DE2410239A1 - AMIDINE, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE IN VICTORY CONTROL - Google Patents

Description

CLBA-GEIGY AG, CH-4002 Basel

8 Munich 2, t.raucusJr ^ ia 4/111

Case 5-8672 / 1 + 2 / ==
Germany

"Amidines, process for their preparation and. Their uses

in pest control "

The present invention relates to amidines, processes for their preparation and their use in Pest Control.

The amidines have the formula

wherein R ^ is hydrogen or methyl.

409837/107?

CIBA-GElGY AG - f. -

The compounds of the formula I can by methods known per se, for example by reacting a compound the formula

CE_-SC \ ^X CH

^ OkHNH ₂ ^D (Ii)

with an acetal of the formula

/ CH

Alkyl-0

are prepared, wherein R, the given for the formula I. Has meaning and alkyl is preferably methyl or ethyl.

The reaction is carried out at atmospheric pressure, at a temperature between O to 10O ⁰ C and a relative to the reactants an inert solvent or diluent. Examples of suitable solvents or diluents are: aromatic hydrocarbons, such as benzene, toluene, halogenated hydrocarbons, chlorobenzene,

409837/1072

CIBA-GEIGYAG - 3 -

Polychiorbenzenes, bromobenzene, chlorinated alkanes with 1 to 3 carbon atoms, ethers such as dioxane, tetrahydrofuran; Esters such as ethyl acetate; Ketones such as acetone, methyl ethyl ketone, Diethyl ketone, nitriles e.g. acetonitrile etc. The starting materials of the formula II and III are known and can be prepared analogously to the methods described in German Offenlegungsschrift No. 1 963 061.

The compounds of the formula I have a broad biocidal action and can be used to combat various plant and animal pests are used.

In particular, they are suitable for combating insects of the families: Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettioniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Diaspdididae, Pseudococcidae, Chrysomelidae, Coccinellidae, Bruchidae, Scarabaeidae, Dermestidiae, Tenebrionidae, Curculionidae, Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culicidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae and acarids of the families: Ixodidae, Argasidae, Tetranychidae, Dermanyssidae.

409837/107?

CLBA-GEIGY AG * ""

The insecticidal or acaricidal effect can be substantially increased by adding other insecticides and / or acaricides broaden and adapt to specified circumstances. The following active ingredients are suitable as additives:

organic phosphorus compounds; Nitrophenols and their derivatives, pyrethrins; Forraamidine; Urea, carbamates and chlorinated hydrocarbons.

409837/107?

CIBA-GEJGYAG - if -

In addition to the properties mentioned above, the compounds of the formula I also have an activity against representatives of the Thallophyta department. Some of these compounds show bactericidal activity. However, they are primarily effective against fungi, in particular against the following classes of phytopathogenic fungi belonging to the following classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes. The compounds of the formula I also show a fungitoxic effect on fungi which attack the plants from the ground. The new active ingredients are also suitable for treating seeds, fruits, tubers, etc. to protect against fungal infections. The compounds of the formula I are also suitable for combating phytopathogenic nematodes.

409837/1072

CLBA-GEiGYAG - 6 -

The compounds of the formula I can be used alone or together with suitable supports and / or aggregates can be used. Suitable carriers and additives can be solid or liquid and correspond to those in the Formulation technology Usual substances such as natural or regenerated substances, solvents / dispersants, wetting agents, adhesives, thickeners, binders and / or fertilizers. For application, the compounds of the formula I can be added to dusts, emulsion concentrates, granules, dispersions, Sprays, solutions or suspensions in the usual way Formulations that are part of general knowledge in application technology can be processed. Furthermore are "cattle dips", i.e. cattle baths, and "spray races", i.e. Sprinkles in which aqueous preparations are used be to mention.

The compositions according to the invention are produced in a manner known per se by intimate mixing and / or Mixing of active ingredients of the formula .1 with the appropriate ones Carriers, optionally with the addition of opposite dispersants or solvents that are inert to the active ingredients. The active ingredients can be used in the following working-up forms are available and applied;

409837/1072

CLBA-GEIGY AG - 7 -

2410233

Forms of processing: dust, grit,

Granules, coating granules, impregnation granules and Homogeneous granules

Liquid

Forms of processing:

a) dispersible in water
Active ingredient concentrates: wettable powders

Pastes, emulsions;

b) Solutions

The content of active ingredient in the means described above is between 0.1 and 95%, it should be mentioned that when applying from an airplane or by means of another Suitable application devices, concentrations of up to 99.5% or even pure active ingredient can be used.

