[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2001044236A1 - Herbicidal chroman and thiochroman metal chelates - Google Patents

Herbicidal chroman and thiochroman metal chelates Download PDF

Info

Publication number
WO2001044236A1
WO2001044236A1 PCT/EP2000/011946 EP0011946W WO0144236A1 WO 2001044236 A1 WO2001044236 A1 WO 2001044236A1 EP 0011946 W EP0011946 W EP 0011946W WO 0144236 A1 WO0144236 A1 WO 0144236A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
compound
formula
independently
metal
Prior art date
Application number
PCT/EP2000/011946
Other languages
German (de)
French (fr)
Inventor
Gregory J. Haley
Robin W. Dexter
Stephen S. Szucs
Kannan Rajamoorthi
Original Assignee
Basf Corporation
Basf Aktiengesellschaft
Idemitsu Kosan Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Corporation, Basf Aktiengesellschaft, Idemitsu Kosan Co., Ltd. filed Critical Basf Corporation
Priority to AU28378/01A priority Critical patent/AU2837801A/en
Publication of WO2001044236A1 publication Critical patent/WO2001044236A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
    • 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
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • Thiochroman and dihydrobenzothiophene (DHBT) herbicidal agents are described in U.S. 5,607,898 and WO 97/08164. Said publications describe the herbicidal nature of thiochroman and DHBT compounds. However, the crop safety or selectivity of said thiochroman and DHBT herbicidal agents is not entirely satisfactory.
  • the present invention provides metal chelates of formula I
  • M is a transition metal or an alkaline-earth metal
  • n is an integer of 1, 2 or 3 ;
  • n is an integer of 0 or 1;
  • Ri, R 2 , R 3 and R 4 are each, independently, H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 2 -C 4 alkoxyalkyl;
  • R 5 , R 6 , Rg, and Rio are each independently, H, C 1 -C 4 alkyl, or C 3 -C 6 cycloalkyl;
  • R 7 and R 3 are each, independently, H, C 1 -C 4 alkyl, or C 3 -C 6 cycloalkyl or R and Rs may be taken together with the atom to which they are attached to form a carbonyl group;
  • R 1 is C ⁇ C 3 alkyl, C -C 4 alkenyl, or C 2 -C 4 haloalkenyl;
  • R ⁇ is H, C 1 -C 4 alkyl, C 1 -C 4 alkenyl, or C -C 4 alkoxyalkyl.
  • X is 0, S, SO or S0 ;
  • Ri 3 is H, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl
  • R 14 is H, C 1 -C 4 alkyl or C 2 -C 4 alkenyl or C 2 -C 4 alkynyl;
  • R 15 and Rig are each, independently H, C 1 -C 6 alkyl optionally substituted with one or more C -Cgalkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl or C 3 -C 6 cycloalkyl groups;
  • Z is H, halogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, C -C 4 alkoxyalkyl , C ⁇ C 4 alkoxy or C 1 -C 4 haloalkoxy;
  • p is an integer of 1, 2, or 3 ;
  • herbicidal compositions, methods, and a process to prepare said chelates are also provided.
  • weed science refers to the cha- racteristic by which undesirable species of plants (weeds) are killed or seriously injured in the presence of desirable plant species (crops) without concomittant injury of the desired plant species.
  • weeds undesirable species of plants
  • crops desirable plant species
  • the formula I metal chelates of the present invention demonstrate good herbicidal efficacy against undesirable plant species along with enhanced crop selectivity when compared to the non-chelated compounds exemplified in U.S. Patent Nos . 5,480,858; 5,468,878; 5,468,722; 5,506,194 and 5,607,898 and in WO 97/08164.
  • the formula I chelates of this invention are surprisingly safe in cereal crops such as corn when applied preemergence or post- emergence, preferably postemergence.
  • Preferred compounds of the present invention are those formula I compounds, wherein G is
  • Another group of more preferred formula I compounds are those compounds wherein G is i is 0; X is S0 2 ; and Y is CR ⁇ 3 R 4 ; especially those wherein R i3 and R 14 are hydrogen or C ⁇ -C 4 alkyl, preferably C 1 -C 4 alkyl.
  • halogen as used in the specification and claims designates chlorine, fluorine, bromine or iodine.
  • haloalkyl and haloalkenyl designates an alkyl group, C n H n+ ⁇ , or an alkenyl group, C n H n , which contain from one halogen atom to 2n+l, or 2n, halogen atoms.
  • haloalkoxy designates a OC n H n+ ⁇ group which contains from one to 2n+l halogen atoms .
  • the halogen atoms may be the same or different.
  • metal chelate refers to the coordination of an organic ligand via two or more sigma bonds to a central metal.
  • the oxygen atom of the ligand coordinates to the central metal cation.
  • metal cations include transition metals such as zinc, copper, iron, manganese, titanium, nickel, or any of the commonly occurring transition elements listed in Groups IB through VIIIB on the periodic chart and alkaline-earth metals such as magnesium, calcium, strontium, barium or any of the commonly occurring alkaline-earth elements listed in Group IIA on the periodic chart.
  • Preferred metal cations include copper, zinc, iron, magnesium, calcium, strontium and ba- siu . Said chelation is distinct from the formation of an ionic salt and results in lipophilic compounds with physical properties distinct from those of an ionic salt.
  • Formula I metal chelates wherein G is a cyclohexandione may be prepared by treating a compound of formula IV with an aqueous base and adding about 1/n equivalents of a solution of a metal halide, metal acetate or metal nitrate in water.
  • Formula I transition metal chelates wherein G is an hydroxypyrazole moiety may be prepared in the presence of an aqueous acid, preferably acetic acid, and 1/n equivalents of the appropriate metal salt.
  • Formula I alkaline-earth metal chelates wherein G is an hydroxypyrrole moiety may be prepared in the presence of an aqueous base, such as sodium or potassium hydroxide, and 1/n equivalents of the appropriate metal salt.
  • n represents the valence of the metal employed. The reactions are shown in flow diagram I wherein X 1 is a halide, acetate or nitrate anion.
  • the formula I compounds of the invention are particularly useful for the selective control of undesirable plants species in the presence of crop plants, seeds or other propagating organs.
  • the compounds of this invention are selective in cereal crops such as corn when applied preemergence or postemergence, preferably postemergence.
  • compositions of the invention comprise a herbicidally effective amount of the compound of formula I dispersed or dissolved in an agronomically acceptable inert solid or liquid carrier.
  • inventive compositions may be applied preemergence or postemergence, preferably postemergence.
  • Herbicidally effective amounts may vary according to the prevailing conditions such as weed pressure, crop species, application timing, soil conditions, weather conditions and the like. In general, amounts sufficient to selectively control weeds when applied at rates of about 0.001 kg/ha to 10.0 kg/ha, preferably about 0.003 to 0.50 kg/ha, more preferably about 0.006 to 0.20 kg/ha are suitable.
  • composition of the present invention may take the form of an emulsifiable concentrate, a concentrated emulsion, a wettable powder, a soluble granule, a suspension concentrate, a flowable concentrate or any convenient conventional form useful for herbicide application.
  • the compounds of the invention may be applied in combination with other pesticides such as other herbicides, for instance dinitroa- nilines, preferably pendimethalin, AHAS inhibitors such as imida- zolinones or sulfonyl ureas, protox inhibitors, or any of the commonly employed, commercially available herbicidal agents.
  • the combination may be applied sequentially or concurrently as a tank mix or co-formulation.
  • Compositions of the invention embrace compounds of formula I alone or in combination with a second pesticide as active ingredient, preferably pendimethalin.
  • the terms 1 HNMR, 13 CNMR designate proton and carbon NMR, respectively and the terms IR and MS designate infrared spectrometry and mass spectroscopy, respectively.
  • a stirred suspension of 4 , 4-dimethyl-5, 8-dimethyl-6- (l-hydroxy-3- oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide (0.500 g, 1.33 mmol) in water is treated with 1 molar sodium hydroxide (1.33 ml, 1.33 mmol) until the reaction mixture is homogeneous. Then, a solution of iron (III) chloride hexahydrate (0.119 g, 0.44 mmol) in water is added dropwise to the reaction mixture.
  • a stirred suspension of 4 , 4-dimethyl-5 , 8-dimethyl-6- (l-hydroxy-3- oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide (0.376 g, 1.00 mmol) in water is treated with 1 molar sodium hydroxide (1.05 ml, 1.05 mmol) until the reaction mixture is homogeneous.
  • a solution of zinc acetate dihydrate (0.120 g, 0.55 mmol) in water is added dropwise to the reaction mixture and stirred for two hours at room temperature.
  • the reaction mixture is filtered to give a white solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.280 g, mp >220° C, 62% yield) .
  • the product is identified by X HNMR, IR, and elemental analyses.
  • the reaction mixture is filtered to give a solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.430 g, mp >220° C, 40% yield) .
  • the product is identified by iH MR, IR, MS and elemental analyses .
  • a stirred suspension of 4-methoximino-5-methyl-6- (l-hydroxy-3- oxocyclohexane-2-yl) carbonyl hiochroman-1, 1-dioxide (1.00 g, 2.65 mmol) in water is treated with 1 molar sodium hydroxide (2.65 ml, 2.65 mmol) and stirred for 30 minutes.
  • a solution of copper (II) chloride dihydrate (0.225 g, 1.32 mmol) in water is added dropwise to the filtrate and stirred for 40 minutes at room temperature.
  • reaction mixture is filtered to give a blue solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (1.21 g, mp >220° C, 92% yield).
  • the product is identified by IR, and elemental analyses.
  • the reaction mixture is filtered to give a brown solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.950 g, mp >220° C, 91% yield)
  • the product is identified by IR and elemen- tal analyses.
  • reaction mixture is filtered to give a yellow solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.400 g, mp >220° C, 46% yield) .
  • the product was identified by 1 HNMR, IR, and elemental analyses.
  • a stirred suspension of 2 , 3-dihydro-5- [ (5-hydroxy-l-methyl- pyrazol-4-yl) carbonyl] -3,3, 4-trimethylbenzo [b] thiophene, 1, 1-dioxide (0.48 g, 1.42 mmol) in water is treated with an aqueous sodium hydroxide solution (3.3 mL, 1.65 mmol) and filtered.
  • the filtrate is treated with a solution of calcium nitrate (0.17 g, 0.73 mmol) in water dropwise over a five-minute period, stirred for sixteen hours at room temperature, and filtered.
  • a stirred suspension of 2 , 3-dihydro-5- [ (5-hydroxy-l-methyl- pyrazol-4-yl) carbonyl] -3,3, 4-trimethylbenzo [b] thiophene, 1, 1-dioxide (0.46 g, 1.39 mmol) in water is treated with a sodium hydroxide solution (3.1 mL, 1.50 mmol) and filtered.
  • the filtrate is treated with a solution of barium chloride dihydrate (0.17 g, 0.69 mmol) in 4 mL water dropwise over a five-minute period, stirred at room temperature for sixteen hours and filtered.
  • the herbicidal activity and enhanced postemergence selectivity of the compounds of the present invention are evaluated and compared to the corresponding free ligand, i.e. the non-chelated compound, by the following tests wherein a variety of dicotyledonous and monocotyledonous plants are treated with test compounds.
  • test plants are grown in jiffy flats for about two weeks.
  • the test compounds are dispersed in 50/50 acetone/ water mixtures containing a 0.5% TWEEN®20, a polyoxyethylene sorbitan monolaurate surfactant of Atlas Chemical Industries, in sufficient quantities to provide the equivalent of about 0.0157 kg to 0.500 kg per hectare of active compound when applied to the plants through a spray nozzle operating at 40 psi for a predetermined time.
  • the plants are placed on greenhouse benches and are cared for in accordance with conventional green- house procedures. From four to five weeks after treatment, the seedling plants are examined and rated according to the rating system set forth below. Data obtained are reported in Table I below. Where more than one test is involved for a given compound, the data are averaged. The results are shown in Table I.
  • Compound A 4- (Methoximino) -5-methyl-6- (l-ethyl-5-hydroxy- pyrazol-4-yl) carbonylthiochroman-1, 1-dioxide
  • the herbicidal activity and enhanced pre-emergence selectivity of the compounds of the present invention are evaluated and compared to the corresponding free ligand, i.e. the non-chelated compound, by the following tests wherein a variety of dicotyledonous and monocotyledonous plants are treated with test compounds.
  • the postemergence herbicidal activity and enhanced postemergence selectivity of compounds of the present invention are evaluated and compared to the corresponding free ligand, i.e. the non-che- lated compound, by the following test wherein a variety of dico- tyledonous and monocotyledonous plants are treated with the test compounds .
  • AMBEL Ragweed Common Ambrosia artemisii folia, L.

