CN101522030A - Fungicides - Google Patents

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Publication number
CN101522030A
CN101522030A CNA2007800368897A CN200780036889A CN101522030A CN 101522030 A CN101522030 A CN 101522030A CN A2007800368897 A CNA2007800368897 A CN A2007800368897A CN 200780036889 A CN200780036889 A CN 200780036889A CN 101522030 A CN101522030 A CN 101522030A
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alkyl
compound
methyl
optional replacement
base
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CN101522030B (en
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F·墨菲凯萨比
R·博戴格尼斯
L·夸兰塔
H-G·布鲁纳
F·策德鲍姆
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Syngenta Participations AG
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Quinoline Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Compounds of the general formula wherein the substituents are as defined in claim (1), are useful as fungicides.

Description

Fungicide
The present invention relates to novel quinoline oxygen phenylalkanoic acid acid amides, prepare their method, relate to the composition that comprises them and also relate to and use them to come, particularly to the fungal infection of plant antimycotic.
Some quinoline oxy alkanoic acid amides derivative and they are disclosed in for example WO 04/047538 and JP2001-89453 as the purposes of agricultural and gardening bactericide.
The present invention relates to the substd quinolines that provides specific-6-base oxygen phenylalkanoic acid acid amides, mainly as plant fungicide.
Thus, according to the compound that the invention provides general formula I
Figure A200780036889D00121
Wherein
Q 1, Q 2And Q 3Be the C of halogen, cyano group, nitro, azido, optional replacement independently of one another 1-6The C of alkyl, optional replacement 3-6The comprising at least one and be selected from sulphur, oxygen or R wherein of cycloalkyl, optional replacement 0Be the C of hydrogen or optional replacement 1-6The NR of alkyl 0Heteroatomic C 3-6The C of-heterocyclic radical, optional replacement 3-6Cycloalkyl (C 1-4) C of alkyl, optional replacement 2-6The C of thiazolinyl, optional replacement 2-6The C of alkynyl, optional replacement 1-6The C of alkoxyl, optional replacement 2-6The C of alkene oxygen base, optional replacement 2-6Aryl (the C of the aryl of alkynyloxy group, optional replacement, the aryloxy group of optional replacement, optional replacement 1-6) aryl (C of alkyl, optional replacement 1-6) heteroaryl (C of alkoxyl, the heteroaryl of optional replacement, the heteroaryloxy of optional replacement, optional replacement 1-6) heteroaryl (C of alkyl, optional replacement 1-6) alkoxyl ,-SF 5Or-S (O) u(C 1-6) alkyl, wherein u is 0,1 or 2 and described alkyl group is optional is replaced by halogen, perhaps
Q 1, Q 2And Q 3Be independently of one another-OSO 2(C 1-4) alkyl, wherein said alkyl group is optional to be replaced by halogen, perhaps
Q 1, Q 2And Q 3Be independently of one another-CONR uR v,-COR u,-CO 2R u,-CR u=NR v,-NR uR v,-NR uCOR v,-NR uCO 2R v,-SO 2NR uR vOr-NR uSO 2R w, R wherein wBe the C of optional replacement 1-6Alkyl and R uAnd R vBe hydrogen or the optional C that is replaced by halogen independently of one another 1-6Alkyl is perhaps at-CONR uR vOr-SO 2NR uR vSituation under, R uR vCan be selected from sulphur, oxygen or NR in conjunction with forming 5-or 6-unit's carbocyclic ring or heterocycle, comprising 0Hetero atom, R wherein 0Be the C of hydrogen or optional replacement 1-6Alkyl is perhaps at-CR u=NR vSituation under, R vBe the C of hydroxyl or optional replacement 1-6The aryloxy group of alkoxyl, optional replacement or the heteroaryloxy of optional replacement, perhaps
Q 1And Q 2Also represent hydrogen independently of one another,
R 1Be the C of optional replacement 1-4The C of alkyl, optional replacement 2-4The C of thiazolinyl, optional replacement 2-4The C of alkynyl or optional replacement 3-4Cycloalkyl,
R 2Be hydrogen, C 1-8Alkyl, C 3-4Cycloalkyl, C 2-8Thiazolinyl, cyano group, hydroxyl, alkoxyl, cyano group (C 1-4) alkyl, C 1-4Alkoxyl (C 1-4) alkyl, C 1-4Alkoxyl (C 1-4) alkoxyl (C 1-4) alkyl or benzyloxy (C 1-4) alkyl, wherein said benzyl ring is alternatively by C 1-4Alkoxyl replaces,
R 3Be-(CR aR b) p(CR cR d) q(X) r(CR eR f) sR 4, wherein
R a, R b, R c, R d, R eAnd R fBe hydrogen, C independently of one another 1-4Alkyl, halogen, cyano group, hydroxyl, C 1-4Alkoxyl or C 1-4Alkoxy carbonyl group, perhaps
R aR b, R cR dOr R eR fCan be in conjunction with forming 3 to 8 yuan of carbocyclic rings or heterocycles, it comprises and is selected from sulphur, oxygen or NR oHetero atom, R wherein oBe the C of hydrogen or optional replacement 1-6Alkyl,
X is (CO), (CO) O, O (CO), O, S (O) t, wherein t is 0,1 or 2, perhaps X is NH or N (C 1-6) alkyl, p, r and s are 0 or 1 independently of one another,
Q is 0,1 or 2,
R 4Be the C of optional replacement 1-6The C of alkyl, optional replacement 2-6Thiazolinyl ,-CR Uu=NR Vv, R wherein UuBe hydrogen or C 1-6Alkyl and R VvBe the C of hydroxyl or optional replacement 1-6The aryloxy group of alkoxyl, optional replacement or the heteroaryloxy of optional replacement or-CH 2-C ≡ C-R 5, wherein
R 5Be the C that the following group of hydrogen, optional quilt replaces 1-8Alkyl: halogen, hydroxyl, C 1-6Alkoxyl, C 1-3Alkoxyl (C 1-3) alkoxyl, cyano group, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkyl amino carbonyl oxy, three (C 1-4) alkyl siloxy or wherein g be 0,1 or 2-S (O) g(C 1-6) alkyl, perhaps
R 5Be the C that the following group of optional quilt replaces 3-6Cycloalkyl: halogen, hydroxyl, C 1-6Alkoxyl, C 1-3Alkoxyl (C 1-3) alkoxyl, cyano group, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkyl amino carbonyl oxy, three (C 1-4) alkyl siloxy or wherein g be 0,1 or 2-S (O) g(C 1-6) alkyl, perhaps
R 5Be C 3-6Cycloalkyl (C 1-4) alkyl, the following group of the optional quilt of wherein said alkyl and/or cycloalkyl moiety replaces: halogen, hydroxyl, C 1-6Alkoxyl, C 1-3Alkoxyl (C 1-3) alkoxyl, cyano group, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkyl amino carbonyl oxy, three (C 1-4) alkyl siloxy or-S (O) g(C 1-6) alkyl, wherein g is 0,1 or 2, perhaps
R 5Be the aryl (C of the aryl of optional replacement, optional replacement 1-4) aryloxy group (C of alkyl, optional replacement 1-4) alkyl, the heteroaryl of optional replacement or the heteroaryl (C of optional replacement 1-4)Heteroaryloxy (the C of alkyl or optional replacement 1-4) alkyl, perhaps
R 4Be the C of optional replacement 3-6The C of cycloalkyl, optional replacement 5-6The 5-of the aryl of cycloalkenyl group, optional replacement, the heteroaryl of optional replacement or optional replacement is to 8-unit ring, and it comprises alternatively and is selected from sulphur, oxygen or NR 0Hetero atom, R wherein oBe the C of hydrogen or optional replacement 1-6Alkyl, perhaps
Work as R 3Be-(CR aR b) p(CR cR d) q(X) r(CR eR f) sR 4The time, R 2And R 3Can be in conjunction with forming 5-or 6-unit ring, it is optional by halogen, C 1-4Alkyl, one-or two-(C 1-4) alkyl amino-carbonyl replaces, and comprise alternatively and be selected from sulphur, oxygen and NR 00Hetero atom, R wherein 00Be alternatively by halogen, C 1-6The C that alkoxyl or cyano group replace 1-4Alkyl, perhaps R 00Be alternatively by nitro, C 1-4Alkyl, halo (C 1-4) alkyl, C 1-4The phenyl that alkyl-carbonyl or heteroaryl replace, perhaps R 2And R 3Can be in conjunction with 6 of the optional replacement of formation, 6-unit dicyclo,
R 3Be-(CR 30R 40) C ≡ CR 50, wherein
R 30And R 40Be hydrogen, C independently of one another 1-6Alkyl, halo (C 1-4) alkyl, C 1-4Alkoxyl (C 1-3) alkyl, C 2-3Thiazolinyl or C 2-3Alkynyl, perhaps
R 30And R 40With the carbon atom that links to each other with them in conjunction with forming 3 to 6 yuan of carbocyclic rings or heterocycles, it comprises and is selected from sulphur, oxygen or NR 000Hetero atom, R wherein 000Be hydrogen or C 1-4Alkyl, wherein said carbocyclic ring or heterocycle are alternatively by halogen or C 1-4Alkyl replaces,
R 50Be the C of hydrogen, optional replacement 1-4The C of alkyl, optional replacement 3-6The aryl of cycloalkyl, optional replacement or the heteroaryl of optional replacement, it comprises and is selected from sulphur, oxygen or NR 000Hetero atom, R wherein 000Be hydrogen or C 1-6Alkyl,
L is sulphur or oxygen, and
N is 0,1 or 2, and
The salt of formula I compound or N-oxide.
The compounds of this invention comprises at least one asymmetric carbon atom and can be used as enantiomer (or as in pairs diastereomer) or exist as its mixture.In addition, when n was 1, The compounds of this invention was a sulfoxide, and it can exist by two kinds of enantiomeric forms, and the carbon of adjacency also can exist by two kinds of enantiomeric forms.So the compound of general formula (I) can be used as racemic modification, diastereomer or single enantiomer exists, and the present invention includes the institute of all proportions might isomer or isomer mixture.To any given compound, expect that all a kind of isomer can have more Fungicidally active than another kind.
The N-oxide of formula I compound is preferably represented the N-oxide by quinoline moiety formation.
The salt that formula I compound can form preferably acts on those that form by these compounds and acid.Term " acid " comprises inorganic acid such as hydrogen halides, sulfuric acid, phosphoric acid etc., and organic acid, preferred normally used alkanoic acid, for example formic acid, acetate and propionic acid.
Except as otherwise noted, the moieties of alkyl group and alkoxyl, alkylthio group etc. comprises 1 to 6, common 1 to 4 carbon atom with the straight or branched form aptly.Example is methyl, ethyl, n-pro-pyl and isopropyl and normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.The example that moieties comprises 5 or 6 carbon atoms is n-pentyl and n-hexyl.The suitable optional substituent example of alkyl group and part comprises halogen, hydroxyl, C 1-4Alkoxyl and C 1-4Alkoxyl (C 1-4) alkoxyl, cyano group, the aryl of optional replacement and the heteroaryl of optional replacement.When optional substituting group was halogen, halogenated alkyl group or part be a chloromethyl, a methyl fluoride, dichloromethyl, difluoromethyl, trichloromethyl or trifluoromethyl normally.
Except as otherwise noted, thiazolinyl and alkynyl part also comprises 2 to 6, common 2 to 4 carbon atoms with the straight or branched form aptly.Example is pi-allyl, acetenyl and propargyl.Optional substituting group comprises the aryl of halogen, alkoxyl, optional replacement and the heteroaryl of optional replacement.
Halogen comprises fluorine, chlorine, bromine and iodine.
Aryl is phenyl but also comprise naphthyl, anthryl and phenanthryl normally.
Heteroaryl normally comprises one or more sulphur, oxygen or NR part as heteroatomic 5-or 6-unit aromatic ring, and it can condense with one or more other aromatic rings or heteroaromatic rings such as phenyl ring.Example is thienyl, furyl, pyrrole radicals, isoxazolyl, oxazolyl, thiazolyl, oxadiazole base, pyrazolyl, imidazole radicals, triazolyl, isothiazolyl, tetrazole radical, thiadiazolyl group, pyridine radicals, pyrimidine radicals, pyrazinyl, pyridazinyl, triazinyl, benzofuranyl, benzothienyl, dibenzofuran group, dibenzothiophenes base, benzothiazolyl, benzoxazolyl, benzimidazolyl, indyl, quinolyl, isoquinolyl, quinazolyl and quinoxalinyl, and its N-oxide and salt when suitable.Above-mentioned any aryl or heteroaryl definition are optional replacements.Except as otherwise noted, the substituting group that can exist comprises one or more following substituting groups: halogen, hydroxyl, sulfydryl, C 1-6Alkyl (particularly methyl and ethyl), C 2-6Thiazolinyl (particularly pi-allyl), C 2-6Alkynyl (particularly propargyl), C 1-6Alkoxyl (particularly methoxyl group), C 2-6Alkene oxygen base (particularly allyloxy), C 2-6Alkynyloxy group (particularly alkynes propoxyl group), halogen (C 1-6) alkyl (particularly trifluoromethyl), halogen (C 1-6) alkoxyl (particularly trifluoromethoxy) ,-S (O) m(C 1-6) alkyl, wherein m is 0,1 or 2 and described alkyl is optional is replaced hydroxyl (C by halogen 1-6) alkyl, C 1-4Alkoxyl (C 1-4) alkyl, C 1-4Alkoxyl (C 1-4) alkoxyl, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4) alkyl, the aryl of optional replacement (the particularly phenyl of optional replacement), the heteroaryl of optional replacement (the particularly pyridine radicals of optional replacement or pyrimidine radicals), the aryloxy group of optional replacement (the particularly phenoxy group of optional replacement), the heteroaryloxy of optional replacement (particularly the pyridine oxygen base or the 2-pyrimidinyl oxy of optional replacement), the wherein m of optional replacement are 0,1 or 2-S (O) mAryl (the particularly thiophenyl of optional replacement), the wherein m of optional replacement are 0,1 or 2-S (O) mHeteroaryl (particularly the pyridine sulfenyl of optional replacement or pyrimidine sulfenyl), the aryl (C of optional replacement 1-4) alkyl (particularly the benzyl of optional replacement, the phenyl n-pro-pyl of the phenethyl of optional replacement and optional replacement), wherein moieties is optional is replaced by hydroxyl, the heteroaryl (C of optional replacement 1-4) alkyl (pyridine radicals of optional replacement-or pyrimidine radicals (C particularly 1-4) alkyl), the aryl (C of optional replacement 2-4) thiazolinyl (the particularly styryl of optional replacement), the heteroaryl (C of optional replacement 2-4) thiazolinyl (particularly the pyridine radicals vinyl of optional replacement or pyrimidine radicals vinyl), the aryl (C of optional replacement 1-4) alkoxyl (the particularly benzyloxy of optional replacement and benzene ethyoxyl), the heteroaryl (C of optional replacement 1-4) alkoxyl (pyridine radicals (C of optional replacement particularly 1-4) alkoxyl or pyrimidine radicals (C 1-4) alkoxyl), the aryloxy group (C of optional replacement 1-4) alkyl (particularly phenoxymethyl), the heteroaryloxy of optional replacement-(C 1-4) alkyl (the pyridine oxygen base (C of optional replacement particularly 1-4) alkyl or 2-pyrimidinyl oxy (C 1-4) alkyl), the wherein m of optional replacement is 0,1 or 2-S (O) m(C 1-4) alkylaryl (the particularly benzylthio of optional replacement and benzene ethylmercapto group), the wherein m of optional replacement is 0,1 or 2-S (O) m(C 1-4) miscellaneous alkyl aryl (pyridine radicals (C of optional replacement particularly 1-4) alkylthio group or pyrimidine radicals (C 1-4) alkylthio group), the wherein m of optional replacement is 0,1 or 2-(C 1-4) alkyl S (O) mAryl (particularly thiophenyl methyl), the wherein m of optional replacement be 0,1 or 2-(C 1-4) alkyl S (O) mHeteroaryl (pyridine sulfenyl (the C of optional replacement particularly 1-4) alkyl or pyrimidine sulfenyl (C 1-4) alkyl), acyloxy comprises C 1-4Alkanoyloxy (particularly acetoxyl group) and benzoyloxy, cyano group, isocyano group, thiocyanogen, isothiocyano, nitro, NR gR h,-NHCOR g,-NHCONR gR h,-CONR gR h,-CO 2R g,-SO 2R i,-OSO 2R i,-COR g,-CR g=NR hOr-N=CR gR h, R wherein iBe C 1-4Alkyl, halo (C 1-4) alkyl, C 1-4Alkoxyl, halo (C 1-4) alkoxyl, C 1-4Alkylthio group, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4) alkyl, phenyl or benzyl, described phenyl and benzyl group are optional by halogen, C 1-4Alkyl or C 1-4Alkoxyl replaces, and R gAnd R hBe hydrogen independently, C 1-4Alkyl, halo (C 1-4) alkyl, C 1-4Alkoxyl, halo (C 1-4) alkoxyl, C 1-4Alkylthio group, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4)-alkyl, phenyl or benzyl, described phenyl and benzyl group are optional by halogen, C 1-4Alkyl or C 1-4Alkoxyl replaces.
Q wherein especially meaningfully 2Be hydrogen, Q 1And Q 3Those formulas (I) compound as above.
Another organizes preferred formula (I) compound is Q wherein 1Be halogen, aryl or heteroaryl, Q 2Be hydrogen and Q 3As above those.
Another organizes preferred formula (I) compound is Q wherein 1Be aryl, Q 2Be hydrogen and Q 3As above those.
Another organizes preferred formula (I) compound is Q wherein 1Be heteroaryl, Q 2Be hydrogen and Q 3As above those.
Another organizes preferred formula (I) compound is Q wherein 1And Q 3Be halogen and Q 2Be those of hydrogen.
Another organizes preferred formula (I) compound is Q wherein 1Be aryl or heteroaryl, Q 2Be hydrogen and Q 3Be those of halogen.
Another organizes preferred formula (I) compound is Q wherein 1And Q 2Be hydrogen and Q 3Be those of alkyl of halogen or optional replacement.
Another organizes preferred formula (I) compound is Q wherein 1Be halogen, Q 2Be hydrogen and Q 3Be those of alkyl of optional replacement.
Another organizes preferred formula (I) compound is Q wherein 1And Q 2Be halogen and Q 3Be those of alkyl of optional replacement.
Another organizes preferred formula (I) compound is Q wherein 1Be those of bromine.
Another organizes preferred formula (I) compound is Q wherein 1Be those of iodine.
Another organizes preferred formula (I) compound is Q wherein 1Be those of chlorine.
Another organizes preferred formula (I) compound is Q wherein 1Be those of fluorine.
Another organizes preferred formula (I) compound is Q wherein 3Be those of halogen.
Another organizes preferred formula (I) compound is Q wherein 3Be those of fluorine.
