• 专利附录
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    • 专利摘要:
    Method of controlling weeds by using a 5-imidazolecarboxylic acid of formula <CHEM> or a stereochemically isomeric form thereof, or a salt thereof, or a quaternised form thereof, or a N-oxide thereof, wherein A is hydrogen; C3-C7cycloalkyl optionally substituted with one or two C1-C5alkyl radicals; C1-C7alkyl optionally substituted with C1-C7alkyloxy or with an Ar radical; or C1-C7alkyl substituted with both a a C1-C7alkyloxy and an Ar radical; or a radical selected from pyridinyl, pyrimidinyl, naphthalenyl, furanyl and thienyl, each unsubstituted or substituted; said radical Ar being unsubstituted or substituted phenyl, pyridinyl, pyrimidinyl, naphthalenyl, furanyl or thienyl; Z is naphthalenyl, thienyl, furanyl, pyrimidinyl, phenyl or pyridinyl, each unsubstituted or substituted; novel compounds of formula (I); compositions containing such agents as an active ingredient and methods of preparing said compositions and novel compounds.
    公开号:SU1558302A3
    申请号:SU874202079
    申请日:1987-03-03
    公开日:1990-04-15
    发明作者:Франс Элизабета Ван Гестель Йозеф；Лутз Вильям；Розалия Эжен Ван Ломмен Ги；Фишер Ханспетер；Франсис Жозефин Шровен Марк；Туммел Рудольф
    申请人:Жансен Фармасетика Нв (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the preparation of new derivatives of 1-methyl-1H-α-imidazole-5-carboxylic acid or to Ax (Yul m having herbicidal activity.
    The purpose of the invention is the synthesis of new imidazole-5-carboxylic acid derivatives, which are superior in their activity to a structural analogue possessing the same type of activity.
    Examples of.
    Example 1. A solution of 1.37 parts of sodium methoxide in 20.5 parts of tetrahydrofuran is prepared by adding the required amounts of methanol and sodium hydride to tetrahydrofuran. If not necessary
    4.1 parts of formic acid methyl ester and 6.0 parts of methyl-K-formyl-M-j (4-methylphenyl) butyl glycine are added until room temperature is cooled to room temperature. After 20 hours, the mixture is treated with 18 parts of deionized water and 28 parts of 1,1-oxybisethane. The aqueous phase is separated and 1A part of methanol and 6.5 parts of 36% hydrochloric acid are added. The solution is heated to and treated with a solution of 3.7 parts of potassium thiocyanate in 6 parts of deionized water. After 2k hours, the mixture is heated to 80 ° C for 5 hours. After cooling, the precipitated product is filtered and dried, yielding 5.23 hours (75%) methyl 1-D (-methylphenyl) butyl-2-mercapto- 1H-imidazole-5-carboxylate, m.p. 209-2114 (compound 1, P).
    Example 2: Dissolve 0.07 h of sodium nitrite and 0.6 parts of nitric acid in 2 parts of deionized water. 1.0 part of methyl 1-1- (- (| -methylphenyl) butyl -2-mercapto-1 -imidazole-5-carboxylate) is added at a temperature between 25 and 30 ° C. Separate, beside, obtain 0.9 h- (86%) methyl-1-. - | j - (Ii-methylphenyl) butyl - 1 H-imidazole-5 carboxylate mononitrate. This colorless salt has a mp. 14 -1hZ ° C (compound 1.15) "
    EXAMPLE 3 A mixture of kk parts of α-phenyl-2-pyridinemethanamine, 27 parts of methyl chloroacetate, 30 hours, M, K-diethylethanamine and 270 parts of M, N-dimethylformamide are mixed throughout overnight at room temperature. The reaction mixture is poured into 1000 parts of water. The product is extracted with 1, 1-oxybisethane. The extract is washed three times with water, dried, filtered and evaporated, yielding 37 h (62.8%) methyl-M-enyl (2-pyridinyl) methyl glycine as a residue.