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)

Abstract

The present invention provides transition metal and alkaline-earth metal chelates of formula (I), wherein G is (1) or (2) X is O, S, SO or SO2; Y is CR13R14, CHOR15, C=NOR16 or C=O; further provided are compositions and methods utilizing formula (I) compounds for the control of undesirable plant species with enhanced cereal crop safety.

Description

HERBICIDAL CHROMAN AND THIOCHROMAN METAL CHELATES
Weeds cause tremendous global economic losses by reducing crop yields and lowering crop quality. Worldwide, agronomic crops must compete with hundreds of weed species. Herbicides, used to combat these weed species are now standard technology on farms and ranches. The proper agronomic use of herbicides results in increased crop yields and quality and, concomitantly, increases production and harvesting efficiency.
In spite of the commercial herbicides available, damage to crops caused by weeds still occurs. In addition, often herbicides do not provide a sufficient margin of safety for the crop, thus damaging the crop as well as the weeds . Accordingly, there is an ongoing need to create more crop-selective as well as more effective herbicidal agents.
Thiochroman and dihydrobenzothiophene (DHBT) herbicidal agents are described in U.S. 5,607,898 and WO 97/08164. Said publications describe the herbicidal nature of thiochroman and DHBT compounds. However, the crop safety or selectivity of said thiochroman and DHBT herbicidal agents is not entirely satisfactory.
It is therefore an object of the present invention to provide compounds which demonstrate herbicidal activity in conjunction with enhanced crop safety.
The present invention provides metal chelates of formula I
Figure imgf000002_0001
(I) wherein G is
Figure imgf000003_0001
M is a transition metal or an alkaline-earth metal;
n is an integer of 1, 2 or 3 ;
m is an integer of 0 or 1;
Ri, R2, R3 and R4 are each, independently, H, C1-C4 alkyl, C1-C4 haloalkyl or C2-C4 alkoxyalkyl;
R5, R6, Rg, and Rio are each independently, H, C1-C4 alkyl, or C3-C6 cycloalkyl;
R7 and R3 are each, independently, H, C1-C4 alkyl, or C3-C6 cycloalkyl or R and Rs may be taken together with the atom to which they are attached to form a carbonyl group;
R1 is Cι~C3 alkyl, C -C4 alkenyl, or C2-C4 haloalkenyl;
Rι is H, C1-C4 alkyl, C1-C4 alkenyl, or C -C4 alkoxyalkyl.
X is 0, S, SO or S0 ;
Y is CR3Ri4, CHOR15, C=NORi6 or C=0;
Ri3 is H, C1-C4 alkyl or C1-C4 haloalkyl;
R14 is H, C1-C4 alkyl or C2-C4 alkenyl or C2-C4 alkynyl;
R15 and Rig are each, independently H, C1-C6 alkyl optionally substituted with one or more C -Cgalkenyl, C2-C6alkynyl, C1-C6 haloalkyl or C3-C6cycloalkyl groups;
Z is H, halogen, Cι-C4alkyl, Cι-C4haloalkyl, C -C4alkoxyalkyl , Cι~C4alkoxy or C1-C4 haloalkoxy; and
p is an integer of 1, 2, or 3 ; or
the tautomers thereof . Also provided are herbicidal compositions, methods, and a process to prepare said chelates.
The term safety or selectivity in weed science refers to the cha- racteristic by which undesirable species of plants (weeds) are killed or seriously injured in the presence of desirable plant species (crops) without concomittant injury of the desired plant species. The use of herbicides frequently causes a varying degree of crop injury. Such crop damage is a problem that genera - tes a continuous need for more selective herbicides worldwide. This is especially true of crops such as cereals which are often unacceptably damaged by herbicides designed to protect said crops against invasive weeds.
Surprisingly, it has now been found that the formula I metal chelates of the present invention demonstrate good herbicidal efficacy against undesirable plant species along with enhanced crop selectivity when compared to the non-chelated compounds exemplified in U.S. Patent Nos . 5,480,858; 5,468,878; 5,468,722; 5,506,194 and 5,607,898 and in WO 97/08164. In particular, the formula I chelates of this invention are surprisingly safe in cereal crops such as corn when applied preemergence or post- emergence, preferably postemergence.
Preferred compounds of the present invention are those formula I compounds, wherein G is
Figure imgf000004_0001
and X is S0 . More preferred compounds of formula I are those compounds wherein G is
Figure imgf000004_0002
m is an integer of 1; X is S0 ; and Y is C=NORιs; especially those wherein Rig is hydrogen or C1-C4 alkyl. Another group of more preferred formula I compounds are those compounds wherein G is
Figure imgf000005_0001
i is 0; X is S02; and Y is CRι3R4; especially those wherein Ri3 and R14 are hydrogen or Cι-C4 alkyl, preferably C1-C4 alkyl.
The term halogen as used in the specification and claims designates chlorine, fluorine, bromine or iodine. The term haloalkyl and haloalkenyl designates an alkyl group, CnHn+ι, or an alkenyl group, CnHn, which contain from one halogen atom to 2n+l, or 2n, halogen atoms. Similarly, the term haloalkoxy designates a OCnHn+ι group which contains from one to 2n+l halogen atoms . The halogen atoms may be the same or different.
The term, metal chelate refers to the coordination of an organic ligand via two or more sigma bonds to a central metal. In the present invention, the oxygen atom of the ligand coordinates to the central metal cation. Examples of such metal cations include transition metals such as zinc, copper, iron, manganese, titanium, nickel, or any of the commonly occurring transition elements listed in Groups IB through VIIIB on the periodic chart and alkaline-earth metals such as magnesium, calcium, strontium, barium or any of the commonly occurring alkaline-earth elements listed in Group IIA on the periodic chart. Preferred metal cations include copper, zinc, iron, magnesium, calcium, strontium and ba- siu . Said chelation is distinct from the formation of an ionic salt and results in lipophilic compounds with physical properties distinct from those of an ionic salt.
Compounds of formula I may exist in enolic tautomeric forms that may give rise to geometric isomers around the enolic double bond. Furthermore, in certain cases the substituents Ri, R , R3, R4, R5, Rδ, R7, Re, R9 , RiO' R11 and Rι may contribute to optical isomerism hereby giving rise to stereoisomeric forms. All such forms are embraced by the present invention.
