• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Novel 1-(2-aryl-1,3-dioxan-2-ylmethyl)-1H-imidazoles and 1H-1,2,4-triazoles wherein the 1,3-dioxane ring is optionally substituted with 1 to 3 substituents.
    公开号:SU1396966A3
    申请号:SU813320781
    申请日:1981-08-19
    公开日:1988-05-15
    发明作者:Херес Ян；Бакс Лео；Хубеле Адольф
    申请人:Жансен Фармасетика Н.В. (Фирма)；
    IPC主号:
    专利说明:

     s
    one
    The invention relates to a process for the preparation of new azole derivatives of the general formula
    where Q is CH or N;
    R is halogen;
    X and Y are independently C -C-alkyl or hydrogen, either in the A and 5th position or both in the 5th position or both in the 5th position of the 1,3-dioxane general nucleus, and at least one of X or Y is different from hydrogen, or their phytopharmaceutically acceptable acid addition salts are added to a solution of an oily residue in methylbenzene, 33.6 g of bromine are slowly added in such a ratio so that the reaction mixture spontaneously discolored, then the mixture is heated with 20 reflux for one more hour. The cooled reaction mixture is washed twice with water, dried, filtered and evaporated. Oily residue containing 2-
    Leas possessing an antimicrobial spectromethyl-2 (2,4-dichlorophenyl) -5-etid4-ASH-1, 3-dioxane are purified by distillation. Bp 150-153 ° C / 0.03 torr.
    rum biological action.
    The purpose of the invention is to obtain new azole derivatives having improved properties as compared with the known 1- (2-aryl-1,3-dioxan-2-ylmethyl) -1H-imidazoles and -1H-1,2,4-triazoles, in which 1,3-dioxane part is not replaced.
    Example 1. To a stirred solution of sodium methoxide, prepared from 3.7 g of sodium in 40 g of methanol, 10.8 g of 1H-imidazole and 270 parts of N, N-dimethylformamide are added. Methanol is distilled off to achieve
    969662
    3.8 g (26.5%) of 1-12- (2,4-dichlorophenyl) -5-ethyl-1, 3-dioxan-2-ylmethyl-1H-imidazole nitrate, m.p. 145.1 ° C,, Example 2. a. A mixture of 37.8 g of 1- (2,4-dichlorophenyl) ethanol, 35 g of 2-ethyl-1,3-hexanediol, 2 g of 4-methyl-benzenesulfonic acid, and 400 g of methylbenzene is heated in reverse
    10 fridge with water separator. After cooling, the reaction mixture is washed twice with 200 ml of water, dried over sodium sulfate, filtered and evaporated. To a heated under reflux solution of the oily residue in methylbenzene, 33.6 g of bromine are slowly added in such a ratio so that the reaction mixture spontaneously discolored, then the mixture is heated under reflux for another one hour. The cooled reaction mixture is washed twice with water, dried, filtered and evaporated. Oily residue containing 2-
     Bromomethyl-2 (2,4-dichlorophenyl) -5-ethidbromomethyl-2 (2,4-dichlorophenyl) -5-etid4-PRESH-1, 3-dioxane is purified by distillation. Bp 150-153 ° C / 0.03 torr.
    b. 23 g of 2-bromomethyl-2- (2,4-dichlorophenyl) -5-ethy-1-4-propyl-1,3-diokeane,
    5.6 g of imidazole and 100 g of dimethyl sulfoxide are mixed with 9.3 g of tertiary potassium butoxide and the mixture is stirred for 16 hours at 130 ° C, Ox. - each mixture is poured into 500 g
    water and extracted three times with 300 g of 1,1-oxybisethane. The combined organic layers are washed with 300 g of water, dried and evaporated. The oily residue is purified by the column method.
