AU730571B2 - Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines - Google Patents
Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines Download PDFInfo
- Publication number
- AU730571B2 AU730571B2 AU33198/97A AU3319897A AU730571B2 AU 730571 B2 AU730571 B2 AU 730571B2 AU 33198/97 A AU33198/97 A AU 33198/97A AU 3319897 A AU3319897 A AU 3319897A AU 730571 B2 AU730571 B2 AU 730571B2
- Authority
- AU
- Australia
- Prior art keywords
- methyl
- group
- pyrimidine
- compound
- pyrazol
- Prior art date
- Legal status (The legal status 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 status listed.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/65—One oxygen atom attached in position 3 or 5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/68—One oxygen atom attached in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/69—Two or more oxygen atoms
-
- 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
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/34—One oxygen atom
-
- 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
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/34—One oxygen atom
- C07D239/36—One oxygen atom as doubly bound oxygen atom or as unsubstituted hydroxy radical
-
- 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
-
- 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
- C07D239/56—One oxygen atom and one sulfur atom
-
- 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
-
- 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
- C07D401/14—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 three or more hetero rings
-
- 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
- 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
- C07D403/14—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 three or more hetero rings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
S F Ref: 388745
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT
ORIGINAL
S
a a *a a
S
Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: American Cyanamid Company Five Giralda Farms Madison New Jersey 07940 0874 UNITED STATES OF AMERICA Axel Kleemann, Helmut Siegfried Baltruschat, Thomas Maler and Stefan Scheiblich Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Herbicidal 2,6-dlsubstltuted pyrldlnes and 2,4-disubstituted pyrimidines The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845 32,483-02 HERBICIDAL 2.6-DISUBSTITUTED PYRIDINES AND 2.4-DISUBSTITUTED PYRIMIDINES The present invention relates to certain 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines, their preparation and use as herbicides.
Pyridines, pyrimidines and their derivatives have many uses in the pharmaceutical area as well as in agriculture (herbicides, fungicides, acaricides, anthelmintics, bird repellents), reagents, intermediates and chemicals for the polymer and textile industry.
2-Arylpyrimidines and 2-pyrimidinyl-6-arylpyridines for example have been described as fungicides (DE 40 29 654 and JO. 2131-480, respectively). EP 263,958&..is concerned with herbicidal 2,6-diphenylpyridines, and structurally related 2,4-diphenylpyrimidines have been disclosed in EP 354,766 and 425,247, respectively, which are also said to be herbicides. Another example are 2,6-diphenoxypyridines, which have been published in EP 572,093 as herbicides. 4- Phenoxy-2-pyrazol-1-yl-pyrmidines are disclosed in DE 29 35 578 to have fungicidal activity.
Huelsen (Diplomarbeit, Konstanz 1993) describes four distinct 2-(1-methyl-3-trifluoromethylpyrazol-5-ylyoxy)-6-phenyl pyridines, however, no biological activity is disclosed.
Surprisingly, it has now been found that good herbicidal activity is present in related, novel pyridine and pyrimidine derivatives having both an aryl group and an aryloxy or a heteroaryloxy group. These compounds unexpectedly show excellent activity and good crop selectivity in preand post-emergence applications on both broadleaf and grassy weed species.
Accordingly, the present invention provides 2,6-substituted pyridines and 2,4-substituted 20 pyrimidines of the general formula I R1 99
(I)
*9 X N R2 wherein A represents an optionally substituted aryl group or an optionally substituted 5- or 6-membered nitrogen-containing heteroaromatic group or a difluorobenzodioxolyl group; 25 represents an integer from 0 to 5; m represents an integer from 0 to n represents an integer from 0 to 2;
R
1 (or each independently represents a hydrogen atom, an halogen atom, an optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkoxyalkyl, dialkoxyalkyl, alkoxyalkoxy, alkylthio, amino, alkylamino, dialkylamino, alkoxyamino or formamidino group;
R
2 (or each R 2 independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl, alkenyl, alkinyl, haloalkyl, haloalkoxy, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, haloalkylthio group or a nitro, cyano, SF or a alkylsulphonyl or alkylsulfinyl group; X represents an oxygen or sulphur atom; and Z represents a nitrogen atom or a CH group; with the provisos that A represents a pyridyl group being substituted by at least one haloalkyl, haloalkoxy or haloalkylthio group,in the event that Z represents N; or m and n are 1, R' denotes an alkyl, alkoxy or alkylamino group attached in the 4position and R 2 represents a trifluoromethyl, in the event that Z represent CH.
An aryl group as substituent or part of other substituents or in the definition of A is suitably an optionally substituted phenyl or naphthyl group. Within the definition of A the 5- or 6-membered heteroaryl group comprises optionally substituted 5- or 6-membered heterocycles containing one or more nitrogen and/or oxygen and/or sulfur atoms, 1 to 3 nitrogen atoms being preferred.
Examples of such groups are pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, isoxazolyl, isothiazolyl and triazinyl groups. As far as A is concerned the definition "aryl" does also include bicyclic systems which consist of a benzene ring condensed with a 5- or 6membered heterocyclic ring as defined above and in turn the 5- or 6-membered heterocycles may be condensed with a benzene ring. Another preferred embodiment of A is a difluorobenzodioxolyl *4 group of formula F F 'O
O
o 0 0 25 Generally, if any of the above mentioned moieties comprises an alkyl, alkenyl or alkinyl group, such groups, unless otherwise specified, may be linear or branched and may contain 1 to 12, preferably 1 to 4, carbon atoms. Examples of such groups are methyl, ethyl, propyl, vinyl, allyl, isopropyl, butyl, isobutyl and tertiary-butyl groups. The alkyl portion of a haloalkyl, haloalkoxy, alkylthio, haloalkylthio or alkoxy group suitably has from 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. The number of carbon atoms in the alkoxyalkyl, alkoxyalkoxy or dialkoxyalkyl v, -i 1
I,
-3groups is up to 6, preferably up to 4, e.g. methoxymethyl, methoxymethoxy, methoxyethyl, ethoxymethyl, ethoxyethoxy, dimethoxymethyl.
"Halogen" means a fluorine, chlorine, bromine or iodine atom, preferably fluorine, chlorine or bromine. Haloalkyl, haloalkylthio and haloalkoxy are preferably mono-, di- or trifluoroalkyl, alkylthio and -alkoxy, especially trifluoromethyl, difluoromethoxy, trifluoromethylthio and trifluoromethoxy.
When any groups are designated as being optionally substituted, the substituent groups which are optionally present may be any of those customarily employed in the modification and/or development of pesticidal compounds and are especially substituents that maintain or enhance the herbicidal activity associated with the compounds of the present invention, or influence persistence of action, soil or plant penetration, or any other desirable property of such herbicidal compounds.
There may be one or more of the same or different substituents present in each part of the molecules. In relation to moieties defined above as comprising an optionally substituted alkyl group, including alkyl parts of haloalkyl, alkoxy, alkylthio, haloalkoxy, alkylamino and dialkylamino groups, specific examples of such substituents include phenyl, halogen atoms, nitro, cyano, hydroxyl, C 1 i 4 -alkoxy, C 1 _4-haloalkoxy and C 1 _4-alkoxycarbonyl groups.
In relation to moieties defined above as comprising an optionally substituted aryl or heteroaryl group, optional substituents include halogen, especially fluorine, chlorine and bromine atoms, and nitro, cyano, amino, hydroxyl, C 1 4-alkyl, Ci4-alkoxy, C 1 4-haloalkyl, C14-haloalkoxy,
C
1 4 -haloalkylthio and haiosulfanyl groups such as SF. 1 to 5 substituents may suitably be employed, 1 to 2 substituents being preferred. Typically haloalkyl, haloalkoxy and haloalkylthio groups are trifluoromethyl, trifluoromethoxy, difluoromethoxy and trifluoromethylthio groups.
The index m preferably means an integer from 1 to 3, n is preferably 1 (then R 1 is not hydrogen).
25 The compounds according to general formula I are oils, gums, or, predominantly, crystalline solid materials. They can be used in agriculture or related fields for the control of undesired plants such as Alopecurus myosuroides, Echinochloa crus-galli, Setaria viridis, Galium aparine, Stellaria media, Veronica persica, Lamium purpureum, Viola arvensis, Abutilon theophrasti, Ipomoea purpurea and Amaranthus retroflexus by pre- and post-emergence application. The compounds of 30 general formula I according to the invention possess a high herbicidal activity within a wide concentration range and may be used in agriculture.
Preferred compounds are those wherein A represents a phenyl, pyridyl, or pyrazolyl group, being substituted by one or more identical or different substituents selected from halogen atoms, alkyl, alkoxy, haloalkyl, haloalkoxy and pentahalosulfanyl groups.
Especially preferred are compounds bearing a substituent in group A in meta-position relative to the point of attachment of this group.
Good results in terms of control of undesired plant growth are obtained when A is metasubstituted by a chlorine atom or a trifluoromethyl group, especially A being a 2-chloropyrid-4-yl, 1or 3-trifluoromethylphenyl group.
Particularly good results in control of weeds are achieved with compounds wherein X represents an oxygen atom. Especially good results are obtained with compounds wherein Z represents a nitrogen atom.
The following formulae I A, I B and IC represent preferred embodiments of the invention: I A a e oe 2
(IB)
oo
(IC)
In the formula IA A represents a 2-trifluoromethylpyrid-4-yl or 2-difluoromethoxypyrid-4-yl 2 group, R 1 has the meaning given above; R 2
R
2 and R 2 independently represent a hydrogen atom, a fluorine, chlorine or bromine atom, one or two of them also a trifluoromethyl, trifluormethoxy or a cyano group, R 2 can further be a C,-C 4 -alkyl group, particularly tert-butyl.
In the formula lB X represents haloalkyl, haloalkoxy or haloalkylthio, preferably difluoromethoxy, and R1 denotes a halogen atom or an alkyl or alkoxy group.
In the formula IC R1 denotes alkyl, alkoxy or alkylamino and A has the meaning given above.
The invention is exemplified by the following compounds: 6-ty--4-dlooehlhnl--2-rfurmty-yi-"yoyprmdn 6-ty--4-dlooehlhnl--2-222tilooty)pd-"yoyprmdn 6-methyl-2-(4-trifluoromethylphenyl)-4-[2"-( 1 ,2,2-tetrafluoroethyl)-pyrid-4"-yloxy]pyrimidine 5-methyl-2-(4-trifluoromethylphenyl)-4-[2"-(1,1 ,2,2-tetrafluoroethyl)-pyrid-4"-yloxy]pyrimidine 4-ethyl-2-(4'-tifluoromethylphenyl)-6-( 1 The compounds according to the invention can be prepared by conventional methods.
*0 A suitable process for the preparation of the compounds of general formula I comprises the 10 reaction of a compound of general formula Ill Hal Nm with a compound of general formula IV
A-XM
(IV)
1 2 wherein Z, A, R R m, n and X are as defined hereinbefore; Hal represents a halogen atom; and M represents a metal atom.
The halogen atom Hal may be any halogen atom, suitably a fluorine, chlorine or bromine atom are employed. The metal atom M may be any metal atom, suitably alkali metal atoms are used, sodium and potassium being preferred.
Alternatively, a compound of general formula XV 0A
A\
N
AR2
(XV)
wherein A, R 2 and m are as defined hereinbefore, may react with R 1 preferable in the presence of a base, if R' is optionally substituted alkoxy, alkoxyalkoxy, alkylthio, amino, alkylamino, dialkylamino or alkoxyamino to give compound of general formula I.
Compounds I, wherein R 1 is alkynyl or alkenyl, e. g. of the allyl or propargyl types, can be prepared from compounds I, wherein R 1 is a halogen atom, preferably chlorine or bromine, by reaction of R 1 -H or organometall derivatives thereof, preferable in the presence of a transition metal catalyst or a base.
Compounds XV can be prepared from III, wherein R 1 is Hal, Z is nitrogen, Hal, R 2 and m are defined as hereinbefore, by reaction with IV as described above, X means oxygen, applying about 15 2 equivalents of IV.
In practice, the reaction may be carried out in the absence or presence of a solvent which promotes the reaction or at least does not interfere with it. Preferred are polar, aprotic or protic solvents, suitably being N,N-dimethylformamide or dimethylsulfoxide or sulfolane, or an ether, such as tetrahydrofurane or dioxane, or alcoholes, or water or mixtures thereof. The reaction is carried out at a temperature between ambient temperature and the reflux temperature of the reaction mixture, preferably at elevated temperature, especially reflux temperature.
