GB1587573A

GB1587573A - 2-cyclo-propylamino-4,6-diamino-s-triazine derivatives and their use as insecticides

Info

Publication number: GB1587573A
Application number: GB34793/77A
Authority: GB
Original assignee: Ciba Geigy AG
Current assignee: Novartis AG
Priority date: 1976-08-19
Filing date: 1977-08-18
Publication date: 1981-04-08
Also published as: YU119182A; IL52765A0; YU41270B; NL930086I2; CY1248A; CH609835A5; NL930086I1; NL184894B; FR2362134B1; NL971032I2; NZ184953A; AT361249B; MY8300055A; CA1084921A; NL7709096A; ES461715A1; BE857896A; AU2804177A; JPS5325585A; SU727104A3

Abstract

The pesticide comprises, as active ingredient, a 2-cyclopropylamino-4-amino-6-hydroxylamino-s-triazine which optionally contains further substituents, or an acid addition salt thereof, with a strong mineral acid. The composition has a larvicidal activity against insect larvae. It causes the destruction of the egg larvae and prevents adults from hatching from the pupae, and is particularly suitable for controlling hygiene pests and animal ectoparasites.

Description

(54) "2- CYCLOPROPYLAMINO-4,6- DIAMINO- S-TRIAZINE DERIVATIVES AND THEIR USE AS INSECTICIDES (71) We, CIBA-GEIGY AG., a Swiss Body Corporate, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to 2-cyclopropylamino-4,6-diamino-s-triazine derivatives and salts thereof, to a process for their manufacture and to the use of 2-cyclopropylamino4,6-diamino-s-triazine derivatives as insecticides. The present invention provides a method of preventing the development of adult insects from larvae or pupae, which comprises applying to the larvae or pupae, a 2-cyclopropylamino-4,6-diamino-s-triazine derivative of the general formula

wherein Rl represents hydrogen, C1 4-alkyl which is unsubstituted or substituted by C1 -4 alkoxy or cyano, or represents C3- or C4-alkenyl, C3- or C4-alkynyl, cyclopropyl, hydroxyl, methoxy or ethoxy; R2 represents hydrogen, methyl or ethyl or Rl and R2 together with the nitrogen atom to which they are attached represent a 5- or 6-membered heterocyclic ring in which the nitrogen atom shown is the sole heteroatom or which contains a further nitrogen atom or an oxygen atom.

R3 represents hydrogen, C1 -C4-alkyl, C3-alkenyl, C3-alkynyl or cyclopropyl, R4 represents hydrogen, methyl or ethyl, or R3 and R4 together with the nitrogen atom towhich they are attached represent a 5- or 6-membered heterocyclic ring in which the nitrogen atom shown is the sole hetero-atom or which contains a further nitrogen atom or an oxygen atom, and R5 represents hydrogen or methyl, or an acid addition salt thereof.

Possible alkyl groups R, and R2 can be straight-chain or branched, unsubstituted or substituted by cyano groups or alkoxy groups of 1 to 4 carbon atoms. Examples of such alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- and tert-butyl, 2-methoxyethyl, 1-cyanoethyl, 1-cyanopropyl and 2-cyano-prop-2-yl. Examples of possible alkenyl and alkynyl groups R1 and R3 include allyl and propargyl respectively.

The term "acid addition salts" of the 2-cyclopropylamino-4,6-diamino-s-triazine derivatives of the formula I is to be understood as meaning salts with strong mineral acids, for example salts with hydrochloric acid or sulphuric acid.

Preferred compounds on account of their action are those compounds of the formula I in which R1 represents hydrogen, C1-C4-alkyl which is unsubstituted or substituted by C1-C4 alkoxy, or represents C3 or C4-alkenyl, C3 or C4-alkynyl, cyclopropyl, hydroxyl, methoxy or ethoxy; R2 represents hydrogen, methyl or ethyl, or R1 and R2 together with the nitrogen atom to which they are attached represent 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl, 1-piperazinyl, 1-(4-methyl)-piperazinyl or 1-imidazolyl; R3 represents hydrogen, C1-C4alkyl, C3-alkenyl, C3-alkynyl or cyclopropyl; R4 represents hydrogen, methyl or ethyl, or R3 and R4 together with the nitrogen atom to which they are attached represent 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl, 1-piperazinyl, 1-(4-methyl)-piperazinyl or 1-imidazolyl; and R5 represents hydrogen or methyl, and the acid addition salts thereof.

