IL47131A - 1,2,4-triazolyl phosphoric thionophosphoric phosphonic and thionophosphonic acid esters and ester amides their preparation and their use as insecticides acaricides and nematicides - Google Patents
1,2,4-triazolyl phosphoric thionophosphoric phosphonic and thionophosphonic acid esters and ester amides their preparation and their use as insecticides acaricides and nematicidesInfo
- Publication number
- IL47131A IL47131A IL7547131A IL4713175A IL47131A IL 47131 A IL47131 A IL 47131A IL 7547131 A IL7547131 A IL 7547131A IL 4713175 A IL4713175 A IL 4713175A IL 47131 A IL47131 A IL 47131A
- Authority
- IL
- Israel
- Prior art keywords
- compound
- formula
- carbon atoms
- process according
- active
- Prior art date
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- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 244000078703 ectoparasite Species 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 230000003032 phytopathogenic effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- 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
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6518—Five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
1454490 Phosphorus-containing triazole derivatives BAYER AG 15 April 1975 [24 April 1974 18 May 1974] 15435/75 Headings C2P and C2C The invention comprises compounds of the formula wherein R is C 1 -C 2 alkyl, R<SP>1</SP> is alkyl, alkylamino or alkoxy each with 1 to 6 carbon atoms, or is phenyl, R<SP>11</SP> is alkenyl with up to 6 carbon atoms and X is O or S. They are obtained by reacting a compound (III) with a halide: (RO)(R<SP>1</SP>)P(X)Hal wherein Hal is halogen, the compound III being used as such in the presence of an acid acceptor, or in the form of an alkali metal-, alkaline earth metal-, or -ammonium salt. The products have pesticidal (including nematicidal) properties and may be used as active ingredients in conventional pesticidal compositions. The triazole derivatives of the above Formula (III) are obtained by reacting a halogenocarbonic acid alkyl ester with KCNS and then with phenylhydrazone to give an intermediate product of the formula which is then reacted with an appropriate halogenoalkene in the presence of an alcoholate. A detailed example is given for the preparation of the compound IV which is isolated and then converted to compounds of Formula III in which R<SP>11</SP> is -CH 2 -C(CH 3 )=CH 2 , and -H 2 -CH=CH-CH 3 respectively.
[GB1454490A]
Description
47131/2 τκ·»το-4,2,1 nisom *?ν ο'¾?τπ D"»T»OK nt>D»i CTDDK nmoaai ηιηρκ ,ο»ρ*ιπ ' oipa bns ¾?»as>m nnjsn Novel 1 ,2,4-triazolyl phosphoric, thionophosphoric, phosphonic and thionophosphonic acid esters and ester amides, their preparation and their use as insecticides, acaricides and nematicides BAYER A TIEWGESELLSCHAFT C:- 44875 47131/2 The present invention relates to certain new O-triazolyl ( thiono)-phosphoric(phosphonic) acid esters and ester amides, to a process for their preparation and to their use as insecticides, acaricides and nematicides.
It is already known that 0,0-dimethyl-0-L3-methyl-pyrazol(5 )yl J- and 0,0-diethyl-0-[ 1 -isopropyl-5-methyl-mercapto-(l ,2,4)-triazol(3)ylJ-thiono-phosphoric acid esters possess insecticidal and acaricidal properties (see U.S.
Patent 2,754,244 and German Offenlegunfisschrift (German Published Specification) 2,259,960).
The present invention provides, as new compounds, the 0-triazolyl-( thiono)-phosphoric(phosphonic) acid esters and ester amides of the general formula in which R is alkyl with 1 to 6 carbon atoms, R' is alkyl, alkylamino or alkoxy each with 1 to 6 carbon atoms, or phenyl, R" is alkenyl with 3 to 6 carbon atoms, and X is oxygen or sulphur.
The compounds of the formula (I) have been found to possess powerful insecticidal, acaricidal and nematicidal properties.
Preferably R is straight-chain or branched alkyl with 1 to 5 (especially 1 to 4) carbon atoms, R* is straight-chain or bran h d 47131/2 (especially 1 to 4) carbon atoms, or is phenyl, R" is alkenyl with ', '3 to 5 (especially 3 ' to 4) carbon atoms, and X is sulphur.
The invention also provides a process for the preparation of an O-triazolyl-(thiono)-phosphoric(phosphonic) acid ester or ester amide of the formula (I), in which a (thiono)phosphoric (phosphonic) acid ester halide or ester amide halide of the general formula in which X, R and R1 have the above-mentioned meanings and Hal is halogen, preferably chlorine, is reacted with a 1 -phenyl-3-hydroxy-5-alkenylmercapto-triazole derivative of the general formula in which R" has the above-mentioned meaning, the compound (ill) being used as such, in the presence of an acid acceptor, or in the form of an alkali metal salt, alkaline earth metal salt or ammonium salt thereof.
