DK159093B - Agent having a gametocidal effect and having a stimulating effect on flower formation - Google Patents

Description

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Den foreliggende opfindelse angår et middel med gametocid virkning og med stimulerende virkning på blomsterdannelsen, der som aktivt stof indeholder et nitroaryl-alkyl-sulfon-derivat med den nedenfor anførte formel I. Opfindelsen angår 5 tillige en fremgangsmåde til stimulering af blomsterdannelsen hos planter samt en fremgangsmåde til udvinding af hybridfrø. Endelig angår opfindelsen anvendelsen af nitroaryl-alkylsulfonylderivater med den nedenfor anførte formel I i midlet ifølge opfindelsen.The present invention relates to an agent having gametocidal activity and stimulating to the flower formation, which contains as an active substance a nitroaryl-alkyl-sulfone derivative of the formula I below. The invention also relates to a method of stimulating the flower formation in plants as well as a method of extracting hybrid seeds. Finally, the invention relates to the use of nitroaryl-alkylsulfonyl derivatives of formula I listed below in the composition of the invention.

10 Nitroaryl-alkylsulfonderivaterne har den almene formelThe nitroaryl-alkylsulfone derivatives have the general formula

°2N2 N °

E4°~\Z^>'S02R1 (I) hvori R^ betyder C^-C^-alkyl, R4 betyder hydrogen, en hydrazinium- eller ammoniumion eller gruppen -COR,., hvor Rj. betyder C^-C^-alhylr C^-C^-alkoxy, C^-C^-halogenalkyloxy, 15 C2”C^Q_alkenyl, C^-C^-halogenalkenyl, C^-Cg-cycloalkyl, phenyl, furyl, tetrahydrofuryl, nitrophenyl eller halogenphenyl.E4 ° ~ \ Z ^> 'SO2R1 (I) wherein R4 represents C1-C4 alkyl, R4 represents hydrogen, a hydrazinium or ammonium ion or the group -COR1 where Rj. means C--C ^ -alkyl, C ^-C ^-alkoxy, C ^-C ^-haloalkyloxy, C₂-C ”-C_-alkenyl, C ^-C ^-halogenalkenyl, C ^-Cg-cycloalkyl, phenyl, furyl, tetrahydrofuryl, nitrophenyl or halophenyl.

Ved udtrykket alkyl selv eller som bestanddel af en anden substituent skal der alt efter antallet af de angivne 20 carbonatomer eksempelvis forstås følgende grupper: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl eller dodecyl, samt de isomere deraf, såsom f.eks. isopropyl, isobutyl, tert-butyl, isopentyl osv.By the term alkyl itself or as a constituent of another substituent, according to the number of the indicated 20 carbon atoms, is meant, for example, the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl, as well as the isomers thereof, such as e.g. isopropyl, isobutyl, tert-butyl, isopentyl, etc.

Alkenyl betyder f.eks. vinyl, propenyl-(1), allyl, butenyl-25 (1), butenyl-(2), butenyl-(3) osv., samt kæder med flere dobbeltbindinger. Halogenalkyl består af en mono- til per-halogeneret alkylsubstituent, f.eks. CHCl2r CE^Cl, CCl^j CCF'3 og CH2CH2C1. Ved halogen skal her og i det følgende forstås fluor, chlor, brom eller iod, fortrinsvis chlor eller 30 brom. Cycloalkyl betyder f.eks. cyclopropyl, cyclobutyl, 2Alkenyl means e.g. vinyl, propenyl (1), allyl, butenyl (1), butenyl (2), butenyl (3), etc., and several double bond chains. Haloalkyl consists of a mono- to per-halogenated alkyl substituent, e.g. CHCl2r CE ^ Cl, CCl ^ j CCF'3 and CH2CH2C1. By halogen is meant herein and hereinafter fluorine, chlorine, bromine or iodine, preferably chlorine or bromine. Cycloalkyl means e.g. cyclopropyl, cyclobutyl, 2

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cyclopentyl/ cyclohexyl eller cycloheptyl, fortrinsvis cyclo-pentyl og cyclohexyl. Halogenalkenyl og halogenalkoxy betyder en med halogen mono- eller polysubstitueret alkenyl-eller alkoxygruppe, idet der som halogen fortrinsvis forstås 5 chlor og brom, især chlor.cyclopentyl / cyclohexyl or cycloheptyl, preferably cyclopentyl and cyclohexyl. Haloalkenyl and haloalkoxy means a halo mono- or polysubstituted alkenyl or alkoxy group, with halogen being preferably understood as chlorine and bromine, especially chlorine.

Ammonium- og hydraziniumsaltene med formlen I er hidtil ukendte forbindelser, som er højaktive, og som udgør en særlig fordelagtig del af opfindelsen.The ammonium and hydrazinium salts of formula I are novel compounds which are highly active and constitute a particularly advantageous part of the invention.

Som eksempler på ammoniumioner kan nævnes: NH^, NH(alkyl)3, 10 NH2(alkyl)^ og NH3(alkyl), såsom NH(CH3)3, NH(C2H3)3, NH2 (CH3) 2, NH2 (c3H7-n) 2 , NH3CH3 og N^C^Hg-n, eller kvaternære ammoniumioner, såsom tetraethyl-, tetrapropy1-, tetrabutyl-, tetrapentyl-, tetrahexyl-, tetraheptyl-, tetraoctyl-, tetra-nonyl-, tetradecyl-, methyltributyl-, dimethyldibutyl-, tri-15 methylbutyl-, methyltrioctyl-, benzyltrimethyl-, benzyltri-ethyl-, benzyltripropyl-, benzyltributyl-, benzyldimethyl-hexadecyl-, benzyldiethylhexadecyl-, diisobutyl-cresoxyethyl-dimethylbenzyl-, trimethylphenyl-, diphenyldimethyl-, butyl-tripropyl-, tributylphenyl- eller tricaprylmethylammonium.Examples of ammonium ions include: NH 1, NH (alkyl) 3, NH 2 (alkyl) 2 and NH 3 (alkyl) such as NH (CH 3) 3, NH (C 2 H 3) 3, NH 2 (CH 3) 2, NH 2 (c 3 H 7) -n) 2, NH 3 CH 3 and N 1 C 2 Hg-n, or quaternary ammonium ions, such as tetraethyl, tetrapropyl, tetrabutyl, tetrapentyl, tetrahexyl, tetraheptyl, tetraoctyl, tetra-nonyl, tetradecyl, methyl tributyl -, dimethyldibutyl, trimethylbutyl, methyltrioctyl, benzyltrimethyl, benzyltriethyl, benzyltripropyl, benzyltributyl, benzyldimethyl-hexadecyl, benzyldiethylhexadecyl, diisobutyl-cresoxyethyl-dimethylbenzyl -tripropyl, tributylphenyl or tricapryl methylammonium.

20 Som eksempler på hydraziniumioner kan anføres usubstituerede og substituerede hydraziniumforbindelser, såsom NH2N(alkyl)3, N^NH (alkyl) 2 og NH2NH2(alkyl).As examples of hydrazinium ions may be cited unsubstituted and substituted hydrazinium compounds such as NH 2 N (alkyl) 3, N 1 NH (alkyl) 2 and NH 2 NH 2 (alkyl).

Blandt ammoniumkationerne foretrækkes foruden NH. især sådan- + 4 ne af typen NH^_a^ (lavalkyl)a, hvor a = 1, 2, 3, 4, og 25 blandt disse først og fremmest tetraalkylammoniumioner, så- somN(CH3)J, N(C2H5)^, N(C4H9-n)^, NtCHj)2(CjHj)+, N(C3H7-n>4 og N(C3H7-i)+.Among the ammonium cations, NH is preferred. in particular such + NH 4 -A 4 (lower alkyl) α, where α = 1, 2, 3, 4, and 25 of these are primarily tetraalkylammonium ions, such as N (CH 3) J, N (C 2 H 5) , N (C4H9-n) +, NtCH2) 2 (CjHj) +, N (C3H7-n> 4, and N (C3H7-i) +.

Forbindelserne med formlen I er ved stuetemperatur stabile olier, harpikser eller overvejende faste stoffer, som udmær-30 ker sig ved meget værdifulde mikrobicide og plantevækstregulerende egenskaber. De anvendes derfor fortrinsvis indenfor agrarsektoren eller beslægtede områder til målrettet indvirkning på blomsterdannelsen hos planter, og de er endvidere egnede til bekæmpelsen af fytopatogene mikroorganismer.The compounds of formula I are at room temperature stable oils, resins or predominantly solids which are characterized by very valuable microbicidal and plant growth regulating properties. Therefore, they are preferably used in the agricultural sector or related areas for a targeted effect on the flowering of plants, and they are also suitable for the control of phytopathogenic microorganisms.

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Særligt foretrukne er virksomme forbindelser med formlen I, hvori betyder methyl/ og R^ betyder hydrogen eller fortrinsvis en hydraziniumion, især en ammoniumion.Particularly preferred are active compounds of the formula I wherein methyl / and R ^ means hydrogen or preferably a hydrazinium ion, especially an ammonium ion.

Typiske eksempler på forbindelser med formlen I er følgende 5 forbindelser: 4-Hydroxy-3-nitrophenyl-methylsulfon, 4-(3-chlor-n-propylcarbonyloxy)-3-nitrophenyl-methylsulfon, 4-hydroxy-3-nitrophenyl-methylsulfon-tetra(n-butyl)-ammoniumsalt, 5 4-acetyloxy-3-nitrophenyl-methylsulfon, 4-cyclopropylcarbonyl-3-nitrophenyl-methylsulfon, 4-hydroxy-3-nitrophenyl-ethylsulfon/ 4-acryloxy-3-nitropheny1-methylsulfon, 4-trichloracryloxy-3-nitrophenyl-methylsulfon/ 10 4-n-propylcarbonyloxy-3-nitrophenyl-methylsulfon, 4-ethylcarbonyloxy-3-nitrophenyl-methylsulfon, 4-phenylcarbonyloxy-3-nitrophenyl-methylsulfon, 4-methoxymethylcarbonyoxy-3-nitrophenyl-methylsulfon, 4-cyclohexylcarbonyloxy-3-nitrophenyl-methylsulfon, 15 4-chlormethylcarbonyloxy-3-nitrophenyl-methylsulfon og 4-methoxycarbonyloxy-3-nitrophenyl-methylsulfon.Typical examples of compounds of formula I are the following compounds: 4-Hydroxy-3-nitrophenylmethylsulfone, 4- (3-chloro-n-propylcarbonyloxy) -3-nitrophenylmethylsulfone, 4-hydroxy-3-nitrophenylmethylsulfone tetra (n-butyl) ammonium salt, 4-acetyloxy-3-nitrophenyl-methylsulfone, 4-cyclopropylcarbonyl-3-nitrophenyl-methylsulfone, 4-hydroxy-3-nitrophenyl-ethylsulfone / 4-acryloxy-3-nitrophenyl-methylsulfone, 4-trichloroacryloxy-3-nitrophenylmethylsulfone / 4-n-propylcarbonyloxy-3-nitrophenylmethylsulfone, 4-ethylcarbonyloxy-3-nitrophenylmethylsulfone, 4-phenylcarbonyloxy-3-nitrophenylmethylsulfone, 4-methoxymethylcarbone -methylsulfone, 4-cyclohexylcarbonyloxy-3-nitrophenylmethylsulfone, 4-chloromethylcarbonyloxy-3-nitrophenylmethylsulfone and 4-methoxycarbonyloxy-3-nitrophenylmethylsulfone.

Forbindelserne med formlen I fremstilles ved, at man hydrolyserer et arylhalogenid med den nedenfor anførte formel II 20 i nærværelse af en base til en aromatisk alkohol med den anførte formel III og, om ønsket, acylerer den phenoliske OH-gruppe med et reaktionsdygtigt derivat, fortrinsvis anhydridet, især syrechloridet eller syrebromidet, af syren med formlen RgCOOH (IV) på i og for sig kendt måde til O-substituerede 25 produkter med formlen I eller omdanner den sure OH-gruppe ved neutralisation med en base til et salt med formlen I og isolerer det dannede produkt på sædvanlig måde.The compounds of formula I are prepared by hydrolyzing an aryl halide of formula II 20 below in the presence of a base to an aromatic alcohol of formula III and, if desired, acylating the phenolic OH group with a reactive derivative, preferably the anhydride, especially the acid chloride or acid bromide, of the acid of formula RgCOOH (IV) in a manner known per se to O-substituted products of formula I or converting the acidic OH group by neutralization with a base to a formula I and isolates the formed product in the usual manner.

4 °2n o2n4 ° 2n o2n

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Hal-<^I>-S02Rl tSt* H°-^I>-S02R1 (II) (III) I formlerne II, III og IV har substituenterne , R^ og R^ de under formlen I anførte betydninger. Hal betyder halogen.Hal - <^ I> -SO2R1 tSt * H ° - ^ I> -SO2R1 (II) (III) In formulas II, III and IV, the substituents, R ^ and R ^ have the meanings set forth in Formula I. Hal means halogen.

Egnede baser er eksempelvis vandige hydrazinium- eller ammo-5 niumhydroxidderivater.Suitable bases are, for example, aqueous hydrazinium or ammonium hydroxide derivatives.

Ved acyleringsreaktionen kan der anvendes reaktionsindifferent opløsnings- eller fortyndingsmidler. Der kan eksempelvis anvendes aliphatiske og aromatiske carbonhydrider, såsom benzen, toluen, xylener og petroleumsether, halogenerede 10 carbonhydrider, såsom chlorbenzen, methylenchlorid, ethylen-chlorid, chloroform, carbontetrachlorid og tetrachlorethylen, ethere og etheragtige forbindelser, såsom dialkylethere (di-ethy lether, diis opr opy lether, tert-bu ty lmethy lether osv.) . anisol, dioxan og tetrahydrofuran, nitriler, såsom aceto-15 nitril og propionitril, Ν,Ν-dialkylerede amider) såsom di-methylformamid, dimethylsulfoxid, ketoner, såsom acetone, diethylketon eller methylethylketon, og blandinger af sådanne opløsningsmidler. I mange tilfælde kan acyleringsmidlet selv anvendes som opløsningsmiddel.In the acylation reaction, reaction-inert solvents or diluents can be used. For example, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes and petroleum ether may be used, halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetrachlorethylene, ethers and ether-like compounds such as dialkyl ethers, diis opr opy lether, tert-bu ty lmethy lether, etc.). anisole, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, Ν, dial-dialkylated amides) such as dimethylformamide, dimethyl sulfoxide, ketones such as acetone, diethyl ketone or methyl ethyl ketone, and mixtures of such solvents. In many cases, the acylating agent itself can be used as a solvent.

20 Ved O-acyleringsreaktionen kan tilstedeværelsen af en reaktionskatalysator, såsom dimethylformamid, være fordelagtigt.In the O-acylation reaction, the presence of a reaction catalyst such as dimethylformamide may be advantageous.

Reaktionstemperaturerne ligger sædvanligvis mellem 0 og 180°C, fortrinsvis mellem 0 og 150°C eller ved kogepunktet for det anvendte opløsningsmiddel eller den anvendte opløs-25 ningsmiddelblanding. I mange tilfælde er det fordelagtigt at anvende syrebindende midler eller kondensationsmidler.The reaction temperatures are usually between 0 and 180 ° C, preferably between 0 and 150 ° C or at the boiling point of the solvent or solvent mixture used. In many cases it is advantageous to use acid binding agents or condensing agents.

Som sådanne kan anvendes organiske og uorganiske baser, f.eks. tertiære aminer, såsom trialkylaminer, f.eks. tri-methylamin, triethylamin, tripropylamin osv.), pyridin og 5As such, organic and inorganic bases, e.g. tertiary amines such as trialkylamines, e.g. trimethylamine, triethylamine, tripropylamine, etc.), pyridine and 5

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pyridinbaser, såsom 4-dimethylaminopyridin, 4-pyrrolidinyl-aminopyridin osv., oxider og hydroxider, carbonater og hydro-gencarbonater af alkalimetal- og jordalkalimetaller, samt alkalimetalacetater.pyridine bases such as 4-dimethylaminopyridine, 4-pyrrolidinylaminopyridine, etc., oxides and hydroxides, carbonates and hydrogen carbonates of alkali metal and alkaline earth metals, as well as alkali metal acetates.

5 Dannet hydrogenhalogenid kan i mange tilfælde også fjernes fra reaktionsblandingen ved gennemledning af indifferent gas, f.eks. nitrogen, eller det kan fjernes fra reaktionsblandingen ved tilsætning af molekylsigter.Formed hydrogen halide can in many cases also be removed from the reaction mixture by passing inert gas, e.g. nitrogen, or it can be removed from the reaction mixture by the addition of molecular sieves.

