DD263687A1 - FUNGICIDAL AGENT WITH ADDITIONAL PLANT GROWTH REGULATORY EFFECT - Google Patents

Abstract

The invention relates to novel N-alkyl-2,6-dimethylmorpholinio-alkyl-phenyl ether salts of general formula I, process for their preparation and their use as fungicides for the control of fungal pathogens in agriculture and horticulture. In addition, the agents according to the invention have plant growth-regulating properties. The meaning of R1, R2, R3, R4, R5 and X can be taken from the description. Formula I

Description

Z636 / 7

The invention relates to novel N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-alkyl-phenyl ether salts and their use as fungicidal agents in agriculture and horticulture with additional plant growth-regulating properties.

Ch.araXte.r.is.fcik. .der, ₇ Ue.kanrtt.en.te.c, hnts.ch, eri JJ.ö.auna, en

It is known to use N-alkylmorpholines and their salts and their molecular and addition compounds as fungicides (DE-PS 1 164 152, DE-PS 1 373 722, DE-PS 24 61 513). It is also known that quaternary ammonium compounds of long-chain N-alkyl-2,6-dimethylmorpholinen with lower alkyl, alkenyl, alkoxyalkyl or aralkyl substituents are fungicidally effective (DE-PS 1,167,588, Angewandte Chemie 77 (1965), Pp. 327-333). Furthermore, agents are known which contain substituted N-benzyl or alkoxymethyl-2,6-dimethylmorpholinium salts as active ingredients for controlling fungal pathogens (DD-PS 134 037, DD-PS 134 474, DD-PS 140 403). It is furthermore known that morpholinoalkylalkyl ethers, 4-alkylcyclohexyl ethers and 4-alkylaryl ethers have fungicidal properties (German Patent 1,190,724, Angewandte Chemie 77 (1965), pp. 327-333; Angewandte Chemie 9Z (1980), p. 176-181). Furthermore, 2,3-dihydro-6-methyl-5-phenylearbamoyl-1,4-oxathiin-4,4-dioxide (oxycarboxine), M, N'-bis- (1-formamido-2,2, 2-trichloroethyl-piperazine (triforine) or zinc ethylene-bis-dithiocarbamate (zineb) as active ingredients in fungicidal plant disease control agents (The Pesticide Manual, British Crop Protection Council, Uondon, 1979) Compounds, however, are not always fully satisfactory in certain areas of indication, especially at low rates and concentrations, and they show a very high selectivity towards certain types of fungal soybean pathogens, thereby greatly increasing their use

is restricted. A further disadvantage is that the plant compatibility of these compounds is not sufficient in many cases.

Goal of. Jer. A training

The aim of the invention is the development of new compounds with improved fungicidal activity and additional growth-regulating properties and a process for their preparation, and fungicidal compositions containing such compounds, and the use of such fungicides in agriculture and horticulture.

D.ap.l.e_g.un g, the. , We3.ena.en.r. .Invention

The invention is based on the object, new N-alkyl-2,6-cis- and / or trans-dime thylmorpholinio-alkyl-phenyl ether-Sa Iz containing fungicidal agent with good efficacy and broad spectrum of activity and the highest possible plant compatibility and additional plant growth-regulating properties provide. To solve this problem, fungicidal agents are proposed, which are characterized in that they contain at least one N-alkyl-2,6-cis- and / or trans-dimethylmorpholinio-alkyl-phenyl ether salt of the general formula I,

0. ISI L nt A (J

..go R ^ -O-

in the

R is straight-chain or branched alkyl having 6 to 20 C atoms, R "~ geradkettiyes or branched alkylene having 1 to 6 C atoms, R, R and R independently of one another the same or different hydrogen, straight-chain or branched alkyl having 1 to 6 C Atoms, alkoxy having 1 to 4 C atoms, acyl having 1 to 4 C atoms, halogen, halogenoalkyl having 1 to 4 C atoms, cycloalkyl having 3 to 7 C atoms, Ary1-lower-alkyl having 7 to 12 C, -atoms,

Aryl, nitro, cyano, thiocyanato, NHCOR ¹ , COOR ¹ and / or CONR ¹ R ", where R ¹ and R ^{11 are} independently hydrogen, straight. Chained or branched alkyl having 1 to 6 C atoms, aryl or aryl-lower-alkyl. with 7 to 12 carbon atoms, and X "mean the anion of a non-phytotoxic acid, in addition to the usual Ljösungsmitteln, carriers and / or formulation excipients included.

The compounds according to the invention can exist in two different geometric structures as N-alkyl-2, cis-dimethylniorpholdioalkylphenyl ether salt or N-alkyl-2,6-trans-dimethylmorpholinioalkylphenyl ether salt or as mixtures of these two isomers.

Surprisingly, it has been found that the novel N-alky1-2,6-cis- and / or trans-dimethylmorpholinio-alkyl-phenyl ether Saize of the general formula I have a strong fungicidal activity and broad spectrum of activity and in particular for controlling phytopathogenic Mushrooms on crops and vegetable stocks are suitable. The active compounds show good plant compatibility in the amounts required for controlling plant diseases. In addition, the compounds according to the invention, with their growth-regulating properties, can positively influence crop plants in the desired manner.

