CS200239B2 - Means and method for adjustment of plant growth - Google Patents

Description

The present invention relates to a plant growth regulating composition comprising as active ingredient beta-azolyl ketones or salts or metal complexes thereof, as well as the use of these compounds for controlling plant growth.

It is already known to use nitrogen compounds such as chlorcholine chloride (CCC) (J. Biol. Chem. 235. 475 (1960)) to control plant growth.

Plant growth regulators may, for example, cause a decrease in the height of growth, or may induce the formation of germs, buds or flowers at a certain point in time, on crop plants not normally prepared for this.

Furthermore, such active substances can increase the frost resistance, promote or suppress the formation of side shoots, or cause defoliation or abscess of the fruit, thus facilitating, for example, harvesting. In particular, avoiding the lodging of cereals before harvest with the help of growth regulators is of considerable economic importance.

Using the known ammonium salt mentioned above as a plant growth regulating agent, for example, in cereals, in which a reduced growth is to be achieved in order to prevent lodging, the effect is often not sufficient.

It has now been found that plant growth regulators which contain beta-azolyl ketones of the formula I as active ingredient

(I) in which^R* represents furyl, thienyl or^- a phenyl group, wherein the bitches The alkyl group may be substituted by a chlorine or alkyl group having 1 to 3 carbon atoms and

A 2 is a 1,2,4-triazolyl or 1,2,3-triazolyl residue, or salts or metal complexes thereof, having a very good ability to control plant growth and are excellent plant tolerance.

Salts are, for example, the hydrochlorides, bromides, sulphates, nitrates, phosphates of avalanins or dodecylbenzenesulfonates. The effectiveness of salts is given by the cation's efficiency, so the choice of anion is free.

Metal complexes are compounds of formula II [Me / R ¹ - C - CH ^G - CH - 0 (03 ^{3) 3} / _m JX _n (II)

Az wherein ^R1 and Az maj ^s defined above and

Mc means metal, such as copper, zinc, tin, manganese, iron, cobalt or nickel,

X is an anion of an inorganic acid and * m and n are 1, 2, 3 or - 4.

It has further been found that the beta-azolyl ketones of the formula I or their salts are obtained when the alpha, beta-unsaturated ketones of the formula III

R ^{1 -} CO ^- CH = CH - 0 (03 ^{3) 3} (шь wherein ^R1 is ^H with Ora-mentioned meanings are reacted with a-1,2,4-triazole or 1,2,3-triazole, optionally in in the presence of a basic catalyst and optionally in the presence of a diluent.

This method of manufacture is preferred.

Compounds of formula (I) may also be obtained when the alpha-haloketones of formula (IV) are used

Y r '- CO - CH - CH 8 - C (CH ₃ ) 3 or beta-haloketones of formula V

Ϊ

R ^{1 -} CO ^- CH ^- CH - C (CH ₃ ) ₃ (iv) (V) in which:

R ¹ has the above uvedeiý vtfzniun and

Y, halogen, or chlorine, is reacted with 1,2,4-triazole or 1,2,3-triazole, optionally in the presence of an acid binding agent and optionally in the presence of a diluent.

The reaction with the alpha-haloketone is preferably carried out in the presence of an acid binding agent and is carried out by first detaching the hydrogen halide to form an alpha, beta-unsaturated ketone, which is secondary reacted as described above to form the beta-azolyl ketone.

Salts can be prepared from the compounds of formula I obtained by the above processes. ‘

It has further been found that complex compounds with metals of formula II are obtained by reacting beta-azolyl ketones of formula I with metal salts of formula IV

MeX _n . аН ₂ 0 (VI) in which

Me, X and n are as defined above and a is 0, 1, 2, 3 or 4, in the presence of a solvent.

