FUNGICIDE COMPOSITIONS

Abstract: The invention relates to synergistic combinations of known fungicide active ingredients and their application in plant protection.

Description: FUNGICIDE COMPOSITIONS Field of invention The invention relates to synergistic combinations of known fungicide active ingredients and their application in plant protection. Technical field N-alkyl-morpholiπes are applied as fungicides in plant protection (DE-PS 1164152 and 1198125 and DD 140112) . A disadvantage of the known agents is that they have only a narro spectrum of activity, preferentially for ildew fungi (Erysiphales) in cereals. By their phyto- toxic si ' de effects they can be used only in a restricted field of application. The various acyla ide derivatives (DO 118 979 and 118 510, DE-PS 2 515 091, I 448 810 and 2 903 612. GB-PS 1 603 730 and EP 26 873) , on the other hand, possess a good efficacy against fungi from the group of Oomycetes, but they are inactive against other plant pathogenic fungi of economical importance. Furthermore, it is known that benzimidazole- and dithiocarbamate fungicides are applied in plant protection to control fungal diseases (G8-PS 1 193 461, 1 190 614 and i 000 137) . A disadvantage of the benzimidazole fungicides results from the quick appearance of resistance in the SUBS " πT 3£SHEET target fungus population. For simultaneous control of different species of fungi the use of a mixture of N-alkyl-morpholines with dithiocarbamates was recommended (DD 111 014). It is also known that N-alkyl- αrpholine derivatives in combination with methyl N-(2-methαxyacetyl)-N-(2.6-xyiyl)- -D,L-alaπinate (HU-P5 T/33363) are beneficially used against fungal diseases. Detailed description of the invention The aim of the invention is. to enrich the prior art with fungicide compositions of better properties for the practical control of fungal diseases. Object of the invention is a fungicide composition containing in addition to the conventional carriers and auxiliaries. 5-95 by weight percents of an active ingredient mixture of the following components: A) one of the following acylamide derivatives: methyl N-(2-methoxyacetyi)-N-(2,6-xylyi)-D .L- -alaπiπate (Metalaxyl); methyl N-(2-furoyl)-N-(2,ό-xylyl)-D,l-alaninate (Furalaxyi) ; meth l N-pheπylacetyl-N-(2.6-xylyl)-D,L-alaninate (Beπalaxyl) ; _÷~alpha-2-chloro- -(2,6- χ ylylacetamido)-gamma-butyro- lactσne (Ofurace); (^)-alpha-^ -N-(3-chloroohen\.I)cycIopropanecarbo - mido -gamma-but rolactone (Cvprofuram ; 2-methoxy-N-(2-oxo-l, 3-oxazoIidiπ-3-yl)-2 ' , 6 ' - - ylidide (Oxadixyl); N-isoxazole-5-yl-N-(2,6-xylyl)-D,L-alanine-methyI ester (LAB 149202F); N-(2,6-dimethyl-phenyl)-2-methoxy-N-(tetrahydro- -2-oxo-furanvl ) -acetamide (RE 26745) ; and B) one of the following morpholine derivatives: 2.6-dimethyl-4-tridecylmorpholiπe (Tridemorph) ;. 4-cyclododecyl-2,6-dimethyImorphαiiπe (Dodemorph; : ( r)-cis-4-/_ 3-/4-tert-butylphenyl)-2-methyIprop \ 7 ■ -2.6-dimethylmorpholiπe (Feπpropimorph) ; the mixture of N-alkyl (C-, ? ) -2 , ό-dimethylmorpholiπe and N-alkyl(C, )-2,5-dimethyl morpholine (Aldimorph) : together with C) one of the following fungicides diethyl 4,4'(o-phenylene)bis(3-thioallophanate) (Thiophaπata ) ; dimethyl 4 , 4 ' -/_ ~ o-phenyleπe )bis ^ 3-thioallophaπata/ (Thiophaπate-methyi) ; methyI-beπzimidazole-2-yl-carbamate (Carbendazim) or (BCMΪ ; methyI-l-(butyicarbamoyl)benzifτιidazole-2-ylcarbamate (Beπomyl) ; 2-(4-thiazolyl)-lH-benzimidazole (Thiabendazole) ; cr SUBSTΪTOTΕ Si& D) one of the following dithiocarba ate or di- sulphide deri tives: zinc ethylenebis(dithiocarbamate) (polymeric) (Ziπeb) ; manganese ethylenebis(dithiocarba ate) (polymeric) (Maπeb) ; manganese εthyleπebis(dithiobarbamate) (polymeric) complex with zinc salt (Mancozeb); zinc ammoniate ethyleπebis(dithiocarbamate)-poly- (ethyiene thiura disuiphide) (Metira ) ; polymeric zinc- propylenebis(dithiocarbamate) (Propineb) ;- the mixture of Metiram [_ zinc a moπiate ethyl- eπebis(dithiocarba ate)-pelyethyieneτhiura bisulphide/ and Prcpineb /_ polymeric zinc propylenebis(dithiocarbamate_7 in a ratio of 1:3 respectively (Polycarbazin) : In the compositions of the invention, the rate of the active ingredients A, B and C is 1-1:3-5:1-6, advantageous ly 1:4:4, the rate of the compounds A, B and D is 1-1:3-3-5:5-10 advantageously 1:4:10. The compositions according to the Invention can be advantageously used to control diseases, which are caused by various species of Surprisingly It was found that using the fungicide composition of the invention in the case of numerous species of fungi an increased activity may be observed, which Is based on a synergistic rather than an additive action. This can be calculated e.g. according to the Colby's formula; SUBSTITUTE SHEET E = X + Y - wherein 100 X is the efficiency of the components A + B and Y is the efficiency of the components C + D . Another method is the HORSFALL model where the toxic effects of various treatments are compared at the same concentration level, i.e. each component of the fungici mixture is tested at the total amount of the mixture applied, and the criterion of synergism was as follows: .SD^ mb ^ = CT. -MRV wherein l max LSD comb = the lowest standard deviation. at P = 5% in the experiment, CT. = effect of the "i" variant of the treatment with the l — fuπgicidal mixture, MR = the maximum response value of the most toxic max combination partner, if it was used alone at the total amount of the mixture concerned. If X, positive, synergism, if X. negative, antagonism occurred . In the SUN's model a Comparative Toxicity Index is used, which is calculated as follows: Co. T.I . = wherein øu g §?j?