    The temperature of the mixture is 150 ° C. Then, 40 grams over silica gel with an addition of 19 g of 2-bromomethyl-2- (2,4-dichlorophenyl) -5-methyl-1,3-dioxane is added, and the mixture is stirred and heated under reflux for 5 hours (t .kip. 153 c). The reaction mixture is cooled and drunk into water. The product is extracted three times with 1,1-oxybisethane. The combined extracts are washed with water, dried, filtered and evaporated. The residue is purified by exchange of starting materials by preparative column chromatography of the compounds listed in Table 1 with silica gel; the first fraction is collected by elution with a mixture of 98% trichloromethane and 2% methanol. The eluent is evaporated and the residue is converted to nitrate in 4-methy-2-2-pentanone and 2,2-oxybis-propane. The salt is filtered off and crystallized from a mixture of 4-methyl-2-pentanone and-2,2-oxybispropane, using ethyl acetate as the eluent. The pure fractions were collected, the solvent was distilled off and the diastereomeric was obtained. a mixture of (2,4-dichlorophenyl) -5-ethyl-45 4-propyl-1,3-dioxan-2-ylmethyl 3-1H-imidazole as a brown oil, n 1.5486.
    According to the described method with the use of equivalent amounts of the corresponding (imidazole derivatives) and table. 2 (triazole derivatives).
    Example 3. a. A mixture of 56.7 g 55 1- (2,4-dichlorophenyl) ethanol, 32.4 g
    1,3-butadiol, 2 g 4-methylbenzene-. Photo acids and 400 g of methylbenzene are stirred and heated under reflux with a water separator in the topography over silica gel. The compounds shown in Table 1 are obtained from the corresponding starting materials.
    using ethyl acetate as eluent. The pure fractions were collected, the solvent was distilled off and the diastereomeric was obtained. a mixture of (2,4-dichlorophenyl) -5-ethyl-4-propyl-1,3-dioxan-2-ylmethyl3-1H-imidazole as a brown oil, n 1.5486.
    According to the described method, using the equivalent amounts of correlation over silica gel, the compounds shown in Table 1 were obtained with the appropriate starting materials.
    (imidazole derivatives) and table. 2 (triazole derivatives).
    Example 3. a. A mixture of 56.7 g of 1- (2,4-dichlorophenyl) ethanol, 32.4 g
    1,3-butadiol, 2 g of 4-methylbenzenesulfonic acid and 400 g of methylbenzene are stirred and heated under reflux with a water separator for 5 hours. After cooling, the reaction mixture is washed with water, dried, filtered and evaporated. 49.6 g of bromine are slowly added to the oily residue, dissolved in 525 g of trichloromethane heated to reflux. After the addition of bromine is complete, the mixture is stirred and heated under reflux for 1 hour. After cooling, the reaction mixture is washed twice with water, dried, filtered and evaporated. The yellow oily residue crystallizes from 500 g of cold petroleum ether (bp 40–60 ° C), digest at a low temperature, filtered, washed with cold petroleum ether (bp 40–60 ° C) and a diaste crystal is obtained rheomer mixture of 2- (2,4-dichlorophenyl) -2-bromomethyl-4-methyl-1,3-dioxane. M.p. 69-70, 5 ° C.
    b. A mixture of 10.8 g of potassium carbonate, 5.4 g of 1H-1,2,4-triazole, 20.5 g of 2- (2,4-dichlorophenyl) -2-bromomethyl-4-methyl-1,3- dioxane, 0.2 g of sodium iodide and 100 g of dimethyl sulfoxide are stirred for 36 hours at 100 ° C, cooled and drunk in 600 g of water. The reaction mixture is extracted three times with ethyl acetate, the combined organic layers are washed with 200 g of water, then dried, filtered and evaporated. The oily residue was purified by column chromatography over silica gel using ethyl acetate as eluant. The pure fractions are collected, the eluent is distilled off, and (2,4-dichlorophene1) -4-methyl-1,3-dioxane-2-; sh1methyl -1H-1,2,4-triazole is obtained. p, 1.5505. .
    Preparation of formulations.
    Example 4. Dusta.
    Dp of preparation of 5% dust is taken 5 hours of the active substance and 95 parts of talc.
    For the preparation of 2% dust, 2 parts of the active substance are used. including reel-dispersed silicic acid and 97 parts of talc.
    The active substances are mixed with carriers and primer. In this form, they can be processed into dusts for use.
    Example 5. Pellet m.
