GB1585219A

GB1585219A - Insecticidal and acaricidal agents

Info

Publication number: GB1585219A
Application number: GB36550/77A
Authority: GB
Original assignee: F Hoffmann La Roche AG
Current assignee: F Hoffmann La Roche AG
Priority date: 1976-09-02
Filing date: 1977-09-01
Publication date: 1981-02-25
Also published as: SE7709863L; NL7709452A; FI772511A; JPS5352623A; FR2363283A1; BE858327A; DE2738361A1; MC1163A1; LU78067A1; IT1086007B; AU2830377A; FR2363283B1; NZ185047A; DK390677A; NO773034L

Description

(54) INSECTICIDAL AND ACARICIDAL AGENTS (71) We, F. HOFFMANN-LA ROCHE & CO., AKTIENGESELL SCHAFT, a Swiss Company, of 124-184 Grenzacherstrasse, Basle; Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention is concerned with insecticidal and acaricidal agents and a process for the manufacture thereof. The invention is also concerned with a method for the control of insects by means of said agents.

The insecticidal and acaricidal agents provided by the present invention contain the compound of the formula

and one or more compounds which synergise this compound of formula I in its insecticidal or acaricidal activity.

There has been found a wide range of different compounds which synergise the compound of formula I either alone or in admixture with other compounds in its insectidal activity. Important groups of such synergists are: a) Methylenedioxy compounds, especially 1,3-methylenedioxybenzenes which can carry one or more substituents.

Preferred methylenedioxy compounds of this type are those of the general formula

wherein R1 represents a hydrogen or halogen atom or a lower alkyl, lower alkoxy, lower alkenyl, lower alkynyl or nitro group and R2 represents a hydrogen atom or a lower alkenyl, lower alkoxy, di-lower alkylamino or lower alkoxy-lower alkyl group, a poly-lower alkenoxy group containing 3 to 6 oxygen atoms in the chain, which can be straight-chain or branched-chain and which contains at least 4 carbon atoms, a poly-lower ethylenoxycarbonyl group containing 2 to 6 oxygen atoms in the chain, which can be straight-chain or branched-chain and which contains at least 4 carbon atoms, or a lower alkyl-sulphoxy-lower alkyl group or R1 and R2 together with the carbon atoms to which they are attached form a saturated 6-membered ring which can include one or two oxygen atoms and which can be substituted by one or two propylcarboxyl groups and/or lower alkyl groups.

Preferred methylenedioxy compounds of formula II are, for example, Acetaldehyde [2- ( 2-ethoxyethoxy) -3,4-methylenedioxyphenyl] acetal, piperonal-bis- [2-(2'-n-butoxyethoxy)ethyl1 acetal, 4- ( 3,4-methylenedioxyphenyl) -5-methyl- 1,3-dioxan, 4-nitro- 1 ,2-methylenedioxybenzene, 4-methoxy-5-nitro-1,2-methylenedioxybenzene, 4-dimethylamino-5-nitro- 1,2-methylenedioxybenzene, 4-dimethylamino-5-nitro-1,2-methylenedioxybenzene, 6-bromo-4-ethoxymethyl-1,2-methylenedioxybenzene, 4- ( 1-ethoxy-2-nitropropyl) - 1,2-methylenedioxvbenzene, Mryisticin (5-allyl-1-methoxy-2,3-methylenedioxybenzene).

and 4,5-methylenedioxybenzoic acid 2- ( 2-butoxyethoxy) -ethyl ester.

Other suitable methylenedioxy compounds are 5,6,7,8-tetrahydro-7-methyl- naphtho(2,3-d) 1,3-dioxol-5,6-dicarboxylic acid dipropyl ester, and 1,2-methylenedioxynaohthalene.

Especially preferred methylenedioxy compounds are: α-[2-(2-Butoxvethoxy)-ethoxyl-4,5-methylenedioxy-2-propyltoluene and 1,2 methylenedioxy-4- (2-octylsulphinyl-propyl) -benzene.

b) Propynyl ethers, especially propynyloxyphenyl, propynyloxybenzyl and pro pynyloxynaphthyl ethers which carry one or more substituents.

Preferred propynyl ethers are those of the general formula

wherein n stands for zero or 1, g3 represents a hydrogen or halogen atom or a nitro group and R4 and R, each represent a hydrogen or halogen atom or and - R, together with the carbon atoms to which they are attached form an unsaturated 6-membered ring and X represents the group -CH2- or M=CH-, in the latter case the nitrogen atom being linked with the oxygen atom.

