DD145990A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The invention relates to novel 1,2,4-triazole derivatives of the formula I in which R & ind1! optionally substituted (C & ind1! -C & ind12!) -alkyl, optionally substituted (C & ind2! -C & ind5!) -alynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted phenyl, furanyl, thienyl, pyridyl or (C & ind1! -C & ind4!) - Alkoxycarbonyl, and R & ind2 !, R & ind3! Which may be the same or different, optionally substituted (C & indl! -C & ind12!) Alkyl, optionally substituted cycloalkyl, optionally substituted phenyl, optionally substituted (C & indl! -C & ind12!) Alkoxy, optionally substituted (C & ind5! -C & ind6!) - cycloalkoxy, (C & ind3! -C & ind6!) - alkenyloxy, halo (C & ind3! -C & ind6!) -Alkenyloxy, (C & ind5! -C & ind6!) -Cycloalkenyloxy, optionally substituted (C & ind3! -C & ind4! ) -Alkinyloxy, optionally substituted phenoxy, (C & ind1! -C & ind4!) - alkylamino, di- (C & ind1! -C & ind4!) - alkylamino or optionally substituted anilino, further a process for their preparation and their use as a pest control.

Description

Berlin, d.17.12.1979

AP CO7D / 215 125 55 380 12

Pesticides Field of application of the invention

The present invention relates to novel 1, 2, 4-triazole derivatives and their use as pesticides, in particular in crop protection.

Characteristic of the known technical solutions

Maneb / manganese (II) -N, N'-ethylenebis-dithiocarbamate 7 is a known fungicide, but its action against various mildews is insufficient. In particular, benzimidazole derivatives show resistance phenomena of true mildew deficiency.

Object of the invention

It is therefore an object of the invention to overcome these disadvantages,

Presentation of the essence of the invention

The invention has for its object to provide new pesticides based on 1,2,4-triazole derivatives «» "

The compounds of the invention have the general

Formula I Jj ν Ο

IL II

M 3

- 2 - Berlin, a · 17.12.1979 55 380 12

(C ₁ -C ₁₂ ) -alkyl which may be additionally optionally substituted by halogen, phenyl which may be mono- to disubstituted by halogen, (C 1 -C 4) -alkoxy or (C ₁ -C 4) -alkyl, (C ₁ -C 4) -alkoxy or phenoxy which may be mono- to disubstituted by halogen, (C ₁ -C 4) -alkoxy or (C ₁ -C ₃ ) -alkyl, is substituted (Cp-CcO-) Alkenyl, which is optionally additionally substituted by phenyl which may be mono- to disubstituted by halogen or (C ,, - (V) -alkoxy substituted, cycloalkyl, preferably having 5 or 6 C-atoms, or substituted cycloalkyl preferably having a total 5 to 9 carbon atoms, especially cycloalkyl substituted by alkyl, cycloalkenyl, preferably with 5 or 6 carbon atoms, or substituted cycloalkenyl having preferably a total of 5 to 9 carbon atoms, in particular alkyl radicals substituted by cycloalkenyl, phenyl or substituted phenyl, in particular one to three times by alkyl, preferably (C ₁ -C ₁₂ ) -alkyl, halogen, (C ₁ -C 4 -alkoxy y, hydroxy, nitro, dialkylamino with preferably (C ₁ -Cg) alkyl groups, or the methylenedioxy radical is substituted, furanyl, thienyl, pyridyl or (C ₁ - C ^) - alkoxycarbonyl, and

Ro "which may be the same or different, (C ₁ -C ₁₂ ) -alkyl, which may also be additionally preferably halogen, in particular one or two times, and / or one or two times by (C ₁ -Cg) -Akoxy, further by (C 1 -C 4 -alkylthio, phenylthio, which

Berlin, d. 17-12-1979 55 380 12

may be substituted once or twice by halogen or (CL-CL) alkyl, (Cj-C ^ alkylamino, di- (Cj-C ^ -alkylamino, phenyl or phenoxy which is mono- or disubstituted by halogen, (C C ₁ -C 4) -alkyl or (C ₁ -C 4) -alkoxy, or cycloalkyl, preferably having 5 or 6 carbon atoms, or substituted cycloalkyl having preferably a total of 5 to 9 carbon atoms, in particular by alkyl substituted cycloalkyl, phenyl or substituted phenyl which is substituted in particular mono- to trisubstituted by alkyl, preferably (C ₁ -CJ ₂₎ alkyl, halogen, (Cj-Cr) -alkoxy or hydroxy, (Cj-C ₁₂₎ alkoxy, optionally additionally by 1 to 6, preferably 1 or 2 halogen atoms and / or (C _x J-Cg) -alkoxy, (Cj-C ^) - alkylthio, (Ο, -C ₆ ) -alkoxy- (C ₂ -C ₆ ) alkoxy, halo (C ₁ -C ₂ ) alkoxy, methoxyethoxyethoxy, (C 1 -C ₄ ) alkylamino, di (C ₁ -C ₂ ) alkylamino, phenyl, the on or by halogen, (Cj-C ^ -alkyl, (C ₁ -Cn) -alkoxy or N- (Cj-C ^) -alkyl-anili oxo, or oxoranyl or phenoxy, which may be mono- or disubstituted by halogen or (C * -Cj,) - alkyl substituted, or (C (- C ₆ ) cycloalkoxy, which may be substituted by halogen or is methyl substituted, (Co-C ₆₎ alkenyloxy, halo (Co-Cg) alkenyloxy, (Cc-C ₆₎ -cycloalkenyloxy, (Co ~ C _Zf) alkynyloxy, which is optionally mono- or disubstituted by (Cj -C ₆ ) -alkyl, phenyl, halogen or (C 1 -C ₂ ) -alkox 5 ^! or phenoxy optionally substituted once to three times by (C ₁ -C 4 alkyl, (C ₁ -C 4) alkoxy, halogen, nitro or trifluoromethyl,