    Dp of preparing 5% granules - the following substances are taken, including:
    Active substance 5 Epichlorohydrin 0,25
    Cetyl polyglycolic ester 0.25 Polyethylene glycol 3.25 Kaolin (particle size 0.3-0.8 mm) 91 The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6 hours of 2-propanone. Polyethylene glycol and cetylpheno left ether are then added. The resulting solution is sprayed onto kaolin and the 2-propanone is stripped by vacuum.
    Such microgranules have been successfully used to combat soil fungi.
    Example 6. Wettable powders.
    To prepare 70% (a), 40% (b); The following components are used in the 25% (c, d) and 10% (d) wettable powder, including a. Active yes 70 Dibutylnaphthyl sodium sulfate 5
    Naphthalene sulfonic acid / phenolsulfonic acid / formaldehyde condensate 3: 2: 1.3
    Kaolin1O
    Talc12
    b.Active substance 40 sodium ligninsulfonate 5
    Acid dibutylnaphthal-sodium linsulfonate 1 Silicon kA: Lot, 54
    V.Active substance 25 Ligninsulfonate
    calcium 4.5
    .Mix talc / hydroxy-. .
    ethyl cellulose 1: 11.9 sodium dibutylnaphthalene sulfonate 1.5
    Silicic acid 19,5 Talc: 19.5
    Kaolin, 28.1
    g. Active substance25. Isoctylphenoxypolyethyleneethanol2, 5 Mixture of talc / hydroxyethylcellulose 1: 11.7
    Sodium aluminosilicate 8.3
    Kieselguhr16,5
    Kaolin46
    d.Active substance10
    five
    82
    A mixture of sodium salts of essential fatty
    sulfate alcohols
    Naphthalenesulfonic acid / formaldehyde condensate
    Kaolin
    The active substances are thoroughly mixed with additives in suitable mixers and ground in suitable mills and rollers. You get wettable powders with excellent wettability and suspension powders. Such wettable powders can be diluted with water to obtain suspensions of the desired concentration and can be used, in particular, to treat leaves.
    Example 7, Emulsifiable concentrates ..
    For the preparation of a 25% emulsifiable concentrate, the following substances are used, including:
    Active substance, l
    Epoxidized
    vegetable oil
    A mixture of alkylarylsulfonate / fatty ether
    alcohol and polyglycol
    Dimethylformamide
    Dimethylbenzene
    By diluting such a concentrate with water MdbcHo to obtain emulsions of the desired concentration, especially suitable for treating leaves.
    Biological examples.
    Example 8, Activity with respect to Cercospora personata (-Cer cospora drachidicolaJI.Ha seedlings of ground nuts.
    Groundnut seedlings at the age of 3 weeks are sprayed with a spray liquid (containing 0.02% of the active substance) prepared from a wettable powder of the active substance. After approximately 12 hours, the treated plants are contaminated by dusting them with a suspension of conidia of the fungi. The infected plants are then left for an incubation period of approximately 24 hours at 22 ° C at a very high relative humidity (90%), after which they are placed in the greenhouse. The extent of infection with the fungi is assessed 12 days after the introduction of the infection according to the number and distribution of parasites. Compared with untreated plants, 2.5
    ten
    five
    57.5
    five
    0
    five
    Q
    0
    five
    five
    0
    five
    In plants treated with a compound of formula (I), only limited growth of fungi is observed, or the growth of fungi is not observed at all.
    Example 9. Activity against Plasmopara viticda (Bert u Curt. Berl u De Toni) on vines.
    Residual protective action.
    Three seedlings of grape vines (Chasla cultivar), each having 10 leaves, are sprayed with a spray liquid (containing 0.06% of the active substance) prepared from a wettable powder of the active substance. After the napetum has dried, the plants are infected with a sporangia suspension of fungi from the lower surface of the leaves, and then placed for 8 days in the humidification chamber. After this period of time, the growth of fungi was observed in untreated plants. The extent of infection by the fungi is estimated based on the number and distribution of the spots.
    Compounds 1.9; 1.21; 2.9; 2.11} 2.16 completely suppressed the growth of fungi.
