CN101522030B - Fungicides - Google Patents

Fungicides Download PDF

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Publication number
CN101522030B
CN101522030B CN2007800368897A CN200780036889A CN101522030B CN 101522030 B CN101522030 B CN 101522030B CN 2007800368897 A CN2007800368897 A CN 2007800368897A CN 200780036889 A CN200780036889 A CN 200780036889A CN 101522030 B CN101522030 B CN 101522030B
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compound
alkyl
optional substituted
hydrogen
methyl
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CN101522030A (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)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (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

Mycocide
The present invention relates to novel quinoline oxygen phenylalkanoic acid acid amides, prepare their method, relate to the compsn 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 verivate is disclosed in for example WO 04/047538 and JP 2001-89453 with them as the agricultural and the purposes of gardening bactericide.
The present invention relates to the substd quinolines that provides specific-6-base oxygen phenylalkanoic acid acid amides, mainly as plant fungicide.
The compound of general formula I is provided according to the present invention thus,
Figure G2007800368897D00011
Wherein
Q 1, Q 2And Q 3Be halogen, cyanic acid, nitro, azido-, optional substituted C independently of one another 1-6Alkyl, optional substituted C 3-6Naphthenic base, optionally substitutedly comprise at least one and be selected from sulphur, oxygen or R wherein 0Be hydrogen or optional substituted C 1-6The NR of alkyl 0Heteroatomic C 3-6-heterocyclic radical, optional substituted C 3-6Naphthenic base (C 1-4) alkyl, optional substituted C 2-6Thiazolinyl, optional substituted C 2-6Alkynyl, optional substituted C 1-6Alkoxyl group, optional substituted C 2-6Alkene oxygen base, optional substituted C 2-6Alkynyloxy group, optional substituted aryl, optional substituted aryloxy, optional substituted aryl (C 1-6) alkyl, optional substituted aryl (C 1-6) alkoxyl group, optional substituted heteroaryl, optional substituted heteroaryloxy, optional substituted heteroaryl (C 1-6) alkyl, optional substituted heteroaryl (C 1-6) alkoxyl group ,-SF 5Or-S (O) u(C 1-6) alkyl, wherein u is 0,1 or 2 and said 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-CON uR vR ,-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 optional substituted C 1-6Alkyl and R uAnd R vBe hydrogen or optional independently of one another by the substituted C of halogen 1-6Alkyl is perhaps at-CONR uR vOr-SO 2NR uR vSituation under, R uR vCan combine to form 5-or 6-unit carbocyclic ring or heterocycle, comprise and be selected from sulphur, oxygen or NR 0Heteroatoms, R wherein 0Be hydrogen or optional substituted C 1-6Alkyl is perhaps at-CR u=NR vSituation under, R vBe hydroxyl or optional substituted C 1-6Alkoxyl group, optional substituted aryloxy or optional substituted heteroaryloxy, perhaps
Q 1And Q 2Also represent hydrogen independently of one another,
R 1Be optional substituted C 1-4Alkyl, optional substituted C 2-4Thiazolinyl, optional substituted C 2-4Alkynyl or optional substituted C 3-4Naphthenic base,
R 2Be hydrogen, C 1-8Alkyl, C 3-4Naphthenic base, C 2-8Thiazolinyl, cyanic acid, hydroxyl, alkoxyl group, cyanic acid (C 1-4) alkyl, C 1-4Alkoxyl group (C 1-4) alkyl, C 1-4Alkoxyl group (C 1-4) alkoxyl group (C 1-4) alkyl or benzyloxy (C 1-4) alkyl, wherein said benzyl ring is alternatively by C 1-4Alkoxyl group 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, cyanic acid, hydroxyl, C 1-4Alkoxyl group or C 1-4Carbalkoxy, perhaps
R aR b, R cR dOr R eR fCan combine to form 3 to 8 yuan of carbocyclic rings or heterocycles, it comprises and is selected from sulphur, oxygen or NR oHeteroatoms, R wherein oBe hydrogen or optional substituted C 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 optional substituted C 1-6Alkyl, optional substituted C 2-6Thiazolinyl ,-CR Uu=NR Vv, R wherein UuBe hydrogen or C 1-6Alkyl and R VvBe hydroxyl or optional substituted C 1-6Alkoxyl group, optional substituted aryloxy or optional substituted heteroaryloxy perhaps-CH 2-C ≡ C-R 5, wherein
R 5Be hydrogen, the substituted C of the following group of optional quilt 1-8Alkyl: halogen, hydroxyl, C 1-6Alkoxyl group, C 1-3Alkoxyl group (C 1-3) alkoxyl group, cyanic acid, 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 substituted C of the following group of optional quilt 3-6Naphthenic base: halogen, hydroxyl, C 1-6Alkoxyl group, C 1-3Alkoxyl group (C 1-3) alkoxyl group, cyanic acid, 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 3-6Naphthenic base (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 group, C 1-3Alkoxyl group (C 1-3) alkoxyl group, cyanic acid, 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 optional substituted aryl, optional substituted aryl (C 1-4) alkyl, optional substituted aryloxy (C 1-4) alkyl, optional substituted heteroaryl or optional substituted heteroaryl (C 1-4) alkyl or optional substituted heteroaryloxy (C 1-4) alkyl, perhaps
R 4Be optional substituted C 3-6Naphthenic base, optional substituted C 5-6Cycloalkenyl group, optional substituted aryl, optional substituted heteroaryl or optional substituted 5-be to 8-unit ring, and it comprises alternatively and is selected from sulphur, oxygen or NR 0Heteroatoms, R wherein oBe hydrogen or optional substituted C 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 combine to form 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 00Heteroatoms, R wherein 00Be alternatively by halogen, C 1-6The substituted C of alkoxyl group or cyanic acid 1-4Alkyl, perhaps R 00Be alternatively by nitro, C 1-4Alkyl, halo (C 1-4) alkyl, C 1-4The substituted phenyl of alkyl-carbonyl or heteroaryl, perhaps R 2And R 3Can combine to form optional substituted 6,6-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 group (C 1-3) alkyl, C 2-3Thiazolinyl or C 2-3Alkynyl, perhaps
R 30And R 40Combine to form 3 to 6 yuan of carbocyclic rings or heterocycles with the carbon atom that links to each other with them, it comprises and is selected from sulphur, oxygen or NR 000Heteroatoms, 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 hydrogen, optional substituted C 1-4Alkyl, optional substituted C 3-6Naphthenic base, optional substituted aryl or optional substituted heteroaryl, it comprises and is selected from sulphur, oxygen or NR 000Heteroatoms, 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 compound.
The compounds of this invention comprises at least one unsymmetrical carbon and can be used as enantiomorph (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 enantiomorph 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 compound of formula I compound is preferably represented the N-oxide compound through quinoline moiety formation.
The salt that formula I compound can form preferably acts on those that form through these compounds and acid.Term " acid " comprises mineral acid such as hydrogen halide, sulfuric acid, phosphoric acid etc., and organic acid, preferred normally used paraffinic acid, for example formic acid, acetate and propionic acid.
Except as otherwise noted, the moieties of alkyl group and alkoxyl group, alkylthio etc. comprises 1 to 6, common 1 to 4 carbon atom with the straight or branched form aptly.Instance is methyl, ethyl, n-propyl and sec.-propyl and normal-butyl, sec.-butyl, isobutyl-and the tertiary butyl.The instance that moieties comprises 5 or 6 carbon atoms is n-pentyl and n-hexyl.Alkyl group comprises halogen, hydroxyl, C with the suitable optional substituents instance of part 1-4Alkoxyl group and C 1-4Alkoxyl group (C 1-4) alkoxyl group, cyanic acid, optional substituted aryl and optional substituted heteroaryl.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.Instance is allyl group, ethynyl and propargyl.Optional substituting group comprises halogen, alkoxyl group, optional substituted aryl and optional substituted heteroaryl.
