DD279814A5 - PESTICIDES, ESPECIALLY INSECTICIDES OR ACARICIDE COMPOSITION - Google Patents

Abstract

The invention relates to pesticides, in particular insecticidal or acaricidal compositions containing as active ingredient a trioxabicyclo & 2,2,2! -Octane of the general formula (I) in addition to traeger or entraining agents. The composition according to the invention is outstandingly suitable for controlling pests, for example in agricultural crops such as cotton, wheat, maize, rice, sorghum, vines, tomatoes, potatoes, fruit trees, spruces etc. Formula (I)

Description

Field of application of the invention

The invention relates to pesticidal compositions containing as active ingredient compounds of the following general formula I in addition to carriers or diluents.

Characteristic of the known technical solutions

The use of certain 2,6,7-trioxybicyclo [2,2,2] octanes as pesticides is described in European Patent Application 152,229.

Object of the invention

The aim of the invention is to provide novel compounds having a strong pesticidal effects that can be applied ι for controlling pests.

Explanation of the essence of the invention

The invention has for its object to provide new pesticides available.

It has now been found that derivatives of 2,6,7-trioxabicyclo [2,2,2] octanes having substituents in the 3-position have an interesting pesticidal activity.

Accordingly, according to the invention, compounds of the formula (I)

(D

where RC _{2 is} -io-alkyl, -alkenyl or -alkynyl, optionally substituted by or methyl, substituted by a cyano group, C _M -cycloalkyl, halo group, C 1-4 -alkoxy group or a group S (O) _m R 2 ^4, wherein R ⁴ is C, -4 alkyl and m is 0,1 or 2, or R Cj - ^ - cycloalkyl, C ^ o-cycloalkenyl or phenyl, each optionally substituted by a C ₁ ^ -AIkOXy-, C 3-alkyl, C ₂ -4-alkynyl, halo, cyano or a group S (O) _m R \ as defined above; R 'is a halo group, C, _3-alkyl, C ₂ -3 alkenyl or alkynyl each optionally substituted by a halo, cyanosis, C ₁ ^ -AIkOXy-, Alkylkarboxygruppe having up to 6 carbon atoms, a group S ( O) _1n R ⁴ , as defined above, or alkynyl, substituted by tri-Ci-4-alkylsilyl, or R 'is a cyano group, spiro-cyclopropyl, gem-dimethyl, gem-Dizyanogruppe, Gem-diethynyl, oxo group or Methylene, optionally substituted by a cyano group, or Ci-3-alkyl optionally substituted by fluoro, or R 'and R and the carbon atoms to which they are attached form a C ^ -carbocyclic ring, optionally substituted by a halo group, 3-alkyl or an alkoxy group or C ₂ _ ₃ alkenyl; R ^{2 is} phenyl, C ₅ -I ₀ -cycloalkyl or cycloalkenyl, each optionally substituted, and R ^{3 is} hydrogen, C 3-3 -alkyl, C ₂ . _{3 is} alkenyl or alkynyl, each optionally substituted by a cyano group, C 1-4 alkylthio, C 1-4 alkoxy or halo group, or R ^{3 is} a cyano or halo group.

A suitable R is propyl, butyl, pentyl, C 1-4 alkenyl or alkynyl, C 1-6 cycloalkyl or phenyl, each optionally substituted by one to three fluoro, chloro or bromo groups. The most suitable R is η-butyl, n-propyl, i-butyl, s-butyl, t-butyl, cyclopentyl or cyclohexyl, and preferably R is n-propyl, η-butyl, i-butyl, t-butyl or cyclohexyl. A suitable R ¹ is a cyano group, ethynyl or methyl or ethyl, optionally substituted by a cyano, methoxy, methylthio or fluoro group. The most suitable R ¹ is methyl, cyano group. Ethynyl, trifluoromethyl or ethyl. Preferably, R 'is methyl, trifluoromethyl, a cyano group or ethynyl. When R ^{2 is} a substituted phenyl, a Cs-μj-cycloalkyl or cycloalkenyl group, suitable substituents are included

a halo, cyano, azido, tetrazolyl group, a group SO ₂ R ⁵ , wherein R ^{6 is} an amino or di-C 1-4 -alkylamino group, a group COR ⁶ , wherein R ^{6 is} a 0, 4-alkoxy- , Benzyloxy, amino or di-C 1-4 -alkylamino group, a nitro group, C _1-3 -alkyl optionally substituted by a halo group, cyano group or aikynyl, or C ₂ -3 alkenyl or alkynyl, each optionally substituted by a halo group or Tri-Ci-4-alkylsilyl. When R ^{2 is} phenyl, C 1-8 cycloalkyl or cycloalkenyl substituted by an acidic or basic group, salts may be formed from the compounds having the formula (I). The invention includes salts of the compounds of the formula (I). The preparation of these salts is carried out by the methods generally known in the art. Typical salts include acid addition salts, such as those formed by mineral acids, and basic salts, such as those formed by the alkaline earth metals.

A suitable R ² is cyclohexyl, cycloheptyl, cyclooctyl or phenyl at the 3-, 4- and / or 5-position optionally substituted by halo, cyano, C 2-3 alkynyl, azido or nitro and / or at 2- and / or 6-position by a fluoro group. The most suitable R ² is cyclohexyl or phenyl optionally substituted at the 3, 4 and / or 5 position by a chloro, bromo, iodo, cyano or ethynyl. Preferably, R ^{2 is} phenyl, substituted at position 4 by chlorine, bromine, ethynyl or a cyano group.

A suitable R ³ is hydrogen or methyl. Preferably, R ^{3 is} hydrogen.

Suitable compounds of formula (I) include those of formula (I A).

R ^a

(IA)

wherein R "is C ^ ₂ alkyl, alkenyl or alkynyl, C ₅ - ₁₀ -Zykloalkyl or phenyl, each optionally substituted by cyanosis or C, -4 alkoxy group, R ^{1 a} cyano group or a C, - ₃ -Alkyi, _{C2. 3,} alkenyl or alkynyl each optionally substituted by one cyanosis, C _1-4 -AIkOXy-, C ^ alkylthio or halo group, or R ^1a is a cyano group, gem-dimethyl, or R ^{a and} R ^a and the carbon atoms to which they are attached form a C 1 -C 4 -cyclocyclic ring optionally substituted by C _1-3 -alkyl or an alkoxy group, R ^{2a is} phenyl, C 1-4 -cycloalkyl or cycloalkenyl, each optionally substituted, and R ^3a is hydrogen, Ci-3-alkyl, _C2 -3 alkenyl or alkynyl each optionally substituted by one cyanosis, C ^ alkylthio, C ^ alkoxy or halo group.

A suitable R ^a is propyl, butyl, Cs-r-cycloalkyl or phenyl. The most suitable R ^a is n-propyl, butyl, cyclopentyl or cyclohexyl, and preferably R ^{a is} propyl, butyl or cyclohexyl.

A suitable R ^1a is a cyano group, methyl or ethyl, optionally substituted by a cyano, methoxy, methylthio or fluoro group. Preferably, R ' ^{a is} methyl or ethyl.

Suitable substituents for R ^2a include halo, cyano, azido, nitro, C _t _ ₃ alkyl groups, optionally substituted by halo group, or C ₂ . ₃ alkenyl or alkynyl, each optionally substituted by a halo group.

Suitable R ^2a are cyclohexyl, cycloheptyl or phenyl optionally substituted at the 3- or 4-position by a halo, cyano, azido or nitro group. The most suitable R ^2a is cyclohexyl or phenyl, optionally substituted at the 4-position by chlorine, bromine or a cyano group.

Preferred compounds of the present invention include:

1- (4-bromophenyl) -4-cyclohexyl-3-methyl-2,6,7-trioxabizyklo [2,2,2 | octane,

1- (4-chlorophenyl) -3-methyl-4-isopropyl-2,6,7-trioxabizyklo [2,2,2loktan,

1- (4-bromophenyl) -3-methyl-4-n-propyl-2,6,7-trioxabizyklo [2,2,2] octane,

1- (4-chlorophenyl) -3-methyl-4-n-propyl-2,6,7-trioxabizykloI2,2,2] octane,

1-cyclohexyl-3-methyl-4-isopropyl-2,6,7-trioxabizyklot2,2,2] octane,

1- (4-bromophenyl) -4-t-butyl-3-methyl-2,6,7-trioxabizyklo [2,2,2] octane,

1,4-Dizyklohexyl-3-methyl-2,6,7-trioxabizyklo [2,2,2] octane,

4-t-Butyl-1- (4-chlorophenyl) -3-methyl-2,6,7-trioxabizyklo [2,2,2] octane,

1- (4-Ethynylphenyl) -3-methyl-4-n-propyl-2,6,7-trioxabizyklo [2,2,2) octane,

3-Methyl-4-n-propyl-1- [4- (2-trimethylsilylethynyl) phenyl] -2,6,7-trioxabicyclo [2,2,2] octane, 1- (4-ethynylphenyl) -4- n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo (2,2,2] octane, 4-n-propyl-3-trifluoromethyl-1- [4- (2-trimethylsilylethynyl) -phenyl] 2.6.7 trioxabicyclo [2,2,2-octane, 1- (4-chlorophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2,2,2-octane, 1- (4-8-romophenyl) -4 -n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1- (4-chlorophenyl) -4-cyclohexyl-3-trifluoromethyl-2,6,7-trioxabicyclo [ 2,2,2-octane, 1- (4-bromophenyl) -4-cyclohexyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2,2,2-octane, 1- (4-bromophenyl) -3-etheryl 4-n-propyl-2,6,7-trioxabizyklo [2,2,2] octane,

1-cyclohexyl-4-n-propyl-3-trifluoromethyl-2,6,7-trioxabizyklo [2,2,2) octane,

1- (4-bromophenyl) -3-cyano-4-n-propyl-2, ö, 7-trioxabizyklo [2,2,2] octane,

3-cyano-1- (4-ethynylphenyl) -4-n-propyl-2,6,7-trioxabizyklol2,2,2] octane,

1- (4-bromophenyl) -4-cyclohexyl-3-methoxymethyl-2,6,7-trioxabicyclo (2,2,2] octane, 1-cyclohexyl-3-methyl-4-n-propyl-2,6, 7-trioxabizyklo (2,2,2 | octane,

1- (4-bromophenyl) -4-t-butyl-3-ethyl-2,6,7-trioxabizyklo [2,2,2] octane,

4-t-butyl-1-cyclohexyl-3-methyl-2,6,7-trioxabizyklo [2,2,2] octane,

1- (4-chlorophenyl) -3,5-dimethyl-4-n-propyl-2,6,7-trioxabizyklo (2,2,2] octane,

1- (4-bromophenyl-3,5-dimethyl-4-n-propyl-2,6,7-trioxabizyklo [2.2.2! Octane,

1-Cyclohexyl-3,5-dimethyl-4-n-propyl-2,6,7-trioxabicyclo [2,2,2-octane, 1- (4-cyanophenyl) -4-n-propyl-3-trifluoromethyl-2, 6,7-trioxabicyclo [2,2,2] octane, 3-cyano-1- (4-cyanophenyl) -4-isopropyl-2,6,7-trioxabicyclo [2.2.2] octane, 4-t Butyl 3-cyano-1- (4-iodophonyl) -2,6,7-trioxabicyclo [2,2,2-octane, and 4-t-butyl-3-cyano-1- [4-! 2-trimethylsilylethynyl) -phenyl!] - 2,6,7-trioxabicyclo [2.2.2] octane, 1- (4-bromophenyl) -4-n-butyl-3-methyl-2,6,7-trioxabicyclo [2,2 , 2) octane, 4-n-butyl-1- (4-chlorophenyl) -3-methyl-2,6,7-trioxabicyclo [2,2,2] octane, 4-t-butyl-3-cyano-1- ( 4-ethynylphenyl) -2,6,7-triexabicyclo [2,2,2-octane, 1- (4-cyanophenyl) -3-ethynyl-4-isopropyl-2,6,7-trioxabicyclo [2,2,2-octane, 1 - (4-Bromo-3,5-dichlorophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1- (4-bromo-3-chlorophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabizyklo [2,2,2] octane.

Particularly preferred compounds include:

1- (4-bromophenyl) -3-methyl-4-n-propyl-2,6,7-trioxabicyclo [2.2.2] octane, 1- (4-bromophenyl) -4-cyclohexyl-3-methyl 2,6,7-trioxabicyclo [2.2.2] octane, 1- (4-chlorophenyl) -3-methyl-4-n-propyl-2,6,7-trioxabicyclool, 2,2,2-octane, 1- (4-bromophenyl) -4-t-butyl-3-methyl-2,6,7-trioxabicyclo-2,2,2] octane, 1- (4-chlorophenyl) -4-t-butyl-3-methyl-2, 6,7-trioxabicyclo [2,2,2] octane, 1- (4-bromophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2.2.2] octane, 1- (4-ethylphenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo-2,2,2] octane, 1- (4-ethynylphenyl) -3-methyl-4-n-propyl-2, 6,7-trioxabicyclo [2,2,2] octane, 1- (4-cyanophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1- (4-bromophenyl) -4-n-butyl-3-methyl-2,6,7-trioxabicyclo [2,2,2-octane, 4-n-butyl-1- (4-chlorophenyl) -3-methyl-2, 6,7-trioxabicyclo-2,2,2] octane, 4-t-butyl-3-cyano-1- (4-ethynylphenyl) -2,6,7-trioxabicyclo [2.2.2] octane, 1- (4 -Cyanophenyl) -3-ethynyl-4-isopropyl-2,6,7-trioxabicyclo [2,2,2-octane, 1- (4-bromo-3-chlorophenyl) -4-n-propyl-3-trifl uoromethyl-2,6,7-trioxabicyclo [2,2,2] octane or 4-n-butyl-1- (4-bromophenyl) -3-trifluoromethyl-2,6,7-trioxabicyclo [2.2.2] octane , 4-n-butyl-1- (4-iodophenyl) -3-methyl-2,6,7-trioxabicyclo [2.2.2] octane, 4-n-butyl-3-methyl-1- (4 - (2-trimethylsilylethynyl) phenyl) -2,6,7-trioxabicyclo [2,2,2] octane, 4-n-butyl-1- (4-ethynylphenyl) -3-methyl-2,6,7-trioxabicyclo [2,2,2-octane, 4-t-butyl-3-cyano-1-cyclohexyl-2,6,7-trioxabicyclo [2.2.2] octane, 1- (4-bromophenyl) -3-cyano-4 -n-propyl-2,6,7-trioxabicyclo [2,2, i!] octane, 3-cyano-1- (4-iodophenyl) -4-n-propyl-2,6,7-trioxabicyclo [2, 2,2-octane, 3-cyano-4-n-propyl-1- (2-trimethylsilylethynyl) phenyl) -2,6,7-trioxabicyclo [2,2,2-octane or 3-cyano-1- (4-ethynylphenyl) -4 n-propyl-2,6,7-trioxabizykio [2,2,2loktan.

