DK142077B - Plant fungicidal halogenacylanilides. - Google Patents
Plant fungicidal halogenacylanilides. Download PDFInfo
- Publication number
- DK142077B DK142077B DK136175AA DK136175A DK142077B DK 142077 B DK142077 B DK 142077B DK 136175A A DK136175A A DK 136175AA DK 136175 A DK136175 A DK 136175A DK 142077 B DK142077 B DK 142077B
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- DK
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- compounds
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- plants
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000003123 plant toxin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003151 propanoic acid esters Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 235000015136 pumpkin Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000003128 rodenticide Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SRAWNDFHGTVUNZ-UHFFFAOYSA-M sodium;3,6-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC(CCCC)=CC2=CC(CCCC)=CC=C21 SRAWNDFHGTVUNZ-UHFFFAOYSA-M 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000001526 topogenic effect Effects 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
- C07C233/46—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/47—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyrrole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Steroid Compounds (AREA)
Description
(11) fremlæggelsesskrift 142077 DANMARK <»<>ι«.α· c 07 c 103/« A Ot N 37/22 §(21) Antegning nr. 156l^5 rø ^ 26. tnar. 1975 (24, Løbedag 2β* mar· 1975 (44) Ansøgningen fremlagt og .(11) Petition 142077 DENMARK <»<> ι« .α · c 07 c 103 / «A Ot N 37/22 § (21) Note No. 156l ^ 5 rö ^ 26. tnar. 1975 (24, Race day 2β * Mar · 1975 (44) The application presented and.
framlaeggelsesekrtftet offentliggjort denthe disclosure notice published on
DIREKTORATET FORDIRECTORATE OF
PATENT-OG VAREMÆRKEVÆSENET (30) 4509/74 CHPATENT AND TRADEMARKET SYSTEM (30) 4509/74 CH
15. feb. 1975, 1785/75, CHFeb 15 1975, 1785/75, CH
(71) CIBA-GrEIGT AG, 4002 Basel, CH.(71) CIBA-GREIGT AG, 4002 Basel, CH.
(72) Opfinder: Adolf Hubele, Im Egg, 4465 Magden, CH.(72) Inventor: Adolf Hubele, Im Egg, 4465 Magden, CH.
(74) Fuldmægtig under sagens behandling:(74) Plenipotentiary in the proceedings:
Dansk Patent Kontor ApS.Dansk Patent Kontor ApS.
(64) Plantefungicide halogenacylanilider.(64) Plant fungicidal haloacyl anilides.
Den foreliggende opfindelse angår hidtil ukendte plantefungicide halogenacylanilider, som er ejendommelige ved, at de har den almene formel γη 0Ηλ CH3 j 3 /CH-COOCH,The present invention relates to novel plant fungicidal haloacyl anilides which are characterized in that they have the general formula γη 0Ηλ CH 3 j 3 / CH-COOCH,
<T>-H<T> -H
z>=r xco-z2 (i) p hvori Z er hydrogen eller methyl, Z"*" er methyl eller ethyl, ogz> = r xco-z2 (i) p wherein Z is hydrogen or methyl, Z "*" is methyl or ethyl, and
OISLAND
Z er en med et chlor-, brom- eller iodatom substitueret C^C^-alk-ylgruppe.Z is a C 1 -C 4 -alkyl group substituted with a chloro, bromo or iodo atom.
2 1420772 142077
Ved en C 2 -C ^-alkylgruppe skal forstås ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s ek.butyl.By a C 2 -C 4 alkyl group is meant ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s.
I tysk offentliggørelsesskrift nr. 2.212.268 angives det i almen form, at N-halogenacylerede anilinoalkancarboxylsyreestere har selektiv herbicid virkning. Der nævnes dog kun ved navn nogle N-halogenacety-lerede 2,β-dialkylanilinoeddikesyrer og deres estere, og kun disses virkning som herbicider dokumenteres. Der er ikke henvisninger til mikrobicid, især piantefungicid virkning.German Patent Specification No. 2,212,268 discloses in general form that N-haloacylated anilinoalkanecarboxylic acid esters have selective herbicidal activity. However, only some N-haloacetylated 2, β-dialkylanilinoacetic acids and their esters are mentioned by name, and only their effect as herbicides is documented. There are no references to microbicide, especially piante fungicide action.
I beskrivelsen til DK patentansøgning nr.5552/73 er endvidere beskrevet 2,6-dialkylanilinoeddikesyreestere, der ligeledes er N-halo— genacetylerede. De har mikrobicid, især plantefungicid, virkning.In the description of DK patent application no. 5552/73, furthermore, 2,6-dialkylanilinoacetic acid esters are also described, which are also N-halogenacetylated. They have microbicide, especially plant fungicide, effect.
Gruppen af N-(l'-methoxycarbonyl-ethyl)-N-halogenacyl-2,6-dialkyl-aniliner med formlen I har hidtil ikke -været beskrevet i litteraturen, og de er således hidtil ukendte. Det er overordentligt overraskende, at denne gruppe i modsætning til de i tysk offentliggørelsesskrift nr. 2.212.268 beskrevne anilinoeddikesyrer og -eddikesyreestere har stærke plantefungicide egenskaber.The group of N- (1'-methoxycarbonyl-ethyl) -N-haloacyl-2,6-dialkyl-anilines of formula I has hitherto not been described in the literature, and thus they are novel. Surprisingly, in contrast to the anilinoacetic acids and acetic acid esters described in German Publication No. 2,212,268, this group has strong plant fungicidal properties.
Således har forbindelserne med formlen I såvel præventiv som kurativ virkning mod fy topatogene svampe hos kulturplanter, såsom korn, majs, ris, grøntsager, sukkerroer, soja, jordnødder, frugttræer, prydplanter, men fremfor alt hos vinplanter, humle, agurkevækster (agurker, græskar, meloner) og solanaceer, såsom kartofler, tobak og tomater, samt banan-, kakao- og kaut s jukplanter.Thus, the compounds of Formula I have both preventive and curative effects against five topogenic fungi in cultural plants, such as cereals, corn, rice, vegetables, sugar beets, soy, peanuts, fruit trees, ornamental plants, but above all in vines, hops, cucumber plants (cucumbers, pumpkins) , melons) and solanas, such as potatoes, tobacco and tomatoes, as well as banana, cocoa and cautery juice plants.
Med disse virksomme stoffer kan svampe, der optræder hos planter eller plantedele (frugter, blomster, løvværk, stængler, knolde, rødder), hæmmes eller tilintetgøres, hvorved også senere tilvoksende plantedele forbliver forskånet for sådanne svampe. De virksomme stoffer er virksomme mod fytopatogene svampe, der tilhører de følgende klasser: Asco-mycetes (Erysiphaceae); Basidiomycetes, såsom fremfor alt rustsvampe; Fungi imperfecti (såsom Moniliales); men især mod de til klassen af Phycomycetes hørende Oomycetes, såsom Phytophthora, Peronospora, Pseudoperonospora, Pythium eller Plasmopara. Desuden virker forbindelserne med formlen I systemisk.With these active substances, fungi that occur in plants or parts of the plant (fruits, flowers, foliage, stems, tubers, roots) can be inhibited or destroyed, so that later growing parts of the plant will also be spared from such fungi. The active substances are effective against phytopathogenic fungi belonging to the following classes: Asco-mycetes (Erysiphaceae); Basidiomycetes, such as, above all, rust fungi; Fungi imperfecti (such as Moniliales); but especially against those of the class of Phycomycetes belonging to Phycomycetes, such as Phytophthora, Peronospora, Pseudoperonospora, Pythium or Plasmopara. In addition, the compounds of formula I act systemically.
3 1420773 142077
De kan endvidere anvendes som bejdsemidler til behandling af såmateriale (frugter, knolde, kom) og plante stiklinger til beskyttelse mod svampeinfektioner samt mod fytopatogene svampe, der optræder i jorden.They can also be used as seed dressings for the treatment of seed material (fruits, tubers, grains) and plant cuttings for protection against fungal infections as well as against phytopathogenic fungi that occur in the soil.
