• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Disclosed is a method of fighting fungus infections by using compounds having the general formula: wherein R is H, C1-C4 alkyl, alkenyl or alkynyl; n is 1 or 2; A represents a C1-C6 alkylene bridge, an arylene or a heterocyclic bridge; X represents 0, S, SO or S02; R1 is selected from C1-C6 alkyl, optionally substituted phenyl, polyfluoroalkyl containing 1 to 4 carbon atoms and at least 2 fluorine atoms, and poiyfluoroalkenyl containing 2 to 4 carbon atoms and at least 2 fluorine atoms, excluding those compounds of general formula (l) wherein A is alkylene, n is 2 and R1 is C1-C6 alkyl.
    公开号:SU1553005A3
    申请号:SU874202402
    申请日:1987-04-14
    公开日:1990-03-23
    发明作者:Менхони Августо；Камаджи Джованни；Гоццо Франко；Миренна Луиджи；Гараваглиа Карло
    申请人:Монтедисон С.П.А.(Фирма)；
    IPC主号:
    专利说明:

    The invention relates to chemical methods of controlling plant fungal diseases based on derivatives of 1- (2-methoxyiminoacetyl) urea.
    The purpose of the invention is to increase the fungicidal activity of the method.
    Example. Preparation of 2- (tetrafluoroethoxy) ethyl urea.
    20.6 g of 2-hydroxyethyl urea obtained from ethanolamine according to known methods, are added to a suspension of 0.5 g of sodium hydride in 100 ml of anhydrous mixture of dimethylformamide and tetrahydrofuran in a 1: 1 ratio. with stirring, kept at 0 ° C in a stream of nitrogen.
    After the exothermic reaction is complete, the mixture is allowed to warm to room temperature and the suspension is again stirred for 30 minutes. Then the reaction apparatus was evacuated and 4.8 L of tetrahydrofluoroethylene was added thereto. The process of gas absorption continues for 2 hours with the release of a small amount of heat, which is removed by means of a water bath with a temperature of 10 C.
    At the end of the reaction, the mixture is carefully acidified by adding concentrated hydrochloric acid, the solvents are evaporated from it under reduced pressure, and the residue is treated with 150 ml of a mixture of diethyl ether and ethyl acetate in a 1: 1 ratio.
    The mass is then filtered and the filtrate is evaporated under reduced pressure until a constant weight is reached, resulting in 36 g of 2- (tetrafluoroethox) -ethyl urea as a light yellow liquid.
    PRI mme R 2. Preparation of 1-cyanoacetyl-3- (2g-tetrafluoroethoxyethyl) urea.
    SP
    ate
    with
    ate

    G4
    A mixture containing 20.0 g of 2- (tetra-} toretoxy) -ethyl urea (example 1), 5 g of cyanoacetic acid and 100 ml of xusic anhydride is gradually heated to 70 a C and maintained at this temperature for 2 hours. Then this the mixture is cooled, evaporated under reduced pressure, the solid residue is filtered off and washed with diethyl ether.
    18.3 g of the crude product is crystallized from ethyl acetate, to give 10 g of 1-cya-ava-acetyl-3-C3-tetra-tapsoroethyl) -urea with a melting point of 115-116 ° C. PRI me R 3. Preparation of 1- (2-hydroxyimino cyanoacetyl) 3- (2-tetrafluoro-ethoxyethyl) -urea.
    11 g of such a compound with a melting point of 164-165 ° C are obtained by passing gaseous hydrogen chloride in the form of bubbles through a solution that includes 20 g of 1-cyanoacetyl-3- (2-tetrafluoroethoxyethyl) urea (example 2) and 46.6 ml n -propyl nitrite in 33.3 ml of tetrahydrofuran, until a clear acid reaction occurs, allowing the temperature to reach 50 ° C. The mixture is then cooled to room temperature, stirred for 2 hours, then left to stand overnight. The solvent is then evaporated under reduced pressure and the residue is washed with a mixture of n-hexane and diethyl ether.