In another aspect, the invention provides a process for the preparation of a compound of formula (I). The process for the preparation of a compound of formula (I) may be a method known in the art for the preparation of analogous compounds, e.g. By condensation of a triol of formula (II) with an ortho-carboxylate of formula R ² (C (OR ⁷ ) ₃ .

HO HO

wherein R to R ^{3 are} as defined above and R ^{7 is} C 1-4 alkyl, phenyl or C ₇ e aralkyl. Suitable for R ⁷ are methyl or ethyl, preferably methyl. The reaction is normally carried out in the presence of an acid, for example a mineral acid, preferably hydrochloric acid, or a sulfonic acid derivative, for example toluenesulfonic acid or an acid resin or in the presence of a trialkylamine, for example a triethylamine, at elevated temperature, for example between 50 ° and 200 ° C., usually between 120 ° and 170 ° C. The reaction can be advantageously carried out in the absence of a solvent, if desired, but also a suitable solvent can be added.

The triol of the formula (II) can be prepared:

(i) from the corresponding triol in which R ¹ and / or R ^{3 are} hydrogen via a protected aldehyde which is reacted with a reagent, for example a Grignard reagent, which is suitable for the extension of the carbon chain after elimination of the protection is, ie as shown in Scheme 1.

In certain cases, it may be advantageous to prepare triol derivatives in which R ¹ , R ^{3 is} hydrogen and one of the hydroxy groups is protected by reduction of an ester of the formula (III):

R ⁹ OOC

(III)

COOR

wherein R ^{8 is} a protecting group such as benzyl and R ^{9 is} C, -4-alkyl. This reduction is advantageously carried out by a complex hydride such as lithium aluminum hydride in a carry solvent, preferably an ether. The compound of the formula (III) can be prepared from the corresponding compound RCH (CO ₂ R ⁹ ) ₂ by reaction with a compound XCH ₂ OR ⁸ in which X is a residual group such as a halogen in the presence of a strong base, for example sodium hydride.

(ii) When a compound of formula (I) is to be prepared in which R ^{3 is} hydrogen by the reduction of a compound of formula (IV):

(IV),

wherein R, R ¹ and R ^{9 are} as defined above. This reduction is advantageously carried out by a complex hydride in an inert solvent such as an ether, for example diethyl ether.

When R and R 'are bonded together to form a carbocyclic ring, the compound of the formula (IV) is advantageously prepared by the reaction of a compound of the formula (V)

CO ₂ R "

(V)

with a compound Hal-CO ₂ R ⁹ , wherein R, R 'and R ^{9 are} as defined above and Hal is a halogen, for example chlorine. This reaction is advantageously carried out in the presence of a Grignard reagent, for example ethylmagnesium bromide, in a solvent such as ether, for example tetrahydrofuran. Other compounds of formula (IV) are advantageously prepared by the reaction of a compound RCH (CO ₂ R ⁹ Ja with a compound HaI-CO.R ¹ , wherein R, R ', R ⁹ and Hai are as defined above, or a This reaction is advantageously carried out in the presence of a strong base, for example a metal hydride, in a nonpolar solvent, for example an aromatic hydrocarbon, such as benzene or toluene

 The compounds of the formula (I) can also be prepared by cyclization of a compound of the formula (VI)

(Vl)

wherein R to R ^{3 are} as defined above in the presence of an acid catalyst. Boron trifluoride etherate is a particularly preferred acid catalyst for the cyclization which is normally carried in a solvent, for example a halogenated hydrocarbon, advantageously dichloromethane, at a temperature below the ambient temperature, for example between -100 ° and ⁰ ° C. and advantageously between -70 ° and 50 ° C is performed.

The compounds of the formula (VI) can be prepared by the reaction of compounds of the formula (VII) and (VIII):

OH

R ² CL

(VII)

wherein R ^{10 is} a group R 'and R to R ^{3 are} as defined above and L is a residual group, for example a halo group. This reaction is advantageously carried out in an inert solvent in the presence of a base at a non-extreme temperature. Halogenated hydrocarbons, for example dichloromethane, are particularly suitable solvents, pyridine is a preferred base and the reaction is advantageously carried out at a temperature between -50 ° C and 100 ° C, preferably at ⁰ ° C.

The compounds of formula (VII), in turn, can be prepared from compounds of formula (II) by reacting with diethyl carbonate in the presence of a strong base, for example potassium hydroxide, in a polar solvent such as an alcohol, for example ethanol, at elevated temperature , for example between 50 ° C and 100 ⁰ C. This is a preferred method for preparing compounds of formula (VII) where R ¹ = R _t0 = CF _3. Alternatively, the compounds of formula (VII) may be prepared by the reaction of a Grignard reagent RiMgHaI or a C ₂ -4 alkynyllithium compound or a sodium cyanide with a compound of formula (IX)

(IX) _t

wherein R, R ¹ and R ^{3 are} as defined above and Hal is a halogen atom, for example, bromine or iodine. This reaction is advantageously carried out in a carry solvent, suitable is a Ethei, for example diethyl ether or dioxane, at a non-extreme temperature, for example -50 ⁰ C and 50 ° C and preferably between -1O ⁰ C and 1O ⁰ C. The Alkynyllithiumverbindung is advantageously present as a complex, for example with ethylenediamine. The sodium cyanide is advantageously added as an aqueous solution. The compounds of formula (IX) may be prepared by the oxidation of compounds of formula (VII) wherein R ^{10 is} hydrogen, using oxalyl chloride and dimethyl sulfoxide in an inert solvent such as a halogenated hydrocarbon, for example dichloromethane, followed by a base such as triethylamine, or using pyridine chlorochromate in an inert solvent such as a halogenated hydrocarbon, for example, dichloromethane.

The compounds of formula (VII) wherein R ' ^{0 is} hydrogen may be prepared in analogous manner to give compounds of formula (VII) wherein R ^{10 is} trifluoromethyl from compounds of formula (II). A compound of the formula (I) can be converted into another compound of the formula (I) by known methods. Thus, the compounds of formula (I) wherein R ^{2 is} an ethynylphenyl group can be prepared from the corresponding iodophenyl group via the intermediate tiimethylsilylethynylphenyl.

The compounds of formula (I) can be used to control arthropods such as insects and acarine pests. Thus, in another aspect, the invention provides a method of controlling arthropods in animals which consists in administering to the animal an arthropodially effective amount of a compound of formula (I). The compounds of formula (I) may be used for these purposes by applying the compounds directly or in diluted form in known manner as dipping agents, sprays, lacquers, foams, dust, powders, aqueous suspensions, pastes, gels, shampoos, lubricants, combustible solid, evaporation emanator such as an evaporating mat, wettable powder, granules, aerosol, emulsifiable concentrate, oil suspensions, oil solutions, impregnated product or infusion composition. Dipping concentrates are not used as such, but diluted with water, and the animals are immersed in a dip with the dipping agent. Know spray by hand or via a spray or spray arch or be introduced with Raumsprühanlagen. The animal, the plant or the surface being treated can be saturated by a high volume application with the spray or superficially coated with the spray by slight or extremely low volume application. Aqueous suspensions may be applied in the same manner as spraying or dipping. Dust can be used by a powder application device or in animals in hole pouches attached to trees or friction poles. Pastes, shampoos and lubricants can be applied by hand or spread over the surface of a sluggish material, where the animals rub and transfer the material to their skin. Infusion compositions are distributed as a low volume liquid unit on the back of the animals so that all or almost all of the liquid adheres to the animals. The compounds of formula (I) may be prepared either as ready-to-use compositions for depth, plants or surfaces, as room sprays or aerosols or as compositions which must be diluted before use, but both types of compositions contain a compound of the formula ( I) in close admixture with one or more carriers or diluents. These carriers may be liquid, solid or gaseous, or mixtures of these substances, and the compound of formula (I) may be present in a concentration of from 0.025 to 99% / w / w depending on whether further dilution is required , to be available. Dust, powder and granules consist of the compound of formula (I) in close admixture with a powdered solid carrier, for example suitable clays, kaolin, silica, talc, mica, gypsum, vegetable carriers, starch and diatomaceous earths.

Sprays of a compound of formula (I) may consist of a solution in an organic solvent (eg those listed below) or an emulsion in water (dip wash or spray wash) made in situ from an emulsifiable concentrate (also referred to as water-miscible oil known), which can also be used for diving purposes. The concentrate preferably consists of a mixture of the active ingredient with or without an organic solvent and one or more emulsifying agents. Solvents can be present within wide limits

but preferably in an amount of 1 to 90% by weight / volume of the composition, and they can be selected from kerosenes, alcohols, xylene, aromatic naphtha, aromatic and aliphatic esters and other solvents known in the art. The concentration of emulsifiers may be varied within wide limits, but is preferably in the range of 0.5 to 25 wt .-% / vol., · Nd the emulsifiers are advantageous nonionic surface active agents including polyoxyalkylene esters of alkyl phenols and polyoxyethylene derivatives of of hexitol anhydrides, and anionic surfactants, including sodium lauryl sulfate, fatty alcohol ether sulfate, Na and Ca salts of alkylaryl sulfones and alkyl sulfosulphonates.

Wettable powders include an inert, solid carrier, one or more surfactants, and optionally stabilizers and / or antioxidants.

Wettable powders and emulsifiable concentrates normally contain between 1 and 95% by weight of the active ingredient and are diluted before use, for example with water.

Paints consist of a solution of the active ingredient in an organic solvent, together with a resin and optionally a plasticizer.

Dipping detergents can be prepared not only from emulsifiable concentrates, but also from wettable powders, soap-based scavengers, and aqueous suspensions consisting of a compound of formula (I) in admixture with a dispersing agent and one or more surface-active agents ,

Aqueous suspensions of a compound of formula (I) may consist of a suspension in water together with suspending, stabilizing or other agents. The suspensions or solutions may be used as such or in a diluted form prepared in a known manner.

Lubricants (or ointments) can be made from vegetable oils, synthetic esters of fatty acids or wool fat, along with a slow-acting base, for example soft paraffin. A compound of formula (I) is preferably uniformly distributed in solution or suspension in the mixture. Lubricants may also be prepared from emulsifiable concentrates by dilution with an ointment base.

Pastes and shampoos are also semi-solid preparations in which a compound of formula (I) may be present as a uniform dispersion in a suitable base such as soft or liquid paraffin, or made on a fat-free basis with glycerin, mucus or a suitable soap. As lubricants, shampoos and pastes are generally applied without further dilution, they should contain the appropriate percentage of the compound of formula (I) needed for the treatment.

Aerosol sprays can be prepared as a simple solution of the active ingredient in the aerosol propellant and cosolvent, such as halogenated alkanane, or the aforementioned solvents. Infusion compositions may be prepared as a solution or suspension of a compound of formula (I) in a liquid medium. A bird or mammalian host may also be protected from attack by ectopic acarinic parasites by carrying appropriately contoured articles made of plastic impregnated with a compound of formula (I). These articles include impregnated neck rings, pendants, bands, sheets and strips that are conveniently attached to appropriate parts of the body.

The concentration of the compound of the formula (I) applied to an animal will vary depending on the compound selected, the interval between treatments, the type of composition and the probable infestation, but generally should be 0.001 to 20.0 Vol.% And preferably 0.01 to 10% of the compound in the applied composition be present. The amount of composition applied to an animal will vary according to the method of application, the size of the animal, the concentration of the compound in the composition used, the factor after which the composition is diluted, and the nature of the composition, but is generally within the range from 0.0001% to 0.5%, except for undiluted compositions such as infusion compositions generally applied at a concentration in the range of from 0.1 to 20.0% and preferably from 0.1 to 10%.

The compounds of formula (I) are also useful in the protection and treatment of plant species, in which case an insecticidal or acaricidal amount of the active ingredient is applied. The rate of application will vary according to the compound chosen, the nature of the composition, the mode of use, plant species, planting density and probable infestation, and similar factors; in general, a useful application rate for agricultural crops is 0.001 to 3kg / ha, and preferably between 0.01 and 1 kg / ha. Typical compositions for agricultural use contain from 0.0001% to 50% of a compound of the formula (I) and advantageously between 0.1 and 15% by weight of a compound of the formula (I).

The special crops include cotton, wheat, corn, rice, Sorf hum, vines, tomatoes, potatoes, fruit trees and spruces.

Dust, lubricants, pastes, surface and room sprays and aerosol compositions are generally applied randomly as described above, and may be used at concentrations of 0.001 to 20% / w / v of the compound of formula (I). be worked in the composition used.

It has been found that the compounds of formula (I) are active against the common housefly (Musca domestica).

In addition, compounds of formula (I) are active against other arthropod pests, including Tetranychusurticai Plutella xylestella, Culex spp. and Blattella germanlca. Thus, the compounds having the formula (I) are useful in the control of arthropods, e.g. Insects and acarines, in any environment where the pests are, e.g. In agriculture, domestic animals, public health and the household.

