IL37666A - Stabilised pesticidal compositions containing phosphoric esters - Google Patents

Description

This concerns a process for stabilising pesticidal phosphoric and compositions based on phoric esters so Phosphoric esters are nowadays very widespread for pesticidal particularly for Their value is due principally to speed of action and the absence of accumulation of these compounds in living tissue as a result of their rapid hydrolysis in This latter characteristic which gives them a net advantage over the so called chlorinated presents however a very grave the sensitivity of certain phosphoric esters to even simply that of the is such that their decomposition takes place without their being able to act on the pest the phosphoric esters which sensitive are more particularly those which contain one or more low alkyl such as propyl or isopropyl groups attached to the phosphoric this on contact with molecules of an at least partial decomposition of these esters by by displacement of one low alkyl group in favour of a hydrogen Among the sensitive phosphoric esters special mention should be made of better known under the common name DICHLORVOS and the abbreviat the use of which in permanent insecticidal devices known evaporators has undergone a tremendous increase in recent years Various means of stabilisation have suggested for limiting the decomposition of these phosphoric esters but they are generally for example amines and low nitrogen another useful class of stabiliser comprises azoic and hydrazonic compounds but these a strong powe so that they cannot always be The proposed use of or epoxides has also been used bu it is known that these compounds act by either of a molecule of water or a molecule of free it can be seen that this process is limited stoichiometrically and that the stabilisation ceases when all the stabiliser has entered into this leads to the necessity of ing substantial Of these stabilisers which is not The present invention has as its object tion of pesticidal phosphoric esters by substances than those noted above and which not possess these substances are sulphur they are suitable in particular at relatively low concentrations for preserving phosphoric esters against Thus the invention consists in pesticidal positions to calculated on the weight of of a phosphoric ester of the formula and to based on the weight of the phosphoric of stabilising ester against ising the said phosphoric ester against protonisatio and comprising at least one stilphur compound as defined in claim if adding thereto 0 to calculated on the weight of the final of one or more solvents for the phosphoric ester which are solid or liquid under pressure or otherwise and 0 to calculated on the weight of the final of one or more inert adjuvants selected from mineral adjuvants and organic adjuvants compatible with the phosphoric adjuvan mineral The quantities of stabilising agent used according to the present invention are preferably between and based on the weight of the phosphoric In the sulphur compounds such as those defined according to the invention the valences of the atom of sulphur which are bonded to another or other atoms in a molecule of the sulphur compound according to the invention can be constituted by a homopolar bond resulting from the displacement from a electron by one or two heteropolar bonds resulting from an exchange of electrons between the sulphur and the atom to which it is bonded or by one or electrovalences resulting from static attraction between two ions of opposite The sulphur compounds preferred for use in the present invention are as Sulfanes defined by formula I H H in is a whole number between 1 and such compounds are for hydrogen monosulfide hydrogen bisulfide hydrogen trisulfide hydrogen tetrasulfide hydrogen pentasulfide hydrogen hexasulfide content by ercaptans defined by formula II H S R which R is chosen from a group Ra chosen a phenyl a benzyl a phenyl group and a benzyl group bearing substituents chosen from alkyl residues containing atoms of an alkyl group containing carbon a heterocyclic group chosen from monocyclic and bicyclic heterocyclic groups comprising 5 to 10 ring atoms in which of the ring members are chosen from the group and a second and a third ring member being chosen from groups C in which is a group chosen from and an alkyl or cycloalkyl group containing carbon atoms and is or an alkyl group containing carbon the groups to noted above carrying substituents chosen from chlorine and bromine an the groups to noted above carrying a stituent chosen from alkoxy carbonyl containing 2 to 6 atoms of carbon and an amino group N in which and are the same or different and are chosen from hydrogen and alkyl residues containing atoms of carbon and a group A S H in which A is a group chosen from alkylene containing carbon toluylene and ethylene are for example the Octadccanethiol acetate acetate benzenethiol benzenethiol benzenethiol 2 benzenethiol benzenethiol of hane hiol butanethiol dodecanethiol benzenethiol benzenethiol j acetate propionate benzoic triazole benzenethiol benzoxazole benzimidazole pyridine ethanethiol 1 benzimidazole benzimidazole benzimidazole benzimidazole benzimidazole propionate hyl imidazole Sulfides defined by formula which Rfe and are independently chosen an alkyl of 1 to 18 carbon phenyl benzyl morpholinyl piperidyl pyridyl benzothiazolyl benzimidazolyl benzoxazolyl the groups to just mentioned carrying substituents chosen from carbonyl of carbon and amino as defined in 2 above and an alkyl containing carbon atoms and n represents a whole number between 1 and Such compositions for the hexane nonane phenol benzimi e benzoxazole benzylthiobenzene nitrobenzene propionate lphenol propane valerianate propyl benzene sulfide sulfide sulfide sulfide sulfide didecyl sulfide dioctadecyl sulfide didodecyl sulfide sulfide sulfide diphenyl sulfide sulfid sulfide sulfide sulfide sulfide dimethyl disulfide dioctyl disulfide dibutyl disulfide bis sulfide didodecyl disulfide dioctadecyl disulfide dibenzyl disulfide disulfide heneicosane benzene othiazole disulfide disulfide disulfide butane nitrobenzene disulfide disulfide disulfide disulfide disulfide disulfide disulfide disulfide disulfide hexane ane 1 diphenyl trisulfide trisulfide trisulfide trisulfide trisulfide dibutyl trisulfide dimethyl trisulfide dibenzyl trisulfide didodecyl trisulfide dioctadecyl trisulfide trisulfide trisulfide tetrasulfide dibutyl tetrasulfide didodecyl tetrasulfide dioctadecyl tetrasulfide diphenyl tetrasulfide tetrasulfide ditertbutylpentasulfide ditertdodecylpentasulfide pentasulfide ditertdodecylhexasulfide didecylhexasulfide dipropylhexasulfide dibenzylhexasulfide hexasulfdde thiobenzothiazole benzothiazole benzothiazole acid Heterocyclic compounds which comprise 5 to 23 ring members forming 1 to 5 rings with at most 2 to 3 which comprise rings which each contain an and 2 other chains members chosen from the groups the remainder of the chain members being chosen from the groupings C and C the heterocyclic compounds with fused rings being chosen from among those of which all the hetero chain members are contained in one and the same this ring being the central ring in the case of 3 fused all the ring members being chosen taking into account all the valences of the heterocyclic compound should be and being independently chosen from alkyl of carbon and as defined under 2 the group S N vnich are the same or differen and are phenyl or alkyl of carbon alkanoyl amino containing carbon alkyl thio containing carbon the oxo phenylazo carrying substituents chosen from nitro and and being chosen from hydrogen and These heterocyclic compounds can be chosen from the and tetrahydrothi Such compounds are for example the tetrahydrothiophene thiazoline thiazole thiazole thiazole thiazole thiazole thiazole thiazole benzothiazole l benzothiazole benzothiazole benzothiazole benzothiazole benzothiazole benzothiazole benzimidazole phenothiazine phenothiazine phenothiazine phenothiazine benzothiazolidine o benzothiazole benzothiazole thiazole to thiadiazole irdiazole l thiazolidine thiazolidine thiazolidine thiazolidine l thiazolidine thiazolidine thiazolidine thiazolidine ne larninothio benzothiazole benzothiazole benzothiazole benzothiazole pyridine benzimidazole benzimidazole benzimidazole benzimidazole methyl benzimidazole benzimidazole Monocyclic heterocyclic compounds chosen from saturated heterocyclic compounds with 6 ring members in which ring members are not contiguous are constituted by one other ring member being chosen from the groups and N and the remainder of the ring members being chosen from the groups C in which and have the definitio given in above Theee heterocyclic compounds can be chosen from amongst trithianes and thiomorpholines Such compounds are for example the 4f thiomorpholine thiomorpholine thiomorpholine thiomorpholine thiomorpholine thiomorpholine thiomorpholine thiomorpholine thiomorpholine thiomorpholine Thioic defined by formula R Y C X in which X and are chosen from those defined under c and the compounds in which R and Q form two distinct groups in which R is a group chosen from allcyl or carbon atoms and an allcyl residue as just mentioned bearing a substituent chosen from carbonyl having 2 to 5 carbon alkyl or cyclo l containing 6 to 10 carbon or alkenyl containing 2 to 5 carbon atoms and X and Y represent an atom chosen from oxygen and at least one of them per molecule being a sulphur atom is chosen from among a a group selected from an alkyl containing 1 to 6 carbon atoms an alkyl carrying a group cycloalkyl containing 6 to 10 carbon alkyl cycloalkyl containing 6 to 10 carbon and phenyl bearing one to three substituents chosen from alkyl of 1 to carbon and hydroxy β a group B