DE3220102A1 - Quaternary phosphoniummethylquinolines, their preparation, and fungicides containing them - Google Patents

Abstract

Phosphoniummethylquinolines of the general formula I <IMAGE> in which R<1>, R<2> and R<3> denote alkyl, cyclohexyl and phenyl, R<4> and R<5> denote hydrogen, alkyl, alkoxy and halogen, and X denotes halogen, and fungicides containing them.

Description

'Quaternary Phosphonium Methylquinolines, Process for Their

Manufacture and Fungicides Containing Them The present invention relates to new quaternary phosphonium methylquinolines, process for their preparation and fungicides containing these phosphonium methylquinolines.

It is known to use N-trichloromethylthiophthalimide (Chemical Week 1972, June 21, page 63) or N-trichloromethylthio - tetrahydrophthalimide (Chemical Week 1972, June 21, page 46) to control fungi. Your effect is but not satisfactory.

It has been found that phosphonium methylquinolines of the formula I in which R1, R2 and R3 are identical or different and an alkyl radical with 1 to 12 carbon atoms, cyclohexyl, phenyl, and R5 are identical or different and are hydrogen, an alkyl radical with 1 to 6 carbon atoms, an alkoxy radical with 1 to 4 carbon atoms, halogen such as fluorine, chlorine, bromine or iodine and X stands for halogen such as chlorine, bromine or iodine, effectively fight fungi.

Alkyl radicals with 1 to 12 carbon atoms are e.g.

Alkyl radicals with 4 to 8 carbon atoms, for example n-butyl, isobuyl, tertiary butyl, pentyl, hexyl, heptyl, octyl or methyl, ethyl, propyl, Decyl, dodecyl.

Alkyl radicals with 1 to 6 carbon atoms are e.g. methyl, ethyl, n-propyl, iso-propyl, butyl, pentyl, hexyl.

Alkoxy radicals with 1 to 4 carbon atoms are e.g. methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy.

Halogen is e.g. fluorine, chlorine, bromine.

The new compounds are prepared, for example, by reacting 8-halomethylquinolines of the formula II with phosphines of the formula III according to the following reaction equation: The radicals R1, R2, R3, R4, R5 and X have the meanings given above.

The reaction is expedient in relation to the reactants inert solvents or diluents carried out, for example suitable: alcohols such as methanol, ethanol, propanol; Ethers such as tetrahydrofuran, dioxane, Diglycol dimethyl ether; Ketones such as acetone, methyl ethyl ketone, diethyl ketone; aromatic Hydrocarbons such as toluene, xylenes, chlorobenzenes; Nitriles such as acetonitrile; Dimethylformamide, Dimethyl sulfoxide. Even Mixtures of this solution and diluent can be used.

To carry out the process, the starting materials are equimolar Circumstances. An excess of one or the other reaction component can in some cases bring benefits.

The reaction temperature can vary within a relatively wide range will. In general, one works at temperatures in the range from 0 to 1500C, preferably in the range from 20 to 120 ° C.

The compounds of the formula II are prepared by adding a compound of the formula IV in which R4 and R5 have the meanings given above, chlorinated with a radical initiator in the absence of light at 140 ° to 1900 ° C., thus obtaining compounds of the formula II wherein R is chloromethyl.

The 8-methylquinolines used in this process are known Links. The preparation is described, for example, by Bradford in J. Chem. Soc. 1947, p. 437, or by Irving in J. Amer. Chem. Soc. 72, (1950), pp. 4059.

The chlorination is carried out in an inert solvent such as dichlorobenzenes or trichlorobenzenes, in the presence of a free radical initiator such as azoisobutyronitrile or benzoyl peroxide, with the exclusion of light, in a temperature range of 140 to 1900C, preferably carried out at 150 to 1600C.

Regulation 1 89 parts of 7-chloro-8-methylquinoline and 0.5 part of azo-bisisobutyronitrile are placed in 500 parts of dichlorobenzene and heated to 140 ° C. At this temperature the introduction of 80 parts of chlorine is started. During the initiation of Chlorine increases the temperature to 1600C. After the addition of chlorine is complete the solution is flushed with nitrogen, most of the solvent is distilled off, the precipitated solid is filtered off with suction and washed with petroleum ether. It will be 113 Parts of 3,7-dichloro-8-chloromethylquinoline of melting point 129 ° C. were obtained. The yield corresponds to 93% d. Theory.

