CS241482B2 - Plant growth regulation agent and fungicide and method of active component production - Google Patents

Abstract

Azole derivs. of formula (I), their acid addn. salts and metal salt complexes are new. R is alkyl or opt. substd. cycloalkyl or phenyl. X is nitrogen or CH. Y is OCH2, CH2CH2 or CH=CH. Z is halo, alkyl (opt. substd. by halo), cycloalkyl, alkoxy or alkylthio (both opt. substd. by halo) or opt. substd. phenyl, phenoxy, phenylalkyl or phenylalkoxy. m is 0-3. Also new are intermediates of formula (II). (I) are useful as fungicides (esp. against true mildews such as Erysiphe species and have both preventative and systemic actions and as plant-growth regulators. Typical responses include inhibiting vegetative growth of cereals etc., increasing sugar content of beet, and protein content of soya; stimulating latex flow in rubber trees; induction of parthenocarpic fruiting; breaking apical dominance, defoliation, acceleration of ripening; improving resistance to adverse climatic conditions etc. They are more effective than known cpds. such as 2-chloroethylphosphonic acid.

Description

The present invention relates to compositions for controlling plant growth and to fungicidal compositions containing as active ingredient the novel 1-hydroxyethyltriazole derivatives. The invention further relates to a process for the preparation of these new active substances.

It is already known that certain 2-haloethyltrialkylammonium halides have the ability to regulate plant growth (cf. U.S. Pat ^. No. 3,156,554). However, the efficacy of this substance, especially at low application rates, is not always sufficient.

It is further known that 2-chloroethylphosphonic acid has the ability to regulate plant growth (cf. DOS 1,667,968). However, the results obtained with this substance are not always satisfactory either.

It is further known that zinc ethylene-1,2-bisdithiocarbamate is a good means of combating fungal diseases of plants [cf. Phytopathology 33, 1113 (1963)]. However, its use is only possible to a limited extent, since it is not always satisfactory in particular at low application rates and concentrations.

Now, new 1-hydroxyethylazole derivatives of the general formula I have been found

OH ^Z rri CH,

N ------ ’(I) in which

R is C 1 -C 4 alkyl, C 1 -C 7 cycloalkyl optionally substituted by C 1 -C 2 alkyl or phenyl optionally substituted by halogen and / or C 1 -C 4 alkyl carbon,

Y is -OCH 2 - or -CH 2 -CH 2 -,

Z represents halogen, (C1-C4) -alkyl, (C1-C4) -alkoxy, (C1-C4) -alkylthio, (C1-C4) -halogenoalkyl or (C1-C5) -halogenoalkoxy; and having from 1 to 5 halogen atoms or a phenyl group optionally substituted by halogen and / or an alkyl group having from 1 to 4 carbon atoms, and rn being 0, 1, 2 or 3, and their addition salts. with hydrochloric acid or with niaphthalene-1,5-disulfonic acid.

The compounds of formula I have an asymmetric carbon atom and can therefore be formed in both optical isomeric forms. The present invention relates to both mixtures of isomers and individual isomers.

The present invention is a composition for regulating plant growth and _л fungicidal composition which comprises as active ingredient at least one derivative 1 ^^^^ (IROC ^ ^^^ (^ l ^] ^^^^ triazole above and a defined general formula (I) or a hydrochloride acid or 1,5-naphthalenedisulfonic acid addition salt thereof.

According to the invention, the 1-hydroxyethyltriazole derivatives of the formula I are prepared by the oxiranes of the formula II

O (CH 2 dl) in which

R, Y, Z and m are as defined above, in reaction with the triazole of formula III

H

Chlorohydroic acid or 1,5-naphthalenedisulfonic acid is preferred.

Surprisingly, the 1-hydroxytriazole derivatives of the formula I according to the invention exhibit a better plant growth regulating ability than the known c-chloroethyltrimethalamouium chloride and also the known 2-chloroethylphosphonic acid, which are - as is well known - well active substances with the same type of action. In addition, the compounds of the invention surprisingly have a better fungicidal action than the zinc methyl-1,2-bis-dithiocarbamate known from the prior art, which is the closest related compound in terms of activity. The active compounds according to the invention thus represent an enrichment of the technique.

Particularly preferred are those compounds of formula (I) wherein:

R represents a tert-butyl group, an isopropyl group or a methyl group, a cyclopropyl group, a cyclopentyl group or a cyclohexyl group, which groups are optionally substituted by a methyl group and optionally once or twice by the same or different fluorine, chlorine and / or methyl substituted phenyl;

Z represents fluoro, chloro, bromo, methyl, tert-butyl ·, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, and optionally once or twice, the same or different fluorine, chlorine and / or methyl-substituted phenyl; and

Y and m · have the meanings given below the formula

AND.

In addition to the compounds exemplifying the process for the preparation of the active compounds, the following compounds of the general formula I can be mentioned individually.

(III) in the presence of a diluent and optionally in the presence of a base at a temperature of from 0 to 200 ° C, followed by optionally obtaining compounds of the formula

Table 1

Zni Y R RD -0-CH ₂ - -C (CH ₃ ) ₃ 4 -0-CH ₂ - -C (CH ₃ ) _{3 3,4-Cl2} -0-CH ₂ - -С (СНз) з 4-CF3 -0-CH ₂ - -C (CH ₃ ) ₃ 4-OCF3 -0-CH ₂ - -C (CH ₃ ) ₃ 4-SCH3 -0-CH ₂ - -C (CH ₃ ) ₃ 4-C (CH3) ₃ -0-CH ₂ - -C (CH ₃ ) ₃ 4gO> -0-CH ₂ - 4 -0-CH ₂ - \ __! _3,4-Cl2 -0-CH ₂ - 4-CF ₃ -0-CH ₂ - g0 ^ -ci 4-OCF ₃ -0-CH ₂ - 4-SCH ₃ -0-CH ₂ - ~ <0> ^CI 4-C (CH3) ₃ -0-CH ₂ - gog ^ct -0-CH ₂ - -CH (CH ₃ hr -0-CH ₂ - -CH (CH _{3) 2 3,4-Cl2} -0-CH ₂ - -CH (CH _{3) 2} 4-CF3 -0-CH ₂ - -CH (CH ₃ hr 4-OCF3 -0-CH ₂ - - CH (CH _{3) 3} 4-SCH3 -0-CH ₂ - -CH (CH _{3) 2} 4-C (CH ₃ hr -0-CH ₂ - - CH (CH _{3) 3} -0-CH ₂ - 4— (б) —Cl —0-CH2- _3,4-Cl2 -0-CH ₂ - 4-cf ₃ -0-CH ₂ - 4-OCF3 -0-CH ₂ - 4) 4-SCH3 -0-CH ₂ - -4} 4-C (CH3) ₃ —0-CH2-