υτι SHSS ED η = the efficiency of the known mixture Y , EDc = the efficiency of the active ingredient _Z-_ a_ and b_ Indicate the current mass parts of the partners Y and _ in the combination. An additional advantage of the composition of the present invention lies in a reduced risk of formation of resistance, that means in the reduced occurence of fungal strains resistant to the above mentioned compounds under the selection pressure of the " claimed fungicides. This is due to the different mode of action cf the components, and to the abscencε of positive cross resistance among the components. Due to the above mentioned reasons, the compositions according to the invention can be used for the reduction of heterogenαus fungal populations, which at the conventional application of the Individual components and/or their binary mixtures can not be controlled satisfactorily. Based on the systemic properties of some components, pπytα- pathogeπlc fungi such as Plasmooara halstedii (Peronosporales Ooomycetes). Peronospora manshurica (Peronosporales, Oomy¬ cetes), Sclerospora graminicola (Peronosporales. Oomycetes), S.macrosoora . Peronospora pisi (Peronosporales Oomycetes), Ustiiaqo mavdis (Ustilaginales , Basidicmycetes) , Listilaαo avsπae (Ustilaginales, Bsidio ycetεs) . Fusariuπ (Deuteromycεtes) , verticillium sop. (Dsu-teromycεtes) , Rhizoctonia solanl (Polyporales , Basiαio ycetes; . Ste eum ourpureum (Basidiomycetes) etc. can be controlled effεctivεiv ana nε i de elooεd parts of nε olant can also be protected. SUBSTITUTE Sfri^T With an optimal combination of the active ingredients according to the invention the following groups of phyto- pathogemc fungi can be controlled: pow ery mildews, for example Ervsiphe spσ. (Erysiphales. Ascomycetes) , Asperqillu spp. (Eurotiales, Ascomycetes), Penicillium spp. (Eurotialεs Ascomycetes), Pho a betae (Dothiales, Ascomycetes), Ph . macdonaldii , Didvmelia applanata (Dothiales, Ascomycetes) , Fusaπuπ graminearum (Hypocreales. Ascomycetes) , Nectr ia cinnaoarina (Hypocreales, Ascomvcetes ) , Venturia inaequal is (Dothiales, Ascomycetes), Khuskia oryzae (Sphaeπales , Ascomycetes) , Colletotrichu atramantarium (Sphaeriales , Ascomycetes) . Coll . dematium . Diaporthe phaseolorum (Sohaeπ aies, Ascomvcetes) , Pho opsis mail (Sphaeriales, Ascomycetes Ceratocystic ulmi (Sphaeriales, Ascomycetes) , Botrvtis spp. (Helotiaies, Ascomvcetes). Sclerotima sclerotloru (Heloti- alεs, Ascom cetes) , Ustilaqo spp. (Ustilaginales, Basidxo- mycεtes) Verticillium sppi Rhizocton a solani (Polvporales . Basiαio cstεs ) , S . purpureurr. Tr . versicoior , Sohaeropsis malorum , Pvthium sop. (Peroπosoorales , Oomvcetes) , Phvto- phthora spp. (Peronosporales, Oomycetes) , Albugo Candida , (Peroπosporalεs , Oomycetes) , Bremia bectucae (Peronosporales, Oomycetes) , Peronospora destructor (Peronosporales, Oomycetes Plasmooara v ticola (Peronosporales, Oomycetes) , Pseudo- peronospora cubensis (Peronosporales, Oomycetes) , Peronospora spp. (Psronosoorales, Oomvcetes) , Aiternaria spp. (Deutεromy- cetes) , Fusaπu oxy sporu and other Fusarium spp. (Deuter- omvcetes' . Verticillium soo (Deutsro ycεtes). They are also useful against Graπr-oositiiε and Gram-negative bacteria BSTΓTIΠΈ SH ET (Corvnebacterium michiqanense, C. πebras eπse , C. flaccum- faciεns and Xantho onas alvacεarε . X_. phasεoii , X_. ans- lucens pv. orvzae) ; and human rεlatεd Bacillus . 5taphylococcu; and Strepto vces spp., too. The compositions according to the invention can be formulated in a conventional way, e.g. to wettable powcers, granulates cr microcapsulεs, emulsion concentrates or flowables ( P , EC, FW, G, SD) . For this purpose the active ingredients are dissolvεd in convεntioπai liquid carriers, if desired, in the presence of surface active auxiliaries, dispergated rεspεctivεly or admixed with solid carriers, or formulated according to other known processes. The compositions of the invention are of 5 to 95 weight percents, advantageously 5 to 50 weight perceπts of the active ingredients. The compositions can bs usεd in a conventional v;ay, e.g. by spraying, dusting, submerging for dispersion or sεεd drεssiπg. The appliεd quantitiεs depend on the aim of applica¬ tion and generally amount to 0.3 to 5 kg active iπgrεdient/ha The composition of the invention may be used for the treat¬ ment of sugar beεt (Bεta vulgaris), sunflowεr. soya, potato, tomato, corn, whεεt, cucumbεr, vinε, tobacco, broom-corn, millet, horse-bean (Vlcia faba), cotton, citrus spp. apple, sugar-cane, avocado, mango (Mungos raungo) , lettuce, onion. tulip, hyacinth, gladiolus (sword-lily), pea, bean, pεanut, εdic (Medicago), clover, batata (Xanthoso a spp.) plants susceptible to pathogenic fungal infections. The composition according to the invention and ;heιr action are illustrated bv the following examples Example 1 In 508 g of water 21.2 g of Tensilin FN 80, 7.6 g of Tensiofix CG 21, 7.6 g of Teπsiofix B 7425 are dissolved To the solution under slow stirring 47.5 g of ethylene- glycol and under vigorous stirring 156 g of Carbendazim and 38 g of LAB 149202 are added. After homogenization the suspension will be transferred in an atπtor of 1.5 liter content which contains siliquartzite pearls of 1 mm diamεte: The atπtor is operated for 30 minutes at 1440 RPM and later at 30 RPM. To the susoensioπ the following solution is added- 156 g of Tridemorph. 