IE51602B1 - 4-trifluoromethylphenyl(di)thiophosphates,their preparation and their use in pest control - Google Patents

4-trifluoromethylphenyl(di)thiophosphates,their preparation and their use in pest control

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Publication number
IE51602B1
IE51602B1 IE2271/81A IE227181A IE51602B1 IE 51602 B1 IE51602 B1 IE 51602B1 IE 2271/81 A IE2271/81 A IE 2271/81A IE 227181 A IE227181 A IE 227181A IE 51602 B1 IE51602 B1 IE 51602B1
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trifluoromethylphenyl
thiophosphate
alkyl
carbon atoms
formula
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IE2271/81A
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IE812271L (en
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Basf Ag
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    • 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
    • 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

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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)

Abstract

1. Claims for the Contracting States : BE, CH (LI), DE, FR, GB, IT, LU, NL, SE A 4-trifluoromethylphenyl (di)thiophosphate of the formula I see diagramm : EP0049383,P15,F4 where R**1 is alkyl of 1 to 3 carbon atoms, R**2 is alkyl, haloalkyl, alkoxyalkyl or alkylthioalkyl of 1 to 6 carbon atoms, R**3 , R**4 and R**5 independently of one another are hydrogen, halogen, cyano or alkyl, alkoxy or alkylthio of 1 to 4 carbon atoms and X is oxygen or sulfur. 1. Claims for the Contracting State : AT A pesticide containing inert additives and a 4-trifluoromethylphenyl (di)thiophosphate of the formula I see diagramm : EP0049383,P16,F4 where R**1 is alkyl of 1 to 3 carbon atoms, R**2 is alkyl, haloalkyl, alkoxyalkyl or alkylthioalkyl of 1 to 6 carbon atoms, R**3 , R**4 and R**5 independently of one another are hydrogen, halogen, cyano or alkyl, alkoxy or alkylthio of 1 to 4 carbon atoms and X is oxygen or sulfur.

Description

The present invention relates to 4-trifluoronefchylphenyl (di)thiophospnates, to a process.for their preparation, andto pest control agents which contain these compounds as the active ingredients.
German Laid-Open Application DOS 2,149,312 and U.S. Patent 4,123,526 disclose 0,0-dialkyl 0-(4-trifluoromethylphenyl) thiophosphates and 0,0-dialkyl 0-(3-trifluoromethylphenyl) thiophosphates which are useful for the control of pests such as insects and nematodes.
German Laid-Open Application No. 2,327,377 discloses trifluoromethyl-nitro-phenyl-thio (dithio) phosphates which are useful for pest control.
We have found that 4-trifluoromethylphenyl (di)thiophosphates of the formula I 2 where R is alkyl of 1 to 3 carbon atoms, R is alkyl, haloalkyl, alkoxyalkyl or alkylthioalkyl of 1 to 6 carbon 3 4 5 atoms, R , R and R independently of one another are hydrogen, halogen, cyano or alkyl, alkoxy or alkyl20 thio of 1 to 4 carbon atoms and X is oxygen or sulfur, effectively control pests from' the classes of insects, and nematodes. Their effect is superior to that of the known 0,0-dialkyl 0-(4-trifluoromethylphenyl) thiophosphates of analogous structure. formula I, Ri is alkyl of 1 to 3 carbon atoms, e.g. methyl, ethyl, n-propyl or i-propyl, especially 51603 ethyl, R2 Is alkyl, haloalkyl, alkoxyalkyl or alkylthioalkyl of 1 to 6 carbon atoms, e.g. methyl, ethyl, n-propyl, i-propyl, n-butyl, sec.-butyl, i-butyl, n-pentyl, 1-methyl-n-butyl, 3-methyl-n-pentyl, 2-chloroethyl, 35 chloro-n-propyl, 2-methoxyethyl, 2-ethoxyethyl, 2-isopropoxyethyl, 2-methylthioethyl or 2-ethylthioethyl. The alkyl radical may be cyclic, as in cycloalkyl, of 3 to 6 carbon 3 It ς atome, e.g. cyclopentyl or cyclohexyl. R , R and R', which can be different, are each hydrogen, halogen, e.g. chlorine, 10 bromine or fluorine, or cyano, or alkyl, alkoxy or alkylthio of 1 to 4 carbon atoms, preferably methyl or ethyl.
R2 is preferably alkyl of 3 or 4 carbon atoms, especially n-propyl, sec.-butyl or isobutyl, R^ is preferably halogen, such as chlorine or bromine, preferably in the 2-position, and R and R are preferably hydrogen. 4-Trifluoromethylphenyl (di)thiophosphates of the formula I may be obtained by reacting an O,S-dialkyl phosphate-chloride of the formula II (II) 2 where R , R and X have the above meanings, with a 4-trifluoromethylphenol of the formula III 4 5 where R , R and R have the above meanings, in the presence or absence of an acid-binding agent and in the pre51802 sence or absence of a diluent, or with a salt of a 4-trifluoromethylphenol of the formula III in the presence or absence of a.diluent.
The course of the reaction can be represented by the following equation: r2sz/X?-C1 + R5 The reaction of the phosphate-chloride of the formula II with the phenol of the formula III can be carried out in an organic diluent, such as acetonitrile, toluene or methyl ethyl ketone, or in a two-phase system, such as toluene/water or methylene chloride/water.
