GB1590578A - Synergist compositions - Google Patents

Description

(54) SYNERGIST COMPOSITIONS (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED Imperial Chemical House, Millbank, London, SWIP 3JF do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to synergist compositions suitable for mixing with an insecticide or composition thereof.

British patent No. 1,148,103 disclosed the use of a class of imidazole derivatives, including In - dodecylimidazole, as insecticide synergists for use with certain "prior art insecticides" (that is those known prior to the application date of the said British patent, viz. 21st July, 1966).

We have now discovered that 1 - n - dodecylimidazole and the related compound 1 - n - dodecyl - 1,2,4 - triazole are especially effective synergists for certain insecticides not discovered until several years after the application date of the aforesaid British patent, and furthermore that compositions comprising these insecticides in combination with dodecylimidazole or dodecyltriazole have unexpected acaricidal properties.

Our copending U.K. patent application 36817/76 (Serial No. 1590577) describes . and claims synergised insecticidal and acaricidal compositions (hereinafter also called "the compositions described above") comprising 9 compound of formula:

wherein Y is hydrogen or cyano, Z is phenyl or 2,2 - dichlorovinyl, and R is (i) a group of formula:

where X is chlorine or bromine, or (ii) a group of formula:

where Q is methyl or chlorine, in combination with a synergistically effective amount of a compound of formula:

where A represents a nitrogen atom or a carbon atom bearing a hydrogen atom.

Compositions in which the synergist is 1 - n - dodecylimidazole are especially preferred.

A particularly useful group of synergised compositions described in U.K.

patent application 36817/76 (Serial No. 1590577) are those comprising a compound of formula:

wherein each X is chlorine or bromine, Y is hydrogen or cyano and Z is phenyl or 2,2 - dichlorovinyl, in combination with a synergistically effective amount of I n - dodecylimidazole.

The insect and acarine pests which may be combated with the synergised compositions include those associated with agriculture (which term includes the growing of crops for food and fibre, horticulture and animal husbandry), forestry, the storage of products of vegetable origin, such as fruit, grain and timber, and also pests associated with the transmission of diseases of man and animals.

Preferred compounds of formula I above are those wherein X is chlorine or bromine, Y is hydrogen or cyano and Z is phenyl, including for example 3 phenoxybenzyl 3(2,2 - dichlorovinyl) - 2,2 - dimethylcyclopropane carboxylate (hereinafter referred to as compound A) and a - cyano - 3 - phenoxybenzyl 3(2,2 - dichlorovinyl)- 2,2 - dimethylcyclopropane carboxylate, and those wherein Q is chlorine, Y is cyano and Z is phenyl, for example, a - cyano - 3 phenoxybenzyl 2 - (4 - chlorophenyl) - 3 - methylbutyrate.

The 1 - n - dodecylimidazole or 1 - n - dodecyl - 1,2,4 - triazole (hereinafter referred to as the synergist) may be present in the composition in an amount by weight greater or less than the amount of compound of formula I, but is preferably present in at least the same amount by weight as, and even more preferably in a greater amount than the compound of formula I. It is particularly preferred to have present about 5 to 50 parts by weight of the synergist for each part of the compound of formula I.

In other respects the compositions described above resemble conventional formulations for pesticidal usage, and in particular will usually comprise in addition to the compound of formula I and compound B an acceptable diluent or carrier material.

The composition may be in the form of dusting powders wherein the active ingredient and the synergist are mixed with a solid diluent or carrier, for example kaolin, bentonite, kieselguhr, or talc, or they may be in the form of granules, wherein the active ingredient and the synergist are absorbed in a porous granular material for example pumice.

Alternatively the compositions may be in the form of liquid preparations to be used as dips or sprays, which are generally aqueous dispersions or emulsions of the active ingredient and the synergist in the presence of one or more known wetting agents, dispersing agents or emulsifying agents.

Wetting agents, dispersing agents and emulsifying agents may be of the cationic, anionic or non-ionic type. Suitable agents of the cationic type include, for example, quaternary ammonium compounds, for example, cetyltrimethyl ammonium bromide. Suitable agents of the anionic type include, for example, soaps, salts of aliphatic monoesters or sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl- and triisopropylnaphthalene sulphonates. Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins.

The compositions may be prepared by dissolving the active ingredient and the synergist in a suitable solvent, for example, a ketonic solvent such as diacetone alcohol, or an aromatic solvent such as trimethylbenzene, and adding the mixture so obtained to water which may contain one or more known wetting, dispersing or emulsifying agents. Other suitable organic solvents are dimethyl formamide, ethylene dichloride, isopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes and trichloroethylene, N - methyl - 2 - pyrrolidone and tetrahydro furfuryl alcohol (THFA).

The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoromethane. The compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient and the synergist, the said concentrate to be diluted with water before use. These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may contain 1085% by weight of the active ingredient and the synergist. When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used.

For agricultural or horticultural purposes, an aqueous preparation containing between 0.00001% and 0.1% by weight of the active ingredient is particularly useful.

In the use the compositions are applied to the pests, to the locus of the pests, to the habitat of the pests, or to growing plants liable to infestation by the pests, by any of the known means of applying pesticidal compositions, for example, by dusting or spraying.

