CA1084922A - Derivatives of 2-cyclopropylamino-4-formamidino-6- amino-s-triazine as insecticides - Google Patents
Derivatives of 2-cyclopropylamino-4-formamidino-6- amino-s-triazine as insecticidesInfo
- Publication number
- CA1084922A CA1084922A CA284,901A CA284901A CA1084922A CA 1084922 A CA1084922 A CA 1084922A CA 284901 A CA284901 A CA 284901A CA 1084922 A CA1084922 A CA 1084922A
- Authority
- CA
- Canada
- Prior art keywords
- methyl
- ethyl
- represents hydrogen
- cyclopropylamino
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
Abstract
Abstract of the Disclosure 2-Cyclopropylamino-4-formamidino-6-amino-s-triazine of the formula
Description
~084922 The present invention relates to novel 2-cyclopropylamino-4-formamidino_6-amino_s_triazine derivatives, to a process for their manufacture and to their use in pest control.
The 2_cyclopropylamino-4-formamidino-6-amino-s-triazine derivatives have the formula ~2 ~1 `~! .
,~, N ~ I
N^CII-N ~ H ~ 5 wherein Rl represents hydrogen, Cl-C4-alkyl which is unsubstituted or substituted by lower alkoxy, or represents C3-C4-alkenyl, C3-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 which can contain a further nitrogen atom or an oxygen atam, R3 represents methyl or ethyl, R4 represents methyl or ethyl, and R5 represents hydrogen or methyl.
The 2_cyclopropylamino-4-formamidino-6-amino-s-triazine derivatives have the formula ~2 ~1 `~! .
,~, N ~ I
N^CII-N ~ H ~ 5 wherein Rl represents hydrogen, Cl-C4-alkyl which is unsubstituted or substituted by lower alkoxy, or represents C3-C4-alkenyl, C3-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 which can contain a further nitrogen atom or an oxygen atam, R3 represents methyl or ethyl, R4 represents methyl or ethyl, and R5 represents hydrogen or methyl.
- 2 -, . -.
, ' . ' , ' ~
~084922 Possible alkyl groups represented by Rl can be straight-chain or branched, unsubstituted or substituted for example by low~r 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 and 2-methoxyethyl. Examples of possible C3-C4-alkenyl and C3-C4-alkynyl groups represented by Rl include allyl and propargyl respectively.
Preferred compounds on account of their action are compounds of the formula I in which Rl represents hydrogen, Cl-C4-alkyl which is unsubstituted or substituted by lower alkoxy, or represents C3-C4-alkenyl, C3-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 l-pyrrolidinyl, l_piperidinyl, 4-morpho-linyl, l_piperazinyl, 1_(4_methyl)-piperazinyl or l-~midazolyl, R3 represents methyl or ethyl, R4 represents methyl or ethyl and R5 represents hydrogen or methyl.
Particularly advantageous compounds are those in wh~ch R
represents hydrogen, methyl, ethyl, isopropyl, 2_methoxy_ ethyl, allyl, propargyl or cyclopropyl, R2 represents hydro-gen or methyl or Rl and R2 together with the nitrogen atom to which they are attached represent l-pyrrolidinyl, 4-morpho-linyl or l-im~dazolyl, R3 represents methyl, R4 represents methyl and R5 represents hydrogen, and in which, if Rl re-presents propargyl, R2 prefera~ly represents hydrogen.
.. . . . .
.
- ~
.
-~084922 Compounds to be particularly highlighted are those in whichRl represents hydrogen, methyl or ethyl, R2 represents hydro-gen, R3 represents methyl, R4 represents methyl and R5 represents hydrogen.
Particularly preferred compounds are:
2-cyclopropylamino-4-dimethylformamidino-6-amino-s-triazine, 2-cyclopropylamino-4-dimethylformamidino_6-ethyl~mino_s-triazine, 2-cyclopropylamino-4-dimethylformamidino-6-methylamino-s-triazine, and 2_cyclopropylæmino-4-dimethylformamidino-6-propargylamino_s_ triazine.
