CH639940A5 - Substituted N-alkoxycarbonylethyl-N-acylanilines, microbicides containing them, and process for the preparation of the compounds - Google Patents

Description

The present invention relates to compounds of the formula I.

chq l 3

40

_ n ch-coor,

c-r, 11 "0

(I)

45

wherein

Rx and R2 independently of one another are C! -C3-alkyl, Ci-Cs-alkoxy or halogen,

R3 is hydrogen, C 1 -C 3 -alkyl or halogen, R4 is hydrogen or methyl,

50 where the total number of carbon atoms in R1; R2, R3 and R4 do not exceed 6.

Rs is Ci-C4-alkyl which is substituted by one of the groups listed below

- C3-C7-55 cycloalkyl optionally substituted by Q-CValkyl

- one to five halogen atoms

- C6-C10-aryl optionally substituted by halogen, cyano, nitro, Cj-Cä-alkyl, Cj-C3-alkoxy or C1-C2-haloalkyl, '

60 _ If necessary C1-C4-Alk-oxy substituted by halogen

- C1-C3 alkoxy- (C2-C4) alkoxy

- Cj-C4-AlkyIthio

- Cj-C4-Alkylsulfinyl 65 - Ci-C4-AlkyIsuIfonyl

- Di- (Ci-C4) -alkylamino or

O II

- -O-C-Y

639 940

where Y is C1-C4-alkyl substituted by halogen or C1-C4-alkoxy; C2-C4-alkenyl optionally substituted by halogen; C2-C4 alkynyl; phenyl or benzyl optionally substituted by halogen, Cj-Cj-alkyl, Q-Q-alkoxy, cyano, nitro or Ci-C2-haloalkyl; or a halogen-substituted, saturated or unsaturated five- or six-membered heterocyclic radical with up to two heteroatoms,

Re optionally 2-furyl or 2-tetrahydrofuryl substituted by halogen,

- ß- (Ci-C4) -alkoxyethyl or

- means the group CH2Z, where

Z for one of groups a) -X-R7

b) -NH-N (R8) (R9)

c) -OSO2R10

d) -OCR! j stands and

II

O

X oxygen or sulfur,

R7 Ci-C6-alkyl, C3-C4-alkenyl or C3-C4-alkynyl optionally substituted by Cj-Q-alkoxy, R8 hydrogen or Q-Q-alkyl,

R9 Q-Q-alkyl or phenyl optionally substituted by halogen or methyl,

R10 is C, -C4-alkyl or mono- or di- (C, -C3) -alkylamine and s Ri i are Q-Ca-alkyl optionally substituted by Q-Q-alkoxy.

Under alkyl or as alkyl part of another substituent, depending on the number of carbon atoms indicated, the following groups are to be understood: methyl, ethyl, propyl, butyl, pentyl, io hexyl, and their isomers, such as. B. iso-propyl, iso-butyl. sec-butyl, tert-butyl, iso-pentyl, etc.

Alkenyl stands for example for allyl, 2-butenyl, etc.

Alkynyl means above all propargyl.

C3-C7-cycloalkyl means cyclopropyl, cyclobutyl, 15 cyclopentyl, cyclohexyl and cycloheptyl.

Aryl primarily means phenyl and naphthyl, halogen stands for fluorine, chlorine, bromine or iodine.

The compounds of formula I can be used in a number of ways, e.g. listed below, 2o. In formulas II to XXIII, R to R! ! and X has the meanings given under formula I, shark stands for halogen, preferably chlorine or bromine and M stands for hydrogen or a metal, preferably alkali or alkaline earth metal.

A.

CH0 I ^

NHCHCOOR,

+ H00CR,

Acylation

(I)

(II)

(III)

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

In some cases, the use of acid-binding agents or condensing 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, bicarbonates, carbonates or hydrides of alkali and alkaline earth metals,

O

like sodium acetate. The starting product II can also serve as the acid-binding agent 40.

Production process A can also be carried out without acid-binding agents, in some cases the passage of nitrogen to expel the hydrogen halide formed is indicated. In other cases, the addition of dimethylformamide as a reaction catalyst is very advantageous.

B. If Re means -CH2OSO2Ri0 or -CH2OCRj 1: 50

CHCOOK,

C-CHo0H

II *

0

Hal-S02R10 or

0

Hal-CR

XI

Hal-R.

(V)

(VI)

(VII)

Cl)

A salt, in particular an alkali or an acid-binding agent, as described under A, salt of the compound of the formula IV, is advantageously used. carried out.

