NZ199100A - Acaricidal hydroquinone diether compositions - Google Patents

Abstract

A method and compositions for combatting mite infestations on useful plants, by treating the hibernating (or over-wintering) eggs with a compound of the general formula: <IMAGE> in which R' represents an alkyl group having from 8 to 11 carbon atoms, R'' represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, an allyl group or a <IMAGE> group, in which R<2> represents an alkyl group having from 1 to 4 carbon atoms, a cycloalkyl having from 3 to 6 carbon atoms or a phenyl group.

Description

New Zealand Paient Spedficaiion for Paient Number 1 99100 199100 $ ■ i9- ■ 80 Priority Dat®(s): CosTspSete Specification Filed: 11 flO/M 3ljife> '' '(U'DEC 1984 3 Vi i* h t Ca *»u w b i tuJCJC.0* ai9aDaeD3asttt««ia P.O. Journal, Mo: .... .......

No.: Date: NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION ACARICIDAL COMPOSITIONS ACTIVE AGAINST HIBERNATING EGGS X/We, MONTEDISON S.p.A., 31 Foro Buonaparte, Milan, Italy, an Italian company, hereby declare the invention for which X / we pray that a patent may be granted to ficse/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - il 991 0 The present invention concerns a method for fighting acari infestations on useful plants, and in particular it relates to a method consisting in treating the hibernating (or overwintering) eggs of mites with compounds belonging to the class of hydroquinone diethers. The invention relates, moreover, to compositions that are active against overwintering eggs of mites, containing the above mentioned compounds.

In evaluating the acaricide activity of a compound active against mite eggs, distinction has to be made between the ovicide activity against the summer eggs and the ovicide activity against the overwintering eggs.

In fact, some mite species . overwinter in the stage of eggs and these overwintering eggs are less sensitive to pesticides in comparison to summer eggs. This is due to the state of quiescence of the embryonal life as well as to the barrier that the chorion of the egg, more resistant than that of the summer eggs, offers to the penetration of the active substance.

Different acaricide compounds are known, some of which are active against the summer eggs of mites r.others -active against ne anides or adult mites. However, because of the particular characteristics of the overwintering eggs of mites, the greatest part of the known acaricide compounds prove to be inactive on this kind of eggs. its 91 QiQ Other compounds prove to be only partially active and exclu sively during the very short period of time close to the hatching of the eggs. The winter control of mites is generally, conducted by using formulations of phosphoric esters (in particular Parathion) in mineral oils. Also in this case, the effecti_ veness of such formulations is never complete and is achieved only by treating in coincidence with the hatching of the eggs.

In the short period of time in which such a treatment may be useful, there often are adverse weather conditions. A treatment preceding the above mentioned period proves little effecti_ ve on winter eggs because they, as previously indicated, are particularly resistant to penetration of the pesticide. On the other hand, a delayed treatment may produce phenomena of phyto-toxicity in as much as the advanced vegetative stage of the plants is sensitive to many mineral oils.

The availability of' specific products active against overwintering eggs would allow to carry out treatments in full win ter, thereby eliminating the afore mentioned difficulties and at the same, time offering the advantage of not causing a damage to numerous species of insects useful for controlling mites (predatory insects). Moreover, under a practical point of view, 199100 the possibility to protect the cultivations from mite attacks in winter time, that is, during a period in which the work in the farm is limited, represents a further undoubted.advantage.

As far as we know, there are no specific acaricide compounds on the market that are active against the overwintering eggs of mites. tyfe have previously found that hydroquinone diethers that may be collected under the following general formula: « - o/oV 0-(CH„)_-X-(CH„) -Y (I) wherein: \ j 2 m 2 n R represents either an alkyl or an alkenyl X represents an oxygen- atom, a -CH=CH- or a -C— C- group; m and n (equal to or different from each other) represent a positive integer from 1 to 4; Y represents an OH or SH group, an -0-R^" or -S-R"*" group, 2 an -0-C-R group II O wherein: R"^ represents an alkyl > an alkenyl or an 2 alkynyl C -C„ while R represents a C -C alkyl, a C -C 2 4 14 36 cycloalkyl or a phenyly N.2. PATENT OFFSCi: 2 0 D E C1983 199100 i are endowed with acaricide activity effective both on adult mites as well as on their summer eggs.

