DE2304584A1 - NEW PYRAZOLINE COMPOUNDS WITH INSECTICIDAL EFFECTIVENESS - Google Patents

Description

PHN. 6112 Ween / WG

Dipi.-Ing. HORST AUER

Applicant: iU. "." U / j ^ w-SFtSI

Akie: PH ¥ 6; 7

"New pyrazoline compounds with insecticidal activity"

It has been found that new pyrazoline compounds surprising biocidal effectiveness on arthropods such as mites, but especially insects, exercise.

These are compounds according to the formula below

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A = a phenyl group, a phenyl group substituted by 1 to 2 substituents, which substituents are selected from the group consisting of halogen atom, cyano group, alkyl group with 1-4 carbon atoms which is optionally substituted with halogen, cycloalkyl group, alkoxy group with 1 - ^ - carbon atoms, alkylthio group with 1-4 carbon atoms and amino group substituted with 1-2 alkyl groups, these alkyl groups contain 1-4 carbon atoms and together with the nitrogen atom of the amino group can form a closed ring in which a second made of sulfur atom, oxygen atom or Nitrogen atom selected heteroatom may be present, or a thienyl or pyridyl group, which can be substituted with a halogen atom or a lower alkyl group,
B = an hydrogen atom, a phenyl group, one with

1-3 substituent-substituted phenyl group, which substituents are selected from the group consisting of Halogen atom, alkoxy group with 1-4 carbon atoms, alkyl group with 1-4 carbon atoms and optionally substituted by halogen, cycloalkyl-thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4 carbon atoms, dioxyalkylene group with 1-4 carbon atoms and with 1-2 alkyl groups substituted amino group, which is alkyl

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groups each contain 1-4 carbon atoms and together with the nitrogen atom of the amino group can form a closed ring in which a second Heteroatom can be present,

or a furyl, pyrryl, thienyl or pyridyl group, those having a halogen atom or a lower alkyl group can be substituted.

R _{1 is} a halogen atom, an alkoxy group with 1-4 carbon atoms, alkyl group with 1-4 carbon atoms and optionally substituted by halogen, cycloalkyl group ", thioalkyl group with 1-4 carbon atoms ^ sulfonylalkyl group with 1-4 carbon atoms, cyano group, nitro group or · with 1- 2 alkyl groups substituted amino group, which alkyl groups together with the nitrogen atom of the amino group can form a ring in which a second hetero atom can be present,

η has the value 1 or 2.

It should be noted that when A represents a second substituent-containing phenyl group, the Substituents not the 2,6-positions of the phenyl group are allowed to take. It is also true that (R ..) is not a 2,6-substituent may be.

The biocidal effectiveness of the new compounds according to the invention was found in a biological evaluation study in which test solutions and Test suspensions of the active ingredients for biocidal effectiveness in relation to u.e. Leptinotarsa decemlineata, Pieris brassicae, Aedes egypti, Delia brassicae, Musca

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domestica, pliylloscoptrata oleivora, periplane ta, atiefioa ^ k *. * ->, Hpteroptera dp, and -Apftidldae sp. .are checked.

The active ingredients are at various concentrations between 1000 mg per liter of test liquid and 1 mg of active ingredient tested per liter of test liquid. For example, when testing for effectiveness in relation to beetles, Larvae of beetles, caterpillars, maggots and mosquito larvae assumed a concentration of 100 mg active ingredient per liter, after which, depending on the activity found, the concentration successively to 30, 10, 3 and 1 mg active ingredients

P per liter of test liquid has been reduced. '

The results of this investigation show that the substances according to the invention have a satisfactory biocidal activity in relation to limb fluids and in particular in relation to insects. In this context it should be noted that the aforementioned Arthropoda (arthropod) sp. are not limiting. The inventive Substances are e.g. also effective against storage insects (Sitophilus granarius) and against insects that attack industrial products such as the carpet beetle (Attagenus piceus) and the real moth (Tineola bisselliela).

In particular, it was found that especially beetles, larvae and beetles, caterpillars, maggots and mosquito larvae very much are sensitive to the substances according to the invention. So the larva of the colorado beetle (Leptinotarsa decemlineata) can be successfully combated at concentrations of 3 to 30 ppm active ingredient.

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Surprisingly, it was found that the substances according to the invention are very special Have mechanism of action. In addition to a more direct one on the toxicity of the substances in relation to arthropods The basic biocidal effectiveness was further influencing the movement pattern of the treated Arthropods noted. The change brought about in movement pattern consists essentially in the fact that uncoordinated movements occur, which on the one hand in immobility of the treated insect and on the other hand a strong increase in the intensity of the Result in movement. The disturbed movement pattern has the consequence that the insect is no longer on the Can maintain leaf of plants; it falls off the leaf and is no longer able to take in food. It will also die as a result of dehydration.

The biological evaluation study also showed that, in particular, the compounds which correspond to the following formulas have a strong biocidal activity: I. Compounds of the formula:

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in the

R = a hydrogen atom, halogen atom, a cyano group, Alkoxy group with 1-4 carbon atoms or alkyl group with 1-4 carbon atoms,

B ¹ = a hydrogen atom, a phenyl group or phenyl group substituted with 1-3 substituents, which substituents. tuents are selected from the group consisting of halogen atom, alkoxy group with 1-4 carbon atoms and alkyl group with 1-4 carbon atoms,

R "= a halogen atom or an alkyl group with 1-4 carbon atoms,

m has the value 1 or 2, and η has the value 1 or 2,

with the proviso that (R) and (R ₂ ) are not 2,6-disub-

are stituents.

II. Compounds of the formula:

in the

2
R is a hydrogen atom, a halogen atom, a cyano group, an alkyl, alkoxy or thioalkyl group with 1 to 4 carbon atoms each, a cycloaJicyl group or an amino group substituted by 1-2 alkyl groups, the alkyl groups 1-4. Contain carbon atoms and together with the nitrogen

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atom of the amino group form a closed ring can, in which a second heteroatom can be present,

R is a substituent present in the para position, which is selected from the group consisting of halogen atom, alkyl group with 1 to 4 carbon atoms and optionally substituted with halogen, cycloalkyl group, thioalkyl group with 1 to 4 carbon atoms, sulfonylalkyl group with 1-4 carbon atoms, cyano group and with 1 -2 alkyl groups of substituted amino groups, which alkyl groups contain 1-4 carbon atoms and which together with the nitrogen atom of the amino group can form a closed ring in which a second hetero atom can be present,
or a 3 »** · dichloro substituent, and

X is a substituent in the para position selected from the group consisting of hydrogen atom, halogen atom, Alkyl group with 1-4 carbon atoms, cycloalkyl group, Alkoxy group with 1-4 carbon atoms and amino group substituted with 1-2 alkyl groups, which Alkyl groups contain 1-4 carbon atoms and together with the nitrogen atom of the amino group a closed one Can form ring in which a second heteroatom can be present.

or R "^ is a 2,4- or 3,4-disubstituent, where the Substituents are selected from halogen atom, lower alkyl group and dioxyalkylene group, or R is a 2,4,6-trihalo group,

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Ill

Compounds of the formula

in the

2 '

R has the aforementioned meaning, and

R is a 3,4-dichloro group or a substituent in Para-. position is selected from the group consisting of halogen atom, alkyl group with 1-4 carbon atoms, optionally substituted by halogen, cycloalkyl group, thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4 carbon atoms, cyano group, nitro group and with 1-2 Alkyl groups of substituted amino groups, which contain alkyl groups from 1 to 4 carbon atoms and can further form a closed ring together with the nitrogen atom.
IV compounds of the formula

in the

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_9 -

3
R represents a hydrogen atom, a halogen atom, a cyano group or

Is methoxy group,

B is a hydrogen atom, a phenyl group, 4-chlorophenyl group, 4-methoxyphenyl group or 2,4-dichlorophenyl group and ρ is 0 or 1.

Examples of highly effective substances according to the invention, which at a concentration of 3 to 10 ppm already complete mortality from leptinotarsa decemlineata or Pieris brassicae are mentioned below. With every substance there is also that Melting point indicated.

1. 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5-

(4-chlorophenyl) A -pyrazoline. Melting point 224 C.

2. 1- (4-sulfonylmethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - & -pyrazoline. Melting point I70 C.

