• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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  • 优先权
    • 专利摘要:
    There is provided a new herbicidal compound of the formula, <IMAGE> wherein R1 is an alkyl group; R2 is an alkynyl group, a halomethyl group, or a haloethyl group; and X is an alkoxy group, an alkenyloxy group, an alkoxy-alkoxy group, an alkynyloxy group, a hydroxy group, a halomethyloxy group, or a haloethyloxy group.
    公开号:SU1309910A3
    申请号:SU823451242
    申请日:1982-06-17
    公开日:1987-05-07
    发明作者:Кадзиока Мицуру；Окава Кацумаса；Таникава Куниаки
    申请人:Нихон Нохияку Ко Лтд (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing novel, 2, 4-triazolin-5-one derivatives of the general formula:
    (one)
    where K C -C4-alksh1;
    Rj - C -C-alkynyl, halomethyl
    or haloethyl;
    X — C — C4 alkoxy, Cj — C alkenyloxy, Cr — C alkoxyalkoxy, —Cy alkynyloxy, halomethyloxy, or halo ethyloxy, possessing 1–1X herbicidal activity.
    The compounds of general formula (D) are listed in Table 1.
    The purpose of the invention is to obtain new triazole derivatives, which have better properties compared with the European Union,
    Example 1, Synthesis of 1- (2,4-dichloro-5-isopropoxyphenyl) 3-methyl-4-difluoromethyl-d -1,2,4-triazolin-5-one
    To the 60 ml of cyclohexane was added 2 g (0.0066 mol) of 1- (2,4-dichloro-5-isogropoxyphenyl) -3-methyl &amp; -1,2,4-triazolin-3-one, 2-tetrabut ammonium ibromide and 2 g of caustic soda to obtain a suspension, in which 2 g (0.023 mol) of chlorodifluoromethane are added during 1 h at reflux The mixture is cooled to room temperature, the reaction mixture is diluted with 100 ml of water and extracted with diethyl ether.
    The resulting organic layer is separated off, washed successively with an aqueous solution of caustic soda, diluted hydrochloric acid and water, dried over anhydrous water.
    sodium sulfate, followed by sodium chloride, with a saturated solution of chloride
    The solvents are distilled off. Get 1.06 g of oily product.
    Oily product stand
    sodium and dry over anhydrous magnesium sulphate.
    After distilling off the solvent, the residue is recrystallized from a mixture
    at room temperature and perebris-, diethyl ether-petroleum tal.pizovyvayut from n-hexane to obtain- (1.5) to obtain 1.47 g of the target
    the desired product, mp, 81.3 C, yield 41%.
    PRI mme R 2. Synthesis of 1- (2,4-dichloro 5 propargyloxyphenyl) -3-methyl-4 propargsh1-D, 2,4-triazol-1-5-one,
    To 30 ml of acetone was added 0.5 g of 1- (2,4-dich. Por-5-proparoxy-1-phenyl) -3-methyl-D-α, 2,4-triazolin-5-one,
    product, i.e. 102-103.5 C, yield 36.5%.
    EXAMPLE 5 Synthesis of 4-di-55 chloro-5- (1,1,2,2-tetrafluoroethoxy) phenyl-3-methyl-4- (1, 1,2,2-tetrafluoro- ethyl), 2,4-triazolin-5-one. .
    0.78 g (0.003 mol) of 1- (2.4%) is suspended in 30 ml of dimethylformamide.
    0
    ,
    1 g of potassium carbonate and 0.5 g of propargyl bromide The mixture is boiled for 2 hours, cooled to room temperature, then excess potassium carbonate is filtered off and the potassium bromide formed is filtered off and the filtrate is subjected to acetone distillation.
    The resulting crystals are recrystallized from ethyl acetate-n-hexane to give the desired product, mp. 140 ,, yield 80.4%.
    The synthesis is carried out as in Example 1, but using different materials, the desired product of the general formula is obtained (O. The data on the obtained compounds are summarized in Table 2.
    DMF is dimethylformamide, and DMSO is dimethyl sulfoxide.
    And p and me R 3. The synthesis is carried out according to example 2, but using the other. gih materials.
    The results are shown in table 3.
    PRI me R 4. Synthesis of 1- (2,4-dichloro-5-isopropoxyphenyl) -3-methyl-4- (1,2,2,2-tetrafluoroethyl), 2,4-triazoln-3-one .
    In 60 ml of dimethylformamide, 3.02 g (0.01 mol) of 1-2,4-dis or-isopropoxyphenyl) -3-methyl-1 -1, 2,4-triazole-5-one is dissolved and added to the resulting solution 0.4 g (0.01 mol) of caustic soda powder. The mixture is heated to 50-60 ° C at
    transmission of gaseous tetrafluoroethylene, which is obtained by dropping 20 g 1 | 2-dibromo-1,1, 2, 2-tetrafluoroethane in 20 ml of methanol to a suspension of zinc dust (16.25 g) in 120 ml
    methanol.
    The reaction mixture is poured into ice-water, extracted with diethyl ether, two times washed with 10% aqueous solution of sodium chloride, water, and a saturated solution of chloride
    sodium and dry over anhydrous magnesium sulphate.
    After distilling off the solvent, the residue is recrystallized from a mixture
    , diethyl ether-petroleum (1.5) to obtain 1.47 g of the target
    product, i.e. 102-103.5 C, yield 36.5%.
    EXAMPLE 5 Synthesis of 4-di-55 chloro-5- (1,1,2,2-tetrafluoroethoxy) phenyl-3-methyl-4- (1, 1,2,2-tetrafluoroethyl ), 2,4-triazolin-5-one. .
    0.78 g (0.003 mol) of 1- (2.4%) is suspended in 30 ml of dimethylformamide.
    313
    dichloro-5-hydroxyphenyl) -3-methyl-l 1,2,4-triazolin-5-one. 0.25 g of caustic soda is added to the resulting suspension, and then heated at 50-60 °.
