SK86783A3 - Herbicidal agent and method of production of effective matters - Google Patents
Herbicidal agent and method of production of effective matters Download PDFInfo
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Description
Herbicídny prostriedok, ktorý ako účinnú látku obsahuje zlúčeninu všeobecného vzorca I, v ktorom R' a R znamenajú nezávisle od seba alkylovú skupinu s 1 až 4 atómami uhlíka alebo alkoxyskupinu s 1 až 4 atómami uhlíka a Y znamená skupinu vzorca A-OR, kde A predstavuje skupinu vzorca CH2, CH2-CH2 alebo CH(CH3)CH2 a R znamená alkylovú skupinu s 1 až 3 atómami uhlíka, v kombinácii s herbicidne použiteľným riedidlom. Účinná látka sa získa N-acyláciou zlúčeniny všeobecného vzorca Π, v ktorom R', R a Y majú vyššie uvedený význam, pôsobením chlóracetylchloridu. Ďalej sa nárokujú zvlášť výhodné acetamidy.A herbicidal composition comprising, as an active ingredient, a compound of formula (I) wherein R 'and R' are independently C 1 -C 4 alkyl or C 1 -C 4 alkoxy and Y is A-OR, wherein A represents a group of the formula CH 2, CH 2 -CH 2 or CH (CH 3) CH 2 and R represents an alkyl group having 1 to 3 carbon atoms, in combination with a herbicidal diluent. The active ingredient is obtained by N-acylation of a compound of formula Π in which R ', R and Y are as defined above with chloroacetyl chloride. Furthermore, particularly preferred acetamides are claimed.
/ŕ m -93/ m -93
- 1 Herbicídny prostriedok a spôsob výroby účinných látokHerbicidal composition and process for the manufacture of active substances
Oblasť technikyTechnical field
Vynález popisuje nové päťčlenné heteroaromatické zlúčeniny, ktoé nesú na jednom uhlíkovom atóme kruhu N-substituovanú chlóracetylaminoskupinu, ich použitie ako herbicídov, poľnohospodárske prostriedky, ktoré uľahčujú použitie týchto látok a spôsoby výroby týchto nových zlúčenín podľa vynálezu.The invention discloses novel five-membered heteroaromatic compounds bearing an N-substituted chloroacetylamino group on one carbon atom of the ring, their use as herbicides, agricultural compositions which facilitate the use of these compounds, and methods of making the novel compounds of the invention.
Doterajší stav technikyBACKGROUND OF THE INVENTION
Sú známe rozličné herbicídne účinné N-substituované α-halogénacetanilidy.Various herbicidally active N-substituted α-haloacetanilides are known.
V americkom patentovom spise č. 4 282 028 sú popísanéU.S. Pat. No. 4,282,028 are described
N-substituované N-(2,5-dialkylpyrol-l-ylJhalogénacetamidy, ktoré vykazujú herbicídnu účinnosť a účinnosť regulátorov rastu rastlín.N-substituted N- (2,5-dialkylpyrrol-1-yl) haloacetamides, which exhibit herbicidal and plant growth regulator activity.
Nové päťčlenné heteroaromatické zlúčeniny sú predovšetkým účinnými herbicídmi s primerane dlhou dobou zotrvania v pôde.In particular, the novel five-membered heteroaromatic compounds are effective herbicides with a reasonably long residence time in the soil.
Podstata vynálezuSUMMARY OF THE INVENTION
Vynález popisuje zlúčeniny všeobecného vzorca IThe present invention provides compounds of formula I
CO-CH,. 01CO-CH ,. 01
v ktoromin which
R' a R'» znamenajú nezávisle od seba alkylovú skupinu s 1 až 4 atómami uhlíka alebo alkoxyskupinu s 1 až 4 atómami uhlíka aR 'and R' 'are each independently C 1 -C 4 alkyl or C 1 -C 4 alkoxy and
Y znamená skupinu vzorca A-OR, kde A predstavuje skupinu vzorca CH2, CH2-CH2 ch(ch3)-ch2 aY is A-OR, wherein A is CH 2 , CH 2 -CH 2 ch (ch 3 ) -ch 2, and
R znamená alkylovú skupinu s 1 až 3 atómami uhlíka.R represents an alkyl group having 1 to 3 carbon atoms.
Predovšetkým výhodné sú zlúčeniny všeobecného vzorca I, v ktorom R' a R'' znamenajú metylové skupiny a Y predstavuje skupinu A-OR, ktorá predstavuje skupinu vzorca CH(CH3)CH2OCH3.Particularly preferred are compounds of formula I wherein R 'and R''are methyl and Y is A-OR which is CH (CH 3 ) CH 2 OCH 3 .
Predmetom vynálezu sú predovšetkým výhodné zlúčeniny všeobecného vzorca I a to 2-chlór-N-(2-metoxyetyl)-N-(2,4-dimetyl) acetamid, 2-chlór-N- [ (l-metyl-2-metoxy)etyl ] -N- (2,4-di-metyl-^J-y^/jyz^.) acetamid a 2-chlór-N- (2-etoxyetyl) -N- (4-metoxy-2-mety l’tJ ) acetamid.More particularly preferred compounds of formula I are 2-chloro-N- (2-methoxyethyl) -N- (2,4-dimethyl) acetamide, 2-chloro-N- [(1-methyl-2-methoxy)] ethyl] -N- (2,4-dimethyl-4-methyl-acetyl) acetamide and 2-chloro-N- (2-ethoxyethyl) -N- (4-methoxy-2-methyl) acetamide.
Predmetom tohoto vynálezu je taktiež spôsob výroby zlúčenín vyššie uvedeného všeobecného vzorca I, ktorý spočíva v tom, že sa zlúčenina všeobecného vzorca IIThe present invention also relates to a process for the preparation of the compounds of formula (I) as described above, which comprises:
(II), v ktorom(II) in which:
R', R'' a Y majú význam uvedený vyššieR ', R' 'and Y are as defined above
N-acyluje pôsobením chlóracetylchloridu.N-acylated with chloroacetyl chloride.
Táto reakcia sa s výhodou uskutočňuje v prítomnosti kyselinu viažúceho činidla, ako uhličitanu draselného.This reaction is preferably carried out in the presence of an acid binding agent such as potassium carbonate.
Zlúčeniny všeobecného vzorca I sa môžu izolovať z reakčnej zmesi, v ktorej vznikli, spracovaním tejto zmesi zvyčajnými postupmi .The compounds of formula (I) may be isolated from the reaction mixture in which they are formed by treating the mixture with conventional methods.
