CA1082718A - Dioxolane derivatives - Google Patents
Dioxolane derivativesInfo
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- CA1082718A CA1082718A CA267,590A CA267590A CA1082718A CA 1082718 A CA1082718 A CA 1082718A CA 267590 A CA267590 A CA 267590A CA 1082718 A CA1082718 A CA 1082718A
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Abstract
ABSTRACT OF THE DISCLOSURE
Novel dioxolane derivatives of tke formula (1), wherein R1 represents a hydrogen atom, a C1-C7-alkyl, C3-C6-cycloalkyl, C2-C3-alkenyl, C2-C3-alkinyl, C2-C4-methoxyalkyl, chloro-methyl or benzyl group, R2 represents a hydrogen atom, a C1-C6-alkyl group, or R1 and R2 together represent the -(CH2)n- group, in which n is 4 or 5, or together with the carbon atom to which they are attached represent the group
Novel dioxolane derivatives of tke formula (1), wherein R1 represents a hydrogen atom, a C1-C7-alkyl, C3-C6-cycloalkyl, C2-C3-alkenyl, C2-C3-alkinyl, C2-C4-methoxyalkyl, chloro-methyl or benzyl group, R2 represents a hydrogen atom, a C1-C6-alkyl group, or R1 and R2 together represent the -(CH2)n- group, in which n is 4 or 5, or together with the carbon atom to which they are attached represent the group
Description
~L~
The ~resent invention provides novel dioxolane derivatives, a process for their manufacture, compositions which contain these novel compounds as active component for use in pest control, in public hygiene, and for regulating plant growth to facilitate the harvesting of agricultural, forestry and garden produce.
The dioxolane derivatives have the formula I
CH2 \ O R
CH2 / C~
wherein Rl represents a hydrogen atom, a Cl-C7-alkyl, C3-C6-cyclo-alkyl, C2-C3-alkenyl, C2-C3-alkinyl, C2-C4-methoxyalkyl, chloromethyl or benzyl group, R2 represents a hydrogen atom or a Cl-C6-alkyl group, or Rl and R2 together represent the -(CH2~n- group~ in which n ;
is 4 or 5, or together with the carbon atom to which they are attached represent the group C~3 C \ ~ C~2 f CH
The ~resent invention provides novel dioxolane derivatives, a process for their manufacture, compositions which contain these novel compounds as active component for use in pest control, in public hygiene, and for regulating plant growth to facilitate the harvesting of agricultural, forestry and garden produce.
The dioxolane derivatives have the formula I
CH2 \ O R
CH2 / C~
wherein Rl represents a hydrogen atom, a Cl-C7-alkyl, C3-C6-cyclo-alkyl, C2-C3-alkenyl, C2-C3-alkinyl, C2-C4-methoxyalkyl, chloromethyl or benzyl group, R2 represents a hydrogen atom or a Cl-C6-alkyl group, or Rl and R2 together represent the -(CH2~n- group~ in which n ;
is 4 or 5, or together with the carbon atom to which they are attached represent the group C~3 C \ ~ C~2 f CH
- 2 - ~, . . .. , :
. . . . - . - , . ~ . . .. : -Preferred compounds on account of their action are those of the formula I wherein R2 represents a hydrogen atom or a Cl-C4-alkyl group. Particularly interesting compounds are also those of the formula I wherein Rl represents a Cl-C4-alkyl group, preferably a methyl, cyclohexyl, ethenyl or ethinyl group, and R2 represents a hydrogen atom or a methyl group.
An alkyl group represented by Rl and an alkyl group represented by R2 is, a straight-chain or branched unsubstituted group having 1 to 7 and 1 to 6 carbon atoms respectively, and the alkinyl and alkenyl groups represented by Rl are those having 2 to 3 carbon atoms. Examples of such groups include:
methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, n-hexyl and isomers thereof, allyl, propargyl.
The cycloalkyl groups which are possible for Rl contain 3 to 6 ring carbon atoms. Preferred cycloalkyl groups are cyclopropyl, cyclopentyl and cyclohexyl.
The methoxyalkyl groups represented by Rl contain altogether 2 to 4 carbon atoms and are preferably methoxymethyl and ethoxymethyl groups.
Where Rl and R2 together represent the alkylene group -(CH2)n-, in which n is 4 or 5, the compounds of the present invention are the corresponding spiro derivatives. The same applies to compounds of the formula I, wherein Rl and R2 together with
. . . . - . - , . ~ . . .. : -Preferred compounds on account of their action are those of the formula I wherein R2 represents a hydrogen atom or a Cl-C4-alkyl group. Particularly interesting compounds are also those of the formula I wherein Rl represents a Cl-C4-alkyl group, preferably a methyl, cyclohexyl, ethenyl or ethinyl group, and R2 represents a hydrogen atom or a methyl group.
An alkyl group represented by Rl and an alkyl group represented by R2 is, a straight-chain or branched unsubstituted group having 1 to 7 and 1 to 6 carbon atoms respectively, and the alkinyl and alkenyl groups represented by Rl are those having 2 to 3 carbon atoms. Examples of such groups include:
methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, n-hexyl and isomers thereof, allyl, propargyl.
The cycloalkyl groups which are possible for Rl contain 3 to 6 ring carbon atoms. Preferred cycloalkyl groups are cyclopropyl, cyclopentyl and cyclohexyl.
The methoxyalkyl groups represented by Rl contain altogether 2 to 4 carbon atoms and are preferably methoxymethyl and ethoxymethyl groups.
Where Rl and R2 together represent the alkylene group -(CH2)n-, in which n is 4 or 5, the compounds of the present invention are the corresponding spiro derivatives. The same applies to compounds of the formula I, wherein Rl and R2 together with
- 3 -: -: . . : .................. . .
. .
. '. ' ....................... ' : :
L~ 71~
the carbon atom to which they are attached form the p-methane structure CH3 Cil~ - CH
~ CH
me compounds of the formula I, which are themselves novel, can be obtained by methods which are known per se (cf. for example Houben-Weyl "Methoden der Organischen Chemie", Stuttgart, 1963, Vol. VI/3, p.l99 ff.), for example as follows:
(a) By reacting the diol of the formula II :
O / IH (~
CH2 ~ ~ .
OH
in the presence of an acid catalyst, wlth a carbonyl compound of the formula III / 1 ~ .
O e C (III) , the reaction preferably being carried out with equivalent amounts of the compounds of the formulae ~I~ and (III), optionally with an excess of the carbonyl compound (III). The reaction temperatures vary in general between 40 and 150C, for example between 70D
and 120C. Inert solvents can be used, for example aromatic hydrocarbons, such as benzene, toluene, xylene or halogenated ~:
hydrocarbons, such as chloroform etc. The inert solvents or diluents are adv~ntageously used as entrainers for distilling :
off the water ~hich forms during the reaction (azeotropic .`.
. .
. '. ' ....................... ' : :
L~ 71~
the carbon atom to which they are attached form the p-methane structure CH3 Cil~ - CH
~ CH
me compounds of the formula I, which are themselves novel, can be obtained by methods which are known per se (cf. for example Houben-Weyl "Methoden der Organischen Chemie", Stuttgart, 1963, Vol. VI/3, p.l99 ff.), for example as follows:
(a) By reacting the diol of the formula II :
O / IH (~
CH2 ~ ~ .
OH
in the presence of an acid catalyst, wlth a carbonyl compound of the formula III / 1 ~ .
O e C (III) , the reaction preferably being carried out with equivalent amounts of the compounds of the formulae ~I~ and (III), optionally with an excess of the carbonyl compound (III). The reaction temperatures vary in general between 40 and 150C, for example between 70D
and 120C. Inert solvents can be used, for example aromatic hydrocarbons, such as benzene, toluene, xylene or halogenated ~:
hydrocarbons, such as chloroform etc. The inert solvents or diluents are adv~ntageously used as entrainers for distilling :
off the water ~hich forms during the reaction (azeotropic .`.