    Example 10. Activity against Erysiphe graminis on barley
    A. Residual protective action.
    Barley seedlings about 8 cm high are sprayed with spraying liquid (containing 0.02% of the active substance) prepared from a wettable powder of the active substance. After 3-4 hours, treated plants absorb conidia of the fungi. Then barley infestation is placed.
    into the greenhouse at a temperature of approximately 22 ° C. The extent of infection with the fungi is assessed 10 days after infection.
    b.Systemic action.
    Spraying fluid (containing 0.006% of the active substance} the amount is proportional to the volume of the soil) obtained from the wettable powder of the active substance is injected
    barley seedlings with a height of approximately 8 cm, and precautions are taken so that the external parts of the plants are not in contact with the spray liquid. After 48 hours, treated plants absorb conidia of the fungi. Infected barley seedlings are placed in a greenhouse at 22 ° C, and after
    At 10 days, the extent of infection with the fungi is assessed.
    Experience a. Compounds 1.9; 1.10; 1.11; 1.21i 2.9; 2.10; 2.11; 2.16; 2.27 complete inhibition is effected.
    Experience b. Compounds 1.16, 2.9, 2.11 completely suppress the growth of fungi.
    The compounds of formula (I) and, in particular, 1H-1,2 4-triazole jg derivatives are particularly active in relation to mildew (Erysiphe spp).
    Example 11. Activity against Botrytis cinerea on fodder beans.
    Seedlings of fodder beans with a height of approximately 10 cm are sprayed with a spray liquid (containing 0.02% of the active substance) prepared from a wettable powder of the active substance. After 48 hours, the treated plants are infected with a suspension of fungal conidia. After incubation of infected plants for 3 days at a relative humidity of 95-100% 25 and a temperature of 21 ° C, the fungal damage is assessed.
    A significant number of compounds of formula (I), for example, compound 1.9J 1.10; 1.11 and 1.21, completely suppress the growth of fungi at a concentration of 0.006% and even lower.
    Example 12. Activity against Hemilua vastatris on coffee trees.
    Residual protective action.
    Coffee trees about 1 cm high are sprayed with spraying liquid (containing 0.06% of the active substance) prepared from the .Q wetting powder of the active substance. After 24 hours, the treated plants are infected with a suspension of spores of rust fungi. Infected coffee trees are placed in a humidifier for 48 hours, then in a greenhouse at 22 ° C until a spore rust pad appears (approximately 4 weeks). The reduction in the number of spore pads serves as a measure of the activity of the substance under test.
    The compounds of formula (I) show a complete protective effect at the indicated concentration. Compounds 2.9; 2.10; 2.11; 2.16 show full protective activity.
    Example 13. Residual protective action against Venturia inaequalis on Blon seedlings.
    five
    g
    0 5
    P
    Q with
    Blon seedlings, 10–20 cm high, are sprayed with a spraying liquid (containing 0.06% of the active substance) prepared from a wettable powder of the active substance. After 24 hours, the treated plants are infected with a conidia suspension of the fungi. Then the plants are incubated at a relative humidity of 90-100% for 10 days in a greenhouse at 20-24 ° C. Fungus infestation is assessed 15 days after infection.
    Derivatives of 1H-1,2,4-triazole of formula (I) have a complete protective effect at a specified concentration of 0.06%. Even at a very low concentration of 0.006% of compound 2.9; 2.10; 2.11, no traces of the fungal infection were found 15 days after the infection.
    Example 14. Activity against Puccinia graminis on wheat.
    but. Residual protective action
    Wheat seedlings are sprayed 6 days after sowing with a liquid spray (containing 0.06% active ingredient) prepared from a wettable powder of the active substance. After 24 hours, the treated plants are infected with a suspension of fungal uredospores. After incubation for 48.4 at a relative humidity of 95-100% and a temperature of approximately, treated plants are placed in a greenhouse at a temperature of approximately 22 ° C. The appearance of spore rust pads is assessed 12 days after infection. Compounds 2.10 and 2.27 showed complete inhibition of fungal growth.
    The compound of formula (I) completely suppresses the growth of fungi.
    at. System action
    5 days after sowing, wheat seedlings are sprayed with spraying liquid (containing 0.006% of the active substance; the amount is proportional to the volume of the soil) prepared from a wettable powder of the active substance. After 3 days, the treated seedlings are infected with a suspension of fungal uredospores. After incubation for 48 hours at a relative humidity of 95–100% and a temperature of 20 ° C, the treated seedlings are placed in a greenhouse at a temperature of approximately 22 ° C. The appearance of spore nodules
    rust is evaluated 12 days after infection.
