PL109937B1 - Herbicide - Google Patents

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PL109937B1
PL109937B1 PL1977200438A PL20043877A PL109937B1 PL 109937 B1 PL109937 B1 PL 109937B1 PL 1977200438 A PL1977200438 A PL 1977200438A PL 20043877 A PL20043877 A PL 20043877A PL 109937 B1 PL109937 B1 PL 109937B1
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PL1977200438A
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Hoechst Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
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    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
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    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/20—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom three- or four-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
    • C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dentistry (AREA)
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Description

Przedmiotem wynalazku jest srodek chwasto¬ bójczy, zawierajacy zwiazki o ogólnym wzorze 1, w którym Ri oznacza chlorowiec, grupe CF3 albo (Ci—C4)-alkil, Z oznacza grupy —CN, —CS—NH2, —CO—R2 albo —CH2—O—R3, R2 oznacza grupe hydroksyilowa, —O—Kat, (Ci—Ci2)-aliko- ksylowa, która moze byc ewentualnie podstawio¬ na przez OH, chlorowiec, CF3, grupe (Ci—^C6)jaliko- ksylowa (Ci—C4)-alkilotiolowa, fenylowa, fenoksy- lowa albo przez grupe chlorowcofenoksylowa; rod¬ niki o wzorach 5, 6, 7, —(OC2H4)2-3—OCmH2m+i, o wzorach 8,9, gdzie grupa o wzorze 10 oznacza rodnik pirolidynylowy, piperydynylowy, morfoli- nylowy albo N-metylo-piperazynylowy; grupe (C5—C6)-cykloalkoksylowa, która moze byc ewen¬ tualnie podstawiona przez (Ci—C4)-alkil i/albo przez chlorowiec; grupe (C3—C4)-alkenyloksylowa, cyklo- heksenyloksylowa, (C3—C4)-alkinyloksylowa, która moze byc ewentualnie podstawiona w polozeniu 1 przez (Ci—C4)-alkil i/albo fenyl; grupe fenoksylo- wa, która moze byc ewentualnie podstawiona przez chlorowiec, przez grupe N02 i/albo (Ci—C4)- -alkil; grupe (Ci—Ce^alkilotiolowa, alililotiolowa, fenylotiolowa, chlorowcofenylotiolowa, aminowa, (Ci—C4)-alkiloaminowa, hydroksyetyloaminowa, dwu-(Ci—C4)-alkiloaminowa, pirolidynowa, pipe- rydynowa, morfolinowa, anilinowa, która moze byc ewentualnie podstawiona przez chlorowiec, grupe CF3 i/albo przez (Ci—C4)-alkil, jak równiez grupe hydrazynowa, R3 oznacza wodór, (Ci—C4)- -alkil, (Ci—C4)-alkilokarbonyl, chlorowco-(Ci—C4)- -alkilokarbonyl, benzoil, który jest ewentualnie podstawiony przez chlorowiec, grupe N02 i/albo przez (Ci—C4)-alkil; (d—C4)^alkiliokarbanioil, dwu- 5 -(Ci—C4)-alkilokarbamoil, fenylokarbamoil, który moze byc ewentualnie podstawiony przez chloro¬ wiec i/albo pr^ez (Ci—C3)-alkil; (Ci—C4)-alkilosul- fonyl, fenylosulfonyl, grupe —SO3H albo —SOsKat, oraz Kat oznacza równowaznik kationu zasady 10 nieorganicznej albo organicznej, n oznacza liczbe 1—3, oraz m oznacza liczbe 1—6.„Kat" oznacza przede wszystkim równowazniki kationu zasad nieorganicznych takie jak Na+, K+, 1/2 Ca++ i 1/2 Mg++ ponadto NH+ i kationy 15 amin organicznych takich jak rózne alifatyczne jedno-, dwu- albo trójalkiloaminy, odpowiednich trójetanoloamin, aniliny, metyloaniliny, benzylo- aminy i dwufenyloaminy. „Hal" oznacza korzyst¬ nie chlor albo brom. 20 Jesli rodniki R2 albo R3 zawieraja jako skladni¬ ki podstawione grupy fenylowe , to te ostatnie zawieraja do trzech, korzystnie jednak jeden pod¬ stawnik. W przypadku gdy podstawnik ten ozna¬ cza grupy alkilowe, korzystne sa metyl albo etyl. 25 Wsród zwiazków o wzorze 1 korzystne sa takie, w których (Ri)n oznacza atom chloru w polozeniu 4, trójfluorometyl w polozeniu 4 albo 2 atomy chloru w polozeniu 2,4, Z oznacza rodnik o wzo¬ rze —CH2—O—R3 i R3 ma wyzej podane znacze- 30 nie. 1099373 109937 4 Wsród zwiazków o wzorze 1 korzystnie sa po¬ nadto takie, w których (Ri)n oznacza atom chloru w polozeniu 4 albo dwa atomy chloru w poloze¬ niu 2 i 4, Z oznacza rodnik o wzorze CO—R2 i R2 oznacza grupe hydroksylowa, OKat, (Ci—Ci2)-alko- ksylowa, która moze byc ewentualnie podstawio¬ na przez grupe —OH, chlorowiec, CF3, (Ci—C6- -alkoksylowa, (Ci—C4)^alkilotiolowa, fenylowa, fe- noksylowa albo przez grupe chlorowcofenoksylo- wa; rodniki o wzorach 5, 6, 7 albo —(OC2H4)2_3— —OCmH2m-i; grupe (C5—Ce^cykloalkoksylowa, któ¬ ra moze byc ewentualnie podstawiona przez (Ci—C4)-alkil i/albo przez chlorowiec; grupe C3— "R^fl^HLUiiluiiwiilu^a, cykloheksenyloksylowa, IC^R)48Mri^&3ylowa, która moze byc ewen¬ tualnie podstawiona w polozeniu i przez (Ci—C4)- LaJJ^^ji^^^njjl;!grupe fenoksylowa, która mo- |ze by4 ewesjju^ln^ef podstawiona przez chlorowiec, grup£ JJU2 i/albiJ(Ci—C4)-alkil; grupe (Ci—C6)- -allkilo"tiolowa, allilotiolowa, fenyloltiolowa albo chlorowcofenylotiolowa i m oznacza liczby 1—6.Przedmiotem wynalazku jest srodek chwasto¬ bójczy, który zawiera zwiazki o wzorze 1.Substancje czynna o ogólnym wzorze 1 srod¬ ka wedlug wynalazku mozna wytwarzac róznymi metodami, znanymi dla analogicznych zwiazków. a) Zwiazki te otrzymuje sie np. przez poddanie reakcji zwiazków o ogólnym wzorze 3 ze zwiaz¬ kami o wzorze 2a wedlug schematu 1. Podstaw¬ nik Y oznacza przy tym chlorowiec, korzystnie brom albo chlor, rodnik mezylanowy albo tozyla- nowy. Reakcje przeprowadza sie korzystnie w wa¬ runkach zasadowych w temperaturze 20°C do tem¬ peratury wrzenia mieszaniny, korzystnie w tem¬ peraturze 80°—160°C w obojetnym rozpuszczalni¬ ku takim jak toluen, ksylen, dwumetyloformamid albo dwumetylosulfotlenek. Jako srodki zasadowe stosuje sie weglany albo wodorotlenki metali al¬ kalicznych albo metali ziem alkalicznych albo trzeciorzedowe aminy organiczne takie jak piry¬ dyna albo trójetyloamina.Substancje wyjsciowe o wzorach 2a i 3 znane sa z literatury lub wytwarza sie je w znany sposób. b) Przez reakcje ewentualnie podstawionych (4- -fenoksy/fenoli o wzorze 2a z równowazna iloscia albo z nadmiarem Y-walerolaktonu o wzorze 4 w warunkach zasadowych w temperaturze 100°— 240°C, korzystnie 160°—220°C, otrzymuje sie zwiazki o wzorze 1, w którym Z=COOKat, we¬ dlug schematu 2.Zwiazki o wzorze 2 stosuje sie korzystnie jako fenolany metali alkalicznych. Reakcje mozna przeprowadzic z zastosowaniem rozpuszczalnika j albo bez niego. » ¦ c) Otrzymane w ten sposób zwiazki o- ogólnym wzorze 1 mozna przeprowadzic w dalszych, ogól¬ nie znanych reakcjach, w inne zwiazki o ogól¬ nym wzorze 1, np. przez zmydlanie, estryfikacje, tworzenie soli, przeestryfikowanie, amidowanie, odwodnienie, przylaczenie wody, redukcje albo u- tlenianie. Grupe funkcyjna Z=COOH mozna np. przeprowadzic za pomoca srodków chlorowcuja¬ cych, np. SOCI2, w halogenki kwasowe, za po¬ moca amin w amidy, za pomoca zasad w sole kwasu karboksylowego, za pomoca alkoholi w estry.Estry mozna równiez wytwarzac przez reakcje odpowiedniego halogenku kwasowego z alkohola- 5 mi albo przez alkilowanie soli kwasu np. za po¬ moca zwiazków chlorowcowych albo dwualkilo- siarczanów.Grupe funkcyjna Z=CN mozna np. otrzymac przez odwodnienie amidów pierwszórzedowych, 10 gdzie Z=CONH3, z pieciotlenkiem fosforu, grupe