The compositions described above are very toxic to wide varieties of insect and other invertebrate pests, including, for example, the following: Aphis fabae (aphids) Megoura -viceae (aphids) Aedes aegypti (mosquitoes) Dysdercus fasciatus (capsids) Musca domestica (houseflies) Pieris brassicae (white butterfly, larvae) Plutella maculipennis (diamond back moth, larvae) Phaedon cochleariae (mustard beetle) Telarius cinnabarinus (carmine spider mite) Aonidiella spp. (scale insects) Trialeuroides spp. (white flies) Blattella germanica (cockroaches) Spodoptera litteralia (cotton leaf worm) Chortiocetes terminifera (locusts) Lucilia sericata (blowflies) Boophilus microplus (ticks) The compositions described above provide several benefits in use. Thus, although the synergist itself is devoid of any insecticidal or acaricidal activity, when it is used in combination with the compound of Formula I (hereinafter referred to as "the insecticide") in the synergised compositions described above it provides control of insect pests with lower rates of the insecticide than are required when the synergist is absent. Apart from this property of increasing insecticidal activity per se the presence of the synergist in the compositions also confers insecticidal activity against "resistant" strains of insects which in the absence of the synergist are substantially unaffected by application of the insecticide alone, because they have developed an ability to detoxify the insecticide through metabolism.

A further useful and unexpected advantage of'the synergised compositions described above lies in their ability to provide useful control of acarine pests of plants. The compounds of Formula I when used without the synergist are very poor acaricides. If therefore, as frequently happens, a growing crop is infested with both insect pests and acarine pests, for example caterpillars and mites in cotton or topfruit, then an insecticide and an acaricide must both be used to provide adequate control. However no separate acaricide is required when the synergised compositions described above are used, since the presence of the synergist, which is not acaricidal in its own right, confers acaricidal properties on the insecticide thus extending its spectrum of activity.

The synergised compositions described above may be prepared with the synergist and insecticidal ingredient both present and then transported to the site of application, or they may be prepared at or adjacent to the site of application as socalled "tank mixes" in which the synergist or a preformulated composition of the synergist is added directly to a preformulated composition of the insecticidal ingredient, and the mixture thus obtained immediately diluted with water to obtain a composition which is ready to apply to the crop or other locus of the pest by, for example, spraying. The advantage of using a tank mix is that it gives the user greater flexibility in choosing the ratio of synergist to insecticide to suit the particular host/pest situation involved.

The present invention therefore provides a synergist composition, suitable for admixture with an insecticide or composition thereof, which consists of a compound of formula:

where A represents a nitrogen atom or a carbon atom bearing a hydrogen atom in association with one or more emulsifying agents and a diluent.

The emulsifying agents and diluents are preferably those to which reference has been made hereinabove in relation to the synergised insecticidal compositions of the invention, and indeed the synergist compositions are in general similar to the synergised insecticidal compositions described above, except of course that they do not contain an insecticidal ingredient. Examples of such preformulated compositions of the synergist are illustrated in Examples I to 3 herein.

Example 1 This Example illustrates a preformulated composition of I - n dodecylimidazole, in the form of an emulsifiable concentrate, suitable for preparing a tank mix with a composition of a compound of Formula 1. It may be obtained by simply mixing together the following ingredients in the proportions given.

Ingredients % w/v l-n-Dodecylimidazole 25.0 "Arylan" CA 3.0 "Lubrol" N13 6.0 "Aromasol" H to 100.0 ("Arylan", "Lubrol" and "Aromasol" are Registered Trade Marks. "Arylan" CA is calcium dodecylbenzenesulphonate, "Lubrol" NB is a condensate of nonylphenol with 13 molar proportions of ethylene oxide, and "Aromasol" H is an aromatic solvent consisting principally ot mixed trimethylbenzenes).

Example 2 This example illustrates another preformulated synergist composition which may be obtained by simply mixing the ingredients listed below in the proportions stated.

Ingredients % w/v l-n-Dodecylimidazole 5.0 "Arylan" CA 3.0 "Lubrol" N13 6.0 "Cerachlor" 65L 20.0 "Aromasol" H to 100.0 ("Cerachlor" is a Registered Trade Mark. "Cerachlor" 65L is a chlorinated liquid paraffinic hydrocarbon resin, containing about 65% chlorine by weight and having an average molecular weight of 460).

Example 3 By substitution of 1 - n- dodecyl - 1,2,4 - triazole for I - n dodecylimidazole in the compositions of Examples 1 and 2 there may be obtained further preformulated compositions suitable for the preparation of tank mixes.

WHAT WE CLAIM IS: 1. A synergist composition, suitable for mixing with an insecticide or composition thereof, which consists of a synergist of formula:

where A represents a nitrogen atom or a carbon atom bearing a hydrogen atom in association with one or more emulsifying agents and a diluent.

2. A composition as claimed in claim I in which the synergist is 1 - n dodecylimidazole.

3. Synergist compositions as claimed in claim I substantially described with particular reference to any one of Examples 1 to 3.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (3)

**WARNING** start of CLMS field may overlap end of DESC **. ("Cerachlor" is a Registered Trade Mark. "Cerachlor" 65L is a chlorinated liquid paraffinic hydrocarbon resin, containing about 65% chlorine by weight and having an average molecular weight of 460). Example 3 By substitution of 1 - n- dodecyl - 1,2,4 - triazole for I - n dodecylimidazole in the compositions of Examples 1 and 2 there may be obtained further preformulated compositions suitable for the preparation of tank mixes. WHAT WE CLAIM IS:

1. A synergist composition, suitable for mixing with an insecticide or composition thereof, which consists of a synergist of formula:

where A represents a nitrogen atom or a carbon atom bearing a hydrogen atom in association with one or more emulsifying agents and a diluent.

2. A composition as claimed in claim I in which the synergist is 1 - n dodecylimidazole.

3. Synergist compositions as claimed in claim I substantially described with particular reference to any one of Examples 1 to 3.