CN1084512A - 2-aryl hydrazono--3-ketone acid pyridine, their preparation method and as the application of agricultural chemicals - Google Patents
2-aryl hydrazono--3-ketone acid pyridine, their preparation method and as the application of agricultural chemicals Download PDFInfo
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- CN1084512A CN1084512A CN93117041A CN93117041A CN1084512A CN 1084512 A CN1084512 A CN 1084512A CN 93117041 A CN93117041 A CN 93117041A CN 93117041 A CN93117041 A CN 93117041A CN 1084512 A CN1084512 A CN 1084512A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/40—Six-membered ring containing nitrogen and carbon only
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members 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
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
- C10M2215/226—Morpholines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/30—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
Abstract
The present invention relates to the 2-aryl hydrazono--3-ketone acid-piperidine compounds shown in the formula I, their preparation method contains the medicament of this compound and they as agricultural chemicals, and particularly as the application of sterilant, every implication sees specification sheets for details in the formula.
Description
The present invention relates to new 2,2,6, the amide derivatives of 6-tetraalkyl-4-amino piperidine, their preparation method contains their medicament and they are as agricultural chemicals, particularly as the application of sterilant.
Known 2,2,6, the composition that the acid amides of 6-tetramethyl--4-amino piperidine is made sterilant is knownly (to see DE-A-3901246, DD-A-138729).The drug effect of this amides, particularly often can not be satisfactory under the low situation of consumption.
Had been found that newly 2,2,6, the acid amides of 6-tetraalkyl-4-amino piperidine confirms that they have wide spectrum to plant pathogenic fungi, and good prevention effect is particularly under low dosage.
The present invention relates to compound shown in the formula I and their salt, the preferred salt of the inorganic or sour addition of organic acid that can bear of those plants,
In the formula
R
1Be hydrogen, (C
1-C
12)-alkyl, (C
2-C
6)-alkenyl, (C
2-C
6)-alkynyl, alkyl wherein can be with dividing to 3 identical or different halogen, (C of being selected from when alkenyl and alkynyl need
1-C
3)-alkoxyl group, (C
1-C
3)-alkylthio, cyano group, (C
3-C
6The substituting group of)-cycloalkyl, if the aryl that also replaces when needing and aryloxy or this three groups of replacing when needing are not included in the definition listed above, can be when needing by halo part or complete, have the identical or different oxygen that are selected from of 3 of as many as when needing, the 5-of the replacement of sulphur and nitrogen heteroatom or 6 yuan of heterocycles, (the C that replaces when needing
3-C
9)-cycloalkyl or can hang the phenyl or naphthyl of replacement when needing;
R
2Be hydrogen, (C
1-C
4)-alkyl, (C
1-C
3)-alkyloyl or (C
1-C
3)-alkoxy carbonyl;
R
3Be (C
1-C
4)-alkyl;
R
4Be hydrogen, cyanoethyl, benzyl, OH, O or COOR
3;
X is identical or different group, is selected from halogen, cyano group, nitro, thiocyano, (C
1-C
6)-alkyl, (C
1-C
6)-alkoxyl group, (C
1-C
6)-alkylthio, can be when alkyl wherein, alkoxyl group need with alkylthio with 3 of as many as identical or different halogen and the (C of being selected from
1-C
3If the substituting group of)-alkoxyl group or this three groups are not included within the top definition, can be when needing by part or all halogenated, (C
1-C
3)-alkoxy carbonyl, aryl, aryloxy or aroyl, preferred phenyl, phenoxy group or benzyl acyl group, they each all can have 5 identical or different substituting groups that are selected from halogen or trifluoromethyl of as many as, (C
3-C
6)-cycloalkyl or NR
5R
6, or n 〉=2,2 an adjacent X with the phenyl ring that carries them form a naphthyl or tetrahydro naphthyl and, if n＞2, remaining X base as top determined implication;
Y is O or NOH;
R
5And R
6Being identical or different, is hydrogen, (C
1-C
4)-alkyl or by identical or different (C
1-C
3Trisubstituted (the C of)-alkyl
3-C
6)-cycloalkyl and
N is the integer of 0-4
Salt of the present invention is hydrochloric acid for example, bromine hydracid or iodine hydracid, sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, acetic acid, propionic acid, toxilic acid, fumaric acid, lactic acid, oxyacetic acid, oxalic acid, succsinic acid, citric acid, tosic acid, Whitfield's ointment, the salt of dodecyl sodium sulfonate addition or the salt of benzoic sulfimide.
Compound shown in the preferred formula I and their salt be following these, in the formula
R
1Be hydrogen, (the C that replaces when needing
1-C
4)-alkyl, the phenyl that replaces when needing, phenyl methyl that replaces when the needing or (C that replaces when needing
3-C
6)-cycloalkyl;
R
2Be hydrogen, (C
1-C
4)-alkyloyl or (C
1-C
3)-alkoxy carbonyl;
R
3It is methyl;
R
4Be hydrogen;
X is identical or different, is halogen, nitro, thiocyano, cyano group, (C
1-C
3)-alkoxy carbonyl, (C
1-C
3)-alkyl, (C
1-C
3)-alkoxyl group, (C
1-C
3)-alkylthio, alkyl wherein, alkoxyl group can all or part ofly be replaced by identical or different halogen atoms with alkylthio, phenyl, phenoxy group or benzyl acyl group, their available halogen one or many replace and/or available trifluoromethyl replaces,
Y be O or NOH and
But n 0-3,
Compound shown in the best formula I, and their salt, the particularly salt of their sour addition (example hydrochloric acid, para Toluic Acid or benzoic sulfimide salt) be following these, in the formula
R
1Be methyl or cyclopropyl;
R
2Be hydrogen,
R
3Be methyl,
R
4Be hydrogen,
X is identical or different, is halogen, cyano group, (C
1-C
3)-alkyl, (C
1-C
3)-alkoxyl group or (C
1-C
3)-alkylthio, alkyl wherein, alkoxyl group can all or part ofly be replaced by identical or different halogen atoms with alkylthio;
Y be O or NOH and
But n 1-3.
