CN1083811A - The pyridine oxyethyl group of quinoline and quinazoline, pyridine ethylamino and pyridine propyl derivatives - Google Patents
The pyridine oxyethyl group of quinoline and quinazoline, pyridine ethylamino and pyridine propyl derivatives Download PDFInfo
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- CN1083811A CN1083811A CN93116448.6A CN93116448A CN1083811A CN 1083811 A CN1083811 A CN 1083811A CN 93116448 A CN93116448 A CN 93116448A CN 1083811 A CN1083811 A CN 1083811A
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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
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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
-
- 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
Abstract
The pyridyl oxyethyl group of quinoline and quinazoline, pyridyl ethylamino and pyridyl propyl derivatives, for example ((2-(2 for 2-for N-, 2, the 2-trifluoro ethoxy)-the 5-pyridyl) ethyl)-8-fluquinconazole quinoline-4-amine, it has the insect of killing, kills acarid, nematicide and mycocidal activity.
Description
The invention provides the novel organic compound that has unusual desinsection, kills mite, nematicide and Fungicidally active.The present invention also provides the composition of the methods and applications novel cpd that uses novel agrochemical.
More specifically, the invention provides the novel cpd of structural formula (1):
Wherein
X
1Be N or CR
1;
R
1Be H, halogen, low alkyl group, lower alkoxy, haloalkyl, halogenated alkoxy, NO independently
2, CN or rudimentary alcoxyl-carbonyl;
Y is CH
2, NR
3Or O, wherein R
3Be selected from H, low alkyl group, low alkyl group-carbonyl, low alkyl group-carbonyl oxygen base, SO
q-low alkyl group, SO
q-phenyl or substituted-phenyl; And q is the integer of 0-2;
X
2And X
3In one be N and another is CR
1;
R
2Be-Z-R
4, phenyl or substituted-phenyl;
Z is O or S; And
R
4Be (C
1-C
4) alkyl, (C
3-C
7) branched-chain alkyl, halo (C
1-C
7) alkyl, halo (C
3-C
7) branched-chain alkyl, (C
1-C
4) (the C that replaces of alkoxyl group
1-C
4) alkyl, perhaps naphthyl or phenyl, they both can be at random by at the most 3 be selected from halogen, (C
1-C
10) alkyl, branching (C
3-C
7) alkyl, halo (C
1-C
7) alkyl, hydroxyl (C
1-C
7) alkyl, (C
1-C
4) alkoxyl group, halo (C
1-C
4) alkoxyl group, O-phenyl, O-substituted-phenyl, phenyl, substituted-phenyl, naphthyl, CN, NO
2, OH, (C
1-C
4) group of alkanoyl oxygen base (alkanoyloxy) or benzyloxy replaces.
The present invention also provides the compound compositions of the methods and applications structure formula I that uses novel agrochemical.
Run through this paper, all temperature are all degree centigrade to provide and all percentage ratio is weight percentage, except as otherwise noted.
Term " halogen " refers to F, Cl, Br and I atom.
Term " low alkyl group " refers to C
1-C
6Straight-chain alkyl and C
3-C
6Side chain with the cyclic alkyl.
Term " low-grade alkenyl " and " low-grade alkynyl " refer to contain the C of at least one unsaturated link(age)
2-C
6Straight-chain alkyl and C
3-C
6Branched hydrocarbyl.
Term " lower alkoxy " and " lower alkylthio " refer to O-low alkyl group and S-low alkyl group.
Term " haloalkyl " refers to the low alkyl group that replaced by one or more halogen atoms.
Term " halogenated alkoxy " refers to the lower alkoxy that replaced by one or more halogen atoms.
Term " substituted-phenyl " refers to that wherein phenyl ring is by low alkyl group, low-grade alkenyl, low-grade alkynyl, lower alkoxy, halogen, hydroxyl, NO
2, haloalkyl, halogenated alkoxy, halogenated alkylthio, CN, phenyl, substituted-phenyl ,-the O-phenyl ,-O-substituted-phenyl, C
1-C
4Alkanoyl oxygen base, benzyloxy or S(O)
pThe group that-low alkyl group (p is 0-2 here) is replaced.
Term " HPLC " refers to high pressure liquid chromatography.
In the present invention, when selecting a plurality of substituting group independently, should be understood that and select them must make them compatible on the space each other.Space compatible refers to not exist sterically hindered, this term is at The Condensed Chemical Dictionary, 7th edition, Reinhold Publishing Co., the N.Y.893 page or leaf defines in (1966), and it is defined as follows:
Sterically hindered.A kind of molecular characterization, wherein this molecule had, their atoms in space arrange to make with another molecule given is reflected at and is stoped on the speed or block.
Space compatible, as at D.J.Cram and G.Hammon, Organic Chemistry, 2nd edtion, Mc Graw-Hill Book Company, discuss in the N.Y.215 page or leaf (1964), it is characterized in that substituting group, their physical size does not need not to be restricted in the volume when being not enough to carry out normal behaviour.
The compound of the structural formula of some kind (1) is preferred, that is:
(1) compound of structural formula (1), wherein R
2Be Z-R
4;
(2) compound of structural formula (1), wherein X
3Be N;
(3) compound of structural formula (1), wherein X
3Be N and R
2Be Z-R
4;
(4) compound of structural formula (1), one of them R
1Group is that the 8-fluorin radical all is H with remaining;
(5) compound of structural formula (1), wherein R
1All be H;
(6) compound of structural formula (1), wherein at least 3 R
1Be selected from H and F;
(7) compound of structural formula (1), wherein Z is O;
(8) compound of structural formula (1), wherein X
3Be N, R
2Be-Z-R
4, Z is O, and R
4Be (C
3-C
4) branched-chain alkyl;
(9) compound of structural formula (1), wherein X
3Be N, R
2Be-Z-R
4, Z is O, and R
4Be (C
1-C
4) alkyl;
(10) compound of structural formula (1), wherein X
3Be N, R
2Be-Z-R
4, Z is O, and R
4Be by a halogen atom or halo (C at 4
1-C
4) the mono-substituted phenyl of alkyl.
Use well-known chemical process to prepare The compounds of this invention.Required starting raw material is the commercial easy synthetic of standard method of buying or use.
