CH639372A5 - AROMATICALLY SUBSTITUTED PYRROL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF, THE FUNGICIDE COMPOSITIONS CONTAINING THEM AND METHOD FOR CONTROLLING FUNGI. - Google Patents

Description

The present invention relates to aromatically substituted pyrol derivatives, fungicidal compositions containing them, their use in a process for

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639372

Control of fungi and also processes for the preparation of these aromatically substituted pyrol derivatives.

It is previously known that various 3-phenylpyroles, for example 3- (2-nitro-3-chlorophenyl) -4-chloropyrene, 1-acetyl-3- (2-nitro-3-chlorophenyl) -4-chloropyrene, 3- (3,4-Di-chlorophenyl) -4-chloropyrol show antibiotic activity and are suitable as remedies.

It is also known that certain 3-phenylpyroles, e.g., 3- (2-nitro-3-chlorophenyl) -4-chloropyrene (see Japanese Patent Application Publication No. 88630/1976) and 3- (3-trifluoromethylphenyl) -4-chloropyrol (see published Japanese patent application No. 2011/1975) are effective for controlling plant diseases.

Surprisingly, it was found that corresponding pyrol derivatives which are substituted in the 3-position with a substituted phenyl nucleus have good fungicidal activity.

The present invention therefore relates to compounds of the formula I.

CA, CZ

ö-

V

CiL

H

having.

The compounds of the formula Ia can be converted into the corresponding compounds of the formula Ib acetylated on the nitrogen atom by acetylene.

Another object of the present invention is therefore a process for the preparation of a compound of formula Ib

^ TT "

m Xn N

Ib

CZ

N

COCH3

Xn c \

V

I.

R

m wherein Xn has one of the following meanings: 2-Cl, 3-Cl, 2,3-Ch and 3-CF3, which is characterized in that 25 a compound of the formula Ia, in which formula Xn has one of the following meanings : 2-Cl, 2-Cl, 2,3-Ch and 3-CF3 and R represents a hydrogen atom or an acetyl group, and it is ensured that Xn means 2,3-Ch when R represents a hydrogen atom.

The present invention further provides a fungicidal composition which is characterized in that it contains an inert carrier material and a fungicidally effective amount of the compound of the formula I.

Another object is a method for combating fungi, which is characterized in that an effective amount of a compound of the formula I is used at the location to be protected.

The present invention further relates to a process for the preparation of a compound of the formula Ia

Yes

30 Xn la wherein Xn has one of the following meanings: 2-Cl, 3-Cl, 2,3-Ch and 3-CF3, which is characterized in that a compound of the general formula II

s

CZ

11

KOOC "COOK H

heated in an inert solvent and thus the compound of formula Ia is obtained.

A preferred compound of the formula Ia prepared in this way is that which acetylates the following structure and thus obtains the compound of the formula Ib.

When carrying out process 35 according to the invention for the preparation of the compounds of the formula Ia, the decarboxylation of the starting material of the formula II is carried out by heating in an inert solvent. Amines which have a boiling point which is at or above the reaction temperature used, such as quinoline and dimethylaniline, can be used as inert solvents. Concentrated sulfuric acid can also be used as a solvent. The reaction can be carried out at a temperature in the range of 100 to 250 ° C and preferably in the range of 120 to 220 ° C 45 if the solvents used are amines, and preferably in the range of 100 to 130 ° C if so Solvent is sulfuric acid. The reaction time is usually about 20 minutes to a few hours, except that the reaction time is in the range of 5 to 20 minutes when the solvent is sulfuric acid. A catalyst is preferably used when the solvent is an amine. Copper (II) oxide or copper (II) salts, e.g. Copper (II) chloride or copper (II) sulfate can be used. 55 The acetylation reaction by which the compounds of the formula Ia are converted into the compounds of the formula Ib is advantageously carried out by reacting the compounds of the formula Ia with acetylimidazole at a temperature of 70 to 150 ° C. and preferably at 60 a temperature of 90 to 120 ° C for about an hour. In this case, the reaction can be carried out by melting the mixture of the compound of formula Ia with acetylimidazole or by heating the compound of formula Ia with a catalytic amount of acetylimidazole or imidazole in acetic anhydride.