4 g of Triton X-15 , 31.2 g of Triton X-114 After stirring the suspension 16.8 g of paraffin oil and 1.8 g of Emulsogen M are added. After stirring the glass pearls (quartzite pεarls) are separated by a sorεen The floating capacity of the suspension con¬ centrate amounts according to the CIPAC method to 95 % . Examole In a powder homogenizer of 3 1 capacity 200 g of Wessaiαn S are introduced. To 261 g of Tridemorph 6.6 g of Triton X-15, 52.8 g of Tritcn X-1I4 and 6 . 6 g of Triton X-45 are added Bv slow stirring a homogeneous solution is oreDarεd. This solution is added to Wεsselon S whilε slow stirring After further stirring 250 g of Carbendazin and 88 g c: LAB I492C2 are added Afts 5 minutes of za ■ tion 50 g of Atiox 5320 and 75 g of Atlox 4862 are added and after further 5 minutes the mixture will be completed by the addition of 10 g of Aεrosil. The powdεr mixturε will bε granulated in 2 parts in a laboratory granulator with water (to 500 g of the powdεr mixture 66 ml of water are added) . The granulate formed is dried in a drying oven at 60 °C till constant weight. Thε particlε sizε of the granulate amounts to 95% bεtwεεπ 0.1 and 0.6 mm. Thε float¬ ing capacity of thε product obtaiπεd amounts according to CIPAC to 84%. Exa plε 3 In a ho ogεnizer of 3 I content 150 g of Zeoiεx 414 arε filled as a carrier. In a separate vessel 266 g of Tridemorph, 6.8 g of Triton X-I5, 6.8 g of Triton X-45 and 54.2 g of Triton X-I14 arε mixed by stirring slowly. A homo¬ geneous solution is obtained, which is transfεrrεd whilε uniform stirring in the homogenize-. After homogenizing 266 g of Carbendazim and 66.6 g of Benalaxyl arε introduced Thε mixturε Is homogenized, thεrεaftεr under continuous stirring 88.6 g of saccharose, 30 g of a wetting agent IS (Hoεchst) and 65 g of sodium ligninε-sulphonate are addεd. Thε powdεr mixturε is ground in an air jet mill to particles of 10 ,um size. The floating capacity of the powdεr mixturε obtainεd amounts according to CIP C to 87%, thε wεtting time is 18 sec. SUBSTITUTE Sϊ^ET Example In an atriter of 1.5 1 content 60.54 g of water and 6.55 g of ethylene glycol are mixed. To the solution 2.21 g of Tensiofix B 7425, 1.7 g of Teπsiliπ FN 80, 12.5 g of Carbendazim and 3.1 g of Benalaxyl arε added. The atritor is filled with siliquartzite glass pearls of 2 mm diameter and the mixing mechanism of the atritor is operated for 30 minutes with an RPS of 800. After this period the follow¬ ing solution ' is added to the suspension: 9.4 g of Tridemorpn 0.23 g of Triton X-15, 0.23 g of Triton X-45 and 1.84 g of Triton X-114 (preliminary homogenized) . After stirring to the mixture 1.35 g of paraffin oil and 0.15 g of Emulsogen ' M are added. The siliquartzite glass pearls are filtεred from the suspension. Applying a stirrer with a big shearing moment 0.2 g Tensiofix 821 are added to the solution. The floating capacity of the suspension is according to CIPAC 97% -(Particle size under 5 ,um in 98%) . Example 5 To 605.4 g of water 65 g of ethylene glycol, 22.2 g Tensiofix CG-2I and 17 g Tensilin FN-80 are added. Applying a stirrer with a big shearing moment continuously 125 g of Carbendazim and 31 g of Metalaxvl are added to the solution. -At a maximum RPS of the stirrer ( 12000/minute ) thε suspension is homogenized. The suspension is poured into a laboratory atritor of 1500 ml and the atritor is filled with ceramic pearls of 1 mm diameter. gUB- sr rTE §?Hrør The stirrer of thε atritor is operated with a maximum RPS (1440/miπute) for 30 minutes. Thεrεaftεr into thε atritor a solution of 94 g of Tridemorph, 2.3 g of Triton X-15. 2.3 g of Tritpπ X-45 and 18.4 g of Triton X-I14 is iπtroducεd and stirring Is continued for further 5 minutes. From tne suspension the glass pearls are rεmoved by a screen. Apply¬ ing a stirrer with a big shearing moment to -the suspεnsion a prεviously similarly suspended mixture consisting of 13.5 g of paraffin oil, 1.5 g of Emulsαgeπ M and 2 g oϊ Teπsicfix 8 21 is added and is homogenized for 3 minutes. The floating capacity of the suspsnsiσπ obtainεd amounts according tc CIPAC 92%. The average particlε size lies under 5 ,um (97% Example 6 In a laboratory powder homogeπizεr of 3 1 content 300 g of Wessaioπ are introducεd. To 266 g of Tridεmorpπ undεr slow stirring 4 g of Triton X-15, 4 g of Triton X-45 and 25 g of Triton X-114 arε added. Undεr stirring thε Tri¬ dεmorph solution is slowly pourεd into the powder homogεnizεr Thereaftεr whilε furthεr stirring a mixture of 266 g of Carbendazim 66 g of Metaiaxyl. 30 g of thε wεtting agent IS and 39 g of sodium llgπinε sulphate arε added. After 2 minu¬ tes of post ho ogeπizatioπ the powdεr mixturε is ground in a laboratory air jet mill to particlεs under 10 ,um particle size. The floating capacity of thε powder mixturε amounts according to CIPAC to 86%, thε wεtting time is 23 sec. SUBSTITUTESHEET Example 7 In a powder homogenizer of 3 1 capacity 549.5 g of Wessalon S are introduced. To 131 g of Tridεmorph 3.3 g of Triton X-15, 26.4 g of Triton X-114 and 3.3 g of Triton X-45 are added. By slow stirring a homogeneous solution is prepared. This solution is added to essalon S whilε slow stirring. After further stirring 175 g of Carbendazim and 44 g of LAB 149202 are added. After 5 minutes of homogeni zation 25 g of Atlox 5320 and 37.5 g of Atlox 4862 are added and after further 5 minutes the mixture will be completed by the addition of 10 g of Aεrosil. The powder mixturε will be granulated in 2 parts in a laboratory granulator with water (to 500 g of the powder mixture 66 ml of water are added) . The granulate formed is dried