Synthetic wherein Y is the compound of O
Wherein Y is that structural formula (1) compound of O can be by with structural formula (4)
Compound, X wherein
1And R
1Be that structural formula (1) defines; With L be a leavings group, as F, Cl, Br, I, NO
2, 1,2,3-triazoles-1-base, 1,2,4-triazol-1-yl, OSiMe
3, arylthio, alkylthio, alkane alkylsulfonyl, arylsulfonyl, alkoxyl group, or fragrant sulfinyl; With structural formula (5)
Alcohol, R wherein
2, X
2And X
3Be such as structural formula (1) definition, carry out condensation reaction and make.This reaction preferably in the presence of a kind of highly basic such as sodium hydride, in nonreactive activity solvent such as DXMF, is carried out under the temperature of 0-25 ℃ of scope.
Synthetic wherein Y is NR
3Compound
Wherein Y be the compound of NH or N-low alkyl group, structural formula (1) be by will be as defined above, the amine of the compound of structural formula (4) and structural formula (6) carries out condensation and makes,
R in the formula
2, X
2And X
3Be as structural formula (1) definition and R
3Be H or low alkyl group.Under the compound and the temperature of this amine in 20-180 ℃ of scope with structural formula (4), preferably in the presence of a kind of acid acceptor such as triethylamine, react.This reaction can merely be carried out, or carries out in a kind of nonreactive activity organic solvent.
R wherein
3The compound that is the structural formula (1) of acyl group is by inciting somebody to action wherein R
3Be the amine of H and acylating reagent such as Acetyl Chloride 98Min. or acetic anhydride and make.
Synthetic wherein Y is CH
2Compound
Wherein Y is GH
2The compound of structural formula (1) be by with structural formula (7)
Compound, X wherein
1And R
1Be to define in the structural formula (1);
With structural formula (8)
The refined reagent of Green, R wherein
2, X
2And X
3Be such as in the structural formula (1) definition, and X
1Be halogen, react and make.In order to obtain 3,4-dihydroquinazoline or quinoline are then with its oxidation.
Wherein Y is CH
2The compound of structural formula (1) also can react and make by lithium reagent with the compound of structural formula (7) and structural formula (9).
R wherein
2, X
2And X
3Be such as structural formula (1) definition.
In order to obtain 3,4-dihydroquinazoline or quinoline are then with its oxidation.Use usual way can from other product, isolate the compound of wanting required for the present invention.Typical reaction conditions be those at Armarego and Smith, J.Chem Soc. has described in 5360 pages (1965).
Wherein Y is CH
2The compound of structural formula (1) also can be by with the compound of structural formula (10),
X wherein
1And R
1Be such as in the structural formula (1) definition;
React in polar proton inert solvent with a kind of sprotic organolithium alkali (especially LDA), then with the compound of structural formula (11)
R wherein
2, X
2And X
3Be as defined above, and X
1Be halogen, react and make.This type of reaction is preferably carried out at-78-0 ℃ preferably at low temperatures.
Wherein Y is CH
2The compound of structural formula (1) also can be by at J.Heterocyclic Chemistry, Vol, 14,1081-1083(1977) present method of describing in (A.Scorille and F.X.Smith) prepares.This method comprises structural formula (12)
The hydrolysis and the decarboxylation of malonylurea.Wherein variable substituting group be such as structural formula (1) definition.Barbituric acid derivatives is dissolved in the solution of sodium hydroxide and water and refluxes.Then this solution is transferred to slant acidity and backflow once more.
Obtain compound N-the oxide-based and salt of structural formula (1) with usual way.
Starting raw material
Use the well-known method to prepare the starting raw material of structural formula (4), for example those are in following european patent application:
FPA326, the application on April 7th, 07/334,422,1989 of 330(corresponding US application number)
EPA326, the corresponding United States Patent (USP) 5,114,939 of 331() and
EPA326，329。
Use usual way to prepare the alcohols of structural formula (5) and the amine of structural formula (6), for example classical chain lengthening method of in following diagram I, representing easily:
In step 1, the KOH hydrolysis of nitrile produces corresponding carboxylic acid.
In step 2, lithium aluminium hydride is reduced the acid of this gate of a lane and is produced alcohol.In addition, this alcohol can be obtained by the corresponding aldehyde of sodium borohydride reduction.
Halogenating reaction in step 3 for example can be to use the thionyl chloride chlorination.
In step 4, handle halogenide and obtain nitrile with NaCN.
Be to use a kind of Lewis acid such as H in step 5
2SO
4Or AlCl
3Reduce this nitrile by lithium aluminium hydride.
In step 6, the hydrolysis of nitrile obtains the pyridyl acetogenin, and it uses lithium aluminium hydride or other common reductive agent to be reduced into pyridyl ethanol in step 7.
Preparation 1
2-(2-(2,2,2-three chloroethoxies)-the 5-pyridyl) ethamine
A. room temperature with 2,2,2 tfifluoroethyl alcohol (11.4ml, 156mmol) be added drop-wise to sodium hydride (60% in mineral oil, 5,72g is 143mmol) in the stirred suspension in 200mlDMF.This mixture about one hour in stirring at room drips 2-chloro-5-cyanogen pyridine during this period.Gained mixture about 3 hours in stirring at room.Water (about 10ml) cancellation reaction then is poured into mixture in the 200ml water, and (4 * 200ml) extract with ether.The organic extract water of these merging (3 * 200ml) washings, dry (Na
2SO
4), filter, and the concentrated 26.85g oil that obtains.Be placed on the silica gel plug it and washing, at first with about 250ml hexane (removing the mineral oil pollutent), then with about 400ml ether.Removing desolvates obtains 24.07g5-cyano group-2-(2, and 2, the 2-trifluoro ethoxy) pyridine, be a kind of oil.
B. under nitrogen, will be at the 5-chloro-2-(2 in the 250ml methylene dichloride, 2,2-trifluoro ethoxy) (51.41g 0.254mol) is chilled to 0 ℃ to pyridine.Dripping 254ml(0.254mol then) (1.0M is at CH for diisobutylaluminium hydride solution
2Cl
2In) handle this mixture.After dripping, allow this mixture heating up to room temperature and stir about 2 hours.This mixture cools off in ice bath then, and by dripping about 100ml saturated ammonium chloride, drips 250ml 2N sulfuric acid subsequently and quenching.Temperature remains on subzero 10 ℃.Then this mixture is warmed up to room temperature and separates each phase.Water extracted with diethyl ether (2 * 250ml).The organic extract water that merges (1 * 250ml) and saturated sodium-chloride (1 * 250ml) washing, drying (Na
2SO
4), filter, and concentrate and obtain 48.15g 2-(2,2, the 2-trifluoro ethoxy)-5-pyridyl carboxylic aldehyde, be yellow solid.