Another organizes preferred formula (I) compound is Q wherein 1Be bromine, Q 2Be hydrogen and Q 3Be those of fluorine.
Another organizes preferred formula (I) compound is Q wherein 1Be bromine, Q 2Be hydrogen and Q 3Be those of chlorine.
Another organizes preferred formula (I) compound is Q wherein 1Be iodine, Q 2Be hydrogen and Q 3Be those of fluorine.
Another organizes preferred formula (I) compound is Q wherein 1Be iodine, Q 2Be hydrogen and Q 3Be those of chlorine.
Another organizes preferred formula (I) compound is Q wherein 1Be those of hydrogen, halogen, aryl or heteroaryl.
Another organizes preferred formula (I) compound is R wherein 1Be C 1-4Alkyl or halo (C 1-4) those of alkyl.
Another organizes preferred formula (I) compound is R wherein 1Be those of methyl.
Another organizes preferred formula (I) compound is R wherein 1Be those of ethyl.
Another organizes preferred formula (I) compound is R wherein 2Be those of hydrogen or methyl.
Another organizes preferred formula (I) compound is R wherein 2Be those of hydrogen.
Another organizes preferred formula (I) compound is Q wherein 1, Q 2And Q 3Be those of halogen.
Another organizes preferred formula (I) compound is Q wherein 1Be halogen, Q 2Be C 1-4Alkyl and Q 3Be those of halogen.
Another organizes preferred formula (I) compound is Q wherein 1Be halogen, Q 2Be C 1-4Alkyl and Q 3Be those of chlorine.
Another organizes preferred formula (I) compound is Q wherein 1Be halogen, Q 2Be C 1-4Alkyl and Q 3Be those of fluorine.
Another organizes preferred formula (I) compound is Q wherein 1Be halogen, Q 2Be methyl and Q 3Be those of halogen.
Another organizes preferred formula (I) compound is Q wherein 1Be halogen, Q 2Be methyl and Q 3Be those of chlorine.
Another organizes preferred formula (I) compound is Q wherein 1Be halogen, Q 2Be methyl and Q 3Be those of fluorine.
Another organizes preferred formula (I) compound is Q wherein 1Be bromine, Q 2Be methyl and Q 3Be those of chlorine.
Another organizes preferred formula (I) compound is Q wherein 1Be bromine, Q 2Be methyl and Q 3Be those of fluorine.
Another organizes preferred formula (I) compound is Q wherein 1Be iodine, Q 2Be methyl and Q 3Be those of chlorine.
Another organizes preferred formula (I) compound is Q wherein 1Be iodine, Q 2Be methyl and Q 3Be those of fluorine.
Another organizes preferred formula (I) compound is Q wherein 1Be halogen, Q 2And Q 3Be C 1-4Those of alkyl.
Another organizes preferred formula (I) compound is these compounds, wherein R 3It is the tert-butyl group; 1-halo-2-methyl-prop-2-base; 1; 1-dihalo-2-methyl-prop-2-base; 1; 1; 1-three halos-2-methyl-prop-2-base; 1-alkoxyl-2-methyl-prop-2-base; 1-alkene oxygen base-2-methyl-prop-2-base; 1-alkynyloxy group-2-methyl-prop-2-base; 1-cyano group-2-methyl-third-2-base; 1-alkoxyl alkoxyl-2-methyl-third-2-base; 1-halo-3-methyl fourth-3-base; 1; 1-dihalo-3-methyl fourth-3-base; 1; 1; 1-three halos-3-methyl fourth-3-base; 1-alkoxyl-3-methyl fourth-3-base; 1-alkene oxygen base-3-methyl fourth-3-base; 1-alkynyloxy group-3-methyl fourth-3-base; 1-cyano group-3-methyl fourth-3-base; 2-cyano group third-2-base; 2-methoxycarbonyl group third-2-base or 2-methylamino carbonyl third-2-base; 1-alkylthio group-2-methyl-prop-2-base; 1-alkyl sulphinyl-2-methyl-prop-2-base; 1-alkyl sulphonyl-2-methyl-prop-2-base; 2-cyano group-1-alkoxypropan-2-base; 2-methyl isophthalic acid-[(E and/or Z)-oxyimino]-third-2-base; 2-methyl isophthalic acid-[(E and/or Z)-Alkoximino]-third-2-base; 2-methyl isophthalic acid-[(E and/or Z)-aryloxy group imino group]-third-2-base; 2-methyl isophthalic acid-[(E and/or Z)-heteroaryloxy imino group]-third-2-base; 1-alkoxyl-third-2-base; 1-halo-third-2-base; 3-methyl-Ding-1-alkynes-3-base; 1-alkyl-3-methyl-Ding-1-alkynes-3-base; 4-methyl-penta-2-alkynes-4-base; 1-hydroxy-4-methyl-penta-2-alkynes-4-base; 1-alkoxyl-4-methyl-penta-2-alkynes-4-base; 1-alkoxyl alkoxyl-4-methyl-penta-2-alkynes-4-base; 1-alkoxy alkoxy alkyl-4-methyl-penta-2-alkynes-4-base; 1-cyano group alkyl-3-methyl fourth-3-base; 1-haloalkyl-3-methyl fourth-3-base; more preferably, R wherein 3It is the tert-butyl group, 1-halo-2-methyl-prop-2-base, 1-fluoro-2-methyl-prop-2-base, 1-methoxyl group-2-methyl-prop-2-base, 1-ethyoxyl-2-methyl-prop-2-base, 1-allyloxy-2-methyl-prop-2-base, 1-(third-2-alkynyloxy group)-2-methyl-prop-2-base, 2-cyano group-1-ethyoxyl-third-2-base, 2-cyano group-1-methoxy propyl-2-base, 1-halo-3-methyl fourth-3-base, 1-fluoro-3-methyl fourth-3-base, 3-methyl fourth-1-alkynes-3-base, 4-methylpent-2-alkynes-4-base, the 5-methyl-oneself-3-alkynes-5-base, 1-methoxyl group-4-methyl-penta-2-alkynes-4-base, 1-allyloxy-4-methyl-penta-2-alkynes-4-base, 1-alkynes propoxyl group-4-methyl-penta-2-alkynes-4-base, 1-ethyoxyl-4-methyl-penta-2-alkynes-4-base.
Another organizes preferred formula (I) compound is these, wherein R 4Be alternatively by C 1-4Alkoxyl-(C 1-4) alkoxyl (C 1-4) C that replaces of alkyl 1-6Alkyl, wherein said alkyl group are alternatively by halogen ,-or two-(C 1-6) alkyl amino or three (C 1-4) replacement of alkyl silicyl, perhaps R 4Be alternatively by benzyloxy (C 1-4) C that replaces of alkyl 1-6Alkyl, wherein said alkyl group are alternatively by halogen ,-or two-(C 1-6) alkyl amino or three (C 1-4) replacement of alkyl silicyl, perhaps R 4Be alternatively by C 2-6Alkene oxygen base or-S (O) x(C 1-6) C that replaces of alkyl 1-6Alkyl, wherein x be 0,1 or 2 and described alkyl group alternatively by halogen ,-or two-(C 1-6) alkyl amino ,-NH (C 1-4) alkyl=NOR replacement, wherein R is hydrogen or C 1-4Alkyl, or wherein said alkyl group is alternatively by three (C 1-4) replacement of alkyl silicyl, perhaps R 4Be-CR Uu=NR Vv, R wherein UuBe hydrogen or C 1-6Alkyl and R VvBe the C of hydroxyl or optional replacement 1-6Alkoxyl.
Another organizes preferred formula (I) compound is these, wherein R 5The ring of the aryl of the optional replacement in the definition and the heteroaryl of optional replacement or part are replaced by following group alternatively: halogen, cyano group, nitro, azido, C 1-6Alkyl, halo (C 1-6) alkyl, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4) alkyl, C 2-6Thiazolinyl, halo (C 2-6) thiazolinyl, C 2-6Alkynyl, halo (C 2-6) alkynyl, C 1-6Alkoxyl, halo (C 1-6) alkoxyl, C 2-6Alkene oxygen base, halo (C 2-6) alkene oxygen base, C 2-6Alkynyloxy group, halo (C 2-6) alkynyloxy group, aryl, aryloxy group, aryl (C 1-6) alkyl, aryl (C 1-6) alkoxyl, heteroaryl, heteroaryloxy, heteroaryl (C 1-6) alkyl, heteroaryl (C 1-6) alkoxyl ,-SF 5,-S (0) g(C 1-4) alkyl, wherein g be 0,1 or 2 and described alkyl replaced by halogen alternatively, perhaps
R 5Alternatively by-OSO 2(C 1-4) the alkyl replacement, wherein said alkyl group is replaced by halogen alternatively, perhaps R 5Alternatively by-CONR gR h,-COR g,-CO 2R g,-R g=NR h,-NR gR h,-NR gCOR h,-NR gCO 2R h,-SO 2NR gR hOr-NR gSO 2R 1Replace, wherein R iBe the C that is replaced by halogen alternatively 1-6Alkyl and R gAnd R hBe hydrogen or independently of one another by the C of the optional replacement of halogen 1-6Alkyl is perhaps at-CONR gR hOr-SO 2NR gR hSituation under, R gR hCan be in conjunction with forming 5-or 6-unit's carbocyclic ring or heterocycle, it comprises and is selected from sulphur, oxygen or NR 0Hetero atom, R wherein 0Be the C of hydrogen or optional replacement 1-6Alkyl.
Another organizes preferred formula (I) compound is these, and wherein the 5-of the heteroaryl of the aryl of optional replacement and optional replacement or optional replacement is to the ring R of 8-unit 4Replaced by following group alternatively: halogen, cyano group, nitro, azido, C 1-6Alkyl, halo (C 1-6) alkyl, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4) alkyl, C 2-6Thiazolinyl, halo (C 2-6) thiazolinyl, C 2-6Alkynyl, halo (C 2-6) alkynyl, C 1-6Alkoxyl, halo (C 1-6) alkoxyl, C 2-6Alkene oxygen base, halo (C 2-6) alkene oxygen base, C 2-6Alkynyloxy group, halo (C 2-6) alkynyloxy group ,-SF 5,-S (O) x(C 1-6) alkyl, wherein x be 0,1 or 2 and described alkyl group replaced perhaps R alternatively by halogen 4Alternatively by-OSO 2(C 1-4) alkyl replaces, wherein said alkyl alternatively by halogen replace ,-CONR xR y,-CON (OR x) R y,-COR x,-CO 2R x,-CR x=NR y,-NR xR y,-NR xCOR y,-NR xCO 2R y,-SO 2NR xR yOr-NR xSO 2R zReplace, wherein R zBy the C of the optional replacement of halogen 1-8Alkyl and R xAnd R yBe hydrogen or the optional C that is replaced by halogen independently of one another 1-6Alkyl.
Another organizes preferred formula (I) compound is these, wherein R 50Be the optional C that is replaced by following radicals 1-4Alkyl: halogen, hydroxyl, C 1-6Alkoxyl, C 2-6Thiazolinyl (particularly pi-allyl), C 2-6Alkynyl (particularly propargyl), C 1-4Alkoxyl (C 1-4) alkoxyl, cyano group, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkyl amino-carbonyl oxygen base, wherein p is 0,1 or 2 S (O) p(C 1-6)-alkyl, triazolyl, pyrazolyl, imidazole radicals, three (C 1-4The benzyloxy of the phenoxy group of)-alkyl siloxy, optional replacement, the thiophene oxy of optional replacement, optional replacement or the thiophene methoxy of optional replacement.
Another organizes preferred formula (I) compound is these, wherein R 50Be the optional C that is replaced by following radicals 3-6Cycloalkyl: halogen, hydroxyl, C 1-6Alkoxyl, C 1-4Alkoxyl (C 1-4) alkoxyl, cyano group, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkyl amino-carbonyl oxygen base, wherein p is 0,1 or 2 S (O) p(C 1-6)-alkyl, triazolyl, pyrazolyl, imidazole radicals, three (C 1-4The benzyloxy of the phenoxy group of)-alkyl siloxy, optional replacement, the thiophene oxy of optional replacement, optional replacement or the thiophene methoxy of optional replacement.
Another organizes preferred formula (I) compound is these, wherein the heteroaryl R of the aryl of optional replacement or optional replacement 50Optionally replaced: halogen, hydroxyl, sulfydryl, C by following radicals 1-4Alkyl, C 2-4Thiazolinyl, C 2-4Alkynyl, C 1-4Alkoxyl, C 2-4Alkene oxygen base, C 2-4Alkynyloxy group, halo (C 1-4) alkyl, halo (C 1-4) alkoxyl, C 1-4Alkylthio group, halo (C 1-4)-alkylthio group, hydroxyl (C 1-4) alkyl, C 1-4Alkoxyl (C 1-4) alkyl, C 3-6Cycloalkyl, C 3-6Cycloalkyl-(C 1-4) alkyl, phenoxy group, benzyloxy, benzoyloxy, cyano group, isocyano group, thiocyanogen, isothiocyano, nitro, NR pR q, NHCOR p,-NHCONR pR q, CONR pR q,-SO 2R o, OSO 2R o, COR p, CR p=NR qOr N=CR pR q, R wherein oBe C 1-4Alkyl, halo (C 1-4) alkyl, C 1-4Alkoxyl, halo (C 1-4) alkoxyl, C 1-4Alkylthio group, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4) alkyl, phenyl or benzyl, described phenyl and benzyl group are alternatively by halogen, C 1-4Alkyl or C 1-4Alkoxyl replaces, and R pAnd R qBe hydrogen, C independently 1-4Alkyl, halo (C 1-4) alkyl, C 1-4Alkoxyl, halo (C 1-4) alkoxyl, C 1-4Alkylthio group, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4) alkyl, phenyl or benzyl, described phenyl and benzyl group are alternatively by halogen, C 1-4Alkyl or C 1-4Alkoxyl replaces.
Another organizes preferred formula (I) compound is that wherein L is those of oxygen.
Another organize preferred formula (I) compound be wherein n be 0 those.
Another organizes the N-oxide that preferred formula (I) compound is the quinoline moiety formation of passing type I compound.
The compound that forms a part of the present invention is illustrated in following table 1 to 192.
Fusing point (mp) and/or identify molecular ion (M for example +, [M+1] +) value and/or spectrum (1HNMR) data are provided in embodiment 1-5, biologically active is provided in embodiment 6.
Table 1
Table 1 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R iBe methyl and R 2And R 3Has the implication that provides in this table.
Figure A200780036889D00251
Figure A200780036889D00271
Figure A200780036889D00281
Figure A200780036889D00291
Figure A200780036889D00301
Figure A200780036889D00311
Figure A200780036889D00321
Figure A200780036889D00331
Figure A200780036889D00341
Figure A200780036889D00351
Figure A200780036889D00361
Table 2
Table 2 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 2 compound 1 is identical with table 1 compound 1, and except Q1 in table 2 compound 1 is a bromine, Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 2 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 2 compound is a bromine, Q2 is a hydrogen, and Q3 is a chlorine.
Table 3
Table 3 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 3 compound 1 is identical with table 1 compound 1, and except Q1 in table 3 compound 1 is an iodine, Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 3 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 3 compound is an iodine, Q2 is a hydrogen, and Q3 is a chlorine.
Table 4
Table 4 compound is general formula (I) compound, and wherein Q1 is a fluorine, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 4 compound 1 is identical with table 1 compound 1, and except Q1 in table 4 compound 1 is a fluorine, Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 4 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 3 compound is a fluorine, Q2 is a hydrogen, and Q3 is a chlorine.
Table 5
Table 5 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 5 compound 1 is identical with table 1 compound 1, and except Q1 in table 5 compound 1 is a chlorine, Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 5 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 5 compound is a chlorine, Q2 is a hydrogen, and Q3 is a fluorine.
Table 6
Table 6 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 6 compound 1 is identical with table 1 compound 1, and except Q1 in table 5 compound 1 is a bromine, Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 6 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 6 compound is a bromine, Q2 is a hydrogen, and Q3 is a fluorine.
Table 7
Table 7 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 7 compound 1 is identical with table 1 compound 1, and except Q1 in table 7 compound 1 is an iodine, Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 7 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 7 compound is an iodine, Q2 is a hydrogen, and Q3 is a fluorine.
Table 8
Table 8 compound is general formula (I) compound, and wherein Q1 is a fluorine, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 8 compound 1 is identical with table 1 compound 1, and except Q1 in table 8 compound 1 is a fluorine, Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 8 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 8 compound is a fluorine, Q2 is a hydrogen, and Q3 is a fluorine.
Table 9
Table 9 compound is general formula (I) compound, and wherein Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 9 compound 1 is identical with table 1 compound 1, and except Q1 in table 9 compound 1 is a hydrogen, Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 9 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 9 compound is a hydrogen, Q2 is a hydrogen, and Q3 is a chlorine.
Table 10
Table 10 compound is general formula (I) compound, and wherein Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 10 compound 1 is identical with table 1 compound 1, and except Q1 in table 10 compound 1 is a hydrogen, Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 10 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 10 compound is a hydrogen, Q2 is a hydrogen, and Q3 is a fluorine.
Table 11
Table 11 compound is general formula (I) compound, and wherein Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a bromine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 11 compound 1 is identical with table 1 compound 1, and except Q1 in table 11 compound 1 is a hydrogen, Q2 is a hydrogen, and Q3 is a bromine.Similarly, table 11 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 11 compound is a hydrogen, Q2 is a hydrogen, and Q3 is a bromine.
Table 12
Table 12 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a methyl, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 12 compound 1 is identical with table 1 compound 1, and except Q1 in table 12 compound 1 is a chlorine, Q2 is a hydrogen, and Q3 is a methyl.Similarly, table 12 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 12 compound is a chlorine, Q2 is a hydrogen, and Q3 is a methyl.
Table 13
Table 13 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a methyl, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 13 compound 1 is identical with table 1 compound 1, and except Q1 in table 13 compound 1 is a bromine, Q2 is a hydrogen, and Q3 is a methyl.Similarly, table 2 compound 13 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 13 compound is a bromine, Q2 is a hydrogen, and Q3 is a methyl.
Table 14
Table 14 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a methyl, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 14 compound 1 is identical with table 1 compound 1, and except Q1 in table 14 compound 1 is an iodine, Q2 is a hydrogen, and Q3 is a methyl.Similarly, table 14 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 14 compound is an iodine, Q2 is a hydrogen, and Q3 is a methyl.
Table 15
Table 15 compound is general formula (I) compound, and wherein Q1 is a fluorine, and Q2 is a hydrogen, and Q3 is a methyl, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 15 compound 1 is identical with table 1 compound 1, and except Q1 in table 15 compound 1 is a fluorine, Q2 is a hydrogen, and Q3 is a methyl.Similarly, table 15 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 15 compound is a fluorine, Q2 is a hydrogen, and Q3 is a methyl.
Table 16
Table 16 compound is general formula (I) compound, and wherein Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a methyl, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 16 compound 1 is identical with table 1 compound 1, and except Q1 in table 16 compound 1 is a hydrogen, Q2 is a hydrogen, and Q3 is a methyl.Similarly, table 16 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 16 compound is a hydrogen, Q2 is a hydrogen, and Q3 is a methyl.
