FI63576B - TRIAZATETRACYKLODEKAENDERIVAT ANVAENDBARA FOER REGLERING AV VAXTERS TILLVAEXT - Google Patents

Description

I- ral ANNOUNCEMENT ^ „dfijt ^ (11) utlAgcninosskrift 6 3 5 7 6 C .... Patent granted 11 07 1983 ^“ Patent meddelat ^^ (Si) Kv.Hc? /Into.3 C 07 D 487/02 // A 01 N 43/90 FINLAND — FINLAND (21) ywntawkniiw — Braiding »802718 (22) H» k ** nl * pily * - AmOtadnfidag 28.08.80 '' (23) Alkupaivt — GlMgMttdac 06.04.77 (41) Translators | ulkiMl (j) - Mhrtt offandlg 2g 08 80 FMMttl. And r * ki »t * rihallltu · NMriUp» »|. kuLMk ^, „* 'nrtwit och ragiatarttyralMn' 'amMcm utkgd och utUkrNkwi pubUcnrad 3x.uj.03 (32) (33) (31) Pyydetty« uoHmu · —Begird prlorknc 10.04.76

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) P 2615878.I

(71) Basf Aktiengesellschaft, D-67OO Ludwigshafen, Federal Republic of Germany (DE) (72) Rolf Platz, Mannheim, Werner Fuchs, Ludwigshafen am Rhein,

Norbert Rieber, Mannheim, Ulf-Rainer Samel, Mutterstadt,

Johann Jung, Limburgerhof, Bruno Wuerzer, Limburgerhof,

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (74) Oy Kolster Ab (54) Triazatetracyclododecene derivatives useful for regulating plant growth - Triazatetracyclododecaenders

This invention relates to novel triazatetracyclododecene derivatives having a strong biological effect on plants.

The compounds of the invention have the formula

R

having phenyl which may be substituted by one or two halogen atoms or one trifluoromethyl group; phenylsulfonyl, benzyl, benzothiazole or thiazole.

63576

The compounds of the invention can be prepared according to the following reaction scheme: + r1 "N3 ^

IV N VII R1 VIII

further,

The reaction of a compound of formula VI with an azide derivative of formula VII (Houben-Weyl, Bd. 10/3, p. 777) is carried out in a neutral solvent at a temperature of -30 to 180 ° C, preferably 20 to 120 ° C. The trazoline derivative of formula VIII is recovered from the reaction solution by cooling or concentrating the solution or, using a polar solvent, by adding a non-polar solvent.

The N, β2,3-triazoline derivative is cleaved with Nj to give the corresponding aziridine derivative. The cleavage takes place in a solvent by heating at 90-140 ° C or, after the addition of the catalyst, at 28-80 ° C. As the catalysts, acids such as sulfuric acid, acetic acid or trifluoroacetic acid, or insoluble supports containing acid groups such as ion exchangers can be used.

Alternatively, the compounds of the invention may be prepared according to the following reaction scheme: VI N VII · R 11 = (CH 3) 3 Si R 1 VIII 1 ethanol / -? - N, ligroilnl n - ^ - n Λ IX x c6H5s ° 2-ha 0 1 <r1 = c6h5so2) 63576

Coupling of the silyl azide to the C = C double bond of the compound of formula VI provides an N-silyl-β-1,2,3-triazoline derivative of formula VIII 'which can be treated with ethanol / ligroin to form NH-Δ-1 of formula IX. , 2,3-triatsoliinijohdannainen. The resulting triazoline compound is converted to the corresponding aziridine compound by cleavage of Nj as described above. The N-H-aziridine derivative of formula X is reacted with a sulfonyl halide to form the corresponding N-substituted aziridine derivative. The reaction is carried out in a manner known per se in a neutral solvent, generally in the presence of a base, for example tertamine, alkali carbonate or bicarbonate, sodium methylate or alkali hydroxide, at a temperature of 20 to 100 ° C.

The starting compound of formula VI is prepared by the following synthetic route; Kyadricyclan (II) is reacted with azodicarboxylic acid esters (III) to give compound IV, which is converted by saponification and decarboxylation to compound V and this is converted without isolation by oxidation with CuCl 2 via the Cu 1 complex to azo compound VI (JACS 91, 5668 (1969)).

