CN1010945B - Process for prepn. of benzoylphenylureas - Google Patents
Process for prepn. of benzoylphenylureasInfo
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- CN1010945B CN1010945B CN 85108238 CN85108238A CN1010945B CN 1010945 B CN1010945 B CN 1010945B CN 85108238 CN85108238 CN 85108238 CN 85108238 A CN85108238 A CN 85108238A CN 1010945 B CN1010945 B CN 1010945B
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Abstract
The invention relates to a manufacturing method of a novel substituted N-benzoyl-N'-2,5-dichloro-4-hexafluoropropyloxyphenylureas andand to the salts thereof. The molecular formula of the compound is as follows: wherein R1 is hydrogen, fluorine, chlorine or methoxy, and R2 is fluorine, chlorine or methoxy, and to the thereof, The invention also relates to proesses and intermediates for the preparation of these compounds and to compositions containing the novel compounds for controlling insects and representatives of the order Acarina, in particular plant-destructive insects.
Description
The present invention relates to class N-benzoyl-N '-2 new, that replace, the preparation method of 5-two chloro-4-hexafluoro propoxy-phenylureas and intermediate product thereof, and relate to this class new compound insect is controlled.
The present invention relates to molecular formula is a compounds and its esters of I.
R wherein
1Be hydrogen, fluorine, chlorine or methoxyl group, and R
2Be fluorine, chlorine or methoxyl group.
What be worth especially emphasizing is that molecular formula is in this compounds of I, R
1Be hydrogen, fluorine or chlorine, and R
2Be those compounds of fluorine, chlorine or methoxyl group.
What be worth especially emphasizing is, molecular formula is the other compound in the compounds of I, R in their molecular formula
1And R
2Be fluorine, chlorine or methoxyl group simultaneously.
What also will further emphasize is, molecular formula is those R in this compounds of I
1Be hydrogen, fluorine or chlorine, and R
2Be those compounds of fluorine or chlorine, and R
1Be hydrogen or fluorine R
2Those compounds for fluorine or chlorine.
Molecular formula is that a compounds of I can prepare (with reference to German Patent prospectus 2123236,2061780 and No. 3240975) with currently known methods
For example, molecular formula is that the preparation of certain compound of I can be passed through:
A) molecular formula is that the compound of II and compound that molecular formula is III react
Perhaps
B) molecular formula is that the compound of IV and compound that molecular formula is V react
Perhaps
C) molecular formula is that the compound of II and compound that molecular formula is VI react
In above-mentioned molecular formula III, in V and the VI, R
1With R
2Definition identical with the molecular formula I, R is c
1-c
8Alkyl.This alkyl is not replaced by halogen (mainly being chlorine) or is replaced by halogen (preferably chlorine).
Above-mentioned a), b) and c) three kinds of methods are preferably in normal pressure, organic solvent or thinner and carry out under existing.The suitable solvent or thinner example have: the compound of ethers and ether, Anaesthetie Ether for example, dipropyl ether, dibutyl ether, dioxane, glycol dimethyl ether and tetrahydrofuran (THF); N, the carboxylic acid amide of N '-dialkyl groupization; Aliphatic series, aromatics and halogenated hydrocarbon, particularly benzene, toluene, dimethylbenzene chloroform, methylene dichloride, tetracol phenixin and chlorinated benzene; Nitrile such as acetonitrile or propionitrile; Dimethyl sulfoxide (DMSO); Ketone such as acetone, methylethylketone, methyl isopropyl Ketone and methyl iso-butyl ketone (MIBK).Method a) is reacted in-10 ° to+200 ℃ temperature ranges usually, and is better in 0 ° to 100 ℃ scope, for example room temperature.If desired, can in the presence of organic bases such as triethylamine, react.Method b) in 0 ° to 150 ℃ temperature range, carries out, preferably under the boiling point of solvent for use, react.If desired, can in the presence of organic bases such as the pyridine and (or) append under basic metal or the alkaline-earth metal (with sodium for well) and react.As for method c), just molecular formula is that the urethane and the molecular formula of VI are the reaction of the aniline of II, temperature range preferably about 60 ℃ between the boiling point of reaction mixture.Solvent for use is with aromatic hydrocarbon, toluene for example, and dimethylbenzene, chlorinated benzene etc. are for well.
