• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    An acylated diketonic compound is produced by rearrangement of the corresponding enol ester in the presence of a cyanide source. In one embodiment the cyanide source is employed with a molar excess of a moderate base, with respect to the enol ester. In another embodiment, the cyanide source is a stoichiometric amount, with respect to the enol ester, of potassium or lithium cyanide and a catalytic amount of a Crown ether is used.
    公开号:SU1697591A3
    申请号:SU853995138
    申请日:1985-12-19
    公开日:1991-12-07
    发明作者:Брайан Хитер Джеймс；Деним Милано Памела
    申请人:Стауффер Кемикал Компани (Фирма)；
    IPC主号:
    专利说明:

    The invention deviates to be refined. cnocoi / y for the production of acylated nickel-onic compounds that possess herbicidal activity and are used in agriculture.
    The purpose of the invention is to simplify the process by reacting the corresponding diketone with the appropriate acyl halide in an organic solvent medium in the presence of a moderate base followed by rearrangement of the resulting enol ether with or without precipitation or in the presence of an alkali metal cyandoidin metmalkyl (Ci - Gj ) ketone or tri (Ci - C4) alkylsilyl cyanide
    PRI me R 1. Rearrangement of the enol ether.
     Getting 2- (2, 3, 4 -trichlorobenzoyl} - Sz-cyclohexanedione
    A series of experiments was performed to obtain 2- (2, 3,4-trichlorobenzoyl) -1,3-cyclohexyl diox by rearranging its tar ether using different cyanide sources and different solvents. The general procedure is as follows: 3.0 g (0 The 0094 mol) enol zirfir (prepared by reacting 2,3,4-trichlorobenzoyl chloride with 1,3-aciohexane monomer in the presence of triethylamine, followed by separation) is dissolved with 10 ml of solvent with 10 mol.% Catalyst and 140 mol. % triethylamine (both quantities are defined in relation to the ether). The mixture was kept at ambient temperature and left to react for 4–18 hours. The reaction mixture was diluted with water and the solvent was removed at high pressure. The resulting aqueous mixture is acidified to a pH of about 1 by the gradual addition (5% hydrochloric acid at the same time. The resulting solids are collected by filtration and lysu.Ftgmt is of light weight at 75 ° C
    The yield of the product - crude acetyrosine dikeets, which is specific for the initial materials, is given in Table. one
    PRI mme R 2. Preparation of solid 1 - (2,3, 1-trmhloro-benzoyl) -1 3-cycloxygene sandisna without discharge and e.
    I put in a kolgch - 3.0 t (O 02 / mop) of 1,3-hmhlogoksandnona, 15 ml is dissolved and 10 mol.% (According to OTi-o t ti-i / cho to the prostate enol ether) cyanide n jTpw - The reaction mixture is layered with a layer of azo and is maintained at a temperature close to v. Room temperature. Then 300 mol.% Triztilamine (counted on enol ether) is added, keeping still at room temperature. Then add a mixture of / kp 10) mol.% (Relative to the diode) of 2.3.4-tr 4-chloro-isoiso-ichloride. I mix the mixture; at ambient temperature and left to react for 24 hours. The product is recovered according to winner 1.
    The yield of 3.04 g unrefined product (73% of the total volume, uncorrected for the purity of the starting materials),
    Examples 3-6. A series of experiments was carried out analogously to example 2, with the difference that various catalysts and solvents were used. All catalysts ncroibe in an amount of 10 mol.%, Including the enol ether,
    The results of the preparation of 2- (2,3.41-tr x lorbenzoyl) -1,3-cyclohexanedione, with the output being uncorrected for the purity of the starting materials, are given in Table 2,
    Example, Preparation of 2 - (. 3, 1-trih lorbenzoyl) -1,3-c / 1clohexgidione without isolation of the intermediate enolic ester.
    Into the flask is placed 1B g (0 13 mop) of 1,3-cyclohexanedione, 75 ml of 1,2-dichloroethane v, 0.24 ml (2 mol.%, Calculated on enol ether) of acetone cyanohydrin. The materials are placed under a layer of nitrogen and the flask is kept in an ice bath.
