WO2005075401A1 - Verfahren zur herstellung von 2,5-dimethylphenylessigsäure - Google Patents

Verfahren zur herstellung von 2,5-dimethylphenylessigsäure Download PDF

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Publication number
WO2005075401A1
WO2005075401A1 PCT/EP2005/000617 EP2005000617W WO2005075401A1 WO 2005075401 A1 WO2005075401 A1 WO 2005075401A1 EP 2005000617 W EP2005000617 W EP 2005000617W WO 2005075401 A1 WO2005075401 A1 WO 2005075401A1
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Prior art keywords
acid
mixture
xylene
mol
process according
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PCT/EP2005/000617
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German (de)
English (en)
French (fr)
Inventor
Thomas Himmler
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Bayer Cropscience Aktiengesellschaft
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Filing date
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Application filed by Bayer Cropscience Aktiengesellschaft filed Critical Bayer Cropscience Aktiengesellschaft
Priority to JP2006551756A priority Critical patent/JP4668212B2/ja
Priority to BRPI0507422-3A priority patent/BRPI0507422A/pt
Priority to AT05701122T priority patent/ATE455087T1/de
Priority to EP05701122A priority patent/EP1713755B1/de
Priority to US10/586,491 priority patent/US7579500B2/en
Priority to CN2005800041299A priority patent/CN1918103B/zh
Priority to DE502005008867T priority patent/DE502005008867D1/de
Publication of WO2005075401A1 publication Critical patent/WO2005075401A1/de
Priority to US12/388,274 priority patent/US7629476B2/en
Priority to IN3160DEN2012 priority patent/IN2012DN03160A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/16—Radicals substituted by halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings

Definitions

  • the present invention relates to a new process for the preparation of 2,5-dimethylphenylacetic acid.
  • 2,5-Dimethylphenylacetic acid is a known compound (for example from: ZJ. Vejdelek et al., Collect. Czech. Chem. Commun. 29 (1964) 776-94).
  • the preparation can be carried out, for example, starting from 2,5-dimethylphenylacetophenone by a Wellergerodt-Kindler reaction (HE Zaugg et al., J. Amer. Chem. Soc. 70 (1948) ' 3224-8).
  • this method produces large amounts of sulfur-containing waste.
  • highly odorous, volatile sulfur compounds can occur.
  • 2,5-dimethylphenylacetic acid is based on 2,5-dimethylbenzylbromide. It is used e.g. with ⁇ afriumcyanid the corresponding ⁇ itrile, which is then saponified.
  • the required 2,5-dimethylbenzyl bromide can be produced, for example, by bromomethylating p-xylene with formaldehyde and hydrogen bromide (H. Hart et al., Tetrahedron Letters 1975, 4639-42; JM Khurana and GC Maikap, J. Ind. Chem. Soc 76 (1999) 216-7).
  • formaldehyde and hydrogen bromide H. Hart et al., Tetrahedron Letters 1975, 4639-42; JM Khurana and GC Maikap, J. Ind. Chem. Soc 76 (1999) 216-7.
  • it is disadvantageous here that undesired secondary reactions to multiply bromomethylated products can take place.
  • 2,5-dimethylphenylacetic acid Another possibility which has become known for the preparation of 2,5-dimethylphenylacetic acid is to start from 2,5-dimethylbenzyl chloride and to produce the nitrile therefrom (J. Amer. Chem. Soc. 58 (1936) 629-35; J. Org. Chem 33 (1968) 2338-42) and then to saponify it.
  • 2,5-dimethylbenzyl chloride is also known and can be prepared by chloromethylating p-xylene (ZJ. Vejdelek et al., Collect. Czech. Chem. Commun. 29 (1964) 776-94).
  • chloromethylation is a method that can only be carried out with great technical effort and cost.
  • this method provides 2,5-dimethylphenylacetic acid only in unsatisfactory yields (e.g. 38% of theory over 3 steps, according to ZJ. Vejdelek et al., Collect. Czech. Chem. Commun. 29 (1964) 776-94).
  • 2,5-dimethylphenylacetic acid important intermediate products for example for active substances in plant are protective (cf. WO 97/36868), there is a need for a technically simple and highly efficient method for producing 2,5-dimethylphenylacetic acid.
  • 2,5-dimethylphenylacetic acid can be obtained in very high yield and purity by first of all p-xylene with chloroacetyl chloride in a Friedel-Crafts reaction to give 2-chloro-l- (2,5-dimethylphenyl) -ethanone of the formula (I), from this ketone with a diol of the general formula (II) produces the corresponding ketal of the general formula (DT), this then to a mixture of the corresponding 2,5-dimethylphenylacetic acid hydroxyalkyl ester of the general Formula (TV) and bis (2,5-dimethylphenylacetic acid) diesters of the general formula (V) rearranged and finally saponified to 2,5-dimethylphenylacetic acid.
  • the compound of the formula (I) is known (see, for example, F. Kunckell, Chem. Ber. 30 (1897) 577-579) and, in addition to Friedel-Crafts acylation, can also be prepared, for example, by chlorination of 2,5-dimethylacetophenone.
  • the present invention also relates to the new compounds of the general formula (TU) in which
  • X represents a direct single bond, CH 2) CHCH3, CHC2H5, C (CH3) 2 or C (C 2 H 5 ).
  • X represents a direct single bond, CH 2 , C (CH3) 2 or C (C 2 H5) 2 .
  • X represents a direct single bond, C (CH3) 2 or C (C 2 H5) 2 .
  • the 2,5-dimethylphenylacetic acid can be prepared in a simpler manner, with better selectivity and in a higher yield than according to the previously known processes by the process according to the invention.
  • Friedel-Crafts catalysts for the preparation of the compound of formula (I) by the process according to the invention for example aluminum chloride, iron (IJI) chloride, tin tetrachloride or zeolites can be used.
  • Aluminum chloride is preferably used as the Friedel-Crafts catalyst.
  • the amount of Friedel-Crafts catalyst to be used in the process according to the invention is not critical.
  • 0.8 to 1.2 moles of catalyst per mole of chloroacetyl chloride can be used.
  • 0.9 to 1.1 moles of catalyst per mole of chloroacetyl chloride are preferred.
