DE3807041A1 - Triazole compounds, process for their preparation, and method of regulating the growth of plants - Google Patents

Abstract

Triazole compounds of the formula I <IMAGE> in which R<1> is hydrogen, cyclopropyl, unsubstituted C1-C4-alkyl or C2-C4-alkynyl, or C1-C4-alkyl or C2-C4-alkynyl, each of which is substituted by methyl, ethyl, ethenyl, ethynyl, hydroxyl, fluorine, chlorine, bromine or C1-C4-alkoxy, or else represents a C1-C4-alkoxy, C2-C4-alkenyloxy or C2-C4-alkynyloxy group, R<2> and R<3> independently of one another are hydrogen, linear or branched C1-C3-alkyl, or the radicals R<2> and R<3> together with the C atom to which they are bonded can form a carbocyclic ring which has up to six members in each ring system and which optionally has bridging members, and with the proviso that, in formula Ia, at least two of the radicals R<1>-R<3> are other than hydrogen, and R<4> is a sulphonyl radical SO2R<5> (where R<5> represents linear or branched C1-C8-alkyl or optionally substituted phenyl), a process for the preparation of the azoles of the formula I, and their use for regulating the growth of plants.

Description

The present invention relates to triazole compounds, agents which these contain triazole compounds, processes for their preparation and Process for regulating plant growth with these Triazole compounds.

It is known that 2-chloroethyltrimethylammonium chloride, CCC, (J. Biol. Chem. 235, 475 (1960)) plant growth regulating properties Has cereals and other crops. It is also known that triazole-substituted alcohols (DE-OS 27 37 489, 24 07 143) the plant growth influence. In the earlier application P 37 16 847.9 Triazole compounds of formula Ia, Ib wherein R⁴ is hydrogen or a Acyl residue means described as growth regulators.

When using the known means for regulating the Plant growth is particularly effective at low application rates and concentrations are often insufficient.

The task was therefore to provide new connections, which the plant growth, especially with low expenses, effective can regulate.

It has now surprisingly been found that triazole compounds of the formula I

in the

R¹ is hydrogen, cyclopropyl or optionally substituted by methyl, ethyl, ethenyl, ethynyl, hydroxyl, fluorine, chlorine, bromine or C₁-C₄alkoxy C₁-C₄alkyl or C₂-C₄alkynyl or also for a C₁-C₄alkoxy -, C₂-C₄-alkenyloxy and C₂-C₄-alkynyloxy group,
R², R³ independently of one another are hydrogen, linear or branched C₁-C₃-alkyl, the radicals R² and R³ also being able to form together a carbocyclic ring which may have bridging elements and have up to six members in each ring system and with the proviso that in the formula Ia at least two of the radicals R¹-R³ are different from hydrogen and
R⁴ is hydrogen, a sulfonyl radical SO₂R⁵ (where R⁵ is linear or branched C₁-C₈-alkyl or optionally substituted phenyl)

means
the z. B. in DE-OS 27 37 489 and DE-OS 24 07 143 agents and other compounds that have been used so far are superior in their effect.

C₁-C₄-alkyl or C₂-C₄-alkynyl groups in the definition of R¹ are for example methyl, ethyl, propyl, butyl, ethynyl, prop-2-ynyl, Prop-1-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, C₁-C₄ alkoxy means for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso-butoxy, sec. butoxy or tert-butoxy. C₂-C₄ alkenyl or alkynyloxy are, for. B. Ethenyl, ethynyl, prop-2-enyl, prop-2-ynyl, prop-1-enyl, but-1-enyl, But-1-ynyl, but-2-enyl, but-3-enyl or but-3-ynyloxy.

In the definition of R², R³ is C₁-C₃-alkyl z. B. for methyl, ethyl, Propyl, iso-propyl. The radicals R² and R³ can also be combined to form one carbocyclic system linked, e.g. B. to a ring with 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. This ring can additionally z. B. bridged by a C₁ or C₂ bridge be such that a bicyclic radical such as bicyclo [2.2.1] heptanyl (norbornyl), Bicyclo [2.2.2] octanyl or bicyclo [2.1.1] hexanyl is formed.

In the sulfonyl radical SO₂R⁵ R⁵ is C₁ to C₈ alkyl such as methyl, ethyl, Propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, iso-pentyl, hexyl, iso-hexyl, heptyl, iso-heptyl, octyl or iso-octyl or for phenyl or substituted phenyl. As a substituent on Phenyl ring come e.g. B. halogen such as fluorine, chlorine, bromine, iodine, C₁-C₄-alkyl, C₂-C₄ alkenyl, C₁-C₄ alkoxy or cyano into consideration. The phenyl ring can 1 to 5, especially 1 to 3 bear inert substituents.

