DE3025694A1 - PHENYLAMINOAL CHANNELS AND PHENYLAMINOACETALS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN MICROBICIDES - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. * ~. Assmann - Dr. R, Koenigsberger Dipl.-Phy &. R. Holzbauer - Dip !, ing. F. KHngseison ■ Dr. F. Zumstein jun.

PATENT LAWYERS

80OO Munich 2 · BräuhausstraDe 4 -Telephone, collective no. 22 53 41 Telegrams Zumpat -Telex 529979

CIBA-GEIGY AG 5-12428 / = 3025694

Basel, Switzerland)

Phenylaminoalkanals and Phenylaminoacetals, experience of their preparation and their use in microbicidal agents.

The present invention relates to compounds of the formula I.

^ "" C 'fi " ^R ₆

in what? ». and R. independently of one another

C ₁ -C ₃ A ^ yI, C ^ -C alkoxy or halogen;

R. Hydrogen, C -C alkyl or halogen; R, hydrogen or methyl mean

where the sum of the carbon atoms in R ₁ , R ₀ , R and R does not exceed the number 6 and R_ stands for hydrogen or C - C, -alkyl, Rg ß- (C -C.) - Alkoxyäthy1 or optionally through Halogen.

substituted 2-furyl, 2-tetrahydrofury! group or -CH ₀ E, where Z is one of the following groups:

a) -OR ₇ , -SR ₇

b) -NH-

c) -

d) -

e) 1,2-pyrasol, 1,3-imidazole, 1,2,4-triasol, including their salts and metal complexes, and R, for a C ₁ -C 4 -alkyl which is optionally substituted by C 1 -C -AlkoKy, C , -C, -Alkenvl- or C ^ -C ^ -alkynyl group; R for hydrogen or C -C -alkyl; R_

030065/0839

for C -C -alkyl or a phenyl group optionally substituted by halogen or methyl and R ₁₀ for C ^ C ^ -alkyl, mono- or di- (CC) -alkylamine, R ₁₁ for a optionally _{substituted by C 1} -C., - Alkoxy substituted Cj-C.-alkyl group and X is -CHO or

OY ₁
-CH ^, wherein Y ₁ and Y_ independently of one another are C ^ -C ^ -alkyl

OY ₂

mean or together one or more times C -C "-Alkyl substituted C_-C_-alkylene bridge form or together form a 1,2-cyclohexane ring.

Compounds of the formula I can be found in the aldehyde form as phenylaminoalkanals and in the acetalized form as phenylaminoacetals describe.

Under alkyl or alkyl part of another substituent are each according to the number of carbon atoms indicated, the following groups are to be understood: methyl, ethyl, propyl, butyl, pentyl, hexyl and their isomers e.g. iso-propyl, iso-butyl, sec-butyl, tert-butyl »iso-pentyl, etc. Alkylene means e.g. methylene, ethylene, propylene, etc. alkenyl stands for e.g. vinyl, allyl, 2-butenyl, etc. Alkynyl means above all propargyl. Halogen stands for fluorine, chlorine, bromine or iodine.

The compounds of the formula I can be prepared by a number of methods, such as those listed below, for example. In the formulas I ab and II to XV, R to R ₁₁ and X, Y ₁ and Y- have the meanings given under formula I, Hal stands for halogen, preferably for chlorine and bromine and M for hydrogen or a metal, preferably alkali - or alkaline earth.

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• f ·

O ^ -NHCH-X + HOOCR, - · »(I)

⁴ "2

(II) (IU)

A reactive derivative, a compound of the formula III, such as acid halide, acid anhydride or esters can be used.

In some cases, the use of acid-binding agents or condensation agents is advantageous. As such, e.g. tertiary amines such as trialkylamines (e.g. triethylamine), pyridine and pyridine bases, or inorganic bases such as the oxides, hydroxides, Hydrogen carbonates, carbonates or hydrides of alkali and alkaline earth metals as well as sodium acetate into consideration. The starting product II can also serve as an acid-binding agent.

The preparation process A can also be carried out without acid-binding agents, in some cases passing through of nitrogen is indicated to drive off the hydrogen halide formed. In other cases, dimethylformamide is added very advantageous as a reaction catalyst.

B. If R, meaning other than
ο

-CH “NH-N; Has:

A / l 0 R ₅

• f / ^ -NK-C-R, + HaICH-J

* ► (I)

'2

03006 ^ / 0839

§02569 ^

Here, the compound of formula IV is first with butyl lithium or Na hydride converted into the corresponding alkali salt, or the process is carried out in the presence of an acid-binding agent Carried out by means of process A analogously, preferably with the addition of catalytic amounts of alkali metal iodide.

C. When R _g -CH OSO R or -CH, OCR means:

(VI)

: -x

(VII)

-OH

8-b

(VIII)

A salt, especially an alkali metal salt of the formula VI, is advantageously used.

D. When R _{g is} -CH ₂ XR ₇ ; -CH ₂ OC-R ₁₁ ; -CH ₂ NH-N (R ₃ ) (R ₉ ) or a

Azolylmethyl stands (azole - 1,2-pyrazole, 1,3-imidazole or 1,2,4-triazole):

X *

\ S (IX)

MXR_ (X) Q
MOCR (XI) NH ₂ N (Rg) (R ₉ ) ( ^χ ΐΐ) M-Aezol (XIIl)

When M = hydrogen, the use of a salt forming Attached by means such as an oxide, hydroxide, hydride, etc. of alkali or alkaline earth metals. When using output

030065/0839

substances of the formula XII, the end product is obtained as a hydrohalide.