    An excess of tetrafluoroethylene, prepared according to the method described in Synthesis Example 5, is passed into the reaction mixture.
    The product obtained is poured into water with ice, extracted with diethyl ether. Received 0.33 g of oily product, PD 1, 4840, yield 23.9%,
    PRI me R 6. Synthesis was carried out as in Example 4, using other materials.
    The results are shown in table 4,
    Example Synthesis of 1- (2,4-dichloro-5-propargyloxyphenyl) -3-methyl-, 2,4-triazolin-5-one, intermediate.
    1.45 g (0.0062 mol) of 2,4-dichloro-5-propargyloxyphenylhydrazine and 1.2 g (0.007 mol) of ethyl-1 ll -. (Ethylthioethyl-iden) carbamata, Solution heated for 30 minutes at, then cooled to room temperature.
    Trietclamine is added and then a kipt of m 2 h. After the reaction mixture is cooled to room temperature, the resulting crystals are collected, m.p. 229.1 ° C, yield 80.6%,
    Example 8, Synthesis of 1- (2,4-Diclor-5-propargypoxyphenyl) -3-isopropyl-, 2,4-triazolin-5-one, intermediate.
    The procedure of Example 8 was repeated, but instead of 1.2 g of ethyl-L- (1-ethylthioethylidene) carbamate, 1.3 g (0.007 mol) of ethyl-K- (1-ethoxyisobutylidene) carbamate was taken to give 1 - (2,4-dichloro-5-propargsh1oxyphenyl) -3- isopropsh1-L -1,2,4-triazolin-5-6na, mp, 162.9 ° C, yield 80.1%,
    The herbicidal effect of the compounds of the present invention. . .
    1. Regulatory effect on the weeds of rice plantations before their shoots.
    The pots (1/10000 acre) are filled with earth to simulate a rice plantation and are planted with a hedgehog, monochoria, mud, and arrowhead leaves, respectively. harmful weeds growing on rice plantations and brought to the stage corresponding to
    transition stage
    seedlings.
    The soil in each pot is sprayed with a solution of each active compound (see Table 1) diluted with a liquid to a certain concentration. After 21 days, a control calculation was carried out in percent of weed growth versus untreated pots, and herbicidal activity was evaluated according to the following criteria.
    Criteria for assessing herbicidal activity.
    Degree of Herbi The level of inhibition of weed growth,%
    100 90-99 80-89 70-79
    70
    The results are shown in the table.
    2. Regulatory effect on weeds of rice plantations after the appearance of their shoots.
    Pots (1/10000 acre) filled with soil to simulate a rice plantation are planted with weed sprouts with the next leaf age. In addition, young sprouts of rice were planted (Niphonbare culture) with leaf age 2.5 days a day before tillage with each herbicide. 21 days after the treatment, the herbicidal effect and the degree of crop damage were evaluated by comparison with untreated pots.
    Age of weed leaf
    one
    2-3 1-2 2-3
    3
    Criterion for assessing the degree of chemical damage: B - high including warning; C - average; H - low; O is absent.
    Evaluation of herbicidal activity was carried out as in Test 1. Gender results are given in Table 6,
    5.13
    3, Regulatory effect on weeds of upland fields before the emergence of their shoots.
    Polyethylene cubes with dimensions of 10x20x5 cm (depth) are filled with soil and are sown with oats, spring leaves, large Elevzina, swan, ordinary wormwood, gishi gishi and umbrella sedge, after which the crops are covered with soil,
    The soil is treated with a solution of each active compound adjusted to the required concentration by dissolving in a liquid. After 21 days, the herbicidal effect was revealed by comparison with untreated cubes. The criterion for determining the herbicidal activity is the same as in test 1.
    The results are summarized in table 7.
    4, Regulatory effect on weeds of upland fields after the appearance of their shoots.
    Polyethylene cubes with dimensions of 10 X 20 X 5 cm (depth) are filled with earth and sown with weeds and seeds of soybean, then covered with soil. Weeds and soybeans are grown to the appropriate leaf age, and then treated with each active compound in a specific dosage,
    After 21 days, the herbicidal effect and the extent of damage to the soybean grade are determined by comparison with the results obtained in the raw cubes.
    yty
    but
    40
    Age sheet
    experimental
    plants
    2
    2 1
    12
    one
    The age of the first -50 double sheet
    45
    The criteria for evaluating the herbicidal activity and the degree of chemical damage are the same as in tests 1 and 2, the results obtained are shown in Table 8.
    Composition 1, Wettable powder composition, get uniform
    ABOUT
    five
    0
    five
    0
    five
    O6
    by swaddling and grinding the following ingredients, May, h ,:
    Compound 2 50 White-carbon clay mixtures with a predominance of clay 45 Polyoxyethylenenonylphenyl
    ether5
    Composition 2, The granular composition is obtained by uniformly mixing and grinding the following ingredients, mixing the resulting mixture with the required amount of water and granulating the kneaded mixture, May, h: Compound 13 5 A mixture of bentonite with clay90
    Calcium Litin Sulfate 5
    iCocTaB 3, The emulsifiable concentrate is obtained by uniformly mixing the following ingredients, May, h ,:
    Compound 15 50 Xylene
    Mixture of polyoxyethylenonylphenyl ether with calcium alkylbenzenesulfonate 10 Formulation 4, An emulsifiable concentrate is obtained by mixing to obtain a homogeneous mixture of the following components, in wt.%:
    0
    0
    five
    five
    Compound 14 Solvent Surface-active agent Composition 4a
    Compound 14 1 Xylene 30 Cyclohexanone 64 A mixture of calcium polyoxyethylene nonylphenyl ether and calcium alkyl benzene sulfonate 5
    1-75 20-98
    1-5
    Soe-Composition
    4b4c
    75 23
    37.5 30
    30.5
    7130
    In this example, instead of compound 14, compounds 1–13 and compounds 15-54 can be used, in addition to ternO (instead of xylene and cyclohexanone solvents used, the following solvents can be used: water, alcohols (for example, methanol, ethanol, isopropanol, butanol, ethylene glycol ), ketones (for example, acetone, methyl ethyl ketone, methylene sulfonyl ketone, diisobutyl ketone), ethers (for example, ethyl ether, dioxane, ethoxyethanol (cellosolve), dipropyl ether, and tetrahydrofuran), aliphatic hydrocarbons (for example, dipropyl ether, and tetrahydrofuran), aliphatic hydrocarbons (for example, dipropyl ether, and tetrahydrofuran), aliphatic hydrocarbons (for example, dipropyl ether, and tetrahydrofuran), aliphatic hydrocarbons (for example,) mineral oils), Romatic hydrocarbons (for example, benzene, toluene, naphtha, and alkylnaphthalenes), halogen-substituted hydrocarbons (for example, dichloroethane, chlorinated benzenes, chloroform, and carbon tetrachloride), esters (for example, ethyl acetate, dibutyl phthalate, diisopropyl phthalate and ethyl acetate. ), amides of acids (for example, dimethylformamide, diethylformamide and dimethylacetamide) nitriles (for example, acetonitrile) and dimethyl sulfoxide or mixtures of the indicated solvents.