Surprisingly, the 0-triazolyl-(thiono)-phosphoric-(phosphonic) acid esters and ester amides according to the invention have a better insecticidal, including soil-insecticidal, acaricidal and nematicidal action than previously known compounds of analogous structure and of the same type of action. They are active not only against insects and mites which damage plants, but also against pests harmful to health and pests of stored products, and in the veterinary medicine field, against ectoparasites, for example against parasitic fly larvae. The compounds according to the invention thus represent a genuine enrichment of -the art.
If, for example, 0,0-dimethylthionophosphoric acid diester chloride and 1 -phenyl-3-hydroxy-5-allylmercapto-triazole-(l ,2,4) are used as starting materials, the course of the reaction can be represented by the following equation: The (thiono)phosphoric(phosphonic) acid ester halides and ester amide halides (II) to be used as starting materials are known from the literature and can be prepared according to customary processes, even on a large industrial scale.
The following may be mentioned as examples thereof: 0,0-d.imethyl-, 0, 0-diethyl-, 0,0-di-n-propyl-, 0,0-di-iso-propyl-, 0,0-di-n-butyl-, 0,0-di-isobutyl-, 0,0-di-tert .-butyl-, 0-ethyl-O-n-propyl-, 0-ethyl-O-isopropyl- and 0-ethyl-0-sec. -butyl-phosphoric acid ester chloride; 0-methyl-, 0-ethyl-, 0-n-propyl-, 0-isopropyl-, 0-n-butyl-, 0-sec. -butyl 0-isobutyl- or 0-tert.-butyl-methane-, -ethane-, -n- ro ane- -isopropane-, -η-butane-, -isobutane-, -sec. -butane-, -tert.1-butane- or -phenyl-phosphonic acid ester chloride; O-methyl-N-methyl-, O-methyl-N-ethyl-, O-methyl-N-n-propyl-, O-methyl-N-isopropyl-, O-methyl-N-n-butyl-, O-ethyl-N-methyl-, O-ethyl N-ethyl-, O-ethyl-N-n-propyl-, O-ethyl-N-isopropyl-, O-ethyl-N-n-butyl-, 0-ethy1-N-sec.-butyl-, O-n-propyl-N-meth l-, O-n-propyl-N-eth l-, O-n-propyl-N-n-propyl-, O-n-propyl-N-isopropyl-, O-n-propyl-N-n-butyl-, O-isopropyl-N-ethyl-, O-isopropyl-N-n-propyl-, O-n-butyl-N-ethyl- or O-tert ,-butyl-N-ethyl-phosphoric acid ester amide chloride; and the thiono analogues of all of the aforesaid compounds.
The 1 -phenyl-3-hydroxy-5-alkenylmercaptotriazoles of the formula (III), some of which have not been described in the literature, can be prepared according to processes which are known in principle. For example, halogenocarbonic acid alkyl esters are reacted with potassium thiocyanate and subsequently with phenylhydrazone to give the intermediate product of the formula from which the desired hydroxytriazoles (III) can then be prepared by reaction with the appropriate halogenoalkenes in the presence of alcoholates.
The following may be mentioned as examples of triazole derivatives (III): 1 -phenyl-3-hydroxy-5~allylmercapto-, -5-buten(2' )yl-mercapto- and -5-[2 '-methyl-propen-(2 ' )-yl-mercapto]-triazole-(l ,2,4).
The process of preparation is preferably carried out in the presence of a suitable solvent or diluent. Practi- r cally all inert organic solvents can be used for this purpose, especially aliphatic and aromatic, optionally chlorinated, hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride or chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxan; ketones, for example acetone methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; and nitriles, such as acetonitrile and propionitrile.
All customary acid-binding agents can be used as acid acceptors. Alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate and potassium carbonate, sodium methylate and ethylate and potassium methylate and ethylate have proved particularly successful, as have aliphatic, aromatic or heterocyclic amines, for example triethylamine and trimeth lamine , dimethylaniline , dimethylbenzylamine and pyridine.
The reaction temperature can be varied within a fairly wide range. In general, the reaction is carried out at between 0° and 120°C, preferably at from 30° to 85°C.
