DE2341777A1 - 2,5,6-Trichloro-3-chloromethylpyridine - with fungicidal activity esp for use on soils and seed dressings - Google Patents

Abstract

(I) has fungicidal activity and is pref. prepd. by (a) reacting 3-chloro-3-chloromethylglutarimide (II) with PCl5 at =75 degrees C and reacting the product with POCl3 at 160-200 degrees C, or (b) reacting (III) with a mixt. of PCl5 and POCl3 at 160-200 degrees C.

Description

2,5,6-trichloro-3-chloromethylpyridine, Yeeahren for its preparation and its use The present invention relates to 2,5,6-trichloro-3-chloromethylpyridine as a new compound, a new process for its preparation, the use of 2, 5,6-trichloro-3-chloromethylpyridine ir; Plant protection, for example as an active ingredient for combating phytopathogenic fungi, and the agents containing the new active ingredient. It has been found that a new trichlorochloromethylpyridine compound, namely 2,5,6-trichloro-3-chloromethylpyridine, is found can be prepared in a simple and economical manner with very good yields and using readily available starting materials by adding 3-chloro-3-chloromethylglutarimide at a temperature of not more than 75 ° C with phosphorus pentachloride to 3,5,6-trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one and this is then treated at a temperature between 160 and 2000 C with phosphorus oxychloride.

The 3-chloro-3-chloromethylglutarimide is preferably reacted (il) with the phosphorus pentachloride at a temperature between 60 and 700C, in particular at 700C. The phosphorus pentachloride is expediently in about 3 to 10-fold excess is used over the stoichiometrically required amount.

The subsequent conversion of the 3,5,6-trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one formed (III) with phosphorus oxychloride is preferred at a temperature between 175 and 185 ° C, especially at approx.

180 ° C, carried out in an autoclave. The phosphorus oxychloride is also used appropriately used in excess, e.g.

an approximately 5- to 10-fold excess over the stoichiometrically required Lot.

Although not essential, it is recommended that it be used as an intermediate formed 3,5,6-trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one (III) before the to isolate subsequent reaction with phosphorus oxychloride.

The 2,5,6-trichloro-3-chloromethylpyridine (I) can also be obtained thereby be that you can 3-chloro-3-chloromethylglutarimide (II) at a temperature between 16C and 200 ° C with a mixture of phosphorus pentachloride and phosphorus oxychloride implements. The phosphorus pentachloride and the phosphorus oxychloride are expedient used in a mutual molar ratio of about 1: 5 to 1: 1.2. The implementation with such a mixture is preferred at a temperature between 175 and 185 ° C, in particular about 1800C, made in the autoclave.

In this reaction, depending on the selected molar ratio from phosphorus pentachloride to phosphorus oxychloride in addition to 2,5,6-trichloro-3-chloromethylpyridine (I) larger or smaller proportions of 2,6-dichloro-5-chloromethylpyridine are also formed.

The isolation and purification of), 5,6-trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one (III) or of 2,5,6-trichloro) - chloromethylpyridine (I) can in the usual way take place, for example by removing the excess phosphorus pentachloride or phosphorus oxychloride by distillation, crystallization of the reaction products from water or an ice / water mixture and, if necessary, further purification subsequent distillation or recrystallization of the crude products.

The method of the present invention used 3-chloro-3-chloromethylglutarimide (II) is in the German patent specification. ... ... (patent application P 22 52 063.4) described. It can, for example, by chlorination of α-methyleneglutaronitrile and cyclization of the resulting 1,2-dichloro-2,4-dicyanbutane can be obtained in an acidic medium.

The intermediate product obtained in the process according to the invention 3,5,6-Trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one is new.

Both 3,5,6-trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one (III) and 2,5,6-trichloro-3-chloromethyl-pyridine (I) fall in the form of easily brownish to white crystals, which in common organic solvents, such as benzene, methanol, ethanol, acetone, dimethylformamide and chlorinated hydrocarbons, e.g. chloroform and methylene chloride are readily to very soluble.

The following examples illustrate the preparation of the inventive 2,5,6-trichloro-3-chloromethyl-pyridines. The temperatures are given in degrees Celsius.

Example] 1 a) Preparation of 3,5,6-trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one 296 g (1.51 mol) of 3-chloro-3-chloromethylglutarimide and 800 g (3.83 mol) of phosphorus pentachloride are mixed well with one another. The mixture is then placed in a 2.5 liter flask equipped with a metal stirrer, thermometer and gas discharge tube. The filled flask is immersed in an oil bath preheated to 800, and the stirrer axtrd is put into operation. After 30 minutes the internal temperature reaches 600; after a further 15 minutes the internal temperature has reached 70-71 ° and the reaction mixture begins to liquefy. This temperature is maintained for a further 8 minutes. The oil bath is then removed and the reaction mixture is stirred for a further 10 minutes, the temperature falling to 550. A dark brown colored mixture is formed, which is slowly poured onto 2.5 to 3.0 kg of ice with thorough stirring. The temperature of the reaction mixture should not exceed 10-20.

