IL48076A - Thiolphosphoric acid esters their preparation and use in insecticidal and acaricidal compositions - Google Patents

Thiolphosphoric acid esters their preparation and use in insecticidal and acaricidal compositions

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Publication number
IL48076A
IL48076A IL48076A IL4807673A IL48076A IL 48076 A IL48076 A IL 48076A IL 48076 A IL48076 A IL 48076A IL 4807673 A IL4807673 A IL 4807673A IL 48076 A IL48076 A IL 48076A
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IL
Israel
Prior art keywords
compound
formula
methyl
dimethyl
methylcarbamate
Prior art date
Application number
IL48076A
Original Assignee
Ciba Geigy Ag
Priority date (The priority date 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 date listed.)
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Publication date
Priority claimed from CH859472A external-priority patent/CH572708A5/en
Priority claimed from CH642873A external-priority patent/CH581434A5/en
Application filed by Ciba Geigy Ag filed Critical Ciba Geigy Ag
Publication of IL48076A publication Critical patent/IL48076A/en

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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
    • A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds

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  • 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)

Description

The present invention relates to thiolphos- phoric acid esters, processes for their manufacture, and to their use in pest control.
The thiolphosphoric acid esters have the general formula wherein represents a methyl or ethyl group, I , represents an i-butyl, sec. -butyl or n-pentyl group, and represents a hydrogen, chlorine or bromine atom or a methyl group .
Preferred compounds on account of their action are those of the formula I, wherein represents isobutyl or sec butyl.
A further particularly preferred group of compounds is that of the general formula o wherein R represents isobutyl, or sec. butyl, Dialkyl-thiolphosphoric acid esters related 'Λ to those of the present invention and including alkylthio and alkoxy moieties of differing chain length are known: see for example U.S. Patent No. 3,742,094. In accordance with the prior art proposals, however, the alkoxy moiety is longer than the alkylthio moiety. In accordance with the present invention it has now surprisingly been found that by reversing this situation, i.e. by producing analogues in which the alkoxy moiety contains 1 or 2 carboi atoms and the alkylthio moiety 3 and more carbon atoms , compounds exhibiting unexpectedly and greatly superior insecticidal properties are obtained. This superiority can readily be demonstrated in comparative tests employing for example, the insect species Spodoptera littoralis and Leptinotarsa decemlineata (cf . Example 6 herein) .
The compounds of the formula I can be manufactured by the following methods which are known per se: In the formulae II, III and IV, R^, R2, and R3 have the meanings given for the formula I and Me represents an alkali metal, in paricular sodium or potassium, or an ammonium group, e.g. the group (R )¾-NH, wherein ' In the formulae II, Ilia, Illb, V, and VI, R^, and Ej have the meanings given for the formula I and Me represents an alkali metal, in particular sodium + or potassium, or represents the group (¾ )o~ H, wherein -J represents hydrogen or alkyl.
Suitable acid acceptors are: tertiary amines, e.g. trialkylamines , pyridine, dialkyl anilines; inorganic bases, e.g. hydrides, hydroxides; carbonates and bicarbonates of alkali metal and alkaline earth metals. It is sometimes necessary to use catalysts in the reactions, e.g. copper or opper chloride. Processes la and lb, 2, 3a and 3b, are carried out at a reaction temperature between 0° and 130°C, at normal pressure, and in solvents or diluents.
Suitable solvents or diluents are for example: ether and ethereal compounds, e.g. diethyl ether, di-propyl ether, dioxan, tetrahydrofuran; amides, e.g. N,N-dialkylated carboxylic acid amides; aliphatic, aromatic, and halogenated hydrocarbons, in particular benzene, to- J ί luene, xylene, chloroform, chlorobenzene ; nitriles, e.g. i acetonitrile; dimethyl sulphoxide; ketones, e.g. acetone, j I methyl ethyl ketone; water (except process 2) . Ethanol is j also suitable for processes 3a and 3b.
The starting materials of the formulate II, V, VI, and XIII can be manufactured by methods analogous ! to known ones. j The compounds of the formula I can be used for combating the most diverse kinds of animal and plant pests. Above all, they show evidence of good activity against insects and representatives of the order Acarina. They can therefore be used against all development stages, e.g. eSSs, larvae, pupae, nymphs, and adults, of insects and representatives of the order Acarina, for example against insects of the families: Teltigonidae, Gryllidae, Gryllotalpidae, Blattidae, Peduviidae, Phyrrhocoriae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae , Scarabaeidae , Dermestidae, Coccinellidae, Tenebrionidae , Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymatriidae, Pyralidae, Culcidae, Tipulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Puli- cidae, as well as Acarida of the families Ixodidae, Argasidae, Tetranychidae, and Dermanysidae.
Compared with the analogous compounds of the prior art, the compounds of the formula I display in particular a surprisingly improved activity against eating insects and also against spider mites.
The insecticidal or acaricidal activity can be substantially broadened and adapted to given circumstances by addition of other insecticides and/ or acaricides.
