CS212334B2 - Mena for regulation of the plant growth - Google Patents

Abstract

1. A substituted sulfonic acid anilide of the formula (I) see diagramm : EP0013742,P14,F1 where R**1 is alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl (each of up to 12 carbon atoms) or arylalkyl (of 7 to 14 carbon atoms), each of which may be unsubstituted or substituted by halogen, cyano, thiocyanato, azido, nitro, C1-4 -alkoxy, C6-10 -aryloxy, C1-4 -alkylthio, C6-8 -arylthio, C1-4 -alkylsulfinyl, C1-4 -alkylsulfonyl, arylsulfinyl, arylsulfonyl, C1-5 -alkanoyl, C1-5 -alkoxycarbonyl, C1-5 -alkylcarbamyl, di-(C1-5 -alkyl)-carbamyl, C1-4 -alkanoylamino, C1-4 -haloalkanoylamino, C1-6 -alkanoyloxy, C1-4 -alkanoylthio, C1-4 -alkoxycarbonyl-amino, C7-13 -aroyloxy, C1-6 -alkylamino, di-(C1-6 -alkyl)-amino, C6-12 -arylamino, C1-6 -alkylcarbamyl-amino, di-(C1-6 -alkyl)-carbamylamino, C1-6 -alkyl-carbamyloxy, di-(C1-6 -alkyl)-carbamyloxy, C1-4 -alkylaminosulfonyloxy or di-(C1-4 -alkyl)-amino-sulfonyloxy or combinations of these groups, or is cyano, thiocyanato, unsubstituted or C1-4 -alkyl-substituted amino, aminosulfonyl, guanyl, N2 -hydroxyguanyl, hydroximoyl or C1-5 -alkoxy-imidoyl, or is unsubstituted or halogen-substituted C1-4 -alkylsulfenyl or C1-4 -alkylsulfinyl, or is unsubstituted or halogen- and/or C1-4 -alkyl-substituted arylsulfinyl or arylsulfonyl, where aryl is of up to 10 carbon atoms, R**2 and R**3 are identical or different and each is halogen, cyano, thiocyanato, nitro or unsubstituted or halogen-substituted C1-4 -alkyl, C1-4 -alkoxy, C1-4 -alkylthio, C1-4 -alkylsulfinyl, C1-4 -alkylsulfonyl or C1-4 -alkanoyl.

Description

is optionally halogen, cyano, thiocyanato, (C1-C4) alkoxy, (C6-C10) aryloxy, (C1-C4) alkyl-sulfonyl, (C1-C4) alkyl-aryl, (C6-aryl) -8-aryl) C 1 -C 5 alkanoyl, C 1 -C 5 alkoxycarbonyl, C 1 -C 5 alkylcarbmoyl or C 1 -C 5 dialkylcarbamoyl, C 1 -C 4 haloalktnioylimino C 1 -C 6 alkanoyloxy, C 1 -C 4 alkyloxycarbonylamino, C 1 -C 6 alkyl or C 1 -C 6 dialkylamino, C 6 -C 12 aryl-amino, C 1 -C 6 -alkyloxy; having 1 to 6 carbon atoms in the alkyl or dialkoxycarbonyl-amino group having 1 and (C 1 -C 6) alkyl, (C 1 -C 6) alkyl, (C 1 -C 6) alkyl or (C 1 -C 6) dialkyl (C 1 -C 6) alkyl, (C 1 -C 4) alkyl or (C 1 -C 4) alkyl or (C 1 -C 4) alkylsulfonyloxy group; alkyl, alkenyl, alkenyl, cycloalkyl, cycloalkenyl having up to 12 carbon atoms in each of the above groups, or arylallyl having 7 to 14 carbon atoms, cyano, thiocarbonyl or alkyl C1-C4-substituted amino-substituted, amino-substituted amino, guanyl, N2-hydroxyguanyl, hydroxiboyl or C1-C5alkoxyibidoyl, optionally halogen-substituted C1-C4-alkylsulfonyl ,

3

R and R 'are the same or different and are hydrogen, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylthio C1-4 alkyl, C1-4 alkylalkyl or C1-4 alkanocyl; R4 is C1-4 alkylcarbonyl, optionally substituted by C1-4 alkanoyl or halogen-substituted C1-4 alkanoyl; C 1-4 alkyl or optionally C 1-4 alkyl or C 1-4 alkyl substituted carbamyl, or a C 1-4 alkyl, R 5 is optionally halogen C 1 -C 4 alkyl is C 1-4 alkyl.

The symbol R 'may mean:

methyl, stylish, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, t-butyl, cyclobutyl, n-pentyl, 2-peityl, J-pentyl a tertiaryl group, a neopentyl group, a 2-betylbutyl group, a N, N-butyl group,

3-benzyl, cyclopentyl, n-hexyl, 4-methyl, 2,3-tributyl, 2-benyl-2-pentyl, 2-hexyl, 3-hexyl, 3-biphenyl-2-pentynyl, J-methyl, J-methyl-J-pentyl, 4,4-dibethyliutyl, cyclohexyl, heptyl, 4-Heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-octyl, 2-octyl, 3-octyl, 4-Ltyl, 6-octyl, S-ethyl - ^ - heptyl, 2,6-dimethyl-4-heptyl, -7-ethyl-2-methyl-4 - ((1) -), 2,4-dimethyl-2,4-dimethyl-3- pentyl, 3-benyl-2-heptolyl, 5-ethyl-2-aminoalkyl, nonyl, decyl, undecyl, dodecyl, 6-β-β-4-cyclic group, 6 -n-1-oct-3-ol, 2-benyl-2-pityl, 2,3-dibethyl-2-itolyl, 2-benyl-2-hexyl-3-ol tlk-3-pityl, 3-661-3-3-xyl, 2,3-dibethyl-3-pentyllU, 2,4,4-6,6-1-2-peritolyl, 2,2,3 - (11-3-4) -yl, 2-benyl-2-naphthylol,

A 4-benzyl-4-nitro group, a 2,4-dibetyl-2-naphtholyl group, a 2-bonyl-2-octanol group,

