CN1168671A - Novel pyrimidinyloxy- and pyrimidinylamino-ethylphenyl-dioxolane derivatives - Google Patents
Novel pyrimidinyloxy- and pyrimidinylamino-ethylphenyl-dioxolane derivatives Download PDFInfo
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- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
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Abstract
The invention discloses 2-[4-(2-(pyrimidin-4-yloxy- and -4-ylamino)-ethyl-phenyl)-dioxolanes of formula (I) wherein R1 is hydrogen, C1-4alkyl, C1-4haloalkyl or C3-6cycloalkyl, R2 is hydrogen, C1-10alkyl, C1-8alkoxy-C1-4alkyl, C3-8alkenyloxy-C1-4alkyl, C3-8haloalkenyloxy-C1-4alkyl, C3-8alkynyloxy-C1-4alkyl, C1-8haloalkoxy-C1-4alkyl, C1-8alkylthio-C1-4alkyl, aryl, aryloxy-C1-4alkyl, aryl-C1-4alkoxy-C1-4-alkyl, heteroaryloxy-C1-4alkyl, C1-4alkoxy-C1-4alkoxy-C1-4alkyl or aryl-C1-8alkyl, R3 and R4 independently are halogen, C1-4alkyl, C1-4alkoxy, C1-4alkoxy-C1-4alkyl, C1-4alkoxycarbonyl-C1-4alkyl, C1-4alkoxycarbonyl, cyano-C1-4alkyl, cyano, or -COOH, or R3 and R4 together form a bridge member selected from 1,4-butylene, 1,4-butadienylene, or -S-CH=CH-, each optionally substituted by one or two radicals selected from halogen or C1-4alkyl, and Z is NH or oxygen; the use of such compounds for the control of undesired acarinae, fungi, and insects, compositions for facilitating such use, and the preparation of the compounds of formula I.
Description
The present invention relates to new 2-(4-(2-(2-pyrimidine-4-base oxygen base-and-the 4-base is amino) ethyl) phenyl) dioxolane class, the application aspect control deleterious acarine, fungi and insect of their synthetic method and this compounds.
2-(4-(2-(2-pyrimidine-4-base oxygen base-and-the 4-base the is amino) ethyl) phenyl) dioxolane that has been found that formula I has very strong insecticidal activity, the activity of particularly very strong tick mite killing, fungi and insect.Formula I compound is particularly suitable for preventing and treating acarina and insect purpose plant insect.In addition, formula I compound also has the Fungicidally active to anti-plant pathogenic fungi.
Wherein
R
1Be hydrogen, C
1-4Alkyl, C
1-4Haloalkyl or C
3-6Cycloalkyl,
R
2Be hydrogen, C
1-10Alkyl, C
1-8Alkoxy-C
1-4Alkyl, C
3-8Alkenyloxy-C
1-4Alkyl, C
3-8Haloalkene oxygen base-C
1-4Alkyl, C
3-8Alkynyloxy group-C
1-4Alkyl, C
1-8Halogenated alkoxy-C
1-4Alkyl, C
1-8Alkylthio-C
1-4Alkyl, aryl, aryloxy-C
1-4Alkyl, aryl-C
1-4Alkoxy-C
1-4Alkyl, heteroaryloxy-C
1-4Alkyl, C
1-4Alkoxy-C
1-4Alkoxy-C
1-4Alkyl or aryl-C
1-8Alkyl,
R
3And R
4Be halogen, C independently
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Alkoxy-C
1-4Alkyl, C
1-4Carbalkoxy-C
1-4Alkyl, C
1-4Carbalkoxy, cyano group-C
1-4Alkyl, cyano group or-COOH, perhaps
R
3And R
4Form one together and be selected from tetramethylene, 1,4-Aden dialkylene or-abutment of S-CH=CH-, they all can randomly be selected from halogen or C
1-4One or two groups replacements of alkyl,
Z is NH or oxygen.
In the definition of each group of formula I, alkyl is understood to include the alkyl of straight chain and side chain, preferred straight chain and rudimentary alkyl.The example of alkyl has amyl group, hexyl, heptyl, octyl group, nonyl or the decyl of methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, isobutyl-and various isomeric form.Cycloalkyl representative ring propyl group, cyclobutyl, cyclopentyl and cyclohexyl.Alkoxyl group comprises pentyloxy, hexyloxy, the heptan oxygen base or octyloxy of for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, isobutoxy and various isomeric form.Halogen is meant fluorine, chlorine, bromine and iodine, preferred fluorine and chlorine.Alkene oxygen base is meant amylene oxygen base, hexene oxygen base, heptene oxygen base or the octene oxygen base of allyloxy, methyl allyloxy, 2-butylene oxygen base, 3-butenyloxy and various isomeric forms.Alkynyloxy group for example is meant third alkynyloxy group, 2-butyne oxygen base, 3-fourth alkynyloxy group and penta alkynyloxy group of various isomeric form, own alkynyloxy group, heptan alkynyloxy group or hot alkynyloxy group.Aryl is represented aromatic hydrocarbyl, for example phenyl or naphthyl, preferably phenyl.The aryloxy representative is by the aryl of Sauerstoffatom bonding.The example has phenoxy group, alpha-naphthoxy base or β-naphthyloxy.Heteroaryloxy is represented the 5-6 acyclic radical of aromatics, wherein contains 1,2 or 3 heteroatoms that is selected from nitrogen, oxygen or sulphur, and this cyclic group is by the Sauerstoffatom bonding.Heteroaryl in the heteroaryloxy also can be and another heteroaryl or aryl condensed form mutually.The example is pyridyl, pyrimidyl, triazolyl, triazinyl, thienyl, oxazolyl, oxadiazole base, pyrazolyl, imidazolyl, pyrryl, furyl, thiadiazolyl group etc.The Qing Wanji representative is preferably replaced by a cyano group by one or two alkyl that cyano group replaces.The example has the various isomer of cyanogen methyl, 1-cyanoethyl, 2-cyanoethyl and cyanogen propyl group or cyanogen butyl.Carbalkoxy typical example such as methoxycarbonyl, ethoxycarbonyl, the positive third oxygen carbonyl, the different third oxygen carbonyl, positive butoxy carbonyl, secondary butoxy carbonyl, tertbutyloxycarbonyl or isobutyl boc.Work as R
3And R
4When forming an abutment together, pyrimidine ring constitutes the part of a condensed-bicyclic system.The example of this bicyclic system is quinazoline, tetrahydro quinazoline, thieno-(2,3-d) pyrimidine or thieno-(3,2-d) pyrimidine.
When defined substituting group is during by various definition be combined into, each definition all has the implication that provides under this definition.For example haloalkyl is represented the alkyl of one one halo to perhalogeno.The example has trifluoromethyl, difluoromethyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-five fluoropropyls, chloromethyl, methyl fluoride etc.Alkoxyalkyl is meant for example methoxyl methyl, ethoxymethyl, the third oxygen methyl, ethoxyethyl, methoxyethyl, fourth oxygen methyl, the different third oxygen methyl, methoxycarbonyl propyl etc.The alkene oxyalkyl is for example allyl oxygen methyl, methyl allyl oxygen methyl, allyl oxygen ethyl, methyl allyl oxygen ethyl, 2-butylene oxygen ylmethyl etc.Haloalkene oxygen base alkyl comprises for example 2-chlorine allyl oxygen methyl etc.The alkynyloxy group alkyl is meant for example propine oxygen methyl or propine oxygen ethyl.The example of halogenated alkoxy alkyl is a 2-fluorine ethoxyl methyl.Alkylthio alkyl comprises for example methylthiomethyl or ethylmercapto group methyl.The example of aryloxy alkyl is 4-chlorophenoxy methyl, phenoxymethyl or 2-methoxycarbonyl phenoxy ylmethyl.The example of alkoxy aryl alkyl is benzyloxymethyl or methyl benzyloxymethyl.The example of heteroaryloxy alkyl is pyrazoles oxygen ylmethyl or 2-pyrimidinyl oxy methyl.The example of alkoxyl group alkoxyalkyl is methoxyl group ethoxymethyl, oxyethyl group ethoxymethyl or propoxy-ethoxymethyl.The example of alkoxycarbonyl alkyl is methoxycarbonyl methyl or ethoxycarbonylmethyl group.The example of aralkyl is phenmethyl, styroyl, 1-phenylethyl, phenyl propyl, phenyl butyl etc.
Formula I compound contains one or more unsymmetrical carbons.Therefore these compounds can exist with form pure in the optically-active or mixture of isomers form.The occasion of pure form all will illustrate specially in all finger optically-actives in the application's book.All mean it is the mixture of isomeric forms in all other situations, as by obtaining in the used synthetic method.Obtain the occasion of isomer mixture in synthetic, pure isomer can be by obtaining with known separation techniques in this mixture, and for example crystallization, chromatography or distillation method are perhaps derived/separation method with bonded.
In formula I compound, respectively organize compound below preferred, wherein
A) R
3And R
4Form optional tetramethylene or an Aden's dialkylene abutment that replaces together, thereby form a tetrahydro quinazoline or the quinazoline part that can choose replacement wantonly with the pyrimidine ring that they connected, or
B) R
1Be hydrogen or methyl, or
C) R
2Be C
1-8Alkyl, C
1-8Alkoxy-C
1-4Alkyl, C
3-8Alkenyloxy-C
1-4Alkyl or C
1-4Alkoxy-C
1-4Alkoxy-C
1-4Alkyl.
Preferred one group of formula I compound comprises such compound, wherein R
1Be hydrogen or methyl, R
2Be C
1-8Alkyl, C
1-8Alkoxy-C
1-8Alkyl, C
3-8Alkene oxygen base-C
1-4Alkyl or C
1-4Alkoxy-C
1-4Alkoxy-C
1-4Alkyl, R
3And R
4Then form tetramethylene or the Aden's dialkylene abutment that to choose replacement wantonly together.