Organic phosphorus compounds Bis-0,0-diethylphosphoric acid anhydride (TEPP) Dimethyl- (2,2 ,2-trichloro-l-hydroxyethyl)-phosphonate (TRICHLORFON) l,2-dibromo-2,2-dichloroethyldimethylphosphate (NALED) 2,2-dichlorovinyldimethylphosphate (DICHLORVOS) 2-methoxyca bamy1-1-methyl inyIdi ethylphosphate (MEVI PHOS) Dimethyl-l-methyl-2-(methylcarbamoyl>vinylphosphate cis I (MONOCROTOPHOS) 3- (dimethoxyphosphinyloxy) -Ν,Ν-dimethyl-cis-crotonamide ! (DICROTOPHOS) ·,. | 2-chloro-2-diethylcarbamoyl-l-methylvinyldimethylphosphate (PHOSPHAMIDON) O,0-diethyl-0(or S) -2- (ethylthio) -ethylthiophosphate (DEMET N) S-ethylthxoethyl-0,0-dimethyl-dithiophosphate (THIOMETON) I ! 0,0-diethy1-S-ethyImercaptomethyIdithiophosphate (PHORATE) ! 0,0-diethyl-S-2-(ethylthio)ethyldithiophosphate (DISULFOTON) - - 0,0-dimethyl-S-2- (ethylsulphinyl)ethylthiophosphate (OXYDEMETON METHYL) 0, 0-dimethy1-S- (1,2 -dicarbethoxyethyldithiophosphate (MAIATHION) 0,0,0,0-1etraethy1-S , S 1 -meth lene-bis-dithiophosphate (ETHION) O-ethyl-S , S-dipropyldithiophosphate 0,0-dimethyl-S- (N-meth 1-N-formylcarbamoylme hyl)-d hiophosphate (F0RM0THI0N) 0,0-dimethy1-S- ( -methylearbamoylmethyl)-dithiophosphate (pIMETHOATE) 0,0-dimethyl-O-p-nitrophenylthiophosphate (PARATHIO -METHYL) 0,0-diethyl-O-p-nitrophenylthiophosphate (PARATHION) 0-ethyl-O-p-nitrophenylphenylthiophosphate (EPN) 0,0-dimethy1-0- (4-nitro-m-toly1) -thiophosphate (FENITROTHIO ) j 0,0-dimethyl-0-2,4,5-trichlorophenylthiophosphate (RONNEL) i ! 0-ethyl-0-2,4,5-trichlorophenylethylthiophosphate (TRICHLORO-- NATE) 0,0-dimethyl-0-2 ,5-dichloro-4-bromophenylthiophosphate (BROMOPHOS) - 1 0,0-dimethyl-O- (2,5-dichloro-4-iodophenyl) -thiophosphate (JODOFENPHOS) j i 4-tert.butyl-2-chlorophenyl-N-methyl-0-methylamidophosphate ' (CRUFOMATE) j j 0,0-dimethyl-0-(3-methy1-4-methylmercaptopheny1) -thiophosphate (FENTHIOM) Isopropylaminq-O-ethyl-O- (4-methylmercapto-3-methylphenyl) -phosphate O,0-diethyl-0-p-(methylsulphinyl)phenyl-thiophosphate (FENSULFOTHION) O-p-(dimethylsulphamido) -phenyl-0,0-dimethylthiophosphate (FAMPHUR) ·' · Ο,Ο,Ο' ,0' -tetramethyl-0,0' -thiodi-p-phenylenethiophosphate 0-ethyl-S-pheny1-ethy1dithiophospha e 0,0-dimethyl-0- (a-methylbenzyl-3-hydroxycrotony1) hosphate 2-chloro-l- (2 ,4-dichlorophenyl)vinyl-diethylphosphate (CHLORFE VINPHOS) 1-chloro-l- (2 ,4,5-trichlorophenyl)vinyl-dimethylphosphate 0-[2-chloro-l-(2,5-dichlorophenyl) ]vinyl-0,0-diethylthio-phosphate PhenyIglyoxylonitriloxime-0,0-diethylthiophosphate (PHOXIM) 0,0-diethyl-O- (3-chloro-4-methyl-2-oxo-2-H-l-benzopyrari-7-yl) *■ thiophos hate (COUMAPHOS) 2,3-p-dioxandithiol-S,S-bis(0,0-diethyldithiophosphate) (DIOXATHION) - [(6-chloro-2-oxo-3-benzoxazolinyl)Tnethyl]0,0-die hyldithio-phosphate (PHOSALONE) 2- (diethoxyphosphinylimi.no) -1, 3-dithiolane 0,0-dimethyl-S-[2-methoxy-l,3,4-thiadiazol-5-(4H)-onyl-(4)-methyl ]dithiophosphate 0,0-dimethyl-S-phthalimidomethyl-dithiophosphate (IMIDAN) 0,0-diethyl-O- (3,5, 6-trichloro-2-py idyl)thiophosphate 0,0-diethyl-0-2-pyrazinylthiophosphate (THIONAZIN) 0,0-diethyl-O- (2-isopropyl-4-methyl-6-pyrimidyl) hiophosphate (DIAZINON) 0,0-diethyl-O- (2-quinoxalyl)thiophosphate 0,0-dime hy1-S- (4-oxo-1,2,3-benzotriazin-3(4H) -ylmethyl)-dithiophosphate (AZINPHOSMETHYL) 0,0-diethyl-S-(4-oxo-l,2, 3-benzotriazin-3(4H) -ylmethyl)-dithiophosphate (AZINPHOSETHYL) S- I (4, 6-diamino-s-triazin-2-yl)methyl]-0,0-dimethyldithio-phosphate (MENAZON) 0,0-diinethyl-0-(3-chloro-4-nitrophe.nyl)thiophosphate (CHLORTHION) O,0-dimethyl-0(or