ARYL TERPENE ETHERS

The present invention. relates to novel aryl ethers of terpene alcohols, their preparation and their application to combat certain invertebrates.

The novel compounds have the general formula

and C/O2 together form a carbon-carbon bond or a bridge oxygen or each represent a hydrogen atom,

R ^ and Rg each represent a methyl or ethyl radical, and Or zj Z ^ together represent a carbon-carbon bond,

Rj represents hydrogen, alkylcarbonyl containing 2 to 5 carbon atoms in its alkyl portion (for abbreviating tell is:

"Cg- Cpj -alkylcarbonyl"), carbamoyl, a mono-C C ^ - ^-alkyl-carbamoyl, a ^- alcénylcarbamoyle C^-C, Cg-C a ^-alkynyl-carbamoyl or aryl-carbamoyl, and

R ^ a ^ - ^ C C-alkyl-carbonyl, carbamoyl, a mono-C C ^ - ^-alkyl-carbamoyl, a ^- alcénylcarbamoyle Cg-C, a ^ C^-C-alkynyl-carbamoyl or aryl-carbamoyl, or

Rj represents a Cg-C ^-alkyl- earbonyle, carbamoyl, a mono-C C ^ - ^-alkyl-carbamoyl, a Cg-C ^-alkenyl-carbamoyl, a ^ alcynylcarbamoyle Cg-C-or aryl-carbamoyl and

R ^ a hydrogen atom, a-Cg-C ^ alIcyl -carbonyl, carbamoyl, a mono-C G ^ - ^-alkyl- cartamoyle, Cg-C a ^-alkenyl-carbamoyl, a ^ alcynylcarbamoyle C^-C-or aryl-carbamoyl,

or Z and Z ^ ^ are each hydrogen atom, and R and R ^ ^ each represent a hydrogen atom, a Cp-C ^ i-alkyl-carbonyl, carbamoyl,

a mono-C C ^ - ^-alkyl-carbamoyl, a Qg-G^ alkenyl-carbamoyl, a ^ alcynylcarbamoyle C^-O-or aryl-carbamoyl.

The alkyl moiety of the alkyl-carbonyl groups entering the substituents R ^ and R₄ of the formula I as defined is linear or branched and * substituted or unsubstituted.

Of es The optional substituents groups include halogens, such as fluorine, chlorine, bromine or iodine, ^ C^-0 of alkoxy, hydroxy or alkoxy carbonyl containing 2 to 4 carbon atoms in the alkoxy portion.

^ C^-C Examples of groups-alkyl-carbonyl for Rj and R ^, the groups include ethyl-, propyl-, isopropyl-, n-butyl-, isobutyl-, sec butylet tert- butylcarbonyles.

Examples of carbamoyl groups for

C- ETi -CH-. -) =- [...] GH₀

O

-C-NH-CH-C ~ ~ = GH

h

C

2,

CH,

R. and E.

%

and Z_L

R,

R"

A particular importance is to be assigned to the compounds of the formula I in which:

Z. j and together form a carbon-carbon bond or

an oxygen bridge,

each represent a methyl or ethyl group, together form a carbon-carbon bond represents an acetyl radical, propionyl, butyryl, carbamoyl, mono-methyl-carbamoyl, mono-ethyl-carbamoyl or mono- phênyl -carbamoyl and represents a hydrogen atom.

Examples of compounds, include:

(propionyl- 4phénoxy ) -1 dimethyl -3,7- ootadiène 2,6, (propionyl -4 phenoxy) -1 dimethyl -3,7 epoxy -6,7-octene 2, (acetyl -4 phenoxy) -1 dimethyl -3,7-nonadiene 2,6, (acetyl -4 phenoxy) -1 dimethyl -3,7- êpoxy 6,7-nonene 2, (N-methylcarbamoyl -4 phenoxy) -1 dimethyl -3,7-octadiene 2,6, (N-methylcarbamoyl -4' phenoxy) -1 dimethyl -3,7 epoxy -6,7-octene 2, (butyryl -4 phenoxy) -1 dimethyl -3,7-octadiene 2,6, (butyryl -4 phenoxy) -1 dimethyl -3,7 epoxy -6,7-octene 2, (H- éthylcarbamcyl -4 phenoxy) -1 dimethyl -3,7-octadiene 2,6, ( ïf -ethylcarbamoyl -4 phêncxy ) -1 dimethyl -3,7 epoxy -6,7-octene 2, (carbamoyl -4 phenoxy) -1 dimethyl -3,7 epoxy -6,7-octene 2, (carbamoyl -4 phenoxy) -1 dimethyl -3,7-octadiene 2,6, (N- phény 1carbamoy1 -4 phenoxy) ^-dimethyl -3,7-octadiene 2, and 6 (N-phenylcarbamoyl -4 phenoxy) -1 dimethyl -3,7 epoxy -6,7-octene 2.

The preparation of the compounds of formula I are in a manner known per se by the reactions below, preferably using equimolar amounts of the reactants. Meanwhile, if desired, use an excess of one or more of the reactants*

acid acceptor R-j

OH, 3 R,

The reactions 2) and 6), i.e. the conversion of the aryl-terpene ethers into derivatives thereof in 6.7 epoxides, are preferably carried out with cooling in an inert solvent, as a chlorinated hydrocarbon, in the presence-d ' an epoxidizing agent, such as a peracid. On a mole of a peracid, there is mainly forming the epoxy 6,7t due to the steric factor. Epoxidized 6.7 The derivatives may also be obtained by action of the IT-bromo- succiniraide on the product epoxidation, by operating in a mixture of water and a solvent, as tetrahydrofuran, the dimethoxy -1,2 ethane, dioxane or tertiary butanol, preferably with cooling, in homogeneous or heterogeneous phase, then treating the bromohydrin -6,7 thus obtained as intermediate product by an alkaline agent, as a carbonate, a hydroxide, or an alkali alcoholate, preferably derived from sodium or potassium.

Peracids are essentially The mentioned peracids first derived from the alkanes, having one to six carbon atoms, such as peracetic acid, or peracids as acids and aromatic perzbenzoic monoperphthalic, but more particularly the acid métachloro - perbenzcïpas < The reagents for the basic Cv! '. v, j. i, ,-' CLiLyu. - '- iju': ic i dsi. i, vo epoxycié in 6.7 feel mainly carbonates, hydroxides and alkali metal alkoxides*

The conversion according to the equation 4), that is say the reaction of an aliphatic allyl halide nor on the suitable phenol, is preferably carried out in the presence of at least one mole of a alkali or alkali earth carbonate with or without the use of a catalytic amount of an alkali metal iodide, in a solvent such as acetone, methyl ethyl ketone or cyclohexanone, at a temperature between room temperature and the boiling point of the solvent employed. The conversioii may also be accomplished under the action of an alkali hydroxide, in a solvent such as dimethylformamide, dimethylsulfoxide, or the the suifdamne dimethoxy -1,2 ethane, between 0 and 100^e .

In the preparation of the compounds of

formula I, it is formed, following to the use of allyl halides for the synthesis, the set of possible geometric isomers * The compounds are therefore mixtures of the isomers by synthesizing géométriquesengendrés *

In the case where the radical R ^ is a alkylou aryl-carbamoyl, aryl-terpene ether may be achieved either according to the equation 1) from the allylic halide and phenolics, or by reacting a (alkoxycarbonyl -4 phenoxy) ~1 dialkyl -3,7-octa (or [...] -) · diene or a (alkoxycarbonyl -4 phenoxy) -1 dialkyl -3,7 octene (or [...] ℮ η ℮ ) -2, a derivative alkyl (or aryl) amino lithium, in a suitable inert solvent.