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.Instance is thienyl, furyl, pyrryl 、 isoxazolyl 、 oxazolyl, thiazolyl 、 oxadiazole base, pyrazolyl, imidazolyl, triazolyl, isothiazolyl, tetrazyl, thiadiazolyl group, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, benzofuryl, benzothienyl, dibenzofuran group, dibenzothiophene base, benzothiazolyl, benzoxazolyl, benzimidazolyl-, indyl, quinolyl, isoquinolyl, quinazolyl and quinoxalinyl, and its N-oxide compound and salt when suitable.Above-mentioned any aryl or heteroaryl definition are optional substituted.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 allyl group), C 2-6Alkynyl (particularly propargyl), C 1-6Alkoxyl group (particularly methoxyl group), C 2-6Alkene oxygen base (particularly allyloxy), C 2-6Alkynyloxy group (particularly alkynes propoxy-), halogen (C 1-6) alkyl (particularly trifluoromethyl), halogen (C 1-6) alkoxyl group (particularly trifluoromethoxy) ,-S (O) m(C 1-6) alkyl, wherein m is 0,1 or 2 and said alkyl is optional is replaced hydroxyl (C by halogen 1-6) alkyl, C 1-4Alkoxyl group (C 1-4) alkyl, C 1-4Alkoxyl group (C 1-4) alkoxyl group, C 3-6Naphthenic base, C 3-6Naphthenic base (C 1-4) alkyl; Optional substituted aryl (particularly optional substituted phenyl); Optional substituted heteroaryl (particularly optional substituted pyridyl or pyrimidyl); Optional substituted aryloxy (particularly optional substituted phenoxy), optional substituted heteroaryloxy (particularly optional substituted pyridyloxy or 2-pyrimidinyl oxy), optional substituted wherein m are 0,1 or 2-S (O) mAryl (particularly optional substituted thiophenyl), optional substituted wherein m are 0,1 or 2-S (O) mHeteroaryl (particularly optional substituted pyridine sulfenyl or pyrimidine sulfenyl), optional substituted aryl (C 1-4) alkyl (particularly optional substituted phenmethyl, optional substituted styroyl and optional substituted phenyl n-propyl), wherein moieties is optional is replaced optional substituted heteroaryl (C by hydroxyl 1-4) alkyl (particularly optional substituted pyridyl-or pyrimidyl (C 1-4) alkyl), optional substituted aryl (C 2-4) thiazolinyl (particularly optional substituted styryl), optional substituted heteroaryl (C 2-4) thiazolinyl (particularly optional substituted pyridyl vinyl or pyrimidyl vinyl), optional substituted aryl (C 1-4) alkoxyl group (particularly optional substituted benzyloxy and benzene oxyethyl group), optional substituted heteroaryl (C 1-4) alkoxyl group (particularly optional substituted pyridyl (C 1-4) alkoxyl group or pyrimidyl (C 1-4) alkoxyl group), optional substituted aryloxy (C 1-4) alkyl (particularly phenoxymethyl), optional substituted heteroaryloxy-(C 1-4) alkyl (particularly optional substituted pyridyloxy (C 1-4) alkyl or 2-pyrimidinyl oxy (C 1-4) alkyl), optional substituted wherein m is 0,1 or 2-S (O) m(C 1-4) alkylaryl (particularly optional substituted benzylthio and benzene ethylmercapto group), optional substituted wherein m is 0,1 or 2-S (O) m(C 1-4) miscellaneous alkyl aryl (particularly optional substituted pyridyl (C 1-4) alkylthio or pyrimidyl (C 1-4) alkylthio), optional substituted wherein m is 0,1 or 2-(C 1-4) alkyl S (O) mAryl (particularly thiophenyl methyl), optional substituted wherein m be 0,1 or 2-(C 1-4) alkyl S (O) mHeteroaryl (particularly optional substituted pyridine sulfenyl (C 1-4) alkyl or pyrimidine sulfenyl (C 1-4) alkyl), acyloxy comprises C 1-4Alkanoyloxy (particularly acetoxyl group) and benzoyloxy, cyanic acid, isocyano-, 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 group, halo (C 1-4) alkoxyl group, C 1-4Alkylthio, C 3-6Naphthenic base, C 3-6Naphthenic base (C 1-4) alkyl, phenyl or benzyl, said phenyl and benzyl group are optional by halogen, C 1-4Alkyl or C 1-4Alkoxyl group replaces, and R gAnd R hBe hydrogen independently, C 1-4Alkyl, halo (C 1-4) alkyl, C 1-4Alkoxyl group, halo (C 1-4) alkoxyl group, C 1-4Alkylthio, C 3-6Naphthenic base, C 3-6Naphthenic base (C 1-4)-alkyl, phenyl or benzyl, said phenyl and benzyl group are optional by halogen, C 1-4Alkyl or C 1-4Alkoxyl group 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 halogen or optional substituted alkyl.
Another organizes preferred formula (I) compound is Q wherein 1Be halogen, Q 2Be hydrogen and Q 3Be those of optional substituted alkyl.
Another organizes preferred formula (I) compound is Q wherein 1And Q 2Be halogen and Q 3Be those of optional substituted alkyl.
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 3Be the tertiary butyl, 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 group-2-methyl-prop-2-base, 1-alkene oxygen base-2-methyl-prop-2-base, 1-alkynyloxy group-2-methyl-prop-2-base, 1-cyanic acid-2-methyl-third-2-base, 1-alkoxyl group alkoxyl group-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 group-3-methyl fourth-3-base, 1-alkene oxygen base-3-methyl fourth-3-base, 1-alkynyloxy group-3-methyl fourth-3-base, 1-cyanic acid-3-methyl fourth-3-base, 2-cyanic acid third-2-base, 2-methoxycarbonyl third-2-base or 2-methylamino carbonyl third-2-base, 1-alkylthio-2-methyl-prop-2-base, 1-alkyl sulphinyl-2-methyl-prop-2-base, 1-alkyl sulphonyl-2-methyl-prop-2-base, 2-cyanic acid-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 imino-]-third-2-base, 2-methyl isophthalic acid-[(E and/or Z)-heteroaryloxy imino-]-third-2-base, 1-alkoxyl group-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 group-4-methyl-penta-2-alkynes-4-Ji, 1-alkoxyl group alkoxyl group-4-methyl-penta-2-alkynes-4-Ji, 1-alkoxy alkoxy alkyl-4-methyl-penta-2-alkynes-4-Ji, 1-cyanic acid alkyl-3-methyl fourth-3-Ji, 1-haloalkyl-3-methyl fourth-3-& CAT[N More preferably, R wherein 3It is the tertiary butyl; 1-halo-2-methyl-prop-2-base; 1-fluoro-2-methyl-prop-2-base; 1-methoxyl group-2-methyl-prop-2-base; 1-oxyethyl group-2-methyl-prop-2-base; 1-allyloxy-2-methyl-prop-2-base; 1-(third-2-alkynyloxy group)-2-methyl-prop-2-base; 2-cyanic acid-1-oxyethyl group-third-2-base; 2-cyanic acid-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 propoxy--4-methyl-penta-2-alkynes-4-base; 1-oxyethyl group-4-methyl-penta-2-alkynes-4-base.
Another organizes preferred formula (I) compound is these, wherein R 4Be alternatively by C 1-4Alkoxyl group-(C 1-4) alkoxyl group (C 1-4) the substituted C of alkyl 1-6Alkyl, wherein said alkyl group are alternatively by halogen ,-or two-(C 1-6) alkylamino or three (C 1-4) replacement of alkyl silyl, perhaps R 4Be alternatively by benzyloxy (C 1-4) the substituted C of alkyl 1-6Alkyl, wherein said alkyl group are alternatively by halogen ,-or two-(C 1-6) alkylamino or three (C 1-4) replacement of alkyl silyl, perhaps R 4Be alternatively by C 2-6Alkene oxygen base or-S (O) x(C 1-6) the substituted C of alkyl 1-6Alkyl, wherein x be 0,1 or 2 and said alkyl group alternatively by halogen ,-or two-(C 1-6) alkylamino ,-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 silyl, perhaps R 4Be-CR Uu=NR Vv, R wherein UuBe hydrogen or C 1-6Alkyl and R VvBe hydroxyl or optional substituted C 1-6Alkoxyl group.