Formula I metal chelates wherein G is a cyclohexandione may be prepared by treating a compound of formula IV with an aqueous base and adding about 1/n equivalents of a solution of a metal halide, metal acetate or metal nitrate in water. Formula I transition metal chelates wherein G is an hydroxypyrazole moiety may be prepared in the presence of an aqueous acid, preferably acetic acid, and 1/n equivalents of the appropriate metal salt. Formula I alkaline-earth metal chelates wherein G is an hydroxypyrrole moiety may be prepared in the presence of an aqueous base, such as sodium or potassium hydroxide, and 1/n equivalents of the appropriate metal salt. For each of the foregoing preparations, n represents the valence of the metal employed. The reactions are shown in flow diagram I wherein X1 is a halide, acetate or nitrate anion.
Flow Diagram I
Figure imgf000006_0001
( I )
Figure imgf000006_0002
Syntheses of compounds IV or V can be found in U.S. Patent Nos. 5,480,858; 5,468,878; 5,468,722; 5,506,194; and 5,607,898 and in WO 97/08164.
Among the inventive compounds of formula I are:
4 , 4-dimethyl-5, 8-dimethyl-6- (l-hydroxy-3-oxocyclohexene-2-yl) car- bonylthiochroman-1, 1-dioxide, iron (+3) chelate;
4 , 4-dimethyl-5 , 8-dimethyl-6- (l-hydroxy-3-oxocyclohexene-2-yl) car- bonylthiochroman-1, 1-dioxide, copper (+2) chelate; 4, 4-dimethyl-5, 8-dimethyl-6- (l-hydroxy-3-oxocyclohexene-2-yl) car- bonylthiochroman-1, 1-dioxide, zinc (+2) chelate;
3 , 3-dimethyl-4-oxo-5-methyl-6- (l-hydroxy-3-oxocyclohe- xene-2-yl) carbonylthiochroman-1, 1-dioxide, zinc (+2) chelate;
3 , 3-dimethyl-4-oxo-5-methyl-6- (l-hydroxy-3-oxocyclohe- xene-2-yl) carbonylthiochroman-1, 1-dioxide, copper (+2) chelate;
3 , 3-dimethyl-4-oxo-5-methyl-6- (l-hydroxy-3-oxocyclohe- xene-2-yl) carbonylthiochroman-1, 1-dioxide, iron (+3) chelate;
4-methoximino-5-methyl-6- (l-hydroxy-3-oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide, zinc (+2) chelate;
4-methoximino-5-methyl-6- (l-hydroxy-3-oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide, copper (+2) chelate;
4-methoximino-5-methyl-6- (1-hydroxy, 3-oxocyclohexane-2-yl) carbo- nylthiochroman-1, 1-dioxide, iron (+3) chelate;
4-methoximino-5-methyl-6- (l-ethyl-5-hydroxypyrazol-4-yl) carbo- nylthiochroman-1, 1-dioxide, iron +3) chelate;
4-methoximino-5-methyl-6- (l-ethyl-5-hydroxypyrazol-4-yl) carbo- nylthiochroman-1, 1-dioxide, zinc (+2) chelate;
4-methoximino-5-methyl-6- (l-ethyl-5-hydroxypyrazol-4-yl) carbo- nylthiochroman-1, 1-dioxide, copper (+2) chelate;
2 , 3-dihydro-5- [ (5-hydroxy-l-methylpyrazol-4-yl) carbonyl] -
3 , 3 , 4-trimethylbenzo [b] thiophene, 1, 1-dioxide, zinc (+2) chelate;
2, 3-dihydro-5- [ (5-hydroxy-l-methylpyrazol-4-yl) carbonyl] - 3 , 3 , 4-trimethylbenzo [b] thiophene, 1, 1-dioxide, copper (+2) chelate;
2, 3-dihydro-5- [ (5-hydroxy-l-methylpyrazol-4-yl) carbonyl] - 3 , 3 , 4-trimethylbenzo [b] thiophene, 1, 1-dioxide, iron (+3) chelate;
2 , 3-dihydro-5- [ (5-hydroxy-l-methylpyrazol-4-yl) carbonyl] -
3 , 3 , 4-trimethylbenzo [b] thiophene, 1, 1-dioxide, magnesium (+2) chelate; 2,3-dihydro-5- [ (5-hydroxy-l-methylpyrazol-4-yl) carbonyl] - 3 , 3, 4-trimethylbenzo [b] thiophene, 1, 1-dioxide, calcium (+2) chelate; and
2, 3-dihydro-5- [ (5-hydroxy-l-methylpyrazol-4-yl) carbonyl] - 3, 3, 4-trimethylbenzo [b] thiophene, 1, 1-dioxide, barium (+2) chelate.
Advantageously, it has been found that the formula I compounds of the invention are particularly useful for the selective control of undesirable plants species in the presence of crop plants, seeds or other propagating organs. In particular, the compounds of this invention are selective in cereal crops such as corn when applied preemergence or postemergence, preferably postemergence.
The compounds of the invention may be applied to the foliage of undesirable plants or to the soil or water containing seeds or other propagating organs thereof in the form of a solid or liquid herbicidal composition. Compositions of the invention comprise a herbicidally effective amount of the compound of formula I dispersed or dissolved in an agronomically acceptable inert solid or liquid carrier. The inventive compositions may be applied preemergence or postemergence, preferably postemergence. Herbicidally effective amounts may vary according to the prevailing conditions such as weed pressure, crop species, application timing, soil conditions, weather conditions and the like. In general, amounts sufficient to selectively control weeds when applied at rates of about 0.001 kg/ha to 10.0 kg/ha, preferably about 0.003 to 0.50 kg/ha, more preferably about 0.006 to 0.20 kg/ha are suitable.
The composition of the present invention may take the form of an emulsifiable concentrate, a concentrated emulsion, a wettable powder, a soluble granule, a suspension concentrate, a flowable concentrate or any convenient conventional form useful for herbicide application.
The compounds of the invention may be applied in combination with other pesticides such as other herbicides, for instance dinitroa- nilines, preferably pendimethalin, AHAS inhibitors such as imida- zolinones or sulfonyl ureas, protox inhibitors, or any of the commonly employed, commercially available herbicidal agents. The combination may be applied sequentially or concurrently as a tank mix or co-formulation. Compositions of the invention embrace compounds of formula I alone or in combination with a second pesticide as active ingredient, preferably pendimethalin. In order to further illustrate the invention, the following examples are set forth below. The terms 1HNMR, 13CNMR designate proton and carbon NMR, respectively and the terms IR and MS designate infrared spectrometry and mass spectroscopy, respectively.
EXAMPLE 1
Preparation of 4 , 4-dimethyl-5, 8-dimethyl-6- (l-hydroxy-3-oxocyclo- hexene-2-yl) carbonylthiochroman-1, 1-dioxide, iron (+3) chelate
Figure imgf000009_0001
A stirred suspension of 4 , 4-dimethyl-5, 8-dimethyl-6- (l-hydroxy-3- oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide (0.500 g, 1.33 mmol) in water is treated with 1 molar sodium hydroxide (1.33 ml, 1.33 mmol) until the reaction mixture is homogeneous. Then, a solution of iron (III) chloride hexahydrate (0.119 g, 0.44 mmol) in water is added dropwise to the reaction mixture. After stirring for 30 minutes at room temperature, the reaction mixture was filtered through filter paper to afford the title product as a brown solid (0.350 g, 67% yield) which was dried overnight in a vacuum oven at 45° C (0.350 g, mp >220° C, 67% yield) . The product is identified by IR, MS and elemental analy- ses.
EXAMPLE 2
Preparation of 4 , 4-dimethyl-5 , 8-dimethyl-6- (l-hydroxy-3-oxocyclo- hexene-2-yl) carbonylthiochroman-1, 1-dioxide, copper (+2) chelate
Figure imgf000009_0002