This procedure is carried out in the presence, if necessary

639 940 4

C. If Re has a meaning other than -CH2NH-N (R8 (R9):

ch,

i 3

+ halchcoor,

* C1)

(viii)

(IX)

Here, the compound of the formula VIII is first converted into an salt using an acid-binding agent analogous to process A, preferably butyl lithium or Na hydride, with the addition of catalytic amounts of alkali iodide, or the process is carried out in the presence.

?

D. If R6 for -CH2XR7, -CH2COR! t or -CH2NH-N (R8) (R9) stands for:

CHo 'i J

CHCOOR.

C-CH0Hal «*

0

0

MOCRlx (XI)

MXR-

(XII).

nh2n (rg) (r9)

t <X)

(X)

If M = hydrogen, use of a salt-forming agent is appropriate, e.g. an oxide, hydroxide, hydride, etc. of alkali or alkaline earth metals. If starting materials of the formula XIII are used, the end product is obtained as the hydrohalide.

(XIII)

With mild bases, the free hydrazino compound can be obtained at room temperature or at a slightly elevated temperature. For this, e.g. Alkali carbonates.

40

E. If R6 is β- (C1-C4) alkoxyethyl:

R,

ch,

I 3

chcoor,

CCH «CH« Hal s 2 2

(XIV)

The procedure is analogous to method D. F. If R6 is ß- (C, -C4) alkoxyethyl:

r3

ch3

chcoor.

(XVI)

+ M- (C1-C ^) alkoxy

(XV) '

CO

+ M (C ^ -C ^) alkoxy (XV)

Ct)

639 940

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

G.

+ listen,

Esterification

-> CD

(XVII)

In this process, an esterification catalyst such as e.g. Mineral acid, chlorosulfonic acid, tolosulfonic acid, acid chlorides such as thionyl chloride, acetyl chloride, phosphorus oxychloride, oxalyl chloride, 20

(XVIII)

Boron trifluoride etherate etc. used. It is also possible to work with an excess of HOR5. In many cases the azeotropic esterification method is appropriate.

H.

ch3

chcoor '

+ (XVIII) transesterification £ l)>

(XIX)

This reaction is catalytically influenced by acids and bases. In order to shift the balance as far as possible in the desired direction, an excess of HOR5 is used. The meanings of R 'and R5 are different.

R 'is predominantly lower alkyl such as methyl or ethyl.

40

CH3

CHCOOMe

I.

+ Hal'R.

* 00

(XX)

(XXI)

Here Me means an alkali, alkaline earth, lead or silver metal atom, Hai 'is halogen, preferably chlorine, bromine or iodine.

j.

R.

CHCOHal

+ '(XVIII)'

■> (1)

639 940 6

This also works with an acid-binding agent.

K.

3 rows,

n

R,

CH.

'-.cooh

■ c-r, h 1 0

+ r5ooc-r "

(I)

(XVII)

(XXIII)

R "here means lower alkyl, preferably methyl.

In principle, solvents can be used in all processes which are inert to the reactants.

Examples of such solvents are:

Aliphatic hydrocarbons such as benzene, toluene, xylene, petroleum ether; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform; Ether and ethereal compounds such as dialkyl ether, di-oxane, tetrahydrofuran; Nitriles such as acetonitrile; N, N-di-alkylated amides such as dimethylformamide; Dimethyl sulfoxide, ketones such as methyl ethyl ketone and mixtures of such solvents with one another.

All starting materials are manufactured according to known methods.

See J. Org. Che. 30,4101 (1965), Tetrahedron 1967,487, Tetrahedron 1967,493, DE-OS 2 417 781, DE-OS 2 311 897, US-PS 3,780,090, US-PS 3 598 859, GB-PS 1 438 311.

Manufacturing variant G is also part of the invention.

Some of the starting materials are new and also belong to the invention. They show a certain fungicidal effect.

The compounds of formula I have an asymmetric carbon atom in the side chain adjacent to COORs and can be cleaved into optical antipodes in the usual way; so e.g. by fractional crystallization of the salts of II with an optically active acid and further reaction of the optically pure compounds of II to I or z. B. by fractional crystallization of XVII with an optically active base and further reaction of the optically pure compounds from XVII to I. The antipodes I have different microbicidal effects.

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

Regardless of the optical isomerism mentioned, an antropisomerism around the phenyl N <is usually

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

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

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

The active substance content in commercially available agents is between 0.1 and 90%.

