DE2736698A1 - NEW INSECTICIDES - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann - Dr. R. Kocnigsberger Dipl.-Phys. R. Holzbauer - Dipl.-Ing. F. K'ingsoisen - Dr. K Zumstein jun.

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 22 5341

TELEX 529978 TELEGRAMS: ZUMPAT

CHECK ACCOUNT: MÖNCHEN 01139-809. BLZ 7OOKJO8O

BANK ACCOUNT: BANKHAUS H. AUFHAUSER ACCOUNT NO. 3979S7. BLZ 7OO3O6OO

8 MUNICH 2.

BRÄUNAUSSTRASSE 4

5-10 667/1 + 2 / y-

CTJBA-GEIGY AG, CH-4002 Basel / Switzerland

New insecticides

The present invention relates to new 2-cyclopropylamino A-formamidino-o-amino-s-triazine derivatives, method too their manufacture and their use for pest control.

The 2-cyclopropylamino-4-formamidino-6-amino-s-triazine derivatives have the formula

Ro R-i

H N

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wherein R, hydrogen, C, -C, -alkyl, optionally substituted by lower alkoxy, C ^ -C ^ -alkenyl, C ^ -C ^ -alkynyl, cyclopropyl, hydroxy, methoxy or ethoxy, R _{2 is} hydrogen, methyl or ethyl or R ₁ and R- together with the adjacent nitrogen atom form one

5- or 6-membered heterocyclic ring, optionally containing another nitrogen atom or an oxygen atom,
R ₃ methyl or ethyl,
R, methyl or Aethyl.und
Rc hydrogen or methyl
mean.

The alkyl groups in question for R, can be straight-chain or branched, unsubstituted or, for example, by 1 to 4 carbon atoms containing Alkoxygruppei be substituted. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec. and tert-butyl and 2-methoxyethyl. Examples of the for R, Co-C, -alkenyl or C, -C, -alkynyl groups include allyl and propargyl.

Because of their action, compounds of the formula I are preferred in which R, hydrogen, C 1 -C 4 -alkyl, optionally substituted by lower alkoxy, C 1 -C 4 -alkenyl, Cn -C 4 -alkynyl, cyclopropyl, hydroxy, methoxy or Ethoxy, R ~ hydrogen, methyl or ethyl or R, and R ₂ together with the adjacent nitrogen atom 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl, 1-piperazinyl, 1- (4-methyl) -piperaziny or 1-imidazolyl, R ^ methyl or ethyl, R, methyl or ethyl and

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Rc is hydrogen or methyl. -

Compounds in which R, hydrogen, methyl, ethyl, isopropyl, 2-methoxyethyl, allyl, propargyl or cyclopropyl, R ₀ hydrogen or methyl or R 1 and R 1 together with the adjacent nitrogen atom 1-pyrrolidinyl, 4 have proven to be particularly advantageous -MorpbJLinyl or 1-imidazolyl, R-, methyl, R, methyl and R _{5 are} hydrogen and in which, when R is propargyl, R «is preferably hydrogen.

Particular attention is paid to the compounds in which R, hydrogen, methyl or ethyl, R2 is hydrogen, R- methyl, R, methyl and R ₁ - is hydrogen.

The following compounds are particularly worth mentioning:

2-Cyclopropylarin.no-4-dimethylformaTtiiditio-6-amino-s-triazine, 2-Cycloprcpylauiino-4-dimethylf orniamidino-6-ethylamino-s-triazine,

>
2-CyclopropylaTnino-4-dimethylformamidino-6-methylamino-s-triazine

2-Cyclopropylamino-4-dimethylformamidino-6-propargylamino-s-triazine.

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The compounds of the formula I are based on known ones Process made by e.g.

a) a 2-cyclopropylamino- ^/ !, 6-diamino-s-triazine of the formula II,

II

where R ,, Kp and R ^ the meaning for the formula I anßngobono have, with a Carbonsa'ureamid-acetal or ketal of formula III

Alkyl - 0. / ^R 3

CH - N III

Alkyl - 0.1 part ₄

vorin R ₃ and R _{4 have} the meaning given for the formula I

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or b) a 2-cycloprpylamino-4-forma! uidirio-6-Cnlcr ~ s-triazine of the formula IV

Cl

K N

IV

in which R ₃ , R and R _{5 have} the meaning given for the formula I, with ammonia or a primary or secondary amine of the formula V

' ^R l

"V

wherein R. and R _{2 have} the meaning given for the formula I, is reacted.