    A mixture of 37 parts of methyl-M-phenyl (2-pyridinyl) methyl glycine, 36 parts of formic acid and 50 parts of dimethylbenzene is stirred and refluxed for 2 hours. The reaction mixture is poured into water. The product is extracted with 1,1-oxybisethane. The extract is washed successively with a 10% sodium hydroxide solution and water, dried,
    The filtrates that have been discarded are evaporated. The residue is purified by chromatography on a column of silica gel, using a mixture of trichloromethane and methane pa (95: 5 by volume) as eluent JQ t. The pure fractions are collected and the eluent is evaporated, obtaining a second fraction of 31 parts (27.8%) of methyl 1-phenyl (2-pyridyl) methyl -1H-imidazole-5-carboxylate as a residue. Overall output
    filtered and evaporated. The residue is purified by chromatography on a column of syl 68.2 parts (61.1%) of methyl 1-phenyl (2-pi-nickel) using a mixture of trichloromeridine) methyl -1H-imidazole-5-carboxane and methanol (90:10 by volume) as eluent. Collect the pure fractions and evaporate the eluent to give
    silat (compound 1.253).
    Example 5: 33.0 parts of ammonium carbonate are added at room temperature5.
    ten
    20
    55
    25 jq
    c $ 583024
    2k parts (60.3%) of methyl-M-formyl-M- {phenyl (2-pyridinyl) methyl glycine as a residue.
    To a stirred solution of 2 parts of a 50% dispersion of sodium hydride in 5 parts of tetrahydrofuran was added 11.5 parts of methyl-L-formyl-M-phenyl (2-pyridinyl) methyl glycine. After 10 minutes, 2 parts of methylformate were added and stirred overnight. The reaction mixture is concentrated to a volume of about 20 hours. The precipitated product is filtered off and treated with 100 parts of water and 70 parts of 1,1-oxybisethane. Mix everything for 15 minutes and separate the layers. The aqueous phase is acidified with 18 parts of concentrated hydrochloric acid, and then 5 parts of potassium thiocyanate are added. After stirring over the weekend (weekend), the product is filtered off and dried, yielding 10.8 parts (83.0%) methyl 2-mercapto-1- - (benil (2-pyridinyl) methyl-Sh-imidazole) 5-carboxylate (compound 1.208).
    Example. A mixture of 123.6 parts of methi-p-2-mercapto-1-phenyl (2-pyridinyl) methyl -1 H-imidazole-5-carboxylate, 0.2 parts of sodium nitrate, 219 parts of nitric acid and IO parts of water stirred for 2 h at room temperature. The reaction mixture was poured into water and the whole was treated with sodium hydroxide solution (in an ice bath). The product is extracted with methylene chloride. The extract is dried, filtered and evaporated. The bed is crystallized twice: the first time from 2-propanone, and then from 4-methyl-2-pentanone. The product is filtered off (the filtrates are discarded) and dried in vacuum at 70 ° C. The first fraction is obtained from 37.2 parts (33.3%) of methyl 1- phenyl (2-pyridinyl) meth and H-imidazole. 5-carboxylate, so pl. 9 &amp; 3 ° C.
    The filtrates that have been discarded are evaporated. The residue is purified by chromatography on a column of silica gel using a mixture of trichloromethane and methano-pn (95: 5 by volume) as eluent JQ t. Pure fractions are collected and the eluent is evaporated, yielding a second fraction of 31 parts (27.8%) of methyl 1-phenyl (2-pyridinyl) methyl -1H-imidazole-5-carboxylate as a residue. Overall output
    35
    40
    “68.2 parts (61.1%) methyl-1-phenyl (2-pyridinyl) methyl -1H-imidazole-5-carbox-
    68.2 parts (61.1%) methyl-1-phenyl (2-pyridinyl) methyl -1H-imidazole-5-carbox
    silat (compound 1.253).
    EXAMPLE 5: 33.0 parts of ammonium carbonate are added at room temperature 2-diphenylethyl) formylamino-3-oxopropanol in 2bO including dimethylbenzene. The mixture was heated to 70 ° C for 1 hour and to 120 ° C for another 3 hours. The reaction mixture was gradually evaporated until a methyl 1- (1,2-diphenylethyl) -1H-imidazol-5-carboxylate precipitated m.p. (compound 1.).
