub.3, K.sub.3PO.sub.4, Na.sub.2CO.sub.3, CsF, Cs.sub.2CO.sub.3, t-BuONa, EtONa, KOH and NaOH, the solvent is THF/water, toluene/water, DMF/water, 1,4-dioxane/water, toluene/ethanol/water, acetonitrile/water, THF, toluene, 1,4-dioxane, acetonitrile, or DMF system; step (2) is carried out in the presence of a halogenated reagent, a catalyst and a solvent, wherein the halogenated reagent is N-chloro succinimide, N-bromo succinimide or N-iodo succinimide, the catalyst is benzoyl peroxide, and the solvent is acetonitrile; step (3) is carried out in the presence of a base and a solvent or in the presence of a solution of boron tribromide, a solution of hydrobromic acid in acetic acid, a solution of hydrochloric acid in methanol or a solution of hydrochloric acid in ethyl acetate, the base is preferably selected from NaOH, KOH, potassium acetate, and sodium acetate, the solvent is preferably water or DMSO; reactions for preparing the ester or ether derivatives and the second step for preparing the oxime or hydroxylamine derivatives are carried out in the presence of a base and a solvent, the base is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, cesium carbonate, triethylamine and diisopropylethylamine; the solvent is THF, 1,4-dioxane, toluene, 1,2-dichloroethane, ethyl acetate, acetonitrile, DMF, acetone, dichloromethane, or chloroform; the first step for preparing the oxime or hydroxylamine derivative is carried out in the presence of a halogenation reagent and a solvent, wherein the halogenation reagent is Phenofluor/cesium fluoride or POCl.sub.3, and the solvent is one or more selected from the group consisting of toluene, 1,2-dichloroethane, and DMF; the reaction temperature is in the range of 0 to 120 C., preferably 20 to 80 C.

7. A herbicidal composition, comprising component (i) a five-membered ring-substituted pyridazinol compound of Formula I or a derivative thereof according to any one of claims 1 to 4; preferably, further comprising component (ii) one or more additional herbicides and/or safeners; more preferably, further comprising component (iii) an agriculturally acceptable formulation auxiliary.

8. The herbicidal composition according to claim 7, wherein the additional herbicide is selected from the group consisting of an HPPD inhibitor, a hormone herbicide, and a PDS inhibitor; preferably, the HPPD inhibitor is selected from the group consisting of Sulcotrione, Mesotrione, Topramezone, Tembotrione, Bicyclopyrone, Tefuryltrione, Benzobicyclon, Lancotrione, Shuangzuocaotong, Huanbifucaotong, Sanzuohuangcaotong, Benzuofucaotong, Pyrasulfotole, Pyrazolate, Benzofenap, Tolpyralate, Fenquinotrione, and Isoxaflutole; the hormone herbicide is selected from the group consisting of Fluroxypyr, Halauxifen-methyl, Florpyrauxifen-benzyl, Quinclorac, Quinmerac, 2-methyl-4-chlorophenoxy acetic acid, 2-methyl-4-chlorophenoxypropionic acid, MCPB, 2,4-D, Dichlorprop, 2,4-DB, Dicamba, Picloram, Trichlopyr, Clopyralid, Triclopyr and derivatives thereof, the PDS inhibitor is selected from the group consisting of Flurochloridone, Flurtamone, Diflufenican, Picolinafen, Beflubutamid, Norflurazon and Fluridone.

9. A method for controlling a harmful plant, comprising applying at least one of herbicidally effective amount of the five-membered ring-substituted pyridazinol compound or derivative thereof according to any one of claims 1 to 4, or the herbicidal composition according to any one of claims 7 to 8 to the harmful plant or an area with the harmful plant.

10. Use of at least one of the five-membered ring-substituted pyridazinol compound or derivative thereof according to any one of claims 1 to 4, or the herbicidal composition according to any one of claims 7 to 8 for controlling a harmful plant; preferably, the five-membered ring-substituted pyridazinol compound or derivative thereof 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.

Description

SPECIFIC MODE FOR CARRYING OUT THE INVENTION

[0101] 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.

