DK167975B1 - 2-ANILINO-PYRIMIDINE DERIVATIVES AND THEIR PREPARATION AND USE AS FUNGICIDE OR INSECTICIDE - Google Patents
2-ANILINO-PYRIMIDINE DERIVATIVES AND THEIR PREPARATION AND USE AS FUNGICIDE OR INSECTICIDE Download PDFInfo
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- DK167975B1 DK167975B1 DK317588A DK317588A DK167975B1 DK 167975 B1 DK167975 B1 DK 167975B1 DK 317588 A DK317588 A DK 317588A DK 317588 A DK317588 A DK 317588A DK 167975 B1 DK167975 B1 DK 167975B1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
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- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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Description
DK 167975 B1DK 167975 B1
Den foreliggende opfindelse angår hidtil ukendte 2-ani-lino-pyrimidin-derivater med den nedenfor anførte almene formel I. Opfindelsen angår tillige fremstillingen af 5 disse forbindelser samt agrokemiske insekticider eller fungicider, der som aktivt stof indeholder mindst én af disse forbindelser. Desuden angår opfindelsen en fremgangsmåde til bekæmpelse af eller beskyttelse mod angreb af skadeinsekter eller fytopatogene fungi på 10 kulturplanter.The present invention relates to novel 2-anino-pyrimidine derivatives of the general formula I. The invention also relates to the preparation of these compounds as well as agrochemical insecticides or fungicides containing as at least one of these compounds. In addition, the invention relates to a method for controlling or protecting against infestation of pest insects or phytopathogenic fungi on 10 culture plants.
Forbindelserne ifølge opfindelsen har den almene formel _ JR·3 · N=* *The compounds of the invention have the general formula: JR · 3 · N = +
OH2XIUOH2XIU
hvori Ri og R2 hver for sig betyder hydrogen, halogen, C( 1-3)-alkyl, C(l-2)-halogenalkyl, C(l-3)-alkoxy eller 15 C(l-3)-halogenalkoxy, R3 betyder hydrogen, C(l-4)-alkyl, med halogen eller hydroxy substitueret C( 1-2)-alkyl, cyclopropyl eller med halogen og/eller methyl substitueret cyclopropyl, R4 betyder C(1-8)-alkyl, med halogen, hydroxy, cyano, C( l-4)-alkoxy, C(3-4)-alkoxyalkoxy eller 20 C(1-3)-alkylthio substitueret C(2-6)-alkyl, C(3-6)- alkenyl, C(3-6)-alkynyl, C(3-7)-cycloalkyl eller med methyl substitueret C(3-7)-cycloalkyl, og X betyder oxygen eller svovl.wherein R 1 and R 2 are each independently hydrogen, halogen, C (1-3) alkyl, C (1-2) haloalkyl, C (1-3) alkoxy or C (1-3) halogenalkoxy, R3 means hydrogen, C (1-4) alkyl, with halogen or hydroxy substituted C (1-2) alkyl, cyclopropyl or with halogen and / or methyl substituted cyclopropyl, R4 means C (1-8) alkyl, with halogen , hydroxy, cyano, C (1-4) alkoxy, C (3-4) alkoxyalkoxy or C (1-3) alkylthio substituted C (2-6) alkyl, C (3-6) alkenyl , C (3-6) -alkynyl, C (3-7) -cycloalkyl or methyl substituted C (3-7) -cycloalkyl, and X means oxygen or sulfur.
Ved alkyl selv eller som bestanddel af en anden sub-25 stituent, såsom halogenalkyl, alkoxy eller halogen- alkoxy, skal der afhængigt af antallet af de nævnte carbonatomer eksempelvis forstås methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl samt deres isomerer, som f.eks. isopropyl, isobutyl, tert-butyl og isopentyl.By alkyl itself or as a constituent of another substituent such as haloalkyl, alkoxy or haloalkoxy, depending on the number of carbon atoms mentioned, is meant, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and their isomers, such as isopropyl, isobutyl, tert-butyl and isopentyl.
30 Halogen betyder fluor, chlor, brom eller iod. Halogen- 2 DK 167975 B1 alkyl og halogenalkoxy betegner mono- til perhalogenerede grupper, som f.eks. CHCI2, CH2F, CCI3, CH2CI, CHF2, CH2CH2Br, C2CI5, CHBr og CHBrCl, fortrinsvis CF3. Alkenyl 5 betyder eksempelvis propenyl-(l), allyl, butenyl-(l), butenyl-(2) eller butenyl-(3) samt kæder med flere dobbeltbindinger. Alkynyl betyder f.eks. propynyl-(2), butynyl-(l), butynyl-(2) eller pentynyl-(4), fortrinsvis propargyl. Cycloalkyl betyder alt efter antallet af de 10 anførte carbonatomer eksempelvis cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl eller cycloheptyl.Halogen means fluorine, chlorine, bromine or iodine. Halo-2 DK 167975 B1 alkyl and haloalkoxy denote mono- to perhalogenated groups, such as e.g. CHCl2, CH2F, CCl3, CH2Cl, CHF2, CH2CH2Br, C2Cl5, CHBr and CHBrCl, preferably CF3. Alkenyl 5 means, for example, propenyl- (1), allyl, butenyl- (1), butenyl- (2) or butenyl- (3) and several double bond chains. Alkynyl means e.g. propynyl (2), butynyl (1), butynyl (2) or pentynyl (4), preferably propargyl. Cycloalkyl means, depending on the number of the 10 carbon atoms listed, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.
Forbindelser med en N-pyrimidylanilinstruktur er kendte.Compounds having an N-pyrimidylaniline structure are known.
Fra beskrivelsen til JP-patentansøgning Sho 56-65804 samt fra DD-patentskrift nr. 151.404 kendes forbindelser med 15 denne grundstruktur og med virkning mod planteskadeorga-nismer. De kendte forbindelser har dog ikke kunnet opfylde de i praksis stillede betingelser på tilfredsstillende måde i fuld udstrækning. Forbindelserne ifølge opfindelsen med formlen I adskiller sig på karakteristisk måde fra de 20 kendte forbindelser ved at indeholde en aliphatoxymethyi-eller aliphatthiomethylgruppe i 4-stillingen i pyrimidin-ringen. Derved opnår de hidtil ukendte forbindelser ifølge opfindelsen en overraskende høj fungicid virkning og insekticid virkning, hvilket illustreres nærmere i det 25. følgende.From the specification for JP patent application Sho 56-65804 and from DD patent specification 151,404, compounds having this basic structure and with effect against plant damage organisms are known. However, the known compounds have not been able to fully satisfy the conditions set in practice in a satisfactory manner. The compounds of the invention of formula I characteristically differ from the 20 known compounds by containing an aliphatoxymethyl or aliphatthiomethyl group at the 4-position of the pyrimidine ring. Thereby, the novel compounds of the invention achieve a surprisingly high fungicidal and insecticidal activity, which is further illustrated in the following.
Forbindelserne med formlen I er ved stuetemperatur stabile olier, harpikser eller faste stoffer, som udmærker sig ved værdifulde mikrobicide egenskaber. De kan anvendes præventivt og kurativt inden for agrarsektoren og beslæg-30 tede områder til bekæmpelse af planteskadelige mikroorganismer. De aktive stoffer ifølge opfindelsen med formlen I udmærker sig ved lave anvendelseskoncentrationer ikke blot ved fremragende insekticid og fungicid virkning men også ved særdeles god planteforligelighed.The compounds of formula I are at room temperature stable oils, resins or solids which are characterized by valuable microbicidal properties. They can be used preventively and curatively in the agricultural sector and related areas to control plant harmful microorganisms. The active substances according to the invention of formula I are distinguished by low application concentrations not only by excellent insecticide and fungicide effect but also by very good plant compatibility.
35 En vigtig gruppe plantefungicider er forbindelser med formlen I, hvori Εχ og R2 betyder hydrogen.An important group of plant fungicides are compounds of formula I wherein Εχ and R 2 represent hydrogen.
3 DK 167975 B1 . En særlig gruppe anilino-pyrimidin-derivater udgør forbindelser med formlen I, hvori og R2 hver for sig betyder hydrogen, halogen, C(1-3)-alkyl, C(l-2)-halogenalkyl, 5 C(l-3)-alkoxy eller C(l-3)-halogenalkoxy, R3 betyder hydrogen, C(1-4)-alkyl eller cyclopropyl, R4 betyder C(1-8)-alkyl, med halogen, hydroxy, cyano, C(l-4)-alkoxy, C(3-4)-alkoxyalkoxy, C(1-3)-alkylthio substitueret C(2-6)-alkyl, C( 3-6)-alkenyl, C(3-6)-alkynyl, 10 C(5-7)-cycloalkyl eller med methyl substitueret C(5-7)-cycloalkyl, og X betyder oxygen eller svovl.3 DK 167975 B1. A particular group of anilino-pyrimidine derivatives are compounds of Formula I wherein and R 2 are each independently hydrogen, halogen, C (1-3) -alkyl, C (1-2) -haloalkyl, 5C (1-3) -alkoxy or C (1-3) haloalkoxy, R3 means hydrogen, C (1-4) alkyl or cyclopropyl, R4 means C (1-8) alkyl, with halogen, hydroxy, cyano, C (1-4) ) -alkoxy, C (3-4) -alkoxyalkoxy, C (1-3) -alkylthio substituted C (2-6) -alkyl, C (3-6) -alkenyl, C (3-6) -alkynyl, 10 C (5-7) -cycloalkyl or methyl-substituted C (5-7) -cycloalkyl, and X means oxygen or sulfur.
Følgende grupper aktive stoffer foretrækkes på grund af deres udtalte biocide virkning, især plantefungicide virkning: 15 Gruppe la:The following groups of active substances are preferred because of their pronounced biocidal activity, especially plant fungicidal activity: Group 1a:
Forbindelser med formlen I, hvori R^ og R2 hver for sig betyder hydrogen, fluor, chlor, brom, C(l-3)-alkyl, C(l-2)-halogenalkyl, C(l-3)-alkoxy eller C(l-2)-halogen-alkoxy, R3 betyder hydrogen, C(l-3)-alkyl eller 20 cyclopropyl, R4 betyder C( 1-6)-alkyl, med halogen, hydroxy, cyano, C(l-3)-alkoxy, C(3-4)-alkoxyalkoxy eller C(1-2)-alkylthio substitueret C(2-4)-alkyl, C3~alkenyl, C3~alkynyl eller usubstitueret eller med methyl substitueret C( 6-7)-cycloalkyl, og X betyder oxygen eller 25 svovl.Compounds of Formula I wherein R 1 and R 2 each represent hydrogen, fluoro, chloro, bromo, C (1-3) alkyl, C (1-2) haloalkyl, C (1-3) alkoxy or C (1-2) halo-alkoxy, R3 means hydrogen, C (1-3) alkyl or cyclopropyl, R4 represents C1-C6 alkyl, with halogen, hydroxy, cyano, C (1-3) -alkoxy, C (3-4) -alkoxyalkoxy or C (1-2) -alkylthio substituted C (2-4) -alkyl, C3-alkenyl, C3-alkynyl or unsubstituted or methyl-substituted C (6-7) - cycloalkyl, and X is oxygen or sulfur.
Blandt de ovenfor anførte forbindelser er en særlig fore-trukken gruppe sådanne, hvori R^ og R2 betyder hydrogen (gruppe laa).Among the compounds listed above, a particularly preferred group is those wherein R 1 and R 2 are hydrogen (group 1 a).
Gruppe lb: 30 Forbindelser med formlen I, hvori R^ og R2 hver for sig betyder hydrogen, fluor, chlor, brom, C(1-3)-alkyl, C(l-3)-alkoxy, trifluormethyl, -OCHF2, -OCF2CHF2, -0CF2CHC1F, -OCF2CHCl2 eller -OCF2CCI2F, R3 betyder hydr- 4 DK 167975 B1 ogen, methyl, ethyl eller n-propyl, R4 betyder C(l-4)-alkyl, med halogen, hydroxy, cyano, C(l-2)-alkoxy eller C(1-2)-alkylthio substitueret C(2-3)-alkyl, 5 C(3-6)-alkenyl, C(3-6)-alkynyl eller cyclohexyl, og X betyder oxygen eller svovl.Group 1b: Compounds of formula I wherein R 1 and R 2 are each independently hydrogen, fluoro, chloro, bromo, C (1-3) -alkyl, C (1-3) -alkoxy, trifluoromethyl, -OCHF 2 - OCF2CHF2, -OCF2CHC1F, -OCF2CHCl2 or -OCF2CCl2F, R3 means hydr, methyl, ethyl or n-propyl, R4 means C (1-4) alkyl, with halogen, hydroxy, cyano, C (1) -2) alkoxy or C (1-2) alkylthio substituted C (2-3) alkyl, 5 C (3-6) -alkenyl, C (3-6) -alkynyl or cyclohexyl, and X means oxygen or sulfur.
Blandt disse forbindelser udgør en særlig foretrukken gruppe sådanne, hvori Ri og R2 betyder hydrogen (gruppe lbb).Of these compounds, a particularly preferred group is those wherein R 1 and R 2 are hydrogen (group 1bb).
10 Gruppe lc;Group lc;
Forbindelser med formlen I, hvori Ri og R2 hver for sig betyder hydrogen, fluor, chlor, brom, C(1-2)-alkyl, C(l-2)-alkoxy, trifluormethyl, -OCHF2, -OCF3, -OCF2CHF2, eller -OCF2CHCIF, R3 betyder hydrogen eller C(l-2)-alkyl, 15 R4 betyder C(1-3)-alkyl, med halogen, hydroxy, cyano, C(l-2)-alkoxy eller C(1-2)-alkylthio substitueret C2-alkyl, C(3-4)-alkenyl eller C(3-4)-alkynyl, og X betyder oxygen eller svovl.Compounds of formula I wherein R 1 and R 2 are each independently hydrogen, fluorine, chlorine, bromine, C (1-2) alkyl, C (1-2) alkoxy, trifluoromethyl, -OCHF2, -OCF3, -OCF2CHF2, or -OCF2CHCIF, R3 means hydrogen or C (1-2) alkyl, R4 means C (1-3) alkyl, with halogen, hydroxy, cyano, C (1-2) alkoxy or C (1-2) ) -alkylthio is substituted C2-alkyl, C (3-4) -alkenyl or C (3-4) -alkynyl, and X is oxygen or sulfur.