    54 is then added in the sequence indicated; 56 ml (34.96 g; 0.39 mop) of triethylamine and 32.86 g (0.13 mol) of 23.4-trichlorobechzoyl chloride, dissolved in 125 ml of 1,2-dichloroethane. After the addition of the amine and benzoyl chloride, the temperature of the reaction mixture is increased to 40 ° C and leave the mixture to react for 2 hours. By the end of this time, the constant state is maintained by
    high pressure chromatograph liquid that marks 84.6% of the surface target product, with most of the residue being unreacted cyclohexanide.
    0 Flowed, the reaction mixture was cooled and 100 ml of water was added. The pH of 8.9 is adjusted to 2.3 Cs: this is the addition of 3 of sulfuric acid, with the addition being added during this step.
    5 100 ml of 1,2-dichloroethane for re-dissolving the 1 verde — substances that began to precipitate. The mixture of rgzdep from IL aqueous and organic phase. The aqueous layer (about 200 ml) has a pH, b
    0Cpi anicic washed with water and
    exchanged again (the aqueous phase has a pH of 4). The organic phase is then washed with 2 portions of a 2 to 5 n aqueous solution of sodium hydroxide and the hydroxides are separated after
    5 each wash The aqueous phases have a pH of 10.7 and respectively 12.8 The organic phase of the dream is washed with 100 ml of water.
    All aqueous fragments obtained after separation, indicating ix above, are combined and
    0 is acidified with 3 M sulfuric acid. The pH value decreases to 2.1. The combined aqueous phases are kept at a low temperature in an ice bath. From the solution solid solids are precipitated, which are bio-filtered by filtration. the solids are dried to constant weight in a vacuum drying oven. 39.19 g of the expected product are obtained, tt. 150-151 ° C. The structure of the target product is confirmed
    0 by means of a liquid chromatographic analysis at high pressure and comparison with the Joaest sample.
    Example 8. Semi - enge 2-propanoyl-, 3-cycloge, sandipna
    5K mixtures 3 0 g (0 02 / vonbj 1,3-cyclohec
    Sandiona 3.8 mp (0 02 / mol) of Griethylamya in 15 ml of methylene chloride are added dropwise 2.3 ml (0.027 mol) of the propyl nichloride npii under stirring and ohpdenii at room temperature of the water bath, after a prolonged stirring with temperature around about 4 hours additionally added. 7.5 & n (0.054 mol) of trigtylamine and 0.025 ml (10 mol.% Relative to ester) of ecetonioanhydrin. The mixture was stirred at ambient temperature overnight, then diluted with water and acidified with 6N hydrochloric acid. The phases are separated and the aqueous phase is xytoagirate with methylene chloride. The combined organic phases are dried over anhydrous sodium sulfate and concentrated under reduced pressure. 4.68 g of crude product is obtained as a mixture of a solid and a liquid. This product is dissolved in methylene chloride and extracted with 2.5N sodium hydroxide solution, then with water. The combined aqueous phases are acidified with 6N hydrochloric acid and extracted with methylene chloride. The organic extract is dried over sodium sulfate anhydride and concentrated under reduced pressure. 3.83 g of oily product are obtained (84% of theory). The structure of the product is confirmed by IR, NMR and mass spectroscopy.
    Example 9 Preparation of 2- {2-nitrobenzoyl) -1,3-cyclohexanedione. 2-Nitrobenzoyl chloride (5.0 g; 0.027 mol) and cyclohexanedione (3.0 g; 0.027 mol) were dissolved in methylene chloride; triethylamine (4.9 ml; 0.035 mol) was added dropwise and the resulting solution was stirred for 1 hour. The solution is washed with 2N hydrochloric acid (2N hydrochloric acid, water, 5% potassium carbonate solution and saturated sodium chloride solution), dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue is dissolved in 20 ml of acetonitrile. Triethylsmine (1 eq.) And potassium cyanide (40 mol.%) Are added, and the solution is stirred for 1 hour at room temperature. After dilution with ether, the solution is washed with 2N hydrochloric acid and extracted with 5% potassium carbonate solution. The aqueous extract is acidified and ether is added. Filtration of the resulting mixture gave 3.2 g of the title compound (mp. 132-135 ° C), which was confirmed by NMR, IR and mass spectrometry.