- 4 - :;
.. . . . : . .
: : , , . ., . : . ~ .. .
:~
distillation).All acid compounds or Lewis acids which are custo-marily used for acetylation reactions,for example p-toluenesul-phonic acid, phosphoric acid, boron trifluoride-diethyl etherate etc., can be used as catalysts.
(b) By reacting the diol of the formula II, in the presence of an acid catalyst, with an acetal or ketal compound of the formula IV
.. . . . : . .
: : , , . ., . : . ~ .. .
:~
distillation).All acid compounds or Lewis acids which are custo-marily used for acetylation reactions,for example p-toluenesul-phonic acid, phosphoric acid, boron trifluoride-diethyl etherate etc., can be used as catalysts.
(b) By reacting the diol of the formula II, in the presence of an acid catalyst, with an acetal or ketal compound of the formula IV
5 ~ C / 1 / \ (I~) , in the course of which reaction 2 moles of the corresponding alcohol are split off. In formula IV, R5 represents a methyl or ethyl group, and the radicals Rl and R2 are as defined above.
This transacetylation or transketalisation, which can be carried out in the presence of an inert solvent or diluent, takes place preferably at temperatures between 50 and 140C, for example between 70 and 120C. Suitable solvents or diluents are chiefly hydrocarbons, such as benzene, toluene or xylenes. The same substances can be used as catalysts as in reaction (a).
(c) By reacting the co~pound of the formula V
~ ~ (V) - _ r ' ' ~ ' . .': ~ ' . , , . ' ~ '7~
i in the presence of a catalyst, wlth a compound of the formula Vl O
HO-CH2 / \ Rl ~ ' . CH C / (Vl~, CH2~ / R2 - :
O .,~ :
frequently without a solvent or diluent. The reaction is carried out at a temperature of 50 to 150C, preferably 80 to 120C, in the presence of a condensation catalyst, for example a N,~-disubstituted carbodiimide. Preferably N,N-dicyclohexyl-carbo~ ~ `
diimide is used and this reaction catalysed with a copper (I) salt, in particular copper (I) chloride. It is also possible to use diisopropylaminoacetylene as condensation agent (for example in benzene).
In the above described processes (a), (b) and (c) for the manufacture of compounds of the formula I, when the radicals Rl and R2 have different meanings mixtures of the corresponding diastereoisomers are obtained. If desired, these mixtures can be separated by physical methods, for example fractional cry-stallisation, gas chromatography, adsorption chromatography (layer or column chromatography) etc., to yield the respective ~;
diastereoisomeric forms.
, ~ , ,
This transacetylation or transketalisation, which can be carried out in the presence of an inert solvent or diluent, takes place preferably at temperatures between 50 and 140C, for example between 70 and 120C. Suitable solvents or diluents are chiefly hydrocarbons, such as benzene, toluene or xylenes. The same substances can be used as catalysts as in reaction (a).
(c) By reacting the co~pound of the formula V
~ ~ (V) - _ r ' ' ~ ' . .': ~ ' . , , . ' ~ '7~
i in the presence of a catalyst, wlth a compound of the formula Vl O
HO-CH2 / \ Rl ~ ' . CH C / (Vl~, CH2~ / R2 - :
O .,~ :
frequently without a solvent or diluent. The reaction is carried out at a temperature of 50 to 150C, preferably 80 to 120C, in the presence of a condensation catalyst, for example a N,~-disubstituted carbodiimide. Preferably N,N-dicyclohexyl-carbo~ ~ `
diimide is used and this reaction catalysed with a copper (I) salt, in particular copper (I) chloride. It is also possible to use diisopropylaminoacetylene as condensation agent (for example in benzene).
In the above described processes (a), (b) and (c) for the manufacture of compounds of the formula I, when the radicals Rl and R2 have different meanings mixtures of the corresponding diastereoisomers are obtained. If desired, these mixtures can be separated by physical methods, for example fractional cry-stallisation, gas chromatography, adsorption chromatography (layer or column chromatography) etc., to yield the respective ~;
diastereoisomeric forms.
, ~ , ,
- 6 -~ : .. -, . ,. , -,;
., - -. ~ : . ..
, ; , : . --m e ~tarting compounds of the formulae II, III, IV, V and VI areknown or they can be prepared with the aid of methods which are known per se. Thus, for example, the compound of the formula II
can be obtained as follows:
H CHb jCH-CH20H
O \ CH ~ (II).
(m.p. 88-89C) 1H2~
The compounds of the formula I have a broad biocidal activity and can be used for controlling a wide variety of pests which are harmful to plants and animals. The compounds of the formula I
are furthermore characterised by a low toxicity, in particular to warm-blooded animals, and possess substantial advantages from the point of view of residue and environmental problems.
In particular, the compounds of the formula I are suitable for controlling insects of the families:
Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Dia8pididae, Pæeudococcidae, Chry~omelidae, Coccinellidae, - ,-. -.
: . , , : .
, ' . . ' ;:
Bruchidae, Scar~baeidae, Dermestidae, Tenebrionidae, Curculionidae, !
Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culi-cidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae and acaridae of the families: Ixodidae, Argasidae, Tetranychidae, Dermanyssidae.
Excellent effects can be obtained with the compounds of the invention when they are used to control insects which damage harvest produce and in storage protection. The compounds are also suitable for use in the field of hygiene.
The compounds of the formula I are furthermore suitable for controlling ectoparasites in domestic animals and productive livestock, for example by treating animals, cowsheds, stables, barns etc., and meadows. The ectoparasites which can be con-trolled wqth the aid of the compounds of the present invention of the formula I, or of compositions which contain these com-pounds, include representatives of the order Acarina, in parti-cular parasitic ticks and mites of the families: Ioxodidae, Argasidae, Sarcoptidae, Psoroptidae, Dermanyssidae and Demodici-dae, and insects affecting productive livestock and domestic animals of the order Diptera, in particular of the families:
Muscidae, Calliphoridae, Oestridae and Hippoboscidae, and of the orders Mallophaga, Amaplura and Siphonaptera.
me insecticidal action of the compoundg of the invention can be substantially broadened and ad3usted to prevailing conditions by ~ddin~ other insecticides or acaricide~. ¦
- 8 - , -. .. ~ .
~ ` . '' .
: . :
Examples of suitable additlves are: organic phosphorus compounds, nitrophenols and derivatives thereof, rormamidines, ureas, carbamates or chlorinated hydrocarbons.
The compounds of the formula I may be used as pure active substance or together with suitable carr~ers and/or add-itives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in the art of formulation, for example natural or regenerated substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders and/or fertilisers.
For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions, or suspensions, in the conventional formu-lation which is commonly employed in application technology.
The compositions according to the invention which contain compounds of the formula I are obtained in known manner by homogeneously mixing and/or grinding active substances of the formula I with the suitable carriers, with or without the add-ition of dispersants or solvents which are inert to the active substances.
The active substances may take, and be used in, the following forms:
Solid forms:
Dùsts, tracking agents and granules (coated granules, impregnated granules and homogeneous granules).
.
~.. .
. - : , : ,. , Liquid fonms: ¦
a) active ~ubstance concentrates which are dispersible in water: wettable powders, pastes and emulsions;
b) solutions.
Solid forms (dusts, tracking agents) are obtained by mixing the active substances wlth solid carriers. Suitable carriers are, for example: kaolin, talc, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, pre-cipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fer~i-lisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder,re-sidues of plant extractions, activated charcoal etc. These sub-stances can either be used singly or in admixture wlth one an-other.
Granules can be prepared by dissolving the active substances in an organic solvent and applying the resultant solution to a granulated material, for example attapulgite, SiO2, granical-cium, bentonite etc., and then evaporating the solvent.
Polymer granules can also be prepared by mixing the active com-pounds with polymerisable compounds (urea/
fonmaldehyde; diacyandiamide/formaldehyde; ~elamine/formaldehyde - 1 o ~ -.