Compounds of formula III in which Z represents a C-H group and n is 0 may be obtained by reacting a compound of general formula V 0
HC
3
C
v -7wherein R 2 and m are as defined hereinbefore, with an aldehyde, suitably formaldehyde, and a dialkylamine, suitably dimethylamine, according to Org. Synthesis Col. Vol. II, 305f, in a solvent, conveniently an alcohol, preferably ethanol, to give a compound of general formula VI, 0
R
2 m x HCI which is subsequently reacted according to DBP 21 47 288 (1971) suitably ammonium acetate, and a compound of general formula VII, N CI 0 with an ammonium salt, wherein Y is an alkoxy group or an NH 2 -group, preferably an ethoxy group, in a solvent, suitably an alcohol, preferably ethanol, to give a compound of general formula VIII, 0 N
IR
2 m
H
10 (VII) which is further converted by reacting VIII with phosphoryl halogenides (MOller, Chem. Ber. 42, 423 (1909); Katritzky et al., J. Chem. Soc., Perkin Trans. Part 1, 1980, 2743-2754), preferably phosphoryl bromide or phosphoryl chloride at elevated temperatures, ideally reflux temperature, to give a compound of general formula III.
An alternative, and preferred process for the preparation of compounds of general formula III in which Z represents a C-H group, comprises reacting a 2,6-dihalopyridine of general formula
IX
R
n Hal 1 N Hal, -8wherein R 1 and n are as defined hereinbefore, and each Hall and Hal 2 independently represents a halogen atom, with an organometallic benzene derivative of general formula in an approximately equimolar ratio,
M
M -R2m
(X)
wherein R 2 and m are defined as hereinbefore, and M represents an alkali metal atom, or borine, or tin, or magnesium, or zinc or copper optionally in the presence of a transition metal catalyst.
The alkali metal may be any alkali metal, preferably lithium, and the reaction. may be carried out in an aprotic, polar solvent, preferably ethers, to give a compound of general formula III, essentially as disclosed in Cook and Wakefield, J. Chem. Soc., 1969, 2376, or in unpolar solvents or water, for example as described in Ali,N.M. et al, Tetrahedron, 1992, 8117.
Compounds of formula III, where Z means CH, Hal is fluorine, R 1 is hydrogen, R 2 and m are as defined hereinbefore, can further be converted to compounds of formula III, where n 1, Z means CH, Hal is fluorine, R 2 m are as defined hereinbefore and R 1 is in position 3 and means methylthio (or another group from the set described before, that is introducable in form of an electrophilic reagent), analogous to the method described by Gungor, T, Marsais,F and Queguiner, G, J.Organometallic Chem., 1981, 139-150.
A process for the preparation of compounds of formula III, in which Z represents a nitrogen atom, comprises the reaction of benzamidine hydrochlorides of the general formula XI
**NH,
R2
(XI)
wherein R 2 and m are as defined hereinbefore with a compound of formula XII or a salt thereof, 0 0 1
(XII)
wherein each R 1 l and R 1 2 independently are as defined hereinbefore; and the O-alkyl group is suitably methoxy or ethoxy, to give a pyrimidinone of general formula XIII, in which R 1 can also be hydroxyl.
-9m
ON
I R 2
H
(XIII)
Compounds of general formula XI are known or may be prepared according to procedures described in the art, for example in Tetrahedron, 33, 1675f (1979) and J. Org. Chem., 26, 412f.
(1960).
The reaction of compounds of formulae XI and XII may be carried out according to Liebigs Ann. 1980, 1392f in an organic solvent, suitably an alcohol and preferably ethanol, and in the presence of a base, suitably metal alkoxides, preferably sodium ethoxide.
Compounds of formula XIII may subsequently be converted into compounds of formula III, essentially as described in Davies and Pigott, J. Chem. Soc., 1945, 347, by reaction with a phosphoryl halogenide or thionyl halogenide or phosgene, preferably phosphoryl chloride, phosphoryl bromide, ideally in the absence of a solvent, at elevated temperatures to obtain compounds of formula IIl.
Compounds of formula III in the meaning above with R1=F may be obtained from compound III when R 1 is chlorine or amino according to procedures known in the art, like described in Tullock C.W. et al, J.Am.Chem.Soc. 1960, 5197 or Kiburis J. Klister J. J.Chem.Soc.Chem.Com. 1969, 381 Compounds of general formula IV are known or may be prepared by known methods. They may be prepared and isolated separately or may be prepared in situ. Generally, a compound of general formula XIV 20
A-XH
(XIV)
wherein A and X are as hereinbefore defined is reacted with a suitable metal base, for example a metal carbonate or hydride. Preferably the metal salt is a sodium or potassium salt.
Compounds of general formula I may, if desired, be isolated and purified using conventional 25 techniques.
The present invention also provides the use of a compound of general formula I as a herbicide. Further, in accordance with the invention there is provided a method of combating undesired plant growth at a locus by treating the locus with a composition according to the invention or a compound of formula I. As a useful action is by foliar spray application, the locus is most suitably the plants in a crop area, typical crops being cereals, maize, soya bean, sunflower or cotton. However, application may also be to the soil for those compounds having pre-emergence herbicidal action. The dosage of active ingredient used may, for example be in the range of from 0.01 to 10 kg/ha, preferably 0.05 to 1 kg/ha.
The present invention also extends to a method of making a herbicidal composition of the invention which comprises blending a compound of formula I with at least one carrier.
Preferably there are at least two carriers in a composition of the present invention, at least one of which is a surface-active agent.
A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may be, as appropriate, a plant, seed or soil, or to facilitate storage, transport or handling. A carrier may be a solid or a liquid, including a material which is normally gaseous but which has been compressed to form a liquid, and any of the carriers normally used in formulating herbicidal compositions may be used. Preferably compositions according to the invention contain 0.5 to 95% by weight of active ingredient.
Suitable solid carriers include natural and synthetic clays and silicates, for example natural silicates such as diatomaceous earths; magnesium silicates, for example talcs; magnesium aluminium silicates, for example attapulgites and vermiculites; aluminium silicates, for example kaolinites, montmorillonites and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates; elements, for example carbon and sulphur, natural and synthetic resins, for example coumaron resins, polyvinyl chloride, and styrene polymers and copolymers; solid polychlorophenols; bitumen; waxes; solid e fertilisers, for example superphosphates.
Suitable liquid carriers include water; alcohols, for example isopropanol and glycols; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; o :25 ethers; aromatic or araliphatic hydrocarbons, for example benzene, toluene and xylene; petroleum fractions, for example kerosene and light mineral oils; chlorinated hydrocarbons, for example carbon tetrachloride, perchloroethylene and trichloroethane. Mixtures of different liquids are often ••suitable.
Agricultural compositions are often formulated and transported in a concentrated form which S 30 is subsequently diluted by the user before application. The presence of small amounts of a carrier which is a surface-active agent facilitates this process of dilution. Thus preferably at least one carrier in a composition according to the invention is a surface active agent. For example, the e composition may contain at least two carriers, at least one of which is a surface-active agent.
A surface-active agent may be an emulsifying agent, a dispersing agent or a wetting agent; it may be non-ionic or ionic. examples of suitable surface-active agents include the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty -11 acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitol, sucrose or pentaerythrol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohol or alkyl phenols, for example p-octylphenol or -octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or earth alkali metal salts, preferably sodium salts, or sulphuric or sulphonic acd esters containing at least 10 carbon atoms in the molecule, for example sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl sulphonates such as dodecylbenzene sulphonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.
The herbicidal composition of the invention may also contain other active ingredients, for example, compounds possessing insecticidal or fungicidal properties, or other herbicides.
A formulation containing a compound according to the invention can consist of 100 g of active ingredient (compound of formula 30 g of disperging agent, 3 g of antifoaming agent, 2 g of structure agent, 50 g of anti-freezing agent, 0.5 g of a biocidal agent and water ad 1000 ml.
Prior to use it is diluted with water to give the desired concentration of active ingredient.
The following examples illustrate the invention. The structures of the compounds prepared in the following examples were additionally confirmed by NMR and mass spectrometry.
Examples Example 1: 13-Dimethylamino propiophenone hydrochloride Acetophenone (29.1 ml, 0.25 mol), para-formaldehyde 12.0 g, 0.40 mol) and dimethyl amine hydrochloride (28.5 g, 0.35 mol) are suspended in ethanol (50 ml). Concentrated 25 hydrochloric acid (0.5 ml) is added and the mixture is heated to reflux for 4 h. Then acetone (200 ml) is added and the resulting clear solution is allowed to cool to ambient temperature. The precipitate is collected by filtration and crystallized from ethanol yielding the title compound (40.7 g, 76.0% of theoretical yield) as colorless crystals with mp. 158 0
C.
Examples 2-4: 30 Additional examples of general formula VI are prepared as exemplified by Example 1.
Details are given in Table I -12- Table I 0 CH3
R
2 1 xHCI UJ CH 3 (Vi) Ex. R 2 mp yield No. 2 3-trifluoromethyl 157 63 3 2,4-dichloro 136 51 4 2,4-dimethyl 134 72 Example 6-Phenvl-2-pyridone Ethyl 2-chloroacetate (10.6 ml, 0.1 mol) is slowly added to hot (105 pyridine (8.9 ml, 0.11 mol whereby the temperature is maintained in the range of 100 °C to 110 The resulting brown oil is dissolved in ethanol (60 ml), p-dimethylamino propiophenone hydrochloride (17.7 g, 0.1 mol; prepared according to Example 1) and ammonium acetate (60 g) are added and the mixture is boiled under reflux for 4 h. After cooling, the mixture is filtered and the solvent is 10 evaporated in vacuo. The residue is crystallized from water, collected by filtration and purified by re-crystallization from toluene. The title compound is obtained as colorless crystals (4.7 g, 28% of th.) with mp. 200 oC.
S. Example 6-8: Additional examples are analogously prepared to Example 5. Details are given in Table II.
o g S S S -13- Table II
(VIII)
Ex. R 2 mp yield No. 6 3-trifluoromethyl 174 36 7 2,4-dichloro 255 56 8 2,4-dimethyl 209 23
S
SS
0* S S *r S SB S
S
S.
S.
*S
S
*SSS
S S
S
S.
9*
S
S
S*
5
S
S.
SS 0
SO
00
S
Example 9: 2-Bromo-6-phenyl pyridine A mixture of 6-phenyl pyridone (3 g, 17.5 mmol; prepared according to Example 6) and phosphoryl bromide (7.2 g, 25.0 mmol) is heated to 100 °C for 5 h. The cooled mixture is poured into water (40 ml) and the pH is adjusted to 9 by addition of saturated aqueous sodium carbonate.
Then the layers are separated and the aqueous layer is extracted with ethyl acetate (50 ml). The 10 combined organic layers are dried with anhydrous magnesium sulphate and the solvent is evaporated in vacuo. The crude product is crystallized from aqueous ethanol. Subsequent purification by flash chromatography (silica gel, hexane/ethyl acetate 9/1 v/v) gives 2-bromo- 6-phenyl pyridine (3.1 g, 76% of th.) as light brown crystals with mp 50 °C.
15 Examples 10-12: Additional compounds of general formula III are prepared by procedures analogous to that of Example 9. Details are given in Table IIl.
14 Table III Ex. R2mp yield No. (00) 3-trifluoromethyl oil 82 11 2,A-dichloro 123 88 12 2,4-dimethyl oil 68 Example 13: 2-Cl '-Methyl-3'-trifluromethyl Pyrazol-5'-vloxv)-6-phenvl-pvridine A mixture of 2-bromo-6-phenyl pyridine (0.5 g, 2.1 mmol; prepared according to Example 9), 1-methyl-3-fluoromethyl-5-hydroxypyrazole (0.65 g, 3.9 mmol), potassium carbonate (0.6 g, 4.3 mmol) and N,N-dimethyl formamide (2 ml) is heated to reflux for 12 h. Then the reaction mixture is directly applied onto a flash chromatography column (silica gel). Elution with hexane/ethyl acetate (9/1 v/v) gives the title compound(0.35 g, 52.0% of th.) as light-yellow oil.
Examples 14-16: The compounds specified in Table IV are obtained by procedures analogous to that of Example 13.
C
S S Table IV
A.
0 'NR2 I1) Ex. A R 2 mp yield No. 14 1 '-CH 3 -3'-CF 3 -pyrazol-5'-yl 3"-CF 3 113 93 1'-CH 3 -3'-CF 3 -pyrazol-51-yl 2",4"-dichloro 91 78 16 1'-CH 3 -3'-CF 3 -pyrazol-5'-yl 2",4"-dimethyl oil Example 17: 2-Fluoro-6-(4'-fluorophenyl)-pyridine Butyl lithium (105.0 ml, 0.26 mol, 2.5 M solution in hexane) is added to a solution of 1bromo-4-fluoro benzene (34. 3 ml, 0.31 mol) in anhydrous diethyl ether (200 ml) at -20 The mixture is stirred for 60 min and then chilled to -40 2,6-Difluoropyridine (22.7 ml, 0.25 mol) is added and the reaction mixture is allowed to warm to ambient temperature. Subsequently, the mixture is washed with saturated aqueous ammonium chloride (300 ml). The layers are separated and the aqueous layer is washed with diethyl ether 3 times (100 ml each). After drying of the combined organic layers with anhydrous magnesium sulphate, the solvent is removed in vacuo.
