DK157002B - 1.3-dihalogen propan-2-oles - Google Patents

Abstract

1.3-dihalogen propan-2-oles with the general formula: <IMAGE>in which X<1> and X<2> which can be joined or separate, each are halogens, and R<1> is any substituted alkyl- cycloalkyl, aryl- or aralkyl group are valuable intermediate products in the production of fungicide and products to regulate plant growth as well as products that are orally or topically effective against fungal disease in humans and other animals.

Description

DK 157002 B

The invention relates to novel 1,3-dihalogenpropan-2-ols which can be used as intermediates in the preparation of triazole and imidazole compounds which are useful as fungicidal and plant growth regulating products and as pharmaceutical and veterinary products, especially such products which are orally or topically effective against fungal diseases in humans and other animals. These products are particularly useful for the treatment of candidiasis and human dermatophyte infections.

10 from DE patent specification 168,941, symmetrical dihalogen derivatives of tertiary alcohols are known, from US patent 2,061,377 a dichloro- and trichloro-tert-butyl alcohol are known, from GB patent specification 1,144,063 are known 1,1,1 , 3-tetrachloro-2-chloromethyl-2-propanol, and from the journal "Journal of the 15 Chemical Society (London)", 1961, pages 3452-3457 are known inter alia 1,3-difluoro-2-phenylpropan-2-ol, which compounds are related to the compounds of the invention.

The invention relates to 1,3-dihalo-propan-2-oils which are properties in that they have the general formula:

OH

X1-CH2-C-CH2-X2 R1 wherein X1 and X2, which are the same or different, are each halogen and R1 is an alkyl or cycloalkyl group, each optionally halogen or (C1-C4) -alkoxy-substituted and each containing 3 to 6 carbon atoms, or R 1 is a (C 1 -C 3 alkoxy-substituted alkyl group of 1-2 carbon atoms, or R 1 is unsubstituted benzyl or phenyl or benzyl, both of which are sub -stituted one or more times with halogen, alkyl, alkenyl or haloalkyl each containing from 1 to 5 carbon atoms, alkoxy or haloalkoxy, each containing from 1 to 35 carbon atoms, nitro, cyano, hydroxy, alkylthio containing from 1 to 4 carbon atoms, or phenyl, halophenyl or phenoxy, wherein the alkyl portion of the benzyl is optionally substituted by alkyl containing from 1 to 4 carbon atoms, or phenyl.

2

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The compounds of the invention can be used as intermediates in the preparation of compounds of general formula I:

5 OH

Y1 — N —CH 2 —c —CH 2 —N Y2 (I) V a * w

N N

wherein γΐ and Y₂, which are the same or different, are N or CH and Rl is as defined above, as well as salts, metal complexes, ethers which are alkyl, alkenyl, alkynyl, aryl or aralkyl ethers, and esters , which are alkanoyl, benzoyl or sulfonyl esters thereof.

15

The bis-azolyl compounds of formula I may contain chiral centers. Such compounds are generally obtained in the form of racemic mixtures. However, these and other mixtures can be separated into the individual isomers by methods known in the art.

The salts of the compounds of formula I may be the salts of inorganic or organic acids, e.g. hydrochloric acid, nitric and sulfuric acid, acetic acid, p-toluenesulfonic acid or oxalic acid. The salts can also be quaternary salts.

2 o The metal complex is suitably a complex containing as metal, copper, zinc, manganese or iron.

The compounds of the invention may be used in the preparation of fungicidal and plant growth regulating products which contain as active ingredient a compound of formula I as defined above or a site, a metal complex, an ether or an ester thereof. These products may contain a carrier for the active ingredient.

The compounds of the invention can also be used to prepare a pharmaceutical or veterinary fungicide.

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product comprising a compound of formula I as defined above or a site, a metal complex, an ether or an ester thereof together with a pharmaceutically or veterinarily acceptable diluent or carrier.

5

Examples of compounds which can be prepared from the compounds of the invention are given in Table I.

