NL8102117A - METHOD FOR PREPARING A PREPARATION WITH INSECTICIDE ACTION AND FOR COMBATING BUGS THEREOF - Google Patents

Description

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A method of preparing an insecticidal composition and controlling insects therewith.

The invention relates to a method for preparing new preparations and for using such preparations for controlling insects.

In particular, the invention provides a composition with inseeticid activity which, as component a), is a compound of formula 1, wherein both X substituents are equal and represent CONI, or both X substituents together are a divalent sulfur atom or a single bond, in a salt form that is acceptable in the agricultural field and component b) contains an agricultural acceptable water-soluble base capable of converting component a) into its free base form in an aqueous medium.

The compound of formula 1 in which both X-sub-15 stituents are equal and represent CON 11 is an insecticide known under the common name cartap.

The compound of formula 1, in which both X substituents together form a divalent sulfur atom, is an insecticide known under the conventional name of thiocyclam.

The compound of formula 1, in which both X substituents together form a single bond, is an insecticide known as nereistoxine.

For various reasons, including stability, ease of assembly, etc., cartap, thiocyclam and nereistoxin are processed in an agriculture acceptable salt form, for example, as hydrogen oxalate or as hydrochloride.

8102117. v 2

Thiocyclam and nereistoxine are commonly used as hydrogen oxalate, cartap as monohydrochloride.

It has now been found that the compounds of formula 1 are considerably more effective when used in free base form and the compositions of the invention represent an excellent practical means of allowing the use of this free base form.

Bases suitable for use in the compositions of the invention are acceptable organic or inorganic bases in the agricultural field. Their water solubility is preferably at least one gram per liter and their pKa values are preferably between 7 and 13, especially between 8 and 12.

Particularly suitable inorganic bases are NH 4 OH, 15 NaHCO 3, NaOH, CaCOH 3, CaO, 2 O 2 O, or mixtures thereof, and in particular CaO and 1 O 2, if used as component b), this is preferably anhydrous .

Suitable organic bases are in particular low volatility organic amines, especially secondary and tertiary amines. The organic bases preferably have a boiling point of more than 120 ° C at a normal atmospheric pressure (760 mm Hg), preferably more than 150 ° C. Examples of suitable organic bases are morpholine, diethylamine ethanol, in particular mono-, di- or triethanolamine, in particular the last compound.

The preparations according to the invention are intended for use in an aqueous spray form.

The amount of component b) to be used will depend on the quality of the water available when the spray liquid is prepared;

In general, satisfactory results are obtained if the preparations according to the invention contain component b) in an amount sufficient to be able to contain at least 80%, preferably at least 90% and especially 100%, of component 8). to its corresponding base form.

The type and amount of component b) to be used will preferably be chosen such that the spray liquid, in particular within a short time, for example within 10 minutes, preferably within 5 minutes, a pH of at least 7.0, preferably of at least 7 1.5, especially from about 8, for example from 7.7-9.0, with the pH preferably not exceeding 10.

In view of the foregoing and for practical reasons, the amount of component b) to be used in a preparation according to the invention can also be expressed in wt.% - and this amount is preferably between 20 and 120%, for example 40 wt. .% of constituent a). If component b) is used in the composition mixed with component a), the amount of component b) will preferably vary between 3% by weight and 20% by weight for technical reasons which are important in the composition. between 4 wt.% and 20 wt.% of the composition. . . .. according to the invention, it is pointed out that the spray liquid to be used will preferably obtain a pH of at least 7.5. The preparations according to the invention can be prepared according to a method known per se by placing component b) in a physical relationship with component a), for example by mixing component a) with component b) and, if desired, other components, for example carriers, diluents and / or surfactants or by providing a double pack, one part of which contains component a) and the other part of component b), with other components optionally present, if desired, being present in the part containing component a).

The insecticidal preparations according to the invention can be in either liquid or solid form, preferably in solid form, especially if component b) is solid. They preferably contain 8 wt% or more, for example 10 to 65 wt%, component a). Solid forms of the preparations vol-35 810 2 117

Preferred sr * r 4 according to the invention are soluble and wettable powders, in particular those containing 10-40 wt%, especially those containing 10-30 wt%, component a). Other preferred compositions of the invention are those containing more than 30% by weight of component a), especially those containing 40% or more of component a) in a double pack form.

When component b) is in liquid form, it can be absorbed on a suitable carrier, for example silicon dioxide, especially in a weight ratio of liquid component b) to the carrier of about 1: 1, for example 1: 0.67 to 1 : 1,2 and are mixed with component (a) or kept separately in a double pack.