Furthermore, it has been found that the N-alkyl-2,6-cis- and / or transdimethylmorpholinio-alkyl-phenyl ether salts of general formula I are obtained by reacting an N-alkyl-2,6-cis- and / or transdimethylmorpholin of formula II,

0 NR ¹ (II)

n ₃ c> -

wherein R has the meaning given in the general formula I, with a compound of the formula Hi

-4- zcnn

χ - R- - ο - (/- * T ~ f (in)

Wherein R, R ₇ R and R are those given in the general formula I.

Have meaning and X is halogen,

implements

or alternatively a 2,6-cis- and / or trans-dimethylmorpholino-

alkylphenyl ethers of the formula IV,

/ \ - R ² - 0 - <f ^ r ^R4 (IV)

2 3 4 5 in which R, R, R and R have the meaning given in the general formula I,

with a compound of the formula V,

R ¹ - X (V)

wherein Λ has the meaning given in the general formula I and X is halogen reacted.

N-alkyl-2,6-cis- and / or trans-dimethylinorpholines of formula II are e.g. n-octyl, n-dodecyl, n-tridecyl, iso-tridecyl, 1,5,9-trimethyldecyl, n-pentadecyl or n-didecyl-2,6-cis- and / or trans-dimethylmorpholine ,

Haloalkylphenyl ethers of the formula III are, for example, 2-bromoethylphenyl ether, 2-chloroethyl-4-tert-butylphenyl ether, 2-bromoethyl-4-nitrophenyl ether, 2-bromoethyl-4-cyano-phenyl ether, 2-3-methylethyl, 6-diclorophenyl ether , 2-bromoethyl 1-3,4-dichlorophenyl ether, 2-bromoethyl] -2,6-dichloro-4-cyanophenyl ether, 2-bromoethyl, 1-3,5-dichloro-phenyl ether, 2-bromo-thi 1-4-benzyl plieny 1 e ther, 2 -0 romet hy 1-4 -a ce tanüdophenylether, 3-Brompropyi-jjhenylether, 3-ßrompropyl-4-tert. butylphenyl ether, 3-bromopropyl-2, ö-dimethylphenyl ether or 3-bromopropyl-2,6-dibroni-4-thiocyanatophenyl ether.

 · 5 -

2,6-cis- and / or trans-dimethylmorpholino-alkyl-phenyl ethers of formula IV are e.g. 2- (2,6-CiS- and / or trans-dimethylmorpholino) ethyl phenyl ether, -4-cyano phenyl ether, -4-tert-butylphenyl ether, -4-nitrophenyl ether, -3,4-dichlorophenyl ether, -2,6 - Diichlbr · ^ - cyanophenyl ether, 3- (2,6-cis- and / or trans-dimethylmorpholino) -propyl-1-phenyl ether, -4-tert-butylphenyl ether, -3,5-thehlorphenylether, -2,6-dinethylphenylether or -2,6-dibromo-4-thiocyanatophenylether.

Alkyl halides of the formula V are, for example, n-decyl chloride, n-dodecyl chloride, n-tridecyl chloride, isotridecyl chloride, 1,5,9-trimethyldecyl chloride, pentadecyl bromide or didecyl bromide.

- e - ZtSCfϊ

The conversion to the novel compounds of formula I are optionally carried out in the presence of a Uösungs- or diluent at a temperature ranging between 10 and 180 ⁰ C, preferably between 30 and 150 ⁰ C. The starting materials of the formula II or of the formula IV are in stoichiometric amounts with a compound of formula III or of formula V or preferably with an excess of 10 to 100 % of a compound of formula III or of formula V over the stoichiometric amount also, based on the starting materials of the formula II or the formula IV, implemented.

Examples of preferred dissolution or diluents are aliphatic or aromatic, optionally halogenated hydrocarbons, such as n-pentane, cyclohexane, benzene, toluene, chlorobenzene, chloroform or methylene chloride; aliphatic ketones, such as acetone, methyl ethyl ketone or cyclohexanone; Ethers, such as diethyl ether, tetrahydrofuran or dioxane; Alcohols, such as methanol, ethanol, propanols, butanols or hexanols; Nitriles, such as acetonitrile; Esters, such as methyl acetate; Amides, such as dimethylformamide, dimethylacetamide or N-methyl-pyrrolidone; Dimethyl sulfoxide or water or mixtures of these solvents can be used.

The isolation of the compounds of the general formula I according to the invention from the reaction mixtures is not absolutely necessary since they can also be used without further purification operation for the production of fungicidal preparations.

The active compounds of the general formula I according to the invention have a strong activity against microorganisms and can accordingly be used for combating fungal pathogens in agriculture and horticulture. The active substances can be used to combat unwanted fungi that occur on plants or plant parts. The active compounds of the general formula I are also suitable as mordants for the treatment of seed and plant cuttings for protection against fungal infections and can be used against occurring in the soil phytopathogenic fungi. In addition, the active ingredients in their application influence the growth processes of crops in a positive way.

