• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 法律状态
  • 优先权
    • 专利摘要:
    The invention provides novel herbicidal sulphonanilides of the formula: <CHEM> where R<1>-R<8> have the meanings given in the specification, and salts thereof, processes for their preparation, and herbicidal compositions containing them.
    公开号:SU1750428A3
    申请号:SU894742212
    申请日:1989-10-03
    公开日:1992-07-23
    发明作者:Стюарт Гейтс Питер；Питер Джоунз Грехем
    申请人:Шеринг Агрокемикалз Лимитед (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing sulfoanilides of heterocyclic compounds with valuable herbicidal properties and which can be used in agriculture.
    3
    Known derivatives of pyrimidine, with herbicidal activity.
    The disadvantage of these known derivatives is their relatively low selectivity.
    The purpose of the invention is a method of half-novels of sulfoanilide derivatives of heterocyclic compounds with a higher herbicidal selectivity.
    The goal is achieved based on a known reaction method for the preparation of sulfoanilides of the general formula

    N-S02 i N
    X-ffTR3
     Xy
    R
    A
    four
    6
    de a
    R
    nitrogen or CR5 group and
    X v w
    Rr
    hydrogen, methyl, fluorine, chlorine, bromine or trifluoromethyl; oxygen or sulfur; nitrogen or methyl group, trifluoromethyl, cyano-methyl, chloromethyl, phenyl, possibly substituted by chlorine or methoxycarbonyl, benzyl, methoxycarbonylamino group, thiazolo (3,2-b) (1,2,4) triazol-2-yl, 5, 7-Dimethyl (1,2,4) triazolo (1) pyrimidin-2-yl or 5-methyl-3-methoxy-carbonylpyrazolo (1,) pyrimidin-2-yl;
    hydrogen, methyl or acetyl; hydrogen, methyl or methoxy;
    hydrogen, methyl, methoxy group, chlorine or cyclopropyl; hydrogen, methyl or chlorine; hydrogen or methyl, or their salts with bases, The method consists in the fact that nilin of the general formula
    H
    R, R l
    R6 R-,
    g
    NH A
    Kb r
    N p
    X-f Y h
    Mu R,
    750428
    Where A, X, Y, R6
    15
    20
    25
    lt
    thirty
    35
    40
    45
    50
    55
    ETC
    and R and have the indicated meanings, are reacted with the sulfoanhydride of the general formula I
    (R1SOZ) 20 or with a sulfonyl halide of the formula
    R, S02Hal,
    where R, have the indicated meanings; Yu Hal - halogen, in the presence of a base, followed by isolation of the target product in free form or in the form of a salt with a base,
    and mer K 2-Chloro-6 - (, b-di-methoxy-2-pyrimidinyloxy) -1,1,1-trifluoromethanesulfonanilide „
    a) 2-Chloro-6- (4,6-dimethoxy-2-pyrimidinyloxy) aniline „
    22.4 Sodium tert-butylate is added with stirring, under nitrogen, to a cooled solution of 22.5 g of 2-chloro-6-oxyaniline-hydrobromide in 100 ml of dimethylformamide. After one minute, 21.8 g of the reaction mixture is added to the reaction mixture. 6-dimethoxy-2-methylsulfonylpyrimidine and heat it with stirring at 80 ° C for 22 hours. After adding an ice-water mixture, the precipitating solid is filtered off, washed thoroughly with water, dried and recrystallized from isopropanol,
    17.5 g of the desired product is obtained from 8k - 86 ° C. After evaporation of the mother liquor, an additional 0.85 g of product is obtained, 86 - 87 ° C.