The compositions according to the invention preferably contain acceptable anionic and / or nonionic surfactants which are acceptable in the agricultural field, which agents act as wetting agents and dispersing and emulsifying agents and, for example, promote dispersion of component a) in the spray liquid. and improving the wetting of waxy and correspondingly leaved with the spray liquid. They thus contribute to the convenience, accuracy and effectiveness of use. Thus, when these preparations are in the form of a double pack, they preferably contain the surfactant (s) mixed with component a).

The anionic and / or non-ionic surfactants which can be suitably used in the compositions of the invention are, in particular, agricultural dispersants or emulsifying agents, or mixtures thereof, which are acceptable, Examples of suitable anionic and / or non- ionic emulsifiers are esters of phosphoric acid of ethoxylated higher alcohols, alkyl aryl sulfonates, such as calcium dodecyl phenyl sulfonate, mixtures of mono- and di-esters of orthophosphoric acid, ethoxylated sorbythan fatty esters, polygl; colethers, among others 81 02 11 7 · # ? Example alkylphenylpolyethylene glycol ethers, such as nonylphenol polyglycol ether, polyoxyethylene triglycerides, polyoxyethylene polyoxypropylene copolymers and mixtures thereof.

Recommended emulsifiers have an average 5 HLB (hydrophilic lipophilic balance) of 9 to 15.

Examples of suitable dispersants are high alcohol sulfates, such as sodium lauryl sulfate. lignin sulfonates, naphthalene sulfonate-formaldehyde condensation products, sodium N-methyl 1-N-o 1 eoy 1 taurate etc.

Examples of commercially available anionic and / or non-ionic surfactants which are used in particular in the compositions according to the invention are: ATLOX 1285 (a non-ionic polyoxyethylene triglyceride with an HLB value of 14, 4, an acid number of 15 up to 1.5-1.8, a saponification number of 40-50 and a hydroxyl number of 50-65, Atlas Chemie GmbH), ANTAR0X CO-880 (a nonionic polyoxyethylenated nonylphenol with 30 mol ethylene oxide per mole of nonylphenol, General Aniline and Film Co), PLURONIC F 108 (a nonionic polyoxyethylene-polyoxypropylene block polymer 20 having a polyoxypropylene base portion having a molecular weight of about 3,250, the total molecule containing about 80% by weight of polyoxyethylene groups, BASF, Wyandotte Co.), in particular GAFAC RS 710 (an anionic mixture of mono- and diesters of orthophosphoric acid with a polyethoxylated higher alcohol with a specific gravity of 1.04-1.06 and an acid value l from 60-75,

General Aniline and Film Co), BES0LIN C (a sodium dodecylphenyl sulfonate, SANDOZ AG), in particular ATLOX 4851 B (a mixture of calcium alkyl aryl sulfonate and a polyoxyethylated triglyceride, which mixture has an HLB value of about 12.5, an acid -30 number of up to 1.5 and a viscosity at 25 ° C of 300-700 cps, Atlas Chemie GmbH), TENSI0FIX KL (an anionic calcium alkyl aryl sulfonate with a specific gravity at 20 ° C of about 1.042, Tensia, Belgium * ), FENOPON T 77 (sodium N-methyl-N-oleoyl taurate, General Aniline and Film Co) and 35 ANTAROX CO 210 (a non-ionic polyoxyethylene phenylphenol phenol 8102117 containing approximately 1.5 moles ethylene oxide per mole contains nonylphenol,

Generalkniline and Film Co).

The maximum amount of surface action agent will of course vary, depending on the insect species to be controlled. A favorable biological activity is generally obtained with preparations having a weight ratio of component a) to surfactant between 1: 0.04-6, preferably 1: 0.1-1, in particular 1: 0.15-0 , 6, for example, 1: 0.5.

The amount of surfactant in the compositions is preferably chosen such that the spray liquid to be used contains 0.01 wt% to 0.4 wt% surfactant, which amount of surfactant is inversely proportional to the volume of spray liquid to be used and a small volume spray liquid, for example, 0.05 to 0.4 wt% surfactant, and a large volume spray liquid, for example 0.01-0, 1 wt% surfactant.

If the surfactant is in a liquid form, it can be absorbed on a suitable support, for example silicon dioxide, as stated for component b).

The compositions of the invention generally contain from 20 to 99% by weight of the components a), b) and the surfactant optionally employed, the compositions containing component b) mixed with component a) preferably 20-80% %, preferably 30-80% by weight, of these components.

