CN1228084A - 4-substituted quinoline derivatives having fungicidal activity - Google Patents
4-substituted quinoline derivatives having fungicidal activity Download PDFInfo
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- CN1228084A CN1228084A CN97196937A CN97196937A CN1228084A CN 1228084 A CN1228084 A CN 1228084A CN 97196937 A CN97196937 A CN 97196937A CN 97196937 A CN97196937 A CN 97196937A CN 1228084 A CN1228084 A CN 1228084A
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-
- 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
-
- 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
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
This invention provides compounds of formula (1) wherein X is CR<5>, where R<5> is H, Cl or CH3; Y is CR<5> where R<5> is H, Cl, or Br; Z is O, S, SO, SO2, NR<6>, where R<6> is H, C1-C4 alkyl, C1-C4 acyl, CR<7>R<8>, where R<7> and R<8> are independently H, C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, C1-C4 acyl, CN, or OH, or R<7> and R<8> together combine to form a carbocyclic ring containing four to six carbon atoms; V is CR<7>R<8> where R<7> and R<8> are independently H, C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, C1-C4 acyl, CN, optionally substituted phenoxy, halo C1-C4 alkyl, or OH, or R<7> and R<8> together combine to form a carbocyclic ring containing four to six carbon atoms; A is (a) a C1-C18 saturated or unsaturated straight or branched hydrocarbon chain, optionally including a hetero atom selected from O, S, SO, or SO2, and optionally substituted with halo, halo C1-C4 alkoxy, OH, or C1-C4 acyl; (b) C3-C8 cycloalkyl or cycloalkenyl; (c) a possibly substituted phenyl group; (d) a furyl group of formula (3); (e) a thienyl group; (f) a group of formula (5) or (5a); (g) a group selected from pyridyl or substituted pyridyl; (h) a group selected from pyrimidinyl or substituted pyrimidinyl; or (i) a group selected from 1-naphthyl, substituted 1-naphthyl, 4-pyrazolyl, 3-methyl-4-pyrazolyl, 1,3-benzodioxolyl, tricyclo[3.3.1.1(3,7)]dec-2-yl,1-(3-chlorophenyl)-1H-tetrazol-5-yl, pyridyl, substituted pyridyl, or an acid addition salt of a compound of formula (1), or an N-oxide of a compound of formula (1) where Y is CH. The compounds of formula (1) are plant fungicides.
Description
The invention provides the novel quinoline that the active 4-of plant sterilization replaces that has.The present invention also provides and has comprised composition and the mix product of one or more The compounds of this invention as active ingredient.Some mix product show synergy to phytopathogen.The present invention also provides sterilising method.
The invention provides the novel cpd of formula (1), the perhaps acid salt of formula (1) compound, perhaps wherein Y is the N-oxide compound of formula (1) compound of CH.
Wherein
X is CR
5, R
5Be H, Cl or CH
3
Y is CR
5 ', R
5 'Be H, Cl or Br;
Z is O, S, SO, SO
2, NR
6, R wherein
6Be H, C
1-C
4Alkyl, C
1-C
4Acyl group, CR
7R
8, R wherein
7And R
8Be H, C independently
1-C
4Alkyl, C
1-C
4Alkenyl, C
2-C
4Alkynyl group, C
1-C
4Acyl group, CN or OH, perhaps R
7With R
8Connect together and form the carbocyclic ring that contains 4-6 carbon atom;
R
1-R
4Be H, OH, NO independently
2, halogen, I, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, C
1-C
4Alkoxyl group, halo C
1-C
4Alkyl, halo C
1-C
4Alkoxyl group, or halo C
1-C
4Alkylthio, perhaps R
1With R
2Or R
2With R
3Connect together and form the carbocyclic ring that contains 4-6 carbon atom;
V is CR
7R
8, R wherein
7And R
8Be H, C independently
1-C
4Alkyl, C
1-C
4Alkenyl, C
2-C
4Alkynyl group, C
1-C
4Acyl group, CN can choose phenoxy group, the halo C of replacement wantonly
1-C
4Alkyl or OH, perhaps R
7With R
8Connect together and form the carbocyclic ring that contains the 4-6 carbon atom.
A is
(a) C
1-C
18The hydrocarbon chain of saturated or undersaturated straight or branched can include in this hydrocarbon chain and is selected from O, S, SO or SO
2Heteroatoms and can be randomly by halogen, halo C
1-C
4Alkoxyl group, OH or C
1-C
4Acyl substituted;
(b) C
3-C
8Cycloalkyl or cycloalkenyl group;
(c) phenyl of formula (2)
Wherein
R
9-R
13Be H, CN, NO independently
2, OH, halogen, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, C
2-C
4Alkanoyl, halo C
1-C
7Alkyl, hydroxyl C
1-C
7Alkyl, C
1-C
7Alkoxyl group, halo C
1-C
7Alkoxyl group, C
1-C
7Alkylthio, halo C
1-C
7The thiophenyl of the phenoxy group of the phenyl of alkylthio, phenyl, replacement, phenoxy group, replacement, thiophenyl, replacement, phenyl C
1-C
4Alkyl, substituted-phenyl C
1-C
4Alkyl, benzoyl, SiR
20R
21R
22Or OSiR
20R
21R
22, R wherein
20, R
21, R
22Be H, C
1-C
6The alkyl of straight or branched, phenyl or substituted-phenyl, prerequisite are R
20, R
21And R
22In at least one is not H; Perhaps R
11And R
12Or R
12And R
13Link up the formation carbocyclic ring; Precondition is if not all R
9-R
13Be H or F, so R
9-R
13In have at least two to be H;
(d) furyl of formula (3)
Wherein
R
14Be H, halogen, monochloromethyl, CN, NO
2, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, phenyl or C
1-C
4Alkoxyl group;
(e) thienyl of formula (4)
Wherein
R
15Be H, halogen, monochloromethyl, CN, NO
2, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, phenyl or C
1-C
4Alkoxyl group;
(f) formula (5) or group (5a)
Wherein
R
16Be H, halogen, monochloromethyl, CN, NO
2, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, phenyl, substituted-phenyl or C
1-C
4Alcoxyl, J are that N or CH and G are O, NR
19Or CH, precondition is or J is that N or G are NR
19, R wherein
19Be H, C
1-C
4Alkyl, C
1-C
4Acyl group, benzenesulfonyl, or substituted benzene alkylsulfonyl;
(g) be selected from the group of pyridyl or substituted pyridinyl;
(h) be selected from the group of pyrimidyl or substituted pyrimidyl; Or
(i) be selected from 1-naphthyl, 4-pyrazolyl, the 3-methyl-4-pyrazolyl, 1 of 1-naphthyl, replacement, 3-benzo dioxolane base, three rings [3.3.1.1 (3,7)] last of the ten Heavenly stems-2-base, 1-(3-chloro-phenyl-)-1H-tetrazolium-5-base, the group of pyridyl, substituted pyridinyl.
In this application, outer except as otherwise noted all temperature are all degree centigrade providing, and all percentage number averages are weight percentage.
No matter term halogen is to use separately or unite use with other term, all refers to F, Cl or Br.
Term " alkyl " is meant straight chained alkyl.
Term " branched-chain alkyl " is meant that all comprise the alkyl isomer that specifies number carbon atom except the straight chain isomer.
Term " alkoxyl group " is meant the alkoxyl group of straight or branched.
Term " haloalkyl " is meant the straight or branched alkyl that is replaced by one or more halogen atoms.
Term " halogenated alkoxy " is meant the alkoxyl group that is replaced by one or more halogen atoms.
Term " halogenated alkylthio " is meant the alkylthio of the straight or branched that is replaced by one or more halogen atoms.
Term " acyl group " is meant the alkanoyl of straight or branched.
