CN1246118A - Chromone derivatives and bactericidal and herbicidal agent containing the same as active ingredient - Google Patents
Chromone derivatives and bactericidal and herbicidal agent containing the same as active ingredient Download PDFInfo
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- CN1246118A CN1246118A CN98802112A CN98802112A CN1246118A CN 1246118 A CN1246118 A CN 1246118A CN 98802112 A CN98802112 A CN 98802112A CN 98802112 A CN98802112 A CN 98802112A CN 1246118 A CN1246118 A CN 1246118A
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- alkyl
- cycloalkyl
- represent hydrogen
- compound
- chromone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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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
- A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
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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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Novel chromone derivatives combining high bactericidal activity with high herbicidal activity and represented by general formula (1), wherein X, Y, and Z are the same or different and each represents oxygen or sulfur; R<1> represents hydrogen, C1-6 alkyl, etc.; R<2> represents hydrogen or C1-6 alkyl; R<3> represents hydrogen, halogeno, etc.; m is an integer of 1 to 3; R<4> represents hydrogen, etc.; and R<5> represents hydrogen, etc.
Description
Invention field
The present invention relates to new chromone derivative and contain sterilant and composition weedicide of this derivative as activeconstituents.
Technical background
Having proposed various herbicidal compositions and some weedicides wherein contributes for improving agricultural productivity.Various types of useful compounds have also been found about the sterilant that agricultural or gardening are used.But, also do not have to find to have the active and efficient weeding activity of efficient sterilizing shows high security and highly selective simultaneously again between weeds and farm crop compound.
For the chromone derivative with fungicidal activity, the Japanese unexamined patent publication number is to have described chromone derivative in 193078/1996, wherein has a benzoyl substituting group on the 3-position of chromone ring.But, in the disclosure thing, do not mention its weeding activity.
Of the present invention open
An object of the present invention is to provide a kind of new chromone derivative with the active and efficient weeding activity of efficient sterilizing.
Another object of the present invention provides a kind of Bactericide composition that contains chromone derivative.
Further purpose of the present invention provides a kind of herbicidal composition that contains chromone derivative.
It is obvious that further feature of the present invention will become by following description.
The invention provides a kind of chromone derivative by general formula (1) expression
X wherein, Y and Z are identical or different, and represent oxygen or sulphur separately; R
1Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, C
1-6Haloalkyl, (C
1-6Alkoxyl group) C
1-6Alkyl, carboxyl, C
1-6Alkoxy carbonyl, cyano group, C
1-6Alkoxycarbonyl amino, C
1-6Alkylthio, C
3-8Cycloalkyl sulfenyl or by the phenyl of optional replacement; R
2Represent hydrogen, C
1-6Alkyl or C
3-8Cycloalkyl; R
3Represent hydrogen, halogen, C
1-6Alkyl, C
3-8Cycloalkyl or C
1-6Alkoxyl group; M is the integer of 1-3; When m is 2 or 3, all R
3Can be identical or different; R
4Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, C
1-6Haloalkyl, C
1-6Alkoxy or halogen; R
5Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, by the benzyl of optional replacement or C
2-6Thiazolinyl.
The present invention further provides a kind of Bactericide composition that contains the chromone derivative of general formula (1) as activeconstituents.
The present invention further provides a kind of herbicidal composition that contains the chromone derivative of general formula (1) as activeconstituents.
The chromone derivative of general formula of the present invention (1) has good fungicidal activity, can resist the caused harm of various pathogenic bacterium in agricultural and the gardening, and also has the good herbicidal activity that can resist the injurious weed growth.Chromone derivative of the present invention in addition also has high security and good selectivity.
The object lesson of each group is seen following listed in this specification sheets.
C
1-6The example of alkyl group is the straight or branched alkyl group with 1-6 carbon atom, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl and n-hexyl etc.
C
3-8The example of group of naphthene base is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group etc.
C
1-6The example of halogenated alkyl group is the straight or branched C that has 1-5 halogen atom
1-6Alkyl group, for example trifluoromethyl, chloromethyl, methyl fluoride, difluoromethyl, a chlorodifluoramethyl-, 2-chloroethyl, 2,2,2-trifluoroethyl, 2-chloro-2,2-two fluoro ethyls, 3-bromopropyl, 3-chloropropyl, 2,3-two chloropropyls, 4-fluorine butyl, 5-chlorine amyl group, 3-chloro-2-methyl-propyl and 5-chlorine hexyl etc.
(C
1-6Alkoxyl group) C
1-6The example of alkyl group is that its alkoxyl group is the alkoxy-alkyl group of alkyl group that has the straight or branched of 1-6 carbon atom, for example methoxymethyl, ethoxyl methyl, propoxy-methyl, 1-ethoxyethyl group, 2-ethoxyethyl group, 2-methoxy-propyl, 3-methoxy-propyl, 4-methoxyl group butyl, 2-methyl-2-methoxy-propyl, 2-methyl-3-methoxy-propyl, 1-methyl isophthalic acid-methoxy ethyl, 3-methoxyl group butyl and 2-methoxyl group butyl etc. for alkoxy base and its moieties of the straight or branched that has 1-6 carbon atom partly.
C
1-6The example of alkoxycarbonyl groups is that its alkoxyl group partly is the alkoxycarbonyl groups that has the straight or branched alkoxy base of 1-6 carbon atom, for example methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, butoxy carbonyl, isobutoxy carbonyl and tert-butoxycarbonyl etc.
C
1-6The example of alkoxycarbonyl amino group is that its alkoxyl group partly is the alkoxycarbonyl amino group that has the straight or branched alkoxy base of 1-6 carbon atom, for example methoxycarbonyl amino, ethoxy carbonyl amino, propoxycarbonyl amino, isopropoxy carbonyl amino, butoxy carbonyl amino, isobutoxy carbonyl amino and tert-butoxycarbonyl amino etc.
C
1-6The example of alkylthio group is the straight or branched alkylthio group with 1-6 carbon atom, for example methylthio group, ethylmercapto group, iprotiazem base, uncle's butylthio and cyclohexyl sulfenyl etc.
C
3-8The example of cycloalkyl sulfenyl group is cyclopropyl sulfenyl, cyclobutyl sulfenyl, cyclopentyl sulfenyl, cyclohexyl sulfenyl, suberyl sulfenyl and ring octyl group sulfenyl etc.
C
1-6The example of alkoxy base is the straight or branched alkoxy base that has 1-6 carbon atom, for example methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, pentyloxy and hexyloxy etc.
The example of halogen atom is fluorine, chlorine, bromine and iodine.
C
2-6The example of alkenyl group is the straight or branched alkenyl group that has 2-6 carbon atom, for example vinyl, allyl group, 2-methacrylic, crotyl and 2-methyl isophthalic acid-propenyl etc.
The example of the phenyl of optional replacement and the benzyl of optional replacement is that those have 1-5 substituting group, preferred 1-3 substituting group, more preferably 1-2 substituent group.Substituent example is halogen, C
1-6Alkyl, C
1-6Haloalkyl, C
1-6Alkoxyl group, C
2-6Thiazolinyl, C
2-6Alkynyl, nitro and cyano group etc.
In compound of the present invention, those wherein have a compound as substituent triazole ring on the 6-position of chromone ring is preferred.
In compound of the present invention, particularly preferably be those R
1Be methyl, R
2Be hydrogen, R
3Be methyl, m is 2, and X and Y are oxygen, and has two by R on the 5-position of chromone ring and 8-position
3The substituting group of expression has a substituent compound of triazole ring on the 6-position.In these compounds further preferably those on triazole ring, R
4For methyl or have 1-3 the substituent methyl of halogen atom, R
5Be C
1-6Alkyl and Z are the compounds of oxygen or sulphur.
Even a spot of use compound of the present invention also can effectively be controlled various fungal diseases, comprise, for example, the fungal disease of following kind: rice blast (Magnaporthe grisea), maize seedling rot (beading sickle spore), apple mildew (white cross hair list softgel shell), scab of apple (venturia inaequalis), apple orchard star disease (apple spot ball chamber bacterium), apple anthracnose (Marssonina genus), apple brown rot (Sclerotinia), persimmon white powder (persimmon is given birth to ball pin shell), persimmon anthrax (colletotrichum gloeosporioides Penz), tea blossom rot (Sclerotinia), peach scab (Blastocladia), apple seedling damping-off (Phomopsis), grape grey mould (Botrytis cinerea), the grape angular leaf spot, uncinula necator (grape snag shell), grapevine anthracnose (Elsinochrome), grape bitter rot (small cluster shell bacterium), beet cercospora leaf spot (beet is given birth to the tail spore), peanut tail spore foxiness (peanut is given birth to the tail spore), peanut blackspot (ball seat tail spore), barley powdery mildew (Gramineae Bu Shi powdery mildew), the wheat basal stem rot, barley red mould (it is mould to avenge rotten form), soybean frogeye tikka (soybean tail spore), wheat powdery mildew (Gramineae Bu Shi powdery mildew), cucumber fusarium axysporum (sharp sickle spore cucumber specialized form), cucumber anthracnose (melon anthrax-bacilus), the Kidney bean Powdery Mildew, gummy stem blight of melon (muskmelon ball chamber bacterium), the capsicum sclerotium disease, peanut gray mold (Botrytis cinerea), cucumber shot hole (melon branch spore), potato late blight (phytophthora infestans), leaf muld of tomato (Fulvia fulva), gray mold of cucumber (Botrytis cinerea), the cucumber brown spot, apple wilt disease (wheel branch spore), powdery mildew of strawberry, beet sickle-like bacteria damping-off (sharp sickle spore), onion stem rot (grape spore), sweet potato sclerotinia (sclerotinite), celery septoria disease (Septoria), Kidney bean angular leaf spot (brown post silk is mould), corn sclerotium disease (sclerotinite), grey mould of sweet potato (Botrytis cinerea), tobacco Powdery Mildew (two spore powdery mildews), Chinese rose black spot (rose bivalve bacterium), citrus scab (oranges and tangerines Elsinochrome), oranges and tangerines penicilliosis (Italian mould), citrus common green mold (Penicillium digitatum) etc.