C Y in which c Y and R have the definition given above and in which B is chosen c from a disulphid group and a hydrocarbon divalent group chosen from alkylenes containing 1 to 8 carbon atoms and and a group Z chosen among groups in which Z is oxygen or sulphur and R is a group chosen from those c defined for R c the compounds in which and form together an alkylene group 3 to 10 carbon atoms in branched or straight chains and compounds in which Q represents the group Z and in which R and R together form a divalent group chosen c c from aliphatic chains containing 2 to 6 carbon and cyclic systems containing 5 to 10 ring members and one or two under which one of the two ring members are chose from the group the group and the group Such compounds are for example the thioacetic acid thiopropionic acid thiobutyric acid dithiobutyric acid dithioacetic acid hexanethioic acid hexanedithioic acid hexane thioic acid cyclohexane carbodithioic acid thiobenzoic acid dithiosalicylic acid thiobenzoic acid thiobenzoic acid thiobenzoic acid thionicotinic acid dithioterephthalic acid ethyl thioacetate methylthiobenzoate diethyldithiolcarbonate diphenyldi hiolcarbonate dibenzyltrithiocarbonate hyltrithiocarbonate thiophenylacetic acid dibutyl rithiocarbonate ylene trithiocarbonate trithiocarbonate trithiocarbonate bis trithiocarbonate bis trithiocarbonate dihexyltrithiocarbonate dioctyltrithiocarbonate trithiocarbonate butyl ethyl xanthate methyl ethyl xanthate phenyl ethyl xanthate cyclohexylethyl xanthate menthyletbylxanthate henzylethylxanthate allylethylxanthate methylcyclohexyl xanthate ethylbenzylxanthate butylallylxanthate phenylphenylxanthate ethoxythiocarbonyl sulfide methoxythiocarbonyl disulfide ethoxythiocarbonyl disulfide gamma thiobutyrolactone thioundecalactone trithiocarbonate isopropyl thiocarbonyl disulfide methyl xanthate dicyclohexyltrithio carbonate divinyltrithio carbonate by formula N C S in which are chosen as defined under and and are each separately chosen from of 1 to 4 carbon phenyl and taken together from an straight or branched chain group containing 4 to 10 carbon E represents a group chosen from a group as v defined under R in a group D C s in which D represents a symbol chosen from a direct bond or a divalent hydrocarbon group chosen from containing 1 to 8 carbon atoms and phenylenes and in which and have the same meaning as above and E represent together a group such as defined under in Such compositions for the following thioacetamide thioacetamide thiobenzarnide thiobenzarnide 2 thiobenzarnide l thiobenzarnide f thiobenzarnide thiobenzarnide thiobenzarnide thiobenzarnide thiobenzarnide thio ormamide thionicotinamide thioisonicotinamide thioheptanoylamide dithio malonamide dithioxamide dithiosuccinamide dithioadipamide dithiosebacamide dithioadipamide thioacetamide thioacetamide dit iosuccinoyl epsilon thiocaprolactani gamma thioundecalactam in is chosen from of 1 to 4 carbon atoms and phenyl and in represents a group chosen from a group chosen from an alkyl containing 1 to 12 carbon alkenyl containing 2 to 12 carbon cycloalkyl or cycloalkenyl containing 5 to 6 carbon alkyl and cycloalkenyl such as defined above bearing 1 to 3 allcyl substituents each 1 to 4 carbon phenyl and a phenyl group carrying 1 to 3 substituents chosen from allcyl and alkenyl groups to 5 carbon chlorine and a group s C in which is alkylene straight or branched chain containing 2 to 6 carbon atoms and and are chosen such as defined in S9 and in which G is chosen from a group has one of the meanings given for defined above and a group D S R in and have the definitio S Such compounds for the dithiocarbamate ethyl dithiocarbamate methyl l dithiocarbamate methyl dithiocarbamate ethyl dithiocarbamate dithiocarbamate dodecyl dithiocarbamate dithiocarbamate dithiocarbamate menthyl dithiocarbamate phenyl l dithiocarbamate dithiocarbamate l dithiocarbamate benzyl dithiocarbamate dithiocarbamate dithiocarbamate phenyl l dithiocarbamate 4 dithiocarbamate bis bis bis phenyl bis bis bis diyl bis l diyl bis diyl bis esters defined by formula in which is chosen from allcyl of 1 to 18 carbon atoms cyclo allcyl or cycloallcyl of 6 to 10 carbon phenyl and phenyl carrying 1 to 3 substituents chosen from and alkyl containing 1 to 4 carbon and and and are chosen as defined under and is chosen from groups defined for in 7 and is a group chosen from the group defined the group C S in which is chosen from a 0 or group and a and substituted by methyl and the signification given and II represent together an alkylene group containing 6 to 9 carbon Such compositions are for example the cyclohexane l nitro benzene benzene carbonylthio benzene carbonylthio benze benzimidazole benzoxazole benzothiazole benzene benzene benzene toluene toluene carbamoylthio benzimidazole methyl dibenzyl thiocarbamate defined by formula in n is a whole number between 1 and R and are chosen as given under 6 or in such a fashion that both on the hand and and two on the other hand form together a phenylene an alkylene group containing 2 to 3 carbon atoms Such compounds for example as bis disulphide bis sulphide bis hyl sulphide disulphide bis i me disulphide disulphide bis disulphide disulphide bis disulphide disulphide bis sulphide disulphide disulphide bis ethyl tetrasulphide hexasulphide diazonine perhydro trithia diazecine diazonine compound commonly called ethylenethiuram sulphide compound commonly called ethylene thiuram disulphide compound commonly called ethylene thiuram trisulphide compound commonly called ethylene thiuram tetrasulphide 26 compound commonly called propylene lphid compound commonly called paraphenylene tetr sulphide compound commonly called piperazine thiuram esters defined by the formula C S in which is chosen from of 1 to carbon phenyl and phenyl carrying 1 to 3 substituents chosen from allcyl of 1 to 5 carbon and allcyl thio groups containing carbon atoms and Such compositions for the isothiocyanate ethyl isothiocyanate isopropyl isothiocyanate butyl isothiocyanate octyl isothiocyanate phenyl isothiocyanate isothiocyanate isothiocyanate isothiocyanate isothiocyanate isothiocyanate isothiocyanate isothiocyanate isothiocyanate isothiocyanate isothiocyanate isothiocyanate ureas defined by the formula in which is or alkyl of carbon atoms and is chosen in one of the defined under and represents a group chosen from alkyl of carbon atoms and and and taken separately represent groups defined above and taken together represent ethylene group and represents a group C in which is as in selected from an alkoxy carbonyl residue containing 2 to carbon atoms and and represent Such compounds for the thiourea hiourea hiourea hiourea benzene benzene benzene benzene toluene benzene imidazolidine product commonly called ethylene thiourea Thiiranes defined by formula C C g S R R 6 in which from the groups selected under and R is alkyl of carbon methyl bearing g one chlorine phenyl bearing one chlorine of carbon carrying one or two substituents chosen from chlorine and R R and R are the same or different and are a s hydrogen or r is chosen from and octyl in which alkoxy group contains carbon R and R are each hydrogen and R is octyl or compounds for the thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane thiirane stearic acid methyl stearate butyl stearate stearate ethyl Sul defined by formula V in which is chosen from methyl bearing substituen selected from chlorine and and ethyl bearing substituents chosen from chlorine and and are chosen in one of the ways defined under and and are l of carbon phenyl or cyclohexyl and are chosen from the groups and as the group chosen in the being chosen from and in which and are selected from ethyl and and form together a cyclic system selected from a cyclic system comprising ring members and 1 or 2 rings in which the nitrogen atom is one of the ring a second ring member being chosen from a hydrocarbon oxygen and nitrogen and the other ring members being hydrocarbon ring a cyclic system as defined under and carrying one or two carbonyl oxygen Such compounds for the butyla ine butylamine dibutylamine dicyclohexylamine succiniinide benzoxazolone benzothiazolone tetrahydrophthalimide phthalimide 2 tetrahydrophthalimide aniline aniline propylamine aniline lphenyl methylamine aniline cyclohexylamine phthalimide hylthiotetrahydrophthalimide diphenylamine dimethylamine Sulfenic esters defined by formula S 0 in which is as defined in 13 and is selected from phenyl carrying substituents chosen from and alkyl and alkoxy containing carbon naphthyl and Such compounds for the phenylethane sulfenate phenyltrichloromethane sulfenate sulfenate phenyl trichloromethane sulfenate sulfenate trichloromethane sulfenate trichloromethane sulfenate trichloromethane sulfenate trichloromethane sulfenate dichlorofluoromethane sulfenate dichlorofluoromethane sulfenate henyl sulfenate sulfenate trichloromethane sulfenate ethane sulfenate methane sulfenate 2 sulfenate rifluoromethane sulfenate phenyl sulfenate sulfenate Thio ketones defined by formula S in which and are chosen from alkyl of carbon ally1 of carbon atoms carrying fluorine and phenyl carrying 1 or 2 substituents selected from alkyl and alkoxy groups containing carbon atom3 Such compounds the following thioacetylcyclohexane luoro hioacetone perfluorothioacetone 3 4j thioacetophenone thiobutyrophenone cyclohexylcarbothioylbenzene thioacetophenone thiobenzoplienone thiobenzophenone 2 thiobenzophenone 2 thiobenzopheneon thioacetophenone erived salts of mercaptans defined in 2 and of thioic acids defined in of sulphanes defined in 1 of acids corresponding to the thio carbamic esters defined in 7 and 8 in which the portion selected from metals such as strontium and aluminium and an ammonium on chosen from ions