15125 - 4 - Berlin, d.17.12.1979

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or (C ₁ -C ₃ ) -alkylamino, D 1 (C ₁ -C 4) -alkylamino, anilino, which may be present on the benzene ring, one or more times by (C ₁ -C 4) -alkyl, halogen, (C _x J-Co alkoxy or substituted on the aniline N-atom by a (Cj-C ^) - alkyl group,

Preferred radicals R, - are z. B. (Cj-Cj ₂ ) alkyl, in particular (Cj-Cg) ~ alkyl, cycloalkyl having 5 or 6 carbon atoms, alkyl-substituted cycloalkyl having a total of 5 to 9 carbon atoms, cycloalkenyl having 5 or 6 carbon atoms , alkyl-substituted cycloalkenyl having a total of 5 to 9 C atoms, phenyl, substituted phenyl, in particular one to three times by (C _x JC _x J ₂ ) -alkyl, halogen, (C _x J-Cc) -alkoxy, hydroxy, nitro, Di- (Cj-Cg) alkylamino or the methylenedioxy radical substituted phenyl, furanyl, thionyl or pyridyl. Particularly preferred radicals are, for example, phenyl, chlorophenyl and methoxyphenyl *

Preferred radicals R ₂ , R- are z, B is (C _x J-Cj ₂ ) -alkyl, optionally substituted (C _x JC _x Jg) -alkoxy, cycloalkyl having 5 or 6 C atoms, alkyl-substituted cycloalkyl having a total of 5 up to 9 C atoms, phenyl, substituted phenyl, in particular monosubstituted to trisubstituted by (C _x , -C _x J ₂ ) -alkyl, halogen, (C _x J-Cc) -alkoxy or hydroxy.phenyl, (C, --Cg) -Cycloalkoxy, benzyloxy or diethoxymethyle

Particularly preferred radicals R ₂ , R ^ are z. B. (C _x J -Cg) alkyl, especially methyl, ethyl, propyl, butyl, phenyl, chlorophenyl, methoxy, ethoxy, propyloxy, butyloxy, octyloxy.

5 125 - 5 - Berlin, d.17.12.1979

55 380 12

The alkyl radicals listed in the radicals R.sup.-, R.sup.p, R.sup.- can be both straight-chain and branched. Halogen is preferably fluorine, chlorine, bromine.

The compounds of the general formula I are obtained by reacting compounds of the general formula II

(II)

wherein R ^, R ~ and R ^ have the meanings v / iθ in formula I, reacted with 1,2,4-triazole.

The reaction components are generally used in stoichiometric amounts. "Although an excess of one of the reaction components is possible in principle, but brings no advantages _β

The compounds of formula II are already known and can be z. Represent B _e by Knoevenagel condensation.

The addition of 1,2,4-triazole to the compounds of formula II is carried out according to the solubility of the starting components either without or, more advantageously, in a solvent which is inert under the reaction conditions. Suitable solvents are ζ, B. chloroform, (C ,, -C ^) - alcohols, triethylamine, methylene chloride, acetone, acetonitrile. The amount of solvent can range from fractions of the amount of reactant mixture

125 - ⁶ - Berlin, d.17.12.i979

55 380 12

amount to their same amount or possibly their multiple. It is also possible to use mixtures of different solvents.

Although the reaction generally already begins when the reaction components are mixed to form the compounds of the formula I, it is expedient and advantageous to add a catalyst to the reaction mixture. Suitable catalysts are inorganic or organic basic compounds, in particular tertiary amines. The amount of basic catalyst to be used is not critical and may, for. From C 0.1% to about 100% by weight, based on the amount of reactant mixture, or even higher. For example, tertiary amines, in particular triethylamine, can advantageously be used simultaneously as a catalyst and as a solvent.

The addition reaction between the starting components is sometimes weak, sometimes more exothermic. Performance and completion of the reaction depend on the reactivity of the compounds of the formula II and the solubility of the compounds of the formulas I and II ».

So it is z. B. in homogeneous systems advantageous to initiate the reaction at room temperature, to let fade the exothermic reaction and then the approach up to. Stand for 24 hours at room temperature.

15125 - 7 - Berlin, d.17.12.1979

55 380 12,

In the case of reaction mixtures whose constituents remain incompletely soluble after the beginning of the reaction or in which the reaction product crystallizes out early, it is expedient to heat the mixture to temperatures of 50 to 90 ^° C. for up to 2 hours.

Otherwise, the reaction temperature is not critical. It is preferably selected in the range between about 0 ⁰ C and 100 ⁰ C, whereby temperatures below 0 ⁰ C are possible and the upper temperature limit, for example, determined by the boiling point of solvents possibly used, but may also be higher than 100 ⁰ C. , Suitably and advantageously, the addition reaction is generally initiated at room temperature.

Isolation and purification of the compounds of the formula I obtained according to the invention are carried out by customary methods *

As a rule, the reaction products crystallize out of the reaction mixture at room temperature. If this is not the case, for example, all volatiles are distilled off under reduced pressure at 20 to 60 ⁰ C from the reaction mixture and the residue recrystallized from a suitable solvent or washed and isolated the reaction product.

The yields of compounds of the formula I which result in the process according to the invention can be very high.

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The claimed compounds of the formula I are distinguished by a very good fungicidal action. With their help, fungal pathogens already infiltrated into the plant tissue can be curatively combated. This is particularly important and advantageous in those fungal diseases that can not be combated after infection with the usual fungicides. The spectrum of action of the claimed compounds recorded in addition to Phytophthora infestans, Plasmopara viticola, Pricularia oryzae and Puccinia triticina especially powdery mildews in fruit, vegetable, cereal and ornamental plants. Particularly noteworthy is the excellent effect of the compounds against Benzimidazolcarbamatresistente Mehltauarten.

For use in crop protection, the compounds of the formula I can be formulated in a customary manner as dusts, wettable powders, mordants, dispersions, solutions or emulsion concentrates. The content of active ingredient of the formula I is in the fungicidal compositions generally between 2 to 95 GeWo-%, preferably at 10 to 90 wt .-%. In addition, the active ingredient formulations mentioned optionally contain the usual adhesion, wetting, dispersing, emulsifying, penetrating, solvent, filling and carrier substances.

