Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
  • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
  • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
  • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
  • C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D215/14—Radicals substituted by oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
  • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
  • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
  • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
  • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
  • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

Definitions

• Benzoylcyclohexanediones and benzoylpyrazoles process for their preparation and their use as herbicides and plant growth regulators
• the invention relates to the technical field of herbicides and plant growth regulators, in particular that of herbicides for the selective control of weeds and weeds in crops of useful plants.
• benzoyl derivatives including those which, for example, have a heterocyclic radical bonded directly in the 3-position of their phenyl ring or have a heterocyclic radical bonded via a mono- or polyatomic bridge, have herbicidal properties.
• WO 99/07697 describes benzoylpyrazoles which, in the position mentioned, carry an optionally substituted heterocyclic radical which is bonded via a carbon atom chain.
• WO 99/10327 and WO 99/10328 disclose benzoylcyclohexanediones and benzoylpyrazoles, respectively, which carry an optionally substituted heterocyclic radical which is bonded via a chain of carbon atoms and a heteroatom.
• the object of the present invention is to provide herbicidal and plant growth-regulating compounds which overcome the disadvantages known from the prior art.
• the present invention therefore relates to benzoyl derivatives of the general formula (I) which are specially substituted in the 3-position of the phenyl ring,
• Q is a radical of the formula (Q1) linked in the 2-position or a radical of the formula (Q2) linked in the 4-position
• X is a straight-chain or branched, by w radicals from the group OR 3a , OCOR 3a , halogen, OCONHR 3a , OSO 2 R 3a , (dC ⁇ alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) - Alkynyl, phenyl and phenyl- (-C-C 6 ) -alkyl substituted (CC 6 ) alkylene, (C 2 -C 6 ) - alkenylene or (C 2 -C 6 ) -alkinylene chain, which is replaced by a heteroatom Oxygen and sulfur group is interrupted or carries this heteroatom at one of the chain ends, the above-mentioned alkyl, alkenyl, alkynyl and phenyl radicals optionally being replaced by one or more radicals from the group halogen, hydroxy, mercapto, amino, cyano, nitro , Formyl
• R 1 and R 2 independently of one another hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, (CC 6 ) alkyl, (C ⁇ -C 6 ) alkoxy- (C ⁇ -C 6 ) alkyl, halogen- (C 1 - C 6 ) - alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, OS (O) n R 10 , (-C -C 6 ) alkyl-A, (C 2 -C 6 ) -Alkenyl-A, (C 2 -C 6 ) -alkynyl-A, (-C-C 6 ) alkoxy- (CrC6) -alkyl-A, by m residues from
• R 3 is hydrogen, hydroxy, halogen, mercapto, amino, cyano, nitro, formyl, through m radicals from the group cyano, formyl, nitro, (CrC) -alkylamino, (C- ⁇ -C 4 ) - dialkylamino, (C - C 4 ) -alkoxycarbonyl, (-C-C 4 ) -alkylcarbonyl, (CC 4 ) - alkylcarbonyloxy, (CC) -alkyl, (C 2 -C 4 ) -alkenyl, (C 2 -C) -alkynyl, halogen- ( CC 4 ) -alkyl, (C 2 -C 4 ) -haloalkenyl, (C 2 -C 4 ) -haloalkynyl, (CC 4 ) -alkylthio, halogen- (CrC) -alkylthio, (C-