derived from ammonia and derived from amines containing groups chosen from groups of carbon atoms and phenyl groups such for a methylaniline and dimethylaniline and ions derived from a nitrogen heterocycle such as piperidine and The use of these salts is particularly valuable when the phosphoric ester used already undergone the salt introduced as stabiliser then acting in a first stage to neutralize the acid phosphoric ester by exchanging its cation therewith against a neutralization is favourable to the stabilisation since it has been noted by the applicants that the conservation of phosphoric esters is better when they do not contain any acid the sulphur compound now having lost its cation preserves its stabilising properties and then acts for a second The solvents for the phosphoric ester can advantageously be hydrocarbons of the alicyclic or aromatic series which are solid or liquid at ambient temperature under pressure or Such solvents may be used separately or in admixture Their solvent power for the phosphoric ester the stabiliser may be optionally reinforced by the addition of which may be from the groups of aliphatic hydroxylated compounds nitriles a d halogenated hydrocarbons solvents usable in compositions according to the present invention are halogenated ethers and esters formed by cyclo aliphatic or aralcoylic alcohols or phenols and aliphatic acids or di acids such as phthalic sebacic acid adipic or again phosphoric esters which are not pesticides such as the phosphoric triesters of tert The solvents usable the compositio according to the present invention can also be solid compounds such for organic synthetic such as polymers and copolymers formed starting vinyl derivatives vinylidene derivatives alkenes styrene vinyl cellulose derivatives butadiene acrylic or esters allyl esters such organic resins can also be obtained by interaction of compounds with reactive as for the resins resulting from the condensation of an epoxide on a polyester resins resulting from the action of a poly acid on a and polyurethanes resulting from the condensation of a polyisocyanate with a polyol of indene Solid able to serve as solvents can be natural such as tallol or a waxy Among inert mineral which may be used in compositions to the present invention the following should be dried calcium glass natural fossil or artificial silica metallic Amongst inert organic adjuvants which may be used in compositions according to the invention there may be for wood cellulose sugars and or diluents which are only slight solvents such as which can have its properties modified by the addition of organic synthetic resins of salts formed by alkoylamino alkoylamines and aliphatic acids a inated derivatives of such as Complementary stabilisers are advantageously chosen from such as epoxidised oil such as apoxidised soya alkoylepoxy stearates and haloalkanes or from azoic pounds or their metalliferous Compositions according to the present invention can also contain one or more natural or synthetic aromatic one or more complementary active materials as insecti fugal bird antifungal growth regulatin herbicides or So the compositions according to the present invention may be solid or They may be disposed on a solid porous or fibrous This support can be constituted for by a a felt of cotton synthetic or a compressed cellulose such as wood cereal fibres and cotton felt a card of old or card of glass According to one valuable node of application of the invention the solid porous or fibrous support for the composition be lined with a permeable membrane constituting a diffusion surface and for of a layer of polyethylene or polypropylene or of a mixture thereof or a copolymer of ethylene and propylene or of a copolymer comprising vinylidene preferabl such a membrane should be constituted by a layer of polyethylene of thickness examples of such devices are described in French Patent of 12th July Such compositions are advantageously used as insecticidal The presence of a body of sulphur containing material as stabiliser confers on the phosphoric ester a heightened resistance to the destructive effect of water contained in the composition and in the ambient as is shown by the following experiments which are merely given as So experiments carried out by the applicants are now set forth in to enable a understanding of that which has gone 1 Sheet 10 cm cut from a cellulose card made by the French Company FIOROII under reference 200 were at the moment of use the card weighed 875 The sheets of card were bonded in back ack by of these doubled cards were divided into two series denoted and The doubled cards were each impregnated with g DDVP ame for and the doubled cards were impregnated with g of a by weight solution of hydrogen sulphide in The solution had been obtained by passing hydrogen sulphide in gaseous form into the The doubled cards were suspended in a room the of which was kept at the relative humidity of which was about At the end 8 days the quantity DDVP destroyed by hydrolysis was measured potentiometrically has been establishe by others that the hydrolysis of DDVP in the conditions of exposure above leads to an acid phosphoric ester and that the potentiometric value of the single acidity or of the first acidity of this ester permit the quantity of DDVP bydrolysed to be The acidity present in the DDVP equivalent was taken into a account and this was deducted from the reaults Percentage quantities of DDVP decomposed by hydrolysis which are expressed in the table the values preceded by the sign represent the dispersion of the results in each series Doubled cards were used as described in Experiment 1 but of 835 These cards were divided into four series to Each card was impregnated with g The other doubled cards were impregnated each with g of DDVP after having been impregnated with g of one of the following salts and disodium sulphide disodium polysulphide disodium tetrasulphide mixture of disodium sulphide and hexasulphide The thus impregnated cards were suspended in a the temperature of which was kept at 21 and the relative humidity of which was about At the end of 15 days the percentage quantities of destroyed were measured as noted in Experiment 1 and tabulated as i o i o i o The results of Experiments 1 and 2 show to what degree the DDVP sensitive to humidity when it is not They also show that hydrolysis can be reduced in substantial degree when a sulphane or a salt thereof is added to phosphoric 3 Double cards were used as described in Experiment 1 but of weight 870 These double cards were divided into two series called and Cards were each impregnated g Cards were each impregnated with g of a by weight solution of pyridine in The thus impregnated cards were suspended in a room of which the temperature was kept at 22 i and the relative humidity of which was about At the end of 15 days the percentage quantities of DDVP destroyed were measured as noted in Experiment 1 and tabulated as 4 Cards of size 10 x 10 cm cut from a cellulose card made by the French company under reference 200 2 were at the moment of use the card weighed 875 g The card squares were divided into three series of three numbered units of and squares were aach impregnated with 17 and the other squares were each impregnated with g of a solution in DDVP of benzothiazole The so impregnated cards were suspended in a the temperature of which was kept at 20 and the relative humidity of which was between 55 and At the end of 15 days the percentage quantities of DDVP destroyed were measured as in Experiment 1 and tabulated as 1 Card s uares were used as dcscribed in Experiment 4 but of 870 These cards were divided into three series to Cards were each impregnated with g the other cards were each impregnated with g of a solution of in LDVP at the following 2i The thus impregnated cards were suspended in a the temperature of which was kept at 22 i and the relative humidity of which was about At the end of 15 days the percentage quantities of DDVP destroyed were measured as noted in Experiment 1 and tabulated as i 6 Squares of card were used as described in Experiment 4 but of weight These cards were divided into two series called and cards were each impregnated with g cards were each impregnated with g of a solution of in The cards were suspended in a the temperature of which was kept at 20 and the relative humidity of which was about At the end of 12 the percentage quantity of DDVP destroyed were measured as noted in Experiment 1 and tabulated as i Squaresof cards were used as described in Experiment These cards were divided into two series called and cards were each impregnated with 17g cards were each impregnated wit 17g of a solution of in The thus impregnated cards were suspended in a the temperature of which was kept at 23 and the relative humidity of which was between 55 and At the end of 8 days the percentage quantities of DDVP destroyed were measured as noted in Experiment 1 and tabulated as i 8 Doubled cards were used as described in Experiment 1 but of weight 900 These cards were divided into two series and The doubled cards were impregnated with while the other doubled cards were each impregnated with g of a solution of ethylimidazole in The so impregnated cards were suspended in a the temperature of which was kept at 22 i and the relative humidity of which was about 7 At the end of 14 the percentage quantities of DDVP destroyed were measured as noted in Experiment 1 and tabulated as i Doubled cards were used as described in Experiment 1 but of weight 880 These cards were divided into five series called to Cards were each impregnated with g The other doubled cards were each impregnated with g of a solution in DDVT at a concentration of of one of the following acetate octadecane strontium