The active compounds according to the invention are particularly suitable for the prevention and cure of plant diseases caused by fungi, e.g. Erysiphe gratninis (powdery mildew), Erysiphe cichoracearum (cucumber powdery mildew), Erysiphe polygon! (Bean powdery mildew), Podosphaera leucotricha (apple downy mildew), Sphaerotheca pannosa (rose mildew), UncinuJo necator (vineyard powdery mildew); Rostkrankheiter, such as those of the genera Puccinia, Uromyces or Hemileia, in particular Puccinia graminis (grain black rust), Puccinia coronata (oat crown rust), Puccinia sorghi (corn rust), Puccinia recondita (cereal rust), Uromyces fabae (bush beans rust), Hemileia vastatrix (coffee rust) ; Botrytis cinerea on vines and strawberries; Monilia fructigena on apples; Plasmopara viticola on vines; Mycosphaerella musicola on bananas; Corticum salmonicolor on Hevea; Ganoderma pseudoferreum on Hevea; Exobasidium vexana to tea; Phytophthora infestans on potatoes and tomatoes; Alternaria solani on tomatoes. Furthermore, various of these agents are also differentially effective against phytopathogenic fungi, such as e.g. Ustilago avenae (flare), Ophiobolus graminis (cereal foot disease), Septoria nodorum (cereal leaf and tuberola), Venturia inaequaJis (apple scab) and various specis of the genera Rhizoctonia, Tilletia, Helminthosporium, Peronospora, Pythium or Mucor.

Particularly interesting are the active compounds according to the invention for combating a variety of fungal diseases on various crops or their seeds, especially wheat, rye, barley, oats, rice, corn, cotton, soybeans, coffee, bananas, sugarcane, fruit, ornamentals in horticulture, vegetables like cucumbers, beans or cucurbits.

In addition, the active compounds according to the invention, with their plant growth-regulating properties, can positively influence the development of crop plants in the desired manner. The effects of the compounds are essentially dependent on the time of application, based on the stage of development of the seed or of the plants, on the amounts of active substance applied to the plants or their surroundings and on the mode of administration.

Furthermore, the active ingredients also provide good activity against wood-discoloring and wood-destroying fungi, such as e.g. Pullaria pullulans, Apsergillus niger, Polystictus versicolor or Chaetomium globosum.

Furthermore, the active compounds of the general formula I according to the invention exhibit a good activity against molds, such as, for example, Penicillium, Fusarium or Aspergillus species that cause varderb of high moisture agricultural products or processed agricultural products during storage or storage. Such products to be treated include e.g. Apples, oranges, mandarins, lemons, grapefruits, peanuts, cereals and cereal products or pulses and meal.

The active compounds according to the invention, in addition to their fungΐη broad fungicidal spectrum of activity and different against phytopathogenic bacteria, such as Xanthomonas or Erwinia species, effective.

Some of the active ingredients also show activity against human pathogenic fungi, e.g. Trichophyte and Candida species.

A part of the active compounds of the general formula I is distinguished, in addition to the protective action, by a systemic development of action. Thus, they are absorbed both via the root and the leaves and transported in the plant tissue or fed via the seed to the aerial parts of the plant.

The active compounds according to the invention are furthermore suitable for controlling resistant strains of fungal pathogens which are resistant to known fungicidal active compounds, e.g. Active substances from the group of dicarboximide fungicides, such as, for example, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine (vinclozolin) or 5-methyl-5 methoxymethyl 1-3- (3,5-dichlorophenyl) -1,3-oxazolidine-2,4-dione (myclozoline); Active substances from the group of the benzimidazole or thiophanate fungicides, such as, for example, methyl l- (n-butylcarbamoyl) -benzimidazol-2-ylcarbamate (benomyl), benzimidazol-2-yl-carbamic acid methyl ester (carbendazim) or l, 2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene (thiophanate); Active ingredients from the

, - 9 - JLGSt H

Group of azole fungicides such as 1- (4-chlorophenoxy-3 _/ 3-dimethyl-1- (1H-l _/ 2 _/ 4-triazol-1-yl) -butan-2-one (triadimefon) or l- / 2 '- (2 "', 4" -dichlorophenyl) -2 '- (propenyloxy) -ethyl / -l, 3-imidazole (imazalil); active compounds from the group of aromatic hydrocarbons-containing fungicides, such as 2 , 5-dichloro-1, 4-dirnethoxy-benzene (Chloroneb) or 2,6-dichloro-4-nitro-aniline (dicloran); active substances from the group of acylalanine fungicides, such as DL'-N- (2. 6-dimethylphenyl) -N- (2'-methoxyacetyl-alanine methyl ester (metalaxyl) or DL! -N- (2,6-dimethylphenyl) -N- (2-furoyl) -alanine methyl ester (furalaxyl) or group of active ingredients the pyrimidine fungicides, such as S-butyl ^ -dimethylamino - ^ - hydroxy-o-methyl-pyrimidine (dimethirimol) or 2-chlorophenyl-4-chlorophenyl-pyrimidin-5-yl-methanol (fenarimol), show signs of resistance.

The anions X.sup.- listed in the general formula I of the active ingredients according to the invention are not decisive for the fungicidal action.