Furthermore, the acetylation reaction can be carried out by reacting the sodium or potassium salt of the compound of the formula Ia with acetyl halides or

639372 4

by reacting the compound of formula Ia with acetic acid according to customary procedures, with reanhydride in the presence of triethylamine. for example by the following reaction, being in the following

The grouping used to prepare the compounds of the formula Ia as reaction equations Y denotes the compound of the formula II required as starting material

XI

Y-COCIÌ3 777 <- ^ 1 ~ Tv Y-COC: H2COCCOC2I! 5 -NH - (, COUC2Ii5) 2 4 J

y-coch2c-cooc2Hs. so, c £

r

V'WI 5 CÌI30H • ■ H 3 CCOO—Ns./^ COOCH

NCH (COOC2H5) 2H

C £ Y CZ

Vir Na ° H

: A /

: X JL

H 3 COGC ^ \ ^ "'--- COOCH 3 HOOG CCOH

H

[III

The compounds according to the invention are listed in Table I.

Table 1

Compound No. Chemical structure

CÄ, ÇI

COCH,

COCK,

CZ

Melting point

'/ w cz

GOCH,

58-59 ° C

97 ° C

70-71.5 ° C

82-84 ° C

! -90 ° C

The preparation of the compounds according to the invention is explained in more detail in the following example:

- 30 Example 1

Preparation of 4-chloro-3- (2,3-dichlorophenyl) pyrol (1) Preparation of ethyl 4- (2,3-dichlorophenyl) -2,4-di-oxobutyrate:

21.3 g of diethyl oxalate, 0.54 ml of ethanol and then 160 ml of ether solution, which contained 30 g of 2,3-dichloroacetophenone, were added dropwise to 14 g of 50% sodium hydride with stirring and with ice-cooling. The reaction was carried out under anhydrous conditions. Subsequently, the reaction was allowed to continue at room temperature 4 # with stirring for 40 minutes after the dropping was finished, and then was heated under reflux condition for 45 minutes. The reaction mixture was then poured into ice-cold water containing 17.5 g of acetic acid and, after stirring, the mixture was filtered. The organic layer was separated, dried and concentrated. The residue was recrystallized from n-hexane, giving 14.5 g of ethyl 4- (2,3-dichlorophenyl) -2,4-dioxobutyrate in the form of white needles with a melting point of 57 to 58 ° C.

(2) Preparation of ethyl 4- (2,3-dichlorophenyl) -2- (diethoxycarbonyI) methylamino-4-oxobutyrate:

A solution of 3.8 g of ethyl 4- (2,3-dichlorophenyl) -2,4-55 dioxobutyrate, 2.8 g of diethyl ester of aminomalonic acid hydrochloride and 2.0 g of pyridine in 80 ml of benzene were refluxed for 8 hours heated while removing the by-product water. After cooling the reaction solution, it was washed with aqueous 60 hydrochloric acid and then with aqueous sodium carbonate solution, then the solution was dried and evaporated to dryness, whereby 1.88 g of ethyl 4- (2,3-dichlorophenyl) -2- (diethoxycarbonyl) methyl-amino-4-oxo-butyrate.

65

(3) Preparation of dimethyl 3- (2,3-dichlorophenyl) pyrol-2,5-dicarboxylate:

1.88 g of ethyl 4- (2,3-dichloro-

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639 372

phenyl) -2-diethoxycarbonyl) methylamino-4-oxobutyrate (this compound was prepared in step 2, see above). 0.22 g of anhydrous sodium carbonate was then added to the solution and the solution was heated under reflux conditions for 4 hours.