• R 3a is hydrogen, (CC 6 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, phenyl, phenyl- (CrC ⁇ J-alkyl), the five last-mentioned radicals in their non-aromatic part w radicals from the group hydroxy, halogen, mercapto, amino, cyano, nitro, formyl, (C -C) alkylamino, (C ⁇ -C 4 ) dialkylamino, (C ⁇ -C) alkoxycarbonyl, (C- ⁇ -C ) - Alkylcarbonyl, halogen (CC) alkyl, (CC 4 ) alkylthio, halogen (C ⁇ -C 4 ) alkylthio, (CrC 4 ) alkoxy and halogen (C- ⁇ -C) alkoxy are substituted ; R 4 straight or branched [C (
• R 5 OR 16 (CC 6 ) alkylthio, halogen dQ alkylthio, (C 2 -C 6 ) alkenylthio, halogen (C 2 -C 6 ) alkenylthio, (C 2 -C 6 ) alkynylthio, Halogen (C 2 -C 6 ) alkynylthio, (dC 6 ) alkylsulfinyl, halogen (CrC6) alkylsulfinyl, (C 2 -C 6 ) alkenylsulfinyl, halogen (C 2 -C 6 ) alkenylsulfinyl, ( C 2 -C 6 ) alkynylsulfinyl, halogen (C 2 -C 6 ) alkynylsulfinyl, (C C ⁇ ) alkylsulfonyl, halogen (CrC 6 ) alkylsulfony,
• R 6 is hydrogen, tetrahydropyranyl-3, tetrahydropyranyl-4, tetrahydrothiopyranyl-3, by w radicals from the group halogen, (CrC 6 ) -alkylthio and (CC 6 ) -alkoxy-substituted (C ⁇ -C 6 ) -alkyl, (C 3 -C 6 ) -cycloalkyl, (CrC 6 ) -alkoxy, (CC 6 ) -alkylcarbonyl, (CrC 6 ) -alkoxy- (-C-C 6 ) -alkyl, (CrC 6 ) -alkoxycarbonyl, (dC 6 ) - alkylthio or phenyl, or two radicals R 6 bonded to a common carbon atom form a chain from the group OCH 2 CH 2 O, OCH 2 CH 2 CH 2 O, SCH 2 CH 2 S and SCH CH CH S,
• R 7 is hydrogen, (dC 6) alkyl or (CrC 6) -haloalkyl
• R 8 (d-C ⁇ J-alkyl, halogen- (CrC 6 ) -alkyl, or optionally by one or more radicals from the group halogen, nitro, cyano, (C- ⁇ -C) alkyl, halogen- (dC) - alkyl, (CrC 4 ) alkoxy and halogen (dC 4 ) alkoxy substituted phenyl;
• R 9 is hydrogen, (dC 6 ) -alkyl, halogen- (CC 6 ) -alkyl, (CC 6 ) -alkylcarbonyl, halogen- (-C-C 6 ) -alkylcarbonyl, (C ⁇ -C 6 ) -alkoxycarbonyl, (dC 6 ) -Alkylsulfonyl, halogen- (-C-C 6 ) -alkylsulfonyl, optionally by one or more radicals from the group halogen, nitro, cyano, (dC 4 ) -alkyl, halogen- (CrC 4 ) alkyl, (dC) alkoxy and halogen (CrC) alkoxy substituted benzoyl, benzoylmethyl, phenoxycarbonyl or phenylsulfonyl;
• R 10 is hydrogen, through w radicals from the group consisting of hydroxy, halogen, mercapto, amino, cyano, (dC 4 ) -alkyl, (CC 4 ) -alkoxy, (CC 4 ) -alkylthio, di- (CC 4 ) -alkylamino, (CrC4) alkoxyimino, (CrC) alkoxythiocarbonyl, (CrC) alkylcarbonyl- (dC 4 ) alkylamino, (CjC 4 ) alkoxycarbonyl, (CC 4 ) alkylthiocarbonyl, di- (dC 4 ) - alkylaminocarbonyl, (dC 4 ) -Alkyliminooxy, (dC 4 ) -alkoxyamino, (dd) - alkylcarbonyl, (-C-C) -alkoxy- (C 2 -C 6 ) -alkoxycarbony
• R 11 is hydrogen, (CC 4 ) alkyl or halogen
• Alkyl R 12 is substituted by w radicals from the group halogen, cyano, formyl, nitro, (C ⁇ -C4) alkyl, halo (C ⁇ -C 4), (dC 4) alkoxy, halo (C ⁇ -C 4 ) alkoxy, (-C-C) alkylthio, halogen (CrC 4 ) alkylthio and R 13 substituted cycloalkyl, cycloalkenyl, aryl, one to four heteroatoms from the group containing oxygen, nitrogen and sulfur containing 5- to 6-membered heterocyclyl or heteroaryl or a radical of the formulas (Va) to (Vt):
• R 13 [(dC 4 ) -alkylene-O- (-C-C 4 ) -alkylene] 0 -O- (CrC 4 ) -alkyl, (dC 4 ) -alkyl substituted by w halogen atoms, (C 2 -C 4 ) Alkenyl or (C 2 -C 4 ) alkynyl;
• R 14 is hydrogen, (dC 4 ) alkyl, (dC 4 ) alkoxy, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, (C 3 -C 9 ) cycoalkyl, aryl, Aryl (dC 6 ) alkyl, heteroaryl, heterocyclyl, halo (dC 4 ) alkyl;
