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    • 专利摘要:
    1,1,2-Triiodo-1-propene and 1-bromo-1,2-diiodo-1-propene derivatives having a formyloxy, alkanoyloxy, alkoxycarbonyloxy, alkoxycarbonylalkoxy, phenoxycarbonylalkoxy or benzyloxycarbonylalkoxy group at the 3-position are valuable anti-fungal and preservative agents having good heat and light stability.
    公开号:SU1519523A3
    申请号:SU802950406
    申请日:1980-07-11
    公开日:1989-10-30
    发明作者:Морисава Есихоро；Кониси Киуоси；Катаока Митсури
    申请人:Санкио Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    soda potassium in 10 ml of water. Then, the resulting mixture was stirred for 2 hours and little by little added to solution 8, A5 g of iodine. The resulting mixture was stirred for 3 hours at room temperature, after which it was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the resulting crystalline product was recrystallized from a mixture of ethnyl acetate and hexase. As a result, 6.9 g of compound No. 28 were obtained, iiMe of the melting point of 49-30 ° C.
    Calculated,%: C 14.19; H 1.38; 1 74.97.
    (% ,one,
    Found,%: C 14.05; H 1.26; 75.22. Infrared Absorption Spectrum
    (Nujol) :) g CM-: 1740.
    Example 2. 3-Octanoyloxy-1,1,2-triyod-1-propene (compound 9
    2 g of 1,1,2-triiodollyl alcohol was dissolved in 10 ml of pyridine, then 0.9 g of octanoyl chloride was added dropwise to the solution while cooling and stirring with ice. The resulting mixture was left overnight at room temperature, after which it was poured into a mixture of ice and water and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The resulting oily substance was absorbed by dried silica gel in a chromatographic column and eluted with a mixture of hexane - ethyl acetate in a 3: 1 volume ratio. As a result, t 9 was obtained as an oil. C 23.51: H 3.05;
    2.4 g of compound Calculated,%; I 67.74.
    C ,, N „0,1
    45
    3
    %:
    C 23.81; H 3.22;
    Found, I 67.80.
    Infrared Absorption Spectrum (liquid film) - cm: 1740.
    The Rf value (thin layer chromatography on silica gel, elution with a mixture of hexane - ethyl acetate in a volume ratio of 1: 1) is 0.59.
    Example 3. 3- (4-Chlorbutyri50
    C - ,. lErl2.
    Found,%: C 16.88; H 1.56; C1 6.93: Br 15.96: I 51.70.
    Infrared Absorption Spectrum (liquid film)), ax cm: 1740.
    The Rf value (thin layer chromatography on silica gel, elution with a mixture of hexane - ethyl acetate in a volume ratio of 1: 1) is 0.45.
    Implemented the processes described
    loxy) -1-bromo-1,2-dg 1od-1-propene (co - in examples 1-3, compounds were prepared.
    unity 1 55).
    5.6 g of propargyl alcohol was dissolved in 100 ml of water, to the solution doped into tab. 1. These compounds are represented by qi (the new symbols assigned to them in the above
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    A solution of 16 g of bromine in 20 ml of water and a solution of 7.2 g of 85% (w / w) potassium hydroxide in 20 ml of water were added simultaneously. After this, the solution was stirred for 3 hours, 25.4 g of iodine and a solution of 7.2 g of 85% (w / w) potassium hydroxide solution in 20 ml of water were added. After stirring for 3 hours at room temperature, the mixture was extracted with ethyl acetate, the extract was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under vacuum. The product formed was recrystallized from a mixture of ethyl adatate and hexane. 22 g of product were obtained with a melting point of 149-15 ° C.
    Calculated,%: C, 9.26; H 0.78; Br 20.56; I 65.28
    C HjOBrlj,
    P1 is found,%: C 9.32; H 0.83; Br 20.62; I 65.59.
    1.0 g of 3-bromo-2,3-diiodoalde alcohol, prepared as described above, was dissolved in 7 ml of pyridine. 0.4 g of 4-chlorobutyryl chloride was added dropwise to the solution with simultaneous cooling with ice and stirring. The reaction mixture was left overnight at room temperature, then diluted with water and extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate, the solvent was distilled off in vacuo. The resulting oily substance was absorbed by silica gel in a chromatographic column, eluted with a mixture of hexane and ethyl acetate in a 3: 1 volume ratio. As a result, 0.9 g of compound No. 55 was obtained in the form of an oil.