The improved insecticidal activity of component a), in particular of the agricultural acceptable acid addition salts of thiocyclam, in particular of thiocyclam hydrogen oxalate when this salt together with component b) and optionally an anionic or non-ionic surfactant, according to the invention, is determined according to the test on usual standard tests, such as the Spray-Potter Tower / Colorato 35 potato beetle larvae and by treatment of Leptinotarsa, 8102117 * 7

Heliothis or Spodoptera eggs and also by field trials, such as treatment of rice cultures, cotton, hops, peaches, pears, potatoes and sugar beet.

Very satisfactory results are obtained against insects of the Thysanoptera class, for example that of family the Thripididae family of the Heteroptera class, for example that of the Pentatomidae, of the Orthoptera class, for example that of the Gryllidae family, and in particular against insects of the Homoptera class, in particular sucking harmful insects of the families Delphacidae, Aphididae, Psyllidae and Coccidae, of the class Lepidoptera, in particular those of the families Geometridae, Yponomeutidae, Gelechiidae, Pyralidae, Pieridae,

Plutellidae, Noctuidae (e.g. Heliothis, Spodoptera,

Alabama), Tortricidae, Cossidae, Heliozelidae, Hepialidae, Hes-15 periidae, Lymantriidae, Lyonetiidae, Nepticulidae, Oecophoridae, in the class Coleoptera, in particular those of the families Chrysomelidae, Curculionidae, Coccinellidae, Nit

Elateridae, of the class Dipt era, in particular those of the families Agromyridae, Itonididae and Chironomidae, of the class 20 Hymenoptera, in particular of the families Tenthredinidae,

Cephidae and Cimbicidae.

Due to their insecticidal action, the compositions according to the invention are particularly indicated for controlling (including breeding) insects in an area, in particular of the aforementioned insects, especially in an area with plants, in particular in grain -crops, such as rice and corn, in fiber crops, such as cotton, in sugar crops, such as sugar cane and beet, in oil crops, such as rape, in fruit crops, such as pome fruits (e.g. pears), stone fruits (e.g. peaches) and citrus fruits (e.g. lemons), in vegetables, such as potatoes, cruciferous vegetables (for example, broccli, Brussels sprouts) and vegetables of the nightshade family (for example, peppers and tomatoes) and in drinks or herbaceous crops, such as tobacco, hops, tea, coffee 35 81 C 2 i 1 7 i S ____ y 8 and cocoa.

The invention therefore provides a method for controlling insects in an area, in particular with plants, preferably in an area with plants as described above, comprising applying an insecticidally effective amount of component a) and substance b. ), separated or mixed, in the field.

The amount of component a) to be used depends. of various factors, such as the nature of constituent a), the insect species to be controlled and the area, for example the stage of development of the insect and the leaf mass of the area with plants, the time and the manner of application.

In general, the desired effect is obtained when component a) is used according to the invention in a dose of between 150 g and 100 g per hectare of the area with plants, whereby acid addition salts of thiocyclam as component a) usually acceptable for agricultural purposes. applied, the amount applied need not exceed 400 g per hectare, unless under extreme conditions, for example, if a serious infection exists or if insects that are difficult to control, such as Tortricidae, are present.

Harmful insects for which the process according to the invention is of particular importance when using in the agricultural field acceptable acid addition salts of thiocyclam as component a) include, for example, in rice: in a dosage of 200 to 500 g, preferably from 300 to 400 g g, per hectare: Thysanoptera, in particular of the family Thripdae, in particular Thrips oryzae Will .: Heteroptera, in particular of the families Pentatomidae and 30 Coreidae, in particular Scotinophara lurida Burm. and Leptocorisa acuta Thunb .; Homoptera belonging to the families Delphacidae, Cicadellidae, Aphididae, in particular Nilaparvata lugens Stal, Nilaparvata oryzae Mats., Sogata Distincta Dist., Calligypona furcifera Horv., Nephotettix bipunctatus F., Nephotettixe apicalis Gothschia Sothschia Sothschia Sothschia. .; Coleoptera of the 8102117 9 Chrysomelidae family, in particular Lema oryzae Kuw .; Lepi-doptera of the families Pyralidae, Woctuidae and Hesperiidae, especially Tryporyza (Schoenohius) incertulas Walk., Chilo suppressalis Walk., Chilo Plejadellus Zck., Chilo zonellus Swinh. , Chilotraea 5 auricillia Dudg., Chilotraea (Proceras) polychrysa Meyr., Scir-pophaga innotata Walk., Cnaphalocrocis medinalis Guen., Sesamia inferens Walk., Parnara guttata Brem., Parnara mathias F .;

Diptera of the families Itonididae, Chloropidae, Agromyzidae and phydridae, in particular Pachydiplosis oryzae W.-M., Chlorops oryzae Mats., Agromyza oryzae Mun. and Hydrellia griseola Fall.