-~ 7~
or others), whereupon a mild polymerisation is carried out which fdoes not affect the active substances, with the granulation being effected during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde polyacr-ylonitrile, polyesters and others) which have a specific surface area and a favourable predeterminable adsorption/
desorption ratio , with the active substances, for example in the form of their solutions -~in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300g/litre to 600 g/litre can also be manufactured with the aid of atomisers.
The dusting can ~e carried out from aircraft over extensive areas of cultures of useful plants.
It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently commi-nuting the product.
To these mixtures can also be added additives which stabilize the active substance and/or nonionics, anionics and cationics, which, for example, improve the adhesion of the active ingredients on plants or parts of plants (tackifiers and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable substances for this purpose are: clein/chalk mixture, cellulose derivatives (methyl '' -- 11 --
., - -. ~ : . ..
, ; , : . --m e ~tarting compounds of the formulae II, III, IV, V and VI areknown or they can be prepared with the aid of methods which are known per se. Thus, for example, the compound of the formula II
can be obtained as follows:
H CHb jCH-CH20H
O \ CH ~ (II).
(m.p. 88-89C) 1H2~
The compounds of the formula I have a broad biocidal activity and can be used for controlling a wide variety of pests which are harmful to plants and animals. The compounds of the formula I
are furthermore characterised by a low toxicity, in particular to warm-blooded animals, and possess substantial advantages from the point of view of residue and environmental problems.
In particular, the compounds of the formula I are suitable for controlling insects of the families:
Acrididae, Blattidae, Gryllidae, Gryllotalpidae, Tettigoniidae, Cimicidae, Phyrrhocoridae, Reduviidae, Aphididae, Delphacidae, Dia8pididae, Pæeudococcidae, Chry~omelidae, Coccinellidae, - ,-. -.
: . , , : .
, ' . . ' ;:
Bruchidae, Scar~baeidae, Dermestidae, Tenebrionidae, Curculionidae, !
Tineidae, Noctuidae, Lymantriidae, Pyralidae, Galleridae, Culi-cidae, Tipulidae, Stomoxydae, Muscidae, Calliphoridae, Trypetidae, Pulicidae and acaridae of the families: Ixodidae, Argasidae, Tetranychidae, Dermanyssidae.
Excellent effects can be obtained with the compounds of the invention when they are used to control insects which damage harvest produce and in storage protection. The compounds are also suitable for use in the field of hygiene.
The compounds of the formula I are furthermore suitable for controlling ectoparasites in domestic animals and productive livestock, for example by treating animals, cowsheds, stables, barns etc., and meadows. The ectoparasites which can be con-trolled wqth the aid of the compounds of the present invention of the formula I, or of compositions which contain these com-pounds, include representatives of the order Acarina, in parti-cular parasitic ticks and mites of the families: Ioxodidae, Argasidae, Sarcoptidae, Psoroptidae, Dermanyssidae and Demodici-dae, and insects affecting productive livestock and domestic animals of the order Diptera, in particular of the families:
Muscidae, Calliphoridae, Oestridae and Hippoboscidae, and of the orders Mallophaga, Amaplura and Siphonaptera.
me insecticidal action of the compoundg of the invention can be substantially broadened and ad3usted to prevailing conditions by ~ddin~ other insecticides or acaricide~. ¦
- 8 - , -. .. ~ .
~ ` . '' .
: . :
Examples of suitable additlves are: organic phosphorus compounds, nitrophenols and derivatives thereof, rormamidines, ureas, carbamates or chlorinated hydrocarbons.
The compounds of the formula I may be used as pure active substance or together with suitable carr~ers and/or add-itives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in the art of formulation, for example natural or regenerated substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders and/or fertilisers.
For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions, or suspensions, in the conventional formu-lation which is commonly employed in application technology.
The compositions according to the invention which contain compounds of the formula I are obtained in known manner by homogeneously mixing and/or grinding active substances of the formula I with the suitable carriers, with or without the add-ition of dispersants or solvents which are inert to the active substances.
The active substances may take, and be used in, the following forms:
Solid forms:
Dùsts, tracking agents and granules (coated granules, impregnated granules and homogeneous granules).
.
~.. .
. - : , : ,. , Liquid fonms: ¦
a) active ~ubstance concentrates which are dispersible in water: wettable powders, pastes and emulsions;
b) solutions.
Solid forms (dusts, tracking agents) are obtained by mixing the active substances wlth solid carriers. Suitable carriers are, for example: kaolin, talc, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, pre-cipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fer~i-lisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder,re-sidues of plant extractions, activated charcoal etc. These sub-stances can either be used singly or in admixture wlth one an-other.
Granules can be prepared by dissolving the active substances in an organic solvent and applying the resultant solution to a granulated material, for example attapulgite, SiO2, granical-cium, bentonite etc., and then evaporating the solvent.
Polymer granules can also be prepared by mixing the active com-pounds with polymerisable compounds (urea/
fonmaldehyde; diacyandiamide/formaldehyde; ~elamine/formaldehyde - 1 o ~ -.
-~ 7~
or others), whereupon a mild polymerisation is carried out which fdoes not affect the active substances, with the granulation being effected during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde polyacr-ylonitrile, polyesters and others) which have a specific surface area and a favourable predeterminable adsorption/
desorption ratio , with the active substances, for example in the form of their solutions -~in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300g/litre to 600 g/litre can also be manufactured with the aid of atomisers.
The dusting can ~e carried out from aircraft over extensive areas of cultures of useful plants.
It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently commi-nuting the product.
To these mixtures can also be added additives which stabilize the active substance and/or nonionics, anionics and cationics, which, for example, improve the adhesion of the active ingredients on plants or parts of plants (tackifiers and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable substances for this purpose are: clein/chalk mixture, cellulose derivatives (methyl '' -- 11 --
7'~t~
cellUlose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dial~yl phenols containing 5 to 15 ethylene oxide radicais per molecule and 8 to 9 carbon atoms in the alkyl moiety, lignin sulphonic acids, the alkali and alkaline earth salts thereof, polyethylene glycol ethers (Carbowaxes*), fatty alcohol polyethylene glycol ethers containing 5 to 20 e~hylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidone, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products. ~-Water-dispersible active substance concentrates, i.e.
wettable powders, pastes and emulsion concentrates, are composi-tions which can be diluted with water to the desired concentration.
They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substances and anti-foam agents and, if appropriate, solvents.
Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverul-ent carriers in suitable devices until homogeneity is attained.
Suitable carriers are, for example, those already mentioned for the solid forms of application. In many cases it is advantageous to use mixtures of different carriers. As dispersing agents *Trade mark -. - 12 -.. -:: - :
.
. . .
.. , ' ~ ~
108Z~18 there can be used, for example, condensation products of sulphon-ated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene-sulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth salts of lignin sulphonic acid, in addition alkylarylsulphonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols, heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary ethylene glycols, dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.
Silicone oils can be used for example as anti-foam agents.
The active substances are so mixed, ground, sieved and strained with the additives mentioned above that, in wettable powders the solid particle size of 0.02 to 0.04 mm and in pastes, of 0.03 mm, is not exceeded. Emulsion concentrates and pastes are prepared by using dispersing agents, such as those cited pre-viously above, organic solvents, and water. Examples of suitable solvents are: alcohols, benzene, xylenes, toluene, dimethyl sul-phoxide, and mineral oil fractions which boil between 120 and 350C. The solvents must be practically odourless and inert to the active substances.
r:~L8 Furthermore, the ccn~po~itions of the present invention which contaill an acti~re cv~ound of the fo~lula I can be applied in ~he form o.. solut;ons. For th s purpose, the active compound is ~issol~ed in suitable organic solven~s, solvent mixtures or in water. Aliphatic and aromatic hydrocarbons, chlorin~ted derivatives thereof, alkylnapht'nalenes and mineral oils, sing7y or in admixture, can be used as organic solvents.
