CH618583A5 - Fungicidal composition - Google Patents

Description

The present invention relates to a fungicidal agent and to its use for combating fungal diseases of plants.

Many compounds with fungicidal activity 15 are already known, for example 1- (2-halo-2-phenylethyl) imidazoles from US Pat. No. 3,679,697,1-substituted 1,2,4-triazoles from US Pat. PS 3 912 752, triazolyl-0, N-acetal from US Pat. No. 3,952,002 and triazolyl alkanones and alkanols from ZA PS 754 111.

The invention relates to an agent which, as an active component, comprises at least one compound of the formula

25th

wherein R6 is hydrogen, halogen or alkyl, or contains a salt of such a compound.

2. Use of agents according to claim 1 for combating fungal diseases of plants.

3. Composition according to claim 1, characterized in that in the compound of formula IZ for> C = S and X are a group of formula (A).

4. Composition according to claim 1, characterized in that in the formula IR is alkyl, alkenyl or alkynyl and X represents a group of formula (A).

5. Composition according to claim 1, characterized in that in the formula IR is optionally substituted aralkyl, in particular with halogen, preferably chlorine, or a nitro, trifluoromethyl, cyano or methoxy group substituted benzyl and X is for a Group of formula (A) is.

6. Composition according to claim 1, characterized in that the compound of formula 12- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone, 2- (l, 2.4 -Triazol-l-yl) -2-t-butyl-4'-chloroacetophenone, 2- (l, 2,4-triazol-l-yl) -2-n-butyl-ace-tophenone, 2- ( l, 2,4-triazol-l-yl) -2-i-propyl-4'-chloroacetophe-non, 2- (l, 2,4-triazol-l-yl) -2-n-propyl-4 ' -chloroacetophenone, 2- (l, 2,4-triazoI-l-yI) -2-benzyl-4'-chloroacetophenone, 2- (l, 2,4-triazol-l-yl) -2-t ~ butylacetophenone, 2- (l, 2,4-triazole-

1-yl) -2-n-butyl-4'-fluoroacetophenone, 2- (l, 2,4-triazol-l-yl) -

2- (4-chlorobenzyl) acetophenone, 2- (l, 2,4-triazoI-l-yl) -2- (2,4-dichlorobenzyl) acetophenone, 2- (l, 2,4-triazole-l -yl) -2- (4-chlorobenzyl) -4'-chloroacetophenone, 2- (l, 2,4-triazol-l-yl) -2- (2,4-dichlorobenzyl) -4'-fluoroacetophenone, 2- (l, 2,4-triazol-l-yl) -2- (2-fluorobenzyl) -4'-chloroacetophenone, 2- (l, 2,4-triazol-l-yl) -2- (2,4- dichlorobenzyl) -4'-chloroacetophenone or a salt thereof.

7. Composition according to claim 1, characterized in that in formula I R is alkyl and X is a group of formula (B).

8. Composition according to claim 1, characterized in that in formula I R is optionally substituted aralkyl, in particular phenyl substituted with halogen, preferably chlorine or a methoxy group, and X represents a group of formula (B).

x-ch-z- "vw * 3

30th

35

wherein R is hydrogen or an optionally substituted hydrocarbon group, Z is> C = O or a ketal, hydrazone, semicarbazone or oxime is> C = S, R1-R5, which may be the same or different, hydrogen, halogen, an optionally substituted Hydrocarbon or hydrocarbonoxy group or a nitro or amino group means and X for a group of the formula

40

45

or

(a)

wherein R6 is hydrogen, halogen or alkyl, or contains a salt of such a compound.

so The term "hydrocarbon group" used here refers to monovalent organic radicals made of hydrogen and carbon, which can be saturated or unsaturated, straight-chain or branched-chain or as a simple ring. Examples include alkyl, alkenyl, alkynyl, cycloalkyl, ss aryl, aralkyl, alkaryl. The hydrocarbon group can be substituted, with one or more hydrogen atoms being replaced by one or more other atoms, for example halogen, or one or more groups. The term “hydrocarbonoxy-60 group” used here refers to a hydrocarbon group as defined above which is bonded via an oxygen atom to the carbon atom bearing group X.

Ketals, hydrazones, semicarbazones and oximes are derivatives of the figuration> C = O.

65 In formula I, R preferably denotes a hydrocarbon group with 1-7 C atoms, such as alkyl, e.g. B. methyl, ethyl, propyl, n- and i-propyl, butyl, n-, i-, t-butyl, amyl, hexyl, heptyl, octyl; Alkenyl, e.g. B. allyl; Alkynyl, e.g. B. Pro

3rd

618 583

pynyl; Phenyl; Methylphenyl; Aralkyl. Examples of optionally substituted aralkyl groups are benzyl optionally substituted with halogen, such as fluorine, chlorine or bromine, nitro, trifluoromethyl, cyano or methoxy.

In formula I, R1 -] * 5 halogen, e.g. B. fluorine, chlorine, bromine, alkyl, alkenyl, alkynyl, as mentioned above, alk-oxy, z. B. methoxy, ethoxy, butoxy, octyloxy, or phenyl, and R6 is suitably hydrogen, bromine or methyl.

The salts of compounds of the formula I can be salts with organic or inorganic acids, such as hydrochloric, sulfuric, acetic or oxalic acid.

Particularly preferred compounds of formula I are those in which R is optionally substituted aralkyl, e.g. B. s is benzyl when X is a group of formula (B).

Compounds of the formula I in which X represents a group of the formula (A) are hereinafter referred to as "1,2,4-triazole derivatives" and those in which X represents a group of the formula (B) as " Imidazole derivatives ».

io Table 1 lists useful 1,2,4-triazole derivatives.

Table 1

Ver R Z R1 R2 R3 R4 R5 R6 Melting point bond, ° C

No.

1

n-C4H9

c = o

H

H

Cl

H

H

H

81-83

2nd

H

c = o

H

H

Cl

H

H

H

148-150

3rd

n-C6H13

c = o

H

H

Cl

H

H

H

70-73

4th

n-c8hi7

c = o

H

H

Cl

H

H

H

90-91

5

t-C4H9

c = o

H

H

Cl

H

H

H

110-112

6

n-C4H9

c = o

H

H

H

H

h h

113-115

7

C2Hs c = o h

h h

h h

H

105-107

8th

c2h5

c = o h

H

Cl h

h h

84-85

9

ch3

c = o h

h och3

h h

H

103-104

10th

Ì-C3H7

c = o h

H

Cl

H

h h

65-66

11

n-C4H9

c = 0

H

h och3

h h

H

116-118

12

n-c4H9

c = o h

h ch3

H

h h

99-101

13

n-QHy c = o h

H

Cl h

h h

81-83

14

n-C4H9

c = o

Cl h

Cl h

h h

01

15

CH2C6HS

c = o

H

H

Cl

H

H

H

120-121

16

ch3

c = o

H

H

Cl

H

H

H

84-85

17th

n-C4H9

c = o och3

H

och3

H

H

H

57-60

18th

t-C4H9

c = o

H

H

H

H

H

H

110-112

19th

n-C4H9

c = o och3

H

och3

OCH3

H

H

90-98

20th

n-C4H9

c = o h

H

F

H

H

H

44-45

21st

n-C4H9

c = o h

H

oc2hs

H

H

H

114-115

22

H

c = o och3

H

H

H

H

H

105-107

23

c2h5

C = NOH

H

H

H

H

H

H

141-143

24th

n-C4H9

c = no

H

H

OQHs

H

H

H

166

25th

n-C4H9

C = NOH

H

h och3

H

H

H

135-137

26

n-C3H7

c = o

H

H

H

H

H

H

110-112

27th

n-C3H7

c = o

H

H

OCH3

H

H

H

103-105

28

CH2-CH = CH2

c = o

H

H

Cl

H

H

H

61-63

29

ch2-c = ch c = o

H

H

Cl

H

H

H

105-108

30th

H

c = o

H

H

H

H

H

H

115-116

31

n-C3H7

c = o ch3

H

CH3

H

H

H

01

32

ch3

c = o

H

H

H

H

H

H

94-95

33

n-C4H9

c = o ch3

H

ch3

H

H

H

01

34

n-CsHu c = o

H

H

H

H

H

H

106-107

35

n-C5Hn c = o

H

H

Cl

H

H

H

80-81

36

n-C3H7

C = NOH

H

H

OCH3

H

H

H

144-146

37

n-C4H9

C = NOH

H

H

Cl

H

H

H

182-185

38

n-C4H9

c = n-nh-r3

CS N

n02 H

H

Cl

H

H

H

117-119

39

ch3

2nd

c = o

H

H

n-OC4H9

H

H

H

54-56

40

n-C4H9

c = o

H

H

n-OC4H9

H

H

H

57-59

41

H

c = o

H

H

Br

H

H

H

176-179

42

n-C4H9

c = o

H

H

Br

H

H

H

104-107

43

H

c = o

H

no2

H

H

H

H

166-168

44

c6h5

c = o

H

H

H

H

H

H

144-145

45

ck2-Qk: i

0

II

u

H

H

H

H

H

H

125-127

618 583

4th

Table 1 (continued)

Ver R

binding,

No.

