NZ241501A - Pyrimidinyl-(and triazinyl-) salicyl- (and picolinyl-) aldehyde derivatives and herbicidal compositions - Google Patents

Pyrimidinyl-(and triazinyl-) salicyl- (and picolinyl-) aldehyde derivatives and herbicidal compositions

Info

Publication number
NZ241501A
NZ241501A NZ241501A NZ24150192A NZ241501A NZ 241501 A NZ241501 A NZ 241501A NZ 241501 A NZ241501 A NZ 241501A NZ 24150192 A NZ24150192 A NZ 24150192A NZ 241501 A NZ241501 A NZ 241501A
Authority
NZ
New Zealand
Prior art keywords
pyrimidinyl
oxy
dimethoxy
formula
phenyl
Prior art date
Application number
NZ241501A
Inventor
Christoph Luthy
Raymond Fisher
Original Assignee
Ciba Geigy Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy Ag filed Critical Ciba Geigy Ag
Publication of NZ241501A publication Critical patent/NZ241501A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen 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
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • 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
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • 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
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • 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
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Description

New Zealand Paient Spedficaiion for Paient Number £41 501 241501 : .Specification | • 1 (5)..(^X&8=A\Cv .Co^OXsAsfc;. Cp^pW®^....^Wvv^\^ .....
...J/c&lKfoislsQr. :.
A&Hcatlen Date: .?.3.„D,EC..t992.......
P.O. Journal, No: v.... !^6i is mflmf! I -r'j ':£> 4. £. A\ 'i'A $J' J l94\J Ut Iftr Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION PYRIMIDINYL- AND TRIAZINYLSALICYL-AND -PICOLINYLALDEHYDE DERIVATIVES WE, CIBA-GEIGY AG, a Swiss corporation of Klybeckstrasse 141, 4002 Basle, SWITZERLAND hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: (followed by page la) N.Z. PATENT OF? "3 FEB 1992 Received 24 1501 - lo- PH/5-18494/A Pyrimidinyl- and triazinylsalicyl- and -picolinylaldehyde derivatives The present invention relates to novel herbicidally active and plant-growth-regulating pyrimidinyl- and triazinylsalicyl- and -picolinylaldehyde derivatives, to processes for their preparation, to compositions containing them as active substances, and to their use for controlling weeds, mainly selectively in crops of useful plants or for regulating and inhibiting plant growth. 2-Phenoxy- and 2-phenylthiopyrimidines and -triazines which have a herbicidal action are generally known. Compounds of this type are described, for example, in European Patent Applications No. 0 223 406, 0 287 079, 0 249 708, 0 336 494, 0 374 839 and 0 435 186.
Novel herbicidally active and plant-growth-regulating pyrimidinyl- and triazinylsalicyl-and -picolinylaldehyde derivatives have now been found.
The pyrimidinyl- and triazinylsalicyl- and -picolinylaldehyde derivatives according to the invention are those of the formula I in which W is oxygen or NR.4; B is nitrogen, methine, or methine which is substituted by fluorine, chlorine, methyl, methoxy, 2-propenyloxy, 2-propynyloxy, difluoromethoxy or benzyloxy; Y I W (followed by page 2) * 24 1 501 Y is oxygen or sulfur; Z is methine or nitrogen; R1 is chlorine, methyl, methoxy, ethoxy, difluoromethoxy, methylamino, ethylamino or dimethylamino; R2 is methyl, methoxy or difluoromethoxy; R3 is hydrogen, fluorine, chlorine, methyl or methoxy; R4 is C^alkyl, or Cj.galkyl which is substituted by up to 3 fluorine atoms, 1 chlorine atom, 1 Cj^alkoxy group, 1 C^alkoxycarbonyl group, 1 dimethylcarbamoyl group, 1 carbamoyl group, 1 cyano group, 1 vinyl group, 1 ethynyl group or 1 phenyl group which is unsubstituted or substituted by fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy, or is phenyl, or phenyl which is up to trisubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro, orNR5R6, or OR7; R5 is hydrogen or CMalkyl; R6 is hydrogen, C^alkyl, phenyl, pyridyl, 1,3-thiazinyl, pyridazinyl, pyrazinyl, pyrimidinyl, or phenyl which is monosubstituted to trisubstituted or pyridyl which is monosubstituted to disubstituted by C^alkyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy or nitro; or pyridazinyl or pyrazinyl each of which is monosubstituted by methyl, fluorine, chlorine, trifluoromethyl or methoxy; or pyrimidinyl which is monosubstituted to disubstituted by methyl, trifluoromethyl or methoxy; or benzylcarbonyl, pyridylcarbonyl, furylcarbonyl, thiophenylcarbonyl or benzoyl each of which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or is Cj^alkylcarbonyl, trifluoromethylcarbonyl, c3_6cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridylcarbonyl, 2- or 3-furyl- or thiophenylcarbonyl, benzoyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or C1_4alkoxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminothiocarbonyl, or aminocarbonyl or aminothiocarbonyl each of which is monosubstituted to disubstituted by phenyl, C^alkyl, C2_6-alkenyl or C2_6-alkynyl it being possible for the phenyl group to be substituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy; or is C1.6-alkylsulfonyl, phenylsulfonyl or phenylsulfonyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, cyano or nitro; 24 1501 R7 is hydrogen, Cj^alkyl or C2_6alkenyl, or C2_6alkenyl which is substituted by halogen or phenyl, or C^alkoxycarbonyl-C^alkyl or Q^alkylthiocarbonyl-Q^alkyl; with the proviso that W is not oxygen when B is unsubstituted or substituted methine; that W is not NOR7 when, simultaneously, Z is methine, B is unsubstituted methine and R7 is hydrogen, Cj_6alkyl or C2_6alkenyl which can be substituted by halogen or phenyl.
In formula I, the alkyl and alkenyl radicals can be straight-chain or branched. The same is also true for the, or each, alkyl moiety of alkoxy-, alkylthio-, alkoxycarbonyl- and of further alkyl-containing groups.
If there is an asymmetric carbon atom in the compounds of the formula I, the consequence is that the compounds can occur in optically isomeric forms. If there is an aliphatic C=C or C=N double bond, geometric isomerism (for example cis or trans, E form or Z form) can also occur. Some compounds of the formula I can occur in tautomeric forms (for example keto-enol or imine-enamine tautomerism). Formula I therefore also embraces all possible configurational isomers and stereoisomers which are present in the form of E/Z isomers, enantiomers, tautomers, diastereomers or their mixtures.
In the definitions, Cj_6alkyl or C^alkyl is, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl and the pentyl isomers, and hexyl and the hexyl isomers. The alkyl groups which are present as, or in, the substituents preferably have 1 to 4 carbon atoms.
The C2_6alkenyl and C2_6alkynyl radicals which occur in the substituents can be straight-chain or branched. Preferred alkenyl radicals are those having a chain length of two to three carbon atoms. Examples of C2_6alkenyl radicals are: vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-l-yl, pentenyl or 2-hexenyl. Vinyl and allyl are preferred. Examples of C2.galkynyl radicals are: vinyl, propargyl, l-methyl-prop-2-yn-l-yl, l-methyl-but-3-yn-2-yl, 2-hexynyl or 4-pentynyl.
The C3.6cycloalkylcarbonyl groups which occur in the definitions of the substituent R6 can be unsubstituted or substituted by halogen, methyl, methylthio or methoxy, and they embrace, for example, cyclopropylcarbonyl, 2-fluorocyclopropylcarbonyl, 2,4-difluorocyclopropylcarbonyl, 2-chlorocyclopropylcarbonyl, 2,3-dichlorocyclo- 2415 01 propylcarbonyl, 2-methylcyclopropylcarbonyl, 2-methylthiocyclopropylcarbonyl, 2,3-dimethylcyclopropylcarbonyl, 2-methoxycyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, 3-methylcyclopentylcarbonyl, 3,4-dimethoxycyclopentylcarbonyl, cyclohexylcarbonyl, 3-fluorocyclohexylcarbonyl, 4-methylcyclohexylcarbonyl or 4-methylthiocyclohexylcarbonyl.
The Cj^alkylcarbonyl groups which occur in the definitions of the substituent R6 can be unsubstituted or substituted by halogen, methyl, methylthio or methoxy, and they embrace, for example, chloromethylcarbonyl, dichloromethylcarbonyl, trifluoromethylcarbonyl, methoxymethylcarbonyl or methylthiomethylcarbonyl.
Preferred compounds amongst those of the formula I are those in which the substituent R6 is hydrogen, C^alkyl, phenyl, pyridyl, or phenyl which is monosubstituted to trisubstituted or pyridyl which is monosubstituted to disubstituted by C^alkyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy or nitro; or is Chalkylcarbonyl, trifluoromethylcarbonyl, c3_6cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridylcarbonyl, 2- or 3-furyl- or thiophenylcarbonyl, benzoyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or C^alkoxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminothiocarbonyl, or aminocarbonyl or aminothiocarbonyl each of which is monosubstituted to disubstituted by phenyl or C^alkyl, it being possible for the phenyl group to be substituted by fluorine, chlorine, methyl or methoxy.