The content o~ active substance in the above described c~mpo-sitions is between 0.1% and 95%, in which connectlon it rnust be mentioned that concentrations up to 99.5% or even pure active substance can also be us~ if the co~positions are applied from an aircraft or other appropriate application devices.
~le active substances of the formula I can be formulated or ex~mpLe as follows. The parts denote parts by weight.
Dusts:
The following substances are used to manufact~re a) a 5% and b) a 2% dus~:
a) 5 parts of active substance, 95 parts of ~alc;
2 parts of acti~e substance, 1 part of highly disperse silicic acid, 97 parts of talc.
.
.~ ' .
: .
~G~ l ~7 ~
l~xample 1 A mixturP or 31.7 g o~ 2,2-dimethyl-4-hydrox~nethyl--1,3-dioxo-lar.e, 45.4 g of N,N'-dicyclohexyl--carbodiimide and 0.1 ~ of copper(I) chloride is stirred for 24 hours at 100~ to lOS~C
to fo~m an almost homogeneous melt. Then 37.2 g of 4 hydroxy-diphenyl ether and 0.025 g of copper(I) chloride are added at 105-110C and the mixture is then kept for a further 24 hours at this temperature. After the mixture has cooled, it is di-luted with diethyl ether, thoroughly stirred and cooled to 0C.
It is then filtered to remove copper salt and precipitated N,N' dicyclohexyl urea and the filtrate is washed with a 10% solu-tlon of potassium hydroxide, subsequently ~.7ith water and then with a saturated solution of sodium chloride. The solution is dried over sodium sulphate, the diethyl etller is distilled off and the resultant crude product is purified by chromatography through silica gel (eluant: diethyl e-;her/hexane 1: 3) . Cry-stalline 4-(4-phenoxy)-phenoxymethyl-~,2-dimethyl-1,3-dioxo-lane is obtained, which has a melting point of 62-63~C after repeated recrystallisàtion from isopropanol.
f -. - - -- , , ' ' 71 ~
Ex~mple . _ .
With stirring~ 12.5 g of 3,3-diethoxypropine are added drop wise at ~0~-85C in the COUl-~e of approx. 3V n~imltes to a solution of 25~9 g of 1,2-dihydroxy--3 (4-phenoxy)-phenoxy-propane of m.p~ 88-89C (prepared from 4~phenoxyphenol and gly-cerol glyeide) and 50 mg of p-toluenesulphoni~ ac~d ;n 150 ml of anhydrous benzene. ~fter stirring or 2 1/2 hours at this temperature, the bulk of the solvent and of the ethanol which has -formed is distilled off in the course of approx. 1 hour The residue is dissolved in diethyl ether and this solution is washed repeatedly with lN potassium hydroxide, then with water and then with a saturated solution of sodiu~ chloride.
After the organic phase has been dried over sodium sulphate, the solvent is distilled o~f and the residue is chromatographe~
through silica gel (eluant: ethyl acetate/hexane 1:2~, to yield pure 4-(4-phenoxy)-phenoxymethyl-2-ethinyl-1,3-dioxolane wi~h a melting point of 74-75C.
/~ :
B`-` ~
.,.
.. .. ... : - . . .~ .. :. .
.
.. . . .. ' . ~ `
. .
..
71 ~
Fx~n~ple 3 .
With stirri.ng,9.1 g ~0.12 mole) of formaldehyde diméthylacetal are added ~ropwise at 80-85C to a sol~tion of 26g (O.lO mo'le) of 1,2-dih~droxy-3-(4-phenoxy)-phenoxy~propane and S0 mg of p-toluénesulphonic acid in 300 ml ~f anhydrous benzene. The mixture is -refluxed or 20 hours. After it has cooled, the so-lution is concentr~ted by rotary evaporation under reduced pressure. ~le oily residue is taken up in ether and the solu tion is washed three times with a 10% so1ution of potassiun~
hydroxide and subse~uently with a saturated solution of sodi~
chloride. After the or~anic phase has been dried over sodium sulphate, the so'vent is dis~illed of and the residue chromato-graphed through silica gel (eluant: ether/hexane 1:3) to yield 4-(4-phenoxy)-phenoxymethyl-1~3-dioxolane with a melting point of 40-42C.
The following compounds of the formula I are prepared in a manner analogous to that described in the foregoing Examples:
.
, .
k~ R? P,^~ysical data . ~ ~ ~ ~
H nD: 1~,5565 *
C 2H5 H nD : 1., 5~ 64 ~'i ~CII(CI~3)2 H ~n,p. .: 51 52C -' (CH2) 2- Cl~3 H . nD 1, 5443 ~';
-C(CH3)3 H . .-- CH2 ~ CH ( CH3 ) 2 H n2 1 . 540i) CH(C,2ll5) ~ H n20: 1~5349 - (C~ s-- C~13 H n20: 1, 5331 -~
( 2)4 3 H nD: 1,5349 2 ) 3 3 H
~(CH)3 CH3 ¦ H ~ ¦ n : 1.5307 *
~CH2C1 nD: 1 ~5621 *
- CH-CH2 H nD : 1 ~ 5 608 ~ CH C~ H - n20: 1,5301 *
_ _ ~
~ mi~ture of diastereoisomers ~71 ~ ~
. . ~
¦ Rl R2 Physical data r~
-~H2-0-C11 H nD : 1,5529 *
-CH2 ~ H nD: 1,5793 *
C2H5 -CH3 nD: 1,5384 *
~CH -CH3 m.p. : 48 -50 C
-C2H5 2 5 nD: 1,5409 -(CH2)4 - m,p. : 80 -82 C
-(CH2)5 - m.p.: 50-51G
. - (cH2~2-fH-cH2-fH~ n20: 1,5363 CH3 CH(CH3~2 -CH3 n20: 1,5418 *
-CH(CH3)2 -CH(CH3)2 n20: 1~5361 -(CH2~3-CH3 . CH3 n20: 1~5340 *
-C~ccH3)~cH2-c~ CH3 n20: 1,5342 *
-cH2-cH(cH3)2 CH3 n20: 1~5311 *
i * mixture of diastereoisomer~ -22 .
: ,, - '- .' - ~ ''- , ' .:, . . ; , . . . . .: ~
.~:
_ _ _ Physical data . . _ _ .. _ _ -C(Cr~3)3 Cl-l nD~) 1.;368 ^
- (CH2)2-CH3 CH3 n2 : 1.537 8 *
-CH(CH3)2 c~l3 nD: 1.5404 - (C~2)4-C~13 CH3 nD: 1.52g2 ~
- (CH2)5-CH3 CH3 nD: 1. 5273 *
-CH2-CH(CH3)2 -CH2-CH(CH3)2 n~: 1.5221 - (CH2)4-CH3 -C2H5 n20: 1,530~ *
- (CH2)2-CH3 - (CH2)2-CH3 nD : 1.532 - (CH2)3-CH3 - (CH2)3-CH3 n20: 1.5257 - CH (CH3~ (~H2 ) 3 CH3 C113 nD : 1 . 5283 *
- (CH2)3-CH3 - (CH2)5-CH3 n20: 1.519 - ~CH2)2-CH(CH3)2 _ (CH2)2-CH(CH3)2nD : 1.5154 - (CH2)5-CH3 - (CH2)5-C~13 nD : 1,5011 - (CH2)2-CH(CH3)2 -CH3 n20: 1.5223 *
(CH2)3-CH3 2 5 nD : 1.5320 * t, (CH2)2 CH3 ___ ( 3)2 n20: 1.5291 *
,- -.
.: , ' ' ~ ' ' ': :~
~ ~ ~ " -~
. ' , Rl - R2 Physical data -CH2-CH(CH3)2 -C2H5 n20: 1.5321 *
- (CH2)4-C~3 -CH~CH3)2 n20: 1. 5229 * .' - (CH2)4-CH3 - (CH2)2-CH3 nD : 1~5245*
- (CH2~2-CH(CH3)z -C2~5 n20: 1,5274 *
* mixture of diastereoisomers .