    Calcium polyoxyethylene nonylphenyl ether and calcium alkyl benzene sulfonate can be replaced by the following surface active agents: polyoxyethylene alkyl esters, polyoxyethylene esters of higher fatty acids, abiene, tinic esters and polyoxy esters:
    ethylene, polyoxyethylene sorbitan monolaurates, polyoxyethylene sorbitan monooleate, alklaryl sulfonates, naphthalene sulfonic acid condensation products, sodium ligninsulfonate and sulfate esters of higher alcohols, as well as any mixtures of these surface active agents.
    Composition 5. The composition in the form of (wettable powder is obtained by mixing to obtain a homogeneous mixture of the following components, May,%.
    Connection 5 Surface-active agent Solid carrier
    5 0 5
    0
    five
    0 5
    0
    five
    O8
    Composition Soe-Sos-5a so tav
    5b 5c
    Compound 5 7 90 42 Polyoxyethylene nonylphenyl
    ether3 0.5 2
    Ligninsulfonate sodium 2 0.5 1 Bela carbon black 50 4 30 Clay 38 5 - 25
    Compound No. 5 can be replaced by compounds 1-4 and compounds 6-54, and the white carbon and clay can be replaced by the following solid carriers: wettable powders, such as soya flour, cereal flour, wood flour, bark flour, sawdust , powdered tobacco stems, powdered walnut shells, bran, powdered cellulose, residues after extraction of plant products; fiber materials such as paper, corrugated cardboard, waste matter; synthetic polymers, for example powdered synthetic resins; inorganic or mineral products, such as clays, (in particular, kaolin, bentonite, etc.) with talcs (for example, talc and pyrophylite), siliceous derivatives (for example, diatomaceous earth, silicon dioxide and myca), activated carbon, powdered sulfur, pumice, calcined diatomaceous earth, clinker, fly ash, sand, calcium carbonate, calcium phosphate, chemical fertilizers, for example ammonium sulfate, ammonium nitrate, urea, ammonium chloride, manure, or any mixtures mentioned spruce.
    Polyoxyethylene nonylphenyl ether and sodium ligninsulfonate can be replaced by the following surface active agents: polyoxyethylene alkyl ethers, polyoxyethylene esters of higher fatty acids, polyoxyethylene abietic esters, polyoxyethylene sorbitan mono poly polyoxyethylene polyoxyethylene esters, polyoxyethylene polyoxyethylene esters, polyoxyethylene ethylene ethylenesulfonate esters, polyoxyethylene ether alkyl esters, polyoxyethylene ethylene ethyl esters, polyoxyethylene ethylene ethyl esters, polyoxyethylene ethylene ethyl esters, polyoxyethylene ethylene ethyl esters - arylsulfonates, naphthalenesulfonic acid condensation products, calcium ligninsulfonate and sulfate esters of higher alcohols, as well as any mixtures of these surface ktivny agents.
    Composition 6, the composition is obtained by mixing to obtain a homogeneous mixture of the following components, wt.%:
    Compound 141-70 Solvent1 10 Surface Active Agent1-5 Thickener1-5 Solid Media5-10
    Composition Soe-Sos14

    s
    6.t
    1 65
    2 2
    thirty
    tav 6b
    70 23
    4 1
    tav .6s
    35
    40
    3 2
    20
    In the above formulation, instead of compound 14, compounds 1-13 and compounds 5-54 | can also be used, and instead of silicon anhydride, the following solid can be used
    carriers: wettable powders, such as hydrocarbons (for example, gasoline
    and mineral oils), aromatics, hydrocarbons (for example, benzene, toluene, xylene, naphtha, and alkylnaphthalenes) halogen-substituted hydrocarbons (for example, soy flour, cereal flour, wood flour, bark flour, sawdust, powdered tobacco stems, powdered shell.
    walnuts, bran, powder, dichloroethane, chlorine cellulose, residues from extrabenzenes, chloroform, and tetrachlorination of plant products; fiber hydrocarbons, esters (raw materials, such as paper, rifrimer, ethyl acetate, dibutyl phthalate, lined cardboard, waste matter, diisopropyl phthalate and dioctyl phthalate),
    40 amides of acids (for example, dimethylformam-MID, diethylformamide and dimethyl acetamide), nitriles (for example, acetonitrile), dimethyl sulfoxide, or mixtures of these solvents.