Further preferred compounds amongst those of the formula I are those in which a) R1 is chlorine, methyl, methoxy, ethoxy or difluoromethoxy; b) R2 is methoxy; c) R1 and R2 are methoxy; d) Y is oxygen; e) Z is methine; f) B is unsubstituted methine or methine which is substituted by methyl, chlorine or methoxy, or is nitrogen, preferably unsubstituted methine; g) R3 is hydrogen; h) W is NR4, R4 being tert-butyl, phenyl or phenyl which is substituted by halogen, methyl, trifluoromethyl or methoxy; i) R4 is an NR5R6 group in which R5 is hydrogen or methyl and R6 is Cj^alkyl, phenyl, or phenyl which is monosubstituted to disubstituted by halogen, C^alkyl, trifluoromethyl, 241501 nitro or methoxy or R6 is 2-pyridyl or 2-pyridyl which is monosubstituted by fluorine, chlorine, bromine, methyl or trifluoromethyl; j) R4 is an NR5R6 group in which R5 is hydrogen and R6 is C1_4alkyl-, cyclopropyl-, benzyl-, 2-,3- or 4-pyridyl-, 2-furyl- or phenylcarbonyl or phenylcarbonyl which is monosubstituted or disubstituted by halogen, methyl, trifluoromethyl, methoxy or nitro; k) R4 is an NR5R6 group in which R5 is hydrogen and R6 is C^alkoxycarbonyl; 1) R4 is an NR5R6 group in which R5 is hydrogen or methyl and R6 is C^alkylamino-, 2-propenylamino- or phenylaminocarbonyl or -aminothiocarbonyl, or phenylaminocarbonyl which is substituted by halogen, methyl, trifluoromethyl or methoxy. Particularly preferred compounds of the group 1) are those, in which R5 is hydrogen and R6 is C^alkylamino- or phenylaminocarbonyl or phenylaminocarbonyl which is substituted by halogen, methyl or methoxy; m) W is NR4, R4 being the OR7 group and R7 being C^alkoxycarbonyl-C^alkyl; n) W is NR4; o) Z is methine; p) B is nitrogen or methine which is unsubstituted and R3 is hydrogen, preferred compounds of the group p) are those in which B is methine which is unsubstituted.
In a preferred group of compounds of the formula I: R1 and R2 are methoxy; R3 is hydrogen; Y is oxygen; Z is methine; B is methine; and R4 is C(CH3)2CH2CH3, C(CH3)2OCH, C(CH3)2ON, CCH3(i-Pr)ON, C(CH3)2CON(CH3)2, CH2COOCH3, CH(CH3)COOCH3, CH(i-Pr)COOCH3, benzyl, 2-chlorobenzyl, 2-Cl-6-F-benzyl, 4-fluorophenyl, 2-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, o-tolyl, m-tolyl, p-tolyl, 4-tert-butylphenyl, 2,4-dichlorophenyl, 3-CF3-4-Cl-phenyl, NHCH2CH=CH2, NH-2-bromophenyl, NH-3-bromophenyl, NH-4-bromophenyl, NH-2-fluorophenyl, NH-4-fluorophenyl, NH-o-tolyl, NH-m-tolyl, NH-p-tolyl, NH-p-(i-Pr)-phenyl, NH-2-trifluoromethylphenyl, NH-4-trifluoromethylphenyl, NH-2-methoxyphenyl, NH-2-nitrophenyl, NH-4-nitrophenyl, NH-o-(3-Cl-tolyl), NH-(3-Cl-p-tolyl), NH-o-(4-Cl-tolyl), NH-m-(4-Cl-tolyl), NH-2,4-xylyl, NH-2,4-Cl2-(3-Cl)-xylyl, NH-2,4-difluorophenyl, NH-2,5-difluorophenyl, NH-2,4-dichlorophenyl, NH-3,5-dichlorophenyl, NH-3,4-dichlorophenyl, NH-(2-Cl-4-CF3)-phenyl, NH-(4-Cl-3-CF3)-phenyl, 24 1 501 NH-2-pyridyl, NH-2-(3-CF3)pyridyl, NH-2-(3-Cl-5-CF3)pyridyl, NH-2-(3-F-5-Cl)pyridyl, N(CH3)phenyl, NHCOCF3, NHCO-m-tolyl, NHCO-p-tolyl, NHCO-4-fluorophenyl, NHCO-4-bromophenyl, NHCO-4-methoxyphenyl, NHCO-3-furyl, NHCOOCH(CH3)2, NHCOO-benzyl, NHCONH2 or NHCSNH2.
In a particularly preferred group of compounds of the formula I: R1 is methyl, chlorine, ethoxy or difluoromethoxy; R2 is methoxy; R3 is hydrogen; Y is oxygen; Z is methine; B is methine; and R4 is 4-chlorophenyl, 3-methoxyphenyl, 3-trifluoromethylphenyl, N(CH3)2, NH-3-chlorophenyl, NH-4-chlorophenyl, NH-4-methoxyphenyl, NH-3-nitrophenyl, NH-2,3-xylyl, NH-2-(3-CF3)pyridyl, NHCOCH3, NHCO-cyclopropyl, NHCO-benzyl, NHCO-3-chlorophenyl, NHCO-4-chlorophenyl, NHCO-2,3-dichlorophenyl, NHCO-2-pyridyl, NHCO-3-pyridyl, NHCO-4-pyridyl, NHCO-2-furyl, NHCOOCH2CH3, NHCONHCH2CH3, NHCSNHCH3, NHCSNHCH2CH=CH2, NHCSNH-phenyl or NHCSNH-2-chlorophenyl.
Other compounds of the formula I which are of particular interest are those in which either: A) R1 is methyl, methoxy, ethoxy, methylamino or dimethylamino; R2 is methoxy; R3 is hydrogen; Y is oxygen; Z is nitrogen; B is methine and R4 is tert-butyl, 4-chlorophenyl, 3-methoxyphenyl, 3-trifluoromethylphenyl, N(CH3)2, NHC(CH3)3, NH-3-chlorophenyl, NH-4-chlorophenyl, NH-4-methoxyphenyl, NH-3-nitrophenyl, NH-2,3-xylyl, NH-2-(3-CF3-pyridyl), NHCOCH3, NHCOCH2CH3, NHCO-cyclopropyl, NHCO-benzyl, NHCO-3-chlorophenyl, NHCO-4-chlorophenyl, NHCO-2,3-dichlorophenyl, NHCO-2-pyridyl, NHCO-3-pyridyl, NHCO-4-pyridyl, NHCO-2-furyl, NHCONHCH2CH3, NHCSNHCH3, NHCSNHCH2CH=CH2, NHCSNH-phenyl or NHCSNH-2-chlorophenyl; or 24 1 5 01 B) R1 and R2 are methoxy; R3 is hydrogen; Y is sulfur; Z is methine; B is methine and R4 is tert-butyl, phenyl, 4-chlorophenyl, 3-methoxyphenyl, 3-trifluoromethylphenyl, N(CH3)2, NHC(CH3)3, NH-3-chlorophenyl, NH-4-chlorophenyl, NH-4-methoxyphenyl, NH-3-nitrophenyl, NH-2,3-xylyl, NH-2-(3-CF3)pyridyl, NHCOCH3, NHCOCH2CH3, NHCO-cyclopropyl, NHCO-benzyl, NHCO-3-chlorophenyl, NHCO-4-chlorophenyl, NHCO-2,3-dichlorophenyl, NHCO-2-pyridyl, NHCO-3-pyridyl, NHCO-4-pyridyl, NHCO-2-furyl, NHCOOCH2CH3, NHCONHCH2CH3, NHCSNHCH3, NHCSNHCH2CH3, NHCSNHCH2CH=CH2, NHCSNH-phenyl or NHCSNH-2-chlorophenyl; or C) R1 and R2 are methoxy; R3 is hydrogen; Z is methine; Y is oxygen; B is nitrogen, or methine which is substituted by chlorine, methyl or methoxy, and R4 is tert-butyl, phenyl, 4-chlorophenyl, 3-methoxyphenyl, 3-trifluoromethylphenyl, N(CH3)2, NHC(CH3)3, NH-3-chlorophenyl, NH-4-chlorophenyl, NH-4-methoxyphenyl, NH-3-nitrophenyl, NH-2,3-xylyl, NH-2-(3-F-5-Cl)pyridyl, NH-2-(3-CF3)pyridyl, NHCOCH2CH3, NHCO-cyclopropyl, NHCO-benzyl, NHCO-3-chlorophenyl, NHCO-4-chlorophenyl, NHCO-2,3-dichlorophenyl, NHCO-2-pyridyl, NHCO-3-pyridyl, NHCO-4-pyridyl, NHCO-2-furyl, NHCOOCH2CH3, NHCONHCH2CH3, NHCSNHCH3, NHCSNHCH2CH3, NHCSNHCH2CH=CH2, NHCSNH-phenyl or NHCSNH-2-chlorophenyl; or D) R1 and R2 are methoxy; R3 is hydrogen; Y is oxygen; Z is methine; B is nitrogen, or methine which is substituted by chlorine, methyl or methoxy; W is NOR7 and R7 is hydrogen, methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, s-butyl, CH2CH2CH(CH3)2, CH2CH=CH(CH3), CH2CH=C(CH3)C1, CH2CH=CHphenyl, 24 1 5 8- CH2COOCH3, CH(CH3)COOCH3, CH(CH2CH3)COOCH3> CH2COOC(CH3)3, CH(i-Pr)COOC(CH3)3, CH2COOCH2CH=CH2, CH2COOCH2CH3, CH(CH3)COOCH2CH3, CH2COSCH2CH3 or CH(CH3)COSCH2CH3.
In a very particularly preferred group of compounds of the formula I, R1 is methyl, chlorine, methoxy, ethoxy or difluoromethoxy; R2 is methoxy; R3 is hydrogen; Y is oxygen; Z is methine; B is methine; W is NOR7; and R7 is CH(CH3)COOCH3, CH(CH2CH3)COOCH3, CH(CH3)COOCH2CH3, CH2COOCH2CH=CH2, CH2COSCH2CH3 or CH(CH3)COSCH2CH3.
A group of compounds of the formula I which excels particularly because of its good biological action is that in which R1 is methyl, methoxy, ethoxy, methylamino or dimethylamino; R2 is methoxy; R3 is hydrogen; Y is oxygen; Z is nitrogen; B is methine or nitrogen; W is NOR7; and R7 is hydrogen, methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, s-butyl, CH2CH2CH(CH3)2, CH2CH=CH(CH3), CH2CH=C(CH3)C1, CH2CH=CHphenyl, CH2COOCH3, CH(CH3)COOCH3, CH(CH2CH3)COOCH3, CH2COOC(CH3)3, CH(i-Pr)COOC(CH3)3, CH2COOCH2CH=CH2, CH2COOCH2CH3, CH(CH3)COOCH2CH3, CH2COSCH2CH3 or CH(CH3)COSCH2CH3.
The following may be mentioned as preferred individual compounds from the scope of the formula I: 3-[(4,6-dimethoxy-2-pyrimidinyl)oxy]pyridine-2-carboxaldehyde, 4,6-dimethoxy-2-[(a-phenylimino-o-tolyl)oxy]pyrimidine, 4,6-dimethoxy-2-[(a-(a,a,a-trifluoro-m-tolyl)imino-o-tolyl)oxy]pyrimidine, 4,6-dimethoxy-2-[(a-(m-methoxyphenyl)imino-o-tolyl)oxy]pyrimidine, 241501 2-[(a-(p-chlorophenyl)imino)-o-tolyl)oxy]-4,6-dimethoxypyrimidine, 2-[(a-(tert-butyl)imino-o-tolyl)oxy]-4,6-dimethoxypyrimidine, o- [(4,6-dimethoxy-2-pyrimidinyl)oxy] benzaldehyde phenylhydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde (p-chlorophenyl)hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde dimethylhydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde tert-butylhydrazone, 3-[(4,6-dimethoxy-2-pyrimidinyl)oxy]pyridine-2-carboxaldehyde phenylhydrazone, 3-[(4,6-dimethoxy-2-pyrimidinyl)oxy]pyridine-2-carboxaldehyde [(3-trifluoromethyl)-2-pyridyl]hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde (p-methoxyphenyl)hydrazone, o- [(4,6-dimethoxy-2-pyrimidinyl)oxy] benzaldehyde (m-nitrophenyl)hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde (2,3-dimethylphenyl)hydrazone, p-chloro-N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]benzohydrazide, N'-io-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]benzohydrazide, N,-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-o-methoxybenzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]nicotinohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]propionohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-o-nitrobenzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-2-pyridinecarboxyhydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-m-chlorobenzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]acetohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-2-phenylacetohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-2-furanecarboxyhydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-2-thienylcarboxyhydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-(2,3-dichloro)benzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-o-trifluoromethylbenzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]cyclopropylcarboxyhydrazide, Ethyl 3-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]carbazate, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-methyl-3-thiosemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-ethylsemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-(o-chlorophenyl)-3-thiosemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-(m-chlorophenyl)-3-thiosemicarbazone, o- [(4,6-dimethoxy-2-pyrimidinyl)oxy] benzaldehyde 4-(p-chlorophenyl)-3-thiosemicarbazone, 241501 o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-phenyl-3-thiosemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-ethyl-3-thiosemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-allyl-3-thiosemicarbazone and 3-[(4,6-dimethoxy-2-pyrimidinyl)oxy]pyridine-2-carboxaldehyde oxime.
