CA1047497A - Heterocyclic derivative - Google Patents
Heterocyclic derivativeInfo
- Publication number
- CA1047497A CA1047497A CA200,703A CA200703A CA1047497A CA 1047497 A CA1047497 A CA 1047497A CA 200703 A CA200703 A CA 200703A CA 1047497 A CA1047497 A CA 1047497A
- Authority
- CA
- Canada
- Prior art keywords
- phosphorothionate
- diethylaminopyrimidin
- pests
- compound
- dimethyl
- 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
- 125000000623 heterocyclic group Chemical group 0.000 title 1
- 241000607479 Yersinia pestis Species 0.000 claims description 20
- 241000238631 Hexapoda Species 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 17
- 230000000361 pesticidal effect Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 19
- 239000004480 active ingredient Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 241001608567 Phaedon cochleariae Species 0.000 description 6
- 241000255969 Pieris brassicae Species 0.000 description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- -1 2-diethylaminopyrimidin-4-yl Chemical group 0.000 description 4
- 241000219198 Brassica Species 0.000 description 4
- 235000003351 Brassica cretica Nutrition 0.000 description 4
- 235000003343 Brassica rupestris Nutrition 0.000 description 4
- 241000500437 Plutella xylostella Species 0.000 description 4
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 235000010460 mustard Nutrition 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 241000256118 Aedes aegypti Species 0.000 description 3
- 241001124076 Aphididae Species 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000008262 pumice Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- ZRVKDGHDCOMYDX-UHFFFAOYSA-N 2-(diethylamino)-1h-pyrimidin-6-one Chemical compound CCN(CC)C1=NC=CC(=O)N1 ZRVKDGHDCOMYDX-UHFFFAOYSA-N 0.000 description 2
- 240000007124 Brassica oleracea Species 0.000 description 2
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 2
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 2
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 2
- 206010061217 Infestation Diseases 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 241000171274 Megoura Species 0.000 description 2
- 241000257159 Musca domestica Species 0.000 description 2
- 241000257226 Muscidae Species 0.000 description 2
- 241000131102 Oryzaephilus Species 0.000 description 2
- 241000254179 Sitophilus granarius Species 0.000 description 2
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- XFBJRFNXPUCPKU-UHFFFAOYSA-N chloro-dimethoxy-sulfanylidene-$l^{5}-phosphane Chemical compound COP(Cl)(=S)OC XFBJRFNXPUCPKU-UHFFFAOYSA-N 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- HAEVLZUBSLBWIX-UHFFFAOYSA-N 2-octylphenol;oxirane Chemical compound C1CO1.CCCCCCCCC1=CC=CC=C1O HAEVLZUBSLBWIX-UHFFFAOYSA-N 0.000 description 1
- 241000256111 Aedes <genus> Species 0.000 description 1
- 241001425390 Aphis fabae Species 0.000 description 1
- 241000238657 Blattella germanica Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000256113 Culicidae Species 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241001127120 Dysdercus fasciatus Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241000243786 Meloidogyne incognita Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 241000257229 Musca <genus> Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 241000254112 Tribolium confusum Species 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- 210000000234 capsid Anatomy 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 231100001225 mammalian toxicity Toxicity 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012746 preparative thin layer chromatography Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
O,O-Dimethyl 2-diethylaminopyrimidin-4-yl phosphoro-thionate, and compositions comprising it, are pesticidal.
O,O-Dimethyl 2-diethylaminopyrimidin-4-yl phosphoro-thionate, and compositions comprising it, are pesticidal.
Description
~o47~7 This invention relates to a novel pyrimidine derivative, which is useful as an insecticide.
Accordingly the invention provides 0,0-dimethyl
Accordingly the invention provides 0,0-dimethyl
2-diethylaminopyrimidin-4-yl phosphorothionate This compound, which is a member of a group of compounds broadly disclosed in U.K. patent specification serial No.1,019,227, is distinguished from other closely related 2-aminopyrimidin-4-yl phosphorus ;esters, including some specifically recited in the above identified specification, by a markedly lower toxicity to mammals. This feature permits the use of the compound as an insecticide in many instances where the closely related compounds cannot be used, for example, in the disinfestation of human and animal dwellings and food stores.