    Calculated,%: C 17.04; H 1.63; C1 7.19; Br 16.20; I 51.45.
    C - ,. lErl2.
    Found,%: C 16.88; H 1.56; C1 6.93: Br 15.96: I 51.70.
    Infrared Absorption Spectrum (liquid film)), ax cm: 1740.
    The Rf value (thin layer chromatography on silica gel, elution with a mixture of hexane - ethyl acetate in a volume ratio of 1: 1) is 0.45.
    Implemented the processes described
    - in Examples 1-3, compounds were prepared.
    given in table. 1. These compounds are represented by qi (the new symbols assigned to them in the above
    51
    Bbmie list of connections. For compounds obtained in the form of crystals, the melting point is given for compounds obtained in the form of oil (which is specified), their Rf value determined by thin layer chromatography on a fused gel with elution with a hexane-benzene mixture in a 1: 1 volume ratio.
    In addition, the corresponding properties of the compounds obtained according to examples 1-3 are indicated.
    T a
    blitz
    Continuation of table 1
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    Example A. 3-FORMSH1-1, 1,2-triyod-1-propene (compound 81).
    2.0 g of 2,2,3-triiodollyl alcohol and 30 ml of formic acid were heated under reflux and simultaneously stirred for 3 hours. After cooling the mixture, the precipitated crystals were removed by filtration, dissolved in ethyl acetate, adsorbed on silica gel in a chromatographic column and eluted with a mixture of hexane and ethyl acetate in a volume ratio of 3: 1. Compound K 81 was obtained as crystals with a melting point of 84-85 ° C. Infrared Absorption Max-CM: 1700.
    Example 5. 3-Formyloxy-1-bromo-1,2-diyod-1-propene (compound No. 82).
    The procedure was as described in Example 4, but 3-bromo-2,3-diiodoallyl alcohol was used. Compound P 82 was obtained as crystals with a melting point of 66-67 ° C.
    Infrared absorption spectrum Jvarc cm-: 1720.
    Example 6. 3-Methoxycarbonylmethoxy-1,1,2-triiod-1-propene (Compound No. 83).
    To an anhydrous solution containing 5.1 g of 55% oily sodium hydrate in 120 ml of diethyl ether was added 24 ml of anhydrous diethyl ether solution containing 5.6 g of propargyl alcohol. The mixture was stirred at room temperature for 1.5 hours, after which 20.9 g of ethyl bromoacetate was added dropwise. The mixture was left overnight, after which the excess sodium hydride was decomposed with methanol. After separation,
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    A filtrate is distilled off. 10 g of ethyl-alpha-propargyloxyacetate having a boiling point of 52-6P s (with A = 6 mm Hg) were obtained.
    Infrared absorption spectrum (liquid film): 3300, 2125, 1750.
    The value of Rf (determined by thin layer chromatography on silica gel with elution with a mixture of hexane: ethyl acetate in a volume ratio of 3: 1) is 0.43.
    17.8 g of iodine at 0-5 ° C was added to an aqueous solution containing 10 g of ethyl- (y-proparfoxytoxylacetate (preparation described above) and 9.3 g of 85% (w / w) potassium oxide gnprat). the mixture was stirred for 4 hours. A portion of the reaction mixture was acidified by adding hydrochloric acid and extracted with ethyl acetate. The extract was washed with water and dried. The solvent was distilled off. The resulting crude crystals were purified by thin layer chromatography on silica gel, eluting with ethyl acetate hexane (by volume) 10: 1. As a result, received 3-iodprop gil hydroxyacetic acid having a melting point from 102-104.