Vzájomnú premenu jednej zlúčeniny podľa vynálezu na zlúčeninu inú je možné taktiež uskutočňovať zvyčajným spôsobom. Ďalej je zrejmé, že zlúčeniny podľa vynálezu môžu obsahovať jedno alebo niekoľko centier asymetrie a môžu teda existovať vo forme opticky aktívnych izomérov, diastereomérov, racemátov alebo geometrických izomérov. V herbicídnych prostriedkoch podľa vynálezu sa tieto zlúčeniny vo všeobecnosti používajú ako zmesi týchto foriem, i keď je možné tieto zmesi známymi postupmi deliť.Conversion of one compound of the invention to another can also be accomplished in the usual manner. It is further understood that the compounds of the invention may contain one or more centers of asymmetry and may therefore exist in the form of optically active isomers, diastereomers, racemates or geometric isomers. In the herbicidal compositions of the invention, these compounds are generally used as mixtures of these forms, although they can be separated by known methods.
Zlúčeniny všeobecného vzorca II spadajú do rozsahu tohoto vynálezu.The compounds of formula II are within the scope of this invention.
Zlúčeniny všeobecného vzorca II je možné získať N-alkyláciou 3-aminotiofénu. Táto alkylácia sa môže uskutočňovať zvyčajným spôsobom za použitia zodpovedajúcich alkylačných činidiel (napríklad halogenidov) alebo tam, kde je to vhodné, redukciou cez Schiffovu bázu alebo amid.The compounds of formula II can be obtained by N-alkylation of 3-aminothiophene. This alkylation may be carried out in a conventional manner using the corresponding alkylating agents (e.g. halides) or, where appropriate, reduction by Schiff base or amide.
Početné zlúčeniny všeobecného vzorca II sú nové.Numerous compounds of formula II are novel.
Východiskové zlúčeniny sa dajú získať redukciou zodpovedajúcich nitrozlúčenín, napríklad katalytickou hydrogenáciouVZätíaku v prítomnosti paládia. 3-Aminotiofény, ktoré nesú metylovú skupinu v polohe 2 alebo 4, je možné získať redukciou zodpoveda júceho tioféirj^arboxylátu komplexným hydridom, ako je nátrium-bis(metoxyetyloxy)alumíniumhydrid. Východiskovú zlúčeninu je možné taktiež získať zo zodpovedajúcich estérov karbámovej kyse liny, napríklad z benzy^Jcarbamátu, hydrolýzou. Karbamáty, používané ako východiskové materiály, je možné získať napríklad z príslušných kyselín cez azidy kyselín Curtiovou reakciou.The starting compounds can be obtained by reduction of the corresponding nitro compounds, for example by catalytic hydrogenation of the catalyst in the presence of palladium. 3-Aminothiophenes which carry a methyl group at the 2 or 4 position can be obtained by reduction of the corresponding thiophene-4-carboxylate with a complex hydride such as sodium bis (methoxyethyloxy) aluminum hydride. The starting compound can also be obtained from the corresponding carbamic acid esters, for example benzylcarbamate, by hydrolysis. The carbamates used as starting materials can be obtained, for example, from the corresponding acids via the Curtiic acid azides by reaction.
Pokiaľ nie je v tomto texte popísaná príprava niektorých východiskových látok, sú tieto zlúčeniny známe alebo je možné ich pripraviť a vyčistiť známymi postupmi alebo spôsobom, ktorý je analogický tu popísaným alebo známym postupom.Unless the preparation of certain starting materials is described herein, these compounds are known or can be prepared and purified by known methods or in a manner analogous to those described or known herein.
Zlúčeniny po vynálezu sú užitočné, pretože potláčajú alebo modifikujú rast rastlín. Rastlinou sa v danom prípade rozumia klíčiace semená, vzídené klíčne rastliny a vyrastená vegetácia, vrátane podzemných častí.The compounds of the invention are useful because they inhibit or modify plant growth. A plant in this case means germinating seeds, emerging germinated plants and grown vegetation, including underground parts.
Predmetom tohoto vynálezu sú taktiež herbicídne prostriedky, ktoré ako účinnú látku obsahujú vyššie vymedzenú zlúčeninu všeobecného vzorca I.The present invention also relates to herbicidal compositions which contain, as active ingredient, a compound of the formula I as defined above.
Zlúčeniny všeobecného vzorca I sú predovšetkým Užitočné ako herbicídy, o čom svedčia okrem iného škody, ktoré pôsobia ako jednoklíčnym tak dvojklíčnym rastlinám, ako sú Lepidium sativum (žerucha), Avena sativä (ovos), Agrostis alba a Lolium perenne (mätonoh), pri testoch, keď sa aplikujú preemergentne alebo postemergentne v dávkach zodpovedajúcich 1,4 až 5,6 kg/ha. Vzhľadom ku svojej herbicídn^ účinnosti sú zlúčeniny podlá vynálezu určene na boj proti dvojklíčnyma trávnatým burinám, ako to potvrdzujú výsledky ďalších testov, pri ktorých boli reprezentatívne zlúčeniny testované v dávkach zodpovedajúcich 0,2 až 5,0 kg účinnej látky na hektár, napríklad v dávkach zodpovedajúcich 0,2,* 1,0 a 5,0 kg účinnej látky na hektár, proti dvojklíčnym burinám, ako sú Amarantus retroflexus (láskavec ohnutý), Capsella bursa pastoris (pastierska kapsička), Chenopodium laria média (hviezdica prostredná), obyčajný) a Gálium aparine (lipkavec alba (mrlík biely), StelSenecio vulgaris (starček obyčajný), a predovšetkým proti trávnatým burinám ako sú Agropyron repens (pýr plazivý), Agrostis alba, Alopecurus myosuroides (psiarka roľná), Apera spica-venti (metlička obyčajná), Avena fatua (ovos hluchý), Echinochloa crus-galli (ježatka kuria), Bromus tectorum (stoklas), Sorghum halepense (cirok halepský), Digitaria spp.(prstovka) a Setaria (bar). Ďalšie testy svedčia o priaznivom pretrvávaní zlúčenín podľa vynálezu v pôde.The compounds of formula (I) are particularly useful as herbicides, as evidenced, inter alia, by the damage caused to both monocotyledonous and dicotyledonous plants such as Lepidium sativum (cress), Avena sativä (oats), Agrostis alba and Lolium perenne when applied pre-emergence or post-emergence at doses corresponding to 1.4 to 5.6 kg / ha. Due to their herbicidal activity, the compounds according to the invention are intended to combat dicotyledonous weeds, as confirmed by the results of further tests in which representative compounds were tested at doses corresponding to 0.2 to 5.0 kg of active substance per hectare, e.g. corresponding to 0.2, * 1.0 and 5.0 kg of active substance per hectare, against dicotyledonous weeds such as Amarantus retroflexus, Capsella bursa pastoris (shepherd's pocket), Chenopodium laria medium (starfish), common) and Gallium aparine (Stag beetle), StelSenecio vulgaris (ragwort), and in particular against grass weeds such as Agropyron repens, Agrostis alba, Alopecurus myosuroides, Apera spica-venti , Avena fatua (Deaf oat), Echinochloa crus-galli, Bromus tectorum (Sorghum halepense) Digitaria spp (finger finger) and Setaria (bar) Further tests show favorable soil persistence of the compounds of the invention.