The free hydrazino compound can be converted from this with mild bases at room temperature or at a slightly elevated temperature obtain. There are z.3. Alkali carbonates.

E. If R, for ß- (C -C.) - Alkoxyäthyl: ο 14

ftA I ^s

/ \ V. / ⁺ M- (C ₁ -C ₄ ) AIkOXy · »(I)

2 ö
(XIV) (XV)

The procedure here is analogous to method D. F. When R _{5 is} ß-i ^ -C ^ -alkoxyethyl:

J3 / 1 P

/) ^ / ⁺ M (C ₁ -C) alkoxy ^ (I)

χ / \
r ' f? ^CHCH

(XVI) (XV)

In this process, the alcohol or the alcoholate is used XV (M = «metal atom) carried out a Michael addition.

G. Specifically, when X is -CHO then so is the following reaction possible:

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2 O

(Ia)

Open acetals of the formula Ia, in which X

y ⁰² i

-CIi. and Y ₁ and Y- are C.-C, -alkyl, become-OY ₂

preferred. The cleavage works best using dilute Acids such as mineral acids.

H. Especially when Y ₁ and Y _{2 form} a C -C alkylene bridge which is optionally substituted one or more times by C -C alkyl or when Y and Y "denote a hydrogenated six-membered ring fused in the 1,2-position :

■ 4

(Iu) (XVII)

Here, an open-chain acetal of the formula Ib, in which Y. and Y _{2 is} preferably C.-C, -alkyl, with a diol of the formula XVII, in which A is 1,2-cyclohexylene or an optionally substituted by one or two C -C, - Alkyl-substituted 1,2-ethylene or 1,3-propylene denotes implemented. In certain cases it can be advantageous to work at higher temperatures *; the presence of acid can also have a beneficial effect in this process.

Solvents can in principle be used in all processes which are inert to the reactants.

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- ^r - .41-

3Q25694

Examples of such solvents are:

Aromatic or aliphatic hydrocarbons such as benzene, toluene, Xylenes, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, tetrachlorethylene; Ethers and ethereal compounds such as dialkyl ethers e.g. t-butyl methyl ether, dioxane, tetrahydrofuran; Nitriles like Acetonitrile; Ν, Ν-dialkylated amides such as dimethylformamide; Dimethyl sulfoxide; Ketones such as methyl ethyl ketone and mixtures thereof Solvents with each other.

All starting materials are produced according to methods known per se.

See J. Org. Chem. 30, 4101 0.965),
Tetrahedron 1967 , 487
Tetrahedron 1967 , 493

The various procedures are also part of "the Invention. Some of the starting materials are also new and form part of the invention; they show a fungicidal effect.

In the following references, acylated anilides are described as herbicides; There are no indications of a fungicidal effect none of the compounds mentioned there has a useful fungicidal effect:

U.S. Patent 3,966,811

U.S. Patent 4,113,464

U.S. Patent 3,946,043

U.S. Patent 3,946,044

U.S. Patent 3,946,045

The compounds of the formula I have an asymmetric carbon atom in the side chain adjacent to X and can are resolved in the usual way into optical antipodes (racemate resolution); e.g. through fractional crystallization of

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Salts of II with an optically active acid (such as D-lactic acid) and further reaction of the optically pure compounds from IT to

Depending on the substitution, further asymmetric carbon atoms can be used be present in the molecule.

Regardless of the aforementioned optical isomerism,

usually atropisomerism around the phenyl sf axis

observed in cases where the phenyl ring is at least in the 2,6-position and at the same time asymmetrical to this axis (if necessary also by the presence of additional substituents is substituted.

If no specific synthesis is carried out to isolate pure isomers, a product of the formula I is normally obtained as a mixture of these possible isomers.

The compounds of the formula I can be used alone or together with suitable carriers and / or other additives be used. Suitable carriers and additives can be solid or liquid and correspond to those used in formulation technology common substances, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, Binders or fertilizers.

The content of active ingredient in hand-icing agents is between 0.1 and 90% jthe proportion of aggregates is 10 to 99.9%, with 0 to 30% of a surfactant among the additives.

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

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Fixed forms of processing: dust and grit (up to 10%) granules, coating granules, impregnation granules and homogeneous granules, pellets (grains) (1 to 80%);

Liquid processing forms:

a) Active substance concentrates dispersible in water: Wettable powders and pastes (25-90% in commercial pack, 0.01 to 15% in ready-to-use solution); Emulsion and solution concentrates (10 to 50%; 0.01 to 15% in ready-to-use solution);

b) solutions (0.1 to 20%); Aerosols

Such means also belong to the invention.

It has surprisingly been found that compounds with the structure of the formula I are very useful for practical needs have favorable microbicide spectrum for protecting crops. For the purposes of the present invention, crop plants are, for example, cereals, sharks, 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, flowers, foliage, stems, tubers, Roots) of these and related crops, the fungi that occur are contained or destroyed, with later growing ones as well Plant parts are spared from such fungi. The active ingredients are against those belonging to the following classes effective phytopathogenic fungi: Ascomyceres (e.g. Venturia); but then especially against those belonging to the Phycomycetes class

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- / Kr

Oomycetes such as Peronosporales (Phytophthora, Pythium, Plasmopara). links of formula I are also effective against Cercospora pathogens.