The favourable mammalian toxicity of the compound of this invention, and the toxicities of several closely related compounds, measured as the single dose L.D.50 for female rats measured in milligrams of 2~ substance orally administered per kilogram of live body weight is given in the foliowing table.
Compound ¦ L D 50(mg/kg) 0,0-Dimethyl 2-diethylaminopyrimidin- 800 4-yl phosphorothionate 0,0-Diethyl 2-dimethylaminopyrimidin- 100-200 4-yl phosphate 0-_-Butyl 2-dimethylaminopyrimidin-4- 12.5-25 yl methylphosphonate -- ~
- , . : , .' TABLE 1 (continued) Compound ~ L.D.50(mg/kg) 0,0-Diethyl 2-ethylaminopyrimidin-4-yl ~ 1.5-3.0 phosphate 0~0-Diethyl 2-(N-ethyl-N-methylamino) 25-50 pyrimidin-4-yl phosphorothionate 0,0-Diethyl 2-dimethylaminopyrimidin-4- 25-50 yl phosphorothionate 0,0-Diethyl 2-diethylaminopyrimidin-4-yl 10-50 phosphorothionate 0,0-Diethyl 2-diethylaminopyrimidin-4-yl ca.10 phosphate 0,0-Diethyl 2-ethylaminopyrimidin-4-yl ca.10 phosphorothionate The invention compound may be prepared by treating 2-diethylamino-4-hydroxypyrimidine, or an alkali metal salt thereof, with dimethylphosphorochloridothionate, preferably in a diluent or solvent, and optionally in the presence of a base. Suitable solvents are ketones, for example, acetone, or methyl isobutyl ketone, and esters, for example, ethyl acetate, but any nonreacting solvent or diluent may be used.
Suitable bases include alkali metal carbonates, for example potassium carbonate, and tertiary amines, for example triethylamine or diethylaniline. The reaction between the hydroxypyrimidinederivative and the halophosphorus compound may be accelerated or completed by heating, for example by refluxing the -mixture of reactants and solvent or diluent at the . .
~0474g7 reflux temperature of the solvent or diluent.
In use the compound may be applied in an undiluted form to combat insect pests, but is best applied in association with a diluent or carrier in the form of a composition.
In a further aspect therefore the invention provides pesticidal compositions comprising 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate in association with a diluent or carrier material.
The compositions may be in the form of granules wherein the active ingredient is absorbed on a porous granular material, for example pumice.
Alternatively the compositions may be in the form of liquid preparations to be used as dips or sprays, which are generally aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents. These compositions are prepared by dissolving the active ingredient in a suitable solvent, for example, a ketonic solvent such as diacetone alcohol, and adding the mixture so obtained to water which may contain one or more known wetting, dispersing or emulsifying agents.
The compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient or ingredients, the said concentrate to be diluted with water before use.
.. . . .
- , .
~04~497 These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable Or dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may contain 10-85% by weight of the active ingredients. When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used.
For agricultural or horticultural purposes, an aqueous preparation containing between 0.0001%
and 0.1% by weight of the active ingredient or ingredients may be used.
The compositions of the present invention, may, if desired, also comprise in addition to the compound of the present invention, at least one other biologically-active ingredient, for example an insecticide, or a fungicide.
In use the compositions are applied to the pests, to the locus of the pests, to the habitat of the pests, or to growing plants liable to infestation by the pests, by any of the known means Or applying pesticidal compositions, for example - by dusting ~r spraylng.
~0474~7 The compound of the invention and compositions comprising it are very toxic to wide varieties of insect and other invertebrate pests, including, for example the following:-Tetran~chus telarius (red spider mites) Aphis fabae (aphids) Megoura viceae (aphids) Aedes aegypti (mosquitos) Musca dome~tica (houseflies) Pieris brassicae (white butterfly, larvae) Plutella maculipennis (diamond back moth, larvae) Phaedon cochleariae (mustard beetle) Calandra granaria (grain beetle) The invention i8 illustrated by the following examples.