Når der ønskes præparater med udvidet eller ændret virkningsspektrum, kan de virksomme stoffer med formlen I blandes med andre kendte fungicider, baktericider, fungistatika, bakteriostatika, men også med insekticider, akaricider, herbicider, og på grund af deres systemiske virkning, der tillader en jordapplikation, også med nematodicider, molluskicider eller rodenticider, hvorved der til dels opnås synergistisk forøgede virkninger.When extended or modified spectrum of action is desired, the active substances of formula I may be mixed with other known fungicides, bactericides, fungistatics, bacteriostatics, but also with insecticides, acaricides, herbicides, and because of their systemic effect permitting a soil application , also with nematodicides, molluscicides or rodenticides, thereby partly achieving synergistically enhanced effects.
Som det fremgår af eksempel 4, er de omhandlede forbindelser fordel-r agtige i forhold til de i ansøgning nr. 5552/73 beskrevne beslægtede forbindelser ved at give en større sikkerhed mod planteforgiftning · ved tilfældig overdosering. ,As can be seen from Example 4, the compounds of this invention are advantageous over the related compounds described in application No. 5552/73 by providing greater safety against plant poisoning by accidental overdose. .
En mikrobicidt foretrukket gruppe af forbindelser er sådanne méd formlen I, hvori er methyl. Disse benævnes forbindelsesgruppe la.A microbicidal preferred group of compounds are those of Formula I wherein is methyl. These are referred to as connecting group 1a.
En anden mikrobicidt vigtig gruppe af forbindelser med formlen I erAnother microbicide important group of compounds of formula I is
1 2 sådanne, hvori Z er hydrogen, og Z er methyl eller ethyl, medens Z1 2 wherein Z is hydrogen and Z is methyl or ethyl, while Z
—CH—R-CH-R
er en gruppe , , hvori R er methyl eller ethyl, og Y er chlor el-is a group wherein R is methyl or ethyl and Y is chloro or
YY
ler brom. Disse benævnes forbindelsesgruppe Ib.smiles of bromine. These are referred to as connecting group Ib.
Forbindelserne med formlen I har et asymmetrisk carbonatom i propion- ester-sidekæden. Forbindelser med formlen I, la og Ib i D-konfigura- tionen har den stærkeste mikrobicide virkning og er derfor foretrukne.The compounds of formula I have an asymmetric carbon atom in the propion ester side chain. Compounds of formula I, Ia and Ib in the D configuration have the strongest microbicidal effect and are therefore preferred.
2 I halogenalkyl-sidekæden Z kan der ved en del af forbindelserne alt efter substitution foreligge et andet asymmetrisk carbonatom. Hvis der ved fremstillingen ikke anvendes optisk aktive udgangsmaterialer, får man nødvendigvis en diast er eomerblanding. Såf remt der i det følgende ikke bemærkes andet, menes der ved omtalen af et af de virksomme stoffer med formlen I altid diastereomerblandingen.2 In the haloalkyl side chain Z, a second asymmetric carbon atom may be present for some of the compounds. If optically active starting materials are not used in the manufacture, a diastereomer is necessarily obtained. Unless otherwise noted in the following, by the mention of one of the active substances of formula I is always meant the diastereomer mixture.
Fremstillingen af forbindelserne sker f. eks. ved, at man først omsætter en anilin med formlen ch3 ^_p>-NH2 (II) Z I η z1 4 142077 med den ønskede α-halo genpropionsyremethyl ester med formlen CHo i 3The compounds of the invention are prepared, for example, by first reacting an aniline of the formula ch3 ^ p> -NH2 (II) Z I η z1 4 142077 with the desired α-halo gene propionic acid methyl ester of the formula CHo in 3
Hal-CH-C00CH3 (III) og derpå omsætter den opnåede forbindelse med formlen CH-j ρ,ττ ,_I 3 |H3 </ V -UH-CH-C00CH3 (IV) (l z p med den ønskede balo genalkane arb o xylsyre H00C-Z eller dens reaktionsdygtige syr ehalo g eni d, syreanhydrid, ester eller amid, fortrinsvis med halogenidet eller anhydridet af den chlor-, brom- eller iodalkancarb-oxylsyre, der kommer på tale.Hal-CH-C00CH3 (III) and then reacting the obtained compound of the formula CH-j ρ, ττ, _I 3 | H3 </ V -UH-CH-C00CH3 (IV) (lzp with the desired balo gene alkane moiety o xylic acid H00C -Z or its reactive acid, or anhydride, acid anhydride, ester or amide, preferably with the halide or anhydride of the chlorine, bromine or iodoalkanecarboxylic acid involved.
1 2 I de ovenstående formler har Z, Z og Z de under formlen I angivne betydninger, medens Hal i formlen III er halogen, fortrinsvis chlor eller brom. Som syrehalogenider foretrækkes syrechlorideme eller syre-bromiderne.In the above formulas, Z, Z and Z have the meanings given under formula I, while Hal in formula III is halogen, preferably chlorine or bromine. As acid halides, the acid chlorides or acid bromides are preferred.
Omsætningerne kan gennemføres i nær- eller fraværelse af opløsningseller fortyndingsmidler, der er inaktive overfor reaktionsdeltageme. Der kan eksempelvis anvendes: aliphatiske eller aromatiske car-bonhydridér, såsom benzen, toluen, xylener ogpetroleumsether; halogenerede carbonhydrider, såsom chlorbenzen, methylenchlorid, ethylenchlo-rid og chloroform; ethere og etheragtige forbindelser, såsomdialkyl-éthere,dioxan og tetrahydrofuran; nitriler, såsom acetonitril; H,H-di-alkylerede amider, såsom dimethylformamid; vandfri eddikesyre, dime-thylsulfoxid, ketoner, såsom methylethylketon, og blandinger af sådanne opløsningsmidler.The reactions may be carried out in the presence or absence of solvents or diluents which are inactive against the reaction participants. For example, aliphatic or aromatic hydrocarbons such as benzene, toluene, xylenes and petroleum ether may be used; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride and chloroform; ethers and ether-like compounds such as dialkyl ethers, dioxane and tetrahydrofuran; nitriles such as acetonitrile; H, H-di-alkylated amides such as dimethylformamide; anhydrous acetic acid, dimethyl sulfoxide, ketones such as methyl ethyl ketone, and mixtures of such solvents.
Reaktionstemperatureme ligger mellem 0 og 180°C, fortrinsvis mellem 20 og 120°C. I mange tilfælde, især ved anvendelse af halogenacylhalo-genider, gennemføres a-halogenacyleringen i nærværelse af et syrebindende middel eller kondensationsmiddel. Der kan anvendes tertiære aminer, såsom tri alkyl aminer (f. eks. tri e thyl amin), pyridin og pyridinbaser, eller uorganiske baser, såsom oxider og hydroxider, hydrogencarbonater og carbonater af alkali- og Jordalkalime-tailer samt natriumacetat. Som syrebindende middel kan desuden anvendes et overskud af det pågældende anilinderivat med formlen II.The reaction temperatures are between 0 and 180 ° C, preferably between 20 and 120 ° C. In many cases, especially using haloacyl halides, the α-haloacylation is carried out in the presence of an acid-binding agent or condensing agent. Tertiary amines such as tri alkyl amines (e.g. triethyl amine), pyridine and pyridine bases, or inorganic bases such as oxides and hydroxides, hydrogen carbonates and alkali and alkaline earth metal carbonates, and sodium acetate may be used. In addition, an excess of the relevant aniline derivative of formula II can be used as an acid binding agent.
5 1420775 142077
Reaktionen kan også gennemføres uden syrebindende middel, og det er da i nogle tilfælde hensigtsmæssigt at gennemlede nitrogen til fjernelse af det dannede hydro genhalo genid. Hvis reaktionen gennemføres uden syrebindende midler, virker dime thylf ormamid i reglen katalyserende.The reaction can also be carried out without an acid-binding agent, and it is then appropriate in some cases to pass nitrogen to remove the hydro-halo genide formed. If the reaction is carried out without acid binding agents, the dime thylph ormamide usually acts as a catalyst.
