WO1996016045A1 - DERIVES DE COMPOSES CARBONYLES HALOGENES α, PROCEDE ET PRODUITS INTERMEDIAIRES POUR LA PREPARATION DE CES DERIVES - Google Patents

DERIVES DE COMPOSES CARBONYLES HALOGENES α, PROCEDE ET PRODUITS INTERMEDIAIRES POUR LA PREPARATION DE CES DERIVES Download PDF

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WO1996016045A1
WO1996016045A1 PCT/EP1995/004453 EP9504453W WO9616045A1 WO 1996016045 A1 WO1996016045 A1 WO 1996016045A1 EP 9504453 W EP9504453 W EP 9504453W WO 9616045 A1 WO9616045 A1 WO 9616045A1
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Prior art keywords
alkyl
alkoxy
alkylthio
halogen
phenyl
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PCT/EP1995/004453
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German (de)
English (en)
Inventor
Ernst Baumann
Albrecht Harreus
Joachim Rheinheimer
Uwe Josef Vogelbacher
Matthias Gerber
Karl-Otto Westphalen
Helmut Walter
Ulf Misslitz
Wilhelm Rademacher
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Basf Aktiengesellschaft
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Priority to AU41163/96A priority Critical patent/AU4116396A/en
Publication of WO1996016045A1 publication Critical patent/WO1996016045A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D411/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to ⁇ -halocarbonyl derivatives of the general formula I,
  • R represents a formyl group, a group CO 2 H or a radical which can be hydrolyzed to COOH and the other substituents have the following meaning: R 2 halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 -alkoxy,
  • X is nitrogen or CR 13 , where R 13 is hydrogen or together with R 3 is a 3- to 4-membered alkylene or
  • R 3 halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy,
  • C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio or R 3 is linked to R 13 as stated above to form a 5- or 6-membered ring;
  • R 4 is a group
  • Y 1 , Y 2 , Y 3 oxygen or sulfur
  • R 14 hydrogen, C 1 -C 8 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl,
  • C 3 -C 8 -cycloalkyl where these radicals one to five halogen atoms and / or may carry one to two of the following groups: C 1 -C 4 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 1 -C 4 alkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 alkynylthio, C 1 -C 4 haloalkoxy, cyano, C 1 -C 4 dialkylamino, phenyl, one or more times by halogen, Nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or C 1 -C 4 alkylthio substituted phenyl,
  • Phenyl which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 - Haloalkoxy or C 1 -C 4 alkylthio,
  • R 15 is hydrogen, C 1 -C 8 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl,
  • C 3 -C 8 cycloalkyl where these radicals can carry one to five halogen atoms and / or one or two of the following groups: C 1 -C 4 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy , C 1 -C 4 alkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 alkynylthio, C 1 -C 4 haloalkoxy, cyano, C 1 -C 4 dialkylamino, phenyl one or more times by halogen, Nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or C 1 -C 4 alkylthio substituted phenyl,
  • Phenyl which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 - Halogenalkoxy or C 1 -C 4 alkylthio, furthermore a radical OR 18 , in which R 18
  • C 3 -C 6 cycloalkyl where these radicals can carry one to five halogen atoms and / or one or two of the following groups: C 1 -C 4 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy , C 1 -C 4 alkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 alkynylthio, C 1 -C 4 haloalkoxy, cyano, C: -C 4 dialkylamino, phenyl, one or more times by halogen , Nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or C 1 -C 4 alkylthio substituted phenyl,
  • Phenyl which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 - Haloalkoxy or C 1 -C 4 alkylthio, furthermore a radical NR 19 R 20 in which R 19 and R 20 can be the same or different,
  • C 3 -C 6 cycloalkyl where these radicals can carry one to five halogen atoms and / or one or two of the following groups: C 1 -C 4 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy , C 1 -C 4 alkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 alkynylthio, C 1 -C 4 haloalkoxy, cyano, C 1 -C 4 dialkylamino, phenyl, one or more times by halogen , Nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or C 1 -C 4 alkylthio substituted phenyl,
  • Phenyl which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 - Haloalkoxy or C 1 -C 4 alkylthio, or R 19 and R 20 together form an optionally substituted C 4 -C 7 alkylene chain which is closed to form a ring or together form an optionally stubstituted C 3 -C 6 alkylene chain which is formulated to form a ring a heteroatom selected from the group consisting of oxygen, sulfur or nitrogen,
  • R 16 and R 17 are C 1 -C 8 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 8 cycloalkyl, these radicals having one to five halogen atoms and / or one or two of the following groups:
  • Phenyl which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 - Haloalkoxy or C 1 -C 4 alkylthio, or R 16 and R 17 together form an optionally substituted C 1 -C 5 alkylene chain which is closed to form a ring;
  • R 5 is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl,
  • the object of the invention was to provide compounds with improved selectivity towards crop plants and / or better herbicidal or bioregulatory activity.