A stirred suspension of 4, 4-dimethyl-5, 8-dimethyl-6- (l-hydroxy-3- oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide (0.500 g, 1.33 mmol) in water is treated with 1 molar sodium hydroxide (1.33 ml, 1.33 mmol) until the reaction mixture is homogeneous. A solution of copper (II) chloride dihydrate (0.113 g, 0.66 mmol) in water (10 ml) is added dropwise to the reaction mixture. After stirring for 60 minutes at room temperature, the reaction mixture is filtered to give a blue solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.350 g, mp >220° C, 65% yield). The product is identified by IR, MS and elemental analyses.
EXAMPLE 3
Preparation of 4 , 4-dimethyl-5 , 8-dimethyl-6- ( l-hydroxy-3-oxocyclo- hexene-2-yl) carbonylthiochroman-1, 1-dioxide, zinc (+2) chelate
Figure imgf000010_0001
A stirred suspension of 4 , 4-dimethyl-5 , 8-dimethyl-6- (l-hydroxy-3- oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide (0.376 g, 1.00 mmol) in water is treated with 1 molar sodium hydroxide (1.05 ml, 1.05 mmol) until the reaction mixture is homogeneous. A solution of zinc acetate dihydrate (0.120 g, 0.55 mmol) in water is added dropwise to the reaction mixture and stirred for two hours at room temperature. The reaction mixture is filtered to give a white solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.280 g, mp >220° C, 62% yield) . The product is identified by XHNMR, IR, and elemental analyses.
EXAMPLE 4
Preparation of 3 , 3-dimethyl-4-oxo-5-methyl-6- ( l-hydroxy-3-oxocy- clohexene-2-yl) carbonyl thiochroman-1 , 1-dioxide, zinc (+2 ) chelate
Figure imgf000010_0002
A stirred suspension of 3 , 3-dimethyl-4-oxo-5-methyl-6- (1- hydroxy-3-oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide (0.900 g, 2.58 mmol) in water is treated with 1 molar sodium hydroxide (2.58 ml, 2.58 mmol) and stirred for 30 minutes. After filtering the reaction mixture, a solution of zinc acetate dihydrate (0.283 g, 1.29 mmol) in water is added dropwise to the filtrate and stirred for an additional 60 minutes at room temperature. The reaction mixture is filtered to give a solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.430 g, mp >220° C, 40% yield) . The product is identified by iH MR, IR, MS and elemental analyses .
EXAMPLE 5
Preparation of 3 , 3-dimethyl-4-oxo-5-methyl-6- (l-hydroxy-3-oxocy- clohexene-2-yl) carbonylthiochroman-1, 1-dioxide, copper (+2) chelate
Figure imgf000011_0001
A stirred suspension of 3 , 3-dimethyl-4-oxo-5-methyl-6- (1- hydroxy-3-oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide (0.900 g, 2.58 mmol) in water is treated with 1 molar sodium hydroxide (2.58 ml, 2.58 mmol) and stirred for 30 minutes. After filtering the reaction mixture, a solution of copper (II) chloride dihydrate (0.220 g, 1.29 mmol) in water is added dropwise to the filtrate. After stirring for 60 minutes at room temperature, the reaction mixture is filtered to give a blue solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.78 g, mp >220° C, 79% yield). The product is identified by IR and elemental analyses.
EXAMPLE 6
Preparation of 3 , 3-dimethyl-4-oxo-5-methyl-6- ( l-hydroxy-3-oxocy- clohexene-2-yl) carbonylthiochroman-1, 1-dioxide, iron (+3) chelate
Figure imgf000012_0001
A stirred suspension of 3 , 3-dimethyl-4-oxo-5-methyl-6- (1- hydroxy-3-oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide (0.900 g, 2.58 mmol) in water is treated with 1 molar sodium hydroxide (2.58 ml, 2.58 mmol) and stirred for 30 minutes. After filtering the reaction mixture, a solution of iron (III) chloride hexahydrate (0.232 g, 0.86 mmol) in water is added dropwise to the filtrate. After stirring for an additional 60 minutes at room temperature, the reaction mixture is filtered to give a solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.66 g, mp >220° C, 65% yield) . The product is identified by IR, MS and elemental analyses .
EXAMPLE 7
Preparation of 4-methoximino-5-methyl-6- ( l-hydroxy-3-oxoeyelohe- xene-2-yl) carbonylthiochroman-1, 1-dioxide, zinc (+2) chelate
Figure imgf000012_0002
A stirred suspension of 4-methoximino-5-methyl-6- (l-hydroxy-3- oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide (1.00 g, 2.65 mmol) in water is treated with 1 molar sodium hydroxide (2.65 ml, 2.65 mmol) and stirred for 30 minutes. A solution of zinc acetate dihydrate (0.290 g, 1.32 mmol) in water is added dropwise to the filtrate and stirred for 40 minutes at room temperature. The reaction mixture is filtered to give a solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.920 g, mp >220° C, 85% yield). The product is identified by ^NMR, IR, and elemental analyses. EXAMPLE 8
Preparation of 4-methoximino-5-methyl-6- ( l-hydroxy-3-oxocyclohe- xene-2-yl) carbonylthiochroman-1, 1-dioxide, copper (+2) chelate
Figure imgf000013_0001
A stirred suspension of 4-methoximino-5-methyl-6- (l-hydroxy-3- oxocyclohexane-2-yl) carbonyl hiochroman-1, 1-dioxide (1.00 g, 2.65 mmol) in water is treated with 1 molar sodium hydroxide (2.65 ml, 2.65 mmol) and stirred for 30 minutes. A solution of copper (II) chloride dihydrate (0.225 g, 1.32 mmol) in water is added dropwise to the filtrate and stirred for 40 minutes at room temperature. The reaction mixture is filtered to give a blue solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (1.21 g, mp >220° C, 92% yield). The product is identified by IR, and elemental analyses.
EXAMPLE 9
Preparation of 4-methoximino-5-methyl-6- (l-hydroxy-3-oxocyclohe- xene-2-yl) carbonylthiochroman-1, 1-dioxide, iron (+3) chelate
Figure imgf000013_0002
A stirred suspension of 4-methoximino-5-methyl-6- (l-hydroxy-3- oxocyclohexene-2-yl) carbonylthiochroman-1, 1-dioxide (1.00 g, 2.65 mmol) in water is treated with 1 molar sodium hydroxide (2.65 ml, 2.65 mmol) and stirred for 30 minutes. Then, a solution of iron (III) chloride hexahydrate (0.238 g, 0.99 mmol) in water (10 ml) is added dropwise to the filtrate and stirred for 40 minutes at room temperature. The reaction mixture is filtered to give a brown solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.950 g, mp >220° C, 91% yield) The product is identified by IR and elemen- tal analyses.
EXAMPLE 10
Preparation of 4-methoximino-5-methyl-6- (l-ethyl-5-hydroxy- pyrazol-4-yl) carbonylthiochroman-1, 1-dioxide, iron +3) chelate
Figure imgf000014_0001
A solution of 4-methoximino-5-methyl-6- (l-ethyl-5-hydroxy- pyrazol-4-yl) carbonylthiochroman-1, 1-dioxide (0.400 g, 1.06 mmol) in warm acetic acid is treated with a solution of iron (III) chloride hexahydrate (0.0572 g, 0.35 mmol) in water and stirred overnight at room temperature. The reaction mixture is filtered to give a dark red solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.420 g, mp >220° C, 33% yield). The product is identified by IR and elemental analyses.