S) -2- (ethylthioethyl)thiophosphate (DEMETON-S-METHYL) 'ί 2-(0,0-dimethyl-phosphoryl-thiomethyl)-5-methoxy-pyrone- i 4-3,4-dichlorobenzyl-triphenylphosphoniumchloride 0,0-diethy1-S- (2,5-dichlorophenylthiomethyl)dithiophosphate (PHENKAPTON) ' . \ 0,0-diethyl-O- (4-methy1-cumariny1-7) -thiophosphate (POTASA ) -amino-bis (dimethylamido)phosphiny1-3-phen l-1,2,4-triazole . i (TRIAMIPHOS) | N-methyl-5-(0,0-dimethylthiolphosphoryl)-3-thiavaleramide j AMIDOTHION) 0,0-diethyl-O- [2-dimethylamino-4-methylpyrimidyl- (6) ]-thiophospha e (DIOCTHYL) - - 0,0-dimethyl-S- (methylcarbamoylmethyl) -thiophosphate (OMETHOATE f^ ', O-ethyl-0- (8-quinolinyl) -phenylthiophosphonate (OXINOTHIOPHOS) O-methyl-S-methyl-amidothiophosphate (MONITOR) O-methyl-O- (2 , 5-dichloro-4-bromophenyl) -benzothiophosphate (PHOSVEL) Ο,Ο,Ο,Ο-tetrapropyldithiophosphate 3- (dimethoxyphosphinyloxy) -N-methy1-N-methoxy-cis-c otonamide 0,0-dimethyl-S- (N-ethylcarbamoylmethyl)dithiophosphate (ETHOATE-METHYL) 0,0-diethyl-S- (N-isopropylcarbamoylmethy1) -dithiophosphate (PROTHOATE) S-N-(l-cyano-l-methylethyl)carbamoylmethyldiethylthiolphosphate (CYANTHOATE) S-(2-acetamidoethyl)-0,0-dimethyldithiophosphate Hexameth lphosphoric acid triamide (HEMPA) 0,0-dimethyl-O- (2-chloro-4-nitrophenyl)thiophosphate ; (DIGAPTHON) 0,0-dimethy1-0-p-cyanophenyl thiophosphate (CYANOX) 0-ethyl-O-p-cyanophenylthiophosphonate j 0,0-diethyl-0-2,4-dichlorophenylthiophosphate (DICHLORFENTHION) 0-2, -dichlorophenyl-O-methylisopropylamidothiophosphate · 0,0-diethyl-0-2 ,5-dichloro-4-bromophenylthiophosphate j (BR0M0PH0S-ETHYL) i dimethyl-p- (methylthio)phenylphosphate j 0,0-dimethyl-O-p-sulphamidophenylthiophosphate 0- [p- (p-chlorophenyl)-azophenyl ]0,0-dimethylthiophosphate (AZOTHOATE) O-ethyl-S-4-chlorophenyl-e hyldithiophosphate O-isobutyl-S-p-chlorophenyl-ethyldithiophosphate 0,0*dimethyl-S-p-chloropheiiylthiophosphate 0,0-dimethy1-S- (p-chloropheiiylthioinethyl)dithiophosphate 0,0-diethyl-p-chlorophenylmercaptomethy1-dithiophosphate (CARBOPHENOTHIO ) 0,0-diethy1-S-p-chlorophenylthiomethy1-thiophosphate 0,0-dimethyl-S- (carbethoxy-phenyl ethyl)dithiophosphate (PHENTHOATE) 0,0-diethyl-S- (carbofluorethoxy-phenylmethyl) -dithiophospha 0,0-dimethyl-S-carboisopropoxy-phenylmethyl) -dithiophospha 0,0-diethy1-7-hydroxy-3,4-tetramethylene-coumarinyl-thiopho phate (COUMITHOATE) 2-methoxy-4-H-1,3,2-benzodioxaphosphorin-2-sulphide 0,0-diethyl-O- (5-phenyl-3-isooxazolyl)thiophosphate 2- (diethoxyphosphiny1imino) - -methy1-1,3-dith olane tris-(2- ethyl-l-aziridinyl)-phosphine oxide (METEPA) S- (2-chloro-l-phthalimidoethy1)-0,0-diethyldithiophosphate N-hydroxynaphthalimido-diethylphosphate dimethyl-3,5, 6-trichloro-2-pyridylphosphate 0,0-dimethyl-0- (3,5, 6-trichloro-2-pyridyl)thiophosphate S-2-(ethylsulphonyl)ethyl dimethy1thioIphosphate (DIOXYDEMETON-S-METHYL) diethyl-S-2-(ethylsulphinyl)ethyl dithiophosphate (OXIDISULFOTON) bis-0,0-diethylthiophosphoric acid anhydride (SULFOTEP) dimethyl-l,3-di(carbomethoxy)-l-propen-2-yl-phosphate dimethyl- (2,2 ,2-trichloro-l-butyroyloxyethyl)phosphate (BUTONATE) 0<0-dimethyl-0-(2)2-dichloro-l-inethoxy-vinyl)phosphate bis- (dimethylamido)fluorphosphate (DIMEFOX) 3, 4-dichlorobeizyl-triphenylphosphoniumchloride dimethyl-N-methoxymethylcarbamoyltnethyl-dithiophosphate (FORMOCARBAM) 0,0-diethyl-O- (2 ,2-dichloro-l-chloroethoxyvinyl) -phosphate 0,0-dimethyl-O- (2 ,2-dichloro-l-chloroethoxyvinyl) -phosphate 0-ethy1-S ,S-diphenyIdithiolphosphate O-ethyl-S-benzyl-phenyldithiophosphonate i 0,0-diethy1-S-benzyl-thiolphosphate ; 0,0-dimethy1-S- (4-chlorophenylthiometiny1)dithiophosphate (METHYLCARBOPHE OTHION) 0,0-dimethyl-S- (ethylthiomethyl)dithiophosphate. 