409837/107?

CLBA-GElGY AG ""%"

The active ingredients of the formula I can, for example, be formulated as follows:

StHubemitLel: To a distribution Hers a) 5Zi gene and b) 27 _o by weight StUubeinittcls uses the following materials:
a) 5 parts of active ingredient

95 parts of talc;
■ b) 2 parts of active ingredient

1 part of highly disperse silica, 97 parts of talc

The active ingredients are mixed with the carriers and marry.

Granules: The following substances are used to produce 5% granules:

5 parts of active ingredient

0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycolate, 3.50 parts of polyethylene glycol

91 parts of kaolin (grain size 0.3-0.8 mm). The active substance ^; is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and added cetyl polyglycol ethers. The solution obtained in this way is sprayed onto kaolin and then the

£ 09837/107?

CIBA-GEIGYAG

Acetone evaporated in vacuo.

Spray powder: The following ingredients are used to produce a) 40%, b) and c) 25% d) 10% spray powder:

a) 40 parts of active ingredient

5 parts of lignin sulfonic acid sodium salt,

1 part dibutylnaphthalenesulfonic acid sodium salt,

Parts of silica;

b) 25 parts of active ingredient

4j5 parts calcium liginsulphonate,

1.9 parts of champagne chalk / hydroxyethyl cellulose mixture (1: 1),

1.5 parts of sodium dibutyl naphthalene sulfonate, 19.5 parts of silica, 19.5 parts of champagne chalk, 28.1 parts of kaolin;

c) 25 parts of active ingredient

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of champagne chalk / hydroxyethyl cellulose

Mixture (1: 1), 8.3 parts of sodium aluminum silicate,

16.5 parts of kieselguhr, parts of kaolin;

409837/1072

CIBA-GEIGYAG _ -j ^ Q

d) 10 parts of active ingredient - "■ 3 parts mixture of the sodium salts of saturated

Fatty alcohol sulfates,
5 parts napthaiinsulfonic acid / formaldehyde condensate

sat,

82 parts of kaolin.

The active ingredients are mixed with the additives in suitable mixers intimately mixed and ground on appropriate mills and rollers. One receives wettable powder that can be diluted with water to form suspensions of any desired concentration.

Emulsifiable concentrates: The following substances are used to produce a) 10% and b) 25% emulsifiable concentrate:

a) IO parts active ingredient

3.4 parts epoxidized vegetable oil,

13.4 parts of a combination emulsifier, consisting.

from fatty alcohol polyglycol ether and alkylaryl

sulfonate calcium salt,
40 parts of dimethylformamide,
43.2 parts of xylene;

b) 25 parts of active ingredient

2.5 parts epoxidized vegetable oil,

10 parts of an alkylarylsulfonate / fatty alcohol polyglycol ether mixture,

409837/1072

CIBA-GEIGYAG

5 parts of dimethylformamide, 57.5 parts of xylene.

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water will.

SprUhmiütel: the following ingredients are vorwendet To prepare a 57 _o solution of spraying agent:

5 parts active ingredient,

1 part epichiorhydrin, 94 parts gasoline (boiling point 160 - 190 ° C);

409837/107?

ciBA-GEiGYAG - 12 -

example 1

Preparation of the compound of formula

O
II X) H

S Ni

CH _V S-Cv

0 ^ 0-N = CH-N (CH _V ) _O

5 grams of methyl 1- (carbamoyl) -N- (methylcarbaraoyloxy) thioformamidate and 3.1 g of methyl formamide dimethyl acetal are stirred to a paste and left to stand at room temperature for 2 hours. The resulting crystalline reaction product is washed with a little acetone, suction filtered and dried. The compound of the formula is obtained

CH _V -SC

v),

with a melting point of 147 ⁰ C.

409837/107?

CIBA-GEIGY AG _] 3 _

The following connection is also established in the same way:

Il / CH.,

_CH- sc / ' ^XCH -' ^Sm P * ¹¹ T - 118 ⁰ C

= CBHET (OH J

A09837 / 107?

CIBA-GEiGY AG,, '

- 34 -

Example 2

A) Insecticidal feed poison effect

Cotton plants and potato plants were with a 0.05% aqueous active substance emulsion (obtained from a 10% emulsifiable concentrate) sprayed.

After the covering had dried on, the cotton plants became each with Spodoptera littoralis or HeIiothis virescens larvae L ~ and the potato plants with Colorado potato beetle larvae (Leptinotarsa decemlineata) occupied. The attempt was carried out at 24 ° C and 60% relative humidity.

