CN1024489C - Method for controlling harmful insects and microbes within plants - Google Patents

Abstract

Compounds of the formula (I) in which: R1 and R2 independently of one another are hydrogen, halogen, C1-C3alkyl, C1-C2haloalkyl, C1-C3alkoxy or C1-C3haloalkoxy; R3 is hydrogen; C1-C4alkyl; or C1-C4alkyl substituted by halogen, hydroxy or by cyano; cyclopropyl; or cyclopropyl mono- to tri-substituted by methyl and/or by halogen; and R4 is C3-C6cycloalkyl or C3-C6cycloalkyl mono-to tri-substituted by methyl and/or by halogen, have valuable microbicidal and insecticidal properties. The novel active ingredients can be used in plant protection for preventing an attack on cultivated plants by phytopathogenic microorganisms or by harmful insects, and for controlling these pests.

Description

Method for controlling harmful insects and microbes within plants

The invention relates to new 2-anilino-pyrimidine derivative, shown in following formula I.The invention still further relates to the method for making of this compounds and at least a this compounds composition pesticide as effective ingredient.The present invention also relates to the method for making of above-mentioned composition and above-mentioned effective ingredient composition at pest control (especially harmful insect) and to the purposes aspect the plant detrimental microorganisms (especially fungi).

The general formula of The compounds of this invention is as follows:

（Ⅰ）

In the formula:

R ₁, R ₂Represent hydrogen, halogen, C independently of one another ₁-C ₃Alkyl, C ₁-C ₂Haloalkyl, C ₁-C ₃Alkoxyl or C ₁-C ₃Halogenated alkoxy;

R ₃Represent hydrogen; C ₁-C ₄Alkyl; Or by the C of halogen, hydroxyl and/or cyano group replacement ₁-C ₄Alkyl; Cyclopropyl or by methyl and/or halogen one to trisubstituted cyclopropyl;

R ₄Represent C ₃-C ₆Cycloalkyl or by methyl and/or halogen one to trisubstituted C ₃-C ₆Cycloalkyl; Also comprise salt and metal salt complex with sour form.

Alkyl itself or as the another kind of group alkyl of a part of haloalkyl, alkoxyl or halogenated alkoxy for example, the carbon number that is provided more than it and deciding, be interpreted as for example methyl, ethyl, propyl group, butyl and isomer thereof, as isopropyl, isobutyl group, the tert-butyl group or sec-butyl.Halogen (also being expressed as the Ha I) is fluorine, chlorine, bromine or iodine.Haloalkyl or halogenated alkoxy are groups to many halos, as CHCl ₂, CH ₂F, CCl ₃, CH ₂Cl, CHF ₂, CF ₃, CH ₂CH ₂Br, C ₂Cl ₅, CH ₂Br, CHBrCl etc., preferably CF ₃Cycloalkyl is looked its above-mentioned carbon number and usual practice cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl in this way.

The N-pyrimidine aniline is a known compound at compound.For example, at disclosed european patent application 0224339 and at the GDR(German Democratic Republic) in the patent specification 151404, all can prevent and treat content effectively to the harmful fungi of plant relevant for having N-2-pyrimidine radicals structural compounds.Yet in actual applications, these known compounds all can not meet the demands so far fully.Feature difference between formula I compound of the present invention and the known compound is, The compounds of this invention is to have introduced at least one cycloalkyl and other substituting group in the anilino-pyrimidine structure, the noval chemical compound that has consequently obtained having high bactericidal activity and insecticidal action unexpectedly.

Formula I compound is oily, resin-like or solid, shaped, and is stable under the room temperature, has very valuable microbicidel character.They can be preventative or control and be applied to relevant place, farming zone reasoningly, with control to the plant detrimental microorganisms.The characteristics of formula I compound of the present invention are not only under low working concentration good desinsection and fungicidal action are arranged, and plant to have extra high tolerance to them.

The compounds of this invention had both comprised the free cpds of formula I, comprised that also itself and salt inorganic or that organic acid forms reach the complex compound that forms with slaine.

The salt that the said salt of the present invention especially forms with suitable inorganic or organic acid.Inorganic acid for example has: halogen acids, example hydrochloric acid, hydrobromic acid or hydroiodic acid; Sulfuric acid; Phosphoric acid; Phosphorous acid; Nitric acid.Organic acid for example has: acetate, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, methanesulfonic acid, salicylic acid, Para-amino-salicylic acid, 2-phenoxy benzoic acid, 2-acetoxy-benzoic acid or 1,2-naphthalenedisulfonic acid.

The metal salt complex of formula I is by constituting as the organic molecule of complex compound main body and inorganic or organic metal salt.This class salt for example have more following elements halide, nitrate, sulphate, phosphate, acetate, trifluoroacetate, trichloroacetate, propionate, tartrate, sulfonate, salicylate, benzoate etc.These yuan have: second major element, as calcium and magnesium; Third and fourth major element is as aluminium, tin and lead; And first to the 8th subgroup element, as chromium, manganese, iron, cobalt nickel, copper, zinc etc.The subgroup element of preferred period 4.These metals can different valence state exist.Metal complex can be monokaryon or polynuclear complex, that is to say, they can contain one or more organic molecules and make ligand.

R ₁, R ₂The formula I compound that is hydrogen constitutes one group of important plant epiphyte agent and insecticide extremely.

Following formula I compound constitutes one group of concrete plant epiphyte agent and insecticide extremely, in these formula I compounds:

R ₁, R ₂Name is represented hydrogen, halogen, C independently ₁-C ₃Alkyl, C ₁-C ₂Haloalkyl, C ₁-C ₃Alkoxyl or C ₁-C ₃Halogenated alkoxy;

R ₃Represent hydrogen, C ₁-C ₄Alkyl or the C that replaces by halogen or cyano group ₁-C ₄Alkyl;

R ₄Be C ₃-C ₆Cycloalkyl or the C that replaces by methyl or halogen ₃-C ₆Cycloalkyl.

Respectively organize active ingredient below preferred,, be worth the thing fungi activity especially extremely because they have outstanding microbicidel:

The 1a group: following formula I compound, wherein:

R ₁, R ₂Each represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, halogenated methyl, methoxyl group, ethyoxyl or halogenated methoxy independently;

R ₃Represent hydrogen, methyl is by methyl, the ethyl of fluorine, chlorine, bromine or cyano group replacement, by the ethyl that fluorine, chlorine, bromine or cyano group replace, n-pro-pyl or sec-butyl;

R ₄Represent C ₃-C ₆Cycloalkyl or the C that replaces by methyl, fluorine, chlorine or bromine ₃-C ₆Cycloalkyl.

In the above-claimed cpd, R ₁=R ₂The compound of=hydrogen constitutes particularly preferred one group, i.e. the 1aa group.

The 1b group: following formula I compound, wherein:

R ₁, R ₂Each represents hydrogen, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxyl group, ethyoxyl or difluoro-methoxy independently;

R ₃Be hydrogen, methyl is by the methyl that fluorine, chlorine or cyano group replace, ethyl or n-pro-pyl;

R ₄Be C ₃-C ₅Cycloalkyl or the C that replaces by methyl or chlorine ₃-C ₅Cycloalkyl.

In the above-claimed cpd, R ₁=R ₂The compound of=hydrogen constitutes particularly preferred one group, i.e. the 1bb group.

The 1c group: following formula I compound, wherein:

R ₁, R ₂Each represents hydrogen, chlorine, methyl, methoxyl group, ethyoxyl or trifluoromethyl independently

R ₃Be hydrogen, methyl, ethyl or trifluoromethyl;

R ₄Be cyclopropyl or the cyclopropyl that replaces by methyl or chlorine.

In the above-claimed cpd, R ₁=R ₂The compound of=hydrogen constitutes particularly preferred one group, i.e. the 1cc group.

The 1d group: formula I compound, wherein:

R ₁Be hydrogen;

R ₂, R ₃Each represents hydrogen or methyl independently;

R ₄For cyclopropyl or by methyl substituted cyclopropyl.