Preferred indivedual formula I compound is:
4-allyloxy methyl-2-methyl-2-(4-(2-(quinazoline-4-base oxygen base) ethyl) phenyl) dioxolane,
4-allyloxy methyl-2-methyl-2-(4-(2-(5,6,7,8-tetrahydro quinazoline-4-base oxygen base) ethyl) phenyl) dioxolane,
4-butyl-2-methyl-2-(4-(2-(quinazoline-4-base oxygen base) ethyl) phenyl) dioxolane and
4-butyl-2-methyl-2-(4-(2-(5-methyl-thieno-(2,3-d) pyrimidine-4-base is amino) ethyl) phenyl) dioxolane.
Wherein Z is that 2-(4-(2-hydroxyethyl) phenyl) dioxolane that the formula I compound of oxygen can through type II and the 4-halogenated pyrimidine reaction of formula III obtain
R wherein
1And R
2With defined identical to formula I,
R wherein
3And R
4With defined identical to formula I, Hal is a halogen, preferred chlorine or bromine.
Reaction (II+III → I) can be according to carrying out for the known mode of etherification method itself.This etherification reaction preferably carries out in the presence of alkali.In addition, this reaction is to be advisable in the presence of inert solvent.Temperature of reaction generally is between the boiling point of 0 ℃ and reaction mixture, preferably between the boiling point of room temperature and solvent for use.Suitable alkali comprises alkalimetal hydride, for example sodium hydride, and alkali metal hydroxide, for example sodium hydroxide, potassium hydroxide.Situation at alkali metal hydroxide, the reaction that generates ether is preferably carried out having under a kind of phase-transfer catalyst (for example chlorination or bromination triethyl hexadecyldimethyl benzyl ammonium TEBA, tetrabutylammonium chloride etc.) and suitable inert solvent (as aromatic hydrocarbons, for example benzene and the toluene) existence.When using alkalimetal hydride (for example sodium hydride), the example of suitable inert solvent has hydro carbons, as the toluene class; Ethers is as ether, tetrahydrofuran (THF) and 1,2-glycol dimethyl ether; Polar solvent is as dimethyl formamide or acetonitrile; And contain two or more mixture in them.In accordance with known methods, for example methods such as evaporating solvent, chromatography or crystallization are separated desired final product and purifying.
Formula II compound can be by obtaining the hydrolysis in the presence of alkali of formula IV compound
R wherein
1And R
2With identical to the definition of formula I, X is hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group, halogen, nitro or cyano group, Y are hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group, halogen or cyano group.
Hydrolysis reaction (IV → II) can carry out according to the known mode of basic hydrolysis itself for carboxylicesters.Reaction is preferably carried out in the presence of alkali.Preferably be reflected in the aqueous solution or in the mixture of water and inert organic solvents and carry out.This kind solvent preferably and water can be miscible, alcohols for example, as methyl alcohol, ethanol or Virahol, or aromatic hydrocarbons, for example toluene and dimethylbenzene preferably use a kind of phase-transfer catalyst in this situation.In general all kinds of mineral alkalis all can use.The example is sodium hydroxide or potassium hydroxide.Temperature of reaction 0 ℃ and+100 ℃ between, preferably+20 ℃ and+50 ℃ between.
Formula IV compound can through type V compound and the glycol generation acetalation of formula VI obtain
R wherein
1, X and Y be with identical to the definition of formula IV
R wherein
2Definition cotype I.
(V+VI → IV) is equivalent to the acetalation of standard, and it can be according to carrying out for the known mode of acetalation itself in reaction.For example, reaction can be by catalysis in the presence of organic acid or inorganic acid (as the vitriol oil), and the water that generates as condensation product can utilize component distillation to separate continuously from reaction mixture.In a typical method, formula V and formula VI reactant are dissolved in the inert solvent (for example benzene,toluene,xylene or chloroform) that is fit to component distillation, the toluenesulphonic acids or the vitriol oil that add catalytic quantity, with the reaction mixture reflux, discharge the water that condensation generates via suitable condenser (for example Dean-stark trap) simultaneously.
In another kind of method, formula II compound also can through type VII compound and the glycol generation acetalation of formula VI prepare
R wherein
1, X and Y be with identical to the definition of formula IV,
R wherein
2Definition cotype I.
(VII+VI → II) can be by obtaining the similar mode of the method for formula IV compound by formula V and formula VI compound and carry out to described for acetalation.
Formula V compound can through type VIII compound and a kind of carboxylic acid derivative reaction of formula X obtain
Wherein the definition of X and Y is identical with formula IV,
R ' wherein
1Be C
1-4Alkyl, C
1-4Haloalkyl or C
3-6Cycloalkyl, L is a chlorine or bromine.
(VIII+IX → V) is equivalent to the acid catalyzed Freed-Kerafyrm thatch acylation reaction of standard in reaction.This reaction should be carried out in the presence of Lewis acid (for example aluminum chloride) or protonic acid (as sulfuric acid).In typical step, formula VIII+IX reactant is added in the suspension of Aluminum chloride anhydrous in solvent (as methylene dichloride, chloroform, oil of mirbane or dithiocarbonic anhydride) of metered amounts.Temperature of reaction preferably 0 ℃ and+30 ℃ between.
Wherein Z is that 2-(4-(2-aminoethyl) phenyl) dioxolane that the formula I compound of NH can through type X and the 4-halogenated pyrimidine reaction of formula III obtain
R wherein
1And R
2With identical to the definition of formula I
R wherein
3And R
4With identical to the definition of formula I, Hal is a halogen, preferred chlorine or bromine.
Reaction (X+III → I) can be according to carrying out for the known mode of reaction itself of amine and alkyl halide or heterocyclic halides (for example 2-haloperidid or 2-or 4-halogenated pyrimidine).This reaction should be carried out in the presence of alkali.Preferably be reflected in the aqueous solution or in the mixture of water and inert organic solvents and carry out.Solvent is preferably miscible with water, alcohols for example, and as methyl alcohol, ethanol or Virahol, or aromatic hydrocarbons, for example at this moment toluene and dimethylbenzene preferably use a kind of phase-transfer catalyst.In general all kinds of mineral alkalis all can use, and specially suitable is sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood.Temperature of reaction is between 0 ℃ to+100 ℃, and is preferred+50 ℃ to+100 ℃.
Formula X compound can obtain by through type XI compound hydrolysis
R wherein
1And R
2Definition cotype I.
Hydrolysis reaction (XI → X) can carry out according to the known mode of hydrolysis itself for phthalimide derivative.Reaction is preferably carried out in the presence of amine or hydrazine.Can use for example hydrazine, methylamine, ethamine, propylamine, 2-propylamine, butylamine or amylamine.
This reaction is preferably carried out in the aqueous solution or in inert organic solvents.Preferred solvent is an alcohols, for example methyl alcohol, ethanol or Virahol.Temperature of reaction is 0 ℃ to+100 ℃, and is preferred+20 ℃ to+50 ℃.
Formula XI compound can obtain with the phthalic imidine conversion by through type XII compound
R wherein
1And R
2Definition cotype I, Hal is a halogen, preferred chlorine or bromine.
Reaction (XII → XI) can carry out according to the known mode of alkylation itself for amine.This reaction is preferably carried out in the presence of alkali.Preferably in organic solvent inert, react.
In another approach, formula XII compound can through type II compound and the phthalic imidine reaction obtain
R wherein
1And R
2Definition cotype I.Reaction (II → XI) can carry out according to the mode that becomes known for the Mitsunobu reaction (O.Mitsunobu, synthetic (Synthesis), 1981, p.1 after; And D.L.Hughes, organic reaction (Org.Reaction), 1982,42 volumes, p.395; After).Reaction is preferably carried out in the presence of organo phosphorous compounds (for example triphenyl phosphine, front three phosphniline or tributylphosphine) and azodicarboxylate (for example diethylazodicarboxylate or diisopropyl azo-2-carboxylic acid).Preferably for example react in ether, diox or the tetrahydrofuran (THF) at inert organic solvents.
Formula XII compound can through type XIII compound and the glycol generation acetalation of formula VI obtain
R wherein
1Definition cotype XII with Hal
R wherein
2Definition cotype I.
(XIII+VI → XII) is equivalent to the acetalation of standard, and it can carry out according to the known way that is used for acetalation in reaction.For example, reaction can be by catalysis in the presence of organic acid or inorganic acid (as the vitriol oil), and the water that generates as condensation product can utilize component distillation to separate continuously from reaction mixture.In typical step, formula XIII and VI reactant are dissolved in the inert solvent (for example benzene,toluene,xylene or chloroform) that is fit to component distillation, the toluenesulphonic acids or the vitriol oil that add catalytic quantity, with the reaction mixture reflux, discharge the water that condensation generates via suitable condenser (for example Dean-stark trap) simultaneously.
At midbody compounds such as II, IVZ, V, X, XI and XII is new compound, and they are preparation formula I active ingredient especial manufacture.Therefore, these compounds belong to identical inventive concept, thereby constitute a part of the present invention.
Initiators such as formula III, VI, VII, VIII, IX and XIII are known on the technology, perhaps can prepare in accordance with known methods.
Formula I compound belongs to arthropods and the control of injury plant of Insecta and acarina in control effective aspect the plant pathogenic fungi.
Their favourable Fungicidally active by following employing 0.5-500mg active ingredient/liter the live test of experimental concentration be confirmed: the Kidney bean uromyce on the control frame beans, wheat handle rest fungus on the control wheat, Siberian cocklebur monofilament shell bacterium on the control cucumber, standing grain powdery mildew on control wheat and the barley, apple mildew handle coccus on the control apple, uncinula necator snag shell on the control grape vine is mould, clever withered shell ball cavity bacteria on the control wheat, standing grain on the control barley revolves spore bacterium and wheat class nuclear cavity bacteria, venturia inaequalis on the control apple, it is mould that the grape on phytophthora infestan on the control tomato and the control grape vine is given birth to single shaft.
A lot of formula I compounds have good plant tolerance.Therefore The compounds of this invention can be used for handling plant, seed and soil, so that kill plant pathogen epiphyte, summer spore rest fungus (rest fungus) purpose Basidiomycetes for example is as handle rest fungus, hunchbacked spore rest fungus, uromyce; The Ascomycetes of Erysiphales, for example powdery mildew, handle coccus, snag shell bacterium, single snag shell bacterium; And it is mould to revolve spore; Nuclear cavity bacteria; Black star bacterium; Ball chamber bacterium; Ball cavity bacteria; Imperfect fungi, as Magnaporthe grisea, film lead fungi, grape spore; And Oomycete, mould as epidemic disease, single shaft is mould.
