WO2001040256A1 - Taccalonolides and their use - Google Patents

Abstract

The invention relates to natural compounds of formula (I) some of which are to processes for obtaining and preparing them, to derivatives of these natural compounds, and to their use for controlling animal pests in which R?6 and R7¿ together represent the group -OCOC(OH)(CH¿3?)-, where the oxygen is linked to the carbon atom carrying the R?6¿ radical, or R?7 and R8¿ together represent the group -C(OH)(CH¿3?)COO-, where the carbon atom is linked to the carbon atom carrying the R?7¿ radical.

Description

Taccalonolides and their use

The invention relates to natural compounds, some of which are novel, to processes for obtaining and preparing them, to derivatives of these natural compounds, and to their use for controlling animal pests.

The natural compounds in question can be isolated from plants of the genus Tacca which belong to the family of the Taccaceae. At present, approximately 50 species of the genus Tacca are known (Tacca aspera; Tacca bibracteata; Tacca cardenasianum; Tacca caudatum; Tacca chanteraeri; Tacca chantrieri; Tacca cheancer; Tacca cristata; Tacca cylindricum; Tacca dubium; Tacca hasslerianum; Tacca josephinae; Tacca laevis; Tacca leontopetaloides; Tacca madagascariensis; Tacca minor; Tacca oceanica; Tacca palmata; Tacca par keri; Tacca paxiana; Tacca peregrinum; Tacca plantaginea; Tacca quanzensis; Tacca samoensis; Tacca subflabellata; Tacca ulei; Tacca umbrarum; Tacca variable; Tacca viridis; Tacca warmingii; Tacca weddelianum (see also Index Kewensis, Oxford University Press 1993)). They originate from the tropics and subtropics, in particular from the Asiatic region. In African ethnobotanics, an ethanolic extract of leaves from Tacca leontopetaloides is used against slugs and snails. Furthermore, an aqueous extract of tubers from Tacca leontopetaloides is used as an agent for controlling roundworms

(A. Abdel-Aziz et al., Phytotherapy Research, 1990, 4, 62-65).

13 different compounds which, owing to their origin, are referred to as taccalonolides have already been isolated from Tacca plantaginea (Z. Chen, B. Wang, M. Chen, Tetrahedron Lett. 1987, 28, 1673; Z. Chen, J. Shen, Y. Gao Heterocycles 1989, 29,

2103; S. Vasanth, R. Hamsaveni Gopal, R. B. Rao J. Scient. Ind. Res. 1990, 49, 68; Z. Chen, B. Wang, J. Shen Phytochemistry 1988, 27, 2999; S. Chen, Z. Gao, Y. Seng Chin. J. Chem. 1991, 1, 92; Z. Chen, J. Shen, Y. Gao, M. Wichtl Planta Medico 1997, 63, 40-43; J. Shen, Z. Chen, Y. Gao Phytochemistry 1996, 42, 891). However, the question of whether these compounds have any biological action and, if so, which has not to date been investigated in detail. Surprisingly, extracts obtained from the tubers of Tacca paxiana, Tacca subflabellata, Tacca plantaginea and Tacca chanteraeri now exhibited nematicidal, insecticidal and ectoparasitic properties. By means of a bioassay-controlled fractionation, 10 ingredients which are active against insects, nematodes, helminths, molluscs and ectoparasites have been isolated. Surprisingly, it has been found that the active components belong to the substance class of the taccalonolides, of which 13 different taccalonolides (A - M) already have been isolated from Tacca plantaginea (see above and Tab. LA). The literature also describes derivatives of taccalonolides; however, the biological activity thereof has hitherto likewise not been disclosed (see Tab. IB).

We now succeeded in isolating the taccalonolides A, B, E, K and the novel taccalonolide N, O, Q, R, S and T from the extracts of Tacca paxiana, Tacca subflabellata, Tacca plantaginea and Tacca chanteraeri. For the first time, it was also possible to correlate the anthelmintic and molluscidal action of the extracts described in ethnobotany with these compounds.

Accordingly, the invention relates to the use of compounds of the general formula (I)

in which

R represents, hydroxyl, hydrogen, Cι-C4-alkoxy, Ci-Cg-alkylcarbonyloxy or hydroxyacetoxy, R² represents hydroxyl, hydrogen,

C_j-Cg-alkylcarbonyloxy or hydroxyacetoxy,

R³ represents hydroxyl, hydrogen, C^-C^alkoxy, Ci-Cg-alkylcarbonyloxy or hydroxyacetoxy,

R ,4 represents hydrogen,

R⁵ represents hydrogen, or

R⁴ and R⁵ together represent a carbon bond, forming a double bond,

R⁶ represents hydrogen, or

R⁵ and R⁶ together with the carbon atom to which they are attached represent a carbonyl group, or

R⁶ and R⁷ together represent the group -OCOC(OH)(CH₃)-, where the oxygen is linked to the carbon atom carrying the R⁶ radical, or

R⁷ and R⁸ together represent the group -C(OH)(CH₃)COO-, where the carbon atom is linked to the carbon atom carrying the R⁷ radical, or

R⁸ represents hydroxyl, hydrogen, hydroxyacetoxy,

Ci-Ce- alkylcarbonyloxy or doubly attached oxygen,

R⁹ represents hydrogen,

R »ιo represents hydrogen, or R⁹ and R¹⁰ together represent a carbon bond, forming a double bond,

R¹¹ represents hydrogen, hydroxyacetoxy, C₁-C -alkoxy, -Ce-alkylcarb- onyloxy or hydroxyl, or

R¹⁰ and R¹¹ together with the carbon atom to which they are attached represent a carbonyl group,

R¹² represents hydroxyl, hydrogen, hydroxyacetoxy,

Ci-Cg- alkylcarbonyloxy or doubly attached oxygen,

R¹³ represents hydroxyl, hydroxyacetoxy,

Ci-Cg-alkylcarbonyloxy or hydrogen,

R¹⁴ represents hydrogen, hydroxyl, Q-C^alkoxy, Ci-Cg-alkylcarbonyloxy or halogen,

R¹⁵ represents hydrogen, hydroxyl, Cι-C₄-alkoxy, C-i-Cg-alkylcarbonyloxy or halogen, or

R¹⁴ and R¹⁵ together represent oxygen, thus forming an epoxy group, or represent a carbon bond, thus forming a double bond

and all possible stereoisomeric forms of the compounds of the formula (I) for controlling pests, such as nematodes, insects, molluscs, ectoparasites and helminths, which are encountered in agriculture, in forests, in the protection of stored products and materials, in animal health and in the hygiene sector. The compounds are especially useful for combating nematodes.

Preferred compounds of the formula (I) are the stereoisomers of the formula (IA) or formula (IB)

Preferred substituents or ranges of the radicals present in the formulae listed above and below are defined below.

R¹ preferably represents hydroxyl, methoxy, ethoxy, C-|-C4-alkylcarbonyloxy or hydrogen.

R² preferably represents hydroxyl, methoxy, hydrogen, acetoxy, ethyl- carbonyloxy, n- or i-propylcarbonyloxy, n-, i-, s- or t-butylcarbonyloxy or hydroxyacetoxy.

R³ preferably represents acetoxy, hydroxyl, methoxy or hydrogen.

R⁸ preferably represents hydroxyl, methoxy, acetoxy, ethylcarbonyloxy, n- or i- propylcarbonyloxy, n-, i-, s- or t-butylcarbonyloxy hydrogen or doubly attached oxygen. Rⁿ preferably represents methoxy, acetoxy, ethylcarbonyloxy, n- or i-propyl- carbonyloxy, n-, i-, s- or t-butylcarbonyloxy or hydroxyl.

1

R preferably represents acetoxy, hydroxyl, methoxy or doubly attached oxygen.

R¹³ preferably represents hydroxyl, methoxy, acetoxy or hydrogen.

R¹⁴ preferably represents hydrogen, hydroxyl, acetoxy, methoxy or chlorine.

R¹⁵ preferably represents hydrogen, hydroxyl, acetoxy, methoxy or chlorine.

R¹⁴ and R¹⁵ preferably represent oxygen, thus forming an epoxy group.

R¹ particularly preferably represents acetoxy, ethylcarbonyloxy, n- or i- propylcarbonyloxy, n-, i-, s- or t-butylcarbonyloxy or hydroxyl.

R particularly preferably represents acetoxy, hydroxyl, hydroxyacetoxy or hydrogen.

R³ particularly preferably represents acetoxy or hydroxyl.

R particularly preferably represents acetoxy, hydroxyl, hydrogen or doubly attached oxygen.

R¹ ' particularly preferably represents hydroxyl or acetoxy.

R¹² particularly preferably represents acetoxy, hydroxyl or doubly attached oxygen.

R¹³ particularly preferably represents acetoxy, hydroxyl or hydrogen. R¹ very particularly preferably represents methoxy, acetoxy, n- or i- propylcarbonyloxy, n-, i-, s-, or t-butylcarbonyloxy or hydroxyl.

R very particularly preferably represents acetoxy, hydroxyl or hydrogen.

R very particularly preferably represents acetoxy or hydroxyl.

R¹ ' very particularly preferably represents hydroxyl.

R¹² very particularly preferably represents hydroxyl or doubly attached oxygen.

R¹³ very particularly preferably represents hydroxyl or hydrogen.

The most preferred compounds are compounds of the formula (II)

in which

R² and R⁸ have the definitions mentioned above as being preferred, particularly preferred or very particularly preferred.

Particular emphasis according to the invention is given to the compounds of the formula (III A) - (III F)

The compounds of the formulae (III A) - (III F) are new and form part of the subject- matter of the present application.

The invention also relates to the use of derivatives of the compounds of the formula (I), (II) or (III A - III F), i.e. compounds according to formula (I) or compounds of the formula (IV)

in which R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁴ and R¹⁵ have one of the definitions mentioned above, and

R¹⁶ represents hydroxymethyl, formyl, carboxyl or carboxyl methyl ester,

, 17 represents formyl, carboxyl or carboxyl methyl ester, and

R , 18 represents hydrogen, acetoxy, hydroxyl or - -alkoxy,

and to all possible stereoisomeric forms of the compounds of the formula (IN) for controlling pests such as nematodes, insects, molluscs, ectoparasites and helminths encountered in agriculture, in forests, in the protection of stored products and materials, in animal health and in the hygiene sector, preferably for controlling nematodes.

Preferred substituents or ranges of the formula (IV) are the definitions mentioned above as being preferred, particularly preferred or very particularly preferred for R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁴ and R¹⁵.

R , 18 preferably represents hydrogen, acetoxy, hydroxyl or methoxy.

Particular preference is given to compounds of the formulae (IVA) - (IV L).

(INB)

(INC)

(IV D)

(IV E)

(INF)

(IV G) IS¬

(IV H)

(IV I)

(IV J)

(IN K)

(IN L)

The compounds of the formulae (IV A) - (IV L) are new and form part of the subject matter of the present application. The compounds of the formulae (IV A) - (IV L) can be present in different stereoisomeric forms. The different stereoisomeric forms are encompassed in full by the present invention.

The abovementioned general or preferred radical definitions or elucidations can be combined with one another at will, i.e. including combinations between the respective ranges and preferred ranges.

Preference according to the invention is given to the compounds of the formula (I), (II) and (IV) which contain a combination of the meanings listed above as being preferred. Particular preference according to the invention is given to the compounds of the formula (I), (II) and (IV) which contain a combination of the meanings mentioned above as being particularly preferred.

Very particular preference according to the invention is given to the compounds of the formula (I), (II) and (IV) which contain a combination of the meanings mentioned above as being very particularly preferred.

Most preference according to the invention is given to compounds of the formula

(II), (III A) - (III F) and (IVA) - (IV L). Within this group, special preference is givent to compounds of formula (II), (III A) - (III F), (IV A) to (IV E) and (IV J) - (IN L).

The compounds of the formula (I), (II), (III A) - (III F), (IV) and (IVA) - (IV L) can be present in different stereoisomeric forms. The different stereoisomeric forms are encompassed in full by the present invention.

The compounds of the formulae (III A) - (III F) and their stereoisomers are novel and also form part of the subject-matter of the present invention. Particular preference is given here to the stereoisomer shown in formulae (III A) - (III F).

In the structural formulae depicted above and below, hydroxyl groups are shown without the hydrogen, to render the formulae more simple.

