CA1084923A - Derivatives of 2-cyclopropylamino-4-formylamino-6- amino-s-triazine as insecticides - Google Patents
Derivatives of 2-cyclopropylamino-4-formylamino-6- amino-s-triazine as insecticidesInfo
- Publication number
- CA1084923A CA1084923A CA284,902A CA284902A CA1084923A CA 1084923 A CA1084923 A CA 1084923A CA 284902 A CA284902 A CA 284902A CA 1084923 A CA1084923 A CA 1084923A
- Authority
- CA
- Canada
- Prior art keywords
- cyclopropylamino
- formylamino
- triazine
- represents hydrogen
- 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
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Classifications
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Abstrflct of the Disclosure 2-Cyclopropylamino-4-formylamino-6-amino-s-triazines 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, hydroxy, 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 hetcrocyclic ring which can contain a further nitrogen atom or an oxygen atom, and R3 represents hydrogen or methyl, and the acid addition salts thereof for combatting developmental stages of insects.
wherein R1 represents hydrogen, C1-C4-alkyl which is unsubstituted or substituted by lower alkoxy, or represents C3-C4-alkenyl, C3-C4-alkynyl, cyclopropyl, hydroxy, 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 hetcrocyclic ring which can contain a further nitrogen atom or an oxygen atom, and R3 represents hydrogen or methyl, and the acid addition salts thereof for combatting developmental stages of insects.
Description
The present invention relates to novel 2-cyclopropylamino-4-formylamino-6-amino-s-triazine derivatives and salts thereof, to a process for their manufacture and to their use in pest control.
The 2-cyclopropylamino-4-formylamino-6-amino-s-triazine deri-vatives have the for~ula R~ 1 N
~ .
N N
OHC-~N ~ ~ NH ~ R3 wherein Rl represents hydrogen, Cl-C4-alkyl which is unsubstituted or substituted by lower alkoxy, or represents C3-C4-alkenyl, C3-C4-alkynyl, cyclopropyl, hydroxy, 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 atom, and R3 represents hydrogen or methyl, and the acid addition salts thereof.
1~84923 Possible alkyl groups represented by Rl can be straight-chain or branched, unsubstituted or substituted for example by 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 also 2-methoxyethyl. Examples of C3-C4-alkenyl and C3-C4-alkynyl groups comprise allyl and pro-pargyl respectively.
The term "acid addition salts" of the 2-cyclopropylamino-4-formylamino-6-amino-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 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-morpholinyl, l-piperaz-inyl, l-(4-methyl)-piperazinyl or l-imadazolyl and R3 represents hydrogen or methyl.
Particularly preferred compounds are those in which Rl repre-sents hydrogen, methyl, e~hyl, isopropyl,2-methoxyethyl, allyl, propargyl or cyclopropyl, R2 represents hydrogen or methyl or .
Rl and ~2 together with the nitrogen atom to which they are attached represent l-pyrrolidinyl, 4-morpholinyl or l-imidazolyl and R3 represents hydrogen.
The most preferred compounds however are those in which Rl represents hydrogen, ethyl, allyl or propargyl, R2 represents hydrogen and R3 represents hydrogen, and, in particular the compounds:
The 2-cyclopropylamino-4-formylamino-6-amino-s-triazine deri-vatives have the for~ula R~ 1 N
~ .
N N
OHC-~N ~ ~ NH ~ R3 wherein Rl represents hydrogen, Cl-C4-alkyl which is unsubstituted or substituted by lower alkoxy, or represents C3-C4-alkenyl, C3-C4-alkynyl, cyclopropyl, hydroxy, 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 atom, and R3 represents hydrogen or methyl, and the acid addition salts thereof.
1~84923 Possible alkyl groups represented by Rl can be straight-chain or branched, unsubstituted or substituted for example by 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 also 2-methoxyethyl. Examples of C3-C4-alkenyl and C3-C4-alkynyl groups comprise allyl and pro-pargyl respectively.
The term "acid addition salts" of the 2-cyclopropylamino-4-formylamino-6-amino-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 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-morpholinyl, l-piperaz-inyl, l-(4-methyl)-piperazinyl or l-imadazolyl and R3 represents hydrogen or methyl.
