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    • 专利摘要:
    2-amino-4-substituted-5-thiazolecarboxylic acids and derivatives thereof, are intermediates for the preparation of 2-substituted-4-substituted-5-thiazolecarboxylic acid derivatives which are herbicidal safeners. The compounds of the invention have the formula …<CHEM>… wherein n is zero or one; R is alkyl having 3 to 9 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, nalo (lower) alkyl, or …<CHEM>… wherein… X and Y independently equal hydrogen, halogen, trifluoromethyl or lower alkyl; when n is one R<1> is hydrogen, alkyl having 1 to 10 carbon atoms, lower alkenyl, lower alkynyl, lower alkoxy lower alkyl, halo(lower)alkyl, benzyl, phenyl or phenyl substituted by one to two halogen, lower alkyl or trifluoromemoieties; when n is zero R<1> is -NR2R3 where R2 and R3 independently equal lower alkyl; provided that when n is one and R<1> is hydrogen, X and Y cannot both equal hydrogen; further provided that when n is one and R1 is alkyl containing 1 to 10 carbon atoms or benzyl, R cannot equal trifluormethyl.
    公开号:SU973022A3
    申请号:SU802984497
    申请日:1980-09-30
    公开日:1982-11-07
    发明作者:Кэннес Хоув Роберт；Фанг Ли Лен
    申请人:Монсанто Компани (Фирма)；
    IPC主号:
    专利说明:

    tert-butyl nitrite and copper chloride (II) in the presence of acetonitrile. The reagents are mixed in equimolar amounts at room temperature (). Higher or lower temperatures are applicable, however. The separation of the Pr 5 of the product from the reaction mixture is easily accomplished by conventional methods. It, for example, can be directly obtained by filtration of the reaction mixture or by trituration of the filtrate with a suitable volume of bn. hydrogen chloride. The mixture is then extracted with an appropriate organic solvent, for example ether. The extract is dried and concentrated by distillation in a spherical tube. Example. 1-7 illustrate the method. obtaining the starting compounds of the formula, and examples 8-21 - the target products of the formula. Example 1. Obtaining ethyl-2-amino-4-ethyl - 5-thiazole carboxylate. Ethyl 2-chloro-3-oxopentanoate is obtained from ethyl 3-ox6 pentanoate and sulphuryl chloride. A mixture of 9.2 g (0.0515 mol) ethyl - 2-chloro-3 oxopentanoate, 3.92 g (0.0515 mol) of thiourea and. 30 ml of ethanol are maintained at reflux for 17 hours. Ethanol is then removed under reduced pressure and the residue is treated with 300 ml of saturated sodium bicarbonate solution. A solid precipitate is collected on a filter to obtain 11.2 g of a white substance with so pl. 165-170s, which, after recrystallization from ethanol, gives 7.7 g (75%) of ethyl 2-amino-4-ethyl-5 thiazolecarboxylate in the form of colorless prisms with m.p. 177-179 C. Found,%: C 47.92; H 6.04; N 14.00. . Calculated,%: C 47.92, H 6.04, N 13.99. 2. Preparation of ethyl Example -2-amino-4-tert-butyl-5-thiazole-carboxylate silate. Using ethyl 2-chloro-4; 4-dimethyl-3-oxopentanoate and taking the sample as described in Example 1, the above named product is obtained with mp. 99,0100, . Found,%: C 52.66, H 7.06, M4HCJteHo,%: C 52.60; H 7.0b | N 12.27. Example 3. Obtaining ethyl-2-amino-4- (p-fluorophenyl) -5-thiazole-car boxylate. A mixture of 10.5 g (0.05 mol) of ethyl p-fluorobenzoyl acetate, 6.7 g (0.05 mol of sulphuryl chloride and 30 ml of chloroform is kept for 18 hours at a temperature of de-light, then it is cooled. The chloroform solution is washed with water, dried by sulphate magnesium and concentrated under reduced pressure. The residue is distilled to give 10.8 g (88%) of ethyl 2-chloro- (p-fluoro) benzoyl acetate in the form of an oil. A mixture of 10.8 g (0.0441 mol) of ethyl -2-chloro- (p-fluoro) -benzoyl acetate, 3.36 g (0.0441 mol) of thiourea, 20 ml of water and 10 ml of