Det er kendt, at der findes biologisk aktive nitroaryl-alkyl-10 sulfon-derivater. Således hører forbindelserne med formlen I til en gruppe nitroarylalkylsulfoner, der er kendt fra beskrivelsen til GB patentskrift nr. 1.128.217 som herbicider til bekæmpelse af skadelige planter. 5-brom-4-hydroxy-3-nitrophenyl-methylsulfon og 5-iod-4-hydroxy-3-nitrophenyl-15 methylsulfon er specifikt anført i ovennævnte patentbeskrivelse, og de øvrige forbindelser med formlen I er omfattet af de almene formler. Fremstillingen af 4-hydroxy-3-nitro-phenyl-methylsulfon samt dens kemiske og fysiske egenskaber er kendt fra Chem-abstr. 5_3, 3110d (1959) , og fremstillingen 20 af 4-acetyloxy-3-nitrophenyl-methylsulfon samt dens kemiske og fysiske egenskaber er kendt fra Zhr.Obsh.Khim. 3J3, 3064-3072 (1960) .Biologically active nitroaryl-alkyl-sulfone derivatives are known to exist. Thus, the compounds of formula I belong to a group of nitroarylalkyl sulfones known from the specification of GB Patent No. 1,128,217 as herbicides for the control of harmful plants. 5-bromo-4-hydroxy-3-nitrophenyl-methylsulfone and 5-iodo-4-hydroxy-3-nitrophenyl-methylsulfone are specifically mentioned in the above patent specification, and the other compounds of formula I are included in the general formulas. The preparation of 4-hydroxy-3-nitro-phenyl-methylsulfone as well as its chemical and physical properties is known from Chem-abstr. 5_3, 3110d (1959), and the preparation 20 of 4-acetyloxy-3-nitrophenylmethylsulfone as well as its chemical and physical properties are known from Zhr.Obsh.Khim. 3J3, 3064-3072 (1960).

Det har overraskende vist sig, at nitroaryl-alkylsulfon-derivater med formlen I eller midler, som indeholder disse 25 virksomme forbindelser, først og fremmest udmærker sig ved, at de på målrettet vis griber ind i planternes fysiologi.Surprisingly, it has been found that nitroaryl-alkylsulfone derivatives of formula I or agents containing these active compounds are first and foremost distinguished by their deliberately interfering with the physiology of plants.

Et sådant indgreb i de fysiologiske processer i planteudviklingen gør de virksomme forbindelser med formlen I anvendelige til forskellige formål, f.eks. til sådanne, der har 30 forbindelse med udbytteforøgelsen hos nytteplanter og især med arbejdsbesparelsen ved dyrkning og produktion af hybridsåsæd.Such an intervention in the physiological processes of plant development makes the active compounds of formula I useful for various purposes, e.g. to those that have 30 associated with the yield increase in utility plants and especially with the labor savings in growing and producing hybrid seed.

Ifølge de hidtidige erfaringer med anvendelsen af vækstregulerende forbindelser forholder det sig således, at de virk- 6According to previous experience with the use of growth regulating compounds, it is found that they are effective 6

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somme forbindelser kan fremkalde en eller flere forskellige virkninger i planterne. Disse forskelligartede virkninger afhænger i det væsentlige af anvendelsestidspunktet, dvs. frøenes fysiologiske tilstand eller plantens udviklings-5 tilstand, anvendelsesmåden samt især de anvendte koncentrationer. Sådanne virkninger er igen forskellige alt efter plantearten.some compounds may cause one or more different effects in the plants. These diverse effects essentially depend on the time of use, ie. the physiological state of the seeds or the state of development of the plant, the mode of application and especially the concentrations used. Such effects are again different depending on the plant species.

Det har vist sig, at anvendelsen af forbindelserne med formlen I gør det muligt at påvirke plantevæksten i ønsket ret-10 ning.It has been found that the use of the compounds of formula I allows to influence plant growth in the desired direction.

Ved anvendelse af nitroaryl-alkylsulfon-derivaterne med formlen I eller agrokemiske midler, der indeholder disse forbindelser som virksom stof, er det muligt at regulere den generative vækst af en hel række enkimbladede og to-15 kimbladede planter, idet den vegetative vækst påvirkes positivt indenfor brede koncentrationsområder for kulturerne. Ved anvendelse af meget store mængder kan der optræde fytotoksiske virkninger. Påvirkningen af den generative plantevækst giver sig forskelligt til kende afhæn-20 gigt af plantekulturen.Using the nitroaryl-alkylsulfone derivatives of formula I or agrochemicals containing these compounds as active ingredient, it is possible to regulate the generative growth of a variety of single-seeded and two-seeded plants, with the vegetative growth being positively affected within broad areas of concentration for the cultures. Phytotoxic effects can occur with very large amounts. The influence of the generative plant growth is different depending on the plant culture.

En fremtrædende form for reguleringen af den generative vækst beror på den særlige egenskab ved de her omhandlede nitroaryl-alkyl-sulfon-derivater, at de udviser en game- · tocid virkning på forskellige kulturplanter,· især ved' 25 anvendelse i enkimbladede planter, såsom hvede, rug, byg, havre, ris, majs, hirse, fodergræsser osv., men også ved andre planter, såsom solsikke og bomuld. Denne fører til en hankønsstérilitet hos planterne, uden at frugtbarheden af de hunkønnede blomsterdele påvirkes kendeligt. Hos 30 talrige kulturplanter kan der samtidig iagttages en tilvækst i biomsteransætningen og/eller dannelsen af parthenokarpe frugter, f.eks. ved tomater. Hankønssteriliteten viser sig enten ved en aktuel hankønssterilitet, dvs. at de hankønne-de blomsterdele overhovedet ikke danner eller ved at 35 blomsterpollenet er sterilt, eller det viser sig ved en funktionel hankønssterilitet, ved hvilken de hankønnede 7A prominent form of the regulation of generative growth is due to the particular property of the nitroaryl-alkyl-sulfone derivatives at issue in that they exhibit a game-tocid effect on various culture plants, especially in use in monocotyledonous plants, such as wheat, rye, barley, oats, rice, corn, millet, fodder grasses, etc., but also by other plants such as sunflower and cotton. This leads to male sterility of the plants, without affecting the fertility of the female parts of the flower. At 30 numerous cultural plants, growth can also be observed in the biomster recruitment and / or formation of parthenocarp fruits, e.g. for tomatoes. Male sterility is shown either by a current male sterility, ie. that the male flower parts do not form at all or that the flower pollen is sterile or that it shows by a functional male sterility at which the male 7

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blomsterdele ganske vist dannes, men ikke er i stand til at fremkalde en befrugtning. De virksomme forbindelser med formlen I kan derfor også fremkalde protogyni, dvs. at der på et tidligt tidspunkt dannes befrugtningsdygtige hun-5 kønnede biomsterdele, eller at udvoksningen af de hankønne-de blomsterdele er så forsinket, at en fremmedbestøvning med udvalgte blomsterpollen kan gennemføres.floral parts are formed but are unable to induce a fertilization. Therefore, the active compounds of formula I can also induce protogyny, viz. that at an early stage fertilized female biomass parts are formed or that the growth of the male flower parts is so delayed that a foreign pollination with selected flower pollen can be carried out.

Disse gametocide virkninger anvendes især med fordel ved dyrkning og markproduktion af hybrid-såsæd. Hybrid-såsæd 10 spiller en betydlig rolle ved hovedernæringsnytteplanterne og prydplanter. Hybrider er sædvsnligvis mere vitale end de rene arter og giver højere udbytter end de mest udbyttegivende stamsorter.These gametocidal effects are particularly used to advantage in the cultivation and field production of hybrid seed. Hybrid seed 10 plays a significant role in main nutrient and ornamental plants. Hybrids are usually more vital than the pure species and give higher yields than the most yielding strains.

Ved hybridiseringen krydser planteavleren to eller flere 15 omhyggeligt udvalgte indavlslinier i et eksperimentelt fastlagt program og får på denne måde hybridsåsæd, hvoraf de udviklede planter udviser forøget vækstevne og udbytte.In hybridization, the plant breeder crosses two or more carefully selected inbreeding lines in an experimentally determined program, thus obtaining hybrid seed, of which the developed plants exhibit increased growth ability and yield.

Med de sambo-synosiske majsplanter kan en hybridisering også gennemføres på konventionel måde, da hankønnede 20 og hunkønnede blomsterdele dannes på forskellige steder på planten (dikline blomster). Støvbladene, som danner pollen, udgør toppen af majsplanterne, medens de kolbeformede blomsterstande med hårtrådene dannes under plantens midte.With the co-synocytic maize plants, hybridization can also be carried out in a conventional manner, since male and female floral parts are formed at various locations on the plant (dicline flowers). The pollen leaves, which form the pollen, form the top of the corn plants, while the flask-shaped inflorescences with the hair strands form below the center of the plant.

Til dyrkning af F,-hybrider udplantes sædvanligvis skiften-25 de rækker af majsplanter af sorterne eller de homozygote linier AA og BB. For at sikre, at AA-majsen ikke danner pollen, aftoppes AA-planterne manuelt eller maskinelt i god tid inden fuldstændig udvikling af hanblomsterstandene, hvorefter der foretages bestøvning med en BB-majs-sort, 30 hvorved der på AA-planterne dannes såsæd af en AB-hybrid (F1).Den hertil nødvendige arbejdsproces er ikke blot tidsrøvende og kostbar, men den fører naturnødvendigt også til en beskadigelse af planterne og især ved maskinel fjernelse af hanblomsterne til en uønsket udbytteformindskelse hos 35 de som hunstamplanter (frøbærere) tjenende linier/sorter.In order to grow F, hybrids are usually transplanted into the rows of maize plants of the varieties or the homozygous lines AA and BB. To ensure that the AA corn does not form pollen, the AA plants are dipped manually or mechanically in good time before complete development of the male inflorescences, after which pollination is carried out with a BB maize variety, 30 whereby the seeds are seeded on the AA plants. An AB hybrid (F1). The work process required is not only time-consuming and costly, but it also naturally leads to damage to the plants and, in particular, by the mechanical removal of the male flowers to an undesirable yield reduction on the lineage (seed-bearing) lines. / varieties.

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Ved sambo-synoniske planter, såsom majs, kan hybridiserin-gen stadig gennemføres på nogenlunde økonomisk måde under anvendelse af den ovenfor beskrevne, almindelige fremgangsmåde. Det er imidlertid væsentligt vanskeligere at 5 gennemføre denne proces med småkornede halmfrugter, især med sådanne, som har tvekønnede blomster, og hvor der normalt forekommer selvbestøvning; men også krydsbestøvning, såkaldt fremmedbefrugtning. I disse tilfælde er den gængse fremgangsmåde særdeles tidsrøvende, arbejdsintensiv og 10 uøkonomisk, og den kræver først og fremmest særligt uddannet arbejdskraft. Småkornede halmfrugthybrider kan kun avles, når selv- og krydsbestøvningen undertrykkes fuldstændigt i moderlinien. I praksis må man derfor i god tid åbne alle de bitte små blomster med håndkraft og 15 omhyggeligt fjerne alle støvknappene og derefter beskytte blomsterne mod uønsket fremmedbestøvning.In co-synonymous plants, such as maize, hybridization can still be carried out in a fairly economical manner using the usual procedure described above. It is, however, considerably more difficult to carry out this process with small-grained straw fruits, especially with those having bisexual flowers, and where self-pollination usually occurs; but also cross-pollination, so-called foreign fertilization. In these cases, the usual approach is extremely time-consuming, labor-intensive and uneconomical, and it requires, above all, specially trained manpower. Small-grain straw fruit hybrids can only be bred when self- and cross-pollination is completely suppressed in the maternal line. In practice, therefore, one must open all the tiny little flowers by hand in good time and carefully remove all the dust buttons and then protect the flowers from unwanted foreign pollination.

Hos nogle kornsorter, såsom hvede, byg, hirse samt majs og ved tokimbladede planter anvendes desuden en anden hy-bridiseringsmetode. Ved denne fremgangsmåde går man ud fra 20 cytoplasmatisk hansterile planter og foretager fremmedbestøvning. Disse cytoplasmatisk sterile planter begrænser sig til moderlinier, som har samme cytoplasma. Ved denne metode overføres cytoplasmatisk nedarvede svagheder eller fejl, f.eks. manglende resistens mod en bestemt sygdoms-25 fremkalder eller følsomhed overfor frost og lignende, naturnødvendigt til alle hybrider, som stammer fra denne moderlinie. Desuden kræver hybridiseringen med cytoplasmatisk hankønssterile linier, især ved småkornede halmfrugter, men også ved dicotyle kulturer, omfattende og van-30 skelige foranstaltninger.In addition, in some cereals, such as wheat, barley, millet as well as maize and in two-seeded plants, another hybridization method is used. In this method, 20 cytoplasmic male sterile plants are used and foreign pollination is performed. These cytoplasmically sterile plants confine themselves to maternal lines that share the same cytoplasm. In this method, cytoplasmically inherited weaknesses or defects are transmitted, e.g. lack of resistance to a particular disease-25 induces or susceptibility to frost and the like, essential for all hybrids derived from this maternal lineage. In addition, the hybridization with cytoplasmic male-sterile lines, especially in small-grained straw fruits, but also in dicotyle cultures, requires extensive and difficult measures.

Uafhængigt af metoden forudsætter dyrkningen af hybridsåsæd altid frembringelse af hankønssterile og hunkønsintakte planter. Anvendelsen af kemiske steriliseringsmidler (gametocider) er en enkel, praktisk gennemførlig 35og økonomisk løsning til fremstilling af en selektiv hankønssterilitet. Nitroaryl-alkylsulfon-derivater med formlen I udviser særdeles gode hankøns-gametocide egen-Regardless of the method, the cultivation of hybrid seed always requires the production of male-sterile and female-intact plants. The use of chemical sterilizers (gametocides) is a simple, practically feasible and economical solution for producing a selective male sterility. Nitroaryl-alkylsulfone derivatives of formula I exhibit extremely good male gametocide properties.

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9 £ skaber og er derfor egnede til dette og beslægtede formål. Anvendelsen af disse forbindelser i nytteplantekulturer bevirker, at de fleste problemer, som er knyttet til de gængse hybridiseringsmetoder, slet ikke optræder.£ 9 creates and is therefore suitable for this and related purposes. The use of these compounds in crop plants means that most of the problems associated with the conventional hybridization methods do not occur at all.

5 Ved frembringelse af hankønssterile planter og dermed til udvinding af hybrid-såsæd kan man nærmere betegnet gå frem på følgende måde: De to forældreplanter, som skal krydses med hinanden, plantes i f.eks. alternerende rækker. Den som frøbærer eller moderplante udvalgte linie 10 behandles ved blomsterdannelsens begyndelse, men endnu inden dannelsen af hankønnede blomsterdele, med en virksom forbindelse med formlen I. På denne måde får man en række hankøns s teriley men frugtbare hunmoderplanter. Den anden række behandles ikke og tjener som pollenafgiver. Disse 15 planters hankønsdele udvikles fuldstændigt og giver pollen til bestøvning af moderplanterne eller frøbæreren. De af moderplanterne dannede frøkorn udgør hybrid-såsæden og kan høstes på konventionel måde. Kornene fra hankøns-forældreplanterne høstes separat og udnyttes på anden måde.In the production of male-sterile plants and thus for the extraction of hybrid seed, it is more particularly possible to proceed as follows: The two parent plants, which must be crossed with each other, are planted in e.g. alternating rows. Line 10 selected as a seed carrier or parent plant is treated at the beginning of flowering, but even before the formation of male flower parts, with an effective compound of Formula I. In this way, a number of male s teriley but fertile female mother plants are obtained. The second row is not processed and serves as a pollinator. The male parts of these 15 plants are fully developed and provide pollen for pollination of the parent plants or seed carrier. The seed seeds formed by the parent plants constitute the hybrid seed and can be harvested in a conventional manner. The grains from the male-parent plants are harvested separately and utilized differently.

20 Den beskrevne fremgangsmåde til frembringelse af hankønssterile planter heholdsvis til udvinding af hybrid-såsæd er omfattet af den foreliggende opfindelse.The described method for producing male-sterile plants, respectively, for the extraction of hybrid seed is included in the present invention.

De virksomme forbindelser med formlen I har også andre vækstregulerende virkninger, f.eks. en tidsmæssig regule-25 ring af blomsterdannelsen og som følge deraf en kontrolleret frø- eller frugtmodning. Denne type blomstringsstimulering har især økonomisk interesse ved sådanne plantesorter, der samtidig blomstrer og bærer frugter. Således kan eksempelvis behandlingen af avocado- og bomuldsplanter 30 med forbindelser med formlen I på den ene side medfører en fordelagtig forøgelse af antallet af blomsterstande, og på den anden side kan blomstrings- og modningsprocessen underkastes en reguleret rytme. På denne måde kan man ikke blot opnå en udbytteforøgels^ men tillige en mere rationel 35 udformning af indhøstningen og således en gunstigere markedsføring. Denne form for stimulering af blomsterdannelsenThe active compounds of formula I also have other growth regulating effects, e.g. a temporal regulation of flower formation and, as a result, controlled seed or fruit ripening. This type of flowering stimulation is of particular economic interest to such plant species that are at the same time blooming and bearing fruit. Thus, for example, the treatment of avocado and cotton plants 30 with compounds of formula I may, on the one hand, result in an advantageous increase in the number of inflorescences, and on the other hand the flowering and ripening process may be subjected to a regulated rhythm. In this way, one can not only achieve a yield increase but also a more rational design of the harvest and thus a more favorable marketing. This kind of stimulation of flower formation

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10 spiller også en afgørende rolle ved frugtdannelsen. Ved frugtavl iagttager man nemlig sædvanligvis en årlig skiften mellem gode år og dårlige år, betinget af genetiske eller ydre faktorer. Denne skiften er et resultat af et misfor-5 hold mellem driftvæksten og biomsteranlæggene, idet ernæringen af frugterne på planten kræver for mange assimila-ter på bekostning af dannelsen af blomsterknopper. De konventionelle foranstaltninger til forbedring af frugtkvaliteten består i en tidsrøvende mekanisk udtømning 10 af helt unge frugter samt af vækstregulerende afskæring af de såkaldte vildskud. Dette fører dog nødvendigvis til en beskadigelse af træerne og til mindre udbytter. Ved anvendelse af nitroaryl-alkylsulfon-derivaterne med formlen I kan driwæksten i vid grad undertrykkes til fordel 15 for den generative vadest, således at vækstkraften i større grad bidrager til blomster- og frugtdannelsen. På denne måde kan man ikke blot forbedre frugtkvaliteten, men der kan også opnås en udbytteforbedring og en faseforskydning i vekselvirkningen.10 also plays a crucial role in fruit formation. In the case of fruit growing, one usually observes an annual shift between good years and bad years, dependent on genetic or external factors. This shift is a result of a mismatch between drift growth and biomster plants, as the nutrition of the fruits on the plant requires too many assimilates at the expense of the formation of flower buds. The conventional measures to improve fruit quality consist of a time-consuming mechanical discharge 10 of very young fruits as well as growth-regulating cutting of the so-called wild shoots. However, this necessarily leads to damage to the trees and to smaller yields. By using the nitroaryl-alkylsulfone derivatives of formula I, the growth of drift can be largely suppressed in favor of the generative crop, so that the growth power contributes to flower and fruit formation to a greater extent. In this way, not only can the fruit quality be improved, but a yield improvement and a phase shift in the interaction can also be obtained.