The following may be further mentioned as preferred individual compounds from the scope of the formula I: o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyde-(o-chlorp henyl)-hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyde-(p-tert-butyl-phenyl)-hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyde-(m-trifluo rmethylphenyl)-hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyde-(2,3-dichl orphenyl)-hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyde-[(3-chloro - 5-trifluormethyl) -2-pyridyl] -hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyde-N-methyl-p henylhydrazone, 3-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-pyridin-2-carboxyaldehy de-(o-chlorphenyl)-hydrazone, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)-oxy)-benzylidene]-o-meth ylbenzohydrazide, N' - [o-((4,6-dimethoxy-2-pyrimidinyl)-oxy) -benzylidene] -4-pyri dincarboxyhydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)-oxy)-benzylidene]-o-meth ylbenzohydrazide, N'-[3-(o-((4,6-dimethoxy-2-pyrimidinyl)-oxy)-pyridyl)-methyli dene]-2-phenylacetohydrazide, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyd-N-methyl-3- thiosemicarbazone, o- [(4,6-dimethoxy-2-pyrimidinyl)-oxy] -benzaldehyd-3-thiosemic arbazone.
Compounds of the formula I in which R!-R4, Z, Y and B are as defined above and W is NR4 can be prepared by reacting an aldehyde of the formula II in which R1, R2, R3, Z, Y and B are as defined under formula I, with an amine, hydrazine, hydrazide, carbazate, semicarbazide or thiosemicarbazide or oxime of the formula III in which R4 is as defined under formula I, if desired in the presence of a water-binding agent and an inert diluent. 241501 - li - h2n in Y ► i o ii Compounds of the formula I can also be prepared by reacting a pyrimidine of the formula IV in which R1, R2 and Z are as defined under formula I and L is a leaving group such as fluorine, chlorine, bromine, C^alkylsulfonyl (for example methylsulfonyl or ethylsulfonyl), benzylsulfonyl, 3-Ci^alkylsulfonyl-lH-l,2,4-triazol-l-yl (for example 3-methylsulfonyl-lH-l,2,4-triazol-l-yl), with an imine, hydrazone, hydrazide, carbazate, semicarbazide, thiosemicarbazide or oxime compound of the general formula V in which R3, R4, B and Y are as defined under formula I, in the presence of an acid-binding agent, for example n-butyllithium, sodium hydride, potassium carbonate or triethylamine, and in the presence of an inert solvent, for example tetrahydrofuran, dimethoxyethane, acetone, methyl ethyl ketone, acetonitrile, propionitrile, dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide.
The process is advantageously carried out at 0°C to the boiling point of the solvent used, preferably between room temperature and about 100°C.
YH I IV V Furthermore, compounds of the formula I in which R1, R2, R3, B, Y and Z are as defined under formula I and in which R6 in the definition NR5R6 is C^alkylcarbonyl, trifluoromethylcarbonyl, 241501 c3_6cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridinyl, 2- or 3-furyl or thiophenylcarbonyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or C^alkoxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminothiocarbonyl, or aminocarbonyl or aminothiocarbonyl each of which is monosubstituted to disubstituted by phenyl or Ci_4alkyl, it being possible for the phenyl group to be substituted by fluorine, chlorine, methyl or methoxy, can be prepared by reacting a compound of the formula II in which R1, R2, R3, Z, Y and B are as defined above, with hydrazine or hydrazine hydrate, and the hydrazide of the formula I' in which R1, R2, R3, B, Y and Z are as defined above and W is NNH2 is then reacted with the corresponding acid chloride, chloroformic ester, carbamoyl chloride or thiocarbamoyl chloride of the formula VI in which U is oxygen or sulfur, or with the corresponding isocyanate or isothiocyanate of the formula VI' in which U is oxygen or sulfur.
VI or U=C=N-R6> I' VI' The particular reaction conditions are known to those skilled in the art.
Furthermore, compounds of the formula I in which R1, R2, R3, B, Y and Z are as defined above and in which R7 in the definition W = NOR7 is C^alkyl, C3.6alkenyl which can be substituted by halogen or phenyl, or is C^alkoxy- or alkylthiocarbonyl-C^alkyl, can be prepared by reacting an oxime of the formula I" in which R!-R3, B, Y and Z are as defined above and in which W is NOH, with an alkyl-, alkenyl- or C^alkoxy- or alkylthiocarbonyl-Cj^-alkyl halide of the formula VII in the presence of an inert diluent, for example toluene, tetrahydrofuran, acetone, 2-butanone, acetonitrile or dimethylformamide, and in the presence of an acid-binding agent, for example potassium carbonate, sodium hydride or triethylamine. 24 1 501 Compounds of the formula II are either known or can be prepared by known processes. For example, aldehydes of the formula II (R3 = H) have been disclosed in European Patent Applications EP-A-0 223 406 (B=C-H), EP-A-0 249 708 (B=C-C1), EP-A-0 287 079 (B=OCHF2, OCH2CH=CH2OCH2OCH, OCH2phenyl, OCH2OCH3) and EP-A-0 336 494 (Z=N, B=C-H).
Compounds of the formula I" in which R1 and R2 are methoxy, Y is oxygen and B is methine, are known from European Patent Application EP-A-0 374 839.
Compounds of the formula IV are also either known (cf. for example, the above references) and/or can be prepared by the processes cited therein.
Compounds of the formula V are also either known or can be prepared by the processes known to those skilled in the art.
For example, compounds of the formula V' can be prepared by oxidising a compound of the formula VIII (cf. for example, Tetr. 3,49-55 (1958) and J. Amer. Chem. Soc. 76, 648-652 (1954)) in which Y is as defined under formula I, by known methods using a suitable oxidising agent [ox], for example manganese dioxide. 24 1 50 YH YH [ox] H OH O VIE V' Compounds of the formula VI, VI' and VII are furthermore known from the literature.
The compounds of the formula I (hereinafter also named "active substances") have herbicidal properties and are suitable for controlling weeds, including grass weeds, for example, inter alia, Agropyron repens, Alopecurus myosuroides, Avena fatua, Bromus inermis, Echinochloa crus-galli, Poa annua, Sorghum halepense, Abutilon theophrasti, Amaranthus retroflexus, Cassia obtusifolia, Chenopodium album, Galium aparine, Matricaria chamomilla, Sinapis arvensis and Stellaria media in a range of crops of useful plants, for example, inter alia, rice crops, in particular paddy rice, wheat, maize, soya, oilseed rape, sunflowers and cotton. Moreover, the compounds are both pre-emergence and post-emergence herbicides. In some compounds of the formula I, a good selectivity was noticed, for example in the control of weeds in wheat, soya crops and cotton crops.
Moreover, the compounds of the formula I have plant-growth-regulating properties and are suitable as active substances for positively influencing the growth of useful plants.
This effect can lead to a desired growth inhibition in crop plants and also inhibit the germination of weeds sufficiently to eliminate them as competitors of the crop plants. From an ecological point of view, this is advantageous and hence extremely desirable. Aspects which should be mentioned in particular are the protection of the soil surface from drying out and/or erosion and the reduction of the bulk of weed seeds in the soil (combined with prevention of flowering and further seed production). This effect may therefore be preferred to the complete prevention of weed formation, which may, however, be limited to a particular period.
In practice, a concentration of 1 g to 3 kg of the compound of the formula I per ha, preferably 10 g to 1 kg/ha, is usually sufficient for achieving the desired herbicidal effect. To achieve the desired herbicidal effect in combination with optimum tolerance by the useful plants, the range from 10 to 100 g/ha is particularly favourable when carrying out a 241501 pre-emergence treatment, and the range from 100 to 1000 g/ha is particularly favourable when carrying out a post-emergence treatment.
The weedkillers and plant-growth regulators according to the invention comprise an effective amount of at least one compound of the formula I and, as a rule, also formulation auxiliaries. Advantageously, they each comprise at least one formulation auxiliary from each of the following groups: - solid carriers; - solvents or dispersants; - surfactants (wetting agents and emulsifiers); - dispersants (without surfactant action); and - stabilisers.
The pesticidal formulations comprise, as a rule, besides the active substances of the formula 11 to 99 % of a formulation auxiliary from the group comprising - solid carriers; - solvents or dispersants; - dispersants (without surfactant action); and - stabilisers; and 0 to 25 %, in particular 0.1 to 25 %, of a surfactant (wetting agents and emulsifiers).
Using these and other auxiliaries, the compounds of the formula I, i.e. the herbicidal active substances, can be converted into the customary formulations such as dusts, powders, granules, solutions, emulsions, suspensions, emulsifiable concentrates, pastes and the like.
The compounds of the formula I are generally water-insoluble and can be formulated by methods customary in the case of water-insoluble compounds, using the known formulation auxiliaries. The compositions can be prepared in a manner known per se, for example by mixing the particular active substance with solid carriers, by dissolving or suspending in suitable solvents or dispersants, with or without the use of surfactants as wetting agents or emulsifiers and/or dispersants, or by diluting prefabricated emulsifiable concentrates with solvents or dispersants.
The following are mainly suitable as solid carriers: - natural minerals, such as chalk, dolomite, limestone, clays and silica and its salts, for example kieselguhr, kaolin, bentonite, talc, attapulgite or montmorillonite; 241501 - synthetic minerals, such as highly-disperse silica, alumina or silicates; - organic substances, such as cellulose, starch, urea or artificial resins; and - fertilisers, such as phosphates or nitrates.
Such carriers can be, for example, in the form of powders or granules.
