A BIOCIDAL, PARTICULARLY FUNGICIDAL AND/OR BACTERICIDAL COMPOSITION AND THIOSEMICARBAZONES AND METAL COMPLEXES THEREOF FOR USE IN THE COMPOSITION

Abstract: A biocidal composition, particularly a fungicidal and/or bactericidal composition, comprising a thiosemicarbazone having the general formula (I), and their complexes formed by reaction with compounds of the metals Cu, Zn, Mn, Fe, Ca, Mg, Al, Sn and Ti and having inorganic and/or organic ligands, and salts of said compounds, in which formula Y represents CH or N, X1 represents hydrogen, straight or branched chain C1-C6 alkyl, C1-C6 alkoxy, phenoxy or halogen, and n is 1, 2 or 3, or (X1)n when taken together form a fused benzene ring, R1 represents hydrogen or straight or branched chain C1-C6 alkyl, and R2 and R3 each independently represents hydrogen, straight or branched chain alkyl or alkenyl having up to 18 carbon atoms, cycloalkyl, arylalkyl, heteroarylalkyl, aryl, substituted aryl, a heterocyclic ring containing one or more hetero atoms, acyl, hydroxy or alkoxy, alkylsulphonyl or arylsulphonyl, amino, alkylamino or dialkylamino, arylamino, hydroxyalkyl or alkoxyalkyl, aminoalkyl, monoalkylaminoalkyl or diakylaminoalkyl, alkoxycarbonylalkyl or alkylideneimino, or R2 and R3 when taken together with the nitrogen atom to which they are attached form a heterocyclic ring which may optionally contain one or more additional hereto atoms selected from O, N and S. The compounds of the invention and their metal complexes may particularly be used for combating or preventing attacks by fungi or bacteria on plants or plant material including seed material.

Description: A biocidal, particularly fungicidal and/or bactericidal composition and thiosemicarbazones and metal complexes thereof for use in the composition. The present invention relates to a biocidal, particularly fungicidal and/or bactericidal, composition comprising a thiosemicarbazone or a metal complex there¬ of which, when using the composition, exhibits hitherto unknown biocidal properties. The invention also relates to thiosemicarbazones and metal complexes thereof, and salts thereof, for use in the composition. Furthermore, the invention relates to a method for ccmbating or preventing attacks by phytopathbgenic organi__τιs on plants or plant material. The biocidal composition of the invention is characterized in that the thiosemicarbazone contained therein belongs to the group of thiosemicarbazones having the general formula I and th n with compounds of the metals Cu, Zn, Mn, Fe, Ca, Mg, Al, Sn and Ti and having inorganic and/or organic ligands, and salts of said compounds, in which formula Y represents CH or N, X, represents hydrogen, straight or branched chain alkyl having up to 6 carbon atoms, alkoxy having up to 6 carbon atoms, phenoxy or halogen, and n is 1, 2 or 3, or (X ι ) n when taken together form a fused benzene ring, R, represents hydrogen or straight or branched chain alkyl having up to 6 carbon atoms, and 12 an< 3 R3 each independently represents hydrogen, straight or branched chain alkyl or alkenyl having up to 18 carbon atoms, cycloalkyl, arylalkyl heteroarylalkyl, aryl, substituted aryl, a heterocyclic ring containing one or more hetero atoms, acyl, hydroxy. or alkoxy, alkylsulphonyl or arylsulphonyl, a ino, alkylamino or dialkylamino, arylamino, hydroxy- alkyl or alkoxyalkyl, aminoalkyl, monoalkylaminoalkyl or dialkylaminoalkyl, alkoxycarbonylalkyl or alkylidene- imino, or R_ and R, when taken together with the nitrogen atom to which they are attached form a heterocyclic ring which may optionally contain one or