Molecular formula is that the raw material of III and V is known, and they can prepare with known those similar approach.Molecular formula is that the raw material aniline of II is a new compound, and it is one of object of the present invention equally.Molecular formula is that the compound of II can will be that the oil of mirbane hydrogenation of VII makes through the molecular formula of suitable replacement by known method, this method with " J.org.chem 29(1964); 1 " described in similar, (can also with reference to the document that is drawn in this piece article):
Yet molecular formula is that the aniline of II can be that the nitro-compound of VII prepares (with reference to Houben-weyl, " Metho-den dorg chemie 11/1,422) through chemical reduction (for example using tindichloride/hydrochloric acid) by molecular formula also.Molecular formula is that the nitro-compound of VII itself can be by 2, the preparation of the haloalkylation of 5-two chloro-4-nitrophenolss.Molecular formula is that other preparation methods of the aniline of II have haloalkylation, and this method is in the corresponding way with 2 of ethanoylization, 5-two chloro-4-hydroxyanilines haloalkylations, and deacetylate promptly carries out acidolysis then; Or with 2,5-two chloro-4-hydroxybenzene amine salt (for example hydrochloride) carry out haloalkylation.
In addition, molecular formula is that the benzoyl isocyanic ester of III can be according to following method preparation (with reference to J.Agr Food chem.21,348 and 993,1973):
Molecular formula is that the 4-hexafluoro propoxy-phenyl isocyanate (95 ℃/0.01 ninth of the ten Heavenly Stems of boiling point) of IV comes down to a new compound, can be by with molecular formula being the method preparation of the aniline phosgenation of II, (this method is used always in the prior art); This compound also is one of object of the present invention.Molecular formula is that the benzamide of V is known, it continue after again as reaction raw materials (for example, with reference to Beilstein " Handbuch der organischenche-mie ", Vol.9, P.336).Molecular formula is that a class urethane of VI is that the benzoyl isocyanic ester and the reaction of suitable alcohol of III obtains by currently known methods by molecular formula in fact, is that the benzamide of V is reacted with the corresponding ester cl-cooR of chloroformic acid under alkaline condition and made with molecular formula perhaps.
According to the present invention, molecular formula is that a class new compound of I comprises that also by they prepared salt, these salt not only demonstrate high insecticidal activity but also are soluble in solvent and thinner, particularly are soluble in organic solvent, but also is easy to preparation.
Be stressed that especially molecular formula is the basic metal and the alkaline-earth metal salt of a compounds of I among the present invention, especially their sodium salt and sylvite are better.These salt come down to by currently known methods preparation, are that the compound of I and metal alkoxide (as sodium ethylate or potassium methylate) react and make with molecular formula for example.Specified a kind of metal-salt can be by being converted into the salt of required another kind of metal with the pure reactant salt of another kind.
Particularly importantly molecular formula is the compound of I and the salt that organic bases generates, and their essential characteristic is to have quaternary nitrogen atoms.The molecular formula of this class salt is I a
Wherein, R
1With R
2Definition as above, X
It is a kind of positively charged ion of organic bases.X
Mainly be one of following organic cation:
Here n is 8 to 12 integer.Molecular formula is that the salt of I a also comprises the mixture that contains different cationic these salt.Molecular formula is the in fact available currently known methods preparation of the salt of I a, promptly is the compound and corresponding ammonium hydroxide prepared in reaction of I by molecular formula.The molecular formula of this class ammonium hydroxide is X
(OH)
, X wherein
As defined above.
We are surprised to find that compound of the present invention and its esters have good character as agricultural chemicals, and plant has good tolerability then to have low toxicity for warm-blooded animal to them.They are particularly suitable for controlling the typical acarine of insects and infringement plant and animal.
Particularly molecular formula is the insect that a compounds of I is applicable to the following kind of control: lepidopteran, Coleoptera, Hemiptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, the typical acarian that Hymenoptera and following section belong to: hard tick section, latent green tick section, tetranychus telarius section and Dermanyssidae.They also have toxic action to the fly class in addition, for example kill the larva of housefly and mosquito.Molecular formula is the pasture insect that a compounds of I also is applicable to the control destruction of plants; these insect growths are in the inflorescence or taper of cash crop; especially in cotton (for example extra large grey wing leaf moth and Heliothis virescens), fruits and vegetables, (for example codling moth, colorado potato beetles and big Epilachna spp).Molecular formula is that a compounds of I is a kind of ovicide of produce effects, especially has the effect of kill insects larva, and is more effective for the larva of deleterious pasture insect.If molecular formula be a compounds of I along with food is eaten by adult, then find many insects, especially beetle (for example cotton boll resembles) reduces spawning rate and or reduces the hatching rate of ovum.