The reactions are preferably carried out in a solvent or diluent which is inert towards the reactants, for example in aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ethers or ethereal compounds or ketones. Catalysts such as p-toluenesulfonic acid can be added to the reaction mixture, but are not required. The reaction temperatures are between 30 and 130 ^° C.

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The starting materials of the formulas II and IV can be used analogously known processes produce that in chlorinated s-triazine derivatives chlorine by a corresponding Amii.'Ogruppe or replaced by several corresponding amino groups.

The preparation of 2-diallylamino-4-amino-6- (N ₎ N-dimethylformamidine) -s-trlazine is described in US Pat. No. 3,073,851.

In (Hu · American Pn L <m! .Schrift. No. 3.189,521 diamino- and triamino-i'-triazlno air. Chomoni.orl LunLirii for adult houseflies (Musca domcuLicu) buüchricbon. Di «; insect-inhibiting effect of 2 , 4,6-Triamlno- «-Lrlazlnrdurivalon (Kolamln-Dorivnte) is also used by S. Nagasawa et al., Botyu-Kagaku. 39 (4), 105 (197Ί) beachriobun, AnBorkovcc and ADDcMiIo (J.Mod.Chom. TLO (5), 4 *> Ί (1967) and CC. LaBrecque, RLFyo, AB DoMiIo and A.13. Horkovuc (J.Econ.Entomol. JjL (6), 1621 (1968) further describe the cheinosterilizing effects of including 2-cyclohexyiamino-4,6-diamino-s-triazine, 2-cyclohexylamino-1,6-dihexylamino-s-triazine and 2,4,6-tris-cyclohexylamino-i: - triazine and their salts on adult houseflies (Musca domestica).

Surprisingly, it has now been found that djc compounds formula I a pronounced larvlzido effect on inur-kLon-

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larvae, preferably on Diptera larvae. In contrast to the above-mentioned Ini3oktenchemo:; Lori Lan ti on, the compounds of formula I act on the juvenile stages of the insects. The effect consists in dying off the larvae or in preventing the hatchers; of adults from the pupae. The mode of action of the compounds i \ ar Formol I cannot be compared with the mode of action vcu kl.'isr.ischf-n insecticides, chemosterilants or Juvon.nhonnon.'itinlor.nn.

The active ingredients of the formula I can be used primarily for combating of hygiene pests and animal parasites from the order Dlptera and the l «;« ni.i Hon

Culicidae

Simuliidae

Mu :: eJduo

and Calliphoridae
can be used.

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The compounds of formula 1 can be used alone or Kusoratnon with suitable tigers and / or aggregates can be used. Suitable carriers and aggregates can be solid or liquid and correspond to the substances customary in formulation technology, such as natural or regenerated substances, solvents and / or dispersants.

»The production of invented means takes place in an xind / or in a known manner by intimate mixing Milling of active ingredients of the formula I with the appropriate ones Activator substances, if necessary, the addition of opposite Directly dispersing or solubilizing agents inert to the active ingredients. The active ingredients can in the following work-up forts are available and provided:

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Forms of processing: dust, grit,

Granulates, coating granulates, Impritgnicrungs & ranulai-.a and

Homogeneous granules premix (feed

zucatz) liquid

Forms of processing:

a) dispersible in water
Active ingredient concentrates: wettable powders

Pastes, emulsions; *

b) Spray solutions (aerosols)

For the production of solid processing tungsten formon (Stüubemittol, scattering agent), the active ingredients are mixed with solid carrier materials. Examples of carriers are kaolin, talc, bolus, LUss, chalk, limestone, kalk grit, ataclay dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum. lum silicates (feldspar and mica), calcium and magnesium sulfates, magnesium oxide, ground plastics, ground vegetable products such as cereal flour, baurar beef flour, wood flour, nutshell flour, cellulose powder. Residues from plant extrusions, activated carbon, etc., each individually or as mixtures with one another.

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Granules can be easily shared by dissolving an active ingredient of formula I in an organic solvent and applying the resulting solution to granulated mineral, e.g. attapulgite, SiO ₀ , green calcium, bentonite, etc. and then evaporating the organic solvent again.

