DE2513788A1 - MICROBICIDAL AGENT - Google Patents

Description

CLBA-GEIGYAG. CH-4002 Base! W'iLJ / V VJLcIVj I

Dr. F.Zumstein son. - Dr. E. Ace "i.?nn

Dr.R. ^Koen:; 'ihe: rpr-you! fr -. · "*.! '! rbauer

Dipl. -Ing. F. Ki ;. ^ -. · 2 ■ ■ i · '· ''■ r v. ;.: t in jun.

8 munch; ·. ?,, .Ίji-ncLiB ^ ßo 4 ->

Germany

Microbicidal Agent

The present invention relates to compounds of the formula I.

CH ₀

-COOCH ₃

(D

V7orin R denotes hydrogen or methyl, a process for the preparation of these compounds, and also microbicidal Agents that contain these compounds as active ingredients, and the use of these compounds as microbicides, preferably for combating phytopathogenic fungi.

Bacterial and fungal diseases in crops favored by two factors. On the one hand, plant breeding is primarily about increasing yields and strive for quality improvement. Often, however, part of the natural resilience of the Plant lost to parasites. Second, experience has shown that bacteria and harmful fungi in the Have developed resistance to the known pesticides to a greater extent over the years.

50984 1 / 098S

There is therefore an urgent need for microbicides, which are compatible with cultivated plants and their direct Kill parasites.

Crop plants are for example within the scope of the present invention Grain. Corn, rice, vegetables, sugar beet, soy, peanuts, fruit trees, ornamental plants, but above all vines, hops, cucumber plants (Cucumbers, pumpkins, melons), Solanaceae such as potatoes, tobacco and tomatoes, as well as banana, cocoa and natural rubber plants.

It has now been found, surprisingly, that with the active ingredients of the formula I on plants or plant parts (fruits, Flowers, foliage, stems, tubers, roots) of these and related crops, the fungi that occur are contained or can be destroyed, with parts of plants that grow later also being spared from such fungi. the Active ingredients are active against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Erysiphaceae); Basidiomycetes, especially rust fungi; Fungi imperfecti; but then especially against those belonging to the Phycomycetes class Oomycetes such as Phytophthora, Peronospora, Pseudoperonospora, Pythium or Plasmopara. In addition, the connections work of formula I systemic.

They can also be used as a dressing agent for the treatment of seeds (fruits, tubers, grains) and plant cuttings to protect against Fungal infections and phytopathogens occurring in the soil Mushrooms are used.

The N- (substituted-phenyl) -N-furanoyl-alanine methyl esters of the formula I. represent a previously unknown class of new microbicidal agents represent, the usual commercial preparations are clearly superior in their field of application.

Compounds of the formula I are according to an inventive Method, for example, by acylation of a compound of formula II

509841/0986

CH ₀ i ³ NH-CH-COOCH ₃ (II)

with furan (2) carboxylic acid, its acid halide, acid anhydride or esters, in individual cases also with a 3m furan (2) carbonamide (Umamidation).

According to another inventive method, the Compounds of the formula I also from the acylanilides of the formula III

N-CO.

(III)

with butyl lithium or sodium hydride into the corresponding alkali salt be transferred, which then with the methyl oc-halopropionate .Leads to the desired end product or with the methyl ct-IIalogenpropionate in the presence of an alkali metal carbonate like K ^ CO- as proton acceptor, preferably with addition catalytic amounts of alkali iodide, e.g., KJ.

In the formulas II and III, R stands for hydrogen or methyl, the term acid halide preferably means acid chloride or acid bromide and the halogen atom in methyl α-halopropionate is preferably chlorine or bromine. The reactions can take place in the presence or absence of the reactants inert solvents or diluents carried out will. For example, the following are possible: aliphatic or aromatic hydrocarbons such as benzene, toluene, xylenes, Petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform; Aether and ethereal compounds such as dialkyl ethers, dioxane, tetrahydrofuran; Nitriles such as acetonitrile; Ν, Ν-dialkylated amides such as

509841/0986

Dimethylformamide; anhydrous acetic acid, dimethyl sulfoxide, ketones such as methyl ethyl ketone and mixtures of such solvents among others.

The reaction temperatures are between 0 ° and 180 ° C,
preferably between 20 and 120. In some cases the
Use of acid-binding agents or condensation agents is advantageous. Tertiary amines such as trialkylamines (eg triethylamine), pyridine and pyridine bases, or inorganic bases such as the oxides and hydroxides, hydrogen carbonates and carbonates of alkali and alkaline earth metals and sodium acetate are suitable as such. As an acid-binding agent, an excess of the
respective aniline derivatives of the formula II are used.

The preparation process proceeding from compounds of the formula II can also be carried out without acid-binding agents, in which case nitrogen is passed through to the
Expulsion of the hydrogen halide formed is indicated.
In other cases, an addition of dimethylformamide is considered
Reaction catalyst very advantageous.

Details of the preparation of the intermediates of the formula II can be found in the methods that are generally used for the
Production of anilino-alkanoic acid esters in the following \
Publication organs are given:

J.Org. Chem. 30, 4101 (1965),
Tetrahedron 1967,. 487,
Tetrahedron 1967 493,

The compounds of formula I have propionic acid esters in the chain an asymmetric carbon atom and can be split into optical antipodes in the usual way. Here the enantiomeric D-form the stronger microbicidal effect.

In the context of the invention, accordingly, those compounds are their means and their use preferred, which relate to the

D configurations of the formula I refer. Have these D-shapes in ethanol or acetone a negative angle of rotation.

