CS198113B2 - Insecticide - Google Patents

Description

The present invention relates to propionyl compounds, to novel synergistic insecticidal compositions comprising a mixture of active ingredients, one of which is a propionyl value, and to the use of these compositions.

It has been found that some propynyl compounds, which are described in more detail below, synergistically enhance the effect of insecticides, in particular carbamates, organophosphates and esters of chrysantemummono and dicarboxylic acid. Moreover, this synergistic effect is highly selective in that the toxicity of the insecticides to warm-blooded animals does not substantially increase.

The compounds of the invention, characterized by synergy, protect the environment in which they are used by allowing the insecticide dose to be reduced, whereas insect mortality is comparable to that achieved using the insecticide alone. This is particularly important when the insecticide is persistent or highly toxic to birds, fish or mammals in the environment used. In many cases, the synergistic propynyl compounds of the invention broaden the spectrum of insecticide activity. They also revert the effect of insecticides when used against insects that have developed insecticide resistance if this resistance is due to metabolism, i.e., enzymatic detoxification of the insecticide. In this case, the propynyl compounds of the invention act as inhibitors of enzymatic detoxification.

Insecticidally active compounds with which the synergistic compounds of the invention may be used include: Phosphoric acid derivatives bis-O, Od ^; .ethylphosphoric acids (TEPP),

Ο, Ο, Ο, tetra-tetrapropyldithiopyrophosphate, dimethyl (2,2,2-trichloro-1-hydroxyethyl) phosphonate (Trichrorion),

1,2-dibromo-1,2-dichloroethyldimethylphosphate (Naled),

2.2-dichlorvinyldimethylphosphate (Dichlorphos),

2-methoxycarbamyl-1-methylvinyldimethylphosphate (Mevinphos), dimethyl-1-methyl-1- (methylcarbamoyl) vinylphosphate-cis (Monocrotophos),

3- (dimethoxyphosphinyloxy) -N-methyl-N-methoxy-cis-crotonamide,

3- (dimethoxyphosphinyloxy) -N, N-dimethyl-cis-crotonamide (Dicrotophos),

2-chloro-2-diethylcarbamoyl-1-methylvinyl dimethyl phosphate (Phosphamidon),

O, O-diethyl-O-2- (ethylthio) ethylthlophosphate (Demeton),

O, O-diethyl S-2- (ethylthio) ethylthiophosphate,

S-ethylthioethyl O, O-dimethyldithiophosphate (Thiometon);

O, O-diethyl-S-ethylmercaptomethyldithiophosphate (Phorate),

O, O-diethyl S-2 - [(ethylthio) ethyl] dithiophosphate (Disulfotone),

O, O-dimethyl-S-2- (ethylsulfinyl) ethylthiophosphate (Oxydemetonmethyl),

O, O-dimethyl-S- (1,2-dicarbethoxyethyl) dithiophosphate (Malathion), (O, O, O, O-tetraethyl-S, S‘-methylene-bis [dithiophosphate] (Ethion),

O-ethyl-S, S-dipropyldithlophosphate,

O, O-dimethyl-S- (N-methyl-N-formylcarbamoylmethyl) -dithiophosphate (Formotion),

S-N- (1-cyano-1-methylethyl) carbamoylmethyldiethylthiolphosphate (Cyantlioate),

S- (2-acetamidoethyl) -O, O-dimethyldithiophosphate, hexamethylphosphoric triamide (Hempa),

0,0-dimethyl-O-p-nitrophenylthiophosphate (Parathion-methyl),

O, O-diethyl-O-p-nitrophenylthiophosphate (Parathion),

O-ethyl-O-p-nitrophenylthiophosphonate (EPN),

O, O-dimethyl-O- (4-nitro-m-tolyl) thiophosphate (Phenitrothion),

O, O-dimethyl-O- (2-chloro-4-nitrophenyl) thiophosphate (Dicapthon),

O, O-dimethyl-O-p-cyanophenyl thiophosphate (Cyanox),

O-ethyl-O-p-cyanophenylphenylthiophosphonate,

O, O-diethyl-O-2,4-dichlorophenylthiophosphate (Dichrofenthion),

0-2,4-dichlorophenyl-O-methylisopropylamidothiophosphate,

O, O-dimethyl 1-0-2,4,5-trichlorophenylthiophosphate (Ronnel),

O-ethyl-O-2,4,5-trichlorophenylethylthiophosphonate (Trichloronate),

J

O, O-dimethyl-O-2,5-dichloro-4-bromophenylthiophosphate (Bromophos),

O, O-diethyl-O-2,5-dichloro-4-bromophenylthiophosphate (Bromophos-ethyl),

4-tert-butyl-2-chloro-phenyl-N-methyl-O-methylaminophosphate (Crufomat), dimethyl-p- (methylthio) phenylphosphate,

O, O-dimethyl-O- (3-methyl-4-methylmercaptophenyl) thiophosphate (Fenthion).

isopropylamino-O-ethyl-O- (4-methylmercapto-3-methylphenyl) phosphate,

O, O-diethyl-O-p - [(methylsulfinyl) phenyl] thiophosphate (Fulfulfon),

O, O-dimethyl-O-p-sulfamidophenyl thiophosphate,

O- [p- (dimethylsulfamido) phenyl] -O, O-dimethylthiophosphate (Famphur),

O, O, O‘, O‘-tetramethyl-O, O‘-thiodi-p-phenylenediophosphate,

O-p- (p-chlorophenylazophenyl) -0,0-dimethylthiophosphate (Azothoat),

O-ethyl-S-phenylethyldithiophosphonate,

O-ethyl-S-4-chlorophenylethyldl thiophosphonate,

O-isobutyl-S-p-chlorophenylethyldithiophosphate,

O, O-dlmethyl-S-p-chlorophenylthiophosphate,

O, O-dimethyl-S- (p-chlorophenylthiomethyl) dithiophosphate,

O, O-diethyl-p-chlorophenyl mercaptomethyldithiophosphate (Carbophenothion),

O, O-diethyl S-p-chlorophenylthiomethylthiophosphate,

O, O-dimethyl-S- (carboethoxyphenylmethyl) dithiophosphate (Phenothoat),

O, O-diethyl-S- (carbofluoroethoxyphenylmethyl) dithiofate,

O, O-dimethyl-S- (carbisopropoxyphenylmethyl) dithiophosphate,

0,0-dimethyl-O- (α-methylbenzyl-3-hydroxycrotonyl) phosphate,

2-chloro-1- (2,4-dichlorophenyl) vinyldiethyl phosphate (Chlorfenvinphos),

2-chloro-1- (2,4,5-trichlorophenyl) vinyldimethylphosphate,

O- [2-chloro-1- (2,5-dichlorophenyl) vinyl] -0,0-diethyithiophosphate, phenylglyoxyionitriloxim-0,0-diethylthiophosphate (Phoxim),