Under each situation, as long as the definition of not biding farewell, alkyl, but alkenyl and alkynyl straight chain or side chain; This also is applicable to the group that is derived from by above-mentioned group, as alkoxyl group, and alkylthio or alkyloyl.Halogen is fluorine, chlorine, bromine or iodine.
" aryl " can be interpreted as the benzenoid form aromatic base of 6-18 carbon atom of a band especially, as phenyl, and naphthyl, xenyl or indenyl; Preferred phenyl.This also is applicable to " aryloxy " (preferred phenoxy group) and " aroyl " (preferred benzyl acyl group).
(C
3-C
9)-cycloalkyl is interpreted as for example cyclopentyl, cyclohexyl or suberyl, wherein preferred cyclohexyl.
Commutable aryl when needing, each can be with 5 of as many as aryloxy or cycloalkyl, preferred 3 identical or different substituting groups at the most, preferably these substituting groups are halogens, nitro, thiocyano, cyano group, (C
1-C
3)-alkoxy carbonyl, (C
1-C
3)-alkyl, (C
1-C
3)-alkoxyl group, (C
1-C
3)-alkylthio, alkyl wherein, alkoxyl group can be replaced by identical or different halogen atoms whole or in part with alkylthio, phenyl and phenoxy group, these two groups can be replaced by the halogen one or many or replace with trifluoromethyl.
" heterocyclic group " preferred heteroaryl groups or saturated group part or temporary transient that derives from by it." heteroaryl " can preferably be interpreted as it is a phenyl group, has at least a CH to be substituted by N in this phenyl and/or wherein at least two adjacent CH-groups are at every turn together by a NH, and O and/or S replace.Such group for example be thienyl, furyl, benzofuryl, pyrryl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl ， oxazolyl ， isoxazolyl, thiazolyl, isothiazolyl and tetrazyl.
Compound shown in the formula I partly has one or more unsymmetrical carbons.So it can produce racemic modification and diastereomer.The present invention comprises that not only pure isomer also comprises their mixture.The mixture of diastereomer can be taked conventional method, for example carries out selective crystallization or isolates each composition by chromatography by a suitable solvent.Racemic modification can be isolated enantiomorph with method commonly used, for example, by with opticity acid salifiable method, the separation of diastereoisomeric salt and a method that makes pure enantiomorph dissociate out by means of an alkali.
New amide compound 1 can prepare by following method:
A) compound of general formula II institute formula and the diazonium salt shown in the general formula III react according to the condition of the reaction of known methylene radical activatory compound and diazonium salt in the common document.
Substituting group in the following formula have in the above given implication, this coupling is in water or alcohol-water mixed liquid, pH is preferably under the condition between 4 and 5 and carries out, and the adjusting of pH value of solution value can be by adding a damping fluid such as sodium-acetate or dripping a kind of alkaline solution simultaneously such as sodium hydroxide solution is achieved.
B) compound shown in compound shown in the general formula IV and the general formula V is between 100 and 200 ℃ in temperature, between preferred 130 and 180 ℃, reacts under the condition that solvent is arranged or do not have solvent to exist.As the spendable solvent of inert solvent be dimethylbenzene for example, dichlorobenzene, dimethyl formamide, dimethyl sulfoxide (DMSO), phenyl ether etc.
R in the formula IV
1And X
nAbove having given implication, R
5But methyl or ethyl,
R in the formula V
2, R
3And R
4Above having given implication.
The preparation of the compound shown in the formula II can be passed through with the reaction shown in 'beta '-ketoester IV and the formula V by known method in the document, or works as R
1=CH
3The time, can react with compound shown in the formula V and diketene by known method in the document
R in the formula IV
1And R
5Above having given implication.
Corresponding oxime shown in the formula I of Y=NOH can be by known method in the document by ketone shown in the formula I of Y=0 and azanol reaction preparation.
Compound exhibits of the present invention shown in the formula I has gone out good protection and therapeutic action.Its those fungal pathogens that invaded in the plant tissue also can carry out effectively preventing.This point can not have been gathered the situation of imitating with conventional sterilant for that and has been even more important and demonstrate its superiority after fungal disease infects.The action spectrum of The compounds of this invention comprises many plant pathogenic fungis with important economic implications, as oidium, and late blight and gray mold.
In addition, compound of the present invention also can be applicable to some other technical field, as Wood protecting agent, and coating antiseptic, the cold lubricant in the metal processing or as the sanitas of drilling machine and cutting oil.
Object of the present invention also comprises such medicament, and this medicament also contains the compound shown in the formula I except containing suitable formulation auxiliary agent.Medicament of the present invention contains 1-95%(weight usually) the formula I shown in effective constituent.Can be processed into various formulation according to biology of being given and/or chemical physics parameter.Machinable formulation is: wettable powder (WP), and missible oil (EC) is the water dispersant (SC) of matrix with oil or water, suspension emulsion (SC), pulvis (DP), soaker, dispersible granules agent (WG) in water, ultralow amount formulation, microcapsule or cerate.