    Example 7. Powder is obtained by mixing to obtain a homogeneous
    45
    tic polymers, for example, powdered synthetic gums, inorganic or mineral products, such as clays (for example, kaolin, bentonite and sour clays), talcs (for example, talc and pyrophyllite), siliceous derivatives, for example, diatomaceous earth, siliceous sand, flour and white carbon black (highly dispersed synthetic silicic acid, the same name is finely divided hydrated silica or hydrated silicic acid, and also some of the products that contain: Calcium silicate), activated coal, powdered sulfur, pumice, calcined diatomaceous earth, clay clay brick, fly ash, sand, carbonate
    a mixture of the following components, wt.%:
    1-90
    . Connection 5 Solid media
    Compound 5 Bela. Sazha Clay
    In this formulation, instead of the compound 5 used, it is possible to use calcium phosphate, chemical fertilizers, for example ammonium sulfate, ammonium nitrate, urea, ammonium chloride, manure, or any mixtures of marked carriers.
    The following surface-active agents can be used instead of sodium lignosulphonate: polyoxyethylene alkali aromatic esters, polyoxyethylene alcohols, polyoxyethylene esters and higher fatty acids, polyoxyethylene sorbitan polyoxyethylene sorbitan monolaurate esters, polyoxyethylene lorbitan monohydrophen, and nitroxyethylene sorbitan mono ethylacetylene esters. calcium ligninsulfonate, sulfate esters of higher alcohols, as well as any mixture of surface-active agents.
    The following solvents can be used instead of water: alcohols (for example, ethanol, methanol, isopropanol, butanol, ethylene glycol), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone), ethers (for example, ethyl ether, dioxane, celloxane) (ethoxyethanol), dipropyl ether and tetrahydrofuran), aliphatic mineral oils), aromatic, hydrocarbons (for example, benzene, toluene, xylene, naphtha and alkylnaphthalenes) halogen-substituted hydrocarbons (as a mixture of the following components, wt.%:
    1-90
    . Connection 5 Solid media
    Compound 5 Bela. Sazha Clay
    In this recipe, instead of the named compound 5, you can
    Compounds 1-4 and compounds 6-54 can also be used, and instead of white soot and clay, you can use the following solid carriers: solid powders, such as soy flour, cereal flour, wood flour, bark flour, sawdust, tobacco powder stems powdered walnut shells, bran, powdered
    cellulose, residues after extraction of plant products; fiber materials such as paper, corrugated cardboard, and waste; synthetic polymers, for example, powdered synthetic gums, inorganic and mineral products, for example clays (for example, kaolin, bentonite), talcs (for example, talc and pyrophyllite), siliceous derivatives (for example, diatomaceous earth, siliceous sand and flour), activated charcoal , powdered sulfur, pumice, calcined diatomaceous earth, clinker, fly ash, sand calcium carbonate, calcium phosphate, chemical fertilizers, such as ammonium sulfate, ammonium nitrate, urea, ammonium chloride, manure, and any mixtures said carriers,
    In the example, the composition in the form of granules is obtained by mixing to obtain a homogeneous mixture and grinding the following components, followed by kneading the resulting mixture with the required amount of water and granulating the substituted mass, wt.%:
    Compound 14 1-70 Auxiliary agent (binder) Solid carrier

    0
    f5
    0
    25
    thirty
    35
    40
    45
    0
    1012
    compounds 1-13 and 15-54 compound, and calcium ligninsulfonate can be replaced by the following adjuvants: casein, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, turpentine oil, rice bran oil, bentonite, and any mixtures of these auxiliary agents,
    Used bentonite and clay can be replaced by the following solid carriers: powders of vegetable origin, such as soy flour, flour of cereal plants, wood flour, flour from bark, sawdust, powdered tobacco stalks, crushed walnut shells, bran, powdered cellulose, residues from the extraction of plant products, fiber materials, such as paper, corrugated cardboard and waste matter, synthetic polymers, such as powdered synthetic gums, inorganic or mines Key products such as clays (e.g., kaolin-J, talcs (e.g., talc and pyrophyllite), siliceous derivatives, e.g. diatomaceous earth, siliceous sand, mica and white carbon black (highly dispersed synthetic silicic acid, the same name is fine hydrated dioxide) silicon or hydrated silicic acid, as well as some industrial products containing calcium silicate as the main component), activated carbon, powdered sulfur, pumice, calcined diatomaceous earth, clinker, volatile ash sand, calcium carbonate, calcium phosphate, chemical fertilizers, for example, ammonium sulfate, ammonium nitrate, urea, ammonium chloride, manure, or any mixtures of these carriers.
    Comparative data on the activity of the proposed and known (a) - (f) compounds are presented in Table. 5-13.
    Known compounds:
    In the above formulation, instead of compound 14, it is also possible to use
    N-CH
    (but)
    13
    G1 O
    ) V-lf% -CH / /
    C1 O
    Q-T TYA-SzN7-1 -N
     X o
    1I D.
    ,) -СзИ7
    ZOR invention formula
    The method of obtaining the derivative, 2,4-triazolin-5-one common forums
    C1 O /
    1 y
    35
    H ji-pz
    X RI
    4P
    de RI - C1-C4-alkyl1
    R is a C3-C-alkynyl group, a halo-methyl or a haloethyl group; X - With - With - alkoxy. Cz-C-alkenyloxy, C2-Sb-alkoxy-alkoxygroup, Cj-C-i -alkynyloxy, ,, halomethoxy, or haloethoxygroup,
    .130991014
    distinguished by the fact that the derivative, 2,4-triazolin-5-one of the general formula
    J5
    0
    ZO
    five
    35
    4P
    where X has the indicated meanings, is reacted with a compound of the general formula
    or haloethylene, where R2 is as described above and Z is a halogen atom, at a temperature of 25 ° C to the boiling point of an inert solvent, in the presence of a base, such as NaOH, KOH, NajCOj, NaHCO, KHCO3, CHiONa, CHjOK, C Hg -ONa or CgH5 OK, in the environment; an inert solvent selected from the group of aromatic hydrocarbons, such as benzene, toluene, chlorobenzene or xylene, ethers such as ethyl ether, tetrahydrofuran or dioxane; alcohols, such as methanol, ethanol, propanol or ethylene glycol; ketones, such as acetone, methyl ethyl ketone or cyclohexanone; lower fatty acid esters such as ethyl acetate; lower fatty acid amides, such as dimethylformamide or dimethylacetamide; water;
    dimethyl sulfoxide or cyclohexane,
    I
    Priority featured:
    25.12.80 when R is C-C4-alkyl; R2-diphthromoethyl and C-C-alkyl groups; X - all values except ha. loidmethoxy and haloethoxy,
    30.04.81 with R-halo-methyl (except difluoromethyl) or a halo-methyl radical, X is a halomethoxy or halo-ethoxy radical.