Zlúčeniny podľa vynálezu sú relatívne menej toxické pre úžitkové plodiny ako pre buriny. Selektívna herbicídna účinnosť bola okrem iného pozorovaná v kukurici, sóji, bavlníku, cukrovej repe, zemiakoch, lucerne, slnečnici, repke, podzemnici olejnej alebo ľane a to v závislosti okrem iného od príslušnej zlúčeniny a aplikovanej dávky. Zlúčeniny podľa vynálezu sa teda rovnako da jú používať ako selektívne herbicídy v úžitkových plodinách.The compounds of the invention are relatively less toxic to crops than weeds. Selective herbicidal activity has been observed, inter alia, in corn, soy, cotton, sugar beet, potatoes, lantern, sunflower, rape, groundnut or flax, depending inter alia on the compound in question and the dose applied. The compounds according to the invention can therefore also be used as selective herbicides in crops.
Vynález taktiež popisuje spôsob ničenia burín na určitom mieste, s výhodou v kultúre úžitkovej plodiny, predovšetkým v kultúre vyššie uvedenej úžitkovej plodiny, vyznačujúci sa tým, že sa na toto miesto aplikuje herbicídne účinné množstvo (selektívne herbicídne účinné množstvo v prípade aplikácie v kultúre úžitkovej rastliny) zlúčeniny podľa vynálezu. Predovšetkým výhodné uskutočnenie tohoto spôsobu spočíva v preemergentnej aplikácii (ako preO^vzídením úžitkových rastlím, tak burín) zlúčeniny všeobecného vzorca I pre selektívne ničenie buriny v kultúre úžitkovej rastliny.The invention also provides a method for controlling weeds at a particular site, preferably in a crop plant culture, in particular in the above crop, wherein a herbicidally effective amount (a selective herbicidally effective amount when applied in a crop plant culture) is applied to the site ) of a compound of the invention. A particularly preferred embodiment of this method consists in the pre-emergence application (both for emergence of crop plants and weeds) of a compound of formula I for selective weed control in a crop plant culture.
Pri použití zlúčenín podľa vynálezu a to jednak ako celkových, taJ\^iež ako selektívnych herbicídov sa množstvo aplikované pre dosiahnutie požadovaného účinku mení v závislosti od príslušnej úžitkovej rastliny v prípade selektívneho použitia a od iných štandardných premenných, ako sú použitá zlúčenina, spôsob aplikácie, podmienky ošetrovania a podobne. Vhodné aplikačné dávky odborník môže zistiť spôsobom bežným v odbore alebo porovnaním účinnosti zlúčenín podľa vynálezu s účinnosťou štandardných porovnávacích látok, pre ktoré sú aplikačné dávky známe, napríklad testy v skleníku. Vo všeobecnosti sa však dosahujú uspokojivé výsledky v prípade, že sa zlúčenina podľa vynálezu aplikuje v dávke pohybujúcej sa od asi 0,1 do 5 kg/ha, s výhodou od asi 0,2 do 4 kg/ha, najvýhodnejšie od 0,5 do 3,0 kg/ha, pričom aplikácia sa v prípade nutnosti opakuje. Pri použití v kultúre úžitkovej plodiny nemá aplikačná, dávka s výhodou prevýšiť 3 kg/ha.When using the compounds according to the invention, both as a whole and as selective herbicides, the amount applied to achieve the desired effect varies depending on the particular crop plant in the case of selective use and other standard variables such as the compound used, the method of application, treatment conditions and the like. Suitable dosages can be determined by one of ordinary skill in the art or by comparing the efficacy of the compounds of the invention with that of standard comparatives for which the dosages are known, for example in a greenhouse assay. In general, however, satisfactory results are obtained when the compound of the invention is applied at a dose ranging from about 0.1 to 5 kg / ha, preferably from about 0.2 to 4 kg / ha, most preferably from 0.5 to 5 kg / ha. 3.0 kg / ha, the application being repeated if necessary. When used in a crop crop, the application rate should preferably not exceed 3 kg / ha.
Zlúčeniny podľa všeobecného vzorca I sa môžu používať i a s výhodou sa taktiež používajú vo forme'herbicídnych prostriedkov v kombinácii s herbicídne prijateľnými riedidlami. Vhodné prostriedky obsahujú 0,01 až 99 % hmôt, účinnej látky, od 0 do 20 % vhodnej povrchovo aktívnej látky a 1 až 99,99 % pevného alebo kvapalného riedidla (riedidiel). V niektorých prípadoch sa požadujú vyššie dávky povrchovo aktívneho činidla v pomere k účinnej látke. Toto vyššie množstvo povrchovo aktívneho činidla sa môže pridať priamo k prostriedku alebo ho možno pridávať pri príprave aplikačného preparátu (tank-mix). Aplikačné formy pros triedkov podľa vynálezu vo všeobecnosti obsahujú 0,01 až 25 % hmôt, účinnej látky. Môžu byť pochopiteľne prítomné nižšie alebo vyššie množstvá účinnej látky, v závislosti od predpokladaného spôsobu použitia a od fyzikálnych vlastností látok. Koncentrované formy prostriedkov podľa vynálezu, určené preeZpoužitľzo na riedenie, vo všeobecnosti obsahujú medzi 2 a. 90 %, s výhodou medzi 10 a 80 % hmôt, účinnej látky.The compounds of the formula I can also be used and are preferably used in the form of herbicidal compositions in combination with herbicidally acceptable diluents. Suitable compositions contain from 0.01 to 99% by weight of active ingredient, from 0 to 20% of a suitable surfactant and from 1 to 99.99% of a solid or liquid diluent (s). In some cases, higher dosages of surfactant relative to the active agent are required. This higher amount of surfactant may be added directly to the composition or may be added in the preparation of a tank mix. The dosage forms according to the invention generally contain from 0.01 to 25% by weight of active ingredient. Obviously, lower or higher amounts of the active ingredient may be present, depending on the intended use and the physical properties of the ingredients. Concentrated forms of the compositions of the present invention intended for use as diluents generally contain between 2 and 5%. 90%, preferably between 10 and 80% by weight of active ingredient.