Table 17
Table 17 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 17 compound 1 is identical with table 1 compound 1, except R in table 17 compound 1 1Be ethyl, Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 17 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 17 compound 1Be ethyl, Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a chlorine.
Table 18
Table 18 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 18 compound 1 is identical with table 1 compound 1, except R in table 18 compound 1 1Be ethyl, Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 18 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 18 compound 1Be ethyl, Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a chlorine.
Table 19
Table 19 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 19 compound 1 is identical with table 1 compound 1, except R in table 19 compound 1 1Be ethyl, Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 19 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 19 compound 1Be ethyl, Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a chlorine.
Table 20
Table 20 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 20 compound 1 is identical with table 1 compound 1, except R in table 20 compound 1 1Be ethyl, Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 20 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 20 compound 1Be ethyl, Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a fluorine.
Table 21
Table 21 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 21 compound 1 is identical with table 1 compound 1, except R in table 21 compound 1 1Be ethyl, Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 21 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 21 compound 1Be ethyl, Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a fluorine.
Table 22
Table 22 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 22 compound 1 is identical with table 1 compound 1, except R in table 22 compound 1 1Be ethyl, Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 22 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 22 compound 1Be ethyl, Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a fluorine.
Table 23
Table 23 compound is general formula (I) compound, and wherein Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 23 compound 1 is identical with table 1 compound 1, except R in table 23 compound 1 1Be ethyl, Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 23 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 23 compound 1Be ethyl, Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a chlorine.
Table 24
Table 24 compound is general formula (I) compound, and wherein Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 24 compound 1 is identical with table 1 compound 1, except R in table 24 compound 1 1Be ethyl, Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 24 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 24 compound 1Be ethyl, Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a fluorine.
Table 25
Table 25 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a methyl, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 25 compound 1 is identical with table 1 compound 1, except R in table 25 compound 1 1Be ethyl, Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a methyl.Similarly, table 25 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 25 compound 1Be ethyl, Q1 is a chlorine, and Q2 is a hydrogen, and Q3 is a methyl.
Table 26
Table 26 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a methyl, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 26 compound 1 is identical with table 1 compound 1, except R in table 26 compound 1 1Be ethyl, Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a methyl.Similarly, table 26 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 26 compound 1Be ethyl, Q1 is a bromine, and Q2 is a hydrogen, and Q3 is a methyl.
Table 27
Table 27 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a methyl, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 27 compound 1 is identical with table 1 compound 1, except R in table 27 compound 1 1Be ethyl, Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a methyl.Similarly, table 27 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 27 compound 1Be ethyl, Q1 is an iodine, and Q2 is a hydrogen, and Q3 is a methyl.
Table 28
Table 28 compound is general formula (I) compound, and wherein Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a methyl, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 28 compound 1 is identical with table 1 compound 1, except R in table 28 compound 1 1Be ethyl, Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a methyl.Similarly, table 28 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, except R in table 28 compound 1Be ethyl, Q1 is a hydrogen, and Q2 is a hydrogen, and Q3 is a methyl.
Table 29
Table 29 compound is general formula (I) compound, and wherein Q1 is a thiene-3-yl-, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 29 compound 1 is identical with table 1 compound 1, and except Q1 in table 29 compound 1 is a thiene-3-yl-, Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 29 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 29 compound is a thiene-3-yl-, Q2 is a hydrogen, and Q3 is a chlorine.
Table 30
Table 30 compound is general formula (I) compound, and wherein Q1 is a thiene-3-yl-, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 30 compound 1 is identical with table 1 compound 1, and except Q1 in table 30 compound 1 is a thiene-3-yl-, Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 30 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 30 compound is a thiene-3-yl-, Q2 is a hydrogen, and Q3 is a fluorine.
Table 31
Table 31 compound is general formula (I) compound, and wherein Q1 is thiophene-2-base, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 31 compound 1 is identical with table 1 compound 1, and except Q1 in table 31 compound 1 is thiophene-2-base, Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 31 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 31 compound is thiophene-2-base, Q2 is a hydrogen, and Q3 is a chlorine.
Table 32
Table 32 compound is general formula (I) compound, and wherein Q1 is thiophene-2-base, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 32 compound 1 is identical with table 1 compound 1, and except Q1 in table 32 compound 1 is thiophene-2-base, Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 32 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 32 compound is thiophene-2-base, Q2 is a hydrogen, and Q3 is a fluorine.
Table 33
Table 33 compound is general formula (I) compound, and wherein Q1 is a thiene-3-yl-, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 33 compound 1 is identical with table 1 compound 1, and except Q1 in table 33 compound 1 is a thiene-3-yl-, Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 33 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 33 compound is a thiene-3-yl-, Q2 is a hydrogen, and Q3 is a chlorine.
Table 34
Table 34 compound is general formula (I) compound, and wherein Q1 is a thiene-3-yl-, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 34 compound 1 is identical with table 1 compound 1, and except Q1 in table 34 compound 1 is a thiene-3-yl-, Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 34 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 34 compound is a thiene-3-yl-, Q2 is a hydrogen, and Q3 is a fluorine.
Table 35
Table 35 compound is general formula (I) compound, and wherein Q1 is thiophene-2-base, and Q2 is a hydrogen, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 35 compound 1 is identical with table 1 compound 1, and except Q1 in table 35 compound 1 is thiophene-2-base, Q2 is a hydrogen, and Q3 is a chlorine.Similarly, table 35 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 35 compound is thiophene-2-base, Q2 is a hydrogen, and Q3 is a chlorine.
Table 36
Table 36 compound is general formula (I) compound, and wherein Q1 is thiophene-2-base, and Q2 is a hydrogen, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be ethyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 36 compound 1 is identical with table 1 compound 1, and except Q1 in table 36 compound 1 is thiophene-2-base, Q2 is a hydrogen, and Q3 is a fluorine.Similarly, table 36 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 36 compound is thiophene-2-base, Q2 is a hydrogen, and Q3 is a fluorine.
Table 37
Table 37 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a methyl, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 37 compound 1 is identical with table 1 compound 1, and except Q1 in table 37 compound 1 is a chlorine, Q2 is a methyl, and Q3 is a chlorine.Similarly, table 37 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 37 compound is a chlorine, Q2 is a methyl, and Q3 is a chlorine.
Table 38
Table 38 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a methyl, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 38 compound 1 is identical with table 1 compound 1, and except Q1 in table 38 compound 1 is a bromine, Q2 is a methyl, and Q3 is a chlorine.Similarly, table 38 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 38 compound is a bromine, Q2 is a methyl, and Q3 is a chlorine.
Table 39
Table 39 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a methyl, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 39 compound 1 is identical with table 1 compound 1, and except Q1 in table 39 compound 1 is an iodine, Q2 is a methyl, and Q3 is a chlorine.Similarly, table 39 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 39 compound is an iodine, Q2 is a methyl, and Q3 is a chlorine.
Table 40
Table 40 compound is general formula (I) compound, and wherein Q1 is a fluorine, and Q2 is a methyl, and Q3 is a chlorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 40 compound 1 is identical with table 1 compound 1, and except Q1 in table 40 compound 1 is a fluorine, Q2 is a methyl, and Q3 is a chlorine.Similarly, table 40 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 40 compound is a fluorine, Q2 is a methyl, and Q3 is a chlorine.
Table 41
Table 41 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a methyl, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 41 compound 1 is identical with table 1 compound 1, and except Q1 in table 41 compound 1 is a chlorine, Q2 is a methyl, and Q3 is a fluorine.Similarly, table 41 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 41 compound is a chlorine, Q2 is a methyl, and Q3 is a fluorine.
Table 42
Table 42 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a methyl, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 42 compound 1 is identical with table 1 compound 1, and except Q1 in table 42 compound 1 is a bromine, Q2 is a methyl, and Q3 is a fluorine.Similarly, table 42 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 42 compound is a bromine, Q2 is a methyl, and Q3 is a fluorine.
Table 43
Table 43 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a methyl, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 43 compound 1 is identical with table 1 compound 1, and except Q1 in table 43 compound 1 is an iodine, Q2 is a methyl, and Q3 is a fluorine.Similarly, table 43 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 43 compound is an iodine, Q2 is a methyl, and Q3 is a fluorine.
Table 44
Table 44 compound is general formula (I) compound, and wherein Q1 is a fluorine, and Q2 is a methyl, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 44 compound 1 is identical with table 1 compound 1, and except Q1 in table 44 compound 1 is a fluorine, Q2 is a methyl, and Q3 is a fluorine.Similarly, table 44 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 44 compound is a fluorine, Q2 is a methyl, and Q3 is a fluorine.
Table 45
Table 45 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a methyl, and Q3 is a bromine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 45 compound 1 is identical with table 1 compound 1, and except Q1 in table 45 compound 1 is a chlorine, Q2 is a methyl, and Q3 is a bromine.Similarly, table 45 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 45 compound is a chlorine, Q2 is a methyl, and Q3 is a bromine.
Table 46
Table 46 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a methyl, and Q3 is a bromine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 46 compound 1 is identical with table 1 compound 1, and except Q1 in table 46 compound 1 is a bromine, Q2 is a methyl, and Q3 is a bromine.Similarly, table 46 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 46 compound is a bromine, Q2 is a methyl, and Q3 is a bromine.
Table 47
Table 47 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a methyl, and Q3 is a bromine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 47 compound 1 is identical with table 1 compound 1, and except Q1 in table 47 compound 1 is an iodine, Q2 is a methyl, and Q3 is a bromine.Similarly, table 47 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 47 compound is an iodine, Q2 is a methyl, and Q3 is a bromine.
Table 48
Table 48 compound is general formula (I) compound, and wherein Q1 is a fluorine, and Q2 is a methyl, and Q3 is a bromine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 48 compound 1 is identical with table 1 compound 1, and except Q1 in table 48 compound 1 is a fluorine, Q2 is a methyl, and Q3 is a bromine.Similarly, table 48 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 48 compound is a fluorine, Q2 is a methyl, and Q3 is a bromine.
Table 49
Table 49 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a chlorine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 49 compound 1 is identical with table 1 compound 1, and except Q1 in table 49 compound 1 is a chlorine, Q2 is a chlorine, and Q3 is a fluorine.Similarly, table 49 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 49 compound is a chlorine, Q2 is a chlorine, and Q3 is a fluorine.
Table 50
Table 50 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a chlorine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 50 compound 1 is identical with table 1 compound 1, and except Q1 in table 50 compound 1 is a bromine, Q2 is a chlorine, and Q3 is a fluorine.Similarly, table 50 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 50 compound is a bromine, Q2 is a chlorine, and Q3 is a fluorine.
Table 51
Table 51 compound is general formula (I) compound, and wherein Q1 is a fluorine, and Q2 is a chlorine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 51 compound 1 is identical with table 1 compound 1, and except Q1 in table 51 compound 1 is a fluorine, Q2 is a chlorine, and Q3 is a fluorine.Similarly, table 51 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 51 compound is a fluorine, Q2 is a chlorine, and Q3 is a fluorine.
Table 52
Table 52 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a chlorine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 52 compound 1 is identical with table 1 compound 1, and except Q1 in table 52 compound 1 is an iodine, Q2 is a chlorine, and Q3 is a fluorine.Similarly, table 52 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 52 compound is an iodine, Q2 is a chlorine, and Q3 is a fluorine.
Table 53
Table 53 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a bromine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 53 compound 1 is identical with table 1 compound 1, and except Q1 in table 53 compound 1 is a chlorine, Q2 is a bromine, and Q3 is a fluorine.Similarly, table 53 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 53 compound is a chlorine, Q2 is a bromine, and Q3 is a fluorine.
Table 54
Table 54 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a bromine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 54 compound 1 is identical with table 1 compound 1, and except Q1 in table 54 compound 1 is a bromine, Q2 is a bromine, and Q3 is a fluorine.Similarly, table 54 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 54 compound is a bromine, Q2 is a bromine, and Q3 is a fluorine.
Table 55
Table 55 compound is general formula (I) compound, and wherein Q1 is a fluorine, and Q2 is a bromine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 55 compound 1 is identical with table 1 compound 1, and except Q1 in table 55 compound 1 is a fluorine, Q2 is a bromine, and Q3 is a fluorine.Similarly, table 55 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 55 compound is a fluorine, Q2 is a bromine, and Q3 is a fluorine.
Table 56
Table 56 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a bromine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 56 compound 1 is identical with table 1 compound 1, and except Q1 in table 56 compound 1 is an iodine, Q2 is a bromine, and Q3 is a fluorine.Similarly, table 56 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 56 compound is an iodine, Q2 is a bromine, and Q3 is a fluorine.
Table 57
Table 57 compound is general formula (I) compound, and wherein Q1 is a chlorine, and Q2 is a fluorine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 57 compound 1 is identical with table 1 compound 1, and except Q1 in table 57 compound 1 is a chlorine, Q2 is a fluorine, and Q3 is a fluorine.Similarly, table 57 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 57 compound is a chlorine, Q2 is a fluorine, and Q3 is a fluorine.
Table 58
Table 58 compound is general formula (I) compound, and wherein Q1 is a bromine, and Q2 is a fluorine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 58 compound 1 is identical with table 1 compound 1, and except Q1 in table 58 compound 1 is a bromine, Q2 is a fluorine, and Q3 is a fluorine.Similarly, table 58 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 58 compound is a bromine, Q2 is a fluorine, and Q3 is a fluorine.
Table 59
Table 59 compound is general formula (I) compound, and wherein Q1 is a fluorine, and Q2 is a fluorine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 59 compound 1 is identical with table 1 compound 1, and except Q1 in table 59 compound 1 is a fluorine, Q2 is a fluorine, and Q3 is a fluorine.Similarly, table 59 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 59 compound is a fluorine, Q2 is a fluorine, and Q3 is a fluorine.
Table 60
Table 60 compound is general formula (I) compound, and wherein Q1 is an iodine, and Q2 is a fluorine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 60 compound 1 is identical with table 1 compound 1, and except Q1 in table 60 compound 1 is an iodine, Q2 is a fluorine, and Q3 is a fluorine.Similarly, table 60 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 60 compound is an iodine, Q2 is a fluorine, and Q3 is a fluorine.
Table 61
Table 61 compound is general formula (I) compound, and wherein Q1 is a thiene-3-yl-, and Q2 is a fluorine, and Q3 is a fluorine, and n is 0, and L is 0, R 1Be methyl, R 2And R 3Has the implication of listing in the table 1.Therefore, table 61 compound 1 is identical with table 1 compound 1, and except Q1 in table 61 compound 1 is a thiene-3-yl-, Q2 is a fluorine, and Q3 is a fluorine.Similarly, table 61 compound 2 to 323 is identical with table 1 compound 2 to 323 respectively, and except Q1 in table 61 compound is a thiene-3-yl-, Q2 is a fluorine, and Q3 is a fluorine.
Table 62 is to 121
Table 62 only is each table 62 to 121 in corresponding to table 1 to 61 (i.e. table 62 strictness is corresponding to table 1, i.e. table 63 strictness is corresponding to table 2, and the rest may be inferred by analogy for it) difference to 121 strictnesses, and L is S rather than 0.
Table 122 is to 181
Table 122 only is each table 122 to 181 in corresponding to table 1 to 61 (i.e. table 122 strictness is corresponding to table 1, i.e. table 123 strictness is corresponding to table 2, and the rest may be inferred by analogy for it) difference to 181 strictnesses, and n is 1 rather than 0.
Table 182 is to 241
Table 182 only is each table 182 to 241 in corresponding to table 1 to 61 (i.e. table 182 strictness is corresponding to table 1, i.e. table 183 strictness is corresponding to table 2, and the rest may be inferred by analogy for it) difference to 241 strictnesses, and n is 2 rather than 0.
General formula (I) compound can be according to the description preparation of following flow process 1 to 8, wherein Q1, Q2, Q3, R 1, R 2And R 3Has the given implication of preamble, R 14According to explanation is H or C 1-4Alkyl, R 10Be C 1-6The benzyl of alkyl, optional replacement, the C of optional replacement 2-6The C of thiazolinyl, optional replacement 2-4Alkynyl, R 6, R 7, R 8, R 9, R 12And R 13Be H or C independently 1-4Alkyl, R gBe H or C 1-3Alkyl, R hBe H or C 1-3Alkyl, R 1Be C 1-6The benzyl of alkyl, optional replacement, the C of optional replacement 2-6The C of thiazolinyl, optional replacement 2-4Alkynyl, m are 0,1 or 2, and DMF is N, and dinethylformamide, NBS are N-bromosuccinimides, and NCS is that N-chlorosuccinimide and MCPBA are metachloroperbenzoic acids.Other abbreviation definition in the text.
When given general or method for optimizing condition (reaction temperature, time, solvent, reactant molar ratio), can also use other method condition except as otherwise noted.The peak optimization reaction condition can be with used concrete reactant or solvent change, and these conditions can be determined by those skilled in the art by the optimization routine method.
Formula (1) compound, wherein n be 0 and L be 0, can by shown in the flow process 1 preparation.Formula (2) ester, wherein R 5Be C 1-4Alkyl, can be provided formula (3) halogen ester by halogenation, wherein Hal is halogen atom such as bromine, chlorine or iodine, arrive under the reflux temperature of solvent in environmental temperature, in the presence of radical initiator such as AIBN (azo-isobutyronitrile) and light source, in The suitable solvent such as carbon tetrachloride or acetonitrile, by obtaining with halogenating agent such as N-bromosuccinimide reaction.Then, with general formula (3) compound and general formula R 1The alkanethiol reaction of SH in the presence of alkali such as sodium hydride, in The suitable solvent such as DMF, provides general formula (6) compound, perhaps with alkanethiol salt R 1S -M +Reaction, wherein M is metal such as sodium or lithium, in The suitable solvent such as DMF, provides general formula (6) compound.
Flow process 1
Figure A200780036889D00511
Alternatively, general formula (4) ester is provided the halogen ester of formula (5) by halogenation, wherein Hal is halogen atom such as bromine, chlorine or iodine, arrive under the reflux temperature of solvent at 0 ℃, in The suitable solvent such as carbon tetrachloride or acetonitrile, by obtaining with halogenating agent such as N-chlorosuccinimide or N-bromosuccinimide reaction.Formula (5) halogen ester and the reaction of 6-oxyquinoline, wherein Q1, Q2 and Q3 as above define, and arrive under the reflux temperature of solvent in environmental temperature, in the presence of alkali such as potassium tert-butoxide, potash or sodium hydride, at the suitable solvent such as the tert-butyl alcohol, 1, among 4-dioxane or the DMF, provide formula (6) compound.Formula (6) compound is hydrolyzed to formula (7) acid, in environmental temperature under the reflux temperature of solvent, in suitable solvent such as moisture methyl alcohol, ethanol or THF (oxolane), by with alkali metal hydroxide M +OH -Reaction, acidifying subsequently obtains.Formula (7) acid can with formula (8) amine condensation, at 0 ℃ under environmental temperature, in suitable solvent such as DMF, use suitable activator such as HOBT (I-hydroxybenzotriazole) and EDC (1-ethyl-3-N, N-dimethylaminopropyl carbodiimide hydrochloride), provide general formula (1) compound, wherein n be 0 and L be 0.
