DE2917914A1 - N- (ALKOXY- OR ALKOXYCARBONYLALKYL) - N-ALKOXYALKOXYACETYL-ANILINE DERIVATIVES - Google Patents

Description

29179H

Dr. F. Zurnstesri sen. - Dr. E. ÄSöii <aP! I - Di. R. s < >: Sepigsberger Dipä.-Phys. R. HoSzbauer - Dipl.-Ing. F. ί · Sin3S2is3n - Dr.s-. For junior

PATENT LAWYERS

80OO Munich 2 - B räu ha usstrasse 4 Telephone collective no. 22 52 41 - Telegrams Zumpat Telex 529979

CIBA-GEIGY AG Basel Switzerland

5-10707 / 1 + 2 / =

H- (alkoxy derivatives

. Alkoxycarbonylalkyl) -N-alkoxyalkoxyacetyl-aniline-

The present invention relates to compounds of the formula I.

^R l
I.

X-R.

. · —N

C - CH. - O - CH - O - R _T

»Ί

^R 6

wherein R is C -.- C, alkyl, C, -C, alkoxy or halogen, R 'is hydrogen, C - C ₃ alkyl C _s - C, alkoxy or halogen, R ₃ is hydrogen, C, -C _{3 are} alkyl or halogen, and R, hydrogen or methyl, the total number of carbon atoms in the substituents R ,, R ₂ , R ^ and R, not being more than eight,

X is -CH ₂ - or -CH -, and R _{5 is} -COOCH ₃ , or COOC ₂ H ₅ or -CH ₀ OCH ₃ , R is hydrogen or "CH-Rs is, R is C 1 -C 4 -alkyl

R ₀ and R _n independently of one another are hydrogen, halogen or

represent or furthermore R-, and Rg together can form C ₂ ~ C ₃ -alkylene.

The invention also relates to a process for the preparation of these compounds, their use in pest control,

030046/0246

29179U

as well as agents containing these compounds as active components.

Under alkyl or alley 1-part of an alkoxy group are depending on Number of specified carbon atoms to understand the following groups:

Methyl, ethyl ₉ n-propyl, iso-propyl, η-butyl, iso-butyl, sec-butyl and tert-butyl.

The term halogen stands for fluorine, chlorine, bromine or iodine. The term C "-C -alkylene includes ethylene and propylene.

The compounds of the formula I are prepared according to the invention, ■

A. If R _{g is} other than hydrogen, by reacting a compound of formula II

R. V C-CHOH

⁴ - \ Ii ι

° ^R 6
with a compound of the formula III

CHOIR

II

CR ₀ (III)

I ⁸

^R 9
in the presence of a catalyst

B. When R _{5 is} hydrogen by reacting a compound of the formula II, preferably a salt thereof with an alkali or alkaline earth metal with a compound of the formula IV

Hal ¹ CH ₂ - 0 - R ₇ IV

030046/02 A 6

-Z-

where in formulas II, III and IV R ₁ to R 1 and X are as defined under formula I and Hal ^f for halogen is preferably chlorine or bromine.

Reactions can be carried out in the presence or absence of solvents or diluents which are inert towards the reactants. For example, the following are possible: aliphatic or aromatic hydrocarbons such as benzene, toluene, xylene ₅ petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, ethers and ethereal compounds such as dialkyl ethers und'Butylmethyläther, dioxane, tetrahydrofuran, nitriles such as acetonitrile; Ν, Ν-dialkylated amides such as dimethylformamide; Dimethyl sulfoxide and mixtures of such solvents with one another, if the compound of the formula II is used as the free alcohol in process B, this is done in the presence of an acid-binding agent.

The reactions are carried out at temperatures between -20 ⁰ C and +120 ⁰ C, preferably from 0 ° and 80 ⁰ C ₉ and under normal pressure. The main catalyst used is an acid such as p-toluenesulphonic acid, conc. Hydrochloric acid, conc. Sulfuric acid in question.

The starting material of the formula II is prepared analogously to methods known per se (see e.g. German Offenlegungsschrift No. 2,417,781).