The compounds of the formula (I), (II) and (III A) - (III F) according to the invention can be obtained by extracting comminuted parts of Tacca spec, plants with an organic solvent and subjecting the concentrated extract to a stepwise liquid- chromatographic purification. Suitable organic solvents and the chromatographic methods which can be used are known to the person skilled in the art or can be found in the literature (Z. Chen. B. Wang, M. Chen, Tetrahedron Lett. 1987, 28, 1673; Z. chen. B. Wang. J. Shen Phytochemistry 1988, 27, 2999; S. Chen. Z. Gao, Y. Seng. Chin. J. Chem. 1991, 1, 92; Z. Chen, J. Shen, Y. Gao, M. Wichtl, Planta Medica 1997, 63, 40-43; J. Shen, Z. Chen, Y. Gao, Phytochemistry 1996, 42, 891).

The compounds of the formula (IV) and (IVA) - (TV L) according to the invention can be obtained in a known manner from the compounds of the formula (I), (II) and (πi A) - (III F) (Z. Chen et al., Heterocycles 1989, 29, 2103) or according to processes described below (Examples 8-11). The compounds of the formula (IV) and (IN A) - (IN L) are preferably obtained from the compounds (taccalonolides) A to Ν (Tab. LA). With particular preference, the compounds of the formula (IV) and (IVA) -

(IV L) are obtained from the compounds (taccalonolides) A, B, E and Ν or from derivatives of these compounds.

The invention furthermore relates to a process for obtaining compounds of the formulae (I), (II) and (III A) to (III F), characterized in that comminuted plant material of Tacca spec, is initially extracted with an optionally water-containing organic solvent, the extract is adsorbed on a solid carrier material and enriched by vacuum liquid-chromatography, subsequently subjected to liquid-liquid partition and finally a liquid-chromatographic purification is carried out.

The process is preferably carried out to obtain compounds of the formula (I), (II) and (III A) - (III F) by extracting comminuted tubers such as Tacca spec, initially with a water-containing aliphatic alcohol, adsorbing the concentrated extract on silica gel, successively desorbing the extract components from the solid carrier using solvents of increasing polarity, then concentrating the desorbates, taking them up in water, then carrying out a liquid-liquid partition against solvents of increasing polarity, followed finally by liquid-chromatographic purification in a manner known to the person skilled in the art.

The invention furthermore relates to a second process for obtaining compounds of the formulae (I), (II) and (III A) - (III F), characterized in that comminuted plant material of Tacca spec, is initially extracted with an optionally water-containing organic solvent, the extract is partially dissolved in solvent-containing water and extracted successively with water-immiscible solvents of increasing polarity and finally subjected to a liquid-chromatographic purification, in a manner known to the person skilled in the art.

This process is preferably carried out to obtain compounds of the formula (I), (II) and (III A) - (III F) by extracting comminuted plant material of Tacca spec, initially with a water-containing lower aliphatic alcohol, partially dissolving the concentrated extract in water containing a small amount of methanol and extracting successively with a hydrocarbon and an ether and finally subjecting the ether phase to a liquid- chromatographic purification.

The invention furthermore relates to a process for preparing taccalonolides from other taccalonolides which is characterized in that taccalonolides are stirred in weak alkaline solution.

Thus, for example, it is possible to prepare the taccalonolides (B) and (N)

(B) (N)

starting from the natural taccalonolides (A) and (E)

(A) (E).

Taccalonolide B can be prepared by stirring taccalonolide A in weak alkali solution. Taccalonolide N can be prepared in the same manner, starting with taccalonolide E.

The compounds of formula (I), (II) or (III A) - (III F) can be prepared analogously from various parts of the Tacca spec, plants. These include the above-ground and below-ground parts and organs of plants, such as, for example, shoot, stem, leaves, flowers, trunk, seeds, roots or tubers. Preference is given to using the roots or tubers of Tacca spec.

Process for obtaining the substances of the formulae (D, (II) and (III)

Solid-phase enrichment (process 1)

The process for obtaining compounds of the formulae (I), (II) and (III A) - (III F) is generally characterized in that comminuted plant material of Tacca spec, is initially extracted with an optionally water-containing organic solvent (for example methanol, ethanol, propanol, isopropanol, acetone, ethyl acetate, diethyl ether, t.-butyl methyl ether, tetrahydrofuran, acetonitrile), the concentrated extract is adsorbed on a solid carrier material (for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, montmorillonite and ground synthetic minerals, such as finely divided silica, alumina, silicates or adsorber resins, such as phenol-formaldehyde resins or polyamide resins), enriched by successively desorbing the components of the extract from the solid carrier using solvents of increasing polarity (for example in the order: 1. heptane, hexane, pentane, cyclohexane, petroleum ether; 2. diethyl ether, toluene, benzene, t-butyl methyl ether, chloroform, dichloromethane, ethyl methyl ketone, dioxane, tetrahydrofuran; 3. ethyl acetate or acetone; 4. n-butanol, n-propanol, i-propanol, acetonitrile, methanol or ethanol), subsequently concentrating the desorbates, taking them up in water, then carrying out a liquid-liquid partition against solvents with increasing polarity (for example 1. heptane, hexane, pentane, cyclohexane, petroleum ether or carbon tetrachloride; 2. diethyl ether, toluene, benzene, t-butyl methyl ether, chloroform, dichloromethane, ethyl methyl ketone, dioxane, tetrahydrofuran, 3. ethyl acetate or acetone) and finally carrying out a liquid-chromatographic purification according to the state of the art.

The preparation of the taccalonolides A, B, E and N is described below by way of example.

Extraction

5 kg of dry Tacca spec, tubers are extracted with MeOH. The solvent is evaporated under reduced pressure, giving the methanolic crude extract (700 g).

Vacuum liquid chromatography The methanolic crude extract is dissolved in 2.1 1 of MeOH and adsorbed on 4.2 kg of silica gel 60 (Macherey & Nagel, 0.04-0.063 mm). The solvent is evaporated under reduced pressure, and the dry extract/silica gel mixture is filled into a large glass frit and eluted with a 4-step gradient (heptane: 10 1; tert-butyl methyl ether: 10 1; ethyl acetate: 10 1, water/MeOH 50:50). This gives 3.6 g of heptane phase, 45.8 g of tert-butyl methyl ether phase, 36.7 g of ethyl acetate phase and 121.8 g of water/MeOH phase. See also Hostettmann et al. (1998), Preparative Chromatography Techniques, pp. 39-47, Springer Verlag, ISBN 3-540-62459-7.