The claimed compounds of formula I are also suitable for use in the technical field, for example in wood preservatives, on dem.Anstrichfarbensektor or as a preservative, eg. B _e in metalworking lubricants,

- 9 - Berlin, d.17.12.1979 55 380 12

The invention is explained in more detail by the following examples: A. Preparation Examples Example 1

2-methoxycarbonyl-4-methyl-3- (1,2,4-triazol-1-yl) valeric ~

acid methyl ester.

t 3

-N

A mixture of 55.8 g (0.3 mol) of Isobutylidenmalonsäuredimethylester, 20.7 g (0.3 mol) of 1,2,4-triazole and 25 ml of triethylamine reached after a few minutes an internal temperature of 70 ⁰ C, with a white Precipitation occurs. After 30 minutes 7 hours at 90 ⁰ C is stirred, the resulting solid was crushed, filtered off under suction washed und.mit petroleum ether. This gives 73.94 g (96.65% d.Th ·) 2-methoxycarbonyl-4 ~ methyl-3 ~ (1,2,4-triazol-1-yl) -valeriansäuremethylester as white crystals, melting at ₆₁₁₈ ⁰ C .. , ,

Analysis? (M = 255.3) calc. C 51.76 %% H 6.71%; N 16 ₉ 46 %

found: C 51.60%; H 6.70 %; N 16.30%.

128 -10- Berlin, d.17.12.1979

55 380 12

Example 2

Diethyl 2-ZTphenyl) - (1,2,4-triazol-1-yl) -methylj-malonate

a) A mixture of 74.4 g (0.3 mol) Benzylidenmalonsäurediäthylester, 20.7 g (0.3 mol) of 1,2,4-triazole, 40 ml of triethylamine and 20 ml of ethanol is stirred for 20 hours at room temperature. Crystallization occurs when rubbed with a glass rod »The white crystals are filtered off with suction, washed with diisopropyl ether, dried, and 82 g of mp. 79 to 82 ⁰ C are obtained. The concentrated mother liquor is crystallized, mixed with diisopropyl ether, the solid filtered off with suction , and we obtain a further 8.2 g, mp 79 ⁰ C. Gesamtausbeutei 90.2 g (94.85% of theory) of diethyl-2 - /. Tphenyl) - (1,2,4-triazole-1 yl) -me thyl7- ^m alonat. Analysis: C ₁₅ H ₁₉ N ₃ O ₄ (M = 217.35)

_e : C 60.6%; H 6.0% · Έ 13.2% found _e: C 60.6%; H 6.2%; N 13.3%

b) A mixture of 7.5 g (0.03 mol) Benzylidenmalonsäurediäthylester, 2.1 g (0.03 mol) of 1,2,4-triazole and 10 drops of triethylamine is stirred for 3 days at room temperature. After heating for 2 hours at 70 ^° C. and distilling off the volatile constituents under water-jet vacuum, the remaining oil is crystallized by seeding.

15125 -11- Berlin, d.17.12.1979

55 380 12

The crystal mass was crushed, washed with diisopropyl ether and filtered with suction. This gives 5.56 g of white crystals of M.P. 80 to 81 ⁰ C, The concentrated mother liquor is again treated with diisopropyl ether. This gives another 1.75 g. Total yield: 7.31 g (76.0% d.Th _e) Diethyl 2- / jCphenyl) - (1,2,4 ~ triazol-1-yl) ~ me thylj malonate.

c) Without basic catalyst

Carrying out the experiment as described under b), but without heating,

Yield: 6.53 S (68.7% of theory) of diethyl 2 - Tphenyl) / ~ -1,2,4-triazol -1-yl) malonate -methyl7 Pp from 76 ⁰ C..

Example · ^.

Ethyl-2-Z-Cphenyl) - (1,2,4-triazol-1-yl) -methyl7-3-oxobutanoate.

To 65.4 g (0.3 mol) Benzylidenacetessigsäureäthylester in 25 ml of triethylamine are added at room temperature (21 ⁰ C) 20.7 g ₍ (0.3, mol) of 1,2,4-triazole _e The internal temperature of the reaction mixture increases after 30 minutes, the reaction mixture solidifies suddenly, the internal temperature rising to 60 ^° C. The resulting white solid is treated with diisopropyl ether

- 12 - Berlin, d.17.12.1979 55 380 1 2

washed, to give 79.6 g (92.5% of theory) ethyl-2 / Tphenyl) - (1,2,4-triazol-1 ~ yl) ~ methyl / 3-o: xo-butanoate from Pp. 88 to 90 ⁰ C. Einengen.der mother liquor yields 5.5 g of impure product of mp. 66 to 69 ⁰ C, was dispensed on its cleaning

Analysis: C ₁₅ H ₁₁₇ N ₃ O ₃ (M = 287.3)

calc .: C 62.7%; H 6.0%; N 14.6% found: C 62.6%; H 5.9%; N 14.6%.

Example 4 3-ZTphenyl) ~ (1,2,4-triazol-1-yl) -methyl-7-pentane-2,4-dione

To 18.8 g (0.1 mol) Benzylidenacetylaceton in 16 ml of triethylamine are added 6.9 g (0.1 mol) of 1,2,4-triazole. The internal temperature rises in 30 minutes by 10 ⁰ C; This forms 2 phases. The mixture is heated for a few minutes to 50 ⁰ C, allowed to stand for 12 hours, the reaction product crystallized, filtered off with suction, washed with diisopropyl ether to give 22.8 g (88.8% of theory) 3 ~ / CPhenyl) -1,2 , -methyl7-pentane-2,4-DIPN, mp. 90 to 92 ⁰ C 4-triazol-1-y ~)

Analyzes C ₁₄ H ₁₅ N ₃ O ₂ (M _a 257.3)