    PRI me R 6. A mixture of 17h. methyl--2-Ј (1, 2-diphenylethyl) formylamino-310
    51558302.6
    Peratura to solution 1b h. Methyl-2- (1, The filtrate, which was set aside,
    evaporated, a second fraction of 5 parts (73%) of 1 - (cyclohexylphenylmethyl) -1H-imidazole-5-carboxylic acid, m.p. , 5 ° C (compound 1.251).
    PRI me R 9. A mixture of 7 parts (nyl (2-pyridinyl) methyl 3-1H-imidazole-5 -carboxylic acid, 5.5 parts of concentrated sulfuric acid and YO, including cyclohexanol, is stirred for 2 days at. OO ° C. The reaction mixture is evaporated
    -oxopropanoate, 65 parts of ammonium acetate (on an oil pump) and a residue and, 100 hours, of acetic acid, are boiled with dichloromethane. Organic under reflux for 8 hours. Adding a J5 layer is washed with a solution of hydroxide with 50 parts of ammonium acetate and continued, dried, filtered and evaporated to reflux. The residue is purified by chromatography on another k hours. The solution is diluted with a silica gel column using a mixture of
    300 hours of water and extracted twice, trichloromethane and methanol (90:10
    each time 85 hours of methylbenzene. Organized-20 volume) as eluent. The pure, pure phases are combined, the fractions are concentrated and the eluent is collected and evaporated. and separated by chromatography on a column. The residue was crystallized from acetonitrile with silica gel. Concentrating The product is filtered and dried.
    methyl-1- (1,2-diphenyl- in vacuo at 60 ° C) is obtained in the eluate; 2.6 parts of ethyl) -1H-imidazole-5-carboxylate (soy-25 (28.8%) cyclohexyl-1- Phenyl (2-pyridine 1.241). Dienyl) methyl -I-imidazole-5-carboxy Example. A mixture of 17 parts of methyl acetate, m.p. 1b1,0 ° C (compound -2- (, 2-diphenylethyl) formylamino -3-1,255)
    α-oxopropanate, 50 parts of formamide and Example 10. A mixture of k, 6 parts of 1- (110 parts of hydrochloric acid is heated to 30-phenylethyl) -1H-imidazole-5 carboxylic
    YO for 4 hours. After cooling to a final temperature, the mixture is extracted with a mixture of 100 parts of water and 70 parts of 1,17-hydroxyethane. The ether phase is separated, and the aqueous phase is extracted twice, 5 dyes, each pas 79 parts 1,1-oxybisethane. The combined organic phases are dried over sodium sulfate and concentrated to dryness to give methyl 1- (1,2-di-Aenylethyl) -1H-imidazole-5-carboxy-40 lat (compound 1.).
    PRI me R 8. A mixture of 8.7 parts of methyl -1- (cyclohexylphenylmethyl) -1H-imidazole-5-carboxylate mononitrate, 9 hours
    acids and k8 parts of thionyl chloride are refluxed for about 2 hours. After cooling, 1, sibisethane is added. The filter cake was added to 20 parts of 1-propanol and the mixture was heated under reflux for 2 hours. The reaction mixture is evaporated in vacuo. The residue is partitioned between 105 parts of anhydrous 1,1-oxybisethane and 20 hours. 10 n. sodium hydroxide solution. The organic solution is washed with water, dried over magnesium sulfate, filtered and a saturated solution of gaseous hydrogen chloride in a 250% sodium hydroxide solution and 45 propanol is added to the filtrate. Dropped in
     45 l. water, stirred for 1 h at reflux. 35 parts of water are added. After cooling, the reaction mixture is neutralized with acetic acid. The product is extracted with 1 tf-oxybisethane. The extract is dried, liter and evaporated. The residue is crystallized from a mixture of ethanol and acetonitic acid; oily hydrochloride solidifies after friction; the solid is filtered off and dissolved in a small volume of 1-propanol. The non-JQ aqueous 1,1-oxybisethane is added to this solution and the precipitate formed is filtered off after cooling. The precipitate is recrystallized when dissolved in 2-propanol, previously saturated. The product is filtered off (the filtrate is set aside) and dried under vacuum at 55 ° C with gaseous hydrogen chloride, to obtain the first fraction from 2.1 parts of water, and adding anhydrous 1,1-ox- (30.8%) 1- (cyclohexylphenylmethyl) -1M-sibisethane to solution. After cooling, the imidazole-5-carboxylic acid, so that the resulting 5 ° C (compound 1.251) is filtered off and the precipitate is dried under vacuum at kQ C,