A spot of The compounds of this invention also can kill various deleterious weeds effectively.The weeds that can effectively be controlled by The compounds of this invention are, for example, Eclipta prostrata belongs to prostrate (L.) L., green amaranth L., Choisy leads a cow, Herba Aeschynonenes Indicae (close and sprout), and amur foxtail belongs to Solo var.amurensis Ohwi, water pepper L., Pamp. chrysanthemum ends, and bitter fleabane belongs to sumatrensis Retz., curled dock L.Subsp.Japonicus Kitam., Brittle Falsepimpernel Herb pxyidaria L., Herba Clinopodii Polycephali belongs to indica koehne, barnyard grass (a kind of wild annual dogstail), knotgrass dogstail (ciliaris Koeler), Herba Eleusines Indicae Gaertner, small brokens sand grass Steud. etc.
The represented chromone derivative of general formula of the present invention (1) can prepare by diverse ways.Typical method is as follows:
Reaction formula-1
R wherein
1, R
2, R
3, R
5, m, X, Y and Z such as front define, R
4aRepresent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl or C
1-6Haloalkyl, R
6Represent C
1-4Alkyl.
According to reaction formula-1, with a kind of (sulphur) the half carbohydrazide chromone and the acid anhydrides of general formula (2) or the compound that ortho ester does not use solvent or reaction generates general formula of the present invention (1a) in appropriate solvent.
Spendable solvent is in this reaction, for example, and aromatic hydrocarbon, halogenated hydrocarbon, alcohols, ethers, amides, sulfoxide class and their mixture.The example of aromatic hydrocarbon comprises benzene, toluene and dimethylbenzene.The example of halogenated hydrocarbon is methylene dichloride and 1, the 2-ethylene dichloride.The example of alcohols is methyl alcohol and ethanol.The example of ethers is dioxane and tetrahydrofuran (THF).The example of acid amides is dimethyl formamide and N-Methyl pyrrolidone.The example of sulfoxide comprises dimethyl sulfoxide (DMSO).
The example of acid anhydrides comprises diacetyl oxide, Monochloro Acetic Acid acid anhydride, Trichloroacetic anhydride, a gifblaar poison acid anhydride, difluoroacetic acid acid anhydride and trifluoroacetic anhydride.
The example of ortho ester comprises triethyl orthoformate, triethly orthoacetate and former propionic acid trimethyl.
These acid anhydrides and ortho ester are industrial easy acquisitions.
The ratio of acid anhydrides or ortho ester and (sulphur) half carbohydrazide chromone without limits.Under the situation of acid anhydrides, with respect to every mole (sulphur) half carbohydrazide chromone, the amount of employed acid anhydrides is about 0.5～about 5 moles, preferred about 1～about 3 moles.Under the situation of ortho ester, with respect to every mole (sulphur) half carbohydrazide chromone, the amount of employed ortho ester is about 0.5～about 20 moles, preferred about 1～about 12 moles.Ortho ester is the effect of act as solvents also.
Carry out in the above-mentioned temperature range that is reflected at boiling point from room temperature to the use solvent.For example, when the carbonyl compound that uses acid anhydrides and Z wherein as oxygen reacted, this reaction was carried out under reflux temperature about 20～about 50 hours usually, or acid catalyst for example tosic acid in the presence of about 1～20 hour of backflow.When the thiocarbonyl group compound that uses acid anhydrides and Z wherein as sulphur reacted, reaction was at room temperature carried out usually and is complete at about 1～5 hour internal reaction.When using ortho ester and carbonyl compound or thiocarbonyl group compound to react, reaction is carried out under 80-110 ℃ temperature usually and is complete at about 0.5～10 hour internal reaction.
(sulphur) half carbohydrazide chromone of general formula in the reaction formula-1 (2) can prepare by known method from corresponding amino chromone.Detailed method can be referring to No. the 4th, 514,419, United States Patent (USP) for example.
The amino chromone of starting raw material can form chromone by currently known methods, then chromone is carried out nitrated and reduction and preparing.The method that forms chromone comprises that for example, " organic reaction " be the described method of 7 page 1 (1953) (OrganicReaction), and this method comprises reacts phenol and 'beta '-ketoester in the presence of Tripyrophosphoric acid; " organic synthesis " (Organic Synthesis) Volume Four, method described in the 478th page (1963) or " chemical education magazine " (Journal of ChemicalEducation) 57 phases the 220th page (1980), this method comprises and hydroxy acetophenone is converted into 1, the step of 3-diketone; Or 104, the 348 pages of (1971) middle methods of describing of Chemische Berichts, this method comprises the step that changes into enamine.
Reaction formula-2
R wherein
1, R
2, R
3, R
5, m, X, Y and Z such as front define, R
4bBe C
1-6Alkoxy or halogen, R
7Represent C
1-4Alkyl.
According to reaction formula-2, with the chromone derivative of the 'beta '-ketoester reaction production (1b) of the oxybenzene compound of formula (3) and formula (4).
This reaction be in the presence of a kind of condensation reagent in appropriate solvent or do not use under the condition of any solvent and carry out.The ratio of the 'beta '-ketoester of the oxybenzene compound of formula (3) and formula (4) is unqualified, can suitably select in the scope of broad.Usually the amount with respect to the employed 'beta '-ketoester of every moles of phenol compound is about 0.5～about 10 moles, preferred about 0.8～about 2 moles.
Spendable solvent is in this reaction, for example, and aromatic hydrocarbon, halogenated hydrocarbon and their mixture.The example of aromatic hydrocarbon comprises benzene, toluene and dimethylbenzene.The example of halogenated hydrocarbon comprises methylene dichloride and 1, the 2-ethylene dichloride.
The example of available condensing agent comprises Tripyrophosphoric acid.This condensing agent uses with the amount excessive with respect to the oxybenzene compound of formula (3) usually.
Above-mentioned reaction is carried out under the condition of heating usually, preferably carries out under 70 ℃-150 ℃ condition, and finished reaction in about 1～about 20 hours.
The oxybenzene compound of the starting raw material formula (3) in reaction formula-2 can easily prepare by currently known methods, for example according to Journal of Organic Chemistry, 54, the 1048-1051 pages or leaves, (1989) method of describing in, or the preparation of the method described in the WO95/14009.
The 'beta '-ketoester of other starting raw material formula (4) in reaction formula-2 is a known compound.The example of the 'beta '-ketoester of formula (4) comprises methyl aceto acetate, 2-methyl-acetoacetic ester and Propionylacetic acid ethyl ester.
Reaction formula-3
R wherein
1, R
2, R
3, R
4, R
5, m and X such as front define.
According to reaction formula-3, the compound of formula of the present invention (1c) is changed into the 4-thiochromone derivative of a kind of formula (1d).
This reaction can be carried out in appropriate solvent usually.Spendable solvent comprises aromatic hydrocarbon such as benzene and toluene in this reaction, or dithiocarbonic anhydride.
The example of sulfuration reagent comprises thiophosphoric anhydride and Lawesson reagent [2,4-two (4-p-methoxy-phenyl)-1,3-two sulphur-2,4-diphosphine alkane (diphosphetane)-2,4-disulphide].The chromone derivative of formula (1c) is unqualified with the ratio of sulfuration reagent, can suitably select in the scope of broad.Usually the amount with respect to every mole of employed sulfuration reagent of described chromone derivative is about 0.5～about 5 moles, preferred about 0.5～about 2 moles.
Above-mentioned reaction is carried out in the temperature range of the boiling point from room temperature to the use solvent usually.Preferably this is reflected under the temperature near the boiling point of solvent for use and carries out, and finishes reaction usually in about 1～about 24 hours.
Reaction formula-4
R wherein
1, R
2, R
3, R
4, R
5, m and X by as top the definition.
According to reaction formula-4, the compound of formula of the present invention (1f) also can be by the compound of formula of the present invention (1e).This reaction can be passed through, and for example, the method described in the Journal of OrganicChemistry 27,976 (1962) is carried out, and this method is used nitric acid or 20% (w/w) Monochloro Acetic Acid of 8N; Or by a kind of oxygenant of use such as pyridinium dichromate (PDC), pyridinium chloro-chromate (PCC), the method for Manganse Dioxide or chromic oxide (VI) is carried out.
In last method, preferably use about 0.5～about 20 moles of the Monochloro Acetic Acid of the nitric acid or 20% (w/w) of 8N with respect to every mole of formula of the present invention (1e) compound.This is reflected in the temperature range from room temperature to this reaction mixture boiling point and carries out, and finishes reaction usually in about 1～10 hour.
In one method of back, employed solvent comprises that those are generally used for carrying out the solvent of the relative broad range of these oxidizing reactions, and these solvents are, for example, aromatic hydrocarbon such as benzene and toluene, halogenated hydrocarbon such as methylene dichloride and ethylene dichloride, acetate, and their mixture.The ratio of formula of the present invention (1e) compound and oxygenant can suitably be selected from the scope of broad without limits.Usually formula (1e) compound with respect to every mole uses about 0.5～about 10 moles, preferred about 1～about 5 moles oxygenant.Above-mentioned reaction is generally carried out in the temperature range of the boiling point from room temperature to the use solvent.This reaction is preferably carried out under reflux temperature, and finishes reaction usually in about 1～10 hour.