    Some compounds of formula (I), for example, compounds 2.9 and 2.10, completely suppress the growth of fungi by systemic action, and compound 2.11 completely suppresses growth even at a concentration of 0.002%.
    The results of biological examples 8-14 prove the exceptionally strong effect and wide spectrum of activity of the compounds of formula (I), especially 1H-1,2,4-triazolacetape, with respect to biologically different pathogenic fungi.
    Comparative tests and data.
    Activity against Puccinia disper sa on rye.
    Rye plants are sprayed 6 days after sowing with a spray formulation (containing various concentrations) prepared from a wettable powder of the active compound in a mixture containing acetone, tween and water. After 4 hours, the treated plants are infected with a suspension of fungi uredospores, after an incubation period of 24 hours at a relative humidity of 95-100% and at 20 ° C.
    The stretch is placed in a greenhouse, where the temperature is about. The appearance of a telepustule is assessed 12 days after infection.
    The first column of the table. 3 illustrates the percentage of antifungicidal activity (as compared to control compositions) after spraying plants with compositions containing 100, 10 and 1 hour / ml of the test compound.
    Residual protective action against Uromyces appendiculatus on beans during foliage treatment.
    Bean hats, having a height of 15 cm, are sprayed with a spray formulation (various concentrations) prepared from a wettable powder of the active substance in a mixture containing acetone, tween and water. After 4 hours, the treated plants are infected with a suspension of conidia of fungi, and infected plants are placed in a growth chamber at a relative humidity of 100% and at 200 ° C. Infection with fungi is assessed 10 days after the infection.
    . The second column of the table. 3 illus vriruet percent antifungicide active j
    0 5 o
    five
    0

    after spraying the plants with compositions containing 100, 10 and 1 ppm of the test compound.
    Activity against ferysiphe graminis on barley.
    Barley plants having a height of about 8 cm are sprayed with a spray formulation (various concentrations) prepared from a wettable powder of the active compound in a mixture containing acetone, Tween and water. After 2 hours, the treated plants are sprayed with conidia of fungi. Then infected barley plants are placed in a glass chamber at 22 ° C and the fungicidal attack is evaluated 10 days after the day of infection,
    In the third column of the table. 3 illustrates the percentage of antifungicidal activity (as compared to control compositions) after spraying plants with compositions containing 100; 10 and 1 h / mpn of the test compound.
    Residual protective action against Erysiphe cichoracearum on a picnic root.
    Young pickled plants of about 10 days old are sprayed with an aqueous solution containing: 100; 10 and 1 ppm of the test compound, while the control plants are left untreated. After the plants have dried, artificial infection with Erysiphe cichoracearum spores is carried out by slightly wiping the plants with abundantly infected leaves. Fifteen days after artificial infection, the degree of fungicidal attack is assessed by counting the number of spots on the plants.
    The results shown in the fourth column of Table 3 demonstrate the percentage of antifungicidal activity compared to control compositions.
    Activity against Botrytis cinerea on fruit (blocks).
    The pieces of the block are treated by immersing them in a solution containing 100, 10 and 1 ppm of the test compound. Next, the treated pieces are inoculated with spore suspensions applied to the surface of the incision and incubated for about a week at about 20 ° C at high humidity.
    The evaluation is carried out by calculating areas damaged by mold, and on the basis of such a calculation, the fungicidal activity of the tested substances is derived. The results presented in the fifth column of the table. 1 shows the percentage of antifungicidal activity compared to the blank compositions.
    The indicated blank positions contain the same components as those tested, but without the active component.
    Formulation of active substances (Table.
    in the form of wettable powders,%:
    four)
    Active substance
    Ligninsulfonate
    on three
    Sodium diisobutylnaphthalene sulfonate
    Silicic acid
    The percentages are given by weight. This formulation can be diluted with water, which leads to any desired stable homogeneous dispersion of the active substance (0, h / mpn).