R1

R2

R3

R4

Rä R6 melting point

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

n-C4 ï 19

Cl ch2

ch2c6h5

ch.

£> cl o6Hs

^ o n-C4H9

n-C4H9

n-C4H9

H

H

H

H

H

n-C4H9 H

ch

H

n-QHg

ch

ci, 2 <g>

CH2C6hs c2h5

CH2c6hs

CH2- ^ ° 2

ch.

ch,

2nd

II-C4H9

ch f

a

^ ci ch2-0c1

Cl

CH2-0-Cl Cl c = o

H

Cl

Cl

H

H

H

01

c = o

H

H

H

h h

H

134-135

c = o

H

H

h h

H

H

144-145

c = o h

h h

H

h h

125-127

C = NNHCONH2 - HCl h

H

Cl h

H

H

149-151

c = o h

H

H

h h

Br

73-74

c = o h

H

Cl h

H

Br

01

c = nnhconh2

H

H

Cl

H

H

H

184-188

c = o h

h h

h h

Br

125-130

c = o h

H

Cl

H

H

Br

171-173

c = o

CI

h h

h h

H

68

c = o f

h h

H

H

H

102-103

c = 0

f h

h h

h h

94-96

C = N-OH

Cl

H

H

H

h h

163-165

c = o h

H

Cl h

h h

99-100

c = o

H

H

f

H

H

H

121-123

c = o h

H

C6Hs h

h h

144-146

c = o

H

H

f

H

h h

80-82

c = o h

H

h h

h h

108-110

c = o h

H

h h

h h

114-116

c = o h

no2

h h

H

H

135-137

c = o

11-OQH9

H

h h

H

H

57-61

c = o h

no2

h h

H

H

135-137

0

ii

0

h h

f h

h h

82-84

c = o h

h f

h h

H

127-129

0

ii

0

h h

f h

h h

136-138

c = o h

h f

h h

H

90-92

c = o

H

H

Cl h

h ch3

0

ii u

H

h f

h h

H

118.5-12

c = o h

h f

h h

H

112-114

c = o h

H

Cl h

h h

112-113,

618 583

Table 1 (continued)

Ver R

binding,

No.

77

cn2 © * ° 2

c = o

78

ch ^ cn c = o

79

cu2-Q

c = o

80

F

o c = o

81

cf-

caïÙ

c = o

82

c = o

83

ch2 <3> f c = o

84

I1-C4H9

c = o

85

cn2- © a c = o

86

87

88

89

n-C4H9 n-C4H9 i-C5Hn i-CsHii

0000

II II II II

Ü 0 u u

90

ch2-on02

c = o

91

ch2-0

0on c = o

R1

R2 R3

R4

R5 R6 melting point

92

93

96

97

98

n-C4H9 ch

KD »08:

94 n-C4H9

95 ch ch ch.

fö «

a o2n

2 ^ 2

c = o c = o c = o c = o c = o c = o c = o

H

H

Cl

H

H

H

158-160

H

H

Cl

H

H

H

146-148

H

H

Cl

H

H

H

110-112

H

H

Cl

H

H

H

97-98

H

H

Cl

H

H

H

84.5-86.

H

H

H

H

H

H

152-154

H

H

H

H

H

H

126-128

H

H

OC8H17

H

H

H

47-49

OCH3

H

H

H

H

H

109-111

ch3

H

H

H

H

H

01

H

OCH3

H

H

H

H

01

H

H

H

H

H

H

64

H

H

Cl

H

H

H

73-74

H

H

Br

H

H

H

168-170

H

H

Br

H

H

H

150-152

Cl

H

H

H

H

H

79-81

H

H

Br

H

H

H

113-115

H

ch3

H

H

H

H

01

Cl

H

H

H

H

H

144-145

F

H

H

H

H

H

147-149

Cl h

H

H

H

H

110-113

Cl

H

H

H

H

H

164-166

The chemical analysis results of the above compounds are summarized in Table 2.

No.

1

2nd

3rd

4th

5

6

7

8th

9

10th

11

12

13

14

15

16

17th

18th

19th

20th

21st

22

23

24th

25th

26

27th

28

29

30th

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

6

Table 2

Analysis results found theory

H N C H N

Table 2 (continued)

Analysis results connection found theory

No. C H N C H N

59.5 5.6 15.5 60.5 5.8

54.2 3.7 19.1 54.2 3.6

62.8 6.6 13.5 62.9 6.6

64.9 7.2 12.5 64.8 7.2 60.9 5.8 15.2 60.5 5.8 67.1 6.7 16.5 69.1 7.0 66.8 6.2 19 , 7 67.0 6.1

57.5 4.9 16.8 57.7 4.9

61.6 5.6 18.2 62.3 5.7 59.0 5.2 15.8 59.2 5.3

66.0 7.0 15.9 65.9 7.0

69.5 7.5 16.4 70.0 7.4

59.1 5.3 15.9 59.2 5.3

53.6 4.8 13.4 53.9 4.8

65.1 4.7 13.4 65.4 4.5

56.2 4.2 17.7 56.1 4.3 60.8 6.5 13.2 63.4 7.0

68.5 7.1 17.2 69.1 7.0 61.1 6.9 12.6 61.2 7.0 64.1 6.2 15.5 64.4 6.1

66.6 7.2 14.7 66.9 7.4 60.4 4.8 19.3 60.8 5.1

62.7 6.1 24.7 62.6 6.1

63.3 7.3 18.7 63.7 7.3

61.8 6.6 19.6 62.5 7.0 68.1 6.6 18.3 68.1 6.6 64.8 6.5 16.5 64.8 6.6

59.8 4.5 16.1 59.7 4.6

60.1 4.0 16.3 60.1 3.9

63.3 4.9 21.3 64.2 4.8

69.4 7.4 16.0 70.0 7.4

65.3 5.4 20.9 65.7 5.5

70.6 7.8 15.4 70.8 7.8

69.9 7.4 16.1 70.0 7.4

60.2 5.7 14.0 61.7 6.2

61.5 6.7 20.4 61.3 6.6

57.4 5.8 19.2 57.4 5.9 19.1

52.7 4.5 21.6 52.5 4.4 21.4 Particularly useful 1,2,4-triazole derivatives are 2- (l, 2.4- £ 5 ^ 14.8 65.9 7.0 15.4 45 xriazol-l-yl) -2-t-butyl-4'-chloroacetophenone (I), 2- (l, 2,4-tria-

zol-l-yl) -2-n-butyl-4'-chloroacetophenone (II), 2- (l, 2,4-tria-zol-1-yl) -2-benzyl-4'-chloroacetophenone (III) .

The triazole derivatives can be obtained by reacting 1,2,4-triazole, which may be substituted accordingly, with a

73.0 5.2 15.6 73.0 5.0 16.0 50 a corresponding halo ketone by any 65.9 4.6 13.7 65.5 4.5 13.5 ^ [known in the art. Thus, 1,2,4-triazole 53.9 5.0 13.1 53.9 4.8 13.5 can be reacted with an a-halo ketone

59.1 3.7 12.1 59.0 3.8 12.1 Formula 74.1 5.5 15.2 73.6 5.4 15.2

63.3 4.2 17.2 63.4 4.4 17.4 55 R1 r2

48.6 5.1 22.3 48.5 5.4 22.6 \ /

51.4 4.9 12.8 52.2 5.0 13.0 /, \ 3 - - x-ch-z- ^ y-r

47.3 4.1 30.3 47.4 4.0 30.2 I V = \

45.6 3.0 15.8 45.1 3.0 15.8 so r c 4

40.1 2.3 14.0 40.0 2.4 14.0 R5 R

54.4 3.6 18.8 54.2 3.6 19.0

58.1 3.8 19.9 58.5 3.9 20.5 where X is halogen, preferably bromine or chlorine.