    II p and me R 4. Preparation of 1- (2-methoxyiminocyanoacetyl) -3- (2-tetrafluoroethoxyethyl) urea (compound 1. Prepare a mixture that contains 2 g of 1- (2-oxyiminoacetyl) -3- (2-tetrafluoroethoxyethyl) urea (Example 3), 0.87 g of potassium carbonate, 0.79 g of dimethyl sulfate and a catalytic amount of 18-crown-6-ether in 11.5 ml of acetone. The whole mass is stirred for 2 hours at room temperature is filtered and the liquid is evaporated under reduced pressure. The solid residue is treated with dichloromethane, and the resulting solution is washed with water, dried over sulfate This is evaporated under reduced pressure and 1 g of 1- (2-methoxyiminocyanoacetyl) -3- (2-tetrafluoro-ethoxyethyl) urea with a melting point of 106 -107 C is obtained in this way.
    PRI me R 5 Preparation of 4-tetrafluoroethoxyaniline.
    ten
    15
    20
    25
    -
    , 1. s, si-
    553005
    5b lina,
    ten
    15
    20
    25
    thirty
    35
    40
    45
    50
    55
    g of 4-hydroxy-P-cyclohexylidene prepared according to known methods, parts are added to the suspension 3.6 g of sodium hydride in the form of an 80% oily suspension in a mixture that includes 200 ml of THF (tetrahydrofuran), free from hydroquinone, and 150 ml of DMF (dimethyl fluoroamide) and which, with stirring, is held at 0 ° C in a stream of nitrogen.
    After the exothermic reaction is complete, the mixture is allowed to warm to room temperature and the suspension is again stirred for 30 minutes. The reaction apparatus is then evacuated and tetrafluoroethylene is added to it. The process of gas absorption (6.9 l) continues for 2 hours with a small amount of heat evolving, which is removed by means of a water bath with a temperature of 10 C. Then the reaction mixture is evaporated in vacuum, obtaining a residue, which is poured into water and extracted with diethyl by ether. The ether extract is treated with a 1: 1 mixture of water and hydrochloric acid at the boiling point of an organic solvent, which ensures hydrolysis of the intermediate imino. The aqueous acid phase is separated, basified to a pH of 10, sodium hydroxide is added, and extracted with diethyl ether. The ether extract is dried over sodium sulfate and evaporated under reduced pressure and the residue is distilled in vacuo (at a temperature of 118-120 ° C and a residual pressure of 0.05 mm Hg), resulting in 14 g of 4-tetrafluoroethoxyaniline.
    Example 6: Preparation of 4-tetrafluoroethoxyphenylurea.
    10 g of 4-tetrafluoro-ethoxyaniline, prepared according to example 1, was reacted in 40 ml of water and 10 ml of a 1: 1 mixture of hydrochloric acid, with 3.9 g of potassium cyanate. This mixture is stirred for 30 minutes, and the resulting solid is filtered, washed with cold water and dried, yielding 10.5 g of the desired substance with a melting point of 167-168 ° C
    The IR and H-NMR spectrogram data corresponded to the structure of the compound of this example.
    Example. Preparation of 1 cyanoacetnp-3- (4-heterofluoroethoxyphenyl) - urea.
    In accordance with the procedure of Example 2, 10.5 g of 4-tetrafluoroethoxyphenyl urea are converted to 10.5 g of the compound of this example with a melting point of 205-2Ub ° C. PC-spectrogram of the product corresponds to the specified structure.
    Irimerv. Preparation of 1- (2-hydroxyimocyanoacetyl) -3- (4-tetrafluoro-ethoxyphenyl) urea.
    This compound, melting point 222-223 ° C, was prepared in Example 3 using as.
    plant) to 0 (fully infected plant).
    In tab. 1 shows the results regarding the determination results when testing compounds I and II, which are used in different doses, however, the inoculation is carried out 1 day after treatment.
    In tab. 2 shows the effects of reduced doses of Compound II in comparison with the reference compound 2-cyano-M- (ethylamino) - the starting material of the compound, semi-15 carbonyl -2- (methoxyimino) -acetamide of Example 7, and isoamyl nitride, which is known as Cymoxanil. that as a nitrosation agent. The data of the IR spectrogram of the product correspond to the specified structure.
    EXAMPLE 9 The preparation of 1- (2-me- 20 of which is summarized in Table 1. toxyimino cyanoacetyl) -3- (4-tetrafluoro- - Some of the tests for the evaluation of prothoxyphenyl) urea (compound II).