• R 15 is hydrogen, tetrahydrofuran-2-yl, (CC 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, (C 3 -C 9 ) cycoalkyl, aryl, aryl - (dC 6 ) alkyl, heteroaryl, heterocyclyl, halogen (-C-C) alkyl, or if R 14 and R 15 are bonded to one atom or to two directly adjacent atoms, they form one together with the atoms that bind them saturated, partially or fully unsaturated five to six-membered ring, which optionally additionally contains a heteroatom from the group consisting of oxygen, nitrogen and sulfur;
• R 16 is hydrogen, (dC 6 ) -alkyl, halogen- (dC 6 ) -alkyl, (C 1 -C 6 ) -alkoxy (C ⁇ -C 6 ) -alkyl, formyl, (C ⁇ -C 6 ) -alkylcarbonyl, ( dC 6 ) -alkoxycarbonyl, (CrC 6 ) -alkylaminocarbonyl, di- (-C-C 6 ) -alkylaminocarbonyl, (C ⁇ -C 6 ) -alkylsulfonyl, halogen- (CrC 6 ) -alkylsulfonyl, benzoyl or phenylsulfonyl, the latter two Groups by w identical or different radicals from the group (d-C ⁇ J-alkyl, halogen (dC 6 ) - alkyl, (C- ⁇ -C 6 ) alkoxy, halogen
• Y is a divalent unit from the group O, S, NH, N- (dC 6 ) alkyl, CHR 6 and C (R 6 ) 2 ;
• Z is a direct bond or a divalent unit from the group O, S, SO, SO 2 , NH, N- (dC 6 ) alkyl, CHR 7 or C (R 7 ) 2 ;
• Het is a bicyclic heteroaromatic or heterocycle, 0, 1 or 2, and if Het is a monocyclic heteroaromatic or heterocycle, 1 or 2;
• n 0, 1 or 2;
• the compounds of the general formula (I) contain an acidic proton which can be removed by reaction with a base.
• bases are, for example, hydrides, hydroxides and carbonates of lithium, sodium, potassium, magnesium and calcium, as well as ammonia and organic amines such as triethylamine and pyridine.
• Such salts are also the subject of the invention.
• chain-like carbon-containing radicals such as alkyl, alkoxy, haloalkyi, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals in the carbon skeleton such as alkenyl and alkynyl can each be straight-chain or branched.
• the lower of these residues are Carbon skeletons, ie with 1 to 6 carbon atoms or, in the case of unsaturated groups, with 2 to 6 carbon atoms, are preferred.
• the groups each having up to 4 carbon atoms are particularly preferred.
• Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i -Hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl;
• Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals;
• Alkenyl means, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl , 1-methyl-but-3-en-1-yl and 1-methyl-but-2
• Cycloalkyl without specifying the number of carbon atoms in the ring means a carbocyclic, saturated ring system, e.g. Cyclopropyl, cyclopentyl or cyclohexyl.
• cycloalkenyl means a monocyclic alkenyl group, e.g. Cyclopropenyl, cyclobutenyl, cyclpentenyl and cyclohexenyl, where cycloalkenyl contains a double bond and this can be located at any position.
• Halogen means fluorine, chlorine, bromine or iodine.
• Haloalkyl, alkenyl and alkynyl are partially or completely substituted alkyl, alkenyl or alkynyl, for example CF 3 , CHF 2 , CH 2 F, CF, by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine 3 CF 2 , CH 2 FCHCI, CCI 3 , CHCI 2> CH 2 CH 2 CI;
• Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 CI; the same applies to haloalkenyl and other halogen-substituted radicals.
• heterocyclyl is the radicals of three- to ten-membered, saturated, partially or completely unsaturated, mono- or bicyclic To understand heterocycles which, in addition to carbon ring members, contain one to four identical or different heteroatoms from the group consisting of nitrogen, oxygen and sulfur. If chemically possible, the linkage can take place at any position on the heterocycle.