Term " substituted-phenyl " be meant by at the most 3 be selected from halogen, C
1-C
10Alkyl, side chain C
3-C
6Alkyl, halo C
1-C
7Alkyl, hydroxyl C
1-C
7Alkyl, C
1-C
7Alkoxyl group, halo C
1-C
7Alkoxyl group, phenoxy group, phenyl, NO
2, OH, CN, C
1-C
4The phenyl that the substituting group of alkanoyloxy or benzyloxy replaces.
Term " substituent phenoxy " be meant by at the most 3 be selected from halogen, C
1-C
10Alkyl, side chain C
3-C
6Alkyl, halo C
1-C
7Alkyl, hydroxyl C
1-C
7Alkyl, C
1-C
7Alkoxyl group, halo C
1-C
7Alkoxyl group, phenoxy group, phenyl, NO
2, OH, CN, C
1-C
4The phenoxy group that the substituting group of alkanoyl oxygen base or benzyloxy replaces.
Term " substituted benzene sulfenyl " is meant and 3 is selected from halogen, C outward at the most
1-C
10Alkyl, side chain C
3-C
6Alkyl, halo C
1-C
7Alkyl, hydroxyl C
1-C
7Alkyl, C
1-C
7Alkoxyl group, halo C
1-C
7Alkoxyl group, phenoxy group, phenyl, NO
2, OH, CN, C
1-C
4The thiophenyl that the substituting group of alkanoyl oxygen base or benzyloxy replaces.
Term " substituted benzene alkylsulfonyl " be meant by at the most 3 be selected from halogen, I, C
1-C
10Alkyl, C
3-C
6Branched-chain alkyl, halo C
1-C
7Alkyl, hydroxyl C
1-C
7Alkyl, C
1-C
7Alkoxyl group, halo C
1-C
7Alkoxyl group, phenoxy group, phenyl, NO
2, OH, CN, C
1-C
4The benzenesulfonyl that the substituting group of alkanoyl oxygen base or benzyloxy replaces.
Term " aliphatic unsaturated hydrocarbon " is meant the hydrocarbon chain that comprises 1-3 Multiple Bonds.
Term " carbocyclic ring " is meant the saturated or unsaturated ring that contains 4-7 carbon atom.
The all compounds of the present invention all have fungicidal activity, and some compounds is owing to have higher efficient or be easy to synthesize etc. former thereby preferred by the present invention.The compound of these preferred class comprises those compounds that the situation that wherein replaces of above-mentioned formula (1) is following
X is CR
5, R wherein
5Be H;
Y is CR
5, R wherein
5Be H;
Z is O
R
1-R
4Be H, halogen or C independently
1-C
4Alkyl, perhaps more preferably halogen;
V is CH or C
1-C
4Alkyl and
A is the phenyl of above-mentioned formula (2), wherein R
9R
13Be halogen, C independently
1-C
4Alkyl or halo C
1-C
7Alkyl; The phenyl of perhaps more preferably above-mentioned formula (2), wherein R
9R
13Be halogen independently; Pyridyl or substituted pyridinyl; The perhaps pyrimidyl of pyrimidyl or replacement.
The compound that has been found that formula (1) can be prevented and treated fungi, especially phytopathogen.When being used to processing or control fungal diseases of plants, The compounds of this invention can be applied to seed or plant with disease amount of suppression and the acceptable amount of plant.Term used herein " disease suppress and the acceptable amount of plant " thus being meant to kill or suppress Plant diseases with The compounds of this invention obtains the prevention effect of being satisfied with, but plant is not had remarkable toxic amount.This amount generally is about 1～1000ppm, preferred 10～500ppm.The definite concentration of required compound changes with the formulation of fungal disease, the employing of control, application process, specific floristics, weather condition etc.Compound of the present invention also can be used for protecting the cereal of storage and other non-plant place to make it not encroached on by fungi.
The test of carrying out is the germ-killing efficiency that is used to measure The compounds of this invention below.
Have been found that compound of the present invention can prevent and treat fungi, especially phytopathogen.When being used for the processing of fungal diseases of plants, described compound suppresses with disease and the acceptable amount of plant is applied to plant.Terminology used here " disease suppress and the acceptable amount of plant " thus be meant that The compounds of this invention kills or suppresses Plant diseases acquisition Satisfactory Control effect, but plant is not had remarkable toxic amount.This amount generally is about 1～1000ppm, preferably 10～500ppm.The definite concentration of required compound changes with the formulation of fungal disease, the employing of control, application process, specific floristics, weather condition etc., and suitable amount of application scope generally is about 0.10～4lb/A.Compound of the present invention also can be used for protection storage cereal and other non-plant place is not encroached on by fungi.
Being listed in the experiment of carrying out in the laboratory down is the fungicidal efficient that is used for determining The compounds of this invention.
The described test compounds that is mixed is used for foliage spray and uses.Phytopathogen below adopting and their corresponding plant tests.
Expression host below the pathogenic bacteria in the form
Erysiphe graminis tritici PMW wheat
(wheat powdery mildew)
The basin dress of wheat C.V.Monon sowing at the peat base of few soil mixed in the soil (" Metromix "), and place the greenhouse to cultivate.The wheat seeding that was in for 1.5 leaf phases is used for test.Compound formulation is by industrial raw material being dissolved in the acetone preparation, carrying out serial dilution then to obtain the required ratio of using in acetone.Obtain final processing volume by the 0.011%Triton X-100 aqueous solution that adds 9 volumes, obtain having the test soln of 10% acetone and 0.01%TritonX-100.A test rate is 400,100,25 and 6.25ppm.
When the heavy body foliage applying, spray plant under the condition of about 138KPa to drop dirty (use two subtend fog systems (two opposing Spraying Systems), 1/4JAUPM air auto spraying mouth sprays).Wheat powdery mildew (E.graminis f.sp.tritici) test inoculum produces in the maternal plant body in the greenhouse.After sprinkling is used 24 hours, spore is dispensed onto the test plant inoculation test plant that comes up by maternal plant.
After the inoculation, test plant was cultivated 7 days the disease zoon on untreated adjoining tree in the greenhouse.Inoculate after 7 days the disease sickness rate on the eye estimate leaf.
Following form has provided the representative activity of compound in these experiments of the present invention.Test compound is prevented and treated the effect of disease and is represented with following grade.