funkcyjna Z o wzorze 11 np. przez przylaczenie siarkowodoru do nitryli, gdzie Z=CN, grupe funk¬ cyjna Z=CONH2 przez przylaczenie .wody do gru¬ py nitrylowej i grupe funkcyjna Z=—CH2OH np. !5 przez redukcje funkcji estrowej za pomoca wo¬ dorku litowoglinowego. Metody te sa ogólnie zna¬ ne i latwo dostepne dla specjalisty.Zwiazki wedlug wynalazku o ogólnym wzorze 1 wykazuja w procesie przed i po wzejsciu do- 20 bre dzialanie chwastobójcze przeciwko szeregowi waznych traw szkodliwych.Z drugiej strony równiez wysokie dawki sa do¬ brze tolerowane przez dwuliscieniowe rosliny uprawne i rózne rodzaje zbóz, tak ze zwiazki te 25 nadaja sie korzystnie do selektywnego zwalcza¬ nia traw szkodliwych w uprawach rolnych.Srodki wedlug wynalazku zawieraja substancje czynne o wzorze 1 na. ogól w ilosci 2—95%. Moz¬ na je stosowac jako proszki zwilzalne, koncen- 30 traty do emulgowania, roztwory do opryskiwania, proszki do opylania albo granulaty w zwyklych preparatach.Proszki zwilzalne stanowia preparaty dysper¬ gujace równomiernie w wodzie, które obok sub- 35 stancji czynnej oprócz substancji rozcienczajacej albo obojetnej zawieraja jeszcze srodki zwilzaja¬ ce, np. polioksyetylowane alkilofenole, polioksy- etylowane oleilo-, albo stearyloaminy, alkilo- albo alkilofenylo-sulfoniany i srodka dyspergujace, np. 40 ligninosulfonian sodu, 2,2/^dwunaftylometano-6,6/- -dwusulfonian sodu albo tez oleilometylotaury- 'nian sodu.Koncentraty do emulgowania otrzymuje sie przez rozpuszczenie substancji czynnej w rozpu- 45 szczalniiku organicznym, np. butanolu, cykloheksa- nonie, dwuimetyloformamiidzie, ksylenie alibo tez wyzej wrzacych zwiazkach aromatycznych i doda¬ nie niejonowego srodka zwilzajacego, np. polioksy- etylowanego alkilofenolu albo polioksyetylowanej 50 oleilo- albo stearylo-aminy.Srodki do opylania otrzymuje sie przez zmie¬ lenie substancji czynnej z mialko rozdrobnionymi substancjami stalymi, np. talkiem, naturalnymi glinami takimi jak kaolin, bentonit, pirofilit albo 55 ziemia okrzemkowa.Roztwory do opryskiwania, jakie wielokrotnie rozprowadzane sa w puszkach do opryskiwania, zawieraja substancje czynna rozpuszczona w or¬ ganicznym rozpuszczalniku, obok tego np. jako 60 srodek porotwórczy mieszanine fluorocttloroweglo- wodorów i/albo dwutlenku wegla.Granulaty mozna wytwarzac albo przez rozpy¬ lanie substancji czynnej na zdolny do adsorpcji, granulowany material obojetny albo przez nano- 65 szenie koncentratów substancji czynnej za porno-109937 6 ca srodków klejacych, np. polialkoholu winylowe¬ go, poliakrylanu sodu albo tez olejów mineral¬ nych na powierzchnie nosników, takich jak piasek, kaolinity, albo granulowanego materialu obojet¬ nego. Mozna równiez wytwarzac odpowiednie sub- 5 stancje czynne w sposób przyjety dla wytwarza¬ nia granaliów nawozów, w razie potrzeby w mie¬ szaninie z nawozami.W srodkach chwastobójczych stezenie substan¬ cji czynnej w preparatach handlowych moze byc io rózne. W proszkach zwilzanych stezenie substan¬ cji czynnej zmienia sie np. od okolo 10°/o do 95%, reszta sklada sie z wyzej podanych dodatków do preparatów, w koncentratach do emulgowania ste¬ zenie substancji czynnej wynosi okolo 10%—80%. 15 Preparaty pyliste zawieraja przewaznie 5—20% substancji czynnej, roztwory do opryskiwania oko¬ lo 2—20%. W granulatach zawartosc substancji czynnej zalezy czesciowo od tego, czy zwiazek czynny wystepuje w stanie cieklym czy stalym 20 i jakie stosuje sie pomocnicze srodki do granulo¬ wania, wypelniacze itd.Do zastosowania koncentraty handlowe ewen¬ tualnie rozciencza sie w znany sposób, np. w przypadku proszków zwilzalnych i koncentratów 25 do emulgowania za pomoca wody. Preparaty py- liste i granulowane oraz roztwory do opryskiwa¬ nia nie sa juz rozcienczane przed zastosowaniem za pomoca dalszych substancji obojetnych. Ze zmiana warunków zewnetrznych takich jak tern- 30 peratura, wilgotnosc i inne zmienia sie ilosc po¬ trzebna- do stosowania. Moze wiec wahac sie w szerokich granicach, np. 0,1—10,0 kg/ha substan¬ cji czynnej, korzystnie jednak wynosi 0,1—5 kg/ha. 35 Przyklady wytwarzania Przyklad I. Kwas 4-[4'-/2",4"-dwuchlorofe- noksy/-fenoksy]-walerianowy. 20,3 g 4^/2',4'-dwu- chlorofenoksyZ-fenolu rozpuszcza sie w 25 ml ab¬ solutnego etanolu. Do tego dodaje sie 2,12 g me- 40 talicznego sodu i oddestylowuje etanol po rozpu¬ szczeniu sodu. Do stalego 4-^2',4'-dwuchlorofeno- ksyi/fenólo-isodiu dodaje sie teraz 10 g y-twoilero- laktonu i ogrzewa w ciagu 24 godzin w tempera¬ turze 210°C. Zakwasza sie za pomoca stezonego 45 kwasu solnego i rozpuszcza pozostalosc w tolue¬ nie.Faze toluenowa ekstrahuje sie kilkakrotnie na¬ syconym wodno-metanolowym roztworem wodoro¬ weglanu (50%Hwym). Polaczone ekstrakty zakwa- 5° sza sie za pomoca stezonego kwasu solnego i eks¬ trahuje toluenem. Po odciagnieciu rozpuszczalni¬ ka pod zmniejszonym cisnieniem otrzymuje sie po przekrystalizowaniu z cykloheksanu 23,9, to zna¬ czy 80% wydajnosci teoretycznej, kwasu 4-[4'-/2", 55 4"-dwuchlorofenoiksy/-fenoksy] -walerianowego o temperaturze topnienia 88°C, o wzorze 12.Analogicznie wytwarza sie: Przyklad II. Kwas 4-[4V4"-chlorofenoksy/- -fenoksy] ^walerianowy o temperaturze topnienia 60 65—66°C.Przyklad III. Kwas 4-[4'-/4"-trójfluoromety- lofenoksyZ-fenoksy]^walerianowy. Obliczono: C= 61,0; H=4,8; F=16,l. Znaleziono: C=61,l; H=4,9; F=15,9. 65 Przyklad IV. Ester butylowy kwasu 4-[4'- -/2",4"-dwuchlorofenoksyi/-fenoksy]-walerianowego. 25,9 g 4n/2',4'-dwuchlorofenoksy/-fenolu i 14,5 g weglanu potasu w 150 ml dwumetyloformamidu ogrzewa sie w ciagu 1,5 godziny pod chlodnica zwrotna. Nastepnie wkrapla sie w temperaturze 80°C 20 g estru butylowego kwasu 4-chlorowale- rlanowego i ogrzewa mieszanine w ciagu 12 go¬ dzin w temperaturze 120°C. Po odsaczeniu osadu soli oddestylowuje sie rozpuszczalnik pod zmniej¬ szonym cisnieniem. Oleista pozostalosc rozpuszcza sie w toluenie, przemywa rozcienczonym lugiem sodowym i woda i suszy. Po odciagnieciu toluenu pod zmniejszonym cisnieniem destyluje sie pozo¬ stalosc pod bardzo niskim cisnieniem.Otrzymuje sie 32,1 g, to znaczy 78% wydajnosci teoretycznej, estru butylowego kwasu 4-[4V2",4"- -dwuchlorofenoksy/-fenoksy] -walerianowego o wzo¬ rze 13 o temperaturze wrzenia Two,o2=206°C.Analogicznie otrzymuje sie z zastosowaniem 4- -chlorowaleroniitrylu: Przyklad V. 4-[4'-/4"-trójfluoroimetylofeno- ksy/-fenoksy]-waleronitryl.Przyklad VI. Ester n-propylowy kwasu 4- -[4V2",4"-dwuchlorofenoksy/-fenoksy]-waleriano¬ wego. 29 g kwasu 4-[4'-/2//,4,/-dwuchlorofenoksy/-feno¬ ksy]^walerianowego (z przykladu I) ogrzewa sie z 30 ml toluenu i 12 g chlorku tionylu az do konca wywiazywania sie gazu w temperaturze 60°C. Nastepnie oddestylowuje sie toluen i nad¬ miar chlorku tionylu pod zmniejszonym cisnie¬ niem. Pozostajacy olej rozpuszcza sie w toluenie i wkrapla do roztworu 6 g n-propanolu i 8,5 g trójetyloaminy w 50 ml toluenu. Po dodaniu mie¬ sza sie dodatkowo w ciagu 1 godziny w tempera¬ turze 50°C, nastepnie odsacza sie chlorowodorek trójetyloaminy i przemywa woda. Po odciagnieciu rozpuszczalnika destyluje sie pod bardzo niskim cisnieniem.Otrzymuje sie 27,5 g estru n-propylowego kwa¬ su 4-[4'-/i2",4"-dwuchlorofenaksy/-fenoksy]-waleria¬ nowego o temperaturze wrzenia Two,oi=200°C, o wzorze 14.Przyklad VII. Ester Il^rzed-butylowy kwasu 4- [4V4"ntrójfluorometylofenoksy/-fenoksy] -wale¬ rianowego. 