U.S. patent application number 09/821261 was filed with the patent office on 2002-05-30 for benzoylpyrazoles and their use as herbicides.
Invention is credited to Almsick, Andreas van, Auler, Thomas, Bieringer, Hermann, Preub, Rainer, Schmitt, Monika, Thurwachter, Felix, Willms, Lothar.
Application Number | 20020065200 09/821261 |
Document ID | / |
Family ID | 7637164 |
Filed Date | 2002-05-30 |
United States Patent
Application |
20020065200 |
Kind Code |
A1 |
Schmitt, Monika ; et
al. |
May 30, 2002 |
Benzoylpyrazoles and their use as herbicides
Abstract
Benzoylpyrazoles of the formula (I) and their use as herbicides
are described. 1 In the formula (I), R.sup.1, R.sup.2, R.sup.3,
R.sup.4, and R.sup.5 are various radicals and n is from 0 to 2.
Inventors: |
Schmitt, Monika; (Frankfurt,
DE) ; Almsick, Andreas van; (Oberursel, DE) ;
Preub, Rainer; (Idstein, DE) ; Willms, Lothar;
(Hofheim, DE) ; Auler, Thomas; (Bad Soden, DE)
; Bieringer, Hermann; (Eppstein, DE) ;
Thurwachter, Felix; (Bad Homburg, DE) |
Correspondence
Address: |
FROMMER LAWRENCE & HAUG LLP
745 Fifth Avenue
New York
NY
10151
US
|
Family ID: |
7637164 |
Appl. No.: |
09/821261 |
Filed: |
March 29, 2001 |
Current U.S.
Class: |
504/282 ;
548/367.1 |
Current CPC
Class: |
C07D 231/20 20130101;
A01N 43/56 20130101 |
Class at
Publication: |
504/282 ;
548/367.1 |
International
Class: |
A01N 043/56; C07D
231/22 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2000 |
DE |
10016116.2 |
Claims
What is claimed is:
1. A benzoylpyrazole of the formula (I) or a salt thereof 11in
which R.sup.1 is methyl or ethyl; R.sup.2 is trifluoromethyl;
R.sup.3 is hydrogen, methyl or ethyl; R.sup.4 is methyl, ethyl or
n-propyl; R.sup.5 is hydrogen,
(C.sub.1-C.sub.6)-alkylcarbonylmethyl,
(C.sub.1-C.sub.4)-alkylsulfonyl, phenylsulfonyl, benzyl,
benzoylmethyl, (C.sub.1-C.sub.3)-alkylsulfonyl which is mono- or
polysubstituted by halogen, phenylsulfonyl which is monosubstituted
by methyl or halogen, benzyl which is substituted by halogen,
nitro, methyl or methoxy or benzoylmethyl which is mono- or
polysubstituted by halogen, nitro, methyl or methoxy and n is 0, 1,
or 2.
2. A benzoylpyrazole as claimed in claim 1, in which R.sup.1 is
methyl and R.sup.3 is hydrogen or methyl.
3. A benzoylpyrazole as claimed in claim 1, in which R.sup.4 is
methyl or ethyl.
4. A benzoylpyrazole as claimed in claim 1, in which R.sup.5 is
hydrogen, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl,
phenylsulfonyl, 4-methylphenylsulfonyl, benzyl, benzoylmethyl,
nitrobenzoylmethyl or 4-fluorobenzoylmethyl.
5. A benzoylpyrazole as claimed in claim 1, in which R.sup.3 is
methyl.
6. A herbicidal composition which comprises a herbicidally
effective amount of at least one compound of the formula (I) as
claimed in claim 1.
7. The herbicidal composition as claimed in claim 6 in a mixture
with formulation auxiliaries.
8. A method for controlling undesirable plants, which comprises
applying an effective amount of at least one compound of the
formula (I) as claimed in claim 1 or a herbicidal composition as
claimed in claim 6 or 7 on to the plants or the location of the
undesirable vegetation.
9. A method for the use of compounds of the formula (I) as claimed
in claim 1 or of herbicidal compositions as claimed in claim 6 or 7
for controlling undesirable plants.
10. The method as claimed in claim 9, wherein the compounds of the
formula (I) are used for controlling undesirable plants in crops of
useful plants.
11. The method as claimed in claim 10, wherein the useful plants
are transgenic useful plants.
Description
[0001] The invention relates to the technical field of the
herbicides, in particular of the herbicides for the selective
control of broad-leaved weeds and weed grasses in crops of useful
plants.
[0002] It is already known from various publications that certain
benzoylpyrazoles have herbicidal properties. Thus, the German
laid-open publication D-A 25 13 750 describes
1-alkyl4-benzoyl-5-hydroxypyrazoles and
1-alkyl-4-benzoyl-5-thiopyrazoles which are preferably substituted
on the phenyl ring by one or two radicals. In addition to hydrogen,
radicals mentioned as being preferred for the 2-position are
bromine, chlorine, iodine, methyl and nitro, for the 3-position
methoxy, for the 4-position chlorine, methoxy, methylsulfonyl and
nitro and for the 5-position methyl. The hydroxy or thio group of
the compounds described therein is optionally substituted by
various radicals, such as acyl radicals. J5 5033-45 mentions
further 5-hydroxypyrazoles and 5-thiopyrazoles in which the hydroxy
or thio group is in principle substituted by various radicals. U.S.
Pat. No. 4,643,757 discloses, as herbicides,
1-methyl-4-benzoylpyrazoles which preferably carry halogen, nitro
or sulfonylmethyl in the 2-position of the phenyl ring, hydrogen,
halogen or methyl in the 3-position and halogen or sulfonylmethyl
in the 4-position. EP-A 0 203 428 discloses, as herbicides,
1-alkyl-4-benzoylpyrazoles which preferably carry halogen or methyl
in the 2-position of the phenyl ring, hydrogen or methyl in the
3-position and halogen or sulfonylmethyl in the 4-position.