    1. Action against Cercospora aga chidicola on peanut plants.
    Peanut plants at the age of 3 honey. sprayed with a diluted liquid obtained from the moistened powder of the active substance (200, 60; 20J 6 and 2 h / mpn of the active substance). After about 12 hours, the treated plants are sprayed with a fungus cannidiospore suspension. The infected plants are then incubated for approximately 24 hours at 90% relative humidity, and then transferred to a greenhouse with a temperature of about 22 ° C. The number of fungal infections is estimated after 12 days. The size and number of typical spots on the sheets present after the test are used in each of the
    criteria for evaluating the efficacy of test compounds.
    Ii. Action against Piccinia graminis on wheat.
    but. Residual-protective action.
    6 days after sowing, the wheat plants are sprayed with a sprinkling liquid prepared from a moistened powder of the active substance (200; 60; 20; 6; 2; 0.6 and 0.2 ppm of the active substance). After 24 hours, the treated plants are infected with a suspension of uredospore fungus. After incubation for 48 hours at approximately
    50
    55
    10 days incubated at 20-24 ° C in the greenhouse. The degree of damage to parto is assessed 15 days after charging. The size and number of typical p on the leaves that are present after the test are used as a criterion for evaluating the effectiveness of the tested substances.
    Iv. Action against Eryaiphe graminis on barley.
    but. Residual protective action
    Barley plants about 8 cm high are sprayed with dispersed liquid prepared from a moisturizer.
    0
    five
    0
    five
    0
    five
    0
    at a relative humidity of 95-100%, the infected plants are kept in a greenhouse at approximately 22 ° C. Evaluation of the telestopus growth is carried out 12 days after infection. The size and number of typical spots after the test are used as a criterion for evaluating the effectiveness of the tested compounds.
    b. Systematic action.
    The spray liquid obtained from the moistened powder of the active substance (60; 20; 6; 2; 0.6 and 0.2 ppm of the active substance relative to the volume of the soil) is applied to the soil with wheat plants 5 days after sowing. After 3 days, the treated plants are infected with a suspension of uredospore fungus. After incubation for 48 hours, approximately 11% 20 ° C 95-100% relative humidity is infected plants are stored in a greenhouse at approximately 22 ° C. An assessment of the development of a telepustress was made 12 days after infection. The size and number of typical spots on the Lis- | Tax that are present after the test are used as criteria for evaluating the effectiveness of the test substances.
    Iii. Residual protective action against Erysiphe graminis on Blon shoots.
    Blony saplings with young. The shoots are 10–20 cm long, sprayed with a sprayed liquid prepared from a moistened powder of the active substance (200; 60; 20; 6, 2; 0.6 and 0.2 parts of the active substance). After 24 hours, the treated plants are sprayed with a suspension of the conidiospores of the fungus. Then the plants are incubated for 5 days at a 90-100% relative.
    humidity, and over the next
    10 days incubated at 20-24 ° C in the greenhouse. The extent of the lesion is assessed 15 days after infection. The size and number of typical spots on the leaves after the test are used as a criterion for evaluating the effectiveness of the test substances.
    Iv. Action against Eryaiphe graminis on barley.
    but. Residual protective action.
    Barley plants about 8 cm high are sprayed with a liquid that is prepared from a moistened liquid.
    1313
    powder of active substance (200; 60; 20; 6; 2; 0.6 and 0.2 ppm of active substance). Treated plants are treated with a dust of fungus conidiospores after 3-4 hours. Infected barley plants are transferred to a greenhouse with a temperature of about 22 ° C, and after 10 days infection by fungus is assessed. The magnitude and number of typical fungus sprouts present on the leaves after the test are used as criteria for evaluating the effectiveness of the test substances.
    b. Systematic action. The sprayed liquid prepared from the moistened powder of the active substance (60; 20, 6, 2; 0.6 and 0.2 ppm of the active substance relative to the volume of the soil) is applied to the soil with a barley ground surface of about 8 cm. Precautionary measures are taken so that the sprayed liquid does not contact the plant above the soil level. After 48 hours, the treated plants are contaminated with dust of the fungus conidiospores. Infected barley plants are kept in a greenhouse at approximately 22 ° C, and after 10 days fungal infections are evaluated. The size and number of typical fungus sprouts present on the leaves after testing is used as a criterion for evaluating the efficacy of the test compounds.