Medzi vhodné prostriedky s obsahom zlúčenín podľa vynálezu patria popraše, granuláty, pelety, suspenzné koncentráty, zmáčateľné prášky, emulgovateľné koncentráty a podobne. Tieto prostriedky sa získavajú zvyčajným spôsobom, napríklad miešaním zlúčenín podľa vynálezu s'riedidlami. Kvapalné prostriedky sa konkrétne pripravujú zmiešaním jednotlivých zložiek, jemné pevné prostriedky zmiešaním a rozdrvením . , suspenzie rozomieľaním za mokra a granule a pelety impregnáciou alebo poťahovaním vopred pripravených granulovaných nosičov účinnou látkou alebo aglomeračnými technikami.Suitable compositions containing the compounds of the invention include dusts, granules, pellets, suspension concentrates, wettable powders, emulsifiable concentrates and the like. These compositions are obtained in a conventional manner, for example by mixing the compounds of the invention with diluents. In particular, liquid compositions are prepared by mixing the individual components, fine solid compositions by mixing and crushing. suspensions by wet grinding and granules and pellets by impregnation or coating of preformed granular carriers with the active ingredient or agglomeration techniques.
Alternantívne sa môžu zlúčeniny podľa vynálezu používať v mikroenkapsulovanej forme.Alternatively, the compounds of the invention may be used in microencapsulated form.
Pri výrobe herbicídnych prostriedkov je možné na zlepšenie efektívnosti účinnej látky a na potlačenie penenia, spekania a korózie používať vhodné prísady.In the manufacture of herbicidal compositions, suitable additives may be used to improve the effectiveness of the active ingredient and to suppress foaming, sintering and corrosion.
Používaným výrazom povrchovo aktívne činidlo sa myslí vhodný materiál, ktorý zlepšuje emulgovatéľnosť alebo iné vlastnosti na rozhraní fáz. Ako príklady povrchovo aktívnych činidiel treba uviesť nátr^mJLignínsulfonáta^aurylsulfát.By the term surfactant is meant a suitable material that improves the emulsifiability or other phase interface properties. Examples of surfactants include sodium lignin sulphonate and auryl sulphate.
Riedtami sa mienia kvapalné alebo pevné materiály využiteľné v oblasti herbicídov, používané na riedenie koncentrovaného materiálu na použiteľnú alebo požadovanú koncentráciu. Pre výrobu popraší sa môžu ako riedidlá používať napríklad mastenec, kaolín alebo infuzóriová hlinka, pre výrobu kvapalných koncentrátov napríklad uhľovodíky ako xylén alebo alkoholy, ako izopropanol, a pre prípravu kvapalných aplikačných foriem okrem iného voda alebo motorová nafta.By dilutes is meant liquid or solid materials useful in the herbicide field, used to dilute the concentrated material to a usable or desired concentration. For the production of dusts, for example, talc, kaolin or diatomaceous earth may be used as diluents, for the production of liquid concentrates, for example, hydrocarbons such as xylene or alcohols such as isopropanol, and for the preparation of liquid dosage forms inter alia water or diesel fuel.
Prostriedky podľa vynálezu môžu taktiež obsahovať iné zlúčeniny, ktoré vykazujú biologickú účinnosť, napríklad zlúčeniny s obdobnou alebo komplementárnou herbicídnou účinnosťou alebo zlúčeniny, ktoré pôsobia ako protijedy, poprípade látky vykazujúce fungicídnu alebo insekticídnu účinnosť.The compositions of the invention may also contain other compounds which exhibit biological activity, for example compounds with similar or complementary herbicidal activity or compounds which act as antidotes or substances having fungicidal or insecticidal activity.
Príklady uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
V nasledujúcej časti sú uvedené príklady herbicidnych prostriedkov podľa vynálezu.The following are examples of herbicidal compositions of the present invention.
Príklad AExample A
Zmáčateľný prášok dielov zlúčeniny všeobecného vzorca I, napríklad nižšie uvedenej zlúčeniny č. 25, sajtmieša a rozomieľa s 25 dielmi jemného syntetického oxidu kremičitého, 2 dielmi nátriun^Laurylsulfátu, 3 dielmi nátriuinJLic^ínsulfátu a 45 dielmi jemne mletého kaolínu tak dlho, pokým stredná veľkosť častíc činí približne 5 μιη. Výsledný zmáčateľný prášok sa pred použitím riedi vodou na postrekový preparát o požadovanej koncentrácii.A wettable powder of parts of a compound of Formula I, e.g. 25, blends and comminutes with 25 parts fine synthetic silica, 2 parts lauryl sulfate, 3 parts sodium lauryl sulfate, and 45 parts finely divided kaolin as long as the mean particle size is approximately 5 µm. The resulting wettable powder is diluted with water before use to spray the desired concentration.
Príklad BExample B
Emulzný koncentrát dielov zlúčeniny všeobecného vzorca I, napríklad nižšie uvedenej zlúčeniny č. 25, 40 dielov xylénu, 30 dielov dimetylformamidu a 10 dielov emulgátora (napríklad Atlox 4851 B, čo je zmes alkyl^rylsulfonátu vápenatého a polyetoxylovaných triglyceridov) sa dôkladne mieša až do získania homogénneho roztoku. Výsledný emulzný koncentrát sa pred použitím riedi vodou.An emulsion concentrate of parts of a compound of formula I, for example compound no. 25, 40 parts of xylene, 30 parts of dimethylformamide, and 10 parts of an emulsifier (e.g., Atlox 4851 B, a mixture of calcium alkylsulfonate and polyethoxylated triglycerides) are thoroughly mixed until a homogeneous solution is obtained. The resulting emulsion concentrate is diluted with water before use.
Príklad CExample C
Granulát kg zlúčeniny všeobecného vzorca I, napríklad nižšie uvedenej zlúčeniny č. 25, sa rozpustí v 25 litroch metylénchloridu, roztok sa pridá k 95 kg granulovaného attapulgitu (veľkosť častíc 0,3 až 0,7 mm), zmes sa dôkladne premieša a rozpúšťadlo sa odparí za zníženého tlaku. Vynález je ilustrovaný nasledujúcimi príkladmi uskutočnenia, ktoré však v .žiadnom smere neobmedzujú rozsah vynálezu. Uvádzané hodnoty Rf sa získali chromatografiou na silikagéle.Granulate kg of a compound of formula I, e.g. 25 is dissolved in 25 liters of methylene chloride, the solution is added to 95 kg of granulated attapulgite (particle size 0.3-0.7 mm), mixed thoroughly and the solvent is evaporated under reduced pressure. The invention is illustrated by the following examples, which are not intended to limit the scope of the invention in any way. Rf values reported were obtained by silica gel chromatography.