It is also possible to reacting a compound (carbamoyl -4 phenoxy) -1 dialkyl -3,7-octadiene 2,6 (or octene -2), or a compound (carbamoyl -4 phenoxy) -1 dialkyl -3,7-nonadiene 2,6 (or [...] ℮ η ℮ -2) in dimethyl-sulfoxide in the presence of an alkali hydroxide, between the ambient temperature and 80^C C, with an alkyl halide, alkenyl or alkynyl to obtain the desired compound, i.e. a (N-alkyl, alkenyl or alkynyl-dialkyl 4 phenoxy-1-3, 7-octadiene 2,6 (or octene -2), or a (N-alkyl, alkenyl or alkynyl -4 phenoxy) -1 nonadien -2,6 (or nonene -2).

the active compounds (I) are useful in

against various animal or plant, in particular insects, mites and nematode plants. Unlike most insecticides, acaricides and nêmatocides known which, by contact effect or by ingestion, kill, paralyze or away from said parasites, the active products of the formula I act on their development.

Therefore, , for example for in-

sects, the driven (for the among hemimetabolous) or insect perfect (for the halométaboles ), and the development of the egg, are prevented, after the generations is thus interrupted so that the animals are killed indirectly, the compounds of the formula I are substantially harmless to warm blooded animals. As other hand they decompose rapidly, their accumulation is impossible.

The novel aryl ethers of terpene alcohols are mainly be used against enemies, specified below, plants, of stored products and the state of health.

Insects orders and families below:

Acrididae Orthoptera

Gryllidés

Blattidés

Isoptera

Hemipterans

Ealotermitidés

Miridés

Piesmidés

Lygaeid Subfamily

Pyrrhocoridés

Pentatomidés

Cimicidés

Héduviidés

Jassidés

Eriosomatidés

Lécaniidés

(e.g. Locusta, Schistocerca)

(e.g. Acheta, Gryllus) (e.g. Blattella germanica. Periplaneta americana, Nauphoeta cinerea)

(e.g. Kalotermes)

(e.g. Distantiella ) (by exempme Piesma )

(e.g. Lygus)

(e.g. Dysdercus )

(e.g. Eurydema )

(e.g. Cimex )

(e.g. Ehodinus )

(e.g. Empoasca)

(e.g. Eriosema)

(e.g. Coccus )

Scarab éidés (e.g. Melolontba ) Lepidopteran Pyralidés (e.g. Diatraea) Phyticidés (e.g. Anagasta ) Pyraustidés (e.g. Pyralis ) Crambidés (example Ohilo panel) Tortricidés (e.g. Pandemis) Galleriidés (example panel Galleria) Lyonetiidés (example Lyonetia panel) Yp. onomeutidés (example Hyponomeuta panel) Piéridés (e.g. Pieris) Plutellidés (for example Plutella) Lymantriidés (e.g. Lymantria) Noctuidés (for example Spodoptera) Diptera Culicidae (e.g. A8des) Simuliidae (e.g. Simulium) Tipulidés (e.g. Chironomus) Acaridés families

Ixodidae

Àrgasidés.

Tétramychidés

Dermanyssidés

Nematodes phytopathogenic, such as Aphelendoides, and Ditylenchoides Meloidogyne.

The compounds of formula I can be used alone, or in combination with suitable carriers, and/or additives. The supports and suitable additives petivent be solid or liquid, and are the same as the products currently used in the corresponding formulation, such as natural products or regenerated, solvents, dispersants, wetting agents, adhesives, thickeners, binders, been., or fertilizers,

: preparing the formulations according to the invention are closed in a manner known by intimately mixing and/or by grinding the active substances (I) with suitable carriers, optionally with the addition of dispersants or solvents, inert towards substances " b active. These may be presented and undergoing used in the following various forms %

Solid formulations: dusting agents, agents d¹ spreading and granules (coated granules, granules impregnated, granules homo^5 genes) 5

Formulationsliquide s:a) active concentrates dispersable water, in the form of wettable powders, pastes, emulsions, b) solutions,

-20 For the preparation of solid formulations, (dusting agents and spreading agent), the active substances are mixed with solid supports. These are for example kaolin, talc, the bowl, the loess, chalk, slaked lime, the powdered limestone, the attaclay, 25 dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, silicates or alumino-potassium aluminosodiques (feldspars and micas), sulfates of calcium or magnesium, magnesia, synthetic resins sprayed, fertilizers, as the sulfate,

50 phosphate had ammonium nitrate and urea, pulverized vegetable products, such as cereal flours, bark, wood, nut of ccques, cellulose powders, extraction residue of plant products, activated carbons, andc ", materials which are used

55 alone or in mixtures.