1-methyl-1-cyclopentyl, 1-methyl-1-cyclohexyl, 1-ethyl-1-cyclohexyl, chloro-tert-butyl, 1,1-dichloro-2-methyl-2-propyl, 1 , 3-dichloro-2-methyl-2-propyl, 1-cyclohexyl-1-style, 1-chloroethyl,

2-chloroethyl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 1-chloro-2-propyl, 2-chlorobutyl, 2-chloro-2-methyl-3-propyl, 1-fluoroethyl a group, 2-fluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 1-fluoro-2-propyl, 2-fluorobutyl,

2-fluoro-2-methyl-3-propyl, 2-bromomethyl, 3-bromopropyl,

4-chlorobutyl, 2-chlorocyclohexyl, 1,1,1-trifluorisopropyl, hexafluoro-2-methylisopropyl, hexafluorisopropyl, hexachlorisopropyl, 1,2-dibromallyl, 2,2,2-trifluoroethyl, 1- chlorobut-2-yn-4-yl, 3-chlorobut-1-yn-4-yl, 1-chlorobut-2-en-4-yl, 2,3-dibromo-1-propyl, 2, 2,2-trichloroethyl, 1-chloropent-2-yn-4-yloy, 2,2,2-tribromomethyl, 3,4,4-trichlorobut-3-en-2-yl-10-group, 1-bromo- 2-ergyl, 1,3-dibromo-2-propyl, 3-chlorobut-1-en-4-yl, allyl, methallyl, crotyl, 2-ethylhex-2-en-1- yl, hex-5-en-1-yl, undec-10-en-1-yl, 2-methylbut-2-en-1-yl,

2-methylbut-1-en-3-yl, but-1-in-3-yl, but-2-in-1-yl, but-1-en-3-yl, propargyl, 2 -methylbut-1-en-4-yl, 2-methylbut-2-en-4-yl, 3-methylbut-1-en-3-yl, 1-ethynylcyclohexyl, methoxyethyl, ethoxyethyl, 3 -methoxypropyl, aetoxyisopropyl, 3-methoxybutyl; i-methoxybut-2-yl, ethoxy-tert-butyl, methoxy-tert-butyl, cyclohexoxy-tert-butyl, 2-methoxybutyl, 4-methoxybutyl, methylmercaptoethyl, ethylmercaptoethyl, 3-methylmercaptopropyl , 3-methylmercaptobutyl, 1-methylmercapto-2-butyl, methylmercapto-tert-butyl, 2-methylmercaptobutyl, 4-methylmercaptobutyl, 3-n-butoxyethyl, 2-ethoxypropyl,

3-ethoxy-2-propyl, 2-methylbutan-3-one-1-yl, 2-methylpentan-4-one-2-yl, 3-butanone-1-yl, 3-butanone-2- yl, 2-propanone-1-yl, 2-pentanone-1-yl, 2-methyl acetate, 2-ethyl acetate,

2-methylpropionate, 3-methylpropionate, 2-ethoxy-2-ethyl acetate, 2-methoxy-2-ethylpropionate, methyl (2-oxyl-2-propionate), ethylcarbamoylethyl, dimethylcarbamoylmethyl, thio cyano , guanyl, N, ^4- methylguanyl, N, ^5- methylguanyl, N, 4-isopropylguanyl, N, ¹ , N, ⁴ dimethylguanyl, N ¹ , Ν ¹ , N ² -trimethylguanyl, N, ^4- hydroxyguanyl, N, metoxyguanylovou group metoxyimidoylovou group isopropoxyimidoylovou group aetankarbohydroximoylovou group benzohydroximoylovou, O-metylbenzphydroximoylovou group, aminocarbonylmethyl, ethyl aminocarbonyl, amino, diaetylaminoskupinu Ni SOPR dipropyl-N-methyl butyl amino group, a _methylamino} isopropylamino, etylsulfenylovou group, 2,4-dinitrophenylsulfenyl, dichlorofluoromethylsulfenyl, trichloromethylsulfenyl group n-methylsulfamoyl, N-isopropyl 1-N-methylsulfamoyl, alpha-cyanethyl, beta-cyanethyl, cyanomethyl, rhodanomethyl, methylsulfinylmethyl, benzylsulfinylmethyl, 4-methylsulfinylbutyl, 1-methyl sulfones1 -2-butyl, etylsulfonyletylovou group metylsulfonylaetylovou, p-chlorbenzylsulfonylmetylovou group fenylsulfonylaetylovou group azidoaetylovou, .beta.-azidoetylovou group, acetylaminomethyl group, p-chloro-benzoylaminometylovou, propionyloxymethyl group, acetoxymethyl group, N- (2 _T 6 -dimethylphenyl) -N-methoxycarbonylaminoethyl, N- (2-ethylphenyl) -N-ethoxycarbonylaminomethyl, N- (2-methyl-6-ethylphenyl) -N-chloroacetylaainomethyl, beta-N, N-dimethylaminoethyl a group, beta-N, N-diisopropylaminoethyl, beta-N-phenylaminoethyl, piperidinomethyl, diaethylaminomethyl, morpho linomethyl, methylsulfonyloxymethyl, N-methylaminosulfonyloxymethyl.

R 4 is preferably fluoro, chloro or bromo substituted acetyl, propionyl, butyryl or isobutyryl. Further, it represents methanesulfonyl, phenylsulfonyl or N-alkyl- or N, N-dialkylaminoaulfonyl, methoxycarbonyl, ethoxycarbonyl, methylthiocarbonyl. isopropylthiocarbonyl, N-methylcarbamoyl, N, K-dimethylcarbanioyl, 3,4-dichlorophenylcarbamoyl.

A particularly preferred group of sulfonic acid anilides of formula (X) are the compounds of formula (I) in which they are

R @ ¹ optionally substituted by halogen, cyano, thiocyanato or azido in the alpha or beta position to the nitrogen atom of the sulfonamino group substituted by an alkyl radical of 1 to 4 carbon atoms, further denotes an alkyl radical having 1 to 3 carbon atoms optionally on the alpha carbon atom; beta substituted by C 1 -C 4 alkoxy, C 1 -C 3 alkylsulfinyl, C 1 -C 2 alkylsulfonyl, N-chloroacetyl-N-arylamino, C 1 -C 4 dialkylcarbamoylamino, alkoxycarbamoyl (C 1 -C 4) alkoxy, (C 1 -C 6) alkanoyloxy or (C 1 -C 13) aroyloxy, furthermore optionally substituted by C 3 -C 4 alkenyl or alkynyl, cyano or thiocyanato,

^R2 and R3 are independently hydrogen, methyl, halogen, methoxy, methylthio or methylsulphonyl group,

R ^{4 is an} optionally substituted C 1 -C 4 alkanoyl group;

R @ 1 is a fluorine alkyl radical having 1 to 4 carbon atoms.