The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, natural and synthetic substances impregnated with active ingredient, very fine encapsulations in polymeric substances and in encapsulants Seeds and IJL'V cold and warm neoen formulations. The preparation of these formulations can be carried out in a known manner, e.g. by mixing or grinding the active compounds of the general formula I according to the invention with solvents and / or carriers, if appropriate using surface-active agents, such as emulsifiers and / or dispersants. As liquid solvents, aromatics such as toluene, xylene or alkylnaphthalenes; chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride; aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions; Alcohols, such as butanols or glycols, and their esters and ethers; Ketones, such as acetone, methyl ethyl ketone,

- ίο -

Methyl isobutyl ketone or cyclohexanone; Strong polcre solvents such as water, dimethylformamide or dimethylsulfoxide used. Likewise, liquefied L 2 solvents which are gaseous under normal conditions, e.g. Aerosol propellants, such as halogenated hydrocarbons, propane, butane, nitrogen and carbon dioxide are used.

As solid carriers are e.g. natural gastric powders such as kaolins, clays, talc, chalk, quartz, montmorillonite or diatomaceous earth, and synthetic greases such as fumed silica, alumina and silicates. As solid carriers for granules, e.g. crushed and fractionated ground natural minerals such as calcite, marble, pumice, dolomite and synthetic granules of inorganic or organic flours and granules of organic materials such as sawdust, cellulose powder, bark and nutshell flour are used. As emulsifying agents, e.g. nonionic and anionic emulsifiers, such as alkali, alkaline earth or Ammonimnsai ze of L 'igninsulfonic, Naphthalensulfonsäuren, Phenolsulfonrväure, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates .. alkali and alkaline earth salts of dibutylnaphthalenesulfonic, L'aurylethersiilfat, fatty alcohol sulfates, fatty acid alkali and Alkaline earth salts, salts of sulfated hexadecanols, lleptdecanoles or octadecanols, salts of sulfated fatty alcohol glycolethorn, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalenes or naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octyl phenol ethers, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isobutylene Tridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal and sorbitol esters.

Suitable dispersants are, for example, L'ignin sulfite derivatives and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic latex-containing polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the formulations. As further additives, dyes and trace nutrients in the

- ii -. ICitf?

Formulations of the active ingredients may be included.

The formulations generally contain between 0.1 and 95% by mass of active ingredient, preferably between 0.5 and 90% by mass.

The inventive method for combating fungi is characterized in that fungicidal agents with the active compounds of the general formula I according to the invention can act on fungi or the objects to be protected against fungal attack in an effective amount.

The active compounds according to the invention can be mixed and applied in the formulations or in the various application forms with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, growth regulators, plant nutrients and soil conditioners. In many cases, a mixture of fungicides results in a broadening of the fungicidal activity spectrum. In a number of mixtures of the active compounds according to the invention with known fungicides, synergistic effects also occur, the fungicidal activity of the combination product being greater than that of the added activity of the individual conjugates. Fungicides which can be combined with the active compounds according to the invention, without restricting the possible combinations, are, for example:

Sulfur,

Dithiocarbamatec and its derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, manganese ethylenebisdithiocarbamate, manganese-ziric-cetylenediamine-bis-dithiocarbanate and zinc thylenebisdithiocarUamate,

Tetramethyl thiuram sulfide,

Ammonia complex of zinc (i \!, N-ethylene-bis-dithiocarbamate) and N, N'-polyethylene ~ bis- (thiocarbamoyl) -disulficl, ammonia complex of zinc (N, N'-propylene-bis -dithiocarbamate) and N, N ¹ -propylcn-bis (thiocarbamoyl) -el-i-sulfide,

N-T r i chlorine t hy 1 th io-te tr any droph thai in id, N-trichloromethylthio-phthalim id,

N- (1,1,2,2-Tetrachlorethy] thio) -tetrahydrophthaiimid,

_{4/6-dinitro-2-} (l-methylheptyl) -phenylcrotonat, _{4/6-DinitΓo 2-8ek.-butylphenyl-3/3-dimethyl} acrylate, _4/6-DinitΓO 2-3ek.-butylphenyl-i8opΓopylcaΓbonat _/

1- (n-Butyl-1-carbamoyl) -benzimidazol-2-yl-carbarninic acid methyl ester, benzimidazol-2-yl-carbamic acid methyl-ghol, 2- / fur-2-yl) -benzimidazole

2- (thiazol-4-yl) -benzimidazole,

1,2-bis- (3-methoxycarbonyl-2-thioureido) -benzene, l, 2-dis- (3-ethoxycarbonyl-2-thioureido) -benzene, 2 _/ 3-dihydro-6-methyl-5-phenylcarbamoylbenzene l, 4-oxathiin, 2 _/ 3-dihydro-6-methyl-5-phenylcarbamoyl-l _/ 4-oxathiin-4 _/ 4-diαxid,

Tetrachloro-isophthalonitrile,

2,3-dichloro-l, 4-naphthoquinone,

2,3-dicyano-l _/ 4-dithioanthraquinone,

N-tridecyl-2,6-dimethylmorpholine or its salts, NC _in -C ₁₄ -alkyl-2,5- and / or 2, G-dimethylinorpholine N-cyclododecyl-2,6-dimethylmorpholine or its salts, N- /3-p-tert.-Butylphenyl)-2-methylpropyl/-2 _/ 6-cis-dimethylmorpholine or its salts

N, N ¹ -Bis (1-formamido-2,2,2-trichloroethyl) -piperazine N- (1-formamido-2,2,2-trichloroethyl) -3,4-dichloroaniline N- (1-formamido) 2,2,2-trichloroethyl) -inorpholin