To carry out the process, the starting materials are generally employed in equimolar amounts. An excess of one or other reactant does not result in any significant advantages. The reaction is preferably carried out in one of the solvents mentioned, in the presence of an acid acceptor, at the stated temperature and whilst stirring, and after a reaction time of one or more hours, in most cases at elevated temperatures, the batch is worked up in the usual manner. In eneral the reaction mixture is oured into wwaatteerr aanndd ttaakkeenn uupp iinn aann oorrggaanniicc ssoollvveenntt,, ffoorr eexxaammppllee ψψ mmeetthhyylleennee cchhlloorriiddee,, tthhee oorrggaanniicc pphhaassee iiss wwaasshheedd aanndd ddrriieedd,, aanndd tthhee ssoollvveenntt iiss ddiissttiilllleedd ooffff uunnddeerr rreedduucceedd pprreessssuurree00 T Thhee nneeww ccoommppoouunnddss aarree ffrreeqquueennttllyy oobbttaaiinneedd iinn tthhee ffoorrmm ooff ooiillss wwhhiicchh iinn mmoosstt ccaasseess ccaannnnoott bbee ddiissttiilllleedd wwiitthhoouutt ddeeccoommppoossiittiioonn bbuutt ccaann bbee ffrreeeedd ffrroomm tthhee llaasstt vvoollaattiillee ccoonn¬ssttiittuueennttss bbyy ssoo--ccaalllleedd ""sslliigghhtt ddiissttiillllaattiioonn"",, tthhaatt iiss ttoo ssaayy pprroolloonnggeedd hheeaattiinngg uunnddeerr rreedduucceedd pprreessssuurree ttoo mmooddeerraatteellyy eelleevvaatteedd tteemmppeerraattuurreess,, aanndd ccaann bbee ppuurriiffiieedd iinn tthhiiss wwaayy.. TThheeyy aarree cchhaarraacctteerriisseedd bbyy tthhee rreeffrraaccttiivvee iinnddeexx.. SSoommee ccoommppoouunnddss aarree oobbttaaiinneedd iinn aa ccrryyssttaalllliinnee ffoorrmm ooff sshhaarrpp mmeellttiinngg ppooiinntt..
A Ass aallrreeaaddyy mmeennttiioonneedd,, tthhee 00--ttrriiaazzoollee--(( tthhiioonnoo))--pphhoosspphhoorriicc((pphhoosspphhoonniicc)) aacciidd eesstteerrss aanndd eesstteerr aammiiddeess ((II)) aaccccoorrddiinngg ttoo tthhee iinnvveennttiioonn aarree ddiissttiinngguuiisshheedd bbyy aann oouutt¬ssttaannddiinngg iinnsseeccttiicciiddaall,, iinncclluuddiinngg ssooiill--iinnsseeccttiicciiddaall,, aaccaarriicciiddaall aanndd nneemmaattiicciiddaall aaccttiivviittyy.. TThheeyy aarree aaccttiivvee nnoott oonnllyy aaggaaiinnsstt ppllaanntt ppeessttss,, ppeessttss hhaarrmmffuull ttoo hheeaalltthh aanndd ppeessttss ooff ssttoorreedd pprroodduuccttss,, bbuutt aallssoo,, iinn tthhee vveetteerriinnaarryy mmeeddiicciinnee ffiieelldd,, aaggaaiinnsstt aanniimmaall ppaarraassiitteess ((eeccttooppaarraassiitteess)),, ssuucchh aass ppaarraassiittiicc ffllyy llaarrvvaaee,, aanndd ccoommbbiinnee aa llooww pphhyyttoottooxxiicciittyy wwiitthh aa ggoooodd aaccttiioonn aaggaaiinnsstt bbootthh ssuucckkiinngg aanndd bbiittiinngg iinnsseeccttss aass wweellll aass mmiitteess..
. . FFoorr tthhiiss rreeaassoonn,, tthhee ccoommppoouunnddss aaccccoorrddiinngg ttoo tthhee iinn¬vveennttiioonn ccaann bbee eemmppllooyyeedd ssuucccceessssffuullllyy aass ppeessttiicciiddeess iinn ppllaanntt pprrootteeccttiioonn aanndd iinn tthhee hhyyggiieennee ffiieelldd,, tthhee ffiieelldd ooff pprrootteeccttiioonn ooff ssttoorreedd pprroodduuccttss aanndd tthhee vveetteerriinnaarryy ffiieelldd..
T Too tthhee ssuucckkiinngg iinnsseeccttss tthheerree bbeelloonngg,, iinn tthhee mmaaiinn,, aapphhiiddss ((AApphhiiddiiddaaee)) ssuucchh aass tthhee ggrreeeenn ppeeaacchh aapphhiidd ((MMyyzzuuss ppeerrssiiccaaee)) ,, tthhee bbeeaann aapphhiidd ((DDoorraalliiss ffaabbaaee)),, tthhee bbiirrdd cchheerrrryy aapphhiidd ((RRhhooppaalloo--sBiipphhuumm ppaaddii))., tthhee eeaa aa hhiidd (("" ** '' ·· aanndd tthhee oottaattoo aphid (Macrosiphum solanifolii) , the currant gall aphid ▼ (Cryptomyzus korschelti) , the rosy apple aphid (Sappaphis mali) , the mealy plum aphid (Hyalopterus arundinis ) and the cherry black-fly (My2us cerasi) ; in addition scales and mealybugs (Coccina) , for example the oleander scale (Aspidio-tus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudococcus maritimus) ; thrips (Thysanoptera) . such as Hercinothrips femoralis , and bugs, for example the beet bug (Piesma quadrata) , the red cotton bug (Dysdercus intermedins) , the bed bug (Cimex lectularius) , the assassin bug (Rhodnius prolixus) and Chagas' bug (Triatoma infestans ) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus.