Liquid-liquid partition The tert-butyl methyl ether phase is dissolved in 700 ml of water and extracted successively with n-heptane (2.5 1), diethyl ether (2 1) and ethyl acetate (1.5 1). The solvent is evaporated, giving from the heptane phase 14.1 g, from the diethyl ether phase 4 g, from the ethyl acetate phase 3.1 g and from the H₂O phase that remains 20.1 g of residue.

Medium-pressure chromatography (MPLC) on silica gel and preparative HPLC on silica gel and reverse phase silica gel (RP18)

The diethyl ether phase is dissolved in dichloromethane and chromatographed over silica gel (Biotage KP-SIL 32-63 μm; column dimension: 160 x 40 mm) (mobile phase A: dichloromethane; mobile phase B: methanol; flow rate: 14 ml/min; gradient: start: 100% A; 1 min: 100% A; 121 min: 95% A; 131 min: 95% A;

141 min: 90% A; 151 min: 80% A; 191 min: 80% A; detection: 210 nm).

Taccalonolide B and N are prepared in pure form from fractions which elute between 30 and 70 min, preferably between 34 and 58 min, by repeated preparative HPLC using the following instrument parameters: hardware Gilson Abimed HPLC (UV detector, binary pump system); software Unipoint 1.71 (Gilson);

1. solid phase: Macherey & Nagel Nucleosil C18 (7 μm; 250 x 20 mm); flow rate: 25 ml min; mobile phase A: 0.1% TFA-containing water; mobile phase B: acetonitrile + 0.1% TFA; gradient: start: 85% A; 1 min 85% A; 30 min:

25% A; 35 min: 25% A;

2. solid phase: Macherey & Nagel Nucleosil C18 (7 μm; 250 x 20 mm); flow rate: 25 ml/min; mobile phase A: 0.1% TFA-containing water; mobile phase B: acetonitrile + 0.1% TFA; gradient: start: 70% A; 1 min 70% A; 30 min:

25% A; 35 min: 25% A.

3. solid phase: Macherey & Nagel Nucleosil C18 (7 μm; 250 x 10 mm); flow rate: 12.5 ml/min; mobile phase A: water + 2 g of ammonium formate/1; mobile phase B: acetonitrile + 2 g of ammonium formate/1; gradient: start:

80% A; 40 min 40% A; 41 min: 0% A. Taccalonolide A and E are prepared in pure form from fractions eluting between 50 and 70, preferably between 59 and 63 min, by preparative HPLC on SiO₂ or alternatively on an RP phase, using the following instrument parameters: hardware Gilson Abimed HPLC (UV detector, binary pump system); software Unipoint 1.71

(Gilson); solid phase: Macherey & Nagel Nucleosil 50-7 (250 x 21 mm); flow rate: 25 ml/min; mobile phase A: dichloromethane; mobile phase B: methanol; gradient: start: 100% A; 1 min 100% A; 41 min: 98% A; 42 min: 80% A; 61 min: 80% A.

Alternative embodiments and preferred alternative embodiments of the substances, instruments and procedures used in process 1 described above are illustrated in an exemplary manner below.

To prepare the individual compounds of the formulae (I), (II) or (III A) - (III F) according to the invention in pure form, a final purification via preparative phase

HPLC separation is carried out.

Suitable separation systems are, alternatively, for example 1. solid phase = Nucleosil C18; mobile phase A = 0.1% trifluoroacetic acid or formic acid or formate buffer or acetate buffer-containing water / B = 0.1% trifluoroacetic acid or formic acid or formate buffer or acetate buffer-containing acetonitrile or methanol; gradient of 0%-10% B initially increasing to 100% B over 45 - 90 minutes; 2. solid phase = silica gel; mobile phase: A = dichloromethane / B = methanol; gradient of 0% B initially increasing to 50% B over a period of 60 to 200 minutes.

Preferred solvents for the extraction are aqueous methanol (95%) or aqueous ethanol (95%). Preferred solid carrier materials are finely divided silicas, aluminas or phenol- formaldehyde resins. Desorption we preferably carried out using 1. heptane or petroleum ether and 2. ether or t-butyl methyl ether. The preferred solvents in the subsequent liquid-liquid partition are successively 1. heptane or petroleum ether and

2. ether or t-butyl ether. The final purification of the compounds of the formulae (I), (II) or (III A) - (III F) according to the invention via preparative phase FfPLC separation is preferably carried out in the first step using separation systems comprising: solid phase = Nucleosil C18; mobile phase: A = 0.1% trifluoroacetic acid-containing water / B = 0.1% trifluoroacetic acid-containing acetonitrile; gradient of 10% B initially increasing to 100% B over a period of 60 minutes and in the second step solid phase = silica gel; mobile phase: A = dichloromethane / B = methanol; gradient of 0% B initially increasing to 50% B over a period of 160 minutes.

In addition to methanol, it is also possible to choose ethanol, propanol, isopropanol, acetone, ethyl acetate, diethyl ether, t-butyl methyl ether, tetrahydrofuran, acetonitrile and other solvents known to the person skilled in the art for the extraction and the partial dissolution prior to application to solid carrier material.

Suitable solid carrier materials are, in addition to finely divided silicas and their modified variants such as, for example, C2, C4, C8, C18, DIOL, phenyl and amino, also ground natural minerals, such as kaolins, clays, talc, chalk, quartz, mont- morillonite and groimd synthetic minerals, such as alumina, silicates or adsorber resins such as phenol-formaldehyde resins or polyamide resins.

For the successive desorption from the carrier material, it is also possible to choose successively 1. petroleum ether or heptane; 2. diethyl ether or ethyl acetate; 3. acetone or n-butanol or isobutanol, 4. methanol or ethanol or isopropanol. It is possible to use mixtures of the solvents with one another, in increasing solvent strength, too.

The compounds of the formulae (I), (II) or (III A) - (III F) according to the invention can also be enriched in the liquid-liquid partition step by extracting with 1. petroleum ether or heptane; 2. t-butyl methyl ether 3. n-butanol. The subsequent purification by preparative phase HPLC can also be carried out by the person skilled in the art using other stationary phases, such as RP8, phenyl, DIOL, C2, C4 or amino. The mobile phase mixtures may also contain additional other acids (for example formic acid) or additional buffers (for example ammonium acetate). The organic component of the mobile phase can also be, for example, methanol in the case of separation on C18 and chloroform in the case of separation on silica gel. The chromatography on the different solid phases can also be carried out on silica gel in the 1^st step and on C18 in the 2^nd step.