29 g kwasu 4-[4V4"-trójfluorometylo- fenaksy/-fenoksy]-walerianowego, 1 ml stezonego kwasu siarkowego i 25 ml butanolu-2 rozpuszcza sie w 300 ml chloroformu i ogrzewa w tempera¬ turze wrzenia do konca oddzielania wody w ciagu okolo 2—4 godzin. Nastepnie przemywa sie neu¬ tralnie nasyconym roztworem wodoroweglanu so¬ du i rozpuszczalnik oddestylowuje pod zmniejszo¬ nym cisnieniem. Oleista pozostalosc destyluje sie pod bardzo niskim cisnieniem.Otrzymuje sie 29,2 g, to znaczy 87,5% wydajno¬ sci teoretycznej, estru Il-rzed* butylowego kwasu 4-[4/-/4"-trójfluorometylofenoksy/-fenoksy] -wale¬ rianowego o wzorze 15, o temperaturze wrzenia Two,i=178°C.Przyklad VIII. 4-[4'-4"-trójfluorometylofeno- ksy/-fenoksy]-ipenjtanol-l. Do zawiesiny 1,25 g wo¬ dorku litowoHglinowego w 50 ml eteru wkrapla sie 20,4 g estru izobutylowego kwasu 4-[4'-/4"-109937 8 -trójfluorametylofenoksyZ-fenoksyl-walerianowego (z przykladu VII). Po zakonczeniu dodawania mie¬ sza sie dodatkowo w ciagu 1 godziny pod chlod¬ nica zwrotna. Nastepnie dodaje sie najpierw po¬ woli 10 ml octanu etylu, nastepnie 40 ml wody, wreszcie silnie mieszajac tyle N—H2SO4, az zo¬ stanie rozpuszczony osad wodorku glinu.Faze eterowa przemywa sie neutralnie rozTwo^ rem wodoroweglanu sodu i rozpuszczalnik odde- stylowuje sie pod zmniejszonym cisnieniem. Po destylacji pod bardzo niskim cisnieniem otrzy¬ muje sie 15,4 g, to znaczy 90,5% wydajnosci teo¬ retycznej, 4-[4'-/4"-trójfluorometylofenoksy/-feno- ksy]-pentanolu-l o temperaturze wrzenia Two,o7= = 174°C, o wzorze 16.Przyklad IX. l-chloroacetoksy-4-[4'-/4"-trój- fluorometylofenoksy/-fenoksy]-pentan. Do roztwo¬ ru 17,0 g 4-[4V4//-trójfluorometylofenoksy/-feno- ksy]-pentanolu-l i 5,55 g trójetyloaminy w 60 ml 15 20 Przyklad XVII. Srodek do opylania otrzy¬ muje sie przez zmieszanie i rozdrobnienie w mly¬ nie udarowym odsrodkowym 10 czesci wagowych substancji czynnej i 90 czesci wagowych talku jako substancji obojetnej.Przyklad XVIII. Granulat sklada sie np. z okolo 2—15 czesci wagowych substancji czynnej i 98—85 czesci wagowych obojetnych materialów granulacyjnych, jak np. atapulgit, pumeks i pia¬ sek kwarcowy.Przyklady biologiczne Nasiona traw wysiano w doniczkach i prepara¬ tami wedlug wynalazku, sporzadzonymi jako pro¬ szki zwilzalne, opryskano powierzchnie ziemi w róznych dawkach. Nastepnie doniczki ustawiono na 4 tygodnie w szklarni. Wyniki traktowania wyznaczono przez bonitacje wedlug schematu Bol- le'go (Nachrichtenblatt des deutschen Pflanzen- schutzdienstes 16, 1964, 92—94).Tablica I Wzór la Tw= temperatura wrzenia Przy¬ klad nr.'¦ X 1 XI XII XIII XIV 1 (R)n 4-CF3 4-CFa 4-CF3 4-CF3 4-CF3 Z ^COOCH3 -COOC2H5 -COOCsHtOi) -COOCH2CH20CH3 -COOCH2CH(CH3)2 Dane fizyczne Two,2=168°C Tw0,oo5=156°C Two,o6=169°C Tw0|o5=177°C Tw0,2=187°C Wytwo¬ rzone wedlug przykladu 4 6 6 7 absolutnego toluenu wkrapla sie w temperaturze pokojowej 6,45 g chlorku chloroacetylu. *o Po dodaniu miesza sie dodatkowo w ciagu 1 go¬ dziny w temperaturze 50°C, nastepnie odsacza sie osad, roztwór toluenowy przemywa sie rozcien¬ czonym kwasem solnym i woda i suszy. Po od¬ ciagnieciu rozpuszczalnika otrzymuje sie 18,5 g, 43 to znaczy 89*/o wydajnosci teoretycznej, 1-chloro- acetyloksy-4-[4V4//-trójfluorometylofenoksyi/-feno- ksy]-pentanu o wzorze 17.Dalsze zwiazki o wzorze 1 otrzymane wedlug powyzszych przykladów zestawiono w tablicy I. 50 Przyklady preparatów Przyklad XV. Koncentrat do emulgowania otrzymuje sie z 15 czesci wagowych substancji czynnej, 75 czesci cykloheksanom! jako rozpusz- 55 czalnika i 10 czesci wagowych oksyetylowanego nonylofenolu (10 AeO) jako emulgatora.Przyklad XVI. Proszek zwilzany latwo dys¬ pergujacy w wodzie otrzymuje sie przez zmiesza¬ nie i zmielenie w dezyntegratorze 25 czesci wa- 60 gowych substancji czynnej, 64 czesci wagowych zawierajacego kaolin kwarcu jako substancje obo¬ jetna, 10 czesci wagowych ligninosulfonianu pota¬ su i 1 czesci wagowej oleilometylotaurynianu so¬ du jako srodka zwilzajacego j. dyspergujacego. 65 Ldcz- 1 ba war¬ tosci 1 2 3 4 5 6 7 8 i 9 Dzialanie szkodliwe w °/o na chwasty 100 97,5 do <100 95 do < 97,5 90 do < 95 85 do < 90 75 do < 85 65 do < 75 32,5 do < 65 0 do < 32,5 rosliny uprawne 0 0 do 2,5 2,5 do 5 5 do 10 10 do 15 15 do 25 25 do 35 35 do 37,5 67,5 do 100 Wyniki w tablicy II wskazuja wyraznie, ze zwiazki stosowane przed i po wzejsciu juz w niskich dawkach maja doskonale dzialanie chwa¬ stobójcze.Zastrzezenia patentowe 1. Srodek chwastobójczy, zawierajacy substancje czynna i znane substancje pomocnicze, znamienny tym, ze jako substancje czynna zawiera zwiazki109937 Tablica II 10 Zwiazek wedlug /przy¬ kladu I VI XII III 1 XIV - XI VIII X XIII Dawka (kg/ha) 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 Stoso¬ wanie przed po przed po przed po przed po przed po przed po przed po przed po przed po EC 1 2 1 SA 1 1 1 4 1 1, 2 5 - 1 DI — — — — — — — 1 1 1 1 — — — 1 1 — — — — — — — — — — — — — AL — — — — — — — 1 2 1 2 2 ¦ 3 1 1 — 1 1 3 J 1 1 1 1 1 2 1 1 1 1 1 1 2 2 1 1 AS substancja aktywna Przed = stosowanie przed wzejsciem PO = stosowanie po wzejsciu EC = (chwastnica jednostronna) Echinochloa SA = (wlosnica) Setaria DI = (palusznik krwawy) Digitaria AL = (wyczyniec polny) Alopecurus o ogólnym wzorze 1, w którym Ri oznacza chloro¬ wiec, grupe CF3 albo (Ci—C4)-alkil, Z oznacza grupy —CN, —CS—NH2, —CO—R2 albo —CHjj— —O—R3, R2 oznacza grupe hydroksylowa, —O— —Kat, (Ci—Ci2)-alkoksylowa, która moze byc ewentualnie podstawiona przez grupe OH, chloro¬ wiec, grupe CF3, (Ci—C6)-alkoksylowa, (Ci—C4)-al- kilotiolowa, fenylowa, fenoksylowa albo przez 60 grupe chlorowcofenoksylowa; rodniki o wzorach 5, 6, 7, —(OC2H4)2-3—OCmH2m+i/ o wzorze 8, 9, ' w którym grupa o wzorze 10 oznacza rodnik pi- rolidynylowy, piperydynylowy, morfolinylowy, al¬ bo N-metylopiperazynylowy; grupe (C5—C6)-cyklo- 65 alkoksylowa, która ewentualnie moze byc pod-109937 11 12 stawiona przez (Ci—C4)-alkil i/albo chlorowiec; grupe (C3—C4)-alkenyloksylowa, cykloheksenylo- ksylowa, (C3—C4)-alkinyloksylowa, która ewentu¬ alnie moze byc podstawiona w polozeniu 1 przez (Ci—C4)-alkil i/albo fenyl; grupe fenotosylowa, któ- 5 ra ewentualnie moze byc podstawiona przez chlo¬ rowiec, grupe N02 i/albo (Ci—C6)-alkil; grupe (Ci—C6)^alkilo:tiolowa, allilotiolowa, fenylotiolowa, chlorowoofenylotiolowa, aminowa, (Ci—C4)-alkilo- aminowa, hydraksyetylo-aminowa, dwu-(Ci—C4)- 10 -alkiloaminowa, piperydynowa, pirolidynowa, mor- folinowa; anilinowa, która ewentualnie moze byc podstawiona przez chlorowiec, grupe CF3 i/albo przez (Ci—C4)-alkil, oraz grupe hydrazynowa, R3 oznacza wodór, (Ci—C4)nalkil, (Ci—C4)^alkilokarbo- 15 nyl, chlorowco-(Ci—C4)-alkilokarbonyl, benzoil, który ewentualnie jest podstawiony przez chloro¬ wiec, grupe N02 i/albo przez (Ci—C4)-alkil; (Ci— C4)-alkilokarbamoil, dwu-(d—C4)-alkilokaribamoil, fenylokanbamoil, który ewentualnie moze byc pod- 20 stawiony przez chlorowiec i/albo pnzez (Ci—C3)- -alkil; (Ci—C4)-alkilosulfonyl, fenylosujfonyl, gru¬ pe —S03H albo —S03Ka1;, oraz Kat oznacza rów¬ nowaznik kationów zasady nieorganicznej albo or¬ ganicznej, n oznacza liczbe 1—3, oraz m oznacza 25 litere 1—6. 