In the case of the biting insects, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Piute11a maculipennis ) , the gipsy moth (Lymantria dispar) , the brown-tail moth (Euproctis chrysorrhoea) and tent caterpillar (Malacosoma neustria) ; further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segetum) , the large white butterfly (Pieris brassicae) , the small winter moth (Cheimatobia brumata) , the green oak tortrix moth (Tortrix viridana) . the fall armyworm (Laphygma frugiperda) and cotton.worm (Prodenia litura) , the ermine moth (Hyponomeuta padella) , the Mediterranean flour moth (Ephestia kuhniella) and greater wax moth (Galleria mellonella) .
Also to be classed with the biting insects are beetles (Coleoptera) , for example the granary weevil (Sitophilus granarius = Calandra granaria) , the Colorado beetle (Leptino-tarsa decemlineata the dock beetle the mustard beetle (Phaedon cochleariae) , the blossom beetle (Meligethes aeneus) . the raspberry beetle (Byturus tomentosus) , the bean weevil (Bruchidius = Acanthoscelides obtectus) , the leather beetle (Dermestes frischi) , the khapra beetle (Trogoderma granarium) , the flour beetle (Tribolium castaneum) , the northern corn billbug (Calandra or Sitophilus zeamais) , the drugstore beetle (Stegobium paniceum) , the yellow mealworm (Tenebrio molitor) and the saw-toothed grain beetle (Oryzae-philus surinamensis) . but also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha) ; cockroaches, such as the German cockroach (Blattella germanica) , American cockroach (Peri-planeta americana) , Madeira cockroach (Leucophaea or Rhyparobia maderae) , oriental cockroach (Blatta orientalis) , the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus uscus ) as well as Henschoutedenia flexivitta: further, Orthop era. for example the house cricket (G-ryllus domesticus) ; termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymen-optera such as ants, for example the garden ant (Lasius niger) .
The Diptera comprise essentially the flies, such as the vinegar fly (Prosophila melanogaster) , the Mediterranean fruit fly (Qeratitis capitata) , the house fly (Musca dome3tica) , the little house fly (Fannia canicularis) , the black blow fly (Phormia re ina) and bluebottle fly (Galliphora erythrocephala) as well as the stable fly (Sto oxys calci-trans ) ; further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti) , the northern house mosquito ( Culex pipiens) and the malaria mosquito (Anopheles With the mites (Acarina) there are classed, in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetranychus urticae) and the European red mite ( Paratetranychus pilosus = Panonychus ulmi) , gall mites, for example the blackcurrant gall mite (Erioph es ribis) and tarsonemids, for example the broad mite (Hemi-tarsonemus latus) and the cyclamen mite (Tarsonemus pallidus ) ; finally, ticks, such as the relapsing fever tick (Ornithodorus moubata) .
When applied against pests harmful to health and pests of stored products, particularly flies and mosquitoes, the process products are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.
The active compounds according to the invention combine a low toxicity to warm-blooded animals with powerful nematicidal properties and can therefore be used to combat nematodes, especially phytopathogenic nematodes. These essentially include leaf eelworms (Aphelenchoides ) , such as the chrysanthemum eelworm (A. ritzemabosi) , the leaf -blotch eelworm (A. fragariae ) , and the rice eelworm (A. oryzae ) : stem nematodes (Ditylenchus ) , such as the stem eelworm (D. Dipsaci ) ; root-knot nematodes (Meloidogyne ) , such as M. arenaria and M. incognita; cyst-forming nematodes (Hetero-dera) , such as the potato cyst eelworm (H. rostochiensis ) , and the beet cyst eelworm (H. schactii) . and also free-living root nematodes, for example of the genera Pratylenchus .
Paratylenchus . Rotylenchus , Xiphinema and Radopholus .
The active compounds according to the present invention solutions, emulsions, suspensions, powders, pastes and granulates. These may be produced in known manner, for example by mixing the active compounds with extenders, that is, liquid or solid or liquefied gaseous diluents or carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents.