The compounds of the formula I are obtained by methods which are known per se, for example by (a) reacting a 2-cyclopropylamino-4,6-diamino_s-triazine of the formula II
N N (II) 2N~ 11 NH~n5 in which Rl, R2 and R5 are as defined in formula I, with .
. . ~ .
.
- ' ~ ' ' ~
- , ;! a carboxy amide acetal or kctal of the formula III
alkyl - O \ / R3 / CH - N (III) alkyl - O R4 in which R3 and R4 are as defined in formula I, or (b) reacting a 2-cyclopropylamino-4-formamidino-6-chloro-s-triazine of the formula IV
Cl N N
/ N-CH-N ~ ~ N~ ~ (IV) in which R3, R4 and R5 are as defined in fonmula I, with ammonia or with a primary or secondary amine of the formula V
HN'~ 1 (V) in which Rl and R2 are as defined in formula I.
The above reactions (a) and (b) are preferably carried out in solvents or diluents which are inert to the reactants, for example in aliphatic or aromatic hydrocarbons, halogenated ~084922 hydrocarbons, ethers or ethereal compounds or ketones.
Catalysts, for example p-toluenesulphonic acid, c~n be added to the reaction mixture, but are not essential. The reaction temperatures are between 30 and 130C.
The starting materials of the formulae II and IV can be prepared ~n accordance with known processes by replacing chlorine in chlorinated s-triazine deriva~ives by a correspon-ding amino group or by several corresponding amino groups.
The manufacture of 2-diallylamino-4-amino-6-(N,N-dimethyl-formamidine)_s_triazine is described in US patent specifi-cation 3,073,851.
Diamino- and triamino-s-triazines are described as chemoste-rilants for adult houseflies (~sca domestica) in US patent specification 3,189,521. The chemosterilising 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 lJ.Econ.Entomol. 61,(6), 1621 (196~)~
also describe the chemosterilising action of, inter alia, 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).
~08~9ZZ
Surprisingly, it has now been found that the compounds of the for~ula 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 actionconsistsin killingthe freshlyhatched larvae or preven-~ing adults from hatching from the pupaeO 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 active c pounds of the formula I can be used in parti-cular for controlling hygiene pests and animal ectoparasites of the order Diptera and of the families: Culicidae, Simulii-dae, Tipulidae, Muscidae and Calliphoridae.
The compounds of the formula I can be used as pure active substance or together with suitable carriers and/or additives.
Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in the art of formulation, for example natural or regenerated substances, solvents and/or dispersants. ~
The compositions according to the invention are manufactured in known manner by homogeneously mixing and/or grinding active substances (compounds) of the formula I with the suitable carriers, with or without the addition of disper--` lQ~49ZZ
sants or solvents which are inert to the active substances.
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).
~iquid formulations:
a) active substance concentrates which are dispersible in water: wettable powders, pastes and emulsions;
b) solutions: sprays (aerosols).
To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talc, bolus, loess, chalk, limestome, 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 vegetable products, such as corn meal, bark ~ust, sawdust, nutshell meal, cellulose powder, residues of plant extrac-tions, activated charcoal etc. These substances can either be used singly or in admixture with one another.
:~08~9Z2 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, SiO2, granicalcium, bentonite etc. and then evaporating the solvent.
Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde;
melamine/formaldehyde or others), whereupon a mild poly-merisation 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 ~tomisers.
It is also possible to obtain granules by compacting the carrier with the active substance and additives and subsequent-ly comminuting the product.
~08~92Z
To these mixtures can also be added additives 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 monoal~yl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl moiety, ligninsulphonic acid, the alkali metal and alkaline earth metal salts thereof, poly-ethylene glycol ethers (carbowaxes), fatty alcohol poly-ethylene glycol ethers having 5 to 20 ethylene oxide radicals per moiecule 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. They consist of active substance, carrier, optionally additives which stabilize the active substancè, surface-active substances and anti-foams and, if appropriate, solvents.
Wettable powders and pastes are obtained by ~ixing and grin-ding the active substances with dispersants and pulverulent carriers in suitable devices until homogeneity is attained.