Enkeltheder angående fremstillingen af mellemprodukterne med formlen IV kan udledes af de metoder, der alment er angivet om fremstillingen af anilinoalkansyreestere i følgende publikationsorganer: J.Org.Chem. 30, 4101 (1965), Tetrahedron 1967, 487, Tetrahedron 1967, 493·Details of the preparation of the intermediates of formula IV can be deduced from the methods generally disclosed for the preparation of anilinoalkanoic acid esters in the following publication bodies: J.Org.Chem. 30, 4101 (1965), Tetrahedron 1967, 487, Tetrahedron 1967, 493 ·
Til fremstilling af de rene optiske former med formlen I fremstiller man f.eks. ud fra anilinen med formlen II og α-halogenpropionsyren, f.eks. α-brompropionsyren, den tilsvarende racemiske anilinopro pi onsyr e med formlen f3 CH3 ^ V-NH-CH-C00H (V) Z '1 zr og omsætter den på i og for sig kendt måde med en H~holdig optisk aktiv base. Ved fraktioneret krystallisation af det opnåede salt og efterfølgende frigørelse af den optiske D-antipode, eventuelt også gentagelse af reaktionen med den optisk aktive base, vinder man en af de enantiomere former af den tilsvarende forbindelse med formlen V. Af denne kan man så på sædvanlig måde, f.eks. i nærværelse af HC1 eller H2S0^, med methanol danne den optisk aktive ester IV. På analog måde kan også de for dannelsen af anilideme med formlen I nødvendige halo- 2 genalkancarboxylsyrer med formlen H00C-Z , såfremt de har et asymmetrisk carbonatom, ved hjælp af en N-holdig optisk aktiv base overføres til en af de to enantiomere former, der på deres side kan bringes til reaktion med en optisk aktiv ester med formlen IV. Således len man målrettet fremstille de forskellige diastereomere med formlen I.For the preparation of the pure optical forms of formula I, e.g. from the aniline of formula II and the α-halo propionic acid, e.g. the α-bromopropionic acid, the corresponding racemic anilinopropionic acid of formula f3 CH3 ^ V-NH-CH-C00H (V) Z '1 zr, and reacting it in a manner known per se with an H-containing optically active base. By fractional crystallization of the salt obtained and subsequent release of the optical D antipode, optionally also repeating the reaction with the optically active base, one of the enantiomeric forms of the corresponding compound of formula V. is obtained. way, e.g. in the presence of HCl or H2SO4, with methanol forming the optically active ester IV. Similarly, for the formation of the anilides of formula I, the haloalkanecarboxylic acids of formula H00C-Z, if they have an asymmetric carbon atom, can also be transferred to one of the two enantiomeric forms by means of an N-containing optically active base. which in turn can be reacted with an optically active ester of formula IV. Thus, it is convenient to prepare the various diastereomers of formula I.
Som optisk aktiv organisk base kan f.eks. α-phenylethylamin anvendes.As an optically active organic base, e.g. α-phenylethylamine is used.
I stedet for ved fraktioneret krystallisation kan de enantiomere D-forrner med formlen IV også fremstilles ved, at man diazoterer amino-gruppen i naturligt forekommende 1-alanin i nærværelse af f.eks. HC1 eller HBr og dermed under N2-fraspaltning og under retention af L-kon- 6 142077 figurationen udbytter med halogen, derefter foresterer med methanol og så omsætter med anilinen med formlen II, hvorved der overvejende indtræder inversion til D-konfigurationeme med formlen IV (j.Am.Chem.Instead of by fractional crystallization, the enantiomeric D-precursors of formula IV can also be prepared by diazotizing the amino group in naturally occurring 1-alanine in the presence of e.g. HCl or HBr, and thus during N2 decomposition and during retention of the L-conjugation, yields with halogen, then esterifies with methanol and then reacts with the aniline of formula II, whereby inversion to the D configurations of formula IV (predominantly) occurs ( j.Am.Chem.
Soc. 76, 6056).Soc. 76, 6056).
Fremstillingen af de virksomme stoffer med formlen I illustreres af de følgende eksempler 1 og 2.The preparation of the active substances of formula I is illustrated by the following Examples 1 and 2.
Eksempel 1.Example 1.
Fremstilling af CHt ?H3 1 3 I J CH-C00CH.Preparation of CHt? H3 1 3 I J CH-C00CH.
<!>-< N-f nC0-CH-CH3 CH3 Cl E-(l' -methoxycarhonyl-ethyl) -H-a-chlorpropionyl-2,6-dimethylanilin (D,I).<1> - <N -FNCO-CH-CH3 CH3 Cl E- (1'-methoxycarhonyl-ethyl) -H-a-chloropropionyl-2,6-dimethylaniline (D, I).
a) Fremstilling af mellemproduktet a-(2,6-dimethylanilino)-propionsyre-methylester.a) Preparation of the intermediate α- (2,6-dimethylanilino) -propionic acid methyl ester.
67 g 2,6-dimethylanilin, 125 g α-brompropionsyremethylester og 53 g NaHCO^ omrøres ved en oliebadstemperatur på 140°C i 17 timer og fortyndes efter afkøling med 300 ml ether. Efter to ganges vask med vand tørres etherekstrakten over natriumsulfat og filtreres. Efter afdestillation af etheren og den overskydende a-brompropionsyremethylester i vandstrålevakuum destilleres råproduktet; kp. 98°C/0,8 mm Hg.67 g of 2,6-dimethylaniline, 125 g of α-bromopropionic acid methyl ester and 53 g of NaHCO 3 are stirred at an oil bath temperature of 140 ° C for 17 hours and diluted after cooling with 300 ml of ether. After washing twice with water, the ether extract is dried over sodium sulfate and filtered. After distilling off the ether and the excess α-bromopropionic acid methyl ester in water jet vacuum, the crude product is distilled; kp. 98 ° C / 0.8 mm Hg.
fa) 51,8 g af den ifølge a) fremstillede propionsyreester og 35 g a-ehlorpropionsyrecblorid bringes sammen i 300 ml chlorbenzen under omrøring, hvorved temperaturen af reaktionsblandingen stiger til 40°C.(fa) 51.8 g of the propionic acid ester prepared in (a) and 35 g of a-ehloropropionic acid chloride are combined in 300 ml of chlorobenzene with stirring, raising the temperature of the reaction mixture to 40 ° C.
Efter tilsætning af 2 ml dimethylformamid opvarmes i 2 timer under tilbagesvaling, og chlorbenzenet afdestilleres i vakuum. Ved rivning med petroleumsether bringes råproduktet til krystallisation.After the addition of 2 ml of dimethylformamide, it is heated under reflux for 2 hours and the chlorobenzene is distilled off in vacuo. By tearing with petroleum ether, the crude product is crystallized.
Efter omkrystallisation i toluen smelter diastereomereblandingen, der i den omkrystalliserede prøve ifølge NMR-spektrum er til stede i et forhold på 2:3, ved 108-110°C (forbindelse nr. l).After recrystallization in toluene, the diastereomer mixture, which is present in the recrystallized sample of NMR spectrum in a ratio of 2: 3, melts at 108-110 ° C (Compound No. 1).
7 1420777 142077
Eksempel 2.Example 2.
Fremstilling af CH-, CH, I 3 I J CH-COOCH, N-r ^C-CH^CH^Cl ch3 II 2 2 -5 o N-(l1 -methoxycarbonyl-ethyl)-]!Mp-chlorethylcarbonyl)-2,6-dimethyl-anilin (forbindelse nr. 13).Preparation of CH-, CH, I 3 IJ CH-COOCH, No. ^ C-CH ^ CH ^ Cl ch3 II 2 2 -5 o N- (11-Methoxycarbonyl-ethyl) -] - (1-mp-chloroethyl-carbonyl) -2,6 -dimethyl-aniline (compound # 13).