    ten
     -phenylethyl) -1H-imidazol-5 carboxylic
    acids and k8 parts of thionyl chloride are refluxed for about 2 hours. After cooling, 1, sibisethane is added. The filter cake was added to 20 parts of 1-propanol and the mixture was heated under reflux for 2 hours. The reaction mixture is evaporated in vacuo. The residue is partitioned between 105 parts of anhydrous 1,1-oxybisethane and 20 hours. 10 n. sodium hydroxide solution. The organic solution is washed with water, dried over magnesium sulfate, filtered and a saturated solution of gaseous hydrogen chloride is added to the precipitate. The oily hydrochloride solidifies after friction; the solid is filtered off and dissolved in a small volume of 1-propanol. Anhydrous 1,1-oxybisethane is added to this solution and the precipitate formed is filtered off after cooling. The precipitate is recrystallized by dissolving in 2-propanol, previously saturated with gaseous hydrogen chloride, and adding anhydrous 1,1-hydroxyethane to the solution. After cooling, the precipitate is filtered off and dried in vacuo at kQ C,
    1.5 parts of propyl-1- (1-phenyl-ethyl) -1 H-imidazole-5-carboxylate, 1.5 ppm; 15b-157 C (compound 1.116).
    Example 11. To a solution of 12.2 parts of ethyl 1- (1-phenylethyl) -Sh-imidazole-5-carboxylate in 160 parts of 2-propanol was added 5 parts of a 65% solution of nitric acid. The product hardens under friction, to obtain part of ethyl -1 -1 (1-phenylethyl) -1H-imidazole-5-carboxyl mononitrate monoxide, mp 138-139 ° C (compound 1.146).
    Example 12. A mixture of 1 part (2-chlorophenyl) butyl -1H-imidazole-5-carboxylic acid, 80 parts of methanol and 35.9 parts of 0.1 n. solution of potassium methoxide is stirred for 1 h under reflux. The reaction mixture is evaporated and the residue is poured in a dry gun at 70 ° C, 0.3 hours (26.7%) of 1-0 (2-chlorophenyl) butyl are obtained -1H-imidazole-5 potassium carboxylate dihydrate, so pl. 70.7 ° C (compound 2..
    Example 13. To a stirred solution of 7 parts of R - (+) - ethyl 1- (phenyl ethyl) -1H-imidazole-5 carboxylate, in part of the sweep, 21.3 parts of dichloromethane are added and everything is stirred for 2k parts room temperature. The reaction mixture is evaporated and the residue is crystallized from 2-propanol. The product is filtered off and washed with petroleum ether, 7.03 parts of ethoxycarbonyl-3 methyl-1- (1-phenylethyl) -1H-imidazolium iodide are obtained, m.p. 159.5 С, (° 0D
     -62.79 ° (Yu% water).
    Example 14. To a stirred and cooled (O C) solution of 5.9 parts of methyl 1 - 1 - (2-chlorophenyl) butyl -1H-IMI dazole-5-carboxylate in 130 parts of dichloromethane was added 3.4. Part 3 chloroperbenzoic acid. After 2k hours of stirring at room temperature, the reaction mixture is washed with 100 parts of a 0.03 M solution of sodium bicarbonate in water and dried, filtered and evaporated (30 ° C). The residue is purified by chromatography on a silica gel column using a mixture of trichloromethane and methanol, saturated with ammonia (95: 5 by volume) as eluent. Collect the pure fractions and evaporate the eluent.
    Data on the obtained compounds are summarized in Table. one.
    Biological examples.