3. 1- (4-sulfonylethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) -J & -pyrazoline. Melting point 150 ° C. h . X _r ( 4-chlorophenylcarbamoyl) -3- ( k- chi orphenyl) -5-

A. O

(4-isopropoxyphenyl) - ^ J -pyrazoline. Melting point 166 ° C.

5. 1- (4-t.Butylphenylcarbamoyl) -5- (4-chlorophenyl) -5- (4-chlorophenyl) - ^ -pyrazoline. Melting point 199 C.

6. 1- (4-n.Propylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - ^ -pyrazoline. Melting point 149 ° C.

7. 1- (4-Ethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - Δ -pyrazoline. Melting point 181 ° C.

8th . 1 - (4-Trifluoromethylphenylcarbamoyl) -3- (4-chloiptenyl) -5- (4-chloiptenyl) - Δ -pyrazoline. Melting point 206 C.

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9. 1 - (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-

fluororpheny 1) - ^ i -pyrazoline. Melting point I76 C.

10. 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-

ethylphenyl) & pyarazoline. Melting point 235 ° C.

11. 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5-

(4-t-butylphenyl) - Λ -pyrazoline. Melting point 222 ° C.

12. 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5-

(2-methyl-4-chlorophenyl) & pyrazoline. Melting point

184 ° C.

13 1- (4-chlorophenylcarbamoyl) -3- (4-dimethylaminophenyl) -5- (4-chlorophenyl) - Δ -pyrazoline. Melting point 23oC.

14. 1 - (4-Chlorophenylcabamoyl) -3 -. (4-chlorophenyl) -5- (2,4-dichlorophenyl) -Δ -pyrazoline. Melting point 166 C.. 15. 1- (4-Chlorophenylcarbamoyl) -3-phenyl-5- (4-methoxyphenyl) - Δ -pyrazoline. Melting point 164 C.

16. 1 - (4-Chlorophenylcarbamoyl) -3- (4-bromophenyl) -5-phenyl-

Δ -pyrazoline. Melting point 158 C.

17 1- (4-chlorophenylcarbamoyl) -3- (phenyl-5- (2,4-dichloro-

phenyl) - A -pyrazoline. Melting point 184 C.

18 .. 1- (4-chlorophenylcarbamoyl) -3-phenyl-5- (4-chlorophenyl) -

Δ -pyrazoline. Melting point 160 C.

19 · 1 - (3 f 4-dichlorophenylcarbamoyl) -3-phenyl-5- (4-methoxyphenyl) - Δ -pyrazoline. Melting point 170 ° C. 20. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5-phenyl- A -pyrazoline. Melting point 17 ^ C. 2Ί. 1- (4-chlorophenylcarbamoyl) -3- (4-cyanoph'enyl) -5-phenyl-

Δ -pyrazoline. Melting point 210 C.

22. 1- (3,4-Dichlorophenylcarbamoyl) -3- (4-cyanophenyl) -5-phenyl- Δ -pyrazoline. Melting point ΐ4θ C.

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23 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-methoxyphenyl) - ^ -pyrazoline. Mp 197 ° C.

24. 1 - (4-Chlorophenylcarbamoyl) -4- (4-chlorophenyl) -5- (4-i.propy! Phenyl) -ifl -pyrazoline. Melting point 190 C.

25. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4- n.propylphenyl) - Λ -pyrazoline. Melting point I78 C.

2.6 . 1 - (4-sulfonylbutylphenylcarbamoyl) - 3- (4-chlorophenyl) -5- (4th-butylphenyl) -4 -pyrazoline. Mp 191 ° C.

27. 1- (4-Iodophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - Δ -pyrazoline. Melting point 228 C.

28. 1- (4-Chlorophenylcarbamoyl) -3- (4-iodophenyl) -5- (4-chlorophenyl) -E -pyrazoline. Melting point 206 ° C.

29. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (5-chlorothienyl-2) - Δ -pyrazoline. Melting point 166 ° C.

30. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (furyl-2) -A -pyrazoline. Melting point 207 ° C.

31. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (3-methy1fury1-2) Δ -pyrazoline. Melting point 190 ° C.

32. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (5-methylthienyl-2) - Δ -pyrazoline. Melting point 154 ° C.

33. 1- (4-chlorophenylcarbamoyl) -3- (pyridyl-2) -5- (4-chlorophenyl) - A pyrazoline. Melting point 2O5 ° C.

34. 1- (4-chlorocarbamoyl) -3- (4-chlorophenyl) -5- (5-chlorofuryl-2) - Δ -pyrazoline. Melting point 195 ° C.

35. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (3,4-dioxymethylphenyl) - Δ -pyrazoline. Mp 193 ° C.

36. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-dimethylaminophenyl) - Δ -pyrazojin. Melting point 189 C.

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37 · 1- (4-chlorophenylcarbamoyl) -3-phenyl- Λ -pyrazoline. Melting point 148 ° C. 2

38. 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) - Δ -

pyrazoline. Melting point 175 C.

39. 1- (4-Ch.lorophenylcarbamoyl) -3- (4-fluorophenyl) - Δ ² -

4θ. 1- (4-chlorophenylcarbamoyl) -3- (4-bromophenyl) - Δ

pyrazoline. Melting point 150 ° C.

pyrazoline. Melting point 144 C. kl. 1- (4-iodophenylcarbamoyl) -3- (4-chlorophenyl) - Δ .. - pyrazoline. Melting point 162 C.

concentration camp. 1- (4-n.Propylphenylcarbamoyl) -3- (4-chlorophenyl) - Δ pyrazoline. Melting point 151 C.

43. 1- (3> 4-dichlorophenylcarbamoyl) -3-phenyl- Δ -pyrazoline "melting point 168 ° C.

44. 1- (3,4-dichlorophenylcarbamoyl) -3- (4-chloroph.enyl) - Δ pyrazoline. Melting point I87 C.

4-5. 1- (3, 4-dichlorophenylcarbamoyl) -3- (4-bromophenyl) - Λ

pyrazoline. Melting point 1 ° -2 ° C.

46. 1- (4-bromophenylcarbamoyl) -3- (4-chlorophenyl) - Δ -

pyrazoline. Melting point 181 C.

47. 1- (4-Chlorophenylcarbamoyl) -3- (4-isopropoxyphenyl) - Δ

pyrazoline. Melting point 141 ° C.

O
pyrazoline. Melting point 14q

48. 1- (4-Ethylphenylcarbamoyl) -3- (4-chlorophenyl -) - Δ

C.

49. 1- (4-ethylsulfonylcarbamoyl) -3- (4-chlorophenyl) - Δ pyrazoline. Melting point 187 C

50. 1- (4-Chlorophenylcarbamoyl) -3- (4-ethereallphenyl) - Δ pyrazoline. Melting point II6 C.

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51. 1- (4-chlorophenylcarbamoyl) -3 - (^ - isopropylph.enyl) -

pyrazoline. Melting point 131 C.

λ 2

52. 1- (4-Chlorophenylcarbamoyl) -3 - (^ - iodophenyl) - ^Δ

pyrazoline. Melting point I65 C.

53. 1- (4-.cyanophenylcarbamoyl) -3 - (^ - chlorophenyl) - ^ * pyrazoline. Melting point 210 C.

5 ^ 1- (4-nitrophenylcarbamoyl) -3 - (^ - chlorphenyl) - ^ -

pyrazoline. Melting point 225 C.

55 · 1 - (^ - chlorophenylcarbamoyl) -3- (4-dimethylaminophenyl) -

Λ -pyrazoline. Melting point 189 C.

Examples of substances according to the invention that are somewhat less active than the above compounds, are:

56. 1- (3> 4-dichlorophenylcarbamoyl) -3- (phenyl-5- (4-chloro * phenyl) - /! -pyrazoline. M.p. 182 ° C. 57 · 1- (3,4-Dichlorophenylcarbamoyl) -3- (4-chlorophenyl) -5-phenyl - "^ -pyrazoline. Melting point 188 C.

58. 1 - (.3, 4-dichlorophenylcarbamoyl) -3-phenyl-5- (2, 4-dichlorophenyl) - ^ -pyrazoline. Melting point 18 ° - ° C.

59. 1- (3,4-dichlorophenyl) -3-chlorophenyl) -5- (4-chlorophenyl) - -pyrazoline. Melting point 208 ° C.