10 15 20 25 30 35 4

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ΤΑΒΈΖ- I

Compound R ^ * Y ^ Y ^ Melting point 1 ° C) 1 4-Cl-C6H4-. = N- = N- 153-155 3 4-F-CgH4- = 11- = N- 124-126 4 2f4-diCl-C6H3- = N- = N- 183-186 5 2,4-diCl-C6H3- CH2- = N- = N- 137-140 6 4-CH - C ^ H, - = N- = N- 179-180 3 6 4 7 4-C6H5-C6H4- = N- = N- 165-170 8 4-CH30-C6K4- = N- = N- 141-143 · 9 2-Cl-C6H4- = N- = N- 145-148 10 4-C6H50-C6H4- = N- = K-163-165 11 2-CF3-C6H4- = N- = N-12 2,4-diCl-C6H3- = CH- = CH-160-175 13 2/4-diCl-C6H3- = N- ^ CH-169-170 14 n -C4H9- = N- = N- 61-62 4-C1-C6H4CH2- = N- = N- 16 _ 2-C1-C6H4CH2- = N- = N-17 2,6-diCl-C6H3CH2- = N - = N- 18 4-CH30-C6H4CH2- = N- = N- 19 C6H5CH2- = N- = N- 101-102 20 2,4-diClC6H3CH- = N- = N- iHj 21 4-Cl-C6H4ÇH- = N- = N- oH5 _______ 5

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TABLE T continued 5

Compound r ^ y ^ · y ^ Melting point (° C) 23 2,6-diClC6H3- = N- = N- 24 4-CF30C5H4- = N- = N-25 '2,4,6-triClC6H2- = N- = N- 26 4- (Cl-C6H4) C6H4- = N- = N- 27 2- (C6H50) C6H4- = N- = N- 28 4-CH2 = CH-C5H4- = N- = N- 126_128 29 t-C4H9- = N- = N- 85-87 30 i-C4K9- = N- = N- 31 / \ = N- = N- 20 '' 32 tC ^ CH ^ = N- = N - 33 3,4-diClC6H3- = N- = N- 140-145 aq. ethanol / water 1: 9 25 34 t-C4Hg- = N- = CH- 129-130 35 4-CF3-C6H4- = N- = N ~ 164-165 The following abbreviations have been used in the above table. T- = tertiary i- = iso- = cyclohexyl 35 '' diCl = dichloro-triCl = trichloro-

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6

The compounds of the general formula I listed above can be prepared by reacting a 1,3-dihalogenpropan-2-ol of the general formula II,

5 OH

χΐ - CH2CCH2 - X1 (II)

Rl wherein χΐ and X ^ being the same or different are each halogen 10 in (chlorine or bromine) and R) is as defined above, with imidazole or 1,2,4-triazole or a site thereof (f. e.g., the sodium salt). This reaction can be carried out in a suitable solvent, such as methanol, ethanol, acetonitrile or dimethylformamide, at a temperature of 20-100 ° C. The dihalogen propan-2-ol is preferably added to an excess of the sodium salt of the heterocyclic base in dimethylformamide at 100 ° C. The product can be isolated by adding the solution to water followed by recrystallization.

The 1,3-dihalogen propan-2 oils can be prepared by reacting a 1,3-dihalogen acetone with the appropriate Grignard reagent according to known methods (e.g., Johnson et al., J. Org. Chem., 1962, 27, 2241-2243 ).

5

The salts and metal complexes of the compounds of general formula I can be prepared from the latter in known manner.

The complexes can e.g. is prepared by reacting the non-complexing compound with a metal salt in a suitable solvent.

30

The ethers can be prepared by treating the sodium salt of the alcohol with a reactive halogenated compound (eg methyl bromide or iodide, benzyl chloride or all lyl bromide). The esters can be prepared in a similar way by treating sodium 35 7

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the salt of the alcohol with an acid chloride (eg acetyl chloride, benzoyl chloride or methanesulfonyl chloride).

The compounds and salts, metal complexes, ethers and 5 esters thereof are effective fungicides especially against the diseases:

Piricularia oryzae on rice

Puccinia recondita, Puccinia striiformis and other forms of rust on wheat, Puccinia hordei, Puccinia striiformis and other forms of rust on barley and rust on other hosts, e.g. coffee, apples, vegetables and ornamental plants,

Plasmopara viticola on wine,

Erysiphe graminis (powdery mildew) on barley and wheat and other I5 powdery mildews on different hosts, such as

Sphaerotheca fuliginea on cucumber plants (eg cucumber), Podosphaera leucotricha on apples and üncinula necator on wine, Helminthosporium spp. and Rhynchosporium spp. on cereals, Cercospora arachidicola on peanuts and other Cercospora species on e.g. sugar beet, bananas and soybeans,

Botrytis cinerea (grass mold) on tomatoes, raspberries, wine and other hosts,

Phytophthora infestans (mold) on tomatoes,

Venturia inaequalis (scab) on apples.