in a drying oven at 60 °C till constant weight. The particle size of the granu¬ late amounts to 95% bεtweεn 0.1 and 0.6 mm. The floating capacity of the product obtained amounts according to CIPAC Example 8 In a hpmogenizer of 3 1 content 575 g of Zeolex 414 are filled as a carrier. In a spearate vessel 133 g of Tride¬ morph, 314 g of Triton X-15, 3.4 g of Triton X-45 and 27.1 g of Triton X-114 are mixεd by stirring slowly. A homogeneous solution is obtained, which is transferred hile uniform stirring in the homogenizer. After homogenizing 133 g of Carbendazim and 33.3 g αf Benalaxyl are introduced. The mixture is homooenized. thereafter under continuous stirrino SUBSHTCΠTE SH^T 44.3 g of saccharosε, 15 g of a wεttiπg agent IS (Hoεchst) and 32.5 g of sodium ligπiπe-sulphoπate are added. Latεr the mixture is stirred for further 3 minutes. The powdεr mixturε is ground in an air jεt mill to particles of 10 ,um size. The floating capacity of the powder mixture obtained amounts according to CIPAC to 87%, the wetting time is 18 sec. Exa plε 9 In a laboratory powder homogenizer of 3 i content 648 g of Wessalon are introducεd. To 133 g of Tridεmorph under slow stirring 2 g of Triton X-15, 2 g of Triton X-45 and 12.5 g of Triton X-114 are added. Under stirring the Tridemαrph-solutloπ is slowly poured into thε pαwdεr nomogεniz Thereafter while further stirring a mixture of 133 g of Carbendazim. and 33 g of Metalaxvl. 15 g of the wetting agent IS and 19.5 g of sodium ligninε sulphαπate are added. After 2 minutes of post homogεπization the powder mixturε Is ground In a laboratory air jet mill to particles under 10 ,um size. The floating capacity of thε pαwdεr mixturε amounts according to CIPAC to 86%, thε wεttiπg timε is 23 sεc. Auxiiiariεs and filling materials usεd a) Surfacε-activε atεrials (wetting agents and emulsifying agents) Tensiiln FN 80 (Kutrilln): alky1-aryI-polyglycolεther ; Triton X-15. X-45 and X-1I4 (Rohm and Haas): octyI-phenol- -polyglycolether; SUBSTITUTE SHE1T Tensiofix CG 21, B 7425 (Tensia): aIky1-aralky1-sulphon te and phosphate, esters and non-ionic surface-active material mixtures respectively; Emulsogeπ M (Hoechst): fatty alcohol-polyglycolether ; Atlox 5320 (Atlas ICI): non-ionic surface-active material; wetting agent IS (Hoechst) : Dialkyl-sulphq-succinate . b ) Dispersing agents: Sodium-lignine-sulphoπate ; Atlox 4862: Alkyl-ary1-sulphonate-formaldehydε-condeπsate . c) Anti-freezing agents: Ethylene glycol d) Filling and carrier materials: essalon S (Degussa): syπthεtic silicic acid; Aerosil 300 (Degussa): silicic acid with great specific surface ; Saccharose ; Zeolex 414 (Zeofin): sodium-aluminium-silicate; Paraffin oil . e) Sedimentation inhibitor Tensiofix 821 (Tenzia): synthetic poiysaccharide. Example 10 Efficiency against downy mildew of sunflower Sunflower germlings with the root initials, 1-5 " mm in length, were inoculated with zoosppre suspension (2.5 x 10 spore/ml) of the downy mildew fungus (Piasmopara halstedii (Farl.) Berlese et dε Ton! , Peronosporales, Oomycetes) . SUBSTΓTOTE §ϋOT Twenty four hours aftεr Inoculation the germiiπgs were immersεd into thε aqueous solutions/ emulsions/ suspensions of thε chεmicals to be tested for 18 hrs. The ger lings were then planted into sterile soil and grown in green- house until the evaluation of the εffectivity of treatments All measures not descripted in detail here, and the assess¬ ments wεrε madε as dεscribed by OROS and VIRANYI (1987): Ann. appl. Biol. 110:53-63. Thε efficiency of treatmεπts was charactεrizεc by EQς q (rcιg/1) valuε and the significance of syπεrgistic effεct was testεd according to SUN (1950). §UBS TΠUΠΠE SHSIT Table 1 Eradicant Effect of Benomyl, Tridemorph, LAB 149202F and of their mixtures against downy mildew of sunflower Active agent mass proportion of combi nat ion , rcsp the active agents ED 50 Co.T .1 1. LAB 149202F 19.08 2. fridemorph 500 3. Benomyl 500 4. 2+3 1:1 500 5. 1.2 1:4 16.86 . 1+2.3 1:4:4 6.55 1.70 Ihe active agents and their- mixtures, respecti ely, were applied in a suitable mass proportion in the form of wettable powder (WP) of the following cornpsition: 40% of the activu agent, or mixtures thereof respectively; Emulsogen 1-40, FWEEN 20, TWEEN 00, TWEEN 40, si l icarjcl, Myflosuporoel1 , dextran, Polyethylene glycol 20 000 a d cyclohexanon , 4.0; 0.5; 0.5; 1.0; 10.0; 10.0; 22.0; 8.0; and 4.0 per cent respect Examplε II Seed dressing against damping off fungi (Pvthiu . Fusarium in oeas) Seeds of the peas (Pisum sativu cv Gloriosa) were surface sterilizεd with 0.1% sublimatε prior to drεssing and treated thereafter with active agents formulated as 25 WP . To improve the adhesion at thε dressing process, a TWEEN 80 solution was added. The drεssεd sesds werε sown into an infεsted soil. 14 days aftεr εmergeπcε both qualitative and quantitative evaluation of fungicidal efficacy were carried out. The efficiency was calculated as follows: Efficiency = 100 A x 100 whεrεiπ A = Iπfεction ratε (%) of thε treated plants, 8 = Iπfεction ratε (%) of thε control plants. Table 2 Sεed dressing against fungi causing damping off Active agent Concentration Efficiency mg/L a .i . % 1. Carbendazim 2 . 0 2 . Metalaxvl 0 . 251 ÷Aldimorph 1 . 0 J 25 85 3. Metalaxvl 0 . 125] +AIdimorph 0 . 5 VI . 25 -Carbendazim 0 . 5 J SUBSTITUTE SHEET Table 3 Seed dressing against fungi causing damping off Active agent Concentration Efficiency mg/L a . i . 