Advantageously’, 1-2 moles o.f an acid acceptor are.added per mole of the phenol of the formula III. An excess of about 10% is preferably used. Suitable . acid acceptors are bases, such as alkali metal carbonates, e.g. potassium carbonate, alkali metal hydroxides, e.g. sodium hydroxide, or tertiary amines, e.g. triethylamine. Instead of'using the base and phenol, it is possible to react ’ the phosphatechloride with a salt of the phenol, for example an alkali metal salt, alkaline earth metal salt or substituted or unsubstituted ammonium salt, such as. the sodiun, potassium, calcium or ammonium salt.
The reaction can be carried out within a substantial temperature range, which is generally from 0 to.100°C; preferably.from to 70’C , and is usually allowed to proceed under atmospheric pressure.
The starting substances are conveniently used in equimolar amounts, but an excess of one or other of the reactants can be advantageous in some cases. Preferably, 0.9 to 1.1 moles of phosphate-chloride are used per mole of phenol.
The reaction mixture may be worked up in the conventional manner, for example by adding water and separating the phases. The crude products can be purified by distillation or column chromatography. 0,S-Dialkyl phosphate-chlorides are known, and they can be prepared by known processes (German Laid-Open Application DOS 2,642,982; and J. Org. Chem. 30, (1965) 3217). The 4-trifluoromethylphenols of the formula III can also be prepared by processes which are known from the literature (German Published Application DAS 1,257,784; and J.Am.Chem.Soc.69, (1947) 2346).
The processes below also lead to ccnpounds according to the invention: 4-Trifluoromethylphenyl thiophosphates of the formula Ia can be prepared in an Arbusow reaction between phosphites of the formula IV and sulfenyl chlorides of 2 the formula R SCI in accordance with the' following equa- 51802 The 4-trifluoromethylphenyl thiophosphates of the formula Ia can also be obtained by alkylating thiophosphate ester- salts of the formula V with alkylating agents of the formula R Y: V Ia Furthermore, phosphate dichlorides of the formula VI can be reacted with alcohols and mercaptans of the 1 2 formula R OH or R SH to give compounds of the formula I: 2 3 4 5 In these equations, R , R , R , R , R and X have the above meanings. Me® is a metal cation or a substituted or unsubstituted ammonium ion, and Y is halide, for example iodide, bromide or chloride, or alkyl-sulfate, for example methyl-sulfate.
PREPARATION EXAMPLE 16.7 ml of bromine are added dropwise to 52.4 g of 4-trifluoromethylphenol in 300 ml of methylene chloride at 20°C. The mixture is left to stand for 24 hours after which the solution is colorless. After stripping 51662 off the solvent, 75 g of 2-bromo-4-trifluoromethylphenol 22 are obtained; = 1.4959. 8.3 g of potassium carbonate are added to 14.5 g of the resulting 2-bromo-4-trifluoromethylphenol in 100 ml 5 of acetonitrile, and 11.1 g of O-ethyl 5-propyl thiophosphate-chloride are then added dropwise. The mixture is stirred at 50’C for four hours and then at room temperature for 12 hours.
The solvent is removed on a rotary evaporator, 400 ml of toluene and 100 ml of water are added, the phases are separated, the organic phase is washed with 2N sodium hydroxide solution and then with water and is dried.with sodium sulfate, and the solvent and volatile impurities are stripped off under reduced pressure at 40°C/0.1 mbar. 13.6 g of O-ethyl S-n-propyl 0-(2-bromo-4-trifluoromethylphenyl) thiophosphate are obtained as the 30 residue: = 1.4949.