The term halogen is preferably fluorine, chlorine and bromine.

The cycloalkyl group is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.

The novel substituted sulfonic acid anilides of formula (I) may be prepared by the formation of:

(a) compounds of formula IX;

NH-R ⁴ (II)

in which

R ^2, R, and R ⁴ have the abovementioned meanings, are reacted with compounds of formula XXI,

(III) in which:

R ¹ has the above meanings and

L is a nucleophilic leaving group, particularly halogen, hydrogen sulphate group, halogensulfonátovou group optionally substituted alkylsulfonyloxy group, _r arylsulfonyloxy group, alkyl sulfate group, an oxonium group, a sulfonium group or an ammonium group, '212 334 optionally in the presence of a diluent and / or acid-binding agent and / or accelerators reaction at temperatures between 0 and 170 ° C, or

(b) compounds of formula IV;

wherein R ^1, R ^2, R and R ⁴ have the abovementioned meanings, are reacted with a sulfonating agent of formula V,

R ⁵ -SO ₂ -Z (V) wherein the above meanings a

Z represents a leaving group, in particular a halogen or a residue of anhydride R @ 5 --SO2 O--, optionally in the presence of a diluent and optionally in the presence of an organic or inorganic base, at temperatures between -60 and +120.

Instead of the free compounds of the formulas II or IV containing hydrogen, the corresponding salts can also be used which are prepared according to known methods in the preceding step or optionally in situ by adding an equivalent amount of an organic or inorganic base, for example alkali metal, alkaline earth metal or alkyl-substituted ammonium salts.

The thus obtained derivative. Wherein R ¹ is alkylthioalkyl or arylthioalkyl groups can be optionally oxidized to the corresponding sulphinyl or sulphonyl derivative ^ alkylcarbonyl.

Derivatives in which R @ ¹ is cyano can be reacted with amines, alcohols or hydroxylamines to give the corresponding guanyl or alkoxyimidoyl derivatives.

When 5-acetamido-2,4-dimethyl-trifluoromethanesulfonanide and methyl bromide are used as starting materials, the reaction sequence according to the invention according to variant a) can be illustrated by the following reaction scheme:

If 5-acetamido-2,4-dimethyl-trifluoromethanesulfonanilide and chloroacetonitrile and sodium iodide sodium salts are used as starting materials as starting materials, the reaction sequence according to the invention according to variant a) can be illustrated by the following reaction scheme:

⁽ Nal)

-NaCI

If 5-acetamido-2-methylphenyl cyanamide and trifluoroethanesulfonic acid chloride are used as starting materials, the reaction according to the invention can be carried out according to the variant

(b) be depicted as follows: '

NHCOCHj

· 4 tSO4CF, -.

NHCOCH3

Ol

T> -s ^o 2 ^c 'f 3 ^{CH 3} C

For example, the following may be used for both process variants. solvents, optionally diluents: water, formamides such as dimethylformamide, formamide, dimethylacetamide, OLtril such as acetetoitil, benzol trH, buttyroittil, sulfoxides such as dimethylsulfuxide, phosphoric acid amides such as hexianeeyytrimide phosphoric acid, ketones such as acetone ethyl acetate acetophenone, ethers such as tetrihydrofuran, anisole, dimethylethyl, n-butylethyl ether, dioxane, nitroalkanes such as oltroethane, nitrobenzene, alcohols such as methanol, ethanol, n-propanol, n-butanol, Z mo -теХу ^^ а ^ !, moleic acids such as auntimide / urea, ethers. alcohols such as ethylergylmethylsulfonylethylsulfones, esters such as ethyl acetate, methyl yroyionic acid, formic acid, halogenated hydrocarbons, especially chlorinated hydrocarbons, for example chlorinated hydrocarbons, e.g. 1,2,2-oybb'1,1,1, e-tathlorocyan-ai, dichloropropane, -tetylsttylto, chlorobenzene, o, m, p-diclorbenzto, fluorobenzene, s, m, p-chlsrtslutn, Ι ^ Ι Aliphatic or cyclooaifate, including hydrocarbons such as leptane, pinane, iodine, and the like. Gasoline fractions boiling in the range of 70 ° C to 190 ° C; Methylcyclohexao, decaine, petroleum ether, Heroin, 2,2,4-trioetilyeotane, octane, aromatic hydrocarbons such as benzene, toluene, cis-xylene, tralio and mixtures thereof. Suitably the solvent is used in an amount of from 100 to 2,000 hours, preferably from 100%. up to 1000% by weight based on the starting materials of formulas II and IV, respectively.

Processes a) and b) according to the invention are preferably carried out in the presence of an organic or inorganic base. In particular, basic hydride compounds, basic oxides, tertiary amines,. alkoxides, carbonates or lydrides, for example, potassium hydroxide, sodium hydroxide, potassium carbonate, calcium okid, barium oxide, barium hydroxide, barium oxide, barium hydroxide, calcium carbonate, barium carbonate, barium hydroxide, zinc hydroxide, zinc oxide, zinc oxide. zinc zinc, zinc hydrogeililine, such as sodium, sodium methoxide, potassium ethoxide, sodium propoxide, aluminum isopropoxide, butoxide. sodium methoxide, calcium methoxide, calcium cyloxoxoxide, sodium isopropoxide, potassium tert-butoxide, -Γίοχ-ιίβοΐη,.