These formulations are known basically, and record is for example arranged in the document below:
Winnacker-küchler，“Chemische Technologie”，Band 7，C-Hauser Verlag München，4.Aufl.1986;van Falkenberg，“Pesticides Formulations”，Marcel Dekker N.Y.，2nd Ed.1972-73;K.Martens，“Spray Drying Handbook”，3rd Ed.1979，G.Goodwin Ltd.London.
Necessary formulation auxiliary material such as inert substance, tensio-active agent, solvent and other additive also are known, and be for example on the books in the document below:
Watkins，“Handbook of Insecticide Dust Diluents and Carrier”，2nd Ed.，Darland Books，Caldwell N.J.;H.v.Olphen，“Introduction to Clay Colloid Chemistry”，2nd Ed.，J.Wiley & Sons，N.Y.;Marschen，“Solvents Guide”，2nd Ed.，Interscience，N.Y.1950;McCutcheon's“Detergents and Emulsifiers Annual”，MC Publ.Corp.，Ridgewood N.J.;Sisley and Wood，“Encyclopedia of Surface Active Agents”，Chem.Publ.Co.Inc.，N.Y.1964;Schoenfeldt，“Grenzflaechenaktive Aethylenoxiaddukte”，Wiss.Verlagsgesell.，Stuttgart 1976;Winnacker-Küchler，“Chemische Technologie”，Band 7，C.Hauser Verlag München，4.Aufl.1986.
On the basis of these formulations, can also with other pesticide active ingredient, fertilizer and/or growth regulator are made mixture together, for example can be processed into the form of finished product preparation or canned mixture.
Wettable powder is can homodisperse preparation in water; it is except effective constituent, outside thinner or the inert substance, also contains wetting agent such as polyoxyethylated alkylphenol; polyoxy ethylization Fatty Alcohol(C12-C14 and C12-C18); alkyl-or alkylphenol-sulfonate, and dispersion agent, as sodium lignosulfonate; 2; 2 '-dinaphthyl methane-6,6 '-sodium disulfonate, sodium dibutyl naphthalene sulfonate or oleoyl N-methyltaurine sodium.Missible oil is that effective constituent is dissolved in an organic solvent, and as butanols, pimelinketone, diethylformamide are in dimethylbenzene or high boiling aromatic hydrocarbons or the hydro carbons and be added into one or more emulsifying agents and make.The example that can be used as the emulsifying agent use has, alkyl aryl sulphonic acid calcium salt such as calcium dodecylbenzene sulphonate or nonionic emulsifier such as fatty acid polyglycol ester, alkylaryl polyglycol ether, fatty alcohol polyglycol ether, propylene oxide-oxyethane-sorbitan fatty acid esters, polyoxyethylene sorbitan-fatty acid ester or polyoxyethylene sorbitol ester.
Pulvis is by with effective constituent and thin, the dispersed solids material, and talcum for example, natural clay such as kaolin, bentonite, leaf wax soil or diatomite grind together and obtain.
Granule is by being sprayed at effective constituent the tool absorption property, be prepared from the particulate inert material, perhaps by means of some binding agents, polyvinyl alcohol for example, sodium polyacrylate or also available mineral oil make effective constituent be attached to carrier substance such as sand, and the surface preparation of kaolin or particulate inert material forms.Some suitable effective constituent can also be with the method for common manufacturing granulated fertilizer-can mix with fertilizer-granulation when needing.
Effective constituent concentration is approximately 10-90%(weight in the wettable powder), 100%(weight) rest part become to be grouped into by formulation commonly used.Effective constituent concentration is approximately 5-80%(weight in the missible oil).Effective constituent concentration mostly is 5-20%(weight greatly in the pulvis).The material agent in active constituent content depend in part on, whether the effective constituent compound is liquid or solid, which type of compound is to be liquid or solid and to use which type of particle auxiliary agent, factors such as filler.
Except that cited effective constituent formulation, when needing, preparation also contains binding agent commonly used, wetting agent, dispersion agent, emulsifying agent, permeate agent, solvent, filler-or carrier substance.
Use with ordinary method dilution back when the enriched material that provides being provided needing with common commodity, wettable powder for example, missible oil, dispersion agent also has part fine granule dilutable water.Pulvis and granular formulations and the solution that can spray do not need to dilute with inert substance more before use usually.
Along with external conditions such as temperature, the variation of humidity, the consumption of effective constituent can in very large range change, for example can 0.05 and 10kg/ha or consumption more more, preferred consumption 0.01 and 5kg/ha between.
Effective constituent of the present invention can with the form of its commodity formulation use separately or can with other, known sterilant is used with together in the document.