^ rVr '"" 00 * + (= N-COOR) _ —->

2 \ N-COOR

H 111 IV

φ: ΙΪ ^ & = ύ

The preparation of the compounds of the invention is described by the following examples. The structure of the compounds was confirmed by NMR, IR and mass spectroscopic or elemental analytical methods. The reported melting points are uncorrected.

63576 4

Example 1

'C CFjCOOH ^ <ΤΤ ^ \ _ N

N -N 1 "O O"

Br Br 2 10 parts of the above -1,2,3-triazoline derivatives and 3 parts of trifluoroacetic acid are stirred for 5 hours in 150 parts of methylene chloride at room temperature. After distilling off the solvent, the residue is degassed with 30 parts of ether. Yield: 8 parts (88% of theory), m.p. 195 ° C (dec.) (From benzene / naphtha).

In a similar manner the following compounds were prepared: R1 (formula I) m.p. (° C) C3 149

Cl_140

Otl 110 ch2-66169 (dec.) Cf3 ^ R1 (formula I) m.p. (° c) C 1-4 / 194 (dec.) 5,63576

Cl 203 (dec.)

Il 146 (haj.)

Example 2 ^ -¾13. > "" T 1 = 6H 5 -SO 2 Cl 3 3 parts of the N-H-aziridine derivative and 3 parts of triethylamine are dissolved in 50 parts of tetrahydrofuran. To this is added dropwise at 0-5 ° C and with stirring 3.9 parts of benzenesulfochloride. After filtration of the precipitated triethylammonium chloride, the solvent is distilled off. The residue is washed with 50 parts of water and dried. Yield: 5.4 parts (88% of theory); mp. 154 ° C (dec.).

The new compounds of the formula I have a strong biological effect on plants, i.e. they affect plant growth either by inhibiting height growth, altering the concentration of substances in plants, or by eliminating unwanted plants while sparing useful plants.

The use takes place, for example, as directly injectable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays, granules by spraying, melting, dusting, sprinkling or wetting. The uses are completely dependent on the uses.

In the preparation of directly injectable solutions, emulsions, pastes and oil dispersions, mineral oil fractions with a medium to high boiling point, such as kerosene or diesel oil, further coal tar oils, etc., as well as vegetable oils or oils of aromatic, aliphatic, alpha, animal origin, , xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or 6,63576 derivatives thereof, e.g. methanol, ethanol, propanol, butanol, chloroform, tetrachloromethane, cyclohexanol, cyclohexanone, dimethylamide, chlorobenzene, chlorobenzene, isforon, strongforone, isforon, -methylpyrrolidone and water.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders), oil dispersions by adding water. To prepare emulsions, pastes or oil dispersions, the substances can be homogenized in water as such or dissolved in oil or solvents with the aid of wetting, tackifying, dispersing or emulsifying agents. The active ingredient can also be formulated with wetting, tackifying, dispersing or emulsifying agents and, if appropriate, concentrates containing solvents or oils, which are suitable for dilution with water.

Surfactants include:

Alkali, alkaline earth, sulphonate, alkyl sulphonates, alkyl sulphates, dibutyl naphthalene sulphonic acid alkali and alkaline earth metal sulphate, alkali metal sulphate sulphate, lauryl sulphate, alkali metal sulphate, lauryl sulphate, alkali metal sulphate ,, salts of sulphated hexadecanols, heptadecanols, octade-canols, salts of sulphated hexadecanols, heptadecanols, octadecanols, salts of sulphated fatty alcohol glycol ethers ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenylpolyglycol ethers, alkylaryl, polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide denaturate t, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powders, materials for spreading and dusts can be prepared by mixing or grinding the active ingredients with a solid carrier.

7 63576

Granules, e.g. coated, impregnated and homogenized granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers include, for example, mineral soils such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, talc, Bolus, loess, clays, dolomite, diatomaceous earth, calcium and magnesium sulfate, technetium oxide, magnesium oxide, magnesium oxide fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal powder, wood bark powder, wood powder and nut shell powder, cellulose powder and other solid carriers.

The formulations contain from 0.1 to 95% by weight, mainly from 0.5 to 90% by weight, of active ingredient.