Blandt de ovenfor anførte forbindelser foretrækkes især 20 sådanne, hvori R^ og R2 betyder hydrogen, og X betyder oxygen (gruppe lcc).Of the compounds listed above, 20 are particularly preferred, wherein R 1 and R 2 are hydrogen and X is oxygen (group 1 cc).
Gruppe ld:Group ld:
Forbindelser med formlen I, hvori R^ og R2 hver for sig betyder hydrogen, fluor, chlor, brom, C(1-2)-alkyl, 25 C(l-2)-alkoxy, trifluormethyl eller -OCHF2, R3 betyder methyl, R4 betyder C(l-2)-alkyl, med fluor, chlor, brom, . cyano, C(l-2)-alkoxy eller methylthio substitueret C2~alkyl, allyl eller propargyl, og X betyder oxygen eller svovl.Compounds of formula I wherein R 1 and R 2 are each independently hydrogen, fluoro, chloro, bromo, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, trifluoromethyl or -OCHF 2, R 3 is methyl, R 4 represents C (1-2) alkyl, with fluoro, chloro, bromo,. cyano, C (1-2) alkoxy or methylthio substituted C2 alkyl, allyl or propargyl, and X is oxygen or sulfur.
30 Blandt disse forbindelser foretrækkes især sådanne, hvori Ri og R2 betyder hydrogen, og X betyder oxygen (gruppe .ldd).Among these compounds, particularly preferred are those wherein R 1 and R 2 are hydrogen and X is oxygen (group .ldd).
5 DK 167975 B15 DK 167975 B1
Gruppe 2a:Group 2a:
Forbindelser med formlen I, hvori og R2 hver for sig betyder hydrogen, halogen, C(1-2)-alkyl, halogenmethyl, 5 C(l-2)-alkoxy eller C( 1-2)-halogenalkoxy, R3 betyder hydrogen, C(1-3)-alkyl, med halogen eller hydroxy substitueret C(1-2)-alkyl, cyclopropyl eller med halogen og/eller methyl en til tre gange ens eller forskelligt substitueret cyclopropyl, R4 betyder C(1-4)-alkyl, med 10 halogen, cyano, C( 1-2)-alkoxy eller C(1-2)-alkylthio substitueret C(2-3)-alkyl, C(3-6)-alkenyl, C(3-6)-alkynyl eller C(3-7)-cycloalkyl, og X betyder oxygen eller svovl.Compounds of formula I wherein and R 2 are each independently hydrogen, halogen, C 1 -C 2 alkyl, halo-methyl, 5 C (1-2) alkoxy or C (1-2) -haloalkoxy, R 3 is hydrogen, C (1-3) alkyl, with halogen or hydroxy substituted C (1-2) alkyl, cyclopropyl or with halogen and / or methyl one to three times the same or differently substituted cyclopropyl, R4 means C (1-4) - alkyl, with halogen, cyano, C (1-2) alkoxy or C (1-2) alkylthio substituted C (2-3) alkyl, C (3-6) -alkenyl, C (3-6) -alkynyl or C (3-7) -cycloalkyl, and X means oxygen or sulfur.
Blandt ovennævnte forbindelser foretrækkes især sådanne, hvori R^ og R2 betyder hydrogen (gruppe 2aa).Of the above-mentioned compounds, especially those in which R 1 and R 2 are hydrogen (group 2aa) are preferred.
15 Gruppe 2b:Group 2b:
Forbindelser med formlen I, hvori Ri og R2 hver for sig betyder hydrogen, fluor, chlor, brom, methyl, trifluor-methyl, methoxy eller dif luorme thoxy, R3 betyder hydrogen, C(1-3)-alkyl, med halogen eller hydroxy substitu-20 ret C(1-2)-alkyl, cyclopropyl, eller med halogen og/eller methyl en til tre gange ens eller forskelligt substitueret cyclopropyl, R4 betyder C( 1-3)-alkyl, med fluor, chlor eller C(l-2)-alkoxy substitueret C(2-3)-alkyl, C(3-6)-alkenyl, C(3-6)-alkynyl eller C(3-6)-cycloalkyl, og X 25 betyder oxygen eller svovl.Compounds of Formula I wherein R 1 and R 2 are each hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or difluoromethoxy, R 3 is hydrogen, C 1 -C 3 alkyl, with halogen or hydroxy substituted C (1-2) alkyl, cyclopropyl, or with halogen and / or methyl one to three times the same or differently substituted cyclopropyl, R 4 represents C (1-3) alkyl, with fluoro, chloro or C ( 1-2-alkoxy substituted C (2-3) -alkyl, C (3-6) -alkenyl, C (3-6) -alkynyl or C (3-6) -cycloalkyl, and X is oxygen or sulfur .
Blandt de umiddelbart ovenfor anførte forbindelser foretrækkes især sådanne, hvori R^ og R2 betyder hydrogen (gruppe 2bb).Among the compounds listed above are particularly preferred, wherein R 1 and R 2 are hydrogen (group 2bb).
Gruppe 2c: 30 Forbindelser med formlen X, hvori R^ og R2 hver for sig betyder hydrogen, fluor, chlor, methyl, trifluormethyl, 6 DK 167975 B1 methoxy eller difluormethoxy, R3 betyder C(1-3)-alkyl, med halogen eller hydroxy substitueret methyl, cyclopropyl eller med halogen eller methyl mono- til trisubstitueret 5 cyclopropyl, R4 betyder C(1-3)-alkyl, med fluor, chlor eller methoxy substitueret C(2-3)-alkyl, C(3-4)-alkenyl, C(3-4)-alkynyl, cyclopropyl eller cyclohexyl, og X betyder oxygen.Group 2c: Compounds of formula X wherein R 1 and R 2 are each independently hydrogen, fluoro, chloro, methyl, trifluoromethyl, B1 methoxy or difluoromethoxy, R 3 is C (1-3) alkyl, with halogen or hydroxy substituted methyl, cyclopropyl or with halogen or methyl mono- to trisubstituted cyclopropyl, R 4 is C 1 -C 3 alkyl, with fluoro, chloro or methoxy substituted C (2-3) -alkyl, C (3-4) -alkenyl, C (3-4) -alkynyl, cyclopropyl or cyclohexyl, and X is oxygen.
Blandt de ovenfor anførte forbindelser er en særlig fore-10 trukken gruppe sådanne, hvori R^ og R2 betyder hydrogen (gruppe 2cc).Among the compounds listed above, a particularly preferred group is those wherein R 1 and R 2 are hydrogen (group 2cc).
Gruppe 2d:Group 2d:
Forbindelser med formlen I, hvori R^ og R2 betyder hydrogen, R3 betyder C(l-3)-alkyl, med fluor, chlor eller brom 15 substitueret methyl, cyclopropyl eller med chlor eller methyl substitueret cyclopropyl, R4 betyder C(1-3)-alkyl, 2-chlorethyl, 2,2,2-trifluorethyl, allyl eller propargyl, og X betyder oxygen.Compounds of Formula I wherein R 1 and R 2 are hydrogen, R 3 is C (1-3) alkyl, with fluoro, chloro or bromo substituted methyl, cyclopropyl or with chloro or methyl substituted cyclopropyl, R 4 is C (1-3) ) -alkyl, 2-chloroethyl, 2,2,2-trifluoroethyl, allyl or propargyl, and X is oxygen.
Som eksempler på særligt foretrukne forbindelser kan 20 nævnes 2-phenylamino-4-methyl-6-methoxymethyl-pyrimidin (forbindelse nr. 1) og 2-phenylamino-4-cyclopropyl-6-methoxymethyl-pyrimidin (forbindelse nr. 10).Examples of particularly preferred compounds may be mentioned 2-phenylamino-4-methyl-6-methoxymethyl-pyrimidine (compound # 1) and 2-phenylamino-4-cyclopropyl-6-methoxymethyl-pyrimidine (compound # 10).
Fremgangsmåden ifølge opfindelsen til fremstilling af forbindelserne med formlen I er ejendommelig ved, at man 25 1. omsætter et phenylguanidinsalt med formlenThe process of the invention for the preparation of the compounds of formula I is characterized by the reaction of a phenylguanidine salt of the formula
Rj. «TU ® 2 A® (n.) ΉΗ2 eller den grundliggende guanidin med formlenRj. «TU ® 2 A® (n.) ΉΗ2 or the basic guanidine of the formula
Vw" kh2 7 DK 167975 B1 med en diketon med formlen O 0Vw "kh2 7 with a diketone of the formula O 0
Il il r3—c—CH2—C—CH2XR4 (III) 5 uden opløsningsmiddel eller i et aprotisk opløsningsmiddel, fortrinsvis dog i et protisk opløsningsmiddel ved temperaturer fra 60 til 160°C, fortrinsvis fra 60 til 110°C, eller 2. i en flertrinsfremgangsmåde: 10 2.1 omsætter urinstof med formlen NH2 0=C^ (IV) NH2 med en keton med formlen 15 0 0In a non-solvent or aprotic solvent, preferably, however, in a protic solvent at temperatures of 60 to 160 ° C, preferably 60 to 110 ° C, or 2. a multistage process: 2.1 2.1 reacting urea of formula NH 2 O = C 2 (IV) NH 2 with a ketone of formula 15 0 0
li IIli II
R3—C—CH2—C—CH2XR4 (III) i nærværelse af en syre i et indifferent opløsningsmiddel ved temperaturer fra 20 til 140°C, fortrinsvis fra 40 til 100°C, og derefter ved det anvendte opløsningsmiddels 20 tilbagesvalingstemperatur cycliserer til en pyrimidinfor-bindelse med formlen /3 H0--( ). (V) N-*\ CH2XRi* og 2.2 omsætter den dannede forbindelse med formlen V med 25 overskud af POCI3 uden opløsningsmiddel eller et over for POCI3 indifferent opløsningsmiddel ved temperaturer fra 50 .til 110°C, fortrinsvis ved tilbagesvalingstemperaturen for 8 DK 167975 B1 POCI3, til dannelse af en forbindelse med formlen /R3 · ,N— ( ci—( ;· (vi) N=.R3-C-CH2-C-CH2XR4 (III) in the presence of an acid in an inert solvent at temperatures from 20 to 140 ° C, preferably from 40 to 100 ° C, and then at the reflux temperature of the solvent used, cyclizes to a pyrimidine feed. compound of formula / 3H0 - (). (V) N - * \ CH 2 X R 1 and 2.2 react the compound of formula V with 25 excess of POCl 3 without solvent or a solvent inert to POCl 3 at temperatures from 50 to 110 ° C, preferably at the reflux temperature of 8 DK 167975 B1 POCl 3, to form a compound of the formula / R 3 ·, N - (ci - (; · (vi) N =.
ch2xr^ og 5 2.3 omsætter den dannede forbindelse med formlen VI med en anilinforbindelse med formlen xRland 2 2.3 react the formed compound of formula VI with an aniline compound of formula xR1
y-VY-V
HZN ' *· (VII) •=,/\ R2 afhængigt af fremgangsmådebetingelserne enten a) i nærværelse af en protonacceptor, såsom overskud af 10 anilinforbindelsen med formlen VII eller en uorganisk base, uden opløsningsmiddel eller i et protisk eller aprotisk opløsningsmiddel eller b) i nærværelse af en syre i et indifferent opløsningsmiddel ved temperaturer fra 60 til 120°C, fortrinsvis fra 15 80 til 100°C, eller 3. i en totrinsfremgangsmåde 3.1 cycliserer et guanidiniumsalt med formlen NH2® H2N—Αθ (VIII) 20 . NH2 med en diketon med formlenHZN + (VII) = =, / R2 depending on the process conditions either a) in the presence of a proton acceptor such as excess of the aniline compound of formula VII or an inorganic base, without solvent or in a protic or aprotic solvent or b) in the presence of an acid in an inert solvent at temperatures from 60 to 120 ° C, preferably from 80 to 100 ° C, or 3. In a two-step process 3.1, a guanidinium salt of the formula NH2® H2N-Αθ (VIII) 20 cycles. NH2 with a diketone of the formula
O OISLAND ISLAND
l> Hl> H
R3—C—ch2—c—ch2xr4 (III) 9 DK 167975 B1 a) uden opløsningsmiddel ved temperaturer fra 100 til 160°C, fortrinsvis fra 120 til 150°C, eller b) i et protisk eller aprotisk opløsningsmiddel eller en 5 blanding af protiske og aprotiske opløsningsmidler ved temperaturer fra 30 til 140°C/ fortrinsvis fra 60 til 120°C, til dannelse af en pyrimidinforbindelse med formlen Μ-/' H2N—*\ /* (IX) N=\ CH2XRi.R3-C-ch2-c-ch2xr4 (III) 9 a) without solvent at temperatures from 100 to 160 ° C, preferably from 120 to 150 ° C, or b) in a protic or aprotic solvent or a mixture of protic and aprotic solvents at temperatures from 30 to 140 ° C / preferably from 60 to 120 ° C, to form a pyrimidine compound of formula Μ- / 'H2N - * \ / * (IX) N = \ CH2XRi.
10 og 3.2 omsætter den dannede forbindelse med formlen IX med en forbindelse med formlen y—( ? <3!) ·=· under fraspaltning af HY i nærværelse af en protonacceptor 15 i aprotiske opløsningsmidler ved temperaturer fra 30 til . 140°C, fortrinsvis fra 60 til 120°C, hvor substituenterne Ri til R4 og X i formlerne II til X har de under formlen I angivne betydninger, A® betyder en syreanion, og Y betyder halogen.10 and 3.2, the compound of formula IX formed is reacted with a compound of formula y - (? <3!) · = Decomposing HY in the presence of a proton acceptor 15 in aprotic solvents at temperatures from 30 to. 140 ° C, preferably from 60 to 120 ° C, where the substituents R 1 to R 4 and X in formulas II to X have the meanings given under formula I, A® means an acid anion and Y means halogen.