One group of formula I compound is aspect control powdery mildew and fungies such as rest fungus, nuclear cavity bacteria and ball cavity bacteria, and the pathogenic agent aspect that particularly prevents and treats monocotyledons such as cereal (comprising wheat and barley) is very effective.Effective especially aspect the Oomycete of another group formula I compound on control dicotyledons such as grape, tomato or potato.
Have been found that formula I compound is particularly useful for control insect, particularly black bean aphid (Aphisfabae), rice green leafhopper (Nephotettix cincticeps), horseradish ape chrysomelid (Phaedoncochleariae) and Aedes aegypti (Aedes aegypti).This application provides a kind of method of controlling insect, and this method comprises the formula I compound of using significant quantity on the desinsection to insect or its habitat.
Find that also formula I compound is particularly useful for control acarina, especially cotton spider mites (T.urticae Koch) and panonychus ulmi (Panonychus ulmi).This application provides a kind of method of preventing and treating acarina, and this method comprises the formula I compound of using the tick mite killing significant quantity to acarina or its habitat.
Formula I compound is to use with unaltered form, promptly, employing is by the form of the pure substance that obtains in synthetic, dry also grinding, perhaps preferably with normally used auxiliary in preparation process, thus solution, rare milk sap, wettable powder, soluble powder, pulvis, granula and the capsule in polymkeric substance that can be processed into emulsion concentrates for example in known manner, can directly spray or dilute.Method that selection is used (for example spraying, become smog, atomizing, spreading or cast) and composition are with suitable purpose of being envisioned and environment on every side.
The compounds of this invention can be used in the many kinds of crops, for example soybean, coffee, ornamental plant (as Flos Pelargonii, rose), vegetables (as pea, cucumber, celery, tomato and fresh kidney beans), beet, sugarcane, cotton, flax, corn, grape circle, the operatic circle and drupe (as apple, pears, plum) and cereal (as wheat, oat, barley, rice).
The present invention also provides and has killed mite, fungicidal and insect-killing composition, wherein contain with thinner (being called thinner later on) that can be agricultural mutually a kind of formula I compound of blended as active ingredient.These compositions obtain with ordinary method, for example, The compounds of this invention and a kind of thinner and the auxiliary component (as tensio-active agent) that can choose adding wantonly are mixed mutually.
Various formulations, promptly, composition, preparation or mixture, the mixture that contains formula I active substance or this active substance and other mycocide, sterilant or miticide and solid in case of necessity or fluid additive, they prepare in a known manner, for example active substance are closely mixed and/or grind with surface active cpd (tensio-active agent) with thinner (as solvent, solid carrier) and when needing.
These compositions can also contain other additive, for example stablizer, defoamer, sanitas, viscosity modifier, tackiness agent, tackifier and fertilizer or be used for reaching other active substance of special-effect.
Here said thinner one speech be meant can be agricultural the liquid or solid material, they can be added to respectively and make its form that becomes more easily or better use in the active agents, and active agents is diluted to available or desired activity intensity.The example of this class thinner has talcum powder, kaolin, diatomite, dimethylbenzene or water.
Particularly, preparation with the Sprayable use, for example water-dispersible enriched material or wettable powder, can contain tensio-active agent, for example wetting agent and dispersion agent are as the alkylphenol of condensation product, alkylaryl sulphonate, sulfonated lignin, aliphatic alkyl vitriol and the ethoxylation of formaldehyde and naphthalenesulfonate and the fatty alcohol of ethoxylation.
In general, contain in the various formulations 1-90% weight active agents, 0-20% can be agricultural tensio-active agent and the thinner of 10-99%.The composition of conc forms, milk sap enriched material for example generally contains the active agents of about 5-70%, preferred 10-50% weight.Various formulations use pattern, for example be applied to the spray suspension liquid of insect and acarina habitat, contain the The compounds of this invention of 1-5000ppm usually as active agents.Typical spray suspension liquid can contain for example active agents of 10-1000ppm, preferred 20-500ppm.The rate of application of per hectare is generally per hectare 10-1000g active substance; Preferred per hectare 20-500g.
More suitably rate of application can be determined by tentative experiment by those skilled in the art, perhaps determines by the activity of comparison expression I compound and the known standard substance of rate of application.In general, when the rate of application with the about 20-500g in per hectare insect habitat, the preferred about 50-400g active ingredient of per hectare uses formula I compound, can obtain satisfied control to insect.When the rate of application with the about 20-100g active ingredient in per hectare acarina habitat uses formula I compound, can obtain gratifying control to acarian.When with the about 20-500g in per hectare plant epiphyte habitat, when preferably the rate of application of about 100-400g is used formula I compound, can realize gratifying control to plant epiphyte.
Except common thinner and tensio-active agent, the present composition can also contain the additive of special purpose, for example stablizer, deactivator (being used to have the solid preparation or the carrier of active surface), improvement and the adhering reagent of plant, corrosion inhibitor, defoamer and tinting material.
Plant is as follows with the example that kills mite, fungicidal and pesticide preparation: a. wettable powder formulation
10 parts of formula I compounds and 4 parts of synthetic fine silica, 3 parts of sodium lauryl sulphate, 7 parts of sodium lignosulfonates and 66 parts of kaolin fine powders and 10 parts of diatomite are mixed and grind, be about 5 μ m up to median size.Formed wettable powder is diluted with water to spraying fluid before use earlier, and it can soak the filling method with foliar spray method and root and use.B. granula
In a tumbler mixer, on the quartz sand of 94.5 weight parts, spray the tackiness agent (nonionic surface active agent) of 0.5 weight part, with whole mixture thorough mixing.The formula I compound of the present invention that adds 5 weight parts then continues thorough mixing, up to obtaining the granular preparation that size of particles is 0.3-0.7mm (when needing, can utilize the talcum powder that adds 1-5% weight with particle drying).This granula can be used with the mode that is incorporated in the soil adjacent with plant to be processed.C. milk sap enriched material
The formula I compound of 10 weight parts is mixed with the emulsifying agent of 10 weight parts and the dimethylbenzene of 80 weight parts.The enriched material dilute with water that will obtain like this before using, the milk sap of the formation concentration of wanting.