In the compound structures of the formula I, when R, ^ is hydrogen, there are three possible centers for asymmetric carbon atoms, which can be found at positions 1, 2 and 3:

3 *

^X - ^R 5

C-CH ₉ -O-CH-OR ₇

Ii i

0 f

^R 9

030046/0246

29179U

-Λ -

1*; asymmetric if R _fi ^ hydrogen

2 ^Ä : asymmetric, if R "& Rg ^ hydrogen,

3 *: asymmetrical, if X means -CH-.

The pure optical isomers can be produced, for example, by using separate antipodes of the starting materials. These xjerden for example through salt formation with optically active bases subsequent fractional crystallization and release of the corresponding antipode obtained.

Regardless of the optical isomerism, a

Atropisomerism about the phenyl N ^- ^ axis observed in the cases where

the phenyl ring is substituted unsymmetrically to this axis (if appropriate also by the presence of additional substituents) is.

Unless a specific synthesis for the isolation of pure isomers is carried out, one product usually falls as a mixture of all of them Isomers.

The compounds of formula I can be used alone or used in conjunction with suitable supports and / or other aggregates. Suitable carriers and aggregates can be fesc or be liquid and correspond to the substances customary in formulation technology, such as natural or regenerated minerals Substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

The content of active ingredient in commercial products is between 0.1 and 90%.

For administration, the compounds of the formula I can be in the following working-up forms (the percentages by weight represent advantageous amounts of active ingredient in brackets):

030046/0246

29179U

-JS -

Fixed forms of processing: dust and grit (up to

10%); Pellets (grains), granules, coating granules, impregnation granules and homogeneous granules (1 to 80%);

Liquid processing forms:

a) Active substance concentrates dispersible in water:

Wettable powders and pastes (25 - 90% in the commercial pack, 0.01 to 15% in a ready-to-use solution): Emulsion and solution concentrates (10 to 50%; 0.01 to 15% in a ready-to-use solution);
Solutions (0.1 to 20%); Aerosols

The compounds of the formula I have a microbicide spectrum which is very favorable for practical needs for the protection of Crops. For the purposes of the present invention, crop plants are, for example, cereals, maize, rice, vegetables, sugar beets, soybeans, Peanuts, fruit trees, ornamental plants, but especially vines, hops, cucumber plants (cucumbers, pumpkins, melons), Solanaceae such as potatoes, Tobacco and tomatoes, as well as banana, cocoa and natural rubber plants.

The active ingredients of the formula I can be used on plants or parts of plants (Fruits, blossoms, Laubxierk, stems, tubers, roots) of these and related crops, the fungi that occur are contained or destroyed, with later growing parts of the plant be spared from such fungi. The active ingredients are effective against the phytopathogenic fungi belonging to the following classes: Ascomycetes; Basidiomycetes, especially rust fungi; Fungi imperfecti such as Cercospora; but then especially against those of the class of Phycomycetes belonging to Oomycetes such as Phytophthora, Peronospora, Pseudoperonospora, Pythium or Plasmopara. Moreover, they work Compounds of the formula I systemic. They can also be used as a mordant

0300A6 / 0246

for the treatment of seeds (fruits, tubers, grains) and plant cuttings can be used to protect against fungal infections and against phytopathogenic fungi that occur in the soil.

A group which is interesting because of their action is formed by those compounds of the formula I in which R. is methyl or methoxy R. Ethyl, chlorine or bromine, R “hydrogen, methyl, chlorine or bromine and R, hydrogen or methyl.

In the case of R ₇ , ethyl or (together with R ") C ₂ _., - alkylene, in the case of Rg hydrogen or (together with R ₇ ) C ^^ - alkylene, and in R_ hydrogen.

Also of interest are compounds of the formula I from the above two groups in which R _{1 is} methyl, R 2 is methyl or ethyl and R 1 and R 2 are hydrogen or methyl.

Also to be emphasized are compounds from the above-mentioned three groups, in which the substituent R _? is in the ortho position to the amino group.

In formula I and especially within these four groups, those compounds are preferred in which X -CH- and R_ represent. CH "

Combinations of the various compound groups are of special interest.

The following examples serve to explain the invention in more detail without restricting the same. The temperature information relate to degrees Celsius. Unless otherwise noted, is at the naming of an active ingredient of the formula I, which can occur in optically active forms, always means the racemic mixture.

