DE2226012A1 - Use of cyclic compounds - Google Patents

Description

CiBA-GEIGY

CLBA-QElGY AG, CH-4002 Basel

Dr, F. Zumstein son. - Dr. E. Assmann Dr. R. Koer. ^ Sb: rgc-r - C!?!. Pi.ys. R. i ■ '. .-! zbauer

Dr. ί ". SuTiSic !:": j- ^! n.

P ei t e η t α ii v / oiled

9 Munich 2, Brsuhausstrasse 4/11!

Case 5-7533 / 1 + 2 / -

Use of cyclic compounds

The present invention relates to methods of controlling insects using s-triazine derivatives the formula

(I)

209851 / 119A

wherein R-. and R "is lower alkyl,

The for R-. and R2 are lower Alkyl chains have 1 to 5 carbon atoms and can be branched or be straight chain.

Examples of such radicals include: methyl; Ethyl; Propyl; Isopropyl; n-, i-, sec-, tert-butyl; n-pentyl.

Of particular importance are connections of

formula

N "
| 3

TSP

(II)

wherein Ro is methyl, ethyl or isopropyl and R, methyl, ethyl _; mean n-propyl, isopropyl, n-, or sec-butyl.

The following are examples of compounds of the formula II:

link Drop: ° C 2-azido-4- (methoxy-methyl-amino) -
6-isopropylamino-s-triazine 120-122 2-Azido-4- ethoxy-methyIamino ^ -
6-isopropylamino-s-triazine 114-116 2-azido-4-'n-propoxymethylamino)
6-isopropylamino-s-triazine 78-80 2-azido-4- (isopropoxymethylamino) -
6-isopropylamino-s-triazine 117-119 2-azido-4- (methoxymethylamino) -
6-ethylamino-s-triazine 112-124

209851/1194

link

M.p .: ° C

2-Azido-4- ( ethoxy-methylamino) -6-ethylamino-s-triazine

2-Azido-4-fisopropoxymethylamino) 6-ethylamino-s-triazine

2-Azido-4- (sec-butoxy-methylamino) -6-ethylamino-s-triazine

2-Azido-4- (sec-butoxy-methylamino) -6-isopropylamino-s-tr iazine

123-124 120-121 100-101 68-70

The compounds of the formula I are prepared

by making a compound of the formula
Cl

N Ή

R ₁ HN- ^ y- KHCH ₂ OR ₂

(in)

where R, and R _? the meaning given for the formula I have reacted with an alkali metal azide in the presence of a basic substance or by reacting the compound of the formula

I.
CH ₃ -N-CH ₃

R HIT - \ J- UHCH ₉ OR

(IV)

where R, and

the meanings given for the formula I have and Y represents an inorganic or organic acid radical, in particular chlorine or bromine, with an alkali metal azide
implements.

2 0 9 8 5 1/119 4

In particular, tertiary amines such as trialkylamines, as well as hydroxides, oxides and carbonates of alkali are used as basic substances and alkaline earth metals. For the reactions, water is preferably used as a solvent or diluent, but it can also be mixed with water organic solvents such as ketones, ethers and ethereal compounds, nitriles, N, N-disubstituted Amides, sulfoxides, etc., as well as those which are immiscible with water Solvents such as aliphatic and aromatic hydrocarbons and hydrogen halides can be used.

In Belgian patent specification No. 730 133, analogous compounds are used as total herbicides and as selective herbicides described.

Analogous compounds are also described as herbicides in French patent specification No. 1.537.312. It will be on indicated their possible insecticidal effects.

Compared to these active ingredients, the compounds of the formula I show a clear superiority in the fly test.

It is well known that phosphoric acid esters, as Representatives of classic insecticides, killing both vertebrates and invertebrates by inhibiting cholinesterase by attacking Acetylcholxn enriches the nerve endings. The accumulated acetylcholine interferes with the functioning of the nervous system, and as a result, death occurs after a few hours.

In contrast to the classic insecticides which, as contact or feeding poisons, kill the insects in a few hours or lame, the active ingredients of the formula I primarily affect the end phase of larval development.

209851/1 1 9 A

- ir -

The development interruption takes place in the larval or pupal stage, depending on the time of application. This mode of action cannot be compared to classic insecticides, chemosterilants or juvenile hormones.