Can use usual method by the compound of the present invention that above-mentioned different methods obtained, for example separate and purifying by filtration, solvent extraction, distillation, recrystallization or column chromatography.
In the rice field, on the lawn or in the farmland, compound of the present invention suppresses to damage the weeds of cereal grass growth selectively, and relatively safe to rice plants, the careless class of turf (turf) [Zoysia camellia, Zoysia matrella, Anacamptis pyromaidalis, bluegrass, rye grass, Tefton], soybean, wheat, Japanese Radix Raphani, buckwheat and cereal.Therefore, compound of the present invention can improve the productivity on farm highly effectively and save the labor force.
The The compounds of this invention that uses for the activeconstituents as sterilant and herbicidal composition can add other composition.Usually; compound of the present invention is mixed with a kind of solid carrier, liquid vehicle, carrier gas or poison bait etc.; and at random with a kind of tensio-active agent or other auxiliary agent as the prescription of said composition, preferably be mixed with emulsifiable concentrate, wettable powder, dried flowable suspending concentrate, flowable suspending concentrate, water-soluble chemical product, particle, fine particle, granulated powder, pulvis, coating composition, spray agent, aerosol, microcapsule, fumigant, fumigant etc.
The example of solid carrier that is used for the prescription of these compositions is weighting agents such as clay (as diatomite, kaolin, the oxidizing aqueous silicon of synthetic, wilkinite, Fubasami clay and acid clay), ceramic clay, white carbon black, talcum; Other inorganic mineral (as diatomite (Celite), quartz, sulphur, gac, lime carbonate and hydrated silica gel); Chemical fertilizer (as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride) etc., these carriers use with forms such as fine powder or particles.
The example of used liquid vehicle is that water, alcohols (as methyl alcohol and ethanol), ketone (as acetone and methyl ethyl ketone), aromatic hydrocarbon (as benzene,toluene,xylene, ethylbenzene and methylnaphthalene), aliphatic hydrocarbon compound (as hexane, hexanaphthene, kerosene and light oil), ester (as ethyl acetate and butylacetate), nitrile (as acetonitrile and isopropyl cyanide), amides are (as N, dinethylformamide and N,N-dimethylacetamide), halogenated hydrocarbon (as methylene dichloride, trichloroethane and tetracol phenixin), dimethyl sulfoxide (DMSO) and vegetables oil (as soybean oil and Oleum Gossypii semen).
Gases used carrier is that the example of propelling agent is CFCs, butagas, LPG (liquefied petroleum gas (LPG)), dimethyl ether and carbon dioxide.
The example of used tensio-active agent is nonionic or anion surfactant.The example of nonionogenic tenside comprises Voranol EP 2001, polyxyethylated ester and polyethenoxy sorbitan alkyl ester.Examples of anionic surfactants comprises alkylbenzene sulfonate, alkyl sulfo succinate, alkyl-sulphate, laureth sulfate, arylsulphonate and xylogen sulphite.
The example of used auxiliary agent such as tackiness agent and dispersion agent of filling a prescription comprises casein, gelatin, polysaccharide, lignin derivative, wilkinite, carbohydrate, synthetic water soluble high-molecular material (as polyvinyl alcohol, polyvinylpyrrolidone and polyacrylic acid), BHT (2,6 di tert butyl 4 methyl phenol), BHA (mixture of the 2-tertiary butyl-4-methoxyphenol and the 3-tertiary butyl-4-methoxyphenol), vegetables oil, mineral oil, tensio-active agent, lipid acid and ester class thereof.
Composition of the present invention can be used the organic or inorganic dye coloring.
Thus the composition that is obtained can directly use or dilute with water after use.When needs, said composition can be mixed use with other sterilant, weedicide, sterilant, nematocides, miticide, plant-growth regulator, synergistic agent, soil improvement agent, animal feedstuff additive etc.
According to the present invention, above-mentioned various compositions can pass through with about 0.1～about 95 weight %, and the amount of preferred about 0.5～about 90 weight % obtains compound of the present invention preparation.
The composition that is obtained can directly use or use with a kind of carrier or water dilution back thus.According to its intended purposes, the concentration that said composition can be diluted to activeconstituents is about 0.0001～100 weight %, and preferred 0.001～10 weight % uses.
When the sterilant, compound of the present invention uses with per 1000 square metres of amounts with activeconstituents 10-100 gram usually, although should amount in this scope without limits.When emulsifiable concentrate, wettable powder or flowable suspending concentrate dilute with water used, this compound was the concentration use of about 10～5000ppm usually with activeconstituents.Preferred directly use of particle or wp formula need not dilution.
When by methods such as soil treatment, water treatment or chemical fertilizer processing when the weedicide, compound of the present invention usually with per 1000 square metres with activeconstituents 10～1000 grams, preferably use with 5～400 amounts that restrain, suppress the growth of weeds thus.But, this amount in this scope without limits.
Implement best way of the present invention
Detailed hereafter relate to formulation Example of the present invention, preparation embodiment and test case, wherein " part " is weight, except that other refers in particular to.Formulation Example 1 (emulsifiable concentrate)
With 10 parts of compound dissolutions of the present invention in the mixture of forming by the N-Methyl pyrrolidone of 45 parts Solvesso 150 (a kind of high solvent of aromatic hydrocarbons amount that contains) and 35 parts.The Sorpol 3005X (emulsification reagent Toho chemical industry Co., Ltd. product) that in this solution, adds 10 parts.Stir this mixture and obtain 10% emulsifiable concentrate.Formulation Example 2 (wettable powder)
20 parts of compounds of the present invention are joined by 2 parts of sodium lauryl sulphate, and 4 parts of sodium lignosulfonates are in the mixture that the fine powder of 20 parts of oxidizing aqueous silicon of synthetic and 54 parts of clays are formed.Stir resulting mixture with a kind of juice extractor, obtain 20% wettable powder.Formulation Example 3 (particle)
Add 2 parts of Sodium dodecylbenzene sulfonatees in 5 parts compound of the present invention, 10 parts of wilkinites and 83 parts of clays then fully stir.In this mixture, add an amount of water, further stir resulting mixture, carry out granulating and carry out dry air obtaining 5% particle with tablets press.Formulation Example 4 (pulvis)
With portion compound dissolution of the present invention in an amount of acetone.The oxidizing aqueous silica fine powder of the synthetic end that in this solution, adds 5 parts, the clay of 0.3 part of acid phosphatase isopropyl ester (PAP) and 93.7 parts.Stir resulting mixture with a kind of juice extractor, and evaporate acetone, obtain 1% pulvis.Formulation Example 5 (suspending concentrate can flow)
The aqueous solution that contains 3 part polyoxyethylene triphenylethylene phenyl ether phosphoric acid ester trolamines and 0.2 part Rhodorsil 426R (polysiloxane anti-pore forming material) of 20 parts The compounds of this invention with 20 parts is mixed, this mixture is carried out wet lapping with the Dyno mill, then 60 parts of aqueous solution that contain 8 parts of propylene glycol and 0.32 part of xanthan natural gum are mixed with them, obtain 20% water suspension.
For other prescription, wettable powder can obtain preparation by uniform mixing and pulverizing described composition.Emulsifiable concentrate can obtain preparation by uniform mixing and the described composition of dissolving.Particle can pass through the described composition of uniform mixing, adds water, fully mediates this mixture, with resulting compound particles granulation, and the particle that obtained of cutting and dry this fine particle and obtain preparation further.The preparation of reference example 12-sec-butyl-4-(2,5,8-trimethylammonium chromone-6-yl) sulphur half carbohydrazide
At room temperature, in 20 milliliters of dichloromethane solutions that contain 0.76 gram (6.11 mmole) sec-butyl hydrazine hydrogenchloride, add the triethylamine of 0.83 gram (8.15 mmole), this mixture was stirred 10 minutes.Contain 1.0 gram (4.08 mmole) 6-isothiocyanic acids-2,5 to wherein being added dropwise to 20 milliliters then, the dichloromethane solution of 8-trimethylammonium chromone stirs this mixture 15 hours.Add entry and isolate organic phase in this reaction mixture, water and saturated brine solution wash this organic solution and with this organic solution of anhydrous magnesium sulfate drying.The pressure reducing and steaming solvent is also used hexane wash gained resistates, obtains faint yellow solid 1.30 grams (productive rate 96%).
The NMR spectral data of resulting compound is as follows:
NMR(CDCl
3)ppm；0.97(3H，t)，1.22(3H，d)，1.50-1.75(2H，m)，2.34(3H，s)，2.40(3H，s)，2.70(3H，s)3.66(2H，s)，5.75-5.90(1H，m)，6.06(1H，s)，7.57(1H，s)，9.38(1H，bs)。The preparation of reference example 22-sec-butyl-4-(2,5,8-trimethylammonium-1-thiochromone-6-yl) sulphur half hydrazine carbonyl
At room temperature, in 20 milliliters of dichloromethane solutions that contain 0.76 gram (6.11 mmole) sec-butyl hydrazine hydrogenchloride, add the triethylamine of 0.83 gram (8.15 mmole), this mixture was stirred 10 minutes.Contain 1.1 gram (4.21 mmole) 6-isothiocyanic acids-2,5 to wherein being added dropwise to 20 milliliters then, the dichloromethane solution of 8-trimethylammonium-2-thiochromone stirs this mixture 15 hours.Add entry and isolate organic phase in this reaction mixture, water and saturated brine solution wash this organic solution and with this organic solution of anhydrous magnesium sulfate drying.Remove solvent under reduced pressure and, obtain faint yellow solid 1.30 grams (productive rate 88%) with hexane wash gained resistates.
