Note: Descriptions are shown in the official language in which they were submitted.
~ ~36~0
-- 1 --
Case 5-13206/=
Novel fluoropyrrolidinones, the production thereof,
herbicidal compositions containing them, and method
of use thereof
The present invention relates to novel herbicidally
active fluoropyrrolidinones, to the production thereof, to
compositions containing them, and to the use thereof for
selectively controlling weeds in various crops of cultivat-
ed plants, e.g. cereals, rice, maize, soybeans and cotton.
The fluoropyrrolidinones have the general formula I
Y- I i-CH -z (I)
0~
wherein R is Cl-C4alkyl, C3-C4alkenyl, alkoxyalkyl of at
most 5 carbon atoms, benzyl or benzyl substituted by
halogen, Cl-C4alkoxy or Cl-C4alkyl, or is phenyl or phenyl
monosubstituted or polysubstituted by halogen~
nitro, cyano, Cl-C4alkoxy, Cl-C4hal~alkoxy,
-C4haloalkylthio, Cl-C4alkylsulfinyl, Cl-C4haloalkylsul-
finyl~ Cl-C4aLkylsulfonyl or Cl-C4haloalkylsulfonyl; Y is
hydrogen, Cl-C4alkyl, fluorine, chlorine or bromine; and Z
is chlorine or bromine.
Alkyl by itself or as moiety of other substituents
such as alkoxy, alkoxyalkyl, alkylthio,
alkylsulfinyl, alkylsulfonyl or the corresponding halo-
aikyl substituents, has the following meanings: methyl,
,~
,,.,~"" ,,., . ` ~ ' ' ' '
' , '
' "' ' ~ ' " .'
~ ~ ~36~ 0
-- 2 --
ethyl, n-propyl, isopropyl, butyl and the isomers thereof.
Halogen by itself or as moiety of another substituent
is fluorine, chlorine, bromine and iodine, with fluorine
and chlorine being preferred.
Accordingly, examples of alkoxy radicals are:
methoxy, ethoxy and propyloxy; examples of haloalkyl
radicals are: fluoromethyl, chloromethyl, trifluoromethyl,
perfluoroethyl or difluoromethyl, with trifluoromethyl
being preferred; examples of alkoxyalkyl radicals are:
methoxymethyl, ethoxymethyl, methoxyethyl or ethoxyethyl;
examples of haloalkoxy radicals are: trifluoromethoxy,
difluoromethoxy or perfluoromethoxy; examples of alkylthio
and haloalkylthio radicals are: methylthio, ethylthio,
trifluoromethylthio, difluoromethylthio, chloromethylthio,
perfluoroethylthio or chlorofluoromethylthio; examples of
alkylsulfinyl and haloalkylsulfinyl radicals are: methyl-
sulfinyl, ethylsulfinyl, tri~uoromethylsulfinyl, difluoro-
methylsulfinyl or perfluoroethylsulfinyl; and examples of
alkylsulfonyl and haloalkylsulfonyl radicals are: methyl-
sulfonyl, ethylsulfonyl, trifluorosulfonyl, difluoro-
methylsulfonyl or perfluoroethylsulfonyl.
Alkenyl is e.g. allyl, methallyl, 2-butenyl or
3-butenyl.
Herbicidally active chloro- and bromopyrrolidinones
of similar structure have been disclosed in German Offen-
legungsschrift 2 612 731. Compared with these compounds,
the fluoropyrrolidinones of the present invention have
better selectivity in crops of useful plants such as
cereals, rice, maize, soybeans and cotton when applied post-
and preemergence, especially in preemergence application.
Preferred for their good activity are those compounds
of the formula I in which R is a phenyl radical which is
monosubstituted or polysubstituted by halogen, nitro, cyano,
methoxy, halomethoxy, methyl, halomethyl, halomethylthio,
halomethylsulfinyl or halomethylsulfonyl, Y is hydrogen,
~ ~63
-- 3 --
methyl, chlorine or bromine, and Z is chlorine or bromine.
More preferred compounds of the formula I are those
in which R is a phenyl radical which is monosubstituted
or polysubstitu~ by halogen, halomethyl or halomethoxy, Y
is hydrogen or chlorine, and Z is chlorine.
The most preferred compounds of the formula I are
those in whîch R is a phenyl radical which is substituted
in the 3-position by halogen, trifluoromethyl, trifluoro-
methoxy or difluoromethoxy, Y is hydrogen or chlorine, and
Z is chlorine.