- 10 _ 1(~849Z2 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 ~ormaldehyde as well as alkali metal, ammonium and alkaline earth metal salts of ligninsulphonic acid, in addition, alkylaryl sulphonates, alkali metal and alkaline earth metal salts of dibutyl-naphthalenesulphonic acid, fatty alcohol sulphates such as salts of sulphated hexa-decanols, heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary 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 are so mixed, grDund,sieved and strained with the additives mentioned above that, in wettable powders, the solid particle size of 0.02 to 0.04 mm and in pastes, of 0.03 m~, is not exceeded. Emulsifiable concentrates and pastes are manufactured by using dispersants, such as those referred to above, organic solvents, and water. Examples of suitable solvents are: alcohols, dimethyl sulphoxide, and mineral oil - 11 _ ~0849ZZ
fractions which boil between 120 and 350C. The solvents must be virtually odourless and inert to the active sub-stances.
Furthermore, the compositions according to the invention can be applied in the form of solutions. For this purpose the active substances or several active substances of the general formula I are dissolved in suitable organic solvents or mixtures of solvents. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkylnaphthalenes and mineral oils, singly or in admixture, can ~e used as organic solvents.
Formulations of the novel active compounds of the formula I
are described hereinafter. The parts denote parts by weight.
Dusts:
The following substances are used to manufacture a) a 0.5%
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 silicic acid 97 parts of talc.
The active substances are mixed with the carriers and ground.
-:~084922 Tracking Agents:
5 parts of active substance are mixed with 95 parts of carbonate of lime and ground to an average particle size of 80~.
Granules:
5 parts of active substance are dissolved in a solvent, e.g. methylene chloride, and mixed with 2 parts of polyethylene glycol ("Carbowax").
91.5 parts of calcium carbonate are impregnated with the mixture and 1.5 parts of precipitated silicic acid are admixed.
The solvent is subsequently evaporated.
Wettable Powder:
50 parts of active substance are mixed with 5 parts of a dispersing agent, e.g. sodium lignin-sulphonate, 5 parts of a wetting agent, e.g. dibutylnaphthalene-sulphonic acid 10 parts of silicic acid and 30 parts of China clay and the mixture is finely ground.
_ 13 -iO849Z~
Emulsifiable Concentrate:
20 parts of active substance are mixed with 20 parts of emulsifier, e.g. a mixture of alkylarylpoly-glycol ether with alkylarylsulphonates, 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 concentration.
Premix (feed additive):
0.25 parts of active substance and 4.75 parts of secondary calcium phosphate, or ~hina clay, aerosil 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 composi-tions of the present invention can obtain; for example, insecticides to broaden the activity spectrum.
_ 14 -~08492Z
The compositions, or the active compounds contained therein, exert their inhibitory action therefore chiefly on the deve-lopment of larvae or pupae of insects, preferably of the order Diptera.
Example 1 2-Cyclopropyl.amino-4-N',N'-dimethylformamidino-_morDholino-s-triazine .
20 g of 2-cyclopropylamino-4-amino-6-morpholino-s-triazine are suspended in 200 ml of benzene and the suspension is treated with 13 g of N,N-dimethylformamide-dimethyl acetal with the addition of 0.5 g of p-toluenesulphonic acid (as catalyst). The reaction mixture is refluxed for 10 hours. The solvent is then removed in vacuo and the residue is suspended in ether. The precipitated solid is recrystallised from iso-propanol Melting point: 160-162C.
The following compounds are prepared in accordance with the above procedure:
~.0849Z2 No. Compound mp. in C
1 2-cyclopropylamino-4-N',N'-dimethylforma- 152-153 midino-6_pyrrolidino-s-triazine 2 2-cyclopropylamino_4-N',N'-dimethylforma- 169-170 midino 6-ethylamino-s-triazine
, ' . ' , ' ~
~084922 Possible alkyl groups represented by Rl can be straight-chain or branched, unsubstituted or substituted for example by low~r 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 and 2-methoxyethyl. Examples of possible C3-C4-alkenyl and C3-C4-alkynyl groups represented by Rl include allyl and propargyl respectively.