As liquid diluents or carriers, there are preferably used aromatic hydrocarbons, such as xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclo-hexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone , or strongly polar solvents, such as dimethyl formamide, dimethyl sulphoxide or acetonitrile, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperatures and pressures, for example aerosol propellants, such as halo-genated hydrocarbons, for example freon.
As solid diluents or carriers, there are preferably used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, or ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates. include non-ionic and anionic emulsifiers, such as polyoxy- ' ethylene-fa t acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkyl sulphonates, alkyl sulphates and aryl sulphonates as well as albumin hydrolyzation products; and preferred examples of dispersing agents include lignin sulphite waste liquors and methyl cellulose„ The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, emulsions, foams, suspensions powders, pastes, soluble powders, dusting agents and granules They may be used in the customary manner, for example by squirting, spraying, atomising, dusting, scattering, fumigating, gassing, watering, dressing or encrusting.
The active-compound concentrations in the ready-to-use preparations can be varied within fairly wide ranges. In general, they are between 0.0001 and 10 , preferably between 0.01 and 1$, by weight.
The active compounds can also be used with good success in the ultra-low volume (ULV) method where it is possible to apply formulations of up to 9 $ active compound or even to use the active compound by itself.
The present invention also provides an insecticidal, acaricidal or nematicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixtur th surface-active agent. ' The present invention also provides a method of combating insects, acarids or nematodes which comprises applying to the insects, acarids or nematodes, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by insects, acarids or nematodes by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier. It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
In the biotest Examples A to E which follow, the active compounds according to the invention were tested, with regard to their activity against a range of plant pests, in comparison to 0,0-dimet¾rrO-i3-niethyl-pyrazol(5)yl]-thionophosphoric acid ester (A), 0,0-diethyl-0-[l -isopropyl-5-methylmercapto-(1 ,2,4)-triazol(3)yl]-thionophosphoric acid ester (B), 0-eth l-0-[l -isopropyl-5-methylmercapto-( 1 ,2,4)-triazol(3)yl]-phenyl-thionophosphonic acid ester (C), 0,0-dimethyl-O-[1 -isopropyl-5-methylmercapto-( 1 ,2,4)-triazol(3)yl]-thionophosphoric acid ester D) , l-ethyl-3-hydroxy-5-allylmercapto- (1 , 2, 4) -triazole (E) and 0 , O-diethyl-0-[l-phenyl-5-methylthio-l , 2 , 4-triazolyl- (3) ] thiophosphate (F) . The present compounds tested are each identified, in the various biotest Examples, by the number of the corresponding preparative Example hereinafter.
Examole A Plutella test Solvent : 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the active compound until dew moist and were then infested with caterpillars of the diamond-back moth (Plutella maculipennis ) .
After the specified periods of time, the degree of destruction was determined as a percentage: 100$ means that all the caterpillars were killed, whereas Ο56 means that none of the caterpillars were killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: a b l e A (Plutella test) Active Active compound Degree of compound concentration destruction in % - in % after days: Cone. 0.05% 3 4 8 12 15 18 (A) 0.1 0 (F) 100 40 0 (4) 0.1 100 (2) 0.1 100 100 100 100 50 100 (3) 0.1 100 (10) 0.1 100 (1) 0.1 100 (8) 0.1 100 (7) 0.1 100 100 100 100 100 100 Example B Myzus test (contact action) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alk laryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.
Cabbage plants (Brassica oleracea) , which had been heavily infested with peach aphids (Myzus persicae ) , were sprayed with the preparation of the active compound until dripping wet.
After the specified periods of time, the degree of destruction was determined as a percentage: 100 means that all the aphids were killed whereas 0% means that none of the were killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table: T a b l e B (Myzus test) Active Active compound con- Degree of destruction compound centration in in j after 1 day (A) 0.1 0 (4) 0.1 100 (2) 0.1 00 (3) 0.1 100 (10) 0.1 100 (8) 0.1 100 (7) 0.1 100 (9) 0.1 100 Example C Critical concentration test/soil insects Test insect: Phorbia antiqua - grubs in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alk laryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration. The preparation of active compound was intimately mixed with the soil. The concentration of the active compound in the preparation was practically immaterial, the only decisive factor being the amount by weight of active compound per unit volume of soil, which is quoted in ppm (for example mg/l). The soil was filled into pots and the pots were left to stand at room temperature. After 24 hours the test insects were introduced into the treated soil and after a further 48 hours the degree of effectiveness of the active compound was determined in # by counting the dead and live test insects. The degree of effectiveness was 100$ if all test insects had been killed and was 0% if exactly as many test insects were still alive as in the case of the control.