trisylemine, trPropyLemine, trispropylpolymine, trbutylimine, trisobutylmine, trisobutylmine, trisobutylmine, trpbutylimine, tricyclohexylemine, tricyclohexylemine, triethylamine, triethylbutyl. N, N-ϋοβΧ-τΙιιΟΙΡο, N, N-dPetyl 01 PPo, Ν-, Ν-ss ss sy sy sy.. Lio lio,, Ν, i-thioethyl P PdPn, N, N-diityl l io Ν io -amPnosyУtdPn, N, N- (lietyl-> paranopyyPdPn, -llpiperidio, N-eeylpPyeyPiin, ^ - ^ о ^ '- У'уг ^ г ^ Ис ^^. п, N-tylyylУoOPiPo, N-motyliyyrol, N N-N-ethylphosphonoOPo, N-motylhexamothylenimine, pyridine, chioplio, alpha-4-picollo, N, N, N *, N * -theeryl ethyl ethylmixture, N-ethyldiproproyl nitride, Ν, imedimethylhydroxydride, sodium hydride, sodium hydride, sodium hydride; Preferred reaction accelerators are preferably iodides and metal bromides, for example sodium iodide, potassium bromide, calcium iodide, crown ethers, quaternary ammonium compounds such as tetrabutylammonium iodide or tetrabutylammonium bromide, or combinations thereof.

Process a) is generally carried out at temperatures of from 0 to 170 ° C, preferably at 0 to 140 ° C, for 30 minutes to 100 hours, preferably 1 to 24 hours, at atmospheric pressure or at elevated pressure, continuously or discontinuously.

Generally, in process a), 0.5 to 2 mol, preferably 0.9 to 1.5 mol, of the compound of formula III or 0.5 to 2 mol of the base and 0.01 to 1.5 mol, respectively 0.1 mol reaction accelerator. In order to isolate the reaction products of the formula I, in the case of using water-miscible solvents or diluents, the reaction solution or residue obtained after removal of the solvent or diluent is transferred to a dilute aqueous alkali solution. An oil is formed which is extracted or the solution is separated by decantation. Any precipitate formed is filtered off. When using solvents that are not miscible with water, the organic phase is generally extracted with a dilute aqueous alkali solution, dried and concentrated. If the desired product precipitates directly during the reaction, it can be isolated by simple filtration. If desired, the reaction products can be further purified in the customary manner, for example by recrystallization or chromatography.

Process variant b) is carried out generally at a temperature of -60 to +120 ° C, preferably at -40 to +80 ° C for 1 to 100 hours, at ambient or elevated pressure, continuously or discontinuously. of the compound of formula IV 0.8 to 1.3 mol, preferably 0.9 to 1.1 mol, of the sulfonating agent and 0.8 to 2 mol of the base. The isolation of the reaction product of the formula I is carried out as in process variant a).

He did

A solution of 5.9 parts of sodium cyanide in 40 parts of water is added dropwise to the suspension of 19.2 parts of bromine in 80 parts of water with stirring over about 10 minutes at 0-10 ° C. After destaining, the mixture was allowed přitéct'roztok 4 parts of sodium hydroxide and 31 parts of 5-acetamido-2,4-dimethyl-trifluormetansulfonaniiidu in 50 parts water and stirred for 5 hours at 50 ^at C. After cooling, the reaction mixture is alkalinized, and by adding a small amount of aqueous alkali metal hydroxide, and then filtering off the precipitate. After drying, 29.5 parts (88% of theory) of 5-acetamido-N-cyano-2,4-dimethyl trifluoromethanesulfonanilide, m.p. 110-111 ° C, are obtained.

Example 2

To a solution of 49.8 parts of 5-acetamido-2,4-dimethyl-trifluoromethylsulfonanilide sodium salt in 150 parts of dimethylformamide, 15.5 parts of chloromethyl methylsulfide was added in one portion. The reaction mixture is stirred for about 8 hours at room temperature, then poured into water, extracted with ether and the organic phase is washed with water and 1N aqueous sodium hydroxide solution. After drying, concentration and stirring with diisopropyl ether, 48.1 parts (86.7% of theory) of 5-acetamido-2,4-dimethyl-N- ¹ -methylthiomethyl-trifluoromethanesulfonanilide of melting point 106 DEG-107 DEG C. are obtained.

Example 3

17.3 parts of 5-acetamido-2,4-dimethyl-N-methylaniline in 100 parts of chloroform were added dropwise separately at 0 ° C, while 17 parts of trifluoromethanesulfonic acid chloride and 10.3 parts of triethylamine were added dropwise. The reaction mixture is stirred overnight at room temperature, then the precipitate is filtered off, washed thoroughly with chloroform and the organic phase is extracted with water and 2N aqueous hydrochloric acid. After drying and concentration, 24 parts (82% of theory) are obtained.

5-acetamido-2,4-dimethyl-N ¹ -methyl-trifluoromethanesulfonanilide, m.p. 128-130 ° ^C ;

Example 4

To a suspension of 10 parts of O-methylhydroxylamine hydrochloride in 100 parts of ethanol is added

7.2 parts of sodium carbonate and the mixture was stirred at room temperature for 1 hour. After addition of 37 parts of 5-acetamido-N ¹ -cyano-2,4-dimethyltrifluoromethanesulfonanide, the reaction mixture was stirred at room temperature for 10 hours and at 50 ° C for 5 hours, the solvent was evaporated in vacuo and the residue poured into water. The oil which has precipitated is extracted with ethyl acetate, the organic phase is washed twice with water, dried and concentrated. The residue is then treated with a mixture of diisopropyl ether and toluene. Yielding 25 parts of 5-acetamido-2,4-dimethyl-N ^I - ^(2-methoxy N), guanyl trifluormetansulfonanilidu mp 105-107 ° C.

Example 5

To 18.6 parts of 5-acetamido-2,4-dimethyl-N ¹ -methylthiomethyltrifluoromethanesulfonanilide (see Example 2) in 200 parts of chloroform at -10 ° C was added a solution of 10 parts of 85% m-chloroperbenzoic acid in 120 parts of chloroform. After standing overnight, the reaction mixture is poured into a saturated solution of bicarbonate in water, which is used in excess, the organic phase is washed again with the bicarbonate solution, dried and concentrated. After stirring with diisopropyl ether, 16.5 parts (82% of theory) of 5-acetamido-2,4-dimethyl-N ¹ -methyl-8-sulfonylmethyl-trifluoromethanesulfonanilide, m.p. 161-163 ° C, are obtained.