Especially preferred propynyl ethers are: 2-Nitro-4-chlorophenyl 2-propynyl ether, 2,4,5-trichlorophenyl 2-propynyl ether, l-naphthyl 2-propynyl ether, 2-nitrobenzyl 2-propynyl ether, a-naphthylmethyl 2-propynyl ether, 2,6-dichlorobenzyl 2-propynyl ether, 2,4-dichlorobenzaldoxamine-2-propynyl ether, l-naphthaldoximine 2-propynyl ether and 2-nitrobenzaldoximine 2-propynyl ether.

c) Thiocyanates, especially substituted methylenethiocyanates such as, for example: p-Nitrobenzylthiocyanate, isobomylthiocyanate, laurylthiocyanate and 2,4-dichlorobenzylthiocyanate.

d) Phthalimides and tetrahydrophthalimides such as, for example, N - (2 - ethyl hexyl) - 5 - norbornene - 2,3 - dicarboximide, N - (2 - butylhexyl) - (1 - methyl4 - iso propyl - 5 - norbornene) - 2,3 - dicarboximide and N - (4 - pentynyl)phthalimide.

e) Polychlorodialkyl esters such as, for example, 3,3'-hexachloro-2,2'-dichlorodipropyl ether.

f) Arylpropynylphosphoric acid esters, especially phenylpropynylalkylphosphoric acid esters such as, for example, propyl-2-propynylphenylphosphonate and isobutyl2-propynylphenylphosphonate.

As used in this specification, the term "lower alkyl" means a straight-chain or branched-chain alkyl group which contains up to 6 carbon atoms. Especially preferred lower alkyl groups are the methyl and ethyl groups. The lower alkyl moieties of the lower alkylamino and lower alkoxy groups likewise contain up to 6 carbon atoms.

Preferred lower alkyl moieties in these groups are methyl and ethyl. The terms "lower alkenyl" and "lower alkynyl" mean alkenyl and alkynyl groups resnectively which contain up to 6 carbon atoms. The term "halogen" means fluorine, chlorine, bromine and iodine unless specifically indicated to the contrary.

The compound of formula I is novel. It can be prepared by reacting 2,2-dimethyl4-hydroxy-1,3-benzodioxol of the formula

with à compound of the general formula

wherein Z represents a chlorine, bromine or iodine atom, in the presence of a base.

The reaction of the compound of formula IV with a compound of formula V is carried out according to methods known per se, conveniently in the presence of an excess of a compound of formula V. The reaction is conveniently carried out in an inert organic solvent such as a hydrocarbon (e.g. benzene or toluene), a chlorinated hydrocarbon (e.g. methylene chloride), an ether (e.g. diethyl ether) and the like.

Examples of bases which can be used are potassium carbonate, sodium carbonate, triethylamine, pyridine and the like. The temperature and pressure are not critical, the reaction being preferably carried out at a temperature between about 0 C and the reflux temperature of the reaction mixture, preferably at between room temperature and 130"C.

In detail, the compound of formula I can be prepared as follows: 5 g of sodium hydride (5OC/o dispersion in oil) are washed our twice with petroleum ether and then suspended in 75 ml of absolute benzene in a four-necked round flask. There are added nortionwise while stirring 16.6 g (0.1 mol) of 2,3 (isopropylidenedioxy)phenol and the mixture is stirred at room temperature for 30 minutes. There are then added dropwise 26.7 g of freshly prepared N-trichloromethylthio-N-methylcarbamic acid chloride in 20 ml of benzene over a period of 1 hour.

The mixture is stirred at room temperature for 4 hours under a nitrogen atmosphere.

The mixture is poured into 200 ml of ice-water and extracted three times with benzene.

The benzene extract is washed twice with water, dried over sodium sulphate, filtered and evaporated. There is obtained 23-(isopropvlidenedioxy) - phenyl - methyl [(trichloromethylZthiolcarbamate in the form of yellow crystals which melt at 880-- 89"C after recrystallisation from high-boiling petroleum ether.

It has been shown that the insecticidal activity of the compound of formula I is substantially increased by combination with synergists in accordance with the present invention. The insecticidal properties of the compound of formula I are thereby improved not only quantitatively but also qualitatively. The insecticidal and acaricidal agents provided by the present invention produce a more rapid knock-down and a more rapid and greater lethality, so that it is henceforth possible to control insects with greater effectiveness than hitherto. Moreover, the present insecticidal and acaricidal agents display complete activity also against resistant insect strains. A particular advantage of the present insecticidal and acaricidal agents is the relatively slight toxicity to warm blooded animals, especially to mammals.

The relative proportions of the active ingredients of the insecticidal and acaricidal agents provided by the present invention can vary within wide limits depending on the intended use, the mode of use, the insects to be controlled and other factors. It is, however, convenient to use 0.1-10 parts by weight of synergist to one part by weight of the compound of formula I. A ratio of 1:1 parts by weight is preferably used.