Can in the document that the compound shown in the formula I of the present invention is used with, be listed below by the example of known sterilant: Aldimorph, Andoprim, anilazine, BAS480F, BAS490F, Benalaxyl, the iodine spirit of withering, F-1991, Niagara 9044, Bitertanol, Bromuconazol, Buthiobat, Difolatan, Vancide 89, derosal, carboxin, CGA-173506, Chlobenzthiazone, m-tetrachlorophthalodinitrile, Cymoxanil, Cyproconzole, C y p r o f uran, Pecudin, Dichlormezin, Diclobutrazol, Diethofencarb, Difenconazol(CGA 169374), Difluconazole, Dimethirimol, Dimethomorph, the speed Poly, Mildex, Delan, dodemorph, dodine, the gram temperature is loose, ethirimol, Truban, fenarimol, the spirit of withering of one first cottonrose hibiscus, Fenpiclonil, Fenpropidin, Fenpropimorph, triphenyltin acetate, triphen hydroxyl tin, Ferimzone(TF164), Fluazinam, Fluobenzimine, the fluorine imines, Fluquinconazol, Flusilazole, fluorine line amine, flutriafol, Phaltan, Fosetylaluminium, fuberidazole, Fulsufamid(MT-F651), Furalaxyl, Furconazol, Furmecyclox, two hot guanamines, Hexaconazole, IMAZALIL, Imazalil, lmiben-conazol, Iprobenfos, different third is fixed, isoprothiolane, KNF317, copper compound such as oxygen base cupric chloride, quinolinone, cupric oxide, zinc manganese ethylenebisdithiocarbamate, maneb, Mepanipyrim(KIF 3535), mebenil, metaxanin, Metconazol, Methasulfocarb, first methuroxam, MON24000, Myclobutanil, Parzate, different third disappears, the spirit of ring bacterium, the spirit of ofurace Evil frost, oxycarboxin, penconazol, the standing grain fringe is peaceful, PP969, the thiophene bacterium is rare, propineb, Prochloraz, procymidone, hundred dimension spirits, Wocosin 50TK, the rosickyite prestige, pyracarbolid, pyrifenox, pyrimethanil, pyroquilon, Rabenzazole, RH7592, Fenbuconazol, sulphur, Tebuconazole, TF167, thiabendazole, Thicyofen, Thiofanatemethyl, thiram, Toclofos-methyl, tolylfluanid, triazolone, triadimenol, triazole benzene thiophene, cyclomorpholine, Te Fuling, triforine, Validamycin, Vinclozoline, XRD-563, zineb, sodium laurylsulfonate, sodium lauryl sulphate, C
13/ C
15-alcohol ether sodium sulfonate, Natrium-cetostarylphosphatester, dioctyl-sodium sulfosuccinate, isopropyl naphthalene sodium sulfonate, the methylene sodium dinaphthalenesulfonate, palmityl trimethyl ammonium chloride, the primary of long-chain, the salt of the second month in a season or tertiary amine, the alkyl allylamine, lauryl bromination pyridine, ethoxylation season aliphatic amide, alkyl-dimethyl-benzyl-ammonium chloride and 1-hydroxyethyl-2-alkyl-tetrahydroglyoxaline.
Mixture pairing compound listed above is known effective constituent; major part in them is to be documented in CH.R.Worthing; U.S.B.Walker; Thepesticide Manual(agricultural chemicals handbook); 7; Auflage(1983), British Crop protection council.(Britain farming protection association).
In addition, mixing with other effective constituent, described other effective constituent is as sterilant, attractive substance, apholate, miticide, nematicide line or weedicide in the effective constituent of the present invention that exists with commodity formulation and the form that is applied with these formulations.Sterilant is meant phosphoric acid ester, amino formate, carboxylic acid esters, formamidine, tin compound, microbial preparations etc. preferably are mixed to liking:
1. organo phosphorous compounds
Acephate, Azamethiphos, triazotion, methyl R-1582, bromofos, bromophos_ethyl, Zaprawa enolofos, chlormephos, Chlorpyrifos, methyl Chlorpyrifos, Systox, S-demeton_S_methyl, sulphur is inhaled sulphur phosphorus, imino-formyl chloride sulphur phosphorus, diazinon, SD-1750, Carbicron, O, O-1,2,2,2-tetrachloro ethyl phosphorothioic acid ester (SD208304), Rogor, thiodemeton, EPN, Nialate, ethoprop, etrimfos, cut down the sulphur phosphorus that goes out, Nemacur kills the toad pine, fensulfothion, Tiguvon, N-2790, peace fruit, Heptenophos, Isozophos, the first third thiodemeton ， isoxazole sulphur phosphorus, Malathion, butylene sulphur phosphorus, acephatemet, first thiophene sulphur phosphorus, water thing sulphur phosphorus, Phosdrin, monocrotophos, naled, omethoate, sulfone is inhaled sulphur phosphorus, thiophos, parathion-methyl, Tsidial, phorate, Phosalone, oxygen cyclammonium phosphorus, R-1504, phosphamidon, Volaton, pirimiphos-ethyl, methylpyrimidine sulphur phosphorus, profenofos, Kayaphos, proetamphos, low toxicity sulphur phosphorus, pyraclofos, pyridaphenthione, quinoline oxane sulphur phosphorus, sulprofos, temephos, special fourth phorate, tetrachlorvinphos, thiometon, triazophos, Trichlorphon, the intact sulphur phosphorus that goes out.