NT=does not test this microorganism
O=0% control
-=1-49% control
+=50-100% control
| Compound | Use ratio (ppm) | ???PMW |
| ????1 | ????400 | ????+ |
| ????1 | ????100 | ????+ |
| ????1 | ????25 | ????+ |
| ????1 | ????6.25 | ????+ |
| ????2 | ????400 | ????+ |
| ????2 | ????100 | ????- |
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| ????2 | ????6.25 | ????- |
| ????3 | ????400 | ????+ |
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| ????5 | ????400 | ????- |
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| ????6 | ????400 | ????- |
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| ????7 | ????400 | ????+ |
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| ????7 | ????6.25 | ????- |
| ????8 | ????400 | ????- |
| ????8 | ????100 | ????- |
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| ????8 | ????6.25 | ????- |
| ????9 | ????400 | ????+ |
| ????9 | ????100 | ????+ |
| ????9 | ????25 | ????+ |
| ????9 | ????6.25 | ????- |
| ????10 | ????400 | ????+ |
| ????10 | ????100 | ????+ |
| ????10 | ????25 | ????+ |
| ????10 | ????6.25 | ????- |
| ????11 | ????400 | ????- |
| ????11 | ????100 | ????- |
| ????11 | ????25 | ????- |
| ????11 | ????6.25 | ????- |
| ????12 | ????400 | ????+ |
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| ????12 | ????25 | ????+ |
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| ????13 | ????400 | ????+ |
| ????13 | ????100 | ????+ |
| ????13 | ????25 | ????- |
| ????13 | ????6.25 | ????- |
| ????14 | ????400 | ????- |
| ????14 | ????100 | ????- |
| ????14 | ????25 | ????- |
| ????14 | ????6.25 | ????- |
| ????15 | ????400 | ????+ |
| ????15 | ????100 | ????+ |
| ????15 | ????25 | ????- |
| ????15 | ????6.25 | ????- |
| ????16 | ????400 | ????+ |
| ????16 | ????100 | ????+ |
| ????16 | ????25 | ????+ |
| ????16 | ????6.25 | ????- |
| ????17 | ????400 | ????+ |
| ????17 | ????100 | ????+ |
| ????17 | ????25 | ????+ |
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| ????18 | ????400 | ????+ |
| ????18 | ????100 | ????+ |
| ????18 | ????25 | ????+ |
| ????18 | ????6.25 | ????+ |
| ????19 | ????400 | ????+ |
| ????19 | ????100 | ????+ |
| ????19 | ????25 | ????+ |
| ????19 | ????6.25 | ????- |
| ????20 | ????400 | ????+ |
| ????20 | ????100 | ????+ |
| ????20 | ????25 | ????+ |
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| ????21 | ????400 | ????+ |
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| ????22 | ????400 | ????+ |
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| ????22 | ????25 | ????- |
| ????22 | ????6.25 | ????- |
| ????23 | ????400 | ????+ |
| ????23 | ????100 | ????+ |
| ????23 | ????25 | ????- |
| ????23 | ????6.25 | ????- |
| ????24 | ????400 | ????+ |
| ????24 | ????100 | ????+ |
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| ????24 | ????6.25 | ????- |
| ????25 | ????400 | ????- |
| ????25 | ????100 | ????- |
| ????25 | ????25 | ????- |
| ????25 | ????6.25 | ????- |
| ????26 | ????400 | ????+ |
| ????26 | ????100 | ????+ |
| ????26 | ????25 | ????- |
| ????26 | ????6.25 | ????- |
| ????27 | ????400 | ????+ |
| ????27 | ????100 | ????+ |
| ????27 | ????25 | ????+ |
| ????27 | ????6.25 | ????- |
| ????28 | ????400 | ????+ |
| ????28 | ????100 | ????- |
| ????28 | ????25 | ????- |
| ????28 | ????6.25 | ????- |
| ????29 | ????400 | ????- |
| ????29 | ????100 | ????- |
| ????29 | ????25 | ????- |
| ????29 | ????6.25 | ????- |
| ????30 | ????400 | ????- |
| ????30 | ????100 | ????- |
| ????30 | ????25 | ????- |
| ????30 | ????6.25 | ????- |
| ????31 | ????400 | ????- |
| ????31 | ????100 | ????- |
| ????31 | ????25 | ????- |
| ????31 | ????6.25 | ????- |
| ????32 | ????400 | ????- |
| ????32 | ????100 | ???- |
| ????32 | ????25 | ???- |
| ????32 | ????6.25 | ???- |
| ????33 | ????400 | ???+ |
| ????33 | ????100 | ???+ |
| ????33 | ????25 | ???- |
| ????33 | ????6.25 | ???- |
| ????34 | ????400 | ???+ |
| ????34 | ????100 | ???+ |
| ????34 | ????25 | ???+ |
| ????34 | ????6.25 | ???+ |
| ????35 | ????400 | ???+ |
| ????35 | ????100 | ???+ |
| ????35 | ????25 | ???+ |
| ????35 | ????6.25 | ???+ |
| ????36 | ????400 | ???+ |
| ????36 | ????100 | ???+ |
| ????36 | ????25 | ???+ |
| ????36 | ????6.25 | ???- |
| ????37 | ????400 | ???+ |
| ????37 | ????100 | ???+ |
| ????37 | ????25 | ???+ |
| ????37 | ????6.25 | ???- |
| ????38 | ????400 | ???+ |
| ????38 | ????100 | ???+ |
| ????38 | ????25 | ???- |
| ????38 | ????6.25 | ???- |
| ????39 | ????400 | ???- |
| ????39 | ????100 | ???- |
| ????39 | ????25 | ???- |
| ????39 | ????6.25 | ???- |
| ????40 | ????400 | ???- |
| ????40 | ????100 | ???- |
| ????40 | ????25 | ???- |
| ????40 | ????6.25 | ???- |
| ????41 | ????400 | ???- |
| ????41 | ????100 | ???- |
| ????41 | ????25 | ???- |
| ????41 | ????6.25 | ???- |
| ????42 | ????400 | ???- |
| ????42 | ????100 | ???- |
| ????42 | ????25 | ???- |
| ????42 | ????6.25 | ???- |
| ????43 | ????400 | ???+ |
| ????43 | ????100 | ???- |
| ????43 | ????25 | ???- |
| ????43 | ????6.25 | ???- |
| ????44 | ????400 | ???- |
| ????44 | ????100 | ???- |
| ????44 | ????25 | ???- |
| ????44 | ????6.25 | ???- |
| ????45 | ????400 | ???- |
| ????45 | ????100 | ???- |
| ????45 | ????25 | ???- |
| ????45 | ????6.25 | ???- |
| ????46 | ????400 | ???- |
| ????46 | ????100 | ???- |
| ????46 | ????25 | ???- |
| ????46 | ????6.25 | ???- |
| ????47 | ????400 | ???- |
| ????47 | ????100 | ???- |
| ????47 | ????25 | ???- |
| ????47 | ????6.25 | ???- |
| ????48 | ????400 | ???- |
| ????48 | ????100 | ???- |
| ????48 | ????25 | ???- |
| ????48 | ????6.25 | ???- |
| ????49 | ????400 | ???- |
| ????49 | ????100 | ???- |
| ????49 | ????25 | ???- |
| ????49 | ????6.25 | ???- |
| ????50 | ????400 | ???- |
| ????50 | ????100 | ???+ |
| ????50 | ????25 | ???- |
| ????50 | ????6.25 | ???- |
| ????51 | ????400 | ???- |
| ????51 | ????100 | ???- |
| ????51 | ????25 | ???- |
| ????51 | ????6.25 | ???- |
| ????52 | ????400 | ???- |
| ????52 | ????100 | ???- |
| ????52 | ????25 | ???- |
| ????52 | ????6.25 | ???- |
| ????53 | ????400 | ???+ |
| ????53 | ????100 | ???+ |
| ????53 | ????25 | ???+ |
| ????53 | ????6.25 | ???+ |
| ????54 | ????400 | ???+ |
| ????54 | ????100 | ???- |
| ????54 | ????25 | ???- |
| ????54 | ????6.25 | ???- |
| ????55 | ????400 | ???+ |
| ????55 | ????100 | ???+ |
| ????55 | ????25 | ???+ |
| ????55 | ????6.25 | ???+ |
| ????56 | ????400 | ???+ |
| ????56 | ????100 | ???+ |
| ????56 | ????25 | ???+ |
| ????56 | ????6.25 | ???- |
| ????57 | ????400 | ???+ |
| ????57 | ????100 | ???+ |
| ????57 | ????25 | ???+ |
| ????57 | ????6.25 | ???+ |
| ????58 | ????400 | ???+ |
| ????58 | ????100 | ???+ |
| ????58 | ????25 | ???+ |
| ????58 | ????6.25 | ???+ |
These compounds of the present invention prepare with known chemical process, and required starting raw material can be bought and obtain, or utilize standard method to be easy to synthesize, and certain methods wherein is disclosed in United States Patent (USP) U.S.5, in 145,843.Then, replace 4-toluquinoline derivative preparation formula (1) compound by handle corresponding 4-V with the derivative of suitable comprising-Z-A.
The embodiment of following unrestricted purpose is used for further explaining the present invention.