The following example illustrates the preparation of the quaternary phosphonium methylquinolines.

Example 3,7-dichloro-8-triphenylphosphonium methylquinoline chloride 24.6 3.7 g of dichloro-8-chloromethylquinoline and 26.1 g of triphenylphosphine were in 120 ml Acetonitrile stirred for 4 hours at reflux temperature (820C). After cooling down 2000 the precipitated solid was filtered off with suction, suspended in ethyl acetate and again sucked off. Yield: 40 g (78% of theory). M.p. 2630C (Compound No. 1) C28H21C13NP (508.5) Calc .: C 66.1 H 4.1 C1 20.9 N 2.8 P 6.1 Found: C 65.6 H 4.3 C1 20.3 N 3.0 P 6.6 The compounds given in the following table were correspondingly of formula I, the melting points (mp.) of which are given. Your structure was secured by elemental analysis. The connections where no information Are made to physical chemistry can in the same way as are obtained in the compounds actually made; it can be expected that, because of their similar constitution, they have effects similar to the have investigated connections.

Compound R1 R2 R3 R4 R5 X m.p. ° C 2 C6H5 C6H5 C4H9 3-C1 7-C1 Cl 226 3 C6H5 C6H5 C6H13 3-Cl 7-C1 Cl 170 4 C6H5 C6H5 C8H17 3-C1 7-C1 Cl 140 5 C6H5 C6H5 C6H5 H 7-Cl Br 254 6 C4H9 C4H9 C4H9 3-C1 7-C1 C1 177 7 C6H5 C6H5 C6H5 3-CH3 7-Cl Cl 8 C6H5 C6H5 C6H5 3-C1 5-C1 C1 9 C6H5 C6H5 C6H5 3-C1 6-Cl Cl 10 C6H5 C6H5 C6fl5 3-C1 7-C1 Cl li C6H5 C6H5 C6H5 3-C1 7-F Cl 12 C6H5 C6H5 C6H5 3-F 5-Cl Cl 1: 3 C6H5 C6H5 C6H5 3-F 6-C1 Cl 14 C6H5 C6H5 C6H5 3-F 7-Cl Cl 15 C6H5 C6H5 C6H5 3-F 7-F Cl the new compounds are characterized by an excellent effectiveness against a broad spectrum of phytopathogenic fungi. They can be used as foliar and soil fungicides can be used.

The new compounds are particularly suitable for combating the following Plant diseases: Phytophthora infestans on tomatoes and potatoes, Phytophthora parasitica on strawberries, Phytophthora cactorum on apples, Pseudoperonospora cubensis on cucumbers, Pseudoperonospora humuli on hops, downy mildew on onions, Peronospora sparsa on roses, Peronospora tabacina on tobacco, Plasmopara viticola on vines, Plasmopara halstedii on sunflowers, Pythium ultimum on pea seedlings, Botrytis cinerea on vines, strawberries and peppers, Septoria nodorum on grain, Venturia inaequalis (scab) on apple trees.

The compounds are applied by making the plants with the Active ingredients sprayed or dusted or the seeds of the plants with the active ingredients treated. The application takes place before or after the infection of the plants or seeds through the mushrooms.

The new substances can be converted into the usual formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granulates, The forms of application depend entirely on the intended use; they should in any case ensure a fine and even distribution of the active substance. The formulations are 9 'made in a known manner, e.g. by extending the active ingredient with solvents and / or carriers, if necessary using emulsifiers and dispersants, with in the case of use from water as a diluent to other organic solvents as auxiliary solvents can be used. The following are the main auxiliaries: Solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), Paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), amines (e.g.

Ethanolamine), dimethylformamide and water; Carriers like natural ones Ground rock (e.g. kaolins, clays, talc, chalk) and synthetic ground rock (e.g.

highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin, sulfite waste liquors and methyl cellulose.

The fungicidal agents generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.

The application rates are between, depending on the type of effect desired 0.1 and 3 kg of active ingredient or more per hectare.

The new compounds can also be used in material protection. When the active ingredients are used in material protection, the application rates are 0.05 Up to 5% (% by weight) of active ingredient, based on the total weight of the product to be preserved Materials. The new active ingredients can also be used as fungicidally active ingredients Wood preservatives can be used to protect wood against wood-discolouring fungi. The application is carried out in such a way that the wood is treated with these agents, for example soaks or paints.