  • the preparation of the compounds according to the invention starts from the epoxides IV, which are carried out in a generally known manner, e.g. as in J. March, Advanced Organic Chemistry, 2nd ed., 1983, p. 862 or p. 750 or in J.Org.Chem. 33 (1968) 3517, from the aldehydes or ketones II or the olefins III:
  • the reaction can also take place in the presence of a diluent. All solvents which are inert to the reagents used can be used for this purpose.
  • solvents or diluents are water, aliphatic, alicyclic and aromatic hydrocarbons, each of which may optionally be chlorinated, such as, for example, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichlorethylene, Ethers such as diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, isopropanol and butanol Ethylene glycol, esters such as ethylene glyco
  • the reaction is preferably carried out in a temperature range between 0 ° C. and the boiling point of the solvent or solvent mixture.
  • reaction catalyst can be advantageous.
  • Organic and inorganic acids as well as Lewis acids can be used as catalysts. Examples include sulfuric acid, hydrochloric acid, trifluoroacetic acid, boron trifluoride etherate and titanium (IV) halides.
  • R 21 is halogen or R 22 SO 2 -, where R 22 is
  • the reaction preferably takes place in one of the inert diluents mentioned above with the addition of a suitable base, ie a base capable of deprotonating compound VI, in a temperature range from room temperature to the boiling point of the solvent.
  • a suitable base ie a base capable of deprotonating compound VI
  • an alkali or alkaline earth metal hydride such as sodium hydride, potassium hydride or calcium hydride, a carbonate, e.g. Alkali metal carbonate such as sodium or potassium carbonate, an alkali metal hydroxide such as sodium or potassium hydroxide, an organometallic compound such as butyllithium or an alkali amide such as lithium diisopropylamide.
  • Y is sulfur and the remaining substituents have the meaning given under the formula I can be prepared, for example, in such a way that ⁇ -halocarbonyl derivatives of the general formula VIII,
  • the reaction preferably takes place in one of the inert diluents mentioned above with the addition of a suitable base, i.e. a base, which is able to deprotonate the intermediate IX, takes place in a temperature range from room temperature to the boiling point of the solvent.
  • a suitable base i.e. a base
  • organic bases such as triethylamine, pyridine, imidazole or diazabicycloundecane can also be used as the base.
  • Carboxylic acid can act on the hydroxyl compound in the presence of a dehydrating agent such as a carbodiimide.
  • compounds of the formula I can also be prepared by starting from the salts of the corresponding carboxylic acids, ie, for example, from compounds of the formula I in which R is a group COR 1 and R 1 is OM, where M is, for example, an alkali metal cation or the Can be equivalent to an alkaline earth metal cation.
  • salts can be reacted with many compounds of the formula R 1 -A, where A is a customary nucleofugic leaving group, for example halogen such as chlorine, bromine, iodine or aryl- or alkylsulfonyl optionally substituted by halogen, alkyl or haloalkyl, such as toluenesulfonyl and Methylsulfonyl or other equivalent leaving group.
  • A is a customary nucleofugic leaving group, for example halogen such as chlorine, bromine, iodine or aryl- or alkylsulfonyl optionally substituted by halogen, alkyl or haloalkyl, such as toluenesulfonyl and Methylsulfonyl or other equivalent leaving group.
  • A is a customary nucleofugic leaving group, for example halogen such as chlorine, bromine, iodine or aryl- or al
  • R in Formula I is widely variable.