    V. Interim protective activity against Bo.trytis on blocks.

    Artificially damaged blocks are treated by applying a drop of the decomposed liquid prepared from the moistened powder of the active substance (200; 60, 6 and 2 parts / mpn of the active substance) to the damaged parts of the block. The treated fruit is then inoculated with a spore suspension of Botrytis cinerea and incubated for about one week at approximately high relative humidity. The presence and size of rotten areas on fruit is used as a basis for assessing the degree of fungicidal activity. Rating scale:
    Indicator Activity,% 1More than 95
    380-95
    650-80
    9Less than 50
    6
    14
    Since each concentration in the above Tests was used in three parallel repeated experiments, each indicator in (the figure is the average of the three test results.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing azole derivatives of general formula (1)
    ABOUT
    Q R Y
    CH or N;
    halogen, independently With-C-alkyl or
    hydrogen, located either in the 4th and 5th position or both in the 5th position of the 1,3-dioxane core, and at least one of X and Y is different from hydrogen, their phytopharmaceutical acid addition salts are that azole
    Formula II
    ABOUT
    N
    H
    where Q has the indicated meanings, is reacted with a compound of the general formula (III)
    AT
    Y
    where R, X and Y have the indicated meanings;
    T - halogen,
    in an aprotic organic solvent, such as N, N-dimethylformamide or dimethyl sulfoxide, at 100-153 0 in the presence of an alkali metal alkoxide or carbonate, followed by
    isolation of the target product in a free-flowing state or in the form of phytopharmaceuticals of a chemically acceptable acidic acid 25.07
    26.07
    unique salt.
    priority according to criteria 25.07
    78 at Q - 07.27.78 at O -
    Tabl
    -n ,, with.
    Continuation of table 2
    100 o 70 o
    17 o
    90 o 50 o
    1.61
    CH
    2, -C1 1396966
    20 Continuation of table 3
    T a .. b l and c a D
    Note: A dash means no test.
    Lethal doses of compounds according to the invention significantly exceed 100 ppm.
    类似技术:
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    SU1431677A3|1988-10-15|Method of producing derivatives of 1h-1,2,4-triazole
    EP0228343A2|1987-07-08|Microbicidal 2-|1-phenyl-ethanone-|-Ketalderivatives
    SU1741597A3|1992-06-15|Method for struggle against fungus infection
    EP0040366A1|1981-11-25|Imidazolyl-vinyl ketones and carbinols, process for their preparation and their use as fungicides
    EP0069289A1|1983-01-12|Azole derivatives, process for their preparation and fungicides containing them
    EP0087105A1|1983-08-31|Fungicide-active derivatives of benzhydrole
    CH639657A5|1983-11-30|Dioxane and dioxolane derivatives having a microbicidal action
    同族专利:
    公开号 | 公开日
    NL7905687A|1980-01-29|
    DK312779A|1980-01-26|
    DD145106A5|1980-11-19|
    YU178179A|1983-06-30|
    DK156005B|1989-06-12|
    IL57875A|1982-12-31|
    ATA509079A|1982-01-15|
    FR2434164A1|1980-03-21|
    ES482662A1|1980-07-01|
    IT7949832D0|1979-07-23|
    PL217329A1|1980-04-21|
    PT69967A|1979-08-01|
    GB2027701A|1980-02-27|
    IT1162369B|1987-03-25|
    AR221889A1|1981-03-31|
    ZW13879A1|1981-02-25|
    AT367971B|1982-08-25|
    SE7906325L|1980-01-26|
    DE2930196C2|1992-10-22|
    IE791407L|1980-01-25|