[0003] However, the compounds known from these publications
frequently have an insufficient herbicidal activity and/or
insufficient crop plant compatibility. Accordingly, it is an object
of the present invention to provide herbicidally active compounds
having improved herbicidal properties and improved crop plant
compatibility than the compounds known from the prior art.
[0004] It has now been found that certain 4-benzoylpyrazoles which
are substituted at specific positions by selected radicals are
particularly suitable for use as herbicides. Accordingly, the
present invention provides compounds of the formula (I) or salts
thereof 2
[0005] in which
[0006] R.sup.1 is methyl or ethyl;
[0007] R.sup.2 is trifluoromethyl;
[0008] R.sup.3 is hydrogen, methyl or ethyl;
[0009] R.sup.4 is methyl, ethyl or n-propyl;
[0010] R.sup.5 is hydrogen, (C.sub.1-C.sub.6)-alkylcarbonylmethyl,
(C.sub.1-C.sub.4)-alkylsulfonyl, phenylsulfonyl, benzyl,
benzoylmethyl, (C.sub.1-C.sub.3)-alkylsulfonyl which is mono- or
polysubstituted by halogen, phenylsulfonyl which is monosubstituted
by methyl or halogen, benzyl which is substituted by halogen, nitro
or methoxy or benzoylmethyl which is mono- or polysubstituted by
halogen, nitro, methyl or methoxy and
[0011] n is 0, 1, or 2.
[0012] If R.sup.5 is hydrogen the compounds of the formula (I)
according to the invention can, depending on external conditions
such as solvent and pH, be present in different tautomeric
structures: 3
[0013] Depending on the type of substituents, the compounds of the
formula (I) may contain an acidic proton which can be removed by
reaction with a base. Suitable bases are, for example, hydrides,
hydroxides and carbonates of lithium, sodium, potassium, magnesium
and calcium, and also ammonia and organic amines, such as
triethylamine and pyridine. Such salts are likewise provided by the
invention.
[0014] In formula (I) and all other formulae hereinbelow, alkyl
radicals having more than two carbon atoms can be straight-chain or
branched. Alkyl radicals are, for example, methyl, ethyl, n- or
isopropyl, n-, iso, t- or 2-butyl, pentyls, hexyls, such as
n-hexyl, isohexyl and 1,3-dimethylbutyl. Halogen is fluorine,
chlorine, bromine or iodine. Tosyl is 4-methylphenylsulfonyl.
[0015] If a group is polysubstituted by radicals, this is to be
understood as meaning that this group is substituted by one or more
identical or different of the radicals mentioned.
[0016] Depending on the type and the attachment of the
substituents, the compounds of the formula (I) can be present as
stereoisomers. If, for example, one or more asymmetrically
substituted carbon atoms are present, enantiomers and diastereomers
may occur. Stereoisomers can be obtained from the mixtures obtained
in the preparation by customary separation methods, for example by
chromatographic separation processes. It is also possible to
prepare stereoisomers by using stereoselective reactions, employing
optically active starting materials and/or auxiliaries. The
invention also relates to all stereoisomers and mixtures thereof
which are embraced by the formula (I) but not defined
specifically.
[0017] Of particular interest are compounds of the formula (I), in
which n is 2.
[0018] Preference is given to compounds of the formula (I), in
which
[0019] R.sup.1 is methyl and
[0020] R.sup.3 is hydrogen or methyl.
[0021] Preference is also given to compounds of the formula (I), in
which
[0022] R.sup.4 is methyl or ethyl.
[0023] Particular preference is given to compounds of the formula
(I), in which
[0024] R.sup.5 is methylsulfonyl, ethylsulfonyl, n-propylsulfonyl,
phenylsulfonyl, 4-methylphenylsulfonyl, benzyl, benzoylmethyl,
nitrobenzoylmethyl or 4-fluorobenzoylmethyl.
[0025] Particular preference is likewise given to compounds of the
formula (I), in which
[0026] R.sup.5 is hydrogen.
[0027] Very particular preference is given to compounds of the
formula (I), in which
[0028] R.sup.3 is methyl.
[0029] In all of the formulae mentioned hereinbelow, the
substituents and symbols have the same meaning as described under
formula (I), unless defined otherwise. Compounds according to the
invention in which R.sup.5 is hydrogen can be prepared, for
example, by the process shown in Scheme 1 and known from DE-A 25 13
750 by base-catalyzed reaction of a benzoyl halide with a
pyrazolone, or according to the process shown in Scheme 2 and
known, for example, from EP-A 0 186 117 by base-catalyzed reaction
of a benzoyl halide with a pyrazolone and subsequent rearrangement.
4 5
[0030] Compounds according to the invention in which R.sup.5 is
different from hydrogen are, according to Scheme 3, expediently
prepared from the compounds obtainable according to Scheme 1 or 2
by base-catalyzed reaction with a suitable acylating agent
R.sup.5--X in which X is a leaving group such as halogen. Such
methods are known, for example, from DE-A 25 13 750. 6
[0031] The starting materials used in the schemes above are either
commercially available or can be prepared by methods known per se.
Thus, the pyrazolones of the formula (II) can be prepared, for
example, by the methods described in EP-A 0 240 001 and J. Prakt.
Chem. 315, 382, (1973), and the benzoyl chlorides of the formula
(III) can be prepared by the process as described in EP-A 0 527
036.