Following examples further specify the present invention.They are not to be limitation of the present invention.All temperature are degree centigrade.Unless otherwise indicated, the tlc that all is used on the silica gel of Rf value obtains.Embodiment 1:4-allyloxy methyl-2-methyl-2-(4-(2-(quinazoline-
4-base oxygen base) ethyl)-and phenyl) dioxolane
A) phenylformic acid 4-acetyl phenylethylester
263g (2.0mole) Aluminum chloride anhydrous is suspended in the methylene dichloride of 1800ml.After mixture is cooled to 0 ℃, add 81g (1.0mole) Acetyl Chloride 98Min. and 212g (0.8mole) phenylformic acid phenyl ethyl ester successively.Subsequently reactant was at room temperature stirred 16 hours, pour into then in the mixture of 500ml trash ice and 900ml concentrated hydrochloric acid.After will respectively being separated, water layer is with 2 * 400ml dichloromethane extraction.The organic layer water and 10% potassium bicarbonate aqueous solution that merge are washed, and use dried over mgso, reduction vaporization.Resistates is recrystallization in the ethyl acetate/hexane mixture.Output: 165g phenylformic acid 4-acetyl phenylethylester, fusing point 90.5-91.5 ℃.B) phenylformic acid 2-(4-(4-allyloxy methyl-2-methyl-dioxolane-2-yl) phenyl) ethyl ester
203g (0.75mole) phenylformic acid 4-acetyl phenylethylester is dissolved in the 1000ml toluene.In this solution, add 150g (1.1mole) glycerine-1-allyl ethers and 2.5g4-toluenesulphonic acids.Formed mixture is used Dean-stark trap reflux 4 hours.Cooling is poured on the 500ml trash ice then.After being separated two, water layer is with 2 * 300ml extracted with diethyl ether.The organic layer that merges is washed with the potassium bicarbonate aqueous solution of 400ml 10%, uses dried over mgso, reduction vaporization.Output: 272g phenylformic acid 2-(4-(4-allyloxy methyl-2-methyl-dioxolane-2-yl) phenyl) ethyl ester.C) 2-(4-(4-allyloxy methyl-2-methyl-dioxolane-2-yl) phenyl) ethanol
5.0g (13mmole) phenylformic acid 2-(4-(4-allyloxy methyl-2-methyl-dioxolane-2-yl) phenyl) ethyl ester was at room temperature stirred 2 hours in 10% potassium hydroxide solution (in the methanol aqueous solution 80%) of 100ml.Mixture is evaporated to half volume, with the dilution of 100ml water, with 3 * 100ml extracted with diethyl ether.The organic layer that merges is washed with 100ml, uses dried over mgso, reduction vaporization.Resistates is chromatography (hexane/ethyl acetate, 7: 3) on silica gel.Output: 2.4g2-(4-(4-allyloxy methyl-2-methyl-dioxolane-2-yl) phenyl) ethanol.D) 0.3g (12mmole) sodium hydride is suspended in 20ml 1, in the 2-glycol dimethyl ether.Mixture is being cooled to after 0 ℃, dropwise is being added to 3.3g (12mmole) 2-(4-(4-allyloxy methyl-2-methyl-dioxolane-2-yl) phenyl) ethanol at 10ml 1, the solution in the 2-glycol dimethyl ether.Reactant was at room temperature stirred 1 hour, be cooled to 0 ℃ once more.Add 2.3g (14mmole) 4-chloro-quinazoline in batches.At room temperature stirred reaction mixture is 3 hours, is cooled to 0 ℃ and also dropwise adds.Subsequently with this mixture of ethyl acetate extraction.The organic layer dried over mgso, reduction vaporization.Resistates is chromatography (hexane/ethyl acetate, 7: 3) on silica gel.Output: 3.5g 4-allyl oxygen methyl-2-methyl-2-(4-(2-(quinazoline-4-base oxygen) ethyl) phenyl) dioxolane.Perhaps e) in 202.5g2-(4-(the 4-allyloxy methyl-2-methyl-dioxolane-2-yl) phenyl) solution of ethanol in 1200ml toluene, adds 600ml 30% aqueous sodium hydroxide solution, 11.4g TEBA (3-ethyl benzyl ammonium chloride) and 131.6g4-chloro-quinazoline (adding) successively in batches.At room temperature stirred the mixture 5 hours, and used extracted with diethyl ether then, water and salt washing.The organic layer dried over mgso, reduction vaporization.Resistates is chromatography on silica gel, with 8: 2 to 1: 1 hexanes/ether wash-out.Output: 215g4-allyloxy methyl-2-methyl-2-(4-(2-(quinazoline-4-base oxygen base) ethyl) phenyl) dioxolane.Fusing point 62-64 ℃.Embodiment 2: phenylformic acid 4-formylphenyl ethyl ester
0 ℃ and stir under to phenylformic acid phenyl ethyl ester (45.2g, 0.2mole) add successively in the solution in methylene dichloride (140ml) titanium tetrachloride (114g, 0.6mole) and 1, the 1-dichlorodimethyl ether (25.3g, 0.22mole).After removing cooling bath, during being warmed to room temperature, there are a large amount of HCl gas to emit.At room temperature stirred reaction mixture spends the night.Then the mixture of brown is slowly poured in the trash ice, used dichloromethane extraction, extraction liquid water, saleratus saturated solution and salt washing.The organic layer dried over mgso that merges, solvent is removed in decompression.On silica gel, carry out column chromatography (elutriant: hexane/ethyl acetate, 9: 1), produce some initiators earlier, follow by the pure phenylformic acid 4-formylphenyl ethyl ester of 25.3g, fusing point 54-56 ℃.Embodiment 3:4-butyl-2-methyl-2-(4-(2-(5-chloro-6-ethyl
Pyrimidine-5-base is amino) ethyl) phenyl) dioxolane
A) N-(4-(4-butyl-2-methyl-dioxolane-2-yl) styroyl) phthalic imidine
In 9.5g (36mmole) 2-(4-(4-butyl-2-methyl-dioxolane-2-yl) phenyl) ethanol, 10g (38mmole) triphenyl phosphine and the solution of 5.8g (40mmole) phthalic imidine in the 400ml tetrahydrofuran (THF), dropwise add 7.3g (42mmole) diethylazodicarboxylate.Reaction mixture was at room temperature stirred 1 hour.Solvent is removed in decompression, and resistates is dissolved in the ether/hexane mixture.The precipitation that forms is washed with the ether/hexane mixture.The filtrate evaporated under reduced pressure that merges, resistates is chromatography (hexane/ethyl acetate, 7: 3) on silica gel.Product: N-(4-(4-butyl-2-methyl-dioxolane-2-yl) phenyl) styroyl) phthalic imidine.B) 2-(4-(4-butyl-2-methyl-dioxolane-2-yl) phenyl) ethamine
4.0g (10mmole) N-(4-(4-butyl-2-methyl-dioxolane-2-yl) styroyl) phthalic imidine is suspended in the 40ml ethanol, slowly add 40ml methylamine solution (33% ethanolic soln), reaction mixture was at room temperature stirred 3 hours, subsequently with the mixture reduction vaporization.The purity of resistates is enough to be directly used in next step.Product: 2-(4-(4-butyl-2-methyl-dioxolane-2-yl) phenyl) ethamine.C) with 2.1g (7.8mmole) 2-(4-(4-butyl-2-methyl-dioxolane-2-yl) phenyl) ethamine, 1.8g (10mmole) 4,5-two chloro-6-ethyl-pyrimidines and 2.4g (23mmole) the yellow soda ash mixture heating up in 40ml water refluxed 3 hours, dilute with water then is with 3 * 60ml ethyl acetate extraction.The organic layer that merges washes with water, uses dried over mgso, reduction vaporization.Resistates is chromatography (hexane/ethyl acetate, 1: 1) on silica gel.Product: 4-butyl-2-methyl-2-(4-(2-(5-chloro-6-ethyl-pyrimidine-4-base is amino) ethyl-phenyl) dioxolane.
Compound in the following table obtains with similar method.Ph in the table represents phenyl.
Table 1:
| Numbering | ????R 1 | ????R 2 | ????Z | Physical data | |
| ????Rf | System | ||||
| ?1.01 | ????H | ????CH 2OCH 2CH＝CH 2 | ????O | ????0.20 | Hexane/ethyl acetate, 1: 1 |
| ?1.02 | ????CH 3 | ????H | ????O | ????0.22 | Hexane/ethyl acetate, 1: 1 |
| ?1.03 | ????CH 3 | ????CH 3 | ????O | ????0.26 | Hexane/ethyl acetate, 7: 3 |
| ?1.04 | ????CH 3 | ????CH 2CH 3 | ????O | ????0.24 | Hexane/ethanol, 95: 5 |