5-Butyl-2-ethyl-4-hydroxy-6-methyl-pyridinium 5-butyl-2-dimethyl-amino-4-hydroxy-6-methyl-pyrimidine

2,4-diclllo-phenyl-phenyl-pyrazole ^ n-5-yl-1-lethanol 2-chlorophenyl-4-chlorophenyl-pyrimidin-5-yl-methanol Bis- (4-chlorophenyl) -pyridin-3-yl-methanol

5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -1,3-oxazolidine-2,4-dione S-methyl-S-methoxymethyl-S-CS-dichloro-1-chloro-1-oxazolidine-2 , 4-dione

3- (3,5-dichlorophenyl) -N-isopropyl-2-.4-dioxo-imidazole idin-1-carboxamide N-C 1-5 -dichlorophenyl-1-dimethylcyclopropane-1-dicarboximide

- 13 - ZC l · 6 f?

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1 _/ 2 _/ 4-triazol-1-yl) -butan-2-one 1- (4-chlorophenyl) -S, 3-dimethyl-1 - (1,2,4-triazol-1-yl) -butan-2-ol 1- / 2- (2,4-dichloro-1-morphhenyl) -2- (propenyloxy) -ethyl / -imidazo!

l / i \ l-propyl-N- (2,4,6-trichlorophenoxy) -ethyl-carbamoyl / -imidazole l- / 2- _{(2/4-dichlorophenyl)} -4-ethyl-l _/ 3-dioxolon- 2-yl-methyiy-lH-1,2,4-triazole

1- / 2- (2 _/ 4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-methyl-1-1,2,4-triazole

1- (2 _/ 4-dichlorophenyl) -2- (1 _/ 2 _/ 4-triazol-1-yl) -4 _/ 4-dimethyl-pentan-3-one

2,5-dichloro-l, 4-dimethoxy-benzene

2 _/ G-dichloro-4-nitroaniline

diphenyl

2-methyl-benzoic acid anilide

2-iodo-benzoic acid anilide

2, S-Diniethyl-fiirane-S-carboxylic acid ani 1 id

2, 4,5-T ri-methyl-furan-3-carboxanilide iM-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxylic acid amide 3- / 3- (3,5-Dimethy] -2-oxycyclohexyl ) -2-hydroxyethyl ⁷ -glutarimide N-dichloro 1 orf luorinethylthio-N ', M' -dimethyl-N-phenyl-sulfuric acid diamide

DL-i \ - (2,6-dimethylphenyl) -M- (2 '-inethoxyacetyl) -alanine methylester DL ^l - \ - (2, G-dimethylphenyl) -N- (2-furoyl) alanine-methylester INJ (2,6-dimethylphenyl) - \ ^l -chloroacetyl-DL-2-aniinobutydol ^ tcton

2,4-Dichloro-6- (2-chloroanilino) -s-triazine 0,0-Di ethyl-phthalimido-phosphonothioate

5-Amino-1- (bis- (diniethyl-amino) -phosphinyl) -3-phenyl-1,2,4-triazole O, O-diethy1-S-benzyl-thiolphosphoric acid ester 2-thio-1,3-dithio-4- (4,7-dimethyl) -phenyl-1-chloro-1-one , 5-b) -chinoxnlin)

4- (2-Chloro-1-hydrazono) -3-methyl-1-5-isoxazolone pyridine-2-thiol-1-oxide

8-hydroxyquinoline or its salts

4-Dimethylaminophenyl diazo-sulponic acid sodium salt 5-nitro-isophthalic acid di-isopropyl ester

2-Cyano-ethyl (2-ethylaminocarbonyl) -2- (ineethoxy-imino) -acetamide 2-lleptüdccyl-2-imidazole in-ace did dodecyl-yuanidine acetate

The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom by further dilution in a conventional manner, e.g. by dipping, spraying, spraying, atomizing, injecting, silting, spreading, dusting, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting.

In the treatment of parts of plants, the active substance concentrations in the use forms can be varied within a substantial range. They are generally between 0.0001 and 1 percent by mass, preferably between 0.5 and 0.001 percent by mass. The amount of active ingredient used depends on the specific application and is generally between 0.1 and 3 kg of active ingredient or more per hectare.

In seed treatment, in general, amounts of active ingredient of 0.001 to 50 g or more per kilogram of seed, preferably 0.01 to 10 g, are required.

For the preservation or post-harvest treatment of agricultural products or processing products of agricultural products, the amounts of active substance required are from 0.01 to 100 g per kilogram of material to be treated, preferably from 0.1 to 50 g. Dei the treatment of soil, eprozent Wirkstoffkonzontrationen from 0.0001 to 0.1 MaSi ^N is required, preferably from 0.001 to 0.05 percent by mass, at the site of action.

The following examples are intended to further illustrate the invention without, however, limiting it and demonstrating the effect of the compounds of general formula I according to the invention.

- is - 1 (, SCt '?

AuafJihjiu.ri (is.b.e, i.s.p.ie.l.e.

The following examples illustrate the preparation of the compounds according to the invention.

The starting compounds for the preparation of the compounds according to the invention are known per se or can be prepared by processes known per se.