After the reaction was completed, the methanol was removed by distillation under reduced pressure, and the residue was dissolved in ethyl acetate. The solution was dried and evaporated to dryness under reduced pressure. The residue was recrystallized from methanol, giving 1 g of dimethyl 3- (2,3-dichlorophenyl) pyroI-2,5-dicarboxy! Ate with a melting point of 143 to 145 ° C.

(4) Preparation of dimethyl 4-chloro-3- (2,3-dichlorophenyl) pyrene-2,5-dicarboxylate:

0.45 g of sulfanil chloride was added to a solution of 1 g of dimethyl 3- (2,3-dichlorophenyl) pyrol-2,5-dicarboxylate in 10 ml of acetic acid and the mixture was stirred overnight at room temperature. The reaction solution was evaporated to dryness under reduced pressure and the residue was dissolved in ethyl acetate. After washing the solution with aqueous sodium bicarbonate solution, the solution was dried and evaporated under reduced pressure to give 1 g of dimethyl 4-chloro-3- (2,3-dichlorophenyl) pyrol-2,5-dicarboxylate in the form of white crystals obtained a melting point of 172 to 173 ° C.

(5) Preparation of 4-chloro-3- (2,3-dichlorophenyl) pyrol-2,5-dicarboxylate:

A mixture of 1 g of dimethyl 4-chloro-3- (2,3-dichlorophenyl) pyrol-2,5-dicarboxylate, 1 g of sodium hydroxide, 30 ml of ethanol and 18 ml of water was heated under reflux conditions for 90 minutes. After the reaction took place, the ethanol was removed by distillation under reduced pressure, and the residue was washed with ether. The aqueous layer was acidified with hydrochloric acid and then extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried and evaporated to dryness under reduced pressure to give 0.93 g of 4-chloro-3- (2,3-dichlorophenyl) pyrol-2,5-dicarboxylic acid in the form of white crystals with a decomposition point of 273 ° C.

(6) Preparation of 4-chloro-3- (2,3-dichlorophenyl) pyrol (Compound No. 1):

A mixture of 53 g of 4-chloro-3- (2,3-dichlorophenyl) pyrol-2,5-dicarboxylic acid, 2.65 g of copper (II) oxide and 80 ml of quinoline was heated to 140 to 150 ° C for 30 Heated for minutes with stirring. To the reaction mixture thus obtained, ethyl acetate, ice and concentrated hydrochloric acid were added in an amount of 10 mol% excess over the quinoline used. The ethyl acetate layer was washed, successively with water, aqueous sodium carbonate solution and water. After drying, the ethyl acetate layer was evaporated to dryness under reduced pressure to give 33.1 g of a brown product. The crude product was purified by chromatography on silica gel and countercurrent distribution to give a pale yellow, oily substance. The oily substance was recrystallized from n-hexane, whereby 22.5 g of the desired product (colorless or pale yellow needles with a melting point of 58 to 59 ° C.) were obtained.

Example 2

Preparation of l-acetyl-4-chloro-3- (2,3-dichlorophenyl) pyrol (Compound No. 2):

A mixture of 0.3 g of 4-chloro-3- (2,3-dichlorophenyl) pyrol and 0.6 g of N-acetylimidazole was melted for one hour at 140 ° C under a protective atmosphere of a stream of argon. The reaction mixture thus obtained was purified by thin layer chromatography, whereby 0.2 g of the desired product was obtained in the form of colorless or slightly colored crystals with a melting point of 97 ° C.

Example 3

Preparation of l-acetyl-4-chloro-3- (3-trifluoromethyl-phenyl) pyrol (Compound No. 3):

A mixture of 1 g of 4-chloro-3- (3-trifluoromethyl-phenyl) pyrol and 2 g of N-acetylimidazole was melted at 140 to 150 ° C. for 1 V2 hours. The reaction mixture thus obtained was purified by chromatography on silica gel using a 10% solution of acetone in n-hexane as a solvent, whereby 0.8 g of the desired product in the form of pale reddish brown crystals with a melting point of 70 to 71.5 ° C received.

