DD236667A1 - FUNGICIDES CONTAINING 2-AMINO-PYRIMIDINES - Google Patents

Abstract

The invention relates to fungicidal agents for combating phytopathogenic fungi containing 2-amino-pyrimidines. The aim of the invention is to provide new agents which have a broad fungicidal spectrum of activity and which can fulfill the requirements of the strategic concepts for avoiding the development of resistant fungal pathotypes or for controlling them. The object is achieved by the fungicidal compositions according to the invention which contain N-acylated 2-anilino-pyrimidines of the general formula I in addition to conventional carrier substances, solvents and / or formulation auxiliaries. The inventive compositions have fungicidal activity against a wide range of phytopathogenic fungi, such as. B. Phytophthora infestans, Erysiphe graminis, Aspergillus niger, Botrytis cinerea, Rhizoctonia solani, and required for their application in agriculture, forestry and horticulture plant compatibility.

Description

Field of application of the invention

The invention relates to novel fungicidal agents for controlling phytopathogenic fungi containing 2-amino-pyrimidines.

Characteristic of the known technical solutions

It is known that in the 5-position substituted 2-amino-6-alkyl-4-hydroxy or -mercapto-pyrimidine derivatives have interesting fungicidal properties and can be used to combat powdery mildew in cereal, fruit and vegetable growing ( DE-AS 1795726 and DE-AS 1795833).

Substituted 2-anilino-pyrimidines have been claimed as active ingredients for fungicidal agents having a preventive and curative action for controlling phytopathogenic fungi, in particular Phytophthora spp. (DD-WP 151 404).

However, the active substances methyrimol and ethyrimol selected from the described substance classes and used industrially have only a narrowly limited fungicidal spectrum of activity.

The increased resistance observed in recent times has further limited the scope of application of these drugs.

Object of the invention

The aim of the invention is to provide new fungicidal agents which have a broad spectrum of activity and can meet the requirements of the strategic concepts for preventing the development of resistant fungal pathotypes or for controlling them.

Features and features of the invention

The invention is based on the object by introducing new, suitable substituents in the 2-amino-pyrimidine molecule to optimize the structure of the active ingredients so that the desired improved utility properties are achieved.

As a result of these investigations, it has been found that N-acylated 2-anilino-pyrimidines of general formula I

(D

's^i) ¹ p' ^xi ^

in the R ¹ optionally halogen-substituted alkyl, aryl, aralkyl, furyl, alkoxycarbonylmethyl, alkoxy, arylamino or cycloalkylamino,

R ^{2 is} alkyl, halogen, alkoxy,

R ³ and R ⁴ independently of one another are hydrogen or alkyl, can be used as active ingredients for fungicidal agents for controlling phytopathogenic fungi.

The N-acylated 2-anilinopyrimidines useful in this invention have very good properties against a broad spectrum of phytopathogenic fungi, such as e.g. Phytophthora infestans, Erysiphegraminis, Aspergillus niger, Botrytiscirierea, Rhizoctonia solani. The pyrimidines of the invention exhibit excellent plant tolerance when used and thus represent a valuable addition to the art.

-2- 631

The preparation of N-acylated 2-anilino-pyrimidines can be carried out by known methods. Thus, the active ingredients listed in Table 1 were prepared by reacting 2-anilino-4,6-dimethylpyrimidines (preparation see DD-WP 151404) with acid chlorides, chloroformates or phenyl isocyanates.

The reactions can be carried out in inert solvents, preferably acetone, chloroform or benzene, it being possible to use sodium bicarbonate or triethylamine as acid-binding agents. The yields in the synthesis of the N-acylated 2-anilino-pyrimidines according to the invention are 60-80% d. Theory (see Examples 1 to 3). The active compounds according to the invention can be mixed with other known fungicides, wherein a synergistic effect occur and in many cases, a broadening of the spectrum of activity against phytopathogenic fungi can be achieved

The active compounds are formulated with suitable carriers and / or diluents and optionally surface-active substances or other auxiliaries by known methods to dusts, wettable powders, pickling agents, granules, pastes, emulsifiable concentrates or solutions and applied by dusting, spraying, scattering or pouring. To ensure the most even distribution of the active ingredient, the application form should be based on the application.

The fungicidal agents generally have an active ingredient content of 10-90% by weight, depending on the intended use.

When using the active compounds according to the invention for the treatment of plants and plant parts against fungal infections, the aqueous spray can contain 2 to 2000 ppm of active ingredient.

The following embodiments are intended to illustrate the invention without, however, limiting it and show the superiority of the 2-anilino-pyrimidines of the invention over the fungicide ethyrimol used in practice.

embodiments example 1

Preparation of 2- [N-trichloroacetyl-N- (4-bromophenyl) amino] -4,6-dimethyl-pyrimidine (Compound No. 22) 14.6 g (0.0523 mol) of 2- (4-bromophenyl-amino) 4,6-dimethylpyrimidine are dissolved in 150 ml of absolute acetone and to the solution is added 6.6 g (0.0784 mol) of sodium bicarbonate. While stirring, T4.27 g (0.0784 mol) of trichloroacetyl chloride are added dropwise at room temperature. The reaction mixture is kept at this temperature for 2-3 hours. The mixture is then added to 300 ml of water, the precipitate is filtered off with suction and recrystallized from ethyl acetate. The yield is 60% d. Theory.