General formula (1) compound, wherein n is 1 or 2, by shown in the flow process 2, is oxidized to sulfoxide (n is 1) or sulfone (n is 2) oxidation state prepares by the compound of n=0 (1) wherein.For example, R wherein 5Be C 1-4The general formula of alkyl (6) ester can 0 ℃ under environmental temperature, in suitable solvent such as ethanol, use oxidant such as sodium periodate oxidation to be formula (9) sulfoxide.Formula (10) sulfone can be at 0 ℃ under the reflux temperature of solvent, in suitable solvent such as carrene, oxidant such as metachloroperbenzoic acid (MCPBA) with two equivalents or more equivalents directly prepare from formula (6) compound, and perhaps the metachloroperbenzoic acid with monovalent or more equivalents prepares from formula (9) sulfoxide.Formula (6) sulphide, formula (9) sulfoxide or formula (10) sulfone can arrive under the reflux temperature of solvent at 0 ℃, in suitable solvent such as ethanol, by reacting and acidifying subsequently with alkali metal hydroxide, are hydrolyzed to corresponding acid (7), (11) or (12).The acid of formula (7), (11) or (12) can with formula (8) amine condensation, 0 ℃ under environmental temperature, use suitable activator such as HOBT and EDC, provide general formula (1) compound, wherein n is 0,1 or 2.
Figure A200780036889D00521
Similarly, wherein n is 1 the formula (11) and the sulfoxide of formula (1), can describe that to use oxidant such as sodium metaperiodate or metachloroperbenzoic acid to prepare from n wherein respectively be 0 the formula (7) and the sulphide of formula (1) by preamble.Wherein n is 2 the formula (12) and the sulfone of formula (1), can describe by preamble, using the oxidant of at least two equivalents such as metachloroperbenzoic acid preparation is 0 the formula (7) and the sulphide of formula (1) from n wherein, perhaps use the oxidant of monovalent or more equivalents such as metachloroperbenzoic acid preparation certainly wherein n be 1 the formula (11) and the sulfoxide of formula (1).
Formula (1) compound can also prepare shown in flow process 3.Formula (13) acid can with formula (8) amine condensation, 0 ℃ under environmental temperature, use suitable activator such as HOBT and EDC, provide formula (14) compound.Formula (14) compound can be formula (a 16) compound by halogenation, 0 ℃ under environmental temperature, in suitable solvent such as carbon tetrachloride or acetonitrile, use halogenating agent such as N-chlorosuccinimide to carry out.Formula (16) acid amides can prepare the acyl chlorides from formula (15), at 0 ℃ under environmental temperature, in suitable solvent such as carrene, in the presence of alkali such as triethylamine, by obtaining with formula (8) amine reaction.
Flow process 3
Figure A200780036889D00531
Formula (16) halo sulphide can with the 6-oxyquinoline reaction that replaces, 0 ℃ under 80 ℃, in The suitable solvent such as DMF, in the presence of alkali such as potash or sodium hydride, provide n wherein and be 0 formula (1) compound.
By shown in the flow process 4, the amine of general formula (18) or (20), it is R wherein 2Be the example of general formula (8) amine of H, can prepare, use suitable alkali such as n-BuLi or sodium hydride, subsequently with suitable alkylating reagent R by the amino alcohol of alkylation general formula (17) or (19) 10LG forms the alkylated compound of general formula (18) or (20) respectively such as alkyl iodide iodomethane reaction for example.Carbonyl derivative R 12COR 13(21),, can react, alpha-amido alkynes (22) (Strecker is synthetic) is provided with the ammoniacal liquor that is generally the ammonium chloride form and with the cyanide that is the sodium cyanide solution form easily as formaldehyde.
Flow process 4
Figure A200780036889D00541
Shown in flow process 5, the amino alkynes of the silicyl of general formula (24) protection can by at suitable alkali such as three grades of organic amine alkali for example in the presence of the triethylamine, with general formula (23) amine and 1,2-is two-(chloro dimetylsilyl) ethane reacts acquisition.General formula (26) amine, it is R wherein 2Be H and R 3Be-(CR 30R 40) C ≡ CR 50The example of general formula (8) amine, the amino alkynes of silicyl protection that can be by alkylation general formula (24) prepares, and uses suitable alkali such as n-BuLi, subsequently with suitable alkylating reagent R 50LG forms the alkylated compound of general formula (25) such as alkyl iodide iodomethane reaction for example.Described silicyl protecting group can be removed from the compound of general formula (25) with for example aqueous acid subsequently, thereby forms the amino alkynes of general formula (26).
Flow process 5
Figure A200780036889D00542
In similar method, the amino alkynes of the silicyl of general formula (24) protection can with carbonyl derivative R aCOR bAs formaldehyde reaction, use suitable alkali such as n-BuLi, the amino alkynes (27) that comprises the hydroxy alkyl part is provided.The compound of general formula (27) can be earlier handled with alkali such as sodium hydride or two (trimethyl silyl) potassamide, passes through compound R subsequently cLG for example iodoethane handles, and provides general formula (29) compound, described R cLG represents leaving group such as halogen among the LG, or sulphonic acid ester such as OSO 2Me, or OSO 2-4-tolyl.After removing the silicyl protecting group, obtain the compound of general formula (30).Alternatively, can remove the silicyl protecting group earlier to produce general formula (28) compound.The amino alkynes of general formula (28) can provide the silylated derivative on oxygen of general formula (31) further by reacting derivatization with sillylation reagent such as tert-butyldimethylsilyl chloride.
Flow process 6
Figure A200780036889D00551
Shown in flow process 6; the amino alkynes of the silicyl of general formula (32) protection can be at suitable alkali such as amino soda or for example two (trimethyl silyl) Sodamides of lithium amide alkali or Sodamide down, obtains by the amine of the silicyl protection of general formula (24) and the chloralkane that has suit leaving group such as a bromine or iodine are reacted.General formula (34) amine, it is R wherein 2Be H and R 3Be-(CR 30R 40) C ≡ CR 50The example of general formula (8), can remove the silicyl protecting group with for example aqueous acid subsequently and prepare by replacing cl anion, thereby form the cyano compound of general formula (34) with cyanide.
In similar method, general formula (35) acid amides can react with for example potassium cyanide, produces the amino alkynes of cyano group of general formula (36).
Shown in flow process 7, R wherein 50Be general formula (1) compound of H, thus substituted aryl or heteroaryl compound that aryl that can be under the Sonogashira condition replaces with chloro, bromo, iodo or the trifluoromethyl sulfonyl of for example optional replacement or heteroaryl reaction form general formula (1), wherein R 50Be the aryl or the heteroaryl groups of optional replacement.Suitable palladium catalyst is that palladium (II) is closed in chlorination two (triphenylphosphine).
Flow process 7
Figure A200780036889D00561
Other amine of general formula (8) or commercially available or can prepare by normative document method or standard method of modifying.
Shown in flow process 8, wherein Q1 is general formula (1) compound of bromine or iodine, thereby the substituted aryl or the heteroaryl compound that can be under the Suzuki condition form general formula (1) with the aryl or the heteroaryl acid reaction of for example optional replacement, wherein Q1 is the aryl or the heteroaryl groups of optional replacement.Suitable palladium catalyst is that four (triphenylphosphines) close palladium (O).
Flow process 8
Figure A200780036889D00562
Thioamides (the wherein general formula of L=S (1) compound) can be from corresponding amide, use vulcanizing agent such as phosphorus pentasulfide, Lawesson reagent or Davy reagent to prepare, perhaps use normative document method or standard method of modifying to prepare from corresponding thio-acid or monothioester.
The 6-oxyquinoline that replaces is obtainable, perhaps can use vitochemical direct method to prepare.When compound is not commercially available, can use in heterocyclic chemistry standard teaching material, encyclopaedize, prepare them at direct method for transformation well known in the art from obtainable precursor.For example, use suitable electrophilic reagent as 2,2,3 tribromo propionic aldehyde, the aromatic amine of replacement can be converted into the quinoline-6-alcohol of replacement easily.The example of such reaction is provided in embodiment 1-3.
Formula (I) compound is an active fungicide, can be used for preventing and treating one or more following pathogene: the Pyricularia Sacc. (Pyriculariaspp.) on the rice blast pears spore on rice and the wheat mould (Pyricularia oryzae) (rice blast pears spore mould (Magnaporthe grisea)) and other host; Puccinia recondita on the wheat (Puccinia triticina (or recondita)), bar shaped handle rest fungus (Puccinia striiformis) and other rest fungus, the rest fungus on the barley handle rest fungus (Puccinia hordei) on the barley, bar shaped handle rest fungus (Puccinia striiformis) and other rest fungus and other host (for example lawn, rye, coffee, pears, apple, peanut, sugar beet, vegetables and ornamental plants); Two spore powdery mildews (Erysiphe cichoracearum) on the cucurbitaceous plant (for example muskmelon); Barley, wheat, other powdery mildew on standing grain powdery mildew on rye and the lawn (Blumeria (or Erysiphe) graminis) (powdery mildew) and the various host is such as the spot monofilament shell (Sphaerotheca macularis) on the hops, monofilament shell on the cucurbitaceous plant (as cucumber) (Sphaerotheca fusca (Sphaerothecafuliginea)), tomato, Tartar's internal thread powdery mildew (Leveillulataurica) on eggplant and the green pepper, grape snag shell (Uncinula necator) on podosphaera leucotricha on the apple (Podosphaera leucotricha) and the grape; Cereal (wheat for example, barley, rye), cochliobolus on lawn and other host belongs to (Cochliobolus spp.), Helminthosporium (Helminthosporium spp.), Drechslera (Drechslera spp.) (nuclear cavity Pseudomonas (Pyrenophora spp.)), Rhynchosporium spp (Rhynchosporium spp.), standing grain green-ball chamber bacterium (Mycosphaerella graminicola) (wheat septoria (Septoria tritici)) and Phaeosphaeria nodorum (Stagonospora nodorum or clever withered septoria musiva (Septoria nodorum)), rotten germ (Pseudocercosporellaherpotrichoides) of wheat-based and gaeumannomyce bacterium (Gaeumannomyces graminis); Other Cercospora (Cercospora spp.) on peanut tail spore (Cercospora arachidicola) on the peanut and Cercosporidiumpersonatum and other host such as sugar beet, rubber, soybean and the rice; Other Botrytis (Botrytis spp.) on Botrytis cinerea on tomato, strawberry, vegetables, grape and other host (Botrytis cinerea) (grey mold) and other host; Alternaria (Alternaria spp.) on vegetables (for example carrot), oilseed rape, apple, tomato, potato, cereal (for example wheat) and other host; Venturia (Venturiaspp.) on apple, pears, drupe, tree nuts and other host (comprising venturia inaequalis (Venturia inaequalis) (scab)); A series of hosts comprise that the spore on cereal (for example wheat) and the tomato belongs to (Cladosporium spp.); Chain sclerotinia sclerotiorum on drupe, tree nuts and other host belongs to (Monilinia spp.); Asia on tomato, lawn, wheat, cucurbitaceous plant and other host belongs to (Didymellaspp.) every the spore shell; Phoma on oilseed rape, lawn, rice, potato, wheat and other host (Phoma spp.); Aspergillus on wheat, timber and other host (Aspergillus spp.) and Aureobasidium (Aureobasidium spp.); Ascochyta on pea, wheat, barley and other host (Ascochyta spp.); Stemphylium on apple, pears, onion and other host (Stemphylium spp.) (Pleospora (Pleospora spp.)); Disease in summer on apple and the pears (bitter rot (enclose little silk shell (Glomerella cingulata)) for example, black rot or fruit rot (Botryosphaeria obtusa), diplostomiasis (Mycosphaerellapomi), Cedar apple rust (Gymnosporangium juniperi-virginianae), coal spot disease (a kind of fruit, such as apple, pear, etc. glues shell spore (Gloeodes pomigena)), coal is selected disease (Schizothyriumpomi) and white rot (grape seat chamber bacterium (Botryosphaeria dothidea))); Grape on the grape is given birth to single shaft mould (plasmopara viticola); Other downy mildew, such as the dish stalk of the lettuce on the lettuce mould (Bremia lactucae), Peronospora on soybean, tobacco, onion and other host (Peronospora spp.), the Cuba artificial downy mildew (Pseudoperonospora cubensis) on false downy mildew (Pseudoperonospora humuli) of the hops on the hops and the cucurbitaceous plant; Pythium (Pythium spp.) (comprising ultimate corruption mould (Pythi umultimum)) on lawn and other host; Phytophthora (Phytophthora spp.) on phytophthora infestans on potato and the tomato (Phytophthora infestans) and vegetables, strawberry, avocado, pepper, ornamental plants, tobacco, cocoa bean and other host; Rhizoctonia (Rhizoctonia spp.) on thanatephorus cucumeris(frank) donk on rice and the lawn (Thanatephorus cucumeris) and various host such as wheat and barley, peanut, vegetables, cotton and the lawn; Sclerotinia (Sclerotiniaspp.) on lawn, peanut, potato, oilseed rape and other host; Sclerotium on lawn, peanut and other host (Sclerotium spp.); Gibberella fujikuroi on the rice (Gibberella fujikuroi); A series of hosts comprise the Colletotrichum (Colletotrichum spp.) on lawn, coffee and the vegetables; Laetisariafuciformis on the lawn; Mycosphaerella on banana, peanut, oranges and tangerines, pecan, pawpaw and other hosts (Mycosphaerella spp.); The seat shell belongs to (Diaporthe spp.) between on oranges and tangerines, soybean, muskmelon, pears, lupine and other host; Elsinoe on oranges and tangerines, grape, olive, pecan, rose and other host (Elsinoe spp.); A series of hosts comprise the Verticillium (Verticillium spp.) on hops, potato and the tomato; Bury Sclerotinia (Pyrenopeziza spp.) on oilseed rape and other host; On cocoa bean, cause the withered Oncobasidium theobromae of dimension pipe striped; Various the hosts particularly Fusarium (Fusarium spp.) on wheat, barley, lawn and the corn, nuclear coral Pseudomonas (Typhulaspp.), snow rotten microtorr bacterium (Microdochium nivale), Ustilago (Ustilagospp.), Urocystis (Urocystis spp.), Tilletia (Tilletia spp.) and ergot (Claviceps purpurea); On sugar beet, barley and other host every Cylindrocarpon (Ramularia spp.); Results back disease, the disease on the fruit (for example the Penicillium digitatum on the orange (Penicillium digitatum), Italian mould (Penicilliumitalicum) and Trichoderma viride (Trichoderma viride), bajiao banana thorn dish spore (Colletotrichum musae) on the rubber and the Botrytis cinerea (Botrytis cinerea) on long spore of banana dish (Gloeosporium musarum) and the grape) particularly; Other pathogene on the grape, especially Eutypa lata, grape Guignardia (Guignardia bidweiiii), phelliuns igniarius (Phellinus igniarus), grape Phomopsis bacterium (Phomopsis viticola), the false cup fungi (Pseudopeziza tracheiphila) of vascular bundle and hair Boreostereum vibrans (Stereumhirsutum); Other pathogene, especially Cephaloascus fragrans on trees (for example Lophodermium seditiosum) or the timber, long beak shell belong to (Ceratocystisspp.), Ophiostoma piceae, Penicillium (Penicillium spp.), false healthy and free from worry wood mould (Trichoderma pseudokoningii), Trichoderma viride (Trichoderma viride), Trichoderma harzianum, aspergillus niger (Aspergillus niger), Leptographium lindbergi and Aureobasidium pullulans (Aureobasidiumpullulans); And the fungi media of virus disease (how sticking mould (the POlymyxa graminis) on the such as grain as the media of barley yellow mosaic virus (BYMV) and the POlymyxa betae on the sugar beet as media) from root disease (rhizomania).
Formula (I) thus compound can be in plant tissue from the bottom up, move from top to bottom or in the part and effectively to resist one or more fungies.In addition, formula (I) thus compound can be enough volatile in vapor phase the effective fungi on one or more plants of antagonism.
Therefore the invention provides the method that antagonism or control cause plant characteristic of disease fungi, it comprises the formula of antifungal effective dose (I) compound administration location, soil or any other plant growing media such as nutrient solution to seed, plant or the seed of plant, plant.
Term " plant " used in the literary composition comprises seedling, shrub and tree.In addition, Fungicidal method of the present invention comprises the processing of protectiveness, therapeutic, interior absorption, radical-ability and anti-spore (antisporulant).
Formula (I) compound preferably is used for agricultural, gardening and turfgrass purpose with composition forms.
For with formula (I) compound administration to the location of seed, plant or the seed of plant, plant, soil or other growth media, usually be composition with formula (I) compound formulation, it comprises suitable inert diluent or carrier except that formula (I) compound, and optional surfactant (SFA).SFA is can be by reducing interfacial tension and causing that thus other character (for example dispersion, emulsification and moistening) changes the chemicals that makes interface (for example, liquid/solid, liquid/gas or liquid/liquid interface) character modification.Preferred all compositions (solid and liquid preparation) comprise 0.0001 to 95% weight, more preferably 1 to 85% weight, for example formula of 5 to 60% weight (I) compound.The general such fungi that is used to prevent and treat of said composition: to the 10kg per hectare, preferred 1g is to the 6kg per hectare with 0.1g, and more preferably 1g uses formula (I) compound to the ratio of 1kg per hectare.
When being used to dress seed, to 10g (for example 0.001g or 0.05g), preferred 0.005g is to 10g with per kilogram seed 0.0001g, and more preferably 0.005g uses formula (I) compound to the ratio of 4g.
Fungicidal composition is provided in another aspect of this invention, and it comprises formula (I) compound of antifungal effective dose and to its suitable carrier and thinner.
The method of antagonism and control fungi is provided in another aspect of the present invention, and it comprises with the described fungi of compositions-treated of the antifungal effective dose that comprises formula (I) compound or the location of described fungi.Said composition can be selected from the several formulations type, comprises pulvis (DP), water solube powder (SP), water-soluble granule (SG), water-dispersible granules (WG), wetting powder (WP), granule (GR) (slow or rapid release), solvable dense dose (SL), finish (OL), ultra low volume liquids (UL), missible oil (EC), can disperse dense dose (DC), emulsion (aqueous emulsion (EW) and oil emu (EO)), microemulsion (ME), suspension concentrates (SC), aerosol, atomizing/sootiness preparation, micro-capsule suspension (CS) and seed treatment preparation.The preparation type of Xuan Zeing will depend on physics, the chemistry and biology character of the specific purposes and formula (I) compound of hope in any case.