in cotton: in a dosage of 200 to 400 g per hectare, Homoptera, in particular that of the family Aleyrodidae, especially Bemisia tabaci Genn .; Coleoptera, in particular of the Chrysomelidae family, especially Podagrica pallida 15 Jac., Podagrica punctiocollis Weise, Syagrus rugruons Baly., Syagrus calcaratus F. in Syagrus morio Harr .; Lepidoptera, in particular of the families Lyonetiidae, Gracilariidae, Gelechiidae, Tortricidae, Pyralidae and Iïocuidae, in particular Bucculatrix thurberiella Busck, Acrocercops bifsciata Wals., Platyedra gos-20 sypiella Saund., Argyroplocr leuc. Mescinia peruella Schaus, Phycita infusella Meyr., Alabama argillacea Hbn., Ileliothis spp. (Especially eggs and small larvae), Earias spp. (especially eggs and small larvae), Spodoptera spp (especially eggs in small larvae) and Laphygma spp.

25 in hop plants: with a spray liquid that 20-

Uo g of constituent a) per hectolitre contains Homoptera, in particular that of the family Aphidae, especially Phorodon humuli, in stone fruit: with a spray liquid containing 20-100 g of constituent a) per hectolitre, in particular that of the family Cicadellidae and Aphididae, especially Ityphlocyla spp., Erythroreura spp., Iyalopterus pruni Koch, 35 8102117 r

V

10

Hysteroneura setariae Ths., Brachycaudus persicaecola Bdv ,,

Myzus cerasi F. and Myzus persicae Sulz; Coleoptera, in particular of the Chrysamelidae family, especially Nodonota puncticollis Say, Galerucellacavicollis LeC .; Lepidoptera, in particular 5 of the families Lyonetiidae, Hyponomeutidae, Gelechiidae,

Tortricidae, Cossidae, Pyralidae, Geometridae, Arctiidae,

Lymantriidae and Pieridae, especially Lyonetia clerkella L .; Hymenoptera, in particular of the Tenthredinidae and Pamphiliidae families, especially Caliroa spp., Hoplocampa spp. in Neurotoma nemoralis L .; 10 in pome fruits: with a spray liquid containing 20 to 100 g of constituent a) per hectolitre, Homoptera, in particular that of the families Cicadellidae, Psyllidae and Aphididae, especially Empoasca maligna Walsh, Psylla spp., (Ex.

Psylla piri L., Psylla piricola Forst., Psylla pirisuga Forst), 15. Sapaphis piro Mats. *, In turnips: at a dosage of 100 to 300 constituent (a) per hectolitre, Coleoptera, in particular of the Nitidulidae and Curculionidae families , especially Meligethes aeneus F. and Ceuthorrhynchus spp .; Hymenoptera, in particular 20 of the Tenthredinidae family, especially Athalia rosae L, in potatoes: with a dosage of 100 to 300 g of constituent a) per hectare, Thysanoptera, in particular of the Thripidae family, especially Hercothrips sundanensis B. and C ., Thrips tabaci; Homoptera, in particular of the families Cicadellidae, Aleyrodidae and Aphididae, especially Empoasca fabae Harr., Circulifer tenellus Baker, Bemisia tabaci Genn., Tria leurodes vaporariorum Westw., Aphis nasturtii Kalt, Macrosiphum spp. and Myzus persicae Sulz; Coleoptera, especially of the Chrysomelidae family, especially Diabrotica spp., Epithrix 30 cucumeris Harr., Leptinotarsa decemlineata Say, Phyllotreta pusilla Horn .; Lepidoptera, especially of the Gelechiidae and Pyralidae families, in particular against Phthorimaea operculella Zeil. and Ostrinia nubilalis Hbr .; Diptera, especially of the family Agromyzidae, in particular Liriomyza spp., 35 8102117 11 in maize: with a dosage of 200-600 g of ingredient a) per hectare of Homoptera, in particular of the families Fulgoridae and Aphididae, especially Pyrilla spp. and Rhopalosiphon maidis Fitch; Coleoptera, in particular of the family 5 Chrysomelidae, especially Chaetocnema pulicaria Melsh., Lema melanopus L., Diabtrotica balteata LeC · and Diabrotica decolor Er .; Lepi doptera, especially from the families Pyralidae and Hesperiidae, especially Ostrinia (Pyrausta) nubilalis Hbn., Chilo. suppressalis Walk., Cnaphalocrocis medinalis Guen., Diatraea crambidoides Grote, 10 Diatraea saccharalis F. and Pamara guttata Brem.