60. 1- (4-Chlorophenylcarbamoyl) -3- (4-methoxyphenyl) -5-phenyl- & pyrazoline. Melting point 157 C.

61. 1- (3,4-dichlorophenylcarbamoyl) -3- (4-bromophenyl) -5-

phenyl-4-pyrazoline. Melting point 188 ° C.

/ -3- (3-methoxyphenyl

62.! - (^ - Chlorophenylcarbamoyiy-S-phenyl- ■ "2 -pyrazoline.

Melting point 1 ^ 5 C.

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63. 1 - (4-chlorophenylcarbamoyl) -3- (3-chlorophenyl) -5-phenyl-

-pyrazoline. Melting point I96 C.

64. 1- (3,4-dichlorophenylcarbamoyl) -3- (3-chlorophenyl) -5-phenyl- Δ -pyrazoline. Melting point 195 ° C. _r 65 · 1 - (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-n-butylphenyl) -Δ -pyrazoline. Melting point 154 ° C. 66. 1- (4-Fluorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-n-butylphenyl) - Δ -pyrazoline. Melting point 190 C. 67. 1 - (4-Methylphenylcarbamoyl) -3- (4-chlorophenyl ) -5 ~ ( ² ^ - η.butylphenyl) - Δ -pyrazoline. Melting point 220 ° C. 68. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (3-chlorophenyl) - * »-pyrazoline. Melting point 207 C · 69 . 1- (4-Chlorophenylcarbamoyl) -3 - (^ - thiomethylphenyl) -5-r (4-chlorophenyl) - " -pyrazoline. Melting point 188 C.

70. 1- ( kn. Butylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - ^ * -pyrazoline. Melting point I38 C.

71. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (2, k, 6-trichlorophenyl) - "-pyrazoline. Melting point 19I C.

72. 1- (4-Chlorophenylcarbamoyl) -3- ( k- 1.butylphenyl) -5- (4-chlorophenyl) -Δ -pyrazoline. Melting point 203 C.

73. 1- (4-thiomethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - ^ -pyrazoline. Melting point 19I C.

74. 1- (4-chlorophenylcarbamoyl) -3- (4-i.propoxyphenyl) -5- (4-chlorophenyl) - ^ -pyrazoline. Melting point 116 ° C.

75. 1- (4-Chlorophenylcarbamoyl) -3- (4-n-butylphenyl) -5- (4-chlorophenyl) - «-pyrazoline. Melting point 7 & C. 76. -1- (4-Chlorophenylcarbamoyl) -3- (4-bromophenyl) -5- (4-chlorophenyl) - & -pyrazoline. Melting point 219 C.

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77. 1- (4-butylphenylcarbanioyl) -3- (4-chlorophenyl) -5- (4-n. Butylphenyl) - Λ -pyrazoline. Melting point 135 C.

78. 1- (4-Chlorophenylcarbamoyl) -3- (4-ethylphenyl) -5- (4-chlorophenyl) -4 -pyrazoline. Melting point 2θ6 C.

79. 1_ (4-chlorophenylcarbamoyl) -3 - (^ - cyclohexylphenyl) -5- (4-chlorophenyl) ~ 4 -pyrazoline. Melting point 175 C.

80. 1- (4-chlorophenylcarbamoyl) -3- (4-t-butylphenyl) -5- (4-chlorophenyl) - ^ -pyrazoline. Melting point 2θ4 C.

81. 1- (2-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (i + _ _c hlorphenyl) - ^ pyrazoline. Melting point 225 ° C.

82. 1- (3-Chlorophenylcarbamoyl) -3- (^ -chlorophenyl) -5- ( ² ^ -chlorophenyl) - <4 -pyrazoline. Melting point 192 C.

83. 1- (2,4-dichlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - ^ -pyrazoline. Melting point 192 C.

84. 1- (4-Dimethylaminophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) -Λ -pyrazoline. Melting point 178 C

85. 1- (it-Clilophenylcarbamoyl) -3- (4-morfolinphenyl) -5- (4-chlorophenyl) - «-pyrazoline. Melting point 16O C.

86. 1- (4-chlorophenylcarbamoyl) -3- (4-piperidinphenyl) -5- (4-chlorophenyl) - ^ * -pyrazoline. Melting point 163 ° C.

87 1- (4-chlorophenylcarbamoyl) -3- (4-pyrazolidinephenyl) -5- (4-chlorophenyl) - ** -pyrazoline. Melting point 208 C.

88. 1- (4-Chlorophenylcarbamoyl) -3- (5-chlorothienyl) -5- (4-chlorophenyl) - A -pyrazoline. Melting point I96 C.

89. 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (2-pyrryl) - pyrazoline. ² Melting point 230 ° C.

90. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (pyridyl -3) - Δ -pyrazoline. Melting point 205 C.

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91. 1- (4-chlorophenylcarbamoyl) -3- (pyridyl-3) -5 - (^ - chloro-

phenyl) - ** -pyrazoline. Melting point 105 C.

92. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (pyridyl-2) - Δ -pyrazoline. Melting point 243 ° C.

93. 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-pyridyl) _ Ä pyrazoline. Melting point 239 ° C.

9k. 1- (4-Chlorophenylcarbamoyl) -3- (3 , 4-dimethoxyphenyl) -5- (4-chlorophenyl) - "-pyrazoline. Melting point 163 ° C.

95. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-methyl-pyrryl-2) - Δ -pyrazoline. Melting point 207 ° G.

96. 1- (3,4-dichlorophenylcarbamoyl) -3 - (^ - methoxyphenyl) - ^ -pyrazoline. Melting point 170 C.

97 x 1- (4-chlorophenylcarbamoyl) -3- (4-methoxyphenyl) - ^ pyrazoline. Melting point 132 C.

98. 1- (3 _i 4-dichlorophenylcarbamoyl) -3- (4-fluorophenyl) - ^ »parazoline. Melting point 162 C.

99. 1- (4-Chlorophenylcarbamoyl) -3- (3-methoxyphenyl) -A pyrazoline. Melting point 129 C.

100. 1- (3,4-dichlorophenylcarbamoyl) -3- (3-methoxyphenyl) - & pyrazoline. Melting point I36 C.

101. 1- (3,4-dichlorophenylcarbamoyl) -3- (3-chlorophenyl) - & ² -pyrazoline. Melting point 180 ° C.

102. 1- (4-Chlorophenylcarbamoyl) -3- (3-chlorophenyl) - ^ pyrazoline. Melting point Ιοί C.

103. 1- (4-Chlorophenylcarbamoyl) -3- (4-methylphenyl ¹ ) = ^ pyrazoline. Melting point 139 C.

104. 1- (4-methylphenylcarbamoyl) -3- (4-methylphenyl) - ^ pyrazoline. Melting point 159 C.

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105. 1- (4-methylphenylcarbamoyl) -3- (4-n-butylphenyl) -4 pyrazoline. Melting point 147 C.

106. 1- (4-methylphenylcarbamoyl) -3- (4-chlorophenyl) - ^ pyrazoline. Melting point 181 C.

107.1 - (4-sulfonylmethylphenylcarbamoyl) -3- (4-chloro-orphenyl) · " -pyrazoline. Melting point 225 C.

108. 1- (4-Chlorophenylcarbamoyl) -3- (4-n.propylphenyl) - Δ pyrazoline. Melting point 153 C.

109. 1- (4-n.butylphenylcarbamoyl) -3- (4-chlorophenyl) - A - pyrazoline. Melting point 134 C.

110. 1- (4-sulfonylethylphenylcarbamoyl) -3- (4-ethylphenyl) - Δ -pyrazoline. Melting point 172 C.

111. 1- (4-Chlorophenylcarbamoyl) -3- (4-thiomethylphenyI) - Λ pyrazoline. Melting point 154 C.

112. 1- (4-chlorophenylcarbamoyl) -3- (4-t-butylphenyl) - A -

pyrazoline. Melting point 150 C.

113. 1-Phenylcarbamoyl) -3-phenyl- ^ * -pyrazoline. Melting

point 16O C.

114. 1- (4-fluorophenylcarbamoyl) -3- (4-chlorophenyl) - aj -

pyrazoline. Melting point 173 C.

115 x 1- (4-fluorophenylcarbamoyl) -3-phenyl- Δ -pyrazoline.

Melting point 137 ° C.

116. 1- (4-t-butylphenylcarbamoyl) -3-phenyl- ^ -pyrazoline.