    An example. Preparation of 2- (2-nitrobenzoyl-5,5-dimethyl-1,3-cyclohexanedione).
    Triethylamine (3.4 ml; 0.025 mol) was added dropwise to a methylene chloride solution of 2-nitrobenzoyl chloride (3.5 g; 0.019 mol) and 5.5-dimethylcyclohexanedione (2.4 g; 0.019 mol). After stirring for 1 hour at room temperature, an additional 3 eq of triethylamine and 0.4 ml of acetone cyanohydrin are added. The solution is stirred for 2.5 hours, then washed with 2N hydrochloric acid and extracted with 5% potassium carbonate solution. The basic extracts are acidified with 2N HCl and extracted with ether. The ether portion was washed with a saturated solution of sodium chloride, dried over anhydrous magnesium sulphate and concentrated in vacuo. The residue is recrystallized from Egyl acetate. The yield is 2.2 g of the target compounds (mp. 130–13 ° C), which is confirmed by NMR, K, and mass spectroscopy.
    EXAMPLE Preparation of 2- (2-cyanobenzoyl-4, 4-dimethyl-1,3-cyclohexenzdione).
    2-Cyanobenzoyl chloride (3.9 g, 0.024 mol) and 4,4-dimethyl-1,3-cyclohexanedione (3.3 g, 0.024 mol) are dissolved in 75 ml of methylene chloride, triethylamine (5.0 ml, 0.036 mol ) is added dropwise, and the resulting solution is stirred for 1.5 hours at room temperature. The solution is washed with water, 2 N. hydrochloric acid, 5%
    5 solution of potassium carbonate and a saturated solution of sodium chloride (brine), dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue is dissolved in 20 ml of acetonitrile. Triethylamine
    0 (4.4 ml, 0.032 mol) and acetone cyanohydrin (5 drops) are added and the solution is stirred for 2 hours. After dilution with ether, the solution is washed with 2N hydrochloric acid and extracted with 5% carbonate. The aqueous extract is acidified with concentrated hydrochloric acid and extracted with ether. The ether phase is washed with water and brine, dried over magnesium sulfate and concentrated in vacuo. The residue is purified by chromatography on silica gel. 1.2 g of a viscous oil are obtained, which is identified as the target compound by NMR, IR and mass spectroscopy.
    5P p and m 12. 12. Preparation of 2- {2 methylbiobenzoip) -4,4, b-trimethyl-1,3-cyclohexes :: dione.
    2-methylthiobenzoylchloride (7.2 g, 0.039 mol) and 4,4,6-trimethylcyclohexanedione (5.0 g. 0.039 mop) are dissolved in methylene chloride, triztilamine (7.0 ml, 0.050 mol) is added dropwise mi and the test solution is stirred for 1 h at room temperature. The solution is washed with 2N hydrochloric acid, 5% potassium carbonate and brine, dried over magnesium sulfate and concentrated in vacuo. The residue is dissolved in 20 ml of acetonitrile. Triethylamine (2.5 eq.) And acetone; cyanohydrin (0.4 ml) were added, and the solution was stirred for 45 minutes at room temperature. After dilution with ether, the solution is washed with 2 "hydrochloric acid and extracted with 5% potassium carbonate.
    5 The aqueous extract was acidified with hydrochloric acid and extracted with ether. The ether layer is washed with brine, dried over magnesium sulfate and concentrated in vacuo. The residue is purified by trituration with ether to give 5.0 g of a viscous oil, which is determined as the target product by NMR, IR and mass spectroscopy.
    PRI me R 13. Preparation of 2- (4-bromo 2 -trmfluoromethylbenzoyl) -4,4,6-trimethyl-1,3-cyclohexanedira.