20 I de ovenfor beskrevne fremgangsmåder kan der som syre-. anionen A® i forbindelserne med formlerne Ila og VIII eksempelvis anvendes følgende salte: carbonat, hydrogencarbonat, nitrat, halogenid, sulfat eller hydrogensulfat. Ved halogenid skal forstås fluorid, 25 chlorid, bromid eller iodid, fortrinsvis chlorid eller bromid.In the above-described methods, as an acid. For example, the anion A® in the compounds of formulas 11a and VIII uses the following salts: carbonate, hydrogen carbonate, nitrate, halide, sulfate or hydrogen sulfate. Halide is meant fluoride, chloride, bromide or iodide, preferably chloride or bromide.
Som syrer anvendes fortrinsvis uorganiske syrer, såsom 10 DK 167975 B1 f.eks. hydrogenhalogenidsyrer, eksempelvis hydrogen-fluoridsyre, hydrogenchloridsyre eller hydrogenbromidsyre, samt svovlsyre, phosphorsyre eller salpetersyre. Der kan 5 imidlertid også anvendes egnede organiske syrer.Preferably as acids are used inorganic acids such as e.g. hydrogen halide acids, for example hydrogen fluoric acid, hydrochloric acid or hydrogen bromic acid, as well as sulfuric acid, phosphoric acid or nitric acid. However, suitable organic acids may also be used.
Som protonacceptorer anvendes eksempelvis uorganiske baser, såsom f.eks. alkalimetal- eller jordalkalimetal-forbindelser, f.eks. hydroxiderne, oxiderne eller carbonaterne af lithium, natrium, kalium, magnesium, 10 calcium, strontium og barium, eller også hydrider, f.eks. natriumhydrid.As proton acceptors, for example, inorganic bases such as e.g. alkali metal or alkaline earth metal compounds, e.g. the hydroxides, oxides or carbonates of lithium, sodium, potassium, magnesium, calcium, strontium and barium, or also hydrides, e.g. sodium hydride.
I de ovenfor beskrevne fremgangsmåder kan der under hensyntagen til de pågældende reaktionsbetingelser eksempelvis anvendes følgende opløsningsmidler: 15 Halogencarbonhydrider, især chlorcarbonhydrider, såsom tetrachlorethylen, tetrachlorethan, dichlorpropan, methylenchlorid, dichlorbutan, chloroform, chlomaphtha-len, carbontetrachlorid, trichlorethan, trichlorethylen, pentachlorethan, difluorbenzen, 1,2-dichlorethan, 20 1,1-dichlorethan, 1,2-cis-dichlorethylen, chlorbenzen, . fluorbenzen, brombenzen, dichlorbenzen, dibrombenzen, chlortoluen eller trichlortoluen, ethere, såsom ethyl-propylether, methyl-tert-butylether, n-butylethylether, di-n-butylether, di-isobutylether, diisoamylether, diiso-25 propylether, anisol, cyclohexylmethylether, diethylether, ethyl englycoldimethylether, tetrahydrofuran, dioxan, . thioanisol eller dichlordiethylether, nitrocarbonhydrider, såsom nitromethan, nitroethan, nitrobenzen, chlornitro-benzen eller o-nitrotoluen, nitriler, såsom acetonitril, 30 butyronitril, isobutyronitril, benzonitril eller m-chlor-benzonitril, aliphatiske eller cycloaliphatiske carbonhydrider, såsom heptan, hexan, octan, nonan, cymol, • benzinfraktioner inden for et kogepunktsinterval fra 70 til 190°C, cyclohexan, methylcyclohexan, decalin, petro-35 leumsether, ligroin, trimethylpentan, såsom 2,3,3-trimeth- 11 DK 167975 B1 ylpentan, estere, såsom ethylacetat, aceteddikeester og isobutylacetat, amider, f.eks. formamid, methylformamid og dimethylformamid, ketoner, såsom acetone og methylethyl-5 keton, alkoholer, især lavere aliphatiske alkoholer, som f.eks. methanol, ethanol, n-propanol, iso-propanol samt butanolerne, og eventuelt også vand. Der kan også anvendes blandinger af de nævnte opløsningsmidler og fortyndingsmidler.For example, in the methods described above, the following solvents may be used, for example: , 1,2-dichloroethane, 1,1-dichloroethane, 1,2-cis-dichloroethylene, chlorobenzene,. fluorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, chlorotoluene or trichlorotoluene, ethers such as ethyl propyl ether, methyl tert-butyl ether, n-butyl ethyl ether, di-n-butyl ether, di-isobutyl ether, diisoamyl ether, diisopropyl ether, anisole, anisole, anisole diethyl ether, ethyl englycol dimethyl ether, tetrahydrofuran, dioxane ,. thioanisole or dichlorodiethyl ether, nitrocarbon hydrides such as nitromethane, nitroethane, nitrobenzene, chloro nitrobenzene or o-nitrotoluene, nitriles such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile or m-chlorobenzonitrile, aliphatic or aliphatic, aliphatic, gasoline fractions within a boiling range of 70 to 190 ° C, cyclohexane, methylcyclohexane, decalin, petroleum ether, ligroin, trimethylpentane, such as 2,3,3-trimethyl ester, esters, such as ethyl acetate, acetate acetic acid and isobutyl acetate, amides, e.g. formamide, methylformamide and dimethylformamide, ketones such as acetone and methylethyl ketone, alcohols, especially lower aliphatic alcohols such as e.g. methanol, ethanol, n-propanol, iso-propanol and butanol, and optionally also water. Mixtures of said solvents and diluents may also be used.
10 Syntesefremgangsmåder, som er analoge med de ovenfor beskrevne fremgangsmåder, er beskrevet i følgende litteratur :Synthetic methods analogous to the methods described above are described in the following literature:
Fremgangsmåde 1: A. Kreutzberger og J. Gillessen, J.Procedure 1: A. Kreutzberger and J. Gillessen, J.
Heterocyclic Chem. 22, 101 (1985).Heterocyclic Chem. 22, 101 (1985).
15 Fremgangsmåde 2: Trin 2.1: 0. Stark, Ber.Dtsch.Chem.Ges.Procedure 2: Step 2.1: 0. Stark, Ber.Dtsch.Chem.Ges.
42, 699 (1909), J. Hale, J.Am.Chem.Soc. 36, 104 (1914), G.M. Kosolapoff, J.Org.Chem. 26, 1895 (1961). Trin 2.2:42, 699 (1909), J. Hale, J.Am.Chem.Soc. 36, 104 (1914), G.M. Kosolapoff, J.Org.Chem. 26, 1895 (1961). Step 2.2:
St. Angerstein, Ber.Dtsch.Chem.Ges. 34, 3956 (1901), G.M. Kosolapoff, J.Org.Chem. 26, 1895 (1961). Trin 2.3: M.P.V.St. Angerstein, Ber.Dtsch.Chem.Ges. 34, 3956 (1901), G.M. Kosolapoff, J.Org.Chem. 26, 1895 (1961). Step 2.3: M.P.V.
20 Boarland og J.F.W. McOmie, J.Chem.Soc. 1951, 1218, T.20 Boarland and J.F.W. McOmie, J.Chem.Soc. 1951, 1218, T.
Matsukawa og K. Shirakuwa, J.Pharm.Soc. Japan 71, 933 (1951), Chem.Abstr. 46, 4549 (1952).Matsukawa and K. Shirakuwa, J.Pharm.Soc. Japan 71, 933 (1951), Chem. Abstr. 46, 4549 (1952).
Fremgangsmåde 3: A. Combes og C. Combes, Bull.Soc.Chem.Procedure 3: A. Combes and C. Combes, Bull.Soc.Chem.
(3), 7, 791 (1892), W.J. Hale og F.C. Vibrans, J.Am.Chem.(3), 7, 791 (1892), W.J. Hale and F.C. Vibrans, J.Am.Chem.
25 Soc. 40, 1046 (1918).Soc. 40, 1046 (1918).
Det har overraskende vist sig, at forbindelser med formlen I har et til praktiske formål særdeles gunstigt biocidt spektrum til bekæmpelse af insekter og fytopatogene mikroorganismer, især svampe. Forbindelserne med formlen I 30 har meget fordelagtige kurative, præventive og især systemiske egenskaber og anvendes til beskyttelse af talrige kulturplanter. Med de aktive stoffer med formlen ISurprisingly, it has been found that compounds of formula I have a very favorable biocidal spectrum for controlling insects and phytopathogenic microorganisms, especially fungi, for practical purposes. The compounds of formula I 30 have very advantageous curative, preventive and especially systemic properties and are used for the protection of numerous cultural plants. With the active substances of formula I
DK 167975 Bl 12 kan skadeorganismer, som optræder på planter eller plantedele (frugter, blomster, løvværk, stængler, knolde, rødder) af forskellige nyttekul turer hæmmes eller 5 udryddes, idet senere udvoksende plantedele også er beskyttet mod f. eks. fytopatogene mikroorganismer.In particular, harmful organisms that occur on plants or plant parts (fruits, flowers, foliage, stems, tubers, roots) of various crops can be inhibited or eradicated, since later growing plant parts are also protected against, for example, phytopathogenic microorganisms.
Forbindelser med formlen I er virksomme mod fytopatogene svampe, som eksempelvis hører til følgende klasser: Fungi imperfecti (især Botrytis, Helminthosporium, Fusarium, 10 Septoria, Cercospora og Alternaria), basidiomyceter (f.eks. slægterne Hemileia, Rhizoctonia, Puccinia), og ascomyceter (f.eks. Venturia, Podosphaera, Erysiphe, Monilinia og Uncinula). De er også virksomme mod oomyceter (Perenosporales, Phytophthora, Plasmopara og Pythium). De 15 kan endvidere anvendes som bejdsemiddel til behandling af planteformeringsmateriale (frugter, knolde, korn) og plan-'testiklinger til beskyttelse mod svampeinfektioner samt mod fytopatogene svampe, som forekommer i jordbunden. Forbindelser med formlen I er desuden virksomme mod skade-20 insekter, f.eks. mod skadeinsekter i korn, såsom ris.Compounds of formula I are effective against phytopathogenic fungi, which belong, for example, to the following classes: Fungi imperfecti (especially Botrytis, Helminthosporium, Fusarium, Sept. 10, Cercospora and Alternaria), basidiomycetes (e.g. the genera Hemileia, Rhizoctonia, Puccinia), and ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia and Uncinula). They are also effective against oomycetes (Perenosporales, Phytophthora, Plasmopara and Pythium). The 15 can also be used as a dressing agent for the treatment of plant propagating material (fruits, tubers, grains) and plant cuttings for protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. In addition, compounds of formula I are effective against insect pests, e.g. against pest insects in cereals, such as rice.
Midlet ifølge opfindelsen til bekæmpelse af eller beskyttelse mod angreb af skadelige insekter eller fungi er ejendommeligt ved, at det som mindst én aktiv komponent indeholder et 2-anilino-pyrimidinderivat ifølge opfin-25 .delsen.The agent according to the invention for controlling or protecting against attacks of harmful insects or fungi is characterized in that it contains as at least one active component a 2-anilino-pyrimidine derivative according to the invention.
Fremgangsmåden ifølge opfindelsen til bekæmpelse af eller beskyttelse mod et angreb af skadeinsekter eller fytopatogene fungi er ejendommelig ved, at man på planterne eller deres voksested eller opholdssted applicerer et 2-anili-30 no-pyrimidinderivat ifølge opfindelsen.The method of the invention for controlling or protecting against an attack by pest insects or phytopathogenic fungi is characterized by applying a 2-aniline no-pyrimidine derivative to the plants or their habitat or habitat.
Som målkulturer for den her beskrevne plantebeskyttelsesindsats kan inden for rammerne af opfindelsen eksempelvis nævnes følgende plantearter: kornarter (hvede, byg, rug, 13 DK 167975 B1 havre, ris, majs, durra og beslægtede arter), roer (sukkerroer og foderroer), kerne-, sten- og bærfrugt (æble, pærer, blommer, fersken, mandel, kirsebær, jordbær, 5 hindbær og brombær), bælgfrugter (bønner, linser, ærter, soja), oliekulturer (raps, sennep, valmue, oliven, solsikke, kokos, ricinus, kakao, jordnød), agurkeplanter (græskar, agurker, meloner), fiberplanter (bomuld, hør, hamp, jute), citrusfrugter (appelsiner, citroner, grapefrugt og 10 mandariner), grønsagssorter (spinat, hovedsalat, asparges, kålarter, gulerødder, løg, tomater, kartofler, paprika), laurbærplanter (avocado, kanel, campher) eller planter, såsom tobak, nødder, kaffe, sukkerrør, te, peber, vindruer, humle, banan- og naturkautsjukplanter samt pryd-15 planter.As target cultures for the plant protection efforts described herein, for example, the following plant species may be mentioned: cereals (wheat, barley, rye, 13 oats, rice, maize, sorghum and related species), beets (sugar beet and fodder beet), kernel -, stone and berry fruits (apple, pears, plums, peaches, almonds, cherries, strawberries, 5 raspberries and blackberries), legumes (beans, lentils, peas, soy), oil cultures (rapeseed, mustard, poppy, olive, sunflower, coconut, castor, cocoa, peanut), cucumber (pumpkin, cucumber, melon), fiber (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit and 10 mandarins), vegetable varieties (spinach, main salad, asparagus, cabbage) carrots, onions, tomatoes, potatoes, peppers), laurel plants (avocado, cinnamon, camphor) or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, grapes, hops, banana and natural rubber plants and ornamental plants.