A preferred individual compound is N-(3-trifluoro-
methylphenyl)-3-fluoro-4-chloromethyl-pyrrolidin-2-one,
together with its diastereomeric forms.
The compounds of the formula I are prepared by
methods analogous to those described in German Offenlegungs-
schrift 2 612 731, by heating a N-allylacetamide of the
formula II
F - C - C - N - CH - CH = CH (II)
Y Z O R
wherein R, Y and Z are as defined for formula I, in the
presence of a catalyst,and in an inert solvent. The
reaction temperature is advantageously in the range from
50 to 180C, with the preferred range being ~rom 120 to
170C.
Suitable catalysts are transi~ion metal ions, e.g.
ions of vanadium, iron, copper, molybdenum, ruthenium or
silver, or their complexes, e.g. copper(I) chloride/piperidine,
copper(I) chloride/2,2'-dipyridyl or ruthenium chloride/
triphenylphosphine.
Examples of preferred inert solvents are: diethylene
glycol dimethyl ether, dimethyl formamide~ dimethyl
sulfoxide, mesitylene, decalin or tetralin.
~ ~636~10
-- 4 --
The starting compounds of the formula II can be obtain-
ed in generally known manner from known allylamines of the
formula III
2 2 (III )
~y reaction with fluoroacetic halidesof the formula IV
O
Y - C - C - Hal (IV)
z
in the presence of a base.
In the formulae III and IV above, R, Y and Z are as
defined for formula I, and Hal is chlorine or bromine.
Examples of bases which can be used are: trialkyl-
amines such as triethylamine; hydroxides such as sodium or
potassium hydroxide; carbamates such as sodium or potassium
carbonate; bicarbonates such as sodium bicarbonate; or
hydrides such as sodium or calcium hydride.
The~cyclisation reaction (I~ can result in the
formation of both possible configuration isomers of the
compounds of formula I, viz. the cis-isomer and the
trans-isomer. Usually a mixture of isomers is obtained,
which can be separated into its individual components by
suitable methods, e.g. fractional crystallisation,
distillation, chromatography or extraction. Unless other-
wise specifically mentioned, a compound of the formula I
will always be understood as meaning a mixture of isomers.
The compounds of formula I have excellent herbicidal
activity against monocot and dicot weeds and they can be
applied both preemergence and postemergence. The compounds
o formula I are particularly suitable for controlling
weeds in crops of cultivated plants such as cereals,rice,
.
,.
,,. - ~ .
.
~ 1~36~
-- 5 --
maize, soybeans and cotton, because ~heir activity is highly
selective. This means that the weeds are destroyed, but the
cultivated plants are not damaged or their development is
only insignificantly affected.
The compounds of formula I have proved particularly
suitable when used preemergence for controlling weeds in
the crops of cultivated plants referred to above. Both
configuration isomers of these compounds have the same or
different biological activity.
The compounds of the formula I are used in unmodified
form or preferably together with the adjuvants
conventionally employed in the art of formulation, and are
therefore formulated in known manner to emulsifiable con-
centrates, directly sprayable or dilutable solutions,
dilute emulsions, wettable powders, soluble powders, dusts,
granulates, and also encapsulations in e.g. polmyer sub-
stances. Just like the nature of the compositions, the
methods of application, such as spraying, atomising,
dusting, scattering or pouring, are chosen in accordance
with the intended ob;ectives and the prevailing circum-
stances.
The formulations, i.e. the compositions or
preparations containing the compound (active ingredient)
of the formula I and, where appropriate, a solid or liquid
adjuvant~ are prepared in known manner, e.g. by homogene-
ously mixing and/or grinding the active ingredients with
extenders, e.g. solvents, solid carriers and, where appro-
priate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, pre-
ferably the f~actions containing 8 to 12 carbon atoms,
e.g. xylene mixtures or substituted naphthalenes, phthalates
such as dibutyl phthalate or dioctyl phthalate, aliphatic
hydrocarbons such as~ cyclohexane,or paraffins, alcohols and
glycols and their ethers and esters, such as ethanol,
.
.