O, O-diethyl-O- (3-chloro-4-methyl-2-oxo-2-H-1-benzopyran-7-yl) thiophostate (Coumaphos),

O, O-diethyl-7-hydroxy-3,4-tetramethylenecoumarinylthiofate (Coumithoat),

2,3-p-dioxarithiol-S, S-bis (Ο, Ο-diethyldithiofate) (Dioxathion),

2-methoxy-4-H-1,3,2-benzodioxaphosphorine-2-sulfide,

O, O-diethyl 1-O- (5-phenyl-3-isoxazoilyl (number)] thiophosphate,

S - [(6-chloro-2-oxo-3-benzoxazolinyl) methyl] -1,2'-diethyldithiofate (Phosalon),

2- (diethoxyphosphinylimino) -4-methyl 1-2,3-dithiolane,

O, O-dimethyl-S- [2-methoxy-1,3,4-thiadiazole-5- (4H) -onyl- (4) -methyl] dithiophosphate, tris (2-methyl-1-aziridinyl 1) - phosphonoxide (Metepa),

O, O-dimethyl-S-phthalimidomethyldithiophosphate,

S- (2-chloro-1-phthalimidoethyl) -0,0-diethyldithiophate,

N-hydroxynaphthalimidodiethylphosphate, dimethyl 3,5,6-trichloro-2-pyridylphosphate,

O, O-dimethyl-O- (3,5,6-trichloro-2-pyridyl) thiophosphate,

O, O-diethyl-O- (3,5,6-trichloro-2-pyridyl) thiophosphate,

O, O-diethyl-O-2-pyrazinylthiophosphate (Thionazinl),

O, O-diethyl-O- (2-quinoxylyl) thiophosphate,

O, O-dimethyl-S- (4-oxo-1,2,3-benzotriazin-3 (4H) -ylmethyl) dithiophosphate (Azinphosmethy 1),

O, O-diethyl-S- (4-oxo-1,2,3-benzotriazin-3 (4H) -ylmethyl) dithiophosphate (Azinphosethyl),

S - [(4,6-diamino-s-triazin-2-yl) methyl] -1,2'-dimethyldithiophosphate (Menazone),

S- [2- (ethylsulfonyl) ethyl] dimethylthiophosphate (Dioxydemeton-s-methyl), diethyl 1-S- [2- (ethylsulfinyl) ethyl] dithiophosphate (Oxydisufotone), bis-O, O-diethylthiophosphoric anhydride ( Sulfotep), dimethyl 1,3-di (carbomethoxy) -1-propen-2-yl phosphate, dimethyl (2,2,2-trichloro-1-butyroyloxyethyl) phosphonate (Butonat),

O, O-dimethyl-O- (2,2-dichloro-1-methoxy vinyl) phosphate,

O, O-dimethyl-O- (3-chloro-4-nitrophenyl) thiophosphate (Chlorthion),

O, O-dimethyl-O- (or S) -2- (ethylthioethyl) thiophosphate (Demeton-s-methyl), bis- (dimethylamido) fluorophosphate (Dimefox),

2- (0,0-dimethylphosphorylthiomethyl) -5-methoxypyrrone-4,

3,4-dichlorobenzyltriphenylphosphanium chloride, dimethyl N-methoxymethylcarbamoylmethyldithiophosphate (Formocarbam),

O, O-diethyl-O- (2,2-dichloro-1-chloroethoxy vinyl) phosphate,

O, O-dimethyl-O- (2,2-dichloro-1-chloroethoxyvinyl) phosphate,

O-ethyl-S, S-diphenyldithiophosphate,

O-ethyl-S-benzylphenyldithiophosphonate,

O, O-diethyl-S-benzylthiol phosphate,

O, O-dimethyl-S- (4-chlorophenylthiomethyl) dithiophosphate (Methylcarbophenothion),

O, O-dimethyl-S- (ethylthiomethyl) dithiophosphate, diisopropylaminofluorophosphate (Mipafox),

O, O-dimethyl-S- (morpholinylcarbamoylmethyl) dithiophosphate (Morphothion), bismethylamidophenyl phosphate,

O, O-dimethyl-S- (benzenesulfonyl) dithiophosphate,

0,0-dimethyl-S and O-ethylsulfinylethylthiophosphate,

O, O-diethyl O-4-nitrophenyl phosphate,

O, O-diethyl-S- (2,5-dichlorophenylthiomethyl) dithiophosphate (Phendapton), triethoxyisopropoxy-bis- (thiophosphinyl) disulfide,

O, O-diethyl-O- (4-methylcoumarinyl-7) thiophosphate (Potasan),

2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-oxide, octamethylpyrophosphoramide (Schradam), bis (dimethoxythiophosphinesulfonyl) phenylmethane,

5-amino-bis (dimethylamido) phosphin-3-phenyl-1,2,4-triazole (Triamiphos),

N-methyl-5-O, O-dimethylthiolphosphoryl) -3-thiavaleramide (Vamidothion) and

N, N, N‘, N‘-tetramethyldiamidofluorophosphate (Dimefoxj.

Carbamic acid derivatives

1-naphthyl-N-methylcarbamate (Carbaryl),

2-butynyl-4-chlorophenylcarbamate,

4-dimethylamino-3,5-xylyl-N-methylcarbamate,

4-Dimethylamino-3-tolyl-N-methylcarbamate (Aminocarb)

3.4.5-trimethylphenyl N-methylcarbamate, i

2-chlorophenyl N-methylcarbamate (CPMC),

5-chloro-6-oxo-2-norbornecarbonitrile-O- (methylcarbamoyl) oxime,

1- (dimethylcarbamoyl) -5-methyl-3-pyrazolyl-N, N-dimethylcarbamate (Dimetilan),

2,3-dihydro-2'-dimethyl-7-benzofuranyl-N-methylcarbamate (Carbofuran),

2-methyl-2-methylthiopropionaldehyde-O- (methylcarbamoyl) oxime (Aldicarb),

8-quinaldyl-N-methylcarbamate and its salts, methyl 2-isopropyl-4- (methylcarbamoyloxy) carbanilate, m- (1-ethylpropyl) phenyl-N-methylcarbamate,

3,5-di-tert-butyl-N-methylcarbamate, m- (1-methylbutyl) phenyl-N-methylcarbamate,

2-isopropylphenyl-N-methylcarbamate,

2-sec-butylphenyl-N-methylcarbamate, m-tolyl-N-methylcarbamate,

2,3-xylyl-N-methylcarbamate,

3-Isopropylphenyl N-methylcarbamate

3-tert-butylphenyl-N-methylcarbamate,

3-sec-butylphenyl-N-methylcarbainate,

3-Isopropyl-5-methylphenyl-N-methylcarbamate (Promecarb)