Calculated: C 65.4%; H 5.9%; N 16.3%. Found: C 65.5%; H 6.0%; N 16.3%,

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example 5

Diäthyl-2-Z, 4-me thoxyphenyl) - (1,2,4-triazol-1-yl) me malonate

83 »4 g (0.3 mol) of 4-Methoxybenzylidenmalonsäurediethylester and 20.7 g (0.3 mol) of 1,2,4-triazole are stirred in 40 ml of triethylamine and 20 ml of ethanol at room temperature, gradually all components in solution go. After initially weak positive heat of about 2 ^° C., the reaction mixture solidifies within one hour, the internal temperature rising to 41 ^° C. It is allowed to stand for 15 hours, then heated for 10 minutes at 70 ⁰ C and allowed to crystallize out slowly. After aspirating and washing with diisopropyl ether to obtain 98.0 g (94.2% d.Ttu) diethyl-2- / 74-methoxyphenyl) ~ (1,2,4-triazol-1-yl) methyl.7 -ittalonate as white crystals from 98 to 101 ⁰ C.

analysis * * C ₁₇ H ₂₁ N 3 ° 5 (M rs 347.4) 12 1 % about. ί C 58.8%; H 6.1 of / ο ; N 12 5 %. Found ,; C 58.3%; H 6.1 cj 7o ; N

2151

Berlin, d.17.12.1979 55 380 12

Example 6

Dimethyl ~ 2 - / (thienien-2-yl) - (1,2,4-triazol-1-yl) -me thy 7 times onat

A mixture of 90.4 g (0.4 mol) Thienylidenmalonsäuredi ~ methyl ester, 27.6 (0.4 mol) of 1,2,4-triazole, 40 ml of triethylamine and 200 ml of methanol shows no exothermic reaction. After briefly heating to 50 ⁰ C and cooling crystallization occurs _e After suction filtration and washing with diisopropyl ether to obtain 77 »0 g of white crystals of melting point 125 to 127 ⁰ C. The mother liquor is largely concentrated, the Kri3tallmasse obtained treated as above. A further 40.7 g of Pp. 122 to 124 ⁰ C are obtained. Total yield: 117.7 g (99.7% of theory) of dimethyl-2-ethyl-2-yl) - (1,2,4 triazol-1-yl) malonate -methyl7 ~. Analyzes C ₁₂ H ₁₃ N ₃ SO ₄ (M = 295.3)

calc .: C 48.8%; H 4.4%; N 14.2%; S 10.9% Found: C 48.8%; H 4.4%; N 14.4%; S 10.9%.

Examples 7 to 126

In Table 1, the radicals R ₁ , R ₂ and R are listed in formula I of the compounds prepared according to Examples 7 to 126 from the corresponding compounds of formula II and 1,2,4-triazole and their melting points. Specifically, the following procedure was used during their production:

Berlin, d.17.12.1979. 53 380 12

Analogously to Example 1, Examples 7 were »8, 11 and 12, but carried out without heating; also Example 27, in which only 10 minutes at 50 ⁰ C was heated; furthermore Examples 63, 64 and 66, 70, 71, 78, 80 to 83, 90, 95 to 99, 109, 110, 111, 115, 116, 123 and 125, in which 15 minutes at 70 ⁰ C was heated the crystallization of the reaction product from, so the reaction mixture was first concentrated on a rotary evaporator under reduced pressure and the remaining oil is optionally brought to crystallization; Further, Example 42, which was heated with the addition of methylene chloride to the Rückflußtsnperatur of 42 ⁰ C '

Examples 2a, 23, 31, 32 and 50 were carried out analogously to Example 2a, with the alcohol corresponding to the ester component in each case being used instead of ethanol for the non-ethyl ester reactants as the solvent component.

Analogously to Example 3, Examples 9, 13 to 20, 24, 33, 34 »48 were carried out; Examples 35, 44, 65, 73, 7 ^, 75, 84, 85, 93, 94, 100 to 108, 112 to 114, 124 and 126, but which were heated at 75 ⁰ C for 10 minutes; also Examples 29, 38, 40, 43, 45, 60, 67, 72, 76 and 86, which were also carried out as in Example 5 with respect to solvent and temperature; also Example 17, which was carried out with the addition of methanol.

1 5 t 2 δ -16- Berlin, d.17.12.1979

55 380 12

Examples 10, 25, 30, 36, 46, 49, 88, 89, 91 and 92 were carried out analogously to Example 4, furthermore Example 22, but with the addition of chloroform as solvent.

Analogously to Examples 5 and 6, wherein in the case of the non-ethyl ester reactants, in each case the alcohol corresponding to the ester component was used as the solvent component instead of ethanol, Examples 26, 28, 37, 39, 41, 42, 47, 51, 54, 56 to 59, 61, 62, 68, 69, 77, 79 and 87; also examples 52, 53 and 55, which, however, were boiled for 2 1 / j hours under reflux.

Table 1 Formula Is

jIJ

I /

R ₁ -CGH (I)

C-Ro ti ->

Example R ₁ R ₂

Mp. ⁰ C 75 - 78 Oei Oei 66 - 68 104 - • 106

CH ₃ CH ₂ CH ₂ -CH ₃ O-CH ₃ O-

8 n-CJt ^ - CH ₃ O- CH ₃ O-

CH ₃ - ⁰ A ⁰ "

5 -17 -

Berlin, d.17.12.1979 55 380 12

example

Kr.

Mp. ⁰ C

12 13

15 16 17 18 19 20 21 22 23 24

CH ₀ -

CH ₃ O-

CH ₃ -

CH ₃ O-CH ₂ CH ₂ CH ₃ O-

C ₂ H ₅ O-CH ₃ --CH ₃ OC ₂ H ₅ O-

134 -

CH ₃ ISO-C ₄ H ₉ O- n _D -1. 5207 CH ₃ - (CH ₃ ) ₃ C0- 104 - 106 CH ₃ - (Ζ) - ⁰ 79 -   84 CH ₃ - UC ₈ H ₁₇ O- h-t-j - ι. 5082 CH ₃ - ⁿ "" ^ 12 ^ 25 ^ "" - CH ₃ - <n> -CH ₂ -0- 97 -   98

114 114 157 81-84

Berlin, d.17.12.1979 55 380 12

example

No.

