IE43688B1

IE43688B1 - Pesticidal compositions

Info

Publication number: IE43688B1
Application number: IE1033/76A
Authority: IE
Original assignee: Celamerck Gmbh & Co Kg
Priority date: 1975-05-14
Filing date: 1976-05-14
Publication date: 1981-05-06
Also published as: MX4390E; NL7605105A; DD127521A5; NL185320C; NZ180854A; DE2521384C2; IT1061275B; AR217054A1; CA1070239A; IL49564A; ZA762872B; TR18806A; IL49564A0; GR60312B; BE841804A; AT350840B; SE436679B; SE7605473L; LU74929A1; CS188137B2

Abstract

The liquid formulation of N,N'-bis-(1-formamido-2,2,2-trichloroethyl)piperazine contains, as emulsifier, a salt of alkylbenzenesulphonic acid. The cation of the salt is Ca<2+>, Li<+>, tert.-C4H9-NH3<+> or an ammonium ion which is derived from a secondary or tertiary aliphatic amine and meets at least one of the criteria a) pKA>10.5; b) branched alkyl chain having 3 to 4 carbon atoms; c) no additional functional groups in the alkyl radicals. The liquid formulation has a fungitoxic and acaricidal activity.

Description

The· present invention relates to composition? for use as fungicides or acaricides or as concentrates therefor. In particular, the present invention relates to compositions or concentrations comprising N,N'-bis[(l-formamido-2,2,2-trichloro)ethyl]-piperazine (hereinafter also referred to as triforine) as active ingredient.

It is known that triforine possesses a pronounced fungitoxic activity. This activity is of particular importance with regard to liquid compositions.

German Offenlegungsschrift No. 2,128,225 describes solution concentrates containing triforine as active ingredient. A special feature of these compositions is the presence therein of dimethylformamide (DMF) and N-methylpyrrolidone (NMP) as solvents as well as the preferred use of the monoisopropylamine salt or triethanolamine salt of dodecylbenzene sulfonic acid as emulsifier. These solution concentrates are highly active pesticides, but suffer the disadvantage that triforine only remains stable for a limited time.

In particular the active ingredient degrades at elevated temperatures, but even starts to degrade at 20nC.

Thus these compositions can only be stored for a short period of time. Alternatively the compositions must be 3 S8 S stored under special conditions which involve substantial extra costs.

Although the shelf-life of these compositions may be improved by the use of non-ionogenic emulsifiers, the use of such emulsifiers results in other disadvantages, such as, for example, insufficient solubility of the active ingredient, weaker biological effect or imperfect spray quality.

It has now been found that by using certain salts of TQ alkylbenzene sulfonic acids, the active ingredient in triforine compositions may, at least in part be stabilized.

This finding is particularly surprising since even small modifications in the structure of the cation oi the emulsifier salt may enable a considerable improvement in the stability of triforine in the composition to be obtained.

Thus., the stability of liquid triforine compositions at 22 C is raised 8-fold, when the commercial emulsifier dodecylbenzenesuifonic acid-monoisopropylamine salt is replaced by the corresponding diisopropylamine salt. The ZO improved shelf-life of compositions of the invention which we have tested is especially pronounced at temperatures below 30 C.

Thus according to the present invention there are 3688 provided compositions suitable for use as fungicides or acaricides or as concentrates therefor which comprise N ,N' -bi s-ft 1 -formami do-2,2,2-tri chi om) ethyl] -piperazine, an optically active or meso isomer thereof or a racemic mixture thereof or mixtures of such isomers as active ingredient, together with a salt of an alkylbenzene sulfonic acid as emulsifier, in which the cation of the acid salt is Ca^ © , Li(T), t-C4HgN(J)H3 or an ammonium cation derived from a secondary or tertiary aliphatic amine which has at least one of the following:a) pKa-value > 10.5 b) a branched alkyl chain with 3 or 4 carbon atoms; c) no further functional groups bonded to the alkyl groups.

The compositions of the present invention preferably comprise a solvent (as hereinafter defined).

The expression solvent as used herein means a liquid or mixture of liquids which is capable of dissolving at least 5% by weight of. the active ingredient based upon the weight of the liquid(s).

The salt of the alkylbenzene sulfonic acid is preferably a salt of n-dodecylbenzene sulfonic acid (DBS) or a salt of tetrapropylenebenzene sulfonic acid.

The triforine molecule contains two asymmetric carbon atoms, each asymmetric carbon atom being bonded to the same radicals so that in the synthesis of the active ingredient 50% of D,L-triforine (meso-forms) and 50% of racemic triforine (25% of L.L-triforine and 25% D,D-triforine) are obtained.