The active compounds, amounts used and results can be seen from the table which follows: T a 1 e C (Phorbia antiqua - grubs in the soil) Active Active compound con- Degree of destruction compound centration in ppm in (B) 20 0 (4) 20 100 10 100 5 100 (5) 20 100 10 100 5 90 (1) 20 100 10 100 5 95 (6) 20 100 10 100 5 50 Example D Test with parasitic fly larvae Solvent : 35 parts by weight of ethylene polyglycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether To produce a suitable preparation of active compound, 30 parts by weight of. the active substance in question were mixed with the stated amount of solvent which contained the above-mentioned proportion of emulsifier and the concentrate thus obtained was diluted with water to the desired concentration.
About 20 fly larvae (Lucilia cuprina) were introduced into a test tube which contained approx. 2 cm of horse muscle 0.5 ml of the preparation of active compound was applied to in # was determined. 100$ means that all larvae had been killed and 0 means that no larvae had been killed.
The active compounds, the concentrations of the active compounds and the results can be seen from the table which follows: a b l e D (Test with parasitic fly larvae/Lucilia cuprina res.) Active Active compound con- Degree of destruc- compound centration in ppm tion in ¾ (4) 100 100 30 100 10 100 (3) 100 100 30 100 10 100 3 <50 Example E Critical concentration test/nematicides Test nematode: eloidogyne incognita Solvent : 3 parts by weight of acetone Emulsifier: 1 part by weight of alkyl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.
The preparation of active compound was intimately mixed with soil which was heavily infested with the test nematodes. The concentration of the active compound in the preparation was of practically no importance; only the amount of active compound per unit volume of soil, which is given in ppm (e.g. mg/l), was decisive. The treated soil was filled into pots, lettuce was sown in and the pots were kept at a greenhouse temperature of 27°C.
After 4 weeks, the lettuce roots were examined for infestation with nematodes (root knots), and the degree of effectiveness of the active compound was determined as a percentage. The degree of effectiveness was 100$ when infestation was completely avoided; it was 0$ when the infestation was exactly the same as in the case of the control plants in untreated soil which had been infested in the same manner.
The active compounds, the amounts applied and the results can be seen from the following table: T a b l e E Critical concentration test/nematodes (Meloidogyne incognita) Active compound Degree of effectiveness in io when using amounts of 20 ppm (C) 0 (D) 0 (E) 0 (2) 100 (7) 100 ( 1 ) 100 The process of this invention is illustrated by the following preparative examples.
Example 1 t 16 g of potassium carbonate and 19 g (0.1 mole) of 0,0-diethylthionophosphoric acid diester chloride were added to a mixture of 24.7 g (0.1 mole) of 1 -phenyl-3-hydroxy-5- [2'-methyl-propen(2)yl-mercapto]-triazole-(l ,2,4) in 200 ml of acetonitrile and after stirring for 4 hours at 80°C the reaction mixture was poured into water and taken up in methylene chloride. The organic phase was washed and dried.
The solvent was then distilled off under reduced pressure.
The residue was subjected to "slight distillation". This gave 28 g (70 of theory) of 0,0-die hyl-0-[l-phenyl-5-(2«-methyl-propen(2)yl-mercapto)-triazol(3)yl]-thionophosphoric 21 acid ester having a refractive index of 1.5593.
The following compounds of the formula could be prepared by methods analogous to that of Example 1.
Example R Rl χ R" Phys Φ -A9-i refr NJ1 2 -0C2H5 "C2¾ s —CH —CH=CH n σ> 3 -OC2H5 0 —CH2—CH=CH2 2 "C2H5 n -CH3 -0CH3 s —CH ~CH=CH 2 n 6 -C2H5 -NH-C^-oso s —CH2_CH=CH2 9 -CH2-CH=CH-CH3 2 "C2¾ -C2H5 s CH3 The hydroxytriazole derivatives (III) used as starting materials could be prepared in, for example, the following manner: 1 09 g of chlorocarbonic acid ethyl ester were added to a suspension of 96 g ( 1 mole) of dried potassium thiocyanate in 5OO ml of acetone, whilst keeping the reaction temperature at 30° to 40°C. The reaction mixture was stirred overnight and a phenylhydrazone solution prepared as follows was then added: 108 g of phenylhydrazine were introduced into 200 ml of acetone at 40° to 45°C and the solution was stirred for three hours and poured into benzene. After drying, the solvent was evaporated off and the residue was combined with the above reaction mixture. After stirring overnight, the solution was filtered, the solvent was evaporated and the residue was boiled for 30 minutes under reflux in a mixture of 800 ml of water and 1 00 ml of hydrochloric acid. After cooling the mixture, the precipitate was filtered off and recrystallised from acetonitrile. 48 g (25 of theory) of 1~phenyl-3-oxo-5-thio-triazolidine-(l ,2,4) of melting point 235°C were obtained. 0.5 mole of a sodium methylate solution was added to 97 g (0.5 mole) of the product obtained as described under (a), in 400 ml of triethylamihe ; thereafter, 46 g of 1-chloro-2-methyl-2-propene were added at 50° to 60°C. The reaction solution was stirred for 3 hours at 70° to 75°C» poured into water and filtered and the residue was dried and recrystallised from1 acetonitrile. 75 g ( 1$ of theory) of 1-phenyl-3-hydroxy-5-(2'-methylpropen(2)ylmercapto]-triazole-( 1 ,2,4) of melting point 141°C were obtained.