3,5-diisopropylphenyl-N-methylcarbamate,

2-chloro-5-isopropylphenyl-N-methylcarbamate,

2-chloro-4,5-dimethylphenyl-N-methylcarbamate,

2- (1,3-dioxolan-2-yl) phenyl-N-methylcarbamate (Dioxacarb),

2- (4,5-dimethyl-1,3-dioxolan-2-yl) phenyl-N-methylcarbamate,

2- (1,3-dioxan-2-yl) phenyl-N-methylcarbamate,

2- (1,3-dithiolan-2-yl) phenyl-N-methylcarbamate,

2- (1,3-dithiolan-2-yl) phenyl-N, N-methylcarbamate,

2-Isopropoxyphenyl N-methylcarbamate (Arprocarb)

2- (2- (propinyloxy) phenyl-N-methylcarbamate)

2- (2-propynyloxy) phenyl-N-methylcarbamate,

3- (2-propynyloxy) phenyl-N-methylcarbamate,

2-dimethylaminophenyl N-methylcarbamate,

2-diallylaminophenyl N-methylcarbamate,

4-diallylamino-3,5-xylyl-N-methylcarbamate (Allyxicarb)

4-Benzothienyl-N-methylcarbamate

2,3-dihydro-2-methyl-7-benzofuranyl-N-methylcarbamate,

3-methyl-1-phenylpyrazol-5-yl-N, N-dimethylcarbamate,

1-Isopropyl-3-methylpyrazol-5-yl-N, N-dimethylcarbamate (Isolan)

2- (N, N-dimethylcarbamoyl) -3-methylpyrazol-5-yl-N, N-dimethylcarbamate,

2-dimethylamino-5,6-dimethylpyrimidin-4-yl-N, N-dimethylcarbamate,

3-methyl-4-dimethylaminomethylenimino-phenyl-N-methylcarbamate,

3-dimethylaminomethylenimino-phenyl-N-methylcarbamate,

1-Methylthioethylimino-N-methylcarbamate (Methomyl)

2-methylcarbamoyloxyimino-1,3-dithiolane,

5-methyl-2-methylcarbamoyloxyimino-1,3-oxathiolane,

2- (1-methoxy-2-propoxy) phenyl-N-methylcarbamate,

2- (1-butin-3-yloxy) phenyl-N-methylcarbamate,

3-methyl-4- (dimethylaminomethylmercaptomethylenimino) phenyl-N-methylcarbamate,

1,3-bis (carbamoylthio) -2- (N, N-dimethylamino) propane hydrochloride,

5,5-dimethylhydroresorcindimethylcarbamate,

2- (propargylethylamino) phenyl-N-methylcarbamate,

2- (propargylmethylamino) phenyl-N-methylcarbamate,

2- (dipropargylamino) phenyl-N-methylcarbamate,

3-methyl-4- (dipropargylamino) phenyl-N-methylcarbamate,

3,5-dimethyl-4- (dipropargylamino) phenyl-N-methylcarbamate,

2- (allyl isopropylamino) phenyl) -N-methylcarbamate a

3- (allyl isopropylamino) phenyl-N-methylcarbamate.

Chlorinated hydrocarbons γ-hexachlorocyclohexane [Gammexan, Lindan, γHCH],

1.2.4.5.6.7.8.8-octachloro-3a, 4,7,7a-tetrahydro-4,7-methylenindane [Chlordane],

1.4.5.6.7.8.8-heptachlor-3a, 4,7,7a-tetrahydro-4,7-methylenindane (Heptachlor),

1,2,3,4,10,10-hexachloro-1,4,4a, 5,8,8a-hexahydroendo-1,4-exo-5,8-dimethanonaphthalene (Aldrin),

1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a, 5,6,7,8,8-octahydro-exo-1,4-endo-5,8 - dimethanonaftalen (Dieldrin),

1.2.3.4.10.10-hexachloro-6,7-epoxy-1,4,4a, 5,6,7,8,8a-octahydroendoendo-5,8-dimethanonaphthalene (Endrin),

6.7.8.9.10.10- hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-methano-2,3,4-benzo [o] -dioxathiepen-3-oxide (Endosulfan), chlorinated camphor (Toxaphen), decachloroctahydro-1,3,4-metheno-2H-cyclobutan [ed] pentalen-2-one, dodecachloroctahydro-1,3,4-metheno-1H-cyclobutan [ed] pentalene (Mirex), ethyl-1 , 1a, 3,3a, 4,5,5,5 ', 5a, 6-decachloroctahydro-2-hydroxy-1,3,4-metheno-1H-cyclobutane [cd] pentalen-2-levulinate, bis (pentachloro- 2,4-cyclopentadlen-1-yl), dinocton, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane (DDT), dichlorophenyldichloroethane (TDE), di- (p-chlorophenyl) trichloromethylcarbinol (Dicofol), ethyl 4,4'-dichlorophenyl glycolate (Chlorobenzylate), ethyl 4,4'-dibromobenzylate (Brombenzylate), isopropyl 4,4'-dichlorobenzylate, 1,1,1-trichloro-2, -bis (p methoxy-phenyl) ethane (methoxychlor) diethyldifenyldichlorethan, dekachlorpentacyklo- (3,3,2,0 ^2,6, 0 ^3,9, 0 ^7,10) decan-4-one (Chlordecone).

Nitrophenols and their derivatives

Sodium 4,6-dinitro-6-methylphenolate (dinitrocresol),

Dinitrobutylphenol 2,2 ‘, 2 '-triethanolamine salt,

2-cyclohexyl-4,6-dinitrophenol (Dinex),

2- (1-methylheptyl) -4,6-dinitrophenyl crotonate (Dinocap),

2-sec-butyl-4,6-dinitrophenyl-3-methylbutenoate (Binapacryl),

2-sec-butyl-4,6-dinitrophenylcyclopropionate a

2-sec-butyl-4,6-dinitrophenylisopropyl carbonate (Dinobuton).

Various substances

Sabadilla,

Rotenon,

Cevadin,

Veratridine.