25

Some of the compounds have also exhibited a wide range of efficacy against fungi in vitro. They are effective against various diseases of fruit after harvest (eg Penicillium digatatum and italicum on oranges and Gloeosporium musarum 30 on bananas). Some of the compounds are also active as agents for: Fusarium spp., Septoria spp., Tilletia spp. (i.e. wheat stink fire, a premature disease of wheat), üstilago spp., Helmithosporium spp. on grain, Rhizoctonia solani on cotton and Corticium sasakii on rice.

The compounds can move mid-point in the plant tissue. In addition, the compounds may be volatile enough to be active in the vapor phase against fungi on the plant.

35

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8

The compounds and their derivatives so defined above also have plant growth regulating effects.

The plant growth regulating effects of the compounds manifest 5 e.g. as a growth inhibitory or dwarf growth-promoting effect on the vegetative growth of woody and herbaceous monocotyledonous plants. Such growth inhibition or dwarf growth may be useful, e.g. in peanuts, cereals, and soybeans, where diminished stem growth can reduce the risk of plants letting and also allowing the supply of increased amounts of fertilizer. Growth reduction in woody plants is useful in regulating the growth of bottom vegetation under high-voltage lines, etc. flowering and maturation can be regulated by supply of the compounds. Growth reduction in peanuts can facilitate harvesting. Growth inhibition in 20 grasses can help preserve lawns. Examples of suitable grasses are Stenotaphrum secundatum (St. Augustine grass)., Cynosurus cristatus, Lolium multiflorum and perennium, Agrostis tenuis, Cynodon dactylon (Bermuda grass), Dactylis glomerata, Festuca spp. (e.g. Festuca rubra) and Poa spp.

25 (e.g., Poa pratense). The compounds can cause reduced grass growth without significant phytotoxic effects and without detrimental effect on the appearance of the grass (especially the color). This makes such compounds attractive for use on ornamental lawns and on grass discounts. They can also have an effect on the flower head marrow in e.g. grasses.

The compounds can also cause reduced growth in weeds found in the grasses. Examples of such weed species are semi-grasses (eg, Cyperus spp.) And two-leafed weeds (eg bellis, broadleaf, willow, honorary price, 35 thistle, acid and scent). The growth of non-crop vegetation (for example, weeds or cover vegetation) can be inhibited and thus help in the maintenance of planting and field crops. In orchards, especially plantations

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9 which is subject to soil erosion, the presence of grass cover is important. Vigorous grass growth, however, requires substantial maintenance. The compounds could be useful in this situation as they could restrict growth without killing the plants, which would lead to soil erosion. At the same time, the degree of competition for nutrients and water of the grass would be reduced and this could result in an increased fruit yield. In some cases, one type of grass can be reduced in size more than another type of grass. This selectivity may be useful, e.g. to improve the quality of a soil turbine by preferably suppressing the growth of undesired species.

Dwarf growth can also be useful when you want small ornamental, living room, oak and nursery plants (eg poinsettia, cherry-santhemum, carnations, tulips and daffodils).

As indicated above, the compounds can also be used to effect dwarf growth in woody species. This property can be used to control the growth of live fences or to shape fruit trees (eg apples). Some conifers do not significantly reduce the growth of the compounds, so that the compounds could be useful in combating unwanted vegetation in coniferous plant shoals.

The plant growth regulating effect may (as indicated above) be demonstrated by an increase in crop yield.

In potato, seedling control in the field and inhibition of germination during storage may be possible.