[0102] 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 1-2. The structure and information of a certain compound are shown in Table 1-2. The compounds in Table 1-2 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-US-00001 TABLE 1 Structure and .sup.1HNMR data of Compound I I [00041] No. X Ar .sup.1HNMR 1 Cl [00042] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.21 (s, 1H), 7.37 (s, 1H), 6.59 (s, 1H), 3.88 (s, 3H), 2.39 (s, 3H). 2 Cl [00043] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.14 (s, 1H), 7.72 (s, 1H), 7.45 (s, 1H), 7.30 (s, 1H), 3.68 (s, 3H). 3 Cl [00044] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 12.92 (s, 1H), 7.39 (d, J = 2.5 Hz, 1H), 7.33 (s, 1H), 7.08 (d, J = 2.5 Hz, 1H), 3.94 (s, 3H). 4 Cl [00045] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.21 (s, 1H), 7.74 (s, 1H), 7.56 (s, 1H), 7.38 (s, 1H), 3.79 (s, 3H). 5 Cl [00046] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 12.12 (s, 1H), 8.26 (s, 1H), 7.98 (s, 1H), 7.34 (s, 1H). 6 Cl [00047] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.87 (s, 1H), 7.90 (d, J = 2.5 Hz, 1H), 7.39-7.32 (m, 2H). 7 Cl [00048] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.25 (s, 1H), 8.12 (s, 1H), 7.75 (s, 1H), 7.31 (s, 1H). 8 Cl [00049] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.20 (s, 1H), 8.74 (d, J = 2.5 Hz, 1H), 7.33-7.26 (m, 2H). 9 Cl [00050] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.23 (s, 1H), 8.36 (s, 1H), 8.17 (s, 1H), 7.31 (s, 1H). 10 Cl [00051] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.58 (s, 1H), 8.23 (d, J = 2.3 Hz, 1H), 7.36 (m, 2H). 11 Cl [00052] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.17 (s, 1H), 9.20 (s, 1H), 8.10 (s, 1H), 7.31 (s, 1H). 12 Cl [00053] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 12.66 (s, 1H), 8.04 (d, J = 2.0 Hz, 1H), 7.53 (d, J = 2.0 Hz, 1H), 7.34 (s, 1H). 13 Cl [00054] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.21 (s, 1H), 9.21 (s, 1H), 8.19 (s, 1H), 7.32 (s, 1H). 14 Cl [00055] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.04 (s, 1H), 8.72 (d, J = 2.5 Hz, 1H), 7.37 (d, J = 2.5 Hz, 1H), 7.30 (s, 1H) 15 Cl [00056] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.19 (s, 1H), 8.72 (s, 1H), 8.00 (s, 1H), 7.31 (s, 1H). 16 Cl [00057] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.49 (s, 1H), 8.10 (d, J = 1.5 Hz, 1H), 7.39-7.33 (m, 2H). 17 Cl [00058] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.28 (s, 1H), 8.21 (s, 1H), 7.28 (s, 1H). 18 Cl [00059] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.12 (s, 1H), 8.19 (s, 1H), 7.27 (s, 1H). 19 Cl [00060] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.22 (s, 1H), 8.28 (s, 1H), 7.26 (s, 1H). 20 Cl [00061] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.03 (s, 1H), 9.49 (s, 1H), 7.25 (s, 1H). 21 Cl [00062] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.17 (s, 1H), 7.92 (s, 1H), 7.27 (s, 1H) 22 Cl [00063] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.71 (s, 1H), 9.41 (s, 1H), 7.31 (s, 1H). 23 Cl [00064] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.11 (s, 1H), 9.11 (s, 1H), 7.33 (s, 1H), 3.78 (s, 3H). 24 Cl [00065] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 9.98 (s, 1H), 7.34 (s, 1H), 4.12 (s, 3H). 25 Cl [00066] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 12.85 (s, 1H), 10.25 (s, 1H), 7.78-7.65 (m, 1H), 7.31 (s, 1H), 6.80-6.72 (m, 1H). 26 Cl [00067] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.17 (s, 1H), 7.85 (s, 1H), 7.33 (s, 1H), 7.01 (s, 1H), 4.33 (t, J = 5.1 Hz, 2H), 1.91 (qt, J = 8.0, 4.9 Hz, 2H), 0.93 (t, J = 7.9 Hz, 3H). 27 Cl [00068] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.19 (s, 1H), 7.62 (d, J = 2.5 Hz, 1H), 7.31 (s, 1H), 7.11 (d, J = 2.5 Hz, 1H), 2.38 (s, 3H). 28 Cl [00069] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.22 (s, 1H), 7.86 (s, 1H), 7.48 (d, J = 2.5 Hz, 1H), 7.31 (s, 1H), 6.65 (d, J = 2.5, Hz, 1H). 29 Cl [00070] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.21 (s, 1H), 7.60 (d, J = 2.0 Hz, 1H), 7.31 (s, 1H), 6.74 (d, J = 2.0 Hz, 1H), 3.90 (s, 3H). 30 Cl [00071] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.21 (s, 1H), 7.93 (s, 1H), 7.40-7.31 (m, 3H), 7.28-7.17 (m, 3H), 7.21 (s, 1H), 5.45 (s, 2H). 31 Cl [00072] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.88 (s, 1H), 8.04-8.01 (m, 1H), 7.98-7.90 (m, 2H), 7.48- 7.35 (m, 1H), 7.45 (s, 1H), 7.32-7.22 (m, 1H). 32 Cl [00073] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.43 (s, 1H), 8.22 (s, 1H), 8.10-8.00 (m, 2H), 7.56-7.49 (m, 2H), 7.47 (s, 1H). 33 Cl [00074] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.79 (s, 1H), 7.85 (d, J = 2.5 Hz, 1H), 7.80 (d, J = 2.5 Hz, 1H), 7.37 (s, 1H). 34 Cl [00075] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.34 (s, 1H), 10.26 (s, 1H), 7.54-7.45 (m, 1H), 7.44 (s, 1H), 7.41 (s, 1H), 7.14-7.00 (m, 3H). 35 Cl [00076] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.20 (s, 1H), 7.88 (s, 1H), 7.38 (s, 1H), 7.23 (s, 1H), 6.06 (t, J = 7.0 Hz, 1H), 3.93-3.88 (m, 1H), 3.79-3.74 (m, 1H), 2.14-2.07 (m, 1H), 2.07-1.95 (m, 1H), 1.85-1.70 (m, 2H), 1.65-1.54 (m, 2H). 36 Cl [00077] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.05 (s, 1H), 7.39 (s, 1H), 2.72 (s, 3H), 2.60 (s, 3H). 37 Br [00078] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.21 (s, 1H), 7.87 (s, 1H), 7.54 (s, 1H), 7.04 (s, 1H), 3.91 (s, 3H). 38 CN [00079] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.18 (s, 1H), 7.85 (s, 1H), 6.87 (s, 1H), 3.92 (s, 3H), 2.39 (s, 3H). 39 Me [00080] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.20 (s, 1H), 7.88 (s, 1H), 7.10 (s, 1H), 6.68 (s, 1H), 6.02 (q, J = 6.9 Hz, 1H), 3.66 (q, J = 8.0 Hz, 2H), 2.22 (s, 3H), 1.36 (d, J = 6.7 Hz, 3H), 1.08 (t, J = 8.0 Hz, 3H). 40 OMe [00081] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.07 (s, 1H), 7.39 (s, 1H), 6.87 (s, 1H), 6.57 (s, 1H), 3.84 (s, 3H). 41 Et [00082] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.19 (s, 1H), 7.23 (s, 1H), 6.74 (s, 1H), 3.90 (s, 3H), 2.60 (q, J = 8.0 Hz, 2H), 1.15 (t, J = 7.9 Hz, 3H). 42 F [00083] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.06 (s, 1H), 7.81 (s, 1H), 7.16 (s, 1H), 6.98 (s, 1H), 4.29 (q, J = 8.0 Hz, 2H), 1.15 (t, J = 7.9 Hz, 3H). 43 Cl [00084] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.29 (s, 1H), 8.01 (s, 1H), 7.90-7.81 (m, 1H), 7.68-7.49 (m, 1H), 7.48 (s, 1H), 7.37-7.21 (m, 2H). 44 Cl [00085] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.08 (s, 1H), 7.41 (s, 1H), 6.64 (s, 1H), 4.08 (q, J = 8.0 Hz, 2H), 1.90-1.84 (m, 1H), 1.15 (t, J = 7.9 Hz, 3H), 0.90-0.85 (m, 2H), 0.71-0.66 (m, 2H). 45 CF.sub.2CF.sub.3 [00086] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.08 (s, 1H), 6.63 (s, 1H), 6.37 (s, 1H), 3.76 (s, 3H), 1.90-1.84 (m, 1H), 0.90-0.85 (m, 2H), 0.71-0.66 (m, 2H). 46 CHF.sub.2 [00087] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.28 (s, 1H), 7.92-7.85 (m, 2H), 7.51-7.41 (m, 4H), 7.01 (s, 1H), 6.95 (s, 1H), 3.95 (s, 3H). 47 CH.sub.2F [00088] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.08 (s, 1H), 6.37 (s, 1H), 5.40 (d, J = 5.0 Hz, 2H), 3.76 (s, 3H), 2.70 (s, 3H). 48 Cl [00089] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.16 (s, 1H), 7.38 (s, 1H), 6.86 (s, 1H), 3.90 (s, 3H). 49 OEt [00090] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.31 (s, 1H), 6.82 (s, 1H), 6.57 (s, 1H), 4.61-4.56 (m, 1H), 4.39 (q, J = 6.0 Hz, 2H), 2.39 (s, 3H), 1.36 (t, J = 5.8 Hz, 3H), 1.26 (d, J = 7.0 Hz, 6H). 50 OCF.sub.3 [00091] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.08 (s, 1H), 6.84 (s, 1H), 6.20 (d, J = 8.0 Hz, 1H), 4.50-4.44 (m, 1H), 1.40 (d, J = 7.0 Hz, 6H). 