    An additional 17.8 g of iodine was added to the rest of the reaction mixture. The mixture was stirred at room temperature for 5 hours, acidified with hydrochloric acid, and extracted with ethyl acetate. The extract was washed successively with an aqueous solution of sodium hydrosulfite and water, after which it was dried. The solvent was distilled off, the crystals were recrystallized from a mixture of ethyl acetate and hexane. 28.13 grams of 2,2,3-triiodollyloxyacetic acid with a melting point of 94-95 C was obtained. 3 grams of thionyl chloride was added to 2 grams of triiodallyloxyacetic acid, obtained as described above, and the mixture was stirred at room temperature for 1.5 hours. The excess thionyl chloride was then removed. The reaction mixture was stirred with 10 ml of methanol, 0.5 ml of pyridine and left overnight. The resulting product was precipitated in a chromatographic column, passed through silica gel and eluted with ethyl acetate-hexane in a 4: 1 volume ratio.
    The result was 0.95 g of compound N 83, having a melting point of 67-68 ° C.
    Calculated. %: C 14.19; H 1.39;
    I 74, P7.
    SbN, 1, Oz
    Found,%: C 14.46; H 1.41; I 74.79.
    Infrared spectrum swallowed
    / woKc: 1735.
    Example 7. 3-Ethoxycarbonylmethoxy-1,1,2-triiod-1-propene (Compound No. 84).
    21.5 g of ethyl oi-propargyloxyacetate were dissolved in 300 ml of ethanol, 20.4 g of sodium ethylate were added to the solution at a temperature of 5-1 ° C, then 37.5 g of iodine for 15 minutes, after
    which the mixture was kept at this temperature for 30 minutes, and then stirred at room temperature for one hour. The reaction mixture was sequentially mixed with
    5 ml of acetic acid and 37.5 g of iodine were stirred at room temperature for 3 hours and left overnight. After that, the peaKiaioH mixture was diluted with 200 ml of water and extracted with ethyl acetate. The extract was successively washed with an aqueous solution of sodium hydrosulfite, an aqueous solution of sodium bicarbonate and water, and dried over anhydrous sodium sulfate. The solvent was distilled off, the resulting crystals were recrystallized from a mixture of ethyl acetate and hexane. As a result, obtain 59 g of compound No. 84, having a melting point of 73-74 ° C.
    Infrared Absorption Spectrum (Nujol). Kc cm-: 1730.
    Calculated,%: C 16.11; H 1.74; I 73.95.
    Found,%: C 16.07; H 1.66;
    I 73.19.
    Example 8. 3-Ethoxycarbonyl-methoxy-1,1,2-triiod-1-propene (compound f 84).
    2.84 g of ethyl-o-propargyloxyacetate was suspended in water, and 5.1 g of iodine and 2 ml of an aqueous solution containing 1.32 g of 85% w / w (weight / weight sodium hydroxide. After stirring at the same temperature for 3 hours, the mixture was mixed with 5.1 g of iodine, stirred

    at room temperature for 2 hours and left overnight. Then the reaction mixture was extracted with ethyl acetate, the extract was passed through sequentially with an aqueous solution of sodium hydrosulfite, an aqueous solution of sodium bicarbonate and water, and dried. After distilling off the solvent, the resulting residual product is passed through a silica gel column chromatography. As a result, 1.7 g of K 84 compound having a melting point of 73-74 ° C were obtained.
    Infrared absorption spectrum is given. on with ethyl acetate in a volume ratio of 3: 1. As a result, 1.7 g of compound No. 101 was obtained in the form of an oil.
    Calculated,%: C, 17.93; H 2.07;
    20
    25
    The corresponding compound corresponded to the spectrum of the compound obtained in Example 7.
    Example 9. 3- (2-Ethoxycarbonyltroxy) -, 1,2-triiodo-1-propene (Compound No. 101).
    25.8 g of methyl acrylate was added dropwise to a mixture of 16.8 g of propargyl alcohol and 0.1 g of sodium methoxide maintained at a temperature of 55-60 ° C. The mixture was heated at 80 ° C for 4 hours, then left overnight. Then the mixture was poured into ice-water and extracted with ethyl acetate. The extract was dried and cleaned by distillation. 25.8 g of methylp-propargypoxypropionate having a boiling point of 80-83 ° C (at a pressure of 10 mm Hg) were obtained.
    Infrared absorption spectrum
    I 71.04.

