• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    Substituted N-benzoyl-N'-3,5-dichloro-hexafluoropropyloxyphenylureas of the formula <IMAGE> wherein R1 is hydrogen or fluorine and R2 is fluorine or chlorine, and salts thereof are useful for controlling insects, representatives of the order Acarina, slugs and snails, particularly plant-destructive insects. Intermediates for these compounds having the formulae <IMAGE> are also disclosed.
    公开号:SU1588277A3
    申请号:SU864028385
    申请日:1986-10-13
    公开日:1990-08-23
    发明作者:Драбек Йозеф
    申请人:Циба-Гейги Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to new substituted N-benzoyl-N-3,5-dichlorop-4-hexafluoropropyloxyfenerm ureas of the general formula
    Rict
    O-CO-NH-CO-NH-O OCFT-CHF-CF; j R7-Cl where R is hydrogen or fluorine;
    R is fluorine or chlorine,
    or their alkaline or ammonium salts, which exhibit a higher insecticidal activity than compounds of similar structure and similar purpose.
    Example 1
    a) Preparation of 3,5-dichloro-4- (1,1,2, - 3,3,3-hexafluoropropyloxy) aniline. 47 g of 4-acetylamino-3, 5-dichlorophenol are stirred in an autoclave together with 154 g of a 90% potassium hydroxide solution and 130 ml of dimethylformamide. 75.8 g of hexafluoropropylene are then pressed into the closed autoclave. The mixture is stirred for 25 hours at an autoclave pressure. After cooling, the mixture is concentrated on a rotary evaporator and the residue is dissolved in methylene chloride. The resulting solution is washed with water.
    ate
    00 00
    Nd 1
     O4
    dried over and concentrated. The residue is obtained and the crude product is chromatographed on a column of silica gel (1 m long, 10 cm in diameter) with a mixture of toluene and acetone (11: 1). 4-acetylamino-3,5 dichloro-1- (1,1,2, 3,3, 3-hexafluoropropyloxy) -be. Nzol is obtained in the form of light yellow crystals (mp, 113-1. 3 C - C) , 26 g of which is kept on the reverse flow for 1U h with 100 ml of ethanol and 30.6 ml of 37% hydrochloric acid. The reaction mixture is then concentrated, diluted with ice-cold soda and slightly basified. The product is extracted from the mixture with methylene chloride. The organic phase of the extract is washed with water, dried over and concentrated. The residue is purified by distillation. In this way receive the proposed compound of the formula
    but
    OCF, -CHF-CF
    in the form of a colorless liquid with so kip.
    91-96 ° C (0.001 torr).
    b) Preparation of N- (2,6-difluorobene.
    l), 5-dichloro-A- (1,1,2,3,3,3-hexafluoropropyloxy) phenyl-urea. A, 3 g 3,5-dichloro-4- (1,1,2,3,3 , 3-hexafluoropropyloxy) aniline is dissolved with stirring in 50 ml of dry toluene
    and at room temperature, excluding the humidity, 2.41 g of 2,6-difluorobenzoyl isocyanate III, dissolved in 10 ml of dry toluene, are added. The mixture is stirred for 1.2 h at room temperature. Then about 75% of the solvent is removed on a rotary evaporator, the precipitated precipitate is filtered under suction, washed with slightly cold toluene and hexane, then dried in vacuum and the proposed compound is obtained
    F С
    rS-CO-NH-CO-NH-OCFrCHF-Cr
    /
    35
    40
    45
    in the form of colorless crystals with so pl. 1 71-172 C. (compound 1).
    Found,%: C 39.90; H 1.50; N 1.50; F 27.70.
    Calculated,%: C 39, E5; H 1.50; N 1.58; F 2U, 23.
    Accordingly, the following compounds 2-4 of the formula (l)
    C1, C1
    iM-CO-JH-CO-NH-Q-O-CF CHF CF 1Cl
    M.p. 178-180 C.
    Found,%: C 41.00; H 1.80; N 5.50; F 21.90.
    Calculated,%: C 40.07; H 1.78; N 5.50; F 22.37.
    G, C1
     CO-NH-CO-NH-O-0-CF 2.CHFCF
    Cl
    m.p. 177-178 ° C.
    Found,%: C 38.50; H 1.60; N 5.20; F 25.00.