Aktive stoffer med formlen I anvendes sædvanligvis i form af præparater og kan appliceres på arealerne eller planterne, som skal behandles, samtidig med andre aktive stoffer eller derefter. Disse andre aktive stoffer kan 20 være såvel gødningsmidler, sporelementstoffer eller andre præparater, som påvirker plantevæksten. Der kan også anvendes selektive herbicider samt insekticider, fungicider, baktericider, nematodicider, molluscicider eller blandinger af flere af disse præparater sammen med even-25 tuelt andre, inden for formuleringsteknikken sædvanligvis anvendte bærestoffer, tensider eller andre applikations-fremmende tilsætninger.Active substances of formula I are usually used in the form of preparations and can be applied to the areas or plants to be treated, at the same time as other active substances or thereafter. These other active substances may be fertilizers, trace elements or other preparations which affect plant growth. Selective herbicides as well as insecticides, fungicides, bactericides, nematodicides, molluscicides or mixtures of several of these compositions may also be used together with any other carriers, surfactants or other application-promoting additives commonly used in the formulation technique.
Egnede bærestoffer og tilsætningsstoffer kan være faste eller flydende og svarer til de i formuleringsteknikken 30 hensigtsmæssige stoffer, såsom f.eks. naturlige eller regenererede mineralstoffer, opløsningsmidler, disper-geringsmidler, fugtemidler, hæftemidler, fortykkelsesmidler, bindemidler eller gødningsmidler.Suitable carriers and additives may be solid or liquid and correspond to the appropriate substances in the formulation technique, such as e.g. natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.
En foretrukken fremgangsmåde til påføring af et aktivt 35 stof med formlen I eller et middel, som indeholder 14 DK 167975 B1 mindst ét af disse aktive stoffer, er påføring på bladværket (bladapplikation). Applikationsfrekvens og anvendelsesmængde afhænger af, hvor kraftigt angrebet med den 5 pågældende sygdomsfremkalder er. De aktive stoffer med formlen I kan imidlertid også nå frem til planterne via jorden gennem rodnettet (systemisk virkning), idet man vander plantens voksested med et flydende præparat eller indbringer stofferne i fast form i jorden, f.eks. i form 10 af granulat (jordapplikation). Ved vandriskulturer kan man sætte sådanne granulater til rismarken, som står under vand. Forbindelserne med formlen I kan imidlertid også påføres på frøkorn (coating), idet man enten fugter kornene i et flydende præparat med det aktive stof eller 15 overtrækker dem med et fast præparat.A preferred method of applying an active substance of formula I or an agent containing at least one of these active substances is application to the foliage (leaf application). The frequency of application and the amount of application depends on the severity of the attack with the 5 pathogen in question. However, the active substances of formula I can also reach the plants via the soil through the root network (systemic effect), by watering the plant's growing site with a liquid preparation or introducing the substances in solid form into the soil, e.g. in the form 10 of granules (soil application). In rice cultivation such granules can be added to the rice field which is under water. However, the compounds of formula I may also be applied to seed (coating) by either wetting the grains in a liquid composition with the active substance or coating them with a solid composition.
Forbindelserne med formlen I kan anvendes i uforandret form eller fortrinsvis sammen med de hjælpemidler, der sædvanligvis anvendes i formuleringsteknikken. Til dette formål forarbejdes de hensigtsmæssigt f.eks. til '20 emulsionskoncentrater, strygefærdige pastaer, direkte sprøjtbare eller fortyndbare opløsninger, fortyndede emulsioner, sprøjtepulvere, opløselige pulvere, pudderpræparater, granulater eller ved indkapsling i f.eks. .polymerstoffer på kendt måde. Anvendelsesfremgangsmåderne 25 såsom sprøjtning, tågedannelse, pudring, udstrøning, udlægning eller udhældning såvel som midlets art vælges svarende til de tilstræbte mål og de givne forhold. Gunstige anvendelsesmængder ligger sædvanligvis fra 50 g til 5 kg aktivt stof (AS) pr. ha, fortrinsvis fra 100 g 30 til 2 kg AS/ha, især fra 200-600 g AS/ha.The compounds of formula I can be used in unchanged form, or preferably together with the auxiliaries commonly used in the formulation technique. For this purpose they are conveniently processed e.g. for '20 emulsion concentrates, iron-ready pastes, direct sprayable or dilute solutions, diluted emulsions, spray powders, soluble powders, powder preparations, granules or by encapsulation in e.g. polymer substances in known manner. The methods of application such as spraying, misting, powdering, scattering, laying or pouring as well as the nature of the agent are selected according to the objectives and conditions given. Favorable amounts of application usually range from 50 g to 5 kg of active substance (AS) per day. ha, preferably from 100 g 30 to 2 kg AS / ha, especially from 200-600 g AS / ha.
Formuleringerne, dvs. midlerne indeholdende det aktive stof med formlen I og eventuelt et fast eller flydende tilsætningsstof, præparaterne eller sammensætningerne fremstilles på kendt måde, f.eks. ved intim blanding 35 og/eller formaling af de aktive stoffer med strækkemidler, som f.eks. opløsningsmidler, faste bærestoffer og even- 15 DK 167975 B1 tuelt overfladeaktive forbindelser (tensider).The formulations, ie. the agents containing the active substance of formula I and optionally a solid or liquid additive, the compositions or compositions are prepared in known manner, e.g. by intimate mixing 35 and / or grinding the active substances with excipients such as e.g. solvents, solid carriers and optional surfactants (surfactants).
Som opløsningsmidler kan anvendes aromatiske carbonhydri-der, fortrinsvis fraktionerne C(8-12), som f.eks. xylen-5 blandinger eller substituerede naphthalener, phthalsyre-estere, såsom dibutyl- eller dioctylphthalat, aliphatiske carbonhydrider, såsom cyclohexan eller paraffiner, alkoholer og glycoler samt deres ethere og estere, såsom ethanol, ethylenglycol, ethylenglycolmonomethyl- eller 10 -ethylether, ketoner, såsom cyclohexanon, stærkt polære opløsningsmidler, såsom N-methyl-2-pyrrolidon, dimethyl-sulfoxid eller dimethylformamid, samt eventuelt epoxi-derede planteolier, såsom epoxideret kokosolie eller sojaolie, eller vand.As solvents, aromatic hydrocarbons, preferably fractions C (8-12), such as e.g. xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or 10 cyclohexanone, highly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized plant oils such as epoxidized coconut oil or soybean oil, or water.
15 Som faste bærestoffer, f.eks. til pudderpræparater og . dispersionspulvere, anvendes i reglen naturlige stenmel, såsom calcit, talkum, kaolin, montmorillonit eller atta-pulgit. Til forbedring af de fysiske egenskaber kan der også tilsættes højdispers kiselsyre eller højdisperse 20 absorptionsdygtige polymerisater. Som kornformige, adsorptive granulatbærere kan anvendes porøse typer, • f.eks. pimpsten, knuste teglsten, sepiolit eller bentonit, og som ikke-sorptive bærematerialer f.eks. calcit eller sand. Desuden kan der anvendes et stort antal forgranule-25 rede materialer af uorganisk natur, såsom især dolomit, eller findelte planterester. Særligt fordelagtige applikations fremmende tilsætningsstoffer, som kan føre til en kraftig reduktion af anvendelsesmængden, er endvidere naturlige (animalske eller vegetabilske) eller syntetiske 30 phospholipider valgt blandt kephalinerae og lecithinerne, som man eksempelvis kan udvinde af sojabønner.As solid carriers, e.g. for powder preparations and. dispersion powders are generally used in natural stone flour such as calcite, talc, kaolin, montmorillonite or atta pulgite. To improve the physical properties, high-dispersion silicic acid or high-dispersion absorbent polymerisers can also be added. Porous types can be used as granular adsorptive granular carriers, e.g. pumice, crushed bricks, sepiolite or bentonite, and as non-sorptive carriers e.g. calcite or sand. In addition, a large number of pre-granulated materials of inorganic nature, such as dolomite in particular, or finely divided plant residues can be used. Particularly advantageous application promoting additives which can lead to a sharp reduction in the use are also natural (animal or vegetable) or synthetic phospholipids selected from the kephalinerae and the lecithins which can be obtained, for example, from soybeans.
Som overfladeaktive forbindelser kan der afhængigt af arten af det aktive stof med formlen I, som skal formuleres, anvendes ikke-ionogene, kationaktive og/eller 35 anionaktive tensider med gode emulgerings-, disperge- 16 DK 167975 B1 rings- og befugtningsegenskaber. Ved tensider skal også forstås tensidblandinger.As surfactants, depending on the nature of the active substance of formula I to be formulated, nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties can be used. Surfactants also include surfactant mixtures.
Egnede anioniske tensider kan være såvel såkaldte vandop-5 løselige sæber som vandopløselige syntetiske overfladeaktive forbindelser.Suitable anionic surfactants may be so-called water-soluble soaps as well as water-soluble synthetic surfactants.
Som sæber kan nævnes alkalimetal-, jordalkalimetal- og eventuelt substituerede ammoniumsalte af højere fedtsyrer (C(10-22)), som f.eks. Na- eller K-saltene af olie- eller 10 stearinsyre, eller af naturlige fedtsyreblandinger, der eksempelvis kan udvindes af kokos- eller talgolie. Der kan endvidere også anvendes fedtsyre-methyllaurinsalte.As soaps, mention may be made of alkali metal, alkaline earth metal and optionally substituted ammonium salts of higher fatty acids (C (10-22)), such as e.g. The Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures which can be extracted, for example, by coconut or tallow oil. Furthermore, fatty acid methyl laurine salts can also be used.
Oftere anvender man dog såkaldte syntetiske tensider, især alkansulfonater, fedtalkoholsulfater, sulfonerede benz-15 imidazolderivater eller alkylsulfonater.More often, however, so-called synthetic surfactants are used, especially alkanesulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkyl sulfonates.
Fedtalkoholsulfonaterne eller -sulfaterne foreligger i reglen som alkalimetal-, jordalkalimetal- eller eventuelt substituerede ammoniumsalte og indeholder en • alkylgruppe med 8-22 carbonatomer, idet alkyl også 20 omfatter alkyldelen af acylrester, f.eks. Na- eller Ca-saltet af ligninsulfonsyre, af dodecylsvovlsyreester eller af en af naturlige fedtsyrer fremstillet fedtalko-holsulfatblanding. Hertil hører også saltene af svovlsyreester og sulfonsyrer af fedtalkohol-ethylenoxid-addi-25 ‘ tionsprodukter. De sulfonerede benzimidazolderivater indeholder fortrinsvis to sulfonsyregrupper og en fedtsyrerest med 8-22 carbonatomer. Alkylarylsulfonater er f.eks. Na-,The fatty alcohol sulphonates or sulphates are usually present as alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain an alkyl group of 8-22 carbon atoms, the alkyl also comprising the alkyl portion of acyl residues, e.g. The Na or Ca salt of lignin sulfonic acid, of dodecyl sulfuric acid ester or of a fatty alcohol sulfate mixture made from natural fatty acids. These include the salts of sulfuric acid ester and sulfonic acids of fatty alcohol-ethylene oxide addition products. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and a fatty acid residue of 8-22 carbon atoms. Alkylarylsulfonates are e.g. Reach-,
Ca- eller triethanolaminsaltene af dodecylbenzensulfonsyre, af dibutylnaphthalensulfonsyre eller af et 30 naphthalensulf onsyre-f ormaldehydkondensationsprodukt.The Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid formaldehyde condensation product.
Der kan endvidere også anvendes tilsvarende phosphater, f.eks. salte af phosphorsyreesteren af et p-nonylphenol-(4-14)-ethylenoxid-additionsprodukt.Further, similar phosphates may also be used, e.g. salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide addition product.
17 DK 167975 B117 DK 167975 B1
Som ikke-ioniske tensider anvendes i første række poly-glycoletherderivater af aliphatiske eller cycloaliphatiske alkoholer, mættede eller umættede fedtsyrer og alkylphe-5 noler, som kan indeholde 3-30 glycolethergrupper og 8-20 carbonatomer i den (aliphatiske) carbonhydridgruppe og 6-18 carbonatomer i alkylgruppen i alkylphenolerne.As nonionic surfactants, poly-glycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkyl phenols which may contain 3-30 glycol ether groups and 8-20 carbon atoms in the (aliphatic) hydrocarbon group and 6-18 are used primarily. carbon atoms in the alkyl group of the alkyl phenols.
Andre egnede ikke-ioniske tensider er vandopløselige, 20-250 ethylenglycolethergrupper og 10-100 propylen-10 glycolethergrupper indeholdende polyethylenoxidaddi-tionsprodukter med polypropylenglycol, ethylendiamino-polypropylenglycol og alkylpolypropylenglycol med 1-10 carbonatomer i alkylkæden. De nævnte forbindelser indeholder sædvanligvis 1-5 ethyl eng lycol enheder pr.Other suitable nonionic surfactants are water-soluble, 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups containing polyethylene oxide addition products with polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1-10 carbon atoms in the alkyl chain. The said compounds usually contain from 1 to 5 ethyl eng lycol units per liter.
15 propylenglycolenhed.15 propylene glycol unit.
Som eksempler på ikke-ioniske tensider kan nævnes nonyl-phenolpolyethoxyethanoler, ricinusoliepolyglycolethere, polypropylen-polyethylenoxidadditionsprodukter, tributyl-phenoxypolyethylenethanol, polyethylenglycol og octyl-20 phenoxypolyethoxyethanol.Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene polyethylene oxide addition products, tributylphenoxypolyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Der kan endvidere også anvendes fedtsyreestere af poly-oxyethylensorbitan, såsom polyoxyethylensorbitan-trioleat.Furthermore, fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate can also be used.
De kationiske tensider er først og fremmest kvaternære ammoniumsalte, der som N-substituent indeholder mindst én 25 alkylgruppe med 8-22 carbonatomer, og som yderligere sub-stituenter lave, eventuelt halogenerede alkyl-, benzyl-eller lave hydroxyalkylgrupper. Saltene foreligger fortrinsvis som halogenider, methylsulfater eller ethylsul-fater, f.eks. stearyltrimethylammoniumchloridet eller 30 benzyldi( 2-chlorethyl )-ammoniumbromidet.The cationic surfactants are primarily quaternary ammonium salts containing as N-substituent at least one alkyl group of 8-22 carbon atoms and as additional substituents low, optionally halogenated alkyl, benzyl or low hydroxyalkyl groups. The salts are preferably present as halides, methyl sulfates or ethyl sulfates, e.g. the stearyl trimethylammonium chloride or the benzyldi (2-chloroethyl) ammonium bromide.