thioglycolate The so impregnated cards were suspended 121 a the temperature of which was kept at 20 and the relative humidity of which was about At the end of 10 the percentage quantities of DDVT destroyed were measured as given in Experiment 1 and tabulated as i The results of Experiments show that the hydrolysis of a phosphoric ester such as DDVT can be reduced to a substantial extent when a sulphur compound chosen from organic compounds having at least one mercaptan group is added to the phosphoric 10 Doubled were used as described in Experiment but of weight 900 These double cards were divided into seven series called to cards were each with g the other cards were impregnated each with g of a solution in DDVP of one of the following didecyl sulphide dioctyl disulphide disulphide called 3 The thus impregnated cards were suspended in a the temperature of which was kept at 22 i and the relative humidity of which was about At the end of 10 days the percentage quantities of DDVP destroyed were measured as in Experiment 1 and tabulated as i ί 1 Squares of card were used as described in Experiment These cards were divided into two series called and cards were each impregnated g cards were each impregnated g of a solution in DDVP of The so impregnated cards were suspended in a the temperature of which was kept at 22 and the relative which was about At the end of 15 the percentage quantity of the DDVP destroyed were measured as given in Experiment 1 and tabulated as 1 22 0 i 1 Doubled cards were used as described in Experiment 1 but of weight 900 These cards were divided into three series to 1 Sards were impregnated each with 1 2 g The other doubled cards were each impregnated with 1 2 g of a solution in DDVP of one of the following 1 disulphide benzothiazole The thus impregnated cards were suspended in a o the temperature of which was at 22 2 and the relative humidity of which was about At the end of 14 the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as 1 44 0 0 Doubled cards were used as described Experiment 1 2 but of weight 880 These cards were divided into fifteen series called to Cards were each impregnated with 1 2 g The other doubled cards were each impregnated g of a solution in of of the following compound benzylthio benzene sulphide lphenol disulphide dibenzyldisulphide sulphide trisulphide ditertiononyl pentasulphide ditertiododecyl polysulphide mixture titrating of sulphur containing about of of pentasulphide and of hexasulphide of The thus impregnated cards were suspended in a the temperature of which was kept at 20 and the relative humidity of which was about At the end of 15 the percentage quantities of destroyed were measured as given in Experiment 1 and tabulated as A 13 8 3 o io 0 The results of Experiments 10 to show that the hydrolysis of phosphoric ester such as DDVP can be easily controlled when a sulphur compound chosen from sulphides is added to this T 14 Card squares used as described in Experiment These cards were divided into four series to Cards were each impregnated with of the other cards were each impregnated with of a 1 or solution in DDVP of one of the following of zinc of compound known under the name of bismuthiol II The thus impregnated cards were suspended in a the temperature of whic was kept at 22 i and the relative humidity of which was about At the end of 15 the percentage quantity of DDVP destroyed measured as given in Experiment 1 and tabulated as i ί i Squares of card were used as in Experiment 4 divided into two series and squares were eac impregnated with 17 g of and squares were each impregnated with 17g of a solution in of 2 benzirnidazo These squares were suspended in a the temperature of which kept at 23 and the relative humidity of which was about 57 At the end of 7 the quantity of DDV destroyed by hydrolysis was measured as in Experiment the percentage tities of DDVP thus decomposed are indicated in the following Card squares were used as in Experiment 4 which were divided into two series numbered and squares eac impregnated with g of and the other squares were impregnated with 17g of a solution in of 2 The thus impregnated squares were suspended in a the temperature of which at 20 and the relative humidity of which was about At the end of 14 the quantity of destroyed by hydrolysis was measured as in Experiment The percentage quantities of decomposed are indicated in the following i Doubled cards were used as described in Experiment 1 p but of These cards were divided into two series and The doubled cards were each imprengated wi of The other doubled cards were each impregnated wi a solution in DDVP of 3 The thus impregnated cards were suspended in a the temperature was kept at 22 and the relative humidity of which was about At the end of 10 percentage quantities of DDVP destro ed were measured as given in Experiment 1 and tabulated as 0 Card were used as described in Experiment 4 p but of weight 880 These cards were divided into three series to the cards were each impregnated with 17s The other cards were each impregnated with 17g of a solution in of one of the following ercapto phenothiazine The thus impregnated cards were suspended in a the temperature of which was kept at and the relative humidity of which was 55 and At the end of 15 the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as Doubled cards were used as described in Experiment 1 but o weight 835 g rn These cards were divided into five series to Cards were each impregnated with The other doubled cards were each impregnated with of a solution in DDVP of one of the following compounds at the concentration of of hiomorpholine of thiazolidine of thiazolidine The thus impregnated cards suspended in a temperature of which was kept at 21 and the humidity of which was about At the end of 15 the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as o i o 20 Doubled were used as described in Experiment 1 but of weight 900 These cards were divided into three series denoted to Cards were each impregnated with The other doubled cards were each impregnated with of a solution at in DDVP of one of the following benzithiazole The thus impregnated cards were suspended in a the temperature of which was kept at 22 ί of which the relative humidity was between 70 and At the end of 15 the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated 0 21 Card squares were used as described in Experiment 4 of weight G70 These cards were divided into two series and Cards were each impregnated with 17g Cards were each impregnated with 17g of a solution in DDVP of The thus impregnated cards were suspended in a the temperature of which was kept at 22 and the relative humidity of which was about At the end of days the quantities DDVP destroyed measured as in Experiment 1 and tabulated as The results of Experiments 14 to 21 show that the hydrolysis of the phosphoric ester such as DDVP can be reduced in substantial proportion when sulphur compound chosen from heterocyclic compounds is added to this t Card scpares used as described in Experiment these cards were divided into two series and cards each impregnated with 15g cards each impregnated with 15g of solution of thiobenzoic acid in The thus impregnated cards were suspended in a the temperature of which was kept at 23 and of which the relative humidity was At the end of 8 the percentage quantities of DDVP destroyed measured as given in Experiment 1 and tabulated as 23 Doubled cards were used as described in Experiment 1 but of weight 895 These cards divided into three series to Cards were each impregnated the other doubled cards were each impregnated with g of a solution in of one of the following compo disulphide The impregnated cards were suspended in a the temperature of which was at 22 ί and the relative humidity of which was about At the end of 15 the percentage quantities of destroyed were measured as given in Experiment 1 and tabulate as 0 ί i 24 Card were used as described in Experiment These cards were divided into three series to Cards were impregnated with g of the other cards were each with g of a solution at one or two percent in DDVP of one of following 1 of potassium butyl trithiocarbonate of potassium butyl trithiocarbonate The thus impregnated cards were suspended in a the temperature of which was kept at 22 ί and of which the relative humidity was about At the end of 15 the percentage quantities of DDVP destroyed were measured as give Experiment 1 and tabulated as Doubled cards were used as described in Experiment 1 but of weight 900 These cards were divided into two series and Cards were each impregnated with of The other doubled cards were each impregnated with a solution in of zinc isopropyl The thus impregnated cards were suspended in a the temperature of which was kept at 22 2 and the relative of which was about At the end of 15 the percentage Quantities of DDV destroyed were measured as given in Experiment 1 and tabulated as 0 26 Doubled cards were used as described in Experiment 1 but of weight 8oG These cards were divided into seven series called to Cards were each impregnated with of The other doubled cards were each impregnated with of a 2 or solution in of one of the following of trithiocarbonate of dibenzyltrithiocarbonate of ethylene trithiocarbonate 3 of of potassium tJiioacetate of sincthiobenzoate The cards were suspended in a the temperature of which was kept at 20 and the relative of which was At the end of 10 the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as 8 0 0 0 0 The results of experiments 22 to 26 show that the hydrolysis of a phosphoric ester such as DDVP can be reduced in notable proportion when a sulphur compound chosen from thioic compounds or salts thereof is added to this Card squares were used described in 4 but of