• Heterocyclyl preferably stands for aziridinyl, tetrahydroquinolinyl, pyrrolidinyl, pyrrolinyl, pyrazolidinyl.pyrazolinyl, imidazolidinyl, imidazolinyl, oxazolidinyl, oxazolinyl, isoxazolidinyl, isoxazolinyl, thiazolinyl, thiazolidinyl, pyrazolidinyl, morpholinyl, piperazinyl, piperazinyl, morpholinyl, pyridolinyl, piperolidine, morpholinyl, pyridine Tetrahydobenzoquinolinyl, 2-oxa-3-aza-bicyclo [3.3.0] -3-octen-yl, 6-oxa-7-aza-bicyclo [4.3.0] -7-nonen-yl and, if not heterocyclyl at
• Heteroaryl stands for the remainder of a three- to ten-membered, mono- or bicyclic heteroaromatic which, in addition to carbon ring members, contains one to four identical or different heteroatoms from the group consisting of nitrogen, oxygen and sulfur. If chemically possible, the linkage can take place at any position of the heteroaromatic.
• Heteroaryl is preferably pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, 1, 2,3-triazolyl, pyridazinyl, 1, 2,4-triazolyl, 1, 2,3-oxadiazolyl, 1, 2,4- Oxadiazolyl, 1, 2,5-oxadiazolyl, tetrazolyl, 1, 3,4-oxadiazolyl, 1, 2,3-thiadiazolyl, 1, 2,4-thiadiazolyl, 1, 2,5-thiadiazolyl, 1, 3,4- Thiadiazolyl, pyridyl, pyrimidinyl, indolyl, pyrazinyl, 1, 2,4-triazinyl, 1, 3,5-triazinyl, benzoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, quinazolinyl, qui
• Aryl represents an aromatic mono- or polycyclic hydrocarbon residue, e.g. Phenyl, naphthyl, biphenyl and phenanthryl.
• radicals can be the same or different.
• the compounds of the general formula (I) can be present as stereoisomers.
• stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation processes. Stereoisomers can also be prepared selectively by using stereoselective reactions using optically active starting materials and / or auxiliary substances.
• the invention also relates to all stereoisomers and their mixtures which are encompassed by the general formula I but are not specifically defined.
• R 1 is nitro, halogen, cyano, (CrC 6 ) alkyl, halogen (CC 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, OR 10 or S (O) n R 10 ;
• R 2 is hydrogen, nitro, halogen, cyano, (dC 6 ) alkyl, halogen (dC 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, OR 10 or S (O) n R 10 and
• R 12 by w radicals from the group halogen, cyano, formyl, nitro, (dC) alkyl, halogen (CC 4 ) alkyl, (dC 4 ) alkoxy, halogen (CC) alkoxy, (CC 4 ) alkylthio, halo (CC 4) -alkylthio and R 13 are substituted (C 3 -C 6) -cycloalkyl, (C 3 -C 6) - cycloalkenyl, phenyl, one to four heteroatoms from the group oxygen, nitrogen and sulfur-containing 5- to 6-membered heterocyclyl or heteroaryl or a radical of the formula (Va) to (Vh).
• benzoyl compounds of the formula (I) in which X is a (dC 3 ) alkylene, (C 2 -C 4 ) alkenylene or (C 2 -C 4 ) alkynylene chain which is interrupted by an oxygen atom or has an oxygen atom on one of the chain ends and R 1 is in the 2-position and R 2 is in the 4-position of the benzoyl ring.
• R 1 is chlorine, bromine, iodine, nitro or methyl
• R 2 is chlorine, bromine, trifluoromethyl or (dC 4 ) alkylsulfonyl
• R 3 is hydrogen
• X is a chain from the group OCH 2 , CH 2 O, OCH 2 CH 2) CH 2 OCH 2 ,
• Preferred benzoyl compounds of the formula (I) are those in which k 1;
• Thiazolyl means, and k stands for 1. Also preferred are benzoyl compounds of formula (I), wherein
• Het represents a residue of the group quinolinyl, 5,6,7,8-tetrahydroquinolinyl, benzoxazolyl and benzothiazolyl, and k stands for 0.
• Benzoyl compounds of the formula (I) in which Q is the rest of the formula Q1 are particularly preferred.
• Q1 is a cyclohexane-1,3-dione ring of the formula (Q1 a) linked in the 2-position;
• R 17 , R 18 , R 20 and R 22 independently of one another are hydrogen or (CC 4 ) alkyl
• R 19 is hydrogen, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, optionally by one to three (dC 4 ) Alkyl radicals substituted 1, 3-dioxolan-2-yl, 1, 3-dioxan-2-yl, 1, 3-oxathiolan-2-yl, 1, 3-oxathian-2-yl, 1, 3-dithiolane 2-yl or 1,3-dithian-2-yl, by w radicals of the halogen group, (dC) -alkylthio and (-C-C) - alkoxy-substituted (CC 4 ) -alkyl or (-C-C 3 ) -cycloalkyl ;
• R 21 is hydrogen, (-CC 4 ) alkyl or (dC 6 ) alkoxycarbonyl, or
• R 19 and R 22 form a bond or a three- to six-membered ring, or
• R 19 and R 20 form a carbonyl group with the carbon atom binding them.