    b) o Potassium salt of 2-chloro-6- (4,6-dimethoxy-2-pyrimidinyloxy) -1,1,1-trifluoromethanesulfonanilide
    Trifluoromethanesulfonic anhydride (3.4 g) in 5 ml of dichloromethane was added dropwise with stirring and ice-cooling to 3.4 g of the product obtained in step a and 1.0 g of pyridine in 25 ml of dichloromethane. After 6 hours of stirring at room temperature, the dichloromethane solutions are washed with water, dilute hydrochloric acid and again with water, dried with magnesium sulfate and evaporated in vacuo. The residue is stirred with sodium hydroxide solution (0.7 g sodium hydroxide in 30 ml of water) and ether in for lx15 min. The aqueous solution is separated, washed with ether and adjusted to pH 3 by the addition of hydrochloric acid, and then a small amount
    sodium bicarbonate. The precipitated orange solid is filtered off and dried, yielding 2, kg of crude product, t „pl, 141-1 3 ° C. The mother liquor is taken up in ether and the resulting solution is vigorously stirred with a solution of potassium bicarbonate (2.0 g in 30 ml of water. The precipitated potassium salt
    filtered and washed with ether to obtain g of product /
    c) “2-Chloro-6- (, 6-dimethoxy-2-pyrimidinyloxy) -1,1,1-trifluoromethanesulfonanilide”
    To regenerate the free product indicated in the title of the example from the potassium salt of stage b, the salt is stirred with ether (30 ml) and water (.30 ml). Then hydrochloric acid is added to adjust the pH of the ether layer, washed with water, dried with magnesium sulfate and evaporated. The residue was washed with petroleum ether (bp 0–60 ° C) and dried, yielding 1.4 g of pure product with m, 0-10 ° C

    PRI me R 20 2 -Chlorb-C +, 6-dimethoxy-2-pyrimidinyloxy) methane sulfonanilide
    Methanesulfonyl chloride (0.8 g) is added dropwise with stirring and ice-cooling to the product obtained according to stage 1 of example 1 in 10 ml of pyridine containing 0.1 g of 4-methylaminopyridine „as a catalyst.
    The mixture is stirred for 4 hours at room temperature and left overnight. After adding ice, water and ether to the mixture while stirring the acidification ... to pH 4, separating and evaporating the ether layer, 2.5 g of the crude product are obtained in the form of a glassy orange mass. This product is again dissolved in ether and stirred with an aqueous solution sodium hydroxide (0.3 sodium hydroxide in 30 ml of water). The mixture is stirred until the ether is distilled off and the precipitated solid is filtered off. The aqueous solution is acidified and the crude product indicated in the title is filtered, washed with water and a small amount stvom ether to give 0.8 g of product m "area, -. After recrystallization from isopropanol, 0.6 g of the compound is obtained. Mp. -






    6
    Example C73: Similarly to those described in examples 1 and 2, the listed compounds of the general formula (I) are obtained, in which X is a cis R7
    hydrogen, Y - -CH a R, R (pregener (Table 1).
    NH-S02R,
    N
    B
    In the same way as described in examples 1 and 2, the following compounds of general formula (I) are obtained, in which R2 and R7 are hydrogens, and R and R4 are methoxy groups (Table 2, examples 38 - 51)
    . NH-S02Ri A A, XOCI:

    R
    R.
    Example
    K-Acetyl-2-chloro-6, (, 6-dimethyl-2-pyrimidinyloxy) thiazolo (3,2-b) (1,2,) triazole-2-sulfonamides
    0.29 g of sodium hydride in the form of an 80% suspension in oil is washed with kerosene and 2.7 g of 2-chloro-6- (A, 6-dimethyl-2-pyrimidinyloxy) acetanilide are added as a suspension to tetrahydrofuran. in 30 ml of tetrahydrofur with stirring and cooling, after which the resulting mixture is stirred for another 70 minutes. Then, 1.03 g of thiazolo (3,2-b) 1,2, -triazole-2-sulfonyl chloride is added to it at 15 ° C and the mixture is stirred for an hour, after which it is evaporated and the residue is stirred with 0.3 g sodium hydroxide in a mixture of water and ether for 3 hours. The mixture is then filtered and the solid is washed with water and ether. Then it is successively recrystallized from a mixture of ether and acetone by evaporation of the solvent and, after filtration, from acetonitrile, to obtain 0.6 g of the desired product ToPL. 190 - 192 C,
    EXAMPLE 53 and 2-Chloro-6 - (, 6-dimethoxy-2-pyrimidinyloxy) -1,1,1-trifluoromethanesulfonanilide (as a salt with triethylamine).
    O, g of triethylamine in 100 ml of diethyl ether is added dropwise with stirring to a cooled solution of the product according to Example 1 (1.5 g) in 40 ml of diethyl ether, and the mixture is stirred for 30 minutes, after which filtered to obtain 1.6 g of the desired product as a white solid.