The means or the ready-to-use preparations made from them such as solutions, emulsions, suspensions, powders, dusts, pastes or granulates applied in a known manner, for example by spraying, misting, dusting, Scattering, pickling or watering.

Examples of such preparations are: I. 90 parts by weight are mixed of the active ingredient 1 with 10 parts by weight of N-methyl-alpha-pyrrolidone and receives a Solution that is suitable for use in the form of tiny drops.

II. 10 parts by weight of the active ingredient 2 are dissolved in a mixture, that from 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 up to 10 moles of N-monoethanolamide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil consists.

III. 20 parts by weight of the active ingredient 3 are dissolved in a mixture, that of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By Pouring the solution into water and finely distributing it therein gives an aqueous dispersion.

IV. 20 parts by weight of the active ingredient 6 are dissolved in a mixture, that of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from boiling point 210 to 28OOC and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring and fine distribution len the solution in water gives an aqueous dispersion.

V. 80 parts by weight of the active ingredient 4 with 3 parts by weight of the Sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the Sodium salt of a lignosulphonic acid from a sulphite waste liquor and 7 parts by weight powdered silica gel mixed well and ground in a hammer mill. A spray liquor is obtained by finely distributing the mixture in water.

VI. 3 parts by weight of active ingredient 5 are 97 parts by weight finely divided kaolin intimately mixed. In this way a dust is obtained Contains 3% by weight of the active ingredient.

VII. 30 parts by weight of the active ingredient 4 with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, which was sprayed onto the surface of this silica gel, intimately mixed. Man In this way, the active ingredient is prepared with good adhesion.

VIII. 40 parts by weight of the active ingredient 3 are mixed with 10 parts of the sodium salt a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water mixed intimately. A stable aqueous dispersion is obtained. By Dilution with water gives an aqueous dispersion.

IX. 23 parts of active ingredient 2 are mixed with 2 parts of the calcium salt Dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde-condensate r sates and 68 parts of a paraffinic mineral oil mixed intimately. You get a stable one oily dispersion.

In these application forms, the fungicides can also be used together with other active substances are present, e.g.

Herbicides, insecticides, growth regulators and fungicides, or can also be mixed with fertilizers and applied. When mixed with fungicides In many cases, the spectrum of fungicidal activity is enlarged.

The following list of fungicides with which the invention Connections can be combined, should explain the possible combinations, but do not limit.

Fungicides that can be combined with the new compounds, are for example: sulfur, dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate, Zinc dimethyldithiocarbamate, manganese-zinc-ethylenediamine-bis-dithiocarbamate and zinc-ethylene bisdithiocarbamate, Tetramethylthiuram disulfide, ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate) and N, N'-polypropylene bis (thiocarbamoyl) disulfide; Zinc (N, N'-propylene-bis-dithiocarbamate), Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate) and N, N'-polypropylene-bis- (thiocarbamoyl) -disulfide; 'Nitro derivatives, such as dinitro (l-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate; heterocyclic substances such as N- (1,1,2,2-tetrachlorethylthio) -tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, 2-heptadecyl-2-imidazoline acetate 2, 4-dichloro-6- (o-chloroanilino) -s-triazine O, O-diethyl phthalimidophosphonothioate 5-Amino-1- (bis- (dimethylamino) -phosphinyl) -3-phenyl-1,2,4-triazole) 2,3-dicyano-1,4-dithioaanthraquinone 2-thio-1,3-dithio- (4,5-b) -quinoxaline 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone pyridine-2-thio-1-oxide 8-hydroxyquinoline or its copper salt 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathtin 2- (furyl- (2)) -benzimidazole piperazine-1,4-diylbis- (1- (2,2,2-trichloro- ethyl) formamide 2- (Thiazolyl- (4) -benzimidazole 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine Bis- (p-chlorophenyl) -3-pyridinemethanol 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene 1,2-bis- (3-methoxyearbonyl-2-thioureido) -benzene and various fungicides, such as dodecylguanidine acetate 3- (3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl) -glutarimide Hexachlorobenzene N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenyl-sulfuric acid diamide 2,5-dimethyl-furan-3-carboxylic acid anilide 2-methyl-benzoic acid anilide 2-iodo-benzoic acid anilide 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane 2,6-dimethyl-N-tridecyl-morpholine or its salts 2,6-dimethyl-N-cyclododecyl-morpholine or its salts DL-methyl-N- (2,6-dimethyl-phenyl) -N-furoyl (2) -alaninate DL-N- (2,6-dimethyl-phenyl) -N- (2'-methoxyacetyl) -alanine - methyl ester 5-nitro-isophthalic acid di-isopropyl ester 1- (1 ', 2', 4'-triazolyl-1 ') - [1- (4'-chlorophenoxy)] - 3,3-dimethylbutan-2-one 1- (1 ', 2', 4'-triazolyl-1 ') - [1- (4'-chlorophenoxy) 2-3,3-dimethylbutan-2-ol N- (2,6-dimethylphenyl) -N- chloroacetyl-D, L-2-aminobutyrolactone N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazolylurea N-cyclohexyl-N-methoxy-2, 5-dimethyl-furan-3-carboxamide 2,4, 5-trimethyl-furan-3-carboxylic acid anilide 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3- -oxazolidine 5-methoxymethyl-5-methyl-3- (3,5-dichloropbenyl) -2,4-dioxo - 1,3-oxazolidine N-E3- (p-tert-butylphenyl) -2-methyl-propyl] - cis-2,6-dimethylmorpholine N-formyl-N-morpholine-2,2,2-trichloroethylacetal 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-rethyl] -lH-1, 2,4-triazole 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-methylj-1H-1,2,4-tiazole.