May be prepared by very simple methods granules by dissolving an active substance (X) in an organic solvent, and then depositing the solution on a mineral support granulate, as the attapulgite, silica, lime 40, the benvenite, etc, the solvent is removed by evaporation.

It is also possible to manufacture of granules

polymer-based. For this purpose, the active compounds are mixed (i) with polymerizable compounds (urea-formaldehyde, eyano -guanidine-formaldehyde, me does lari formaldehyde, etc). Is then performed a polymerization provided, not acting on the substances activas, and forming the granules during gelation. However, more interesting impregnating using the active substances, for example in the form of a solution in a low-boiling solvent, porous pellets prepared separately (urea-formaldehyde, polyacrylonitrile, polyesters, etc,), of given surface area and having a ratio given adsorption/desorption, then remove the solvent. These polymer granules may be in the form of micropellets bulk density preferably between 300 and 600 grams per litre, and be spread by spraying. This can be made for large surfaces cultured, for example by means of aeroplanes or helicopters.

Said granules may also be obtained by compressing ensenfole the support materials with the active substances and additives, followed by milling the resulting product.

May be added to the mixtures of compounds having activity for stabilizing the active substance and/or the body non-ionic, anionic or cationic, for example that improve the adhesion of the active substances to the plants and plant parts (adhesives) and/or improve their wettability (wetting) and their dispersibility (dispersants). Since adhesives may be envisaged for example the following products:

mixtures of olein and lime, cellulose derivatives (methyl-cellulose, carboxymethyl cellulose), ethers hydroxy-ethylene-glycol monoou of di-alkyl phenols comprising 5 to 15 ethylene oxide units per molecule and containing 8 or 9 carbon atoms in the alkyl substituent, lignin-sulphonic acids, their alkali metal salts or alkaline earth metal, polyethylene-glycol ethers (carbowax), polyethoxylation products of fatty alcohols containing from 5, to 20 ethylene oxide units per molecule and containing 8 to 18 carbon atoms in the alkyl portion of the fatty alcohol, the condensation products of ethylene oxide and propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea with formaldehyde and latex products.

Concentrates active substance water-dispersible, i.e. powders slurry (wettable powders), pastes and concentrates for emulsions, are products that can be water-up to any desired concentration. They are comprised of the active substance, of a support, optionally additives having the effect of stabilizing the active substance, of surfactants and anti-foams as well as, if necessary, of solvents.

Powders are obtained slurry (wettable powders), and by mixing and grinding to homogeneity, in appropriate devices, the active substances with dispersants and powdery supports. The supports may be for example those mentioned above with respect to solid formulations. In many instances it is advantageous to use mixtures of different media.

As dispersants may be used, e. g.: condensation products of naphthalene or sulfones sulfone derivatives naphthalene with formaldehyde, condensation products of naphthalene or naphthalenesulphonic acids with the phenol and formaldehyde as well as alkali metal salts, ammonium or alkaline earth metal lignin-sulphonic acid, also of the alkyl-aryl-sulfonates, alkali metal salts and alkaline earth metal of the dibutyl-naphthalene-sulfonic acid, fatty alcohol sulphates, such as salts of sulfuric esters of hexadécanols, or of heptadécanols octadécanols and salts of sulfuric esters of fatty alcohol ethoxylates, the sodium salt of the oléylméthyl - tauride, the ditertiary aeétylèneglycols, dialkyl dilaurylammonium chlorides and alkali metal salts or alkaline earth metal salts of fatty acids.