5 Parts by weight of 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate were thoroughly mixed in a suitable mixer with 95 parts by weight of talc. There was thus obtained a dusting powder.
10 Parts by weight of 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate 10 parts of an ethylene oxide-octylphenol condensate ~ . .
("Lissapol" NX; "Lissapol" is a Trade Mark) and 80 parts by weight of diacetone alcohol were thoroughly mixed. There was thus obtained a concentrate which, in mixing with water, gave an aqueous dispersion suitable for application as a spray in the control of insect pests.
A granular composition was prepared by dissolving the active ingredient in a solvent, spraying the solution obtained on to the granules of pumice and allowing the solvent to evaporate.
% wt.
0,0-dimethyl 2-diethylaminopyrimidin-4-yl 5 phosphorothionate Pumice Granules 95 100%
An aqueous dispersion formulation was prepared by mixing and grinding the ingredients recited below in the proportions stated.
% wt.
0,0-dimethyl 2-diethylaminopyrimidin-4-yl 40 phosphorothionate Calcium lignosulphonate 10 Water 5 100%
' .
'. ~: ', ,' ' , ~.
~o47~97 The activity of 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate was tested against a variety of insect and other invertebrate pests. The compound was used in the form of a liquid preparation containing 0.1% by weight of the compound except in the test with Aedes aegypti where the preparations contained 0.01% by weight Or the compound. The preparations 1~ were made by dissolving the compound in a mixture of solvents consisting of 4 parts by volume of acetone and 1 part~by volume of diacetone alcohol.
The solutions were then diluted with water containing 0.01% by weight of a wetting agent sold under the trade name "LISSAPOL" NX until the liquid preparations contained the required concentration of the compound. "Lissapol" is a Trade Mark.
The test procedure adopted with regard to each pests was basically the same and comprised supporting a number of the pests on a medium which was usually a host plant or a foodstuff on which the pests feed, and treating either or both the pests and the medium with the preparations.
The mortality of the pests was then assessed at periods usually varying from one to three days after th-e t~eatment.
. .
The results of the tests are given below in Table 2. In this table the first column indicates the name of the pest species. Each of the subsequent columns indicates the host plant or medium on which it was supported, the number of days which were allowed to elapse after the treatment before assessing the mortality of the pests, and the results obtained for the compound.
The assessment is expressed in integers which range from 0-3.
0 represents less t han 30% kill 1 represents 30-49% kill 2 represents 50-90% kill
The favourable mammalian toxicity of the compound of this invention, and the toxicities of several closely related compounds, measured as the single dose L.D.50 for female rats measured in milligrams of 2~ substance orally administered per kilogram of live body weight is given in the foliowing table.
Compound ¦ L D 50(mg/kg) 0,0-Dimethyl 2-diethylaminopyrimidin- 800 4-yl phosphorothionate 0,0-Diethyl 2-dimethylaminopyrimidin- 100-200 4-yl phosphate 0-_-Butyl 2-dimethylaminopyrimidin-4- 12.5-25 yl methylphosphonate -- ~
- , . : , .' TABLE 1 (continued) Compound ~ L.D.50(mg/kg) 0,0-Diethyl 2-ethylaminopyrimidin-4-yl ~ 1.5-3.0 phosphate 0~0-Diethyl 2-(N-ethyl-N-methylamino) 25-50 pyrimidin-4-yl phosphorothionate 0,0-Diethyl 2-dimethylaminopyrimidin-4- 25-50 yl phosphorothionate 0,0-Diethyl 2-diethylaminopyrimidin-4-yl 10-50 phosphorothionate 0,0-Diethyl 2-diethylaminopyrimidin-4-yl ca.10 phosphate 0,0-Diethyl 2-ethylaminopyrimidin-4-yl ca.10 phosphorothionate The invention compound may be prepared by treating 2-diethylamino-4-hydroxypyrimidine, or an alkali metal salt thereof, with dimethylphosphorochloridothionate, preferably in a diluent or solvent, and optionally in the presence of a base. Suitable solvents are ketones, for example, acetone, or methyl isobutyl ketone, and esters, for example, ethyl acetate, but any nonreacting solvent or diluent may be used.
