IL44737A

IL44737A - 5-substituted-3-(3,5-dichlorophenyl)-2,4-oxazolidinedione derivatives and fungicidal compositions containing them

Info

Publication number: IL44737A
Application number: IL44737A
Authority: IL
Original assignee: Basf Ag
Priority date: 1973-05-16
Filing date: 1974-04-30
Publication date: 1977-02-28
Also published as: DE2324591C2; HU168167B; YU133774A; FR2229698A1; JPS5756445B2; CH562561A5; AT334137B; ATA401974A; BG23204A3; IT1049283B; IL44737A0; DE2324591A1; JPS5013531A; ES426303A1; FR2229698B1; AU6843174A

Description

44737/3 - 7 jKXT3»"i»,?iTKO itt-4,2~(,>»3Dini,?-j« '-5,3)-3 nit in o» aan ni»nDs 'beip o'Twani 5 ms» nnonian 5-Substituted-3-(5, 5-dichlorophenyl)-2,4- oxazolidinedione derivatives and fungicidal compositions containing them BASF AKTIENGESELLSCHAFT C. 42874 O.Z. 29,882 The present in ■vention relates to new and valuable oxazo «lidine derivatives having fungicidal properties; fungicides containing these compounds; and the use of these compounds as fungicides.

It is known (German Laid-Open Application 1,811,843) to use N-2, 5-dichlorophenyloxazolidines, e.g. , N-3,5-dichlorophenyl-5, 5-dimethyloxazolidine-2,4-dione, as fungicides. However, their fungicidal action is unsatsifactory.

We have now found that oxazolidine derivatives of the formula where R denotes alkoxyalkyl or alkylthioalkyl of 2 to 4 carbon 2 atoms or chloromethyl and R denotes hydrogen or lower alkyl of 1 or 2 carbon atoms, have a fungicidal action superior to that of known compounds .

The following are examples of compounds of the invention: N- ( ,5-dichlorophenyl)-5-methyl-5-methoxymethyloxazolidine-2,4-dione, N- (3,5-dichlorophenyl)-5-methyl-5-methoxyethyloxazolidine-2,4-dione, N-(3,5-dichlorophenyl)-5-methyl-5-ethoxymethyloxazolidine-2, 4-dione, N- (3, 5-dichlorophenyl)-5-methyl-5-methylthiomethyloxazolidine-2,4-dione, ' O.Z. 29,882 N- ,5-dichlorophenyl )-5-methyl-5-methylthioethyloxazolidine-2 I-dione, N- (3, 5-dichlorophenyl ) -5-methyl-5-ethyl thiomethyloxazolidine-2, 4-dione, N- (3> 5-dichlorophenyl )-5-methyl-5-propylthiomethyloxazolidine-; 2, 4-dione, N- (3, 5-dichlorophenyl)-5-methyl-5-chloromethyloxazolidine-2,4~ dione.

The new compounds have a very good action on phytopathogenic fungi and on fungi which destroy industrial goods, e.g., Erysiphe graminis (in cereals), Erysiphe cichoriacearum (in cucumbers and melons), Botrytis cinerea (in strawberries, vines and ornamentals), Monilia fructigena (in apples), Piricularia oryzae (in rice), Pellicularia fllamentosa (in rice), Sclerotlnia sclerotiorum (in tobacco and tomatoes), Aspergillus niger (in groundnuts, paper and textiles), and Chaetomium globosum (in textiles, paper and leather) .

The agents of the invention may be incorporated into conventional formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These formulations are prepared for instance by mixing the active ingredient with solvents and/or carriers, if necessary using emulsifiers and dispersants. If water is used as diluent, other organic solvents may be used as auxiliary solvents. The most important auxiliaries are solvents such as aro-matics (e.g. xylene and benzene), chlorinated aromatics (e.g. chlo-robenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. o.z. 29, 2 methanol and butanol), amines (e.g. §fctianolamine and dimethyl.?' rm-amide) and water; carriers such as flours of naturally occurin^ rocks (e.g. kaolins, clays, talc and chalk) and synthetic rock flours (e.g. highly disperse silicic acid, silicates); emulsifying agents such as non-ionogenic and anionic emulslfiers (e.g. poly-oxyethylene fatty alcohol ethers, alkyl sulphonates and aryl sul-phonates) and dispersants such as lignin, sulphite waste liquors and methylcellulose.