• R 5 is a radical containing sulfur with a Oxidation reagents, such as peroxyacetic acid, hydrogen peroxide, m-chloroperoxybenzoic acid and potassium peroxymonosulfate
• a Oxidation reagents such as peroxyacetic acid, hydrogen peroxide, m-chloroperoxybenzoic acid and potassium peroxymonosulfate
• R 5 is alkylsulfinyl, haloalkylsulfinyl, alkenylsulfinyl, haloalkenylsulfinyl, alkynylsulfinyl, haloalkynylsulfonyl, alkylsulfonylylylonylsulfonyl, alkylsulfonylylonylsulfonyl, alkylsulfonylylonylsulfonyl, alkylsulfonylylylsul
• benzoic acid derivatives of the formulas (IVa) and (IVb) used in schemes 1 and 2 can be prepared in accordance with reactions known to the person skilled in the art.
• benzoic acid derivatives of the formula (IVa) in which R represents alkoxy can be prepared according to scheme 6a by reacting a benzoic acid ester of the formula (IVc) with a heterocycle or heteroaromatics of the formula (Via).
• X 1 and X 2 each represent partial sections of X.
• Such reactions are, for example, from Houben-Weyl, Methods of Organic Chemistry, Volume E8a, pp. 45 to 176 (1993), and Volume E8c, pp. 397 to 630 (1994) Georg Thieme Verlag, known.
• Benzoic acid derivatives of the formula (IVa) in which R represents alkoxy can also be prepared according to Scheme 6b by reacting a benzoic acid ester of the formula (IVd) with a heterocycle or heteroaromatics of the formula (VIb).
• the reactions mentioned in schemes 6a and 6b are known, for example, from Houben-Weyl, Methods of Organic Chemistry, Volume VI / 3, 4th edition, p. 493ff., Georg Thieme Verlag, 1965. 18
• Benzoic acid derivatives of the formula (IVa) in which R represents alkoxy can also be obtained according to scheme 6c by so-called 1,3-dipolar cycloaddition of a benzoic acid ester of the formula (NT) with a 1,3-dipolar compound of the formula (VIIa) produce.
• X 3 denotes an alkenylene or alkynylene unit which may have an oxygen or sulfur atom.
• ABC stands for the 1,3-dipolar unit of the compound (Vlla). Examples include azides, nitrile oxides and diazo compounds.
• 1,3-dipolar cycloaddition can be used to prepare benzoic acid derivatives of the formula (IVa) according to Scheme 6d from a compound of the formula (IVf) and a compound of the formula (Villa).
• X 4 denotes an alkenylene or alkynylene unit which may have an oxygen or sulfur atom.
• the above-mentioned 1,3-dipolar cycloadditions and the preparation of the 1,3-dipolar compounds are, for example, from Houben-Weyl, Methods of Organic Chemistry, Volume 10/4, pp. 55 to 91 (1968), Volume E5, p. 1591 to 1592 and 1607 (1985), volume E4b, pp. 968 to 1051 (1990), and volume 8b, pp. 499 to 506 (1994) Georg Thieme Verlag.
• Scheme 6d :
• Benzoic acids of the formula (IVa) are new and also an object of the invention.
• the compounds of formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants.
• Perennial weeds that are difficult to control and that sprout from rhizomes, rhizomes or other permanent organs are also well captured by the active ingredients. It is usually irrelevant whether the substances are applied by pre-sowing, pre-emergence or post-emergence.
• Some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned in detail, which can be controlled by the compounds according to the invention without the name being intended to restrict them to certain species.
• weed species for example, Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria as well as Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum as well as perennial Cyperus species are well recorded.
• the spectrum of activity extends to species such as Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Sida, Matricaria and Abutilon on the annual side as well as Convolvulus, Cirsium, Rumex and Artemisia for the perennial weeds.
• Harmful plants occurring in the rice under the specific culture conditions such as, for example, Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus, are also excellently combated by the active compounds according to the invention. If the compounds according to the invention are applied to the surface of the earth before germination, either weed seedlings are prevented completely or the Weeds grow to the cotyledon stage, but then stop growing and eventually die completely after three to four weeks.