Preferred compounds on account of their action are compounds of the formula I in which Rl represents hydrogen, Cl-C4-alkyl which is unsubstituted or substituted by lower alkoxy, or represents C3-C4-alkenyl, C3-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 l-pyrrolidinyl, l_piperidinyl, 4-morpho-linyl, l_piperazinyl, 1_(4_methyl)-piperazinyl or l-~midazolyl, R3 represents methyl or ethyl, R4 represents methyl or ethyl and R5 represents hydrogen or methyl.
Particularly advantageous compounds are those in wh~ch R
represents hydrogen, methyl, ethyl, isopropyl, 2_methoxy_ ethyl, allyl, propargyl or cyclopropyl, R2 represents hydro-gen or methyl or Rl and R2 together with the nitrogen atom to which they are attached represent l-pyrrolidinyl, 4-morpho-linyl or l-im~dazolyl, R3 represents methyl, R4 represents methyl and R5 represents hydrogen, and in which, if Rl re-presents propargyl, R2 prefera~ly represents hydrogen.
.. . . . .
.
- ~
.
-~084922 Compounds to be particularly highlighted are those in whichRl represents hydrogen, methyl or ethyl, R2 represents hydro-gen, R3 represents methyl, R4 represents methyl and R5 represents hydrogen.
Particularly preferred compounds are:
2-cyclopropylamino-4-dimethylformamidino-6-amino-s-triazine, 2-cyclopropylamino-4-dimethylformamidino_6-ethyl~mino_s-triazine, 2-cyclopropylamino-4-dimethylformamidino-6-methylamino-s-triazine, and 2_cyclopropylæmino-4-dimethylformamidino-6-propargylamino_s_ triazine.
The compounds of the formula I are obtained by methods which are known per se, for example by (a) reacting a 2-cyclopropylamino-4,6-diamino_s-triazine of the formula II
N N (II) 2N~ 11 NH~n5 in which Rl, R2 and R5 are as defined in formula I, with .
. . ~ .
.
- ' ~ ' ' ~
- , ;! a carboxy amide acetal or kctal of the formula III
alkyl - O \ / R3 / CH - N (III) alkyl - O R4 in which R3 and R4 are as defined in formula I, or (b) reacting a 2-cyclopropylamino-4-formamidino-6-chloro-s-triazine of the formula IV
Cl N N
/ N-CH-N ~ ~ N~ ~ (IV) in which R3, R4 and R5 are as defined in fonmula I, with ammonia or with a primary or secondary amine of the formula V
HN'~ 1 (V) in which Rl and R2 are as defined in formula I.
The above reactions (a) and (b) are preferably carried out in solvents or diluents which are inert to the reactants, for example in aliphatic or aromatic hydrocarbons, halogenated ~084922 hydrocarbons, ethers or ethereal compounds or ketones.
Catalysts, for example p-toluenesulphonic acid, c~n be added to the reaction mixture, but are not essential. The reaction temperatures are between 30 and 130C.
The starting materials of the formulae II and IV can be prepared ~n accordance with known processes by replacing chlorine in chlorinated s-triazine deriva~ives by a correspon-ding amino group or by several corresponding amino groups.
The manufacture of 2-diallylamino-4-amino-6-(N,N-dimethyl-formamidine)_s_triazine is described in US patent specifi-cation 3,073,851.
Diamino- and triamino-s-triazines are described as chemoste-rilants for adult houseflies (~sca domestica) in US patent specification 3,189,521. The chemosterilising 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 lJ.Econ.Entomol. 61,(6), 1621 (196~)~
also describe the chemosterilising action of, inter alia, 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).
~08~9ZZ
Surprisingly, it has now been found that the compounds of the for~ula 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 actionconsistsin killingthe freshlyhatched larvae or preven-~ing adults from hatching from the pupaeO 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 active c pounds of the formula I can be used in parti-cular for controlling hygiene pests and animal ectoparasites of the order Diptera and of the families: Culicidae, Simulii-dae, Tipulidae, Muscidae and Calliphoridae.