30

Other plant growth regulating effects caused by the compounds include changing the leaf angle and forming a greater number of shoots from the stem of monocotyledonous species. The aforementioned effect may be useful, e.g. by changing the blade orientation of e.g. potato crops with the purpose of facilitating the light supply to the crop and causing a bird's eye view of photosynthesis and tuber weight. By increasing shoots in single-seeded crops (eg rice) the number of flowering shoots can

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10 pr. area of land is increased, thereby increasing the total grain yield of such crops. In severe weather conditions, an increase in the firing rate could result in a closer grass layer, which may result in increased tension in use.

5

The treatment of plants with the compounds may cause the leaves to assume a more dark green color.

The compounds may inhibit or at least delay the flowering of sugar beet and may thereby increase sugar yield. They can also reduce the size of the sugar beet without thereby significantly reducing the sugar yield and thereby allowing the plants to stand closer. Similarly, in other root crops (eg turnips, cauliflower, cuttlefish, 15 parsnip, root beets, yams and cassava) it may be possible to increase the density of the plants.

The compounds could be useful for limiting the vegetative growth of cotton and thereby leading to an increased cotton yield.

The compounds can be useful in making the plants resistant to climatic effects, as the compounds can delay the emergence of plants grown by seeds, shorten the stem height and delay flowering. These properties could be useful in preventing frost damage in countries where there is a significant snowfall in winter, as the treated plants would then remain under snowfall during the cold period. In addition, the compounds can make certain plants resistant to drought or cold.

When used for seed treatment in small quantities, the compounds can have a growth stimulating effect on plants.

In carrying out plant growth regulation with the compounds, the amount of compound to be added to regulate the growth of plants will depend on a number of factors, e.g. the particular connection one chooses to use, and the identity

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Eleven of the plant species whose growth is to be regulated. However, in general, an amount of 0.1-15, preferably 0.1-5 kg / ha, is used. However, in certain plants, amounts outside these ranges may also produce undesirable phytotoxic effects. It is necessary to conduct routine examinations to determine the optimal amount of a particular compound for a particular purpose for which it is suitable.

The compounds can be used as such for fungicidal or plant growth regulating purposes, but are more conveniently prepared for products for such use. To this end is provided a fungicidal or plant growth regulating product which comprises a compound of the general formula (I) as previously defined or a site, a metal complex, an ether or an ester thereof and optionally a carrier or diluent.

A method for controlling fungi is that a compound, a site, a metal complex, an ether or an ester thereof is added to a plant, to the seed of a plant or to the site of a plant or seed. previously defined.

One method of regulating plant growth is that a compound, a seed or a seed, a metal complex, an ether or an ester thereof is added to a plant, to a plant or to a plant or seed, as previously defined. .

The compounds, salts, metal complexes, ethers and esters 30 can be added in a variety of ways, e.g. prepared or prepared directly for the law of a plant, or they may also be fed to shrubs or trees, to or from another medium in which plants, shrubs or trees are grown or to be planted, or they can be sprayed, powdered or applied as a cream or paste or they can be applied as a vapor. The feed can be done to any part of the plant, bush or tree, e.g. to the law, the stems, the branches or the roots or the soil surrounding the roots or to the seeds for sowing

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12

The term "plant" in the present text should also include sprouts, shrubs and trees. The fungicidal process further includes preventive, protective, prophylactic and extinct treatment.

5

The compounds are preferably used for agricultural and horticultural purposes in the form of a prepared product. The product type used will in many cases depend on the intended use.

The following examples illustrate the invention.

Example 1

This example illustrates the preparation of Compound 15 1,3-Bis- (1,2,4) -triazolyl-2-p-chlorophenylpropan-2-ol (Compound No. 1 in Table 1). T ri η 1. A Grignard reagent [prepared from p-chloroiodine benzene (0.22 mol) in sodium-tar diethyl ether (65 ml) and magnesium-span (0.24 g atoms)] was added dropwise in a 1 hour solution to a stirred solution of 1.3- dichloroacetone (0.2 mol) in sodium-tarred diethyl ether (270 ml) kept at -60 ° C. The mixture was stirred for a further 1 hour at -60 ° C after completion of addition. Glacial acetic acid (21 ml) in diethyl ether (320 ml) was added dropwise to the solution and the temperature was allowed to rise to 0 ° C. The solution was washed with water (2 x 150 ml) and tarred (Na 2 SO 4). Removal of the solvent gave a pale yellow oil which was distilled off at the oil pump to give 1,3-dichloro-2-p-chloro-phenylpropane ~ 2-ol (85%), boiling point 100-102 ° C / 30 ° C. 2 mmHg.