Beisgiele_l

3- (N-iso-tridecyl-2,6-cis- and / or trans-dimethylmorpholinio) -propyl-2,6-dimethylphenyl ether bromide

15 g of N-iso-tridecyl-2/6-cis- and / or trans-dimethylmorpholine and 12.2 g of 3-bromopropyl-2 _/ 6-dimethylphenyl ether in 50 ml of acetonitrile are refluxed with the addition of a catalytic amount of sodium iodide for 23 hours , After cooling, the solvent is distilled off in vacuo. It is taken up in a little acetone and the solution is added until complete precipitation with η-hexane. The oily phase is separated and freed from Uösungsmittelresten in vacuo. This gives 21 g of a yellow-brown viscous oil (compound no. 26). IR spectrum (film): cm " ¹ 2960, 2925, 2870, 2490, 1470, 3380, 1260,

Π95, 1090, 3040

Beisf) iele_2

2- (N-iso-tridecyl-2,6-cis- and / or trans-dimethylmorpholinio) -ethy 1-3,4-dichlorophenyl ether chloride

17 g of 2- (2,6-cis- and / or trans-dimethylmorpholinio) -ethyl-3,4-dichlorophenyl ether and 33 g of iso-tridecyl chloride (mixture of various C 1 -C -alkyl halides containing 60 to 70% contains n-tridecyl chloride) in 50 ml of dimethylformamide are heated to reflux for 10 hours. It is allowed to cool and the solvent is distilled off in vacuo. The remaining residue is dissolved in a little acetone and in 1L. η-hexane until complete deposition as an oily phase

The product is separated off and freed of solvent residues in vacuo. This gives 19 g of a brown resinous product (compound no. 25)

IR spectrum (film) cm " ¹ 2950, 2020, 2690, 2620, 2480, 1590, 1570,

1470, 1385, 1330, 1280, 1225, 1175, 1120,

1085, 1060, 1015

In a corresponding manner, the following compounds of general formula I are prepared, which are generally yellow to brown viscous oils or resins, in polar solvents, such as alcohols, acetone, dimethylformamide and Dimethylsul fox ic ¹ , are well soluble and have the characteristic absorption bands in the IR spectrum.

(I)

1 n-octyl (CHg) ₂ "" 2-Cl 6-Cl Il br 2 n-dodecyl (CH ₂ ) ₃ 4-Cl Il Il br 3 n-tridecyl (CH ₂ ) ₃ 4-Cl H H or 4 5 1,5,9-trimethyldecyl iso-tridecyl (Cl LU (L O 4-Cl H H H H Il Br Dr 6 iso-tridecyl (CH ₂ ) 2 4-Cl Hi Il Cl 7 iso-tridecyl (CII ₂ ) _? 3-F H il br 8th iso-tridecyl (CHg) ₂ 4-tert-butyl H H Cl 9 iso-tridecyl (CH ₀ ) ,, 4-tert-butyl Il Il br 30 iso-tridncyl (Cu ^ 4-0CH ₃ H Il pr 31 iso-tridecyl (CHg) ₃ 3-CH ₃ H Il br 12 iso-tridecyl (CHg) ₂ 4-Co-CiI ₃ Il H br 13 iso-tridecyl (CHg) ₂ 3-NH-CO-CH ₃ Il H br 34 iso-tridecyl (CH ₂ ) ,, 3-CO-OC ₀ H _n H H br 15 iso-tridecyl 2 2 3-CO-N (C ₂ Hg) ₂ Il Il 3r 16 iso-tridecyl (CH _O ) _O £ · L-. 4-NO ₂ Il Il br 17 iso-tridecyl (CH ₂ ) ₂ 4-CN H Il br 18 iso-tridecyl 4-phenyl H Il Cl 19 iso-tridecyl (CIL) ₂ 4-benzyl !! LI I I Cl 20 iso-tridecyl (CH ₂ ) 2 2-Br 4-Br Il 3r 23 iso-tridecyl (CIIp) ₂ 2-Cl 3-Cl Il br 22 iso-tridecyl (CH ₂ ) ₃ 2-Cl 4-Cl H br 23 iso-tridecyl (CIL) 2-Cl 5-Cl H br

No.

24 iso-tridecyl (CH ₂ ) 2 2-Cl 6-Cl Il br 25 iso-tridecyl (CH ₂ ) ₂ 3-Cl 4-Cl H gl 26 iso-tridecyl (CH ₂ ) ₃ 2-CH ₃ 6-CH ₃ Hi br 27 iso-tridecyl ( r * u ^ 3-ChI ₃ 4-CH ₃ Il br 28 iso-tridecyl (CH ₂ ) ₂ 3-Cl 5-Cl H br 29 iso-tridecyl (CH ₂ ) ₂ 2-Cl 4-NO ₂ H "Br 30 iso-tridecyl (CH ₂ ) ₂ 2-Cl 4-Cl 6-Cl br 31 iso-tridecyl (CH ₂ ) ₂ 2-CH ₃ 3-CH ₃ 6-CH ₃ br 32 iso-tridecyl (CH ₂ ) ₂ 2-CH ₃ 4-Cl 6-CH ₃ br 33 iso-tridecyl (CHg) ₄ 2-CH ₃ 4-Cl 6-CH ₃ br 34 iso-tridecyl (CH ₂ ) ₂ 2-Cl 4-CN 6-Cl br 35 iso-tridecyl (CH ₂ ) ₂ 2-Cl 4-NO ₂ 6-Cl br 36 iso-tridecyl (CH ₉ ) " 2-Br 4-SCN 6-Br br 37 HC ₁₅ H ₃₁ (Chi ₂ ) ₂ 4-Cl H Il br 38 HC ₂₀ H (CH ₂ ) ₂ 4-Cl H H br

The compounds of the general formula I according to the invention can be used, for example, in the form of the following preparations:

I .. Be is p. i.e. I

Solution concentrates: 80 parts by weight of compound 5 are mixed with 20 parts by weight of N-methyl-2-pyrrolidinyl. A solution is obtained which is suitable for application in the form of very small drops.