- ~ :
. :, ., : . .
. ~ . - - . . . ... :: .. . -- .
.~
Example 4 A) Contact action on Dysdercus fasciatus (larvae) A specific amount of a 0.1% solution of active compound in acetone (corresponding to 10 mg active substance/m2) was pipetted into an aluminium dish and evenly distributed. I~;
After evaporation of the acetone, 10 larvae of Dysdercus fascia-tus in the fifth stage were put into the dishes containing feed and moist cotton wool. The dish was then covered with a per-forated top.
After about 10 days, i.e. after the untreated controls had shed and emerged fully to the adult stage, the test subjects which had developed from the larvae treated as described above were }
examined for the number of normal adults.
B) Action on Aëdes aegypti ~larvae):
Active substance concentrations of 10, 5 and 1 ppm respectively were obtained by pipetting a specific amount of a 0.1% solution I ?
of the active substance in acetone onto the surface of 150 ml of water in each of a number of beakers. After the acetone had evaporated, 30 to 40 two-day-old larvae of Aëdes aegypti were put into each of the beakers containing the active substance i~
solution. Two beakers per concentration of active substance were used for the test. Then-ground feed was added to the beakers, j . .
- ..- - .- . ~ . . . --- - .. - ~ .- ~ ~-.. .
R2 Physical data .
-C(Cr~3)3 Cl-l nD~: 1 .;368 ^
-(C~2)2-CH3 C~13 nD : 1.5378 -Cl~(CH3)2 C~13 nD: 1.5404 ~
-(C~2)4-C}13 CH3 nD: 1.5292 *
-(CH2)5-CH3 CH3 nD : 1.5273 *
-CH2-CH(CH3)2 -CH2-CH(CH3)2 n20: 1.5221 -(CH2)4-CH3 -C2H5 n20: lf,530~ *
-(CH2)2-CH3 -(CH2)2-CH3 nD: 1.532g -(CH2)3-CH3 -(CH2)3-CH3 n20: 1.5257 -CH(CH3~(CH2)3-CH3 C1~3 nD : 1. 5283 *
-(CH2)3-CH3 -(CH2)5-CH3 nD: 1.5199 ~
-~CH2)2-C~(CH3)2 -(CH2)2-CH(CH3)2 nD: 1.5154 ff -(CH2)s-CH3 -(CH2)5-CH3 n~: 1.5011 _ -(CH2)2-CH(CH3)2 -CH3 n20: 1.5223 *
(CH2)3-CH3 2 5 nD: 1.5320 * `
-~CH2)2-cH3 -CH(CH3)2 ~ : ~.5~9~
1.
-- 2 3 -- f ~f , .
' ~ ' ' - l~
. R~ Physical data -CH2-CH(CH3)2 -C2H5 nD : 1,5321 *
-(CH2)4-c~3 -CH~CH3)2 n20 1.5229 ~ ~' -(CH2)4-CH3 -(CH2)2-C~3 nD : 1,5245*
-(CH2)2-CH(cH3)2 ~2~5 n20: 1,5274 *
* mixture of diastereoisomers ~, ", ", Example 4 .
A) Contact action on Dysdercus fasciatus (larvae) A specific amount of a 0.1% solution of active compound in acetone (corresponding to 10 mg active substance/m2) was pipetted into an aluminium dish and evenly distributed, After evaporation of the acetone, 10 larvae of Dysdercus fascia-tus in the fifth stage were put into the dishes containing feed and moist cotton wool. The dish was then covered with a per-forated top~
After about 10 days, i.e, after the untreated controls had shed and emerged fully to the adult stage, the test subjects which had developed from the larvae treated as described above were examined for the number of normal adults.
B) Action on Aëdes ae~yRti (larvae):
Active substance concentrations of 10, 5 and 1 ppm respectively were obtained by pipetting a specific amount of a 0.1% solution of the active substance in acetone onto the surface of 150 ml of water in each of a number of beakers. After the acetone had _ evaporated, 30 to 40 two-day-old larvae of Aëdes aegypti were put into each of the beakers containing the active substance solution. Two beakers per concentration of active substance were used for the test, Then ground feed was added to the beakers, ~. . I
, .. . .. .
~ ....... ..
. . .
which were covered with a copper gauze top.
Evaluation of mortality was made after 1, 2 and 5 days respecti-vely. Subsequently, evaluation was made of the inhibiting action on pupation, metamorphosis, and shedding and emergence to the adult stage.
C) Contact action on Tenebrio molitor (pupae) A specific amount of a 0.1% solution of active substance in acetone, corresponding to 10 mg active substance/m2, was pipetted into an aluminium dish and evenly distributed.
After evaporation of the acetone, lO pupae which had just shed ~heir cocoon were placed onto the treated plate.
The dish was covered with a perforated top.
After the untreated controls had emerged from the pupae cocoons as imagines, the test subjects were examined for the number of adults.
The compounds of formula I displayed good activity in the above test.
, - - ~ -. :
'' . ~ ' , ' , ,. , .,'; ' ''. ' , ' '71~
Example 5 Action against Ephestia kuhniella The active substance to be tested was formulated with suitable carrier materials to a 5% dust. Then 50 g of corn meal were mixed in two beakers with a specific amount of the 5% dust preparation so as to give an active substance concentration of .05% in the meal.
Then 10 larvae of Ephestia kuhniella were put into each beaker ~contents: 25 g of meal). The population development was observed over a period of 8 weeks and the number of developed imagines determined.
The compounds of the formula I exhibited a good action in this test.
, , ~ .
. .
Example 6 Action against Musca domestica 50 g of freshly prepared CSMA nutrient substrate for maggots were charged into beakers. A specific amount of a 1%
acetonic solution of the respective active substance was pipetted onto the nutrient substrate present in the beakers. The substrate was then thoroughly mixed and the acetone subsequently allowed to evaporate over a period of at least 2U hours.
Then 25 one-day-old maggots of Musca domestica were put into each of the beakers containing the treated nutrient substrate for testing with each active substance at one of its given concen-trations. After the maggots had pupated, the pupae were separated from the substrate by flushing them out with water and then de-posited in containers closed with a perforated top.
Each batch of flushed out pupae was counted to determine the toxic effect of the active substance on the maggot develop-ment. The number of flies which had hatched out of the pupae was then counted after 10 days and any influence on the metamo~phosis thereby determined.
2Q The compounds of the formula I displayed good activity in this test.
' , ~ . : ~ , . - ' ' .
. ~
~ '7 F'~ p~e 7 Act:ion a~ai.nst stora~e pcsts Grains o~ l~heat ~7ere trea~ed witll a dusl- formulation containing 5% by weight o active substance, so t,hat an active substance concentration of 10 ppm, referl-ed to t:he weight of the graîns, was obt&i.ned. ~en a n~ber o~ 50~ g portions o the trea.ed grains were popu'lated witll 25 adult beetles of the species nc-uned he-reinbelow. After an exposure time of 3 months, the number o~ living and dead beetles was determined in comparison wi th controls in untreated grains of wheat.
Th.e compo~mds of the formula I exnibited a good action agai.nst Trogoderma granarium, Sitophilus granarius, Rhyzoperta dominica, Tribolium castane~m and Oryzaephilus surinamensis.
~ ~9 ~
- . , , -.. . .. . .. .
. .
. .
~3 E~a1r.p:le ~CtiOII agains~ tic~s: (Rhipi~ephalus bursa and Boophilus micro-plus) .. ~
Five adults or appro~. 50 larvae of the species Rhipicephalus bursa, or 20 0P sensitive or ?.0 0P~resistant larvae o~ the species BGophilus microplus (the resistance refers to the tolerance to~ards diazinone), were counted into eacll of a numDer of test tubes and i~mersed for 1 to 2 minutes in 2 ml of an a~ueous emu]slon contail~ing 100, 10, 1 and 0.1 ppm of test sub-stance. Each test tube was then sealed with a cotton wool plug and placed on its head to enable the cotton wool to absorb excess active substance emulslon.