1 diisopropylaminofluorophosphate (MIPAFQX) 0,0-dimethyl-S- (morpholinylcarbamoylmethy1)dithiophosphate | (MORPHOTHION) bismethylamido- henylphospha e 0,0-dimethyl-S- (benzenesulphonyl)dithiophosphate 0,0-dimethyl-(S and 0) -ethylsulphinylethylthiophosphate 0,0-dieiu 1-0-4- ίtropheny1p dsp.bεte triet oxy-isoprop'oxy-bis (thiophosphiny1)disulphide 2-methoxy-4H-1,''3„2 -ber.Kodioxaphosphorin-2-oxide actamethyIpyrophcsphoraird.de -(.SGHRADAN) bis- (divnethoxythiophosphinylsulphido) -phen lmethane Ν,Ν,Ν' ,Ν'* -tetratnethyldiaiiiiclofluorophosphate (3)IMEF0X) 0-pheny1-0-p-.nitropheny1-methanethiophosphonate (COLS?) 0--methy1-0-(2-ch1oro-4-1er .buty1-pheny1) -N-methylamidothio- phosphate ( ARLENE) 0 0-ethyl-0-(2 4-dichlorophenyl)-phe1ylthiophosphohata 0,0-d ethy1-0- -methylmercapto~3,5-diit.e hy1pheny1) - h ophos- . phate 4/4' -bis-(0-s"©-dime hylthlopho.sphoryloxy) -diphe/ayl disulphide · "0,0.-di-{'&-chloroethyl)-0~ (3-chlOrO"4-raethyl-coUvaa in l-7)-5 phosphate S- (l- iv£halItni oethy-1)-O^0-diethyldi-thiophospba.te ■ '0»0-dimel¾yl-0-(3-chloro- -diethylsulphamylp'heriyl)-thiophosp'hai:e 0-.methyl-0- (2~carbisopropoxyphenyl) -amidothiophospha e • 5-(0,0-d'irae'th lpbGsphoryl) -δ-chlor -bicyclo(3,2,0) -heptaoiene(1, 5) G 0-raethy1-0- (2-i-proρo yearbon 1-1-me hyIvin 1) «ethyl&miάo- thiophos.p'hate♦ ' itrcphenols and derivatives 4„6«-discii ro-δ-methyiphefto1p sodium salt [Dihitrccres lj dinitrob-titylphenoi- (2,,21 s2i:) -triethanolamine sale 3 -2~-cycl hexyl-4s 5-dinitropiv:nyl [Din¾x] 2-1-methylheptyl) -4, 6-dinitrophenyl-crotonate [Dinocap ] 2-sec.butyl-4, 6-dinitrophenyl-3-methyl-butenoate [Binapacryl] 2-sec.butyl-4, 6-dinitrophenyl-cyclopropionate 2-sec.butyl-4, 6-dinitrophenylisopropylcarbonate iDinobuton] Miscellaneous pyrethrinJI pyretin*in II 3-allyl-2-methyl-4-oxo-2-cyclopentan-l-yl-chrysanthemumate (Allet in) 6-chloropiperonyl-chrysanthemumate (Barthrin) 2 ,4-dime hylbenzyl-chrysanthemumate (Dimethrin) 2 , 3,4, 5-tetrahydrophthalimidomethylchrysanthemumate 4-chlorobenzyl-4-chlorophenylsulphide [Chlorobensid] 6-methyl-2-oxo~l, 3-dithiolo- [4, 5-b ]-quinoxaline (Quino- i methionate) (I) -3- (2-furfuryl)-2-methyl-4-oxocyclopent-2-enyl(l)- (cis+ i trans) -chrysanthemum-monocarboxylate [Furethrin] ! 2-pivaloyl-indane-l,3-dione [Pindon] 4-chlorobenzyl-4-fluorophenyl-sulphide [Fluorobenside ] ; 5, 6-dichloro-1-phenoxycarbamy1-2-t ifluoromethyl-benzimidazble [Fenozaflor j I p-chlbrophenyl-p-chlorobenzenesulphonate [Ovex] p-chlorophenyl-benzenesulphonate [Fenson] p-chlorophenyl-2 ,4, 5-trichlorophenylsulphoie [Tetradifon] p-chlorophenyl-2,4, 5-trichlorophei.iyIsulphi.de [Tetrasul] p-chlorobenzyl-p-chlorophe'nylsulphide [Chlorobenside ] 2-thio-l,3-dithiolo-(5,6)-quinoxaline [Thiochinox] prop-2-ynyl- (4-t-butylphenoxy) -cyclohexylsulphite [Propargil] . Forroamidines l-ditnethyl-2- (21 -methyl-4' -chlorophenyl) -formamidine (CHLORPHENA IDIN) l-raethyl-2- (21 -methy1-4' -chlorophenyl) -formamidine l-methyl-2- (2 ' -methyl-4' -bromophenyl) -formamidine 1-methy1-2- (2 ' ,4' -dimethylphenyl) -formamidine 1-n-butyl-l-methyl-2- (2 ' -methyl-4' -chlorophenyl) -formamidine 1-methyl-l- (2 ' -methyl-41 -chloroaniline-methylene) -formamidine 2- (2"-methyl-4"-chlorophenyl-formamidine l-n-butyl-2-(2' -methyl-4' -chlorophenyl-imino) -pyrolidine.