Other compounds of formula (I) are prepared analogously to the procedures described above and are summarized in the following table:

Example R ¹ R T R <R ⁴ R ^? Melting point (° C) no

π in Рч m m <n m € _f * X Рч m СП (М fe сП m СП IR CM Рч Рч Рч Рч OJ Рч Гч Рч й Рч Рч Рч O O O O O O O ω О О О о о no о

я л л о о о см см см л л я no о Q

o íf

яГ см и см л sP Л г Л я и 8 8 8 8 и о о о 8 О о см л см л см л СМ. л яГ яГ см л яГ 0 л о о о ϋ О о no О no

CH-0CH H _{K of} the CM, CRL · CH .CO- GF-93-95

cm

5rl

Р О г1 а.

Ен

I о о

<4 о

о о о и о о о о Ó о о о и о иГ о ίχΓ no Í ¹ Í ¹

and

сП вР д ' ¹ СП д н вР гЧ НгГ д д д ⁹ « о О Д о о о Д о о о о

см_ д вР Д ° Sleeping д ^ иГ * н вР Д ³ Д « о о ООО о о о о о о

вР

см СП lř \ 40 г- см см см см см см

тГ * δ сп СП m ώ 1 3 (AT and еГ вР о еГ ? r

аэ см σ \ о см сп сп

Example R ¹ R ² R ³ R ⁴ R- Temperature ⁴ ° (° C) no

CM

TJ о гН Н А4 м * нм к *

см В Рч СЧ СМ СМ Рч

со ГО , со го „Со со „Со СО -СО со й см см Рч со ч Рч Рч δ Рч Рч Рч & Рч Рч л л со δ 3 no О О О о о О О о no о о

Л .г » см . со <Í Ó и о I о о 4 č 4 О 4 no 4 č 4 О 4 no 4 О 4 О о см £ о л СО СО яГ со со со со со со со со 1 о Рч Р л л Л Л л Л Л Л н • н о о о о no о О О no О о о

о о о J) яГ яГ о о 5 ¹ еГ <* ·> 5 йР о я аР лол • яГ о Г žT яГ £ * о о

гГ

яГ

яГ л ^ яР Р о о О о

о \. о -М- ш

СМ (И «1

1Г \ и \

1Г \ ίο \ С · СО ш 1Г »о

1Г \ 40> N CO f04> N

гэ 0Ί m m Рч Рч Рч Í4 Рч O O O O O O

OH cn m m m X X and X X O O O O O

OD HO

O CO X aP x ^ m X O O O O

continued table

M * rl

CM (П -in in КО Ο- СО Ок О см vo КО ко КО КО ΚΟ КО КО г- 0- t-

».

.

Μ

Ρ • Ρ ο Η Ρ.

• ti

O \ O

’<N OJ cn Сч <* ”> σ 4ГК fe Рч Рч Рч O О ϋ О

oa ^m uioo юк «

CM ϋ u

u m δ

o o jm o

«M o« * Ί sT o

.0

^ ι «· ^!

* £ ^ю

sT m И ₽Г сП М _ σ and о о О no. • ϋ · O

sT.? O

AND

OJ

ι

ο-

КО Оo- o-

Oo oo γ! T

ítT δ

what WHAT what WHAT rO what in Рч Рч Рч Рч X Рч X O O O at O O

what WHAT what WHAT what WHAT what X X X X X X X O O O O O O

AND 1 o 4 4 O O at O WHAT what what what X X X X O O O O x ^ x * ¹ m X яГ O O o. O

cm ^ |, X ^ sT co X co X co X r X X 'O O O no ω O O

if continued table

Af m ЖМ

t 1 o ⁴ CO cT co Á CM CM 1 § 1 cP 2 ω o \ ’ч / \ CO CM CM з s _s í S <M i § tg яГ ± i § f ά и x co O 1 • H CM O X ^ CO č 1 • H Q 1 « от X X o o about what s w / O 1 in O in o 1 IN O 1 in O 1

WHAT • M · if\ 40 what what 00 what

what

pers O CM what 04 / 04 / 04 /

ΙΛ

1 About Q aP u 4 O gf 4 O sT aP ‘ O δ if - яГ o 8 ° with*

О 1 O and 1 о 1 о O no O о о о what СО со со Г П δ 8 8 я и 8 no aP я ^п аР я яГ я O о no о no what со го fh СО со Я я я я я Я O о о о б no

continued table

O H c4

ь · со 04 / О 04 / 04 / 04 / 04 / О

101 -CH _o COCH.

o From ok

OJ

KD O

CD

ГП

Рч

O

O

o <n

O

continued table

r

O <n o

ко o o-co o o

Example R ¹ R ² R ³ R ⁴ R ⁵ Melting point (° C) no

what what what WHAT WHAT what what WHAT X fa X fa Рч fa fa fa ϋ O O O O O O O

AND O 4 ω 4 no «Г» X яГ · аР O о no x ⁿ яГ X о о

4 4 4 4 О О О О яГ no > Р 3 <г> 5 г X о аР о ►Р 8 г

-CH ₂ NHCO-N (CH ₃ ) ₂ CH ₃ CH ₃ CH ₃ CO-

UX

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-СН ₉ ОС-СН, СН, Н СН, СО-CF, 125-130

The novel active substances have a potent biological effect on plants, i. affect the growth of plants, either by suppressing the height of plant growth, or by changing the concentration of substances contained in the plant, or by destroying undesirable plants while tolerating the snake plant.

The application is carried out, for example, in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, poppers, scatters, granules, by spraying, fogging, dusting, spreading or watering. The dosage forms are entirely guided by the purpose of use. .

Directly sprayed solutions, emulsions, pastes and oil dispersions are prepared for the preparation. the medium to high boiling mineral oil fractions, such as kerosene or oil for petroleum oils, coal tar oils, etc., as well as vegetable or animal oils, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene are considered. , paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, for example methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanoo, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents such as dimethylformamide, dimethylformamide, dimethylformamide; , N-methyl-pyrrolidkn and water.