EXAMPLE 11
Preparation of 4-methoximino-5-methyl-6- (l-ethyl-5-hydroxy- pyrazol-4-yl) carbonylthiochroman-1, 1-dioxide, zinc (+2) chelate
Figure imgf000014_0002
A solution of 4-methoximino-5-methyl-6- (l-ethyl-5-hydroxy- pyrazol-4-yl) carbonylthiochroman-1, 1-dioxide (0.400 g, 1.06 mmol) in warm acetic acid (2 ml) is treated with zinc acetate dihydrate (0.116 g, 0.53 mmol) and the reaction mixture heated until homogeneous. After adding water (2 ml) the reaction mixture is again heated to redissolve precipitated product, then cooled to room temperature and is stirred overnight at room temperature. The reaction mixture is filtered to give a yellow solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.400 g, mp >220° C, 46% yield) . The product was identified by 1HNMR, IR, and elemental analyses.
EXAMPLE 12
Preparation of 4-methoximino-5-methyl-6- (l-ethyl-5-hydroxy- pyrazol-4-yl) carbonylthiochroman-1, 1-dioxide, copper (+2) chelate
Figure imgf000015_0001
A solution of 4-methoximino-5-methyl-6- ( l-ethyl-5-hydroxy- pyrazol-4-yl) carbonylthiochroman-1, 1-dioxide (0.755 g, 2.00 mmol) in warm acetic acid (15 ml) is treated with a solution of copper (II) acetate monohydrate (0.170 g, 1.00 mmol) in water. The solution is allowed to cool to room temperature and stirred for one hour. The reaction mixture is filtered to give a blue solid which is washed with water and dried overnight in a vacuum oven at 45° C to afford the title product (0.800 g, mp >220° C, 98.7% yield) . The product was identified by IR, and elemental analyses .
EXAMPLES 13 - 16
Preparation of 2 , 3-dihydro-5- [ (5-hydroxy-l-methyl- pyrazol-4-yl) carbonyl] -3 , 3-dimethylbenzo [b] thiophene, 1 , 1-dioxide, chelates
Figure imgf000015_0002
Using essentially the same procedures described in Examples 10, 11 and 12, and substituting the appropriate dihydrobenzothiophene substrate, the following chelates are obtained and identified by XHNMR, IR, MS and elemental analyses.
Figure imgf000016_0001
Figure imgf000016_0003
EXAMPLE 17
Preparation of 2 , 3-dihydro-5- [ (5-hydroxy-l-methyl- pyrazol-4-yl) carbonyl] -3,3, 4-trimethylbenzo [b] thiophene, 1, 1-dioxide, magnesium (+2) chelate
Figure imgf000016_0002
A stirred suspension of 2 , 3-dihydro-5- [ (5-hydroxy-l-methyl- pyrazol-4-yl) carbonyl] -3,3, 4-trimethylbenzo [b] thiophene, 1, 1-dioxide (0.50 g, 1.5 mmol) in water is treated with 3.5 L of an aqueous sodium hydroxide (1.99 mmol) solution and filtered. The filtrate is treated with a solution of magnesium bromide etherate
(0.19 g, 0.75 mmol) in water dropwise over a five-minute period, stirred at room temperature for six hours and filtered. The fil- tercake is washed with water and dried overnight in a vacuum oven at 45-50°C to give the title product as a yellow solid, 0.44 g
(85% yield), mp 260°, identified by IR, iHNMR, "CNMR, MS, X-ray emission and elemental analyses as a hydrate.
EXAMPLE 18
Preparation of 2 , 4-dihydro-5- [ (5-hydroxy-l-methylpyrazol-4- yl) carbonyl] -3,3, 4-trimethylbenzo [b] thiophene, 1 , 1-dioxide, calcium (+2) chelate
Figure imgf000017_0001
A stirred suspension of 2 , 3-dihydro-5- [ (5-hydroxy-l-methyl- pyrazol-4-yl) carbonyl] -3,3, 4-trimethylbenzo [b] thiophene, 1, 1-dioxide (0.48 g, 1.42 mmol) in water is treated with an aqueous sodium hydroxide solution (3.3 mL, 1.65 mmol) and filtered. The filtrate is treated with a solution of calcium nitrate (0.17 g, 0.73 mmol) in water dropwise over a five-minute period, stirred for sixteen hours at room temperature, and filtered. The filter- cake is washed with water and dried overnight in a vacuum oven at 45-50°C to give the title product as a pale yellow solid, 0.41 g (82% yield), mp 260°, identified by IR, ^NMR, 13CNMR, MS, X-ray emission and elemental analyses as a hydrate.
EXAMPLE 19
Preparation of 2, 4-dihydro-5- [ (5-hydroxy-l-methylpyrazol-4- yl) carbonyl] -3 , 3 , 4-trimethylbenzo [b] thiophene, 1, 1-dioxide, ba- rium (+2) chelate
Figure imgf000017_0002
A stirred suspension of 2 , 3-dihydro-5- [ (5-hydroxy-l-methyl- pyrazol-4-yl) carbonyl] -3,3, 4-trimethylbenzo [b] thiophene, 1, 1-dioxide (0.46 g, 1.39 mmol) in water is treated with a sodium hydroxide solution (3.1 mL, 1.50 mmol) and filtered. The filtrate is treated with a solution of barium chloride dihydrate (0.17 g, 0.69 mmol) in 4 mL water dropwise over a five-minute period, stirred at room temperature for sixteen hours and filtered. The filtrate is washed with water and dried overnight in a vacuum oven at 45-50°C to give the title product as a pale yellow solid, 0.48 g (86% yield), mp 260°, identified by IR, i-HNMR, 13CNMR, MS, X-ray emission and elemental analyses as a hydrate. EXAMPLE 20
Comparative postemergence herbicidal evaluation of test compounds
The herbicidal activity and enhanced postemergence selectivity of the compounds of the present invention are evaluated and compared to the corresponding free ligand, i.e. the non-chelated compound, by the following tests wherein a variety of dicotyledonous and monocotyledonous plants are treated with test compounds.
In the tests, seedling plants are grown in jiffy flats for about two weeks. The test compounds are dispersed in 50/50 acetone/ water mixtures containing a 0.5% TWEEN®20, a polyoxyethylene sorbitan monolaurate surfactant of Atlas Chemical Industries, in sufficient quantities to provide the equivalent of about 0.0157 kg to 0.500 kg per hectare of active compound when applied to the plants through a spray nozzle operating at 40 psi for a predetermined time. After spraying, the plants are placed on greenhouse benches and are cared for in accordance with conventional green- house procedures. From four to five weeks after treatment, the seedling plants are examined and rated according to the rating system set forth below. Data obtained are reported in Table I below. Where more than one test is involved for a given compound, the data are averaged. The results are shown in Table I.
COMPARATIVE COMPOUNDS
Compound A = 4- (Methoximino) -5-methyl-6- (l-ethyl-5-hydroxy- pyrazol-4-yl) carbonylthiochroman-1, 1-dioxide
Compound B = 2 , 3-Dihydro-5- [ (5-hydroxy-1-methyl -pyrazol-4-yl! carbonyl] -3,3, 4-trimethyl -benzo [b] thio-phene- 1, 1-dioxide
Herbicide Rating Scale
Rating Meaning % Control
9 Complete Kill 100
8 Approaching Complete Kill 91-99
7 Good Herbicidal Effect 80-90
6 Herbicidal Effect 65-79
5 Definite Injury 45-64
4 Injury 30-44
3 Moderate Effect 16-29
2 Slight Effect 6-15
1 Trace Effect 1-5
0 No Effect 0
PLANT SPECIES EMPLOYED
Figure imgf000019_0001
TABLE I