64.8 6.2 16.2 64.4 6.2 16.1 In certain cases, the preparation can be heated

50.6 3.9 '23.4 50.8 3.8 23.7 65 of the reactants in the absence of a solution or diluent

58.7 3.8 12.1 59.0 3.8 12.1 solvent, but is preferably carried out in the presence of 58.0 3.9 20.4 58.5 3.9 20.5 of a solvent. Suitable solvents are 74.7 6.8 12.9 75.2 6.6 13.2 non-hydroxyl solvents such as the preferred acetonitrile

15.1

63

59.1

3.68

11.6

59.5

3.58

11.6

19.0

64

69.2

4.79

14.2

68.7

4.3

15.0

13.8

65

62.8

4.09

12.2

62.6

4.06

12.2

12.6

10 66

62.1

4.4

16.9

63.4

4.4

17.4

15.1

67

65.5

7.2

14.2

66.9

7.4

14.6

17.3

- 68

57.2

3.8

15.8

57.2

3.7

15.7

19.5

: 69

68.2

4.9

14.2

69.2

4.8

14.2

16.8

70

59.7

4.03

16.4

60.0

3.12

16.5

18.2

15 71

67.0

4.28

17.4

67.5

4.06

17.5

15.9

72

64.9

4.19

13.4

65.2

4.15

13.4

15.4

73

-

-

-

-

-

16.3

74

61.8

4.07

12.7

61.9

3.94

12.7

15.9

75

56.0

3.29

11.6

56.0

3.30

11.5

13.5

20 76

53.4

3.22

11.0

53.6

3.15

11.0

13.4

77

57.0

3.73

15.4

57.2

3.64

15.7

17.8

78

63.9

3.91

16.6

64.2

3.86

16.6

13.9

79

61.7

3.90

12.6

61.9

3.94

12.7

17.3

"80

63.9

6.0

14.0

63.2

5.9

13.8

12.6

25 81

56.9

3.49

11.2

56.9

3.43

11.1

16.1

82

71.3

4.70

18.1

71.5

4.64

18.5

14.6

83

68.7

4.78

14.2

69.2

4.78

14.2

19.4

84

71.1

8.9

11.2

71.1

9.0

11.3

24.3

85

62.4

4.7

12.2

63.3

4.7

12.3

18.5

30 86

69.3

7.5

15.0

70.0

7.4

16.3

19.4

87

65.7

7.1

12.4

65.9

7.0

15.4

18.3

88

70.3

7.4

16.4

70.0

7.4

16.3

16.2

89

61.8

6.2

14.3

61.8

6.2

14.4

16.1

90

51.0

3.3

14.0

50.9

3.3

14.0

16.2

35 91

50.9

3.4

13.8

50.9

3.3

14.0

21.4

92

60.7

5.9

15.2

60.5

5.8

15.1

16.3

93

55.6

4.3

10.8

56.0

4.2

10.9

20.9

94

70.1

7.6

16.4

70.0

7.4

16.4

15.5

95

63.7

4.0

16.3

64.2

3.9

16.6

16.3

40 96

60.2

4.0

16.4

60.0

3.9

16.5

14.4

97

57.3

3.8

15.1

57.2

3.7

15.7

20.4

98

57.1

3.7

15.7

57.2

3.7

15.7

68.8 8.0 13.4 68.5 8.0 13.3

44.8 3.0 16.0 45.1 3.0 15.8

52.2 5.0 12.9 52.2 5.0 13.0

51.2 3.6 24.1 51.7 3.5 24.1

7

618 583

as well as dimethylformamide, dimethyl sulfoxide, sulfolane and tetrahydrofuran.

Hydroxylated solvents such as methanol and ethanol can be used in certain circumstances if the hydroxyl group does not interfere with the progress of the reaction. The process can also be carried out in the presence of a base, but preferably in the presence of excess triazole to remove released HX from the reaction. Other suitable bases are, for example, sodium hydride, but not when using a hydroxylated solvent or diluent, alkali metal carbonates, such as potassium carbonate, and alkali metal hydroxides, such as potassium hydroxide. The temperature at which the reaction is carried out depends on the reactants, solvents and bases used, but the reaction mixture is generally heated to the reflux temperature.

In general, the production process comprises dissolving the reactants in a solvent and, after the reaction has taken place, separating the product obtained by removing the solvent in vacuo. Unreacted triazole can then be removed by solvent extraction and washing the solvent with water. If desired, the product obtained can be recrystallized or purified by another method.

The a-haloketone used as the starting material can be prepared by any of the methods known in the literature.

1,2,4-Triazoles of formula I, wherein R represents a hydrocarbon group, can also be treated by treating the corresponding triazol-l-yl-acetophenone of the formula to introduce the hydrocarbon group, for example first with an alkali metal hydride such as sodium hydride in a solvent such as Dimethylformamide or tetrahy-

drofuran, with the formation of the sodium salt and this thereafter, for example with an alkyl or aralkyl halide, preferably a bromide or a chloride.

In general, such a manufacturing process involves dissolving the triazol-l-yl-acetophenone in the solvent and adding an equivalent amount of the alkali metal hydride and, after the reaction has taken place, adding the alkyl or aralkyl halide dropwise. After the reaction, the end product can be separated off by pouring it into water and purified by recrystallizing the solid formed from a solvent or the oil obtained by means of column chromatography or another suitable method.

15 The triazol-1-yl-acetophenone can be prepared by reacting the appropriately substituted phenacylhalogenide with a 1,2,4-triazole by one of the methods described above.

2- (l, 2,4-Triazol-l-yl) -l-benzyl-3'-nitroacetophenone (IV) 20 can be obtained by reaction of 2- (l, 2,4-triazol-l-yl) -3 '-ni-troacetophenone with benzyl chloride by one of the methods described above.

2- (l, 2,4-Triazol-l-yl) -3'-nitroacetophenone can be obtained by nitrating 2- (l, 2,4-triazol-l-yl) acetophenone by one of the methods known from the literature.

The carbonyl derivatives can be prepared by any of the methods known in the literature. So 2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone oxime (V), 2- (l, 2,4-triazol-l-yl) - 2-n-butyl-4'-chloroacetophenone-30 2,4-di-nitrophenyl-hydrazone (VI) and 2- (l, 2,4-triazol-l-yl) -2-n-butyl-4./ -chloroacetophenone-semicarbazone hydrochloride (VII) are prepared by reacting 2- (l, 2,4-trizol-l-yl) -2-n-buryl-4'-chloroacetophenone (II) with the customary carbonyl addition agents.

35 compounds of formula I, wherein R6 is bromine, can be obtained by bromination of the corresponding 1,2,4-triazol-1-yl ketone with the usual brominating agents, such as bromine or N-bromosuccinimide. 2- (5-Bromo-2,3,4-triazol-l-yl) -2-n-butyl-acetophenone (VIII) can thus be obtained by bromination of 2- (l, 2,4-triazol-l- yl) -2-n-butylacetophenone with N-bromosuccinimide in the presence of a polyhalogenated solvent, such as carbon tetrachloride or methylene chloride. Usually the reaction is carried out at reflux temperature and is better in the presence of an initiator 45 such as benzoyl peroxide.

Useful imidazole derivatives are listed in Table 3.

Table 3

Connection, no.

R1

R2 R3 R4 R5

R6

Melting point ° C

99

100

101

ch2c6hs ch ch

K>

-QJ

ci ci c = 0 h h h h h h oil c = 0 h h F h h h 59-61

c = 0 h h h h h h 01

102

103

104

ch2c6hs ch30

ch.

ch.

c = o c = o c = o h h Cl h h h 01 h h h h h h 01

H H H H H H

01

618 583

8th

Table 3 (continued)

Connection, no.

R

e.g.

