IL43353A - Fungicidal and plant growth regulating compositions containing alpha-cyano-alpha-hydroxyimino-acetamide derivatives - Google Patents

Description

43353/2 D*y»3Bn o»n»s >n»A ntom nicies *TA3 a*Y¾t5 n Ihangicidal and plant grovrt regulating compositions containing a^cya o*&-hy0zO3^ derivatives CIBA-GEIGY AG 0. 41520 The present invention relates to new compositions for regixlating plant growth and for the control of phytopathogenic fungi, these new compositions containing, as active substances, a-cyano-a-hydroxyimino-acetamides and salts of these compounds.

The active substances contained in the new agents correspond to formula I 0 II NC-C-C-NH-R, II 1 (I) NOR2 wherein R^ represents hydrogen or aminocarbonyl, and R2 represents hydrogen, a metal ion, or an ammonium ion optionally substituted by one or more C^-C^- alkyl , dodecyl or 3-hydroxyethyl groups.

Ions denoted by R2 are, for example, ions of the following mono- or bivalent metals : alkali metals such as, e.g. sodium, potassium or lithium, alkaline-earth metals such as, e.g. calcium or magnesium, as well as iron, cobalt, zinc, manganese or copper.

If R2 denotes a bivalent cation, then the second charge is likewise neutralised by an anion Suitable C^-C^ alkyl groups are ethyl, n- propyl, i-propyl, ri-butyl, i-butyl, s-butyl, t-butyl and, in particular, methyl.

Particularly preferred compounds of formula I are those wherein R2 represents hydrogen or a sodium, potassium or calcium ion, and especially the compound 0 II NC-C-C-NH 2 NOH as free oxime or as sodium, potassium or calcium salt.

The compounds of formula I are prepared by methods known per se; they are, for example, prepared as follows: w ere n ormu ae I to V, t e sym os ^ an R2 ave the meanings given for formula I, and R represents an alkyl group, particularly, however, a methyl group.

Salts that are formed in the course of the process of preparation of the active substances can be converted by acidification into the free oxime, or by salt formation direct into other, salts . The free oxime can be converted by the usual methods into a desired salt, e.g. by addition of a metal hydroxide solution or metal salt solution.

The following examples serve to further illustrate the invention without, however, in any way limiting its scope. Temperatures are expressed in degrees Centigrade.

Preparation examples a) Preparation of a-cyano-a-hydroxyimino-acetyl-urea 50 g of cyanoacetylurea is added at 80° in the course of 5 minutes, with thorough stirring, to 50 g of sodium nitrite in 250 ml of water, and the whole subsequently heated at 100° . After everything has dissolved, stirring is continued for a further hour at room temperature, and the solution then cooled to 10° . The formed precipitate is filtered off and, with heating, dissolved in 200 ml of water. An amount of 70 ml of concentrated hydrochloric acid is now added to the solution; the whole is then cooled and filtered. The resulting a-cyano-a-hydroxyimino-acetyl-urea melts at 210° - 212° with decomposition. (compound 1) b) Preparation of the iron (II) salt of a-cyano-a-hydroxy- imino-acetyl-urea 36.2 g of iron (II) chloride in 250 ml of water is added at room temperature, with stirring, to 32 g of α-cyano-a-hydroxyimino-acetyl-urea in 250 ml of water; stirring is then continued for half an hour, after which the brown-coloured iron salt is filtered off, washed the (compound 2) melts above 300° . c) Preparation of the sodium salt of a-cyano-a-hydroxy- imino-acetamide 85 g of cyanoacetamide and 85 g of sodium nitrite are suspended in 350 ml of water. '120 g of glacial acetic acid is added dropwise to this solution, and the reaction mixture is then stirred for 18 hours at room temperature. The suspension obtained is concentrated by evaporation to a third of its volume, cooled and then filtered. The substance filtered off (consisting of 61% of sodium salt and 39% of free oxime) is dissolved in warm water, and the calculated amount (160 ml) of a 10% aqueous NaOH-solution added to the solution; This reaction mixture is concentrated, mixed with ethanol, filtered, and the filtered substance ^ washed with ethanol.

The dried final product melts at 298° (decomposition) (compound No. 3) .

Acidification of this product produces the free oxime o "'■ 0 . NC-C-C-NH NOH which melts at 183° (decomposition) (compound No. 4).