  • R stands for a group
  • R 1 has the following meaning: a) hydrogen; b) a succinylimidoxy group; c) a 5-membered heteroaromatic linked via a nitrogen atom, such as pyrrolyl, pyrazolyl, imidazolyl and triazolyl, which can carry one or two halogen atoms, in particular fluorine and chlorine and / or one or two of the following radicals:
  • C 1 -C 4 alkyl such as methyl, ethyl, 1-propyl, 2-propyl,
  • C 1 -C 4 haloalkyl in particular C 1 -C 2 haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- Trifluoro ethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
  • C 1 -C 4 haloalkoxy in particular C 1 -C 2 haloalkoxy such as difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy,
  • C 1 -C 4 alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, in particular methoxy, ethoxy, 1-methylethoxy;
  • C 1 -C 4 alkylthio such as methylthio, ethylthio, propylthio,
  • R 1 is also a radical - (O) m -NR 6 R 7 in which m is 0 or 1 and R 6 and R 7 , which may be the same or different, have the following meaning:
  • C 3 -C 6 alkynyl such as 2-propynyl, 2-butynyl, 3-butynyl,
  • C 3 -C 8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohepthyl and cycclooctyl, these alkyl, cycloolkyl, alkenyl and alkynyl groups each having one to five, in particular one to three, halogen atoms, preferably fluorine or chlorine and / or wear one or two of the following groups:
  • C 1 -C 4 alkylcarbonyl such as in particular methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl, 1,1-dimethylethylcarbonyl;
  • C 1 -C 4 alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, 1-methylethoxycarbonyl, butyloxycarbonyl, 1-methylpropyloxycarbonyl, 2-methylpropyloxycarbonyl,
  • Alkynyl radicals are preferably defined as detailed above; Phenyl, optionally substituted one or more times by halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,
  • C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or C 1 -C 4 alkylthio such as 2-fluorophenyl, 3-chlorophenyl, 4-bromophenyl, 2-methylphenyl, 3-nitrophenyl, 4-cyanophenyl, 2 -Trifluoromethylphenyl, 3-methoxyphenyl, 4-trifluoroethoxyphenyl,
  • Di-C 1 -C 4 alkylamino such as especially dimethylamino, dipropylamino, N-propyl-N-methylamino, N-propyl-N-ethylamino, diisopropylamino, N-isopropyl-N-methylamino, N-isopropyl-N-ethylamino, N -Isopropyl-N-propylamino;
  • R 6 and R 7 furthermore phenyl, which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy or C 1 -C 4 alkylthio, as mentioned in detail above; or R 6 and R 7 together form an optionally substituted C 4 -C 7 alkylene chain which is closed to form a ring and which may contain a heteroatom selected from the group consisting of oxygen, sulfur or nitrogen, such as - (CH 2 ) 4 -, - (CH 2 ) s-,
  • R 1 also a group
  • R 1 is also a radical OR 9 , where R 9 is: i) hydrogen, the cation of an alkali metal or the cation of an alkaline earth metal such as lithium, sodium, potassium, calcium, magnesium and barium or an environmentally compatible organic ammonium ion such as tert.
  • C 3 -C 8 cycloalkyl as mentioned above, which can carry one to three C 1 -C 4 alkyl groups; iii) C 1 -C 8 alkyl, such as in particular methyl, ethyl, propyl,
  • C 1 -C 4 haloalkyl C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy and / or C 1 -C 4 alkylthio substituted phenyl or phenoxy, as mentioned above in particular; iv) a C 1 -C 8 -alkyl group as mentioned above which can carry one to five, preferably one to three halogen atoms, in particular fluorine and / or chlorine and carries one of the following radicals: a 5-membered heteroaromatic containing one to three Nitrogen atoms or a
  • heteroaromatic containing a nitrogen atom and an oxygen or sulfur atom, such as pyrazolyl, imidazolyl, benzimidazolyl, triazolyl, benztriazolyl, isooxazolyl, oxazolyl, thiazolyl, bonded via a carbon atom or, if possible, nitrogen atom, the heteroaromatic atom being one to can carry four halogen atoms and / or one or two of the following radicals:
  • C 1 -C 4 alkylthio The following may be mentioned in particular: 1-pyrazolyl, 3-methyl-1-pyrazolyl, 4-methyl-1-pyrazolyl,
  • C 1 -C 4 alkyl C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, phenyl, C 1 -C 4 haloalkoxy and / or C 1 -C 4 alkylthio.