51 OCF.sub.2CF.sub.3 [00092] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.21 (s, 1H), 7.60 (d, J = 2.5 Hz, 1H), 6.94 (s, 1H), 6.62 (d, J = 2.5 Hz, 1H), 4.08 (q, J = 8.0 Hz, 2H), 1.30 (t, J = 8.0 Hz, 3H). 52 Cl [00093] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.33 (s, 1H), 7.60 (d, J = 2.5 Hz, 1H), 7.35 (s, 1H), 6.62 (d, J = 2.5 Hz, 1H), 4.59-4.53 (m, 1H), 1.26 (d, J = 6.7 Hz, 6H). 53 Cl [00094] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.31 (s, 1H), 7.95 (d, J = 2.5 Hz, 1H), 7.66-7.54 (m, 4H), 7.56- 7.48 (m, 1H), 7.43 (s, 1H), 6.77 (d, J = 2.5 Hz, 1H). 54 Cl [00095] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.09 (s, 1H), 7.64 (d, J = 2.5 Hz, 1H), 7.39-7.31 (m, 3H), 7.32- 7.24 (m, 1H), 7.22-7.16 (m, 2H), 6.61 (d, J = 2.5 Hz, 1H), 5.46 (s, 2H). 55 Cl [00096] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.13 (s, 1H), 7.63 (d, J = 2.5 Hz, 1H), 7.38 (s, 1H), 6.66 (d, J = 2.5 Hz, 1H), 5.32 (q, J = 8.9 Hz, 2H). 56 Cl [00097] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.08 (s, 1H), 7.41 (s, 1H), 6.20 (d, J = 8.0 Hz, 1H), 3.76 (s, 3H). 57 Cl [00098] 58 Cl [00099] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.16 (s, 1H), 7.37 (s, 1H), 6.99 (s, 1H), 3.89 (s, 3H). 59 Cl [00100] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.08 (s, 1H), 7.41 (s, 1H), 6.20 (s, 1H), 3.76 (s, 3H). 60 Cl [00101] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.22 (s, 1H), 7.37 (s, 1H), 6.59 (s, 1H), 3.88 (s, 3H), 2.60 (q, J = 8.0 Hz, 2H), 1.19 (t, J = 8.0 Hz, 3H). 61 Cl [00102] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.08 (s, 1H), 7.41 (s, 1H), 6.63 (s, 1H), 3.76 (s, 3H), 1.90-1.84 (m, 1H), 0.90-0.85 (m, 2H), 0.71-0.66 (m, 2H). 62 Cl [00103] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.22 (s, 1H), 7.37 (s, 1H), 5.84 (s, 1H), 3.89 (s, 3H), 3.84 (s, 3H). 63 Cl [00104] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.22 (s, 1H), 7.37 (s, 1H), 5.84 (s, 1H), 3.89 (s, 3H), 3.84 (s, 3H). 64 Cl [00105] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.16 (s, 1H), 7.46 (s, 1H), 7.43-7.27 (m, 5H), 5.87 (s, 1H), 5.35 (s, 2H), 3.90 (s, 3H). 65 Cl [00106] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.20 (s, 1H), 8.01 (s, 2H), 7.37 (s, 1H), 5.56 (s, 1H), 3.88 (s, 3H). 66 Cl [00107] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.81 (s, 1H), 8.17 (s, 1H), 7.37 (s, 1H), 5.56 (s, 1H), 3.88 (s, 3H), 3.01 (s, 3H). 67 Cl [00108] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.60 (s, 1H), 7.15 (s, 1H), 5.56 (s, 1H), 3.88 (s, 3H), 3.19 (s, 6H). 68 Cl [00109] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.82 (s, 1H), 10.38 (s, 1H), 7.36 (s, 1H), 5.56 (s, 1H), 3.92 (s, 3H), 2.13 (s, 3H). 69 Cl [00110] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.76 (s, 1H), 9.56 (s, 1H), 7.87 (s, 1H), 7.14 (s, 1H), 5.76 (s, 1H), 3.94 (s, 3H), 2.71 (s, 3H). 70 Cl [00111] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.79 (s, 1H), 10.01 (s, 1H), 7.40 (s, 1H), 5.56 (s, 1H), 3.94 (s, 3H), 1.29 (s, 9H). 71 Cl [00112] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.62 (s, 1H), 7.38 (s, 1H), 7.01 (s, 1H), 3.92 (s, 3H). 72 Cl [00113] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.54 (s, 1H), 7.55 (s, 1H), 7.38 (s, 1H), 3.92 (s, 3H). 73 Cl [00114] .sup.1H NMR (500 MHz, Chloroform-d) 7.90-7.82 (m, 2H), 7.42-7.28 (m, 3H), 7.34 (s, 1H), 7.29 (s, 1H), 5.85 (s, 1H), 4.07 (s, 3H). 74 Cl [00115] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.62 (s, 1H), 7.37 (s, 1H), 6.93 (t, J = 57.5 Hz, 1H), 6.83 (s, 1H), 3.89 (s, 3H). 75 Cl [00116] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.50 (s, 1H), 7.38 (s, 1H), 6.69 (s, 1H), 3.89 (s, 3H), 3.07 (q, J = 8.9 Hz, 2H). 76 Cl [00117] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.58 (s, 1H), 7.50 (d, J = 5.5 Hz, 1H), 7.41 (s, 1H), 3.76 (s, 3H). 77 Cl [00118] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.55 (s, 1H), 7.86 (s, 1H), 7.36 (s, 1H), 3.88 (s, 3H). 78 Cl [00119] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.39 (s, 1H), 8.11 (s, 1H), 7.37 (s, 1H), 3.86 (s, 3H). 79 Cl [00120] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.48 (s, 1H), 7.60 (s, 1H), 6.37 (s, 1H), 3.76 (s, 3H). 80 Cl [00121] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.37 (s, 1H), 7.56 (s, 1H), 7.35 (s, 1H), 3.85 (s, 3H), 2.07 (s, 3H). 81 Cl [00122] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.37 (s, 1H), 7.67 (s, 1H), 7.35 (s, 1H), 3.84 (s, 3H), 2.70 (q, J = 8.0 Hz, 2H), 1.19 (t, J = 8.0 Hz, 3H). 82 Cl [00123] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.38 (s, 1H), 7.76 (s, 1H), 7.41 (s, 1H), 3.76 (s, 3H), 2.41-2.36 (m, 1H), 1.12-1.02 (m, 2H), 0.82-0.72 (m, 2H). 83 Cl [00124] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.73 (s, 1H), 7.37 (s, 1H), 7.18 (s, 1H), 3.90 (s, 3H), 3.80 (s, 3H). 84 Cl [00125] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.81 (s, 1H), 7.37 (s, 1H), 7.18 (s, 1H), 4.10 (q, J = 8.0 Hz, 2H), 3.90 (s, 3H), 1.34 (t, J = 8.0 Hz, 3H). 85 Cl [00126] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.73 (s, 1H), 7.68-7.16 (m, 7H), 5.15 (s, 2H), 3.91 (s, 3H). 86 Cl [00127] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.99 (s, 1H), 7.69 (s, 1H), 7.33 (s, 1H), 5.83 (s, 2H), 3.89 (s, 3H). 87 CF.sub.2CF.sub.3 [00128] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.12 (s, 1H), 7.67 (s, 1H), 6.82 (s, 1H), 5.95 (s, 1H), 3.88 (s, 3H), 2.74 (s, 3H). 88 I [00129] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.28 (s, 1H), 7.69 (s, 1H), 6.29 (s, 1H), 3.87 (s, 3H), 2.85 (s, 6H). 89 Cl [00130] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.04 (s, 1H), 9.94 (s, 1H), 7.87 (s, 1H), 7.44 (s, 1H), 3.90 (s, 3H), 2.07 (s, 3H). 90 Cl [00131] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.10 (s, 1H), 8.60 (s, 1H), 7.87 (s, 1H), 7.44 (s, 1H), 6.16 (s, 1H), 3.91 (s, 3H), 2.68 (s, 3H). 91 Cl [00132] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.04 (s, 1H), 9.78 (s, 1H), 7.87 (s, 1H), 7.42 (s, 1H), 3.92 (s, 3H), 1.49 (s, 9H). 92 Cl [00133] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.15 (s, 1H), 7.93 (s, 1H), 7.37 (s, 1H), 3.89 (s, 3H). 93 Cl [00134] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.27 (s, 1H), 8.22 (s, 1H), 7.60 (s, 1H), 3.86 (s, 3H). 94 Cl [00135] 95 Br [00136] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.55 (s, 1H), 7.71 (s, 1H), 7.58 (s, 1H), 3.85 (s, 3H). 96 Cl [00137] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.48 (s, 1H), 7.88 (s, 1H), 7.36 (s, 1H), 6.69 (q, J = 57.5 Hz, 1H), 3.85 (s, 3H). 97 Cl [00138] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.25 (s, 1H), 7.76 (s, 1H), 7.39 (s, 1H), 3.85 (s, 3H), 3.07 (q, J = 8.9 Hz, 2H). 98 Cl [00139] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 9.49 (s, 1H), 8.11 (d, J = 2.5 Hz, 1H), 7.65 (s, 1H), 7.02 (d, J = 2.5 Hz, 1H), 1.61 (s, 9H). 99 Cl [00140] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.28 (s, 1H), 7.60 (d, J = 2.5 Hz, 1H), 7.36 (s, 1H), 6.63 (d, J = 2.5 Hz, 1H), 4.08 (q, J = 8.0 Hz, 2H), 1.30 (t, J = 8.0 Hz, 3H). 100 Cl [00141] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.33 (s, 1H), 7.60 (d, J = 2.5 Hz, 1H), 7.35 (s, 1H), 6.62 (d, J = 2.5 Hz, 1H), 4.56 (m, 1H), 1.26 (d, J = 6.7 Hz, 6H). 101 Cl [00142] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.76 (s, 1H), 7.60 (d, J = 2.2 Hz, 1H), 7.49 (s, 1H), 6.58 (d, J = 2.5 Hz, 1H), 6.10-6.07 (m, 1H), 3.93-3.88 (m, 1H), 3.79-3.74 (m, 1H), 2.47-2.37 (m, 1H), 2.07- 1.96 (m, 2H), 1.79-1.68 (m, 1H), 1.63-1.54 (m, 2H). 102 Cl [00143] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.04 (s, 1H), 8.40 (d, J = 1.3 Hz, 1H), 8.27 (d, J = 1.6 Hz, 1H), 7.42 (s, 1H), 1.61 (s, 9H). 