50984 1/0986

To establish the purely optical D-AnL: pod cn, for example, the spatial connection for Vor-fc I TV

^C ' ³ Y »3

NH-CH-COOH (IV)

(R - H or CH)

prepared and then reacted in a manner known per se with an N-containing optically active base to give the corresponding salt. By fractional crystallization of the salt and subsequent release of the acid of the formula IV enriched with the optical D antipode and optionally repetition (including multiple repetitions) of the salt formation, crystallization and release of the α-anilinopropionic acid of the formula IV, the pure D form is gradually obtained. This can then be used in the usual way, for example in the presence of HCl or H _? SO ,, with methanol the optical D configuration of the Ksterert; win the formula II. An example of an optically active organic base is oc-l'henylethylamine.

Instead of fractional crystallization, the enantiomeric D-form of the formula IV also by exchanging the hydroxyl group in the naturally occurring L (-f) hi-ich acid against halogen and further reaction of this product under configuration reversal with the desired 2,6-dimethylaniline or 2,3,6-Tr line thy lan Hin win.

In addition to the optical isomerism, in the case of R = CIl _{3, one occurs} with the furanoylation of the compound II (or with the reaction of the compound III with methyl α-halopropionate)

Atropisomerism around the phenyl N <C axis due to

the steric hindrance of the two on the N-atom of the trimethylaniline additionally introduced residues. If no specific synthesis for the isolation of pure isomers is carried out, the Compound No. 2 mentioned below in the preparation as a mixture of 4 isomers. The more beneficial fungicidal effect of the enantiomeric D-form (compared to D, L-form or L-form) remains, however, and is not significantly influenced by the Atrο ρ i somerIe.

5098A1 / 0988

The production of the l.'iikt-to Cfe dor forme 1.T is illustrated by the example 1 and 2 illustrate! ... (temperature data in Ce Lsius degrees)

Ee ijr pi el 1

Production of

ο-

\: η

(Connection no.1)

N- (I ¹ -methoxy-carbonylethyl) -N- (furan- (2 ") -carbonyl) -2,6-dimethylaniline.

To 18.2 g of N- (l-methoxycarbonylethyl) -2,6-dimethy! Aniline in 10 ml of anhydrous toluene and 0.2 ml of dimethylformamide were under Stirring 12.6 g of furan-2-carboxylic acid chloride were added dropwise. After this The "weakly exothermic reaction" subsided, the mixture was refluxed for five hours and the hydrogen chloride formed passed through Passing through nitrogen completely eliminated. After removing the solvent, the following was distilled in vacuo:

Bp -166-168 / 0.06 torr. The solidified end product melts after recrystallization from toluene / petroleum ether

81-84. X-ray powder diagrams show the connection is polymorphic. One of the two modifications melts at

,-O

Have the enantiomeric D configuration and its precursors following phys. Data:

CH.

CH ₀

1 3

NH- * CH-COOH

CH ₀ I 3

Nile -'VCH -COOCIL

(D) shape

(a) l ° = + 10.7 + 0.3 °; C = 1.56 % w / v

in ethanol

(D) shape
20th

3 U) _n = +29.8 + 0.5 °; C = 1.52% g /

in methanol

509841/0986

Verb number la)

Example 2

CH

CIL

CH ₃ CH ₃

* CH -COUCH ₃ ( _D ) _ _{Form Smp m} I ₀₂ _ _l03 '.

(a) ^ ⁰ - -47.0 + 0.7 ° I | 1 C = 1.737o g / v in acetone

Production of

COOCH.

(Connection no.2)

N- (I ¹ -methoxycarbonyl-ethyl) -N- (Euran- (2 ") -carbonyl-2,3,6-trimethyl aniline.

a) A suspension of 51.5 g (0.382 mol) 2,3,6-trimethylaniline, 35.3 g NaHCO ₃ and 126 ml (1.15 mol) 2-bromopropionic acid methyl ester is 6 hours at a bath temperature of 130 stirred, then cooled, filtered from the salt and distilled: 67.3 g of methyl a- (2,3,6-trimethylanilino) propionate, bp 144 ° -146 ° c / 9 torr.

b) A suspension of 33.5 g (0.152 McI) of the according to a) obtained ester and 18 g (0.17 mol) of soda in 200 ml of absolute benzene, is added dropwise with 16.7 ml (0.17 mol) Furan-2-carboxylic acid chloride was added at 60-70 and held for a further 4 hours. After cooling, filtering and the Concentration of the filtrate crystallizes the end product

from isopropyl ether; M.p. 98-102 ° C.

If you use the D-form of methyl a- (2,3,6-trimethylanilino) propionate acylated with furan (2) carboxylic acid or one of its reactive derivatives, the D-form of the compound is obtained as a mixture of atropisomers (= compound no. 2a). The accruing percentage of each of these isomers depends on the particular manufacturing conditions.

509841/0986

The compounds of the formula I can be used alone or together with suitable carriers and / or other additives be used. Suitable carriers and aggregates can be fixed or be liquid and correspond to the substances customary in formulation technology, such as natural or regenerated mineral Substances, solvents, dispersants, wetting, HaEt, thickening, Binders or fertilizers.

The content of active ingredient in commercial products is between 0.1 and 90 "L.