The active ingredients of the formula I can be used in particular to combat the following pests of stored products and hygiene will:

Orthoptera

Blattidae

Isoptera Coleoptera

Diptera

Kalotermit idae Carabidae Elateridae Tenebrionidae Dermestidae Cucuj idae Scarabaeidae CuIicidae Simuliidae Tipulidae Muscidae

Calliphoridae

The compounds of the formula I can be used alone or used together with suitable carriers and / or additives. Suitable carriers and aggregates can be solid or liquid and correspond to those in the formulation

technically common substances such. B. natural or 209851/1194

regenerated substances, solvents, dispersants, wetting, adhesive, Thickeners, binders and / or fertilizers.

The agents according to the invention are prepared in a manner known per se by intimately mixing and / or grinding active ingredients of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active ingredients. The active ingredients can be present and used in the following working-up forms:
solid processing forms: dusts, grit,

Granules, coating granules, impregnation granules and homogeneous granules Premix (feed additive) liquid processing forms:

a) dispersible in water

Active ingredient concentrates: wettable powder,

Pastes, emulsions;

b) Solutions aerosols

For the production of solid processing forms (dusts, grit), the active ingredients are mixed with solid carriers mixed. Carriers include kaolin, talc, bolus, loess, chalk, limestone, lime grit, ataclay, Dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, Sodium and potassium aluminum silicates (feldspars and mica), secondary calcium phosphate, calcium and magnesium sulfates,

2 0 9 8 5 1/119 4

Magnesium oxide, ground plastics, fertilizers such as ammonium sulfate , Ammonium phosphate, "ammonium nitrate, urea, ground vegetable products such as grain flour, tree bark flour, wood flour, nutshell flour, cellulose powder, residues from plant extractions, Activated charcoal, etc., can be used individually or as mixtures with one another.

Granules can be produced very easily by one an active ingredient of the formula I in an organic solvent dissolves and the solution thus obtained on a granulated Mineral, e.g. attapulgite, SiOg> Applies granicalcium, bentonite, etc. and then evaporates the organic solvent again.

Polymer granules can also be produced by mixing the active ingredients of the formula I with polymerizable Compounds are mixed (urea / formaldehyde; dicyandiamide / formaldehyde; Melamine / formaldehyde or others), whereupon a gentle polymerization is carried out, of which the Active substances remain unaffected, and granulation is still carried out during gel formation. It is cheaper finished, porous polymer granules (urea / formaldehyde, Polyacrylonitrile, polyester and others) with a specific surface area and a favorable, predeterminable adsorption / desortation ratio to impregnate with the active ingredients e.g. in the form of their solutions (in a low-boiling solvent) and that Remove solvent. Such polymer granules can be in the form of microgranules with a bulk density of preferably 300 g / liter to 600 g / liter also with the help of atomizers

209851/1194

be applied. The atomization can be carried out with the help of airplanes.

Granules can also be obtained by compacting the carrier material available with the active ingredients and additives and subsequent chopping.

These mixtures can also stabilize the active ingredient Additives and / or non-ionic, anion-active and cation-active substances are added, for example, the adhesive strength the active ingredients (adhesives and adhesives) and / or better wettability (wetting agents) and dispersibility (dispersants) guarantee.

For example, the following substances come into question: olein-lime mix ung, cellulose derivatives (methyl cellulose, carboxymethyl cellulose) , Hydroxyethylene glycol ethers of mono- and dialkylphenols with 5-15 ethylene oxide residues per molecule and 8-9 carbon atoms in the alkyl radical, ligninsulphonic acid, its alkali and alkaline earth salts, polyethylene glycol ethers (Carbowaxes), fatty alcohol polyglycol ethers with 5 - 20 ethylene oxide residues per molecule and 8-18 carbon atoms in the fatty alcohol part, condensation products of Ethylene oxide, propylene oxide, polyvinylpyrrolidones, polyvinyl alcohols, condensation products of urea-formaldehyde and latex products .

Active ingredient concentrates dispersible in water, i.e. wettable powders, pastes and emulsion concentrates represent means that work with water to any desired concentration can be diluted. They consist of active ingredient, carrier and, if necessary, additives that stabilize the active ingredient,

BAD ORfGMNAL

2098 5 1/1194

surface-active substances and anti-foaming agents and, if applicable Solvents.