The NMR spectral data of resulting compound is as follows:
NMR(CDCl
3)ppm；0.98(3H，t)，1.23(3H，d)，1.50-1.75(2H，m)，2.42(3H，s)，2.46(3H，s)，2.69(3H，s)，3.63(2H，s)，5.65-5.85(1H，m)，6.74(1H，s)，7.63(1H，s)，9.47(1H，bs)。Preparation embodiment 16-(1-normal-butyl-3-trifluoromethyl-5-sulfo--1,2,4-triazole-4-yl)-2,5, the preparation of 8-trimethylammonium chromone (compound sequence number 32)
2-normal-butyl-4-(2,5,8-trimethylammonium chromone-6-yl) sulphur half carbohydrazide of 0.5 gram (1.5 mmole) is suspended in 20 milliliters of toluene, and at room temperature to the trifluoroacetic anhydride that wherein is added dropwise to 0.38 gram (1.8 mmole).This mixture stirring after 1 hour, is poured in the frozen water.Organic phase is separated the water ethyl acetate extraction.Extraction liquid and organic phase are lumped together, and water and saturated this organic phase of salt water washing are also used anhydrous magnesium sulfate drying.Solvent is removed under reduced pressure, and the gained resistates is with the silica gel column chromatography (hexane: ethyl acetate=3: 1), obtain the white crystals (productive rate 75%) of 0.46 gram of purifying.Preparation embodiment 26-(1-normal-butyl-3-methyl-5-sulfo--1,2,4-triazole 4-yl)-2,5, the preparation of 8-trimethylammonium chromone (compound sequence number 12)
To reflux 3.5 hours by the mixture heating up that 0.9 gram (2.7 mmole) 2-normal-butyl-4-(2,5,8-trimethylammonium chromone-6-yl) sulphur half carbohydrazide and 4.0 gram triethly orthoacetates are formed.This reaction mixture is poured in the frozen water.Organic phase is separated the water ethyl acetate extraction.Extraction liquid and organic phase are merged, and water and saturated this organic phase of salt water washing are also used anhydrous magnesium sulfate drying.Solvent is removed under reduced pressure, and the gained resistates is with the silica gel column chromatography (hexane: ethyl acetate=1: 1), obtain the yellow-white crystallization (productive rate 70%) of 0.68 gram of purifying.Preparation embodiment 36-(1-methyl-3-trifluoromethyl-5-sulfo--1,2,4-triazole-4-yl)-2,5, the preparation of 8-trimethylammonium-4-thiochromone (compound sequence number 71)
Will be by 0.72 gram (2.0 mmole) 6-(1-methyl-3-trifluoromethyl-5-sulfo--1,2,4-triazole-4-yl)-2,5,8-trimethylammonium chromone (compound sequence number 24), the mixture heating up that 0.61 gram (1.5 mmole) Lawesson reagent and 10 milliliters of toluene are formed refluxed 6 hours.With this reaction mixture cool to room temperature, solvent is removed under reduced pressure.The gained resistates is with the silica gel column chromatography (hexane: ethyl acetate=4: 1), obtain the purple crystal (productive rate 82%) of 0.62 gram of purifying.Preparation embodiment 46-(1-methyl-3-trifluoromethyl-5-ketone group-1,2,4-triazole-4-yl)-2,5, the preparation of 8-trimethylammonium-1-thiochromone (compound sequence number 70)
With 1.0 gram (2.6 mmole) 6-(1-methyl-3-trifluoromethyl-5-sulfo--1,2,4-triazole-4-yl)-2,5,8-trimethylammonium-1-thiochromone (compound sequence number 61), 2.8 gram (13 mmole) pyridinium chlorochromate and 2.8 gram diatomite (Celite) are suspended in 50 milliliters of toluene.With this suspensoid reflux 2 hours.This reaction mixture is filtered by Celite.Filtrate decompression steamed desolventize, the gained resistates is with the silica gel column chromatography (hexane: ethyl acetate=1: 1), obtain the white crystals (productive rate 38%) of 0.39 gram of purifying.Preparation embodiment 56-(3-chloro-1-methyl-5-ketone group-1,2,4-triazole-4-yl)-2,5, the preparation of 8-trimethylammonium chromone (compound sequence number 89)
Will be by 20 gram polyphosphoric acids and 0.63 gram (3-chloro-1-methyl-5-ketone group-1,2,4-triazole-4-yl)-2, the mixture heating up to 90 that the 5-xylenol is formed ℃ and to wherein being added dropwise to 0.39 gram methyl aceto acetate.This mixture was stirred 1.5 hours under uniform temp.Pour into reaction mixture in the frozen water and use ethyl acetate extraction.With extracting solution with saturated sodium bicarbonate aqueous solution and saturated salt water washing and use anhydrous magnesium sulfate drying.Siccative is filtered, filtrate decompression is concentrated, gained crystallization hexane wash obtains 0.15 white crystals (productive rate 19%) that restrains.
Following table 1-12 has listed prepared compound and physical properties thereof in preparation embodiment 1-5, according to the compound that method obtained and the physical properties thereof that prepare embodiment 1-5.The meaning of abbreviation is as follows in table: Me=methyl, Et=ethyl, Pr=n-propyl, i-Pr=sec.-propyl, Bu=normal-butyl, the t-Bu=tertiary butyl, sec-Bu=sec-butyl, Pen=n-pentyl, Hex=n-hexyl, c.Hex=cyclohexyl, Ph=phenyl, Allyl=allyl group and Bn=benzyl.For example in table 1, at R
3Row in " 5,8-Me
2" be meant that 5-position and 8-bit strip on the chromone ring have methyl substituents.The following listed compound of chemical molecular formula (1A) representative table 1-3.Following chemical molecular formula (1B) is represented the listed compound of table 4.
Table 1No. X Y Z R
1R
2R
3R
4R
51 O O S H H H CF
3Me 2 O O S H H 8-Me CF
3Me 3 O O S H H 5,8-Me
2CF
3Me 4 O O S Me H H CF
3Me 5 O O S Me H 5-Me CF
3Me 6 O O S Me H 8-Me CF
3Me 7 O O S Me H 5,8-Me
2H Me 8 O O S Me H 5,8-Me
2Me Me 9 O O S Me H 5,8-Me
2Me Et10 O O S Me H 5,8-Me
2Me Pr11 O O S Me H 5,8-Me
2Me i-Pr12 O O S Me H 5,8-Me
2Me Bu13 O O S Me H 5,8-Me
2Me Pen14 O O S Me H 5,8-Me
2Me Hex15 O O S Me H 5,8-Me
2Me Allyl16 O O S Me H 5,8-Me
2Me Bn17 O O S Me H 5,8-Me
2Et Me18 O O S Me H 5,8-Me
2Pr Me19 O O S Me H 5,8-Me
2CF
3H20 O O S Me H 5,8-Cl
2CF
3Me21 O O S Me H 5-Cl, 8-Me CF
3Me22 O O S Me H 8-Cl, 5-Me CF
3Me23 O O S Me H 5,7-Me
2CF
3Me24 O O S Me H 5,8-Me
2CF
3Me25 O O S Me H 7,8-Me
2CF
3Me26 O O S Me H 5-Me, 8-i-Pr CF
3Me27 O O S Me H 8-Me, 5-i-Pr CF
3Me28 O O S Me H 8-Me, 5-OMe CF
3Me29 O O S Me H 5,8-Me
2CF
3Et30 O O S Me H 5,8-Me
2CF
3Pr31 O O S Me H 5,8-Me
2CF
3I-Pr32 O O S Me H 5,8-Me
2CF
3Bu
Table 2No. X Y Z R
1R
2R
3R
4R
533 O O S Me H 5,8-Me
2CF
3Pen34 O O S Me H 5,8-Me
2CF
3Hex35 O O S Me H 5,8-Me
2CF
3C.Hex36 O O S Me H 5,8-Me
2CF
3Bn37 O O S Me H 5,8-Me
2CF
3Allyl38 O O S Et H 5,8-Me
2CF
3Me39 O O S Pr H 5,8-Me
2CF
3Me40 O O S i-Pr H 5,8-Me
2CF
3Me41 O O S Bu H 5,8-Me
2CF
3Me42 O O S t-Bu H 5,8-Me
2CF
3Me43 O O S CH
2Br H 5,8-Me
2CF
3Me44 O O S CF
3H 5,8-Me
2CF
3Me45 O O S CH
