DE3013921A1 - Herbicidal agents contg. nucleoside derivs. - e.g. cyclo:cytidine, n-benzyl-adenosine or cytosine arabinoside - Google Patents

Abstract

New herbicidal agents contain at least one nucleoside deriv. of formula (I) or at least 1 physiologically tolerable acid addition salt thereof (where R1 is an N-glycosidically linked, opt. substd. residue of a purine or pyrimidine base and R2 is H, OH, amino, N3 or a residue -O-CO-R5 in which R5 is alkyl, provided that when R1 is the residue of a pyrimidine base and R2 is an OH group (is to R1 the cpd. can also be present in the form of the corresp. cycloanhydro-pyrimidine form; R3 is H, OH, amino, N3 or a residue -O-CO-R5, provided that R2 and R3 are not simultaneously amino and/or N3; and R4 is H or -CO-R5). With the exclusion of the nucleosides 9-beta-D-arabinofuranosyl-adenine and 2'-amino-2'-deoxy-9-beta-D- arabinofuranosyladenine. (I) influence plant growth and can be used as defoliants, desiccants, haulm-killing agents, germination inhibitors and, especially, herbicides. Depending on the rate of application, (I) can be used as total or as selective herbicides. Some cpds. (I) also have fungitoxic activity.

Description

Herbicidal agents based on nuceoside derivatives

The present invention relates to the use of widely known Nucleoside derivatives as herbicides.

It is already known that the nucleosides 9-B-D-arabinofuranosyladenine (Arabino-adenosine, ARA-A) and 2'-amino-2 2'-amino-2'-deoxy-9-B-D-arabinofuranosyladenine (Herbiplanin) can be used as herbicides (see JP Patent Application No. 54/41 327 or Hoppe-Seylers Physiol. Chem. Vol. 361 (1980)). The effectiveness of this However, connections is not always completely satisfactory.

It has also become known that certain nucleoside derivatives of are of medical interest (see e.g.

J. Amer. Chem. Soc. 77, p. 5911 (1955) and Cell and Tissue Research 186, p. 269 (1978)). However, there is no known herbicidal activity of these substances.

It has now been found that the nucleoside derivatives of the general formula in which R1 stands for each N-glycosidically linked, optionally substituted radicals of purine bases, pyrimidine bases or 6-azauracil, R2 stands for hydrogen, hydroxy, amino or the radicals -N3 or -O-CO-R5, where in the cases where R1 stands for the remainder of a pyrimidine base and R2 for - relative to R1 - cis-position hydroxy, the compounds (1) can also be in the corresponding cycloanhydro-pyrimidine form, 3 R3 for hydrogen, hydroxy, amino or the radicals - N3 or -o-Co-R5, with the proviso that R2 and R3 do not simultaneously stand for amino and / or the radical -N3, 5 R4 stands for hydrogen or the radical -CO-R5 and R5 stands for alkyl, However, the nucleosides 9-ß-D-arabinofuranosyladenine and 2'-amino-2'-deoxy-9-ß-D-arabinofuranosyladenine are excluded, and the physiologically acceptable acid addition salts of the compounds of the formula (I) have good herbicidal properties exhibit.

Surprisingly, the nucleoside derivatives which can be used according to the invention show of formula (I) a better herbicidal activity than the aforementioned, from the Prior art known nucleoside derivatives, which chemically and in terms of action are the closest connections. The use of the substances according to the invention of formula (I) thus represents an enrichment of the technology.

The nucleoside derivatives which can be used according to the invention are by the Formula (I) generally defined. In this formula R1 preferably stands for in each case N-glycosidically linked, optionally substituted residues of the purine bases purine, Adenine, hypoxanthine and guanine, the preferred substituents being: Hydroxy, amino, halogen (especially chlorine), alkyl with 1 to 4 carbon atoms and nitro. In addition, the amino group of the adenine can optionally be substituted be through alkyl of 1 or 2 carbon atoms, through furylmethyl, through optionally in the phenyl part by halogen (especially chlorine) or alkyl having 1 to 4 carbon atoms substituted phenyl or benzyl, as well as by alkylcarbonyl with 1 to 4 carbon atoms in the alkyl part. R1 furthermore preferably stands for each N-glycosidically linked, optionally substituted radicals of the pyrimidine bases Cytosine, uracil and thymine, the preferred substituents being: Amino, halogen (especially chlorine), alkyl of 1 to 4 carbon atoms and nitro. R1 also preferably represents the optionally substituted 6-azauracil radical, preferred substituents being: amino, halogen (in particular Chlorine) and alkyl with 1 to 4 carbon atoms.