Aqueous use forms can be prepared from ammonium concentrates, pastes or wettable powders, oil dispersions by adding water. For the production of emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent may be hydrogenated in water by means of adhesives, dispersants or emulsifiers. However, concentrates composed of the active ingredient, wetting agent, adhesive, dispersant or emulsifier and, optionally, solvent or oil, which are suitable for dilution with water, can also be prepared.

Among the surfactants there may be mentioned: alkali metal, alkaline earth metal or ammonium salts of lignin, alkali metal or alkaline earth metal salts of lignin, alkali earth metal or alkaline earth metal sulfonic acid salts of lignin, alkaline earth metal sulfonate, sulfonic acid, alkali metal sulphate fatty alcohols, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfonated hexadecanols, heptfecanols, octadecanols, salts of dried fatty alcohol glacol ether, condensation products of sulfonated πaltflile and derivatives of naphalene with formsldehyde, condensation products of n-phthalene or β-phthalene with phenol «F ormaldehyrdem, lolyoxχetylentkiylflntOéter, ttoxylovaπý iskkktylltпol- about yHeno ^! -, 'and nonylphenol _{fliylltпollklyglykikétee>} tribltylftnyllklyglykkOltee, fliylaryllklyéterflioholy, isktrideiylfliohkl, kojic dc ^ ^ e ^ s ^ i ^ c ^ i ^ ne pr fatty alcohol and fatty acid wastes, ethoxylated castor oil, glycol hexylphenyl ether, ethoxylated polycyclopropene, phosphoryl glycol ether, acetal, esters of sulfite, lignin, sodium hydroxide and sodium hydroxide.

Powders, dusts and dusts can be prepared by mixing or grinding the active ingredients together with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. The solid and carrier are, for example, clays such as silicas, silicas, silica, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomite, calcium sulphate and magnesium sulphate, magnesium oxide, ground plastics, fertilizers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea and vegetable products such as cereal flour, tree bark flour, wood flour and shell flour nuts, powdered cellulose, and other solid carriers.

The compositions contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90% by weight of active ingredient.

In various cases, the preferred combinations or mixtures of the compounds according to the invention with other plant growth regulating active compounds, such as, among others, various chemical structures having the ability to form ethylene (e.g. phosphonic acid and silanes, ethylhydrazines), onium compounds (e.g. trimethyl ammonium salts) , hydrazonium salts and sulfonium salts, derivatives of morpholinium, piperidinium and pyridazinium derivatives). Other substances which have the ability to control plant growth are also of importance, among others maleic acid hydrazides, abscisic acid derivatives, chlorinated phenoxy fatty acids with auxin-like effect, as well as higher alcohols and fatty acid esters and specific activity on meristemic tissue. .

The application rate of the compositions of the invention may vary. The application rate depends! mainly on the kind of desired effect.

The application rate is generally 0.1 to 15 or more, preferably 0.2 to 6 kg of active ingredient per ha.

The compositions according to the invention affect the growth of aboveground and underground parts of plants in various ways and have a low warm-blooded toxicity at the concentrations normally used.

The novel compositions interfere with physiological processes in plant development and can be used for a variety of purposes. The various effects of these active ingredients depend essentially on the time of application with respect to the seed or plant developmental stage as well as the concentrations used.

The new agents influence the vegetative and generative growth of the plants as well as the germination at the appropriate concentration.

Influencing the vegetative development mainly consists in decreasing the height of growth, which in many plants, especially cereals, achieves increased stalk strength and decreases the tendency to so-called lodging. At the same time, it will improve rooting, resulting in a higher number of cob-bearing stalks per unit area.

In grass, the decrease in height is reflected in a denser, more resistant crop and, above all, in saving more mowing. The above-mentioned effect results in considerable labor savings in the treatment of ornamental grasses, and especially in the treatment of grassy areas along roads on park areas. In addition, in parallel to the decrease in height, the chlorophyll content increases, thus giving the treated grass areas, but also the other vegetation, a much darker green color.

Influencing the vegetative growth in many plants, such as cotton and soybeans, causes a significant increase in the number of flowers and fruit planted.

In particular, it should be pointed out that the treatment with the substances according to the invention promotes root growth. This leads to more efficient use of water and nutrients by the treated plants. This not only increases the drought resistance but also the cold resistance (frost resistance).

The application possibilities for fruit and ornamental plants as well as for cultivation of soil, including the relevant influence on eel vegetation as well as on airfields and training grounds, are also multifaceted and extensive.

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The compounds according to the invention can also be used successfully in influencing inflorescences and maturation processes as well as in particular cultivation methods.

Last but not least, new agents can also positively influence the concentration of important substances in plants, such as sugar and protein.

The degree and type of effect depends on various factors, in particular the time of application in relation to the developmental stage of the plant and the concentration applied. Again, these factors vary depending on the plant species and the desired effect. For example, grass areas are treated throughout the growth period. Ornamental plants in which the intensity and number of flowers are to be increased are treated before the flowers are planted. Plants, the fruit of which is used or used, shall be treated in the appropriate period of time before harvest. The various derivatives of the group of compounds described herein have herbicidal properties. These compounds are therefore suitable for the removal and suppression of undesirable plant growth.

Examples of compositions of the invention

Parts and percentages are by weight unless otherwise indicated.

Example 1 parts of the compound described in Example 1 were well mixed with 3 parts of diisobutylnaphthalenesulfonic acid sodium salt, 17 parts of ligninsulfonic acid sodium salt from sulphite waste liquors and 60 parts of powdered silica gel and ground in a hammer mill. By finely distributing this mixture in 20,000 parts of water, a spray suspension is obtained which contains 0.1% of active ingredient.

Example 2 parts of the compound described in Example 2 are intimately mixed with 97 parts of finely dispersed kaolin. In this way, a dust containing 3% of the active ingredient is obtained.

EXAMPLE 3 30 parts of the compound described in Example 3 are intimately mixed with a mixture of 92 parts of powdered silica gel and 8 parts of paraffin oil which has been sprayed onto the surface of the silica gel. In this way, an active substance preparation with good adhesion is obtained.