Melting point 146 ° C.

117 · 1- (4-n.Propylphenylcarbamoyl) -3-phenyl- Δ -pyrazoline.

Melting point 120 ° C.

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230A584

From the above list of 117 substances, those with the rank numbers 1 to 15 have Compounds are so potent that at a dose of 3 ppm and lower ' Already a complete or almost complete mortality of colorado beetle larvae and / or cabbage caterpillars is achieved. The connections with the ranking numbers have the same very high level of effectiveness 37— ^ 2 available. It was also found that the Substances that have a hydrogen atom in the fifth para position of the pyrazoline ring, like the substances with the rank numbers 37-55, although they may not be the most effective in greenhouse tests nevertheless show unexpectedly favorable results in the field. Interesting connections from of this group are the aforementioned substances with the rank numbers 37 - ^ - 2 as well as the compounds 47-51

Because of their insecticidal activity, the substances according to the invention can be used in the control of insects and plant parasitic mites that occur in arable and horticultural fields, such as caterpillars, Mosquito larvae, cockroaches, cycads, beetle larvae, especially the colorado beetle, Phyllocoptruta oleivora, as well as in the control of stock insects, such as Sitofilus granarius, and insects that produce industrial products, attack such as wood and textiles. Insects harmful to industrial products are e.g. Moth, carpet beetle, longhorn beetle and woodworm.

3 09833/1126

For practical use, the compounds according to the invention are processed into preparations. In these preparations, the active ingredient is mixed with a solid carrier material or dissolved or dispersed in a liquid carrier material, with H ^! Excipients, such as surface-active substances and stabilizers, can be added.

Examples of preparations according to the invention are aqueous solutions and dispersions, oil solutions and Oil dispersions, pastes, dust powder, spray powder, mixable oils, granules, invert emusions, aerosol preparations and smoke candles.

Wettable powders, pastes and mixable oils are preparations in concentrate form that can be used before or during the Use to be diluted with water.

The invert emulsions are mainly

Used for air application, especially when large surfaces be treated with a relatively small amount of the preparation. The invert emulsion can be just before or can even be produced during the spraying in the spray apparatus that water in an oil solution or an oil dispersion of the active ingredient is emulsified. For example, some forms of preparation are explained below explained.

Granular preparations are made by, for example, the active ingredient in a solvent added and the resulting solution in

309833/1 126

Presence of a binder on a granular Carrier material such as porous granules e.g. pumice and attaclay), mineral non-porous granules (sand or ground marl), organic granules (e.g. dried coffee grounds and cut tobacco stalks) is impregnated.

A granular preparation can also be used as a result be prepared that in the presence of lubricants and binders the active ingredient together with powdery Minerals are compressed and the compressed material is disintegrated to the desired grain size and sieved out.

Dust powder can be obtained by

that the active ingredient is intimately mixed with an inert solid carrier material, for example in a concentration of 1-50% by weight. Examples of suitable solid support materials include: talc, kaolin, pipe clay, diatomaceous earth, dolomite, gypsum, chalk, bentonite, attapulgite and colloidal SiO ₂ or mixtures of these and similar substances. Organic carrier materials, such as ground walnut shells, can also be used.

Spray powders are made by

that 10-80 parts by weight of a solid inert carrier, such as the aforementioned carrier materials, with 10-80 Parts by weight of the active ingredient, 1-5 parts by weight of a dispersant such as those known for this purpose Lignosulfonates or alkylnaphthalene sulfonates,

309833/1126

23Q4584

and preferably also with 0.5-5 parts by weight a wetting agent such as fatty alcohol sulfates, alkylarylsulfonates or fatty acid condensation products.

To produce miscible oils, the active compound dissolved in a suitable solvent, preferably poorly miscible with water or finely divided and an emulsifier is added to this solution. Suitable solvents are e.g. xylene, Toluene, petroleum distillates rich in aromatic compounds, e.g. solvent Naphtha, distilled tar oil, and mixtures of these liquids. As emulsifiers, e.g. alkylphenoxy polyglycol ethers, Polyoxyethylene sorbitan esters of fatty acids or PoXyoxyethylene sorbitan esters of fatty acids are used will. The concentration of the active compound in these miscible oils is not restricted to narrow limits and can vary, for example, between 2 and 50 wt. Except for a mixable oil, it can be used as a liquid and highly concentrated oil primary composition also a solution of the active ingredient in a well miscible with water Liquid, e.g. acetone, can be mentioned, which solution contains a dispersant and optionally a wetting agent are added, if diluted with water shortly before or during the spraying, then an aqueous Formed dispersion of the active ingredient.

An aerosol preparation according to the invention is obtained in a conventional manner in that the

309833/1126

Active ingredient, optionally in a solvent, in a volatile liquid to be used as a propellant gas, such as a mixture of chlorine-fluorine derivatives of methane and ethane is absorbed.

Smoke candles or smoke powder, i.e. preparations that can develop a pesticide smoke when burned, are obtained by turning the active ingredient into a flammable Mixture is absorbed, which e.g. as fuel a sugar or a wood, preferably in ground Form, a substance used to maintain combustion, such as ammonium nitrate or potassium chlorate, and more may contain a substance to retard combustion, e.g. kaolin, bentonite, and / or colloidal silica.

Except for the above items

The agents according to the invention can also contain other substances known for use in agents of this type.

For example, a lubricant such as calcium can be added to a wettable powder or a mixture to be granulated or magnesium stearate. Also e.g. "Adhesives" such as polyvinyl alcohol cellulose derivatives or other colloidal-like materials such as casein may be added to prevent the pesticidal composition from adhering to the surface to be protected.

In addition, pesticide compounds known per se can be incorporated into the preparations according to the invention will. This expands the range of action of the preparation and synergism can occur.

309833/1126

The following per se known insecticide, fungicide and acaricide compounds are suitable for use in such a combination preparation. Insecticides such as ;

1. chlorinated hydrocarbons, e.g. 2,2-bis-p-chlorophenyl) -1,1,1-trichloroethane and Hexachlorepoxy-octahydr ο dime thanonap ththa1en;

2. Carbamates, e.g., N-methyl-1-naphthyl carbamate: j

3. Dinitrophenols such as 2-methyl-4,6-dinitrophenol and 2- (2-butyl) -4,6-dinitrophenyl -3,3-dimethyl acrylate;

4. organic phosphorus compounds such as dimethyl 1-2-methoxycarbonyl-1-methyl vinyl phosphate; O, O-diethyl-O-p-nitrophenyl phosphorothioate; N-monomethylamide of 0,0-dimethyldithiophosphorylacetic acid;

Acaricides such as :

5 "diphenyl sulfides, for example p-chlorobenzyl, p-chlorophenyl sulfide and 2,4, k " -5-tetraphlodiphenyl sulfide;

6. Diphenyl sulfonates, such as p-chlorophenyl benzenesulfonate

7. methyl carbinols, e.g., 4,4-dichloro-α-trichloromethylbenzhydrol;

8. Quinoxaline compounds such as methylquinoxaline dithiocarbonate;

Fungicides such as ;

9. Organic mercury compounds, e.g. phenyl mercury acetate and methylmercury cyanoguanidj

10. organic tin compounds such as triphenyltin hydroxide and triphenyltin acetate;

309833/1126

11. Alkylene bisdithiocarbamates, e.g., zinc ethylene bisdithiocarbamate and manga ethylene bisdithiocarbamate;

12. and also 2,4-dinitro-6- (2-octylphenyl crotonate), 1-bis (dimethylamino) -phosphoryl-3-phenyl-5-amino-1 »2,4-triazole, 6-methylquinoxaline-2,3-dithiocarbonate,

1,4-dithioanthraquinone-2,3-dicarbonitrile, N. trichloromethylthiophthalimide, N-trichloromethylthiotetrabydrophthalimide,

N- (1, 1, 2,2-tetrachloroethylthio) -tetrahydrophthalimide, N-dichlorofluoromethylthio-N-phenyl ~ N'-dimethyIsulfonyl-

diamide and tetrachloroisophthalonitrile.

The one desired for practical use

Dosage of the preparation according to the invention is natural of various factors, such as the area of application, the selected active ingredient, the preparation form, the type and the size of the infection.

5kg of active will yield per hectare favorable results - for agricultural purposes, that in general a dosage equivalent to 0.5 applies.