Andre tensider, der er almindeligt anvendt i formuleringsteknikken, er velkendt for fagmanden eller er beskrevet i faglitteraturen.Other surfactants commonly used in the formulation technique are well known to those skilled in the art or are described in the art literature.
18 DK 167975 B118 DK 167975 B1
Midlerne indeholder i reglen 0,1-99%, især 0,1-95%, aktivt stof med formlen I, 99,9-1%, især 99,8-5%, faste og flydende tilsætningsstoffer og 0-25%, især 0,1-25%, ten-5 sid.The agents generally contain 0.1-99%, especially 0.1-95%, active substance of formula I, 99.9-1%, especially 99.8-5%, solid and liquid additives and 0-25%, especially 0.1-25%, ten-sid.
Medens man som handelsvare foretrækker koncentrerede midler, anvender slutforbrugeren i reglen fortyndede midler.While as a commodity prefer concentrated funds, the end consumer usually uses diluted funds.
Midlerne kan også indeholde andre tilsætningsstoffer, 10 såsom stabilisatorer, skumdæmpende midler, viskositetsregulerende midler, bindemidler, hæftemidler samt gødningsmidler eller andre aktive stoffer til opnåelse af særlige virkninger.The agents may also contain other additives, such as stabilizers, antifoaming agents, viscosity regulators, binders, adhesives, and fertilizers or other active substances to achieve particular effects.
Opfindelsen illustreres nærmere i de efterfølgende 15 eksempler.The invention is further illustrated in the following examples.
Eksempel 1Example 1
Fremstilling af 2-phenylamino-4-methyl-6-methoxymethyl-pyrimidin /Η3 \τ=· (forb. nr. 1) XCH20CHa 20 En blanding af 7,5 g phenylguanidin-hydrogencarbonat og 7,4 g methoxyacetylacetone opvarmes under omrøring i 4 timer til 100eC, hvorved den indtrådte carbondioxidudvikling bliver svagere, jo længere tid reaktionen forløber. Efter afkøling til stuetemperatur sættes 60 ml diethyl-25 ether til den brune emulsion, hvorpå der vaskes med 3 x 20 ml vand, tørres med natriumsulfat, filtreres, og opløs- 19 DK 167975 B1 ningsmidlet afdampes. Der fås 10,5 g olieformig remanens, som opløses i 140 ml diethylether, hvorpå der under omrøring tilsættes 4,4 g 65%’s salpetersyre. Suspensionen 5 af det udfældede nitratsalt efterrøres i yderligere 20 minutter, hvorpå der filtreres og eftervaskes med 100 ml diethylether. Til en blanding bestående af 11 g af nitratsaltet, 80 ml diethylether og 60 ml vand sættes under omrøring 6 g 30%'s natriumhydroxidopløsning, hvorpå den 10 organiske fase isoleres, vaskes med 2 x 40 ml vand, tørres med natriumsulfat, filtreres, hvorpå opløsningsmidlet afdampes. Der fås 8,7 g lysebrun olieformig remanens, som med 100 ml petroleumsether (kogeinterval 50-70°C) bringes til krystallisation, hvorpå der filtreres og tørres. Der 15 fås 8 g lyst, beigefarvet krystalpulver med smp. 59-60°C, Udbytte: 92% af det teoretiske, beregnet på phenylguan-idin-hydrogencarbonatet.Preparation of 2-phenylamino-4-methyl-6-methoxymethyl-pyrimidine / Η3 \ τ = · (Compound No. 1) XCH20CHa 4 hours to 100 ° C, whereby the occurrence of carbon dioxide evolution becomes weaker, the longer the reaction proceeds. After cooling to room temperature, 60 ml of diethyl ether are added to the brown emulsion, which is washed with 3 x 20 ml of water, dried with sodium sulfate, filtered and the solvent evaporated. 10.5 g of oily residue are obtained, which is dissolved in 140 ml of diethyl ether, and with stirring 4.4 g of 65% nitric acid is added. The suspension 5 of the precipitated nitrate salt is stirred for an additional 20 minutes, then filtered and washed with 100 ml of diethyl ether. To a mixture consisting of 11 g of the nitrate salt, 80 ml of diethyl ether and 60 ml of water is added with stirring 6 g of 30% sodium hydroxide solution, whereupon the organic phase is isolated, washed with 2 x 40 ml of water, dried with sodium sulfate, filtered and the solvent is evaporated. 8.7 g of light brown oily residue are obtained which are crystallized with 100 ml of petroleum ether (boiling range 50-70 ° C), filtered and dried. There are 15 g of light, beige colored crystal powder with m.p. Yield: 92% of theory, based on the phenylguanidine hydrogen carbonate.
Eksempel 2Example 2
Fremstilling af 2-(p-chlorphenylamino)-4-methyl-6-20 methoxymethy 1 -pyrimidin /CH3Preparation of 2- (p-chlorophenylamino) -4-methyl-6-20 methoxymethyl 1-pyrimidine / CH 3
Cl—^ NH— ^ (forb. nr. 70) CHz0CH3C— NH NH—— forb (Compound No. 70) CH₂OCH3
En opløsning af 6,4 g 4-chloranilin og 8,6 g 2-chlor-4-methy 1-6-methoxymethyl-pyrimidin indstilles under omrøring med 5 ml koncentreret saltsyre på pH-værdien 1, hvorefter 25 der opvarmes i 20 timer under tilbagesvaling. Efter afkøling til stuetemperatur gøres den brune emulsion basisk med 12 ml 30%'s ammoniak, hvorpå den hældes i 100 ml isvand og ekstraheres med 3 x 50 ml ethyl acetat. De sammenblandede ekstrakter vaskes med 50 ml vand, tørres med 30 natriumsulfat og filtreres, og opløsningsmidlet afdampes.A solution of 6.4 g of 4-chloro aniline and 8.6 g of 2-chloro-4-methyl 1-6-methoxymethyl-pyrimidine is stirred with 5 ml of concentrated hydrochloric acid at pH 1, then heated for 20 hours. under reflux. After cooling to room temperature, the brown emulsion is made basic with 12 ml of 30% ammonia, then poured into 100 ml of ice water and extracted with 3 x 50 ml of ethyl acetate. The combined extracts are washed with 50 ml of water, dried with 30% sodium sulfate and filtered and the solvent is evaporated.
20 DK 167975 B120 DK 167975 B1
Der fås 11,8 g rød olie, som kromatograferes på en 30 cm lang kiselgelsøjle ved hjælp af dichlormethan/diethyl-ether (3:2). Efter afdampning af elueringsmidlet bringes 5 den i begyndelsen olieformige remanens til krystallisation ved udrivning med petroleumsether. Efter omkrystallisation fra diisopropylether/petroleumsether (50-70°C) fås 9,8 g beige farvet krystalpulver, som smelter ved 57-59°C, udbytte: 74% af det teoretiske.11.8 g of red oil are obtained which are chromatographed on a 30 cm silica column using dichloromethane / diethyl ether (3: 2). After evaporation of the eluent, the initially oily residue is crystallized by rubbing off with petroleum ether. After recrystallization from diisopropyl ether / petroleum ether (50-70 ° C), 9.8 g of beige colored crystal powder melting at 57-59 ° C is obtained: 74% of theory.
21 DK 167975 B121 DK 167975 B1
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Det aktive stof opløses i methylenchlorid, opløsningen sprøjtes på bæreren, hvorefter opløsningsmidlet afdampes i vakuum.The active substance is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is evaporated in vacuo.
5 2.4 Pudderpræparat a) b)5 2.4 Powder Preparation a) b)
Aktivt stof fra tabellen 2% 5% Højdispers kiselsyre 1% 5%Active substance from the table 2% 5% High-dispersion silicic acid 1% 5%
Talkum 97% -Talc 97% -
Kaolin - 90% 10 Der fremstilles brugsfærdige pudderpræparater ved intim blanding af bærestoffer med det aktive stof.Kaolin - 90% 10 Ready-made powder formulations are prepared by intimate mixing of carriers with the active substance.
Formuleringseksempler på faste aktive stoffer med fontilen I (% = vægt-%) 2.5 Sprøj tepulver a) b) c) 15 Aktivt stof fra tabellen 25% 50% 75%Formulation examples of solid active substances with the fontile I (% = wt%) 2.5 Spray tea powder a) b) c) 15 Active substance from the table 25% 50% 75%
Na-Ligninsulfonat 5% 5%Na-lignin sulfonate 5% 5%
Na-Laurylsulfat 3% - 5%Na-Lauryl Sulfate 3% - 5%
Na-Diisobutylnaphthalensulfonat - 6% 10%Na-Diisobutylnaphthalenesulfonate - 6% 10%
Octylphenolpolyethylenglycolether 20 (7-8 mol ethylenoxid) - 2% - Højdispers kiselsyre 5% 10% 10%Octylphenol polyethylene glycol ether 20 (7-8 moles of ethylene oxide) - 2% - High-dispersed silicic acid 5% 10% 10%
Kaolin 62% 27%Kaolin 62% 27%
Det aktive stof blandes grundigt med tilsætningsstofferne, og der foretages formaling på en egnet mølle. Man får 25 sprøjtepulver, som kan fortyndes med vand til suspensioner af en vilkårlig ønsket koncentration.The active substance is thoroughly mixed with the additives and grinding is performed on a suitable mill. 25 syringes of powder are obtained, which can be diluted with water to suspensions of any desired concentration.
2♦6 Emulsionskoncentrat2 ♦ 6 Emulsion Concentrate
Aktivt stof fra tabellen 10%Active substance from table 10%
Octylphenolpolyethylenglycolether 30 (4-5 mol ethylenoxid) 3% 47 DK 167975 B1 2. Formuleringseksempler for flydende aktive stoffer med formlen I (% = vægt-%) 2.1 Emulsionskoncentrater a) b) c) 5 Aktivt stof fra tabellen 25% 40% 50%Octylphenol polyethylene glycol ether 30 (4-5 moles of ethylene oxide) 3% 47 2. Formulation examples for liquid active substances of formula I (% = wt%) 2.1 Emulsion concentrates a) b) c) Active substance from table 25% 40% 50 %
Ca-Dodecylbenzensulfonat 5% 8% 6%Ca-Dodecylbenzenesulfonate 5% 8% 6%
Ricinusolie-polyethylenglycolether (36 mol ethylenoxid) 5%Castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5%
Tributylphenoy1-polyethylenglycol-10 ether (30 mol ethylenoxid) - 12% 4%Tributylphenoy1-polyethylene glycol ether (30 moles of ethylene oxide) - 12% 4%
Cyclohexanon - 15% 20%Cyclohexanone - 15% 20%
Xylenblanding 65% 25% 20%Xylene blend 65% 25% 20%
Ved fortynding med vand kan man ud fra sådanne koncentrater fremstille emulsioner af en vilkårlig ønsket 15 koncentration.By dilution with water, emulsions of any desired concentration can be prepared from such concentrates.
2.2 Opløsninger a) b) c) d)2.2 Solutions a) b) c) d)
Aktivt stof fra tabellen 80% 10% 5% 95%Active substance from the table 80% 10% 5% 95%
Ethylenglycolmonomethylether 20% - - -Ethylene glycol monomethyl ether 20% - - -
Polyethylenglycol 400 - 70% 20 N-Methyl-2-pyrrolidon - 20%Polyethylene Glycol 400 - 70% 20 N-Methyl-2-pyrrolidone - 20%
Epoxideret kokosolie - 1% 5%Epoxidized Coconut Oil - 1% 5%
Benzin (kogeinterval 160-190°C) - - 94%Gasoline (boiling range 160-190 ° C) - - 94%
Opløsningerne er egnede til anvendelse i form af ganske små dråber.The solutions are suitable for use in the form of very small droplets.
25 2.3 Granulater a) b)2.3 Granules a) b)
Aktivt stof fra tabellen 5% 10%Active substance from the table 5% 10%
Kaolin 94% Højdispers kiselsyre 1%Kaolin 94% High-dispersion silicic acid 1%
Attapulgit - 90% 49 DK 167975 B1Attapulgit - 90% 49 DK 167975 B1
Ca-Dodecylbenzensulfonat 3%Ca-Dodecylbenzenesulfonate 3%
Ricinusoliepolyglycolether (35 mol ethylenoxid) 4% 5 Cyclohexanon 34%Castor oil polyglycol ether (35 moles of ethylene oxide) 4% Cyclohexanone 34%
Xylenblanding 50%Xylene Mixture 50%
Ved fortynding med vand kan man ud fra dette koncentrat fremstille emulsioner med en vilkårlig ønsket koncentration.By dilution with water, emulsions of any desired concentration can be prepared from this concentrate.
10 2.7 Pudderpræparat a) b)2.7 Powder Preparation a) b)
Aktivt stof fra tabellen 5% 8%Active substance from the table 5% 8%
Talkum 95%Talc 95%
Kaolin - 92%Kaolin - 92%
Man får brugsfærdige pudderpræparater ved blanding af det 15 aktive stof med bærestoffet og formaling af blandingen på et egnet formalingsapparatur.Ready powder preparations are obtained by mixing the active substance with the carrier and grinding the mixture on a suitable grinding apparatus.
2.8 Ekstrudergranulat2.8 Extruder granules
Aktivt stof fra tabellen 10%Active substance from table 10%
Na-Ligninsulfonat 2% 20 Carboxymethylcellulose 1%Na-lignin sulfonate 2% Carboxymethyl cellulose 1%
Kaolin 87%Kaolin 87%
Det aktive stof blandes med tilsætningsstofferne, blandingen formales og befugtes med vand. Derefter ekstruderes blandingen, som til sidst tørres i en luftstrøm.The active substance is mixed with the additives, the mixture is ground and wetted with water. Then the mixture is extruded, which is eventually dried in an air stream.