Zm Y R

M / 5) -0-CH ₂ - CH3 —O — CH2— CH ₃ 3,4 - C —O — OH2— ^CH3 4-CF3 —O — CH2— CH3 4-OCF3 —O — CH3— Ά ^CH 3 4-SCH3 —0 — CH2—

_-O-CH2 - -CH2-CH2-

-CH 2 -CH 2 - —C (CH ₃ h

-O (CH ₃ ) ₃

_3,4-Cl2

4-CF3

4-OCF ₃

4-SCF3

4-С (СНз) з

4 - / (5) -

3,4-Cl ₂ ,

4-CF3

4-OCF3

4-SCH3

4-C (CH 3) 3

-CH 2 -CH 2 —Cfy-C 1-4 -CH 2 -CH 2 —CH 2 —CH 2 - -CH 2 -CH 2 —CH 2 -CH 2 —CH 2 —CH 2 -

-CH2-CH2-CH2-CH2-CH2-CH2-

—CH2 — CH2—

-C (CH 3) 3 - C (CH 3) 3 - C (CH 3) 3 -C (CH 3) 3 - C (CH 3) 3

gO> -ci goga - <O) - ^Cf +> c <ХоУ-ct from _m YR

4 °) —CH ₂ —CH ₂ - -СН (СНз) ₂ 4-4 ^ -ct —CH ₂ —CH ₂ - -CH (CH _{3) 2 3,4-Cl2} —CH ₂ —CH ₂ - -CH (CH 2) ₂ 4-CF ₃ —CH ₂ —CH ₂ - -CH (CH _{3) 2} 4-OCF3 —CH ₂ —CH ₂ - -СН (СНз) ₂ 4-SCH3 -CH2-CH2- -CH (CH _{3) 2} 4-C (CH3) ₃ —CH ₂ —CH ₂ - -CH (CH _{3) 2} 4 °) —CH ₂ —CH ₂ - ЧЕ) -CH2-CH2- _3,4-Cl2 -CH ₂ -CH ₂ - 4D 4-CF ₃ -CH ₂ -CH ₂ - <E> - 4-OCF3 —CH ₂ —CH ₂ - 4-SCH3 -CH ₂ -CH ₂ - - <E> 4-C (CH3) ₃ —CH ₂ —CH ₂ - ЧЕ) ⁴ Ú2> —CH ₂ —CH2— CH * CH ₃ k- © -Ci -CH2-CH2- 3,4-012 —Сн ₂ —ch ₂ - ch ₃ 4-CF3 —CH ₂ —CH ₂ - CH ₃ 4-OCF3 -CH ₂ —CH ₂ - 4-SCH3 -CH ₂ -CH ₂ - 41 CH ₃ 4-С (СНэ) з -CH ₂ -CH ₂ - 41 C » ₃ 4-C1 -O-CH ₂ - - СН (СНз) _а 4-F -0-CH2- -CH (CH _{a) 2}

Grains Y R 4-CH3 —0 — CH2— ....... ^{R UII} H _{3) 2} 4-C1 —0 — CH2— -0 4-F —0 — CH2— _4-CH3 —0 — CH2— 0 4-C1 —0 — CH2— CH ₃ 4-F —0 — CH2— Ch 4-CH3 —0 — CH2— 0 CM ₃ 4-C1 —CH2 — CH2— —CH (CH3) 2 4-F —CH2 — CH2— -CH [CH _3] 2 ·· .. 4-CH3 -CH2-CH2- —CH (CH3) 2 4-C1 -CH2-CH2- 0) 4-F -CH2-CH2- -0 4-CH3 _CH2-CH2- -0. 4-Č1 -CH2-CH2- 0! CH ₃ 4-F · .. -CH2-CH2- ^CH 3 4-CH3 -CH2-CH2- 0 ^{1 С} 'з 2,4-Cl ₂ _CH ₂ -CH2- -C _{(CH3). 3} 4-CH3 -CH2-CH2- -CÍCHah 4-Cl, 2-CH 3 -CH2-CH2- -C (CH ₃ ) 3 4-F —0 — CH2— -C (CH _a) 3 2-CH3 -CH2-CH2- -C (CH ₃ ) ₃

If, for example, 2- (4-chlorenooxymethyl) -2-tert-butyloxirane and 1,2,4-triazole are used as starting materials, the reaction sequence of the invention can be illustrated by the following reaction scheme:

The oxiranes used in the process of the invention as starting materials are generally defined by Formula II. In this formula, the symbols R, Y, Z and the index m preferably have the meanings already mentioned in the description of the compounds of the formula I according to the invention as advantageous for these substituents, as well as the index m.

In addition, 1,2,4-triazole, which is used as a starting material in the process according to the invention, is a well-known compound of organic chemistry.

Suitable diluents for the reaction according to the invention are preferably all inert organic solvents. These preferably include alcohols such as ethanol and methoxyethanol, ketones such as 2-hutane, nitriles such as acetonitrile, esters such as ethyl acetate, ethers such as dioxane, aromatic hydrocarbons such as benzene and toluene, or amides such as dimethylformamide.