Embodiment 1
4-((4-fluorophenoxy) methyl)-8-chloroquinoline
Stir down, with 4-bromomethyl-8-chloro quinoline (0.8g, 3.11mmol) be dissolved in anhydrous THF (10mls) and add sodium hydride (0.15g, 60% the dispersion liquid in mineral oil, 6.23mmol).Stirring at room miscellany 15 minutes, and adding 4-fluorophenol (0.52g, 3.11mmol).The mixture stirred overnight at room temperature is also carried out aftertreatment and is obtained white solid product (0.46g, 51.2%), mp:144-5 ℃
Experimental value: C, 66.41; H, 3.67; N, 4.88%;
Calculated value: C, 66.87; H, 3.67; N, 4.88%.
Embodiment 2
4-(2-styryl)-7-chloroquinoline
With 4-bromo-7-chloro quinoline (24.3g, 0.1mol), vinylbenzene (12.0g, 0.125mol), three (o-tolyl) phosphine, (0.4g, 1.3mmol), acid chloride (0.2g, 0.89mol) and the miscellany of triethylamine (120mls) join in the pressurized vessel that 300ml stirs, and 120 ℃ of heating 17 hours.Cool off miscellany, remove by filter triethylamine hydrobromide, and wash solid with ethyl acetate (250ml).The pressure reducing and steaming solvent also is dissolved in resistates in the ethyl acetate (500ml).Gained solution with water and salt water washing, and use anhydrous sodium sulfate drying.Pressure reducing and steaming solvent and with the resistates ethyl acetate: the hexane recrystallization obtains orange solids product (13.5g, 51%), mp.120～122 ℃
Experimental value: C, 76.50; H, 4.62; N, 5.38%;
Calculated value: C, 76.84; H, 4.55; N, 5.27%;
Embodiment 3
4-((3-trifluoromethyl-2-pyridyloxy) methyl)-7-chloroquinoline
Stir down with 4-methylol-7-chloro quinoline (0.6g 3.12mmol) is dissolved among the anhydrous THF (20mls), and add sodium hydride (0.15g, 60% the dispersion liquid in mineral oil, 3.75mmol).Miscellany stirring at room 1 hour and add 2-chloro-3-5-flumethiazine (0.62g, 3.42mmol).The stirring of gained miscellany is spent the night and is carried out aftertreatment, obtains mp.125-7 ℃ of brown solid product (0.9g)
Experimental value: C, 56.68; H, 2.90; N, 8.17%;
Calculated value: C, 56.74; H, 2.98; N, 8.27%.
Embodiment 4
The 4-[1-[(4-fluorophenyl) oxygen base] ethyl]-5, the 7-dichloroquinoline
With bromine (15ml, 0.30mol) be dissolved in the acetonitrile (200ml) and be added drop-wise to 4-hydroxyl-5,7-dichloroquinoline (60g, 0.28mol) (Swiss Patent CH93-3640 931207) and triphenylphosphine (78ml, 0.30mol) in the suspension in acetonitrile (1L), about 3 hours of time spent.Placing response and stir 24 hours after, filter the collecting precipitation thing.Solids is suspended in water (1L) and the methylene dichloride (500ml) and with sodium bicarbonate neutralizes.When the approaching neutrality of water layer, extract repeatedly, and when pH10, obtain the extraction liquid of 5 * 500ml equal portions altogether at last, merge organic phase, dry (sal epsom) filters with silica gel plug, vacuum concentration to cumulative volume is 1L, heats until solid dissolving then and places crystallization 12 hours.Filtration obtains analytically pure product (46g, 65%), and concentrated mother liquor obtains spectroscopically pure product (14g, 20%, mp:131 ℃).
With 4-bromo-5,7-dichloroquinoline (5.7g, 21mmol), acid chloride (II) (0.93g, 4.2mmol), three (o-tolyl) phosphine (2.5g, 8.2mmol), vinylbenzene (5ml, 26.2mmol), cupric iodide (0.80g, 4.2mmol) and triethylamine (4ml, 28mmol) vlil in acetonitrile (41ml) is 3 hours.After being cooled to room temperature, use ethyl acetate diluting reaction miscellany, and filter with silica gel plug.This material is used for analysis and characterization (178mg, 242 ℃ of mp) on a small quantity.The gained solid is dissolved in methyl alcohol, the dichloromethane solution (1: 1,600ml) and be cooled to-78 ℃, in system, feed ozone till determining that by GCMS reaction has been finished.(5g, 600mmol) also placement is warm to room temperature, filters and use eluent methylene chloride by silica gel plug to add thiocarbamide.The vacuum low-grade fever is removed and is desolvated until being settled out white solid.Collect the solid that is settled out several times and obtain required aldehyde (2.1g, 45% (two steps), mp.154 ℃).By obtain analyzing the sample of usefulness with re-crystallizing in ethyl acetate.
(100mg 0.44mmol) is dissolved in the toluene (6ml), and is cooled to 0 ℃ with resulting aldehyde.Be added dropwise to methylmagnesium-bromide (toluene/tetrahydrofuran solution of 1.4M), depleted up to detecting starting raw material by TLC.Reaction mixture dilutes and places with ethyl acetate (50ml) and 0.5NHCl (50ml) and makes it rise to room temperature.Organic layer is used 0.5N HCl (3 * 50ml) extractions again.Combining water layer and with sodium bicarbonate neutralization, (4 * 50ml) extractions are with organic phase drying (sal epsom), filter and concentrate and obtain purified product (101mg, 94%, mp, 112 ℃) to use ethyl acetate then.
With purified diethyl azodiformate (0.30ml, 1.9mmol) join secondary alcohol (secondary alcohol) (300mg, 1.25mmol), triphenylphosphine (600mg, 2.3mmol) and 4-fluorophenol (200mg, 1.7mmol) in the solution in chloroform (6ml), 15 minutes times spent.To react and stir 2 hours, vacuum concentration is also by middle pressure chromatogram purification (10: 1, heptane/ethyl acetate), and gained solid pentane recrystallization obtains phenoxy group-4-toluquinoline (325mg, 78%, mp101 ℃)
Embodiment 5
The 4-[(4-fluoroanilino) methyl]-5, the 7-dichloroquinoline
Stir down at electromagnetism, with 5, (500mg, 2.2mmol) (264mg 2.2mmol) mixes in 20ml benzene 7-dichloroquinoline-4-formaldehyde with the 4-fluoroaniline.Flask is equipped with the Dean-Stark water trap and reflux is spent the night.By the TLC monitoring reaction, show after 16 hours that reaction finishes.Vacuum is removed benzene, and with ethyl acetate/heptane recrystallization gained solid.Mp153 ℃ of productive rate: 0.5g (71%).
(600mg 1.9mmol) is dissolved in the 10ml ethanol with the product that obtains above.Under nitrogen protection, (90mg 2.4mmol) also at room temperature spends the night with the electromagnetism stirring reaction to add sodium borohydride.Finish until showing to react by the TLC monitoring reaction.The dilute with water reaction mixture is also used ethyl acetate extraction.The organic layer dried over mgso is filtered and vacuum-evaporation.Gained solid ethyl acetate/heptane recrystallization.Productive rate: 180mg (30%), mp166.5 ℃.