Ihe above mentioned compounds of formula I are, moreover, endowed with a practically negligible toxicity towards: warm-blooded animals and fish, and they are characterized by the absence of whatsoever phytotoxicity, even at heavy doses, towards the most diffused agrarian cultivations.

We have now found that some of the compounds of formula I are endowed with a particularly high "acaricide activity against the overwintering eggs of mites. These compounds may be collected under the following restricted formula: R* - 0<O>0-(CH2)3 - CEC-CH5-0-R" (II) wherein: R' represents an alkyl with C -C and 8 11 R" represents a hydrogen atom, an alkyl with C^-C^, allyl , or 2 2 - a -C-R group in which R represents an alkyl C^-C^, a cy~ 0 cloalkyl C -C or phenyl. 3 6 i ■ iimri amr-Ti N.Z. PATENT OFFICE 2 ODECI98S 1 99 Thus, object of this invention is a method for fighting mite infestations on useful plants, said method consisting in treating the overwintering eggs of mites with the compounds of formu la II, either as such or in the form of suitable compositions.

Further object of the present invention are acaricidal compo sitions active against the overwintering eggs of mites, having as an active ingredient one or more of the compounds of formula II .

The effectiveness of formula II compounds against the overwintering eggs is more than satisfactory for a practical use in agriculture. In fact the compounds of formula II are endowed with a high acaricide activity against the overwintering eggs even at rather low doses.

Moreover, said compounds, when applied in the right manner so as to contact all the mite eggs, exert a practically complete acaricide action and, consequently, the plants remain disin-fested for a long period of time (even for two months after the period of hatching of the eggs), thus allowing to considerably delay the treatments against the adult mites which may be present later on as a consequence of re-infestations of a different origin.

The known products used against the winter eggs of mites (fpr instance mineral oils additioned with phosphoric esters), 199100 besides displaying the afore mentioned applicational drawbacks, do not possess a complete activity and thus, in order to obtain the same results, it is necessary to carry out at least two further spring treatments with acaricide products.

For practical applications in agriculture, i-t is better to use the compounds of formula II in the form of suitable compositions; with the main scope of obtaining the best possible distribution of the product so as to reach all the mite eggs which are often placed on parts of the plants difficult to be reached.

The above indicated compositions may contain, besides one or more of the compounds of formula II as active ingredient, an inert carrier and a surfactant.

The choice of the vehicle (carrier) and of the additives depends on the type of formulation needed.

Suitable formulations are the emulsifiable concentrates that consist of the active ingredient, of a liquid vehiculant such as an organic solvent, and of surfactants. Examples of organic solvents that may be used in the above said compositions, consist of aromatic or alkylaromatic hydrocarbons such as for instance xylol or other commercial mixtures of alkylaromatic hydrocarbons alcohols such as butyl or isoamyl alcohol, ketones such as ethyl -amyl-ketone or cyclohexanone.

I ^ ^ I cP O 199100 Examples of surfactants that may be used in the above cited compositions, consist of alkylbenzenesulphonates, polyoxyethyla ted alkylphenols, polyoxyethylated vegetable oils, glycerides of polyoxyethylated fatty acids, polyoxyethylated sorbitan olea tes or mixtures thereof.

In the above cited compositions the ingredients may be present in the following quantities: A - Active ingredient (compound of formula II) 0.5-50 & by weight B - Organic solvent 30-80 £ by weight C - Surfactant 0.5-20 % by weight It is well known that mineral oils possess a certain activity against the overwintering eggs of mites. Such activity which, however, is not very pronounced, is due essentially to an activity of physical character, in as much as said oils may cover with a very thin film the mite eggs thus hindering the gaseous exchanges and thus often even causing the death of the embryo.