    DE2930196A1|1980-02-21|
    GB2027701B|1982-12-15|
    TR20789A|1982-08-04|
    GR65805B|1980-11-05|
    US4939162A|1990-07-03|
    YU41873B|1988-02-29|
    BR7904721A|1980-05-20|
    IE48600B1|1985-03-20|
    DK156005C|1989-11-06|
    FR2434164B1|1984-11-16|
    HU185766B|1985-03-28|
    CA1164463A|1984-03-27|
    NZ191015A|1981-04-24|
    SE432688B|1984-04-16|
    AU524832B2|1982-10-07|
    AU4842579A|1980-01-31|
    PL123930B1|1982-12-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3575999A|1968-08-19|1971-04-20|Janssen Pharmaceutica Nv|Ketal derivatives of imidazole|
    US4079062A|1974-11-18|1978-03-14|Janssen Pharmaceutica N.V.|Triazole derivatives|
    US3936470A|1975-01-27|1976-02-03|Janssen Pharmaceutica N.V.|1,3-Dioxolan-2-ylmethylimidazoles|
    GB1533705A|1975-03-10|1978-11-29|Ici Ltd|Method of combating fungal infections in plants using imidazoles and 1,2,4-triazoles|NZ196075A|1980-02-04|1982-12-07|Janssen Pharmaceutica Nv|Agent to protect wood coatings and detergents from micro-organisms using a triazole|
    DE3025879A1|1980-07-09|1982-02-11|Basf Ag, 6700 Ludwigshafen|1,3-DIOXAN-5-YL-ALKYLTRIAZOLE, THEIR PRODUCTION, THEIR USE FOR REGULATING THE PLANT GROWTH AND MEANS THEREFOR|
    DE3026140A1|1980-07-10|1982-02-18|Basf Ag, 6700 Ludwigshafen|1,3-DIOXAN-5-YL-ALKENYLTRIAZOLE, THEIR PRODUCTION, THEIR USE FOR REGULATING THE PLANT GROWTH AND MEANS THEREFOR|
    DE3039087A1|1980-10-16|1982-05-19|Hoechst Ag, 6000 Frankfurt|1--AZOLES, THEIR SALTS, METHOD FOR THE PRODUCTION AND THEIR USE|
    US4479004A|1980-11-03|1984-10-23|Janssen Pharmaceutica N.V.|1-[2--1,3-dioxolan-2-yl-methyl]-1-H-triazoles|
    DE3043250A1|1980-11-15|1982-06-03|Degussa Ag, 6000 Frankfurt|2--AETHYL) -5,5-DIMETHYL-1,3-DIOXANE, METHOD FOR PRODUCING IT AND USING IT|
    EP0055059B1|1980-12-12|1985-03-27|Sankyo Company Limited|Diazole and triazole derivatives, processes for their preparation and anti-microbial compositions containing them|
    US5266585A|1981-05-12|1993-11-30|Ciba-Geigy Corporation|Arylphenyl ether derivatives, compositions containing these compounds and use thereof|
    DE3232737A1|1982-09-03|1984-03-08|Bayer Ag, 5090 Leverkusen|2-ARYL-2-AZOLYLMETHYL-1,3-DIOXEPINE|
    DE3401694A1|1984-01-19|1985-07-25|Basf Ag, 6700 Ludwigshafen|AZOLYLMETHYLCYCLOACETALE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A MEDICINAL PRODUCT|
    US5039332A|1985-09-19|1991-08-13|Uniroyal Chemical Company, Inc.|Substituted oxathiolanes|
    IT1196528B|1986-07-21|1988-11-16|Donegani Guido Ist|AZOLYL DERIVATIVES FOR ANTI-Fungal activity|
    US5274108A|1992-06-18|1993-12-28|SyntexInc.|Process for preparing 1,3-dioxolane derivatives|
    WO2010146115A1|2009-06-18|2010-12-23|Basf Se|Triazole compounds carrying a sulfur substituent|
    WO2010146116A1|2009-06-18|2010-12-23|Basf Se|Triazole compounds carrying a sulfur substituent|
    MX2011012425A|2009-06-18|2011-12-12|Basf Se|Triazole compounds carrying a sulfur substituent.|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH800578A|CH634842A5|1978-07-25|1978-07-25|2-Phenyl-2--imidazolylmethyl)-1,3-dioxane derivatives, processes for their preparation, microbicides containing these active substances, and their use|
    CH804178A|CH636873A5|1978-07-26|1978-07-26|2-Phenyl-2--1,3-dioxane derivatives, processes for their preparation, microbicides containing these active substances, and their use|
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