Compounds to be singled out for special mention are those in which R1 represents hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, hydroxyl or methoxy; R2 represents hydrogen, methyl or ethyl, or R, and R2 together with the nitrogen atom to which they are attached represent 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl or 1imidazolyl; R3 represents hydrogen, methyl, ethyl, n-propyl, isopropyl or cyclopropyl; R4 represents hydrogen, methyl or ethyl; and R5 represents hydrogen, and the acid addition salts thereof.

Particularly preferred compounds are those in which Rl represents hydrogen, ethyl or cyclopropyl; R2 represents hydrogen; R3 represents hydrogen or methyl; R4 represents hydrogen, methyl or ethyl; and R5 represents hydrogen, whilst at least one of the symbols R1, R3 and R4 represents hydrogen, and the hydrochlorides thereof, in particular 2-cyclopropylamino-4-amino-6-ethylamino-s-triazine dihydrochloride, 2,4-bis (cyclopropylamino)-6-amino-s-triazine, 2-cyclopropyl-amino-4-amino-6-methylamino-striazine dihydrochloride, 2-cyclopropylamino-4 ,6-diamino-s-triazine, 2-cyclopropylamino4-amino-6-dimethylamino-s-triazine, 2-cyclopropylamino-4,6-bis-(ethylamino)-s--tnazine dihydrochloride and 2-cyclopropylamino-4-amino-6-(N-methyl-N-ethylamino)-s-triazine.

The invention also includes as compounds per se, compounds of formula (I) except those in which Rt is butyl, hydroxyl, methoxy or ethoxy, or in which R3 is butyl and with the provisos that: (1) Rl does not represent cyclopropyl when simultaneously (a) R2 and R3 represent hydrogen and R4 represents methyl or ethyl or (b) R2 and R4 represent hydrogen and R3 represents methyl, ethyl, n-propyl or cyclopropyl (2) R3 does not represent cyclopropyl when simultaneously (a) R, and R4 represent hydrogen and R2 represents methyl or ethyl or (b) R2 and R4 represent hydrogen and Rl represents methyl ethyl, n-propyl or cyclopropyl.

The invention includes also insecticidal compositions comprising such a compound and a carrier.

The compounds of the formula I can be obtained by methods which are known per se, for example by a) reacting a 2-cyclopropylamino-4-amino-6-halogeno-s-triazine of the formula II, in which R1, R2 and R5 are as defined in formula I and X represents halogen, preferably chlorine, with ammonia or a primary or secondary amine of the formula V, in which R3 and R4 are as defined in formula I:

or b) reacting a 2,4-diamino-6-halogeno-s-triazine of the formula III, in which R1, R2, R3 and R4 are as defined in formula I and X represents halogen, preferably chlorine, with a compound of the formula VI, in which R5 is as defined in formula I:

or c) if in the compounds of the formula I R1 has the same meaning as R3 and R2 has the same meaning as R4, reacting a 2-cyclopropylamino-4,6-dihalogeno-s-triazine of the formula IV, in which R5 is as defined in formula I and X represents halogen, preferably chlorine, with ammonia or a primary or secondary amine of the formula VII, in which R', has the meaning of R1 = R3, as defined in formula I, and R'2 has the meaning of R2 = R4, as defined in formula I:

The substitution of the halogen atoms with ammonia or a primary and!or secondary amine of the formulae V, VI and VII can be efected by dissolving the starting material of the formulae II, III and IV in an inert solvent, for example acetone, acetone/water mixtures, methyl ethyl ketone, dioxane or dioxane/water mixtures, and reacting the mixture at normal or, if appropriate, elevated pressure and at a temperature between 20 and 1500C, preferably between 50 and 140"C, with ammonia or a primary and/or secondary amine.

Most of the starting materials of the formulae II, III and IV are known or they can be obtained in accordance with known methods.

Diamino- and triamino-s-triazines are described as chemosterilants for adult houseflies (Musca domestica) in US patent specification 3,189,521. The cheomsterilising action on insects of 2,4,6-triamino-s-triazine derivatives (melamine derivatives) is also described by S.

Nagasawa et al., Botyu-Kagaku 39 (4), 105 (1974). A.B. Borkovec and A.B. DeMilo [J.

Med. Chem. 10 (5), 457 (1967)] and G.C. LaBrecque, R.L. Fye, A.B. DeMilo and A.B.

Borkovec [J. Econ. Entomol. 61, (6), 1621(1968)] also describe the chemosterilising action of, among other compounds, 2-cyclohexylamino-4,6-diamino-s-triazine, 2 cyclohexylamino-4 ,6-dihexylamino-s-triazine and 2 ,4,6-tris-cyclohexylamino-s-triazine, and the salts thereof, on adult houseflies (Musca domestica).