Molecular formula is that the compound of I also can be used for being controlled at parasitic epizoon class (for example lucilia sericata) in the domestic animal of domestic animal and breeding, and its method is to realize by handling animal, cowshed stable, horse grid and herbage.
Molecular formula is that a compounds of I also is applicable to the little of the following infringement of control fruits and vegetables
Class: cotton spider mites, tetranychus telarius, elm Panonychus citri, Broybia rubrioculus, tangerine Panonychus citri, pears bud mite, tea sugarcane goitre mite, grape erineum mite (Eriophyes vitis), grey lines mite, grape rust mite and tangerine cloud rust mite.
Molecular formula of the present invention is that the good pesticide activity of a compounds of I shows that the lethality rate to above-mentioned insect is not less than 50～60%.
Molecular formula be the compound of I and the mixture that contains these compounds activity can by add other pesticides and (or) Acaricide significantly strengthened and applicable to existing situation.Suitable example additives has: organo phosphorous compounds, nitrophenyl phenolic and derivative thereof, formamidine, ureas, amino formate, pyrethroid, chlorinated hydrocarbon and thuringiensis Rod bacteria preparation.
Molecular formula is that a compounds of I uses with unmodified form, and perhaps the auxiliary that preferably routine is used in current technology is used.Therefore by currently known methods with they be made into emulsifiable concentrate, directly can spray or dilutable solution, dilute emulsion, wettable powder, soluble powder, fine powder, particle, also can the capsule dress, for example capsule is loaded in the polymkeric substance.Select application method for use according to the character of batching and application target and at that time environment, for example: spray, spray, raise spread, spreading or pour.
By known method, for example with active constituent and dispersion agent (as solvent, solid-state carrier, and add Surfactant sometimes) uniform mixing and (or) grind, can prepare the compound (active constituent) or this compound and other sterilant or miticide (and the needs that contain the molecular formula I, sneak into solid-state or liquid auxiliary) the finished product medicament of mixture, that is mixture, preparation or mixture.
The suitable solvent has: aromatic hydrocarbons, preferably contain 8 fractions to twelve carbon atom, for example xylene mixture or replacement naphthalene; Phthalic acid ester class, for example dibutyl phthalic acid ester or diisooctyl phthalic acid ester; Aliphatic hydrocarbon, for example hexanaphthene or straight-chain paraffin class; Alcohols and glycols and their ether and ester, for example ethanol, ethylene glycol monomethyl ether or single ether; Ketone, for example pimelinketone; Intensive polar solvent, for example N-methyl-2 pyrrolidone, dimethyl sulfoxide (DMSO) or dimethyl formamide; And vegetables oil or epoxidized vegetable oil, for example epoxidation Oleum Cocois or soybean oil; Also has water.
Used solid-state carrier (for example dust and dispersible powder) is generally the natural mineral filler, such as calcite, talcum powder, kaolin, montmorillonite or attapulgite.In order to improve physical properties, also can add the silicic acid of high dispersive or the superpolymer sorbent material of high dispersive.Suitable granular adsorption type carrier is the multi-hole type material, for example float stone, queen closer, sepiolite or wilkinite; Suitable non-adsorptive type carrier has calcite or sand etc.In addition, inorganic or organic crude substance of pulverizing in advance in a large number also can use, for example especially rhombspar and comminuted plants slag.
According to used molecular formula in the batching is the character of the compound of I or they and sterilant, acaricidal mixture, selects the superficiality compound for use.Suitable surface active cpd have non-ionic type, cationic and (or) the anionic Surfactant, this class material has good emulsifying, dispersiveness and wettability.Term " surfactant-based " speech refers to and contains some surfactant mixtures.
Suitable tensio-active agent has water-soluble soap class and synthetic water-soluble surface-active compound.
Suitable soap class is higher lipid acid (c
10-c
22) alkaline metal salt, alkaline earth salt or replace and do not replace the ammonium salt of higher fatty acid, for example oleic acid or stearic acid sodium salt or sylvite.Can obtain the sodium salt or the sylvite of blended natural acid from Oleum Cocois or animal tallow.Other tensio-active agent also has lipid acid taurine salt and modification and unmodified phosphatide.
Yet, more usually so-called synthetic tensio-active agent, especially fatty sulfonate, fat sulphate, sulphonated benzimidazole derivative or alkylaryl sulphonate.