R1

R2

R3

R4

Rs

R6

Melting point ° C

105

ch2c6hs

c = o h

H

Br h

h h

01

106

ch2c6h5

c = o h

H

F

h h

H

01

Cl \ <

107

CH2 ^

)

c = o h

H

F

h h

H

125-126

108

CH2C

^ C1

c = o

H

H

H

H

H

H

97-98

cir

/

109

n-C4H9

c = o

H

H

Cl

H

H

H

01

110

n-cshn

c = o

H

H

CI

H

H

H

01

111

t-C4H9

c = o h

H

Cl

H

H

H

127-128

112

n-C8Hi7

c = o

H

H

Cl

H

H

H

01

113

n-C4H9

c = o

H

H

H

H

H

H

01

114

c2h5

c = o

H

H

Cl

H

H

H

01

115

H

c = o

H

H

Cl

H

H

H

158-160

116

H

c = o

Cl

H

Cl

H

H

H

01

117

H

c = o

H

H

H

H

H

H

115-117

118

n-C4H9

c = o

H

H

och3

H

H

H

01

119

CH2C6Hs

c = o

Cl

H

Cl

H

H

H

01

The chemical analysis results of the above compounds are summarized in Table 4.

Table 4

Analytical results

connection

found

theory

No.

C.

H

N

C.

H

N

Ili

65.5

6.1

10.2

65.1

6.2

10.1

115

59.5

4.2

12.6

59.9

4.1

12.7

117

71.1

5.4

14.9

71.0

5.4

15.0

118

67.6

7.1

9.8

70.5

7.4

10.3

Particularly useful imidazole derivatives are 2-imidazol-l-yl) -2-t-butyl-4'-chloroacetophenone (IX), 2-imidazol-l-yl) -2-n-butyl-4'-chloroacetophenone (X) and 2- (imidazol-l-yl) -2-ben-zyI-4'-chloroacetophenone (XI).

The imidazole derivatives can be obtained by reacting imidazole with the corresponding a-halo ketone by any of the methods known from the literature, so that imidazole can be reacted with an a-halo ketone as described above.

Imidazole derivatives of formula I, wherein R is a hydrocarbon group, can also be prepared by treating the corresponding imidazolyl acetophenone as described above for 1,2,4-triazolyl derivatives, for example by alkylation.

The manufacturing options include:

a) reaction of optionally appropriately substituted imidazole or 1,2,4-triazole or a salt thereof with a compound of the formula I in which X is halogen, preferably chlorine or bromine;

b) introducing a hydrocarbon group into a compound of formula I in which R is hydrogen or in a salt thereof to give a compound of formula I in which R is a hydrocarbon group or a salt of such a compound;

c) nitration of a compound of formula I in which R 35 is hydrogen or a hydrocarbon group, namely alkyl, alkenyl or alkynyl, or a salt thereof, to give a compound of formula I in which R is hydrogen or alkyl, alkenyl or alkynyl and R2 represent a nitro group;

40 d) halogenation of an unsubstituted triazole derivative of the formula I or a salt thereof, whereby a compound of the formula I is obtained in which X represents a group of the formula (A) in which R6 is halogen or a salt thereof; if desired, if a compound of the formula I in which Z is C = 0 or a salt thereof is obtained by one of the above processes a) -d),

this compound can be converted in a known manner to a compound of the formula I in which Z is a derivative of C = 0, or to a salt thereof.

The 1,2,4-triazole and imidazole derivatives and embodiments of the agent according to the invention, which contain such derivatives as active components, are effective in a wide range against fungal diseases of plants, for example against:

Puccinia recondita and other rotting fungi Rhizoctonia solani on various host plants Tilletia caries of wheat Pyrenophora avenae and P. graminea Fusarium spp. and Botrytis cinerea also most powdery mildew species, including Erysiphe graminis on cereals Sphaerotheca fuliginea Podosphaera leucotricha and Uncinula necator and other fungal diseases of economic importance.

A particularly valuable feature of the effectiveness of the derivatives described is their systemic effect, i. H.

50

55

60

65

9

618 583

their ability to move around in a plant to fight infection or infection in locations distant from the original application site of the agent. The agent according to the invention can thus be applied to the planting base which surrounds the roots of a plant, to the seeds or to other places on the plant, for example the leaves thereof, and is then taken up by the plant through the roots or other places to combat fungi at this or other parts of the plant.

The derivatives described could be used as a pure substance for combating fungal diseases, but are used in the agent according to the invention as an active component in a preparation in a mixture with a carrier.

Various embodiments of the agent according to the invention can be used to combat fungal diseases of plants by treating the plants or their seeds in various ways, for example by directly applying them to the foliage of a plant which has already been infected or exposed to infection or to shrubs and trees, or on Planting ground or other growth media for existing plants, shrubs and trees or before planting by spraying, dusting or applying in the form of a cream or paste. It can be applied to any place on plants, shrubs or trees, for example on foliage, stems, twigs, seeds or roots, or on the planting ground surrounding the roots.

The term "treatment" used here encompasses all the types of application mentioned above, and the term "plant" used here includes, apart from plants, seeds, bushes and trees. The use of the agent according to the invention includes preventive, protective, preventive and destructive treatment.

The agent according to the invention is suitable for use in agriculture and horticulture, the particular embodiment of the preparation being dependent on the particular intended use.

Embodiments of the agent according to the invention are atomizable powders or granules, for example ordinary or slow-acting granules, the active component being mixed with a solid carrier, such as kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesium oxide, chalk, gypsum, Hwitt's earth , Diatomaceous earth, chinaclay. Preparations for the treatment of seeds can contain, for example, an agent which supports the adhesion of the preparation to the seed, such as mineral oil.

Other embodiments include dispersible powders or granules that contain a wetting agent to aid dispersion in liquids and can also contain fillers and suspending agents.

Aqueous dispersions or emulsions can be obtained by dissolving the active component in an organic solvent, which can contain wetting agents, dispersing agents and / or emulsifying agents, and incorporating the resulting mixture into water, which also contain wetting agents, dispersing agents and / or emulsifying agents can. Suitable organic solvents are, for example, ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichlorethylene.

Spray preparations can also be produced in the form of aerosols, the preparation being kept under pressure in a pressure vessel together with a propellant, for example fluorotrichloromethane or dichlorodifluoromethane.

By adding appropriate aids, for example to improve the distribution, the adhesion and the rainwater resistance on treated surfaces, the different preparations can be better adapted to the respective purpose.

The preparations can also be produced in a mixture with fertilizers, for example nitrogen or phosphorus fertilizers, preferably in the form of a granular fertilizer, the granules being coated with the active component.

The agent according to the invention can also be produced in liquid preparation for immersion or spray treatments, generally as an aqueous dispersion or emulsion which contains the active component in the presence of wetting agents, dispersants, emulsifiers and / or suspending agents. Such aids can be cationic, anionic or nonionic. Suitable cationic agents are, for example, quaternary ammonium compounds, such as cetyltrimethylammonium bromide. Suitable anionic agents are, for example, soaps, salts of aliphatic monoesters of sulfuric acid, such as sodium lauryl sulfate, salts of sulfonated aromatic compounds, such as sodium dodecylbenzenesulfonate, 20 sodium, calcium or ammonium lignosulfonate, butylnaphthalenesulfonate, mixtures of sodium diisopropyl and triisopropyl naphthalenesulfonates. Suitable nonionic agents are, for example, condensation products of ethylene oxide and fatty alcohols, such as oleyl or cetyl alcohol, or alkylphenols, such as octyl or nonylphenol and octylcresol. Other suitable nonionic agents are, for example, partial esters derived from long-chain fatty acids and hexitol anhydrides and their condensation products with ethylene oxide and lecithins. Suitable suspending agents are, for example, hydrophilic colloids, such as polyvinylpyrrolidone and sodium carboxymethyl cellulose, and also plant gums, such as acacia and tragacanth.

Preparations for use as an aqueous dispersion or emulsion are generally prepared in the form of a concentrate with a high proportion of the active component, which is diluted with water before use. Such concentrates are usually said to be stable in storage for a longer period of time and then to be dilutable with water to form aqueous preparations which remain homogeneous for a sufficiently long period of time in order to enable distribution by means of conventional spraying devices. Such concentrates expediently contain 10-85% by weight, generally 25-60% by weight, of the active component, based on the weight of the concentrate. After dilution to a 45 ready-to-use aqueous preparation, this can contain the active component in various concentrations, depending on the intended use, use concentrations of the active component of, for example, 0.0005% by weight or 0.01-10% by weight being used can be long.