The following compounds are obtained in an analogous manner: The active substances of formula I are used for the control of diverse plant pests, such as phytopathogenic microorganisms (fungi and bacteria) . To be emphasised is their action against fungi . After application of the new agents, these microorganisms are destroyed or inhibited in growth. The new agents have a good systemic and curative action. Treated plants, parts of plants and growth substrates are protected from new infections for a certain length of time (persistent action); and even microorganisms that have penetrated into the plant tissue are destroyed.

In accordance with the present invention it has now surprisingly been found that the growth of plants may be advantageously ·— controlled or modified by the application of the compounds of the formula I.

In particular the compounds of the formula I have been found to restrict vegetative growth and/or growth in height in a variety of plant species, both mono- and di-cotyledenous such as for example grasses, cereal, crops, ornamental plants, leguminosnc and other cultures. The compounds of the formula I are. par ica ly suited for inhibiting and or regulating the growth of grasses, cereal crops and soyabean plants.

In the case of grasses, the application of the compounds of the formula I results in a slower rate of growth, so that, e.g. lawns, golf-courses and green shoulders along motor-ways and ✓turnpikes will require less frequent cutting. The economic advantages accru ng are self-evident.

With cereal crops application of the active substances results in the development of shorter sturdier stems and a concommitant improvement in fruit development.

The effect of growth inhibition in ornamental plants and ornamental shrubs is that they develop as strong, smaller plants of greater uniformity. Moverever ornamental plants normally growing to a substantial height can, by treatment with the compounds of the formula I, be cultivated as compact pot-plants.

Of these various forms of plant growth regulation the most interesting aspects for the purposes of the present invention have been found to be 1. The diminution and control of vegetative growth in grasses and cereal crops and ί 2. The diminution and control of vegetative growth in soyabean plants. 1. CONTROL OF VEGETATIVE GROWTH IN GRASSES AND CEREAL CROPS The compounds of the formula I can be used in the control and in particular retardation of growth in grasses. One of the benefits of this reduced growth in for example, lawns, sports fields and other grassed -over areas is the saving in manure and/or fertilizer and in the case of the latter the reduced frequency at which they must be mown or scythed. The prime importance of this property becomes clear when grasses on roadsides, river and canal banks, airports and the like are considered. Under normal circumstances such areas require regular mowing or scything which involves high labour and machinery costs. In addition the danger to the working for example beside highways and in airports is considerable.

In cereal crops the primary effect achieved by the compounds of the formula I is a reduction in plant size especiall height of growth. As a direct result of the reduction in height the plant gains in sturdiness, the leaves and stems grow stronger and in the case of cereals a reduction of the internodal distance results in greater resistance to bending and breaking.

The following test illustrates the effectiveness of the compounds of the invention in regulating the growth of grasses Growth inhibition in grasses (postemergence method) .

Seeds of the grasses folium perenne, Poa pratensis, Festuca ovina, and Dactylis glomerata were sown in plastic dishes filled with an earth/turf/sand mixture. After 20 days the germinated grasses were cut back to a height of 4 cm above the soil and 2 days later sprayed with aqueous spray broths of the active substance.

The amount of active substance corresponded to a rate of application of 5 kg of active substance per hectare. 21 days after application the growth of the grasses was evaluated according to the following linear rating: 1 = strong inhibition (no growth from the time of application) 9 = no inhibition (growth as untreated control) TlYe following results were obtained.

Compound Lolium Poa Festuca Dactylis perenne pratensis ovina glomerata - 9b - 43353/2 2. CONTROL OF VEGETATIVE GROWTH IN SOYABEAN PLANTS ~~—■~~ ~~~"———————————_——_——________ , > In accordance with a further aspect of the present invention it has been found that the application of compounds of the formula I as described above results in marked reduction in vegetative growth in soyabean plants. As a direct consequence of this growth inhibition it is possible to sow the soya bean plants with less space between individual rows of plants.

This results in a substantial saving of space and a consequential increase in crop yield per unit of cultivated ground .

Furthermore the treated plants have been found to develop stronger, greener leaves than untreated control plants and to produce, in proportion to the foliage, an increased, degree of blossom and fruit setting. The smaller size of the plants and the possibility of growing the plants closer together also provide better protection against flattening or other damage by wind and rain.