The 2a group: formula I compound, wherein:

R ₁, R ₂Each represents hydrogen, halogen, C independently ₁-C ₂Alkyl, halogenated methyl, C ₁-C ₂Alkoxyl or C ₁-C ₂Halogenated alkoxy;

R ₃Be hydrogen; C ₁-C ₄Alkyl; C by halogen or hydroxyl replacement ₁-C ₂Alkyl; Cyclopropyl; Or by methyl and/or halogen one to trisubstituted cyclopropyl;

R ₄Be C ₃-C ₆Cycloalkyl or by methyl and/or halogen one to trisubstituted C ₃-C ₄Cycloalkyl.

In the above-claimed cpd, R ₁=R ₂The compound of=hydrogen constitutes particularly preferred one group, i.e. the 2aa group.

The 2b group: formula I compound, wherein:

R ₁, R ₂Each represents hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxyl group or difluoro-methoxy independently;

R ₃Be hydrogen, C ₁-C ₃Alkyl is by the C of halogen or hydroxyl replacement ₁-C ₂Alkyl; Cyclopropyl; Or by methyl and/or halogen one to trisubstituted cyclopropyl;

R ₄Be C ₃-C ₆Cycloalkyl or by methyl and/or halogen one to trisubstituted C ₃-C ₄Cycloalkyl.

In the above-claimed cpd, R ₁=R ₂The compound of=hydrogen constitutes particularly preferred one group, i.e. the 2bb group.

The 2c group: following formula I compound, wherein:

R ₁, R ₂Each represents hydrogen, fluorine, chlorine, methyl, trifluoromethyl, methoxyl group or difluoromethyl independently;

R ₃Be hydrogen, C ₁-C ₃Alkyl is by the C of halogen or hydroxyl replacement ₁-C ₂Alkyl; Cyclopropyl; Or by methyl and/or halogen one to trisubstituted cyclopropyl;

R ₄Be C ₃-C ₆Cycloalkyl or by methyl and/or halogen one to trisubstituted C ₃-C ₄Cycloalkyl.

In the above-claimed cpd, R ₁=R ₂The compound of=hydrogen constitutes particularly preferred one group, i.e. the 2cc group.

The 2d group: formula I compound, wherein:

R ₁, R ₂Be hydrogen;

R ₃Be C ₁-C ₃Alkyl; Methyl by fluorine, chlorine, bromine or hydroxyl replacement; Cyclopropyl; Or the cyclopropyl that replaces by methyl, fluorine, chlorine or bromine;

R ₄Be C ₃-C ₄Cycloalkyl or by methyl and/or fluorine, chlorine or bromine one to trisubstituted C ₃-C ₄Cycloalkyl.

In particularly preferred individualized compound, can enumerate the following, for example:

2-phenylamino-4-methyl-6-cyclopropyl pyrimidine (No. 1.1 compounds)

2-phenylamino-4-ethyl-6-cyclopropyl pyrimidine (No. 1.6 compounds)

2-phenylamino-4-methyl-6-(2-methyl-propyl) pyrimidine (No. 1.14 compounds)

2-phenylamino-4.6 pair (cyclopropyl) pyrimidine (No. 1.236 compounds)

2-phenylamino-4-methylol-6-cyclopropyl pyrimidine (No. 1.48 compounds)

2-phenylamino-4-methyl fluoride-6-cyclopropyl pyrimidine (No. 1.59 compounds)

2-phenylamino-4-methylol-6-(2-methyl cyclopropyl) pyrimidine (No. 1.13 compounds)

2-phenylamino-4-methyl-6-(2-fluorine cyclopropyl) pyrimidine (No. 1.66 compounds)

2-phenylamino-4-methyl-6-(2-chlorine cyclopropyl) pyrimidine (No. 1.69 compounds)

2-phenylamino-4-methyl-6-(2-difluoro cyclopropyl) pyrimidine (No. 1.84 compounds)

2-phenylamino-4-methyl fluoride-6-(2-fluorine cyclopropyl) pyrimidine (No. 1.87 compounds)

2-phenylamino-4-methyl fluoride-6-(2-chlorine cyclopropyl) pyrimidine (No. 1.94 compounds)

2-phenylamino-4-methyl fluoride-6-(2-methyl cyclopropyl) pyrimidine (No. 1.108 compounds)

2-phenylamino-4-ethyl-6-(2-methyl cyclopropyl) pyrimidine (No. 1.131 compounds)

2-(is right-fluoroanilino)-4-methyl-6-cyclopropyl pyrimidine (No. 1.33 compounds)

Formula I compound can prepare as follows:

1. make phenyl guanidinesalt or the free guanidine alkali of formula II b and two reactive ketones of formula III of formula II a,

Reaction can not carried out at solvent or in aprotic solvent, is preferably in the proton solvent and carries out; Reaction temperature is 60-160 ℃ preferably 60-110 ℃; Perhaps

2. adopt a kind of multistep method, that is:

2.1 make the urea of formula IV and two reactive ketones of formula III:

Be reflected at acid and exist down, in atent solvent, carry out; Reaction temperature is 20-140 ℃, preferably 20-40 ℃; Cyclization takes place in the reaction and obtain the pyrimidine compound of formula V:

（Ⅴ）

With

2.2. with the OH group displacement in the gained formula V compound is halogen, method is further to make formula V compound and excessive POHHal ₃Reaction; Be reflected at solvent or in solvent, do not carry out.Reaction temperature is 50-110 ℃.Be preferably in POHHal ₃Reflux temperature under carry out; Reaction production VI compound:

（Ⅵ）

In the formula Hal be halogen, especially chlorine or bromine and

2.3 further make the aniline compound reaction of formula VI compound and formula VII:

（Ⅶ）

According to reaction condition, can make reaction

A) at the proton accepting agent, for example excessive formula VII aniline compound or inorganic base exist down, react under the condition of solvent being with or without, or

B) in the presence of acid, in atent solvent, carry out, in the above two kinds of cases, reaction temperature all is 60-120 ℃, preferably 80-100 ℃.Or

3. employing two-step method, that is:

3.1 make the guanidinesalt of formula VIII and the diketone generation cyclization of formula III:

（Ⅷ）

（Ⅲ）

This cyclization carries out under the following conditions:

A) reaction in without solvent, reaction temperature is 100-160 ℃, preferably 120-150 ℃, or

B) be reflected in the atent solvent and carry out, reaction temperature is 30-140 ℃, preferably 60-120 ℃, obtains the pyrimidine compound of formula IX:

（Ⅸ）

3.2 make the reaction of gained formula IX compound and formula (X) compound, HY removed:

（Ⅹ）

Be reflected at the proton accepting agent and exist down, carry out in aprotic solvent, reaction temperature is 30-140 ℃, preferably 60-120 ℃, and formula II substituent R to the formula X ₁-R ₄Definition identical with these substituting groups in the formula I, A ^θBe the anion of acid, Y is a halogen; Or

4. employing multistep processes, that is:

4.1a) diketone that makes the thiocarbamide of formula XI and formula III in the presence of acid, in atent solvent, react:

Reaction temperature is 20-140 ℃, preferably 20-60 ℃; Cyclisation takes place, production XII compound:

（Ⅻ）

Make the alkali metal of formula XII compound or the compound reaction of alkali salt and formula X III:

ZR ₅（ⅩⅢ）

R in the formula X III ₅Be C ₁-C ₈Alkyl, or do not replace or by halogen and/or C ₁-C ₄The benzyl that alkyl replaces, Z is a halogen, obtains formula X IV compound:

（ⅩⅣ）

Or

B) make the isothiuronium salts of formula X V and two reactive ketones of formula III:

（ⅩⅤ）

Reaction is preferably in the proton solvent to be carried out; Reaction temperature is 20-140 ℃, preferably 20-80 ℃; Obtain equally formula X IV pyrimidine compound and

4.2 use oxidant, peroxy acid for example, with gained formula X IV compound oxidation, formula X VI compound:

（ⅩⅥ）

With

4.3 make the formailide reaction of gained formula X VI compound and formula X VII:

（ⅩⅦ）

Be reflected in the atent solvent, in the presence of alkali, carry out as the proton accepting agent; Reaction temperature is-30 ℃-120 ℃, gets formula X VIII compound:

（ⅩⅧ）

With

4.4 with gained formula X VIII compound hydrolysis; Hydrolysis carries out in water or nonelectrolyte mixed aqueous solution in the presence of alkali or acid; Alkali for example has alkali metal hydroxide; Acid for example has hydrogen halogen or sulfuric acid; Hydrolysis temperature is 10-110 ℃, preferably 30-60 ℃; Identical in the definition of the substituent R-R of formula XI in the formula X VIII and the formula I, and A ^θBe the anion of acid, Y is a halogen.