The following are mainly suitable as solvents or dispersants: - aromatic substances, such as benzene, toluene, xylene and alkylnaphthalenes; - chlorinated aromatic substances and chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylenes or methylene chloride; - aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions; - alcohols, such as butanol or glycol, and their ethers and esters; - ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; and - strongly polar solvents or dispersants, such as dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide (such solvents preferably having flash points of at least 30°C and boiling points of at least 50°C), or water.
Other suitable solvents or dispersants are also so-called liquefied gaseous, extenders or carriers, which are products which are gaseous at room temperature and under atmospheric pressure. Examples of such products are, in particular, aerosol propellants, such as halohydrocarbons, for example dichlorodifluoromethane.
If the weedkiller according to the invention is in the form of a pressurised gas pack, it is advantageous to employ a solvent in addition to the propellant.
The surfactants (wetting agents and emulsifiers) can be non-ionic compounds, such as: - condensation products of fatty acids, fatty alcohols or fat-substituted phenols with ethylene oxide; - fatty acid esters and fatty acid ethers of sugars or polyhydric alcohols; - the products which are obtained from sugars or polyhydric alcohols by condensation with ethylene oxide; - block polymers of ethylene oxide and propylene oxide; or - alkyldimethylamine oxides. 24 1 501 The surfactants can also be anionic compounds, such as: - soaps; - fatty sulfate esters, for example dodecyl sodium sulfate, octadecyl sodium sulfate or cetyl sodium sulfate; - alkylsulfonates, arylsulfonates or fatty-aromatic sulfonates, such as alkylbenzenesulfonates, for example calcium dodecylbenzenesulfonate or butylnaphthalenesulfonates; or - more complex fatty sulfonates, for example the amide condensation products of Isure and N-methyltaurine, or the sodium sulfonate of dioctyl succinate.
Finally, the surfactants can be cationic compounds, such as alkyldimethylbenzylammonium chlorides, dialkyldimethylammonium chlorides, alkylmethylammonium chlorides or ethoxylated ammonium chlorides.
The following are mainly suitable as dispersants (without surfactant action): lignin, sodium salts and ammonium salts of ligninsulfonic acids, sodium salts of maleic anhydride/diisobutylene copolymers, sodium salts and ammonium salts of sulfonated polycondensation products of naphthalene and formaldehyde, or sulfite waste liquors.
Dispersants which are particularly suitable as thickeners or anti-settling agents which can be employed are, for example, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, alginates, caseinates or blood albumin.
Examples of suitable stabilisers are: - acid-binding agents, for example epichlorohydrin, phenyl glycidyl ether or soya epoxides; - antioxidants, for example gallic esters or butylatedhydroxytoluene; - UV absorbers, for example substituted benzophenones, diphenyl-(3-cyano acrylic acid esters or cinnamic esters; or - deactivators, for example salts of ethylenediaminotetraacetic acid, or polyglycols.
In addition to the compounds of the formula I, the weedkillers and plant-growth regulators according to the invention can also contain other active substances, for example insecticides, acaricides, nematicides, molluscicides, bactericides, fungicides, herbicides, plant-growth-regulating substances, fertilisers and trace-element sources. Such combined compositions are suitable for widening the spectrum of action. 241501 In general, the weedkillers according to the invention comprise between 0.001 and 95 %, preferably between 0.5 and 75 %, by weight of one or more of the compounds of the formula I as active substance. For example, they can be in a form which is suitable for storage and transport. In such formulations, for example emulsifiable concentrates, the active substance concentration is usually in a higher range, preferably between 1 and 50 % by weight, in particular between 5 and 30 % by weight. These formulations can then be diluted, for example with identical or different inert substances, down to the active substance concentration which is suitable for use in practice, viz. preferably about 0.001 to 10 % by weight, in particular about 0.005 to 5 % by weight. However, the active substance concentrations can also be lower or higher.
As mentioned, the weedkiller according to the invention can be prepared in a manner known per se.
For preparing preparations in the form of powders, the active substance, i.e. at least one compound of the formula I, can be mixed with a solid carrier, for example by simultaneous grinding. Alternatively, the solid carrier can be impregnated with a solution or suspension of the active substance, and the solvent or dispersant can then be removed by evaporation, heating or filtering off under reduced pressure. By adding surfactants or dispersants, it is possible to render such agents, which are in the form of powders, readily wettable with water, so that they can be converted into aqueous suspensions which are suitable, for example, as sprays.
Alternatively, the active substance can be mixed with the surfactant and a solid carrier to give a wettable powder which is dispersible in water, or it can be mixed with a solid, pregranulated carrier to give a product in the form of granules.
If desired, the active substance can be dissolved in a solvent which is not miscible with water, for example a high-boiling hydrocarbon. This solvent expediently contains a dissolved emulsifier, so that the solution is self-emulsifying when added to water. On the other hand, the active substance can be mixed with an emulsifier, and the mixture can then be diluted with water to the desired concentration. Moreover, the active substance can be dissolved in a solvent, and the solution can then be mixed with an emulsifier. Such a mixture can also be diluted with water to the desired concentration. In this manner, emulsifiable concentrates or ready-for-use emulsions are obtained. 24 1 501 The weedkillers described can be used according to the invention in customary application methods, such as spraying, atomising, dusting, pouring or scattering.
The examples which follow are intended to further illustrate the invention.
Preparation examples: Example 1: 3-[(4,6-Dimethoxy-2-pyrimidinyl)oxy]-pyridine-2-carboxaldehyde can be prepared as follows: g of 3-hydroxy-2-hydroxymethylpyridine are suspended in 1000 ml of chloroform, and the suspension is heated to boiling point. 80-100 ml of ethanol are subsequently added slowly until a clear solution has formed. 40 g of activated manganese oxide are then carefully introduced at reflux temperature. The mixture is heated for a further 3 hours and then filtered under hot conditions. The solvents are stripped off under reduced pressure. The resinous product in 10 ml of ethyl acetate is transferred to a "dry column flash chromatography" silica gel column and eluted using ethyl acetate/hexane 1:3. 3-Hydroxypyridine-2-carboxaldehyde is obtained as yellowish crystals; melting point: 15-1TC. 8.6 g of the above 3-hydroxypyridine-2-carboxaldehyde are dissolved in a mixture of 125 ml of tetrahydrofuran and 100 ml of dimethylformamide. 2.7 g of a 60 % suspension of sodium hydride in oil is washed with dry tetrahydrofuran and then added carefully to the above reaction mixture. When the evolution of hydrogen has ceased, 15 g of 4,6-dimethoxy-2-pyrimidinyl methyl sulfone are added, and the mixture is heated for 20 hours at reflux temperature, under a nitrogen atmosphere. When the mixture has cooled, the solvents are removed under reduced pressure and the product is then taken up in 500 ml of dichloromethane. The dark suspension is treated with active charcoal under hot conditions and filtered. The solvent is removed under reduced pressure, and the residue which remains is recrystallised from ethyl acetate/hexane 7:8. 3-[(4,6-Dimethoxy-2-pyrimidinyl)oxy]pyridine-2-carboxaldehyde, of melting point 102 to 104°C, is obtained as an almost white solid.
Example 2: 4,6-Dimethoxy-2-[[a-[(E and/or Z)-phenylimino]-o-tolyl]oxy]pyrimidine (Compound No. 1.007) can be prepared as follows: 2 A 1 5 01 2.60 g of 2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde and 1.05 g of aniline in 25 ml of ethanol and in the presence of 3 drops of acetic acid are maintained at reflux temperature for 45 minutes. The reaction mixture is cooled to -5°C, and the product which has precipitated is filtered off and washed with ice-cold ethanol. Pure 4,6-dimethoxy-2-[[<x-[(E and/or Z)-phenylimino]-o-tolyl]oxy]pyrimidine (Compound No. 1.007), of melting point 74-75°C, are obtained by recrystallisation from hot ethanol.
Example 3: 4,6-Dimethoxy-2-[[a-[(E and/or Z)-phenylimino]-o-tolyl]oxy]pyrimidine (Compound No. 1.007) can also be prepared as follows: 2.0 g of N-phenyl-2-hydroxybenzimine and 2.2 g of 4,6-dimethoxy-2-pyrimidinyl methyl sulfone are heated at reflux temperature for 24 hours in the presence of 10 g of potassium carbonate in 150 ml of ethyl acetate. When cold, the reaction mixture is diluted with 150 ml of dichloromethane and filtered. The solvents are stripped off, and the residue is purified by means of dry flash chromatography. 4,6-Dimethoxy-2-[[a-[(E and/or Z)-phenylimino]-o-tolyl]oxy]pyrimidine (Compound No. 1.007) is obtained; *H NMR(CDC13): 3.80, s, 2xOCH3; 5.79, s, CH; 7.1 - 7.5 8H, 8.26, m, 1H; 8.67, s, CH=N.
Example 4:2-[[a-[(E and/or Z)-tert-butylimino]-o-tolyl]oxy]-4,6-dimethoxypyrimidine (Compound No. 1.008) can be prepared as follows: 4.2 g of 2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde and 10 g of tert-butylamine are initially introduced into 100 ml of dry tetrahydrofuran. The sealed reaction vessel is allowed to stand for one week in the presence of 5 g of 4A molecular sieve. The mixture is subsequently evaporated to dryness, and 4.9 g of 2-[[a-[(E and/or Z)-tert-butylimino]-o-tolyl]oxy]-4,6-dimethoxypyrimidine (Compound No. 1.008) are obtained as an oil; 1HNMR(CDC13): 1.19, s, C(CH3)3; 3.80, s, 2x OCH3; 5.77, s, CH; 7.1 - 8.1 4H; 8.40, s, CH=N.