ethanol are kept for 3 hours at reflux temperature, after which ethanol is removed under reduced The residue is made alkaline with a saturated solution of sodium bicarbonate. The solid is filtered, washed with water and recrystallized from ethanol to give 8.9 g (76%) of ethyl 2-amino-4- (p-fluorophenyl) -5-thiazolecarboxylate in in the form of white prisms with a melting range of 205-208 s. Found: C 54.12; H 4.16 N 10.52. H. B.1 number,%: C 54, li; H 4.16; M 10.52. Example 4. Preparation of ethyl 2I-amino-4-p-chlorophenyl-5-thiazolecarboxylate. To a cold (5 ° C) strongly stirred mixture of 121; 87-g (O, 936 mol) of ethyl acetate-acetate, 314 ml of benzene and 626 ml of water, 41.25 ml of 33% sodium hydroxide solution are added. 177.0 g (1.01 mol) of p-chlorobenzoyl chloride and 188.8 ml of a 33% sodium hydroxide solution are simultaneously added to this mixture through two dropping funnels over two hours. The pasty reaction mixture is then heated for one hour at a time, cooled and filtered to obtain 170.0 g of sodium ethyl 2-benzoyl acetoacetate. A portion (150 g) of this salt is added to a mixture of 39.0 (0.729 mol) ammonium chloride and 78 ml of concentrated ammonium hydroxide in 780 ml of water. This mixture was stirred at 40-50 ° C for 3 hours and cooled in an ice bath. The precipitate is filtered to obtain 115.5 g of a yellow solid, which is distilled in a spherical expansion tube to obtain 76.0 g (38% based on ethyl acetoacetate) of crude ethyl p-chlorobenzoate. A mixture of 40.0 g (o, 175 mol) of crude α-ethyl-p-chlorobenzoyl acetate, 24.2 g (0.18 mol) of sulphuryl chloride and a small amount of chloroform is kept at reflux for 6 hours, cooled and concentrated to give 49, 0 g of crude-about ethyl 2-chloro-p-chlorobenzoate. A mixture of 46.0 g (0.174 mol) of crude ethyl 2-chloro-p-chlorobenzoyl acetate, 13.25 g (0.174 mol) of thiourea and 174 ml of ethanol is maintained at reflux for two hours and cooled. The precipitate is filtered and neutralized with a saturated sodium bicarbonate solution. The insoluble material was filtered to obtain 37.0 g (80%) of ethyl 2-amino-4-p-chlorophenyl-4-thiazolecarboxylate with mp. 198-200s. Found,%: C 50.88; H 3.93; N 9.90. c iV-jCiNiO s. Calculated,%: C 50.96) H 3.92, N i9.90. For example 5. Preparation of ethyl-2-amino-4- (o-chlorophenyl) -5-thiazolecarboxylate. To a cold () strongly stirred mixture, 55.0 g of C (0.423 mol) of ethyl acetoacetate, 70 m of benzene, 18.3 ml of 33% sodium hydroxide solution, and 141 ml of water are added simultaneously 80.0 g (0.457 mol) of chlorobenzoyl chloride and 76 ml of a 33% sodium hydroxide solution for 1 h. An aqueous solution of sodium ethyl-O-5-orbenzoyl acetoacetate is mixed with 22.5 g (0.424 mol of ammonium chloride for 18. Then the aqueous solution is pumped in with 25.0 sodium chloride. A precipitate is immediately deposited, which is filtered. According to analytical data, this material mainly consists of sodium sulphate. Ethyl o-chlorobenzoyl acetoacetate (Natrivuk) salt and aqueous filtrate were collected and acidified with dilute hydrochloric acid. The extractant is extracted with ether. Ether solution. dried (MgSO4) and concentrated under reduced pressure. The residue is subjected to distillation in a tube with a prominent expansion, after which 30.0 g of oil is obtained, which mainly contains ethyl o-chlorobenzoyl acetate. This substance is mixed with a mixture of 7.2 g of ammonium chloride, 14 ml of concentrated ammonium hydroxide and 150 ml of water, after which it continues to work as indicated in example 4. Obtain 16.6 g (15%) of not purified ethyl o-chlorobenzoate acetate about 92%. A mixture of 15.0 g of vO, 065 mol) ethyl o-chloro benzoyl acetate, 9.5 g (0.070 mol) of sulfuryl chloride and 20 ml of chloroform is kept at reflux temperature