2. Liquid-liquid enrichment (process 2)

The second process for obtaining compounds of the formulae (I), (II) and (III A) - (III F) is generally characterized in that comminuted plant material of Tacca spec, is initially extracted with an optionally water-containing organic solvent (for example methanol, ethanol, propanol, isopropanol, acetone, ethyl acetate, diethyl ether, t-butyl methyl ether, tetrahydrofuran, acetonitrile, methylene chloride, chloroform), the concentrated extract is partly dissolved in solvent-containing water (for example methanol, ethanol, propanol, isopropanol, acetone, acetonitrile or other water- miscible solvents) and extracted successively with water-immiscible solvents of increasing polarity (for example in the order 1. heptane, hexane, pentane, cyclohexane, petroleum ether; 2. diethyl ether, toluene, benzene, t-butyl methyl ether, chloroform, dichloromethane, ethyl methyl ketone, dioxane, tetrahydrofuran; 3. ethyl acetate) and subsequently subjected to a liquid-chromatographic purification, according to the state of the art.

The isolation of the taccalonolides A, B, E and N is described in detail below.

Extraction

1.8 kg of dry Tacca spec, tubers are extracted with MeOH. Evaporation of the solvent under reduced pressure gives 248 g of methanolic crude extract. Liquid-liquid partition

In a stiπed vessel, 248 g of Tacca spec, crude extract are dissolved in 500 ml of water / methanol (95:5) and extracted in each case four times with in each case 200 ml of n-heptane and tert-butyl methyl ether. The solvent is removed on a rotary evaporator, giving 16.4 g of n-heptane phase and 2.6 g of tert butyl methyl ether phase.

Medium-pressure chromatography (MPLC) on silica gel

The tert butyl ether phase is dissolved in methanol and adsorbed on 30 ml of silica gel 60 (Macherey & Nagel, 0.04-0.063 mm). The solvent is evaporated under reduced pressure and the dry extract/silica gel mixture is filled into the injection module of a Biotage Flash 40 unit (Hertford, UK). Chromatography is carried out on silica gel (Biotage KP-SIL 32-63 μm; column dimension: 80 x 40 mm), under the following conditions: mobile phase A: dichloromethane; mobile phase B: methanol; flow rate: 14 ml min; gradient: start: 100% A; 1 min: 100% A; 121 min: 95% A;

131 min: 95% A; 141 min: 90% A; 151 min: 80% A; 191 min: 80% A; detection: 210 nm. The taccalonolide-containing fractions (413 mg) elute between 45 and 75, preferably between 54 and 64, min. The further isolation of the pure taccalonolides A, B, E and N is carried out as described under process 1.

Alternative embodiments and prefeπed alternative embodiments of the substances, instruments and procedures used in process 1 described above are illustrated in an exemplary manner below.

To prepare the individual compounds of the formulae (I), (II) or (III A) to (III F) according to the invention in pure form, a final purification via preparative phase HPLC separation is carried out. Suitable separation systems are, alternatively, for example 1. solid phase = Nucleosil C18; mobile phase A = 0.1% trifluoroacetic acid or formic acid or formate buffer or acetate buffer-containing water / B = 0.1 % trifluoroacetic acid or formic acid or formate buffer or acetate buffer-containing acetonitrile or methanol; gradient of 0%-10% B initially increasing to 100% B over 45 - 90 minutes; 2. solid phase = silica gel; mobile phase: A = dichloromethane / B = methanol; gradient of 0% B initially increasing to 50% B over a period of 60 to 200 minutes.

Prefeπed solvents for the extraction are aqueous methanol (95%) or aqueous ethanol

(95%). Preference is given to using a mixture of methanol/water (5:95) for partly dissolving the concentrated crude extract. The preferred solvents for the liquid-liquid partition that follows are 1. heptane or petroleum ether and 2. diethyl ether or t-butyl ether.

The final purification of the compounds of the formulae (I), (II) or (III A) - (III F) according to the invention via preparative phase HPLC separation is preferably carried out in the first step using separation systems comprising: solid phase = Nucleosil C18; mobile phase: A = 0.1% trifluoroacetic acid-containing water / B = 0.1% trifluoroacetic acid-containing acetonitrile; gradient of 10% B initially increasing to 100% B over a period of 60 minutes and, in the second step, solid phase = silica gel; mobile phase: A = dichloromethane / B = methanol; gradient of 0% B initially increasing to 50% B over a period of 160 minutes.

In addition to methanol, it is also possible to choose ethanol, propanol, isopropanol, acetone, ethyl acetate, diethyl ether, t-butyl methyl ether, tetrahydrofuran, acetonitrile and other solvents known to the person skilled in the art for the extraction.

The compounds of the formulae (I), (II) or (III A) - (III F) according to the invention can also be enriched in the liquid-liquid partition step by extracting with 1. petroleum ether or heptane; 2. t-butyl methyl ether or ethyl acetate; 3. n-butanol.

The final purification by preparative phase HPLC can also be carried out by the person skilled in the art using other stationary phases, such as RP8, phenyl, DIOL, C2, C4 or amino. The mobile phase mixtures may also contain additional other acids

(for example formic acid) or additional buffers (for example ammonium acetate). The organic component of the mobile phase can also be, for example, methanol in the case of separation on C18 and chloroform in the case of separation on silica gel. The chromatography on the different solid phases can also be carried out on silica gel in the 1^st step and on C18 in the 2^nd step.

3. Process for preparing taccalonolides (process 3) and their derivatives

Taccalonolide B from A

At a temperature between 0 and 50°C, 10 mg of taccalonolide A are, if appropriate with addition of 1-10 ml of solubilizer, such as, for example, methanol, ethanol or acetone, stirred in 1-20 ml of alkaline aqueous solution (pH 7.5-10) for a period of 5- 160 h. The solvent is evaporated and the aqueous phase is then extracted three times with a solvent such as, for example, chloroform, dichloromethane, diethyl ether, t- butyl methyl ether or ethyl acetate. The solvent is removed, giving 6.7 mg of taccalonolide B as a colourless solid.

Taccalonolide N from E

At a temperature between 0 and 50°C, 10 mg of taccalonolide E are, if appropriate with addition of 1-10 ml of solubilizer, such as, for example, methanol, ethanol or acetone, stirred in 1-20 ml of alkaline aqueous solution (pH 7.5-10) for a period of 5-

160 h. The solvent is evaporated and the aqueous phase is then extracted three times with a solvent such as, for example, chloroform, dichloromethane, diethyl ether, t- butyl methyl ether or ethyl acetate. The solvent is removed, giving 6.7 mg of taccalonolide N as a colourless solid.