C. under nitrogen in 0 ℃, in batches with sodium borohydride (8.89g 0.235mol) is added to 2-(2,2,2-trifluoro ethoxy)-(48.10g is 0.235mol) in the solution in about 50ml absolute ethanol for 5-pyridyl carboxylic aldehyde.After adding, mixture was warmed up to room temperature and stir about 30 minutes.This mixture is poured in about 300ml water also with extracted with diethyl ether (3 * 500ml).The organic extract of this merging (NaSO that is dried
4), filter, and concentrate and obtain 47.08g(2-(2,2, the 2-trifluoro ethoxy)-the 5-pyridyl) methyl alcohol, be yellow semi-solid state thing.
D. under nitrogen in 0 ℃, (47.08g is 0.277mol) in the solution in 250ml toluene with thionyl chloride (80ml 1.1mol) is added drop-wise to (2-(2,2,2-trifluoro ethoxy)-5-pyridyl) methyl alcohol.After adding, this mixture was warming up to room temperature and stir about 2 hours.Under reduced pressure remove toluene and superfluous thionyl chloride.Residual collection in methylene dichloride and once more concentrated obtain 51.03g oil, it contains some insolubles.This crude product collected in ground ether (about 250ml) and with 1N sodium hydroxide (1 * 150ml), water (1 * 150ml) and saturated sodium-chloride (1 * 150ml) washs.Organic phase (the Na that is dried
2SO
4), filter, and concentrate and obtain 48.87g(2-(2,2, the 2-trifluoro ethoxy)-the 5-pyridyl) Methochloride, be yellow oil.
E. under nitrogen, at room temperature, with (2-(2,2, the 2-trifluoro ethoxy)-and the 5-pyridyl) (48.86g, 0.217mmol) drips of solution in 100ml DMSO is added to sodium cyanide (31.91g is 0.651mol) in the mixture of 200ml DMSO Methochloride.After adding, this mixture is raised to 50 ℃, and remains on 45-50 ℃ temperature stir about 2 hours.Then mixture is chilled to room temperature, and is poured in the 300ml water, extract (3 * 300ml) with ether/methylene dichloride (2: 1).Water (2 * 400ml) and saturated sodium-chloride (organic extract that 1 * 400ml) washing merges, dry then (Na
2SO
4), filter and concentrate and obtain 45.19g(2-(2,2, the 2-trifluoro ethoxy)-the 5-pyridyl) acetonitrile, be dark-brown oil.
F. under nitrogen in 0 ℃, with lithium aluminium hydride (3.70g, 92.5mmol) join in batches be stirred, (12.33g is 92.5mmol) in the solution in the 150ml ether for ammonium chloride.This mixture is stirred about 15 minutes, drips (2-(2,2 then, the 2-trifluoro ethoxy)-and the 5-pyridyl) acetonitrile (20.00g, 92.5mmol) solution in the 50ml ether handles, and after adding, this mixture is warming up to room temperature and in stirring at room about 2 hours.Then this mixture is cooled off in ice bath, quenching transfers to alkalescence and is warming up to room temperature with 2N sodium hydroxide by dripping saturated ammonium chloride (about 50ml).The gained mixture is filtered by filtering medium and separates each phase.(2 * 200ml) extract water with ether.The organic extract of this merging (Na that is dried
2SO
4), filter and concentrate and obtain 14.24g2-(2-(2,2, the 2-trifluoro ethoxy)-the 5-pyridyl) ethamine, be yellow oil.
Preparation 2
2-(2-(2,2, the 2=trifluoro ethoxy)-the 5-pyridyl) ethanol
A. to (2-(2,2,2-trifluoro ethoxy)-5-pyridyl) (16.98g, 78.6mmol) solution in the 120ml diox adds 120ml2N sodium hydroxide (240mmol) to acetonitrile, while and stir and reflux 18 hours.Then this mixture is chilled to room temperature, washs (2 * 200ml) with 0.5N sodium hydroxide (about 100ml) dilution and with ether.Water transfers to pH3 and uses ethyl acetate extraction (2 * 200ml) with dense HCl solution.This acetic acid ethyl ester extract (Na that is dried
2SO
4), filter, and the concentrated 17.40g brown solid that obtains.Recrystallization is also dried (60 ℃) from hexane/ethyl acetate, obtains (2-(2,2,2-the trifluoro ethoxy)-5-pyridyl acetate of 13.24g brown needle-like form.M.P.106℃。
B. under nitrogen in 0 ℃, with (2-(2,2,2-trifluoro ethoxy)-5-pyridyl) acetate (and 24.56g, 100ml diethyl ether solution 0.104mmol) be added drop-wise to stirring, (4.15g is in 300ml diethyl ether solution 0.104mmol) for lithium aluminium hydride.After adding, this mixture is warming up to room temperature and stirring at room 2 hours.In ice bath, cool off this mixture then, the quenching by dripping saturated ammonium chloride (about 75ml), (about 75ml) transfers to alkalescence and is warming up to room temperature with 2N sodium hydroxide.Filter the gained mixture and separate each phase by filtering medium.Water extracted with diethyl ether (2 * 200ml).The organic extract that the merges (Na that is dried
2SO
4), filter, and concentrate and obtain 19.53g2-(2-(2,2, the 2-trifluoro ethoxy)-the 5-pyridyl) ethanol, be yellow oil, its fast setting crystallization.M.P.38.5℃。
Embodiment 1
N-(2-(2-(2,2, the 2-trifluoro ethoxy)-the 5-pyridyl) ethyl)-8-fluoro quinazoline-4-amine
(compound 21)
With 4-chloro-8-fluquinconazole quinoline (0.482g, 2.64mmol), 2-(2-(2,2,2-trifluoro ethoxy)-the 5-pyridyl) ethamine (0.528g, 2.4mmol) and triethylamine (0.34ml, 2.4mmol) mixture in 15ml ethanol (2B) is heated to backflow.After refluxing about 20 hours, this mixture is chilled to room temperature, with the dilution of 75ml methylene dichloride, wash with water (2 * 50ml), with the saturated nacl aqueous solution washing (1 * 50ml), dry (Na
2SO
4), filter, and the concentrated 0.90g brown solid that obtains.Separate at the enterprising circumstances in which people get things ready for a trip layer of silica gel, with hexane/ethyl acetate (20/80) wash-out.The principal product of emanating out obtains the filbert solid of 0.68g.Recrystallization from hexane/acetate, and dry, obtain the 0.443g white solid.