Polymer granules can also be produced by mixing the active ingredients of the formula I with polymerizable compounds (urea / formaldehyde; dicyandiamide / fortnaldehyde; melamine / formaldehyde or others), after which a gentle polymerization is carried out, which does not affect the active ingredients, and granulation is still carried out while the gel is being formed. It is more favorable to impregnate finished, porous polymer granules (urea / formaldehyde, polyacrylonitrile, polyester and others) with a certain surface area and a favorable adsorption / desorption ratio that can be determined in advance with the active ingredients, e.g. in the form of their solutions (in a low-boiling solvent), and to impregnate the solvent remove. Such polymer granules can also be applied in the form of microgranules with bulk weights of preferably 300 g / liter to 600 g / liter with the aid of atomizers.

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Granules are also available by contacting the carrier terminator with the active ingredients and additives and then crushing available.

These mixtures can also stabilize the active substance Additives and / or nonionic, anionaktivo and Cation-active substances are added, for example, a better wettability (wetting agent) and dispersibility (Dispergators) ensure.

For example, the following substances are possible: olein / lime mixture, cellulose derivatives (ethyl cellulose, carboxymethyl cellulose), hydroxyl ethylene glycol tether of mono- and dinlkylphenols with 5-15 nylon oxide rents per molecule and 8-9 carbon atoms, 5m alkyl radical, ligninsulfonic acid, their alkali metal and alkaline earth metal salts (Carbow axis), l ^? ettalkoholpolyglykolather with 5-20 ethylene oxide residues per molecule and 8-18 carbon atoms in the fatty alcohol part, condensation product: of ethylene oxide, propylene oxide, polyvinylpyrrolidone, polyvinyl alcohol, condensation products of urea / formaldehyde as well as latex products.

Active ingredient concentrates dispersible in water, i.e. wettable powders (wettable powders) Pastes and emulsion concentrates are agents that can be mixed with water to any desired level

• ·

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Concentration can be diluted. Sin exists «aur. Active ingredient, carrier, optionally the active ingredient stabilizing additives, surface-active substances and antifoam agents !! and optionally solvents. The wettable powders and buttons are obtained by mixing the active ingredients with dispersants and powder-form carriers in suitable devices am mixed and married to homogeneity. as Carriers come, for example, those mentioned above the fixed processing forines mentioned in question. In For some fillings it is advantageous to use mixtures of different carriers. Can be used as a dispersant for example: condensation products are used of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene. or. of naphthalene sulfonic acids with phenol and Formaldehyde as well as alkali, ammonium and alkaline earth salts of lignin sulfonic acid, further alkylarylsulfonates, alkali and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, Fatty alcohol sulphates, v / ie salts of sulphated hexadecanols, Heptadecaioles, octadecanols and salts of sulfated Fcttalkoholglykol'a'theri · !, the sodium a Iz. 01 oy! Methyl tauride, ditertiary ethylene glycols, dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.

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ORIGINAL

Silicone oils, for example, can be used as antifoam agents Question. The active ingredients come with those listed above Adding so mixed, mixed, »sieved and passed, that in the case of wettable powders the solid portion has a particle size of 0.02 to 0.04 and in the case of pastes 0.03 mm does not exceed. For the production of emulsion concentrates and pastes become dispersants as listed in the previous sections, organic Solvent and water used. For example, alcohols are used as solvents,

IJimethylsulfoxid and boiling in the range from 120 to 35O * C Mineral oil fractions in question. The solvents should be practically odorless and inert towards the active ingredients be. - "

Furthermore, the agents according to the invention can be in the form of Solutions are applied. For this purpose, the active ingredient is bsiw. several active ingredients of the general formula I. Mix in suitable organic solvents or solvents mixed in. .Aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkyl naphthalenes, mineral oils Can be used alone or as a mixture with one another.

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ORIGINAL

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

Sttiubom itcel:

For the production of a) 0.5% and b) 2% dust the following substances are used:

a) 0.5 part active ingredient 99.5 part talc

b) 2 parts of active ingredient

1 part of highly disperse silica 97 parts of talc.

The active ingredients are mixed and ground into the carrier materials.
Stroiin »ttel:

5 Ttiile active ingredient are with

95 parts of carbonate of lime mixed and ground to an average particle size of 80/1.