    Calculated,%: C 38.70; H 1.52; N 5.31, F 25.21.
     .- (
     // - CO-NH-CO-NH- (v / -0-CF2CHFCF3

    five
    0
    m.p. 156-1584.
    Found,%: C 41.30; H 1.84; N 5.80; F 26.60.
    Calculated,%: C 41.40; H 1.90; N 5.68; F 26.97.
    c) Preparation of the sodium salt of compound 1. 9.58 g (2,6-difluorobenzoyl) -N-C3, 5-dichloro-4- (1,1,2,3,3,3-hexa-fluoropropyloxy) -phenyl J -Urea suspended in 20 ml of absolute methanol. A solution of 0.43 g of sodium in 30 ml of absolute methanol is added dropwise to this suspension while stirring. A clear solution is obtained which is concentrated and the remaining product is dried in vacuo at room temperature. In this way receive the proposed compound of the formula
    45 /
    C1
    / -CO-N-CO-NH-4 0-CF7CnFCF3 No
    Cl
    in the form of colorless crystals.
    Next, get the salt of compound 2
    Formula I
    O- CO-N-CO-NH-- -0-CF2CHFCF3
    Cl lijaCl
    d) Preparation of the tetrabutylammonium salt of compound 1. 2.56 g of H- (2,6-di5. 158 fluorobenzoyl), 5-dichlorop-4- (1,1,2, 3,3,3-hexafluoropropyloxy) phenylJ-Mo - Cheviny suspended in 30 ml of methanol. While stirring, 5.2 g of a methanol solution containing 1.3 g of tetra-n-butylammonium hydroxide are added to this suspension. Get a bright solution. This solution is concentrated and the crude product remaining in the form of a precipitate is suspended in hexane, the filter is removed, washed with hexane once more and then dried. Thus obtained the proposed compound of the formula

    CO-N-CO-NH-.O-CF CHFCFji FCl
    s (pC, H9) ®
    in the form of colorless crystals.
    Example 2. Preparation of N- (2,6-difluorobenzoyl), 5-dichloro-4 - (. 1, 1
    2,3,3,3-hexafluoropropyloxy) phenyl J-urea.
    3.54 g of 3,5-dichloro-4-i, 1, 2,3,3,3-hexa-tho-propane-propyloxy) -phenylisocyanate is dissolved from 1.57 g of 2,6-difluorobenzamide while stirring in 30 ml of dried xylene. Then the mixture is stirred further for 15 hours at a temperature of 130 ° C. After that, xylene is removed in a rotary evaporator and the precipitated precipitate is filtered off with Kutch and re-crystallized from a mixture of toluene and hexane. Thus receive the target compound of the formula
    I FC1
    -CO-NH-CO-NH- 0 0CFrCHF-Cr3
    , R -
    in the form of colorless crystals with so pl. 171-172 ° C (compound 1).
    Example 3. Action against Musca domestica.
    50 g of freshly prepared nutrient medium for the larvae are weighed into glasses. From a 1% by weight acetone solution of the corresponding active substance, a certain amount is pipetted to the nutrient medium in the glasses, so that an active substance concentration of 800 ppm is created. After stirring the medium, the acetone is evaporated for at least 20 hours.
    Then, depending on the active substance and the concentration in the glasses containing the treated in this way
    ten
    20
    25
    nutrient medium, placed on 25 one-day larvae of Musca domestica. After the larvae have pupated, the pupae are separated from the medium by washing with water and deposited in the vessels covered with reticulate lids. The pupae washed from each composition were counted (toxic effect of the active substance on the development of larvae). Then after 10 days. The number of flies hatched from the pupae is determined. The compounds of formula (I) according to example 1 exhibit 50-60% efficiency in the indicated experiment.
    Example 4. Action against Lucilia sericata.
    To 9 ml of growth medium is added with 1 ml of an aqueous preparation containing 0.5% by weight of the active substance. Then, about 30 newly formed Lucilia sericata larvae are added to the growth medium, and after 48 and 96 hours, the insecticidal activity is determined by determining the kill.
    The compounds of the formula (1 according to example 1) in this experiment show 50-60% effectiveness against Lucilia sericata.
    Example 5. Action against AeJdes argypti.