It is, thus, possible to add to the above described compositions also mineral oils with the function of'vehicle but at the same time also as active substance.

The suitable mineral oils are the commercial oils having a content in unsulphonable substances greater than or equal to 80^ by weight. The solvents and surfactants that may be used are those mentioned previously. iu MP K. 2 017- 199100 9 In these compositions the ingredients may be' present in the following amounts: Whenever a special situation should require it, it is possible to add to the compositions or formulations object of this invention, also other active substances useful for the winter control of other plant pests and diseases.

Said active substances may comprise insecticides, but above all, fungicides.

The acari species that may be effectively controlled in the stage of overwintering eggs with the method and the compositions object of this invention, belong to the family of Tetranychidae, genera: Panonychus, Bryobia, and Oligonychus.

Amongst these species, the most important one for the extent of the damages inflicted to the plants and for the wide diffusion in all temperate areas, is Panonychus ulmi which almost everywhere shows a high level of resistance to the different pesticides due to the intensive chemical attack to which it is systematically subjected.

A - Compound of formula II B - Mineral oil 0.5-30 % by weight 40-80 % by weight C - Organic solvent D - Surfactant -30 % by weight 0.5-20 % by weight The amount of active substance to be distributed in order to ensure an effective action against the overwintering eggs of mites, may vary depending on different factors.

In general, amounts comprised between 0.1 and 3 Kg/ha are quite sufficient.

The preparation of the compositions object of the invention does not require any particular procedure.

The active ingrediente (compound of formula II), the solvent and the surfactant are mixed together without any preferred order at room temperature. To this mixture the mineral oil is admixed when necessary.

In order to better illustrate the invention, in the following are given a set of examples.

EXAMPLE 1 Preparation of acaricide compositions.

Representative examples of acaricide compositions are reported on the following Table 1.

With the scope of simplifying the comprehension of Table 1, the following abbreviations have been used. a.i. = active ingredient; the following compounds of formula II have been usee, as active ingredient: Ca3&JN3dffL . JE 0 {?■ 1) ch3-Cch2)9-o-(5> o-ch2-cb2-ch2-c = c-ch2-o-ch3 2) CH - ( CH ) -oYO V O-CH-CH-CH-C— C-CH-O-CH 3 2 10 \ / 2 2 2 — 2 3 3) CH -(CH ) -0-<O V O-CH -CH -CH -C = C-CH -O-CH-CH 3 2 7 \ J 2 2 2 2 £ 3 3 4) ch3-(ch2) 7-o^O^ o-ch2-ch2-ch2-c = c-ch2-o-ch3 ) CH3-(CH2)7-0^5y 0-CH2-CH2-CH2-C=C-CH2-0-CH2-CH3 6) ^-(CH,)^-^ 0-CH2-CH2-CH2-C = C-CH2-OH 7) CH3-(CH2) 9-0^>- 0-CH2-CH2-CH2-C=C-CH2-0-C-<^ 0 8) ch3-(ch2)9-o-<^Q^-o-ch2-ch2-ch2-c = c-ch2-o-c-ch3 0 9) CH -(CH ) -0-/ OV O-CH -CH-CH-C=C-CH -O-C-CH(CH) o d 9 \ / d <L 2. 2 || 3 2 0 >-0^0-' ) CH3-(CH2) g-oY O 0-CH2-CH2-CH2-C = C-CH2-0-CH2-CH=CH2 i1 9 91 00 Solvents Sol 1 = Xylol, commercially available mixtures have been used Sol 2 = Isobutyl alcohol Sol 3 = Cyclohexanone.

Mineral oils MO 1 = Mineral oil with a content of unsulphonable substances greater than or equal to 90$ MO 2 = Mineral oil with a content of unsulphonable substances greater than or equal to 80$.

Surfactants Sur 1 = Mixture of polyoxyethylated nonyl-phenol (7 moles of ethylene oxide per mole of substrate), polyoxyethylated sorbitan-oleate (20 moles of ethylene oxide per mole of substrate) and calcium dodecylbenzenesulphonate in the ratio 4.9 : 2.1 : 3.