COMPARATIVE POSTEMERGENCE HERBICIDAL EVALUATION
Example Rate
Number (kg/ha) ABUTH AMBEL CASOB CHEAL IPOSS ECHCG PANDI SETVI ZEAMX
1 0.0500 9.0 6.0 7.0 9.0 6.0 8.0 3.0 4.0 0.0
0.0125 9.0 5.0 4.0 9.0 5.0 6.0 0.0 0.0 0.0
2 0.0500 9.0 6.0 6.0 9.0 6.0 9.0 4.0 2.0 0.0
0.0125 9.0 5.0 6.0 9.0 4.0 7.0 2.0 0.0 0.0
3 0.0500 8.0 7.0 6.0 9.0 6.0 8.0 3.0 2.0 0.0
0.0125 7.0 6.0 1.0 9.0 2.0 7.0 1.0 0.0 0.0
4 0.0500 8.0 9.0 7.0 9.0 4.0 8.0 5.0 2.0 0.0
0.0125 7.0 6.0 2.0 9.0 1.0 7.0 0.0 3.0 0.0
5 0.0500 9.0 9.0 4.0 9.0 4.0 8.0 5.0 1.0 0.0
0.0125 6.0 7.0 0.0 9.0 1.0 7.0 0.0 0.0 0.0
6 0.0500 9.0 9.0 4.0 9.0 3.0 9.0 2.0 0.5 0.0
0.0125 7.0 7.0 0.0 9.0 2.0 7.0 0.0 0.0 0.0
7 0.0500 9.0 9.0 5.0 9.0 7.0 8.0 6.0 3.0
Figure imgf000020_0001
0.0
0.0125 9.0 7.0 0.0 9.0 4.0 7.0 5.0 3.0 0.0
Figure imgf000021_0001
Example Rate ABUTH AMBEL CASOB CHEAL IPOSS ECHCG PANDI SETVI ZEAMX Number (kg/ha)
Compound 0.0500 7.9 8.6 6, .4 9, .0 2, .1 8.2 8.1 8.7 4.2
A 0.0125 6.1 8.3 2, .7 9, .0 2 .2 7.4 6.9 8.4 1.2
13 0.0500 9.0 8.0 7.5 8.0 8.5 0.3
0.0125 7.0 7.0 7.0 6.5 8.0 0.0
14 0.0500 7.5 8.0 7.0 8.0 8.5 0.0
0.0125 6.5 7.5 7.5 7.0 7.0 0.0
15 0.0500 5.0 7.0 8.0 8.0 9.0 0.0
0.0125 4.0 7.0 4.0 7.0 5.0 0.0
16 0.0500 7.0 8.0 8.0 7.0 8.0 0.0 0.0125
Compound 0.0500 7.5 8.0 8.0 8.5 8.5 1.8
B 0.0125 7.0 7.5 8.0 8.5 8.0 0.3
Figure imgf000022_0001
EXAMPLE 21
Comparative preemergence herbicidal evaluation of test compounds
The herbicidal activity and enhanced pre-emergence selectivity of the compounds of the present invention are evaluated and compared to the corresponding free ligand, i.e. the non-chelated compound, by the following tests wherein a variety of dicotyledonous and monocotyledonous plants are treated with test compounds.
In these tests, seeds of a variety of monocotyledonous and dicotyledonous plants are separately mixed with potting soil and planted on top of approximately one inch of soil in separate pint cups. After planting, the cups are sprayed with the selected aqueous acetone solution containing test compound in sufficient quantity to provide the equivalent of about 0.0156 to 0.500 kg per hectare of test compound per cup. The treated cups are then placed on greenhouse benches, watered and cared for in accordance with conventional greenhouse procedures. From four to five weeks after treatment, the tests are terminated and each cup is examined and rated according to the rating system provided in Example 20. The comparative compounds and plant species employed are also as described above in Example 20. The results obtained are shown in Table II.
Figure imgf000024_0001
TABLE II
COMPARATIVE PREEMERGENCE HERBICIDAL EVALUATION
Example Rate
Number (kg/ha) ABUTH AMBEL CASOB CHEAL IPOSS ECHCG PANDI SETVI ZEAMX
0. .0500 8.0 7.0 2.0 9.0 6.0 4.0 8.0 2.5 0.0
0, .0125 5.0 4.0 9.0 2.0 0.0 3.0 0.0 0.0
0. .0500 9.0 7.0 3.0 9.0 6.0 6.0 8.0 3.5 0.0
0, .0125 5.0 4.0 9.0 2.0 0.0 3.0 0.0 0.0
0. .0500 9.0 7 7..00 5 5..00 9 9..00 6 6..00 8 8..00 8 8..00 1 1..00 0 0..00
0. .0125 7.0 7.0 9.0 9.0 4.0 0.0 5.0 0.0 0.0
0. .0500 8.0 9.0 5.0 9.0 5.0 5.0 5.0 1.5 2.0
0, .0125 0.0 5.0 0.0 3.0 0.0 0.0 0.0 0.0 0.0
0. .0500 7.0 8.0 2.0 9.0 8.0 7.0 2.0 1.0 0.0
0, .0125 0.0 6.0 9.0 1.0 0.0 0.0 0.0 0.0
0.0500 7.0 7.0 9.0 4.0 0.0 8.0 1.0 0.0
0.0500 9.0 8.0 0.0 9.0 7.0 7.0 8.0 1.0 0.0
0.0125 2.0 7.0 0.0 9.0 1.0 0.0 0.0 0.0 0.0
Figure imgf000025_0001
Example Rate ABUTH AMBEL CASOB CHEAL IPOSS ECHCG PANDI SETVI ZEAMX
Number (kg/ha)
Compound 0.0500 8.9 8.7 3. .5 9, .0 3. .0 8.4 8.2 8.6 0.3
A 0.0125 7.0 6.1 0, .4 7. .8 2, .0 3.4 5.6 4.4 0.3
13 0.0500 9.0 8.0 7.5 8.0 8.5 0.8
0.0125 7.0 7.0 7.0 6.5 8.0 0.0
14 0.0500 7.5 8.0 7.0 8.0 8.5 0.0
0.0125 6.5 7.5 7.5 7.0 7.0 0.0
15 0.0500 4.0 7.0 7.0 7.0 4.0 0.0
0.0125 1.0 0.0 0.0 2.0 2.0 0.0
16 0.0500 5.0 6.0 5.0 7.0 9.0 0.0
0.0125 0.0 0.0 0.0 1.0 1.0 0.0
Compound 0.0500 7.5 8.0 8.0 8.5 8.5 1.8
B 0.0125 7.0 7.5 8.0 8.5 8.0 0.3
EXAMPLE 22
Comparative postemergence herbicidal evaluation of test compounds
The postemergence herbicidal activity and enhanced postemergence selectivity of compounds of the present invention are evaluated and compared to the corresponding free ligand, i.e. the non-che- lated compound, by the following test wherein a variety of dico- tyledonous and monocotyledonous plants are treated with the test compounds .
In this evaluation, seeds of a variety of monocotyledonous and dicotyledenous plants are grown for about two weeks in 26 x 52 x 6.5 cm plastic flats with plastic inserts containing 8 x 8 x 6 cm cells. Test compounds are dispersed in 80/20 acetone/water mixtures containing 1% methylated sunflower oil (v/v) in quantities calculated to provide the equivalent of 100 grams to 6 grams per hectare of compound when applied to the plants over a predetermi- ned time. Treatments are applied with a belt sprayer calibrated to deliver a spray volume of 400 L/ha. Visual ratings on all weed and crop species are made 18 days after treatment using the rating scale shown below. The results obtained are shown in Table III.
COMPARATIVE COMPOUND
Compound B = 2 , 3-Dihydro-5- [ (5-hydroxy-l-methyl- pyrazol-4-yl) carbonyl] -3,3, 4-trimethyl* benzo [b] thiophene-1, 1-dioxide
HERBICIDE RATING SCALE
Rating Meaning % Control
9 Complete Kill 100 8 Approaching Complete Kill 91-99 7 Good Herbicidal Effect 80-90 6 Herbicidal Effect 65-79 5 Definite Injury 45-64 4 Injury 30-44 3 Moderate Effect 16-29 2 Slight Effect 6-15 1 Trace Effect 1-5 0 No Effect 0 PLANT SPECIES EMPLOYED
Header Common Name Scientific Name Abbr.
ABUTH Nelvetleaf Abutilon theophrasti,
Medic.
AMBEL Ragweed, Common Ambrosia artemisii folia, L.
IPOHE Morningglory, Ivyleaf Ipomoea hederacea, (L)
Jacq.
XANST Cocklebur Xanthium strumarium
ECHCG Barnyardgrass Echinochloa crus-galli, (L)
Beau
PANDI Panicum, Fall Panicum dichotomif lorum,
Michx
SETVI Foxtail, Green Setaria viridis, (L)Beauv
ZEAMXK Corn, Field Zea mays L. var dekalb 623
ZEAMX Corn, Field Zea mays L. (Sammel-Be- zeichnung)
Figure imgf000029_0001
TABLE III
COMPARATIVE POSTEMERGENCE HERBICIDAL EVALUATION
Example Rate
Number (kg/ha) ABUTH AMBEL IPOHE XANST ECHCG PANDI SETVI ZEAMXK ZEAMX
13 0.100 9.0 9.0 7.0 9.0 9.0 9.0 9.0 0.0 0.0
0.050 9.0 9.0 7.0 9.0 9.0 9.0 8.0 0.0 0.0
14 0.100 9.0 9.0 5.0 9.0 9.0 9.0 8.0 0.0 0.0
0.050 9.0 9.0 5.0 9.0 9.0 9.0 8.0 0.0 0.0
17 0.100 9.0 9.0 7.0 9.0 9.0 9.0 9.0 0.0 0.0
0.050 8.0 9.0 6.0 9.0 9.0 9.0 9.0 0.0 0.0
18 0.100 9.0 9.0 7.0 9.0 9.0 9.0 8.0 0.0 0.0
0.050 9.0 9.0 7.0 9.0 9.0 9.0 7.0 0.0 0.0
19 0.100 9.0 9.0 8.0 9.0 9.0 9.0 9.0 2.0 2.0
0.050 9.0 9.0 6.0 9.0 9.0 9.0 9.0 2.0 0.0
Compound 0.100 8.0 9.0 6.0 9.0 9.0 9.0 9.0 4.0 4.0
B 0.050 8.0 9.0 6.0 9.0 9.0 9.0 9.0 3.0 3.0