M.P.174℃。
Embodiment 2
4-(2-(2-n-butoxy-5-pyridyl) quinazoline oxyethyl group)
(compound 3)
Following at nitrogen in room temperature, will (0.586g be in 10ml DMF solution 3.0mmol) with sodium hydride (0.120g 3.0mmol) the joins 2-(2-n-butoxy-5-pyridyl) ethanol of 60% dispersion form in mineral oil in batches.This mixture is stirred about 10 minutes.Then, add 0.494g(3.0mmol in batches) the 4-chloro-quinazoline, this mixture at room temperature stirred 4 hours.Then this mixture is poured in the 50ml water also with ether/methylene dichloride (2: 1) solution extraction (4 * 50ml).The organic extract water that merges (3 * 50ml) and saturated nacl aqueous solution (1 * 50ml) washing, drying (Na then
2SO
4) filter, and the concentrated 1.02g yellow solid that obtains.Separate at the enterprising circumstances in which people get things ready for a trip layer of silica gel, with hexane/ethyl acetate (90/10) wash-out.Merge the fraction that contains primary product, and concentrate, obtain the 0.423g water white oil.
The following table I is identified the representative compounds of structural formula (1), and in fact they use aforesaid method and prepare.
Fungicidally active
The compounds of this invention is found and is used for controlling fungi, particularly plants pathogenic agent.Ke bestows these plants with this compound with acceptable amount on disease inhibition and the phytology when being used to administer plant epiphyte venereal disease evil.Terminology used here " acceptable amount on disease inhibition and the phytology " refers to that The compounds of this invention is enough to eliminate and suppress the Plant diseases of required control, but not obvious phytotoxic consumption.This consumption is generally at about 1-1000ppm, preferred 10-500ppm.The accurate concentration of required compound will be with the fungal disease that will control, used preparaton type, using method, special floristics, weather condition, or the like and change.Suitable usage rate is generally in the scope of 0.25-4lb/A.The compounds of this invention also can be used for protecting the cereal of storage and other non-plant place to encroach on to exempt from fungi.
Controlled representative activity fungal disease biological body comprises:
Wild cabbage lattice chain spore (Brassica plants leaf spot)
Mali chain lattice spores (apple leaf spot)
Alternaria tenuis (leaf spot)
Botrytis cinerea (gray mold)
Sativus revolves spore (spot is withered)
Coffee hair disc spore (coffee paste fruit disease)
Colletotrichum Lindemuthianum (anthrax)
Big wheat powdery mildew (barley powdery mildew)
Wheat powdery mildew (wheat powdery mildew)
Scythe spore bacterium (head blight)
The Kidney bean Fusarium oxysporum
Gerlachia nivalis (snow mold)
Nodorum ball cavity bacteria (clever mildew)
Citrus health phytophthora
Phytophthora parasitica (balck shank)
Grape is given birth to single shaft mould (downy mildew of garpe)
Apple mildew bacterium (apple mildew)
The false little white smear spore (cereal eyespot) of calopo shell plant
Puccinia recondita (leaf rust)
Circle nuclear cavity bacteria (net blotch)
Pyricularia oryzae (rice blast)
Ultimate corruption mould (moist canker)
Cereal rhizoctonia (wheat point eyespot)
Dry thread Pyrenomycetes (leaf sheath seasonal febrile diseases)
Rye beak spore (blade brown spot)
Wheat septoria
Sclerotium rolfsii (hickie corruption)
Sclerotinite
Uncinula necator (uncinula necator)
Ustilago maydis (wheat bunt)
Albo-atrum verticillium sp (tomato is withered)
Do not wait black star bacterium (scab of apple)
Below experiment is used for the effectiveness of evaluation table I institute compounds identified when resisting various, as to cause Plant diseases organism.
These test compounds are prepared use by this compound of 50mg is dissolved in the 1.25ml solvent.This solvent is made by 50ml " polysorbas20 (Tween 20) " (polyoxyethylene (20) sorbitan monolaurate floating agent) is mixed with 475ml acetone and 475ml ethanol.This solvent/compound solution is diluted to 125ml with deionized water.The formulation thus obtained 400ppm test compound that contains.By obtaining low concentration with solvent-surfactant mixture serial dilution.
The test compound of these preparations is used by foliage spray.Following plants pathogenic agent or their corresponding plants have been used.
The code name Su Yan of pathogenic agent in Table II
Wheat powdery mildew (Powdery Mildew) ERYSGT wheat
Pyricularia oryzae PYRIOR rice
(rice blast)
Wheat concealment rest fungus PUCCRT wheat
(leaf rust)
Leptosphaeria nodorum LEPTNO wheat
(clever mildew)
Grape is given birth to single shaft mould (oidium) PLASVI grape
The specialized compound of preparation is sprayed on all blade faces of host plant to overflow.Every kind of host plant of single basin is placed on the rotary bracket of projection in the stink cupboard.Testing liquid is sprayed on all blade faces.All processing allow dry and these plants carried out inoculation culture with suitable pathogenic agent in 24 hours.
When with this test evaluation, the table II has been enumerated the activity of typical compound of the present invention.Use the effect of following level evaluation test compound control disease.
0=is not to specific organism test
-=at 400ppm control 0-19%
+=at 400ppm control 20-89%
++=at 400ppm control 90-100%
++ +=is at 100ppm control 90-100%
Insecticidal activity
The compound of structural formula (1) shows the activity of opposing many insects, acarid and nematode.More specifically, this compound shows the activity of opposing cotten aphid, and cotten aphid is a member in the Homoptera insect.Its member of Homoptera comprises leafhopper, lantern fly, pear psyllid, apple sucker, scale insect, aleyrodid, foam worm and many other hosts specific aphid kind.Also observed the activity of opposing greenhouse thrips, these thrips are the members in the Thysanoptera.This compound also shows the activity of the southern mythimna separata of opposing, and it is a member in the lepidopteron.The typical member of in this order other is the moth-eaten moth of fruit, sugared moth, casemaking clothes moth, Indian meal moth, beanpod leaf roll snout moth's larva, mealie noctuid, European corn borer, small white, cabbage looper, bollworm, psychid larva, the canopy of the heavens, east Candle-sticks, the beet mythimna separata, oriental tobacco budworm, the wild snout moth's larva in meadow and the autumn mythimna separata.This compound also shows the activity of opposing Groton bug, and it is the member in the Orthoptera.The typical member of in this order other is the Asia blattaria, oriental cockroach, and the big Lian of the U.S., stupid locust (magic locust) is very planted grasshopper, and red leg grasshopper moves empty grasshopper, the America grasshopper, grasshopper and indoor cricket vacillate.This compound also shows the activity of opposing corn rootworm, and it is a member in the Coleoptera.The typical member of in this order other is the west corn rootworm, Colorado colorado potato bug, confused flour beetle, mexican bean ladybird, plum ball neck resembles, Egyptian alfalfa snout beetle, alfalfa weevil, rice weevil, the southern corn curculionid, cotton (bell) resembles (nose) worm, and sweet potato weevil.