Surprisingly, it has now been found that the compounds of the formula I possess a marked larvicidal action on insect larvae, preferably on Diptera larvae. In contrast to the above mentioned insecticidal chemosterilants, the compounds of the formula I act on the developmental stages of the insects. The action consists in killing the freshly hatchet larvae or preventing adults from hatching from the pupae. The mode of action of the compounds of the formula I is not to be compared with that of classical insecticides, chemosterilants or juvenile hormone analogues.

The compounds of the formula I can be used in particular for controlling hygiene pests and animal ectoparasites of the order Diptera especially of the families: Culicidae, Simuliidae, Tipulidae, Muscidae and Calliphoridae.

The compounds of the formula I without any additive or together with suitable carrier(s) and/or additive(s). Suitable carriers and additives can be solid or liquid and can be any conventionally used in the art of formulation of a larvicidal insecticide, for example natural or regenerated substances, solvents and/or dispersants.

The compositions according to the invention can be manufactured in known manner by homogeneously mixing and/or grinding an active substance (compound of the formula I) with a suitable carrier, which can include a dispersants or solvent and which is inert to the active substance.

The active substances may be processed to the following formulations: Solid formulations: Dusts, tracking agents and granules (coated granules, impregnated granules and homogeneous granules), premix (feed additive Liquid formulations: a) active substance concentrates which are dispersible in water: wettable powders, pastes and emulsions; b) solutions: sprays (aerosols).

To manufacture a solid formulation (dusts, tracking agents), the active substance is mixed with a solid carrier. Suitable carriers are, for example: kaolin, talc, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegctable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These carriers can either be used alone or in admixture with one another.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the solution thereby obtained to a granulated mineral, for example attapulgite, Six2, granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing an active substance of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having preferably a bulk density of 300 g/litre to 600 g/litre can also be manufactured with the aid of atomisers.

It is also possible to obtain granules by compacting the carrier with the active substance and additive(s) and subsequently comminuting the product.

To these mixtures can also be added additivies which stabilize the active substance and/or nonionics, anionics and cationics, which, for example, ensure a better wettability (wetting agents) and dispersibility (dispersants). Examples of suitable substances are: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 or 9 carbon atoms in the alkyl moiety, ligninsulphonic acid, the alkali metal and alkaline earth metal salts thereof, polyethylene glycol ethers, fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidone, polyvinyl alcohol. condensation products of urea and formaldehyde.

and also latex products.

Water-dispersible concentrates, i.e. wettable powders, pastes and emulsifiable concentrates, are compositions which can be diluted with water to the desired concentration. Thev consist of active substance. carrier. optionally additive(s) which stabilize the active substance, surface-active substance(s) and anti-foam(s) and, if appropraite, solvent(s).

Wettable powders and pastes are obtained by mixing and grinding the active substance with dispersant(s) and pulverulent carrier(s) in suitable devices until homogeneity is attained. Suitable carriers are. for example, those already mentioned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. Examples of dispersants are: condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde. condensation products of naphthalene or naphthalene sulphonic acids with phenol and formaldehyde. as well as alkali metal.

ammonium and alkaline earth metal salts of ligninsulphonic acid. in addition alkvlarvlsulphonates. alkali metal and alkaline earth metal salts of dibutylnaphthalenesulphonic acid.

fatty alcohol sulphates such as salts of sulphated hexadecanols. heptadecanols. octadecanols, and salts of sulphated fatty alcohol glycol ethers. the sodium salt of olevl methvl tauride. ditertiarv ethylene glycols. dialkyl-dilaurylammonium chloride and fatty acid alkali metal and alkaline earth metal salts.

Suitable anti-foams are for example silicone oils.

The active substances is so mixed. ground. sieved and strained with the additive(s) mentioned above that. in wettable powders. the solid particle size of 0.02 to 0.04 mm and in pastes. of 0.03 mm. is not exceeded. Emulsifiable concentrates and pastes are manufactured bv using dispersants. such as those referred to above. organic solvents and water.

Examples of suitable solvents are: alcohols. dimethyl sulphoxide. and mineral oil fractions which boil between 120 and 350"C. The solvents must be virtuallv odourless and inert to the active substances.

Furthermore. the compositions of compounds of formula I can take the form of solutions.

For this purpose the compound or compounds of the general formula I are dissolved in a suitable organic solvent or mixture of solvents. Aliphatic and aromatic hydrocarbons.

chlorinated derivatives thereof. alkylnaphthalenes and mineral oils. singlv or in admixture.

can be used as organic solvents.

Formulations of the compounds of the formula I are described hereinafter. The parts denote parts by weight.

Dldsts: The following substances are used to manufacture a) a 0.5cos and b) a 2% dust: a) 0.5 part of active substance 99.5 parts of talc b) 2 parts of active substance 1 part of highly disperse silica 97 parts of talc.