[0032] The compounds of the formula (I) according to the invention
have an outstanding herbicidal activity against a broad spectrum of
economically important monocotyledonous and dicotyledonous harmful
plants. The active compounds also act efficiently on perennial
weeds which produce shoots from rhizomes, root stocks or other
perennial organs and which are difficult to control. In this
context, it is generally immaterial whether the substances are
applied pre-sowing, pre-emergence or post-emergence. Specifically,
examples may be mentioned of some representatives of the
monocotyledonous and dicotyledonous weed flora which can be
controlled by the compounds according to the invention, without
these being a restriction to certain species. Examples of weed
species on which the active compounds act efficiently are, from
amongst the monocotyledons, Avena, Lolium, Alopecurus, Phalaris,
Echinochloa, Digitaria, Setaria and also Cyperus species from the
annual sector and from amongst the perennial species Agropyron,
Cynodon, Imperata and Sorghum, and also perennial Cyperus
species.
[0033] In the case of the dicotyledonous weed species, the spectrum
of action extends to species such as, for example, Galium, Viola,
Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Sida,
Matricaria and Abutilon from amongst the annuals, and Convolvulus,
Cirsium, Rumex and Artemisia in the case of the perennial weeds.
The active compounds according to the invention also effect
outstanding control of harmful plants which occur under the
specific conditions of rice growing such as, for example,
Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus.
If the compounds according to the invention are applied to the soil
surface prior to germination, then the weed seedlings are either
prevented completely from emerging, or the weeds grow until they
have reached the cotyledon stage but then their growth stops, and,
eventually, after three to four weeks have elapsed, they die
completely. If the compounds according to the invention are applied
to the soil surface prior to germination, then the weed seedlings
are either prevented completely from emerging, or the weeds grow
until they have reached the cotyledon stage but then their growth
stops, and, eventually, after three to four weeks have elapsed,
they die completely. In particular, the compounds according to the
invention exhibit excellent activity against Apera spica venti,
Chenopodium album, Lamium purpureum, Polygonum convulvulus,
Stellaria media, Veronica hederifolia, Veronica persica, Viola
tricolor and against Amaranthus, Galium and Kochia species.
[0034] Although the compounds according to the invention have an
excellent herbicidal activity against monocotyledonous and
dicotyledonous weeds, crop plants of economically important crops
such as, for example, wheat, barley, rye, rice, corn, sugarbeet,
cotton and soya, are not damaged at all, or only to a negligible
extent. In particular, they have excellent compatibility in
cereals, such as wheat, barley and corn, in particular wheat. For
these reasons, the present compounds are highly suitable for
selectively controlling undesired plant growth in plantings for
agricultural use or in plantings of ornamentals.
[0035] Owing to their herbicidal properties, these active compounds
can also be employed for controlling harmful plants in crops of
known or still to be developed genetically engineered plants. The
transgenic plants generally have particularly advantageous
properties, for example resistance to certain pesticides, in
particular certain herbicides, resistance to plant diseases or
causative organisms of plant diseases, such as certain insects or
microorganisms such as fungi, bacteria or viruses. Other particular
properties relate, for example, to the quantity, quality,
storage-stability, composition and to specific ingredients of the
harvested product. Thus, transgenic plants having an increased
starch content or a modified quality of the starch or those having
a different fatty acid composition of the harvested produce are
known.
[0036] The use of the compounds of the formula (I) according to the
invention or their salts in economically important transgenic crops
of useful and ornamental plants, for example of cereal, such as
wheat, barley, rye, oats, millet, rice, maniok and corn, or else in
crops of sugarbeet, cotton, soya, rapeseed, potato, tomato, pea and
other vegetable species is preferred. The compounds of the formula
(I) can preferably be used as herbicides in crops of useful plants
which are resistant or which have been made resistant by genetic
engineering toward the phytotoxic effects of the herbicides.
[0037] Conventional ways for preparing novel plants which have
modified properties compared to known plants comprise, for example,
traditional breeding methods and the generation of mutants.
Alternatively, novel plants having modified properties can be
generated with the aid of genetic engineering methods (see, for
example, EP-A 0 221 044, EP-A 0 131 624). For example, there have
been described several cases of
[0038] genetically engineered changes in crop plants in order to
modify the starch synthesized in the plants (for example WO
92/11376, WO 92/14827, WO 91/19806),
[0039] transgenic crop plants which are resistant to certain
herbicides of the glufosinate- (cf., for example, EP-A 0 242 236,
EP-A 0 242 246) or glyphosate-type (WO 92/00377), or of the
sulfonylurea-type (EP-A 0 257 993, U.S. Pat. No. 5,013,659),
[0040] transgenic crop plants, for example cotton, having the
ability to produce Bacillus thuringiensis toxins (Bt toxins) which
impart resistance to certain pests to the plants (EP-A 0 142 924,
EP-A 0 193 259),
[0041] transgenic crop plants having a modified fatty acid
composition (WO 91/13972).
[0042] Numerous molecular biological techniques which allow the
preparation of novel transgenic plants having modified properties
are known in principle; see, for example, Sambrook et al., 1989,
Molecular Cloning, A Laboratory Manual, 2nd ed. Cold Spring Harbor
Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker "Gene und
Klone" [Genes and Clones], VCH Weinheim, 2nd edition 1996, or
Christou, "Trends in Plant Science" 1 (1996) 423-431). In order to
carry out such genetic engineering manipulations, it is possible to
introduce nucleic acid molecules into plasmids which allow a
mutagenesis or a change in the sequence to occur by recombination
of DNA sequences. Using the abovementioned standard processes it is
possible, for example, to exchange bases, to remove partial
sequences or to add natural or synthetic sequences. To link the DNA
fragments with each other, it is possible to attach adaptors or
linkers to the fragments.