2. amino formate
Aldicarb, 2-secondary butyl phenenyl methyl carbamate, (BPMC), SevinCarbaryl, furans pellet, hundred mu of fourth sulphur grams, cloethocarb, Benfuracarb, ethiofencarb, Furathiocarb, isoprocarb, Insecticide 1179,5-methyl-m-Cu-menybutyryl(methyl)-Carbamate, grass oxime prestige is gone out and is decided fear, Propoxur, Thiodicarb, the ethyl ketone oxime, ethyl-4,6,9-three nitrogen-4-benzyl-6,10-dimethyl-8-Evil-7-oxo-5,11-dithia-9-dodecylene acid esters (OK135), 1-methylthio group (ethyleneimino)-N-methyl-N-(morpholinyl sulfenyl) carbamate (UC51717);
3. carboxylic acid esters
Allethrin, alphacypermethrin, 5-benzyl-3-furyl methyl-(E)-(1R)-cis-2,2-dimethyl-3-(2-oxygen tetramethylene sulfide-3-ylidenylmethyl) cyclopropanecarboxylcompound, dextrorotation counter-propylene chrysanthemum ester, dextrorotation counter-propylene chrysanthemum ester (S)-cyclopentyl isomer), resmethrin, Biphenate, (RS)-and 1-cyano group-1-(6-phenoxy group-2-pyridyl) methyl-(1R)-and cis-3-(4-tert-butyl-phenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (NCI 85193), Cycloprothrin, cyhalothrin, Cypermethrin, Cyphenothrin, Deltamethrin, Empenthrin, cis fenvalerate, Fenfluthrin, go out and sweep profit, fenvalerate, flucythrinate, flumethrin, taufluvalinate (D-isomer), permethrin, phenothrin ((R)-isomer), d-pralethrin, pyrethrin I (natural product), resmethrin, Tefluthrin, Tetramethrin, Tralomethrin;
4. amidine class
Amitraz, chlordimeform;
5. tin compound
Cyhexatin, mite is finished tin;
Other
Love power mite gram, Bacillus thuringiensis, Bensultap; Niagara 9044, bromine kills mite, excellently readily takes the opportunity to; toxaphene, Padan, G-23922; UC 62644, the 2-(4-chlorophenyl)-4,5-diphenyl thiophene (UBI-T930); chlorfentezine, cyclopropane-carboxylic acid-(2-naphthyl methyl) ester (RO12-0470), cyromazin; N-(3; 5-two chloro-4-(1,1,2; 3; 3,3-hexafluoro-1-propyl group oxygen base) phenyl) formamyl)-2-chlorophenyl carbonyl imines carboxylic acid, ethyl ester, dichlorodiphenyl trichloroethane; kelthane; N-(N-(3,5-two chloro-4-(1,1; 2; 2-tetrafluoro oxyethyl group) carbonyl phenyl amino))-2,6-difluorobenzamide (XRD473), diflubenzuron; N-(2; 3-dihydro-3-methyl isophthalic acid, the 3-thiazole-2-ylides)-2, the 4-xylidine; dinobuton; Mildex, 5a,6,9,9a-hexahydro-6,9-methano-2,4, trebon; (4-ethoxyl phenenyl)-(dimethyl) (3-(3-Phenoxyphenyl) propyl group) silane; (4-ethoxyl phenenyl)-(3-(4-fluoro-3-Phenoxyphenyl) propyl group) dimethyl alkane, Fenoxycarb, 2-fluoro-5-(4-(4-ethoxyl phenenyl)-4-methyl-1-pentene base) diphenyl ether (MTI800); Dian Fentang; and Kernpolyederviren, Fenthiocarb, Flubenzzimine; Flucycloxuron; stuck gram, r-phenyl-hexachloride, hexythiazox; Hydramechylnon(AC217300); Ivermectin, 2-nitro methyl-4,5-dihydro-6H-thiazine (SD52618); 2-nitro methyl-3; 4-thiazoline (SD35651), 2-nitro methylene-1,2-thiazines alkane-3-base amino-formaldehyde (WL108477); propargite; farming dream spy, tetradifon, tetradifon; thiocyclam, Triflumuron.
Can in very large range be changed by active constituent content in the formulation of the application form of common commodity formulation preparation, the concentration of effective constituent can be in 0.0001 to 95%(weight in the application form formulation), preferably 0.001 and 1%(weight) between.The method commonly used that the use of the formulation of application form optional is suitable.
Following Example is used to explain the present invention, but is not limited to this.
A. formulation preparation example
A) pulvis is that the talcum as inert substance with 10 parts of heavy effective constituents and 90 parts heavy mixes to be incorporated in and grinds in the hammer mill and make.
B) in water easily the dispersive wettable powder be effective constituent with 25 parts of weights; 65 parts of recasts are containing of inert substance of kaolinic quartz, and 10 parts of heavy calcium lignin sulphonates and the 1 part heavy oleoyl N-methyltaurine sodium as wetting agent and dispersion agent mix mutually to be incorporated in and grinds in the plain grinding and make.
C) in water easily dispersive to disperse enriched material be sulphur succinic acid half-ester with 40 parts of heavy effective constituents and 7 parts of weights, 2 parts heavy lignosulfonic acid sodium salts and 51 parts of heavy water is mixed to be incorporated in and to be milled to granularity in the ball mill below 5 microns and make.
D) missible oil is the effective constituent by 15 parts of weights, and the 75 parts heavy nonyl phenol (10AeO) as the ethoxylation of emulsifying agent as the pimelinketone of solvent and 10 parts of weights is formed.
E) granule is by 2-15 part heavy effective constituent and an inert particulate carrier substance such as an atlapulgite, and float stone particle and/or quartz sand are formed.People can use by routine b) wettable powder that makes is mixed with the suspension that contains wettable powder solids component 30%, this suspension is sprayed onto atlapulgite particulate surface, dry and thoroughly mix, the finished particle agent that obtains of method contains about 5%(weight thus) wettable powder and about 95% inert support material.