For application, the compounds of the formula I can be present in the following working up forms (the 20 percentages by weight in brackets representing advantageous amounts of active ingredient):

Fixed processing forms:

Dusts and grit (up to 10%) granules, 25 coating granules, impregnation granules and homogeneous granules, pellets (grains) (1 to 80%);

Liquid processing forms:

a) Active ingredient concentrates dispersible in water:

30 wettable powders and pastes (25 to 90% in retail packs, 0.01 to 15% in ready-to-use solutions); Emulsion and solution concentrates (10 to 50%; 0.01 to 15% in ready-to-use solution);

b) solutions (0.1 to 20%); Aerosols

35 Such means also belong to the invention.

It has surprisingly been found that compounds with the structure of the formula I have a microbicide spectrum which is very favorable for practical needs for the protection of crop plants. In the context of the present invention, crop plants are, for example, cereals, maize, rice, vegetables, sugar beets, soybeans, peanuts, fruit trees, ornamental plants, but above all vines, hops, cucumber plants (cucumbers, pumpkins, melons), Solanaceae such as potatoes, tobacco and tomatoes and also banana, cocoa and natural 45 rubber plants.

With the active ingredients of the formula I, the fungi that occur on plants or parts of plants (fruits, flowers, leaves, stems, tubers, roots) of these and related crops can be contained or destroyed, where such fungi are spared in later growing plant parts. The active substances are active against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Erysiphaceae, Sclerotinia, Helminthosporium); Basidiomycetes such as especially Rostpil-55 ze, Rhizoctonia; Fungi imperfecti (e.g. Moniliales, Piricula-ria); then especially against the Oomycetes belonging to the class of Phycomy-cetes such as Phytophthora, Perono-spora, Pseudoperonospora, Pythium or Plasmopara. In addition, the compounds of the formula I have a systemic action. 60 They can also be used as dressing agents for the treatment of seeds (fruits, tubers, grains) and plant cuttings to protect against fungal infections and against phytopathogenic fungi occurring in the soil.

The invention thus further relates to the use of the 65 compounds of the formula I for combating phytopathogenic microorganisms.

The following types of substituents or combinations thereof are preferred.

7

639 940

For Rj: a) Ci-C, -alkyl or Ci-C2-alkoxy b) CH3, 0CH3 For R2: a) CH3, OCH3, halogen b) CH3, chlorine For R3: a) hydrogen, CH3, halogen b) hydrogen With R4: hydrogen With R5: a) Cj-Q-alkyl which is substituted by one of the groups listed below:

- C3-C7-cycloalkyl optionally substituted by Ci-C3-alkyl

- one to five halogen atoms

- Phenyl optionally substituted by halogen, cyano, nitro, Q-Ca-alkyl, Q-Q-alkoxy, Q-Q-haloalkyl

- Cj-Q-alkoxy optionally substituted by halogen

- C1-C3 alkoxy- (C2-C4) alkoxy

- C! -C4 alkylthio

- C1-C4-Alkylsulfmyl ^

- Cj-C4-Alkylsulfonyl ||

- Di- (C! -C4) alkylamino or -OCY b) Q-Q-alkyl which is substituted by one of the groups listed below:

- C3-C7 cycloalkyl

- one to three halogen atoms

- Phenyl optionally substituted by halogen, C, -C3-alkyl

- C1-C4-alkoxy optionally substituted by halogen

- C1-C3 alkoxy- (C2-C4) alkoxy

- Cj-Q-alkylthio

- C1-C4-alkylsulfinyl

- Cj-C4-alkylsulfonyl 9

- Di- (C1-C4) alkylamino or -OCY For R6: a) -2-furyl, 2-tetrahydrofuryl

-ß- (Cj-C2-alkoxy) ethyl

-CH2XR7 (X = oxygen or sulfur)

-CH2NH-N (R8) (R9)

-ch2oso2 r10

b) -2-furyl, 2-tetrahydrofuryl

-ch2ch2och3 -ch2or7

-CH2NH-N (R8) (R9)

-CH2OSO2 (R10)

In R7: a) Q-Q-alkyl, C3-C4-alkenyl or C3-C4-alkynyl optionally substituted by Cj-Q-alkoxy b) C1-C3-alkyl

At R8 and

R9: a) Cj-Cj-alkyl b) Cj-Cz-alkyl at R10: Q-Q-alkyl, methylamine.

This results in e.g. the following preferred groups Rj, R2, R3, R4 and R6 as defined under formula I R5 = a) Q-Q-alkyl which is substituted by one of the groups listed below:

- C3-C7-cycloalkyl optionally substituted by Ci ~ C3-alkyl

- one to five halogen atoms

- Phenyl optionally substituted by halogen, cyano, nitro, Cj-C3-alkyl, C! -C3-alkoxy, Q-Q.-haloalkyl

- optionally substituted by halogen-substituted Q-Q-alkoxy

- C! -C3 alkoxy- (C2-C4) alkoxy

- C, -C4 alkylthio

- C1-C4-alkylsulfinyl q

C1-C4-alkylsulfonyl y

- Di- (C: -C4) alkylamino or -OCY or

Ri = Ci-C2-alkyl, C, -C2-alkoxy R2 = CH3, -OCH3, halogen R3 = hydrogen, CH3, halogen R4 = hydrogen, CH3