Suitable bases include alkali metal carbonates, for example potassium carbonate, and tertiary amines, for example triethylamine or diethylaniline. The reaction between the hydroxypyrimidinederivative and the halophosphorus compound may be accelerated or completed by heating, for example by refluxing the -mixture of reactants and solvent or diluent at the . .
~0474g7 reflux temperature of the solvent or diluent.
In use the compound may be applied in an undiluted form to combat insect pests, but is best applied in association with a diluent or carrier in the form of a composition.
In a further aspect therefore the invention provides pesticidal compositions comprising 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate in association with a diluent or carrier material.
The compositions may be in the form of granules wherein the active ingredient is absorbed on a porous granular material, for example pumice.
Alternatively the compositions may be in the form of liquid preparations to be used as dips or sprays, which are generally aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents. These compositions are prepared by dissolving the active ingredient in a suitable solvent, for example, a ketonic solvent such as diacetone alcohol, and adding the mixture so obtained to water which may contain one or more known wetting, dispersing or emulsifying agents.
The compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient or ingredients, the said concentrate to be diluted with water before use.
.. . . .
- , .
~04~497 These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable Or dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may contain 10-85% by weight of the active ingredients. When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used.
For agricultural or horticultural purposes, an aqueous preparation containing between 0.0001%
and 0.1% by weight of the active ingredient or ingredients may be used.
The compositions of the present invention, may, if desired, also comprise in addition to the compound of the present invention, at least one other biologically-active ingredient, for example an insecticide, or a fungicide.
In use the compositions are applied to the pests, to the locus of the pests, to the habitat of the pests, or to growing plants liable to infestation by the pests, by any of the known means Or applying pesticidal compositions, for example - by dusting ~r spraylng.
~0474~7 The compound of the invention and compositions comprising it are very toxic to wide varieties of insect and other invertebrate pests, including, for example the following:-Tetran~chus telarius (red spider mites) Aphis fabae (aphids) Megoura viceae (aphids) Aedes aegypti (mosquitos) Musca dome~tica (houseflies) Pieris brassicae (white butterfly, larvae) Plutella maculipennis (diamond back moth, larvae) Phaedon cochleariae (mustard beetle) Calandra granaria (grain beetle) The invention i8 illustrated by the following examples.
5 Parts by weight of 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate were thoroughly mixed in a suitable mixer with 95 parts by weight of talc. There was thus obtained a dusting powder.
10 Parts by weight of 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate 10 parts of an ethylene oxide-octylphenol condensate ~ . .
("Lissapol" NX; "Lissapol" is a Trade Mark) and 80 parts by weight of diacetone alcohol were thoroughly mixed. There was thus obtained a concentrate which, in mixing with water, gave an aqueous dispersion suitable for application as a spray in the control of insect pests.
A granular composition was prepared by dissolving the active ingredient in a solvent, spraying the solution obtained on to the granules of pumice and allowing the solvent to evaporate.
% wt.
0,0-dimethyl 2-diethylaminopyrimidin-4-yl 5 phosphorothionate Pumice Granules 95 100%
An aqueous dispersion formulation was prepared by mixing and grinding the ingredients recited below in the proportions stated.
% wt.
0,0-dimethyl 2-diethylaminopyrimidin-4-yl 40 phosphorothionate Calcium lignosulphonate 10 Water 5 100%
' .
'. ~: ', ,' ' , ~.
~o47~97 The activity of 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate was tested against a variety of insect and other invertebrate pests. The compound was used in the form of a liquid preparation containing 0.1% by weight of the compound except in the test with Aedes aegypti where the preparations contained 0.01% by weight Or the compound. The preparations 1~ were made by dissolving the compound in a mixture of solvents consisting of 4 parts by volume of acetone and 1 part~by volume of diacetone alcohol.