In addition, the compounds of the formula I have a systemic effect. They can also be used as a dressing agent for the treatment of seeds (fruits, Tubers, grains) and plant cuttings for protection against fungal infections and against phytopathogenic fungi that occur in the soil can be used.

The invention thus also relates to the use of the compounds of the formula I for combating phytopathogenic microorganisms.

The following types of substituents or combinations of these with one another are preferred.

For R ₁ : - a) C -C ₂ -alkyl, C ₁ -C ₂ -AlkOXy b) CE-, OCH-

For R-: - a) CH-, OCH-, halogen b) CH-, chlorine

For R_: - a) hydrogen, CH-, halogen b) hydrogen

For R,: - a) hydrogen, CH-b) hydrogen

For R ₅ : - CH-

"/ ^0Υ ι

At X: - a) CHO, ChT

b)

"OY,

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Y ₁ and Y denote C -C -alkyl or optionally together a C -C -alkylene bridge which is monosubstituted or polysubstituted by C ... -C -alkyl or together form a 1,2-cyclohexane ring.

For R,: - a) 2-furyl, 2-tetrahydrofuryl, β- (C - C ₂ alkoxy) ethyl, CH ₂ Z

b) 2-furyl, 2-tetrahydrofuryl, CH ₂ CH OCH-, CH ₃ Z with meaning for Z of

a) -0-R ₇ (R ₇ -C ₁ -C ₃ -alkyl)

b) -NH-H ^ ⁸ (R ₈ and R ₉ - C ^^

c) -OSO-R ₁ (R. -C -C - alkyl, methylamine)

d) 1,2,4-triazole

At R_: - optionally substituted by C -C -alkoxy

., CC ₄ alkenyl, C ₃ -C ^

For R-: - C -C -alkyl

At R ₉ : - Cj-C.-alkyl

For R: -C -C -alkyl, methylamine

This results in the following preferred groups, for example:

R ₂ »CH ₃ , -OCH ₃ , halogen

R- »hydrogen, CH-, halogen R ₄ » hydrogen, CH-

R. - methyl

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X = CHO

Y \

, CH

⁰ Y

⁰ Y

Y .. and Y- C -C ^ -alkyl or together represent a single or polysubstituted or unsubstituted by C -C alkyl C -C -Alkylenbrückii or together form a 1,2-cyclohexane ring.

R - 2-furyl, 2-tetrahydrofuryl, ß-C ^ - ^ where Z means:
a) -OR ₇ , -SR ₇

b) -NH- ^
O -

d) l ^ -Pyrazole ^^ - Imidazo !, 1,2,4-TriazoL including inclusion their salts and metal complexes.

optionally substituted by C.-C ₂ alkoxy-substituted C -C alkyl, C.-C ^ alkenyl, C ₃ -C _z

C ₁ -C alkyl, methylamine;

Another preferred group is:
R ₁ »CH ₃ , OCH ₃

R- »CH, chlorine
R »hydrogen
R, - hydrogen
R ₅ -CH ₃

^0Y 2

Y ₁ and Y represent "C ^ jC.-alkyl or together form a mono- or polysubstituted or unsubstituted alkylene bridge by C - C -alkyl,

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R, = »2-furyl, 2-tetrahydrofuryl, -GH ₀ CH ₀ OCH., -CH ₀ Z where Z means:

a) -OR ₇ (R ₇ = ■ C ₁ -C

b) -NH- / ^{8 (R} 8

9 (R ₉

c) -OSO ₂ R ₁₀ (R ₁₀ »C ₁ -C ₂ -AIkYl, methylamine)

d) 1,2,4-triazole.

The following examples serve to provide a more detailed explanation of the invention without limiting the same. The temperatures are given in degrees Celsius.

Unless otherwise noted, when an active ingredient of the formula I is mentioned, the racemic mixture is always meant.

Example 1 ;

a) Manufacture of the intermediate

—NHCH ₂ CH (OCH ₃ )

N- (2,6-Dimethylphenyl) -amino-acetaldehyde-dimethylacetal 8.8 g of 553 sodium hydride in 50 ml of toluene were added with stirring and passing through nitrogen at a bath temperature of 140 ° 24.2 g of 2,6-dimethylaniline in 20 ml of toluene were added dropwise, 3 hours heated under reflux until the evolution of hydrogen ceases and then 37.2 g of bromoacetaldehyde dimethyl acetal were added. After refluxing for a further 24 hours, the mixture was cooled with 500 ml of water diluted, the toluene phase separated, with a little Washed water, dried over sodium sulfate, filtered and

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the solvent evaporated. The oily residue was fractionally distilled in a high vacuum; Bp. 100 ^S / O, 09 mbar.

b) Manufacture of the final product

CH 3

N- (2,6-Dimethylphenyl) -N-methoxyacetyl-amino-acetaldehyde-dimethylacetal

To 15.4 g of N- (2,6-dimethylphenyl) -amino-acetaldehyde-dimethyl acetal and 6.3 g of pyridine in 100 ml of toluene were at 10 ° 8.7 g of methoxyacetic acid chloride added dropwise. After the weakly exothermic reaction had subsided, stirring was continued for 3 hours at room temperature, from Pyridine hydrochloride filtered off, the reaction solution twice with Washed 50 ml of water each time, dried over sodium sulfate, filtered and the solvent was evaporated. The oily residue in a high vacuum fractionally distilled; Sdp: 129-130VO, 05 mbar.