Príklad 1Example 1
N- (4-Metoxy-2-metylt5r//6/i/4>l )-N- (2-etoxyetyl )chlóracetamid (/N- (4-methoxy-2-metylt5r // 6 / i / 4>) -N- (2-ethoxyethyl) chloroacetamide (/
K intenzívne miešanej zmesi 6,05 g (0,03 mol) N-(2-etoxyetyl)-4-metoxy-2-metyltiofén-3-amínu, 4,15 g (0,03 mol) uhličitanu draselného, 10 ml vody a 100 ml dichlórmetánu sa bez chladenia prikvapká roztok 3,4 g (0,03 mol) chlóracetylchloridu v 10 ml dichlórmetánu. Po doznení exotermickej reakcie (27* C) sa v miešaní pokračuje pri laboratórnej teplote ešte ďalšiu hodinu.To a vigorously stirred mixture of 6.05 g (0.03 mol) of N- (2-ethoxyethyl) -4-methoxy-2-methylthiophen-3-amine, 4.15 g (0.03 mol) of potassium carbonate, 10 ml of water and 100 ml of dichloromethane was added dropwise without cooling a solution of 3.4 g (0.03 mol) of chloroacetyl chloride in 10 ml of dichloromethane. After the exothermic reaction (27 ° C) had passed, stirring was continued at room temperature for an additional hour.
Metylénchloridová vrstva sa oddelí, premyje sa dvakrát vždy s 100 ml vody, vysuší sa síranom sodným a odparí za vákua. Zvyšná zlúčenina uvedená v názve je analyticky čistá.The methylene chloride layer was separated, washed twice with 100 ml of water each time, dried over sodium sulfate and evaporated in vacuo. The remaining title compound is analytically pure.
Rf = 0,23 (hexán - diétyléter 1 : 2).Rf = 0.23 (hexane-diethyl ether 1: 2).
Malá časť tohoto materiálu sa podrobí destilácii v límcovej baničke. Produkt má teplotu varu 168 až 170 ’C/6,7 Pa.A small portion of this material was distilled in a collar flask. The product has a boiling point of 168-170 ° C / 6.7 Pa.
Príklad 2Example 2
Pri použití postupu popísaného v príklade 1 sa vyrobí zlúčenina pomenovaná v nadpise. Získa sa zlúčenina, ktorá sa chromatografuje na stĺpci silikagélu za použitia zmesi hexánu a etylacetátu (2 : 1) ako elučného činidla. Získajú sa analyticky čisté kryštály s teplotou topenia 76 až 78 ’C.Using the procedure described in Example 1, the title compound was prepared. The product was chromatographed on a silica gel column eluting with hexane: ethyl acetate (2: 1). Analytically pure crystals having a melting point of 76-78 ° C are obtained.
Príklad 3Example 3
N- (2,4-Dimetyl->“3ir^/t^#. )-N-metoxyetyl-chlóracetamidN- (2,4-Dimethyl-3'-methyl) -N-methoxyethyl-chloroacetamide
Za použitia postupu popísaného v príklade 1 sa vyrobí zlúčenina pomenovaná v nadpise. Získa sa olejovitá látka, ktorá po chromatografii na stĺpci silikagélu za použitia dietyléteru ako elučného činidla po ochladení na teplotu -20 *C stuhne. Pevný produkt sa topí pri teplote 54 až 55 C.Using the procedure described in Example 1, the title compound was prepared. An oily substance is obtained which solidifies after chromatography on a silica gel column using diethyl ether as the eluent. The solid melted at 54-55 ° C.
Príklad 4Example 4
Etylester N-(chlóracetyl)-N-(2-metoxykarbonyl alanínu )Za použitia postupu popísaného v príklade 1 sa vyrobí zlúčenina pomenovaná v nadpise. Výsledná hnedá olejovitá látka sa po chromatografii na silikagéle za použitia zmesi dietyléteru a hexánu (2 : 1) ako elučného činidla podrobí destilácii v límcovej banke. Získa sa analyticky čistá zlúčenina uvedená v názve, s teplotou varu 135 C/0,7 Pa.N- (Chloroacetyl) -N- (2-methoxycarbonyl alanine) ethyl ester Using the procedure described in Example 1, the title compound was prepared. The resulting brown oil was chromatographed on silica gel using diethyl ether / hexane (2: 1) as the eluent to distil in a collar flask. An analytically pure title compound is obtained with a boiling point of 135 C / 0.7 Pa.
Príklad 5Example 5
N- (ÍH-Pyrazol- 1-ylmety 1) -N- (2,4 -dimety 1 )chlóracetamidN- (1H-Pyrazol-1-ylmethyl) -N- (2,4-dimethyl) chloroacetamide
Za použitia postupu popísaného v príklade 1 sa vyrobí zlúčenina pomenovaná v nadpise. Získa sa zvyšok, ktorý sa podrobí chromatografii na stĺpci silikagélu. Eluovaním zmesou rovnakých podielov hexánu a dietyléteru sa získa zlúčenina uvedená v názve, ako analyticky čistý sirupovitý materiál, ktorý skryštalizujeypo· ochladení na teplotu -20 ’C. Produkt sa topí po prekryštalizovaní z dietyléteru pri teplote 88 až 89 C.Using the procedure described in Example 1, the title compound was prepared. The residue is chromatographed on a silica gel column. Elution with a mixture of equal portions of hexane and diethyl ether gives the title compound as an analytically pure syrupy material which crystallizes upon cooling to -20 ° C. The product melts after recrystallization from diethyl ether at 88-89 ° C.
Príklad 6Example 6
Etylester N-(chlóracetyl)-N-(3,5-dimetylizoxazol-4-yl)alanínuN- (chloroacetyl) -N- (3,5-dimethylisoxazol-4-yl) alanine ethyl ester
Za použitia postupu popísaného v príklade 1 sa vyrobí zlúčenina pomenovaná v nadpise. Získaná látka sa vyberie so 100 ml di etyléteru, zmes sa odfiltruje, filtrát sa odparí a olejovitý odparok sa chromatografuje na stĺpci silikagélu. Eluovaním stĺpca zmesou rovnakých podielov dietyléteru a hexánu sa získa zlúčenina uvedená v názve, s teplotou topenia 49 až 50 *C.Using the procedure described in Example 1, the title compound was prepared. The material obtained is taken up in 100 ml of diethyl ether, the mixture is filtered, the filtrate is evaporated and the oily residue is chromatographed on a silica gel column. Elution of the column with a mixture of equal portions of diethyl ether and hexane gave the title compound, m.p. 49-50 ° C.