[0043] Plant cells having a reduced activity of a gene product can
be prepared, for example, by expressing at least one appropriate
antisense-RNA, a sense-RNA to achieve a cosuppression effect, or by
expressing at least one appropriately constructed ribozyme which
specifically cleaves transcripts of the abovementioned gene
product.
[0044] To this end it is possible to employ both DNA molecules
which comprise the entire coding sequence of a gene product
including any flanking sequences that may be present, and DNA
molecules which comprise only parts of the coding sequence, it
being necessary for these parts to be long enough to cause an
antisense effect in the cells. It is also possible to use DNA
sequences which have a high degree of homology to the coding
sequences of a gene product but which are not entirely
identical.
[0045] When expressing nucleic acid molecules in plants, the
synthesized protein can be localized in any desired compartment of
the plant cells. However, to achieve localization in a certain
compartment, it is, for example, possible to link the coding region
with DNA sequences which ensure localization in a certain
compartment. Such sequences are known to the person skilled in the
art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227;
Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850;
Sonnewald et al., Plant J. 1 (1991), 95-106).
[0046] The transgenic plant cells can be regenerated to whole
plants using known techniques. The transgenic plants can in
principle be plants of any desired plant species, i.e. both
monocotyledonous and dicotyledonous plants. In this manner, it is
possible to obtain transgenic plants which have modified properties
by overexpression, suppression or inhibition of homologous
(=natural) genes or gene sequences or by expression of heterologous
(=foreign) genes or gene sequences.
[0047] When using the active compounds according to the invention
in transgenic crops, in addition to the effects against harmful
plants which can be observed in other crops, there are frequently
effects which are specific for the application in the respective
transgenic crop, for example a modified or specifically broadened
spectrum of weeds which can be controlled, modified application
rates which can be used for the application, preferably good
combinability with the herbicides to which the transgenic crops are
resistant, and an effect on the growth and the yield of the
transgenic crop plants. The invention therefore also provides for
the use of the compounds according to the invention as herbicides
for controlling harmful plants in transgenic crop plants.
[0048] In addition, the substances according to the invention have
outstanding growth-regulating properties in crop plants. They
engage in the plant metabolism in a regulating manner and can this
be employed for the targeted control of plant constituents and for
facilitating harvesting, for example by provoking desiccation and
stunted growth. Furthermore, they are also suitable for generally
regulating and inhibiting undesirable vegetative growth, without
destroying the plants in the process. Inhibition of vegetative
growth plays an important role in many monocotyledon and
dicotyledon crops because lodging can be reduced hereby, or
prevented completely.
[0049] The compounds according to the invention can be applied in
the customary formulations in the form of wettable powders,
emulsifiable concentrates, sprayable solutions, dusts or granules.
The invention therefore also provides herbicidal compositions
comprising compounds of the formula (I). The compounds of the
formula (I) can be formulated in various ways depending on the
prevailing biological and/or chemico-physical parameters. Examples
of suitable formulation options are: wettable powders (WP),
water-soluble powders (SP), water-soluble concentrates,
emulsifiable concentrates (EC), emulsions (EW), such as
oil-in-water and water-in-oil emulsions, sprayable solutions,
suspension concentrates (SC), oil- or water-based dispersions,
oil-miscible solutions, dusts (DP), capsule suspensions (CS),
seed-dressing compositions, granules for broadcasting and soil
application, granules (GR) in the form of microgranules, spray
granules, coating granules and adsorption granules,
water-dispersible granules (WG), water-soluble granules (SG), ULV
formulations, microcapsules and waxes. These individual formulation
types are known in principle and are described, for example, in
Winnacker-Kuhler, "Chemische Technologie" [Chemical Technology],
Volume 7, C. Hauser Verlag Munich, 4th. Edition 1986; Wade van
Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K.
Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd.
London.
[0050] The necessary formulation auxiliaries, such as inert
materials, surfactants, solvents and other additives, are likewise
known and are described, for example, in Watkins, "Handbook of
Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books,
Caldwell N.J., H. v. Olphen, "Introduction to Clay Colloid
Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden,
"Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's
"Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood
N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents",
Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzflchenaktive
thylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss.
Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, "Chemische
Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag
Munich, 4th Edition 1986.
[0051] Wettable powders are preparations which are uniformly
dispersible in water and which contain, in addition to the active
compound and as well as a diluent or inert substance, surfactants
of ionic and/or nonionic type (wetting agents, dispersants), for
example polyethoxylated alkyl phenols, polyethoxylated fatty
alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol
ethersulfates, alkanesulfonates, alkylbenzenesulfonates, sodium
ligninsulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate,
sodium dibutyinaphthalenesulfona- te or else sodium
oleoylmethyltaurinate. To prepare the wettable powders, the
herbicidally active compounds are finely ground, for example in
customary apparatus such as hammer mills, fan mills and air-jet
mills, and are mixed simultaneously or subsequently with the
formulation auxiliaries.
[0052] Emulsifiable concentrates are prepared by dissolving the
active compound in an organic solvent, for example butanol,
cyclohexanone, dimethylformamide, xylene or else relatively
high-boiling aromatic compounds or hydrocarbons or mixtures of the
solvents, with the addition of one or more surfactants of ionic
and/or nonionic type (emulsifiers). Examples of emulsifiers which
can be used are calcium alkylarylsulfonates, such as Ca
dodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty
acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol
polyglycol ethers, propylene oxide-ethylene oxide condensation
products, alkyl polyethers, sorbitan esters, for example sorbitan
fatty acid esters or polyoxyethylene sorbitan esters, for example
polyoxyethylene sorbitan fatty acid esters.