2. Srodek wedlug zastrz. 1, znamienny tym, ze, jako substancje czynna zawiera zwiazki o wzorze 1, w którym (Ri)n oznacza atom chloru w polo¬ zeniu 4, trójfluorometyl w polozeniu 4 albo dwa 30 atomy chloru w polozeniu 2 i 4 i Z oznacza rod¬ nik o wzorze —CH2—O—R3 i R3 ma znaczenie podane w zastrz. 1. 3. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazki o wzorze 1, w którym (Ri)n oznacza atom chloru w polo¬ zeniu 4 albo dwa atomy chloru w polozeniu 2 i 4 i Z oznacza rodnik o wzorze —CO—R2 i R2 ma znaczenie podane w zastrz. 1. 4. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 12. 5. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 18. 6. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 13. 7. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 14. 8. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 15. 9. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 16. • 10. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 19. 11. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 20. 12. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 21.109937 S NH2 WZÓR 11 Ct CH- a"O"0™O"°"^H~CH2CH2C00H WZÓR 12 Cl CH- CI-^)-0- S N0CH2CH2CH2CH3 WZÓR 13 ,Cl , CH3 O Cl-Q^dHQH0-CH-CH2CH2-C NOCH2CH2CH3 / WZÓR 14 CH3 /0 CF3^^°^Q"°"CH"CH2-CH2-C( /C2H5 O-CH \ WZÓR 15 CH3 CH3 CF3-Q-0hQh0-CH-CH2CH2CH20H WZÓR 16109937 (R, CH, 0^O^0-CH-CH2-CH2- WZÓR 1 (R1]n o Koy-oH WZÓR 2 ChL I 3 Y-CH-CH2CH2Z WZÓR 3 OCH.No' -OCH2—lo5 WZÓR 5 WZÓR 6 -OCH2J^3 -OGA-N, ;C-C)alkyl \C}- C^JalkyL WZÓR 7 WZÓR 8 -°W..A -N A WZÓR 9 WZÓR 10109937 CH-, 0 /—\ —v I II Cf3 \2/ ° \0/ °"CH"CH2CH2 CH2°~C~CH2Cl WZÓR 17 ?H3 CL -((3)-O -/CJ)- O- CH- CH2CH2COOH WZÓR 18 CH3 O CF3-(O)-0-(^-0-CH-CH2CH2-C -OCH, WZÓR A9 ChL O Cf3 \2/ ° \Q/ ° " CH" CH2CH2_C "OC3H7(n) WZÓR 20 CH3 O CF3 -\O)-0 -^O)- O- CH - CH2CH2 C-OC^CHICH^ WZÓR 2-f109937 CH3 R)n-^Q^O^g-OH + Y-CH-CH2CH2Z Za5ada WZÓR 2a WZÓR 3 9H3 R)—^^-0-^^-O-CH-CHCH Z + HY WZÓR 1a SCHEMAT 1 UV^®-o-®-ch ? chJ^Ko WZÓR 2a WZÓR U CH3 zasada R) —^Vo^O^OCH-CH2-CH2-COOKat SCHEMAT 2 Drukarnia Narodowa, Zaklad Nr 6, 863/80 Cena 45 zl PLThe subject of the invention is a herbicide containing compounds of the general formula I, in which R 1 is halogen, CF3 or (Ci-C4) -alkyl groups, Z represents -CN, -CS-NH2, -CO-R2 or -CH2 groups —O — R3, R2 is hydroxyoyl, —O — Kat, (C1-C12) alkyloxyl which may be optionally substituted with OH, halogen, CF3, (C1-6C6) yalikoxyl ( Ci-C4) alkylthio, phenyl, phenoxy or via a halophenoxy group; radicals of the formulas 5, 6, 7, - (OC2H4) 2-3-OCmH2m + i, of the formulas 8.9, where the group of formula 10 is a pyrrolidinyl, piperidinyl, morpholinyl or N-methyl-piperazinyl radical; a (C5-C6) cycloalkoxy group which may be optionally substituted with (Ci-C4) alkyl and / or by halogen; a (C3-C4) -alkenyloxy, cyclohexenyloxy, (C3-C4) -alkynyloxy group which may be optionally substituted in the 1-position by (Ci-C4) -alkyl and / or phenyl; a phenoxy group which may be optionally substituted by halogen, by NO2 and / or (Ci-C4) -alkyl; (C 1 -C 6 -alkylthio, allylthio, phenylthio, halophenylthio, amino, (C 1 -C 4) -alkylamino, hydroxyethylamino, di- (C 1 -C 4) alkylamino, pyrrolidine, piperidine, morpholino, aniline groups, and substituted by halogen, CF3 and / or (Ci-C4) -alkyl as well as hydrazine, R3 is hydrogen, (Ci-C4) -alkyl, (Ci-C4) -alkylcarbonyl, halo- (Ci-C4) ) - -alkylcarbonyl, benzoyl, which is optionally substituted with halogen, NO 2 and / or with (C 1 -C 4) -alkyl; (C 1 -C 4) -alkylcarbamoyl, di- 5- (C 1 -C 4) -alkylcarbamoyl, phenylcarbamoyl, which may be optionally substituted by halogen and / or by (C 1 -C 3) -alkyl; (C 1 -C 4) -alkylsulfonyl, phenylsulfonyl, the group —SO 3 H or —SO 5 Kat, and Kat is the equivalent cation of an inorganic base or organic, n is the number 1-3, and m is the number 1-6. "Kat" primarily denotes cation equivalents of inorganic bases such as Na +, K +, 1/2 Ca ++ and 1/2 Mg ++ furthermore NH + and cations of organic amines such as various aliphatic mono-, di- or trialkylamines, the corresponding triethanolamines, anilines, methylanilines, benzylamines and diphenylamines. "Hal" is preferably chlorine or bromine. If the radicals R2 or R3 contain substituted phenyl groups as constituents, the latter contain up to three, but preferably one, substituent. When this substituent represents alkyl groups. , methyl or ethyl are preferred. Among the compounds of formula I, preference is given to those in which (R 1) n is chlorine in position 4, trifluoromethyl in position 4 or 2 chlorine atoms in position 2.4, Z is a radical of formula Either —CH2 — O — R3 and R3 have the meanings given above. 1099373 109937 4 Among the compounds of formula I, there are also preferably those in which (R1) n is a 4-chlorine atom or two chlorine atoms in the position of In 2 and 4, Z is a radical of the formula CO — R2 and R2 is a hydroxyl group, OKat, (C 1 -C 12) alkoxy which may optionally be substituted by the group —OH, halogen, CF 3, (C 1 -C 12) -alkoxy, -C6-alkoxy, (Ci-C4) -alkylthio, phenyl, phenoxy or via a halophenoxy group; radicals of formulas 5, 6 , 7 or - (OC2H4) 2_3— —OCmH2m -1; (C 5 -C 6 cycloalkoxy, which may be optionally substituted by (C 1 -C 4) -alkyl and / or by halogen; C 3 - "R 5 -f 2 HLUiiluilvinyl, cyclohexenyloxy, IC 2 R) 48Mri-3-yl which may be optionally substituted in position and by (Ci — C4) - LaJJ ^^ ji ^^^ njjl;! a phenoxy group which may be otherwise substituted by a halogen, a group £ JJU2 and (C 1 -C 4) -alkyl; (C 1 -C 6) -allkyl "thiol, allylthio, phenyltiol or halophenylthiol group and m are numbers 1-6. The invention relates to a herbicide containing compounds of formula 1. The active agent of the general formula I according to the invention can be prepared by various methods known for analogous compounds. a) These compounds are obtained, for example, by reacting compounds of formula III with compounds of formula IIa according to scheme 1. The substituent Y here represents a halogen, preferably bromine or chlorine, a mesylate or tosylate radical. The reactions are preferably carried out under basic conditions at a temperature of 20 ° C to the boiling point of the mixture, preferably at a temperature of 80 ° -160 ° C in an inert solvent such as toluene, xylene, dimethylformamide or dimethylsulfoxide. The basic agents used are carbonates or hydroxides of alkali metals or alkaline earth metals, or tertiary organic amines such as pyridine or triethylamine. The starting materials of the formulas 2a and 3 are known from the literature or are prepared in a known manner. b) By reacting optionally substituted (4-phenoxy / phenols of formula 2a with an equal amount or excess of Y-valerolactone of formula 4 under basic conditions at a temperature of 100-240 ° C, preferably 160 ° -220 ° C, compounds of formula I in which Z = COOKat, according to Scheme 2. Compounds of formula II are preferably used as alkali metal phenates. The reactions can be carried out with or without the use of solvent j or without the use of the solvent j. general formula I can be converted in further, generally known reactions into other compounds of general formula I, for example by saponification, esterification, salt formation, transesterification, amidation, dehydration, addition of water, reductions or oxidation. The Z = COOH function group can be converted, for example, with halogenating agents, e.g. SOCl2, into acid halides, with amines into amides, with bases into carboxylic acid salts, with alcohols into esters. Esters can also be prepared by by reaction of the corresponding acid halide with alcohols or by alkylation of the acid salt, for example with halogen compounds or dialkyl sulfates. The function group Z = CN can be obtained, for example, by dehydration of primary amides, where Z = CONH3, with pentoxide phosphorus, the Z function of formula 11, e.g. by attaching hydrogen sulfide to nitriles, where Z = CN, the Z = CONH2 function by attaching water to the nitrile group and the Z = —CH2OH function, e.g. by reducing ester function with lithium aluminum hydride. These methods are generally known and readily available to those skilled in the art. The compounds according to the invention of the general formula I show a good herbicidal action in the pre-emergence and post-emergence process against a number of important harmful grasses. On the other hand, also high doses are well tolerated. by dicotyledonous crops and various types of cereals, so that these compounds are advantageously suitable for the selective control of harmful grasses in agricultural crops. The compositions according to the invention contain the active compounds of the formula (I). total in the amount of 2-95%. They can be used as wettable powders, emulsifiable concentrates, spraying solutions, dusting powders or granules in conventional formulations. Wettable powders are formulations dispersing evenly in water, which, in addition to the active ingredient, in addition to the diluent or inert, they also contain wetting agents, for example polyoxyethylated alkylphenols, polyoxyethylated oleyl or stearylamines, alkyl or alkylphenyl sulfonates, and dispersants, for example sodium lignin sulphonate, 2.2 (di-naphthylmethane-6.6). Sodium disulfonate or sodium oleyl methyl taurate. Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene and also above-boiling aromatic compounds and addition of nonionic compounds. a wetting agent, e.g. polyoxyethylated alkylphenol or polyoxyethylated 50 oleyl or stearyl amine. Dusting is obtained by grinding the active ingredient with finely divided solids, e.g. talcum, natural clays such as kaolin, bentonite, pyrophyllite or diatomaceous earth. The spray solutions which are repeatedly distributed in the spray cans contain the active ingredient dissolved in an organic solvent, in addition, for example, as a blowing agent with a mixture of fluorocarbon hydrocarbons and / or carbon dioxide. The granules can be prepared either by spraying the active ingredient onto an adsorbable granular inert material or by nanosizing concentrates of substances active in porno 109937 6 adhesives, for example polyvinyl alcohol, sodium polyacrylate or also mineral oils on the surface of carriers such as sand, kaolin or granular inert material. It is also possible to prepare the corresponding active ingredients in a manner customary for the production of fertilizer granules, if desired in admixture with fertilizers. In herbicides, the concentration of the active ingredient in commercial preparations can be different. In wettable powders, the active ingredient concentration varies, for example, from about 10% to 95%, the remainder consists of the above-mentioned formulation additives, and in emulsifiable concentrates, the active ingredient concentration is about 10% to 80%. Dust formulations usually contain 5-20% of active ingredient, spray solutions about 2-20%. In granules, the active ingredient content depends in part on whether the active compound is in a liquid or solid state, and what granulation auxiliaries, fillers, etc. are used. Commercial concentrates can be diluted in a known manner, e.g. in the case of wettable powders and concentrates which are emulsifiable with water. Dust and granular formulations and spraying solutions are no longer diluted with further inert substances before use. That a change in external conditions such as temperature, humidity, etc. changes the amount required to be applied. It can therefore vary within wide limits, for example 0.1 to 10.0 kg / ha of active compound, but preferably 0.1 to 5 kg / ha. Preparation Examples Example I. 4- [4 '- / 2 ", 4" -dichlorophenoxy / -phenoxy] -valeric acid. 20.3 g of 4'-2 ', 4'-dichlorophenoxyZ-phenol are dissolved in 25 ml of absolute ethanol. 2.12 g of metallic sodium are added thereto, and the ethanol is distilled off after dissolving the sodium. 10 g of y-trylo-lactone are now added to the solid 4- 2 ', 4'-dichlorophenoxy / phenol-isodium and heated to 210 ° C for 24 hours. It is acidified with concentrated hydrochloric acid and the residue is dissolved in toluene. The toluene phase is extracted several times with a saturated aqueous-methanolic hydrogencarbonate solution (50% Hwim). The combined extracts are acidified with concentrated hydrochloric acid and extracted with toluene. After drawing off the solvent under reduced pressure, recrystallization from cyclohexane gives 23.9, i.e. 80% of theoretical yield, of 4- [4 '- (2 ", 55 4" -dichlorophenoxy) -phenoxy] -valeric acid with mp 88 ° C, formula 12. Example II is prepared analogously. 4- [4V4 "-chlorophenoxy] -phenoxy] -valeric acid, m.p. 60 65-66 ° C. Example 3 4- [4 '- / 4" -trifluoromethylphenoxy] -phenoxy] -valeric acid. Calculated: C = 61.0; H = 4.8; F = 16.1. Found: C = 61.1; H = 4.9; F = 15.9. 65 Example IV. 4- [4'- - (2 ", 4" -Dichlorophenoxy) -phenoxy] -valeric acid butyl ester. 25.9 g of 4n (2 ', 4'-dichlorophenoxy) phenol and 14.5 g of potassium carbonate in 150 ml of dimethylformamide were heated under reflux for 1.5 hours. Thereafter, 20 g of 4-chlorovaleuranoic acid butyl ester are added dropwise at 80 ° C. and the mixture is heated to 120 ° C. for 12 hours. After the precipitate of salt has been filtered off, the solvent is distilled off under reduced pressure. The oily residue is dissolved in toluene, washed with dilute sodium hydroxide solution and water, and dried. After the toluene is stripped off under reduced pressure, the residue is distilled at very low pressure. 32.1 g, i.e. 78% of theory, of 4- [4V2 ", 4" -dichlorophenoxy] -phenoxy] -valeric acid butyl ester are obtained. formula 13 boiling point Two, o2 = 206 ° C. By analogy with 4-chlorovaleronitrile: Example 5 4- [4 '- (4 "-trifluoroimethylphenoxy) -phenoxy] -valeronitrile. VI. 4- [4V2 ", 4" -Dichlorophenoxy) -phenoxy] -valeric acid n-propyl ester. 