    4-Bromo-2-trifluoro methylbenzoyl chloride (4.3 g, 0.015 mol) and 4,4,6-trimetal 1, letexandion (2.3 g, 0.015 mol) are dissolved in 100 ml of methylene chloride. The solution is cooled in an ice bath and triethylamine (2.1 ml, 0.015 mol) in 10 ml of methylene chloride is added dropwise. The ice bath was then removed and the resulting solution was stirred for 30 minutes at room temperature. The solution is washed with 2% hydrochloric acid, 5% potassium carbonate solution and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate and concentrated in vacuo. The residue (5.1 g) is dissolved in 20 ml of acetonitrile, added triethylamine (3.5 ml, 0.025 mol) and 0.4 ml of acetone cyanohydrin. The solution is stirred for 2 hours at room temperature, while being protected by a calcium sulfate drying tube. After dilution with ether, the solution is washed with 2N. HCI and 5% K2COz. The aqueous extract is acidified with a concentrated hydrochloric acid brush and extracted with ether. The ether is washed with brines, dried with MgS04 and concentrated in vacuo. The resulting oil is purified on a silica gel column (80: 20: 1-hexane-ethyl acetate: acetic acid), the eluent that gives 1.5 g of a viscous oil, which is identified by NMR, IR and mass spectroscopy.
    EXAMPLE 14. Preparation of 2- (2-chloro-6-shn-soyl) -5,5-dimethyl-1,3-cyclohexanedione.
    Carrying out the process with hydrogen cyanide, which is obtained by the reaction of sodium cyanide with sulfuric acid as the source of cyanide.
    5,5-Dimethylcyclohexane-1,3 dione-1,3-dione (7.01 g, 0.05 mol), acetonitrile (80 ml) and trymethylamine (21 ml, 0.15 mol) are mixed in a flask and provide an atmosphere nitrogen. A solution of 4-chlorob (2Nzoyl chloride (6.4 ml, 0.05 mol) in acetonitrile (20 ml) is added over 15 minutes with stirring and cooling in a water bath at ambient temperature. In a separate flask for the reaction, attached to the first flask through a gas supply tube, the end of which is lowered below the liquid layer contained therein, a solution of sulfuric acid (0.25 g, 0.0025 mol) in water (30 m) is added 10 minutes to a solution of nitri cyanide (0 , 25 g, 0.005 mol) in water (30 ml) at 85 ° C with stirring,
    the primary reactor also passes nitrogen through the second reactor slowly and continuously. Then the primary reactor is heated and stirred at 40 ° C for about 2 hours, after which
    the reaction is stopped,
    The reaction mixture is diluted with 60 ml of water and gradually acidified with 40 ml of 6 N, HCl, followed by precipitation of the product. After stirring for about 5 minutes
    0 solid sell collected by filtration
    washed with water and dried. Get
    11.85 g (85.0% of theoretical yield) not
    completely white crystals, so pl. 134-134,5 ° C.
    Example 15. 2- (4-Chlorobenzoyl) -5,5-di5 methyl-1,3-cyclohexanedio.
    5,5-Dimethylcyclohexane-1,3-dione (7.01 g, 0.05 mol), acetoiitrile (80 ml) and trm tilimign (21 ml, 0.15 mol) are mixed in a flask and provide an atmosphere of nitrogen.
    0 A solution of 4-chlorobenzoyl chloride (6.4 ml, 0.05 mol) in acetonitrile (20 ml) is added for 15 minutes while stirring and cooling in a water bath at ambient temperature, trimethylsiyl lyl cyanide (0.33 ml, 2.55 mol). The reaction mixture is heated at 40 ° C and stirred for 3 hours, after which the reaction is complete.
    The reaction mixture is diluted 160 ml.
    0 of water and acidified with 40 ml of b.N. hydrochloric acid solution, and the product precipitates. After stirring for about 10 minutes, the product is collected by filtration, washed with water and dried. A yield of 13.2 g (95.0% of the theoretical yield) of a not quite white solid is obtained, m.p. 134.5-135 ° C.
    Example 6. 2- (2-Cyanobenzoyl) -1,3-cyclohexanedione.
    0 1.2 g (0.005 mol) of an enol ester obtained by the reaction of 1,3-cyclohexanedione with 2-cyanobenzoyl chloride, potassium cyanide (0.3 g, 0.005 mol), 18-Crown-6 (0, 1 g, 0.0005 mol) m
    5 10 ml of acetonitrile. The mixture is stirred at room temperature for 10 minutes and poured into 300 ml of water. The pH is carefully adjusted to about 6 with concentrated hydrochloric acid, then the solution
    0 is extracted with 200 ml of ethyl acetate. The resulting solution, in turn, is extracted with 300 ml of a saturated aqueous solution of sodium bicarbonate. The bicarbonate extract is acidified (to a pH of about 3) with concentrated hydrochloric acid and extracted with 200 ml of ethyl acetate. The resulting solution was dried over sodium sulfate and stripped. Obtain 0.7 g (58% of theoretical yield) of the target product as an orange-brown oil. Structure
    confirmed by NMR, K, and mass spectroscopy.