The compounds of the invention are

new substances that are produced by processes known per se for the production of similar substances or by analogous processes Process can be produced. Thus, the compounds according to the invention can be prepared by that a compound of the formula

309833/1126

in which A and B have the aforementioned meaning with a "compound of the formula

N = C = O

in which R ₁ and η have the aforementioned meaning, is reacted, whereby a compound of the formula

H,

A-P HC'-B

is formed.

The reaction takes place in the presence of a

Solvent, such as an ether, e.g. diethyl ether, If desired, a catalyst such as an organic Base, e.g. triethylamine, can be added.

The starting materials of the above process can be obtained in two different ways . Thus, the starting materials can be produced using the following reactions:

309633/1126

& / CH

AC- CH ₃ + H ₂ C = O + ΗΝ /. HCl

Γ
0 CH ₂ - CH ₂ - < ^ CH ₃ + H ₂ O V
0 CH ₂ - CH ₂ •
HCl / T [T
^ CH ₃ + HN-N ^ CH ₃

A - -ΩΤΎμΐ + 2HO + (CH ")" NH. HCl

- H.

The second method of making the raw materials includes the reactions:

AC- CH "+ Nc = 0 B

A-C-Q = Q-B

Ar-C ₁ -C = GB + H ₂ N - NH ₂ .

H,

A -

.1: 1

The symbols used in the above reaction equations have the aforementioned meanings. The reaction indicated above with I takes place

SL

in the presence of a solvent such as an alcohol, e.g. ethanol. The reaction temperature is equal to the boiling point the solvent used. The reaction I, is also in a solvent such as ethanol, and at increased Temperature carried out. The above reaction II

309833 / 112S

is carried out in the presence of a solvent such as methanol at room temperature. The reaction environment is made alkaline by adding a base such as sodium hydroxide solution * Reaction II also takes place in the presence a solvent such as ethanol. The reaction temperature is equal to the boiling point of the solvent used.

The invention is explained in more detail below using a few exemplary embodiments.

1 · Preparation of 1- (3. H- dichlorophenylcarbamoyl) -3-pyrazoline pheiiyl- ^.

a_ Production of / 3 -Dimethylamino-propiophenone-

hydrochloride according to the formula

_ - CH ₉ - Ν '. HCl 2 Z \ ^

120 g acetophenone, 105 g dimethylamine hydrochloride and 39 »6 g of paraformaldehyde were concentrated along with 2 ml Hydrochloric acid and 16O ml of ethanol are placed in a 1 liter round bottom flask. After 2 hours Boiling, the solution obtained was filtered and diluted with 800 ml of acetone.

After standing at 0 C for 16 hours, the crystals formed were filtered off with suction, with 50 ml Acetone washed and dried.

309633/1126

The yield was 145 g of β- dimethylamino-propi.ophenone hydrochloride with a melting point of 155 C.

b Production of 3-Pb.enylder formula

-pyrazoline accordingly

-N-H

A mixture of 105 ml of 100% hydrain hydrate, 6 ° - ml of 40% sodium hydroxide solution and 150 ml of methanol was added at a temperature of 50 ° C. 1 ^ 5 g / 3 -dirnethylamino-propiophenone hydrochloride. The whole was boiled for an hour and after it was left to stand overnight, diluted with 350 ^m l of water.

The mixture was extracted three times with ether, after which the ether layer was washed three times with water. After drying on sodium sulfate, the mixture was distilled under nitrogen.

Yield 51 »5 S 3-phenyl-Δ pyrazoline mm with a boiling point 99- 1OO ° C / O; 5.

c_ Production of 1- (3> 4-dichlorophenylcarbamoyl)

-3-phenyl- Λ -pyrazoline according to the formula '

T - ^

3 O 9 8 3 3/1 1 1

16. Ο g of 3-phenyl- ^ -pyrazoliii were dissolved in 100 ml of ether. A solution of 20.4 g of 3,4-dichlorophenyl isocyanate in 200 ml of ether was then added dropwise with vigorous stirring and cooling. After this addition was completed, the reaction mixture was stirred for an additional 30 minutes. The precipitate formed was filtered off with suction, washed with ether and dried. After recrystallization from acetonitrile, 22 g of 1- (3> 4-dichlorophenylcarbamoyl) -3-phenyl- Δ- pyrazoline with a melting point of 168-169 ° C. were obtained.

In exactly the same way as described above, the substances indicated with the rank numbers 37-55 and 98-120 were prepared according to the invention. 2. Preparation of 1- (4-chlorophenylcarbamoyl) -3- (4-chloro-

phenyl) -5- (4-chlorophenyl) - Δ -pyrazoline . for the production of h, h '-dichlorochalcone according to the formula:

- CH = CH

30.9 g of 4-chloroacetophenone and 28.1 g of 4-chlorobenzaldehyde were dissolved in 200 ml of methanol.

While cooling to 20 ° C., 30 ml of 2N sodium hydroxide solution were added dropwise with stirring. After stirring for 2 hours, open 200 ml of water were added at 20 ° C. and the precipitate formed was filtered off with suction. The precipitate was with Washed water, then dried and again, now with

309833/1126

Washed petroleum ether (40: 6o). The yield was 52.0 g k, 4'-Dichlorchalkon having a melting point of 151-153 ^O C.

b Preparation of 3- (4-chlorophenyl) -5- (4-chlorophenyl) - Δ -pyrazoline according to the formula:

13.8 g 4,4'-dichloro chalcone and 5 ml 100% hydrazine hydrate were dissolved in 50 ml of ethanol and for one hour cooked. Then the alcohol was distilled off. The residue was cooled and treated with water. The precipitate formed was filtered off with suction, washed with water, in ml of ether taken up and then dried over sodium sulfate under nitrogen.

c) Preparation of 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - Δ -pyrazoline according to the formula

An ethereal solution of 7.6 g of 4-chlorophenyl isocyanate was added dropwise with stirring to the precipitate obtained under b_. 5 drops were used as a catalyst

309033/1126

Triethylamine added. The white precipitate obtained was dried. The yield was 18.4 g * 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) -

-pyrazoline with a melting point of 222-224 C. In the same manner as described above, the with the rank numbers 1-36 and 56-97 specified substances manufactured according to the invention.

3. Of the active ingredients according to the invention

Wettable powder made by having 25 parts by weight of the active ingredient with 3 parts by weight of calcium lignosulfonate, 2 parts by weight of dibutylnaphthalene sulfonate and 70 parts by weight of kaolin are mixed.

k. Of the active ingredients according to the invention

liquid concentrates produced by dissolving 10 parts by weight of the active ingredient in dimethylformamide, to which a little cyclohexanone can optionally be added, after which the resulting solution-6-7 parts by weight of an emulsifier s, such as a mixture of nonylphenol polyglycol ether and alkaline earth alkylbenzenesulfonate, may be added. 5 · The active ingredients according to the invention are in

Water dispersed in concentrations of 100, 30, 10, 3 and 1 mg of the active ingredient per liter of aqueous dispersion. Cut stems from potato plants are cut up to drain with an aqueous dispersion of the substance to be examined and then sprayed in with tap water filled bottles housed. After the plants have dried, perspex cylinders are made around the plants

309833/1126

appropriate. The plants are then with

five larvae of Leptionotarsa decemlineata (colorado beetle) infected. The cylinders are covered with a gauze and kept at a temperature of 2k C and a relative humidity

Stored from $ 60-70.

After 5 days, the mortality percentage of the larvae is established. Each attempt is carried out in triplicate.

The results of the experiments are shown below

Given in the table. The symbols used in the table

have the following meaning:

+ = $ 90--100 mortality + = $ 50-90 mortality and - = less than $ 50 mortality.