The agent according to the invention can additionally contain one or more other biologically active compound (s) as well as stabilizing agents, for example epoxides, such as epichlorohydrin.

55 Methods A-N for the preparation of compounds of the formula I are explained below, for example. (Analysis results =% by weight.)

Method A

60 In a first stage, 0.02 mol of bromine was stirred dropwise into a solution of 0.02 mol of 4'-chlorohexane phenone in 20 ml of anhydrous diethyl ether of 10-20PC within 1 h. The ether was then removed from the reaction mixture in vacuo to give, after distillation, 2-bromo-4'-chloro-65 xanphenone with a boiling point of 124-126 ° C./0.04 mm Hg in the form of a light yellow liquid, of which 0.02 Mol in a second stage together with 0.1 mol 1,2,4-triazole and 50 ml acetonitrile at reflux temperature for 48 h

618 583

10th

were heated. The acetonitrile was removed in vacuo, the residue was extracted with 150 ml of chloroform, washed with 5 × 100 ml of water and dried over anhydrous sodium sulfate. The solvent was removed in vacuo to give an oil which crystallized on trituration with 5 X 50 ml of petroleum ether. Recrystallization from petroleum ether gave 2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophe-non with melting point 81-83 ° C.

Method B

In a first stage, 0.03 mol of 2,4'-dichloroacetophe-non was added in portions to a solution of 0.03 mol of 1,2,4-triazole and triethylamine in 40 ml of acetonitrile at -15 to -20 ° C. Speed stirred in that the temperature of -20 ° C was maintained. After the reaction mixture had been stirred at -20 ° C. for 2 h, the reaction mixture was allowed to warm to room temperature and the triethylamine hydrochloride was filtered off. After removal of the acetonitrile and recrystallization of the solid residue from a water / ethanol mixture, 2- (l, 2,4-triazol-l-yl) -4'-chloro-cetophenone with melting point 148-150 ° C. was in the form obtained from light yellow needles.

Analysis: Ci0H8ON3C1

theor .: C 54.2 H 3.6 N 19.0%

found: C 54.2 H 3.7 N 19.1%

In a second stage, 0.5 g of sodium hydride in 50% suspension in oil was washed several times with petroleum ether, suspended in 5 ml of dimethylformamide and then 0.01 mol of 2- (l, 2,4-triazol-l-yl) with stirring -4'-chloroacetophenone from stage 1 was added in portions and stirred at room temperature for several hours until the foaming stopped, after which 0.01 mol of n-butyl bromide was stirred dropwise into the solution at room temperature and the solution was then added to complete the reaction at 50-60 ° C was heated. After cooling to room temperature, the solution was poured into water and the solid formed was filtered off, after recrystallization from petroleum ether at 60-80 ° C 2- (l, 2,4-triazol-l-yl) -2-n-butyl-4 '-chloroacetophenone with melting point 81-83 ° C was obtained in the form of colorless crystals.

•

Method C

In a first stage, 0.02 mol of bromine was stirred dropwise into a solution of 0.02 mol of 2-benzyl-4'-chloroacetophenone in 20 mol of anhydrous diethyl ether at 10-20 ° C. within 1 h, and then the ether in vacuo removed and the residue dissolved in 100 ml of ether, washed with 2 x 100 ml of a saturated aqueous solution of sodium bicarbonate and then 4 x 100 ml of water and dried over anhydrous sodium sulfate. Removal of the solvent and recrystallization of the solid obtained from petroleum ether at 60-80 ° C. gave 2-bromo-2-benzyl-4'-chloroacetophenone with a melting point of 88-90 ° C. in the form of colorless crystals, of which 0.02 in a second stage Mol with 0.1 mol 1,2,4-triazole in 50 ml acetonitrile were heated to reflux temperature for 48 h. Then the acetonitrile was removed in vacuo and the residue was extracted with 150 ml of chloroform, washed 4 × 100 ml with water and dried over anhydrous sodium sulfate. After removal of the solvent and recrystallization of the oil residue from a methylene dichloride / petroleum ether mixture at 60-80 ° C., 2- (l, 2,4-triazol-l-yl) -2-benzyl-4'-chloroacetophenone obtained with melting point 120-121 ° C in the form of colorless crystals.

Method D

0.5 g of 100% sodium hydride was suspended at room temperature in 13 ml of anhydrous dimethylformamide and a solution of 0.015 mol of 2- (l, 2,4-triazol-l-yl) -4'-chloroacetophenone in 15 ml of anhydrous dimethylformamide was added dropwise and stirring continued until the foaming stopped. The solution was then decanted from excess sodium hydride and a solution of 0.015 mol of benzyl chloride in 15 ml of dimethylformamide was stirred in dropwise at -5 to 0 ° C. After stirring for 2 hours at room temperature, the solution was poured into water and the solid formed was filtered off. Recrystallization of the solid from a methylene chloride / petroleum ether mixture at 60-80 ° C gave 2- (l, 2,4-triazol-l-yl) -2-benzyl-4'-chloroaceto-phenone with a melting point of 120-121 ° C in the form of colorless crystals.

Method E

In a first stage, 0.45 mol of 1,2,4-triazole and 0.4 mol of phenacyl chloride were stirred at room temperature in 100 ml of acetonitrile and, with gentle cooling, 0.45 mol of triethylamine was added dropwise, and the reaction mixture was then stirred at room temperature for a further 4 h was stirred. The precipitated triethylamine hydrochloride was filtered off and the acetonitrile was removed in vacuo. After recrystallization of the solid residue from an ethanol / water mixture, 2- (l, 2,4-triazol-l-yl) acetophenone with a melting point of 115-116 ° C was obtained in the form of light yellow needles.

Analysis: C10H9ON3

theor .: C 64.2 H 4.8 N 21.4%

found: C 63.3 H 4.9 N 21.3%

In a second stage, 0.02 mol of the 2- (l, 2,4-triazol-l-yl) acetophenone from stage 1 was concentrated to a mixture of 7.5 ml of sulfuric acid. and nitric acid at a maximum of 10 ° C and then the mixture heated to 50 ° C for 1 h and then to 60 ° C for 10 min. After cooling to room temperature, the mixture was poured into 400 liters of water, neutralized with sodium bicarbonate and the yellow solid formed was filtered off and washed with petroleum ether. After recrystallization from a chloroform / petroleum ether mixture at 60-80 ° C., 2- (l, 2,4-triazol-l-yl) -3'-nitroacetophenone with a melting point of 166-168 ° C. became in the form of a crystalline solid receive.

Analysis: C10HsO3N4 ■ theor .: C 51.7 H 3.5 N 24.1%

found: C 51.2 H 3.6 N 24.1%

In a third stage, 0.24 g of sodium hydride in a 50% suspension in oil was washed at 40-60 ° C. with petroleum ether and suspended in 150 ml of dimethylformamide. Then 0.005 mol of the 2- (l, 2,4-triazol-1-yl) -3! -Nitroacetophenone from stage 2 were stirred in portions into the cooled suspension and stirring was continued until the foaming stopped. In the solution obtained, 0.005 mol of benzyl chloride was stirred in dropwise at room temperature and, after stirring for 2 hours, the solution was poured into 50 ml of water and the solid formed was filtered off. After recrystallization from a chloroform / petroleum ether mixture at '40-60 ° C, 2- (1,2,4-triazol-1-yl) -2-benzyl-3'-nitroace-tophenone with a melting point of 135-137 ° C obtained in the form of colorless crystals.

Method F

0.1 mol each of 2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone and hydroxylamine hydrochloride were dissolved in 10 ml of pyridine and 100 ml of methanol for 3 hours Reflux temperature heated. After removal of the methanol in vacuo, 200 ml of water were added, and after recrystallization of the precipitated crystalline solid from toluene, 2-

5

10th

is

20th

25th

30th

35

40

45

50

55

60

65

11

618 583

(1,2,4-Triazol-l-yl) -2-n-butyl-4'-chloroacetophenone oxime with melting point 182-185 ° C was obtained.