103 Cl [00144] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.23 (s, 1H), 8.18 (s, 1H), 7.38 (s, 1H), 2.74 (s, 3H), 1.61 (s, 9H). 104 Cl [00145] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.01 (s, 1H), 7.78 (s, 1H), 7.40 (s, 1H), 6.93 (s, 1H), 4.57-4.52 (m, 1H), 1.30 (d, J = 6.7 Hz, 6H). 105 Cl [00146] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.31 (s, 1H), 7.35 (s, 1H), 3.82 (s, 3H), 2.52 (s, 3H), 2.39 (s, 3H). 106 Cl [00147] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 9.95 (s, 4H), 7.94 (s, 1H), 7.79 (t, J = 57.5 Hz, 1H), 7.71 (s, 1H), 7.41 (s, 1H). 107 Cl [00148] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.11 (s, 1H), 7.81 (s, 1H), 7.45 (s, 1H), 7.04 (s, 1H), 4.30-4.27 (m, 1H), 3.91-3.86 (m, 2H), 3.66-3.61 (m, 2H), 1.97-1.90 (m, 2H), 1.78-1.71 (m, 2H). 108 Cl [00149] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 12.60 (s, 1H), 8.22 (d, J = 2.5 Hz, 1H), 7.38 (s, 1H), 7.13 (d, J = 2.5 Hz, 1H), 1.61 (s, 9H). 109 Cl [00150] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.04 (s, 1H), 7.81 (s, 1H), 7.45 (s, 1H), 7.32-7.26 (m, 2H), 7.03 (s, 1H), 6.95-6.89 (m, 2H), 5.45 s, 2H), 3.79 (s, 3H). 110 Cl [00151] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.00 (s, 1H), 7.81 (s, 1H), 7.48 (s, 1H), 7.06 (s, 1H), 4.45-4.32 (m, 1H), 3.00-2.94 (m, 4H), 1.98-1.91 (m, 2H), 1.79-1.72 (m, 2H), 1.42 (s, 9H). 111 Cl [00152] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.11 (s, 1H), 7.38 (s, 1H), 6.90 (s, 1H), 3.94 (s, 3H). 112 Cl [00153] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.03 (s, 1H), 7.87 (s, 1H), 7.77-7.71 (m, 6H), 7.43-7.31 (m, 10H), 7.24 (s, 1H). 113 Cl [00154] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 12.65 (s, 1H), 7.69 (s, 1H), 7.34 (s, 1H), 2.42 (s, 3H). 114 Cl [00155] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 12.74 (s, 1H), 7.34 (s, 1H), 7.12 (s, 1H), 2.48 (s, 3H). 115 Cl [00156] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.81 (s, 1H), 7.98 (s, 1H), 7.36 (s, 1H), 2.34 (s, 3H). 116 Cl [00157] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.93 (s, 1H), 8.34 (s, 1H), 7.37 (s, 1H), 4.35 (q, J = 5.9 Hz, 2H), 1.32 (t, J = 5.8 Hz, 3H). 117 Cl [00158] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.76 (s, 1H), 8.28 (s, 1H), 7.35 (s, 1H), 4.27 (q, J = 5.9 Hz, 2H), 1.30 (t, J = 5.9 Hz, 3H). 118 Cl [00159] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.83 (s, 1H), 8.30-8.27 (m, 2H), 7.85 (s, 1H), 7.59-7.55 (m, 3H), 7.44 (s, 1H). 119 Cl [00160] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.27 (s, 1H), 7.31 (s, 1H), 2.63 (s, 3H). 120 Cl [00161] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 12.18 (s, 1H), 7.44 (s, 1H), 4.29-4.20 (m, 4H), 3.44-3.31 (m, 2H), 1.42 (s, 9H). 121 Cl [00162] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.92 (s, 1H), 7.68-7.61 (m, 2H), 7.60-7.52 (m, 3H), 7.46 (s, 2H). 122 Cl [00163] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.72 (s, 1H), 7.31 (s, 1H), 2.48 (s, 3H). 123 Cl [00164] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 11.33 (s, 1H), 7.99-7.96 (m, 2H), 7.66-7.54 (m, 3H), 7.40 (s, 1H). 124 Cl [00165] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 9.80 (s, 1H), 7.43 (s, 1H), 7.05-6.96 (m, 2H), 6.47 (s, 1H), 3.85 (s, 3H), 0.08 (s, 9H). 125 Cl [00166] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.08 (s, 1H), 7.39 (s, 1H), 5.88 (s, 1H), 3.89 (s, 3H), 0.21 (s, 9H). 126 Cl [00167] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.08 (s, 1H), 7.41 (s, 1H), 6.20 (s, 1H), 3.76 (s, 3H), 0.33 (s, 9H). 127 Cl [00168] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.23 (s, 1H), 7.37 (s, 1H), 6.82 (s, 1H), 3.89 (s, 3H), 1.97 (s, 6H). 128 Cl [00169] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.22 (s, 1H), 7.37 (s, 1H), 5.88 (s, 1H), 3.89 (s, 3H), 2.49 (s, 6H). 129 Cl [00170] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.35 (s, 1H), 7.35 (s, 1H), 5.56 (s, 1H), 3.89 (s, 3H), 1.91 (s, 6H). 130 Cl [00171] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 10.10 (s, 1H), 7.98 (d, J = 2.5 Hz, 1H), 7.37 (s, 1H), 6.86 (d, J = 2.5 Hz, 1H), 2.11 (s, 3H). 131 Cl [00172] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 9.57 (s, 1H), 8.79 (dd, J = 5.1, 1.3 Hz, 1H), 7.95-7.82 (m, 3H), 7.50 (s, 1H), 6.64 (s, 1H), 2.39 (s, 3H). 132 Cl [00173] .sup.1H NMR (500 MHz, DMSO-d.sub.6) 9.54 (s, 1H), 7.21 (s, 1H), 6.67 (d, J = 6.2 Hz, 1H), 6.28 (dd, J = 10.9, 6.2 Hz, 1H), 6.11-6.02 (m, 1H), 2.90-2.81 (m, 2H). 133 CN [00174] 134 NH.sub.2 [00175] 135 Ph [00176] 136 Br [00177] 137 Cl [00178] 138 Cl [00179] 139 OH [00180] 140 Cl [00181] 141 Cl [00182] 142 Cl [00183] 143 CONH.sub.2 [00184] 144 Cl [00185] 145 Cl [00186] 146 Cl [00187] 147 Cl [00188] 148 CH.sub.2F [00189] 149 Cl [00190] 150 Cl [00191] 151 Cl [00192] 152 Cl [00193] 153 Cl [00194] 154 Cl [00195] 155 Cl [00196] 156 Cl [00197] 157 Cl [00198] 158 Cl [00199] 159 Cl [00200] 160 Cl [00201] 161 Cl [00202] 162 Cl [00203] 163 Cl [00204] 164 Cl [00205] 165 Cl [00206] 166 Cl [00207] 167 Cl [00208] 168 Cl [00209] 169 Cl [00210] 170 Cl [00211] 171 Cl [00212] 172 Cl [00213] 173 Cl [00214] 174 Cl [00215] 175 Cl [00216] 176 Cl [00217] 177 Cl [00218] 178 Cl [00219] 179 Cl [00220] 180 Cl [00221] 181 Cl [00222] 182 Cl [00223] 183 Cl [00224] 184 Cl [00225] 185 Cl [00226] 186 Cl [00227] 187 Cl [00228] 188 Cl [00229] 189 Cl [00230] 190 Cl [00231] 191 Cl [00232] 192 Cl [00233] 193 Cl [00234] 194 Cl [00235] 195 Cl [00236] 196 Cl [00237] 197 Cl [00238] 198 Cl [00239] 199 Cl [00240] 200 Cl [00241] 201 Cl [00242] 202 Cl [00243] 203 Cl [00244] 204 Cl [00245] 205 Cl [00246] 206 Cl [00247] 207 Cl [00248] 208 Cl [00249] 209 Cl [00250] 210 Cl [00251] 211 Cl [00252] 212 Cl [00253] 213 Cl [00254] 214 Cl [00255] 215 Cl [00256] 216 Cl [00257] 217 Cl [00258] 218 Cl [00259] 219 Cl [00260] 220 Cl [00261] 221 Cl [00262] 222 Cl [00263] 223 Cl [00264] 224 Cl [00265] 225 Cl [00266] 226 Cl [00267] 227 Cl [00268] 228 Cl [00269] 229 Cl [00270] 230 Cl [00271] 231 Cl [00272] 232 Cl [00273] 233 Cl [00274] 234 Cl [00275] 235 Cl [00276] 236 Cl [00277] 237 Cl [00278] 238 Cl [00279] 239 Cl [00280] 240 Cl [00281] 241 Cl [00282] 242 Cl [00283] 243 Cl [00284] 244 Cl [00285] 245 Cl [00286] 246 Cl [00287] 247 Cl [00288] 248 Cl [00289] 249 Cl [00290] 250 Cl [00291] 251 Cl [00292] 252 Cl [00293] 253 Cl [00294] 254 Cl [00295] 255 Cl [00296] 256 Cl [00297] 257 Cl [00298] 258 Cl [00299] 259 Cl [00300] 260 Cl [00301] 261 Cl [00302] 262 Cl [00303] 263 Cl [00304] 264 Cl [00305] 265 Cl [00306] 266 Cl [00307] 267 Cl [00308] 268 Cl [00309] 269 Cl [00310] 270 Cl [00311] 271 Cl [00312] 272 Cl [00313] 273 Cl [00314] 274 Cl [00315] 275 Cl [00316] 276 Cl [00317] 277 Cl [00318] 278 Cl [00319] 279 Cl [00320] 280 Cl [00321] 281 Cl [00322] 282 Cl [00323] 283 Cl [00324] 284 Cl [00325] 285 Cl [00326] 286 Cl [00327] 287 Cl [00328] 288 Cl [00329] 289 Cl [00330] 290 Cl [00331] 291 Cl [00332] 292 Cl [00333] 293 Cl [00334] 294 Cl [00335] 295 Cl [00336] 296 Cl [00337] 297 Cl [00338] 298 Cl [00339] 299 Cl [00340] 300 Cl [00341] 301 Cl [00342] 302 Cl [00343] 303 Cl [00344] 304 Cl [00345] 305 Cl [00346] 306 Cl [00347] 307 Cl [00348] 308 Cl [00349] 309 Cl [00350] 310 Cl [00351] 311 Cl [00352] 312 Cl [00353] 313 Cl [00354] 314 Cl [00355] 315 Cl [00356] 316 Cl [00357] 317 Cl [00358] 318 Cl [00359] 319 Cl [00360] 320 Cl [00361] 321 Cl [00362] 322 Cl [00363] 323 CF.sub.3 [00364] 324 CF.sub.3 [00365] 325 CF.sub.3 [00366] 326 CF.sub.3 [00367] 327 CF.sub.3 [00368] 328 CF.sub.3 [00369] 329 CF.sub.3 [00370] 330 CF.sub.3 [00371] 331 CF.sub.3 [00372] 332 CF.sub.3 [00373] 333 CF.sub.3 [00374] 334 CF.sub.3 [00375] 335 CF.sub.3 [00376]

