DD155030A1 - BIOZIDE MEDIUM - Google Patents

Abstract

The invention relates to biocidal agents with a wide range of applications. As active ingredient they contain substituted hexahydro-s-triazino (1,2-a) -benzimidazoles of the general formula in which R = an alkyl group having 1 to 12 C atoms, a cycloalkyl group, a phenyl radical which is optionally substituted by alkyl, halogen, Alkoxy, nitro, phenoxy or acetyl may be substituted, also a phen (C deep 1-C deep 4) alkyl or an alkoxyalkyl group having 1 to 4 carbon atoms.

Description

22 5 76 1 -4--

VEB OHEMIEKOMBINAiD BITTERFELD Bitterfeld, 27. 11. 1980

2043

Biocidal agent Field of application of the invention

The invention can be used to regulate metabolic and growth processes in balances, to influence the harmful organisms attack, furthermore to reduce the losses by insect feeding, to regulate the infestation flight or the invasion of pests into agricultural and horticultural crops.

Characteristic of the known technical solutions

It is known that it is possible to specifically intervene in the plant's metabolic and growth processes and to promote or inhibit the occurrence of pests by treating the plants with certain natural or artificial substances via their effects on the host plant; such effects have become known from chloroquine chloride, 2-chloroethanephosphonic acid, succinic acid dimethylhydrazide, benomyl and maleic hydrazide. Thus, EMDEN, HF (Nature, 1964, 201, S ₀ 946-948), HINZ, B. and DAEBELER, F. (Arch. Phytopathol., And Pflanzenschutz, 1973, H. 1, pp. 21-27), HONEYBORNE , 0. HB (J.Sea.Food Agric., 1969, 20, pp. 388-39O) and SMITH, BD (Nature, 1968, 212, pp. 643-644) and TAHORI, A. (J.

225761

2043

Be. Pood Agric. 1965 »16, 568-569, 570-572) noted the inhibitory effect of chlorocholine chloride on the development of aphids and Lepidopteran larvae while the use of maleic hydrazide was reported by ROBINSON, AG. (Ganad., 1960, 22, pp. 494-499) and SGHEUEER, S. (SYMP Biol. Hung., 1976, 16, pp. 255-259) leads to increased mortality in aphids. According to the communications of HINZ, B. and DAEBELER, F. (Arch. Phytopathol., And Pflanzenschutz 1973, H. 5, 337-339), ZIMMERMANN, G. (Ztschr. Pflanzenenkrankh., Pflanzenschutz 1976, 8, p. 261-269) and BAILISS, KW (Ann. Appl. Biology, 1978, p. 8, pp. 443-44-9), the use of benomyl elicits pest excitation inhibition, as exemplified by substituted benzimidazoles (DD-PS 142 279) became known in a similar manner. The work of RICHTER, S. (Arch. Phytopathol .. _o and crop protection 1977, 12., pp 127-136) and SOHEURER, S. (Symp Biol Hug 1976, 16>, pp 255-259) illustrate that by treating plants with 2-chloroethanephosphonic acid growth, weight and development of certain types of aphids can be promoted, while by the application of succinic acid dimethylhydrazide according to TAHORY, AS (J.Sep.Food, Agric., 1965, 16_, p 568 - 569) a corresponding inhibition can occur.

Artificial regulators of plant metabolism and growth can attack a wide variety of receptors and trigger different responses depending on the stage of development of the plant, the concentration and the mode of preparation of the active ingredient. This results in a variety of applications:

For example, in addition to general morphological changes in the plant, it is possible to control growth in length and thickness, as well as to influence vegetative and generative bud formation, flowering and sex determination

    - 3 - 2 2 5 7.6 1 2043

decisive influence on nutrient uptake, nutrient transport as well as on the formation of contents and storage materials of the plant are taken. The regulators are taken up by the plant, transported to the whereabouts of the pathogens, and act on their pathogens by their life processes such as mycelial growth, conidia formation, sporulation, virulence, reproduction rate, population density, growth and development, molting , Symbionts, feeding activity, hatching rate, etc.

On the other hand, they also attack the receptors of plant metabolism and development in such a way that the host plant, depending on the mode of administration, time of application, concentration and formulation of the active ingredient and the chemical composition of the ingredients of the PhIoemsaftes and due to an accelerated or delayed senescence temporal shifts in the Succession of their developmental sections learns. Such artificial regulators can be used to control the nutrient transport and the metabolic physiological processes which are expressed among others in a change in the chemical composition of contents and storage substances of the plant. As a result, the food supply to insects can be altered to achieve both less infestation and population dynamics bias. The host plant therefore no longer corresponds to the host pattern necessary for the individual pathogens.