For administration, the compounds of the formula 1 can be present in the following working-up forms (the percentages by weight represent advantageous amounts of active ingredient in brackets):

Solid forms of processing: dust and grit (up to 10%);

Granules, coating granules, impregnation granules and homogeneous granules (1 to 80%);

Liquid processing forms:

a) Active substance concentrates dispersible in water:

Wettable powders and pastes (25-90% in the hand-pack, 0.01 to 15% in ready-to-use solution);

Emulsion and solution concentrates (10 to 50%; 0.01 to 15% in ready-to-use solution);

b) solutions (0.1 to 20 %) ;

The active ingredients of the formula I can, for example, as follows be formulated:

509841/0986

Stäubemi t tel: To prepare a) a 57, and lgen 27olgen b)

The following substances are used as a dusting agent

a) 5 parts of active ingredient No. 2 95 parts of talc;

b) 2 parts of active ingredient No. 1

1 part of highly disperse silica, 97 parts of talc;

The active ingredients are mixed with the carriers and ground and can be dusted in this form for use.

Granules: The following substances are used to produce 5% granules:

5 parts of active ingredient No. 1

0.25 part of epichlorohydrin,

0.25 part of cetyl polyglycol ether,

3.50 parts of polyethylene glycol

91 parts of kaolin (grain size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and Cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin, and then the acetone is in vacuo evaporates. Such microgranules are advantageously used to control soil fungi.

Spray powder: For the production of a) 70 7 _above b) 40%

c) and d) 25 7 _o igen e) lü Toigen spray powder the following ingredients are used:

a) 70 parts of N- (I '-Hethoxycarbonyl-ethyl) -N- [furan- <2 ") carbonyl] 2,6-dimethylaniline.Active substance No. la (D-form), according to the present invention 5 parts of sodium dibutylnaphthylsulfonate,

3 parts of naphthalenesulphonic acids-phenolsulphonic acids-Forma ! .deliyd condensate 3: 2: 1,

509841/0986

-LO-

10 parts kaolin, 12 parts champagne chalk;

b) 40 parts of active ingredient no.

5 parts of lignin sulfonic acid, sodium salt, 1 part of dibutylnaphthalene sulfonic acid, sodium salt, 54 parts of silica;

c) 25 parts of active ingredient No. 2a (D-form) 4.5 parts of calcium lignosulfonate,

1.9 parts of champagne chalk / hydroxyethyl cellulose mixture (L: L),

1.5 parts of sodium dibutyl naphthalene sulfonate, 19.5 parts silica, 19.5 parts Champagne chalk, 28.1 parts of kaolin;

d) 25 parts of active ingredient No.

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of Chainpagne chalk / hydroxyethyl cellulose

Mixture (1: 1), 8.3 parts of sodium aluminum silicate,

16.5 parts of kieselguhr, 46 parts of kaolin;

e) 10 parts of active ingredient no. la (D-form)

3 parts mixture of the sodium salts of saturated fatty alcohol sulfates,

5 parts naphthalenesulfonic acid / formaldehyde condensate, 82 parts of kaolin;

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. Spray powder of excellent quality is obtained Wettability and suspensibility, which can be diluted with water to form suspensions of any desired concentration and can be used especially for foliar application.

509841/0

Επ.ί 1 gi.erbare concen tra t ο: To prepare a 25% emulsifiable concentrate: verv the following substances: closing:

25 parts of active ingredient No. 1

2.5 parts epoxidized vegetable oil,

10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture,

5 parts of dimethylformamide, 57.5 parts of xylene.

Such concentrates can be made by diluting with water Emulsions of any desired concentration can be prepared, which are particularly suitable for foliar application.

The compounds of formula 1 can be used to broaden their spectrum of activity with other suitable pesticidal or the Active ingredients promoting plant growth are used. Known microbicidal active ingredients are, for example, the following Mixing components called, with which partly synergistically increased Effects are achieved:

509841/0986

Aanoniuin polysulfide Sodium polysuifide Barium polysulfide

Calcium polysulphide and calcium thiosulphate Calcium hypochlorite boric acid

Sodium tetraborate decahydrate (BORAX) Zinc chloride Magnesiuniborate Hfckelsulfat Kai iumchroBiat Lead arsenate Cadmium chloride Cadmium carbonate Copper (l) oxide (COPPER OXIDE) Bordeaux broth

Copper (11) su1fate pentahydrate (COPPER SULFATE) Basic copper (ll) chloride (COPPER OXICHLORIDE) Copper phosphate

Tribasic Copper Dsuifat (THREE BASIC COPPER SULFATE) Basic copper carbonate (KHPFERCARBOIJAT) Copperd O-dihydrazine sulphate Copper amrin complexes Copper sulfate-ammonium carbonate mixture copper-chloride-basic copper I) sulfate-mixture basic copper-carbonate-zinc salt-mixture copper-D-zinc-chromate-complex COPPER ZINC CHROMATE) copper-D-Z'nk-cadiut-calciuiü-chromate-Konplei copper oleic acid (copper oleate) KupferdDsalze of fatty acids KupferdDsalz naphthenic KupferdDsalz of the 8-hydroxyquinoline Kupferd Dsalz of l _f 2-Naphthochinonoxins- (2) of the 3-phenyl salicylate KupferdDsalz bis (tri-n-butylzlnn) oxide

Triphenyltin Hydroxide (MENTINE HYDROXIDE)

Triphenyltin Acetate (FENT INACETAT) Bis- (tributyltin) succinate QuechsilberdJchlorid (KALOMEL) MercurydOchloride Mercury (II) oxide Mercury-zinc-chromate-Komp1 ex Mercury lactate, ethyl mercury chloride Z-hydroxyethyl mercury acetate ethyl mercury isothiocyanate 3-ethoxypropyl mercury broniid Chlorine thoxypropylene mercury iberacetate Ethoxyethyric mercury chloride 2-methoxyethylmercury cat Bis (methyl mercury) su1fate bis methyl mercury, nonium acetate Ethylene mercury overacetate 2-ethoxyethylacetate - Ethyl mercury phosphate Isopropylethylmercury acetate 509841/0986