The crude product is purified by flash column chromatography (silica gel, hexane/AcOEt 8/2) Syielding colorless crystals of 2-fluoro-6-(4'-fluorophenyl)-pyridine (19.8 g, 41.0% of th.) with mp 34 °C.
Example 18: 2-Fluoro-6-(4'-fluorophenvl)-4-methylpvridine A mixture of 2-bromo-6-fluoro-4-methylpyridine (9.5 g, 50 mmol), 4-fluorobenzeneboronic acid (7.8 g, 56 mmol), sodium bicarbonate (12.6 g, 150 mmol), water (200 ml) and catalytic 20 amounts of tetrakis(triphenylphosphine)palladium(0) in DME under nitrogen is heated to reflux overnight. After filtration of the reaction mixture the solvents are removed under reduced pressure.
The residue is partitionated between water and ethyl acetate. The layers are separated and the aqueous layer is washed with ethyl acetate. After drying of the combined organic layers with .i -16anhydrous magnesium sulphate, the solvent is removed in vacuo. The crude product is purified by flash column chromatography (silica gel, pentane/ethyl acetate 9/1) yielding colorless crystals of 2fluoro-6-(4'-fluorophenyl)-4-methylpyridine (3.7 g, 36.1% of th.) with mp 49 °C.
Example 19: 2-Fluoro-6-(4'-trifluorophenyl)-3-methylthio-pyridine To a solution of 2-fluoro-6-(4'-trifluorophenyl)pyridine (2.4 g, 10 mmol, prepared according to example 17) in dry THF (35 ml) is added dropwise a solution of 2 M LDA in THF (7.5 ml, 15 mmol) at -70 After 2 h at -70 0 C dimethyl disulfide (1.41 g, 15 mmol) is added and the reaction mixture is allowed to warm at -20 The mixture is hydrolysed and extracted with diethylether. After separation the organic layer is dried with anhydrous magnesium sulphate. The solvents are removed and the crude product is purified by flash column chromatography (silica gel). Elution with hexane/ethyl acetate (20/1 v/v) gives the title compound (1.2 g, 42 with mp 70-73 *C.
Examples 20-23: Analogously to Example 17, the examples of general formula III are prepared as specified in Table V.
e -17- Table V
R
1
(III)
Ex. R 1
R
2 mp yield No. -oil 47 21 4'-trifluoromethyl 58 22 3'-trifluoromethyl oil 72 23 3,4-difluoro oil 24 Example 24: 2-(3-Chlorprid-5-loxV)-6-(4-fluorohenloxV)-phridine r o r r o A mixture of 2-fluoro-6-(4'-fluorophenyl)-pyridine (1.9 g, 10.0 mmol, prepared according to Example 17), 3-chloro-5-hydroxypyridine (1.4 g, 11.0 mmol) and potassium carbonate (1.5 g, 11.0 mmol) in sulfolane (10 ml) is heated to reflux for 8 h. The mixture is allowed to cool to ambient temperature and is then filtered through a bed of silica gel which is subsequently washed with ethyl acetate. The organic solutions are combined and the solvent is evaporated in vacuo. The remaining material is applied onto the top of a flash chromatography column (silica gel) and eluted with hexane/ethyl acetate. Elution with hexane/ethyl acetate (8/2 v/v) gives 2-(3'-chlorpyrid-5'yloxy)-6-(4"-fluorophenyloxy)-pyridine (1.4 g, 46% of th.) as light brown crystals with mp 139 °C.
Examples 25-43: Additional compounds are prepared analogously to example 24. Details are found in Table
VI.
-18- Table VI Ex. R 1 A R2mp yield No. 0 C) M% -3'-CF 3 -phenyl 4"-fluoro oil 48 26 2'-chloropyrid-4'-yl 4"-fluorc, 137 37 27 2'-chloropyrid-4'-yl 109 28 2'-chloropyrid-4'-yl 4'-trifluoromethyl 105 51 29 1'-CH 3 -3'-CF 3 -pyrazol-5'-yl 4"-fluoro 87 44 I '-CH 3 -3'-CF 3 -pyrazol-5'-yl 4-trifluoromethyl 94 59 31 1'-CH 3 -3'-CF 3 -pyrazol-5'-yl 3"-trifluoromethyl 112 44 32 2'-chloropyrid-4'-yl 3"-trifluoromethyl 92 54 33 4'-difluorophenyl 3-trifluoromethyl oil 72 34 3'-CF 3 -phenyl 4"-trifluormethyl oil 44 35 4-CH 3 1'-CH 3 -3'-CF 3 -pyrazol-5'-yl 4"-fluoro 85 43 36 4-CH 3 2'-chloropyrid-4'-yl 4"-fluoro 115 37 3-CH 3 S 3'-CF 3 -phenyl 4"-trifluormethyl 133-136 67 38 3-CH 3 S 1 -CH 3 -3'-CF 3 -pyrazol-5'-yl 4"-trifluormethyl 154-156 41 39 1 -CH 3 -3'-CF 3 -pyrazol-5'-yl 3" ,4"-difluoro oil 29 Example 4-Fluorobenzamidine hydrochloride 4-Fluorobenzonitrile (10 g, 83 mmol) is dissolved in a mixture of anhydrous ethanol (5 ml) and diethyl ether (70 ml). The reaction mixture is cooled to ice-bath temperature and saturated with gaseous hydrogen chloride for 90 minutes. The mixture is allowed to warm to ambient temperature and stirred overnight.
-19- The colourless precipitates are filtered off, washed with diethyl ether and dissolved in anhydrous ethanol (20 ml). Diethyl ether (100 ml) saturated with gaseous ammonia is added and the solution is stirred for 3 hours.
The resulting suspension is filtered and the solvent of the filtrate is removed in vacuo. The residue is washed with diisopropyl ether. After drying colourless crystals (5.15g, 35.5%) of melting point 210°C are obtained.
Examples 41 to By methods analogous to that of example 40, further compounds of the general formula XI are prepared. Details are given in table VII.
Table VII
NH
H2N R2 x HCI (Xi) *o e e• Ex. R 2 mp yield No. 41 4-trifluoromethyl 167 21.4 42 3-methyl 243 29.7 43 3-chloro 148 17.5 44 3,4-difluoro 185 17.4 3-trifluoromethyl 181 17.6 46 3-fluoro 143 20.0 47 4-bromo 245 39 48 4-chloro >250 49 4t bu 153 92 4-trifluormethoxy 210 57 r r r r r r Example 51: 2-(4'-Fluorophenvl)-5-methyl-4-pyrimidinone Sodium hydride (0.52 g, 13 mmol) is added to 20ml of anhydrous ethanol and stirred for 5 minutes at ambient temperature. To this, 4-fluorobenzamidine hydrochloride (1.47 g, 8.5 mmol) (from example 40) is added and the mixture is stirred for further 30 minutes. Methyl 2formylpropionate (1 g, 10.6 mmol) is added dropwise and the reaction mixture is left for 4 days under stirring at ambient temperature.
After cooling, the solvent is removed in vacuo and the residue is dissolved in aqueous 10 sodium hydroxide (10 ml, 1M). Then the mixture is brought to pH 5 with 2 molar hydrochloric acid.
The precipitate is filtered off and washed with diisopropyl ether. After drying, colourless crystals (0.44g, 10.3%) of melting point >250°C are obtained.
-21- Example 52: 6-Hydroxv-2-(4'-trifluoromethylphenyl)-4-pyrimidinone 4-Trifluormethylbenzamidine hydrochlorid (22.4 g, 0.1 mol, from example 41) is added to a solution of potassium methylate (0.22 mol) in anhydrous methyl alcohole (65 ml) and stirred for minutes at ambient temperature. Dimethyl malonate (12.6 ml, 0.11 mol) is added and the mixture ist heated to reflux for 4 hours. After cooling, the resulting suspension is diluted with methyl alcohole (50 ml).
The solvent is removed in vacuo and the residue is dissolved in water (50ml). Then the mixture is brought to pH 1 with concentrated hydrochloric acid. The precipitate is filtered off and washed with water. After drying, pale yellow crystals (15.1g, 59%) of melting point >200 0 C are obtained.
Example 53: 5-Methoxv-2-(4'-trifluoromethylphenyl)-4-pyrimidinone To a suspension of sodium hydride (60 6 g, 0.15 mol) in dry THF (225 ml) a solution of methyl methoxyacetate (14.9 ml, 0.15 mol) in methyl formate (11.1 ml, 0.18 mol) is added during a period of 30 min. The mixture is stirred for 2 hours at ambient temperature. After adding of diethylether (300 ml) the resulting sodium salt of methyl methoxymalonate monoaldehyde can be isolated by suction. Now the sodium salt (0.075 mol) is added to 4-trifluoromethylbenzamidine hydrochloride (16.8 g, 0.075 mol, from example 41) in dry ethyl alcohole (150 ml) and the mixture 20 is stirred for 48 hours at ambient temperature. After heating to reflux for 1 hour water (100 ml) is added to the mixture and the soluion is filtered.
The fliltrate is brought to pH 5 with acetic acid and the ethyl alcohole is removed in vacuo.
S• The precipitate is filtered off and washed with ethyl alcohole. After drying crystals (13.7g, 68%) of melting point >200°C are obtained.
25 Examples 54 to 78 .o By the method exemplified in example 53, further compounds of the general formula III are prepared. Details are given in table VIII.
-22 Table VII I 0 N R 2 R 2 9 99 99 9.
99 .9 9. 99 99 S 99 .9.9 9.
9* 99 9 99 .9 6-methyl 6-methyl 6-methyl 6-methyl 6-methyl 6-methyl 5,6-dimethyl 5,6-dimethyl 6-methyl 6-methyl 6-ethyl 6-methyl 5-methyl 6-methyl .4'-fluoro 4'-trifluoromethyl 4'-trfluoromethyl 3-methyl 3'-methyl 3'-chloro 3-chloro 3',4'-difiuoro 3',4'-difluoro 3'-trifluoromethyl 3'-trifluoromethyl T-trifluoromethyl 4'-trifiuoromethyl 4'-chloro 4'-chloro 3-fiuoro 3'-fluoro 4'-trifluoromethyl 4'-bromo 4'-bromo 4' 2 bu 4'jbu mp yield (OC) M% 267 56.8 >250 58.7 209 82.2 169 34.3 185 41.6 260 61.4 218 51 >250 59.4 225 51.3 204 39.8 109 26.6 215 70.4 242 63.5 >250 27.2 227 238 194 181 >250 245 218 213 6.8 56 48.4 87 39 81 76 5,6-dimethyl 76 ,6dietyl 4'-chloro 276 44 -23- 77 5,6-dimethyl 4'-trifluoromethoxy 228 78 6-methyl 4'-trifluoromethoxy 196 Example 79: 2-(4'-Fluorophenvl)-4-chloro-5-methylpyrimidine A mixture of 2-(4'-fluorophenyl)-5-methyl-4-pyrimidinone (0.79 g, 3.9 mmol) (from example and phosphorous oxychloride (3 ml) is heated to reflux for 1 hour.
The main excess of phosphorous oxychloride is removed in vacuo and the residue is quenched with water (10 ml) to hydrolyze the remaining reagent. The mixture is neutralized and then extracted with ethyl acetate (50 ml). After drying of the organic layer with anhydrous magnesium sulphate, the solvent is removed in vacuo. The title compound. (0.63g, 72.6%) is obtained as colourless crystals of melting point 133°.
Example 2-(4'-Chlorophenyl)-4,5-dichloro-6-methoxpyvrmidine To a solution of 2-(4'-chlorophenyl)-4,5,6-trichloropyrimidine (1.85 g, 6.3 mmol) in methyl alcohole (30 ml) and THF (60 ml) is added a solution of sodium (0.145 g, 6.3 mmol) in methyl alcohole (10 ml) and the mixture is stirred at ambient temperature overnight. After removal of the solvents in vacuo dichloromethane is added to the residue and the resulting mixture is washed with water. After drying of the organic layer with anhydrous magnesium sulphate, the solvent is removed. Treating of the residue with pentane affords the title compound (1.75g, 96 as colourless crystals of melting point 157-159 0
C.
Examples 81-108: The compounds of general formula (XIII) listed in table IX are prepared analogously to the method of example 83.
Table IX
R
(III)
-24- R 2 Ex.
No.