Another organizes preferred formula (I) compound is these, wherein R 5The optional substituted aryl in the definition and the ring of optional substituted heteroaryl or part are replaced by following group alternatively: halogen, cyanic acid, nitro, azido-, C 1-6Alkyl, halo (C 1-6) alkyl, C 3-6Naphthenic base, C 3-6Naphthenic base (C 1-4) alkyl, C 2-6Thiazolinyl, halo (C 2-6) thiazolinyl, C 2-6Alkynyl, halo (C 2-6) alkynyl, C 1-6Alkoxyl group, halo (C 1-6) alkoxyl group, C 2-6Alkene oxygen base, halo (C 2-6) alkene oxygen base, C 2-6Alkynyloxy group, halo (C 2-6) alkynyloxy group, aryl, aryloxy, aryl (C 1-6) alkyl, aryl (C 1-6) alkoxyl group, heteroaryl, heteroaryloxy, heteroaryl (C 1-6) alkyl, heteroaryl (C 1-6) alkoxyl group ,-SF 5,-S (O) g(C 1-4) alkyl, wherein g be 0,1 or 2 and said 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 iReplace, wherein R iBe alternatively by the substituted C of halogen 1-6Alkyl and R gAnd R hBe hydrogen or independently of one another by the optional substituted C of halogen 1-6Alkyl is perhaps at-CONR gR hOr-SO 2NR gR hSituation under, R gR hCan combine to form 5-or 6-unit carbocyclic ring or heterocycle, it comprises and is selected from sulphur, oxygen or NR 0Heteroatoms, R wherein 0Be hydrogen or optional substituted C 1-6Alkyl.
Another organizes preferred formula (I) compound is these, and wherein optional substituted aryl and optional substituted heteroaryl or optional substituted 5-are to the ring R of 8-unit 4Replaced by following group alternatively: halogen, cyanic acid, nitro, azido-, C 1-6Alkyl, halo (C 1-6) alkyl, C 3-6Naphthenic base, C 3-6Naphthenic base (C 1-4) alkyl, C 2-6Thiazolinyl, halo (C 2-6) thiazolinyl, C 2-6Alkynyl, halo (C 2-6) alkynyl, C 1-6Alkoxyl group, halo (C 1-6) alkoxyl group, 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 said 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 optional substituted C of halogen 1-8Alkyl and R xAnd R yBe hydrogen or optional independently of one another by the substituted C of halogen 1-6Alkyl.
Another organizes preferred formula (I) compound is these, wherein R 50Be optional by the substituted C of following radicals 1-4Alkyl: halogen, hydroxyl, C 1-6Alkoxyl group, C 2-6Thiazolinyl (particularly allyl group), C 2-6Alkynyl (particularly propargyl), C 1-4Alkoxyl group (C 1-4) alkoxyl group, cyanic acid, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base,--or two (C 1-4) alkylamino-carbonyl oxygen base, wherein p is 0,1 or 2 S (O) p(C 1-6)-alkyl, triazolyl, pyrazolyl, imidazolyl, three (C 1-4)-alkyl siloxy, optional substituted phenoxy, optional substituted thiophene oxy, optional substituted benzyloxy or optional substituted thiophene methoxy.
Another organizes preferred formula (I) compound is these, wherein R 50Be optional by the substituted C of following radicals 3-6Naphthenic base: halogen, hydroxyl, C 1-6Alkoxyl group, C 1-4Alkoxyl group (C 1-4) alkoxyl group, cyanic acid, C 1-4Alkyl carbonyl oxy, amino carbonyl oxygen base ,-or two (C 1-4) alkylamino-carbonyl oxygen base, wherein p is 0,1 or 2 S (O) p(C 1-6)-alkyl, triazolyl, pyrazolyl, imidazolyl, three (C 1-4)-alkyl siloxy, optional substituted phenoxy, optional substituted thiophene oxy, optional substituted benzyloxy or optional substituted thiophene methoxy.
Another organizes preferred formula (I) compound is these, wherein optional substituted aryl or optional substituted heteroaryl R 50Optionally replaced: halogen, hydroxyl, sulfydryl, C by following radicals 1-4Alkyl, C 2-4Thiazolinyl, C 2-4Alkynyl, C 1-4Alkoxyl group, C 2-4Alkene oxygen base, C 2-4Alkynyloxy group, halo (C 1-4) alkyl, halo (C 1-4) alkoxyl group, C 1-4Alkylthio, halo (C 1-4)-alkylthio, hydroxyl (C 1-4) alkyl, C 1-4Alkoxyl group (C 1-4) alkyl, C 3-6Naphthenic base, C 3-6Naphthenic base-(C 1-4) alkyl, phenoxy, benzyloxy, benzoyloxy, cyanic acid, isocyano-, 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 group, halo (C 1-4) alkoxyl group, C 1-4Alkylthio, C 3-6Naphthenic base, C 3-6Naphthenic base (C 1-4) alkyl, phenyl or benzyl, said phenyl and benzyl group are alternatively by halogen, C 1-4Alkyl or C 1-4Alkoxyl group replaces, and R pAnd R qBe hydrogen, C independently 1-4Alkyl, halo (C 1-4) alkyl, C 1-4Alkoxyl group, halo (C 1-4) alkoxyl group, C 1-4Alkylthio, C 3-6Naphthenic base, C 3-6Naphthenic base (C 1-4) alkyl, phenyl or benzyl, said phenyl and benzyl group are alternatively by halogen, C 1-4Alkyl or C 1-4Alkoxyl group 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 compound that preferred formula (I) compound is the quinoline moiety formation of through type I compound.
The compound that forms the present invention's part is illustrated in following table 1 to 192.
Fusing point (mp) and/or identify molion (M for example +, [M+1] +) value and/or spectrum (1HNMR) data are provided in embodiment 1-5, biological activity 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 O, R 1Be methyl and R 2And R 3Has the implication that provides in this table.
Figure G2007800368897D00141
Figure G2007800368897D00151
Figure G2007800368897D00161
Figure G2007800368897D00181
Figure G2007800368897D00191
Figure G2007800368897D00201
Figure G2007800368897D00211
Figure G2007800368897D00231
Figure G2007800368897D00251
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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 chlorine, and n is 0, and L is O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 Q 3 is a chlorine, and n is 0, and L is O, 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 Q 3 is fluorine, and n is 0, and L is O, 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 O, 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 O, 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 Q 3 is a chlorine, and n is 0, and L is O, 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 O, 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 O, 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 Q 3 is fluorine, and n is 0, and L is O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O, 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 O.
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 1-6Alkyl, optional substituted phenmethyl, optional substituted C 2-6Thiazolinyl, optional substituted C 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 iBe C 1-6Alkyl, optional substituted phenmethyl, optional substituted C 2-6Thiazolinyl, optional substituted C 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 preferred method condition (temperature of reaction, 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 confirmed by those skilled in the art through 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, arrives under the reflux temperature of solvent, in the presence of radical initiator such as AIBN (azo-isopropyl cyanide) and light source in envrionment temperature; In The suitable solvent such as tetracol phenixin or acetonitrile, through 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.
Figure G2007800368897D00401
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; At 0 ℃ under the reflux temperature of solvent, in The suitable solvent such as tetracol phenixin or acetonitrile, through obtaining with halogenating agent such as N-chlorosuccinimide or N-bromosuccinimide reaction.Formula (5) halogen ester and the reaction of 6-hydroxyquinoline, wherein Q1, Q2 and Q3 as above define, and arrive under the reflux temperature of solvent in envrionment temperature; In the presence of alkali such as potassium tert.-butoxide, salt of wormwood or sodium hydride; At the suitable solvent such as the trimethyl carbinol, 1, among 4-dioxane or the DMF, provide formula (6) compound.Formula (6) compound is hydrolyzed to formula (7) acid, in envrionment temperature under the reflux temperature of solvent, in suitable solvent such as aqueous methyl alcohol, ethanol or THF (THF), through with alkali metal hydroxide M +OH -Reaction, acidifying subsequently obtains.Formula (7) acid can with formula (8) amine condensation; At 0 ℃ under envrionment temperature; In suitable solvent such as DMF, use suitable acvator 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 O.
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 through the compound of n=0 (1) wherein.For example, R wherein 5Be C 1-4The general formula of alkyl (6) ester can 0 ℃ under envrionment temperature, in suitable solvent such as ethanol, use oxygenant 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 methylene dichloride; Directly prepare from formula (6) compound with two equivalents or more how normal oxygenant such as metachloroperbenzoic acid (MCPBA), perhaps with monovalent or the preparation of more how normal metachloroperbenzoic acid from formula (9) sulfoxide.Formula (6) sulfide, formula (9) sulfoxide or formula (10) sulfone can arrive under the reflux temperature of solvent at 0 ℃, in suitable solvent such as ethanol, through 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 envrionment temperature, use suitable acvator such as HOBT and EDC, provide general formula (1) compound, wherein n is 0,1 or 2.