Particularly preferred compounds are those in which Rl repre-sents hydrogen, methyl, e~hyl, isopropyl,2-methoxyethyl, allyl, propargyl or cyclopropyl, R2 represents hydrogen or methyl or .
Rl and ~2 together with the nitrogen atom to which they are attached represent l-pyrrolidinyl, 4-morpholinyl or l-imidazolyl and R3 represents hydrogen.
The most preferred compounds however are those in which Rl represents hydrogen, ethyl, allyl or propargyl, R2 represents hydrogen and R3 represents hydrogen, and, in particular the compounds:
2-cyclopropylamino-4-formylamino-6-ethylamino-s-triazine, 2-cyclopropylamino-4-formylamino-6-allyl~mino-s-triazine, 2-cyclopropylamino-4-formylamino-6-propargylamino-s-triazine and 2-cyclopropylamino-4-formylamino-6-amino-s-triazine.
The compounds of the formula I are obtained by methods which are known per se, for example by (a) converting a 2-cyclopropylamino-4-formamidino-6-amino-s-triazine of the formula II
n2 ~1 '~ ' N N
N-Cl~=N ~ ~ R3 II
wherein Rl, R2 and R3 are as defined in formula I and R4 and R5 are the same or different and represent methyl or ethyl, into the corresponding 2-cyclopropylamino-4-formylamino-6-amino-s-triazine by hydrolysis, or (b) reacting a 2-cyclopropylamino-4,6-diamino-s-triazine of the formula II
N
H2~ ~ ~ NH ~ R3 lII
in which R3 is as de~ined in formula I and in which Rl and R2 have the meanings assigned to Rl and R2 in formula I with the exception of hydrogen, with a formylating agent.
The hydrolysis (a) can be carried out with the addition of an acid, such as hydrochloric acid, at 0 to 100C under normal pressure. Advantageously, water is used as solvent or diluent, if appropriate with the addition of an organic solvent, such as dioxane, an alcohol, etc.,`whereupon the reaction product precipitates, The reaction (b) is preferably carried out using formic acid and acetic anhydride as formylating reagent or by condensation of a compound of the formula III with an ortho-formate in the ~84923 presence of catalytic amounts of a strong acid and subsequent partial hydrolysis. In the former case it is possible to use in the reaction a solvent or diluent which is inert to the react-ants, and in the latter case the orthoester is used as solvent.
The starting material of the formula II can be obtained by reacting a tria~ine derivative of the formula III
N N
132N ~ R NH ~ R3 III
in which Rl, R2 and R3 are as defined in formula I, with an acetal of the formula V
CH-N ~
Alkyl-O ~ R5 in which R4 and R5 have the meanings given in formula I.
The starting material of the formula III can be prepared by conventional methods from chlorine-substituted s-triazine derivatives by replacing chlorine with the corresponding amino group or groups.
Diamino- and triamino-s-triazines are described as chemo-sterilants for adult houseflies ~usca 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. I0 (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-cyclohexyl-amino-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). The chemo-sterilising action of acetylmelamines is described in US patent specification 3,520,974.
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 hatched 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.
~8~9Z3 The active compounds of the foL~ula I can be used in particular for controlling hygiene pests and animal ectoparasites of the order Diptera and of the families: Cu}icidae, Simuliidae, Tipulidae, Muscidae and Calliphoridae.
The compounds of the formula I can be used as pure activ~
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 dispersants 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).
~ 0849Z3 Liquid formulations:
a) active substance concentrates ~7hich are dispersible in water: wettable powders, pastes and emulsions;
b) solu~ions: 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, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, pre-cipitated silica, alkaline earth silicates, sodium and po~assium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, ferti-lisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances 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, SiO2, granicalcium, bentonite etc. and then evaporating the solvent.
~08~9Z3 Polymer granules can also be manufactured by mixing the actlve substances of the formula I with polymerlsable compounds (urea/formaldehyde; dicyandiamide/formaldehyde; mela~ine/form-aldehyde 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 fonmation. It is more advantageGus to impregnate finislled, porous polymer granules (urea/formaîdehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, witn the active substances, for example in the form of their solu-tions (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 ~lso be manufactured with the aid of atomisers.