Insect pests are members of the orders Coleoptera (eg Anoblum, Tribolium, Sitophilus, Diabrotica, Anthonomus or Anthrnus spp.), Lepidoptera (eg Ephestia, Plutella, ChIIo, Heliothis, Spodoptera or Tineola spp.), Diptera (e.g. B. Musca, Aedes,

Culex, Glossina, Stomoxys, Haematoblr, Tabanus, Hydrotaea, Lucilia, Chrysomia, Oallitroga, Dermatobia, Hypoderma,

Liriomyza and Melophagus spp.), Phthiraptera (Malophaga eg Damaiina spp and Anoplura, eg Pediculus humanus capitis, Pediculus humanus humanus, Phythirus pubis Linognathus and Kaematopinus spp.), Hemiptera (eg Aphis, Bemisia , Aleurodes, Nilopavata, Nephrotetix or Cimes spp.), Orthoptera (eg Sehistocerca or Acheta spp.), Dictyoptera (eg.

Blattella, Periplaneta or Baltta spp.), Hymenoptera (eg Solenopsis or Monomorium spp.), Isoptera (eg Reticulitermes spp.), Siphonaptera (eg Ctenocephalides or Pulex spp.), Thysanura (e.g. Lepisma spp), Dermaptera (eg Forficula spp.) And Pscoptera (eg Perlpsocus spp.).

The acarine pests include ticks, z. B. members of the genes Boophilus, Rhipicephalus, Amblyomma, Hyalomma, Ixodes, Haemaphysalis, Dermocentor and Anocentor, and mites and mange such as Sarcoptes scabiai and Tetranychus, Psorpptes, Notoedres, Psorergates, Chorioptes and Demodex spp.

Compounds of the invention may be combined with one or more other active ingredients (e.g. pyrethroids, carbamates and organophosphates) and / or with attractants and / or with fungicides. In addition, it has been found that the activity of the compounds of the invention can be enhanced by the addition of a synergistic or enhancing agent, for example a synergistic agent of the oxydase inhibitor class, such as piperonyl butoxide or NIA16388; an intermediate compound of the invention, or a pyrethroid pesticidal compound. When a synergistic oxidase inhibitor is present in j1 in a formula of the compound, the ratio of synergistic agent to compound of formula (I) ranges from 25: 1 to 1:25, e.g. B. at about 10: 1. Stabilizers to prevent chemical degradation that may occur in the compounds of the invention include, for example, antioxidants (such as tocopherol, butylhydroxyanisole and butylhydroxytoluene) and deoxidants (such as epichlorohydrin

 It is believed that the invention extends in its claim to:

(a) compounds of formula (I);

(b) Process for the preparation of compounds of formula (I);

(c) insecticidal and acaricidal compositions consisting of a compound of formula (I) in admixture with a carrier;

(d) methods for the preparation of such pesticidal compositions;

(e) methods of combating arthropod pests, such as insects or acarin pests, which consist in the application of a compound of formula (I) to the pests or their environment;

(f) synergistic pesticidal compositions comprising a compound of formula (I), and

(g) potentiating or non-potentiating mixtures of a compound of formula (I) and another pesticidal compound;

(h) novel intermediates in the preparation of compounds of formula (I).

Ausführungsbev'spiol

The following examples illustrate, in a non-limiting manner, preferred aspects of the invention.

The physical data for each of the compounds with the forms! (I) are given in the tables according to the examples. All indicated temperatures are in ° C.

Example A:

1-cyclohexyl-4-eihyl-3-methyl-2,6,7-trioxabizyklo [2,2,2] octane

(i) Notrium hvdrid (24 g, 50% dispersion in oil) was added to a stirred solution of diethyl ethyl malonate (94 g) in dry benzene (300 mL) at room temperature. The mixture was kept at 6CTO with stirring for one hour.

The mixture was cooled, to which was added acetyl chloride (36 ml), and the reaction mixture was stirred at room temperature for three hours. The reaction mixture was poured into ice, and the aqueous mixture was extracted with ether. The ether extracts were washed with water, dried over magnesium sulfate and the solvent removed in vacuo.

Distillation afforded diethyl 2-acetyl-2-ethylmalonate '54g), a colorless oil (b.p. 94 ° C, 1.5mm).

The following nuclear magnetic resonance spectrum was obtained: (NMR) Ή (particles / mill. Of TMS in CDCl ₃ , integral, number of peaks, J _Hj ) ×. 4,25,4H, q, 6; 2,36,3H, s; 2,2,2H, m; 1 /, 6 !!, t, 6; 1,0,3H, t, 6.

(ii) (Lithium aluminum hydride (8.0g) in dry diethyl ether (200ml) was stirred under a stream of dry nitrogen at ⁰ ° C. Diethyl 2-acetyl-2-ethylmalonct (30g) in dry ether (50ml) was added. The mixture was stirred at room temperature for three hours, then refluxed with stirring over eight hours, and to the cooled reaction mixture was added carefully a solution of sodium hydroxide (20 g) and potassium hydrogen phosphate (20 g) in water (150 ml) The pH was adjusted to 5.0 with glacial acetic acid, the solid was removed by filtration and washed with water (20 ml) The combined filtrate and washings were evaporated in vacuo and the residue was washed with acetone (3 × 100 ml). The acetone washes were evaporated in vacuo.

The residue was washed with chloroform (3 × 100 ml) and the washings were evaporated in vacuo. 2-Ethyl-2-hydroxymethylbutan-1,3-diol was obtained as a pale yellow oil (8.0g). The following nuclear magnetic resonance (NMR) spectrum was determined: Ή (particles per millimeter, TMS in CDCl ₃ , integral, number of peaks, J _{H /} ): 4.2, _H , broad singlet; 4,1,1H, m; 3,8,4H, m; 1,4,5H, m; 1,0,3H, m.

(iii) Trimethyl orthocyclohexylcarboxylate (1.1g) was added to 2-ethyl-2-hydroxyhydroxybutane-1,3-diol (0.75g). One drop of concentrated hydrogen chloride was added and the mixture was held at 130 ^° C. under nitrogen flow for one hour.

The volatile components were removed in vacuo (3.0tim) at 130 ° C.

The residue was purified by chromatography on alumina (Alumina Woelm TSC) eluting with 1: 4 dichloromethane: hexane saturated with ammonia. 1-Cyclohexyl-4-ethyl-3-methyl-2,6,7-trioxabicyclo [2.2.2] octane was obtained as a colorless oil (0.3 g).

The gas-liquid chromatography (glc) OV210 at 150 ⁰ C gave a peak.

In the same way but starting from diethyl n-propyl malonate, diethyl i-propyl malonate or diethyl n-butyl malonate and acetyl chloride, propionyl chloride, butyryl chloride or methoxyacetyl chloride, as appropriate, and carrying out the final condensation with trimethyl orthocyclohexyl carboxylate, trimethyl-4 Chloroorthobenzoate or trimethyl-4-bromoorthobenzoate, the following compounds were prepared:

1- (4-chlorophenyl) -4-ethyl-3-methyl-2,6,7-trioxabizyklo [2,2,2] octane,

1- (4-bromophenyl) -4-ethyl-3-methyl-2,6,7-trioxabizyklo [2,2,2] octane,

1- (4Chlorophenyl) -4-n-propyl-3-methyl-2, 'j, 7-trioxabizyklo [2,2,2] octane,

1-Zyklohexyi-4-n-propyl-3-methyl-2,6,7-trioxabizyklo | 2,2,2) octane,

1-cyclohexyl-4-i-propyl-3-rr.öthyl-2,6,7-trioxabizyklo [2,2,2loktan,

1- (4-bromophenyl) -4-n-propyl-3-methyl-2,6,7-trioxabizyklo [2,2,2] okton,

1- (4-chlorophenyl) -4-propyl-l · 3-methyl-2,6,7-trioxybizyklo (2,2,2] octane,

1- (4-bromophenyl) -3-ethyl-4-n-propyl-2,6,7-trioxabizyklo [2,2,2] octane,

1-Zyk! Ohexyl-3-ethyl-4-n-propyl-2,6,7-trioxabizyklo [2,2,2Joktan,

1- (4-bromophenyl) -3-ethyl-4-i-propyl-2,6,7-trioxabizyklo | 2,2,2] octane,

1- (4-Broinophenyl) -3-n-propyl-4-i-propyl-2,6,7-trioxabizykloI2,2,2] oktaii,

1-cyclohexyl-3-n-propyl-4-i-propyl-2,6,7-trioxabizyklo [2,2,2] octane,

1- (4-Bromophenyl) -3-methoxy>: hyl-4-i-propyl-2,6,7-trioxabicyclo [2.2.2] octane, 1-cyclohexyl-3-methoxymethyl-n-propyl-2 , 6,7-trioxabizyklol2,2,2] octane,

1- {4-Bromophenyl) -3-methoxy, ethyl 4-n-propyl-2,6,7-trioxabicyclo [2,2,2] octyne, 1-cyclohexyl-3-methoxymethyl-4-i-propyl-2 , 6,7-trioxabizyklo [2,2,2] octane,

1- (4-Bromophenyl) -1-cyclohexyl-3-methoxymethyl-2,6,7-trioxybicyclo [2.2.2] octane, V (4-bromophenyl) -4-n-butyl-3-methyl-2 , 6,7-trioxabizykloI2,2,2) octane,

4-n-Butyl-1- (4-chlorophenyl) -3-methyl-2,6,7-trioxabizyklo | 2,2,2] octane.

Example B:

1-cyclohexyl-3,4-diethyl-2,6,7-trioxabizyklo [2,2,2] octane

(i) 2-Ethyl-2-hydroxyethylpropane-1,3-diol (34g), Aietun (J7ml) and p-toluenesulfonic acid (0.5g) were refluxed in benzene (140ml) and water was added to a Dean and Stark equipment removed. After ten hours of refluxing, the mixture was cooled and washed with saturated aqueous sodium hydrogen carbonate solution.

The benzene solution was dried over anhydrous magnesium sulfate. The solvent was removed in vacuo. Distillation gave 2,2-Oimethyl-5-ethyl-5-hydroxymethyl-1,3-dioxane (35g) as a colorless oil (b.p. \ ir, kt 80-82 ⁰ C, 0.9 mm).

The following nuclear magnetic resonance spectrum (NMR) was determined: Ή (particles / mill. Of TMS in CDCl, integral, number of peaks, J _Hi ): 3.90, 2H, c, 6; 3,85,4H, s; 3,10,1 H, 6, t; 1.60, 6H, s; 1,55,2H, m; 1.05. 3H, m.

(ii) 2,2-Dimethyl-5-ethyl-5-hydroxymethyl-1,3-dioxane (33g) was added to a stirred suspension of pyridine chlorochromate (122.6g) and anhydrous sodium acetate (7.8g) in dry dichloromethane (200ml). added at ⁰ ° C under a stream of nitrogen. The mixture was stirred at room temperature for six hours. The mixture was diluted with dry ether (500 ml) and the organic solution was decanted. The oily residue was treated with ether and the combined extracts were evaporated in vacuo. The residue was purified by chromatography on silica, eluting at a ratio of 1: 3 from ether to hexane. 2,2-Dimethyl-5-ethyl-5-formyl-1,3-dioxane (30g) was obtained as a colorless

Gas-liquid chromatography (glc) OV210 at 13O ⁰ C gave a peak.

It was determined the following nuclear magnetic resonance spectrum (NMR): ¹ H (part / million from TMS in CDCI _3, integral, number of peaks, J _Hl.): 9,6,1H, s; 4,2,2 H, d, 12; 3,8,2 H, d, 12; 1,4,8 H, m; 0.86.3 H, t, 6.

(iii) A solution of Ethylmagnesiumbrorrid (70ml), 1.3 M in tetrahydrofuran) was stirred b * i O ⁰ C under nitrogen. 2,2-Dimethyl-5-ethyl-5-formyl-1,3-dioxane (IU, 3g) in dry tetrahydrofuran (20 ml) was added. and the mixture was stirred at room temperature for three hours. The mixture was then refluxed with stirring for one hour, saturated aqueous ammonium chloride solution was added to the cooled reaction mixture. The aqueous mixture was extracted with ether. The ether extracts were washed with water, dried over anhydrous magnesium sulfate and the solvent removed in vacuo. The residue was purified by chromatography on silica gel, eluting with 40% etherhexane. 2,2'-Dimethyl-5-ethyl-5- (1-hydroxypropyl) -1,3-dioxane was obtained as a colorless oil (10.0 g).

The gas-liquid chromatography (glc) OV210 at 140 ⁰ C gave a peak.

It has been determined following magnetic Kernrescnanzspektrum (NMR): Ή (particles / Mill from TMS in CDCI _3, integral, number of peaks, J _Hl.): 3,70,5H, m; 2,20,1 H, d, 6; 1.40, 10H, m; 1,00,6H, m.

(iv) 2,2-Dimethyl-5-ethyl-5- (1-hydroxypropyl) -1,3-dioxane (LOG) and Dowex 50X8-200 ion exchange resin (H ^f-form) (1.0 g) in methanol ( 200 ml) containing water (40 ml) was refluxed with stirring for three hours.

The mixture was filtered and the filtrate removed in vacuo. 2-Ethyl-2-hydroxymethylpentane-1,3-diol (6.0 g) was recovered as a colorless, viscous oil.

The following nuclear magnetic resonance spectrum (NMR) was determined: ¹ H (particles / millimeter of TMS in CDCl ₃ , integral number of peaks, J _{H /} ): 3.80, 5H, m; 3,00,3H, m; 1.8 to 0.8, 10H, m.

(v) From 2-ethyl-2-hydroxymethylpentane-1,3-diol (0.7 g), using the method described in Example A, 1-cyclohexyl-3,4-diethyl-2,6,7-trioxabicyclo [ 2,2,2 | octane (0,3g) as a colorless oil.

Gas-liquid chromatography (glc) OV210 at 18O ⁰ C gave a peak.