Example 5: o-[ (4,6-Dimethoxy-2-pyrimidinyl)oxy] benzaldehyde (E and/or Z)-phenylhydrazone (Compound No. 1.054) can be prepared as follows: 2.6 g of 2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde are introduced into a warm solution of 1.2 g of phenylhydrazine in 30 ml of ethanol, 3 drops of acetic acid are added, and the mixture is kept at boiling point for a further 5 minutes. The mixture is cooled and 24 1 5 0 the product which has precipitated is filtered off and purified by recrystallisation from hot ethanol. o-[(4,6-Dimethoxy-2-pyrimidinyl)oxy]benzaldehyde (E and/or Z)-phenylhydrazone (Compound No. 1.054) are obtained, melting point: 107-108°C.
Example 6: N'-(E and/or Z)-o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzylidene]-propionohydrazide (Compound No. 1.055) can be prepared as follows: 4 g of 2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde are introduced into a solution of 15 g of hydrazine hydrate in 100 ml of methanol, during which process the temperature is allowed to rise to +50°C. After the mixture has been cooled to room temperature, 150 ml of dichloromethane are added, the mixture is washed four times with water, and the organic phase is dried over sodium sulfate. 4 g of triethylamine are then added and the reaction mixture is treated dropwise with 1.7 g of propionyl chloride. Stirring is continued for 10 minutes, and the mixture is then washed twice with 200 ml of water, separated, dried and evaporated to dryness under reduced pressure. The crude product is recrystallised from ethyl acetate/hexane 2:1. N'-[(E and/or Z)-o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzylidene]propionohydrazide (Compound No. 1.055) is obtained, melting point: 144-146°C.
Example 7: 2-[(4,6-Dimethoxy-2-pyrimidinyl)oxy]benzaldehyde o-ethoxycarbonylmethyl oxime (Compound No. 4.003) can be prepared as follows: 2.0 g of 2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldoxime, 0.94 ml of ethyl chloroacetate and 2.1 g of potassium carbonate are heated at reflux temperature for 2 hours in the presence of a spatula tip each of sodium iodide and 18-crown-6 in 20 ml of acetonitrile. The mixture is then extracted with ethyl acetate using water and sodium chloride solution as the aqueous phase, and, after evaporation to dryness, the crude product is purified on a silica gel column using 20 % acetic acid in hexane. 2-[(4,6-Dimethoxy-2-pyrimidinyl)oxy]benzaldoxime ethoxycarbonyl methyl ether (Compound No. 4.003) is obtained as a yellow oil; *H NMR (CDC13): 1.29, t, J=7.5 Hz, OCH2CH3; 3.80, s, 2xOCH3; 4.24, q, J=7.5 Hz, OCH2CH3; 5.78, s, CH, 4.68, s, NOCH2; 7.19, txd, J=7.5xl.5 Hz, CH; 7.41, txd, J=7.5xl.5 Hz, CH; 7.86, dxd, J=7.5xl.5 Hz, CH; 8.38, s, CH=N.
Example 8: 3-[(4,6-Dimethoxy-2-pyrimidinyl)oxy)pyridine-2-carboxaldehyde oxime (Compound No. 4.004) can be prepared as follows: 24 1 5 0 A methanolic solution of 1.0 g of sodium acetate and 0.7 g of hydroxylamine hydrochloride is briefly heated to reflux temperature. 1.8 g of 3-[(4,6-dimethoxy-2-pyrimidinyl)oxy]pyridine-2-carboxaldehyde (Example 1) are introduced after 1 minute. The reaction mixture is kept at reflux temperature for a further 5 minutes, and such an amount of water is then added until a clear solution is obtained. On cooling, 3-[(4,6-dimethoxy-2-pyrimidinyl)oxy]-pyridine-2-carboxaldehyde oxime (Compound No. 4.004) precipitates as white crystals; melting point 169-171°C.
The compounds listed in the tables below can be prepared analogously to Examples 2 to 8. In those cases where no melting point or *11 NMR spectrum is indicated, the Rf values (refractive index) were determined in ethyl acetate/hexane. 241501 23 Table 1: Compounds of the formula la: ch30 Ri II ° aa) n —r4 b 24 1 5 01 Comp. No.
B R1 R4 Melting point [°C]/physical data Rf: (ethyl acetate/hexane) 1.001 c-h och3 o cf3 73-75° 1.002 c-h och3 OMe liquid Rf: 0.58 (1:2) 1.003 c-h och3 -Q-a 76-78° 1.004 c-h och3 101-102° 1.005 c-h ch3 \ / phenyl liquid Rf: 0.43 (1:2) 1.006 c-h ch3 c(ch3)3 liquid Rf: 0.30(1:2) 1.007 c-h och3 -o 74-75° 1.008 c-h och3 c(ch3)3 oil Rf: 0.66 (1:2) 1.009 c-h och3 c(ch3)2och liquid Rf: 0.48 (1:2) 1.010 N och3 c(ch3)3 oil Rf: 0.52 (2:1) 1.011 N och3 Phenyl oil Rf: 0.34 (2:1 1.012 N och3 -0-a 137-138°C 241501 Table 2: Compounds of the formula lb: ch3o och3 n-^ n o h (lb) N —N R, b R, 24 1 501 Comp. No. b r5 R6 Melting point [°C]/physical data Rf: (ethyl acetate/hexane) 2.001 ch h Oc> 134-137° 2.002 ch ch3 ch3 80-82° 2.003 ch h c(ch3)3 86-90° 2.004 N h phenyl ci \ 115-118° 2.005 N h 158-160° 2.006 N h N —' ci . / 106-109° 2.007 ch h 152-153° 2.008 ch h 0 \\ .
N — o" / 128-129° 2.009 ch h 169-170° 2.010 ch h ci \—. 143-145° 2.011 ch h -"t) 157-159° 2.012 ch h ^CF3 116-118° 2.013 ch h Cl CI \ / 141-143° 2.014 ch h 185-186° Ik 1 5 Table 2, continuation: Comp. No.
B R5 R6 Melting point [°C]/physical data Rf: (ethyl acetate/hexane) CI \ 2.015 c-h h 144-147° 2.016 c-h h $ o U 149-151° 2.017 c-h h coc(ch3)3 154-157° 2.018 c-h h co^>cl 209-211° 2.019 c-h h °°-0 -o \ 219-221° 2.020 c-h h c0\l_y 157-159° 2.021 c-h h ccr-Q> 166-168° 2.022 N h co-^> no2 152-154° 2.023 N h coch3 180-182° 2.024 ch h Qsr o u 159-160° 24 1 5 Table 2, continuation: Comp. No.
B R5 R6 Melting point [°C]/physical data Rf: (ethyl acetate/hexane) 2.025 C-H H c°-Q> 169-171° 2.026 C-H H co-o* 148-150° 2.027 C-H H co-q CI 163-165° 2.028 C-H H COCH3 168-170° 2.029 C-H H c°co 162-163° 2.030 C-H H <*-0 196-198° 2.031 C-H H 192-193° 2.032 C-H H CO-Q 0- 188-189° 2.033 C-H H CGH^ CI CI 207-209° 2.034 C-H H c°-@ cf3 160-162° 2.035 C-H H CO—<| 192-194° 2.036 C-H H COCH2CH(CH3)2 160-161° 2.037 C-H H COCH(CH3)2 132-134° 241 Table 2, continuation: Comp. No. b R5 R6 Melting point [°C]/physical data Rf: (ethyl acetate/hexane) 2.038 ch h csnhch3 176-178° 2.039 ch ch3 csnh2 147-150° 2.040 ch h co-O 150-152° 2.041 ch h conhch2ch3 156-158° 2.042 n h conhr^) 180-183° 2.043 ch h csnlh^) ci 154-155° 2.044 ch h csnh^) ci 186-187° 2.045 ch h csni^<^>-c1 168-169° 2.046 ch h csnh-<^> 171-172° 2.047 ch h csnhch2ch3 162-164° 2.048 ch h csnhch2ch=ch2 170-171° 2.049 ch h conh-^^ 172-175° 241501 - Table 2, continuation: Comp. No. b R5 R6 Melting point [°C]/physical data Rf: (ethyl acetate/hexane) 2.050 ch h cooch3 173-174° 2.051 ch h cooc(ch3)3 102-105° 2.052 ch h cooch2ch3 171-173° 2.053 N h cooch3 190-193° 2.054 ch h O 107-108° 2.055 ch h coch2ch3 144-146° 2.056 N h cooch2ch3 181-183° 241501 Tabelle 1: 2415 Tabelle 1: Comp. No B R5 R6 Melting point [°C] physical data CI V 2.070 c-h h CO-fA 188-191°C 2.071 N h co-/~\ 192-194°C CO—v 2.072 N h o 179-180°C 2.073 N h coch2ch3 142-143°C CI nv 2.074 N h CO^Q> 224-226°C CI 2.075 N h conh2 193-196°C 2.076 N h csnh2 237-239°C 2.077 N h CSNH 181-183°C 2.078 c-h h csnhch2ch3 168-169°C 2.079 c-h h csnhch2ch=ch2 172-173°C 2.080 c-h ch3 conh \ 157-158°C ^Cl 2.081 c-h ch3 conh fi \ 128-130°C CI 2.082 N N conh 0 \ 157-159°C \ 241501 Table 3: Compounds of the formula Ic: O Ri NyN O H (Ic) .Rs N-N' \ Ra Comp. No.
R1 R5 R6 Melting point [°C]/physical data Rf: (ethyl acetate/hexane) O — / 3.001 ch3 h -o liquid Rf: 0.60 (2:1) 3.002 ch3 h csnhch2ch3 194-195° 3.003 ch3 h phenyl O r.—a 167-169° 3.004 ch3 h -"o 198-199° 3.005 ch3 h c(ch3)3 liquid Rf: 0.58 (2:1) 3.006 ch3 h coch2ch3 97-99° 241501 Table 4: Compounds of the formula Id: o h dd) Comp. No.
B R1 R7 Melting point [°C]/physical data Rf: (ethyl acetate/hexane) 4.001 c-h och3 ch2cooc(ch3)3 oil 4.002 c-h och3 COOC(CH3)3 oil 4.003 c-h och3 ch2cooch2ch3 oil 4.004 N och3 h 169-171° 4.005 N och3 c(ch3)2och3 oil 4.006 N och3 ch2cooc(ch3)3 COOC(CH3)3 Rf: 0.39 (2:1) 4.007 N och3 > Rf: 0.48 (2:1) 4.008 N och3 / ch3 84-86°c 4.009 N och3 ch2cooch3 Rf: 0.36(2:1) 4.010 N och3 ch2ch=c(ch3)2 Rf: 0.67 (2:1) 4.011 N och3 ch2ch=ch ^ ^ Rf: 0.48 (2:1) 241501 Table 5: Compounds of the formula Ie: CH3° y VRl O H (Ie) N — R4 B Comp. No.
B R1 R4 Melting point [°C]/physical data Rf: (ethyl acetate/hexane) .001 CH och3 nh-cooch2ch3 147-148° .002 CH och3 NH-phenyl 161-162° .003 CH och3 phenyl 137-138° -36 Table 6: Compounds of the formula If: 24 1 501 CH3° ^ OCH, N Y H (If) N —N .Rs .B R« 24 1 501 Comp. No.
Y B R5 R6 Phys. Data 6.001 S C-H H C(CH3)3 6.002 S C-H H -o 6.003 S C-H H -O-' 6.004 S C-H H CI 6.005 s C-H H CI 6.006 s C-H H C(S)NHCH2CH=CH2 6.007 o C-F H C(CH3)3 6.008 o C-F H -O-' 6.009 o C-F H -O 6.010 o C-F H ^OF, -p CI 6.011 o C-F H C(S)NH—y 6.012 o C-F H C(S)NHCH2CH3 6.013 o C-F H C(S)NHCH2CH=CH2 6.014 o C-F H CO—^ ^ 6.015 o C-F H COOCH2CH3 24 15 01 Comp. No. y b r5 r6 Phys. Data 6.016 o c-f h conh—^ ci 6.017 0 c-f h coch2 —i 6.018 o c-f h coch2 —^ y 6.019 0 c-f h -o 6.020 o c-f h -P A ^ 6.021 o c-f h s-> ci 6.022 o c-ch3 h -o 6.023 o c-ch3 h -p ci 6.024 o c-ch3 h -O-' 6.025 o c-ch3 h c(s)nhch2ch3 6.026 o c-ch3 h c(s)nh—^ ^—f 6.027 o c-ch3 h coch2 —^ ^ 6.028 o c-och3 h -o Comp. No.
Y B R5 R6 Phys. Data 6.029 0 C-och3 H -0-f 6.030 0 C-och3 H C(S)NH—^ —F 6.031 0 C-och3 H coch2 —^ y 6.032 O C-H H -O 6.033 0 C-H H -Q 6.034 o C-H H / \ F -0-* 6.035 o C-H H _0-c, 6.036 o C-H H -Q-' 6.037 o C-H H ci 6.038 o C-H H 6.039 o C-H H c(s)nh —^ ^— f 6.040 o C-H H c(s)-nh—^ ^—cf3 6.041 o C-H H C(S)NHCH2C=CH 6.042 0 C-H H C(S)N(CH3)2 24 1 5 -40 Comp. No. y b R5 R6 Phys. Data 6.043 o c-h h so2ch3 6.044 o c-h h so2ch2ch3 6.045 o c-h h s02-Q 6.046 o c-h h s02 —^ ^— f 6.047 o c-h h so2-Q ci 6.048 o c-h h s°2H0> 6.049 o c-h h \ / \ CF3 SOg —if ^ OCHg 6.050 o c-h h so2_p ci 6.051 o c-h h so2-p> 6.052 o c-h h so2np ch3 6.053 o C-F h so2ch3 6.054 o C-F h s02-^} 6.055 o c-cl h so2^j^ 241501 Comp. No. y b R5 r6 Phys. Data 6.056 o c-ch3 h so2 -0 6.057 o c-och3 h s02 -<0 6.058 o c-h h so2 -p Na 6.059 o c-h h so2 - —cn 6.060 o c-h h so2 — Oci C. Formulation examples Example Fl: To prepare a 25 % wettable powder, the components listed below are mixed with each other: Per cent by weight Compound of the formula I according to tables 1-6 25 Hydrated silica (carrier, grinding auxiliary) 20 Sodium lauryl sulfate (wetting agent) 2 Sodium lignosulfate (dispersant) 4 Kaolin (carrier) 49 100 First, the liquid or molten active substance is applied to the silica which has been introduced into a grinding apparatus. The other components are subsequently admixed. The mixture is ground finely using a pin mill or a comparable grinding apparatus.