-W-

9 R 1 ^ 7 R R

ethylmercury cyanide * 1b

Methyl mercury benzoate

> -Cyano-H '("ethylmercury) guan5din

Methyl mercury pentachlorophenate Ethyl mercury 2,3-di hydroxypropyl cap i d Methyl mercury e-hydroxyquinolate (Ortho LH) N- (methyl mercury) -1, 4,5,6,7,7-hexachlorobicyclo [2.2.l] hept-5-ene-2,3-dicarboxii1 N- (ethylmercury) -1, 4,5,6,7,7-hexachlorobicyclo [2.2.1] hept-5-ene-2,3-dicarboxuid Sodium salt of ethylmercury thiosalicylate R- (Ethyl mercury) -p-toluene sulfonic acid anind Phenylmercuric boron acetate (PAH) Phenyl mercury propionate Phenylmercury Triethanolan Bonun Lactate (PAS) Phenyl mercury urea N- (Phenylmercury) -1, 4,5,6,7,7-hexachlorobicyclo [Z.2.1] hept-5-ene-2,3-d! Carboxy «1d Phenylmercuric diethyldithiocarbaate Phenylmercury forpamide Phenyl mercuric chloride Phenyl mercury acetate Phenylmercuric benzoate Phenylmercuric superborate Phenyl mercury hydroxide Phenyl mercury iodide Basic phenyl mercury! Phenylmercury aonoethanol anine lactate Phenyl mercury salicylate Hydroxy mercury chlorophenol Hydroxymercury trichlorophenol Hydroxymercury imbues i trophenol N-phenylmercuric ethylenedianine Phenylmercuric monoethanol anodine acetate Pyridyl mercury acetate Diphenyl mercury over-3-hydroxyquinolate Mercury chloride complex with organic phosphates Mixture of methylmercury-2,3-dihydroxypropylcaptide and methylmercury acetate Mixture of ethyl mercury 2,3-dihydroxypropyl mercaptide and ethyl mercury acetate Mixture of hydroxymercury chlorophenol and hydroxymercury-nitrophenol Mercury-Cad «iu-organic coaplex Cadi'unsuccinate

Cadaiua di-fi-propyl xanthate Cadil um-8-hydroxycMnol at Phenylaninocadsium acetate (henylaninocadaiuiKiirlactat Methyl arsine sulfide zinc octate Zinc oleate Foraal in Paraforaaldehyde acrolein Methylbroaid Methyl isothiocyanate tetraiodithylene T, 3-dichloropropene and related chlorinated C, hydrocarbons 1-chloro-3-broapropen (i)

5098A1 / 0986

2 R 1? 7 8

trans-M-DibroBbutenß) '& -

1,3-dichloropropene) 1-chloro-2-ni tro-propane 2- chi or-1-ni tropropane trichloronitromethane dichlorotetrafluoroacetone sodium salt of propionic acid calcium salt of propionic acid chiorfumaric acid bis-ß-chloroethyl ester sorbic acid and its potassium salt 2-propene-1, l-diol acetate 2-aminobutane

Oodecyclguanidinacetat (dodine) Oodccylguanidinphthalat o-chloroacetyl-1,3-aniinopropioni tri 1 o-bromoacetylvalinamide 1,2-dichloro-1- (nieihylsulfonyl) -ethylene 1,2 -dichloro-1- (butylsulfonyl) -ethylene trans-1, 2-bis (n-propy1sulfony1) ethyl en

p-dichlorobenzene hexachlorobenzene

l ^ .i.S-Tetrachlor-A-nitrobenzene (TECHAZEN)

Pentachlornitrobe.nzol. (QUINTOZEN)

1,3,4-TrIChIOr-Zj ^, 6-trinitrdbenzene

Isomeric of l ^^ - trichloro-Zfß-dinitrobenzene and l, 2,3-trichloro-4,6-dinitrobenzene

2,4,5,6-tetrachloroisophthalic acid nitrile 2,4-dinitrophenyl thiocyanate Diphenyl

0-IJi trod i phenyl] -chloro-2,4-dinitronaphthal in acenaphthene

2,4,6-trichlorophenol 2,4,5-trichlorophenol 2,4,5-triclilorphenyl acetate 2,4,5-trichlorophenyl chloroacetate Trichlorophenol, zinc salt, m-cresyl acetate

2,3,4,6-tetrachlorophenol pentachlorophenol (PCP)

O-hydroxybenzene

2,4-dioxy-n-hexylbenzene 2-phenylphenol

3,5-Dibromosalicylaldehyde 2-Benzyl-4-chlorophenol 2,2'-Oihydroxy-5,5i-dichloro-di-pheny1 methane (DiCHLORPHCN) 2,2'-Dihydroxy-3.3 ^l , 5.5 ^l , 6.6 ^l -hexachlorodiphenyl (nethaa 2.2 ^l -dihydroxy-5,5'-dichloro-diDhenylsulfid 2.2 ^l -0ihydroxy-3 _I 3 ', 5.5 ^l -tetrachloro-di-phenyl sulfide 2.2 ^l -0ihydroxy-3 , 3 ^I _I 5,5 ^! -Tetrachloro-diphenylsulphide-disodium salt 4-chloro-0-pheny1-phenol 1,4-di-chloro-2,5-di-niethoxybenzo 1 (CHLORNEB) salicylanilide