~ ~636~0
- 6 -
ethylene glycol, ethylene glycol monomethyl or monoethyl
ether; ketones such as cyclohexanone, strongly polar
solvents such as N-methyl-2-pyrrolidone, dimethyl
sulfoxide or dimethyl formamide; as well as epoxidised
vegetable oils such as epoxidised coconut oil or soybean
oilj or water.
The solid carriers used e.g. for dusts and
dispersible powders are normally natural mineral fillers
such as calcite, talcum, kaolin, montmorillonite or
attapulgite. In order to improve the physical properties
it is also possible to add highly dispersed silicic acid
or highly dispersed absorbent polymers~ Suitable granulated
adsorptive carriers are porous types, for example pumice,
broken brick, sepiolite or bentonite; and suitable nonsor-
bent carriers are materials such as calcite or sand. In
addition, a great number of pregranulated materials of
inorganic or organic nature can be used, e.g. especially
dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I
to be formulated, suitable surface-active compounds are
nonionic, cationic and/or anionic surfactants having good
emulsifying, dispersing and wetting properties, The term
"surfactants" will also be understood as comprising
mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble
soaps and water-soluble synthetic surface-active
compounds.
Suitable soaps are the alkali, alkaline earth or
unsubstituted or substituted ammonium salts of higher fatty
acids (C10-C22), e.g. the sodium or potassium salts of
oleic or stearic acid, or of natural fatty acid mixtures
which can be obtained e.g. from coconut oil or tallow oil.
Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synth~tic sur-
factants are used, especially fatty sulfonates, fatty
. .
,..
~ ~3~Q
-- 7 --
sulfates, sulfonated benzimidazole derivatives or alkyl-
arylsulfonates.
The fatty sulfonates or sulfates are us~ally in the
~nm of alkali, alkaline earth or unsubstituted or substitut-
ed ammonium salts and contain a C8-C22alkyl radical which
also includes the alkyl moiety of acyl radicals, e.g. the
sodium or calcium salt of lignosulfonic acid, of dodecyl-
sulfate or of a mixture of fatty alcohol sulfates obtained
from natural fàtty acids These compounds also comprise
the salts of sulfuric acid esters and sulfonic acids of
fatty alcohol/e~hylene oxide adducts. The sulfonated
benzimidazole derivatives preferably contain 2 sulfonic acid
groups and one fa~y acid radical containing 8 to 22 carbon
atoms. Examples of alkylarylsulfonates are the sodium,
calcium or triethanolamine salts of dodecylbenzenesulfonic
acid, dibutylnaphthalenesulfonic acid, or of a
naphthalenesulfonic acid/formaldehyde condensation product.
Also suitable are corresponding phosphates, e.g. salts of
the phosphoric acid ester of an adduct of p-nonylphenol
with 4 to 14 moles of ethylene oxide.
Non-ionic surfactants are preferably polyglycol ether
derivatives of aliphatic or cycloaliphatic alcohols, or
saturated or unsaturated fatty acids and alkylphenols,
said derivatives containing 3 to 30 glycol ether groups
and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon
moiety and 6 to 18 carbon atoms in the alkyl moiety of the
alkylphenols.
Further suitable non-ionic surfactants are the
water-soluble adducts of polyethylene oxide with poly-
propylene glycol, ethylenediaminepolypropylene glycol and
alkylpolypropylene glycol containing 1 to 10 carbon atoms
in the alkyl chain, which adducts contain 20 to 250
ethylene glycol ether groups and 10 to 100 propylene glycol
ether groups. These compounds usually contain 1 to 5
glycol units per propylene glycol unit.
~.
~ ~36
-- 8 --
Representative examples of non-ionic surfactants are
nonylphenol-polyethoxyQthanols, castor oil polyglycol
ethers, polypropylene/polyethylene oxide adducts, tributyl-
phenoxypolyethoxyethanol, polyethylene glycol and octyl-
phenoxypolye~hoxyethanol. Fatty acid esters of polyoxy-
ethylene sorbitan and polyoxyethylene sorbitan trioleate
are also suitable non-ionic surfactants.
Cationic surfac~ts are preferably quaternary
ammonium salts which contain, as N-substituent, at least
one polyglycol ether or C8-C22alkyl radical and, as further
substituents, lower unsubstituted or halogenated alkyl,
benzyl or lower hydroxyalkyl radicals. The salts are
preferably in the form of halides, methylsulfates or
ethylsulfates, e.g. stearyltrimethylammoniu~ chloride or
benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in the art of
formulation are described e.g. in the following publications:
"McCutcheon's Detergents and Emulsifiers Annual",
MC Publishing Corp., ~ingwood, New Jersey, 1979; Sisely and
Wood, "Encyclopedia of Surface Active Agents", Chemical
Publishing Co. Inc., New York, 1964.