The active sbstance is mixed with the carrier and ground.

Tracking Agezlts.

5 parts of active substance are mixed with 95 parts of carbonate of lime and ground to an average particle size of Sort.

Grallldes: parts of active substance are dissolved in a solvent. e.g. methylene chloride. and mixed with 2 parts of polyethylene glycol ( Carbox ax Registered Trade Mark) 91.5 parts of calcium carbonate are impregnated xxith the mixture and 1.5 parts of precipitated silica are admixed.

The solvent is subsequently evaporated.

U'ettable Po1sder: 50 parts of active substance are mixed with parts of a dispersing agent. e.g. sodium ligninsulphonate.

5 parts of a wetting agent. e.g. dibutylnaphthalenesulphonic acid 10 parts of silica and 30 parts of China clay and the mixture is finely ground.

Emulsifiable Concentrate: 20 parts of active substance are mixed with 20 parts of emulsifier, e.g. a mixture of alkylarylpolyglycol ether with alkylarylsul phonates, and 60 parts of solvent until the solution is completely homogeneous.

By diluting this concentrate with water it is possible to obtain an emulsion of the desired concentrate.

Premix (feed additive): 0.25 part of active substance and 4.75 parts of secondary calcium phosphate, or China clay, "Aerosil" (Registered Trade Mark) or carbonate of lime are homogeneously mixed with 95 parts of an animal feed, e.g. poultry food.

Spray: The following constituents are used to manufacture a 2% spray: 2 parts of active substance 98 parts of kerosene.

Other biocidal active substances or agents can be admixed with the compositions described hereinabove. Thus in addition to the cited compounds of the general formula I, the compositions of the present invention can obtain, for example, insecticides to broaden the activity spectrum.

The compositions, or the compounds of the formula (I) contained therein, exert their inhibitory action therefore chiefly on the development of larvae or pupae of insects, preferably of the order Diptera.

EXAMPLE 1 2-Cyclopropyla,nitio-4-aniiio-6-ediyla,nitios-tnazitie A mixture of 13.7 g of 2-cyclopropylamino-4-chloro-6-ethyl-amino-s-triazine, 17.4 g of 25% conc. aqueous ammonia and 30 ml of dioxane is heated for 2 hours in an autoclave to 1300C. After cooling, the reaction mixture is poured into water, whereupon the crude product precipitates. After drying, the product is recrystallized from ether/hexane. Melting point: 141-145"C.

EXAMPLE 2 2, 4-Bis-cyclopropylamino-6-isopropylamino-s-triazine A mixture of 30 g of 2-cyclopropylamino-4-chloro-6-isopropylamino-s-triazine, 15.1 g of cyclopropylamine and 50 ml of dioxane is heated for 10 hours in an autoclave to 1300C.

After cooling, the reaction mixture is concentrated to half its volume in vacuo and then poured into 300 ml of water and extracted with ethyl acetate. The extract is dried over sodium sulphate and the ethyl acetate und dioxane are removed in vacuo. The crude product is recrystallised from dioxane/petroleum ether. Melting point: 88"-93"C.

EXAMPLE 3 a) 2-Cyclopropylamino-4-amino-6-morpholino-s-triazine 9.3 g of 2-cyclopropylamino-4-chloro-6-amino-s-triazine are suspended in a mixture of 45 ml of dioxane and 9 ml of ether. Then 8.7 g of morpholine are added dropwise at room temperature. The reaction is exothermic and the reaction mixture becomes fluid. The reaction mixture is allowed to continue to react for 16 hours at room temperature and the dioxane and ether are then removed in vacuo. The residue is diluted with water and filtered. After drying the residual crude product is recrystallised from methanol. Melting point: 186"C.

b) 5 g of 2-cyclopropylamino-4-amino-6-morpholino-s-triazine are dissolved in 700 ml of abs. ether and then gaseous hydrogen chloride is introduced at 10 C until the solution is saturated. The precipitated crystals are filtered off and washed with a small amount of methanol. The resultant hydrochloride of 2-cyclopropylamino-4-amino-6-morpholino-striazine melts at 2500C.

EXAMPLE 4 2-Cyclopropylarnino-4, 6-bis-dimethylamino-s-triazine 123 g of 2-cyclopropylamino-4,6-dichloro-s-triazine are dissolved in 300 ml of dioxane.

Then 397 g of 40.8 % aqueous dimethylamine are added dropwise with gentle cooling in such a manner that the internal temperature does not exceed 55"C. The reaction is allowed to continue for 4 hours at room temperature. The reaction mixture is then taken up in ether and the aqueous phase is separated. The ether and dioxane are removed in vacuo after washing with water and drying over sodium sulphate. The crude product is recrystallised from isopropanol. Melting point: 82-83"C.