in beet with a dosage of 200-600 g of constituent a) per hectare, Homoptera, in particular of the families Cicadellidae and Aphididae, especially Aceratagallia sanguino-lenta Prov., Circulifer tenellus Baker, Aphis fabea Scop., macro-15 siphum euphorbiae Ths . and Myzus persicae Sulz .; Coleoptera, in particular from the families Silphidae, Chrysomelidae, Curculionidae and Cryptophagidae, especially Blitophaga spp. (Such as Blitophaga opaca L. and Blitophaga undata Mull), Chaetocnema tibialis 111., Lixus spp. (such as Lixus junci Boh. and Lixus ascanii L.) and Bothynoderes punctiventris Germ .; Lepidoptera, in particular those of the Gelechiidae and Pyralidae families, especially Phthorimaea ocellatella Boyd, Loxostege sticticalis L., Psara bipunctalis F .; Diptera, in particular that of the Anthomyiidae family, especially Pegomyia hyoscyami betae Curt .; Hymenoptera, in particular those of the Tenthredinidae family, especially Athalia rosae L.

The preparations according to the invention are preferably used as a mixture in a tank. The invention also provides aqueous dosage forms containing the compositions of the invention.

Generally, the aqueous use forms will contain 0.01-0.8 wt% (10-800 g per hectolitre) of component a), depending on the method to be used (spray volume). For use on field crops such as corn, wheat crops, cotton, turnips, potatoes, sugar beet and rice, the spray liquid will preferably be 0.01-0.6 wt.%, Especially 0.015-0.2 8102117 12 wt. .%, component a). Good results are generally also obtained in vegetables with concentrations of 0.01-0.06 wt.%, In citrus fruits and coffee of 0.02-0.1 wt.% And in tea 0.02-0.04 wt. .% constituent a).

The method according to the invention is particularly effective for combating sucking harmful insects, in particular of the Homoptera class, especially against Myzus persicae, Psylla spp, Prhorodon humuli, Aleutroxis flocco-sus, Nilaparvata spp, especially Nilaparvata lugens and Heliothis spp. Specific examples of preparations according to the invention are given below. The parts herein are parts by weight.

Preparation A) -soluble powder.

10 parts of an emulsifier, for example ANTAROX C0-210, was added to 7 parts of a carrier, for example silicon dioxide, in a mixer and mixed for 30 minutes. Thereafter, 74 parts of technical thiocyclam was added thereto. hydrogen oxalate (containing about 88% thiocyclam. hydrogen oxalate) and 9 parts of a base, for example calcium oxide, added thereto, mixed the mixture for 20 minutes and then crushed in a hammer mill.

Preparation B) wettable powder.

28 parts of thiocyclam was mixed. hydrogen oxalate (technical), 12 parts of a surfactant (for example, FEN0P0N T-77), 8 parts of a carrier, for example, silicon dioxide, 15 parts of clay, 4 parts of a base, for example, -CaO, and 33 parts of sodium sulfate during a hour. Crushing this mixture in a hammer mill yielded a wettable / wet powder.

30 Preparations C, D, E, and F.

Proceed as described in preparing Examples A and B, but now replace the thiocyclam. hydrogen oxalate by the same amount (parts) of cartap (in monohydrochloride form) or nereistoxine hydrogen-35 8102117 13 * oxalate, whereby preparation C (soluble, powdered cartap), preparation D (wettable, powdered cartap), preparation E (soluble powder, nerealoxine. ) and obtained preparation F (wettable powder, nereistoxine, hydrogen oxalate).

5 The preparations G-K soluble powder.

In the same manner as described for preparation example A, the following preparations were prepared: 810 2 117 14 a rt <D Hi Ω CO> O ft cn to (B rt to pi H-HXP4 to

O rt to * g O h * £ r * to ηB

^ H ^ to H · O H * o <p toi- * to o> <i to o to

I, (DHH-to "<! CD

to (BN ejSHO rt

N .to to B 00 Η1 (B

Η · I · to OUl '-' toH · (-J. OuH - rt B h> ton · (D · H · n to to * w to. S! To

eg (D to ^ to KN

toH- to rt h to · n> to ^ i-i

I CO

1 rt 0

Hi - cn

CO t 'Ο Nl Μ K O

I u v v u v v Ο Ο Ο Μ ΙΌ Cn Ο Ο O Ui Ui

- M

4S ο 00 ffi vo I I »» »» n

<· Ο ΙΌ 00 -O- (D

cn s! H · to * rt

CO

co to - no "to

CO O Ό O 00 (D

* · *** »*» * · Μ H

σι ο to oo ί "o

(D

to rt to oo

(D

- - - 4> - 4> vo no oo cn u I I V V V «Cj

Ui Ο Ο O Ui - O '-J o Ό "J 00 ^ v I (***» * »** Ps Ο O to to Ui

Onion Onion 810 2 117 15

Preparation L.