20 I mange tilfælde bevirker anvendelsen af forbindelser med formlen I en tydelig forlængelse af blomstringsperioden, hvorved man opnår en større mulighed for bestøvning af alle blomster. En tidsmæssig forlængelse af blomstringsfasen er også ønsket hos et stort antal prydplanter, især hos 25 blomster.In many cases, the use of compounds of formula I causes a distinct prolongation of the flowering period, thereby providing a greater opportunity for pollination of all flowers. A temporal extension of the flowering phase is also desired in a large number of ornamental plants, especially in 25 flowers.

Ved en lang række forskellige kulturplanter iagttager man efter behandling med virksomme forbindelser med formlen I parallelt med hankønssteriliseringen en positiv indvirkning på hunblomsterne. På denne måde opnås ofte en forøgelse 30 af antallet af hunblomster pr. blomsterstand eller pr.In a wide variety of culture plants, after treatment with effective compounds of formula I, a positive effect on the female flowers is observed in parallel with the male sterilization. In this way, an increase of 30 in the number of female flowers is often achieved. inflorescence or per.

plante, hvorved der således også opnås en udbytteforøgelse. Sådanne virkninger er også konstateret hos småkornede halmfrugter, såsom byg, agurkeplanter, solsikkeplanter, bælgfrugter, såsom soja, træagtige vækster og prydplanter, så-35 som kompositer. I nogle tilfælde optræder andre, beslægtede vækstregulerende virkninger. Tillige kan der ved visse 11plant, thus also yielding an increase in yield. Such effects have also been observed in small-grain straws, such as barley, cucumber, sunflower, legumes such as soy, woody growths and ornamental plants, such as composites. In some cases, other related growth-regulating effects occur. Also, in certain 11

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plantesorter også konstateres en formindsket følsomhed overfor frost og en forøget resistens overfor sygdomsfremkaldere .plant varieties also found a reduced susceptibility to frost and an increased resistance to pathogens.

Den foreliggende opfindelse angår således også anvendelsen 5 af nitroaryl-alkylsulfon-derivater med formlen I eller af midler, som indeholder disse forbindelser som aktiv stof, til regulering af plantevæksten, især til opnåelse af en sterilisering af hankønnede blomsterdele, anvendelse som gametooid og/eller til at begunstige de hunkønnede 10 blomsterdele og alle deraf resulterende sekundæreffekter, såsom f.eks. udbyttestigning, forlængelse af blomstringstiden, forøget blomsterdannelse, regulering af frugtdannelsen eller modningsprocessen og lignende.Thus, the present invention also relates to the use of nitroaryl-alkylsulfone derivatives of formula I or of agents containing these compounds as active ingredient for regulating plant growth, in particular for obtaining a sterilization of male flower parts, use as gametoid and / or to favor the female 10 floral parts and all resulting secondary effects, such as e.g. yield increase, prolongation of flowering time, increased flowering, regulation of fruit formation or ripening process and the like.

Det har endvidere vist sig, at forbindelser med formlen I 15 har et til praktiske formål særdeles gunstigt mikrobicid-spektrum mod fytopatogene svampe og bakterier. De har således fordelagtige kurative, præventive og systemiske egenskaber og kan anvendes til beskyttelse af kulturplanter. Med de virksomme forbindelser med formlen I kan man 20 hæmme eller udrydde mikroorganismer, som optræder på planter eller plantedele (frugter, blomster, løv, stængler, knolde, rødder) af forskellige nyttekulturer, idet også senere udvoksende plantedele er beskyttet mod sådanne mikroorganismer. Forbindelserne med formlen I er især 25 virksomme mod svampesygdomme, såsom rust, skurv, ægte meldug og mod fungi imperfecti, f.eks. Puccinia, Rhizotoc-tonia, Venturia, Erypsiphe og Cercospora, samt mod bakterier af familien Pseudomonadaceae, især Xanthomonasarter.Furthermore, it has been found that compounds of formula I 15 have a very favorable microbicide spectrum for practical purposes against phytopathogenic fungi and bacteria. Thus, they have advantageous curative, preventive and systemic properties and can be used to protect cultural plants. With the active compounds of formula I, one can inhibit or eradicate microorganisms that occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of various utility cultures, since later growing plant parts are also protected against such microorganisms. In particular, the compounds of formula I are effective against fungal diseases such as rust, scab, real mildew and against fungi imperfecti, e.g. Puccinia, Rhizotoctonia, Venturia, Erypsiphe and Cercospora, as well as against bacteria of the family Pseudomonadaceae, especially Xanthomonas species.

De kan endvidere anvendes som bejdsemiddel til behandling 30 af planteformeringsmateriale (frugter, knolde, korn) og plantestiklinger til beskyttelse mod bakterie- og svampeinfektioner samt mod andre i jorden optrædende fytopatogene mikroorganismer.They may also be used as a dressing agent for the treatment of plant propagating material (fruits, tubers, grains) and plant cuttings for protection against bacterial and fungal infections as well as from other phytopathogenic microorganisms occurring in the soil.

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Som målkulturer for de heri anførte indikationsområder gælder indenfor rammerne af opfindelsen eksempelvis følgende plantearter: Korn/ såsom hvede, byg, rug, havre, ris, durra og beslægtede kornsorter, roer, såsom sukkerroer og 5 foderroer, kerne-, sten- og bærfrugter, såsom æble, pærer, blomme, fersken, mandel, kirsebær, jordbær, hindbær og brombær, bælgfrugter, såsom bønner, linser, ærter og soja, olieplantekulturer, såsom raps, sennep, valmue, oliven, solsikke, kokos, ricinus, kakao og jordnødder, agurkeplan-10 ter, såsom græskar, agurker og meloner, fiberplanter, såsom bomuld, hør, hamp og jute, citrusfrugter, såsom appelsiner, citroner, grapefrugt og mandariner, grøntsater, såsom spinat, hovedsalat, asparges, kålarter, gulerødder, løg, tomater, kartofler og paprika, laurbærplanter, såsom 15 avocado, kanel og kampher, eller planter såsom majs, tobak, nødder, kaffe, sukkerrør, te, vindruer, humle, banan- og naturkautjukplanter, samt prydplanter (kompositer).As target cultures for the indicated ranges herein, within the scope of the invention, for example, the following plant species apply: Cereals / such as wheat, barley, rye, oats, rice, sorghum and related cereals, beets such as sugar beet and fodder beets, kernel, stone and berry fruits, such as apple, pears, plum, peach, almond, cherry, strawberry, raspberry and blackberry, legumes such as beans, lentils, peas and soy, oilseed crops such as rape, mustard, poppy, olive, sunflower, coconut, castor, cocoa and peanuts , cucumber plants such as pumpkins, cucumbers and melons, fiber plants such as cotton, flax, hemp and jute, citrus fruits such as oranges, lemons, grapefruit and mandarins, vegetables such as spinach, main lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes and peppers, laurel plants, such as 15 avocados, cinnamon and camphor, or plants such as corn, tobacco, nuts, coffee, sugar cane, tea, grapes, hops, banana and natural beetle plants, and ornamental plants ( composites).

Nitroaryl-alkylsulfon-derivater kan anvendes pre- eller postemergent. Fortrinsvis foretages imidlertid posternergent 20 anvendelse, dvs. efter planternes spiring.Nitroaryl-alkylsulfone derivatives can be used pre- or post-merge. Preferably, however, posterergent use is made, i.e. after germination of plants.

Anvendelsesmængderne afhænger af den ønskede vækstregulerende eller mikrobicide virkning og skal fordelagtigt bestemmes ved forsøg afhængigt af plantearten og udviklingsstadiet, dvs. afhængigt af applikations tidspunktet., 25 Ved de forskellige indikationsområder gælder følgende tommelfingerregler: Til vækstregulering, især til opnåelse af en gametocid virkning, ligger anvendelsesmængderne sædvanligvis fra 0,05 til 12, fortrinsvis fra 0,5 til 8, især fra 1 til 4 kg virksom forbindelse pr. ha pr. applika-30 tion. Gunstige applikationstidspunkter især ved kornkulturer, er perioden efter spiringen, men før aksdannelse og dannelse af støvdragere henholdsvis 5 1/2-bladsstadiet eller den begyndende blomsterdannelse.Quantities of application depend on the desired growth regulating or microbicidal effect and should be advantageously determined by experiments depending on the plant species and stage of development, ie. 25 For the various indication ranges, the following rules of thumb apply: For growth control, especially to achieve a gametocide effect, the rates of application are usually from 0.05 to 12, preferably from 0.5 to 8, especially from 1 to 4 kg. effective connection per ha pr. application. Favorable times of application, especially in cereal crops, are the period after germination, but before axing and dusting, respectively, at the 5 1/2 leaf stage or the beginning of flower formation.

Hvis man ønsker at forøge antallet af blomsterstande el-35 ler at forlænge blomstringsfasen, f.eks. ved solsikke, bomuld, agurkeplanter, såsom græskar, agurker og meloner,If one wishes to increase the number of inflorescences or to prolong the flowering phase, e.g. by sunflower, cotton, cucumber plants such as pumpkin, cucumbers and melons,

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13 bælgfrugter, såsom bønner, linser, ærter og soja, eller prydplanter, ligger fordelagtige doseringer ved 0,5-4 kg as/ha, idet applikationen nødvendigvis skal foretages inden blomstringens begyndelse, især inden begyndende knopdannelse.13 legumes, such as beans, lentils, peas and soy, or ornamental plants, are advantageous doses at 0.5-4 kg ash / ha, the application necessarily having to be made before the beginning of flowering, especially before beginning bud formation.

5 Ved planter, som f.eks. bomuld, hvor blomsterne og frugterne optræder samtidigt, er såkaldt splitapplikation hensigtsmæssig, dvs. applikationen gentages periodisk, fortrinsvis med små anvendelsesmængder. Sædvanligvis afhænger anvendelsesmængderne også af applikationsmåden og ligger 10 ved den enkle bladapplikation fortrinsvis mellem 2 og 6 kg as/ha, ved splitapplikation mellem 2 og 4 kg as/ha, og ved jordapplikation (drench) fra 3 til 12 kg as/ha, alt efter jordtypen.5 For plants, such as cotton, where the flowers and fruits appear simultaneously, so-called split application is appropriate, ie. the application is repeated periodically, preferably with small amounts of application. Usually, the amounts of use also depend on the method of application, and 10 for the single leaf application is preferably between 2 and 6 kg as / ha, for split application between 2 and 4 kg as / ha, and for soil application (drench) from 3 to 12 kg as / ha, all according to the soil type.

Ved såsædbejdsning ligger anvendelsesmængderne fra ca. 0,02 15 til ca. 1 kg as pr. 100 kg såsæd. Når forbindelserne med formlen I anvendes som mikrobicider, er de fordelagtige anvendelsesmængder fra 0,5 til 5 kg pr. ha. Anvendelseskoncentrationen afhænger i praksis dog af sværhedsgraden af det mikroorganismeangreb, som kan bekæmpes.In the case of seed cultivation, the application rates range from approx. 0.02 to approx. 1 kg as per 100 kg seed. When the compounds of formula I are used as microbicides, the advantageous amounts of use are from 0.5 to 5 kg per day. ha. In practice, however, the concentration of application depends on the severity of the microorganism attack that can be combated.

20 De beskrevne anvendelsesmængder og applikationsmåder udgør en del af foreliggende opfindelse.The amounts of application and modes of application described form part of the present invention.

Virksomme forbindelser med formlen I anvendes sædvanligvis i form af præparater og kan samtidig eller efter påføres på overflader eller planter, som skal behandles, sammen med 25 andre virksomme forbindelser. Disse andre virksomme forbindelser kan være gødningsmidler, midler indeholdende sporelementer eller andre præparater til påvirkning af plantevæksten. Det kan også være selektive herbicider, insekticider, fungicider, baktericider, nematodicider, mollusci-30 cider eller blandinger af flere af disse præparater sammen med eventuelt andre indenfor formuleringsteknikken almindeligt anvendte bærerstoffer, tensider eller andre applikationsfremmende tilsætningsstoffer.Active compounds of formula I are usually used in the form of compositions and may be applied simultaneously or subsequently to surfaces or plants to be treated, along with 25 other active compounds. These other active compounds may be fertilizers, agents containing trace elements or other preparations for influencing plant growth. It may also be selective herbicides, insecticides, fungicides, bactericides, nematodicides, molluscicides or mixtures of several of these compositions together with any other carrier substances, surfactants or other application-promoting additives commonly used in the formulation technique.

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1414

Egnede bærerstoffer og tilsætningsstoffer kan være faste eller flydende og svarer til de ved den pågældende formulerings teknik anvendte hensigtsmæssige stoffer, såsom f.eks. naturlige eller regenererede mineralstoffer, opløs-5 ningsmidler, dispergeringsmidler, fugtemidler, hæftemidler, fortykningsmidler, bindemidler eller gødningsmidler.Suitable carriers and additives may be solid or liquid and correspond to the appropriate substances used in the art of the particular formulation, such as e.g. natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

En foretrukken fremgangsmåde til påføring af en virksom forbindelse med formlen I eller et agrokemisk middel, som indeholder mindst én af disse virksomme forbindelser, er 10 påføring på løvet (bladapplikation). Anvendes denne fremgangsmåde rettidigt i forhold til blomstringens begyndelse, kan der på denne måde opnås en særdeles selektiv hankønssterilitet. De virksomme forbindelser med formlen I kan imidlertid også via jorden gennem rodnettet trænge ind i 15 planterne (systemisk virkning), idet man mætter planternes voksested med et flydende præparat eller inkorporerer stofferne i fast form i jorden, f.eks. i form af et granulat (jordapplikation). Forbindelserne med formlen I kan imidlertid også påføres på frøkorn (coating), idet man enten mæt-20 ter kornene med et flydende præparat indeholdende den virksomme forbindelse eller overtrækker den med et fast præparat. Desuden er det i særlige tilfælde muligt at foretage andre former på påføring, f.eks. målrettet behandling af plantestængelen eller knopperne.A preferred method of applying an effective compound of formula I or an agrochemical agent containing at least one of these active compounds is application to the foliage (leaf application). If this method is used in a timely manner relative to the beginning of flowering, a highly selective male sterility can be obtained in this way. However, the active compounds of formula I can also penetrate through the soil through the root network into the plants (systemic effect), saturating the growth site of the plants with a liquid preparation or incorporating the substances in solid form into the soil, e.g. in the form of a granule (soil application). However, the compounds of formula I may also be applied to seed (coating) by either saturating the grains with a liquid composition containing the active compound or coating it with a solid composition. In addition, in special cases it is possible to perform other forms of application, e.g. targeted treatment of the plant stem or buds.

25 Forbindelserne med formlen I anvendes, i uforandret form eller fortrinsvis sammen med de indenfor formuleringsteknikken almindeligt anvendte hjælpemidler og forarbejdea på i og for sig kendt måde, f.eks. til emulsionskoncentrater, strygefærdige pastaer, sprøjteklare eller fortyndelige opløsnin-30 ger, fortyndede emulsioner, sprøjtepulvere, opløselige pulvere, støvmidler, granulater, samt indkapslinger i f.eks. polymere stoffer. Anvendelsesfremgangsmåderne, såsom sprøjtning, tågedannelse, forstøvning, ustrøning, påstrøning eller udhældning, vælges på samme måde som 35 midlets art under hensyntagen til de tilstræbte resultater og de givne forhold.The compounds of formula I are used, in unchanged form, or preferably together with the aids and preparations commonly used in the formulation technique in a manner known per se, e.g. for emulsion concentrates, irradiated pastes, spray-ready or dilute solutions, diluted emulsions, spray powders, soluble powders, dusting agents, granules, and enclosures in e.g. polymeric substances. The methods of application, such as spraying, misting, spraying, sprinkling, sprinkling or pouring, are selected in the same manner as the nature of the agent, taking into account the desired results and conditions.