The formulations generally contain from 0.1 to 95 by weight of active ingredient, preferably from 0.5 to 90$ by weight. The ready-to-use formulations such as solutions, emulsions, suspensions, powders, pastes and granules, may be applied in conventional manner, for example by spraying, atomizing, dusting, scattering and watering.

The agents of the invention may also be employed together with other active ingredients, for instance herbicides, insecticides, growth regulators, fungicides and fertilizers. Examples of fungicides which may be combined with the compounds of the invention are dithiocarbamates and derivatives thereof, such as fen±idimethyldithiocarbamate (ferbam) , zincEdimethyldithiocarbamate (ziram) , manganeseethylensibisdithiocarbamate (maneb) , manganese zinc ethylenediamine-bis-dithiocarbamate (mancozeb), zinc ethylerasbisdithiocarbamate (zineb), tetramethylthiuram disulphide (thiram), ammonia complex of zinc- (Ν,Ν-ethylene-bis-dithiocarbamate) and O.Z. 29,882 Ν,Ν' -polyethylene-bis- (thiocarbamoyl ) -disulphide (metiram), zinc- (Ν,Ν' -propylene-bis-dithiocarbamate) (propineb) , ammonia complex of zinc- (Ν,Ν' -propylene-bis-dithiocarbamate) and Ν,Ν' -polypropylene-bis- (thiocarbamoyl )-disulphide (methyl-metiram) , nitrophenol derivatives, such as dinitro- (1-methylheptyl )-pheny]|crotonate (dinocap) , 2-sec-butyl 6-dinltrophenyl 5,3-dimethylacrylate (binapacryl ) , 2-sec-butyl- ,6-dinitrophenyl^isopropyl carbonate; heterocyclic structures such as N- (trichloromethylthio) tetrahydrophthalimide (captan) , N- (trichloromethylthio) phthalimide (fdpet) , 2-heptadecyl-2-imidazoline acetate (glyodin), 2, -dichloro-6- (o-chloroanilino)-s-triazine (anilazin), 0, 0-d'iethylphthalimidophosphonothioate (plondrel ) , 5-amino-l- fbis- ( - phenyl-l,2, -tri-azole, 5-ethoxy-5-trichloromethyl-l,2, -thiadiazole, 2,3-dicyano-l, -dithioanthraquinone (dithianon), 2-thioxo-l , 3-dithio- [ , 5-b] -quinoxaline (thioquinox) , methyl 1- (butylcarbamoyl ) -2-benzimidazolecarbamate (benomyl), 2-raethoxycarbonylamino benzimidazole, 2-rthiocyanomethylthiobenzothiazole (busan), - (2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridino-2-thiol-l-oxide, 8-hydroxyquinoline or its copper salt 2 , 3-dihydro-5-carbaniloyl-6-methyl-l, 4-oxathiine-4 , 4-dioxide , 2 , 3-dihydro-5-carbaniloyl-6-methyl-l , 4-oxathiine , ^ 2- |furyl-(2) -benzimidazole, ^ piperazine-l,4-diyl-bis- [l- (2,2,2-trichloroethyl)-formamide] (tri- forine) , 2- jthiazolyl- (4)] -benzimidazole, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine (dimethirimol) , bis-(£-chlorophenyl)-3-pyridinemethanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene (thiophanate), 1,2-bis- (2-methoxycarbonyl-2-thioureido) -benzene (thiophanate M), and various fungicides such as dodecylguanidine acetate (dodine), 3_ ^2-(3,5-dimethyl-2-oxocyclohexyl)-2-hydroxyethyl] -glutarimide (cycloheximide) , hexachlorobenzene, N-dichlorofluoromethylthio-N' ,Ν' -dimethyl -N-phenyl sulphuric di- amide, 2, 5-dimethylfuran-3-carboxanilide, N-cyclohexyl-2 , 5-dimethylfuran-3-carboxamide , 2-methylbenzanilide, 2-iodobenzanilide, 1- (3,4-dichloroanilino)-l-formylamino-2,2,2-trichloroethane, 2,6-di'methyl-N-tridecylmorpholine and its salts, 2, 6-dimethyl-N-cyclodecylmorpholine and its salts, 2.3-dichloro-l, 4-anthraquinone, 1.4-dichloro-2, 5-dimethoxybenzene, sodium £-dimethylaminobenzenediazosulphonate (dexon) , l-chloro-2-nitropropane (lanstan) , . . , 2 polychloronitrobenzenes such as pentachloronitrobenzene, methyl isocyanate, fungicidal antibiotics such as griseofulvin and ka.au-gamycin, tetrafluorodichloroacetone, 1 -phenylthiosemicarbazide, Bordeaux mixture, nickel-containing compounds and sulphur.