It is also possible to obtain granules by compacting the carrier with the active substance and additives and subsequently comminuting the product.
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 cellu-lose, carboxymethyl cellulose), hydroxyethyl glycol ethers of ~4923 monoalkyl 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, polyethylene glycol ethers (carbo-waxes), fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide rad~cals per molecule and 8 to 18 carbon a~oms in the fatty alcohol moiety, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidone, poly-vinyl alcohol, condensation products of ure~ and formaldehyde, and also latex products.
Water-dispersible concentratesj i.e. wettable p~wders, pastes and emulsifiable concentrates, are compositions which can b~
diluted with water to the desired concentration.
They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substances and anti-foams and, if appropriate, solvents.
Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersants and pulverulent carriers in suitable devices until homogeneity is attained. Suitable carriers are, for example, those already mentioned for the solid forms of applica~ion. In some cases it is advantageous to use mixtures of different carriers. Examples of dispersants are: condensation products of sulphonated naphthalene and sul-phonated naphthalene derivatives with formaldehyde, conden-sation products of naphthalene or naphthalene sulphonic acids 10849;23 wi.h phenol and formaldehyde, as well as alkali metal, ammonium and alkaline earth metal salts of lignin sulphonic acid, in addition~ alkylaryl sulphonates, alkali metal and alkaline earth metal salts of dibutyl naphtha'ene sulphonic acid, fatty alcohol sulphates such as salts of sulphated hexa-decanols, heptadecznols, oc-adecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium sal~ of oleyl methyl tauride, ditertiary ethylene glycols, dialkyl dilauryl ammonium 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, ground, 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 mm, 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 fractions which boil between 120 and 350C, The solvents must be virtually odourless and inert to the active substances.
Furthermore,the compositions according to the invention can be applied in the form of solutions. For this purpose the active substance 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, alkylnaphthale~es and mineral oils, singly or in admixture, can be used as organic solvents.
Formulations of the novel active compounds of the for~ula 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.S parts of talc 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.
Trackin~ Agents:
parts of active substance are mixed with parts of carbonate of lime and ground to an average particle size of 80 ~.
Granules:
S parts of active subs~ance are dissolved in a solvent, e.g. methylene chloride, and mixed wi~h ~084923 2 parts of polyethylene glycol ("Carbowax").
91.5 parts or calcium carbonate are impregnated with the mixture and 1 5 parts of precipitated silicic acid are ad mixed.
The solvent is subsequently evaporated.
Wettable Powder:
parts of active substance are mixed w~th S parts of a dispersing agent, e.g. sodium lignin sulphonate, parts of a wetting agent, e.g. dibutyl-naphthalene-sulphonic acid parts of silicic acid and parts of China clay and the mixture is finely ground.
Emulsifiable Concentrate:
parts of active substance are mixed with parts of emulsifier, e.g. a mixture of alkylarylpolyglycol ether with alkylaryl-sulphonates, and 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.
1~84923 Premix (feed a ditive):
0.25 part of active substance and 4.75 parts of secondary calcium phosphate, or China clay, aerosil or carbonate of lime ar~ homogeneously mixed WL th 95 parts of an animal feed, e.g. poultry food.
Spray:
The following constituents are used to manufacturc a 2% spray:
2 parts of active substance 98 parts of kerosene.
Other biocidal active substances or agents can be admixed with the compositions describe~ hereinabove. Thus in addition to the cited compounds of the general formula T, the compositions of the present invention can contain, for example, insecticides to broaden the activity spectrurn.
Ihe compositions, or the active compounds contained therein, exert their inhibitory action therefore chiefly on the develop-ment of larvae or pupae of insects, preferably of the order Diptera.
.,, ~ - .
'' ~084923 E X A M P L E
2-Cyclopropy-l-a~rlino-4-formylamino-6-m-orpholino-s-triazine 25 g of 2-cyclopropylamino-4-N',N'-dimethylformamidino-6-mor-pholino-s-triazine are dissolved in 1000 ml of ~ater and the solution is treated with 100 ml of lN hydrochloric acid. After stirring for 15 minutes at room temperature, the 2-cyclopropyl-amino-4-formylamino-6-morpholino-s-triazine with a melting po~r.t of 288C begins to precipitate. The crude product is recristal-lised from dimethylformamide. Melting point: 291-292C.