Figure G2007800368897D00411
Similarly, wherein n is 1 the formula (11) and the sulfoxide of formula (1), can describe that to use oxygenant such as sodium periodate or metachloroperbenzoic acid to come to prepare respectively from n wherein be 0 the formula (7) and the sulfide of formula (1) by preamble.Wherein n is 2 the formula (12) and the sulfone of formula (1); Can describe by preamble; Using the preparation of at least two normal oxygenants such as metachloroperbenzoic acid is 0 the formula (7) and the sulfide of formula (1) from n wherein, and perhaps using monovalent or more how normal oxygenant such as metachloroperbenzoic acid to prepare certainly n wherein is 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 envrionment temperature, use suitable acvator such as HOBT and EDC, provide formula (14) compound.Formula (14) compound can be formula (a 16) compound by halogenation, 0 ℃ under envrionment temperature, in suitable solvent such as tetracol phenixin 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 envrionment temperature, in suitable solvent such as methylene dichloride, in the presence of alkali such as triethylamine, through obtaining with formula (8) amine reaction.
Figure G2007800368897D00421
Formula (16) halo sulfide can with the reaction of substituted 6-hydroxyquinoline, 0 ℃ under 80 ℃, in The suitable solvent such as DMF, in the presence of alkali such as salt of wormwood 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 instance of general formula (8) amine of H, can prepare, use suitable alkali such as n-Butyl Lithium or sodium hydride, subsequently with suitable alkylating reagent R through 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-amino group alkynes (22) (Strecker is synthetic) is provided with the ammoniacal liquor that is generally the ammonium chloride form and with the prussiate that is the sodium cyanide solution form easily like formaldehyde.
Figure G2007800368897D00431
Shown in flow process 5, the amino alkynes of the silyl of general formula (24) protection can through suitable alkali such as three grades of organic amine alkali for example triethylamine down, with general formula (23) amine and 1,2-pair-(chloro dimetylsilyl) ethane reacts acquisition.General formula (26) amine, it is R wherein 2Be H and R 3Be-(CR 30R 40) C ≡ CR 50The instance of general formula (8) amine, the amino alkynes of silyl protection that can be through alkylation general formula (24) prepares, and uses suitable alkali such as n-Butyl Lithium, subsequently with suitable alkylating reagent R 50LG forms the alkylated compound of general formula (25) such as alkyl iodide iodomethane reaction for example.Said silyl protection base 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).
Figure G2007800368897D00432
In similar method, the amino alkynes of the silyl of general formula (24) protection can with carbonyl derivative R aCOR bLike formolite reaction, use suitable alkali such as n-Butyl Lithium, the amino alkynes (27) that comprises the hydroxyalkyl part is provided.The compound of general formula (27) can be earlier handled with alkali such as sodium hydride or two (trimethyl silyl) potassium amide, passes through compound R subsequently cLG for example iodoethane handles, and provides general formula (29) compound, said R cLG represents leavings group such as halogen among the LG, or sulphonate such as OSO 2Me, or OSO 2-4-tolyl.After removing silyl protection base, obtain the compound of general formula (30).Alternatively, can remove silyl protection base earlier to produce general formula (28) compound.The amino alkynes of general formula (28) can provide the silylated verivate on oxygen of general formula (31) further through reacting derivatize with sillylation reagent such as tert-butyldimethylsilyl chloride.
Flow process 6
Figure G2007800368897D00441
Shown in flow process 6; The amino alkynes of the silyl of general formula (32) protection can be at suitable alkali such as amino soda or for example two (trimethyl silyl) sodium amides of Lithamide alkali or sodium amide down, obtains through the amine of the silyl protection of general formula (24) and the chloroparaffin that has suit leavings 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 instance of general formula (8), can remove silyl protection base with for example aqueous acid subsequently and prepare through replacing cl anion, thereby form the cyano compound of general formula (34) with prussiate.
In similar method, general formula (35) acid amides can react with for example Potssium Cyanide, produces the amino alkynes of cyanic acid of general formula (36).
Shown in flow process 7, R wherein 50Be general formula (1) compound of H, thereby can under the Sonogashira condition, react substituted aryl or the heteroaryl compound that forms general formula (1), wherein R with for example optional substituted chloro, bromo, iodo or the substituted aryl of trifluoromethyl sulfonyl or heteroaryl 50Be optional substituted aryl or heteroaryl groups.Suitable palladium catalyst is that palladium (II) is closed in chlorination two (triphenylphosphine).
Other amine of general formula (8) or commercially available or can prepare through normative document method or standard modifying method.
Shown in flow process 8; Wherein Q1 is general formula (1) compound of bromine or iodine; Thereby can be under the Suzuki condition form the substituted aryl or the heteroaryl compound of general formula (1) with for example optional substituted aryl or heteroaryl acid reaction, wherein Q1 is optional substituted aryl or heteroaryl groups.Suitable palladium catalyst is that four (triphenylphosphines) close palladium (0).
Figure G2007800368897D00452
Thioamides (the wherein general formula of L=S (1) compound) can be from corresponding amide; Use vulcanizing agent such as thiophosphoric anhydride, Lawesson reagent or Davy reagent to prepare, perhaps use normative document method or standard modifying method to prepare from corresponding thioic acid sulfoacid or monothioester.
Substituted 6-hydroxyquinoline 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, substituted aromatic amine can be converted into substituted quinoline-6-alcohol easily.The instance 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 pathogenic agent: 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 plant); Two spore powdery mildews (Erysiphe cichoracearum) on the cucurbitaceous plant (for example muskmelon); Other Powdery Mildew on standing grain powdery mildew on barley, wheat, rye and the lawn (Blumeria (or Erysiphe) graminis) (Powdery Mildew) and the various host is such as the Tartar's internal thread powdery mildew (Leveillulataurica) on the spot monofilament shell (Sphaerotheca macularis) on the hops, monofilament shell (Sphaerotheca fusca (Sphaerothecafuliginea)), tomato, eggplant and the green pepper on the cucurbitaceous plant (like cucumber), podosphaera leucotricha (Podosphaera leucotricha) and the grape snag shell (Uncinula necator) on the grape on the apple; 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 Semen arachidis hypogaeae tail spore (Cercospora arachidicola) on the peanut and Cercosporidiumpersonatum and other host such as sugar beet, rubber, soybean and the rice; Other Staphlosporonites (Botrytiss pp.) 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 Radix Dauci Sativae), oilseed rape, apple, tomato, yam, cereal (for example wheat) and other host; Venturia (Venturiaspp.) on apple, pears, drupe, tree nuts and other host (comprising venturia inaequalis (Venturia inaequalis) (black spot)); 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.) at a distance from the spore shell; Phoma on oilseed rape, lawn, rice, yam, wheat and other host (Phoma spp.); Aspergillus on wheat, timber and other host (Aspergillus spp.) and aureobasidium genus (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 (for example bitter rot (enclosing little silk shell (Glomerella cingulata)), Black Rotten or fruit rot (Botryosphaeria obtusa), diplostomiasis (Mycosphaerellapomi), Cedar rust of apple (Gymnosporangium yamadai) (Gymnosporangium juniperi-virginianae), coal spot disease (a kind of fruit, such as apple, pear, etc. glues shell spore (Gloeodes pomigena)), coal are 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 oidium; 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 (Pythium ultimum)) on lawn and other host; Phytophthora (Phytophthora spp.) on phytophthora infestans on yam and the tomato (Phytophthora infestans) and vegetables, strawberry, avocado, pepper, ornamental plant, tobacco, cocoa beans and other host; Rhizoctonia (Rhizoctonia spp.) on thanatephorus cucumeris(frank) donk on rice and the lawn (Thana tephorus cucumeris) and various host such as wheat and barley, peanut, vegetables, cotton and the lawn; Sclerotinia (Sclerotiniaspp.) on lawn, peanut, yam, 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 (Colietotrichum 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, yam and the tomato; Bury Sclerotinia (Pyrenopeziza spp.) on oilseed rape and other host; On cocoa beans, 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 (Ustiiagospp.), Urocystis (Urocystis spp.), Tilletia (Tilletia spp.) and ergot (Claviceps purpurea); Separated Cylindrocarpon on sugar beet, barley and other host (Rammularia spp.); Results back disease; The disease on the fruit (for example the Penicillium digitatum on the orange (Penicillium digitatum), Italian mould (Penicilliumitalicum) and 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 pathogenic agent on the grape, especially Eutypa lata, grape Guignardia (Guignardia bidwellii), phelliuns igniarius (Phellinus igniarus), grape Phomopsis bacterium (Phomopsis viticola), the false cup fungi (Pseudopeziza tracheiphila) of vascular bundle and hair Boreostereum vibrans (Stereumhirsutumn); Other pathogenic agent, especially Cephaloa scusfragrans on trees (for example Lophodermium seditiosum) or the timber, long beak shell belong to (Ceratocystisspp.), Ophiostoma piceae, penicillium (Penicilliumm spp.), false healthy and free from worry wood mould (Trichoderma pseudokoningiii), viride (Trichoderma viride), Trichoderma harzianum, black mold (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 present invention provides antagonism or control to cause the method for plant characteristic of disease fungi, and it comprises the location of the formula of fungicidal significant quantity (I) compound administration to seed, plant or the seed of plant, plant, soil or any other plant-growth media such as nutritive medium.