As antifoaming agents is preferred for example silicones.

Is mixed, is ground, sieving and passes the active substances with the additives indicated above, such that, in the powders slurry, the solid portion has a granularity not exceeding 0.02 to 0.04 mm and that, in the pulps, the granularity is not greater than 0.03 mm.

To prepare emulsions, pastes is used and dispersants, such as those which have been mentioned in paragraphs, organic solvents and water. As solvents may be envisaged for example the following: alcohols, benzene, xylenes, toluene, dimethyl-sulfoxide and mineral oil fractions boiling between 120° and 350.

The solvents are to be substantially odorless, be no phytotoxicity, and be inert towards active substances.

The products according to the invention can also be applied in the form of solutions. To this end the active substance is dissolved (i), or more of these active ingredients, in suitable organic solvents or mixtures of such solvents, or in water. Since organic solvents can be used aliphatic or aromatic hydrocarbons, chlorinated derivatives thereof, alkyl-naphthalenes and mineral oils, alone or in mixture between them.

The content of active substance in the above-described products is between 0.02 and 95% * however in case of application by aircraft or other appropriate system, this content can be up to 99.5 S *.

The active substances (I) can be used according to the formulae © below as examples.

Acrents of powdering.

For the preparation of dusting agents, to 5 respectively to ' (has) and 2 % (b), is used the following products:

a) 5 portions of the active substance and

95 parts of talc;

b) 2 parts of the active substance,

1 part silica dispersion and high

9? parts talc.

The active agents are mixed with the support materials, and the assembly is then ground.

For the preparation of a granulated product to 5

the following products are used:

5 parts of the active substance,

0,25 P ection epichlorohydrin,

0,25 part of a polyglycol cetyl ether, 5.50 parts of a polyethylene-glycol (" Carbovax") 91 and parts of kaolin (grain size: of 0.3 to 0.8

The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone. Alora is added polyethylene glycol cetyl ether and the polyglycol * The solution thus prepared is sprayed onto the kaolin, and acetone is removed by evaporation under vacuum.

For the preparation of powders slurry, respectively to 40 % (a), to 25 C/O (b) and (g) and 10% (d), is used the following products:

a) 40 parts of the active substance,

5 parts sodium lignin- suifonate,

1 part of dibutyl naphthalene sulfonate, sodium 54 parts of silica;

b) 25 portions of the active substance,

4.5 parts lignin- suifonaue calcium,

1,9 part of a mixture of white chalk and hydroxyethyl- eellulcse,

1.5 part of dibutyl naphthalene sulfor ate sodium, 19_} 5 parts of silica,

19.5 parts chalk white and

28.1 parts kaolin;

c) 25 portions of the active substance,

2.5 portions iscoctyl -phenoxy-polyoxy-ethylene ~ éth.aroi, . 1.7 part of a mixture of white chalk and hydrcxy -ethyl- eellulose,

8,3 parts alumina-sodium silicate,

16.5 parts kieselguhr and

46 parts of kaolin;

d) 10 parts of the active substance,

3 parts of a mixture of sodium salts of saturated fatty alcohol sulphates,

5 parts of a condensate formaldéhydeacide naphthalene and

82 parts of kaolin.

The active substances are mixed intimately with the auxiliaries in suitable mixers, then crushed in mills cylinders. The powder obtained gives, with the desired amount of water, a suspension to the desired concentration.

Emulsifiable concentrates .

For preparation of emulsifiable concentrates, respectively to 10% to 25% (a) and (b), is used the following products:

a) 10 parts of the active substance,

3, 4parties epoxidized vegetable oil,

13, of an emulsifier 4parties complex, formed of a fatty alcohol polyglycol, and an alkylaryl sulfonate Ca,

40 parts dlnéthylformaaide and

43.2 xylene 5 parts

b) 25 portions of the active substance,

2,5 portions epoxidized vegetable oil,

10 parts of a mixture and alkylaryl-sulfonates ether fatty alcohol polyglycol,

5 parts of dimethylformamide and

57" 5 parts of xylene.