Suitable bases for the reaction according to the invention are all customary inorganic and organic bases. These preferably include alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydroxides such as sodium hydroxide, alkali metal alkoxides such as sodium and potassium methoxide and ethoxide, alkali metal hydrides such as sodium hydride, as well as lower tertiary alkylamines, cycloalkylamines and aralkylamines, in particular triethylamine.

The reaction temperatures can be varied within a wide range when carrying out the process according to the invention. In general, it is carried out at temperatures between 0 and 200 ° C, preferably between 60 and 150 ° C.

The reaction according to the invention can optionally be carried out at elevated pressure. In general, the pressures are carried out at pressures of 0.1 to 5.0 MPa, preferably between 0.1 and 2.5 MPa.

In the process according to the invention, preferably 1 to 2 mol of 1,2,4-riazole and optionally 1 to 2 mol of base are used per mole of oxirane of the formula II.

The isolation of the reaction products is carried out in a generally conventional manner.

The compounds of the formula I obtained by the process according to the invention can be converted into addition salts with hydrochloric acid or with 1,5-naphthalenedisulphonic acid.

These addition salts can be obtained in a simple manner according to conventional salt preparation methods, for example by dissolving the compound of formula I in a suitable inert solvent and adding hydrochloric acid or 1,5-naphthalenedisulphonic acid, and can be isolated in a known manner, for example by filtration. an inert organic solvent.

The active substances used in the context of the invention interfere with the metabolism of plants and can therefore be used as growth regulators.

For the type of action of the plant growth regulators, it has been hitherto known that the active substance can exert one or several different effects on the plants. The effects of the substances depend essentially on the time of application, based on the developmental stage of the seed or plant, as well as on the amount of active substance applied to or in the vicinity of the plants, and further on the mode of application. In any case, plant growth regulators have a positive effect on crop plants in an undesirable manner.

Plant growth regulators can be used, for example, to suppress vegetative plant growth. Such growth suppression is of economic importance, inter alia, in grassland, since the suppression of grass growth can, for example, reduce the frequency of mowing in ornamental gardens, parks, and sports facilities, at roadside, airports and orchards. Also of importance is the inhibition of the growth of herb241482

In woody and woody plants at the edges of roads and close to overhead lines, or quite generally where strong growth is undesirable.

It is also important to use plant growth regulators to suppress crop growth in grain, as this reduces or eliminates the risk of plants lying down before harvest due to crop shortening. In addition, plant growth regulators can cause the stalks to increase in stalks, which also acts against the lodging. The use of growth regulators to shorten the stalks and strengthen the stalks allows the application of higher amounts of fertilizer to increase yields, without worrying about the lodging of grain.

Suppression of vegetative growth allows for many crops to be denser or planted, so that yields per unit area can be increased. The smaller plants thus grown also have the advantage that the culture is easier to cultivate and harvest.

Suppression of vegetative growth of plants can also lead to increased yields as nutrients and assimilates are used more intensively for the formation of flowers and fruits than for the growth of vegetative parts of plants.

Stimulators of vegetative growth can also often be achieved with growth regulators. This is of great importance when vegetative parts of plants are harvested. However, stimulation of vegetative growth can also simultaneously lead to stimulation of generative growth by producing more assimilates, so that for example more fruits can be formed or larger fruits can be produced.

Increased yields can also be achieved in many cases by interfering with plant metabolisms without observing changes in vegetative growth. Growth regulators can also act on changes in the composition of plants, which in turn can achieve a better quality of harvested products. Thus, for example, it is possible to increase the sugar content of sugar beet, cane, pineapple as well as citrus fruit or to increase the protein content of soy or grain. Furthermore, it is also possible, for example, to inhibit the degradation of the desired substances contained in plants, such as sugar in sugar beet or sugar cane, by means of growth regulators before or after harvesting.

In addition, the production or efflux of secondary plant substances can be positively influenced. An example is the stimulation of latex effluent in rubber trees.

Parthenocarpic (seedless) fruits can also be produced by growth regulators. Furthermore, it is possible to influence the sex of the flowers with these regulators. Pollen sterility can also be achieved, which is of great importance in breeding and hybrid seed production.

By using growth regulators, it is possible to control the formation of side shoots in plants. On the one hand, the development of side shoots can be promoted by violating the application of domination, which may be very desirable, especially in the cultivation of ornamental plants, even in conjunction with the suppression of growth. On the other hand, it is also possible to inhibit the growth of the side shoots. This effect is of particular interest, for example, in tobacco growing or tomato planting.

The effect of the active substances on the foliage of the plants can be controlled so that the plants can be completely de-leafed at the desired time. Such defoliation is important for facilitating the mechanical harvesting of cotton, but it also plays a major role in other cultures, such as the vine, where it facilitates harvesting. Plant defoliation can also be performed to reduce plant transpiration before transplanting.

Growth regulators can also be used to control the fall of fruit. On the one hand, premature fruit loss can be prevented. On the other hand, it is also possible to support the fall of fruits or even flowers in the sense of a kind of “chemical thinning” to break the so-called “alternation”.

As an alternative, we mean the special behavior of some fruits by endogenously conditioned very different yields from year to year. Growth regulators can also serve to reduce the force required for harvesting fruit at harvest time so that mechanical harvesting or manual harvesting is facilitated.

By means of growth regulators, it is furthermore possible to accelerate or slow down the ripening of the harvested products before or after harvesting. This is particularly advantageous since it can be optimally adapted to market requirements. Furthermore, growth regulators can in many cases serve to improve the coloring of the fruit. In addition, growth regulators can achieve a concentration of fruit ripening within a certain period of time. This creates the prerequisites for, for example, tobacco, tomatoes or coffee plants to be able to carry out fully mechanical or manual harvesting in only one working stage.

The use of growth regulators can also affect seed or bud rest periods, i.e. endogenous annual rhythm, so that plants, such as pineapple or ornamental plants in horticulture, germinate, sprout or bloom when they would not normally rest, sprout or . nekvetly.