The process is preferably carried out at a pH of from 7.5 to 9, particularly preferably at a pH of from 8.0 to 8.5 and very particularly preferably in 0.05 molar sodium bicarbonate solution (pH = 8.2). The prefeπed solubilizer used is methanol. The prefeπed reaction temperature is in the range between 10 and 30°C, particularly preferably room temperature (20°C). At this temperature, the prefeπed reaction time is 20 - 90 h, particularly preferably 40 - 45 h. Preferred solvents for the extraction are ether or methylene chloride.

Derivatives Derivatives of the taccalonolides can be prepared from the taccalonolides described in the present invention (Table I A). Derivatives 3, 4, 5 and 9 of Table I B are known compounds and can be prepared from taccalonolide A according to Z. Chen., J. Shen, Y. Gao (1989) Heterocycles 29, 2103 - 2108.

Derivatives 10, 11, 14 and 18 have not been described in literature before. They can be prepared from taccalonolide E in an analogous manner to the preparation of derivatives 3, 4, 5 and 9 from taccalonolide A (Z. Chen, J. Shen, Y. Gao (1989), Heterocycles 29, 2103 - 2108).

Derivatives 12 and 13 have also not been described in literature before. They can be prepared from taccalonolide N (Derivative 12) and taccalonolide B (Derivative 13), respectively, according to the above-mentioned process described for derivatives of taccalonolide A (Z. Chen et al. 1989).

Derivatives 15, 16, 17, 19 and 20 have also not been described in literature before.

The preparation of these compounds is described below (Examples 8, 9 and 10).

Further derivatives can be obtained in an analogous way by opening the epoxide-ring with other nucleophilic reagents, for example phenoxides or other nucleophilic reagents well known to a person skilled in the art.

The compounds of the formulae (I), (II), (III A) - (III F), (IV) and (IVA) - (IV L) are suitable for controlling animal pests, in particular nematodes, insects, molluscs, ectoparasites and helminths, encountered in agriculture, in forests, in the protection of stored products and materials, in animal health and in the hygiene sector, and they are tolerated well by plants and have favourable homoiotherm toxicity. Within this group, the compounds of the formulae (I), (II), (III A) - (IH F), (IV A) - (IV E) and (IV J) - (IV L) are especially suitable for controlling pests. They are active against normally sensitive and resistant species and against all or some development stages. The compounds of the formula (I), (II), (ITI A) - (LII F), (IV) and (IVA) - (IV L) are particularly effective against nematodes, insects and helminths. The compounds of the formula (I), (II), (III), (IV) and (IVA) are preferably suitable for controlling biting insects and nematodes and especially suitable for controlling plant pathogenic nematodes. The compounds of the formula (I), (II), (III A) - (III F), (IV) or (IVA) - (IV L) can be isolated from plants or be obtained fully synthetically or semi- synthetically. The compounds mentioned above and below are active on their own or in combination with one another or in combination with other compounds or formulations suitable for controlling animal pests, microorganisms or fungi. The present invention also provides the use of extracts of Tacca spec, which comprise at least one of the compounds of the formula (I), (II) or (III A) - (III F) for controlling pests. The extracts can also be used in combination with other compounds or formulations which are suitable for controlling animal pests, microorganisms or fungi.

The extracts can be obtained as described in a general manner in processes 1 and 2 and be used in various grades of purity, the content of the compounds of the formula

(I), (II) or (III A) - (III F) in these extracts varying between 0.01 and 2%, preferably between 0.1 and 1% (w/w).

The invention also provides the use of parts of plants of Tacca spec, for controlling pests. Preference is given to using optionally dried parts of plants in comminuted form, for example as a suspension, a paste, as granules, powder, meal or crumbs. Preference is given to using the leaves, roots and tubers of the plants, very particularly preferably its roots and tubers, for this purpose. The comminuted parts of plants can also be used as additives for other compounds or formulations which are suitable for controlling animal pests, microorganisms or fungi. The abovementioned pests include:

From the order of the Isopoda, for example, Omscus asellus, Armadilhdium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp..

From the order of the Anoplura, for example, Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp. From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphisgossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphisfabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus an dinis,

Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii,Aspidiotus hederae, Pseudococcus spp. Psylla spp.

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysoπhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofinannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnama and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcarus, Cosmopolites sordidus, Ceuthoπhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp.,

Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp..

From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.

From the order of Acarina z.B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,

Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp..

The compounds of the formula (I), (II), (III A) - (in F), (IV) and (IVA) - (IV E) and (IV J) - (IV L) according to the invention exhibit, in particular, excellent activity against phytoparasitic nematodes. The phytoparasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp. and Bursaphelenchus spp..

The compounds of the formula (I), (II), (III A) - (III F), (IN) and (IVA) - (IV L) according to the invention exhibit, in particular, excellent activity against the larvae of the mustard beetle (Phaedon cochleariae), the caterpillars of the diamond back moth (Plutella maculipennis), the caterpillars of the owlet moth (Spodoptera frugiperda), the larvae of the green rice leafhopper (Νephotettix cincticeps), peach aphids (Myzus persicae) and all stages of the greenhouse red spider mite (Tetranychus urticae).

The active compounds and, if appropriate, also the extracts and comminuted parts of the Tacca spec, plant can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound and very fine capsules and polymeric substances.

These formulations are prepared in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, if appropriate with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.

If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, mineral or vegetable oil, alcohols, such as butanol or glycol, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.

Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam- formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. The formulations in general contain between 0.01 and 95 per cent by weight of active compound, preferably between 0.1 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, to widen, for example, the activity spectrum or to prevent the development of resistance. In many cases, this results in synergistic effects, i.e. the activity of the mixture exceeds the activity of the individual components.