more additional hetero atoms selected from 0, N and S. Examples of the ligands forming part of the metal complexes of the invention include neutral ligands such as H-O, NH-, amines and phosphines, anionic ligands such as the inorganic chlorides and sulphates and the organisk alcoholates, phenolates, thiolates, 'carboxyla- tes (including substituted carboxylates and amino acid anions) , sulphonates and anions of organic CH acids, e.g. anions of β-dicarbonyl compounds. It is known that certain thiosemicarbazones and their metal complexes possess antimicrobial, antitumor, antiviral and antimalarial activities, confer the references 1-13 mentioned below, but thiosemicarbazones of the general formula I and particularly their metal complexes exhibit surprising fungicidal and/or bacteri¬ cidal activities which are substantially higher than those of, or hitherto unknown in, the known thiosemi¬ carbazones and their metal complexes as well as commer¬ cial substances of reference. References: 1. B.A. Gingras, G. Colin, and CH. Bayley; Journal of Pharmaceutical Sciences, 1965, Vol. 54, 1674-1675. 2. Japan 68 00,517 (Cl 16 E 431), 09 Jan 1968, Appl. 12 May 1965 (Takeda Chemical Industries Ltd.) , Chemi- cal Abstracts, Vol. 69 (1968), abstract No. 59112r. 3. D.M. Wiles and T- Suprunchuk, Journal of Medicinal Chemistry, 1971, Vol.14, No. 3, 252-254. 4. U.S. Patent No. 3,824,276, issued July 16, 1974. (The ϋpjohn Company, Kalamazoo, Mich.). 5. Yun Sung Chough, Hyang Sook Yoo, and Moo Bae, Seoul .University Faculty Papers, Vol. 3 (D) , Oct. 1975, 45-57. OMPI 6. W. Levinson, W. Rohde, P. Mikelens, J. Jackson, A. Antony, and T. Ramakrishnan, Annals New York Academy of Sciences, 1977, 525-532. 7. L. Heinisch, W.F. Fleck and H.-E, Jacob, .Zeitschrift fur Allgemeine Mikrobiologie, 20, 10, 1980, 619-626. 8. S.N. Pandeya and P. Ram, Indian Journal of Chemistry 1981, Vol. 20B, 9, 825-827. 9. A. Saxena, J. K. Koacher and J. P. Tandon, J. Antibact. Antifung. Agents, Vol. 9, 1981, 435-438. 10. J. P. Scovill, D. L. Klaymann, and C. F. Franchino, J. Med. Chem. 1982, 25, 1261-1264. 11. V. N. Biyushkin, Yu. M. Chumakov, Khim.-Farπi. Zh., 1982, 16, 9, 1090-1091. 12. S. Giri, Nizamuddin and U.C. Srivastava, Agric. Biol. Chem., 47, 1, 1983, 103-105. 13. C. J. Pfau, Handbook of Experimental Pharmacology, Vol 61, 147-198, 1982. It has surprisingly been found that the compounds of formula I and their metal complexes for practical requirements have a very favourable fungicidal and bac¬ tericidal activity for protecting cultivated plants. Cultivated plants are here, e.g., cereals, maize, rice, vegetables, sugar beets, soya, peanuts, fruit trees, ornamental plants, but above all grape vines, hop, cucumber plants (cucumber, pumpkin, melon) , solanaceae, such as potato, tobacco, and tomato, and also banana, cocoa, and natural caoutchouc plants. Fungi occurring on plants or parts ' of plants (fruits, blossoms, flowers, foliage,- stems , tubers, roots) can be inhibited or destroyed by the active compounds of the invention, whereby also plant parts growing up later on remain spared of such fungi. The compounds of the invention are active against phytopatogenic fungi belonging to the following classes: Ascomycetes, Basidiomycetes such as rust fungi. Fungi imperfecti, e.g., Fusarium oxysporum and Botrytis cinerea, but particularly against the Oomycetes belonging OMPI to the class of Phycomycetes, such as Pythium sp. , Phytophthora sp. , Peronospora sp., Pseudoperonospora sp., and Plasmopara sp. Furthermore, the compounds of the invention can be used for treating seed material (fruits, tubers, seed corn) and cuttings to protect them against fungal infec¬ tions and against phytopatogenic fungi occurring in the soil. The compounds of the invention are active against rot fungi belonging to the class of basidiomycetes. The compounds of the invention are bactericides which have shown activity against, e.g., Pseudomonas mors prunorum. In accordance with the above the invention rela- tes specifically to a biocidal composition as defined above intended for combating or preventing attacks by fungi or bacteria on plants or plant material, including seed material. A particularly advantageous composition of this type is intended for combating or preventing attacks by oomycetes. The invention also relates to thiosemicarbazones of the general formula I or their metal complexes or salts thereof as defined above, for use in the -fipositioπs defined above. Furthermore the invention relates to a method for combating or preventing attacks by fungi or bacteria on plants or plant material, including seed material, which method is characterized by treating the plants or plant material with an active amount of a thiosemi¬ carbazone or a metal complex thereof, or a salt thereof, as defined above. Among the compounds of formula I and their com¬ plexes mention should particularly be made of those described in Test Examples 1 to 4 below. Preparation of thiosemicarbazones. The thiosemicarbazones of the general formula I are prepared by one of the following methods known from OMPI the literature: Method 1: Reaction of a carbonyl compound with a thio- semicarbazide. Method 2: Reaction of a hydrazone with a isothiocyanate. 5 Method 3: Reaction of methyl 3-[1-(2-pyridyDethylideneJ- hydrazinecarbodithioate with an amine. These three preparation methods are described in the References A and B mentioned below. Three detailed Examples on the use of these gene- 10 ral preparation methods are given below. Example 1 (compound No. 8, method 1) A mixture of 1.55 g of 2-acetyl-4-chloropyridine, 1.45 g of 1-pyrrolidinethiocarbohydrazide, 0.5 g of glacial acetic acid, 0.5 g of potassium acetate and 50 ' 15 ml of ethanol is boiled under reflux for 7 hours. On cooling to 20°C and filtering the thiosemicarbazone is obtained as yellow needles of melting point 160-161 C. Example 2 (compound No. 25, method 2) A mixture of 1.35 g of 2-acetylpyridinehydrazone, 20 1.49 g of 3-tolyl isothiocyanate and 25 ml of diethyl ether is stirred for 4 hours at 20 C. The precipitated crystals of the thiosemicarbazone 25 are filtered off and recrystallized from methanol and has a melting point of 148-150°C. 25 Example 3 (compound No. 17, method 3) A mixture of 2.25 g of methyl 3-[1-(2-pyridyl)- ethylidene]hydrazinecarbodithioate, 2 g of furfuryl ami¬ ne and 50 ml ethanol is boiled under reflux for 7.hours. On cooling to 20 C the thiosemicarbazone ' 17 is precipi- 30 tated which is filtered off and washed with ethanol and has a melting point of 144-146 C. References: A. D. L. Klayman, J. F. Bartosevich, T. S. Griffin, C.J. Masonand J. P. Scovill, J. Med. Chem. 22., 855, 1979. 