Various types of oils, herbicides, fungicides, wormicides, insecticides, bactericides, trace elements, fertilizers, antifoaming agents (e.g. silicones) or growth regulators may be added to the mixtures or private active ingredients.

In various cases, a combination or mixture of the compounds of the invention and other growth regulating agents may prove advantageous, such as e.g. a mixture with ethylene-forming substances of various chemical structures (e.g. phosphonic acid derivatives and silanes, ethylhydrazines), onium compounds (e.g. trimethylammonium, hydrazonium and sulphonium salts, morpholinium, piperidinium and pyridazinium compounds). Other growth regulators are also interesting, e.g. substances belonging to the group of trifluoromethylsulfonamido-β-acetotoluidide, maleic acid hydrazide, abscisic acid derivatives, chlorinated phenoxy fatty acids having an auxin-like effect, and polyhydric alcohols and fatty acid esters having a specific effect on plant cell tissue.

The application rates of the compounds of the invention may vary. The amount used depends mainly on the quality of the desired effect.

The amount to be applied is generally 0.1 to 15 kg of active ingredient per hectare or more, mainly 0.2 to 6 kg per hectare.

They affect the growth of above-ground or underground plant parts in different ways and at normal use concentrations their toxic effect on warm-blooded animals is negligible.

8,635 76

The new compounds affect the physiological events of plant development and can be used for various purposes. The wide variety of effects of these compounds depends essentially on the time of use, taking into account the stage of development of the seed or plant, and on the concentrations used.

The new compounds affect the vegetative and generative growth of the plants, as well as the germination by means of a corresponding concentration.

The effect on vegetative development is manifested in particular in the reduction of growth height, which can help to improve the survival of numerous plants, especially cereals, and reduce the tendency for so-called "storage". At the same time, the growth rate improves, as a result of which the number of stalks carrying cones per unit area increases.

In the case of grass, as a result of the reduced growth height, the herd is denser, more resilient and, above all, several cuts are saved. The latter is of great economic benefit when it comes to decorative lawns but also roadside lawns and park areas. As a result, as the growth height decreases, the chlorophyll content increases, which makes the green color of the treated grasslands, as well as other vegetation, clearly darker.

The effect on vegetative growth strongly increases the flowering and fertilization of numerous plants such as cotton and soybeans.

Particular emphasis should be placed on the surprising phenomenon that treatment with the substances according to the invention promotes root growth. As a result, plants make more rational use of water and nutrients; this improves not only the drying resistance but also the resistance to cold (frost resistance). There are also diverse and wide-ranging uses for fruit and ornamental crops, as well as for landscaping, including objective impact on set-aside areas as well as airports and training grounds.

The compounds can also be used successfully in an effort to influence flowering and maturation events, such as in the context of special plant cultivation.

63576 9

Finally, the new substances can also have a positive effect on the levels of important substances in plants, such as sugar and protein.

The amount and quality of the effect depends on various factors, in particular the time of application, taking into account the stage of development of the plants and the concentration of use. Again, these factors are different depending on the plant species and the desired effect. Thus, for example, lawn areas are treated throughout the growing season; ornamental plants for which it is desired to increase the intensity and number of inflorescences, before planting the flowers; plants the fruit of which is used or harvested for an equivalent period before harvest. The various derivatives of the class of compounds described herein have herbicidal properties.

Therefore, they are suitable for controlling and controlling the growth of unwanted plants.

Example 1

Effect on growth of cereals and grasses.

The test vessels were plastic pots with a volume of 1130 cm "* (Table A) or paraffinized cardboard cups with a volume of 3 170 cm (Table B). The pots and plates were filled with clayey sand. The seeds of the test plants were sown separately low depending on the species. (soil treatment) took place immediately after sowing before the seeds germinated.The grains on the surface came into contact with the active ingredients.The treatment after seedling (leaf treatment) took place when the average growth height of the test plants was between 6-10 cm depending on the growth capacity of the species. or also dissolved in water used as a diluent using fine nozzles.The vessels were kept in a greenhouse at a temperature between 12 and 25 ° C. They were regularly sprinkled during the test period.The length of the observation period varied from 6 weeks to 8 weeks.

The results are shown in Table A.

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11 63576

Example II

herbicidal

The new compounds mentioned in Table B below proved to be effective herbicides for inhibiting the growth of undesired plants. The substances were tested by the following method: Paraf-refined cardboard dishes with a volume of 170 ° C were filled with clayey sand and seeded with seeds of the plants to be tested separately by species.