weight These cards were divided into three series called and Cards were each impregnated with 17 g the other cards were each impregnated with of a solution in DDVP of one of the following thiobenzamide thionicotinarnide The thus impregnated cards were suspended in a the temperature of which was kept at 23 and the relative humidity of which was about 5 At the of S days percentage quantities of DDVT destroyed were measured as given in Experiment 1 and tabulated as i i Doubled cards were vised as described in Experiment These cards were divided into two series and Cards were each impregnated 1 card were each impregnated with 14g of a solution of in The thus impregnated cards were suspended in a the temperature of which vas kept at 22 and the relative of which was about At the end of 8 the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulat as ί Card squares were used as described in Experiment These cards were divided into two series and Cards were each impregnated with of cards were each impregnated with g of a solution in DDVP of thiobenzamide compound known under the common name of i The thus cards were suspended in a the temperature which was kept at 22 and the relative humidity of which was about At the end of 15 the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as 2 22 i 1 i 30 Doubled cards were used as described in Experiment 1 but of weight 900 These cards were divided into three series to were each impregnated with of The other doubled cards were each impregnated g of a solution in DDVT of thioisonicotinamid of thioisonico inamide of thioisonicotinamide The thus impregnated cards were suspended in a the temperature of was kept at 22 and the relative humidity of which was about 75 At the end of 20 percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as ί Doubled were used as described in Experiment 1 but weight These cards were divided into three series to Cards were each with g of other doubled cards were each impregnated solution in of one of the following epsilon The thus impregnated cards were suspended in the temperature of which was kept at 20 and the relative humidity of which was about At the end of 10 the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as The results of Experiments 27 to 31 that the of a phosphoric ester such as DDVP can be reduced by substantial proportion when a sulphur chosen from thiamides is added to this Card squares used as described in Experiment These cards were divided into seven series to Cards were each impregnated with g of the other cards impregnated with g of a solution in DDVP of one of the folio ing compounds at the concentration c of ethyl I o methyl amate of m thyl of methyl of methyl entamethy1ene dithiocarbamate The thus impregnated cards were suspended in a the temperature of which was kept at 22 and the relative humidity of which about At the end of 15 percentage of destroyed were measured as given in Experiment 1 tabulated as 3 3 1 33 Double cards were used as those described in Experiment 1 but of weight These doubled cards were divided into two series and cards were each impregnated with 1 g of the other doubled cards were impregnate with 1 g of a solution in DDV at of zinc The thus impregnated cards were suspended in a the temperature of which was kept at 22 the relative humidity of which was about At the end of 15 the percentage quantities of destroyed were measured as given in Experiment 1 and tabulated as ί Card squares were used as those described in Experiment These cards were divided into three series 3 to cards were each impregnated with of the other cards were each impregnated of a solution in of one of the following compounds at the concentration of zinc dithiocarbamate zinc l dithiocarbamate compound known under the common name of The thus cards were in a the temperature cf which was kept at 22 and the relative humidity of which was about At the end of days the percentage quantity of destroyed were measured as given in Experiment 1 and tabulated as 0 0 i 35 Squares of card were as described in Experiment These cards were divided into ten series denoted to cards were each impregnated with g the other cards were each impregnated with of a solution in DDVP of one of the following compounds at the concentration of zinc of zinc of cadmium of of cupric h of silver of zinc of zinc The thus impregnated cards were suspended in a the temperature of which was kept at 22 i and the relative humidity of which was about At the end of 15 the percentage quantities destroyed were measured as given in Experiment 1 and tabulated as 0 0 0 Doubled cards were used as described in Experiment These doubled cards were divided into three series to cards were each impregnated the other cards were each impregnated with of a solution in DDVP of one of the following at the concentration ate compound under the common of zinebe The thus impregnated cards were suspended in the temperature of which was kept at 22 ί and the relative humidity of which was about 45 At the end of 8 days the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as ί Doubled cards were used as described in Experiment 1 but of weight 8o5 These cards were divided into ten series to Cards were each impregnated with the other doubled cards were each impregnated with of a solution in DDVP of one of the following zinc dithiocarbamate sodium d sodium di sine dithiocarbarnate bismuth dithiocarbarnate nickel hylene dithiocarbarnate pyridine ethylene dithiocarbarnate lead lene di The thus impregnated cards were suspended in a the of which was kept at 21 and the relative humidity of which was about 65 At the end of 15 the percentage quantities of destroyed were measured as given in Experiment 1 and tabulated as 34 0 0 0 0 0 0 The results of experiments 32 to 37 show that the hydrolysis of a phosphoric ester such as can be reduced by a very great degree when a dithiocarbamic sulphur compound is added thereto j the results of experiment 35 show furthermore that it is possible to obtain a very good stabilisation by using certain compounds of at a concentration as weak as 0 38 Doubled cards were used as described in Experiment 1 of weight 890 These cards were divided into two series and Cards were each impregnated with 12 g The other doubled cards were each impregnated vdth 1 2 g of a solution in of The thus impregnated cards were suspended in a the temperature of which was at 22 and of which the relative was about 7 At the end of 15 the percentage quantity of DDVP destroyed were as is given in Experiment 1 and tabulated as 41 4 1 0 o o E 39 Card squares were used as described in Experiment 4 but of weight These cards divided into two series Cards were impregnated each with 17g The other cards were impregnated each with 17g of a solution in DDVP of 2 benzimidazole The thus impregnated cards were suspended in a the temperature of which was kept at and the relative humidity of which was about 4 At the end of 14 the percentage quantities of DDVP destroyed were measured Experiment 1 and tabulated as 27 9 ί 1 1 The results of experiments and 39 that the hydrolysis of a phosphoric ester such as DDVP can be reduced to a very great degree when a sulphur compound chosen from carbamic esters is added to this phosphoric Squares of card were used as described in These cards were divided into three series to cards were each impregnated with the other cards were each impregnated with of a solution in DDVP of the following compounds at the following of disulphide 2J of bis disulphide This compound is commonly called tetraeth disulphide The thus cards were suspended in a of which the temperature was kept at 22 2 C and of which the relative humidity was about At the end o 15 days the percentage Quantity DDV destroyed were as given in Experiment 1 and tabulated as Card squares were used described in Experiment These cards were divided into three series to cards were each impregnated with g the other cards were each impregnated with of a solution in DDVP of one of the following bis sulphide disulphide compound commonly called monosulphide compound commonly called tetramethylthiuram disulphide and known under the common name of The thus impregnated were hung up in a the temperature of which was kept at 22 and the relative humidity of which was about At the end of 15 days the percentage quan ity of DDVP destroyed were measured as given in Experiment 1 and tabulated as 0 0 Doubled cards were used as described in 1 but of weight These cards were divided into seven series to Cards were each impregnated With the other doubled cards were each impregnated with g of a solution in DDVP of one of the following bis tetrasulphide bis disulphide bis disulp ide bis bis disulphide bis tetrasulphide The thus impregnated cards were suspended in a the temperature of which was kept at 21 20C and of which the relative humidity was about At the end of 15 percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as 0 0 0 0 The 40 show that the of the phosphoric ester such as DDVP can he reduced in substantial proportion when a thiuram compound of sulphur is added to the Doubled cards were used as described in Experiment 1 but of weight 900 These doubled cards were divided into three series to the doubled cards were each with the other doubled cards were each impregnated of a solution in DDVP of one of the follo ing ethylisothiocyanate The thus impregnated doubled cards were suspended in a the temperature of which was kept at 22 i and of which the relative humidit was about At the end of 15 days the percentage quantities of DDVP destroyed were measured as given in Experiment 1 tabulated as i The results of this experiment show that the hydrolysis of the phosphoric ester such as DDVP can be reduced in substantia proportions when a sulphur compound selected