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 property (antisporulant).
Formula (I) compound preferably is used for agricultural, gardening and turfgrass purpose with composition forms.
Be location, soil or other growth media with formula (I) compound administration to seed, plant or the seed of plant, plant; Usually be compsn with formula (I) compound formulation; It comprises suitable inert diluent or carrier except that formula (I) compound, and optional tensio-active agent (SFA).SFA is can be through reducing IT and causing that thus other character (for example dispersion, emulsification and moistening) changes the chemical that makes interface (for example, liquid/solid, liquid/gas or liquid/liquid interface) character modification.Preferred all compsns (solid and liquid preparation) comprise 0.0001 to 95% weight, more preferably 1 to 85% weight, the 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.
Fungicide composition is provided in another aspect of this invention, and it comprises formula (I) compound of fungicidal significant quantity 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 said fungi of compositions-treated of the fungicidal significant quantity that comprises formula (I) compound or the location of said 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), wettable powder (WP), granule (GR) (slow or snap-out 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-emulsion (EO)), microemulsion (ME), suspension concentrates (SC), smoke substance, atomizing/sootiness preparation, micro-capsule suspension (CS) and seed treatment preparation.The preparation type of selecting in any case will depend on physics, the chemistry and biology character of the specific purposes and formula (I) compound of hope.
Can be through formula (I) compound and one or more solid diluents (for example natural clay, kaolin, pyrophyllite, wilkinite, alumina, smectite, zeyssatite (kieselguhr), chalk, zeyssatite (diatomaceous earths), calcium phosphate, lime carbonate and magnesiumcarbonate, sulphur, lime, flour, talcum and other organic with inorganic solid support) being mixed and becoming fine powder to prepare pulvis (DP) this mixture mechanical mill.
Can pass through formula (I) compound and one or more water-soluble inorganic salts (such as sodium hydrogencarbonate, yellow soda ash or sal epsom) or one or more water-soluble organic solid (such as polysaccharide); And alternatively, the mixture that one or more wetting agents, one or more dispersion agents or said are used for improving water dispersible/deliquescent reagent mixes and prepares water solube powder (SP).Then this mixture is worn into fine powder.Also can make the similar compositions prilling 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 dispersion agents; And alternatively, one or more are used for promoting dispersive suspension agent in the liquid to mix preparing wettable powder (WP).Then this mixture is worn into fine powder.Also can make the similar compositions prilling to form water-dispersible granules (WG).
Can be through making the compound particles granulation of formula (I) compound and one or more powdery solid diluent or carriers; Perhaps through making formula (I) compound (or its solution in suitable reagent) be absorbed into honeycombed grain material (such as float stone, attapulgite clay, fuller's earth, zeyssatite (kieselguhr), zeyssatite (diatoma ceous earths) or corn cob meal) from preformed blank granule, perhaps through make formula (I) compound (or its solution in suitable reagent) be adsorbed onto on the stone material (such as sand, silicate, mineral carbonic acid salt, vitriol or phosphoric acid salt) also optionally drying form 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 tackiness agent (such as Yodo Sol VC 400, Z 150PH, dextrin, sugar and vegetables oil).One or more other additives also can be included in the granule (for example emulsifying agent, wetting agent or dispersion agent).
Can disperse dense dose (DC) through preparing in formula (I) compound is water-soluble or the organic solvent like ketone, alcohol or glycol ether.These solvents can comprise surface-active agents (for example be used in spray cistern, improving water-dilutable or prevent crystallization).
Can prepare missible oil (EC) or aqueous emulsion (EW) through formula (I) compound being dissolved in the organic solvent (mixture that comprises one or more wetting agents, one or more emulsifying agents or said reagent alternatively).The organic solvent that is suitable for EC comprise aromatic hydrocarbon (such as korenyl or alkylnaphthalene, for example SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a registered trademark), the dimethylformamide of ketone (such as pimelinketone or methylcyclohexanone), alcohol (such as phenyl alcohol, furfuryl alcohol or butanols), N-alkyl pyrrolidone (such as N-Methyl pyrrolidone or N-octylpyrrolidone), lipid acid is (such as C 8-C 10The lipid acid dimethylformamide) and chlorinated hydrocarbon.Spontaneous emulsification when the EC product can be in adding entry produces and has enough stability to allow the emulsion through 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 (through 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 vegetables oil, chlorinated hydrocarbon (such as chlorobenzene), aromatic solvent (such as korenyl or alkylnaphthalene) and other have the suitable organic solvent of low solubility in water.
Can prepare microemulsion (ME) through water is mixed with the thermodynamically stable isotropic liquid preparation of spontaneous generation with the foreign body of one or more solvents and one or more SFA.Formula (I) compound is present in the said water or in said solvent/SFA foreign body 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 through the existence of this system of specific conductivity measurements determination) and can be suitable in same preparation, mixing water miscible and oil-soluble agricultural chemicals.ME is suitable in water, diluting, and perhaps still perhaps forms conventional O/w emulsion as microemulsion.
Suspension concentrates (SC) can comprise the segmentation insoluble solids particulate water-based or the non-aqueous suspension-s of formula (I) compound.Can use one or more dispersion agents alternatively through ball milling in appropriate medium or pearl mill solid type (I) compound, prepare SC with the fine particle suspension-s that produces said compound.Can comprise one or more wetting agents in the compsn, can also comprise that suspension 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 finished product of hoping.
The smoke substance preparation comprises formula (I) compound and suitable propellant (for example normal butane).Can formula (I) compound be dissolved in or be scattered in the appropriate medium (for example water or liquid that can be miscible with water, like n-propyl alcohol) to be provided at the compsn that uses in non-pressurized, the manual atomizing pump.
Can formula (I) compound be mixed the compsn that is suitable in enclosed space, producing the smog that comprises said compound with formation with firework mixture under dryness.
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 aqueous dispersion of oil droplet; Wherein each oil droplet by polymkeric substance shell packing and comprise formula (I) compound and, alternatively, carrier for this reason or thinner.Can produce above-mentioned polymkeric substance shell through the interfacial polycondensation reaction or through agglomeration 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 said compound slowly, controlled release.
Compsn can be included as the biology performance that improves said composition (for example through 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 MO or crude vegetal (such as soybean or rapeseed oil), and the foreign body 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 agent; 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 liquid compsn.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 compsn of handling seed can comprise that auxiliary composition is adhered to the reagent of seed (for example MO or one-tenth envelope barrier).
Wetting agent, dispersion agent and emulsifying agent can be the SFA of positively charged ion, negatively charged ion, both sexes or non-ionic type.