B. chemical preparation example
Example 1
2-(4-chloro-phenyl-hydrazono-)-acetoacetic acid-(2,2,6,6-tetramethyl--piperidin-4-yl)-amide salt acidulants
0.02 mole 4-chloroaniline 2.55g is dissolved in by carrying out diazotization reaction with 0.02 mole of Sodium Nitrite (1.38g) in 10ml water down in the mixture of 20ml water and 9ml concentrated hydrochloric acid and at 0 ℃.
After ℃ following stirring 10 minutes, with this diazonium salt solution be added drop-wise to 0 ℃ to+3 ℃ under violent stirring by containing 0.02 mole of acetoacetic acid-(2,2,6,6-tetramethyl piperidine-4-yl) the 30ml aqueous solution of acid amides is in the mixture that 10ml methyl alcohol and 8g sodium-acetate are formed.At room temperature stir suction filtration after 2 hours, wash residue with water and heat in acetone, obtain the crystallization of 6.5g lacteous, it is in fusing more than 260 ℃.
Nuclear magnetic data (CDCl
3, δ-value, TMS is as interior mark)
4-chlorophenyl: m; 7,15-4H
CH
3-CO：s;2，5-3H
Residual piperidines-hydrogen m; 1,38-2,15
Example 2
2-(4-chloro-phenyl-hydrazono-)-acetoacetic acid-(2,2,6,6-tetramethyl--piperidin-4-yl) acid amides
The acid amides of 0.01 mole (4.15g) that will be obtained by example 1 is suspended in the mixture of being made up of 30ml water and 15ml methyl alcohol, and to add to the pH value of solution value with the NaOH drips of solution of 0.5N be 10.
With unnecessary water it is precipitated fully then, obtain the crystallization (3.6g) of light orange, fusing point: 164-165 ℃.
Nuclear magnetic data
4-chloro-phenyl-: m; 7,3-4H
CH
3-CO：s;2，5-3H
Residual piperidines-hydrogen: m; 1,0-1,42 und 1,82-2,06-17H
Example 64
2-(4-chloro-phenyl-hydrazono-) acetoacetic acid-(2,2,6,6-tetramethyl piperidine-4-yl)-amidoxime-hydrochloride
The 30ml methyl alcohol that contains 0.03 mole of hydroxylammonium chloride (2.08g) neutralizes with the 15ml frozen water that contains 0.03 moles of NaOH (1.2g), this hydroxylamine solutions is added drop-wise to contains 0.03 mole of 2-(4-chloro-phenyl-hydrazono--acetoacetic acid-(2,2,6,6-tetramethyl piperidine-4-yl) in the 150ml dimethyl sulfoxide (DMSO) of amide hydrochloride (product that 12.5g is obtained by example 1).At room temperature stir 5 hours postcooling to 0 ℃, leach sedimentary crystallization, water and ice-cold methanol wash obtain the crystallization of 9.3g tawny, and its fusing point is greater than 260 ℃.
C
19H
29Cl
2N
5O
2（430，38）
At table 1, example number can be with the method preparation that is similar to example 1 and 2 for the compound of 3-63a and 68-102 in 3 and 4, and the compound of routine 65-67 can be with the method preparation that is similar to example 64 in table 2.Other hydrochloride can be by adding equimolar amount acid free acid amides (preparing) to the methanol solution by example 2 methods prepare.
C. biological Examples
Example 1: oidium
It is wetting with children's product to drop for the seedling in after planting about six weeks of grape of " Riesling/Ehrenfelder " to handle kind with the aqeous suspension of The compounds of this invention.After treating that topped soup is done, plant makes plant wetting by full sub-suspension with the inoculation of oidium zoospore suspension, and it is 23 ℃ that postvaccinal plant is placed temperature, and relative humidity is in 80-90 ℃ the phytotron 4-5 hour.
In the greenhouse, hatch after 7 days, plant is placed in the phytotron once more spends the night, to promote the formation of fungal spore.Only then carry out the evaluation that disease infects situation.The degree that infects is represented by the per-cent that is infected with the blade face of comparing with the adjoining tree (degree of infecting is 100%) that medication is not handled.
When containing 500mg effective constituent in every liter of spray liquid, following compounds can suppress infecting of disease fully:
Compound is 1,2,3,4 routine number, 5,6,11,64,65,66 and 67.
Example 2: late blight
Spraying kind with the aqeous suspension of The compounds of this invention be that extremely whole plant is evenly wetting by drop for the tomato of 3-4 leaf phase of " Rheinlands Ruhm ".After soup does, with the zoospore suspension of late blight plant is inoculated, after the inoculation plant placed disease to infect the phytotron 2 days of top condition.Then plant is placed the greenhouse to cultivate until the disease symptom occurring.A week is estimated the situation that infects after hatching.The degree that plant is infected is to represent by the per-cent that is infected with the blade face of comparing with untreated control plant (degree of infecting is 100%).
When containing 500mg effective constituent in every liter of spray liquid, following compounds can suppress infecting of disease fully:
Compound is 1,2,3,4 routine number, 5,6,7,12,13,15,20,21,23,64,65,66 and 67.