Sur 2 = Mixture of polyoxyethylated nonylphenol (7 ET0) and sorbitan-oleate (20 ET0) in the ratio 5:3.

Sur 3 = Mixture of polyoxyethylated nonylphenol (7 ET0) and sorbitan-oleate (20 ET0) in the ratio 7:3.

Table 1 Acaricide compositions (amounts of components expressed as percentage by weight).

Components 1 2 Com] 3 3 o s i 4 t i o n 5 N° 6 7 8 9 a.i. (%) 50 2 . 5 MO 1 (%) MO 2 (%) ■ - - - - — 80 80 45 80 Sol 1 (%) Sol 2 (%) Sol 3 (%) 70 70 70 80 40 7 7 9.5 Sur 1 (%) Sur 2 (%) Sur 3 (%) • 8 8 8 CO i ><> 3 ■Caac K. 2-Q17 199100 The compositions reported on Table 1 have been prepared by simply mixing together the ingredients at room temperature. The compositions containing also mineral oils have been prepared by admixing the oil to the mixture of the other ingredients.

EXAMPLE 2 Determination of the acaricide activity on winter eggs of Panonychus ulmi.

Twigs heavily infested with P. ulmi eggs have been cut off in autumn from apple-trees grown in an orchard naturally infested by mites .

The twigs have been then kept in the open under natural conditions .

During the winter, by operating in an unheated environment, from the twigs were cut small portion on which the presence of eggs was particularly concentrated and for each of these portions was counted the number of eggs that were clearly vital, removing all the damaged eggs and those of uncertain hatching.

With each of the compounds being tested were prepared suitable compositions and formulations, and with each of them were treated by spraying twenty twig-portions carrying about 800-1000 eggs in total.

After drying, the twig portions were kept in the open under a shelter in natural conditions until the end of the test.

T9W5o The results were assessed, several days after the end of the hatching of the eggs in the check (portions of infested twigs treated only with a hydroacetonic solution and a surfactant), by counting the unhatched eggs in comparison with the eggs present before the treatment and taking into account the unhatched eggs in the check.

Following the same procedure, infested twig portions have been treated also with a commercial formulate containing Parathion in mineral oil.

In the following Table 2 have been reported the activity data against winter eggs of Panonychus ulmi of some compounds of the invention and of some known compounds.

Because of the fact that a certain number of mite eggs, both in the test and in the check, can be altered or missing for natural undefined causes, the results have been expressed by classes of activity rather than by percentage values that would not be suit_ ed for the practical character of the experiment, as follows: ++++ = practically complete acaricide activity +++ = high activity + + = partial activity + = negligible or any activity.

Bt the data reported on Table 2 it appears that the compounds of the invention possess a high activity against mites winter eggs.

Nn K. 2017 199100 Said activity is high even when they are tested as simple hydro acetonic solutions and becomes practically complete when they are formulated, independently from the presence of a mineral oil .

Table 2 Acaricide activity against P. ulmi winter eggs. (a) Active ingredient (b) Formulation Dose a.i.(%) £ % min.oil_7 (c) Acaricide activity Compound No. 1 Hydroacetonic solution 0. 05 0.01 + + + + + + + EC 20 0. 05 0. 01 + + + + + + + + EC 20 + mineral oil 0.01 L 2 J + + + + Compound No. 2 Hydroacetonic solution in r-l o o o o + + + + + Compound No. 6 EC 20 0. 05 0.01 + + + + +++ + EC 20 + mineral oil 0. 01 £ 2 J + + + + Compound No. 9 EC 20 0. 05 0. 01 + + + + + + + + EC 20 + mineral oil 0. 01 £ 2 _7 + + + + Compound No.10 EC 20 0. 05 0. 01 + + + + + + + + EC 20 + mineral oil o.oi ZT2 _7 + + + + Compound A ( Ref. ) EC 2 0 0. 05 0. 01 + + EC 20 + mineral oil 0.01 C 2 J7 ++ Parathion in mineral oil Commercial formulate 0.06 £ 0.96 J + + Mineral oil - C2J + + 1991 00 Case N" K. 301? 17 Notes to Table 2 (a) Active ingredients: Compounds 1, 2, 6, 9 and 10 according to the invention, have been identified by their formula in Example 1; Compound A is a reference compound of formula: according to U.S. Pat N° 4,061,683; Parathion is the common name of compound 0 , 0-diethyl-0-p . ni^ trophenyl-phosphorothioate.