Claims

Claims :
A compound of formula I
Figure imgf000030_0001
( I ) wherein G is
Figure imgf000030_0002
M is a transition metal or an alkaline-earth metal;
n is an integer of 1, 2 or 3 ;
m is an integer of 0 or 1;
Rl, R , R3 and R are each independently, H, Cι~C alkyl, C1-C4 haloalkyl or C -C4 alkoxyalkyl;
R5, Rς, Rg , and Rio are each independently, H, C1-C4 alkyl, or C3-C6 cycloalkyl;
R7 and R$ are each independently, H, C1-C4 alkyl, or C3-C6 cycloalkyl or R and Rs may be taken together with the atom to which they are attached to form a carbonyl group;
R11 is Cι~C alkyl, C -C4 alkenyl, or C2-C4 haloalkenyl;
Rι is H, C -C4 alkyl, C1-C4 alkenyl, or C2-C4 alkoxyalkyl.
X is 0, S, SO or S02;
Y is CRi3Ri4 , CHOR15 , C=NOR g or C=0;
Rι3 is H, C1-C4 alkyl or C1-C4 haloalkyl ; Ri4 is H, C1-C4 alkyl or C2-C alkenyl or C2-C4 alkynyl;
R15 and R16 are each, independently H, Cι~Cg alkyl optionally substituted with one or more C -Cgalkenyl, C2-C6alkynyl, Cι~Cg haloalkyl or C3-Cgcycloalkyl groups;
Z is H, halogen, Cι-C4alkyl, Cι-C4haloalkyl ; C -C alkoxyalkyl , Cι~C4alkoxy or C1-C4 haloalkoxy; and
p is an integer of 1, 2, or 3; or
the tautomers thereof .
2. The compound according to claim 1 wherein M is Cu, Zn, Fe, Mg, Ca, Sr or Ba.
3. The compound according to claim 1 wherein
G is
Figure imgf000031_0001
4. The compound according to claim 3 wherein
m is 1; X is S02; and Y is C=NOR15.
5. The compound according to claim 3 wherein
m is 0; X is S0 ; and Y is CRι3Rι4.
6. The compound according to claim 4 wherein Rg is H or Cι~C4alkyl.
7. The compound according to claim 5 wherein Rι3 and R14 are each independently C ~C4alkyl .
8. A method for the control of undesirable plant species which comprises applying to the foliage of said plants or to the soil or water containing seeds or other propagating organs thereof, a herbicidally effective amount of a compound of formula I
Figure imgf000032_0001
( I )
10 wherein X, Y, Z, G, Rl t R2, R3 , R4, M, m, n, and p are as described in claim 1.
. The method according to claim 8 wherein said compound is applied to the foliage of said plants.
15
10. The method according to claim 8 wherein said undesirable plant species are in the presence of a crop.
11. The method according to claim 10 wherein said crop plant is a 20 cereal crop plant.
12. The method according to claim 11 wherein said cereal crop plant is Zea mays .
25 13. The method according to claim 8 having a formula I compound wherein G is
Figure imgf000032_0002
14. The method according to claim 13 having a formula I compound 35 wherein m is 1; X is S02; and Y is C=NORιg.
15. The method according to claim 13 having a formula I compound wherein m is 0; X is S0 ; and Y is CR3Rι4.
40 16. The method according to claim 12 wherein the herbicidally effective amount is about 0.001 kg/ha to 10.0 kg/ha.
17. A herbicidal composition which comprises an agriculturally acceptable carrier and a herbicidally effective amount of a 45 compound of formula I
Figure imgf000033_0001
(I)
10 wherein X, Y, Z, G, Ri, R2, R3 , R4, M, m, n, and p are as described in claim 1.
The composition according to claim 17 wherein G is
Figure imgf000033_0002
20 19. The composition according to claim 18 wherein m is 1; X is
Figure imgf000033_0003
20. The composition according to claim 18 wherein m is 0; X is S02; and Y is CRι3Rι4.
25
21. A process for the preparation of a compound of formula I
Figure imgf000033_0004
(I)
35 wherein G is
1
Figure imgf000033_0005
5 M is a transition metal or an alkaline-earth metal; n is an integer of 1, 2 or 3 ;
m is an integer of 0 or 1;
Ri, R2, R3 and R4 are each, independently, H, C1-C4 alkyl, C1-C4 haloalkyl or C2-C4 alkoxyalkyl;
R5, Rg, R9, and Ro are each, independently, H, C1-C4 alkyl, or C3-Cg cycloalkyl;
R7 and Re are each, independently, H, C1-C4 alkyl, or C3-Cg cycloalkyl or R7 and Rs may be taken together with the atom to which they are attached to form a carbonyl group;
Rll is Cι~C3 alkyl , C -C4 alkenyl , or C2- 4 haloalkenyl ;
Rι is H, C1-C4 alkyl, C1-C4 alkenyl, or C -C4 alkoxyalkyl,
X is 0, S, SO or S0 ;
Y is CRι3Ri4 , CHOR15 , C=NORιg or C=0 ;
Ri3 is H, C1-C4 alkyl or C1-C4 haloalkyl ;
R14 is H, C1-C4 alkyl or C -C4 alkenyl or C -C4 alkynyl ;
R15 and Rig are each, independently, H, Ci-Cgalkyl optionally substituted with one or more C -Cgalkenyl, C -Cgalkynyl, Ci-Cghaloalkyl or C3-Cgcycloalkyl groups;
Z is H, halogen, Cι~C4alkyl, Cι~C4haloalkyl; C2-C4alkoxyalkyl, Cι~C4alkoxy or C1-C4 haloalkoxy; and
p is an integer of 1, 2, or 3
which process comprises:
(a) treating a compound of formula IV
Figure imgf000034_0001
(IV) with a base to form an anion;
(b) treating said anion with a metal halide, metal acetate or metal nitrate of formula Mn(X1)n wherein X1 is Cl, Br, F, I, 0C0CH3 or N03; M is a transition metal or an alkaline- earth metal; and n is an integer of 1, 2 or 3 to form the compound of formula I wherein G is
Figure imgf000035_0001
(c) treating a compound of formula V
Figure imgf000035_0002
with an aqueous acid; and
(d) treating said compound with a metal halide, metal acetate or metal nitrate of formula Mn(X1)n wherein X1 is Cl, Br, F, I, OCOCH3 or N0 ; M is a transition metal or an alkaline-earth metal; and n is an integer of 1, 2 or 3 to form the compound of formula I wherein G is
Figure imgf000035_0003
PCT/EP2000/011946 1999-12-02 2000-11-29 Herbicidal chroman and thiochroman metal chelates WO2001044236A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU28378/01A AU2837801A (en) 1999-12-02 2000-11-29 Herbicidal chroman and thiochroman metal chelates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US45310299A 1999-12-02 1999-12-02
US09/453,102 1999-12-02