  • largely inert solvents such as nitrobenzene, carbon disulfide, methylene chloride, 1,2-dichloroethane or p-xylene itself are used as solvents for the Friedel-Crafts reaction.
  • Carbon disulfide, 1,2-dichloroethane and p-xylene are preferred.
  • P-Xylene is particularly preferred.
  • the amount of chloroacetyl chloride to be used in the process according to the invention is not critical and can be varied within wide limits.
  • a solvent for example, 0.8 to 1.2 moles of chloroacetyl chloride per mole of p-xylene can be used. 0.9 to 1.1 moles of chloroacetyl chloride per mole of p-xylene are preferred.
  • the ratio of chloroacetyl chloride to p-xylene will of course be significantly smaller. Since it is known (see, for example, L. Friedman and R. Koca, J. Org. Chem. 33 (1968) 1255-7) that p-xylene can be isomerized by a Friedel-Crafts catalyst such as A1C1 3 , it is expedient to proceed so that p-xylene and chloroacetyl chloride are introduced and the Friedel-Crafts catalyst is metered in.
  • a Friedel-Crafts catalyst such as A1C1 3
  • the first step of the method according to the invention can be carried out at temperatures between -20 and + 60 ° C. Temperatures between -10 and + 30 ° C are preferred.
  • reaction times of the first step of the process according to the invention are between 1 and 24 hours.
  • the ketal of the general formula (TU) is prepared by heating the ketone of the formula (I) with a diol of the general formula (II) in the presence of a catalyst.
  • diols of the general formula (II) examples include ethylene glycol, 1,2-propanediol (propylene glycol), 1,3-propanediol (trimethylene glycol), 2,2-dimethyl-1,3-propanediol (neopentyl glycol) and 2,2 -Diethyl-l, 3-propanediol called.
  • Ethylene glycol and neopentyl glycol are preferred.
  • Neopentyl glycol is particularly preferred.
  • Acids such as hydrochloric acid, sulfuric acid, phosphoric acid, methylsulfonic acid, p-toluenesulfonic acid, acidic ion exchangers, etc. come as catalysts for the second step of the process according to the invention. into consideration. Hydrochloric acid, sulfuric acid and p-toluenesulfonic acid are preferred.
  • Inert organic solvents such as, for example, aliphatic and aromatic hydrocarbons, and the diols themselves are suitable as solvents for the second step of the process according to the invention.
  • Aromatic hydrocarbons are preferably used, particularly preferably xylene itself.
  • the procedure is expediently such that the water of reaction is azeotropically distilled off with the solvent, preferably the aromatic hydrocarbon.
  • Another method for the 1,2-aryl shift of the ketal of the general formula (HI) consists in heating in the presence of a Lewis acid, for example FeCl 2 , FeCl 3 , CaCl 2 , CuCl 2 or ZnCl 2 (EP-A 034 871).
  • a Lewis acid for example FeCl 2 , FeCl 3 , CaCl 2 , CuCl 2 or ZnCl 2
  • the 1,2-aryl shift in substituted 1,3-dioxane ketal derivatives can be carried out using catalytic amounts of a zinc carboxylate salt which is soluble in the reaction mixture, such as zinc 2-ethylhexanoate (DE-A 33 22 459).
  • the latter processes have the disadvantage that the catalysts, such as zinc compounds, have to be removed using complex methods (precipitation; treatment of the reaction mixture with activated carbon).
  • chlorinated alcohols are created as waste products that have to be disposed of.
  • Water, alcohols, diols, polyols and mixtures thereof can be used as polar-protic solvents for the third step of the process according to the invention.
  • the radical X within the definition given above can also have a different meaning than in the formulas (H) and (IU) have.
  • the amount of solvent can be varied within wide limits. Typically between 200 ml and 2000 ml of solvent are used per mole of ketal.
  • Alkali salts of formic acid, acetic acid, propionic acid or benzoic acid, alkali metal phosphates, carbonates and bicarbonates can be used as bases in the third step of the process according to the invention.
  • the bases can be used in amounts of 1 to 3 moles per mole of ketal. 1.2 to 1.6 moles per mole of ketal are preferred.
  • an alkali salt of formic acid, acetic acid, propionic acid or benzoic acid and additionally to add sodium or potassium hydroxide.