The following compounds of the formula I are prepared in ac-cordance with the above procedure:
~08~9;Z3 No. ~ompound mp. in CC
. ...._ _ 1 2-cyclopropylamino-4-formylamino-6-morpho-lino-s-triazinehydrochloride 244-245 2 2-cyclopropylamino-4-formvlamino-6-pyrroli-dino-s-triazine 260-261
The compounds of the formula I are obtained by methods which are known per se, for example by (a) converting a 2-cyclopropylamino-4-formamidino-6-amino-s-triazine of the formula II
n2 ~1 '~ ' N N
N-Cl~=N ~ ~ R3 II
wherein Rl, R2 and R3 are as defined in formula I and R4 and R5 are the same or different and represent methyl or ethyl, into the corresponding 2-cyclopropylamino-4-formylamino-6-amino-s-triazine by hydrolysis, or (b) reacting a 2-cyclopropylamino-4,6-diamino-s-triazine of the formula II
N
H2~ ~ ~ NH ~ R3 lII
in which R3 is as de~ined in formula I and in which Rl and R2 have the meanings assigned to Rl and R2 in formula I with the exception of hydrogen, with a formylating agent.
The hydrolysis (a) can be carried out with the addition of an acid, such as hydrochloric acid, at 0 to 100C under normal pressure. Advantageously, water is used as solvent or diluent, if appropriate with the addition of an organic solvent, such as dioxane, an alcohol, etc.,`whereupon the reaction product precipitates, The reaction (b) is preferably carried out using formic acid and acetic anhydride as formylating reagent or by condensation of a compound of the formula III with an ortho-formate in the ~84923 presence of catalytic amounts of a strong acid and subsequent partial hydrolysis. In the former case it is possible to use in the reaction a solvent or diluent which is inert to the react-ants, and in the latter case the orthoester is used as solvent.
The starting material of the formula II can be obtained by reacting a tria~ine derivative of the formula III
N N
132N ~ R NH ~ R3 III
in which Rl, R2 and R3 are as defined in formula I, with an acetal of the formula V
CH-N ~
Alkyl-O ~ R5 in which R4 and R5 have the meanings given in formula I.
The starting material of the formula III can be prepared by conventional methods from chlorine-substituted s-triazine derivatives by replacing chlorine with the corresponding amino group or groups.
Diamino- and triamino-s-triazines are described as chemo-sterilants for adult houseflies ~usca 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. I0 (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-cyclohexyl-amino-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). The chemo-sterilising action of acetylmelamines is described in US patent specification 3,520,974.
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 hatched 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.
~8~9Z3 The active compounds of the foL~ula I can be used in particular for controlling hygiene pests and animal ectoparasites of the order Diptera and of the families: Cu}icidae, Simuliidae, Tipulidae, Muscidae and Calliphoridae.
The compounds of the formula I can be used as pure activ~
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 dispersants 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).
~ 0849Z3 Liquid formulations:
a) active substance concentrates ~7hich are dispersible in water: wettable powders, pastes and emulsions;
b) solu~ions: 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, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, pre-cipitated silica, alkaline earth silicates, sodium and po~assium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, ferti-lisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances 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, SiO2, granicalcium, bentonite etc. and then evaporating the solvent.
~08~9Z3 Polymer granules can also be manufactured by mixing the actlve substances of the formula I with polymerlsable compounds (urea/formaldehyde; dicyandiamide/formaldehyde; mela~ine/form-aldehyde 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 fonmation. It is more advantageGus to impregnate finislled, porous polymer granules (urea/formaîdehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, witn the active substances, for example in the form of their solu-tions (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 ~lso be manufactured with the aid of atomisers.
It is also possible to obtain granules by compacting the carrier with the active substance and additives and subsequently comminuting the product.