The mortali~y ra~e of the adults was evaluated after 2 weeks and that of the larvae of both species after 2 days. Each test was repeated twice.
The minim~m concentration for complete control was determined.
In these tests, the com?ounds of Exampl~ 1 acted against adults and larvae of Rhipicephalus bursa and on OP-sensitive and 0P resistant larvae of Boophilus microplus.
.
.
.. ~ ~ . .. .
cellUlose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dial~yl phenols containing 5 to 15 ethylene oxide radicais per molecule and 8 to 9 carbon atoms in the alkyl moiety, lignin sulphonic acids, the alkali and alkaline earth salts thereof, polyethylene glycol ethers (Carbowaxes*), fatty alcohol polyethylene glycol ethers containing 5 to 20 e~hylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidone, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products. ~-Water-dispersible active substance concentrates, i.e.
wettable powders, pastes and emulsion concentrates, are composi-tions which can be diluted with water to the desired concentration.
They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substances and anti-foam agents and, if appropriate, solvents.
Wettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverul-ent carriers in suitable devices until homogeneity is attained.
Suitable carriers are, for example, those already mentioned for the solid forms of application. In many cases it is advantageous to use mixtures of different carriers. As dispersing agents *Trade mark -. - 12 -.. -:: - :
.
. . .
.. , ' ~ ~
108Z~18 there can be used, for example, condensation products of sulphon-ated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene-sulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth salts of lignin sulphonic acid, in addition alkylarylsulphonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols, heptadecanols, octadecanols, and salts of sulphated fatty alcohol glycol ethers, the sodium salt of oleyl methyl tauride, ditertiary ethylene glycols, dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.
Silicone oils can be used for example as anti-foam agents.
The active substances are so mixed, ground, sieved and strained with the additives mentioned above that, in wettable powders the solid particle size of 0.02 to 0.04 mm and in pastes, of 0.03 mm, is not exceeded. Emulsion concentrates and pastes are prepared by using dispersing agents, such as those cited pre-viously above, organic solvents, and water. Examples of suitable solvents are: alcohols, benzene, xylenes, toluene, dimethyl sul-phoxide, and mineral oil fractions which boil between 120 and 350C. The solvents must be practically odourless and inert to the active substances.
r:~L8 Furthermore, the ccn~po~itions of the present invention which contaill an acti~re cv~ound of the fo~lula I can be applied in ~he form o.. solut;ons. For th s purpose, the active compound is ~issol~ed in suitable organic solven~s, solvent mixtures or in water. Aliphatic and aromatic hydrocarbons, chlorin~ted derivatives thereof, alkylnapht'nalenes and mineral oils, sing7y or in admixture, can be used as organic solvents.
The content o~ active substance in the above described c~mpo-sitions is between 0.1% and 95%, in which connectlon it rnust be mentioned that concentrations up to 99.5% or even pure active substance can also be us~ if the co~positions are applied from an aircraft or other appropriate application devices.
~le active substances of the formula I can be formulated or ex~mpLe as follows. The parts denote parts by weight.
Dusts:
The following substances are used to manufact~re a) a 5% and b) a 2% dus~:
a) 5 parts of active substance, 95 parts of ~alc;
2 parts of acti~e substance, 1 part of highly disperse silicic acid, 97 parts of talc.
.
.~ ' .
: .
~G~ l ~7 ~
l~xample 1 A mixturP or 31.7 g o~ 2,2-dimethyl-4-hydrox~nethyl--1,3-dioxo-lar.e, 45.4 g of N,N'-dicyclohexyl--carbodiimide and 0.1 ~ of copper(I) chloride is stirred for 24 hours at 100~ to lOS~C
to fo~m an almost homogeneous melt. Then 37.2 g of 4 hydroxy-diphenyl ether and 0.025 g of copper(I) chloride are added at 105-110C and the mixture is then kept for a further 24 hours at this temperature. After the mixture has cooled, it is di-luted with diethyl ether, thoroughly stirred and cooled to 0C.
It is then filtered to remove copper salt and precipitated N,N' dicyclohexyl urea and the filtrate is washed with a 10% solu-tlon of potassium hydroxide, subsequently ~.7ith water and then with a saturated solution of sodium chloride. The solution is dried over sodium sulphate, the diethyl etller is distilled off and the resultant crude product is purified by chromatography through silica gel (eluant: diethyl e-;her/hexane 1: 3) . Cry-stalline 4-(4-phenoxy)-phenoxymethyl-~,2-dimethyl-1,3-dioxo-lane is obtained, which has a melting point of 62-63~C after repeated recrystallisàtion from isopropanol.
f -. - - -- , , ' ' 71 ~
Ex~mple . _ .
With stirring~ 12.5 g of 3,3-diethoxypropine are added drop wise at ~0~-85C in the COUl-~e of approx. 3V n~imltes to a solution of 25~9 g of 1,2-dihydroxy--3 (4-phenoxy)-phenoxy-propane of m.p~ 88-89C (prepared from 4~phenoxyphenol and gly-cerol glyeide) and 50 mg of p-toluenesulphoni~ ac~d ;n 150 ml of anhydrous benzene. ~fter stirring or 2 1/2 hours at this temperature, the bulk of the solvent and of the ethanol which has -formed is distilled off in the course of approx. 1 hour The residue is dissolved in diethyl ether and this solution is washed repeatedly with lN potassium hydroxide, then with water and then with a saturated solution of sodiu~ chloride.
After the organic phase has been dried over sodium sulphate, the solvent is distilled o~f and the residue is chromatographe~
through silica gel (eluant: ethyl acetate/hexane 1:2~, to yield pure 4-(4-phenoxy)-phenoxymethyl-2-ethinyl-1,3-dioxolane wi~h a melting point of 74-75C.
/~ :
B`-` ~
.,.
.. .. ... : - . . .~ .. :. .
.
.. . . .. ' . ~ `
. .
..
71 ~
Fx~n~ple 3 .
With stirri.ng,9.1 g ~0.12 mole) of formaldehyde diméthylacetal are added ~ropwise at 80-85C to a sol~tion of 26g (O.lO mo'le) of 1,2-dih~droxy-3-(4-phenoxy)-phenoxy~propane and S0 mg of p-toluénesulphonic acid in 300 ml ~f anhydrous benzene. The mixture is -refluxed or 20 hours. After it has cooled, the so-lution is concentr~ted by rotary evaporation under reduced pressure. ~le oily residue is taken up in ether and the solu tion is washed three times with a 10% so1ution of potassiun~
hydroxide and subse~uently with a saturated solution of sodi~
chloride. After the or~anic phase has been dried over sodium sulphate, the so'vent is dis~illed of and the residue chromato-graphed through silica gel (eluant: ether/hexane 1:3) to yield 4-(4-phenoxy)-phenoxymethyl-1~3-dioxolane with a melting point of 40-42C.
The following compounds of the formula I are prepared in a manner analogous to that described in the foregoing Examples:
.
, .
k~ R? P,^~ysical data . ~ ~ ~ ~
H nD: 1~,5565 *
C 2H5 H nD : 1., 5~ 64 ~'i ~CII(CI~3)2 H ~n,p. .: 51 52C -' (CH2) 2- Cl~3 H . nD 1, 5443 ~';
-C(CH3)3 H . .-- CH2 ~ CH ( CH3 ) 2 H n2 1 . 540i) CH(C,2ll5) ~ H n20: 1~5349 - (C~ s-- C~13 H n20: 1, 5331 -~
( 2)4 3 H nD: 1,5349 2 ) 3 3 H
~(CH)3 CH3 ¦ H ~ ¦ n : 1.5307 *
~CH2C1 nD: 1 ~5621 *
- CH-CH2 H nD : 1 ~ 5 608 ~ CH C~ H - n20: 1,5301 *
_ _ ~
~ mi~ture of diastereoisomers ~71 ~ ~
. . ~
¦ Rl R2 Physical data r~
-~H2-0-C11 H nD : 1,5529 *
-CH2 ~ H nD: 1,5793 *
C2H5 -CH3 nD: 1,5384 *
~CH -CH3 m.p. : 48 -50 C
-C2H5 2 5 nD: 1,5409 -(CH2)4 - m,p. : 80 -82 C
-(CH2)5 - m.p.: 50-51G
. - (cH2~2-fH-cH2-fH~ n20: 1,5363 CH3 CH(CH3~2 -CH3 n20: 1,5418 *
-CH(CH3)2 -CH(CH3)2 n20: 1~5361 -(CH2~3-CH3 . CH3 n20: 1~5340 *
-C~ccH3)~cH2-c~ CH3 n20: 1,5342 *
-cH2-cH(cH3)2 CH3 n20: 1~5311 *
i * mixture of diastereoisomer~ -22 .