Suitable cationic SFA comprises quaternary ammonium compound (for example cetyl trimethylammonium bromide), imidazolines and amine salt.Suitable negatively charged ion SFA comprise an alkali metal salt of lipid acid, the salt of sulfuric acid aliphatic mono (for example sodium lauryl sulphate), sulfonated aromatic compound salt (the for example mixture of X 2073, calcium dodecylbenzene sulphonate, butyl naphthalene sulfonate and di-isopropyl sodium naphthalene sulfonate and triisopropyl sodium naphthalene sulfonate), ether sulfate, ether alcohol sulfate (for example three laureth 9 sodium sulfate (sodium laureth-3-sulphate)), ether carboxylate (for example three laureth 9 carboxylic acid sodium (sodiumlaureth-3-carboxylate)), SULPHOSUCCINIC ACID ESTER (product of one or more Fatty Alcohol(C12-C14 and C12-C18) and phosphatase reaction (mainly being monoesters) or and the product (mainly being diester) that reacts of Vanadium Pentoxide in FLAKES, for example dodecanol and four phosphatase reactions; These products can be by ethoxyquin in addition), sulphosuccinamate, alkane or alkene sulfonate, taurate and sulfonated lignin.Suitable amphoteric SFA comprises trimethyl-glycine, propionic salt and glycinate.Suitable non-ionic type SFA comprise as the epoxy alkane of oxyethane, propylene oxide, butylene oxide ring or its mixture and Fatty Alcohol(C12-C14 and C12-C18) (such as oleyl alcohol or octanol) or with the condensation product of alkylphenol (such as octyl phenol, nonylphenol or octyl group cresylol); The partial ester of derivation of self-long chain lipid acid or hexitan mixture; The condensation product of said partial ester and oxyethane; Block polymer (comprising oxyethane and propylene oxide); Alkylolamide; Simple ester (for example fatty acid polyglycol ester); Amine oxide (for example dodecyl dimethyl amine oxide); And Yelkin TTS.
Suitable suspension agent comprises hydrophilic colloid (such as polysaccharide, Vinylpyrrolidone polymer or Xylo-Mucine) and swelling soil (such as wilkinite or attapulgite).
Formula (I) compound can be used through any currently known methods of using Fungicidal compounds.For example; It can with preparation or not dosage form be applied directly to any plant part that comprises leaf, stem, branch or root; Before cultivation, be applied to seed; Perhaps be applied to growing plant wherein or other media (such as the soil around the root, soil, paddy field water either or soilless culture system in general sense) that will cultivated plant, perhaps in soil or aqueous environment, spray, dust, use, use, use or distribution through compsn (such as particulate compsn or be packaged in the compsn in the water-soluble bag) or mix and use as steam as creme or paste through dipping.
Can also use electric atomizing technology or other lower volume method formula (I) compound injection is gone into plant or to be sprayed on the vegetation, or use through land or aerial irrigation system.
Usually with the stoste supplied that comprises activeconstituents at high proportion compsn, before use this stoste is added in the water as aqueous compositions (aqs soln or dispersion liquid).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 after such storage, can be added to and form aqueous compositions in the water that it keeps evenly so that it can be used through habitual spraying equipment in time enough.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 up to the formula of 25% weight (I) compound aptly.
So the present invention also provides the Ru 2006101161 that comprises fertilizer and formula (I) compound.
Compsn of the present invention can comprise the compound of other biologically active, for example micro-nutrients or the compound that has the compound of similar or additional Fungicidally active or have plant growth regulating, weeding, desinsection, nematicide or acaricidal activity.
Through comprising other mycocide, resulting composition can have than wideer activity profile of independent formula (I) compound or higher intrinsic activity level.Further, this other mycocide can play synergy to the Fungicidally active of formula (I) compound.
Formula (I) compound can be the unique activeconstituents in the compsn or can mix with one or more additional activity compositions when suitable that said additional activity composition is as murdering agent, mycocide, synergistic agent, weedicide or plant-growth regulator.The additional activity composition can: provide to have broad spectrum of activity more or at persistent compsn of on-site increase; The activity of the activity of synergy formula (I) compound or compensation type (I) compound (for example through increasing onset speed or overcoming repellency); Or help to overcome or prevent to develop the resistance that to be directed against single composition.Concrete additional activity composition will depend on the hope purposes of said compsn.
The compositions of the invention may be included in the fungicidal compounds are AC? 382042 (N-(1 - cyano-1 ,2 - dimethyl-propyl) -2 - (2,4 - dichlorophenoxy ) propionamide), activated esters, boll Granville, Austria tears morpholine (aldimorph), enemy benomyl, oxygen propiconazole, grass yl piperidine ketone, azoxystrobin, Benalaxyl, benomyl, thiabendazole benzene amine, biloxazol , Bitertanol, blasticidin (blasticidin? S), boscalid (nicobifen new name), bromuconazole, ethirimol sulfonate, captafol, captan, carbendazim, carbendazim hydrochloride, carboxin, cyclopropane acid bacteria amines, carvone, CGA? 41396, CGA? 41397, Chinomethionate, chlorobenzene race ketone (chlobenzthiazone), chlorothalonil, B bacteria Lee, clozylacon , copper compounds such as copper oxychloride, copper hydroxy quinoline, sulfate, fatty acids, copper and Bordeaux mixture, cyazofamid, cyazofamid (IKF-916), cyflufenamid, cymoxanil, cyproconazole, cyprodinil, microphone from Wei, di - 2 - pyridyl disulfide, 1,1 '- dioxide, dichlofluanid, bis amine cypermethrin bacteria, pyridazine, cycloheximide, Dicloran, diethofencarb, benzene ring yl ether, wild Yan dry, fluorine MEPANIPYRIM, O, O-two - isopropyl-S-benzyl phosphorothioate, dimefluazole, dimetconazole, dimethyl ethyl phenol, Dimethomorph, Kresoxim amine, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodecyl morpholine ring, dodine, doguadine, edifenphos, epoxiconazole, thiazole pyraclostrobin, ethirimol, (Z)-N-benzyl-N ([methyl (methyl - thio ethylideneaminooxy butoxycarbonyl) amino] thio)-β-alanine ethyl ester, soil benomyl , famoxadone, imidazole cycloheximide, fenarimol, fenbuconazole, ofurace, cycloalkyl amine acid bacteria, cyano bacteria amine (AC? 382042), fenpiclonil, Fenpropidine, fenpropimorph, triphenyl tin acetate, triphenyl tin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, amine fluoride acid bacteria, flumorph, chlorofluorocarbons sclerotia Lee, fluoxastrobin, mefloquine azole, Flusilazole, flusulfamide, fluorine amide, Flutriafol, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furosemide topiramate bacteria amines, guazatine, Hexaconazole, hydroxyisoxazole evil azole, hymexazol, imazalil, imines azole, Iminoctadine amines, amine triacetate Iminoctadine, Ipconazole, iprobenfos, iprodione, isopropyl bacteria amine, isopropyl butyl carbamate esters, Isoprothiolane, kasugamycin, Kresoxim, LY186054, LY211795, LY? 248908, mancozeb, maneb, metalaxyl, MEPANIPYRIM, mepronil, metalaxyl, fine A Cream Spirit Metconazole, metiram, metiram zinc, phenoxy bacteria amines, benzene table cycloheximide, MON65500 (N-allyl -4,5 - dimethyl-2 - trimethyl silyl thiophene-3 - carboxamide), myclobutanil, NTN0301, Tian An, dimethyl dithiocarbamate, nickel phthalate ester bacteria, nuarimol, furosemide amides, organic mercury compounds, kresoxim-amine oxime, oxadixyl epoxy ethyl, oxolinic acid, evil imidazole, oxidation Vitavax, pefurazoate, penconazole, Pencycuron, leaf blight net, phosphorous acid, tetrachlorophthalide, Picoxystrobin, Polyoxin D, METIRAM (polyram), allyl benzene thiazole, prochloraz, procymidone, Propamocarb, propamocarb hydrochloride, propiconazole, Propineb, propionic acid, quinoline propoxyphene morpholine, prothioconazole, pyraclostrobin, topiramate bacteria phosphorus, pyridine spot oxime, pyrimethanil, pyroquilon, chlorine topiramate furosemide ether, pyrrole Nigerian group, quaternary ammonium compounds, Chinomethionate, phenoxy quinoline, PCNB, silicon thiabendazole amine (MON? 65500), S-imazalil simeconazole, simeconazole (sipconazole), PeCB sodium oxide, amine Spiro bacteria, streptomycin, sulfur, tebuconazole, leaf blight phthalocyanine, tecnazene, PTFE ether triazole, thiabendazole, ceftiofur amide 2 - (thio Cyanomethylthio) benzothiazole, thiophanate-methyl, thiram , thiazole acid bacteria amine, imine yl (timibenconazole), tolclofos-methyl, Tolyfluanid, triadimefon, triadimenol, butyl triazole, imidazole, triazine, tricyclazole, tridemorph, trifloxystrobin esters, triflumizole, triforine, sterilization azole, validamycin A, metam sodium, vinclozolin, XRD-563, zineb, ziram, zoxamide and style
Figure G2007800368897D00571
compounds.
