CA2006231A1 - Substituted propargyl cyclopropanecarboxylates, their preparation and their use for controlling pests - Google Patents

Abstract

O.Z. 0050/40460 ABSTRACT OF THE DISCLOSURE: Novel, substituted propargyl cyclopropane-carboxylates of the general formula I

Description

- Z006231.
O.Z. 0050/40460 Substituted ~ropar~yl cyclopropanecarboxylates.
their preDaration a~d their use for controlling pest~
The present invention relate~ to novel sub-stituted propargyl cyclopropanecarboxylate~ of the general formula I

~C=CH--Cll'C~R5 where R1 and R2 are each Cl-C4-haloalkyl or halogen, both radicals not simultaneously being halogen, R3 to R' independently of one another are each hydrogen, halogen, cyano, Cl-C6-alkyl, C2-C6-alkenyl, C2-C~-alkynyl or C1-C5-alkoxy, the hydrocarbon radicals each being un~ub-stituted or ~ubstituted by halogen, or two ad~acent radicals being bonded via an -O-X-O- group, and X is an unsubstituted or halogen-substituted methylene or ethylene group, with the proviso that R~ is not trifluoromethyl when R5 i9 chlorine.
The present invention furthermore relates to pesticides which contain these compounds I as active ingredients and methods for controlling pests with these active ingredients.
Japanese Preliminary Published Applications 144 349/1983, 121 246/1983 nnd 095 940/1982 disclose that speclally ~ub~tituted propargyl cyclopropanecarboxylates have an in8ecticidal ~ction. DB-A-31 45 448 discloses 2,2-dih~lovinyl-substituted propargyl cyclopropane-carboxylate~ for controlling pests. However, the insect-icidal actlvity of the esters described in the literature is unsatis~ctory ln most cases under certain conditions, for example at low application rates.
It is an ob~ect of the pre~ent invention to pro-vide novel substituted propargyl cyclopropanecarboxylate~
having an improved action.

;~OV6231.