The reaction product falls in the form of slightly brown colored Crystals on, which is suctioned off from the resulting aqueous solution, washed neutral with water and dried in a vacuum drying cabinet at 400 over diphosphorus pentoxide. Man receives 288.9 g (76.9% of theory) of crude 3,5,6-trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one of m.p. 138-143 °. Recrystallization of the crude product from chloroform / petroleum ether (1: 1) gives crystals with a melting point of 143-145 °.

IR spectrum (Nujol): 1700 cml (C = O); NMR spectrum (CDCl3): # = 4.22 and 3.80 ppm, J = 11.0 (-CH2Cl), 2.85 and 3.56 ppm, J = 18.0 (HA, HB); UV spectrum (CH3OH): # max = 266.5; # = 3700.

Analysis for C6H5Cl4NO (mol. Wt. 248.86): calculated C 28.95% H 2.02% Cl 56.97% N 5.63% found C 28.92% H 2.10 C1 56.76 $ N 5.71%.

The 3-chloro-3-chloromethyl-glutarimide used as a starting point (M.p. 134-135 °) is according to methods known per se by chlorination of α-methyleneglutaronitrile, e.g. with C12 in pyridine, with formation of 1,2-dichloro-2,4-dicyanobutane (m.p. 130-133 ° / 1.5 Torr; nD20 = 1.4883) and subsequent cyclization of the latter, e.g. in acetic acid / sulfuric acid, obtain.

b) Preparation of 2,5,6-trichloro-3-chloromethylpyridine 82.8 g (0.3D3 mol) of the 3,5,6-trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one prepared according to section a) of this example and 400 ml (4.4 mol) Phosphorus oxychloride are heated to 1800 in an autoclave for 3 hours. Excess phosphorus oxychloride is then removed from the reaction solution on a rotary evaporator, and the dark brown residue is poured onto ice. The deposited crystals are filtered off with suction, washed with water and dried over diphosphorus pentoxide overnight. Distillation at 87-89 ° / 0.1 Torr gives 71 g (92.3% of theory) of 2,5,6-trichloro-3-chloromethylpyridine in the form of white crystals; M.p. 27-290.

IR spectrum (Nujol): 6.31 µ, 6.40 µ.

LMWH spectrum (CDCl3): # = 8.00 ppm (s, 4H) 4.70 ppm (s, -CH2Cl).

Analysis for C6H3Cl4N (mol. Wt. 230.91): calculated C 31.21% H 1.31% Cl 61.42% N 6.07% found C 31.18 H 1.29 C1 61.30% N 6.00%.

Example 2 19.6 g (0.1 mol) of 3-chloro-3-chloromethylglutarimide are suspended in 75 g (p, 49 mol) of phosphorus oxychloride and 25 g (0.12 mol) of phosphorus pentachloride. The suspension obtained is then heated to 1800 in an autoclave for 2 hours. A dark colored reaction solution is formed. The excess phosphorus compounds are distilled off in vacuo, the oily residue is mixed with ice and water and stirred for 30 minutes. The organic phase is then taken up in diethyl ether, washed with sodium bicarbonate and finally dried with sodium sulfate. After evaporation of the diethyl ether, 19 g of a dark-colored oil remain, which after distillation at 1G9-120 ° / 3 Torr yields 15 g (65% of theory) of a semicrystalline reaction product. The examination of miotel's gas chromatography and IR spectra showed that the reaction product consists of a mixture of 2,6-dichloro-3-chloromethylpyridine and 2,5,6-trichloro-3-chloromethylpyridine in a ratio of 2: 3.

The 2,5,6-trichloro-3-chloromethylpyridine according to the invention can be used for plant protection are used; the new Compound (1) possesses E.g. good fungicidal eyesight, especially as a soil fungicide and seed dressing. against phytopathogenic fungi on various crops, such as cereals, rtais, Rice, vegetables, ornamental plants, fruits, vines, field crops, etc.

With the new active ingredient, tubers and tubers in particular can be used on seeds Roots, but also fungal infections that occur on fruits, flowers, foliage and stems can be contained or destroyed, with later overgrown parts of the plant be spared from such infections.

The active ingredient is applied in solid or liquid form Means both on seeds or above-ground parts of plants as well as in the soil or on the floor.