  • 0.1 to 0.3 moles per mole of ketal are preferably used in combination with 1 to 3 moles of sodium or potassium hydroxide per mole of ketal.
  • 0.1 to 0.3 moles of sodium acetate per mole of ketal are particularly preferably used in combination with 1 to 3 moles of sodium hydroxide per mole of ketal.
  • an alkali salt of formic acid, acetic acid, propionic acid or benzoic acid it is also possible to completely dispense with the use of an alkali salt of formic acid, acetic acid, propionic acid or benzoic acid and to effect the reaction of the third step solely by adding an alkali metal hydroxide.
  • the alkali metal hydroxide can be used in solid form or as an aqueous solution.
  • Potassium and sodium hydroxide are preferably used.
  • the third step of the process according to the invention for the preparation of 2,5-dimethylphenylacetic acid can be carried out at temperatures between 100 and 250 ° C. Temperatures between 150 and 230 ° C. are preferred, particularly preferably between 170 and 220 ° C.
  • reaction times of the third step of the process according to the invention are between 1 and 24 hours.
  • esters of the general formulas (TV) and (V) are saponified to give 2,5-dimethylphenylacetic acid by known methods in organic chemistry.
  • the saponification is preferably carried out by heating with sodium hydroxide solution.
  • the process according to the invention for the preparation of 2,5-dimethylphenylacetic acid is preferably designed such that all steps are carried out in succession without isolation of the intermediates. This eliminates time-consuming and costly processing and cleaning steps such as crystallization, filtration, drying, etc. It can be described as extremely surprising that, despite the lack of cleaning operations on the intermediate stages, the 2,5-dimethylphenylacetic acid is obtained not only in very high yield but also in excellent purity by the process according to the invention.
  • p-xylene is reacted with chloroacetyl chloride in the presence of aluminum chloride according to Friedel-Crafts to give 2-chloro-l- (2,5-dimethylphenyl) ethanone.
  • An excess of p-xylene serves as the solvent.
  • the solution of 2-chloro-1- (2,5-dimethylphenyl) -ethanone in xylene is mixed with neopentyl glycol and a catalytic amount of p-toluenesulfonic acid.
  • the mixture is then heated to reflux on the water separator until at least the expected theoretical amount of water has been removed.
  • the reaction mixture can be used in the next stage without further working up.
  • the solution of 2-chloromethyl-5,5-dimethyl-2- (2,5-dimethylphenyl) - [1,3] dioxane in xylene is first mixed with sodium acetate. Ethylene glycol is then added and the xylene is then distilled off until a reaction temperature of about 180 to 190 ° C. has been reached. This temperature is held for 4 to 7 hours. The mixture is then allowed to cool to about 90 ° C. and the reaction mixture is used in the next step without further working up.
  • the reaction mixture from the third stage is mixed with sodium hydroxide solution at about 90 to 95 ° C. and heated to 100 to 105 ° C. for 1 to 2 hours.
  • the mixture is then allowed to cool to room temperature, water is added, the mixture is made acidic by adding an acid, for example hydrochloric or sulfuric acid, and the 2,5-dimethylphenylacetic acid is then isolated by filtration.
  • an acid for example hydrochloric or sulfuric acid
  • the cloudy organic phase is separated off, the aqueous phase is extracted three times with 300 ml of ethyl acetate, the combined organic phases are extracted twice with 200 ml of water and once with 100 ml of saturated, aqueous NaCl solution.
  • the organic phase is dried, evaporated and distilled to a bath temperature of 70 ° C./1 mbar. The result is 363.6 g of yellowish oil which, according to GC, contains 97.2% of the target product (96.8% of theory).
  • a mixture of 4.1 g [0.05 mol] sodium acetate and 10.75 g [0.04 mol] 2-chloromethyl-5,5-dimethyl-2- (2,5-dimethylphenyl) - [1,3 ] dioxane in 50 ml of ethylene glycol is heated to 180 to 185 ° C for 5 hours. Then allowed to cool to 90 to 95 ° C, 20 ml of 30% sodium hydroxide solution is added and heated to 100 to 105 ° C for 1 hour. At room temperature, the reaction mixture is diluted with 80 ml of water and extracted twice with 10 ml of methylene chloride. The aqueous phase is then concentrated.