    Found,%: C 18.19; H 2.18; 70.83. Infrared absorption spectrum
    (liquid film),
    CM
    1740.
    cm-: 3300, 2120.35 chromatography
    (liquid film) - max 1740.
    3.2 g of methyl fi-propargyloxypropionate, prepared as described above, were suspended in 30 ml of water. 5.7 g of iodine and 5 ml of an aqueous solution containing 3 g of a 85% strength were added dropwise at 0-5 ° C to suspension-dd ZIN.
    The Rf value (thin layer chromatography: a silica gel, elution with a mixture of hexane - etchtacetate in a volume ratio of 3: 1) is 0.54.
    Carrying out the procedures described in examples 6-9, the compounds shown in Table 2 were obtained. 2 (for compounds obtained in the form of crystals, their melting points are given, and dp obtained in the form of oil (which is specified) is the primary moiety Rf (thin layer
    on silica gel, elution with a mixture of hexane - ethyl acetate in a volume ratio of 3: 1)). In addition, the corresponding properties of the compounds obtained according to examples 6-9.
    table 2
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    thioiyl chloride and heated until complete dissolution. Chatham mixture was stirred at room temperature for one hour, an excess of thionyl chloride was distilled off under reduced pressure. The resulting acid chloride was introduced into 10 MP of ethanol, the mixture was stirred for 2 hours. The solvent was distilled off, the residual distillation product formed was purified by passing it through a silica gel-filled chromatographic column, and elution was carried out with a mixture of hexa 71.04.

    Found,%: C 18.19; H 2.18; 70.83. Infrared absorption spectrum
    (liquid film),
    CM
    1740.
    chromatography
    The Rf value (thin layer chromatography: a silica gel, elution with a mixture of hexane - etchtacetate in a volume ratio of 3: 1) is 0.54.
    Carrying out the procedures described in examples 6-9, the compounds shown in Table 2 were obtained. 2 (for compounds obtained in the form of crystals, their melting points are given, and dp obtained in the form of oil (which is specified) is the primary moiety Rf (thin layer
    chromatography
    on silica gel, elution with a mixture of hexane - ethyl acetate in a volume ratio of 3: 1)). In addition, the corresponding properties of the compounds obtained according to examples 6-9.
    table 2
    Continuation of table 2
    Specific examples of the proposed compounds are listed below. Each of these compounds is numbered.
    1.3-Al (etoxy-1,1, 2-triyod-1-pro foam
    2. Z-Propionshuksi-1,1,2-tripod-1-propene
    3.3-Butyr1shoxy-1,1,2-triyod-1-propene
    -i Z-Isobutyryloxy-1, 1,2-trinod 1-propene
    5. W-Valeryloxy-1,1,2-triyod-1-propene
    7.Z-Hexansyloxy-1,1,2-triyod-1-propene
    8.3-Heptanosiloxy-1,1,2-triyod 1-propene
    9.Z-Octanesyloxy-1,1,2-triyod-1-propene
    10.3-Nonansyloxy-1,1,2-triyod-1-propene
    11.Z-Drkansiloxy-1,1,2-triyod-1-propene
    12.Z-Cromoacetoxy-1,1,2-triyod-1-propene
    13.3-Chloroacetoxy-1,1,2-triyod-1-propene
    14.Z-Dichloroacetoxy-1,1,2-triyo 1-propene
    15.Z-Trichloroacetoxy-1,1,2-triy one-1-drink
    16.3- (2-Bromopropionyloxy) -1,1, triiod-1-propene
    21. 3- (4-Chlorobutyryloxy) -1,1,2yod-1-propene
    27.З-Methoxycarbonyloxy-1,1,2-triyod-1-propene