- 2 - O.Z. 0050~40460 We have found that thi~ ob~ect i3 achieved by the propargyl cyclopropanecarboxylate~ described at the out-set. We have al~o found that the compound~ I are very suitable for controlling pest~.
The esters of the formula I can be obtained by reacting an acid II or a derivative thereof with an ~-ethynyl alcohol III in accordance with the following general equation:
Rl R3 R~
C=CH--CH--CH--C0011 I HC~C--CH~R5 R2/ ~ \1H R~(R6 -H2 II III
The reaction can be accelerated in a known manner by adding a catalyst, such as sulfuric acid, a hydrogen halide, a ~ulfonic acid or an acidic ion exchanger, and the equilibrium of the esterification can be ~hifted in the desired direction by removing water or the ester I
from the reaction mixture, for example by azeotropic di~tillation or by binding the water to sulfuric acid or a hydrohalic acid.
It i8 also possible for reactive carboxylic acid derivatives, such as the corresponding acyl halides, for example acyl chlorides, to be reacted with the alcohols of the formula III in the presence of an acld acceptor (cf. Houben-Weyl, Methoden der organischen Chemle, Volume VIII, page 541 et ~eq., Georg-Thleme-Verlag, Stuttgart 1952).
Suit~ble acid acceptors are the conventional basic agents, in particular aliphatic, aromatic and heterocyclic ~mines, eg. triethylamine, dimethylamine, piperidine, dimethylaniline, dimethylbenzylamine, pyrid-ine and 2-picoline.
The reaction can be carried out in a solvent or diluent. The st~ted acid acceptors themselve3 or, for example, the following solvent~ or diluents or mixtures ~()06~1 - 3 - O.Z. 0050t40460 thereof are ~uitable for this purpose:
aliphatic and aromatic hydrocarbons and chlorohydro-carbons, ~uch as petroleum ether, benzene, toluene, xylene, ga~oline, dichloromethane, chloroform, tetra-chloromethane, 1,2-dichloroethane or chlorobenzene, ethers, ~uch a~ diethyl ether, di-n-butyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, ketone~, for example aeetone, methyl ethyl ketone or methyl i80-propyl ketone, and nitriles, ~uch as acetonitrile or propionitrile.
The starting materials are usually u~ed in a ~toichiometric ratio. An excess of one or other of the starting materials may be quite advantageous in specific cases.
~he reaction of the aeyl halides usually proeeeds at an adequate rate at above 0C. Since it may take place with evolution of heat, it may be advantageous to provide a means of eooling.
The novel esters may furthermore be prepared by virtually all known methods of ester synthe~is, for example by reaeting eorresponding anhydrides with the alcohols of the formula III, by reaeting eorresponding salts with derivatives of the aleohols of the formula III
or by transe~terifie~tion (ef. Houben-Weyl loe. cit., pages 508-628).
The aeid component~ of the general formula II
whlch are regulred a~ startlng materlals, ~nd the derlva-tlve- of the ~ald aeid components, ~re known from the literature, for example from Wegler, Chemie der Pflanzen-sehutz- und Sehadlingsbekampfung~mittel, Volume 7, Springer-Verlag, Berlin, Heidelberg, New York 1981.
The aleohols of the formul~ III which are re-quired a8 starting materlals ean be prepared by reseting the eorrespondlng aldehydes wlth organometallie compounds of acetylene, for example Grlgnard compounds or organo-lithium eompound~.
The reaetions with the org~nometallie eompounds ZO~)6Z31 , - 4 - O.Z. 0050/40460 can be carried out in a conventional manner, for example a~ described in Houben-Weyl, Methoden der organischen Chemie, Volume 13/2a, page 285 et seq., 1973, in an inert organic ~olvent, such a~ ether or tetrahydrofuran, under a protective gas, 80 that no further description i8 required here.
Of course, the compounds of the formula I in every case occur in the form of pure diastereomers, at least one pair of optical antipodes, and in many cases in the form of diastereomer mixtures, and can be u~ed as active ingredients, which, depending on the starting materials and the reaetion conditions, occur in pure form or as mixtures. The mixtures can be sep~rated into their sterieally pure component~ in a conventional manner.
Their biologieal action is dependent on their steric confi~uration in ~peeific cases.
In the novel compounds I, Rl to R7 have the following specific meanings s Rland R2 are e~eh C1-C~-h~loalkyl, prefer~bly C1-C~-fluoro-or ehloroalkyl, sueh a8 trifluoromethyl, difluoromethyl, fluoromethyl, triehloromethyl, pentafluoroethyl, 2,2,2-trifluoroeth-l-yl,2,2,2-triehloroeth-1-yl,1,3-difluoro-isopropyl or 1,3-diehloroisopropyl, trifluoromethyl being partieularly preferred, or halogen, sueh a~ fluorine, ehlorine or bromine7 R3 to R7 are eaeh hydrogen7 haloq n, sueh a- fluorlne, ehlorlne, bromine or iodine;
cy~no;
C1-C0-alkyl, in partieular Cl-C~-alkyl, sueh as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, see-butyl or tert-butyl, where the stated r~dieals may be substituted by one or more, in partieular from 1 to 4, halogen atoms, eg. ehlorlne or fluorines C2-C0-alkenyl, sueh as vinyl, allyl, l-methylallyl, 1,3-dimethylbut-2-enyl, 1-methylbut-2-enyl or but-3-en-1-yl, where the statod radieals may be substituted by one or more, in partieular from 1 to 4, h~logen atoms, eg.

;~OO~Z3~

- 5 - O.Z. 0050/40460 chlorine or fluorine;
C2-C~-alkynyl, such a~ ethynyl, prop-l-yn-l-yl, prop-2-yn-l-yl, l-methylprop-2-ynyl, but-2-yn-2-yl or but-3-yn-l-yl, where the stated radicals may be substituted by one or more, in particular from l to 4, halogen atoms, eg.
chlorine or fluorine, or C,-C6-alkoxy, such as methoxy, ethoxy, propoxy, i~oprop-oxy, butoxy or tert-butoxy, where the alkyl groups may be substituted by one or more, in particular from 1 to 4, halogen atoms, eg. chlorine or fluorine, or two ad~acent radicals R3 and R~, R~ and R5, R5 and R6 or R6 and R7 may furthermore be bonded to one another via an O-X-O group, and X i~ an unsubstituted or halogen-substituted methylene or ethylene group, particularly suitable halogen sub-stituents being fluorine and chlorine.
Particularly preferred compounds I are tho~e in which Rl is trifluoromethyl and R2 is fluorine, chlorine or bromine, and the phenyl radical is unsubstituted or carries from l to 3 of the abovementioned substituents.