The compounds of the formula I can be used as pure active substance or together with suitable carriers and/or additives.
Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in the art of formulation, for example natural or regenerated substances, solvents and/or dispersants. ~
The compositions according to the invention are manufactured in known manner by homogeneously mixing and/or grinding active substances (compounds) of the formula I with the suitable carriers, with or without the addition of disper--` lQ~49ZZ
sants or solvents which are inert to the active substances.
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).
~iquid formulations:
a) active substance concentrates which are dispersible in water: wettable powders, pastes and emulsions;
b) solutions: sprays (aerosols).
To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talc, bolus, loess, chalk, limestome, 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 vegetable products, such as corn meal, bark ~ust, sawdust, nutshell meal, cellulose powder, residues of plant extrac-tions, activated charcoal etc. These substances can either be used singly or in admixture with one another.
:~08~9Z2 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, SiO2, granicalcium, bentonite etc. and then evaporating the solvent.
Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde;
melamine/formaldehyde or others), whereupon a mild poly-merisation 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 ~tomisers.
It is also possible to obtain granules by compacting the carrier with the active substance and additives and subsequent-ly comminuting the product.
~08~92Z
To these mixtures can also be added additives 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 monoal~yl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl moiety, ligninsulphonic acid, the alkali metal and alkaline earth metal salts thereof, poly-ethylene glycol ethers (carbowaxes), fatty alcohol poly-ethylene glycol ethers having 5 to 20 ethylene oxide radicals per moiecule 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. They consist of active substance, carrier, optionally additives which stabilize the active substancè, surface-active substances and anti-foams and, if appropriate, solvents.
Wettable powders and pastes are obtained by ~ixing and grin-ding the active substances with dispersants and pulverulent carriers in suitable devices until homogeneity is attained.
- 10 _ 1(~849Z2 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 ~ormaldehyde as well as alkali metal, ammonium and alkaline earth metal salts of ligninsulphonic acid, in addition, alkylaryl sulphonates, alkali metal and alkaline earth metal salts of dibutyl-naphthalenesulphonic acid, fatty alcohol sulphates such as salts of sulphated hexa-decanols, heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary 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 are so mixed, grDund,sieved and strained with the additives mentioned above that, in wettable powders, the solid particle size of 0.02 to 0.04 mm and in pastes, of 0.03 m~, is not exceeded. Emulsifiable concentrates and pastes are manufactured by using dispersants, such as those referred to above, organic solvents, and water. Examples of suitable solvents are: alcohols, dimethyl sulphoxide, and mineral oil - 11 _ ~0849ZZ
fractions which boil between 120 and 350C. The solvents must be virtually odourless and inert to the active sub-stances.
Furthermore, the compositions according to the invention can be applied in the form of solutions. For this purpose the active substances or several active substances of the general formula I are dissolved in suitable organic solvents or mixtures of solvents. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkylnaphthalenes and mineral oils, singly or in admixture, can ~e used as organic solvents.
Formulations of the novel active compounds of the formula I
are described hereinafter. The parts denote parts by weight.
Dusts:
The following substances are used to manufacture a) a 0.5%
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 silicic acid 97 parts of talc.
The active substances are mixed with the carriers and ground.
-:~084922 Tracking Agents:
5 parts of active substance are mixed with 95 parts of carbonate of lime and ground to an average particle size of 80~.
Granules:
5 parts of active substance are dissolved in a solvent, e.g. methylene chloride, and mixed with 2 parts of polyethylene glycol ("Carbowax").
91.5 parts of calcium carbonate are impregnated with the mixture and 1.5 parts of precipitated silicic acid are admixed.
The solvent is subsequently evaporated.
Wettable Powder:
50 parts of active substance are mixed with 5 parts of a dispersing agent, e.g. sodium lignin-sulphonate, 5 parts of a wetting agent, e.g. dibutylnaphthalene-sulphonic acid 10 parts of silicic acid and 30 parts of China clay and the mixture is finely ground.