from isothiocyanic esters is added to the this Card s uares were used as described Experiment 4 but of g These cards were divided into five series to cards were each impregnated with other cards were each impregnated with 17g of a solution in of one of the following thiourea ethylthiourea ethylene The thus impregnated cards were suspended in a of which the temperature was kept at 20 2 C and of which the relative humidity was between 55 and At the end of 15 the percentage quantities of the destroyed were measured as given in Experiment 1 and tabulated as ί 45 Card squares were used as described in Experiment but the weight of which was 885 These cards were divided into four series to cards were each impregnated with 17g the other cards were each impregnated with 17g of solution in of one of the following ethylthiourea also the of thiosinamine The thus impre nated cards were in a the temperature of which was kept at 22 and the relative humidi y of which about 65 At the end of days the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as i i ΕΧΡ Ι 46 Doubled cards used as described in Experiment 1 but of weight These cards were divided into two series and Cards were each impregnated with The other cards were each impregnated with solution in DDVP of The thus impregnated cards were suspended in a temperature of which was kept at 21 the relative humidi y of which was about At the end of 15 the percentage quantities of destroyed were measured as in Experiment 1 and tabulated as The results Experiments 43 to 46 show that the hydrolysis of a phosphoric ester such as DDVP c n be reduced in notable proportions when a sulphur compound chosen from thioureas is added this Doubled cards used as described 1 but of These cards were divided into two series or Cards were each impregnated with g The doubled cards were each impregnated with g of a solution in of The thus cards were suspended in a the of which was kept at 20 and the relative humidity of which was about At the end of 10 the percentage quantities of destroyed were measured as given in Experiment 1 and tabulated as 0 i EXPERIMENT 48 Doubled cards were used as described in Experiment 1 but of weight 895 These cards were divided into three series to the doubled cards were each impregnated with of the other doubled cards were each impregnated with of a solution in of one of the following thiirane The thus impregnated cards were suspended in a the temperature of which was kept at 22 ί and the relative of which was 70 At end of the percentage quantities of DDVP destroyed were measured as in Experiment 1 tabulated 0 This experiment shows the particularly results which can be obtained in the stabilisation of phosphoric esters such from as DDVP when a sulphur compound c is added Doubled cards were used as described in Experiment 1 but of 900 These double cards are divided into four series to cards were each impregnated with the other cards being each impregnated with of a solution in DDVP of one of the following compounds at the concentration of of compound under the common name of compound under the common name of The thus impregnated cards were suspended in a the temperature of which was kept at 22 ί and the relative humidity of which was about At the end of 1 the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as The of this Experiment show the hydrolysis of ifnosphoric ester such as can be reduced in notable proportion w sulphur chosen from is added Doubled cards were used as described in Experiment 1 but of 900 These cards were divided into four series to were eac impregnated with of The other doubled cards were each impregnated with of a solution in of one of the following uinolyltrichloromethane sulphanate ane sul ate The thus impregnated cards were suspended in a o the temperature of which was kept 22 2 and of which the relative humidity about At the end of 10 the percentage quantities of destroyed were measured as given in Experiment 1 tabulated as JO Ί Ί The results of this experiment show that the hydrolysis of a phosphoric ester such as can reduced in notable proportions when a sulphur compound selected from sulphenic esters is added to t is 1 Doubled cards used as described in Experiment 1 p but of 890 These doubled cards were divided into two series 5 cards were each with of the other double cards were each impregnated with of a solution in DDVP of The thus impregnated cards were suspended in a o the temperature of which was kept at 22 2 C and the relative humidity of which was about At the end of 15 the percentage quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as The results of this Experiment show that the hydrolysis of a phosphoric ester such as can be reduced in substantial proportion when a sulphur compound chosen from thio ketones is added Cards size 5 10 cm were used as described in Experiment 1 but left at a single These cards were divided into three series to Cards were each with 6g of The other cards were each impregnated with 6g of a solution of one of the following compounds at in 0 dimethyl 2 zinc h The thus car were suspended in a the temperature of wh was kept at 22 and the relative humidity of which was about At the end the percentage quantities of ester destroyed were Account was taken of the starting acidity present in the phosphoric ester to of and this was deducted from the 5 Card squares of size 5 x 10 cm as those described in Experiment were used but left at a single These cards were divided into five series called to Cards were each impregnated with of 2 diethyl The other single cards each impregnated with of a solution of one of the following compounds at in 2 benzothiazole zinc io carbamate bis bis disulphide The thus impregnated cards were suspended a the which was kept at 22 and the relative humidity of was about At the end of percentage of destroyed were as in Experiment 1 and tabulated as 0 cards were used as described in Experiment 1 but of 885 These cards were divided into four series to were each impregnated with 14g DD7 The other double cards were each with 14g of a solution in of one of the following of 2 ole of azobenzene of 2 methyl idazole 0 of azobenzene The thus impregnated cards were suspended in a o the temperature of which was kept at 22 2 and the relative humidity of which At the end of 12 the percentage quantities of destroyed were measured as given in Experiment 1 and tabulated 46 10 1 3 1 7 55 Doubled cards were used as described in Experiment These doubled cards were divided into five series to Cards were each impregnated with g the other cards were each impregnated with g of a solution in DDVP as th azobenzene azobenzene After imprecation the double cards vere each placed in a sachet nylon by a of made from thread and formed into a made by the Tripette et The devices thus prepared in a the of which was kept at 22 the relative humidity of which was about At the end of 15 the percentage ies of the destroyed were measured as in Experiment 1 and tabulated as 5 0 Doubled in sachet cards were used described in Experiment The doubled cards were divided into six series to The were each impregnated the other doubled cards were each impregnated with of a solution in as of of h of j of 0 thus were suspended in a the which was kept at 22 and the relative humidity of which was 35 At the end of 30 the percentage quantities of destroyed ere measured as in Experiment 1 and tabulated as 5 ί i cards in sachets were used as described in but in which the of the card was 900 The double cards were divided into eight series to cards were each impregnated with 1 the other double cards were each impregnated w th 2 of a solution in as of bis 1 of bi pyrazole 1 of 1 of disulphide of inoazobenzene 1 of 1 25 of hy uisulphide 0 The thus impregnated cards were suspended in a the of which was kept at 22 and the relative humidity of which was about At the of 30 the quantities destroyed were as in Experiment 1 tabulated as 9 The results of Experiments 54 to 57 the value provided by of stabilisers according to the invention stabilisers to the family of azoic There is in effect a synergistic effect u these two types of stabilisers as the of these cards were used as described in Experiment 1 but of weight These doubled cards were divided into six series to Cards were each impregnated with the other doubled cards were each with 2 of a solution in of one of the di lsulphoxide iona e ethyl The thus impregnated cards were suspended in a the temperature of which was kept at 22 and of which the relative y of which about At the end of 15 the percentage quantities of destroyed were as in Experiment 1 and tabulated as Doubled cards were used as described in Experiment 1 p but 895 These double cards were divided into four series to cards were each with the other double cards were each impregnated with of a solution in DDVP of one of the following sulfone diphen l one paratoluene sulfonic acid The were suspended in a the tempera of which was a 22 20C of w the relative humidity was about At the end of 15 the quantities of DDVP destroyed were measured as given in Experiment 1 and tabulated as 36 The results of Experiments and 59 that it is not possible to stabilise a phosphoric ester such as DDVP with a sulphur conpound different from those defined and recommended by the present Several are described below with the object illustrating the invention not of limiting For simplicity oO of the sulphur are denoted as A salt Compound C sulphide ound D bi thioacetamide Compound zinc Compound sulphide methyl 7 asoic used in several cases as complementary abilisers are denoted as with the of oy Diazo pound A h laminonaphthalene Diazo pound B cyclohexane Diazo pound Diazo pound D Diazo chromium complex in admixture of the pound azoic salt sodium salt sodium salt Diazo