    This compound with a melting point of 162-163 ° C was prepared in Example 4 using the compound obtained in Example 8 as the starting material.
    The data of the IR and H-NMR spectrograms of the product correspond to the specified structure.
    II p and mep 10. Definition of profiT Such an action is evaluated in accordance with the same method used in the assessment, the results
    the phylactic fungicidal action against the microorganism Plasmopara viticola is carried out in accordance with the proposed
    25, but in this case, the inoculation is carried out 7 days after the treatment; at the same time, compound I is compared in a dosage of 0.03 g / l with the compound Cymoxanil in dosage
    30 0.03 g / l. From the averaged results obtained, it was concluded that the leaves treated with compound 1 were free of disease traces, whereas the leaves treated with the standard fungicidal action against the microorganism Plasmopara viticola (V. and C.) Berl and de Toni.
    Leaves of Dolzetto grapes grown in pots, which are kept at an ambient temperature of 25 ° C and 60% relative humidity, are sprayed on both sides with a water-acetone solution (20% by volume of acetone) containing test compounds per 1000 l / ha After t or 7 days after treatment, the leaves are sprayed (inoculated) from the bottom surface with an aqueous suspension of conidia Plasrao-para viticola with a concentration of 200,000 conidia / cube, cm; after soaking for 24 hours in a room with a saturated moisture atmosphere at 2 ° C, the plants are removed, placed in a room with 70% relative humidity, which is kept at 21 ° for a 7-day incubation period.
    Finally, the degree of infection is assessed using a rating scale ranging from 100 (health
    In tab. Figure 2 shows the effects of reduced doses of compound II in comparison with the reference compound 2-cyano-M- (ethylamino) -carbonyl -2- (methoxyimino) -acetamide, which is known as Cymoxanil.
    which are summarized in table. 1. - Some of the tests to assess the
    Such an action is evaluated in accordance with the same methodology used in the assessment, the results
    which are summarized in table. 1. - Some of the tests to assess the

    the phylactic fungicidal action against the microorganism Plasmopara viticola is carried out in accordance with the proposed
    method, but in this case, inoculation is carried out 7 days after treatment; at the same time, compound I in the dosage of 0.03 g / l is compared with the compound Cymoxanil in the dosage
    0.03 g / l. From the averaged results obtained, it was concluded that the leaves treated with compound 1 were free of traces of disease, whereas on leaves treated with the reference compound, only 33% of the surface was free of infection.
    In tab. 3 shows the evaluation data of the prophylactic fungicidal action of Compound II, which was used in various doses, with the inoculation being carried out 1 day after treatment, in comparison with the reference compound.
    In tab. Figure 4 shows the test data on the prophylactic effect of the compound I, which was used in different doses, and the inoculation was carried out 7 days after the treatment in comparison with the results obtained for the comparative compound.
    II p and mep 11. Determination of therapeutic fungicidal action against the microorganism Plasrnopara viticola (V. and C.) Berl. and de Toni. Leaf of Dolzetto grapes grown in pots that are kept at ambient temperatures
    than the treatment is carried out 24 hours after infection.
    权利要求:
    Claims (1)
    [1]
    25 ° C air and 60% relative humidity, sprayed from the lower surface of the leaf with an aqueous suspension of conidia Flasmopara viticola con-, invention formula with a concentration of 200,000 conidia / ml; after
    exposure for 24 hours in the room, a method of combating fungal infency in which the air is saturated with moisture, take plants by treating plants,
    21 ° C plants on both sides of the leaves which foresees the disease
    sprayed with a water-acetone solution of JQ or K ° T ° ORE this ° disease with pro-rum (20 vol. acetone), which contains, by derivative, 1- (2-methoxy | sting the tested compounds. nano-acetyl) urea, differs For a 7-day incubation period, so that, for the purpose of an extended period, the degree of fungicidal activity is visually assessed as an infection rate using the estimated indices of the derived 1- (2-methoxyimine-rating scale, the range of which is til) ureas use compound
    indices range from 100 (healthy plant formula) to 0 (completely infected ras Q
    TEN) .NC- -CNHCNH-A-0-CF4-CHI
    In tab. 5 shows the treatment data- 20NOCH
    action of compound I, which is A, is ethylene, phenylene,
    used in various doses, in the amount of 0.0018-0.0300 kg / ha.