9 The following known active ingredients are used for the following experiments used as comparative active ingredients: N-trichloromethylthiophthalimide A N-trichloromethylthiotetrahydrophthalimide B.

Experiment 1 Efficacy against Plasmopara viticola leaves from potted vines of the Mller-Thurgau variety are mixed with an aqueous spray liquor containing 80% (% by weight) of active ingredient and contains 20% emulsifier in the dry substance, sprayed. About the duration of the effect To be able to assess the active ingredients, the plants are after the Spray coating placed in the greenhouse for 10 days. Only then will the leaves begin with infected by a zoospore suspension of Plasmopara viticola (vine peronospora). Then the vines are first saturated with water for 16 hours Chamber at 240C and then for 8 days in a greenhouse with temperatures between 20 and 300C. After this time the plants will speed up of the sporangia carrier outbreak again placed in the humid chamber for 16 hours. The extent of the fungal outbreak on the underside of the leaves is then assessed.

The result of the experiment showed that, for example, the connection 1 a better fungicidal effectiveness when used as a 0.025% spray liquor (for example 97% effect) showed as the active ingredient A (for example 90% effect).

Experiment 2 Efficacy against Botrytis cinerea on paprika Paprika seedlings of the variety "Neusiedler Ideal Elite, after 4 to 5 leaves have developed well have, with aqueous suspensions, the 80% active ingredient and 20% emulsifier in the dry substance contained, sprayed dripping wet. After the spray coating has dried on the plants become suspended in conidia of the fungus Botrytis cinerea sprayed and placed at 22 to 24 ° C in a chamber with high humidity. After 5 days the disease became so severe on the untreated control plants developed that the resulting leaf necrosis most of the leaves cover.

The result of the experiment showed that, for example, the compounds 3 and 4 have a better fungicidal effect when used as a 0.05% spray liquor (for example 90% effect) showed as the active ingredient B (for example 70% effect).

Claims (5)

Claims {½i. Phosphonium methylquinolines of the general formula I in which R1, R2 and R3 are identical or different and an alkyl radical with 1 to 12 carbon atoms, cyclohexyl, phenyl, R4 and R5 are identical or different and hydrogen, an alkyl radical with 1 to 6 carbon atoms, an alkoxy radical with 1 to 4 carbon atoms or Are halogen and X is halogen. 2. Process for the preparation of the phosphonium salts of the formula I, characterized in that 8-halomethylquinolines of the formula II in which R4, R5 and X have the meanings given in claim 1 with phosphines of the formula III P (R1R2R3) III, in which R1, R2 and R3 have the meanings given in claim 1, is reacted. 3. Use of phosphonium salts of the formula I for combating Mushrooms. 4. Compounds according to claim 1, in which R1 and R2 are phenyl or butyl, R3 phenyl, octyl or butyl, R4 and R5 hydrogen or chlorine and X chlorine or bromine mean. 5. Fungicide containing a compound according to claim 1.