The following compounds of the formula I can be prepared, for instance, by a process similar to this ex20 ample or by one of the processes described above: CQ I a cm rH ϋ I CM o in ON in 03 e— CO O\ «ST Λ* rH rH rH II 11 II <ο σ\ ο CM QH Qcn Q c c c r4 a o a on —I CM tn in in in on on on on on a a a a a a a a a CM CM CM CM o o o O ϋ o ϋ ϋ o on in M3 e- co ON o rH «1Θ02 J3 in x if X cn X iH X z co cn cn cn \O in 03 σ> σ' o rH CM in tn in (I II It H n in cm cm CM Q CM Q CM Ω CM Q C CCC iH £- rH «Η C rH ϋ CQ & 1 o t o | CQ | o ι x 33 a a a X X CM 1 CM 1 CM 1 m M3 M3 ό rH ϋ I M3 C CQ I M3 EC rH o I uT ϋ Z o X o co 1 rH ϋ cn CM I CM CM c CQ I CM rH SO CQ I I X CM CM O I CM co co co co co co 53 KEKEE EXKXKffi zT j cT cr cT J0 m AAAAAAAAAAAAA in in m in in in in in in in in in m Jin X X X X X X X X X X X X X X CM CM CM CM CM CM CM CM CM CM CM CM CM ϋ O ϋ ϋ O ϋ υ o O υ o O O o CM cn in M3 C- GO σ\ o rH CM cn •=r in pK «Η rH fH »H «Η iH fH CM CM CM CM CM CM cn ί* in cn SC Ll x 2 ϋ cn o o co 1 VO 04 04 1 04 X X X X X X as X X X X X X X X X X X X X X X X s X X cn cn Ll Li X rH rH Li X rH X o X o o I fe Q X I o 1 o I fe I 1 Ol X X X 1 OJ 1 OJ 1 OJ t cn cn OJ 1 OJ OJ cn cn X cc o z co CO co co o o o co co in in n in in tn in in in X X X X X X X X X 04 OJ OJ OJ OJ OJ Ol 04 04 O ϋ ϋ o o o ϋ O Q VO ¢- co o o rH 04 cn XT OJ OJ OJ OJ cn cn cn cn cn co co co t- c* t- ¢- c- Ο- X X X X X Χ cn cn cn cn co cn o o o o o ϋ 1 •H 1 iH .,Η J) Λ •τΗ in in in in in in X X X X X X OJ OJ 04 OJ OJ OJ o o o o o o in VO t— co σ% o cn cn cn cn cn 43· S1602 CJ O in VO 00 Or <=T •ST «—1 rH II II CJ CJ if EC M in στ CJ IO cn cn vo στ o rH Cl in in in • • * • <— rH i-H i-H II II II II m in CJ cn Cl Gt c V CJ Q G rH fc« o 1 VO 1 VO a a a K X O fe I I ί—I ti o ta ft I I I CJ CJ CJ I cn O I cn X EC EC EC a X X cn cn cn cn G EC EC r—f & 03 o O ϋ I m I 1 CJ i CJ 1 cn X 1 CJ 1 CJ CJ X X co r"t ffi στ στ στ στ στ στ στ στ X X X X X X X X JT .a· a· a· a* a* ^Γ o ϋ ο I ϋ I Ο ϋ | ο | ϋ 1 φ 1 ο 1 φ 1 Φ 1 φ 1 φ φ φ Φ φ φ Φ φ φ φ φ co GO CQ 03 β 03 «ο 03 στ στ στ στ στ στ στ X X X X X X X -Τ ΕΓ ^Γ a· a* ο ο ϋ ϋ ϋ I ϋ ο I ι φ φ I φ I φ 1 Φ φ 1 Φ φ φ φ φ Φ φ Φ 00 03 03 03 03 (0 Φ ιη ιη ιη in tn in in in in in in in in u X X X X X X X X X X X X X X CJ 04 CJ CJ CJ CJ CJ CJ CJ Cl CJ Cl CJ c o ο ϋ ϋ ϋ o ϋ O ϋ ϋ o o O o 04 cn a· in vo e- 00 στ O rH CJ cn xr in a· jg· •ar a* a· ET sr in in in in in in in o oo cP in cP in cc 2CQ CQ 1 k£> 1 KO X X X X X X I KO I Ό X X X X X cn X r-l rd o o Q | X x cn X X 1 cn X X X X X m X X X L, cn X rd 24 rd 2- rd 24 Q CQ O o I X 1 O | X I O 1 X I 1 OJ 1 OJ X 1 OJ X X 1 OJ 1 OJ 1 OJ 1 OJ X X Ol OJ X CO CO w co co co co co OJ on ON a\ ON X X X X X xr sr sT ON ON on σ\ σκ ΟΝ σ\ ΟΝ ΟΝ ΟΝ o ϋ ϋ Q X X χ χ χ X X X X X 1 J | 1 I ST ST -a- sr «· ST ST ST ST -=r Ο o o O O o o ο Ο ϋ ϋ ϋ Ο ο o J* Φ o 0 0 I 1 ι 1 1 I I ι ι. | χ co co CO CO vd «Η •Η •Η •Η Η Ή vd vd Η ο ιη ιη ιη ιη ιη ιη ιη ιη ιη ιη ιη ιη ιη ιη ιη χ χ χ X X χ χ χ X X X X X X χ OJ OJ οι Οί Οί Οί Οί οι ΟΙ 0J OJ Οί οι 04 Οί ο ο ο ϋ ϋ ο ϋ ϋ ϋ ϋ ο Ο ο ϋ Ο κ£> C— CO ΟΝ ο rd OJ cn -sr ιη κο C- co ΟΝ ο ιη ιη ιη ιη κθ Κθ κθ κο Κθ κο Κθ κο κθ ΚΟ t* in a .=3a co OS rH το-s ο - ( HO )-0 HO in os .=r oo on nip a o I a cc a a a a a a a a a a a on b rH t- rH rH L. rH rH t. m ϋ r on o a Q O a I O o a < l CM a 1 CM CM 1 on a 1 CM 1 CM cn a CM CM a co co CQ GO CQ CQ 1 CM 1 CM 1 CM CM I CM 1 CM CM CM Z»k CM z*% CM s—* CM CM CM CM Z~* z«s z~k z··. Z*k CM CM CM CM CM CM CM ni CM CM CM CM CM CM a a a a a a a a a a a a a a o o o o o o o o o o o o o o *-z *vZ •ν' s_z S-Z •ν' 1 •ν' 'W'' 1 1 •ν' 1 1 o 1 o 1 o ό 1 o ό 1 o 1 o ό o ό o o o in in in in in in in in cn cn cn nf1 on on a a a a a a a a a a a a a CM CM CM CM CM CM CM CM o o o o o o o o o O o O o O in in in in in in in in in in in US in in in a a a a a a a a a a a a a a a CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM O o o O o o O O O o o o o o o rH CM on •SP m SO t- CO OS o rH CM on js· in t* t- t*· C*· t*- c— t- >- >- co CO CO co co co 81602 in x cn X rM X O ΠΊ OJ 00 ο- vo CO OS O .g- -=r in OJ OJ CM Q CM QCM P fi c c X X X X X X X X X X X X X X X rM rM Ο O X X X 1 cn X X X cn X X X X X X X t, pM L. rM Li rM rM p o a o X o | X o 1 O | X X 1 CM l CM X X 1 CM 1 CM X X CM OJ CM X CM CM OOOO cn co co co o o o o co co co CM 1 CM I CM 1 CM 1 CM 1 CM I CM Z-X z—» z— z-K z—>. CM CM OJ CM OJ CM CM X X X X X X X o o o O O o o s»/ 'w' 1 I 1 CM { CM ( CM 1 CM 1 CM 1 CM I CM X X X X X X X o o o o o o O rM rM rM rM rM rM rM O O O O O O o 'ru I I I I I I r-s OJ cm OJ OJ OJ < | /—·. CM CM CM CM OJ z">> CM z— CM z~s CM X OJ CM X CM CM CM o X X X X X X CM o o o o o o X 1 s_z •XzZ •w o o 1 | I 1 I 1 o o o o o o I Ο- ο- s- t- Ο- e- Ο- 0J Χ χ X X Χ X Χ X cn cn cn cn cn cn cn o o o o o o | © O 1 rH O I 1 Ή tM t Ή 1 •ri •ri 1 •ri Lf\ IT\ in in in in in in X X X X X X X X CM OJ OJ 0J CM CM CM OJ O © © o o Ο O o M3 o- co os o rM CM m CO co co co σ\ OS O' os in in in in in in in X X X X X X X CM CM CM CM CM CM CM © O O O O O O -=r in \O 0— 00 OS o os ON ON On on ON o Ή o o in cn in στ >- in o σ\ o e- in a· in a* • • > rH »H rH rH g N n n in in a· inW(P cya «Ρ cuya OJ αΰ rH fi O CQ I I CM CJ rH fi O X I CJ CJ Cl 1 | I CJ Cl CJ X CJ CJ CJ z~s z"«. o CJ z·*» CJ z*. Cl X™ sP CJ X 1 i X X X ϋ ϋ o cj o o u ϋ s^· Z X t·» >»> y^> 1 1 1 ϋ X 1 1 1 03 03 03 w cn co M w in in in o | cn X bT bT X CJ X CJ X CJ x^ wH ϋ o o o o ϋ o m in in in in in in ΙΠ cn X X X X X X X X o CJ Cl CJ CJ CJ CJ CJ CJ | o Q Q o o o o o fi rH CI cn a· in vo fr— co στ o o O O O o o o O rH rH rH rH rH w rH rH rH The 4-trifluoromethylphenyl (di)thiophosphates of the formula I, and pesticides containing them, are suitable for effectively combating pests from the classes of Insects, arachnids and nematodes. They may be employed for protecting crops, and in the hygiene, stores protection and veterinary sectors as pesticides.
Examples of injurious insects from the Lepidoptera order are Plutella maculipennis, Leucoptera coffeella, Hyponomeuta malinellus, Argyresthla conjugella, Sitotroga cerealella, Phthorimaea operculella, Capua reticulana, Sparganothis pilleriana, Cacoecia murinana, Tortrix vlridana, Clysia ambiguella, Evetria buoliana, Polychrosis botrana, Cydia pomonella, Laspeyresia molesta, Laspeyresia funebrana, Ostrlnla nubilalis, Loxostege sticticalis, Ephestia kuehniella, Chilo suppressalis, Galleria mellonella, Malacosoma neustria, Dendrolimus plni, Thaumatopoea pityocampa, Phalera bucephala, Cheimatobia brumata, Hibernia defoliarla, Bupalus piniarus, Hyphantria cunea, Agrotls segetum, Agrotis ypsilon, Barathra brassicae, Cirphis unipuncta, Prodenia lltura, Laphygma exigua, Panolis flammea, Earias lnsulana, Plusia gamma, Alabama argillacea, Lymantria dispar., Lymantria monocha, Pieris brassicae, and Aporia crataegi; examples from the Coleoptera order are Blitophaga undata, Melanotus communis, Limonlus californicus, Agriotes lineatus, Agricotes obscurus, Agrilus sinuatus, Meligethes aeneus, Atomarla linearis, Epilachna varlvestris, Phyllopertha horticola, Popillia japonica, Melolontha melolontha, Melolontha hippocastani, Amphimal· lus solstitialis, Crioceris asparagi, Lerna melanopus, Leptinotarsa decemllneata, Phaedon cochleariae, Phyllotreta nemorum, Chaetocnema tibialis, Phylloides chrysocephala, Diabrotica 12-punctata, Cassida nebulosa, Bruchus lentis, Bruchus rufimanus, Bruchus pisorura, Sltona lineatus, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Hylobies abietis, Byctlscus betulae, Anthonomus pomorum, Anthonomus grandis, Ceuthorrhynchus assimllis, Ceuthorrhynchus napi, Sitophilus granaria, Anisandrus dispar, Ips typographus, and Blastophagus piniperda; examples from the Diptera order are Lycoria pectoralis, Mayetiola destructor, Dasyneura brassicae, Contarinia tritici, Haplodiplosis equestris, Tlpula paludosa, Tlpula oleracea, Dacus cucurbltae, Dacus oleae, Ceratitis capitata, Rhagoletis cerasi, Rhagoletis pomonella, Anastrepha ludens, Oscinella frit, Phorbia coarctata, Phorbia antiqua, Phorbia brassicae, Pegomya hyoscyami, Anopheles maculipennls, Culex pipiens, Aedes aegyptl, Aedes vexans, Tabanus bovinus, Tipula paludosa, Musca domestica, Fannla canicularis, Muscina stabulans, Glossina morsltans, Oestrus ocis, Chrysomya macellaria, Chrysomya hominivorax, Lucilia cuprina, Lucilla sericata, and Hypoderma lineata; examples from the Hymenoptera order are Athalia rosae, Haplocampa minuta, Monoraorium pharaonis, Solenopsis geminata, and Atta sexdens; examples from the Heteroptera order are Nezara viridula, Eurygaster integriceps, Blissus leucopterus, Dysdercus cingulatus, Dysdercus intermedlus, Piesma quadrata, and Lygus pratensis; examples from the Homoptera order are Perkinsiella sacchari25 cida, Nilaparvata lugens, Empoasca fabae, Psylla mail, Psylla piri, Trialeurodes vaporariorum, Aphis fabae, Aphis poml, Aphis sambuci, Aphldula