Pp. C ⁰

25 CH,

CH,

29

30

31 Cl 32 Cl 33 Cl 34 Cl

Cl

Cl

CH ₃ - CH ₃ - CH3O- CH ₃ O- CH ₃ O- CH ₃ O- CH ₃ O- CH ₃ O- CH ₃ - C ₂ H ₅ O CH ₃ - CH ₃ - CH ₃ O- CH ₃ O-

CH ₃ -

CH ₃ -

C ₂ H ₅ O-

(CH

91 - 93 126 - 128 79 - 82 117 - 119

Semi Crystalline

70 - 74 144 _ 146 104 - 109 86 - 90 108 - 114

Berl in, d.17.12.1979 55 380 12

example

No.

Mp. ⁰ C

35 Cl 36 Cl

CH

CH, CH

40 41 cl

CHO CH ₃ - CH ₃ O- CH ₃ O- C ₂ H ₅ O CHoO- CHO

C ₂ H ₅ O-

CH ₃ O- -CHO ₁ O-

CH ₃ O-

CH ₃ - ^σ 2 ^Η 5 ° "

116 - 120

103 - 111

93 - 95

105-109

150 - 152

88 - 93

82 - 86 108 127 - 129 Semicrystal lin 98 -

Berlin, _e 17.12.1979 55 380 12

example

No,

, ° C

45 46

CH,

CH.

80 - 96

99-101

47

49

52 HO

54 Q

CH ₃ -

OCH.

CH ₃ O-

C ₂ H ₅ O-

C ₂ H ₅ O-C ₂ H ₅

O-

110 -

77 - 83

97 - 100

58 - 60

V-O

CH ₃ - C ₂ H ₅ O- 82 - £ 54 CH ₃ O- CH ₃ O- 150 - 154 CHoO- CH ₃ O- 118 - 121 CH ₃ O- CH ₃ O- 152 - 155

Example no.

Berlin , A.17. 12 .1979 55,380 12 Mp. ° c

Br HO Br

CH ₃ O- CH ₃ O-

-α

CH ₃ O- CH ₃ O-

CH ₃ O- CH ₃ O-

93 -

129 -

127 -

CH ₃ O-

133 ~

60 cl

CH ₃ O

130 -

= 1.5056

HC ₄ H ₉ O- HC ₄ H ₉ O-

₌ 1.4988

84-87

= 1.4990

Berlin, d.17.12 · 1979 55 380 12

Example no.

R ₁ mp. ⁰ C

69 cl

70 cl

71 cl

72 cl

73 cl

Cl

CH ₃ - CH ₃ O- Cl CH ₃ O- 11-C ₃ H ₇ - C ₂ H ₅ O- nc ₃ H _? O- HC ₃ H ₇ O- JU-C ₃ H ₇ O- n-C3H ₇ O- ISO-C ₃ H ₇ O- iso-C ₃ H ₇ 0 HC ₄ H ₉ O- CH ₃ - CH ₃ O- HC ₃ H ₇ - C ₂ H ₅ O-

78 - 87

-

80 - 82

NJF = 1.5075

59 - 65

85 - 87

64-67

114 -

100 -

74 ch:

CH

11-C ₃ H ₇ - C ₂ H ₅ O-103 -

Example no.

R ₁

Berlin, d.17.12.1979 ^ 380 12

η (refractive index)

Ro Fp. ⁰ C

UHr, -n ³ ° = 1.5172

76 CH ₃ O

77 CH ₃ O

CH ₃ O

HC ₃ H ₇ O- 59-60

78 CH ₃ O

HC ₄ H ₉ O-

NJP = 1.5090

3 '

OCH,

OCH,

OCH-C ₃ H ₇ O-

OCH

³ nC ₄ H ₉ 0-

OCH,

OCH 58-63

53 -

³ iso-C ₃ H ₇ O- ISO-C ₃ H ₇ O 82-88

n ³⁰ = 1.5058

iso-C ₄ H ₉ O-

C ₂ H ₅ O-

C ₂ H ₅ O-

ί = 1.5172

77 - 80

Berlin, d.17.12.79 55 380 12

example

Fr.

η (refractive index)

CH ₃ O-,

107 -

88

CH ₃ -

CH ₀ O-

CH ₃ -

CIL

68 -

C ₂ H ₅ O-. C ₂ H ₅ O- n | ⁵ = 1.4775

CH ₃ -

C ₂ H ₅

ti QC-CH ₃ -

CH ₃ OC-

CH ₃ O-

114 -

C ₂ H ₅ OC-

o-c-0-

C ₂ H ₅ O- ^C 2 ^H 5 ° "

Example no.

Berlin I 380 , D.17 .12.1979 55 H 12 Fp. ⁰ C η (refractive index)

0-CH ₂ - C ₂ H ₅ OC ₂ H ₅

0-

C ₂ H ₅ O-

CH = CHC ₀ H ₁ -OC ₂ H ₅ O-

CH = CH-n-CoHo-J ₂ H ₅ O-

CH ₃ O-CH ₂ -CH ₃ O-

C ₂ H ₅ O-

) -CIL

C.

C ₂ H ₅ O-

C ₂ H ₅ O-

Berlin, d.17.12.1979 55 380 12

example

R ₁

Pp. C ⁰

η (refractive index)

0-CH ₂ -C ₂ H ₅ OC ₂ H ₅ O-

CH ₃ O-CH ₂ -C ₂ H ₅ O-

C ₂ H ₅₁

0-

CH = CH- C

C ₂ H ₅ O-

100

CH ₃ O-CH ₂ -CH ₃ O-

S-CH 1 - CoH ₁ -O-

C ₂ H ₅

102

C ₂ H ₅ O-

0-CH ₂ -

C ₂ II ₅ O-

2 5

) ₂ cH

₃ ) ₂

CH ₂ -

Berlin, d.17.12.1979 55,380 12

example

No. _β

Mp. ⁰ C

η (refractive index)

106

(C ₂ H ₅ O) ₂ CH- C ₂ H ₅ O-

107 Cl 108 109 110 Cl-111

OCH.