81 82 83 84 86 87 88 89 91 92 93 94 96 97 98 99 100 101 102 103 104 105 106 107 6-methyl 6-methyl 5-methyl 5-methyl 6-methyl 5-methyl 6-methyl 5-methyl 6-methyl 5,6-dimethyl 5,6-dimethyl 5-methyl 6-methyl 5-methyl 6-methyl 5-methyl 6-methyl 6-ethyl 5-methyl 6-methyl 5-methyl 6-methyl 5,6-dimethyl 5,6-dimethyl 5-methyl 6-methyl 6-chloro 4'-fluoro 4'-trifluoromethyl 4'-trifluoromethyl 3'-methyl 3-methyl 3'-chloro 3'-chloro 3',4-difluoro 3',4-difluoro 3-trifluoromethyl 4'-trifluoromethyl 3'-trifluoromethyl 3'-trifluoromethyl 4'-chloro 4'-chloro 3'-fluoro 3-fluoro 4'-trifluoromethyl 4'-bromo 4'-bromo 4'-Ibu 4't bu 4'-chloro 4'-trifluoromethoxy 4'-trifluoromethoxy 4'-trifluoromethoxy 4'-trifluoromethyl mp
(OC)
143 62 109 154 134 87 101 114 94 83 57 101 62 162 101 95 86 35 156-1 58 110-112 103-1 05 70-72 87 76 129 64 80 yield
M%
97 71.8 87.3 98.8 73.7 94.1 26.1 92 90.7 81.6 54.5 81.4 87.3 85.2 83.6 83.7 71.5 86 94 94 98 99 71 81 91 94 33 a..
a.
a a a a a a a.
25 108 5-methoxy 4'-trifluoromethyl Example 109: 2-(4'-Fluorophenvl)-4-(3"-trifluoromethylphenoxv)-6-methvlovrimidine A mixture of 2-(4'-fluorophenyl)-4-chloro-6-methylpyndine (0.6 g, 2.7 mmol) (from example a,a,a-3-hydroxybenzotrifluoride (0.49 g, 3 mnmol) and potassium carbonate (0.41 g, 3 mmol) in N,N-dimethylformamide (3 ml) is heated to reflux for 2 hours.
After cooling, ethyl acetate (10 ml) is added and the suspension is filtered through a bed of silica gel using ethyl acetate. The solvent of the filtrate is removed in vacuo and the residue purified by flash silica gel -column chromatography using hexane/ethyl acetate 7/2. Removal of the solvent affords colourless crystals (0.53g, 56.4%) of melting point 58 0
C.
Examples 110-183: Further compounds of the general formula I are prepared by the procedure of example 109.
Details are given in table X.
Table X 0 9 9 9.
9*99 *9 99 9 *9 99 9 9 9 Ex. RiR2A mp yield No. (CC) M%) 6-methyl 6-methyl 6-methyl 5-methyl 4'-fluoro 4'-fluoro 4'-CF3 4'-CF 3 4'-CF3 4'-CF 3 3'-CH 3 3'-CH3 1 "-CH3-3"-CF3-pyrazol-5'-yl 1 "-CH3-3"-CF3-pyrazol-5'-yl 1 "-CH3-3'-CF3-pyrazoi-5'-yl 3"-CF3-phenyl 1 '-CH 3 -3"-CF3-pyrazol-5'-yl 3'-CF3-phenyl 1 '-CH 3 -3'-CF3-pyrazol-5"-yl 3'-CF 3 -phenyl 133 54.7 21 39.5 79.9 147 27.6 95 97.6 74.9 74.5 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 6-methyl 6-methyl 5-methyl 5-methyl 6-methyl 5-methyl 5-methyl 6-methyl 6-methyl 6-methyl 5-methyl 5,6-dimethyl 5,6-dimethyl 5,6-dimethyl 5,6-dimethyl 6-methyl 6-methyl 6-ethyl 6-ethyl 6-methyl 6-ethyl 5-methyl 5-methyl 6-methyl 5-methyl 6-methyl 5-methyl 6-methyl 6-methyl 3'-CH3 3'-CH3 3'-chloro 3'-chloro 3'-chloro 2',4'-difluoro 2',4'-difluoro 2',4'-difluoro 2',4'-difluoro 2',4-difluoro 4'-CF3 4'-CF3 4'-CF3 3'-CF3 3'-CF3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 3'-CF 3 4'-CF 3 3'-CF 3 4'-Br 4'-Br 4'-Bu 4'tBu 4't Bu 4'-'Bu 4'-CI 26 I "-CH3-3'.'-CF3-pyrazol-5"-yl 3"-CF3-phenyl 1 '-CH3-3-CF3-pyrazol-5'-yl 3"-CF3-phenyl 1 '-CH3-3"-CF3-pyrazol-5'-yI 3"-CF3-phenyl 2'-chloropyrid-4"-yl 1 "-CH3-3"-CF3-pyrazol-5"-yl 3'-CF3-phenyl 2'-chloropyrid-4"-yl 2'-chloropyrid-4-yl 1 '-CH3-3'-CF3-pyrazol-5'-yl 3'-CF3-phenyl 1 "-CH3-3"-CF3-pyrazol-5'-yl 3-CF3-phenyl 1 "-CH3-3"-C 2
F
5 ,-pyrazol-5'-yl 2"-difluoro-1 ,3"-be nzodioxol-4"-yl 1 "-CH3-3'-CF3-pyrazol-5'-yl 2'-chloropyrid-4'-yl 4"-fluorophenyl 3"-CF 3 -phenyl 4"-fluorophenyl 3"-CF 3 -phenyl 3"-CF 3 -phenyl 1 "-CH3-3'-CF3-pyrazol-5"-yl 1 '-CH3-3'-CF3-pyrazol-5"-yl 3"-CF 3 -phenyl 3"-CF 3 -phenyl 3"-CF 3 -phenyl 113 60 116 105 96 68 146 78 64 162 99 136 73 132 105 128 86 75 97 78 65 109-111 110 86-88 149-151 119-1 21 123-1 24 oil 68 74.9 73.2 35.4 52.4 27.1 40.4 58.8 56.4 65.3 31.7 44.1 13.2 65.6 30.3 67.5 41 46 41 92 38 86 100 89 92 78 91 99 29 a a..
a a a a a a a a. a 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 **.164 *165 '16 167 169 170 5,6-dimethyl 5,6-dimethyl, 5,6-dimethyl 5-methyl 5,6-dimethyl 5-methyl 5-methyl 5-methyl 6-methyl 6-methyl 5-methyl 6-methyl 6-methyl 6-methyl 5-methyl 6-methyl 5-methyl 6-methyl 6-methyl 6-methyl 6-methyl 5-methyl 5,6-dimethyl 5,6-dimethyl 6-methyl 5,6-dimethyl 4'-CI 4'-Cl 4'-CI 3'-F 4'-Cl 4'-CI 4'-Cl 4'-CI 4'-CI 3',4-difluoro 3'A4-difluoro 3',4'-difluoro 3' 4'-difluoro 4'-CF 3
O
4'-CF 3
O
4'-CF 3
O
4'-CF 3
O
4'-CF 3 4'-CF 3
O
4'-CF 3
O
4'-CF 3
O
4'-CF 3
O
4'-CF 3
O
4'-CF 3
O
3',4'-difluoro 4'-CF 3
O
4'-CF 3
O
4'-CF 3
O
-27- 1 "-CH3-3"-CF3-pyrazol-5'-yl 2"-chloropyrid-4'-yl 3"-CF 3 -phenyl 1 "-CH3-3"-CF3-pyrazol-5"-yl 1 "-CH3-3"-CF3-pyrazol-5"-yl 1 "-CH3-3"-CF3-pyrazol-5"-yl 2"-chloropyrid-4"-yl 3"-CF 3 -phenyl 1 "-CH3-3"-CF3-pyrazol-5"-yl 2"-chloropyrid-4"-yl 2"-chloropyrid-4'-yl 1 "-CH3-3"-CF3-pyrazol-5"-yl 3"-CF 3 -phenyl 2"-chloropyrid-4'-yl 1 "-CH 3 -3"-CH 3 -pyrazol-5"-yl 1 "-CH3-3"-CH 3 -pyrazol-5"-yl 1 "-CH 3 -3"jbu-pyrazol-5"-yl 1 "-CH3-3"t bu-pyrazol-5"-yl 1 "-CH3-3"-'bu-pyrazol-5"-yl 3"-CF 3 -phenyl 2'-chloropyrid-4"-yl 3"-CF 3 -phenyl 2"-chloropyrid-4'-yl 3"-CF 3 -phenyl 2"-chloropyrid-4"-yl 3"-CF 3 -phenyl 1 "-CH3-3"-CF 3 -pyrazol-5"-yl 1 "-CH3-3"-CF 3 -pyrazol-5"-yl 1 "-CH3-3"-CF 3 -pyrazol-5"-yl 142 150 102 140-150 117 141 125 101 99 151 146 78 64 162 117-121 102-1 04 96-98 88-89 87-90 52 72 83 82 107 68 116 98 128 -28- 176 6-meth oxy methyl .177 6-methoxymethyl 6-methoxymethyl 4'-CI 4'-CI 4'-CI 4'-CF 3 4'-CF 3 4'-CI 2"-chloropyrid-4"-yl 1 "-CH3-3"-CF 3 -pyrazol-5'-yl 3"-CF 3 -phenyl 2"-chloropyrid-4"-yl 3"-CF 3 -phenyl 1 "-CH3-3'-CF 3 -pyrazol-5"-yl 89-91 113-115 140-142 96 173-1 76 95-98 181 5-chloro-6-methoxy 182 5-chloro-6-methoxy 4'-CI 3"-CF 3 -phenyl 4'-CF, 1 "-CH3-3"-CF 3 -pyrazol-5"-yl 80 180 Example 184: 4.6-Bis(2"-chloropyrid-4"-vloxv)-2-(4'-tnfluormethVlphenvl)pvlmidifle 0 RS 0 0 9@ A mixture of 4,6-dichloro-2-(4'-trifiuormethylphenyl)pynmidine (2.93 g, 10 mmol) (from example 111), 2-chloro-4-hydroxypyridine (2.85 g, 22 mmol) and potassium carbonate (3.04 g, 22 mmol) in anhydrous N,N-dimethylformamide (20 ml) is heated at 80 0 C for 1 hour.
After cooling, the solvent is removed in vacuo, ethyl acetate/hexane 1/1 (10 ml) is added and the suspension is filtered through a bed of silica gel. The resulting solution is washed 3 times with water. After drying of the organc layer with anydrous magnesium sulphate, the solvent is removed and the residue is purified by flash silica gel chromatography using hexane/ethyl acetate 8/2. Removal of the solvent affords colourless crystals (4.l1g, 86 of melting point 141 0
C.
Examples 185-1 87 The compounds of general formula (XV a) listed in table Xl are prepared analogously to the method of example 184.
Table Xl 29-
N
A Z-1 0 N (XV a) Ex. R2A mp yield No. (OC) M% 185 4'-trifluoromethyl 1"-CH 3 -3"-CF3-pyrazol-5'-yl 168 86 186 4'-trifl~uoromethyl 3"-CF 3 -phenyl 92 88 187 4'-chloro 1 '-CH 3 -3"-CF3-pyrazol-5'-yl* 156 93 Example 188 6-Methoxv-4-(2"-chloropvid-4"-vlox)-2-(4'-trifluormethlphelvl)pvrimidifle 4,6-Bis(2"-chloropyrid-4-yloxy)-2-(4'-trifluormethylphenyl)pyrimidifle (2.0 g, 4.2 mmol) (from example 184) is dissolved in anhydrous methyl alcohole (5mi), a solution of potassium methylate (4.2 mmol) in methyl alcohole (1.2 ml) is added dropwise to this solution and the mixture is heated to reflux for 30 min.
The solvent is removed in vacuo and the residue is purified by flash silica gel chromatography using hexanefethyl acetate 9/1. Removal of the solvents affords colourless 0 Example 189 4,6-Dibromo-2-(4'-trifluoromethlphenvl)pvflmidine 000e0. 15 A mixture of 4,6-dihydroxy-2-(4'-trifluoromethylphenyl)pyrimidine (5.12 g, 20 mmol) and phosphorous oxybromide (10 ml) is heated for 3 hours at 100 The resulting hot suspension is :~:added to ice and the product can be isolated by suction. After drying, one obtain nearly colourless crystals (6.5g, 86 of melting point 87 OC.
Examples 190-203 Compounds of the general formula I are prepared by the procedures of example 188 or 109.
Details are given in table XII.