Ryania,

Pyrethrin,

3-Allyl-2-methyl-4-oxo-2-cyclopenten-1-yl-thirysanthemumate (Allethrin)

6-chloropiperonylchrysanthemumate (Barthrin),

2,4-dimethylbenzylchrysanthemumate (Dimethrin),

2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate, (5-benzyl-3-furyl) methyl 2,2-dimethyl-3- (2-methylpropanyl) cyclopropanecarboxylate, nicotine,

Bacillus thuringiensis Berliner, dicyclohexylcarbodiimide, diphenyldiimide,

4-chlorobenzyl-4-chlorophenyl sulfide (chlorobenside), creosote oil,

6-methyl-2-oxo-1,3-dithiolo- [4,5-b] quinoxaline (Quinomethionate), (1) -3- (2-furfuryl) -2-methyl-4-oxocyclopent-2 -enyl [I] - (cis + trs) chrysanthemum monocarboxylate (Furethrin),

2-pivaloylindan-1,3-dione (Pindon),

2-Fluoroethyl (4-bisphenyl) acetate

2-fluoro-N-methyl-N- (1-naphthyl) acetamide, pentachlorophenol and its salts,

2,2,2-trichloro-N- (pentachlorophenyl) acetimidoyl chloride,

N- (4-chloro-2-methylphenyl) -N, N-dimethylformamidine (Chlorphenamidine),

4-chlorobenzyl-4-fluorophenyl sulfide (Fluorobenside),

5,6-dichloro-1-phenoxycarbonyl-2-trifluoromethylbenzimidazole (Phenozaflor), tricyclohexyl stannate,

2-thiocyanatoethyl laurate, 3-butoxy- t -thiocyanatodiethyl ether, isoboronothiocyanatoacetate, p-chlorophenyl-p-chlorobenzenesulfonate (Ovex),

2,4-dichlorophenylbenzenesulfonate, p-chlorobenzenesulfonate (Fenson), p-chlorophenyl-2,4,5-trichlorophenylsulfone (Tetradifon), p-chlorophenyl-2,4,5-trichlorophenylsulfide (Tetrasul), methyl bromide, p-chlorophenylphenylsulfone, p -chlorobenzyl-p-chlorophenyl sulfide (chlorobenside),

4-chlorophenyl-2,4,5-trichlorophenylazosulfide,

2- (p-tert-butylphenoxy) -1-methylethyl-2-chloroethylsulfite,

2- (p-tert-butylphenoxy) cyclohexyl-2-propynylsulfite,

4,4‘-dichloro-N-methylbenzenesulfonjanilide,

N- (2-fluoro-1,1,2,2-tetrachloroethylthio) methanesulfonanilide,

2-thio-1,3-dithiolo- (4,5-6) quinoxaline (Thioquinox), chloromethyl-p-chlorophenylsulfone,

1,3,6,8-tetranitrocarbazole and prop-2-ynyl- (4-t-butylphenoxy) cyclohexylsulfite (Propargil).

Esters of chrystanthemum mono- and dicarboxylic acids

3- (2,4-Pentadienyl) -4-oxo-2-cyclopenten-1-ylchrysenthemumate,

3- (12,2-Butenyl) -4-oxo-2-cyclopenten-1-ylchrysanthemumate,

3-allyl-2-methyl-4-oxo-2-cyclopenten-1-ylchrysanthemumate,

6-chloropiperonylchrysanthemumate,

2,4-dimethylbenzylchrysanthemumate,

2,3,4,5-tetrahydrophthalimidomethylchrysanthemumate, (5-benzyl-3-furyl) methylchrysanthemumate, methyl 1-3- (2,4-, pentadienyl) -4- (oxo-2-cyclopenten-1-yl) chrysanthemum dicarboxylate and methyl 3- (2-butenyl) -4-oxo-2-cyclopenten-1-ylchrysanthemum dicarboxylate.

The present invention provides an insecticidal composition comprising an insecticidally active compound selected from the group consisting of insecticidally active carbamates, organophosphorus compounds and pyrethroids, and benzylpropionylether of formula (Ia),

X

IF when X is hydrogen,

Y and Z taken together are methylenedioxy, with the proviso that when both X and Y are hydrogen, Z is other than nitro.

Preferred are benzyl propionyl ethers in which all X, Y and Z are chlorine atoms, and especially compounds containing these chlorine atoms in 2,3,4; 2,3,6 a

2,4,5 configurations.

The lethality of the insecticidal compounds, in particular the carbamates, is synergistically increased by the addition of the benzyl 2-propionyl ethers of the formula Ia

X

CH-O-CH-CHCW f / aJ where

X, Y and Z are hydrogen, nitro or chloro or when X is hydrogen,

Y and Z taken together are methylenedioxy, with the proviso that when both X and Y are hydrogen, Z has a different meaning from that of the nitro group.

Examples of these benzyl-2-propynyl ethers are shown in Table I and their synergistic activity with indecticidally active carbamates is illustrated in Example 6.

where

X, Y and Z are hydrogen, nitro or chloro, or

Table I

Compound No. X Y OF II-A H H 4-CI II-B H 2-C1 4-CI II-C H 3-C1 4-CI II-D 2-C1 3-C1 4-CI II-E 2-C1 3-C1 6-C1 II-F 2-C1 4-CI 5-C1 II-G H 3,4-CH2O2 II-H H 2-C1 6-C1 II-I H 2-NO2 3-C1 II-J H 2-NO2 4-CI II-K H 2-NO2 6-C1 II-L H 3-NO2 2-C1 II-M H 3-NO2 4-CI II-N H 4-NO2 2-C1 II-O H 4-NO2 3-C1

The lethality of the insecticidally active organophosphates and cyclopropanecarboxylic acid esters is synergistically increased by the addition of 2-propynyl ethers of the general formula

R = CH2-O-CH2-C == CH where

R is an aromatic hydrocarbon radical selected from the group consisting of naphthyl and radicals of the formula

X

where

X, Y and Z are hydrogen, nitro, and niobo halogen, except iodine.

Examples of benzyl-2-propynyl ethers include compounds II-A to II-F and II-H to II-O and compounds listed in Table II.

Preferred insecticides are carbamates, especially those

1-naphthylmethylcarbamate (carbaryl),

4-benzo (b) henyl-N-methylcarbamate (Mobam),

3-methyl-1-phenyl-5-pyrazolyl-N-methylcarbamate (pyrolan),

1- (Dimethylcarbamoyl) -5-methyl-3-pyrazolyldimethylcarbamate (Dimetilanj, o-isopropoxyphenylmethylcarbamate (Baygon))

8- (2-Methylquinolyl) -N-methylcarbamate (GS 13798) a

3,5-diisopropylphenylmethylcarbamate (HRS 1422).

Preference is also given to phosphoric acid derivatives, in particular

O, O-dimethyl-S- [2-methoxy-1,3,4-thiadiazole-5- (4H) -onyl- (4) -methyl] dithiophosphate (GS 13005),

O, O-diethyl-O- (2-isopropyl-4-methyl-6-pyrimidyl) phosphorothioate (Diazinone),

2-chloro-1- (2,4,5-trichlorophenyl) 18 vinyldimethylphosphate (Gordona); and

3-hydroxy-N, N-dimethyl-cis-crotonamide dimethyl phosphate (bidrin).

Table II

Compound i i. R II-P (2-NO2) C6H4— II-Q (4-NO2) C6H4- II-R a-CioH7—

The preparation of these compounds is illustrated in the following example.