Fat sulfonate or vitriol often are to occur with basic metal, alkaline-earth metal or replacement and unsubstituted ammonium salts, and these salt contain c
8-c
22Alkyl, also comprise the moieties of acyl group.For example, sodium lignosulfonate or calcium salt, the sodium sulfate salt or the calcium salt of sodium lauryl sulphate or calcium salt or the blended Fatty Alcohol(C12-C14 and C12-C18) from natural acid, obtained.These compounds also comprise the sulfonate of sulfuric acid ester and Fatty Alcohol(C12-C14 and C12-C18) ethylene oxide adduct.Sulfonation imdazole derivatives class preferably contains two sulfonic acid groups and one and contains c
8-c
22Fatty acid group.The example of alkylaryl sulphonate has: sodium salt, calcium salt or the triethanolamine salt of dodecylphenyl sulfonic acid, dibutyl naphthene sulfonic acid/formaldehyde condensation products.Corresponding phosphoric acid salt, the salt of the phosphoric acid ester of the adducts of for example right-nonyl phenol and 4 to 14 molar oxyethane also is suitable for.
Nonionic surface active agent is the polyglycol ether derivative of Fatty Alcohol(C12-C14 and C12-C18) or ring-shaped fat alcohol, saturated or unsaturated fatty acids and alkylphenol preferably, and said derivative contains 3 to 30 glycol ethers, 8-20 carbon atom arranged and at the moieties of alkylphenol 6 to 18 carbon atoms are arranged at aliphatic hydrocarbon moiety.
Other suitable nonionogenic tensides have the water-soluble addition thing of polyethylene oxide and propylene glycol, quadrol base polypropylene glycol and contain the alkyl polypropylene glycol of 1 to 10 carbon atom in alkyl chain, this adducts contains 20 to 250 ethylene glycol ethers and 10 to 100 propylene glycol ethers.These compounds each propylene glycol unit often have 1 to 5 ethylene glycol unit.
The representative example of nonionic surface active agent is a nonylphenol polyethoxyethanols class, Viscotrol C polyoxyethylene glycol ethers, polypropylene/poly(propylene oxide) adducts, tributyl phenoxy group polyethoxyethanols, polyoxyethylene glycol and octyl phenoxy group polyethoxyethanols.The fatty acid ester of polyoxygenated ethylene sorbitan (for example polyoxygenated ethylene sorbitan oleate) also is the nonionic surface active agent that suits.
Cationic surfactant is quaternary ammonium salt preferably, comprising substituent as N-, has at least an alkyl to contain c
8-c
22, substituent unsubstituted or halogenated low-carbon alkyl, phenyl or hydroxyl-low-carbon alkyl can be arranged as other.These salt preferably occur with the form of halogenide, methyl sulfate or sulfovinic acid, for example, and chlorination stearic acid trimethyl ammonium or cylite two (2-chloroethyl) ethyl ammonium.
Tensio-active agent commonly used in blending process has narration in some document, " washing composition of McCutcheon and emulsifying agent annual report " (" McCutcheon ' s Detergents and Emulsifiers An-nual ", MC Publishing C of publishing of MC publishing company 1979 for example
oRp.Ridgewood, New Jer-sey, 1979); " tensio-active agent handbook " (Dr.Helmut St that publish in Ka Er-Han Saier-work glug press, Helmut doctor Stache work
aChe, " Tensid Taschenbuch " Curl Hanser Verlag, Mun-ish/Vienna).
Pesticide mixture often contains 0.1～99%(preferably 0.1～95%) molecular formula be the compound of I or they and other sterilants and acaricidal mixture, also contain 1～99.9% solid or liquid auxiliary agent and 0～25%(preferably 0.1～20%) tensio-active agent.
Yet the commercially available prod mainly is made into enriched material, and operator is used the dilution preparation of extremely low concentration usually.
Mixture also can contain other batching, stablizer for example, and defoamer, viscosity modifier, tackiness agent, tackifier and chemical fertilizer or other active Synergist S-421 95s are so that obtain some special efficacy.