The pesticidal formulations usually contain 0.1 to
90 % of a compound of the formula I, 10 to 99 % of a solid
or liquid adjuvant, and 1 to 25 % of a surfactant.
Preferred formulations are composed in particular
of the following constituents (% = percentage by weight):
Solutions
active ingredient: 5 to 90 ~/0, preferably 10 to 80 %
solvent: 95 to 5 %, preferably 90 to 0 %
surfactants: 1 to 25 %, preferably 2 to 20 %
Emulsifiable concentrates
active ingredient: 10 to 50 %~ preferably 10 to 40 %
surfartant: 5 to 30 %, pre~erably 10 to 20 %
li~uid carrier: 50 to 95 %. preferably 40 to 80 %
Dusts
active ingredient: 0.5 to 10 %, preferably 2 to 8 %
solid carrier: 99,5 to 90 %, preferably 98 to 92 %
Suspension concentrates
active ingredient:5 to 75 %, preferably 10 to 50 %
water:94 to 25 %, preferably 90 to 30 %
surfactant:1 to 40 %, preferably 2 to 30 %
Wettable powders
active ingredient:5 to 90 %, preferably 10 to 80 %, and
most preferably, 20 to 60 %,
surfactant:1 to 20 %, preferably 1 to 15 %
solid carrier:5 to 90 %, preferably 30 to 70 %
Granulates
. ~ .
active ingredient: 1 to 30 %, preferably 3 to 15 %
solid carrier: 99 to 70 %, preferably 97 to 85 %.
Whereas commercial products will be pre~erably
formulated as concentrates, the end user will normally employ
di~ute formulations. The formulations can be diluted to a
eoncentration as low as 0.001 %. The rates of application
are normally 0.1 to 10 kg a~i./ha, preferably 0.25 to
5 kg a.i./ha.
The compositions can also contain further ingredients
such as stabilisers, antifoams, viscosity regulators,
binders, adhesives, as well as fertilisers or other active
compounds, in order to attain special effects.
The following Examples illustra~e the invention in
.. ,.,~, - ~ .
~ \
~ ~3~
-- 10 -
more detail,but imply no restriction to what is disclosed
therein. Parts and percentages are by weight and pressures
are given in millibars (mb),
Preparatory Examples
Example 1
.
a) Preparation of an intermediate
H O
1 11
F - C~ - C - N - CH2 - CH = CH2
Cl .~ ~.
~ I-cF
N-allyl-N-chlorofluoroacetYl-3-trifluoromethylaniline
A solution of 116.7 g of N-allyl-3-trifluoromethyl-
aniline and 60 g of triethylamine in 700 ml of diethyl
ether is cooled to 10-15C. 86 g of chlorofluoroacetyl
chloride are then added dropwise to this cooled ~olution
and the reaction mixture is subsequently stirred for 3
hours at room temperature. The precipitated salt is removed
by filtration and the filtrate is washed first with 5 %
hydrochloric acid and then with 5 V/o sodium hydroxide
solution, dried and concentrated. High vacuum distillation
of the residue yields 138.5 g of N-allylN-chlorofluoroacetyl-
3-trifluoromethylaniline with a boiling point of
93-94C/0.02 mb
.
b) Preparation of a final product
i 2
y
.~ \-
~ cF (compound 35)
.,
,
.
3 ~
N-~3-trifluoromethylphenyl)-3-fluoro-4-chloromethylpyrroli-
din-2-one
60 g of N-allyl-N-chlorofluoroacetyl-3-trifluoro-
methylaniline are added dropwise over 1/2 hour to a boiling
solution of 1 g of copper(I) chloride and 1.5 g of
2,2'-dipyridyl in 50 ml of diethylene glycol dimethyl
ether. The reaction mixture is boiled under reflux for
another 5 hours, cooled, and then taken up in a mixture of
diethyl ether and 5 % hydrochloric acid. The ethereal phase
is washed with water, dried, and concentrated. High
vacuum distillation of the residue yields 52 g of
N-(3-trifluromethylphenyl)-3-1uoro-4-chloromethyl-
pyrrolidin-2-one with a boiling point of 115-120C/0.002 mb.