Method G

0.001 mol each of 2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloro-tophenone and 2,4-dinitrophenyl-hydrazine were heated to reflux temperature in 12 ml of methanol for 10 min , after cooling to room temperature with 0.25 ml of hydrochloric acid conc. added and the solution is then heated on a steam bath. After cooling, 2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone-2,4-dinitrophenyl-hydrazone hydrochloride with a melting point of 126-128 ° C was in the form yellow crystals were obtained, which were suspended in 10 ml of an aqueous solution of sodium bicarbonate, mixed with 10 ml of ether and left to stand until the solid had completely dissolved. Then the ether layer was washed with 2 x 10 ml of water and dried over anhydrous sodium sulfate. After removing the ether in vacuo, and after recrystallizing it from a chloroform / petroleum ether mixture at 60-80 ° C., 2- (l, 2,4-triazol-l-yl) -2-n-butyl- 4'-Chloroacetophenone-2,4-dinitrophenyl-hydrazone with melting point 117-119 ° C in the form of yellow crystals.

Method H

Each 0.005 mol of semicarbazide hydrochloride and 2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone and 2 drops of pyridine were in a mixture of 5 ml of water and methanol during a Day heated to reflux temperature. After cooling, an oil separated out, which after recrystallization from a chloroform / petroleum ether mixture at 60-80 ° C 2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone -semi-carbazone hydrochloride with melting point 149-151 ° C.

Method I

In a first stage, 0.063 mol of bromine was stirred dropwise into a solution of 0.063 mol of 3,3-dimethyl-4'-chlorobutanphenone in 50 ml of anhydrous diethyl ether at 10-20 ° C., and the ether was then removed from the reaction mixture in vacuo, after recrystallization of the yellow solid formed from petroleum ether at 60-80 ° C., 2-bromo-3,3-dimethyl-4'-chlorobutanphenone with a melting point of 77-78 ° C. was obtained, of which 0.0086 mol and 0.043 mol of 1,2,4-triazole were heated to 160 ° C. over 4 h. The reaction mixture was cooled, added to 200 ml of water and extracted with methylene chloride, after which the extract was washed with 2 x 100 ml of water, dried over magnesium sulfate and the methylene chloride was removed in vacuo. Recrystallization of the solid obtained from petroleum ether at 60-80 ° C gave 2- (l, 2,4-triazol-l-yl) -2-t-butyl-4'-chloroacetophenone with a melting point of 110-112 ° C.

Method J

0.01 mol of 2- (l, 2,4-triazol-l-yl) -2-n-butyl-acetophenone was dissolved in 10 ml of carbon tetrachloride and 0.01 mol of N-bromosuccinimide was added in one go. The solution was then heated to reflux temperature for 15 hours with the addition of a small amount of benzoyl peroxide as a free radical generating catalyst. After cooling to room temperature, the succinimide was filtered off and the filtrate was concentrated in vacuo. The residue was taken up in 100 ml of petroleum ether, washed with 4 × 70 ml of water and dried over anhydrous sodium sulfate. After removal of the petroleum ether and recrystallization of the semi-solid residue from petroleum ether at 60-80 ° C., 2- (5-bromo-l, 2,4-triazoi-l-yl) -2-n-butyl-acetophenone with melting point 73 -74 ° C obtained as colorless crystals.

Method K

In a solution of 0.02 mol of 4'-chlorohexane phenone in 20 ml of anhydrous diethyl ether, 0.02 mol of bromine was stirred in dropwise at 10-20 ° C. over the course of 1 hour. The petroleum ether was then removed in vacuo and the pale yellow liquid which remained was distilled, giving 2-bromo-4'-chlorohexane-phenone with a boiling point of 124-126 ° C./0.04 mm Hg, of which in a second stage 0. 02 mol and 0.1 mol of imidazole in 50 ml of acetonitrile was heated for 48 hours under reflux temperature. The acetonitrile was then removed in vacuo, the residue was extracted with 150 ml of chloroform, the extract was washed with 5 × 100 ml of water and dried over anhydrous sodium sulfate. After removal of the solvent in vacuo, 2- (imidazol-l-yl) -2-n-butyl-15 4'-chloroacetophenone was obtained in the form of an oil.

Mathode L

In a first stage, 0.063 mol of bromine was stirred dropwise into a solution of 0.063 mol of 3,3-dimethyl-4'-chlorobutanphenone in 50 ml of anhydrous 20 diethyl ether at 10-20 ° C. within 1 h. After removal of the ether in vacuo, a yellow solid was obtained and after recrystallization from petroleum ether at 60-80 ° C 2-bromo-3,3-dimethyl-4'-chloro-butanephenone with a melting point of 77-78 ° C, of which in 25 a second stage, 0.0086 mol and 0.043 mol imidazole were heated to 160 ° C. for 4 h. The reaction mixture was cooled, added to 200 ml of water and extracted with methylene chloride. The extract was washed with 2 × 100 ml of water, dried over magnesium sulfate and the methylene chloride was removed in vacuo, with 2- (imidazol-l-yl) -2- after recrystallization of the solid obtained from petroleum ether at 60-80 ° C. t-butyl-4'-chloroacetophenone with melting point 127-128 ° C was obtained.

35 Method M

0.02 mol of 2-bromo-2-benzyl-4'-chloroacetophenone and 0.1 mol of imidazole were heated to reflux temperature in 50 ml of methanol for 6 hours. The methanol was then removed in vacuo and the residue was taken up in 100 ml of diethyl ether 40, washed with 4 × 100 ml of water and dried over anhydrous sodium sulfate. Removal of the solvent gave an orange oil, from which 2- (imidazol-1-yl) -2-benzyl-4'-45 chloroacetophenone was obtained in the form of a light yellow oil after purification by column chromatography on silica and elution with ethyl acetate.

Method N

In a first stage, 0.5 mol of 4'-chlorophenacyl-50 bromide and 2 mol of imidazole in 200 ml of methanol were stirred at 0 ° C. for 3 h. The methanol was then removed in vacuo, the residue was taken up in 500 ml of methylene chloride, washed with 6 × 250 ml of water and dried over anhydrous sodium sulfate. Removal of the solvent and recrystallization of the solid obtained from methanol gave 2- (imidazol-l-yl) -4'-chloroacetophenone with a melting point of 158-160 ° C. in the form of light brown needles.

In a second stage, 0.5 g of 100% sodium hy-60 drid were suspended in 15 ml of anhydrous dimethylformamide at room temperature and added dropwise with stirring with a solution of 0.015 mol of 2- (imidazol-l-yl) -4'-chloroacetate tophenons from stage 1 are added to 15 ml of anhydrous dimethylformamide and stirring is continued until the foaming stops. The solution was then decanted from excess sodium hydride and a solution of 0.015 mol of benzyl chloride in 15 ml of dimethylformamide was added dropwise with stirring at -5 to 0 ° C. After stirring

618 583

12

After a further 2 h at room temperature, the solution was poured into water and the precipitated oil was taken up in petroleum ether, dried over anhydrous sodium sulfate and, after removal of the petroleum ether, purified by column chromatography on silica and eluted with ethyl acetate, 2- (imidazol-l-yl) - 2-benzyl-4'-chloroacetophenone was obtained in the form of a light yellow oil.

example 1

An emulsifiable concentrate was prepared by mixing the following components in the specified proportions and stirring until all components were completely dissolved.

2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloro

acetophenone

Ethylene dichloride

Calci um dodecylbenzosulfate

"Lubrol" L

"Aromasol" H

Wt. '

10 40 5

10 35

Example 2

A preparation in the form of granules which are readily dispersible in a liquid, for example water, was prepared by grinding the first three components mentioned below in the presence of water and then admixing the sodium acetate, the mixture obtained being dried and sieved through a sieve to obtain the desired particle size a mesh size of 0.152-0.353 mm was driven.

% By weight

2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone 50

"Dispersol" T 25

"Lubrol" APN 5 1.5

Sodium acetate 23.5

Example 3

The following components were ground together in the stated proportions to form a powdery preparation which was readily dispersible in liquids.

% By weight

2- (l, 2,4-triazol-l-yl) -2-t-butyl-4'-chloro

acetophenone

"Dispersol" T

"Lissapol" NX

"Cellofas" B600

Sodium acetate

45 5

0.5 2 47.5

Example 4

The active component below was dissolved in a solvent to prepare a granular preparation, and the resulting liquid was sprayed on granular china clay, after which the solvent was evaporated to give a preparation of the following composition by weight.

% By weight

2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone 5

Chinaclay granules 95

Example 5

A preparation suitable for the treatment of seeds was prepared by mixing the following components in the stated proportions.