Example 1

Compounds II-A to II-F are prepared according to literature procedures (JP Guermont, Mem. Ser. Chim. Eitat (Paris, 147 (1955) and I. Marszak, G. Diament and JP Guermont, Mem. Ser. chim. e'tat (Paris) 35, 67 (1950) To a solution of 0.23 g (0.10 mol) of sodium metal dissolved in 90 ml of propynyl alcohol is added with stirring 0.01 mol of the appropriate benzyl halide. The reaction mixture is poured into 100 ml of water and the oil layer is extracted into ether. The ether layer is separated, washed with water, 10% sodium hydroxide solution, saturated sodium chloride solution, dried (Na 2 SO 4) and concentrated in vacuo, compounds II-A, II-B and II-C were distilled under reduced pressure and compounds II-D, II-E and II-F recrystallized to 95% Compound II-H can be prepared similarly using the corresponding benz ylhalide.

Compound II-R was prepared similarly, but purified by silica gel chromatography eluting with benzene.

Compounds II-P and II-Q are prepared as follows:

A mixture of 1.38 g (0.01 mol) of anhydrous potassium carbonate, 0.01 mol of the appropriate benzyl halide and 1.38 g of propynyl alcohol is dissolved in 100 ml of acetone and the solution is refluxed for 24 hours. The reaction mixture was poured into 100 mL of water and the oil layer was extracted with ether. The ether layer was separated, washed with water. 10% sodium hydroxide solution, saturated sodium chloride solution, dried (Na 2 SO 4) and concentrated in vacuo. Compound II-P is distilled under reduced pressure, Compound II-Q is recrystallized from 95% ethanethol.

Compound II-G was prepared by a modified procedure for the preparation of compounds II-P and II-Q. Instead of propynyl alcohol 3,4-methylenedioxybenzyl alcohol is used and instead of benzyl halide propynyl bromide is used. The crude oily compound II-G was dissolved in hot hexane and the starting material, methylenedioxybenzyl alcohol precipitated during cooling. The solution was filtered and the filtrate was concentrated in vacuo. The residue is chromatographed on a silica gel column and eluted with benzene.

2-Propynylchlorobenzyl ethers, compounds II-I to Π-O, inclusive, are prepared as follows: A solution of 5% (w / v) sodium propylate in propynyl alcohol is prepared by reacting sodium metal or sodium hydride with anhydrous propynyl alcohol. To 170 ml of the sodium propylate / propylalcohol mixture was added 0.1 mol of chloronitrobenzyl bromide or chloronitrobenzyl chloride, and the mixture was stirred at room temperature for 5 hours and then refluxed until essentially free of benzyl halide (1-2 hours). Most of the propynyl alcohol was distilled off under reduced pressure, 100 ml of water were added to the residue, and the mixture was extracted with ether or benzene. The organic layer was separated, washed with saturated sodium chloride, dried (Na 2 SO 4) and subjected to fractional distillation. The corresponding chloronitrobenzyl-2-propynyl ether obtained is identified by infrared and nuclear magnetic resonance spectra.

Yields, melting points, boiling points, analyzes and spectral data are shown in Tables III, IV and V.

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The melting points given in the previous example were measured on a Fischer Johns instrument. Melting points and boiling points are uncorrected. Infrared spectra were obtained on a Perkin-Elmer 137 grid spectrophotometer. Nuclear magnetic resonance spectra were obtained on a Varian A-60 and Varian A-60A NMR spectrophotometer, at 38 degrees Celsius, with signals relative to the tetramethylsilane internal standard. both nuclear magnetic resonance and infrared spectra were taken in carbon tetrachloride. Thin layer chromatography was performed on sillkagel G coated glass plates. Column chromatography was performed on neutral alumina (Woelmj activity grade I. The yields are based on the isolated product and were not improved by further processing of the by-products.

The efficacy of the synergists of the invention is likely to be highly dependent on their ability to interfere with or inhibit the effect of mixed functional oxygenase (MFO). Said enzyme is contained in insects and in many cases can at least metabolize insecticides to relatively harmless products that do not act lethal. Consequently, the synergistic effect of any particular synergistic agent in combination with any insecticidally active agent is dependent not only on the effectiveness of the synergist in inhibiting MFO metabolism, but also on the degree to which the particular insecticide is subject to detoxification by MFO metabolism.

For example, the insecticide 'Carbaryl' has a relatively low lethality for a common housefly, since it is easily subject to the metabolism of MFO into harmless insect products. The synergistic substances of the invention are therefore very effective in increasing the lethality of Carbaryl. On the other hand, the insecticide "Dimetilan" is relatively lethal to the housefly, and although its effect can be greatly enhanced by the synergistic substances of the invention, the increase in lethality is lower (and consequently the degree of synergism is lower) than that of Carbaryl.

The synergistic mixtures of the insecticidally active carbamates with the compounds of the invention usually have the effect that the combination has the same lethality as the substantially higher dose of the insecticide itself. This also applies to the insecticidally active chrysantemum mono and dicarboxylic acid esters.

Combining synergistic compounds with insecticidally active organic phosphorus compounds in many cases results in increased lethality. In some cases the lethality does not change and in some cases it even drops. Based on current knowledge, this decrease in lethality can be explained, in particular in the case of some phosphorothioates or -dithioates, by the fact that at least some MFO metabolites of these insecticides are more lethal to insects than the parent compounds and derivatives by metabolism of MFOs By inhibiting or interfering with MFO metabolism, the resulting effect is likely to have a greater effect on inhibition of metabolic potency enhancement than inhibition of metabolic detoxification.

Where pure synergy is observed in conjunction with organophosphates as insecticides, the magnitude of the metabolic potency enhancement is either small or less important than metabolic detoxification. No effect of the synergistic agent can be explained either by the balance of metabolic enhancement of efficacy with detoxification, or by the absence of inhibition of either.

The following examples illustrate the increased lethality of insecticidally active carbamates, organic phosphorus compounds, and pyrethrum insecticide when used in conjunction with the above-described propynyl compounds of the invention.

Insecticidal compositions of the invention comprising one of the above insecticidally active compounds and one of the propynyl synergists of the invention may contain about 0.1 to about 10 parts by weight of the synergistic compound per part by weight of the insecticidally active compound. Preferably, the ratio is at least about 0.5 parts by weight of the synergist per weight. part insecticide.

The insecticidal compositions of the invention may be used in a variety of ways and may be mixed with other substances, such as vehicles, carriers and excipients, the nature of which depends on the routes of administration. Thus, for example, the active ingredients, i.e. the insecticide and the synergistic substance, can be used in the form of a powder. In this case, these substances are mixed with solid carriers such as clays, for example, fuller clay, bentonite, talc, diatomaceous earth or diatomaceous earth. Carriers other than clay may also be used, for example lignin by-products, wood meal or walnut shell meal.