The product solidifies to a crystalline mass after a time.
Separation of the configuration isomers
F~ ~CH2-Cl F~ CH2-Cl
~!~! and ~! !
"cis", compound 50 "trans", compound 51
cis-N-(3-trifluoromethyl- trans-N-(3-trifluoromethyl-
phenyl)-3-fluoro-4-chloro- phenyl)-3-fluoro-4-chloro-
methyl-pyrrolidin-2-one methyl-pyrrolidin-2-one
10 g of the mixture of cis-trans-isomers obtained in
Example 1 are chromatographed on a column of silica gel
with a 1:3 mixture of ethyl acetate/hexane as eluant~
affording 2.5 g of cis-N-(3-trifluoromethylphenyl)-3-
fluoro-4-chloromethyl-pyrrolidin-2-one with a melting point
'
~3~0
- 12 -
of 54 -55 C, and 7.5 g of trans-N-(3-trifluoromethylphenyl)-
3-fluoro-4-chloromethyl-pyrrolidin-2-one with a melting point
of 72-74C.
Further compounds obtained by methods similar to
those described in the foregoing Examples are listed in
the following table:
Table: Compounds of formula 1
.
No. R Y z Physical data
1 CH2=CH-CH2- Cl Cl
2 n~C4H9~ H Cl
3 C6H5-CH2- H Cl ~ 1.4898
4 3-Cl-C6H4-CH2- H Cl nD 1.5391
3-Cl-C6H4-CH2- Cl Cl
6 CH3-0-CH2-CH2- H Cl
7 3-F-C6H4- H Cl nD 1.5439
8 3-Cl-C6H4- H Cl ~ 1.5542
9 3-Br-C6H4 H Cl m.p. 79.93C
3_I_C6H4_ H Cl m.p. 88-102C
11 3-CH -C H - H Cl nD 1.5348
12 3-OCH -C H - H Cl m.p. 84-87C
13 H Cl m.p. 124-130C
14 3-N0 -C U - H Clm.p. 80-90C
¦15 4-F-C H - H Clm.p. 96-114C
:,
~ - ,
-
~ ~3
- 13 -
Tabl e (continuation)
r I
Mo. R Y Z I Physical data
16 3-CF -4-Cl-C H - Cl m.p.107-109C.
17 3-CF -6-Cl-C H - H Cl
18 3-CF3-5-CF3 C6 3 H Cl b.p. 108-llO~C~'0,02 mb
19 3-N02-6-OCH3 C6 3 H Cl m.p.122-128C
3-OCH3-S-OC~3 C6H3 Cl Cl m . p . 87-94C
21 3-OCH3-6-OCH3 C6 3 H Cl ~ = 1.5481
22 3-C1-6-OCH3-C6H3- H Cl ~ = 1,5457
23 3-C1-5-Cl-C6H3- H Cl S emicrystall ine
24 3-F-6-F-c6H3- H Cl m . p . 117-124C
3-N02-4-CH3 C6 3 H Cl m.p.98-104C
26 3-C1-4-OCH -6-OCH -C6H2- H Cl m . p . 159-164C
27 3-Cl-4-Cl-6-Cl-C6H - H Cl m . p . 105-113C
28 C6F5- H Cl m.p.89-94C
29 3-OCF -C H - H Cl ~ = 1,4920
3-CHF2-0-C6H4- H Cl ~ = 1,5268
31 3 6 4 H Cl
32 3-CHF -S-C6H4- H Cl
~ 33 3-CHF2-S0-C6H4- H Cl
: : 34 3-CHF2-S02 C6 4 H Cl
; : 35 3-CF -C H - H Cl b.p. 115-120C/0,002mb
36 3-CF -C H - Cl Cl
37 ~ 3-CHF2-0-C6H4- Cl Cl
~ i_ ' I _ .
,,
.~ ,
36~1
- 14
Table (continuation)
_ ~ , . ,
No. z ¦ Physical data .
38 3-Cl-C6H4- Cl Cl
39 3-Br-C6H4- Cl Cl
3-CF -C H - H Br
41 3-Cl-C6H4- H Br
42 3-CH -C H - H Br
43 3-CF -C H - Br Br
44 3-Cl-C6H4- Br Br
3-Br-C6H4- Br Br
46 3-CF -C H - CH3 Cl
47 3-CHF2-0-C6H4 : CH3 Cl
48 3-Cl-C6H4- CH3 Cl .