Step 2. 1,2,4-triazole (0.045 mol) was added portionwise to a stirred suspension of sodium hydride (0.045 mol - using a 50% suspension in oil) in dimethylformamide (15 ml), and stirring was continued. until the shower started. 1,3-Dichloro-2-p-chlorophenylpropan-2-ol (0.015 mol) in dimethylformamide (5 ml) was added dropwise to the solution at 20 ° C and stirring was continued at 100 ° C for 6 hours. After descaling to the living room 13

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At temperature, the mixture was poured into water and the resulting solid was filtered off and washed with diethyl ether. Recrystallization from ethyl acetate gave the title compound as a crystalline solid (yield 50%), m.p. 153-155eC.

5

The remaining compounds in Table I, i.e., compounds no.

3-32 were prepared in a similar manner as described in steps 1 and 2 using appropriate starting compounds. Crystallization details and other purification methods 10 are as follows:

Compound No. Recrystallization Details and Comments on Preparation 1 From ethyl acetate.

15 3 From ethyl acetate: 60-80 gasoline after chromatography on silica.

4 From ethyl acetate after chromatography on 1 ica.

5 From chromatography on silica.

20 6 From ethyl acetate after chromatography on silica.

7 From chromatography on silica.

8 Chromatographed on alumina. Recrystallize in the methanol / ethyl acetate serine as oxalate salt.

9 Solid raw product probed with ether.

Recrystallization from ethyl acetate.

Example 2 30

This example illustrates the preparation of the compound 1,3-bis- (1,2,4) -triazolyl-2- (2,4-dichlorophenyl) propan-2-ol (Compound No. 4 from Table I) Step 1. A Grignard Reagent (prepared by adding 30 g of 2,4-dichlorodiodo benzene (0.11 mol) to 3.0 g of magnesium chips (0.125 g of atoms) in refluxing ether (200 ml of ait) over 3 hours) to 12.7 g of 1,3-dichloroacetone 14

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(0.10 mol) - stirred in 100 ml of tor ether in a toris-ace tone bath - for 45 minutes. The reaction mixture was stirred for a further 4 hours, allowing the bath to assume the temperature for approx. 0 ° C and 10 ml of acetic acid was added in 5 100 ml of ether over 5 minutes.

It was diluted with 400 ml of water and the ethereal layer separated and washed successively with potassium metabisulphite solution (about 10%), water and saturated brine. Filtration through anhydrous sodium sulfate and evaporation in vacuo afforded 27.2 ml of a light brown oil. This crude mixture of 1,3-dichloro-2- (2,4-dichlorophenyl) -propan-2-ol and 1,2-epoxy-3-chloro-2- (2,4-dichlorophenyl) -propane was used directly in the next step.

Step 2. Sodium hydride (50% dispersion in oil) 14.4 g (0.3 mole) was washed with 60-80 gasoline twice, suspended in 50 ml ter DMF under argon, and 1,2,4-triazole 21 g (0.30 mol) in 60 ml of DMF was added over 30 minutes at a temperature below 1 g of 50 ° C. After the onset of hydrogen evolution (about 30 minutes after the addition), the crude dichloride / epoxide mixture from fer, 27.2 g ait, was added to the reaction mixture, dissolved in 25 ml DMF including washing liquids over 10 minutes at 25-35 ° C with stirring. After the addition, the reaction mixture was heated under stirring for 6 hours at 100 ° C. It was then stirred overnight at room temperature and most of the DMF evaporated in vacuo at ca. 50-80 ° C. The labeled residue was partitioned between 200 ml of water and 200 ml of chloroform. The perfect one! was extracted again with chloroform (2 x 100 ml) and the combined extracts washed with 100 ml of water and 100 ml of brine. Filtration through anhydrous sodium sulfate and evaporation in vacuo gave 20.5 g of moist brown solid. Transmitting with 200 ml of boiling ether and filtration (cold) gave 10.2 g of 1,3-bis- (1,2,4) triazolyl-2- (2,4-dichlorophenyl) propan-2-ol as a light brown solid, m.p. 182-185eC, purely by H.c. (silica gel K60, ethyl acetate: methanol 4: 1). The mother liquor from the chromatography on silica gel in CH 2 Cl 2 and developing with ethyl acetate followed by methanol / ethyl acetate (1: 4) gave an additional 0.90 g of material of the same purity. Total yield: 33% (calculated on DCA).