The wettable powder (wettable powder) and pastes are obtained by mixing the active ingredients with dispersants and powdery carriers in suitable devices up to mixed and / or ground to homogeneity. Suitable carriers are, for example, those mentioned above for the solid work-up forms. In some cases it is beneficial to Use mixtures of different carriers. As dispersants For example, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives can be used with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde as well Alkali, ammonium and alkaline earth salts of lignin sulfonic acid, furthermore alkylarylsulfonates, alkali and alkaline earth metal salts of Dibutylnaphthalene sulfonic acid, fatty alcohol sulfates, such as sulfated salts Hexadecanols, heptadecanols, octadecanols and salts of sulfated fatty alcohol glycol ether, the sodium salt of Oleymethyltraurid, ditertiary acetylene glycols, dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.

^! Silicones, for example, can be used as antifoam agents. -

The active ingredients are made with the additives listed above so mixed, wedded, sifted and happened, that at the wettable powders the solid fraction has a particle size of 0.02 to 0.04 and 0.03 mm for the pastes. For the production of emulsion concentrates and pastes, dispersants, as listed in the previous sections

2 0 9 8 5 1/119 4

organic solvents and water were used. For example, alcohols, benzene, xylenes, toluene, dimethyl sulfoxide and mineral oil fractions boiling ^{in the range from 120 to 350 ° C. come into consideration as solvents.} The solvents must be practically odorless, non-phytotoxic and inert to the active ingredients.

The agents according to the invention can also be used in the form of solutions. For this purpose, the active ingredient or are several active ingredients of the general formula I in suitable organic solvents, solvent mixtures or Dissolved in water. Aliphatic and aromatic hydrocarbons, their chlorinated derivatives, Alky! Naphthalenes, mineral oils alone or as a mixture with one another be used.

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

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

Dusting agent: The following substances are used to produce a) 0.5% and b) 2% dust:

a) 0.5 parts of active ingredient

99.5 parts of talc,

■ 'b) 2 parts of active ingredient

1 part of highly dispersed silica,

97 parts of talc.

209851/1194

The active ingredients are mixed and ground with the carrier substances.
Grit:

5 part active ingredient will be with

95 parts of carbonate mixed with lime and ground to a mean particle size of 80 u. Granules:

5 parts of active ingredient are in a solvent such as

Dissolved methylene chloride and mixed with 2 parts of polyethylene glycol ("Carbowax").

Be with the mix

91.5 parts impregnated with calcium carbonate and 1.5 parts of precipitated silica mixed in and

finally the solvent evaporates. Bait granules:

2.0 parts active ingredient

0.05 part of a dye

1.0 part celite or kaolin is mixed and fine

marry. Thereupon 96.85 parts of crystallized sugar are made with the above

Mixture mixed and dissolved with 0.10 part of an adhesive in e.g. a little

Isopropanol, impregnated and the solvent evaporated.
Wettable powder:

50 parts of the active ingredient are included
5 part of a dispersant e.g. lignin sulfonic acid

2 0 9 B F, 1/1 1 9

Sodium salt

5 part of a wetting agent e.g. dibutylnaphthalenesulfonic acid

10 parts silica and

30 parts of kaolin mixed and finely ground

Emulsifiable concentrate:

20 parts of active ingredient are included

20 parts emulsifier e.g. mixture of alkylaryl poly-

glycol ether mixed with alkyl aryl sulfonates and 60 parts solvent e.g. xylene until the

Solution is completely homogeneous. This concentrate - with water gives an emulsion of any desired Concentration.

Premix (feed additive):

0.25 part active ingredient and

4.75 parts secondary calcium phosphate, or kaolin

or Aerosil or carbonate of lime are mixed with 95.00 parts of a feed such as rabbit feed mixed homogeneously.

Aerosol:

0.25 part active ingredient
25.00 part of trichloroethane
24.75 parts of gasoline are used in an aerosol filling system

ν with
50.00 parts propellant, consisting of Freon 11/12 im

2 0 9 8 fi 1/1 1 9 4

Ratio 1: 1 filled in aerosol cans, ' Sprühm i ttel:

For the manufacture of an a) 5% and b) 2 7 _ö strength spraying agent the following components are used:

a) 5 parts of active ingredient

1 part epichlorohydrin
- 94 parts of gasoline (boiling limits 160-190 ⁰ C),

b) 2 parts of active ingredient
1 part diazinon

97 parts of kerosene.