Example 2 ;

a) Manufacture of the intermediate

: —NH-CH-CH

(OCH ₃ ) ₂

2- [N- (2,6-Dimethylphenyl) amino] propionaldehyde dimethylacetal 60.5 g of 2,6-dimethylaniline, 71.5 g of methylglyoxal dimethylacetal and

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1.3 g of concentrated sulfuric acid were in the presence of 1.3 g of 5% Pt on activated carbon at 40-50 ° and a pressure of 5 bar Hydrogen treated- The hydrogenation mixture was treated with 300 ml of ethyl acetate diluted, filtered off from the catalyst, washed with 100 ml of 10% sodium bicarbonate solution and with water. After this Drying over sodium sulfate, the solvent was evaporated and the oily residue is fractionally distilled in a high vacuum; Sdp. 77-81VO, 05 mbar.

b) Manufacture of the final product

.CH f ³
- < ^J .CH-CH (OCH-),

W ^{3 2} (comp. No. 2) · - <^ CCH ₂ OCH

2- [N- (2, δ-dimethylphenyD-N-methoxyacetyl-aminol-propionaldehyde di-ethyl acetal.

In 14.1 g of 2- [N- (2,6-dimethylphenyl) amino] propionaldehyde dimethyl acetal and 7.5 g of soda in 150 ml of benzene, 6.4 ml of methoxyacetic acid chloride were added dropwise with stirring. The reaction mixture warmed to 35 ° C. during this process. The mixture was left to stir for one hour at room temperature, filtered and the filtrate was evaporated to dryness in vacuo. The oily residue was crystallized from gasoline. 10 g final product was obtained, mp. 44-45 C ^e

Example 3 ;

Manufacture of the final product

(Verb. No. 12)

CH-OCH

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2- [N- (2,6-dimethylphenyl) -N-methoxyacetyl-amino] -propionaldehyde 20 g of 2- [N- (2,6-dimethylphenyl) -N-methoxyacetyl-aniino] -propionaldehyde dimethylacetal were introduced into 100 ml of 2N hydrochloric acid at room temperature with stirring. From the initially clear solution After some time, a white precipitate separated out, which was filtered off after 1 hour and washed neutral with ice-cold water and dried. After recrystallization from ethyl acetate, the white crystals melt at 73-75 °.

Example 4:
Production of

(Verb. No. 87)

^ CH ₃

2- [N- (2,6-Dimethylpheny1) -N-methoxyacety1-amino] -propionaldehyde-propylene acetal

30.0 g of 2- [N- (2,6-dimethylphenyl) -N-methoxyacetyl-amino] -propionaldehyde dimethylacetal, 7.7 g of 1,3-propanediol and 0.1 g of p-toluenesulfonic acid were heated in 150 ml of dry toluene. A mixture between 61 ° and 110 ° was formed over a 10 cm long Vigreux column distilled off from methanol and toluene. The distillation was continued until the temperature reached 110 ° and only Toluene distilled. The reaction solution was then brought to room temperature cooled and twice with 100 ml of dilute sodium carbonate solution each time and washed 1 time with 100 ml of dilute sodium chloride solution. The organic phase was dried and the solvent was distilled off away. After digestion with petroleum ether, the white crystals of the compound of formula I melted at 96.5-97.5 °.

The following compounds of the formula I can be prepared in an analogous manner or by one of the methods described here:

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-. 3/1

Table I.

CH ₃ , R ₂ - CH ₃ , R ₄ - H)

Verb.
No. H ^R 5 X / ^CH 3
» • ^R 6 Physcal.
constant 1 H H -CH (OC ₂ H ₅ ) ₂ -CH (OCH ₃ ) ₂ I.
I. -CH ₂ OCH ₃ Sdp.
146 ° /
0.04 mbar 2 H CH ₃ -CH (OCH ₃ ) ₂ Λ ■ -CH ₂ OCH ₃ Smp
44-45 ° 3 H H -CH (OCH ₃ ) ₂ 0— *
0— * -CH (OCH ₃ ) ₂ -CH ₉ OCH ₃ Bp. 129 ° /
0.05 mbar 4th H H -CH (OCH ₃ ) ₂ " ⁽ V.
0— < l1 M
- · ·
V M.p. 90-92 ° 5 H H -CH (OC ₂ H ₅ ) ₂ -CH ₂ OC ₂ H ₅ 122-124 °
0.05 mbar 6th H CH ₃ \ - i1 il
• ■
'V OeI 7th H CH ₃ NH
• · M.p.
74-76 ° 8th H CH ₃ ί τ
• · OeI 9 H -C ₃ H ₇ -I -CH ₂ OCH ₃ OeI 10 H - ^CH 3 -CH ₂ OCH ₃ M.p.
69-71 ° 11 H H ΐ ΐ
- · ·
V OeI

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A?