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15

Analysis: Calculated for C 13 H 21 Cl 2 N 6 ° (339) C, 46.0; H, 3.50; N, 24.8. Found: C, 45.9; H, 3.6; N, 24.7.

P.m.r. CDCl3 (90 MHz) δ 4.83 (q, 4H, CH 2 N) δ 5.64 (s, 1H, OH), 7.31 (m (ABX), 3H, Ar), 7.83 (s, 2H, Tr), 8.07 (s, 2H, Tr) ppm.

Example 3 This example illustrates the preparation of the compound 1,3-bis- (1,2,4) -triazolyl-2-n-butylpropan-2-ol (Compound No. 14 from Table I) T ri η 1. Et Grignard Reagent [prepared from n-butyl bromide 15 (0.08 mol) in sodium-dried ether (50 ml) and magnesium flakes (0.08 g atoms)] was added dropwise over 1 hour to a stirred solution of 1.3- dichloroacetone (0.08 mol) in sodium-dried diethyl ether (100 ml) kept at -60 ° C. The mixture was stirred for a further 1 hour at -60 ° C after addition. Glacial acetic acid (10 ml) was added dropwise and the temperature allowed to rise to 0 ° C. The solution was washed with water (2 x 150 ml) and dried over anhydrous sodium sulfate. Removal of the solvent gave a pink liquid which was distilled at the oil pump to obtain 1,3-dichloro-2-n-butylpropan-2-ol 25 (30%), boiling point 44 ° C / 0.04 mm Hg.

Step i n 2. 1.2.4-1 ri azo 1 (0.067 mol) was added portionwise to a stirred suspension of sodium hydride (0.076 mol - using 50% suspension in oil) in dimethylformamide (30 ml) and stirring was continued until the shower ceased. 1,3-dichloro-2-n-butylpropan-2-ol (0.022 mol) in dimethylformamide (5 ml) was added dropwise to the solution at 20 ° C and stirring was continued at room temperature for 24 hours. The mixture was poured into water and the resulting solid was filtered off and dried. Recrystallization from ethyl acetate gave the title compound (30%), m.p.

61-62 e C.

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16

Biological tests, fungicidal activity

The compounds were tested against a wide variety of leaf fungal diseases in plants. The techniques used were of different kinds: 5 The plants were grown in John Innes Potting Compost (no. 1 or 2) in mini pots with a diameter of 4 cm. A layer of fine sand was placed at the bottom of the pots containing the dicotyledonous plants to facilitate the uptake of the test compound by the roots. The test compounds were prepared either by ball milling with aqueous Dispersol T or as a solution in acetone or acetone / ethanol, which was diluted to the required concentration immediately for use. For leaf diseases, suspensions (100 ppm active ingredient) were sprayed on the ground. Exceptions to this were the studies on Botrytis cine-15 rea and Venturia inaequalis. The spray liquids were added to the maximum retention and the roots soaked to a final concentration of approx. 40 ppm a.i./tor soil. Tween 20 to reach a 0.05¾ concentration was added when the spray liquids were used for cereals.

20

For the majority of studies, the compound was applied to the soil (the roots) and to the promised (by spraying), one or two days before the plant became infected with the diseases. An exception was the study on Erysiphe graminis, where the plants were infected 25 days before treatment. After infection, the plants were placed in an appropriate environment which allows infection to occur and then incubated until the disease is ready for determination. The period between infection and determination ranged from 4-14 days depending on the disease and the environment.

30

Disease control was determined using the following scale: 4 = no disease 3 = trace - 5¾ disease on untreated plants 2 = 6-25% disease on untreated plants 35 1 = 26-59% disease on untreated plants 0 = 60-100% disease on untreated plants

The results are shown in Table II.

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17 03

<H

M J

OS I

p in ^^ σ® ssal

> B

H

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2 S | ·.