Other biocides can be used with the agents described Add active ingredients or agents. So can the new funds in addition to the compounds of general formula I mentioned, for example insecticides and fungicides. Bactericides, fungistats, bacteriostats for the distribution of the effect specimen.

The active ingredients of the formula I are suitable as development inhibitors for combating insects. In contrast to classic Insecticides that act as contact or feed poisons the insects kill or paralyze in a few hours, the active ingredients of formula I primarily affect larval development. The effect consists in the death of the larvae or in preventing the hatching of adult insects from pupae. These Activity cannot be compared to classic insecticides, chemosterilants or juvenile hormones. '*

Since the active ingredients of the formula I are harmless to warm-blooded animals, the main area of application

209851/1194

namely the fly maggot control, new aspects. Instead of treating large areas as with insecticides, the active ingredients can of formula I administered with the feed to farm animals, e.g. chickens will. The active ingredients pass through the digestive tract undamaged and are present in the excreted feces. The fresh one Feces are ideal breeding grounds for hygienic pests such as flies. The larvae that hatch from the eggs come into contact with the new active ingredient immediately and their further development is prevented. The larger maggots that migrate from the old manure to the fresh manure also come into contact with the active substances and their final phase is disturbed. The maggots pupate without significant mortality, but the pupae do not produce flies.

In addition to the selective development inhibition in insects, the environmentally friendly application via feed can be emphasized because only the faeces contain the active ingredients.

The means, or the active ingredients contained therein unfold their development-inhibiting effect primarily on larval stages of insects, preferably of the order Diptera. They are also suitable for the protection of stored products, especially for the Protection of food and supplies in which insect larvae, e.g. of the order Coleoptera, normally develop.

209851/1 1 9 Λ

example 1

Test substances:

Test animal:

Concentration:

Test method:

Active ingredients of formula I formulated as acetone solutions
Musca domestica
0.05 7o active ingredient

50 grams of CSMA maggot substrate are placed in cups weighed. From a 1% acetone solution per active substance (AS) two 2.5 ml pipetted onto 50 g grub substrate. After mixing the treated. Substrates leaves you evaporate the solvent. 25 one-day maggots of Musca domestica attached. After 5 days the pupae are flushed out (and after 10 days we determines their hatching rate; thus a possible influence on the metamorphosis is determined.

Result:

Active ingredient

2-Azido-4- (methoxy-methyl-amino) -6-isopropylamino-s-triazine

2-Azido-4- (ethoxy-methylamino) -6-isopropylamino-s-triazine

2- Azido-4- (n-propoxymethylamino) - 6-isopropylamino- s-triazine

2-azido-4- (isopropoxymethylamino) · 6-isopropylamino-s-triazine

2-Azido-4- (methoxymethylamino) -6-ethylamino-s-tri azin

η dolls

29 0

43 18 34

η flyα

0 0 0 0

2 0 9 B Fig. 1/11

BATH

2-Azido-4- (ethoxy-methylamino) -
• 6-ethylamino-s ~ triazine 24 0 2-azido-4- (isopropoxymethylamino) -
6-ethylamino-s-triazine 23 0 2-azido-4- (isopropoxymethylamino) -
6-ethylamino-s-triazine 23 0 2-azido-4- (sec-butoxy-methylamino) -
6-ethylamino-s-triazine 34 0 2-azido-4- (sec-butoxy-methylamino) -
6-isopropylamino-s-triazine 50 0 control 50 49

209851/119

Claims (6)

Claims 1. Method of combating insects using s-triazine derivatives of the formula N N ■ NHCH ₂ OR ₂ wherein R, and R ₂ each signify lower alkyl. 2. The method according to claim 1 using compounds the formula N N R- ^{HN- 1} ^ y- NHCH OR wherein Ro is methyl, ethyl or isopropyl and R, methyl, ethyl mean n-propyl, isopropyl, n- or sec-butyl. 3. The method according to claim 2 using the compound the formula N N X-NHCH ₉ OC ₉ H, ^S N ' 209851/1194 111 b UI Z 4. The method according to claim 2 using the compound of the formula K K CH CH, 5. The method according to claim 2 using the Compound of formula IT C ₀ H-KB ² 5 NHCH ₀ OCiH-2 6. The method according to claim 2 using the Compound of formula C ₀ H -KH KH-CH _O O-CH < λ 209851/119