Object of the invention

The aim of the invention is to develop new biocidal agents with a broader spectrum of activity. ·

-4- 225761 .204-3

, Explanation of the essence of the invention

This object is achieved in that the biocidal agent in addition to conventional excipients and carriers as active ingredient substituted hexahydro-s ~ triazino (1,2-a) benzimidazoles the general formula

COOGH,

in the

RS = an alkyl group having 1 to 12 C atoms, a cycloalkyl group, a phenyl radical which may optionally be substituted by alkyl, halogen, alkoxy, nitro, phenoxy or acetyl, furthermore a phen-C 1 -C 4 -alkyl radical or a Alkoxyalkyl group having 1 to 4 carbon atoms,

contain. The application rates may be 100 g to 6 kg of active ingredient per hectare, depending on the intended use.

The active compounds according to the invention can be prepared by known processes (for example DE-OS 2 224 244, DE-OS 2 308 067, DE-OS 2 356 258, US Pat. No. 3,896,120). ,

Benzimidazolyl-2-carbamic acid methyl ester is suspended in a low-boiling inert organic solvent and, after addition of a primary amine with 35% aqueous formaldehyde solution at 38 ⁰ C 40 his implemented.

The three-phase mixture is stirred at 38 to 40 ⁰ C for 2 hours and the hexahydro-s-triazino- (1,2-a) -benzimidazoles are isolated after working up of the mixture of the organic phase. The course of the reaction is formulated as follows:

225761

COOCH ₃

¹ V * -

H H -

COOCH ₃

Bine series of active compounds according to the invention are compiled in Table I.

2 ° table I; Srf indungsgemaße active substances of the general formula

COOCH ₃

R Mp ( ⁰ C)

C ₂ H ₅ 163-165

OH ₃ -CH ₂ -OH ₂ - 13ο - 139

CH-110 - 112

0-CH ₂ -CH ₂ -CH ₂ - 72-75

, -CH ₂ - 104 - 108

CH ₃

-CH ₀ - (JH-CH ₀ 142-145

Mr. R.

2 2 5 7 6 1

"PP ( ⁰ G)

2043

9 10

OH,

CH,

143 - 14-5

83 - 85

148 - 152

192-197

200 - 210 (Zers.)

non-distillable oil

J V> -0IL 192 "- 195

14 15 156 - 158

non-distillable oil

16

non-distillable oil

- / ^ - OCH, 145 - 146

No. R

2 5 7 6 1 2043

Pp. ( ⁰ C)

18

Supreme Court,

186-190

CH

155-158

20

I Cl

Cl

21

Cl

22

2 ₃

Cl

212 - 215

193-1998 193-196 168 .- 175

24

Cl

Cl

148 - 152

- β - 2 2 5 7 6 1 2043

No. R

, ( ⁰ )

25 -ff

160 - 162

26 Jf V) -COCH

150 - 155

J / \ 155 - 158

28

- / Ms 135 - 138

29 Jf \\ - GH

198 - 205

30

CH, 165-167

31 - // V

CH, 184-188

• -9- 225761 2043

No. R Fp. ( ⁰ G)

32 // \\ _ nrr 152 - 153

33 "OE ₀ - (J V". 143 - 146

2 2

34 -OH ₀ -OH ₀ - </ VV 140-145

35 - // 193-196

fo ₂

36 CH ₃ 162-165

The biocidal agents according to the invention are brought to the end in the form of solutions, emulsions, suspensions, powders, pastes or granules which are prepared in a known manner. The application forms must ensure a fine distribution of the active substance. The application can be made directly on the plant.

The compositions according to the invention in particular influence the side shoot formation, the flower formation and the growth, have a stabilizing effect on halts and retard the natural senescence of the plants. they lessen,

, * "- ίο - 2 2 5 7 6 1 2043

This is evidenced by the fact that on plants which were treated with the agents according to the invention before the plant sucker infestation, the aphids born on these host plants either die off in leafais also in root application or die Propagation rate compared to the control animals for a long time is reduced.

Such a high mortality or inhibition of growth, development and reproduction is also evident in eating insects.

In the following examples-in particular in the corresponding tables-the active ingredient numbers correspond to the data from Table I.

embodiments

Example 1: Cotyledon test of the cytokinin-analogous action of the agents according to the invention

From pre-germinated radish seeds cotyledons were removed and determined the fresh weight of 10 pieces. Subsequently, the cotyledons remained in the test solution under continuous light for several days before a new determination of the fresh weight took place. The differences between the starting weight and the final weight were determined. The values obtained were related to those of water control and kinetin. The results expressed as equivalent values were calculated as follows:

A =

Cotyledon weight in test solution - Koty1.-gew. in

aqua of the t.