R ₃Be CH ₂The formula I compound of OH group can prepare by following specific process:

A1.1 makes guanidinesalt or the guanidine of formula II b and the reactive ketone of formula X IX of formula II a:

R in the formula X IX ₆Be C ₁-C ₄Alkyl;

Be reflected at proton solvent or in solvent, do not carry out; Reaction temperature is 40-160 ℃, preferably 60-110 ℃; Get formula XX compound

（ⅩⅩ）

With

A1.2 is with gained formula XX compound hydrolysis; Hydrolysis is carried out in water or nonelectrolyte mixed aqueous solution (for example mixed solvent of water and alcohol or dimethyl formamide etc.) in the presence of acid (for example hydrogen halogen or sulfuric acid); Hydrolysis temperature 20-100 ℃, preferably 30-60 ℃; Get formula X XI compound:

（ⅩⅪ）

With,

A1.3 perhaps uses reductant (as sodium borohydride) with its reduction using under the condition of catalyzer with element hydrogen gained formula X XI hydrogenation of compounds, corresponding formula X XII compound:

（ⅩⅫ）;

A2.1 makes guanidinesalt and the guanidine of formula II b and two reactive ketones of formula XX III of formula II a:

（ⅩⅩⅢ）

R in the formula ₇For unsubstituted or by halogen or C ₁-C ₄The benzyl that alkyl replaces; Be reflected in the proton solvent (or solvent-free) and carry out; Reaction temperature is 40-60 ℃, preferably 60-110 ℃; Obtain the pyrimidine compound of formula XX IV

（ⅩⅩⅣ）

With

A2.2 is with the CH in the gained formula XX IV compound ₂OR ₇Group changes CH into by hydrogenation ₂OH; Hydrogenation preferably in aprotic solvent (for example dioxane or oxolane), at 20-90 ℃, is preferably carried out under 50-90 ℃ temperature at solvent, uses for example palladium-charcoal, and preferably Raney nickel is as catalyzer; Or

A3.1 makes guanidinesalt or the guanidine of formula II b and two reactive ketones of formula XX V of formula II a:

（ⅩⅩⅤ），

R in the formula ₈Be C ₁-C ₆Alkyl, C ₃-C ₆Alkenyl or unsubstituted or by halogen or C ₁-C ₄The benzyl that alkyl replaces; Use proton solvent in the reaction or do not use solvent; Reaction temperature is 40-160 ℃, preferably 60-110 ℃; Get the pyrimidine compound of formula XX VI:

（ⅩⅩⅥ）

A3.2 carries out ether to gained formula XX VI compound under the following conditions and dissociates: use halogen acids, hydrobromic acid preferably, or use lewis acid is as aluminum halide (AlCl for example ₃) or halogenation boron (Hal) ₃(BBr for example ₃Or BCl ₃), and use aprotic solvent, for example hydrocarbon or halogenated hydrocarbons, temperature is-80 ℃ to 30 ℃, preferably-70 ℃ to 20 ℃.

R ₃Be CH ₂The formula I compound of Hal can prepare like this: make formula XX II compound and phosphorus Halides or thionyl halide at tertiary amine, for example pyridine or triethylamine exist down, react in atent solvent; Reaction temperature is 0-110 ℃, preferably 0-80 ℃.

R ₃Be CH ₂The formula I compound of F can prepare like this: make formula XX VII compound:

（ⅩⅩⅦ）

X is a chlorine or bromine in the formula, with potassium fluoride, and the preferably potassium fluoride of freeze-drying reaction, the cesium fluoride or the crown ether (for example the 18-hat-6) that are reflected at catalytic amount exist down, and atent solvent on matter for example carries out in the acetonitrile, and reaction temperature is 50-160 ℃, the working pressure still.

Preparation R ₃Be CH ₂The other method of the formula I compound of F is, in aprotic solvent such as carrene, chloroform, oxolane or diox, fluoridizes-N with three, and N-diethylamino sulphur (DAST) carries out fluorination reaction to formula XX II compound; Reaction temperature is 0-100 ℃, preferably 10-50 ℃.

Superincumbent formula X VIII in formula X VII, R ₁, R ₂And R ₄Definition also with the formula I in identical.

In the described in the above method, the acid anion A in formula II a and the formula VIII compound ^θBe preferably for example following acid group: carbonate, bicarbonate radical, nitrate anion, halogen ion, sulfate radical and bisulfate ion.

In above method, the acid anion A in the formula X V compound ^θShould adopt for example following acid group: halogen ion, sulfate radical and bisulfate ion.

In each case, the halogen ion all should be understood fluorine ion, chlorion, bromide ion or iodide ion, preferably bromide ion or chlorion.

Used acid is inorganic acid preferably, for example halogen acids, as hydrofluoric acid, hydrochloric acid or hydrobromic acid, also have sulfuric acid, phosphoric acid or nitric acid; But also can adopt suitable organic acid, for example acetate and toluenesulfonic acid.

Used proton accepting agent for example has inorganic or organic base, and for example alkali metal or alkaline earth metal compounds as hydroxide, oxide or the carbonate of lithium, sodium, potassium, magnesium, calcium, strontium and barium, also have hydride, for example sodium hydride.Organic base has tertiary amine for example, as triethylamine, triethylenediamine, pyridine.

In above-mentioned each method, except that already mentioned solvent, decide on concrete reaction condition, can also use for example following solvent:

Halogenated hydrocarbons, particularly chlorohydrocarbon, as tetrachloro-ethylene, tetrachloroethanes, dichloropropane, carrene, chloroform, chloronaphthalene, carbon tetrachloride, trichloroethanes, trichloro-ethylene, pentachloroethane, two fluorobenzene, 1, the 2-dichloroethane, 1,1-dichloroethane, 1,2-is along (formula) dichloroethylene, chlorobenzene, fluorobenzene, bromobenzene, dichloro-benzenes, dibromobenzene, chlorotoluene, benzotrichloride; Ether is as second (base) third (base) ether, methyl tertiary butyl ether, normal-butyl ether, di-n-butyl ether, diisobutyl ether, isoamyl ether, diisopropyl ether, methyl phenyl ethers anisole, cyclohexyl methyl ether, ether, glycol dimethyl ether, oxolane ， diox, THIOANISOLE, dichlorodiethyl ether; Nitro hydrocarbon, as nitromethane, nitroethane, nitrobenzene, chloronitrobenzene, ortho-methylnitrobenzene; Nitrile, as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile, m-chloro benzonitrile; Aliphatic or clicyclic hydrocarbon, as heptane, hexane, octane, nonane, decane, the petroleum cuts that boiling range is 70 ℃～190 ℃, cyclohexane, hexahydrotoluene, naphthalane, benzinum, ligroin, trimethylpentane, as 2,3, the 3-trimethylpentane; Ester, as ethyl acetate, ethyl acetoacetate, isobutyl acetate; Acid amides, as formamide, methylformamide, dimethyl formamide; Ketone, as acetone, MEK, alcohol, particularly lower aliphatic alcohols, as methyl alcohol, ethanol, normal propyl alcohol, the isomer of isopropyl alcohol and butanols; Also available water under suitable situation also can adopt the mixture of above-mentioned solvent and thinner.