The compounds of the following formulas could be prepared analogously: of melting point 137 C, and of melting point 145°C<
Claims (27)
1. 0-Triazolyl-( thiono)-phosphoric(phosphonic) acid esters and ester amides of the general formula in which R is alkyl with 1 to 6 carbon atoms, R1 is alkyl, alk lamino or alkoxy each with 1 to 6 carbon atoms, or phenyl, R" is alkenyl with 3 to 6 carbon atoms, and X is oxygen or sulphur.
2. Compounds according to claim 1 , in which R is straight-chain or branched alkyl with 1 to 5 carbon atoms, R' is straight-chain or branched alkyl, alkoxy or monoalk lamino each with 1 to 5 carbon atoms, or is phenyl, R" is alkenyl with .3 to 5 carbon atoms, and X is sulphur.
3. The compound of the formula
4. The compound of the formula
5. The compound of the formula
6. The compound of the formula
7. The compound of the formula
8. The compounds hereinbefore disclosed in Examples 5» 6 and 8 to 11.
9. A process for the preparation of an O-triazolyl-(thiono) phosphoric(phosphonic) acid ester or ester amide according t any of claims 1 to 8, in which a (thiono)phosphoric(phosphonic) acid ester halide or ester amide halide of the general formula in which X, R and R' have the meanings stated in claim 1 , and Hal is halogen, is reacted with a 1 -phenyl-3-hydroxy-5-alkenylmercapto-triazole derivative of the general formula in which R" has the meaning stated in claim 1 , the compound (III) being reacted as such, in the presence of an acid acceptor, or in the form of an alkali metal salt, alkaline earth metal salt or ammonium salt thereof0
10. A process according to claim 9» in which Hal is chlorine .
11. A process according to claim 9 or 10, in which the reaction is effected in the presence of a diluent or solvent.
12. A process according to claim 9, 10 or 11, in which the reaction is effected at between 0° and 120°C.
13. A process according to claim 12, in which the reaction is effected at from 30° to 85°C.
14. A process according to any of claims 9 to 1 » in which the reaction is effected in the presence, as an acid acceptor, of an alkali metal carbonate, alkali metal alcoholate or an aliphatic, heterocyclic or aromatic amine.
15. A process according to any of claims 9 to 14, in which the halide (II) is one that is hereinbefore specifically mentioned.
16. A process according to an of claims 9 to 15» in which the triazole derivative (ill) is one that is hereinbefore specifically mentioned.
17. A process according to any of claims 9 to 16, in which the reactants are employed in substantially equimolar amounts
18. A process for the preparation of a compound according to claim 1 , substantially as hereinbefore described in Example 1.
19. Compounds according to claim 1, whenever prepared by a process according to any of claims 9 to 18.
20. An insecticidal, acaricidal or nematicidal composition containing as active ingredient a compound according to any of claims 1 to 8 and 19 in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
21. A composition according to claim 20 containing from 0.1 to 95$ of the active compound, by weight.
22. A composition according to claim 21 containing from 0.5 to 90$ of the active compound, by weight.
23. A method of combating insects, acarids or nematodes which comprises applying to the insects, acarids or nematodes, or to a habitat thereof, a compound according to any of claims 1 to 8 and 19 alone or in the form of a composition containing as active ingredient a compound ' according to any of claims 1 to 8 and 19 in admixture with a diluent or carrier.
24. A method according to claim 23 in which a composition is used containing from 0.0001 to 10 of the active compound, by weight.
25. A method according to claim 24 in which a composition is used containing from 0.01 to 1% of the active compound, by weight.