The reaction of alpha, beta-unsaturated ketones with 1,2,4-triazole or 1,2,3-triazole according to the above-described process is conveniently carried out without diluent or in an inert solvent, for example methanol, ethanol, isopropanol, n-butanol, tetrahydrofuran, dioxane, toluene, xylene, dimethylformamide at temperatures from about 0 to 100 ° C, preferably from +20 to +50 ° C. It is expedient to add an alkaline compound, for example sodium hydroxide, potassium hydroxide, triethylamine or Ν, Ν-dimethylcyclohexylamine in a catalytic amount.

The compounds of formula III used as starting materials are known in the literature and can be prepared from ketones and aldehydes by conventional methods.

The metal salts used to make the metal complexes are generally defined by Formula VI.

In this formula, Me is preferably metals I, II. and IV · to VIII. the secondary groups of the periodic system of elements and the metals II · and IV · the main groups, in particular copper, zinc, tin, manganese, ⁴ iron, cobalt or nickel.

The metal salts of the formula VI are generally known, readily available compounds.

For the production of metal complexes of the formula II, all solvents miscible acetone, tetrahydrofuran and preferably between 10 and 35 ° C are suitable.

These are preferably methanol, ethanol, isopropanol, dioxane. In this case, it is generally carried out at temperatures between 0 and 100 [deg.] C,

Example 1

Cl

C (CH ₃ ) ₃

CO-CH ₂ -CH ^/ \\

22.2 g 1- (4 * - ⁽

-4,4- <

, 2-en-1-one, 11 g

1,2,4-triazole and 0.3 g of potassium hydroxide are dissolved in 200 ml of ethanol and stirred at 50 ° C for 6 hours. The solvent was then distilled off under vacuum, the residue was dissolved in 250 ml of methylene chloride and the organic solution was washed twice with ~ 100 ml of water each time. The organic phase is then dried over sodium sulphate, filtered and the filtrate is concentrated. The residue was stirred with -8 75 mL isooctane, filtered and dried.

^{September KA 2} 7.7 g (95% ^t EOR ^and e) 3- ^{(1> 2> 4'-triazol-1-yl)} - ¹ - (4 ^/ chlorophenyl ^yl) -4> 4 - ^di meth ^of pentan-1-one in the form of white crystals of mp 113-115 ° C. The corresponding hydrochloride melts ^{at 156-1} ° C 5 ^7. Anal ^g icky in carried out with ^{y l y} ou ^No. enyne Uve ^d Ene in the following - the ^b ulcerative first

Table 1

R1 ^- CO-CH2 ^- CH

C (CH3) ₃

Az

Az

Temperature Te ^pl OTA counting point ⁱ ° C ^'(C) (hydrochloride)

104 to 106

125 to 127

160 to 162

130 to 132

- up to 72

128 to 130

135 to 137

206 to 208

112 to 114

142-143 / C (CH3) _3>

СО-СН, —CH 1

A 'n- ^{7 2}

8.5 g of copper (II) chloride (CuCl2.2H2O) are dissolved in 100 ml of ethanol and this solution is slowly added dropwise to 24.7 g of 3- (1 &gt; 2 > 4-triazol-1-yl) -1- with good stirring. Of (2'-furyl) -4,4-dimethylpentan-1-one dissolved in 150 ml of ethanol. The reaction mixture was further stirred at room temperature for 3 hours. The precipitated turquoise colored crystals were filtered off and washed with ml of ice-cold ethanol. 30 g (95% 'of theory) of bis- (3-1>'2> 4-triazol-1-yl) -1- (i2 * ^u -f furyl) ^-4-gamma 4 ^PE dim ^e thyl nten- -one 1 -C ^{u2 + u ChI} of ^hydride ol p ^{l e u} t nd the tote ^{123 to 124}

Example d '10

6.8 g of zinc chloride are dissolved in 50 ml of ethanol and this solution is slowly added dropwise to 29.1 g of 3- (1,2,4-triazol-1-yl) -1- (4'-chlorophenyl) with stirring. -4,4-dimethylpentan-1-one dissolved in 200 ml of ethanol. After 2 hours stirring at. The precipitated colorless crystals are filtered off at room temperature and washed with ice-cooled ethanol. 26 g (80%) ^{- Bis- (3- (1, 2,} 4-triazol-L-1-yl) -1 - ^{(4'-chlorophenyl)} -43' ^{dlmethylpentan--1-one) 2+} -chloridu- -Z o-'teplotě mp 149-152 ° C.