49 3-Cl-5-Cl-C6H3- CH3 Cl
3-CF -C H - H Cl cis-isomerO
Cl ¦ trsns-isomgr
:::, . ~ . --~ .
.
:: :,. ~ : '' , , - I
-
~ ~36
- 15 -
Formulation Examples
Example l
Formulation Examples for liquid active in,~redients of the
formula I
(throughout, percentages are by weight)
a) Emul _fiable concentrates a) b) c)
compound 30 20 % 40 % 50 %
calcium dodecylbenzenesulfonate 5 % 8 % 5.8 %
castor oil polyethylene glycol ether 5 % - -
(36 moles of ethylene oxide)
tributylphenol polyethylene glycol ether - 12 % 4.2 %
(30 moles of ethylene oxide)
cyclohexanone - 15 % 20 %
xylene mixture 70 % 25 % 20 %
Emulsions of any required concentration can be
produced from such concentrates by dilution with water.
b) Solutions a) b) c) d)
compound II 80 % 10 % 5 % 95 %
ethylene glycol monomethyl ether 20 % - - -
polyethyleneglycol 400 - 70 %
N-methyl-2-pyrrolidone - 20 %
epoxidised coconut oil - - l % 5 %
petroleum distillate - - 94 %
(boiling range 160-190C)
These solut~ons are suitable for application in the
form of microdrops.
6 ~ 0
c) Granulates a) b)
compound 8 5 % 10 %
kaolin 94 %
highly dispersed silicic acid 1 ~/O
attapulgite - 9o %
The active ingredient is dissolved in methylene
chloride, the solution is sprayed onto the carrier, and
the solvent is subsequently evaporated off in vacuo.
d) Dusts a) b)
compound 8 2 % 5 %
highly dispersed silicicacid 1 % 5 %
talcum 97 %
kaolin - 90 %
Ready-for-use dusts are obtained by intimately mixing
the carriers with the active ingredient.
Example 2
Formulation examples for solid active in~redients of the
~ormula I
(throughout, percentages are by weight)
a) Wettable powders a) b)
c~mpound 35 20 % 60 %
sodium lignosulfonate 5 % 5 %
sodium lauryl~ulfate 3 %
sodium diisobutylnaphthalenesulfonate - 6 %
octylphenol polyethylene glycol ether - 2 %
7-8 moles of ethylene oxide)
highly dispersed silicic acid 5 % 27 %
kaolin 67 %
- - .
. ` . ' ',:
36~0
- 17 -
The active ingredient is thoroughly mixed with the
adjuvants and the mixture is thoroughly ground in a suitable
mill, affording wettable powders which can be diluted with
water to give suspensions of the desired concentration.
b) Emulsifiable concentrate
.
compound 50 10 %
octylphenol po~yethylene glycol ether ~ %
(4-5 moles of ethylene oxide)
calcium dodecylbenzenesulfonate 3 %
castor oil polyglycol ether 4 %
(36 moles of ethylene oxide)
cyclohexanone 30 %
xylene mi~ture 50 %
Emulsions of any required concentration can be ob-
tained from this concentrate by dilution with water.
c) Dusts a) b)
compound 51 5 % 8 %
talcum 95 %
kaolin - 92 %
Ready-~or-use dusts are obtained by mixing the active
ingredient with the carriers, and grinding the mixture in
a suitable mill.
d) Extruder ~ranulate
compound 19 10 %
sodium lignosulfonate 2 %
carboxymethylcellulose 1 %
kaolin 87 %
3 ~ ~ ~
The active ingredient is mixed and ground with the
adjuvants, and the mixture is subsequently moistened with
water. The mixture is extruded and then dried in a stream
of air.
-e) Coated ~ranulate
compound 12 3 %
polyethylene glycol 200 3 %
kaolin 94 %
The finely ground active ingredient is uniformly
applied, in a mixer, to the kaolin moistened with
polyethylene glycol. Non-dusty coated granulates are ob-
tained in this manner.
f) Suspension concentrate
compound 10 40 %
ethylene glycol 10 %
nonylphenol polyethylene glycol ether 6 %
(15 moles of ethylene oxide)
sodium lignosulfonate 10 %
carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 %
silicone oil in the form of a 75 % 0.8 %
aqueous emulsion
water 32 %
The finely ground active ingredient is intimatelymixed with the adjuvants, giving a suspension concentrate
from which suspensions of any desired concentration can be
~ obtained by dilution with water.