26. A method according to any of claims 23 to 25 in which the active compound is one of those hereinbefore mentioned in any of Examples A to E,
27. Crops protected from damage by insects, acarids or nematodes by being grown in areas in which immediately prior to and/or during the time of the growing a compound according to any of claims 1 to 8 and 19 was applied alone or in admixture with a diluent or carrier.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2419623A DE2419623A1 (en) | 1974-04-24 | 1974-04-24 | 0-TRIAZOLYL- (THIONO) -PHOSPHORUS (PHOSPHONE) ACID ESTER OR. -ESTERAMIDE, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDE, ACARICIDE AND NEMATICIDE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL47131A0 IL47131A0 (en) | 1975-06-25 |
| IL47131A true IL47131A (en) | 1977-11-30 |
Family
ID=5913715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL7547131A IL47131A (en) | 1974-04-24 | 1975-04-21 | 1,2,4-triazolyl phosphoric thionophosphoric phosphonic and thionophosphonic acid esters and ester amides their preparation and their use as insecticides acaricides and nematicides |
Country Status (21)
| Country | Link |
|---|---|
| JP (1) | JPS50148360A (en) |
| AT (1) | AT330800B (en) |
| BE (1) | BE828162A (en) |
| BR (1) | BR7502459A (en) |
| CH (1) | CH576987A5 (en) |
| DD (1) | DD122319A5 (en) |
| DE (1) | DE2419623A1 (en) |
| DK (1) | DK138231C (en) |
| ES (1) | ES436876A1 (en) |
| FR (1) | FR2268810B1 (en) |
| GB (1) | GB1454490A (en) |
| HU (1) | HU171548B (en) |
| IE (1) | IE41334B1 (en) |
| IL (1) | IL47131A (en) |
| LU (1) | LU72336A1 (en) |
| NL (1) | NL7504712A (en) |
| PL (1) | PL93325B1 (en) |
| RO (1) | RO66670A (en) |
| SU (1) | SU673142A3 (en) |
| TR (1) | TR18171A (en) |
| ZA (1) | ZA752618B (en) |
-
1974
- 1974-04-24 DE DE2419623A patent/DE2419623A1/en active Pending
-
1975
- 1975-04-10 SU SU752121990A patent/SU673142A3/en active
- 1975-04-15 GB GB1543575A patent/GB1454490A/en not_active Expired
- 1975-04-21 BE BE155591A patent/BE828162A/en unknown
- 1975-04-21 CH CH506875A patent/CH576987A5/xx not_active IP Right Cessation
- 1975-04-21 IL IL7547131A patent/IL47131A/en unknown
- 1975-04-21 NL NL7504712A patent/NL7504712A/en not_active Application Discontinuation
- 1975-04-22 AT AT306875A patent/AT330800B/en not_active IP Right Cessation
- 1975-04-22 LU LU72336A patent/LU72336A1/xx unknown
- 1975-04-22 RO RO7582045A patent/RO66670A/en unknown
- 1975-04-22 TR TR18171A patent/TR18171A/en unknown
- 1975-04-22 DD DD185603A patent/DD122319A5/xx unknown
- 1975-04-23 BR BR3126/75D patent/BR7502459A/en unknown
- 1975-04-23 JP JP50048729A patent/JPS50148360A/ja active Pending
- 1975-04-23 ES ES436876A patent/ES436876A1/en not_active Expired
- 1975-04-23 PL PL1975179886A patent/PL93325B1/pl unknown
- 1975-04-23 IE IE912/75A patent/IE41334B1/en unknown
- 1975-04-23 ZA ZA00752618A patent/ZA752618B/en unknown
- 1975-04-23 DK DK174875A patent/DK138231C/en active
- 1975-04-24 FR FR7512822A patent/FR2268810B1/fr not_active Expired
- 1975-04-24 HU HU75BA00003255A patent/HU171548B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL7504712A (en) | 1975-10-28 |
| PL93325B1 (en) | 1977-05-30 |
| ZA752618B (en) | 1976-04-28 |
| SU673142A3 (en) | 1979-07-05 |
| DK138231C (en) | 1979-01-15 |
| LU72336A1 (en) | 1976-03-17 |
| CH576987A5 (en) | 1976-06-30 |
| FR2268810B1 (en) | 1978-10-13 |
| ATA306875A (en) | 1975-10-15 |
| DD122319A5 (en) | 1976-10-05 |
| HU171548B (en) | 1978-02-28 |
| AT330800B (en) | 1976-07-26 |
| ES436876A1 (en) | 1976-12-01 |
| DK138231B (en) | 1978-07-31 |
| DK174875A (en) | 1975-10-25 |
| FR2268810A1 (en) | 1975-11-21 |
| DE2419623A1 (en) | 1975-11-06 |
| GB1454490A (en) | 1976-11-03 |
| BE828162A (en) | 1975-10-21 |
| AU7978775A (en) | 1976-10-07 |
| IL47131A0 (en) | 1975-06-25 |
| IE41334L (en) | 1975-10-24 |
| JPS50148360A (en) | 1975-11-27 |
| IE41334B1 (en) | 1979-12-05 |
| RO66670A (en) | 1981-07-30 |
| BR7502459A (en) | 1976-03-09 |
| TR18171A (en) | 1976-11-01 |
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