Growth regulators can also achieve delayed bud sprouting or delayed seed germination, for example, to prevent damage caused by frost in the cold in areas with colder climates.

Finally, it is possible to use the rs241482 я controllers

This has caused the plants to resist frost, drought or high salt content in the soil, allowing the plants to be grown in areas that would be favorable to these plants. normally inappropriate.

The active compounds according to the invention also show a strong microbicidal action and can be used in practice to combat undesirable microorganisms. The active compounds described are suitable for use as plant protection agents.

Fungicidal agents are used in plant protection to combat fungi of the classes Plasmodiophoromycetes, Oomycetes, Chytridlomycetes,. Zygomycetes, Asco-mycetes, Basidiomycetes and Deuteromycetes.

Since the plants active substances according to. . of the invention at concentrations necessary to combat fungal diseases of the plants well. They can be used for the treatment of aboveground parts of plants, seedlings and seeds, as well as for the treatment of soil.

As . plant protection agents can be active substances. According to the invention, particularly good results are used for combating fungi causing disease with true powdery mildew, such as k. combating Erysiphe species, for example to fight. against powdery mildew or cereal powdery mildew. (Erysiphe graminls).

Particularly. . it is preferred that the active ingredients according to the invention. - they show not only a protective effect, but ... that they are also systemically effective, which makes it possible. protect plants against fungal infestation. by delivering the active ingredient to the aerial parts of the plant via soil and the root system or through seeds.

Effective. the substances can be converted to the usual ones. compositions, such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, small particles coated with polymeric substances, and. ULV-means.

These compositions are prepared in a manner known per se. for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or. foaming agents. In the case of using water as. plmdla is possible as. co-solvents, for example, also use organic solvents.

As liquid solvents, they essentially come in. aromatics such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as. chlorobenzenes, cetorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol, but also 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; and water.

By liquefied gaseous fillers and carriers are meant liquids which are gaseous at normal temperature and pressure, for example aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells , corn sticks and tobacco stalks.

Suitable emulsifiers and / or foaming agents are nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyothylene ethers of fatty alcohols, e.g. waste liquors and methylcellulose.

The compositions of the present invention may contain binders. such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate

In addition, these compositions may contain dyes such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as aljzarine dye and metallic azo-phthalocyanine dyes, as well as trace elements such as iron, manganese, bpru, copper salts. , cobalt, molybdenum and zinc.

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

The active compounds according to the invention may be present in the formulations in admixture with other known active compounds, such as fungicides, infectious agents, acarides, herbicides, as well as in mixtures with fertilizers and other plant growth regulators.

The active compounds can be applied as. such in the form of concentrates or dosage forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The application is carried out in the usual manner, for example by watering, spraying, spraying, sprinkling, dusting, dusting, foaming, brushing, etc. Further, it is possible to apply the active substances by the so-called ULV process or as appropriate. inject the active agent or even the active agent alone into the soil. Plant seed can also be treated.

When the compounds of the invention are used as plant growth regulators, the application rates can vary within wide limits. In general, 0.01 to 50 kg, preferably 0.05 to 10 kg, of active substance are used per hectare of soil surface.

When using the substances according to the invention as plant growth regulators, the application is carried out within a convenient period of time, the exact definition of which is governed by climatic and vegetative conditions.

When the compounds according to the invention are used as fungicides, the application rate can vary within wide limits depending on the type of application. Thus, the concentration of the active ingredients in the treatment - the parts of the plants vary in application forms - in general ^: - between 1 and 0.0001% - by weight, - preferably - between 0.5 - and 0.001% by weight. In general, an amount of active compound of from 0.001 to -50- g per 1 kg of seed, preferably from 0.01 to 10-g per kg, is required. - oisiva. In the treatment of the soil, - at a location where the effect is to be achieved - a concentration of the active compound of from -0.00001 to - 0.1 -% - by weight, preferably from 0.0001 to - 0.02, is required - -%. .

Examples illustrating a process for the preparation of active substances.

Ex - 1 - - - - - - · - - - - · ·

Production of starting material:

Cl-H-O-CH 2 Cl 2 (CH ₃ ) ₃

O — Cfy

I-1)

To a solution of 189 ml (2.0 mol) of dimethylsulfate in 1200 ml of absolute acetonitrile at room temperature is added a solution of 162 ml (2.2 mol) of dimethylsulfide in 400 ml of absolute acetonitrile. -CON when heat-I RT. After ^1h it was added 118.8 g (2.2 mol] of sodium methoxide. the reaction mixture was allowed to stir for 30 minutes - and then during 30 -minut solution of 272 g (1, 2 mol] 1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one in 600 ml of absolute acetonitrile The reaction mixture is allowed to stir overnight, then the reaction mixture is concentrated, the residue is partitioned between water and - ethyl acetate, the organic phase is separated, - washed twice with water and once with saturated sodium chloride solution, dried - with - sodium sulphate, concentrated - and the residue is distilled in vacuo to give 242.4 g. (84 -% of theory) of 2- (4-chlorophenoxymethyl) -2-tert-butyloxirane, b.p. Deň: 32 ° C.

Example 2

72.15 g (0.3 mol) 2- (4-chlorophenoxymethyl) -2-tert-butyloxirane and 24.15 g (0.35 mol)

The 1,2,4-triazole is heated to reflux in 120 ml of ethanol for ~ 48 hours. The reaction mixture is concentrated, the residue is taken up in 200 ml of ethyl acetate and heated.

Then, the reaction solution is cooled in an ice bath, the solid is filtered off and washed with ethyl acetate. The filtrate is concentrated, the residue is dissolved in a mixture of ether and hexane and hydrogen chloride gas is introduced into the solution. The precipitate was filtered off, washed with ether and the free base was added after addition of a mixture of ethyl acetate and 1N sodium hydroxide solution. 60.2 g (65% of theory) of 2- (4-chlorophenoxymethyl) -3,3-dimethyl-1- (1,2,4-thiazol-1-yl) butan-2-ol are obtained, m.p. Noc: 2 ° C.