R5 = b) Cj-Cralkyl which is substituted by one of the groups listed below:

- C3-C7 cycloalkyl

- one to three halogen atoms

- Phenyl optionally substituted by halogen, C1-C3-alkyl

- Cj-C4-alkoxy optionally substituted by halogen

- C1-C3 alkoxy- (C2-C4) alkoxy

Ci-C4-alkylthio

Ci-C4-alkylsulfinyl q

- C, -C4-Alkylsulfonyl ||

- Di- (C! -C4) alkylamino or -OCY R6 = -2-furyl, 2-tetrahydrofuryl

-ß- (C1-C2-alkoxy) ethyl

-ch2z,

with a meaning of z from a) -XR7 (X = oxygen or sulfur)

b) -NH-NCT

^ r9

c) -OSO2R10, where

R7 = C! -C4-alkyl optionally substituted by C! -C2-alkoxy, C3-C4-alkenyl, C3-C4-alkynyl

R8 and

R9 = C1-C3 alkyl

R10 = C1-C2-alkyl or monomethylamine, or

Rj = CH3, OCH3

R2 = CH3, chlorine

R3 = hydrogen

R4 = hydrogen

R5 = Ci-C4-alkyl which is substituted by one of the groups listed below:

- C3-C7 cycloalkyl

- one to three halogen atoms

- Phenyl optionally substituted by halogen, C 1 -C 3 alkyl

- Optionally substituted by halogen C! -C2 alkoxy

- CH30-C2-alkoxy

C1-C2 alkylthio

- C1-C2-alkylsulfinyl

Ci-C2-alkylsulfonyl

- Di- (C1-C2-alkylamino) or

O

- -o4y, where Y is C1-C2-alkyl substituted by halogen or C1-C2-alkoxy; C2-C4-alkenyl optionally substituted by halogen; C2-C4 alkynyl; phenyl optionally substituted by halogen, C1-C3-alkyl, Cî-Ca alkoxy or an optionally substituted by halogen saturated or unsaturated five- or six-membered heterocyclic radical having a hetero atom

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

639940

8th

Ra = -2-furyl, 2-tetrahydrofuryl -CH2CH2OCH3

-ch2z

Z = a) OR7, where R7 = Q-Cj-alkyl

/ RS

b) -NH-N, where R8 and R9 =

Rg Cl-C2-alkyl are c) -OSO2Ri0 where R10 = C1-C2-alkyl, monomethylamine.

The following examples serve to explain the invention in more detail without restricting it. The temperatures are given in degrees Celsius. Percentages and parts relate to weight. Unless otherwise noted, the term racemic mixture is always used when referring to an active ingredient of the formula I.

Production of

Production Examples Example 1

CH ~ 0

i J H

15

ch-coch2ch2och2ch2och3

ccho0ch ~

N Y

0

N- (1 '-2- [2-methoxy-ethoxy] ethoxycarbonyl-ethyl) -

N-methoxyacetyl-2,6-dimethylaniline 26.5 g of N- (r-carboxyethyl) -N-methoxyacetyl-dimethyl-aniline, 21 g of diethylene glycol monomethyl ether, 2 g of conc. Sulfuric acid and 150 ml of toluene were heated under reflux for 4 hours, the water formed being separated off using a water separator. After cooling, the mixture was diluted with ice water, the organic phase was separated off, washed twice with dilute sodium carbonate solution and twice with water, dried over sodium sulfate, filtered and the solvent was evaporated off. The crude product was distilled in a high vacuum;

Bp 168-17070.05 mbar.

Manufacture of CH

ch-cooch2ch2cl cch0ocho m ^ o 0

N- (1 '-ß-chloroethoxycarbonyl-ethyl) -N-methoxyacetyl-

2,6-dimethylaniline 39.7 g of N- (l'-carboxyethyl) -N-methoxyacetyl-2,6-dimethylaniline, 40 g of 2-chloroethanol, 1 g of p-toluenesulfonic acid and 400 ml of carbon tetrachloride were refluxed for 20 hours heated, the resulting water was separated with a water separator. The solvent and excess 2-chloroethanol were evaporated in vacuo and the oily residue was crystallized by rubbing with diethyl ether. After recrystallization from hexane, the white crystals melt between 86-89 °.

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

Formulation examples Example 3

Dusts: The following substances are used to produce a) 5% and b) 2% dusts:

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

b) 2 parts of active ingredient

1 part of highly disperse silica,

97 parts talc;

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

Example 4

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

5 parts of active ingredient 0.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether,

3.50 parts of polyethylene glycol 30 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. The solution thus obtained is sprayed onto kaolin, and then the acetone is evaporated in vacuo. Such microgranules are advantageously used to control soil fungi.