The solutions were then diluted with water containing 0.01% by weight of a wetting agent sold under the trade name "LISSAPOL" NX until the liquid preparations contained the required concentration of the compound. "Lissapol" is a Trade Mark.
The test procedure adopted with regard to each pests was basically the same and comprised supporting a number of the pests on a medium which was usually a host plant or a foodstuff on which the pests feed, and treating either or both the pests and the medium with the preparations.
The mortality of the pests was then assessed at periods usually varying from one to three days after th-e t~eatment.
. .
The results of the tests are given below in Table 2. In this table the first column indicates the name of the pest species. Each of the subsequent columns indicates the host plant or medium on which it was supported, the number of days which were allowed to elapse after the treatment before assessing the mortality of the pests, and the results obtained for the compound.
The assessment is expressed in integers which range from 0-3.
0 represents less t han 30% kill 1 represents 30-49% kill 2 represents 50-90% kill
3 represents over 90% kill In Table 2 "contact test" indicates that both the pests and the medium were treated, "residual test" indicates that the medium was treated before infestation with the pests, and "systemic test"
indicates that the leaves of the host plant were infested after the roots of the plant had been treated with the aqueous preparation.
. ~ , . . ~
. , :: . : :: . . .. . .
-: - - - : . . . -- . . . . . . . .
- , .
, ~
1~)47497 ! Pest Species, Support No of Grading Medium Days ~ - ! --Tetranychus telarius I French 3 3 red spider mites, adults I Bean fabae 1 Broad 2 3 aph1ds) Bean Megoura viceae ~ Broad 2 3 (aphids) I Bean Dysdercus fasciatus Grain 2 3 (capsids) .
Aedes ae~Y~ti Water 1 3 T~squito larvae) Aedes aegypti Plywood 1 3 (mosquito adults) Musca domestica Milk/ 2 3 (hou~eflies - contact test) Sugar Musca domestica Plywood 2 3 (houseflies - residual test) Blattella germanica _ 2 3 chroaches) ~
Pieris brassicae Cabbage 2 3 (cabbage white, larvae -systemic test) . .
Pieris brassicae Cabbage 2 3 (cabbage white, larvae -contact test) . .
Plutella maculipenni~ Mustard 2 2 (diamond back, ~arvae -systemic test) Plutella maculipennis Mustard 2 3 (diamond back, larvae -residual test) Phaedon cochleariae Mustard 2 3 (mustard beetles - systemic . test) . .
.
- , , :
- ~, TABLE 2 (continued) _____ . _., ., . ._ , ., .. .. __ Pest Species Support No of Grading Medium Days t ~ _ ._ ___ Phaedon cochleariae Mustard 2 3 (mustard beetles -residual test) Calandra granaria Grain 2 3 (grain beetles~
Tribolium confusum Grain 2 3 (flour beetles) Meloidogyne incognita Tomato 14 3 nemat ode s .
This example illustrates the prepàration of 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate.
To a solution of 2-diethylamino-4-hydroxypyrimidine (3.0 ~) in dry acetone (50 ml.) was added anhydrous potassium carbonate (4.96 g.) and dimethylphosphorochlorido-thionate (3.03 g.). The mixture was stirred at the ambient temperature for 24 hours and then filtered to remove the insoluble material. The filtrate was evaporated under reduced pressure at 35C, and the residual oil dissolved in methylene chloride (50 ml.) The solution was washed successively with aqueous sodium hydroxide solution (1%, 2 x 15 ml.), water (2 x 15 ml.) and brine (20 ml.), and dried over anhydrous magnesium sulphate. After filtration and evaporation of the solvent - : . -,' .
:
:
- ':
, :
, ~047497 the residual oil was purified by preparative thin layer chromatography to yield 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate, pale yellow oil, ~4 1.5340. The structure of the product was confirmed by infra-red and nuclear magnetic spectroscopy.
' ' ' :
indicates that the leaves of the host plant were infested after the roots of the plant had been treated with the aqueous preparation.