1515

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Præparaterne, dvs. midlerne indeholdende den virksomme forbindelse med formlen I og eventuelt et fast eller flydende tilsætningsstof, fremstilles på kendt måde, f.eks. ved grundig blanding og/eller formaling af de virksomme for-5 bindeiser med strækkemidler, som f.eks. opløsningsmidler, faste bærestoffer og eventuelt overfladeaktive forbindelser (tensider). I de tilfælde, hvor et salt med formlen I skal bringes på præparatform, kan man undlade at isolere saltet, da også den vandige opløsning af phenol 10 med formlen I, som forinden er blevet neutraliseret med en base, direkte kan blandes med andre formuleringshjælpestoffer.The preparations, ie. the agents containing the active compound of formula I and optionally a solid or liquid additive are prepared in known manner, e.g. by thoroughly mixing and / or grinding the active interconnectors with extensives such as e.g. solvents, solid carriers and optionally surfactants (surfactants). In those cases where a salt of formula I is to be prepared in preparative form, the salt may not be isolated, since also the aqueous solution of phenol 10 of formula I, which has previously been neutralized with a base, can be directly mixed with other formulation auxiliaries.

Som opløsningsmidler kan eksempelvis anvendes aromatiske carbonhydrider, fortrinsvis Cg-C^"carlxmhydriderf såsom 15 f.eks. xylenblandinger eller substituerede naphthaiener, phthalsyreestere, såsom dibutyl- eller dioctylphthaiat, aliphatiske carbonhydrider, såsom cyclohexan eller paraffiner, alkoholer og glycoler samt deres ethere og estere, såsom ethanol, ethylenglycol, ethylenglycolmonomethyl-20 eller -ethylether, ketoner, såsom cyclohexanon, stærkt polære opløsningsmidler, såsom N-methyl-2-pyrrolidon, dimeth-ylsulfoxid eller dimethylformamid, samt eventuelt epoxy-derede planteolier, såsom epoxyderet kokosolie eller sojaolie, eller vand. Tilsætningen af mineralske olier eller 25 vegetabilske olier er især fordelagtigt ved præparater, som skal anvendes ved bladapplikation.As solvents, for example, aromatic hydrocarbons may be used, preferably Cg-C such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, highly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized plant oils such as epoxidized coconut oil or soybean oil. or water The addition of mineral oils or vegetable oils is particularly advantageous in compositions to be used in leaf application.

Som faste bærestoffer, f.eks. til støvmidler og disperger-bare pulvere, anvendes i reglen naturlige stenmel, såsom calcit, talkum, kaolin, montmorillonit eller attapulgit.As solid carriers, e.g. for dusting agents and dispersible powders, natural stone flour, such as calcite, talc, kaolin, montmorillonite or attapulgite, are generally used.

30 Til forbedring af de fysiske egenskaber kan der også tilsættes højdispers kiselsyre eller højdisperse, absorberende polymere. Som kornformigt absorberende granulatbæremate-riale kan anvendes porøse typer, såsom f.eks. pimpsten, knuste teglsten, sepiolit eller bentonit, og som ikke-ab-35 sorberende bærematerialer, f.eks. calcit eller sand. Desuden kan der anvendes et stort antal forgranulerede materialer af uorganisk eller organisk natur, såsom især dolomit eller findelte planterester.To improve the physical properties, high-dispersion silicic acid or high-dispersive absorbent polymers can also be added. As granular absorbent granular carrier material, porous types such as e.g. pumice, crushed bricks, sepiolite or bentonite, and as nonabsorbent carriers, e.g. calcite or sand. In addition, a large number of pre-granulated materials of inorganic or organic nature can be used, such as especially dolomite or finely divided plant residues.

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1616

Som overfladeaktive forbindelser kan der alt efter arten af den virksomme forbindelse med formlen I, som skal formuleres, anvendes ikke-ionogene, kationaktive og/eller anionaktive tensider med gode emulgerings-, dispergerings-5 og befugtningsegenskaber. Ved tensider skal også forstås tensidblandinger.As surfactants, depending on the nature of the active compound of formula I to be formulated, nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties can be used. Surfactants also include surfactant mixtures.

Egnede anioniske tensider kan være såvel såkaldte vandopløselige sæber som vandopløselige syntetiske overfladeaktive forbindelser.Suitable anionic surfactants may be so-called water-soluble soaps as well as water-soluble synthetic surfactants.

10 Som sæber kan eksempelvis anvendes alkalimetal-, jordalka-limetal- eller eventuelt substituerede ammoniumsalte af højere fedtsyrer (ciq-C22^· som f*eks. Na- eller K-saltene af olie- eller stearinsyre, eller af naturlige fedtsyreblandinger, som eksempelvis kan udvindes fra kokosolie 15 eller talgolie. Der kan endvidere også anvendes fedtsyre-methyllaurinsalte.For example, as soaps, alkali metal, alkaline earth metal or optionally substituted ammonium salts of higher fatty acids (ciq-C22 +) can be used as, for example, the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, such as may be recovered from coconut oil or tallow oil, and fatty acid methyl laurine salts may also be used.

Ofte anvendes imidlertid såkaldte syntetiske tensider, især fedtsulfonater, fedtsulfater, sulfonerede benzimidazol-derivater eller alkylarylsulfonater.However, so-called synthetic surfactants are often used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

20 Fedtsulfonaterne eller fedtsulfaterne foreligger i reglen som alkalimetal-, jordalkalimetal- eller eventuelt substituerede ammoniumsalte og indeholder en alkylgruppe med 8-22 carbonatomer, idet alkyl også omfatter alkyldelen af acylgrupper, f.eks. Na- eller Ca-saltet af ligninsulfon-25 syre, af dodecylsvovlsyreester eller af en af naturlige fedtsyrer fremstillet fedtalkoholsulfatblanding. Hertil hører også saltene af svovlsyreestrene og sulfonsyrerne af fedtalkohol-ethylenoxid-addukter. De sulfonerede benz-imidazolderivater indeholder fortrinsvis 2-sulfonsyregrup-30 per og en fedtsyregruppe med 8-22 carbonatomer. Alkylarylsulf onaterne er f.eks. Na-, Ca- eller triethanolamin-saltene af dodecylbenzensulfonsyre, af dibutylnapthalen-sulfonsyre eller af et naphthalensulfonsyre-formaldehyd-kondensationsprodukt.The fatty sulphonates or fatty sulphates are generally present as alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain an alkyl group of 8-22 carbon atoms, the alkyl also comprising the alkyl portion of acyl groups, e.g. The Na or Ca salt of lignin sulfonic acid, of dodecyl sulfuric acid ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. These include the salts of the sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid group of 8-22 carbon atoms. The alkylarylsulfonates are e.g. The Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnapthalene sulfonic acid or of a naphthalenesulfonic acid formaldehyde condensation product.

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Endvidere kan der også anvendes tilsvarende phosphater, f.eks. salte af phosphorsyreesteren af et p-nonylphenol-(4-14)-ethylenoxid-addukt.Furthermore, similar phosphates can also be used, e.g. salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct.

Som ikke-ioniske tenisder anvendes i første række polygly-5 coletherderivater af aliphatiske eller cycloaliphatiske alkoholer, mættede eller umættede fedtsyrer og alkylphe-noler, som kan indeholde 3-30 glycolethergrupper og 8-20 carbonatomer i den (aliphatiske) carbonhydridgruppe og 6-18 carbonatomer i alkylgruppen i alkylphenolerne.As non-ionic surfactants, polygly 5 carbon ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkyl phenols which may contain 3-30 glycol ether groups and 8-20 carbon atoms in the (aliphatic) hydrocarbon group and 6-18 are used primarily. carbon atoms in the alkyl group of the alkyl phenols.

10 Andre egnede ikke-ioniske tensider er de vandopløselige, 20-250 ethylenglycolethergrupper og 10-100 propylenglycol-grupper indeholdende polyethylenoxidaddukter med poly-propylenglycol, ethylendiaminpolypropylenglycol og alkyl-polypropylenglycol med 1-10 carbonatomer i alkylkæden.Other suitable nonionic surfactants are the water-soluble, 20-250 ethylene glycol ether groups and 10-100 propylene glycol groups containing polyethylene oxide adducts with polypropylene glycol, ethylene diamine polypropylene glycol and alkyl polypropylene glycol having 1-10 carbon atoms in the alkyl chain.

15 De nævnte forbindelser indeholder sædvanligvis 1-5 ethylen-glycolenheder pr. propylenglycolenhed.The said compounds usually contain 1-5 ethylene glycol units per liter. propylene glycol unit.

Som eksempler på ikke-ioniske tensider kan nonylphenolpoly-ethoxyethanoler, ricinusoliepolyglycolethere, polypropylen-polyethylenoxid-addukter, tributylphenoxypolyethoxyethanol, 20 polyethylenglycol og octylphenoxypolyethoxyethanol.As examples of nonionic surfactants may be nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Endvidere kan der også anvendes fedtsyreestere af polyoxy-ethylensorbitan, såsom polyoxyethylensorbitan-trioleat.Furthermore, fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate can also be used.

De kationiske tensider er først og fremmest kvaternære ammoniumsalte, der som N-substituent indeholder mindst én 25 alkylgruppe med 8-22 carbonatomer og som yderligere substi-tuenter lavere, eventuelt halogenerede alkyl-, benzyl-eller lavere hydroxyalkylgrupper. Saltene foreligger fortrinsvis som halogenider, methylsulfater eller ethylsul-fater, f.eks. stearyltrimethylammoniumchlorid eller benzyl-30 di (2-chlorethyl) ethylammoniumbromid.The cationic surfactants are primarily quaternary ammonium salts which contain as N-substituent at least one alkyl group of 8-22 carbon atoms and as additional substituents lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl groups. The salts are preferably present as halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyl-di (2-chloroethyl) ethylammonium bromide.

De i formuleringsteknikken almindeligt anvendte tensider er bl.a. beskrevet i følgende publikationer:The surfactants commonly used in the formulation technique include: described in the following publications:

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18 "McCutcheon1s Detergents and Emulsifiers Annual" MC Publishing Corp., Ringwood New Jersey, 1980 Sisely og Wood, "Enclyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 198018 "McCutcheon1's Detergents and Emulsifiers Annual" MC Publishing Corp., Ringwood New Jersey, 1980 Sisely and Wood, "Enclyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1980

De agrokemiske præparater indeholder i reglen 0,1-99, især 5 0,1-95% virksom forbindelse med formlen I og 99,9-1, især 99,8-5% fast eller flydende tilsætningsstof. Det er fordelagtigt, at tilsætningsstoffet indeholder 0-25, fortrinsvis 0,1-25% tensid.The agrochemicals generally contain 0.1-99, in particular 0.1-95% of active compound of Formula I and 99.9-1, especially 99.8-5% solid or liquid additive. Advantageously, the additive contains 0-25, preferably 0.1-25% surfactant.

Medens der som handelsvare sædvanligvis foretrækkes koncen-10 trerede midler, anvender slutforbrugeren i reglen fortyndede midler.While, as a commodity, usually concentrated agents are preferred, the end consumer usually uses diluted funds.

Midlet kan også indeholde andre tilsætninger, såsom stabilisatorer, skumdæmpningsmidler, viskositetsregulerende midler, bindemidler, hæftemidler samt gødningsmidler og 15 andre virksomme forbindelser til opnåelse af særlige virkninger.The agent may also contain other additives, such as stabilizers, antifoaming agents, viscosity regulators, binders, adhesives, and fertilizers, and other active compounds to achieve particular effects.

Sådanne agrokemiske midler er omfattet af den foreliggende opfindelse.Such agrochemicals are encompassed by the present invention.

Opfindelsen illustreres nærmere ved hjælp af de følgende 20 eksempler. Procenter og dele er på vægtbasis.The invention is further illustrated by the following examples. Percentages and parts are by weight.

1919

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Fremstillingseksempler a) Fremstilling afPreparation Examples a) Preparation of

0oN0oN

\ HO-<^V-S02CH3 (2.1) 4-Hydroxy-3-nitrophenyl-methylsulfon 5 Til 4 kg 30%'s natriumhydroxidopløsning sættes langsomt under omrøring 25,6 kg 4-chlor-3nitro-phenyl-methylsulfon, og blandingen fortyndes kontinuert med vand, indtil rumfanget udgør ca. 50 liter. Reaktionsblandingen opvarmes til 90°C, og i løbet af 3 til 4 timer tilsættes yderligere 10 29 kg 30%'s natriumhydroxidopløsning under omrøring. Der på opvarmes blandingen i 90 minutter til 103°C. Efter afkøling til ca. 60°C indstilles opløsningen med 16%'s svovlsyre på en pH-værdi på ca. 1,5. Derved udfælder produktet, som frafiltreres, vaskes og omkrystalliseres fra ethanol.(2) 4-Hydroxy-3-nitrophenyl-methylsulfone 5 To 4 kg of 30% sodium hydroxide solution is slowly added with stirring 25.6 kg of 4-chloro-3-nitro-phenyl-methylsulfone and the mixture is diluted continuous with water until the volume is approx. 50 liters. The reaction mixture is heated to 90 ° C and within 3 to 4 hours an additional 10 29 kg of 30% sodium hydroxide solution is added with stirring. The mixture is heated to 103 ° C for 90 minutes. After cooling to approx. At 60 ° C, the solution is adjusted with 16% sulfuric acid to a pH of approx. 1.5. Thereby, the product which is filtered off, washed and recrystallized from ethanol precipitates.

15 Udbytte: 24 kg farveløse krystaller. Smp. 166-168°C.Yield: 24 kg of colorless crystals. Mp. 166-168 ° C.

b) Fremstilling af(b) Preparation of

0oN0oN

O \_ ~V.-S02CH3 (1.14) 4-Cyclopropylcarbonyloxy-3-nitrophenyl-methylsulfon 32,6 g 4-hydroxy-3-nitrophenyl-methylsulfon suspenderes i 20 250 ml tetrahydrofuran, og der tilsættes 21 ml triethyl- amin. Til den dannede gule opløsning sættes dråbevis 15,7 g cyclopropancarboxylsyrechlorid under omrøring. Når den svagt eksoterme reaktion er stilnet af, omrøres blandingen i yderligere 3 timer ved stuetemperatur, hvorefter dannet 25 triethylammoniumchlorid frafiltreres, og filtratet inddampes.O-V 2 SO 2 CH 3 (1.14) 4-Cyclopropylcarbonyloxy-3-nitrophenyl-methylsulfone 32.6 g of 4-hydroxy-3-nitrophenyl-methylsulfone are suspended in 250 ml of tetrahydrofuran and 21 ml of triethylamine is added. To the yellow solution formed, 15.7 g of cyclopropane carboxylic acid chloride are added dropwise with stirring. When the slightly exothermic reaction is quenched, the mixture is stirred for an additional 3 hours at room temperature, then the resulting triethylammonium chloride is filtered off and the filtrate is evaporated.

Man får 42 g sej olie, som efter digerering med petroleums-ether giver 40,5 g lysegult, krystallinsk produkt.42 g of cool oil are obtained, which after digestion with petroleum ether gives 40.5 g of pale yellow crystalline product.

Smp. 114-116°C.Mp. 114-116 ° C.

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20 c) Fremstilling afC) Preparation of

" "T"" T

°2^ 0-<^ V-S02CH3 N(C4H9-n)4 (2.20) 4-Hydroxy-3-nitrophenyl-methylsulfon-tetra(n-butyl)ammoniumsalt__ 5 Til en opløsning af 13,5 g 4-hydroxy-3-nitrophenyl-methyl-sulfon i 100 ml ethanol sættes 41 g 40%'s vandig tetra-butylammonium-hydroxidopløsning. Den dannede dybgule opløsning inddampes på en rotationsfordamper til tørhed. Man får 28 g af en gul krystalmasse, smp. 98-100°C.2 (O) -SO 2 CH 3 N (C 4 H 9 -n) 4 (2.20) 4-Hydroxy-3-nitrophenyl-methylsulfone-tetra (n-butyl) ammonium salt 5 To a solution of 13.5 g 3-nitrophenylmethyl sulfone in 100 ml of ethanol is added 41 g of 40% aqueous tetra-butylammonium hydroxide solution. The resulting deep yellow solution is evaporated on a rotary evaporator to dryness. 28 g of a yellow crystal mass is obtained, m.p. 98-100 ° C.

10 På tilsvarende måde fremstilles også forbindelserne anført i de efterfølgende tabeller 1 og 2.Similarly, the compounds listed in subsequent Tables 1 and 2 are also prepared.

Tabel 1: Forbindelser med formlenTable 1: Compounds of formula

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21 S °2\_.21 S ° 2 \ _.