nasturtil, Cerosipha gossypli, Sappaphis mall, Sappaphis mala, Dysphls radlcola, Brachycaudus cardul, Brevicoryne brassicae, Phorodon humuli, Rhopalomyzus ascalonicus, Myzodes persicae, Myzus cerasi, Dysaulacorthum pseudoaolani, Acyrthoslphon onobrychis, Macrosiphon rosae, Megoura viclae, Schizoneura lanuginosa, Pemphigus bursarius, Dreyfusia nordmannianae, Dreyfusia piceae, Adelges laricis, and Viteus vitifolli; examples from the Isoptera order are Reticulitermes lucifugus, Calotermes flavicollis, Leucotermes flavipes and Termes natalensis; examples from the Orthoptera order are Forficula auricularia, Acheta domestica, Gryllotalpa gryllotalpa, Tachycines asynamorus, lo Locusta mlgratorla, Stauronotus maroccanus, Schistocerca peregrlna, Nomadacris septemfasciata, Melanoplus spretus, Melanoplus femur-rubrum, Blatta orientalis, Blattella germanica, Periplaneta americana, and Blabera gigantea.
Examples of mites and ticks (Acarina) belonging to the Arachnida class are Tetranychus telarius, Tetranyehus atlanticus, Tetranychus pacificus, Paratetranyehus pilosus, Bryobia praetiosa, Ixodes ricinus, Ornithodorus moubata, Ablyomma americanum, Dermacentor silvarum, and Boophilus microplus.
Examples from the Nemathelminthes class are root-knot nematodes, e.g., Meloidogyne incognita, Meloidogyne hapla, and Meloldogyne javanica, cyst-forming nematodes, e.g., Heterodera rostochiensls, Heterodera schachtii, Heterodera avenae, Heterodera glycines, and Heterodera trlfolii, and stem and leaf eelworms, e.g., Ditylenchus dipsaci, Ditylenchus destructor, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus goodeyi, Pratylenehus curvitatus and Tylenchorhynehus dubius, Tylenchorhynchus claytonl, Rotylenchus robustus, Heliocotylenchus multicinctus, Radopholue slmllls, Belonolalmus longlcaudatua, Longldorus elongatus, and Triehodorus primltlvus.
The active ingredients may be applied as such, in the form of formulations or ready-to-use preparations produced therefrom, e.g., directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure as fine a distribution of the active ingredient as possible.
For the preparations of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, lsophorone, etc., and strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredlents as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
I SI 802 Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dlbutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglyool ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients' with a solid carrier.
Examples of formulations are given below.
I. 5 parts by weight of compound no. 18 is intimately mixed with 95 parts by weight of particulate kaolin. A dust is obtained containing 5? by weight of the active ingredient.
II. 30 parts by weight of compound no. 19 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed 51802 onto the surface of this silica gel. A formulation of the active Ingredient is obtained having good adherence.
III. 10 parts by weight of compound no. 50 is dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
IV. 20 parts by weight of compound no. 70 is dissolved in a mix10 ture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of isooctylphenol, and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil.
V. 80 parts by weight of compound 8 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-«<-sulfonic acid, 1.0 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel , and triturated in a hammer mill.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc. 61603 The formulations generally contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.
The amount of active ingredient in the ready-to-use preparations may vary within a wide range; it is generally from 0.0001 to 10%, preferably from 0.01 to 1%.
The active ingredients may also be successfully used in the ultra-low volume method, where it is possible to apply formulations containing more than 95 wt% of active ingredient, or even the 100% active ingredient.
When the active ingredients are employed in the open, application rates are from 0.2 to 10, and preferably from 0.5 to 2, kg/ha.