Príklad 7Example 7
N-l- (lH-Pyrazol-l-yl) etyl-N- (2,4-dimetyl'h’i3' chlóracetamidN-1- (1H-Pyrazol-1-yl) ethyl-N- (2,4-dimethyl'h '1,3' chloroacetamide
Za použitia postupu popísaného v príklade 1 sa vyrobí zlúčenina pomenovaná v nadpise. Získaná reakčná zmes sa odfiltruje, odparí za vákua a sirupovitý odparok sa chromatografuje na stĺpci silikagélu. Eluovaním stĺpca zmesou hexánu a dietyléteru (3 : 2) sa získa zlúčenina uvedená v názve vo forme bezfarebných kryštálov, ktoré sa po prekryštalizovaní z dietyléteru topia pri teplote 76 až 78 ’C.Using the procedure described in Example 1, the title compound was prepared. The reaction mixture obtained is filtered, evaporated in vacuo and the syrupy residue is chromatographed on a silica gel column. Elution of the column with hexane / diethyl ether (3: 2) afforded the title compound as colorless crystals, which melted at 76-78 ° C after recrystallization from diethyl ether.
Podlá postupu popísaného v príkladoch 1 až 7 sa pripravia ďalej uvedené zlúčeniny všeobecného vzorca I.The following compounds of formula I were prepared according to the procedure described in Examples 1 to 7.
Zlúčeninacompound
Arylaryl
YY
Charakterizáciacharacterization
Tabuľka A </Table A </
ch2oc2h5 ch2ch2och3 ch 2 oc 2 h 5 ch 2 ch 2 och 3
CH2CH2OCH3 CH 2 CH 2 OCH 3
t.t. 25 až 26 ’Cmp 25 to 26 'C
Rf=0,45 (cyklohexán/etylacetát 1:1) Rf = 0.45 (cyclohexane / ethyl acetate 1: 1)
Rf=0,3 (cyklohexán/ /etylacetát 6:4) Rf = 0.3 (cyclohexane / / ethyl acetate 6: 4)
Zlúčenina Aryl Y CharakterizáciaCompound Aryl Y Characterization
t.t. 132 až 133 eCmp 132-133 e C
Zlúčenina ArylCompound Aryl
ť.___________________ť .___________________
2,4-diMe-3iénCharakteri zácia2,4-diMe-3-eneCharacterization
CH2-(2-furyl)CH 2 - (2-furyl)
CH2-(2-tienyl)CH 2 - (2-thienyl)
t.t. 78 až 79 ’Cmp 78 to 79 ’C
t.t. 57 až 59 *Cmp 57-59 ° C
t.t. 66 až 67 ’Cmp 66 to 67 ’C
YY
Zlúčenina ArylCompound Aryl
ť.____________________ť .____________________
2,4-diMe-+3<?<-2,4-dimethyl-3 <? <-
Charakterizácia t.t. 77 až 78 *CCharacterization m.p. 77-78 ° C
t.t. 54 až 56 *Cmp 54-56 ° C
t.t. 71 až 72mp 71 to 72
t.t. 110 až 115 *Cmp 110-115 ° C
t.t. 119 až 125 ‘Cmp 119 to 125 ° C
t.t. 120 až 122 *Cmp 120-122 ° C
Charakteri záciaCharacterization
C(Me)2CH2OMeC (Me) 2 CH 2 OMe
CH(Me)OCH2CH2C1CH (Me) OCH 2 CH 2 Cl
CH(OMe)CH2OMeCH (OMe) CH 2 OMe
CH2OCH2CH2OMeCH 2 OCH 2 CH 2 OMe
t.t. 76 až 78 ’Cmp 76 to 78 ’C
t.t. 62 až 64 ’Cmp 62 to 64 ’C
Rf=0,3 (dietyléter/ /hexán 1:1) Rf = 0.3 (diethyl ether / / hexane 1: 1)
t.v. 117 až 118 ’C/ /0,7 Pabp 117 to 118 ´C // 0.7 Pa
Zlúčenina ArylCompound Aryl
2,4-diMe-*Jiri-:>2,4-dimethyl Jiri * -:>
Charakteri zácia t.t. 59 až 64 ’CCharacteristics m.p. 59 to 64 'C
CH(Me)OC2CH2CNCH (Me) OC 2 CH 2 CN
Zlúčenina Aryl Y Charakterizácia :Compound Aryl Y Characterization:
Zlúčenina Aryl Y CharakterizáciaCompound Aryl Y Characterization
-pyrazol-4-ylpyrazol-4-yl
Vo vyššie uvedenej tabuľke majú jednotlivé symboly nasledujúce významy:In the above table, the symbols have the following meanings:
Me = metylMe = methyl
Et = etylEt = ethyl
t.t. = teplota topeniamp = melting point
t.v. = teplota varubp = boiling point
V nasledujúcej časti sú popísané príklady testov herbicídnej účinnosti.Examples of herbicidal activity tests are described below.
Príklad 8Example 8
Ničenie burín - preemergentné ošetrenieWeed control - pre-emergence treatment
Kvetináče s priemerom 7 cm sa nap^ia zmesou rašelinového substrátu a piesku. Povrch zmesi rašelinového substrátu a piesku sa postrieka kvapalným preparátom s obsahom testovanej látky (pripraveným napríklad postupom podlá príkladu B) a do každého črepníka sa zasejú semená Lepidium sativum (žerucha), Agrostis alba, Avena sativa (ovoš hluchý) a Lolium perenne (mätonoh), pričom semená ovsa hluchého a mätonohu sa po zasiatí prikryjú slabou vrstvou (0,5 cm) zmesi rašelinového substrátu a piesku. Osiate kvetináče sa 21 dní uchovávajú pri laboratórnej teplote za osvetlovania denným alebo jemu ekvivantným svetlom počas 14 až 17 hodín denne.The pots with a diameter of 7 cm are stretched with a mixture of peat substrate and sand. The surface of the peat substrate / sand mixture is sprayed with a liquid preparation containing the test substance (prepared, for example, as described in Example B), and seeds of Lepidium sativum (cress), Agrostis alba, Avena sativa (but deaf) and Lolium perenne ( , wherein the seeds of deaf oat and buttermilk are covered with a thin layer (0.5 cm) of the mixture of peat substrate and sand after sowing. Seeded pots shall be kept at room temperature for 21 days under illumination with daylight or equivalent light for 14 to 17 hours per day.
Po 21 dňoch sa vyhodnotí herbicídny účinok jednotlivých účinných látok. Toto hodnotenie sa uskutočňuje vizuálnym zistením rozsahu a kvality poškodenia jednotlivých klíčnych rastlín.After 21 days, the herbicidal activity of the individual active ingredients is evaluated. This evaluation is carried out by visually assessing the extent and quality of damage to individual key plants.
Zlúčeniny všeobecného vzorca I sa vyššie popísaným spôsobom aplikujú v dávkach zodpovedajúcich 1,4 a 5,6 kg účinnej látky na hektár.The compounds of the formula I are applied in the manner described above in doses corresponding to 1.4 and 5.6 kg of active compound per hectare.