Examples of the group CR¹R²R³ are 2-propyl, t-butyl, 1-methylpropyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-ethylpropyl, 1-ethylpropyl, 1-ethyl-propen-1-yl, cyclopentyl, cyclohexyl, 1-methyl Called 1-methoxyethyl or 1-methyl-1-ethoxyethyl.  

The triazole compounds Ia or Ib are prepared by reaction of triazole compounds Ia or Ib, in which R⁴ is hydrogen, with Sulfonic acid halides X-SO₂-R⁵, wherein X is halogen such as chlorine, bromine or iodine means and R⁵ has the meaning given above or accordingly substituted sulfonic anhydrides in the presence of a base.

As bases or acid scavengers, conventional compounds such as alkali or alkaline earth compounds e.g. B. carbonates, hydroxides or alcoholates, tertiary amines, pyridine or substituted pyridine can be used. For example, sodium carbonate, sodium hydroxide, potassium hydroxide, Potassium tert-butoxide, trimethylamine, triethylamine, N-methylpiperadine or Called pyridine. The reaction in the presence of catalytic can be advantageous Amounts of 4-N, N'-dimethylaminopyridine are made.

The base can be advantageous in stoichiometric amounts or in excess in amounts of 1 to 2 mol per mol of hydroxy compound I with R mit = H be used.

The sulfonic acid halide or anhydride is usually in equimolar Amounts based on the hydroxy compound used. An over or Deficit, e.g. B. 0.5 to 2 mol, is also possible.

The reaction takes place in the presence or absence of a solvent at temperatures from -50 to + 150 ° C. Suitable solvents or diluents are z. B. ethers such as tetrahydrofuran, diethyl ether, methyl tert.- Butyl ether, dioxane; chlorinated hydrocarbons such as methylene chloride, aromatic hydrocarbons such as toluene or xylene, ketones, e.g. B. acetone, Alcohols such as tert-butanol, amides such as dimethylformamide or sulfoxides such as Dimethyl sulfoxide.

The production of the hydroxy compounds I with R⁴ = H is in the older Application P 37 16 847.9 described.

You are using acylation of triazolylacetonitrile Acylating agents of the formulas R¹R²R³CCOX prepared, wherein R¹-R³ the have the meaning given above and X represents chlorine, bromine or iodine. The chloride is preferred for economic reasons.

Suitable acylating agents are, for example, propionic acid chloride, Butyric acid chloride, isobutyric acid chloride, 2-methylbutyric acid chloride, Pivalic acid chloride, 2,2-dimethylbutyric acid chloride, 2-ethylbutyric acid chloride, 2,2-methyl-2-ethylbutyric acid chloride, 2-methylvaleric acid chloride,  2,2-dimethylvaleric acid chloride, 2-ethylvaleric acid chloride, 2-methyl-2-ethylvaleric acid chloride, 2,2-diethylvaleric acid chloride, 2-isopropylpropionic acid chloride, 2-methoxy-propionic acid chloride, 2-methoxy- 2-methylpropionic acid chloride, cyclopentylcarboxylic acid chloride and 1-methyl cyclopentyl carboxylic acid chloride.

The reaction is carried out in the presence or in the presence of a suitable Diluent carried out at temperatures between -50 and + 150 ° C. Suitable solvents are e.g. B. diethyl ether, tetrahydrofuran, dioxane, Methylene chloride, toluene, xylene, acetone, dimethylformamide, dimethyl sulfoxide, Methyl tert-butyl ether and tert. Butanol.

The compounds I are obtained as Z / E isomer mixtures by conventional chromatographic processes can be separated. The individual isomers like their mixtures are the subject of the present invention.

Production Example 1

To a suspension of 50 g (0.24 mol) 1-Cyano-1- (1,2,4-triazol-1-yl) -3-ethyl-1-penten-2-ol in 300 ml of toluene after adding 0.5 g of 4-N, N'-dimethylaminopyridine, 50 g (0.25 mol) p-Toluenesulfonic acid chloride added. Then 50 ml (0.36 mol) Triethylamine added dropwise. The mixture is stirred at room temperature for 40 hours, shake out with water, concentrate and leave the product crystallize. After recrystallization from ethanol, 60 g (68%) 2- (4-Methylphenylsulfonyl) -1-cyano-1- (1,2,4-triazol-yl) -3-ethyl-1-pe-nten obtained as a Z / E isomer mixture. Mp 78-87 ° C

C₁₇H₂₀N₄O₃S
calcd. C 56.7 H 5.6 N 15.5 S 8.9
found C 56.7 H 5.8 N 15.6 S 8.8

In the table below, the compound obtained is No. 15 listed.