16 parts of an emulsifier, for example ATLOX 4851 B, and 16 parts of monoethanolamine were mixed with 23 parts of silica in a grinder. A free-flowing powder was thus obtained. To this was added 45 parts of thiocyclam hydrogen oxalate (technical) and the mixture was crushed in a hammer mill.

Preparation M mixture in a tank.

30 g of morpholine were added to 100 liters of water. To this solution was added 100 g of a preparation containing 58% thiocyclam hydrogen oxalate (technical), 20.1% ATLOX 4851 B, 13.4% silicon dioxide and 8.5% sodium chloride with stirring. Stirring was continued until the powder was completely dissolved. (The% and are percent by weight).

15 Preparation N mixture in a tank.

Proceed as described in Preparation Example M, using 50 g of calcined sodium carbonate instead of 30 g of morpholine.

Preparation 0 mixture in a tank.

The spray tank was filled with 100 liters of water and 40 g of granular, calcined sodium carbonate (which did not contain water) were slowly added to this, while stirring or circulating the water, until the sodium carbonate had completely dissolved. 80 g of the preparation containing 58% thiocyclam were then added.

Hydrogen oxolate (technical), 20.1% ATLOX 4851 B, 13.4% silica and 8.5% sodium chloride were added with stirring until the product was completely dissolved.

ATLOX 4851 B used in Examples G-0 is a surfactant marketed by ICI-Atlas 30 Chemie GmbH Germany. It is a mixture of the calcium salt of an alkyl aryl sulfonate with polyoxyethylenated triglyceride in the form of a yellow-brown, viscous liquid with a water content of less than 1%, a specific gravity at 20 ° C of 1.0-1.04 g / cm3 and an HLB of 13.2 ^ 1.0.

35 8102 11 7% 16 ATLOX 4851 B can be replaced by equivalent emulsifiers.

Example APP-I

Cotton infected with eggs of Heliothis zea ^ 5 was treated in Georgia (United States of America) with an aqueous solution of preparation G (see Preparation Example G) in an amount of 136 g thiocyclam. Hydrogen oxalate (technical) per hectare with a spray volume of 8 gals' / acre.

Treatment efficiency (in%) was evaluated by determining the number of dead eggs (7 days after treatment) according to Abbott's calculation. The results were compared to the results obtained with a standard product (S) containing 95% thiocyclam, hydrogen oxalate (technical) ^ 1% TENSIOFIX XN 10 (an ethoxylated phosphate surfactant; Tensia, Belgium), 1% silicon oxide> Contained 3% ethylenediamine tetraacetic acid and was administered in the same amount (136 g active ingredient per hectare).

The following results were obtained the percentage yield 7 test ~ 1 test 2 test 3 preparation preparation preparation

GS GS GS

25 86 47 82 27 79 22

G = preparation G

S = standard • Example APP-2 30

A correspondingly improved yield was obtained if formulation G was replaced by an equivalent amount of formulations A, B, C, D, E, F, Η, I, J, K, L, M, N or 0.

35 8102117 ♦ 17 *

Example APP-3

The effectiveness of formulation A for rice was compared to that of standard formulation S (field trials in South Korea). The dose could be reduced from 600-750 g 5 to 330-375 g active ingredient per hectare if formulation A was used. Preparation A is particularly effective against Pyralidaei Cicadellidae, Delphacidae and Chrysomelidae. '

Example APP-4

A corresponding improvement in rice efficiency was obtained when formulation A in Example APP-3 was replaced with one of formulations B-0.

Example APP-5

The yield of preparations A, B and 6-0 was compared with that of preparation S against Lepitinotarsa (adults and larvae) in potatoes in an amount of 300 g of component a) per hectare. A significant improvement in yield with the formulations A, B, and G-0 over formulation S was observed.

Example APP-6 The efficiency of formulations A, B and G-0 was compared to that of formulation S over Phorodon humuli in hop plants. The preparations were used in the form of an aqueous spray containing 0.02% by weight of thiocyelam hydrogen oxalate (thus preparations Μ, N and 0 will have to be diluted) until its preparation was dripping. A significant improvement in the efficiency over formulation S was observed.

Example APP-7

Pere trees infected with Psylla pirisuga were treated (until dripping) with an aqueous spray containing 0.06 wt% thiocyclam hydrogen oxolate processed according to preparation example A, B and G-L. A significant improvement in the efficiency over formulation S was observed.