VC“°" \ y "S02R1 (V) • =s· ------.-VC “°" \ y "S02R1 (V) • = s · ------.-

R RR R

^orb-nr. 1 5 Fysisk konstant Λ^ Orb-No. 1 5 Physically constant Λ

1.1 C2H5 CC1=CC12 smp. 89-91° C1.1 C2H5 CC1 = CC12 m.p. 89-91 ° C

1.2 CH3 CC1=CC12 Smp. 129-131°C1.2 CH3 CC1 = CC12 m.p. 129-131 ° C

1.3 c H (n) CC1=CC12 Harpiks 1.4 C3H7(i) CC1=CC12 Harpiks1.3 c H (n) CC1 = CC12 Resin 1.4 C3H7 (i) CC1 = CC12 Resin

1.5 CH3 CH3 Smp. 139-141°C1.5 CH3 CH3 Mp. 139-141 ° C

1.6 C3H7(n) CH3 1.7 C3H7(i) CH31.6 C3H7 (n) CH3 1.7 C3H7 (i) CH3

1.8· C2H5 CH3 Smp. 87-90,5°C1.8 · C2H5 CH3 Mp. 87 to 90.5 ° C

1.9 CHo C0Hc Smp. 88-90^ J Z j1.9 CHo COHc Mp. 88-90 ^ J Z j

1.10 CH3 C3H7(n) Smp. 83-85 “C1.10 CH3 C3H7 (n) Mp. 83-85 ° C

1.11 CH3 c3h7 (i) Smp. 77-79331.11 CH3 c3h7 (i) Mp. 77-7933

1.12 C0Hc 0oHc Smp. 79-82C1.12 C0Hc 0oHc Mp. 79-82C

2 5 2 52 5 2 5

1.14 CH3 Cyclopropyl Smp. 114-116°C1.14 CH3 Cyclopropyl Mp. 114-116 ° C

1.15 CH3 Cyclobutyl1.15 CH3 Cyclobutyl

1.16 CH3 Cyclopentyl I1.16 CH3 Cyclopentyl I

1.17 CH3 Cyclohexyl Smp. 110-112°C1.17 CH3 Cyclohexyl Mp. 110-112 ° C

1118 CH3 Cycloheptyl1118 CH3 Cycloheptyl

1.19 CH C H (n) Smp. 63-65° C1.19 CH C H (n) Mp. 63-65 ° C

3 4 93 4 9

1.20 CH3 CH2C(CH3)2CH3 Smp. 89-91° C1.20 CH3 CH2C (CH3) 2CH3 Mp. 89-91 ° C

1.21 C2H5 C4Hg(n) 1.22 C2H5 CH2C(CH3)2CH3 itmt urifir»wimi-n--im_mimjijl· iiwiu- j-n___t.....i. . _ .11.21 C2H5 C4Hg (n) 1.22 C2H5 CH2C (CH3) 2CH3 itmt urifir »wimi-n - im_mimjijl · iiwiu- j-n ___ t ..... i. . _ .1

Tabel 1: (fortsat) 22Table 1: (continued) 22

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^ J^ J

Forb.nr. 1 5 ' fysisk konstantComp 1 5 'physically constant

1.23 CH3 (CH2)10CH3 Smp. 84-87°C1.23 CH3 (CH2) 10CH3 Mp. 84-87 ° C

1.24 CH3 CH=CH2 Smp. 114-117° C1.24 CH3 CH = CH2 Mp. 114-117 ° C

1.25 C2H5 CH=CH2 1.26 : C3H7(n) CH=CH21.25 C2H5 CH = CH2 1.26: C3H7 (n) CH = CH2

1.27 C2H5 CII=CHCH3 . Smp * 71-75 °C1.27 C2H5 CII = CHCH3. Mp * 71-75 ° C

1.28 CH3 CH=CHCH Smp. 100-102° C1.28 CH3 CH = CHCH Mp. 100-102 ° C

1.29 C2H5 CH=C(CH3)2 1.30 c2h5 c(ch3)=chch3 1.31 CH3 CH=C(CH3)2 Smp.88-90eC ....1.29 C2H5 CH = C (CH3) 2 1.30 c2h5 c (ch3) = chch3 1.31 CH3 CH = C (CH3) 2 Mp.88-90eC ...

1.32 CH3 C(CH3)=CHCH3 Smp.87-89°C1.32 CH3 C (CH3) = CHCH3 Mp.87-89 ° C

1.33 CH3 CH2C1 Smp. 108-110° C1.33 CH3 CH2C1 Mp. 108-110 ° C

1.34 CH3 C2H4C1 Smp. 123-125° C1.34 CH3 C2H4C1 Mp. 123-125 ° C

1.35 C2H5 CH2C1 Smp.69-72°C1.35 C 2 H 5 CH 2 Cl 1 mp 69-72 ° C

1.39 CH3 (CH=CH)2CH3 Smp.112-114°C1.39 CH3 (CH = CH) 2CH3 Mp.112-114 ° C

1.40 C2H5 (CH=CH)2CH3 Smp. 88-93°C1.40 C2H5 (CH = CH) 2CH3 Mp. 88-93 ° C

1.41 CH„ (0Ho) CH=CH„ Smp.56-58°C1.41 CH + (OH) CH = CH + Mp.56-58 ° C

ό L o l 1.42 : C3H?(i) CC1=CHCH3ό L o l 1.42: C3H? (i) CC1 = CHCH3

1.43 CH3 CC1=CHCH3 Smp. 120-122° C1.43 CH3 CC1 = CHCH3 Mp. 120-122 ° C

1.44 CH3 0CH3 Smp.163-165° C1.44 CH3 OCH3 Mp.163-165 ° C

I1.45 C2H5 0CH3 1-46 C3H7(n) 0CH3 1.47 CH3 0C2H5 1.48 CH3 OC3H7(i)I1.45 C2H5 0CH3 1-46 C3H7 (s) 0CH3 1.47 CH3 0C2H5 1.48 CH3 OC3H7 (i)

1.49 CH3 CH2Br Smp.98-100° C1.49 CH3 CH2Br Mp.98-100 ° C

1.50 CH3 CH2J1.50 CH3 CH2J

1.51 CH3 CF31.51 CH3 CF3

1.52 CH3 0(CH2)3C1 Smp.87-89°C1.52 CH3 O (CH2) 3Cl Mp.87-89 ° C

2323

Tabel 1: (fortsat)Table 1: (continued)

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i-1—:—r i-1 [Forb.nr. 1 5 [fysisk konstant 1.53 CH3 0C2H4C1 1.54 CH, OC.H Br 3 42 1.55 CH3 CC1=CHC1 Smp .129-130¾ 1.56 C2H5 CC1=CHC1i-1 -: - r i-1 [Prod. 1 5 [physically constant 1.53 CH3 OC2H4C1 1.54 CH, OC.H Br 3 42 1.55 CH3 CC1 = CHC1 Mp.

1.57 CEL CH,0C„H1.57 CEL CH, 0C "H

O l l o 1.58 CH3 (CH2)20CH3O l l o 1.58 CH3 (CH2) 20CH3

1.59 CH3 CH20CH3 Smp. 91-92° C1.59 CH3 CH20CH3 Mp. 91-92 ° C

1.60 C2H5 CH20CH3 1.61 C„H, C,H, 2 5 6 51.60 C2H5 CH20CH3 1.61 C „H, C, H, 2 5 6 5

1.62 CH3 C6H5 Smp. 142-'l44°C1.62 CH3 C6H5 Mp. 142 ° C-'l44

1.63 CH, C H (4-C1) 3 6 4 1.64 CH, C,H,(3-C1) 3 6 4 1.65 CH, C,H.(2-C1) 3 6 4 1.66 C2H5 C6H4(4-C1)1.63 CH, C H (4-C1) 3 6 4 1.64 CH, C, H, (3-C1) 3 6 4 1.65 CH, C, H. (2-C1) 3 6 4 1.66 C2H5 C6H4 (4-C1)

1.67 CH CrH;(4-NO,) Smp. 205-208°C1.67 CH CrH; (4-NO,) m.p. 205-208 ° C

3 6 4 ‘ . . . 1.68 CH, C,HQC1_(2,4) 3 o il.3 6 4 '. . . 1.68 CH, C, HQCl 1 (2.4) 3 o il.

1.69 CH3 C6H4(4-F) Smp. 157-159°C1.69 CH3 C6H4 (4-F) m.p. 157-159 ° C

1.71 C H C H (4-NO ) 2 5 6 4 2 1.72 CH3 C6H3(N02)2(2,4)1.71 C H C H (4-NO) 2 5 6 4 2 1.72 CH3 C6H3 (NO2) 2 (2.4)

1.73 CH3 CH=CHC6H5 Smp. 152-155° C1.73 CH3 CH = CHC6H5 Mp. 152-155 ° C

1.74 2-Tetrahydrofuryl Harpiks 1.75 CH3 2-Tetrahydro£uryl Harpiks 1.76 C2H5 2-Furyl1.74 2-Tetrahydrofuryl Resin 1.75 CH3 2-Tetrahydrouryl Resin 1.76 C2H5 2-Furyl

1.77 CH3 2-Furyl Smp. 173-175°C1.77 CH3 2-Furyl Mp. 173-175 ° C

1.78 CH3 (CH2)3C1 Smp. 83-85° C1.78 CH3 (CH2) 3C1 Mp. 83-85 ° C

1.79 CH3 CHBrCH3 Smp. 89-92° C1.79 CH3 CHBrCH3 Mp. 89-92 ° C

1.80 CH3 C(CH3)3 Smp. 117-119°C1.80 CH3 C (CH3) 3 m.p. 117-119 ° C

" ' ——1 ' 1 - * 111 ..... .1 I I i T . ^ 24"'——1' 1 - * 111 ..... .1 I I i T. ^ 24

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Tabel 2; Forbindelser med formlen °2\ ·— · \°-< ;-so2Ri (I)Table 2; Compounds of Formula ° 2 \ - - · \ ° - <; -so2Ri (I)

Forb.nr. R^ Fysisk konstantComp R ^ Physically constant

2.1 CH3 H Smp. 166-168°C2.1 CH3 H Mp. 166-168 ° C

2.2 C2H5 H Smp. 138°C2.2 C2H5 H Mp. 138 ° C

2.10 C3H7-n H2.10 C3H7-n H

2.11 C3H7~i H2.11 C3H7 ~ i H

2.19 CH3 N(CH3)4+ Smp. 151-153°C2.19 CH3 N (CH3) 4+ Mp. 151-153 ° C

2.20 CH- N(C.H -n) „+ Smp. 98-100°C2.20 CH- N (C.H-n) + Mp. 98-100 ° C

2.21 CH3 N(C2H5)4 Smp. 130-137 C2.21 CH3 N (C2H5) m.p. 130-137 ° C

2.22 CH3 N (CH3) 3CH2CgH,-+ Orangegul harpiks 2.23 CH3 N(CH3)3C^2H23 Orange harpiks 2.24 CH3 N(CH3)2N(CH3)3+ Orange harpiks 2.24 CH3 NH2NH3+2.22 CH3 N (CH3) 3CH2CgH + Orange yellow resin 2.23 CH3 N (CH3) 3C2H23 Orange resin 2.24 CH3 N (CH3) 2N (CH3) 3+ Orange resin 2.24 CH3 NH

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Formuleringseksempler for flydende virksomme forbindelser med formlen I (% = vægt-%)_ 1. Emulsionskoncentrater a) b) c)Formulation Examples for Liquid Active Compounds of Formula I (% = wt -%) - 1. Emulsion Concentrates a) b) c)

Aktiv forbindelse fra tabel 1 eller 2 25% 40% 50% 5 Ca-dodecylbenzensulfonat 5% 8% 6%Active compound from Table 1 or 2 25% 40% 50% 5 Ca-dodecylbenzenesulfonate 5% 8% 6%

Ricinusolie-polyethylenglycolether (36 mol ethylenoxid) 5% -Castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5% -

Tributylphenoyl-polyethylenglycolether (30 mol ethylenoxid) - 12% 4% 10 Cyclohexanon - 15% 20%Tributylphenoyl-polyethylene glycol ether (30 moles of ethylene oxide) - 12% 4% Cyclohexanone - 15% 20%

Xylenblanding 65% 25% 20%Xylene blend 65% 25% 20%

Ud fra sådanne koncentrater kan der ved fortynding med vand fremstilles emulsioner af en vilkårlig ønsket koncentration.From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

2. Opløsninger a) b) c) d) 15 Virksom forbindelse fra tabel 1 eller 2 80% 10% 5% 95%2. Solutions a) b) c) d) 15 Active compound from Table 1 or 2 80% 10% 5% 95%

Ethylenglycol-monomethylether 20% -Ethylene glycol monomethyl ether 20% -

Polyethylenglycol 400 - 70% N-Methyl-2-pyrrolidon - 20%Polyethylene Glycol 400 - 70% N-Methyl-2-pyrrolidone - 20%

Epoxideret kokosolie - - 1% 5% ' 20 Benzin (kogeområde 160-190°C) - - 94%Epoxidized Coconut Oil - 1% 5% Gasoline (Boiling range 160-190 ° C) - - 94%

Opløsningerne er egnede til anvendelse i form af små dråber.The solutions are suitable for use in the form of small droplets.

3. Granulater a) b)3. Granules a) b)

Virksom forbindelse fra tabel 1 eller 2 5% 10%Active compound from Table 1 or 2.5 5% 10%

Kaolin 94% 25 Højdispers kiselsyre 1%Kaolin 94% 25 High-dispersion silicic acid 1%

Attapulgit - 90%Attapulgit - 90%

Den virksomme forbindelse opløses i methylenchlorid, hvorefter opæløsningen sprøjtes på bærestoffet^ og opløsningsmidlet fordampes derefter i vakuum.The active compound is dissolved in methylene chloride, after which the dissolving solution is sprayed onto the carrier and the solvent is then evaporated in vacuo.

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4. Støvmidler a) b)4. Dust a) b)

Virksom forbindelse fra tabel 1 eller 2 2% 5% Højdispers kiselsyre 1% 5%Active compound from Table 1 or 2 2% 5% High-dispersion silicic acid 1% 5%

Talkum 97% 5 Kaolin - 90%Talc 97% 5 Kaolin - 90%

Ved grundig blanding af bærestofferne med den virksomme forbindelse fås brugsfærdige støvmidler.By thoroughly mixing the carriers with the active compound, ready-to-use dusting agents are obtained.

Formuleringseksempler for faste virksomme forbindelser med formlen I (% = væqt-%)_ 10 5. Sprøjtepulver a) b) c)Formulation Examples for Solid Active Compounds of Formula I (% = wt -%) _ 10 5. Spray Powder a) b) c)

Virksom forbindelse fra tabel 1 eller 2 25% 50% 75%Active compound from Table 1 or 2 25% 50% 75%

Na-Ligninsulfonat 5% 5%Na-lignin sulfonate 5% 5%

Na-Laurylsulfat 3% - 5%Na-Lauryl Sulfate 3% - 5%

Na-Diisobutylnaphthalensulfonat - 6% 10% 15 Octylphenylpolyethylenglycolether (7-8 mol ethylenoxid) - 2% - Højdispers kiselsyre 5% 10% 10%Na-Diisobutylnaphthalenesulfonate - 6% 10% Octylphenyl polyethylene glycol ether (7-8 moles of ethylene oxide) - 2% - High-dispersion silicic acid 5% 10% 10%

Kaolin 62% 27% -Kaolin 62% 27% -

Den virksomme forbindelse blandes grundigt med tilsætnings-20 stofferne, og der foretages grundig formaling på en egnet mølle. Der fås et sprøjtepulver, som kan fortyndes med vand til suspensioner af en vilkårlig ønsket koncentration.The active compound is thoroughly mixed with the additives and thorough grinding is performed on a suitable mill. A spray powder is obtained which can be diluted with water to suspend any desired concentration.

6. Emulsionskoncentrat6. Emulsion concentrate

Virksom forbindelse fra tabel 1 eller 2 10% 25 Octylphenolpolyethylenglycolether (4-5 mol ethylenoxid) 3%Active Compound from Table 1 or 2 10% Octylphenol polyethylene glycol ether (4-5 moles ethylene oxide) 3%

Ca-Dodecylbenzensulfonat 3%Ca-Dodecylbenzenesulfonate 3%

Ricinusoliepolyglycolether (35 mol ethylenoxid) 4% 30 Cyclohexanon 20%Castor oil polyglycol ether (35 moles of ethylene oxide) 4% Cyclohexanone 20%

Xylenblanding 50%Xylene Mixture 50%

Kokosolie 10%Coconut oil 10%

Ved fortynding af koncentratet med vand kan der fremstilles emulsioner af en vilkårlig ønsket koncentration.By diluting the concentrate with water, emulsions of any desired concentration can be prepared.

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27 7. Støvmiddel a) b) c)27 7. Dust a) b) c)

Virksom forbindelse fra tabel 1 eller 2 5% 8% 6%Active compound from Table 1 or 2.5 5% 8% 6%

Talkum 95% - 44%Talc 95% - 44%

Kaolin - 92% 50% 5 Der fås brugsfærdige støvmidler ved blanding af den virksomme forbindelse med bærestoffet og formaling på en egnet mølle.Kaolin - 92% 50% 5 Ready-to-use dusting agents are obtained by mixing the active compound with the carrier and grinding on a suitable mill.

8. Extruderet granulat8. Extruded granules

Virksom forbindelse fra tabel 1 eller 2 10% 10 Na-Ligninsulfonat 2%Active Compound from Table 1 or 2 10% 10 Na-Lignin Sulfonate 2%

Carboxymethylcellulose 1% - Kaolin 87%Carboxymethylcellulose 1% - Kaolin 87%

Den virksomme forbindelse blandes med tilsætningsstofferne, hvorpå der formales og fugtes med vand. Blandingen extrude-15 res og tørres derpå i en luftstrøm.The active compound is mixed with the additives, then ground and wetted with water. The mixture is extruded and then dried in an air stream.

9. Omhylningsqranulat a) b)9. Envelope granulate a) b)

Virksom forbindelse fra tabel 1 eller 2 3% 5%Active compound from Table 1 or 2 3% 5%

Polyethylenglycol 200 3% 3%Polyethylene Glycol 200 3% 3%

Kaolin 94% 92% 20 Den fintformalede virksomme forbindelse påføres ensartet på kaolin fugtet med polyethylenglycol i et blandeapparatur.Kaolin 94% 92% 20 The finely ground active compound is uniformly applied to kaolin moistened with polyethylene glycol in a mixing apparatus.