Cotyledon weight in kinetin solution - Kotyl.-gew. in

dist.

If the equivalent value is 1, the substance tested corresponds in its effect to kinetin; if the value O,

  - 11 - 22 5 76 1

so the substance is ineffective.

Id Table II shows the cytokinin-analogous effects of the active compounds according to the invention.

Table II: Radish cotyledon test

Active ingredient no.

Conc.% By weight

equivalent value

.jj

-NHCOOOH,

10 "10"

+ 0.31 + 0.17

33. 9

3 5

11

26

24

10 "10 '

_O

10

10 '

, -2

+ 0.58 + 0.34

+ 0.39 + 0.85

10 - + 0.45 + 0.32 10 ~ ² + 0.43 10 ~ ² ΙΟ " ³ + 0.63 + 0.51 10 * " ² 10"" ³ + 0.52 + 0.35 10 "* ² 10 ~ ² + 0.48 + 0.47 + 0.49 10 ~ ² + 0.42

> 12 - 22 57 6 1 ₂₀₄₃ Active ingredient no. % Konz.Gew. equivalent value 22 20 35 10 ~ ² , 10 "* ² 10 ~ ³ + 0.85 "+ 0.44 + 0.38

Example 2: Sex determination and compression in cucumber Cucumber plants (Oucumis sativus) of the cultivar "Eva" cultivated in the greenhouse were applied in the 2-4 leaf stage with the test solution.

The number of female flowers and plant length was determined in relation to the control.

Table Uli sex determination and compression at cucumber

Active ingredient no. it ^ yXi Coz. ppm Number of female Flowers (in% for control) plant length (in% for control) (known) 100 500 1000 119 151 193 115 95 77 10 13 100 1000 10000 162 157 205 100 79 110 12 100 1000 10000 273 195 211 126 99 107 25 100 1000 10000 _ 257 265 223 103 101 129 20. 100 1000 10000 ^v 219 138 124 133 100 91 100 1000 10000 40 26 150 88 110 130

- 13 - JL Δ *> * Ό \ 2043

Active ingredient conc. Number v / eibl. Plant length No. ppm flowers (in % (in % to

for control) control)

114 119 115

100 128 1000 165 10000 131

Example 3 ^: Mortality of Aphis fabae Scop. on Vicia faba - studies on plant parts

Plant parts of Vicia faba were treated via the stem part base with the agents according to the invention in the concentrations 1000 ppm, 100 ppm, 10 ppm and 1 ppm. Subsequently, the colonization of each part of the plant with adult Aphis fabae, which settle on the previously treated parts of the plant expert. The dams were killed after 24 hours, while the mortality was determined in 50 offspring from 5 "to 5 days after the application

 The results are summarized in Table IV.

TABLE IV Effect of the agents of the invention on Aphis fabae Scop. on Vicia faba

Active Conc. 1000 ppm 100 ppm .10 ppm · 1 ppm

material - _: > -

No. Days ¹ D. d. Appl.

5 6 7 8 5 6 7 8 5 6 7 8 5 6 7 8

Control 0.0 2 3 - -.- * ---- - - «- -

Benomyl 100 100 100 100 100 100 100 100 82 84- 86 86 80 80 80 80

1 100 100 100 100 100 100 100 100 100 100 100 100 94 96 96 96

33 100 100 100 100 100 100 100 100 66 66 66 66 66 66 66 69 69 -λ

9 100 100 100 100 100 100 100 100 100 100 100 100 74- 76 76 76 ι

• . Λ

5 100 100 100 100 100 100 100 100 76 78 80 82 30 30 30 30

2 100 100 100 100 100 100 100 100 100 100 100 100 2 2 2.2

10 100 100 100 100 100 100 100 100 100 100 100 100 0 0 0 0 Ul

13 98 98 98 100 100 100 100 100 88 90 92 92 0-0 0 0 cn

11 100 100 100 100 - 100 100 100 100 52 52 52 52 22 2 8 10

12 100 100 100 100 100 100 100 100 41 4-1 41 4-1 2 2 4 6

25 100 100 100 100 100 100 100 100 60 64 64 64 0 0 0 0 ο

22 576 1

ιΗ Φ, Ω

lsi -P

S Pj

V *

O ν

R ¹ ft

ft

O O O

V "

οο.