    PRI me R 17. Preparation of 2- (4-chlorobenzoyl} -5,5-dimethyl-1,3-cyclohexanedione.
    5,5-Dimethylcyclohexane-1,3-dione (3.50 g, 0.025 mol), potassium carbonate (10 g, 0.1 mol), potassium cyanide (0.2 g) and dimethyl formamide (40 ml) are mixed in a flask and provide an atmosphere of nitrogen, p-chlorobenzoyl chloride (3.5 ml, 0.025 mol) is added dropwise and the mixture is stirred at 40 ° C for 3 hours and at 70 ° C for 24 hours.
    The reaction mixture is diluted with methylene chloride and acidified with 3N hydrochloric acid. The organic phase is washed with water and extracted with 2.5N sodium hydroxide solution. The main extract is acidified with 3N hydrochloric acid. The precipitated product is collected by filtration, washed with water and dried. 5.46 g (78.0% of theoretical yield) of the crude product are obtained. Analysis of the product by means of high performance liquid chromatography shows the presence of 63% by weight of 2- (4-chlorobenzoyl) -5,5-dimethyl-1,3-cyclohexanedione, p-chlorobenzoic acid is the only significant impurity.
    Example 18. 2- (2-Chloro-4-methane-sulfonyl-benzoyl) -1,3-cyclohexanedione.
    0.376 mol of 1,3-cyclohexanedione, 1.0 mol of triethylamine, 0.026 mol of acetone cyanohydrin and 1.5 mol of toluene are placed in a flask. The temperature is maintained below 20 ° C. Then, 0.366 mol of 2-chloro-4-methylene sulfonium benzoyl chloride is added through a separating funnel, which is then washed with toluene. The temperature is maintained at about 60 ° C. The reaction mixture is treated with water, neutralized with caustic soda, and the aqueous phase is reacted with 20 wt.% Hydrochloric acid. The reaction product is isolated, filtered and analyzed by IR. NMR and mass spectroscopy, which confirm the structure. The target substance has a mp. 140-141 ° C.
    PRI me R 19. Obtaining 2- (2-chloro-3-ethoxy-4-ethane-sulfonylbenzoyl) -1,3-cycle - oghexanedione.
    355 g (3.07 mol) of 1,3-cyclohexanedione, 2.7 l of 1,2-dichloroethane and 1.29 l (9.21 mol) of triethylamine are placed in the reactor. The mixture is cooled at 3 ° C and then a solution of 1.003 g (3.00 mol) of crude 2-chloro-4-ethanesulfonyl-3-ethoxybenzoyl chloride in 900 ml of 1,2- dichloroethane, maintaining the temperature of the reaction mixture at 0 ° C. Analysis of the aliquot of the mixture using gas chromatography at the end of this time period shows that the formation of the enol ester is complete, along with traces of the remaining acid chloride. Then 25 g (0.252 mol) of trimethylsilyl cyanide are added in one step and the temperature allowed to rise. By the end of a 4.5 h period of time, analysis by gas chromatography shows the absence of unreacted enol ester. The mixture is allowed to stand overnight vi, then it is treated with hydrochloric acid, water, sodium hydroxide and dichloromethane. 952 g (78.3% of theoretical yield) of the desired product are obtained, the structure of which is confirmed by spectroscopic methods.
    The proposed method allows to simplify the process in comparison with the known method by eliminating the use of expensive and hard-to-reach benzoyl cyanide, for the preparation of which copper cyanide is used, and also by eliminating the additional catalyst ZnCla.