Table XII
N
Ex. R 1 A mp yield No. (OC) 190 6-methoxy 4'-CF 3 1 -CH3-3-CF3-pyrazol-5-yl 130 64 191 6-methoxy 4'-CF 3 3"-CF 3 -phenyl 94 94 192 6-methylthio 4'-CF 3 1 "-CH3-3"-CF3-pyrazol-5-yi 127 193 6-methylthio 4'-CF 3 2'-chloropyrid-4"-yl 106 41 194 6.-dimnethylamnino 4-CF 3 1 "-CH 3 -3"-CF3-pyrazol-5"-yl 148 195 6-ethylamino 4-CF 3 1 '-CH 3 -3"-CF3-pyrazol-5'-yl 102 23 196 6-methoxy 4'-CI 1 "-CH 3 -3"-CF3-pyrazol-5"-yl 144 197 *6-methoxyamino 4'-CI 1 '-CH3-3"-CF3-pyrazol-5'-yi 178 16 198 6-dimnethylamino 4'-CI 1 '-CH 3 -3'-CF3-pyrazol-5'-yl 143 13 199 6-amnino 4'-CI 1 "-CH 3 -3"-CF3-pyrazol-5-yl 149 200 6-methylamnino 4'-CI 1!"-CH 3 -3"-CF3-pyrazol-5"-yi 114 97 201 6-bromo 4'-CF 3 1 "-CH 3 -3'-CF3-pyrazol-5"-yl 110 57 202 6-chloro 4'-CI 1 '-CH 3 -3-CF3-pyrazol-5-yl 122 26 203 6-chloro 4'-CF 3 1 "-CH 3 -3"-CF3-pyrazol-5-yI 113 69_ Example 204 6-Vinyl-4-( "-methyl-3"-trifluormethylhyrazol-5"-l)-2-(4'-tfluormethlphenVl)pyrimidine A mixture of 6-bromo-4-(l1 -methyl-3"-trifluormethylpyrazol-5"-yl)-2-(4'-trifluormethylphenyl)pyrimidine (2 g, 4.3 mmol, from example 201), vinyltributylstannate (1.4 ml, 4.7 mmol), *9 31 tetrakis(triphenylphosphine)palladium(0) (0.1 g, 0.09 mmol), toluene (20m1) and 3 crystalls of 2,6ditertbutyl-4-methylphenol is heated to reflux for 90 min. After cooling, a 1.2 N solution of pyridinium fluoride in THF/pyridine (4 ml) and pyridine (2ml) is added. The solution is stirred for 17 h at ambient temperature. To the resulting mixture ethyl acetate (100 ml) is added and the solution is washed twice with water and a satured solution of sodium bicarbonate. After drying of the organc layer with anydrous magnesium sulphate, the solvent is removed and the residue is purified by flash silica gel chromatography using hexanelethyl acetate 7/3. Removal of the solvent affords nearly colourless crystals (1.45g, 82 of melting point 1 12*C.
Examples 205-214: Additional compounds are prepared analogously to example 24. Details are found in Table XII1.
Table XIII
R
1
N
Ex. R' A R 2 mp No. 0 c) 205 3-ethyl 3'-CF 3 -phenyl 4"-trifluoromethyl 72-75 206 5-ethyl 3'-CF 3 -phenyl 4"-trifluoromethyl 44-46 207 4-methyl l'-CH 3 -3'-CF 3 -pyrazol-5'-yl 4"-trifluoromethyl 98 208 4-methyl 3'-CF 3 -phenyl 4"-trifluoromethyl oil 209 4-methyl 1 '-CH 3 -3'-CF 3 -pyrazol-5'-yl 5"-dichloro 117 210 4-methyl 1 '-CH 3 -3'-CF 3 -pyrazol-5'-yl 5"-di (trifi uoromethyl1) 126 211 4-methyl 1'-CH 3 -3'-CF 3 -pyrazol-5'-yl 3"-chloro-4"- fluoro 101 212 4-methyl 1 '-CH 3 -3'-CF 3 -pyrazol-5'-yl 3,4'-diclbro 97 213 3-methyl 3'-CF 3 -phenyl 4"-trifluoromethyl 71-73 214 3-methyl 1 '-CH 3 -3'-CF 3 -pyrazol-5'-yi 4"-trifluormethyl 130-133 32 Examples 215-221: Additional compounds are prepared analogously to example 188 starting with 2,4-bisaryloxy-6arylpyridines. Details are found in Table XIV.
Table XIII a a.
Ex. RA R2mp No. (0C) 215 4-methoxy l'-CH 3 -3'-CF 3 -pyrazol-5'-yl 4"-trifluoromethyl 102 216 4-methyl- I '-CH 3 -3'-CF 3 -pyrazol-5'-yl 4'-trifluoromethyl 168 amino 217 4-methoxy 3'-CF 3 -phenyl 4"-trifluoromethyl oil 218 4-C 2
H
5 I -CH 3 -3'-CF 3 -pyrazol-5'-yl 4"-trifluormethyl 61 219 4-CH 3 2'-difluoromethoxypyrid-4'-yl 4"-trifluormethyl 76-79 220 4-CH 3 2'-trifluoromethylpyrid-4'-yl 4"-trifluormethyl 112-115 221 4-C 2
H
5 2'-trifluoromethylphenyl 4"-trifluormethyl oil The required 2,4-bisaryloxy-6-arylpyridines are obtained in anlogous way as explizitly descibed below for: 2.4-Bis-(1 "-methVl-3'-trifluoromethvlpyrazol-5"-vloxv)-6-(4'-trifluormethVlophenl) pyrid ine A mixture of 4-nitro-2,6-dichloropyridine (3.9 g, 20 mmol), 1 hydroxypyrazole (7.3 g, 44 mmol) and potassium carbonate (6.7 g, 48 mmol) in anhydrous sulfolane isT heated-to 1 10*C overnight. The reaction mixture is cooled to ambient temperature, deluted with pentane/ethyl acetate (volume ration of 1/1) and filtered through a bed of silica gel.
15 The filtrate is washed 10 times with water, dried over anhydrous magnesium sulfate and the solvents are removed in vacua. The residue is purified by flash silica gel chromatography using pentane/ethyl acetate. One obtains 2,4-bis-(l1'-methyl-3'-trifluoromethylpyrazol-5'-yloxy)-6chloropyridine (4.3 g, m.p.:105 0
C).
33- A mixture of bis(benzonitrile)palladium(ll)chloride (0.19 g, 0.5 mmol) and 1,4bis(diphenylphosphino)butane (0.2 g, 0.5 mmol) in anhydrous toluene (10 ml) is heated to reflux under a atmosphere of nitrogen. After 2 hours 4-trifluoromethylbenzeneboronic acid (1.2 g, mmol), 2,4-bis-(l1 -methyl-3"-trifluoromethylpyrazol-5"-yloxy)-6-chloropyidine (2.2 g, 5 mmol).
ethanol (2.5 ml) and a 1 M hydrous solution of sodium carbonate (5 ml) is added and the mixture is heated to reflux for additional 2 hours under a nitrogen atmosphere. The reaction mixture is deluted with ethyl acetate and filtered through a bed of silica gel. The filtrate is washed with water, dried over anhydrous magnesium sulfate and the solvents are removed in vacuo. The residue is purified by flash silica gel chromatography using pentane/ethyl acetate (volume ratio One obtain colorless crystals of the title compound (2 g, 73 yield) of melting point 133 0
C
Examples 222-300: Further compounds of the general formula I are prepared by the procedure of example 113.
Details are given in table XIV.
Table XIV
N
0 N
R
2 Ex. RR2A mp No. C 0
C)
222 5-methyl 4'-CF3 4"-chloro-pyrimidine-6-yi 107 223 6-methylthio 4'-chloro 1 "-CH3-3"-CF3-pyrazol-5-yl 131 224 6-bromo 4'-CF3 2"-chloro-pyridine-4"-yi 108 225 6-bromo 4'-CF3 3"-CF3-phenyl 96 226 6-(dimethylamino)- 4'-chloro 1 "-CH3-3"-CF3-pyrazol-5'-yl 126 methylenamino 227 6-ethinyl 4'-CF3 1 "-CH 3 -3"-CF3-pyrazol-5"-yl 117 228 6-methoxymethyl 4'-CF3 1 "-CH 3 -3"-CF3-pyrazol-5"-yl 114-116 229 6-methoxymethyl 4'-CF3 3"-CF3-4"-fluorophenyl 71-73 230 6-methoxymethyl 4'-CF3 2"-ch loro-py rid ine4"-yI 100-1 02 S *5 241 242 243 244 245 246 247 248 249 250 251 252 253 254 255 256 257 258 6-methyl 6-methyl 6-methyl 4-fl uoro 6-ethyl 6-ethyl 6-ethyl 6-ethyl 6-ethyl 6-ethyl 6-ethyl 6-ethyl 4-chloro 4-chloro 4-chloro 6-methyl 4-methylamino 6-ethoxy 6-(2-fluoroethoxy) 6-(2,2,2trifluoroethoxy) 6-allyloxy 5,6-diethoxy 6-methoxymethyl -6-cyeinomethyl 6-hydrazino 4-fluoro 4-fluoro 4'-chloro 4'-SO 2
CH
3 4'-SO 2
CH
3 4'-SO 2
CH
3 4'-CF3 4'-CF3 4'-CF3 4'-CF3 4'-CF3 4'-CF3 4'-CF3 4'-CF3 4'-CF3 4'-CF3 4'-CF3 4'-CF3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4--CF 3 4'-CF 3 4'-CF 3 34- 1 "-CH3-3"-CF3-pyrazol-5-yl 1 '-CH 3 -3'-CF3-pyrazol-5-yl 3"-CF3-phenyl 2"-chloro-pyrid-4"-yl I "-CH 3 -3"-CF3-pyrazol-5-yl 1 "-CH3-3"-CF3-pyrazol-5"-yl 3"-CF 3 -phenyl 2'-chloro-pyrid-4"-yl 4"-chloro-pyrimidine-6"-yl 6'-(2,2,2-trifluoroethoxy)-pyrimidine-.
4 1-yl ichloro-pyrid-4"-yl 6"-cyano-pyrid-4"-yl 3"-CF3-4"-fluorophenyl 3"-CF3-phenyl 2"-chloro-pyrid-4"-yJ 1 "-CH 3 -3'-C 2
F
5 -pyrazol-5'-yl 2"-difluoromethoxy-pyrid-4'-yl 1 "-CH3-3'-CF3-pyrazol-5"-yl 1 "-CH3-3'-CF3-pyrazol-5"-yl 1 "-CH3-3"-CF3-pyrazol-5 -yl 1 "-CH 3 -3"-CF3-pyrazol-5'-yl 1 "-CH3-3'-CF3-pyrazol-5"-yl 1 "-CH3-3'-CF3-pyrazol-5'-yl 3"-CF 3 -phenyl 1 "-CH3-3"-CF3-PYrazol-5'-yl 1 "-CH3-3'-CF3-pyrazol-5'-yl 3"-CF 3 -phenyl 2"-chloropyrid-4"-yl 156-1 132 162 168 124 77 97 86 105 158 130 62 89 104 108 89-92 167 162 148 133 127 93 56-59 127-1 187 oil 136 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 4-iodo 6-methyl 6-difluoromethoxy 4-chloro-5-methyl 4-fluoro-5-methyl 4-fluoro-5-methyl 4-fluoro-5-methyl 6-methyl 6-methyl 5-chioro 6-methyl 4-chioro 6-methyl 5-isopropyl 6-methoxy 5-methyl 4-chioro 6-methyl 6-methyl 6-methyl 4-difluoromethoxy 6-methoxy 5-methyl 4-chloro 6-methoxy 5-methyl 5-methyl 6-methyl 5-methyl 4'-CF 3 4'-CHCI 2 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CN 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 5'-di(CF 3 5'-di(CF 3 4',5'-di(CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 35 1 "-CH3-3"-CF3-pyrazol-5"-yl 1 '-CH373"-CF3-pyrazol-5"-yl 3"-CF 3 -phenyl I "-CH3-3"-CF3-pyrazol-5"-yl 1 "-CH3-3"-CF3-pyrazol-5'-yl 3"-CF 3 7phenyl 2"-chloropyrid-4"-yl 2'-trifiuoromethylpyrid-4"-yl 1 '-CH3-3"-CF3-pyrazol-5"-Yl 1 "-CH3-3"-CF3-pyrazol-5"-yl 2"-(2,2,2-trifluoroethoxy)pyid-4"-yI 2"-difluoromethoxypyrid-4"-yl 3"-CN-phenyl 3"-CF 3 7phenyl 2"-trifluoromethylpyrid-4'-yl 2"-trifluoromethylpyrid-4'-yi 2"-trifluoromethylpyrid-4"-yl 1 "-CH3-3"-CF3-pyrazol-5'-yl 3"-CF 3 -phenyl 2"-chloropyrid-4'-yl 1 "-CH3-3"-CF3-pyrazol-5'-yl 2"-difluoromethoxypyrid-4'-yl 2'-difluoromethoxypyid-4"-yl 2'-(2,2,2-trifluoroethoxy)pynd-4'-yI 2"-(2,2,2-trifluoroethoxy)pyrid-4"-yI 2'-(2,2,2-trifluoroethoxy)pyrid-4'-yI 3"-CF 3 O-phenyl 3"-CF 3 O-phenyl 2"-cyanopyrid-4'-yi 108 116 92-95 146 150 69 129 105 177 135-140 104-1 06 101-1 04 138 66 84 109 97 132 93 128 108-110 88-91 101-103 98-101 91-94 74-76 73 63 133 4 6-methyl 6-methoxymethyl 6-methoxy 6-ethyl 6-ethyl 6-ethyl 6-methoxymethyl 6-methoxymethyl 6-methyl 6-methyl 6-methoxy 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 4'-CF 3 36 2 t -pentafluoroethylpyrid-4'-yI 2'-pentafluoroethylpyrid-4'-yl 2"-trifIuoromethylpyrid-4'-yI 2"-pentafluoroethylpyrid-4"-yI 2'-trifluoromethylpyrid-4'-yi 2'-(2,2,2-trifluoroethoxy)pydA-yI 2"-difluoromethoxypyrid4-y 2'-difluoromethoxypyrid-4'-y 2-(2,2,2-trifluoroethoxy)pyrid-4'-yI 1, 1,2,2-tetrafluoroethyl)pyrid-4'-y.J 2"-difluoromethylthiopyrid-4"-yI 2"-difluoromethylthiopyrid-4-yI 2-difluoromethylthiopynd-4'-yI 134 91 100 59 86 92 118 70-73 80-95 67-70 a. a a a a a.
a a a. a a a.