6 O.Z. 0050/40460 The propargyl cyclopropanecarboxylates of the formula I are suitable for effectively combating pests from the class of insects, mites and nema-todes. ~hey may be used as pesticides in crop protection, and in the hygiene, stores protection and veterinary sectors.
s Examples of injurious insects from the Lepidoptera order are Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, IO Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothis 15 zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keifferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra 20 brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scarbra, Plutella xylostella, Pseudoplusia includens, Phyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerelella, Sparganothis pilleriana, 25 Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis.
Examples from the Coleoptera order are Agrilus sinuatus, Agrlotes 30 lineatus, ~griotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, ByctiScuS betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetocnema tibialis, 35 Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Oiabrotica 12-punctata, Oiabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus 40 oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Onlema oryzae, Ortiorrhynchus sulcatus, Ortiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria.

2006Z~

7 o.z. 0050/40460 Examples from the Diptera order are Aedes aegypti, Aedes vexans, Anastrepha-ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, 5 Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina 10 stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhago-letis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa.
Examples from the Thysanoptera order are Frankliniella fusca, 15 Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci.
Examples from the Hymenoptera order are Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, 20 Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta.
Examples from the Heteroptera order are Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster Integriceps, Euchistus impictiventris, 25 Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, P1esma quadrata, Solubea insularis and Thyanta perditor.
Examples from the Orthoptera order are Forficula auricularia, Acheta domestica, Gryllotalpa gryllotalpa, tachycines asynamorus, Locusta 30 migratoria, Stauronotus meroccanus, Schistocerca peregrina, Nomadacris septemfasciata, Melanoplus spretus, Metanoplus femur-rubrum, Blatta orientalis, Blattella germanica, Periplaneta americana and Blabera gigantea.
35 Examples from the Arachnida order are Ixodes ricinus, Ornithodorus moubata, Amblyomma americanum, Dermacentor silvarum, Boophilus microplus, Tetranychus telarius, Tetranychus pacificus, Paratetranychus pilosus, Bryobia praetiosa.
40 Examples from the nematode class are root-knot nematodes, e.g., Meloi-dogyne hapla, Meloidogyne incognita and Meloidogyne javanica, cyst-forming nematodes, e.g., Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schachtii, Heterodera triflolii, stem and leaf eelworms, e.g., Belonolaimus longicaudatus, Ditylenchus destructor, ZOOGX3~

8 O.Z. 0050/40460 Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus-similis, Rotylenchus robustus, Trichodorus primitivus, Tylen-chorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, PratylenchuS goodeyi.

The active ingredients may be applied for instance as such, or in the form of formulations or application forms prepared therefrom, e.g., directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, paste~, dusts, broadcasting agents, or granules by spraying, 10 atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients accord-ing to the invention as possible.
IS For the preparation 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 vege-table or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated 20 naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, 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 ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing 30 agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dlspersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and 35 ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutyl-naphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of 40 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 isooctyl-XO~ iZ3~