Embodiment 1:
A) 2,5-two chloro-4-(1,1,2,3,3,3 ,-hexafluoro propoxy-) preparation of aniline
With 47 gram 4-acetamidos-2, the potassium hydroxide solution of 5-chlorophenesic acid and 154 grams 90% and 130 milliliters of dimethyl formamides are put into an autoclave and are stirred.Then, 75.8 gram R 1216s are pressed in the autoclave of this sealing.This mixture was stirred 20 hours under 70 ℃ and the existing pressure of autoclave.After the cooling, mixture concentrates with the rotary evaporation method, and residue is dissolved in methylene dichloride.Wash the solution of gained with water, use dried over sodium sulfate, concentrate then.The crude product that obtains with the residue form carries out chromatographic separation (column length: 1 meter by silicagel column; Diameter: 10 centimetres), with 11: 1 toluene-acetone mixed solvent drip washing, the 4-acetamido-2 that obtains, 5-two chloro-1-(1,1,2,3,3,3 ,-hexafluoro propoxy-) benzene is faint yellow crystallization (fusing point: 93～95 ℃).Get 26 these products of gram with the hydrochloric acid reflux of 110 milliliters of ethanol and 35.6 milliliter 37% 10 hours.Then, reaction mixture is concentrated,, make to be weakly alkaline with the dilution of ice/water.With methylene dichloride product is extracted from mixed solution.Wash the organic extraction phase with water, use Na
2SO
4Drying concentrates then.With steaming refining this enriched material of filling method, this title compound that obtains having following molecular formula:
This product is a colourless liquid, and boiling point was 81～83 ℃/0.05 ninth of the ten Heavenly Stems.
B) N-(2,6-difluoro benzoyl)-and N '-(2,5-two chloro-4-(1,1,2,3,3,3-hexafluoro propoxy-) phenyl) preparation of urea
With 4.7 grams 2,5-two chloro-4-(1,1,2,3,3,3-hexafluoro propoxy-) aniline under agitation is dissolved in 50 milliliters of exsiccant toluene and gets rid of moisture at any time.Then, at room temperature add 10 milliliters and contain 2.62 grams 2, the toluene solution of 6-difluoro benzoyl isocyanic ester.Reactor continues at room temperature to stir 10 hours.Afterwards, remove about 75% solvent, use the suction filtration filtering-depositing,, place vacuum dry again, obtain this following title compound of molecular formula at last with a small amount of cold toluene and hexane wash with the rotary evaporation method:
This compound is crystalline white powder, and fusing point is 174～175 ℃ (compounds 1).
Make following some compounds that molecular formula is an I according to above-mentioned with quadrat method:
Melting point compound
C) preparation of the sodium salt of compound 1
With 9.58 gram N-(2,6-difluoro benzoyl)-N '-(2,5-two chloro-4-(1,1,2,3,3,3-hexafluoro propoxy-) phenyl) urea is suspended in 20 milliliters of absolute methyl alcohol.30 milliliters of absolute methanol solutions of 0.43 gram sodium under agitation are added drop-wise in the suspension.Then, the clear solution with gained concentrates.Enriched product is vacuum-drying at room temperature, and this title compound that obtains is a clear crystal, and its molecular formula is:
Fusing point before this compound decomposition is 169～171 ℃ (compounds 10).
The salt of the compound 2 that molecular formula is following also can prepare as stated above.
Melting point compound
To decomposing
D) preparation of the tertiary butyl ammonium salt of compound 1
With 2.56 gram N-(2,6-difluoro benzoyl)-N '-(2,5-two chloro-4-(1,1,2,3,3,3-hexafluoro propoxy-) phenyl) urea is outstanding
Embodiment 2:
Preparation (same operating weight percentage ratio in the present embodiment) with the composition that to be the compound of I or its constitute with sterilant and miticide of the molecular formula according to embodiment 1 preparation
1. c a) b of wettable powder))
Molecular formula is the compound of I or its composition 25% 50% 75%
Sodium lignosulfonate 5% 5%-
Sodium laurate 3%-5%
Diisobutyl sodium naphthalene sulfonate-6% 10%
Octyl phenol polyglycol ether
(7～8 molar oxyethane)-2%-
The silicic acid of high dispersive 5% 10% 10%
Kaolin 62% 27%-
Active constituent or its composition are mixed fully with auxiliary, and this mixture is in suitable floating in 30 ml methanol.Under agitation, the 5.2 gram methanol solutions that will contain 1.3 gram 4-n-butyl ammonium hydroxides add in this suspension, and the result has generated clear solution.The thick product of this solution after concentrating is suspended in the hexane.Use the suction method filtering suspension liquid, use the hexane wash filter residue, dry then, obtain this following title compound of molecular formula, be clear crystal, fusing point is 110 ℃ (compounds 12):
Molecular formula is that the following salt of I a also can prepare by this method:
Compound
Fully grind in the ball mill, the wettable powder that makes can obtain the suspension formulation of desired concn behind the dilute with water.