030046/02 4

29T79U

Manufacturing example

Example 1 Preparation of N- (l'-methoxycarbonyl ~ ethyl) -N- (2-pyranyloxy) acetyl-2,6-dimethylaniline of the formula

CH T 3
_{# =} T 3 JtB - COOCH ₃

ν . · —N ^ / \

j ί (verb. no. 1)

^l 2 - "~

IC - CH_ - 0— *
^CH 3 yy

13.3 g of N- (1'-methoxycarbonylethyl) -N-hydroxyacetyl-2,6-dimethylaniline in 60 ml abs. Essxgsäureäthylester were after the addition of 0.3 g of p-toluenesulfonic acid 'inter occasional cooling with ice water and under Stirring at approx. 20 ° within 20 minutes, 6.3 ml of tetrahydropyran were added dropwise. After two hours the reaction mixture became cooled to 0 °, mixed with solid potassium carbonate and stirred for 10 min. The mixture was then filtered and the solvent evaporated. The oil thus obtained has a refractive index of n ^ ° 1.5066.

Example 2 Production of

CH f ³
/ ^utl 3 CHCOOCH ₀

CH ₃ j

N- (I'-methoxycarbony1-ethyl) -N- (ethoxymethyloxy-acety1) -2,6-dimethylani 1 in.

13.3 g of N- (I'-methoxycarbony1-ethyl) -N-hydroxyacetyl-2,6-dimethylaniline, in 18 ml of abs. Dissolved tetrahydrofuran were added to 2.4 g of sodium hydride (50% strength oil dispersion) in 8 ml of abs under a nitrogen atmosphere and stirring. Tetrahydrofuran was added dropwise. After stirring for 3 hours, 4.7 g of chloromethyl ethyl ether ^{were added at 8-10 0 C with ice cooling}

030 0A6 / 0 24 6

added dropwise and stirred for a further 3 hours at room temperature. Aqueous tetrahydrofuran was then added dropwise, and water and ether were added and the organic phase separated. The water phase was extracted three times with ether, the extracts washed with water and washed over Dried potash. An oil remained evaporated for the purpose of removal paraffin oil was digested three times with hexane. The now solidified residue was recrystallized from cyclohexane and showed a melting point of 78-81 °.

Example 3 Preparation of

CH
/ H ₃ ■

^ CH CH,

W \ A

CCH ,, -

2 I I

³ I V

N- (1'-methyl-2'-methoxyethyl) -N- (2-pyranyloxy) -acetyl-2,6-dimethylaniline.

17.6 g of N- (I'-methyl-2'-methoxyethyl) -N-hydroxyacety1-2,6-dimethy1-aniline, 80 ml abs. Ethyl acetate and 0.42 g of p-toluenesulfonic acid 8.1 g of 3,4-dihydro-2H-pyran were added within 30 minutes with cooling and stirring at about 20 °. After one hour the mixture was cooled to 0 °, 10 g of potassium carbonate were added and the mixture was stirred for 10 minutes. After filtering, the filtrate passed through Evaporation of the solvent concentrated. The OeI thus obtained has a Refractive index of il: 1.5130.

030046/0246

29179U

ΛΑ

In an analogous manner or by one of the methods described herein, the following compounds of the formula I can be prepared:

Table I (XR ₅ = -CH-COOCH)

Verb. 2 ^R l ^R 2 ^R 3 ^R 4 5-CHg -CH-OR ₇ 'hy sical No. 3 H O aten 1 4th CH ₃ 6-CH ₃ H H H * *
Y n ^ ° = 1.5066 5 CH ₃ 6-CHg 3-CHg 5-CHg H CHg
-CHOC ₂ H ₅ 6th CH ₃ 6-CHg H H Γ ³
-CHOC ₂ H ₅ n ^ ° = 1.5030 7th CH ₃ 6-CHg 3-CHg 4-Br CH ₃
-CHOC ₂ H ₅ CH ₃ 6-CHg H H CHg
-CHOC ₄ H ₉ (n) 8th Cl 6-Cl 4-CHg H I 1
V 9 Br 6-Br 4-CHg CHg
-CHOC ₂ H ₅ 10 4-Cl β
β Φ CH ₃ 6-Br 3-CHg I!
"V 11 CH ₃ 6-CHg H CH ₂ Cl
-CH-OC ₂ H ₅ P. Cl 6-Cl 4-CHg P.
-CHOC ₂ H ₅ * Φ CH ₃ 6-Cl 3-CHg II
- 9
Y

Q30046 / 024

29179U

Verb. No.