TABLE-US-00002 TABLE 2 Structure of group M in the derivative Compound I-1 I-1 [00377] No. M M-1 [00378] M-2 [00379] M-3 [00380] M-4 [00381] M-5 [00382] M-6 [00383] M-7 [00384] M-8 [00385] M-9 [00386] M-10 [00387] M-11 [00388] M-12 [00389] M-13 [00390] M-14 [00391] M-15 [00392] M-16 [00393] M-17 [00394] M-18 [00395] M-19 [00396] M-20 [00397] M-21 [00398] M-22 [00399] M-23 [00400] M-24 [00401] M-25 [00402] M-26 [00403] M-27 [00404] M-28 [00405] M-29 [00406] M-30 [00407] M-31 [00408] M-32 [00409] M-33 [00410] M-34 [00411] M-35 [00412] M-36 [00413] M-37 [00414] M-38 [00415] M-39 [00416] M-40 [00417] M-41 [00418] M-42 [00419] M-43 [00420] M-44 [00421] M-45 [00422] M-46 [00423] M-47 [00424] M-48 [00425] M-49 [00426] M-50 [00427] M-51 [00428] M-52 [00429] M-53 [00430] M-54 [00431] M-55 [00432] M-56 [00433] M-57 [00434] M-58 [00435] M-59 [00436] M-60 [00437] M-61 [00438] M-62 [00439] M-63 [00440] M-64 [00441] M-65 [00442] M-66 [00443] M-67 [00444] M-68 [00445] M-69 [00446] M-70 [00447] M-71 [00448] M-72 [00449] M-73 [00450] M-74 [00451] M-75 [00452] M-76 [00453] M-77 [00454] M-78 [00455] M-79 [00456] M-80 [00457] M-81 [00458] M-82 [00459] M-83 [00460] M-84 [00461] M-85 [00462] M-86 [00463] M-87 [00464] M-88 [00465] M-89 [00466] M-90 [00467] M-91 [00468] M-92 [00469] M-93 [00470] M-94 [00471] M-95 [00472] M-96 [00473] M-97 [00474] M-98 [00475] M-99 [00476] M-100 [00477] M-101 [00478] M-102 [00479] M-103 [00480] M-104 [00481] M-105 [00482] M-106 [00483] M-107 [00484] M-108 [00485] M-109 [00486] M-110 [00487] M-111 [00488] M-112 [00489] M-113 [00490] M-114 [00491] M-115 [00492] M-116 [00493] M-117 [00494] M-118 [00495] M-119 [00496] M-120 [00497] M-121 [00498] M-122 [00499] M-123 [00500] M-124 [00501] M-125 [00502] M-126 [00503] M-127 [00504] M-128 [00505] M-129 [00506] M-130 [00507] M-131 [00508] M-132 [00509] M-133 [00510] M-134 [00511] M-135 [00512] M-136 [00513] M-137 [00514] M-138 [00515] M-139 [00516] M-140 [00517] M-141 [00518] M-142 [00519] M-143 [00520] M-144 [00521] M-145 [00522] M-146 [00523] M-147 [00524] M-148 [00525] M-149 [00526] M-150 [00527] M-151 [00528] M-152 [00529] M-153 [00530] M-154 [00531] M-155 [00532] M-156 [00533] M-157 [00534] M-158 [00535] M-159 [00536] M-160 [00537] M-161 [00538] M-162 [00539] M-163 [00540] M-164 [00541] M-165 [00542] M-166 [00543] M-167 [00544] M-168 [00545] M-169 [00546] M-170 [00547] M-171 [00548] M-172 [00549] M-173 [00550] M-174 [00551] M-175 [00552] M-176 [00553] M-177 [00554] M-178 [00555] M-179 [00556] M-180 [00557] M-181 [00558] M-182 [00559] M-183 [00560] M-184 [00561] M-185 [00562] M-186 [00563] M-187 [00564] M-188 [00565] M-189 [00566] M-190 [00567] M-191 [00568] M-192 [00569] M-193 [00570] M-194 [00571] M-195 [00572] M-196 [00573] M-197 Me M-198 Et M-199 [00574] M-200 CN M-201 [00575] M-202 [00576] M-203 [00577] M-204 [00578] M-205 [00579] M-206 [00580] M-207 [00581] M-208 [00582] M-209 [00583] M-210 [00584] M-211 [00585] M-212 [00586] M-213 [00587] M-214 [00588] M-215 [00589] M-216 [00590]