A solution of 17.9 g (0.075 mol) of 2- (4-chlorophenylthyl) -2-tert-butyloxyxane and 6.9 g (0.1 mol)

The 1,2,4-triazole in 30 ml of ethanol was heated at 150 ° C in a sealed tube for 20 hours. The reaction mixture is allowed to cool and then the reaction solution is concentrated. The residue was dissolved in ether, washed three times with water and then once with brine, dried over sodium sulfate and concentrated. The residue is chromatographed over a silica gel column (solvent system: dichloromethane / ethyl acetate 1: 1) to give 12.3 g (53.2% of theory) of 1- (4-chlorophenyl) -4,4-dimethyl-3t ( 1,2,4-triazol-1-ylmethyl] penaan-3-ol as a viscous oil.

In analogy to the preceding examples, the compounds of the general formula I are obtained in Table 2 and Table 2b.

Table 2

Example Z _m numbers.

temperature (° C)

1— 5 4-C1, 2-CH _3, -0.-CH ₂ - I— 6 2,4-Cl ₂ —O — CH— I— 7 4-CH3 _C H ₂ - I— 8 2-CHg -О-сщ- I- 9 4-F -CH2-CH2- 1—1.1 4-C1 —CH2 — CH2— 1—26 4-CH 3 —CH2 — CH., - 1-30 2-C1 —0 — CH2- 1-31 2,4-Cl2 —CH ₂ —CH2— 1-32 2-CH3 -CH2-CH2- 1—34 —0 — CH2— 1—35 4-C1 -0-CH2-

-C (.CH ₃ ..). 3

-C '(CH ₃ ) _{: i}

-C (CH ₃ ) 3

-C (CH ₃ ) 3

-C (CH 3) 3

-C [CH _; .) 3

-CCH 3) 3

-C (CH 3) 3

-C (CH ₃ ) ₃

-C (CH ₃ ) ₃

125.5.-129, 120.5—123.5: 98—101.5 89—101 91—95.5 212 (decomposition) (x HCl) oil 109—111 94—95 82—83

118—119,5

1—36 4-C1 —0 — CH2— 1—38 4-F —0 — CH2— 1-41 3-C1 —0 — CH2— 1—42 2-Cl, 4-F —0 — CH2— 1—43 _3,4-Cl2 —0 — CH2— 1—47 Whose —0 — CH2— 1-48 _ —0 — CH2— 1—49 4-OCH3 —0 — CH2— 1—50 4-C (CH _{:)) 3} —0 — CH2— 1—51 4-OCF3 —0 — CH2—

81—85

-C (CH 3) ₃

-C (CH ₃ ) ₃

-C (CH3) 3

-C (CH 3) ₃

-C (CH ₃ ) ₃

-C (CH 3) 3

-C (CH ₃ ) ₃

-C (CH3h

-C (CH ₃ ) ₃

149—151

73—75

130

124

109—111

84—85

63—66

75—78 no »= 1.4902

Example Z _m Y Number Melting point (° С)

1-52 4-SCH ₃

1-53 4-C1 -O-CH ₂ -, -CH ₂ -CH ₂ -

-С (СН ₃ ) з

-C (CH ₃ ) ₃

1-54 2,3- (CH ₃₎

1-55 2-CH-1,3-C1

1-56 2.5- (СНзЬ

1-57 2,4- (СН ₃ ) ₂

1-58 3-СНз, 4-С1

-O-CH ₂ - -O-CH ₂ - -O-CH ₂ - -O-CH ₂ - -O-CH ₂ - -O-CH ₂ -

1-61 4-С1

1—62

1—63

1—64

1—65

2,4,6- (СНз) з

4-C1, 2,6- (CH ₃ ) ₂ 3-Cl, 2-CH 3 2,3- (СНзЪ

1-66 4-C1

-CH ₂ -CH ₂ —O — CH ₂ - —O — CH ₂ - —O — CH ₂ - —O — CH ₂ - —O — CH ₂ - —O — CH ₂ -

-C (CH ₃ h

-С (СНз) з

-С (СН ₃ ) for -С (СНз) for -С (СН ₃ ) for -О

- С (СН ₃ ) з

-С (СН ₃ ) ₂

-С (СН ₃ ) з —СН (СН ₃ ) ₃ -СН (СН ₃ ) ₃

1-67 4-С1 —О — СН ₃ -

1-68 2,4- (С1) ₂ —О — СН ₂ -

1-69 4-F —О — СН ₃ -

1-70 4-С1, 2-СНз —О — СН ₃ - * 'NDS = 1,5-naphthalenedisulphonic acid

The good performance of the compounds of the invention is illustrated by the following examples.

In the following examples, A, V, C and D and G, the following compounds were tested as comparators.

(AND)

54—58> 250 (х 1/2 NDS) * ’133—134 157 94

119

115

133

75—76 102—103,5 140—141 124—125

107

- СН (СНз) ₂ 107 - СН (СНз) ₂ 104 -СН (СНз) ₂ 89 -СН (СН ₃ ) ₂ 88

(compound known from U.S. Pat. No. 3,156,554)

(compound known from DE-OS 1667 968) (compound known from DE-OS 2 838 847) (F)

(H)

(a compound known from DE-OS 2 654 890) (a compound known from DE-OS 2 838 847) (J) (G)

\

(a compound known from DE-OS 2,654,890) (a compound known from DE-OS 2,736,122).