1 - (4-chlorophenyl) -3,4-diethyl-2,6,7-trioxabicyclo [2.2.2] octane was recovered in an analogous manner when trimethyl orthocyclohexylcarboxylate was replaced in the final condensation with trimethyl 4-chloroorthobenzoate.

1-cyclohexyl-4-t-butyl-3-methyl-2,6,7-trioxabizyklo [2,2,2] octane,

1- (4-bromophenyl) -4-t-butyl-3-methyl-2,6,7-trioxabizyklo [2,2,2] octane,

4-t-Butyl-1- (4-Chlorophenyl) -3-methyl-2,6,7-trioxabizyklo [2,2,2loktanund

1- (4-8romophenyl) -4-t-butyl-3-ethyl-2,6,7-trioxabizyklo [2,2,2] octane

were prepared by an analogous procedure starting from 2-t-butyl-2-hydroxymethylpropane-1,3-diol.

1- (4-bromophenyl) -3-ethenyl-4-n-propyl-2,6,7-trioxabizyklo [2,2,2loktan

was prepared in an analogous manner by using vinylmagnesium bromide instead of ethylmagnesium bromide in step (iii) and using triethylamine in place of hydrochloric acid in step (v).

Examples:

1- (4-bromophenyl) -4-z'klohexyl-3-methyl-2,6,7-trioxabizyklo [2,2,2] octane

(i) Diethyl cyclohexyl manolate (18.7 g) was added to a stirred suspension of sodium hydride (4.8 g, 50% dispersion in oil) in dry tetrahydrofuran (50 mL) under nitrogen. The mixture was stirred for one hour

Reverse treatment subjected. The mixture was cooled and benzyl chloromethyl ether (13.9g) in dry tetrahydrofuran (50ml) was added and the mixture stirred under reflux for three hours. The mixture was cooled and poured into water. The aqueous mixture was extracted with ether. The ether extracts were washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo. Diethyl 2-benzyloxymethyl-2-lyclohexyl malonate (30g) was further used as a brown oil and without further purification.

(ii) Diethyl 2-benzyl oxymethyl 2-cyclohexyl malonate (2g) was added to a suspension of lithium lithium hydride (0.63g) in dry ether (30ml) at ⁰ ° C under nitrogen. The mixture was stirred at room temperature for twelve hours. Water (5 ml) was added carefully, and the mixture was stirred for 10 minutes. Add 10% sulfuric acid solution (10 mL) and extract the mixture with ether. The ether extracts were washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo. The residue was purified by chromatography on silica, eluting with 1: 1 etherhexane. There was recovered 2-ßenzyloxy.Tiethyl-2-cyclohexylpropane-1,3-diol as oin colorless oil (1, Og).

The gas-liquid chromatography (glc) OV210 at 230 ⁰ C gave a peak.

It has the following magnetic Kernresonanzsper .. to (NMR) determined: Ή (particles / Mill from TMS in CDCI _3, integral, number of peaks, J _Hl.): 7,35,5H, s; 4,55,2H, s; 3.75,4H, d, i, 3,60,2H, s; 2,90,2H, t; 2,00 - 0,90,11H, m.

(iii / 2-8enzyloxymethyl-2-cyclohexylpropane-1,3-diol (3g) 2,2-dimethoxypropane (8ml), p-toluenesulfonic acid (150mg) and molecular sieves (Type 4A) were heated in refluxing, dry toluene (50ml) four The mixture was cooled and passed, the filtrate was diluted with ether, and the ethereal solution was extracted with aqueous sodium hydrogencarbonate solution The ethereal solution was washed with water, dried over anhydrous magnesium sulfate, evaporated in vacuo, the residue was purified by chromatography on silica eluting with 1: 5 ether: hexane to give 5-benzyloxymethyl-5-cyclohexyl-2,2-dimethyl-1,3-dioxane (3.0 g) as a colorless oil.

Gas-liquid chromatography (glc) OV210 at 230 ° C gave a peak.

The following nuclear magnetic resonance (NMR) spectrum was determined: Ή (particles / millimeter of TMS in CDCN, integral number of peaks): 7.30, 5H, s; 4.50, 2H, s; 3.70, "H, s; 3.60, 2H, s; 2.00 - 0.9, 17H, m.

(iv) 5-Benzyloxymethyl-5-cyclohexyl-2,2-dimethyl-1,3-dioxane (3.0g) in dry ether (10ml) was added at -70X to liquid ammonia (100ml). To the stirred solution was added sodium (0.5 g). Was allowed to warm to -3O ⁰ C the mixture, and it was added solid ammonium chloride (2.0g) was added. The ammonia was removed from the reaction mixture under a stream of nitrogen. Water was added and the aqueous mixture was extracted with diethyl ether. The ethereal extracts were washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo.

5-Cyclohexyl-2,2-dimethyl-5-hydroxymethyl-1,3-dioxane was obtained as a creamy solid (2.15 g), which was used without further purification.

The gas-liquid chromatography (glc) OV210 at 200 ⁰ C gave a peak.

The following nuclear magnetic resonance spectrum (NMR) was determined: Ή (particle / millimeter of TMS in CDCl ₃ , integral, number of peaks): 3.80.2H, s; 3,65,4H, s; 2,30,1H, s, wide; 2,00 - 0,8,17 H, m.

(v) 5-Cyclohexyl-2,2-dimethyl-5-hydroxymethyl-1,3-dioxane (2.2 g) was added to a stirred suspension of pyridine chlorochromate (6.1 g) and anhydrous sodium acetate (3.0 g) in dry dichloromethane (50ml) at 0 ° C under a stream of nitrogen. The mixture was stirred at room temperature for six hours. The mixture was diluted with dry ether (100ml) and the organic solution decanted. The oily residue was treated with ether and the combined extracts were evaporated in vacuo. 5-Cyclohexyl-2,2-dimethyl-5-formyl-1,3-dioxane was recovered as a pale yellow oil (1.8 g) and used without further purification.

The following nuclear magnetic resonance spectrum (NMR) was determined: ¹ H (particles / mill. Of TMS in CDCl ₃ , integral, number of peaks, J _Hj ): 9.80.1 H, s; 4,25,2H, d, 12; 3, 90, 2H, d, 12; 2,00 - 0,8,17H, m.

Infrared spectrum (IR) (liquid film): v ¹ 1730cm "'.

(vi) Methylmagnesium iodide (3.0 mL of 3M solution in ether) was added to a solution of 5-cyclohexyl-2,2-dimethyl-5-formyl-1,3-dioxane (1.8 g) in dry ether (SOmI). The gomish was refluxed for two hours with stirring, cooled and poured into a mixture of 2N hydrochloric acid solution in ice. The aqueous genic was extracted with ether. The ether extracts were washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo. 5-Cyclohexyl-2,2-dimethyl-5- (1-hydroxyethyl) -1,3-dioxanol gave a creamy solid (1.5 g).

Gas-liquid chromatography (glc) OV210 at 17O ⁰ C gave a peak.

It has the following nuclear magnetic resonance (NMR) spectrum obtained: ¹ H (particles / Mill from TMS in CDCI _3, integral, number of peaks, J _Hl.): 4,15,1 H, q, 6: 3.90 to 3, 50.4H, m; 3,10 1 H, s, wide; 2,00 - 0,9,2OH, m.

(vii) 5-cyclohexyl-2,2-dimethyl-5- (1-hydroxyethyl) -1,3-dioxane (1.5 g) and ion exchange resin Dowex 50X8-200 ^(f H form) (1.0 g) in methanol (30ml) and water (10ml) was refluxed with stirring for six hours. The mixture was filtered and the filtrate was evaporated in vacuo. It became 2-cyclohexyl-2-hydroxymethyl-butane-1,3-dio! recovered as a pale yellow oil (1.2 g) and used without further purification.

Gas-liquid chromatography (glc) OV210 at 160 ⁰ C gave a peak.

It has the following magnetic Kemresonanzspektrum (NMR) determined: ¹ H (Tnilchen / Mill from TMS in CDCI _3, integral, number of peaks, J _Hl.): 4,30,1H, m; 4,00,2 H, s; 3,95,2H, s; 3,20,3H, s, wide; 2,00 - 0,90,14H, m.

(vii) From 2-cyclohexyl-2-hydroxymeti ^'l .ylbutan-1,3-diol (0.27 g) and trimethyl-4-bromoorthobenzoat was prepared using the procedure described in Example A 1- (4-bromophenyl) -4 -cyclohexyl-3-methyl-2,6,7-trioxabicyclo [2,2,2-octane, a colorless, solid substance! won (0.14g).

Gas-liquid chromatography (glc) OV210 at 24 ° C gave a peak.

1,4-Dicyclohexyl-3-methyl-2,6,7-trioxabicyclo (2,2,2) octane was prepared in an analogous manner using trimethyl orthocyclohexylcarboxylate in place of trimethyl 4-bromooorthobenzoate in the final condensation reaction.

Example D:

2- (4-Bromophenyl) -4,4a, 5,6,7,8,8a-heptahydro-2,4a-epoxymethanobenzo-1,3-dioxin

(i) A tetrahydrofuran solution (30 ml) of ethylmagnesium bromide was prepared from bromomethane (7.05 g) and magnesium (1.5 g). The solution was cooled to ⁰ ° C and carefully added to 2-carbethoxycyclohexanone (10.0g). The

The reaction mixture was stirred at room temperature for 30 minutes, and under nitrogen was added dropwise ethyl chloroate (7.0 g). It formed a white precipitate. Sulfuric acid solution (80 ml, 1%) was added and the aqueous mixture extracted with ether. The ether extracts were washed with dilute aqueous sodium hydrogen citrate solution, water and then dried over anhydrous magnesium sulfate. The solvent was removed in vacuo. Distillation gave 2,2-dicarbethoxycyclohexanone (7.8g), a colorless oil (b.p. 98 ° C-102 ° C, 0.9mm).

The following nuclear magnetic resonance spectrum (NMR) was determined: ¹ H (particle / millimeter of TMS in CDCl ₃ , integral, number of peaks, J _Hi ): 4,3,4H, q, 6; 2.5,4H, m; 1,8,4H, m; 1,4,6H, t, 6.

(ii) A solution of 2,2-dicarbethoxycyclohexanone (3.0g) in dry ether (1GmL) was added dropwise to a stirred suspension of lithium aluminum hydride (1.4g) in dry ether (50ml) at ⁰ ° C under nitrogen. The mixture was refluxed for six hours with stirring. To the stirred mixture was added potassium hydroxide (6g) in water (100ml). Dipotassium hydrogen phosphate (4.2 g) and potassium dihydrogen phosphate (3.3 g) in water (50 ml) were added; the ether was removed by passing a stream of nitrogen through the mixture. The resulting slurry was acidified with glacial acetic acid and the solid was filtered off. The filtrate was evaporated in vacuo. The residue was extracted with acetone and the solution evaporated in vacuo. 2,2-Di (hydroxymethyl) -cyclohexanol (1.2 g) was obtained as a pale yellow oil.

Gas-liquid chromatography (glc) OV210 at 150 ° C gave a peak.

It has the following nuclear magnetic resonance (NMR) spectrum obtained: ¹ H (particles / Mill from TMS in CDCI _3, integral, number of peaks, J _Hl.): 4,6,3H, s; 4,00-3,70,5H, m; 1,800-0,9,8H, m.

(iii) 2,2-Di (hydroxymethyl) -cyclohexanol (0.76 g) was added to trimethyl 4-bromoo-thobenzoate (1.1 g). One drop of concentrated hydrochloric acid was added and the mixture heated at 140 ° C for three hours. The volatile components were removed at 15O ⁰ C in vacuo (3.0 mm). The residue was purified by chromatography on alumina (Alumina-Woehm, TSC) eluting with 1: 1 dichloromethane: hexane saturated with ammonia.

There was recovered 2- (4-bromophenyl) -4,4a, 5,6,7,8,8a-heptahydro-2,4a-epoxymethanobenzo-1,3-dioxin as a colorless oil (0.27g).

In an analogous manner, 2-cyclohexyl-4,4a, 5,6,7,8,8a-heptahydro-2,4a-expoxymethanobenzo-1,3-dioxin was prepared.

Example E:

1- (4-chlorophenyl) -3,5-dimethyl-4-ethyl-2,6,7-trioxabizyklo- [2,2,2] octane

(i) 2,2-Dimethyl-b-ethyl-5-hydroxymethyl-1,3-dioxane (10g) was added to a stirred suspension of sodium hydride (2.4g, 50% dispersion in oil) in dry tetrahydrofuran (80ml) , The mixture was subjected to a reflux treatment for one hour with stirring. Benzyl chloride (9.2 ml) was added and the mixture was refluxed for three hours with stirring, then the mixture was poured into water and the aqueous mixture extracted with ether. The ethereal extract was washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo. 5-Benzyloxymethyl-2,2-dimethyl-5-ethyl-1,3-dioxane was recovered as a pale brown oil (15g) and used without further purification.

(ii) 5-Benzyloxymethyl-2,2-dimethyl-5-ethyl-1,3-dioxane (15.0 g) and Dowex 50 χ 8-200 (H ^f -form) ion exchange resin (2.0 g) in methanol (250 ml) containing 50 ml of water was subjected to reflux treatment with stirring for three hours. The mixture was filtered and the filtrate was evaporated in vacuo. 2-Benzyloxymethyl-2-hydroxymethylbutane-1-oil was recovered as a yellow oil (9.7 g).

It has the following nuclear magnetic resonance (NMR) spectrum obtained: ¹ H (particles / Mill from TMS in CDCI _3, integral, number of peaks, J _Hl.): 7,35,5 H, s; 4,55,2 H, s; 3,65,4 Hm, s; 1.40.2 H, m; 0.90.3 H, t, 6.