% By weight

15

2- (l, 2,4-triazol-l-yl) -2-t-butyl-4'-chloro

acetophenone

mineral oil

Chinaclay

50 2 48

20th

Example 6

A powdery preparation suitable for atomization was prepared by mixing the active component specified below with talc in the specified proportions.

30 2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone talc

Gew.1;

5 95

35

Example 7

A surface-adhering liquid preparation was prepared by grinding the components listed below in the proportions indicated in a ball mill and suspending the resulting mixture in water.

40

Gew.1

2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloro-45 acetophenone "Dispersol" T "Lubrol" APN 5

40 10 1

50

Example 8

A dispersible, powdered preparation was prepared by mixing the components listed below in the proportions indicated and grinding the mixture until thoroughly mixed.

55

% By weight

2- (1,2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone 25 60 "Aerosol" OT / B 2 "Dispersol" A.C. 5 Chinaclay 28 silicon dioxide 40

65

Example 9

A dispersible, powdery preparation was prepared by mixing the below

Components in the stated proportions and grinding of the mixture until thorough mixing.

% By weight

2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloro

acetophenone 25

"PERMINAL" BX 1

"Dispersol" T 5

Polyvinyl pyrrolidone 10

Silicon dioxide 25

Chinaclay 34

Example 10

A dispersible, powdered preparation was prepared by mixing the components listed below in the proportions indicated and grinding the mixture until thoroughly mixed.

% By weight

2- (l, 2,4-triazol-l-yl) -2-n-butyl-4'-chloroacetophenone 25

"Aerosol" OT / B 2

"Dispersol" A 5

Chinaclay 68

Example 11

An emulsifiable concentrate was prepared by mixing the components listed below in the stated proportions and stirring the mixture until all components had completely dissolved.

% By weight

2- (imidazol-l-yl) -2-n-butyl-4'-chloro

acetophenone 10

Ethylene dichloride 40

Calcium dodecylbenzenesulfonate 5

"Lubrol" L 10

"Aromasol" H 35

Example 12

A preparation in the form of grains which are readily dispersible in a liquid, for example water, was prepared by grinding the first three components mentioned below in the presence of water and then admixing the sodium acetate, the mixture obtained being dried and sieved through a sieve to obtain the desired grain size a mesh size of 0.152 to 0.353 mm was driven.

% By weight

2- (imidazol-l-yl) -2-n-butyl-4'-chloro

acetophenone 50

"Dispersol" T 5

"Lissapol" NX 0.5

"Cellofas" B600 2

Sodium acetate 47.5

Example 13

The active component below was used to prepare a granular preparation in a solvent.

13 618 583

tel dissolved and the liquid obtained sprayed onto granular china clay, after which the solvent was evaporated, so that a preparation of the following weight composition resulted.

5

% By weight

5 95

Example 14

A preparation suitable for the treatment of seeds was prepared by mixing the following components in the stated proportions.

% By weight

50 2 48

25th

Example 15

A powdery preparation suitable for atomization was prepared by mixing the active component specified below with talc in the specified proportions.

% By weight

5

95

Example 16

A surface-adhering liquid preparation was prepared by grinding the components listed below in the proportions indicated in a ball mill and suspending the resulting mixture in water.

% By weight

40 10 1

Example 17

55 A dispersible, powdery preparation was prepared by mixing the components listed below in the proportions indicated and grinding the mixture until thoroughly mixed.

60

% By weight

25 2 5 28 40

2- (imidazol-l-yl) -2-n-butyl-4'-chloroacetophenone 10 quinaclay granules

2- (imidazol-l-yl) -2-n-butyl-4'-chloro-35 acetophenone talc

2- (imidazol-l-yl) -2-n-butyl-4'-chloroacetophenone 65 "Aerosol" OT / B "Dispersol" A.C.

Chinaclay silicon dioxide

2 2- (imidazol-l-yl) -2-t-butyl-4'-chloroacetophenone mineral oil Chinaclay

2- (imidazol-l-yl) -2-n-butyl-4'-chloroacetophenone 50 "Dispersol"

"Lubrol"

618 583

14

Example 18

A dispersible, powdered preparation was prepared by mixing the components listed below in the proportions indicated and grinding the mixture until thoroughly mixed.

% By weight

2- (imidazol-l-yl) -2-t-butyl-4'-chloro

acetophenone

25th

"PERMINAL" BX

1

"Dispersol" T

5

Polyvinyl pyrrolidone

10th

Silicon dioxide

25th

Chinaclay

34

10th

Example 19

A dispersible, powdered preparation was prepared by mixing the components listed below in the proportions indicated and grinding the mixture until thoroughly mixed.

% By weight

2- (Imidazol-l-yl) -2-n-butyl-4'-chloroacetophenone "Aerosol" OT / B "Dispersol" A Chinaclay

25 2 5

68

Below are explanatory notes related to the tools listed in the examples under your trademarks:

"Lubrol" L

"Aromasol" H

"Dispersol" T and AC

"Lubrol" APN 5

"Cellofas" B600

"Lissapol" NX

"Aerosol" OT / B "Perminal" BX

Example 20

The effect of the triazole derivatives as an active component of the agent according to the invention was tested against a number of different fungal diseases of the foliage of plants. For the test, the foliage of infected or non-infected plants was sprayed with a solution which contained 100 ppm (parts by weight / million parts by weight) of the derivative to be tested, and the planting base of these plants was also impregnated with an identical solution.

Depending on the particular test, the plants were infected with the respective type of disease before or after treatment with the solution to be tested and then assessed depending on the type of disease after a number of days, the extent of the disease being determined visually and with a grade corresponding to below graduation.

The various types of disease and the plants used as test plants, the time in days between treatment and visual assessment and the code letters of the diseases are shown in Table 5 and the compounds tested according to the numbering in Table 1 and the results obtained are shown in Table 6.

graduation

Test grade

Extent of the disease

%

15

61-100 26-60 6-25 0-5 0

Table 5

a condensate of 1 mol nonylphenol and 13 mol ethylene oxide a solvent mixture of alkylbenzenes a mixture of sodium sulfate and a condensate of formaldehyde and sodium naphthalenesulfonate a condensate of 1 mol nonylphenol and 5.5 mol naphthalene oxide a sodium carboxymethyl cellulose thickener a condensate a sodium alkylnaphthalene sulfonate of 1 mole of nonylphenol and 8 moles of ethylene oxide dioctyl sodium sulfosuccinate

Disease type and test plant

Test duration

Code letter

25th

Days

the type of disease

1.

Puccinia recondita

wheat

10th

A

2nd

Phytophthora infestans

30th

tomatoes

3rd

B

3rd

Plasmopara biticola

Vines

7

C.

4th

Piriçularia oryzae

rice

7

D

35 5.

Botrytis cinerea

tomatoes

5

E

6.

Erysiphe graminis

barley

7

F

7.

Podosphaera leucotricha

40

Apple tree

7

G

Table 6

4S Ver

Disease type

binding A

B

C.

D

E

F

G

No.

1

2nd

0

2nd

3rd

4th

4th

50 2

0

0

-

1

0

0

2-3

3rd

0

0

-

0

p

0

1

4th

0

0

-

0

0

3-4

0-2

5

2-3

0

-

1-3

4th

4th

4th

6

3rd

0

-

0

1

3rd

-

55 7

0

0

-

0

0

3rd

-

8th

3rd

0

-

2nd

0

4th

-

9

0

0

-

0

0

3rd

-

10th

2nd

1

-

0

3rd

4th

-

11

1-3

1

-

1

0

3rd

-

60 12

0

2-3

-

0

0-2

4th

-

13

2nd

0

-

1

0

4th

-

14

1

0

-

0-1

2nd

3rd

-

15

3rd

0

-

0

0

4th

-

16

3rd

0

-

0

0

4th

_

65 17

0

0

-

0

0-1

3-4

-

18th

3rd

4th

-

-

3-4

3rd

-

19th

2nd

0

0

-

0

2-3

-

20th

4th

3rd

-

-

1-3

3rd

-

A

0

1

0

0

2nd

3rd

2nd

2nd

3rd

0

0

0

0

2nd

1

1

0

0

0

2nd

0

0

0

0

2nd

0

0

3rd

4th

0

0

0

0

0

0

0

0

4th

1

3rd

2nd

3rd

1

4th

0

0

0

1

4th

4th

4th

3rd

4th

4th

3rd

4th

3rd

4th

3rd

2nd

4th

15 618 583

Table 6 (continued) Table 6 (continued)