Example 3: gray mold
Aqeous suspension sprinkling kind with The compounds of this invention makes it wetting by soup for the broad bean plant that " Herz-Freya " or " Frank ' s Ackerperle " grown 14 days.Plant is inoculated with gray mold spore suspension (1.5 percentages spore/milliliter) etc. the dried back of topped soup.It is 20-22 ℃ that postvaccinal plant places temperature, and relative humidity is approximately and continues in 99% the phytotron to cultivate.Disease takes place and infects and can the black scab occur at leaf and stem in plant.After inoculating about 1 week test is estimated.Plant is determined that by comparing with the adjoining tree (infect is 100%) of not medication processing it infects per-cent by the degree that disease infects.
When containing 500mg effective constituent in every liter of spray liquid, following compounds can suppress infecting of disease fully:
Routine number of compound: 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,18,19,21,23,24,25,64,65,66 and 67.
Claims (13)
1, compound shown in the formula I or their salt,
In formula
R
1Be hydrogen, (C
1-C
12)-alkyl, (C
2-C
6)-alkenyl, (C
2-C
6)-alkynyl, alkyl wherein, when alkenyl and alkynyl need can with 3 of as many as identical or different be selected from halogen, (C
1-C
3)-alkoxyl group, (C
1-C
3)-alkylthio, cyano group, (C
3-C
6The substituting group of)-cycloalkyl, if the aryl that also replaces when needing and aryloxy or this three groups of replacing when needing are not included in the definition listed above, can be when needing by halo part or complete, also have identical or different the oxygen, (C that also replace when the 5-of the replacement of sulphur and nitrogen heteroatom or 5 yuan of heterocycles need of being selected from of 3 of as many as when needing
3-C
9)-cycloalkyl or the phenyl or naphthyl that replaces when needing;
R
2Be hydrogen, (C
1-C
4)-alkyl, (C
1-C
3)-alkyloyl or (C
1-C
3)-alkoxy carbonyl;
R
3Be (C
1-C
4)-alkyl;
R
4Be hydrogen, cyanoethyl, benzyl, OH, O or COOR
3
X is identical or different group, is selected from halogen, cyano group, nitro, thiocyano, (C
1-C
6)-alkyl, (C
1-C
6)-alkoxyl group, (C
1-C
6)-alkylthio, can be when alkyl wherein, alkoxyl group need with alkylthio with 3 of as many as identical or different halogen and the (C of being selected from
1-C
3The substituting group of)-alkoxyl group, if or these three groups be not included within the top definition, they can be by partially or completely halogenation, (C when needing
1-C
3)-alkoxy carbonyl, aryl, aryloxy or aroyl, 5 identical or different substituting groups that are selected from halogen or trifluoromethyl of each had as many as of these three groups wherein, (C
3-C
6)-cycloalkyl or NR
5R
6, or n 〉=, 2 adjacent X with the phenyl ring that carries them form a naphthalene-or tetrahydro naphthyl and, if n＞2, remaining X base as top determined implication;
Y is O or NOH;
R
5And R
6Be identical or different, but hydrogen, (C
1-C
4)-alkyl or by identical or different (C
1-C
3Trisubstituted (the C of)-alkyl
3-C
6)-cycloalkyl and
N is the integer of 0-4,
2, according to compound shown in the formula I of claim 1 or their salt, in formula
R
1Be hydrogen, (the C that replaces when needing
1-C
4)-alkyl, the phenyl that replaces when needing, phenyl methyl that replaces when the needing or (C that replaces when needing
3-C
6)-cycloalkyl;
R
2Be hydrogen, (C
1-C
4)-alkyloyl or (C
1-C
3)-alkoxy carbonyl;
R
3It is methyl;
R
4Be hydrogen;
X is identical or different, is halogen, nitro, thiocyano, cyano group, (C
1-C
3)-alkoxy carbonyl, (C
1-C
3)-alkyl, (C
1-C
3)-alkoxyl group, (C
1-C
3)-alkylthio, alkyl wherein, alkoxyl group can all or part ofly be replaced by identical or different halogen atoms with alkylthio, phenyl, phenoxy group or benzyl acyl group, wherein each of these three groups can be replaced by the halogen one or many and/or can be replaced by trifluoromethyl,
Y be O or NOH and
But n 0-3,
3, according to compound shown in claim 1 or the 2 Chinese style I or their salt, in formula
R
1Be methyl or cyclopropyl;
R
2Be hydrogen,
R
3Be methyl,
R
4Be hydrogen,
X is identical or different, is halogen, cyano group, (C
1-C
3)-alkyl, (C
1-C
3)-alkoxyl group or (C
1-C
3)-alkylthio, alkyl wherein, alkoxyl group can all or part ofly be replaced by identical or different halogen atoms with alkylthio;
Y be O or NOH and
But n 1-3.
4, the method for the compound shown in one the formula I among the preparation claim 1-3, its characteristics are, can use
A) reaction of the diazonium salt shown in compound shown in the general formula II and the general formula III,
Substituting group in the formula have in claim 1 given implication, or
B) reaction of the compound shown in compound shown in the general formula IV and the general formula V
R in the formula IV
1And X
nHave in the above given implication and R
5But methyl or ethyl,
R in the formula V
2, R
3And R
4Above having given implication,
Can be converted into their salt when needing with the compound shown in the resulting formula I of top method.
5, medicament contains one compound and at least one formulation material at least one claim 1 to 3.
6, according to the sterilant of claim 5, additive or the auxiliary material commonly used that contains one compound among at least one claim 1-3 and add for application therewith with germicidal action dosage.