9 O.Z. 0050/40460 phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenolpolyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated poly-5 oxypropylene, 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. I is intimately mixed with 9S parts by weight of particulate kaolin. A dust is obtained containing 5% by 15 weight of the active ingredient.
Il. 30 parts by weight of compound no. 2 is intimately mixed with a mix-ture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this 20 silica gel. A formulation of the active ingredient is obtained having good adherence.
111. 10 parts by weight of compound no. 4 is dissolved in a mixture con-sisting of 90 parts by weight of xylene, 6 parts by weight of the adduct 25 of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanol-amide, 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 and I mole of castor oil.
30 IV. 20 parts by woight of compound no. 13 iS dissolved ln a mixture consisting of 60 parts by welght of cyclohexanone, 30 parts by welght of isobutanol, 5 partS by weight of the adduct of 7 moles of ethylene oxide and I mole of isooctylphenol, and 5 partS by weight of the adduct of 40 moles of ethylene oxide and I mole of castor oil.
V. 80 parts by weight of compound no. 19 is well mixed with 3 parts byweight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 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, 40 and triturated in a ha_er 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, 20~231 O.Z. 0050/40460 silicates, talc, kaolin, attapulgus clay, timestone, 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 5 products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations generally contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.
The active ingredient concentrations in the finished formulations may vary over a wide range. Generally, they are from 0.0001 to 10, and preferably from 0.01 to 1, #. The active ingredients may also successfully be used in the ultra-low-volume (ULV) method, where it is possible to apply formula-15 tions containing more than 95wt% of active ingredient, or even the activeingredient without additives.
In the open, the amount of active ingredient applied is for example from 0.02 to 10, particularly from 0.1 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 in-gredients according to the invention in a weight ratio of from 1:10 to 25 10:1.
The compounds according to the invention may be prepared in accordance with the following example:
30 Manufacturing example 2,2-Dimethyl-3-(3 ,3 ,3 -trifluoro-2 -chloropropen-(1~-yl)-cyclopropane-carboxylic acid-1 -(2 ,6 -difluorophenyl)-propyne-(2 )-ester (trans form) At 15-20C, 7.8 9 (0.03 mol) of 2,2-dimethyl-3-(2 -chloro-3 ,3 ,3 -trifluoropropen-(1))-cyclopropanecarboxylic acid-(1)-chloride (trans form) is added dropwise to a solution of 5 9 (0.03 mol) of 1-hydroxy-1-(2 ,6 -difluorophenyl)-propyne-(2) and 4 9 (0.04 mol) of triethylamine in 100 ml 40 of toluene. After the exothermic reaction is complete, the mixture is stirred for 4 hours at 40C. It is then cooled and washed with water, the organic phase is dried, and the solvent is removed. There is obtained 11 9 (93.4% of theory) of a light yellow oil.

Z0~)623~

11 O.Z. 0050/40460 CH analysis (molecular weight = 392.5) C H Cl F
Calc.: 55.1 3.6 9.0 24.2 5 Found: 55.3 4.0 9.1 23.9 300 MHz NMR spectrum in CDC13 (ppm):
1.24~6H); 1.83(1H); 2.42(1H); 2.62(1H); 6.14(1H); 6.79(1H); 6.86-7.0(2H);
7.37(1H).
The compounds listed in the following table are prepared analogously:

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200623~
17 o.Z. OOS0/40460 Use examples ~n the following examples the action of the compounds according to the invention on pests was compared with that of the following compounds from 5 DE-AS 31 45 448:

Cl\ IclH R
/ \ 5 ~ R

Cl / \

I R = CF3 R,, = H
Il R, = H R,, = CF3 111 R = CH3 R = H

The concentratlons at whlch the investigated compounds exhibit 100% kill or inhibition are the minimum concentrations. At least one replicate was 10 used for each concentration.
The purity of all compounds investigated was at least 95%.
The following formulations were employed:
A: A 0.1~ strength solution of the active ingredient in acetone is prepared and this stock solution is further diluted according to the dosage rates with acetone.
20 B: The active ingredlent is formulated as an emulsion concentrate by emulsifying it in a mlxture conslsting of 70* of cyclohexanone 20% of Nekanil LN (ethoxylated castor oll) and 10% of Emulphor EL (ethoxylat-ed isooctylphenol). Oilution with appropriate amounts of water gives suspensions containing the stated active ingredient concentrations.
A) Blatta orientalis ~cockroaches); contact action The bottoms of 1 liter jars is treated with acetonic solutions of the active ingredients. After the solvent has evaporated 5 adult cock-roaches are placed in each jar. The kill rate is determined after 48 hours.
In this experiment compounds nos. 31 41 44 56 60 61 66 and 67 have a better action than comparative agent 11.