| ?1.05 | ????CH 3 | ????CH 2CH 2CH 3 | ????O | ????0.37 | Hexane/ethyl acetate, 7: 3 |
| ?1.06 | ????CH 3 | ????CH 2CH 2CH 2CH 3 | ????O | ????n D 20：1,5581； ????0.26 | Hexane/ethanol, 9: 1 |
| ?1.07 | ????CH 3 | ??CH 2Cl | ????O | ????0.16 | Hexane/ethyl acetate, 7: 3 |
| ?1.08 | ????CH 3 | ??CH 2OCH 3 | ????O | ????0.14 | Hexane/ethanol, 95: 5 |
| ?1.09 | ????CH 3 | ??CH 2OCH 2CH＝CH 2 | ????O | ????m.p.62-64℃； ????0.21 | Hexane/ethyl acetate, 7: 3 |
| ?1.10 | ????CH 3 | ?CH 2OCH 2C(CH 3)＝CH 2 | ????O | ????0.32 | Ether/CH 2Cl 2，9∶1 |
| ?1.11 | ????CH 3 | ?CH 2OCH 2C(Cl)＝CH 2 | ????O | ????0.38 | Ether/CH 2Cl 2，9∶1 |
| ?1.12 | ????CH 3 | ?CH 2OCH 2CH＝CHCH 3 | ????O | ????0.34 | Ether/CH 2Cl 2，9∶1 |
| ?1.13 | ????CH 3 | ?CH 2OCH 2C≡CH | ????O | ????0.21 | Hexane/ethyl acetate, 1: 1 |
| ?1.14 | ????CH 3 | ?CH 2SCH 3 | ????O | ????0.16 | Hexane/ethanol, 95: 5 |
| ?1.15 | ????CH 3 | ?CH 2O(4-Cl)Ph | ????O | ????m.p.93-94℃； ????0.18 | Hexane/ethyl acetate, 7: 3 |
| ?1.16 | ????CH 3 | ?CH 2O(2-CH 3O)Ph | ????O | ????0.1 | Hexane/ethyl acetate, 7: 3 |
| ?1.17 | ????CH 3 | ?CH 2OCH 2Ph | ????O | ????0.32 | Ether/CH 2Cl 2，1∶1 |
| ?1.18 | ????CH 2Cl | ?H | ????O | ????m.p.106-107℃； ????0.33 | Hexane/ethyl acetate, 1: 1 |
| ??1.19 | ????CH 2CH 3 | ????CH 2OCH 2CH＝CH 2 | ??O | ????m.p.66℃ | |
| ??1.20 | ????CH 2CH 3 | ????CH 2OCH 2C≡CH | ??O | ????m.p.57-60℃ | |
| ??1.21 | ????CH 2CH 2CH 3 | ????H | ??O | ????0.14 | Hexane/ethyl acetate, 7: 3 |
| ??1.22 | ????CH 2CH 2CH 3 | ????CH 2CH 3 | ??O | ????0.18 | Hexane/ethyl acetate, 7: 3 |
| ??1.23 | ????CH 2CH 2CH 3 | ????CH 2OCH 2CH＝CH 2 | ??O | ????0.21 | Hexane/ethyl acetate, 7: 3 |
| ??1.24 | ????CH 3 | ????CH 2CH 2Ph | ??O | ||
| ??1.25 | ????CH 3 | ????Ph | ??O | ????0.34 | Hexane/ethyl acetate, 1: 1 |
| ??1.26 | ????CH 3 | ????n-C 6H 13 | ??O | ????0.27 ????n D 20＝1.5525 | Hexane/ethyl acetate, 7: 3 |
| ??1.27 | ????CH 3 | ????n-C 8H 17 | ??O | ????0.26 ????n D 20＝1.5444 | Hexane/ethyl acetate, 7: 3 |
| ??1.28 | ????CH 3 | ????n-C 10H 21 | ??O | ????0.32 | Hexane/ethyl acetate, 7: 3 |
| ??1.29 | ????CH 3 | ????CH 2OCH 2CH 2OCH 3 | ??O | ????0.20 | Hexane/ethyl acetate, 7: 3 |
| ??1.30 | Cyclopropyl | ????CH 2OCH 2CH＝CH 2 | ??O | ????0.32 | Ether/CH 2Cl 2，9∶1 |
| ??1.31 | ????CH 3 | ????n-C 4H 9 | ??NH | ????0.29 | Ethyl acetate |
| 1.32 | ????CH 3 | ????CH 2-0-(4-t.C 4H 9)-Ph | ??NH | ????0.23 | Ethyl acetate |
| 1.33 | ????CH 3 | ????n-C 8H 17 | ??NH | ????0.27 | Ethyl acetate |
Table 2:
| Numbering | ????R 1 | ????R 2 | ?Z | Physical data Rf system | |
| 2.01 | ????CH 3 | ????CH 2CH 3 | ?O | ????0.30 | Hexane/ethyl acetate, 7: 3 |
| 2.02 | ????CH 3 | ????CH 2CH 2CH 3 | ?O | ????0.25 | Hexane/ethyl acetate, 7: 3 |
| 2.03 | ????CH 3 | ????CH 2OCH 2CH 3 | ?O | ????0.20 | Hexane/ethyl acetate, 7: 3 |
| 2.04 | ????CH 3 | ????CH 2OCH 2CH 2CH 3 | ?O | ????0.23 | Hexane/ethyl acetate, 7: 3 |
| ?2.05 | ????CH 3 | ??CH 2OCH 2CH(CH 3) 2 | ?O | ??0.24 | Hexane/ethyl acetate, 7: 3 |
| ?2.06 | ????CH 3 | ??CH 2OCH(CH 3) 2 | ?O | ??0.20 | Hexane/ethyl acetate, 7: 3 |
| ?2.07 | ????CH 3 | ??CH 2OCH 2CH＝CH 2 | ?O | ??0.27 | Hexane/ethyl acetate, 7: 3 |
| ?2.08 | ????CH 3 | ??CH 2OCH 2C(CH 3)＝CH 2 | ?O | ??0.20 | Hexane/ethyl acetate, 7: 3 |
| ?2.09 | ????CH 3 | ??CH 2OCH 2C(Cl)＝CH 2 | ?O | ??0.20 | Hexane/ethyl acetate, 7: 3 |
| ?2.10 | ????CH 3 | ??CH 2OCH 2C≡CH | ?O | ??0.14 | Hexane/ethyl acetate, 7: 3 |
| ?2.11 | ????CH 3 | ??CH 2OCH 2OCH 3 | ?O | ??0.09 | Hexane/ethyl acetate, 7: 3 |
| ?2.12 | ????CH 3 | ??CH 2OCH 2CH 2OCH 3 | ?O | ??0.14 | Hexane/ethyl acetate, 1: 1 |
| ?2.13 | ????CH 3 | ??CH 2O(2-CH 3O)Ph | ?O | ??0.12 | Hexane/ethyl acetate, 7: 3 |
| ?2.14 | ????CH 3 | ??CH 2OCH 2Ph | ?O | ??0.16 | Hexane/ethyl acetate, 7: 3 |
| ?2.15 | ????CH 2CH 2CH 3 | ??H | ?O | ??0.31 | Hexane/ethyl acetate, 7: 3 |
| ?2.16 | ????CH 2CH 2CH 3 | ??CH 2CH 3 | ?O | ??0.26 | Hexane/ethyl acetate, 7: 3 |
| ?2.17 | ????CH 2CH 2CH 3 | ??CH 2OCH 2CH＝CH 2 | ?O | ??0.26 | Hexane/ethyl acetate, 7: 3 |
| 2.18 | ????CH 3 | ??CH 2CH 2CH 2CH 3 | ?O | 1H-NMR(CDCl 3)；8,49(s，1H)；7,48-7,17(m， 4H)；4,54(tr，2H)；4,25-3,3(m，3H)；3,07 (tr，2H?)；2,78(tr，2H)；2,54(tr，2H)；1,90- 1,75(m，4H)；1,62(s，3H)；1,45-1,18(m， 6H)；0,9(m，3H)ppm. | |
| 2.19 | ????CH 3 | ??CH 2Cl | ?O | 1H-NMR(CDCl 3)：8,49(s，1H)；7,48-7,17(m， 4H)；4,55(tr，2H)；4,33-4,15(m，1H)；3,98- 3,45(m，4H)；3,08(tr，2H)；2,78(tr，2H)； 2,52(tr，2H)；1,92-1,70(m，4H)；1,68(s， 3H)ppm. | |
| 2.20 | ????CH 3 | ??CH 2OCH 2CH＝CHCH 3 | ?O | 1H-NMR(CDCl 3)：8,49(s，1)；7,48-7,17(m， 4H)；5,85-5,43(m，2H)；4,54(tr，2H)；4,47- 3,38(m，7H)；3,08(tr，2H)；2,78(tr，2H)； 2,54(tr，2H)；1,90-1,75(m，4H)；1,78-1,60 (m，6H)ppm. | |
| 2.21 | ????CH 3 | ??CH 2CH 2CH 2CH 3 | ?NH | ?0.26 | Ethyl acetate |
| 2.22 | ????CH 3 | ??CH 2OCH 2CH＝CH 2 | ?NH | ?0.19 | Ethyl acetate |
Table 3:
| Numbering | ??E | ??R 1 | ????R 2 | ??Z | Physical data Rf system | |
| ??3.01 | ??H | ??CH 3 | ?CH 2CH 2CH 2CH 3 | ??O | ????0.19 | Hexane/ethyl acetate, 9: 1 |
| ??3.02 | ??CH 3 | ??CH 3 | ?CH 2CH 2CH 2CH 3 | ??O | ????0.17 | Hexane/ethyl acetate, 9: 1 |
| ??3.03 | ??H | ??CH 3 | ?CH 2OCH 2CH＝CH 2 | ??O | ????0.56 | Ether/CH 2Cl 2，4∶1 |
| ??3.04 | ??CH 3 | ??CH 3 | ?CH 2OCH 2CH＝CH 2 | ??O | ??m.p.：56-58℃ | |
| ??3.05 | ??H | ??CH 3 | ?CH 2OCH 2C(CH 3)＝CH 2 | ??O | ????0.15 | Hexane/ethyl acetate, 9: 1 |
| ??3.06 | ??CH 3 | ??CH 3 | ?CH 2OCH 2C(CH 3)＝CH 2 | ??O | ????0.34 | Hexane/ethyl acetate, 7: 3 |
| ??3.07 | ??H | ??CH 3 | ?CH 2OCH 2C(Cl)＝CH 2 | ??O | ????0.39 | Hexane/ethyl acetate, 7: 3 |
| ??3.08 | ??CH 3 | ??CH 3 | ?CH 2OCH 2C(Cl)＝CH 2 | ??O | ????0.31 | Hexane/ethyl acetate, 7: 3 |
| ??3.09 | ?H | ?CH 3 | ????CH 2OCH 2CH＝CHCH 3 | ?O | ????0.14 | Ethane/hexane, 3: 7 |
| ??3.10 | ?CH 3 | ?CH 3 | ????CH 2OCH 2CH＝CHCH 3 | ?O | ????m.p.：47-49℃ | |
| ??3.11 | ?CH 3 | ?CH 3 | ????CH 2SCH 3 | ?O | ????0.24 | Ether/hexane, 1: 1 |
| ??3.12 | ?CH 3 | ?CH 3 | ????CH 2SCH 2CH 3 | ?O | ????0.30 | Ether/hexane, 1: 1 |
| ??3.13 | ?CH 3 | ?CH 3 | ????Ph | ?O | ||
| ??3.14 | ?CH 3 | ?CH 3 | ????CH 2CH 2Ph | ?O | ||
| ??3.15 | ?CH 3 | ?CH 3 | ????CH 2CH 2CH 2CH 3 | ?NH | ????0.17 ????n D 20＝1.5792 | Hexane/ethyl acetate, 7: 3 |
| ??3.16 | ?CH 3 | ?CH 3 | ????n-C 6H 13 | ?NH | ????0.15 | Hexane/ethyl acetate, 7: 3 |
Table 4:
| Numbering | ?R 1 | ?????????R 2 | ??R 3 | ????R 4 | ?Z | Physical data Rf system | |
| 4.01 | ?H | ??CH 2OCH 2CH＝CH 2 | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.11 | Hexane/ethyl acetate, 1: 1 |
| 4.02 | ?CH 3 | ??CH 2CH 2CH 2CH 3 | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.22 | Hexane/ethyl acetate, 1: 1 |
| 4.03 | ?CH 3 | ??CH 2OCH 2CH 3 | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.32 | Hexane/ethyl acetate, 1: 2 |
| 4.04 | ?CH 3 | ??CH 2OCH(CH 3) 2 | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.28 | Hexane/ethyl acetate, 1: 2 |
| 4.05 | ?CH 3 | ??CH 2OCH 2CH＝CH 2 | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.28 | Hexane/ethyl acetate, 1: 2 |
| 4.06 | ?CH 3 | ??CH 2OCH 2CH＝CH 2 | ?Cl | ?CH 2CH 3 | ?O | ?0.27 | Hexane/ethyl acetate, 7: 3 |
| 4.07 | ?CH 3 | ??CH 2OCH 2C(CH 3)＝CH 2 | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.32 | Hexane/ethyl acetate, 1: 2 |
| ?4.08 | ??CH 3 | ??CH 2OCH 2C(CH 3)＝CH 2 | ??Cl | ?CH 2CH 3 | ?O | ?0.19 | Hexane/ethyl acetate, 9: 1 |
| ?4.09 | ??CH 3 | ??CH 2OCH 2C(Cl)＝CH 2 | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.28 | Hexane/ethyl acetate, 1: 2 |