    PRI me R 15- Pre-emergence herbicidal action.
    In the greenhouse, immediately after sowing the test plants in sowing cups, the soil surface is treated with an aqueous dispersion of the test compounds ps obtained from a 25% emulsifiable concentrate or from a 25% wettable powder with test compounds that, taking into account their insufficient solubility, cannot formulated in emulsifiable concentrates. Two series of different concentrations were used, corresponding to 2 and 1 kg of the test compound per hectare, respectively. Cups with sprouted seeds are kept in a greenhouse at 22–25 ° C and relative humidity of 50–70%. The test is evaluated after 3 weeks according to the following method of assessment: 1 - the plants did not germinate or were completely affected; 2-3 - very strong effect; 4-6 - medium action; 7-8 - weak action; 9 - no action - not tested.
    In this test, the test compounds of Formula (l) are most effective against monocotyledonous weeds, whereas they are ineffective or only cause minor damage to cultivated plants such as corn at given application doses.
    The results are shown in Table. 2 (pre-emergence test).
    at
    II p and me R 16. Post-harvest germicidal action (contact herbicide).
    A large number of weeds and cultivated plants are sprayed after sprouting at the 4-6 leaf stage with an aqueous dispersion of the active ingredient in doses of 4 and 2 kg of the test compound per hectare and kept at 24-26 ° C and relative humidity. The test is evaluated at least 15 days after treatment according to the same rating scale that was used for pre-emergence processing.
    In this test, the compounds of formula (I) also proved to be the most effective against the tested weeds. Cultivated plants, such as corn or rice, were either not affected or were affected at higher doses of application of the test compound.
    The results (post-harvest test) are given in table. 3 "
    . PRI me R 17. Herbicidal action in the culture of the transplanted ri-1 sa.
    25-day old rice seedlings of the Yamabiko variety are transplanted into wide plastic containers. In the same containers, weed seeds are sown between rice plants, which are found in rice culture, namely ammonia, syta yellow, millet cockerel, rotala. The containers are filled with water to such an extent that the water layer is 2.5 cm above the surface. After 3 days of exposure to greenhouse conditions, diluted aqueous dispersions of the active compounds are added to the aqueous layer at a deposition rate of 2000, 1000, 500, 250 and 125 g a.i. per hectare. The containers are then kept covered with water at 25 ° C and high humidity in
    greenhouse for k weeks. Evaluation of tests carried out in accordance with the rating scale above.
    The results are shown in Table. k.
    Comparative data.
    Herbicidal activity during pre-emergence treatment.
    In the greenhouse, the seeds of the test plants were sown in plastic pots filled with sandy soil, which is covered with a layer of 0.5 cm of the same soil. Test compounds are dissolved in acg-tone (100 g of compound in ml of acetone) and then diluted with tap water immediately prior to use. 20 ml of the test solution is fed to each pot, which is carefully distributed over the soil surface using a plastic syringe. The test solution is diluted in such a way that the amount of active ingredient per pot is absent with a consumption rate of 4 kg per hectare. During the entire test period (4 weeks), the pots were stored on the shelves under the conditions common to those who were to be found. Temperature and humidity varied according to time of year and day.
    Herbicidal activity was assessed by the degree of plant development according to the following semi-log scale: 1 - no effect (development corresponds to untreated plants); 2 - 2.5% lesion; 3,5% lesion; ft - 10% lesion; 5-15% lesion; S-- 25% defeat; 7 - 35% lesion;


    7-8 - 50% lesion; 8 - 67.5% of the time; 9 100% damage (complete destruction of plants); N.T. - not tested.
    A score of 8.9 indicates that the herbicide activity was about 85%, a score of (8) 9 corresponds to an activity that is closer to 9 than to 8, and 8 (9) is closer to 8 than to 9.
    Data on the obtained compounds are summarized in Table. five.