chrome complex in admixture of diaso compounds pound F salt and q so 1 to Insecticidal compositions comprising D phosphoric nd at least one sulphur compound principal stabiliser for this these also optionally ning a solvent for the ester stabiliser selected from azoic compounds and epoxidised Values in the following table and in the tables appended to the remainder of are in parts by 11 to 90 Insecticidal compositions comprising as phosphoric ester at least one sulphur compound as principal stabiliser a vaseline or paraffin oil as a heavy as and in some cases a complementary stabiliser selected from azoic and epoxidised oil having a density of at C and a gelation point of about oil having a density of at and a viscosity of at l compositions phosphoric at one sulphur iliser solid or ed from vaseline and a heavy some a c stabiliser selected of colour having a point greater chestnut product having a dropping point of about Insccticidal compositions usable in a wick evaporator formed by a reservoir and a wick dipping into the composition and having a part exposed to the free These comprise as phosphoric a solvent from the ester chosen from among a selected from chlorodeca and at least one sulphur as principal stabiliser for the phoric ester and in some cases a complementary stabiliser select from azoic and under of diethyl ether and manufac ured under the the united States Company Union Carbide Chemicals of known under the name of utyl ether sold under the Trade by the Union Carbide Chemicals distillation cut between and of aliphatic brcinched chain hydrocarbons obtained by containing a mixture of and produced by the company Standard phosphoric at one sulphur compound as principal iliser for this o material selected from linalol linalyl and citron terpenes and in con selected from azoic epoxidised to phosphoric at one div la t sulphur compound as principal synthetic thermoplastics resin solid and a heavy ester used as at the time as in some cases piasticiser for the resin and in some cases a complementary selected and epoxidised copolymer of ethylene of vinyl acetate an intrinsic viscosity of for 100 toluene a product sold the Trade Mark and defined in t e colour index under lue comprising phosphoric at least one divalant sulphur compound as principal stabiliser for this a paraffin as solid a fossil silica as mineral in some cases a mentary stabiliser selected from azoic and epoxidised a copolymer of ethylene and vinyl improving mechanical properties of the a as dispersing agent the homogeneity of composition to be maintained before TABLE VII 61 64 65 66 67 68 69 70 i 25 25 25 24 5 ordinary paraffin 6o 57 46 54 54 58 Copolymer of ethylene 12 12 and vinyle acetate fossil diatoms 15 16 15 15 15 15 15 15 amin oleat 5 5 monmorillonite 1 1 pigment epoxidised soja oil cyclohexyl epoxystearat Azobenzene Diazene B Compound A Compound B Compound D Compound F Compound I product under the defined in the colour index under the 21100 product the reaction in ratio of between oleic acid and a mixture of the amine adecylaminepropylene a mixture of dimethyl dihexadecylaimnonium and dimethyl of tetrachlorobiphen having a density between and sold under the Trade Hark by the French Company Electrochemie acieries ixture of octachlorobiphenyls having a softening point of 110 the Trade by the It is that the invention is not limited to the formulations set which are merely given as examples of the manifold possibilities of use of the In the of these formulations can be replaced by a phosphoric ester chosen vinyl dimethyl phosphate vinyl diethyl phosphate vinyl dipropyl phosphate vinyl dibutyl vinyl dimethyl phosphate vinyl diethyl phosphate vinyl dipropyl phosphate vinyl dimethyl phosphate vinyl diethyl phosphate ethyl methyl phosphate ethyl dimethyl phosphate ethyl diethyl phosphate ethyl dimethyl phosphate ethyl diethyl phosphate j ethyl dimethyl phosphate ethyl diethyl phosphate propyl dimethyl phosphate propyl diethyl phosphate 2y dimethyl phosphate vinyl diethyl phosphate vinyl thiophosphate insufficientOCRQuality

Claims (1)

1. CLAIMS A pesticidal composition to calculated on the weight of the of a phosphoric ester the formula where and are the same or different l and a dihalomethylvinyl when and are each independently methyl or may also he a or to 10 based on the weight of the phosphoric of an agent stabilising said ester against decomposition by and comprising at least containing 5 to by weight sulphur and containing at least one divalent sulphur atom which is either by one to a nitrogen or hydrogen o a metal capable of salt formation by the other to a or metal or bonded by one valency to an oxygen by the valency to a sulphur or carbon atom o bonded via both valencies a carbon nitrogen or metal 0 to based on the weight of of one or solvents for the phosphoric liquid or solid under pressure o and 0 to based o the of composition of one or more inert adjuvants chosen frost mineral adjuvants and organic compatible with the phosphoric Λ process for stabilising a pestieidal este phosphoric acid as defined in Claim 1 which process prises mixing the ester or a which contains with to calculated o the weight of the phosphoric acid ester of agent capable of ing said phosphoric ester against protonisation prisin at leas one sulphu compound as defined i claim if thereto to the weight of the final of one or more solvents fo the phosphoric ester which are solid or under pressure or otherwise and calculated on the weight of the final of one or more inert adjuvants selected from mineral adjuvants and organic adjuvants compatible with the phosphoric A composition or process according to claims or 2 characterised in tha the proportio of sulphur in the stabilising agent at least by A composition or according to claims characterised in tha the stabilising agent is selected de by 1 H by II H S in which R is chosen from a group Ra chosen a phenyl a benzyl a phenyl group and a benzyl group bearing substituents chosen from residues containing atoms of an alkyl group containing carbon a heterocyclic group chosen from monocyclic and bicyclic heterocyclic groups comprising 5 to 10 ring atoms in which of the ring members are chosen from the group and a second and a third ring member being chosen from the groups C in which is a group chosen from and an alkyl or cycloalkyl group containing carbon atoms and or an alkyl group containing carbon the groups to noted above carrying substituents chosen from chlorine and bromine an the groups to noted above carrying a stituent chosen from alkoxy alkoxy carbonyl containing 2 to 6 atoms of carbon and an amino group in which and are the same or different and are chosen from hydrogen and alkyl residues containing atoms of carbon and group A H which A is a group chosen containing carbon toluylene and ethylene 6 A or process to claims 1 in that the stabilising agent is selected from defined by formula in and are chosen an alkyl of 1 to 18 phenyl morpholinyl piperidyl pyridyl benzothiazolyl benzimidazolyl benzoxazolyl the groups to just mentioned carrying substituents chosen from bromine hydrox alkoxy carbonyl of carbon and amino as defined in 2 above and an alkyl containing 1 carbon atoms and n represents a whole number between 1 and 6 7 A or process according to claims 1 characterised in that the stabilising agent is selected from o which comprise 5 to 23 ring members forming 1 to 5 rings with at most 2 to 3 which comprise rings which each contain an chain and 2 other chains members chosen from the groups C the remainder of the chain members being chosen from among the groupings C and heterocyclic compounds with fused rings being chosen from among those of which all the hetero chain members are contained in one and the same this ring being the central ring in the case of 3 fused all the ring members being chosen taking into account that all the valences of the heterocyclic compound should be and being independently chosen from alkyl of carbon and as defined under 2 ri the group S which and are the same or different and are phenyl or alkyl carbon alkanoyl amino containing carbon alkyl thio containing carbon the oxo phenylazo substituents chosen from nitro and and being chosen from hydrogen and 1 A or process claims characterised in that the sta ilising agent is selected from Monocyclic heterocyclic compounds chosen from saturated heterocyclic compounds with 6 ring members in which ring members which not contiguous are constituted by one other ring being chosen rom the groups and and the remainder of the ring members being chosen from the groups in which have the definitio given claim A composition or process according to claims characterised in that the stabilising agent is selected from compounds defined by formula R C Q Λ in which R X and Q are chosen from those defined under and the compounds in which R and form two distinct groups and in which is a group chosen from allcyl or carbon atoms and an l residue as just mentioned bearing a substituent chosen from alkoxy carbonyl having 2 to 5 carbon cyclo alkyl or alkyl cyclo alkyl containing 6 to 10 carbon or alkenyl containing 2 to 5 carbon atoms and X and Y represent an atom chosen from oxygen and sulphur at least one of them per molecule being a sulphur is chosen from among a a group R selected from an alkyl containin 1 to 6 carbon atoms an carrying a group cycloalkyl containing 6 zo 10 carbon alkyl cycloalkyl containing 6 to 10 carbon and phenyl bearing one to three substituents chosen from alkyl of 1 to carbon and hydroxy β a group B C Y in which Y and R have the Λ ition given above and in which B is chosen from a disulph group and a hydrocarbon divalent group chosen from alkylenes containing 1 to 8 carbon atoms and and henylenes a group Z chosen among groups in which Z is oxygen or