På denne måde fås støvfri omhylningsgranulater.In this way, dust-free casing granules are obtained.

10. Suspensionskoncentrat10. Suspension concentrate

Virksom forbindelse fra tabel 1 eller 2 40% 25 Ethylenglycol 10%Active compound from Table 1 or 2 40% Ethylene glycol 10%

Nonylphenolpolyethylenglycolether (15 mol ethylenoxid) 6% N-Ligninsulfonat 10%Nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% N-lignin sulfonate 10%

Carboxymethylcellulose 1% 30 37%'s vandig formaldehydopløsning 0,2%Carboxymethyl cellulose 1% 37% aqueous formaldehyde solution 0.2%

Silikoneolie i form af en 75%'s vandig emulsion 0,8%Silicone oil in the form of a 75% aqueous emulsion 0.8%

Vand 32%Water 32%

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Den fintformalede virksomme forbindelse blandes grundigt med tilsætningsstofferne. Der fås således et suspensionskoncentrat, hvoraf man ved fortynding med vand kan fremstille suspensioner af en vilkårlig ønsket koncentration.The finely ground active compound is thoroughly mixed with the additives. Thus, a suspension concentrate is obtained from which, by dilution with water, suspensions of any desired concentration can be prepared.

5 Formuleringstilsætninger, som forøger vedhæftningen af den virksomme forbindelse på planterne, såsom f.eks. mineralske eller vegetabilske olier, virker særdeles fordelagtig ved bladapplikation.Formulation additives which enhance the attachment of the active compound to the plants, such as e.g. mineral or vegetable oils, seems particularly advantageous in leaf application.

Biologiske eksempler 10 Eksempel 11: Gametocid virkning ved.småkornede halmfrugter a) Induktion af hankønssterilitetBiological Examples 10 Example 11: Gametocid Effect on Small Grain Straw Fruits a) Induction of Male Sterility

Hvedeplanter sprøjtes ensartet ved blomstringens begyndelse, dvs. på ca. 5 1/2-bladsstadiet, med en sprøjtevæske (3000 ppm virksom forbindelse) fremstillet ud fra et sprøj-15 tepulver indeholdende den virksomme forbindelse. 2 til 4 uger efter applikationen, dog inden støvbladene er skudt frem, beskyttes hvert aks mod fremmedbestøvning ved tildækning. Bedømmelsen af den gametocide virkning foretages på høsttidspunktet ved optælling af antallet af dannede 20 korn pr. aks. Som sammenligning anvendes ubehandlede hvedeplanter .Wheat plants are sprayed uniformly at the beginning of flowering, ie. of approx. 5 1/2 leaf stage, with a spray liquid (3000 ppm effective compound) prepared from a spray powder containing the active compound. 2 to 4 weeks after application, however, before the dust leaves are pushed out, each axis is protected from foreign dust by cover. The gametocidal effect is assessed at the time of harvest by counting the number of 20 grains formed per day. aks. By comparison, untreated wheat plants are used.

b) Frugtbarhedstest (dannelse af hybridsåsæd)(b) Fertility test (hybrid seed production)

En kontrolgruppe af hvedeplanter behandles som beskrevet ovenfor under a), tildækkes og holdes isoleret og fremmed-25 bestøves med blomsterpollen fra en anden hvedesort. Bedømmelsen af befrugtningsevnen foretages på høsttidspunktet ved optælling af antallet af dannede hybridkorn pr. aks. Til sammenligning anvendes ubehandlede hvedeplanter og behandlede, men tildækkede planter.A control group of wheat plants is treated as described above under (a), covered and kept isolated, and foreign-pollinated with flower pollen from another wheat variety. The fertilization ability is assessed at the time of harvest by counting the number of hybrid grains formed per day. aks. In comparison, untreated wheat plants and treated but covered plants are used.

30 Nitroaryl-alkylsulfonderivaterne i tabel 1 og 2 udviser i ovenstående forsøg a og b en særdeles god gametocid virkning.30 The nitroaryl-alkylsulfone derivatives in Tables 1 and 2 show a very good gametocidal effect in the above experiments a and b.

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Forbindelserne nr. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.14, 1.17, 1.19, 1.20, 1.23, 1.24, 1.28, 1.31, 1.32, 1,33, 1.34, 1.39, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55,1.59, 1.62, 1.67, 1.69, 1.73, 1.77-1.79, 2.1, 2.2 og 2.19-2.21 reducerer dannelsen 5 af korn pr. aks ved 0-15%. Selv ved en koncentration af virksom forbindelse på 750 ppm undertrykker bl.a. forbindelserne nr. 1.2, 1.5, 1.14, 1.24,2.1 og 2.20 korndannelsen fuldstændig (ubehandlede kontrolplanter = 100% korn). De med de anførte forbindelser behandlede to kontrolgrupper 10 (forsøg b) udvikler sig efter fremmedbestøvning på samme måde som de ubehandlede planter. Antallet af høstede hybridkorn udgør 85 til 100%. Hos de med en af forbindelserne nr. 1.2, 1.5, 1.14, 1,24, 2.1 og 2.20 behandlede hvedeplanter ligger antallet af hybridkorn endda endnu 15 højere end ved den ubehandlede sammenligningsgruppe.Compounds Nos. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.14, 1.17, 1.19, 1.20, 1.23, 1.24, 1.28, 1.31, 1.32, 1.33, 1.34, 1.39, 1.41, 1.43, 1.44, 1.49, 1.52 , 1.55.1.59, 1.62, 1.67, 1.69, 1.73, 1.77-1.79, 2.1, 2.2 and 2.19-2.21 reduce the formation of 5 grains per day. axis at 0-15%. Even at a concentration of active compound of 750 ppm, Compounds Nos. 1.2, 1.5, 1.14, 1.24.2.1 and 2.20 complete granulation (untreated control plants = 100% grain). The two control groups 10 (experiment b) treated with the compounds listed develop after extraneous pollination in the same way as the untreated plants. The number of harvested hybrid grains is 85 to 100%. In the wheat plants treated with one of the compounds 1.2, 1.5, 1.14, 1.24, 2.1 and 2.20, the number of hybrid grains is even 15 higher than in the untreated comparison group.

Sammenlignelige resultater iagttages ved analoge forsøg med byg og rug.Comparable results are observed in analogous experiments with barley and rye.

Eksempel 12; Gametocid virkning på majs a) Induktion af hankønssterilitet 20 Majsplanter sprøjtes ensartet ved blomsterdannelsen, dog før hanblomsterne er blevet synlige, med en suspension af den virksomme forbindelse (3000 ppm virksom forbindelse).Example 12; Gametocid effect on maize a) Induction of male sterility 20 Maize plants are sprayed uniformly during flowering, however, before male flowers become visible, with a suspension of the active compound (3000 ppm active compound).

Kolbe og faner på de behandlede planter tildækkes omhyggeligt. Efter dannelse af hanblomsterdelen, dvs. ca. 3 uger 25 efter applikationen, bedømmes den gametocide virkning ved hjælp af fane- og støvbladsdannelsen, og pollensteriliteten konstateres ved hjælp af en selvbestøvning. Dertil overføres blomsterpollen, såfremt det er dannet, fra samme plante til kolbenes tråde (selvbestøvning), og på høsttids-30 punktet optælles antallet af majskorn pr. kolbe. Som sammenligning anvendes ubehandlet majs.Cover the flask and tabs on the treated plants carefully. After forming the male flower section, ie. ca. 3 weeks 25 after application, the gametocidal effect is assessed by tab and dust leaf formation and pollen sterility is assessed by self-pollination. In addition, the pollen, if formed, is transferred from the same plant to the flasks of the flask (self-pollination), and at the harvest-time point the number of corn grains per flask. By comparison, untreated corn is used.

b) Frugtbarhedstest (dannelse af hybridsåsæd)(b) Fertility test (hybrid seed production)

En kontrolgruppe af majsplanter behandles som beskrevet ovenfor under a), og hanblomsterdelene og hunblomsterdele-35 ne tildækkes omhyggeligt. Ca. 3 uger efter applikationenA control group of maize plants is treated as described above under (a), and the male flower parts and female flower parts are carefully covered. Ca. 3 weeks after application

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30 fremmedbestøves kolberne på de behandlede planterne med biomsterpollen fra en anden udvalgt majssort. På høsttidspunktet bedømmes frugtbarheden ved optælling af antallet af hybridkorn pr. kolbe. Som sammenligning anvendes ube-5 handlede majs.30, the flasks are sprayed on the treated plants with biomster pollen from another selected maize variety. At harvest time, fertility is assessed by counting the number of hybrid grains per day. flask. By comparison, untreated corn is used.

I de ovenfor beskrevne forsøg a og b fremkalder forbindelserne fra tabel 1 og 2 en næsten fuldstændig hankønssterilitet. Sålede medfører f.eks. behandlingen med forbindelserne nr. 1.1, 1.2, 1.5, 1.9, 1.14, 1.17, 1.19, 1.20, 1.24, 10 1.28, 1.31 til 1.35, 1.41, 1.43, 1.44, 1.49, 1.55, 1.59, 1.62, 1.69, 1.77, 1.78, 1.79, 2.1, 2.2 og 2.19-2.21 en reduktion af majskornene pr. kolbe på mindre end 20%. Ved en koncentration af virksom forbindelse på 2000 ppm undertrykker forbindelserne nr. 1.2, 1.5, 1.14, 1.24, 1.77, 2.1 15 2.2, 2.19 og 2.20 dannelsen af korn fuldstændig (ubehandlet kontrol = 100% korn). Ingen af forbindelserne har kendelig indflydelse på fremmedbestøvningen. Udbyttet af hybridkorn udgør 85 til 100%.In the experiments described above a and b, the compounds of Tables 1 and 2 elicit an almost complete male sterility. For example, sold soles treatment with Compounds Nos. 1.1, 1.2, 1.5, 1.9, 1.14, 1.17, 1.19, 1.20, 1.24, 10 1.28, 1.31 to 1.35, 1.41, 1.43, 1.44, 1.49, 1.55, 1.59, 1.62, 1.69, 1.77, 1.78, 1.79, 2.1, 2.2 and 2.19-2.21 a reduction of the corn grains per year. flask of less than 20%. At a concentration of active compound of 2000 ppm, Compounds Nos. 1.2, 1.5, 1.14, 1.24, 1.77, 2.1, 2.2, 2.19 and 2.20 completely suppress the formation of grain (untreated control = 100% grain). None of the compounds have any appreciable influence on foreign pollination. The yield of hybrid grains is 85 to 100%.

Eksempel 13: I Gametocid virkning på solsikke (bladappli-20 _kation)_ a) Induktion af hankønssterilitetExample 13: In Gametocid Effect on Sunflower (Leaf Appliance 20) a) Induction of Male Sterility

Solsikkeplanter af en selvbestøvende sort sprøjtes ensartet ca. 3 uger inden blomstringen med en emulsion af den virksomme forbindelse (3000 ppm virksom forbindelse). Blomster-25 knopperne på de behandlede planter beskyttes mod fremmedbestøvning ved omhyggelig tildækning, og på høsttidspunktet bedømmes den gametocide virkning ved optælling af antallet af dannede hele korn. Som sammenligning tjener ubehandlede solsikkeplanter.Sunflower plants of a self-pollinating variety are sprayed uniformly approx. 3 weeks before flowering with an emulsion of the active compound (3000 ppm effective compound). The flower-25 buds of the treated plants are protected from foreign pollination by careful coverage, and at the time of harvest, the gametocidal effect is assessed by counting the number of whole grains formed. By comparison, untreated sunflower plants serve.

30 b) Frugtbarhedstest (dannelse af hybridsåsæd)30 b) Fertility test (hybrid seed production)

En kontrolgruppe solsikkeplanter behandles som beskrevet ovenfor under a). Knopperne på de behandlede planter tildækkes omhyggeligt. Efter åbning af blomsterne foretages en fremmedbestøvning med blomsterpollen fra en anden 35 udvalgt solsikkesort. Til dette formål anbringes de intakte DK 1590938 31 blomsterpollen under tildækningen. Bedømmelsen af frugtbarheden foretages på høsttidspunktet ved optælling af antallet af dannede hybridkorn. Som sammenligningsgrundlag anvendes ubehandlede solsikkeplanter.A control group of sunflower plants is treated as described above under (a). The buds of the treated plants are carefully covered. After opening the flowers, a foreign pollination is performed with the flower pollen from another 35 selected sunflower varieties. For this purpose, the intact flower pollen is placed under the cover. The fertility assessment is done at harvest time by counting the number of hybrid grains formed. As a basis for comparison, untreated sunflower plants are used.

5 II Gametocid virkning på solsikke (jordapplikation) a) Induktion af hankønssterilitet5 II Gametocid effect on sunflower (soil application) a) Induction of male sterility

Solsikkeplanter af en selvbefrugtende sort udplantes i potter. 3-6 uger inden blomstringens begyndelse vandes jorden i potterne med en sprøjtevæske (0,006% virksom 10 forbindelse, beregnet på jordrumfanget), fremstillet ud fra et sprøjtepulver indeholdende den virksomme forbindelse. Der drages omsorg for, at overjordiske plantedele ikke befugtes. Knopperne på de behandlede planter tildækkes omhyggeligt, og på høsttidspunktet bedømmes den gametocide 15 virkning ved optælling af antallet af fuldstændige korn i sammenligning med ubehandlede solsikkeplanter.Sunflower plants of a self-fertilizing variety are planted in pots. Three to six weeks before flowering begins, the soil in the pots is irrigated with a spray liquid (0.006% effective compound, based on soil volume), prepared from a spray powder containing the active compound. Care will be taken to ensure that soil parts of the soil are not wetted. The buds of the treated plants are carefully covered, and at the time of harvest, the gametocide effect is assessed by counting the number of complete grains in comparison with untreated sunflower plants.

b) Frugtbarhedstest (dannelse af hybridsåsæd)(b) Fertility test (hybrid seed production)

En kontrolgruppe af solsikkeplanter udplantes og behandles som beskrevet ovenfor under a). Knopperne på de behandlede 20 planter tildækkes omhyggeligt. Efter blomstringens begyndelse foretages en fremmedbestøvning med blomsterpollen fra en anden, udvalgt solsikkesort. Til dette formål anbringes de intakte blomsterpollen under tildækningen. Bedømmelsen foretages på høsttidspunktet ved optælling af an-25 tallet af dannede hybridkorn. Som sammenligning tjener ubehandlede solsikkeplanter.A control group of sunflower plants is transplanted and treated as described above under (a). The buds of the treated 20 plants are carefully covered. After flowering, a foreign pollination is carried out with flower pollen from another selected sunflower variety. For this purpose, the intact flower pollen is placed under the cover. The assessment is made at the time of harvest by counting the number of hybrid grains formed. By comparison, untreated sunflower plants serve.

I ovenstående forsøg I og II udviser forbindelserne anført i tabel 1 og 2 en sammenligning gametocid virkning.In Experiments I and II above, the compounds listed in Tables 1 and 2 show a comparative gametocide effect.

Efter behandling med en af de virksomme forbindelser nr.After treatment with one of the active compounds no.

30 1.1, 1.2, 1.5, 1.9, 1.10 1.11, 1.14, 1.17, 1.19, 1.24, 1.28, 1.31, 1.32, 1.33, 1.34, 1.35, 1.39, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55, 1.59, 1.62, 1.67, 1.69, 1.73, 1.77-1.79, 2.1, 2.2 og 2.19-2.24 undertrykkes dannelsen af frøkorn i sammenligningmed ubehandlede planter til mindre end 35 15%. Forbindelserne nr. 1.1, 1.2, 1.5, 1.14, 1.24, 1.77,1.1, 1.2, 1.5, 1.9, 1.10 1.11, 1.14, 1.17, 1.19, 1.24, 1.28, 1.31, 1.32, 1.33, 1.34, 1.35, 1.39, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55, 1.59, 1.62, 1.67, 1.69, 1.73, 1.77-1.79, 2.1, 2.2 and 2.19-2.24 the formation of seed grains in comparison with untreated plants is suppressed to less than 35 15%. Compounds Nos. 1.1, 1.2, 1.5, 1.14, 1.24, 1.77,

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32 2.1, 2.2 og 2.19-2.24 giver endog 100%"s hankønssterilitet, hvorved fremmedbestøvningen ikke påvirkes i kendelig grad og fører til et udbytte af hybridkorn på 80 til 100%.32 2.1, 2.2 and 2.19-2.24 even provide 100% male sterility, thereby not significantly affecting foreign pollination and leading to a yield of 80 to 100% hybrid grains.

Eksempel 14; Blomsterstimulering hos bomuld 5 Bomuldsplanter sprøjtes ensartet inden blomstringens begyndelse med en vandig dispersion af den virksomme forbindelse (500 ppm virksom forbindelse), og applikationen gentages afhængigt af vækstraten med mellemrum på 1 til 3 uger. På høsttidspunktet bedømmes kapsel- og frødannelsen 10 i sammenligning med ubehandlede kontrolplanter.Example 14; Flower stimulation in cotton 5 Cotton plants are sprayed uniformly before the beginning of flowering with an aqueous dispersion of the active compound (500 ppm effective compound) and the application is repeated depending on the growth rate at intervals of 1 to 3 weeks. At the time of harvest, capsule and seed formation 10 is assessed in comparison with untreated control plants.