The following active compounds of the formula I are also prepared by proceeding as described in Examples 1 to 4: No. Compound mp. in "C 1 2-cyclopropylamino-4-amino-6- 159-162 methylamino-s-triazine 2 2-cyclopropylamino-4,6-bis-(isopropyl- 119-121 amino)-s-triazine 3 2,4,6-tris-(cyclopropylamino)-s-triazine 75-76 4 2-cyclopropylamino-4-amino-6- 186 pyrrolidino-s-triazine 5 2-cyclopropylamino-4-ethylamino-6- 90-91 morpholino-s-triazine 6 2-cyclopropylamino-4-ethylamino-6- 169-170 pyrrolidino-s-triazine 7 2-cyclopropylamino-4-amino-6- 186 morpholino-s-triazine 8 2-cyclopropylamino-4-ethylamino-6- 90-91 morpholino-s-triazine 9 2-cyclopropylamino-4-amino-6- 250 morpholino-s-triazine hydrochloride 10 2-cyclopropylamino-4-amino-6- 244-245 imidazolo-s-triazine 11 2-cyclopropylamino-4-amino-6-pyrroli- 196-197 dino-s-triazine dihydrochloride 12 2-cyclopropylamino-4-amino-6-ethylamino- 199-200 s-triazine dihydrochloride 13 2-cyclopropylamino-4-ethylamino-6- 226-227 pyrrolidino-s-triazine hydrochloride 14 2-cyclopropylamino-4-ethylamino-6- 230-231 morpholino-s-triazine hydrochloride 15 2-cyclopropylamino-4-amino-6-isopropyl 172-173 amino-s-triazine dihydrochloride 16 2-cyclopropylamino-4-amino-6-allylamino- 183-185 s-triazine dihydrochloride 17 2-cyclopropylamino-4-amino-6-propargyl- 225-226 amino-s-triazine 18 2,4-bis-(cyclopropylamino)-6-amino-s- 137-140 triazine 19 2,4-bis-(cyclopropylamino)-6-dimethyl- 136-137 amino-s-triazine 20 2-cyclopropylamino-4-amino-6-methyl- 197-199 amino-s-triazine dihydrochloride 21 2-cyclopropylamino-4,6-diamino-s- 219-222 triazine 22 2-cyclopropylamino-4-amino-6-(2-methoxy- 154-156 ethylamino)-s-triazine 23 2-cyclopropylamino-4-amino-6-dimethyl 182-184 amino-s-triazine 24 2-cyclopropylamino-4,6-bis-(ethylamino)- (viscous) s-triazine 25 2-cyclopropylamino-4-methylamino-6-n- (viscous) propylamino-s-triazine 26 2-cyclopropylamino-4-ethylamino-6-n- (viscous) propylamino-s-triazine 27 2,4-bis-(cyclopropylamino)-6-diethyl- 76-77 amino-s-triazine 28 2-cyclopropylamino-4-amino-6-(N-methyl- 150-152 N-ethylamino)-s-triazine 29 2-cyclopropylamino-4,6-bis-(methyl- 158-162 amino)-s-triazine dihydrochloride 30 2-cyclopropylamino-4-methylamino-6- 164-165 dimethylamino-s-triazine dihydrochloride 31 2.4-bis-(cyclopropylamino)-6-ethyl- 168-170 amino-s-triazine dihydrochloride 32 2-cyclopropylamino-4,6-bis-(ethylamino)- 170-172 s-triazine dihydrochloride 33 2-cyclopropylamino-4-methylamino-6-n- 164-165 propylamino-s-triazine dihydrochloride 34 2-cyclopropylamino-4-ethylamino-6-n- 164-165 propyl-amino-s-triazine dihydrochloride 35 2,4-bis-(cyclopropylamino)-6-n-propyl 166-168 amino-s-triazine dihydrochloride 36 2,4-bis-(cyclopropylamino)-6-methyl 174-176 amino-s-triazine dihydrochloride 37 2-cyclopropylamino-4-ethylamino-6- 198 hydroxylamino-s-triazine 38 2-cyclopropylamino-4-dimethylamino-6- 140-142 isopropylamino-s-triazine 39 2-cyclopropylamino-4-dimethylamino-6- 148-150 morpholino-s-triazine 40 2-cyclopropylamino-4-amino-6- 128-129 diethylamino-s-triazine 41 2,4-bis-(cyclopropylamino)-6- 137-138 morpholino-s-triazine 42 2,4-bis-(cyclopropylamino)-6- 193-196 pyrrolidino-s-triazine 43 2-cyclopropylamino-4-dimethylamino-6- 178-180 propargylamino-s-triazine hydrochloride 44 2-cyclopropylamino-4-dimethylamino-6- 208 morpholino-s-triazine hydrochloride 45 2-cyclopropylamino-4-methylamino-6-di- 153-154 ethylamino-s-triazine hydrochloride 46 2-cyclopropylamino-4-ethylamino-6-di- 144-145 ethyl-amino-s-triazine hydrochloride 47 2-cyclopropylamino-4-dimethylamino-6- 153-154 diethylamino-s-triazine hydrochloride 48 2-cyclopropylamino-4-dimethylamino-6- 220 ethylamino-s-triazine hydrochloride 49 2-cyclopropylamino-4-dimethylamino-6- 214 pyrrolidino-s-triazine hydrochloride 50 2-cyclopropylamino-4-6-bis-(diethylamino (oilv) s-triazine hydrochloride 51 2-cyclopropylamino-4-dimethylamino-6- 19()-19l isobutylamino-s-triazine dihydrochloride 52 2-cyclopropylamino-4-ethylamino-6-iso- 94.5-96 propylamino-s-triazine 53 2-cyclopropylamino-4-ethylamino-6- 111- 112 dimethylamino-s-triazine 54 2-cyclopropylamino-4-ethylamino-6-tert. 261-263.5 butytamino-s-triazine hydrochloride 55 2-cyclopropylamino-4,6-bis-(ethylamino)- 140-142 s-triazine hydrochloride 56 2-cyclopropylamino-4-ethylamino-6-n- 141.5- t43 butylamino-s-triazine dihydrochloride 57 2-cyclopropylamino-4-ethylamino-6-iso 154-155 butylamino-s-triazine dihydrochloride 58 2-cyclopropylamino-4-ethylamino-6-sec. 75-77 butylamino-s-triazine EXANIPLE 5 Test substance: compounds of the formula I formulated as acetonic solutions Test subject: i (sca dostlestica Test material: CSMA nutrient substrate for maggots Concentration: 0.1C; 0.05%, 0.01% of active substance Test method: 50 of freshly prepared CSMA nutrient substrate for maggots are charged into beakers. A specific amount of a 1% acetonic solution of the respective active substance is pipetted onto the nutrient substrate present in the beakers. The substrate is then thoroughly mixed and the acetone subsequently allowed to evaporate over a period of at least 20 hours.