Til 74 g N-(l-m ethoxy carbonyl-et hyl) -2,6-dimethyl anilin i 300 ml chlorbenzen dryppes 57 g 3~cblorpropionsyrechlorid i 200 ml chlor-benzen. Efter at den svagt eksoterme reaktion er klinget af, tilsattes 2 ml dimethyl formamid, og blandingen opvarmes i 4 timer tinder tilbagesvaling. Efter afkøling vaskes reaktionsblandingen to gange med fortyndet natriumcarbonatopløsning og to gange med vand, tørres over natriumsulfat, filtreres, og opløsningsmidlet afdestilleres i rotationsfordamper. Efter omkrystallisation af petroleums ether har forbindelsen et smp. på 6g-71°C.To 74 g of N- (1-ethoxy carbonyl-ethyl) -2,6-dimethyl aniline in 300 ml of chlorobenzene are dropped 57 g of 3-chlorobropionic acid chloride in 200 ml of chlorobenzene. After the slightly exothermic reaction was quenched, 2 ml of dimethyl formamide was added and the mixture was heated for 4 hours to reflux. After cooling, the reaction mixture is washed twice with dilute sodium carbonate solution and twice with water, dried over sodium sulfate, filtered and the solvent is distilled off in rotary evaporator. After recrystallization of petroleum ether, the compound has a m.p. at 6g-71 ° C.
På en med eksempel la) analog måde fremstilles også følgende propion-syremethylestere som mellemprodukter: a-(2-ethyl-6-methylanilino)-, kp. 88-90°C/0,Gl mm Hg, a-(2-ethyl-3,6-dimethylanilino)-, kp. 96-99°0/0,03 mm Hg, a-(2,3,6-trimethylanilino)~, kp. 83-85°C/0,03 mm Hg; kp. 144-146°C/ 9 mm Hg, a-(2,4,6-trimethylanilino)-, kp. 88-90°C/0,04 mat Hg, q-( 2-ethyl-5,6-dim ethyl anil ino) -, kp. 87-90° C/0,04 mm Hg.In an analogous manner to Example 1a) the following propionic acid methyl esters are also prepared as intermediates: α- (2-ethyl-6-methylanilino) -, b.p. 88-90 ° C / O, Gl mm Hg, α- (2-ethyl-3,6-dimethylanilino) -, b.p. 96-99 ° 0 / 0.03 mm Hg, α- (2,3,6-trimethylanilino) ~, bp. 83-85 ° C / 0.03 mm Hg; kp. 144-146 ° C / 9 mm Hg, α- (2,4,6-trimethylanilino) -, bp. 88-90 ° C / 0.04 with Hg, q- (2-ethyl-5,6-dimethyl anilino) -, b.p. 87-90 ° C / 0.04 mm Hg.
På denne måde eller efter en af de ovenfor angivne metoder fremstilles følgende forbindelser med formlen I, idet de som jordfungicider og/eller bejdsemidler særligt egnede iodholdige forbindelser f.eks. kan fremstilles ud fra de chlorholdige forbindelser ved halogenudbytning med alkalimetaliodid (Z^ = 6-stilling): 8 142077In this way or by any of the methods set forth above, the following compounds of formula I are prepared, having as iodine fungicides and / or dressing agents particularly suitable iodine-containing compounds, e.g. can be prepared from the chlorine-containing compounds by halogen exchange with alkali metal iodide (Z + = 6 position): 8 142077
Forbindelse Z Z^ Z^ Fysisk nr. kons tantCompound Z Z ^ Z ^ Physical No. Contant
_°C_ ° C
1 Ξ CH3 -CH-CH^ Smp.108-110°1 Ξ CH 3 -CH-CH 2 Mp.108-110 °
Cl 2 Ξ CH, -CH-OH, Kp. 148-152°/ ? ^ 0,05 mm Hg 5 H CH, -CH-CHp-CH, Kp. 143-145°/ 5 σι " 0,1131111 Hs 4 H- CH, -CH-CHp-CH, Kp. 140-142°/ 5 gr 5 0,1 mm Hg 5 H CpHt- -CH-CH, Kp. 127-130°/ ^ 5 Cl 0,03 111111 Hs 6 H CX -CH-CH, Kp. 149-155°/ ^ ir 3 0,0? mm Hg 7 H C0Hc -CH-CHo-0H, Kp. 140-142°/ 25 01 0,1 mm Hg 8 H C XX -CH-CH0-CH, Kp. 147-149°/ 25 ir 0,1 mm Hg 9 H CH, -CHo-CHo-CHo-01 Kp. 150-152°/ 3 2 2 2 * o,03 mm Hg 10 3-0¾ CH-, -CH„-CH„-CH„-C1 Kp. 158-162°/ 3 3 2 2 2 * 0,03 mm Hg 11 Ξ C2H5 -CH2-CH2-CH2-C1 viskos 12 3-CH^ C2H5 -CH2-CH2-CH2-C1 viskos 13 H CH^ -CH2-CH2-C1 Smp. 69-71° 14 3-CH^ CH3 -CH2-CH2-C1 Smp. 85-89° 15 H ^2^5 -CH2-CH2-C1 kalvkrystallinsk 16 3-OH, C XX -0Ho-CHo-Cl viskos 3 2 5 2 2 17 4—CH, CH, -CHo-0Ho-Cl Smp. 99-100° 5 5 2 2 18 H CH^ -CH2-CH2-Br viskos 19 3-0¾ 0¾ -CHo-0Ho-Br viskos 5 5 2 2 20 H CH, -CH-CH, Kp. 156-159°/ 0 ^ 5 0,02 mm Hg 21 3-OH, OH, -CH-CH, Kp. 162-164°/ 'j 5 0,01 mm Hg 22 5-CH. OH. -CH-CH. Kp. 171-175°/ 5 5 j 5 * 0,02 mm Hg U20 77 9Cl 2 Ξ CH, -CH-OH, Kp. 148-152 ° /? 0.05 mm Hg 5 H CH, -CH-CHp-CH, Kp. 143-145 ° / 5 σι 0.1131111 Hs 4 H- CH, -CH-CHp-CH, bp 140-142 ° / 5 gr 5 0.1 mm Hg 5 H CpHt- -CH-CH, Kp. 127-130 ° / 5 Cl 0.03 111111 Hs 6 H CX -CH-CH, bp 149-155 ° / ir 3 0.0? Mm Hg 7 H COHc -CH-CHo-OH, bp 140 -142 ° / 25 01 0.1 mm Hg 8 HC XX -CH-CHO-CH, bp 147-149 ° / 25 ir 0.1 mm Hg 9 H CH, -CHo-CHo-CHo-01 bp 150 -152 ° / 3 2 2 2 * o, 03 mm Hg 10 3-0¾ CH-, -CH₂ -CH₂ -CH₂-C1 bp 158-162 ° / 3 3 2 2 2 * 0.03 mm Hg 11 Ξ C 2 H 5 -CH 2 -CH 2 -CH 2 -C1 viscose 12 3-CH 2 C 2 H 5 -CH 2 -CH 2 -CH 2 -C1 viscose 13 H CH 2 -CH 2 -CH 2 -C1 mp 69-71 ° 14 3-CH 2 CH 3 - CH2-CH2-C1 Mp 85-89 ° H ^ 2 ^ 5 -CH2-CH2-C1 Calc crystalline 16 3-OH, C XX-OH-CHo-Cl viscose 3 2 5 2 2 17 4 — CH, CH, -CHo-OH-Cl mp 99-100 ° 5 5 2 2 18 H CH 2 -CH 2 -CH 2 -Br viscose 19 3-0¾ 0¾ -CHo-OH-Br viscose 5 5 2 2 20 H CH, -CH- CH, bp 156-159 ° / 0 5 0.02 mm Hg 21 3-OH, OH, -CH-CH, bp 162-164 ° / 5 0.01 mm Hg 22 5-CH. OH .CH-CH CHP 171-175 ° / 5 5 j 5 * 0.02 mm Hg U20 77 9
Forbindelse Z T? Fysisk nr. konstant oc 23 H CH, -CH-CH0-CH, viskos 3 t 2 5Compound Z T? Physical No. constant and 23 H CH, -CH-CHO-CH, viscous 3 t 2 5
JJ
24 3-CH, CH, -CH-CH„-CH, halvkrystallinsk 2 3 t 2 224 3-CH, CH, -CH-CH 2 -CH, semi-crystalline 2 3 t 2 2
JJ
25 H CH5 -CH-CH(CH5)2 olie, n^° =H CH5 -CH-CH (CH5) 2 oil, n + ° =
Cl 1,5275 26 3-CH, CH, -CH-CH(CH,), viskos 3 3 i 3 4Cl 1.5275 26 3-CH, CH, -CH-CH (CH,), viscous 3 3 in 3 4
Cl 27 H CgHj- -CH-CH(CH^)2 viskosCl 27 H Cg H 2 - -CH-CH (CH 2) 2 viscose
Cl 28 3-CH^ C^ -CH-CH(CH5)2 halvkiystallinskCl 28 3-CH 2 C 2 -CH-CH (CH 5) 2 semi-crystalline