Bismuth salicylate kit chlorine or bromine halogenated trifluoromethyl salicylanilide

509841/0986

Bropied salicylanilide

(3,5-Dinethyl-4-chlorophenoxy) ethanol 2- (l-methyl-n-propyl) -4,6-dinitropheny1-2-methylcrotonate (BINAPACRYL) 2- (l-methyl-n-propyl) -4,6-dinitrophenyl isopropyl carbonate (DlNOBUTON) 2- (l-methyl-n-heptyl) -4,6-dinitrophenyl crotonate (DIHOCAP)

Methyl-2,6-dinitro-4- (l-ethyl-hexyl) phenyl carbonate + methyl-2,6-dinitro-4- (l-propyl-penty]) phenyl carbonate (DINOCTON)

4-nony] 2,6-dinitro-phenylbutyrate

S-i-methyl-2- (1-methyl-n-heptyl) -4,6-dinitrophenyl thiocarbonate

2,6-dichloro-4-nitroanil.in (0ICHLORANE) 2-cyanoethyl-N-phenylcarbanate Propyny 1 -N-pheny 1 carbaitat s- (2-bron; acetoxy) -acetanilide

2,3,5,6-tetrachlorobenzoquinone (1,4) (CHLORANIL) 2,3-dichloro-naphthoquinone (1,4) (DICHLON) 2-Amino-3-ch] or-naphthoquinone (1,4) 2-chloro-3-acetamino-naphthoquinone (l, 4) 44; ethyl-2,3,5,10-tetrahydro-3,5,10-trioxo-4H4-H-naphtho (l, 3, -b) -l, 4- triazine 2 _l 3,6,7-TetΓachloΓo -4a, 8a-epoxy-l, 2,3,4,4a, 8a-hexahydro-l, 4-bethanonaphthaΠn-5,8-dione quinone oxime benzoyl hydrazone (BE'IQUIN'OX) N4richloromethylthio) phthaliniid (FOlPET) N- (trichloroethylthio ) cyclohex-4-en-l, 2-dicarboxiinid (CAPTAN) N- (l ^ 2,2-tetrachlorä ^ hylthio) cyclohex-4M3n-1,2-dicarboxiraid (CAPTAFOL) N-k'ethanesulfonyl-N-trichloromethylthio- p-chloroaniline N'-dichloroiluomethylthio-NN-diijethyl-N'-phenylsulphanide (DICHLORFLUABID) S- (2-pyridyl-1-oxide) -S'-trichloroethyl disulphide; Hydrochloride

0,0,0-trinethyl thiophosphate 0,0-diethyl phthalimidophosphonothioate 5-Amino-bis (diiiiethylanido) phosphinyl-3-phenyl-1,2,4-triazole (TRIAMIPHOS) 5-Hethylamino-bis (di-diethylamine) phosphinyl-3-phenyl-1,2, A-triazole

OjO-diethyl-O ^ -pyrazinyl-phosphorothioate

0-ethyl-S, S-diphenyl dithiol phosphate

O-Ethy1-S-benzy1-pheny1di thiophosphonate

0,0 diethyl S-benzyl thiol phosphate

Zinc salt of dithiocarbasic acid Natriuni-N-ethyl-dithiocarbaiiat (METHAM) NatriuRi-N-methoxyethyl-dithiocarbamate Sodium-N, N-diirethyl-dithiocarban; at (DDC) Araraonium-N, N-diRiethyl-di thiocarbaraat Zinc-N.li-dinethyl-dithiocarbaiüat (ZIRAM) Iron-HjN-dimethyl-dithiocarbanate (FERBA) Copper H.H. dimethyl dithiocarbamate Oinatriun-ethylene-l ^ -bis-dUhiocarbamate (NABAU) Zinc-ethylene-l ^ -bis-dithiocarbacate (ZINEB) Iron-ethylene-l ^ -bis-dithiocarbaaat

fc! angan (l I) -äthy 1 en-1,2-bis-dHhiocarbaraat (MANEB)

Calclum-ethylene-t, 2-b5s-dithiocarbacate Ammonium-ethylene-1,2-bis-di-thiocarbamate Zinc-propylene-l.Z-bis-dithiocarbaniat (WEZINEB) (PROPINEB) Bis (diethylthiocarbanyD-ethylene-l.Z-bis-dUhiocarbamate Koaplex consisting of (UANEB) and zinc salt (MANCOZEB) Tetraäthylthiuraa aonosulfid

Bis-fN.N-direthyldithiocarbarayUerkaptoi-Bethylarsine Tetramethylthiura disulfide (THIRAM) '509841/0986

DlpyrrolIdylthiuramdisulfid N, N ¹ -ßis-idimethylamino) thiuramdi9uIfid Polyäthylenethiuramulfid complex consisting of (ZINEB) and Polyäthylenethiuraradisulfid (METfRAM) Bis- (3,4-dichloro-2 (5) -ethicethyl-anymethyl-24! nitrofuran 5-nitro-furfuraldoxine- (2) 5-nitro-furfuryl-amidoxine) - (2) l-oxy-3-acetyl-6-methyl-cyclohexen- (5) dione- (2,4) (dehydroacetic acid )

³ - [- i ³ » ⁵ -Di ⁽ⁱ ie'thyl-2-oxycyclohexyl) -2-hydroxyethyl] -glutariinide (cycloheximide)