2. concentrate formulation that can floating
Molecular formula is compound or its composition 10% of I
Octyl phenol polyglycol ether
(4～5 mol oxyethane) 3%
Dodecylphenyl calcium sulphonate 3%
The Viscotrol C polyglycol ether
(36 mol oxyethane) 4%
Pimelinketone 30%
Xylene mixture 50%
This concentrate formulation of dilute with water can make the emulsion of required any concentration.
3. a) b of fine powder)
Molecular formula is the compound of I or its composition 5% 8%
Talcum powder 95%-
Kaolin-92%
Active constituent is mixed with carrier and place suitable grinding in ball grinder, obtain standby fine powder.
4. use the extrusion machine granulation
Molecular formula is compound or its composition 10% of I
Sodium lignosulfonate 2%
Carboxymethyl cellulose 1%
Kaolin 87%
Active constituent or its composition are mixed with auxiliary and grind, then with this mixture of water-wet.This mixture places airflow dry after extrusion moulding.
5. coating granulation
Molecular formula is compound or its composition 3% of I
Macrogol 200 3%
Kaolin 94%
The active constituent of fine grinding or its composition evenly are coated on the kaolin surface of soaking with polyoxyethylene glycol in mixer.This method can make non-dusting coating particle.
6. suspension concentrate formulation
Molecular formula is compound or its composition 40% of I
Ethylene glycol 10%
Nonoxynol-9
(15 mol oxyethane) 6%
Sodium cellulose xanghate 10%
Carboxymethyl cellulose 1%
37% formalin 0.2%
Silicone oil (75% aqueous emulsion) 0.8%
Water 32%
The active constituent of fine grinding or its composition with the auxiliary thorough mixing, are obtained suspension concentrate.This concentrated solution of dilute with water can obtain the suspension of required any concentration.
Embodiment 3: to the toxic action of housefly
The fly maggot nutraceutical matrix of the existing preparation of 50 grams is placed some beakers respectively.Contain in each beaker of nutraceutical matrix with the acetone soln immigration of transfer pipet, make active constituent concentration reach 800ppm each experimental compound of 1% specified amount.Then, with the matrix thorough mixing, then at least 20 hours time, the acetone volatilization is done.
In containing the beaker of nutraceutical matrix of the experiment usefulness that useful active constituent handled, each puts into 25 fly maggots.After treating fly maggot nymphosis, pupa is taken out from matrix, clean and place the container of a usefulness perforated lid capping with water wash.
Write down the number of every batch of pupa of drip washing, with the toxic effect of confirmed test compound to the maggot growth.After 10 days, write down the number that pupa hatches fly.
According to the molecular formula of embodiment 1 preparation is that a compounds of I has good activity in this experiment.
Embodiment 4: to the toxic action of lucilia sericata
The 1 ml water solution that will contain 0.5% experimental compound is added in 9 milliliters of developing mediums, and experimental temperature is 50 ℃.Get 30 lucilia sericata larvaes that just hatched then and put into developing medium, after 48 hours and 96 hours, determine the effect of pesticide by estimating mortality ratio respectively.
In this test, be that a compounds of I demonstrates the excellent activity to lucilia sericata according to the molecular formula of embodiment 1 preparation.
Embodiment 5: to the toxic action of Aedes aegypti
The acetone soln that contains 0.1% test compound that pipettes specified amount is put into the surface of beaker 150 ml waters, makes the solution of 800ppm concentration.After treating the acetone volatilization, get the Aedes aegypti larva in 30 to 40 two day ages and put into the beaker that contains test compound.After 1,2 day and 5 days, obtain the numeral of their death.
In this test, be that a compounds of I demonstrates the excellent activity to Aedes aegypti according to the molecular formula of embodiment 1 preparation.
Embodiment 6: to the toxic action of pasture insect
About 25 centimetres high some cotton seedling is planted in basin, is 0.75,12.5 and the test compound solution of 100ppm spray with concentration respectively, treat the spraying layer drying after, with extra large spodoptera and L
8The Heliothis virescens larva of-growth phase is implanted on the cotton seedling.Under the condition of 24 ℃ and relative humidity 60%, experimentize.The percentage mortality ratio of experiment insect was determined after 120 hours.