    权利要求:
    Claims (7)
    [1]
    Claim 1, A method for producing acylated diketone compounds of Formula
    YU
    where RI - Re is a hydrogen atom or Ci - Sv-alkyl;
    R is a halogen atom, nitro or cyano group, trifluoromethyl or mercapto-C1-C-alkyl;
    Rs is Rio is a hydrogen or halogen atom, a Ci is a C-alkoxy group or a Ci is a C4 alkylsulfonyl group by appealing a diketone using a cyanide derivative, a base and an organic solvent as a source of cyanide, characterized in that, in order to simplify the process and expanding the range of target products, diketone of the general formula
    55
    6
    where RI - Re have the indicated meanings, is reacted with an acyl halide of the formula IIIД s r
    Rs -coci
    where R - Rio have the indicated meanings, in the medium of an organic solvent in the presence of a moderate base, followed by rearrangement of the obtained enol ether of formula IV
    RS
    where Ri - Rio have the indicated meanings, in the presence of an alkali metal cyanide cyanide, methyl alkyl (Ci - C (1) ketone, or three (Cu - C4) alkylsilyl cyanide) as a source.
    [2]
    2. A method according to claim 1, in that the rearrangement of the enol ether is carried out without isolation from the reaction mixture.
    [3]
    3. A method according to claim 1, characterized in that the rearrangement is carried out with either a catalytic amount of a source of cyanide and a molar excess with respect to the enol ester of a moderate base, or a stoichiometric amount in proportion to the enol ether of potassium cyanide or lithium cyanide and a catalytic amount cyclic crown ether.
    [4]
    4. A method according to claim 1, characterized in that sodium or potassium cyanide or acetone cyanide is used as a source of cyanide.
    [5]
    5. The method according to claim 1, characterized in that the cyanide derivative is used in
    the number of 2-10 mol. % relative to the enol ether.
    [6]
    6. A method according to claim 1, characterized in that triethylamine or an alkali metal carbonate is used as a moderate base.
    [7]
    7. The method according to claim 1, characterized in that the moderate base is used in an amount of 1-4 moles per 1 mole of enol ether.
    Priority items and features:
    12.20.84p. 2, 4, 5, 7 and 6-triethylamine, with RI - Re, a hydrogen atom or Ci - Cb-alkyl; R is a halogen atom, nitro or
    cyano, trifluoromethyl, or mercapto-CH-C4-alhil; Re is Rio a hydrogen or halogen atom, a Ci is a C4 alkoxy group or a Ci is a Q-alkylsulfonyl group;
    11/20/85 in paragraphs 3 and b - alkali metal carbonate, with Rt - Re - hydrogen atom
    or Ci is Cb alkyl; RT is a halogen atom, a nitro or cyano group, trifluoromethyl or mercapt is an o-C1-C4 alkyl, RB is a Rio-hydrogen or halogen atom, a Ci is a C4 alkoxy group or a Ci is a C4 alkylsulfonyl group.
    Table 1
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1697591A3|1991-12-07|Method of acylated diketonic compounds preparation
    US4695673A|1987-09-22|Process for the production of acylated 1,3-dicarbonyl compounds
    US4169840A|1979-10-02|Method of preparing furocoumarins
    HU204044B|1991-11-28|Process for producing trans-aryltetraloncarboxylic acid derivatives
    Sinsky et al.1984|The reactions of some ortho‐substituted anilines with various α, β‐acetylenic ketones. A route to substituted quinolines
    US4849535A|1989-07-18|Production of cyclopentenylheptanoic acid derivatives
    EP0176142A2|1986-04-02|Process for the preparation of aryl alkyl ketones