Cl 29 4-CH, CH, -GH-CH(CH,)D Kp. 172-174°/ '2 * ^ 5 £ 0,08 raa Hg 30 4-CH, GÆ,- -CH-CH(CH,)„ Kp. 152-154°/ 5 ^ -7 ^ 5 2 0,04 ran Hg 31 H CH^ -CH2-CH-CH2-CH5 halvkrystallinskCl 29 4-CH, CH, -GH-CH (CH,) D b.p. 172-174 ° / 2 ° 5 £ 0.08 ra Hg 4-CH, GÅ, - -CH-CH (CH 152-154 ° / 5 ^ -7 ^ 5 2 0.04 Ran Hg 31 H CH 2 -CH 2 -CH-CH 2 -CH 5 semi-crystalline
Cl 32 3-CH, CH, -CH0-CH-CH--GH, Kp. 161-163°/ 5 5 d Q,i 2 0,02 mm Hg 33 H C 2^ -CH2-CH-CH2-CH^ viskosCl 32 3-CH, CH, -CHO-CH-CH - GH, bp. 161-163 ° / 5 d Q, 2 0.02 mm Hg 33 H C 2 -CH 2 -CH 2 -CH 2 -CH 2 viscose
ClCl
CHCH
34 H CH, -C^ 5 Smp. 67-69° 5 c70H3 35 4-CH, CH, -CHCH, Smp. 120-122° j 0 * o34 H CH2 -C5 Mp. 67-69 ° C70H3 4-CH, CH, -CHCH, m.p. 120-122 ° j 0 * o
Cl 36 4-CH, CH, -CH0CH0CH0C1 Kp. 158-164°/ 5 5 2 2 2 0,03 jjjjh Hg 37 3-CH, C0H, -CHCH, Kp. 137-139°/ 525 £ 5 0,04 mm Hg 38 3-CH3 C2H5 -CHCHj viskos j 39 5-CH3 C2H5 -CHCH^ viskosCl 36 4-CH, CH, -CHOCHOCHOCl1 Kp. 158-164 ° / 5 5 2 2 2 0.03 yyyy Hh 37 3-CH, COH, -CHCH, Kp. 137-139 ° / 525 £ 5 0.04 mm Hg 38 3-CH 3 C 2 H 5 -CHCH 2 viscose 39 5-CH 3 C 2 H 5 -CHCH 3 viscose
Cl 40 5-CH, CÆ -CHCH, Kp. 155-157°/ 5 2 2 .2 0,03 mm Hg cl 142077 ίοCl 40 5-CH, CÆ -CHCH, Kp. 155-157 ° / 5 2 2 .2 0.03 mm Hg cl 142077 ίο
Forbindelserne med formlen I kan til udvidelse af deres virkningsspektrum anvendes sammen med andre egnede pesticide eller plante-vaekstfremmende virksomme stoffer.The compounds of formula I can be used to extend their spectrum of action with other suitable pesticides or plant growth promoting agents.
Forbindelserne med formien I kan anvendes for sig alene eller sammen med egnede bærere og/eller andre tilsætningsstoffer. Egnede bærere og tilsætningsstoffer kan være faste eller flydende og svarer til de i formuleringsteknikken sædvanlige stoffer, såsom naturlige eller regenererede mineralske stoffer, opløsnings-, dispergerings-, befugtnings-, kæfte-, fortykkelses-, binde- eller gødningsmidler.The compounds of Form I can be used alone or together with suitable carriers and / or other additives. Suitable carriers and additives may be solid or liquid and are similar to those of the art of the formulation technique, such as natural or regenerated mineral substances, solvents, dispersants, wetting, jawing, thickening, binder or fertilizers.
Indholdet af virksomt stof i midler til forhandling ligger mellem 0,1 og 90$.The content of the active substance in the means of negotiation is between $ 0.1 and $ 90.
Til applikation kan forbindelserne med formlen I foreligge i følgende oparbejdningsformer (idet vægtprocent angivelserne i parentes er fordelagtige mængder af virksomt stof):For application, the compounds of formula I may be in the following working forms (the percentages by weight of which are given in parentheses are advantageous amounts of active substance):
Faste oparbejdnings former: støvemidler og strømidler (op til 10$), granulater, omhylningsgranulater, imprægneringsgranulater og homogengranulater (1-80$).Solid forms of reprocessing: dusting agents and powders (up to $ 10), granules, wrapping granules, impregnating granules and homogeneous granules (1-80 $).
Flydende oparbejdningsformer: a) i vand dispergerbare koncentrater af virksomt stof: sprøjtepulvere (befugtelige pulvere) og pastaer (25-90$ i handelspakning, 0,01-15$ i brugsfærdig opløsning), emulsions- og opløsningskoncentrater (10-50$, 0,01-15$ i brugsfærdig opløsning) ; b) opløsninger (0,1-20$).Liquid reprocessing forms: (a) water dispersible active ingredient concentrates: spray powders (wettable powders) and pastes ($ 25-90 in commercial packing, $ 0.01-15 in ready-to-use solution), emulsion and solution concentrates ($ 10-50, 0 , $ 01-15 in ready-to-use solution); b) solutions ($ 0.1-20).
De virksomme stoffer med formlen I kan f. eks. formuleres som følger: Støvemidler:For example, the active substances of formula I may be formulated as follows:
Til fremstilling af et a) 5$'s og b) 2$'s støvemiddel anvendes følgende stoffer: u H2077 a) 5 dele virksomt stof 95 dele talkum; b) 2 dele virksomt stof 1 del bøjdispers kiselsyre 97 dele talkum.For the preparation of an a) 5 $ and b) 2 $ dust, the following substances are used: u H2077 a) 5 parts active substance 95 parts talc; b) 2 parts active substance 1 part bend dispersion silicic acid 97 parts talc.
De virksomme stoffer blandes med bærestofferne og kan forstøves i denne form til anvendelse.The active substances are mixed with the carriers and can be atomized in this form for use.
Granulat;granules;
Til fremstilling af et 5$' s granulat anvendes følgende stoffer; 5 dele virksomt stof 0,25 dele epichlorhydrin 0,25 dele cetylpolyglycolether 3,50 dele polyethylenglycol 91 dele kaolin (komstørrelse 0,3-0,8 mm).For the preparation of a 5 $ granule, the following substances are used; 5 parts active substance 0.25 parts epichlorohydrin 0.25 parts cetyl polyglycol ether 3.50 parts polyethylene glycol 91 parts kaolin (grain size 0.3-0.8 mm).
Det aktive stof blandes med epichlorhydrin og opløses med 6 dele acetone; herpå tilsættes po ly ethyl englycol og cetylpolyglycolether. Den således opnåede opløsning sprøjtes på kaolin, og derpå afdampes acetonen i vakuum. Et sådant mikro granulat anvendes med fordel til bekæmpelse af jordsvampe.The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; to this is added polyethyl ethyl glycol and cetyl polyglycol ether. The solution thus obtained is sprayed on kaolin and then the acetone is evaporated in vacuo. Such a micro granule is advantageously used to control soil fungi.