Example 4 parts of the compound described in Example 4 are intimately mixed with 10 parts of the sodium salt of the condensation product of phenolsulfonic acid, formaldehyde and urea, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts of water gives an aqueous dispersion containing 0.04% active ingredient.

EXAMPLE 5 parts of the compound described in Example 5 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenolsulfonic acid, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

Example 6 parts of the compound described in Example 1 are mixed with 10 parts of N-methyl-alpha-pyrrolidone to give a solution which is suitable for application as minimal drops.

. '23. ”212334

Example 1 and d 7. .

parts of the compound described in Example 2 is dissolved in a mixture of 80 parts. xylene, 10 parts of an adduct of 8 to 10 ml of ethylene oxide with 1 mole of N-mononitric acid oleic acid, 5 parts of dendecylbenzenesulfonic acid calcium salt and 5 parts of an adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring and finely distributing this solution in 100,000 parts of water, an aqueous dispersion is obtained which contains 0.02% active ingredient.

Example parts of the compound described in Example 3 are dissolved in a mixture consisting of 40 parts cyclohexanone, 30 parts isobutanol, 20 parts addition. 7 moles of ethylene oxide with 1 mol of isooctylphenol and 10 parts of an adduct of 40 moles of ethylene oxide with 1 mol of castor oil. By pouring and finely distributing the solution in 100,000 parts of water, an aqueous dispersion is obtained which contains · 0.02% active ingredient.

EXAMPLE 9 parts of the compound described in Example 3 are spun in a mixture consisting of 25 holes of cyclohexanol, 65 parts of a mineral oil fraction boiling at 21 DEG-280 DEG C. and 10 parts of a 40 mol addition product. ttlleioxide with · 1 mole of October oil. By dispersing and finely distributing this solution into 100,000 parts of water, an aqueous dispersion is obtained which contains 0.02% of active ingredient. ·

The compositions according to the invention can also be present in these dosage forms together with other active substances, for example mixed with herbicides, insecticides, plant growth regulators and fungicides or also with fertilizers. However, when mixed with fungicides, the spectrum of action and effect increase (SiO2) are also very rarely achieved. .

Fungicides that can be combined. with the compounds according to the invention are, for example, dithiocarbamates and derivatives thereof. such as ferric dioyldithiocarbonate;

Zinc diisopropylene diisopropylene diisocyanate, 1,1-diisocyanobenzoate, mono-zinc diisocyanobloate, zinc diisopropylene diisocyanate; . * '.

Zinc tertiaryl-thiocarbocate, tetramethylthiaremisulfide, amoonacal complex of Ν, t-tertyl-lis-dithiocarboxylate and zinc. . -.

N, N-ponyltylenibis- (thiocariaooyl) disslide,

Zinc N, N * -phenyletibis dithiocarbate,,.

and N, N * -ponylltibis-dithioker * stannate and N, N * -ponyl-propyltibis- (thiocarbemoyl) -disulfide;

iitnaphthin derivatives, such as ... · di-β- (1-betyllhptyl) phthyltarotinate, ’.

2-stutyl-4,6-dinitrophthiyl-3,3-dioethylacrylate, 2-stutyl-4,6-diitropherylpropionicinate ^, heterocyclic compounds such as

N-trichloroethylthin tetrahydrophthalioid, N-trichloroethylthinphthalioid, ..

212334 24 .2-Heptadeeyl-2-imldazolyl acetate _t

2,4-dichloro-6- (o-chloremilino) -α-triazine,

O, O-diethylphthylimidophosphonone,.

5-cm-no-1- (bis- [dimethyl-milno] phosphinyl) -3-phenyl-1,2,4-tricool,

5-ethoxy-ethoxy-ethoxy-methyl-5-ethoxy-ethoxy-ethyl-1-yl. 2,4-thiocool, 4-Dicyclo-1 H -dithiinium-mttoquinone,

2-thio-1,3-dithio [4,5-b] chinoxalln, ieeylaster butykkaramlbyl-L-2-nendimddozokarrCα! Acid methyl ester, 2-ietooxykwrtN>_{xnrlaii.nobbnn0iiiddcoe>} ^ -rhodicn iejtltl ^ ^ l ^ c ^ o ^ e O O ^ ^ ai ai ai ai ai

4- (2-chlorophenyl) urea (3-chloro-5-isoacoolene),

Oyrldin-2-thdol-1-oaid,

_8-t iydrochinolin oopřípcdé m Ženatá a salt thereof ,.

2,3- diiydro 5-kec'bobaailldUo eeyl-6 _{H-1,4-bxaahiin-4,4-dibxiU} ·

2,3-diidogb-5-yl-oxaailido-6-methyl-1, 2-oxachiine, 2- (t-2-yl) benzimiddzob,

Oioθгngine-1,4-dlyl-bis-1- (2,2,2-t-chloroethyl) -bomcmide,

2-thicobl-4-ylbenoimidazole

5-Butyl-2-dimethyl-indol-4-hydroxy-6-methyl-yimidine, bis- (o-chlorophenyl) -3-oyridirritol,

1,2- bis- (3-mntoayk £ a: 'bor] yl-2-thibureido) bnnonn;

c various fungicides such as doddeylLglaaiddnnceeУt,

3- [2- (3,5-Dimethyl-2-bicyclohexyl) -2-pyridyl] glucamide | ^ a ^^ o ^ e ^ en, ~

DioЫ.orfluoImetylthib N-N, N * N -Uimntyl fenyldiamiU sulfuric acid, _D> L · -mθeyl-N- (2,6-ddiθnylfeцyL) -N-lfu'-2-yl-alanindt,, meeyleeter D _L L · N- _(2> б-dimeeylfenyl) -N · (2 * -meeybalcetylLalandnu, ddisopropylester 5-nitro isophthalate,

2,5-dimethyliuwine-3-carbonylbaid, 2,5-dimethyliuine-3-carbeaylic acid, 2-menylbenzoylide,

1- (3,4-Dichloro-4-ol) ·· 1-formylmino-2 _> 2 _> 2-trilcilbrethane,

2.6-Uimθeyl-N-tddecylmbbfblin, 'optionally its sbld,

Ddmetyl ^2,6-N-cyclo- lbdodenylL] mrffbin, its popřípcdě. sbld,

2,3-dichloro-1'-n-phthtochinone, 4-dichloro-2,5-dihydroxybenzene,

O-ddmethylmethyldnobbnzonddaa0n-ηatrdumsulfonate,

L-Clor-2-ydboobO;

The olefinic bromobenzene, such as oentcchloradbrobenoene, methyl isocyanate, fungidic bibiotics, such as griseofulvin, or potassium tetrafluorobenzene, 1-phenylthosemicarbazide, a sulfuric acid mixture, a clarifying compound.