Example 4

Preparation of 1-acetyl-3- (2-chlorophenyl) -4-chloropyrene (Compound No. 4):

A mixture of 4.35 g of 3- (2-chlorophenyl) -4-chloropyrene and 5.3 g of N-acetylimidazole was heated at 100 to 110 ° C for 4 hours. After the reaction mixture was cooled, it was dissolved in 200 ml of ether, and the ether solution thus obtained was washed successively with dilute hydrochloric acid and water. The ether solution was then dried with anhydrous sodium sulfate and evaporated to dryness under reduced pressure. The remaining crude product was purified by chromatography on silica gel using a mixed solvent of n-hexane and benzene (1: 1) to give 2.5 g of the desired product as colorless crystals with a melting point of 82 to 84 ° C received.

Example 5

Preparation of I-AcetyI-3- (3-chlorophenyi) -4-chloropyrene (Compound No. 5):

A mixture of 6.5 g of 3- (3-chlorophenyl) -4-chloropyrene and 10.1 g of N-acetylimidazole was heated at 100 to 110 ° C for one hour. After cooling, the reaction mixture was dissolved in a mixture of 200 ml of ether and 20 ml of water, and the ether solution thus obtained was treated as described in Example 4 to give 4.5 g of the desired product as colorless crystals with a melting point obtained from 88 to 90 ° C.

The compounds of the invention have excellent fungicidal activities when used to prevent plant damage, and especially acetyl compounds, and preferably Compounds Nos. 2 to 5, have exceptional residual activity.

The compounds can be used directly without being mixed with a suitable carrier material.

An active component of a fungicidally active composition can be formulated, for example, in a manner according to the invention by using suitable carrier materials.

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639372

6

rialien in a form, as they are usually used in pesticide compositions, for example wettable powders, emulsifiable concentrates and dust formulations. Bentonite, diatomaceous earth, apatite, gypsum, talc, pyrophyllite, vermiculite and clay, for example, can be used as solid carrier materials. Kerosene, mineral oils, petroleum, petrol, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, benzene and water can be used as liquid carrier materials, for example. If desired, surfactants can be added to ensure a homogeneous stable formulation.

The concentration of the active agent in the fungicidally active composition can vary depending on the type of formulation, and is, for example, between 5 and 80 percent by weight and preferably between 20 and 80 percent by weight for wettable powders; between about 5 and about 70 weight percent and preferably between about 10 and about 50 weight percent for emulsifiable concentrates and between about 0.5 to about 20 weight percent and preferably between about 1 and about 10 weight percent for dust formulations.

In addition, the compounds can be used in a mixture with other fungicides, insecticides, mild control agents and herbicides.

Some preferred examples of fungicidally active compositions according to the invention are as follows:

Example 6 Wettable Powder:

Parts by weight

Compound No. 1

20th

Diatomaceous earth

73

S atrium higher alkyl sulfate

7

The ingredients are mixed homogeneously and reduced to small particle sizes, whereby a wettable powder is obtained which contains 20% of the active ingredient.

Example 7 Emulsifiable concentrate:

Parts by weight

Compound No. 2 20

Xylene 42

Dimethylformamide 30

Polyoxyethylene alkylphenyl ether 8

The ingredients are mixed and dissolved to give an emulsifiable concentrate containing 20% of the active ingredient.

Dust formulation:

Parts by weight

Compound No. 3

2nd

Talk

98

The ingredients are mixed homogeneously and comminuted to a small particle size, which gives a dust formulation which contains 2% of the active ingredient.

The wettable powder or the emulsifiable concentrate is diluted with water to a suitable concentration and is used as a suspension or emulsion for the treatment of soil, plants or seeds. The dust formulation is used directly to treat the soil, plants or seeds.