The compound of structural formula (1) is useful on minimizing insect, acarid and line insect population and is employed with a kind of method that suppresses insect, acarid or nematode, and this method comprises the compound that is applied to the structural formula (1) of effective insect, acarid or nematode order amount alive to the dwelling place of this insect, acarid or nematode.Here " dwelling place " of employed term insect, acarid or nematode means the environment of these insects, acarid or nematode life or their ovum existence, comprises their ambient airs, their food, the soil of their existence, or the object of their contacts.For example can be applied to this active compound and control insect or the acarid of eating plant by the plant part of eating to insect or acarid (particularly leaf).It will also be appreciated that, by to fabric, paper, the grain of storage, or seed is applied to active compound, and this compound perhaps can be protected them.Term " suppress insect, acarid, or nematode " refers to the insect that lives, the minimizing quantitatively of acarid or nematode; Perhaps viable insect, the ovum of acarid or nematode minimizing quantitatively.Certainly, reached the minimizing degree, depended on the usage rate of this compound, employed specific compound and targeted insect, acarid or line insect types by compound.Should use at least a insect inactivation, acarid inactivation or nematode inactivation amount, term " insect inactivation amount ", " acarid inactivation amount " and " nematode inactivation amount " is used to describe a kind of consumption, and it is enough to make processed insect, acarid or nematode to obtain measurable minimizing.Generally adopt the consumption in the about 1000ppm active compound of about 1-scope.
Test the acarid extremely of eight kinds of institute's compounds identified opposing in the table I and killed insect active.The result is set forth in the table III, writes a Chinese character in simplified form below using in the table III:
ALH refers to the aster leafhopper
BAW refers to the beet mythimna separata
CA refers to cotton aphid
NEM refers to the peanut root-knot eel-worm
SCRW guide side corn rootworm
TBW refers to oriental tobacco budworm
TSSM refers to T.urticae Koch
GECR refers to Groton bug
When carrying out the assessment of insecticidal activity, each test compound is formulated into 400ppm solution, and this solution of dilute with water obtains low concentration then.This 400ppm solution is by Tween20(polyoxyethylene (20) sorbitan monolaurate with 19.2ml0.05%) the solution of this compound of solution and 8mg in 0.8ml acetone (9/1) in water mixes and makes.
Resist the active tested as follows of aster leafhopper (Macrosteles fascifrons).Use the concentration of 400ppm and 50ppm to test.Use a flat fan nozzle to spray one ounce of plastic cup that a cotton core is housed with the raw material that 0.4ml prepares.Allow redundant moisture volatilize.Add 5 to 10 by the leafhopper adult of carbon dioxide narcosis to each cup then.Cover these cups, and at room temperature deposited 24 hours.Measure per cent death loss then.
Resist the active evaluated as follows of beet mythimna separata (Spodoptera exiqua beet spodoptera).Use the concentration of 400ppm and 50ppm to carry out this test.Refer to general objects lepidopteran artificial food is diluted to half intensity with 5% no nutrition fine jade.This foodstuff raw material of 8ml is assigned in one ounce of food cup.Handled preceding one hour, and 35-40 ovum was assigned to the surface of this food.Spray these cups by a flat fan nozzle with the raw material for preparing then.Processed cup is sealed up with plastic closure after dry air.These cups were at room temperature deposited 6 days.Add up to the basis with the larva that lives then and be that estimated activity is come on the basis with the size of the larva that lives with dead.
Resist the active evaluated as follows of cotton aphid (Aphis gossypii) and T.urticae Koch (Tetranychus urticae).Golden yellow curved neck pumpkin plant strain growth is arrived the exhibition cotyledon stage (about 6-8 days).Before the use-testing raw material, allow cotton aphid and T.urticae Koch encroach on these plant 16-24 hours by moving into the leaf that the quilt that downcuts from former population (a stock colony) encroached on.From these pumpkin plant, take away after the leaf of immigration, spray immediately and use this test raw material.Use the concentration of 400ppm to test.Use Dey-Dose that testing liquid is sprayed these plant with 17 pounds/inch pressure.The two sides of these leaves is capped until overflow air-dry then.After three days that handle, survey the activity of each compound.According to coming calculated activity based on the percentage ratio that only is present in the acarid/aphid on the plant of spraying with solvent.
Resist the active evaluated as follows of peanut root-knot eel-worm (Meloidogyne arenaria sandwort root knot nematode).5 untreated cucumber seeds are put into the bottom of one ounce of cup of a cleaning, add 20 clean white sands, cup rotates on carriage on one side, on one side to wherein spraying so that the 1.0ml400ppm solution deposition on sand.Distribute 2.5-3.0ml to contain the deionized water of 300-500 bar nematode to each cup.These cups are that 76-85 ℃ and ambient moisture are to put 10-12 days in the ambient growth chamber of 50-60% is deposited in temperature.After 10-12 days,, observe nemic death rate and, assess these cups the infringement that cucumber plant causes by the upset cup.
Resist the active evaluated as follows of southern corn rootworm (Diabrotica undecimpuctata howardi Bar-ber cucumber 11 asterophyllite first).1 milliliter of testing liquid that contains the predetermined concentration test compound is added in wherein the 16g sterile soil contains in the cup of a corn seed.Obtain the soil concentration of 24ppm like this.After 1.5-2 hour drying, 5 the 4th larvas that slough off the corn rootworm of phase are added in the cup.3-4 days by with cup turned letter on a dish and check that the rootworm that lives in the soil surveys mortality ratio.
Resist the active evaluated as follows of oriental tobacco budworm (Heliothis virescens, Heliothis virescens).With 5% no nutrient agar medium general objects and lepidopteran artificial food are diluted to half intensity.This foodstuff raw material of 8ml is assigned in each one ounce of food cup.Before processing 1 hour is assigned to foodstuff surface with the 18-20 ovum.Then, spray to these cups by the raw material of a flat fan nozzle with preparation.Use the concentration of 400ppm and 50ppm to carry out this test.Processed cup is sealed up with plastic closure by after air-dry.These cups were deposited 6 days in room temperature.Ading up to the basis and be that estimated activity is come on the basis with that live and dead larva then with the size of the larva that lives.