Can formula (I) compound 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 activeconstituents 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 activeconstituents is that water-soluble solid and another kind of activeconstituents are when being water-insoluble liquid, through said solid active agent is disperseed (using and the similar preparation method of SC) and said liquid actives still can be dispersed in same continuous aqueous phase with every kind of activeconstituents as emulsion dispersion (using and the similar preparation method of EW) as suspension-s.Resulting composition is suspended emulsion agent (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=THF DMSO=methyl-sulphoxide
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=nucleus magnetic resonance of bs=
T=triplet HPLC=performance liquid chromatography
Q=quartet TLC=thin-layer chromatography
M=multiplet glc=gas liquid chromatography
Ppm=1,000,000/EDC=1-base-3-N, the N-dimethylamino
M=volumetric 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-tertiary butyl-2-methylthio group-ethanamide (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-anisidine (10g) in the acetate (100ml), after this dilute with water and use ethyl acetate extraction.Organic phase is with 2N NaOH washing, and is dry on sodium sulfate, 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)δppm：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 Hydrogen bromide (the 48 weight % aqueous solution) (100ml x2) were refluxed 62 hours.Mixture is cooled to envrionment temperature, and ethyl acetate extraction is handled and used to dilute with water with sodium hydrogencarbonate.Extract is dry on sal epsom, filters, and reduction vaporization provides desired product, 3-bromo-7-chloro-quinoline-6-alcohol (M+260). 1H?NMR(DMSO)δppm：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)-methylthio group-methyl acetate
Step 1
In stirring, be cooled in-15 ℃ methylene dichloride (300ml) solution of (methylthio group) methyl acetate (10.8ml) and drip SULPHURYL CHLORIDE (8.1ml).This mixture put be warmed to room temperature, last 2 hours, then concentrating under reduced pressure provides thick chloro-methylthio group-methyl acetate, is colourless liquid.Product do not added to be further purified be used for subsequent step. 1H?NMR(CDCl 3)δppm：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-methylthio group-methyl acetate (0.79g).This mixture was heated 1 hour down at 60-65 ℃, be cooled to envrionment temperature then, dilute with water is also used ethyl acetate extraction.Merge extract, use brine wash, dry on sal epsom, filter reduction vaporization.Through chromatography (silica gel, the ethyl acetate/hexane of 1: 4 volume ratio) purifying roughage, title compound is provided, 3-bromo-7-chloro-quinoline-6-base oxygen base)-methylthio group-methyl acetate (M+378). 1H?NMR(CDCl 3)δppm：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)-methylthio group-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 deposition, use cold water washing, vacuum-drying provides (3-bromo-7-chloro-quinoline-6-base oxygen base)-methylthio group-acetate (M+364). 1H?NMR(DMSO-d6)δppm：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-tertiary butyl-2-methylthio group-ethanamide
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 methylthio group-acetate (85mg) is with TERTIARY BUTYL AMINE (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 sal epsom subsequently with saturated aqueous sodium carbonate, water (three times) washing, filter, reduction vaporization provides oily matter.Through chromatography (silica gel; The hexane/ethyl acetate of 3: 1 volume ratios) this oily matter of chromatography provides desired product, be white solid (m.p.172-174 ℃, M+419). 1H?NMR(CDCl 3)δppm：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 with 1.84 (3H, 2xs); 2.18 with 2.20 (3H, 2xs); 3.52 with 3.53 (3H, 2xs); 3.64-3.84 (2H, 2xdd); 5.76 with 5.77 (1H, 2xs); 7.29 with 7.30 (1H, 2xs); 7.59 with 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-tertiary butyl-2-methylthio group-ethanamide (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 phase is used NH 4The OH solution washing, dry on sodium sulfate, filter, reduction vaporization provides desired product, and 3-bromo-7-methyl-6-quinoline-6-alcohol directly is used for 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-methylthio group 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-methylthio group acetate methyl esters, provide 3-bromo-7-methyl-quinolyl-6-oxygen base-2-methylthio group-methyl acetate (M +358). 1H?NMR(CDCl 3)δppm：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)-methylthio group-acetate
With with embodiment similar method of 1 stages 3,, provide (3-bromo-7-methyl-quinoline-6-base oxygen base)-methylthio group-acetate (M with 3-bromo-7-methyl-quinolyl-6-oxygen base-2-methylthio group-methyl acetate hydrolysis +344). 1H?NMR(DMSO)δppm：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-tertiary butyl-2-first sulphur Base-ethanamide
With with embodiment similar method of 1 stages 4, with 2-(3-bromo-7-methyl-quinolyl-6-oxygen base)-2-methylthio group acetate and TERTIARY BUTYL AMINE condensation, provide 2-(3-bromo-7-methyl-quinoline-6-base oxygen base)-N-tertiary butyl-2-methylthio group-ethanamide (m.p.132-134 ℃, M +344). 1H?NMR(CDCl 3)δppm：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 (CDCl 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 with 1.83 (3H, 2xs); 2.20 with 2.21 (3H, 2xs); 2.48 (3H, s); 3.50 with 3.53 (3H, 2xs); 3.61-3.82 (2H, 2xdd); 5.72 with 5.75 (1H, 2xs); 7.11 with 7.13 (1H, 2xs);
7.32 with 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) 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-tertiary butyl-2-methylthio group-ethanamide (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)δppm：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 Hydrogen bromide from the 3-bromo-7-fluoro-6-methoxy yl-quinoline of last-step, provide 3-bromo-7-fluoro-quinoline-6-alcohol (M +244). 1H?NMR(DMSO-d6)δppm：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)-methylthio group-methyl acetate
With with the similar method of embodiment 1 stages 2 step 2; 2-bromo-2-methylthio group acetate methyl esters pure from 3-bromo-7-fluoro-quinoline-6-of a last step and from embodiment 1 stages 2 step 1 is reacted, provide 3-bromo-7-fluoro-quinolyl-6-oxygen base-2-methylthio group acetate methyl esters (M +362). 1H?NMR(CDCl 3)δppm：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)-methylthio group-acetate
With with embodiment similar method of 1 stages 3,, provide (3-bromo-7-fluoro-quinoline-6-base oxygen base)-methylthio group-acetate (M with 3-bromo-7-fluoro-quinolyl-6-oxygen base-2-methylthio group-methyl acetate hydrolysis +348). 1H?NMR(DMSO-d6)δppm：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-tertiary butyl-2-methylthio group-ethanamide
With with embodiment similar method of 1 stages 4, with 2-(3-bromo-7-fluoro-quinolyl-6-oxygen base)-2-methylthio group acetate and TERTIARY BUTYL AMINE condensation, provide 2-(3-bromo-7-fluoro-quinoline-6-base oxygen the base)-N-tertiary butyl-2-methylthio group-ethanamide (m.p.144-145 ℃, M +403). 1H?NMR(CDCl 3)δppm：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) ppm: diastereo-isomerism mixture (1/1); 1.81 with 1.83 (3H, 2xs); 2.21 with 2.22 (3H, 2xs); 3.52 with 3.54 (3H, 2xs); 3.64-3.84 (2H, 2xdd); 5.75 with 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, b s); 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) 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-oxyethyl group-1,1-dimethyl--ethamine, m.p.111-113 ℃; 1H NMR (CDCl 3) 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-tertiary butyl-2-methylthio group-ethanamide (table 7 compound N o.12)
Stage 1: preparation 3-iodo-6-hydroxyquinoline
In ST; Add N, N, N ' in the 3-bromo-7-fluoro-6-hydroxyquinoline (0.50g) from embodiment 3 stage 1 step 2, Soiodin (0.62g) and the mixture of cupric iodide (0.08g) in dioxane (3.0ml) in stirring; N '-tetramethyl--ethane-1,2-diamines (0.07g).Mixture is stirred 14h down at 120 ℃, when cooling, use WITH AMMONIA TREATMENT, handle with aqueous hydrochloric acid subsequently.Use ethyl acetate extraction, dry organic phase on sal epsom is filtered, and reduction vaporization provides desired product (M +290), be light brown powder, it directly is used for subsequent step. 1H?NMR(CDCl 3)δppm：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-tertiary butyl-2-(3-iodo-7-fluoro-quinoline-6-base oxygen base)-2-methylthio group-ethanamide
With with the similar method of embodiment 1 stages 2 step 1,, provide (the basic oxygen base of 3-iodo-7-fluoro-quinoline-6-)-methylthio group-ETHYLE ACETATE (M with 3-iodo-7-fluoro-6-hydroxyquinoline and chloro methylthio group-acetic acid ethyl reaction +408).