Bola zistená herbicídna účinnosť, t.j. výrazné poškodenie pokusných rastlín.Herbicidal activity, i.e. significant damage to the test plants.
Príklad 9 íExample 9 i
Ničenie burín - postemergentné ošetrenieWeed control - post-emergence treatment
Pracuje sa analogickým postupom ako v príklade 8 s tým rozdielom, že sa testované zlúčeniny aplikujú v čase, keď sú pokusné rastliny v štádiu dvoch až štyroch listov. Semená jednotlivých druhov rastlín sa vysievajú odstupňované tak, aby rastliny dosiahli štádium dvoch až štyroch listov približne v rovnakom čase.The procedure is analogous to Example 8, except that the test compounds are applied at the time when the test plants are in the two to four leaf stage. The seeds of the individual plant species are sown in stages so that the plants reach the stage of two to four leaves at about the same time.
I v tomto prípade sa zlúčeniny všeobecného vzorca aplikujú v dávkach zodpovedajúcich 1,4 kg/ha a 5,6 kg/ha. Herbicídny účinok sa vyhodnocuje ndl· 21. deň po aplikácii testovaných látok a to analogickým spôsobom ako v príklade 8. Bola zistená herbicídna účinnosť.Again, the compounds of the formula are applied at doses corresponding to 1.4 kg / ha and 5.6 kg / ha. The herbicidal activity is evaluated ndl · 21 days after application of the test substances in a manner analogous to Example 8. Herbicidal activity was found.
Príklad 10Example 10
Účinnosť reprezentatívnych zlúčenín podľa vynálezu sa hodnotí za použitia nasledujúceho testu účinnosti pri preemergentnej aplikácii.The potency of representative compounds of the invention is evaluated using the following potency test for pre-emergence application.
Výsevné misky o rozmeroch 30 x 40 cm sa do výšky 6 cm naplnia zmesou rašelinového substrátu a piesku a postriekajú sa vodným preparátom testovanej látky (pripraveným napríklad podľa príkladu B), ktorý obsahuje zlúčeninu podľa vynálezu v požadovanej koncentrácii. Objem postreku zodpovedá aplikácii 600 litrov vodného preparátu na hektár. Rovnaký test sa opakuje s rôznymi koncentráciami kvapalného preparátu, pričom tieto koncentrácie sa volia tak, aby sa dosiahli požadované aplikačné dávky. Do každej misky sa zasejú semená 6 druhov rastlín. Počet vysievaných semien jednotlivých druhov rastlín závisí od klíčivosti jednotlivých druhov, ako aj od veľkosti klíčnych rastlín jednotlivých druhov. Po zasiatí semien sa ošetrený povrch pôdy prikryje tenkou vrstvou (približne 0,5 cm) zmesi rašelinového substrátu a piesku.The 30 x 40 cm seed pans are filled to a height of 6 cm with a mixture of peat substrate and sand and sprayed with an aqueous preparation of the test substance (prepared, for example, according to Example B), containing the compound of the invention at the desired concentration. The spray volume corresponds to the application of 600 liters of aqueous preparation per hectare. The same test is repeated with different concentrations of the liquid preparation, these concentrations being selected to achieve the desired application rates. Seeds of 6 plant species are sown in each dish. The number of seeds sown for each plant species depends on the germination of each species as well as the size of the key plants of each species. After sowing the seeds, the treated soil surface is covered with a thin layer (approximately 0.5 cm) of the peat substrate / sand mixture.
Takto pripravené výsevné misky sa 28 dní udržiavajú pri teplote 20 až 24 *C, pričom sa osvetľujú 14 až 17 hodín denne.The trays thus prepared are kept at 20 to 24 ° C for 28 days, illuminating for 14 to 17 hours per day.
Stanovenie herbicídneho účinku príslušnej zlúčeniny podľa vynálezu sa uskutočňuje po 28 dňoch. Toto'stanovenie spočíva vo vizuálnom vyhodnotení stupňa a charakteru poškodenia rôznych rastlín. Predovšetkým výhodné herbicídne vlastnosti sa okrem iného pozorovali u zlúčenín č. 25, 26, 47, 48, 55, 75, 84 a 86 z tabuľky A. Niektoré výsledky dosiahnuté pri aplikácii týchto účinných látok v dávkach zodpovedajúcich 1 kg/ha, sú uvedené v nasledujúcej tabuľke B.The herbicidal activity of the compound of the invention is determined after 28 days. This determination consists in a visual evaluation of the degree and nature of damage to various plants. Particularly advantageous herbicidal properties have been observed, inter alia, in compounds no. 25, 26, 47, 48, 55, 75, 84 and 86 of Table A. Some of the results obtained with the application of these active ingredients at doses corresponding to 1 kg / ha are shown in Table B below.
Príklad 11Example 11
Postemergentné ošetreniePost-emergence treatment
Ďalšie hodnotenie účinnosti reprezentatívnych zlúčenín všeobecného vzorca I sa uskutočňuje za použitia postemergentného testu, ktorý sa uskutočňuje obdobne ako preemergentné testy popísané v príklade 10 s tým rozdielom, že sa kvapalný preparát testovanej látky aplikuje v čase, keď rastliny sú v štádiu dvoch až štyroch listov. Aby bolo možné dosiahnuť, že rôzne druhy rastlín dospejú do štádia dvoch až štyroch listov približne v rovnakom čase, vysievajú sa semená jednotlivých druhov rastlín v príslušne odstupňovaných intervaloch.Further evaluation of the efficacy of representative compounds of Formula I is performed using a post-emergence test which is performed similar to the pre-emergence tests described in Example 10 except that the liquid preparation of the test substance is applied at a time when the plants are in the two to four leaf stage. In order to achieve that the different plant species reach the stage of two to four leaves at about the same time, the seeds of the individual plant species are sown at appropriate intervals.
V skleníku sa udržiavajú rovnaké podmienky (teplota, osvetlenie) ako v príklade 10. Stanovenie herbicídneho účinku sa taktiež uskutočňuje za 28 dní po aplikácii, a to spôsobom popísaným v príklade S..The greenhouse is maintained at the same conditions (temperature, illumination) as in Example 10. The determination of the herbicidal effect is also carried out 28 days after application, as described in Example S.
Predovšetkým výhodné herbicídne vlastnosti sa okrem iného zistili u zlúčenín č. 25, 26, 47, 48, 55, 75, 84 a 86 z tabuľky A. Niektoré výsledky dosiahnuté pri aplikácii týchto látok v dávkach zodpovedajúcich 5 kg/ha sú zhrnuté v nasledujúcej tabuľke C.Particularly advantageous herbicidal properties have been found, inter alia, in compounds no. 25, 26, 47, 48, 55, 75, 84, and 86 of Table A. Some results obtained with the application of these compounds at doses corresponding to 5 kg / ha are summarized in Table C below.