TABLE-US-00003 TABLE 3 Structure and .sup.1HNMR data of the derivative Compound I-1 I-1 [00591] No. X Ar M .sup.1HNMR 1-1 Cl [00592] M-29 .sup.1H NMR (500 MHz, Chloroform-d) 7.46 (s, 1H), 6.47 (s, 1H), 4.23 (t, J = 7.5 Hz, 2H), 3.98 (s, 3H), 2.35 (s, 3H), 1.79-1.69 (m, 2H), 1.39-1.16 (m, 4H), 0.95 (t, J = 8.0 Hz, 3H). 1-2 Cl [00593] M-54 .sup.1H NMR (500 MHz, Chloroform-d) 7.43 (s, 1H), 6.49 (s, 1H), 3.98 (s, 3H), 2.85 (t, J = 8.0 Hz, 2H), 2.35 (s, 3H), 1.94-1.79 (m, 2H), 1.38-1.21 (m, 14H), 0.89 (t, J = 8.0 Hz, 3H). 1-3 Cl [00594] M-79 .sup.1H NMR (500 MHz, Chloroform-d) 7.74 (dd, J = 7.5, 2.0 Hz, 1H), 7.63-7.55 (m, 2H), 7.53 (dd, J = 7.5, 2.0 Hz, 1H), 7.32-7.21 (m, 1H), 6.48 (s, 1H), 3.91 (s, 3H), 2.35 (s, 3H). 1-4 Cl [00595] M-88 .sup.1H NMR (500 MHz, Chloroform-d) 8.25 (d, J = 2.0 Hz, 1H), 7.83 (dd, J = 7.5, 2.0 Hz, 1H), 7.57-7.50 (m, 2H), 6.49 (s, 1H), 4.00 (s, 3H), 2.35 (s, 3H). 1-5 Cl [00596] M-52 .sup.1H NMR (500 MHz, Chloroform-d) 7.50 (s, 1H), 7.30 (d, J = 2.5 Hz, 1H), 6.56 (s, 1H), 6.39 (dd, J = 2.5, 2.0 Hz, 1H), 5.51 (d, J = 2.0 Hz, 1H), 4.12 (s, 3H), 2.35 (s, 3H). 1-6 Cl [00597] M-205 .sup.1H NMR (500 MHz, Chloroform-d) 7.56 (s, 1H), 7.00 (q, J = 6.5 Hz, 1H), 6.48 (s, 1H), 5.22 (hept, J = 6.5 Hz, 1H), 3.98 (s, 3H), 2.35 (s, 3H), 1.77 (d, J = 6.5 Hz, 3H), 1.29 (d, J = 6.5 Hz, 6H). 1-7 Cl [00598] M-156 .sup.1H NMR (500 MHz, Chloroform-d) 7.52 (s, 1H), 6.41 (s, 1H), 4.03 (s, 3H), 3.60 (t, J = 7.5 Hz, 2H), 2.35 (s, 3H), 1.65-1.51 (m, 2H), 1.44-1.31 (m, 6H), 0.93 (t, J = 7.5 Hz, 3H). 1-8 Cl [00599] M-40 .sup.1H NMR (500 MHz, Chloroform-d) 7.41 (s, 1H), 6.33 (s, 1H), 3.97 (s, 3H), 2.91 (q, J = 6.5 Hz, 2H), 2.35 (s, 3H), 1.36 (t, J = 6.5 Hz, 3H). 1-9 Cl [00600] M-63 .sup.1H NMR (500 MHz, Chloroform-d) 7.47 (s, 1H), 6.38 (s, 1H), 3.99 (s, 3H), 3.64-3.50 (m, 4H), 3.47-3.37 (m, 4H), 2.35 (s, 3H). 1-10 Cl [00601] M-150 .sup.1H NMR (500 MHz, Chloroform-d) 7.43 (s, 1H), 6.50 (s, 1H), 3.97 (s, 3H), 2.35 (s, 3H), 2.16 (t, J = 7.5 Hz, 2H), 1.65-1.51 (m, 2H), 1.44-1.31 (m, 10H), 0.89 (t, J = 7.5 Hz, 3H). 1-11 Cl [00602] M-53 .sup.1H NMR (500 MHz, Chloroform-d) 7.43 (s, 1H), 6.49 (s, 1H), 3.98 (s, 3H), 2.85 (t, J = 8.0 Hz, 2H), 2.35 (s, 3H), 1.94-1.83 (m, 2H), 1.38-1.24 (m, 10H), 0.89 (t, J = 8.0 Hz, 3H). 1-12 CN [00603] M-1 1-13 NH.sub.2 [00604] M-2 1-14 Ph [00605] M-7 1-15 Br [00606] M-12 1-16 OH [00607] M-24 1-17 Cl [00608] M-27 .sup.1H NMR (300 MHz, Chloroform-d) 7.65 (s, 1H), 7.51 (d, J = 2.4 Hz, 1H), 7.41 (s, 1H), 6.20 (d, J = 2.4 Hz, 1H), 4.23 (t, J = 7.3 Hz, 2H), 1.64-1.36 (m, 4H), 0.98 (t, J = 7.7 Hz, 3H). 1-18 CONH.sub.2 [00609] M-37 1-19 Cl [00610] M-58 .sup.1H NMR (300 MHz, Chloroform-d) 9.34 (s, 1H), 7.36 (s, 1H), 3.17 (s, 6H). 1-20 Cl [00611] M-60 1-21 Cl [00612] M-77 1-22 Cl [00613] M-92 1-23 Cl [00614] M-104 1-24 Cl [00615] M-108 1-25 Cl [00616] M-119 .sup.1H NMR (300 MHz, Chloroform-d) 8.09- 7.99 (m, 2H), 7.91 (s, 1H), 1.72-1.62 (m, 1H), 1.07-0.89 (m, 2H), 0.72-0.63 (m, 2H). 1-26 Cl [00617] M-120 1-27 Cl [00618] M-121 1-28 OEt [00619] M-125 1-29 OCF.sub.3 [00620] M-126 1-30 Cl [00621] M-127 1-31 Cl [00622] M-128 .sup.1H NMR (300 MHz, Chloroform-d) 8.17 (s, 1H), 8.10 (s, 1H), 7.92 (s, 1H), 7.78-7.68 (m, 2H), 7.51-7.41 (m, 2H), 2.42 (s, 3H). 1-32 Cl [00623] M-131 1-33 Cl [00624] M-132 1-34 Cl [00625] M-160 .sup.1H NMR (300 MHz, Chloroform-d) 7.53 (d, J = 2.4 Hz, 2H), 7.48-7.31 (m, 4H), 7.30- 7.17 (m, 2H), 6.86 (d, J = 2.4 Hz, 1H). 1-35 CHF.sub.2 [00626] M-162 1-36 Cl [00627] M-165 .sup.1H NMR (300 MHz, Chloroform-d) 9.38 (s, 1H), 7.31 (s, 1H), 2.63 (s, 3H), 2.47 (s, 3H). 1-37 CF.sub.2CF.sub.3 [00628] M-168 1-38 Cl [00629] M-198 .sup.1H NMR (300 MHz, Chloroform-d) 7.57 (s, 1H), 7.35 (d, J = 2.5 Hz, 1H), 7.02 (d, J = 2.5 Hz, 1H), 4.34 (q, J = 8.1 Hz, 2H), 3.75 (s, 3H), 1.61 (t, J = 8.0 Hz, 3H). 1-39 Br [00630] M-199 1-40 CN [00631] M-200 1-41 Me [00632] M-203 1-42 Cl [00633] M-204 .sup.1H NMR (300 MHz, Chloroform-d) 7.73 (s, 1H), 7.60-7.47 (m, 2H), 6.71 (q, J = 6.8 Hz, 1H), 6.37 (d, J = 2.4 Hz, 1H), 4.79 (d, J = 8.0 Hz, 2H), 1.85 (d, J = 6.8 Hz, 3H), 1.32 (t, J = 8.0 Hz, 3H). 1-43 Cl [00634] M-207 1-44 Cl [00635] M-208 1-45 Cl [00636] M-209 1-46 OMe [00637] M-211 1-47 Cl [00638] M-212 .sup.1H NMR (300 MHz, Chloroform-d) 7.34 (s, 1H), 6.76 (s, 1H), 4.02 (s, 3H), 2.47 (s, 6H). 1-48 Et [00639] M-123 1-49 F [00640] M-216 1-50 Cl [00641] M-40 .sup.1H NMR (300 MHz, Chloroform-d) 9.35 (s, 1H), 7.38 (s, 1H), 2.91 (q, J = 8.0 Hz, 2H), 1.37 (t, J = 8.0 Hz, 3H).