. ~ , . . ~
. , :: . : :: . . .. . .
-: - - - : . . . -- . . . . . . . .
- , .
, ~
1~)47497 ! Pest Species, Support No of Grading Medium Days ~ - ! --Tetranychus telarius I French 3 3 red spider mites, adults I Bean fabae 1 Broad 2 3 aph1ds) Bean Megoura viceae ~ Broad 2 3 (aphids) I Bean Dysdercus fasciatus Grain 2 3 (capsids) .
Aedes ae~Y~ti Water 1 3 T~squito larvae) Aedes aegypti Plywood 1 3 (mosquito adults) Musca domestica Milk/ 2 3 (hou~eflies - contact test) Sugar Musca domestica Plywood 2 3 (houseflies - residual test) Blattella germanica _ 2 3 chroaches) ~
Pieris brassicae Cabbage 2 3 (cabbage white, larvae -systemic test) . .
Pieris brassicae Cabbage 2 3 (cabbage white, larvae -contact test) . .
Plutella maculipenni~ Mustard 2 2 (diamond back, ~arvae -systemic test) Plutella maculipennis Mustard 2 3 (diamond back, larvae -residual test) Phaedon cochleariae Mustard 2 3 (mustard beetles - systemic . test) . .
.
- , , :
- ~, TABLE 2 (continued) _____ . _., ., . ._ , ., .. .. __ Pest Species Support No of Grading Medium Days t ~ _ ._ ___ Phaedon cochleariae Mustard 2 3 (mustard beetles -residual test) Calandra granaria Grain 2 3 (grain beetles~
Tribolium confusum Grain 2 3 (flour beetles) Meloidogyne incognita Tomato 14 3 nemat ode s .
This example illustrates the prepàration of 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate.
To a solution of 2-diethylamino-4-hydroxypyrimidine (3.0 ~) in dry acetone (50 ml.) was added anhydrous potassium carbonate (4.96 g.) and dimethylphosphorochlorido-thionate (3.03 g.). The mixture was stirred at the ambient temperature for 24 hours and then filtered to remove the insoluble material. The filtrate was evaporated under reduced pressure at 35C, and the residual oil dissolved in methylene chloride (50 ml.) The solution was washed successively with aqueous sodium hydroxide solution (1%, 2 x 15 ml.), water (2 x 15 ml.) and brine (20 ml.), and dried over anhydrous magnesium sulphate. After filtration and evaporation of the solvent - : . -,' .
:
:
- ':
, :
, ~047497 the residual oil was purified by preparative thin layer chromatography to yield 0,0-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate, pale yellow oil, ~4 1.5340. The structure of the product was confirmed by infra-red and nuclear magnetic spectroscopy.
' ' ' :
Claims (2)
1. O,O-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate.
2. A method of combating insect pests at a locus which comprises applying to the locus an insecticidally effective amount of O,O-dimethyl 2-diethylaminopyrimidin-4-yl phosphorothionate in association with a dilent or carrier.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2655573A GB1434764A (en) | 1973-06-04 | 1973-06-04 | Pesticidal phosphorus-containing pyrimidine derivative |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1047497A true CA1047497A (en) | 1979-01-30 |
Family
ID=10245485
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA200,703A Expired CA1047497A (en) | 1973-06-04 | 1974-05-23 | Heterocyclic derivative |
Country Status (8)
Country | Link |
---|---|
JP (1) | JPS5031049A (en) |
CA (1) | CA1047497A (en) |
CH (1) | CH585017A5 (en) |
DE (1) | DE2426609A1 (en) |
FR (1) | FR2231680B1 (en) |
GB (1) | GB1434764A (en) |
IL (1) | IL44847A (en) |
IT (1) | IT1046645B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5832226B2 (en) * | 1977-01-18 | 1983-07-12 | 三菱マテリアル株式会社 | Tungsten carbide-based cemented carbide for bits |