    28.3-Ethoxycarbonyl 11-oxy-1,1,2-triiod-1-propene
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    29.3-PropokgikarG) P11ipokg, and-1,1,2-triyod-1-propene
    30.Z-Isopropoxycarbonshuksi-1,1,2-triyod-1-propene
    31.3-Kutoxycarbonyloxy-1,1,2-triyod-1-propene
    32.Z-Isobutoxycarbonyloxy-1,1,2-thr yud-1-propene
    33.3-Pentyloxycarbonyloxy-1,1, 2-TRIODE-1-propene
    35.3-Hexyloxycarbonyloxy-1,1,2-triyod-1-propene
    36.Z-Heptyloxycarbonyloxy-1,1,2-triyod-1-propene
    37.Z-Octyloxycarbonyloxy-1,1,2-triiod-1-propene
    38.3-Acetoxy-1-bromo-1,2-diiod-1-propene
    39.3-Propionyloxy-1-bromo-1,2-diiod-1-propene
    40.Z-Kutiryloxy-1-bromo-1,2-di-iodo-1-propene
    4 2 g 3-Valeryloxy-1-bromo-1,2-diiodo-1-propene
    48.3-Bromoacetoxy-1-bromo-1,2-diiod-1-propene
    49.3-Chloroacetoxy-1-bromo-1,2-diiod-1-propene
    50.3-Dichloroacetoxy-1-bromo-1,2-diiod-1-propene
    51.3-Trichloroacetoxy-1-bromo-1,2-diyod-1-propene
    52.3- (2-Bromopropionyloxy) -1-bromo-1,2-DIODO-1-propene
    55.3- (4-Chlorobutyryloxy) -1-bromo-1,2-diyod-1-propene
    56.3- (2-Bromisobutyrene) -1-bromo-1,2-diyod-1-propene
    58.Z-Methoxycarbonyloxy-1-bromo-1,2-diyod-1-propene
    59.S-Ethoxycarbonyloxy-1-bromo-1,2-diyod-1-propene
    60 3-Propoxycarbonyloxy-1-bromo-1,2-diyod-1-propene
    61.Z-Isopropoxycarbonyloxy-1-bromo-1,2-diyod-1-propene
    62.3-Nutoxycarboxy-1-bromo-1,2-diyod-1-propene
    63.Z-Isobutoxycarbonnloxy-1-bromo-1,2-diyod-1-propene
    64.3-Pentyloxycarbonyloxy-1-bromo-1,2-diyod-1-propene
    65.3-Hex1shoxycarbonyloxy-1-bromo-1,2-diyod-1-propene
    67. 3- (2-Chlortoxycarbonyloxy) - 1,1,1-triiodo-1-propene
    70. 3- (4-Chlorobutoxycarbonyloxy) - 1,1, 2-Tr1 Syiod-1-propene

    73, i- (2-o c:: with Ik pG1onilocox 1,1,2-triyod-1-propy
    75. 3; - (2-Chlotoethoxy) This is a hydrochloride space 1, 1,2-triyod-1-propene
    77. 3- (2-Bromethoxycarbonshox) 1-bromo-1,2-diyod-1-propene
    81.Z-Lormyloxy-1,1,2-triyod-1-propene
    82.3-T) ormyloxy-1-bromo-1,2-diyo 1-propene
    83.Z-Methoxycarboshitmethoxy-1,1 triiod-1-propene
    84.3-Ethoxycarbonate methoxy-1,1, triiod-1-propene
    85.Z-Propoxycarbonylmethoxy-1, 2-tripod-1-propene
    87.3-Kutoxycarbonylmethoxy-1,1 triiod-1-propene
    88.3-Methoxycarbonylmethoxy-1-bromo-1,2-DIOD-1-propene
    89.3-Ethoxycarbosh1lmethoxy-1-bromo-1,2-DIODO-1-propene
    90.3-Propoxycarbonylmethoxy-1-bromo-1,2-DIODE-1-propene
    91.3-Venzyloxycarbonylmethoxy-1,1,2-triyod-1-propene
    92.3-para-chlorobenzyloxycarbonyl methoxy-1,1,2-triiod-1-propene
    93.Z-phenoxycarbonylmethoxy-1,1 2-triyod-1-propene
    95.3-para-Chlorophenoxycarbonylmetoxy-1,1,2-triiod-1-propene
    96.3-ortho-methylphenoxycarbonyl-methoxy-1,1,2-triiod-1-propene
    97.3-meta-methylphenoxycarbonylmethoxy-1,1,2-triiodo-1-propene
    98.Z-para-Methylphenoxycarbonyl-methoxy-1,1,2-triiod-1-propene
    99.3- (2, D-Dichlorophenoxycarbonyl methoxy) -1,1,2-triiod-1-propene
    100.3- (2-Methoxycarboxy-1ethoxy) 1,1,2-triiod-1-propene
    101.3- (2-Ethoxycarbonylethoxy) - 1,1,2-triiod-1-propene
    102.3- (2-Propoxycarbonylethoxy 1,1,2-triiod-1-propene
    103.3- (2-Butoxycarbonyleto tox) 1,1,2-triyod-1-propene
    10A. 3- (2-phenoxycarbonylethoxy) 1,1,2-triyod-1-propene
    105. 3- (2-para-Chlorobenzyloxycar boncloethoxy) -, 1,2-triyod-1-propene.