The following Examples A and B illustrate the biological effect of the novel compounds. 5-Cetamiddcb2-π-methyl-trifluoromethylluronamide (Fluoride, cf. U.S. Pat. No. 3,639,474), as well as 5-cetamido-, 44dimethylsulphonamide (methanesulfonamide), was used as a comparator. .

Example A

Effect on cereals

In a greenhouse, seeds of wheat cereals (Kolibri species) and barley (Unnon species) are sown in 11.5 cm diameter plastic dishes filled with an organic substrate with a low nutrient content. - The active substances are fed to the leaves of the plants in various amounts applied. The application is carried out at a plant height of 10. cm by conventional spraying.

During the 18-day growth period, the treated plants showed a significantly lower height increase compared to untreated plants, which could be as follows. by measuring the height of increase. 100 plants were measured from each row of treated plants.

Results:

Spring wheat (Koolbbi species):

Active ingredient of the example Applied. mnoství. kg / ha . cm Plant height relative - - 26.8 100 ALIGN! fluoridimide '.5 17.0 63.4 6.0 15.0 56.0 67 1.5 13.5 50.4 6.0 12.0 44.8 1 1 »5 13.0 48.5 6.0 12.6 46.6

Spring barley (type U ^ ohí: and) Active ingredient of the example Application rate kg / ha cm Plant height relative - · - 26.0 100 ALIGN! fluorddmid 1.5 20.0 76.9 6.0 16.0 61.5 67 1.5 13.0 50.0 • 6.0. 13.0 50.0 1 1.5 13.0 50.0 6.0 13.0 50., 0

(b)

Active ingredient of the example Application rate kg / ha Výika rostlin ca relative - - 26.0 100 ALIGN! Mefluidide 0.25 27.0 96.4 0.75 18.0 64.3 Mefluidide 1.50 17.5 62.5 3.00 16.0 57.1 111 0.25 26.5 94.6 0.75 16.0 57.1 1.50 16.0 57.1 3.00 15.0 53.6

Example В

Effect on grass or grass

In the vegetation test, ifitscherlich clay pots are planted with grass, the following standard mixtures are: grass (Agrostis tenuis) 10%, Cynosurus oristatua 10%, fescue (Festuca rubra) 15%, rye (Lolium perenne) 35%, and meadowgrass (Po and pratenaia) 30%. Fertilization was carried out using 1.5 g of nitrogen as ammonium nitrate and 1 g of phosphorus pentoxide as secondary potassium phosphate. After the two previous mowings, the active compounds are applied in different application rates at a height of 4 cm in the usual way by spraying. The height of growth is determined 20 days after treatment. After the first mowing, regrowth is observed for 4 weeks up to the second mowing, and the grass height is also measured to examine the additional effect. Compared to the control, the plants from the treated rows react very strongly by reducing the height of growth. The additional effect was judged to be superior to the known substance that was used for comparison, as shown in the following table.

Table

Active ingredient of the example Application rate kg / ha 1 · Cutting height of plants 2. Cutting the height of the plants cm relative cm relative - - 14.3 100 ALIGN! 11.0 100 ALIGN! Fluoramidamide 0.5 13.5 94.4 11.0 100 ALIGN! 0.75 12.5 87.4 10.0 90.9 67 0.5 14.0 97.4 11.0 100 ALIGN! 0.75 12.5 87.4 9.0 81.8 1 0.5 5.5 38.5 8.0 72.7 0.75 4,5 31.5 7.0 63.6

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Claims (1)

SUBJECT OF THE INVENTION A composition for controlling plant growth, comprising a solid or liquid carrier and at least one substituted sulfonic acid anilide of the formula (I) in which it is optionally halogen, oxygen, thiocyanato, (C 1 -C 4) alkoxy, aryloxy (C až-C uhlíku) alkyl, (C až-C alkyl) alkylsulfinyl, (C až-C alkyl) alkylsulfonyl, (C až-Cry a) arylsulfinyl, (C až-C alk) alkanoyl, (C až-C alko) alkoxycarbonyl C 1 -C 5 alkylcarbamoyl or C 1 -C 5 dialkylcarbamoyl, C 1 -C 4 haloalkanoylamino, C 1 -C 6 alkanoyloxy, C 1 -C 4 alkoxycarbonylamino in the alkoxy moiety, C 1 -C 6 alkylamino or dialkylamino (C 1 -C 6) alkyl, (C 6 -C 12) arylamino, (C 1 -C 6) alkylcarbamoylamino or (C 1 -C 6) dialkylcarbamoylamino, (C 1 -C 6) alkylcarbamoyloxy or di (C 1 -C 6) alkylcarbamoyloxy, (C 1 -C 4) alkylaminosulfonyloxy or C 1 -C 4 dialkylaminosulfonyloxy or a combination of ^{4 of} these substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or a (C až-Claklak) arylaclyl group, a cyano group, a thiocyanato group, or an alkyl group having from 1 to 4 carbon atoms, an amino group, aainoaulfonyl group, a guanyl group, an N ² -hydroxyguanyl group a hydroximoyl group or an alkoxyimidoylo group C 1 -C 5 alkoxy or optionally substituted C 1 -C 4 alkylsulfenyl; R ² and R 4 are the same or different and are hydrogen, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and C 1 -C 4 alkylsulfinyl. , (C 1 -C 4) alkylsulfonyl or (C 1 -C 4) alkanoyl, R @ 1 is C1 -C4 alkoxycarbonyl, optionally halogen-substituted alkanoyl and C1 -C4, or optionally phenyl. C 1-4 alkyl or substituted carbamoyl or aminosulfonyl, R1 is optionally halogen-substituted alkyl and 1 to 4 carbon atoms;