  • the following may be mentioned in particular: 1-pyrazolyl, 3-methyl-1-pyrazolyl,
  • R 10 and R 11 which may be the same or different, mean:
  • Phenyl which can be substituted by one or more of the following radicals: halogen, nitro, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 -haloalkoxy or C 1 -C 4 -alkylthio, these radicals corresponding in particular to those mentioned above for R 1 ; or R 10 and R 11 together form a C 3 -C 12 alkylene chain which carry one to three C 1 -C 4 alkyl groups and can contain a heteroatom from the group consisting of oxygen, sulfur and nitrogen, as in particular in the case of R 6 and R Called 7 .
  • R 1 is also a radical -NH-SO 2 -R 12 where R 12 is: C 1 -C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 8 - Cycloalkyl as mentioned above in particular for R 1 , where these radicals can carry a C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and / or a phenyl radical as mentioned above;
  • R 2 those mentioned for R 1 in each C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 Alkylthio groups and halogen atoms, in particular chlorine,
  • X is nitrogen or CR 13 , wherein
  • R 3 is the C 1 -C 4 -alkyl-, C 1 -C 4 -haloalkyl- mentioned for R 1 ,
  • substituted phenyl means b) a radical
  • R 15 is the C 1 -C 8 -alkyl mentioned in detail for R 1 ,
  • C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 8 cycloalkyl or R 15 is a radical OR 18, wherein R 18 is as set out in detail for R 1 C 1 -C 8 - Alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl,
  • R 15 is a radical NR 19 R 20 , where R 19 and R 20 represent the radicals mentioned in detail for R 6 and R 7 , c) a radical
  • Y2 and Y3 are oxygen or sulfur and R 16 and R 17 are the radicals mentioned in detail for R 6 and R 7 .
  • R 5 is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl,
  • both the racemates and the respective enantiomers are the subject of the invention.
  • R 1 preferably represents a group OR 9 , where R 9 is in particular hydrogen and
  • variable Y is preferably sulfur and especially oxygen.
  • Particularly preferred compounds of the formula I are listed in Table 1 below. The definitions given therein and in Table 2 for R 4 are also to be regarded as preferred, regardless of the further radical definitions.
  • the compounds I or the herbicidal compositions comprising them and their environmentally compatible salts, e.g. of alkali metals, alkaline earth metals or ammonia and amines or the herbicidal compositions containing them, can be very well combated in crops such as wheat, rice and corn, soybeans and cotton, weeds and harmful grasses without damaging the crop plants, an effect which, above all occurs even at low application rates.
  • crops such as wheat, rice and corn, soybeans and cotton, weeds and harmful grasses without damaging the crop plants, an effect which, above all occurs even at low application rates.
  • the compounds I according to the invention or compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops come into consideration, for example: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus
  • napobrassica Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora ,, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck where possible, while the active ingredients are applied to the leaves underneath growing unwanted plants or the uncovered floor area (post-directed, lay-by).
  • the compounds I or the herbicidal compositions comprising them can be sprayed, atomized, for example in the form of directly sprayable solutions, powders, suspensions, also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules. Dusting, scattering or pouring can be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the compounds I are generally suitable for the preparation of directly sprayable solutions, emulsions, pastes or old dispersions.
  • Inert additives include Mineral oil fractions from medium to high boiling point, such as kerosene or diesel oil, also coal tarols and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • highly polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water .
  • Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or oil dispersions the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, as well as of fatty alcohol glycol ethers, condensation products of sulfonated and its derivatives with formaldehyde, condensation products of naphthalene or
  • Naphthalenesulfonic acids with phenol and formaldehyde polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulfite waste liquors or methyl cellulose.
  • Powders, materials for spreading and dusting can be produced by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are mineral soils such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products, such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the formulations generally contain between 0.01 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient.
  • the active ingredients are used in a purity of 90 to 100%, preferably 95 to 100% (according to the NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows: I. 20 parts by weight of compound no. 1.1 are in one
  • Dissolved mixture which consists of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor sol.
  • Dissolved mixture which consists of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of ricinusol.
  • a pouring and finely distributing the solution in 100,000 parts by weight of water gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.
  • active ingredient no. 1.7 are in a
  • Dissolved mixture which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
  • the ⁇ -halocarbonyl derivatives can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together.