When stirred into water, the resulting wettable powder gives a fine suspension which is suitable as 241501 a ready-for-use spray mixture.
Active substances which are particularly suitable for this formulation are compounds of the formula I which are liquid or which have a low melting point, i.e. up to about +100°C.
Example F2: Compounds of the formula I which have a high melting point, i.e. above about +100°C, can preferably be used as active substances in concentrated wettable powders, for example as follows: The components are mixed with each other and ground finely using a pin mill or a comparable grinding device, in particular a jet mill.
When stirred into water, the resulting wettable powder gives a fine suspension of any desired concentration which is suitable as a ready-for-use spray mixture.
Example F3: A wettable powder based on the composition of Example F3 can also be converted into dispersible granules. For this purpose, the ground powder is sprayed with an aqueous solution of the binder in a suitable granulation apparatus (for example granulation plate, mixing drum, high-speed stirrer or fluidised-bed granulator) until agglomerations have formed. After this, the water which has been added is removed again in a drying process. The granules of the desired size are collected by sieving.
Compared with the wettable powder, the resulting granules have a series of advantages (no dust formation on application, easier metering because of better flow properties). They are applied in just the same fashion as in the case of the wettable powder, after the preparation has been stirred into water and the granules have disintegrated completely into the primary particles.
Per cent by weight Compound of the formula I according to tables 1-6 Hydrated silica (carrier, grinding auxiliary) Alkylnaphthalenesulfonate and alkyl-carboxylate-sulfate as sodium salts Sulfonated naphthalene/formaldehyde condensate as the sodium salt (dispersant) Polyvinylpyrrolidone (binder) Kaolin (carrier) 1 J1 100 75 1 2 24 1 5 01 Example F4: The compounds of the formula I have limited solubility in the customary organic solvents. Accordingly, emulsifiable concentrates of relatively low concentration are possible; for example: The active substance and the emulsifier are introduced into the solvent, with stirring. The mixture is stirred until a homogeneous solution has formed.
The resulting emulsifiable concentrate can be emulsified in water, which gives a ready-for-use spray mixture of the desired concentration.
Example F5: Compounds of the formula I having a melting point higher than about +60°C can also be formulated as so-called suspension concentrates ("flowables"); for example: Compound of the formula I according to tables 1-6 250 g/1 Ethylene glycol (antifreeze agent) 80 g/1 Silica (anti-settling agent) 5 g/1 Xanthan gum (thickener) 2 g/1 Silicone defoamer 5 g/1 Nonylphenol polyethoxylate (wetting agent) 20 g/1 Sulfonated naphthalene/formaldehyde condensate as the sodium salt (dispersant) 40 g/1 Water to 1000 ml The formulation auxiliaries are dissolved in water. The pre-ground active substance is dispersed in the solution, with stirring. The resulting coarse suspension is now subjected to wet grinding (for example in a colloid mill or a stirred ball mill). If desired, small amounts of further additives are now possible, such as antifoam agents, anti-settling agents and biocides.
Compound of the formula I according to tables 1-6 Emulsifier N-Methyl-2-pyrrolidone (solvent) to 125 g/1 300 g/1 1000 ml For use, the resulting "flowable" can be diluted with water as desired, giving a ready-for-use spray mixture of the desired concentration. 241501 Biological examples Example Bl: Pre-emergence herbicidal action Immediately after the test plants (a number of weeds, both monocotyledon and dicotyledon) have been sown in seed dishes in a greenhouse, the soil surface is treated with an aqueous spray mixture, corresponding to a rate of application of 3 kg of active substance/hectare.
The test substances are preferably formulated as emulsifiable concentrate (EC) and diluted with water to the desired concentration immediately before application. Insoluble substances are formulated as a wettable powder (WP), using kaolin as the inert carrier. This wettable powder is suspended in water immediately before application. - The dosage rates in g of active ingredient/ha relate to the soil surface in the containers, unless otherwise indicated. The spray volume is 5001/ha.
The seeds of the plants are sown in plastic plant pots of various sizes containing heat-sterilised (steamed) soil (terrestial soil 2.6 % peat, 20 % clay, 30 % silt, 47 % sand). The plants are kept in the greenhouse at an average temperature (17 - 25°C in winter, 18 - 35°C in summer) (atmospheric humidity 30 - 90 %). The length of the photoperiod is 13 to 16 hours/day; if necessary, artificial light is added (15000 to 18000 lux). Artificial illumination is also activated automatically when the daylight intensity is insufficient.
After 3 weeks, the herbicidal action is rated in comparison with an untreated control group, using a three-step, linear key (2 = 80-100 % damage, 1 = 30-79 % damage, 0 = 0-29 % damage).
In this test, the compounds of the formula I described in the examples have a powerful herbicidal action.
Examples of the good herbicidal action of the compounds of the formula I which are described in the tables of the present application are listed in Table Bl: 241501 Table Bl: Pre-emergence herbicidal action Compound No.
SEAACSADMC OCVLHTBAAA RHEOEEUTTS GINPNLTURS 1 1 1 1 2 2 2 2 2 2 2 2 2 2 001 002 007 008 002 003 012 013 026 027 028 029 048 054 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 2 2 2 2 2 2 2 2 2 2 2 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 2 2 2 2 2 2 2 2 2 2 2 2 In the table SORG denotes ECHI denotes AVEN denotes ALOP denotes CHEN denotes STEL denotes ABUT denotes DATU denotes MATR denotes CASS denotes Sorghum halepense Echinochloa crus-galli Avena fatua Alopecurus myosuroides Chenopodium album Stellaria media Abutilon theophrasti Datura stramonium Matricaria chamomilla Cassia obtusifolia Johnsongrass Barnyard grass Wild oat Blackgrass Lambs quarters Chickweed Velvetleaf Jimsonweed Wild chamomile Sicklepod 241501 Example B2: Post-emergence herbicidal action (contact herbicide) After emergence (in the 4- to 6-leaf stage), a number of weeds, both monocotyledon and dicotyledon, were treated with an aqueous dispersion of active substance at a dosage rate of 3 kg of active ingredient per hectare.
The test substances are preferably formulated as an emulsifiable concentrate (EC), and diluted with water to the desired concentration immediately before application. Insoluble substances are formulated as a wettable powder (WP), using kaolin as the inert carrier.
This wettable powder is suspended in water immediately before application.
Unless otherwise indicated, dosage rates in g of active ingredient/ha are based on the soil surface in the containers. The spray volume is 5001/ha.
The seeds of the plants are sown in plastic plant pots of various sizes containing heat-sterilised (steamed) soil ("Optima" soil 80 % peat, 20 % loess). The plants are kept in the greenhouse at an average temperature (17 - 25°C in winter, 18 - 35°C in summer) (atmospheric humidity 30 - 90 %). The length of the photoperiod is 13 to 16 hours/day; if necessary, artificial light is added (15000 to 18000 lux). Artificial illumination is also activated automatically when the daylight intensity is insufficient.
After 3 weeks, the herbicidal action is rated in comparison with an untreated control group, using a three-step, linear key (2 = 80-100 % damage, 1 = 30-79 % damage, 0 = 0-29 % damage).
In this test, the compounds described in the examples also have a powerful herbicidal action.
Examples of the good herbicidal action of the compounds of the formula I which are described in the tables of the present application are listed in Table B2: Zk 1 501 Table B2: Post-emergence herbicidal action: Compound No. S E A A C S A 0 C V L H T B R H E O E E U G I N P N L T 2.003 2.007 2.012 2.037 5.002 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 2 2 1 1 2 2 2 2 2 In the table SORG denotes Sorghum halepense Johnsongrass ECHI denotes Echinochloa crus-galli Barnyard grass AVEN denotes Avena fatua Wild oat ALOP denotes Alopecurus myosuroides Blackgrass CHEN denotes Chenopodium album Lambs quarters STEL denotes Stellaria media Chickweed ABUT denotes Abutilon theophrasti Velvetleaf Example B3: Herbicidal action for paddy rice The seeds of the plants are sown in plastic beakers or boxes of various sizes, sealed at the bottom end and containing fertilised soil. The soil is heat-sterilised (steamed) and contains about 80 % (w/v) loam and 20 % peat and 0.05 % Nutricote (16/10/10) and 0.05 % "Plantamaag" as fertiliser. The plants are kept in a special greenhouse cabin at a high temperature (20-35°C) and high atmospheric humidity (60-80 %), the latter being kept constant by means of a sprinkler system. The length of the photoperiod is 13 to 16 hours/day; if necessary, artificial light (15000 to 18000 lux) is added. Artificial illumination is also activated automatically when the daylight intensity is insufficient.