• the compounds of the invention have excellent herbicidal activity against mono- and dicotyledon weeds, crop plants of economically important crops such as e.g. Wheat, barley, rye, rice, corn, sugar beet, cotton and soy are only slightly or not at all damaged. For these reasons, the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops or in ornamental crops.
• the active compounds can also be used to control harmful plants in crops of known or still to be developed genetically modified plants.
• the transgenic plants are generally distinguished by special advantageous properties, for example resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
• Other special properties concern e.g. B. the crop in terms of quantity, quality, storability, composition and special ingredients.
• transgenic plants with an increased starch content or altered starch quality or those with a different fatty acid composition of the crop are known.
• the compounds of the formula (I) can preferably be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made resistant to genetic engineering.
• new plants which have modified properties in comparison to previously occurring plants are, for example, classic breeding methods and the generation of mutants.
• new plants with modified properties can be produced using genetic engineering methods (see, for example, EP-A-0221044, EP-A-0131624). For example, several cases have been described
• transgenic crop plants which are active against certain herbicides of the glufosinate type (see, for example, EP-A-0242236, EP-A-242246) or glyphosate (WO 92/00377) or the sulfonylureas (EP-A-0257993, US-A -5013659) are resistant,
• transgenic crop plants for example cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A-0142924, EP-A-0193259),
• transgenic crop plants with modified fatty acid composition (WO 91/13972).
• numerous molecular biological techniques with which new transgenic plants with modified properties can be produced are known; see, e.g., Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker “Gene and Clones”, VCH Weinheim 2nd edition 1996 or Christou, "Trends in Plant Science” 1 (1996) 423-431).
• nucleic acid molecules can be introduced into plasmids which allow mutagenesis or a sequence change by recombination of DNA sequences. With the help of the above standard procedures such. B. base exchanges, partial sequences removed or natural or synthetic sequences added. To connect the DNA fragments to one another, adapters or linkers can be attached to the fragments.
• the production of plant cells with a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect or the expression of at least one appropriately constructed ribozyme which specifically cleaves transcripts of the gene product mentioned above.
• DNA molecules can be used that comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules that only comprise parts of the coding sequence, these parts having to be long enough to be in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but which are not completely identical.
• the synthesized protein can be located in any compartment of the plant cell. Around but to reach the localization in a certain compartment can e.g. B. the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1: 95-106 (1991).
• the transgenic plant cells can be regenerated into whole plants using known techniques.
• the transgenic plants can in principle be plants of any plant species, i.e. both monocot and dicot plants.
• compounds of the invention in transgenic crops can be used, which are resistant to herbicides from the group of the sulfonylureas, glufosinate-ammonium or glyphosate-isopropylammonium and analogous ⁇ *
• the active compounds according to the invention are used in transgenic crops, in addition to the effects on harmful plants which can be observed in other crops, there are often effects which are specific to the application in the respective transgenic culture, for example a changed or specially expanded weed spectrum which can be controlled changed Amounts that can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influencing the growth and yield of the transgenic crop plants.
• the invention therefore also relates to the use of Compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
• the substances according to the invention have excellent growth-regulating properties in crop plants. They intervene in the plant's metabolism in a regulating manner and can thus be used to influence plant constituents in a targeted manner and to facilitate harvesting, e.g. by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesired vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage.
• the compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations.
• the invention therefore also relates to herbicidal and plant growth-regulating compositions which comprise compounds of the formula (I).
• the compounds of formula (I) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified. Possible formulation options are, for example: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), dusts (DP), pickling agents, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and Adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
• WP wettable powder
• SP water-soluble powder
• EC emulsifiable concentrates
• EW emulsion
• Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or an inert substance, but also ionic and / or nonionic surfactants (wetting agents, dispersing agents), e.g.
• the herbicidal active ingredients are finely ground, for example in conventional apparatus such as hammer mills, fan mills and air jet mills, and mixed simultaneously or subsequently with the formulation auxiliaries.
• Emulsifiable concentrates are obtained by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more surfactants ionic and / or nonionic type (emulsifiers).
• organic solvent for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more surfactants ionic and / or nonionic type (emulsifiers).
• emulsifiers may be used, for example: calcium alkylarylsulfonates such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxyethylene sorbitan fatty acid such as Polyoxethylensorbitanester.