2OMe H 5,8-Me
2CF
3Me46 O O S CO
2H H 5,8-Me
2CF
3Me47 O O S CO
2Me H 5,8-Me
2CF
3Me48 O O S CO
2Et H 5,8-Me
2CF
3Me49 O O S CN H 5,8-Me
2CF
3Me50 O O S NHCO
2Me H 5,8-Me
2CF
3Me51 O O S SMe H 5,8-Me
2CF
3Me52 O O S Ph H 5,8-Me
2CF
3Me53 O O S Me Me 5,8-Me
2CF
3Me54 S O S Me H 5,8-Me
2Me Me55 S O S Me H 5,8-Me
2Me Et56 S O S Me H 5,8-Me
2Me Pr57 S O S Me H 5,8-Me
2Me i-Pr58 S O S Me H 5,8-Me
2Me Bu59 S O S Me H 5,8-Me
2Me Allyl60 S O S Me H 5,8-Me
2Me Bn61 S O S Me H 5,8-Me
2CF
3Me62 S O S Me H 5,8-Me
2CF
3Et63 S O S Me H 5,8-Me
2CF
3Pr64 S O S Me H 5,8-Me
2CF
3I-Pr
Table 3No. X Y Z R
1R
2R
3R
4R
565 S O S Me H 5,8-Me
2CF
3Bu66 S O S Me H 5,8-Me
2CF
3Allyl67 S O S Me H 5,8-Me
2CF
3Bn68 O O O Me H 5,8-Me
2CF
3Me69 O O O Me Me 5,8-Me
2CF
3Me70 S O O Me H 5,8-Me
2CF
3Me71 O S S Me H 5,8-Me
2CF
3Me72 O O O Me H 8-Cl, 5-Me CF
3Me73 O O O Me H 5,8-Me
2CF
3Allyl74 O O O Me H 5,8-Me
2CF
3I-Pr75 O O O Me H 5,8-Me
2CF
3Sec-Bu76 O O O Me H 5,8-Me
2CF
3Bu77 O O O Me H 5,8-Me
2CF
3Pen78 O O O Me H 5,8-Me
2CF
3Hex79 O O O Me H 5,8-Me
2CF
3C.Hex80 O O O Me H 5,8-Me
2CF
3Bn81 S O O Me H 5,8-Me
2CF
3Et82 S O O Me H 5,8-Me
2CF
3Allyl83 S O O Me H 5,8-Me
2CF
3I-Pr84 S O O Me H 5,8-Me
2CF
3Pr85 S O O Me H 5,8-Me
2CF
3Sec-Bu86 S O O Me H 5,8-Me
2CF
3Bu87 S O O Me H 5,8-Me
2CF
3Bn88 O O O Me H 5,8-Me
2OMe Me89 O O O Me H 5,8-Me
2Cl Me90 O O S Me H 5-Me, 8-F CF
32-Butenyl91 O O S Me H 8-Me CH
3Allyl92 O O S Me H 5,8-Me
2CH
32-Butenyl93 O O S Me H 5-Me, 8-F CH
3Bu94 O O S Me H 5,8-Me
2CF
3Sec-Bu95 S O S Me H 5,8-Me
2CF
3Sec-Bu
Table 4NO. X Y Z R
1R
2R
3R
4R
596 O O S Me H 5,7-Me
2CF
3Me
Table 5No. mp (℃) NMR (CDCl
3) ppm1 155-156 3.92 (3H, s), 6.41 (1H, d), 7.55-7.75 (2H, m), 7.91 (1H, d),
8.20(1H，d)2????160-162??2.55(3H，s)，3.92(3H，s)，6.38(1H，d)，7.47(1H，d)，
7.93(1H，d)，8.04(1H，d)3????209-210??2.46(3H，s)，2.53(3H，s)，3.93(3H，s)，6.34(1H，d)，
7.27(1H，d)，7.84(1H，d)4????156-158??2.43(3H，s)，3.92(3H，s)，6.23(1H，s)，7.61(1H，d)，
7.62(1H，d)，8.16(1H，s)5????148-150??2.37(3H，s)，2.57(3H，s)，3.93(3H，s)，6.15(1H，s)，
7.38(1H，d)，7.44(1H，d)6????176-177??2.45(3H，s)，2.54(3H，s)，3.91(3H，s)，6.23(1H，s)，
7.43(1H，d)，8.00(1H，d)7????172-173??2.40(3H，s)，2.48(3H，s)，2.60(3H，s)，3.88(3H，s)，
6.10(1H，s)，7.35(1H，s)，7.80(1H，s)8????175-176??2.10(3H，s)，2.38(3H，s)，2.45(3H，s)，2.50(3H，s)，
3.80(3H，s)，6.10(1H，s)，7.22(1H，s)9????149-150??1.48(3H，t)，2.10(3H，s)，2.39(3H，s)，2.46(3H，s)，
2.51(3H，s)，4.30(2H，q)，6.16(1H，s)，7.28(1H，s)
1.02(3H，t)，1.91-1.99(2H，m)，2.01(3H，s)，2.39(3H，s)，10???235-236??2.46(3H，s)，2.51(3H，s)，4.23-4.33(2H，m)，6.16(1H，s)，
7.28(1H，s)11???213-214??1.49(6H，d)，2.01(3H，s)，2.42(3H，s)，2.46(3H，s)，
2.49(3H，s)，5.18-5.27(1H，m)，6.15(1H，s)，7.29(1H，s)
Table 6No. mp (℃) NMR (CDCl
3) ppm
1.00(3H，t)，1.35-1.40(2H，m)，1.80-1.95(2H，m)，12????151-152??2.10(3H，s)，2.40(3H，s)，2.46(3H，s)，2.51(3H，s)，
4.24(2H，t)，6.15(1H，s)，7.28(1H，s)
0.93(3H，t)，1.35-1.45(4H，m)，1.85-1.96(2H，m)，13????129-130??2.10(3H，s)，2.39(3H，s)，2.46(3H，s)，2.51(3H，s)，
4.23(2H，t)，6.15(1H，s)，7.28(1H，s)14????109-110??0.90(3H，t)，1.20-1.50(4H，m)，1.80-2.05(2H，m)，
2.10(3H，s)，2.39(3H，s)，2.46(3H，s)，2.50(3H，s)，
4.22(2H，t)，6.15(1H，s)，7.28(1H，s)
2.10(3H，s)，2.39(3H，s)，2.46(3H，s)，2.52(3H，s)，15????167-168??4.87(2H，dd)，5.34(1H，d)，5.38(1H，dd)，
5.95-6.10(1H，m)，6.15(1H，s)，7.28(1H，s)
2.07(3H，s)，2.39(3H，s)，2.46(3H，s)，2.52(3H，s)，16????174-175??5.40(1H，d)，5.48(1H，d)，6.15(1H，s)，7.28(1H，s)，
7.30-7.45(3H，m)，7.50-7.55(2H，m)17????100-103??1.18(3H，t)，2.25-2.40(5H，m)，2.46(3H，s)，2.51(3H，s)，
3.86(3H，s)，6.15(1H，s)，7.26(1H，s)
0.90(3H，t)，1.50-1.75(2H，m)，2.20-2.35(2H，m)，18????168-170??2.39(3H，s)，2.46(3H，s)，2.51(3H，s)，3.86(3H，s)，
6.15(1H，s)，7.25(1H，s)19????229-231??1.30-2.00(1H，bs)，2.39(3H，s)，2.45(3H，s)，2.82(3H，s)，
6.14(1H，s)，7.53(1H，s)20????208-209??2.45(3H，s)，3.92(3H，s)，6.25(1H，s)，7.67(1H，s)21????180-181??2.41(3H，s)，2.50(3H，s)，3.93(3H，s)，6.21(1H，s)，
7.40(1H，s)22????166-167??2.44(3H，s)，2.53(3H，s)，3.93(3H，s)，6.20(1H，s)，
7.52(1H，s)23????176-177??2.17(3H，s)，2.34(3H，s)，2.52(3H，s)，3.95(3H，s)，
6.11(1H，s)，7.28(1H，s)24????134-136??2.35(3H，s)，2.43(3H，s)，2.50(3H，s)，3.86(3H，s)，
6.09(1H，s)，7.18(1H，s)
Table 7No. mp (℃) NMR (CDCl
3) ppm25 215-216 2.14 (3H, s), 2.44 (3H, s), 2.49 (3H, s), 3.93 (3H, s),
6.20(1H，s)，7.91(1H，s)26????169-170??1.29(3H，d)，1.32(3H，d)，2.39(3H，s)，2.53(3H，s)，
3.51-3.56(1H，m)，3.93(3H，s)，6.16(1H，s)，7.27(1H，s)27????211-212??1.36(3H，d)，1.45(3H，d)，2.38(3H，s)，2.45(3H，s)，
2.80-3.30(1H，m)，3.93(3H，s)，6.17(1H，s)，7.15(1H，s)28????139-141??2.40(3H，s)，2.46(3H，s)，3.88(3H，s)，3.96(3H，s)，
6.16(1H，s)，7.33(1H，s)29????78-79????1.53(3H，t)，2.39(3H，s)，2.46(3H，s)，2.51(3H，s)，
4.31-4.41(2H，m)，6.16(1H，s)，7.26(1H，s)30????143-144??1.04(3H，t)，1.93-2.05(2H，m)，2.39(3H，s)，2.46(3H，s)，
2.50(3H，s)，4.23-4.33(2H，m)，6.16(1H，s)，7.27(1H，s)31????161-162??1.52(6H，d)，2.39(3H，s)，2.46(3H，s)，2.49(3H，s)，
5.05-5.28(1H，m)，6.16(1H，s)，7.27(1H，s)
1.01(3H，t)，1.39-1.51(2H，m)，1.89-2.02(2H，m)，32????118-119??2.39(3H，s)，2.46(3H，s)，2.50(3H，s)，4.20-4.35(2H，m)，
6.16(1H，s)，7.26(1H，s)
0.94(3H，t)，1.35-1.45(4H，m)，1.90-2.00(2H，m)，33????78-79????2.39(3H，s)，2.46(3H，s)，2.50(3H，s)，4.25-4.35(2H，m)，
6.16(1H，s)，7.26(1H，s)
0.91(3H，t)，1.20-1.50(4H，m)，1.85-2.05(2H，m)，34????87-88????2.39(3H，s)，2.46(3H，s)，2.50(3H，s)，4.15-4.40(2H，m)，
6.16(1H，s)，7.26(1H，s)35????170-172??1.20-2.15(10H，m)，2.38(3H，s)，2.46(3H，s)，2.48(3H，s)，
4.78-4.90(1H，m)，6.15(1H，s)，7.27(1H，s)
2.38(3H，s)，2.45(3H，s)，2.50(3H，s)，5.46(1H，d)，36????143-144??5.53(1H，d)，6.16(1H，s)，7.25(1H，s)，7.30-7.45(3H，m)，
7.50-7.55(2H，m)
2.39(3H，s)，2.46(3H，s)，2.51(3H，s)，4.92(2H，d)，37????103-104??5.39(1H，d)，5.43(1H，dd)，5.96-6.10(1H，m)，6.16(1H，s)，
7.26(1H，s)
Table 8No. mp (℃) NMR (CDCl
3) ppm38 66-68 1.33 (3H, t), 2.47 (3H, s), 2.52 (3H, s), 2.68 (2H, q),
3.93(3H，s)，6.17(1H，s)，7.25(1H，s)39????114-115??1.05(3H，t)，1.70-1.90(2H，m)，2.46(3H，s)，2.52(3H，s)，
2.61(2H，t)，3.93(3H，s)，6.16(1H，s)，7.24(1H，s)40????134-135??1.34(6H，d)，2.48(3H，s)，2.52(3H，s)，2.80-2.95(1H，m)，
3.93(3H，s)，6.18(1H，s)，7.25(1H，s)
0.98(3H，t)，1.39-1.53(2H，m)，1.68-1.80(2H，m)，41????121-122??2.47(3H，s)，2.53(3H，s)，2.64(2H，t)，3.93(3H，s)，
6.17(1H，s)，7.27(1H，s)42????91-93????1.37(9H，s)，2.49(3H，s)，2.53(3H，s)，3.93(3H，s)，
6.23(1H，s)，7.26(1H，s)43????137-138??2.51(6H，s)，3.93(3H，s)，4.29(2H，s)，6.38(1H，s)，
7.30(1H，s)44????117-119??2.52(6H，s)，3.94(3H，s)，6.73(1H，s)，7.40(1H，s)45????108-110??2.46(3H，s)，2.53(3H，s)，3.51(3H，s)，3.93(3H，s)，
4.38(2H，s)，6.40(1H，s)，7.27(1H，s)，46????225-226??2.54(3H，s)，2.58(3H，s)，3.94(3H，s)，7.23(1H，s)，
7.38(1H，s)47????108-110??2.52(3H，s)，2.55(3H，s)，3.93(3H，s)，4.03(3H，s)，
7.07(1H，s)，7.34(1H，s)48????72-74????1.44(3H，t)，2.51(3H，s)，2.56(3H，s)，3.93(3H，s)，