    Of the compounds listed above, compounds 1, 28, 38, 59, 83 and 100 are preferred.
    The compounds prepared according to the invention are valuable antifungal and protective agents.





    ten
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    IQS.T)
    thirty
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    gadfi They are effective in combating the wide variety of fungi, especially I enicil 1 iuni, Asjierpil bis, Rhi: opus, niaotomium, C aclosporium, Fvisariuin, Pull ul aria and Aureobasidiiim, as well as other types of fungi, including Trichodemia and Mushrooms causing staining of wood. They are used to protect materials from damage under the influence of fungi that cause wood rot and the appearance of soft rot.
    Materials that can be protected and stained from the harmful effects of fungi by treating with the compounds obtained according to the invention include, in particular, wood, as well as various industrial-Fcne materials, such as moist wood pulp, b-mag, mat (or mat), fibers, leather, adhesives, dyes and synthetic resins (any organic materials that are susceptible to the harmful effects of fungi, can be washed (en)).
    The antifungal effect of the compounds of the invention is exemplified by the following experiments.
    Experiment 1. Resistance to light.
    Each of the year-tested compounds was dissolved in ethylene glycol monomethyl ether to produce a solution of 0.5% concentration (w / v). Each solution was then exposed to ultraviolet rays for 2 hours using a sterilization lamp. A paper disc with a diameter of 8 mm was immersed in each of the irradiated solutions. After removing the excess solution, the disks were air dried.
    Using paper discs prepared in this way, the compounds were tested for antifungal and protective action by the diffusion method. Antifungal activity was determined. using an agar medium containing a mixture of spores of Aspergillus niger, Trichoderma viride, usarium nioniliforme and Pullyularia pulliilans, the protective effect is on an agar medium containing Tyremyces palustris or Pycnoporus coccinens. Temperature
    maintained equal to) 25 ° C. Anti-IgG tests were performed using the proposed compounds and two controls; compounds, eliminating exposure to ultraviolet rays. In all cases, both npe; uiara and control compounds had an antifungal and preventive effect, estimated I as +.
    Experiment 2. Antifungal effects.
    Each of the tested compounds was dissolved in dimethylformamide to obtain a solution at a concentration of 1% (w / v). Then, to obtain test samples, pieces of bamboo meso and beech were cut in dimensions of 2x2x0.2 cm. Each of the samples was immersed in one of the test solutions for 5 s, dried
    in the air, made water (flow rate approximately 2 l / min) for one hour, high; in air for 24 hours, heated at 6 () (for 2 hours and sterilized with dry air.
     each sample was subjected to exposure for resistance to the growth of fungi. A suspension of one of the tested fungi was injected into each sample and cultured at 25 t for three weeks in a sterilized Petri dish containing wet filter paper. The following mushrooms were used: Aspergillus nip, er (mushroom No. 1); Trichoderrna viride (mushroom M 2); Fusa- rium moniliforrne (mushroom No. 3); Pullu laria pxilliilans (mushroom No. A). Nzuchadsh
    mycelium growth.
    The results are presented in table.5. T a b l Tf And a 5
    nineteen
    Used the following evaluation system:
    + no fungal growth was observed on the sample;
    i. only weak growth of fungi was observed on the sample;
    - on the sample was the growth of fungi.