^R l

^R 2

-CH-O-

R ₇

Physical data

12th

Br CHg

CH ₃ CH "

CHg

6-Br

6-CHg

6-Cl

6-CHg

6-CHg

6-CHg

6-CH,

6-Cl

6-CH ₀ | 3-Br

6-CHg

4-CH "

3-CHg

3-CHg

3-CHg

3-C1

3-CH,

6-CH ₀ j 3-CH "

-Cl! 4-CH.

4-Cl

5-CHg

5-CHg

4-Cl

5-CHg

• ·

I I

• ·

I I

CH ₃ -CHOC ₂ H ₅

• • ·

__i I

v "

CgH ₇ (i) OCH "

-CH-

Γ ³

-CHOC ₄ K ₉ (Xi)

I.

• ·

1 i

i ϊ

^C 2 ^H 5 -CHOC ₂ H ₅

CH ₂ Cl -CH-OC ₂ H ₅

• II

—— · ·

1.5067

Q30046 / 0246

-yc-

Verb. \ ^S 2 * 3 ^R 4 No. 24 CH ₃ 6-CH ₃ H H 25th CH ₃ 6-Cl 4-CH ₃ H 26th Cl 6-Cl 3-CH ₃ 4-Cl 27 CH ₃ 6-Cl 4-Cl H 28 CH_ 6-CH ₃ H H 29 Br 6-Br 3-CH ₃ 4-Br 30th CH ₃ 6-Br 4-Cl H 31 Br 6-Br 3-CH ₃ 4-Br 32 CH ₃ 6-C ₂ H ₅ 3-CH ₃ H 33 CH ₃ 6-Cl 4-Cl 5-CH ₃ 34 CH ₃ 6-C ₂ H ₅ H H 35 CH ₃ 6-OCH ₃ H H 36 CH ₃ 6-C ₂ H ₅ H H

-CH-OR ₇

, 2 5
-CHOCH ₃

CH ₃

-CHOC ₂ H ₅ CH ₃

-CHOC ₉ H-CH ^{L Λ} -CHOC ₄ H ₉ (Ii)

C ₃ H ₇ (n)

₃₇
-CHOCH ₃

• · i i

• *

I I

/ ν

• ·

I I

CH ₃

CH "

-CHOC ₄ H ₉ (n)

30046/024

29Ί79Η

^R 2 -CH-O-

Physical data

37

38

39

CH ₃

6-Br

4-Br

CH_

CEL

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

6-Br

-Br

6-Br

6-C ₂ H ₅

6-Cl

6-Cl

6-CH ₃

5-CH ₃

CH ₃ 6 -C ₂ H ₅

CH ₃

CH ₃

^C 2 ^H 5

CH ₃

6-CH ₃

6-CH ₃

6-C ₂ H ₅

6-CH ₃

4-Br

3-Cl

4-Br H

4-Cl 4-Cl

4-Cl H

4-Cl 4-Br

H 4-Cl

4-Br

H H

H H

H H κ \

_# κ \

_J ϊ

^ κ'χ ^ _ί ί

CHo
-CHOC ₂ H ₅ Cl OC ₂ H ₅

CH ₂
-CH-

κ \

CH ₃ °
-CHOC ₂ H ₅ CH ₃
H-Cl

-CH-OC ₂ H ₅

Γ ³

-CHOC ₂ H ₅

__ΐ T

'ν'