35 8102 117 ί * 18

Example ΑΡΡ-8

Orange apple trees infected with Aleurothrixus floccosus were treated (until dripping) with an aqueous spray containing Q.04 wt.% Thiocyclam. preparation S where.

8102117

Claims (68)

1. Process for preparing a composition having the insecticidal action, characterized in that a component a), a compound of the formula 1, in which both X substituents are equal and CON 2 is represented, or both 5 X substituents form a divalent sulfur atom or a single bond, in an agriculture-acceptable salt form and component b), an agricultural water-soluble base capable of component a) in an aqueous medium in its free base form into a suitable form of application for such an application. 2. Process according to claim 1, characterized in that both X substituents together form a divalent sulfur atom. 3. Process according to claim 2, characterized in that component a) is present in hydrogen oxalate form. Method according to claims 1-3, characterized in that component b) has a pKa value of 7-13. Method according to claim 4, characterized in that the pKa value is between 8 and 12. 6. Process according to claims 1-5, characterized in that component b) is an inorganic base. 7. Process according to claim 6, characterized in that the constituent b) is NH 4 OH, NaHCO 2, NaOH, CaOH 2, CaO, Na 2 CO 2 or a mixture thereof. 8. Process according to claim 7, characterized in that as constituent b) calcium oxide is used. Process according to claim 7, characterized in that component b) is ^ 2 ^ ^. 10. Process according to claim 9, characterized in that anhydrous sodium carbonate is used. Process according to any one of the preceding claims, characterized in that component b) is used in a sufficient amount of 81 02 117 · Jt h to convert at least 80% of component a) into its corresponding base form. 12. A method according to claim 11, characterized in that component b) is present in an amount sufficient to convert at least 90% of component a) into its corresponding base form. 13. A method according to claim 11, characterized in that component b) is present in an amount sufficient to convert at least 100% of component a) into its corresponding base form. 14. A process according to any one of the preceding claims for use as an aqueous spray, characterized in that the type and amount of component b) is chosen such that the spray liquid has a pH between 7.0 and 10. 15. Process according to claim 14, characterized in that the type and amount of component b) is chosen such that the spray liquid achieves a pH of at least 7.5. The method according to claim 15, characterized in that the type and amount of component b) is selected such that the spray liquid achieves a pH between 7.7 and 9. 17. Process according to any one of the preceding claims, characterized in that component b) is used in an amount of 20-120% by weight of component a). 18. Process according to claim 17, characterized in that 4 to 20% by weight of component b) is mixed with component a). 19. Process according to any one of the preceding claims, characterized in that an anionic and / or non-ionic surfactant that is acceptable for agricultural purposes is also included in the preparation. A process according to claim 19, characterized in that the surfactant used is a dispersant or emulsifier acceptable for agricultural purposes or a mixture thereof. 21. Process according to claim 20, characterized in that the emulsifier used is a phosphonic acid ester of ethylenedyl alcohols, an alkylarysulfonate, a mixture of mono and diesters of orthophosphonic acid, an ethoxylated sorbitan high ester, an alkylphenylpolyethylene glycol ether, polyoxyethylene triglyceride or a polyoxyethylene polyoxypropylene / 10 -. ... 1 copolymer. 22. Process according to claim 20 or 21, characterized in that an emulsifier with an average hydrophilic lipophilic balance between 9-15 is used. 23. Process according to claim 20, characterized in that the dispersant used is a high alcohol sulfate, a lignin sulfonate, a naphthalene sulfonate-formaldehyde condensation product or sodium N-methyl-N-oloyltaurate. 24. Process according to claims 19-23, characterized in that a weight ratio of component a) to 20 surfactant between 1: 0.04-6 is used. Process according to claim 24, characterized in that a weight ratio of component a) to surfactant between 1: 0.1-1 is used. 26. Process according to claim 25, characterized in that a weight ratio of component a) to surfactant between 1: 0.015-0.6 is used. 27. Process according to claims 1-26, characterized in that 20-99% by weight of component a), component b) and, if desired, a surfactant are included in the preparation. 28. Process according to claim 27, characterized in that a preparation is prepared which contains component b) mixed with component a) and in which 20-80% by weight of component a), component b) and optionally a surfactant are present. 35 8102117 Λ * 29. Process according to claim 28, characterized in that a preparation is prepared comprising 30-80% by weight of the constituent. a), component b) and optionally contains a surfactant. A method for preparing an aqueous dosage form of a preparation according to claims 1-29, characterized in that a preparation is prepared in which the concentration of component a) is between 0.01 and 0.9% by weight. 