The extent and mode of action will of course depend on the quantity of active substance applied, the time of application and the variety of plant treated as well as upon ambient condi tions .

The following test illustrates the effectiveness of the compounds of the invention in the control of vegetative growth in soya bean plants .

Example 2 Plots of soya bean plants of the variety "Wayne" each 2 averaging 25 m were sprayed in the 5 - 6 trifoliate leaf stage with aqueous preparations of the active substance to give application rates of 2,0 and 0,5 kg/hectare of active substance. - 9c - Several plote were maintained as untreated controls.

The following Table gives the harvest yield in .Bushels /Acre as a percentage of the control harvest.

The compounds of formula I can be applied together with other suitable pesticides or plant-growth-promoting ✓agents in order to adapt the said compounds to suit the given circumstances and to broaden their sphere of action. - 9d - The compounds of formula I can be used or together with suitable carriers and/or additives.

Suitable carriers and additives may be solid or liquid, and correspond to the substances common in formulation practice, such as, for example, natural and regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders and/or fertilisers.

The agents according to the invention are produced in a manner known per se by the intimate mixing and/or grinding of the active substance of formula I with suitable carriers, optionally with the addition of, dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms : solid preparations; dusts, scattering agents, granulates, coated granulates, impregnated granulates and homogeneous granulates; liquid preparations : a) water-dispersible active-substance concentrates: wettable powders, pastes and emulsions; b) solutions . - 10 - The solid preparations (dusts, scattering agents) are V· produced by the mixing of the active substances with solid carriers. Suitable carriers are, e.g. kaolin, talcum, bole, loess, chalk, limactono, ground limestone, attapulgite, dolomite, diatomaceous earth, precipitated silicic acid, alkaline-earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium oxide, ground synthetic materials, fertilisers such as ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as bran, bark dust, sawdust, ground nutshells, cellulose powder, residues of plant extracts, active charcoal, etc., singly or in admixture with each other.

Granulates can be very easily prepared by a process in which an active substance of formula I is dissolved in an organic solvent, the solution thus obtained applied to a granulated mineral, e.g. attapulgite, SiC^, granicalcium, bentonite, etc., and the organic solvent then evaporated off.

It is also possible to produce polymer granulates by impregnation of the finished porous polymer granulates (urea/formaldehyde, polyacrylonitrile, polyesters and others), having a specific surface area and favourable predeterminable adsorption/desorption ratio, with the active substance, e.g. in the form of a solution in a low boiling solvent; and subsequent removal of the solvent. - 11 - Polymer granulates of this kind can be also sprayed in the form of microgranulates , having bulk weights of preferably 300 g/litre to 600 g/litre, with the aid of spraying equipment. Spraying can be carried out over extensive areas of useful plant crops by the use of aeroplanes . .

Granulates can also be obtained by the compacting of the carrier material with the active substances and additives, and a subsequent particle-size-reducing operation.

Furthermore, it is possible to add to these mixtures additives' stabilising the active substance and/or nonionic, anion-active and cation-active substances which improve, e.g. the adhesiveness of the active substances on plants and parts of plants (adhesives and agglutinants), and/or ensure a better wettabilit (wetting agents), as well as dispersibility (dispersing agents) .

The following substances are, for example, suitable: - 12 - olein/lime mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethylene glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin-sulphonic acid, the alkali metal and alkaline -earth metal salts thereof, polyethylene glycol ethers (^arbowaxes) , fatty alcohol polyglycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, as well as latex products.

Water-dispersible concentrates of active substances, i.e. wettable powders, pastes and emulsion concentrates, are agents which can be diluted with water to obtain any desired concentration. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface -active substances, and anti-foam agents and, optionally, solvents.

The wettable powders and pastes are obtained by the mixing and grinding of the active substances with dispersing' agents and pulverulent carriers, in suitable devices, until homogeneity is obtained. Suitable carriers are, e.g. those previously mentioned in the case of solid preparations. It is advantageous in some cases to use mixtures of different carriers. As dispersing agents it is possible to use, e.g.: condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, ^ condensation products of naphthalene or of naphthalene-sulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline-earth metal salts of ligninsulphonic acid, also alkylarylsulphonates , alkali metal salts and alkaline -earth metal salts of dibutyl naphthalenesulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols , heptadecanols , octadecanols , and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary ethylene glycols, dialkyl dilauryl ammonium chloride, and fatty, acid alkali-metal and alkaline-earth metal salts.