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 cellu-lose, carboxymethyl cellulose), hydroxyethyl glycol ethers of ~4923 monoalkyl 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, polyethylene glycol ethers (carbo-waxes), fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide rad~cals per molecule and 8 to 18 carbon a~oms in the fatty alcohol moiety, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidone, poly-vinyl alcohol, condensation products of ure~ and formaldehyde, and also latex products.
Water-dispersible concentratesj i.e. wettable p~wders, pastes and emulsifiable concentrates, are compositions which can b~
diluted with water to the desired concentration.
They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substances and anti-foams and, if appropriate, solvents.
Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersants and pulverulent carriers in suitable devices until homogeneity is attained. Suitable carriers are, for example, those already mentioned for the solid forms of applica~ion. In some cases it is advantageous to use mixtures of different carriers. Examples of dispersants are: condensation products of sulphonated naphthalene and sul-phonated naphthalene derivatives with formaldehyde, conden-sation products of naphthalene or naphthalene sulphonic acids 10849;23 wi.h phenol and formaldehyde, as well as alkali metal, ammonium and alkaline earth metal salts of lignin sulphonic acid, in addition~ alkylaryl sulphonates, alkali metal and alkaline earth metal salts of dibutyl naphtha'ene sulphonic acid, fatty alcohol sulphates such as salts of sulphated hexa-decanols, heptadecznols, oc-adecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium sal~ of oleyl methyl tauride, ditertiary ethylene glycols, dialkyl dilauryl ammonium 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, ground, 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 mm, 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 fractions which boil between 120 and 350C, The solvents must be virtually odourless and inert to the active substances.
Furthermore,the compositions according to the invention can be applied in the form of solutions. For this purpose the active substance 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, alkylnaphthale~es and mineral oils, singly or in admixture, can be used as organic solvents.
Formulations of the novel active compounds of the for~ula 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.S parts of talc 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.
Trackin~ Agents:
parts of active substance are mixed with parts of carbonate of lime and ground to an average particle size of 80 ~.
Granules:
S parts of active subs~ance are dissolved in a solvent, e.g. methylene chloride, and mixed wi~h ~084923 2 parts of polyethylene glycol ("Carbowax").
91.5 parts or calcium carbonate are impregnated with the mixture and 1 5 parts of precipitated silicic acid are ad mixed.
The solvent is subsequently evaporated.
Wettable Powder:
parts of active substance are mixed w~th S parts of a dispersing agent, e.g. sodium lignin sulphonate, parts of a wetting agent, e.g. dibutyl-naphthalene-sulphonic acid parts of silicic acid and parts of China clay and the mixture is finely ground.
Emulsifiable Concentrate:
parts of active substance are mixed with parts of emulsifier, e.g. a mixture of alkylarylpolyglycol ether with alkylaryl-sulphonates, and 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.
1~84923 Premix (feed a ditive):
0.25 part of active substance and 4.75 parts of secondary calcium phosphate, or China clay, aerosil or carbonate of lime ar~ homogeneously mixed WL th 95 parts of an animal feed, e.g. poultry food.
Spray:
The following constituents are used to manufacturc a 2% spray:
2 parts of active substance 98 parts of kerosene.
Other biocidal active substances or agents can be admixed with the compositions describe~ hereinabove. Thus in addition to the cited compounds of the general formula T, the compositions of the present invention can contain, for example, insecticides to broaden the activity spectrurn.
Ihe compositions, or the active compounds contained therein, exert their inhibitory action therefore chiefly on the develop-ment of larvae or pupae of insects, preferably of the order Diptera.
.,, ~ - .
'' ~084923 E X A M P L E
2-Cyclopropy-l-a~rlino-4-formylamino-6-m-orpholino-s-triazine 25 g of 2-cyclopropylamino-4-N',N'-dimethylformamidino-6-mor-pholino-s-triazine are dissolved in 1000 ml of ~ater and the solution is treated with 100 ml of lN hydrochloric acid. After stirring for 15 minutes at room temperature, the 2-cyclopropyl-amino-4-formylamino-6-morpholino-s-triazine with a melting po~r.t of 288C begins to precipitate. The crude product is recristal-lised from dimethylformamide. Melting point: 291-292C.