Urea . i . N-2-methyl-4-ch.loropheny.l-N1 ,Ν' -dimethyl-thiourea.
Carbamates | 1-naphthyl-N-methylcarbamate (CARBARYL) ¾ 2-butinyl-4-chlorophenylcarbamate ', 4-dime hylamino-3, 5-xylyl-N-methylcarbamate ' ! · 4-dimethylamino-3-tolyl-N-methylcarbamate (AMINOCARB) 4-methylthio-3, 5-xylyl-N-methylcarbamate (METHIOCARB) j t .3,4,5-trimethylphenyl-N-methylcarbamate I 2-chlorophenyl-N-methylcarbamate (CPMC) -chloro-6-oxo-2-norboraiie-carbonitrile-0- (methylcarbamoyl) oxime 1- (dimethylcarbamoyl-5-met'hyl-3-pyrazolyl-N,N-dimethylcarba mate (DIMETILAN) 2 , 3-dihydro-2 , 2 -dimethyl-7-benzofuranyl-N-methylcarbamate (CARBOFURAN) 2-methyl-2-methylthio-propionaldehyde-0- (methylcarbamoyl) -oxime (ALDICARB) 8-quinaldyl-N-methylcarbamate and its salts methyl-2-isopropyl-4- (me h lcarbamoyloxy)carbanilate m- (1-ethylpropy1) hen l-N-methylcarbamate 3,5-di-tert.butyl-N-methylcarbamate m-(l-methylbutyl)phenyl- -methylcarbama e 2 -isopropylphenyl-N-me hylcarbama e 2-sec .butylphenyl-N-methylcarbama e m-tolyl-N-methylcarbamate 2 , 3-X)'ly1-N-methylcarbamate 3-isopropylphenyl-N-methylcarbamate 3-tert . butylpheny1-N-methylcarbamate 3-sec .butyIpheny1- -methylcarbamate 3-isopropy1-5-methylphenyl-N-methylcarbamate (PROMECARB) 3, 5-diisoprop3»^lpheny1-N-methylcarbama e 2-chloro-5-isopropylphenyl-N-methylcarbamate 2-chloro-4,5-dimethylphenyl-N-me hylcarbamate 2- (l,3-dioxolan-2-yl)phenyl-N-methylcarbamate (DIOXACARB) - (4, 5-dimethyl-l, 3-dioxolan-2-yl) -phenyl-N-methylcarbamate - (1, 3-dioxolan-2-yl)pheiiyl-N,N-dimethylcarbamate - (1, 3-dithiolan-2-yl) - ,N-dimethylcarbamate - (1, 3-dithiolan-2-yl)pheiiyl-N,N-dimethylcarbamate -isopropoxypheny1-N-methylcarbamate (APROCARB) - (2-propinyloxy)phenyl-N-methylcarbamate 3- (2-propinyloxy)phenyl-N-methylcarbamate -dimethylaminopheny1-N-methylcarbama e 2-diallylaminopheny1-N-methylcarbamate 4-diallylamino-3,5-xylyl-N-methylcarbamate (ALLYXICARB) 4-benzothienyl-N-meth lcarbamate 2.3-dihydro-2-me hyl~7-benzofuranyl-N~inethylcarbatnate 3-methyl-l~phenylpyrazol-5~y1- ,Ν-dime hylcarbamate 1-isopropyl-3-methylpyrazol-5-yl-N,N-dimethylcarbamate (ISOIAN) 2-dimethylamino-5 , 6-dimethylpyrimidin-4-yl-N,N-dimethyl- ; carbamate 3-methy1- -dimethylaminomethyleneiminopheny1- -me hy1-carbamate 3.4-dimethylphenyl-N-methylcarbamate 2-cyclopentylpher0.-N-methylcarbamate ' ; 3-dimethylamino-methyleneiminopheny1-N-methylcarbamate (FORMETANATE) and its salts 1-methylthio-ethylimino-N-methylcarbamate (METHOMYL) | 2-methylcarbamoyloximino-1, 3-di hiolane -meth 1-2-meth lcarbamo loximino-1, 3-ox thiolane 2- (l-methoxy-2-propoxy)phenyl-N-methylcarbamate 2- (1-butin-3- 1-oxy) eny1- -methylearbamate l-diTtiethylcarbamyl-l-methyithio-O-methylcarbamyl-formoxime l-(2' -cyanoethylthio) -O-methylcarbamyl-acetaldoxitne 1-methy1 hio-0-ca bam 1-acetaldoxime 0- (3-sec.butylphenyl) -N-phenylthio-N-methylcarbamate 2 ,5-dimethyl-1, 3-dithiolane-2- (O-me hylcarbamyl) -aldoxime) 0-2-diphenyl-N-methylcarbamate 2- (N-methylcarbamyl-oximino) -3-chloro-bicyclo [2.2. l]heptane 2- (N-methylcarbamyl-oximino) -bicyclo [2.2. l]heptane 