    On the surface, 150 ml of water in the tank is pipetted with a 0.1% by weight aqueous acetone solution of the active substance in such an amount that a concentration of 800 ppm is formed. After evaporation of the acetone, 30-40 2-day-old Aedes larvae are placed in a container. After 1.2 and 5 days. determine the killing rate.
    The compounds of formula (I) according to example 1 show 50-60% efficacy against Aeidee aegypti in this test.
    Example 6. Insecticidal intestinal action.
    a) Cotton plants about 25 cm tall in a pot are sprayed with aqueous emulsions of the active substance containing the active substance at concentrations of 3, 12, 5 and 50 ppm. After the sprayed coat has dried on, the cotton plants are populated with Spocloptera littoralis or Heliothis virescens in the third larval stage. The test was carried out at 24 s and a relative humidity of 60%. After 2 days, the percentage is determined.
    thirty
    five
    0
    five
    0
    larvae frustrations with respect to and treated control samples.
    Compounds 1-4 according to Example 11 show an efficacy of 80-100% against the Spodoptera larvae at a concentration of 3 ppm. Compound 1 at concentration of 12.5 ppm and compound 2 and 3 at a concentration of 50 ppm-JQ e show 80-100% efficacy (killing) against Feliothis larvae.
    b) Comparative experience. Experiment A is repeated with the aid of the proposed compound 1 and two compounds known from the prior art. In contrast to experiment, the larvae of the larvae were determined only after 7 days. Table 1-1 shows the concentration of JQ 11 active substances used, the compounds used and the results obtained,
    I
    I PRI me R 7. Action against
    ijlpilachna varivestis. . 25: Phaseolus vulgar plants with a height of (|) about 15-20 cm (common beans, sustova) are sprayed with aqueous emulsion preparations containing the active substance in concentration of 800 ppm. After drying the sprayed coating, 5) larvae of Epilachna Varivestis (Mexican boar weevil) in the fourth larval stage are placed on each) vestania. Subject invasions are covered with a plastic cylinder covered with a copper mesh lid. The test was carried out at 28 ° C and a relative humidity of 60%. After 2-3 days, the percentage of deaths was determined. To assess the possible damage from the gluttony (Antifuding effect), impaired development and molting of experimental insects, they are observed for another 3 days.
    45
    The compound of formula (l) according to example 1 shows 50-60% efficacy in this test.
    Example 8. Ovtsidnoe action against Heliothis vireseens ;.
    The appropriate quantities of the wettable powder preparation, containing 25 wt.% Of the test active substance, are mixed with a corresponding amount of water so that a water emulsion is obtained with an active substance concentration of 800 ppm.

    five
    0
    five
    In these containing the active substance in the emulsion, one-day masonry of Heliothis eggs on cellophane is immersed for 3 minutes and then filtered on a round filter. Processed eggs are laid out in Petri dishes and kept in the dark. H-8 days set hatching in comparison with untreated control samples.
    The compounds of formula (I) according to example 1 exhibit high efficacy in this test.
    Example 9. Effect on Laspeyresia pomonella (egg).
    Put the eggs of Laspeyresia pomonella at the age not older than 24 hours on the filter paper for 1 min in an acetone-water solution, containing 800 ppm of the test substance. After drying, the egg solution is laid out in Petri dishes and left at. After 6 days, the percentage of hatching from the treated eggs is determined for the percentage of killing.
    The compound of formula (I) according to example 1. shows 50-60% efficiency in the indicated experiment.
    Example 10. Effect on reproduction of Anthonomus grandis.
    Adults of Anthonomus grandis not older than 24 hours after hatching are placed in groups of 25 beetles in cages with lattice walls. Cells with beetles are then immersed for 5-10 s in an acetone solution containing 400 pro-millet of the test active substance. After the beetles have dried, they are placed for the purpose of copulating and laying eggs into closed cups of food. Delayed eggs are drained two or three times a week with running water, counted, disinfected by placing for 2-3 hours in an aqueous disinfectant and then deposited in cups containing a suitable larval diet. After 7 days, the percent mortality of the eggs is determined, i.e. number of larvae developed from deposited eggs.
    In order to determine the duration of the reproduction effect of the test active substance, another control test is performed on the laying of eggs of beetles, i.e. within 4 weeks Bonding is performed on the basis of a decrease in the number of deposited eggs and larvae that have developed on them.
    in comparison with untreated control samples.