The following compounds of the formula I are prepared in ac-cordance with the above procedure:
~08~9;Z3 No. ~ompound mp. in CC
. ...._ _ 1 2-cyclopropylamino-4-formylamino-6-morpho-lino-s-triazinehydrochloride 244-245 2 2-cyclopropylamino-4-formvlamino-6-pyrroli-dino-s-triazine 260-261
3 2-cyclopropylamino-4-formylamino-6-methyl-amino-s-triazine 244-245
4 2-cyclopropylamino-4-formylamino-6-ethyl-amino-s-triazine 257-258 2-cyclopropylamino-4-formylamino-6-allyl-amino-s-triazine 245-246 6 2-cyclopropylamino-4-formylamino-6-isopro-pylamino-s-triazine 199-201 7 2-cyclopropylamino-4-formylamino-6-propargyl-amino-s-triazine 258-260 8 2-cyclopropylamino-4-formylamino-6-imidazolo-s-triazine 256-259 9 2-cyclopropylamino-4-formylanino-6-dimethyl-amino-s-triazine 259-261 2-cyclopropylamino-4-formylamino-6-(2-methoxyethylamino)-s-triazine 214-215 11 2,6-bis-(cyclopropylamino)-4-formylamino-s-t7-iazine 259-260 12 2-cyclopropylamino-4-formylamino-6-amino-s-triazine 269-271 13 2-cyclopropylamino-4-formylamino-6-(N-methyl-N-ethylamino)-s-triazinei 2~5 1~84923 . .
Action agains. Musca domestica -50 g of freshly prepared CSMA nutrient substrate for maggots were charged into beakers. ~.5 ml portions of a l~o acetonic solution of the respective active substance were pipetted onto the nutrient substr~te present in the beakers. The substra~e was then thoroughly mixed and the solvent subse~uently allowed to e~raporate.
Then 25 one-, two- and three-day-old maggots and approx.
50 eggs of Musca domes~ica were put into each of the beakers containing the treated nutrient substrate for testing with each active substance. After the maggots had pupated, the pupae were separated from the substrate by flushing them out with wa-ter and counted. The number of flies which had ha~ched out of the pupae was then counted after 10 days and any influence on the metamorphosis thereby determined.
In the above text, the compounds of Example 1 displayed a good action against Musca domestica.
E X A M P L E
. . _ ction against Lucilia sericata 1 ml of an aqueous solution containing 0.5% of ac~ive sub-stance was added to 9 ml of a culture medium at 50C. Then approx. 30 freshly 'natched larvae of Lucilia sericata were added to the culture mediu,m and the insecticidal action was deLer-mined by evaluation of mortality after 4~ and ~ hours respectively.
In this test, the compounds of the formula I acted well against Lucilia sericata.
E X A ~ P L E 4 Action agains~ Aëd_s aegypti larvae Active substance concentrations of 10, 5 and 1 ppm respectively were obtained by pipetting a specific amount of a 0.1 % solu-tion of the active substance in acetone onto the surface of 150 ml of water in each of a number of beakers.
After the acetone had evaporated, 30 to 40 two-day-old larvae of Aëdes aegypti were 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 acted well against Aedes aegypti.
Action agains. Musca domestica -50 g of freshly prepared CSMA nutrient substrate for maggots were charged into beakers. ~.5 ml portions of a l~o acetonic solution of the respective active substance were pipetted onto the nutrient substr~te present in the beakers. The substra~e was then thoroughly mixed and the solvent subse~uently allowed to e~raporate.
Then 25 one-, two- and three-day-old maggots and approx.
50 eggs of Musca domes~ica were put into each of the beakers containing the treated nutrient substrate for testing with each active substance. After the maggots had pupated, the pupae were separated from the substrate by flushing them out with wa-ter and counted. The number of flies which had ha~ched out of the pupae was then counted after 10 days and any influence on the metamorphosis thereby determined.
In the above text, the compounds of Example 1 displayed a good action against Musca domestica.
E X A M P L E
. . _ ction against Lucilia sericata 1 ml of an aqueous solution containing 0.5% of ac~ive sub-stance was added to 9 ml of a culture medium at 50C. Then approx. 30 freshly 'natched larvae of Lucilia sericata were added to the culture mediu,m and the insecticidal action was deLer-mined by evaluation of mortality after 4~ and ~ hours respectively.