29 g of 4- [4 '- (2H, 4,) -dichlorophenoxy) -phenoxy xy] -valeric acid (from Example 1) is heated with 30 ml of toluene and 12 g of thionyl chloride until gas evolution is complete at 60 ° C. The toluene and excess thionyl chloride are then distilled off under reduced pressure. is dissolved in toluene and added dropwise to a solution of 6 g of n-propanol and 8.5 g of triethylamine in 50 ml of toluene. After the addition, the mixture is stirred for 1 hour at a At 50 ° C, then the triethylamine hydrochloride is filtered off and washed with water. After the solvent has been stripped off, it is distilled under very low pressure. 27.5 g of n-propyl 4- [4 '- (i2 ", 4" -dichlorophenax) -phenoxy] -valeric acid ester are obtained, boiling point Two. oi = 200 ° C, of the formula 14. Example VII. 4- [4V4 "N-trifluoromethylphenoxy] -phenoxy] -valeric acid II-tert-butyl ester. 29 g of 4- [4V4" -trifluoromethyl-phenax / -phenoxy] -valeric acid, 1 ml of concentrated sulfuric acid and 25 ml of butanol 2 is dissolved in 300 ml of chloroform and heated to reflux until the removal of water is complete for about 2 to 4 hours. The mixture is then washed with a neutrally saturated sodium bicarbonate solution, and the solvent is distilled off under reduced pressure. The oily residue is distilled at very low pressure. The yield is 29.2 g, i.e. 87.5% of theory, of 4- [4- (4 "-trifluoromethylphenoxy] -butyl ester) - valeric acid of formula 15, boiling point Two, i = 178 ° C. EXAMPLE VIII 4- [4'-4 "-trifluoromethylphenoxy] -phenoxy] -ipenethanol-1. To a suspension of 1.25 g of lithium aluminum hydride in 50 ml of ether, 20.4 g of 4- [4 '- / 4 "-109937 8-trifluoramethylphenoxyZ-phenoxy-valeric acid isobutyl ester (from Example VII) was added dropwise. the mixture is stirred for an additional hour under reflux, then first slowly added 10 ml of ethyl acetate, then 40 ml of water, and finally stirring vigorously enough N — H 2 SO 4 until the aluminum hydride precipitate is dissolved. The ether is washed neutrally with sodium bicarbonate solution and the solvent is distilled off under reduced pressure. After distillation under very low pressure, 15.4 g, or 90.5% of theoretical yield, 4- [4 ') is obtained. - (4 "-trifluoromethylphenoxy) -phenoxy] -pentanol-1 with boiling point Two, o7 = 174 ° C, with the formula 16. Example IX. 1-chloroacetoxy-4- [4 '- (4 "-trifluoromethylphenoxy) -phenoxy] -pentane. For a solution of 17.0 g of 4- [4V4 H -trifluoromethylphenoxy] -pentanol-1 and 5.55 g of triethylamine in 60 ml. EXAMPLE XVII Dust is obtained by mixing and grinding 10 parts by weight of the active ingredient and 90 parts by weight of talc as inert material in a centrifugal mill. consists, for example, of about 2 to 15 parts by weight of the active ingredient and 98 to 85 parts by weight of inert granulating materials such as attapulgite, pumice and quartz sand. Biological Examples Grass seeds are sown in pots and the preparations according to the invention are formulated as wettable powders were sprayed on the ground surface in different doses. Then the pots were placed in a greenhouse for 4 weeks. The results of the treatment were determined by valuation according to the Bolle's scheme (Nachrichtenblatt des deutschen Pflanzenschutzdienstes 16, 1964, 92-94). I Formula la Tw = temperature Boiling point Example No. 'X 1 XI XII XIII XIV 1 (R) n 4-CF3 4-CFa 4-CF3 4-CF3 4-CF3 Z ^ COOCH3 -COOC2H5 -COOCsHtOi) -COOCH2CH20CH3 -COOCH2CH (CH3) 2 Physical data Two, 2 = 168 ° C Tw0, oo5 = 156 ° C Two, o6 = 169 ° C Tw0 | o5 = 177 ° C Tw0.2 = 187 ° C. Prepared according to example 4 6 6 7 absolute toluene is added dropwise 6.45 g of chloroacetyl chloride is mixed at room temperature. After the addition, the mixture is stirred for an additional hour at 50 ° C., then the precipitate is filtered off, the toluene solution is washed with dilute hydrochloric acid and water and dried. After dragging off the solvent, 18.5 g, i.e. 89% theoretical, of 1-chloroacetyloxy-4- [4V4 H -trifluoromethylphenoxy] pentane of formula 17 are obtained. 1 obtained according to the above examples are summarized in Table I. Preparation examples Example XV. An emulsifiable concentrate is made from 15 parts by weight of active ingredient, 75 parts by weight of cyclohexanes! as a solvent and 10 parts by weight of ethoxylated nonylphenol (10 AeO) as emulsifier. Example XVI. A powder which is easily dispersible in water is obtained by mixing and grinding in a disintegrator 25 parts by weight of the active ingredient, 64 parts by weight of quartz-containing quartz as inert substances, 10 parts by weight of potassium lignin sulphonate and 1 part by weight. sodium oleyl methyl taurate as a wetting and dispersing agent. 65 Ldw- 1 value 1 2 3 4 5 6 7 8 and 9 Harmfulness in% on weeds 100 97.5 to <100 95 to <97.5 90 to <95 85 to <90 75 to < 85 65 to <75 32.5 to <65 0 to <32.5 arable crops 0 0 to 2.5 2.5 to 5 5 to 10 10 to 15 15 to 25 25 to 35 35 to 37.5 67.5 to 100 The results in Table II clearly show that the pre- and post-emergence compounds already at low doses have an excellent herbicidal effect. Claims 1. A herbicide containing active substances and known adjuvants, characterized by the fact that the active ingredient is compounds 109 937 Table II 10 Compound according to example I VI XII III 1 XIV - XI VIII X XIII Dose (kg / ha) 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0, 6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2 , 5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 Application before after before after before after before after before after before after before after before after before after EC 1 2 1 SA 1 1 1 4 1 1, 2 5 - 1 DI - - - - - - - 1 1 1 1 - - - 1 1 - - - - - - - - - - - - - AL - - - - - - - 1 2 1 2 2 ¦ 3 1 1 - 1 1 3 J 1 1 1 1 1 2 1 1 1 1 1 1 2 2 1 1 AS active substance Before = pre-emergence use PO = post-emergence use EC = (single-sided weed) Echinochloa SA = (trichinosis) Setaria DI = (bloodstayer) Digitaria AL = (field fox) Alopecurus of general formula I, where Ri is chlorine, group CF3 or (Ci-C4) -alkyl, Z is -CN, -CS-NH2, -CO-R2 or -CHjj— -O-R3, R2 is hydroxy, -O- -Kat, (Ci-Ci2) - alkoxy, which may be optionally substituted with OH, halogen, CF3, (Ci-C6) alkoxy, (Ci-C4) -alkylthio, phenyl, phenoxy or 60 halophenoxy; the radicals of the formulas 5, 6, 7, - (OC2H4) 2-3-OCmH2m + and / of the formula 8, 9, in which the group of formula 10 is pyrrolidinyl, piperidinyl, morpholinyl, or N-methylpiperazinyl ; a (C5-C6) cycloalkoxy group which may optionally be substituted with (Ci-C4) alkyl and / or halogen; a (C3-C4) alkenyloxy, cyclohexenylxyl, (C3-C4) alkynyloxy group which may optionally be substituted in the 1-position by (Ci-C4) alkyl and / or phenyl; a phenotosyl group which may optionally be substituted by halogen, NO 2 and / or (C 1 -C 6) alkyl; (C 1 -C 6) 4 alkyl: thiol, allylthio, phenylthio, chlorophenylthio, amine, (C 1 -C 4) -alkylamino, hydraoxyethyl-amino, di- (C 1 -C 4) -10-alkylamino, piperidine, pyrrolidine, mor - folin; anilino, which may optionally be substituted by halogen, CF3 and / or (C1-C4) alkyl, and hydrazine, R3 is hydrogen, (C1-C4) nalkyl, (C1-C4) alkylcarbonyl, halo- (C 1 -C 4) alkylcarbonyl, benzoyl which is optionally substituted with halogen, NO 2 and / or with (C 1 -C 4) alkyl; (Ci-C4) -alkylcarbamoyl, di- (Ci-C4) -alkylcaribamoyl, phenylcarbamoyl, which may optionally be substituted by halogen and / or by (Ci-C3) -alkyl; (Ci-C4) -alkylsulfonyl, phenylsulfonyl, group -SO3H or -SO3Ka1; and Cat is equal to the cations of an inorganic or organic base, n is 1-3, and m is 1-6. 2. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is compounds of formula I in which (R 1) n is chlorine in position 4, trifluoromethyl in position 4 or two chlorine atoms in positions 2 and 4 and Z is rhodium n of the formula —CH2 — O — R3 and R3 is as defined in claim 1. 1. 3. The measure according to claim 1 A compound according to claim 1, characterized in that the active ingredient is compounds of formula I, in which (R 1) n is a chlorine atom in position 4 or two chlorine atoms in position 2 and 4, and Z is a radical of formula —CO — R2 and R2 has the meaning given in claim 1. 4. The measure according to claim 1. A composition according to claim 1, characterized in that the active ingredient is a compound of formula 12. The composition according to claim 1, A composition according to claim 1, characterized in that the active ingredient is a compound of formula 18. 6. A composition according to claim 1, A composition according to claim 1, characterized in that the active ingredient is a compound of formula 13. A composition according to claim 1, A composition according to claim 1, characterized in that the active ingredient is a compound of formula 14. 8. A composition according to claim 1, 8. A composition according to claim 1, characterized in that the active ingredient is a compound of formula 15. A composition according to claim 1, 9. A composition according to claim 1, characterized in that the active ingredient is a compound of formula 16. A composition according to claim 1, characterized in that the active ingredient is a compound of the formula 19. A composition according to claim 1, A composition according to claim 1, characterized in that the active ingredient is a compound of formula 20. A composition according to claim 1, A compound according to claim 1, characterized in that the active ingredient is a compound of formula 21.109937 S NH2 FORMULA 11 Ct CH- a "O" O ™ O "°" ^ H ~ CH2CH2C00H FORMULA 12 Cl CH- Cl - ^) - O- S N0CH2CH2CH2CH3 FORMULA 13, Cl, CH3 O Cl-Q ^ dHQH0-CH-CH2CH2-C NOCH2CH2CH3 / FORMULA 14 CH3 / 0 CF3 ^^ ° ^ Q "°" CH "CH2-CH2-C (/ C2H5 O-CH \ FORMULA 15 CH3 CH3 CF3-Q-0hQh0-CH-CH2CH2CH20H FORMULA 16109937 (R, CH, 0 ^ O ^ 0-CH-CH2-CH2- FORMULA 1 (R1] no Koy-oH FORMULA 2 ChL I 3 Y-CH-CH2CH2Z FORMULA 3 OCH.No '-OCH2 — lo5 MODEL 5 MODEL 6 -OCH2J ^ 3 -OGA-N,; CC) alkyl \ C} - C ^ JalkyL MODEL 7 MODEL 8 - ° W..A -NA MODEL 9 MODEL 10109937 CH- , 0 / - \ —v I II Cf3 \ 2 / ° \ 0 / ° "CH" CH2CH2 CH2 ° ~ C ~ CH2Cl FORMULA 17? H3 CL - ((3) -O - / CJ) - O- CH- CH2CH2COOH FORMULA 18 CH3 O CF3- (O) -0 - (^ - 0-CH-CH2CH2-C -OCH, FORMULA A9 ChL O Cf3 \ 2 / ° \ Q / ° "CH" CH2CH2_C "OC3H7 (n) FORMULA 20 CH3 O CF3 - \ O) -0 - ^ O) - O- CH - CH2CH2 C-OC ^ CHICH ^ FORMULA 2-f109937 CH3 R) n- ^ Q ^ O ^ g-OH + Y-CH-CH2CH2Z Formula 2a MODEL 3 9H3 R) - ^^ - 0 - ^^ - O-CH-CHCH Z + HY MODEL 1a SCHEME 1 UV ^ ®-o-®-ch? chJ ^ Ko MODEL 2a MODEL U CH3 rule R) - ^ Vo ^ O ^ OCH-CH2-CH2-COOKat SCHEME 2 National Printing House, Plant No. 6, 863/80 Price PLN 45 PL

Claims (12)

Zastrzezenia patentowe 1. Srodek chwastobójczy, zawierajacy substancje czynna i znane substancje pomocnicze, znamienny tym, ze jako substancje czynna zawiera zwiazki109937 Tablica II 10 Zwiazek wedlug /przy¬ kladu I VI XII III 1 XIV - XI VIII X XIII Dawka (kg/ha) 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 2,5 0,6 Stoso¬ wanie przed po przed po przed po przed po przed po przed po przed po przed po przed po EC 1 2 1 SA 1 1 1 4 1 1, 2 5 - 1 DI — — — — — — — 1 1 1 1 — — — 1 1 — — — — — — — — — — — — — AL — — — — — — — 1 2 1 2 2 ¦ 3 1 1 — 1 1 3 J 1 1 1 1 1 2 1 1 1 1 1 1 2 2 1 1 AS substancja aktywna Przed = stosowanie przed wzejsciem PO = stosowanie po wzejsciu EC = (chwastnica jednostronna) Echinochloa SA = (wlosnica) Setaria DI = (palusznik krwawy) Digitaria AL = (wyczyniec polny) Alopecurus o ogólnym wzorze 1, w którym Ri oznacza chloro¬ wiec, grupe CF3 albo (Ci—C4)-alkil, Z oznacza grupy —CN, —CS—NH2, —CO—R2 albo —CHjj— —O—R3, R2 oznacza grupe hydroksylowa, —O— —Kat, (Ci—Ci2)-alkoksylowa, która moze byc ewentualnie podstawiona przez grupe OH, chloro¬ wiec, grupe CF3, (Ci—C6)-alkoksylowa, (Ci—C4)-al- kilotiolowa, fenylowa, fenoksylowa albo przez 60 grupe chlorowcofenoksylowa; rodniki o wzorach 5, 6, 7, —(OC2H4)2-3—OCmH2m+i/ o wzorze 8, 9, ' w którym grupa o wzorze 10 oznacza rodnik pi- rolidynylowy, piperydynylowy, morfolinylowy, al¬ bo N-metylopiperazynylowy; grupe (C5—C6)-cyklo- 65 alkoksylowa, która ewentualnie moze byc pod-109937 11 12 stawiona przez (Ci—C4)-alkil i/albo chlorowiec; grupe (C3—C4)-alkenyloksylowa, cykloheksenylo- ksylowa, (C3—C4)-alkinyloksylowa, która ewentu¬ alnie moze byc podstawiona w polozeniu 1 przez (Ci—C4)-alkil i/albo fenyl; grupe fenotosylowa, któ- 5 ra ewentualnie moze byc podstawiona przez chlo¬ rowiec, grupe N02 i/albo (Ci—C6)-alkil; grupe (Ci—C6)^alkilo:tiolowa, allilotiolowa, fenylotiolowa, chlorowoofenylotiolowa, aminowa, (Ci—C4)-alkilo- aminowa, hydraksyetylo-aminowa, dwu-(Ci—C4)- 10 -alkiloaminowa, piperydynowa, pirolidynowa, mor- folinowa; anilinowa, która ewentualnie moze byc podstawiona przez chlorowiec, grupe CF3 i/albo przez (Ci—C4)-alkil, oraz grupe hydrazynowa, R3 oznacza wodór, (Ci—C4)nalkil, (Ci—C4)^alkilokarbo- 15 nyl, chlorowco-(Ci—C4)-alkilokarbonyl, benzoil, który ewentualnie jest podstawiony przez chloro¬ wiec, grupe N02 i/albo przez (Ci—C4)-alkil; (Ci— C4)-alkilokarbamoil, dwu-(d—C4)-alkilokaribamoil, fenylokanbamoil, który ewentualnie moze byc pod- 20 stawiony przez chlorowiec i/albo pnzez (Ci—C3)- -alkil; (Ci—C4)-alkilosulfonyl, fenylosujfonyl, gru¬ pe —S03H albo —S03Ka1;, oraz Kat oznacza rów¬ nowaznik kationów zasady nieorganicznej albo or¬ ganicznej, n oznacza liczbe 1—3, oraz m oznacza 25 litere 1—6. Claims 1. A herbicide containing active substances and known adjuvants, characterized in that the active substance is compounds 109937 Table II 10 Compound according to example I VI XII III 1 XIV - XI VIII X XIII Dose (kg / ha) 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2, 5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0.6 2.5 0 , 6 2.5 0.6 Use before after before after before after before after before after before after before after before after EC 1 2 1 SA 1 1 1 4 1 1, 2 5 - 1 DI - - - - - - - 1 1 1 1 - - - 1 1 - - - - - - - - - - - - - AL - - - - - - - 1 2 1 2 2 ¦ 3 1 1 - 1 1 3 J 1 1 1 1 1 2 1 1 1 1 1 1 2 2 1 1 AS active substance Before = pre-emergence use PO = post-emergence use EC = (single-sided