It will be appreciated that the present invention relates to compositions and concentrates comprising Ν,Ν'-bis -/l-formamido-2,2,23trichloro)ethyijpiperazine in any of its optically active, meso or racemic forms or in any mixture of its optically active, meso or racemic forms as active ingredient together with an emulsifier as hereinbefore defined.

Secondary and tertiary aliphatic amines which may, for example, be employed include: dimethylamine, diethylamine, di-n-propylamine, di-isopropyl amine, di-sec.butyl amine, trimechylamine, triethylamine, tri-n-propylamine, tri-isopropylamine triisopropanolamine, tert.butyl amine. The triethylamine salt and the di-isoprcpylamine salt of DBS are preferred.

Certain of the emulsifiers for use according to the present invention are known. Those emulsifiers that are not known may be produced according to conventional processes, for example, by neutralizing the acids with a base in the melt or in the presence of a solvent. The solvents for use in the compositions of the present invention are those solvents which are preferred for the hitherto known triforine compositions. 288 The compositions of the present invention preferably contain from 5 to 45% by weight, especially 15 to 35% by weight of an alkylbenzene sulfonic acid salt. The compositions of the present invention may additionally comprise from 0.5 to 10% by weight of a non-ionogenic emulsifier, for example an ethoxylated alkylphenol, with the proviso that the total emulsifier content does not exceed 45% by weight.

Solvents for the solution concentrates according to the invention include, for example, dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide (DMAC) or mixtures of these solvents.

DMF or DMF/NMP mixtures in the ratio 9:1 to 4:6 (w/w) are preferably used. A portion of the above-mentioned solvent may, if desired, be replaced by conventional solvents to a maximum of 40% by weight, especially where the active ingredient content is less than 20% by weight. Such conventional solvents include, for example, aromatic hydrocarbons or triethyleneglycol. Moreover, the solution concentrates according to the invention may further contain a dyestuff and, if desired, up to 5% by weight of a defoaming agent, for example, a conventional defoaming agent. A long-chain, branched alcohol e.g. with 12 to 20 carbon atoms such as 2,2,4,8,10,10-hexamethyl-5-hydroxymethyl undecane may, if desired, be used as the defoaming agent.

The triforine content of compositions of the present invention is conveniently 3 to 30% by weight; preferably 5 to 25% by weight.

Mixtures of triforine with other fungicidally, acaricidally or insecticidally active substances may also be employed; in which case the active ingredient content may exceed 30 by weight Hitherto the production of liquid triforine formulations has been made particularly difficult by the fact that the active ingredient is only slightly soluble in most of the solvents used for pesticides. It is true that the solubility of triforine in DMF, NMP and DMAC as well as mixtures thereof is good, however, such ‘θ solubility is restricted by the addition of commercial emulsifiers. When using higher proportions of these emulsifiers, it is therefore only possible to produce liquid formulations having a relatively low percentage of active ingredient with an often insufficient coldIo resistance. We have found that the solubility of triforine in solvents which have been tested does not decrease very markedly even when the preferred emulsifiers are used in large quantities. This effect is especially pronounced with the triethylamine salt, and somewhat more weakly pronounced with the di-isopropy]ene salt ot n-dodecyIbenzene sulfonic acid.

The differing influence on solubility is illustrated by the following table: :688 No. Quantity of Emulsifier Solvent Quantity of Sol- J-l O P RJ TJ P 3 O P a >4 cd 0 •rl β w O 3 0 σ •rl 3 P φ P O Cd P ϋ •rl 3 P Ό P Ό 3 ω 3 O «Ρ P GJ o i> (X co P « P O •rl P Ρ P O P cd H oo 60 00 00 oo 00 oo 00 CM P -3· -tf σ» Γ-- in CM P CM o σ» in in cn CM P P P P P P P Z— CQ CM — cn cn cn CQ cn cn CQ cn CQ p CQ CQ a CQ P 1 < <: < P 1 P I < <; Q 5 < < a (X> p Ω P cu P < Q cu o P o ω O CP O H o P O H 60 o 00 60 H 00 P oo H 60o 00 oo 00 b 00 OO 00e -tf -tf -3 -tf -tf 3 o o o • o O O φ + ω + aO + aD + aD + AD + 00 00 00 oo 00 oo oo 00 CM CM CM CM CM CM CM CM -tf -tf -tf -tf -tf -tf -tf •tf lp CM co -tf ΓΟΟ ’OS; (1) Comparison test ¢) IPA-DBS = moncisopropylamine salt of dodecylbenzene sulfonic acid ODA - isooctadecyl alcohol (3) DIPA-DBS (4) TEA-DBS di-isopropylamine salt of dodecylbenzene sulfonic acid triethylamine salt of dodecylbenzene sulfonic acid.