40 Example 5

Spray powder: The following ingredients are used to produce a) 70% b) 40% c) and d) 25% e) 10% spray powder:

a) 70 parts of active ingredient 45 5 parts of sodium dibutylnaphthyl sulfonate,

3 parts of naphthalenesulfonic acids-phenolsulfonic acids-

Formaldehyde condensate 3: 2: 1,

10 parts kaolin 12 parts champagne chalk;

so b) 40 parts of active ingredient

5 parts of sodium lignosulfonic acid,

1 part of dibutylnaphthalenesulfonic acid sodium salt, 54 parts of silica;

c) 25 parts of active ingredient

55 4.5 parts of calcium lignin sulfonate,

1.9 parts champagne chalk / hydroxyethyl cellulose

Mixture (1: 1),

1.5 parts of sodium dibutyl naphthalenesulfonate,

19.5 parts of silica,

60 19.5 parts of champagne chalk,

28.1 parts kaolin;

d) 25 parts of active ingredient

2.5 parts isooctylphenoxy polyoxyethylene ethanol, 1.7 parts champagne chalk / hydroxyethyl cellulose 65 mixture (1: 1),

8.3 parts of sodium aluminum silicate,

16.5 parts of diatomaceous earth,

46 parts of kaolin;

9

639940

Table I (R! In 2-position)

Verb.Rj R2 R3 R4 Rs R6 Physical

No constant

1

ch3

ch3

H

H

2nd

ch3

ch3

h h

3rd

ch3

ch3

h h

4th

ch3

ch3

h h

5

ch3

ch3

h h

6

ch3

ch3

h h

7

ch3

ch3

h h

8th

ch3

ch3

h h

9

ch3

ch3

h h

10th

ch3

ch3

h h

11

ch3

ch3

h h

12

ch3

ch3

h h

13

ch3

ch3

h h

14

ch3

ch3

h h

15

ch3

ch3

3-c1

H

16

ch3

ch3

h h

17th

ch3

ch3

h h

18th

ch3

ch3

h h

19th

ch3

ch3

h h

20th

ch3

ch3

3-ch3

H

21st

ch3

ch3

h h

22

ch3

ch3

h h

23

ch3

ch3

3-c1

H

24th

ch3

ch3

h h

25th

ch3

ch3

3-ch3

H

26

ch3

ch3

h h

27th

ch3

ch3

h h

28

ch3

ch3

h h

29

ch3

ch3

h h

30th

ch3

ch3

h h

31

ch3

ch3

h h

32

ch3

ch3

h h

33

ch3

ch3

h h

34

ch3

ch3

h h

35

ch3

ch3

h h

-ch2ch2och3

-ch2ch2och2ch2ci -ch2ch2och2ch2och3

-ch2ch2so2ch3 -ch2ch2och3

-ch2ch2och3

-ch2ch2och2ch2oc2h5 -ch2ch2och3

-ch2ch2och2ch2och3

-ch2ch2n (ch3) 2

-ch2ch2och3

o il

-ch2ch2occh2oc2h5 -ch2ch2n (c2hs) 2

-ch2ch2n (ch3) 2

-ch2ch2och3 ch3

I.

-chch2och3

-ch2ch2och3

-ch2ch2ch2n (ch3) 2

-ch2ch2sch3

-ch2ch2och3

ch3

[

-chch2och3

-ch2ch2och3 -ch2ch2och2ch2och3 -ch2ch2sch3 -ch2ch2och2ch2och3 -ch2ch2soc2h5 -ch2ch2och3 o

U

-ch2ch2oc.

-ch2ch2so2ch3 ch3

I.

-chch2och3

ch3

I.

-chch2och3

-ch2ch2so2ch3

"" CH2CH2

- <3>

-ch2ch2c1

-ch2ch2och3

-ch2och3

-ch2och3 -ch2och3

-ch2nhn (ch3) 2 -ch2nhnh- ^ ö ^

-ch, och3

-ch2nhn (ch3),

-U

-ch2och3

-ch2oso2ch3

-ch, oc2h5 -ch2och3

ju

-ch2oc2h5

4ÓÌ

-ch2sch3 -ch2och3 -ch2oc2h5

-O

-ch2och3

-ch2oso2c2h5

-ch2och3

-ch2och3

-ch2oc2h5

-ch2och3

-ch2och2c = ch

-loil

-0 '

-ch2och3

-ch2och2ch = ch2

-ch2oc2h5 -ch2oso2c2h5

-ch2och3 -ch2och3

Bp 150-152 ° c / 0.2 mbar

Bp 168-170 ° c / 0.05 mbar

Bp 170-175 ° c / 0.1 mbar

Oil oil

Oil oil

Mp 86-89 ° C

639 940 10

Table I (continued)