and concentrated to give 17.3 g of crude ethyl 2-chloro o-chlorobenzoate acetate. A mixture of 17.0 g (0 mol). ethyl 2-chloro-o-chloro-benzoyl acetate, 4.94 g (0.065 mol) of thiourea and 65 ml of ethanol are kept for 2 hours at reflux temperature, after which they continue to work as indicated in example 4 to obtain 15.0 g of solid from m.p. 114-13bc This substance is recrystallized two times from ethanol to obtain 5.8 g (31%) of ethyl 2-amino-4- (o-chlorophenyl) -5-thiazolecarboxylate, m.p. 165-166 C. Found,%: C 50.96; H 3.9 b) N 9.91-, C1 12.54. .N .5. calculated,%: C 50, .96; H 3.92, N 9.90, CE 12.54. Example 6. Preparation of ethyl 2-amino-4- (m-tolyl) -5-thiazolecarboxylate. X cold () mixture of 137.5 g (1.05 mol) of ethyl acetoacetate, 175 ml of benzene, 325 ml of water and 45.8 ml of 33% sodium hydroxide solution were added simultaneously, as indicated in Example 4.221.05 g (1.430 mol) m-toluoyl chloride and 190 ml of a 33% sodium hydroxide solution. An aqueous solution of the sodium salt of ethyl-m-toluoylacetoate is stirred with 56.3 g of ammonium chloride overnight, then continue to work as indicated in example 4 and receive 38.0 g (17%) of crude ethyl-mtoluoyl acetate after distillation of the mixture in the nodule expansion (95-980C at 0.05 mm Hg). A mixture of 20.6 g (0.1 mol) of crude ethyl m-toluoyl acetate, 13.6 g (0.105 mol) of sulfuryl chloride and 30 ml of chloroform was held for 6 hours at reflux temperature, then pro-. the operation is as described in Example 4. Get 25.0 g of ethyl 2-chloro-m-toluoylacetate, which is used directly, as indicated below. A mixture of 22.5 g (0.1 mol) of ethyl 2-chloro-m-toluoyl acetate, 7.6 g (0.11 mol) of thiourea and 100 ml of ethanol is left to stand for 2 hours at reflux temperature, and then continue working as indicated in Example 4. 23.0 j of a solid is obtained which is recrystallized from ethanol to obtain 11.6 g (44%) of ethyl 2-amino-4-m-tolyl-5-thiazolecarboxylate with mp: - 185- 187 ° C. Found,%: C 59.55) H 5.42, N 10.68. C4, S. Calculated,%: C 59.52, H 5.38, N 10.68. Example 7. Preparation of ethyl 2: α-amino-4-isopropyl-5-thiazolecarboxylate. Using the procedure specified in Example 1, a mixture of 1.97 g of vO, 01 mol) ethyl 2-chloro-4-methylpentanoate, 0.76 g (0.01 mol) of thiourea and 30 ml of ethanol for 18 hours at reflux temperature is maintained. Ethanol is removed under reduced pressure. The residue is crystallized from hexane. The solid residue is dissolved in ether, and the ethereal solution is rotted with water, dried with magnesium sulfate and concentrated under reduced pressure. The residue is recrystallized from benzene / ether to obtain 0.85 g (39.6%) of ethyl 2-amino-4-isopropyl-5-thiazolcarboxylate with mp. 173-176С. Found,%: C 50.47J H 6, b) N 13.07. Wed -a-OaS. Calculated,%: C 50.47, H 6.61, N 13.07. Example 3. Preparation of ethyl 2-chloro-4-isopropyl-5-thiazolecarboxylic acid. . . 12.36 g (0.12 mol) of tert-butyl nitrate, Rita; 12.90 g (0.0963 mol) of CuEl and 320 ml of acetonitrile are added in portions to 16.7 g. (0/078 mol) ethyl-2-amino-4-isopropyl-5-thiazolecarboxylate for 40 minutes The reaction mixture is stirred at room temperature for 1 h, then heated to 65 ° C. After that, the mixture Filtersygut, the filtrate is drunk in 400 ml 6 in. hydrochloric acid. Water extracted with ether. The ether extracts are dried with magnesium sulfate and concentrated to give 17.0 g of oil, which is distilled in a round bottom flask at 1.5 mm Hg. to yield 15, .7 g (86%) of the title product. 