| ?4.10 | ??CH 3 | ??CH 2OCH 2CH＝CHCH 3 | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.28 | Hexane/ethyl acetate, 1: 2 |
| ?4.11 | ??CH 3 | ??CH 2OCH 2C≡CH | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.30 | Hexane/ethyl acetate, 1: 2 |
| ?4.12 | ??CH 3 | ??CH 2SCH 3 | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.32 | Hexane/ethyl acetate, 1: 2 |
| ?4.13 | ??CH 3 | ??CH 2SCH 2CH 3 | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.34 | Hexane/ethyl acetate, 1: 2 |
| ?4.14 | ??CH 3 | ??CH 2O(2-CH 3O-)Ph | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.32 | Hexane/ethyl acetate, 1: 2 |
| ?4.15 | ??CH 3 | ??CH 2OCH 2Ph | ?OCH 3 | ?CH 2OCH 3 | ?O | ?0.32 | Hexane/ethyl acetate, 1: 2 |
| ?4.16 | ??CH 3 | ??CH 2CH 2CH 2CH 3 | ?CL | ?CH 2CH 3 | ?NH | ?0.21 | Hexane/ethyl acetate, 7: 3 |
| ?4.17 | ??CH 3 | ??CH 2CH 2CH 2CH 3 | ?OCH 3 | ?CH 2OCH 3 | ?NH | ?0.17 | Ethyl acetate |
| ?4.18 | ??CH 3 | ??CH 2OCH 2CH＝CH 2 | ?Cl | ?CH 2CH 3 | ?NH | ?0.18 | Hexane/ethyl acetate, 7: 3 |
| ?4.19 | ??CH 3 | ??CH 2OCH 2(CH 3)＝CH 2 | ?Cl | ?CH 2CH 3 | ?NH | ?0.28 | Hexane/ethyl acetate, 7: 3 |
| ?4.20 | ??CH 3 | ??CH 2OCH 2C≡CH | ?Cl | ?CH 2CH 3 | ?NH | ?0.25 | Hexane/ethyl acetate, 7: 3 |
| ?4.21 | ??CH 3 | ??CH 2O(2-CN)Ph | ?Cl | ?CH 2CH 3 | ?NH | ?0.33 | Hexane/ethyl acetate, 7: 3 |
| ?4.22 | ?CH 3 | ??CH 2O(CH 2(2-CN)Ph | ??Cl | ?CH 2CH 3 | ?NH | ?0.1 | Hexane/ethyl acetate, 7: 3 |
| ?4.23 | ?CH 3 | ??CH 2OCH 2(4-Cl)Ph | ??Cl | ?CH 2CH 3 | ?NH | ?0.14 | Hexane/ethyl acetate, 7: 3 |
| ?4.24 | ?CH 3 | ??CH 2O(3-CF 3)Ph | ??Cl | ?CH 2CH 3 | ?NH | ?0.14 | Hexane/ethyl acetate, 7: 3 |
| ?4.25 | ?CH 3 | ??CH 2OCH 2CH 2CH 2Ph | ??Cl | ?CH 2CH 3 | ?NH | ?0.25 | Hexane/ethyl acetate, 7: 3 |
Table 5:
| Numbering | ????R 1 | ??????R 2 | Physical data | |
| ????Rf | System | |||
| ??5.01 | ????H | ??CH 2OCH 2CH＝CH 2 | ????0.09 | Hexane/ethyl acetate, 7: 3 |
| ??5.02 | ????CH 3 | ??H | ????0.10 | Hexane/ethyl acetate, 7: 3 |
| ??5.03 | ????CH 3 | ??CH 3 | ????0.06 | Hexane/ethyl acetate, 7: 3 |
| ??5.04 | ????CH 3 | ??CH 2CH 3 | ????0.17 | Hexane/ethyl acetate, 7: 3 |
| ??5.05 | ????CH 3 | ??CH 2CH 2CH 3 | ||
| ??5.06 | ????CH 3 | ??CH 2CH 2CH 2CH 3 | ????0.25 | Hexane/ethyl acetate, 9: 1 |
| ??5.07 | ????CH 3 | ??CH 2Cl | ????0.15 | Hexane/ethyl acetate, 7: 3 |
| ??5.08 | ????CH 3 | ??CH 2OCH 3 | ||
| ??5.09 | ????CH 3 | ??CH 2OCH 2CH＝CH 2 | ????0.08/ ????0.15 | Hexane/ethyl acetate, 7: 3 |
| ??5.10 | ????CH 3 | ??CH 2OCH 2C(CH 3)＝CH 2 | ????0.07/ ????0.15 | Hexane/ethyl acetate, 7: 3 |
| ??5.11 | ????CH 3 | ??CH 2OCH 2C(Cl)＝CH 2 | ????0.07/ ????0.13 | Hexane/ethyl acetate, 7: 3 |
| ??5.12 | ????CH 3 | ??CH 2OCH 2CH＝CHCH 3 | ||
| ??5.13 | ????CH 3 | ??CH 2OCH 2C≡CH | ||
| ??5.14 | ???CH 3 | ????CH 2SCH 3 | ||
| ??5.15 | ???CH 3 | ????CH 2O(4-Cl-)Ph | ????0.20 | Hexane/ethyl acetate, 7: 3 |
| ??5.16 | ???CH 3 | ????CH 2O(2-CH 3O-)Ph | ||
| ??5.17 | ???CH 3 | ????CH 2OCH 2Ph | ||
| ??5.18 | ??CH 2Cl | ????H | ||
| ??5.19 | ??CH 2CH 3 | ????CH 2OCH 2CH＝CH 2 | ||
| ??5.20 | ??CH 2CH 3 | ????CH 2OCH 2≡CH | ||
| ??5.21 | ??CH 2CH 2CH 3 | ????H | ????0.10 | Hexane/ethyl acetate, 7: 3 |
| ??5.22 | ??CH 2CH 2CH 3 | ????CH 2CH 3 | ????0.07/ ????0.13 | Hexane/ethyl acetate, 7: 3 |
| ??5.23 | ??CH 2CH 2CH 3 | ??CH 2OCH 2CH＝CH 2 | ????0.10/ ????0.18 | Hexane/ethyl acetate, 7: 3 |
| ??5.24 | ????CH 3 | ????CH 2SCH 2CH 3 | ||
| ??5.25 | ????CH 3 | ????Ph | ????0.30 | Hexane/ethyl acetate, 1: 1 |
| ??5.26 | ????CH 3 | ????CH 2CH 2Ph | ||
| ??5.27 | ????CH 3 | ????n-C 6H 13 | ????0.23 | Hexane/ethyl acetate, 7: 3 |
| ??5.28 | ????CH 3 | ????n-C 8H 17 | ????0.22 | Hexane/ethyl acetate, 7: 3 |
| ??5.29 | ????CH 3 | ????n-C 10H 21 | ????0.40 | Hexane/ethyl acetate, 1: 1 |
| ??5.30 | ????CH 3 | ????CH 2OCH(CH 3) 2 | ????0.10 | Hexane/ethyl acetate, 7: 3 |
Table 6.
| Numbering | ????R 1 | ????R 2 | ?X | ?Y | Physical data | |
| ??Rf | System | |||||
| ??6.01 | ????H | ??CH 2OCH 2CH＝CH 2 | ?H | ?H | ?0.29 | Hexane/ethanol, 95: 5 |
| ??6.02 | ????CH 3 | ????H | ?H | ?H | ?m.p.69-70℃ | |
| ??6.03 | ????CH 3 | ????CH 3 | ?H | ?H | ?0.55 | Hexane/ethanol, 95: 5 |
| ??6.04 | ????CH 3 | ????CH 2CH 3 | ?H | ?H | ?0.52 | Hexane/ethyl acetate, 7: 3 |
| ??6.05 | ????CH 3 | ????CH 2CH 2CH 3 | ?H | ?H | ?0.46 | Hexane/ethyl acetate, 7: 3 |
| ??6.06 | ????CH 3 | ????CH 2CH 2CH 2CH 3 | ?H | ?H | ?0.20/ ?0.24 | Hexane/ether, 9: 1 |
| ??6.07 | ????CH 3 | ????CH 2Cl | ?H | ?H | ?0.39 | Hexane/ethyl acetate, 7: 3 |
| ??6.08 | ????CH 3 | ????CH 2OCH 3 | ?H | ?H | ?0.25/ ?0.30 | Hexane/ethanol, 95: 5 |
| ??6.09 | ????CH 3 | ??CH 2OCH 2CH＝CH 2 | ?H | ?H | ?0.26/ ?0.30 | Hexane/ethyl acetate, 7: 3 |
| ??6.10 | ????CH 3 | ??CH 2OCH 2C(CH 3)＝CH 2 | ?H | ?H | ||
| ??6.11 | ????CH 3 | ??CH 2OCH 2C(Cl)＝CH 2 | ?H | ?H | ||
| ??6.12 | ????CH 3 | ??CH 2OCH 2CH＝CHCH 3 | ?H | ?H | ||
| ?6.13 | ????CH 3 | ????CH 2OCH 2C≡CH | ?H | ?H | ||
| ?6.14 | ????CH 3 | ????CH 2SCH 3 | ?H | ?H | ||
| ?6.15 | ????CH 3 | ????CH 2O(4-Cl-)Ph | ?H | ?H | ?0.47/ ?0.49 | Hexane/ethyl acetate, 7: 3 |
| ?6.16 | ????CH 3 | ??CH 2O(2-CH 3O-)Ph | ?H | ?H | ||
| ?6.17 | ????CH 3 | ????CH 2OCH 2Ph | ?H | ?H | ||
| ?6.18 | ??CH 2Cl | ????H | ?H | ?H | ||
| ?6.19 | ??CH 2CH 3 | ??CH 2OCH 2CH＝CH 2 | ?H | ?H | ||
| ?6.20 | ??CH 2CH 3 | ??CH 2OCH 2C≡CH | ?H | ?H | ||
| ?6.21 | ??CH 2CH 2CH 3 | ????H | ?H | ?H | ?0.23 | Hexane/ethyl acetate, 9: 1 |
| ?6.22 | ??CH 2CH 2CH 3 | ????CH 2CH 3 | ?H | ?H | ?0.24/ ?0.30 | Hexane/ethyl acetate, 7: 3 |
| ?6.23 | ??CH 2CH 2CH 3 | ??CH 2OCH 2CH＝CH 2 | ?H | ?H | ?0.42/ ?0.48 | Hexane/ethyl acetate, 7: 3 |
| ?6.24 | ????CH 3 | ????CH 2SCH 2CH 3 | ?H | ?H | ||
| ?6.25 | ????CH 3 | ????CH 2OCH(CH 3) 2 | ?H | ?H | ?0.35 | Hexane/ethyl acetate, 7: 3 |
Table 7:
| Numbering | ????R 1 | ??X | ??Y | Physical data m.p. (℃) |
| ??7.01 | ????H | ??H | ??H | ????54-56℃ |
| ??7.02 | ????CH 3 | ??H | ??H | ??90.5-91.5℃ |
| ??7.03 | ????CH 2Cl | ??H | ??H | |
| ??7.04 | ????CH 2CH 3 | ??H | ??H | |
| ??7.05 | ??CH 2CH 2CH 3 | ??H | ??H | ????56-58℃ |
Table 8
Bioassay
| Numbering | ??R 1 | ??????R 2 | Physical data | |
| ????Rf | System | |||
| ??8.01 | ??CH 3 | ??CH 2OCH 2＝CH 2 | ????0.15 | Hexane/ethyl acetate, 7: 3 |
| ??8.02 | ??CH 3 | ??CH 2OCH 2C(CH 3)＝CH 2 | ????0.15 | Hexane/ethyl acetate, 7: 3 |
| ??8.03 | ??CH 3 | ??CH 2OCH 2C≡CH | ????0.2 | Hexane/ethyl acetate, 7: 3 |
| ??8.04 | ??CH 3 | ??CH 2O(3-CF 3)Ph | ????0.25 | Hexane/ethyl acetate, 7: 3 |
| ??8.05 | ??CH 3 | ??CH 2OCH 2(2-CN)Ph | ????0.2 | Hexane/ethyl acetate, 7: 3 |
| ??8.06 | ??CH 3 | ??CH 2CH 2CH 2CH 3 | ????0.2 | Hexane/ethyl acetate, 7: 3 |
In following test, the preparation of the formula I compound of embodiment a, b or c uses with the form of dilution.Desinsection with kill that the mite test contacts and through a) aphis fabae (black bean aphid) of stomach effect
Handling a few days ago, potted plant broad bean plant (broad bean) is infectd the adult and the pupa of black bean aphid (aphis fabae).The plant that every strain is had 30 insects approximately with atomizer with 500 and 100mg active ingredient/liter two kinds of concentration spray medicines (every kind of concentration 1 strain plant).Handled back 2 days, by measuring drug effect to compare the close dew situation of aphid excretory in the same old way with untreated.Handled back 8 days, and utilized the remaining insect number of range estimation to calculate effectiveness according to the Abbott method.