Embodiment 6
4-methylol-5, the 7-dichloroquinoline
With 4-bromo-5, the 7-dichloroquinoline (5.7g, 21mmol), acid chloride (II) (0.93g, 4.2mmol), three (o-tolyl phosphine) (2.5g, 8.2mmol), vinylbenzene (5ml, 26.2mmol), cupric iodide (0.80g, 4.2mmol) and triethylamine (16ml, 115mmol) vlil in acetonitrile (41ml) is 3 hours, be cooled to room temperature after, reaction mixture is with ethyl acetate dilution and with dilute hydrochloric acid and salt water washing.Organic layer drying (MgSO
4) and the concentrated white solid that obtains.The gained solid be dissolved in the methanol/dichloromethane solution (1: 1,400ml) and be cooled to-78 ℃, in system, feed ozone until determine complete reaction by GCMS till.(5.0g, 600mmol) also placement rises to room temperature to add thiocarbamide.Reaction mixture filters with the methylene dichloride dilution and by silica gel plug, with ethanol/methylene (1: 1) drip washing.Solution is cooled to 0 ℃ and add solid sodium borohydride, one hour time spent.Till determining that by GCMS reaction finishes.Reaction stops and washing with 1N hydrochloric acid.Combining water layer also filters with tampon, and with the sodium bicarbonate neutralization, solid collected by filtration, dry air obtain required product (2.8g, purity＞80%) obtains analyzing usefulness through the ethyl acetate/methanol recrystallization sample (mp196 ℃) afterwards.
Embodiment 7
4-methylol-7-chloroquinoline
In the 200ml stainless steel autoclave, add 4-bromo-7-chloroquinoline (1.2g, 5.0mmol) (Canadian Patent CA94-2133620 941004), chlorination two (triphenylphosphine) palladium (0.1g), triethylamine (3ml) and ethanol (40ml) also are forced into 200psi with carbon monoxide, reactor heated 12 hours down at 120 ℃, cooling, and emptying.Remove solid with diatomite filtration, the vacuum concentration mother liquor.Resistates is dissolved in the chloroform (50ml), water (3 * 50ml), saturated brine (50ml) washing and dry (Na
2SO
4), filter and remove to desolvate and stay brown liquid (1.3g), with containing 1vol%CH
3The CH of CN
2Cl
2As eluent, purification by flash chromatography obtains colourless syrup shape product, and is solidified into waxy solid.This solid is dissolved in (50ml) in the methyl alcohol, and 2 hours times spent added sodium borohydride till judging that by TLC reaction is finished.The dilute with water reaction mixture is also used the 1N hcl acidifying, then with the sodium bicarbonate neutralization, reclaims the solid of gained after filtration, is dissolved in the ethyl acetate and dry (MgSO
4).Filter and concentrate and obtain (mp:160 ℃ of required compound; 0.66g, 68% (two steps)).
Embodiment 8
8-chloro-4-toluquinoline
(200g 1.56mol) is dissolved in the 600ml ethanol, and bubbling fed exsiccant HCl gas 10 minutes, obtains the hydrochloride of dichlorphenamide bulk powder with the 2-chloroaniline buied.(130g, 0.793mol), (25.7g, 0.095mol), (10.9g is 0.0799mol) with 500ml 2B ethanol for Zinc Chloride Anhydrous for ferric chloride hexahydrate to add 2-chloroaniline hydrochloride in another flask.Mixture heating up to 60 ℃ reaction 10 minutes.In about 1 hour, drip 1,3,3-trimethoxy butane.Then miscellany is refluxed also at room temperature to place in 2 hours and spend the night.The distillation remove most ethanol and with 25% sodium hydroxide solution with resistates furnishing alkalescence.The cooling reaction mixture.Filter, and use the toluene wash filter plate.Be concentrated into toluene dried mutually.Product with methylene dichloride/pentane recrystallization obtain the spectroscopically pure sample (mp:110 ℃, 37.0g, total recovery 25%).
Embodiment 9
4-brooethyl-8-chloroquinoline
With 8-chloro-4-methyl-quinoline (20.0g, 0.113mol) and N-bromosuccinimide (20.0g 0.113mol) is dissolved in the anhydrous tetracol phenixin of 200mol and under nitrogen protection miscellany was stirred 3 hours.Simultaneously with 250 watts of high strength sun lamp irradiations.Solution is cooled to room temperature, filters and be evaporated to dried, resistates is crossed silicagel column, with ethyl acetate/pentane drip washing, obtains brooethyl-4-toluquinoline (10.8g, productive rate: 37.4%; Mp.92 ℃)
Embodiment 10
7-chloro-α-(trifluoromethyl)-4-quinoline methanol
Under nitrogen protection; (1.00g 5.22mmol) is dissolved in the tetrahydrofuran solution of 0.5M trimethylammonium (trifluoromethyl) silane of 12.5ml and with gained solution and is cooled to 0 ℃ with 4-aldehyde radical-7-chloroquinoline in the 100ml round-bottomed flask of crossing with oven drying, nitrogen purge.Stir down, add solid form fluoridize tetra-n-butyl ammonium Trihydrate (0.014g, 0.052mmol).And allow miscellany in about two hours, slowly be warming up to room temperature, (hexane: ethyl acetate/2: 1) the demonstration starting raw material is exhausted thin-layer chromatography at this moment.Reaction mixture is cooled to 0 ℃ and add 10% aqueous hydrochloric acid (3ml), at room temperature stirs miscellany and show that up to thin-layer chromatography trimethyl silyl ether decomposes (1h) fully.Reaction mixture distributes between saturated sodium bicarbonate and ethyl acetate, and layering is also used in addition a ethyl acetate extraction with water layer.Merge organic layer and dry (MgSO
4), filter and be concentrated into dried.(hexane: ethyl acetate/2: 1) obtain 7-chloro-α-(trifluoromethyl)-4-quinoline methanol (1.32g, 96%), product is a yellow solid with the fast silica gel chromatogram purifying.The sample of analyzing usefulness is by using ethyl acetate: hexane recrystallization preparation (mp161 ℃).
Embodiment 11
5-fluoro-2-(methylsulfonyl) pyrimidine
In the 250ml round-bottomed flask of crossing, with iodate N-(2,3 with oven drying, nitrogen purge, 3-three fluoro-1-propenyl) trimethyl ammonium (10.0g, 35.6mmol) (tetrahedron communication [Tetrahedron Lett.1995,36 (9), 1527]) be dissolved in the 70ml acetonitrile.Stir down, (15.6g, 213mmol), flask is loaded onto reflux exchanger and was stirred 1 hour under nitrogen protection in 75-80 ℃ to add diethylamine with syringe.Miscellany is cooled to room temperature and under agitation add 2-methyl-2-sulfo-pseudo-urea sulfuric ester (19.8g, 71.2mmol) and sodium methoxide (3.80g.71.2mmol, 15ml 25% methanol solution), gained reaction mixture reflux 6 hours.The refrigerative reaction mixture is poured in the water into standing demix.(3 * 50ml), the merging organic phase is drying (Na also with dichloromethane extraction for water
2SO
4), filter and be concentrated into small volume.Fast silica gel chromatogram purifying (hexane: ethyl acetate/10: 1), obtain volatile 5-fluoro-2-(thiomethyl) pyrimidine, in the 500ml round-bottomed flask it is dissolved in the 100ml methylene dichloride immediately, (21.6g 125mmol) handles with the 3-chloroperoxybenzoic acid under 0 ℃ and the condition that stirs.Stir under the room temperature after 15 hours, through thin-layer chromatography (hexane: ethyl acetate/1: 2) judge, after oxidizing reaction finishes, in reaction mixture impouring saturated sodium bicarbonate, standing demix, the water dichloromethane extraction washs the organic layer that merges and dry (Na with saturated sodium bicarbonate
2SO
4), filter and concentrate.(hexane: ethyl acetate/1: 2), (product is a colorless oil to the fast silica gel chromatogram purifying for 4.3g, 68% (by iodate N-(2,3,3-three fluoro-1-propenyl) trimethyl ammonium meter) to obtain 5-fluoro-2-(methylsulfonyl) pyrimidine.
Ultimate analysis (C
5H
5F
1N
2O
2S):
Calculated value: C, 34.09; H, 2.86; N, 15.9; S, 18.2;
Experimental value: C, 34.09; H, 2.79; N, 15.81; S, 18.3.