1. Propineb 1.50 0 2. Meta1axy1 0.25 ÷ Tridemorph 1.0 25 63 Mεta1axy1 25 - Tridemorph 0.5 1.325 91 ■ * ■ Propineb 0.7 Table 4 Seed dressing agains fungi causing damping off Active agent Concentration Efficiency mg/L a . i . i Benomyl ? .50 28 2. LAB 1492Q2F 0 •5 | 2 .5 fa / +Aldimorph 2 .0 J 3. LAB 149202F 0, ■3 1 ÷Aldimorph 1. +Bεπomyl • 2, .5 1. ■n o f Thε used 25 P had the following composition 25 weigh 9 , active ingredient or ingredients, respectively; 5 weight's Ca-lignin-sulphonate _ 5 weights Tween 80 7 weights Silicic acid 5 weight"s kaolin sυBsrrrøre sH^r E xampl e 12 P rotεct lvε e f fect aga inst Phytoohthora in festans on tomatoes Solanum lycoperslcum - plants, cv . "Tamina" at four- -leaf stage were drop-wet sprayεd with thε combinations in 25 P form. Thε Inoculation of thε plants with a zoo- spore-suspensioπ was carried out after thε fungicide was dried up. After the inoculation thε plants were kept for one day in a humid chamber at 16 C to 18 C and for five furthεr days in thε grεεnhouse at 20 C. Tnereaftεr the typical lεaf-lεsions appεarεd and their extension was a measure for thε intεnsity of Infection. Table 5 Protective effect against Phvtoohthora infestans on tomatoes Active agεnt Concentration Efficiency mg/L . a . i . 1. Metalaxvl Aldimorph 30 61 2. Zineb 30 18 3. Metalaxvl 2 Aldimorph 8 30 84 Zineb 20 SUBSΓTTP TΈ SHST T ab l e 6 Protective effect against Phvtoohthora infestans on tomatoes Active agent Concentration Efficiency mg/L a . i . 1. Propineb 30 27 2. etalaxyi 6.0 + Tridemorph 24 30 62 Metalaxyi 2.0 ÷ Tridemorph 8.0 30 88 + Propineb 20.0, Table 7 Protective effεct against Phvtoohthora iπfεstans on tomatoes Active agent Concentration Efficiency mg/L a . i . h 1. Maπeb 10 40 2. ancozeb 10 25 3. Oxadixyl 2 "- Tridemorph 8 10 47 ) 4. Oxadixyl -r Mancozeb 10 45 5. Oxadixyl • ^ Maπeb * 10 6 5 6. Oxadixyl - Tridemorph 78 ■ *- Maneb 7. Oxadixyl -I- Tridemorph 65 + Mancozeb Bm S ^E Table 8 Protectivε effect against Phvtophthora iπfestan's on tomatoεs Active agent Concentration Efficiency mg/L % L: Metiram 5.0 20 LAB 147202F 1.0] ÷ Tridemorph 4.0 j 5.0 54 LAB I47202F 0.8 ÷ Metiram 5.0 5.8 28 4. " LAB 147202F 0.5 ^ ÷ ' Tridεmorph 2.0 V 5.5 68 + Mεtiram 3.0 J Example 13 Effect on the growth of Phvtoohthora parasitica The acetαnic solution of the fungicides to be tested was in a suitable amount admixed to the agar mediums and 4 hours after pouring out the plates the Petri dishes werε inoculated with 3-3 mycelium cuts; after an inocula- tion period of 72 hours thε diameter of the cultures was measured. Thε growth inhibition was εxprεssed - refεrred to thε untrεatεd control - according to the following equation X.. - 7 j 100 - ( 100 x ) = inhibition in \ . wherein X Ikontr.-7 X- - = population dia etεr measured on j-cαmpounds (or combination thereof) containing medium plate of the given speciεs (i) sυBSTmsπ SHSET l > X ikoπtr.= population diameter measured on xeπobiotica not containing medium plate of the given species i . The data were analysed by means. of variance analysis and thε results are summarized in Table 9. Table 9 Effect of combinations o-f Tridemorph ^ Carbendazim ÷ an acylamide derivative on the growth (colony diameters) of Phytophthora para- sitica f.sp. πicotianae v ar tomato Active agent Concentration Inhibition or comoiπation mg/L 1. Metala yi 2.6 50 2. Tridεmorph 1.0 ] + Carbendazim 1.0 (, 2.25 81 - RE 26745 0.25 3. Tridemorph 1.0 ~ + Carbendazim 1.0 L 2.25 73.6 - Ofurace 0.25 Ex.ample 14 Control of a mixed ildew infection on cucumber leaves The both powdery and downy mildew pathogens when associated in a leaf disease complex on cucumber can severely damage the leaf surface causing a serious yield loss. sυBSTϊro Sεriεs of lεaf trεat ents werε carried out when first symptoms occurred caused by powdery mildews (Sphaerothεca fulgiπεa and Ervsiphe cichoracearum, Erysiphales, Ascomycetεs) and Downy mildεw (Pseudoperoncspora cubεπsis, Pεrαnosporalεs ? Oomycεtεs). Thε disεasε dεvεlαpmεπt was checked after days from the treatment by counting the number of visible pustules on thε leaves. The Inhibition of disease rate was calculated and expressed in percent of thε untrεatεd control. Results. Table 10 Active agents Concentration Inhibition of or ratio Mg/L disεasε ratε combinations (%) 1. Bεnalaxyl 10 32 2 . Tridemorph 10 55 3. Benomyl 10 26 4. 1+2(9:11) 10 61 5 . 1+3(9:10) 10 21 6 . 2-3(11:10) 10 16 7. 1+2+3 (9:10:11) 10 72 Example 15 Seed-dressing experiments with maizs Thε iπfεctiαn rats of maize sεεd lot by Fusariuπ species usεd for laboratory purposes amounted to 29.5%, out total contamination has reached 100% sc it was unsuitable suBsτmι?ε iHIϊt for sowing . After the treatment the infection rate of 4 x 100 seed pieces was evaluated following an incubation on Papa- vizas-medium. The effεct of combination (CHBA 6-11) was compared with the standard mixture Kolfugo Extra (20% Carbendazim) + Quiπolate V-4-X (2.0 1/t + 1.0 kg/t, respectively) commonly used in Hungary. The results are presented in Table 11. Table 11 Treatment Dose Agent Infection rate g/kg mg/100 g seed of seεd % CHBA 6 2.0 312+312+76 0.25 CHBA 7 2.0 262+350+88 0.75 CHBA 8 2.3 306+306+76 0.00 CHBA 9 2.8 263+350+87 0.25 CHBA 10 2.3 306+306+76 0.50 CHBA 11 2.8 263-350+87 1.0 Kolfugo Extra÷ 2.0 400 Quinolate V-4-X 1.0 500+150 1.0 Surface sterilized 29,5 Control 100,0 Tablε 1 '. Prεparation Activε rate of active act. agent formulation agent agent content act. agent g/1000 contεnt CHBA 6 Tridεmorph+ 4:4:1 156+156+38 350 +BCM+LAB 149202 CHBA 7 3:4:1 131+175+44 353 CHBA 8 4:4:1 133+133+33 300 ÷ Benalaxyl CHBA 9 3:4:1 94+125-31 250 CHBA 10 4:4:1 133+133-33 300 + Metalaxyi CHBA II 3:4:1 94+125+31 