ί *

CH,

030046/0248

29179H

Verb. ^R l CH ₃ ^R 2 ^R 3 ^R 4 H H H -CH-OR ₇ Physical No. K data OCHg H H •
• · 50 CH, 6-Cl H H i I 3 H V ? ^H 3 51 CHg 6-Cl H H -CHOC ₂ H ₅ CHg 52 CH ₂ 6-Cl H H -CHOC ₄ H ₉ (n) CHg 53 CH ₃ 6-Br 4-CHg H -CHOC ₄ H ₉ (n) • · 54 CH ₃ 6-Br H H II
- · ·
V / \ 55 CH ₀ 6-Br 4-CH ₃ H _i i 3 V / \
• · 56 CH ₃ 6-CHg 4-Cl I I
- · ·
V CH ₃ 57 CH ₃ 6-Br H -CHOC ₂ H ₅ CH. 58 CH ₃ 6 "" CHq 4-CHg - ^ C ₂ H ₅ •
• · 59 OCH ₀ 6-Cl H I I
- · · 3 V CH ₃ 60 6-Br 4-CHg -CHOC ₂ H ₅ •
• · 61 6-Br H - · ·
ν

0300A6 / 0246

- vc-

Verb.
No.

CH.

GH,

Cl

CIL

CH-,

CH.

CH,

CH.

CH.

CH.

CH.

CH.

6-CH.

6-C ₂ H ₅

6-C1

6-CH.,

6-C ₂ H ₅

6-CH.

6-C ₂ H ₅

6-CH.

6-CH.

6-CH.

6-CH.

6-CH.

6-CH.

4-CH ₃ 4-Br

4-OC ₄ H ₉ 3-CH ₃

4-Cl

3-CH ₃

4-Cl

3-CH ₃

3-CH

H 3-CH ₃

H 3-Cl -CH-OR ₇ K

H H

H H H

H H H

H H

HH [I.

a

CH

κ \

O ·

• ·

I I

CH ₃ -CHOC ₂ H ₅

CH ₃ -CHOC ₂ H ₅

• ·

(n)

Cl

Q30046 / 0246-CH-OC ₂ H ₅

-CH ₂ OC ₂ H ₅

-CH ₂ OC ₄ H ₉ (n)

-CH ₂ OCH ₃

-CH ₂ OC ₂ H ₅

iPh-ysical. constant

M.p. 78-81 '

20th

= 1.5034

29179H

-45--.

Verb.
No. ^R l ^R 2 ^R 3 ^R 4 -CH-OR ₇ Phy s ika1i s ehe
data 76
77 CH3
CH ₃ 6-CH ₃
6-C ₂ H 3-CH ₃
H 5-CH ₃
H -CH ₂ OCH ₃
-CH ₂ OC ₃ H ₇ (i)

Table II (XR ₅ = CH ₂ -COOCH ₃ )

Verb. ^R l R ₂ H ^R 4 -CH-OR ₇ No. I.
^R 6 78 CH ₃ 6-CH ₃ H H ΐ ΐ
V 79 CH ₃ 6-CH ₃ H H CH ₃
-CHOC ₂ H / \
φ β 80 C ₂ H ₅ 6-C ₂ H ₅ H H I ί
- ν a
V 81 CH ₃ 6-C ₂ H ₅ H H I ί
V CH ₃ 82 CH ₃ 6-CH ₅ H H -CHOC ₂ H ₅ 4m -J 83 CH ₃ 6-CH ₃ 3-CH ₃ H ΐ ϊ
- ce
V 84 CH ₃ 6-CH ₃ H H CH ₃
-CHOC ₄ H ₉ (η) 85 CH ₃ 6-Cl H H ί ί
V * * 86 Cl 6-Cl H H * ι
V

030046/0246

Verb.
No. ^R l ^R 2 ^R 3 ^R 4 -CH-OR ₇
I '
^R 6 87 ^CH 3 6-CH ₃ 3-CH ₃ H -CH ₂ OC ₂ H

Γ ³

Table III (XR ₅ = -OH COOC ₂ H ₅ )

^R l R ₂ R ₃ ^R 4 -CH-OR ₀
O
CH-R ₇ Verb.
No. K / \
• « CH ₃ 6-CHg H H II
- · ·
V 88 ■ · CHg 6-CHg 3-CH ₃ H 1 I.
- · ·
V 89 *
/ \
• · CH ₃ 6-CH ₃ 3-CH ₃ 5-CH ₃ II
- · ·
V 90 CHg 6-CHg H H -CH ₂ OCH ₃ 91