There may be added to the active Ingredients (if desired, Immediately before use (tankmix)) oils of various types, herbicides, fungicides, other pesticides and bactericides. These agents may be added to the active ingredients according to the invention in a weight ratio of from 1:10 to 10:1. · Examples of active ingredients which may be admixed are as follows: 1.2- dibromo-3-chloropropane, 1,3-dichloropropene, 1,3-dichloropropene + 1,2-dichloropropane, 1,2-dibromoethane, 2-sec-butylphenyl-N-methylcarbamate, o-chlorophenyl-N-methylcarbamate, 3-isopropyl-5-methylphenyl-N-methylcarbamate, o-isopropoxyphenyl-N-raethylcarbamate, 3,5-dimethyl-4-methylmercaptophenyl~N-methylcarbamate, 4-dimethylamino-3,5-xylyl-N-methylcarbamate, 2-(1,3-dioxolan-2-yl)-phenyl-N-methylcarbamate, 1-naphthyl-N-methylcarbamate, 2.3- dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate, 2,2-dimethyl-1,3-benzodioxol-4-yl-N-methylcarbamate, 2-dimethylamlno-5,6-dimethyl-4-pyrlmidinyldimethylcarbamate, 2-methyl-2-(methylthio)-propionaldehyde-0-(methylcarbamoyl)-oxime, S-methyl51602 -N-[-(methylcarbaaoyl)-oxy)-thioacetlmldate, methyl-Ν',Ν'-dimethyl-N-C(methylcarbamoyl)-oxy]-l-thiooxamidate, N-(2-methyl-4-chlorophenyl)-N'N'-dimethylformamidlne, tetrachlorothlophene, 1-(2,6-difluorobenzyl)-3-(4-chlorophenyl)-urea, 0,0-dimethyl-05 -(p-nltrophenyl)-phosphorothioate, 0,0-dlethyl-0-(p-nitrophenyl)-phosphorothloate, 0-ethyl-0-(p-nltrophenyl)-phenylphosphonothioat e, 0,0-dlmethyl-O-(3-methyl-4-nitrophenyl)-phosphorothioate, 0,0-dlethyl-0-(2,4-dichlorophenyl)-phosphorothioate, 0-ethyl-0-(2,4-dichlorophenyl)-phenylphosphonothioate, 0,O-dimethyl-O10 -(2,4,5-triohlorophenyl)-phosphorothioate, O-ethyl-O-(2,4,5-trichlorophenyl)-ethyl-phosphonothloate, 0, O-dimethyl-O-(4-bromo-2,5-diehlorophenyl)-phosphorothioate, 0,O-dimethyl-O-(2,5-dichloro-4-iodophenyl)-phosphorothioate, O,O-dimethyl-O-(3-methyl-4-methylthiophenyl)-phosphorothioate, O-ethyl-0-(3-methyl-4-methylthio15 phenyD-isopropylphosphoramidate, 0,O-diethyl-O-(p-(methylsulfynyl)-phenyl3-phosphorothioate, O-ethyl-S-phenylethyl-phosphonodithioate, 0,O-dlethyl-(2-chloro-l-(2,4-dlchlorophenyl)-vinyl3-phosphate, 0,0-dimethyl-[-2-chloro-l-(2,4,5-trlchlorophenyl)3-vinylphosphate, O,O-dlmethyl-S-(l-phenyl)-ethylacetate phosphoro20 dlthioate, bis-(dimethylamino)-fluorophosphine oxide, octamethyl-pyrophosphoramlde, 0,0,0,O-tetraethyldithiopyrophosphate, S-chloromethyl-0,0-dlethyl-phosphorodithioate, O-ethyl-S,S-dlpropyl-phosphorodithloate, 0,0-dimethyl-0-2,2-dichlorovinylphosphate, 0,0-dimethyl-l,2-dibromo-2,2-dichloroethylphosphate, 0,0-dl25 methyl-2,2,2-t rlchloro-l-hydroxyethylphosphonate, 0,O-dimethyl-S-El,2-biscarbethoxyethyl-(l)]-phosphorodithioate, O,O-dimethyl-O-(l-methyl-2-carbomethoxyvinyl)-phosphate, 0,0-dlmethyl-S-(N-methylcarbamoylmethyl)-phosphorodithloate, 0,O-dimethyl-S-(N-methylcarbamoylmethyD-phosphorothioate, O,O-d.imethyl-S-(N-meth51602 oxyethylcarbamoylmethyl)-phosphorodithioate, 0,0-dimethyl-S-(N-formyl-N-methylcarbamoylmethyl)-phosphorodithioate, 0,0-dimethyl· -0-[l-methyl-2-(methylcarbamoyl)-vinyll-phosphate, 0,0-dimethyl-0-[ (l-methyl-2-dimethylcarbamoyl)-vinyl]-phosphate, 0,0-dimethyl-0· -[(l-methyl-2-chloro-2-diethylcarbamoyl)-vinyl]-phosphate, 0,0-diethyl-S-(ethylthiomethyl)-phosphorodithioate, 0,O-diethyl-S-[(p-chlorophenylthio)-methyl]-phosphorodithloate, 0,0-dimethyl-S-(2-ethylthloethyl)-phosphorothioate, 0,0-dimethyl-S-(2-ethylthioethyl ) -phosphorodithioate, 0,0-dimethylsulf ynylethyl)-phosphoro10 thioate, 0,0-diethyl-S-(2-ethylthioethyl)-phosphorodithioate, 0,0-diethyl-S-(2-ethylsulfynylethyl)-phosphorothioate, 0,0-diethyl thiophosphoryllmlnophenyl-acetonitrile, 0,0-diethyl-S-(2-chloro-l-phthalimidoethyD-phosphorodithioate, 0,0-diethyl-S-[6-ohlorobenz oxazolon-(2)-yl-(3)1-methyldithiophosphate, 0, O-dimethyl-S-[215 -methoxy-1,3,4-thiadiazol-5-onyl-(4)-methyl1-phosphorodithioate, 0,0-diethyl-0-[3,5,6-triohloropyridyl-(2)]-phosphorothioate, 0,0-diethylO-(2-pyrazlnyl)-pho sphorothloat e, 0,0-diethyl-0-[2-isopropyl-4-methylpyrimidinyl-(6)1-phosphorothioate, 0,0-diethyl-0-[2-(dlethylamino)-6~methyl-4—pyrimidlnyll-thionophosphate, o,O-dimethyl-S-(4-oxo-l,2,3-b