(iii) 2-Benzyloxymeth "l-2-hydroxymethylbutane 1-oil (9.7 g) was added to a stirred suspension of pyridine chlorochromate (9.7 g) and anhydrous magnesium acetate (2.0 g) in dry dichloromethane (200 ml) at 0 ⁰ C added under a stream of nitrogen.

The mixture was stirred at room temperature for six hours. The mixture was diluted with dry ether (200 ml) and the organic solution was decanted. The oily residue was treated with ether and the combined extracts were evaporated in vacuo. The residue was purified by chromatography on silica, eluting with 1: 2 ether: hexane. 2-Benzyloxymethyl-2-ethylpropane-dial was obtained as a pale brown oil (3.3 g) which was used immediately.

Infrared spectrum (liquid film): ω 1720 cm "'.

(iv) Methylmagnesium iodide (16 ml), 3M solution in ether) was added to a solution of 2-benzyloxymethyl-2-ethylpropanedial (3.2 g) in dry ether (70 ml). The mixture was refluxed for two hours with stirring and cooled. Aqueous ammonium chloride solution was added (30ml, 10%) and the aqueous mixture extracted with ether. The ethereal extracts were washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo.

The residue was purified by chromatography on silica, eluting with ether. 3-Benzyloxymethyl-3-ethylpentane-2,4-diol was obtained as a pale yellow oil (2.1 g).

Gas-liquid chromatography (glc) OV210 at 185 ° C showed a peak.

The following nuclear magnetic resonance (NMR) spectrum was determined: ¹ H (particles / millimeter of TMS in CDCl ₃ , integral, number of peaks: 7.40.5H, s, 4.60.2 H, s, 4.40- 3.40.6H, m; 1.60-0.75, 11H, m.

(v), 3-ethyl-3-hydroxymethylpentane-2,4-diol was prepared from 3-Ben ₁ ^t yloxymethyl-3-ethylpentane-2,4-diol, using in step (iv) described in Example C Method prepared. 3-Ethyl-3-hydroxyethylpentane-2,4-diol was obtained as a pale brown oil.

Dia gas-liquid chromatography (glc) OV210 at 170 ° C gave a peak.

The following nuclear magnetic resonance spectrum (NMR) was determined: ¹ H (particle / millimeter of TMS in CDCl ₃ , integral, number of peaks): 4.60-3.50.7H, m; 1,80-0,70,11 H, m.

(vi) 1- (4-chlorophenyl) -3,5-dimethyl-4-ethyl-2,6,7-trioxabicyclo [2.2.2] octane (0.21 g), a colorless oil, became 3 Ethyl 3-hydroxymethylpentane-2,4-diol (0.7g) was prepared using the method described in step (iii) of Example A.

The gas-liquid chromatography (glc) 0V210 at 220 ⁰ C gave a peak.

In an analogous manner, the following compounds were prepared:

1-cyclohexyl-3,5-dimethyl-4-n-propyl-2,6,7-trioxabizyklo- [2,2,2 | octane,

1- (4-bromophenyl) -3,5-dimethyl-4-n-propyl-2,6,7-trioxabizykio [2,2,2] octane,

1- (4-chlorophenyl) -3,5-dimethyl-4-n-propyl-2,6,7-trioxabizyklo [2,2,2] octane.

Example F:

1- (4-Chloro-phenyl) -4-n-propyl-3-trifluoromethyl-2,6,1-trioxabicyclo [2,2,2] octane, sodium hydride (8.0g), 60% dispersion in oil) became stirred solution of Oiethyl-n-propyl malonate (40g) in dry benzene (200ml). The mixture was kept at 60 ° C with stirring for one hour. The mixture was cooled and trifluoroacetic anhydride (28 ml) was added carefully. The mixture was stirred at room temperature for two hours.

Water was added and the aqueous mixture was extracted with diethyl ether. The ethereal extracts were washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo.

Distillation gave 2-n-propyl-2-trifluoroazetylmalonat, a colorless oil (bp 73 ⁰ C, 0.2 mm) (35g).

Gas-liquid chromatography (glc) OV210 at 13O ⁰ C gave a peak.

It was determined the following nuclear magnetic resonance spectrum (NMR): Ή (particles / Mill from TMS in CDCI _3, integral, number of peaks, J _Hl.): 4,30,4H, 1.8; 2,00,2 H, m; 1.50 to 0.70, 11H, m.

3,3-Di (hydroxymethyl) -1,1,1-trifluorohexan-2-ol was prepared from diethyl 2-n-propyl-2-trifluoroacetylmalonate using the procedure described for the preparation of 2-ethyl-2-hydroxymethylbutane-1 , 3-diol method described (Example A (ii)).

1- (4-chlorophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2.2.2-octane, i-cyclohexyl] -n-propyl-S-trifluoromethyl-2,6,7 trioxabicyclo [2,2,2,] octane and 1- (4-bromophenyl-4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2.2.2] octane were prepared from 3.3- Di- (hydroxymethyl-1,1,1-trifluorohexan-2-ol prepared by an analogous method to Example A (step (ii)).

Using similar techniques, 1- (4-chlorophenyl) -4-cyclohexyl-3-trifluoromethyl-2,6,7-trioxabicyclo-2,2,2-octane, 1,4-dicyclohexyl-3-trifluoromethyl-2,6 was obtained , 7-trioxabicyclo [2.2.2] octane and 1- (4-bromophenyl) -4-cyclohexyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2.2.2] octane.

When diethyl n-propyl malonate was replaced by diethyl prop-2-enyl malonate or diethyl 2-methylprop-2-enyl malonate, the following compounds were prepared:

1- (4-bromophenyl) -4-prop-2-enyl-3-trifluoromethyl-2,6,7-trioxabicyclo-2,2,2] octane, i -cyclo-prop-1-enyl-S-trifluoromethyl-2, 6,7-trioxabicyclo [2.2.2] octane, 1- (4-bromophenyl) -4- (2-methylprop-2-enyl) -3-trifluoromethyl-2,6,7-trioxabicyclo [2.2 , 2-octane, 1-cyclohexyl-4- (2-methylprop-2-enyl) -3-trifluoromethyl-2,6,7-trioxabicyclo (2,2,2] octane.

Example G

1- (4-Ethynylphenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabizyklo [2,2,2] octane

(i) A mixture of 3,3-di- (hydroxymethyl) -1,1,1-trifluorohexan-2-ol (2.8g), diethyl carbonate (1.6ml), potassium hydroxide (0.1g) and dry ethanol (4.0 mL) was added (under a stream of nitrogen fo (the duration of thirty minutes a gentle reflux treatment oil bath 11O ⁰ C) subjected. Then, the ethanol was removed by distillation. distillation gave 3- (1-hydroxy-2,2, 2-trifluoroethyl) -3n-propyl-oxetane (1.7g), a colorless oil (b.p. 112 ° C, 20-25mm).

Gas-liquid chromatography (glc) OV210 at 12O ⁰ C gave a peak.

Infrared spectrum (IR) (liquid film): 3450 (s, br), 1300 (s), 1170 (s), 1130 (s), 1045 (s).

(ii) A solution of 4-iodobenzoyl chloride (2.1 g) in dry dichloromethane (25 ml) was added to a stirred solution of 3- (1-hydroxy-2,2,2-trifluoroethyl) -3-n-propyloxetane (1, 55g) and pyridine (1.0ml) in dry dichloromethane at ⁰ ° C.

The reaction mixture was stirred at room temperature for 24 hours. The mixture was poured into water, and the aqueous mixture was extracted with diethyl ether. The ethereal extracts were washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo. The residue was purified by column chromatography on silica, eluting with 1% triethylamine in hexane.

There was recovered 3- [1- (4-iodobenzoyloxy) -2,2,2-trifluoroethyl] -3-n-propyloxetane as a colorless oil (2.4 g).

The gas-liquid chromatography (glc) OV2 ¹ 0 at 200 ⁰ C gave a peak.

The following nuclear magnetic resonance spectrum (NMR) was determined: ¹ H (particle / millimeter of TMS in CDCl ₃ , integral, number of peaks): 7.70.4H, m; 4.80-4.20.5H, m; 2.20 to 0.80.7H, m.

(iii) To a stirred solution of 3- [1- (4-Jodobenzoy oxy!) -2,2,2-trifluoroethyl] -3-n-propyloxetane (2.3g) in dry dichloromethane (50ml) was added at -7O ⁰ C boron trifluoride etherate (0.54 ml) was added. The mixture was allowed to warm slowly to room temperature and then stirred for 12 hours. Triethylamine (1.0 ml) was added and the mixture was poured into water. The aqueous mixture was extracted with diethyl ether. The ethereal extracts were washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo. The residue was purified by column chromatography on alumina eluting with 1: 4 dichloromethane: hexane saturated with ammonia.

There was recovered 1- (4-iodophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2,2,2-octane as a colorless solid (0.53 g).

Gas-liquid chromatography (glc) OV210 at 220 ° C gave a peak.

The following nuclear magnetic resonance spectrum (NMR) was determined: ¹ H (particles / millimeter of TMS in CDCl ₃ , integral number of peaks, J _H , i: 7.70, 2H, d, 8, 7.30.2 H , d, 8; 4.80-3.80.5H, m; 1.40.4H, m; 1.00.3H, m.

1- (4-cyanophenyl) -4-n-propyl-3-trifluoromethyl-2,8,7-trioxabicyclo [2,2,2] octane was prepared in an analogous manner by using 4-cyanobenzoyl chloride instead of 4-iodobenzoyl chloride in step (ii) produced.

1- (4-Bromo-3,5-dichlorophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo-2,2,2) octane and 1- (4-bromo-3-chlorophenyl) -4-n-p : opyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2.2.2] octane was prepared in an analogous manner by using 4-bromo-3,5-dichloroenzyzyl chloride or 4-bromo-3-chlorobenzoyl chloride instead of 4-Jcdobenzoyl chloride prepared in step (ii).

(iv) bis-triphenylphosphinepalladium dichloride (20 mg) and copper (I) iodide (5 mg) were added to a stirred solution of 1- (4-iodophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo [ 2,2,2] octane (0.5g) and trimethylsilylacetylene (0.24ml) in dry diethylamine (20ml). The mixture was stirred at room temperature for twelve hours. The mixture

was evaporated in vacuo and the residue was then dissolved in diethyl ether. The ethereal solution was washed with water, dried over anhydrous magnesium sulfate and evaporated in vacuo. The residue was purified by column chromatography on alumina eluting with 1: 4 dichloromethane: hexane saturated with ammonia. There was thus obtained 4-n-propyl-3-trifluoromethyl-1- [4- (2-trimethylsilylethynyl-2,6,6-trioxabicyclo [2,2,2-octane as a pale brown solid (0.36 g).

Gas-liquid chromatography (glc) OV210 at 23O ⁰ C gave a peak.

(v) Vetrabutylammonium fluoride solution (0.84 mL, 1M solution in tetrahydrofuran) was added to a stirred solution of 4-n-propyl-3-trifluoromothyl-1- [4- (2-trimethylsilylethynyl) phenyl] -2,6,7- trioxabicyclo [2.2.2] octane (0.28g) in dry tetrahydrofuran (5ml). The mixture was stirred at room temperature for 30 minutes. The solvent was removed in vacuo and the residue was dissolved in dry diethyl ether. The ethereal solution was washed with water, dried over anhydrous magnesium sulfate and evaporated in acetone. The residue was recrystallized from hexane. There was obtained 1- (4-ethynylphenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo [2.2.2] octane as a pale yellow solid (70 mg). Gas-liquid chromatography (glc) OV210 at 23O ⁰ C gave a peak.

Example H:

i - ^ - methyl ^ Ethynylphenyfl-S-propyl ^ ej-trioxflbizyklo ^^ lokten

(i) A mixture of 2,2-di (hydroxymethyl) pentan-1-ol (24.6g), diethyl carbonate (20.1ml), potassium hydroxide (0.3g) and dry ethanol (2ml) was added under a Nitrogen stream for 30 minutes on gentle reflux heated (oil bath, 11O ⁰ C to 12O ⁰ C). After this time, the ethanol formed was removed by distillation at atmospheric pressure (oil bath 130 ° C-140 ° C, distillation head temperature 76 ° C). The pressure was reduced to 20 mm Hg and the oil bath temperature adjusted to 23O ⁰ C. 3-Hydroxymeyl-3-n-propyloxetane was distilled as a colorless liquid (16.7 g, head temperature 120 ° C-126 ° C). Gas-liquid chromatography (glc) OV210 at 120 ° C gave a peak. The following nuclear magnetic resonance spectrum (NMR) was determined: ¹ K (particles / millimeter of TMS in CDCl ₃ , integral, multiplicity): 4.35.4H, s; 3,60,2H, m; 1.80 to 0.7.7H, m.

(ii) A solution of dimethyl sulfoxide (12ml) in dry dichloromethane (4.0ml) was added to a solution of oxalyl chloride (7.4ml) in dichloromethane (25ml) with stirring at -70X under nitrogen. After completion of the addition the resulting mixture was stirred for an additional five minutes at -7O ⁰ C before a solution of S-hydroxymethyl-Sn-propyloxetane (10.0g) in dichloromethane (25ml) was added dropwise over a period of 10 minutes. The resulting mixture was stirred for a further 30 minutes, then pure triethylamine (54 ml) was added over about 30 minutes.

The reaction mixture was allowed to warm to room temperature over 3 hours, after which it was poured into water.

The organic phase was separated and the aqueous layer was further extracted with fresh dichloromethane. The combined organic extracts were washed with dilute hydrochloric acid, saturated sodium bicarbonate and brine. The resulting organic phase was dried over anhydrous magnesium sulfate and evaporated in vacuo to give 3-formyl-3-n-propyloxetane (10.5 g) as a yellow oil.

Gas-liquid chromatography (glc) OV-210 at 12O ⁰ C gave a peak.

Infrared spectrum (IR) liquid film): 1730 cm "'.