4.47(2H，q)，7.07(1H，s)，7.34(1H，s)49????160-161??2.43(3H，s)，2.69(3H，s)，3.60(3H，s)，6.70(1H，s)，
7.30(1H，s)50????133-135??2.45(3H，s)，2.60(3H，s)，3.60(3H，s)，4.05(3H，s)，
6.96(1H，s)，7.28(1H，s)51????149-150??2.47(3H，s)，2.52(3H，s)，2.57(3H，s)，3.93(3H，s)，
6.20(1H，s)，7.24(1H，s)52????202-204??2.57(3H，s)，2.63(3H，s)，3.95(3H，s)，6.84(1H，s)，
7.32(1H，s)，7.54-7.58(3H，m)，7.91-7.94(2H，m)53????195-196??2.00(3H，s)，2.41(6H，bs)，2.52(3H，s)，3.86(3H，s)，
7.14(1H，s)
Table 9No. mp (℃) NMR (CDCl
3) ppm54 236-237 2.11 (3H, s), 2.46 (3H, s), 2.51 (6H, s), 3.85 (3H, s),
6.80(1H，s)，7.23(1H，s)55????175-176??1.48(3H，t)，2.11(3H，s)，2.46(3H，s)，2.50(3H，s)，
2.51(3H，s)，4.29(2H，q)，6.80(1H，s)，7.25(1H，s)
1.02(3H，t)，1.91-2.01(2H，m)，2.11(3H，s)，2.46(3H，s)，56????151-152??2.49(3H，s)，2.51(3H，s)，4.21(2H，t)，6.80(1H，s)，
7.25(1H，s)57????169-170??1.45-1.50(6H，m)，2.11(3H，s)，2.46(3H，s)，2.48(3H，s)，
2.51(3H，s)，5.15-5.28(1H，m)，6.79(1H，s)，7.26(1H，s)
1.00(3H，t)，1.35-1.40(2H，m)，1.80-1.95(2H，m)，58????139-140??2.11(3H，s)，2.46(3H，s)，2.49(3H，s)，2.51(3H，s)，
4.24(2H，t)，6.79(1H，s)，7.24(1H，s)
2.12(3H，s)，2.46(3H，s)，2.51(6H，s)，4.88(2H，dd)，59????146-148??5.35(1H，s)，5.39(1H，dd)，5.90-6.20(1H，m)，6.80(1H，s)，
7.24(1H，s)
2.06(3H，s)，2.46(3H，s)，2.50(6H，s)，5.40(1H，d)，60????171-172??5.48(1H，d)，6.80(1H，s)，7.24(1H，s)，7.30-7.40(3H，m)，
7.45-7.55(2H，m)61????181-182??2.46(3H，s)，2.51(6H，s)，3.93(3H，s)，6.80(1H，s)，
7.20(1H，s)，62????142-143??1.55(3H，t)，2.45(3H，s)，2.50(3H，s)，2.51(3H，s)，
4.37(2H，q)，6.80(1H，s)，7.22(1H，s)63????138-139??1.04(3H，t)，1.93-2.05(2H，m)，2.42(3H，s)，2.45(3H，s)，
2.46(3H，s)，4.22-4.35(2H，m)，6.80(1H，s)，7.22(1H，s)64????158-159??1.52(6H，d)，2.46(3H，s)，2.48(3H，s)，2.51(3H，s)，
5.15-5.30(1H，m)，6.79(1H，s)，7.23(1H，s)
1.01(3H，t)，1.40-1.50(2H，m)，1.85-2.03(2H，m)，65????153-154??2.45(3H，s)，2.47(3H，s)，2.50(3H，s)，4.20-4.35(2H，m)，
6.79(1H，s)，7.21(1H，s)66????150-151??2.46(3H，s)，2.50(6H，s)，4.93(2H，d)，5.39(1H，s)，
5.44(1H，dd)，5.95-6.20(1H，m)，6.80(1H，s)，7.21(1H，s)
Table 10No. mp (℃) NMR (CDCl
3) ppm
2.45(3H，s)，2.49(6H，s)，5.46(1H，d)，5.53(1H，d)，67????178-179?????6.79(1H，s)，7.20(1H，s)，7.35-7.50(3H，m)，
7.55-7.65(2H，m)68????153-154?????2.36(3H，s)，2.43(3H，s)，2.57(3H，s)，3.59(3H，s)，
6.10(1H，s)，7.23(1H，s)69????194-195?????2.01(3H，s)，2.40(6H，s)，2.59(3H，s)，3.58(3H，s)，
7.21(1H，s)70????190-191?????2.45(3H，s)，2.48(3H，s)，2.58(3H，s)，3.63(3H，s)，
6.79(1H，s)，7.24(1H，s)71????178(decom-??2.25(3H，s)，2.51(3H，s)，2.59(3H，s)，3.86(3H，s)，
position)???7.06(1H，s)，7.18(1H，s)72????163-164?????2.43(3H，s)，2.61(3H，s)，3.63(3H，s)，6.20(1H，s)，
7.58(1H，s)
2.38(3H，s)，2.44(3H，s)，2.58(3H，s)，4.55(2H，d)，73????123-125?????5.33(1H，s)，5.38(1H，d)，5.92-6.06(1H，m)，
6.15(1H，s)，7.30(1H，s)74????175-176?????1.47(6H，d)，2.38(3H，s)，2.44(3H，s)，2.57(3H，s)，
4.56-4.66(1H，m)，6.14(1H，s)，7.32(1H，s)
0.85-1.00(3H，m)，1.45(3H，d)，1.65-2.00(2H，m)，75????172-173?????2.38(3H，s)，2.44(3H，s)，2.56(3H，s)，4.25-4.45
(1H，m)，6.14(1H，s)，7.31(1H，d)
0.99(3H，t)，1.35-1.48(2H，m)，1.78-1.89(2H，m)，76????143-144?????2.38(3H，s)，2.44(3H，s)，2.57(3H，s)，3.93(2H，t)，
6.14(1H，s)，7.30(1H，s)
0.93(3H，t)，1.35-1.39(4H，m)，1.82-1.90(2H，m)，77????86-88???????2.38(3H，s)，2.44(3H，s)，2.57(3H，s)，3.91(2H，t)，
6.14(1H，s)，7.30(1H，s)
0.90(3H，t)，1.15-1.35(6H，m)，1.78-1.87(2H，m)，78????72-73???????2.38(3H，s)，2.44(3H，s)，2.57(3H，s)，3.92(2H，t)，
6.14(1H，s)，7，30(1H，s)
Table 11No. mp (℃) NMR (CDCl
3) ppm
1.23-1.49(4H，m)，1.70-2.01(6H，m)，2.38(3H，s)，79????174-175????2.44(3H，s)，2.56(3H，s)，4.15-4.26(1H，m)，
6.14(1H，s)，7.31(1H，s)80????171-172????2.37(3H，s)，2.43(3H，s)，2.57(3H，s)，5.09(2H，s)，
6.14(1H，s)，7.29(1H，s)，7.32-7.45(5H，m)81????154-155????1.43(3H，t)，2.45(3H，s)，2.48(3H，s)，2.57(3H，s)，
4.00(2H，q)，6.79(1H，s)，7.25(1H，s)
2.45(3H，s)，2.48(3H，s)，2.57(3H，s)，4.55(2H，d)，82????145-146????5.27(1H，s)，5.38(1H，d)，5.92-6.06(1H，m)，
6.79(1H，s)，7.26(1H，s)83????148-149????1.47(6H，d)，2.45(3H，s)，2.48(3H，s)，2.55(3H，s)，
4.56-4.66(1H，m)，6.79(1H，s)，7.26(1H，s)84????123-124????1.01(3H，t)，1.82-1.95(2H，m)，2.45(3H，s)，2.49(3H，s)
2.56(3H，s)，3.90(2H，t)，6.79(1H，s)，7.26(1H，s)
0.85-1.00(3H，m)，1.45(3H，d)，1.65-2.00(2H，m)，85????136-137????2.45(3H，s)，2.49(3H，s)，2.55(3H，s)，4.25-4.45
(1H，m)，6.79(1H，s)，7.27(1H，d)
0.99(3H，t)，1.36-1.49(2H，m)，1.79-1.89(2H，m)，86????142-143????2.44(3H，s)，2.48(3H，s)，2.57(3H，s)，3.94(2H，t)，
6.78(1H，s)，7.26(1H，s)87????181-182????2.44(3H，s)，2.47(3H，s)，2.56(3H，s)，5.09(2H，s)，
6.79(1H，s)，7.26(1H，s)，7.33-7.45(5H，m)88????230-232????2.37(3H，s)，2.42(3H，s)，2.61(3H，s)，3.46(3H，s)，
3.94(3H，s)，6.12(1H，s)，7.30(1H，s)89????184-185????2.39(31，s)，2.45(3H，s)，2.61(3H，s)，3.55(3H，s)，
6.15(1H，s)，7.28(1H，s)
1.77(3H，q)，2.12(3H，s)，2.42(3H，s)，2.50(3H，s)，90????180-181????4.65-4.90(2H，m)，5.60-6.00(2H，m)，6.18(1H，s)，
7.28(1H，d)
2.22(3H，s)，2.45(3H，s)，2.54(3H，s)，4.86(2H，q)，91????163-172????5.30-5.45(2H，m)，5.90-6.10(1H，m)，6.23(1H，s)，
7.53(1H，q)，7.92(1H，d)
Table 12No. mp (℃) NMR (CDCl
3) ppm
1.77(3H，q)，2.10(3H，s)，2.39(3H，s)，2.46(3H，s)，92????-??????????2.52(3H，s)，4.70-4.90(2H，m)，5.60-5.95(2H，m)，
6.15(1H，s)，7.28(1H，s)
1.00(3H，t)，1.35-1.55(2H，m)，1.80-2.00(2H，m)，93??130-131??????2.12(3H，s)，2.42(3H，s)，2.49(3H，s)，4.23(3H，t)，
6.18(1H，s)，7.29(1H，d)
0.85-1.05(3H，m)，1.49(3H，d)，1.75-2.10(2H，m)，94??177-178??????2.39(3H，s)，2.46(3H，s)，2.49(3H，s)，4.95-5.15
(1H，m)，6.15(1H，s)，7.28(1H，d)
0.90-1.05(3H，m)，1.49(3H，d)，1.75-2.10(2H，m)，95??132-134??????2.45(3H，s)，2.48(3H，s)，2.51(3H，s)，4.95-5.15
(1H，m)，6.79(1H，s)，7.23(1H，d)96??173-174??????2.19(3H，s)，2.23(3H，s)，2.87(3H，s)，3.96(3H，s)，
6.08 (1H, s), 7.14 (1H, s) herbicidal effects of test case 1 soil treatment
Be placed on paddy soils in the plastic tub that diameter is 12cm and sow green amaranth L., the seed of Herba Aeschynonenes Indicae (close and sprout) and barnyard grass.Water and make soil surface wet slightly.Make every square metre soil surface absorb the activeconstituents of this test compounds of 0.4 gram the parallel sprinkling of test compounds.This test plants is grown under the condition of spilling water paddy.Handled back 21 days, and estimated the herbicidal effect of each test compounds according to following standard these plants that detect by an unaided eye.
| Ranking | Control % |
| 0 (invalid) | ????0％ |
| ????1 | ????1-24％ |
| ????2 | ????25-49％ |
| ????3 | ????50-74％ |
| ????4 | ????75-90％ |
| ????5 | ????91-100％ |
Table 13 has shown this result.The sequence number of the test compounds in the table is corresponding with the sequence number in table 1～4.Also will use in the numbering system of the same compound test case below.
Table 13
The herbicidal effect of test case 2 under spilling water paddy condition
| The compound sequence number | Green amaranth L. | Herba Aeschynonenes Indicae | Barnyard grass |