enzotriazin-3-[4H1-yl-methyl)-phosphorodlthioat e, 0,O-dimethyl-S-[(4,6-diamino-l,3,5-triazin-2-yl)-methyl]-pho sphorodithioat e, 0,0-dlethyl-(1-phenyl-l,2,4-t riazol-3· -yl)-thionophosphate, 0,S-dimethylphosphoroamidothioate, O,S-dimethyl-N-aoetylphosphoramidothloate,a-hexachlorocyclohexane, 1,125 -di-(p-methoxyphenyl)-2,2,2-trichloroethane, 6,7,8,9,10,10-hexachloro-l,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide, pyrethrins, DL-2-allyl-3-niethyl-cyclopenten-(2)-on-(l)-yl-(4)-DL-cis,trans-chrysanthemate, 5-benzylfuryl-(3)-methyl-DL-c is,trans-chrysanthemate, 3-phenoxybenzyl(+)-cis,trans51602 -2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylate, θζ-c yano-3-phenoxybenzyl (+) -c Is, t rans-2,2-dlmethyl-3-( 2,2-dichlorovinyl)-cyclopropane carboxyiate, (s)-t^-cyano-3-phenoxybenzyl-cis(lR,3R)-2,2-dimethyl-3-(2,2-dlbromovinyl)-cyclopropane carb5 oxylate, 3,4,5,6-tetrahydrophthallmldoethyl-DL-cls,trans-chrysanth emate, 2-methyl-5-(2-propynyl)-3-furylmethyl-chrysanthemate, and οι. -cyano-3-phen-oxybenzyl-t<-isopropyl-4-chlorophenylacetate.
The biological action of the new compounds of the formula I is illustrated in the following examples. The agent used for com10 parlson purposes was the prior art active ingredient 0,0-diethyl-0-(4-trlfluorphenyl)-thlophosphate (German Laid-Open Application DE-OS 21 49 312).
The active Ingredients are numbered as in the foregoing table.
EXAMPLE 1 Contact action on houseflies (Musca domestica) Both covers and bottoms of Petri dishes 10 cm in diameter are lined with a total per dish of 2 ml of acetonic solutions of the active ingredients. After the solvent has evaporated (about rains.), 20 4-day old flies are introduced into each dish. The kill rate Is determined after 4 hours.
In this test, compounds nos. 8, 9, 10, 18, 19, 20, 40, 41, 42, 50, 51, 52, 70, 72, 78, 80 and 87 achieve a very high kill rate. EXAMPLE 2 Contact action on aphids (Aphis fabae); spray experiment Potted bean plants (Vicia faba) with large aphid colonies were sprayed to runoff in a spray cabinet with aqueous formulations of the active ingredients. Assessment took place after 48 hours.
In this test, for example compounds nos. 9, 10, 19, 40, 70 and 78 had a better action than the comparative agent.
EXAMPLE 3 Contact action and effect of ingested food on caterpillars of the diamondback moth (Plutella macullpennls) Leaves of young cabbage plants are dipped for 3 seconds in aqueous emulsions of the active ingredients, and placed, after excess liquid has been briefly allowed to drip off, on a moist filter paper in a Petri dish. 10 caterpillars in the 4th stage are then placed on each leaf.
The action is assessed after 48 hours.
Active ingredients nos. 8, 9, 10, 18, 19, 20, 40, 41, 42, 50, 51, 52, 70 and 80 had an action superior to that of the prior art compound.
EXAMPLE 4 Contact action on mosquito larvae (Aedes aegyptl) The active ingredient formulations are added to 200 ml of tapwater, 30 to 40 Aedes larvae in·the 4th stage are then introduced. 2o The temperature is kept at 20°C. The action is assessed after hours.
In this test, active ingredient nos, 8, 9, 10, 18, 19, 20, 40, 41, 42, 50, 51 and 52 exhibited an action superior to that of the comparative agent.
EXAMPLE 5 Contact action on oriental cockroaches (Blatta orientalis) The bottoms of 1 liter preserving jars are treated with acetonic solutions of the active ingredients. After the solvent has evaporated, 5 adult cockroaches are placed in each jar, and the kill rate is determined after 48 hours.
In this test, active ingredients nos. 8, 9, 10, 18, 19, 20, 40, 41, 42, 50 and 51 proved to have an action superior to that of the comparative agent.
EXAMPLE 6 Contact action on granary weevils (Sltophilus granarius) Petris dishes 10 cm in diameter are lined with acetonic solutions of the active ingredients. After the solvent has evaporated, 100 granary weevils are placed in each dish.
After 4 hours, the weevils are transferred to untreated 10 vessels. The kill rate is determined after 24 hours, by counting how many weevils are, after this period has elapsed, capable of leaving an untreated cardboard dish (40 mm in diameter, 10 mm high) within 60 minutes.