From thereof, is obtained, by dilution with water, emulsions the desired concentration.

For preparation of applicable liquid

spray, respectively to 5% to 2% (a) and (b), is used the following components:

a) 5 portions of the active substance,

1 part of epichlorohydrin and

94 parts heavy gasoline (boiling point level i 160-190°) level i

b) 2 parts of the active substance,

3 parts of dichloro -4,4 ' diphenyl-trichloroethane and 95 parts kerosene.

These solutions are used at pulvérisâteur under pressure. The solution has) is employed with advantage against aphids on fruit trees and other plants.

EXAMPLE 1;

(Propionyl -4 phenoxy) -1 dimethyl -3,7-octadiene 2,6 (active substance 1).

Solution In charge of 30 g of 4-hydroxy propiophenone and 43.5 g of bromo -1 dimethyl -3,7-octadiene 2,6 in 320 ml of dimethoxy -1,2 ethane, is dropped and stirring, at room temperature and in 7 hours, a solution of 12.8 g potassium hydroxide about 86% in 200 ml of absolute ethanol. The stirred for 12 hours at ordinary temperature, and is heated for one hour at 50°. Is cooled and is separated by filtration potassium bromide precipitate.

The filtrate is concentrated under vacuum. The residue is recovered by the ether, and washed three times with a 10% aqueous potassium hydroxide solution, and finally water. After drying of the solution in the ether to anhydrous sodium sulfate,

the solvent is removed by evaporation under vacuum. Is purified by silica gel chromatography the (propionyl -4

phenoxy) -1 dimethyl -3,7-octadiene 2,6. The eluting agent

OA

is a mixture of ether-hexane ratio 1:4. n^ = 1.5370.

EXAMPLE 2:

(Propionyl -4 phenoxy) -1 epoxy -6,7 dimethyl -3,7-octene 2 (active substance № 2).

In a solution of 17.2. of g (propionyl -4 phenoxy) -1 dimethyl -3,7-octadiene 2,6 in 180 ml of methylene chloride, is dropped in he pulls 3 s at a temperature of 0 °C -2 ° to a solution of 12.3 g chloro perbenzoic acid to 85-3 % about in 120 ml of a methylene chloride-ether mixture (report 9 level i 1), and is stirred 3 hours at 0 °C. The reaction mixture is, with the ether, extended to 3 volumes G °C by potassium hydroxide solution cooled to 0 °C, and washed to ' water to a neutral reaction. After drying of the organic phase over sodium sulfate, the solvent is evaporated under vacuum, and the (propionyl -4 phenoxy) -1 epoxy -6,7 dimethyl -3,7-octene 2 is purified again by adsorption on silica gel. Elution The agent is a mixture of ether-hexane (ratio 1:2) · η ^ " 1.5326 (supercooled solution).

Pentane After crystallization in a melting point of 54-57 ° (mixture of isomers).

EXAMPLE 3:

(N-ethylcarbamoyl -4 phenoxy) -1 dimethyl -3,7-octadiene 2,6 (active substance № 3) ·

In a solution of mono-ethylamide 16.5 g of 4-hydroxy benzoic acid (H. Schonenberger, Arzneimittelforschung 14 p. 324-328 (1964)) and 22-1. g of bromo dimethyl -3,7-octadiene 2,6 in 150 ml of dimethoxy -1,2 ethane, is dropped at room temperature, in 6 hours and stirring, a solution of 6.4 g potassium hydroxide about 86% in 100 ml of absolute ethanol. The stirred 16 hours at room temperature " is separated by filtration potassium bromide precipitate, the filtrate is concentrated under vacuum, the residue is taken up by the ether and washed 3 times with 10% potassium hydroxide solution to to 0 °, and then 3 times with water. After drying

of the ethereal solution on anhydrous sodium sulfate, the solvent is removed and dried to bottom the vacuum residue.