When using DMF/NMP 1 : 1 as solvent, comparison test 10 No. 2 shows that the required DMF/NMP-quantity is increased by the addition of the mono-isopropylamine salt of DBS.

In constrast, tests Nos. 3 and 1 show, that the required quantity of solvent is reduced by the addition of the di-isopropyl- or triethyl-amine salt.

With DMF as solvent the quantity of solvent required for the production of solution Nos. 7 and 8 according to the invention is lower than that required for comparison test No. 6.

The liquid formulations according to the invention possess very low toxicity in warm-blooded animals and a good compatibility for plants. The compositions of the present invention may be employed in the control of phytopathogenic fungi and spider mites, especially for leaf-treatment by means of spraying after dilution with water. For ultra-low25 volume (ULV) treatment the solution concentrates may also be used in undiluted form.

According to a further feature of the present invention there is provided a method of preventing or inhibiting the growth or proliferation of fungi which comprises applying, either directly or indirectly via systemic action, to a site infested with or subject to infestation by fungi an effective amount of a composition as hereinbefore defined.

According to a still further feature of the present invention there is provided a method of preventing or inhibiting the growth or proliferation of acarids which comprises applying to a site infested with or subject to infestation by acarids an effective amount of a composition as hereinbefore defined.

The solution concentrates of the present invention may also be employed for liquid protection of seeds, e.g. cereals, in order to avoid fungal infections.

Stability Trials using compositions of the present invention; Example A A liquid triforine composition containing 210 g of active substance, 20 g of isooctadecyl alcohol and 300 g of various amine salts of DBS (solvent: DMF/NMP l:l)/litre was shelved at 23°C. After a shelf life of a) 5 months and b) 1 year the triforine degradation was determined analytically.

Emulsifier Degradation of (relative) activ c- stilos esneti 5 nionths/23 C 1 year/23 °C Mcnu-isopropylamine-DBS 7.0% 8.2% triethylamine-DBS 1.2% 2.1% di-i sopropylamine-DBS 0.8% 1.3% Example B A liquid triforine composition containing 160 g of active substance, 20 g of isooctadecyl alcohol and 240 g of various amine salts per litre (solvent: DMF) was shelved at 23:,C. After a shelf life of a) 6 and b) 11. months the triforine degradation x/as determined analytically.

Emulsifier Degradation of active substance 6 months/'23°C (relative) 11 months/23'C Mono-isopropylamine-DBS 7.0% 8.3% triethylamine-DBS 1 Hi/q 1.8% di-isopropylamine-DBS 1.2% 1.5% Example: HI I I Mil II lUllll·· I P ro due tion of the triisopropanolamine salt of the η-dodecylbenzenesulfonie acid 573 g (3 mol) of molten triisopropanolamine is added, xiith vigorous stirring to 978 g (3 mol) of n-dodecylbenzenesulfonic acid at 55°C in portions. Towards the end of the neutralization the temperature is raised to 85°C.

After the addition of the amine has been completed, the reaction mixture is heated for 1 hour to 90°C and then cooled to room temperature. After several days the viscous mass solidifies to a wax-like condition.

The following Examples are given by way of illustration only: Formulation Examples: 1. 10 g of triforine g of triethyiamine salt of DBS 3 g of isotridecyl alcohol g of DMF lOlg = 100 ml of solution concentrate 2. 15 g of triforine g of diisopropylamine salt of DBS 2 g of isooctadecyl alcohol g of DMF 102 g = 100 ml of solution Concentrate 3. ‘ 15 g of triforine g of triethyiamine salt of DBS g of isohexadecyl alcohol g of nonylphenol, condensed with 14 mol of ethylene oxide g of DMF 101 g = 100 ml of solution concentrate - 12 Ci cj g of triforine g of di-isopropylamine salt of DBS 29 g of DMF g of NMP 108 g = 100 ml of solution concentrate 20 g of triforine g of triethylamine salt uf DBS g of isooctadecyl alcohol g of DMF g of NMP 108 g = 100 ml of solution concentrate g of triforine g of triethylamine salt of DBS g of isooctadecyl alcohol g of polyvinylpyrrolidone modified by alkyl g of DMF g OF NMP 108 g = 100 ml of solution concentrate g of triforine g of lithium salt of DBS g of DMF g of NMP 106 g - 100 ml of solution concentrate 8. 688 g of triforine g of triethylamine salt of DBS 2 g of isooctadecyl alcohol g of 50% isopropanol solution and a copolymerisate from vinyl pyrrolidone and vinyl acetate 1:1 g of DMF g of NMP 108 g = 100 ml of solution concentrate The isooctadecyl alcohol mentioned in Examples 2, 5, 6 and 8 is a mixture of highly branched alcohols, the main component being 2,2,4,8,10,10-hexamethyl-5-hydroxymethyl undecane.