250 Apron 35 SP Metalaxvl Kolfugo 25 FW BCM Kolfugo extra BCM Quinolate V-4-X Carbαxiπ ÷ Cu-αxyquinolate Example 16 Sεεd-drεssing εxpεriments with sovabean (Acternaria. Fusarium, Asperqillus) Thε εfficiεπcy of thε individual trεatmεπts was evaluated first in thε laboratory by determining the composi- tion of pathogens (the contamination rate cf 2 x 100 sεεcs of soyabean) . In a field εxpεrimεnt, the yield of soyaoεan trεated with differεnt fungicidεs was measured, and expressed The results obtained are contained in Table T R E A T M E N T M o . o f s e e d Y I E L 0 i n f e c t e iinπ icide Dose of Dose of k g / 2 m K % formulation active (mean of 4 π/k(] seed ingredient re l i ca tes my/kg seed ) IIHΛ G (IKL) 2.0 312-ι312 t-76 5.5 2.15 100.6 IIUΛ 7 (IKL) 2.0 262050 i OB 1.5 2.10 110.1 :ill)Λ ϋ (I ' Kϋ) 2.3 3ϋ6 0fπ76 2.5 2.30 116.2 ;III1A 9 (1KB) 2.0 26313501-87 1.0 2.45 123.0 :illJΛ 10 (IKM) 2.3 306+306i-76 1.0 2.05 103.5 ;ill!Λ 11 (IKM) 2.8 263-1-350107 3.5 2.10 110.1 Λμrun 35 2.0 700 16 2.03 102.! Kolfugo 25 fW 2.0 700 11 2.07 104.5 Control 76.5 1.90 100.0 Example 17 Possibility of control population of pathogenic fungi associated with the root rot complex of seedlings Plant at seeding stage are εndaπgered by a πumbεr of soil- and seed-borne seedling- and foot diseasεs caused by fungi of various taxonomic position (usually namεd pathogεπε "associated with the root rot complex" of plants - of G. 0IX0N (1981): Vegetable Crop Diseasεs, The Macmillan Press Ltd, London). It is possible to eliminate certain pathogenic species with an efficient fungicide prεparate. However, thε speciεs non-sεπsitive to a given compound can build up in an explαsivε way. Thε use of broad-spectral fungicides may circumvεnt this problem. Such compounds, however, are often harmful pollutants of the environmεnt. Thε accumulation of toxic materials (ε.g. mercury, tin, aluminium or carcinogenic metabolite, such as ETU) can not be exluded and αnε must renounce their use. Against thε highly εfficiεπt and selectivε fungicide preparations that are harmless to nature and man¬ kind (e.g. Carbendazim, Metalaxyi), the targεt organisms (plant parasitεs) bεcomε quickly resistant. The resistance is due to genεtic reasons. In the population of the pathogens there appear individuals that carry genes rεsponsiblε for the reduction of fungicide sensitivity. Individuals carrying such genes that had been treated with the given fungicide will increase in number dramatically, moreover, in thε soil fungi of various taxonomic position are associated with thε root rot complex that makes a necessity to use a broad- -spεctrum fungicide. The use of especially selected and optimalized mixtures is necεssary duε to thε requirement of treatment as highly selective as possible and at the same time combating the formation of established resistant populations to the given fungicides. In Table 14 a model experiment is shown, which proves that in the case of a fungal population consisting of individuals of different fungicide sensitivity and associated with root roτ complex. by the appropriate combination of syπergis ically interact¬ ing fungicides a successful control can be achieved. Beside the fact, that the pathogenes associated with root rot complex can be controlled with certainty, a synergistic fungicide combination will reduce costs and decrease pesticid pressure to nature simply due to its increased efficacy τo the target organisms. Furthermore there occurs an economic synergism too. by thε rεduceα amount of chemicals applied for having thε sa ε εffect, by the reduced costs of application, and the by insurance increased of yield due to decreasing the probability of resistance. Performance of experiments By means of somatic hybridization ( olnar et. al. , (1985): Exp. Mycol. 9:326-333 ). and by mεans of mass sεlec- tion of spontaneous mutants (Oros (1987): Tag.-Ber. Akad. Ld . DDR.. Berlin 253, S 177-183), respectively, Fusarium oxvsporum and Phvtophthora parasitica strains/clones of different fungicide sensitivity were prepared for thε εxpεrimεπts. The efficacy of the fungicides was determine in conventional agar plates by measuring the radial mycelium growth after 48 hours. Fungicide effect was characterized by the % of inhibition of radial growth of colonies. As the survival of thε population in the presence of a harmful factor Is always determined by the most resistant part of this population, the Most Potent Treatment (MPT) was usεd for comparing εfficaciεs in thε experiment. SUBSTITUTESHEET Table 14 Control of mixed populations consisting of Fusariuin oxysporum and Phytophthnra parasitica individu ls of different fungicide sensitivity in the case of their simultaneous occurrence on toma toe . Active agen t Inhibition of fungal species. (to combi na t i on , res . ra tio F . oxysfirnuin' P. paras i Lice 50 0/L) Hi va . nico tianae /I MNc Carhenda ini 42.7 125 12.5 1 r i deinorph 06.6 510 1.8 1-1u ta 1 axy 1 5 0 4.2 0 1.2 (1:1) 0.1 105 10.5 1 i 3 (4:1) 57.2 1 .9 5.7 2 i 3 (4:1) 117 9.05 11.7 1.2.3 (4:4:1) 0.9 10.07 1.0 - A population consisting of resistant and sensitive strains to benomyl. Ratio 1:1 li = A population consisting of resistant and sensitive strains to metalaxyi. Ratio 1:1. c = • •/T M τ = ' the factor, which shows how mπnyfold the concentration of the preparate should be increased to have the same effect as it was obtained at the application of the most potent one (No. 7). T. = ED,- n value (mg/L) of the "i" treatment, and I.. T = the Eϋrη value (mg/L) of the most potent treatment (MPT) .