Tabuľka BTable B
Účinnosť preemergentnej aplikácie v dávke 1 kg/haEffectiveness of pre-emergence application at 1 kg / ha
Pokusná rastlina Poškodenie v % pri aplikácii zlúčeniny všeobecného vzorca I z príkladu č.Test Plant Damage% in application of the compound of Formula I of Example 1.
Tabuľka CTable C
Účinnosť pri postemergentnej aplikácii v dávke 5 kg/haEfficiency in post-emergence application at 5 kg / ha
Pokusná rastlina Poškodenie v % pri aplikácii zlúčeniny všeobecného vzorca I z príkladu č.Test Plant Damage% in application of the compound of Formula I of Example 1.
Legenda: *) aplikovaná dávka 4 kg/haLegend: *) application rate of 4 kg / ha
1) normálne podmienky1) normal conditions
2) závlahové podmienky2) irrigation conditions
Príklad 12Example 12
Poľný pokusField trial
Zlúčenina č. 25 sa ďalej testuje v poľných podmienkach v prítomnosti niekoľkých druhov úžitkových plodín. Účinná látka sa aplikuje preemergentne. Pokus sa uskutočňuje za nasledujúcich podmienok:Compound No. 25 is further tested under field conditions in the presence of several crop species. The active substance is applied pre-emergence. The test is performed under the following conditions:
pokusné úžitkové plodiny sója (odroda Steele) (So) bavlník (Stoneville 213) (Ba) kukurica (LG 11) (Ku) pšenica (Svenno) (Pš) burinyexperimental crops of soya (Steele variety) (Sat) cotton (Stoneville 213) (Ba) maize (LG 11) (Ku) wheat (Svenno) (Ps) weeds
Alopecurus nsis (Al)Alopecurus nsis
Echinochloa crus galli (Ech)Echinochloa crus galli
Gálium aparine — ckojb/fenšsGalium aparine - ckojb / fenšs
Chenopodium album a polyspermum - dvojklíčneChenopodium album and polyspermum - dicots
Amaranthus retroflexus - dvojklíčneAmaranthus retroflexus
Všetky vyššie uvedené buriny boli na pokusnom pozemku už prítomné (prirodzené zaburinenie), s výnimkou psiarky Alopecurus pratensis, ktorá bola vysiata.All of the above weeds were already present on the test plot (natural deprivation), with the exception of Alopecurus pratensis, which was sown.
Objem postreku: Počet opakovaní: Vyhodnotenie:Spray volume: Number of repetitions: Evaluation:
750 litrov/ha za 28 dní po aplikácii750 liters / ha in 28 days after application
Štandardy: Alachlór [a-chlór-2',6'-dietyl-N-metoxymetylacetanilid] a Metolachlor [a-chlór-2'-etyl-6'-metyl-N-(l-metyl metoxyetyl)acetanilid]Standards: Alachlor [α-chloro-2 ', 6'-diethyl-N-methoxymethylacetanilide] and Metolachlor [α-chloro-2'-ethyl-6'-methyl-N- (1-methylmethoxyethyl) acetanilide]
Bola zistená nasledujúca herbicídna účinnosť.The following herbicidal activity was found.
Tabuľka DTable D
Účinnosť pri postemergentnej aplikácii v dávke 1,5 kg/haEfficiency in post-emergence application at 1.5 kg / ha
xyetyl)-acetanilid rífa -g)xyethyl) -acetanilide rifa -g)
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| EP2052606A1 (en) | 2007-10-24 | 2009-04-29 | Bayer CropScience AG | Herbicide combination |
| DE102008037620A1 (en) | 2008-08-14 | 2010-02-18 | Bayer Crop Science Ag | Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides |
| CN103220911B (en) | 2010-10-15 | 2017-02-15 | 拜耳知识产权有限责任公司 | Use of ALS inhibitor herbicides for control of unwanted vegetation in ALS inhibitor herbicide tolerant beta vulgaris plants |
| AU2012251597B2 (en) | 2011-05-04 | 2015-11-05 | Bayer Intellectual Property Gmbh | Use of ALS inhibitor herbicides for control of unwanted vegetation in ALS inhibitor herbicide tolerant Brassica, such as B. napus, plants |
| UA115577C2 (en) | 2012-12-13 | 2017-11-27 | Байєр Кропсайєнс Акцієнгезелльшафт | Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant beta vulgaris plants |
| AR127377A1 (en) | 2021-10-15 | 2024-01-17 | Kws Saat Se & Co Kgaa | BETA VULGARIS MUTANTS TOLERANT TO ALS-INHIBITING HERBICIDES |
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| US3749775A (en) | 1969-07-07 | 1973-07-31 | Stauffer Chemical Co | Insecticidal 2-aminothiazole phosphates and phosphonates |
| JPS4975572A (en) * | 1972-08-31 | 1974-07-20 | ||
| JPS5031039A (en) * | 1973-07-27 | 1975-03-27 | ||
| GB1497536A (en) * | 1973-12-17 | 1978-01-12 | Lilly Industries Ltd | 2-acylaminooxazoles methods for their preparation and their use |
| GB1548398A (en) * | 1975-06-05 | 1979-07-11 | Lilly Industries Ltd | Acylamino pyrroles furans and thiophenes |
| GB1552125A (en) * | 1975-06-07 | 1979-09-05 | Lilly Industries Ltd | 2-acylamino oxazoles |
| US4155744A (en) * | 1977-06-17 | 1979-05-22 | Monsanto Company | Herbicidal α-haloacetamides |
| JPS572276A (en) * | 1980-06-07 | 1982-01-07 | Otsuka Chem Co Ltd | 1-methyl-5- n-alkyl-n-chloroacetylamino pyrazole-4- carboxylic acid ester derivative, its preparation, and herbicide for paddy rice field |
| JPS588087A (en) * | 1981-07-03 | 1983-01-18 | Toyama Chem Co Ltd | Novel cephalosporin compound and its intermediate |
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- 1983-02-08 HU HU83429A patent/HU193036B/en unknown
- 1983-02-08 KR KR1019830000493A patent/KR880002359B1/en not_active IP Right Cessation
- 1983-02-08 CA CA000421147A patent/CA1248538A/en not_active Expired
- 1983-02-09 EG EG85/83A patent/EG16720A/en active
- 1983-05-09 FR FR8307966A patent/FR2530631B1/en not_active Expired
- 1983-05-09 FR FR8307965A patent/FR2523967B1/en not_active Expired
-
1987
- 1987-12-30 MY MY168/87A patent/MY8700168A/en unknown
-
1994
- 1994-02-14 BG BG098475A patent/BG60498B2/en unknown
-
2002
- 2002-09-30 NL NL350007C patent/NL350007I2/en unknown
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