[0103] 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.

[0104] 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.

[0105] 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 beany 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.

[0106] Examples of representative compounds are as follows:

[0107] 1. Synthesis of Compound 1

##STR00642##

[0108] (1) To a three-necked round bottom flask, compound 1-a (10 g, 67 mmol), compound 1-b (14.9 g, 67 mmol) and potassium carbonate (27.8 g, 201 mmol) were charged, and nitrogen replacement was performed three times after the addition of 1,4-dioxane (100 mL)/water (20 mL). Pd(dppf)Cl.sub.2CH.sub.2Cl.sub.2 (0.2 g) was added quickly under nitrogen protection and then nitrogen replacement was performed three times. The reaction solution was treated by nitrogen replacement for another three times and reacted at 100 C. for 16 h. After high performance liquid chromatography detection showed the completion of the reaction, the reaction system was concentrated and subjected to column chromatography separation to obtain 10 g (48 mmol, yield 71%) of compound 1-c (grey solid).

[0109] (2) To a three-necked round bottom flask, compound 1-c (10 g, 48 mmol), N-chloro succimide (6.4 g, 48 mmol), benzoyl peroxide (0.5 g, catalytic amount) and acetonitrile (100 mL) were charged and reacted at 80 C. for 16 h. A small amount of the raw material was detected to remain by high performance liquid chromatography. The reaction system was concentrated and subjected to column chromatography separation to obtain 5 g (21 mmol, yield 42%) of compound 1-d (white solid).

[0110] (3) To a three-necked round bottom flask, compound 1-d (1 g, 4 mmol), potassium acetate (2 g, 20 mmol) and 10 mL of DMSO were charged and reacted at 120 C. for 2 h. After high performance liquid chromatography detection showed the completion of the reaction, the reaction solution was cooled to 25 C. and added with 1M HCl in a dropwise manner with temperature control (no higher than 25 C.) till pH of the solution was around 5. Solid was precipitated out, which was collected by suction filtration, washed with a large quantity of water, purified by beating with methyl tert-butyl ether (20 mL) and a small amount of methanol (1 mL). After suction filtration, the solid was dried to obtain 300 mg (1.3 mmol, yield 32%) of compound 1 (off-white solid).

[0111] 2. Synthesis of Compound 1-1

##STR00643##

[0112] To a 50 mL eggplant-shaped flask, compound 1 (1 equiv.), potassium carbonate (3 equiv.) and acetonitrile (10V) were charged at room temperature, then added with

##STR00644##

(1.2 equiv.) and stirred for 30 minutes after the addition. TLC detection showed the completion of the reaction. The reaction system was concentrated to remove acetonitrile, then dissolved with water (5V) and extracted with ethyl acetate (5V*3), then ethyl acetate was removed by vacuum distillation. The residue was separated through silica gel column chromatography (100 mesh to 200 mesh) to obtain the product with yield of 72%.

[0113] 3. Synthesis of Compound 1-5

##STR00645##

[0114] To a 50 mL eggplant-shaped flask, compound 1 (1 equiv.), triethyl amine (2 equiv.) and dichloromethane (5V) were charged in ice bath, and

##STR00646##

(1.2 equiv.) was added in ice bath and stirred for 30 minutes at room temperature. TLC detection showed the completion of the reaction. The reaction system was added with water and extracted with dichloromethane (5V*3), and then subjected to vacuum distillation to remove dichloromethane. The residue was separated through silica gel column chromatography (100 mesh to 200 mesh) to obtain the product with yield of 73%.

[0115] 4. Synthesis of Compound 1-6

##STR00647##

[0116] To a 50 mL eggplant-shaped flask, compound 1 (1 equiv.),

##STR00648##

(1.2 equiv.), potassium carbonate (3 equiv.) and acetonitrile (10 V) were charged, then heated to 80 C. and stirred for 12 h. TLC detection showed the completion of the reaction. The reaction system was subjected to vacuum distillation to remove acetonitrile, then dissolved with water (5V) and extracted with ethyl acetate (5V*3), and then ethyl acetate was removed by vacuum distillation. The residue was separated through silica gel column chromatography (100 mesh to 200 mesh) to obtain the product with yield of 79%.

[0117] 5. Synthesis of Compound 1-8

##STR00649##

[0118] To a 50 mL eggplant-shaped flask, compound 1 (1 equiv.), potassium carbonate (3 equiv.) and acetonitrile (10 V) were charged, and

##STR00650##

(1.2 equiv.) was added in a dropwise manner and stirred for 30 min at room temperature after the addition. TLC detection showed the completion of the reaction. The reaction system was subjected to vacuum distillation to remove acetonitrile, then dissolved with water (5V) and extracted with ethyl acetate (5V*3), and then ethyl acetate was removed by vacuum distillation. The residue was separated through silica gel column chromatography (100 mesh to 200 mesh) to obtain the product with yield of 72%.

[0119] 6. Synthesis of Compound 1-9

##STR00651##

[0120] To a 50 mL eggplant-shaped flask, compound 1 (1 equiv.)

##STR00652##

(1.2 equiv.), potassium carbonate (3 equiv.) and acetonitrile (10 V) were charged, then heated to 80 C. and stirred for 12 h. TLC detection showed the completion of the reaction. The reaction system was subjected to vacuum distillation to remove acetonitrile, then dissolved with water (5V) and extracted with ethyl acetate (5V*3), and then ethyl acetate was removed by vacuum distillation. The residue was separated through silica gel column chromatography (100 mesh to 200 mesh) to obtain the product with yield of 85%.

[0121] 7. Synthesis of Compound 1-25

##STR00653##

[0122] With reference to the preparation method of compound 1, compound 9 was prepared. Then to a 50 mL eggplant-shaped flask, compound 9 (1 equiv.), triethyl amine (3 equiv.) and dichloromethane (10 V) were charged in ice bath, and

##STR00654##

(1.2 equiv.) was added in dropwise manner in ice bath, and then stirred at room temperature for 30 min. TLC detection showed the completion of the reaction. The reaction system was added with water (5V) and extracted with dichloromethane (5V*3), and then subjected to vacuum distillation to remove dichloromethane. The residue was separated through silica gel column chromatography (100 mesh to 200 mesh) to obtain the product with yield of 81%.

