CA1163640A - Fluoropyrrolidinones, the production thereof, herbicidal compositions containing them, and method of use thereof - Google Patents

Abstract

Abstract of the Disclosure The invention relates to fluoropyrrolidinones of the formula I
(I) wherein R is C1-C4alkyl, C3-C4alkenyl, alkoxyalkyl of at most 5 carbon atoms, benzyl or benzyl substituted by halogen, C1-C4alkoxy or C1-C4alkyl, or is phenyl or phenyl monosubstituted or polysubstituted by halogen, nitro, cyano, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4haloalkylthio, C1-C4alky-sulfinyl, C1-C4haloalkylsul-finyl, C1-C4alkylsulfonyl or C1-C4haloalkylsulfonyl; Y is hydrogen, C1-C4alkyl, fluorine, chlorine or bromine; and Z
is chlorine or bromine.
These compounds have selective herbicidal properties and can be used for controlling weeds in different crops of useful plants, e.g. cereals, rice, soybeans and cotton.

Description

~ ~36~0 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 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 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 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~

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 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

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 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~

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

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 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 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 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 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 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 , . :
- . . - :

.

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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 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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a ~ ,~ ~: O ~ ~ ~ ~ d ~o ~n ~ ~ ~: o 'S ~ C ~1 ~ UP` ` ~0~ i o ~ ~ ~ X ~ ~ ~

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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 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 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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Claims (9)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A fluoropyrrolidinone of the general formula I

(I) wherein R is C1-C4alkyl, C3-C4alkenyl, alkoxyalkyl of at most 5 carbon atoms, benzyl or benzyl substituted by halogen, C1-C4alkoxy or C1-C4alkyl, or is phenyl or phenyl monosubstituted or polysubstituted by halogen, nitro, cyano, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4haloalkylthio, C1-C4alkylsulfinyl, C1-C4,haloalkylsul-finyl, C1-C4alkylsulfonyl or C1-C4haloalkylsulfonyl; Y is hydrogen, C1-C4alkyl, fluorine, chlorine or bromine; and Z
is chlorine or bromine.

2. A compound of the formula I, wherein R is a phenyl radical which is monosubstituted or polysubstituted by halogen, nitro, cyano, methoxy, halomethoxy, methyl, halomethyl, halomethylthio, halomethylsulfinyl or halomethyl sulfonyl, Y is hydrogen, methyl, chlorine or bromine, and Z is chlorine or bromine.

3. A compound of the formula I according to claim 2, wherein R is a phenyl radical which is monosubstituted or polysubstituted by halogen, halomethyl or halomethoxy, Y
is hydrogen or chlorine, and Z is chlorine.

4. A compound according to claim 3, wherein R is a phenyl radical which is substituted in the 3-position by halogen, trifluoromethyl, trifluoromethoxy or difluoro-methoxy, Y is hydrogen or chlorine, and Z is chlorine.

5. N-(3-Trifluoromethylphenyl)-3-fluoro-4-chloromethyl-pyrrolidin-2-one and the diastereomers thereof.

6. A process for the production of a compound of the formula I according to claim 1, which process comprises heating a N-allylacetamide of the formula II

(II) wherein R, Y and Z are as defined for formula I, in the presence of a catalyst and in an inert solvent.

7. A method of selectively controlling weeds in crops of cultivated plants, which method comprises applying there to or to the locus thereof a herbicidally effective amount of a compound according to claim 1.

8. A method according to claim 7, wherein the compound according to claim 1 is applied pre- or postemergence.

9. A method according to claim 7, wherein the crop is cereals, rice and cotton.