The following nuclear magnetic resonance spectrum (NMR) was determined: Ή (particle / millimeter of TMS in CDCl ₃ , integral, multiplicity, J _Hi ): 9.0.1 H, s; 4.90, 2H, d, 6; 4, 60, 2H, d, 6; 2,30-1,0,7H, m.

(iii) A solution of 3-formyl-3-n-propyloxetane (10g) in dry ether (50ml) was added to a stirred solution of methylmagnesium iodide (0.078mol) in ether (100ml) at ⁰ ° C under nitrogen. The reaction mixture was allowed to warm to room temperature and stirred for an additional three hours. Thereafter, it was cooled to ⁰ ° C. and a sufficient amount of saturated ammonium chloride solution was added slowly to dissolve the resulting precipitate. The organic phase was separated and the aqueous layer reextracted with fresh ether. The combined organic extracts were washed with brine, dried over anhydrous magnesium sulfate and then evaporated in vacuo. The residue was purified by column chromatography on silica, with gradient elution of methanol / ether mixtures.

Elution with pure ether gave 3- (1-hydroxyethyl) -3-n-propyloxetane as an oil (2.5g).

Gas-liquid chromatography (glc) OV-210 at 12O ⁰ C gave a peak.

Infrared spectrum (IR) (liquid film): 3420 (s, br), 1470 (s), 1120 (s), 985 (s) cm ^-1 .

It was determined the following nuclear magnetic resonance spectrum (NMR): Ή (particles / Mill from TMS in CDCI _3, integral, multiplicity, J _Hl.): 4,65,2H, d, 6; 4,35,2H, d, 6; 3,9,1H, q, 6; 1,15,3H, d, 6; 1.9-0.8.7H, m.

(iv) A solution of 4-iodobenzoylchloride (3.5g) in dry ether (25ml) was added to a stirred solution of 3- (1-hydroxyethyl) -3-n-propyloxetane (1.7g) and pyridine (1.8ml). in ether (50ml) at 0 ^° C. The resulting mixture was stirred at room temperature for 24 hours. Thereafter, the mixture was washed with water and brine. The organis. Extracts were dried over anhydrous magnesium sulfate and then evaporated in vacuo. The residue was purified by column chromatography on S'lika (pre-eluted with 1% triethylamine in hexane), eluting with hexane-ether mixtures. There was obtained 3-1- (4-iodobenzoyloxy) ethyl) -3-n-propyloxetane as a colorless oil (1.8 g).

The gas-liquid chromatography (glc) OV-210, programmed from 120 ⁰ C to 25O ⁰ C, yielded a peak.

Infrared Spectrum (IR) (liquid film): 1730 (s), 1285 (s), 1115 (s), 1020 (s), / 70 (s) cm- ¹ .

The following nuclear magnetic resonance (NMR) spectrum was determined: 'H (particle / millimeter of TMS in CDCl ₃ , integral, multiplicity): 7.8, H, s; 5.4, 1H, q; 4,85-4,35,4H, m; 1.9-0.8, 10H, m.

(v) 3- [1- (4-iodobenzoyloxy) ethyl] -3-n-propyloxetane was dissolved in 1- (4-ethynylphenyl) -3-methyl-4-propyl-2,6,7-trioxabicyclo [2.2 , 2] octane by a method which is exactly the same in Example G, steps (iii), (iv) and (v), and the corresponding intermediates were isolated and characterized.

Gas-liquid chromatography (glc) on the final product OV-17 at 240 ° C gave a peak.

Example I:

4-t-butyl-3-cyano-V (4-ethynylphenyl) -2,6,7-trioxabizyklo- [2,2,2] okton

(i) To a stirred solution of pyridinechlorochromate (6.5g) in dry dichloromethane (50ml) under a nitrogen atmosphere was added 3-t-butyl-3-hydroxymethyloxetane (2.9g) in dichloromethane (10ml). The mixture was stirred overnight and dry diethyl ether (100 ml) was added. The mixture was passed through a Fluorosii column

filtered. The column was washed with further Etherporiionen (2 χ 50 ml). The combined filtrates were evaporated in vacuo. 3-t-Butyl-3-formyloxetane was recovered as a colorless solid (2.3 g).

The following nuclear magnetic resonance (NMR) spectrum was determined: ¹ H (particle / millimeter of TMS in CDCl ₃ , integral, number of peaks): 9.90.1H, s; 4.70-4.40 (4H, q); 1.05,9H, s.

(ii) To a stirred solution of 3-t-butyl-3-formyloxetane (1.0g) and 4-iodobenzoyl chloride (2.6g) in dry diethyl ether (35ml) under nitrogen was added a solution of sodium cyanide (1.25g) in water (1.0ml) added. The mixture was stirred overnight. The mixture was poured into water (50 ml) and the aqueous mixture was extracted with diethyl ether. The ethereal solution was dried over anhydrous sodium sulfate and then evaporated in vacuo. The residue was chromatographed on silica pretreated with triethylamine, eluting with hexane: chloroform 1: 3. The 4-iodobenzoate of 3-t-butyl-3- (cyanohydroxymethyl) oxetane was recovered as a colorless solid (2.54 g). The following nuclear magnetic resonance spectrum (NMR) was determined: ¹ H (particles / millimeter of TMS in CDCl ₃ , integral number of peaks): 7.90-7.70.4H, q; 5.80.1 H, s; 4,80-4,60,4H, m; 1,10,9H, s.

4-t-Butyl-3-cyano-1- [4- (2-trimethylsilylethynyl) -phenyl-2,6,7-trioxabicyclo [2,2,2] octane was prepared from the 4-iodobenzoate of 3-t-butyl 3- (cyanohydroxymethyl) oxetane using the method described in Example G. A mixture of 4-t-butyl-3-cyano-1- | 4- (2-trimethylsilylethynyl) phenylJ-2,6,7-trioxabicyclo [2.2.2loctane (1.3 g) and anhydrous potassium carbonate in dry methanol ( 125 ml) was stirred under dry nitrogen for two hours. The resulting solution was evaporated in vacuo. The residue was taken up in diethyl ether and the ethereal solution washed with water. The ethereal solution was dried over anhydrous sodium sulfate and evaporated in vacuo. The residue was purified by chromatography on alumina, eluting with hexane: dichloromethane in the ratio 4: 1, saturated with ammonia. 4-t-Butyl-3-cyano-1- (4-ethylphenyl) -2,6,7-trioxabicyclo [2.2.2] octane was obtained as pale yellow needles (600 mg). From 3-formyl-3-isoptopyloxetane and 4-cyanobenzoyl chloride, using the procedure described above, 3-cyano-1- (4-cyanophenyl) -4-isopropyl-2,6,7-trioxabicyclo [2.2.2] octane manufactured.

Example J:

1- (4-Zyanophenyl) -3-ethynyl-4-isopropyl-2,6,7-trioxabizyklo- [2,2,2] octane

To a stirred suspension of lithium azetylidene-ethylene diamine complex (2.76g) in dry dioxane (25ml) under nitrogen was added at ⁰ ° C a solution of 3-formyl-3-isopropyloxetane (2.56g) in dry dioxane (10ml). The mixture was allowed to warm to room temperature. After three hours, nuclear magnetic resonance analysis showed that 3-formyl-3-isopropyloxetane was still present. An additional portion of the lithium azetylidene-ethylenediamine complex (3.0 g) was added and stirring continued overnight. The mixture was poured into ice-shifted water, and the aqueous mixture was extracted with diethyl ether. The ethereal extracts were washed with water and dried over anhydrous sodium sulfate. The ethereal solution was evaporated in vacuo. 3- (1-Hydroxyprop-2-ynyl) -3-isopropyloxetane was recovered as an orange oil (0.8g). The following nuclear magnetic resonance (NMR) spectrum was determined: ¹ H (particles / mill. Of TMS in CDCl ₃ , integral, number of peaks): 4.45.1H, s; 4,70-4,40,4 H, m; 2,50,1H, s; 2.5.1 H, s; 2,10,1 H, m; 1.10, -1.00, 6H, m.

From 3- (1-hydroxyprop-2-ynyl) 3-isopropyloxetane and 4-cyanobenzoyl chloride was added 1- (4-cyanophenyl) -3-ethynyl-4-isopropyl-2,6,7- using the procedure described in Example G. trioxabicyclo [2,2,2-octane produced.

The data on the mass spectra, infrared spectra and magnetic resonance spectra for the compounds given in the examples are given in Table I.

Table I

No. R ' R R ¹ enamel masses infrared spectrum Method off Point spectrum example ( ⁰ C) Chem. ionization M + 1 1 4-CI-phenyl et me 48-50 269 1100 (s), 1080 (m), 1200 (m) A 2 4-Br-phenyl et me 53-54 313315 1105 (s), 1080 (w), 1020! S) A 3 c. Hex. et me oil 241 , 1080 (s), 1010 (s), 9/5 (m) A 4 4-CI-phenyl et et 73-74 283 1110 (s), 1100 (s), 1025 (s), B 1010 (s) 5 c. Hex. et et oil 255 , 1080 (s), 1020 (s), 970 (m) B 6 4-CI-phenyl n-pr me 39-41 283 1110 (s), 1025 (sj, 1000 (s) A 7 4-Br-phenyl η me 40 327329 1100 (s), 1080 (w), 1020 (s), A 8th c. Hex. n-pr me oil 255 108 (J (BM1017 (s), 975 (m) A 9 4-CI-phenyl i-pr me oil 283 1100 (s), 1 075 (w), 1 020 (s) A 10 c-Hex. i-pr me oil 255 1 090 (w), 1 055 (m), 1 020 (s), 975 (w)

R ^? R c. Hex. t-Bu R ' enamel iVlassen- 297 - Infrarotspektrurn 16-279 814 No. nPr n-pr Point spectrum 339341 Method off ( ⁰ C) Chem. 309 example nPr n-pr ionization nPr n-Bu M + 1 381 383 4-Br-phenyl -CH2CH2CH2 n-Bu CH ₂ solid 3Ϊ5327 11 c. Hex. -CH2CH2CH2 CH ₂ - 43- ^ 16 253 337 1080 (m), 1060 (m), 1015 (s), D 12 nPr 970 (s) D 4-Br-phenyl c. Hex. iPr me solid fuel 367369 421 423 13 4-Br-phenyl t-Bu me 104-113 341343 1085 (m), 1060 (w), 1010 (s) C 14 4-Br-phenyl t-Bu IPr et 122-128 355357 377 1 090 (m), 1 060 (w), 1 020 (s) B 15 c. Hex. c. Hex. nPr me 55-56 295 1 090 (m), 1 020 (s) 8th 16 4-CI-phenyl t-Bu 2-methyl- me 96-98 1140 (s), 1100 (s), 1025 (s) C 18 4-Br-phenyl nPr prop-2-enyl CH = CH ₂ solid fuel 1620 (w), 1105 (s), 1020 (s) B 19 c. Hex. nPr 2-methyl- CF ₃ 48-49 397 399 1170 (s), 1140 (s), 1090 (m), B 20 prop-2-enyl 1 030 (s) F 4-Br-phenyl η Pr c. Hex. CF ₃ 54-56 1170 (s), 1135 (m), 1 120 (m) 21 Prop-2-enyl 273 1050 (m), 1,025 (m) F 4-CI-phenyl nPr CF ₃ 71-73 345 1170 (s), 1140 (m), 1120 (m) 22 Prop-2-enyl 1 045 (s), 1 020 (s) F 4-Br-phenyl c. Hex. CF ₃ solid fuel 1180 (s), 1145 (s), 1115 (s), 23 t-Bu 375 1045 (m), 1,025 (s) F 4-CI-phenyl c. Hex. n-pr CF ₃ solid fuel 355357 1070 (s), 1100 (s), 1120 (s) 24 4-Ethynylphenyl nPr n-pr CF ₃ solid fuel 3310 (w), 1172 (s), 1130 (m), F 25 4-I2- (trimethyl-nPr i-pr CF ₃ solid fuel 283 m G 26 silyl) ethynyl] phenyl npr 328 G 4-Br-phenyl n-pr MeOCH ₂ solid fuel 393395 1100 (s), 1020 (s) 27 4-l-phenyl i-pr CF ₃ solid fuel 1180 (s), 1145 (s), 1120 (s), A 28 i-pr 321 1 025 (s) G 4-Ethynylphenyl n-Bu me solid fuel 29 4- [2-trimethyl- n-Bu me solid fuel 349 H 30 silyOethynyl) I-pr 307 H phenyl i-pr 4-l-phenyl t-Bu me 58-63 379381 1110 (s), 1020 (s), 830 (s) 31 4-Br-phenyl 4- [2-trimethylsilyl) ethynyl) nPr waxy 1105 (s), 1085 (m), 1020 (s) H 35 phenyl solid fuel A c. Hex. 4-Ethynylphenyl nPr oil 341 343 1050 (m), 1020 (s), 980 (m) 36 4-CN-phenyl 4-Br-3,5-di-CI- CF ₃ solid fuel 269 2250 (m), 1170 (s), 1140 (s) A 37 4-Br-phenyl phenyl CF ₃ solid fuel 341 343 1185 (s), 1065 (m), 1110 (s), G 38 4-Br-3-CI-phenyl 357359 1 020 (s) F c. Hex. 4-Br-phenyl CF ₃ oil 285 1160 (w), 1165 (s), 1! 20Im), 39 4-l-phenyl 357359 1 085 (m). 1 030 (m) F c. Hex. CF ₃ solid fuel 285 1180 (S) JIOO (S) ₁ IOSO (S). 40 c. Hex. CF ₃ oil 341 343 1650 (w) J180 (s) J140 (m), F 41 297 1 090 (m), 1 030 (m) F 4-Br-phenyl CF ₃ solid fuel 285 1 650 (w) J 180 (s) J 140 (m), 42 284 1110 (s) J020 (s) F c. Hex. me 69-71 400 1 055 (s), 1 025 (s) 43 4-Br-phenyl et solid fuel 1 105 (s) J 032 (s) J 020 (s) B 44 c. Hex. et oil 1 090 (m), 1 062 (m), 1 020 (s) A 45 4-Br-phenyl et Oily solid 298 1110 (m) J020 (s) A 46 4-Br-phenyl MeOCH ₂ solid fuel 449451 1110 (m) J020 (s) 47 c. Hex. MeOCH ₂ oil 1105 (m) J 080 (m) J 020 (s) A 48 4-Br-phenyl MeOCH ₂ solid fuel 415417 1140 (m) J 100 (s) J 000 (s) A 49 c. Hex. MeOCH ₂ oil 395397 1 100 (m) J 055 (m) J 025 (s) A 50 4-Br-phenyl me 389 1 100 (s) J010 (s), 990 (m) A 51 4-CI-phenyl me 1095 (s) J015 (s), 990 (m) A 52 4-CN-phenyl CN 141-143 A 53 4-CN-phenyl C = CH 84-85 54 4-l-phenyl CN 155-157 55 t-Bu CN 56 CN 123-125 5 / CF ₃ solid fuel 58 CF ₃ solid fuel 59 CF ₃ 50-52 1155 (s) J125 (m) J100 (m) 60 me solid fuel 1 005 (s) F 61 H