Claims (28)

24 1 -48- The test substances are preferably formulated as emulsifiable concentrates (EC) and diluted to the desired concentration with water immediately before application. Insoluble substances are formulated as a wettable powder (WP), using kaolin as the inert carrier. This wettable powder is suspended in water immediately before application. The dosage rates in g of active ingredient/ha are relative to the soil surface in the containers, unless otherwise indicated. The spray volume is 5001/ha. The tests are rated after 3 or 4 weeks (post-emergence or pre-emergence treatment) in comparison with an untreated control group, using a ten-step, linear key (10 = complete damage, 0 = no action). Here, too, the compounds of the formula I have a selective herbicidal action against the weeds. 241501 -49- \m^0^^bAm£Dl£: WHAT)K?WE CLAIM IS:-
1. A pyrimidinyl- and triazinylsalicyl- and -picolinylaldehyde derivative of the formula I in which W is oxygen or NR4; B is nitrogen, methine, or methine which is substituted by fluorine, chlorine, methyl, methoxy, 2-propenyloxy, 2-propynyloxy, difluoromethoxy or benzyloxy; Y is oxygen or sulfur; Z is methine or nitrogen; R1 is chlorine, methyl, methoxy, ethoxy, difluoromethoxy, methylamino, ethylamino or dimethylamino; R2 is methyl, methoxy or difluoromethoxy; R3 is hydrogen, fluorine, chlorine, methyl or methoxy; R4 is C^alkyl, or Cj.galkyl which is substituted by up to 3 fluorine atoms, 1 chlorine atom, 1 Cj^alkoxy group, 1 C^alkoxycarbonyl group, 1 dimethylcarbamoyl group, 1 carbamoyl group, 1 cyano group, 1 vinyl group, 1 ethynyl group or 1 phenyl group which is unsubstituted or substituted by fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy, or is phenyl or phenyl which is up to trisubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro, or NR5R6, or OR7; R5 is hydrogen or C^alkyl; R6 is hydrogen, Cj.galkyl, phenyl, pyridyl, 1,3-thiazinyl, pyridazinyl, pyrazinyl, pyrimidinyl, or phenyl which is monosubstituted to trisubstituted or pyridyl which is 241501 -50- monosubstituted to disubstituted by C^alkyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy or nitro; or pyridazinyl or pyrazinyl each of which is monosubstituted by methyl, fluorine, chlorine, trifluoromethyl or methoxy; or pyrimidinyl which is monosubstituted to disubstituted by methyl, trifluoromethyl or methoxy; or benzylcarbonyl, pyridylcarbonyl, furylcarbonyl, thiophenylcarbonyl or benzoyl each of which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or is C^galkylcarbonyl, trifluoromethylcarbonyl, c3_6cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridylcarbonyl, 2- or 3-furyl- or thiophenylcarbonyl, benzoyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or C^alkoxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminothiocarbonyl, or aminocarbonyl or aminothiocarbonyl each of which is monosubstituted to disubstituted by phenyl, Q^alkyl, C2_6-alkenyl or C2.6-alkynyl it being possible for the phenyl group to be substituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy; or is C^g-alkylsulfonyl, phenylsulfonyl or phenylsulfonyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, cyano or nitro; R7 is hydrogen, Cj.galkyl or C2_6alkenyl, or C2_6alkenyl which is substituted by halogen or phenyl, or C^alkoxycarbonyl-Ci^alkyl or C^alkylthiocarbonyl-C^alkyl; with the proviso that W is not oxygen when B is unsubstituted or substituted methine; that W is not NOR7 when, simultaneously, Z is methine, B is unsubstituted methine and R7 is hydrogen, Cj^alkyl or C2_6alkenyl which can be substituted by halogen or phenyl.
2. A compound of the formula I according to claim 1, in which R6 is hydrogen, C^alkyl, phenyl, pyridyl, or phenyl which is monosubstituted to trisubstituted or pyridyl which is monosubstituted to disubstituted by Cj.4alkyl, fluorine, chlorine, bromine, trifluoromethyl, methoxy or nitro; or is C^alkylcarbonyl, trifluoromethylcarbonyl, C3_6cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridylcarbonyl, 2- or 3-furyl- or thiophenylcarbonyl, benzoyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or C^alkoxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminothiocarbonyl, or I 241501 -51 - aminocarbonyl or aminothiocarbonyl each of which is monosubstituted to disubstituted by phenyl or C^alkyl, it being possible for the phenyl group to be substituted by fluorine, chlorine, methyl or methoxy;
3. A compound of the formula I according to claim .1, in which W is NR4.
4. A compound of the formula I according to claim 1, in which R1 and R2 are methoxy.
5. A compound of the formula I according to claim 1, in which Y is oxygen.
6. A compound of the formula I according to claim 1, in which Z is methine.
7. A compound of the formula I according to claim 1, in which B is nitrogen or methine which is unsubstituted and R3 is hydrogen.
8. A compound of the formula I according to claim 7, in which B is methine which is unsubstituted.
9. A compound of the formula I according to claim 1, in which R3 is hydrogen.
10. A compound of the formula I according to claim 1, in which W is NR4 and R4 being tert-butyl, phenyl, or phenyl which is substituted by halogen, methyl, trifluoromethyl or methoxy.
11. A compound of the formula I according to claim 1, in which R4 is an NR5R6 group in which R5 is hydrogen or methyl and R6 is C^alkyl, phenyl, or phenyl which is monosubstituted to disubstituted by halogen, C^alkyl, trifluoromethyl, nitro or methoxy or R6 is 2-pyridyl or 2-pyridyl which is monosubstituted by fluorine, chlorine, bromine, methyl or trifluoromethyl.
12. A compound of the formula I according to claim 1, in which R4 is an NR5R6 group in which R5 is hydrogen and R6 is C^alkyl-, cyclopropyl-, benzyl-, 2-,3- or 4-pyridyl-, 2-furyl- or phenylcarbonyl or phenylcarbonyl which is monosubstituted or disubstituted by halogen, methyl, trifluoromethyl, methoxy or nitro.
13. A compound of the formula I according to claim 1, in which R4 is an NR5R6 group in Ik 1 501 - 52 - which R5 is hydrogen and R6 is C^allcoxycarbonyl.
14. A compound of the formula I according to claim 1, in which R4 is an NR5R6 group in which R5 is hydrogen or methyl and R6 is C^alkylamino-, 2-propenylamino- or phenylaminocarbonyl or -aminothiocarbonyl, or phenylaminocarbonyl which is substituted by halogen, methyl, trifluoromethyl or methoxy.
15. A compound of the formula I according to claim 14, in which R5 is hydrogen and R6 is C^alkylamino- or phenylaminocarbonyl or phenylaminocarbonyl which is substituted by halogen, methyl or methoxy.
16. A compound of the formula I according to claim 1, in which R1 and R2 are methoxy; R3 is hydrogen; Y is oxygen; Z is methine; B is methine; and R4 is C(CH3)2CH2CH3, C(CH3)2OCH, C(CH3)2ON, CCH3(i-Pr)C=N, C(CH3)2CON(CH3)2, CH2COOCH3, CH(CH3)COOCH3, CH(i-Pr)COOCH3, benzyl, 2-chlorobenzyl, 2-Cl-6-F-benzyl, 4-fluorophenyl, 2-chlorophenyl, 4-bromophenyl, 4-trifluoromethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, o-tolyl, m-tolyl, p-tolyl, 4-tert-butylphenyl, 2,4-dichlorophenyl, 3-CF3-4-Cl-phenyl, NHCH2CH=CH2, NH-2-bromophenyl, NH-3-bromophenyl, NH-4-bromophenyl, NH-2-fluorophenyl, NH-4-fluorophenyl, NH-o-tolyl, NH-m-tolyl, NH-p-tolyl, NH-p-(i-Pr)phenyl, NH-2-trifluoromethylphenyl, NH-4-trifluoromethylphenyl, NH-2-methoxyphenyl, NH-2-nitrophenyl, NH-4-nitrophenyl, NH-o-(3-Cl)tolyl, NH-(3-Cl)p-tolyl, NH-o-(4-Cl)tolyl, NH-m-(4-Cl)tolyl, NH-2,4-xylyl, NH-2,4-(3-Cl)xylyl, NH-2,4-difluorophenyl, NH-2,5-difluorophenyl, NH-2,4-dichlorophenyl, NH-3,5-dichlorophenyl, NH-3,4-dichlorophenyl, NH-(2-Cl-4-CF3)phenyl, NH-(4-Cl-3-CF3)phenyl, NH-2-pyridyl, NH-2-(3-CF3)pyridyl, NH-2-(3-Cl-5-CF3)pyridyl, NH-2-(3-F-5-Cl)pyridyl, N(CH3)phenyl, NHCOCF3, NHCO-m-tolyl, NHCO-p-tolyl, NHCO-4-fluorophenyl, NHCO-4-bromophenyl, NHCO-4-methoxyphenyl, NHCO-3-furyl, NHCOOCH(CH3)2, NHCOO-benzyl, NHCONH2 or NHCSNH2.
17. A compound of the formula I according to claim 1, in which R1 and R2 are methoxy; 24 1 -53- R3 is hydrogen; Y is sulfur; Z is methine; B is methine and R4 is tert-butyl, phenyl, 4-chlorophenyl, 3-methoxyphenyl, 3-trifluoromethylphenyl, N(CH3)2, NHC(CH3)3, NH-3-chlorophenyl, NH-4-chlorophenyl, NH-4-methoxyphenyl, NH-3-nitrophenyl, NH-2,3-xylyl, NH-2-(3-CF3)pyridyl, NHCOCH3, NHCOCH2CH3, NHCO-cyclopropyl, NHCO-benzyl, NHCO-3-chlorophenyl, NHCO-4-chlorophenyl, NHCO-2,3-dichlorophenyl, NHCO-2-pyridyl, NHCO-3-pyridyl, NHCO-4-pyridyl, NHCO-2-furyl, NHCOOCH2CH3, NHCONHCH2CH3, NHCSNHCH3, NHCSNHCH2CH3, NHCSNHCH2CH=CH2, NHCSNH-phenyl or NHCSNH-2-chlorophenyl.
18. A compound of the formula I according to claim 1, in which R1 and R2 are methoxy; R3 is hydrogen; Z is methine; Y is oxygen; B is nitrogen, or methine which is substituted by chlorine, methyl or methoxy, and R4 is tert-butyl, phenyl, 4-chlorophenyl, 3-methoxyphenyl, 3-trifluoromethylphenyl, N(CH3)2, NHC(CH3)3, NH-3-chlorophenyl, NH-4-chlorophenyl, NH-4-methoxyphenyl, NH-3-nitrophenyl, NH-2,3-xylyl, NH-2-(3-F-5-Cl)pyridyl, NH-2-(3-CF3)pyridyl, NHCOCH2CH3, NHCO-cyclopropyl, NHCO-benzyl, NHCO-3-chlorophenyl, NHCO-4-chlorophenyl, NHCO-2,3-dichlorophenyl, NHCO-2-pyridyl, NHCO-3-pyridyl, NHCO-4-pyridyl, NHCO-2-furyl, NHCOOCH2CH3, NHCONHCH2CH3, NHCSNHCH3 NHCSNHCH2CH3, NHCSNHCH2CH=CH2, NHCSNH-phenyl or NHCSNH-2-chlorophenyl.
19. A compound of the formula I according to claim 1, selected from amongst 3-[(4,6-dimethoxy-2-pyrimidinyl)oxy]pyridine-2-carboxaldehyde, 4,6-dimethoxy-2-[(a-phenylimino-o-tolyl)oxy]pyrimidine, 4,6-dimethoxy-2-[(a-(a,a,a-trifluoro-m-tolyl)imino-o-tolyl)oxy]pyrimidine, 4,6-dimethoxy-2-[(a-(m-methoxyphenyl)imino-o-tolyl)oxy]pyrimidine, 2-[(a-(p-chlorophenyl)imino)-o-tolyl)oxy]-4,6-dimethoxypyrimidine, 2-[(a-(tert-butyl)imino-o-tolyl)oxy]-4,6-dimethoxypyrimidine, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde phenylhydrazone, 24 1501 -54- o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde (p-chlorophenyl)hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde dimethylhydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde tert-butylhydrazone, 3-[(4)6-dimethoxy-2-pyrimidinyl)oxy]pyridine-2-carboxaldehyde phenylhydrazone, 3-[(4,6-dimethoxy-2-pyrimidinyl)oxy]pyridine-2-carboxaldehyde [(3-trifluoromethyl)-2-pyridyl]hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde (p-methoxyphenyl)hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde (m-nitrophenyl)hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde (2,3-dimethylphenyl)hydrazone, p-chloro-N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]benzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]benzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-o-methoxybenzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]nicotinohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]propionohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-o-nitrobenzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-2-pyridinecarboxyhydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-m-chlorobenzohydrazide, N1- [o-((4,6-dimethoxy-2-pyrimidinyl)oxy)] benzylidene] acetohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-2-phenylacetohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-2-furanecarboxyhydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-2-thienylcarboxyhydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-(2,3-dichloro)benzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]-o-trifluoromethylbenzohydrazide, Nl-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]cyclopropylcarboxyhydrazide, Ethyl 3-[o-((4,6-dimethoxy-2-pyrimidinyl)oxy)]benzylidene]carbazate, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-methyl-3-thiosemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-ethylsemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-(o-chlorophenyl)-3-thiosemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-(m-chlorophenyl)-3-thiosemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-(p-chlorophenyl)-3-thiosemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzaldehyde 4-phenyl-3-thiosemicarbazone, o- [(4,6-dimethoxy-2-pyrimidinyl)oxy] benzaldehyde 4-ethyl-3-thiosemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)oxy] benzaldehyde 4-allyl-3-thiosemicarbazone and 24 1 501 -55 - 3-[(4,6-dimethoxy-2-pyrimidinyl)oxy]pyridine-2-carboxaldehyde oxime. '
20. A compound of the formula I according to claim 1, selected from amongst o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyde-(o-chlorphenyl)-hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy] -benzaldehyde- (p-tert-butyl-phenyl)-hydrazone, o- [(4,6-dimethoxy-2-pyrimidinyl)-oxy] -benzaldehyde- (m-trifluo rmethylphenyl)-hydrazone, o- [(4,6-dimethoxy-2-pyrimidinyl)-oxy] -benzaldehyde-(2,3-dichl orphenyl)-hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyde-[(3-chloro -5 -trifluormethyl)-2-pyridyl] -hydrazone, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyde-N-methyl-p henylhydrazone, 3-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-pyridin-2-carboxyaldehy de-(o-chlorphenyl)-hydrazone, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)-oxy)-benzylidene]-o-meth ylbenzohydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)-oxy)-benzylidene]-4-pyri dincarboxyhydrazide, N'-[o-((4,6-dimethoxy-2-pyrimidinyl)-oxy)-benzylidene]-o-meth ylbenzohydrazide, N' - [3-(o-((4,6-dimethoxy-2-pyrimidinyl)-oxy)-pyridyl)-methyli dene]-2-phenylacetohydrazide, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyd-N-methyl-3- thiosemicarbazone, o-[(4,6-dimethoxy-2-pyrimidinyl)-oxy]-benzaldehyd-3-thiosemic arbazone.
21. A process for preparing the compounds of the formula I according to claim 1, which comprises, a) in the case of compounds of the formula I in which W is NR4, reacting an aldehyde of the formula II in which R1, R2, R3, Z, Y and B are as defined under formula I in claim 1, with an amine, hydrazine, hydrazide, carbazate, semicarbazide or thiosemicarbazide or oxime of the formula III in which R4 is as defined under formula I in claim 1, if desired in the presence of a water-binding agent and an inert diluent, or b) reacting a pyrimidine of the formula IV in which R1, R2 and Z are as defined under formula I in claim 1 and L is a leaving group, -56- 241501 h2n r4 III II VYRl N^N + L YH "► I iv V with an imine, hydrazone, hydrazide, carbazate, semicarbazide, thiosemicarbazide or oxime compound of the general formula V in which R3, R4, B and Y are as defined under formula I in claim 1, in the presence of an acid-binding agent and in the presence of an inert solvent, or c) in the case of compounds of the formula I in which R1, R2, R3, B, Y and Z are as defined under formula I in claim 1, and in which R6 in the definition NR5R6 is C^alkylcarbonyl, trifluoromethylcarbonyl, C3.6cycloalkylcarbonyl, benzylcarbonyl, 2-, 3- or 4-pyridinyl-, 2- or 3-furyl- or thiophenylcarbonyl, or benzoyl which is monosubstituted to disubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or nitro; or C^alkoxycarbonyl, benzoyloxycarbonyl, aminocarbonyl, aminothiocarbonyl, or aminocarbonyl or aminothiocarbonyl each of which is monosubstituted to disubstituted by phenyl or C^alkyl, it being possible for the phenyl group to be substituted by fluorine, chlorine, methyl or methoxy, reacting a compound of the formula II in which R1, R2, R3, Z, Y and B are as defined above, 24 1 5 01 -57 VI or U=C=N-R6. I' VI' with hydrazine or hydrazine hydrate, and then reacting the hydrazide of the formula I' in which R1, R2, R3, B, Y and Z are as defined above and W is NNH2, with the corresponding acid chloride, chloroformic ester, carbamoyl chloride or thiocarbamoyl chloride of the formula VI in which U is oxygen or sulfur, or with the corresponding isocyanate or isothiocyanate of the formula VI' in which U is oxygen or sulfur, or d) in the case of compounds of the formula I in which R1, R2, R3, B, Y and Z are as defined under formula I in claim 1 and in which R7 in the definition W = NOR7 is C^alkyl, C3_6alkenyl which can be substituted by halogen or phenyl, or is C^alkoxy- or alkylthiocarbonyl-C^alkyl, VY82 NyN Y T-Ov n^oh I" I reacting an oxime of the formula I" in which R^R3, B, Y and Z are as defined under f formula I in claim 1, and in which W is NOH, with an alkyl, alkenyl or C^alkoxy- or alkylthiocarbonyl-C^alkyl halide of the formula VII in the presence of an inert diluent Hal-R7' VII 241501 -58- and in the presence of an acid-binding agent.
22. A herbicidal and plant-growth-inhibiting composition, which comprises one or more pyrimidinyl- and triazinylsalicyl- and -picolinylaldehyde derivatives of the formula I according to claim 1.
23. A composition according to claim 22, which comprises between 0.001 % and 95 % by weight of active substance of the formula I according to claim 1.
24. A method of controlling undesired plant growth, in which an effective amount of an active substance of the formula I according to claim 1, or a composition comprising this active substance, is applied to the plants or their environment.
25. A method according to claim 24, in which an amount of active substance between 0.001 and 3 kg is applied per hectare.
26. A method of regulating plant growth, in which an effective amount of an active substance of the formula I according to claim 1, or a composition comprising this active substance, is applied to the plants or their environment.
27. A method according to claim 24 for the selective pre- or post-emergence control of weeds in crops of useful plants.
28. The use of a compound of the formula I according to claim 1 as an active substance in weedkillers. FO 7.5/M ciba-geigy ag BY THEIR ATTORNEYS BALDWIN, SON & CAREY
NZ241501A 1991-02-05 1992-02-03 Pyrimidinyl-(and triazinyl-) salicyl- (and picolinyl-) aldehyde derivatives and herbicidal compositions NZ241501A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB919102423A GB9102423D0 (en) 1991-02-05 1991-02-05 Pryimidinyl-and triazinylsalicyl-and-picolinylaldehyde derivatives