Verb.R, R, R, Rt R5 R (1 physical

No constant

36

ch3

ch3

H

37

ch3

ch3

H

38

ch3

ch3

H

39

ch3

ch3

H

40

ch3

ch3

H

41

ch3

ch3

H

42

ch3

ch3

H

43

ch3

ch3

3-c1

44

ch3

ch3

H

45

ch3

ch3

H

46

ch3

ch3

H

47

ch3

ch3

H

48

ch3

ch3

H

49

ch3

ch3

H

50

ch3

ch3

3-ch;

51

ch3

ch3

H

52

ch3

ch3

3-c1

53

ch3

ch3

H

54

ch3

ch3

H

55

ch3

ch3

H

56

ch3

ch3

3-ch

57

ch3

ch3

H

58

ch3

ch3

3-ch;

59

ch3

ch3

H

60

ch3

c2h5

H

61

ch3

Cl h

62

ch3

ch3

H

63

ch3

ch3

H

64

ch3

ch3

H

65

ch3

ch3

H

66

ch3

ch3

H

67

ch3

ch3

h h h h h h h

H H

H

h h h h

h h h h h h

h h h

5-CH3

h h h h h h

h h h

-ch2ch2f

-ch2ch2och3

-ch2ch2n (ch3) 2

0

1

-ch2ch2occh2cl -ch2ch2och2ch2och3

o il

-ch2ch2ocçh2

och3

-ch2ch2och3 -ch2ch2och3

O

II

-ch2ch2oc-ccl = cc12

ch3

I.

-chch2och3

-ch2ch2och2ch2och3 -ch2ch2f ch3

I.

-chch2och3 0

-ch, och3

-ch2och2ch = ch2

-ch2oc2h5

s-g

-ch2och3 JQL Br

-ch2och.

-ch2ch2oc

-ch2ch2och3 ch3

I.

-chch2och3

-ch2ch2och2ch2och3

-ch2ch2och3

-ch2ch2och3

-ch2ch2so2ch3

-ch2ch2och2ch2och3

-ch2ch2och3

-ch2ch2och3

ch3

I.

-CHCH2OCH3

-ch2ch2och2ch2och3 -ch2ch2och3

O

II

-CH2CH2OCCH2OC2H5

-ch2ch2och2ch2och3

-ch2ch2och2ch2ci o

II

-CH2CH2OCCH2CH2OCH3

-ch2ch2o-c-QP

-CH2CH2Br

-ch2oso2nhch3 -ch2och3

-ch2och3

-CH2OC3H7-i -CH2OC2H5

-ch2och2ch = ch2

-ch2oso2nhch3

-ch2och3 -ch2oc2h5

-igLBr

-CH2oc2hs

-ch2ch2och3

O

II

-ch2occh3

-ch2och3

-CH2OC3H7-i

-ch2och3

O

II

-ch2occh3

-ch2och3 -ch2och3

-ch2och3

-ch2oc2h5

-ch2och3 -ch2och,

01

Mp 91-93 ° C

11

639 940

Table i (continued)

Verb.

R,

R2

Ri

R4

Rs

R "

Physical

No.