The total concentration of the active ingredients in the ready-for-use insecticidal and acaricidal agents depends on the form in which they are used and the mode of use. The present insecticidal and acaricidal agents can be used in the form of concentrates, granulates or, together with carriers, in the form of sprays, aerosols or powders. For certain purposes it can be advantageous to use emulsions, suspensions or solutions which contain emulsifying or wetting agents. As solid carrier materials there come into consideration, for example, chalk, talc, bentonite, kaolin, diatomaceous earth, siliceous earth, Fuller's earth, limestone, gypsum, powders and dusts from organic waste products etc.

The invention is also concerned with a process for the manufacture of insecticidal and acaricidal agents as hereinbefore defined, which process comprises mixing the compound of formula I with one or more compounds which synergise this compound of formula I in its insecticidal activity and inert carrier material.

In general, the insecticidal and acaricidal agents provided by the present invention can be manufactured according to the procedures which are described, for example, in Farm Chemicals, volume 128, page 52 et seq.

The insecticidal and acaricidal agents provided by the present invention can also contain other additives such as emulsifiers or masking agents and/or also other known substances having insecticidal activity The insecticidal and acaricidal agents provided by the present invention can be made up in the form of concentrates which are suitable for the storage and the transport. Such concentrates can contain, for example, 590% of the combination of active ingredients. The concentrate can be diluted with the same or a different carrier material to provide concentrations which are suitable for practical use. In a ready-for-use agent there can be present, for example, active ingredient concentrations of 2-75 per cent by weight, preferably 5-50 per cent by weight. The active ingredient concentration can, howeverj also be lower or higher.

The insecticidal and caraicidal agents provided by the present invention can be used against insects, ticks and mites according to the usual methods such as, for example, by contact or by intake with the food. The agents are active against the widest variety of insects; for example, against Diptera, especially against representatives of the families Muscidae, Culicidae, Simuliidae, Tabanidae, Calliphoridae, Oestridae, Ceratopogonidae such as, for example, Musca spp., Stomoxys calcitrans, Haematobia irritans; Culex spp., Anopheles spp. and Aedes spp.; Simulum spp.; -Tabanus spp.; Cochiomyia hominivorax, Lucilia spp. and Calliphora spp.; Hypoderma spp.; Culicoides spp.; Leptoconops spp.; Lepidoptera such as, for example, Plodia interpunctella, Ephestia kuehniella, Cadra cautella; Sitotroga cerealella, Heliothis virescens; or Coleoptera such as Sitophilus granarius, Sitophilus oryzae, Oryzaephilus surinamensis, Oryzaephilus mercator, Tribolium confusum, Tribolium castaneum, Tribolium audax, Rhizopertha dominica, Trogoderma variabile; or Orthoptera such as Blattella germanica, Blatta orientalis, Periplaneta americana, Nauphoeta cinerea; or Hemiptera such as Rhodnius prolixus, Cimex spp; or Homoptera such as Myzus persicae; Psylla spp.; Diaspididae such as, for example, Aonidiella aurantii, Coccidae such as, for example, Saissetia coffeae, Pseudococcidae such as, for example, Planococcus citri; or Anoplura such as, for example, Haematopinus spp., Linognathus spp. and Pediculus humanus subspp; or Diphonaptera such as, for example, Xenopsylla cheopis, Ctenocephalides spp. In addition, the agents are also active against various other Arthropods (e.g. against ticks and mites).

It will be appreciated that the present invention also includes within its scope a method for providing a locus subject to or subjected to attack by pests free from such attack, which method comprises, applying to said locus an effective amount of an agent provided by the present invention.

The following Examples illustrate biological tests carried out with various combinations against test insects and the results- thereby obtained: The structural formulae and nomenclature of the compounds mentioned in the Examples are as follows: Carbamate:

2,3-(Isopropylidenedioxy) phenylmethylt(trichloro- methyl)thio]carbamate Synergists:

2-Nitro-4-chlorophenyl 2-propynyl ether a-[2-(2-Butoxyethoxy)- -ethoxy]-4,5-methylenedioxy-2-propyltoluene (Piperonyl butoxide) N-(2-Ethylhexyl)-5-norbornene-2,3-dicarboximide MGK 264) D CCl3-CHCl-CH2-O-CH2-CHCl-CCl3 3,3'-Hexachloro-2,2' -dichloro-dipropyl ether (S 421)

1,2-Methylenedioxy-4-(2 -octylsulphinylpropyl) -benzene (Sulphoxide) Commercial insecticides:

2,3-Isopropylidenedioxyphenylmethylcarbamate (Bendiocarb) O,O-Dimethyl-S- (2-oxo-3- -aza-butyl)-dithiophosphate (Dimethoat) Commercial insecticides:

O,O-Diethyl-O-3,5,6- -trichloro-2-pyridyl -monothiophosphate (Chlorpyrifos) 1,1,1-Trichloro-2,2- -di(chlorophenyl)ethane (DDT) 2- (1, 3-Dioxolan-2-yl) - phenyl methylcarbamate (Dioxacarb) S- [1,2-di (ethoxycarbonyl) ethyl] -0,0-dimethyl- -dithiophosphate (Malathion) Example 1.