Granules:

5 parts of active ingredient are in a solvent

vie methylene chloride dissolved and mixed with Z.Teile polyethylene glycol ("Carbowax") leave the mixture pure

91.5 parts of calcium carbonate impregnated and 1.5 parts of precipitated silica mixed in and then the solvent evaporated.

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j J: -powder:

Parts of the active ingredient have been τη it parts of a dispersant e.g. Ligninsvil fön acid-Na Lr iviiTi 5 al ζ, Parts of a wetting agent e.g. dibutylnaphthalenesulfonic acid, Mix parts of silica and parts of kaolin and grind finely.

s concentrate;

Parts of active ingredient are mixed with parts of emulsifier, for example

Alkyl aryl polyglycol alcohols with alkyl aryl sulfonates and
Share LUsungsmittcl mixed up

the solution is completely homogeneous.

This concentrate gives with water

an emulsion of any desired

Concentration.

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r em i > : (Fu t tr o r z \\ s at ζ )

0.25 4.75

95

Parts of the active ingredient and parts of secondary calcium phosphate, or kaolin, aerosil or carbonic acid coldness with parts of a feed such as * 2, B. Chicken feed mixed homogeneously.

Fame ·;

For Herstcll-ung a 27 _e strength Sprlihmittels the following ingredients are used:

98

Share Wirketof £
Share kerosene.

Other biocidal active ingredients or agents can be admixed with the agents described. So can the new ones Means other than the compounds of general formula I mentioned, for example insecticides for widening the Effective spectrum included.

The agents, or the active ingredients contained therein, develop their development-inhibiting effect primarily on larvae or pupae of insects, preferably of the order Diptera.

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example 1

2-Cvclopropylamino-4-NN-dimethylformami di no-6-morpholinos-triazine

20 g of 2-cyclopropylamino-4-amino-6-morpholino-s-triazine v / earth suspended in 200 ml of benzene and treated with 13 g of Ν, Ν-dimethylformaniicldimethylacetal and 0.5 g of p-toluenesulfonic acid (as a catalyst). The reaction mixture is refluxed for 10 hours. The solvent is removed in vacuo and the residue is suspended in ether. The deposited solid product is recrystallized from i-propanol. Mp. 160-162 ⁰ C.

The following connections are established in the same way:

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No connection snip, in ⁰ C

1 2-Cyclopropylamino-4-N ', N ¹ -dimethylformamidino-6-pyrrolidino-s-triazine 152-153

2 2-Cyclopropylamino-4-N ', N ¹ -dimethylformamidino-6-ethylamino-s-triazine 169-170

3 2-Cyclopropylatnino-4-N ', N ¹ -dimethyl-

formamidino - 6-me thy latnino - s - tr ia zin 186-188

4 2-Cyclopropylamino-4-N ', N ¹ -dimethylformatnidino-6-allylamino-s-triazine 158-159

5 2-cyclopropylamino-4-N ', N'-dimethyl-

formamidino-6-isopropylamino-s-triazine 193-194

6 2-CycloprpylaTnino-4-N ', N ¹ -dimethy 1-formamidino-6-propargylamino-s-triazine 126

7 2,6-Bis (cyclopropy latnino) -4-N ', N ¹ -ditnethylformamidino-s-triazine 220-223

8 2-Cyclopropylamino-4-N ¹ , N ¹ -dimethylformatnidino-6-imidazolo-s-triazine 184-185

9 2-Cyclopropylamino-4-N ¹ , N ¹ -dimethylformamidino-6- (2-methoxyethylamino) -s-trdasin 151-153

10 2-Cyclopropylamino-4-N ¹ , N ¹ -dimethylformamidino-6-dimethylamino-s-triazine 132-134

11 2-Cyclopropylamino-4-N ¹ , N ¹ -dimethylformamidino - 6- (N-methyl-N-e "thylamino) -s-triazine 96-98

12 2-Cyclopropylamino-4-N ', N'-dimethy1-

formamidino-6-amino-s-triazine 196-198

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Example 2 Effect against Musca domestica

50 g of maggot substrate each were weighed into beakers. An oily acetone solution was used for each active substance 2.5 ml each pipetted onto 50 g maggot substrate. After the treated substrate has been thoroughly mixed, the solvent is left in evaporate. 25 1-, 2- and 3-day maggots and approx. 50 fly eggs were then used for each active ingredient. To At the end of pupation, the pupae were flushed out and counted. After 10 days, the number of hatched flies became determined and thus a possible influence on the metamorphosis was determined.