In Examples A, B, C, D and G, the following compounds of Formula I were tested as compounds of the invention

OH

(!) example Z _m YR number

I— 1 4-C1 —O — CH2— -C (CH ₃ ) ₃ I— 4 4-C1 -CH2-CH2- -C (CH ₃ ) ₃ I— 5 4-Cl, 2-CH 3 —O — CH2— -C (CH ₃ ) ₃ I— 6 2,4-Clh —O — CH2— -C (CH ₃ ) 3 I— 7 4-CH3 —O — CH2— -C (CH ₃ h 1-30 2-C1 —O — CH2— -CCHjja 1—31 2,4-Cl ₂ -CH2-CH2- -C (CH ₃ ) ₃ 1—32 _2-CH3 -CH2-CH2- -C (CH ₃ ) ₃ 1—35 4-C1 —O — CH2—

O — CH2— ГДУ

1-36 4-C1 —O — CH2— ct 1—38 4-F —O — CH2— -C (CH ₃ ) ₉ 1—43 3,4-Cl2 —O — CH2— -C (CH ₃ ) ₃

example number ^Z m Y 1-48 -. —0 — СИ2— 1—51 4-OCF3 —0 — СИ2— 1—52 4-SCR3. —0 — СИ2— 1—53 4-C1 —CH2 — CH2— 1—55 2- SID, 3-C1 —O — сн ₂ - 1—56 2.5- (СИз) 2 —O — СН2— 1—57 ТНСИзЪ —0 — CH2— 1—58 3-СИз, 4-С1 —0 — CH2— 1—11 4-С1 -CH2 — CH2—

* NDS = 1,5-naphthalenedisulfonic acid

-С (СИз) ₃

-CfCHah

-С (СИ _Э Ь —С (СИз) for x 1/2 · NDS * »

-С (СИз) з

-С (СНз) з

-С (СИз) з

-Cl 2 h

-CtCtyja x ИС1

Example A

Growth inhibition solvent beet:

parts by weight of dimethylformamide emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate

To prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of solvent and emulsifier, and mixture ¹ is made up to the desired concentration with water.

Sugar beet plants are grown in the greenhouse until the cotyledons are fully developed. At this stage, the plants are sprayed until dripping with active ingredients. After 14 days, the plant growth is measured and the growth retardation is calculated as a percentage of the control plant growth. In doing so, 0 ·% growth retardation means a condition corresponding to that of the control plants. 100% inhibition of growth means that the plants no longer grow.

The active substances tested, their concentrations and the results obtained are summarized in the following table.

Table A

Growth inhibition of sugar beet active ingredient concentration in% inhibition of growth in%

- (review} - 0 B (known substance) 0.05 0 I— 1 0.05 90 * · ' I— 4 0.05 80 * » * *) I— 6 0.05 55 » * *) I— 7 0.05 85 » I — 11 0.05 50 1-30 0.05 40 1—31 0.05 40 1—35 0.05 85 * » **) 1—36 0.05. 40 * » * *) 1—38 0.05 95 » * *) 1-48 0.05 65 » * *) 1—51 0.05 45 » 1—53 0.05 55 » * *) 1—58 0.05 45 » E (known substance) 0.05 25

* »Strongly green leaves”> thick leaves

Example Β

Soybean growth inhibition solvent:

parts by weight of methanol emulsifier:

parts by weight of polyoxyethylene sorbitan monolaurate

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and emulsion Table B-1 and the mixture is made up to the desired concentration with water.

Young soybean plants are sprayed with preparations of the active ingredient until dew formation is fully developed. After two weeks, the increment is measured and the growth retardation is calculated as a percentage of the increment of the control plants. 100% means that the plants no longer grow and 0% is the condition corresponding to the growth of untreated control plants.

The test compounds, the concentrations used and the results obtained are summarized in the following Tables Β-1 and B-2.

Soy growth inhibition

active substance concentration in% growth inhibition in% - (control) - 0 B (known substance) 0.05 30 I— 1 0.05 95 * 1 I— 5 0.05 70 1—32 0.05 60 1—38 0.05 80 1—43 0.05 50 1-48 0.05 80 ** strong green leaves Table B - 2 Soy growth inhibition active substance concentration in% growth inhibition in% - (control) - 0 I — 1 0.1 92 0,025 85 G 0.1 81 0,025 23 H 0.1 13 0,025 9 J 0.1 11 0,025 9

Example C

Cotton growth retardant solvent:

parts by weight of dimethylformamide emulsifier:

• 1 part by weight of polyoxyethylene sorbitan monolaurate

Cotton plants are grown in the greenhouse until the 5th assimilation leaf is fully unfolded. At this stage, the plants are sprayed with the preparations of the active compound until dripping. After 3 weeks, the plant growth is measured and the growth retardation is calculated as a percentage of the control plant growth. 100% inhibition of growth means that the plants no longer grow and 0% inhibition of growth means that the plants grow as untreated control plants.

The active substances used, the concentrations used and the test results are given in Table C below.

To prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is made up to the desired concentration with water.

Table C

Cotton growth inhibition active substance concentration% growth inhibition% - (control) - 0

A (known) 0.05 40 F (known) 0.05 5 I— 1 0.05 70 * ’ I— 4 0.05 70 I— 7 0.05 90 *> 1—53 0.05 75 1—55 0.05 50 1—58 0.05 55

*> strong green leaves

Example D

Stimulation of carbon dioxide fixation · Soy solvent:

parts by weight of dimethylformamide emulsifier:

part by weight of polyoxyethylene sorbitan monolaurate

To prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is diluted with water to the desired concentration.

Soybean plants are grown in the greenhouse until the first assimilation leaf unfolds. At this stage, the plants are sprayed with the prepared active ingredient until they are wet. In the further course of the experiment, the fixation of carbon dioxide ^{1 by} plants is usually measured. The measured values are compared with those found in control plants not treated with the active substances.

Individual values are denoted by symbols with the following meaning:

- inhibition of carbon dioxide fixation carbon dioxide fixation as in control plants * low stimulation of carbon fixation ** strong stimulation of carbon fixation *** very strong stimulation of carbon fixation

The active ingredients used, concentrations of test compounds and results are summarized in the following Table D.