35 B. D. L. Klayman, J. P. Scovill, J. F. Bartosevich & C. J. Mason, J. Med. Chem. 22., 1367, 1979. The thiosemicarbazones prepared according to the Examples 1 to 3 are tabulated in Table I below together with a number of further thiosemicarbazones of the in¬ vention prepared in a similar way. > . Preparation of thiosemicarbazone complexes. Complexes of the thiosemicarbazones of the inven¬ tion are prepared by reacting the latter with metal salts of inorganic or organic acids, optionally in the presence of neutral ligands. The preparation takes place by dissolving the two starting materials - together or separately - usually at elevated temperature in suitable solvents such as water, methanol, ethanol, ethylene chloride, acetonitrile and dimethylformamide (DMF) or combinations thereof. The temperature at which the starting materiale have been combined is maintained for a shorter or longer time, whereupon the reaction mixture is filtered, if necessa¬ ry, before cooling. On this cooling the product often crystallizes, but it may be necessary to add another solvent in order to promote this crystallization, or to evaporate the reaction mixture. Subsequently the products may be recrystallized from various solvents. After this general preparation procedure two de- tailed Examples will now be given. Example 4 (compound No. 204) . 3.2 g (0.015 mole) of cupric glycolate is suspen¬ ded i 200 ml of DMF at 100°C, and 3.3 g (0.015 mole) of 2-acetylpyridine-N 4,N4-dimethyl-3-thiosemicarbazone dissolved in 20 ml of hot DMF is added thereto while stirring. The stirring was continued i 2 1/4 hours at 60 C and then in 48 hours at room temperature. Filtering of the reaction mixture and drying of the matter filte¬ red off gave 4.4 gof product which was recrystallized from methanol. The product isolated therefrom had a melting point of 212°C (dec). Example 5 (compound No. 102) . ' 4 4.0 g (0.016 mole) of 2-acetylpyridine-N ,N -te- tramethylene-3-thiosemicarbazone was dissolved in 100 ml of hot methanol, and 2.15 g (0.016 mole) of cupric chloride dissolved in 50 ml of hot methanol was added . thereto while stirring. The stirring was continued for 24 hours at room temperature. ' Filtering of the reaction mixture and drying of the matter filtered off gave a product which was directly recrystallized from DMF.After cooling a product was isolated by filtering and drying which had a melting point of 290 C. The composition of the compound was determined by microanalysis. C 12 H 15 C1CuN 4 S rec 3 uires: c 41 - 61 , H 4 - 37 , cl 10.23, N 16.18%. Found: C 41.50, H 4.41, Cl 10.18, N 16.60%. Related compounds are mentioned in the following references: C. J. P. Scovill, D. L. Klayman and C. F. Franchino, J. Med. Chem. 25, 1261-1264, (1982). D. Y. K. Bhoon, S. Mitra, J. P. Scovill and D. L. Klay¬ man, Transition Met. Chem. 1_, 264-266, (1982). The thiosemicarbazone complexes prepared accor- ding to the Examples 4 to 5 are tabulated in Tables II to IV below together with a number of further thiosemi¬ carbazone complexes of the invention prepared in a similar way. - OREΛ OMPI Λ Table IV The compounds of the invention may be formulated as compositions such as wettable powders, dusts, gran¬ ules, solutions, emulsifiable concentrates, emulsions, suspension concentrates or aerosols. Wettable powders are usually formulated to con¬ tain 25, 50 or 75% of toxicant and usually contain, in addition to solid carrier, 3-10% by weight of a disper¬ sing agent and, where necessary 0-10% by weight of sta¬ bilisers and/or additives such as penetrants or stickers. Dusts are usually formulated as a dust concentra¬ te having a similar composition to that of a wettable powder but without a dispersant and are diluted in the field with further solid carrier to give a composition usually containing 1/2-10% by weight of toxicant. Granu- les are usually prepared to have a size between 10 and 100 BS mesh, (1.676-0.152 mm) and may be manufactured by agglomeration or impregnatio techniques. Generally, granules will contain 1/2-25% by weight toxicant and 0-10% by weight of additives such as stab- ilisers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w/v toxicant, 2-20% w/v emulsifiers and 0-20% w/v of appropriate additives such as stabilisers, penetrants and corrosion inhibitors. Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 10-75% by weight of toxicant, 1/2-15% by weight of dispersing agents, 0.1- 10% by weight of suspending agents such as protective colloids and thixotropic agents, 0-10% by weight of appropriate additives such as defoa ers, corrosion in¬ hibitors, stabilisers, penetrants and stickers, and as carrier, water or an organic liquid in which the toxi¬ cant is substantially insoluble. Certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as antifreeze agents for water. Aqueous dispersions and emulsions, . for example. compositions obtained .by diluting a wettable powder or a concentrate according to the invention with water, - also lie within the scope of the present invention. The - said emulsions may be of the water-in-oil or of the 5 olie-in-water type, and may have a thick "mayonnaise"- like consistency. The compositions may also contain other ingredi¬ ents, for example, other compounds having pesticidal, particularly acaricidal, herbicidal or fungicidal pro- 10 perties. The activities of the compounds of the invention are illustrated in detail by the following Test Examples. Test Example 1 15 Agar plate test. Testing for fungistatic activity and the breadth of the activity spectrum. Solvent: Ethanol. Test concentration in ppm (mg substance per 1 agar) : 20 200, 20, 2, O.Z. The solution of activ substance is added to ste- ril agar liquefied by heating, in such an amount that the desired concentration of active substance therein is obtained. After thorough shaking to uniform distribution 25 of the active substance, the agar is poured into Petri dishes under sterile conditions. After solidification of the mixture of substrate and active substance, test fungi from pure cultures are inoculated thereon in discs of a diameter of 5 mm. The Petri dishes are left 30 in 5x 24 hours at 22 C for incubation. After this period the inhibitory effect of the active substance on the mycelial growth is determined in categories in relation to untreated control dishes. + no mycelial growth 5 - mycelial growth, but inhibited in relation to control o mycelial growth like control. Active substances, concentrations of active sub¬ stance, test fungi and inhibitory effect obtained appear from the Table below. OMPI Agar plate test Cαn- Test con¬ o o =_. zc pσuid centration V, — < = No. ppm 200 + • + . 1 20 -r - + + ? — 0 + 0 0,2 + 200 + + -r- 2 20 + + -. 0 0 -*- 0, 200 + + + 20 + + 2 + 0, 200 X + 20 + 2 0,2 :oo 20 0,2 200 20 • > 0,2 OMΠ Agar plate test con¬ . Cαn- Test pouπl centration No. ppm 2Q0 20 9 -> 0,2 200 -i- + 10 20 -> o 0,2 200 ■ + 20 + + 11 • > Q,2 200 + 12 20 + o 0,2 200 + 20 O + 13 2 o 0,2 200 + 20 o 14 7 0,2 200 + 20 o 15 z> 0,2 200 + + + o o -f 16- 20 2 ' 0,2 Agar plate test —I !Λ mm ZZ = — ■ n o — • ^_ .— — — * Ξ -— s_ __ _ ™-l 5-s. _; « # _ — — — o 3 3 iJ o • — 3- ϋ *— — 3 3 * — . X — Ξ o _= C • __ 3. ϋ O «-, __. ~ -J. - O N e •-. ϋ •— - Cαn- Test con¬ _ _ • X. i-s ~> __ -J — — — -^ i. o - pourrl centration — — O — ■ <; — i" c o * 3- c " i*s— =_: - '-_ -J No. ppm 17 200 - -r + ÷ 20 O + . + ~> 0 0 - 0,2 200 18 20 o,-: 200 - + + + 19 20 o o o o 0, 20 200 + + 20 0 n 0 o,: 200 21 20 - + o o 0,2 20C o - o 22 20 . o o,- Agar plate test Com¬ Test con¬ pound centration No. ppm 200 +• + 25 20 — — O -> 0 0 0,2 200 + ^. 