    EXAMPLE 54 59o The following salts are prepared as described in Example 53:
    54 ° The sodium salt of the compound of Example 1 (b), mp above 350 ° C;
    55. Triethylamine salt of the compound of example 1 (b), Topl 121-122 ° C;
    56 o Salt of diisopropylamine compound of example T (b), m.p. 148 - T49 ° C
    57c Piperidine salt of the compound of Example Kb), ToPl 162 - 1b3 ° C;
    58. The cyclohexylamine salt of the compound of example I (b), m.p. 165 - 166 ° C;
    59.Kaliev salt of the compound of example 32
    PRI me R 60. 2-Chloro-6- (4,6 dimethoxy-2-pyrimidinyloxy) M-mile 1,1,1-trifluoromethanesulfonanilide „
    0.64 g of methyl iodide is added with stirring to a solution of the product of example 1B (1.8 g) in 1C ml of dimethylformamide and stirring is continued for 30 minutes. The mixture is left overnight, after which it is added with ice-water and extracted diethyl ether The extract is washed with 3 portions of water, dried and evaporated, the desired product is obtained in the form of a yellow glassy mass I, g After recrystallization from petroleum ether (m.p. 80-100 ° C), 0.95 g of product is obtained with 102 use °,
    Example of herbicidal testing A (pre-emergence treatment)
    The seeds of the following weed are sown in a tank of anodized aluminum, 19 cm long, 9.5 seconds wide and 6 cm deep, containing sterilized sandy loam. The crops are watered and sprayed with the coilacHo compounds listed in the form of a solution (suspension 1: 1 by volume) of acetone and a solution of wetting agent 0 — poly (ethylene oxide) (20 mol) of monolaurate (2 g / l).
    0
    five
    five
    0
    The concentration of each of the tested compounds and the volume of the composition used are selected so as to have the desired dose of the test substance at 450 l / ha. After 3 4 weeks of growth in a room with controlled conditions (20 ° C, relative humidity 75 95% 0 artificial lighting during
    14 h / day) estimate the effect of the herbicide exposure visually
    All differences compared with control samples that did not undergo treatment were correlated with a scale according to WHICH 0 — no effect, 1– 1-24% damage, 2–25–691 damage, 3–70-89% damage, and 4 - woo-100% damage. The following letter designations are used in the tabloz for plant species:
    and - peach (Polygonum lapathifolium); b - tenacious bed-bed (Galium ararine); c — gold flowers (Chrysanchenium segetum);
    d - field foxtail (Alopecurus 0 myosuroides);
    h e - creeping wheatgrass (Agropyron Repens); f - wild oat (AVetia f atua) 5
    g - limnokharis (Abutilon theoph- 5 rasti);
    h - yellow sedge (Gyperus esculeucus); i - ipome (bindweed purple)
    (Pharbitis purpurea) j 0 -j - chicken millet (hedgehog)
    (Echinochloa crussgalli); k - foxtail (Setaria viridis);
    1 - nightshade (Solanum nigrum). Example of herbicidal testing B (post-harvest processing)
    The seeds of the weed species listed below are sown in anodized aluminum tanks, 19 cm long, 9.5 cm wide and 6 cm deep, containing sterilized sandy loam. Cropped tanks are watered and placed in a greenhouse with controlled climatic conditions (temperature 20 ° С, relative humidity 75 - 95 ° С, artificial lighting during And h / day After And or 21 days after sowing (depending on
    plants, however always in those cases
    For example, when most of the plants have from 2 to 3 leaflets formed, the plants are sprayed on the leaf surface with the compounds listed below according to the above examples in the form of a composition consisting of a solution (suspension 1: 1 by volume) of acetone and a wetting solution — polyoxyethylene (20 mol) monolaurate
    (2 g / l).
    Concentrations of each of the test compounds are calculated so as to obtain the desired dose of the test compound at a flow rate of 50 l / ha. After 2-3 weeks of cultivation in a greenhouse with controlled climatic conditions, the effect of the herbicidal effect is assessed visually.
    All differences compared to non-treated control samples are evaluated according to
    with a scale according to which 0 - no effect, 1 - lesions, 2 - lesions, 3 - 0-89% of lesions, and H - 90-1001 lesions. In Table D. The letter designations correspond to the weed species shown in the example of the herbicide test A. When testing obtained results are given in Table.,.