Test insect: Musca domestica, common house fly.

Test method: (Simple adulticide test).

Petri dishes (diameter 90 mm) are treated with a solution of the preparation in acetone. Ten 4-5 day old female flies of a multiresistant strain are Dlaced on each petri dish and incubation is carried out at 250C and 60 / relative humiditv. Untreated petri dishes and petri dishes treated with acetone are used as the controls. The duration of the test is 24 hours. The results are expressed as the percentage reduction in the survival rate of the flies in comparison with the controls.

Active Dosage Dosage ingredient rg/cm2 Synergist /lg/cm2 % activity 1 10 - - 24 1 - - 0 - - A 10 13 - - B 10 0 - - C 10 18 - - E 10 0 I 0.01 A 0.01 100 I 0.1 B 0.1 100 0.01 0.01 15 I 0.1 C 0.1 100 0.01 0.01 5 I 1 E 1 100 0.1 0.1 75 0.01 0.01 0 F 1 - - 75 0.1 - - 35 0.01 - - 5

The mortality in the controls is 2%.

Example 2.

Test insect: Musca domestic, common house fly, Test method: (Persistence test on surfaces which are customary in practice, for example in cattle sheds).

Two plates each of gypsum or concrete (area 70 cm2) are treated with a preparation formulated as a wettable powder with sugar addition (formulation usually used in practice, see Example 13-15) and incubated for the given time span at 26 C and 60% relative humidity. Five 3 day old female flies of a multiresistant strain are placed on each plate and covered with a perforated plastic petri dish. Untreated plates are used as the controls. The evaluation is carried out every 24 hours after the commencement of the test. The results are expressed as the percentage reduction in the survival rate of the flies in comparison to the controls.

Surface: Gypsum

Days after treatment Active Dosage Dosage Formulation 0 7 14 ingredient tlg/cm2 Synergist mg/cm2 (see Example) % activity I 10 A 10 13 100 100 0 6. 10 - - 14 0 0 0 H 10 - - 15 .0 0. 0 Mortality in the controls: 10% 20% 107 Surface: Concrete

Days after treatment Active Dosage Dosage Formulation 0 7 14 ingredient gg/cm2 Synergist llg/cm2 (see Example) % Activity I 10 A 10 13 100 44 0 G 10 - - 14 0 0 0.

H 10 - - 15 30 33 0 Mortality in the controls: 0%. 10% 10% Example 3.

Test insect: Musca domestica, common house fly.

Test method: (Persistence test in ammonia atmosphere as is found under practical conditions in cattle sheds).

Filter paper (100 cm2) is treated with a preparation formulated as a wettable powder with sugar addition (Example 13-15), moistened with 0.5 ml of water and incubated for 6 days in a closed flask (1000 cm8). A small container with 5 ml of 1% ammonia solution is placed in the flask. Subsequently, the filter papers are fitted into large dishes and ten 4 day old female flies of a multiresistant strain are placed in each dish. The dishes are incubated at room temperature. Untreated filter papers are used as the controls. The evaluation is carried out after 1 hour and 4 hours. The results are expressed as the percentage reduction in the survival rate of the flies in comparison to the controls.

Hours after commencement Active Dosage Dosage Formulation 1 4' ingredient gg/cm2 Synergist llg/cm2 (see Example) % Activity I 10 A 10 13 40 100 G 10 - - 14 0 0 H 10 - - 15 10 40 Mortality in the controls: 0% 0% Example 4.

Test insect: Culex fatigans, house mosquito.

Test method: Filter paper (100 cm2) is treated with the preparation formulated as a wettable powder. Yoghurt cartons are lined with the dried filter paper. Ten freshly fed female mosquitoes are placed in each carton, the cartons are closed with Cellophane (trade mark) and incubated at room temperature. Untreated filter papers are used as the controls. The evaluation is carried out 4 hours after commencement of the test. The results are expressed as the percentage reduction in the survival rate of the mosquitoes in comparison to the controls.

Activity Dosage Dosage Formulation ingredient llg/cm2 Synergist llg/cm 2 (see Example) % Activity 1 1 - - 16 37 01 - - 3 A - A 1 18 0 I 1 A 1 17 100 0.1 0.1 0 i 1 - - 19 3 The mortality in the controls is 5% Example 5.

Test in sect: Anopheles stephensi, malaria mosquito.