constant

68

ch3

cl h

H

-ch2ch2och2ch2och3

-ch2och3

69

ch3

ch3

h h

-ch2ch2och2ch2oc2h5

70

ch3

ch3

h h

-ch2ch2och3

71

ch3

ch3

3-ch3

H

-ch2ch2so2ch3

-ch2och3

72

ch3

ch3

h h -

-CH2CH2OÔ-Cgl

0

-ch2och3

J ^ jLßr

73

ch3

ch3

h h -

'Ch2ch2oc -Iq jl-Br

74

ch3

cl h

H

-ch2ch2ci

-ch2och3

75

ch3

ch3

h h

-ch2ch2och3

-ch2oc2h5

76

ch3

ch3

h h

-ch2ch2och2ch2ci ch3

1 year

77

ch3

och3

h h

-chch2och3

-ch2och3

78

ch3

Cl h

H

-ch2ch2och3

-ch2oc2h5

oil

79

ch3

och3

h h

-ch2ch2och3

-ch2och3

80

ch3

ch3

h h

-ch2ch2n (ch3) 2

JLHJ

-ch2och3

81

ch3

ch3

3-ch3

5-ch3

-ch2ch2och2ch2och3

82

ch3

ch3

3-ch3

H

-ch2ch2och3 ch3

1 year

-ch2och3

83

ch3

ch3

3-ch3

5-ch3

-chch2och3

-ch2och3

ch,

84

ch3

ch3

h h

-chch2och3

85

ch3

ch3

3-ch3

5-ch3

-ch2ch2so2ch3

86

ch3

och3

h h

-ch2ch2och2ch2och

87

ch3

c2h5

h h

-ch2ch2och3

88

ch3

ch3

h h

-ch2ch2j

89

ch3

ch3

h h

-ch2ch2ci

90

ch3

ch3

h h

-ch2ch2ci

-CH2OCH3

-ch2och3 -ch2och3 -ch2och3

-CH2OC3H7i

-ch2occh3

II

O

91

ch3

ch3

3-ch3

5-ch3

-ch (ch2f) 2

-ch2och3

92

ch3

och3

h h

-ch2ch2c1

-ch2och3

93

ch3

ch3

h h

-ch (ch2c1) 2

-ch2och3

94

ch3

ch3

3-ch3

5-ch3

-ch2ch2ci

-ch2och3

95

ch3

ch3

h h

-ch2ch2ci

-ch2oso2nh-ch3

96

ch3

ch3

h h

-ch (ch2f) 2

-ch2och3

97

ch3

ch3

h h

-ch2ch2f

-CH2OC3H7i

98

ch3

c2h5

h h

-ch2ch2ci

-ch2och3

99

ch3

ch3

h h

-ch2chchch3 21 l Cl Ci

-ch2och3

100

ch3

Cl h

H

-ch (ch2c1) 2

-ch2och3

101

ch3

ch3

3-c1

H

-ch2ch2ci

-ch2oc2h5

102

ch3

ch3

h h

-ch2ch2f

-ch2ch2och3

103

ch3

ch3

3-c1

H

-ch2ch2ci

-ch2och3

104

ch3

ch3

h h

-ch2ch2ci

-ch2oc2hs

105

ch3

Cl h

H

-ch2ch2ci

-ch, oc2h5

106

ch3

ch3

h h

-ch (ch2c1) 2

-ch2oc2h5

107

ch3

ch3

3-ch3

H

-ch2ch2ci

M

108

ch3

ch3

h h

-ch2ch2ci

11

Mp 60.5-62 ° C

Oil

Oil

639 940

12

Table I (continued)

Verb.No.

R>

Ra

R4

Rs

Rd

Physical constant

109

ch3

ch3

h h

-ch (ch2c1) 2

-ch2oso2ch3

110

ch3

ch3

h h

-ch2ch2ci

-ch2sch3

111

ch3

ch3

h h

-ch2ch2ci

-ch2oso2ch3

112

ch3

ch3

h h

-ch2ch2ci jP

113

ch3

ch3

h h

-ch (ch2f) 2

114

ch3

ch3

3-c1

H

-ch2ch2f

-ch, och3

115

ch3

ch3

3-ch3

H

-ch2ch2ci

-CH2oc2hs

116

ch3

ch3

h h

-ch2ch2ci

-ch2nh-n (ch3) 2

resin

117

ch3

ch3

h h

-ch2ch2ci

-ch2nh-nh- ^ o

>

118

ch3

ch3

h h

-ch (ch2f) 2

-ch2nhn (ch3) 2

119

ch3

ch3

H

H

-ch2ch2ci

JTT

e) 10 parts of active ingredient

3 parts mixture of saturated sodium salts

Fatty alcohol sulfates,

5 parts of naphthalenesulfonic acid / formaldehyde condensate,

82 parts of kaolin;

The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. This gives wettable powders of excellent wettability and suspension which can be diluted with water to form suspensions of the desired concentration and can be used in particular for leaf application.

Example 6

Emulsifiable concentrates: The following substances are used to produce a 25% emulsifiable concentrate:

25 parts of active ingredient 2.5 parts of epoxidized vegetable oil,

10 parts of an alkyl aryl sulfonate / fatty alcohol polyglycol

colether mixture,

5 parts of dimethylformamide,

57.5 parts xylene.

Such concentrates can be used to produce emulsions of the desired application concentration, which are particularly suitable for foliar application.

Biological Examples Example 7

Effect against Phytophthora on tomato plants a) Residual protective effect

After growing for 3 weeks, tomato plants 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 sporangial suspension of the fungus. The fungal attack was assessed after incubation of the infected plants for 5 days at 90-100% relative atmospheric humidity and 20 C.

b) Residual curative effect

After growing for 3 weeks, tomato plants were infected with a sporangia suspension of the fungus. After a 30-hour incubation in a moist chamber at 90-100% relative atmospheric humidity and 20 ° C., the infected plants were dried and sprayed with a spray mixture (0.06% active substance) prepared from wettable powder of the active ingredient. After the spray coating 35 had dried on, the treated plants were brought back into the moist chamber. The fungal infection was assessed 5 days after the infection.

c) Systemic effect

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

50

Example 8

Effect against Plasmopara viticola on vines In the 4-5 leaf stage, vine seedlings were sprayed with a spray mixture 55 (0.06% active substance) 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.