    Comparative Tests Two known compounds related to the substances of the present invention were tested using the method of Herbicidal Examples A and B given: in the description. These known compounds have the formula
    СООС2Н5
    MAIN-
    N
    50
    OCH3
    Example A Compound K1 C-C1 Compound K2 N-H The results with respect to Beta vulgaris (sugar beet) in comparison with the proposed substances are as follows:
    . Pre-emergence period "
    The compound at the dose, g / ha Resulurate
    test
    50428
    Jq
    -7o
    K1
    K2
    one
    k
    li
    31
    33
    k2
    50
    ten
    32 16 125 32 500 16 125 250 425
    Post-emergence period
    K116
    K28
    132
    k32
    3232
    33125 35125
    3
    C 1 1 1 About
    Ltd
    4 it 1 1 1 о о о

    Compounds of other examples with similar tests showed results of 0 or 1 at a dose of 32 g / ha.
    The proposed substances are much safer than sugar beet when used in the same or higher doses than known substances, and can be used as selective herbicides for sugar beets.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of producing sulfoanilides of the general formula
    2
    i N-S02r4i N
    And p-X-tC f 3,
    R "
    7
    Ri
    where a is nitrogen or a group of CR,
    Where
    R5 is hydrogen, methyl, fluorine, chlorine, bromine or trifluoromethyl;
    X is oxygen or sulfur;
     - nitrogen or group
    R is methyl, trifluoromethyl, cyano-methyl, chloromethyl, phenyl, possibly substituted by chlorine or methoxycarbonyl, benzyl, methoxycarbonylamino group, thiazolo (3,2-b) (1,2, Mtriazol-2-yl, 5,7- Dimethyl (1,2,4) triazolo (1,5-a) pyrimidin-2-yl or 5-methyl-Zmethoxycar Sunypirazo (1,5-a) pyrimidin-2-yl, R - hydrogen, methyl or acetyl; R3 is hydrogen, methyl or methoxy group; K4 is hydrogen, methyl, methoxy group, chlorine or cyclopropyl; K is hydrogen, methyl or chlorine; R / is hydrogen, or methyl, or their bases with bases, what is aniline of the general formula
    2
    NH A
    .R,
    X-fir 3 NYY Ri
    where A, X, Y, RЈ-R4, Rg,
    R and X have
    specified values
    subjected to interaction with sulfo-anhydride of the general formula
    50g) gO or with a sulfonyl halide of the formula
    R4S02Hal,
    where R1 has the indicated meanings; Hal - halogen,
    in the presence of a base, followed by isolation of the desired product in free form or salt with a base
    (1,2,) triazol-2-yl
    5,7-Dimethyl (1,
    2, A) thiazolo
    (1,) pyrimidin-2-yl
    i 5-Me-3-COOMePirazolo (1,5-a) pyrimidin-2-yl
    Thiazolo (3,2-b) (1,2,) triazol-2-yl
    Table 1
    Ome
    Ome
    161-163
    Ome
    Ome
    223-225
    Ome
    H
    C1
    Ome
    H
    Me
    C1
    su
    Me
    Ome
    H
    155-156
    222-224
    137-139
    133-134
    143-146
    206-09
    163-165
    139-140
    136-137
    50-60
    229-232
    13
    14 Continued tlll. one
    T a b l and c a 3
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    引用文献:
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    GB8610530D0|1986-04-30|1986-06-04|Fbc Ltd|Herbicides|
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    EP0596899B1|1991-06-29|1995-04-26|Hoechst Schering AgrEvo GmbH|New mixtures of herbicides and antidotes|
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    DE4217928A1|1992-05-30|1993-12-02|Hoechst Ag|Aceto:lactase synthase inhibiting herbicide compsn. - contg. new or known aryloxy cpd. as safener, giving increased selectivity esp. in cereals or maize|
    US5494888A|1993-01-27|1996-02-27|Lucky Ltd.|6-chloro-2-oxybenzoic acid imino ester derivatives, processes for their production and a method for their application as herbicides|
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    ES2209466T3|1998-07-29|2004-06-16|Ihara Chemical Industry Co., Ltd.|DERIVATIVES OF DIFLUORMETANOSULFONILANILIDA, PROCEDURE FOR PREPARATION AND HERBICIDES CONTAINING SUCH DERIVATIVES AS ACTIVE INGREDIENT.|
    KR100987591B1|2002-03-29|2010-10-12|구미아이 가가쿠 고교 가부시키가이샤|Granular agricultural­chemical composition|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GB888823288A|GB8823288D0|1988-10-04|1988-10-04|Herbicides|
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