Test method: Filter paper (100 cm2) is treated with the preparation formulated as a wettable powder. Yoghurt cartons are lined with the dried filter paper. Ten freshly fed female mosquitoes are placed in each carton, the cartons are closed with Cellophane and incubated at room temperature. Untreated filter papers are used as the controls. The evaluation is carried out 4 hours after commencement of the test. The results are expressed as the percentage reduction in the survival rate of the mosquitoes in comparison to the controls.

Active Dosage Dosage Formulation ingredient ug/cm2 Synergist gg/cm2 (see Example) % Activity 1 1 - - 16 41 0.1 - - 6 - - A 1 18 0 1 1 A 1 17 100 0.1 0.1 12 i 1 - - 19 .45 0.1 - - 0 The mortality in the controls is 3%.

Example 6.

Test insect: Blattella germinica, German house cockroach.

Test method: Filter paper roundels (64 cm2) are treated with a solution of the preparation in acetone and fitted into petri dishes. Five male cockroaches are placed in each petri dish and incubation is carried out at 250C and 60% relative humidity. Untreated filter paper and filter paper treated with acetone are used as the controls. The duration of the test is 24 hours. The results are expressed as the percentage reduction in the survival rate of the cockroaches in comparison to the controls.

Active Dosage Dosage ingredient gg/cm2 Synergist gg/cm2 % Activity 1 100 - - 20 10 - - 10 1 - - 0 A - A 100 0 - - D 100 0 1 100 A 100 100 10. 10 100 1 1 0 I 100 D 100 100 10 10 100 1' 1 0 F 100 - - 90 10 - - 40 1 - - 0 J 100 - - 0 The mortality in the controls is 0% Example 7, Test insects: Blattella germanica (B.g.), German cockroach.

Blatta orientalis (B.o.), Oriental cockroach.

Periplaneta americana (P.a.), American cockroach.

Neuphoeta cinerea (N.c.), Grey cockroach.

Test method: Filter paper (200 cm2) is treated with the preparation formulated as a wettable powder. The dry filter papers are fitted into Teflonised Cellophane boxes ("Teflon" is a trade mark). Five adults (mixed female and male) of each cockroach type are placed in each box and incubation is carried out at room temperature. Untreated filter papers are used as the controls. The evaluation is carried out 24 hours after commencement of the test. The results are expressed as the percentage reduction in the survival rate of the cockroaches in comparison to the controls.

Cockroach type Active Dosage Dosage Formulation B.g. B.o. P.a. N.c. ingredient g/cm Synergist zg/cm 2 (see Example) % Activity 1 10 - - 16 20 30 80 0 - - A 100 18 0 0 0 0 1 10 A- 10 17 100 90 100 50 J 10 - - 20 0 0 0 0 Mortality in the controls: 0% 0SO Oqlo. 00

Example 8 Test insect: Rhodnius prolixus, kissing bug.

Test method: Filter paper roundels (64 cm2) are treated with the preparation formulated as a wettable powder and, after drying, fitted into petri dishes. Ten unfed adult bugs are placed in each dish and incubation is carried out at room temperature. Untreated filter papers are used as the controls. The evaluation is carried out 96 hours after the commencement of the test. The results are expressed as the percentage reduction in the.

survival rate of the bugs in comparison to the controls.

Active Dosage ~ Dosage Formulation ingredient llg/cm2 Synergist jig/cm' (see Example) % Activity 1 1 - - 16 20 - - A 10 18 0 I 1 A 1 17 100 0.1 0.1 0 i 1 - - 19 0 The mortality in the controls is 0% Example 9.

Test insect: Tribolium castaneum, red-brown flour beetle.

Test method: Petri dish bases (diameter 90 mm) are treated with a solution of the preparation in acetone. Twenty beetles are placed in each dish and incubation is carried out at 250C and 60% relative humidity. Untreated petri dishes and petri dishes treated with acetone are used as the controls. The duration of the test is 48 hours. The results are expressed as the percentage reduction in the survival rate of the beetles in comparison to the controls.

Active Dosage Dosage ingredient gtg/cm' Synergist {Lg/cm' % Activity 1 1 - - 88 0.1 - - 43 0.01 - - 0 A - A 10 0 - - C 10 0 I 1 A 8 100 0.1 0.8 98 0.01 0.08 18 1 1 C 8 98 0.1 0.8 73 0.01 0.08 5 K 1 - - 60 0.1 - - 15

The mortality in the controls is 2% Example 10.

Test insects: Tribolium castaneum (T.c.), red-brown flour beetle.

Sitophilus granarius (S.g.), common grain beetle.

Sitophilus oryzaec (S. o.), rice beetle.

Oryzaephilus surinamensis (O.s.), saw-toothed grain beetle.