25 2♦9 Omhylningsgranulat25 2 ♦ 9 Envelope granules
Aktivt stof fra tabellen 3%Active substance from table 3%
Polyethylenglycol (200) 3%Polyethylene glycol (200) 3%
Kaolin 94% 50 DK 167975 B1Kaolin 94% 50 DK 167975 B1
Det fint formalede aktive stof påføres ensartet i et blandeapparatur på kaolin, som er befugtet med polyethyl-englycol. På denne måde fås støvfri omhylningsgranulater.The finely ground active ingredient is uniformly applied in a kaolin wetting apparatus wetted with polyethylene glycol. In this way, dust-free casing granules are obtained.
5 2.10 Suspensionskoncentrat2.10 Suspension concentrate
Aktivt stof fra tabellen 40%Active substance from the table 40%
Ethylenglycol 10%Ethylene glycol 10%
Nonylphenolpolyethylenglycolether (15 mol ethylenoxid) 6% 10 Na-Ligninsulfonat 10%Nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% Na-lignin sulfonate 10%
Carboxymethylcellulose 1% 37%'s vandig formaldehydopløsning 0,2%Carboxymethyl cellulose 1% 37% aqueous formaldehyde solution 0.2%
Silikoneolie i form af en 75%'s vandig emulsion 0,8% 15 Vand 32%Silicone oil in the form of a 75% aqueous emulsion 0.8% Water 32%
Det fint formalede aktive stof blandes grundigt med tilsætningsstofferne. På denne måde får man et suspensionskoncentrat, hvoraf man ved fortynding med vand kan fremstille suspensioner af en vilkårlig ønsket koncen-20 tration.The finely ground active substance is thoroughly mixed with the additives. In this way, a suspension concentrate is obtained from which, by dilution with water, suspensions of any desired concentration can be prepared.
3. Biologiske eksempler3. Biological examples
Eksempel 3.1: Virkning mod Puccinia graminis på hvede a) Residual-protektiv virkningExample 3.1: Effect against Puccinia graminis on wheat a) Residual protective effect
Hvedeplanter sprøjtes 6 dage efter udsåningen med en 25 sprøjtevæske (0,02% aktivt stof) fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. Efter 24 timers forløb inficeres de behandlede planter med en uredosporesuspension af svampen. Efter en inkubationstid på 48 timer ved en relativ luftfugtighed på 95-100% og ca.Wheat plants are sprayed 6 days after sowing with a 25 spray liquid (0.02% active substance) prepared from a spray powder containing the active substance. After 24 hours, the treated plants are infected with an uredospores suspension of the fungus. After an incubation period of 48 hours at a relative humidity of 95-100% and approx.
30 20°C anbringes de inficerede planter i et væksthus ved ca.At 20 ° C, the infected plants are placed in a greenhouse at approx.
22°C. Bedømmelsen af rustudviklingen foretages 12 dage 51 DK 167975 B1 efter infektionen, b) Systemisk virkning22 ° C. The assessment of rust development is carried out 12 days after infection, b) Systemic effect
Til hvedeplanter hældes 5 dage efter udsåningen en 5 sprøjtevæske (0,006% aktivt stof, beregnet på jordrumfanget), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. Efter 48 timers forløb inficeres de behandlede planter med en uredosporesuspension af svampen. Efter en inkubationstid på 48 timer ved en relativ luft-10 fugtighed på 95-100% og ca. 20°C anbringes de inficerede planter i et væksthus ved ca. 22°C. Bedømmelsen af rustudviklingen foretages 12 dage efter infektionen.For wheat plants, 5 days after sowing, a 5 spray liquid (0.006% active substance, calculated on the soil volume) is poured from a spray powder containing the active substance. After 48 hours, the treated plants are infected with an uredospores suspension of the fungus. After an incubation period of 48 hours at a relative humidity of 95-100% and approx. At 20 ° C, the infected plants are placed in a greenhouse at approx. 22 ° C. Assessment of rust development is done 12 days after infection.
Forbindelser fra tabellen viser god virkning mod Puccinia (angreb: <20%). Ubehandlede men inficerede kontrolplanter 15 udviser derimod et Puccinia-angreb på 100%.Compounds from the table show good effect against Puccinia (attack: <20%). Untreated but infected control plants, on the other hand, exhibit a 100% Puccinia attack.
Eksempel 3.2: Virkning mod Phytophthora på tomatplanter a) Residual-protektiv virkningExample 3.2: Effect against Phytophthora on tomato plants a) Residual protective effect
Efter 3 ugers dyrkning sprøjtes tomatplanter med en sprøjtevæske (0,02% aktivt stof), som er fremstillet ud 20 fra et sprøjtepulver indeholdende det aktive stof. Efter 24 timers forløb inficeres de behandlede planter med en sporangiesuspension af svampen. Bedømmelsen af svampeangrebet foretages efter en inkubationstid for de inficerede planter på 5 dage ved en relativ luftfugtighed på 90-100% 25 og 20°C.After 3 weeks of cultivation, tomato plants are sprayed with a spray liquid (0.02% active substance) prepared from 20 from a spray powder containing the active substance. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. The fungal attack is assessed after a 5-day incubation period for the infected plants at a relative humidity of 90-100% 25 and 20 ° C.
b) Residual-kurativ virkningb) Residual curative effect
Efter 3 ugers dyrkning inficeres tomatplanter med en sporangiesuspension af svampen. Efter en inkubationstid på 22 timer i et fugtighedskammer ved en relativ luftfugtig-30 hed på 90-100% og 20°C tørres de inficerede planter og 52 DK 167975 B1 sprøjtes med en sprøjtevæske (0,02% aktivt stof), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. Efter tørring af sprøjtebelægningen anbringes 5 de behandlede planter atter i fugtighedskammeret. Bedømmelsen af svampeangrebet foretages 5 dage efter infektionen.After 3 weeks of cultivation, tomato plants are infected with a sporangia suspension of the fungus. After an incubation time of 22 hours in a humidity chamber at a relative humidity of 90-100% and 20 ° C, the infected plants are dried and sprayed with a spray liquid (0.02% active substance) prepared from a spray powder containing the active substance. After drying the spray coating, the treated plants are placed back in the humidity chamber. The assessment of the fungal attack is made 5 days after the infection.
c) Systemisk virkningc) Systemic effect
Til tomatplanter hældes efter 3 ugers dyrkning en 10 sprøjtevæske (0,002% aktivt stof, beregnet på jordrumfanget), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. Der drages omsorg for, at sprøjtevæsken ikke kommer i berøring med planternes overjordiske dele. Efter 48 timer inficeres de behandlede 15 planter med en sporangiesuspension af svampen. Bedømmelsen af svampeangrebet foretages efter en inkubationstid for de inficerede planter på 5 dage med en relativ luftfugtighed på 90-100% og 20°C.For tomato plants, after 3 weeks of cultivation, a 10 spray liquid (0.002% active substance, based on soil volume) is poured, which is made from a spray powder containing the active substance. Care is taken to ensure that the spray liquid does not come into contact with the plants' soil. After 48 hours, the treated 15 plants are infected with a sporangia suspension of the fungus. The fungal attack is assessed after a 5-day incubation period for the infected plants with a relative humidity of 90-100% and 20 ° C.
Forbindelser fra tabellen viser god virkning mod 20 Phytophthora (angreb: <20%). Ubehandlede men inficerede kontrolplanter uviser derimod et Phyphthora-angreb på 100%.Compounds from the table show good effect against 20 Phytophthora (attack: <20%). Untreated but infected control plants, on the other hand, show a Phyphthora attack of 100%.
Eksempel 3.3: Virkning mod Plasmopara viticola på druerExample 3.3: Effect against Plasmopara viticola on grapes
Residual-protektiv virkning 25 Vinplanter på 4-5-bladsstadiet sprøjtes med en sprøjtevæske (0,02% aktivt stof), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. Efter 24 timer inficeres de behandlede planter med en sporangiesuspension af svampen. Efter en inkubationstid på 6 dage 30 ved en relativ luftfugtighed på 95-100% og 20°C bedømmes . svampeangrebet.Residual protective effect 25 4-5 leaf stage vine plants are sprayed with a spray liquid (0.02% active substance) prepared from a spray powder containing the active substance. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. After an incubation period of 6 days 30 at a relative humidity of 95-100% and 20 ° C is evaluated. fungus attack.
53 DK 167975 B153 DK 167975 B1
Forbindelser fra tabellen viser god virkning mod Plasmopara. Ubehandlede med inficerede kontrolplanter udviser derimod et Plasmopara-angreb på 100%.Compounds from the table show good effect against Plasmopara. Untreated with infected control plants, on the other hand, exhibit a 100% Plasmopara attack.
5 Eksempel 3.4: Virkning mod Cercospora arachidicola på jordnøddeplanterExample 3.4: Effect against Cercospora arachidicola on peanut plants
Residual-protektiv virkningResidual protective effect
Jordnøddeplanter med en -højde på 10-15 cm sprøjtes med en sprøjtevæske (0,02% aktivt stof), som er fremstillet ud 10 fra et sprøjtepulver indeholdende det aktive stof, og 48 timer senere inficeres planterne med en konidiesuspension af svampen. De inficerede planter inkuberes i 72 timer ved 21eC og høj luftfugtighed, hvorefter de anbringes i et væksthus, indtil der optræder typiske bladpletter.Peanut plants with a height of 10-15 cm are sprayed with a spray liquid (0.02% active substance) made out of 10 from a spray powder containing the active substance, and 48 hours later the plants are infected with a conidial suspension of the fungus. The infected plants are incubated for 72 hours at 21 ° C and high humidity, then placed in a greenhouse until typical leaf spots appear.
15 Bedømmelsen af den fungicide virkning foretages 12 dage efter infektionen og er baseret på antallet og størrelsen af de optrædende pletter.The fungicidal effect is assessed 12 days after infection and is based on the number and size of the spots occurring.
Forbindelser fra tabellen viser god virkning modCompounds from the table show good effect against
Cercospora (angreb: <20%). Ubehandlede men inficerede kon-20 trolplanter udviser derimod et Cercospora-angreb på 100%.Cercospora (attack: <20%). Untreated but infected control plants, on the other hand, exhibit a 100% Cercospora attack.
Eksempel 3.5: Virkning mod Venturis inaequalis på æbleskudExample 3.5: Effect against Venturis inaequalis on apple shoots
Residual-protektiv virkning Æblestiklinger med 10-20 cm lange friske skud sprøjtes med 25 en sprøjtevæske (0,02% aktivt stof), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. Efter . 24 timers forløb inficeres de behandlede planter med en konidiesuspension af svampen. Planterne inkuberes derefter i 5 dage ved en relativ luftfugtighed på 90-100%, hvorpå 30 de anbringes i yderligere 10 dage i et væksthus ved 20-24°C. Skurvangrebet bedømmes 15 dage efter infektionen.Residual-protective effect Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray liquid (0.02% active substance), which is made from a spray powder containing the active substance. After . Within 24 hours, the treated plants are infected with a conidial suspension of the fungus. The plants are then incubated for 5 days at a relative humidity of 90-100% and then placed for an additional 10 days in a greenhouse at 20-24 ° C. The scab attack is assessed 15 days after the infection.
54 DK 167975 B154 DK 167975 B1
Forbindelser fra tabellen viser god virkning mod Venturia. Således reducerer eksempelvis forbindelserne nr. 1, 10, 38, 59, 231, 262 og 276 Venturia-angrebet til mindre end 5 10%. Ubehandlede men inficerede kontrolplanter udviser derimod et Venturia-angreb på 100%.Compounds from the table show good effect against Venturia. For example, compounds Nos. 1, 10, 38, 59, 231, 262 and 276 reduce the Venturia attack to less than 5 10%. Untreated but infected control plants, on the other hand, exhibit a 100% Venturia attack.
Eksempel 3.6: Virkning mod Botrytis cinerae på æble- frugterExample 3.6: Effect against Botrytis cinerae on apple fruit
Residual-protektiv virkning 10 Kunstigt beskadigede æbler behandles ved podning på de beskadigede steder med en sprøjtevæske (0,002% aktivt stof), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. De behandlede frugter inokuleres derefter med en sporesuspension af svampen, hvorpå de 15 inkuberes i en uge ved høj luftfugtighed og ca. 20°C. Ved bedømmelsen optælles de beskadigede steder, hvor der optræder råd, og ud fra dette resultat beregnes forsøgsforbindelsens fungicide virkning.Residual Protective Effect 10 Artificially damaged apples are treated by grafting at the damaged sites with a spray liquid (0.002% active ingredient) prepared from a spray powder containing the active substance. The treated fruits are then inoculated with a spore suspension of the fungus, whereupon they are incubated for a week at high humidity and ca. 20 ° C. In the assessment, the damaged places where advice occurs are counted and from this result the fungicidal effect of the test compound is calculated.
. Forbindelser fra tabellen viser god virkning mod Botrytis 20 (angreb: <20%). Således reduceres eksempelvis forbindelse nr. 1, 3, 7, 10, 38, 59, 231, 256, 262, 268 og 276 Botry-tis-anbrebet til 0-5%. Ubehandlede men inficerede kontrolplanter udviser derimod et Botrytis-angreb på 100%.. Compounds from the table show good effect against Botrytis 20 (attack: <20%). For example, Compound Nos. 1, 3, 7, 10, 38, 59, 231, 256, 262, 268 and 276 Botrytis infestation are reduced to 0-5%. Untreated but infected control plants, on the other hand, exhibit a 100% Botrytis attack.
Eksempel 3.7: Virkning mod Erysiphe graminis på byg 25 Residual-protektiv virkningExample 3.7: Effect against Erysiphe graminis on barley 25 Residual protective effect
Bygplanter med en højde på ca. 8 cm sprøjtes med en sprøjtevæske (0,02% aktivt stof), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. Efter 3-4 timer bestøves de behandlede planter med konidier af 30 svampen. De inficerede bygplanter anbringes i et væksthus ved ca. 22eC, og svampeangrebet bedømmes efter 10 dage.Barley plants with a height of approx. 8 cm is sprayed with a spray liquid (0.02% active substance) prepared from a spray powder containing the active substance. After 3-4 hours, the treated plants are pollinated with conidia of the 30 fungus. The infected barley plants are placed in a greenhouse at approx. 22 ° C and the fungal attack is assessed after 10 days.