The exemplary active ingredients shown in the table below were produced, insofar as physical information is included. The rest of the measures can be taken from the corresponding measures Preliminary products are obtained; they leave due to Equivalence considerations expect a comparable effect.  

Table 1

Triazole compounds of the formula

The triazole derivatives of formula I can practically all stages of development influence a plant differently and are therefore considered Growth regulators used. The variety of effects of Plant growth regulators depend above all

• a) the plant species and variety,
• b) from the time of application, based on the development stage the plant and the season,
• c) the place and method of application (seed dressing, soil treatment or leaf application)
• d) climatic factors, e.g. B. temperature, rainfall, also day length and light intensity
• e) the soil conditions (including fertilization),
• f) the formulation or application form of the active ingredient and in the end
• g) the concentrations of active substance used.

From the range of different applications of the Plant growth regulators according to the invention in plant cultivation some mentioned below.

• A. With the compounds which can be used according to the invention, the vegetative growth of the plants can be strongly inhibited, which manifests itself in particular in a reduction in the growth in length. The treated plants accordingly have a compact stature; a darker leaf coloration can also be observed.
  As an advantage in practice, z. B. the reduction of grass cover on roadsides, hedges, canal embankments and on lawns such as parks, sports and orchards, ornamental lawns and airfields, so that the labor and costly grass clippings can be reduced.
  It is also of economic interest to increase the stability of crops that are susceptible to storage such as cereals, corn, rice, sunflowers and soybeans. The resulting shortening and strengthening of the stem reduces or eliminates the risk of "storing" (twisting) of plants under unfavorable weather conditions before the harvest.
  It is also important to use growth regulators to inhibit the growth of length and to change the ripening process of cotton over time. This enables fully mechanized harvesting of this important crop.
  The use of growth regulators can also increase or inhibit the lateral branching of the plants. There is interest if, for. B. in tobacco plants the formation of side shoots (stinging shoots) should be inhibited in favor of leaf growth.
  With growth regulators, for example, frost resistance can also be increased considerably in winter rape. On the one hand, the growth in length and the development of a lush (and therefore particularly susceptible to frost) leaf or plant mass are inhibited. On the other hand, the young rapeseed plants are retained in the vegetative development stage after sowing and before the onset of winter frosts, despite favorable growth conditions. This also eliminates the risk of frost for plants that tend to prematurely degrade flowering and switch to the generative phase. Also with other cultures, e.g. B. Winter cereals, it is advantageous if the stocks are well stocked by treatment with compounds according to the invention in autumn, but do not go into the winter too abundantly. This can prevent increased sensitivity to frost and - due to the relatively low leaf or plant mass - infestation with various diseases (e.g. fungal disease). The inhibition of vegetative growth also enables denser planting of the soil in many crop plants, so that an additional yield, based on the soil area, can be achieved.
• B. With the new funds, additional yields can be achieved both on parts of plants and on plant ingredients. For example, it is possible to induce the growth of larger quantities of buds, flowers, leaves, fruits, seeds, roots and tubers, to increase the sugar content in sugar beets, sugar cane and citrus fruits, to increase the protein content of cereals or soybeans or to grow rubber trees to stimulate the increased latex flow.
  The triazole derivatives of formula I can increase yields by interfering with the plant metabolism or by promoting or inhibiting vegetative and / or generative growth.
• C. Finally, plant growth regulators can both shorten or lengthen the development stages and accelerate or delay the ripeness of the harvested parts of the plant before or after the harvest.
  Ease of harvest, for example, is of economic interest, which is made possible by the time-related falling or decreasing of the adhesive strength on the tree in the case of citrus fruits, olives or other types and varieties of pome, stone and nuts. The same mechanism, that is, the promotion of the formation of separating tissue between the fruit or leaf and shoot part of the plant is also essential for a well controllable defoliation of useful plants.
• D. Growth regulators can further reduce the water consumption of plants. This is particularly important for agricultural land that has to be artificially irrigated at a high cost, e.g. B. in arid or semi-arid areas. By using the substances according to the invention, the intensity of the irrigation can be reduced and thus more economical management can be carried out. Under the influence of growth regulators there is a better use of the water available because, among other things
  • - The opening width of the stomata is reduced
  • - A thicker epidermis and cuticle are formed
  • - The root penetration of the soil is improved
  • - The microclimate in the crop is favorably influenced by a more compact growth.