Test method: Filter paper roundels (64 cm2) are treated with a solution of the preparation in acetone and, after drying, fitted into petri dishes (diameter 90 mm). Twenty adult beetles are placed in each dish (one dish for each kind of insect) and incubation is carried out at 260C and 55% relative humidity. Untreated filter paper and filter paper treated with acetone are used as the controls. The evaluation is carried out 24 hours after commencement of the test. The results are expressed as the percentage reduction in the survival rate of the beetles in comparison to the controls.

Test insect Active Dosage Dosage T.c. S.g. S.o. O.s. ingredient slg/cm2 Synergist llg/cm2 % Activity 1 10 - - 45 30 85 1 - - 0 A - A 100 0 0 0 0 1 10 A 10 100 100 100 1 1 93 K 10 - - 23 0 0 1 - 0 K 10 A 10 0 0 0 Mortality in the controls: 7% 3% 2% 5%

Example 11.

Test insect: Myzus persicae, green peach aphid.

Test method: (Simple curative test with sensitive aphid strain).

Pea seedlings are infected with a mixed aphid population. The infected seedlings are treated with a solution of the preparation in acetone and incubated at 200C and 60% relative humidity. Untretaed seedlings and seedlings treated with acetone are used as the controls. The duration of the test is 48 hours. The results are expressed as the percentage reduction in the survival rate of the aphids in comparison to the controls.

Active Dosage Dosage ingredient ag/cm2 Synergist llg/cm2 % Activity 1 10 - - 49 1 - - 4' - - A 10 0 - - B 10 0 - - C 10 0 10 0 I 10 A 10 100 1 1 99' 0.1 0.1 6 1 10 B 10 98 1 1 14' 1 10 C 10 94 1 1 1 I 10 E 10 100 1 1 59 0.1 0.1 2 F 10 - - 12

The mortality in the controls is 3%.

Example 12.

Test insect: Myzus persicae, green peach aphid.

Test method: (Curative test with sensitive and resistant aphid strain).

Chinese mustard is infected with a mixed population of a sensitive aphid strain (strain 1) and a resistant aphid strain (strain 2). The infected plants are sprayed with a spray liquor until the liquor drips off the plants. The incubation is carried out in a climatic cabin at 20 C and 60% relative humidity, with 16 hours day and 8 hours night. Untreated infected plants are used as the controls. The evaluation of the test is carried out after 48 hours. The results are expressed as the percentage reduction in the population in comparison to the controls.

Active Conc. Conc. Formulation Strain 1 Strain 2 ingredient % a.i.* Synergist % a.i. (see Example) % Activity 1 0.01 - - 21 83 25 0:003 - - 29 - - A 0.01 23 0 0 I 0.01 A 0.01 22 100 100 0.003 0.003 94 41 G. 0.0t - - 24 86 3 i 0.003 j - - 19 1

* a.i. active ingredient.

Example 13.

The active ingredient of formula I and the synergist of formula A are formulated for the biological testing as follows: % weight/weight Active ingredient of formula I 5.00% Synergist of formula A 5.00% Silcasil S 1.00% [silicic acid, hydrated, ca 87% SiO2] Kaolin B 24 12.65% [prinipally Al, Si2O5 (OH)4] Tensiofix BCZ 0.20% [sodium lauryl sulphate Tensiofix LX specia! 0.40% [sodium lignosulphate] Orotan (Tamol) 731 (trade marks) 0.50% [sodium salt of a copolymer of diisobutylene and maleic acid anhydride, molecular weight: ca 3000] Texadril 8780 (trade mark) 0.25% [block polymerisate of propylene oxide and ethylene oxide. Ethylene oxide content: 80%; melting point ca500C] Crystalline sugar 75.00% Example 14.

The commercial preparation Sum 8 (trade mark-active ingredient content: 13% dimethoat, Formula G) from Dr. R. Mag AG, Dielsorf, is used for the biological testing.

Example 15.

The active ingredient of formula H (Chlorpyrifos) is formulated for the biological testing as follows: % weight/weight Active ingredient of formula H 10.000% (Chlorpyrifos) Silcasil S 1.250% [silicic acid, hydrated, ca 87% SiO2] Celite 209 (trade mark) 12.87S% [siliceous earth, ca 87% SiO2] Oroton (Tamol) 731 0.625% [sodium salt of a copolymer of diisobutvlene and maleic acid anhvdride, molecular weight ca 3000] Emkalyx-Pluronic L 62 (trade mark) 0.250% [block polymerisate of propylene oxide and ethylene oxide. Erhylene oxide content: 20%. Density: 1.03/250C] Crystalline sugar 75.000 /O Example 16.

The active ingredient of formula I is formulated for the biological testing as follows: % weight/weight Active ingredient of formula I 500 /O Silcasil S 5.0O/o [silicic acid, hydrated, ca 87% SiO2] Kaolin B 24 42.0% [principally Al, Si,O, (OH)4] Tensiofix BCZ 1.0% [sodium lauryl sulphates Tensiofix LX special 2.0% [sodium lignosulphonate] Example 17.