Table D

Stimulation of carbon dioxide fixation in soybean active substance concentration in -% efficiency

- (control) - 1—52 0.1 0.05 0,025 1—56 0.05 1—57 0.05

Example G

Growth inhibition of fescue (Festuca pratensisj solvent):

parts by weight of dimethylformamide emulsifier:

part by weight of polyoxyethylene sorbitan monotaurate

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the mixture is diluted with water to the desired concentration.

* * * * * * * * * *

The fescue plants are grown in a greenhouse to a height of 5 cm. At this stage, the plants are sprayed with the active agents until the spraying agent drips. After 3 weeks, the increment is measured and the growth retardation is calculated as a percentage of the increment in the control plants. 100% inhibition of growth means that plants do not grow any more and Ό -% represents the same growth as untreated control plants.

The active substances to be tested, the concentrations used and the test results are given in the following Table G.

Growth inhibition of fescue (Festuca pratensis) active substance concentration in%

Table G growth retardation in%

- (control) - 0 G (known) 0.1 0 0,025 0 H (known) 0.1 0 0,025 0 J (known) _; 0.1 10 0,025 0 I — 1 0.1 79 0,025 55

In the following examples E-1 and H, the following compounds were tested: known compound:

(C) [compound known [1963], 1113] from Phytopathology 33 of the compound of the invention:

С Hy NH - C - S ^Z II

WITH

example number Zm Y R I— 4 4-C1 —CH ₂ —CH ₂ - -C [CH 3] 3 1—11 4-C1 —CH2 — CH2— -C [CH 3] ₃ x HCl 1-30 2 — C1 —0 — CH2— -C (CH ₃ ) ₃ 1—31 2,4-Cl ₂ - ^ 2- ^ 2- -C [CH 3] ₃ 1—32 2-CH3 -Haha- -C [CH 3] 3 1—34 -O —0 — CH3— -C (CH 3) 3 1—35 4-C1 —0 — CH2— gČgcí 1—36 4-C1 —0 — CH2— Cl

1-38 4-F

1-42 2-C1.4-F

1-53 4-Cl-CH ₂ -O -, -O-CH2-CH2-CH2 --C _(CH3)}

-C (CH ₃ , h

-C (CH ₃ ) ₃ x 1/2 NDS *>

* NDS = 1,5-naphthalenedisulfonic acid

Example E - 1

Test for Erysiphe graminis (protective effect) barley solvent:

100 parts by weight of dimethylformamide emulsifier:

0.25 parts by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To determine the protective activity, young test plants are sprayed until wetted with the active agent. After the spray coating has dried, the plants are dusted with spores of Erysiphe graminis f. Sp. hordei.

The plants are then stored in a greenhouse at a temperature of about 20 ° C and a relative air humidity of about 80% to create favorable conditions for the development of typical powdery mildew spots.

days after inoculation, evaluation of the experiment is performed.

The active substances to be tested, the test substance concentrations used and the test results are summarized in Table E-1 below.

Table E - 1

Test for Erysiphe graminis (barley) - protective effect active substance concentration of active substance in spray suspension in% weight attack in% of untreated control plants infected

(C) (known substance) 0,025 100 ALIGN! I— 4 0,025 0.0 I — 11 0,025 0.0 1-30 0,025 0.0 1—31 0,025 0.0 1—32 0,025 0.0 1—34 0,025 12.5 1—35 0,025 0.0 1—36 0,025 8.8 1—38 0,025 0.0 1—42 0,025 0.0 1—53 0,025 0.0

Example H

Powdery mildew test Erysiphe graminis f. Sp. hordei (barley) - seed treatment

The active ingredient is used in the form of a dry mordant which is prepared by thoroughly mixing the respective active ingredient with a mineral to form a fine powder mixture which ensures an even distribution of the active ingredient on the seed surface.

The application of the mordant is carried out by shaking the seed together with the mordant for 3 minutes in a closed glass bottle.

The barley seed is then sown in standard soil to a depth of 2 cm (3 x 12 grains). 7 days after sowing, when young plants develop their first leaf, they are dusted with spores of Erysiphe graminis f. Sp. hordei.

The plants are then placed in a greenhouse where they are stored at about 20 ° C and about 80% relative humidity to create favorable conditions for the development of typical powdery mildew piles.

days after inoculation, the experiment is evaluated.

The active substances used, their concentrations and the results obtained are summarized in the following Table H.

Erysiphe graminis f properties Sp. hordei (barley) - seed treatment amount of active substance used in mg / kg of seed infestation in% of untreated control plants infected C (known) 2 500 100 ALIGN! I— 4 1000 0.0 I — 11 1000 0.0 1—38 1000 0.0 1—42 1000 33.8 1—53 1000 0.0

In the following Examples E and F, the following compounds were tested: known compound (C) [compound known from Phytopathology 33 (1963), 1113] compounds of the invention

example number

I — 1 4-C1 —O — CH2— -C _(CH3) .3 1—5 4-Cl, 2-CH 3 —O — CH2— -C (CH ₃ h 1—6 2,5-Cl ₂ —O — CH2— _C [CH3) ₃ 1—7 4-CH3 —O — CH2— -C (CH ₃ ) ₃ 1—8 _2-CH3 —O — CH2— -C (CH _and h 1-9 4-F -CH2-CH2- -C (CH ₃ ) 3

Tests E and F are performed as follows:

Example E

Test for Erysiphe graminis (protective effect) barley solvent:

100 parts by weight of dimethylformamide emulsifier:

0.25 parts by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To determine the protective activity, young test plants are sprayed until wetted with the active agent. After the spray coating has dried, the plants are dusted with spores of Erysiphe graminis f. Sp. hordei.

The plants are then stored in a greenhouse at a temperature of about 20 ° C and a relative air humidity of about 80 ° / o to create favorable conditions for the development of typical powdery mildew spots.

days after inoculation, evaluation of the experiment is performed.

The active compounds tested, the active compound concentrations used and the results are summarized in the following Table E.