Can be by formula (I) compound and one or more solid diluents (for example natural clay, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, diatomite (kieselguhr), chalk, diatomite (diatomaceous earths), calcium phosphate, calcium carbonate and magnesium carbonate, sulphur, lime, flour, talcum and other organic with inorganic solid support) being mixed and becoming fine powder to prepare pulvis (DP) this mixture mechanical lapping.
Can pass through formula (I) compound and one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solid (such as polysaccharide), and alternatively, one or more wetting agents, one or more dispersants or the described mixture that is used for improving water dispersible/deliquescent reagent mix and prepare water solube powder (SP).Then this mixture is worn into fine powder.Also can make the similar compositions granulating to form water-soluble granule (SG).
Can pass through formula (I) compound and one or more solid diluents or carrier, one or more wetting agents, and preferably, one or more dispersants, and alternatively, one or more are used for promoting the suspending agent of the dispersion in the liquid to mix preparing wetting powder (WP).Then this mixture is worn into fine powder.Also can make the similar compositions granulating to form water-dispersible granules (WG).
Can be by making the compound particles granulation of formula (I) compound and one or more powdery solid diluent or carriers; perhaps by making formula (I) compound (or its solution in suitable reagent) be absorbed into honeycombed grain material (such as float stone; attapulgite clay; bleaching earth; diatomite (kieselguhr); diatomite (diatomaceous earths) or maize cob meal) from preformed blank granule, perhaps by formula (I) compound (or its solution in suitable reagent) is adsorbed onto on the stone material (such as sand; silicate; mineral carbonic acid salt; sulphate or phosphate) also optionally drying forms granule (GR).The reagent that is commonly used to promote to absorb or adsorbs comprises solvent (such as aliphatic series and aromatic petroleum solvent, alcohol, ether, ketone and ester) and sticker (such as polyvinyl acetate, polyvinyl alcohol, dextrin, sugar and vegetable oil).One or more other additives also can be included in the granule (for example emulsifier, wetting agent or dispersant).
Can disperse dense dose (DC) by preparing in formula (I) compound is water-soluble or the organic solvent as ketone, alcohol or glycol ether.These solvents can comprise surface-active agents (for example be used for improving water-thinned or prevent crystallization in spray cistern).
Can prepare missible oil (EC) or aqueous emulsion (EW) in the organic solvent (mixture that comprises one or more wetting agents, one or more emulsifier or described reagent alternatively) by formula (I) compound is dissolved in.The organic solvent that is suitable for EC comprise aromatic hydrocarbon (such as alkylbenzene or Fluhyzon, for example SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a registration mark), the dimethylformamide of ketone (such as cyclohexanone or methyl cyclohexanone), alcohol (such as phenyl alcohol, furfuryl alcohol or butanols), N-alkyl pyrrolidone (such as N-Methyl pyrrolidone or N-octylpyrrolidone), fatty acid is (such as C 8-C 10The fatty acid dimethylformamide) and chlorinated hydrocabon.Spontaneous emulsification when the EC product can be in adding entry produces and has enough stability to allow the emulsion by the suitable equipment spray application.The preparation of EW relates to as liquid (if it is not liquid at ambient temperature, it can melt being usually less than under 70 ℃ the reasonable temperature) or in solution (by it being dissolved in suitable solvent), obtain formula (I) compound, under high shear, gained liquid or solution are comprised emulsification in the water of one or more SFA then, producing emulsion.The solvent that is suitable for EW comprises that vegetable oil, chlorinated hydrocabon (such as chlorobenzene), arsol (such as alkylbenzene or Fluhyzon) and other have the suitable organic solvent of low solubility in water.
Can prepare microemulsion (ME) by water is mixed with the thermodynamically stable isotropic liquid preparation of spontaneous generation with the admixture of one or more solvents and one or more SFA.Formula (I) compound is present in the described water or in described solvent/SFA admixture at the very start.The solvent that is suitable for ME comprises those of aforementioned EC of being used for of this paper and EW.ME can be oil-in-water system or Water-In-Oil system (can by the existence of this system of electrical conductivity measurements determination) and can be suitable for mixing water miscible and oil-soluble agricultural chemicals in same preparation.ME is suitable for diluting in water, perhaps still as microemulsion or form conventional O/w emulsion.
Suspension concentrates (SC) can comprise the water-based or the non-aqueous suspension of the segmentation insoluble solids particle of formula (I) compound.Can use one or more dispersants alternatively by ball milling in appropriate medium or pearl mill solid type (I) compound, prepare SC with the fine grained suspension that produces described compound.Can comprise one or more wetting agents in the composition, can also comprise that suspending agent is to reduce the particles settling rate.Alternatively, the formula of can dry grinding (I) compound also comprises its adding in the water of this paper aforementioned agents, produces the final products of wishing.
The aerosol preparation comprises formula (I) compound and suitable propellant (for example normal butane).Formula (I) compound can be dissolved in or be scattered in the appropriate medium (for example water or liquid that can be miscible, as normal propyl alcohol) to be provided at the composition that uses in non-pressurized, the manual atomizing pump with water.
Formula (I) compound can be mixed the composition that is suitable for producing the smog that comprises described compound with formation in enclosure space with firework mixture under drying regime.
Can be by similar but have the mode of the polymerization stage of an increase to prepare micro-capsule suspension (CS) with preparation EW preparation, so obtain the water-borne dispersions of oil droplet, wherein each oil droplet be aggregated thing shell packing and comprise formula (I) compound and, alternatively, carrier for this reason or thinner.Can produce above-mentioned polymer shell by the interfacial polycondensation reaction or by coacervation process.Said composition can provide the sustained release of formula (I) compound, and it can be used to seed treatment.Formula (I) compound can by preparation in Biodegradable polymeric matrix with provide described compound slowly, controlled release.
Composition can be included as the biology performance that improves said composition (for example by improve lip-deep moistening, keep or distribute; Anti-rainwash on treated surface; The picked-up of formula (I) compound and mobile) one or more additives.Such additive comprises surface-active agents, spray additives based on oil, for example some mineral oil or crude vegetal (such as soybean or rapeseed oil), and the admixture of these reagent and other biology-reinforcing aids composition of the effect of modification formula (I) compound (can promote or).
All right preparation formula (I) compound is to be used as seed treatment, for example as powder composition, comprise seed treatment dry powder doses (DS), seed treatment soluble powder (SS) or slurry kind of processing water-dispersible powder (WS), perhaps, comprise seed treatment suspension concentrates (FS), seed treatment liquor (LS) or micro-capsule suspension (CS) as fluid composition.DS, SS, WS, FS and LS preparation of compositions are very similar with above-mentioned DP, SP, WP, SC and DC preparation of compositions respectively.The composition of handling seed can comprise that aid composition is adhered to the reagent of seed (for example mineral oil or one-tenth envelope barrier).
Wetting agent, dispersant and emulsifier can be the SFA of cation, anion, both sexes or nonionic.
Suitable cationic SFA comprises quaternary ammonium compound (for example softex kw), imidazolines and amine salt.Suitable anion SFA comprises the alkali metal salt of fatty acid, the salt of sulfuric acid aliphatic mono (for example lauryl sodium sulfate), the salt of sulfonated aromatic compound (neopelex for example, calcium dodecyl benzene sulfonate, the mixture of butyl naphthalene sulfonate and diisopropyl sodium naphthalene sulfonate and triisopropyl sodium naphthalene sulfonate), ether sulfate, ether alcohol sulfate (for example three laureth 9 sodium sulphate (sodium laureth-3-sulphate)), ether carboxylate (for example three laureth 9 carboxylic acid sodium (sodiumlaureth-3-carboxylate)), phosphate (product of one or more fatty alcohols and phosphatase reaction (mainly being monoesters) or the product (mainly being diester) that reacts with phosphorus pentoxide, for example dodecanol and four phosphatase reactions; These products can be by ethoxyquin in addition), sulfosuccinamic acid ester, alkane or alkene sulfonate, taurate and lignosulfonates.Suitable amphoteric SFA comprises betain, propionate and glycinate.Suitable nonionic SFA comprise as the epoxyalkane of oxirane, expoxy propane, epoxy butane or its mixture and fatty alcohol (such as oleyl alcohol or octanol) or with the condensation product of alkyl phenol (such as octyl phenol, nonyl phenol or octyl group cresols); The partial ester of derivation of self-long chain fatty acid or hexitan mixture; The condensation product of described partial ester and oxirane; Block polymer (comprising oxirane and expoxy propane); Alkanolamide; Simple ester (for example fatty acid polyethylene glycol ester); Amine oxide (for example dodecyl dimethyl amine oxide); And lecithin.
Suitable suspending agent comprises hydrophilic colloid (such as polysaccharide, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelled ground (such as bentonite or attapulgite).
Formula (I) compound can be used by any known method of using Fungicidal compounds.For example, its can with preparation or not dosage form be applied directly to and comprise leaf, stem, any plant part of branch or root, before cultivation, be applied to seed, perhaps be applied to growing plant wherein or other media that will cultivated plant (such as the soil around the root, soil in general sense, paddy field water either or soilless culture system), perhaps in soil or aqueous environment, spray, dust, use by dipping, use as creme or paste, use or distribution by composition (such as particulate composition or be packaged in composition in the water-soluble bag) or mix and use as steam.
Can also use electric atomizing technology or other low capacity method formula (I) compound injection is gone into plant or to be sprayed on the vegetation, or use by land or aerial irrigation system.
Usually to comprise the composition that the stoste form supply of active component at high proportion is used as aqueous compositions (aqueous solution or dispersion liquid), before use this stoste is added in the water.These can comprise that the stoste of DC, SC, EC, EW, ME, SG, SP, WP, WG and CS need be stood long storage usually and can be added to and form aqueous compositions in the water that it keeps evenly so that it can be used by habitual spraying apparatus in time enough after such storage.According to its application target, such aqueous compositions can comprise formula (I) compound (for example 0.0001 to 10% weight) of variable quantity.
Formula (I) compound can with fertilizer (for example nitrogenous-, contain potassium-or phosphorous-fertilizer) mix use.Suitable preparation type comprises the granule of fertilizer.This mixture comprises aptly up to the formula of 25% weight (I) compound.
So the present invention also provides the Ru 2006101161 that comprises fertilizer and formula (I) compound.
Composition of the present invention can comprise the compound of other biologically active, for example micronutrient or the compound that has the compound of similar or additional Fungicidally active or have plant growth regulating, weeding, desinsection, nematicide or acaricidal activity.
By comprising other fungicide, resulting composition can have than wideer activity profile of independent formula (I) compound or higher intrinsic activity level.Further, this other fungicide can play synergy to the Fungicidally active of formula (I) compound.
Formula (I) compound can be the unique active component in the composition or can mix with one or more additional activity compositions when suitable that described additional activity composition is as murdering agent, fungicide, synergist, weed killer herbicide or plant growth regulator.The additional activity composition can: provide to have broad spectrum of activity more or at persistent composition of on-site increase; The activity of the activity of synergy formula (I) compound or compensation type (I) compound (for example by increasing onset speed or overcoming anti-repelling properties); Or help to overcome or prevent to develop the resistance that at single composition.Concrete additional activity composition will depend on the hope purposes of described composition.
The example of the Fungicidal compounds that can comprise in the composition of the present invention is AC 382042 (N-(1-cyano group-1,2-dimethyl propyl)-2-(2,4 dichloro benzene oxygen base) propionamide), Acibenzolar, alanycarb, tears morpholine difficult to understand (aldimorph), anilazine, oxygen ring azoles, azafenidin, Fluoxastrobin, M 9834, benomyl, the benzene metsulfovax, biloxazol, bitertanol, blasticidin-S (blasticidin S), Boscalid (newname of nicobifen), bromuconazole, bupirimate, difoltan, captan, carbendazim, carbendazim hydrochloride, carboxin, ring propionyl bacterium amine, carvol, CGA 41396, CGA 41397, chinomethionat, chlorobenzene match ketone (chlobenzthiazone), tpn, chlozolinate, clozylacon, copper-containing compound such as COPPER OXYCHLORIDE 37,5, oxyquinoline copper, copper sulphate, fatty acid copper and bordeaux mixture, cyanogen frost azoles, cyanogen frost azoles (IKF-916), cyflufenamid, frost urea cyanogen, Cyproconazole, cyprodinil, debacarb, two-2-pyridyl disulfide 1,1 '-dioxide, dichlofluanid, two chlorine zarilamids, diclomezin, the fluorine nitramine, the mould prestige of second, Difenoconazole, difenzoquat, the fluorine mepanipyrim, O, O-two-isopropyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethirimol, dimethomorph, ether bacterium amine, alkene azoles alcohol, karathane, dithianon, chlorination dodecyl dimethyl ammonium, dodemorph, dodine, doguadine, edifenphos, fluorine ring azoles, Guardian, the phonetic phenol of second, (Z)-N-benzyl-N ([methyl (methyl-sulfo-ethyleneimino oxygen base carbonyl) amino] sulfo-)-Beta-alanine ethyl ester, Grandox fumigant oxazole bacterium ketone, Fenamidone, Fenarimol, RH-7592, fenfuram, fenhexamid, zarilamid (AC 382042), fenpiclonil, fenpropidin, butadiene morpholine, fentin acetate, triphenyl tin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluorine acyl bacterium amine, flumorph, fluoromide, fluoxastrobin, Fluquinconazole, Flusilazole, flusulfamide, flutolanil, Flutriafol, folpet, phosethyl-Al, furidazol, furalaxyl, furan pyrrole bacterium amine, guazatine, own azoles alcohol, hydoxyisoxazole ， hymexazo presses down mould azoles, glyoxalin, iminoctadine, the iminoctadine triacetate is planted the bacterium azoles, iprobenfos, iprodione, iprovalicarb, butyl carbamic acid isopropyl ester, Isoprothiolane, kasugarnycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, maneb, Metalaxyl-M, mepanipyrim, mebenil, metalaxyl, Metalaxyl-M, metconazole, Carbatene, Carbatene zinc, SSF 126, the table metrafenone, MON65500 (N-pi-allyl-4,5-dimethyl-2-trimethyl silyl thiophene-3-formamide), nitrile bacterium azoles, NTN0301, neoasozin, nickel dimethyldithiocarbamate, nitrothalisopropyl, nuarimol, ofurace, organomercurial compound, the spirit of orysastrobin Evil frost, oxasulfuron, oxolinic acide Evil imidazoles, oxycarboxin, pefurazoate, penconazole, Pencycuron, phenazine oxide, phosphorous acid, Rabcide, ZEN 90160, polyoxin D, Carbatene (polyram), probenazole, Prochloraz, procymidone, Propamocarb, Propamocarb hydrochloride, propiconazole, Propineb, propionic acid, the third oxygen quinoline, prothioconazoles, pyraclostrobin, pyrazophos, pyrifenox, phonetic mould amine, pyroquilon, chlorine pyrrole furan ether, pyrrolnitrin, quaternary ammonium compound, chinomethionat, benzene oxygen quinoline, pcnb, silicon metsulfovax (MON 65500), S-presses down mould azoles, simeconazoles, simeconazoles (sipconazole), the pentachlorobenzene sodium oxide molybdena, volution bacterium amine, streptomycin, sulphur, Tebuconazole, tecloftalam, tecnazene, tetraconazole, probenazole, thifluzamide, 2-(sulfo-cyanomethylthio) benzothiazole, thiophanate-methyl, tmtd, tiadinil, glyoxalin (timibenconazole), tolelofos-methyl, Tolylfluanid, triazolone, Triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, oxime bacterium ester, fluorine bacterium azoles, triforine, triticonazole, Validacin (Takeda), metham-sodium, vinclozolin, XRD-563, zineb, ziram, zoxamide and formula
Figure A200780036889D00681
With
Figure A200780036889D00682
Compound.
Formula (I) compound can be mixed with soil, peat or other rooting media with seed dispersal, the soilborne or leaf fungal disease of protective plant antagonism.
Some mixture can comprise the active component with remarkable different physics, chemistry or biological property, so that they are difficult for being used in the same conventional formulation type.In this case, can prepare other preparation type.For example, when a kind of active component is that water-soluble solid and another kind of active component are when being water-insoluble liquid, by described solid active agent is disperseed (using and the similar preparation method of SC) and described liquid actives still can be dispersed in every kind of active component same continuous aqueous phase as emulsion dispersion (using and the similar preparation method of EW) as suspension.Resulting composition is suspension emulsion (SE) preparation.
The present invention is illustrated by following embodiment, the abbreviation below wherein using:
Ml=milliliter m.p.=fusing point (not proofreading and correct)
G=gram b.p.=boiling point
THF=oxolane DMSO=methyl-sulfoxide
M +=mass ion (mass ion) DMF=N, dinethylformamide
The unimodal d=doublet of s=
HOBT=1-hydroxybenzotriazole HOAT=7-azepine-1-hydroxy benzo three
Azoles
The wide unimodal NMR=nuclear magnetic resonnance of bs=
T=triplet HPLC=high performance liquid chromatography
Q=quartet TLC=thin layer chromatography
M=multiplet glc=gas liquid chromatography
Ppm=1,000,000/EDC=1-ethyl-3-N, the N-dimethylamino
M=molar concentration base propyl group carbodiimide hydrochloride
Embodiment 1
This embodiment illustrates the preparation of 2-(3-bromo-7-chloro-quinoline-6-oxygen the base)-N-tert-butyl group-2-methyl mercapto-acetamide (table 2 compound N o.12)
Stage 1. preparation 3-bromo-7-chloro-quinoline-6-alcohol
Step 1
With 2,2,3 tribromo propionic aldehyde (18.8g) are handled, and at room temperature stir this mixture 2h with the 3-chloro-4-aminoanisole (10g) in the acetate (100ml), after this dilute with water and use ethyl acetate extraction.Organic facies is with 2N NaOH washing, and is dry on sodium sulphate, filters and reduction vaporization, provides the product of hope through chromatography (silica gel, hexane/ethyl acetate), and 3-bromo-7-chloro-6-methoxy yl-quinoline is yellow solid (M +274).