The synthetic method that is similar to above-mentioned preparation process is disclosed in the document.

Can reference have:

Method 1:A.Kreutzberger and J.Gillessen, and " heterocyclic chemistry magazine " (J.Hererocyclic Chem.22,101(1985).

Method 2: step 2.1:O.Stark, Ber.Dtsch.Chem.Gs.42,699(1909); J.Hale, J.Am.Chem.Soc.36,104(1914);

G.M.Kosolapoff，J.Org.Chem.26，1895（1961）。Step 2.2:St, Angerstein, Ber.Dtsch.Chem.Ges.34,3956(1901);

G.M.Kosolapoff，J.Org.Chem.26，1895（1961）。

Step 2.3:M.P.V.Boarland and J.F.W.Mcomie, J.Chem.Soc, 1951,1218; T.Matsukawa and K.Shirakuwa, J.Pharm.Soc.Japan71,933(1951); " chemical abstracts " 46,4549(1952).

Method 3:A.Combes and C.Combes, Bull.Soc.Chem.(3), 7,791(1892); W.J.Hale and F.C.Vibrans, J.Am, Chem.Soc.40,1046(1918).

Described preparation method comprises all individual steps, is partial content of the present invention.

The following midbody compound that is used for preparation is novel, and it is a part of the present invention:

1) has the compound of following formula

R wherein ₀Be halogen or R ₃SO ₂; R ₃Be hydrogen; C ₁～C ₄Alkyl; Or by halogen, the C that hydroxyl and/or cyano group replace ₁～C ₄Alkyl; Cyclopropyl; Or by methyl and/or halogen one to trisubstituted cyclopropyl; R ₄Be C ₃～C ₆Cycloalkyl or by methyl and/or halogen one to trisubstituted C ₃～C ₆Cycloalkyl; R ₅Be C ₁～C ₈Alkyl or by halogen and/or C ₁～C ₄Alkyl replaces the benzyl of (or not replacing).Halogenic substituent R ₀It is good getting chlorine or bromine.

2) formula X XI compound:

（ⅩⅪ）

R in the formula ₁And R ₂Represent hydrogen independently of one another, halogen, C ₁～C ₃Alkyl, C ₁～C ₂Haloalkyl, C ₁～C ₃Alkoxyl or C ₁～C ₃Halogenated alkoxy; R ₄Be C ₃～C ₆Cycloalkyl or the C that replaces by 1 to 3 methyl and/or halogen ₃～C ₆Cycloalkyl.

Wonderful discovery is a formula I compound when using in the field, to insect with cause phytopathy microorganism (particularly fungi) and have good Biocidal spectrum.Formula I compound has good improvement and prevention performance, and particularly interior absorption can be used for protecting multiple cultivated plant.Use formula I compound can suppress or eliminate in the plant of multiple different useful plant crops or plant part (fruit, flower; leaf, stem, stem tuber; root) the middle insect that occurs, and this part plant also is protected when growing afterwards, for example prevents to cause the infringement of phytopathy microorganism.

For example, formula I compound is effective to the phytopathogenic fungi that belongs to following class; Fungi Imperfecti (particularly grape spore, and Helminthosporium, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (for example Rhizoctonia, hunchbacked spore Rust, Puccinia).Formula I compound also is effective to Ascomycetes class bacterium (as Venturia and Erysiphe, Podosphaera, chain sclerotinia sclerotiorum genus, Uncinula) and Oomycete class bacterium (as ramie mould, pythium, Plasmopara).Formula I compound also can be used to protect seed (fruit; stem tuber, grain) and plant transplant and avoid occurring in the fungal infection in the soil and the infringement of phytopathogenic fungi, in addition; formula I compound also is effectively to insect pest, for example to the insect of cereal (as rice).

The present invention also relates to the composition, particularly plant protection composition of formula I compound as active ingredient, and the application in agricultural or association area.

The present invention also comprises the preparation method of above-mentioned composition, and this method comprises evenly mixes above-mentioned active component with one or more compounds as herein described or one or more groups compound.The invention still further relates to the method for administering plant pest, this method comprises to plant uses new-type I compound or new compositions.

The plant that within the scope of the present invention can protected target crop comprises following kind: cereal (wheat, barley, naked barley, rice, oat; corn, jowar etc.), beet (sugaring garden beet, fodder beet), the operatic circle; drupe and mushy fruit (apple, pears, plum, peach, almond; cherry, strawberry, rasp berry and blackberry, blueberry), leguminous plant (Kidney bean, lentil; pea, soybean), oil crop (rape, mustard, opium poppy; olive, sunflower, coconut, castor oil plant, cocoa bean; peanut), melon (cucumber, cucurbitaceae vegetable, muskmelon), fibre plant (cotton; flax, hemp, jute), citrus fruit (orange, lemon; grape, oranges and tangerines), vegetables (spinach, lettuce, asparagus; cabbage, Hu Luobu, onion, tomato; potato, red pepper), camphor tree class (avocado, cinnamon; camphor tree), or other plant, as tobacco, nut; coffee, sugarcane, tea, pepper; liane, hop, banana, natural rubber plant and ornamental plants.

Formula I compound generally uses with the form of composition.Can impose on during use on pending crop surface or the plant, can simultaneously or use other active substance in succession.This class active substance can be a fertilizer, and micro-donor or other can influence the preparation of plant growing, also can be selective weedkiller, insecticide, fungicide, bactericide, nematocide, the mixture of invertebrate poison or these several preparations.When needing, also can use carrier commonly used in the preparation technique together, surfactant, or use the promotion auxiliary agent.

Suitable carriers and auxiliary agent can be solid or liquid, can adopt in the preparation technique material commonly used, inorganic substances, solvent, dispersant, wetting agent, tackifier, thickener, adhesive or the fertilizer of for example natural or regeneration.

When using formula I compound or containing a kind of agriculturally useful compositions of this compound at least, a kind of method preferably is to use on the leaf.Application times and amount of application depend on by the degree of pathogenic infection.If yet with the location of liquid preparation dipping plant, or this compound is applied in (soil application method) in the soil with solid form (as granule), and formula I compound also can enter plant (systemic action) by root by soil.For rice crop, the granule that measured can be applied in the rice field of water-filling.Also can use (coating) formula I compound to seed, method is to give seed coating with the liquid preparation dipping seed that contains formula I compound or with solid pharmaceutical preparation.

Formula I compound can use with the form of not modification, but the auxiliary agent of preferably using always in formulation art uses; Under latter event, preferably make preparation by known method, for example make emulsifiable concentrate, can apply paste, can directly spray or dilutable solution, dilute emulsion, wettable powder, soluble powder, pulvis and granula also can be with wrapping capsule as polymer etc.According to using purpose and prevailing circumstances, select the composition of application process (as spraying, atomize, dust formation is sowed, coating or pouring) and appropriate format.Favourable amount of application is generally 50g～50kg active ingredient (brief note is a.i.)/hectare, is preferably 100g～2kg a.i./hectare, more preferably 200g～600ga.i./hectare.

Prepare preparation by known method, promptly contain composition, ingredients or the mixture of formula I compound (active ingredient) and (if required) solid or liquid assistant agent.For example, active ingredient and replenishers (as solvent, solid carrier can be surface active cpd, i.e. surfactant when needing) are evenly mixed and/or grind.

Suitable solvent has aromatic hydrocarbons, and it is better to contain 8～12 carbon atoms, as xylene mixture or substituted naphthalene, or benzoic ether (as dibatyl phithalate or dioctyl ester); Aliphatic hydrocarbon is as cyclohexane or alkane, alcohol, glycol or their ether and ester, as ethanol, ethylene glycol, glycol monomethyl first or single ether, ketone, as cyclohexanone, intensive polar solvent, as the N-N-methyl-2-2-pyrrolidone N-, methyl-sulfoxide or dimethyl formamide, and vegetable oil or epoxidized vegetable oil are as epoxidation cocoa butter or soybean oil; Or water.