Claims: What wε claim is 1. A fungicide composition containing as activε ingrεdieπt a mixture of: A) one of the following fungicides: methyl N-(2-methαxyacεtyl)-N-(2,6-xylyl)-D,L-alaninate; mεthyl N-(2-furoyl)-N-(2. -xylyl)-D,L-alaninate ; methyl N-phεnylacetyl-N-(2.6-xylyl)-D r L-alaπinate; ^-aIpha-2-chloro-N-2,6-xyIylacεtamido-gamma-butyrolactonε: (+_)-alpha-/_N-(3-chlorophenyl)cyclopropanecarboxamid 7-gamma- -butyrolactonε; 2-mεtho y-N-(2-oxo-l,3-oxazoIIdiπ-3-yl-2'6 J -xylidide; N-isoxazolε-5-yl-N-(2,6-xylyl)-D,L-alaπinε-mεthylester; N-/_ ~ 2,6-dimethyI-phεnyl(-2-mεthoxy-N-)tεtrahydro-2-oxo- -furaπyjlZ-acεtamide; and B) a fuπgicidε of the group of morpholines 2,6-dimethy-l-4-tridecylmorpholIπε; 4-cyclododεcyI-2, -dimεthylmorphαllnε; (÷_)-cis-4-/3-(4-tεrt-butylphεπyi)-2-mεthylpropyI/-2,6-di- εthylmorpholinε; thε mixturε of N-alkyl (C-, „)-2,6-dimεthylmαrpholinε and N-alkyl(C, )-2,5-dimethyl mo pholine; togethεr with C) one of the following fungicides diethyl ,4'/o-phenylεnε(bis)3-thioallophaπatε/; dimethyl 4,4'-(o-phenylεπε(bis)3-thiαallophaπatε/; methyl-benzimida2ole-2-yl-carbamatε; methyl l-(butylcarbamoyl)bεnzimidazαIe-2-ylcarbamate : 2-(4-thiazolyl)-lH-benzimidazole, or D) one of the following dithiocarbamate or disulphid derivatives: zinc ethylenebis(dithiocarba ate) (polymeric); manganese ethylenebis(dithiocarbamate) (polymεric); manganese ethylenebis(dithiocarba ate) (polymεric) compiεx with zinc salt; zinc ammoπiatε ethylenebis /dithiocarbamate( -ρoly)εthylene- thiura disulphide/; polymeric zinc propylenebis (dithiocarbamate); the mixture of zinc ammoniate ethyleπebis(dithiocarbamate/-po ethyleπethiuram disulphide) and pelymeric zinc propyienebis/d thiocarbamate/ in a ratio of 1:3, respectively; wherein the weight ratio of thε compounds A. B and 0 is 1-1:3-5:5-10 and the weight ratio of the compounds A, B and C is 1-1:3-5:1-6; together with a fuπgicidally acceptable inert carrier . 2. A fungicide composition containing as active ingredient one of thε following mixtures: A) one of the following fungicides: methyl N-(2-methoxyacetyl)-N-(2 ,6-xylyl)-D,L-alaniπate; methyl N-(2-furoyl)-N-(2, 6-xylyl)-D, L-alaninate; methyl N-phenylace + yl-N-(2,6-xylyl)-D,L-alaniπatε; +_-alpha-2-chlorα-N-2,6-xylylacεtamido-gamma-butyrolactoπe; (+_) -a1pha-A N-/3-chIorophεny1/cyc1opropanecarboxa ido_7- -gamma-butyrolactone ; 2-methoxy-N-/2-oxo-l ,3-oxazolidiπ-3-yl-2' ,6'-xylidide: M-isαxazole-5-yl-N-(2,6-xylyl)-D,L-aianine-methylεster-. N-/_ ~ 2 , 6-dimethyl-ph en yl(-2-mεthoxy-N -)tεtrahydro_- 2-oxo- -f uraπyj^7-acεtamidε ; and B) a fungicide of the group of morphc-lines 2,6-dimεthyl-4-tridεcylmorpholinε; or the mixturε of N-alkyl (C-, 9 )-2,6-dimεthyImorpholinε and N-alkyKCA ? )-2.5-dimεthyl morpholine; tαgεther with C) one of the following fungicides rπethyl-bεnzimIdazolε-2-yl-carbamate; or mεthyl l-(butylcarbamoyl)beπzimidazol-2-ylcarbamate; wherein in each of the mixtures the weight ratio αf the compounds A, B and C is 1:4:4, togethεr with a fuπglcidally acceptablε inεrt carrier. 3. A fungicide composition containing as active ingredient • A) one of the following fungicides: mεthyl N-pheπylacεtyl-N-2.6-xylyl-Q.L-aIaπInate; or +_-alpha-2-chloro-N-2,6-xylylacetamido-gam a-butyrolactoπe; or 2-methoxy-N-(2-oxo-l,3-oxazαlidiπ-3-yl)-2',6'-xylidide and B) 2,6-dImethyl-4-tirdecylmαrpholine; together with C) methyl-benzimidazole-2-yI-carbamate ; SUBSTITUTESHEET wherein in each of the mixtures the weight ratio of the compounds A , B and C is 1:4:4, together with a fuπgicidal- ly acceptable inert carrier. 4. A fungicide composition containing as active ingredient A) one of the follo ing fungicides: methyl N-phenylacεtyl-N-2,6-xylyl-D,L-alaπinatε, or ^-alpha-2-chloro-N-2,6-xylylacetamido-gamma-butyrolactone; or 2-mεthoxy-N-(2-oxo-l ,3-oxazoϊidiπ-3-yl)-2' ,6'-xylidide; and B) the mixture of N-al yl(C, ? )-2,6-dimethyl- morpnoliπe and N-ai yI(C, )-2,5-dimεthyl morpholine; together with C) methyl-benzimidazoie-2-yl-carbamate ; wherein in each of -the mixtures the weight ratio of the compounds A, B and C is 1:4:4, together with a fungicidally acceptable inert carrier. 