  • the application rates of active ingredient are 0.001 to 3.0 kg / ha, preferably 0.01 to 1.0 kg / ha active substance (a.S.) depending on the control target, the season, the target plants and the growth stage.
  • the compounds of formula I can influence practically all developmental stages of a plant in various ways and are therefore used as growth regulators.
  • the variety of effects of the plant growth regulators depends above all a) on the plant type and variety,
  • climatic factors e.g. Temperature, amount of precipitation, day length and light intensity
  • the resulting shortening and strengthening of the stalk reduce or eliminate the risk of "storing" (twisting) of plants under unfavorable weather conditions before harvesting.
  • growth regulators it is also important to use growth regulators to inhibit the growth of length and to change the ripening process of cotton over time. This enables fully mechanized harvesting of this important crop.
  • the growth regulators can save cutting costs.
  • the alternance of fruit trees can be broken by growth regulators.
  • the use of growth regulators can also increase or inhibit the lateral branching of the plants. There is interest in this, e.g. if in tobacco plants the formation of side shoots (stinging shoots) should be inhibited in favor of leaf growth.
  • frost resistance can also be significantly increased in winter rape.
  • the growth in length and the development of a lush (and therefore particularly susceptible to frost) leaf or plant mass are inhibited.
  • the young rapeseed plants are held back after sowing and before the onset of winter frosts, despite favorable growth conditions in the vegetative development stage. This also eliminates the risk of frost for plants that tend to prematurely degrade flowering and switch to the generative phase. It is also advantageous for other crops, for example winter cereals, if the stocks are well planted in autumn by treatment with the compounds according to the invention, but do not go into the winter too abundantly.
  • the compounds of formula I can increase yields by interfering with the plant metabolism or by promoting or inhibiting vegetative and / or generative growth.
  • Harvest relief which is made possible by the temporally concentrated drop or decrease of the adhesive strength on the tree with citrus fruits, olives or other types and varieties of pome, stone and nuts.
  • the same mechanism i.e. The promotion of the formation of separating tissue between the fruit, leaf or shoot part of the plant is also essential for a well controllable defoliation of useful plants such as cotton.
  • Growth regulators can further reduce the water consumption of plants.
  • the intensity of irrigation can be reduced and thus more economical management can be carried out because, among other things, the opening width of the stomata is reduced,
  • the microclimate in the crop is favorably influenced by a more compact growth.
  • Compounds I are particularly suitable for shortening the stalks of crops such as barley, rapeseed and wheat.
  • the active compounds of the formula I to be used according to the invention can be added to the crop plants both from the seed (as a seed dressing) and via the soil, ie through the root and particularly preferred - be supplied by spraying over the sheet.
  • the amount of active ingredient is not critical due to the high tolerance to plants.
  • the optimal application rate varies depending on the control target, season, target plants and growth stages.
  • amounts of active ingredient of 0.001 to 50 g, preferably 0.01 to 10 g, are generally required per kilogram of seed.
  • doses of 0.001 to 10 kg / ha preferably 0.01 to 3 kg / ha, in particular 0.01 to 0.5 kg / ha, are generally sufficient.
  • the mixture from 2b) was reacted analogously to 1c) with 4,6-dimethoxy-2-methylsulfonylpyrimidine. After working up, the mixture was purified by flash chromatography on silica gel with n-hexane / ethyl acetate 9: 1 as the eluent. The second fraction contained the desired product.
  • Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • test plants In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
  • the test plants depending on the growth habit, are first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. The test plants are either sown directly and grown in the same containers, or they are first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the application rate for follow-up treatment is 0.5 or
  • the plants used in the greenhouse experiments are composed of the following types:

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  • Agronomy & Crop Science (AREA)
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Abstract

Des dérivés de carbonyle halogéné α répondent à la formule générale (I), dans laquelle R désigne un groupe formyle, un groupe CO2H ou un reste hydrolysable en COOH et les autres substituants ont la signification suivante: R2 désigne halogène, alkyle C¿1?-C4, halogénure d'alkyle C1-C4, alcoxy C1-C4, halogénure d'alcoxy C1-C4 ou alkylthio C1-C4; X désigne azote ou CR?13, où R13¿ désigne hydrogène ou forme avec R3 une chaîne alkylène ou alcénylène de 3 ou 4 éléments dans laquelle un groupe méthylène est substitué par oxygène; R3 désigne halogène, alkyle C¿1?-C4, halogénure d'alkyle C1-C4, alcoxy C1-C4, halogénure d'alcoxy C1-C4 ou alkylthio C1-C4, ou R?3¿ est lié à R13 comme ci-dessus de façon à former un cycle de 5 ou 6 éléments; R4 est un groupe carbonyle ou un dérivé d'un groupe carbonyle; R5 désigne hydrogène, alkyle C¿1?-C4, alcényle C3-C6, alkinyle C3-C6, cycloalkyle C3-C8, halogénure d'alkyle C1-C4, alcoxyalkyle C1-C4, alkylthioalkyle C1-C4 ou phényle; Y désigne soufre ou oxygène ou une liaison simple, Z désigne halogène.