  • A1C1 3 are added to a mixture of 400 g p-xylene and 113 g [1 mol] chloroacetyl chloride within 70 minutes. The mixture is stirred for 2 hours at 20-25 ° C and the reaction mixture is then mixed with 750 ml of ice-cold water and 35 g ' conc. Hydrochloric acid. After stirring for 30 minutes, the organic phase is separated off and used in the second step.
  • the still warm and liquid reaction mixture from the second step is mixed with 137.4 g [1.4 mol] of potassium acetate and 1250 ml of ethylene glycol.
  • the mixture is then heated to 183 to 189 ° C. for 5 hours, small amounts of distillate being removed.
  • the mixture is then used without further 'worked up in the fourth step.
  • the reaction mixture from the third step is cooled to 90 to 95 ° C., 500 ml of 30% sodium hydroxide solution are added and the mixture is heated at 100 to 105 ° C. for 1 hour.
  • the reaction mixture is then diluted with 2000 ml of water and extracted twice with 150 ml of methylene chloride.
  • the aqueous phase is then concentrated. " Hydrochloric acid is adjusted to pH 1, the solid which has precipitated is filtered off with suction, washed twice with 500 ml of water each time and dried. 117 g of solid are obtained with a purity according to GC of 95.2%. This gives a yield of 67.5% of theory. Th. Over 4 steps, ie on average approx. 90 to 91% per level.
  • Example 8 Carrying out the process according to the invention with catalytic amount of sodium acetate and sodium hydroxide solution in 3 steps
  • A1C1 3 are added to a mixture of 400 g p-xylene and 113 g [1 mol] chloroacetyl chloride within 70 minutes. The mixture is stirred for 2 hours at 20-25 ° C. and the reaction mixture is then mixed with 750 ml of ice-cold water and 35 g of conc. Hydrochloric acid. After stirring for 30 minutes, the organic phase is separated off and used in the second step.
  • Example 9 Execution of the process according to the invention with sodium hydroxide solution in 3 steps
  • A1C1 3 are added to a mixture of 400 g p-xylene and 113 g [1 mol] chloroacetyl chloride within 60 minutes. Stir for 2 hours at 20- 25 ° C and the reaction mixture is then mixed with 750 ml of ice-cold water and 35 g of conc. Hydrochloric acid. After stirring for 30 minutes, the organic phase is separated off and used in the second step.
  • the residue obtained from the second step (315.6 g) is mixed with 1000 ml of ethylene glycol and 267 g of 45% sodium hydroxide solution [corresponds to 3 mol of NaOH].
  • the mixture is heated in an autoclave under autogenous pressure at 190 to 195 ° C. for 6 hours.
  • the reaction mixture is then diluted with 2500 ml of water at room temperature. It is extracted three times with 300 ml of MTBE, the aqueous phase is made up with conc. Hydrochloric acid to pH 1 and sucks off the solid. After washing twice with 1000 ml of water and drying, 139.7 g of solid with a purity according to GC of 99% are obtained. This results in a yield of 84.2% of theory over 3 steps, i.e. on average approx. 94.5% of theory per step.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/EP2005/000617 2004-02-04 2005-01-22 Verfahren zur herstellung von 2,5-dimethylphenylessigsäure WO2005075401A1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
JP2006551756A JP4668212B2 (ja) 2004-02-04 2005-01-22 ２，５−ジメチルフェニル酢酸の調製方法
BRPI0507422-3A BRPI0507422A (pt) 2004-02-04 2005-01-22 processo para produção de ácido 2,5-dimetilfenilacético
AT05701122T ATE455087T1 (de) 2004-02-04 2005-01-22 Verfahren zur herstellung von 2,5- dimethylphenylessigsäure
EP05701122A EP1713755B1 (de) 2004-02-04 2005-01-22 Verfahren zur herstellung von 2,5-dimethylphenylessigsäure
US10/586,491 US7579500B2 (en) 2004-02-04 2005-01-22 Method for producing 2,5-dimethylphenyl acetic acid
CN2005800041299A CN1918103B (zh) 2004-02-04 2005-01-22 2,5-二甲基苯乙酸的制备方法
DE502005008867T DE502005008867D1 (de) 2004-02-04 2005-01-22 Verfahren zur herstellung von 2,5-dimethylphenylessigsäure
US12/388,274 US7629476B2 (en) 2004-02-04 2009-02-18 Method for producing 2,5-dimethylphenyl acetic acid
IN3160DEN2012 IN2012DN03160A (forum.php) 2004-02-04 2012-04-12