R2, R3 and R4 also preferably have the meanings given above. R5 preferably represents alkyl having 1 to 4 carbon atoms.

The active ingredients to be used according to the invention are for the most part already known (cf. e.g. Chem. Ber. 109, p. 433 (1976); J. Heterocycl. Chem. 7, p. 713 (1970); J. Org. Chem. 39, p. 1564 and p. 2182 (1974), Biochem.

et Biophys. Acta. 220, p. 491 (1970) and Cancer Research 20, p. 1362 (1960)). They are obtained by adding the appropriate bases - according to the definition from R1 -n-glycosidically linked in the usual way with the corresponding sugars and optionally derivatized on functional groups in a generally customary manner (see.

also the following preparation examples).

For the preparation of the acid addition salts of the compounds gene of the formula (I) are all physiologically acceptable acids. These include preferably the hydrohalic acids such as hydrochloric acid and hydrobromic acid, especially hydrochloric acid, also phosphoric acid, Nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, e.g. fumaric acid, acetic acid, maleic acid, succinic acid, tartaric acid, citric acid, Salicylic acid, sorbic acid, lactic acid, and sulfonic acids such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid.

The salts of the compounds of the formula (I) can be used in a simple manner by customary salt formation methods, e.g.

by dissolving a compound of formula (I) in a suitable inert one Solvent and adding the acid such as hydrochloric acid and in a known manner, for example by filtering off, isolated and optionally by Wash with an inert organic solvent.

Preparation examples Example 1 150 mg (0.00056 mol) of arabinoadenosine are added to 50 ml of acetic anhydride and the mixture is stirred at 1000 ° C. for 4 hours. It is then concentrated in vacuo. 195 mg (80% of theory) (9-N-, 2 ', 3', 5'-O) -tetraacetylarabinoadenosine (1) are obtained as a viscous oil.

In a manner which is also generally customary, the following can be used Compounds listed in Table 1 are produced.

Table 1 Example compound according to formula (I) melting No. point (OC) NH (2) HO-CH2 0 \ | 185-87 HH HO H NH NH2 (3) X> 190-92 2 HHH HO r L NH, t N> -CH2 | 193-94 H HNH, Table 1 (continued) Example compound according to formula (I) melting No. point (OC) STH, 0 f) (5) 0 \ jX 0 209-11 H HH H HO H NH (6) HO-CH2β4ç1C1 (dec.) xHCl (dec.) H0 0 I. HO HO-CH2Xz Os, / xHCl 247-49 (7) W / k (decomp.) HO H Table 1 (continued) Example compound according to formula (I) melting No. point (OC) NH-CH, iNf (8) HO-CH2 OXI 184-86 H H HH HO OH 0 O; N) (9) HO-CH to iX 157-59 HO \ 2 / H E. 0 BrY 8th (10) HO-CH2? << 9 191-94 HH H NO H HO Table 1 (continued) Example compound according to formula (I) melting No. point (OC) NHC7) 1 NyN \ (11) HO-CH2 o +; 152-54 H HHH HO OH NH, (12) <2234-36 HIGH, HG "according to HH HO 2 Ni 191-94 (13) HO-CH x HCl (dec.) HH HO H H Table 1 (continued) Example compound according to formula (I) melting No. point (OC) 0: a, N, (14) EO O 4 164-65 HHH H <H H, N (15) öw51N 260 HIGH, H OH NH, N / 250-51 (16) 250-51 HO-CH8 NH2H H OH Table 1 (continued) Example compound according to formula (I) melting No point (° C) NH2 (17) HO-CH2 0.4 245-47 1 'R HO H H2 NH, (18) X> 350 2 HR HO N3 H NH, % NN " (19) O-CH2 | 177-78 Ns HH H OH The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, haulm killers, sprout inhibitors and, in particular, as weed killers. Weeds in the broadest sense are to be understood as meaning all plants which grow in locations where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, for example, in the following plants are used: Dicot weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Monocot weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

However, the use of the active ingredients according to the invention is by no means limited to these genera, but extends in the same way to other plants.