PCT/EP1995/004453 1994-11-23 1995-11-13 DERIVES DE COMPOSES CARBONYLES HALOGENES α, PROCEDE ET PRODUITS INTERMEDIAIRES POUR LA PREPARATION DE CES DERIVES WO1996016045A1 (fr)

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AU41163/96A AU4116396A (en) 1994-11-23 1995-11-13 Derivatives of alpha-halogen carbonyl compounds, process and intermediate products for preparing the same

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DE19944441678 DE4441678A1 (de) 1994-11-23 1994-11-23 Derivate von alpha-Halogencarbonylverbindungen, Verfahren und Zwischenprodukte zu ihrer Herstellung
DEP4441678.4 1994-11-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8361927B2 (en) 2009-12-21 2013-01-29 Bayer Cropscience Ag Synergistic combination of Prothioconazole and Metominostrobin

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2051947A1 (de) * 1969-10-22 1971-04-29 LOreal, Paris Mittel zur Färbung der Haut
EP0285526A2 (fr) * 1987-02-24 1988-10-05 Zaidan Hojin Biseibutsu Kagaku Kenkyu Kai 1-N-(4-amino-3-fluoro-2-hydroxybutyl)-kanamycines
EP0468766A1 (fr) * 1990-07-24 1992-01-29 Mitsubishi Chemical Corporation Composés contenant des halogènes, compositions herbicides les contenant comme ingrédient actif, et composés intermediaires
DE4035758A1 (de) * 1990-11-08 1992-05-14 Schering Ag Substituierte (alpha)-pyrimidinyloxy(thio)- und (alpha)-triazinyloxy(thio)-carbonsaeurederivate, verfahren zu ihrer herstellung und ihre verwendung als mittel mit herbizider, fungizider und pflanzenwachstumsregulierender wirkung
DE4313411A1 (de) * 1993-04-23 1994-10-27 Basf Ag 3-Halogen-3-hetarylcarbonsäurederivate, Verfahren und Zwischenprodukte zu ihrer Herstellung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2051947A1 (de) * 1969-10-22 1971-04-29 LOreal, Paris Mittel zur Färbung der Haut
EP0285526A2 (fr) * 1987-02-24 1988-10-05 Zaidan Hojin Biseibutsu Kagaku Kenkyu Kai 1-N-(4-amino-3-fluoro-2-hydroxybutyl)-kanamycines
EP0468766A1 (fr) * 1990-07-24 1992-01-29 Mitsubishi Chemical Corporation Composés contenant des halogènes, compositions herbicides les contenant comme ingrédient actif, et composés intermediaires
DE4035758A1 (de) * 1990-11-08 1992-05-14 Schering Ag Substituierte (alpha)-pyrimidinyloxy(thio)- und (alpha)-triazinyloxy(thio)-carbonsaeurederivate, verfahren zu ihrer herstellung und ihre verwendung als mittel mit herbizider, fungizider und pflanzenwachstumsregulierender wirkung
DE4313411A1 (de) * 1993-04-23 1994-10-27 Basf Ag 3-Halogen-3-hetarylcarbonsäurederivate, Verfahren und Zwischenprodukte zu ihrer Herstellung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8361927B2 (en) 2009-12-21 2013-01-29 Bayer Cropscience Ag Synergistic combination of Prothioconazole and Metominostrobin

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AU4116396A (en) 1996-06-17
DE4441678A1 (de) 1996-05-30

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