No. R ²

R '

enamel masses infrared spectrum Method off Point spectrum example ( ⁰ o Chem. ionization M + 1

62 4- (2-trimethyl-n-Bu = tertiary butyl me solid fuel silylethynyl) = normal propyl phenyl = Isopropyl 63 4-Ethynylphenyl n-Bu me solid fuel 64 Cyclohexyl t-Bu CN oil 65 4-Br-phenyl n-pr CN 116-118 66 4-l-phenyl n-pr CN solid fuel 67 4- (2-trimethyl-n-pr CN solid fuel silyljethynyl) phenyl 68 4-Ethynylphenyl n-pr CN solid fuel c. Hex. = Cyclohexyl t-Bu n-Pr i-Pr

359

287

1 2 3 4 5 6 7 8 9 10 11 12 13 14 1b 16 18 19 20 21 22 23 24 25 26 27 28 29 30 31 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49

Nuclear Magnetic Resonance Spectrum ( ¹ H, expressed in CDCl ₃ and expressed as particles / millimeter of TMS, number of protons, number of peaks, and J _H z (as indicated) 7.55.2 H, d, 8, 7.30, 2 H, d, 8; 4.50-3.80.5 H, m; 1.70 to 1.90.5 H, m; 0.95.3 H, 7.45,4 H, s; 4, 40-4,0,5H, m; 1,7-1,2,5H, m; 0,9,3H, t,. 6

4,00,5H, m; 2,00-0,6,19H, m.

7,50,2H, d, 8; 7,30,2H, d, 8; 4,1-3,8,5H, m; 2,0bis0,8,10H, m.

3,90,5H, m; 2.0-0.9.21 H, m.

7,40,2H, d; 8; 7,65,2H, d, 8; 4,4-3,9,5H, m; 1,7-0,9,10H, m.

4,25-3,6,5H, m; 2,00-0,8,21, m.

7, 50, 2 H, d, 7; 7,25,2 H, d, 7; 4.5-4.00.5 H, m; 1.80 to 1.20.4, m; 0.95.6 H, d, 4.25, 1H, q, 6, 4.0, 4H, s, 2.00-0.8, 21H, m.

7,40,4H, s; 4,55,1H, dd, 8.3; 4,00,4H, m; 2,20-0,90,8H, m.

4.35.1 H, dd, 7.3; 3,80,4H, m; 2,2-0,8,19H, m. 7,40,4H, s; 4,55,1H, q, 6; 4,15,4H, s; 2,00-0,80,14H, m. 7,40,4H, s; 4,60-4,00,5H, m; 1,55,3H, d, 6; 1,00,9H, s. 7,40,4H, s; 4,40-4,00,5H, m; 2,00,2H, m; 1,20,3H, t, 6; 1, C0,9H, s. 4,30,1H, q, 6; 4,00,4H, s; 2.20 to 0, a0,25H, m. 7,40,2H, d, 8; 7,20,2H, d, 4,80-3,80,5H, m; 1,60,3H, d, 7; 1,00,9H, s. 7,50,4H, s; 6.20-5.20.1 H, m; 4,50,2H, m; 4,30-3,90,5H, m; 1,40-0,70,7H, m. 4.60-3.60.5H, m; 2,20-0,80,18H, m. 7,50,4H, m; 4,80-3,80,5H, m; 1,70-0,80,7H, m.

7.45.2 H, d, 8; 7,35,2 H, d, 8; 4,60-3,80,5H, m; 1.60 to 0.80.7H, m. 7,50,4H, s; 4,70,1H, m; 4,20,4H, m; 2,00-0,90,11 H, m.

7, 50, 2 H, d, 8; 7, 30, 2 H, d, 8; 4,80,1H, m 1 4,30,4 H, m; 2,00 - 0,90,11 H, m.

7,40,4H, m; 4,70-3,80,5H, m; 3,05,1H, s; 1,50-0,80,7H, m.

7,50,4H, m; 4,80-3,90,5H, m; 1,60-0,80,7H, m; 0,40,9H, s.

7,50,4H, s; 4.80-3.50, 10H, m; 2,20-1,00,11 H, m.

7,40,2H, d, 8; 7,30,2H, 8; 4,70-3,80,5H, m; 1,40,4H, m; 1,00,3H, m.

7,40,4H, m; 4.5-3.8.5H, m; 3.0.1 H, s; 1,3,3H, d, 6; 1,3-0,7,7H, m.

7,45,4H, m; 4,4-3,9,5H, m; 1,4,3H, d, 6; 1,4-0,8,7H, m; 0,3,9H, s.

7,70,2H, d, 8; 7,30,2H, d, 8; 4,5-3,9,5H, m; 1,45,3H, d, 6; 1.7 to 0.8, 7H, m.

7,40,4H, s; 4,40-4,00,5H, m; 0,75,14H, m.

4.30-3.70.5H, m; 2,20-0,70,25H, m.

7,65,4 H, s; 4.80-3.80.5 H, m; 1.75 - 0.80.7 H, m.

7,50,4H, s; 5.05.1 H, s; 4,80,1 H, s; 4,60-4,00,5H, m; 2.30.1 H, d, 14; 2,20,1 H, d, 14; 1,75,3Hs.

4.95.1 H, s; 4,72,1 H, s; 4.40-3.70.5H, m; 2,17,1 H, d, 14; 2.07.1 H, d, 14; 1,90-0,90,14H, m.

4,60-3,80,5H, m; 2,0U-O ₁ PO, 22H, m.

5,65,1 H, m; 5,15,2H, m; 4,60-3,75,5H, m; 2,35-0,90,13H, m.

7,50,4H, s; 5,65,1 H, m; 5,20,2H, m; 4,60-4,00,5H, m; 2,40-2,10,2H, m.

4.40-3.80.5H, m; 2,0-0,95,23H, m.

7,40,4H, s; 4,20-3,80,5H, m; 1,70,2H, m; 1,40-0,90,10H, m.

4,00 - 3,75,5 H, m, 2,00 - 0,80,23 H, m.

7,40,4H, s; 4,20,5H, m; 1,80,3H, m; 1,30,3H, m; 1,00,6H, d,. 6

7,40,4H, s; 4,40-4,00,5H, m; 3,80,2H, d; 3,40,3H, s; 1,40,4H, m; 1,00,3H, m.

4,40-4,00,5H, m; 3,80,2H, d; 3,55,3H, s; 2,20-1,00,18H, m.

7,40,4 H, s; 4,50,1H, m; 4,20,4H, s; 3,80,2 H, d wide), 3,40,3 H, s; 2,00,1H, m; 1.00.6H, dd.

50 4,30,1H, m; 4,00,4H, m; 3,65,2 H, m; 3,40,3 H, s; 2.00 to 0.80.18 H, m.

51 7,50,4 H, s; 4.50-3.90.5 H, m; 1,50 -0,90,12H, m.

52 7.60,2H, d, 7; 7,40,2H, d, 7; 4,50-3,90,5H, m; 1,50 to 0,90,12, m.

53 7,65,4H, q; 5.05.1H, d; 4.40-4, i'0.4H, m; 1,95,1H, m; 1,00,6H, m.

54 7,75,4H, q; 5,00,1H, m; 4,40-4,00,4H, m; 2.55.1H 2s; 1,90,1H, m; 0.95.6H, m.

55. 7,70-7,30,4H, q; 4,95,1H, d; 4,50-4,00,4H, m; 1,05,9H, s.

56 7.60-7.40,4H, q; 4,95,1H, d; 4,50-4,00,4H, m; 1,00,9H, s; 0,20,9H, s.

57 7.60-7.40,4H, q; 4,95,1H, d; 4,50-4,00,4H, m; 3,05,1H, s; 1,05,9H, s.

58 7,60,2 H, s; 4,50,1H, m; 4,35,1 H, m; 4,10,3 H, m; 1.60 to 0.85.7 H, m.

59.7.70.1 H, d, 1.5; 7, 60, 1 H, d, 7; 7, 35, 1 H, dd, 7, a, 5; 4,50,1 H, m; 4.35.1 H, m, 4.05.3 H, m; 1,60-0,80,7H, m.

60 7,50,4 H, s; 4,50,1H, mgm, rmtngh, m; 4.05.3 H, mgm, qmtpapmipnoh, mm.

61 umupnwh, d. 7; 7, 40, 2H, d, 7; 4,60-4,00,5H, m; 1.80 to 0.80, 12H, m.

62 7.55,2H, d, 7; 7,45,2H, d, 7; 4,40-3,90,5H, m; 1,40,3H, d, 6; 1,30,6H, m ; 0,90,3H, 6, t; 0,25,9H, s.

63,75,2H, d, 7; 7, 50, 2H, d, 7; 4,35,1 H, m; 4,25-3,95,4H, m; 3.05.1 H, s; 1,50-1,10,9H, m; 0,95,3H, t, 7.

64 4,75,1H, d; 4.30-3.75.4H, m; 1.85-1,50,6H, mgm, qmwpaqmppnth, m; 0.95,9H, s.

65 7.45m, 4H, m; 4,90,1 H, d; 4.40-4.05.4 H, mgm, qmrtaqmwpnrh, m; 0.95m 3H, t.

66 7,70,2H, d; 7,30,2H, d; 4,90,1 H, d; 4.35-4.05,4H, mgm, qmrtaqmqtnerh.m; 0,953Ht.

67 7.50,2H, d; 7,45,2H, d; 4.90.1 H, d; 4.40-4.05 H, m; 1,50-1,10,4H, m; 0.95.3 H, t; 0,20,9 H, s.

68 7,50,2H, d; 7,45,2H, d; 4.95.1 H, d; 4,35-4,05,4H, m; 3,05,1H, s; 1,45-1,10,4H, m; 0,95,3H, t.

No. R ' R R ^{1 RJ} enamel mass Infrared method Point spectral. spectrum out Chem.lon. M + 1 example 17 4-CI-phenyl et me me oil 283 1105 (s), 1080 (w), e 1025 (s), 1000 (s) 32 4-Br-phenyl n-Pr me me oil 341343 e 33 4-CI-phenyl nPr me me oil 297 1100 (s), 1027 (s) LJU 34 c. Hex. nPr me me oil 269 1100 (s), 1020 (s) e

No. Magnetic nuclear magnetic resonance spectrum

17 7,45,2 H, d, 8; 7,20,2 H, d, 8; 4,40,2 H, q, 6; 4,00,2 H, m; 1.30.8 H, m; 0.90.3 H, m.

32 7.50,4H, s; 4,50-3,50,4H, m; 1,70-0,80,13H, m;

33 7.45,2H, d, 8; 7,35,2H, d, 8; 4,50-3,90,4H, m1; 1,50 to 1,1,10,10H, m; 0,90,3Hm.

34 4,30-3,70,4H, m; 2,00-1,00,21H, m; 0,90,3H, m.

Biological activity

The numbers given for the compounds refer to the number of the compound in the table above.

A. Deadly activity against the housefly

The activity of the compounds of the invention against the unaesthetized female muscadomestica (WRL strain) was demonstrated by the topical application of a solution of the compound to be tested in butanone to the experimental insect.

The effect of the compound was also assessed at local application in conjunction with a synergic (6pg piperonyl butoxide (PB] per insect) Mortality was estimated at 24 and 48 hours.

The following compounds were active at less than 30 μg / fly:

1,11,12,15,16,19,20, 22, 37,38,40,41,42,14,45,46,47,48,49, 50,17, 32, 33,34.

The following compounds were active at less than 1 μg / fly:

6, 7, 8, 9, 10, 13, 14, 18, 21, 23, 24, 25, 26, 27, 29, 30.

B. Lethal activity against Blattella germanica

The activity of compounds of the invention against uneaten male Blattella germanica (WRL strain) was demonstrated by the topical application of a solution of the compound to be tested in butanone to the experimental insect.

The activity of the compound was also assessed in the topical application of the compound in conjunction with a synergic agent (10 μg piperonyl butoxide [PB] per insect), the mortality was assessed at 24 and 48 hours.

The following compounds were active at less than Opg / insect: 1,5,11,12,13,15,18,19,20,21,23,25,26,27,36,37,38,39,40, 41 , 42,44,48,32,33,34.

The following compounds were active at less than 5 μg / insect: 6,7,8,9,29,30.

C. Lethal activity against Sitophilus granarius

The activity of the compounds of the invention against S. granarius (adult animals) was demonstrated by the addition of the compound in acetone solution to corn, which was later infected with the insects. The mortality rate was estimated after 6 days.

The following compounds were less than 200 particles / mill. Acetone solution active: 16,18,19,20,22,23, 26,27,37,41,42,43, 44, 32,33, 34.

The following compounds were less than 50 particles / mill. Acetone solution active: 6,14,15,21,25,29.