_ 13 -iO849Z~
Emulsifiable Concentrate:
20 parts of active substance are mixed with 20 parts of emulsifier, e.g. a mixture of alkylarylpoly-glycol ether with alkylarylsulphonates, 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 concentration.
Premix (feed additive):
0.25 parts of active substance and 4.75 parts of secondary calcium phosphate, or ~hina clay, aerosil 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 composi-tions of the present invention can obtain; for example, insecticides to broaden the activity spectrum.
_ 14 -~08492Z
The compositions, or the active compounds contained therein, exert their inhibitory action therefore chiefly on the deve-lopment of larvae or pupae of insects, preferably of the order Diptera.
Example 1 2-Cyclopropyl.amino-4-N',N'-dimethylformamidino-_morDholino-s-triazine .
20 g of 2-cyclopropylamino-4-amino-6-morpholino-s-triazine are suspended in 200 ml of benzene and the suspension is treated with 13 g of N,N-dimethylformamide-dimethyl acetal with the addition of 0.5 g of p-toluenesulphonic acid (as catalyst). The reaction mixture is refluxed for 10 hours. The solvent is then removed in vacuo and the residue is suspended in ether. The precipitated solid is recrystallised from iso-propanol Melting point: 160-162C.
The following compounds are prepared in accordance with the above procedure:
~.0849Z2 No. Compound mp. in C
1 2-cyclopropylamino-4-N',N'-dimethylforma- 152-153 midino-6_pyrrolidino-s-triazine 2 2-cyclopropylamino_4-N',N'-dimethylforma- 169-170 midino 6-ethylamino-s-triazine
3 2_cyclopropylamino_4-N',N'-dimethylforma- 186-188 midino-6-methylamino-s-triazine
4 2-cyclopropylamino-4-N',N'-dimethylforma 158-lS9 midino-6-allylamino-s-triazine 2-cyclopropylamino_4_N',N'-dimethylforma- 193-194 midino-6-isopropylamino-s_triazine 6 2-cyclopropylamino-4-N',N'-dimethylforma- 126 midino-6_propargylamino-s_triazine 7 2,6-bis-(cyclopropylamino)_4_N',N'-dimethyl- 220-223 formamidino-s-triazine 8 2-cyclopropylamino-4-N',N'-dimethyl- 184-185 formamidino-6-imidazolo-s-triazine 9 2-cyclopropylamino-4-N',N'-dimethyl- 151-153 formamidino_6-(2-methoxyethylamino)-s-triazine 2-cyclopropylamino-4-N',N'-dimethylforma- 132-134 midino-6-dimethylamino-s-triazine 11 2-cyclopropylamino-4-N',N'-dimethylforma- 96-98 midino-6-(N-methyl-N-ethylamino)-s-triazine 12 2-cyclopropylamino-4-N',N'-dimethylforma- 196-198 midino-6-amino-s-triazine ~084922 Example 2 Action against Musca domestica 50 g of freshly prepared CSMA nutrient substrate for maggots are charged into beakers, 2,5 ml portions of a 1% acetonic solution of the respective active substance are pipetted onto the nutrient substrate present in the beakers. The substrate is then thoroughly mixed and the solvent subsequently allowed to evaporate.
Then 25 one-, two- and three- day-old maggots and approx. 50 eggs of Musca domestica are put into each of the beakers containing the treated nutrient substrate for testing with each active substance, After the maggots have pupated, the pupae are separated from the substrate by flushing them out with water and counted, The number of flies which have hatched out of the pupae is then counted after 10 days and any influence on the meta-morphosis thereby determined.
The compounds of the formula I displayed good activity in this test, Example 3 _ction against Lucilia sericat 1 ml of an aqueous solution containing 0.5% of active substance is added to 9 ml of a culture medium at 50C. Then approx. 30 freshly hatched larvae o Lucilia sericata are added to the culture medium and the insecticidal action is determined by evaluation of mortality after 48 and 96 hours respectively. In this test, the compounds of the formula I
act well against Lucilia sericata.