In this test, the compounds of the formula I acted well against Lucilia sericata.
E X A ~ P L E 4 Action agains~ Aëd_s aegypti larvae Active substance concentrations of 10, 5 and 1 ppm respectively were obtained by pipetting a specific amount of a 0.1 % solu-tion of the active substance in acetone onto the surface of 150 ml of water in each of a number of beakers.
After the acetone had evaporated, 30 to 40 two-day-old larvae of Aëdes aegypti were 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 acted well against Aedes aegypti.
Claims (16)
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, hydroxy, 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, and R3 represents hydrogen or methyl, and the acid addition salts thereof.
wherein R1 represents hydrogen, C1-C4-alkyl which is unsubstituted or substituted by lower alkoxy, or represents C3-C4-alkenyl, C3-C4-alkynyl, cyclopropyl, hydroxy, 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, and R3 represents hydrogen or methyl, and the acid addition salts thereof.
2. The compound according to claim 1 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 hy-drogen, methyl or ethyl, or R1 and R2 together with the nitrogen atom to which they are attached represent 1-pyrroli-dinyl, 1-piperidinyl, 4-morpholinyl, 1-piperazinyl, 1-(4-methyl)-piperazinyl or 1-imadazolyl and R3 represents hydrogen or methyl and the acid addition salts thereof.
3. The compound according to claim 1 wherein R1 represents hydrogen, methyl, ethyl, isopropyl, 2-methoxyethyl, allyl, propargyl or cyclopropyl, R2 represents hydrogen or methyl or R1 and R2 together with the nitrogen atom to which they are attached represent 1-pyrrolidinyl, 4-morpholinyl or 1-imidazolyl and R3 represents hydrogen and the hydrochlorides thereof.
4. The compound according to claim 1 wherein R1 represents hydrogen, ethyl, allyl or propargyl, R2 represents hydrogen and R3 represents hydrogen.
5. 2-Cyclopropylamino-4-formylamino-6-ethylamino-s-tria-zine according to claim 1.
6. 2-Cyclopropylamino-4-formylamino-6-allylamino-s-tria-zine according to claim 1.
7. 2-Cyclopropylamino-4-formylamino-6-propargylamino-s-triazine.
8. Cyclopropylamino-4-formylamino-6-amino-s-triazine.
9. A process for the manufacture of 2-cyclopropylamino-4-formylamino-6-amino-s-triazines of the formula I defined in claim 1, wherein (a) a 2-cyclopropylamino-4-formamidino-6-amino-s-triazine of the formula:
II
in which R1, R2, and R3 are as defined in claim 1 and R4 and R5 are the same or different and represent methyl or ethyl, is con-verted by hydrolysis into the corresponding 2-cyclopropylamino-4-formylamino-6-amino-s-triazine, or (b) a 2-cyclopropylamino-4,6-diamino-s-triazine of the formula:
III
in which R3 is as defined in claim 1 and in which R1 and R2 have the meanings assigned to R1 and R2 in claim 1 with the exception of hydrogen, is reacted with a formylating agent.
II
in which R1, R2, and R3 are as defined in claim 1 and R4 and R5 are the same or different and represent methyl or ethyl, is con-verted by hydrolysis into the corresponding 2-cyclopropylamino-4-formylamino-6-amino-s-triazine, or (b) a 2-cyclopropylamino-4,6-diamino-s-triazine of the formula:
III
in which R3 is as defined in claim 1 and in which R1 and R2 have the meanings assigned to R1 and R2 in claim 1 with the exception of hydrogen, is reacted with a formylating agent.
10. A process for the manufacture of 2-cyclopropylamino-4-formylamino-6-amino-s-triazines of the formula I defined in claim 1, wherein a 2-cyclopropylamino-4-formamidino-6-amino-s-triazine of the formula:
II
in which R1, R2 and R3 are as defined in claim 1 and R4 and R5 are the same or different and represent methyl or ethyl, is con-verted by hydrolysis into the corresponding 2-cyclopropylamino-4-formylamino-6-amino-s-triazine.