1H?NMR(CDCl 3)δ?ppm：8.78(1H，d)；8.21(1H，d)；8.10(1H，s)；7.03(1H，s)。
Step 2
The product (1.4g) of step 1 and the mixture of hydrobromic acid (the 48 weight % aqueous solution) (100ml x2) were refluxed 62 hours.Mixture is cooled to environmental temperature, and ethyl acetate extraction is handled and used to dilute with water with sodium bicarbonate.Extract is dry on magnesium sulfate, filters, and reduction vaporization provides required product, 3-bromo-7-chloro-quinoline-6-alcohol (M+260). 1H?NMR(DMSO)δ·ppm：7.34(1H，s)；7.07(1H，s)；8.60(1H，d)；8.73(1H，d)；11.12(1H，s)。
Stage 2:Preparation (3-bromo-7-chloro-quinoline-6-base oxygen base)-methyl mercapto-methyl acetate
Step 1
In stirring, be cooled in-15 ℃ carrene (300ml) solution of (methyl mercapto) methyl acetate (10.8ml) and drip sulfonic acid chloride (8.1ml).This mixture put be warmed to room temperature, last 2 hours, then concentrating under reduced pressure provides thick chloro-methyl mercapto-methyl acetate, is colourless liquid.Product do not added to be further purified be used for subsequent step. 1H?NMR(CDCl 3)δ?ppm：2.33(3H，s)；3.83(3H，s)；5.49(1H，s)。
Step 2
At ambient temperature, in dry DMF (17ml) solution in stirring, 3-bromo-7-chloro-quinoline that comprise Anhydrous potassium carbonate (3.1g), stage 1 step 2-6-alcohol (1.1g), drip chloro-methyl mercapto-methyl acetate (0.79g).This mixture was heated 1 hour down at 60-65 ℃, be cooled to environmental temperature then, dilute with water is also used ethyl acetate extraction.Merge extract, use the salt water washing, dry on magnesium sulfate, filter reduction vaporization.By chromatography (silica gel, the ethyl acetate/hexane of 1:4 volume ratio) purifying roughage, provide title compound, 3-bromo-7-chloro-quinoline-6-base oxygen base)-methyl mercapto-methyl acetate (M+378). 1H?NMR(CDCl 3)δ?ppm：2.29(3H，s)；3.89(3H，s)；5.74(1H，s)7.18(1H，8)；8.16(1H，s)；8.23(1H，s)；8.82(1H，s)。
Stage 3:Preparation (3-bromo-7-chloro-quinoline-6-base oxygen base)-methyl mercapto-acetate
At ambient temperature, the aqueous solution (2.2ml) that adds 2N sodium hydroxide in the solution of product (1.1g) in ethanol (14ml) of stages 2 step 2 in stirring.This mixture was at room temperature stirred 1 hour, subsequently in the impouring frozen water, and with the hcl acidifying of 2M.With the elimination from solution of obtaining precipitation, use cold water washing, vacuum drying provides (3-bromo-7-chloro-quinoline-6-base oxygen base)-methyl mercapto-acetate (M+364). 1H?NMR(DMSO-d6)δ?ppm：2.20(3H，s)；6.18(1H，s)7.57(1H，s)；8.19(1H，s)；8.28(1H，d)；8.88(1H，d)；13.7(1H，bs)。
Stage 4:Preparation 2-(3-bromo-7-chloro-quinoline-6-base oxygen the base)-N-tert-butyl group-2-methyl mercapto-acetamide
At ambient temperature, with anhydrous N, the product 3-bromo-7-chloro-quinoline in the above-mentioned stage 3 in the dinethylformamide (2ml)-6-base oxygen base)-and methyl mercapto-acetate (85mg) is with tert-butylamine (17mg), N-(3-dimethylamino-propyl group)-N '-ethyl-carbodiimide hydrochloride (45mg), HOAt (32mg) and triethylamine (24mg) processing, stirred 3 hours.In this mixture impouring water, with ethyl acetate extraction (three times), merge extract, dry on magnesium sulfate subsequently with saturated aqueous sodium carbonate, water (three times) washing, filter, reduction vaporization provides grease.By chromatography (silica gel; The hexane/ethyl acetate of 3:1 volume ratio) this grease of chromatography provides required product, be white solid (m.p.172-174 ℃, M+419). 1H?NMR(CDC?l 3)δ?ppm：1.46(9H，s)；2.18(3H，s)；5.63(1H，s)；6.89(1H，bs)；7.28(1H，s)；7.28(1H，s)；8.18(1H，s)，8.27(1H，d)；8.83(1H，d)。
Use similar approach to prepare following acid amides.
Table 2 compound N is o.238: use 1,1-dimethyl-Propargyl amine, m.p.169-171 ℃; 1H NMR (CDCl 3) δ ppm:1.75 (6H, s); 2.19 (3H, s); 2.41 (1H, s); 5.69 (1H, s); 7.16 (1H, bs); 7.29 (1H, s); 8.18 (1H, s); 8.27 (1H, d); 8.83 (1H, d).
Table 2 compound N is o.52: use 2-amino-3-methoxyl group-2-methyl-propionitrile, 1H NMR (CDCl 3) δ ppm: diastereo-isomerism mixture (1/1); 1.82 and 1.84 (3H, 2xs); 2.18 and 2.20 (3H, 2xs); 3.52 and 3.53 (3H, 2xs); 3.64-3.84 (2H, 2xdd); 5.76 and 5.77 (1H, 2xs); 7.29 and 7.30 (1H, 2xs); 7.59 and 7.61 (1H, 2xbs); 8.18 (1H, s); 8.29 (1H, d); 8.85 (1H, s).
Table 2 compound N is o.244: use 1,1-dimethyl-Ding-2-alkynylamine, m.p.160-162 ℃; 1H NMR (CDCl 3) δ ppm:1.71 (6H, s); 1.83 (3H, s); 2.19 (3H, s); 5.66 (1H, s); 7.15 (1H, bs); 7.27 (1H, s); 8.18 (1H, s); 8.27 (1H, d); 8.83 (1H, d).
Table 2 compound N is o.251: use 4-methoxyl group-1,1-dimethyl-Ding-2-alkynylamine, m.p.124-125 ℃; 1H NMR (CDCl 3) δ ppm:1.75 (6H, s); 2.19 (3H, s); 3.39 (3H, s); 4.13 (2H, s); 5.67 (1H, s); 7.17 (1H, bs); 7.28 (1H, s); 8.18 (1H, s); 8.28 (1H, d); 8.84 (1H, d).
Embodiment 2
This embodiment illustrates the preparation of 2-(3-bromo-7-methyl-quinoline-6-base oxygen the base)-N-tert-butyl group-2-methyl mercapto-acetamide (table 13 compound N o.12)
Stage 1. preparation 3-bromo-7-methyl-quinoline-6-alcohol
With 2,2,3 tribromo propionic aldehyde (11.9g) are handled, and at room temperature stir this mixture 3h with the 4-amino-2-methyl phenol (5g) in the acetate (60ml), after this dilute with water and use ethyl acetate extraction.Organic facies NH 4The OH solution washing, dry on sodium sulphate, filter, reduction vaporization provides required product, and 3-bromo-7-methyl-6-quinoline-6-alcohol is directly used in subsequent step (M with it +240), 1H NMR (DMSO-d6) δ ppm:2.32 (3H, s); 7.12 (1H, s); 7.75 (1H, s); 8.46 (1H, d); 8.64 (1H, d); 10.35 (1H, bs).
Stage 2:Preparation 3-bromo-7-methyl-quinolyl-6-oxygen base-2-methyl mercapto acetate methyl esters
With with the similar method of embodiment 1 stages 2 step 2, with 3-bromo-7-methyl-quinoline-6-alcohol and the reaction of 2-bromo-2-methyl mercapto acetate methyl esters, provide 3-bromo-7-methyl-quinolyl-6-oxygen base-2-methyl mercapto-methyl acetate (M +358). 1H?NMR(CDCl 3)δ?ppm：2.25(3H，s)；2.50(3H，s)；3.88(3H，s)；5.73(1H，s)；6.99(1H，s)；7.86(1H，s)；8.19(1H，d)，8.76(1H，d)。
Stage 3: preparation (3-bromo-7-methyl-quinoline-6-base oxygen base)-methyl mercapto-acetate
With with embodiment similar method of 1 stages 3,, provide (3-bromo-7-methyl-quinoline-6-base oxygen base)-methyl mercapto-acetate (M with 3-bromo-7-methyl-quinolyl-6-oxygen base-2-methyl mercapto-methyl acetate hydrolysis +344). 1H?NMR(DMSO)?δ?ppm：2.19(3H，s)；2.42(3H，s)；6.07(1H，s)；7.42(1H，s)；7.86(1H，s)；8.52(1H，s)，8.78(1H，s)，13.55(1H，bs)。
Stage 4: preparation 2-(3-bromo-7-methyl-quinoline-6-base oxygen the base)-N-tert-butyl group-2-first sulphur Base-acetamide
With with embodiment similar method of 1 stages 4, with 2-(3-bromo-7-methyl-quinolyl-6-oxygen base)-2-methyl mercapto acetate and tert-butylamine condensation, provide 2-(3-bromo-7-methyl-quinoline-6-base oxygen base)-N-tert-butyl group-2-methyl mercapto-acetamide (m.p.132-134 ℃, M +344). 1H?NMR(CDCl 3)δ?ppm：1.44(9H，s)；2.19(3H，s)；2.49(3H，s)；5.60(1H，s)；6.48(1H，bs)；7.10(1H，s)；7.89(1H，s)；8.21(1H，d)，8.78(1H，d)。
Use similar approach to prepare following acid amides.
Table 13 compound N is o.16: use 1,1-dimethyl-propylamine, m.p.135-137 ℃; 1H NMR (CDC l 3) δ ppm:0.88 (3H, t); 1.39 (6H, s); 1.79 (2H, q); 2.20 (3H, s); 2.48 (3H, s); 5.59 (1H, s); 6.39 (1H, bs); 7.10 (1H, s); 7.89 (1H, s); 8.21 (1H, d); 8.78 (1H, d).
Table 13 compound N is o.238: use 1,1-dimethyl-Propargyl amine, m.p.141-146 ℃; 1H NMR (CDCl 3) δ ppm:1.74 (6H, s); 2.19 (3H, s); 2.41 (1H, s); 2.50 (3H, s); 5.65 (1H, s); 6.77 (1H, bs); 7.10 (1H, s); 7.89 (1H, s); 8.21 (1H, d); 8.78 (1H, d).
Table 13 compound N is o.52: use 2-amino-3-methoxyl group-2-methyl-propionitrile, 1H NMR (CDCl 3) δ ppm: diastereo-isomerism mixture (1/1); 1.81 and 1.83 (3H, 2xs); 2.20 and 2.21 (3H, 2xs); 2.48 (3H, s); 3.50 and 3.53 (3H, 2xs); 3.61-3.82 (2H, 2xdd); 5.72 and 5.75 (1H, 2xs); 7.11 and 7.13 (1H, 2xs);
7.32 and 7.34 (1H, 2xbs); 7.90 (1H, s); 8.23 (1H, s); 8.79 (1H, s).
Table 13 compound N is o.221: use 1,1-dimethyl-2-third-2-alkynyloxy group-ethamine, m.p.114-116 ℃; 1H NMR (CDCl 3) δ ppm:1.41 (3H, s); 1.44 (3H, s); 2.18 (3H, s); 2.50 (1H, t); 3.54 (2H, dd); 4.19 (2H, d); 5.61 (1H, s); 6.92 (1H, bs); 7.10 (1H, s); 7.88 (1H, s); 8.22 (1H, d); 8.77 (1H, d).
Table 13 compound N is o.251: use 4-methoxyl group-1,1-dimethyl-Ding-2-alkynylamine, m.p.129-132 ℃; 1H NMR (CDCl 3) δ ppm:1.73 (6H, s); 2.20 (3H, s); 2.49 (3H, s); 3.37 (3H, s); 4.11 (2H, s); 5.63 (1H, s); 6.76 (1H, bs); 7.10 (1H, s); 7.89 (1H, s); 8.21 (1H, d); 8.78 (1H, d).
Embodiment 3
This embodiment illustrates the preparation of 2-(3-bromo-7-fluoro-quinoline-6-base oxygen the base)-N-tert-butyl group-2-methyl mercapto-acetamide (table 6 compound N o.12)
Stage 1. preparation 3-bromo-7-fluoro-quinoline-6-alcohol
Step 1
With with the similar method of embodiment 1 stage 1 step 1, with 2,2, the processing of 3 tribromo propionic aldehyde (4.2g) provides 3-bromo-7-fluoro-6-methoxy yl-quinoline (M with the 3-fluoro-4-methoxyl group-aniline (2g) in the acetate (25ml) +258). 1H?NMR(CDCl 3)δ?ppm：4.02(3H，s)；7.07(1H，d)；7.75(1H，d)；8.23(1H，d)；8.78(1H，d)。
Step 2
With with the similar method of embodiment 1 stages 2 step 1, will handle with hydrobromic acid from the rapid 3-bromo-7-fluoro-6-methoxy yl-quinoline of previous step, provide 3-bromo-7-fluoro-quinoline-6-alcohol (M +244). 1H?NMR(DMSO-d6)δ?ppm：7.35(1H，d)；7.77(1H，d)；8.59(1H，d)；8.74(1H，d)，10.93(1H，s)。
Stage 2:Preparation (3-bromo-7-fluoro-quinoline-6-base oxygen base)-methyl mercapto-methyl acetate
With with the similar method of embodiment 1 stages 2 step 2,2-bromo-2-methyl mercapto acetate methyl esters pure from the rapid 3-bromo-7-fluoro-quinoline of previous step-6-and from embodiment 1 stages 2 step 1 is reacted, provide 3-bromo-7-fluoro-quinolyl-6-oxygen base-2-methyl mercapto acetate methyl esters (M +362). 1H?NMR(CDCl 3)δ?ppm：2.27(3H，s)；3.89(3H，s)；5.77(1H，s)7.26(1H，d)；7.77(1H，s)；8.23(1H，s)；8.83(1H，s)。
Stage 3: preparation (3-bromo-7-fluoro-quinoline-6-base oxygen base)-methyl mercapto-acetate
With with embodiment similar method of 1 stages 3,, provide (3-bromo-7-fluoro-quinoline-6-base oxygen base)-methyl mercapto-acetate (M with 3-bromo-7-fluoro-quinolyl-6-oxygen base-2-methyl mercapto-methyl acetate hydrolysis +348). 1H?NMR(DMSO-d6)δ?ppm：6.16(1H，s)；7.71(1H，d)7.90(1H，d)；8.62(1H，d)，8.88(1H，d)，13.69(1H，bs)。
Stage 4:Preparation 2-(3-bromo-7-fluoro-quinoline-6-base oxygen the base)-N-tert-butyl group-2-methyl mercapto-acetamide
With with embodiment similar method of 1 stages 4, with 2-(3-bromo-7-fluoro-quinolyl-6-oxygen base)-2-methyl mercapto acetate and tert-butylamine condensation, provide 2-(3-bromo-7-fluoro-quinoline-6-base oxygen the base)-N-tert-butyl group-2-methyl mercapto-acetamide (m.p.144-145 ℃, M +403). 1H?NMR(CDCl 3)δ?ppm：1.45(9H，s)；2.19(3H，s)；5.62(1H，s)；6.62(1H，bs)；7.30(1H，d)；7.79(1H，d)；8.26(1H，d)，8.84(1H，d)。
Use similar approach to prepare following acid amides.
Table 6 compound N is o.238: use 1,1-dimethyl-Propargyl amine, m.p.167-169 ℃; 1H NMR (CDCl 3) δ ppm:1.75 (6H, s); 2.21 (3H, s); 2.41 (1H, s); 2.50 (3H, s); 5.68 (1H, s); 6.89 (1H, bs); 7.33 (1H, d); 7.79 (1H, d); 8.26 (1H, d); 8.84 (1H, d).
Table 6 compound N is o.52: use 2-amino-3-methoxyl group-2-methyl-propionitrile, 1H NMR (CDCl 3) δ ppm: diastereo-isomerism mixture (1/1); 1.81 and 1.83 (3H, 2xs); 2.21 and 2.22 (3H, 2xs); 3.52 and 3.54 (3H, 2xs); 3.64-3.84 (2H, 2xdd); 5.75 and 5.76 (1H, 2xs); 7.33-7.36 (2H, m); 7.80 (1H, d); 8.28 (1H, d); 8.85 (1H, d).
Table 6 compound N is o.221: use 1,1-dimethyl-2-third-2-alkynyloxy group-ethamine, m.p.115-117 ℃; 1H NMR (CDCl 3) δ ppm:1.44 (3H, s); 1.46 (3H, s); 2.20 (3H, s); 2.45 (1H, t); 3.61 (2H, dd); 4.20 (2H, d); 5.63 (1H, s); 6.90 (1H, bs); 7.28 (1H, d); 7.78 (1H, d); 8.26 (1H, d); 8.83 (1H, d).
Table 6 compound N is o.251: use 4-methoxyl group-1,1-dimethyl-Ding-2-alkynylamine, m.p.115-117 ℃; 1H NMR (CDCl 3) δ ppm:1.74 (6H, s); 2.21 (3H, s); 2.49 (3H, s); 3.38 (3H, s); 4.12 (2H, s); 5.65 (1H, s); 6.88 (1H, bs); 7.31 (1H, d); 7.79 (1H, d); 8.26 (1H, d); 8.84 (1H, d).
Table 6 compound N is o.244: use 1,1-dimethyl-Ding-2-alkynylamine, m.p.130-132 ℃; 1H NMR (CDCl 3) δ ppm:1.70 (6H, s); 1.83 (3H, s); 2.21 (3H, s); 5.65 (1H, s); 6.86 (1H, bs); 7.31 (1H, d); 7.78 (1H, d); 8.25 (1H, d); 8.84 (1H, d).
Table 6 compound N is o.68: use 2-ethyoxyl-1,1-dimethyl-ethamine, m.p.111-113 ℃; 1H NMR (CDCl 3) δ ppm:1.21 (3H, t); 1.43 (H, s); 1.46 (3H, s); 2.20 (3H, s); 3.43 (2H, dd); 3.51-3.58 (2H, m), 5.63 (1H, s); 7.17 (1H, bs); 7.28 (1H, d); 7.78 (1H, d); 8.25 (1H, d); 8.83 (1H, d).
Table 6 compound N is o.277: use 5-methoxyl group-1,1-dimethyl-penta-2-alkynylamine, m.p.104-106 ℃; 1H NMR (CDCl 3) δ ppm:1.71 (6H, s); 2.20 (3H, s); 2.48 (2H, t); 3.37 (3H, s); 3.50 (2H, t); (5.65 (1H, s); 6.88 (1H, bs); 7.31 (1H, d); 7.79 (1H, d); 8.26 (1H, d); 8.84 (1H, d).
Table 6 compound N is o.256: use 6-chloro-1, and the 1-dimethyl-oneself-the 2-alkynylamine, m.p.95-97 ℃; 1H NMR (CDCl 3) δ ppm:1.70 (6H, s); (1.96 2H, quintet), 2.20 (3H, s); 2.90 (2H, t); 3.68 (2H, t); 3.50 (2H, t); 5.66 (1H, s); 6.87 (1H, bs); 7.31 (1H, d); 7.79 (1H, d); 8.26 (1H, d); 8.84 (1H, d).