OCH.

22

(C ₂ H ₅ O) ₂ CH- C ₂ H ₅ O- ng = 1.5139 (C ₂ H ₅ O)

₂ CH- C ₂ H ₅ O-

ClCH ₂ CH ₂ O-ClCH ₂ CH ₂ O-CH ₃ O-CH ₂ CH ₂ O-CH ₃ O-CH ₂ CH ₂ O-

HC ₄ H ₉ O-CH ₂ CH ₂ O-

n ^ ° = 1.494 to 1

112

CH ₃ -

^υ 2 "5 ^η 2 ^υη 2 ^υ ~

113 114 115

CH ₃ -CH ₃ -

0-CH ₂ CH ₂ O-

CH. CH ₀

ch; CH.

Berlin, d.17.12.1979 55 380 12

example

Fp. ⁰ C ⁿ

(Refractive index)

116 117

CH ₀ = CH-CH ₀ O-

C.C.

CH ₀ = CH-CH ₀ O-

118 119 120 Cl

121

CH.O

122 CH ₃ O

123 124

CH.

CH ₃ -

CH ₃ -

C ₂ H ₅

CH ₃ -

O-

Br-CH = CH-CH ₂ O-

^C 2 ^H 5 "(° CH = C-CH ₂ O-CH = C-CHO

CH ₃

Phenyl CH = C-CHO

Cl

CH ₃ -CHO

CH ₂ Cl

 0-

125 126 cl

OCH.

0-

CH ₃ O-CH ₂ CH ₂ O-

143 -

215

- 28 - Berlin, d.17.12.1979 55 380 12

Β »Formulation examples

Example A

Dust is obtained by mixing 10 parts by weight of active compound and 90 parts by weight of talc as an inert substance and comminuting in a hammer mill.

Ex iel B

A wettable powder easily dispersible in water is obtained by adding 25 parts by weight of active substance, 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of sodium oleoylmethyltaurinate as wetting agent.

and dispersants. mixed and ground in a pin mill.

Example C

A dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of active compound with 6 parts by weight of nonylphenol polyglycol ether (10AeO), 3 parts by weight of isotridecanol polyglycol ether (8AeO) and

71 parts by weight of paraffinic mineral oil (boiling range

255 to> 377 ° C / normal pressure)

mixed and ground in a ball mill to a fineness of less than 5 microns.

\ && - 29 - Berlin, ά.17.12.1979

55 380 12

Example P

An emulsifiable concentrate is obtained from 15 parts by weight of active ingredient

^ Parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated Uonylphenol (10 AeO) as

Emulsifier.

C. Biological Examples Example I

Wheat plants were heavily inoculated in the 3-leaf stage with conidia of wheat powdery mildew (Erysiphe graminis) and placed in a greenhouse at 20 ⁰ C and a relative humidity of 90 to 95%. 3 days after inoculation, the plants were sprayed to drip point with the compounds listed in Table I in the active compound concentrations of 500, 250, and 125 mg / liter of spray. As comparison comparison Maneb was used. After an incubation period of 10 days, the plants were examined for infestation with wheat powdery mildew. The degree of infestation was expressed in% of infected leaf area relative to untreated, infected control plants (= 100% infestation). The result is summarized in Table I.

30 - Berlin, d.17.12.1979

55 380 12

Table I infected with wheat powdery mildew Active ingredient / liter 125 3 Leaf area in % 3 30 connection at mg 250 O 5 spray mixture according to 500 O O - 5 60 3 example 0 O 3 - 3 47 0 O O - 3 48 0 O O 3 33 0 O O - 5 3 41 Ö O 5 29 0 O 3 - 36 0 O O 43 0 O O 32 0 O O 3 O 2 0 O O O 5 0 O O O 3-5 61 0 O O O 0-3 62 0 O O O - 3-5 63 0 O O O 3-5 64 0 O O O - O 65 0 O O O - 3-5 67 0 O O O 3 68 0 O O O - 0-3 69 Ό O O O - 0-3 72 0 ο O O O 77 0 O O O O 78 0 O O O 3-5 79 0 O O O O 80 0 O O O - 81 0 O O O O 82 0 O O O O 83 0 O O O 0-3 84 0 O O 85 0 O 87

15125 -31- Berlin, d.17.12.1979

55 380 12

Compound with wheat powdery mildew affected leaf area in %

according to mg active ingredient / liter spray mixture Example 500 250 125 60 30

Maneb ⁺ . 5 10 15 100 100

unheated "

infiz, 100

plants

⁺ Maneb - L5angan (II) - (N, N-bis ~ ^t -äthylen (dithiocarbamt))

Example II

Grukenpflanzen (variety Delikateß) were heavily inoculated in the 2-leaf stage with a conidia suspension of cucumber powdery mildew (Erysiphe cichoracearum). After a drying time of the spore suspension of 30 minutes, the plants were placed in a greenhouse at 22 ⁰ C and'90 % relative humidity. 3 days after infection, the plants were sprayed to drip point with the compounds listed in Table 2 and drug concentrations. As comparison comparison Maneb was used. After 10 days, the rating was done. The degree of infestation was expressed in% of infected leaf area, based on untreated, infected control plants (= 100 % infestation). The result is summarized in Table II