II
in which R1, R2 and R3 are as defined in claim 1 and R4 and R5 are the same or different and represent methyl or ethyl, is con-verted by hydrolysis into the corresponding 2-cyclopropylamino-4-formylamino-6-amino-s-triazine.
11. A process for the manufacture of 2-cyclopropylamino-4-formylamino-6-amino-s-triazines of the formula I defined in claim 1, wherein a 2-cyclopropylamino-4,6-diamino-s-triazine of the formula:
III
in which R3 is as defined in claim 1 and in which R1 and R2 have the meanings assigned to R1 and R2 in claim 1 with the exception of hydrogen, is reacted with a formylating agent.
III
in which R3 is as defined in claim 1 and in which R1 and R2 have the meanings assigned to R1 and R2 in claim 1 with the exception of hydrogen, is reacted with a formylating agent.
12. The process according to claim 9 or 11 wherein the formylating agent is formic acid and acetic anhydride or ortho-formic acid.
13. 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.
14. The method according to claim 13 for combatting insects in their larval or pupal stage in sufficient amount to inhibit metamorphosis.
15. The method according to claim 14 for combatting in-sects of the order Diptera.
16. The method according to claim 15 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 |
|---|---|---|---|
| CH1055976A CH603049A5 (en) | 1976-08-19 | 1976-08-19 | (2)-Cyclopropyl-amino-(4)-formyl-amino-(1,3,5)-triazine cpds. |
| CH10559/76 | 1976-08-19 | ||
| CH271977 | 1977-03-04 | ||
| CH2719/77 | 1977-03-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1084923A true CA1084923A (en) | 1980-09-02 |
Family
ID=25691230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA284,902A Expired CA1084923A (en) | 1976-08-19 | 1977-08-17 | Derivatives of 2-cyclopropylamino-4-formylamino-6- amino-s-triazine as insecticides |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5325586A (en) |
| AU (1) | AU518857B2 (en) |
| CA (1) | CA1084923A (en) |
| DE (1) | DE2736699A1 (en) |
| ES (1) | ES461716A1 (en) |
| FR (1) | FR2362135A1 (en) |
| GB (1) | GB1587571A (en) |
| IL (1) | IL52766A (en) |
| NL (1) | NL7709098A (en) |
| NZ (1) | NZ184954A (en) |
| YU (1) | YU198977A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ221262A (en) * | 1986-08-06 | 1990-08-28 | Ciba Geigy Ag | Preventing the reinfestation of dogs and cats by fleas by administering to the host a flea growth inhibiting substance orally, parenterally or by implant |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 DE19772736699 patent/DE2736699A1/en not_active Withdrawn
- 1977-08-17 YU YU01989/77A patent/YU198977A/en unknown
- 1977-08-17 NL NL7709098A patent/NL7709098A/en not_active Application Discontinuation
- 1977-08-17 CA CA284,902A patent/CA1084923A/en not_active Expired
- 1977-08-17 IL IL52766A patent/IL52766A/en unknown
- 1977-08-18 FR FR7725248A patent/FR2362135A1/en active Granted
- 1977-08-18 NZ NZ184954A patent/NZ184954A/en unknown
- 1977-08-18 GB GB34791/77A patent/GB1587571A/en not_active Expired
- 1977-08-18 ES ES461716A patent/ES461716A1/en not_active Expired
- 1977-08-19 JP JP9939977A patent/JPS5325586A/en active Granted
- 1977-08-19 AU AU28042/77A patent/AU518857B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2362135B1 (en) | 1980-06-27 |
| YU198977A (en) | 1982-08-31 |
| JPS5325586A (en) | 1978-03-09 |
| ES461716A1 (en) | 1978-12-16 |
| AU518857B2 (en) | 1981-10-22 |
| NZ184954A (en) | 1980-05-08 |
| NL7709098A (en) | 1978-02-21 |
| AU2804277A (en) | 1979-02-22 |
| DE2736699A1 (en) | 1978-06-22 |
| GB1587571A (en) | 1981-04-08 |
| IL52766A (en) | 1981-02-27 |
| FR2362135A1 (en) | 1978-03-17 |
| JPS638105B2 (en) | 1988-02-19 |
| IL52766A0 (en) | 1977-10-31 |
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