    Table 1
    ShzSN SNSO SNZ
    CH
    CH2 CCH20 ss
    SNG
    CHjCH CHCHjO CHj
    gn
    Ln
    С1СН СНСН2020 СНз
    C1CH2CH CHO CHj
     "
    SNS
    СН2 СНСН2СНО with «s
    SNS
    HS. SNS
    NP N

    n
    njf 1.5432 73.5
    116.9
    74.9
    133.8
    138
    83.5
    47.6 115.1
    69.1
    129.5 132.7 nj 1.5423
    n: "1.5423
    CHF,
    n 1,5323
    CHF,
    1 18.1
    CHF,
    81.5
    |
    CHj
    50
    ABOUT
    sn.
    CHF,
    115.7
    51
    i
    CH,
    CFjBr
    . 119; b
    ABOUT
    C1 O
    Tabl
    .. -sh5 53rd aO-L-snr2
     / u /
    , / -MH,
    1 R,
    RI
    C1 O
    table 2
    -L-snr2
    ,
    RI
    Table 3
    23
    Ci o
    130991024
    Table4
    Cl q
    Table 5
    Table 10
    Table 13
    39
    1309910
    40 Continuation of table 13
    权利要求:
    Claims (1)
    [1]
    The claims where R d HX have the indicated meanings, are reacted with compound J5 of the General formula
    R 2 Z or haloethylene, where R z is as defined above, a Z is a halogen atom, at a temperature of 25 ° C to a temperature
    20 boiling inert solvent, in the presence of a base such as NaOH, KOH, Na 2 CO 3, K 2 C0 Oe, NaHCO 3, KHCO 3, CHgONa, CHjOK, C ^ ONa or C2H5 OK, in a medium inert rast25 voritelya, selected from the group of aromatic hydrocarbons, such as benzene, toluene, chlorobenzene or xylene, ethers, such as ethyl ether, tetrahydrofu30 wounds or dioxane; alcohols, such as methanol, ethanol, propanol or ethylene
    Δ 2 - !, 2,4-triazoline ~ 5-one of the general formula where Rf is C 1 -C 4 alkl;
    R 2 is a C e —C 6 alkynyl group, a galmethylmethyl or haloethyl group;
    X is C 4 -C 4 alkoxy, * Cj-C ^ alkenyloxy, Cj-Cg alkoxyalkoxy, Cj-C- | -alkynyloxy group, halo methoxy group or halo ethoxy group, glycol; ketones such as acetone, methyl ethyl ketone or cyclohexanone; lower fatty acid esters,, 35 such as egyl acetate; lower fatty acid amides such as dimethylformamide or dimethypacetamide; water; dimethyl sulfoxide or cyclohexane,
    Priority by signs:
    25.12.80 g at - C 1 -C 4 alkyl;
    H 2 difluoromethyl and C 3 -C 5 alkyl groups; X - all values, except for halomethoxy and haloethoxy, 04/30/81 at R 1 -halogenomethyl (except difluoromethyl) or haloethyl radical, X - halogenmethoxy or haloethoxy radical.
    Table 1
    Compound XR 1 f. r II II l/ II I II 1eleveneleveneleven1_________________________________________________1 Melting point, ° C, or refractive index 1 2 3 4 5 1 sn = ssn 2 about CH 3CH; CCH 2140.6 2 ί -С 3 Н 7 О Chj checch 2n 2 J 1, 5589 3 CH 3 OCH 2 O CH 3ch = cch 2n 2 J 1-, 5527 4 sn 2 = sns 2 o i-CjH, ch = cch 2109.0 . 5 i -С 3 н 7 о Chj chf 281.3 6 sn 3 main 2 about Ch j chf 2116.4 7 sn g = sns 2 o ch 3CHF 296.4 8' sn 2 = sns 2 o i -c 3 H 7chf 293.5 9 i -s 3 n 7 o i -C 3 H 7chf 279.0 • 10 sn 3 main 3 o i -C 3 H 7CHF 2nJ 1.5312 eleven sun 3 o Chj chf 2154.5 12 chf 2 o CH 3chf 282,4 14' sn = ssn 2 about CH 3chf 21 14.4 fifteen CH £ CCH 4 0 i -c 3 H 7chf 291.2 16 chf 2 cf 2 o CH 3chf 2n 1 J e 1, 5013 17 CHFCICFjO Chj chf 279-81 18 i -C 3 H 7 O Chj chf 2 cf 2102-103.5, 19 CHj-CHCH 2 O Chj chf 2 cf 281, 8 20 CH = CCH 2 0 ch 3chf 2 cf 2116-118 21 CHF 2 CF 2 O CH 3chf 2 cf 21.4840 22 i -C 3 H 7 O sun 3chfcicf 2131.5 23 CH g = CHCHjO CH 3chfcicf 296.1 24 i -CjH., 0 ch 3CHFBrCF 2n “' 5 1, 5308 25 ch 2 = chcho CH1chf 2n} 1, 5372
    CHS .17 1309910 '18
    Continuation of table 1
    ί 1 3 4 F 26 CH 3 CH = CHSS sun 3chf 2nJ 8 1.5432 27 sn 3 CH 2 = ^ CH 2 0 CH sun 3Chfj 73.5 28 sn 5 sn = sns 2 about sun 3chf 2116.9 29th CH 3x ' sun 3chf 274.9