Resist the active evaluated as follows of Groton bug (Blattella germanicus Groton bug).8ml is that the light green insect foodstuff raw material of base is assigned in the ounce food cup with the clover.In these cups, spray with preparation raw material by a flat flat nozzle.Use the concentration of 400ppm and 50ppm to carry out this test.These processed cups are through air-dry 24 hours, then with 5 evenings the 3rd or the Groton bug infringement of the fourth phase early.Seal up these cups and in temperature is 76-85 ℃ ambient growth chamber, deposited ten days.Add up to the basis with the insect that lives then and come estimated activity with dead.
Composition
The compound of structural formula (1) is employed with the form of composition, and said composition is an important embodiment of the present invention, and this comprises receivable a kind of inert support on a kind of compound of structural formula (1) and the phytology.Said composition or be dispersed in the concentrated preparaton that uses in the water, or do not need further to handle and the powdery or the particulate state preparaton that use.Said composition can prepare according to method and prescription commonly used in the agrochemistry technology, but they are novel with important, because wherein there is The compounds of this invention.Yet we will provide some descriptions of said composition prescription, can prepare any required composition easily to guarantee the chemurgy scholars.
Aq suspension or the emulsion of wherein using the dispersion liquid of these compounds normally to make by the concentrated preparaton of these compounds.These water solubles, water is suspensible or emulsible preparaton, or usual known be the solid of wettable powder, but or be known as the liquid of the concentrated or aq suspension of emulsification usually.But can be pressed the wettable pulvis that forms the water discrete particles and comprise this active compound, the intimate mixture of a kind of inert support and tensio-active agent.The concentration of active compound is usually at the about 90%(weight of about 10%-meter).Inert support can be selected from attapulgite, polynite, diatomite or purifying silicon hydrochlorate usually.The effective surface promoting agent of about 0.5%-10% is to seek from the ethylene oxide adduct of sulfonated lignin, condensation naphthalenesulfonate, naphthalenesulfonate, alkylbenzene sulfonate, alkyl-sulphate and nonionogenic tenside such as induced by alkyl hydroxybenzene in the wettable pulvis.
The emulsible concentrated solution of this compound comprises the compound of suitable concentration, as every liter of about 500 grams (being equivalent to about 10%-about 50%) of the about 50-of liquid, this compound is dissolved in the inert support, this carrier or water-miscible solvent, or the mixture of water immiscible organic solvent and emulsifying agent.Useful organic solvent comprises arene (especially xylene) and petroleum fractions (especially the high boiling point naphthalene of oil belongs to or olefinic part as heavy aromatic naphthas).Also can use other organic solvent, as terpenes solvent (comprising rosin derivative), alkanones (as pimelinketone) and complicated alcohols (as 20 ethoxy ethanols).But the suitable emulsifying agent of emulsifying concentrated solution is to be selected from common nonionogenic tenside, and example is crossed as discussed above.
Aq suspension comprises the suspension of the insoluble compound of water of the present invention, and this compound is with in the about 50%(weight of about 5%-) concentration of scope is dispersed in the aqueous carrier.Suspension is to be mixed into consumingly in the carrier that comprises water and the tensio-active agent that is selected from above-mentioned same-type by this compound of fine grinding and with it to prepare.Be density and the viscosity that aqueous carrier is provided, also can add inert component such as inorganic salts and synthetic or natural natural gum.By preparing aqueous mixture and in a utensil such as sand mill, ball mill or piston-type homogenizer, making its homogenizing, usually can levigate most effectively at one time and this compound of mixing.
This compound can also the granular composition form be applied, and this composition is particularly useful in soil application.Granular composition contains the about 10%(weight of about 0.5-usually) this compound, this compound be dispersed in all or most of inert support of forming by clay or similar cheap material in.This based composition normally makes by this compound being dissolved in the suitable solvent and it being put on the granular carrier of being made suitable particle size (in the scope of about 0.5-3mm) in advance.This based composition also can be by making dough/pasta or pasty state with carrier and compound, and pulverize and dryly prepare to obtain required particle size.
The pulvis that comprises this compound is this compound and suitable Powdered agricultural carrier such as kaolin that passes through simply powder type, and levigated volcanized rock and analogue closely mix to be made.Pulvis can contain this compound of about 1%-about 10% more suitably.
For any reason, using this compound with the solution form in suitable organic solvent is feasible equally, and the oil that this solvent normally has no irritating odor is as being widely used in the spray oil of agrochemistry.
Sterilant and miticide use with the form of the dispersion liquid of activeconstituents in liquid vehicle usually.Represent that according to the concentration of activeconstituents in carrier application rate is common.The most widely used carrier is a water.
The compound of structural formula (1) can also the smoke substance composition form be applied.In these compositions, active compound dissolves or is dispersed in the inert support, and this carrier is the propellant mixture that produces pressure.This smoke substance composition is contained in the container, by atomization valve said composition is sprayed out from container.Propellant mixture or comprise lower boiling halocarbon class (can mix) or comprise aq suspension with the pressurization of rare gas element or gaseous hydrocarbons with organic solvent.
The actual amount that is applied to the compound in insect and place, acarid place is not strict, and it can be determined in view of the foregoing description by person skilled in the art.In general, the chemicals control effect that just can be hopeful to obtain to the concentration of 500ppm with 10ppm.For many these compounds.The concentration of 100-1500pm just can be satisfied the demand.For farm crop such as soybean and cotton, the ratio of using that compound is suitable is about 0.5-1.5 pound/mu (1b/A), typically uses with the spray formulations that contains the 1200-3600ppm compound of 50 gallons/mu (gal/A).For the oranges and tangerines crop, suitable usage rate is the spray formulations of about 100-1500 gallon/mu (gal/A), and it is the ratio of 100-1000ppm.
The place that applies compound can be any place of insect or spider perch, for example, and vegetable crop, fruit and nutwood, grape and decorative plant.Because many acarid kinds are specific with respect to special host, the example that the listed acarid kind in front provides the wide region environment can use compound of the present invention in these environment.
Because the acarid ovum has the special ability of opposing poisonous substance effect, need repetitive administration controlling emerging larva, and this also is the same for other known miticide.
The following prescription of compound of the present invention be typical, be used to implement composition of the present invention.