[0053] Dusts are obtained by grinding the active compound with
finely divided solid substances, for example talc, natural clays,
such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspension concentrates can be water- or oil-based. They can be
prepared, for example, by wet milling using commercially customary
bead mills, with or without the addition of surfactants as already
mentioned above, for example, in the case of the other formulation
types.
[0054] Emulsions, for example oil-in-water emulsions (EW), can be
prepared for example by means of stirrers, colloid mills and/or
static mixers using aqueous organic solvents and, if desired,
surfactants as already mentioned above, for example, in the case of
the other formulation types.
[0055] Granules can be prepared either by spraying the active
compound onto adsorptive, granulated inert material or by applying
active-compound concentrates to the surface of carriers such as
sand, kaolinites or granulated inert material, by means of adhesive
binders, for example polyvinyl alcohol, sodium polyacrylate or else
mineral oils. Suitable active compounds can also be granulated in
the manner which is customary for the preparation of fertilizer
granules, if desired as a mixture with fertilizers.
Water-dispersible granules are generally prepared by the customary
processes, such as spray-drying, fluidized-bed granulation, disk
granulation, mixing using high-speed mixers, and extrusion without
solid inert material.
[0056] For the preparation of disk, fluidized-bed, extruder and
spray granules, see for example processes in "Spray-Drying
Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning,
"Agglomeration", Chemical and Engineering 1967, pages 147 ff.;
"Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New
York 1973, pp. 8-57. For further details on the formulation of crop
protection products, see for example G. C. Klingman, "Weed Control
as a Science", John Wiley and Sons Inc., New York, 1961, pages
81-96 and J. D. Freyer, S. A. Evans, "Weed Control Handbook", 5th
Ed., Blackwell Scientific Publications, Oxford, 1968, pages
101-103.
[0057] The agrochemical formulations generally contain from 0.1 to
99% by weight, in particular from 0.1 to 95% by weight, of active
compound of the formula (I). In wettable powders the concentration
of active compound is, for example, from about 10 to 90% by weight,
the remainder to 100% by weight consisting of customary formulation
constituents. In emulsifiable concentrates the concentration of
active compound can be from about 1 to 90%, preferably from 5 to
80%, by weight. Formulations in the form of dusts contain from 1 to
30% by weight of active compound, preferably most commonly from 5
to 20% by weight of active compound, while sprayable solutions
contain from about 0.05 to 80%, preferably from 2 to 50%, by weight
of active compound. In the case of water-dispersible granules the
content of active compound depends partly on whether the active
compound is in liquid or solid form and on the granulation
auxiliaries, fillers, etc. that are used. In water-dispersible
granules the content of active compound, for example, is between 1
and 95% by weight, preferably between 10 and 80% by weight.
[0058] In addition, said formulations of active compound may
comprise the tackifiers, wetting agents, dispersants, emulsifiers,
penetrants, preservatives, antifreeze agents, solvents, fillers,
carriers, colorants, antifoams, evaporation inhibitors and pH and
viscosity regulators which are customary in each case.
[0059] Based on these formulations it is also possible to produce
combinations with other pesticidally active substances, for example
insecticides, acaricides, herbicides and fungicides, and also with
safeners, fertilizers and/or growth regulators, for example in the
form of a ready-mix or tank mix.
[0060] Suitable active compounds which can be combined with the
active compounds according to the invention in mixed formulations
or in a tank mix are, for example, known active compounds as
described in for example Weed Research 26, 441-445 (1986), or "The
Pesticide Manual", 11th edition, The British Crop Protection
Council and the Royal Soc. of Chemistry, 1997 and in the literature
cited therein. For example the following active compounds may be
mentioned as herbicides which can be combined with the compounds of
the formula (I) (note: the compounds are either named by the
"common name" in accordance with the International Organization for
Standardization (ISO) or by the chemical names, if appropriate
together with a customary code number):
[0061] acetochlor; acifluorfen; aclonifen; AKH 7088, i.e.
[[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyeth-
ylidene]amino]oxy]acetic acid and its methyl ester; alachlor;
alloxydim; ametryn; amidosulfuron; amitrol; AMS, i.e. ammonium
sulfamate; anilofos; asulam; atrazine; azimsulfurone (DPX-A8947);
aziprotryn; barban; BAS 516 H, i.e.
5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin;
benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap;
benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox;
bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron;
buminafos; busoxinone; butachlor; butamifos; butenachlor;
buthidazole; butralin; butylate; cafenstrole (CH-900); carbetamide;
cafentrazone (ICI-A0051); CDAA, i.e.
2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e. 2-chloroallyl
diethyldithiocarbamate; chlomethoxyfen; chloramben;
chlorazifop-butyl, chlormesulon (ICI-A0051) chlorbromuron;
chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon;
chlorimuron ethyl; chlornitrofen; chlorotoluron; chloroxuron;
chlorpropham; chlorsulfuron; chlorthal-dimethyl; chiorthiamid;
cinmethylin; cinosulfuron; clethodim; clodinafop and its ester
derivatives (for example clodinafop-propargyl); clomazone;
clomeprop; cloproxydim; clopyralid; cumyluron (JC 940); cyanazine;
cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop
and its ester derivatives (for example butyl ester, DEH-112);
cyperquat; cyprazine; cyprazole; daimuron; 2,4-DB; dalapon;
desmedipham; desmetryn; di-allate; dicamba; dichlobenil;
dichlorprop; diclofop and its esters such as diclofop-methyl;
diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron;
dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone,
clomazon; dimethipin; dimetrasulfuron, dinitramine; dinoseb;
dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC;
eglinazine-ethyl; EL 77, i.e.