31. Method for controlling insects in an area, characterized in that a preparation is prepared in or in this area, according to a method of any one of the preceding claims. 32. A method according to claim 31, characterized in that in or in the area in an aqueous medium separated or mixed, in an insecticidally effective amount, component a) as defined in claim 1 and component b) as defined in claim 1. 33. Process according to claim 31, characterized in that component b) is an inorganic base with a pKa value of 7-13. A method according to claim 33, characterized in that component b) is calcium oxide. A method according to claim 33, characterized in that component b) is sodium carbonate. 36. Process according to claims 31-35, characterized in that an amount of component b) is used which is 20-120% by weight of component a). 37. The process of claim 36, characterized in that component b) is used in an amount sufficient to convert at least 80% of component a) into its corresponding base form. 38. Process according to claim 37, characterized in that component b) is used in an amount sufficient to set up at least 90% of component a) in its corresponding base form. 39. Process according to claim 38, characterized in that component b) is used in an amount sufficient to convert at least 100% of component a) into its corresponding base form. 40. Process according to claims 31-39, characterized in that component a) is used mixed with an anionic and / or non-ionic surfactant acceptable for agricultural purposes. A method according to claim 40, characterized in that the surfactant is an agricultural purpose tolerant dispersant or emulsifier or a mixture thereof. 42. A process according to claim 41, characterized in that the weight ratio of component a) to surfactant used is between 1: 0.1-1. A method according to claims 31-42, characterized in that the area is an area with plants. 44. Method according to claim 43, characterized in that the plants in the area rice, sugar beet, cotton, rape, rapeseed, pear trees, citrus fruits, potatoes, cruciferous vegetables, vegetables of the nightshade family , hop plants, tea, coffee or cocoa. 45. Process according to claim 43 or 44, characterized in that the insects are Pyralidae, Noctuidae, Chrysomelidae or sucking insects of the families Delphacidae, Cicadellidae, Aphididae, Psyllidae or Aleyrodidae. 46. Process according to claims 43-45, characterized in that component a) is used in a dosage of 150-1000 g per hectare of the area with plants. 47. A method according to claims 43-46, characterized in that the preparation is used in the form of an aqueous spray and the amount of the component b) is chosen such that the pH of the spray liquid achieves a pH between 7.0 and 10. 35 8102117 4 * * A method according to claim 47, characterized in that the amount of component b) is chosen such that the spray liquid reaches a pH of at least 7.5. 49. A method according to claim 48, characterized in that the amount of component b) is chosen such that the spray liquid achieves a pH between 7.7 and 9. 50. A process according to claims 31-49, characterized in that component a) is a compound of formula 1 as defined in claim 1, wherein both X substituents 10 together form bivalent sulfur. A method according to claim 50, characterized in that component a) is in the hydrogen oxalate form. 52. Process according to claim 50 or 51, 15, characterized in that component a) is used in a dosage of 150 to 400 g per hectare of area with plants. A method according to claim 52, characterized in that the area with plants is a rice paddy. 54. A method according to claim 53, characterized in that the harmful insects are Pyralidae, Cicadellidae, Delphacidae and / or Chrysomelidae. A method according to claim 52, characterized in that the area with plants is a cotton field. 56. A method according to claim 55, characterized in that the harmful insects are Noctuidae. A method according to claim 56, characterized in that the harmful insects Alabama argillacea Hbn, Heliothis spp. Earias spp., Spodoptera spp and / or Laphygma spp. to be. 58. A method according to claim 52, characterized in that the area with plants is an area with hop plants. 59. Method according to claim 58, characterized in that the harmful insect is Phorodon 'humuli' The method according to claim 52, characterized in that the harmful insect is Myzus persicae Sulz. 35 8102117 V. ' V. _ * * # * · A method according to claim 60, characterized in that the area with plants is an area with stone fruit, sugar beet or tobacco. 62. A method according to claim 52, characterized in that the harmful insect Psylla spp.is. A method according to claim 62, characterized in that the harmful insect is Psylla piri, Psylla piricola or Psylla pirisuga. 64. Method according to claim 62 or 63, characterized in that the area with plants has been washed with an area with pome fruits. A method according to claim 64, characterized in that the area with plants is an area with pear trees. 66. Process according to claims 31-65, characterized in that component a) and component b) are used as a mixture in a tank. 67. Method as described in the description and / or examples. 68. Preparations obtained according to the method of claims 1-30. ί ^% \ 02117 s— * CH ^ SX (ct ^ N-CH _Ll- ^ CHfeSX 1 - -i SANDOZ AG, Basel, Switzerland 8102 11 7