Embodiment 12
7-chloro-4-[2,2,2-three fluoro-1-[(5-fluoro-2-pyrimidyl) the oxygen base]
Ethyl] quinoline
Under nitrogen protection, in the 25ml round-bottomed flask of crossing with oven drying, nitrogen purge, (0.25g 0.96mmol) is dissolved in the 5ml tetrahydrofuran (THF), and gained solution is cooled to 0 ℃ with 7-chloro-α-(trifluoromethyl)-4-quinoline methanol.Stir down-inferior property all adds NaH (0.042g, 1.1mmol, 60% decomposed solution in mineral oil).After 15 minutes, with syringe Dropwise 5-fluoro-2-(methylsulfonyl) pyrimidine (0.17g, the 0.96mmol) solution in tetrahydrofuran (THF) (2.5ml), about 5 minutes of time spent.The flask and the syringe that contain sulfone in addition again with the drip washing of 2ml tetrahydrofuran (THF).Milky solution is warming up to room temperature, and stirs 15 hours.(hexane: ethyl acetate/1: 1) the demonstration starting raw material is exhausted thin-layer chromatography at this moment.Reaction mixture distributes between water and ethyl acetate, and standing demix is again with the organic layer MgSO of other a ethyl acetate extraction water layer, merging
4Dry.Filtration also is concentrated into dried.The fast silica gel chromatogram purifying (hexane: ethyl acetate/2: 1), obtain 7-chloro-4-[2,2,2-three fluoro-1-[(5-fluoro-2-pyrimidyl) the oxygen base] ethyl] quinoline (0.32g, 94%), product is a white solid.The sample of analyzing usefulness is by the preparation of hexane recrystallization.(mp?92℃)。
Listed the compound of formula (1) in the following form, they all are according to being similar to the prepared in various methods shown in the previous embodiment.
| Compound number | R 1 -R 4 | ? X | ? Y | ? V | ? Z | ??? A | ?? m.p??(℃) |
| ?1 | ?7-Cl | ?CH | ?CH | CHCH 3 | ?O | The 4-fluorophenyl | 104-106 |
| ?2 | ?7-Cl | ?CH | ?CH | CHC 6H 13 | ?O | The 4-fluorophenyl | 38-40 |
| ?3 | ?7-Cl | ?CH | ?CH | CHCN | ?O | The 4-fluorophenyl | 118-123 |
| ?4 | ?7-Cl | ?CH | ?CH | CHCH-CH 2 | ?O | The 4-fluorophenyl | 186-190 |
| ?5 | ?7-Cl | ?CH | ?CH | CH 2 | ?O | 2,5-three fluoro-methyl-6-pyridyl | 83-85 |
| ?6 | ?7-Cl | ?CH | ?CH | CH 2 | ?O | 4,6-methoxyl group-2-pyrimidyl | 134-136 |
| ?7 | ?5，7- ?diCl | ?CH | ?CH | CH 2 | ?O | 2-trifluoromethyl-6-pyridyl | 108.1- 110.1 |
| ?8 | ?5，7- ?diCl | ?CH | ?CH | CH 2 | ?O | 4-methoxyl group-6-methyl-2-pyrimidyl | 166-167 |
| ?9 | ?7-Cl | ?CH | ?CH | CH 2 | ?O | 4-methoxyl group-6-methyl-2-pyrimidyl | 114-116 |
| ?diCl | |||||||
| ?54 | ?H | ?CH | ?CH | ?CH 2 | ?O | The 4-fluorophenyl | 111-113 |
| ?55 | ?5，7- ?diCl | ?CH | ?CH | ?CH 2 | ?N | The 4-fluorophenyl | 167 |
| ?56 | ?5，7- ?diCl | ?CH | ?CH | ?CH 2 | ?O | 2-trifluoromethyl-phenyl | 145-146 |
| ?57 | ?5，7- ?diCl | ?CH | ?CH | ?CH 2 | ?O | The 2,4 difluorobenzene base | 154-156 |
| ?58 | ?5，7- ?diCl | ?CH | ?CH | ?CH 2 | ?O | The 4-fluorophenyl | 133-134 |
Compound of the present invention is to use with the form of composition, and this also is an important embodiment of the present invention, and composition comprises acceptable inert support on the compound of one or more formulas (1) and the phytology.Described composition also can randomly comprise the mixed agent with fungicidal activity, and it comprises compound of at least 1% one or more formulas (1) and other sterilant.
The present composition or concentrate formulation are scattered in the water for using, or pulvis or granula, and need not further processing can use.These compositions are according to the preparation of the ordinary method of field of agrochemicals.Because it contains compound of the present invention, so be novel and significant.Yet, will provide some descriptions of present composition preparation below, can prepare any required composition at an easy rate to guarantee agricultural agent teacher.
The compound dispersion liquid of using is aqueous suspension or the emulsion by the concentrate formulation preparation of described compound mostly.But the solid of the outstanding property of this water-soluble, water or emulsification preparation or so-called wettable powder, or the liquid of so-called missible oil or aqueous suspension.Wettable powder (it can be compacted and form water-dispersible granules) comprises active compound, inert support and surface-active tight miscellany.The concentration of active compound normally about 10%～90%.Inert support is selected from attapulgite, polynite, diatomite usually, or pure silicate.Effectively tensio-active agent (content account for greatly wettable powder 0.5%～10%) can be sulfonated lignin, naphthalenesulfonate, alkylbenzene sulfonate, alkyl-sulphate and non-from surfacant, for example ethylene oxide adduct of alkylphenol.
The missible oil of described compound comprises the compound of conventional concentration, for example accounts for 10%～50% of liquid greatly, and compound is dissolved in inert support, inert support or solvent that can be miscible with water, or organic solvent miscellany that can be miscible with water, and emulsifying agent.Appropriate organic solvent comprises aromatic substance, and especially the high boiling point naphthalene belongs to and olefinic fraction such as heavy aromatics petroleum naphtha in the petroleum cuts, also can use other organic solvent, for example: the terpenes solvent comprises rosin derivative, aliphatic ketone, as pimelinketone and compound alcohol, as cellosolvo.The suitable emulsifying agent that is used for missible oil is selected from conventional nonionogenic tenside, As mentioned above those.
Aqueous suspension comprises the suspension of the water-fast compound of the present invention, and the concentration that is approximately 5%-50% with scope is scattered in the water-bearing media.Suspension prepares by acutely sneaking in the medium that comprises water and tensio-active agent with described compound fine grinding and with it, and wherein tensio-active agent is selected from type as indicated above equally.Also can add inert component (as inorganic salt, synthetic or natural glue) to increase the density and the viscosity of water-bearing media.Usually effective means is described compound is ground simultaneously and to mix by preparing moisture miscellany, and is placed on (as sand mill, ball milling (ball mill) or piston-type homogenizer) homogenizing in the suitable utensil.
Described compound can also be used with the form of granule composition, and it is particularly suitable for soil application.Granular preparation comprises about 0.5%～10% described compound usually, is scattered in mainly in the inert support of being made up of the cheap material of clay or analogue.This composition according to the preparation of following method, is about to described compound and is dissolved in the suitable solvent usually, and it is spread loose to having formed in advance on the particulate vector of suitable particles size, and wherein the granular size scope is about 0.5～3mm.This composition can also be mixed by following method, is about to described carrier and compound and makes dough or mashed prod, obtains required granule thereby pulverize then with drying.
The pulvis that comprises described compound can be simply by closely mixing the described compound of powder type and the suitable agricultural carrier of powdery with preparation, and described agricultural carrier for example is kaolin, levigated volcanics etc.Comprise about 1%～10% described compound in the general pulvis.