Embodiment 4
This embodiment illustrates the preparation of 2-(3-iodo-7-fluoro-quinoline-6-base oxygen the base)-N-tert-butyl group-2-methyl mercapto-acetamide (table 7 compound N o.12)
Stage 1: preparation 3-iodo-6-oxyquinoline
In sealed tube, add N in the 3-bromo-7-fluoro-6-oxyquinoline (0.50g) from embodiment 3 stage 1 step 2, sodium iodide (0.62g) and the mixture of cupric iodide (0.08g) in dioxane (3.0ml) in stirring, N, N ', N '-tetramethyl-ethane-1,2-diamines (0.07g).Mixture is stirred 14h down at 120 ℃, when cooling, use ammonia treatment, handle with aqueous hydrochloric acid solution subsequently.Use ethyl acetate extraction, dry organic facies on magnesium sulfate is filtered, and reduction vaporization provides required product (M +290), be light brown powder, it is directly used in subsequent step. 1H?NMR(CDCl 3)δ?ppm：7.30(1H，d)；7.72(1H，d)；8.02(1H，d)，8.73(1H，d)；8.83(1H，d)，10.88(1H，s)。
Stage 2: the preparation N-tert-butyl group-2-(3-iodo-7-fluoro-quinoline-6-base oxygen base)-2-methyl mercapto-acetamide
With with the similar method of embodiment 1 stages 2 step 1,, provide (the basic oxygen base of 3-iodo-7-fluoro-quinoline-6-)-methyl mercapto-ethyl acetate (M with 3-iodo-7-fluoro-6-oxyquinoline and chloro methyl mercapto-acetic acid ethyl reaction +408).
With with embodiment similar method of 1 stages 3, will (3-iodo-7-fluoro-quinoline-6-base oxygen base)-methyl mercapto-hydrolysis of ethyl acetate, provide (3-iodo-7-fluoro-quinoline-6-base oxygen base)-methyl mercapto-acetate (M +394).
With with embodiment similar method of 1 stages 4, with (3-iodo-7-fluoro-quinoline-6-base oxygen base)-methyl mercapto-acetate and tert-butylamine condensation, provide the N-tert-butyl group-2-(3-iodo-quinoline-6-base oxygen base)-2-methyl mercapto-acetamide, be white solid (m.p.165-166 ℃, M +449).
1H?NMR(CDCl 3)δppm：1.44(9H，s)；2.18(3H，s)；5.60(1H，s)；6.62(1H，bs)；7.27(1H，d)；7.76(1H，dd)；8.47(1H，d)；8.97(1H，d)。
Use similar approach to prepare following acid amides.
Table 7 compound N is o.238: use 1,1-dimethyl-Propargyl amine, m.p.150-152 ℃; 1H NMR (CDCl 3) δ ppm:1.75 (6H, s); 2.20 (3H, s); 2.40 (1H, s); 5.66 (1H, s); 6.88 (1H, bs); 7.27 (1H, s); 7.77 (1H, s); 8.47 (1H, d); 8.97 (1H, d).
Table 7 compound N is o.52: use 2-amino-3-methoxyl group-2-methyl-propionitrile, 1H NMR (CDCl 3) δ ppm: non-enantiomer mixture (1/1); 1.82 and 1.84 (3H, 2xs); 2.20 and 2.22 (3H, 2xs);
3.53 and 3.54 (3H, 2xs); 3.64-3.84 (2H, 2xdd); 5.73 and 5.75 (1H, 2xs); 7.27-7.36 (3H, m); 7.77 (1H, d); 8.49 (1H, d); 8.98 (1H, s).
Table 7 compound N is o.244: use 1,1-dimethyl-Ding-2-alkynylamine, m.p.142-145 ℃; 1H NMR (CDCl 3) δ ppm:1.70 (6H, s); 1.83 (3H, s); 2.20 (3H, s); 5.64 (1H, s); 6.87 (1H, bs); 7.27 (1H, d); 7.76 (1H, d); 8.47 (1H, d); 8.96 (1H, d).
Table 7 compound N is o.251: use 4-methoxyl group-1,1-dimethyl-Ding-2-alkynylamine, m.p.110-112 ℃; 1H NMR (CDCl 3) δ ppm:1.74 (6H, s); 2.20 (3H, s); 3.38 (3H, s); 4.13 (2H, s); 5.65 (1H, s); 6.89 (1H, bs); 7.27 (1H, d); 7.78 (1H, d); 8.47 (1H, d); 8.97 (1H, d).
Embodiment 5
This embodiment illustrates the preparation of the N-tert-butyl group-2-(7-fluoro-3-thiene-3-yl--quinoline-6-oxygen base)-2-methyl mercapto-acetamide (table 30 compound N o.12).
Stage 1:With in stirring from the embodiment 2-in 3 stages 4 (3-bromo-7-fluoro-quinoline-6-base oxygen base)-N-tert-butyl group-2-methyl mercapto-acetamide (160mg), chlorination two (triphenylphosphine) close palladium (II) (1.4mg), 3 thienylboronic acid (56mg) and sodium bicarbonate (101mg)) at dioxane/water (1:1 mixture, 4.8ml) in mixture be heated to 70 ℃, continue 14h.During cooling, reactant mixture is handled with saturated sodium bicarbonate aqueous solution (5ml).Use ethyl acetate extraction, organic facies is dry on magnesium sulfate, filters, and reduction vaporization provides thick product, by chromatography (silica gel; The hexane/ethyl acetate 2:1 of 2:1 volume) chromatography provides required product, be white solid (m.p.170-173 ℃, M+405). 1H?NMR(CDCl 3)δ?ppm：1.46(9H，s)；2.20(3H，s)；5.64(1H，s)；6.66(1H，bs)；7.42(1H，d)；7.51(2H，m)；7.66(1H，m)，7.80(1H，d)，8.22(1H，d)；9.13(1H，d)。
Use similar approach to prepare following acid amides.M.p.132-134 ℃ of 2-(7-fluoro-3-thiene-3-yl--quinoline-6-base oxygen base)-N-(4-methoxyl group-1,1-dimethyl-Ding-2-alkynyl)-2-methyl mercapto-acetamide (table 30 compound N o.251); 1H NMR (CDCl 3) δ ppm:1.75 (6H, s); 2.22 (3H, s); 3.39 (3H, s); 4.13 (2H, s); 5.68 (1H, s); 6.93 (1H, bs); 7.42 (1H, d); 7.51 (2H, m); 7.66 (1H, m), 7.82 (1H, d), 8.22 (1H, d); 9.13 (1H, d).Preparation is certainly from the preamble embodiment 2-in 3 stages 4 (3-bromo-7-fluoro-quinoline-6-base oxygen base)-N-(4-methoxyl group-1,1-dimethyl-Ding-2-alkynyl)-2-methyl mercapto-acetamide.
Embodiment 6
This embodiment is the fungicidal property of Ming Dynasty style (I) compound for example.
Use method described below test compounds in blade wafer is measured.Test compounds is dissolved in DMSO and is diluted to 200ppm in water.Under the situation of ultimate corruption mould (Pythium ultimum) test, test compounds is dissolved in DMSO and is diluted to 20ppm in water.
Wheat standing grain powdery mildew (Erysiphe graminis f.sp.tri tici) (wheat powdery mildew): the wheat leaf blade nodal plate is placed on the agar of 24-orifice plate, with the solution spray of test compounds.After placement parches,, continue 12 to 24 hours with the spore suspension inoculation of blade wafer with above-mentioned fungi.Through suitable incubation, in inoculation activity according to preventative Fungicidally active assessing compound after four days.
Puccinia recondita f. sp. tritici (puccinia recondite f.sp.tritici) (brown rust of wheat): the wheat leaf blade nodal plate is placed on the agar of 24-orifice plate, with the solution spray of test compounds.After placement parches,, continue 12 to 24 hours with the spore suspension inoculation of blade wafer with above-mentioned fungi.Through suitable incubation, behind the inoculation Ninth Heaven according to the activity of preventative Fungicidally active assessing compound.
Grain husk withered septoria musiva (Septoria nodorum) (wheat glume blight): the wheat leaf blade nodal plate is placed on the agar of 24-orifice plate, with the solution spray of test compounds.After placement parches,, continue 12 to 24 hours with the spore suspension inoculation of blade wafer with above-mentioned fungi.Through suitable incubation, in inoculation activity according to preventative Fungicidally active assessing compound after four days.
Circle nuclear cavity bacteria (Pyrenophora teres) (net blotch of barley): the barley leaves nodal plate is placed on the agar of 24-orifice plate, with the solution spray of test compounds.After placement parches,, continue 12 to 24 hours with the spore suspension inoculation of blade wafer with above-mentioned fungi.Through suitable incubation, in inoculation activity according to preventative Fungicidally active assessing compound after four days.
Rice blast pears spore mould (Pyricularia oryzae) (rice blast): rice blade nodal plate is placed on the agar of 24-orifice plate, with the solution spray of test compounds.After placement parches,, continue 12 to 24 hours with the spore suspension inoculation of blade wafer with above-mentioned fungi.Through suitable incubation, in inoculation activity according to preventative Fungicidally active assessing compound after four days.
Botrytis cinerea (Botrytis cinerea) (gray mold): Kidney bean blade nodal plate is placed on the agar of 24-orifice plate, with the solution spray of test compounds.After placement parches,, continue 12 to 24 hours with the spore suspension inoculation of blade wafer with above-mentioned fungi.Through suitable incubation, in inoculation activity according to preventative Fungicidally active assessing compound after four days.
Phytophthora infestans (Phytophthora infestans) (potato late blight on the tomato): the tomato leaf nodal plate is placed on the agar of 24-orifice plate, with the solution spray of test compounds.After placement parches,, continue 12 to 24 hours with the spore suspension inoculation of blade wafer with above-mentioned fungi.Through suitable incubation, in inoculation activity according to preventative Fungicidally active assessing compound after four days.
Grape is given birth to single shaft mould (plasmopara viticola) (grape vine downy mildew): grape vine blade nodal plate is placed on the agar of 24-orifice plate, with the solution spray of test compounds.After placement parches,, continue 12 to 24 hours with the spore suspension inoculation of blade wafer with above-mentioned fungi.Through suitable incubation, in inoculation activity according to preventative Fungicidally active assessing compound after seven days.
Wheat septoria (Septoria tritici) (leaf blight): will directly sneak into (PDB potato glucose meat soup) in the nutrient broth from this fungus conidium of cryogenic memory.After (DMSO) solution of test compounds put into titer plate (96-hole gauge lattice), add the nutrient broth that comprises fungal spore.At 24 ℃ of incubation test boards, use the spectrphotometric method for measuring growth inhibition after 72 hours.
Yellow sickle spore bacterium (Fusarium culmorum) (root rot): will directly sneak into (PDB potato glucose meat soup) in the nutrient broth from this fungus conidium of cryogenic memory.After (DMSO) solution of test compounds put into titer plate (96-hole gauge lattice), add the nutrient broth that comprises fungal spore.At 24 ℃ of incubation test boards, use the spectrphotometric method for measuring growth inhibition after 48 hours.
Ultimate corruption mould (Pythium ultimum) (damping off): will prepare from the mycelial fragment of the above-mentioned fungi of fresh liquid culture and sneak in the potato glucose meat soup.The dimethyl sulfoxide solution of test compounds is diluted with water to 20ppm, inserts subsequently in the titer plate of 96-hole, add the nutrient broth that contains fungal spore.At 24 ℃ of incubation test boards, use the spectrphotometric method for measuring growth inhibition after 48 hours.
Following compound (front is a compound number, in its unquote be table numbering) provides at least 60% control to following fungal infection under 200ppm:
Grape is given birth to single shaft mould (plasmopara viticoia), compound 9 (6), 12 (7), 38 (6), 52 (6), 52 (7), 60 (6), 95 (6), 221 (6), 221 (13), 235 (6), 238 (7), 238 (10), 244 (6), 244 (7), 251 (2), 251 (7), 251 (10), 251 (13), 251 (30), 256 (6), 264 (6), 277 (6), 278 (6), phytophthora infestans (Phytophthora infestans), compound 12 (6), 12 (10), 52 (7), 52 (13), 221 (6), 221 (13), 238 (7), 238 (10), 238 (13), 244 (6), 244 (7), 251 (7), 251 (10), 256 (6), 275 (7), 277 (6), 278 (6), standing grain powdery mildew (Erysiphe graminisf.sp.tritici), compound 9 (6), 12 (6), 12 (13), 28 (6), 38 (6), 52 (6), 52 (7), 52 (13), 68 (6), 86 (6), 181 (6), 189 (6), 221 (6), 221 (13), 235 (6), 238 (6), 238 (7), 238 (10), 238 (13), 244 (6), 251 (6), 251 (7), 251 (13), 251 (30), 256 (6), 264 (6), 268 (6), 275 (6), 275 (7), 277 (6), 278 (6), 281 (6), 284 (6), rice blast pears spore mould (Pyriculariaoryzae), compound 9 (6), 52 (6), 52 (7), 68 (6), 221 (6), 238 (6), 244 (7), 251 (6), 251 (7), 275 (7), 277 (6), 278 (6), Puccinia recondita (Puccinia recondita f.sp.tritici), compound 52 (6), 52 (7), 68 (6), 221 (6), 238 (7), 251 (2), 264 (6), grain husk withered septoria musiva (Septorianodorum), compound 9 (6), 12 (2), 12 (7), 12 (10), 12 (13), 12 (30), 52 (6), 52 (7), 68 (6), 221 (6), 235 (6), 238 (6), 238 (7), 244 (6), 244 (7), 244 (13), 251 (6), 251 (7), 251 (13), 256 (6), 264 (6), 277 (6), 278 (6), 281 (6), wheat septoria (Septoria tritici), compound 9 (6), 12 (6), 12 (7), 12 (13), 16 (13), 38 (6), 52 (2), 52 (6), 52 (7), 52 (13), 68 (6), 95 (6), 122 (6), 221 (6), 221 (13), 224 (6), 235 (6), 238 (6), 238 (7), 238 (13), 244 (2), 244 (6), 244 (7), 251 (6), 251 (7), 251 (13), 251 (2), 251 (30), 256 (6), 264 (6), 268 (6), 275 (7), 277 (6), 278 (6), 281 (6), 284 (6), 287 (6), 291 (6), yellow sickle spore bacterium (Fusarium culmorum), compound 9 (6), 12 (6), 12 (7), 221 (6), 238 (6), 238 (7), 244 (6), 244 (7), 251 (6), 251 (7), 251 (13), 284 (6)
(front is a compound number to following compound, be table numbering in its unquote) under 20ppm, following fungal infection provided at least 60% control: ultimate corruption mould (Pythiumultimum), compound 9 (6), 12 (10), 52 (6), 52 (13), 221 (6), 221 (13), 235 (6), 238 (6), 244 (6), 251 (6), 251 (10), 251 (13), 251 (30), 264 (6), 275 (7), 278 (6), 281 (6).

Claims (51)

1. compound of Formula I
Figure A200780036889C00021
Wherein
Q 1, Q 2And Q 3Be the C of halogen, cyano group, nitro, azido, optional replacement independently of one another 1-6The C of alkyl, optional replacement 3-6The comprising at least one and be selected from sulphur, oxygen or R wherein of cycloalkyl, optional replacement 0Be the C of hydrogen or optional replacement 1-6The NR of alkyl 0Heteroatomic C 3-6The C of-heterocyclic radical, optional replacement 3-6Cycloalkyl (C 1-4) C of alkyl, optional replacement 2-6The C of thiazolinyl, optional replacement 2-6The C of alkynyl, optional replacement 1-6The C of alkoxyl, optional replacement 2-6The C of alkene oxygen base, optional replacement 2-6Aryl (the C of the aryl of alkynyloxy group, optional replacement, the aryloxy group of optional replacement, optional replacement 1-6) aryl (C of alkyl, optional replacement 1-6) heteroaryl (C of alkoxyl, the heteroaryl of optional replacement, the heteroaryloxy of optional replacement, optional replacement 1-6) heteroaryl (C of alkyl, optional replacement 1-6) alkoxyl ,-SF 5Or-S (O) u(C 1-6) alkyl, wherein u is 0,1 or 2 and described alkyl group is optional is replaced by halogen, perhaps
Q 1, Q 2And Q 3Independently be separately-OSO 2(C 1-4) alkyl, wherein said alkyl group is replaced by halogen alternatively, perhaps
Q 1, Q 2And Q 3Be independently of one another-CONR uR v,-COR u,-CO 2R u,-CR u=NR v,-NR uR v,-NR uCOR v,-NR uCO 2R v,-SO 2NR uR vOr-NR uSO 2R w, R wherein wBe the C of optional replacement 1-6Alkyl and R uAnd R vBe hydrogen or the optional C that is replaced by halogen independently of one another 1-6Alkyl is perhaps at-CONR uR vOr-SO 2NR uR vSituation under, R uR vCan be selected from sulphur, oxygen or R wherein in conjunction with forming 5-or 6-unit's carbocyclic ring or heterocycle, comprising 0Be the C of hydrogen or optional replacement 1-6The NR of alkyl 0Hetero atom, perhaps at-CR u=NR vSituation under, R vBe the C of hydroxyl or optional replacement 1-6The aryloxy group of alkoxyl, optional replacement or the heteroaryloxy of optional replacement, perhaps Q 1And Q 2Also represent hydrogen independently of one another,
R 1Be the C of optional replacement 1-4The C of alkyl, optional replacement 2-4The C of thiazolinyl, optional replacement 2-4The C of alkynyl or optional replacement 3-4Cycloalkyl,
R 2Be hydrogen, C 1-8Alkyl, C 3-4Cycloalkyl, C 2-8Thiazolinyl, cyano group, hydroxyl, alkoxyl, cyano group (C 1-4) alkyl, C 1-4Alkoxyl (C 1-4) alkyl, C 1-4Alkoxyl (C 1-4) alkoxyl (C 1-4) alkyl or benzyloxy (C 1-4) alkyl, wherein said benzyl ring is alternatively by C 1-4Alkoxyl replaces,
R 3Be-(CR aR b) p(CR cR d) q(X) r(CR eR f) sR 4, wherein
R a, R b, R c, R d, R eAnd R fBe hydrogen, C independently of one another 1-4Alkyl, halogen,
Cyano group, hydroxyl, C 1-4Alkoxyl or C 1-4Alkoxy carbonyl group, perhaps
R aR b, R cR dOr R eR fCan be in conjunction with forming 3 to 8 yuan of carbocyclic rings or heterocycles, it comprises and is selected from sulphur, oxygen or NR oHetero atom, R wherein oBe the C of hydrogen or optional replacement 1-6Alkyl,
X is (CO), (CO) O, O (CO), O, S (O) t, wherein t is 0,1 or 2, perhaps X is NH or N (C 1-6) alkyl, p, r and s are 0 or 1 independently of one another,
Q is 0,1 or 2,
R 4Be the C of optional replacement 1-6The C of alkyl, optional replacement 2-6Thiazolinyl ,-CR Uu=NR Vv, R wherein UuBe hydrogen or C 1-6Alkyl and R VvBe the C of hydroxyl or optional replacement 1-6The aryloxy group of alkoxyl, optional replacement or the heteroaryloxy of optional replacement or-CH 2-C ≡ C-R 5, wherein
R 5Be the C that the following group of hydrogen, optional quilt replaces 1-8Alkyl: halogen, hydroxyl, C 1-6Alkoxyl, C 1-3Alkoxyl (C 1-3) alkoxyl, cyano group, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkyl amino carbonyl oxy, three (C 1-4) alkyl siloxy or wherein g be 0,1 or 2-S (O) g(C 1-6) alkyl, perhaps R 5Be the C that the following group of optional quilt replaces 3-6Cycloalkyl: halogen, hydroxyl, C 1-6Alkoxyl, C 1-3Alkoxyl (C 1-3) alkoxyl, cyano group, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkyl amino carbonyl oxy, three (C 1-4) alkyl siloxy or wherein g be 0,1 or 2-S (O) g(C 1-6) alkyl, perhaps
R 5Be C 3-6Cycloalkyl (C 1-4) alkyl, wherein said alkyl and/or cycloalkyl moiety are replaced by following group alternatively: halogen, hydroxyl, C 1-6Alkoxyl, C 1-3Alkoxyl (C 1-3) alkoxyl, cyano group, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkyl amino carbonyl oxy, three (C 1-4) alkyl siloxy or-S (O) g(C 1-6) alkyl, wherein g is 0,1 or 2, perhaps
R 5Be the aryl (C of the aryl of optional replacement, optional replacement 1-4) aryloxy group (C of alkyl, optional replacement 1-4) alkyl, the heteroaryl of optional replacement or the heteroaryl (C of optional replacement 1-4) heteroaryloxy (C of alkyl or optional replacement 1-4) alkyl, perhaps
R 4Be the C of optional replacement 3-6The C of cycloalkyl, optional replacement 5-6The 5-of the aryl of cycloalkenyl group, optional replacement, the heteroaryl of optional replacement or optional replacement is to 8-unit ring, and it comprises alternatively and is selected from sulphur, oxygen or NR 0Hetero atom, R wherein oBe the C of hydrogen or optional replacement 1-6Alkyl, perhaps
Work as R 3Be-(CR aR b) p(CR cR d) q(X) r(CR eR f) sR 4The time, R 2And R 3Can be in conjunction with forming 5-or 6-unit ring, it is alternatively by halogen, C 1-4Alkyl, one-or two-(C 1-4) alkyl amino-carbonyl replaces, and comprise alternatively and be selected from sulphur, oxygen and NR 00Hetero atom, R wherein 00Be alternatively by halogen, C 1-6The C that alkoxyl or cyano group replace 1-4Alkyl, perhaps R 00Be alternatively by nitro, C 1-4Alkyl, halo (C 1-4) alkyl, C 1-4The phenyl that alkyl-carbonyl or heteroaryl replace, perhaps R 2And R 3Can be in conjunction with 6 of the optional replacement of formation, 6-unit dicyclo,
R 3Be-(CR 30R 40) C ≡ CR 50, wherein
R 30And R 40Be hydrogen, C independently of one another 1-6Alkyl, halo (C 1-4) alkyl, C 1-4Alkoxyl (C 1-3) alkyl, C 2-3Thiazolinyl or C 2-3Alkynyl, perhaps
R 30And R 40With the carbon atom that links to each other with them in conjunction with forming 3 to 6 yuan of carbocyclic rings or heterocycles, it comprises and is selected from sulphur, oxygen or NR 000Hetero atom, R wherein 000Be hydrogen or C 1-4Alkyl, wherein said carbocyclic ring or heterocycle are alternatively by halogen or C 1-4Alkyl replaces,
R 50Be the C of hydrogen, optional replacement 1-4The C of alkyl, optional replacement 3-6The aryl of cycloalkyl, optional replacement or the heteroaryl of optional replacement, it comprises and is selected from sulphur, oxygen or NR 000Hetero atom, R wherein 000Be hydrogen or C 1-6Alkyl,
L is sulphur or oxygen, and
N is 0,1 or 2, and
The salt of formula I compound or N-oxide.