: ,, - '- .' - ~ ''- , ' .:, . . ; , . . . . .: ~
.~:
_ _ _ Physical data . . _ _ .. _ _ -C(Cr~3)3 Cl-l nD~) 1.;368 ^
- (CH2)2-CH3 CH3 n2 : 1.537 8 *
-CH(CH3)2 c~l3 nD: 1.5404 - (C~2)4-C~13 CH3 nD: 1.52g2 ~
- (CH2)5-CH3 CH3 nD: 1. 5273 *
-CH2-CH(CH3)2 -CH2-CH(CH3)2 n~: 1.5221 - (CH2)4-CH3 -C2H5 n20: 1,530~ *
- (CH2)2-CH3 - (CH2)2-CH3 nD : 1.532 - (CH2)3-CH3 - (CH2)3-CH3 n20: 1.5257 - CH (CH3~ (~H2 ) 3 CH3 C113 nD : 1 . 5283 *
- (CH2)3-CH3 - (CH2)5-CH3 n20: 1.519 - ~CH2)2-CH(CH3)2 _ (CH2)2-CH(CH3)2nD : 1.5154 - (CH2)5-CH3 - (CH2)5-C~13 nD : 1,5011 - (CH2)2-CH(CH3)2 -CH3 n20: 1.5223 *
(CH2)3-CH3 2 5 nD : 1.5320 * t, (CH2)2 CH3 ___ ( 3)2 n20: 1.5291 *
,- -.
.: , ' ' ~ ' ' ': :~
~ ~ ~ " -~
. ' , Rl - R2 Physical data -CH2-CH(CH3)2 -C2H5 n20: 1.5321 *
- (CH2)4-C~3 -CH~CH3)2 n20: 1. 5229 * .' - (CH2)4-CH3 - (CH2)2-CH3 nD : 1~5245*
- (CH2~2-CH(CH3)z -C2~5 n20: 1,5274 *
* mixture of diastereoisomers .
- ~ :
. :, ., : . .
. ~ . - - . . . ... :: .. . -- .
.~
Example 4 A) Contact action on Dysdercus fasciatus (larvae) A specific amount of a 0.1% solution of active compound in acetone (corresponding to 10 mg active substance/m2) was pipetted into an aluminium dish and evenly distributed. I~;
After evaporation of the acetone, 10 larvae of Dysdercus fascia-tus in the fifth stage were put into the dishes containing feed and moist cotton wool. The dish was then covered with a per-forated top.
After about 10 days, i.e. after the untreated controls had shed and emerged fully to the adult stage, the test subjects which had developed from the larvae treated as described above were }
examined for the number of normal adults.
B) Action on Aëdes aegypti ~larvae):
Active substance concentrations of 10, 5 and 1 ppm respectively were obtained by pipetting a specific amount of a 0.1% solution I ?
of the active substance in acetone onto the surface of 150 ml of water in each of a number of beakers. After the acetone had evaporated, 30 to 40 two-day-old larvae of Aëdes aegypti were put into each of the beakers containing the active substance i~
solution. Two beakers per concentration of active substance were used for the test. Then-ground feed was added to the beakers, j . .
- ..- - .- . ~ . . . --- - .. - ~ .- ~ ~-.. .
R2 Physical data .
-C(Cr~3)3 Cl-l nD~: 1 .;368 ^
-(C~2)2-CH3 C~13 nD : 1.5378 -Cl~(CH3)2 C~13 nD: 1.5404 ~
-(C~2)4-C}13 CH3 nD: 1.5292 *
-(CH2)5-CH3 CH3 nD : 1.5273 *
-CH2-CH(CH3)2 -CH2-CH(CH3)2 n20: 1.5221 -(CH2)4-CH3 -C2H5 n20: lf,530~ *
-(CH2)2-CH3 -(CH2)2-CH3 nD: 1.532g -(CH2)3-CH3 -(CH2)3-CH3 n20: 1.5257 -CH(CH3~(CH2)3-CH3 C1~3 nD : 1. 5283 *
-(CH2)3-CH3 -(CH2)5-CH3 nD: 1.5199 ~
-~CH2)2-C~(CH3)2 -(CH2)2-CH(CH3)2 nD: 1.5154 ff -(CH2)s-CH3 -(CH2)5-CH3 n~: 1.5011 _ -(CH2)2-CH(CH3)2 -CH3 n20: 1.5223 *
(CH2)3-CH3 2 5 nD: 1.5320 * `
-~CH2)2-cH3 -CH(CH3)2 ~ : ~.5~9~
1.
-- 2 3 -- f ~f , .
' ~ ' ' - l~
. R~ Physical data -CH2-CH(CH3)2 -C2H5 nD : 1,5321 *
-(CH2)4-c~3 -CH~CH3)2 n20 1.5229 ~ ~' -(CH2)4-CH3 -(CH2)2-C~3 nD : 1,5245*
-(CH2)2-CH(cH3)2 ~2~5 n20: 1,5274 *
* mixture of diastereoisomers ~, ", ", Example 4 .
A) Contact action on Dysdercus fasciatus (larvae) A specific amount of a 0.1% solution of active compound in acetone (corresponding to 10 mg active substance/m2) was pipetted into an aluminium dish and evenly distributed, After evaporation of the acetone, 10 larvae of Dysdercus fascia-tus in the fifth stage were put into the dishes containing feed and moist cotton wool. The dish was then covered with a per-forated top~
After about 10 days, i.e, after the untreated controls had shed and emerged fully to the adult stage, the test subjects which had developed from the larvae treated as described above were examined for the number of normal adults.
B) Action on Aëdes ae~yRti (larvae):
Active substance concentrations of 10, 5 and 1 ppm respectively were obtained by pipetting a specific amount of a 0.1% solution of the active substance in acetone onto the surface of 150 ml of water in each of a number of beakers. After the acetone had _ evaporated, 30 to 40 two-day-old larvae of Aëdes aegypti were put into each of the beakers containing the active substance solution. Two beakers per concentration of active substance were used for the test, Then ground feed was added to the beakers, ~. . I
, .. . .. .
~ ....... ..
. . .
which were covered with a copper gauze top.
Evaluation of mortality was made after 1, 2 and 5 days respecti-vely. Subsequently, evaluation was made of the inhibiting action on pupation, metamorphosis, and shedding and emergence to the adult stage.
C) Contact action on Tenebrio molitor (pupae) A specific amount of a 0.1% solution of active substance in acetone, corresponding to 10 mg active substance/m2, was pipetted into an aluminium dish and evenly distributed.
After evaporation of the acetone, lO pupae which had just shed ~heir cocoon were placed onto the treated plate.
The dish was covered with a perforated top.
After the untreated controls had emerged from the pupae cocoons as imagines, the test subjects were examined for the number of adults.
The compounds of formula I displayed good activity in the above test.
, - - ~ -. :
'' . ~ ' , ' , ,. , .,'; ' ''. ' , ' '71~
Example 5 Action against Ephestia kuhniella The active substance to be tested was formulated with suitable carrier materials to a 5% dust. Then 50 g of corn meal were mixed in two beakers with a specific amount of the 5% dust preparation so as to give an active substance concentration of .05% in the meal.