According to the compound 1 of embodiment 1 preparation, when its concentration is 0.75ppm, be 80-100% to the lethality rate of extra large spodoptera larva and Heliothis virescens larva.When compound 3 is 12.5ppm in its concentration, be 80～100% to the lethality rate of extra large spodoptera larva and Heliothis virescens larva.
Embodiment 7: to the toxic action of big Epilachna spp
With concentration is the test compound water emulsion preparation spray Kidney bean seedling of 800ppm, the high 15-20 of bean seedlings centimetre (short and small beans).After the spray coating drying, move on every strain bean seedlings and grow 5 L
4The big Epilachna spp larva of-growth phase (Mexico beans beetle).Plastic barrel is enclosed within on the plant of handling, covers with copper mesh.Under the condition of 28 ℃ and relative humidity 60%, test.After two days or three day, determine the percentage lethality rate.Continue to observe three days, with the degree of estimating pasture degree of damage (the anti-effect of herding) and stoping herbage growth and come off.
According to the molecular formula of embodiment 1 preparation is that a compounds of I demonstrates good activity in this test.
Embodiment 8: to the ovicidal action of Heliothis virescens
Get a certain amount of wettable powder formulation that contains the test compound of 25% weight, be mixed and made into it with the water of capacity and contain the water miscible liquid that active constituent concentration is 800ppm.The Heliothis virescens egg that is placed on the age on the glassine paper piled up in the emulsion soaked 3 minutes.Then, they are placed on the type filter paper of garden and blot.The egg of handling is deposited on the Petri dish, in the dark preserves.After 6～8 days, by they relatively more definite hatching rate with the background egg heap that is untreated.
According to the molecular formula of embodiment 1 preparation is that a compounds of I demonstrates good activity in this experiment.
Embodiment 9: to the toxic action (egg) of codling moth
The codling moth egg that is placed on the filter paper that is no more than 24 hour age is piled, in containing water-acetone soln that test compound concentration is 800ppm, soaked 1 minute.After the solution drying, egg is deposited in places the dark place to preserve on the Petri dish.Storage temperature is 28 ℃.After six days, estimate the percentage ratio and the percentage mortality ratio that from the egg of handling, hatch larva.
According to the molecular formula of embodiment 1 preparation is that the compound of I demonstrates good activity in this experiment.
Embodiment 10: the influence that cotton boll is resembled the breeding effect
The back cotton boll less than 24 hour age of hatching is resembled adult transfer in the sealing cage, per 25 is one group.Then, cage is placed to contain concentration be that the acetone soln of 400ppm test compound soaked for 5 to 10 seconds.After treating the beetle drying, they are placed on the plate with cover of food and leaf, make it mating and lay eggs.Wash egg heap gently 2～3 times with mobile water, counting is placed on them to soak in the sterilant aqueous solution and carried out disinfection in 2 to 3 hours, then egg is deposited in the dish that contains the food that is suitable for larva.After seven days, determine the percentage lethality rate of egg according to the larva number of from egg, hatching.
By the time length of further supervision egg heap, that is further observe many times in 4 weeks with the breeding retarding effect of definite compound.Estimate with the method that the background that is untreated compares by minimizing then egg of piling up and the number of hatching larva.
Compound 1 and 3 according to embodiment 1 preparation demonstrates 80% to 100% ovicidal activity in this test.
Embodiment 11: the effect that cotton boll is resembled (adult)
Implant the cotton seedling in 6 leaf stages of two strains in basin, spray them with wettable water emulsion preparation, the concentration that contains test compound in the milk sap is 400ppm.After the spray, make coating drying (about 1 1/2 hours), on every young plant, put 10 sophisticated beetles (cotton boll resembles).For preventing that beetle from runing away from cotton seedling, going up illiteracy with the top has the plastic barrel cover of husky net to be buckled on the cotton seedling that chemicals treatment is crossed, that experimental insect is being lived away from home.Then, the cotton seedling of handling is placed the environment of 25 ℃ and relative humidity about 60%.By determining beetle mortality ratio (percentage ratio on blade back) and anti-ly herding relatively estimating of effect and the background that is untreated.