    AU2003203479B2|2005-10-06|Process for the preparation of bicyclic diketone salts
    Shin et al.1975|α, β-Unsaturated Carboxylic Acid Derivatives. VIII. The Synthesis and Reaction of Esters N-Acyl-N-bromo-α-dehydroamino Acid
    US3845076A|1974-10-29|Method of preparing aldehydes
    Dvořák et al.1987|Michael reaction of methylenemalonaldehydes: Synthetic approach to 4H-pyran-5-carboxaldehydes and 2-amino-4H-pyran-5-carboxaldehydes
    US5569776A|1996-10-29|Process for the preparation of 4-fluoroalkoxycinnamonitriles
    US5945565A|1999-08-31|Process for the manufacture of acetonylbenzamides
    SE435278B|1984-09-17|5-CYANO-1-LEGRE | ALKYL-PYRROL-2-ETHIC ACID, PREPARATION OF IT AND USE AS INTERMEDIATE IN THE PREPARATION OF THERAPEUTICALLY EFFECTIVE PYRROL DERIVATIVES
    US3962281A|1976-06-08|Method of preparing aldehydes
    Baumgarten et al.1981|Napthyridines. IV. Synthesis of benzo [f]‐1, 7‐naphthyridines
    US5420300A|1995-05-30|Substituted 2-ethylbenzo [b] thiophene, process for preparation thereof and use thereof as synthetic intermediate
    Baer et al.1970|Synthesis of 2-| benzoates
    Hamilakis et al.1994|Acylaminoacetyl derivatives of active methylene compounds. 3. C‐Acylation Reactions via the Hippuric Acid Azlactone
    US5142091A|1992-08-25|α, β-unsaturated ketones and ketoxime derivatives
    JP2801647B2|1998-09-21|Method for producing 6-fluorochromone-2-carboxylic acid derivative
    EP0578849A1|1994-01-19|Process for the preparation of 1,3-dioxane-4,6-dione derivates
    EP0005145B1|1981-12-30|Process for preparing 5-|-2|-4a-methyl-4,4a,5,6,7,8-hexahydronaphthalene-2-one and 5-ethenyl-2|-4a-methyl-4,4a,7,8-tetrahydronaphthalene-2-one therefrom by dehydrobromination
    US4578484A|1986-03-25|Process for the preparation of lineatin
    SU1027168A1|1983-07-07|Process for preparing 6z or 6e-isomers of 2e-8-triphenyl-silyloxy-2,6-dimethylocta-2,6-dien-4-in-1-al
    同族专利:
    公开号 | 公开日
    JPH0710787B2|1995-02-08|
    DK594585D0|1985-12-19|
    FI86542B|1992-05-29|
    DE3580657D1|1991-01-03|
    PT81730A|1986-01-01|
    PT81730B|1988-07-01|
    IL77350A|1991-01-31|
    FI86542C|1992-09-10|
    AU5133585A|1986-06-26|
    CA1317976C|1993-05-18|
    PL256982A1|1987-03-09|
    NO163402C|1990-05-23|
    MX170385B|1993-08-19|
    EP0186117B1|1990-11-22|
    ZW23785A1|1986-03-19|
    CN1003588B|1989-03-15|
    YU45754B|1992-07-20|
    BR8506421A|1986-09-02|
    EP0186117A3|1987-06-16|
    BG45042A3|1989-03-15|
    GR853110B|1986-04-22|
    FI855047A0|1985-12-18|
    RO93561A|1987-12-31|
    JPS61171449A|1986-08-02|
    DK594585A|1986-06-21|
    NO163402B|1990-02-12|
    DK174911B1|2004-02-16|
    PL148102B1|1989-09-30|
    FI855047A|1986-06-21|
    NO855163L|1986-06-23|
    HU204753B|1992-02-28|
    EP0186117A2|1986-07-02|
    KR860004825A|1986-07-14|
    TR23030A|1989-02-10|
    YU200985A|1988-02-29|
    KR920000907B1|1992-01-31|
    CN85109777A|1987-02-04|
    AU592069B2|1990-01-04|
    HUT41368A|1987-04-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4350705A|1979-03-31|1982-09-21|Eisai Co., Ltd.|Cyclohexane derivatives, process for preparation thereof and medicines containing these cyclohexane derivatives|
    DE3382601T2|1982-03-25|1993-01-07|Stauffer Chemical Co|2- -1,3 CYCLOHEXANDIONE.|
    JPH0429659B2|1983-04-22|1992-05-19|
    US4482727A|1983-07-01|1984-11-13|Stauffer Chemical Company|Certain 1,3-cyclohexanedione adducts of substituted phenoxyphenoxypropionic acids and their use as an herbicide|