weed) Echinochloa SA = (hairbrush) Setaria DI = (bloody finger) Digitaria AL = (foxtail field) Alopecurus of general formula I, in which R 1 is halogen, CF 3 or (C 1 -C 4) -alkyl, Z represents -CN, -C S — NH2, —CO — R2 or —CHjj— —O — R3, R2 is a hydroxyl group, —O— —Kat, (C1 — C12) -alkoxy, which may be optionally substituted by an OH group, a halogen group, CF3, (C 1 -C 6) alkoxy, (C 1 -C 4) alkylthio, phenyl, phenoxy or through the 60 halophenoxy group; the radicals of the formulas 5, 6, 7, - (OC2H4) 2-3-OCmH2m + and / of the formula 8, 9, in which the group of formula 10 is pyrrolidinyl, piperidinyl, morpholinyl, or N-methylpiperazinyl ; a (C5-C6) cycloalkoxy group which may optionally be substituted with (Ci-C4) alkyl and / or halogen; a (C3-C4) alkenyloxy, cyclohexenylxyl, (C3-C4) alkynyloxy group which may optionally be substituted in the 1-position by (Ci-C4) alkyl and / or phenyl; a phenotosyl group which may optionally be substituted by halogen, NO 2 and / or (C 1 -C 6) alkyl; (C 1 -C 6) 4 alkyl: thiol, allylthio, phenylthio, chlorophenylthio, amine, (C 1 -C 4) -alkylamino, hydraoxyethyl-amino, di- (C 1 -C 4) -10-alkylamino, piperidine, pyrrolidine, mor - folin; anilino, which may optionally be substituted by halogen, CF3 and / or (C1-C4) alkyl, and hydrazine, R3 is hydrogen, (C1-C4) nalkyl, (C1-C4) alkylcarbonyl, halo- (C 1 -C 4) alkylcarbonyl, benzoyl which is optionally substituted with halogen, NO 2 and / or with (C 1 -C 4) alkyl; (Ci-C4) -alkylcarbamoyl, di- (Ci-C4) -alkylcaribamoyl, phenylcarbamoyl, which may optionally be substituted by halogen and / or by (Ci-C3) -alkyl; (Ci-C4) -alkylsulfonyl, phenylsulfonyl, group -SO3H or -SO3Ka1; and Cat is equal to the cations of an inorganic or organic base, n is 1-3, and m is 1-6. 2. Srodek wedlug zastrz. 1, znamienny tym, ze, jako substancje czynna zawiera zwiazki o wzorze 1, w którym (Ri)n oznacza atom chloru w polo¬ zeniu 4, trójfluorometyl w polozeniu 4 albo dwa 30 atomy chloru w polozeniu 2 i 4 i Z oznacza rod¬ nik o wzorze —CH2—O—R3 i R3 ma znaczenie podane w zastrz. 1. 2. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is compounds of formula I in which (R 1) n is chlorine in position 4, trifluoromethyl in position 4 or two chlorine atoms in positions 2 and 4 and Z is rhodium and R3 and R3 are as defined in claim 1, 1. 3. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazki o wzorze 1, w którym (Ri)n oznacza atom chloru w polo¬ zeniu 4 albo dwa atomy chloru w polozeniu 2 i 4 i Z oznacza rodnik o wzorze —CO—R2 i R2 ma znaczenie podane w zastrz. 1. 3. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is compounds of formula I, in which (R 1) n is a chlorine atom in position 4 or two chlorine atoms in position 2 and 4, and Z is a radical of formula —CO — R2 and R2 has the meaning given in claim 1. 4. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 12. 4. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula 12. 5. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 18. 5. The measure according to claim A composition according to claim 1, characterized in that the active ingredient is a compound of formula 18. 6. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 13. 6. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula 13. 7. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 14. 7. The measure according to claim A composition according to claim 1, characterized in that the active ingredient is a compound of formula 14. 8. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 15. 8. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula 15. 9. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 16. • 9. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula 16. • 10. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 19. 10. The measure according to claim The compound of claim 1, wherein the active ingredient is a compound of formula 19. 11. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 20. 11. The measure according to claim A process as claimed in claim 1, characterized in that the active ingredient is a compound of formula 20. 12. Srodek wedlug zastrz. 1, znamienny tym, ze jako substancje czynna zawiera zwiazek o wzorze 21.109937 S NH2 WZÓR 11 Ct CH- a"O"0™O"°"^H~CH2CH2C00H WZÓR 12 Cl CH- CI-^)-0- S N0CH2CH2CH2CH3 WZÓR 13 ,Cl , CH3 O Cl-Q^dHQH0-CH-CH2CH2-C NOCH2CH2CH3 / WZÓR 14 CH3 /0 CF3^^°^Q"°"CH"CH2-CH2-C( /C2H5 O-CH \ WZÓR 15 CH3 CH3 CF3-Q-0hQh0-CH-CH2CH2CH20H WZÓR 16109937 (R, CH, 0^O^0-CH-CH2-CH2- WZÓR 1 (R1]n o Koy-oH WZÓR 2 ChL I 3 Y-CH-CH2CH2Z WZÓR 3 OCH. No' -OCH2—lo5 WZÓR 5 WZÓR 6 -OCH2J^3 -OGA-N, ;C-C)alkyl \C}- C^JalkyL WZÓR 7 WZÓR 8 -°W..A -N A WZÓR 9 WZÓR 10109937 CH-, 0 /—\ —v I II Cf3 \2/ ° \0/ °"CH"CH2CH2 CH2°~C~CH2Cl WZÓR 17 ?H3 CL -((3)-O -/CJ)- O- CH- CH2CH2COOH WZÓR 18 CH3 O CF3-(O)-0-(^-0-CH-CH2CH2-C -OCH, WZÓR A9 ChL O Cf3 \2/ ° \Q/ ° " CH" CH2CH2_C "OC3H7(n) WZÓR 20 CH3 O CF3 -\O)-0 -^O)- O- CH - CH2CH2 C-OC^CHICH^ WZÓR 2-f109937 CH3 R)n-^Q^O^g-OH + Y-CH-CH2CH2Z Za5ada WZÓR 2a WZÓR 3 9H3 R)—^^-0-^^-O-CH-CHCH Z + HY WZÓR 1a SCHEMAT 1 UV^®-o-®-ch ? chJ^Ko WZÓR 2a WZÓR U CH3 zasada R) —^Vo^O^OCH-CH2-CH2-COOKat SCHEMAT 2 Drukarnia Narodowa, Zaklad Nr 6, 863/80 Cena 45 zl PL12. The measure according to claim A compound according to claim 1, characterized in that the active ingredient is a compound of formula 21.109937 S NH2 FORMULA 11 Ct CH- a "O" O ™ O "°" ^ H ~ CH2CH2C00H FORMULA 12 Cl CH- Cl - ^) - O- S N0CH2CH2CH2CH3 FORMULA 13, Cl, CH3 O Cl-Q ^ dHQH0-CH-CH2CH2-C NOCH2CH2CH3 / FORMULA 14 CH3 / 0 CF3 ^^ ° ^ Q "°" CH "CH2-CH2-C (/ C2H5 O-CH \ FORMULA 15 CH3 CH3 CF3-Q-0hQh0-CH-CH2CH2CH20H FORMULA 16109937 (R, CH, 0 ^ O ^ 0-CH-CH2-CH2- FORMULA 1 (R1] no Koy-oH FORMULA 2 ChL I 3 Y-CH-CH2CH2Z FORMULA 3 OCH. No '-OCH2 — lo5 PATTERN 5 PATTERN 6 -OCH2J ^ 3 -OGA-N,; CC) alkyl \ C} - C ^ JalkyL PATTERN 7 PATTERN 8 - ° W..A -NA PATTERN 9 MODEL 10109937 CH- , 0 / - \ —v I II Cf3 \ 2 / ° \ 0 / ° "CH" CH2CH2 CH2 ° ~ C ~ CH2Cl FORMULA 17? H3 CL - ((3) -O - / CJ) - O- CH- CH2CH2COOH FORMULA 18 CH3 O CF3- (O) -0 - (^ - 0-CH-CH2CH2-C -OCH, FORMULA A9 ChL O Cf3 \ 2 / ° \ Q / ° "CH" CH2CH2_C "OC3H7 (n) FORMULA 20 CH3 O CF3 - \ O) -0 - ^ O) - O- CH - CH2CH2 C-OC ^ CHICH ^ FORMULA 2-f109937 CH3 R) n- ^ Q ^ O ^ g-OH + Y-CH-CH2CH2Z Formula 2a MODEL 3 9H3 R) - ^^ - 0 - ^^ - O-CH-CHCH Z + HY MODEL 1a SCHEME 1 UV ^ ®-o-®-ch? chJ ^ Ko MODEL 2a MODEL U CH3 rule R) - ^ Vo ^ O ^ OCH-CH2-CH2-COOKat SCHEME 2 National Printing House, Plant No. 6, 863/80 Price PLN 45 PL
PL1977200438A 1976-08-25 1977-08-24 Herbicide PL109937B1 (en)

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DE2433067B2 (en) * 1974-07-10 1977-11-24 a- [4-(4" Trifluormethylphenoxy)-phenoxy] -propionsäuren und deren Derivate, Verfahren zu ihrer Herstellung und diese enthaltende herbizide Mittel Hoechst AG, 6000 Frankfurt ALPHA SQUARE BRACKETS ON 4- (4 'TRIFLUORMETHYLPHENOXY) -PHENOXY SQUARE BRACKETS ON PROPIONIC ACIDS AND THEIR DERIVATIVES, METHOD FOR THEIR PRODUCTION AND HERBICIDAL AGENTS CONTAINING THESE
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