    The proposed connections are listed under the numbers assigned to km in the above list of connections. 151952320
    Continuing} Table 1. five
    SRI; The known antifungal agent, pentachlorenol- (PCP) laurate, was used as a control. Untreated control samples of two woods were also exposed to various types of fungi.
    Experiment 3. Wood Preserving Effect.
    Each test compound was dissolved in methanol with the tightening of a solution of 0.05% (w / v) concentration.
    The compounds of the invention were tested under the numbers assigned to them in the list above and pentachlorophenodes (PCP).
    Samples of sapwood Sup, i, 2x2x1 cm in size, were cut out, each sample was sucked in vacuum by one of the solutions under study, then dried in air. After this treatment, the test samples were subjected (twice) to the next exposure; leaching with water (water feed rate about 2 l / min) for 5 hours, drying in air for 24 hours and heating at 60 ° C for 24 hours. After that, the samples were sterilized with dry air.
    Thus prepared each (each) was placed on a fungal mushroom 11, decomposed lignin of Corioli versicolor fungi or cellulose of Tyremyces palustrius fungi, which were preincubated in a sterilized Petri dish containing medium consisting of 2% maltose extract, 1% glucose and 0.5% peptone. In this case, the samples were subjected to forced decomposition by fungi during three weeks. To assess the safety effect of the tested compounds, the growth of the mycelium on the samples and the decrease in the compressive strength of the samples were determined. The results are presented in table 6.
    Table 6
    231
    The protective effect was evaluated according to the following evaluation systems
     no fungal growth was observed on the test samples; no change in compressive strength;
    + there is a weak growth of the mycelium on the tested samples, the compressive strength is slightly reduced;
    - growth of mycelium was observed on the tested samples, compressive strength decreased significantly.
    Experiment 4. Resistance to ultraviolet radiation.
    Each test compound was dissolved in 5 MP of ethylene glycol monomethyl ether of ether, resulting in a solution with a concentration of 0.2% (w / v). Each solution was injected into a suspended bottle and exposed to ultraviolet rays from a 15 W sterilization lamp installed at a distance of 18 cm from the bottle: the proposed compounds are for 10 hours; connections — prototypes — within an hour.
    A paper disk with a diameter of 8 mm was immersed in one of the solutions subjected to irradiation, the excess solution was removed with filter paper, and then the paper disks were dried. After that, the antifungal effect of each compound was determined by the diffusion method using a 45 mm diameter Petri dish with 4 ml of agar medium containing a mixture of fungi. The mixture of test fungi used in this experiment was identified in accordance with the following codes:
    (i) a mixture of wood-destroying fungi, namely: Coriolus versicolo Tyromyces palustrius and Pycnoporus coccineus;
    (ii) - a mixture of other mushrooms, a in the name: Trichoderma viride, Fesarium moniliforme, Aspergillus niger and Pul lularia pullulans.
    Mixture (i) was incubated for 7 days, mixture (ii) for 12 days.
    Determine the ability of test compounds to withstand exposure to fungi. The results are presented in table. 7
    The following evaluation system was used:
    + zone of slow growth of fungi was observed around the paper disk;




    24 watched
    on paperTable 7
    1 ++
    28 ++
    38 ++
    59 ++
    Triiodolyl alcohol - Experiment 5. Resistance to ultraviolet radiation.
    The tests were carried out in the same manner as described in Experiment 4, the difference was that the concentration of the solution was 0.3% (weight, / oO}, the duration of radiation was 20 hours both for the proposed compounds of the present invention and for Comparative compounds. Petri dishes had a diameter of 35 mm and contained 3 ml of agar medium. The incubation period was 7 days. The results are presented in Table 8.