F: 132-135 ° C

MW: C ₁₄ H ₁₁ BrCl ₃ N ₃ O (423.551)

Elemental analysis:

th. gef.

t 39,70 39,37 · ''

H 2,62 .3.03

N 9,92 9,30

Example 2

Preparation of 2- [N-phenylcarbamoyl-N- (4-methoxyphenyl) amino] -4,6-dimethyl-pyrimidine (Compound No. 50) 12 g (0.0523 mol) of 2- (4-methoxyphenyl-amino) -4 , 6-dimethylpyrimidine are dissolved in 80 ml of dry benzene and mixed with 6.23 g (0.0523 mol) of phenyl isocyanate. The mixture is then refluxed for 4-5 hours, the precipitate is filtered off with suction and recrystallized from toluene. The yield is 76% d. Theory.

F: 166-168 ⁰ C

MW: C ₂₀ H ₂₀ N ₄ O ₂ (348.426)

Elemental analysis:

th. gef.

C 68,95 69,47

H 5.78 5.98

N 16.08 15.79

Example 3

Preparation of 2- [N-methoxycarbonyl-N- (4-chlorophenyl) amino] -4,6-dimethyl-pyrimidine (Compound No.48) 12.2 g (0.0523 mol) of 2- (4-chlorophenyl-amino) 4,6-dimethylpyrimidine and 11 ml (0.0784 mol) of triethylamine are dissolved in 200 ml of dry chloroform. At room temperature, 6 ml (0.0784 mol) of methyl chloroformate are slowly added dropwise. It is refluxed for 3 hours and then treated with 4QmI -2 η hydrochloric acid. The organic phase is washed three times with water, dried and the chloroform aodistilled. The residue is recrystallized from methanol. The yield is 70% d. Theory.

F: 165 ° C

MW: C ₁₄ H ₁₄ CIN ₃ O ₂ (291.752)

Elemental analysis:

th. gef.

C 57.64 57.32

H 4,83 4,83

N 14,40 14,64

-3- 631 8!

Example 4

Fungicidal effect in spore germination test

The dissolved compounds of the invention were added to spore suspensions of the test fungi Aspergillus niger and Botrytis cinerea in concentration increments between 0.025 and 0.00025 moles. After incubation in the incubator for 20 hours, microscopic counting of germinated and non-germinated spores was carried out. Using these results, the ED ₆₀ and ED ₉₅ values were determined graphically. The ED ₉₅ values are summarized in Table 2.

Example 5

Fungicidal activity in mycelium growth test

The compounds according to the invention were dissolved in concentrations of 0.025.0.0025 and 0.00025 mol, added to a liquefied agar medium and poured into sterile petri dishes. After evaporation of the solvent, the agar plates were inoculated with the test fungus Rhizoctonia solani. After 7 days of incubation in the breeding area, the radial mycelial growth of the fungal colony was determined. The inhibition of mycelium growth in% is given in Table 3.

Example 6

Fungicidal activity against Phytophthora infestans

The substances according to the invention formulated as wettable powders with 20% active ingredient were sprayed onto tomato plants of about 10 cm in size. After the spray coating has dried on, the plants were inoculated with a zoospore suspension of the pathogen. The plants were incubated under favorable conditions for disease development. In the course of the disease symptom development, the control success shown in Table 4 was scored.

Example 7

Funigicidal activity against powdery mildew (Erysiphe graminis)

Winter barley plants grown in test vessels were sprayed in the single-leaf stage at about 10 cm height with the substances according to the invention formulated as wettable powders with 20% active ingredient. After the spray coating had dried on, the plants were inoculated by dusting with conidia of the pathogen. The plants were incubated under favorable conditions for disease development. In the course of the disease symptom development, the control success shown in Table E was achieved.

Table 1

COR

Ser. No.

F: ⁰ C

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

CH ₃

-CH ₂ CI

-CH ₂ CI

-CH ₂ CI

-CHCI ₂

-CHCI ₂

- ^ HCI ₂

-CHCI ₂

-CHCI ₂

-CHCI ₂

-CCI ₃

-CCI ₃

-CCI ₃

-CCI ₃

2-OCH ₃ 122-124 3-OCH ₃ 67-72 4-OCH ₃ 113-114 3-CH ₃ 108-110 4-CH ₃ 122 2-CI 65-67 4-CI 115-117 4-Br 125-126 2-OCH ₃ 106-127 3-OCH ₃ 160-162 4-OCH ₃ 160-161 4-OCH ₃ 127-129 3-CH ₃ 124-125 4-CH ₃ 105-106 4-Br 129-131 3-CI 105-107 4-CI 138-139 4-OCH ₃ 108-115 2-CH ₃ 93-196 3-CH ₃ 131-132 4-CI 135-138

Ser. No.