Table I ;

CH ₃ , R ₉ - CH ₃₁ R ₄ »H)

Verb.
No. H ^R 5 X 6th Phys.
constant 12th H -CH ₃ -CHO -CH ₂ OCH ₃ M.p. 73-75 ° 13th H -CH ₃ <f -v-Ci Viscos 14th H H -CH (OCH ₃ ) ₂ -CH ₂ OC ₂ H ₅ Sdp. ISO ⁰ /
0.05 mbar 15th H - ^C 2 ^H 5 O- -CH OCH Viscos 16 H -CH ₃ 0— · -CH-OCH M.p. 55-68 ° 17th H H -CH (OC ₂ H ₅ ) ₂ - «*
V OeI 18th H -CH ₃ -C!
C- * -CH ₂ OSO ₂ NHCH ₃ OeI 19th H -CH ₃ ■ ° ci ³
0— · -CH ₂ OC ₉ H ₅ Sep. 63-75'C 20th H -CH ₃ -CHO ίί Μ
- · ·
V OeI 21st H -C ₃ H ₇ -X -CH (OCH ₃ ) ₂ -CH ₂ OCH ₃ Viscos

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- .33.

Table I ; (R ₁ = CH ₃ , R ₂ - CH ₃

Verb. No.

-CH,

-CHO

-CH, -CH_0CH

-CH, -CH ₂ HH-

-CH,

-CHO

-CH, Il Il

-CH, I I

-CH OCH

-CH,

-CH (OCH ₃ ) Il I! _

V '" ^Br

-CH,

-CH,

/ ^C 2 ^H 5

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- 2 (T-

Table I : (R. * CH ₃ , R ₂ *> CH ₃ , R ₄ * H)

Verb.
No. E. ^S 5 X / ^C 2 ^H 5 ■ / ^C 3V ^R 6 Physically.
constant 32 H -CH ₃ -CH (OCH ₃ ) ₂ / A
t -CH (OCH ₃ ) ₂ i ί
V OeI 33 H -CH ₃ -CH (OCH ₃ ) ₂ -CH (OCH ₃ ) ₂ -CH (OCH ₃ ) ₂ -CH, CH ₀ OCH ₃ 34 H -CH ₃ ■ 0- -CH (OC ₂ H ₅ ) ₂ -CH ₂ OC ₂ H. OeI 35 E. -CI
0 - ' -CI
0— « 'Κ -CH-OSO ₀ NHCH- 36 H -CH ₃ .-A Viscos 37 H - ^C 2 ^H 5 -CH ₂ OCH ₃ 38 3-CH ₃ -CH ₃ -CH ₂ <fj
"SBC" Viscos 39 H -CH ₃ i η ΐ
V njpl. 5469 40 H -CH, -CH ₂ OC ₂ H. 41 -CH ₃ -CH ₂ CCH ₃

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-35

Table I ; <Ε _χ - CH ₃ , R, = CH ₃ , R ₄ - H)

Verb. ■ i ^R 5 X ^R 6 Physically. No. 3-CH, j 0 constant 42 H -CH ₃ -CHO -CH ₂ OCH ₃ 43 -CH. -CH (0CH ₃ ) ₂ -Cl ₂ OC ₃ H ₇ -I OeI H 44 3-CH ₃ • - ^C 2 ^H 5 -CH (OCH ₃ ) ₂ -CH ₂ OOi ₃ Viscos 45 H -CH ₃ -CHO -CH ₂ OSO ₂ NHCH Viscos 46 H -CH ₃ -CH (OCH-J ₀ -CH ₂ OCH ₂ CH = CH ₂ OeI 47 - ^C 2 ^H 5 -CH (OCH ₃ J ₂ -CH ₂ OC ₂ H ₅ OeI

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Table II ; CH ₃ , R ₂ - CH ₃ , R ₄ - H, R ₃ - CH ₃ )

Verb. No.

Phys. constant

48

.1 ι

OeI

49

3-CH, -CH, oci :,

2 j

50

viscous oil

51

-CE (OCH ₃ )

-CH,

3-CH,

-CH (OCH ₃ )

-CH ₂ OC ₂ H.

. 5071

/
V.

-CH OCH

-CH (OCH ₃ )

-CH ₂ SCH.

-CH (OC ₄ H ₉ -Ii) ₂

-CH OCH.

3-CH.,

-CH (OCH ₃ )

-CH ₂ OSO ₂ NHCH ₃

-CH ₂ OCH ₃

Sqo. 63-05 °

CH.

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-.23--

Table II ; (R ₁ «GH ,, R_ - CH ,, R. - H, R. - CH,)

Verb.

No.

Phys. Const.

58

-CH (OCH ₃ )

-CE ^ iHN (CH ₃ ) ₂

59

i y Y

60

-CH (OC ₃ H ₇ -H) ₂

J, ^{1 1} y

61

-CH (OCH,

62

e CH

\ / 25

-CH-OCH ₁

^c -v

63

64

CH (OCH ₃ )

-CH ₂ OSO ₂ CH ₃

65

-CH OCH

66

03006B / 0839

Table II ; (R ₁ -CH ₃ , R ₂ - CH ₃ , R ₄ - H, R ₅ - CH ₃ )

Verb.
No. ^R 3 X > / C ₂ ^H 5 / \ ^R 6 V Phys.
Const. 67 3-CH ₃ -a -CH (OCH ₃ ) ₂ -CH (CC ₃ H ₇ - ,,, H -CH ₂ OC ₂ H ₅ OeI 68 H -CHCOC ₃ H ₇ -U ₂ -CH (OCH ₃ ) ₂ -CH ₂ OCH ₃ 69 H < 0 -CH ₂ N ^ j M.p.
80-83 ° 70 H "C
0 ' -CH ₂ OSO ₂ C ₂ H ₅ 71 H -CH-OCH ₃ OeI 72 3-CH ₃ 73 H -CH ₂ OC ₂ H ₃ Viscos 74 3-C1 -CH ₂ OC, 75 H Snip
55.5 -
57 °

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-μτ-

Table II : (R ₁ - CH ₃ , R ₂ - CH ₃ , R ₄ -H, R. - CH ₃ )

Verb. Sr. Phys Konst,

-CH ₂ OgCH ₃

3-Cl -CH OCH

CH (OC ₂ H ₅ )

/ ^C 2 ^H 5 -CH ₀ OC ₀ H ..