0300A6 / 0246

Table IV (XR ₅ = «"<- «■ ₂ ^^^ ₃ ,

Verb.
No. ^R l ^R 2 ^R 3 ^R 4 - CHOIR ₇
K Phys ically.
data 5 92 CH ₃ 6-CH ₃ H H •
• ·
II
- · ·
V OeI
τξ °: 1.5130 ₅ (η)
1 • · 93 CH ₃ 6-C ₂ H ₅ H H II
—— · ·
Y 94 CH ₃ 6-CH ₃ H H Γ ³
-CHOC ₂ H ₅
• OeI
τξ °: 1.4992 95 CH ₃ 6-CH ₃ 3-CH ₃ 5-CH ₃ II
- · ·
V 96 CH ₃ 6-CH ₃ H H -CH ₂ OC ₂ H ₅ •
• · 97 CH ₃ 6-CH ₃ 4-Cl H II
- · ·
V CH ₂ Cl 98 CH ₃ 6-CH ₃ 3-CH ₃ H -CHOC ₂ H ₅ •
• · 99 CH ₃ 6-Cl H H - »·
V 100 CH ₃ 6-Cl H H CH ₃
-CHOC ₂ H 101 CH ₃ 6-CH ₃ 3-CH ₃ 5-CH ₃ CH ₂ Cl
-CH-OC ₂ I. 102 CH ₃ 6-CH ₃ 3-CH ₃ H Γ ³
-CHOC.H
4th

030046/0246

29179H

Verb. ^R l R ₂ R ₃ ^R 4 - CHOIR ₇
K Physically. No. P.
-CH OC H constant 103 CH ₃ 6-CH ₃ 4-Cl H CH ₃ -CHOC ₄ H ₉ Cn) 104 CH ₃ 6-CH ₃ H H ? ^H 3 -CHOC ₂ H ₅ 105 CH ₃ 6-C ₂ H ₅ H H -CHOC ₂ H ₅ 106 CH ₃ 6-CH ₃ 3-CH ₃ 5-CH ₃ CH ₃ -CHOC ₂ H ₅ 107 CH ₃ 6-CH ₃ 3-Cl H CH ₂ Cl -CH-OC ₂ H ₅ 108 CH ₃ 6-CH ₃ H H C ₃ H ₇ (i) -CHOC ₂ H 109 CH ₃ 6-CH ₃ 4-Cl H C-H-, Ci) 13 7
-CHOC ₂ H ₅ 110 CH ₃ 6-CH ₃ 3-Cl H -CH ₂ OCH ₃ 111 CH ₃ 6-CH ₃ 3-Cl H CH ₃ -CHOC ₄ H ₉ (n) 112 CH ₃ 6-CH ₃ 3-Cl H C ₃ H ₇ (i) -CHOC ₂ H ₅ 113 CH ₃ 6-CH ₃ 3-CH ₃ H C ₃ H ₇ Ci) -CHOC ₂ H ₅ 114 CH ₃ 6-Cl H H * · II
- · ■
V 115 CH ₃ 6-Cl 4-Cl H ' I.
VI 116 CH ₃ 6-CH ₃ 3-Cl H

0300A6 / 0246

29179U

Verb. ^R l ^R 2 R "
j ^R 4 - CHOIR ₇ Physically. No. ^R 6 Cons aunt C ₃ H ₇ (i) 117 CH ₃ 6-C ₂ H ₅ H H -CH-OC ₂ H ₅ C ₃ H ₇ (i) 118 CH ₃ 6-CH ₃ 3-CH ₃ 5-CH ₃ -CHOC ₂ H ₅ CH ₃ 119 CH ₃ 6-CH ₃ 3-CH ₃ H -CHOC ₂ H ₅ CH ₃ 120 CH ₃ 6-C ₂ H ₅ H H -CHOC ₄ H ₉ (n) • · 121 CH ₃ 6-CH ₃ 3-CH ₃ H - » ·
V CH ₃ 122 CH ₃ 6-CH ₃ 3-CH ₃ 5-CH ₃ -CHOC ₄ H ₉ (η) CH ₃ 123 CH ₃ 6-Cl 4-Cl H -CHOC ₂ H ₅

030046 / 02A6

Formulation examples

Example 4 Dust: To produce a) 5% and b) 2% dust, the following substances are used:

a) 5 parts of active ingredient
95 parts of talc;

b) 2 parts of active ingredient

1 part of highly dispersed silica,
97 parts of talc;

The active ingredients are mixed and ground with the carrier substances and can be dusted in this form for use.