A formulation corresponding to that of Example 16 is prepared, but instead of 50% of active ingredient of formula I there are used 25% of active ingredient of formula I and 25% of synergist of formula A.

Example 18.

A formulation corresponding to that of Example 16 is prepared, but instead of 50% of active ingredient of formula I there are used 50 /O of synergist of formula A.

Example 19.

The commercial prepaartion Dedelo (trade mark-active ingredient content: 73% DDT, Formula i) from Dr. R. Maag AG, Dielsdorft) is used for the biological testing.

Example 20.

The commercial preparation Famid (trade mark-active ingredient content: 50% Dioxacarb, Formula J) from Ciba-Geigy AG, Basle, is used for the biological testing.

Example 21.

The active ingredient of formula I is formulated for the biological testing as follows: grams/litre Active ingredient of formula I 250 Phenylsulphonate CA 25 [calcium dodecylbenzenesulphonate] mixture of calcium alkylarylsulphonate, 100 alkylphenolethoxylate, block polymerisate of propylene oxide and ethylene oxide, solvent consisting of Shellsol A and butanol NMP 300 [N-methyl-2-pyrrolidonel Shellsol AB (trade mark) ad 1000 ml [mixture of mono-, di- and tri(lower alkylbenzenes] Example 22.

A formulation corresponding to that of Example 21 is prepared, but instead of 250 g of active ingredient of formula I there are used 125 g of active ingredient of formula I and 125 g of synergist of formula A.

Example 23.

A formulation corresponding to that of Example 21 is prepared, but instead of 250 g of active ingredient of formula I there are used 250 g of synergist of formula A.

Example 24.

The commercial preparation Perfection (trade mark-active ingredient content: 40% Dimethoat, formula G) from Dr. R. Maag AG, Dielsdorft, is used for the biological testing.

Exampe 25.

A spray powder (wettable powder) containing, for example, 25% 2,3 - isopropylidenedioxy)phenyl - methyl [ (trichloromethyl)thio] carbamate (active ingredient of formula I), 25% 2-nitro-4-chlorophenyl 2-propynyl ether, 5% highly-dispersible silicic acid, 1% sodium lauryl sulphate, 2% sodium lignosulphate (sulphate cellulose waste liquor) and 42% kaloni.

is manufactured by mixing these components and finely milling the mixture in a suitable mill. For the manufacture of the finished spray solution, the powder is stirred up in the desired amount of water.

Spray powders containing all active ingredient mixtures in accordance with the present invention can be manufactured as previously described.

Claims

WHAT WE CLAIM IS:

1. An insecticidal and acaricidal agent containing the compound of the formula

2. An agent according to claim 1, wherein the synergist is a methylenedioxy compound of the general formula

wherein R, represents a hydrogen or halogen atom or a lower alkyl, lower alkoxy, lower alkenyl, lower alkynyl or nitro group and R2 represents a hydrogen atom or a lower alkenyl, lower alkoxy, di-lower alkylamino or lower alkoxy-lower alkyl group, a poly-lower alkylenoxy containing 3 to 6 oxygen atoms in the chain, which can be straight-chain or branched-chain and which contains at least 4 carbon atoms, a poly-lower alkylenoxycarbonyl containing 2 to 6 oxygen atoms in the chain, which can be straight-chain or branched-chain and which contains at least 4 carbon atoms, or a lower alkyl-sulphonyl-lc4wer alkyl group or R1 and R, together with the carbon atoms to which they are attached form a saturated 6-membered ring which can include one or two oxygen atoms and which can be substantially by one or two propylcarboxyl groups and/or lower alkyl groups.

3. An agent according to claim 2, wherein the synergist is acetaldehyde [2 - (2 ethoxyethoxy) - 3,4 - methylenedioxyphenyl] acetal.

4. An agent according to claim 1, wherein the synergistic is 5,6,7,8 --tetrahydro 7 - methvlnaphth(2,3-d) - 1,3 - dioxol - 5,6 - dicarboxylic acid dipropyl ester.

5. An agent according to claim 2, wherein the synergist is piperonal - bis - [2 (2' - n - butoxyethoxy) - ethyl]acetal.

6. An agent according to claim 2, wherein the synergistic is 4 - (3,4 - methylene dioxyphenyl) - 5 - methyl - 1,3 - dioxan.