26 20 0 o 2 0 0,2 200 + -f- 27 20 -r o 0,2 200 28 20 2 + 0,2 Agar plate test ' • x. V. o O -*-ι Can- Test con¬ zz> — 'X. • X. >s pound centration 3 X < = No. ppm 33 200 20 -> 0,2 + + 36 200 20 O + 2 0 0,2 37 200 20 -> 0,2 39 200 20 -> 0,2 OMPI Agar plate - test V * re re -— J- re tr. o O —i -H •* *■ _ t" C 3 * -• — K *J >-. E Co - Test .concen- ~1 "7 £_ *-> ϋ —I C O JZ 3 >s J- o c o _o C_ O ΌOUΠG tration in o c* -^-— re c. »- α •*- ) re •r . ϋ o _c *-> c • ι— ^ C J- o re NO. o in—i 3 _: __ >-; -** ■ "- -J= o O V r-. J- < c c c u. c εa u C- ir. U U ; xi 200 + + 4 4 4 + - 4 4 •+ 100 20 2 + + — — 4 4 0.2 200 + + 101 20 + + 2 + 0,2 200 + + + + 102 20 + + + + 2 + + 0,2 200 + + 03 20 + + 2 + 0,2 + 200 + + + + + 04 20 + + + 4 + 2 + + + 0,2 + + 200 + + + 4 4 4 4 4 05 20 + + 4 + 4 4 4 4 2 + + + + 0.2 4 200 + + + + + 06 20 + + + + + 2 + + + + 0.2 ■ + 4 200 + +- 4 4 4 07 20 + 4- 4 4- 4 4 2 + + 4 4 0,2 + 4 -^JRSX o I I O I I O I I + o i i + O I + + O + + O I + + O I I I Λsperpillus niger > Ώ O I + + O I I + I + + + I 4- + + 1 4. , 1 4- + + + + + + 4 + + 4 Pullularin pulInland H 1-* O I I + O i l I I + + 1 1 + 1 1 4 + 1 1 + 1 1 4 . I l l Pus rium fu oxysporum ct (0 et + + + + + + + + + + + + + + 4 4 4 4 4 + 4 4 4 4 4 4 4 4 4 4 4 4, Pyt ium (D to ultimum et O I + + O l l l I + + 4 1 4 4 4 1 4 4 4 1 4 + 1 4 + 4 I I, I Hotrytis cincrca O I I + O l l l 1 + + 4 4 4 + 1 4 4 4 1 4 4 4 1 4 4 4 I I I I Rhi zoctonia solani Agar plate test Com¬ Test concen¬ pound tration in No. ppm 200 4 4 4 4 4 4 4 4 4 4 208 20 2 4 4 - 4 0.2 4 200 4 4 4 4 4 -209 20 4- 4 4 4 4 2 4 4 4 0.2 200 4- 4 4 4- 210 20 4 4 4 4 2 4 0.2 200 4 4 4 4 4 4 211 20 4 4 4- 4 4 4 2 :-+ 4 4 4 4 0.2 o 200 4 4 4 212 20 4 4 4 2 ' 4 0.2 o 200- 4 4 4 4 21-3 20 4- 4 4 4- 2 4 0,2 + 200 20 2 0,2 200 20 2 0,2 Agar plate test 200 -. __. X + + 30.0 20 — + - + + + 2 " 4 + — 0,2 0 200 + 301 20 + 2 0,2 200 4 302 20 + X -> 0,2 200 303 20 7 0,2. 200 304 20 2 0,2 200 305 20 2 0,2 200 306 20 2 0,2 Test Example 2 Seed dressing test. Testing for protective activity against decay of bean seedlings caused by Pythium ultimum. Solvent: 10% acetone in water. Emulsifier: Triton X-155 100 ppm. Test concentrations in ppm (mg of substance per liter of solvent) : 400, 200, 20 and 2. In dressing beans, they are immersed in a solu- tion of active substance for one minute and air-dried, 10 beans being immersed for each test concentration. The beans are incubated in closed Petri dishes, on moist filter paper inoculated with Pythium ultimum, for 6 x 24 hours at 22°C. Thereby the germination of the beans and the mycelial growth of Pythium ultimum are initiated. After this period of time the number of healthy seedlings are determined in relation to untreated, non-inoculated control dishes. The more active the active substance is, the more seedlings are healthy. Active substances, concentrations of active sub¬ stances in the dressing solution and the number of healthy seedlings in % appear from the Table below. Seed dressing test Con- Test concentration pound in ppm % Heait. No, ώ00 80 200 90 1 20 60 2 10 400 80 200 60 2 20 20 2 0 400 100 7 200 100 20 80 2 10 400 100 200 90 37 20 70 ? 30 >., Seed dressinα test Compound Test concentration No. in ppm % Healthy seedlinos 400 100 100 200 60 20 40 -> 10 400 70 102 200 50 20 30 10 400 90 103 200 90 20 0 7 400 100 104 200 100 20 10 2 0 400 100 105 200 90 20 60 20 400 100 106 200 90 20 • 50 ? 0 400 90 07 200 90 20 70 0 Seed dressinα test Compound Test concentration ?ά Healthy seedlings No. in ppm 400 100 200 200 100 20 100 50 400 ' 100 201 200 100 20 60 10 400 90 202 200 60 20 30 n 0 400 80 203 200 70 20 60 ? 10 400 90 204 200 80 20 70 • > 20 400 80 205 200 80 20 70 *> 0 400 80 06 200 20 20 10 -* 0 400 100 0 ' 200 100 20 90 •*• 10- 400 80 08 200 70 20 60 ? 