Example 5 Granules: The following substances are used to produce 5% granules:

5 parts of active ingredient

0.25 part of epichlorohydrin,

0.25 part of cetyl polyglycol ether,

3.50 parts of polyethylene glycol

91 parts of kaolin (grain size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added added. The solution obtained in this way is sprayed onto kaolin, and the acetone is then evaporated in vacuo. A Such microgranules are advantageously used for combating soil fungi.

Q30046 / 0246

29Ί79Η

-or-

Example 6 wettable powder: To produce a) 70% b)% c) and d) 25% e) 10% wettable powder, the following ingredients are used:

a) 70 parts of active ingredient

5 parts of sodium dibutylnaphthylsulphonate, 3 parts of naphthalenesulphonic acid-phenolsulphonic ren-formaldehyde condensate 3: 2: 1, parts kaolin, parts Champagne chalk;

b) 40 parts of active ingredient

5 parts of lignin sulfonic acid, sodium salt, 1 part of dibutylnaphthalenesulfonic acid, sodium salt, Parts of silica;

c) 25 parts of active ingredient

4.5 parts calcium lignosulfonate, 1.9 parts of champagne chalk / hydroxyethyl cellulose mixture

(1: 1),

1.5 parts of sodium dibutyl naphthalene sulfonate, 19.5 parts of silica, 19.5 parts of champagne chalk, 28.1 parts of kaolin;

d) 25 parts of active ingredient

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of champagne chalk / hydroxyethyl cellulose mixture

(1: 1), 8.3 parts of sodium aluminum silicate, 16.5 parts of kieselguhr, 46 parts of kaolin;

e) 10 parts of active ingredient

3 parts mixture of the sodium salts of saturated fatty alcohol

030046/0246

29179H

sulfates,

5 parts of naphthalenesulfonic acid / formaldehyde condensate, 82 parts of kaolin;

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. The wettability and wettability of wettable powders is obtained Suspensions of the desired suspensions with water Dilute the concentration and especially let it be used for foliar application.

Example 7 Emulsifiable Concentrates: The following substances are used to produce a 25% emulsifiable concentrate:

25 parts of active ingredient

2.5 parts epoxidized vegetable oil,
10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture,

5 parts of dimethylformamide
57.5 parts of xylene.

From such concentrates, emulsions of the desired concentration can be prepared by dilution with water are particularly suitable for foliar application.

The compounds of the formula I can be used with other suitable pesticides to broaden the spectrum of action of such agents or active ingredients that promote plant growth can be used.

Q30046 / 0246

2ς

Biological examples Example 8 Action against Phytophthora infestans on tomatoes

a) Curative effect

Tomato plants of the "Red Gnome" variety were grown after three weeks sprayed with a zoospore suspension of the fungus and incubated in a cabin at 18 to 20 ° and saturated humidity. Interruption of humidification after 24 hours. After the plants had dried off, they were sprayed with a broth that was used as a wettable powder contains formulated active ingredient in a concentration of 0.06%. After the spray coating had dried on, the plants were again in the humid cabin for 4 days. Number and size of Typical leaf spots that appeared after this time were the benchmark for the effectiveness of the substances tested.

b) Preventive-systemic effect

The active substance, formulated as a wettable powder, was applied in a concentration of 0.006 Z (based on the soil volume) to the soil surface of three-week-old potted tomato plants of the "Red Gnome" variety. After a three-day waiting period, the underside of the leaves of the plants was sprayed with a zoospore suspension of Phytophthora infestans. They were then kept for 5 days in a spray booth at 18 to 20 ° and saturated humidity. After this time, typical leaf spots formed, the number and size of which were used to assess the effectiveness of the substances tested.