55 DK 167975 B155 DK 167975 B1
Forbindelser fra tabellen viser god virkning mod Erysiphe. Således reducerer eksempelvis forbindelserne nr. 1, 5, 6, 10, 38, 59, 135, 175, 231 og 262 Erysiphe-angrebet til 5 mindre end 20%. Ubehandlede men inficerede kontrolplanter udviser derimod et Erysiphe-angreb på 100%.Compounds from the table show good effect against Erysiphe. Thus, for example, compounds Nos. 1, 5, 6, 10, 38, 59, 135, 175, 231 and 262 reduce the Erysiphe attack to 5 less than 20%. Untreated but infected control plants, on the other hand, exhibit a 100% Erysiphe attack.
Eksempel 3.8: Virkning mod Helminthosporium gramineumExample 3.8: Effect against Helminthosporium gramineum
Hvedekom kontamineres med en sporesuspension af svampen, hvorpå de tørres. De kontaminerede korn bejdses med en af 10 et sprøjtepulver fremstillet suspension af forsøgsforbindelsen (600 ppm aktivt stof, beregnet på kornenes vægt). Efter 2 dage udlægges komene på egnede agarskåle og efter yderligere 4 dage bedømmes udviklingen af svampekolonier .omkring kornene. Antal og størrelsen af svampekolonierne 15 anvendes til bedømmelsen af forsøgsforbindelsen. Forbindelserne fra tabellen forhindrer svampeangrebet i vid udstrækning (0-10%).Wheat grains are contaminated with a spore suspension of the fungus and dried. The contaminated grains are stained with a suspension of the test compound prepared from a spray powder (600 ppm active substance, based on the weight of the grains). After 2 days the grains are laid on suitable agar dishes and after a further 4 days the development of fungal colonies around the grains is evaluated. The number and size of the fungal colonies 15 are used to evaluate the test compound. The compounds from the table largely prevent the fungal attack (0-10%).
Eksempel 3.9: Virkning mod Fusarium nivaleExample 3.9: Effect against Fusarium levels
Hvedekorn kontamineres med en sporesuspension af svampen, 20 hvorpå kornene atter tørres. Kontaminerede korn bejdses med en af et sprøjtepulver fremstillet suspension af forsøgsforbindelsen (600 ppm aktivt stof, beregnet på kornenes vægt). Efter 2 dage udlægges kornene på egnede agarskåle, og efter yderligere 4 dage bedømmes udviklingen 25 af svampekolonier omkring kornene. Antal og størrelse af svampekolonierne anvendes til bedømmelse af forsøgsforbindelsen.Wheat grains are contaminated with a spore suspension of the sponge, after which the grains are again dried. Contaminated grains are stained with a suspension of the test compound made from a spray powder (600 ppm active substance, based on the weight of the grains). After 2 days, the grains are laid on suitable agar dishes, and after a further 4 days the development of 25 fungal colonies around the grains is assessed. Number and size of the fungal colonies are used to evaluate the test compound.
Ved de kom, som er blevet behandlet med et sprøjtepulver, der som aktivt stof indeholder en forbindelse fra 30 tabellen, undertrykkes udviklingen af svampekolonierne næsten fuldstændigt (0-5%).In the cereals that have been treated with a spray powder containing as an active substance a compound from the table, the development of the fungal colonies is almost completely suppressed (0-5%).
Eksempel 3.10: Virkning mod Tilletia caries 56 DK 167975 B1Example 3.10: Effect against Tilletia caries 56 DK 167975 B1
Bygkorn kontamineres med en sporesuspension af svampen, hvorpå kornene atter tørres. De kontaminerede korn bejdses 5 med en af sprøjtepulver fremstillet suspension af forsøgs-forbindelsen (600 ppm aktivt stof, beregnet på kornenes vægt). Efter 2 dage udlægges kornene på egnede agarskåle, og efter yderligere 4 dage bedømmes udviklingen af svampekolonier omkring kornene. Antal og størrelse af svampeko-10 lonierne anvendes til bedømmelse af forsøgsforbindelsen.Barley is contaminated with a spore suspension of the sponge, after which the grains are again dried. The contaminated grains are stained with a suspension of the test compound prepared from spray powder (600 ppm active substance, based on the weight of the grains). After 2 days, the grains are laid on suitable agar dishes and after a further 4 days the development of fungal colonies around the grains is assessed. The number and size of the fungal colonies are used to evaluate the test compound.
• Forbindelserne fra tabellen forhindrer svampeangrebet i vid udstrækning (0-10%).• The compounds from the table largely prevent the fungal attack (0-10%).
Eksempel 3.11: Virkning mod Colletotrichum lagenarium på agurker (Cucumis sativus L.) 15 · Efter 2 ugers dyrkning sprøjtes agurkeplanter med en sprøjtevæske (koncentration 0,02%), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. Efter 2 dages forløb inficeres planterne med en sporesuspension (1,5 x 10^ sporer /ml) af svampen, og der inkuberes i 36 20 ' timer i mørke ved 23eC og høj luftfugtighed. Derefter ' gennemføres inkuberingen ved normal luftfugtighed og ca.Example 3.11: Effect against Colletotrichum lagenarium on cucumbers (Cucumis sativus L.) 15 · After 2 weeks of cultivation, cucumber plants are sprayed with a spray liquid (concentration 0.02%) prepared from a spray powder containing the active substance. After 2 days, the plants are infected with a spore suspension (1.5 x 10 5 spores / ml) of the fungus and incubated for 36 20 hours in the dark at 23 ° C and high humidity. Then the incubation is carried out at normal humidity and approx.
22-23eC. Det opståede svampeangreb bedømmes 8 dage efter infektionen. Ubehandlede men inficerede kontrolplanter udviser et svampeangreb på 100%.22-23eC. The fungal attack that occurs is assessed 8 days after infection. Untreated but infected control plants exhibit a 100% fungal attack.
25 Forbindelser fra tabellen viser god virkning og forhindrer udbredelsen af sygdomsangrebet. Svampeangrebet bekæmpes til 20% eller mindre.25 Compounds from the table show good effect and prevent the spread of the disease attack. The fungal attack is fought to 20% or less.
Eksempel 3.12: Virkning mod Septoria nodorum på hvedeExample 3.12: Effect against Septoria nodorum on wheat
Residual-protektiv virkning 30 7 dage gamle hvedeplanter sprøjtes med en sprøjtevæske (koncentration 0,02%) fremstillet ud fra den formulerede 57 DK 167975 B1 forsøgsforbindelse, og 2 dage senere foretages inficering med en konidiesuspension (400.000 konidier/ml med tilsætning af 0,1% "Tween"®20 som fugtemiddel) af Septoria 5 nodorum. Efter en inkubationstid på 2 dage i en væksthuskabine ved 20°C og en relativ luftfugtighed på 95-100% anbringes forsøgsplanterne frem til forsøgets afslutning utildækket i en væksthuskabine ved 21°C og en relativ luftfugtighed på 60%. Bedømmelsen af 10 svampeangrebet foretages 7-10 dage efter infektionen.Residual Protective Effect 30 7-day-old wheat plants are sprayed with a spray liquid (concentration 0.02%) prepared from the formulated test compound, and 2 days later infested with a conidial suspension (400,000 conidia / ml with the addition of 0, 1% "Tween" ®20 as a wetting agent) of Septoria 5 nodorum. After a 2-day incubation period in a greenhouse cabin at 20 ° C and a relative humidity of 95-100%, the experimental plants are placed uncovered in a greenhouse cabin at 21 ° C and a relative humidity of 60% until the end of the experiment. The assessment of the 10 fungal infestation is done 7-10 days after the infection.
Medens ubehandlede, men inficerede kontrolplanter er helt angrebne, udviser planter, som er behandlet med forbindelser fra tabellen, et svampeangreb på mindre end 20%.While untreated but infected control plants are completely infected, plants treated with compounds from the table exhibit a fungal attack of less than 20%.
Eksempel 3.13: Virkning mod Alternaria solani på tomater 15 Residual-protektiv virkning 3 uger gamle tomatplanter sprøjtes med en sprøjtevæske (koncentration 0,02%), som er fremstillet ud fra et middel indeholdende det aktive stof, og 2 dage senere foretages inficering fra begge sider med en konidiesuspension 20 (20.000 konidier/ml) af Alternaria solani. For at forhindre en afvaskning af sprøjtebelægningen i form af fine dråber, tildækkes de inficerede planter i en første 3 dages inkubationsfase i en væksthuskabine ved 20°C og klimabefugtning med finmaskede net. Derefter anbringes 25 planterne frem til forsøgets afslutning i en væksthuskabine ved 24°C. Bedømmelsen af svampeangrebet foretages 4 dage efter infektionen.Example 3.13: Effect against Alternaria solani on tomatoes 15 Residual-protective effect 3-week-old tomato plants are sprayed with a spray liquid (concentration 0.02%) prepared from an agent containing the active substance, and two days later infections from both pages with a conidia suspension 20 (20,000 conidia / ml) of Alternaria solani. To prevent washing of the spray coating in the form of fine droplets, the infected plants are covered in a first 3 day incubation phase in a greenhouse at 20 ° C and climate humidification with fine mesh. Then, the plants are placed until the end of the experiment in a greenhouse at 24 ° C. The assessment of the fungal attack is done 4 days after the infection.
Medens ubehandlede, men inficerede kontrolplanter er fuldstændigt angrebne, udviser planter, som er behandlet 30 med forbindelser fra tabellen, et svampeangreb på mindre end 20%.While untreated but infected control plants are completely infected, plants treated with compounds from the table exhibit a fungal attack of less than 20%.
Eksempel 3.14: 58 DK 167975 B1 a) Insekticid kontaktvirkning mod Nephotettix cincticeps og Nilaparvata lugens (nymfer) 5 Forsøget gennemføres på risplanter i vækst. Til hvert forsøg udplantes 4 planter (14-20 dage gamle) med en højde på ca. 15 cm i potter (diameter på 5,5 cm).Example 3.14: 58 DK 167975 B1 a) Insecticidal contact action against Nephotettix cincticeps and Nilaparvata hatch (nymphs) 5 The experiment is carried out on growing rice plants. For each experiment 4 plants (14-20 days old) with a height of approx. 15 cm in pots (5.5 cm diameter).
Planterne sprøjtes på en drejeskive med 100 ml vandig emulsionspræparat, som indeholder 400 ppm af den 10 pågældende forsøgsforbindelse. Efter tørring af sprøjtebelægningen besættes hver plante med 20 nymfer af forsøgsdyret på 3. stadium. For at forhindre cikaderne i at undvige, anbringes de besatte planter i en glascylinder, som er åben i begge ender, hvorpå disse lukkes med et 15 gazelåg. Til opnåelse af voksenstadiet holdes nymferne i 6 dage på de behandlede planter. Bedømmelsen af den procentvise mortalitet foretages 6 dage efter besætningen. Forsøget gennemføres ved ca. 27°C og en relativ luftfugtighed på 60% samt en belysningsperiode på 16 timer.The plants are sprayed onto a turntable with 100 ml of aqueous emulsion preparation containing 400 ppm of the 10 test compound. After drying the spray coating, each plant is infested with 20 nymphs of the third-stage experimental animal. To prevent the cicadas from evading, the occupied plants are placed in a glass cylinder which is open at both ends and closed with a gauze cover. To reach the adult stage, the nymphs are kept for 6 days on the treated plants. The percentage mortality is assessed 6 days after the herd. The experiment is carried out at approx. 27 ° C and a relative humidity of 60% and an illumination period of 16 hours.
20 b) Systemisk insekticid virkning mod Nilaparvata lugens (i vand)B) Systemic insecticidal action against the Nilaparvata hatch (in water)
Ca. 10 dage gamle risplanter (højde ca. 10 cm) anbringes i et plastbæger, som indeholder 150 ml emulsionspræparat af forsøgsforbindelsen i en koncentration på 100 ppm, og som 25 er lukket med et plastlåg forsynet med flere huller. Risplantens rod skubbes gennem et hul i plastlåget ned i det vandige forsøgspræparat. Derefter besættes risplanten med 20 nymfer af Nilaparvata lugens i N 2- til N 3-sta-diet, hvorpå de overdækkes med en plastcylinder. Forsøget 30 gennemføres ved ca. 26°C og en relativ luftfugtighed på 60% med en belysningsperiode på 16 timer. Efter 5 dages forløb optælles antallet af døde forsøgsdyr, som sammenlignes med ubehandlede kontroller. Det konstateres herved.Ca. 10 day old rice plants (height about 10 cm) are placed in a plastic beaker containing 150 ml of emulsion preparation of the test compound at a concentration of 100 ppm and which is closed with a plastic lid provided with several holes. The root of the rice plant is pushed through a hole in the plastic lid into the aqueous test preparation. Then, the rice plant is filled with 20 nymphs of the Nilaparvata lugens in the N 2- to N-3 state, and then covered with a plastic cylinder. Experiment 30 is performed at ca. 26 ° C and a relative humidity of 60% with an illumination period of 16 hours. After 5 days, the number of test animals is counted, which is compared to untreated controls. It is hereby ascertained.
DK 167975 ΒΊ 59 om det aktive stof, som er optaget over rødderne, dræber forsøgsdyrene på de øvre plantedele.DK 167975 ΒΊ 59 on the active substance absorbed over the roots kills the test animals on the upper plant parts.
Forbindelser fra tabellen viser såvel ved kontaktforsøget 5 som ved det systemiske forsøg en virkning på mere end 80% mod de anvendte risskadeorganismer.Compounds from the table show an effect of more than 80% against the rice damage organisms used in both contact experiment 5 and systemic experiment.
I det følgende foretages sammenligningsforsøg med en fra DD-patentskrift nr. 151.404 nært beslægtet kendt sammenligningsforbindelse med den nedenfor anførte formel X og 10 et repræsentativt udvalg af forbindelserne med den almene formel I. Nedenfor anføres formel og nr. for de anvendte forsøgsforbindelser.In the following, comparative experiments with a known comparative compound of DD Patent No. 151,404 with Formula X and 10 below are made representative of the compounds of General Formula I. Formula and No. of the test compounds used are listed below.