Forbindelser fra tabel 1 og 2 har hos bomuld en udpræget stimulerende virkning på blomsterdannelsen. Efter gentagen •e behandling med en af forbindelserne nr. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.14, 1.17, 1.19, 1.28, 1.31, 1.32, 1.33, 1.34, 15 1.35, 1.39, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55,1.59, 1.62, 1.67, 1.69, 1.73, 1.77-1.79, 2.1, 2.2 og 2.19-2.21 forøges antallet af blomsterstande med 5-25% i sammenligning med ubehandlede planter. Planterne har et sundt udseende og har en kvalitativ normal kapsel- og frødannelse.Compounds from Tables 1 and 2 in cotton have a pronounced stimulating effect on flower formation. After repeated treatment with one of compounds Nos. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.14, 1.17, 1.19, 1.28, 1.31, 1.32, 1.33, 1.34, 1.35, 1.39, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55.1.59, 1.62, 1.67, 1.69, 1.73, 1.77-1.79, 2.1, 2.2 and 2.19-2.21 the number of inflorescences increased by 5-25% compared to untreated plants. The plants have a healthy appearance and have a qualitative normal capsule and seed formation.

20 Eksempel 15; Gametocid virkning på tomater a) Induktion af hankønssterilitetExample 15; Gametocid effect on tomatoes a) Induction of male sterility

Tomatplanter sprøjtes ensartet inden blomstringens begyndelse med en sprøjtevæske indeholdende den virksomme forbindelse (1000 ppm virksom forbindelse), fremstillet 25 ud fra et sprøjtepulver, og applikationen af den virksomme forbindelse gentages med intervaller afhængigt af planternes vækstrate. Bedømmelsen af den gametocide virkning foretages på høsttidspunktet ved optælling af antallet af frø i de helt udviklede frugter pr. plante sammenlignet 30 med ubehandlede tomatplanter.Tomato plants are uniformly sprayed before the beginning of flowering with a spray liquid containing the active compound (1000 ppm effective compound) prepared from a spray powder and the application of the active compound is repeated at intervals depending on the growth rate of the plants. The assessment of the gametocidal effect is made at the time of harvest by counting the number of seeds in the fully developed fruits per day. plant compared 30 with untreated tomato plants.

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b) Frugtbarhedstest.b) Fertility test.

En gruppe kontrolplanter behandles som beskrevet ovenfor under a), idet der dog under blomstringen foretages fremmedbestøvning med udvalgte blomsterpollen fra en anden 5 tomatsort. Bedømmelsen af de behandlede planters befrugtningsevne foretages på høsttidspunktet ved optælling af antallet af frø i de fuldstændigt udviklede frugter pr. plante og i sammenligning med ubehandlede tomatplanter.A group of control plants is treated as described above under (a), however, during flowering, foreign pollination is carried out with selected flower pollen from another 5 tomato variety. The fertilization ability of the treated plants is assessed at the time of harvest by counting the number of seeds in the fully developed fruits per year. plant and in comparison with untreated tomato plants.

I ovenstående forsøg har forbindelser fra tabel 1 og 2 10 en særdeles god gametocid virkning i tomatkulturer. Efter behandling med en af de virksomme forbindelser nr. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.14, 1.17, 1.19, 1.24, 1.28, 1.31, 1.32, 1.33, 1.34, 1.35, 1.39, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55, 1.59, 1.62, 1.67, 1.69, 1.73, 1.77-1.79, 15 2.1, 2.2, 2.19, 2.20, 2.21 og 2.22 formindskes frugtstør relsen i sammenligning med ubehandlede planter, og det konstateres, at frugterne indeholder færre eller ingen frø. Ved behandling med en af forbindelserne nr. 1.1, 1.2, 1.5, 1.14, 1.24, 1.77 og 2.1 opnås en fuldstændig hankøns-20 sterilisering. Fremmedbefrugtningen påvirkes ikke i kendelig grad, hvilket ligeledes er tilfældet ved forbindelse nr. 2.19 og 2.20.In the above experiments, compounds from Tables 1 and 210 have a particularly good gametocide effect in tomato cultures. After treatment with one of the active compounds Nos. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.14, 1.17, 1.19, 1.24, 1.28, 1.31, 1.32, 1.33, 1.34, 1.35, 1.39, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55, 1.59, 1.62, 1.67, 1.69, 1.73, 1.77-1.79, 15 2.1, 2.2, 2.19, 2.20, 2.21 and 2.22, the fruit size is reduced in comparison with untreated plants and it is found that the fruits contain fewer or no seeds. By treatment with one of compounds Nos. 1.1, 1.2, 1.5, 1.14, 1.24, 1.77 and 2.1, complete male sterilization is achieved. Foreign fertilization is not appreciably affected, as is the case with compounds Nos. 2.19 and 2.20.

Eksempel 16: Gametocid virkning på leguminoser a) Induktion af hankønssterilitet (postemergent behandling) 25 Buskbønner af sorten "Mity" sprøjtes ensartet på blomsterknopstadiet med en suspension af den virksomme forbindelse (2000 ppm virksom forbindelse), hvorefter knopperne omhyggeligt tildækkes. Efter udvikling af blomsterne bedømmes pollendannelsen, og pollensteriliteten afprøves 30 ved krydsning med udvalgte, håndsteriliserede blomster fra ubehandlede kontrolplanter. Som kontrol foretages analoge krydsninger på ubehandlede planter. I et parallelforsøg foretages Drenchapplikation (udhældning i rodzonen af 4 kg/AS/ha) i stedet for bladapplikation.Example 16: Gametocid Effect on Leguminoses a) Induction of Male Sterility (Post-Energy Treatment) 25 "Mity" shrub beans are sprayed uniformly at the flower bud stage with a suspension of the active compound (2000 ppm effective compound) and the buds are carefully covered. After developing the flowers, pollen formation is assessed and pollen sterility is tested by crossing with selected, hand-sterilized flowers from untreated control plants. As analogue crossings are made on untreated plants. In a parallel experiment, Drench application (pouring in the root zone of 4 kg / AS / ha) is made instead of leaf application.

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34 b) Frugtbarhed34 b) Fertility

En kontrolgruppe buskbønner behandles som beskrevet ovenfor under a) , og blomsterknopperne tildækkes omhyggeligt. Efter blomsternes åbning bestøves blomsterne med pollen fra ube-5 handlede blomster, og befrugtningsraten sammenlignes med befrugtningsraten for krydsbestøvede, ubehandlede, håndsteriliserede blomster fra forsøg a).A control group of bush beans is treated as described above under (a) and the flower buds are carefully covered. After the opening of the flowers, the flowers are pollinated with pollen from untreated flowers and the fertilization rate is compared with the fertilization rate of cross-pollinated, untreated, hand-sterilized flowers from Experiment a).

I ovenstående forsøg fremkalder forbindelserne nr. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.14, 1.17, 1.19, 1.20, 1.23, 1.27, 10 1.28, 1.31-1.34, 1.39, 1.40, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55, 1.59, 1.67, 1.69, 1.73, 1,77-1.79, 2.1, 2.20 og 2.21 en pollenreduktion med 85-90% og en pollenstabilitet på 90-100% i sammenligning med ubehandlede kontrolplanter, hvis pollen er helt udviklede og intakte. Hos de behandle-15 de planter iagttages ingen kendelig påvirkning af hunblomsterdelene ved befrugtningen med ubehandlet fremmed pollen (90-100% frugtdannelse), dog udvikles der delvis partheno-carpe frugter.In the above experiments, Compounds Nos. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.14, 1.17, 1.19, 1.20, 1.23, 1.27, 10 1.28, 1.31-1.34, 1.39, 1.40, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55, 1.59, 1.67, 1.69, 1.73, 1.77-1.79, 2.1, 2.20 and 2.21 a pollen reduction of 85-90% and a pollen stability of 90-100% compared to untreated control plants whose pollen is fully developed and intact. In the treated plants, no appreciable effect on the female flower parts is observed during fertilization with untreated foreign pollen (90-100% fruit formation), however, partial partheno-carp fruits are developed.

Eksempel 17: Gametocid virkning på hør 20 a) Induktion af hankønsterilitet Hørplanter af sorten "Blaubluhender" sprøjtes ensartet på knopstadiet med en suspension af virksom forbindelse (500 og 100 ppm virksom forbindelse), hvorefter knopperne omhyggeligt tildækkes. Efter blomsternes udvikling,bedømmes pol-25 lendannelsen, og pollensteriliteten testes ved krydsning med udvalgte håndsteriliserede blomster fra ubehandlede kontrolplanter. Som sammenligning foretages analoge krydsninger med ubehandlede planter.Example 17: Gametocid effect on flax 20 a) Induction of male sterility Flax plants of the "Blaublu hands" variety are sprayed uniformly on the bud stage with a suspension of active compound (500 and 100 ppm active compound), after which the buds are carefully covered. Following the development of the flowers, pollen formation is assessed and pollen sterility is tested by crossing with selected hand sterilized flowers from untreated control plants. By comparison, analogous crossings are made with untreated plants.

I. et parallelforsøg foretages Drenchapplikation (udhæld-30 ning i rodzonen af 3 kg/AS/ha) i stedet for bladapplikation.In a parallel experiment, Drench application (pouring into root zone of 3 kg / AS / ha) is made instead of leaf application.

b) Frugtbarhedstestb) Fertility test

En kontrolgruppe af hørplanter behandles som beskrevet oven-A control group of flax plants is treated as described above.

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35 for under a), og blomsterknopperne tildækkes omhyggeligt.35 for under a) and the flower buds are carefully covered.

Efter åbningen bestøves blomsterne med pollen fra ubehandlede blomster, og befrugtningsraten sammenlignes med raten for krydsbestøvede ubehandlede håndsteriliserede blomster 5 fra forsøg a).After opening, the flowers are pollinated with pollen from untreated flowers and the fertilization rate is compared with the rate of cross-pollinated untreated hand sterilized flowers 5 from Experiment a).

I ovenstående forsøg fremkalder forbindelserne nr. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.17, 1.20, 1.23, 1.24, 1.27, 1.28, 1.31-1.34, 1.39, 1.40, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55, 1.59, 1.67, 1.69, 1.73, 1.77-1.79, 2.1, 2.2 og 2.19-2.21 10 en pollenreduktion på ca. 90% og i næsten fuldstændig sterilitet (95-100%) af pollen sammenlignet med ubehandlede kontrolplanter, hvor pollen er fuldstændigt udviklet og befrugtningsdygtigt. Hos de behandlede planter konstateres ingen kendelig påvirkning af hunblomsterdelene ved befrugt-15 ningen med ubehandlet fremmedpollen (95-100% frugtdannelse), dog udvikles til dels parthenocarpe frugter.In the above experiment, compounds Nos. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.17, 1.20, 1.23, 1.24, 1.27, 1.28, 1.31-1.34, 1.39, 1.40, 1.41, 1.43, 1.44, 1.49, 1.52, 1.55 , 1.59, 1.67, 1.69, 1.73, 1.77-1.79, 2.1, 2.2 and 2.19-2.21 10 a pollen reduction of approx. 90% and in almost complete sterility (95-100%) of pollen compared to untreated control plants, where pollen is fully developed and fertile. In the treated plants, no appreciable effect on the female flower parts is found in fertilization with untreated foreign pollen (95-100% fruit formation), however, some parthenocarp fruits are developed.

Eksempel 18; Virkning mod Cercospora arachidicola på jordnødplanter a) Residual-protektiv virkning 20 10-15 cm høje jordnødplanter sprøjtes med en sprøjtevæske (0,02% virksom forbindelse) fremstillet ud fra et sprøjtepulver indeholdende den virksomme forbindelse, og 48 timer senere inficeres planterne med en konidiesuspension af svampen. De inficerede planter inkuberes i 72 timer ved ca.Example 18; Effect against Cercospora arachidicola on peanut plants a) Residual protective effect 20 10-15 cm tall peanut plants are sprayed with a spray liquid (0.02% effective compound) prepared from a spray powder containing the active compound and 48 hours later the plants are infected with a conidial suspension. of the fungus. The infected plants are incubated for 72 hours at ca.

25 21°C og høj luftfugtighed, hvorefter de henstilles i et væksthus, indtil der indtræder typiske bladpletter. Bedømmelsen af den fungicide virkning foretages 12 dage efter infektionen og er bseret på antallet og størrelsen af de optrædende pletter.25 21 ° C and high humidity, after which they are recommended in a greenhouse until typical leaf spots occur. The fungicidal effect is assessed 12 days after infection and is based on the number and size of the spots that appear.

30 b) Systemisk virkningB) Systemic effect

Til 10-15 cm høje jordnødplanter hældes en sprøjtevæske (0,006% virksom forbindelse, beregnet på jordrumfanget), fremstillet af et sprøjtepulver indeholdende den virksomme forbindelse. Efter 48 timers forløb inficeres de behand-To 10-15 cm tall peanut plants, pour a spray liquid (0.006% effective compound, calculated on the soil volume), made from a spray powder containing the active compound. After 48 hours, they are infected

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36 lede planter med en konidiesuspension af svampen, og der inkuberes i 72 timer ved ca. 21°C og høj luftfugtighed.36 lead plants with a conidial suspension of the fungus and incubate for 72 hours at approx. 21 ° C and high humidity.

Derefter henstilles planterne i et væksthus, og efter 11 dages forløb bedømmes svampeangrebet.The plants are then placed in a greenhouse and after 11 days the fungal attack is assessed.

5 I sammenligning med ubehandlede, men inficerede kontrolplanter (antal og størrelse af pletter = 100%), udviser jordnødplanter, som er blevet behandlet med virksomme forbindelser fra tabellerne 1 og 2, et kraftigt formindsket cercosporeangreb. Således forhindrer forbindelserne nr.Compared to untreated but infected control plants (number and size of spots = 100%), peanut plants, which have been treated with active compounds from Tables 1 and 2, exhibit a markedly reduced cercospore attack. Thus, compounds no.

10 1.1, 1.2, 1.24, 1.31, 1.35, 1.43, 1.79, 1.80, 2.1 og 2.2 næsten fuldstændigt (0-10%) optræden af pletter i ovenstående forsøg.10 1.1, 1.2, 1.24, 1.31, 1.35, 1.43, 1.79, 1.80, 2.1 and 2.2 almost completely (0-10%) the appearance of blemishes in the above experiments.

Eksempel 19: Virkning mod Puccinia graminis på hvede a) Residual-protektiv virkning 15 Hvedeplanter sprøjtes 6 dage efter udsåningen med en sprøjtevæske (0,06% virksom forbindelse), fremstillet ud fra et sprøjtepulver indeholdende den virksomme forbindelse. Efter 24 timers forløb inficeres de behandlede planter med en uredosporesuspension af svampen. Efter en inkubationstid 20 på 48 timer ved en relativ luftfugtighed på 95-100% og temperatur på ca. 20°C anbringes de inficerede planter i et væksthus ved ca 22°C. Bedømmelsen af rustpusteludviklin-gen foretages 12 dage efter inficeringen.Example 19: Effect against Puccinia graminis on wheat a) Residual protective effect 15 Wheat plants are sprayed 6 days after sowing with a spray liquid (0.06% effective compound), prepared from a spray powder containing the active compound. After 24 hours, the treated plants are infected with an uredospores suspension of the fungus. After an incubation time 20 of 48 hours at a relative humidity of 95-100% and temperature of approx. At 20 ° C, the infected plants are placed in a greenhouse at about 22 ° C. The evaluation of the rust pustule development is done 12 days after infection.

b) Systemisk virkning 25 Til hvedeplanter hældes 5 dage efter udsåningen en sprøjtevæske (0,06% virksom forbindelse, beregnet på jordrumfanget) , fremstillet ud fra et sprøjtepulver indeholdende den virksomme forbindelse. Efter 48 timers forløb inficeres de behandlede planter med en uredosporesuspension af svampen.b) Systemic effect 25 For wheat plants, a spray liquid (0.06% effective compound, based on soil volume), made from a spray powder containing the active compound, is poured 5 days after sowing. After 48 hours, the treated plants are infected with an uredospores suspension of the fungus.

30 Efter en inkubationstid på 48 timer ved en relativ luftfugtighed på 95-100% og ca. 20°C henstilles de inficerede planter i væksthus ved ca. 22°C. Bedømmelsen af rustpustel-udviklingen foretages 12 dage efter inficeringen.After an incubation period of 48 hours at a relative humidity of 95-100% and approx. At 20 ° C, the infected plants in greenhouses are recommended at approx. 22 ° C. Assessment of rust pustule development is made 12 days after infection.

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Forbindelserne med formlen I har en god virkning mod puccinia-svampe. Ubehandlede, men inficerede kontrolplanter udviser en et pucciniaangreb på 100%. Blandt andre hæmmer forbindelserne nr. 1.33, 1.34, 1.35, 1.78, 1.79 og 1.80 5 svampeangrebet til 0-5%.The compounds of formula I have a good effect against puccinia fungi. Untreated but infected control plants exhibit a puccinia attack of 100%. Among others, Compounds Nos. 1.33, 1.34, 1.35, 1.78, 1.79, and 1.80 inhibit the fungal attack to 0-5%.