The fungicides according to the invention are effective for controlling many plant diseases, for example when combating by application to plants, the gray mold, the schlerotinx rot in vegetables, the leaf mold in tomatoes, the anthracnose, the fusari withered and the gum stalk rot in the cucumber, mildew, fire, Leaf disc burn and Helminthosporal leaf spots from rice, streak disease from barley, black spots from pears, brown rot from peaches, the gray mold from grapes and the scab from apples; by applying it to the ground one can fight the anthracnose, the fusarium wilt and the cucumber rubber stalk; by treating the seeds, the mildew and the helminthosporal leaf spot disease of the rice, the barley strip disease, the wilting of the wheat and the wheat cereal can be combated.

The fungicidal activity of the compounds according to the invention is explained using the following tests:

Test 1: Test for the control of gray mold on beans:

The removed leaves of kidney beans (Phaseolus vulgaris) were immersed for 30 seconds in aqueous suspensions prepared by diluting wettable powders to various concentrations containing the test compound. After air drying, the treated leaves were inoculated with botrytis cinerea mycelium and kept at 20 ° C in a humid climate chamber. The fungal control activity was assessed 4 days after inoculation. The results are summarized in Table 2. No phytotoxicity was observed.

Table 2

Combat test value (%)

Test compound No. Concentration of the active ingredient

12.5 ppm

6.3 ppm

1

100

100

2nd

100

100

3rd

94

80

4th

100

95

5

100

100

Reference substance *

la

95

70

2a

39

8th

3a

75

33

4a

79

5a

35

* Comparative substances:

1 a 4-Chloro-3- (2-nitro-3-chlorophenyI) pyrol, see published Japanese Unexamined Patent Application No. 88630/1976

2a 4-chloro-3- (3,4-dichlorophenyl) pyrol, see Published Examined Japanese Patent Application No. 6748/1967

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25th

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639372

3a 4-chloro-3- (3-trifluoromethylphenyl) pyrol, see published examined Japanese Patent Application No. 2011/1975 4a Rovral (trade name):

l-Isopropylcarbamoyl-3- (3,5-dichlorophenyl) -hydantoin 5a Euparen (trade name):

N'-dichlorofluoromethylthio-N, N-dimethyl-N'-phenylsulfamide 5

Test 2: Test to control gray mold on beans (residual activity test)

Kidney beans (Phaseolus vulgaris L.) seedlings ("Nagauzura", 1.5 leaf size) placed in pots were sprayed once with a chemical solution with a concentration of 200 ppm of an active ingredient and then kept in a greenhouse. The leaves were separated and inoculated with Mycelium Botrytis cinerea 7 days after spraying and in a moist climate chamber at 20 ° C. i5

held. The effectiveness was examined 4 days after inoculation. The results are summarized in Table 3. No phytotoxicity was observed.

Table 3 20

Table 4

Test connection no.

Fungus control value (%)

1

2nd

3rd

4th

5

Comparative substance * la

PCNB

100 100 100 100 100

93 70

Test connection no.

Fungal control value

(%)

2nd

3rd

4th

5

Reference substance *

la

2a

3a

4a

5a

100 100 100 98

22 10 62 89 64

25th

* Comparative substances:

la: same connection as in test 1.

PCNB: pentachloronitrobenzene

Test 4: Test for the Effectiveness of Barley Strip Disease by Seed Treatment:

Barley seed Kashima was treated with chemically wettable powders and the field was sown one day after the seed treatment. The effectiveness of the treatment was assessed 120 days after sowing the seed. The results are summarized in Table 5. No phytotoxicity was observed.

30th

Test connection no.

Table 5

Protective effect (%)

Active ingredient (g) / 100 kg seed

* Comparative substances: The same comparative substances as in test 1 were used.