Phthalimide Pyridine-2-thiol-1-oxide or. l-hydroxypyridine-2-thione Zinc salt of pyridine-2-thiol-1-oxide

llangan (ll) salt of pyridine-2-thiol-1-oxide

S-I (1 - Oci do-2-pyridy I jisothiuronium chloride

a, a-bis (4-chlorophenyl) -3-pyridinemethanol (PARIHOL) 8-hydroxyquinoline (8-QUINOLINOL) 8-hydroxyquinoline sulfate (CHINOSOL)

Benzoyl 8-hydroxyquinoline salicylate

3- (2-methylpiperidino) propyl 3,4-dichlorobenzoate 6-ethoxy-1,2-dihydro-2,2,4-trine; ethylquinoline (ETHOXYQUIN)

N-lauryl-isoquinolium bromide

9- (p-n-Hexy 1 oxyphenyl J-IO-methyl-acridiniunichlorid 9- (p-n-Hexyl oxyphenyl J-10-niethyl-acridiniura-p-toluenesulfonate 2-n-heptadecylimidazolidine acetate (GLYODINE) l-hydroxyethyl-2-heptadecylimidazolidine 1-phenyl-3,5-dimethyl-i-nitrosopyrazole 1-p-chloropheny] -3,5-dim1: hyl-4-nitrosopyrazole 1-p-Suifamylphenyl-3 _f 5-dimethyl-A-nitrosopyrazole

K- (1-phenyl-2-nitropropyi) piperazine

2-Dirr.ethylaf! Uno-6-methyl-5-n-butyl-4-hydroxypyrimidine

N-dodeyl-1,4,5,6-tetrahydric pyrimidine H-dodecyl-2-methyl-1,4,5,6-tetrahydropyrimidine

2-n-heptadecyl tetrahydropyrimidine 1- (4-Amino-4-propy1-5-pyramidyl-niethyl) -2-methylpyr1dinium chloride hydroxychloride 2- (2'-furyl) benzimidazole (FÜRIDAZOL) 3-dodccyl-1-methy] -2-phenylbenzimidazolium ferricyanide

Meihyl-N-benzimidazol ^ -yl-N-ibutylcarbamoyDcarbamat "(BENOMYL)

2- (0-chloroanilino) -4,6-dichloro-sym.-triazine 2-ethy 1 aniπο-6-methy ] -5-n-buty1-4-hydroxy pyrinfdin

5-chloro-'i-phenyl-1,2-dithiol-3-one 2,3-Dicyano-1,4-dlthia-anthraquinone (DITHIANON) 2- (4-thiazolyl) benzinidazole 4- (2-chlorophenylhydrazono) -3-, iiethyl-5-isoxazolone (DRAZOLON)

Thiazolidines-4-thione- (2) (RHODANINE)

3- (p-chloropheny1) -5-methy1rhodan in

S.S-Dinethyltetrahydro-l ^ .S-thiadiazin ^ -thione (DAZOHET)

3 _J 3 ^f -Aeihylen-bis- (tetrahydro-4,6-dimethy1) -2H-1,3,5-th1ada2in-2-thione) («ILNEB) 3-ßenzylideneamino-4-phenylthiazolin-2-thione e-chlorobenzothiazole ^ -thiol, zinc salt

G-P-diethylamino-ethoxy ^ -dimethylaniino-benzothiazole dihydrochloride Monoethanol, ionium benzothiazole-2-thiol Laurylpyridinium-S-chloro ^ -mercaptoberethiazole

509841/0986

Zinc and sodium salts of 2-mercaptobenzothiazole and dimethyldithiocarbamate Mß-DfäthylarainoäthoxyM -diinethylaninobenzthiazol-dihydrochloride S-trichloromethylthiobenzothiazolone

3-trichloroethylthiobenzoxazolone 3- (Trlchloromethyl) -5-ethoxy-1,2,4-thiadiazoI 6-methyl-2-oxo-1,3-dithiolo [4,5-b] -quinoxaline (QUIKOMETHiONATE) 2-thio-1,3-dithiolo [4,5-bj-quinoxaline (THIOQUINOX)

Z ^ -Olhydro-S-carboxanilido-B-niethyl-lji-oxathine

3,3,4,4-tetrachlorotetrahydrothiophene-l _f 1-dioxide 2,3-0ihydro-5-carbxanU ido-6-methyl-1,4-oxaquin-4,4-dloxide

Ethyl-trimethylaimaoniunbronid

n-alkyl (C ", C, C _fi ) dimethylbenzylammonius dichloride

Alkeny1-dι me tfty1ätfiy1ammon i unbrom i d Dialkyldiitethylamraoniufibronide Alkytdinethylbenzylammonium chloride C -C alkyl tolylraethyltrimethylammonium dichloride Oi-isobuty IKresoxyäthoxyäthyldiirethylbenzylammonlumchlorid

p-Di-isobutylphenoxyethoxyethyl dimethyl benzylannononium chloride

Benzoyl trimethyl ammonium bromide

Gliotoxin 2,4-diguanidino-3,5j6-trihydroxycyclohexyl S-deoxy ^ -O-fZ-deoxy-Z-methylainino-ii-L-glucopyranosynS-C-foriiiyl-p-

L-lyxopentofuranoside (STREPTOMYCIN) T-ChloM.e-dimethoxycuniaran-a-on-Z-spiro-l'-fZ'-nethoxy-e'-iiiethylcyclohex ^ '- en-'iOn) (GRISEOFULVIN) A-dimethylamino-1,4,4a, 5,5a, 6,11,12o-octahydro-3,5,6,10,12,12a-hexahydroxy-6-niethy] -1,11-dioxo-Z -naphthacencarboximu!