Z00623~

18 O.Z. 0050/40460 B) Sitophilus granarius (granary weevils); contact action The bottoms of glass Petri dishes 10 cm in diameter and whose edges have been treated with polytetrafluoroethylene to prevent the weevils S from escaping are treated with lcm3 of acetonic solutions of the active ingredients. After the acetone has evaporated, about 50 weevils are placed in each dish. After 4 hours the weevils are transferred to cardboard dishes (40 mm in diameter and 10 mm high), which are then placed in the Petri dishes. The action is determined after 24 hours in percentage kill. Weevils unable to leave the cardboard dish are con-sidered to be dead or severely disabled.
In this experiment, compounds nos. 21, 29, 31, 41, 51, 55, 56, 61, 66, 67 and 72 have a better action than comparative agents I, Il and Ill.
C) Aedes aegypti (yellow-fever mosquito); contact action Aqueous active ingredient formulations are added to 200 ml of tapwater in 250 ml plastic beakers, and 20-30 mosquito larvae in the 3rd to 4th larval stage are introduced. The temperature is kept at 25C. The action is assessed after 24 hours.
In this experiment, compounds nos. 21, 29, 31, 32, 41, 51, 54, 55, 56, 57, 60, 61, 66, 67 and 72 were superior to comparative agents 1, II
and III.
O) Musca domestica ~houseflies); continuous contact action Both tops and bottoms of Petri dishes 10 cm in diameter are treated with a total of 2 ml o- acetonic solutlons of the dctive ingredients.
After the solvent hds evaporated (about 30 mins.), 10 flies are placed in each diSh. The kill rate is assessed after 4 hours.
In this experiment, compounds nos. 21, 29, 31, 32, 41, 43, 44, 51, 54, 55, 56, 57, 60, 66, 67 and 72 had a better action than comparative agents I and III.
E) Dysdercus intermedius (cotton Stainer); contact action 200 g of quartz sand iS mixed with 25 ml of the aqueous active ingredient formulations, and intrcduced into 1 liter jars. About 20 cotton stainer larvae in the 3rd larval stage are placed in each jar.
The contact action is assessed after 24 hours as percentage kill.

19 O.z. 0050/40460 In this experiment, compounds nos. 31, 32, 41, 43, 44, 51, 54, 55, 56, 57, 60, 61, 66 and 67 have a better action than comparative agents Il and III.
F) Plutella maculipennis (diamondback moth); contact action 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 of the 4th stage are then placed on each leaf. The kill rate is assessed in % after 48 hours.
In this experiment, compounds nos. 41, 43, 44, 51, 54, 55, 56, 57, 60 and 61 have a better action than comparative agents II and III.
15 G) Prodenia litura; contact action Glass Petri dishes 10 cm in dlameter are treated with acetonic solutions of the active ingredients. After the solvent has evaporated, 5 caterpillars in the 4th larval stage are placed in each dish and the dishes closed. The kill rate is assessed after 4 hours.
In this experiment, compounds nos. 21, 29, 41, 43, 44, 54, 56, 57, 61, 66 and 67 have a better action than comparative agents I, II and III.
25 H) Prodenia litura; antifeedant action The experiment is carried out in plastic beakers. Per vessel, 2 cater-pillars in the 3rd larval stage are used which have had no food for 24 hours. The substrate is baking wafers (1.5 x 2 cm) dipped for 5 seconds in aqueous formulations of the active ingredients. The per-centage kill rate is assessed after 24 hours.
In this experiment, compounds nos. 56, 61 and 66 have a better action than comparative agents Il and III.

Claims (6)

1. Substituted propargyl cyclopropanecarboxylates of the general formula I, where R1 and R2 are each C1-C4-haloalkyl or halogen, both radicals not simultaneously being halogen, R3 to R7 independently of one another are each hydrogen, halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl or C1-C6-alkoxy, the hydrocarbon radicals each being unsubstituted or substituted by halogen, or two adjacent radicals being bonded via an O-X-O- group, and X is an unsubstituted or halogen-substituted methylene or ethylene group, with the proviso that R4 is not trifluoromethyl when R5 is chlorine.

2. A substituted propargyl cyclopropanecarboxylate of the general formula I as set forth in claim 1, where R1 is trifluoromethyl and R2 is fluorine, chlorine or bromine.

3. A process for the manufacture of substituted propargyl cyclopropane-carboxylates of the general formula I as set forth in claim 1, wherein an acid of the general formula II

II, where R1 and R2 have the meanings given in claim 1, or a derivative thereof, is esterified in conventional manner with an .alpha.-ethynyl benzyl alcohol of the general formula III

III, where R3, R4, R5, R6 and R7 have the meanings given in claim 1.

CA, KR, TW
2 1 O.Z. 0050/40460

4. A pesticidal agent containing a substituted propargyl cyclopropane-carboxylate of the general formula I as set forth in claim 1 and conventional inert additives.

5. A pesticidal agent as set forth in claim 4, containing from 0.1 to 95wt% of a propargyl cyclopropanecarboxylate of the formula 1.

6. A process for combating pests, wherein a propargyl cyclopropanecarb-oxylate of the formula I as set forth in claim 1 is allowed to act on the pests or their habitat.