A. emulsifiable concentrate
The compound 9.38% of structural formula (1)
“TOXIMUL D” 2.50%
(nonionic/anionic surfactant mixture)
“TOXIMUL H” 2.50%
(nonionic/anionic surfactant mixture)
“EXXON 200” 85.62%
(naphthalene belongs to solvent)
B. emulsifiable concentrate
The compound 18.50% of structural formula (1)
“TOXIMUL D” 2.50%
“TOXIMUL H” 2.50%
“EXXON 200” 76.50%
C. emulsifiable concentrate
The compound 12.50% of structural formula (1)
N-methylpyrrolidone 25.00%
“TOXIMUL D” 2.50%
“TOXIMUL H” 2.50%
“EXXON 200” 57.50%
D. aq suspension
The compound 12.00% of structural formula (1)
“PLURONIC P-103” 1.50%
(segmented copolymer of propylene oxide and oxyethane,
Tensio-active agent)
“PROXEL GXL” 0.05%
(biocides/anticorrosion preservatives)
“AF-100” 0.20%
(nitre defoamer)
“REAX 88B” 1.00%
(lignosulfonic acid dipersant)
Propylene glycol 10.00%
Fillite 0.75%
Synthesising biological polymeric gel (Xanthan) 0.25%
Water 74.25%
E. aq suspension
The compound 12.50% of structural formula (1)
“MAKON 10” 1.00%
(10 mole ethylene oxide nonyls
The phenol tensio-active agent)
“ZEOSYL 200” 1.00%
(silica)
“AF-100” 0.20%
“AGRIWET FR” 3.00%
(tensio-active agent)
2% synthesising biological polymeric gel hydrate 10.00%
Water 72.30%
F. aq suspension
The compound 12.50% of structural formula (1)
“MAKON 10” 1.50%
" ZEOSYL 200 " (silica) 1.00%
“AF-100” 0.20%
“POLYFON H” 0.20%
(lignosulfonic acid dipersant)
2% synthesising biological polymeric gel hydrate 10.00%
Water 74.60%
G. aq suspension
The compound 10.20% of structural formula (1)
“TERGITOL TMN-6” 3.40%
“ZEOSYL 200” 0.90%
2% " KELZAN " solution 8.60%
“AF-100” 0.20%
Water 76.70%
G. wettable pulvis
The compound 25.80% of structural formula (1)
“POLYFON H” 3.50%
“SELLOGEN HR” 5.00%
“STEPANOL ME DRY” 1.00%
Gum arabic 0.50%
“HISIL 233” 2.50%
A crust soil 61.70%
H. granula
The compound 5.0% of structural formula (1)
Propylene glycol 5.0%
EXXON 200 5.0%
FLorex 30/60 granular soil 85.0%
Claims (10)
1, acceptable salt on the compound of a kind of structural formula (1) or its N-oxide compound or the agronomy,
Wherein
X
1Be N or CR
1
R
1Be H, halogen, low alkyl group, lower alkoxy, haloalkyl, halogenated alkoxy, NO independently
2, CN or rudimentary alcoxyl-carbonyl;
Y is CH
2, NR
3Or O, wherein R
3Be selected from H, low alkyl group, low alkyl group-carbonyl, low alkyl group-carbonyl oxygen base, SO
q-low alkyl group, SO
q-phenyl or substituted-phenyl; And q is the integer of 0-2;
X
2And X
3In one be N and another is CR
1
R
2Be-Z-R
4, phenyl or substituted-phenyl;
Z is O or S; And
R
4Be (C
1-C
4) alkyl, (C
3-C
7) branched-chain alkyl, halo (C
1-C
7) alkyl, halo (C
3-C
7) branched-chain alkyl, (C
1-C
4) (the C that replaces of alkoxyl group
1-C
4) alkyl, perhaps naphthyl or phenyl, among both any can be at random by at the most 3 be selected from halogen, (C
1-C
10) alkyl, branching (C
3-C
7) alkyl, halo (C
1-C
7) alkyl, hydroxyl (C
1-C
7) alkyl, (C
1-C
4) alkoxyl group, halo (C
1-C
4) alkoxyl group, O-phenyl, O-substituted-phenyl, phenyl, substituted-phenyl, naphthyl, CN, NO
2, OH, (C
1-C
4) group of alkanoyloxy or benzyloxy replaces.
2, the compound of claim 1, wherein X
3Be N.
3, the compound of claim 1, wherein Z is O.
4, the compound of claim 1, wherein R
2Be-Z-R
4, Z is O, and R
4Be (C
1-C
4) branched-chain alkyl.
5, the compound of claim 1, wherein R
2Be-Z-R
4, Z is O, and R
4Be halo (C
1-C
4) alkyl.
6, the compound of claim 1, wherein R
2Be-Z-R
4, Z is O, and R
4Be by a halogen atom or halo (C at 4
1-C
4) the mono-substituted phenyl of alkyl.
7, the compound of claim 1, it is N-(2-(2-(2,2, the 2-trifluoro ethoxy)-the 5-pyridyl) ethyl)-8-fluorine quinoline-4-amine; 4-(2-(2-(2,2, the 2-trifluoro ethoxy)-the 5-pyridyl) oxyethyl group)-8-fluquinconazole quinoline; The 4-(2-(2-n-butoxy)-and the 5-pyridyl) oxyethyl group) quinazoline, or the 4-(2-(2-(1-methyl ethoxy)-the 5-pyridyl) oxyethyl group)-8-fluquinconazole quinoline.
8, the method for a kind of insect, acarid or nematode, it comprises the compound that is applied to the claim 1 of a kind of insect, acarid or nematode inactivation amount to the dwelling place that insect, acarid or nematode suppress.
9, a kind of method that suppresses phytopathogen, it comprises the compound that is applied to the claim 1 of significant quantity to the dwelling place of this pathogenic agent.