The compounds of the formula I show a good activity in this test.

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Example 3 Action against Lv:; Ilia, sericata

Ral be given a 0.5% active substance-containing aqueous solution at 5O ⁰ C 1 to 9 ml of a culture medium. so

30 freshly hatched Lucilia sericata larvae are used Growing medium was given and after 48 and 96 hours the insecticidal effect was determined by determining the kill rate.

The compounds of the formula I show a good action against Lucilia sericata in this test.

Example 4

Effect against Aedes aegypti.

There is enough acetone on the surface of 150 ml of water in a container Solution of the active ingredient pipetted so that concentrations of 10, 5 and 1 ppm each are obtained. After the acetone has evaporated the containers are filled with 30-40 2-day Aedes larvae. Mortality is checked after 1, 2 and 5 days. The compounds of the formula I show one in this test good effect against Aedes aegypti.

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Claims (12)

Pate ntansprüche and where R _n R ₂ mean. Hydrogen, C 1 -C 4 -alkyl, optionally substituted by lower alkoxy, C ^ -C, -alkenyl, C3-C, -alkynyl, cyclopropy1, hydroxy, methoxy or ethoxy, Hydrogen, methyl or ethyl or, together with the adjacent nitrogen atom, a 5- or 6-membered, optionally also a further nitrogen atom or an oxygen atom, heterocyclic ring, methyl or ethyl,
Methyl or ethyl and
Hydrogen or methyl 809808/0822 ORIGINAL INSPECTED 2. Compounds according to claim 1, characterized in that R, hydrogen, C.-C, -alkyl, optionally substituted by lower alkoxy, C ^ -C, -alkenyl, CjC, -alkynyl, cyclopropyl, hydroxy, methoxy or ethoxy, R ₂ hydrogen, methyl or ethyl or R, and R _? together with the attached nitrogen atom 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl, 1-piperazinyl, 1- (4-methyl) -piperazinyl or 1-imidazolyl, IU methyl or ethyl, R, methyl or ethyl and R ₁ - hydrogen or methyl. 3. Compounds according to any one of claims 1 or 2, characterized in that R-, hydrogen, methyl, ethyl, isopropyl, 2-methoxyethyi, allyl, propargyl or cyclopropyl, R ₂ hydrogen or methyl or R, and R «together with the adjacent nitrogen atom 1-pyrrolidinyl, 4-morpholinyl or 1-imidazolyl, R ~ methyl, R, methyl and R ₁ . Signify hydrogen and in which, when R, signifies propargyl, R _? preferably represents hydrogen. 4. Compounds according to any one of claims 1 to 3, characterized in that R, hydrogen, methyl or ethyl, R _{2 is} hydrogen, Ro is methyl, R, methyl and Rr is hydrogen. 5. 2-Cyclopropylamino-4-dimethylformamidino-6-aminotriazine. 6. 2 -Cyc lopropy lamino-4-dime thy If ormamidino-6-a 'thy lamino s-triazine. 809808 / 082.2 -VS- 7. 2-Cyclopropylamino-4-dimethylfortnamidino-6-methy] -amino-s-tria interest. 8. 2-Cyclopropylamino-4-dimethylformamidino-6-propargy1-amino-s-triazine. 9. Process for the preparation of 2-Cyclopropyiainino-4-forniamidino-6-amino ~ s-triazines of the formula I vegetables claim 1, characterized in that one 2-Cyclopropylamino-4,6-dlaiTiino-5-triazine of the formula II »2» 1 Y. ^N II vorin R ^, R «and Rc have the meaning given for the formula I, with a carboxamide acotal or ketal of the formula III Al.kyl-0 ^ ^ ^N'J III Alkyl-0 ^ R ₄ vorin Rq and R _- , which have the meaning given for formula I , is implemented. 809808/0822 -2A- M. 10. Means for combating pests, thereby * "" "" characterized in that the active ingredient is a 2-cyclopropylamino-4 ~ formamidino-6-amino-s-triazine of formula I according to claim 1 contains. 11. Use of compounds of the formula I according to claim 1 for combating insects of the order Diptera. 12. Use of compounds of the formula I according to claim U for combating insects of the order Diptera belonging to families Culicidae, Simuliidae, Tipulidae, Muscidae and Calliphoridae. 809808/0822