4th Ly

-i

3-CH "-CH ₂ OCH ₃

-CH (OC ₃ H ₇ -I) ₂ II

-CH OCH

V ₃

-CH (OC ₂ H ₅ ).

030065/0839

.30

Table II : (R ₁ - CH ₃ , R ₂ - CH ₃ , R ₄ - H, R ₅ - CH ₃ )

Verb. No.

^R 3 Phya. KonsC.

3-CH,

/ ^C 2 ^H 5 -CH OSO NHCH

96.5-97.5 °

-CH OCH ₁

Snp. 87-90-C

3-CH,

CH ₂ OC ₂ H ₅

-CH (OC ₃ H ₇ -I) ₂ II II

3-CH "

3-Cl

CH (OCH) -CH

-CH (OC ₃ H ₇ D ₂ -CH ₂ OCH ₃

-CH ₇ OCH

030065/0839

- 27 * -

.34

Table II :

CH ₃ , R _£ - CH ₃ , R ₄ - H, R ₅ - CH ₃ )

Verb. No.

Phys. "Const.

3-CH,

-CHO 26

1.5396

3-Cl -CH OCH

OeI

3-Cl

-CH (OCH ₃ ) CH ₂ OCH ₃

OeI

-CH ₂ OCH ₃

CH (OCH ₃ ) -CH ₂ OSO ,, NHCH ₃

OeI

-CH-OSO ₂ NHCH ₃

-ά

CH ₃ -CH OCH ₃

-CH (OC ₂ H.) -CH ₂ OC ₂ H ₅

OeI

3-CH-

-CH-OCH

M.p. 76-78 °

030065/0839

-ψ-

Table II

; (R ₁ - CH ₃ , R - CH ₃ , R ₄ «E, R ₅ * CH,)

Verb. No.

105

3-CE,

-C

-CH OCH

Phys. Const.

1 ³ L 5239

106

3-CH,

/ ^C 3 ^H 7 (n)

-CH ₂ OCH ₃

030065/0839

-.yr-

.33

Table III ; (R ₁ - CH, R ₃ »H, R» H, R.

Verb. No.

Cl

-CH (OCH, -CH ₂ OCH ₃

^C 2 ^H 5

Cl

-CH (OC ₂ H.) ₂ -CH OCH

^C 2 ^H 5

C ₂ H ₅

-CH (OCH ₃ ) ₂

Cl

^N 0

CH ₂ OCH ₃

C ₂ H ₅

-CH (OCH ₃ ) CH ₂ OCH ₃

^C 2 ^H 5

-CE -CH ₂ OCH ₃

Cl

Λ ^Η 5 -CH OCH

C "H

2 -CH ₂ OCH ₃

030065/0839

Table III :

CH ₃ , R ₃ - H, R ₄ - H, R ₅ - CH ₃ )

Verb.
No. * 2 Σ -CH OCH 117 OCH ₃ CH
_Q / TS
0—— · -CH ₂ OCH ₃ 118 Cl - ^ ₀ ) ' -CH ₂ OCH ₃ 119 OCH -CH (OCH ₃ ) ₂ -CH ₂ OCH 120 OCH <J

030065/0839

Table IV :

: (R ₁ - CH ₃ , R ₉ - CH ,, R ₃ - 3-CH ₃ , R ₄ «5-CH ₃ , R ₅ - CH ₃ )

Verb.
No. X ^: 2 ^H 5 •
• ^R 6 121 -CH (OCH ₃ ) ₂ -CH OCH 122 -CH (OCV ₂ -CH-OSO NHCH 123 -CH (OCH) -CH ₂ OC ₂ H ₅ 124 A, -CH OCH 125 -CH ₂ OC ₂ H ₅ 126 -CH OCH 127 -CH OSO NHCH 128 -CH.OC-H, 2 2 3

030065/0839

Formulation examples 3example 5 ι Dust

For the production of a) 5% and b) 2% dust the following substances are used:

a) 5 parts of active ingredient No. 1 - 128
95 parts of talc;

b) 2 parts of active ingredient No. 1 - 128

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 6 : Granules :

The following are used to produce a 5% granulate Substances used:

5 parts of active ingredient No. 2
0.25 part epoxidized vegetable oil
0.25 part of cetyl polyglycol ether,
3.50 parts of polyethylene glycol
91 parts of kaolin (particle size 0.3 to 0.8 mm).

The active ingredient is mixed with epoxidized vegetable oil and dissolved with 6 parts of acetone, then polyethylene glycol and Cetyl polyglycol ether added. The solution thus obtained is on Kaolin is sprayed on, and then the acetone is evaporated in vacuo. Such a microgranulate is advantageous for combating used by soil fungi.