    gn / C = cf N g 0
    thirty cich = chch 2 o ch 3chf 2133.8 31 CICH2CH = CH0 CH 3chf 2138 32 CH 2 = CCH 2 CH 2 O CH 3chf 283.5 CH 3 33 CH 2 = CHCH 2 CHO CH 3chf 247.6 34 > = c 4 H 4 H CH 3chf 2115.1 35 C 2 H f CHz CH 2 ° ch 3chf 269.1 c = c ./ H h 36 CH 3 CECCH 2 O CH 3chf 2129.5 37 C 2 E 5 C-CCH 2 0 CH 3chf 2132.7 38 heavenly Gh 3chf 2nJ 8 1, 5423 |• SNZ nJ 1, 5423 39 HC = CCH0 Ch j chf 2
    40 HCsCCHO C 3 H 7 -n Chj chf 2nJ 1,5323 41 HC = £ CO ^SNZ SSH ch 3chf 2118.1 42 HC = CC0 CH j chf 281.5
    cfC x c 2 H5
    19 13099Y 20Continuation of table 1 1 '2 i5 43 HtaCCO CH 3 CgHe-I: ch 3chf 2η 2 / 1.5310 44 HCSCCH 2 CH 2 O CH 3chf 2118.0 45 CH = C = CHCH 2 O CH 3chf 292.0 46 CH 3 CHCCH 2 CH 2 0 CH 3chf 2146.8 47 C 2 H 2 C = CCH 2 CH Z O CHj chf 2104.5 48 No.CH 2 CH0 CH ^  Chj chf 2nJ 8 1,5442 . 49 CH 3 C = CCH 2 CHO CH SCh j chf 2nJ 1.5425 fifty | hY ° Chj chf 2115.7  51 i -C 3 H 7 O CH 3CF 2 Br  119; 6
    Table
    C1CHF Z n-chf 2
    Bi
    Compound XR 1 Solvent Temperature ° C Base 5 i -PrO Chj Toluene 80 NaOH 14 CH = CCH 2 O; Chj Thf Reflux (65) NaOH 9 ί -PrO i -Pr DMF U0-1U. NaH 8 ch = chch 2 o i-pr Chlorobenzene 130 KOH 6 Chjoch sun 3dmso 100 Cjhjok eleven ch 3 o Chj Xylene 100 KOH fifteen CH = CCH 2 O i -Pr Dioxane 80 NaOH thirteen Chfjo sun 3DMF . 100 CH ^ ONa 9 i -PrO i -Pr Dimethyl 80 Koh
    acetamide
    Table and 3 Compound X R. Dissolve-tel Temperature ° C Base 2 i-PrO CH 3EtOH thirty NaOH 4 sn g sns 2 o i-pr ch 3 ci Reflux (82) K 2 C0 3 1 sn = ssn 2 about CH 3Benzene fifty Na 2 CO 3 4 sn g = sns g o i-pr Xylene 100 NaHC0 3 3 sn 3 main 2 about ch 3Dioxane 80 knso 3 3 CH 3 OCH 2 O ch 3Chlorobenzene 60 con 2 i-PrO ch 3Diethyl ether thirty sun 3 o 1 - sn = ssn 2 about CH 3Yeon 20 sn r ok 4 sn 2 = sns 2 o i-pr Propanol 25 C 2 H 5 0Na 2 i-PrO CH 3DMSO thirty C 2 N 3 sn 3 main 2 about sun 3dmso thirty KOH 5 i-PrO CH 3Ethylene Glycol 70 KOH T 1 sun 3 o CH 3Methyl ethyl ketone 60 NaOH 9 i-PrO i-pr Cyclohexane 80 NaOH eleven CH s of CH 3Ethyl acetate 70 KOH 5 i-PrO CH 3Water 60 Kjcoj<7
    Table 4
    Compound XSolvent Temperature ° C Base 18 i-PrO sun 3DMSO 60 C 2 H 5 OK 20 sn = ssn 2 about sun 3DMF 50-60 con 22 i-PrO sun 3DMSO . 40-50 con 24 i-PrO CH 3DMF 60 CH 3 About Na 19 sn 2 = sns 2 o sun 3DMF 60 NaOH 21 chf 2 cf 2 o sun 3DMSO 50-60 KOH 23 sn 2 = sns 2 o sn }DMF 60 CH 3 ONa
    Table 5
    Compounds - Amount of stain in the applied active ingredient, g / acre
    Processing action before germination Bramble Monochoria Wipe Reeds Gunner
    1 thirty 5 5 5 5 5 2. thirty 5 5 5 4 5 3 thirty 5 . 5 5 5 5 5 thirty 5 5 5 5 5 6 thirty 5 5 5 5 5 7 thirty 5 5 5 5 5 8 thirty 5 5 5 5 5 9 thirty . 5 5 ' 5 5 5 thirteen thirty 5 5 5 5 5 14 thirty 5 5 5 5 5 fifteen thirty 5 5 5 5 5
    25 1309910 26
    Continuation of Table 5
    - η - Connected Quantity Act processing up emergence of seedlings phenomenon in applicable Bramble Monocho Wipe Reeds Gunner activeria ingredient, g / acre 16 1 1 1 '1 ° 1 m 1 1 5 15 5 5 5 17 thirty 5 5 5 5 5 18 thirty 5 5 5 5 5 19 thirty 5' 5 5 5 5 20 thirty f5 5 5 5 5 21 thirty 5 5 5 5 5 22 thirty 5 5 5 5 5 23 thirty 5 5 5 4 5 24 thirty 5 5 5 4 5 40 thirty 5 5 5 5 5 · 41 thirty 5 5 5 5 5 42 thirty 5 5 5 5 5 43 thirty 5 5 5 5 5
    Table 6
    Compound The amount of active ingredient, g / acre Action of treatment after, emergence of seedlings Chemical damage to rice plantag Hedgehog Monochoria Wipe Reeds Arrowsheet 1 . thirty. 5 ' 5 5 4 5 N 2 thirty 5 4 4 2 5 0 3 thirty 5 5 5 4 5 0 5 thirty 5 5 5 4 4 N 6 thirty 5 5 5 4 4 N 7 thirty 5 5 5 4 4 N
    28.