Example 4 Action against Aëdes aegypti Active substance concentrations of 10, 5 and 1 ppm respecti-vely are obtained by pipetting a specific amount of a 0.1%
solution of the active substance in acetone onto the surface of 150 ml of water in each of a number of beakers. After the acetone has evaporated, 30 to 40 two-day-old larvae of Aëdes aegypti are put into each of the beakers containing the active substance solution~ Evaluation of mortality is made after 1, 2 and 5 days respectively.
In this test, the compounds of the formula I exhibit good action against Ae'des aegypti.
.
Then 25 one-, two- and three- day-old maggots and approx. 50 eggs of Musca domestica are put into each of the beakers containing the treated nutrient substrate for testing with each active substance, After the maggots have pupated, the pupae are separated from the substrate by flushing them out with water and counted, The number of flies which have hatched out of the pupae is then counted after 10 days and any influence on the meta-morphosis thereby determined.
The compounds of the formula I displayed good activity in this test, Example 3 _ction against Lucilia sericat 1 ml of an aqueous solution containing 0.5% of active substance is added to 9 ml of a culture medium at 50C. Then approx. 30 freshly hatched larvae o Lucilia sericata are added to the culture medium and the insecticidal action is determined by evaluation of mortality after 48 and 96 hours respectively. In this test, the compounds of the formula I
act well against Lucilia sericata.
Example 4 Action against Aëdes aegypti Active substance concentrations of 10, 5 and 1 ppm respecti-vely are obtained by pipetting a specific amount of a 0.1%
solution of the active substance in acetone onto the surface of 150 ml of water in each of a number of beakers. After the acetone has evaporated, 30 to 40 two-day-old larvae of Aëdes aegypti are put into each of the beakers containing the active substance solution~ Evaluation of mortality is made after 1, 2 and 5 days respectively.
In this test, the compounds of the formula I exhibit good action against Ae'des aegypti.
.
Claims (13)
1. A compound of the formula (I) wherein R1 represents hydrogen, C1-C4-alkyl which is unsubstituted or substituted by lower alkoxy; or represents C3-C4-alkenyl, C3-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 a 5- or 6-membered heterocyclic ring which can contain a further nitrogen atom or an oxygen atom, R3 represents methyl or ethyl, R4 represents methyl or ethyl, and R5 represents hydrogen or methyl.
2. The compound according to claim 1 wherein R1 represents hydrogen, C1-C4-alkyl which is unsub-stituted or substituted by lower alkoxy, or represents C3-C4-alkenyl, C3-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 methyl or ethyl, R4 represents methyl or ethyl and R5 represents hydrogen or methyl.
3. The compound according to claim 1 wherein R1 represents hydrogen, methyl, ethyl, isopropyl, 2-methoxy-ethyl, allyl, propargyl or cyclopropyl, R2 represents hydrogen or methyl or R1 and R2 together with the nitrogen atom to which they fire attached represent 1-pyrrolidinyl, 4-morpho-linyl or 1-imidazolyl, R3 represents methyl, R4 represents methyl and R5 represents hydrogen and in which, if R1 repre-sents propargyl, R2 preferably represents hydrogen
4. The compound according to claim 1 wherein R1 represents hydrogen, methyl or ethyl, R2 represents hydro-gen, R3 represents methyl, R4 represents methyl and R5 repre-sents hydrogen.
5. 2-Cyclopropylamino-4-dimethylformamidino-6-amino-s-triazine according to claim 1.
6. 2-Cyclopropylamino-4-dimethylformamidino-6-ethylamino-s-triazine according to claim 1.
7. 2-Cyclopropylamino-4-dimethylformamidino-6-methylamino-s-triazine according to claim 1.
8. 2-Cyclopropylamino-4-dimethylformamidino-6-propargyl-amino-s-triazine according to claim 1.
9. A process for the manufacture of 2-cyclopropylamino-4-formamidino-6-amino-s-triazines of the formula I according to claim 1, wherein a 2-cyclopropylamino-4,6-diamino-s-triazine of the formula II
(II) in which R1, R2 and R5 are as defined in formula I, is reacted with a carboxy amide acetal of the formula III
(III) in which R3 and R4 are as defined in formula I.