Table II

Connection with cucumber mildew infested leaf surface

in % at mg active substance / liter spray mixture Example 5 00 2 50 125 60 30

3 0 0 0-3

48 0 0 5

33 0 0 0

Berlin, d.17.12.1979 55 380 12

connection with grass mildew infested 125 leaf area 30 according to in % at mg active substance / liter 5 spray mixture example 500 250 3-5 60 29 0 0 15 51 0 0 0 32 0 5 5 2 0 0 15 - 25 5 0 0 5 4 0 5-10 0 0 30 0 0 0 0 61 0 0 0 0 0-3 62 0 0 0 0 0 63 0 0 0 0 0 64 0 0 0 0 0 67 0 0 0 0 0-3 68 0 0 0 0 3-5 69 0 0 0 0 O 72 0 0 0 0-3 O 77 0 0 0 O 0-3 78 0 0. 0 O O 79 0 0 0 O 0-3 80 0 0 0 O O 81 0 0 0 O O 82 0 0 0 O 0-3 83 0 0 0 O O 75 0 0 0 O O 84 0 0 0 O O-3 85 0 0 35 O 100 87 0 0 O Maneb. ⁺ 15 25 100 100 unheated. infiz _o plants

⁺ cf. Table I

Berlin, d.17.12.1979 55 380 12

connection with grass mildew infested 125 leaf area 30 according to in % at mg active substance / cit 5 spray mixture example 500 250 3-5 60 29 0 0 15 51 0 0 0 32 0 "5 5 2 0 0 15 - 25 5 0 0 5 4 0 5 - 10 0 0 30 ο 0 O 0 61 0 0 0 0 0-3 62 0 0 0 0 0 63 0 0 0 0 0 64 0 0 0 0 0 67 0 0 0 0 0-3 68 0 0 0 0 3-5 69 0 0 0 0 0 72 0 0 0 0-3 0 77 0 0 0 0 0-3 78 0 0. 0 0 0 79 0 0 0 0 0-3 80 0 0 0 0 0 81 0 0 0 0 0 82 0 0 0 0 0-3 83 0 0 0 0 0 75 0 0 0 0 0 84 0 0 0 0 0 - 3 85 0 0 35 0 100 87 0 0 0 Maneb ⁺ · 15 25 100 100 discomfort » plants

see. Table I

15 125 - 33 - Berlin, d.17.12.1979

55 380 12

Example III

Garkenpflanzen (variety Delikateß) were in the 2-leaf stage with a conidia suspension of a benomyl-resistant Gur-. kenmehltaustammes (Erysiphe cichoracearum) strongly inoculated. After a drying time of the spore suspension of 30 minutes, the plants were placed in a greenhouse at 22 ⁰ C and 90% relative humidity. 3 days after infection, the plants were sprayed to drip point with the compounds listed in Table III and drug concentrations. Maneb and benomyl were used as comparative compounds. After 10 days, the rating was done. The degree of infestation was expressed in % of infected leaf area, based on. untreated, infected control plants (= 100 % infestation). The result is summarized in Table III.

Table III with cucumber mildew infested (Benomyl resistant 250 125 60 at connection Tribe) Leaf area in % O 3-5 according to mg of active ingredient / liter of cooking broth O 5 - 10 30 example 500 O O 3 O 3-5 5-10 3 O 5-10 15 - 25 48 O 0-3 5 33 O O O O 29 O O O O 4 O O O O O 30 O O O O O 61 O 3 62 O O 63 O 64

Berlin, d.17.12.1979 55 380 12

connection

example

leaf area affected with cucumber mildew (Benomyl-resistant strain) in % at mg active substance / liter spray mixture 500 250 125 60 30

67 0 0 0 0 0-3 68 0 0 0 0 0 69 0 0 0 0-3 3 77 0 0 0 0 0 78 0 0 0 0 0 79 0 0 0 0 0 80 0 0 0 0 0 81 0 0 0 0 3 82 0 0 0 0 0 83 0 0 0 0 0 73 0 O 0 0 vj 84 0 0 0 0 0 85 0 0 0 0 0-3 87 0 0 0 0 3 Maneb ⁺ 15 25 35 100 100 Benomyl ⁺⁺ 35 60 100 unheated. infiz. plants 100

t cf. Table I;

Benomyl = 1- (N-butylcarbamoyl) -2- (methoxycarboxamido) benzimidazole

Example IY

Barley plants were heavily inoculated in the 3-leaf stage with conidia of the barley powdery mildew (Erysiphe graminis sp. Hordei) and in a greenhouse at 20 ⁰ C and a relative

- 35 - Berlin, d.17.12.1979

^ 380

Humidity of 90 to 95 % set up. 3 days after inoculation, the plants were sprayed to drip point with the compounds listed in Table IV in the active compound concentrations of 500, 250 and 125 mg / liter of spray. As comparison comparison Maneb was used. After an incubation period of 10 days, the plants were examined for infestation with barley powdery mildew. The degree of infestation "was expressed in% of infected leaf area, based on untreated, infected control plants (= 100 % infestation) .The result is summarized in Table IV.

Table IV

Compound with leafy mildew attacked leaf area in % according to mg active ingredient / liter spray mixture Example 500 25O 125 60

47 33 29 51 30 61 62 64

O O 10 - 15 O O O 3 ö - 3 O 5 10 ~ 15 O O 3 O - 3 O 5 10 - 15 O O O O 5 10 - 15 O O O O 5 10 - 15 O O O O O 5 - 10 O O O O O O O - 3 - 3 O O O O - 3 O O O O O O O O O O O O O O O O

O 0 O 0-3 O 0 O 0 0-3 3rd-5th 0 0 0 0-3 0-3 3-5 0 0 0 0 0 0 100 100

- 36 - Berlin, d.17.12.1979 ^ 380 12

Compound with leafy mildew attacked leaf area according to in% at mg active ingredient / liter spray mixture Example 500 250 125 60 30

77 0 0 0

78 0 0 0

79 0 0 0

80 0 0 0

81 0 0 0

82 0 0 0

83 0 0 0 75 0 0 0 84- 0 0 0 85 0 0 0 87 0 0 0 Maneb ⁺ 25 35 60

unheated. infiz.

Plants .100

⁺ See Table I Example V

Vine plants grown from cuttings of the Plasmopara-susceptible variety Muller-Thurgau were dripped wet at the 4-leaf stage with aqueous suspensions of the compounds and active substance concentrations listed in Table V.