    The biological activity of a known compound is as follows:
     Rosichka1
    Millet Petus1
    Corn 1
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of obtaining derivatives of 1-methyl-1H-imidazole-5 carboxylic acid of the general formula I
    Al DgChoon2
    R,
    thirty
    35
    0
    i
    from where
    sn
    s
    where R is hydrogen or mercapto; Ru is hydrogen, -St-alkyl; A is C3-St-cycloalkyl, C-St-alkyl, C, -Ct-alkyl, substituted with an alkoxy group or aryl, or simultaneously a C-C7 alkoxy group and aryl, or with unsaturated naphthalenyl or pyridinyl, wherein when A is n-propyl, Z is not phenyl and wherein said aryl is phenyl or pyridinyl;
    Z is phenyl, unsubstituted or substituted by one or two substituents selected from the group C4-C-alkyl, C, -C5-alkoxy, halogen,
    or salts thereof, characterized in that a compound of the general formula II is condensed
    about
    HC-N-CH2-COOR2 CH-Z A
    A and Z have the indicated meanings.
    TO
     Where
    with C4-C-alkyl of formic acid in the presence of a base in an inert solvent and the obtained intermediate is treated with the general formula III
    about - th
    fc
    NA
    HC-N-C-COOR H-Z A
    Z have the specified characters.
    ; Le R, A and j
    M is an alkali metal atom, an alkali metal isothiocyanate in the presence of an acid, obtained in the manner of 2-mercaptoimidazole of the common mule 1a
    IT-N
    R2OOC- N SH CH-Z
    or naphthalenyl, wherein when A is n-propyl, Z is phenyl and said aryl is phenyl or pyridinyl D is phenyl unsubstituted or substituted by one or two substituents selected from the group: C-g-Cs-alkyl, alkoxy, halogen.
    IA
    where R, A, Z have the indicated meanings, 25 19-112.8 A — C, is C7 alkyl substituted by alkoxy and aryl.
    isolated or treated with sodium nitrite in the presence of nitric acid
    in an aqueous medium at 25–30 ° C with isolation of the target product, where R is hydrogen in free form, or with treatment with an appropriate acid or base and isolation of the target product, where R is hydrogen or a mercapto group as a salt.
    Priority by attribute m: 10о03.86 R, - hydrogen or mercapto;
    R is hydrogen; C, -C7 alkyl; Aco-C7-alC-C7-cycloalkyl,
    or naphthalenyl, wherein when A is n-propyl, Z is phenyl and said aryl is phenyl or pyridinyl D is phenyl unsubstituted or substituted by one or two substituents selected from the group: C-g-Cs-alkyl, alkoxy, halogen.
    13
    1558302
    14 . Continued table. T
    15
    1558302
    16 Continued table. one
    17
    155830213
    Continued table. 2
    Table k
    nineteen
    1558302
    20
    Table b
    Al RI N juice2
    Table 6 the activity of the obtained compounds
    N-JI
    % icOOCH5
    | T6Nx
    % BUT
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    同族专利:
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    FR4499M|1964-04-16|
    US3991072A|1975-03-10|1976-11-09|Janssen Pharmaceutica N.V.|Racemization of lower alkyl imidazole carboxylates|
    DE2732531A1|1977-07-19|1979-02-01|Hoechst Ag|IMIDAZOLE CARBONIC ACIDS AND THEIR DERIVATIVES|
    US4595400A|1984-10-18|1986-06-17|Stauffer Chemical Company|Herbicidal esters of 2-bromo-4-methylimidazole-5-carboxylic acid|US4878940A|1987-04-02|1989-11-07|Janssen Pharmaceutica N.V.|Herbicidal 1,5-substituted 1H-imidazoles|
    EP0305330A1|1987-08-25|1989-03-01|Ciba-Geigy Ag|Imidazole derivatives|
    EP0314852B1|1987-11-06|1993-11-18|Ciba-Geigy Ag|Process for the preparation of 1-substituted imidazole-carbonic acid and derivatives|
    US4992090A|1988-06-13|1991-02-12|Ciba-Geigy Corporation|Herbicidally active 5,6-dihydrocyclopentathiophenyl-imidazole derivatives|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US83806786A| true| 1986-03-10|1986-03-10|
    US06/944,694|US4770689A|1986-03-10|1986-12-19|Herbicidal imidazole-5-carboxylic acid derivatives|
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