Forbindelse Formel ch3Compound Formula ch3
x rv-Mx rv-M
\=/ N=/ CH3 (kendt) CHg 0""ø ch2-och3 ch3 2 fy \=/ N=\ ch2-och2ch=ch2 60 DK 167975 B1 CH3 5 O—\ = / N = / CH3 (known) CHg 0 "" ø ch2-och3 ch3 2 fy \ = / N = \ ch2-och2ch = ch2 60 DK 167975 B1 CH3 5 O—
CH2-OCH2-C=CHCH 2 OCH 2 C? CH
ch3 7 \==z/ N=/ ch2-s-ch3 10 / \ NH—/ \ \=/ \=/ ch2-och3 c2h5 38 / \—nh—ζ \=S Ν==ζ\ ch2-och3 ch3 138 F i \ NH—^ \ • v==/ N=/ ch2-och3 ch3 231 ^ \ NH—^ \ \=/ N=/ ch2-och3 DK 167975 Bl 61 ch2-ci 256 f \—NH—^ \ ch2-och3 I nedenstående biologiske forsøg anvendes forbindelserne i form af fortyndede vandige opløsninger af sprøjtepulvere. Ubehandlede men inficerede kontrolplanter udviser et 5 angreb på 100%.ch3 7 \ == z / N = / ch2-s-ch3 10 / \ NH— / \ \ = / \ = / ch2-och3 c2h5 38 / \ —nh — ζ \ = S Ν == ζ \ ch2-och3 ch3 138 F i \ NH— ^ \ • v == / N = / ch2-och3 ch3 231 ^ \ NH- ^ \ \ = / N = / ch2-och3 DK 167975 B1 61 ch2-ci 256 f \ -NH- In the biological experiments below, the compounds are used in the form of dilute aqueous solutions of spray powders. Untreated but infected control plants exhibit a 5% attack of 100%.
Eksempel 3.15:Example 3.15:
Residual-protektiv virkning mod Venturia inaequalis på æbleskud Æblestiklinger med 10-20 lange friske skud sprøjes med en 10 sprøjtevæske (0,002% aktivt stof), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. Efter 24 timers forløb inficeres de behandlede planter med en konidiesuspension af svampen. Planterne inkuberes derefter i 5 dage ved en relativ luftfugtighed på 90-100%, hvorpå 15 de anbringes i yderligere 10 dage i et væksthus ved 20-24°C. Skurvangrebet bedømmes 15 dage efter infektionen.Residual protective effect against Venturia inaequalis on apple shoots Apple cuttings with 10-20 long fresh shoots are sprayed with a 10 spray liquid (0.002% active ingredient), which is made from a spray powder containing the active substance. After 24 hours, the treated plants are infected with a conidial suspension of the fungus. The plants are then incubated for 5 days at a relative humidity of 90-100%, after which they are placed for an additional 10 days in a greenhouse at 20-24 ° C. The scab attack is assessed 15 days after the infection.
Forbindelserne nr. 1, 2, 5, 7, 10, 38, 138, 231 og 256 reducerer skurvangrebet til 0-10%.Compounds Nos. 1, 2, 5, 7, 10, 38, 138, 231 and 256 reduce the scab grip to 0-10%.
Sammenligningsforbindelsen X reducerer angrebet til 20 .10-20%.Comparison compound X reduces the attack to 20 .10-20%.
Eksempel 3.16: 62 DK 167975 B1Example 3.16: 62 DK 167975 B1
Virkning mod Botrytis cinera på æblefrugter Residual-protektiv virkning 5 Kunstigt beskadigede æbler behandles ved podning på de beskadigede steder med en sprøjtevæske (0,002% aktivt stof), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. De behandlede frugter inokule-res derefter med en sporesuspension af svampen, hvorpå de 10 inkuberes i 1 uge ved høj luftfugtighed og en temperatur på ca. 20°C. Ved bedømmelsen optælles de beskadigede steder, hvor der optræder råd, og ud fra dette resultat beregnes forsøgsforbindelsernes fungicide virkning.Effect against Botrytis cinera on apple fruit Residual protective effect 5 Artificially damaged apples are treated by grafting at the damaged sites with a spray liquid (0.002% active substance) prepared from a spray powder containing the active substance. The treated fruits are then inoculated with a spore suspension of the fungus, whereupon they are incubated for 1 week at high humidity and a temperature of approx. 20 ° C. In the assessment, the damaged places where advice occurs are counted and from this result the fungicidal effect of the test compounds is calculated.
Forbindelserne nr. 1, 2, 5, 7, 10, 38, 138, 231 og 256 15 redcderer Botrytis-angrebet til 0%.Compounds Nos. 1, 2, 5, 7, 10, 38, 138, 231 and 256 15 reduce the Botrytis attack to 0%.
Sammenligningsforbindelsen X reducerer angrebet til 20-40%.Comparative compound X reduces the attack to 20-40%.
Eksempel 3.17:Example 3.17:
Virkning mod Erysiphae graminis på byg 20 Residual-protektiv virkningEffect against Erysiphae graminis on barley 20 Residual protective effect
Ca. 8 cm høje bygplanter sprøjtes med en sprøjtevæske (0,006% aktivt stof), som er fremstillet ud fra et sprøjtepulver indeholdende det aktive stof. Efter 3-4 timer bestøves de behandlede planter med konidier af svampen. De 25 inficerede bygplanter anbringes i et væksthus ved ca. 22°C, og svampeangrebet bedømmes efter 10 dages forløb.Ca. 8 cm tall barley plants are sprayed with a spray liquid (0.006% active ingredient), which is made from a spray powder containing the active substance. After 3-4 hours, the treated plants are pollinated with conidia of the fungus. The 25 infected barley plants are placed in a greenhouse at approx. 22 ° C and the fungal attack is evaluated after 10 days.
Forbindelserne nr. 1, 2, 5, 10, 38 og 231 reducerer angrebet med ægte meldug til 10-20%.Compounds Nos. 1, 2, 5, 10, 38 and 231 reduce the attack with real mildew to 10-20%.
Sammenligningsforbindelsen X reducerer angrebet til 30 20-40%.Comparative compound X reduces the attack to 20-40%.
Eksempel 3.18: 63 DK 167975 B1Example 3.18: 63 DK 167975 B1
Virkning mod Septoria nodorum på hvede Residual-protektiv virkning 5 7 dage gamle hvedeplanter sprøjtes med en sprøjtevæske (koncentration 0,02%), som er fremstillet ud fra den formulerede forsøgsforbindelse, og efter 2 dages forløb foretages inficering med en konidiesuspension (400.000 konidier/ml med tilsætning af 0,1% "Tween"® som fugtemid-10 del) af Septoria nodorum.' Efter en inkubationstid på 2 dage i et væksthuskammer ved 20°C og en relativ luftfugtighed på 95-100% anbringes forsøgsplanterne frem til forsøgets afslutning utildækket i et væksthuskammer ved 21°C og en relativ luftfugtighed på 60%. Bedømmelsen af 15 svampeangrebet foretages 7-10 dage efter infektionen.Effect against Septoria nodorum on wheat Residual protective effect 5 7-day-old wheat plants are sprayed with a spray liquid (concentration 0.02%) prepared from the formulated test compound, and after 2 days infection is done with a conidial suspension (400,000 conidia / ml with the addition of 0.1% "Tween" (as a wetting agent) of Septoria nodorum. After an incubation period of 2 days in a greenhouse chamber at 20 ° C and a relative humidity of 95-100%, the experimental plants are placed uncovered in a greenhouse chamber at 21 ° C and a relative humidity of 60% until the end of the experiment. The assessment of the 15 fungal attack is done 7-10 days after the infection.
Forbindelserne nr. 1, 7, 10, 38 og 138 reducerer svampeangrebet til 20-40%.Compounds Nos. 1, 7, 10, 38 and 138 reduce the fungal attack to 20-40%.
Sammenligningsforbindelsen X reducerer praktisk taget ikke angrebet (til 50-100%).Comparative compound X practically does not reduce the attack (to 50-100%).
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GB9625184D0 (en) * | 1996-12-04 | 1997-01-22 | Celltech Therapeutics Ltd | Chemical compounds |
EP0946523A1 (en) | 1996-12-23 | 1999-10-06 | Celltech Therapeutics Limited | Fused polycyclic 2-aminopyrimidine derivatives, their preparation and their use as protein tyrosine kinase inhibitors |
GB9705361D0 (en) * | 1997-03-14 | 1997-04-30 | Celltech Therapeutics Ltd | Chemical compounds |
GB9713087D0 (en) * | 1997-06-20 | 1997-08-27 | Celltech Therapeutics Ltd | Chemical compounds |
GB9914258D0 (en) | 1999-06-18 | 1999-08-18 | Celltech Therapeutics Ltd | Chemical compounds |
GB9924862D0 (en) | 1999-10-20 | 1999-12-22 | Celltech Therapeutics Ltd | Chemical compounds |
JP2001247411A (en) * | 2000-03-09 | 2001-09-11 | Tomono Agrica Co Ltd | Pest-controlling agent |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD151404A1 (en) * | 1980-06-13 | 1981-10-21 | Friedrich Franke | FUNGICIDAL AGENTS |
US4659363A (en) * | 1983-07-25 | 1987-04-21 | Ciba-Geigy Corporation | N-(2-nitrophenyl)-2-aminopyrimidine derivatives, the preparation and use thereof |
US4694009A (en) * | 1984-06-25 | 1987-09-15 | Ciba-Geigy Corporation | Pesticidal compositions |
DE3618353A1 (en) * | 1986-05-31 | 1987-12-03 | Hoechst Ag | PEST CONTROLS BASED ON AMINOPYRIMIDINE DERIVATIVES AND NEW AMINOPYRIMIDINE COMPOUNDS |
EP0264348B1 (en) * | 1986-10-13 | 1993-12-15 | Ciba-Geigy Ag | Ureas |
JPH0784445B2 (en) * | 1986-12-03 | 1995-09-13 | クミアイ化学工業株式会社 | Pyrimidine derivatives and agricultural and horticultural fungicides |
ES2054867T3 (en) * | 1987-09-28 | 1994-08-16 | Ciba Geigy Ag | PESTICIDES AND PESTICIDES. |
-
1988
- 1988-06-02 ES ES88810361T patent/ES2058332T3/en not_active Expired - Lifetime
- 1988-06-02 DE DE8888810361T patent/DE3882821D1/en not_active Expired - Lifetime
- 1988-06-02 EP EP88810361A patent/EP0295210B1/en not_active Expired - Lifetime
- 1988-06-07 CZ CS883926A patent/CZ281586B6/en unknown
- 1988-06-08 FI FI882709A patent/FI98912C/en not_active IP Right Cessation
- 1988-06-08 BG BG84407A patent/BG48205A3/en unknown
- 1988-06-08 BG BG87226/89A patent/BG49939A3/en unknown
- 1988-06-08 BG BG87225/89A patent/BG49923A3/en unknown
- 1988-06-09 ZW ZW75/88A patent/ZW7588A1/en unknown
- 1988-06-09 NZ NZ224969A patent/NZ224969A/en unknown
- 1988-06-09 PL PL1988272950A patent/PL154960B1/en unknown
- 1988-06-09 PT PT87707A patent/PT87707B/en not_active IP Right Cessation
- 1988-06-09 CA CA000568999A patent/CA1305483C/en not_active Expired - Lifetime
- 1988-06-09 IL IL8886666A patent/IL86666A/en not_active IP Right Cessation
- 1988-06-10 DK DK317588A patent/DK167975B1/en not_active IP Right Cessation
- 1988-06-10 IE IE175988A patent/IE62436B1/en not_active IP Right Cessation
- 1988-06-10 AU AU17606/88A patent/AU615912B2/en not_active Ceased
- 1988-06-10 HU HU883006A patent/HU208961B/en not_active IP Right Cessation
- 1988-06-10 BR BR8802852A patent/BR8802852A/en not_active IP Right Cessation
- 1988-06-10 DK DK317588D patent/DK317588A/en unknown
- 1988-06-11 CN CN88103496A patent/CN1032338A/en active Pending
- 1988-06-11 KR KR1019880007066A patent/KR970001478B1/en not_active IP Right Cessation
- 1988-06-11 JP JP63144552A patent/JP2632187B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
FI882709A0 (en) | 1988-06-08 |
PL272950A1 (en) | 1989-03-06 |
PT87707A (en) | 1989-05-31 |
BG49923A3 (en) | 1992-03-16 |
JP2632187B2 (en) | 1997-07-23 |
ZW7588A1 (en) | 1989-01-18 |
HU208961B (en) | 1994-02-28 |
KR890000436A (en) | 1989-03-14 |
CA1305483C (en) | 1992-07-21 |
KR970001478B1 (en) | 1997-02-06 |
FI98912C (en) | 1997-09-10 |
FI882709A (en) | 1988-12-12 |
DK317588D0 (en) | 1988-06-10 |
JPS63316774A (en) | 1988-12-26 |
FI98912B (en) | 1997-05-30 |
CZ281586B6 (en) | 1996-11-13 |
PL154960B1 (en) | 1991-10-31 |
IL86666A0 (en) | 1988-11-30 |
AU1760688A (en) | 1988-12-15 |
EP0295210B1 (en) | 1993-08-04 |
IE62436B1 (en) | 1995-02-08 |
CZ392688A3 (en) | 1996-09-11 |
BG48205A3 (en) | 1990-12-14 |
BR8802852A (en) | 1989-01-03 |
EP0295210A1 (en) | 1988-12-14 |
HUT47383A (en) | 1989-03-28 |
BG49939A3 (en) | 1992-03-16 |
ES2058332T3 (en) | 1994-11-01 |
AU615912B2 (en) | 1991-10-17 |
IL86666A (en) | 1992-09-06 |
IE881759L (en) | 1988-12-11 |
DK317588A (en) | 1988-12-12 |
CN1032338A (en) | 1989-04-12 |
DE3882821D1 (en) | 1993-09-09 |
NZ224969A (en) | 1991-04-26 |
PT87707B (en) | 1995-01-31 |
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