Claims (14)
1. the compound of formula (1), the perhaps acid salt of formula (1) compound, perhaps wherein Y is the N-oxide compound of formula (1) compound of CH
Wherein
X is CR
5, R
5Be H, Cl or CH
3
Y is CR
5 ', R
5 'Be H, Cl or Br;
Z is O, S, SO, SO
2, NR
6, R wherein
6Be H, C
1-C
4Alkyl, C
1-C
4Acyl group, CR
7R
8, R wherein
7And R
8Be H, C independently
1-C
4Alkyl, C
1-C
4Alkenyl, C
2-C
4Alkynyl group, C
1-C
4Acyl group, CN or OH, or R
7With R
8Connect together and form the carbocyclic ring that contains 4-6 carbon atom;
R
1-R
4Be H, OH, NO independently
2, halogen, I, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, C
1-C
4Alkoxyl group, halo C
1-C
4Alkyl, halo C
1-C
4Alkoxyl group, or halo C
1-C
4Alkylthio, perhaps R
1With R
2Or R
2With R
3Connect together and form the carbocyclic ring that contains 4-6 carbon atom;
V is CR
7R
8, R wherein
7And R
8Be H, C independently
1-C
4Alkyl, C
1-C
4Alkenyl, C
2-C
4Alkynyl group, C
1-C
4Acyl group, CN can choose phenoxy group, the halo C of replacement wantonly
1-C
4Alkyl or OH, perhaps R
7With R
8Connect together and form the carbocyclic ring that contains the 4-6 carbon atom;
A is
(a) C
1-C
18Saturated or undersaturated straight or branched hydrocarbon chain can randomly include in this hydrocarbon chain and is selected from O, S, SO or SO
2Heteroatoms and can be randomly by halogen, halo C
1-C
4Alkoxyl group, OH or C
1-C
4Acyl substituted;
(b) C
3-C
8Cycloalkyl or cycloalkenyl group;
(c) phenyl of formula (2)
Wherein
R
9-R
13Be H, CN, NO independently
2, OH, halogen, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, C
2-C
4Alkanoyl, halo C
1-C
7Alkyl, hydroxyl C
1-C
7Alkyl, C
1-C
7Alkoxyl group, halo C
1-C
7Alkoxyl group, C
1-C
7Alkylthio, halo C
1-C
7The phenoxy group of alkylthio, phenyl, substituted-phenyl, phenoxy group, replacement, thiophenyl, substituted benzene sulfenyl, phenyl C
1-C
4Alkyl, substituted-phenyl C
1-C
4Alkyl, benzoyl, SiR
20R
21R
22Or OSiR
20R
21R
22, R wherein
20, R
21And R
22Be H, C
1-C
6The alkyl of straight or branched, phenyl or substituted-phenyl, prerequisite are R
20, R
21And R
22In at least one is not H; Perhaps R
11And R
12Or R
12And R
13Form carbocyclic ring altogether; Precondition is if not all R
9-R
13Be H or F, so R
9-R
13In have at least two to be H;
(d) furyl of formula (3)
Wherein
R
14Be H, halogen, monochloromethyl, CN, NO
2, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, phenyl or C
1-C
4Alkoxyl group;
(e) thienyl of formula (4)
Wherein
R
15Be H, halogen, monochloromethyl, CN, NO
2, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, phenyl or C
1-C
4Alkoxyl group;
(f) formula (5) or group (5a)
Wherein
R
16Be H, halogen, monochloromethyl, CN, NO
2, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, phenyl, substituted-phenyl or C
1-C
4Alkoxyl group, J are that N or CH and G are O, NR
19Or CH, precondition is or J is that N or G are NR
19, R wherein
19Be H, C
1-C
4Alkyl, C
1-C
4Acyl group, benzenesulfonyl or substituted benzene alkylsulfonyl;
(g) be selected from the group of pyridyl or substituted pyridinyl;
(h) be selected from the group of pyrimidyl or substituted pyrimidyl; Or
(i) be selected from 1-naphthyl, 4-pyrazolyl, the 3-methyl-4-pyrazolyl, 1 of 1-naphthyl, replacement, 3-benzo dioxolane base, three rings [3.3.1.1 (3,7)] last of the ten Heavenly stems-2-base, 1-(3-chloro-phenyl-)-1H-tetrazolium-5-base, the group of pyridyl, substituted pyridinyl.
2. according to the compound of claim 1, wherein
X is CR
5, R wherein
5Be H;
Y is CR
5, R wherein
5Be H;
Z is O
R
1-R
4Be H, halogen or C independently
1-C
4Alkyl, perhaps more preferably halogen;
V is CH or C
1-C
4Alkyl and
A is the phenyl of formula (2) mentioned above, wherein R
9R
13Be halogen, C independently
1-C
4Alkyl or halo C
1-C
7Alkyl; The phenyl of formula (2) perhaps more preferably as indicated above, wherein R
9R
13Be halogen independently; The pyridyl of pyridyl or replacement; Or the pyrimidyl of pyrimidyl or replacement.
3. according to the compound of claim 2, wherein
R
1-R
4It is halogen;
A is the phenyl of formula (2) as indicated above, wherein R
9R
13Be halogen independently.
4. oxygen base compound 4-[1-[4-fluorophenyl)] ethyl]-the 7-chloroquinoline.
5. compound 4-(cyano group (4-fluorophenoxy) methyl)-7-chloroquinoline.
6. chemical combination is in the 4-[1-[(4-fluorophenyl) the oxygen base] fourth-4-thiazolinyl]-the 7-chloroquinoline.
7. compound 4-[6-trifluoromethyl-2-pyridyloxy methyl]-the 7-chloroquinoline.
8. compound 4-[(4-trifluoromethyl-2-pyridyloxy methyl-5, the 7-dichloroquinoline.
9. oxygen base compound 4-[1-[(4-fluorophenyl)] ethyl]-5, the 7-dichloroquinoline.
10. compound 4-[two-(4-fluorophenoxy)] methyl]-5, the 7-dichloroquinoline.
11. methyl compound 4-[(4-fluorophenoxy)] quinoline.
12. compound 4-[(2,4-two fluorophenoxies) methyl]-5, the 7-dichloroquinoline.
13. methyl compound 4-[(4-fluorophenoxy)]-5, the 7-dichloroquinoline.