Suitable for application to seeds or above-ground parts of plants especially solutions or aqueous dispersions. For the treatment of the growth substrate In addition to solutions and dispersions, there are also dusts, granulates and Suitable for grit.

The new active ingredient is particularly against the following classes, Phytopathogenic fungi belonging to orders or species are effective: Smut fungi of all kinds, such as Ustilaginales, e.g. Ustilage species (Ustilage avenae), Tilletia species (tilletia tritici, tilletia caries), Urocystis and Tuburcinia species, Phoma species (Phoma betae).

Oomycetes, such as Plasmodiophora species, Aphanomyces species, Pythium species, e.g. Pythium debaryanum, Phytophthora species (Phytophthora infestans, Phytophthora cactorum), Plasmopara species (Plasmopara viticola). Bremia species (Bremia lactucae), Peronospora species (Peronospora tabacina), Pseudoperonospora species (Pseudoperonospora humuli).

Zygomycetes, such as Rhizopus species.

Ascomycetes such as Eurotiales, e.g. Aspergillus species, Penicillium species (Penicillium digitatum, Penieillium italicum), Taphrinales, e.g. Taphrina species (Taphrina deformans), Erysiphales, e.g. Erysiphes species (Erysiphes cichoracearum, Erysiphes graminis), Podosphaera leucotricha, Sphaerotheca species (Sphaerotheca pannosa), Uncinula species (Uncinula necator), Helotiales. like Monilinia species (Monilinia [Sclerotinia] fructicola, Monilinia laxa), Diplocarpon species (Diplocarpon rosae), Pscudopeziza species, Sphaeriales, like Neetria species (Nectria galligcna), Ceratocystis species, Pseudesnhaeriales, such as Venturia species (Venturia inaequalis), Mycosphaerella species, Ophiobolus species (Ophiobolus grami -nus), Cochliobolus species (Helminthosporium miyabeanus), Cercospora species (Cercospora beticola, Cercospora musae).

Basidiomycetes such as Aphyllophorales, e.g. Pellicularia species (Pellicularia filainentora = [Phizoctonia solani]), Uredinales, e.g.

Puccinia species (Puccinia triticina), Uromyces species (Uromyces phaseoli ?, Hemileia species (Hemileia vastatrix), Cronartium species (Cronartium ribicola), Phragmidium species (Phragmidium subcorticium), Gymnosspcrangium species.

Deuteromycetes = (Fungi imperfecti) e.g. Piricularia species (Piricularia oryzae), Corynespora species, Thielaviopsis species, Clasterosporium species, Botrytis species (Botrytis cinerea), Cladosporium species, Alternaria species (Alternaria solani), Verticillium species (Verticillium albo-atrum), Phialophora species, Melanconiales, e.g. Colletotrichum species, Fusarium species (Fusarium oxysporum, Fusarium nivale), Gloeosporium species (Gloeosporium fructigenum), Sphaeropsidales, e.g. Septoria species (Septoria apicola), Diplodia species (Diplodia natalensis), Mycelia sterilia, e.g. Sclerotium species (Sclerotium rolfsii).

The new 2,5,6-trichloro-3-chloromothylpyridine (I) can also be used with others Compounds, e.g. other fungicides, insecticides, herbicides, bactericides, fungistatic agents, Bacteriosticides or nematicides formulated in various mixing ratios be, with mixtures of compounds having advantages over the individual components develop. The agents according to the invention can also contain plant fertilizers, trace elements, etc., included.

For formulation with the 2,5,6-trichloro-3-chloromethylpyridine according to of the present invention are e.g.

Dodecylguanidine acetate (Dodine), pentachloronitrobenzene (Quintozene), Pentachlorophenol (PCP), 2- (1-methyl-n-propyl) -4,6-dinitrophenyl-2-methylerotonate (Binapacryl), 2- (1-methyl-n-hypthl) -4,6-dinitrophenyl crotonate (Dinocap), 2,6-dichloro-4-nitroaniline (Dichlorane), 2,3,5, 6-tetrachloro-benzoquinone (1,4) (chloranil), 2,3-dichloro-naphthoquinone (1,4) (Dichlone), N- (Trichloromethylthio) phthalimide (Folpet).