CN VD

00

CN

VO

CO

VD

^! CO

ft CN

-ö VO α

Φ ΙΑ

SiO co EH

"Μ

¥ ^C H U O ^ j -P '

VD

ι VO

VD

IA IA

IA

OJ LT \

O O V

O O

O O V

O O V-

O O

O O V-

O O ν

O O V

VD CAJ

CA V-

CN (N

CN CN

CN CN

CN CN

VD

VD

VD

VD

O O V

O O ν

O O

100

OJ

O O V-

- 16 - 2 2.5 7 6 1 2034

Example 4: Mortality of Aphis fabae Scop. on Vicia faba «Investigations on potted Vicia peons

Potted Vicia plants with 2 unfolded leaves were subjected to foliar application in the concentration levels 10000 ppm and 1000 ppm. Subsequently, the Besiediungs- and killing mode was analogous to Example 3 · However, at certain intervals, these operations were repeated to explore the long-term effect of the inventive means.

Table Y: Effect of the agents according to the invention on Aphis fabae Scop. on potted Vicia EClanzen

Colonization: 1 day n. Application 6 days n. Application mortality: 7 days n. Application 15 days n.applikation

Active ingredient Concentration 10000 ppm 1000 ppm 10000 ppm 1000 ppm No.

Control 0 % 2 %

80 % 70 % 76% 60%

Benomyl (known)

1 ^! 100 % 100% 100 % 88

33 100% 100% 100% 100

- "- 17 - 22 57 6 1 2034

Example 5: Reduction of the stocking density of Rhopalosiphum padi on spring barley (Trumpf variety) under laboratory conditions

Spring barley of the Trumpf variety was treated in the 2-leaf stage both via the leaf and over the root with the inventive compositions in the concentrations 1000 ppm and 100 ppm and then converted to hydroponic culture. After application, Rhopalosiphum padi was grown on the treated and untreated barley plants, which in turn began immediately with the birth of the offspring. These offspring were then rearranged on treated and untreated barley plants and, on the 7th, 14th and 16th day after the application, determined the aphid number and compared them to the values of the control (control = 100).

Table VI: Relative number of Rhopalosiphum padi on spring barley treated before aphids colonization Trumpf species under laboratory conditions

more concentration after the 9th 11th 100 1000 Opm 100 • 100 ppm 100 100 100 100 fabric no. Days 7. 100 6 Application 14. 16. 0 20 27 29 31 control 100 7 0 100 0 Days after application 7. 9. 11. 14. 16. 20 6 0 0 benomyl 5 0 0 2 0 100 0 0 0 0 1 0 0 0 0 0 15 " 8th 4 5 0 33 0 0 0th 0 9 0 0 0 • 6

It is clear from Tables IV to VI that the agents according to the invention greatly reduce or inhibit the aphid content and the colony formation on the crop plants.

- 18 .- 2 2 5 7 6 1 2034

Example 6: Influence on the Development of Minimizing Insect Insects

In the greenhouse attracted, potted plants of Beta vulgaris L. were in the 6-8-leaf stage with eggs of the beet fly (Pegomyia betae Gurt.) Occupied. The spraying with the agents according to the invention took place in two different ways:

1. Application 3 days before filling with eggs

2. Application immediately after oviposition '

In the following period, the influence of the remedy was examined, taking into account different treatment times, on the development of the eylviruses, the number of jups, the hatching rate and the sexual relationship. '

Table VII (a and b): Effect of the agents according to the invention

on insect pests (application 3 days before oviposition)

Control Benomyl

Concentration - 100 1000

(Ppm)

Number of Eilarven "100 91.2 55.7 (rel.)

Number of dolls 100 65.7 9.7

(rel.).

Slip rate (%) ^ 7 * 5 34.8 23.1

Sex ratio 1: 1 4.2: 1 -2: 1

Voting behavior 100

(Rel.)

Table VII a: (application 3 days before oviposition)

Active substance no.

Concentration (ppm)

1 33 9 10

100 1000 10000 100 1000 10000 100 1000 10000 100 1000 10000

Number of Eilarven (rel.)

Number of Puopen (rel.).

Hatching rate (%)

sexual behavior

Voting behavior (rel.)

79.4 86.3 79.9 84.8 91.2 100.5 114.9 93.5 67.3 92.1 92.8 71.7

86.5 15.9 6.3 70.0 39.7 2.4 74.3 61.0 6.7 105.1 53.8 9.7 27.9 10.0 0 34.6 30.0 0 38, 5 28.1 0 14.1 1.3 0

1: 1.1 44.2

1: 0.7 1: 1.1 54.6

- 1: 1 1: 1.3

0.6: 1 0: 1. Not

evaluable

ro cn cn

Table VII b: (application immediately after, oviposition)

concentration

control

benomyl

100 1000

Number of Eilarven (rel.)