sulphur and R is a group chosen from those defined for c the compounds in which R Q form together alkylene group containing 3 to 10 carbon atoms in branched or chains and compounds in which Q represents the group Z and R and R form a divalent group chosen from aliphatic chains containing 2 to 6 carbon cyclic systems containing 5 to 10 ring members one or two under which one of the two ring members chosen from the group the group N v and the group A composition or process according to claims characterised in that stabilising agent is selected from s defined by formula C E in which are chosen as defined under and a a and are each separately chosen from alk l of 1 to 4 carbon phenyl and taken together from an straight or branched chain group containing 4 to 10 carbon S represents a group chosen from a group as claim 9 defined under in a group C S in which D represents a symbol chosen from a direct bond or a divalent hydrocarbon group chosen from alkylenes containing 1 to 8 carbon atoms and phenylenes and in which and have the same meaning as above and E represent together a group such as defined under in claim A composition or process according to claims characterised in that the stabilising agent is selected from defined G S C in which is chosen of 1 to 4 carbon and phenyl and in which represents a group chosen from a group chosen from an alkyl containing 1 to 12 carbon alicenyl containing 2 to 12 carbon cycloallcyl or cycloalkenyl containing 5 6 carbon allcyl and cycloalkenyl such as defined above bearing 1 to 3 allcyl substituents each containing 1 to 4 carbon phenyl a phenyl group carrying 1 to 3 substituents chosen from allcyl and groups containing to 5 carbon chlorine and a group S in which is alkylene straight or branched chain containing 2 to 6 carbon atoms and and are chosen such as defined claim 10 in and in which is chosen a group has one of the meanings given for defined above and a group S R in and have the definiti S given above A composition or according to claism x characterised in that the stabilising agent is from s defined by formula S C a o in which is chosen from of 1 to 18 carbon atoms cyclo alkyl or alkyl cycloalkyl of 6 to 10 carbon phenyl and phenyl carrying 1 to 3 substituents chosen and alkyl containing 1 to 4 carbon and and and are chosen as defined under and is chosen from groups defined for in claim and is a group chosen from the group defined the group S in which is chosen from a o or group and a grou substituted by methyl and has the signification given and LI represent together an allcylene group containing 6 to 9 carbon atoms A composition or process according to claims characterised in that the stabilising agent is selected from defined by formula in n is a whole number between Ί and and are claim 10 chosen as given under in such a fashion both on the ond hand and and two on the other hand form together phenylene an allcylene group containing 2 to 3 carbon atoms A or process according to characterised in the is selected from ers defined by in which is of 1 to 8 carbon phenyl and phenyl carrying 1 to 3 substituants chosen from of 1 to 5 carbon and ally1 thio groups containing carbon atoms and A composition or process according to claims characterised in that the stabilising agent is selected from Thio ureas defined by the formula in which 1 is or alkyl of carbon atoms and is chosen in one of the ways defined under and W represents a group chosen from alkyl of carbon atoms and and taken separately represent groups defined above and taken together represent ethylene group and vV represents a group NH C NH II s claim in which is as defined in selected from an carbonyl residue containing 2 to carbon atoms and and represent A composition or process according to claims characterised in tha the stabilising agent is selected from defined by in which R R R and R are chosen from the groups selected g g g under and R is of carbon methyl bearing g one chlorine phenyl bearing one chlorine alkoxy of carbon phenoxy carrying one or two substituents chosen from chlorine and R R and R are the same or different and are hydrogen or is chosen from and octyl in the alkoxy group contains carbon R and R are each hydrogen and is octyl or A composition or process according to characterised in that the agent is from defined by formula S in which is chosen from methyl bearing substituents selected from chlorine and and ethyl bearing substituents chosen from chlorine and and are chosen in one of the ways under and and are of carbon phenyl or and are chosen from the and the group chosen in the group being chosen from in which and are selected from ethyl and form together a cyclic system selected from a cyclic system comprising ring members and 1 or 2 rings in which the nitrogen atom is one of the ring a second ring member being chosen from a hydrocarbon oxygen and nitrogen and the other ring members being hydrocarbon ring a cyclic system as defined under and carrying one or two carbonyl oxygen A composi ion or to claims characterised in that the agent selected from defined by formula in which is in claim 17 and selected from phenyl carrying substituents chosen and alkyl and containing carbon naphthyl and A composition or process according to claims characterised in that the stabilising is selected from defined by S in which and are chosen alkyl of carbo alley1 of carbon and carrying fluorine and phenyl carrying 1 or 2 selected from alley1 and alkoxy groups containing carbon A composition or process to claims characterised in the stabilising agent is selected from salts derived from defined in claims and 8 and in which the cation c part is chosen from a metal and an ammonium ion chosen from derived from ions derived an amine containing groups of carbon derived from an aromatic and ions derived from a nitrogen heterocycl 0 A composition or process to claims characterised in that stabilising agent is from salts from t acids defined in claim and in which the part is chosen from a metal and an ion chosen ions derived from ions derived from an amine groups of carbon atovas and an aromatic ions deprived from a nitrogen A composition or process according to claims characterised in that the stabilising agent is from salts corresponding to ester defined in claims ctnd in which the cationic part is chosen from a and an ammonium ion chosen from ions derived from ions derived from an containing alkyl groups of carbon atoms and derived from an aromatic and ions derived from a nitrogen composition or process to of the preceding wherein the proportion of stabilising is between 0 2 and by of the phosphoric A composition or process according to any o the preceding cl the of the phosphoric ester contains one or groups chosen from ethyl and A composition or process according to any of the preceding claims wherein the molecule of the phosphoric ester contains at least one methyl A composition or process according to any of the preceding wherein the phosphoric ester is selected from phosphate 2 phosphate phosphate diohlorovinylrli phosphate phosphate phosphate phosphate phosphate phosphate phosphate phosphate phosphate phosphate phosphate phosphate 4 phosphate p phosphate A composition or process according to any of the preceding wherein the phosphoric ester is vinyldimethyl A composition according to of claims 1 and wherein it contains solvent which is solid or liquid at ambient temperature under pressure or otherwise selected from aliphatic alicyclic aromatic esters formed by alipViatic or aralcoylic or phenols and aliphatic mono carboxylic acids or aliphatic or dicarboxylic esters formed by phosphoric acid and the said alcohols and mixtures between two or more of these A according to each of claims 1 and when it contains a solid solvent for the phosphoric ester selected from homopolytners and copolymers based on vinyl derivatives vinylidene derivatives styrene vinyl cellulose derivatives acrylic and methacrylic esters or co from the reaction of compounds with reactive groups selected from epoxy resins formed by the condensation of an epoxide and a resins by the action of a the condensation or resins of the A according each of 1 it contains a solid solvent for the phosphoric ester selected from and waxy natural A according to each of 1 and when it contains an inert mineral or organic which is a or only slight solvent for the phosphoric acid ester A composition according to claim 31 wherein the inert adjuvant is selected dried calcium glass fibre natural fossil or synthetic silica and metallic wood cellulose and A composition according to claim 31 wherein the inert adjuvant is a a petrolatum or a paraffin optionally modified by the addition of synthetic organic resins salts formed by alkoylamino alkoylamines and acids derivatives of ontmorillonite such as A composition according to each of claims 1 and comprising an epoxidised compound in a proportion of to based on the weight of a pesticidal phosphoric A composition according to each of claims 1 and an azoic compound in an of to the weight of the phosphoric pesticidal A composition according to claims 1 and substantially as described herein ence to the A porous or fibrous support having applied thereto a compoei as claimed in any one of claims 1 and 3 A support according to claim 37 whic is a a paper card of agglomerate of A support according claim 37 or lined with a permeable A support according to claim wherein the permeable membrane is formed by a layer of polyethylene or propylene or mixture thereof or a copolymer of ethylene and propylene or of a copolymer comprising A support according to claim 39 or 40 wherein the permeable membrane is formed by a layer of polyethylene ing a thickness of A support to claim 37 substantially as cribed herein with reference to the insufficientOCRQuality