N- (Trichloromethylthio) cyclohex-4-ene-1,2-dicarboximide (Captan) J. N- (1,1,2,2-tetrachloroethylthio) cyclohex-4-ene-1,2-dicarboximide (Captafol), N-methylsulfonyl-N-trichloromethylthio-p-chloroaniline, N'-dichlorofluoromethylthio-N, N-dimethyl-N'-phenylsulfamide (Dichlorofluamid), O-ethyl-S-benzyl-phenyldithiophosphonate, O, O-diethyl-S-benzyl-thiol phosphate, Disodium ethylene-1,2-bis-dithiocarbamate (Nabam), zinc-ethylene-1,2-bis-dithiocarbamate (Zineb), manganese (II) ethylene-1,2-bis-dithiocarbamate (Maneb), tetramethylthiuram disulfide (Thiram), 1-Hydroxy-3-acetyl-6-methyl-cyclohex-5-en-2,4-dione (dehydroacetic acid), 8-hydroxyquinoline (8-quinolinol), 2-dimethylamino-6-methyl-5-n-butyl-4-hydroxypyrimidine, Methyl-N-benzimidazol-2-yl-N- (butylcarbamoyl) carbamate (benomyl), 2-ethylamino-6-methyl-5-n-butyl-4-hydroxypyrimidine, 2,3-dicyano-1,4-dithia-anthraquinone (dithianon), 2- (4-thiazolyl) -benzimidazole, 3,5-dimethyltetrahydro-1,3,5-thiadiazine-2-thione (Dazomet), 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathine, pentachlorobenzyl alcohol.

The production of fungicidal agents according to the invention he follows in a manner known per se by intimately mixing and grinding the 2,5,6-trichloro-3-chloromethylpyridine - (i) with approved carriers, optionally with the addition of compared to the Active ingredient, inert dispersants or solvents. The active ingredient can be used to manufacture of dusts, grit, granules, coating granules, impregnation granules, Wettable powders, pastes, emulsions, solutions or aerosols are used will.

For the production of solid processing forms (dust, grit, Granules) the active ingredient is mixed with the remaining carrier substances. The grain size the carrier material for dust is expediently up to approx. 0.1 mm, for grit approx. 0.075 to 0.2 mm and for granulates 0.2 mm or more. The active ingredient concentrations in the solid preparation forms are usually 0.5 to 8Q10.

These mixtures can also contain additives stabilizing the active ingredient and / or nonionic, anionic and cationic substances are added which for example the adhesive strength of the active ingredient on plants and parts of plants improve (adhesive and adhesive) and / or better wettability (wetting agent) and ensure dispersibility (dispersants).

Active ingredient concentrates dispersible in water, wettable powders (wettable powders), pastes and emulsion concentrates are agents that can be mixed with water any desired concentration can be diluted. They consist of active ingredient, Carrier, surface-active substances and anti-foaming agents and optionally Solvents. The concentration of active ingredients in these agents is 5-80%. the Wettable powders and pastes are obtained by adding the active ingredient with dispersants and powdery carriers in suitable devices mixed and ground until homogeneous. In some cases it is beneficial to Use mixtures of different carriers. Come as an anti-foam agent zu'Bebeispiel silicones, etc. in question. The active ingredient comes with those listed above Additives mixed, ground, sifted and happened that with the wettable powders the solid part has a grain size of 0.02 to 0.04 mm and that of the pastes of 0.03 mm. For the production of emulsion concentrates and pastes dispersants, organic solvents and water are used. The solvents must be practically odorless, non-phytotoxic, inert to the active ingredient and must not be easily flammable.

The agents according to the invention can also be used in the form of solutions will. For this purpose, the active ingredient is dissolved in suitable organic solvents or I.ssuncsmitbelgemischen dissolved. The solutions are intended to give the active ingredient a concentration range from 1 - 20 included.

The following are working-up forms of the active ingredient for crop protection Unless otherwise noted, parts mean parts by weight.

Dusts To produce a 2% dust, the the following substances are used: 2 parts of 2,5,6-trichloro-3-chloromethylpyridine, 5 parts colloidal silica and 93 parts of talc.

The active ingredient is intimately mixed and ground with the carrier substances. The fungicidal dust obtained in this way is used to treat seedbeds.

Granulate To produce a 4iQen granulate, the following Substances used: 4 parts of a 1: 1 mixture of 2,5,6-trichloro-3-chloromethylpyridine with silica, 92 Telle granulated limestone (lime grit), 5 Parts of a mixture of 0.5 parts of C8-C9-alkylphenoxypolyoxyethylene glycol and 2.5 parts of polyethylene glycol and 1 part of kieselguhr.

The lime grits are impregnated with the polyethylene glycol mixture and then mixed with the solution of active ingredient and silica. Afterward Diatomaceous earth is added as an anticaking agent. This granulate is particularly suitable for the treatment of potting soil.

Dry pickling agent It is a dry pickling agent with the following composition used: 20 wt. - 2,5,6-trichloro-5-chloromethylpyridine, 1 wt .-% paraffin oil and 79 wt. Talc.