5. A fungicide composition containing as active ingredient A) methyl N-( 2-methoxyacstyl ) -N-( 2 , 6-xylyl ) -D , L- -alaninate ; and B) a fungicide of the group of morpholines 2,6-dimethyi-4-tridecylmorpholiπe; or the mixture of N-alkyl(C- 9 )-2,6-dimethylmorpholiπe and N-al vl(C,r,)-2,5-dlmεthyl morpholine; SUBSTITUTE together with C) methyl-bεnzimidazoiε-2-yi-carbamatε; wherein In each of the mixtures the weight ratio of the compounds A, B and C 1:4:4, togεthεr with a fuπgicidally accεptablε inert carriεr. 6 . A fungicide composition containing as active ingrediεnt a mixture of: A) one of thε following fungicidεs: methyl N-(2-methoxyacetyl)-N-(2 ! 6-xylyl)-D,L-alaπinate; methyl N-(2-furoyl)-N-(2,6-xyiyl)-D .L-alaninatε; mεthyi N-pheπylacetyl-N-(2,6-xylyl)-D.L-alaninate; ÷_-alpha-2-chIorα-H-2,6-xylylacetamido-gamma-butyrolactonε; (+_)-aIpha-_ _ N-/3-chlαrophεnyl/cyclαpropanecarboxamido_7- -gamma-butyrolactonε; 2-mεthoxy-N-/2-oxo-l,3-oxazolidiπ-3-y * I-2 ' ,6' ,-xylididε; N-isoxazolε-5-yI-N-(2,6-xylyl)-D,L-alaninε-mεthylester; N-(2, -dimethyl-pheπyl)-2-mεthoxy-N-(tεtrah dr0-2-oxo- -furanyDacεtamidε; and B) 2,6-dimethyl-4-tridecyImorphoIine; togεthεr with D) one of thε following dithiocarbamate or disulphide dεrlvativεs : manganese ethyiεnebis(dithiαcarbamatε) (polymεric); or manganese ethylεnεbis(dithlocarbamatε) (polymεric) complex with zinc salt; or polymεric zinc propyIεnεbis(dithiocarbamatε or zinc ammαπiatε ethylenebis/dithiocarbamate(-poly)εthvlεπε SUBSTITUTE SHEET thiuram disulphide^ wherein in each of the mixtures the weight ratio of thε compounds A, 3 and 0 is 1:3,5-5:10, togεthεr with a fungicidaily acceptable inert carrier. 7. A fungicide composition containing as active ingrediεnt a mixture of: A) methyl N -( 2-methoxyacetyl) -N-( 2 , 6-xyly1 ) -0 , L- -alaniπate ; and B) 2 , 6-dιmeτhyl-4-trιdecvlmorpholιne ; together with D) polymeric zinc propylenebιs( dithiocarbamate ) wherein the weight ratio of thε compounds A, B and 0 is 1:4.5-6, togetner with a fungicidaily acceptable inert carrier . 8. A fungicide comoositioπ containing as active ingredient a mixture of A) methyl N-(2-methoxvaceτ I)-N-( 2 , 6-xyly1) -D , L- -alaninatε and B) 2 ,6-dιmεthyl-4-trιdεcylmαrpholιne together with D) zinc ethylεπεbιs(dιthιocarbamatε) (polvmεπc) wherein the weight ratio of the compounds A. 3 and D is 1:4:10, together ith a fungicidallv acceptablε iner carrier . 9. A fuπgicid composition containing as active lπαrecient a mixture of: A) 2-mεthoxy-N-/2-oxo-1.3-oxazolidin-3-yi-2' ,6 ' - -xylididε; and B) a fungicide of the group of morphoiinεs: . -dimεthyI-4-tridεcylmorphαlinε; or the mixturε of N-alkyl(C 9 )-2,6-dimεthylmorpholinε and N-alkyl(C T9 )-2 J 5-dimethyl morpholine; togεthεr with 0) one of thε following dithiccarbamatε of di- sulphidε derivativεs: manganese ethylεnεbls(dithiocarbamatε) (polymeric), or manganese ethyiεnebis(dithiocarbamate) (polymεric) complεx with- zinc salt; or polymεric zinc propylεnebis(dithlocarbamate) wherein in each of the mixtures the weight ratio of the compounds A, B and D Is 1:4:4-10, together with a fungicidaily acceptable inert carrier- 10. A funglcidal method of treatment, which compr i se s the step of administering to a ' plant susceptiblε to pathogεnic fungal infεction, a fungicidaily effectivε amount of the composition dεfinεd in claim 1. 11. A fuπgicidal mεthod of trεatmεπt, which comp r i ses thε stεp of administεring to cultivatεd plants susceptible to pathogenic fungal infection a fungi¬ cidaily εffεctivε amount of thε composition dεfinεd in- SUBSTITUTESBSEF

Inventors: ANGYAN SANDOR, DETRE TAMAS, ERSEX TIBOR, HORNOK LASZLO, LENNER BRITA, LYR HORST, MARMAROSINE KELLNER KATALIN, MOLNAR ATTILA, NAGYNE HEGYI GYOENGYVER, OROS GYULA, REJTOE LAJOS, SCHUESZLER ERZSEBET, SOS JOZSEF, STRUMP MARLIES, SZEGOE ANDRAS, VIRANYI FERENC, ZANKE DIETER, ANGYAN, SANDOR, DETRE, TAMAS, ERSEX, TIBOR, HORNOK, LASZLO, LENNER, BRITA, LYR, HORST, MARMAROSINE KELLNER, KATALIN, MOLNAR, ATTILA, NAGYNE HEGYI, GYOENGYVER, OROS, GYULA, REJTOE, LAJOS, SCHUESZLER, ERZSEBET, SOS, JOZSEF, STRUMP, MARLIES, SZEGOE, ANDRAS, VIRANYI, FERENC, ZANKE, DIETER
Applicants: CHINOIN GYOGYSZER ES VEGYESZET, CHINOIN GYOGYSZER- ES VEGYESZETI TERMEKEK GYARA R.
Application year: 1988
Main classification: A01N37
IPC codes: A01N37, A01N43, A01N47, A01N53