: ~
Biolo~ical Examples
The following test methods are employed to deter-
mine the pre- and postemergence herbicidal activity of the
,
. :
- . . - :
.
`` ` 1 ~3~
- 19 -
compounds of the formula I:
Example 1: Preemergence herbicidal action
In a greenhouse, plant seeds are sown in flower pots
of 12-15 cm diameter. Immediately after sowing, the surface
of the soil is treated with an aqueous dispersion or
solution of the compounds to be tested. Concentrations of
4 kg a.i./ha are employed. The pots are then kept in the
greenhouse at 22-25C and 50-70 % relative humidity. The
test is evaluated 3 weeks later in accordance with the
following rating:
1 = plants have not germinated or are totally withered
2-3 = very pronounced action
4-6 = medium action
7-8 = insignificant action
9 = no action (as untreated controls)
~m~r~ence Action
Rate of application: 4 kg a.i./ha
Com- Avena Setaria Sinapis Stellaria
~: : ~
: ,
36~0
- 20 -
Example 2: SPlective preemergence action
A large number of plant seeds are treated with
compounds to be tested at different rates of application
in the same test procedure as described in Example 8.
Evalua~ion is made in accordance with the same rating.
In this test the compounds of formula I exhibit
excellent activity against dicot weeds and against most
grass weeds, whilst cultivated plants such as cereals,
maize, millet, rice~ soybeans and cotton are not damaged,
or are damaged to only an insignificant extent, at
appropriate rates of application.
,,............... , , ~
,
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~ ~36
- 21 -
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g ~ l ~
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r~l ~ 0~ ~ a~
g oo cs~ r~
cd ~ ~ c~
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oo ~ ~ l
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- 23 -
I .
o~ ~ ~ I I I
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u~O~ ~ I I
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- 24 -
Example 3: Postemergence herbicidal action (contact action)
A number of weeds and cultivated plants in pots, both
monocots and dicots, are sprayed postemergence, in the 4-
to 6-leaf stage, with an aqueous active ingredient
dispersion at a rate of application of 4 kg a.i./ha, and
then kept at 24-26C and 45-60 % relative humidity. The
test is evaluated 15 days after treatment and the action
is assessed in accordance with the same rating as employed
in Example 1.
In this test also the compounds of formula I exhibit
excellent activity against dicot weeds and most grass
weeds, whilst the cultivated plants such as cereals, maize,
millet, rice, cotton and soybeans are not damaged or are
damaged only at higher rates of application.
Postemergence action
Rate of application: 4 kg a.i./ha
Com- Setaria Solanum Sinapis Stellaria
i I ~ 2 1 2
,,, ,, ,, . ~.....
~36'~0
- 25 -
Fxample 4: Comparison test to det~rmine better tolerance of
cultivated plants to compounds of the formula I
Using the same test procedure as in Example 1, seeds
of different varieties of cereals and the principal weeds
in crops of cereals are treated with active ingredient at
different rates of application. Evaluation is made 3 weeks
later.
The comparison compounds employed are
compound 35 .~ CH2cl
and compound A ~ ¦ 2
disclosed in German Offenlegungsschrift 2 612 731.
The results reported in the following table indicate
the percentage growth in comparison with untreated
controls.
Preemer~ence comparison test in crops of cereals
. .
Growth in % compound 35 compound A
_ '
Test plant 2 1 0.5 kg a.i.~ 2 10.5kg ~i.
,
summerwheatC'Sveno"y 75 90 100 40 50 9o
winter ~eat ("Probus")75 loo loo 60 7s go
winter ~rley ("Nymphe") 90 90 10025 so 9o
Alopecurus myos. O 0 50 O O O
Sinapis alba O O O O O O
Matricaria cham. O O O O O O
Stellaria media O O O O O O
Veronica pers. O O O O O O
Viola tricolor O O O O 0 10
,~ ~..., -
.
" ~ .
~ ~36~0
- 26 -
The test results clearly indicate that compound
35 is better tolerated at higher rates of application by
the cereals plants than comparison compound A.
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