22 23 24 25 26 27 28 29 30 31 32 33 34

J?

-CCI ₃

CH2-C6H5

CH2-cehs

-CH ₂ -C ₆ H ₅

CH2-cehs

-CH ₂ -C ₆ H ₅

- (CH ₂ J ₃ -CH ₃

- (CH ₂ I ₃ -CH ₃

- (CH ₂ J ₃ -CH ₃

- (CH ₂ J ₃ -CH ₃

- (CH ₂ J ₃ -CH ₃

- (CH ₂ I ₃ -CH ₃

- (CH ₂ I ₃ -CH ₃

-4- 631 85 F: ⁰ C R ² 132-135 4-Br 98-100 2-OCH ₃ 66-68 4-OCH ₃ 117-118 4-CH ₃ 113-115 3-CI 115-117 4-CI 55-158 4-OCH3 85-90 2-CH ₃ 52-54 3-CH3 57-58 4-CH ₃ 51-52 3-CI 115.5 to 117.5 4-CI 168-175 4-Br

3-OCH ₃

100-103

I 1

4-OCH ₃

70-73

98-100

115-116

123-126

42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58

-V 3-CH ₃ 78-182 -O 4-CH ₃ 120-126 -CH ₂ -COOC ₂ H ₅ 4-0CH ₃ 75-76 -CH ₂ -COOC ₂ H ₅ 4-CI 118-119 -CH ₂ -COOC ₂ H ₅ 4-Br 104-105 -CH ₂ -COOC ₂ H ₅ ' 4-CH ₃ 71-75 -OCH ₃ 2-CH ₃ 84-85 -OCH ₃ 4-0CH ₃ 150-154 -OCH ₃ 4-CI ab165subl -OCH ₃ 4-Br 125-126 -NH-C ₆ H ₅ 4-OCH ₃ 166-168 -NH-C ₆ H ₅ 2-CH ₃ 149-151 -NH-C ₆ H ₅ 3-CH ₃ 154-156 -NH-C ₆ H ₅ 4-CH ₃ 158-160 -NH-C ₆ H ₅ 2-CI 159-160 -NH-C ₆ H ₅ 3-CI 154-155 -NH-C ₆ H ₅ 4-CI 173-175 -NH-C ₆ H ₅ 4-Br 187-189 -NH-C ₆ H ₁₁ 4-OCH ₃ 162-164

-5- 631 8!

Table 2

Inhibition of spore germination

Active ingredient *

Aspergillus ED ₉₅ [-10- ^e mol] Botrytiscinerea ED ₉₅ I-10 " ⁶ mol]

No 7 No 16 No 17 No 21 No 22 No 26 No 27 No 32 No 33 No 37 No 38 No 48 No 56 No 57 known **

0.016

0.12

0.0005

0.00025

2.4

0.28

0.31

0.29

0.46

0.27

0.7

0,035

0.05

0.072

9.3 3.5

20 5.2

62 2.5 2.5 0.44 0.56 6.5 0.47 5.8

42

25 260

86

* For the chemical name of the active substances cf. Information under the corresponding No. in Table 1. ** 2- (3-Chloroanilino) -4-methyl-pyrimidine (Compound 45 from DD-WP 151404)

Table 3 dose (0.0 Inhibition of mycelial growth (in%) 0,025 98 Active ingredient * 100 100 100 98 No. 7 100 98 No. 13 100 100 No. 16 iodo 98 No. 17 99 98 No. 21 100 98 No. 27 100 100 No. 35 100 100 No. 38 100 97 No. 48 100th 100 No. 56 100 No. 57 known**

0,00025 molar

98

100

100

100

Table 4

Control of Phytophthora infestans

Active ingredient *

Efficiency> 95% at ... ppm (active substance)

(untreated control

known***

*** 2- (4-Methylanilino) -4,6-dimethyl-pyrimidine (Compound 6 of DD-WP 151404)

100% infestation) 400 weak phytotoxicity 190 no phytotoxicity 110 no phytotoxicity 80 no phytotoxicity 150 no phytotoxicity 80 no phytotoxicity 150 no phytotoxicity 100 no phytotoxicity 250 no phytotoxicity 100 no phytotoxicity 200 no phytotoxicity

-6- 631 85

Table 5

Control of powdery mildew

Active ingredient * Efficiency> 95% at ... ppm (active substance) no phytotoxicity (untreated control 100% infestation) no phytotoxicity No. 16 200 no phytotoxicity No. 25 300 no phytotoxicity No. 27 200 no phytotoxicity No. 31 130 known*** 250

Claims (2)

-1 - 631 85 Claim: New fungicidal agents for controlling phytopathogenic fungi, characterized by a content of N-acylated 2-Anilinopyrimidinen of the general formula I. > 3 in the R ¹ optionally halogen-substituted alkyl, aryl, aralkyl, furyl, alkoxycarbony I methyl, alkoxy, arylamino or cycloalkylamino, R ^{2 is} alkyl, halogen, alkoxy R ³ and R ⁴ independently of one another are hydrogen or alkyl, in addition to customary carriers, solvents and / or formulation auxiliaries.