5-cyano-1-(1,1-dimethylethyl)-N-methyl-1H-pyrazole-4-carboxamide;
endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl;
ethidimuron; ethiozin; ethofumesate; F5231, i.e.
N-[2-chloro-4-fluoro-5-[-
4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]-phenyl]ethanesulfon-
amide; ethoxyfen and its esters (for example ethyl ester, HN-252);
etobenzanid (HW 52); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P
and their esters, for example fenoxaprop-P-ethyl and
fenoxaprop-ethyl; fenoxydim; fenuron; flamprop-methyl;
flazasulfuron; fluazifop and fluazifop-P and their esters, for
example fluazifop-butyl and fluazifop-P-butyl; fluchloralin;
flumetsulam; flumeturon; flumiclorac and its esters (for example
pentyl ester, S-23031); flumioxazin (S-482); flumipropyn; flupoxam
(KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil
(UBIC4243); fluridone; flurochloridone; fluroxypyr; flurtamone;
fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate;
halosafen; halosulfuron and its esters (for example methyl ester,
NC-319); haloxyfop and its esters; haloxyfop-P (=R-haloxyfop) and
its esters; hexazinone; imazapyr; imazamethabenz-methyl; imazaquin
and salts such as the ammonium salt; ioxynil; imazethamethapyr;
imazethapyr; imazosulfuron; isocarbamid; isopropalin; isoproturon;
isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil;
linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidid; metamitron;
metazachlor; metham; methabenzthiazuron; methazole; methoxyphenone;
methyldymron; metobenzuron; metobromuron; metolachlor; metosulam
(XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH; molinate;
monalide; monolinuron; monuron; monocarbamide dihydrogensulfate; MT
128, i.e.
6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazin-amine;
MT 5950, i.e.
N-[3-chloro-4-(1-methylethyl)-phenyl]-2-methyl-pentanamide;
naproanilide; napropamide; naptalam; NC 310, i.e.
4-(2,4-dichlorobenzoyl)- -1-methyl-5-benzyloxypyrazole; neburon;
nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen;
norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630);
oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin;
perfluidone; phenisopham; phenmedipham; picloram; piperophos;
piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl;
procyazine; prodiamine; profluralin; proglinazine-ethyl; prometon;
prometryn; propachlor; propanil; propaquizafop and its esters;
propazine; propham; propisochlor; propyzamide; prosulfalin;
prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyrazolinate;
pyrazon; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate; pyrithiobac
(KIH-2031); pyroxofop and its esters (for example propargyl ester);
quinclorac; quinmerac; quinofop and its ester derivatives,
quizalofop and quizalofop-P and their ester derivatives, for
example quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl;
renriduron; rimsulfuron (DPX-E 9636); S 275, i.e.
2-[4-chloro-2-fluoro-5-(2-propynylo-
xy)phenyl]-4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim;
siduron; simazine; simetryn; SN 106279, i.e.
2-[[7-[2-chloro-4-(trifluoro-
methyl)phenoxy]-2-naphthalenyl]oxy]propanoic acid and its methyl
ester; sulfentrazon (FMC-97285, F-6285); sulfazuron;
sulfometuron-methyl; sulfosate (ICI-A0224); TCA; tebutam
(GCP-5544); tebuthiuron; terbacil; terbucarb; terbuchlor;
terbumeton; terbuthylazine; terbutryn; TFH 450, i.e.
N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1H-1,2,4-triazol-1--
carboxamide; thenylchlor (NSK-850); thiazafluron; thiazopyr
(Mon-13200); thidiazimin (SN-24085); thiobencarb;
thifensulfuron-methyl; tiocarbazil; tralkoxydim; tri-allate;
triasulfuron; triazofenamide; tribenuron-methyl; triclopyr;
tridiphane; trietazine; trifluralin; triflusulfuron and its esters
(for example methyl ester, DPX-66037); trimeturon; tsitodef;
vernolate; WL 110547, i.e.
5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1H-tet- razole; UBH-509;
D-489; LS 82-556; KPP-300; NC-324; NC-330; KH-218; DPX-N8189;
SC-0774; DOWCO-535; DK-8910; V-53482; PP-600; MBH-001; KIH-9201;
ET-751; KIH-6127 and KIH-2023.
[0062] For use, the formulations which are present in commercially
available form are, if appropriate, diluted in the customary
manner, for example using water in the case of wettable powders,
emulsifiable concentrates, dispersions and water-dispersible
granules. Products in the form of dusts, granules for soil
application or broadcasting and sprayable solutions are usually not
further diluted with other inert substances prior to use. The
application rate of the compounds of the formula (I) required
varies with the external conditions, such as temperature, humidity,
the nature of the herbicide used and the like. It can vary within
wide limits, for example between 0.001 and 1.0 kg/ha or more of
active substance, but it is preferably between 0.005 and 750 g/ha,
in particular between 0.005 and 250 g/ha.
[0063] The examples below illustrate the invention.
A. CHEMICAL EXAMPLES
[0064] The preparation of the starting materials
2-methylsulfenyl-4-triflu- oromethylbenzoic acid,
2-methylsulfinyl-4-trifluoromethylbenzoic acid and
2-methylsulfonyl-4-trifluoromethylbenzoic acid was carried out
according to EP-A 0 527 036, the 5-hydroxypyrazoles were prepared
according to EP-A 0 240 001 or are commercially available.