    DE3568975D1|1984-05-21|1989-04-27|Stauffer Chemical Co|Certain 2-acetyl)-1,3-cyclohexanediones|
    IL77349A|1984-12-20|1990-07-12|Stauffer Chemical Co|2--1,3-cyclohexanediones,their preparation and their use as herbicides|
    TR22585A|1984-12-20|1987-12-07|Stauffer Chemical Co|SOME 2- -1,3-SIKLOHEKSANDIONS|TR22585A|1984-12-20|1987-12-07|Stauffer Chemical Co|SOME 2--1,3-SIKLOHEKSANDIONS|
    IL77348A|1984-12-20|1991-05-12|Stauffer Chemical Co|2--1,3-cyclohexanediones,their preparation and their use as herbicides|
    IL77349A|1984-12-20|1990-07-12|Stauffer Chemical Co|2--1,3-cyclohexanediones,their preparation and their use as herbicides|
    AU583089B2|1985-02-15|1989-04-20|Ici Australia Limited|Process for the preparation of 2-acylcyclohexane-1,3-dione derivatives|
    US4724263A|1986-06-09|1988-02-09|Stauffer Chemical Company|Certain 2-phenylacetyl-1,3,5-cyclohexanetriones|
    US4783213A|1986-10-16|1988-11-08|Stauffer Chemical Company|Certain 2--4--1,3-cyclohexanediones|
    KR890003680A|1986-10-16|1989-04-17|죤 알.페넬|2--4--1,3-cyclohexanedione and methods for preparing the same and methods for inhibiting compositions and plants using the same|
    US4808214A|1986-10-16|1989-02-28|Stauffer Chemical Company|Certain 2--4--1,3-cyclohexanediones|
    DE3743695A1|1987-12-18|1989-06-29|Schering Ag|4-BENZOYL-3-HYDROXY-5-OXO-3-CYCLOHEXENCARBONIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION OF THESE COMPOUNDS AND THEIR USE AS AGENTS WITH A PLANT GROWTH REGULATING EFFECT|
    HUT50312A|1988-02-01|1990-01-29|Sandoz Ag|Herbicide composition containing new dion-compounds and process for producing these compounds|
    AU616956B2|1988-04-18|1991-11-14|Sandoz Ltd.|Substituted phenyl or pyrimidine bicyclodiones|
    US4869748A|1988-12-02|1989-09-26|Ici Americas Inc.|Certain 3--3:2:1-bicyclooctan-2,4-diones|
    US5336662A|1989-04-25|1994-08-09|Sandoz Ltd.|Heterocyclic diones as plant growth regulators|
    CA2072134A1|1990-10-25|1992-04-26|Shy-Fuh Lee|Heterocyclic dione derivatives as pesticides and plant growth regulators|
    GB9501433D0|1995-01-25|1995-03-15|Zeneca Ltd|Chemical process|
    GB9501434D0|1995-01-25|1995-03-15|Zeneca Ltd|Chemical process|
    DE10113137C2|2001-03-17|2003-05-15|Bayer Cropscience Gmbh|Process for the preparation of substituted 2-benzoyl-1,3-cyclohexanediones|
    AU2003203482B2|2002-04-09|2005-06-02|Syngenta Participations Ag|Process for the preparation of cyclic diketones|
    TWI348999B|2003-10-02|2011-09-21|Syngenta Participations Ag|Process|
    DE102004016496A1|2004-04-03|2005-10-20|Bayer Cropscience Gmbh|Herbicidal 3-amino-2-thiomethylbenzoylpyrazole|
    DE102007026875A1|2007-06-11|2008-12-24|Bayer Cropscience Ag|3-Cyclopropyl-4-pyrazoles and their use as herbicides|
    PT104664A|2009-07-07|2011-01-07|Sapec Agro S A|STABLE CRYSTALLINE POLYMER OF 2-CYCLOHEXANE-1,3-DIONA AND PROCESS FOR PREPARING THE SAME|
    CN102781235B|2010-02-19|2015-04-22|拜耳知识产权有限责任公司|3-aminocarbonyl-substituted benzoylcyclohexanediones and their use as herbicides|
    DK2595963T3|2010-07-21|2015-02-16|Bayer Ip Gmbh|4-pyrazoles and their use as herbicides|
    CN103748075B|2011-07-15|2016-09-07|拜耳知识产权有限责任公司|2,3-diphenyl valeronitrile derivant, its preparation method and as herbicide and the purposes of plant growth regulator|
    CN113233998B|2021-05-24|2021-12-28|浙江新安化工集团股份有限公司|Preparation method of mesotrione|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US68388284A| true| 1984-12-20|1984-12-20|
    US79884285A| true| 1985-11-20|1985-11-20|
    [返回顶部]