The following examples illustrate the preparation of the new heterocyclic compounds starting from substituted glycolic esters, 1 2 R and R having the above meanings and R denoting a lower allphati radical, in accordance with the following scheme: The glycolic esters are in turn obtained from ketones which are converted in conventional manner via cyanohydrins to the glycolic acids which are then esterified: 1 2 R and R having the above meanings and R denoting a lower aliphatic radical.

EXAMPLE 1 18 parts (by weight) of methyl l-methyl-l-methoxymethylglycol-ate is dissolved in 80 parts of methylene chloride. 0.3 part of o. z . 29, 2 di utyl tin diacetate is then added. A solution of 20 parts of , , 5-dichlorophenyl isocyanate in 50 parts of methylene chloride is^ dripped into this solution. The mixture is then boiled under reflux for 3 hours and evaporated. The residue is dissolved in 300 parts 02 of benzene and 1 part of triethylamlne, and the solution is boiled for 8 hours under reflux, cooled, washed with hydrochloric acid and water, dried over sodium sulphate and evaporated. The crystalline residue is recrystalllzed from a mixture of methanol and water (9 : 1 ) . There is obtained 20 parts o'f N- (3, 5-dichlorophenyl ) -5--me-thyl-5-methoxymethyloxazolidine-2, -dione which melts at 110° to 111°C. Recrystallization increases the melting point to 113° to 11 °C.

EXAMPLE 2 0.3 part of dibutyl tin diac.e ate is added to a solution of 18 parts of methyl 1-methyl-l-chloromethylglycolate in 80 parts of absolute ether. A solution of 20. 1 parts of 3> 5-dichlorophenyl isocyanate in 50 parts of methylene chloride is dripped into this solution. The mixture is then -boiled for 3 hours under reflux and evaporated. The residue is dissolved in 300 parts of benzene and 1 part ,o£ triethylamlne and the solution is boiled for 8 hours un-der reflux, cooled, washed with 2% hydrochloric acid and water, dried over sodium sulphate and evaporated. The crystalline resi<∑bu£ is recrystalllzed from methanol. There is obtained 22 parts of N- > 5-dichlorophenyl ) -5-methyl-5-chloromethyloxazolidine-2, -dione having a melting point of 115°C.

The oxazolidine-2, -diones listed below were obtained in the same manner. o.z. 29, 2 CH^-0-CH2-CH2- CH,- CH^-CHg-O-CHg- CH,- 68-69 CH-^—S—CHg— CH,- 72-75 CH-j—S—CHg—CHg— CH,- 94-95 CH-j-CHg—S—CHg— CH,- viscous > C1-CH2- H- 140-141 CH,-0-CHo- H- 83-84 3 2 CH_—S—CH — H- viscous 3 «= The action of the new compounds is demonstrated in the follow ing examples.

EXAMPLE 3 The active ingredients are added to a nutrient solution ideal ly suited for promoting the growth of the fungus Aspergillus niger in amounts of 100, 75» 50, 10, 5 and 1 part(s) by weight per million parts of nutrient solution. 20 ml of this nutrient solution \ O.Z. 29,882 to is placed in/ 100 ml Erlenmeyer flasks and inoculated with 0.3 "g of Aspergillus spores. The flasks are heated at 36°C for 120 hours. After this time the extent of fungus spread, which takes place mainly on the surface of the nutrient solution, is assessed employing the following scale: 0 = no fungus growth, graduated down to 5 = uncontrolled fungus ^.-.JW growth (surface of nutrient solution completely covered by fungus).