[0065] 1. Preparation of
4-(4-trifluoromethyl-2-methylsulfonylbenzoyl)-5-h-
ydroxy-1-ethyl-3-methylpyrazole
[0066] Step 1:
1-Ethyl-3-methyl-5-pyrazolyl-4-trifluoromethyl-2-methylsulf-
onylbenzoate
[0067] 2.1 g (7.8 mmol) of 2-methylsulfonyl4-trifluoromethylbenzoic
acid were dissolved in 90 ml of CH.sub.2Cl.sub.2. 2 drops of DMF
and 2.98 g (2.4 mmol) of (COCl).sub.2 were added, and the mixture
was boiled under reflux for 4 h. The mixture was then concentrated
and the residue was taken up in 300 ml of CH.sub.2Cl.sub.2 and, at
0.degree. C., admixed with 1.46 g (9 mmol) of
1-ethyl-3-methyl-5-hydroxypyrazole and 4.45 ml of NEt.sub.3. The
mixture was stirred at room temperature for 4 h and then
concentrated, and the residue was purified by chromatography
(silica gel, ethyl acetate:hexane=3:2). This gave
1-ethyl-3-methyl-5-pyrazolyl-4-trifl-
uoromethyl-2-methylsulfonylbenzoate as a solid.
[0068] Yield: 2.7 g (95% of theory) R.sub.f(ethyl ester): 0.75
[0069] .sup.1H-NMR: .delta.[CDCl.sub.3] 1.42 (t, 3H), 2.25 (s, 3H),
3.25 (s, 3H), 4.05 (q, 2H), 6.08 (s, 1H), 7.45 (d, 1H), 7.65 (s,
1H), 8.24 (d, 1H).
[0070] Step 2:
4-(4-Trifluoromethyl-2-methylsulfonylbenzoyl)-5-hydroxy-1-e-
thyl-3-methylpyrazole
[0071] 1.27 g (3.4 mmol) of
1-ethyl-3-methyl-5-pyrazolyl4-trifluoromethyl--
2-methylsulfonylbenzoate, 2 drops of acetone cyanohydrin and 0.8 ml
(5.8 mmol) of NEt.sub.3 were dissolved in 80 ml of CH.sub.3CN, and
the mixture was stirred at room temperature overnight. The mixture
was then concentrated to dryness and the residue was admixed with
water and the mixture was acidified using 2 N HCl. The precipitated
product was filtered off with suction and recrystallized from
ethanol. This gave
4-(4-trifluoromethyl-2-methylsulfonylbenzoyl)-5-hydroxy-1-ethyl-3-methylp-
yrazole as a yellowish oil.
[0072] Yield: 1.22 g (96% of theory)
[0073] .sup.1H-NMR: .delta.[CDCl.sub.3] 1.45 (t, 3H), 2.25 (s, 3H),
2.95 (s, 3H), 4.00 (q, 2H), 7.65 (d, 1H), 7.85 (d, 1H), 8.58 (s,
1H).
[0074] 2. Preparation of
4-(4-trifluoromethyl-2-methylsulfonylbenzoyl)-1-e-
thyl-3-methyl-5-pyrazolyl tosylate
[0075] 0.37 g (1 mmol) of
4-(4-trifluoromethyl-2-methylsulfonylbenzoyl)-5--
hydroxy-1-ethyl-3-methylpyrazole and 0.20 g (1.1 mmol) of p-Tos-Cl
were dissolved in 20 ml of CH.sub.3CN. 0.26 g (1.8 mmol) of
potassium carbonate was then added, and the mixture was stirred at
room temperature for 12 h. The mixture was diluted with water and
extracted with ethyl acetate. The extract was dried with MgSO.sub.4
and concentrated. This gave
4-(4-trifluoromethyl-2-methylsulfonylbenzoyl)-1-ethyl-3-methyl-5-pyr-
azolyl tosylate as a wax.
[0076] Yield: 0.51 g (98% of theory)
[0077] .sup.1H-NMR: .delta.[CDCl.sub.3] 1.90 (t, 3H), 2.05 (s, 3H),
2.45 (s, 3H), 3.25 (s,3H), 4.05 (q, 2H), 7.35 (d, 2H), 7.45 (d,
1H), 7.75 (d, 2H), 8.05 (d, 1H), 8.40 (s, 1H).
[0078] The examples listed in the tables below were prepared
analogously to the methods mentioned above or are obtainable
analogously to the methods mentioned above.
1TABLE A Compound of the formula (I) according to the invention in
which the substituents and symbols are as defined below: R.sup.1 =
Me R.sup.2 = CF.sub.3 n = 2 7 No. R.sup.3 R.sup.4 R.sup.5 Physical
data 1 Me Et H .sup.1H-NMR data see Preparation Example 1 2 Me Et
Tos .sup.1H-NMR data see Preparation Example 2 3 Me Et Bz-CH.sub.2
4 Me Me H m.p. 202-204.degree. C. 5 Me Me 4-F-Bz-CH.sub.2 oil 6 Me
Me Ph-SO.sub.2 7 Me Me Bz-CH.sub.2 oil 8 Me Me
4-NO.sub.2-Bz-CH.sub.2 oil 9 Me Me 3-NO.sub.2-Bz-CH.sub.2 oil 10 Me
Me Tos m.p. 130-132.degree. C. 11 Me Me n-Pr--SO.sub.2 wax 12 Me Me
Bn m.p. 179.degree. C. 13 Me Me Me-SO.sub.2 m.p. 147.degree. C. 14
Me Me 2-NO.sub.2-Bn m.p. 146.degree. C. 15 Me Et Me-SO.sub.2 oil 16
Me Et Me-SO.sub.2 oil 17 Me Et Bn glasslike 18 Me Et
4-F-Bz-CH.sub.2 The following abbreviations were used: Bn = benzyl
Bz = benzoyl Et = ethyl Me = methyl Pr = propyl Ph = phenyl Tos =
Tosyl m.p. = Melting point
B. FORMULATION EXAMPLES
[0079] 1. Dust
[0080] A dust is obtained by mixing 10 parts by weight of a
compound of the formula (I) and 90 parts by weight of talc as inert
substance and comminuting the mixture in a hammer mill.