1.5145. H .5.22 Found: C 46.40, 6.06. . C 2M02.S: Calculated,% C 46.24} H 5.18, 5.99. Example 9. Preparation of ethyl 2-chloro-4-tert-butyl-5-thiazolecarboxylate. .In a thoroughly stirred mixture. Of 38.62 g (0.375 mol) of tert-butyl nitrate, 43.3 g (0.4 mol) of CuCta. and 300.0 ml of acetonitrile, 57.0 g (0.25 mol) of ethyl 2-amino-4-tert-butyl-5-thiazolecarboxylate are added over 1 hour. The reaction mixture was treated in the same manner as in Example 8 to obtain 55.9-g of crude oil, which was distilled at 1 mg Hg. to obtain the first fraction in the amount of 4.4 g with BP. 90 ° C (p 1,5008) and the second fraction in the amount of 47.6 g (79%). With so kip. (p 1.5160) 2-ChloE-4-tert-butyl-5-thiazolcarbyksilata. . Found: C 48.41 H 5.73, N 5.62, d oH 4Ctiia2.s. calculated%: C 48.48, H 5.70 N 5, .56. Example 10. Preparation of ethyl 2-chloro-4-p-chlorophenyl-5-thiazolecarboxylate. 14.7 g (0.17 mol) of copper and 100 ml of acetone (cyxot-o) were added to a thoroughly stirred mixture of 14.6 g of t07i42 mol) - tert-butyl nitrite 15.7 g (0.0875 mol) of ethyl 1-2 amino-4 -p-chlorophenyl-5-thiazolecarboxylate within 30 minutes. The reaction mixture was kept below with an ice bath. It is then stirred for 10 minutes and filtered. The insoluble product is washed with dilute hydrochloric acid and recrystallized from ethanol-chloroform to obtain 14.1 g of a white solid with mp. 117-119c, which is distilled in a round bottom flask at 1 mm Hg. j to obtain 13.8 g of ethyl 2-chloro-4-p-chlorophenyl-5-thiazolecarboxylate with m.p. 120-12lc. The initial acetonitrile filtrate is poured into 20% hydrogen chloride, the precipitate is collected and distilled in a round bottom flask at 1 mm Hg. to obtain 7.0 g of a white solid, which is stirred together with hexanes-chloroform to obtain another 4.7 g of the intended product in 70% overall yield. Found,%: C 47.71J H 2.97, N 4.55. s-gdnr .s. Calculated,%: C 47.70, H 3.00, N4.64. In accordance with the method described in examples 8-10, the compounds listed in the table in examples 11-21 are prepared. The thiazolecarboxylates of formula I are suitable for reducing herbicide damage to agricultural crops, in particular sorghum and rice. These compounds are used to treat the seeds of useful crops and habitats 5c or the cultivated plants themselves in order to reduce damage to the latter due to the use of the herbicide, and without juice; Increasing Herbicide Effects on Debris Protective agent can be applied to a plant's habitat sequentially in a mixture with a herbicide or directly to the seeds of a cultivated plant. By application to a habitat, a plant is understood to mean an environment in which a plant grows, such as soil, seeds, seedlings, roots, stems, leaves, flowers, fruits, or other parts of the plant. Protective agents can be applied to the place of plant growth as a mixture, for example, a mixture of an herbicidal amount of butachlor and a protective agent in an amount sufficient for a protective effect, or in addition, that is, the place of plant growth can be treated first with a quantity of butachlor, and then protective agent or vice versa. The ratio of butachlor and preservative can vary depending on a number of factors, such as the type of weeds being destroyed, the type of treatment, etc., although you can usually work with a ratio of herbicide and protective agent from 1:25 to 25: 1 (preferably 1: 5-5: 1) weight.h. With a herbicide, protective agent or mixture thereof, the plant growing place can be treated in pure form or else with a herbicide, protective agent or mixture thereof can be processed in combination with a known auxiliary agent in liquid or solid form. : Mixtures containing the appropriate herbicide and protective agent are usually obtained by mixing the herbicide and the protective agent with an auxiliary agent, which includes diluents, fillers and conditioning agents and carriers, in order to obtain cestav in the form of finely distributed solid particles, granules, tablet, wettable powders, dusts, solutions and aqueous dispersions or emulsions. Thus, the