Correspondingly, the metal complexes listed in the following Table 2 can be produced:

Tab, u, 1 · 'k and 2 1 / _х с ^<СНз 'Л Me I _R 1 = co-CH ₂ -CH ₂ Yn 1 V A Example li R ¹ Az AND C. TI Cu AND - N> W Cl

n m Melting point ° C 2 2 208-210

OF\ Cl 2 2 215-218 1 G  Cl 2 2 155-157 ά Cl 2 2 213-215

The azolyl ketones useful in the present invention are useful in a number of plants for growth regulation. which 'manifests itself in particular' in reducing growth to height. This effect -a quenchability. they are better than. known growth regulators.

springs - formulas - i - 'and - II. they can also be used together with other plant protection agents, i.e. - together and - herbicides, insecticides, in particular also fungicides. It is advantageous in practice that it has also shown a combined use with fertilizer, in particular by mixing with urea. .

The growth-regulating effect is particularly pronounced in cereals, e.g. - &. rice and oats, but also in dicotyledonous plants (for example, sunflowers, tomatoes, apples, grape vines, rape) and various ornamental plants such as poinsettia and. hibiscus. Treated plants are lower in stature and ¹ - are generally - condensed

Habitus than untreated plants; in addition, a more persistent coloration of the leaves is observed.

Due to the high plant compatibility, the application rate can vary considerably;

in general, 0.05 to 12 kg, preferably 0.1 to 4 kg of active substance per ha are used per 1 ha of soil area. .

Examples of beta-azolyl ketones useful in the present invention include:

3- (1,2,4-triazol-1-yl) -1- (2'-furyl) -4,4-dimethylpentan-1-one, 3- (1,2,4-triazol-1-yl) -1- (2'-thienyl) -4,4-dimethylpentan-1-one, 3- (1,2,4-triazol-1-yl) -1-phenyl-4,4-dimethylpentan-1-one, 3- (1,2,3-triazol-1-yl) -1- (4'-chlorophenyl) -4,4-dimethylpenten-1-one and its hydrochloride, 3- (1,2,4-triazole- 1-yl) -1- (2 *, 4'-dichlorophenyl) -4,4-dimethylpentin-1-one, and its hydrochloride, 3- (1,2,4-triazol-1-yl) -1- (4'-methylphenyl) -4,4-dimethylpentan-t-one and its hydrochloride, 10,4-triazol-1-yl-1-t-methyl-4-chlorophenyl-4-dimethylethylpentan-4-one ,

Examples of metal complexes according to the invention are:

^{bis- (3-} (1, ^2, 4-nriazo ^l - ^1-yl) - ¹ - ⁽² * - ^{f uгy) -4,} 4-d ⁱ me ^t hylpenttn- ^{1 -one)} -Cu ² -c ^{+ h} Lorido, '. Bis / 3- ^(1,2, 4-triazol-1-yl) -1- ^(2'-e Thiel yl) -4,4-dimethyl ⁿ TE ⁿ hylpee -OC ¹ / c -Cu ^{2+ hl} chloride · ^bis- / 3- ^{(1, 2,} 4-triazol-1-yl) -1- ⁽⁴ * -c), ^f гLor e ^ey l) -4,4-dimethylpen TE- ^{t 1} - he ^/ -Cu ²⁺ chloride, ^bis- · / 3- ^{(1, 2, 4-triazol-1-yl-1} - ^{(4 / f} e ^{e -chloro-4-yl,} 4-d ^{i n} methylpee tn -OC ^{1/2 +} c -Z ^h lor ^and d '·· ^{bis- /} 3 ^(t ^^ - ^triazol-1 -ylM - ^{(4-chlorophenyl} ^^ - methyl ^ l ^^ an- ¹ -one ^/ c -Cu ^{2+ hl} oiid »· ^{bis- /} 3 ^{(1/2, 4-triazol-1} -ylM - ^{(2 ', 4'} -di to R ^f 1 ^ 61 ° 4,4-dimethyl ^^ IPEN ^t h ^t n- ¹ -onACu ^ CCH ^ RID ;, · ^{bis- /} 3- ^{(1, 2,} 4-Tritz ^l - ¹ - ^yl) -1- ⁽⁴ * ^{methylphenyl)} -4,4- ^di: methylene ^{lp t} tn en-1-one / -Cu ²⁺ -chlo2dtú ,. · · bis / 1- (1, ^2, 4-triazol-1-yl ) -1 ^{+ (2} * -methyl-4 '-chtarfenyl N, N -dimethylamine hylpee ^{t n} шl bϊ-3 / - ^{2 +} Cl ^- chloride.