2. the compound of claim 1, wherein Q 2Be hydrogen, Q 1And Q 3Definition as claimed in claim 1.
3. the compound of claim 1, wherein Q 1Be halogen, aryl or heteroaryl, Q 2Be hydrogen and Q 3Definition as claimed in claim 1.
4. the compound of claim 1, wherein Q 1Be aryl, Q 2Be hydrogen and Q 3Definition as claimed in claim 1.
5. the compound of claim 1, wherein Q 1Be heteroaryl, Q 2Be hydrogen and Q 3Definition as claimed in claim 1.
6. the compound of claim 1, wherein Q 1And Q 3Be halogen and Q 2Be hydrogen.
7. the compound of claim 1, wherein Q 1Be aryl or heteroaryl, Q 2Be hydrogen and Q 3It is halogen.
8. the compound of claim 1, wherein Q 1And Q 2Be hydrogen and Q 3It is the alkyl of halogen or optional replacement.
9. the compound of claim 1, wherein Q 1Be halogen, Q 2Be hydrogen and Q 3It is the alkyl of optional replacement.
10. the compound of claim 1, wherein Q 1And Q 2Be halogen and Q 3It is the alkyl of optional replacement.
11. the compound of claim 1, wherein Q 1It is bromine.
12. the compound of claim 1, wherein Q 1Be iodine.
13. the compound of claim 1, wherein Q 1Be chlorine.
14. the compound of claim 1, wherein Q 1It is fluorine.
15. the compound of claim 1, wherein Q 3It is halogen.
16. the compound of claim 1, wherein Q 3It is fluorine.
17. the compound of claim 1, wherein Q 1Be bromine, Q 2Be hydrogen and Q 3It is fluorine.
18. the compound of claim 1, wherein Q 1Be bromine, Q 2Be hydrogen and Q 3Be chlorine.
19. the compound of claim 1, wherein Q 1Be iodine, Q 2Be hydrogen and Q 3It is fluorine.
20. the compound of claim 1, wherein Q 1Be iodine, Q 2Be hydrogen and Q 3Be chlorine.
21. the compound of claim 1, wherein Q 1Be hydrogen, halogen, aryl or heteroaryl.
22. the compound of claim 1, wherein R 1Be C 1-4Alkyl or halo (C 1-4) alkyl.
23. the compound of claim 1, wherein R 1It is methyl.
24. the compound of claim 1, wherein R 1It is ethyl.
25. the compound of claim 1, wherein R 2Be hydrogen or methyl.
26. the compound of claim 1, wherein R 2Be hydrogen.
27. the compound of claim 1, wherein Q 1, Q 2And Q 3It is halogen.
28. the compound of claim 1, wherein Q 1Be halogen, Q 2Be C 1-4Alkyl and Q 3It is halogen.
29. the compound of claim 28, wherein Q 1Be halogen, Q 2Be C 1-4Alkyl and Q 3Be chlorine.
30. the compound of claim 28, wherein Q 1Be halogen, Q 2Be C 1-4Alkyl and Q 3It is fluorine.
31. the compound of claim 1, wherein Q 1Be halogen, Q 2Be methyl and Q 3It is halogen.
32. the compound of claim 31, wherein Q 1Be halogen, Q 2Be methyl and Q 3Be chlorine.
33. the compound of claim 31, wherein Q 1Be halogen, Q 2Be methyl and Q 3It is fluorine.
34. the compound of claim 31, wherein Q 1Be bromine, Q 2Be methyl and Q 3Be chlorine.
35. the compound of claim 31, wherein Q 1Be bromine, Q 2Be methyl and Q 3It is fluorine.
36. the compound of claim 31, wherein Q 1Be iodine, Q 2Be methyl and Q 3Be chlorine.
37. the compound of claim 31, wherein Q 1Be iodine, Q 2Be methyl and Q 3It is fluorine.
38. the compound of claim 1, wherein Q 1Be halogen and Q 2And Q 3Be C 1-4Alkyl.
39. the compound of claim 1, wherein R 3It is the tert-butyl group; 1-halo-2-methyl-prop-2-base; 1; 1-dihalo-2-methyl-prop-2-base; 1; 1; 1-three halos-2-methyl-prop-2-base; 1-alkoxyl-2-methyl-prop-2-base; 1-alkene oxygen base-2-methyl-prop-2-base; 1-alkynyloxy group-2-methyl-prop-2-base; 1-cyano group-2-methyl-third-2-base; 1-alkoxyl alkoxyl-2-methyl-third-2-base; 1-halo-3-methyl fourth-3-base; 1; 1-dihalo-3-methyl fourth-3-base; 1; 1; 1-three halos-3-methyl fourth-3-base; 1-alkoxyl-3-methyl fourth-3-base; 1-alkene oxygen base-3-methyl fourth-3-base; 1-alkynyloxy group-3-methyl fourth-3-base; 1-cyano group-3-methyl fourth-3-base; 2-cyano group third-2-base; 2-methoxycarbonyl group third-2-base or 2-methylamino carbonyl third-2-base; 1-alkylthio group-2-methyl-prop-2-base; 1-alkyl sulphinyl-2-methyl-prop-2-base; 1-alkyl sulphonyl-2-methyl-prop-2-base; 2-cyano group-1-alkoxypropan-2-base; 2-methyl isophthalic acid-[(E and/or Z)-oxyimino]-third-2-base; 2-methyl isophthalic acid-[(E and/or Z)-Alkoximino]-third-2-base; 2-methyl isophthalic acid-[(E and/or Z)-aryloxy group imino group]-third-2-base; 2-methyl isophthalic acid-[(E and/or Z)-heteroaryloxy imino group]-third-2-base; 1-alkoxyl-third-2-base; 1-halo-third-2-base; 3-methyl-Ding-1-alkynes-3-base; 1-alkyl-3-methyl-Ding-1-alkynes-3-base; 4-methyl-penta-2-alkynes-4-base; 1-hydroxy-4-methyl-penta-2-alkynes-4-base; 1-alkoxyl-4-methyl-penta-2-alkynes-4-base; 1-alkoxyl alkoxyl-4-methyl-penta-2-alkynes-4-base; 1-alkoxy alkoxy alkyl-4-methyl-penta-2-alkynes-4-base, 1-cyano group alkyl-3-methyl fourth-3-base; 1-haloalkyl-3-methyl fourth-3-base.
40. the compound of claim 39, wherein R 3It is the tert-butyl group, 1-halo-2-methyl-prop-2-base, 1-fluoro-2-methyl-prop-2-base, 1-methoxyl group-2-methyl-prop-2-base, 1-ethyoxyl-2-methyl-prop-2-base, 1-allyloxy-2-methyl-prop-2-base, 1-(third-2-alkynyloxy group)-2-methyl-prop-2-base, 2-cyano group-1-ethyoxyl-third-2-base, 2-cyano group-1-methoxy propyl-2-base, 1-halo-3-methyl fourth-3-base, 1-fluoro-3-methyl fourth-3-base, 3-methyl fourth-1-alkynes-3-base, 4-methylpent-2-alkynes-4-base, the 5-methyl-oneself-3-alkynes-5-base, 1-methoxyl group-4-methyl-penta-2-alkynes-4-base, 1-allyloxy-4-methyl-penta-2-alkynes-4-base, 1-propargyloxy-4-methyl-penta-2-alkynes-4-base, 1-ethyoxyl-4-methyl-penta-2-alkynes-4-base.
41. the compound of claim 1, wherein R 4Be alternatively by C 1-4Alkoxyl-(C 1-4) alkoxyl (C 1-4) C that replaces of alkyl 1-6Alkyl, wherein said alkyl group are alternatively by halogen ,-or two-(C 1-6) alkyl amino or three (C 1-4) replacement of alkyl silicyl, perhaps R 4Be alternatively by benzyloxy (C 1-4) C that replaces of alkyl 1-6Alkyl, wherein said alkyl group are alternatively by halogen ,-or two-(C 1-6) alkyl amino or three (C 1-4) replacement of alkyl silicyl, perhaps R 4Be alternatively by C 2-6Alkene oxygen base or-S (O) x(C 1-6) C that replaces of alkyl 1-6Alkyl, wherein x be 0,1 or 2 and described alkyl group alternatively by halogen ,-or two-(C 1-6) alkyl amino ,-NH (C 1-4) alkyl=NOR replacement, wherein R is hydrogen or C 1-4Alkyl, or wherein said alkyl group is alternatively by three (C 1-4) replacement of alkyl silicyl, perhaps R 4Be-CR Uu=NR Vv, R wherein UuBe hydrogen or C 1-6Alkyl and R VvBe the C of hydroxyl or optional replacement 1-6Alkoxyl.
42. the compound of claim 1, wherein R 5The ring of the aryl of the optional replacement in the definition and the heteroaryl of optional replacement or part are replaced by following group alternatively: halogen, cyano group, nitro, azido, C 1-6Alkyl, halo (C 1-6) alkyl, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4) alkyl, C 2-6Thiazolinyl, halo (C 2-6) thiazolinyl, C 2-6Alkynyl, halo (C 2-6) alkynyl, C 1-6Alkoxyl, halo (C 1-6) alkoxyl, C 3-6Alkene oxygen base, halo (C 2-6) alkene oxygen base, C 2-6Alkynyloxy group, halo (C 2-6) alkynyloxy group, aryl, aryloxy group, aryl (C 1-6) alkyl, aryl (C 1-6) alkoxyl, heteroaryl, heteroaryloxy, heteroaryl (C 1-6) alkyl, heteroaryl (C 1-6) alkoxyl ,-SF 5,-S (O) g(C 1-4) alkyl, wherein g be 0,1 or 2 and described alkyl replaced perhaps R alternatively by halogen 5Alternatively by-OSO 2(C 1-4) the alkyl replacement, wherein said alkyl group is replaced by halogen alternatively, perhaps R 5Alternatively by-CONR gR h,-COR g,-CO 2R g,-R g=NR h,-NR gR h,-NR gCOR h,-NR gCO 2R h,-SO 2NR gR hOr-NR gSO 2R 1Replace, wherein R iBe the C that is replaced by halogen alternatively 1-6Alkyl and R gAnd R hBe hydrogen or the C that replaced by halogen alternatively independently of one another 1-6Alkyl is perhaps at-CONR gR hOr-SO 2NR gR hSituation under, R gR hCan be in conjunction with forming 5-or 6-unit's carbocyclic ring or heterocycle, it comprises and is selected from sulphur, oxygen or NR 0Hetero atom, R wherein 0Be the C of hydrogen or optional replacement 1-6Alkyl.
43. the compound of claim 1, wherein the 5-of the heteroaryl of the aryl of optional replacement and optional replacement or optional replacement is to the ring R of 8-unit 4Replaced by following group alternatively: halogen, cyano group, nitro, azido, C 1-6Alkyl, halo (C 1-6) alkyl, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4) alkyl, C 2-6Thiazolinyl, halo (C 2-6) thiazolinyl, C 2-6Alkynyl, halo (C 2-6) alkynyl, C 1-6Alkoxyl, halo (C 1-6) alkoxyl, C 2-6Alkene oxygen base, halo (C 2-6) alkene oxygen base, C 2-6Alkynyloxy group, halo (C 2-6) alkynyloxy group ,-SF 5,-S (O) x(C 1-6) alkyl, wherein x be 0,1 or 2 and described alkyl group replaced perhaps R alternatively by halogen 4Alternatively by-OSO 2(C 1-4) alkyl, wherein said alkyl alternatively by halogen replace ,-CONR xR y,-CON (OR x) R y,-COR x,-CO 2R x,-CR x=NR y,-NR xR y,-NR xCOR y,-NR xCO 2R y,-SO 2NR xR yOr-NR xSO 2R zReplace, wherein R zBy the C of the optional replacement of halogen 1-8Alkyl and R xAnd R yBe hydrogen or independently of one another by the C of the optional replacement of halogen 1-6Alkyl.
44. the compound of claim 1, wherein R 50By the C of the optional replacement of following radicals 1-4Alkyl: halogen, hydroxyl, C 1-6Alkoxyl, C 2-6Thiazolinyl, C 2-6Alkynyl, C 1-4Alkoxyl (C 1-4) alkoxyl, cyano group, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkyl amino-carbonyl oxygen base, wherein p is 0,1 or 2 S (O) p(C 1-6)-alkyl, triazolyl, pyrazolyl, imidazole radicals, three (C 1-4The benzyloxy of the phenoxy group of)-alkyl siloxy, optional replacement, the thiophene oxy of optional replacement, optional replacement or the thiophene methoxy of optional replacement.
45. the compound of claim 1, wherein R 50By the C of the optional replacement of following radicals 3-6Cycloalkyl: halogen, hydroxyl, C 1-6Alkoxyl, C 1-4Alkoxyl (C 1-4) alkoxyl, cyano group, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkyl amino-carbonyl oxygen base, wherein p is 0,1 or 2 S (O) p(C 1-6)-alkyl, triazolyl, pyrazolyl, imidazole radicals, three (C 1-4The benzyloxy of the phenoxy group of)-alkyl siloxy, optional replacement, the thiophene oxy of optional replacement, optional replacement or the thiophene methoxy of optional replacement.
46. the compound of claim 1, wherein the heteroaryl R of the aryl of optional replacement or optional replacement 50By the optional replacement of following radicals: halogen, hydroxyl, sulfydryl, C 1-4Alkyl, C 2-4Thiazolinyl, C 2-4Alkynyl, C 1-4Alkoxyl, C 2-4Alkene oxygen base, C 2-4Alkynyloxy group, halo (C 1-4) alkyl, halo (C 1-4) alkoxyl, C 1-4Alkylthio group, halo (C 1-4)-alkylthio group, hydroxyl (C 1-4) alkyl, C 1-4Alkoxyl (C 1-4) alkyl, C 3-6Cycloalkyl, C 3-6Cycloalkyl-(C 1-4) alkyl, phenoxy group, benzyloxy, benzoyloxy, cyano group, isocyano group, thiocyanogen, isothiocyano, nitro, NR pR q, NHCOR p,-NHCONR pR q, CONR pR q,-SO 2R o, OSO 2R o, COR p, CR q=NR qOr N=CR pR q, R wherein oBe C 1-4Alkyl, halo (C 1-4) alkyl, C 1-4Alkoxyl, halo (C 1-4) alkoxyl, C 1-4Alkylthio group, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4) alkyl, phenyl or benzyl, described phenyl and benzyl group are alternatively by halogen, C 1-4Alkyl or C 1-4Alkoxyl replaces, and R pAnd R qBe hydrogen, C independently 1-4Alkyl, halo (C 1-4) alkyl, C 1-4Alkoxyl, halo (C 1-4) alkoxyl, C 1-4Alkylthio group, C 3-6Cycloalkyl, C 3-6Cycloalkyl (C 1-4) alkyl, phenyl or benzyl, described phenyl and benzyl group are alternatively by halogen, C 1-4Alkyl or C 1-4Alkoxyl replaces.
47. the compound of claim 1, wherein L is an oxygen.
48. the compound of claim 1, wherein n is 0.
49. describe the method for the formula I compound of preparation claim 1 by this paper.
50. a Fungicidal composition, its comprise the antifungal effective dose claim 1 compound and to its suitable carrier or thinner.
51. antagonism or control cause the method for plant characteristic of disease fungi, it comprises the compound administration of the claim 1 of antifungal effective dose location or soil or any other plant growing media to seed, plant or the seed of plant, plant.
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