Suitable anti-foam agents are, e.g. silicone oils.

The active substance is so mixed, ground, sieved and strained with the above mentioned additives that the solid constituent in the case of wettable powders has a particle size not exceeding 0.02 to 0.04 mm, and in the case of pastes not exceeding 0.03 mm. For the preparation of emulsion concentrates and pastes, dispersing agents, such as those mentioned in the preceding paragraphs, organic solvents and water are used. Suitable solvents are, e.g. alcohols, benzene, xylene, toluene, dime hyljsulphoxide, and mineral oil fractions boiling in the range of 120 to 350°C. The solvents must be practically odourless, non- phytotoxic, and inert to the active substances.

Furthermore, the agents according to the invention can be used in the form of solutions; these are obtained by -fe-h-e- dissolving -QJC the active substance in suitable organic solvents or solvent mixtures. The organic solvents employed can be aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkylnaphthalenes or mineral oils on their own or in admixture with each other .

The content of active substance in the above described agents is between 0.1 and 95%.

An active substance of formula I can be formulated, for example, as follows: Dust: The following substances are used in the preparation of a) a 5% dust, and b) a 2% dust: x a) 5 parts of active substance, 95 parts of talcum; b) 2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.

The active substances are mixed and ground with the carriers. - 15 - Granulate : The following substances are used to produce a ^ 5% granulate : 5 parts of active substance, o 0.25 parts of epichlor^iydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin ( particle size 0.3 - 0.8 mm). o The active substance is mixed with epichlorhydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed on to kaolin, and »—* the acetone subsequently evaporated in vacuo.

Wettable powder: The following constituents are used for the preparation n&f a) a 40%, b) and c) a 25%, and d) a 10% wettable powder: a) AO parts of active substance, 5 parts of sodium lignin^sulphonate , 1 part of sodium dibutyl-naphthalene^sulphonate, 54 parts of silicic acid. b) 25 parts of active substance, 4.5 parts of calcium lignin^sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, - 16 - 19.5 parts of Champagne chalk, 28.1 parts of kaolin. c) 25 parts of active substance, 2.5 parts of isooctylphenoxy r-polyoxyethylene-ethan 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, •/ ' ' 46 parts of kaolin. d) 10. parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/formaldehyd condensate, 82 parts of kaolin. ■ ■ ' The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then-ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to ύ give suspensions of any desired concentration.

Emulsifiable concentrates: The following substances are used to produce a) a 10% and b) a 257e emulsifiable concentrate: a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, - 17 - I 3.4 'parts of a combination emulsifier consisting^ of fatty alcohol polyglycol ether and alkylaryl - sulphonate calcium salt, 40 parts of dimethylformamide , 43.2 parts of xylene. b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, 10 parts of· an alkylarylsulphonate/fatty alcohol - polyglycol ether mixture 5 parts of dimethylformamide , 57.5 parts of xylene.

From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration, Spray : The following constituents are used to prepare a 5% spray : 5 parts of active substance, o 1 part of epichlorhydrin, 94 parts of ligroin (boiling limits 160°-190°C). - 18 - The following tests illustrate the fungicidal properties of the active substances of formula I.

Action against Phytophthora infestans on Solanum lycopersicum a) Residual action Solanum lycopersicum plants of the same variety and in the same stage of development are sprayed with a liquor containing 0.05% of active substance (prepared with the active substance in the form of a wettable powder) ; the applied coating is allowed to dry, and the plants are then infested with a zoospore suspension of Phytophthora infestans. They afterwards remain for 6 days in a controlled- atmosphere chamber at 18° - 20° with high atmospheric humidity produced by an artificial spray. Typical leaf spots appear after this period of time, and an evaluation of the tested substance is made on the basis of their number and size.

The compounds Nos . 1, 3, 4, 12, 13, 14, 15, 16 and 23 exhibited a good action, i.e. plant infestation 5-207o. b) Curative action Tomato plants of the variety "Roter Gnom" are sprayed, after three weeks ' cultivation, with a zoospore suspension of the fungus, and incubated in a chamber at 18° - 20° with saturated atmospheric humidity.