10, a kind of pesticide composition, it comprise with a kind of agronomy on the compound of claim 1 of acceptable carrier blended insect, acarid, nematode or phytopathogen amount of suppression.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US932,397 | 1978-08-09 | ||
| US93239792A | 1992-08-19 | 1992-08-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1083811A true CN1083811A (en) | 1994-03-16 |
Family
ID=25462244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93116448.6A Pending CN1083811A (en) | 1992-08-19 | 1993-08-18 | The pyridine oxyethyl group of quinoline and quinazoline, pyridine ethylamino and pyridine propyl derivatives |
Country Status (5)
| Country | Link |
|---|---|
| CN (1) | CN1083811A (en) |
| AU (1) | AU4790893A (en) |
| IL (1) | IL106723A0 (en) |
| MX (1) | MX9305026A (en) |
| WO (1) | WO1994004527A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100349890C (en) * | 2002-01-22 | 2007-11-21 | 纳幕尔杜邦公司 | Quinazoline(di) ones for invertebrate pest control |
| WO2011128837A1 (en) * | 2010-04-15 | 2011-10-20 | Basf Se | Fungicidal mixtures ii comprising quinazolines |
| WO2011128843A1 (en) * | 2010-04-15 | 2011-10-20 | Basf Se | Fungicidal mixtures i comprising quinazolines |
| CN105348298A (en) * | 2014-07-04 | 2016-02-24 | 沈阳中化农药化工研发有限公司 | Substituted aryl pyridine compounds and use thereof |
| CN109776427A (en) * | 2017-11-13 | 2019-05-21 | 沈阳中化农药化工研发有限公司 | Double aminated compounds of pyrimidine and application thereof |
| CN110194761A (en) * | 2019-07-05 | 2019-09-03 | 华东理工大学 | Quinazolyl ramification of carboxylic esters and its antibacterial application |
| US10487091B2 (en) | 2015-10-05 | 2019-11-26 | The Trustees Of Columbia University In The City Of New York | Activators of autophagic flux and phospholipase D and clearance of protein aggregates including tau and treatment of proteinopathies |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6987096A (en) * | 1995-09-12 | 1997-04-01 | Basf Aktiengesellschaft | Fungicidal quinolines |
| US6521618B2 (en) | 2000-03-28 | 2003-02-18 | Wyeth | 3-cyanoquinolines, 3-cyano-1,6-naphthyridines, and 3-cyano-1,7-naphthyridines as protein kinase inhibitors |
| US8268843B2 (en) | 2008-08-29 | 2012-09-18 | Dow Agrosciences, Llc. | 5,8-difluoro-4-(2-(4-(heteroaryloxy)-phenyl)ethylamino)quinazolines and their use as agrochemicals |
| WO2011025505A1 (en) * | 2009-08-31 | 2011-03-03 | Dow Agrosciences Llc | Pteridines and their use as agrochemicals |
| US8461164B2 (en) | 2009-08-31 | 2013-06-11 | Dow Agrosciences, Llc. | Pteridines and their use as agrochemicals |
| WO2014063642A1 (en) | 2012-10-25 | 2014-05-01 | 中国中化股份有限公司 | Substituted pyrimidine compound and uses thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GT198900005A (en) * | 1988-01-29 | 1990-07-17 | QUINOLINS AND SUBSTITUTED CINOLINS. | |
| IL89028A0 (en) * | 1988-01-29 | 1989-08-15 | Lilly Co Eli | Quinoline,quinazoline and cinnoline derivatives |
| IL89027A (en) * | 1988-01-29 | 1993-01-31 | Lilly Co Eli | Quinazoline derivatives, process for their preparation and fungicidal, insecticidal and miticidal compositions containing them |
-
1993
- 1993-07-29 WO PCT/US1993/007120 patent/WO1994004527A1/en active Application Filing
- 1993-07-29 AU AU47908/93A patent/AU4790893A/en not_active Abandoned
- 1993-08-18 MX MX9305026A patent/MX9305026A/en unknown
- 1993-08-18 CN CN93116448.6A patent/CN1083811A/en active Pending
- 1993-08-18 IL IL106723A patent/IL106723A0/en unknown
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100349890C (en) * | 2002-01-22 | 2007-11-21 | 纳幕尔杜邦公司 | Quinazoline(di) ones for invertebrate pest control |
| WO2011128837A1 (en) * | 2010-04-15 | 2011-10-20 | Basf Se | Fungicidal mixtures ii comprising quinazolines |
| WO2011128843A1 (en) * | 2010-04-15 | 2011-10-20 | Basf Se | Fungicidal mixtures i comprising quinazolines |
| CN102843911A (en) * | 2010-04-15 | 2012-12-26 | 巴斯夫欧洲公司 | Fungicidal mixtures ii comprising quinazolines |
| CN105348298A (en) * | 2014-07-04 | 2016-02-24 | 沈阳中化农药化工研发有限公司 | Substituted aryl pyridine compounds and use thereof |
| CN105348298B (en) * | 2014-07-04 | 2019-03-19 | 沈阳中化农药化工研发有限公司 | Substituted aryl pyridine compounds and their and application thereof |
| US10865214B2 (en) | 2015-10-05 | 2020-12-15 | The Trustees of Columbia University in they City of New York | Activators of autophagic flux and phospholipase D and clearance of protein aggregates including tau and treatment of proteinopathies |
| US10487091B2 (en) | 2015-10-05 | 2019-11-26 | The Trustees Of Columbia University In The City Of New York | Activators of autophagic flux and phospholipase D and clearance of protein aggregates including tau and treatment of proteinopathies |
| US11008341B2 (en) | 2015-10-05 | 2021-05-18 | The Trustees Of Columbia University In The City Of New York | Activators of autophagic flux and phospholipase D and clearance of protein aggregates including tau and treatment of proteinopathies |
| US11230558B2 (en) | 2015-10-05 | 2022-01-25 | The Trustees Of Columbia University In The City Of New York | Activators of autophagic flux and phospholipase D and clearance of protein aggregates including tau and treatment of proteinopathies |
| US11261199B2 (en) | 2015-10-05 | 2022-03-01 | The Trustees Of Columbia University In The City Of New York | Activators of autophagic flux and phospholipase d and clearance of protein aggregates including tau and treatment of proteinopathies |
| CN109776427A (en) * | 2017-11-13 | 2019-05-21 | 沈阳中化农药化工研发有限公司 | Double aminated compounds of pyrimidine and application thereof |
| CN109776427B (en) * | 2017-11-13 | 2022-08-23 | 沈阳中化农药化工研发有限公司 | Pyrimidine diamine compound and application thereof |
| CN110194761A (en) * | 2019-07-05 | 2019-09-03 | 华东理工大学 | Quinazolyl ramification of carboxylic esters and its antibacterial application |
| CN110194761B (en) * | 2019-07-05 | 2021-08-20 | 华东理工大学 | Quinazoline carboxylic ester derivative and antibacterial application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| IL106723A0 (en) | 1993-12-08 |
| WO1994004527A1 (en) | 1994-03-03 |
| MX9305026A (en) | 1994-03-31 |
| AU4790893A (en) | 1994-03-15 |
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