When using, for example, the compounds 1, 3, 13, 72, 74 and 94, a good effect was achieved (reduction of the infestation to less than "O Z in comparison with untreated controls).

Q30046 / 02A6

29179U

- «r- 2C

Example 9 Effect against. Plasmopara viticola (Bert, et Curt.) (Berl. Et DeToni) on vines Residual preventive effect Vine cuttings of the "Chasselas" variety were grown in the greenhouse. At the 10-leaf stage, 3 plants were sprayed with a broth (0.06% active ingredient) prepared from the active ingredient formulated as a wettable powder. After the spray coating had dried on, the plants on the underside of the leaves were evenly infected with the spore suspension of the fungus. The plants were then kept in a humid chamber for 8 days. After this time, clear symptoms of disease appeared on the control plants. The number and size of the infection sites on the treated plants served as an assessment standard for the effectiveness of the substances tested.

Example 10 Action against Pythium debaryanum on sugar beet (Beta vulgaris) Action after soil application The fungus was cultivated on sterile oat grains and added to a soil-sand mixture. The soil infected in this way was filled into flower pots and sown with sugar beet seeds. Immediately after sowing, the test preparation, formulated as a wettable powder, was poured over the soil as an aqueous suspension (20 ppm of active ingredient based on the volume of soil). The pots were then placed in the greenhouse at about 0 ^° C. for 2-3 weeks. The earth was always kept evenly moist by lightly showering over it.

When evaluating the tests, the emergence of the sugar beet plants and the proportion of healthy and diseased plants is determined.

When using compounds of the formula I, including compounds No. 1 and 3, the infestation was reduced to less than 20% inhibited.

030046/0246

Claims (6)

29179U -JtS- - Claims
1. Compounds of formula I ι TB
! A SH- X / ⁵ / \ C-CH-O-CH-OR ₇ (I) wherein R _{1 is} C ₁ -G ₄ -AlCyI, C ₁ -C ₄ -AlIcOXy or halogen, R _{2 is} hydrogen, C ₁ -C ₃ -AlCyI _{8 is} C ₁ -C ₄ alkoxy or halogen, R _{3 is} hydrogen ,. C ₁ -C ₃ alkyl or halogen ,, and?., Hydrogen or methyl, the total number of carbon atoms of the substituents R ₁ , R _35, R ₃ and R ₄ not exceeding eight XSt ₃ X is -CH ₂ - or -CH -, and R _{5 is} -COOCH ₃₉ or COOC ₂ H ₅ or -CH ₂ OCH ₃ , E _{g is} hydrogen or -CH-H, R _{7 is} C 1 -C 4 -alkyl R "and R" independently of one another are hydrogen, halogen or C ₁ -C ₄ -AllIyI
can form. represent or also S ₇ and Rg together C ₂ -C alkylene 2. Compounds according to claim 1 wherein in the formula I R_ is methyl or methoxy, R _{7 is} methyl, ethyl, chlorine or bromine, R _{3 is} hydrogen, methyl, chlorine or bromine and R is hydrogen or methyl. 3. Compounds according to claim 2 wherein in the formula I E is methyl, R "in the ortho position is methyl or ethyl and R ₃ and R are hydrogen or methyl. 4. Compounds according to any one of claims 1 to 3 wherein in the Ibrmel I -XR, - for -CHCOOCH, stands.
5 y 5. Fungicidal agents containing as at least one active component 030046/02 4 6 ORIGINAL INSPECTED nente a compound according to any one of claims 1 to 6. Process for the preparation of compounds of the formula I characterized when R, has a meaning other than hydrogen, by reaction of a compound of formula II P-, V C- CHOH ⁴ * 2 II I 0 R ₆ with a compound of the formula III CH - OR ₇ Il C-Rg (III) la presence of a catalyst _s or when R 1 = hydrogen by reaction of a compound of the formula H _1, preferably a salt thereof, with an alkali or alkaline earth metal with a compound of the formula IV - 0 - R ₇ IV where iß the formulas II, III and IV R. to R- and X are as defined under formula I and Hal ' sees halogen, preferably chlorine or bromine * FO 7.5 / NOR / lf * 030046/0246