7. An agent according to claim 1, wherein the synergist is 1,2 - methylenedioxynaphthalene.

8. An agent according to claim 2, wherein the synergist is 4 - nitro - 1,2methylenedioxybenzene.

9. An agent according to claim 2, wherein the synergist is 4 - methoxy - 5nitro - 1,2 - methylenedioxybenzene.

10. An agent according to claim 2, wherein the synergist is 4 - dimethylamino S - nitro - 1,2 - methylenedioxybenzene.

11. An agent according to claim 2, wherein the synergist is 6 - bromo - 4- ethoxymethyl - 1,2 - methylenedioxybenzene.

12. An agent according to claim 2, wherein the synergist is 4 - (1 - ethoxy - 2 nitropropyl) - 1,2 - methylenedioxybenzene.

13. An agent according to claim 2, wherein the synergist is Myristicin ( 5 - allyl1 - methoxy - 2,3 - methylenedioxybenzene).

14. An agent according to claim 2, wherein the synergist is 4,5 - methylenedioxybenzoic acid 2 -(2 - butoxyethoxy) - ethyl ester.

15. An agent according to claim 2, wherein the synergist is ry - [2 - (2 - butoxyethoxy) - ethoxy] - 4,5 - methylenedioxy - 2 - propyltoluene.

16. An agent according to claim 2, wherein the synergist is 1,2 - methylenedioxy - 4 - [2 - (octylsulphinyl) - propyl] - benzene.

17. An agent according to claim 1, wherein the synergist is a propynyl ether of the general formula

wherein n stands for zero or 1, R, represents a hydrogen or halogen atom or a nitro group and R4 and R, each represent a hydrogen or halogen atom or -and R, together with the carbon atoms to which they are attached from an unsaturated 6-membered ring and X represents the group ---CH22- or -N= CH-, in the latter case the nitrogen atom being linked with the oxygen atom.

18. An agent according to claim 17, wherein the synergist is 2 - nitro - 4chlorophenyl 2 - propynyl ether.

19. An agent according to claim 17,-'wnerein the synergist ts 2,4,5 - trichlorophenyl 2 - propynyl ether.

20. An agent according to claim 17, wherein the synergist is 1 - naphthyl- 2 - propynyl ether.

21. An agent according to claim 17, wherein the synergist is 2 - nitrobenzyl 2 - propynyl ether.

22. An agent according to claim 17, wherein the synergist is,, - naphthylmethyl 2 - propynyl ether.

23. An agent according to claim 17, wherein the synergist is 2,6 - dichlorobenzyl 2 - propynyl ether.

24. An agent according to claim 17, wherein the synergist is Z4 -~dichloro- benzaldoximine 2 - propynyl ether.

imine 2 - propynyl ether.

25. An agent according to claim 17, wherein the synergist is 1 - naphthaldoximine 2 - propynyl ether.

26. An agent according to claim 17, wherein the synergist is 2 - nitrobenzaldoximine 2 - propynyl ether.

27. An agent according to claim 1, wherein the synergist is a substituted methylenethiocyanate.

28. An agent according to claim 27, wherein the synergist is p-nitrobenzylthiocyanate.

29. An agent according to claim 27, wherein the synergist is isobornylthiocyanate.

30. An agent according to claim 27, wherein the synergist is laurylthiocyanate.

31. An agent according to claim 27, wherein the synergist is 2,4-dichlorobenzylthiocyanate.

32. An agent according to claim 1, wherein the synergist is a phthalimide or tetrahydrophthalimide.

33. An agent according to claim 32, wherein the synergist is N - (2 - ethylhexyl) - 5 - norbornene - 2,3 - dicarboximide.

34. An agent according to claim 32, wherein the synergist is N - (2 - butylhexyl) - (1 - methyl - 4 - isopropyl - S - norbomene) - 2,3 - dicarboximide.

35. An agent according to claim 32, wherein the synergist is N - (4 - pentynyl)- phthalimide.

36. An agent according to claim 1, wherein the synergistic is a polychlorodialkyl ether.

37. An agent according to claim 36, wherein the synergist is 3,3' - hexachloro2,2' - dichloro - dipropyl ether.

38. An agent according to claim 1, wherein the synergist is an arylpropynylphosphoric acid ester.

39. An agent according to claim 38, wherein the synergist is a phenylpropynylalkylphosphoric acid ester.

40. An agent according to claim 38, wherein the synergist is propyl - 2propynylphenylphosphonate.

41. An agent according to claim 38, wherein the synergist is isobutyl - 2propynylphenylphosphonate.

42. A process for the manufacture of an insecticidal and acaricidal agent, which process comprises mixing the compound of formula I given in claim 1 with one or more compounds which synergise this compound in its insecticidal activity and inert carrier material.

43. A process according to claim 42, wherein there is used a synergist as set forth in any one of claims 2 to 41 inclusive.

44. A method of providing a locus subject to or subjected to attack by pests free from such attack, which method comprises applying to said locus an effective amount of an agent as claimed in any one of claims 1 to 41 inclusive.