E

Test for Erysiphe graminis (protective effect) barley active substance concentration of active substance infestation in% untreated sprayed in% weight control

C (known) 0,025 100 ALIGN! I — 1 0,025 0.0 1—5 0,025 0.0 1—6 0,025 0.0 1—7 0,025 0.0 1—8 0,025 0.0 1-9 0,025 0.0

Example F

Test for systemic action on powdery mildew (Erysiphe graminis var. Hordei) - fungal disease of grain shoots

The active ingredient is used in the form of powdered mordant. seed. The mordant is prepared by mixing the respective active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth to form a finely divided powder containing the active ingredient at the desired concentration.

The barley seed is treated by shaking with prepared mills in a closed glass container. The seed is then sown (3 x 12 grains) 2 cm deep into pots containing a mixture of one volume of standard peat soil and one volume of quartz sand. Germination and emergence of plants takes place under favorable conditions in the greenhouse. 7 days after sowing, when barley plants unfold their first leaf, they are dusted with fresh spores of Erysiphe graminis var. hordei and kutivují at 21-22 DEG C. and 80-90% relative humidity ¹ at sixteen to light. Typical powdery mildew spots are formed on the leaves of the plants within 6 days.

The degree of infestation is expressed as the percentage of infestation of untreated control plants, with 0% representing no infestation and 100% / o representing the same infestation as untreated control plants. The more active the active substance, the lower the extent of the disease.

The active substances tested, the concentrations used and the results are summarized in the following Table F.

Table F

Systemic effect test on powdery mildew (Erysiphe graminis var. Hordei) Active substance Concentration Effective amount of infestation used in% of the substance in the mordant of the mordant in g / kg Untreated controls in% of seed

C (known)

1-5

100 ALIGN!

25.0

In the following Examples J and K, the following compounds were tested:

(a compound known from DE-OS 27 36 122) The compounds according to the invention:

Compounds known in the art:

(D)

Cl - CH 2 CH-CO-C (C ₃ ) _Э

(I) (a compound known from DE-OS 27 34 426)

Cl

31 Example Number Zm I— 4 4-CI 1-30 2-CI 1—34 1—35 4-C1 1—36 4-C1 1 - 38 4-F 1—42 2-Cl, 4-F 1—43 _3,4-Cl2 Tests J and K are performed as follows. described below Example J

Seal on powdery mildew Sphaerotheca fuliginea (cucumber) /protective effect solvent:

4.7 parts by weight of acetone emulsifier:

0.3 part by weight of alkylaryl polyglycol ether

To obtain a suitable active agent, 1 part by weight of the active ingredient is mixed with the indicated amounts, solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To determine the protective activity, young plants are sprayed with the active ingredients up to the wetting stage. After the spray layer has dried, the plants are dusted with conidia of Sphaerotheca fuliginea.

The plants are then placed in a greenhouse at 23-24 ° C and a relative air humidity of about 75%.

Evaluation is carried out 10 days after inoculation.

The active ingredients used, the concentrations applied and the results are summarized in Tables J-1 and J-2 below.

Y R -CH2-CH2— -C (CH ₃ ) ₃ -0-CH ₂ - -C (CH ₃ ) ₃ —0 — CH2— -C (CH ₃ ) ₃ -0-CH ₂ - - —0 — CH2— / Λ ( Ct —0 — CH2— -C (CH ₃ ) ₃ —0 — CH2— -C (CH ₃ ) ₃ —0 — CH2— -C (CH ₃ ) ₃

Table J — 1

Test for powdery mildew (Sphaerotheca fuliginea) (o kuirkaj / protective effect of active substance attack in% at active substance concentration of 1 ppm

D (known) 84 I— 4 12 1-30 16 1—34 12 1—35 12 1—36 15 Dec 1—38 15 Dec 1—43 12

Table J - 2

Powdery mildew test (Sphaerotheca fuliginea (cucumber / protective effect active substance attack in% at active substance concentration 1 ppm

J (Known) 45

1—3019

1—425

Example K

Test for apple scab (Venturia inaequalis) (apple tree) / protective effect solvent:

4.7 parts by weight of acetone emulsifier:

0.3 part by weight of alkylaryl polyglycol ether

To obtain a suitable active ingredient, 1 part by weight of the active ingredient is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To determine the protective activity, young plants are sprayed with the active preparation up to the wetting stage. After the spray layer has dried, the plants are inoculated with an aqueous suspension of apple scab (Venturia · inaequalis) conidia and then incubated (at 20 ° C and 100% relative humidity for one day).

The plants are then placed in a greenhouse where they are kept at 20 ° C and 70% relative humidity.

The test compounds, concentrations used and results are shown in Table K below:

Table K

Test for apple scab (Venturia inaequalis) (apple tree j / protective effect active substance attack in ·% at active substance concentration 1 ppm

96

I— 412

1—341

1—367

Claims (2)

vynalezu A plant growth regulating agent and a fungicidal agent, characterized in that it contains as active ingredient one derivative of 1-hydroxyethylazole of the formula I, at least generally being the number · 0, 1, 2 or 3, or · an addition salt thereof with with hydrochloric acid or with naphthalene-1,5-disulfonic acid. 2. A process for the preparation of an active ingredient according to claim 1, which comprises treating the oxiranes of the formula II OH R O - CH ₂ (II) in which R represents an alkyl group having carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms which is optionally substituted by an alkyl group having 1 to 2 carbon atoms, or a phenyl group which is optionally substituted by halogen and / or an alkyl group having 1 to 4 atoms carbon, Y denotes -OCH 2 or -CH ₂ -CH ₂ -, Z is halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, haloalkyl 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 or 2 carbon atoms; 2 · carbon atoms having 1 to 5 halogen atoms or a phenyl group optionally substituted by halogen and / or alkyl having 1 to 4 carbon atoms, and 1 to 4 wherein R, Y, Z and m are as defined above, with triazole III (III) in the presence of a diluent and optionally in the presence of a base at a temperature of 0 to 200 ° C, followed by addition of hydrochloric acid or 5-Naphthalenedisulfonic acid.