II. Example

Emulsifiable concentrates: 25 parts by weight of compound 24 are mixed with 2.5 parts by weight of epoxidized vegetable oil, 10 parts by weight of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture, 5 parts by weight of dimethylformamide and 57.5 parts by weight of xylene. From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

III .. Beiaßiel

Injection powder: 40 parts by weight of compound 6 are mixed well with 5 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite liquor, 1 part by weight of sodium salt of di-iso-butylnaphthalene-sulfonic acid and 54 parts by weight of silica gel and ground in a corresponding mill. A spray powder is obtained which can be diluted with water to give suspensions of any desired concentration.

Dusts: 5 parts by weight of compound 25 are intimately mixed and ground with 95 parts by weight of finely divided kaolin. The dusts can be dusted in this form for use.

V. Example

Granules: 5 parts by weight of compound 6 are mixed with 0.25 part by weight of epichlorohydrin and dissolved with 6 parts by weight of acetone. Dnnec-h is added to 3.5 parts by weight of ethylene glycol and 0.25 parts by weight of cetyl polyglycol ether. The resulting solution is sprayed on kaolin. Subsequently, the acetone is evaporated in vacuo. It is obtained a micro-granules that can be used in this form.

/ it crt

The following examples are intended to further illustrate the invention without, however, restricting it and to demonstrate the effect of the compounds of general formula T:

Bei8giele_A

Mycelial growth test

The fungicidal activity of the agent against the test fungi is in a conventional manner as inhibition of radial mycelial growth on malt agar medium (2% malt) determined in Petri dishes of 9 cm in diameter at an incubation temperature of 25 ⁰ C. The active compounds are dissolved in dimethylformamide / diluted with water and thus added to the liquid agar / that the desired Wirkstoffkonzantration is achieved in the nutrient medium. The DMF content does not exceed 0.5% by volume. After cooling, the plates are inoculated. The evaluation takes place depending on the growth rate of the fungi, if the controls without the addition of active ingredient are interspersed to 70 to 90% of the shell diameter. The percentage growth inhibition of the active substances compared to the controls without active ingredient addition is calculated (Table A).

Table A: Growth inhibition of fungi in mycelial growth test Growth inhibition in percent

drug Botrytis Phytophthora cin ^ rea cactorum Connection no. IO pg / ml 50 μg / ml Oxycarboxine (known) 20 50 1 22 5 90 6 87 9 85 16 78 67 17 86 100 24 88 81

Continuation Table A:

Growth inhibition in percent

Connection no. 25 26 34 Active substance conc. Botrytis cinerea 10 pg / ml Phytophthora cactorum 50 pg / ml 88 80 92 100 Examples B

Barley thiauze test (Erysiphe graminis / barley)

In tubes with sand barley plants of the variety "Astacus" in the single-leaf stage are dewy sprayed with active ingredient preparations prepared from 1 part by weight of active ingredient, 100 parts by weight of dimethylformamide and 0.25 parts by weight of alkylaryl and diluted with water to the desired active ingredient concentration. After the spray coating has dried on, the plants are pollinated with conidia of barley powdery mildew (Erysiphe graminis var. Hordei). Subsequently, the test plants for a period of 2 to 3 hours at 90 to 100% relative humidity in an incubation cabin and then at temperatures between 20 and 22 and 75 to 80% relative humidity in the greenhouse aufgestelIt.

After 7 days, the powdery mildew of barley plants is determined. The grading values obtained according to STEPHAN (Arch. Phytopath. PfI.-schutz 14 (1978), 163-175) are converted into the level of infestation according to KRÜGER (Nachr.-Bl. Pflanzenschutz GDR 1.9.8.1,, 145-147). This results in the efficiency according to ABBOTT accordingly

Wirkiinnqnrnri (%) - level of infestation control degree of _infestation variant _1nn efficiency (J>) - _ΕΈ ^ _η φ ^ _Ύό ^ _ΓοΎγ . jl χ loo

The results are shown in Table B.

- 22 - ZtSCf t

Table B: Action against Erysiphe graminis on barley Active substance concentration: 10 pg / ml

Connection No. Efficiency in percent

Triforine (known) 86

5 96

24 92 *

25 93

26 95 34 97

Examples

Grain egg test (Puccinia recondita / wheat)

Potted "Alcedo" wheat plants are cut back to a height of 12 cm in the two-leaf stage. The secondary leaf of the plants is removed. Thereafter, di i wheat are plants with active ingredient preparations sprayed / consisting of 20 parts by weight of active ingredient, 10 Gewichtrteilen polyoxyethylene sorbitan monostearate (Tween 60), 5 Gewichtsteiien polypropylene glycol, 25 parts by weight of cyclohexanone and 40 parts by weight of toluene prepared and are diluted with water to the desired concentration of active ingredient. After the spray coating has dried on, the plants are inoculated with spores of the wheat brown rust (Puccinia recondita), which are applied as a suspension in water with Tween 60 additive. The test plants are then placed in a greenhouse-saturated incubation cubicle for a period of hours and then at temperatures of 20 to 22 ⁰ C and at 70 to 80% relative humidity in the greenhouse.