Publications (1)

Publication Number Publication Date
NZ241501A true NZ241501A (en) 1992-12-23

Family

ID=10689542

Family Applications (1)

Application Number Title Priority Date Filing Date
NZ241501A NZ241501A (en) 1991-02-05 1992-02-03 Pyrimidinyl-(and triazinyl-) salicyl- (and picolinyl-) aldehyde derivatives and herbicidal compositions

Country Status (7)

Country Link
AU (1) AU1153892A (en)
GB (1) GB9102423D0 (en)
MX (1) MX9200468A (en)
NZ (1) NZ241501A (en)
TW (1) TW222624B (en)
WO (1) WO1992013846A1 (en)
ZA (1) ZA92786B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3889065B2 (en) * 1994-03-15 2007-03-07 株式会社東芝 Organic nonlinear optical material
AU738197C (en) 1997-04-22 2002-05-16 Cocensys, Inc. Carbocyclic and heterocyclic substituted semicarbazones and thiosemicarbazones and the use thereof
JPH10338673A (en) * 1997-06-04 1998-12-22 Nippon Bayeragrochem Kk Isonicotinic acid hydrazide derivative and pest controlling agent
DE102004030987A1 (en) * 2004-06-26 2006-01-12 Merck Patent Gmbh Ortho-substituted (3-hydroxyphenyl) -acetic acid benzylidene hydrazides

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0287079B1 (en) * 1987-04-14 1994-10-12 Kumiai Chemical Industry Co., Ltd. 2-Phenoxypyrimidine derivatives and herbicidal compositions
DE3832237A1 (en) * 1988-09-22 1990-03-29 Basf Ag AROMATIC CARBONATEURED DERIVATIVES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS HERBICIDES
JPH02262565A (en) * 1988-12-19 1990-10-25 Mitsui Toatsu Chem Inc Pyrimidine derivative, its production and herbicide containing same and herbicide composition
BR9006558A (en) * 1989-12-26 1991-10-01 Mitsui Toatsu Chemicals PYRIDYL OXYPYRIMIDINE DERIVATIVE AND PROCESS FOR THEIR PREPARATION, PROCESSES FOR THE PREPARATION OF 2- (2-FORMYL-3-PYRYDYLOPHYL) -4,6-DIMETOXYPYRIMIDINE AND 3- (2-PYRIMIDINYLYXY) -2-PYRIDINOCARBOXYDALHYDROHYDIC

Also Published As

Publication number Publication date
AU1153892A (en) 1992-09-07
WO1992013846A1 (en) 1992-08-20
GB9102423D0 (en) 1991-03-20
TW222624B (en) 1994-04-21
ZA92786B (en) 1992-09-30
MX9200468A (en) 1992-08-01

Similar Documents

Publication Publication Date Title
KR100263409B1 (en) Sulfonamide herbicides
US5053072A (en) Heterocyclic n-acylsulfonamides, and their use as herbicides or growth regulators
US5159078A (en) 2-analino pyrimidine compounds
US5104443A (en) Heterocyclic 2-alkoxyphenoxysulfonylureas and the use thereof as herbicides or plant growth regulators
US4511392A (en) Herbicidal sulfonamides
KR850000993B1 (en) Process for preparing n-phenylpyrazole derivatives
KR100846649B1 (en) Process for producing pyridine compound
US4685961A (en) Herbicidal sulfonylureas
JPH01275572A (en) Substituted triazole
US4992549A (en) Herbicidal compositions
NZ241501A (en) Pyrimidinyl-(and triazinyl-) salicyl- (and picolinyl-) aldehyde derivatives and herbicidal compositions
HU206592B (en) Herbicide and growth controlling compositions containing substituted sulfonyl-diamide derivatives as active components and process for producing the active components
US5462914A (en) Herbicidal n-cyanopyridazinones
US7414011B2 (en) Phenylsulfonyl ureas, process for their preparation and their use as herbicides and plant growth regulators
CA1228859A (en) N-phenylpyrazole derivatives
US5102443A (en) Heterocyclically substituted phenoxysulfonylureas, and the use thereof as herbicides or plant growth regulators
US5262386A (en) Pyrimidinyl- and triazinyl-salicylamides and their use and preparation
AU1882892A (en) Substituted benzothiazole derivatives, their preparation and use as herbicides
JPS63280060A (en) Alkyl-n-aryl tetrahydrophthalimides, manufacture and use for plant protection
IL32113A (en) 1-alkoxycarbonyl uracils,their preparation and herbicidal compositions containing them
HU189221B (en) Herbicide compositions and process for producing heterocyclic compounds utilizable as active agents too
US5374639A (en) Benzotriazolesulfonic acid derivatives as microbicides
US5380701A (en) 3-aryluracil derivatives and the use thereof for weed control
DK170374B1 (en) 1-Carbamoyl-2-pyrazoline derivatives, method of preparation thereof, agent with herbicide and / or plant growth regulating action containing such derivative, and method of preparation of the agent, and method of controlling and / or preventing unwanted plant growth therewith
US4846881A (en) 3,4,6-trisubstituted 1,2,4-triazin-5(4H)-one herbicides