(OXYTETRACYCLINE) 7-chloro-4-dimethylamino-l, *, ia _f 5,5a, 6, ll _f 12a-octahydro-3,6,10,12, I2a pentahydroxy-S-methyl-ljll-dioxo ^ -naphthacencar boximid (CHLORINE TRACYCLIN) (PIHARICIN) (LAHCOMYCIfI) (PHLEOMYCIN) (CASUGAMYCINE) (PHYTOACTIN)

Df-J-threo ^^ - dichlor-N-tS-hydroxy-a-fhydroxymeihyn-p-niirophen-äthyl! Acetamid (CHLORAMPHENICOL) Blasticidin-S-benzylanino-benzo-isulfonate N- (3-nitrophenyl) haconin "d Phenoxyacetic acid Sodium p-dir.ethylamino-benzenediazosulfonate Acrolein phenylhydrazone

2-chloroacetaldehyde (2,4-dinetropheny1) hydrazone 2-chloro-3- (iolylsulfonyl) propionitrile l-chloro-2-phenyl-pentane-diol (4,5) -thione (3) p-Nonylphenoxy polyethyleneoxyethanol-iodine complex (c-Nitro ^ ethyD-O-chlorobenzylthioethylamine hydrochloride 3- (p.-t.-buty1-pheny! Sulfony1) acry1 onϊ tri1

Octachlorocyclohexenone Pentachlorobenzyl alcohol Pentachlorobenzyl did Pentachlorobenzaldehyde cyanohydrin

2-horcapphane ethanol 2 _f 6-bis (dif! 'EthylaTinoniethyl) -cycIohexanone 0ec3chloroctahydro-1,3, * -ir.etheno-2H-cyclobuta [cd] -pentalen-2-one 1- (3-Chl oral IyI J-S ^ .T-triaza-l-azoniaadamantane chloride

Coal tar and blast furnace tar

509841/0986

Hische Nickel Sulphate Maneb

Mixture of maneb-iferkaptobenzothiazole 2513 7 8 8

Zineb-Merkaptobenztbiazole mixture Mixture of Zineb-NickeKl l) chloride Zineb-nickel mixture (I D-sul fat Mixture of Ziram-basic copper sulphate Mixture of Ziram-zinc-nerkaptobenzthiazole Mixture of thirara-cadnriuachloride hydrate Mixture of thiram-hydroxy mercury chlorophenol Mixture of thira ^ .- Phenylqjecksiberacetat

Mixture of polyethylene-bis-thiuram sulfide-copper oxychloride Mixture MethyJarsin-bis- (dimethyldithiocarbamatj-ziram-thirani

Mixture of FbIpet- ^ henylmercuric acetate Mixture of Oodine-Ferbam-Sulfur Oithianon copper oxychloride mixture Mixture Oichlone-Feroa.ii-Schsiefe] Mixture of dinocap-dinitrooctylphenol

Mixture of captan-quintozene-tribasic copper sulphate Mixture of cadraium propionate and fhenyl mercury propionate

Formaldehyde-urea mixture

Mixture of phenylamraonium calcium chloride lactate-phenyl mercury formamide

Mixture of basic copper sulphate zinc salts

509841/0986

Example 3

Action against Phytophthora infestans on Solanum lycopersicum (= Tomatoes).

Ia) Residual preventive effect

Solanum lycopersicum- plants of the cultivar "Roter Gnom" after 3 weeks of cultivation after spraying with a 0.05% Broth containing active substance (made from the active substance processed into a wettable powder) and their After drying, infected with a zoospore suspension of Phytophthora infestans. You will then stay in one for 6 days Climatic chamber at 18 to 20 and high humidity, which is generated by means of an artificial spray. To typical leaf spots appear at this time. Your number and sizes are the assessment criteria for the tested substance.

509841/0986

Ib) curative o '.M yI .un :;

Tomato plants of the variety "Red Gnome" become after three weeks Cultivation with a zoospore suspension of the fungus and sprayed in a booth at 18 to 20 and incubated at saturated humidity. Interruption of humidification after 24 hours. After drying the plants are sprayed with a broth that contains the active substance formulated as a wettable powder at a concentration of 0.05%. After the spray coating has dried on, the plants are back set up in the humid cabin for 4 days. The number and size of those occurring after this time typical leaf spots are the benchmark for the effectiveness of the tested substances.

II) Preventive-systemic effect

The formulated as a wettable powder is in Einei "concentration of 0.05 ⁰ L (based on the soil volume) onto the soil surface of three week-old potted tomato plants of the variety" Roter Gnom "added. After three days of waiting time, the lower leaf surface of the plants with a zoospore suspension is They are then kept in a spray booth at 18 to and saturated humidity for 5 days, after which time typical batting stains form, the number and size of which are used to assess the effectiveness of the substances tested.

In these three experiments, the compounds of the formula I show a strong leaf fungicidal action, ie the fungal attack is below 5%. In the D-forms of the compounds, ie the active ingredients no. La and 2a, the fungus infestation is even at application rates of 0.02% in all three tests under 5%.