For use as a liquid spray, the active ingredients may be dispersed or dissolved in a liquid carrier. Various commonly known carriers can be used, such as water, hydrocarbon solvents of various types, lower ketones, alcohols, and mixtures thereof, provided that the carriers used are inert to the active ingredients.

In some cases the desired emulsion or dispersion of active ingredients ^one in liquid carrier. Such systems can be prepared by mixing the active ingredients in a carrier. Surfactant emulsifiers or dispersants such as fatty alcohol sulphates such as sulphonated castor oil or alkyl benzene sulphonates, soaps such as sodium oleate and nonionic surfactants such as high molecular weight alkyl polyglycol ethers can be used as excipients for this purpose. These emulsifiers and dispersants usually have wetting properties.

The compositions of the invention may also contain adjuvants such as wetting and wetting agents.

The compositions of the invention, also containing carriers and various excipients, can be prepared by conventional methods and usually contain about 2 to about 20% by weight. of active ingredients (i.e. synergists and insecticides), although it is of course also possible for the market to produce concentrates containing about 10 to 80% of the active ingredients, which are then diluted by the user himself. It is understood that the compositions of the present invention may also be used in aerosol containers, in which case the propellant is not included in the above proportions. The propellant content of the aerosol formulation is usually 25 to 95% based on the total weight.

Example 2

Synergistic effect of mixtures of insecticidally active carbamates with 2-propynyl ethers

The synergistic effect of compounds II-A to II-H in conjunction with carbaryl and pyrolan was found. It is operated using a method using containers with an insecticide film. The test insects are 5 days old domestic birds of the Wilson strain, sex-independent, for which no insecticide pre-selection was performed. Insecticide and synergistic compound solutions were prepared in acetone at a concentration of 1 mg / ml. An appropriate combination of insecticide and synergist diluted with 3 ml of acetone was placed in a 0.57 liter wide-necked glass vessel and a film of the test system was formed on the vessel walls after evaporation of the acetone by rolling the vessel. The flies are transferred to the vessel after anesthesia with carbon dioxide and kept in the vessel at room temperature. The container is covered with perforated aluminum foil, which also holds a piece of cotton with a 10% sugar solution soaked. The number of dead flies is determined at intervals, but the reported mortality is related to the total result over 24 hours. All tumbled stagnant flies are considered dead. The "contact synergistic ratio" (SR), which is the ratio of the LC 50 of the Insecticide itself to the LC 50 of the insecticide used together with the synergistic, is then determined. The insecticide LC 50 value was determined from a logarithmic plot of% mortality versus dose used.

The LC 50 of carbaryl alone is 1.0 mg per flask for a Wilson strain, in the assay described above, for pyrolan itself, the LC 50 is 0.15 mg per flask. The LC 50 of the combination of insecticide and synergist is determined at a 5: 1 weight ratio of synergist to insecticide. The results are shown in Table VI:

Compound number

Table VI

Contact Synergy Ratio Carbaryl Pyrolan

II-A 50 II-B 50 II-C 100 ALIGN! II-D 200 II-E 120 II-F 150 II-G 100 ALIGN! II-H 300

The effect of compounds II-C, II-D and II-E with dimetilane and GS 13 798 was determined by multi-agent resistant CH strain testing of domestic strains. The flies are cooled and a 2: 1 acetone solution of the synergistic substance and insecticide is applied to the dorsal portion. After treatment, the flies are transferred to a plastic petri dish with cotton soaked in a solution of sugar in water. The mortality in% after 24 hours, calculated as the average of both assays, is shown in Table VII. If equal doses of insecticide without synergistic agent are used, the mortality is 10 to 40%.

In Table VII and the following tables, dosages of topically applied insecticides and synergists are expressed in micrograms per fly ((Ug / fly) unless otherwise stated).

Insecticide dose:

Dose of synergistic agent: 10

Table VII

Diraetilan

GS 13 798 1 2 synergistic compound no

II - C 0

II-D

II-E 10

100 92

100 100

100 100

The synergistic effect of benzyl-2-propynyl ethers in conjunction with the insecticide 'mobam' is determined by tests on flies IN / WHO strain and Rutgers A. three- to five-day female housefly anesthetized with carbon dioxide contained the required dose. After treatment, the flies are sealed in 10 to 3-5 gypsum petri dishes, where they are kept for 24 hours to determine mortality. Place the cotton wick with reconstituted cream in the dishes. % mortality at 24 hours for the IN / WHO strain is shown in Table VIII, for the Rutgers A strain in Table IX.

Table VIII

Dose

"Mobamu": A dose of sy- 0 0.20 0.20 0.10 0.10 0.05 0.05 riergické Substances: 1.0 0 1.0 0 0.50 0 0.25 Synergic compound number II-C - « 2 99 0 27 Mar: 0 4 II-D 0 2 100 ALIGN! 0 50 0 10 II-E 0 2 100 ALIGN! O 33 0 5 II-H 10 25 100 ALIGN! II-I 7 '25 97 II-J 13 25 100 ALIGN! II-K 10 25 100 ALIGN! II-L 3 25 89 1I-M 10 25 90 II-N - 12 97 II-O 10 25 60

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The effect of varying the dose of insecticide and the ratio of synergistic agent to insecticide is further illustrated for combinations of synergistic compounds II-D, II-E, II-F and Mohan insecticide in Tables X, XI, and XII. Table X shows the mortality in the housefly IN / WHO housefly hours following topical application of the Mobam insecticide, both with and without the synergistic substance II-D. Table XI shows mortality using the synergistic compound II-E and Table XII using the synergistic compound II-F.

Table X

Synergistic to insecticide ratio: Alone insecticide 0.5 / 1 '1/1 2/1 5/1 Dose insecticide 1.0 73 97 100 ALIGN! 100 ALIGN! 100 ALIGN! 0.50 33 57 100 ALIGN! 97 100 ALIGN! 0.25 7 30 63 83 97 0.13 0 7 17 - 50 Table XI Synergy ratio Alone . 0.5 / 1 1/1 2/1 5/1 '- insecticide substances insecticide Dose insecticide 1.0 93 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 0.50 83 97 97 93 100 ALIGN! 0.25 27 Mar: 53 77 73 67 0.13 - 30 27 Mar: 17 40 Table XII Synergy ratio Alone 0.5 / 1 1/1 2/1 5/1 Insecticide substances: insecticide Dose insecticide 1.0 93 100 ALIGN! 93 93 100 ALIGN! 0.50 83 70 83 80 97 0.25 27 Mar: 33 57 27 Mar: 73 0.13 - 3 10 0 23 The data in Table X shows that amount Mobamu and II-D, is achieved insecticide (1.0 µg / fly) which did not LD100 already at 0.5 µg. provides satisfactory control (LD73) Synergistic effect of compound II-K in provides this 1 control when it will be used in insecticide Dimetilan, Pyrolan, Bay- mixtures with 0.5 µg synergist (LD97). When gon and HRS 1422 is illustrated by mortality data a combination of the same shall be used after 24 hours at Table XIII, XIV, and XV. Table XIII Dose of Dimetilane Dimetilan itself Dimethilane with 5 parts of compound II-K 0.25 100 ALIGN! _ 0.13 43 100 ALIGN! 0,063 17 70 0,031 0 7