The compounds are suitable depending on the concentration for total weed control e.g. on industrial and railway systems and on paths and Places with and without trees. Likewise, the compounds can be used for weed control in permanent crops e.g. forest, ornamental wood, fruit, wine, citrus, nut, banana, Coffee, tea, rubber, oil palm, cocoa, berry fruit and hops plants and for selective weed control can be used in annual crops.

The active compounds according to the invention can be used as such or in their formulations can also be used in a mixture with known herbicides for weed control, finished formulation or tank mixing is possible.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, impregnated active ingredients Natural and synthetic materials and finest encapsulation in polymer materials.

These formulations are prepared in a known manner, e.g. by mixing the active ingredients with plug-in agents, i.e. liquid solvents and / or solid carriers, optionally using surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents Means.

In the case of using water as an extender, e.g. organic solvents can be used as auxiliary solvents. As a liquid solvent are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water.

The following can be used as solid carriers: E.g. natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals such as fumed silica, alumina and Silicates; as solid carrier materials for granulates are possible: e.g.

broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic Flours and granulates made from organic material such as sawdust flour, Coconut shells, corn on the cob and tobacco stalks; as an emulsifier and / or foam generator Agents are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as Alizarin, azole, metal phthalocyanine dyes and trace nutrients such as salts of Iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active ingredients which can be used according to the invention can be used as such or in their formulations also as a mixture with known herbicides for weed control Find use, finished formulation or tank mixing is possible. Even a mixture with other known active ingredients, such as fungicides, insecticides, acaricides, Nematicides, Protective substances against bird damage, growth substances, plant nutrients and soil structure improvers is possible.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granulates can be used. It is used in the usual way, e.g. by pouring, squirting, spraying, Sprinkle.

The active ingredients according to the invention can both before and after Emergence of the plants are applied.

The application is preferably before the emergence of the plants, that is in the pre-emergence procedure.

They can also be incorporated into the soil before sowing.

The amount of active ingredient used can fluctuate over a wide range. It essentially depends on the type of effect you want. In general the application rates are between 0.1 and 50 kg of active ingredient per hectare, preferably between 1 and 30 kg / ha.

Some of the active ingredients of the formula (I) are also fungitoxic Efficacy, for example compounds (1), (9), (11) and (14).

Examples of use Pre-emergence test: In bowls filled with vermiculite are filled, seeds of cress (Lepidium) and millet (Panicum) are laid out.

The dishes are then poured with a Hoagland nutrient solution, the the active ingredients according to the invention and the known compound (A) in certain amounts are added.

After 2 weeks the degree of damage to the plants is compared to rated the untreated plants. It means: 0% = no effect (like untreated Control); 100% = total destruction.

Active ingredients, application rates and results are based on the following Table 2 shows.

The known compound (A) of the formula is used as a comparison agent: 9-ß-D-arabinofuranosyladenine (arabino-adenosine).

Table of pre-emergence test / greenhouse efficacy rate % Kill (see Table 1) kg / ha Lepidium Panicum (A) 25 95 75 (known) (6) 25 100 90 (7) 25 100 90 (8) 25 100 90 (13) 25 100 90

Claims (4)

Claims 1. Herbicidal agents, characterized by a content of at least one nucleoside derivative of the general formula in which R1 stands for each N-glycosidically linked, optionally substituted radicals of purine bases, pyrimidine bases or 6-azauracil, R2 stands for hydrogen, hydroxy, amino or the radicals -N3 or -o-Co-R5, in the cases where R1 stands for the radical of a pyrimidine base and R2 stands for - relative to R1 - cis-position hydroxy, the compounds (I) can also be present in the corresponding cycloanhydro-pyrimidine form, 3 R3 stands for hydrogen, hydroxy, amino or the radicals -N3 or -o-Co-R5, with the proviso that R2 and R3 do not simultaneously stand for amino and / or the radical -N3, R4 stands for hydrogen or the radical -CO-R5 and 5 stands for alkyl, -R stands for Alkyl is, -which, however, excludes the nucleosides 9-BD-arabinofuranosyladenine and 2-amino-21-deoxy-9-β-D-arabinofuranosyladenine, -or on at least one of the physiologically acceptable acid addition salts of the compounds of the formula (I). 2. A method of combating weeds, characterized in that that nucleoside derivatives according to claim 1 on the weeds or their habitat can act. 3. Use of nucleoside derivatives according to claim 1 for combating of weeds. 4. Process for the preparation of herbicidal agents, characterized in that that nucleoside derivatives according to claim 1 with extenders and / or surface-active Means mixed up.