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004005318A DE102004005318A1 (de) 2004-02-04 2004-02-04 Verfahren zur Herstellung von 2,5-Dimethylphenylessigsäure
DE102004005318.9 2004-02-04

Related Child Applications (2)

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US10/586,491 A-371-Of-International US7579500B2 (en) 2004-02-04 2005-01-22 Method for producing 2,5-dimethylphenyl acetic acid
US12/388,274 Division US7629476B2 (en) 2004-02-04 2009-02-18 Method for producing 2,5-dimethylphenyl acetic acid

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WO2005075401A1 true WO2005075401A1 (de) 2005-08-18

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US (2) US7579500B2 (forum.php)
EP (1) EP1713755B1 (forum.php)
JP (1) JP4668212B2 (forum.php)
CN (1) CN1918103B (forum.php)
AT (1) ATE455087T1 (forum.php)
BR (1) BRPI0507422A (forum.php)
DE (2) DE102004005318A1 (forum.php)
IN (1) IN2012DN03160A (forum.php)
WO (1) WO2005075401A1 (forum.php)

Cited By (5)

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Publication number Priority date Publication date Assignee Title
DE102008020361A1 (de) 2007-04-24 2008-12-04 Daicel Chemical Industries, Ltd. Verfahren zum Herstellen eines Derivats von 2,5-Dimethylacetophenon, Verfahren zum Herstellen von 2,5-Dimethylphenylessigsäure aus dem 2,5-Dimethylacetophenonderivat, und Verfahren zum Herstellen eines Derivats von 2,5-Dimethylphenylessigsäure
WO2010069525A1 (de) 2008-12-19 2010-06-24 Bayer Cropscience Ag Herbizid und insektizid wirksame 4-phenylsubstituierte pyridazinone
WO2011035878A1 (de) 2009-09-25 2011-03-31 Bayer Cropscience Ag Herbizid wirksame phenylsubstituierte pyridazinone
WO2011045271A1 (de) 2009-10-15 2011-04-21 Bayer Cropscience Ag Herbizid wirksame heterocyclylsubstituierte pyridazinone
WO2012028582A1 (de) 2010-09-01 2012-03-08 Bayer Cropscience Ag Herbizid wirksame ketosultame und diketopyridine

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JP2012087113A (ja) * 2010-09-22 2012-05-10 Daicel Corp フェニル酢酸化合物
CN102140062B (zh) 2011-03-13 2012-11-14 联化科技股份有限公司 一种2，5-二甲基苯乙酸的制备方法
CN104628551A (zh) * 2015-02-13 2015-05-20 中国药科大学 一种2,5-二甲基苯乙酸的制备方法
CN110305010B (zh) * 2019-07-17 2022-05-13 江苏中旗科技股份有限公司 一种2,5-二甲基苯乙酸的制备方法
EP4100385A1 (en) * 2020-02-03 2022-12-14 DSM IP Assets B.V. Rearrangement of dimethylphenylacylates using zeolites

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008020361A1 (de) 2007-04-24 2008-12-04 Daicel Chemical Industries, Ltd. Verfahren zum Herstellen eines Derivats von 2,5-Dimethylacetophenon, Verfahren zum Herstellen von 2,5-Dimethylphenylessigsäure aus dem 2,5-Dimethylacetophenonderivat, und Verfahren zum Herstellen eines Derivats von 2,5-Dimethylphenylessigsäure
WO2010069525A1 (de) 2008-12-19 2010-06-24 Bayer Cropscience Ag Herbizid und insektizid wirksame 4-phenylsubstituierte pyridazinone
EP2204366A1 (de) 2008-12-19 2010-07-07 Bayer CropScience AG Herbizid und insektizid wirksame phenylsubstituierte Pyridazinone
WO2010078912A1 (de) 2008-12-19 2010-07-15 Bayer Cropscience Ag Herbizid und insektizid wirksame phenyl-substituierte pyridazinone
WO2011035878A1 (de) 2009-09-25 2011-03-31 Bayer Cropscience Ag Herbizid wirksame phenylsubstituierte pyridazinone
WO2011045271A1 (de) 2009-10-15 2011-04-21 Bayer Cropscience Ag Herbizid wirksame heterocyclylsubstituierte pyridazinone
WO2012028582A1 (de) 2010-09-01 2012-03-08 Bayer Cropscience Ag Herbizid wirksame ketosultame und diketopyridine

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JP4668212B2 (ja) 2011-04-13
US7629476B2 (en) 2009-12-08
CN1918103B (zh) 2012-08-08
BRPI0507422A (pt) 2007-06-26
JP2007522139A (ja) 2007-08-09
EP1713755A1 (de) 2006-10-25
EP1713755B1 (de) 2010-01-13
US7579500B2 (en) 2009-08-25
DE102004005318A1 (de) 2005-08-25
US20080234501A1 (en) 2008-09-25
US20090156839A1 (en) 2009-06-18
DE502005008867D1 (de) 2010-03-04
IN2012DN03160A (forum.php) 2015-09-18
CN1918103A (zh) 2007-02-21

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