03 Q 2 · «* ^ O H« U βΈ «O g H §-F, - - V KO, <03

'H

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W S CO O CO

. - Ο Μ π ffl UC- h 'H <

T H

jri PS w. · S <<PP J N -

<B>> - * uî O O

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a 03 PP H PU B - H M Cn 03 2> 1 ^ ^> * <Λ os «w o <<· H H ^ B H Ci) H Q 13 _ CJ B <D co ^ U O> D U Λ PU W'- '

U.S

S

^. rH CO ^ p | i 1 1 18

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Biological assay, plant growth regulating action

These seals illustrate the compounds' plant growth regulating properties. The compounds were applied in the form of a 4000 ppm solution in distilled water and the solution was fed to young sprouts of different plants. The seals were repeated twice. At 12 or 13 days after treatment, the plants were examined for plant growth regulating effects and phytotoxic symptoms.

10

Table III shows the growth inhibitory effect of the compounds on vegetative growth using the following grading scale: 1 = 0-30% deceleration 15 2 = 31-95% deceleration 3 = 75% deceleration.

If no number is given, the compound was essentially inactive as growth inhibitor. Additional plant-20 growth-regulating properties are given as follows: G = more dark leaf color A = apical effect T - impact on shoot phrase.

25 30 35 19 r -.........

g '* DK 157002 B

g O O

O CN ΟΊ

EH

co

b O

H

SJ

EH

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si

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H

-. CO Εη- Η ρ £ · - P K -η

. . -. > h H H

Eh S!

U O are P Q O

H

H

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H

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ffl W H S

rtj O iH | ~ (eh 5 rfj

S

CJ

CO CO H H Eh P

co P 04

O P Pi P

0 rfj j

Pi w

PH

«O 2 2

P Pi rM H

CO

sS CO H

δ

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CO

Il H *

Pu__

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20

Example 4

This example illustrates the preparation of the 2,6-dichlorobenzyl ether of the compound of Example 1 (Compound No. 1 in Table I). The reaction was as follows: Ο. Ο Λ r \ - * S / v0

Xe * · y. O p O Q.

cl 20 The compound of Example 1 (Compound No. 1 of Table I) was added 3.04 g (10 mmol) in portions to 0.50 g of 50% NaH dispersion in oil (washed oil-free with 50-80 gasoline) at 20-35 ° C in 15 ml of DMF. After H2 development ceased, 2.0 g of 2,6-dichlorobenzyl chloride (10 mmol) in 20 ml of DMF was added and the reaction mixture was stirred at 90-100 ° C for 48 hours. It was partitioned between ethyl acetate and water and the organic layer separated and washed three times with water and once with brine. Anhydrous Na 2 SO 4 ring and evaporation in vacuo gave 4.40 g of a pale yellow oil. After cooling in ether / ethyl acetate, 1.2 g of a tar-like solid and 1.35 g of a light-yellow solid (second yield) were obtained, and the first yield had a melting point of 133-139 ° C. Recrystallization of the combined yields yielded 2.20 g of tinted colorless plates, m.p. 133-138 ° C.

Pure by thin layer chromatography on silica gel (ethyl acetate / 35 CH 3 OH; 9: 1).

Analysis: C 48.0 / 4.2 / 16.8 for 020 ΐΐ7 ^ ΐ3Νρ0 2H2Û (463.5; 36)

Claims (1)

R 1 wherein X 1 and X 2, which are the same or different, are each halogen, and R 1 is an alkyl or a cycloalkyl group, each optionally halogenated or (C 1 -C 4) -alkoxy substituted and each containing 3 -6 carbon atoms, or R * is a (C 1 -C 4) alkoxy-substituted alkyl group of 1-2 carbon atoms, or R 1 is unsubstituted benzyl or phenyl or benzyl, both of which are substituted one or more times by halogen , alkyl, alkenyl or haloalkyl each containing from 1 to 5 carbon atoms, alkoxy or haloalkoxy, each containing from 1 to 25 carbon atoms, nitro, cyano, hydroxy, alkylthio containing from 1 to 4 carbon atoms, or phenyl, halogenophenyl or phenoxy and wherein the alkyl portion of the benzyl is optionally substituted by alkyl containing from 1 to 4 carbon atoms, or phenyl. 30 35