The compounds according to Example 1 showed in the above test a good insecticidal milling poison action against Spodoptera, Heliothis and Leptinotarsa decemlineata larvae.

B) Systemic insecticidal effect

To determine the systemic effect, rooted bean plants (Vicia faba) were in a 0.01% strength aqueous active ingredient solution (obtained from a 10% emulsifiable concentrate). After 24 hours, aphids were found on the above-ground parts of the plant (Aphis fabae) set. The animals were slit in front of the contact and gas effects by a special device. The experiment was carried out at 24 ° C. and 70% relative humidity.

409837/1072

CtBA-GEIGYAQ - 15 -

The compounds according to Example 1 worked in the above Systemic test against Aphis fabae.

Example 3 Effect against Chilo suppressalis

6 rice plants of the Caloro variety were placed in plastic pots with an upper diameter of 17 cm. transplanted and raised to a height of approx. 60 cm. The infestation with Chilo suppressalis Larvae (L ...; 3-4 mm long) took place 2 days after the Active ingredient addition in granulate forums (application rate 8 kg of active ingredient per hectare) in the paddy water. The insecticidal activity is evaluated 10 days after the granules have been added.

The compounds according to Example 1 were effective against Chilo suppressalis in the above test.

409837/107?

ciBA-QEiQYAQ. - 16 -

Example 4 Effect against ticks

A) Rhipicephalus bursa

5 adult ticks or 50 tick larvae were counted in a glass tube and for 1 to 2 minutes in 2 ml one aqueous emulsion from a dilution series of 100 each, 10, 1 or 0.1 ppm test substance immersed. The tube was then closed with a standardized cotton ball and turned upside down so that the active ingredient emulsion could be absorbed by the wadding. The evaluation of the adults took place after 2 weeks and in the larvae after 2 days. Two repetitions were run for each attempt.

B) Boophilus microplus (larvae)

With an analogous dilution series as in test A were each with 20 sensitive resp. OP-resistant larval experiments were carried out. (The resistance refers to the compatibility of diazinon) The compounds according to Example 1 acted in these Tests against adults and larvae of Rhipicephalus bursa and sensitive resp. OP-resistant larvae of Boophilus microplus.

409837/1072

CLBA-GEIGY AG - 17 -

Example 5 Acaricidal effect

Phaeolus vulgaris (plants) were covered with an infested piece of leaf from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal action. The moving stages that had overflowed were dusted with the emulsified test preparations from a chromatography atomizer so that the spray mixture did not run off. After two to 7 days, larvae, adults and eggs were evaluated for living and dead individuals under the dissecting microscope, and the result was expressed as a percentage. During the "holding time ¹¹ ", the treated plants stood in greenhouse cabins at 25.degree.

The compounds according to Example 1 worked in the above test against adults, larvae and eggs of Tetranychus urticae.

Example 6 Effect against soil nematodes

To test the effect against soil nematodes, the active ingredients were used in the specified concentration in soil infected by root cell nematodes (Meloidogyne arenaria) and mixed thoroughly. In the one so prepared Soil tomato seedlings were planted immediately afterwards in one test series and in another Test series sown tomatoes after a waiting period of 8 days.

409837/107?

CIBA-GEIGYAG

The nematocidal effect was assessed for 28 days after planting or after sowing, the galls present on the roots are counted.

In this test, the active ingredients were shown in Example 1 a good effect against Meloxdogyne arenaria.

409837/1072

Claims (8)

CLBA-GEIGY AG patent claims 1. Compounds of the formula CH_- JSh-O-C-JK X) H. wherein R, hydrogen or methyl. 2. Compound according to claim 1 of the formula CH - T = CH-N (CHJ. 3. Compound according to claim 1 of the formula 409837/107? CIBA-GEIGYAG - 20 - 4. Process for the preparation of compounds according to claims 1 to 3, characterized in that a compound of the formula 0 ^ C-NH ₂ with a compound of the formula 3IL Alkyl-0 converts, wherein R-, the meaning given in claim 1 • has and alkyl is preferably methyl or ethyl. 409837/107? CLBA-GEIGY AG - 21 - 5. Pesticides which contain a compound according to claims 1 to 3 and suitable carriers and / or other additives as the active component. 6. Use of compounds according to the claims 1 to 3 for combating various animal and vegetable pests. . 7. Use according to claim 6 for combating insects and representatives of the order Akarina. 8. Use according to claim 6 for combating phytopathogenic nematodes. 409837/107?