Examp~le 301: Herbicidal activity To evaluate'their herbicidal activity, compounds according to the invention are tested using 5 a representative range of plants: TRZAS Triticumn aestivumn HORVW Hordeum vulgare GOSHI Gossypium hirsutum H ELAN Helianthus annuus 10 ORYSA Oryza sativa GLXMA Glycine max BEAVA Beta vulgaris ZEAMX Zea mays ALOMY Alopecurus myosuroides 15 AVEFA Avena fatua ECHCG Echinocloa crus-galli SElVI Setaria viridis GALAP Galium aparine -37- STEME Stellaria media CHEAL Chenopodium album VERPE Veronica persica LAMPU Lamium purpureum VIOAR Viola arvensis SIDSP Sida spinosa AMBAR Ambrosia artemisifolia ABUTH Abutilon theophrasti IPOPU Ipomoea purpurea SINAL Sinapis alba AMARE Amaranthus retroflexus The tests fall into two categories, pre-emergence and post-emergence. The pre-emergence tests involve spraying a liquid formulation of the compound onto the soil in which the seeds of the plant species mentioned above had recently be sown. The post-emergence tests involve spraying seedlings of the above species with a such a formulation.
The soil used in the tests is a prepared horticultural loam. The formulations used in the test are prepared from solutions of the test compounds in acetone containing 0.4% by weight of an alkylphenyl/ethylene oxide condensate surfactant available under the trade mark TRITON X 155.
The acetone solutions are diluted with water and the resulting formulations at dosage levels corresponding to 1000 g or 300 g of active material per hectare in a volume equivalent to 400 litres per hectare. In the pre-emergence tests untreated sown soil and in the post-emergence tests untreated soil bearing untreated seedling plants are used as controls.
The herbicidal effects of the test compounds are assessed visually twenty days after spraying the foliage and the soil (in the case of examples 13-16 thirteen days after treatment) and 25 are recorded on a 0-9 scale. A rating 0 indicates growth as untreated control, a rating 9 indicates Sdeath. An increase of 1 unit on the linear scale approximates to a 10% increase in the level of effect. An asterisk indicates that the specified plant species was not treated in the test.
The results of the test are set out in the tables shown below in which the compounds are identified by reference to the preceding examples. An asterisk indicates that the specified plant 30 species was not treated in the test.
Table XV S: Efficacy of the compounds of the invention in pre-emergence and post-emerbence application 38- TH G HOG B Z AA E SG S CV L V S AA I S A RO 0 E R L E E LVC E A T H E A I I M B P I M ZR S L Y XAA OE H T L E ERMO D B U O N A Ex. dose appl. A V H A S M V M M F C V A M A P P A S A T P A R No g/ha time WIW I .N A A A X Y AIG I P E L E U R P R H U L E 13 100 pre 0 0 4 2 2 4 .5 0 post 2 5 8 4 2 5 8 14 100 pre 3 4 9 9 6 8 8 0 post 4 6 9 6 6 7 8 100 pre 0 2 8 2 2 5 6 0 post 2. 6 9 5 2 7 6* 6 16 100 pre 0 0 2 0 0 2 2 0 post 0 2 7 4 212 5 24 300 pre 1 0 0 0 0 0 0 0 0 0 0 0 post 0 0 1 1 1 0 0 0 0 0 0 0 300 pre 0 0 0 0 0 0 1 0 0 0 0 0 post 0012***2 0 0 0 *1 *1 26 300 pre 1 0 1 1 0 2 0 0 0 0 0 0 post 1 2 3 2 0 2 4 0 4 4 1 27 300 pre 00*0* 0 0 0 0 0 0 0 0 post 2 2 3 3 1 1 2 0 3 3 2 4 28 300 pre 0 3 0 0 3 5 6 9 2 7 9 8 8 4 4 4 2 9 post 3 3 4 5 4 5 4 6 5 4 6 6 6 5 4 4 6 29 300 pre 0 1 0 0 8 0 7 8 8 0 0 9 post 4 3 4 3 3 3 5 6 8 5 4 7 30 300 pre 4 6 3 3 4 9 8 9 6 9 9 9 8 8 8 6 6 9 post 4 5 6 6 4 6 6 7 5 6 6 7 8 5 6 6 31 300 pre 14 2 0 3 1 8 59 7 9. *9 9 8 8 5 9 post 3 5 8 5 5 8 7 4 7 6 7 9 7 8 8 6 7 32 300 pre 1 0 0 0 0 0 3 2 8 1 6 8 3 8 3 1 9 post 2 2 5 4 3 3 3 2 4 4 5 9 5 7 4 5
U
U. U U U U U U
U.
U U U U U U U U
U.
39 T H G HOG BZ A AE S G S CV L V S AA IS A ROO E R L EE L VC E A T H EA I I1MB P1I M Z R S LY X A A 0OE H T L E E R MO0D B U O N A Ex. dose app. A V H A S M V M M F C V A M AP P A S AT P A R No: giha time WWIN AAA XjYAG I IP E LE U RPR HU L E 33 300 pre 2 00 0*2*00*00 00*0 0 0* 05 *0 post 0 0 0 0 *0 0 0 *0 2 0 0 *0 0 0 0 1 0 34 300 pre 1 3 3 *3 1 *2 7 8 8 2 .8 *9 8 9 *8 3 5 8 ___post 2 2 5 1 217 1 2 4 *14 15 6 161 19 61 6 1 516 6 17 7 39 300 pre 1 3 0*0* 0 5* 4 9 2 9 9 8 9 3 3 3 9 post 1 .24 3.3 2 7.5 5 9 5 7 3 3 5 109 300 pre 0 0 0 0* 00*0 00 06 0 000*0 0*6 __post 0 0 2 0 1 0 0 0 1 0 10 0 7 0 0 1 0 2 1 110 300 pre 34 21 2 *869 2 9*19 999*53*9 pot 4 5 6 6 *4 7 7 6 8 7 *9 7 8 6 *6 4 6 i11 300 pre 1 3 0 0 *0 8 9 5 9 8 9 8 6 5 3 9 __ps 5 4 4 6 6 8 9 9 8 6 6 4 6 112 300 pre 3 5 6 3 *5 *4 9 *8 9 8 9 *9 9 8 8 9 *9 post 4 5- 8 8 8 5 7 6 8 7 8 *9 8 9 8 7 8 113 300 pre 3 6 6 2 *3 *3 9 *8 9 8 9 *9 8 8 *9 9 *9 __post 4 5 8 8 8 5 6 7 9 7 8 *9 8 8 8 8 7 114 300 pre 4 5 8 3 *4 *3 8 *8 9 8 9 *9 8 8 *9 9 *9 post 4 5 8 6 6 6 8 5 8 7 8 *9 8 8 8 8 7 115 300 pre 4 7 8 3 *5 *4 8 *8 9 8 9 *9 9 8 *9 9 *9 post 4 6 98 8 6 7 68 78 888 8 8.
116 300 pre 0 3 0 0 *0 *0 6 *4 9 0 6 *9 8 7 *2 4 *8 post 2 3 4 4 *5 *3 3 *2 8 3 4 *9 7 5 *4 5 117 300 pre 0 2 0 0 *0 *12 7. 5 9 1 5 *9 6 8 4 4 9 post 3 3.4 4 4 4 4 3 4 4 9 .5 .7 4 5 7 118 300 pre 0 0 0 0 0 0 3 4 7 1 2 *8 3 7 1 2 9 ___post 0 2 4 4 3 2 3 3 4 3 3 *9 4 5 2 4 40 T H GHOG B ZA AES GS C VLV S AA IS A ROO0ER L EE LV CE ATHEA I I M B P I1 M Z R S LY X A A 0 E H T L E E R MO0D B U O N A Ex. dose app. A V H A S M V M M F C V A M AP P A S AT P A R No giha time IWW I NAA A X Y A G, I P EI L IE IUI R P RI H UI L E1 119 300 pre 0 0 0 0 0 *0 0 1 0 0 0 *0 0 2 0 0 0 post 0 2 0 2 1 1 1 0 1 2 2 *3 1 5 1 3 4 120 300 pre 1 32 0*0*28 *6 969*88 8*5 5* 9 post 2 4 5 4 5 *3 5 4 5 6 4 *9 8 7 5 4 121 300 pre 23 20*1*3 8* 7913 8*9 78 4* 9 __post 3 4 8 4 5 5 5 6 7 6 5 *9 7 8 4 5 6 122 1300 pre 123 300 pre 0 00 000 0*000 0 *22 4*0 0*4 post 1 1 2 3 2 1 1 2 2 3 41 15 13 5 2 6 4 124 300 pre 1 3 2 1 5 *5 5 6 8 3 9 9 8 9 7 9 9 post 4 4 6 5 5 5 5 6 7 4 5 *9 6 8 6 7 6 125 300 pre 3 4 32*3*5 8*7 94 9*999*9 79 __post 4 5 .5 5 6 5 5 6 7 5 61 19 6 8 5 7 6 126 300 pre 000 0 3* 091 7*88 2 3 *9 post 2 2 5 4 3 3 3 3 3 4 4 *9 5 8 4 6 127 300 pre 0 0 1 0 *0 2 2 0 8 0 7 *7 3 8 2 4 8 post 0 1 14 3 2 2 3 2 4 3 5 *6 4 8 4 61* 6 128 300 pre 4 5 7 2 3 15 18 7 9 5 19, *19 9 9 9 9 9 post 5 5 6 5 5 6 61 7 7 6 6 *9 6 8 6 8 7 129 300 pre 3 35 4 3 3 8 699 5 9 99 91 1 91 post 214 7 5 15 3 5 5 6 5 5 916 8 6 9 6 130 300 pre 2 5 3 2 3 3 7 6 9 4 9 *9 6 9 7 6 *8 __post 2 4 6 5 5 4 5 5 7 15 6 *8 6 8 5 9 6 131 300 pre 0 0 2 2 0 *2 1 0 8 0 4 *7 0 8 0 5 8 1 1 3 4 2 1 2 2 2 4 4 *7 4 7 1* 4 5 4 -41- T H G HO0G B Z A A E S G S C V L V S A A I S A RO0 0 E R L EE L V C E A T HE A I I M B P I. M Z R S L YXA AOE HT L EE R MOD B UON A Ex. dose app. A V H A S M V M M F C V A M AP P A S AT P A R No g/ha time WWIINAAIA XIYAIGI PE L E URIP IRH U LE 132 300 pre 0 0 0 0 *3 *0 0 *0 3 0 0 *0 0 3 3 post 0 1 3 2 2 1 0 1 2 3 3 *4 3 5 2 5 133 400 pre 5 5 5 7 *4 8 9 7 *9 9 9 9 ___post 3 4 15 6 4 181 1 8 9 8 8 9 91* 134 400 pre 3 4 *34*48* 9 93 9 *7 6. *64** post 2 3 2 6 3 4 8 9 8 9 9 135 300 pre 6 7 *5 4 *3 8 8 9 3 8 *9 8 8 9 post 4 61* 4 6 3 7 6 7 6 7 819 9 1 7 9 136 300 pre 6 8 *5 4 *4 8 8 8 1 9 9 8 6 9 post 5 6 *5 6 *4 6 *7 7 6 8 6 9 7 8 8 137 300 pre 0 0 *0 0 *0 0 *0 0 0 0 5 0 0 0 0 ___post 10 1 1 1 0 1 0 0 1 1 2 2 1 2 138 300 pre 6 7 *4 4 *3 8 8 9 4 9 9 9 7 9 ___post 4 7 *4 7 *3 6 6 7 5 7 7 9 8 7 8 139 300 pre 0 0 0 0 0 0 0 *00 0** post 1 2 1 2 0 1 1 1 1 1 4 012*0 2 4 140 1300 pre 4 515 *3 2 2 8 8 8 4 9 *9 9 9 *8 4 6 8 ___post. 3 4 5. *15 5 3 7 4 8.7 6, 9 8 6 6 8 9 9.