(II) in which R1, R2 and R5 are as defined in formula I, is reacted with a carboxy amide acetal of the formula III
(III) in which R3 and R4 are as defined in formula I.
10. A method for combatting insects which comprises apply-ing to their developmental stages an insecticidally effective amount of a compound of the formula I of claim 1.
11. The method according to claim 10 for combatting in-sects in their larval or pupal stage in sufficient amount to inhibit metamorphosis.
12. The method according to claim 11 for combatting in-sects of the order Diptera.
13. The method according to claim 12 for combatting in-sects of the families Culicidae, Simuliidae, Tipulidae, Muscidae and Calliphoridae which belong to the order Diptera.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1056076A CH604518A5 (en) | 1976-08-19 | 1976-08-19 | Insecticidal cyclopropyl-amino-formamidino amino triazine cpds. |
| CH10560/76 | 1976-08-19 | ||
| CH2720/77 | 1977-03-04 | ||
| CH272077 | 1977-03-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1084922A true CA1084922A (en) | 1980-09-02 |
Family
ID=25691235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA284,901A Expired CA1084922A (en) | 1976-08-19 | 1977-08-17 | Derivatives of 2-cyclopropylamino-4-formamidino-6- amino-s-triazine as insecticides |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5325587A (en) |
| AU (1) | AU516804B2 (en) |
| CA (1) | CA1084922A (en) |
| DE (1) | DE2736698A1 (en) |
| FR (1) | FR2362136A1 (en) |
| GB (1) | GB1587572A (en) |
| IL (1) | IL52767A (en) |
| IT (1) | IT1086009B (en) |
| NL (1) | NL7709099A (en) |
| NZ (1) | NZ184955A (en) |
| YU (1) | YU41301B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3073851A (en) * | 1957-12-04 | 1963-01-15 | Hoffmann La Roche | Formamidines of primary amines |
| US3189521A (en) * | 1964-12-24 | 1965-06-15 | Alexej B Borkovec | Diamino- and triamino-s-triazines as chemosterilants for insects |
| IL39385A (en) * | 1971-06-01 | 1974-12-31 | Ciba Geigy Ag | A method for combating insects by the use of 4-azido-2,6-diamino triazine derivatives,certain such novel derivatives and their manufacture |
-
1977
- 1977-08-16 DE DE19772736698 patent/DE2736698A1/en not_active Withdrawn
- 1977-08-17 NL NL7709099A patent/NL7709099A/en not_active Application Discontinuation
- 1977-08-17 IL IL52767A patent/IL52767A/en unknown
- 1977-08-17 YU YU1990/77A patent/YU41301B/en unknown
- 1977-08-17 CA CA284,901A patent/CA1084922A/en not_active Expired
- 1977-08-18 NZ NZ184955A patent/NZ184955A/en unknown
- 1977-08-18 FR FR7725249A patent/FR2362136A1/en active Granted
- 1977-08-18 GB GB34792/77A patent/GB1587572A/en not_active Expired
- 1977-08-18 IT IT7726769A patent/IT1086009B/en active
- 1977-08-19 AU AU28043/77A patent/AU516804B2/en not_active Expired
- 1977-08-19 JP JP9940077A patent/JPS5325587A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NZ184955A (en) | 1980-05-27 |
| YU41301B (en) | 1987-02-28 |
| AU516804B2 (en) | 1981-06-25 |
| AU2804377A (en) | 1979-02-22 |
| JPS5325587A (en) | 1978-03-09 |
| DE2736698A1 (en) | 1978-02-23 |
| YU199077A (en) | 1982-08-31 |
| NL7709099A (en) | 1978-02-21 |
| IL52767A (en) | 1981-02-27 |
| IT1086009B (en) | 1985-05-28 |
| JPS638106B2 (en) | 1988-02-19 |
| FR2362136B1 (en) | 1980-02-01 |
| FR2362136A1 (en) | 1978-03-17 |
| IL52767A0 (en) | 1977-10-31 |
| GB1587572A (en) | 1981-04-08 |
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