3-isopropylpbenyl-N-methyl-N-chloroacetal-carbamate 3-isopropylphenyl-N-m hyl-N-methylthiomethyl-carbamate 0-(2,2-dimethyl-4-chloro-2, 3-dihydro-7-benzofuranyl)-N-methyl carbamate 0- (2 ,2 ,4-trimethyl-2 , 3-dihydro-7-benzofuranyl) -N-niethylcarba-mate O-naphthyl-N-me hyl-N-acetal-carbamate 0-5, 6,7 , 8-tetrahydronaphthyl-N-methyl-carbamate 3-isopropyl-4-me hylthio-phenyl-N-methylcarbamate 3, 5-dimethy1-4-methox -pheny1-N-meth lc rbama e 3-me hoxymethoxy-pheny1-N-methylcarbamate 3-allyloxyphenyl-N-methylcarbamate 2-propargyloxymethoxy-pheny1-N-methy1-carbamate 2-a1ly1oxypheny1- -meth 1-carbamate 4-methoxycarbonylamino-3-isopropylphenyl-N-methyl-carbamate 3, 5-dimethy1-4-methoxycarbonylamino-phenyl-N-methy1-carbamai 2 -γ-me hylthiopropylphenyl-N-methy1-carbamate 3- (a-methoxymethyl-2-propehyl) -phenyl-N-methy1-carbamate 2-chloro-5-ter . -butyl-phenyl-N-me hy1-carbamate 4- (iTiethyl-propargylamino-3, 5-xylyl-N-methyl-carbamate 4- (me hyl-Y-chloroallylamiiio) -3, 5-xylyl-N-methyl-carbamate 4- (methyΙ-β-chloroallylamino) -3,5-xylyl-N-methyl-carbamate 1- (B -ethoxyca bonylethy1) -3-methy1~5 -pyrazoly1-N, -dimethy1 carbama e 3- methyl-4- (dimethylamino-methylmercapto-methyleneimino) -pheny1-N-methy1-carbamate 1, 3-bis (carbamoylthio) -2- (Ν,Ν-dimethylamino) -propanehydro-chlbride ,5-dimethylhydroresorcinoldimethylcarbamate 2- [ethyl-propargylamino ]-phenyl-N-methylcarbamate ί 2- [m thyl-propargylamino J -phenyl-N-methylcarbamate j 4- [dipropargylamino ]-3-tolyl-N-methylcarbamate 4- [dip opa ylamino ]-3 , 5 -xyly1- -methylcarbamate 2- [allyl-isopropylamino ] -phenyl-N-me hylcarbamate 3- [allyl-isopropylamino ]- henyl-N-methylcarbamate ! Chlorinated Hydrocarbons ■ Ύ-hexachlorocyclohexane [GAMMEXANE j LINDAN; ϊ HCH] , ' 1,2,4,5, 6,7,8, 8-octachloro-3a,4, 7, 7a -tetrahydro-4,7-methylene indane [CHLORDAN] 1,4,5, 6, 7, 8,8-heptachloro-3a,4, 7,7a-tetrahydro-4, 7- methylene indane [HEPTACHLOR] 1, 2 , 3 ,4, 10, 10-hexachloro-1, 4,4cc , 5 , 8 , 8a-hexahydro-endo-1,4-exo-5,8-dimethanonaphthalene [ALDRIN] 1 ,2 , 3, 4, 10, 10-hexachloro-6, 7-epoxy-1, 4,4a , 5 , 6, 7 , 8, 8a-octa-hydro-exo-1, -endo-5 , 8-dimethanonapYthalene [DIFLORIN ] 1 »2 , 3, 4, 10, lO-hexachloro-5 , 7-epoxy-1, 4, 4a ,5,6,7,8, 8a-octa-hydro-endo-endo-5,8-dimethanonaphthalene [ENDRIN] The compounds of the formula I may be used as pure active substance or together with suitable carriers and/or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technique such, for example, as solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.
For application, the compounds of the formula I ma be processed to dusts, emulsion concentrates, granules, dis- persions, sprays * to solutions, or suspensions, in the conventional formulation which is commonly employed in appli- j cation technology. Mention may also be made of cattle dips ; and spray races, in which aqueous preparations are used. j The agents according to the invention are anufac- < tured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may take, and be used in, the following forms; Solid forms: Dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules.