After the spray coating has dried, the plants were inoculated with a zoosporangia suspension of Plasmopara viticola and to runoff in a climate chamber at a temperature of 20 ⁰ C and detected at a relative humidity of 100%. After 24 hours, the infected plants were removed from the climate chamber and placed in a greenhouse with a temperature of 23 ° C and a humidity of about 80 to 90 % .

- 37 - Berlin, d.17.12.1979 55 380 12

After an incubation period of 7 days, the plants were moistened, placed overnight in the climatic chamber and brought the disease to the outbreak. Subsequently, the infestation evaluation took place. The degree of infestation was expressed in % of infected leaf area compared to the untreated, infected control plants and is reproduced in Table "V".

Table V % Plasmopara infestation at 250 125 connection mg active ingredient / liter Spritzbrüho 0-3 30 according to 500 O 3-5 example 0 O 3-5 3 0 O 5-10 30 O O 5-10 33 0 O 3-5 59 0 O 3-5 24 0 O O 29 0 64 0 100 unheated. infiz. plants

Claims (3)

15125 -38- Berlin, d. 17.12.1979 55 380 12 Inventory 1 § t 25-40- Berlin, ά.17.12.1979 55 380 12 (C ₁ -C ₃ ) -Alkoxy or N- (C ₁ -C ₄ ) -Alkylanilino substituted, oxiranyl or phenoxy, which may be monosubstituted or disubstituted by halogen or (C ₁ -C ₄ ) alkyl, substituted or (C 1 -C 9) -cycloalkoxy, which is optionally substituted by halogen or methyl, (Co-C ₆ ) -alkenyloxy, halogeno (Co-Cg) -alkenyloxy, (C ₁ -C ₆ ) -cycloalkenyloxy, (C ₃ -C ₄ ) -Alkynyloxy, which is optionally monosubstituted or disubstituted by (C ₁ -Cg) -alkyl, phenyl, halogen or (C ₁ -Cg) -alkoxy, or phenoxy, which is optionally substituted once or twice by (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy, halogen, nitro or trifluoromethyl, or (C ₁ -C _/> ) -alkylamino, di (C ₁ -C ₄ ) -alkylamino , Anilino, optionally substituted on the benzene ring once or twice by (C ₁ -C.) - Alkyl, halogen, (C ₁ -CO-AIkOXy or at the aniline-N atom by a (C ₁ -C ₄ ) alkyl group is, mean next to customary formulation aids. 1. pest control agent, characterized by a content of 2 to 95 wt .-%, preferably 10 to 90 wt .-%, of a compound of general formula I. ml E ₁ -C. , ft 3
O wherein (Cx | -CxJ ₂₎ -alkyl, which optionally additionally preferably by halogen, phenyl which is monosubstituted or disubstituted by halogen, (C ^ -C ^ _-) can be alkoxy, or (CI (V) -alkyl, (C 1 -C 4) -alkoxy or phenoxy which may be monosubstituted or disubstituted by halogen, (O 1 -C ₂ ,) -alkoxy or (C 1 -C 3 -alkyl-substituted (C ₂ -) C 1 -C 3) -alkenyl which is optionally additionally substituted by phenyl which may be mono- to disubstituted by halogen or (C 1 -C 3) -alkoxy, cycloalkyl, preferably with 5 or 6 C atoms, or substituted cycloalkyl preferably having a total of 5 to 9 carbon atoms, especially cycloalkyl substituted by alkyl, cycloalkenyl, preferably with 5 or 6 carbon atoms, or substituted cycloalkenyl preferably having a total of 5 to 9 carbon atoms, especially substituted by alkyl radicals cycloalkenyl, phenyl or substituted phenyl , the - 39 - Berlin, d. 17.12.1979 380 12 especially one to three times by alkyl, preferably (C ₁ -C ₁₂ ) -alkyl, halogen, (C ₁ -C, -) - alkoxy, hydroxy, nitro, Dialkylanri.no with preferably (C, -Cg) -Alky! groups, or the methylenedioxy radical is substituted furanyl, thienyl, pyridyl or (^ -C ^ alkoxycarbonyl, and which may be identical or different, (C 1 -C 4) -alkyl, which may be additionally additionally preferably denoted by halogen, in particular one or two times, and / or one or two times by (C 1 -C 9) -alkoxy, furthermore by (C 1 -C 4) -alkoxy; C ^ -alkylthio, phenylthio, which may be monosubstituted or disubstituted by halogen or (C ₁ -C 4) -alkyl, (C ₁ -C 4) -alkylamino, di- (C ₁ -C 3) -alkylamino, phenyl or Phenoxy, which may be monosubstituted or disubstituted by halogen, (C ₁ -C ₂ ,) - alkyl or (C, -CO-alkoxy substituted or cycloalkyl, preferably having 5 or 6 carbon atoms, or substituted cycloalkyl preferably having a total of 5 to 9 C atoms, in particular cycloalkyl substituted by alkyl radicals, phenyl or substituted phenyl which is in particular monosubstituted to trisubstituted by alkyl, preferably (C ₁ -C 3) -alkyl, halogen, (C ₁ -C 4) - Alkoxy or hydroxy is substituted, (C ₁ -C ₁₂ ) ~ ^Alkox y »which may additionally be replaced by 1 to 6, preferably 1 or 2 halogen atoms and / or (Cj-Cg) -Alko xy, (C ₁ -C ₄ ) -alkylthio, (C ₁ -Cg) -alkoxy (C ₂ -C ₆ ) -alkoxy, halo (Cj-Cp) -alkoxy, methoxy-ethoxyethoxy, (C ₁ -C ₂ ,) -alkylamino, di- (C ₁ -C 4) -alkylamino, phenyl which is mono- or disubstituted by halogen, 2. Use of compounds of the formula I according to item 1, characterized in that they are used for pest control in crop protection. 3 «A method for controlling harmful fungi, characterized in that bringing them affected areas and / or plants and / or substrates with effective amounts of active compounds of the formula I according to item 1 in contact.