141 300 pre 1 4 2 1 2 1 2 7 8 9 1 9 9 8 8 *5 2 4 __post 2 3 9 2 4 3 .4 3 5 5 5 *8 7 6 6 5 9 9 142 300 pre 0 0 1 0 1 *0 0 1 5 1 4 *5 1 7 0 0 1 0 ___post 0 1 5 0 4 *2 0 1 1 2 3 *5 4 6 5 3 5 143 300 pre 0 1 4 *2 2 *2 6 *5 8 3 9 *9 8 9 *8 4 5 *8 post 1 2 81 1 0 3 3 1 2 3 6 5 1 8 5 6 7 6 7 8 8 144 300pr 00*0 2*0 0*0 3.0*4 4 4*0 04*3 pot 1 1 6 0 3 2 0 1 4 61315 5 3 4 6 4 4O 4* .4 4*4**4 4
S
4. 4*
S
S
S
555 S S 4* .4 54 4 5 S S 5 4 S 44 5* 4 S S .5 -42 T H G H 0 GB Z A A E S G S C V L V S A A I S A RO0 0 E R L EE L V C E A T H EA I I M B P I M Z R SL Y XAA 0E H TL EE R MOD B UON A Ex. dose appl. HA SVAMM C V AM AP PA SAT PA R No giha time W W I N A A A XY YA G I IP E L EUR P, R, H U L E 145 300 pre 0 0 2 0 1 *1 2 *2 5 0 3 *6 3 6 *2 0 2 post 1 2 8 0 4 *3 1 2 2 5 5 *7 5 6 6 5 5 8 146 300 pre 0 0 0 0 1 0 7 *3 8 0 8 *9 4 8 *413 1 9 __post 0 0 1415 1 1 4 5 1 4 91 147 300 pre 0 1 0 0 *1 *0 5 *3 7 0 6 9 3 7 *3 3 3 *9 post 0 101415 *4 1 4 3 5 4 5 6 4 5 4 4 5 4 148 300 pre 0 0 0 0 *0 *0 0 2 0,0 8 10 8 0 1 0 9 post 0 0 3 4 2 *2 1 1 3 4 3 4 3 6 3 2 4 1 141 149 300 pre 0 0 3 0 *0 *0 0 *0 0 0 0 *2 1 5 *0 0 0 8 post 00 04* 2*2 0*0 24 3*5 4 4*L414 4 150 300 pre 2 4 4 2 *3 *4 8 *7 9 2 9 *9 9 9 *7 4 6 *9 post .2 4 651*4*46*6 85 5*77 7*6 66 7 151 300 pre 0 0 0 2 *0 *0 4 *0 0 0 6 *8 2 9 *4 1 1 9 __post 0 1 4 5 3 *3 2 2 4 4 5 *6 4 7 *4 2 4 6 152 300 pre 3 4 5 4 *3 *4 8 *7 7 4 9 *9 8 9 *8 7 9 *8 post 2 4 616 5 5 8 6 9 7 7 7 7 7 7 6 5 71 153 300 pre 1 3 3 0 *1 3 8 *7 7 1 9 *9 8 9 *4 5 5 9 post 4 4 5 6 4 4 6. 5 8 5 6 8 15 4 5.5. 154 300 pre 4 5 4 2 *2 *4 8 18 9 3 9 *9 9 9 *8 7 7 9 post 5 6 5 7 155 300 pre 3 4 4 1 1 *3 8 8 9 4 9 *9 8 9 *18 8 6 9 post 1 5 6 6 *5 *6 6 *7 8 6 7 *7 5 7 *5 6 5 156 300 pre 2 2 0 0 *0 6 *4 9 0 8 *9 4 9 *4 4 3 9 ___post 0 1 14 5 4 4 5 4.9 5 7 7 4 6 4 4 4 17 300 pre 1 3 2 1 5 *5 5 *6 8 3 9 *9 8 9 *7 7 9 9 post 4 4 6 5 5 5 5 6 7 4 5 9 61 8 5 6 7 6, 0 *0 0000 a a 00 a a. a.
a a a. *a a a a a a a V a a.
0 a a a as aa a a a a a. a a.
a.
em S S 0O t
S@
mm..
C CS mm mm 0 mm SO S 0 0
S
mm om S S 0
S
mm mm 00*
S
mm..
S C
C
S.
S@
me C C
SS
me me mm S mm mm C C 0e mm m 43 T H GHOG BZ AA ES GS CV LV S AA IS A R00E R L EE L V CE AT H EA I I1MB P1I M Z R S L YX AAO0E HT L EE R MOD B UON A Ex. dose app. A V H A SM VMM FC VA M AP P A S AITP A R No Ig/ha time IWW I IN IA IA AXIYI AG I IIP IE L IE IU R P R H U L E 158 300 pre 3 4 3 2 *3 5 8 *7 9 4 9 *9 9 9 *7 9 7 *9 post 4 5- 5 5 *6 5. 5 *6 7 5 6 *9 6 8 *5 5 7 *6 159 300 pre 0 0 0 0 *0 0 3 *0 9 1 7 *8 4 8 412 131 9 ___post 2 2 5 4 3 *3 3 *3 3 4 4 *9 5 8 *4 4 6 160 300 pre 0 0 1 0 0 212 0 8 01 7 71 3 81 2 2 4 2 ___post 10 1 4 3 2 2 3 *2 4 3 5 6 4 2 5 4 6 6 161 300 pre 0 0 0 *0 1 0 0 *0 0 0 0 1 0 0 0 10 0 0 post 0 1 3 0 2 0 0 0 -1 0 1 1 1 5 1 1 3 2 162 300 pre 0 0 0 *0 0 *0 0 0 0 0* 0 0 0 0 0 0 0 post 10 10- 3 0 2 0 0 0 0 1 1 5 5 0 0 2 0 163 300 pre 0 0 0 0 0 010 *0 3 1 0 *3 0 21* 010 12 0 post 1 15 0 04 2 20*0 22 3*645 3 324 164 300 pre 0 0 0 *2 0 *0 0 *0 5 0 6 *4 1 7 1 0 1 3 __ps 1 4 *31 12 4*656 3 335 *8 165 300 pre 0 3 5 *2 2 *2 8 *8 9 4 9 *9 9 9 *8 4 6 *8 __post 12 3 9 0 6 3 3 21 5 8 6 9 7 16 6 7 9 8 166 300 pre 0 1 4 *2 1 1 5 *7 5 2 5 *8 7 8 6 2 4 8 ___post 1 2 5 2 17 121 3 1* 3 4 6 5 8 5 7 141 6 5 8 167 300 pre 2 3 5 *4 2 3 8 8 9 2 8 *9 8 8 8 4 9 *8 post 2 -3 6 5 6 3 6 *6 8 5 7 *8 6 6 *4 6 5 8 168 300 pre 2 3 4 *0 3 *1 7 *5 8 1 5 *9 6 9 5 4 3 9 post 2 3 8 2 7 2 4 *4 515 5 *9 8 8 61 5 8 7 169 300 pre 3 3 5 *5 2 *3 8 *6 9 1 9 *9 8 9 *5 4 6 *9 post 133 9*516*35*5 6 54*877 7 566 7 170 300 pre 0 0 0 *0 0 *0 0 *0 2 0 0 *0 1 5 *0 0 2 6 __post 0 14*0 5*1 0*0 02 1*33 5*324*5 -44 TH G HOG BZ AA ES G SCV LV S AA IS A RO0 0 E R L EE L V C E A T HE A I I M B P I M Z R S LY X A A 0 E H T L E ER MO0D B U O N A Ex. dose app. A V H A S M V M M F C V A M AP P A S AT P A R No1 g/ha time WIW I I NI AI A AIX YI AG, I PI E L IEIU R, PR, H U L E 171 300 pre 0 0 1 *0 0 *0 3 *2 6 0 0 *3 2 8 *0 0 1 7 _post 1 2 4 0 4 1 2 *2 3 4 2 5 5 7 4 4 172 300 pre 0 0 0 0 *0 0 *0 0 0 0 *2 2 4 1 0 0 1 4 __post 1 1 2 2 1 1 2 2 3 4 5 3 5 2 2 6 4 173 300 pre 1 3 6 2 2 8 *8 9 6 8 *9 9 9 *8 5 8 *8 post 12136 1* 36*6 76 7*967*6168 *81 174 300 pre 3 3 5 *0 3 *2 8 5 8 4 8 *9 8 9 *6 4 6 *9 ot 2 3 6 4 7 3 5 5 5 15 41* 9 718 6 175 300 pre 0 0 2 *0 1 *0 4 1 7 0 2 *7 4 8 1 0 0 8 __post 1 1 6 1 7 1 5 5 5 5 4 9 7 8 6 5 8 7 176 400 pre 3 2 2 3 2 17 8 3 *9 18,* 2 8 post 3 4 2 2 2 4 6 8 8 7 8 9 177 400 pre 7 5 5 4 *4 8 9 5 *9 6 9 post 3 5 4 6 4 6 7 7 *9 7 6 178 400 pre 2 2 2 1 1 6 8 4 8 2 3 post 1 3 4 4 3 3 4 5 9 5 4 188 400 pre 14 15 1 6 4 5 9 9 8 9 9 9 9 post 3 4 3 5 3 7 8 9 9 81 1 8 9 190 400 pre 5 6 5 5 5 9 9 9 9 9 9 9 4 5 4 191 400 pre 4 4 5 5 *4 9 9 8 *9 9 9 9 post 4 4 4 7 3 8 8 9 9 8 9 9 192 400 pre 4 4 3 5 4 8 9 7 *9 8 9 9 post 3 14 3 6 2 71 8 9 9 8 *1 9 9 1* 193 400 pre 4 5 3 4 *4 8 9 7 9 8 8 9 post 4 4 4 5 3 8 9 81 8 7 8 9 e Table XVI Efficacy of the compounds of the invention in pre-emergence application Example Rate G H O T Z A A C G I L M S V A D E S [kg/ha] L O R R E B M A A P A A T E L I C E X R Y Z A U B S L O M T E R O G H T M V S A M T E O A H P I M P M S C V A WAWX HL B P E U N E E Y A G I 218 0.4 4 5 3 5 4 9 9 7 8 9 8 9 8 9 9 9 8 9 0.1 4 4 2 4 3 8 9 7 7 5 8 9 8 9 7 9 6 8 0.025 3 3 1 2 2 8 9 6 2 5 8 9 7 8 5 8 2 8 0.01252 2 1 11 6 8 6 1 3 8 8 X X 2 7 1 6 219 0.4 6 5 4 5 4 9 9 9 8 9 8 9 X 9 9 9 9 9 0.1 4 4 2 4 3 9 9 9 7 9 8 9 X 9 8 9 7 9 0.025 3 3 2 2 2 8 7 8 3 7 8 9 X--9 5 9 5 9 0.01253 2 1 1 1 57 8 X 6 7 9 X 9 3 7 3 6 220 0.4 6 6 4 6 5 9 9 9 8 9 8 9 X 9 9 9 9 9 0.1 4 5 3 4 3 8 8 9 8 9 X 9 X 9 8 9 7 9 0.025 2 4 1 2 2 7 8 7 2 4 8 9 X 9 7 9 4 9 0.01252 3 1 1 4 7 3 X 3 7 9 X 8 6 8 3 7 292 0.4 5 7 4 6 5 9 9 9 8 9 8 9 9 9 9 9 9 9 0.1 4 5 3 4 4 8 9 8 7 7 8 9 9 9 9 9 8 9 0.025 2 4 1 2 2 6 8 7 5 5 8 9 9 9 7 9 5 9 0.01252 301 1 4 6 5 1 3 7 9 8 8 5 8 3 9 293 0.4 3 5 3 4 4 9 9 8 8 9 9 9 9 9 9 9 8 9 0.1 3 4 2 2 3 6 8 8 6 6 7 8 9 8 8 9 5 9 0.025 2 3 1 1 2 6 7 2 3 3 X 8 9 6 5 6 2 8 0.0125 1 2 0 0 0 2 4 1 1 3 5 6 5 6 2 4 0 294 0.4 4 6 4 5 3 9 8 9 8 9 8 9 9 9 9 9 8 9 0.1 3 5 3 4 2 7 8 5 5 9 8 9 9 8 8 9 7 9 0.025 3 4 1 2 1 5 7 5 4 4 8 8 6 8 6 7 5 9 0.0125 1 3 0 2 0 4 7 X 2 3 7 8 X 7 5 6 5 8 295 0.4 3 5 2 3 3 6 9 8 6 6 8 9 8 8 6 9 7 9 0.1 2 3 1 1 2 4 8 2 4 5 7 9 8 8 5 9 4 9 0.025 X 2 0 0 1 X 6 2 1 5 7 8 7 7 2 6 4 8 0.01250 1 0 0 0 26 1 0 3 6 8 7 7 1 2 1 3 296 0.4 4 3 1 2 2 7 9 9 8 9 8 9 X 8 7 9 4 9 0.1 2 2 0 1 1 5 7 7- 7 5 5 9 X 8 4 8 2 8 0.025 1 1 0 0 0 4 3 1 X 4 5 6 X 3 2 4 1 4 0.0125 1 0 0 0 0 4 3 1 1 3 4 6 X X 1 1 0 3 298 0.4 5 5 4 8 9 9 9 9 9 8 9 0.1 5 3 3 8 9 9 7 9 7 8 9 0.025 2 1 1 X X 5 X X X 3 X 0.0125 2 1 1 5 7 5 5 8 3 2 6 299 0.4 3 3 3 8 9 9 9 9 8 8 9 0.1 3 2 2 6 9 9 5 9 7 5 9 0.025 2 1 1 5 9 7 5 9 5 3 7 0.0125 2 1 1 3 7 3 3 8 2 1 300 0.4 -3 44 8 98 9 9 8 8 9 0.1 2 22 59 7 5 9 6 5 9 0.025 2 1 1 38 6 4 8 4 2 6 0.0125 1 0 1 1 3 1 1 8 2 1 X assessment not possible Table XVII Efficacy of the compounds of the invention in post-emergence application Example Rate G H 0 T Z A A C G I L M S V A D E S [kg /ha]LL0ORR REBMMAA P AA TE LI C E X R YZ AU B SLO0MT E R0G H T M V SA MTEO0A H PI M PM..SC V A_ AWA W XH LB PE U NEE YA G1 218 0.48 5 65 48 86 8 989 98 88 8 0.1 6 4 6 4 4 8 7 X 7 9 8 7 9 8 8 8 8 0.02645643 3 6 66 6986 95 76 6 219 0.47 5 65 57 6.7 898 88 98 7 88 0.1 6 4 5 4 4 7 6 7 8 9 8 8 8 9 7 6 7 8 0.025 5 4 4 3 3 6 5 6 8 9 7 7 7 9 6 4 6 7_ 220 0.4 17 5 6 5 5 7 7 7 8 9 8 9 8 9 9 7 8 8 0.1 6 4 5 4 5 7 6 6 8 9 8 8 8 9 7 5 8 8 0.025 5 4 3 3 4 6 6 6 7 9 7 7 7 9 5 3 6 7 292 0.4 7 5 6 5 5 8 7 7 8 9 8 8 9 9 8 8 8 8 0.1 6 5 5 4 5 7 7 7 8 9 8 8 9 9 8 8 8 8 0.025 5 4 3 3 4 6 6 7 8 9 8 7 7 9 6 6 5 6 293 0.4 5 4 5 4 5 8 8 7 8 9 8 7 9 9 8 8 8 8 0.1 5 4 4 3 4 7 7 7 8 9 8 7 8 9 7 8 7 8 4 3 3 3 3 5 5 7 8 5 8 7 8 9 -5 5 4 6 294 0.4 7 5 6 4 5 8 8 7 8 9 9 8 9 9 8 7 8 8 0.1 5 4 4 4 4 7 7 7 8 9 8 8 9 9 8 7 8 8 0.025 5 4 3 3 3 5 5 6 6 5 8 7 5 9 6 6 5 7 295 0.4 5 4 2 3 3 7 6 7 6 9 8 8 6 9 5 6 5 8 0.1 5 3 2 2 3 5 5 7 5 8 8 8 0 9 4 6 5 6 0.025 4 2 2 2 2 4 4 6 4 6 8 5 X 9 2 4 2 4 296 0.4 6 3 4 3 3 7 7 6 8 9 8 7 9 9 5 3 4 8 0.1 5 2 3 2 2 7 6 6 8 9 7 6 7 9 4 3 3 7 0.025 14 2 2 2 2 4 5 5 7 5 6 .4 4 8 3 3 3 a a a a.