Sprøjtepulver;Injection Powder;
Til fremstilling af et a) 70#'s, b) 40$'s, c) og d) 25$'s, e) 10#'s sprøjtepulver anvendes følgende bestanddele: a) 70 dele virksomt stof 5 dele natriumdibutylnaphthalensulfonat 3 dele napht hal ensul f o nsyr e-ph enol sul fonsyre-formald ehy d-kondensat 3:2:1 10 dele kaolin 12 dele Champagne-kridt; b) 40 dele virksomt stof 5 dele ligninsulfonsyre-natriumsalt 1 del dibutylnaphthalensulfonsyre-natriumsalt 54 dele kiselsyre; c) 25 dele virksomt stof 4,5 dele calcium-ligninsulfat 1,9 dele Champagne-kridt/hydroxyethylcellulose-blanding (1:1) 12 142077 1.5 dele natrium-dibutyl-naphthalensul fonat 19.5 dele kiselsyre 19.5 dele Champagne-kridt 28,1 del kaolin; d) 25 dele virksomt stof 2.5 dele i s o o c tylpheno xy-polyo xyethylen-ethanol 1,7 dele Champagne-kridt/hydroxyethylc ellulose-bl ånding (l:l) 8,3 dele natriumaluminiumsilicat 16.5 dele kiselgur 46 dele kaolin; e) 10 dele virksomt stof 3 dele blanding af natriumsalte af mættede fedtalkoholsulfater 5 dele naphthaiensulfonsyre/formaldehyd-kondensat 82 'dele kaolin.For the preparation of an a) 70 #, b) 40 $, c) and d) 25 $, e) 10 # spray powder, the following ingredients are used: a) 70 parts active substance 5 parts sodium dibutyl naphthalenesulfonate 3 parts napht hal ensul fo nsyr e-ph enol sul phonic acid formal ehy d condensate 3: 2: 1 10 parts kaolin 12 parts Champagne chalk; b) 40 parts active substance 5 parts lignin sulfonic acid sodium salt 1 part dibutylnaphthalenesulfonic acid sodium salt 54 parts silica; c) 25 parts active substance 4.5 parts calcium lignin sulfate 1.9 parts Champagne chalk / hydroxyethyl cellulose mixture (1: 1) 12 parts 1.5 sodium dibutyl-naphthalenesulphonate 19.5 parts silicic 19.5 parts Champagne chalk 28.1 del kaolin; d) 25 parts active substance 2.5 parts in s o o c tylpheno xy-polyo xyethylene ethanol 1.7 parts Champagne chalk / hydroxyethylcellulose bl breath (l: l) 8.3 parts sodium aluminum silicate 16.5 parts diatomaceous earth 46 parts kaolin; e) 10 parts active ingredient 3 parts mixture of sodium salts of saturated fatty alcohol sulphates 5 parts naphthalene sulfonic acid / formaldehyde condensate 82 'parts kaolin.
De virksomme stoffer blandes grundigt i egnede blandere med tilsæt ningsstofferne og formales på møller og valser. Man får sprøjtepulvere med fortrinlig befugtelighed og svæveevne, hvilke pulvere kan fortyndes med vand til suspensioner af enhver ønsket koncentration, og som især kan anvendes til bladapplikation.The active substances are thoroughly mixed in suitable mixers with the additives and ground on mills and rollers. Spray powders with excellent wettability and buoyancy are obtained, which powders can be diluted with water to suspensions of any desired concentration, and which can be used especially for leaf application.
Emulgerb are kone entr at er;Emulgerb are wife entr at er;
Til fremstilling af et 25$' s emulgerbart koncentrat anvendes følgende stoffer: 25 dele virksomt stof 2.5 dele epoxideret planteolie 10 dele af en alkylarylsulfonat/fedtalkoholpolyglycolether-blanding 5 dele dimethylformamid 57.5 dele xylen.For the preparation of a 25 $ emulsifiable concentrate, the following substances are used: 25 parts of active substance 2.5 parts of epoxidized vegetable oil 10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture 5 parts of dimethylformamide 57.5 parts of xylene.
Af sådanne koncentrater kan der ved fortynding med vand fremstilles emulsioner med enhver ønsket koncentration, hvilke er særlig egnet til bladapplikation.From such concentrates, by dilution with water, emulsions of any desired concentration can be prepared which are particularly suitable for leaf application.
Eksempel 3.Example 3
Virkning mod Rhytophthora infestans på Solanum -lyeopersieum (tomater). Ia) Resi dual-præventiv virkningEffect against Rhytophthora infestans on Solanum-lyeopersieum (tomatoes). Ia) Resi dual preventive effect
Solanum lycopersicum-planter af sorten "Roter Gnom" inficeres efter 13 142077 3 ugers dyrkning efter sprøjtning med en sprøjtevæske, der indeholder 0,05$ aktivt stof (fremstillet ud fra det til et sprøjtepulver oparbejdede virksomme stof) og tørring med en zoosporesuspension af Phyto-phthora infestans. De forbliver så i 6 dage i et klimakammer ved 18 til 20°C og høj luftfugtighed, som frembringes ved hjælp af en kunstig forstøvningståge. Efter denne tid viser der sig typiske bladpletter. Deres antal og størrelse er bedømmelsesmålestok for det undersøgte stof.Solanum lycopersicum plants of the "Rotate Gnom" variety are infected after 13 weeks of post-spray cultivation with a spray liquid containing $ 0.05 active substance (prepared from the active ingredient processed into a spray powder) and dried with a zoospore suspension of Phyto -phthora infestans. They then stay for 6 days in a climate chamber at 18 to 20 ° C and high humidity, which is produced by an artificial spray mist. After this time, typical leaf spots appear. Their number and size are the benchmark for the substance under study.
Ib) Kurativ virkningIb) Curative effect
Tomatplanter af sorten "Roter Gnom" besprøjtes efter 3 ugers dyrkning med en zoosporesuspension af svampen og inkuberes i en kabine ved 18 til 20°C og mættet luftfugtighed. Afbrydelse af befugtningen efter 24 timer. Efter tørring af planterne besprøjtes disse med en sprøjte-væske, der indeholder det som sprøjtepulver formulerede virksomme stof i en koncentration på 0,05$. Efter tørring af sprøjtebelægningen opstilles planterne atter i den fugtige kabine i 4 dage. Antallet og størrelsen af de efter denne tid optrædende typiske bladpletter er bedømmelsesmålestok for de undersøgte stoffers virkning.Tomato plants of the "Rotary Gnom" variety are sprayed after 3 weeks of cultivation with a zoospore suspension of the fungus and incubated in a cabin at 18 to 20 ° C and saturated humidity. Wetting off after 24 hours. After drying the plants, they are sprayed with a spray liquid containing the active ingredient formulated as spray powder at a concentration of 0.05 $. After drying the spray coating, the plants are put back in the damp cabin for 4 days. The number and size of the typical leaf spots occurring after this time are the benchmark for the effect of the substances studied.
II) Præventiv-systemisk virkningII) Preventive-systemic effect
Det som sprøjtepulver formulerede virksomme stof påføres i en koncentration på 0,05$ (regnet på jordrumfanget) på jordoverfladen ved 3 uger gamle, i potter værende tomatplanter af sorten "Roter Gnom).The active substance formulated as a spray powder is applied at a concentration of $ 0.05 (calculated on soil volume) on the soil surface at 3 weeks old, in pots of tomato plants of the variety "Rotate Gnom").
Efter·3 dages ventetid besprøjtes undersiden på planternes blade med en zoosporesuspension af Phytophthora infestans. De holdes så i 5 dage i en sprøjtekabine ved 18 til 20°C og mættet luftfugtighed.' Efter denne tid dannes der typiske bladpletter, hvis antal og størrelse tjener til bedømmelse af de undersøgte stoffers virkning.After · 3 days of waiting, the underside of the leaves of the plants is sprayed with a zoospore suspension of Phytophthora infestans. They are then kept for 5 days in a spray booth at 18 to 20 ° C and saturated humidity. ' After this time, typical leaf spots are formed, the number and size of which serve to judge the effect of the substances studied.
Ved disse tre forsøg viser forbindelserne med formlen I den i den følgende tabel viste stærke bladfungicide virkning.In these three experiments, the compounds of formula I show the strong leaf fungicidal activity shown in the following table.