mixtures may contain an adjuvant such as finely divided solid particles, a liquid solvent of organic origin, water, a wetting agent, a dispersant or an emulsifier, or any combination of these agents. When treated with a herbicide, a protective agent, or their mixtures of plants, useful carriers (solid finely divided particles) or the same excipients include, for example, talc, clay, pumice, silica diatomaceous earth, quartz, Fuller's earth, sulfur, powder plug , powdered wood, walnut flour, chalk, vegetable or charcoal tobacco dust and. etc. Typical liquid diluents. for example, is Stodzard solvent, acetone, alcohols, glycol, ethyl acetate, benzene, and the like. Such formulations, in particular liquid and wettable powders, usually contain as conditioning agents one or more PLVs in quantities sufficient to give this composition a slight solubility in water or oil. By surfactant is meant wetting agents, dispersing agents, suspending agents and emulsifying agents. The compositions typically contain from about 5 to 95 hours of the herbicide and a protective agent, from about 1 to 50 hours of surfactant and from about 4 to 94 hours of solvent / all parts are based on the total weight of the composition. Use of a herbicide, a protective agent, or mixtures thereof c. in liquid form or in the form of solid particles, conventional technologies can be carried out using, for example, sprinklers, motor sprays, sucker-rod and hand sprays, sprinklers and devices for applying granules. The formulations can also be applied by air treatment from an aircraft in the form of dust or dusting. In appropriate case, the treatment with formulations can be done by adding the composition to the soil or medium. Since usually only a very small amount of protective agent is required for seed treatment, the compound is preferably prepared in the form of a powder or emulsifiable concentrate, which can be diluted with water during seed treatment with an appropriate device or apparatus. It is natural that under certain conditions it is recommended to dissolve the protective agent in an organic solvent when using it for seed treatment, or to use a pure compound under suitably controlled conditions.
    权利要求:
    Claims (1)
    [1]
    1. Patent of the USSR 306626, cl. C 07 D 277/56, 1966.
    2 Heterocyclic Compounds Ed. R. Elderfield, M ,, IL, T961, V.5, p. 432.
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    同族专利:
    公开号 | 公开日
    BR8006288A|1981-04-07|
    AT4898T|1983-10-15|
    ES8107205A1|1981-10-01|
    EP0027018B1|1983-10-05|
    BG32849A3|1982-10-15|
    AR228436A1|1983-03-15|
    MY108185A|1985-12-31|
    ZA806026B|1981-11-25|
    RO80662B|1983-04-30|
    CA1151654A|1983-08-09|
    EP0027018A1|1981-04-15|
    CS231979B2|1985-01-16|
    RO80662A|1983-06-29|
    IL61179A|1984-11-30|
    KR850000572B1|1985-04-29|
    PL227012A1|1982-04-26|
    US4308391A|1981-12-29|
    DK413380A|1981-04-02|
    NO152872C|1985-12-11|
    DE3065179D1|1983-11-10|
    AU6282380A|1981-04-09|
    KR830003457A|1983-06-20|
    AU530565B2|1983-07-21|
    IN151250B|1983-03-12|
    IL61179D0|1980-11-30|
    CS660880A2|1984-01-16|
    PL128997B1|1984-03-31|
    NZ195099A|1983-09-02|
    ES495439A0|1981-10-01|
    NO802889L|1981-04-02|
    JPS5668676A|1981-06-09|
    NO152872B|1985-08-26|
    引用文献:
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    FR1546183A|1966-12-07|1968-11-15|Uniroyal Inc|Carboxamidothiazoles, their substituents and derivatives, their manufacturing processes as well as their agricultural applications and application processes|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US06/080,752|US4308391A|1979-10-01|1979-10-01|2-Amino-4-substituted-thiazolecarboxylic acids and their derivatives|
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