Number of dolls (rel.)

Hatching rate (%)

Sexua! Ratio (5: 0 ")

100

100W, 5 '

1: 1

95.3 79.5

47.5 25.5

3,7:

ro ο

IO

to

cn

ro

Table VII b ^: (application immediately after, oviposition)

Active ingredient no.

33

10

Concentration .100 1000 10000 100 1000 10000 100 1000 10000 100 1000 10000

(ppm) '·

Number of 109.8 104.4- 89.7 105.9 79.9 63.2 114.3 125.0 92.9 -78 91.8.89.6

Eilarven (rel.)

Number of '

Dolls 88.1 4.0 8.0 97.6 11.9 0.8 121.0.19.0 1.0 77.5 17.8 33.5

(Rel.)

Slip rate 43.2 0 0 19.5 20.0 0 49.2 15.8 0 16.7 4.5 20.0

Sexual behavior (0: Cf)

1: 1.1 -

1: 2.4 1: 2 - 1: 1

- D, 6: 1 0: 1 0.8: 1

- 22 - 2 2 5 7 6 1 2043

Example 7

The active ingredient Kr. 10 was administered under field conditions after oviposition until the pinworm of Pegomyia betae (Curt.) In the concentrations 5OOO ppm and 10000 ppm at an application rate of 600 l / ha on beta beets, with dimethoate (at the beginning of Minierfraß sprayed) as a comparative preparation (0.05%) served. Achieved a Dimethoat treatment up to the 12 "day after the application, an efficiency (according to Abbott) of 89 - 100 '%, the corresponding values of the presented product were between 86 to 100%,

Example 8: Influence on the development of biting noxious insects (Oarausius morosus Br. /Phasmat./)

Twenty-four rodent insect larvae were placed on the test plants at the age of 21 days per test vessel 24 hours after the application. The stem cut off from the sprayed pot plant (Tradescantia albi flora or Vicia faba) stood in the water.

22 576.1

Table VII: Effect of the agents according to the invention on pest insects

Active substance * Konzen no. tration ppm

Mortality in% after. meet

14

21

28

Kotmenge in

g / animal

rel.

Control Benomyl

10

100

1000

100

1000

10000

10

100

1000

100

1000

10000

10

100

1000

100

1000

10000

0 0 0

12.5 0

0 0

2.5

0 0 0

5.0 10.0

0 0 0

2.5

2.5

32.5

7.5 57.5 87.5

2.5

30 100

27.5 100 100

0 27.5

55 82.5 100

5.0 22.5 45.0 92.5

2,550

80.0

35.0 85.0

10 45.0 27.5 97.5 100 87.5 97.5 100

25.0

2.5 27, .5 90.0 15.0 90.0 100 100

100 76.4

31.3

50.8

39.3 23.0

52.1 26.9 21.9

62.2 51.1 31.1

50.7 27.4

21.5

36.6

29.5 26.8

Example 9J Influence on the development of biting insects

(Epilachna varivestis MuIs.)

Fresh, hatched larvae of Epilachna varivestis MuIs. are fed with cut leaves from 24-hour previously treated Phaseolus plants and observed the development and growth of insects to 10 days after hatching of the beetle or larval hatching of eggs deposited by these animals. Although the larvae weight at 10000 ppm and the weight of the adult beetles at 100, 1000 and 10000 ppm are only insignificantly reduced, the ones hatched from the pupae and continue to be treated. Plant matter-eating beetles only such eggs

2 2 5 7 6 1

2043

in which embryonic development does not occur and therefore no larvae hatch.

Table IX: Effect of experimental agents on biting insects

Compound concentrate weight v. tration 10 larvae

ppm

10 days η slip

in mg weight ν. Embryo-hatching-1 beetle nolent rate of 3 days α. ^wickl ° ^larvae slip

in mg

in days _in

control

Active ingredient No. 10

100

1000

10000

128.3

125.7 123.7

77.6 48.0

44.2 43.7 42.2

70.3

0 0 0

Claims (1)

25 .- 225761 2043 invention claim Biocidal agent, characterized in that it is next to
conventional excipients and carriers as active ingredient substituted hexahydro-s-triazino (1,2-a) benzimidazoles of the general formula COOGH ₃ in the R = an alkyl group having 1 to 12 C atoms, a cycloalkyl group, a phenyl radical which may optionally be substituted by alkyl, halogen, alkoxy, nitro, phenoxy or acetyl, furthermore a phen ~ (C _/ j ~ C _z ,) - alkyl or an alkoxyalkyl group having 1 to 4 C atoms, depending on the intended use 0.1 to 6 kg of active ingredient per hectare.