[0123] 8. Synthesis of Compound 1-36

##STR00655##

[0124] With reference to the preparation method of compound 1, compound 22 was prepared. Then to a 50 mL eggplant-shaped flask, compound 22 (1 equiv.), Phenofluor (1.5 equiv.), cesium fluoride (3 equiv.) and toluene (10 V) were charged, then heated to 80 C. and stirred for 18 h. TLC detection showed the completion of the reaction. Intermediate 1-36-a was obtained after work-up. To another 50 mL eggplant-shaped flask, compound 1-36-a (1 equiv.),

##STR00656##

(1.2 equiv.), potassium carbonate (3 equiv.) and acetonitrile (10 V) were charged, then heated to 80 C. and stirred for 18 h. TLC detection showed the completion of the reaction. The reaction system was subjected to vacuum distillation to remove acetonitrile, then added with water (5V) and extracted with ethyl acetate (5V*3), and then ethyl acetate was removed by vacuum distillation. The residue was separated through silica gel column chromatography (100 mesh to 200 mesh) to obtain the product with yield of 65%.

[0125] 9. Synthesis of Compound 1-47

##STR00657##

[0126] With reference to the preparation method of compound 1, compound 48 was prepared. Then to a 50 mL eggplant-shaped flask, compound 48 (1 equiv.), POCl.sub.3 (1.5 equiv.), 1,2-dichloroethane (10 V) and 5% N,N-dimethylformamide were charged, then heated to 80 C. and stirred for 6 h. TLC detection showed the completion of the reaction. Water (5V) was added for dissolution and extracted with 1,2-dichloromethane (5V*3), and then 1,2-dichloroethane was removed by vacuum distillation to obtain compound 1-47a. To another 50 mL eggplant-shaped flask, compound 1-47-a (1 equiv.),

##STR00658##

(1.2 equiv.), potassium hydroxide (3 equiv.) and N,N-dimethyl formamide (10 V) were charged, then heated to 100 C. and stirred for 18 h. TLC detection showed the completion of the reaction. The reaction system was diluted with water (5V) and extracted with ethyl acetate (5V*3), and then ethyl acetate was removed by vacuum distillation. The residue was separated through silica gel column chromatography (100 mesh to 200 mesh) to obtain the product with yield of 48%.

[0127] Evaluation of Biological Activity:

[0128] The activity level standard of harmful plant destruction (i.e. growth inhibition rate) is as follows:

[0129] Level 10: completely dead;

[0130] Level 9: above 90% growth inhibition rate;

[0131] Level 8: above 80% growth inhibition rate;

[0132] Level 7: above 70% growth inhibition rate;

[0133] Level 6: above 60% growth inhibition rate;

[0134] Level 5: above 50% growth inhibition rate;

[0135] Level 4: above 40% growth inhibition rate;

[0136] Level 3: above 30% growth inhibition rate;

[0137] Level 2: above 20% growth inhibition rate;

[0138] Level 1: below 20% growth inhibition rate;

[0139] Level 0: no effect.

[0140] The above described growth inhibition rates are fresh weight inhibition rates.

[0141] 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-US-00004 TABLE 3 Experiment on weed control effect of compounds of Formula I in Post-emergence stage Compound Rorippa Amaranthus Veronica No. Chenopodiaceae indica retroflexus polita Dose 1 10 10 10 10 3000 g/ha 3 10 10 10 10 3000 g/ha 4 10 10 10 10 3000 g/ha 27 10 10 10 10 3000 g/ha 29 10 10 10 10 3000 g/ha 33 10 10 10 10 3000 g/ha 44 10 10 10 10 3000 g/ha 45 10 10 10 10 3000 g/ha 48 10 10 10 10 3000 g/ha 54 10 10 10 10 3000 g/ha 56 10 10 10 10 3000 g/ha 61 10 10 10 10 3000 g/ha 71 10 10 10 10 3000 g/ha 72 10 10 10 10 3000 g/ha 73 10 10 10 10 3000 g/ha 74 10 10 10 10 3000 g/ha 75 10 10 10 10 3000 g/ha 76 10 10 10 10 3000 g/ha 77 10 10 10 10 3000 g/ha 78 10 10 10 10 3000 g/ha 79 10 10 10 10 3000 g/ha 80 10 10 10 10 3000 g/ha 81 10 10 10 10 3000 g/ha 82 10 10 10 10 3000 g/ha 95 10 10 10 10 3000 g/ha 130 10 10 10 10 3000 g/ha

TABLE-US-00005 TABLE 4 Experiment on weed control effect of derivatives of Formula I-1 in Post-emergence stage (2000 g/ha) Compound Amaranthus Setaria Veronica No. retroflexus Chenopodiaceae viridis polita 1-1 10 10 10 10 1-2 10 10 10 10 1-3 10 10 10 10 1-4 10 10 10 10 1-5 10 10 10 10 1-6 10 10 10 10 1-7 10 10 10 10 1-8 10 10 10 10 1-9 10 10 10 10 1-10 10 10 10 10 1-11 10 10 10 10

[0142] Comparative Experiment:

[0143] The post-emergence test conditions were the same as above, and the results are shown in Table 5.

[0144] Control Compound A:

##STR00659##

Control Compound B:

[0145] ##STR00660##

TABLE-US-00006 TABLE 5 Results of comparison experiment Compound Echinochloa Setaria Digitaria Rorippa Veronica NO. crus-galli viridis sanguinalis indica polita Dose 1 8 10 7 10 10 300 g/ha 29 8 10 6 10 9 300 g/ha 33 N N N 10 10 300 g/ha 1-1 8 10 8 10 10 300 g/ha 1-2 8 10 10 10 10 300 g/ha 1-3 9 10 9 10 10 300 g/ha 1-11 9 9 7 10 10 300 g/ha Control 0 2 0 2 5 300 g/ha Compound A Control 0 2 0 3 5 300 g/ha Compound B Note: N means no data.

[0146] It can be seen from the above table, the compounds of the present invention have better herbicidal activity than the control compounds A and B.

[0147] Experiment of Pre-Emergence Test:

[0148] 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 0.5-2 cm 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 250 g/ha, especially to weeds such as Echinochloa crusgalli, Digitaria sanguinalis and Abutilon theophrasti, etc., and many compounds had good selectivity for corn, wheat, rice, soybean, oilseed rape, etc.

[0149] It is found in the experiment that the compounds of the present invention generally have good weed control efficacy, especially for major weeds 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 broadleaf weeds, which are resistant to ALS inhibitor.

[0150] Transplanted rice safety evaluation and weed control effect evaluation in rice field:

[0151] Rice field soil was loaded into a 1/1,000,000 ha pot. The seeds of Echinochloa crusgalli, Scirpus juncoides, Bidens tripartite and Sagittaria trifolia L. were sowed and gently covered with soil, then left to stand still in greenhouse in the state of 0.5-1 cm of water storage. The tuber of Sagittaria trifolia L. was planted in the next day or 2 days later. It was kept at 3-4 cm 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.

[0152] In addition, the rice field soil that loaded into the 1/1,000,000 ha pot was leveled to keep water storage at 3-4 cm depth. The 3 leaf stage rice (japonica rice) was transplanted at 3 cm of transplanting depth the next day. The compound of the present invention was treated by the same way after 5 days of transplantation.

[0153] The fertility condition of Echinochloa crusgalli, Scirpus juncoides, Bidens tripartite and Sagittaria trifolia 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 of the present invention have excellent activity and selectivity, especially for Sagittaria trifolia L. and Echinochloa crusgalli.

[0154] Note: The seeds of Echinochloa crusgalli, Scirpus juncoides, Sagittaria trifolia L. and Bidens tripartite were collected from Heilongjiang Province of China. Tests indicated that the weeds were resistant to common rate of pyrazosulfuron-ethyl.

[0155] At the same time, it is found after several tests that the compound and the composition 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 wheat, corn, rice, sugarcane, soybean, cotton, oil sunflower, potato, orchards and vegetables in different herbicide application methods.