| ????4 | ????4 | ????5 | ????4 |
| ????5 | ????5 | ????5 | ????5 |
| ????6 | ????4 | ????5 | ????5 |
| ????20 | ????4 | ????3 | ????5 |
| ????21 | ????3 | ????5 | ????5 |
| ????22 | ????5 | ????5 | ????5 |
| ????23 | ????3 | ????4 | ????5 |
| ????24 | ????5 | ????4 | ????5 |
| ????29 | ????4 | ????3 | ????5 |
| ????37 | ????4 | ????3 | ????5 |
| ????38 | ????5 | ????5 | ????5 |
| ????44 | ????5 | ????5 | ????5 |
| ????45 | ????5 | ????5 | ????5 |
| ????68 | ????5 | ????4 | ????5 |
| ????71 | ????5 | ????4 | ????5 |
| ????72 | ????4 | ????5 | ????5 |
Be placed on paddy soil in the vinylbenzene basin that diameter is 12cm and water, this soil then stirs and flattens.In basin, pour water to the certain sea line that surpasses soil surface.With barnyard grass (in a slice leaf stage) and rice sprouts (1.2～1.3 leaf stages) culture transferring in this basin.After four days, make every square metre water surface absorb the activeconstituents of this test compounds of 0.4 gram the parallel water surface that is sprayed at of test compounds.Then with the planting seed of an amount of small brokens sand grass and barnyard grass in this basin, then feed water with the water yield that is suitable for the test plants growth.Handled back 21 days, and estimated the herbicidal effect of each test compounds according to test case 1 specified standard these plants that detect by an unaided eye.Table 14 has been listed this result.
Table 14
The herbicidal effect that test case 3 leaves are handled
| The compound sequence number | Barnyard grass | Small brokens sand grass | The barnyard grass of culture transferring | Rice (rice plants) |
| ????3 | ????5 | ????5 | ????3 | ????0 |
| ????8 | ????5 | ????5 | ????4 | ????1 |
| ????20 | ????5 | ????5 | ????4 | ????0 |
| ????23 | ????5 | ????5 | ????4 | ????1 |
| ????25 | ????5 | ????5 | ????4 | ????1 |
| ????26 | ????5 | ????5 | ????5 | ????0 |
| ????28 | ????5 | ????5 | ????3 | ????1 |
| ????30 | ????5 | ????5 | ????3 | ????0 |
| ????38 | ????5 | ????5 | ????5 | ????1 |
| ????39 | ????5 | ????5 | ????5 | ????1 |
| ????40 | ????5 | ????5 | ????3 | ????1 |
| ????41 | ????5 | ????5 | ????5 | ????0 |
| ????42 | ????5 | ????5 | ????4 | ????0 |
| ????43 | ????5 | ????5 | ????3 | ????1 |
| ????45 | ????5 | ????5 | ????5 | ????0 |
| ????51 | ????5 | ????5 | ????4 | ????0 |
| ????61 | ????5 | ????5 | ????3 | ????0 |
| ????71 | ????5 | ????5 | ????4 | ????1 |
Paddy soil is placed in the plastic tub that diameter is 12cm and plants go up the lead a cow seed of (Pharbitis nil Choisy) and wheat L. (wheat) of Choisy.Stretch the stage rough leaf, make every square metre soil surface absorb the activeconstituents of this test compounds of 0.4 gram on the plant parallel being sprayed on of test compounds with pneumatic paint brush.This test plants is grown under the condition of spilling water paddy.Handled back 21 days, and estimated the herbicidal effect of each test compounds according to test case 1 specified standard these plants that detect by an unaided eye.Table 15 has been listed this result.
Table 15
The inhibition of test case 4 paddy rice blights
| The compound sequence number | Choisy leads a cow | Wheat L. (wheat) |
| ????24 | ????3 | ????0 |
| ????29 | ????5 | ????0 |
| ????30 | ????5 | ????0 |
| ????37 | ????5 | ????0 |
| ????38 | ????4 | ????0 |
The concentration such as the table 16 that the wettable powder compound of the present invention that is obtained in the formulation Example 2 are diluted with water to activeconstituents are listed.The amount of this diluent with 5 milliliters is sprayed on the rice sprouts that is in 2 true leaf stages in the basin.After 5 hours, brood cell with rice blast (Magnaporthe grisea) carries out spray inoculation and holds it in the indoor of 25 ℃ of humidities with the rice shoot in the basin of rice shoot in the basin of treated mistake and unprocessed mistake, then under the irradiation of fluorescent lamp with the further inoculation 6 days of 25 ℃ and 90% humidity.The quantity of calculating the damage of paddy rice leaf also calculates " % inhibition " according to following equation thus with the infection that decision has the area of institute's pilot blade of how much per-cent to be subjected to rice blast (Magnaporthe grisea):
Table 16 compound sequence number concentration (ppm) suppresses (%)
1??????????????100????????＞90
5??????????????100????????＞90
8??????????????100????????＞90
9??????????????100????????＞90
10?????????????100????????＞90
11?????????????100????????＞90
12?????????????100????????＞90
15?????????????100????????＞90
16?????????????100????????＞90
22?????????????100????????＞90
24?????????????100????????＞90
28?????????????100????????＞90
29?????????????100????????＞90
30?????????????100????????＞90
31?????????????100????????＞90
32?????????????100????????＞90
33?????????????100????????＞90
37?????????????100????????＞90
38?????????????100????????＞90
58?????????????100????????＞90
61?????????????100????????＞90
62?????????????100????????＞90
68?????????????100????????＞90
70?????????????100????????＞90
73?????????????100????????＞90
74?????????????100????????＞90
76?????????????100????????＞90
79?????????????100????????＞90
80?????????????100????????＞90
94?????????????100????????＞90
95?????????????100????????＞90
The inhibition of 96 100＞90 test cases, 5 tomato blights in late period
The concentration such as the table 17 that the wettable powder compound of the present invention that is obtained in the formulation Example 2 are diluted with water to activeconstituents are listed.The amount of this diluent with 10 milliliters is sprayed on cherry tomato (Cultivar " the red cherry ") rice shoot that is in 5 true leaf stages.After the dry air 5 hours, this tomato sprout being carried out spray inoculation with the zoosporangium suspension of potato late blight (phytophthora infestans) (Phytophthorainfestans f.Sp.Infestans) and hold it in 20 ℃ and humidity is 100%, in the inoculation tank under the condition that promptly is suitable for infecting, then under the irradiation of fluorescent lamp with the further inoculation 5 days of 25 ℃ and 90% humidity.Observe " % inhibition " that the degree that infects has the area of institute's pilot blade of how much per-cent to be subjected to the infection of potato late blight (phytophthora infestans) with decision and calculates each test compounds thus according to the equation in the test case 4.Table 17 has been listed this result.