• calcium alkylarylsulfonates such as Ca dodecylbenzenesulfonate
• nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters
• Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
• finely divided solid substances e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
• Suspension concentrates can be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally adding surfactants, such as those e.g. already listed above for the other types of formulation.
• Emulsions e.g. Oil-in-water emulsions (EW) can be used, for example, with stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those e.g. already listed above for the other formulation types.
• EW Oil-in-water emulsions
• Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, for example polyvinyl alcohol, sodium polyacrylic acid or mineral oils, to the surface of carriers such as sand, kaolinite or granulated inert material.
• Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
• Water-dispersible granules are generally produced using the customary methods, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
• the agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active ingredient of the formula (I).
• the active substance concentration in wettable powders is e.g. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components. In the case of emulsifiable concentrates, the active substance concentration can be about 1 to 90, preferably 5 to 80,% by weight.
• Dust-like formulations contain 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight of active ingredient.
• the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulating aids, fillers, etc. are used.
• the active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
• the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and Agents influencing viscosity.
• combinations with other pesticidally active substances such as insecticides, acaricides, herbicides, fungicides, and with safeners, fertilizers and / or growth regulators can also be prepared, for example in the form of a ready-to-use formulation or as a tank mix.
• Known herbicides which can be combined with the compounds of the formula (I) are, for example, the following active ingredients (note: the compounds are either with the "common name” according to the International Organization for Standardization (ISO) or with the chemical Names, if necessary together with a usual code number): acetochlor; acifluorfen; aclonifen; AKH 7088, ie [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetic acid and methyl acetate; alachlor; alloxydim; ametryn; amidosulfuron; amitrol; AMS, ie ammonium sulfamate; anilofos; asulam; atrazine; azimsulfurone (DPX-A8947); aziprotryn; barban; BAS 516 H, ie 5-fluoro-2
• the formulations present in commercial form are optionally diluted in the customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules, using water. Dust-like preparations, ground or scatter granules as well as sprayable Solutions are usually no longer diluted with other inert substances before use.
• the required application rate of the compounds of formula (I) varies. It can fluctuate within wide limits, e.g. between 0.001 and 10.0 kg / ha or more of active substance, but it is preferably between 0.005 and 5 kg / ha.
• the starting compound ethyl 2,4-dibromo-3-hydroxy-benzoic acid was prepared in accordance with US 5026896, the preparation of 2-chloro-3-hydroxy-4-methylsulfonyl-benzoic acid was carried out in accordance with EP 0 195 247.
• Step 3 2-chloro-3- (3-phenyl-isoxazol-5-yl) -methoxy) -4-methylsulfonyl-benzoic acid methyl ester
• Step 5 (3-oxo-1-cyclohexenyl) -2-chloro-3- (3-phenyl-isoxazol-5-yl) methoxy) -4-methylsulfonyl benzoate
• Step 1 Methyl 2,4-dibromo-3- (propargyl-3-oxy) benzoate 14.72 g (10.65 mmol) potassium carbonate and 12.95 g (10.70 mmol) 3-bromo-propene were dissolved in 300 ml N, N-dimethylformamide. At RT, 17.00 g (5.25 mol) of ethyl 2,4-dibromo-3-hydroxybenzoate were added and the mixture was heated at 70 ° C. for 5 h. The mixture was then poured onto water and extracted with diethyl ether.
• Step 3 2,4-dibromo- (3-phenyl-isoxazolin-5-yl) -methoxy) -4-benzoic acid 3.70 g (7.70 mmol) 2,4-dibromo- (3-phenyl-isoxazolin-5-yl) -methoxy) -4- ethyl benzoate were dissolved in a mixture of 20 ml of tetrahydrofuran and 20 ml of water, and 0.34 g (8.40 mmol) of sodium hydroxide was added. The mixture was stirred at RT for 12 h and completely concentrated on a rotary evaporator. The residue was taken up in water and treated with 6 N HCl.
• Step 5 2 - ((2,4-dibromo-3- (3-phenyl-isoxazolin-5-yl) methoxy) benzoyl) - cyclohexan-1, 3-dione
• Step 1 (2-chloro-3 - ((3-phenyl-isoxazol-5-yl) methoxy) -4-methylsulfonyl-benzoic acid) -1, 3-dimethylpyrazol-5-one-enol ester
• Dimethylaminopyridine was stirred in 10 ml of methylene chloride for 5 hours at room temperature. The mixture was then diluted with methylene chloride and with 0.5 N HCl, with
• Step 2 4- (2-chloro - ((3-phenyl-isoxazol-5-yl) methoxy) -4-methylsulfonyl-benzoyl) -1, 3-dimethylpyrazolone
• R 1 2-CI
• R 7 , R 8 Me
• a dusting agent is obtained by mixing 10 parts by weight of a compound of the general formula (I) and 90 parts by weight of talc as an inert substance and comminuting it in a hammer mill.