The incubation is stopped 24 hours . After the plants have dried, they - 19 - are sprayed with a liquor containing the active substance, ^ formulated as a wettable powder, in a concentration of 0.05%. The spayed-on coating is allowed to dry, and the plants are then returned to the moist-atmosphere chamber for 4 days .

The typical leaf spots appearing after this time are used, on the basis of their size and number, for an assessment of the effectiveness of the substances examined.

The compounds Nos. 1, 2, 3, 4, 5, 11, 12, 16, 17, 18, 19, 20 and 23 exhibited a good action, i.e. plant infestation 5-20%. c) Systemic action The active substance in the form of a wettable powder is applied in a concentration of 0.05% (relative to the volume of soil) to the surface of the soil of three-week-old potted tomato plants of the variety "Roter Gnom" (red gnome) . After a waiting time of three days, the underside of the leaves of the plants is sprayed with a zoospore suspension of Phytophthora infestans . The plants are then stored for 5 days in a spray chamber at 18°.- 20° with a saturated atmosphere. The typical leaf spots appear after this time; on the basis of their number and size, an evaluation is then made of the effectiveness of the tested substances.

The compounds Nos. 1, 2, 3, 4, 5, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 and 24 exhibited a good action, i.e. 5-207© plant infestation. - 20 -

Claims (11)

1. Claims 2.10.73 1. A process for regulating plant growth which comprises for underlined meanapplying thereto a' plant growth regulating amount of a ings except compound of the formula for the processes 0 of Clains il 2 & 3. NC - C - C - NHR II N0R„ wherein R^ represents hydrogen or an^aminocarbonyl group and R2 represents an unsubstituted or mono or poly-C-^-C^-aIky1- , β-hydroxyethyl-, or dodecyl-substituted ammonium ion or a metal ion or hydrogen.

2. A process as claimed in Claim 1 , wherein in the active compound of formula I, R1 is hydrogen and is a metal ion, hydrogen or an unsubstituted ammonium ion.

3. A process as claimed in Claim 1 , wherein in the active compound of formula I, is an aminocarbonyl group and R2 is a metal ion or hydrogen..

4. A process as claimed in Claim 1 , wherein in the active compound of formula I, R^ represents hydrogen and fi^ represents a sodium ion.

5. A process as claimed in. Claim 1, wherein in the active compound of formula I, R1 and represent hydrogen.

6. A process as claimed in any one of Claims 1 to 5» wherein said compound is applied to grain crops or grasses. 2.10.73 7.

7. A process for combatting phytopathogenic fungi at a locus except for which comprises applying thereto a fungicidally effective process of Claim 8 amount of a compound of the formula i C - C NHR II N0R„ wherein represents hydrogen or an aminocarbonyl group and 33:? 3/3 - Q.

8. A process an claimed in Claim 7, wherein in the active compound of t e '.formula I, ?1 represents hydrogen and R,, represents an unsubstituted ainmoniu.-) ion. φ i — :.

9. A fungic ■idal or plant-growth regulating composition comprising a compound of the formula 0 il NC - C - C - NHR, 11 1 N0R2 wherein represents hydrogen or an aminocarbony 1 group and R2 represents an unsubstituted 'or mono or poly-C^-C^-alkyl-, /3-hydroxyethy 1- , or dodecy 1-subst ituted ammonium ion together with a solid extender and optionally a surfactant.

10. A fungicidal or plant-growth regulating composition comprising a compound of th«2 formula 0 II NC - C - C NHR. wherein represents hydrogen or an aminocarbony1 group and 2 represents an unsubs ituted or mono or poly-C^-C^ -alky 1- , μ-hydroxyethy 1- , or dodecyl- substituted ammonium ion together with a liquid diluent and a surfactant.

11. A fungicidal or plant-growth regulating composition comprising a compound of the formula 0 II NC - C - C - NIIR. 11 1 N0R wherein represents hydrogen or an aminocarbony1 group and R^ represents an unsubs ituted or mono or poly-C^-C^-alky 1- , β-hydroxyethyl-, or dodecyl- substituted ammonium ion together with a solid extender and/or a liquid diluent made up in the form of a dust, scattering agent granulate, wettable powder, paste, emulsion emulsifiable concentrate or spray. 43353/2 12· A composition as claimed in any one of .claims 9 to t1 wherein R, represents hydrogen and R_ represents an unsubstituted ammonium ion. For fhe Applicants - 23 -