Table 17 compound sequence number concentration (ppm) suppresses (%)
4?????????????500????????＞90
20????????????500????????＞90
24????????????500????????＞90
28????????????500????????＞90
32????????????500????????＞90
37????????????500????????＞90
38????????????500????????＞90
39????????????500????????＞90
40????????????500????????＞90
42????????????500????????＞90
43????????????500????????＞90
44????????????500????????＞90
45????????????500????????＞90
48????????????500????????＞90
51????????????500????????＞90
57????????????500????????＞90
58????????????500????????＞90
61????????????500????????＞90
64????????????500????????＞90
68????????????500????????＞90
71????????????500????????＞90
The inhibition of 72 500＞90 test cases, 6 cucumber powdery mildews
Wettable powder diluted chemical compound of the present invention to the predetermined concentration (500ppm) that is obtained in the formulation Example 2 also is sprayed on this diluent on cucumber (Cultivar " the Suzunarishiyo ") rice shoot of having planted about 2 week in the greenhouse with enough amounts.After the dry air, this cucumber rice shoot is carried out spray inoculation with the conidium suspension of Kidney bean Powdery Mildew and it was kept in the greenhouse 10 days.Observe " % inhibition " that the degree that infects has the area of institute's pilot blade of how much per-cent to be subjected to the infection of Kidney bean Powdery Mildew with decision and calculates each test compounds thus according to the equation in the test case 4.Table 18 has been listed this result.
Table 18 compound sequence number concentration (ppm) suppresses (%)
15????????????500????????＞90
24????????????500????????＞90
28????????????500????????＞90
29????????????500????????＞90
30????????????500????????＞90
31????????????500????????＞90
33????????????500????????＞90
38????????????500????????＞90
39????????????500????????＞90
48????????????500????????＞90
52????????????500????????＞90
68????????????500????????＞90
71????????????500????????＞90
73????????????500????????＞90
74????????????500????????＞90
75????????????500????????＞90
76????????????500????????＞90
78????????????500????????＞90
94????????????500????????＞90
Claims (6)
1. chromone derivative by general formula (1) expression
X wherein, Y and Z are identical or different, and represent oxygen or sulphur separately; R
1Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, C
1-6Haloalkyl, (C
1-6Alkoxyl group) C
1-6Alkyl, carboxyl, C
1-6Alkoxy carbonyl, cyano group, C
1-6Alkoxycarbonyl amino, C
1-6Alkylthio, C
3-8Cycloalkyl sulfenyl or by the phenyl of optional replacement; R
2Represent hydrogen, C
1-6Alkyl or C
3-8Cycloalkyl; R
3Represent hydrogen, halogen, C
1-6Alkyl, C
3-8Cycloalkyl or C
1-6Alkoxyl group; M is the integer of 1-3; When m is 2 or 3, all R
3Can be identical or different; R
4Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, C
1-6Haloalkyl, C
1-6Alkoxy or halogen; R
5Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, by the benzyl of optional replacement or C
2-6Thiazolinyl.
2. according to the chromone derivative of claim 1, this derivative is represented by general formula (1a)
X wherein, Y, Z, R
1, R
2, R
3, m, R
4And R
5As above-mentioned definition.
3. Bactericide composition that contains the chromone derivative of general formula (1) as activeconstituents
X wherein, Y and Z are identical or different, and represent oxygen or sulphur separately; R
1Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, C
1-6Haloalkyl, (C
1-6Alkoxyl group) C
1-6Alkyl, carboxyl, C
1-6Alkoxy carbonyl, cyano group, C
1-6Alkoxycarbonyl amino, C
1-6Alkylthio, C
3-8Cycloalkyl sulfenyl or by the phenyl of optional replacement; R
2Represent hydrogen, C
1-6Alkyl or C
3-8Cycloalkyl; R
3Represent hydrogen, halogen, C
1-6Alkyl, C
3-8Cycloalkyl or C
1-6Alkoxyl group; M is the integer of 1-3; When m is 2 or 3, all R
3Can be identical or different; R
4Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, C
1-6Haloalkyl, C
1-6Alkoxy or halogen; R
5Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, by the benzyl of optional replacement or C
2-6Thiazolinyl.
4. according to the Bactericide composition of claim 3, said composition contains the chromone derivative by general formula (1a) expression as activeconstituents
X wherein, Y, Z, R
1, R
2, R
3, m, R
4And R
5As above-mentioned definition.
5. herbicidal composition that contains the chromone derivative of general formula (1) as activeconstituents
X wherein, Y and Z are identical or different, and represent oxygen or sulphur separately; R
1Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, C
1-6Haloalkyl, (C
1-6Alkoxyl group) C
1-6Alkyl, carboxyl, C
1-6Alkoxy carbonyl, cyano group, C
1-6Alkoxycarbonyl amino, C
1-6Alkylthio, C
3-8Cycloalkyl sulfenyl or by the phenyl of optional replacement; R
2Represent hydrogen, C
1-6Alkyl or C
3-8Cycloalkyl; R
3Represent hydrogen, halogen, C
1-6Alkyl, C
3-8Cycloalkyl or C
1-6Alkoxyl group; M is the integer of 1-3; When m is 2 or 3, all R
3Can be identical or different; R
4Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, C
1-6Haloalkyl, C
1-6Alkoxy or halogen; R
5Represent hydrogen, C
1-6Alkyl, C
3-8Cycloalkyl, by the benzyl of optional replacement or C
2-6Thiazolinyl.
6. according to the herbicidal composition of claim 5, said composition contains the chromone derivative by general formula (1a) expression as activeconstituents
X wherein, Y, Z, R
1, R
2, R
3, m, R
4And R
5As above-mentioned definition.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13670/1997 | 1997-01-28 | ||
| JP1367097 | 1997-01-28 | ||
| JP298313/97 | 1997-10-30 | ||
| JP9298313A JPH10273487A (en) | 1997-01-28 | 1997-10-30 | Chromone derivative and fungicide and herbicide containing the same as active ingredient |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1246118A true CN1246118A (en) | 2000-03-01 |
Family
ID=26349499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98802112A Pending CN1246118A (en) | 1997-01-28 | 1998-01-27 | Chromone derivatives and bactericidal and herbicidal agent containing the same as active ingredient |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH10273487A (en) |
| KR (1) | KR20000070486A (en) |
| CN (1) | CN1246118A (en) |
| AU (1) | AU5577698A (en) |
| WO (1) | WO1998032752A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104068031A (en) * | 2014-06-30 | 2014-10-01 | 苏州派腾生物医药科技有限公司 | Application of hamaudol to preparation of insecticide |
| CN107513059A (en) * | 2016-06-17 | 2017-12-26 | 南京工业大学 | A kind of 23 azacyclo- Thiochromone compounds of substitution and its synthetic method and the application in antifungal drug |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11116564A (en) * | 1997-10-09 | 1999-04-27 | Otsuka Chem Co Ltd | Chromone derivative |
| JP4647757B2 (en) * | 1999-08-18 | 2011-03-09 | 富山化学工業株式会社 | Chromone derivatives or salts thereof and antifungal agents containing them |
| JP4561245B2 (en) * | 2004-08-31 | 2010-10-13 | 住友化学株式会社 | Chromone compounds and uses thereof |
| WO2017115333A1 (en) * | 2015-12-30 | 2017-07-06 | Investigaciones Biológicas En Agroquímicos Rosario S.A. | Herbicidal composition comprising chromone derivatives and a method for weed control |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08193078A (en) * | 1995-01-12 | 1996-07-30 | Hokko Chem Ind Co Ltd | Chromone derivative and agricultural and horticultural germicide |
-
1997
- 1997-10-30 JP JP9298313A patent/JPH10273487A/en active Pending
-
1998
- 1998-01-27 KR KR1019997006729A patent/KR20000070486A/en not_active Application Discontinuation
- 1998-01-27 WO PCT/JP1998/000309 patent/WO1998032752A1/en not_active Application Discontinuation
- 1998-01-27 CN CN98802112A patent/CN1246118A/en active Pending
- 1998-01-27 AU AU55776/98A patent/AU5577698A/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104068031A (en) * | 2014-06-30 | 2014-10-01 | 苏州派腾生物医药科技有限公司 | Application of hamaudol to preparation of insecticide |
| CN107513059A (en) * | 2016-06-17 | 2017-12-26 | 南京工业大学 | A kind of 23 azacyclo- Thiochromone compounds of substitution and its synthetic method and the application in antifungal drug |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998032752A1 (en) | 1998-07-30 |
| JPH10273487A (en) | 1998-10-13 |
| AU5577698A (en) | 1998-08-18 |
| KR20000070486A (en) | 2000-11-25 |
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