Liquid forms: a) active substances which are dispersible in water: we table powders, pasts, emulsions; b) solutions.
To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, ; diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feld- : spar and mica), calcium ad magnesium sulphates, magnesium ' oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used singly 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 resulting solution to a granulated material, for example attapulgite, SIC^, granicalcium, bentonite etc. and the evaporating the solvent.
Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/ formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/liter to 600 g/ liter can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.
It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product.
To these mixtures can also be added additives which stabilise the actrve substance and/or non-ionic, anionic and cationic surface active substances, which, for example, improve the adhesion of the active ingredients on plants or - - parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents) . Exam les of suitable adhesives are the following: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrro- lidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also late products.
The water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface-active substance and anti-foam agents and, optionally, solvents.
Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatus until homogeneity is attained. Suitable carriers are, for example, those mentioned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulphonated naphthalene and sulphonated naphtha- . lene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulphonic acid, in addition, alkylaryl . sulphonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols , heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salts of oleoyl methyl tauride, ditertiary acetylene glycols, dialkyl di-lauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.
Suitable anti-foam agents are silicones.
The active substances are mixed, ground, sieved and strained with the additives cited hereinabove, in. such a manner that, the size of the solid particles does not exceed 0.02 to 0.04 U in \-7e able powders, and 0.03 J, in pastes.
To produce emulsifiable concentrates and pastes, dispersing agents such as those cited above, organic solvents, and water are used. Examples of suitable solvents are: alcohols, benzene, xylene, toluene, dimethyl sulphoxide, and mineral oil fractions which boil between 120° and 350°C. The solvents must be' practically odourless, not phytotoxic, and inert to the active substances. · Furthermore , the agents according to the invention can be applied in the form of solutions. For this purpose \ the active substances, or several active substances of the general formula I, are dissolved in suitable organic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils, singly or in admixture with each other, can be used as organic solvents. | The content of active substance in the above described agents is between 0.1% to 95%, in which connection it should be mentioned that, in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.
The active substances of the formula I can, for example, be formulated as follows: Dusts The following substances are used to manufacture a) a 5% and b) a 2% dust: a) 5 parts of active substance 95 parts of talcum ! b) 2 parts of active substance ; 1 part of highly disperse silicic acid 97 parts of talcum.
The active svibstances are mixed with the carriers \ i and ground.
Granules The following substances are used to produce 5% !■ granules : parts of active substance, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol,. 91 parts of kaolin (particle size 0.3 - 0.8 mm).
The active svibstance is mixed with epichlorohydriii and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on kaolin, and the acetone subsequently evaporated in vacuo.
Wettable powder; The following constituents are used for the pre-paration of a) ' a 40%, b) and c) a 25%, and d) a 10% wettable powder : a) 40 parts of active substance, parts of sodium lignin sulphonate, 1 part of sodium dibu yl-naphthalene sulphonate, ; 54 parts of silicic acid. > b) 25 parts of active substance, ' 4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydrox ethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin. ; c) 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, - - 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, « 46 parts of kaolin, d) 10 parts of active substance, 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.
The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.
Emulsifiable concentrates: j The following substances are used to produce a) a j 107, and b) a 257» emulsifiable concentrate: ! a) 10 parts of active substance, ! 3.4 parts of epoxidised vegetable oil, 13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkyl- arylsulphonate calcium saltj 40 parts of dimethylformamide, i - - 43.2 parts of xylene, b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, parts of an alkylarylsulphonate/fatty alcohol polyglycol ether mixture, parts of dimeth lformamide, 57.5 parts of xylene.
From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.
Spray; The following constituents are used to prepare a 57o spray: parts of active substance, 1 part of epichlorohydrin, 94 parts of benzine (boiling limits 160° - 190°C) - - EXAMPLE I The following compounds were prepared by method analogou^ to that described in Example I Israel Patent Specification No. 42383» Compound Physical Data E X AM P L E 2 Insecticidal ingest poison action Tobacco and potato plants were sprayed with a 0.05% aqueous emulsion of the active substance obtained from a 10% emulsifiable concentrate). After the coating had dried, the tobacco plants were populated with Spodoptera littoralis and Heliothis virescens larvae and the potato plants with Colorado potato bettle larvae (Leptinotarsa de-cemlineata) . The test was carried out at 2 °C and 60% relative humidity. In the above test, the compounds according to Example 1 displayed good ingest poison · action against Spodoptera littoralis, Heliothis virescens and Leptinotarsa decemlineata.
E X A M P L E 3 Action against Chilo suppressalis Six rice plants at a time of the variety Caloro were transplanted into plastic pots (diameter at the top « 17 cm) and reared to a height of about 60 cm. Infestation with Chilo suppressalis larvae (L- 3-4 mm long) took place 2 days after the active substance had been applied in granule form to the paddy water (rate of application: 8 kg of active substance per hectare) . Evaluation of the insecticidal action took place 10 days after application of the granules.