Table XIV Pyrolan itself

Pyrolan with 5 parts of compound II-K

A dose of Pyrolan

5.0 43 - 2.5 10 - 1.3 3 - 0.63 0 - 0.25 - 80 0.13 - 40 0,063 - 7 Table XV Synergistic effect of various benzyl-2-propynyl ethers listed in Tables I and II in Insecticide 0.125 with insecticide Diazinon and GS 13 005 se Baygon itself 0 by testing topical application on my- Baygon with 5 parts compound Our IN / WHO strains, Rutgers A and II-K 83 not CH, multi-drug resistant, HRS 1422 0 using the procedure described in Example 2. HRS 1422 with 5 parts % mortality after 24 hours in strain IN / of compound II-K 77 / WHO are shown in Table XVI, ^for Rutgers A in Table XVII and CH in T- Example 3 bulce XVIII. The same dose of insecticide alone applied to the CH strain Synergistic effect of benzyl-2-propynyl- causes a mortality of 10 to 40%. in conjunction with insecticidal phosphorus compounds effective orga-

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Example 4

Synergistic effect in combination with insecticide Mobam and GS 13 005 in male Russian russia

Synergistic effect of compounds. II-H and II-K in conjunction with moban is illustrated; mortality data after 24 hours in male Russian blatella (Blatella Germanicus). The results are shown in Table XXI. The synergistic substance and the insecticide are each dissolved in acetone and the mixture is applied in the form of small droplets to the insect thorax. The same doses of only the synergistic substance have no insecticidal activity.

0.12

0.60 (a)

Table XXI

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Dose of synergist: O

Synergistic compound no.

II-H 10

II-K 10 control experiment (b) - control experiment (c) -

100 &

a) The synergistic agent was applied 2 hours before the insecticide was administered.

b) At the time of administration of the synergistic substance as well as at the time of the insecticide administration, the insect is only coated with acetone.

(c) Insects not treated

The synergistic effect in conjunction with the insecticide GS 13,005 of the compounds of the invention II-H, II-K, II-P, II-Q and II-R is illustrated by the 24 hours Russian domestic mortality data presented in Table XXII. The same doses of the synergistic alone provide zero mortality.

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Table XXII

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b) prior to administration of the insecticide.

At the time of administration of the synergistic agent as well as at the time of administration of the insecticide, the insects were only coated with acetone.

Insects not treated.

thrum was determined by topical application to a resistant CH-strain of the housefly as described in Example 2. Mortality in% after 24 hours is shown in Table XXIII. After application of the insecticide alone, the mortality is 10-40%.

Example 5

Synergy of the insecticide Pyrethrum

Table XXIII

Pyrethrum insecticide dose: 0

Dose of synergistic substance:

Synergistic compound no.

II-C o

II-D 0

II-E 10

The average percentages of% of dead CH strain as a function of time after spraying with the insecticide Pyrethrum alone and after spraying its mixtures with the synergistic agent are shown in Table XXVI. The assays are performed 2X using 50 CH strain flies per test. Solutions are prepared, each containing 100 mg and 200 mg of Pyrethrum, respectively, in 1 ml of acetone

200 mg of a synergistic agent and a mixture of 100 milligrams of Pyrethrum and 100 mg of a synergistic agent. 50 flies of CH strain were placed in a 40 L spray chamber and sprayed with 1 ml of test solution into the chamber with a spray gun. A solution containing 200 mg of the synergistic substance per ml does not cause any mortality.

Table XXIV

198113 O what cm c * s id CO 00 Ó) 50 CM CD CO CO 00 05 40 00 CM bs U0 00 4 30 F-T | 1 ffl co co m F Minutes 25 cm oin · ........................... co co in 20 May in o * cx co xr vn r-f Tfl Tf rH τ — 1 O 1—1 co 0) CM ID co co in '(8 O PH & 0 t-1 / H Sxtť d O O O o i — l and Dose mg / ml Pyrethrui o o o o o o c i-1 CM τ — 1 Synergic substance II-E

The selectivity of the synergistic compounds of the present invention is illustrated by the results of a test in which sleep duration is prolonged and the results of an acute toxicity test performed on the satin beds of Swiss albino white mice.

Example 6

Prolongation of sleep caused by administration of a barbiturate and non-barbiturate type depressant in admixture with a synergistic agent

The effect of various synergistic compounds on sleep time after administration of sodium secarbarbital (Secarbarbital) and 3,3-diethyl-5-methyl-2,4-dioxypiperidine (Noludar) was determined. Control experiments are also carried out in which no synergistic substance is administered. About 38 days old male mice weighing 25 to 30 grams are used as test animals. The synergistic substance is administered in a dose

74.0 mg / kg (dilution 2.0 mg / 0.1 ml corn oil), at a dose of 110.0 mg / kg (dilution 3.0 mg / 0.1 ml oil j. Secobarbital is given at a dose of 37, 0 mg / kg (dilution 1.0 mg / 0.1 ml water) and Noludar at a dose of 110.0 mg / kg (dilution 3.0 mg / 0.1 ml water) The synergist is administered one hour before Secobarbital or The sleep times of Secobarbital and Noludar mice, both alone and in conjunction with the synergistic agent, are determined as the time elapsing from administration of the substance to recovery of the upright reflex, i.e., the time of regaining consciousness, when the animal is able to climb up The relative sleep time (RSj, which is defined as the ratio of prolonged sleep time in treated mice (synergistic substance - (- drug) to the sleep time of control mice (drug only)) is also determined. of treated mice and RS shown in Table X XV.

Table XXV

Secobarbital (37 mg / kg)

Noludar (110 mg / kg)

Synergic substance 110 mg / kg Relative time sleep Synergic Medium time sleep (min,) substance (74 mg / kg) Synergistic substance Synergic compound C. Medium time sleep (min) Relative time sleep 110 mg / kg Medium time sleep (min) Relative time sleep II-C 33 1.0 - - 50. 1.3 II-D 60 1,2 - 46 1.0 II-E 44 1.4 - - 45 1.1 II-P 46 1.0 - - 38 1.3 II-H 51 2.1 44 1.4 68 2.2 II-I 32 1.3 31 1,2 56 1,8 II-J 30 1.4 27 Mar: 1.0 70 2.2 II-K 44 2 48 1.5 75 : 2,4 II-L 42 1,8 31 1.0 56 1,8 II-M 47 2 29 1.0 47 2.1 II-N 39 1.7 20 May 1.0 58 1.9 II-O 26 1.1 - 52_ 2.4 II-P 46 1.0 -  ; -: 44 Ť. 1.5 II-Q 73 1.6 30 1.1 41 2.1 II-R 96 1.6 35 1,2 49 1.7 Lesoxane - 8.3 - 6.1 - 3.1 Example 7 dinu after administration of the same dose of ki alone

chicken oil.