JPH116025A (en) * | 1997-04-25 | 1999-01-12 | Sumitomo Electric Ind Ltd | Cemented carbide, and coated alloy and coated hard tool using this cemented carbide as base material |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL129225C (en) * | 1963-03-28 | 1900-01-01 |
-
1973
- 1973-06-04 GB GB2655573A patent/GB1434764A/en not_active Expired
-
1974
- 1974-05-16 IL IL44847A patent/IL44847A/en unknown
- 1974-05-23 CA CA200,703A patent/CA1047497A/en not_active Expired
- 1974-05-28 IT IT23279/74A patent/IT1046645B/en active
- 1974-05-31 FR FR7418925A patent/FR2231680B1/fr not_active Expired
- 1974-05-31 DE DE19742426609 patent/DE2426609A1/en not_active Withdrawn
- 1974-06-03 JP JP49061958A patent/JPS5031049A/ja active Pending
- 1974-06-04 CH CH758274A patent/CH585017A5/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
FR2231680B1 (en) | 1978-01-20 |
IT1046645B (en) | 1980-07-31 |
CH585017A5 (en) | 1977-02-28 |
FR2231680A1 (en) | 1974-12-27 |
AU6889874A (en) | 1975-11-20 |
IL44847A (en) | 1976-10-31 |
JPS5031049A (en) | 1975-03-27 |
GB1434764A (en) | 1976-05-05 |
DE2426609A1 (en) | 1975-01-02 |
IL44847A0 (en) | 1974-07-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4081536A (en) | N-[(phosphinyl) amino]thio- and N-[(phosphinothioyl)amino]-thio-methylcarbamates and methods for controlling insects | |
JP3086924B2 (en) | Insecticidal composition | |
US4014882A (en) | Trifluoromethyl substituted pyrimidine derivatives useful as insecticides | |
US3932631A (en) | Certain organophosphorus compounds used to control insects | |
CA1047497A (en) | Heterocyclic derivative | |
US4237168A (en) | N-(4-Chloro-2-methylphenyl)-N-hydroxy methanimidamide and its pesticidal use | |
US4024277A (en) | Phosphoro-aminosulfenyl derivatives of benzofuran carbamates | |
EP0000528B1 (en) | Organophosphonic ester compounds, process for their preparation and their utilisation as insecticides, acaricides and nematocides | |
US4225595A (en) | Piperazine phosphates and phosphonate insecticides | |
IL44555A (en) | Pyrimidyl (thio)phosphoric acid esters | |
US4048172A (en) | Carbonylmethylpyrimidin-6-yl phosphates and phosphorothionates | |
HU183194B (en) | Insecticide compositions containing substituted ester of5-pyrimidino-phosphoric acid as active agent, and process for producing the active agent | |
US3590074A (en) | Chlor-methyl-isopropyl-phenyl-n-methyl carbamate | |
US3551529A (en) | Di-lower alkyl phosphites of 2-(lower-alkylthio)alkanaldoximes | |
US4363804A (en) | Phosphonodithioylacetylamino phenyl pyrazoles | |
US3935212A (en) | Pesticidal substituted 2-hydroxylaminopyrimidinyl phosphorus esters | |
US4201733A (en) | Process for preparing N-[(phosphinyl)amino]thio- and N-[(phosphinyl)amino]th | |
US3767662A (en) | Certain 1,3-thiazolidin-4-ones | |
US4197295A (en) | Pyrazole phosphates and phosphonates - insecticides | |
US3470229A (en) | O,o-dialkyl-o-(dithiocarbonato) ethyl-phosphoric acid esters | |
US4356022A (en) | S-Alkyl and alkenyl-thiophenylacetamido thiophosphates and phosphonates as plant growth regulants | |
US4283395A (en) | S-Alkyl and alkenyl-thiophenylacetamido thiophosphates and phosphonates and method of controlling insects | |
CA1078399A (en) | Insecticidal active thiophene phosphorous derivatives | |
US4223028A (en) | Butynylamide phosphate and phosphonates and method for controlling insects | |
US4716156A (en) | Phosphonodithioylacetyl phenyl aminoacid ethyl esters |