    The compounds of formula (I) according to example 1 exhibit high efficacy in this experiment.
    Example 11, Action against Anthonomus grandis (adults).
    Two planted cotton plants in the sixth deciduous stage are sprayed with a water-wettable emulsion preparation containing 400 ppm of the test substance, respectively. After drying the sprayed coating (approximately 1.5 hours), each plant is colonized with 10 adult beetles (Anthonomus grandis. Then, treated plants populated with experimental insects wear plastic cylinders, the upper openings of which are closed with gauze to prevent the beetles from spreading. The plants treated in this way withstand and a relative humidity of 60%. The evaluation was carried out after 2, 3, 4, and 5 days compared to untreated control samples.
    The compound of formula (l) according to example 1 shows 50-efficacy in this test.
    Example 12. Insecticidal action against Plutella xylostella.
    Planted Chinese cabbage plants (pot size 10 cm in diameter) in the fourth deciduous stage are sprayed with aqueous emulsions of the active substance, which contain the active substance at a concentration of 0.8 ppm and dry on plants
    After 2 days, the treated Chinese cabbage plants were populated each with 10 Plutella xylostella larvae in the second larval stage. The test was carried out at 24 ° C and a relative humidity of 60%. The test is performed after 2 and 5 days, the percentage of larvae killing is determined.
    In this experiment, compound 1 according to example 1 shows 100% efficacy (kill).
    Example 18. Activity, reducing the voracity of snails.
    Under controlled conditions, five slugs (Arion rufus) are left in one cage for four fresh lettuce leaves for 17 hours. In this case we are talking about
    0
    0
    five
    j
    compulsory experiments in the course of which either untreated or untreated leaves are offered. The concentration of the active substance in the aqueous preparation used for the application is 0.5% by weight. The indicator of voracity is determined on the basis of the difference in mass, photocopies of the blasting and in accordance with the criteria for visual assessment in comparison with untreated control specimens. Along with this, the possible killing of experimental animals is also determined.
    The compounds of formula (I) according to example 1 show 50-60% efficiency in this experiment.
    The compounds obtained are low-toxic compounds and exhibit higher activity compared to lime compounds of similar structure.
    Formula of invention
    A process for the preparation of substituted N-benzoyl-N-3,5-dichloro-4-hexafluoropropyl-oxyphenylureas of the general formula
    .RI
    -CO-NH-CO-NH fy-OCb-CHF-CF.
    -, - -C -W
    R
    Cl
    Where
     hydrogen or fluorine;
    fluorine or chlorine, or their alkaline, or ammonium salts, characterized in that the compound of formula
    topics
    40
    45
    subjected to interaction with the compound of the General formula:
    50
    five
    where at x nh or if x n
    ,, Y N С О, Y NH
    2
    in an organic solvent, the compounds thus obtained are converted into alkali or ammonium salts, if necessary.
    FCl
    i0-CO-NH-CO-NH-iS O-CF -aiFCF,
    FCl
    (Compound 1)
    J I -CO- H-CO - NH-O-0-CF2-CHFi
    Cl (.Analog J
    , F / Cl Q-CO-Nll-CO-NH-O-O-CIr-CHF
    . TCl
    (Analog
    100 100 90 100
    67 90 23 70
    8 10
    权利要求:
    Claims (1)
    [1]
    The claims of tsami.
    The compound of formula (i) according to example 1 exhibit 5060% efficiency in this experiment.
    Example 12. Insecticidal action against Plutella xylostella.
    Chinese cabbage plants planted in a pot (pot size 10 cm in diameter) in the fourth deciduous stage are sprayed with aqueous emulsions of the active substance, which contain the active substance at a concentration of 0.8 ppm and dry on the plants.
    After 2 days, the treated Chinese cabbage plants populate each with 10 larvae of Plutella xylostella in the second larval stage. The experiment is carried out at 24 ° C and relative humidity of 60%. Valuation is carried out after 2 and 5 days, determine the percentage of killing larvae.
    In this experiment, compound 1 according to example 1 shows 100% efficiency (killing).
    Example 18. Activity, reducing the gluttony of snails.