Test 3: Test for Rhizoctonia Decay in Cucumbers:

Pot-seeded cucumber seedlings were treated by injecting an aqueous suspension containing the test compound at a concentration of 100 ppm into the soil in an amount of 10 ml per pot after inoculating with Rhizoctonia solani mycelium would have. The control effect was assessed 4 days after inoculation. The results are summarized in Table 4. No phytotoxicity was observed.

10th

20th

30th

50

1

100

100

100

2nd

94

98

100

40 3

97

98

99

4th

96

97

100

5

97

93

100

Comparative-45 substance * Vitavax

52

* Vitavax: 5,6-dihydro-2-methyl-l, 4-oxathiin-3-carboxyanide

B

Claims (25)

639372 CLAIMS Compound of the general formula (I) where in this formula Xn has one of the following meanings: 2-Cl, 3-Cl, 2,3-Ch and 3-CF3, and where R denotes a hydrogen atom or an acetyl group, it being ensured that Xn has the meaning 2,3 -Ch when R represents a hydrogen atom. 2. A compound according to claim 1, characterized in that Xn has the meaning, 2,3-Ch, and that R represents a hydrogen atom. 3. A compound according to claim 1, characterized in that R denotes an acetyl group. 4. A compound according to claim 3, characterized in that Xn has the meaning 2-Cl. 5. A compound according to claim 3, characterized in that Xn has the meaning 3-Cl. 6. A compound according to claim 3, characterized in that Xn has the meaning 2,3-Ch. 7. A compound according to claim 3, characterized in that Xn has the meaning 3-CF3. 8. Fungicidal composition, characterized in that it contains an inert carrier material and a fungicidally effective amount of the compound of formula (I). 9. Fungicidal composition according to claim 8, characterized in that it contains a fungicidally effective amount of a compound according to claim 2. 10. Fungicidal composition according to claim 8, characterized in that it contains a fungicidally effective amount of a compound according to claim 3. 11. Fungicidal composition according to claim 8, characterized in that it contains a fungicidally effective amount of a compound according to claim 4. 12. Fungicidal composition according to claim 8, characterized in that it contains a fungicidally effective amount of a compound according to claim 5. 13. Fungicidal composition according to claim 8, characterized in that it contains a fungicidally effective amount of a compound according to claim 6. 14. Fungicidal composition according to claim 8, characterized in that it contains a fungicidally effective amount of a compound according to claim 7. 15. A method for combating fungi, characterized in that an effective amount of a compound of the formula I is used at the site to be protected. 16. The method according to claim 15, characterized in that an effective amount of a compound according to claim 2 is used at the location to be protected. 17. The method according to claim 15, characterized in that an effective amount of a compound according to claim 3 is used at the location to be protected. 18. The method according to claim 15, characterized in that an effective amount of a compound according to claim 4 is used at the location to be protected. 19. The method according to claim 15, characterized in that an effective amount of a compound according to claim 5 is used at the location to be protected. 20. The method according to claim 15, characterized in that an effective amount of a compound according to claim 6 is used at the location to be protected. 21. The method according to claim 15, characterized in that one is effective at the location to be protected Use amount of a compound according to claim 7. 22. Process for the preparation of a compound of formula Ia Ia in which Xn has one of the following meanings: 2-Cl, 3-Cl, 2,3-Ch and 3-CF3, characterized in that a compound of the general formula II 35 15 CZ ij. H00C "C00H XI 20th 30th heated in an inert solvent and thus the compound of formula Ia is obtained. 23. The method according to claim 22, characterized in that the compound of the following formula Cv_ / C £ Ö-killing " N H prepared by using the compound of formula as starting material of formula II CZ CZ .CZ 40 N HOOC * H 'COOH. 24. Process for the preparation of a compound of formula Ib 45 ^ C £ * jD-oT ' Ib N ÓOCH: so wherein Xn has one of the following meanings: 2-Cl, 3-Cl, 2,3-Ch and 3-CF3, characterized in that a compound of formula Ia Ia acetylated and thus receives the compound of formula Ib. 65