The active compounds are applied, for example, in the form of directly sprayable solutions, powders, suspensions, or also high-purity aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scatters, granulates and spraying agents. , fogging, dusting, sprinkling or watering. The application forms are entirely guided by the purposes of use; in any case, they are intended to ensure the finest possible dispersion of the substances.

For the preparation of directly injectable solutions, emulsions, pastes and oil dispersions, suitable are: medium to high boiling mineral oil fractions, such as petriolea or diesel oil, tar oils, etc., and vegetable oils, or Animal origin, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydioeaphnalee alkylated naphthalenes or derivatives thereof, alcohols (e.g. methanol, butanol), amines (e.g. ethepolamine ^, dimethylformamide) and water; carriers such as natural stone meal (e.g., kaolins, clays, talc, chalk) and synthetic stone meal (e.g., highly dispersed acidic silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene-fatty alcohol · yethylenethery and ^{LK; yl} sulfoeán ^y and ^y αr lsul ^f oe ^{and Ty)} and d ^ ^ Perg ^ORY, Jata sulfit.ov ^é. 'opadni. ^l OUH ^y and methylcellulose.

The compositions contain generally between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90% by weight of active ingredient.

For the duration of application, the application of the compositions according to the invention is carried out over a favorable period of time, the exact determination of which is governed by geographical, climatic and vegetative conditions.

The following examples demonstrate the effect on height growth without excluding the possibility of uses other than those described above.

Pří kl. ad · A ‘

Experiments in the greenhouse according to the Neubauer system

In a greenhouse, the seeds of the test plants are sown in 12.5 cm diameter plastic containers using a peat substrate that is sufficiently supplied with nutrients. The application of the active compounds is carried out in the form of an aqueous solution or dispersion in different amounts applied to the soil on the day of sowing. The substances are sprayed directly onto the soil surface. During a growth period of 18 days, the plants treated with the compositions according to the invention show a markedly smaller increase in height compared to the untreated control plants, as confirmed by the following plant height measurements. 100 plants are measured for each row of treated plants. The action of the substances according to the invention exceeds that of the known comparator, i.e. chlorocholine chloride (N-2-chloroethyl-N, N, N-trimethylaminium chloride = CCC).

Table 3

Effect on height growth in wheat in soil treatment (Neubauer system)

Active Substance · Amount used kg / ha Plant height cm relative inspection (untreated) -. 30.0 100 ALIGN! CCC · (known substance) 3.0 21.5 71.7 12.0 1 ⁹ '5 65.0 1 3.0 18.5 61.7 12.0 11.5 38.3 . · K and 4 to grow to the height of barley at soil treatment (Neubauer system) LV ^{and teaches} substance · Quantity used Plant height · · kg / ha cm relative control '· (untreated) . - 32.0 100 ALIGN! QČC -. (known substance) 3.0 26.0 81.3 12.0 23.5 73.4 1 3.0 22.0 68.8 12.0 16.0 50.0

200239 6

Table ⁵

Influence on plant height in rape during soil treatment (Neubauer system)