The treatments took place immediately after sowing before the seeds germinated (treatment before germination = soil treatment). The flat-lying, completely uncovered seeds of the soil then came into contact with the active ingredients. The compounds were applied by means of finely divided nozzles and using water in which the substances had been suspended or emulsified as a diluent. The amounts of active ingredients used are shown in Table B. During the experiment, the plants were well watered. The growth site was a greenhouse with a temperature between 12-25 ° C and 18-35 ° C depending on the temperatures required by private species. The length of the observation period ranged from two to six weeks. The effect was examined visually using a scale of 0-100. In this case, meant 0 = no damage, 100 = the plants had not germinated or were completely damaged.

List of plant species in Table B.

Latin name Finnish name English name

Alopecurus myosuroides Fieldgrass Blackgrass

Cynodon dactylon Dog Millet Bermudagrass

Cyperus esculentus Maamanteli Yellos nutsedge

Digitaria sanguinalis - Hairy crabgrass

Euphorbia spp. Cuckoo species Spurge family of us. E. geniculata

Ipomoea spp. Lifeline Morningglory about us. I. lacunosa

Matricaria chamomilla Wild chamomile Wild chamomile

Panicum virgatum Millet Switchgrass

Poa annua Village grass Annual bluegrass

Setaria faberii Roll millet Giant foxtail 12 63576

Latin name Finnish name English name

Mustard Alba White Mustard White mustard

Sorghum halepense Villidurra Johnsongrass

Stellaria media Yard Constellation Chickweed

Result 1. The herbicidal effect of the new compounds for controlling and keeping the growth of undesired plants was confirmed. In doing so, it was the same whether monocotyledonous or dicotyledonous species were treated.

2. In the case of soil treatment, the resistance of herbaceous crops to the compounds listed in Table B proved to be low. However, the substances described in this experiment are suitable for the removal or attenuation of unwanted vegetation if the crops use an application technique which does not come into direct contact with the young leaves of the cultivated plants. This is quite possible when using the underside of the magazine ruiskuttamismenetelmiä (postdirected spray, lay-by treatments) or by granulating the active ingredients. Likewise, in the case of perennial species, their use after harvest or during the growing season come into question. One area of application is also the control of weeds in connection with missing crops such as berry bushes and stands of all kinds. In addition, the growth of unwanted plants can be controlled or kept to a minimum in places where crops need not be taken into account.

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Example III

Additional experiments were performed under the same conditions as described in Example I. The internal volume of the plastic pots used as test vessels was 300 cm. Because heat-retaining experimental plants (Euphorbia geniculata = South American horseradish, Arachis hypogaea = peanut, Cynodon dactylon - Bermuda) were kept at a temperature of 20-30 ° C. vesas were treated by the methods used for seedling after emergence.

Result: Treatment with the compounds of the invention shown in Table C of this example using the post-emergence method significantly inhibited the growth of spores in the case of peanuts (A. hyogae) and bermuda grass (dog millet = C.dactylon) in a cultivation technique. The same result can be obtained using a pre-emergence method, as shown, for example, in Table D for Euphorbia geniuculata. Of particular significance is the fact that the reference substances only affect very specifically defined plant species. The compounds of the invention, on the other hand, may have use in the context of a large number of plant species. Similar results were obtained with the new compounds for soybeans (Clysine max), maize (Zea mays) and other plant species.

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Example IV

Two summer grain - wheat (variety 'Opal') and barley (Variety "Union") was grown during the winter half-year period kasvihuoneolo relations in glass dishes peat culture medium with the addition of appropriate quantities of nutrients.

To treat the soil (by methods used before germination), the active ingredients were poured into aqueous preparations, each in two different doses, immediately after sowing the grain on the surface of the peat.

The leaves were treated by spraying cereals with a growth height of 11 cm with aqueous preparations of the active ingredients, each using two different doses.

The growth height shortages caused by the active substances were determined by measuring the plant lengths at the end of the experiment after a growth period of 30 days and the values were compared with the growth height of the untreated plants.

In this case, the growth-shortening effect of the tested substances could be demonstrated. Private results are available in the following Tables E and F.

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