a..
a.
a.
a a.
a a a a.
a. a a a.
298 0.4 5 4 5 8 8 t1 8 0.1 4 3 3 X 7 7 9 8 0.025 3 22 6 65 9 7 299 0.4 6 4 3 9 8 7 9 8 0.1 4 3 2 8 7 7 9 7 0.02513 2 2 54 7 9 7 300 0.4 4 4 3 9 8 7 9 8 0.1 4 3 2 8 7 7 9 8 0.025 2 22 5 46 9 7
Claims (8)
1. A compound of the general formula (I) R 1 A, X NR2 rn (I) wherein A represents an optionally substituted aryl group or an optionally substituted
5- or 6 1, membered nitrogencontaining heteroaromatic group or a difluorobenzodioxolyl group; m represents an integer from 0 to n represents an integer from 0 to 2; R 1 (or each R independently represents a hydrogen atom, an halogen atom, an optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkoxyalkoxy, alkoxyalkyl, dialkoxyalkyl, alkylthio, amino, alkylamino, dialkylamino, alkoxyamino or formamidino group; '15 R 2 (or each R 2 independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl, alkenyl, alkinyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl group or a nitro, cyano, haloalkyl, haloalkoxy, haloalkylthio or SF 5 group, SX represents an oxygen or sulphur atom; and Z represents a nitrogen atom or a CH group; with the provisos that A represents a pyridyl group being substituted by at least one haloalkyl, haloalkoxy or haloalkylthio group,in the event that Z represents N; or ol m and n are 1, R 1 denotes an alkyl, alkoxy or alkylamino group attached in the 4-position and R 2 represents a trifluoromethyl, in the event that Z represent CH. S 2. A compound as claimed in Claim 1 wherein A represents a phenyl, pyridyl or pyrazolyl group being substituted by one or more of the same or different substituents selected from halogen atoms, alkyl groups, alkoxy groups, haloalkyl groups, haloalkoxy groups, haloalkylthio groups and SF 5 groups. t 2 E JlW -48-- 3. A compound of formula I A I A wherein A represents a 2-trifluoromethylpyrid-4-yl or 2-difluoromethoxypyrid-4-yl group, R 1 has the meaning given above; R 2 R 2 and R 2 independently represent a hydrogen atom, a fluorine, chlorine or bromine atom, one or two of them also a trifluoromethyl, trifluormethoxy or a cyano group, R 2 can further be a C 1 -C 4 -alkyl group, particularly tert-butyl. 4. A compound of formula I B R0 X O N (IB) wherein X represents haloalkyl, haloalkoxy or haloalkylthio, and R 1 denotes a halogen atom or an alkyl or alkoxy group. 5. A compound of formula IB selected from the group consisting of
6-methyl-2-(4'-trifuoromethylphenyl)-4-(2"-difluoromethoxy-pyrid-4"-yloxy)pyrimidine 6-ethyl-2-(4'-trifluoromethylphenyl)-4-(2"-trifluoromethyl-pyrid-4"-yloxy)pyrimidine I -4-9- 6-ethyl-2-(4'-trifluoromethylphenyl)A4-2"-(2,2,2-tifluoroethyl)-pyrnd-4'-yloxyjpyrimidine 6-ethyI-2-(4'-trifluoromethylphenyl)-4-(2"-difluoromethoxy-pyrid-4"-yloxy)pyrimidine 6-methoxymethyl-2-(4-trifluoromethylphenyl)-4-(2"-difluoromethoxy-pyid-4"-yloxy)pyrimidine 6-methoxmethyl-2-(4-tifluoromethylphenyl)-4-[2 m -(2,2,2-trifiuoroethyl)-pyrid-4"- yloxy~pyrimidine 6-methyl-2-(4-trifluoromethylphenyl)-4-[2"-(1 ,1I 2,2-tetrafluoroethyl)-pyrid-4"-yloxy~pyrimidine 5-methyl-2-(4'-trifluoromethylphenyl)-4-[2-(1 2,2-tetrafluoroethyl)-pyrid-4"-yloxy]pyrimidine 6-methyl-2-(4'-tifluoromethylphenyl)-4-(2"-difluoromethylthio-pyrid-4'-yloxy)pyrimidine 5-methyl-2-(4'-trifluofomethylphenyl)-4-(2"-difluoromethylthio-pynd-4'-yloxy)pyrimidine 6-methoxy-2-(4'-trifluoromethylphenyl)-4-(2"-difluoromethylthio-pyrid-4- 4oxy)pyrimidine 6. A compound of formula I C AN, N 0 1 N. CF 3 wherein R' denotes alkyl, alkoxy or alkylamino and A has the meaning given in any of the preceding claim.
7. A compound of formula IC selected from the group consisting of S.4-ethyl-2-(4'-trifluorornethylphenyl)-6-.( 4-methyl-2-(4'-trifluoromethylphenyl)-6-(2"-difluoromethoxpyrid-4"-yloxy)pyridine 4-methyl-2-(4'-trifluoromethylphenyl)-6-(2"-trifluoromethylpyrid-4"-yloxy)pyridine 4-methyl-2-(4'-trifluoromethylphenyl)-6-(3"-trifluoromethylphenyloxy)pyridine
8. A 2,6-disubstituted pyridine or pyrimidine derivative according to claim 1, substantially as hereinbefore described with reference to any one of the Examples.
9. A process for the preparation of a 2,6-disubstituted pyridine or pyrimidine derivative according to claim 1, substantially as hereinbefore described with reference to any one of the Examples. A herbicidal composition which comprises at least one compound as claimed in any one of claims 1 to 8 and a carrier and/or a surface-active agent.
11. A method of combating undesired plant growth at a locus, which comprises treating the locus with an effective amount of at least one compound as claimed in any one of claims 1 to 8 or of a composition as claimed in claim
12. The use of an effective amount of a compound of any one of claims 1 to 8 for combating undesired plant growth. 24 November 2000 i, American Cyanamid Company Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON o IR:\LIBZ105322.doc:lam
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU33198/97A AU730571B2 (en) | 1995-01-26 | 1997-08-06 | Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95101057 | 1995-01-26 | ||
| AU42164/96A AU710816B2 (en) | 1995-01-26 | 1996-01-24 | Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines |
| US08/693,422 US5849758A (en) | 1995-05-30 | 1996-08-07 | Herbicidal 2, 6-disubstituted pyridines and 2, 4-disubstituted pyrimidines |
| US08/693422 | 1996-08-07 | ||
| AU33198/97A AU730571B2 (en) | 1995-01-26 | 1997-08-06 | Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU42164/96A Division AU710816B2 (en) | 1995-01-26 | 1996-01-24 | Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU3319897A AU3319897A (en) | 1998-02-12 |
| AU730571B2 true AU730571B2 (en) | 2001-03-08 |
Family
ID=25625883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU33198/97A Ceased AU730571B2 (en) | 1995-01-26 | 1997-08-06 | Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU730571B2 (en) |
-
1997
- 1997-08-06 AU AU33198/97A patent/AU730571B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU3319897A (en) | 1998-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0723960B1 (en) | Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines | |
| CA1110627A (en) | Bis-pyrimidyl-oxy(thio)-benzenes | |
| KR100316679B1 (en) | Herbic Heterocyclic-Substituted Pyridine | |
| US5849758A (en) | Herbicidal 2, 6-disubstituted pyridines and 2, 4-disubstituted pyrimidines | |
| EP0488474B1 (en) | Herbicidal carboxamide derivatives | |
| CA2375303A1 (en) | Herbicidal 2-alkynyl-pyri(mi)dines | |
| AU710816B2 (en) | Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines | |
| US6313072B1 (en) | Herbicidal 2-aryloxy-or 2-arylthio-6-arylpyrimidines | |
| AU730571B2 (en) | Herbicidal 2,6-disubstituted pyridines and 2,4-disubstituted pyrimidines | |
| US6008161A (en) | Herbicidal 2-(hetero)aryloxy-6-arylpyridines and 2-aryl-4-(hetero) aryloxypyrimidines | |
| US5747423A (en) | Herbicidal 6-thienyl and 4-thienyl pyrimidines | |
| US6110871A (en) | Herbicidal cyanopyridines | |
| US5922726A (en) | Herbicidal 6-thienyl pyridines and 4-thienyl pyrimidines | |
| EP0820996A1 (en) | Herbicidal cyanopyridines | |
| IL121492A (en) | 2,6-disubstituted pyrimidines and 2,4-disubstituted pyrimidines and herbicidal compositions containing them | |
| MXPA97006048A (en) | 2.4-disustitute pyrimidines and 2,6-disused pirimidines herbici | |
| US5922738A (en) | Heteroarylpyridine herbicides | |
| CZ290340B6 (en) | Pyrimidine derivatives | |
| US5981437A (en) | Herbicidal substituted pyridine compounds | |
| JPH1087655A (en) | Herbicidal cyanopyridines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGA | Letters patent sealed or granted (standard patent) |