Disease type Ver disease type

D E F G bond A B C D E F G

-

-

2nd

1

4th

-

83 2 1

0

0 0

4th

-

-

0

1

3rd

-

84 0 0

0

0 0

3rd

-

-

0

0

2-3

-

85 4 1

0

0 0

4th

0

-

0

0

3rd

-

io 86 3 0

3rd

0 0

4th

0

-

0

0

4th

-

87 0 0

3rd

0 0

4th

2nd

2nd

0

0

4th

-

88 4 3

0

0 0

4th

4th

3rd

2nd

1

4th

-

89 3 0

0

1 1

4th

0

4th

0

0

4th

-

90 3 1

0

1

- -

0

4th

-

0

4th

-

15 91 1 0

0

2 0

- -

1

0

3rd

0

2nd

-

92 3 3

1

3 3

4th

0

0

3rd

0

3rd

-

93

-

-

3rd

1

3rd

0

2nd

-

94

2nd

4th

0

0

0

2nd

3rd

-

95 1 0

0

1 0

4th

2nd

0

1

3rd

4th

-

20 96 1 0

1

1 0

4th

2nd

3rd

1

1

4th

97 0 0

0

1 0

4th

0

0

3rd

2nd

0

98

1

4th

1

0

3rd

1

4th

0

0

2nd

3rd

4th

Table 7

3rd

O

0 0

3rd

O

1

O

1

/ i

25 Effect of watering the root area compared to the

L

• 2

z 0

e.g.

4th

y |

Spray treatment against various types of powdery

0 0

4th

Powdery mildew with an interval of 2 days between

-

3 2

0

4 3

Treatment and infection of the test plants

3rd

0

3rd

3rd

3rd

30 Type of disease and type of

Assessment grade as a through

0

0

0

0

4th

treatment

cut from 3 test pots

0

0

0

0

4th

Use of 2- (l, 2,4-

1

0

0

0

4th

Triazol-l-yl) -2-n-butyl-4'-

0

0

0

0

4th

chloroacetophenone as active

1

0

0

0

4th

35

component

1

-

0

1

3rd

0

1

0

Concentration of active

1

O

A

Component m ppm

x

L

~

4th

50 25

10 5

0

-

0

0

4th

1 0 0

2 0

-

î

1

0 0 0 0 0

1 1

A

40 Podosphaera leucotricha

1

1 n

Spray treatment

4 4

3 1

1

3rd

0

1

4th

4th

A

Root impregnation Erysiphe graminis,

4 1

0 0

-

JL

4th

wheat

1 1 1 1

n

2 0 0 0

0 0 0 0

4th

A

45 spray treatment

0 0

0 0

Z

3 0

4th

4 4

Root impregnation Erysiphe graminis, barley

3 2

2 2

0 0 0

-

0 0 0

0 0 0

4th

/ I

Spray treatment of root impregnation

1 1

2 1

4 3

4 4

3 2

3rd

1

0

3rd

3rd

1

3rd

4th

Table 8

O

1

4th

Effect as a protective spray treatment against various

3rd

2nd

0

0

4th

55 types of powdery mildew and rotting diseases

1

0

0

4th

A

0

0

zi

Disease type

Assessment grade at Verwen

H*

formation of 2- (l, 2,4-triazole

1

0

-

2nd

4th

l-yl) -2-t-butyl-4'-chlorace-

2nd

-

0-2

2-3

4th

tophenon in a conc

1

2nd

3rd

1

'4

-

60

tration of 100 ppm for the

1

0

0

0

4th

-

protective spray treatment

0 0

0

1

0 0

2nd

4th

0

4th

-

Erysiphe graminis, wheat '

4th

0

0

1

1

4th

-

Podosphaera leucotricha

4th

0

0

0

3rd

4th

-

65 Botrytis cinerea

4th

0

0

0

4th

4th

-

Puccinia recondita

2-3 *

0

0

0

0

4th

-

1

3rd

0

0

4th

-

* in combination with root watering.

618 583

16

Tables 7 and 8 show that the triazole derivatives are particularly effective against a wide range of powdery mildew species and other diseases.

Table 9

Efficacy as root watering treatment against powdery

Powdery mildew on wheat and barley interval of 4 days between treatment and infection of the test plants. The evaluation grades are the average of 2 test pots

Tested active substance: «Ethirimol» *

2- (l, 2,4-triazol-l-yl) -2-n-butyl-

4'-chloroacetophenone

Application powdery mildew powdery mildew concentration, wheat barley wheat barley ppm

50

4th

4th

4th

4th

25th

4th

4th

3rd

3rd

12.5

3rd

4th

2nd

3rd

6.3

2.5

4th

1.5

2.5

3.1

1.0

3rd

0.5

0.5

* "Ethirimol" is Compound No. 30 in Table I of UK Patent 1,182,584.

From Table 9 it can be seen that the compound used as the active component in the application concentrations according to the invention, which are lower than the commercial agent, is the well-known pyrimidine fungicide according to GB-PS

Formula I with powdery mildew on wheat and barley at 30 1 182 584 gives better results.

According to the procedure described in Example 20, the effect of the imidazole derivatives as an active component was also tested in embodiments of the agents according to the invention against diseases of the foliage of plants. The types of disease used for the experiments correspond to

> iel 21

Code letters according to Table 5. Test plants, each 35 compounds tested as active components according to the numbering in Table 3 and their application concentration are summarized in Tables 10 and 11.

Table 10

Effect as root impregnation and spray treatment against different types of fungal diseases of the foliage 2-day interval between treatment and infection

Assessment grade active component 109 110 112 111

Connection no.

Disease type application concentration - 100 50 100 50 100 100

tration, ppm

Podosphaera leucotricha

3rd

2-3

3rd

3rd

2-3

-

Erysiphe graminis, wheat

4th

3-4

4th

3-4

2-3

3rd

Erysiphe graminis, barley

, 3rd

3rd

-

-

0

0

Puccinia recondita

3rd

2-3

3rd

3rd

0

-

Botrytis cinerea

3rd

0

3rd

1

0

0

Puccinia hordei

3rd

3rd

-

-

-

-

17th

618 583

Table 11

Connection no.

A

B

c

Disease type D

E

F

99

4th

0

0

0

3rd

3rd

100

3rd

0

0

1

3rd

4th

101

3rd

0

0

3rd

0

4th

102

3rd

0

3rd

1

0

4th

103

2nd

4th

104

2nd

4th

105

3rd

4th

106

1

4th

107

1

4th

108

4th

4th

109

3rd

0

0

0

3rd

3rd

110

2nd

0

0

0

3rd

4th

111

0

0

0

0

0

3rd

112

0

0

0

-

0

3rd

113 -

4th

0

-

0

4th

4th

114

0

0

-

0

3rd

4th

115

0

0

-

2nd

0

0

116

0

0

0

2nd

3rd

4th

117

1

0

0

1

3rd

1

118

3rd

0

0

3rd

4th

119

3rd

4th

Tables 10 and 11 show that the imidazole residues are effective in a wide range of fungal diseases of the foliage vate as an active component in the agent according to the invention in plants.

s

Claims (2)

618 583 2nd PATENT CLAIMS 1. Fungicidal agent, characterized in that it is at least one compound of the formula as an active component R x-ch-z- ^ ^ -r3 I. r r " r wherein R represents hydrogen or an optionally substituted hydrocarbon group, Z represents> C = O or a ketal, hydrazone, semicarbazone or oxime or represents> C = S, R1-R5, which may be the same or different, hydrogen, halogen, one optionally substituted hydrocarbon or hydrocarbonoxy group or a nitro or amino group, and X represents a group of the formula n — n— u (a) or N "V O (b) 9. Composition according to claim 1, characterized in that the compound of formula I 2-imidazole-1-yl-2-n-butyl-4'-chloroacetophenone, 2-imidazole-1-yl-2-n-butylacetophe -non, 2-imidazol-l-yl-2- (4-chlorobenzyl) -acetophenone, 2-imid-azol-l-yl-2-benzyl-4'-chloroacetophenone or a salt thereof. (I) 10th