• a wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the general formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of lignosulphonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium as a wetting and dispersing agent grinds in a pin mill.
• a dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the general formula (I), 6 parts by weight of alkylphenol polyglycol ether ( ⁇ Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight. Mixes parts of paraffinic mineral oil (boiling range approx. 255 to above 277 ° C) and grinds in a friction ball mill> to a fineness of less than 5 microns.
• An emulsifiable concentrate is obtained from 15 parts by weight of a compound of general formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier.
• a water-dispersible granulate is obtained by adding 75 parts by weight of a compound of the general formula (I), 10 "calcium lignosulfonic acid,
• a water-dispersible granulate is also obtained by adding 25 parts by weight of a compound of the general formula (I),
• Seeds of monocotyledonous and dicotyledonous weed plants are laid out in sandy loam in cardboard pots and covered with soil.
• the compounds according to the invention formulated in the form of wettable powders or emulsion concentrates are then applied to the surface of the covering earth as an aqueous suspension or emulsion with a water application rate of the equivalent of 600 to 800 l / ha in a dosage of the equivalent of 1 kg of active substance or less per hectare.
• the pots are placed in the greenhouse and kept under good growth conditions for the weeds.
• the optical damage to the plants or the emergence damage is assessed after a test period of 3 to 4 weeks in comparison to untreated controls.
• the compounds of Examples Nos. 4.5 and 4.44 show at least 70% activity against Amaranthus retroflexus and one. at least 60% activity against Stellaria media. 2.
• Seeds of monocotyledonous and dicotyledonous weeds are placed in cardboard pots in sandy loam soil, covered with soil and grown in the greenhouse under good growing conditions.
• the test plants are treated three to three weeks after sowing.
• the compounds according to the invention formulated as wettable powder or as emulsion concentrates are sprayed onto the green parts of the plant in a dosage of the equivalent of 1 kg of active substance or less per hectare with a water application rate of the equivalent of 600 to 800 l / ha. After the test plants have stood in the greenhouse for 3 to 4 weeks under optimal growth conditions, the effect of the preparations is assessed in comparison with untreated controls.
• the agents according to the invention also have good herbicidal activity against a broad spectrum of economically important grasses and weeds, even after emergence.
• the compounds of Examples Nos. 4.2 and 4.26 show an at least 70% activity against Amaranthus retroflexus.
• the compounds of Examples Nos. 4.5, 4.26 and 4.44 show an at least 80% activity against Sinapis alba and Stellaria media.
• Typical harmful plants in rice crops are grown in the greenhouse under paddy rice conditions (water retention level: 2 - 3 cm). After the treatment with the formulated compounds according to the invention in a dosage of the equivalent of 1 kg of active substance or less per hectare, the test plants are placed in the greenhouse under optimal growth conditions and are kept for the entire test period. About three weeks after application, the evaluation of the plant damage is carried out visually in comparison to untreated controls.
• the compounds according to the invention have very good herbicidal activity against harmful plants. For example, the compounds of Examples Nos. 4.5, 4.26 and 4.44 show an at least 70% activity against Echinocloa crus-galli. 4. Compatibility with crops

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• Quinoline Compounds (AREA)
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• 1999
  • 1999-11-04 DE DE19953136A patent/DE19953136A1/de not_active Withdrawn
• 2000
  • 2000-10-24 JP JP2001534787A patent/JP2003513081A/ja active Pending
  • 2000-10-24 EP EP00974443A patent/EP1235816A1/de not_active Withdrawn
  • 2000-10-24 CA CA002397361A patent/CA2397361A1/en not_active Abandoned
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  • 2000-10-24 AU AU12749/01A patent/AU1274901A/en not_active Abandoned
  • 2000-10-24 WO PCT/EP2000/010460 patent/WO2001032636A1/de active Application Filing
  • 2000-10-31 CO CO00082896A patent/CO5221080A1/es not_active Application Discontinuation
  • 2000-11-02 AR ARP000105781A patent/AR026337A1/es not_active Application Discontinuation
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