Therefore, 1 * (N-ethylcarbamoyl -4 phenoxy) -1 dimethyl -3,7-octadiene 2,6, which is converted into (Hence he-ethyl-carbamoyl -4 phenoxy) -1 epoxy -6,7 dimethyl -3,7 and en. e-2 o as described in the following example.

EXAMPLE 4:

(N-ethylcarbamoyl -4 phenoxy) -1 epoxy -6,7 dimethyl -3,7-octene 2 (active substance [...] ° 4),

A solution of 15.5 In S of (H-ethyl-carbamoyl -4 phenoxy) -1 dimethyl -3,7-octadiene 2,6 in 160 ml of methylene chloride, is dropped, to 0 °C, in 3 hours and stirring, a solution of 10.7 S chloro perbenzoic acid to 86-3 % in 120 ml of a methylene chloride-ether mixture (9:1 ratio).

The stirred 3 hours at 0° G after the addition of the peracid.

The extends the reaction mixture in the ether and washed, first 3 times with a 10% potassium hydroxide solution cooled to 0° G, and then 3 times with water, the organic phase is dried on sodium sulfate, the solvent is evaporated under vacuum, and is purified by the silica gel chromatography (N-ethylcarbamoyl -4 phënoxy )" 1-epoxy -6,7 dimethyl -3,7-octene 2.

The éluc -ion is a mixture of equal volumes of methyl acetate and hexane. Melting point ° = 67-69 G.

For the methods of examples 1 to 4, the following compounds are prepared:

(see table next page)

EXAMPLE 5!

Larvae fasciatus Ten Dysdercus are, of

8 to 10 days before the imaginal driven, treated directly with a solution of acetone active product. Subjects are maintained at atmosphere 28 °C to 80-90% relative humidity. The larvae receive as feed crumb cottonseed inflated. After 1C about days, i.e. immediately after the moved completely in the adult state, the subjects are studied. The housing rigidly houses of normal adults and larvae dead, there are special shapes as " extralarves" (larvae with an additional driven larval) and " adultoïdes" (larval adults character). Special These forms correspond to stages of development non-viable, not in the normal cycle for development.

The table below indicates the number of

subjects β ℮ located, for each concentration indicated, in one or the other of the various stages of the development:

EXAMPLE 6:

Ten nymphs freshly made of Dermestes lardarius are treated directly by acetone solutions of active products. The nymphs are then maintained at 28" to 80-90 atmosphere % relative humidity. After about 10 days, i.e. as soon as the control subjects are released from their shell to the state of perfect insects, the subjects of the experience are examined. There is, from normal adult and dead nymphs, of " adultoïdes" (larval adults character). These adultoïdes correspond to stages of development non-viable, not existing in the regular cycle of development.

A = normal adult

= extralarves B

C = adultoïdes

= dead larvae D

A = normal adult

C = adultoïdes

= dead nymphs D

EXAMPLE 7:

Ten nymphs freshly made of Tenebrio molitor are treated directly by acetone solutions of active substances. The nymphs are then maintained at atmosphere 28 °C to 80-90% relative humidity. After 10 days, i.e. as soon as the control subjects are released from their shell to the state of perfect insects, the proband are studied. There is, from normal adult and dead nymphs, of " adultoïdes" (larval adults character-). These adultoïdes correspond to stages of development non-viable, not existing in the regular cycle of development.

A = normal adult

C = adultoïdes

= dead nymphs D

₁₀ EtEBEEE 8:

Ten nymphs freshly made of Leptinotarsa decemlineata are treated directly by acetone solutions of active substances. The nymphs are then maintained at atmosphere 28 °C to 80- Ç0 % relative humidity. After about 10 days, that is say as soon as the control subjects are released from their shell to the state of perfect insects, the proband are studied. There is, from normal adult and dead nymphs, of " adultoïdes" (larval adults character). 2o These adultoïdes correspond to stages of development non-viable, not existing in the regular cycle developing"

A = normal adult

C = adultoïdes

2' = dead nymphs D

Active substance

Quantities

active

^ in g

ïenebrio molitor

3. C

D

35

10