7, plant protection product; contain other effective constituent of one compound at least one claim 1 to 3 and at least one with germicidal action dosage; preferred fungicide; sterilant; attractive substance; apholate, miticide, nematocides and weedicide and auxiliary agent and the additive materials commonly used that adds for application therewith.
8, be applied to wood protection or, contain in the claim 1 to 3 of at least one useful effect dosage one compound and auxiliary agent and the additive materials commonly used that adds for application therewith as coating antiseptic and as the medicament of boring in the metal processing and cutting cutting oil.
9, the method for one preparation among the preparation claim 5-8, its characteristics are that people make it to become a suitable applications form together with effective constituent and other additive.
10, the compound of among the claim 1-3 or a medicament of one among the claim 5-8 are as the purposes of sterilant.
11, a medicament of one in one formula I compound among the claim 1-3 or the claim 5,6 and 8 is as Wood protecting agent or as coating antiseptic and the purposes of making cutting oil in metal processing in boring and the cutting.
12, the method for control plant pathogenic fungi, its characteristics are that people can will have the compound of germicidal action dosage or require a plant that medicament is applied to these pathogenic fungies or is infected by them of one among the 5-7, surface or matrix or seed according to claim according to one among the claim 1-3 one.
13, use according to compound of one among the claim 1-3 or according to the seed of a chemicals treatment of one among the claim 5-7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4228793A DE4228793A1 (en) | 1992-08-29 | 1992-08-29 | 2-Arylhydrazono-3-ketoacid piperidides, process for their preparation, compositions containing them and their use as pesticides, in particular fungicides |
| DEP4228793.6 | 1992-08-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1084512A true CN1084512A (en) | 1994-03-30 |
Family
ID=6466725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93117041A Pending CN1084512A (en) | 1992-08-29 | 1993-08-28 | 2-aryl hydrazono--3-ketone acid pyridine, their preparation method and as the application of agricultural chemicals |
Country Status (8)
| Country | Link |
|---|---|
| CN (1) | CN1084512A (en) |
| AU (1) | AU4701893A (en) |
| DE (1) | DE4228793A1 (en) |
| IL (1) | IL106819A0 (en) |
| MX (1) | MX9305213A (en) |
| TR (1) | TR27221A (en) |
| WO (1) | WO1994005636A1 (en) |
| ZA (1) | ZA936308B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330465A (en) * | 2019-06-28 | 2019-10-15 | 深圳市三启药物开发有限公司 | Hydrazone amide derivatives and its application in preparation prevention and treatment alopecia agent |
| WO2020258971A1 (en) * | 2019-06-28 | 2020-12-30 | 深圳市三启药物开发有限公司 | Hydrazone amide derivatives and use thereof in preparation of anti-osteoporosis drugs |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4233337A1 (en) * | 1992-10-05 | 1994-04-07 | Bayer Ag | Microbicidal agents |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2727385A1 (en) * | 1976-06-23 | 1977-12-29 | Ciba Geigy Ag | NEW DIAZOCARBONIC ACID DERIVATIVES AND THEIR USE FOR STABILIZING POLYMERS |
| DE3901246A1 (en) * | 1989-01-18 | 1990-07-19 | Basf Ag | USE OF 2,2,6,6-TETRAMETHYL-4-AMINOPIPERIDINAMIDES AS A FUNGICIDE |
-
1992
- 1992-08-29 DE DE4228793A patent/DE4228793A1/en not_active Withdrawn
-
1993
- 1993-07-23 AU AU47018/93A patent/AU4701893A/en not_active Abandoned
- 1993-07-23 WO PCT/EP1993/001963 patent/WO1994005636A1/en active Application Filing
- 1993-08-27 TR TR00710/93A patent/TR27221A/en unknown
- 1993-08-27 IL IL106819A patent/IL106819A0/en unknown
- 1993-08-27 ZA ZA936308A patent/ZA936308B/en unknown
- 1993-08-27 MX MX9305213A patent/MX9305213A/en unknown
- 1993-08-28 CN CN93117041A patent/CN1084512A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330465A (en) * | 2019-06-28 | 2019-10-15 | 深圳市三启药物开发有限公司 | Hydrazone amide derivatives and its application in preparation prevention and treatment alopecia agent |
| WO2020258971A1 (en) * | 2019-06-28 | 2020-12-30 | 深圳市三启药物开发有限公司 | Hydrazone amide derivatives and use thereof in preparation of anti-osteoporosis drugs |
| WO2020258972A1 (en) * | 2019-06-28 | 2020-12-30 | 深圳市三启药物开发有限公司 | Hydrazone amide derivative and application thereof in preparation of medicaments for preventing and treating alopecia |
| CN110330465B (en) * | 2019-06-28 | 2021-05-11 | 深圳市三启药物开发有限公司 | Hydrazone amide derivative and application thereof in preparation of alopecia prevention and treatment medicines |
| CN113105411A (en) * | 2019-06-28 | 2021-07-13 | 深圳市三启药物开发有限公司 | Hydrazone amide derivatives and pharmaceutical compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| IL106819A0 (en) | 1993-12-08 |
| ZA936308B (en) | 1994-03-25 |
| WO1994005636A1 (en) | 1994-03-17 |
| TR27221A (en) | 1994-12-20 |
| AU4701893A (en) | 1994-03-29 |
| MX9305213A (en) | 1994-05-31 |
| DE4228793A1 (en) | 1994-03-10 |
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