In this test, compound 1.01,1.03,1.05,1.06,1.08,1.09,1.14,1.22,1.23,1.30,1.31,3.15,3.16,3.09,4.01,4.12,4.13.4.16,4.17,4.18,4.18,4.19,4.20 and 4.25 show to render a service when 500mg/l be 90% or higher.B) rice green leafhopper
Use atomizer to spray medicine (every kind of concentration 1 strain) to rice strain (rice) with 500mg active ingredient/liter a kind of concentration.After sprayed deposit thing drying, every strain rice infects the pupa (L2 to L3) of 10 rice green leafhoppers (Nephotettix cincticeps).Handled back 2 days and 5 days, and counted dead and the pupa number of living.Calculate and press the corrected mortality ratio % of Abbott method.In this test, compound 1.05,1.07,1.13,1.15,1.31,3.02,3.03,3.11,3.12,3.15,4.12,4.13,4.16,4.17 and 4.18 demonstrates when 500mg/l that to render a service be 90% or higher.C) cotton spider mites (two-spotted spider mite)
Before 2 days, infected potted plant Kidney bean strain (Kidney bean) the spray medicine of about 20 cotton spider mites (two-spotted spider mite, the mictium of adult, pupa and larva) with atomizer.Use 2 kinds of concentration (500 and the 100mg active ingredient/rise spray dilution liquid).The remaining mite of counting when handling back 2 days and 8 days.Calculate effectiveness % according to the Abbott method, in this test, compound 1.01,1.02,1.03,1.04,1.05,1.06,1.07,1.08,1.09,1.10,1.11,1.12,1.21,1.23,1.29,1.30,1.31,2.01,2.02,2.03,2.06,2.10,2.12,2.14,2.18,2.19,3.03,3.04,3.11,3.12,3.15,3.16,4.01,4.02,4.03,4.05,4.06,4.11,4.14,4.16,4.17,4.18,4.19,4.20 4.21,4.22,4.23,4.24 and 4.25 concentration at 500ml/l demonstrate after 8 days and render a service is 90% or higher.The active horseradish daikon leaf beetle of residual contact
10 horseradish daikon leaf beetles (Coleoptera, Chrysomelidae, horseradish daikon leaf beetle) adult is limited in sprayed in the plastics matter Petri dish (9cm diameter) of medicine with atomizer in advance.Use 2 kinds of concentration (500 and the 100mg active ingredient/rise spray dilution liquid).Handle and measured mortality ratio % (making Abbott proofreaies and correct) in back 2 days.In this test, compound 1.13,1.20 and 3.02 demonstrates when 500mg/l that to render a service be 90% or higher.Ovicidal activity cotton spider mites (two-spotted spider mite)
The only female cotton spider mites adult of 5-7 is limited in the glue ring of the diameter 2cm on the Kidney bean leaf front, in 24 hours, allows it lay eggs.After removing female insect, spray medicine to the plant that has ovum with atomizer.Use a kind of concentration (every liter of spray dilution liquid 100mg active ingredient).Handle and calculated mortality ratio % (making Abbott proofreaies and correct) in back 5 days, that is, and corrected % of not hatching ovum.In this test, compound 1.03,1.04,1.05,1.06,1.07,1.09,1.10,1.11,1.13,1.14,1.15,1.17,1.30,1.31,2.01,2.02,2.04,2.06,2.10,2.14,2.18,3.01,3.02,3.03,3.04,3.06,3.09,3.11,3.15,4.02,4.03,4.04,4.06 4.07,4.11,4.13,4.17,4.18 and 4.19 demonstrate that to render a service be 90% or higher.Fungicidal test a) is prevented and treated the active Siberian cocklebur monofilament shell bacterium of powdery mildew:
With the cucumber plant in 7 day age (cotyledon stage) with every liter of suspension spray that contains the 250mg active ingredient up near overflow.Settling drying in addition then.After 1 day, the plant of handling is with containing 1 * 10
5The conidial spore suspension inoculation of the Siberian cocklebur monofilament shell bacterium that/ml has just collected, incubation 7 days under+24 ℃ and 60% relative humidity at room temperature then.By comparing the infringement situation of fungi, the effectiveness of confirmed test compound with adjoining tree unprocessed but same inoculation.In this test, compound 1.02,1.03,1.05,1.07,1.09,1.11,1.12,1.13,1.15,1.16,1.17,1.18,1.20,1.21,1.29,1.31,2.02,2.07,2.10,2.13,2.14,2.19,3.03,3.04,3.09,3.11,3.12,3.15,4.09,4.10 4.13,4.15,4.16,4.17 and 4.18 demonstrate that to render a service be 90% or higher.
With the preventing efficiency of each compound of similar method test to following pathogenic agent:
Apple mildew handle coccus on the apple,
Standing grain powdery mildew on wheat or the barley (stem grafting kind),
Grape snag shell on the grape is mould.B) prevent and treat the active Kidney bean uromyce of rust, shot hole, caryosphere shell bacterium, ball cavity bacteria:
The Kidney bean plant in 14 day age (2 leaf stages) is sprayed near overflow with every liter of suspension that contains the 250mg active ingredient.Make the settling drying subsequently.After one day, with the plant of handling with containing 1 * 10
5The spore suspension inoculation of the Kidney bean uromyce spore that/ml has just collected.Incubation is 3 days in the high humidity case of 23 ℃ and relative humidity＞95%, then incubation 10 days under+24 ℃ and 60% relative humidity.By comparing the degree of fungi infringement, determine the effectiveness of compound with adjoining tree unprocessed but same inoculation.In this test, compound 1.20,1.21,2.02,2.07,2.08,2.09,2.10,2.13,2.14,2.19,2.20,3.03,3.04,3.09,3.11,3.12,4.09,4.10,4.14,4.15,4.20,4.22 and 4.23 demonstrates that to render a service be 90% or higher.
Use each compound of similar method test to prevent and treat the effectiveness of following pathogenic agent:
Wheat handle rest fungus on the wheat (plant in 10 day age),
Wheat class nuclear cavity bacteria on the barley,
Clever withered shell ball cavity bacteria on the wheat,
Venturia inaequalis on the apple (21 day age plant; Spore suspension contains 1% Fructus Hordei Germinatus).C) control downy mildew activity
The tomato (Lycopericum esculentum) of 6 leaves is sprayed near overflow with every liter of spray suspension liquid that contains the 250mg active ingredient.Make the settling drying then.After 1 day, the plant of handling contains 1 * 10 with what just collected
5The inoculation of the sporangial spore suspension of/ml phytophthora infestan, incubation is 7 days in the high humidity case of+18 ℃ and＞95% relative humidity.By comparing the degree of fungi infringement, the effectiveness of confirmed test compound with adjoining tree unprocessed but same inoculation.In this test, compound 1.07,1.11,1.12,1.18,1.29,1.31,2.02,2.07,2.09,2.19,3.15,3.16,4.16,4.18,4.19,4.20 and 4.25 demonstrates that to render a service be 90% or higher.
With similar method test compound grape on the grape vine is given birth to the mould preventing efficiency of single shaft.D) activity after the seed treatment
The compounds of this invention also can be used for seed treatment.Confirmed favourable Fungicidally active by the test of doing with following pathogenic agent in vitro:
Wheat class nuclear cavity bacteria,
Naked smut,
Snow-white gelechiid (Gerlachia nivalis)
The withered shell ball cavity bacteria of grain husk.
The wheat seed that hot-pressing processing is crossed is with the spore of pathogenic agent or mycelium inoculation and with the test compound coating of different concns, and dosage is every 1000kg seed 50g active ingredient.The seed that to handle is placed on the agar plate then, makes pathogenic agent grow 3-8 days in the dark place under+24 ℃.
By relatively by the fungal growth situation of handling and the seed of untreated inoculation bears, the effectiveness of confirmed test compound.
For the crop tolerance of assessing compound, apply sound wheat and barley seed by above-mentioned dosage.Make seed in Petri dish, under+18 ℃ and high humidity, on wet filter paper, germinate 10 days then.Comparison process and untreated seedling growth situation, the degree of injury of record plant.