After 10 days, the rust attack of the wheat plants is determined. The efficiency of the means is calculated according to the method described in Example B.

 The results are listed in Table C.

Table C: Action against Puccinia recondita on wheat. Active substance concentration: 500 mg / l

Connection No. Efficiency in percent

Triforine (known) 85

24 99

26 98

BeisgielQ

Botrytis test (Botrytis cinerea / field bean (Vicia faba) leaf fiddle)

Cut leaf leaflets of pot-grown field crops (Vicia faba) of the "Fribo" variety at the VienMatt stage are coated with active compound preparations / which are prepared from 1 part by weight active ingredient, 100 parts by weight dimethylformamide and 0.25 parts by weight alkylaryl polyglycol ether and diluted with water to the desired active substance concentration. After the spray coating has dried on, the leaves are inoculated with a conidia suspension of Botrytis cinerea, which is obtained by washing away 12 to 16-day-old fungal cultures on malt agar medium (2% malt). The broadleaf leaflets are kept in an incubation booth in trays at a temperature of 22 ⁰ C and 90 to 100% relative humidity.

After 4 days, the Botrytis infestation of field bean leaflet is determined. The percentage of attack on the entire leaf area is converted into the efficiency of the means according to ABBOTT. The results are shown in Table D.

Table D: Action against Botrytis cinerea on field bean (Vicia faba) leaf drop Drug concentration: 100 mg / l

Connection No. Efficiency in percent

Tridemorph (known) 42

24 62

25 47

26 51

Beisgiel_E

Phytophthora test (Phytophchora infestans / Tornate)

Tomato plants of the cultivar "Tamina" grown in pots are dewatered with active substance preparations prepared from 1 part by weight of active substance / 100 parts by weight of dimethylformamide and 0.25 part by weight of alkylaryl polyglycol ether and diluted with water to the desired active substance concentration The test plants are then placed in an incubation chamber at temperatures between 18 and 20 ^° C. and 95 to 100% relative atmospheric humidity.

After 5 days, the Phytophthora infestation of the tomato plants begins! Right. The obtained rating values are converted into the degree of infestation and the efficiency of the agents as described in Example B.

 The results are listed in Table E,

Table E: Action against Phytophthora infestans on tomatoes

Compound No. Active substance concentration efficiency in percent

in mg / l

Zineb (known) 100 57

200 61

24 100 66

200 79

BeisgielF

Pflanzenwachstumaregulations test

Gurkeripflanzen of the variety "Eva" are used in pots in humus soil, which is sufficiently supplied with nutrients, up to a stature height of 9 cm in the greenhouse. 10 plants are used per experimental variant. The cucumber plants are sprayed with active compound preparations which are prepared from 1 part by weight of active compound, 100 parts by weight of dimethylformamide and 0.25 parts by weight of alkylaryl polyglycol ether and diluted with water to the desired active substance concentration.

After a growth time of 14 days after the medium application, initial measurements are made on the treated plants and the untreated control plants

 The results are shown in Table F.

Table F: Effect on the growth of cucumber plants in foliar treatment. Active ingredient concentration: 1000 mg / l

Compound No. Plant height

in cm relative

Untreated Control 23 100 24 15 65

Claims (3)

1. Fungicidal agents with additional plant growth regulating effect, such labeled in eichnet characterized in that it comprises at least one N-alkyl-2,6-cis and / or trans-dimethylmorpholinio alkyl phenyl-Saiz of the general formula I, (I) in the R is straight-chain or branched alkyl having 6 to 20 C atoms, 2
R is straight-chain or branched alkylene having 1 to 6 C atoms, 3 4 5
R, R and R independently of one another are identical or different, hydrogen, straight-chain or branched alkyl having 1 to 6 C atoms, alkoxy having 1 to 4 C atoms, acyl having 1 to 4 C atoms, halogen, halogenoalkyl having 1 to 4 C, -Atomen, cycloalkyl having 3 to 7 carbon atoms, aryl-lower-alkyl having 7 to 12 carbon atoms, aryl, nitro, cyano, thiocyanato, NHCOR ', COOR ¹ and / or CONfi'R ", wherein R" and R '' independently of one another represent hydrogen, straight-chain or branched alkyl having 1 to 6 C atoms, aryl or aryl-lower-alkyl having 7 to 12 carbon atoms, and X ~ denote the anion of a non-phytotoxic acid, in addition to the usual solvents, carriers and / or Formu-1ierungshilfsstoffen included. Method for combating fungi, characterized in that means according to item 1 are allowed to act on fungi or on objects to be protected against fungal attack. Use of means according to item 1, fjin_7Rjchnfih in that they are used to combat fungi. Use of means according to item 1, gekennz eichnet dad urch that they are used for regulating plant growth.