600 g of this agent, which has good adhesiveness to seed grains with 100 kg of barley seeds in a tightly closing rotatable Drum introduced. The filled drum is rotated for 45 minutes; after this Time is practically the entire amount of Mitüels used as a coating on the seed grains.

Wet pickling agent It is a wet pickling agent with the following composition used: 23.00% by weight of 2,5,6-trichloro-3-chloromethylpyridine, 1.65% by weight of alkaryl polyglycol ether (Emulsifier), 1.65% by weight NaHSO4.H2O, finely ground and 73.70% by weight diethylene glycol monoethyl ether acetate.

A bath is made up which consists of 250 g of the above agent and 15 Liters of water at room temperature; this bath is then prepared thoroughly mixed. This aqueous preparation produces 100 kg of rye seeds showered over. The seeds are then allowed to drain on a sieve and then well dried.

Spray powder For the production of a) 10% and b) 50% spray powder the following ingredients are used: a) 10 parts of 2,5,6-trichloro-3-chloromethylpyridine, 1 part dibutylnaphthalenesulfonic acid sodium salt, 4 parts ligninsulfonic acid calcium salt, 2 parts mixture of champagne chalk and hydroxyethyl cellulose (1: 1), 50 parts Kaolin, 10 parts sodium aluminum silicate and 23 parts champagne chalk.

b) 50 parts of 2,5,6-trichloro-3-chloromethylpyridine, 2 parts of octylphenoxyethylene glycol with 9-10 vol ethyleneoxy groups per mole of phenol, 2 parts mixture of Champagne chalk and hydroxyethyl cellulose (1: 1), 5 parts of heptadecyl-hydroxyethyl-imidazoline and 45 parts of kaolin.

The fungicidal effectiveness of the new active ingredient was determined from the following Experiments found: A. Soil test -In dry sterilized soil will be 500 ppm Active ingredient (2,5,6-trichloro-3-chloromethylpyridine) incorporated by intensive mixing. 100 cc of this soil are poured into a plastic container with a capacity of 250 ccm. Approx. 10 sterilized oat kernels are placed below the surface of the earth in this container introduced that with mycelium of the species Verticillium albo-atrum or Phytium debaryanum are streaky.

Then is iessend with 34 ml of dist. Moistened water, and the container is incubated at 20-24 °.

After 5 days an assessment is carried out, whereby it is determined whether from the grains Pllzriycelia grow into the surrounding soil. The tested 2,5,6-trichloro-3-chloromethylpyridine showed a good effect.

B. Pickling test wheat is used with the. Fungus Tilletia caries artificially infected. The wheat is then with 500 ppm active ingredient (2,5,6-trichloro-3-chloromethylpyridine) Pickled and laid out on moist filter paper in Petri dishes.

After 10 days of incubation at 20-24, fungal mycelium will develop rated. The 2,5,6-trichloro-3-chloromethylpyridine showed a good effect.

Claims (8)

P a t e n t a n s p r ü c h e 1. 2,5,6-trichloro-3-chloromethylpyridine 2. Process for the preparation of 2,5,6-trichloro-3-chloromethylpyridine characterized in that 3-chloro-3-chloromethylglutarimide at a temperature of not more than 750C with phosphorus tachloride to 3,5,6-trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one and this is then treated at a temperature between 160 ° C and 200 ° C with phosphorus oxychloride. 3. The method according to claim 2, d a d u r c h g e k e n n -drawn, that the implementation of 3-chloro-3-chloromethylglutarimide with phosphorus pentachloride at a temperature between 60 ° C and 700C. 4. The method according to claims 2 and 3, characterized in that to implement the 3,5,6-trichloro-3-chloromethyl-5,6-dehydropiperidin-2-one with Phosphorus oxychloride at a temperature between 1750C and 185CC. 5. The method according to claim 1, characterized in that one 3-chloro-3-chloromethylglutarimide at a temperature between 160 ° C and 2000C with a mixture of phosphorus pentachloride and phosphorus oxychloride. 6. The method according to claim 5, d a d u r c h g e k e n n -drawn, that the implementation of the 3-chloro-3-chloromethylglutarimide with a mixture full Phosphorus pentachloride and phosphorus oxychloride at a temperature between 175 ° C and 185 ° C. 7. Agents for combating phytopathogenic fungi, characterized in that that it contains as active ingredient 2,5,6-trichloro-3-chloromethylpyridine according to claim 1. 8. Use of 2,5,6-trichloro-3-chloromethylpyridine according to claim 1 or of agents according to claim 7 as a soil fungicide or seed dressing.