With with embodiment similar method of 1 stages 3, will (3-iodo-7-fluoro-quinoline-6-base oxygen base)-methylthio group-hydrolysis of ethyl acetate, provide (3-iodo-7-fluoro-quinoline-6-base oxygen base)-methylthio group-acetate (M +394).
With with embodiment similar method of 1 stages 4, will (3-iodo-7-fluoro-quinoline-6-base oxygen base)-methylthio group-acetate and TERTIARY BUTYL AMINE condensation, provide the N-tertiary butyl-2-(the basic oxygen base of 3-iodo-quinoline-6-)-2-methylthio group-ethanamide, 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 with 1.84 (3H, 2xs); 2.20 with 2.22 (3H, 2xs);
3.53 with 3.54 (3H, 2xs); 3.64-3.84 (2H, 2xdd); 5.73 with 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-tertiary butyl-2-(7-fluoro-3-thiene-3-yl--quinoline-6-oxygen base)-2-methylthio group-ethanamide (table 30 compound N o.12).
Stage 1: in will stirring from the embodiment 2-in 3 stages 4 (3-bromo-7-fluoro-quinoline-6-base oxygen the base)-N-tertiary butyl-2-methylthio group-ethanamide (160mg), chlorination two (triphenylphosphine) close palladium (II) (1.4mg), 3 thienylboronic acid (56mg) and sodium hydrogencarbonate (101mg)) at dioxane/water (1: 1 mixture; 4.8ml) in mixture heating up to 70 ℃, continue 14h.During cooling, reaction mixture is handled with saturated sodium bicarbonate aqueous solution (5ml).Use ethyl acetate extraction, organic phase is dry on sal epsom, filters, and reduction vaporization provides thick product, through chromatography (silica gel; The hexane/ethyl acetate of 2: 1 volumes 2: 1) chromatography provides desired product, be white solid (m.p.170-173 ℃, M+405). 1H?NMR(CDCl 3)δppm：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-methylthio group-ethanamide (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-methylthio group-ethanamide.
Embodiment 6
This embodiment is the fungicidal property of Ming Dynasty style (I) compound for example.
Method test compounds in blade wafer is measured of using hereinafter to describe.Test compounds is dissolved in DMSO and in water, is diluted to 200ppm.Under the situation of ultimate corruption mould (Pythiumultimum) test, test compounds is dissolved in DMSO and in water, is diluted to 20ppm.
Wheat standing grain powdery mildew (Erysiphe graminis f.sp.tritici) (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) (late blight of potato 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) (grapevine oidium): grapevine 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 panels, use the spectrphotometric method for measuring growth-inhibiting 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 panels, use the spectrphotometric method for measuring growth-inhibiting after 48 hours.
Ultimate corruption mould (Pythium ultimum) (samping 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 panels, use the spectrphotometric method for measuring growth-inhibiting 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 viticola); 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 graminis f.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 (5)

1. compound of Formula I
Figure FSB00000738405600011
Wherein
Q 1And Q 3Be halogen and Q 2Be hydrogen,
R 1Be optional substituted C 1-4Alkyl, optional substituted C 2-4Thiazolinyl, optional substituted C 2-4Alkynyl or optional substituted C 3-4Naphthenic base,
R 2Be hydrogen, C 1-8Alkyl, C 3-4Naphthenic base, C 2-8Thiazolinyl, cyanic acid, hydroxyl, alkoxyl group, cyanic acid (C 1-4) alkyl, C 1-4Alkoxyl group (C 1-4) alkyl, C 1-4Alkoxyl group (C 1-4) alkoxyl group (C 1-4) alkyl or benzyloxy (C 1-4) alkyl, wherein said benzyl ring is alternatively by C 1-4Alkoxyl group 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,
Cyanic acid, hydroxyl, C 1-4Alkoxyl group or C 1-4Carbalkoxy, perhaps
R aR b, R cR dOr R eR fCan combine to form 3 to 8 yuan of carbocyclic rings or heterocycles, it comprises and is selected from sulphur, oxygen or NR oHeteroatoms, R wherein oBe hydrogen or optional substituted C 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 optional substituted C 1-6Alkyl, optional substituted C 2-6Thiazolinyl ,-CR Uu=NR Vv, R wherein UuBe hydrogen or C 1-6Alkyl and R VvBe hydroxyl or optional substituted C 1-6Alkoxyl group, optional substituted aryloxy or optional substituted heteroaryloxy perhaps-CH 2-C ≡ C-R 5, wherein
R 5Be hydrogen, the substituted C of the following group of optional quilt 1-8Alkyl: halogen, hydroxyl, C 1-6Alkoxyl group, C 1-3Alkoxyl group (C 1-3) alkoxyl group, cyanic acid, 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 substituted C of the following group of optional quilt 3-6Naphthenic base: halogen, hydroxyl, C 1-6Alkoxyl group, C 1-3Alkoxyl group (C 1-3) alkoxyl group, cyanic acid, 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 3-6Naphthenic base (C 1-4) alkyl, wherein said alkyl and/or cycloalkyl moiety are replaced by following group alternatively: halogen, hydroxyl, C 1-6Alkoxyl group, C 1-3Alkoxyl group (C 1-3) alkoxyl group, cyanic acid, 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 optional substituted aryl, optional substituted aryl (C 1-4) alkyl, optional substituted aryloxy (C 1-4) alkyl, optional substituted heteroaryl or optional substituted heteroaryl (C 1-4) alkyl or optional substituted heteroaryloxy (C 1-4) alkyl, perhaps
R 4Be optional substituted C 3-6Naphthenic base, optional substituted C 5-6Cycloalkenyl group, optional substituted aryl, optional substituted heteroaryl or optional substituted 5-be to 8-unit ring, and it comprises alternatively and is selected from sulphur, oxygen or NR 0Heteroatoms, R wherein oBe hydrogen or optional substituted C 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 combine to form 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 00Heteroatoms, R wherein 00Be alternatively by halogen, C 1-6The substituted C of alkoxyl group or cyanic acid 1-4Alkyl, perhaps R 00Be alternatively by nitro, C 1-4Alkyl, halo (C 1-4) alkyl, C 1-4The substituted phenyl of alkyl-carbonyl or heteroaryl, perhaps R 2And R 3Can combine to form optional substituted 6,6-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 group (C 1-3) alkyl, C 2-3Thiazolinyl or C 2-3Alkynyl, perhaps
R 30And R 40Combine to form 3 to 6 yuan of carbocyclic rings or heterocycles with the carbon atom that links to each other with them, it comprises and is selected from sulphur, oxygen or NR 000Heteroatoms, 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 hydrogen, optional substituted C 1-4Alkyl, optional substituted C 3-6Naphthenic base, optional substituted aryl or optional substituted heteroaryl, it comprises and is selected from sulphur, oxygen or NR 000Heteroatoms, 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 compound.
2. the compound of claim 1, wherein R 1Be C 1-4Alkyl or halo (C 1-4) alkyl.
3. the compound of claim 1, wherein R 2Be hydrogen or methyl.
4. fungicide composition, its comprise the fungicidal significant quantity claim 1 compound and to its suitable carrier or thinner.
5. antagonism or control cause the method for plant characteristic of disease fungi, and it comprises the location of seed, plant or the seed of compound administration to the plant of the claim 1 of fungicidal significant quantity, plant or soil or any other plant-growth media.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0326331A2 (en) * 1988-01-29 1989-08-02 DowElanco Substituted quinolines and cinnolines
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