14. a sterilising method, it comprises that the place that is not subjected to the fungi infringement to needing protection uses formula (1) compound of sterilization significant quantity, the perhaps acid salt of formula (1) compound, or wherein Y is the N-oxide compound of formula (1) compound of CH;
Wherein
X is CR
5, R
5Be H, Cl or CH
3
Y is CR
5 ', R
5 'Be H, Cl or Br;
Z is O, S, SO, SO
2, NR
6, R wherein
6Be H, C
1-C
4Alkyl, C
1-C
4Acyl group, CR
7R
8, R wherein
7And R
8Be H, C independently
1-C
4Alkyl, C
1-C
4Alkenyl, C
2-C
4Alkynyl group, C
1-C
4Acyl group, CN or OH, perhaps R
7With R
8Connect together and form the carbocyclic ring that contains 4-6 carbon atom;
R
1-R
4Be H, OH, NO independently
2, halogen, I, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, C
1-C
4Alkoxyl group, halo C
1-C
4Alkyl, halo C
1-C
4Alkoxyl group, or halo C
1-C
4Alkylthio, perhaps R
1With R
2Or R
2With R
3Connect together and form the carbocyclic ring that contains 4-6 carbon atom;
V is CR
7R
8, R wherein
7And R
8Be H, C independently
1-C
4Alkyl, C
1-C
4Alkenyl, C
2-C
4Alkynyl group, C
1-C
4Acyl group, CN can choose phenoxy group, the halo C of replacement wantonly
1-C
4Alkyl or OH; Perhaps R
7With R
8Connect together and form the carbocyclic ring that contains the 4-6 carbon atom;
A is
(a) C
1-C
18The hydrocarbon chain of saturated or undersaturated straight or branched can randomly include in this hydrocarbon chain and is selected from O, S, SO or SO
2Heteroatoms and can be randomly by halogen, halo C
1-C
4Alkoxyl group, OH or C
1-C
4Acyl substituted;
(b) C
3-C
8Cycloalkyl or cycloalkenyl group;
(c) phenyl of formula (2)
Wherein
R
9-R
13Be H, CN, NO independently
2, OH, halogen, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, C
2-C
4Alkanoyl, halo C
1-C
7Alkyl, hydroxyl C
1-C
7Alkyl, C
1-C
7Alkoxyl group, halo C
1-C
7Alkoxyl group, C
1-C
7Alkylthio, halo C
1-C
7The phenoxy group of alkylthio, phenyl, substituted-phenyl, phenoxy group, replacement, thiophenyl, substituted benzene sulfenyl, phenyl C
1-C
4Alkyl, substituted-phenyl C
1-C
4Alkyl, benzoyl, SiR
20R
21R
22Or OSiR
20R
21R
22, R wherein
20, R
21And R
22Be H, C
1-C
6The alkyl of straight or branched, phenyl or substituted-phenyl, prerequisite are R
20, R
21And R
22In at least one is not H; Perhaps R
11And R
12Or R
12And R
13Form carbocyclic ring altogether; Precondition is if not all R
9-R
13Be H or F, so R
9-C
13In have at least two to be H;
(d) furyl of formula (3)
Wherein
R
14Be H, halogen, monochloromethyl, CN, NO
2, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, phenyl or C
1-C
4Alkoxyl group;
(e) thienyl of formula (4)
Wherein
R
15Be H, halogen, monochloromethyl, CN, NO
2, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, phenyl or C
1-C
4Alkoxyl group;
(f) formula (5) or group (5a)
Wherein
R
16Be H, halogen, monochloromethyl, CN, NO
2, C
1-C
4Alkyl, C
3-C
4Branched-chain alkyl, phenyl, substituted-phenyl or C
1-C
4Alkoxyl group, J are that N or CH and G are O, NR
19Or CH, precondition is or J is that N or G are NR
19, R wherein
19Be H, C
1-C
4Alkyl, C
1-C
4Acyl group, benzenesulfonyl or substituted benzene alkylsulfonyl;
(g) be selected from the group of pyridyl or substituted pyridinyl;
(h) be selected from the group of pyrimidyl or substituted pyrimidyl; Or
(i) be selected from 1-naphthyl, 4-pyrazolyl, the 3-methyl-4-pyrazolyl, 1 of 1-naphthyl, replacement, 3-benzo dioxolane base, three rings [3.3.1.1 (3,7)] last of the ten Heavenly stems-2-base, 1-(3-chloro-phenyl-)-1H-tetrazolium-5-base, the group of pyridyl, substituted pyridinyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2290796P | 1996-08-01 | 1996-08-01 | |
| US60/022,907 | 1996-08-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1228084A true CN1228084A (en) | 1999-09-08 |
Family
ID=21812051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97196937A Pending CN1228084A (en) | 1996-08-01 | 1997-07-31 | 4-substituted quinoline derivatives having fungicidal activity |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0925282A1 (en) |
| JP (1) | JP2001508029A (en) |
| KR (1) | KR20000029694A (en) |
| CN (1) | CN1228084A (en) |
| AU (1) | AU723758B2 (en) |
| BR (1) | BR9711110A (en) |
| CA (1) | CA2261916A1 (en) |
| WO (1) | WO1998005645A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11839216B1 (en) | 2022-08-23 | 2023-12-12 | Qingdao Agricultural University | Quinoline-2,3-fused nine-membered ring scaffold compound, and preparation method and application thereof as effective component in plant fungicide |
| WO2024040639A1 (en) * | 2022-08-23 | 2024-02-29 | 青岛农业大学 | Quinoline-2,3-fused nine-membered ring skeleton compound, preparation method therefor and use thereof as active ingredient in plant bactericide |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2336117A1 (en) | 2005-05-26 | 2011-06-22 | Neuron Systems, Inc | Heterocyclic compounds for treating retinal diseases |
| CA2782015C (en) | 2009-12-11 | 2020-08-25 | Neuron Systems, Inc. | Topical ophthalmic compositions and methods for the treatment of macular degeneration |
| US9604997B2 (en) | 2012-12-20 | 2017-03-28 | Aldeyra Therapeutics, Inc. | Peri-carbinols |
| KR102243169B1 (en) | 2013-01-23 | 2021-04-22 | 알데이라 테라퓨틱스, 아이엔씨. | Toxic aldehyde related diseases and treatment |
| CA2996183A1 (en) | 2015-08-21 | 2017-03-02 | Aldeyra Therapeutics, Inc. | Deuterated compounds and uses thereof |
| EP3454858A4 (en) | 2016-05-09 | 2020-01-15 | Aldeyra Therapeutics, Inc. | Combination treatment of ocular inflammatory disorders and diseases |
| ES2968462T3 (en) | 2017-03-16 | 2024-05-09 | Aldeyra Therapeutics Inc | Polymorphic salt of 6-chloro-3-amino-2(2-hydroxyprolyl) quinoline and uses thereof |
| MX2020003425A (en) | 2017-10-10 | 2020-07-29 | Aldeyra Therapeutics Inc | Treatment of inflammatory disorders. |
| WO2020033344A1 (en) | 2018-08-06 | 2020-02-13 | Aldeyra Therapeutics, Inc. | Polymorphic compounds and uses thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2862103D1 (en) * | 1977-08-19 | 1982-11-18 | Sandoz Ag | Propenyl amines, processes for their production and pharmaceutical compositions containing them |
| DE3702039A1 (en) * | 1986-01-29 | 1987-07-30 | Sandoz Ag | Novel amine derivatives, processes for their preparation, and their use |
| IL89028A0 (en) * | 1988-01-29 | 1989-08-15 | Lilly Co Eli | Quinoline,quinazoline and cinnoline derivatives |
| IL89026A (en) * | 1988-01-29 | 1993-02-21 | Lilly Co Eli | Substituted quinolines and cinnolines, process for their preparation and fungicidal, insecticidal and miticidal compositions containing them |
-
1997
- 1997-07-31 BR BR9711110A patent/BR9711110A/en unknown
- 1997-07-31 JP JP50798998A patent/JP2001508029A/en active Pending
- 1997-07-31 WO PCT/US1997/013090 patent/WO1998005645A1/en not_active Application Discontinuation
- 1997-07-31 KR KR1019997000773A patent/KR20000029694A/en not_active Application Discontinuation
- 1997-07-31 CN CN97196937A patent/CN1228084A/en active Pending
- 1997-07-31 AU AU38948/97A patent/AU723758B2/en not_active Ceased
- 1997-07-31 CA CA002261916A patent/CA2261916A1/en not_active Abandoned
- 1997-07-31 EP EP97936228A patent/EP0925282A1/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11839216B1 (en) | 2022-08-23 | 2023-12-12 | Qingdao Agricultural University | Quinoline-2,3-fused nine-membered ring scaffold compound, and preparation method and application thereof as effective component in plant fungicide |
| WO2024040639A1 (en) * | 2022-08-23 | 2024-02-29 | 青岛农业大学 | Quinoline-2,3-fused nine-membered ring skeleton compound, preparation method therefor and use thereof as active ingredient in plant bactericide |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3894897A (en) | 1998-02-25 |
| BR9711110A (en) | 1999-08-17 |
| EP0925282A1 (en) | 1999-06-30 |
| CA2261916A1 (en) | 1998-02-12 |
| JP2001508029A (en) | 2001-06-19 |
| AU723758B2 (en) | 2000-09-07 |
| WO1998005645A1 (en) | 1998-02-12 |
| KR20000029694A (en) | 2000-05-25 |
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