Examples of particularly advantageous mixing components are the following:

Fungicides: aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polysulphide, capsimycin, captafol, captan, carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram, debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon, ediphenphos, epoxiconazole, etaconazole, ethirimol, etridiazole, famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide, fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole- cis, furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione, irumamycin, isoprothiolane, isovaledione, kasugamycin, kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin, paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinconazole, quintozene (PCNB), sulphur and sulphur preparations, tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole, tridemo h, triflumizole, triforine, triticonazole, uniconazole, validamycin A, vinclozolin, viniconazole, zarilamide, zineb, ziram and also

Dagger G, OK-8705,

OK-8801, α-( 1 , 1 -dimethylethyl)- 5 -(2-phenoxyethyl)- 1 H- 1 ,2,4-triazole- 1 -ethanol, α-(2,4-dichlorophenyl)- Ξ-fluoro-b-propyl-lH-l,2,4-triazole-l-ethanol, α-(2,4-dichlorophenyl)- 3-methoxy-a-methyl-lH-l,2,4-triazole-l-ethanol, α-(5-methyl-l,3-dioxan-5-yl)-Ξ-[[4-(trifluoromethyl)-phenyl]-methylene]-lH-l,2,4- triazole- 1 -ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-( 1 H- 1 ,2,4-triazol- 1 -yl)-3-octanone,

(E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide, isopropyl 1 - {2-methyl- 1 -[[[ 1 -(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl} - carbamate, 1 -(2,4-dichlorophenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)-ethanone O-(phenyhnethyl) oxime,

1 -(2-methyl- 1 -naphthalenyl)- 1 H-pyrrol-2,5-dione, l-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,

1 - [(diiodomethyl)-sulphony 1] -4-methyl-benzene,

1 - [ [2-(2,4-dichlorophenyl)- 1 ,3 -dioxolan-2-yl] -methyl] - 1 H-imidazole, 1 - [ [2-(4-chlorophenyl)-3 -phenyloxiranyl] -methyl] - 1 H- 1 ,2,4-triazole, l-[l-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-lH-imidazole, l-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,

2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4^l-trifluoro-methyl-l,3-thiazole-5- carboxanilide, 2,2-dichloro-N-[ 1 -(4-chlorophenyl)-ethyl]- 1 -ethyl-3 -methyl-cyclopropane- carboxamide,

2,6-dichloro-5-(methylthio)-4-pyrimidinyl thiocyanate,

2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,

2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide, 2-(2,3,3-triiodo-2-ρroρenyl)-2H-tetrazole,

2-[(l-methylethyl)-sulphonyl]-5-(trichloromethyl)-l,3,4-thiadiazole,

2-[[6-deoxy-4-O-(4-O-methyl- -D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4- methoxy-lH-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

2-aminobutane, 2-bromo-2-(bromomethyl)-pentanedinitrile,

2-chloro-N-(2,3-dihydro-l,l,3-trimethyl-lH-inden-4-yl)-3-pyridinecarboxamide, 2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,

2-phenylphenol (OPP),

3,4-dichloro- 1 -[4-(difluoromethoxy)-phenyl]- 1 H-pyπol-2,5-dione,

3,5-dichloro-N-[cyano-[(l-methyl-2-propynyl)-oxy]-methyl]-benzamide, 3-( 1 , 1 -dimethylpropyl- 1 -oxo- 1 H-indene-2-carbonitrile,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)- 1 H-imidazole- 1 -sulphonamide,

4-methyl-tetrazolo[ 1 ,5-a]quinazolin-5(4H)-one,

8-( 1 , 1 -dimethylethyl)-N-ethyl-N-propyl- 1 ,4-dioxaspiro[4.5]decane-2-methanamine, 8-hydroxyquinoline sulphate,

9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide, bis-( 1 -methylethyl) 3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate, cis- 1 -(4-chlorophenyl)-2-(l H- 1 ,2,4-triazol- 1 -yl)-cycloheptanol, cis-4-[3-[4-(l,l-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholine hydrochloride, ethyl [(4-chlorophenyl)-azo]-cyanoacetate, potassium hydrogen carbonate, methanetetrathiol sodium salt, methyl 1 -(2,3-dihydro-2,2-dimethyl-lH-inden- 1 -yl)- 1 H-imidazole-5-carboxylate, methyl N-(2 ,6-dimethylphenyl)-N-(5 -isoxazoly lcarbonyl)-DL-alaninate, methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2 ,3 -dichloro-4-hydro xyphenyl)- 1 -methy 1-cyclohexanecarboxamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide, N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,

N-(4-cyclohexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidineamine,

N-(4-hexylphenyl)- 1 ,4,5,6-tetrahydro-2-pyrimidineamine,

N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,

N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide, N-[2,2,2-trichloro- 1 -[(chloroacetyl)-amino]-ethyl]-benzamide,

N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N'-methoxy-methanimidamide, N-formyl-N-hydroxy-DL-alanine-sodium salt,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate, O-methyl S-phenyl phenylpropylphosphoramidothioate, S-methyl l,2,3-be__zothiadiazole-7-carbothioate, and spiro[2H]- 1 -benzopyran-2, 1 '(3'H)-isobenzofuran]-3'-one,

Bactericides: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

Insecticides / acaricide / nematicides: abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb, aldoxycarb, alpha- cypeπnethrin, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M, azocyclotin,

Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin, bio- permethrin, BPMC, bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin, cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron, diazinon, dichlorvos, diflubenzuron, dimethoat, dimethylvinphos, diofεnolan, disulfoton, docusat-sodium, dofenapyn, eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp., eprinomectin, esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox, etoxazole, etrimfos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazinam, fluazuron, flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate, fubfenprox, furathiocarb, granulosis viruses, halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox, hydroprene, imidacloprid, isazofos, isofenphos, isoxathion, ivermectin, nuclear polyhedrosis viruses, lambda-cyhalothrin, lufenuron malathion, mecarbam, metaldehyde, methamidophos, Metharhizium anisopliae, Metharhizium flavoviride, methidathion, metbiocarb, methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, monocrotophos, naled, nitenpyram, nithiazine, novaluron, omethoat, oxamyl, oxydemethon M,

Paecilomyces fumosoroseus, parathion A, parathion M, permethrin, phenthoat, phorat, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb, propoxur, prothiofos, prothoat, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen, pyriproxyfen, quinalphos, ribavirin, salithion, sebufos, selamectin, silafluofen, spinosad, sulfotep, sulprofos, tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb, vamidothion, vaniliprole, Verticillium lecanii, Yl 5302, zeta-cypermethrin, zolaprofos, (lR-cis)-[5-(phenylmethyl)-3-furanyl]-methyl 3-[(dihydro-2-oxo-3(2H)-furanyhdene)- methyl]-2,2-dimethylcyclopropanecarboxylate,

(3-phenoxyphenyl)-methyl 2,2,3,3-tetramethylcyclopropanecarboxylate, l-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-l,3,5-triazine- 2(lH)-imine,

2-(2-chloro-6-fluorophenyl)-4-[4-(l,l-dimethylethyl)phenyl]-4,5-dihydro-oxazole,

2-(acetlyoxy)-3-dodecyl- 1 ,4-naphthalenedione,

2-chloro-N-[[[4-(l-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,

2-chloro-N-[[[4-(2,2-dichloro- 1 , 1 -difluoroethoxy)-phenyl] -amino] -carbonyl] - benzamide,

3-methylphenyl propylcarbamate.