The active compounds to be used according to the invention can be used in crop plants both from the seed (as a seed dressing) and via the soil, d. H. through the root and through the leaf.

Due to the high plant tolerance, the application rate can be strong can be varied.

In the seed treatment, amounts of active ingredient are generally 0.001 up to 50 g per kilogram of seed, preferably 0.01 to 10 g.  

For leaf and soil treatment, doses are generally from 0.01 to 10 kg / ha preferably 0.05 to 3 kg / ha should be considered sufficient.

The agents according to the invention can be in the form of conventional formulations are used like solutions, emulsions, suspensions, dusts, powders, Pastes and granules. The application forms depend entirely on the Uses; in any case, they should be fine and even Ensure distribution of the active substance. The wording will be made in a known manner, e.g. B. by stretching the active ingredient with Solvents and / or carriers, optionally using Emulsifiers and dispersants, where in the use of Water as a diluent other than organic solvents Auxiliary solvents can be used. As auxiliaries come for it essentially in question: solvents such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), Alcohols (e.g. methanol, butanol), amines (e.g. ethanolamine), N, N-dimethylformamide and water; solid carriers such as natural stone powder (e.g. Kaolins, clays, talc, chalk) and synthetic stone powder (e.g. finely divided silica, silicates); Emulsifier or other surface-active Agents such as nonionic and anionic emulsifiers (e.g. Polyoxyethylene fatty alcohol ethers, alkyl sulfonates) and dispersants such as Lignin, sulfite liquor and methyl cellulose. Application is preferred of the compounds according to the invention in aqueous solution, if appropriate, under Add water-miscible organic solvents such as methanol or other lower alcohols, acetone, N, N-dimethylformamide or N-methylpyrrolidone. The formulations generally contain between 0.1 and 95 wt .-% active ingredient, preferably between 0.5 and 90 wt .-%.

Ready-to-use formulations or those made from them Preparations, such as solutions, emulsions, suspensions, powders, dusts, Pastes or granules are used in a known manner, for example pre-emergence, post-emergence or as a mordant.

The agents according to the invention can also be used together in these forms of use with other active ingredients or with fertilizers are mixed and applied. When mixed with growth regulator mixtures synergistic effects can also occur, i. H. the effectiveness of the combination product is greater than the added efficacies of the individual components.

Claims (6)

1. Triazole compounds of the formula I. in the
R¹ is hydrogen, cyclopropyl, unsubstituted C₁-C₄-alkyl or C₂-C₄-alkynyl or optionally C₁-C₄-alkyl or C₂- substituted with methyl, ethyl, ethenyl, ethynyl, hydroxyl, fluorine, chlorine, bromine or C₁-C₄-alkoxy C₄-alkynyl means or also represents a C₁-C₄-alkoxy, C₂-C₄-alkenyloxy and C₂-C₄-alkynyloxy group,
R², R³ independently of one another are hydrogen, linear or branched C₁-C₃-alkyl, or the radicals R² and R³ together with the C atom to which they are attached are a carbocyclic ring which may have bridging members and have up to six members in each ring system can form and with the proviso that in formula Ia at least two of the radicals R¹-R³ are different from hydrogen and
R⁴ is a sulfonyl radical SO₂R⁵ (where R⁵ is linear or branched C₁-C₈ alkyl or optionally substituted phenyl)
means. 2. A process for the preparation of azoles of the formula I according to claim 1, characterized in that an appropriate acid halide R¹R²R³CCOX (X = halogen) in the presence of a suitable base or an acid scavenger and optionally in the presence of a Reacts diluent with triazolylacetonitrile and that Reaction product with a sulfonic acid halide or anhydride for Brings reaction. 3. Process for regulating plant growth, thereby characterized in that the soil, the plants or their seeds with treated a triazole compound of formula I in which R¹-R⁵ the have previously mentioned meaning.   4. Means for regulating plant growth, containing one Triazole compound of formula I according to claim 1. 5. Agent for regulating plant growth, containing a triazole compound of formula I according to claim 1 and inert additives. 6. Process for regulating plant growth, thereby characterized in that at least one triazole compound of formula I. according to claim 1 or an agent according to claim 3 or 4 on plants or let their habitat take effect.