309833/1126

TABLE of biocidal activity on larvae of Leptionotarsa decemlineata

link Biocidal activity
7th 30th + + 10 3 + 1 O) Rank number as above Concentration in mg active ingredient per liter (PPM) + + + . + + ⁺ - mentioned 100 + + + - 1. ₊ + + + - 2 + + + + + 3 + + ⁺ - ₊ 4th + + + - 5
6th ₊ . + + '+ _± 7th + + + + - 8th + + + + 230A 9 + - 584 ι 10 + + 11 ⁺ . + + - 12th + - 13th 14th * 15th
16
17th 18th
19th

link Biocidal activity 30th 10 3 1 - - Rank as above Concentration in mg active ingredient per liter (PPM) _± ■ + _± - mentioned 100 + + - - 20th + + + - ■ - 21 + + + - 22nd + + + _± - 23 + + + + ' 2k + + 25th + + + - - 27 + + + + 28 + + + - - 29 + + + ■ + 30th + + + - 31 + ^{+ +} - 32 + + + 33 ⁺ + + 35 + + + + 36 + + + + 37 + + +. + 38 + ^{+ +} 39 + 40 ⁺

CD OO Ca> CO

link Biocidal activity 30th 10 3 + 1 M. Rank number as above Concentration in mg active ingredient per liter (PPM) + + + mentioned 100 + + + _ 41 + + + _ + - 42 + + + - 43 + + + - 44 + + + - 45 + + + _ - 46 + + + - 47 + + + - 48 + ' + + _ - 49 + + + - 50 + + + 51 + + + 52 + + + 53 + + + 54 + + _ - - 55 + + _ + _ - 56 + _ + + _ 51 + + - 58 + + + _ 59 + 60 +

ca ο co

Link Biocidal activity 30th 10 3 1 Rank number as above Concentration in mg active ingredient per liter (PPM) _{+ +} mentioned 100 - 61 ₊ - 62 + - 63 + + - 6k + + _± 65 + + + _± 66 + _± - 61 + · + - 68 + i - 69 + i - 70 + - 71 + - 72 + 73 ⁺ _± - 75 + + • + - 76 + - 78 + ⁺ - 19th . 80 ⁺

link Biocidal activity '100 30th 10 * ± 3 1 Rank number as above Concentration in mg active ingredient per liter (PPM) + mentioned + + _± • + + + 86 + + - 87 + + + - 88 + + ± - 89 + - 90 + + - 91 + + - 92 93 + + + 9h + + + - 95 . + + - 96 + + + - 97 + + - 98 + - 99 + - 100 + + 101 ^{+ +} 102 103

co OO Ca>

(O

link Biocidal activity 100 30th 10 3 • - 1 Rank number as above Concentration in mg active ingredient per liter (PPM) + _ - - mentioned + + + _ 105 + + 106 + + - 107 + + - 108 + + - 109 + + - 110 + + - 111 + 112 + + 113 + + IU + + + 115 + + + 116 117

OQ

CO CD

cn co

Claims (1)