D. Deadly activity against Culex guinguefasciatus

The activity of the compounds of the invention against adult female Culex was demonstrated by directly spraying 0.5 ml of the compound in OPD / methylene chloride. The lethality was estimated after 24 hours.

The following compounds were active at less than 1.0%:

6,12,14,15,18,19, 21,22, 23,24, 25,26, 27, 37,39,41,43,33,48,50,44.

The following compounds were active at less than 0.1%:

E. Toxicity in mammals

Compound 15 has an LD ₅₀ more than 20 mg / kg when administered orally to mice (Charles River DC1).

compositions

Emulsifiable concentrate

Connection 11

Ethylene KEO

xylene

Butylieries Hydroxyanisole

10.00

20.00

67,50

2.50

100.00 Wettable powder Connection 11 25,00 Attpulgit 69,50 Natriumisopropylbenzensulfonat 0.50 Sodium salt of condensed naphthalenesulfonic 2.50 Butylated hydroxytoluene 2.50 100.00 dust Connection 11 0.50 Butylated hydroxyanisole 0.10 talc 99.40 100.00 bait Connection 11 40,25 powdered sugar 59.65 Butylated hydroxytoluene 0.10 100.00 paint Connection 11 2.5 resin 5.0 Butylated hydroxyanisole 0.5 Highly aromatic white spirit 92.0 100.00 aerosol Connection 11 0.30 Butylated hydroxyanisole 0.10 1,1,1-trichloroethane 4.00 Odorless Kerosen 15,60 Areton 11/12. Mixture 50:50 80,00 100.00 spray Connection 11 0.1 Butylated hydroxyanisole 0.1 xylene 10.0 Odorless Kerosen 89.8

100.00

8. Potent Spray Compound 11 Piperonyl Butoxide Butylated Hydroxyanisole Xylene Odorless Kerosen

0.1

0.5

0.1

10.1

89.2

100.0

Scheme 1

R ¹⁰ O OH

Protection of one or two hydroxy groups

R ¹⁰ O OR ¹⁰

Conversion of the remaining hydroxy group (s) in ι i i <

I OR aldehyde, for example I

HO OH through the use of pyridinechorochromate

HO

0R ^J

R ¹⁰ O

ν R

R ¹⁰ O OH

Reaction with the Gr "" Nard reagent R "^1" MgHaI

OHC

^S CHO

11

R elimination of protection \>

the hydroxy groups

HO OH

(R ³ ^ B ¹ )

^R R ³ ? R ¹

OH HO OH J

wherein R ¹⁰ , R "are protecting groups which can be removed under different conditions, for example by hydrogenolysis and acid hydrolysis Advantageously, both groups R ^{10 are} joined to form an isopropylidene group and R" is benzyl.

Claims (7)

1. pesticides, in particular insecticidal or acaricidal composition, characterized in that it comprises as active ingredient a trioxabicyclo / 2,2,2 / octane of the general formula I. wherein R is C ₂ _ ₁₀ alkyl, alkenyl or alkynyl, each optionally substituted by or methyl-substituted by a cyano, C 1-6 cycloalkyl, halo, C 1-4 alkoxy group or a group S (O ⁾ m R ⁴ , wherein R ⁴ C ₁ ^ ₄ -AlkYl and m is equal to 0.1 or 2, or R is C ^, ₀ -cycloalkyl, C ₄ ^ ₀ -cycloalkenyl or phenyl, each optionally substituted by a C ^ alkoxy, C, _ ₃ alkyl, _C2 -4 alkynyl, halo, cyanosis, or a group S (0) mR ^4, as defined above; R ¹ is a halo group, C -, _ ₃ alkyl, C ₂ _3 alkenyl or alkynyl, each optionally substituted by a halo, cyanosis, C ₁ ^ -AIkOXy-, Alkylkarbalkoxygruppe having up to 6 carbon atoms, a group S (0) mR ^4, as defined above, or alkynyl substituted by tri C 1-4 alkylsilyl, or R ^{1 is} a cyano group, spiro-cyclopropyl, gem-dimethyl, gem-dicyano, gem-diethylnyl, oxo or methylene group, optionally substituted by a cyano group or C 1-4 alkyl, optionally subst ituiert by fluorine, or R ¹ and R and the carbon atoms to which they are attached, form a carbocyclic C ^ ring, optionally substituted by a halo, C ^ alkyl or alkoxy group or C ₂ _5-alkonyl; R ² is phenyl, C ^ o-cycloalkyl or cycloalkenyl each optionally substituted and R ³ is hydrogen, C ^ alkyl, C ₂ _ ₃ alkenyl or alkynyl each optionally substituted by one cyanosis, Ci_4 alkylthio, Ci-4-alkoxy or halo group, or R ^{3 is} a cyano or halo group, in addition to carriers or diluents. 2. Composition according to claim 1, characterized in that in addition to the active ingredient a synergistic agent for the pesticidal compound is included. 3. Composition according to claim 1 or 2, characterized in that in addition to the active ingredient is still a second pesticidal compound is included. 4. The composition according to any one of claims 1 to 3, characterized in that the active ingredient is a compound of formula I in which R is propyl, butyl, pentyl, C ₂ _ ₅ alkenyl or alkynyl, C ^ y-cycloalkyl or phenyl each optionally substituted by one to three chloro, fluoro or bromo groups; R ^{1 is} a cyano group, ethynyl or methyl or ethyl, optionally substituted by a cyano, methoxy, methylthio or fluoro group; R ² is phenyl, C ^ ₁₀ -Zykloalkyl or cycloalkenyl is, each optionally substituted (by a halogen, cyanosis, azido, tetra-zolylgruppe or group S OJmR ^5, wherein m is 1 and R ⁵ is C ^ - Alkyl or rn is 2 and R ⁵ is C ^ alkyl, an amino or di-C ^ alkylamino group, a group COR ⁶ , wherein R ⁶ -C ₁ _ ₄ alkoxy, benzyloxy, amino, or di-C ₁ ^ alkylamino, nitro, C ^ alkyl group optionally substituted by a halo, cyano group or ethynyl, or C ₂ _ ₃ alkenyl or ethynyl each optionally substituted by a halo group or tri-C ^ - Alkylsilyl; and R ³ is hydrogen or methyl. 5. Composition according to one of claims 1 to 3, characterized in that as active ingredient 1- (4-bromophenyl) -4-cyclohexyl-3-methyl-2,6,7-trioxabicyclo (2,2,2) octane, 1 - (4-chlorophenyl) -3-methyl-4-iso-propyl-2,6,7-trioxabicyclo (2,2,2) octane, 1- (4-bromophenyl) -3-methyl-4-n- propyl 2,6,7-trioxabicyclo (2,2,2) octane, 1- (4-chlorophenyl) -3-methyl-4-n-propyl-2,6,7-trioxabicyclo (2,2,2) octane, 1-cyclohexyl-3-methyl-4-iso-propyl-2,6,7-trioxabicyclo (2,2,2) octane, 1- (4-bromophenyl) -4-6-butyl-3-methyl- 2,6,7-trioxabicyclo (2,2,2) octane, 1,4-dicyclohexyl-3-methyl-2,6,7-trioxabicyclo (2,2,2) octane, 4-t-butyl-1- {4-chlorophenyl) 3-methyl-2,6,7-trioxabicyclo (2,2,2) octane, 1- (4-ethylenediphthyl) -3-methyl-4-n-propyl -2,6,7-trioxabicyclo (2,2,2) octane _/ 3-methyl-4-n-propyl-1- (4- (2-trimethylsilylethynyl) -phenyl) -2,6 _/ 7-trioxabicyclo (2 , 2,2) octane _/ 1- (4-ethynylphenyl) -4-p.propyl-3-trifluoromethyl-2,6,7-trioxabicyclo (2,2,2) octane, 3-cyano-1- (4- ethynylphenyl) -4-n-propyl-2,6,7-trioxabicyclo (2,2,2) octane, 4-n-propyl-3-trifluoromethyl-1- (4 (2-trimethylsilylethynyl) -phonyl) -2 _/ 6,7-trioxabicylHo (2,2,2) octane, 1- (4-chlorophenyl) -4-n-piOpyl-3-tiifluoromethyl-2,6,7-trioxabicyclo (2,2,2) octane, 1- (4-Bromophenyl) -4-n-propyl-3-trifluoromethyl-2 _/ 6,7-trioxabicyclo (2,2,2) octane, 1- (4-chlorophenyl) -4-cyclohexyl-3-trifluoromethyl-2, 6,7-trioxabicyclo (2,2,2) octane, 1- (4-bromophenyl) -4-cyclohexyl-3-trifluoromethyl-2,6,7-irioxabicyclo (2,2,2) octane, 1- {4 -Bromophenyl) -3-ethenyl-4-n-propyl-2,6,7-trioxabicyclo (2,2,2) octane, 1-cyclohexyl-4-n-propyl-3-trifluoromethyl-2,6,7- trioxabicyclo {2,2,2) octane _/ 1- (4-bromophenyl) -3-cyano-4- n-propyl-2,6,7-trioxabicyclo (2,2,2) octane, 3-cyano-1- (4-ethynylphenyl) -4-n-propyl-2,6,7-trioxabicyclo (2,2, 2) octane, 1- (4-bromophenyl) -4-cyclohexyl-3-methoxymethyl-2,6,7-trioxabicyclo (2 _/ 2,2) octane, 1-cyclohexyl-3-methyl-4-n-propyl 2,6 _/ 7-trioxabicyclo (2,2,2) octane, 1- (4-bromophenyl) -4-t-butyl-3-ethyl-2,6 _/ 7-trioxabicyclo (2,2,2) octane, 4-t-butyl-1-cyclohexyl-3-methyl-2,6,7-trioxabicyclo (2,2,2) octane, 1- (4-chlorophenyl) -3,5-dimethyl-4-n-propyl 2,6,7-trioxabicyclo (2,2,2) octane, 1- (4-bromophenyl) -3,5-dimethyl-4-n-propyl-2,6,7-trioxabicyclo (2,2,2) octane, 1-cyclohexyl-3,5-dimethyl-4-n-propyl-2,6,7-trioxabicyclo (2,2,2) octane, 1- (4-cyanophenyl) -4-n-propyl-3- trifluoromethyl-2,6 _/ 7-trioxabicyclo (2,2,2) octane _/ 1- (4-bromophenyl) -4-n-butyl-3-methyl-2,6,7-trioxabicyclo (2,2,2) octane, 4-n-butyl-1- (4-chlorophenyl) -3-methyl-2,6,7-trioxabicyclo (2,2,2) octane, 4-t-butyl-3-cyano-1- (4 -ethynylphenyl) -2,6,7-trioxabicyclo (2,2,2) octane _/ 1- (4-cyanophenyl) -3-ethynyl-4-isopropyl-2,6,7-trioxabicyclo (2,2,2) octane, 3-cyano-1- ( 4-cyano-phenyl) -4-isopropyl-2,6,6-trioxabicyclo (2,2,2) octane _/ 4-t-butyl-3-cyano-1- (4-iodophenyl) -2,6,7- trioxabicyclo (2,2,2) octane, 4-t-butyl-3-cyano-1- (4- (2-trimethylsilylethynyl) phenyl) -2,6,7-trioxabicyclo (2,2,2) octane _/ 1 - (4-Bromo-3,5-dichlorophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabicyclo (2,2,2) octane, 1- (4-bromo-3-chlorophenyl) -4-n-propyl-3-trifluoromethyl-2,6,7-trioxabizyklo (2..2,2) octane _/ or 4-n-butyl-1- (4-bromophenyl) -3-trifluoromethyl-2 .. 6,7-trioxabicyclo (2,2,2) octane, 4-n-butyl-1- (4-iodophenyl) -3-methyl-2,6,7-trioxabicyclo (2 _/ 2,2) octane, 4- n-Butyl-3-methyl-1- (4- (2-trimethylsilylethynyl) phenyl) -2 _/ 6,7-trioxabicyclo (2,2,2) octane, 4-n-butyl-1- (4-ethynylphenyl) 3-methyl-2,6,7-trioxabicyclo (2,2,2) octane, 4-t-butyl-3-cyano-1-cyclohexyl-2,6,7-trioxabicyclo (2,2,2) octane , 1- (4-Bromophenyl) -3-cyano-4-n-propyl-2,6,8-trioxabicyclo (2,2,2) octane, 3-cyano-1- (4-iodophenyl) -4-n-propyl -2,6,7-trioxabicyclo (2,2,2) octane, 3-cyano-4-n-propyl! -1- (4- (2-trimeth-isilylethynyl) phenyl) -2,6,7-trioxabicyclo lo (2,2,2) octane is included. 6. A composition according to any one of claims 1 to 3, characterized in that the active ingredient is a compound of the formula IA R ^a
_R 3a I "1 · i ^2a is wherein R ^a is C ^ ₂ alkyl, alkenyl or alkynyl, C ^ o-cycloalkyl or phenyl, each optionally substituted by a Ci cyanosis ode ^r - ^ - alkoxy, R ^1a is a cyano group or CI_ ₃ alkyl, C ₂ _ ₃ alkenyl or alkynyl, each optionally substituted by a cyano, C ₁ ^ alkoxy, C 1-4 alkylthio or halo group, or R ^{1a is} a cyano group, Gem dimethyl or R ^1a and R ^a and the carbon atoms to which they are attached form a carbocyclic C ^ ring which is optionally substituted by C 1-4 alkyl or an alkoxy group; R ^2a is phenyl, C ^ ₀ -Zykloalkyl or cycloalkenyl is each optionally substituted and R ^3a is hydrogen, CI_ ₃ alkyl, C ₂ -3 alkenyl or alkynyl each optionally substituted by one cyanosis, C ₁ ^ -AlKyItMo , C 1-4 alkoxy or halo group. 7. A method of combating arthropod pests, which involves the application of a pesticidal compound to the pest or to a pest-prone environment, characterized in that the pesticidal compound is a compound of formula I as described in any of the above 1 to 6 has been defined.