Claims (21)
1. the dioxolane 2-of formula I (4-(2-pyrimidine-4-base oxygen base-or-the 4-base is amino) ethyl) phenyl)
Wherein:
R
1Be hydrogen, C
1-4Alkyl, C
1-4Haloalkyl or C
3-6Cycloalkyl,
R
2Be hydrogen, C
1-10Alkyl, C
1-8Alkoxy-C
1-4Alkyl, C
3-8Alkene oxygen base-C
1-4Alkyl, C
3-8Haloalkene oxygen base-C
1-4Alkyl, C
3-8Alkynyloxy group-C
1-4Alkyl, C
1-8Halogenated alkoxy-C
1-4Alkyl, C
1-8Alkylthio-C
1-4Alkyl, aryl, aryloxy-C
1-4Alkyl, aryl-C
1-4Alkoxy-C
1-4Alkyl, heteroaryloxy C
1-4Alkyl, C
1-4Alkoxy-C
1-4Alkoxy-C
1-4Alkyl or aryl C
1-8Alkyl,
R
3And R
4Be halogen, C independently of one another
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Alkoxy-C
1-4Alkyl, C
1-4Carbalkoxy-C
1-4Alkyl, C
1-4Carbalkoxy, cyano group-C
1-4Alkyl, cyano group or-COOH, perhaps
R
3And R
4Form one together and be selected from tetramethylene, 1,4-Aden dialkylene or-abutment of S-CH=CH-, they all can randomly be selected from halogen or C
1-4One or two group of alkyl replaces,
Z is NH or oxygen.
2. the compound of claim 1, wherein R
3And R
4Form tetramethylene or the Aden's dialkylene abutment that to choose replacement wantonly together, thereby form an optional tetrahydro quinazoline or a quinazoline part that replaces with the pyrimidine ring that they connected.
3. each a kind of compound, wherein R in the claim 1 or 2
1Be hydrogen or methyl.
4. each a kind of compound, wherein R in the claim 1 to 3
2Be C
1-8Alkyl, C
1-8Alkoxy-C
1-4Alkyl, C
3-8Alkene oxygen base-C
1-4Alkyl or C
1-4Alkoxy-C
1-4Alkoxy-C
1-4Alkyl.
5. be selected from a kind of compound of following material: 4-allyloxy methyl-2-methyl-2-(4-(2-(quinazoline-4-base oxygen base) ethyl) phenyl) dioxolane, ((2-(5 for 4-for 4-allyloxy methyl-2-methyl-2-, 6,7,8-tetrahydro quinazoline-4-base oxygen base) dioxolane phenyl ethyl)), 4-butyl-2-methyl-2-(4-(2-(quinazoline-4-base oxygen base) ethyl) phenyl) dioxolane, and 4-butyl-2-methyl-2-(4-(2-(5-methyl-thieno-(2,3-d) pyrimidine-4-base is amino) ethyl) phenyl) dioxolane.
6. the method for preparing the formula I compound of claim 1, this method comprise 2-(4-(2-hydroxyethyl) phenyl) dioxolane or 2-(4-(2-aminoethyl) phenyl) dioxolane of formula X and the 4-halogenated pyrimidine reaction of formula III that makes formula II
R wherein
1And R
2It is identical with the definition of claim 1 couple formula I,
R wherein
3And R
4Identical with the definition of claim 1 couple formula I, Hal is a halogen, preferred chlorine or bromine.
7. the agricultural composition that contains claim 1 formula I compound and a kind of agricultural thinner.
8. killing the method for acarian and insect, is the formula I compound of the claim 1 of effective quantity comprising using for killing mite and desinsection to acarian and insect or its habitat.
9. kill the method for plant pathogenic fungi, comprising the formula I compound of using the claim 1 of the effective quantity of fungicidal to fungi or its habitat.
10. a kind of 2-of formula II (4-(2-hydroxyethyl) phenyl) dioxolane
R wherein
1And R
2Identical with the definition of claim 1 couple formula I.
11. the method for 2-(4-(2-hydroxyethyl) phenyl) dioxolane of preparation claim 10 Chinese style II is comprising with the hydrolysis in the presence of acid or alkali of formula IV compound
R wherein
1And R
2Identical with the definition of claim 1 couple formula I, X is hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group, halogen, nitro or cyano group, Y are hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group, halogen or cyano group.
12. formula IV compound
R wherein
1And R
2Identical with the definition of claim 1 couple formula I, X is hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group, halogen, nitro or cyano group, Y are hydrogen, C
1-4Alkyl, C
1-4Alkoxyl group, halogen or cyano group.
13. the method for the formula IV compound of preparation claim 12 is carried out acetalation comprising the glycol that makes formula V compound and formula VI
R wherein
1, identical to the definition of formula IV in X and Y and the claim 12
R wherein
2With identical in the claim 1 to the definition of formula I.
14. formula V compound
R wherein
1, identical to the definition of formula IV in X and Y and the claim 5.
15. the method for 2-(4-(2-hydroxyethyl) phenyl) dioxolane of preparation claim 10 Chinese style II is comprising the glycol generation acetalation that makes formula VII compound and formula VI
R wherein
1, X is identical with the definition of claim 12 couple formula IV with Y
R wherein
2Identical with the definition of claim 1 couple formula I.
16. formula X compound
R wherein
1And R
2Identical with the definition of claim 1 couple formula I.
17. the method for the formula X compound of preparation claim 16 is comprising the compound hydrolysis that makes formula XI
R wherein
1And R
2Definition cotype I.
18. formula XI compound
R wherein
1And R
2With identical in the claim 1 to the definition of formula I.
19. the method for the formula XI compound of preparation claim 18 is comprising making the reaction of formula II compound and phthalic imidine
R wherein
1And R
2With identical in the claim 1 to the definition of formula I.
20. formula XII compound
R wherein
1And R
2With identical to the definition of formula I in the claim 1, Hal is a halogen, preferred chlorine or bromine.
21. the method for the formula XII compound of preparation claim 20 is comprising the glycol acetalation that makes formula XIII compound and formula VI
R wherein
1With identical in Hal and the claim 20 to the definition of formula XII,
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9424676A GB9424676D0 (en) | 1994-12-07 | 1994-12-07 | Organic compounds |
| GB9424676.6 | 1994-12-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1168671A true CN1168671A (en) | 1997-12-24 |
Family
ID=10765538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95196639 Pending CN1168671A (en) | 1994-12-07 | 1995-12-06 | Novel pyrimidinyloxy- and pyrimidinylamino-ethylphenyl-dioxolane derivatives |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0796259A2 (en) |
| JP (1) | JPH10512236A (en) |
| CN (1) | CN1168671A (en) |
| AU (1) | AU4260296A (en) |
| BR (1) | BR9509877A (en) |
| CA (1) | CA2206306A1 (en) |
| GB (1) | GB9424676D0 (en) |
| MX (1) | MX9703363A (en) |
| WO (1) | WO1996017843A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596968A (en) * | 2009-07-30 | 2012-07-18 | 梅里亚有限公司 | Insecticidal 4-amino-thieno[2,3-d]-pyrimidine compounds and methods of their use |
| CN101084224B (en) * | 2004-10-21 | 2013-12-04 | 美国陶氏益农公司 | Thieno-pyrimidine compounds having fungicidal activity |
| CN104185628A (en) * | 2012-02-01 | 2014-12-03 | 日本农药株式会社 | Arylalkyloxy pyrimidine derivative, pesticide for agricultural and horticultural use containing arylalkyloxy pyrimidine derivative as active ingredient, and use of same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7601725B2 (en) | 2004-07-16 | 2009-10-13 | Sunesis Pharmaceuticals, Inc. | Thienopyrimidines useful as Aurora kinase inhibitors |
| EP2078721B1 (en) * | 2005-10-21 | 2014-01-22 | Dow AgroSciences LLC | Thieno-pyrimidine compounds having fungicidal activity |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU734184A1 (en) * | 1977-11-02 | 1980-05-15 | Белорусский Ордена Трудового Красного Знамени Государственный Университет Им.В.И.Ленина | Method of preparing p-formylstyrene |
| DE69500091T2 (en) * | 1994-02-01 | 1997-05-15 | Ube Industries | 4-phenylamino-pyrimidine derivatives, process for their preparation and pesticides for agriculture and horticulture containing them |
-
1994
- 1994-12-07 GB GB9424676A patent/GB9424676D0/en active Pending
-
1995
- 1995-12-06 CN CN 95196639 patent/CN1168671A/en active Pending
- 1995-12-06 EP EP95941073A patent/EP0796259A2/en not_active Withdrawn
- 1995-12-06 CA CA 2206306 patent/CA2206306A1/en not_active Abandoned
- 1995-12-06 AU AU42602/96A patent/AU4260296A/en not_active Abandoned
- 1995-12-06 JP JP8517320A patent/JPH10512236A/en active Pending
- 1995-12-06 MX MX9703363A patent/MX9703363A/en unknown
- 1995-12-06 WO PCT/EP1995/004795 patent/WO1996017843A2/en not_active Application Discontinuation
- 1995-12-06 BR BR9509877A patent/BR9509877A/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101084224B (en) * | 2004-10-21 | 2013-12-04 | 美国陶氏益农公司 | Thieno-pyrimidine compounds having fungicidal activity |
| CN102596968A (en) * | 2009-07-30 | 2012-07-18 | 梅里亚有限公司 | Insecticidal 4-amino-thieno[2,3-d]-pyrimidine compounds and methods of their use |
| CN102596968B (en) * | 2009-07-30 | 2015-05-06 | 梅里亚有限公司 | Insecticidal 4-amino-thieno[2,3-d]-pyrimidine compounds and methods of their use |
| CN104185628A (en) * | 2012-02-01 | 2014-12-03 | 日本农药株式会社 | Arylalkyloxy pyrimidine derivative, pesticide for agricultural and horticultural use containing arylalkyloxy pyrimidine derivative as active ingredient, and use of same |
| CN104185628B (en) * | 2012-02-01 | 2017-03-08 | 日本农药株式会社 | Alkoxy aryl pyrimidine derivatives, containing alkoxy aryl pyrimidine derivatives as active component agricultural and horticultural pesticide and their purposes |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996017843A3 (en) | 1996-08-22 |
| MX9703363A (en) | 1998-02-28 |
| WO1996017843A2 (en) | 1996-06-13 |
| BR9509877A (en) | 1997-09-30 |
| AU4260296A (en) | 1996-06-26 |
| JPH10512236A (en) | 1998-11-24 |
| GB9424676D0 (en) | 1995-02-01 |
| CA2206306A1 (en) | 1996-06-13 |
| EP0796259A2 (en) | 1997-09-24 |
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