Claims

1. Compositions suitable for use as fungicides or acaricides or as concentrates therefor which comprise N,N'-bis[jl-formanrido

2. ,2,2-trichloro)ethylJpiperazine, an optically active or meso 5 isomer thereof or a racemic mixture thereof or mixtures of such isomers as active ingredient, together witn a salt of an alkylbenzene sulfonic acid as emulsifier, in which the cation of the derived from a secondary or tertiary aliphatic amine which has at >0 least one of the fol lowing :a) pK a -value >10.5: b) a branched alkyl chain with 3 or 4 carbon atoms; c) no further functional groups bonded to the alkyl groups. i. Compositions as claimed in claim 1 which comprise a solvent •15 (as herein defined).

3. Compositions as claimed in claim 1 or claim 2 wherein the salt of the alkylbenzene sulfonic acid is a salt of n-dodecylbenzene sulfonic acid or a salt of tetrapropylenebenzene sulfonic acid.

4. Compositions as claimed in any one of the preceding claims go wherein the salt of the alkylbenzene sulfonic acid is the triethyiamine or di-isopropylamine salt.

5. Compositions as claimed in any one of claims 1 to 3 wherein the salt of the alkylbenzene sulfonic acid is selected from the dimethylamine; diethylamine, di-n-propylamine, di-sec.butyl amine, 25 trimethylamine, tri-n-propylamine, tri-isopropanolamine, triisopropanol amine and tert.butylsmine. 3683

6. Compositions as claimed in any one of the preceding claims which contain from 5 to 45% by weight of the alkylbenzene sulfonic acid salt.

7. Compositions as claimed in claim 6 which contain from 15 to 35% by weight of the alkylbenzene sulfonic acid salt.

8. Compositions as claimed in any one of the preceding claims which further contain from 0.5 to 10% by weight of a nonionogenic emulsifier with the proviso that the total emulsifier content does not exceed 45% by weight.

9. Compositions as claimed in claim 8 wherein the nonionogenic emulsifier is an ethoxylated alkylphenol.

10. Compositions as claimed in any one of the preceding claims which contain from 3 to 30% by weight of li,N'-bis-Qformamido2,2,2-trich1oro)ethyl]-piperazine, in optically active, meso or racemic form or a mixture thereof, as active ingredient.

11. Compositions as claimed in claim 10 which contain from 5 to 25% by weight of the said active ingredient.

12. Compositions as claimed in claim 10 or claim 11 which contain a further fungicidally, acaricidally or insectici dally active substance.

13. Compositions as claimed in any one of the preceding claims which are liquid and which comprise dimethylformamide, N-methylpyrrolidone or dimethylacetamide or a mixture thereof as solvent.

14. Compositions as claimed in claim 13 wherein the solvent is a mixture of dimethylformamide and N-metnyl pyrrolidone in the ratio of from 9:1 to 4:6 by weight,

15. Compositions as claimed in any one of the preceding claims which contain up to 5% by weight of a defoaming agent.

16. Compositions as claimed in claim 15 wherein the defoaming agent is a highly branched alcohol with 12 to 20 carbon atoms.

17. Compositions as claimed in claim 15 wherein the defoaming agent is 2,2,4,8,10,lO-hexamethyl-5-hydroxymethyl undecane.

18. Compositions as claimed in any one of the preceding claims wherein the Ν,Ν'-bis Ql-formamido-2,2,2-trichloro)ethyljpiperazine employed as active ingredient, comprises 50% of the raeso isomer and 50% of the racemic mixture.

19. Compositions as claimed in claim 1 substantially as herein described.

20. Compositions as claimed in claim 18 substantially as herein described.

21. Compositions for use as fungicides or acaricides or as liquid concentrates therefor substantially as herein described in any one of Examples 1-8.

22. A method of preventing or inhibiting the growth or prolifer- . ation of fungi which comprises applying» either directly or indirectlyvia systemic action, to a site infested with or subject to infestation by fungi an effective amount of a composition as claimed in claim 1.

23. A method of preventing or inhibiting the growth or proliferation of fungi which comprises applying, either directly or indirectly via systemic action, to a site infested with or subject to infestation by fungi as effective amount of a composition as claimed in claim 18.

24. A method of preventing or inhibiting the growth or proliferation of acarids which comprises applying to a site infested with or subject to infestation by acarids an effective amount of a composition as claimed in claim 1.

25. A method of preventing or inhibiting the growth or proliferation of acarids which comprises applying to the site infested with or Subject to infestation by acarids an effective amount of a composition as claimed in claim 18.