Then 10 larvae of Ephestia kuhniella were put into each beaker ~contents: 25 g of meal). The population development was observed over a period of 8 weeks and the number of developed imagines determined.
The compounds of the formula I exhibited a good action in this test.
, , ~ .
. .
Example 6 Action against Musca domestica 50 g of freshly prepared CSMA nutrient substrate for maggots were charged into beakers. A specific amount of a 1%
acetonic solution of the respective active substance was pipetted onto the nutrient substrate present in the beakers. The substrate was then thoroughly mixed and the acetone subsequently allowed to evaporate over a period of at least 2U hours.
Then 25 one-day-old maggots of Musca domestica were put into each of the beakers containing the treated nutrient substrate for testing with each active substance at one of its given concen-trations. After the maggots had pupated, the pupae were separated from the substrate by flushing them out with water and then de-posited in containers closed with a perforated top.
Each batch of flushed out pupae was counted to determine the toxic effect of the active substance on the maggot develop-ment. The number of flies which had hatched out of the pupae was then counted after 10 days and any influence on the metamo~phosis thereby determined.
2Q The compounds of the formula I displayed good activity in this test.
' , ~ . : ~ , . - ' ' .
. ~
~ '7 F'~ p~e 7 Act:ion a~ai.nst stora~e pcsts Grains o~ l~heat ~7ere trea~ed witll a dusl- formulation containing 5% by weight o active substance, so t,hat an active substance concentration of 10 ppm, referl-ed to t:he weight of the graîns, was obt&i.ned. ~en a n~ber o~ 50~ g portions o the trea.ed grains were popu'lated witll 25 adult beetles of the species nc-uned he-reinbelow. After an exposure time of 3 months, the number o~ living and dead beetles was determined in comparison wi th controls in untreated grains of wheat.
Th.e compo~mds of the formula I exnibited a good action agai.nst Trogoderma granarium, Sitophilus granarius, Rhyzoperta dominica, Tribolium castane~m and Oryzaephilus surinamensis.
~ ~9 ~
- . , , -.. . .. . .. .
. .
. .
~3 E~a1r.p:le ~CtiOII agains~ tic~s: (Rhipi~ephalus bursa and Boophilus micro-plus) .. ~
Five adults or appro~. 50 larvae of the species Rhipicephalus bursa, or 20 0P sensitive or ?.0 0P~resistant larvae o~ the species BGophilus microplus (the resistance refers to the tolerance to~ards diazinone), were counted into eacll of a numDer of test tubes and i~mersed for 1 to 2 minutes in 2 ml of an a~ueous emu]slon contail~ing 100, 10, 1 and 0.1 ppm of test sub-stance. Each test tube was then sealed with a cotton wool plug and placed on its head to enable the cotton wool to absorb excess active substance emulslon.
The mortali~y ra~e of the adults was evaluated after 2 weeks and that of the larvae of both species after 2 days. Each test was repeated twice.
The minim~m concentration for complete control was determined.
In these tests, the com?ounds of Exampl~ 1 acted against adults and larvae of Rhipicephalus bursa and on OP-sensitive and 0P resistant larvae of Boophilus microplus.
.
.
.. ~ ~ . .. .
Claims (20)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A dioxolane derivative of the general formula I
(I), wherein R1 represents a hydrogen atom or a C1-C7-alkyl, C3-C6-cycloalkyl, C2-C3-alkenyl, C2-C3-alkinyl, C2-C4-methoxy-alkyl, chloromethyl or benzyl group, R2 represents a hydrogen atom or a C1-C6-alkyl group, or R1 and R2 together represent the -(CH2)n- group, in which n is 4 or 5, or together with the carbon atom to which they are attached represent the group
(I), wherein R1 represents a hydrogen atom or a C1-C7-alkyl, C3-C6-cycloalkyl, C2-C3-alkenyl, C2-C3-alkinyl, C2-C4-methoxy-alkyl, chloromethyl or benzyl group, R2 represents a hydrogen atom or a C1-C6-alkyl group, or R1 and R2 together represent the -(CH2)n- group, in which n is 4 or 5, or together with the carbon atom to which they are attached represent the group
2. A compound according to claim 1, wherein R2 in the general formula I represents a hydrogen atom or a C1-C4 alkyl group.
3. A compound according to claim 2, wherein in the general formula I R1 represents a C1-C4-alkyl, cyclohexyl, ethenyl or ethinyl group and R2 represents a hydrogen atom or a methyl group.
4. A compound according to claim 1, wherein R2 in the general formula I represents a hydrogen atom.
5. The compound according to claim 4 of the formula .
6. The compound according to claim 4 of the formula .
7. The compound according to claim 4 of the formula .
8. The compound according to claim 4 of the formula .
9. The compound according to claim 1 of the formula .
10. The compound according to claim 3 of the formula .
11. The compound according to claim 3 of the formula .
12. The compound according to claim 3 of the formula .
13. The compound according to claim 1 of the formula
14. The compound according to claim 4 of the formula
15. Process for the manufacture of compounds as claimed in claim 1, which comprises reacting (a) the compound of the formula II
(II) in the presence of an acid catalyst with a compound of the formula III
(III) or (b) the compound of the formula II in the presence of an acid cata-lyst with a compound of the formula IV
(IV) or (c) the compound of the formula V
(V) in the presence of a catalyst with a compound of the formula VI
(VI) in which formulae R1 and R2 have the meanings given in claim 1 and R5 represents a methyl or ethyl group.
(II) in the presence of an acid catalyst with a compound of the formula III
(III) or (b) the compound of the formula II in the presence of an acid cata-lyst with a compound of the formula IV
(IV) or (c) the compound of the formula V
(V) in the presence of a catalyst with a compound of the formula VI
(VI) in which formulae R1 and R2 have the meanings given in claim 1 and R5 represents a methyl or ethyl group.
16. A method of combating pests which are harmful to animals and plants, at a locus, which method comprises applying to the locus a compound as claimed in claim 1, 2 or 3.
17. A method of combating pests of the class Insecta or of the order Acarina at a locus, which method comprises applying to the locus a compound as claimed in claim 1, 2 or 3.
18. A method of combating pests of the class Insecta or of the order Acarina at a locus comprising growing agricultural or horticultural crops, fruits, plants or produce, which method comprises applying to the locus a com-pound as claimed in claim 1, 2 or 3.
19. A method of combating pests of the class Insecta or of the order Acarina at a locus, which pests comprise ectoparasites in productive livestock or domestic animals, the method comprising applying to the locus a compound as claimed in claim 1, 2 or 3.
20. A method of combating pests of the class of Insecta or of the order Acarina at a locus, which pests comprise storage pests, the method comprising applying to the locus a compound as claimed in claim 1, 2 or 3.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1458475A CH594656A5 (en) | 1974-11-13 | 1975-11-11 | |
| CH16153/75 | 1975-12-12 | ||
| CH1615375 | 1975-12-12 | ||
| CH16783/75 | 1975-12-24 | ||
| CH1678375 | 1975-12-24 | ||
| CH11069/76 | 1976-09-01 | ||
| CH1106976 | 1976-09-01 | ||
| CH14584/75 | 1976-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1082718A true CA1082718A (en) | 1980-07-29 |
Family
ID=27429334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA267,590A Expired CA1082718A (en) | 1975-11-11 | 1976-12-10 | Dioxolane derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1082718A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115267020A (en) * | 2022-07-25 | 2022-11-01 | 开封龙宇化工有限公司 | Method for detecting methanol concentration in formaldehyde solution by gas chromatography |
-
1976
- 1976-12-10 CA CA267,590A patent/CA1082718A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115267020A (en) * | 2022-07-25 | 2022-11-01 | 开封龙宇化工有限公司 | Method for detecting methanol concentration in formaldehyde solution by gas chromatography |
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| MKEX | Expiry |