Mineral oil is a mineral oil having a content of unsulphonable substances greater than 80%. An emulsion of mineral oil (80% by weight) in water was used in the tests. (b) EC 20 means emulsifiable concentrate at 20% by weight of active ingredient; EC 20 + mineral oil is a mixture prepared at the moment of the treatment.

Hydroacetonic solution is a solution or dispersion of the ac tive ingredient in a water-acetone mixture (acetone 10% by weight). (c) Similarly good results have been obtained by using compositions according to example 1 and containing the other active compounds of formula II listed in example 1, both with mineral oil and without.

(A) 199100

Claims (1)

1. WHAT WE CLAIM IS: 1) Acaricidal compositions, suitable for fighting mite infestations by treatment of the overwintering eggs of mites, characterized in that they contain as active ingredient one or more of the compounds of formula: R'-°-( O V" °-CHp-CHp~CHp-C — C-CH -O-R" (II) \ / w w b Cm wherein: R' represents a Cg-C alkyl and R" represents a hydrogen atom, a C -C alkyl, allyl or a 2 -C-R group in which II 0 2 R represents a C^-C^ alkyl, a C^-C^ cycloalkyl or phenyl- 2) 'Acaricidal compositions according to claim 1, containing a compound of formula II as active ingredient and one or more inert carriers, surfactants and optionally mineral oils. 3) ' Acaricidal compositions according to claim 2 in the form of emulsifiable concentrates in which the carrier is an organic solvent. 4) Acaricidal compositions according to claim 3 and consisting of A - Active ingredient (compound of formula II) 0.5-50% by weight B - Organic solvent 30-80% by weight : and C - Surfactant 0.5-20% by weight 199100 - 19 - 5) acaricidal compositions according to claim 3 and consisting of A - Active ingredient (compound of formula II) 0.5-30% by weight B - Mineral oil 40-80% by weight C - Organic solvent 5-30% by weight and D - Surfactant 0.5-20% by weight. 5) Acaricidal ccxiipositions according to claim 4 or 5 characterized in that the organic solvent is selected from alkyl--aromatic hydrocarbons, alcohols and ketones. 7) Acaricidal compositions according to claim 4 or 5 characterized in that the surfactant is selected from alkylbenzenesulphonates, polyoxyethylated alkylphenols, polyoxyethylated vegetable oils, polyoxyethylated sorbitan-oleates and mixtures thereof. 8) Acaricidal; compositions according to claim 5 characterized in that the mineral oil is selected from mineral oils having a content of unsulphonable substances greater than or equal to 80% by weight. 9) A method for fighting mite infestations on useful plants consisting in the treatment of the overwintering eggs of mites J*?;,30 AUG 1984;f;199100;- 20 -;by distributing on the infested area or plants, an effective amount of an acaricidal cariposition according to any one of claims 1 to 8.;10) A method for fighting mite infestations according to claim;9, characterized in that the mites to be fought belong to the family Tetranychidae, genera: Panonychus, Brvobia and 01igonychus.;11) A method for fighting mite infestations according to claim;10, characterized in that the mites to be fought belong to the species Panonychus ulmi.;12) Acaricidal compositions according to claim 1 and substantially as hereinbefore described with particular reference to the foregoing Example 1.;dated Ti-:iS ^ 7* hay cf ^ . o r. >! A. J. : - ' PER \/i ^ AGENTo FCR Tr.E APPLICANTS