    Table 8
    40
    Triiodallyl methyl ether
    Thus, testing the solutions of the compounds showed that they possess antifungal activity against a wide range of fungi, resistant to light and ultraviolet radiation in the presence of triffiol alcohol and its methyl ether. The preparations exhibit a higher fungicidal activity compared to pentachlorophenol.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    An antifungal composition containing the active compound and a solvent, characterized in that, in order to increase its activity and resistance to atmospheric conditions, it contains the compound of the general formula as an active compound
    C CY-CH20R
    de x r
    iodine or bromine;
    a formyl group, an alkanol group without a substituent or having 1 bromine atom of 15 or chlorine as a substituent, a C2-C8 alkoxycarbonyl group without a substituent or having 1 atom of bromine or chlorine as a substituent of 20 C, , -H, 4-alkoxy group, C, -C-alkoxycarbonylmethyl or ethyl group, phenoxycarbonylmethyl or ethyl group, benzyl 25 zyloxycarboxychroxy or ethyl group, and phenoxy or benzyloxy
    O
    5 0 5
    are unsubstituted or have 1 chlorine atom or 1 methyl group as a substituent,
    and as a solvent it contains ethylene glycol monomethyl ether, di-ethylformamide or methanol, in the following ratio, wt.%:
    Active connection 0.05-1.0
    SolventExtra
    Priority featured:
    09/14/79 when R is benzyloxy, an arbonyl methyl or an ethyl group, and phenoxy benzyloxy is unsubstituted or has 1 chlorine atom or methyl group as a substituent;
    05/13/79 with R-Cj-Cjg-alkanoyl group without a substituent or having 1 bromine atom of chlorine as a substituent, C2-Cd-apkoxycarbonyl group without a substituent or having 1 bromine atom or chlorine as a substituent. With, -C4-alkoksk-on group. C, -C-alkoxycarbonylmethyl or ethyl.
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    同族专利:
    公开号 | 公开日
    FR2460917B1|1982-12-10|
    SE448374B|1987-02-16|
    NO802066L|1981-01-14|
    DE3026431A1|1981-01-29|
    GB2053916A|1981-02-11|
    DE3026431C2|1988-07-21|
    FR2460917A1|1981-01-30|
    GB2053916B|1983-03-16|
    NO153966B|1986-03-17|
    CA1165327A|1984-04-10|
    NO153966C|1986-06-25|
    SE8005119L|1981-01-14|
    US4487781A|1984-12-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR2166143B1|1971-12-28|1980-02-15|Meiji Seika Kaisha|
    JPS5435430B2|1975-08-14|1979-11-02|
    JPS5379862A|1976-12-24|1978-07-14|Dainippon Pharmaceut Co Ltd|Iodepropargyl ethers|
    US4259350A|1978-03-15|1981-03-31|Sankyo Company Limited|Iodopropargyl derivatives, their use and preparation|
    EP0015044A3|1979-01-22|1980-10-15|Imperial Chemical Industries Plc|Tri-iodoalkenyl esters of n-substituted carbamic esters, their preparation and their use as biocides|
    GB2053916B|1979-07-13|1983-03-16|Sankyo Co|Trihaloallyl derivatives having anti-fungal and preservative activities|
    JPS57116026A|1981-01-13|1982-07-19|Sankyo Co Ltd|Preparation of trihaloallyl derivative|
    JPH05320006A|1991-02-18|1993-12-03|Sds Biotech Kk|Agricultural and horticultural fungicidal composition|
    JPH05320484A|1992-05-27|1993-12-03|Sanko Chem Co Ltd|Copolyester composition|GB2053916B|1979-07-13|1983-03-16|Sankyo Co|Trihaloallyl derivatives having anti-fungal and preservative activities|
    FR2586415B1|1985-08-23|1987-11-20|Poudres & Explosifs Ste Nale|NOVEL DIHALOGENO-2,2 VINYL HALOGENOFORMIATES, THEIR PREPARATION PROCESS AND THEIR APPLICATIONS|
    JP3011937B2|1988-05-13|2000-02-21|ソニー株式会社|Magnetic recording media|
    US5919992A|1996-06-11|1999-07-06|Lonza, Inc.|Synthesis of haloalkynol|
    JP2852289B2|1997-02-26|1999-01-27|長瀬産業株式会社|Iodopropargyl derivative and antimicrobial agent containing the derivative as active ingredient|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP8909379A|JPS5615240A|1979-07-13|1979-07-13|Trihaloallyl derivative and antimildew and antiseptic containing the same|
    JP11811879A|JPS623828B2|1979-09-14|1979-09-14|
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