Active ingredient Amount of active ingredient in nutrient solution in parts per million parts of nutrient solution 100 75 50 25 10 5 1 (prior art compound used for comparison purposes) Control (untreated) 5 5 5 5 5 5 o.z. 29,882 EXAMPLE 4 Leaves of cucumber seedlings grown in pots are sprayed with aqueous emulsions of a mixture consisting -d" the extent of Q0% of active ingredient and 20$ emulsifier and, after the sprayed-on layer has dried, dusted with spores of cucumber mildew (Erysiphe .to cichoriacearum) . The plants are then placed in a greenhouse kept at a temperature of from 20° to 22°C and having a relative humidity of from 75 to Qo%. After 10 days the extent of fungus spread is assessed employing the following scale: 0 = no attack, graduated down to 5 = all leaf surface covered by fungus.

Active ingredient Leaf attack after spraying with liquor containing the active ingredient in amounts of 0.2% 0.1% 1 0 0 2 1 3 4 5 (prior art compound used for comparison purposes) Control (untreated) 5 5 EXAMPLE 90 parts by weight of compound 1 is mixed with 10 parts by weight of N-methyl- o( -pyrrolidone . A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 6 20 parts by weight of compound 2 is dissolved in a mixture . . , consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of οΐέΫο-' acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene sulphonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100, 000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained cons, taining 0. 02$ by weight of the active ingredient.

EXAMPLE 7 20 parts by weight of compound 1 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100, 000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0. 02$ by weight of the active ingredient.

EXAMPLE 8 20 parts by weight of compound 2 is dissolved in a mixture consisting of 25'pparts by weight of cyclohexanol, 65 parts by weight f a mineral oil fraction having a boiling point between 210° and 280°C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100, 000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0. 02$ by weight of the active ingredient. o. z . 29, 2 EXAMPLE 9 20 parts by weight of compound 1 is well mixed with j5 parts" by weight of the sodium salt of diisobutylnaphthalene- & -sulphonic acid, 17 parts by weight of the sodium salt of a lignin-sulphonic acid obtained from a sulphite waste liquor, and βθ parts by weight of powdered silica gel, and triturated in a hammer mill. By uniform ly distributing the mixture in 20, 000 parts by weight of water, a spray liquid is obtained containing 0. 1$ by weight of the active ingredient.

EXAMPLE 10 3 parts by weight of compound 2 is Intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 5$ by weight of the active ingredient.

EXAMPLE 11 JO parts by weight of compound 1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

Claims

1. 44737/2 o.z. 29,882 What we claim is:- 1. An oxazolidine derivative of the formula where R denotes alkoxyalkyl or alkylthloalkyl of 2 to 4 carbon 2 atoms or chloromethyl and R denotes hydrogen or lower alkyl of 1 or 2 carbon atoms.

2. A fungicidal composition comprising an oxazolidine derivative of the formula where R1 denotes alkoxyalkyl or alkylthloalkyl of 2 to 4 carbon atoms or chloromethyl and R2 denotes hydrogen or lower alkyl of 1 or 2 carbon atoms. ,

3. A fungicidal composition comprising a solid or liquid carrier and an oxazolidine derivative of the formula where R1 denotes alkoxyalkyl or alkylthloalkyl of 2 to 4 carbon atoms or chloromethyl and R denotes hydrogen or lower alkyl of 1 or 2 carbon atoms. 44737/2

4. A process for producing a fungicidal composition wherein a solid or liquid carrier is mixed with an oxazolidine derivative of the formula where R denotes alkoxyalkyl or alkylthioalkyl of 2 to 4 carbon atoms or chloromethyl and R denotes hydrogen or lower alkyl of 1 tor 2 carbon atoms.

5. A process for controlling gungi Vherein the fungi are treated with an oxazolidine derivative of the formula where R denotes alkoxyalkyl or alkylthioalkyl of 2 to 4 carbon 2 atoms or chloromethyl and R denotes hydrogen or lower alkyl of- 1 or 2 carbon atoms.

6. N- (3,5-dichlorophenyl)-5-methyl-5-methoxymethyloxazolidine-3,5-d one.

7. N- (3,5-dichlorophenyl)-5-methyl-5-ethoxymethyloxazolidine-2,4-dione.

8. N- (3, 5-dichlorophenyl )-5-methyl-5-chloromethyloxazolidine-2,4-dione.

9. N- (3, 5-dichlorophenyl )-5-methyl-5-methylthiomethyloxazoli-dine-2,4-dione.