14 142077 •Tabel til eksempel 3 (gennemsnitsværdier)14 142077 • Table for example 3 (average values)
Porb. nr. Svampeangreb Forb. nr. Svampeangreb i procent i procent 1 0-5$ 25 < 20$ 2 < 20$ 26 < 20$ 3 0-5$ 27 < 20$ 4 <20$ 28 < 20$ 5 <20$ 29 < 20$ 7 20-40$ 30 20-40$ 9 < 20$ 31 < 20$ 11 .< 20$ 32 < 20$ 12 < 20$ 34 0-5$ 13 < 20$ 35 0-5$ 14 < 20$ 36 < 20$ .15 < 20$ 37 < 20$ 17 < 20$ 39 < 20$ 19 < 20$Porb. No. Mushroom attack Forb. No. Fungus Percentage Percentage Percentage 1 0-5 $ 25 <20 $ 2 <20 $ 26 <20 $ 3 0-5 $ 27 <20 $ 4 <20 $ 28 <20 $ 5 <20 $ 29 <20 $ 7 20-40 $ 30 20-40 $ 9 <20 $ 31 <20 $ 11. <20 $ 32 <20 $ 12 <20 $ 34 0-5 $ 13 <20 $ 35 0-5 $ 14 <20 $ 36 < 20 $ .15 <20 $ 37 <20 $ 17 <20 $ 39 <20 $ 19 <20 $
Forbindelsen nr. 1 mindsker ved de samme forsøg ved anvendelseskoncentrationer på kun 0,02$ svampeangrebet til under 20$.The compound # 1 decreases in the same trials at application concentrations of only $ 0.02 fungal attack to below $ 20.
Eksempel 4.Example 4
('Sammenligningsforsøg)(Comparative Experiment)
Forb. A = F-Ethoxycarbonylmethyl-N-( 2,6-dimethylphenyl) -chlorac et amid (eks. 8 i DE-offentliggørelsesskrift nr. 2.212.268).Conn. A = F-Ethoxycarbonylmethyl-N- (2,6-dimethylphenyl) chlorac et amide (Example 8 of DE Publication No. 2,212,268).
Forb. B = N-Chloracetyl-E-2,6-dimethylph.enyl-alaninmetb.ylester (dansk patentansøgning nr. 5552/73).Conn. B = N-Chloroacetyl-E-2,6-dimethylphenyl-alanine methyl ester (Danish Patent Application No. 5552/73).
Forb. C = E-Bromacetyl-N-2,6-dimeth.ylph.enyl-alaninmetlaylester (dansk patentansøgning nr. 5552/73).Conn. C = E-Bromoacetyl-N-2,6-dimethylphenyl-alanine methyllayter (Danish Patent Application No. 5552/73).
Virkning mod Plasmopara viticola (Bert, et Curt.) (Berl. et DeToni) på vinplanter.Effect against Plasmopara viticola (Bert, et Curt.) (Berl. Et DeToni) on vine plants.
a) Residual-præventiv virkning.a) Residual-preventive effect.
I væksthus dyrkes vinplantestiklinger af sorten "Chasselas". I 10-bladsstadiet sprøjtes 3 planter med en ud fra et som sprøjtepulver 15 142077 formuleret virksomt stof fremstillet sprøjtevæske (0,05$ virksomt stof). Efter tørring af sprøjtebelægningen inficeres planterne ensartet på bladenes underside med en sporesuspension af svampen. Planterne holdes derpå 8 dage i et fugtkammer. Efter denne tid viser der sig tydelige sygdomssymptomer hos kontrolplanterne. An tal og størrelse af infektionssteder hos de behandlede planter tjener som bedømmel-sesmålestok for virkningen af de undersøgte stoffer.In greenhouses, grapevine cuttings of the "Chasselas" variety are grown. At the 10-leaf stage, 3 plants are sprayed with an active substance prepared from spray powder (0.05 $ active substance) formulated as a spray powder. After drying the spray coating, the plants are uniformly infected on the underside of the leaves with a spore suspension of the fungus. The plants are then kept for 8 days in a humid chamber. After this time, clear disease symptoms appear in the control plants. The number and size of infection sites in the treated plants serve as a benchmark for the efficacy of the substances studied.
b) Kurativ virkning.b) Curative effect.
Vinplantestiklinger af sorten "Chasselas" dyrkes i væksthus og inficeres i 10-bladstadiet med en sporesuspension af Plasmopara viticola på bladenes underside. Efter 24 timers ophold i en fugtkabine besprøj-tes planterne med en 0,05$'s sprøjtevæske af virksomt stof, hvilken er fremstillet af et sprøjtepulver af det virksomme stof. Derpå holdes planterne i yderligere 7 dage i fugtkabine. Efter denne tid viser der sig sygdomssymptomer hos kontrolplantemé. Antal og størrelse af infektionssteder hos de behandlede planter tjener som bedømmelsesmålestok for virkningen af de undersøgte stoffer.Vine cuttings of the "Chasselas" variety are grown in greenhouses and infected at the 10-leaf stage with a spore suspension of Plasmopara viticola on the underside of the leaves. After a 24 hour stay in a humidity booth, the plants are sprayed with a 0.05 $ active ingredient spray liquid made from an active ingredient spray powder. The plants are then kept for a further 7 days in a humidifier. After this time, disease symptoms appear in control plant moth. The number and size of infection sites in the treated plants serve as a benchmark for the effect of the substances studied.
Ved forsøg a) ifølge eksempel 4 viser forbindelserne med formlen I stærk fungicid virkning:In experiment a) of Example 4, the compounds of formula I show strong fungicidal activity:
Tabel til eksempel 4 (gennemsnitsværdier)Example 4 Table (Average Values)
Porb. nr. Svampeangreb Porb. nr. Svampeangreb i procent i procent 1 0-5$ 14· °" 2 < 20$ 15 < 20$ 3 0-5$ 16 < 20?δ 4 < 20$ 17 < 20* 5 < 20$ 18 < 20^ 6 < 20$ 19 < 2 8 20-40$ 20 < 20$ g 0-5$ 21 < 20$ 10 0-5$ 22 < 20$ 11 0-5$ 25 20-40$ 12 0-5$ 26 20-40$ 13 0-5$ 27 < 20$ 16 142077Porb. No. Mushroom attack Porb. No. Fungus Percentage Percentage Percentage 1 0-5 $ 14 · ° "2 <20 $ 15 <20 $ 3 0-5 $ 16 <20? δ 4 <20 $ 17 <20 * 5 <20 $ 18 <20 ^ 6 <20 $ 19 <2 8 20-40 $ 20 <20 $ g 0-5 $ 21 <20 $ 10 0-5 $ 22 <20 $ 11 0-5 $ 25 20-40 $ 12 0-5 $ 26 20-40 $ 13 0-5 $ 27 <20 $ 16 142077
Tabel fortsat:Table continued:
Forb. nr. Svampeangreb i procent 28 20-40$ 29 < 20$ 30 20-40$ 31 20-40$ 32 20-40$ 33 20-40$ 34 0-5$ 35 0-20$ 36 0-5$ 37 < 20$ 38 . < 20$ 39 < 20$ A 50-100** B 0-5* C 0-5*Conn. No. Mushroom attacks as a percentage 28 20-40 $ 29 <20 $ 30 20-40 $ 31 20-40 $ 32 20-40 $ 33 20-40 $ 34 0-5 $ 35 0-20 $ 36 0-5 $ 37 <20 $ 38. <20 $ 39 <20 $ A 50-100 ** B 0-5 * C 0-5 *
Forbindelserne nr. 1, 3, 9, 10, 13, 14 og 34 mindsker ved de samme forsøg ved anvendelseskoncentrationer på kun 0,02% svampeangrebet til ligeledes 0-5%. De af D-konfigurationen af N-(1'-methoxyearbonyl-ethyl)-2,6-dimethylanilin afledte D-former af forbindelserne nr- 1, 3, 9, 13 og 34 mindsker ved anvendelseskoncentrationer på 0,02% svampeangrebet til 0-10%.Compounds Nos. 1, 3, 9, 10, 13, 14 and 34 decrease in the same experiments at application concentrations of only 0.02% fungal attack to also 0-5%. The D-forms of compounds Nos. 1, 3, 9, 13 and 34 derived from the D-configuration of N- (1'-methoxyearbonyl-ethyl) -2,6-dimethylaniline decrease to 0.02% fungal attack to 0 -10%.