Then 25 one-day-old maggots of Musca doniesdc'z are put into each of the beakers containing the treated nutrient substrate for testing with each active substance at one of its given concentrations. After 5 days, the pupae are separated from the substrate by flushing them out with water and then deposited in the same beaker.

Each batch of flushed out pupae is counted to determine the toxic effect of the active substance on the maggot development. The number of flies which have hatched out of the pupae are then counted after 10 days and any influence on the metamorphosis thereby determined.

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

EXAMPLE 6 Test substance: compound of the formula I formulated as acetonic solutions Test subject: Andes aegypti Test material: yoghourt beakers filled with water Concentration: 10 ppm, 5 ppm, and 1 ppm of active substance Test method: Yoghourt beakers are each filled with 150 ml of water and a specific amount of a 0.1% solution of the active substance in acetone is pipetted onto the surface of the water. After the acetone has evaporated, 30 to 40 two-day-old larvae of Aedes aegypti are put into each of the beakers containing the active substance solution. Two beakers per concentration of active substance are used for the test.

Then ground dog-biscuit is added to the beakers, which are covered with a copper gauze top.

Evaluation of mortality is

Claims

**WARNING** start of CLMS field may overlap end of DESC **. with each active substance at one of its given concentrations. After 5 days, the pupae are separated from the substrate by flushing them out with water and then deposited in the same beaker. Each batch of flushed out pupae is counted to determine the toxic effect of the active substance on the maggot development. The number of flies which have hatched out of the pupae are then counted after 10 days and any influence on the metamorphosis thereby determined. The compounds of the formula I exhibit good activity in this test. EXAMPLE 6 Test substance: compound of the formula I formulated as acetonic solutions Test subject: Andes aegypti Test material: yoghourt beakers filled with water Concentration: 10 ppm, 5 ppm, and 1 ppm of active substance Test method: Yoghourt beakers are each filled with 150 ml of water and a specific amount of a 0.1% solution of the active substance in acetone is pipetted onto the surface of the water. After the acetone has evaporated, 30 to 40 two-day-old larvae of Aedes aegypti are put into each of the beakers containing the active substance solution. Two beakers per concentration of active substance are used for the test. Then ground dog-biscuit is added to the beakers, which are covered with a copper gauze top. Evaluation of mortality is made after 1, 2 and 5 days respectively. Subsequently, evaluation is made of the inhibiting action on pupation, metamorphosis, and shedding and emergence to the adult stage. The compounds of the formula I have a good action in this test. EXAMPLE 7 Test substances: Active substances of the formula I formulated as 25% wettable powder or as aqueous solution or suspension of the hydrochlorides. Test subject: Lucilia sericata (blowfly), fresly hatched - larve I Concentration: 250 ppm of acrtive substance Test method: 1 ml of an aqueous suspension or solution of the active substance in a concentration of 1000 ppm is added at 50"C to 3 ml of a special culture medium so as to give a homogeneous mixture with an active substance content of 250 ppm. Approx. 30 Lucilia larvae are used for each test. Evaluation of mortality is made after 4 days. In this test, the compounds of formula I exhibit good action. WHAT WE CLAIM IS:

1. 2-Cyclopropylamino-4,6-diamino-s-triazines of the formula I

wherein R, represents hydrogen, C,-C-alkyhl which is unsubstituted or substituted by C1-C4- alkoxy or cyano or represents C3- or C4-alkenyl C3- or C4-alkynyl or cyclopropyl, R2 represents hydrogen, methyl or ethyl or R, and R, together with the nitrogen atom to which they are attached represent a 5- or 6-membered heterocyclic ring in which the nitrogen atom shown is the sole hetero-atom or which contains a further nitrogen atom or an oxygen atom, R3 represents hydrogen, C,-C,-alkyl, C3-alkenyl, C3-alkynyl or cyclopropyl, R4 represents hydrogen, methyl or ethyl, or Rl and R4 together with the nitrogen atom to which they are attached represent a 5- or 6-membered heterocyclic ring in which the nitrogen atom shown is the sole

hetero-atom or which contains a further nitrogen atom or an oxygen atom, and R5 represents hydrogen or methyl, and the acid addition salts thereof, provided that: (1) R1 does not represent cyclopropyl when simultaneously (a) R2 and R3 represent hydrogen and R4 represents methyl or ethyl or (b) R2 and R4 represent hydrogen and R3 represents methyl, ethyl, n-propyl or cyclopropyl; and (2) R3 does not represent cyclopropyl when simultaneously (a) R1 and R4 represent hydrogen and R2 represents methyl or ethyl or (b) R2 and R4 represent hydrogen and R1 represents methyl, ethyl, n-propyl or cyclopropyl.

2. Compounds according to claim 1 wherein R1 represents hydrogen, C1 -C3-alkyl which is unsubstituted or substituted by C1-C4-alkoxy, or represents C3- or C4-alkenyl, C3or C4-alkynyl, cyclopropyl; R2 represents hydrogen, methyl or ethyl, or R1 and R2 together with the nitrogen atom to which they are attached represent 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl, 1-piperazinyl or 1-(4-methyl)-piperazinyl; R3 represents hydrogen , C1-C3- alkyl, C3-alkenyl, C3-alkynyl or cyclopropyl; R4 represents hydrogen, methyl or ethyl, or R3 and R4 together with the nitrogen atom to which they are attached represent 1-pyrrolidinyl, 1-piperidinyl, 4-morpholinyl, 1-piperazinyl or 1-(4-methyl)-piperazinyl and R5 represents hydrogen or methyl.

3. Compounds according to claim 1 wherein R1 and R2, together with the nitrogen atom to which they are attached, represent a 1-imidazolyl group and/or R3 and R4 together with the nitrogen atom to which they are attached represent a 1-imidazolyl group and all other symbols are as defined in claim 2.

4. Compounds according to claim 1 wherein R1 represents hydrogen, methyl, ethyl, n-propyl, isopropyl, or cyclopropyl; R2 represents hydrogen, methyl or ethyl, or R1 and R2 together with the nitrogen atom to which they are attached represent 1-pyrrolidinyl, 1-piperidinyl or 4-morpholinyl; R3 represents hydrogen, methyl, ethyl, n-propyl, isopropyl or cyclopropyl; R4 represents hydrogen, methyl or ethyl; and R5 represents hydrogen.

5. Compounds according to claim 1 wherein R1 and R2 together with the nitrogen atom to which they are attached represent an imidazolyl group and all other symbols are as defined in claim 4.

6. Compounds of formula (I) defined in claim 1 wherein R1 represents hydrogen, ethyl, or cyclopropyl; R2 represents hydrogen; R3 represents hydrogen or methyl, R4 represents hydrogen, methyl or ethyl and R5 represents hydrogen, but at least one of the symbols R1, R3 and R4 represents hydrogen, and the hydrochlorides thereof.