Patent claims : ( ^R 1> n in which the symbols have the following meanings: A = a phenyl group, one substituted with 1-2 substituents Phenyl group, which substituents from the Are selected from the group consisting of halogen atom, cyano group, alkyl group with 1-4 carbon atoms and given- · if substituted by halogen, cycloalkyl group, alkoxy group with 1-4 carbon atoms, alkylthio group with 1-4 carbon atoms and with 1-2 alkyl groups Substituted 'amino group, which alkyl groups Contains 1-4 carbon atoms and together with the Nitrogen atom of the amino group can form a closed ring, in which a second made of sulfur atom, Oxygen atom or nitrogen atom selected atom is present may be, or A is a thienyl or pyridyl group substituted with a halogen atom or a lower Alkyl group can be substituted, B = a hydrogen atom, a phenyl group, with 1-3 Substituent substituted phenyl group, which substituents are selected from the group consisting of halogen 309833/1126 atom, alkoxy group with 1-4 carbon atoms, alkyl group with 1-4 carbon atoms and optionally substituted with halogen, cycloalkyl group, thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4 carbon atoms, dioxyalkylene group with 1-4 carbon atoms and substituted with 1-2 alkyl group Amino group, which alkyl groups each contain 1 - 4 carbon atoms and together with the nitrogen atom of the amino group can form a closed ring in which a second heteroatom can be present, or B is a furyl, pyrryl, thienyl or pyridyl group, which with a halogen atom or a lower alkyl group, R ₁ = a halogen atom, an alkoxy group with 1-4 carbon atoms, alkyl group with 1-4 carbon atoms and optionally substituted with halogen, cycloalkyl group, thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4 Carbon atoms, cyano group, nitro group or with 1-2 alkyl groups see below Substituted amino group, which alkyl groups together with the nitrogen atom of the amino group can form a ring in which a second hetero atom can be present,
η has ¥ ert 1 or 2, with the proviso that if A represents a phenyl group containing 2 substituents, the substituents must not occupy the 2,6-positions of the phenyl group, and further that (R ₁ ) must not be a 2,6-disubstituent. 309833/1126 Compounds of the formula in the R ¹ = a hydrogen atom, halogen atom, cyano group, alkoxy group with 1-4 carbon atoms or alkyl group with 1-4 carbon atoms, B ¹ = a hydrogen atom, a phenyl group or phenyl group substituted with 1-3 substituents, which substituents are selected from the group consisting of halogen atom, alkoxy group with 1-4 carbon atoms and alkyl group with 1-4 carbon atoms, Rp == a halogen atom or an alkyl group with 1-4 carbon atoms, m has the value 1 or 2 and η has the value 1 or 2, with the proviso that (R ¹ ) and (l are substituted.
3. Compounds of the formula no 2,6-di- in the O H 309833/1126 2
R = a hydrogen atom, halogen atom, cyano group, alkyl, alkoxy or thioalkyl group with 1 - 4 carbon atoms, cycloalkyl group or amino group substituted with 1 - 2 alkyl groups, the alkyl groups containing 1 - 4 carbon atoms and, together with the nitrogen atom of the amino group, a closed one Can form a ring in which a second heteroatom can be present, 3
R = a substituent present in the para position, which is selected from the group consisting of halogen atom, alkyl group with 1-4 carbon atoms, optionally substituted with halogen, cycloalkyl group, thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4 carbon atoms, cyano group and with 1 -2 alkyl groups of substituted amino groups, which alkyl groups each contain 1-4 carbon atoms and together with the nitrogen atom of the amino group can form a closed ring in which a second hetero atom can be present, or R is a y-, 4-dichloro substituent, and X = a substituent present in the para position which is selected from the group consisting of hydrogen atom, halogen atom, alkyl group with 1-4 carbon atoms, cycloalkyl group, alkoxy group with 1-4 carbon atoms and amino group substituted with 1-2 alkyl groups, which alkyl groups each contain 1-4 carbon atoms and, together with the nitrogen atom of the amino group, can form a closed ring in which a second hetero- 309833/1126 atom can be present, or X is a 2,4- or 3> 4-disubstituent, which substituents are selected from halogen atom, lower alkyl group and dioxyalkylene group or X is a 2,4,6-trihalo group. 4. Compounds of the formula HC-H
-NCN V in the 2
R has the meaning mentioned in claim 3, and R = a 3 »4-dichloro group or a substituent in para position, which is selected from the group consisting of halogen atom, alkyl group with 1-4 carbon atoms, optionally substituted with halogen, cycloalkyl group, thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1- 4 carbon atoms, cyano group, nitro group and amino group substituted by 1-2 alkyl groups, which alkyl group each contain 1-4 carbon atoms and can further form a closed ring together with the nitrogen atom of the amino group, in which a second hetero atom can be present.
5 · Compounds of the formula 309833/1126 \ V_C1 (ci) _p in the 3
R = a hydrogen atom, halogen atom, a cyano group or Methoxy group, B = a hydrogen atom, a phenyl group, a 4-chlorophenyl group, 4-methoxyphenyl group or 2,4-dichlorophenyl group, and ρ is 0 or 1. 6. 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - ^ -pyrazoline. 7. 1- (4-Sulphonylmethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - Δ -pyrazoline. 8. 1- (4-Sulphonylethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - Δ -pyrazoline. 9. 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-isopropoxyphenyl) - Δ -pyrazoline, 10. 1- (4-t.Butylphenylcabamoyl) -3- (4-chlorophenyl) -j _v x - ^^^ - ^^^^^ üj. jy- -pyrazoline. 1 1. 1- (4-n-propylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - - ^ -pyrazoline. 12. 1- (4-Ethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - ** -pyrazoline. 13. 1- (4-Trifluoromethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - Λ -pyrazoline. 14. 1- (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-fluorophenyl) - Δ -pyrazoline. 309833/1126 15. 1 - (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) A P -5- (4-ethylphenyl) - pyrazoline. 16. 1 - (4-Chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-1.butylphenyl) - ^ * -pyrazoline. 17 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (2-methyl-4-chlorophenyl) -4-pyrazoline. 18. 1- (4-chlorophenylcarbamoyl) -3- (4-dimethyl- aminophenyl) -5- (4-chlorophenyl) - Δ -pyrazoline. 19 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (2,4-dichlorophenyl) - «-pyrazoline. 20. 1- (4-Chlorophenylcarbamoyl) -3-phenyl-5- (4-methoxyphenyl) - Δ -pyrazoline. 21. 1- (4-Chlorophenylcarbamoyl) -3-phenyl- ^ ² -pyrazoline. 22. 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) - -pyrazoline. 23. 1- (4-chlorophenylcarbamoyl) -3- (4-fluorophenyl) - ^ -pyrazoline. 24. 1- (4-chlorophenylcarbamoyl) -3- (4-bromophenyl) - A pyrazoline. 25. 1- (4-Iodophenylcarbamoyl) -3- (4-chlorophenyl) _ 4 -pyrazoline. 26. 1- (4-Propylphenylcarbamoyl) -3- (4-chlorophenyl) Δ -pyrazoline. 27. 1- (4-Chlorophenylcarbamoyl) -3- (4-isopropoxyphenyl) - Δ -pyrazoline. 28. 1- (4-Ethylphenylcarbamoyl) -3- (4-chlorophenyl) -pyrazolxn. 29. 1- (4-Ethylsulphonylphenylcarbamoyl) -3- (4-chlorophenyl) - Δ ² -pyrazoline. 309833/1128 ι *
30.. 1- (4-chlorophenylcarbamoyl) -3- (4-ethylphenyl) - A 2 _Ί . * ^J -pyrazolm. 31. 1- (4-chlorophenylcarbamoyl) -3- (4-isopropyl- phenyl) - "-pyrazoline. 32. Process for making compounds the general formula H A- in the A = a phenyl group, one substituted with 1-2 substituents Phenyl group, which substituents are selected from the group consisting of halogen atom, cyano group, alkyl group having 1 carbon atom and optionally substituted by halogen, cycloalkyl group, alkoxy group with 1-4 carbon atoms, Alkylthio group with 1-4 carbon atoms and with 1-2 Alkyl group of substituted amino group, which alkyl group each contain 1 - 4 carbon atoms and together can form a closed ring with the nitrogen atom of the amino group, in which a second made of sulfur atom, Oxygen atom or nitrogen atom selected atom may be present, or A is a thienyl group or pyridyl group with a halogen atom or a lower alkyl group can be substituted, B = a hydrogen atom, a phenyl group, one with 1-3 309833/1126 Substituent substituted phenyl group, which substituents are selected from the group consisting of halogen atom, alkoxy group having 1-4 carbon atoms, alkyl group with 1 - 4 carbon atoms and optionally substituted by halogen, cycloalkyl group, thioalkyl group with 1 - 4 carbon atoms, sulphonylalkyl group with 1-4 carbon atoms, dioalkylene group with 1-4 Carbon atoms and substituted with 1-2 alkyl groups Amino group, which alkyl groups contain 1-4 carbon atoms and together with the Nitrogen atom of the amino group is a closed ring can form, in which a second heteroatom can be present, or B is a furyl, pyrryl, thienyl or pyridyl groups which may be substituted with a halogen atom or a lower alkyl group; R ₁ = a halogen atom, an alkoxy group with 1-4 carbon atoms, alkyl group with 1-4 carbon atoms and optionally substituted by halogen, cycloalkyl group, thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4 carbon atoms, cyano group, nitro group or with 1- 2 alkyl groups substituted amino group, which alkyl groups together with the nitrogen atom of the amino group can form a ring in which a second hetero atom can be present, η has the value 1 or 2, with the proviso that if A represents a phenyl group containing 2 substituents, the substituents may not occupy the 2,6-positions of the phenyl groups, and further that (Ri) _{11 may} not be a 2,6-substituent, 309833/1 1 28 characterized in that the substances are manufactured by such substances known processes or processes analogous to these processes are produced. 33 · Method according to Ansoruch 32, characterized in that that the compounds are prepared in that a compound of the formula A-C HC-B Ü— ~ N - H in which A and B have the meaning mentioned in claim 32, with a compound of the formula: .N = C = O in which R ₁ and η have the meaning mentioned in claim 32, is reacted, whereby a compound of the formula A-C HC-B N-N-G- is blared. 34.Biocidal preparation for combating limb feet, characterized in that the preparation next to a solid or liquid inert carrier material, a compound of the formula below as an active ingredient contains: ^Η Λ A - C HC-B N- - - N - C - N 1 / V (R ₁ ) in what formula A = a phenyl group, one substituted with 1-2 substituents Phenyl group, which substituents are selected from the group consisting of halogen atom, cyano group, alkyl group with 1-4 carbon atoms and optionally with halogen substituted, cycloalkyl group, alkoxy group with 1-4 carbon atoms, alkylthio group with 1-4 carbon atoms and amino groups substituted with 1-2 alkyl groups, which alkyl groups contain 1 - 4 carbon atoms each and, together with the nitrogen atom of the amino group, can form a closed ring in which a second heteroatom selected from sulfur atom, oxygen atom or nitrogen atom may be present, or A. is a thienyl or pyridyl group which may be substituted with a halogen atom or a lower alkyl group, 3Ö9833 / 1126 so so- B s is a hydrogen atom, a phenyl group, a phenyl group substituted by 1-3 substituents, which substituents are selected from the group consisting of halogen atom, alkoxy group with 1-4 carbon atoms, alkyl group with 1 · h carbon atoms and optionally substituted with halogen, cycloalkyl group , Thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4. Carbon atoms, dioxyalkylene group with 1-4 carbon atoms and amino group substituted with 1-2 alkyl groups, which alkyl groups each contain 1-4 carbon atoms and together with the nitrogen atom of the amino group can form a closed ring in which a second hetero atom can be present, or B is a furyl, pyrryl, thienyl or pyridyl group, which can be substituted with a halogen atom or a lower alkyl group, R ₁ = a halogen atom, an alkoxy group with 1-4 carbon atoms, an alkyl group with 1-4 carbon atoms and optionally substituted by halogen, cycloalkyl group, thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4 carbon atoms, cyano group, nitro group or with 1- 2 alkyl group substituted amino group, where the alkyl group together with the nitrogen atom of the amino group can form a ring in which a second hetero atom can be present, η has the value 1 or 2%: y. provided that when A represents a phenyl group containing 2 substituents, the substituents are not may occupy the 2,6 positions of the phenyl group and 309833/1126 further that (R-) must not be a 2,6-substituent. 