Be used for pulvis for example and solid carrier that can the branch divided powder and be generally the natural inorganic filler, as calcite, talcum, kaolin, imvite or aluminium iron silicate carrier.In order to improve physical property, also can add the silicic acid of high degree of dispersion or the absorbent polymer of high degree of dispersion.Suitable granular absorption carrier is a porous type, as float stone, and brickbat, sepiolite or bentonite; The example of suitable non-adsorptive support has calcite or sand.In addition, can use a variety of inorganic in nature arranged make granular material in advance, particularly as dolomite or the residual body of comminuted plants.

Can significantly reduce particularly advantageous natural (animal or vegetables) or the synthetic phospholipid that promotes auxiliary agent to also have cephalin and lecithin series of using of amount of application, they for example can obtain from soybean.

According to the character of formula I compound to be prepared, suitable surface active cpd is to have well emulsify, the nonionic of dispersion and wettability, cationic and/or anionic surfactant.The meaning of " surfactant " speech also comprises surfactant mixtures.

So-called water-soluble soap class and water-soluble synthetic surface reactive compound are suitable anion surfactants.

Suitable soap class comprises higher fatty acid (C ₁₀～C ₂₂) the ammonium salt of alkali metal salt, alkali salt or replacement (or not replace), for example oleic acid or stearic sodium salt or sylvite, the sodium salt or the sylvite of natural acid mixture (for example can obtain), and fatty acid methyl bay refined salt from cocoa butter or fatty oil.

More usually so-called synthetic surfactant, particularly paraffin sulfonate, aliphatic alcohol sulfate, the benzimidizole derivatives of sulfonation or alkylsulfonate.

Fatty alcohol sulfonate or sulphate are alkali metal salt usually, the ammonium salts of alkali salt or replacement (or not being substituted), and contain include acyl group moieties at interior C ₈～C ₂₂Alkyl, lignosulphonic acid for example, the sodium salt or the calcium salt of lauryl sulfate or the fatty alcohol sulphuric acid salt mixture that from natural acid, obtains.These compounds also comprise the salt of adduct of the fatty alcohol/ethylene oxide of sulphation and sulfonation.Sulphonated benzimidazole derivative better contains the fatty acid radical of 2 sulfonate radicals and 8 to 22 carbon atoms.The example of alkylaryl sulfonates has DBSA, the sodium salt of dibutyl naphthalene sulfonic acids or naphthalene sulfonic acids and formaldehyde condensation products, calcium salt or triethanolamine salt.

Suitable phosphate also has, for example to the salt of the phosphate of nonyl phenol and 4 to 14 mole ethylene oxide adducts.

Nonionic surface active agent better is fat or alicyclic ring alcohol, or polyglycol ether derivative saturated or unsaturated fatty acid and alkylphenol.This derivative contains 3 to 30 ethylene glycol ethers, and aliphatic hydrocarbon moiety contains 8 to 20 carbon atoms, and the moieties of alkyl phenol contains 6 to 18 carbon atoms.

Suitable nonionic surface active agent also has PEO and polypropylene glycol, amino polypropylene glycol of ethylene and alkyl chain length are the water-soluble addition thing of the alkyl polypropylene glycol of 1 to 10 carbon atom, and this adduct contains 20～250 ethylene glycol ethers and 10～100 propane diols ethers.Usually each propane diols unit contains 1～5 ethylene glycol unit in these compounds.

Representational examples of nonionic surfactants is the nonyl phenol polyethoxy ethanol, the castor oil polyglycol ether, and poly(propylene oxide)/PEO adduct, the tributyl phenoxy group gathers ethylidene ethanol, polyethylene glycol and octylphenoxy polyethoxy ethanol.

The fatty acid ester of polyoxy ethylidene anhydro sorbitol also is suitable nonionic surface active agent as polyoxy ethylidene sorbitan trioleate.

Cationic surface active agent better is a quaternary ammonium salt, and wherein at least one N-substituting group is C ₈～C ₂₂Alkyl, other substituting group are unsubstituted or the low alkyl group of halo, the low alkyl group of benzyl or hydroxyl.Salt is halide preferably, and Methylsulfate or sulfovinate are as octadecyl trimethyl ammonium chloride or bromination benzyl two (2-chloroethyl) ammonium.

Other surfactant that is usually used in the formulation art is known to those skilled in the art, can learn from relevant technical literature.

Agrochemical compositions generally contains 0.1～99%, is preferably 0.1～95% formula I compound, contains 99.9～1%, is preferably 99.9～5% solid or liquid adjuvants, and 0～25%, be preferably 0.1～25% surfactant.

Commercial product better are to be mixed with concentrate, and the user then generally uses the preparation of dilution

Said composition also can contain other assistant agent, as stabilizing agent, and defoamer, viscosity modifier, adhesive, tackifier, fertilizer or other have the active component of special role.

Following example will illustrate in greater detail (but not being to limit) the present invention

1. preparation embodiment

The preparation of embodiment 1.1:2-anilino--4-methyl-6-cyclopropyl pyrimidine (No. 1.1 compounds)

[No. 1.1 compound]

With the 10g[51mmol(mM)] bicarbonate guanidines and 9.7g(77mmol) 1-cyclopropyl-1, the 3-diacetyl was 110 ℃ of following heated and stirred 6 hours, and along with the carrying out of reaction, the effusion of carbonic acid gas reduces, after the dark-brown emulsion is cooled to room temperature, add the 50ml diethyl ether.Wash mixture twice with water, each 20ml through dried over sodium sulfate, filters and steams solvent.The dark-brown oil (13.1g) that obtains is through silica gel column chromatography (diethyl ether/toluene: 5/3) purifying.After steaming mixture of eluents, contain this brown oil under 30 ℃～50 ℃ from ether/benzinum crystallization and recrystallization, obtain the light brown crystallization.Fusing point: 67～69 ℃, output: 8.55g(38mmol) (theoretical yield 74.5%).

The preparation of embodiment 1.2:2-anilino--4-diethoxymethyl-6-cyclopropyl pyrimidine

With 11.7g[59.2mmol) bicarbonate guanidines and 13.3g(62.2mmol) 1-cyclopropyl-3-formyl diethyl acetal-1, the 3-propanedione is in 40ml methyl alcohol and under agitation added hot reflux 5 hours, and along with the carrying out of reaction, the carbonic acid gas emission reduces.Cooling dark-brown emulsion adds the 80ml ether, and washes the mixture secondary with water to room temperature, and each 30ml filters and steam solvent after dried over sodium sulfate.By silica gel column chromatography (toluene/ethyl acetate: 5/2) the dark-brown oil (17g) that obtains of purifying, steam mixture of eluents, obtain erythroid palm fibre oil, refractive index n ²⁵ _D: 1.5815, output: 15g(48mmol; Theoretical yield 81.1%).

The preparation of embodiment 1.3:2-anilino--4-formyl-6-cyclopropyl pyrimidine (No. 2.1 compounds)

With 12.3g(39.3mmol) 2-anilino--4-formyl diethyl acetal-6-cyclopropyl pyrimidine, 4g(39.3mmol) concentrated hydrochloric acid and 75ml water are strong agitation and 50 ℃ of following heating 14 hours.Add 2g(19.6mmol) behind the concentrated hydrochloric acid, continuous stirring 24 hours again under this temperature.Cool off cream-coloured suspension and to room temperature, add 50ml ethyl acetate, make mixture be neutral with the 7ml30% sodium hydroxide solution.Tell ethyl acetate solution then,, filter, steam solvent, in the presence of active carbon, make above-mentioned light brown solid from the 20ml isopropyl alcohol, be recrystallized, make its purifying, obtain pale yellow crystals and in the time of 112～114 ℃, melt through dried over sodium sulfate.Output 7.9g(33mmol; Theoretical yield 84%).