7. 2-Cyclopropylamino-4-amino-6-ethylamino-s-triazine dihydrochloride.

8. 2 ,4-Bis-(cyclopropylamino)-6-amino-s-triazine.

9. 2-Cyclopropylamino-4-amino-6-methylamino-s-triazine dihydrochloride.

10. 2-Cyclopropylamino-4,6-diamino-s-triazine.

11. 2-Cyclopropylamino-4-amino-6-dimethylamino-s-triazine .

12. 2-Cyclopropylamino-4,6-bis-(ethylamino)-s-triazine dihydrochloride.

13. 2-Cyclopropylamino-4-amino-6-(N-methyl-N-ethylamino)-s-triazine.

14. 2 ,4-Bis-cyclopropylamino-6-isopropylamino-s-triazine.

15. 2-Cyclopropylamino-4,6-bis-dimethylamino-s-triazine.

16. Each of the compounds 2, 4, 5 and 6 hereinbefore specifically named.

17. Each of the compounds 8 to 30, 32, 33, 34, 38 to 50, 52, 53 and 55 hereinbefore specifically named.

18. A process for the manufacture of 2-cyclopropyl-amino-4,6-diamino-s-triazines claimed in claim 1, which comprises reacting a 2-cyclopropylamino-4-amino-6-halogeno-striazine of the formula II

in which Rl, R2 and R5 are as defined in claim 1 and X represents halogen, with ammonia or a primary or secondary amine of the formula V

in which R3 and R4 are as defined in formula I.

19. A process according to claim 18 in whih X is chlorine.

20. A process for the manufacture of 2-cyclopropylamino-4,6-diamino-s-triazines claimed in claim 1, in which Rl and R3 are identical and R2 and R4 are identical, wherein a 2-cyclopropylamino-4 ,6-dihalogeno-s-triazine of the formula IV

in which R5 is as defined in formula I and X represents halogen, is reacted with ammonia or with a primary or secondary amine of the formula VII

in which R'1 has the same meaning as R, and R3 and R'2 have the same meanings as R2 and R4 respectively.

21. A process according to claim 20 wherein X represents chlorine.

22. 2-Cyclopropylamino-4,6-diamino-s-triazines claimed in claim 1 when obtained by a process claimed in claim 18, 19, 20 or 21.

23. An insecticidal composition comprising a 2-cyclopropylamino-4,6-diamino-striazine claimed in any one of claims 1 to 17 and a carrier.

24. A composition according to claim 23 in the form of a dust, tracking agent, granules, wettable powder, emulsifiable concentrate, animal feed additive or spray.

25. A method of preventing the development of adult insects from larvae or pupae, which comprises applying to the larvae or pupae a 2-cyclopropylamino-4,6-diamino-striazine of the formula

wherein R, represents hydrogen, C,-C4-alkyl which is unsubstituted or substituted by C1-C4- alkoxy or cyano or represents C3- or C4-alkenyl, C3- or C4-alkynyl, cyclopropyl, hydroxyl, methoxy or ethoxy R2 represents hydrogen, methyl or ethyl or R, and R, together with the nitrogen atom to which they are attached represent a 5- or 6-membered heterocyclic ring in which the nitrogen atom shown is the sole hetero-atom or which contains a further nitrogen atom or an oxygen atom, R3 represents hydrogen, C1-C4-alkyl C3-alkenyl, C3-alkynyl or cyclopropyl, R4 represents hydrogen, methyl or ethyl, or R3 and R4 together with the nitrogen atom to which they are attached represent a 5- or 6-membered heterocyclic ring in which the nitrogen atom shown is the sole hetero-atom or which contains a further nitrogen atom or an oxygen atom, and R5 represents hydrogen or methyl, or an acid addition salt thereof.

26. A method according to claim 25 wherein the insects are of the order Diptera.

27. A method according to claim 26 wherein the insects are of the families Culicidae, Simuliidae, Tipulidae, Muscidae and Calliphoridae which belong to the order Diptera.

28. A method according to claim 25, 26 or 27 wherein a compound claimed in any one of claims 2, 4, 7, 8, 9, 14, 15 and 16 is applied.

29. A method according to claim 25, 26 or 27 wherein the compound 3 hereinbefore specifically named is applied.

30. A method according to claim 25, 26 or 27 wherein a compound claimed in any one of claims 3, 5, 6, 10 to 13, and 17 is applied.

31. A method according to claim 25, 26, or 27 wherein any of the compounds 31, 35 to 37, 51, 54 and 56 to 58 hereinbefore specifically named is applied.