The compounds according to Example 1 displayed good action! in the above test against Chilo suppressalis. ' E X AM P L E 4 Action against ticks A) Rhipicephalus bursa Five adult ticks or 50 tick larvae were counted into a glass tube and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from an emulsion series each containing 100, 10, 1 and 0.1 ppm of test substance. The tube was then sealed with a standardised cotton wool plug and placed on its head, so that the active substance emulsion could be adsorbed by the cotton wool. In the case of the adults evaluation took place after 2 weeks, and in tha of the larvae after 2 days. Each test was repeated twice. b) Boophilus microplus Tests were carried out in each case with 20 OP-sensitive ! larvae using an analogous dilution series as in the case of test A. (The resistence refers to the tolerability of Diazinon) . The compounds according to Example 1 displayed good ■ j action in the above test against adults and larvae of Rhipicephalus bursa and sensitive and OP-resistent larvae of Boophilus microplus.
E XAM P L E 5 Action against spider mites Phaseolus vulgaris (dwarf beans) have an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test for the acaricidal action. The mobile stages which have migrated are sprayed with the emulsified test preparations from a chromatography atomiser so that the spray broth does not run off. The number of living and dead larvae, adults and eggs are evaluated after 2 to 7 days under a stereoscopic microscope and the result expressed in j percentages. During the "interim", the treated plants are kept in greenhouse compartments at 25°C.
The compounds according to Example 1 were i active in the above test against eggs, larvae and adults > of Tetranychus urticae. i i COMPARATIVE TEST - EXAMPLE 6 It.
TEST COMPOUNDS (I) A compound according to the present Israeli paten Application,.
(II) CH3 A compound according to U.S. Patent No .3 ' 742 ' 094 (III) A compound according to the present Israeli patent Application (IV) A compound according to U.S. Patent No .31742 ' 0¾ (V) N A compound according to the present Israeli patent , Ap lication t- -.. - 36b - (XII) (XIII) (XIV) (n> A compound according t U.S. Patent No. 3' 742' TEST METHOD Potato plants and cotton plants were sprayed until dripping with a 0.05% aqueous emulsion of the compound under test, the emulsio being prepared from 25% wettable powder.
After drying the potato plants were populated with Colorado pota beetle larvae (Leptinotaraa decemiineafc:a) and the cotton plants with Egytian cotton leaf worm larvae (Spodoptera littoralis).
Assessement was made 24 hours after infestation of the treated plants. The test was conducted at 24°C and 60% relative humidity.

Claims (11)

1. Compounds of the formula I wherein Rj^ represents a methyl or ethyl group, 1*2 represents an i-butyl, sec.-butyl or n-pentyl group, and *' R3 represents a hydrogen, chlorine or bromine atom or a methyl group,
2. , Compounds according to claim 1 wherein Rj^ represents an ethyl group,
3. Compounds according to claim 1 or 2 wherein ¾2 represent an i-butyl or n-pentyl group, and represents a chlorine or bromine atom or a methyl group.
4. The compound of the formula
5. The compound of the formula
6. The compound of the formula
7. compound of the formula - 38 - compound of the formula The compound of the formula The compound of the formula The compound of the formula (1)¾H9S A solid pesticidal composition comprising (i) a compound according to any one of claims 1, 2 and 7 to (ii) a solid extender and optionally (iii) a surfactant. A liquid pesticidal composition comprising (i) a compound according to any one of claims 1, 2 and 7 to (ii) a liquid diluent and (iii) a surfactant. A method of combatting pests of the class Inse.cta or Acarina at a locus, which comprises applying to said locus a compound as claimed in any one of claims "1, 2 and 7 to 11. A method according to claim ,1 wherein the locus comprises growing plants. A method according to claim 14 or claim 15 wherein the pests are insects of the species Spodoptera littoralis or Leptino- tarsa decemlineata . A solid pesticidal composition comprising (i) a compound according to any one of claims 3 or 4 to 6 (ii) a solid extender and optionally (iii) a surfactant. - 40 -
8. A liquid pesticidal composition comprising ¾ (i) a compound according to any one of claims 3 or 4 to 6 (ii) a liquid diluent and (iii) a surfactant.
9. 19. A method of combatting pests of the class Insecta or Acarina at a locus, which comprises applying to said locus a compound as claimed in any one of claims 3 or 4 to 6
10. 20. A method according to claim 19 wherein the locus comprises growing plants .
11. 21. A method according to claim 19 or claim 20 wherein.the pests are insects of the species Spodoptera littoralis or Heliothis virescens. . 43. *
IL48076A 1972-06-08 1973-05-29 Thiolphosphoric acid esters their preparation and use in insecticidal and acaricidal compositions IL48076A (en)

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CH859472A CH572708A5 (en) 1972-06-08 1972-06-08 Cyanophenyl-thiolphosphates - insecticides and acaricides
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IL48076A IL48076A (en) 1972-06-08 1973-05-29 Thiolphosphoric acid esters their preparation and use in insecticidal and acaricidal compositions
IL48076A IL48076A0 (en) 1972-06-08 1975-09-11 New thiolphosphoric acid esters,their preparation and use for combating pests

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DE3039086A1 (en) * 1980-10-16 1982-05-27 Basf Ag, 6700 Ludwigshafen 2-FLUORPHENYL- (DI) THIOPHOSPHORIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING PESTIES

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