The preparation of embodiment 1.4:2-anilino--4-methylol-6-cyclopropyl pyrimidine (No. 1.48 compounds)

A) with 2.3g(60mmol) boric acid hydrogen sodium is in room temperature with under stirring, in 15 minutes by batch joining the 14.1g(59mmol that is present in the 350ml absolute methanol) in 2-anilino--4-formyl-6-cyclopropyl pyrimidine.Reactant mixture is heated to 28 ℃, has hydrogen to overflow.Drip the 10ml concentrated hydrochloric acid after 4 hours and make the mixture acidifying, drip the sodium bicarbonate solution of 120ml10% again, use 250ml water diluted mixture thing then, filter the sediment of generation, be dried, and make its major part be dissolved in the 600ml ether at elevated temperatures.With filtering after the charcoal treatment, concentrate clear filtrate to muddy, with the benzinum dilution, and leach light yellow brilliant end; Fusing point: 123～125 ℃, output: 10.8g(44.8mmol, theoretical yield 75.9%).

B) with 5.9g(23mmol) 2-anilino--4-methoxy-6-cyclopropyl pyrimidine (by benzene guanidine and 1-cyclopropyl-4-methoxyl group-1,3-diacetyl preparation) is dissolved in the 200ml carrene, and cooling solution is to-68 ℃.In half an hour and under the strong agitation, in orange-red solution, slowly drip 6.8g(27mmol) Boron tribromide.After removing cooling bath, continue at room temperature to stir 2 hours.Add the 150g frozen water, leach the crude product of precipitation, from methyl alcohol, be recrystallized with active carbon.The pale yellow crystals that obtains is at 124～126 ℃ of fusings, output 4.7g(19.5mmol; Theoretical yield 84.7%).

The preparation of embodiment 1.5:2-phenyl amido-4-bromomethyl-6-cyclopropyl pyrimidine (No. 1.4 compounds)

Under agitation, in half an hour, will be present in the 15.6g(75mmol in the 50ml ether) thionyl bromide is added drop-wise to the 12g(50mmol that is present in the 350ml diethyl ether) 2-anilino--4-methylol-6-cyclopropyl pyrimidine and 0.4g(50mmol) in the pyrimidine.Stir after 2 hours under the room temperature, add 0.4g(50mmol again) pyrimidine.With mixture heating 5 hours under refluxing, be cooled to room temperature after, add 20ml water, regulate pH value to 7 by dripping the 140ml saturated sodium bicarbonate solution.Isolate the ether phase, wash twice then with water, each 100ml.Through dried over sodium sulfate, filter, steam solvent, the brown oil that obtains is through silica gel chromatograph [toluene/chloroform/ether/benzinum (boiling point: 50～70 ℃): 5/3/1/1] purifying.Steam mixture of eluents, with ether/benzinum (boiling point: 50～70 ℃) dilution yellow oil, and crystallization at low temperatures, yellow crystalline flour is 77.5～79.5 ℃ of fusings.Output 9.7g(32mmol, theoretical yield 64%).

The preparation of embodiment 1.6 2-phenyl amino-4-methyl fluoride-6-cyclopropyl pyrimidine

(compound number 1.59)

A) 2-phenyl amino-4-bromomethyl-6-cyclopropyl pyrimidine, 1.5g(26mmol) spray-dired potassium fluoride and 0.3g(1.13mmol 3.9g(12.8mmol)) 18-hat-6-ether refluxes in the 50ml acetonitrile and heated 40 hours.Add 0.75g(13mmol again) behind the potassium fluoride, heated this mixture again 22 hours.After reaction is finished, add 0.75g(13mmol again) spray-dired potassium fluoride and 0.1g(0.38mmol) 18-hat-6-ether and reflux to heat this mixture again 24 hours.Suspension adds the 150ml ether after being chilled to room temperature, and with this mixture of current 3 times, each 20ml, dried over sodium sulfate is filtered, and then, steams solvent.The brown oil that stays is through silica gel column chromatography purification [toluene/chloroform/ether/benzinum (b.p.50-70 ℃) 5/3/1/1].Steam the solvent that removes in the elution mixture, with 10ml benzinum (b.p.50-70 ℃) dilution gained yellow oil and crystallization at low temperatures.The yellow crystal fusing point is 48-52 ℃, and output is 21g(8.6mmol), 67.5% of theoretical yield.

B) under agitation in 1 hour, slowly drip 6.1g(37.8mmol) diethylaminosulfur trifluoride is dissolved in solution in the 15ml carrene to 9.1g(37.8mmol) in the suspension of 2-phenyl amino-4-methylol-6-cyclopropyl pyrimidine and 80ml carrene.The sodium bicarbonate aqueous solution of Dropwise 5 0ml10% after adding the 50ml frozen water.When carbonic acid gas stops to emit, tell organic facies and extract water twice, each 20ml with carrene.Combined dichloromethane solution, with the 15ml washing, dried over sodium sulfate is filtered, and steams then to desolventize.The dark oil thing that stays is through silica gel column chromatography purification [toluene/chloroform/ether/benzinum (b.p.50-70 ℃) 5/3/1/1].After this elution mixture is desolventized by steaming, with 20ml benzinum (b.p.50-70 ℃) dilution gained yellow oil, decrease temperature crystalline.Faint yellow crystalline melt point is 50-52 ℃, output 4.9g(20.1mmol), 53% of theoretical yield.

The preparation of embodiment 1.7 2-hydroxy-4-methyl-6-cyclopropyl pyrimidine

Under room temperature, the 15ml concentrated hydrochloric acid is added to 6g(100mmol) urea and 12.6g(100mmol) 1-cyclopropyl-1, in the solution of 3-diacetyl and 35ml ethanol.This mixture is no more than under 45 ℃ concentrated in rotary evaporation in the bath temperature after placing 10 days under the room temperature.Residue is dissolved in the 20ml ethanol, moments later is settled out the hydrochloride of product.Under agitation add the 20ml ether, leach the white crystals that is settled out, with ethanol/ether mixture washing, drying.Concentrated filtrate also is recrystallized a part of hydrochloride of getting back from ethanol/ether mixture (1/2).This white crystals fusing point＞230 ℃, the output of hydrochloride is 12.6g(67.5mmol, theoretical yield 67.5%)

The preparation of embodiment 1.8 2-chloro-4-methyl-6-cyclopropyl pyrimidines

(compound number 3.1)

Under stirring at room, with 52.8g(0.24mmol) 2-hydroxyl 4-methyl-6-cyclopropyl pyrimidine hydrochloride adds 100ml(1.1mol) phosphorous oxychloride and 117g(0.79mol) in the mixture of diethylaniline, then, be warming up to 63 ℃.In 110 ℃ of following these mixtures of heating after 2 hours, be cooled to room temperature and shift in frozen water/dichloromethane mixture in stirring down.Tell organic facies and be washed till neutrality with saturated sodium bicarbonate aqueous solution.Steaming desolventizes and obtains 116.4g grease, and this grease is made up of product and diethylaniline.With silica gel column chromatography (hexane/ethyl acetate: 3/1) tell diethylaniline and purification reaction product.The refraction index n of colorless oil ²⁵ _DBe 1.5419, become crystallization, output 35.7g(0.21mol after a couple of days; For theoretical yield 87.5%), fusing point is 33-34 ℃.