With comparable amounts of active ingredient per Petri dish, 15 the number of weevils killed after treatment with active ingredients nos. 8, 9, 10, 19, 40, 41, 42, 50, 78 and 80 is much greater than the number killed after treatment with the comparative agent.
EXAMPLE 7 Contact action on ticks (Omlthodorus moubata) Ticks in the 3rd larval stage are placed in paper bags and dipped for 3 seconds in the emulsion under investigation. The bags are then suspended. The action on the ticks is assessed after 48 hours.
In this test, a higher kill rate is achieved with emulsions having a lower concentration of active ingredients nos. 40, 42, 78 and 80 than of the comparative agent.
BIQOSi EXAMPLE 8 Action on root-knot nematodes (Meloidogyne Incognita) Young tomato plants are each planted in 500 g of compost heavily infested with root-knot nematodes. The plants are treated 3 days later by spraying than in a spray booth with 50 ml of aqueous active ingredient formulation.
The roots are assessed for knot formation after 6 to 8 weeks In this test, for example active ingredients nos. 18, 42, 70 and 72 had an action superior to that of the comparative agent.

Claims (11)

1. A 4-trifluoromethylphenyl. (di)thiophoaphate of the formula 5 where R 1 is alkyl of 1 to 3 carbon atoms, R 2 is alkyl, haloalkyl, alkoxyalkyl or alkylthioalkyl of 1 to 6 carbon atoms, r\ r 1 * and R^ independently of one another are hydrogen, halogen, cyano or alkyl, alkoxy or alkylthio of 1 to 4 carbon atoms and X is oxygen or sulfur. 10 2. A 4-trifluoromethylphenyl thiophosphate of the formula
2. 5 where R is alkyl of
3. Or 4 carbon atoms, R is halogen, 5. And R and R are hydrogen. 15 3. A 4-trifluoromethylphenyl (di)thiophosphate as claimed in claim 1 and identified in any one of the foregoing Examples 1 to 109.
4. 0-Ethyl-S-n-propyl-0-(2-chloro-4-trifluoromethylphenyl) thiophosphate. 2o
5. 0-Ethyl-S-n-propyl-0-(2-bromo-4-trifluoromethy1phenyl) thiophosphate.
6. A process for the manufacture of a 4-t,ri ΓΙοουοmethylphenyl (di)thiophosphate claimed in claim 1, wherein an O,S-dialkyl phosphate-chloride of the formula 516 0 2 r 2 s // X P-Cl (II), 12 ... where R , R and X have the meanings given in claim 1, is reacted with a 4-trifluoromethylphenol of the formula III z H c ..... where R , R and R have the meanings given m claim 1, m the presence or absence of an acid-binding agent and in the presence or absence of a diluent, or with a salt of a 4trifluoromethylphenol of the formula III in the presence or absence of a diluent.
7. A process for the manufacture of a 4-trifluoromethylphenyl (di)thiophosphate claimed in claim 1 carried nut. substantially as hereinbefore described or exemplified.
8. A 4-trifluoromethylphenyl (di)thiophosphate as claimed in claim 1 when manufactured by a process as claimed in claim δ or 7.
9. The use as a pesticide of a 4-trifloromethylphenyl (di)thiophosphate as claimed in any of claims 1 to 5 or 8.
10. A pesticide comprising one or more inert additives and a 4-trifluoromethylphenyl (di)thiophosphate as claimed in any of claims 1 to 5 or 8.
11. A process for combating pests, wherein a 4-trifluoromethylphenyl (di)thiophosphate as claimed in any of claims 1 to 5 or 8 is allowed to act on the pests and/or their habitat.
IE2271/81A 1980-10-03 1981-09-30 4-trifluoromethylphenyl(di)thiophosphates,their preparation and their use in pest control IE51602B1 (en)

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DE3134136A1 (en) * 1981-08-28 1983-03-17 Basf Ag, 6700 Ludwigshafen 3-FLUORPHENYL- (DI) THIOPHOSPHORIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING Pests
DE3231191A1 (en) * 1982-08-21 1984-02-23 Basf Ag, 6700 Ludwigshafen 4-TRIFLUORMETHYLPHENYL (THIO) PHOSPHORIC ACID AMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING PESTS
DE10040051A1 (en) * 2000-08-11 2002-02-21 Basf Ag Derivatives of 4- (trifluoromethyl) phenol and derivatives of 4- (trifluoromethylphenyl) -2- (tetrahydropyranyl) ether and process for their preparation

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BE789439A (en) * 1971-09-30 1973-03-29 Ciba Geigy THIOPHOSPHORIC ESTERS WITH PROPERTIES
BE789463A (en) * 1971-10-02 1973-03-29 Bayer Ag NEW ESTERS OF THIOPHOSPHORIC ACIDS, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS NEMATICIDES AND SOIL INSECTICIDES
CA1048048A (en) * 1972-06-01 1979-02-06 Odd Kristiansen Esters
US3830882A (en) * 1972-11-16 1974-08-20 Velsicol Chemical Corp Semicarbazono phosphorus compounds
JPS56147794A (en) * 1980-04-17 1981-11-16 Kumiai Chem Ind Co Ltd Organic phosphoric ester derivative, its preparation and insecticide, acaricide, nematocide, and fungicide comprising it

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DE3160442D1 (en) 1983-07-21
DK437081A (en) 1982-04-04
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