[0081] 2. Dispersible Powder
[0082] A wettable powder which is readily dispersible in water is
obtained by mixing 25 parts by weight of a compound of the formula
(I), 64 parts by weight of kaolin-containing quartz as inert
substance, 10 parts by weight of potassium lignosulfonate and 1
part by weight of sodium oleoylmethyltaurinate as wetter and
dispersant and grinding the mixture in a pinned-disk mill.
[0083] 3. Dispersion Concentrate
[0084] A dispersion concentrate which is readily dispersible in
water is obtained by mixing 20 parts by weight of a compound of the
formula (I) with 6 parts by weight of alkylphenol polyglycol ether
(.RTM.Triton X 207), 3 parts by weight of isotridecanol polyglycol
ether (8 EO) and 71 parts by weight of paraffinic mineral oil
(boiling range for example approx. 255 to above 277.degree. C.) and
grinding the mixture in a ball mill to a fineness of below 5
microns.
[0085] 4. Emulsifiable Concentrate
[0086] An emulsifiable concentrate is obtained from 15 parts by
weight of a compound of the formula (I), 75 parts by weight of
cyclohexanone as the solvent and 10 parts by weight of ethoxylated
nonylphenol as the emulsifier.
[0087] 5. Water-dispersible Granules
[0088] Water-dispersible granules are obtained by mixing
[0089] 75 parts by weight of a compound of the formula(I),
[0090] 10 parts by weight of calcium lignosulfonate,
[0091] 5 parts by weight of sodium lauryl sulfate,
[0092] 3 parts by weight of polyvinyl alcohol and
[0093] 7 parts by weight of kaolin
[0094] grinding the mixture on a pinned-disk mill and granulating
the powder in a fluidized bed by spraying on water as the
granulation liquid.
[0095] Water-dispersible granules are also obtained by homogenizing
and precomminuting, on a colloid mill,
[0096] 25 parts by weight of a compound of the formula (I),
[0097] 5 parts by weight of Sodium
2,2'-dinaphthylmethane-6,6'-disulfonate- ,
[0098] 2 parts by weight of sodium oleoylmethyltaurinate,
[0099] 1 part by weight of polyvinyl alcohol,
[0100] 17 parts by weight of calcium carbonate and
[0101] 50 parts by weight of water
[0102] subsequently grinding the mixture in a bead mill and
atomizing and drying the resulting suspension in a spray tower by
means of a single-substance nozzle.
C. BIOLOGICAL EXAMPLES
[0103] 1. Post-emergence Herbicidal Action on Harmful Plants
[0104] Seeds of monocotyledonous and dicotyledonous harmful plants
are placed in sandy loam soil in cardboard pots, covered with soil
and grown in a greenhouse under good growth conditions. Two to
three weeks after sowing, the test plants are treated at the
three-leaf stage. The compounds according to the invention which
were formulated as wettable powders or emulsion concentrate are
sprayed, at one of the dosages given in Tables 1 to 5, onto the
surface of the green parts of the plants at an application rate of
from 600 to 800 l of water/ha (converted). After the test plants
had remained in the greenhouse for about 3 to 4 weeks under optimum
growth conditions, the effect of the preparations is scored
visually by comparison with compounds disclosed in the prior art.
As shown by the results of Comparative Tables 1 to 4, the selected
compounds according to the invention have better herbicidal
activity against a broad spectrum of economically important
monocotyledonous and dicotyledonous harmful plants than the
compounds disclosed in the prior art.
[0105] 2. Tolerance by Crop Plants
[0106] In further greenhouse experiments, seeds of barley and
monocotyledonous and dicotyledonous harmful plants are placed in
sandy loam soil, covered with soil and placed in a greenhouse until
the plants had developed two to three leaves. The treatment with
the compounds of the formula (I) according to the invention and, by
comparison, with the compounds disclosed in the prior art is then
carried out as described above under Item 1. Four to five weeks
after the application and after the plants had been in the
greenhouse, visual scoring reveals that the compounds according to
the invention, in contrast to the compounds disclosed in the prior
art, do not inflict any damage on the crop plant, even at
relatively high dosages of active compound (see Table 5).
[0107] Compounds used in the comparative experiments and disclosed
in the prior art
2 No. Structure S1 8 S2 9 S3 10
[0108]
3 APSEV Apera spica venti CHEAL Chenopodium album LAMPU Lamium
purpureum POLCO Polygonum convolvulus STEME Stellaria media VERHE
Veronica hederifolia VERPE Veronica persica VIOTR Viola tricolor
HORVS Hordeum vulgaris Comparative Table 1 Dosage Damage to the
harmful plants in % Compound No. [g off a.i./ha] POLCO VERHE VIOTR
4 from Table A 200 90 90 80 S1 200 20 30 30 Comparative Table 2
Dosage Damage to the harmful plants in % Compound No. [g off
a.i./ha] CHEAL POLCO STEME 10 from Table A 50 95 60 70 S2 50 0 10
10 Comparative Table 3 Dosage Damage to the harmful plants in %
Compound No. [g off a.i./ha] CHEAL STEME 4 from Table A 100 90 85
S2 100 0 10 Comparative Table 4 Dosage Damage to the harmful plants
in % Compound No. [g off a.i./ha] LAMPU VERHE VERPE 8 from Table A
50 70 60 100 S3 50 20 10 10 Comparative Table 5 Dosage Damage to
the useful plants in % Compound No. [g off a.i./ha] HORVS 1 from
Table A 200 0 4 from Table A 200 0 S2 200 20 S3 200 20
* * * * *