20 400 90 09 200 80 20 60 ? 10 Seed dressinα test Compound Test concentration in ppm Healthy seedlings NO. 400 90 210 200 80 20 60 2 0 400 100 211 200 60 20 40 2 10 400 90 212 200 80 20 80 2 10 400 100 213 200 70 20 70 2 40 Seed dressiπα test Compound Test concentration No. in ppm % Health 400 100 300 200 90 20 40 2 20 400 80 302 200 80 20 50 2 10 400 100 303 200 80 20 10 2 0 400 . 90 304 200 0 20 2 400 100 305 200 80 20 80 2 10 Comparative Tests To compare the activity of the compounds of the invention to the activity of known commercial fungici¬ des of the formulae A, B, C, D, E, and F and to the activity of a thiosemicarbazone and its metal complex of similar, structures having the formulae G and I, tests were carried out according to the methods stated in the Examples 1 and 2. + C opper OMPI Agar plate test Comparative test Com- Test concen- pound tration in No. ppm 200 + 20 + 2 + , 0.2 O O B 200 + 20 * 2 o o 0 .2 o 200 o 20 - + o . o ' 2 0.2 200 •+ + + + + 20 + + - + «*• 2 -+ 0.2 200 •+ 20 ■ + + 2 + 0.2 200 + + + + 20 + + + . + + 2 + o 0 .2 o 200 o 20 2 0.2 200 + + 20 + + + 2 + o 0.2 oro O I + O Aspergillus niger + + + + O Pullularia pullulans 1 1 + 4 O w Fusarium . oxysporum « + + + 4 O. Pythium ultimum I 1 + + Botrytis cinerea Seed dressinα test Comoarative test Compound Test concentration No. % Healthy seedlings in ppm 400 A 200 20 -> B 400 200 20 2 400 90 C 200 SO 20 40 2 0 400 D 200 20 2 400 E 200 20 ' F 400 20 200 20 2 G 400 200 20 2 1. 400 SO 200 20 2 I 400 200 20 2 104 400 100 200 20 2 Test Example 3 Bacterial growth inhibition test. Testing of bactericidal activity against Pseudomonas mors prunorum. Solven : Ethanol. Test concentrations in ppm (mg of substance per liter og solvent): 500, 250, 125. Active substance is dissolved in ethanol in an amount such as to obtain the concentration required. Filter paper discs of 13 mm in diameter are immersed therein, air-dried and placed in Petri dishes (90 mm) with cooled solidified meat peptone agar inoculated on the surface with the test organism. The Petri dishes- are incubated in 48 hours at 22°C. After this period of time the inhibitory effect of the active substance is ' determined, the radius of the zone of inhibition being measured and recorded in % of the maximum inhibition which is obtained by using 250 ppm of chloramphenicol. Bacterial αrowth inhibition test Compound Testconcentration Inhibition No. in p .- 1 '*• 500 100 250 81 125 62 7 500 100 250 6ό 125 25 4 500 67 250 53 125 33 8 500 61 250 53 125 39 500 ' 92 18 250 61 125 50 500 100 37 ' 250 87 125 65 Bacterial qrowth inhi b iti on test Compound Testconcentration % Inhibition No. in ppm 500 100 72 250 47 125 44 500 67 104 250 56 125 53 1Q5 500 67 250 56 125 44 500 67 107 250 44 125 59 Bacterial αrowth inhibition test Compound Testconcentration % Inhibition No. in p r^ 500 83 201 250 58 125 500 61 202 250 125 500 61 203 250 50 125 33 500 50 204 250 33 125 17 ' 500 88 205 250 67 125 • 25 500 80 207 250 61 125 47 208 500 70 250 67 125 56 500 61 210 250 56 125 39 500 72 211 250 67 125 50 300 . 500 72 250 67 125 Δ 303 500 65 250 50 125. 