Between embodiment 1.9 2-(-fluorophenyl amino)-preparation of 4-methyl-6-cyclopropyl pyrimidine

(compound number 1.63)

5.5g(50mmol) 3-fluoroaniline and 9.3g(55mmol) the 2-chloro-4-methyl-solution of 6-cyclopropyl pyrimidine in 100ml ethanol, under agitation regulating pH with the 5ml concentrated hydrochloric acid is 1.Then, the backflow heating is 18 hours.After brown emulsion is cooled to room temperature with this, make it be alkalescence with 10ml30% ammoniacal liquor, be poured into and also use extracted by ether twice, each 150ml in the 100ml ice-water.Merge extract, use the 50ml water washing, dried over sodium sulfate is filtered, and steaming desolventizes.The faint yellow crystallization of gained with diisopropyl ether/benzinum (b.p.50-70 ℃) recrystallization purifying it, obtain white crystals, fusing point 87-89 ℃, output 8.3g(34mmol, for theoretical yield 68%).

Following formula I compound can prepare with this method or above-mentioned a certain method.(table is seen the literary composition back)

But c 2.1 a) b of emulsifying concentrated solution))

Table 1 compound 25% 40% 50%

Calcium dodecyl benzene sulfonate 5% 8% 6%

The castor oil polyglycol ether

(36mol oxirane) 5%--

The tributyl phenol polyglycol ether

(30mole oxirane)-12% 4%

Cyclohexanone-15% 20%

Xylene mixture 65% 25 20

This concentrate of dilute with water can obtain the emulsion of any desired concn.

2.2 solution is b a)) c) d)

Table 1 compound 80% 10% 5% 95%

Glycol monoethyl ether 20%---

Polyethylene glycol (molecular weight 400)-70%--

N-N-methyl-2-2-pyrrolidone N--20--

Epoxidation cocoa butter--1% 5%

Petroleum distillate (boiling range--94%-

160-190℃）

These solution are suitable for using with the droplet form.

2.3 granule is b a))

Table 1 compound 5% 10%

Kaolin 94%-

The silicic acid 1% of high degree of dispersion-

Aluminium iron silicate carrier (attapulgite)-90%

Solubilization of active ingredient in carrene, is sprayed onto this solution on the carrier again, boils off solvent under the vacuum then.

2.4 a） b）

Table 1 compound 2% 5%

The silicic acid of high degree of dispersion 1% 5%

Talcum 97%-

Kaolin-90%

Get the pulvis that to use by close mixed carrier and active component.

The formulation examples (all being weight percentage) of the solid active component by I

2.5 wetting powder is b a)) c)

Table 1 compound 25% 50% 75%

Sodium lignosulfonate 5% 5%-

Lauryl sodium sulfate 3%-5%

Diisobutyl sodium naphthalene sulfonate-6% 10%

Octyl phenol polyglycol ether

(7-8mole oxirane)-2%-

The silicic acid of high degree of dispersion 5% 10% 10%

Kaolin 62% 27%-

Active component and auxiliary agent fully mixed being incorporated in the suitable cracker fully levigate this mixture, gained wetting powder dilutable water becomes the suspending agent of desired concn.

2.6 emulsifiable concentrate a)

Table 1 compound 10%

Octyl phenol polyglycol ether

(4-5mole oxirane 3%

Dodecyl sulphate calcium 3%

The castor oil polyglycol ether

(35mole oxirane) 40%

Cyclohexanone 34%

Xylene mixture 50%

This concentrate of dilute with water can obtain any required emulsion.

2.7 pulvis is b a))

Table 1 compound 5% 8%

Talcum 95%-

Kaolin-92%

By mixed active component and carrier and in suitable cracker, grind this mixture and obtain the pulvis that can directly use.

2.8 extruding pulvis

Table 1 compound 10%

Sodium lignin sulfonate 2%

Carboxymethyl cellulose 1%

Kaolin 87%

Mixed active component and auxiliary agent and levigate, then water this mixture of getting wet, extruding is also dry in air flow.

2.9 coating granula

Table 1 compound 3%

Polyethylene glycol (molecular weight 200) 3%

Kaolin 94%

Active component with meticulous pulverizing in blender is coated on the kaolin of getting wet with polyethylene glycol equably, obtains the coating granula of non-powdery.

2.10 suspension concentrates

Table 1 compound 40%

Ethylene glycol 10%

The nonyl phenol polyglycol ether

(15mole oxirane) 6%

Sodium lignosulfonate 10%

Carboxymethyl cellulose 1%

37% formalin 0.2%

The silicone oil 0.8% of aqueous emulsion form

Water 32%

The active component of meticulous pulverizing is fully mixed with auxiliary agent, obtains suspension concentrates, and this suspension concentrates dilute with water can get any suspending agent of wanting concentration.

3. the effect residual protective of the apple scab (Venturia inaequalis) on 3.1 pairs of apple branches of biological example embodiment

Spray Mixing thing (active component 0.006%) spraying that the cutting of 10-20cm stool apple is made with the wetting powder of test compound.Plant after the processing infected 24 hours with the conidial suspension of fungi.Cultivated 5 days and under 20-24 ℃, placed again at room temperature 10 days these plants under the 90-100% relative moisture.Infect 15 days post-evaluation spot infection conditions.

Table 1 compound presents good active (disease is less than 20%) to scab.For example, compound 1.1,1.6,1.13,1.14,1.59,1.66,1.69,1.84,1.87,1.94,1.108,1.126,1.145,1.158,1.180,1.200 and 1.236 reduce the scab disease to 0-10%.On the other hand, be untreated and the check plant that infects, the scab disease is 100%.

The stiff rotten sick effect of the grey mold of 3.2 pairs of apples of embodiment

Residual protective effect

Handle the apple of artificial injury in the injury position by the Spray Mixing thing (0.002% active constituent) of the wetting powder preparation of test compound by dropping.The apple of handling with the inoculation of the spore suspension of this fungi and in high humility and about 20 ℃ times one weeks of cultivation.Estimate by the Fungicidally active that calculates rotten position and draw test compound.

The listed compound of table 1 is to the stiff rotten sick good active (disease is less than 20%) that shows of grey mold.For example, compound 1.1,1.6,1.13,1.14,1.31,1.33,1.35,1.48,1.59,1.66,1.69,1.84,1.87,1.94,1.108,1.126,1.131,1.145,1.158,1.180 and 1.236 reduce the stiff rotten sick disease of grey mold to 0-10%.On the other hand, be untreated and the stiff rotten disease of the check plant grey mold that infects is 100%.

The effect of 3.3 pairs of barley powdery mildews of embodiment

Residual protective

To the Spray Mixing thing (0.006% active component) of about 8 centimetres high barley seedling spraying by the wetting powder preparation of test compound.The plant of handling was sprayed the conidium of fungi after 3-4 hour.Metainfective barley seedling is placed 10 days post-evaluation fungal diseases in about 22 ℃ greenhouse.

The listed compound of table 1 shows good active (disease is less than 20%) to powdery mildew.For example, compound 1.1,1.6,1.13,1.14,1.35,1.48,1.59,1.66,1.69,1.84,1.87,1.94,1.108,1.131,1.158 and 1.236 reduce the powdery mildew disease to 0-10%.On the other hand, the untreated and check plant that infects, the powdery mildew disease is 100%.

The effect of 3.4 pairs of wheat stripe diseases of embodiment

Pollute wheat berry and dry with fungal spore suspension.Grain after the pollution uses the suspension by the test compound of wetting powder preparation to clean (based on the weight of wheat berry, active component is 600ppm).Two days later grain is put in the suitable agar disks development that fungi falls around 4 days post-evaluation grain.The effect of coming the evaluation test compound based on bacterium colony number and size.The listed compound of table 1 has prevented fungal disease (0-10%) on substantially.

The effect of 3.5 pairs of cucumber ashes of embodiment subcutaneous ulcer disease

Cucumber seedling to two weeks of cultivation sprays the Spray Mixing thing (concentration is 0.002%) for preparing with the wetting powder by test compound.Two days later, infect cucumber seedling and hatching 36 hours under 23 ℃ and high humility, then, continue down to hatch normal humidity and about 22-23 ℃ with fungal spore suspension (1.5 * 105 spore/milliliter).Infect and estimated fungal disease in back 8 days.The check plant that is untreated and dyes, fungal disease are 100%.