According to the molecular formula of embodiment 1 preparation is that a compounds of I demonstrates good activity in this experiment
Claims (17)
1, the method for the compound or its salt of the following molecular formula I of preparation:
R in the formula
1Be hydrogen, fluorine, chlorine or methoxyl group, R
2Be fluorine, chlorine or methoxyl group, it is characterized in that this method is included under the condition of a kind of organic solvent or thinner existence, in-10 to+200 ℃ of temperature ranges, will
A) compound of following molecular formula II
React with the compound of following molecular formula III
Or with b) compound of following molecular formula IV
React with the compound of following molecular formula IV,
Or with c) compound of molecular formula II and the compound of following molecular formula VI react,
In molecular formula III, V and VI, R
1And R
2The definition of group as mentioned above, and R be a kind of not by or by the plain C that replaces of fontanel
1-C
8Alkyl group, and, when needed, resulting formula I compound is converted into its salt.
2, according to the method for the compound of the preparation molecular formula I of claim 1, it is characterized in that, wherein R
1Be hydrogen, fluorine or chlorine, R
2Be fluorine, chlorine or methoxyl group.
3, according to the method for the compound of the preparation molecular formula I of claim 1, it is characterized in that, wherein R
1And R
2Be fluorine, chlorine or methoxyl group simultaneously.
4, according to the method for the compound of the preparation molecular formula I of claim 1, it is characterized in that, wherein R
1Be hydrogen, fluorine or chlorine, R is a fluorine or chlorine.
5, according to the method for the compound of the preparation molecular formula I of claim 4, it is characterized in that, wherein R
1Be hydrogen or fluorine, R
2It is fluorine or chlorine.
6, according to the method for the compound of the following molecular formula of preparation of claim 3:
7, according to the method for the compound of the following molecular formula of preparation of claim 5:
8, according to the method for the compound of the following molecular formula of preparation of claim 3:
9, according to the method for the compound of the following molecular formula of preparation of claim 5:
10, according to the method for the compound of the following molecular formula of preparation of claim 2:
11, according to the method for the compound of the following molecular formula of preparation of claim 5:
12, according to the method for the compound of the following molecular formula of preparation of claim 2:
13, according to the method for the compound of the following molecular formula of preparation of claim 3:
14, according to the method for the compound of the following molecular formula of preparation of claim 2:
15, according to the basic metal of the compound of the preparation molecular formula I of claim 1 or the method for alkaline earth salt, it is characterized in that, this method is included under a kind of condition of solvent existence, the compound of prepared molecular formula I is reacted with the alkoxide of described relevant metal, or with prepared salt, by reacting, be converted into the salt of needed another kind of basic metal or alkaline-earth metal with corresponding alkoxide.
16, according to the method for the salt of the compound of the preparation molecular formula 1 of claim 1 and organic bases, in described salt, have quaternary nitrogen atoms to exist with following molecular formula I a thereby make:
R in the formula
1And R
2Definition and claim 1 in identical, X
Be a kind of positively charged ion of organic bases, it is characterized in that this method is included under a kind of situation of solvent existence, with the compound and the formula X of prepared molecular formula I
(OH)
Corresponding ammonium hydroxide react X wherein
Be following a kind of positive Guo:
N is 8 to 12 integer in the formula.
17, according to the method for the compound of the preparation molecular formula I of claim 1, the compound of intermediate molecular formula II wherein,
Be by at pressurize with having under the condition that a kind of solvent exists, with 2 of acidylate, 5-two chloro-4-hydroxyanilines and 1,1,2,3,3, the method that the 3-R 1216 reacts prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90108572 CN1017958B (en) | 1984-10-18 | 1985-10-18 | Insecticidal and acaricidal composition contg. benzoylphenylureas or salts thereof and use thereof |
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH4993/84-1 | 1984-10-18 | ||
| CH499384 | 1984-10-18 | ||
| CH5361/84-2 | 1984-11-08 | ||
| CH536184 | 1984-11-08 | ||
| CH2048/85-1 | 1985-05-14 | ||
| CH350285 | 1985-08-14 | ||
| CH3502/85-2 | 1985-08-14 | ||
| CH8502/85-2 | 1985-08-14 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90108572 Division CN1017958B (en) | 1984-10-18 | 1985-10-18 | Insecticidal and acaricidal composition contg. benzoylphenylureas or salts thereof and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85108238A CN85108238A (en) | 1986-04-10 |
| CN1010945B true CN1010945B (en) | 1990-12-26 |
Family
ID=27174375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85108238 Expired CN1010945B (en) | 1984-10-18 | 1985-10-18 | Process for prepn. of benzoylphenylureas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1010945B (en) |
-
1985
- 1985-10-18 CN CN 85108238 patent/CN1010945B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85108238A (en) | 1986-04-10 |
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