    Continuation of Table 6
    Connected Quantity Post-Appearance Processing Action Chemical nation ak-seedlings damage tivnogorice yngredi- Hedgehog Mono- Wipe Reeds Arrow plantations entachoria sheetg / acre
    8 thirty 5 5 9 thirty 5 5 thirteen thirty 5 5 14 thirty 5 5 fifteen thirty 5 5 16 thirty 5 4 17 thirty 5 4 18 thirty 5 5 19 thirty 5 5 20 thirty 5 4 21 thirty 5 4 22 thirty 4 ' 4 23 thirty 4 4 24 thirty 3 4 40 thirty 5 5 41 thirty 5 5 42 thirty 5 5 43 thirty 5 5
    5 4 4 n 5 4 4 n 5 4 5 n 5 - 5 5 n 5 4 4 n 4 3 2 n 5 3 2 0 5 4 3 n 5 5 3 n 5 . 4 3 n 5 3 2 n 5 2 2 0 4 3 2 0 4 3 2 0 5 4 4 n 5 5 5 n 5 4 . 4 n 5 3 3 n
    I
    29 1309910 30
    Table 7
    Compound The amount of active ingredient used, g / acre Action from processing to emergence Oats Bramble Big Elovina Quinoa Sagebrush Gishigishi Umbrella sedge 1 thirty 4 5 5 5 5 5 5 2 thirty 2 5 5 5 5 5 5 3 thirty 5 5 5 5 5 5 5 5 thirty 5 .. 5' 5 5 5 5 5 6 * thirty 5 5 5 5 5 5 5 7 thirty 5 5 5 5 5 5 5 8 thirty 5 5 5 5 5 5 5 9 thirty 5 5 5 5 5 5 5 thirteen thirty 5 5 5 5 5 5 5 14 thirty 5 5 5 5 5 5 ' 5 13 . thirty - 5 5 5 5 5 5 5 16 thirty 4 5 5 5 5 5 5 17 thirty 2 4 5 5 5 5 5 18 thirty 4 5 5 5 5 5 5 19 thirty 5 5 5 5 5 5 5 20 thirty 5 5 5 5 5 5 5 21 thirty 4 5 5 5 5 5 5 ABOUT 22 thirty 3 4 4 5 5 5 5 23 thirty 2- 2 3 5 5 4 5 24 thirty 2- 3 5 5 4 5 5 '40 thirty 5 5 5 5 5 5 5 41 thirty 5 5 5 5 5 5 5 42 thirty 5 5 5 5 5 5 5 43 zo 5 5 5 5 5 5 5
    31 1309910 32
    T a b l
    Connectednation The amount of active ingredient used, g / ar. The effect of processing after emergence Oats Big electric car Quinoa Sagebrush Gishigishi Umbrella sedge 1 thirty 2 2 5 5 5 5 2 thirty 2 4 5 5 5 . 5 3 thirty 3 5 5 5 5 5 5 thirty 5 5 5 5 5 5 6 thirty 5 5 5 5 5 5 7 thirty 5 5 5 5 5 5 8 thirty 5 5 5 5 5 5 9 thirty 5 5 5 5 5 5 thirteen thirty 5. 5 5 5 5 5 14 thirty 5 5 5 5 5 5 fifteen thirty 5 5 5 5 5 5 16 thirty 2 5 5 5 5 5 17 thirty 2 4 5 5 5 5 18 thirty 3 4 5 5 5 5 19 thirty 5 5 5 5 5 5 20 thirty 5 5 • 5 5 5 5 21 thirty 2 5 5 5 5 5 22 thirty 2 5 · 5 5 5 5 23 thirty 2 4 5 4 4 5 24 thirty 2 3 5 5 5 5 40 thirty 5 5 5 5 5 5 41 thirty 5 5 5 5 5 5 42 thirty 5 5 5 5 5 5 43 thirty ' 5 5 5 5 5 5
    Ts a 8
    Chemical damage
    N N N N N N N N N N N N N N N N
    Table9
    Compound The applied amount, g / ar The effect of treatment before weeds Bramble Monochoria Galingale Reeds Gunner 14 12.5 5 5 5 5 5 6.25 5 5 5 5 5 5 12.5 5 5 5 5 5 6.25 5' 5 5 5 4 (a) fifty 1 1 1 1 1 (B) fifty 1 1 1 1 1 (from) fifty 1 1 1 1 1 (d) fifty 1 1 1 1 1 (e) fifty 2 about2 1 2 1 (f) fifty 2 1 1 1 1
    Table 10
    Compound The applied amount, g / ar The effect of processing after the emergence of weeds Bramble Monochoria Galingale Reeds Gunner 14 1,5 5 4 5 3 5 6.25 5 4 5 3 5 5 12.5 5 4 4 2 5 6.25 4 4 4 2 4 (a)' fifty. 1 1 1 1 1 (B) *fifty 1 1 1 1 1 (from) fifty 1 1 1 1 1 ' (d) fifty 1 1 1 1 1 (e) fifty 1 2 1 1 1 (f) fifty 1 1 1 1 1
    Table II
    Compound The applied amount, g / ar The effect of treatment before weeds Oats Bramble Blood red dewdrop Mary Red Common wormwood Gishigishi Umbrella sedge 14 12, * 5 3 5 5 5 5 5 5 6.25 2 5 5 5 5 5 5 5 12.5 3 5 5 5 5 5 5 6.25 2. 3 5 5' 5 5 5 (a) fifty 1 1 2 2 3 3 1 (B) fifty 1 1 1 2 1 1 1 (from) fifty 1 1 1 1 1 1 1 (d) fifty 1 1 1 1 3 2 1 (e) fifty 1 1 1 1 1 1 1 (f) fifty 1 1 1 1 1 1 1
    Table 12
    Compound The applied amount, g / ar The effect of processing after the emergence of weeds Oats Blood Rosichka Mary Red Wormwood is common. Quenches gishi Umbrella sedge 14 12.5 5 5 5 5 5 5 6.25 3 5 5 5 5 5 5 12.5 2 4 5 5 5 5 6.25 2 3 5 5 5 5 (a) fifty 1 2 2 2 2 1 (B) fifty 1 1 1 1 1 1 (from) fifty 1 1 1 1 1 1 (d) fifty 1 1 1 1 1 1 (e) fifty 1 1 1 1 1 1 (f) fifty 1 1 1 1 1 1