Active substance WITH. Amount used kg / ha Plant height cm relative inspection (untreated) - 17.0 100 ALIGN! CCC (known) 3.0 17.0 100 ALIGN! 12.0 17.0 100 ALIGN! 1 3.0 15.0 88.2 12.0 13.0 76, ⁵ 7 3.0 16.0 94.1 12.0 14.0 82.4 3 3.0 15.0 88.2 12.0 14.0 82.4

Example В

Vegetation experiment according to Líitscherlich system

In order to ascertain the effect of the treatment with the compositions according to the invention on monocotyledonous plants grown under conditions close to field conditions, a vegetation experiment is carried out in large containers containing 10 liters of β spring barley.

The plants are grown on clay sandy soil, fertilizing per vessel of 1.5 g of nitrogen in the form of ammonium nitrate and 1 g of phosphorus pentoxide in the form of secondary potassium phosphate. The active ingredients were applied in the form of an aqueous dispersion after sowing barley onto the soil surface. However, N-2-Chloroethyl-N, N, N-trimethylammonium chloride (CCC) used as a comparative substance was applied at a plant growth height of about 40 cm in the form of an aqueous solution by spraying on the leaf since it is known that a period (longer than 4 weeks) is inactivated for this substance. At the end of the ear development, the plants treated with the active compound according to the invention, at an otherwise identical development state, were found to exhibit a markedly lower height growth compared to the untreated control plants.

The known comparative substance (CCC) was clearly superior in its effect to the substances according to the invention, even at lower application rates.

Table 6

Influence on height of barley in soil treatment during vegetation experiment (Mitscherlich system),

Active substance no. Amount used kg / ha Height of plants cm relative inspection (untreated) - 101.0 and 100 ALIGN! CCC (known) 3.0 94.0 93.1 6.0 94.5 93.6 1 1.5 91.5 90.6 3.0 85.5 84.6

Example 15 parts by weight of compound 1 are mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone to give a solution which is suitable for application as minimal drops.

Example 16 parts by weight of compound. 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide with 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts by weight of the addition product. mol of ethylene oxide with 1 'mol of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example ... 17 <

parts by weight of compound 3. is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 18 parts by weight of Compound 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction at a temperature. boiling point 210 DEG-280 DEG C. and 10 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 19.

parts by weight of active ingredient 2 are well mixed with 3 parts by weight of diisobutylnaphthalene-alpha-sulfonic acid sodium salt, 17 parts by weight of ligninsulphonic acid sodium salt from sulphite waste liquors and 60 parts by weight of powdered silica gel, and the mixture is ground in a hammer mill. By finely distributing this mixture in 20,000 parts by weight of water, a spray suspension is obtained which contains 0.1% by weight of active ingredient.

Example 20 parts by weight of compound 3 are intimately mixed with 97 parts by weight of finely dispersed kaolin. In this way, a dust is obtained which contains 3% by weight of active ingredient.

Example 21 parts by weight of compound 4 are intimately mixed. mixtures consisting of 92 parts by weight of powder. silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of the silica gel. In this way a composition with good adhesion is obtained.

Example 22 parts by weight of active ingredient. 1 is thoroughly mixed with 10 parts of sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution of 100,000 parts by weight. water, an aqueous dispersion is obtained which contains 0.04% by weight of the active ingredient.

Example 23 parts of active ingredient 2 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenolsulfonic acid, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil. A stable oil dispersion is obtained.

Claims (1)

SUBJECT OF THE INVENTION A plant growth regulating agent comprising at least one compound of the general formula in addition to a solid or liquid carrier R ¹ -CO-CH ₂ -CH -C (CH ₃ ) ₃ Az wherein ^R1 is ^{f ur-yl} group verifies ^ th ^ ny ^ Vou slcupwu not a ^{f b} en verifies ^yl group, ^{wherein f} enyl radical may be substituted by chlorine or by alkyl of 1 to 3 carbon atoms, and Az is 1,2,4-triazolyl or 1,2,3-triazolyl, or a salt thereof or a metal complex thereof.