Publications (1)

Publication Number Publication Date
WO2001044236A1 true WO2001044236A1 (en) 2001-06-21

Family

ID=23799212

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/011946 WO2001044236A1 (en) 1999-12-02 2000-11-29 Herbicidal chroman and thiochroman metal chelates

Country Status (2)

Country Link
AU (1) AU2837801A (en)
WO (1) WO2001044236A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003073856A1 (en) * 2002-03-01 2003-09-12 W. Neudorff Gmbh Kg Transition metal chelates as selective herbicide
US8076267B2 (en) 2002-03-01 2011-12-13 W. Neudorff Gmbh Kg Enhancers for water soluble selective auxin type herbicides
WO2011154541A1 (en) * 2010-06-11 2011-12-15 W. Neudorff Gmbh Kg Selective herbicides with activator adjuvants
US9980479B2 (en) 2004-06-07 2018-05-29 Syngenta Crop Protection, Llc Method of reducing nematode damage

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5468878A (en) * 1992-10-15 1995-11-21 Idemitsu Kosan Co., Ltd. Cyclohexanedione derivatives
US5506194A (en) * 1992-07-13 1996-04-09 Idemitsu Kosan Co., Ltd. Pyrazole derivatives and herbicidal compositions
EP0712853A1 (en) * 1993-08-02 1996-05-22 Idemitsu Kosan Company Limited Pyrazole derivative
WO1997001550A1 (en) * 1995-06-29 1997-01-16 E.I. Du Pont De Nemours And Company Herbicidal ketals and spirocycles
WO1997012885A1 (en) * 1995-10-04 1997-04-10 Idemitsu Kosan Co., Ltd. Pyrazole derivatives
EP0841335A1 (en) * 1995-07-12 1998-05-13 Idemitsu Kosan Company Limited Triketone derivatives
WO1998028291A1 (en) * 1996-12-20 1998-07-02 E.I. Du Pont De Nemours And Company Substituted benzothiopyranes salts and their use as herbicides
EP0949257A1 (en) * 1996-12-27 1999-10-13 Idemitsu Kosan Company Limited Cyclohexanedione derivatives and herbicides prepared therefrom

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5506194A (en) * 1992-07-13 1996-04-09 Idemitsu Kosan Co., Ltd. Pyrazole derivatives and herbicidal compositions
US5468878A (en) * 1992-10-15 1995-11-21 Idemitsu Kosan Co., Ltd. Cyclohexanedione derivatives
EP0712853A1 (en) * 1993-08-02 1996-05-22 Idemitsu Kosan Company Limited Pyrazole derivative
WO1997001550A1 (en) * 1995-06-29 1997-01-16 E.I. Du Pont De Nemours And Company Herbicidal ketals and spirocycles
EP0841335A1 (en) * 1995-07-12 1998-05-13 Idemitsu Kosan Company Limited Triketone derivatives
WO1997012885A1 (en) * 1995-10-04 1997-04-10 Idemitsu Kosan Co., Ltd. Pyrazole derivatives
EP0970956A1 (en) * 1995-10-04 2000-01-12 Idemitsu Kosan Company Limited Pyrazole derivatives
WO1998028291A1 (en) * 1996-12-20 1998-07-02 E.I. Du Pont De Nemours And Company Substituted benzothiopyranes salts and their use as herbicides
EP0949257A1 (en) * 1996-12-27 1999-10-13 Idemitsu Kosan Company Limited Cyclohexanedione derivatives and herbicides prepared therefrom

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003073856A1 (en) * 2002-03-01 2003-09-12 W. Neudorff Gmbh Kg Transition metal chelates as selective herbicide
US6972273B2 (en) 2002-03-01 2005-12-06 W. Neudorff Gmbh Kg Composition and method for selective herbicide
US8076267B2 (en) 2002-03-01 2011-12-13 W. Neudorff Gmbh Kg Enhancers for water soluble selective auxin type herbicides
US9980479B2 (en) 2004-06-07 2018-05-29 Syngenta Crop Protection, Llc Method of reducing nematode damage
WO2011154541A1 (en) * 2010-06-11 2011-12-15 W. Neudorff Gmbh Kg Selective herbicides with activator adjuvants
US8987171B2 (en) 2010-06-11 2015-03-24 W. Neudorff Gmbh Kg Selective herbicides with activator adjuvants

Also Published As

Publication number Publication date
AU2837801A (en) 2001-06-25

Similar Documents

Publication Publication Date Title
CA2252543C (en) Benzene derivatives substituted by heterocycles and herbicides
CA1316175C (en) 3-(substituted phenyl) pyrazole derivatives, salts thereof, herbicides therefrom, and process for producing said derivatives or salts
DE60026318T2 (en) ISOXAZOLINE DERIVATIVES AND HERBICIDES CONTAINING THESE AS AN ACTIVE INGREDIENT
CN107629035B (en) Pyrazolone compound or salt thereof, herbicide composition and application
IE70909B1 (en) 1-{[o-(cyclopropylcarbonyl)phenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl) urea and method for the preparation thereof
EP0447055B1 (en) 3-(Substituted phenyl)pyrazole derivatives, a process for producing the same, herbicidal composition containing the same and method of controlling weeds using said composition
RO104332B1 (en) Method for preparation of benzamide derivatives
EP0282303B1 (en) 1,5-diphenyl-1h-1,2,4-triazole-3-carboxamide derivatives and herbicidal composition containing the same
KR20170029528A (en) Herbicidal pyridazinone derivatives
EA023765B1 (en) Herbicidal compounds
CS203162B2 (en) Fungicide and process for preparing efective compounds thereof
KR890003849B1 (en) Substituted pyridine herbicides
CN110963973A (en) Triketone compound containing quinazolinedione fragment, preparation method and application thereof, and herbicide
WO2001044236A1 (en) Herbicidal chroman and thiochroman metal chelates
JPS6365669B2 (en)
JP2752141B2 (en) 2- (3-pyridyl) propanenitrile derivatives, their production and use
CN112694452A (en) Aryl formamide compound containing chiral oxysulfide or salt thereof, preparation method, herbicidal composition and application
JPS63295555A (en) Substituted tetrahydrophthalimides, manufacture and use as herbicide
HU203187B (en) Herbicidal compositions comprising 2,6-substituted pyridinecarboxylic acid derivatives as active ingredient
JPS61200968A (en) Heterocyclic compound, manufacture and fungicidal or plant growth regulator composition
CN107629046B (en) Pyrazolone compound or salt thereof, herbicide composition and application
EP3288924A1 (en) Herbicidal compounds
JPS59181290A (en) Triazole or imidazole compound, manufacture and fungicidal or plant growth regulant composition
JPS62249978A (en) Triazole compound, manufacture and plant growth regulant composition
HU204664B (en) Herbicidal compositions comprising 2,6-disubstituted 1,2- or 1,6-dihydro-3,5-pyridinedicarboxylic acid derivatives

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)