    Table 13
    Compound Composition composition The amount of active component used in the processing, g / ar Pre-emergence efficiency Millet Chicken Galingale Gunner 14 4a thirty 5 5 5 5 5 14 4j zo 5 5 5 5 5 5 5a thirty 5 5 5 5 5 5 5b thirty 5 5 5 5 5 14 6a thirty 5 5 5 5 5 14 6 b thirty 5Q 5 5 5 5 5 7a thirty 5 5 5 5 5 5 7b thirty 5 5 5 5 5 14 8a thirty 5 5 5 5 5 14 8b . thirty ' 5 5 5 5 5 2 4a thirty 5 5 5 5 5 2 5b ‘ thirty 5 5 5 5 5 3 . Behind thirty 5 5 5 5 5 5' 7a thirty 5 5 5 5 •5 6 4j thirty 5 5 5 5 5 7 6a thirty 5 5 5 5 5· 8 6b thirty 5 5 5 5 5 9 4a thirty 5 5 5 5 5 thirteen 7j thirty 5 5 5 .5 5 14 5a thirty 5 5 5 5 5 ' fifteen 7a thirty 5 5 5 5 5 16 8b thirty 5 5 5 5 5 17 8a thirty 5 5 5 5 5
    39 1309910 40
    Continuation of Table 13
    Compound Composition composition" The amount of active component used in the processing, g / ar Efficiency in pre-treatment about- Millet Chicken Galingale Arrow leaf 18 5a thirty 5 5 5 5 5 19 5a thirty 5 5 5 ' 5 5 20 5a thirty 5 5 5 5 5 21 6b thirty 5 5 5 5 5 22 7a thirty 5 5 5 5 5 23 4a thirty 5 5 5 4 5 24 4a thirty 5 5 5 4 5 40 5a thirty 5 5 5 5 5 41 5b thirty 5 5 5 5 5 42 6a thirty 5 5 5 5 5 43 6s zo 5 5 5 5 5 (a) 8a thirty 1 1 1 1 1 (B) 8a thirty 1 1 1 1 1 (from) 8a thirty 1 1 1 1 1 (d) 8th thirty 1 1 1 1 1 (e) 8a thirty 1 1 1 1 1 (f) 8a thirty 1 1 1 1 1
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    同族专利:
    公开号 | 公开日
    ES8304102A1|1983-02-16|
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    引用文献:
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    US4276420A|1978-05-24|1981-06-30|Chevron Research Company|Herbicidal and plant-growth-regulating 1,2,4-trisubstituted-1,2,4-triazolidin-3-one-5-thione|
    IT1096333B|1978-05-25|1985-08-26|Montedison Spa|1,2,4-TRIAZOLIDIN-3-ONI E-TIONI|
    US4318731A|1979-08-25|1982-03-09|Nihon Nohyaku Co., Ltd.|Δ2 -1,2,4-triazolin-5-one derivatives and herbicidal usage thereof|US4919708A|1983-10-13|1990-04-24|Fmc Corporation|Haloalkyl triazolinones and herbicidal use thereof|
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    CA1242730A|1984-05-31|1988-10-04|Atsushi Tsushima| .delta..SUP.2-1,2,4-TRIAZOLIN-5-ONE DERIVATIVES ANDHERBICIDAL COMPOSITIONS CONTAINING THE SAME|
    US4705557A|1984-09-13|1987-11-10|Fmc Corporation|Herbicidal 1-aryl-Δ2 -1,2,4-triazolin-5-ones and sulfur analogs thereof|
    JPS61501991A|1984-10-31|1986-09-11|
    US4818276A|1984-11-20|1989-04-04|Fmc Corporation|Herbicidal 1-aryl-Δ2 -1,2,4-triazolin-5-ones|
    WO1987000730A1|1985-08-08|1987-02-12|Fmc Corporation|HERBICIDAL 1-ARYL-delta2-1,2,4-TRIAZOLIN-5-ONES|
    EP0193660A1|1985-03-01|1986-09-10|Nihon Nohyaku Co., Ltd.|1--3-methyl-4-difluoromethyl--1,2,4-triazolin-5-one derivatives|
    JPH0529225B2|1985-10-26|1993-04-28|Nihon Nohyaku Co Ltd|
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    US5294595A|1985-12-20|1994-03-15|Fmc Corporation|Herbicidal aryl triazolinones|
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    US5125958A|1988-08-31|1992-06-30|Fmc Corporation|Herbicidal triazolinones|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP18455780A|JPS57108079A|1980-12-25|1980-12-25|Delta2-1,2,4-triazolin-5-one deriviative, its preparation and use|
    JP18455880A|JPS57108080A|1980-12-25|1980-12-25|Delta2-1,2,4-triazolin-5-ones, their preparations and uses|
    JP6549781A|JPS57181069A|1981-04-30|1981-04-30|Delta2-1,2,4-triazolin-5-one and its preparation and use|
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