509841/0986

Example 4

Action against Plasmopara viticola (Bert, et Curt.) (Berl. et DeToni) on vines

a) Residual preventive effect

Vine cuttings of the "Chasselas" variety were grown in the greenhouse. In the 10 ßlatt stage, 3 plants were sprayed with a broth (0.05 ° L active ingredient) prepared from the active ingredient formulated as a wettable powder. After the spray coating had dried on, the plants on the underside of the leaves were evenly infected with the spore suspension of the fungus. The plants were then kept in a humid chamber for 8 days. After this time, clear symptoms of disease appeared on the control plants. The number and size of the infection sites on the treated plants served as an assessment standard for the effectiveness of the substances tested.

b) Curative effect

Vine cuttings of the "Chasselas" variety were grown in the greenhouse used and in the ΙΟ-leaf stage with a spore suspension infected by Plasmopara viticola on the underside of the leaf. After 24 hours in the humid cabin, the plants were with a 0.05 ug active substance broth sprayed from a wettable powder of the active ingredient had been manufactured. The plants were then kept in the humid cabin for 7 days. To at this time the symptoms of the disease appeared on the control plants. The number and size of the infection sites on the treated plants were used as a benchmark for the Effectiveness of the substances tested.

509841/0986

• Μ.

In these two experiments of Example 4, the compounds show of formula I strong fungicidal effect with the following concentrate: ions:

Active ingredient no. concentration Mushroom
a) and - 5th fall at
b) 1 0.05 7o 0 - 5th Vo 0.02 7o 0 - 5th 7th
/O la 0.02 Vo 0 - 5th 7th
la 2 0.05 Vo 0 - 5th 7th
/ ο 0.02 % 0 - 5th ^ o 2a 0.02 7o 0 100 I. 7th
/ ο control

Example 5

Action against Pythium debaryanum on Beta vulgaris (sugar beet)

a) Effect after application to the soil

The mushroom is cultivated on sterile oat kernels and added to a soil / sand mixture. The soil infected in this way is filled into flower pots and sown with sugar beet seeds. Immediately after sowing, the test preparations, formulated as wettable powders, are poured over the soil as aqueous suspensions (0.002 V _{0 of} active ingredient based on the volume of the soil). The pots are then placed in a greenhouse at 20-24 ° C. for 2-3 weeks. The earth is kept evenly moist by lightly spraying it with water. When evaluating the tests, the emergence of the sugar beet plants and the proportion of healthy and diseased plants are determined.

b) Effect after pickling application

The mushroom is cultivated on sterile oat kernels and added to a mixture of soil and sand. The earth so infected will bottled in flower pots and sown with sugar beet seeds that

5 0 9 8 4 1/0986

pickled with the test preparations formulated as pickling powder (0.1% active ingredient based on the weight of the seeds). The sown pots are kept in the greenhouse for 2-3 weeks 20-24 C. The earth is kept evenly moist by lightly spraying it with water. During the evaluation, the emergence of the sugar beet plants and the proportion of healthy and diseased plants are determined ".

Under the conditions of both test a) and b), after treatment with one of the active ingredients 1, 1a, 2 or 2a, over 85 Vo of sugar beet plants emerged and had a uniformly healthy appearance. In the case of the untreated control, fewer than 20 % of the plants emerged, some of which had a sickly appearance.

509841/0986

Claims (13)

Claims 1. Anilides of the formula I R. CH (D where R is water to df or methyl. 2. The compound N- (1'-methoxycarbonyl-euhyl) -N- (Euran- (2 ") carbonyl) -2,6-dimethylaniline of the formula CH. according to claim 1. 3. The compound N- (I ¹ -methoxycarbonyl-ethyl) -N- (furan- (2 ") -carbonyl) -2,3,6-trimethylaniline. 4. The enantiomeric D configurations of the compounds according to any one of claims 1 to 3. 5. Process for the preparation of compounds of the formula I. (D wherein R is hydrogen or methyl., by acylation of a Compound of formula II 509841/0986 R CH CH ₀ I 3 NH-CH-COOClI. (H) with furan (2) carboxylic acid, its acid halide, acid anhydride or one of their esters or amides, where R has the aforementioned meaning Has. 6. The method according to claim 5, wherein the acylation is furan (2) carboxylic acid chloride or furan (2) carboxylic acid bromide is used. 7. Process for the preparation of compounds of the formula I. (D wherein R is hydrogen or methyl, by reaction of the furan (2) carbonanilide of the formula III R CH (III) where R has the aforementioned meaning, initially with butyl lithium or Na hydride to the corresponding alkali salt and reaction with methyl a-halopropionate or by reaction of the anilide of formula III with methyl a-halopropionate in Presence of alkali carbonate as a proton acceptor. 8. The method according to claim 7, wherein the reaction with α-chlorine or methyl a-bromopropionate in the presence of alkali carbonate: is carried out with the addition of catalytic amounts of alkali iodide, 509341/0986 9. A microbicidal agent containing a compound as an active ingredient of formula I. CH. R CH CH-COOCH (D where R is hydrogen or methyl, together with suitable carriers and / or application-promoting additives. 10. Microbicidal agent according to claim 9 containing as active ingredient N- (I ¹ -methoxycarbonyl-ethyl) -N- (furan (2 ") - carbonyl) -2,6-dimethy! Aniline. 11. A microbicidal agent according to claim 9 containing as active ingredient N- (I ¹ -methoxycarbonyl-ethyl) -N- (furan (2 ") -carbonyl-2,3,6-trimethy! Aniline. 12. Use of the compound N- (I'-methoxycarbonyl-ethyl) -N- (furan- (2 ^M ) -carbonyl) -2,6-dimethylaniline for combating phytopathogenic fungi. 13. Use of the compound N- (I '-methoxycarbonyl-ethyl) -N- (furan (2 ^l! ) -Carbonyl) -2, 3, 6-trimethylaniline for combating phytopathogenic fungi. 503841/0986