030065/0839

Example 7 ί Spitzpüiver :

To produce a) 70% b) 40% c) and d) 25% e) the following ingredients are used:

a) 70 parts of active ingredient No. 1 - 128

5 parts of sodium dibutylnaphthylsulfonate, 3 parts of naphthalenesulfonic acids-phenolsulfonic acids-formaldehyde-

Condensate 3: 2: 1,
10 parts of kaolin
12 parts of champagne chalk;

b) 40 parts of active ingredient No. 1 - 128

5 parts of sodium lignin sulfonic acid, 1 part of sodium dibutylnaphthalenesulfonic acid, 54 parts of silica;

c) 25 parts of active ingredient No. 2

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 No. 42

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 kieselguhr,
46 parts of kaolin;

e) 10 parts of active ingredient No. 2

3 parts mixture of the sodium salts of saturated fatty alcohol

030065/0839

sulfates,

5 parts of naphthalenesulfonic acid / phenolic aldehyde condensate, 32 parts kaolin:

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. A wettable powder with excellent wettability is obtained and suspensions, which can be diluted with water to form suspensions of the desired concentration, and in particular for Let the foliar application use.

Example 8 : Emulsifiable concentrates:

For the production of a 25% emulsifiable concentrate the following substances are used:

25 parts of active ingredient No. 2 or another of the formula I 2.5 parts of epoxidized vegetable oil, 10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture,

5 parts of dimethylformamide,
57.5 parts of xylene.

Such concentrates can be diluted with water to produce emulsions of the desired application concentration that are particularly suitable for foliar application.

Biological examples Example 9: Action against Phytophthora infestans on tomato plants

a) Residual protective effect

Tomato plants were grown with one after 3 weeks Spray liquor (0.06% active ingredient) produced by spraying a wettable powder of the active ingredient. After 24 hours the treated Plants infected with a sporangia suspension of the fungus. the The fungal attack was assessed after the infected plants had been incubated for 5 days at 90-100% relative air

030085/0839

humidity and 2O ° C.

b) Residual curative effect

After 3 weeks of cultivation, tomato plants were infected with a sporangia suspension of the felt. After an incubation of 22 hours in a humidity chamber at 90-100% relative humidity and 20 ⁰ C, the infected plants are dried and prepared with a wettable powder of the active ingredient spray mixture (0.06% of active substance). After the spray coating had dried on, the treated plants were returned to the humid chamber. The fungal attack was assessed 5 days after infection.

c) Systemic effect

After 3 weeks of cultivation, a spray mixture prepared from wettable powder of the active ingredient was poured into tomato plants (0.006% active ingredient, based on the volume of the soil). Care was taken to ensure that the spray mixture did not come into contact with the above-ground parts of the plant. After 48 hours, the treated plants were infected with a sporangia suspension of the fungus. The fungal attack was assessed after the infected plants had been incubated for 5 days at 90-100% relative humidity and 20 ^° C.

Example 10 : Action against Plasmopara viticola on vines

In the 4-5 leaf stage, vine seedlings were sprayed with a spray mixture (0.06% active ingredient) prepared from wettable powder of the active ingredient. After 24 hours, the treated plants were infected with a sporangia suspension of the fungus. After incubation for 6 days at 95-100% relative humidity and 20 ^° C., the fungal attack was assessed.

030065/0839

- ho-

Example 11 : Action against Pythium debaryanum on beets Action after soil application

The mushroom was cultivated on carrot pulp nutrient solution and added to a mixture of soil and sand. The soil infected in this way was filled into flower pots and sown with sugar beet seeds. Immediately after sowing, the test preparations formulated as wettable powders were poured over the soil as aqueous suspensions (20 ppm of active ingredient based on the volume of the soil). The pots on eye provides for 2-3 weeks in a greenhouse at about 20 ⁰ G. The earth was always kept evenly moist by lightly showering over it.

In the evaluation of the tests, the emergence of the sugar beet plants and the proportion of healthy and diseased plants is determined.

Effect after pickling application

The fungus was cultivated on carrot pulp nutrient solution and added to an earth-sand mixture. The soil infected in this way was filled into soil bowls and sown with sugar beet seeds had been pickled with the test preparations formulated as pickling powder (0.06% active ingredient).

The sown pots were placed for 2-3 weeks in a greenhouse at about 2O ⁰ C. The earth was always kept evenly moist by lightly showering over it. The run-out of the sugar beet plants was determined during the evaluation.

Example 12 ; Effect against Venturia inaequalis on apples Residual protective effect

Apple seedlings with about 5 developed leaves were mixed with a spray mixture prepared from a wettable powder of the active ingredient (0.06% active substance) sprayed. After 24 hours, the treated plants were treated with a conidia suspension of the fungus infected. The plants were then grown for 5 days at 90-100%

030065/0839

-yr-

• 4 *.

Incubated relative humidity and placed in a greenhouse at 20-24 ⁰ C for a further 10 days. The eschar infestation was assessed 15 days after infection.

Example 13 : Action against Cercoapora arachidicola on peanuts Residual protactive action

10-15 cm high peanut plants were sprayed with a spray mixture (0.023 active substance) prepared from a wettable powder of the active substance and infected 48 hours later with a conidia suspension of the fungus. The infected plants were incubated for hours at about 21 ^° C. and high atmospheric humidity and then placed in a greenhouse until the typical leaf spots appeared. The fungicidal effect was assessed 12 days after infection based on the number and size of the spots that occurred.