The listed compound exhibits good active of table 1 has suppressed the diffusion of disease.Fungal disease is reduced to 20% or littler.

Embodiment 3.6

A) to rice leafhopper and brown plant-hopper (nymph) contact action

Rice seedling with growth carries out this test.For this reason, every dish is transplanted the rice seedling of 4 strains about 15 centimetres high (14-20 days seedling ages), and the diameter of each basin is 5.5 centimetres.

These rice seedlings are sprayed the aqueous emulsion that 100ml contains the 400ppm test compound on turntable.After the coating of spraying is done, the nymph of every strain plant propagation test organism in 20 three length of time.In order to prevent the cicada escape, cover on every strain rice seedling with the glass cylinder of a both ends open, seal with net at the top.These nymphs stay in rice seedling last 6 day of handling until the adult stage.Evaluation is based on behind the plant propagation 6 days percentage lethality.Test under about 27 ℃ and 60% relative moisture and carry out.These rice seedling illumination every day 16 hours.

B) to the systemic action (in water) of brown plant-hopper

The rice seedling of (about 10 centimetres high) was placed in the plastic cup with about 10 day age, and in the cup 150ml concentration being arranged is the aqueous emulsion of the test compound of 100ppm, builds cup with the vinyl cover of a punching.The root of every strain rice seedling inserts vinyl cover from a hole, puts in the aqueous emulsion of test compound always.20 N of breeding on every strain rice seedling ₂-N ₃The nymph of the brown plant-hopper of phase is also covered a plastic cylinder.Test under about 26 ℃ and 60% relative moisture and carry out rice seedling illumination every day 16 hours.Relatively calculate the death toll of test organism after 5 days with the untreated control group.The test compound that whether absorbs through root of proof has killed the test organism at the rice seedling top thus.

The listed compound of table 1 to the test a) and b) in rice grub all demonstrate significant lethal effect.Lethality rate is 80% or bigger.With compound 1.1,1.6,1.14,1.59,1.66,1.87, the lethality rate of 1.94,1.108 and 1.236 gained almost is that 100%(is 98-100%).

Table 1

The general formula of compound

Compound number R ₁R ₂R ₃R ₄Physical constant

1.1 H H CH ₃

m.p.67-69℃

1.2 2-Cl H CH ₃

1.3 H H H

m.p.53-56℃

1.4 H H -CH ₂Br

m.p.77，5-79，5℃

1.5 3-Cl H CH ₃

m.p.104-105℃

1.6 H H -C ₂H ₅

m.p.42-45℃

1.7 4-Cl H -CH ₃

m.p.86-87℃

1.8 H H -CH ₂Br

1.9 H H -CH ₂Cl

m.p.50-52℃

Below table 2, enumerated midbody product of the present invention in 3 and 4.

Table 2

The general formula of compound

Table 3

Table 3(is continuous)

Table 3(is continuous)

Table 3(is continuous

Table 3(is continuous)

Chemical combination Hal R ₃R ₄Physical constant

Thing number

3.46 Br -CH ₂OH

Table 4

Table 4(is continuous)

Table 4(is continuous)

2. the formulation Example (all being weight percentage) of general formula I liquid active component

Claims (9)

1, a kind of control or prevention harmful insect or plant pathogenic microorganisms infringement method of growing plants, this method comprise use contain 0.1-99% general formula I compound as active component be suitable for and carry the composition of stopping on certain part or plant growing zone of plant, plant:

(Ⅰ)

In the general formula

R ₁And R ₂The hydrogen of respectively doing for oneself, halogen, C _1-3Alkyl, C _1-2Haloalkyl, C _1-3Alkoxyl or C _1-3Halogenated alkoxy;

R ₃Be hydrogen, C _1-4Alkyl, the perhaps C that replaces by halogen, hydroxyl and/or cyano group _1-4Alkyl, cyclopropyl or the cyclopropyl that replaces by 1 to 3 methyl and/or halogen;

R ₄Be C _3-6Cycloalkyl or the C that replaces by 1 to 3 methyl and/or halogen _3-6Cycloalkyl.

2, the process of claim 1 wherein R in the generalformula ₃And R ₄Definition with claim 1, and R ₁And R ₂Be hydrogen.

3, the process of claim 1 wherein R in the generalformula ₁And R ₂The hydrogen of respectively doing for oneself, halogen, C _1-3Alkyl, C _1-2Haloalkyl, C _1-3Alkoxyl or C _1-3Halogenated alkoxy, R ₃Be hydrogen, C _1-4Alkyl or the C that replaces by halogen or cyano group _1-4Alkyl; And R ₄Be C _3-6Cycloalkyl or the C that replaces by methyl or halogen _3-6Cycloalkyl.

4, the method for claim 3, wherein R in the generalformula ₁And R ₂The hydrogen of respectively doing for oneself, fluorine, chlorine, bromine, methyl, ethyl, halomethyl, methoxyl group, ethyoxyl or halogenated methoxy; R ₃Be hydrogen, methyl, ethyl, n-pro-pyl or sec-butyl, or the methyl or the ethyl that are replaced by fluorine, chlorine, bromine or cyano group separately; And R ₄Be C _3-6Cycloalkyl or the C that replaces by methyl, fluorine, chlorine or bromine _3-6Cycloalkyl.

5, the process of claim 1 wherein R in the generalformula ₁And R ₂The hydrogen of respectively doing for oneself, fluorine, chlorine, methyl, trifluoromethyl, methoxyl group or difluoro-methoxy; R ₃Be hydrogen, C _1-3Alkyl is by the C of halogen or hydroxyl replacement _1-2Alkyl, cyclopropyl or the cyclopropyl that is replaced by 1 to 3 methyl and/or halogen; And R ₄Be C _3-6Cycloalkyl or the C that is replaced by 1 to 3 methyl and/or halogen _3-6Cycloalkyl.

6, the process of claim 1 wherein R in the generalformula ₁And R ₂The hydrogen of respectively doing for oneself, R ₃Be C _1-3Alkyl, by the methyl that fluorine, chlorine, bromine or hydroxyl replace, cyclopropyl or the cyclopropyl that is replaced by methyl, fluorine, chlorine or bromine; And R ₄Be C _3-4Cycloalkyl or the C that is replaced by 1-3 methyl and/or fluorine, chlorine or bromine _3-4Cycloalkyl.

7, the method for claim 3, wherein compound is selected from:

2-phenyl amino-4-methyl-6-cyclopropyl pyrimidine,

2-phenyl amino-4-ethyl-6-cyclopropyl pyrimidine,

2-phenyl amino-4-methyl-6-(2-methyl cyclopropyl) pyrimidine and,

2-(is right-fluorophenyl amino)-4-methyl-6-cyclopropyl pyrimidine,

8, the process of claim 1 wherein that compound is selected from:

2-phenyl amino-4,6-two (cyclopropyl) pyrimidine,

2-phenyl amino-4-methylol-6-cyclopropyl pyrimidine,

2-phenyl amino-4-methyl fluoride-6-cyclopropyl pyrimidine,

2-phenyl amino-4-methylol-6-(2-methyl cyclopropyl) pyrimidine,

2-phenyl amino-4-methyl-6-(2-fluorine cyclopropyl) pyrimidine,

2-phenyl amino-4-methyl-6-(2-chlorine cyclopropyl) pyrimidine,

2-phenyl amino-4-methyl-6-(2-difluoro cyclopropyl) pyrimidine,

2-phenyl amino-4-methyl fluoride-6-(2-fluorine cyclopropyl) pyrimidine,

2-phenyl amino-4-methyl fluoride-6-(2-chlorine cyclopropyl) pyrimidine,

2-phenyl amino-4-methyl fluoride-6-(2-methyl cyclopropyl) pyrimidine and 2-phenyl amino-4-ethyl-6-(2-methyl cyclopropyl) pyrimidine.

9, the method for claim 1 makes phytopathogenic fungi controlled with this method.