Ved forsøg b) ifølge eksempel 4 viser forbindelserne med formlen I stærk fungicid virkning ved følgende koncentrationer:In experiment b) of Example 4, the compounds of formula I show strong fungicidal activity at the following concentrations:
Tabel til eksempel 4 (gennemsnitsværdier)Example 4 Table (Average Values)
Forb. nr._ Kone._Svampeangreb i procent 9 0,06 0-5 0,02 0-5 0,006 0-5 13 0,06 0-5 0,02 0-5 0,006 0-5 14 0,06 0-5 0,02 0-5 0,006 0-5 17 142077 A 0,06 50-100** B 0,06 0-5» 0,02 0-5 0,006 0-5 C 0,06 0-5» 0,02 0-5 0,006 0-5 * Let fytotoksicitet ved koncentrationer på 0,05% eller højere.Conn. No._ Wife_Sponge attack as a percentage 9 0.06 0-5 0.02 0-5 0.006 0-5 13 0.06 0-5 0.02 0-5 0.006 0-5 14 0.06 0-5 0 , 02 0-5 0.006 0-5 17 142077 A 0.06 50-100 ** B 0.06 0-5 »0.02 0-5 0.006 0-5 C 0.06 0-5» 0.02 0 -5 0.006 0-5 * Light phytotoxicity at concentrations of 0.05% or higher.
** Graden af fytotoksicitet sløres af svampeangrebet.** The degree of phytotoxicity is blurred by the fungal attack.
Den som herbicid angivne sammenligningsforbindelse A viser overhovedet ingen fungicid virkning. De som fungicider angivne sasmen-ligningsforbindelser B og C har i høje koncentrationer en uønsket, let fyto toksicitet, der i det angivne koncentrationsområde ikke forekommer ved forbindelserne ifølge opfindelsen.The Comparative Compound A listed as herbicide shows no fungicidal effect at all. The sasma equation compounds B and C designated as fungicides have, at high concentrations, an undesirable, slight phytotoxicity which does not occur in the indicated concentration range of the compounds of the invention.
Ved forbindelserne ifølge opfindelsen forekommer der ved de angivne koncentrationer ingen fytotoksicitet. Forbindelserne ifølge opfindelsen har i forhold til sammenligningsforbindelseme B og Q fordelen ved en større sikkerhed ved tilfældig overdosering.In the compounds of the invention no phytotoxicity occurs at the indicated concentrations. The compounds of the invention have the advantage of greater safety in case of accidental overdose over the comparative compounds B and Q.
Eksempel 5.Example 5
Virkning mod Pythium debaryanum på Beta vulgaris (sukkerroe).Effect against Pythium debaryanum on Beta vulgaris (sugar beet).
a) Virkning efter .jordapplikation(a) Effect after soil application
Svampen dyrkes på sterile havrekom og sættes til en jord-sand-blanding. Den således inficerede jord fyldes i urtepotter og besås med sukkerroefrø. lige efter udsåningen hældes de som sprøjtepulvere formulerede forsøgspræparater som vandige suspensioner ud over jorden (0,002% virksomt stof regnet på jordrumfanget). Urtepotterne opstilles derpå i 2-3 uger i væksthus ved 20-24°C. Jorden holdes ensartet fugtig ved let besprøjtning med vand. Ved bedømmelse af forsøgene bestemmes opvæksten af sukkerroeplanter samt antallet af sunde og syge planter.The fungus is grown on sterile oatmeal and added to a soil-sand mixture. The soil thus infected is filled in herb pots and sown with sugar beet seeds. just after sowing, test formulations formulated as spray powders are poured into the soil as aqueous suspensions (0.002% active substance calculated on soil volume). The herb pots are then set up for 2-3 weeks in greenhouses at 20-24 ° C. The soil is kept uniformly moist by light spraying with water. When assessing the experiments, the growth of beet plants as well as the number of healthy and diseased plants is determined.
b) Virkning efter bejdseapplikationb) Impact after pickling application
Svampen dyrkes på sterile havrekom og sættes til en jord-sand-blan-ding. Den således inficerede jord fyldes i urtepotter og besås medThe fungus is grown on sterile oatmeal and added to a soil-sand mixture. The soil thus infected is filled in herb pots and sown with
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH450974A CH587605A5 (en) | 1974-04-01 | 1974-04-01 | |
CH450974 | 1974-04-01 | ||
CH178575 | 1975-02-13 | ||
CH178575A CH599749A5 (en) | 1974-04-01 | 1975-02-13 |
Publications (3)
Publication Number | Publication Date |
---|---|
DK136175A DK136175A (en) | 1975-10-02 |
DK142077B true DK142077B (en) | 1980-08-25 |
DK142077C DK142077C (en) | 1981-01-19 |
Family
ID=25688666
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK136175AA DK142077B (en) | 1974-04-01 | 1975-03-26 | Plant fungicidal halogenacylanilides. |
Country Status (19)
Country | Link |
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AR (1) | AR206017A1 (en) |
BG (1) | BG26355A3 (en) |
CS (1) | CS183786B2 (en) |
DD (1) | DD118789A5 (en) |
DK (1) | DK142077B (en) |
EG (1) | EG12051A (en) |
ES (1) | ES436151A1 (en) |
FI (1) | FI61475C (en) |
HU (1) | HU175452B (en) |
IE (1) | IE41330B1 (en) |
IL (1) | IL46970A (en) |
IT (1) | IT1049393B (en) |
NO (1) | NO144963C (en) |
PH (1) | PH11151A (en) |
PL (1) | PL98630B1 (en) |
SE (1) | SE411449B (en) |
SU (1) | SU793353A3 (en) |
TR (1) | TR18470A (en) |
YU (1) | YU81475A (en) |
-
1975
- 1975-01-01 AR AR258180A patent/AR206017A1/en active
- 1975-03-26 NO NO751087A patent/NO144963C/en unknown
- 1975-03-26 DK DK136175AA patent/DK142077B/en unknown
- 1975-03-26 SE SE7503515A patent/SE411449B/en unknown
- 1975-03-26 FI FI750918A patent/FI61475C/en not_active IP Right Cessation
- 1975-03-27 IE IE697/75A patent/IE41330B1/en unknown
- 1975-03-27 HU HU75CI1560A patent/HU175452B/en not_active IP Right Cessation
- 1975-03-28 IT IT21854/75A patent/IT1049393B/en active
- 1975-03-30 EG EG176/75A patent/EG12051A/en active
- 1975-03-31 PH PH16993A patent/PH11151A/en unknown
- 1975-03-31 ES ES436151A patent/ES436151A1/en not_active Expired
- 1975-03-31 BG BG7529501A patent/BG26355A3/xx unknown
- 1975-03-31 YU YU00814/75A patent/YU81475A/en unknown
- 1975-03-31 DD DD185112A patent/DD118789A5/xx unknown
- 1975-03-31 IL IL46970A patent/IL46970A/en unknown
- 1975-04-01 PL PL1975179256A patent/PL98630B1/en unknown
- 1975-04-01 SU SU752118251A patent/SU793353A3/en active
- 1975-04-01 TR TR18470A patent/TR18470A/en unknown
- 1975-04-01 CS CS7500002210A patent/CS183786B2/en unknown
Also Published As
Publication number | Publication date |
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BG26355A3 (en) | 1979-03-15 |
IL46970A0 (en) | 1975-05-22 |
NO751087L (en) | 1975-10-02 |
IE41330B1 (en) | 1979-12-05 |
FI61475C (en) | 1982-08-10 |
EG12051A (en) | 1978-06-30 |
HU175452B (en) | 1980-08-28 |
IE41330L (en) | 1975-10-01 |
AR206017A1 (en) | 1976-06-23 |
PL98630B1 (en) | 1978-05-31 |
IL46970A (en) | 1978-08-31 |
DK136175A (en) | 1975-10-02 |
NO144963C (en) | 1981-12-16 |
DD118789A5 (en) | 1976-03-20 |
SE7503515L (en) | 1975-10-02 |
IT1049393B (en) | 1981-01-20 |
NO144963B (en) | 1981-09-07 |
PH11151A (en) | 1977-10-27 |
ES436151A1 (en) | 1977-02-01 |
TR18470A (en) | 1977-02-24 |
FI61475B (en) | 1982-04-30 |
CS183786B2 (en) | 1978-07-31 |
DK142077C (en) | 1981-01-19 |
YU81475A (en) | 1983-04-27 |
FI750918A (en) | 1975-10-02 |
SU793353A3 (en) | 1980-12-30 |
SE411449B (en) | 1979-12-27 |
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