60

Example 9

Effect against Pythium debaryanum on beets Effect after soil application The fungus was cultivated on carrot schnitzel nutrient solution 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 preparations formulated as wettable powder became aqueous

13

639 940

Suspensions poured over the earth (20 ppm active ingredient based on the volume of the earth). The pots were then placed in the greenhouse at about 20 ° for 2-3 weeks. The earth was always kept evenly moist by light showering.

When evaluating the tests, the emergence of the sugar beet plants and the proportion of healthy and sick plants were determined.

Effect after pickling application The mushroom was cultivated on carrot schnitzel nutrient solution and added to a soil-sand mixture. The soil infected in this way was filled into earth trays and sown with sugar beet seeds which had been stained with the test preparations formulated as mordant powder (0.06% active ingredient).

The sown pots were placed in the greenhouse at about 20 ° C. for 2-3 weeks. The earth was always kept evenly moist by light showering. During the evaluation, the emergence of the sugar beet plants was determined.

Compounds of formula I showed a good effect in the experiments above. The disease infestation in Phytophtora was less in comparison to control plants (100% infestation) when treated with the compounds No. 1,3,5,23, io 24, 34,43, 67, 78,93, 99, 103 and 116 pushed back as 10%. In the case of Plasmopara, the compounds No. 1, 3, 5, 34, 67, 93 and 103 also brought about an infection reduction to less than 10% and after treatment with one of the compounds No. 1, 5, 23, 24, 34, 67 or 93 against i5 pythium over 80% of the sugar beet seeds came up. The plants showed a healthy appearance.

s

Claims (4)

639 940 2nd PATENT CLAIMS 1. Compounds of Formula I CH3 ch-coor, n contains at least one compound of the formula I according to claim 1 as active component. 3. Use of compounds of formula I according to claim 1 for combating phytopathogenic mi 5 microorganisms. 4. A process for the preparation of the compounds of the formula I defined in claim I, characterized in that CI) that an acid of the formula XVII c-r, 11 o 0 wherein R, and R2 independently of one another are C, -C3-alkyl, C! -C3-alkoxy or halogen, R3 is hydrogen, Cj-Q-alkyl or halogen, R4 is hydrogen or methyl, the total number of carbon atoms in R 1, R 2, R 3 and R 4 does not exceed 6. Rs represents Cr-C4-alkyl which is substituted by one of the groups listed below - C3-C7-Cycloalkyl optionally substituted by C ^ -C ^ alkyl - one to five halogen atoms - C6-Cjo aryl optionally substituted by halogen, cyano, nitro Cj-C3-A1-alkyl, Ci-C3-alkoxy or C, -C2-haloalkyl; - Cj-Q-Alk-oxy optionally substituted by halogen Ci-C3-alkoxy- (C2-C4) -alkoxy - C, -C4 alkylthio Ci-C4-alkylsulfmyl Ci-C4-alkylsulfonyl - Di- (C [-C4) alkylamino or O I! - -O-C-Y where Y is halogen or C: -C4-alkoxy-substituted Cj-C ^ alkyl; C2-C4-alkenyl optionally substituted by halogen; C2-C4 alkynyl; phenyl or benzyl optionally substituted by halogen, C1 -C3 alkyl, C1 -C3 alkoxy, cyano, nitro or C1 -C2 haloalkyl; or a halogen-substituted, saturated or unsaturated five- or six-membered heterocyclic radical with up to two heteroatoms, R6 2-furyl or 2-tetrahydrofuryI optionally substituted by halogen, - ß- (C1-C4) -alkoxyethyl or - means the group CH2Z, where Z for one of groups a) -X-R7 b) -NH-N (R8) (R9) c) -OSO2R10 d) -OCRn stands and A X oxygen or sulfur, R, C1-C6-alkyl, C3-C4-alkenyl or C3-C4-alkynyl optionally substituted by Cj-C2-alkoxy, R8 hydrogen or C1-C3-alkyl, R9 CI-C3-alkyl or phenyl optionally substituted by halogen or methyl, R10 Ci-C4-alkyl or mono- or di- (C1-C3) -alkyl amine and Rh represents Q-Cj-alkyl optionally substituted by Ci-C2-alkoxy. 2. Microbicidal agent for controlling or preventing an infestation of plants, characterized in that it 10th % > # 9 r> chcooh * 4 (xvn) in the presence of an esterification catalyst with an Al-20 alcohol of the formula XVIII hor5 (xviii) implemented, the substituents Rj to R6 in the formulas 25 XVII and XVIII as defined under formula I.