44 306 500 56 250 50 125 33 OMPI A. wi TEST EXAMPLE 4 Potato Late Blight Test Testing for protectant activity of foliar applied against potato late blight caused by Phytophthora infest- ans. Solvent; 10% acetone in water Emulsif±er: Triton X-155 lOOppm Test concentration in ppm (mg of substance per liter of solvent): 260, 130, 65, 33, 16, 8. Potato plants with 5-7 expanded leaves were sprayed until run off with the test compound.Two hours after the sporangialsuspension is sprayed directly onto the treated plants, which immediately are placed in a humid chamber, 100% RH and an air temperature of 18°C. After two days under these conditions, the plants are placed in a growth chamber with 70-80% RH and an air temperature of 18°C. 7-10 days after inoculation the plants are rated on a scale of 0 -10 where 0 = no disease control to 10 = 1QQ% disease control. POTATO LATE BLIGHT TEST Compound Rate Rating No. ppm 250 10 130 10 65 8 33 8 16 4.5 iόL. 10 1 0 10 65 10 33 10 . -lO & 5 37 10 130 10 65 10 33 9 15 o 8 260 130 £5 33 15 3 s i_rU lc 26-C * 65 33 16 POTAT O L ATE BL I GHT TEST - Compound Rate Rating No. ppm 100 260 20 130 10 65 10 33 10 x• * -* 10 6 9.5 104 260 10 130 10 65 10 33 10 16 10 8 10 105 260 10 130 10 65 10 33 ID 16 10 B , 8 106 260 10 130 10 65 10 33 9 16 9 3 6 107 260 10 130 10 65 10 33 10 2-. 9.5 6 9.0 201 260 - ID 130 10 65 10 33 10 16 8.5 8 5 204 260 10 130 10 65 10 . 33 10 16 10 8 10

Claims: Patent Claims 1. A biocidal composition, particularly a fungicidal and/or bactericidal composition, comprising a thiosemicarbazone which, when using the composition, exhibits hitherto unknown biocidal properties, characterized in that said thiosemicarbazone belongs to the group of thiosemicarbazones having the general formula I and their complexes formed by reaction with compounds of the metals, Cu, Zn, Mn, Fe, Ca, Mg, Al, Sn and Ti and having inorganic and/or organic ligands, and salts of said compounds, in which formula Y represents CH or N, X, represents hydrogen, straight or branched chain alkyl having up to 6 carbon atoms, alkoxy having up to 6 carbon atoms, phenoxy or halogen, and n is 1, 2 or 3, or (X-ι) n when taken together form a fused benzene ring, R, represents hydrogen or straight or branched chain alkyl having up to 6 carbon atoms, and R_ and R- each independently represents hydrogen, straight or branched chain alkyl or alkenyl having up to 18 carbon atoms, cycloalkyl, arylalkyl, heteroaryl¬ alkyl, aryl, substituted aryl, a heterocyclic ring containing one or more hetero atoms, acyl, hydroxy or alkoxy, alkylsulphonyl or arylsulphonyl, a ino, alkyl- amino or dialkylamirio, arylamino, hydroxyalkyl or alkoxyalkyl, aminoalkyl, monoalkylaminoalkyl or dialkyl- aminoalkyl, alkoxycarbonylalkyl or alkylideneimino, or R_ and R 3 when taken together with the nitrogen atom to which they are attached form a heterocyclic ring which may optionally contain one or more additional hetero atoms selected from 0, N and S. 2. A composition according to claim 1, intended for combating or preventing attacks by fungi and bacteria on plants or plant material, including seed material. 3. A composition according to claim 2, intended for combating or preventing attacks by oomycetes 4. Thiosemicarbazones or their metal complexes, or salts thereof, as defined in claim 1, for use in a composition as claimed in claim 1, 2 or 3. 5. A method for combating or preventing attacks by fungi or bacteria on plants or plant material, including seed material, characterized by treating the plants or plant material with an active amount of a thiosemicarbazone or a metal complex thereof, or a salt thereof, as defined in claim 1.

Inventors: JACOBSEN NIELS, KLEMMENSEN PER DAUSELL, KOLIND-ANDERSEN HANS, SVENDSEN AXEL KRISTIAN, WENGEL ANITA, JACOBSEN, NIELS, KLEMMENSEN, PER, DAUSELL, KOLIND-ANDERSEN, HANS, SVENDSEN, AXEL, KRISTIAN, WENGEL, ANITA
Applicants: CHEMINOVA AS, A/S CHEMINOVA
Application year: 1984
Main classification: A01N47
IPC codes: A01N37, A01N47, C07D213, C07D215, C07F1, C07F3, C07F13, C07F15