Table XXVI

Synergistic effect of compounds of the invention on acute toxicity of Dimetilane, GS 13 005, Secobarbital and Methadone.

To determine the acute toxicity of Dimetilane alone, 8 male Swiss albino white mice were each dosed with Dimetilane ranging from 4 to 32 mg (a total of 8 different doses, 8 mice each). Mice of about 23 to 27 go age 5 to 6 weeks are used. The number of dead mice 48 hours after administration of Dimetilane (lethality) is shown in Table XXVI. Dimetilane is administered intraperitoneally in 0.1 ml corn oil for 1 hour Dimethilane dose (mg / kg _: Lethality)

4.0. 0

8,0 0

12,0 1

16,0 3

20,0 4

24.0 7

28,0 8

32,0 8 i

In the tests for the synergistic effect of the compounds of the invention on acute toxicity, a dose of 8 mg / kg of dimetilane is considered to be just below that at which dimetilane itself is lethal to mice.

To determine the acute toxicity of the synergists alone, each mouse of a group of 8 animals is dosed intraperitoneally with 1000 mg / kg of the synergist. The number of dead animals after 72 hours is shown in the left column of Table XXVII.

The synergistic effect of the various compounds of the invention on the acute toxicity of Dimetilane is determined by testing in male Swiss albino white mice aged 5-6 weeks weighing 23-27 g. All compounds are administered by intraperitoneal injection into the lower abdomen. The snyergic is administered in 0.1 ml corn oil one hour before the insecticide is administered. Each dose of synergist is administered to 8 mice each. Mice are monitored for a minimum of 6 hours after intraperitoneal administration while being individually maintained in a glass jar. Mice are weighed and food and water are introduced into observation vessels. Control mice are administered 0.1 ml of corn oil at the time of administration of the synergistic substance to test mice and 0.1 ml of corn oil + Dimetiiah at the time of insecticide administration to the test mice. The number of dead mice after 48 hours is shown in Table XXVII.

Table XXVII

Dimetilane dose (mg / kg): 0 8

Synergistic dose (mg / kg): 1000 240

Synergistic compound no.

II-D 0

II - E II - F II - H 0

II-I -

II-J

II-K: 1

------------- ----------- II-L ----------------------- - II-M 'II-N

II - O - II - P ^: 2

II - Q 7

II-R -

Sesoxane 1 control (0.1 ml oil) 0 attempt -

- -

0

0

0

0 .5 ............; . ____________O

0

0

0 -

-

0

8

0

In the same way, the synergistic effect of the compounds of the invention on GI is determined. 13005, Secobarbital and 6-dimethylamino-4,4

diphenyl-3-heptanone (Methadone). The lethality is given in Table XXVIII.

Dose of insecticide or drug (mg / kg); Synergy dose (mg / kg): Table XXVIII Methadone 32 215 GS 13005 71 213 Secobarbital 90 215 Synergistic compound no. II-D 3 1 2 II-H 7 0 4 n-J 6 0 3 II-K 3 1 2 II-P 6 0 0 II-Q 6 - - Sesoxane 0 6 5 control experiment 5 (a) 0 (b) 2 (c)

(a) GS 13005 (71 mg / kg) in 0,1 ml corn oil.

(b) Secobarbital (90 mg / kg) in 0,1 ml corn oil.

(c) Methadone (32 mg / kg) in 0,1 ml corn oil.

Claims (13)

P R E D Μ Ε Τ An insecticidal composition comprising an insecticidally active compound selected from the group consisting of insecticidally active carbamates, organophosphorus compounds and pyrethroids, and a benzylpropinylether of formula (Ia), X CH £ CHjrCžCH ^O-Z (wherein laj X, Y and Z are hydrogen, nitro or chloro, or when X is hydrogen, Y and Z taken together are methylenedioxy, with the proviso that when both X and Y are hydrogen, Z is other than nitro. 2. An insecticidal composition according to claim 1, wherein the insecticidal active compound is an insecticidally active carbamate. 3. An insecticidal composition according to claim 2, wherein said insecticidally active carbamate is present 1-naphthyl-N-methylcarbamate, 4-benzo (b) -thienyl 1-N-methylcarbamate, 3-methyl-1-phenyl-5-pyrazolyl-N-dimethylcarbamate, 1- (dimethylcarbamoyl) -5-methyl-3-pyrazolyldimethylcarbamate, o-isopropoxyphenylmethylcarbamate, 3,5-diisopropylphenylmethylcarbamate and / or 8- (2-Methylquinolyl) -N-methylcarbamate. ynAlezu 4. An insecticidal composition according to claim 2 comprising a compound of formula (Ia) wherein X is hydrogen, Z is chloro, and Y is nitro. 5. An insecticidal composition according to claim 2 comprising a compound of formula (Ia) wherein X, Ϋ and Z are hydrogen and / or chlorine. 6. An insecticidal composition according to claim 2, wherein the benzylpropinylether of formula (Ia) is 2-nitro-6-chlorobenzyl-2-propynyl ether. 7. The insecticidal composition of claim 1, wherein said insecticidally active compound comprises an insecticidally active organic phosphorus compound. 8. An insecticidal composition according to claim 7, wherein the insecticidally active organic phosphorus compound comprises O, O-dimethyl-S- [2-methoxy-1,3,4-thiadiazole-5 (4H) -onyl- (4)]. -methyl] dithiophosphate, O, O-diethyl O- [2-isopropyl-4-methyl-6-pyrimidyl) thiophosphate, 2-chloro-1- (2,4,5-trichlorophenyl) vinyl dimethyl dimethyl phosphate or / and 3-hydroxy-N, N -dimethyl-cis-crotonamide dimethyl dimethyl phosphate. 9. An insecticidal composition according to claim 7, wherein the compound of formula (Ia) wherein X is hydrogen, Z is chlorine and Y is nitro. 10. An insecticidal composition according to claim 7 comprising a benzylpropinylether of formula (Ia) wherein X, Y and Z are hydrogen and / or chlorine. 11. An insecticidal composition according to claim 8, wherein the benzylproipinylether of formula (Ia) is 2-nitro-6-chlorobenzyl-2-propynyl ether. 12. An insecticidal composition according to claim 1, wherein the insecticidally active compound is Pyrethrum. 13. An insecticidal composition according to claim 12 comprising a benzylpropinylether of formula (Ia) wherein X, Y and Z are hydrogen or chlorine. Severography, n. P., Plant 7, Most