    Table 1
    The degree of infection at the dose, g / l
    0.5 T 0.25 | O, 125 1 0.06 I 0.03
    II 100 100 100 100 100
    I100 100 100 100 100
    I ...
    Table2 Compound Infection rate at dose, g / l
    0,0150,0075 G 0.0037 1 0,018
    II100100100100 Tsimoksanil 90 50 25O
    Table3
    The degree of infection at the dose, g / l
    0.03 T 0.0075 | 0,0018
    II.100100100
    1- (2-Methoxy-imine cyanoacetyl) -3- (2-methoxyethyl) urea (known) 1006620
    than the treatment is carried out 24 hours after infection.
    Invention Formula
     1553005
    TableA.
    Infection Degree
    at dose, g / l
    0.03
    I100
    1- (2-Methoxyiminocyanoacetyl) -32- (methoxyethyl) urea (known) 55
    Table5 Compound Dose, g / l
    0.125 T 0.03
    I100100
    1- (2-methoxyimino cyanoacetyl) -3- (2-methoxyethyl) urea (known) 7335
    ten
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    同族专利:
    公开号 | 公开日
    ES2046181T3|1994-02-01|
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    DE3782362T2|1993-05-19|
    EP0250744A2|1988-01-07|
    BR8701808A|1988-01-26|
    AR242557A1|1993-04-30|
    CS262587A2|1989-07-12|
    DD262359A5|1988-11-30|
    EP0250744A3|1989-03-22|
    HU201647B|1990-12-28|
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    KR870009988A|1987-11-30|
    AU7135987A|1987-10-22|
    AU603357B2|1990-11-15|
    AT81847T|1992-11-15|
    IL82175A|1992-02-16|
    DE3782362D1|1992-12-03|
    JPS62242656A|1987-10-23|
    HUT44400A|1988-03-28|
    CS268689B2|1990-04-11|
    EP0250744B1|1992-10-28|
    ZA872567B|1987-11-25|
    CA1325810C|1994-01-04|
    KR940010278B1|1994-10-22|
    NZ219949A|1990-07-26|
    IL82175D0|1987-10-30|
    引用文献:
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    GB1452256A|1975-02-26|1976-10-13|Du Pont|Carbamoylacetamide derivatives|
    DK333276A|1975-09-11|1977-03-12|Du Pont|FUNGICIDE, SUBSTITUTED 2-CYANOACET AMID DERIVATIVES|
    US3979518A|1975-09-11|1976-09-07|E. I. Du Pont De Nemours And Company|Fungicidal alkoxy substituted 2-cyanoacetamide derivatives|
    DE2837863A1|1978-09-04|1980-03-13|Ciba Geigy Ag|OXIME DERIVATIVES FOR THE PROTECTION OF PLANT CULTURES|
    DE3327013A1|1983-07-27|1985-02-07|Basf Ag, 6700 Ludwigshafen|2-Cyano-2-oxyimino-N-carbamoylacetamides, fungicides containing them, and their preparation|US5231109A|1986-09-10|1993-07-27|Bayer Aktiengesellschaft|2-cyano-2-alkoximino-acetamides|
    DE3630732A1|1986-09-10|1988-03-17|Bayer Ag|2-CYANO-2-ALKOXIMINO ACETAMIDE|
    FR2646847B1|1989-05-12|1991-07-12|Rhone Poulenc Sante|N-PHENYL AMIDES, PROCESSES FOR THEIR PREPARATION AND THE MEDICAMENTS CONTAINING THEM|
    US6231660B1|1997-12-22|2001-05-15|The National Lime And Stone Co.|Manufactured granular substrate and method for producing the same|
    US8404259B2|2005-10-11|2013-03-26|The National Lime And Stone Co.|Dispersible granular substrate for pesticide delivery|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT20081/86A|IT1188653B|1986-04-15|1986-04-15|CYANACETOAMIDE-DERIVATIVES WITH ANTI-Fungal Action|
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