35. Preparation according to claim 34, characterized in that that the active ingredient is a compound that of the formula 1 -L corresponds to, in the R ¹ = a hydrogen atom, a halogen atom, a cyano group, an alkoxy group with 1-4 carbon atoms or an alkyl group with 1 - 4 carbon atoms, B '= a hydrogen atom, a phenyl group or one with 1-3 Substituent substituted phenyl group, -relike substituents are selected from the group consisting of halogen atom, alkoxy group with 1-4 carbon atoms and alkyl group consists of 1-4 carbon atoms, m has the value 1 or 2 and η has the value 1 or 2 _E with the proviso that (R ^! ) and (P -.-,) are not 2,6-Di subsituents » 36, preparation according to Atispi-u.eii 34 _} characterized in that the · active 3sstar? .Citai.l sins "compound is that of the formula 3 \ _ L - I - C - N -ff V) 1 i ^ = ^ ³ corresponds to, in the 2
R = a hydrogen atom, halogen atom, cyano group, alkyl, alkoxy or thioalkyl group with 1 - 4 carbon atoms each, cycloalkyl group or an amino group substituted with 1-2 alkyl groups, the alkyl groups each containing 1 - 4 carbon atoms and together with the nitrogen atom Amino group can form a closed ring in which a second heteroatom can be present, 3
R = a substituent present in the para position, which is selected from the group consisting of halogen atom, alkyl group with 1 - 4 carbon atoms, optionally substituted by halogen, cycloalkyl group, thipalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4 carbon atoms, cyano group and with 1-2 alkyl groups of substituted amino groups, which alkyl groups each contain 1 carbon atom and, together with the nitrogen atom of the amino group, can form a closed ring in which a second hetero atom can be present, or R is a 3,4-dichloro substituent and X = a substituent present in the para position, which is selected from the group consisting of hydrogen atom, halogen atom, Alkyl group with 1-4 carbon atoms, cycloalkyl group, alkoxy group with 1-4 carbon atoms and with 1-2 309833/1126 Substituted amino group alkyl groups, which Alkylgruppei each contain 1 - 4 carbon atoms and together with the nitrogen atom of the amino group one can form closed ring, in which a second heteratom can be present, or X is a 2,4- or 3 »4 -disubstituent, where the Substituents are selected from halogen atom, lower alkyl group and dioxyalkylene group, or X is a 2,4,6-trihalo group. 37 · Preparation according to claim 34, characterized draws that the active ingredient is a compound that corresponds to the formula corresponds to, in the R has the meaning mentioned in claim 54, and R = a 3> 4-dichloro group or a substituent in para position which is selected from the group consisting of halogen atom, alkyl group with 1-4 carbon atoms, optionally substituted by halogen, cycloalkyl group, thioalkyl group having 1-4 carbon atoms, SuIfonylalkylgruppe having 1-4 carbon atoms, cyano group, nitro group and with 1-2 Alkylgruppai substituted amino group is, which alkyl groups each 1 - contain 4 carbon atoms and may form a closed ring with the nitrogen atom of the amino group in D is an _em 309833/1126 second heteroatom may be present. 38. Preparation according to claim 3 ^ 4 ', characterized in that that the active ingredient is a compound that of the formula corresponds to, in the 3
R = an hydrogen atom, a halogen atom, a cyano group or a methoxy group,
B = a hydrogen atom, a phenyl group, k- chlorophenyl group, 4-methoxyphenyl group or 2,4-dichlorophenyl group, and ρ has the value 0 or 1. 39 · Preparation according to claim 3 ^ -, characterized in that the active ingredient 1 - (^ - chlorophenylcarbamoylJ ^ -i ^ -chlorphenyl) -. 5- (^ -chlorphenyl) - & - pyrazoline. 40. Preparation according to claim 3 ^ »characterized in that the active ingredient 1- (4-sulfonylmethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - Δ - is pyrazoline. kl. Preparation according to claim 3 ^, - characterized in that the active ingredient is 1- (4-sulfonylethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) -1 \ pyrazoline. 309833/1126 42. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-chlorophenylcarbamoyl-5- (4-chlorophenyl) -5- (4-isopropoxyphenyl) - " is pyrazoline. 43. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-t.Butylphenyl- carbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - Δ - pyrazoline. 44. Preparation according to claim 34, characterized in that the active ingredient 1- (4-n.Propylphenylcarbamoyl) -5- (4-chlorophenyl) -5- (4-chlorophenyl) - ** is pyrazoline. 45. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-ethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - ^ pyrazoline is. 46. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-trifluoromethylphenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-chlorophenyl) - ^ * is pyrazoline. 47. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-fluorophenyl) - ^ pyrazoline is. 48. Preparation according to claim 34, characterized in that the active ingredient 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (4-ethylphenyl) - & - is pyrazoline. 49. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-chlorophenyl- 309833/1126 carbamoyl) -3- (4-chlorophenyl) -5- (4-t-butylphenyl) - Δ is pyrazoline. 50. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) -5- (2-methyl-4-chlorophenyl) - -pyrazoline is. 51. Preparation according to claim 54, characterized in that that the active ingredient 1- (4-chlorophenylcarbamoyl) -3- (4-dimethylaminophenyl) -5- (4-chlorophenyl) - -pyrazoline is. 52. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-chlorophenyl-, carbamoyl) -3- (4-chlorophenyl) -5- (2,4-dichlorophenyl) - ^ pyrazolinist. 53 · Preparation according to claim 34, characterized in that the active ingredient 1- (4-chlorophenyl- Λ? carbamoyl) - ^ - phenyl-5- (4-methoxyphenyl) - -pyrazoline. 54. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-chlorophenylcarbamoyl) -3-phenyl- ^ -pyrazoline is. 55 · Preparation according to claim 34, characterized in that the active ingredient is 1- (4-chlorophenylcarbamoyl) -3- (4-chlorophenyl) - £ -pyrazoline. 56. Preparation according to claim 34, characterized in that the active ingredient is 1- (4-chlorophenylcarbamoyl) -3- (4-fluorophenyl) - / 3 -pyrazoline. 30 9 833/1126 57— Preparation according to claim 34, characterized in that the active ingredient is 1- (4-chlorophenylcarbamoyl) -3- (4-bromophenyl) - -pyrazoline.
58. Preparation according to claim 34, characterized in that the active ingredient 1- (4-iodophenyl- A 2 carbamoyl) -3- (4-chlorophenyl) - ^A pyrazoline is. 59 · Preparation according to claim 34, characterized in that the active ingredient 1- (4-n-propylphenylcarbamoyl) -3- (4-chlorophenyl) - «-Pyrazoline is. 60. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-chlorophenylcarbamoyl) -3- (4-isopropoxyphenyl) - ^ -pyrazoline is. 61. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-ethylphenyl- Λ C ^ carbamoyl) -3- (4-chlorophenyl) - ^ -pyrazoline. 62. Preparation according to claim 34, characterized in that that the active ingredient 1- (4-ethylsulfonyl- A P phenylcarbamoyl) -3- (4-chlorophenyl) - ^ -pyrazoline. 63. ν preparation according to claim 34, characterized in that that the active ingredient 1- (4-chlorophenylcarbamoyl) -3- (4-ethylphenyl) - ^ -pyrazoline is. 64. Preparation according to claim 34, characterized in that the active ingredient is 1- (4-chlorophenylcarbamoyl) -3- (4-isopropylphenyl) - P -pyrazoline. 65. Preparation according to claim 34, characterized in that the preparation is also a different one per se known biocidal compound contains. 309833/1126 66. Process for the production of a biocidal preparation, characterized in that a compound the formula AC HC-B in the A = a phenyl group, one substituted with 1-2 substituents » tuated phenyl group, which substituents are selected from the group consisting of halogen atom, cyano group, alkyl group with 1-4 carbon atoms and optionally ind ± c halogen • substituted, cycloalkyl group, alkoxy group with 1-4 carbon atoms, alkylthio group with 1-4 carbon atoms and amino group substituted by 1-2 alkyl groups, which alkyl groups have 1-4 carbon atoms and can form a closed ring together with the nitrogen atom of the amino group, in to which a second heteroatom selected from a sulfur atom, an oxygen atom or a nitrogen atom may be present, or A is a thienyl or pyridyl group substituted with a halogen atom or a lower alkyl group could be, B = a hydrogen atom, an ffheroyl group, one with 1-3 Substituents! substituted phenyl group, which substituents are selected from the group consisting of halogen atom, alkoxy group with 1-4 carbon atoms, alkyl group ι with 309833/1126 1-4 carbon atoms and optionally substituted with halogen, cycloalkyl group, thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4 carbon atoms, dioxyalkylene group with 1-4 carbon atoms and amino group substituted by 1-2 alkyl groups, which alkyl groups each have 1-4 Contain carbon atoms and. together with the nitrogen atom the amino group can form a closed ring in which a second heteroatom can be present, or B is a furyl, pyrryl, thienyl or pyridyl group, which may be substituted with a halogen atom or a lower alkyl group, R = a halogen atom, an alkoxy group with 1-4 carbon atoms, Alkyl group with 1-4. Carbon atoms and optionally substituted by halogen, cycloalkyl group, thioalkyl group with 1-4 carbon atoms, sulfonylalkyl group with 1-4 carbon atoms, cyano group, nitro group or amino group substituted with 1-2 alkyl groups, wherein the alkyl groups together with the nitrogen atom of the amino group can form a ring in which a second Heteroatom can be present, η has the value 1 or 2, provided that when A is a phenyl group containing 2 substituents, the substituents are not the May take 2,6-i-para divisions of the phenyl group and further that (R ..) must not be a 2,6-substituent, 309833 / 112b with a solid or liquid inert carrier material is mixed, if desired auxiliaries or another biocidal compound already known per se was added will, 67 «Procedures for combating limb fluids in agriculture and horticulture, characterized in that the infected areas are treated with a preparation according to one of the preceding claims 34 to 65 in a dosage corresponding to 0.5-5 kg of active ingredient per hectare. 309833/1126