Eksempel 20; Virkning mod Erysiphe graminis på byg a) Residual-protektiv virkningExample 20; Effect against Erysiphe graminis on barley a) Residual-protective effect

Ca. 8 cm høje bygplanter sprøjtes med en sprøjtevæske (0,02% virksom forbindelse), fremstillet ud fra et sprøj-10 tepulver indeholdende den virksomme forbindelse. Efter 3-4 timers forløb bestøves de behandlede planter med konidier af svampen. De inficerede bygplanter henstilles i et væksthus ved ca. 22°C, og svampeangrebet bedømmes efter 10 dages forløb.Ca. 8 cm tall barley plants are sprayed with a spray liquid (0.02% effective compound), made from a spray powder containing the active compound. After 3-4 hours, the treated plants are pollinated with conidia of the fungus. The infected barley plants are recommended in a greenhouse at approx. 22 ° C and the fungal attack is evaluated after 10 days.

15 b) Systemisk virkning15 b) Systemic effect

Til ca. 8 cm høje bygplanter hældes en sprøjtevæske (0,006% virksom forbindelse, beregnet på jordrumfanget), fremstillet ud fra et sprøjtepulver indeholdende den virksomme forbindelse. Der drages omsorg for, at sprøjtevæsken ikke 20 kommer i berøring med plantens overjordiske dele. Efter 48 timers forløb bestøves de behandlede planter med konidier af svampen. De inficerede bygplanter henstilles i et væksthus ved ca. 22°C, og svampeangrebet bedømmes efter 10 dages forløb.For approx. 8 cm tall barley plants are poured into a spray liquid (0.006% effective compound, calculated on soil volume), made from a spray powder containing the active compound. Care shall be taken to ensure that the spray liquid does not come into contact with the plant's aboveground parts. After 48 hours, the treated plants are pollinated with conidia of the fungus. The infected barley plants are recommended in a greenhouse at approx. 22 ° C and the fungal attack is evaluated after 10 days.

25 Forbindelser med formlen I udviser en god virkning mod erysiphesvampe. Ubehandlede, men inficerede kontrolplanter udviser et erysipheangreb på 100%. Blandt andre hæmmer forbindelserne nr. 1.1, 1.2, 1.24, 1.33, 1.34, 1.78, 1.79 og 1.80 svampeangrebet hos byg til mindre end 10%.Compounds of formula I exhibit a good effect against erysiphesis fungi. Untreated but infected control plants show a 100% erysiphane attack. Among others, compounds Nos. 1.1, 1.2, 1.24, 1.33, 1.34, 1.78, 1.79 and 1.80 inhibit fungal attack in barley to less than 10%.

30 Eksempel 21; Virkning mod Xanthomonas oryzae på ris a) Residual-protektiv virkningExample 21; Effect against Xanthomonas oryzae on rice a) Residual protective effect

Risplanter af sorten "Caloro" eller "S6" sprøjtes efter 3Rice plants of the "Caloro" or "S6" variety are sprayed after 3

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38 ugers dyrkning i et væksthus med forsøgsforbindelsen i form af en sprøjtevæske (0,06% virksom forbindelse). Efter 1 dags tørring af sprøjtevæsken anbringes planterne i et klimarum ved en temperatur på 24°C og en relativ luft-5 fugtighed på 75-85%, hvorefter de inficeres. Inficeringen foretages på den måde, at bladspidserne afklippes med en saks, der forinden er blevet neddyppet i en suspension af Xanthomonas oryzae. Efter 10 dages inkubation i samme rum visner de klippede blade, ruller sig sammen og bliver 10 nekrotiske. Omfanget af dette sygdomssymptom tjener til bedømmelse af forsøgsforbindelsens residualvirkning.38 weeks of cultivation in a greenhouse with the test compound in the form of a spray liquid (0.06% effective compound). After 1 day of drying the spray liquid, the plants are placed in a climate room at a temperature of 24 ° C and a relative humidity of 75-85% and then infected. The infestation is done by cutting the tips of the leaves with scissors that have been previously immersed in a suspension of Xanthomonas oryzae. After 10 days of incubation in the same room, the cut leaves fade, roll together and become 10 necrotic. The extent of this disease symptom serves to assess the residual effect of the test compound.

b) Systemisk virkningb) Systemic effect

Til risplanter af sorten "Caloro" eller "S6" hældes efter 6 ugers dyrkning i et væksthus en suspension af forsøgs-15 forbindelsen (0,006% virksom forbindelse, beregnet på jordrumfanget). 3 dage efter denne behandling henstilles planterne i et klimarum ved 24°C og en relativ luftfugtighed på 75-85%, hvorefter de inficeres. Inficeringen foretages på den måde, at bladspidserne afklippes med en saks, 20 som forinden er blevet neddyppet i en suspension afFor rice plants of the "Caloro" or "S6" variety, after 6 weeks of cultivation in a greenhouse, a suspension of the test compound (0.006% effective compound, based on soil volume) is poured. Three days after this treatment, the plants are left in a climate room at 24 ° C and a relative humidity of 75-85% and then infected. The infecting is done by cutting the blade tips with scissors 20 which have been previously immersed in a suspension of

Xanthomonas oryzae. Efter 10 dages inkubation i samme rum visner de klippede blade, ruller sig sammen og bliver nekrotiske. Omfanget af dette sygdomssymptom tjener til bedømmelse af forsøgsforbindelsens systemiske virkning.Xanthomonas oryzae. After 10 days of incubation in the same room, the cut leaves fade, roll together and become necrotic. The extent of this disease symptom serves to assess the systemic efficacy of the test compound.

25 Forbindelser fra tabel 1 og 2 udviser en god virkning mod xanthomonasbakterier. Således hæmmer ved residual-protek-tiv behandling af ris blandt andre forbindelserne nr. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.14, 1.19, 1.20, 1.23, 1.24, 1.28, 1.31, 1.32, 1.34, 1.35, 1.39, 1.41, 1.43, 1.44, 1.49, 30 1.52, 1.59, 1.69, 1.73, 1.77, 2.1 og 2.2 næsten fuldstæn digt (0-5%) forekomsten af nekrotiske pletter. Desuden udviser forbindelserne nr. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.19, 1.20, 1.23, 1.24, 1.28, 1.31, 1.32, 1.34, 1.39, 1.41, 1.43, 1.49, 1.52, 1.59, 1.69, 1.73, 2.1 og 2.2 også ved 35 systemisk virkning en fuldstændig virkning (0-5% nekrose).Compounds from Tables 1 and 2 show a good effect against xanthomonas bacteria. Thus, by residual protective treatment of rice, among other compounds Nos. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.14, 1.19, 1.20, 1.23, 1.24, 1.28, 1.31, 1.32, 1.34, 1.35, 1.39, 1.41, 1.43, 1.44, 1.49, 30 1.52, 1.59, 1.69, 1.73, 1.77, 2.1 and 2.2 almost completely (0-5%) the occurrence of necrotic spots. In addition, Compounds Nos. 1.1, 1.2, 1.5, 1.9, 1.10, 1.11, 1.19, 1.20, 1.23, 1.24, 1.28, 1.31, 1.32, 1.34, 1.39, 1.41, 1.43, 1.49, 1.52, 1.59, 1.69, 1.73, 2.1 and 2.2 also at complete systemic effect (0-5% necrosis).

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Ubehandlede, men inficerede risplanter (kontrolplanter) udviser en nekrose på 100%.Untreated but infected rice plants (control plants) exhibit 100% necrosis.

Eksempel 22: Virkning mod Xanthomonas vesicatoria på paprika a) Residual-protektiv virkning 5 Paprikaplanter af sorten "California Wonder" sprøjtes efter 3 ugers dyrkning i et væksthus med forsøgforbindelsen i form af en sprøjtevæske (0,06% virksom forbindelse). Efter 1 dags tørring af sprøjtevæsken anbringes planterne i et klimarum ved 26°C og en relativ luftfugtighed på 95-100%, 10 og de inficeres ved sprøjtning af bladundersiderne med en standardiseret suspension af Xanthomonas vesicatoria. Efter 6 dages inkubering i samme rum dannes der runde, i begyndelsen vandholdige, senere nekrotiske, lyse pletter på bladene. Omfanget af disse pletter tjener til bedømmelse af 15 forsøgsforbindelsens residualvirkning.Example 22: Effect against Xanthomonas vesicatoria on paprika a) Residual protective effect 5 Paprika plants of the "California Wonder" variety are sprayed after 3 weeks of cultivation in a greenhouse with the test compound in the form of a spray liquid (0.06% active compound). After 1 day of drying the spray liquid, the plants are placed in a climate room at 26 ° C and a relative humidity of 95-100%, 10 and they are infected by spraying the leaf undersides with a standardized suspension of Xanthomonas vesicatoria. After 6 days of incubation in the same compartment, round, initially aqueous, later necrotic, bright spots are formed on the leaves. The extent of these spots serves to assess the residual effect of the test compound.

b) Systemisk virkningb) Systemic effect

Til paprikaplanter af sorten "California Wonder" hældes efter 3 ugers dyrkning i væksthus en suspension af forsøgsforbindelsen (0,006% virksom forbindelse, beregnet på 20 jordrumfanget). 3 dage efter behandlingen henstilles planterne i et klimarum ved 26°C og en relativ luftfugtighed på 95-100%, og de inficeres ved sprøjtning af blandundersiderne med en standardiseret suspension af Xanthomonas vesicatoria. Efter 6 dages inkubation i samme rum dannes 25 runde, i begyndelsen vandholdige, senere nekrotiske, lyse pletter på bladene. Udstrækningen af disse pletter tjener til bedømmelse af forsøgsforbindelsens systemiske virkning. Forbindelser fra de to tabeller forhindrer næsten fuldstændigt forekomsten af pletter.For paprika plants of the "California Wonder" variety, after 3 weeks of cultivation in the greenhouse, a suspension of the test compound (0.006% effective compound, calculated on the 20 soil volume) is poured. Three days after treatment, the plants are left in a climate room at 26 ° C and a relative humidity of 95-100% and infested by spraying the blend subspaces with a standardized suspension of Xanthomonas vesicatoria. After 6 days of incubation in the same compartment, 25 round, initially aqueous, later necrotic, bright spots are formed on the leaves. The extent of these spots serves to assess the systemic effect of the test compound. Compounds from the two tables almost completely prevent the appearance of stains.

Claims (9)

1. Middel med gametocid virkning og med stimulerende virkning på blomsterdannelsen, kendetegnet ved, at de.t sammen med et eller flere gængse bære- eller fortyn- 5 dingsstoffer som mindst én virksom komponent indeholder et nitroaryl-alkylsulfonderivat med formlen °2N R40-<t>S02Rl (I) hvori R^ betyder C^-C^-alkyl, betyder hydrogen, en hydrazinium- eller ammoniumion eller gruppen -COR,., hvor 10 R^ betyder C^-C-^-alkyl, C^-C^-alkoxy, C^-C^-halogenalkoxy, C2~Cio-alkenyl, C2-C3-halogenalkenyl, C3-Cg-cycloalkyl, phenyl, furyl, tetrahydrofuryl, nitrophenyl eller halogen-phenyl.An agent with gametocide action and stimulating effect on the flower formation, characterized in that it, together with one or more common carriers or diluents, contains at least one active component a nitroaryl-alkylsulfone derivative of the formula ° 2N R40- t> SO 2 R 1 (I) wherein R 1 represents C 1 -C 4 alkyl, hydrogen, a hydrazinium or ammonium ion or the group -COR 1, wherein R 1 represents C 1 -C 2 -alkyl, C 1 - C ^-alkoxy, C ^-C ^-haloalkoxy, C₂-Cio alkenyl, C₂-C3 halogenalkenyl, C3-Cg cycloalkyl, phenyl, furyl, tetrahydrofuryl, nitrophenyl or halogen-phenyl. 2. Middel ifølge krav 1, kendetegnet ved, 15 at det som aktiv komponent indeholder mindst én forbindelse valgt blandt 4-hydroxy-3-nitrophenyl-methylsulfon, 4-[3-chlor-n-propylcarbonyloxy]-2-nitrophenyl-methylsulfon, 4-hydroxy-3-nitrophenyl-methylsulfon-tetra(n-butyl)ammonium-20 salt, 4-acetyloxy-3-nitrophenyl-methylsulfon, 4-cyclopropylcarbonyl-3-nitrophenyl-methylsulfon, 4-hydroxy-3-nitrophenyl-ethyIsulfon, 4-acryloxy-3-nitrophenyl-methylsulfon, 25 4-trichloracryloxy-3-nitrophenyl-methylsulfon, 4-n-propylcarbonyloxy-3-nitrophenyl-methylsulfon, 4-ethylcarbonyloxy-3-nitrophenyl-methylsulfon, 4-phenylcarbonyloxy-3-nitrophenyl-methylsulfon, 4-methoxymethylcarbonyloxy-3-nitrophenyl-methy1sulfon, 30 4-cyclohexylcarbonyloxy-3-nitrophenyl-methylsulfon, 4-chlormethylcarbonyloxy-3-nitrophenyl-methylsulfon og 4-methoxycarbonyloxy-3-nitrophenyl-methylsulfon. DK 159093 BAn agent according to claim 1, characterized in that it contains as active component at least one compound selected from 4-hydroxy-3-nitrophenyl-methylsulfone, 4- [3-chloro-n-propylcarbonyloxy] -2-nitrophenyl-methylsulfone, 4-hydroxy-3-nitrophenyl-methylsulfone-tetra (n-butyl) ammonium salt, 4-acetyloxy-3-nitrophenyl-methylsulfone, 4-cyclopropylcarbonyl-3-nitrophenyl-methylsulfone, 4-hydroxy-3-nitrophenyl-ethylsulfone , 4-acryloxy-3-nitrophenyl-methylsulfone, 4-trichloroacryloxy-3-nitrophenyl-methylsulfone, 4-n-propylcarbonyloxy-3-nitrophenyl-methylsulfone, 4-ethylcarbonyloxy-3-nitrophenyl-methylsulfone, 4-phenylcarbonyloxy nitrophenylmethylsulfone, 4-methoxymethylcarbonyloxy-3-nitrophenylmethylsulfone, 4-cyclohexylcarbonyloxy-3-nitrophenylmethylsulfone, 4-chloromethylcarbonyloxy-3-nitrophenylmethylsulfone and 4-methoxycarbonyloxy-3-nitoxenyl DK 159093 B 3. Fremgangsmåde til stimulering af blomsterdannelsen hos planter, kendetegnet ved, at planterne, plantedelene, deres frø eller deres voksested behandles med en forbindelse med formlen I ifølge krav 1-2. 5A method of stimulating flower formation in plants, characterized in that the plants, plant parts, their seeds or their growing site are treated with a compound of formula I according to claims 1-2. 5 4- Fremgangsmåde ifølge krav 3, kendetegnet ved, at man behandler kulturplanter.Method according to claim 3, characterized in that cultivated crop plants are treated. 5·· Fremgangsmåde ifølge krav 4, kendetegnet ved, at man behandler småkornede halmfrugtplanter, kornplanter eller fodergræsser.Process according to claim 4, characterized in that the processing of small grain straw fruit plants, cereal plants or fodder grasses is treated. 6. Fremgangsmåde ifølge krav 3-5, kendeteg net ved, at man anvender de aktive forbindelser med formlen I i en mængde på 0,05-12 kg virksom forbindelse pr. ha.Process according to claims 3-5, characterized in that the active compounds of formula I are used in an amount of 0.05-12 kg of active compound per day. ha. 7. Fremgangsmåde til udvinding af hybridfrø, k e n -15 detegnet ved, at en som hunforældreplante udvalgt stamplante underkastes hankønsterilisation ved begyndelsen af blomsterdannelsen, men inden dannelsen af hanblomsterdele ved applikation af en forbindelse med formlen I ifølge krav 1 og fremmedbestøves med pollen 20 fra en udvalgt genetisk-lignende plante, og de modne hybridfrø høstes.7. A method of extracting hybrid seeds, characterized in that a stem plant selected as a female parent plant is subjected to male sterilization at the beginning of flowering, but prior to the formation of male flower parts by application of a compound of formula I according to claim 1 and foreign pollinated with pollen 20 from a selected genetic-like plant and the mature hybrid seeds are harvested. 8. Fremgangsmåde ifølge krav 7, kendetegnet ved, at den virksomme forbindelse anvendes i en mængde på 0,05-12 kg virksom forbindelse pr. ha på hunforældreplan- 25 terne eller deres voksested.Process according to claim 7, characterized in that the active compound is used in an amount of 0.05-12 kg of active compound per day. ha on the female parent plants or their growing place. 9. Anvendelse af nitroaryl-alkylsulfonderivater med formlen 02n r4°_<>—(I) DK 159093 B hvori betyder C^-Cg-alkyl, betyder hydrogen, en hydr-azinium- eller ammoniumion eller gruppen -CORg, hvor Rg betyder .C^-C12-alkyl, C^-Cg-alkoxy, C^-Cg-halogenalkyloxy, C2-Cio“alkenyl, C2-Cg-halogenalkenyl, Cg-Cg-cycloalkyl, 5 phenyl, furyl, tetrahydrofuryl, nitrophenyl eller halogen-phenyl i midlet ifølge krav 1.Use of nitroaryl-alkylsulfone derivatives of the formula 02n r4 ° <<- (I) DK 159093 B wherein C 1 -C 8 -alkyl means hydrogen, a hydrazinium or ammonium ion or the group -CORg where Rg means. C ^-C12 alkyl, C ^-Cg alkoxy, C ^-Cg halogenalkyloxy, C₂-Cio “alkenyl, C₂-Cg halogenalkenyl, Cg-Cg cycloalkyl, phenyl, furyl, tetrahydrofuryl, nitrophenyl or halogeno phenyl in the agent of claim 1.