In the experiments of Examples 9, 10, 11, 12 and 13, compounds of the formula I showed a strong plant fungicidal action. (Disease incidence below 25%). Complete disease prevention was achieved with the following preparations. Example 9: Comp. No. 2, 3, 10, 42, 49, 65; Example 10: Comp. No. 2, 3, 42; Example 11: Comp. No. 2, 10, 65; Example 12: Verb. No. 2.

030065/0839

Claims (12)

3025634 claims 1. "j compounds of formula I < Y ^M ' 2 O wherein R ₁ and R "independently of one another are C -C -alkyl, C -C -alkoxy or halogen, R, hydrogen, C -C -alkyl or halogen, R waterj 13 4 Substance or methyl, where the sum of the carbon atoms in R ₁ , R_, R_ and R does not exceed the number 6 and R- is hydrogen or C -C alkyl, R-ß- (C -C) -alkoxyethyl or a 2-furyl, 2-tetrahydrofuryl group or -CH.Z which is optionally substituted by halogen, where Z is one of the following groups:
a) -0-R ₇ , -SR ₇ b) -NH- O - ₂₁₀ d) -OgR _n e) 1,2-pyrazole, 1,3 imidazole, 1,2,4-triazole including its salts and metal complexes, and R_ for a C -Cg-alkyl, _{C -C -alkenyl or C -C -alkynyl group, optionally substituted by CC 2 -AIkOXy, R 3} for hydrogen or C -C -alkyl, R "for C -C - Alkyl or a phenyl group which is optionally substituted by halogen or methyl and R for C ₁ -C 4 -alkyl is mono- or di- (C -C) -alkylamine, R _{11 is} for a C -C -alkyl group which is optionally substituted by C -C -alkoxy and X for 030065/0839 -CHO or -CH ^, in which Y and Y _{9 are} C -C alkyl or OY ₂ together, optionally one or more times, by C.-C-alkyl form substituted C -C -alkylene bridge or together optionally form a 1,2-cyclohexane ring. 2. Compounds of formula I according to claim 1, wherein R-CH ₃ , -OCH ₃ , halogen R »hydrogen, CH ₃ , halogen R, ■ hydrogen, CH ₃ R ₅ - methyl χ - CHO, ^OT 2 Y- and Y _{2 represent} C 1 -C 4 -alkyl or together are mono- or _{polysubstituted by C, -C 3} -alkyl or unsubstituted C 1 -C 4 -alkylene bridges or together form a 1,2-cyclohexane ring. R ₆ ■ 2-furyl, 2-tetrahydrofury1, ß- (C -C -alkoxy) -ethyl, -CH-Z, where Z means: a) -OR ₇ , -SR ₇ b) -ΝΗ-Ϊ * 9 ^C) - ° ^S0 2 ^R 10 d) 1,2-pyrazole, 1,3-iidazole, 1,2,4-triazole with inclusion their salts and metal complexes. R ₇ «C ₁ -C ₂ alkyl, C ₃ -C ₄ alkenyl optionally substituted by C 1 -C 2 alkoxy, 030065/0839 R ■ C -C -alkyl, methylamine. 3. Compounds of formula I according to claim 1, wherein R ₁ - CH ₃ , OCH ₃ R ₂ «CH ₃ , chlorine R_» is hydrogen R, »hydrogen R ₅ - CH ₃ X - -CH OY ₂ Y 1 and Y _{2 represent} C.-C.-alkyl or together form a mono- or polysubstituted or unsubstituted alkylene bridge by C.-C.-alkyl. 2-furyl, 2-tetrahydrofuryl, -CH-CH-OCH ₃ , where Z means: a) -OR ₇ (R ₇ -C _{1 -C} b) -NH- / ^{8 (R} 3 - ^ ₉ (R ₉ - c) -OSO ₂ R ₁₀ (R ₁₀ - C ₁ -C ₂ -AlCyI, methylamine) d) 1,2,4-triazole. 4. The compound 2- [N- (2,6-dimethylphenyl) -N-methoxyacetyl amino] propionaldehyde dimethylacetal according to claim 5. The compound 2- [N- (2,6-dimethylphenyl) -N-methoxyacetyl amino] acetaldehyde dimethyl acetal according to claim 030065/0839 6. Agent for combating microorganisms, characterized in that that there is as at least one active component a compound of the formula I according to claim 1 together with or with contains several suitable carriers. 7. Agent for combating microorganisms according to claim 6, containing at least one compound of the formula I according to claim 2. 8. Agent for combating microorganisms according to claim 6, containing at least one compound of the formula I according to claim 3. 9. Agent for combating microorganisms according to claim 6, containing 2- [N- (2,6-dimethylphenyl) -iI-methoxyacetyl-amino] -propionaldehyde dimethylacetal. 10. Agent for combating microorganisms according to claim 6, containing 2- [N- (2,6-dimethylphenyl) -N-methoxyacetylamino] acetaldehyde dimethylacetal. 11. Use of a compound according to claim 1 for combating and / or prevention of infestation by phytopathogenic microorganisms. 12. Use of compounds according to any one of claims 2 to for controlling and / or preventing infestation by phytopathogens Microorganisms. FO 7.5 PK / rz * 030065/0839