    Under controlled experimental conditions, five slugs · (Arion rufus) are left for 17 hours in one cup with four fresh lettuce leaves. In this case, we are talking about
    The method of obtaining substituted N-benzoyl-N'-3,5-dichloro-4-hexafluoropropyl30 'oxyphenylureas of the General formula
    -C0-NH-C0-NH
    S2 C1 where R is hydrogen or fluorine;
    R - fluorine or chlorine, or their alkaline, or ammonium salts, characterized in that that a compound of the formula is reacted with a compound of the general formula:
    where at X or if X =, NH ^, in an organic solvent, the compounds obtained in this case are converted, if necessary, into alkaline or ammonium salts.
    eleven
    Compound Efficiency (killing),% at compound concentration, ppm 0.4 | 0.8 | 0.8 | 1,5
    ((5-CO-NH-CO-NH- <0H 0-tf 2 -CHFCF)
    F vl
    (Compound 1)Λ IO-SO-MN-SO-IN-O-O-SGG-CISg(Analog)Q-C0-NH-C0-NH-Q-O-CF! -CHF2 100 100 90 100 67 90 23 70 (Analog) C * 8 10 0 0
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    同族专利:
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    DK488186A|1987-04-15|
    EP0219460B1|1991-05-02|
    CN1014110B|1991-10-02|
    DK111692D0|1992-09-10|
    ES2038125T3|1993-07-16|
    CY1683A|1993-10-10|
    ZW20486A1|1987-06-17|
    GB8910036D0|1989-06-21|
    JPS6293268A|1987-04-28|
    IL80271A|1991-12-15|
    DE3679024D1|1991-06-06|
    KR870003975A|1987-05-06|
    BR8604995A|1987-07-14|
    GB2217324A|1989-10-25|
    GB2182329A|1987-05-13|
    KR900008136B1|1990-10-31|
    EG17946A|1992-06-30|
    GB8624335D0|1986-11-12|
    GB8910035D0|1989-06-21|
    GB2217323B|1990-03-28|
    SG117592G|1993-01-29|
    ZA867736B|1987-06-24|
    MX4015A|1993-09-01|
    HK33893A|1993-04-16|
    IL80271D0|1987-01-30|
    GB2182329B|1990-02-14|
    EP0219460A3|1988-04-20|
    CA1291151C|1991-10-22|
    EP0219460A2|1987-04-22|
    MX173307B|1994-02-15|
    GB2217324B|1990-03-28|
    TR23026A|1989-02-10|
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    DK488186D0|1986-10-13|
    GB2217323A|1989-10-25|
    AU597278B2|1990-05-31|
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    引用文献:
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    DE2726684A1|1977-06-14|1979-01-04|Hoechst Ag|Insecticidal di:halo-benzoyl-phenylurea derivs. - useful for plant protection or textile preservation|
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    US4418991A|1979-09-24|1983-12-06|Breger Joseph L|Presbyopic contact lens|
    ZA825470B|1981-07-30|1984-03-28|Dow Chemical Co|Substituted n-aroyl n'-phenyl urea compounds|
    DE3217620A1|1982-05-11|1983-11-17|Bayer Ag, 5090 Leverkusen|2,5-DIHALOGENBENZOYL UREA, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PEST CONTROL|
    DE3580444D1|1984-10-18|1990-12-13|Ciba Geigy Ag|Benzoylphenylharnstoffe.|EP0221847A3|1985-10-29|1988-03-23|Ciba-Geigy Ag|Benzoyl urea salts|
    DE3613062A1|1986-04-18|1987-10-29|Hoechst Ag|N-BENZOYL-N'-PHENYLUREAS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PEST CONTROL|
    IT1213420B|1986-12-19|1989-12-20|Donegani Guido Ist|"N-N'-3-CHLORINE -41,1,2-TRIFLUORO-2-ETHOXYOUS PHENYL UREA WITH INSECTICIDE ACTIVITY.|
    IT1230675B|1987-09-04|1991-10-29|Donegani Guido Ist|N--N'-2-ALO-4ETHOXY) PHENYL UREE INSECTICIDE ACTIVITY|
    DE3740633A1|1987-12-01|1989-06-15|Bayer Ag|SUBSTITUTED BENZOYLUREA|
    GB8905741D0|1989-03-13|1989-04-26|Shell Int Research|Process for preparing carbamates,and intermediates therin|
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    法律状态:
    2007-09-20| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: MM4A Effective date: 20031014 |
    优先权:
    申请号 | 申请日 | 专利标题
    CH442085|1985-10-14|
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