4- [4-(4-ethoxyphenyl)-4-methylpentyl] - 1 -fluoro-2-phenoxy-benzene,

4-chloro-2-( 1 , 1 -dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-

3 (2H)-pyridazinone, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)- pyridazinone,

4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)- pyridazinone,

Bacillus thuringiensis strain EG-2348, [2-benzoyl- 1 -( 1 , 1 -dimethylethyl)-hydrazinobenzoic acid,

2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo- 1 -oxaspiro[4.5]dec-3-en-4-yl butanoate,

[3- [(6-chloro-3 -pyridiny l)methyl] -2-thiazolidinylidene] -cy anamide, dihydro-2-(nitromethylene)-2H- 1 , 3 -thiazine-3 (4H)-carboxaldehyde, ethyl [2-[[l,6-dihydro-6-oxo-l-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate, N-(3,4,4-trifluoro-l-oxo-3-butenyl)-glycine,

N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-lH- pyrazole- 1 -carboxamide,

N-[(2-chloro-5-thiazolyl)methyl]-N'-methyl-N"-nitro-guanidine,

N-methyl-N'-( 1 -methy 1-2-propenyl)- 1 ,2-hydrazinedicarbothioamide, N-methyl-N'-2-propenyl- 1 ,2-hydrazinedicarbothioamide,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoroamidothioate. A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators is also possible.

Furthermore, when used as insecticides, the active compounds according to the invention can be present in their commercial formulations and in the use forms, prepared from these formulations, as a mixture with synergists. Synergists are compounds which increase the action of the active compounds, without it being necessary for the synergist added to be active itself.

The active-compound content of the use forms prepared from the commercial formulations can vary within wide limits. The active-compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.

Application is carried out in a customary manner adapted to the use forms.

When used against hygiene pests and pests of stored products, the active compound has residual activity on wood.

Arthropods

The active compounds according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medicine sector against animal parasites (ectoparasites), such as hard ticks, soft ticks, mange mites, leaf mites, flies

(biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.. From the order of the Mallophagida and the suborders Amblycerma and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp..

From the order of the Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp.,

Xenopsylla spp. and Ceratophyllus spp..

From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp..

From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp.,

Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp..

From the order of the Actinedida (Prostigmata) und Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds of the formula (I), (II), (HI A) - (in F), (IV) and (IVA) - (IV L) and the Tacca spec, extracts according to the invention are also suitable for controlling arthropods which infest agriculturally useful animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees and other pets, such as, for example, dogs, cats, caged birds and aquarium fish, and also so-called laboratory animals, such as, for example, hamsters, guinea pigs, rats and mice. By controlling these arthropods, cases of death and reduction in productivity (for meat, milk, wool, hides, eggs, honey etc.) should be diminished, so that more economic and easier animal husbandry is possible by use of the active compounds according to the invention.

The active compounds and extracts according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed- through process and suppositories, by parenteral administration, such as, for example, by injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, by dermal use in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of moulded articles containing active compound, such as collars, ear marks, tail marks, limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compounds of the formula

(I) , (π), (III A) - (III F), (IV) und (IVA) - (IV L), but also the extracts according to the invention, can be used as formulations (for example powders, emulsions, free- flowing compositions), which comprise the active compounds in an amount of 1 to 80%) by weight, directly or after 100 to 10,000-fold dilution, or they can be used as a chemical bath.

The active compounds and extracts according to the invention are furthermore suitable for controlling endoparasites encountered in the husbandry of useful animals, pets, laboratory animals and wild animals, in particular for controlling helminths such as

Trematodes

From the sub-class of the Monogenea, for example Gyrodactylus spp., Dacrylogyrus spp. and Polystoma spp.

From the sub-class of the Digenea, for example Diplostomum spp., Schistosoma spp., Trichobilharzia spp., Ornithobilharzia spp., Austrobilharzia spp.,

Gigantobilharzia spp., Echinostoma spp., Fasciola spp., Fasciolides spp., Fasciolopsis spp., Paramphistomum spp., Dicrocoelium spp., Troglotrema spp., Paragonismus spp., Opisthrochis spp., Chonorchis spp., Metorchis spp. and Heterophyes spp.

Cestodes

From the order of the PseudophyUidea, for example Diphyllobothrium spp., Ligula spp., Mesocestodes spp., Anoplocephala spp., Monieazia spp., Thysanosoma spp., Thysaniezia spp., Avitellina spp., Stilesia spp., Cittotaenia spp., Taenia spp.,

Echinococcus spp., Hydatigera spp., Davainea spp., Raillietina spp., Hymenolepsis spp. and Dipylidium spp. Nematodes

From the order of the Enoplida, for example Trichuris spp., Capillaria spp. and Trichinella spp.

From the order of the Rhabditida, for example Strongyloides spp.

From the order of the Strongylida, for example Strongylus spp., Trichonema spp., Oesophagostomum spp., Chabertia spp., Stephanurus spp., Ancyclostoma spp., Uncinaria spp., Bunostomum spp., Syngamus spp., Metastrongylus spp.,

Dictyocaulus spp., Muellerius spp., Protostrongylus spp., Neostrongylus spp., Angiostrongylus spp., Filaroides spp., Parafilaroides spp., Trichostrongylus spp., Heamonchus spp., Ostertagia spp., Cooperia spp., Nematodirus spp., Hyosfrongylus spp., Amidostomum spp. and Ollulanus spp.

From the order of the Oxyurida, for example Oxyuris spp., Enterobius spp., Passalurus spp., Syphacia spp., Aspiculuris spp. and Heterakis spp.

From the order of the Ascaridida, for example Ascaris spp., Toxascaris spp., Toxocara spp., Parascaris spp., Ansiakis spp. and Ascaridia spp.

From the order of the Spiruida, for example Gnathostoma spp., Thelazia spp., Gongylonema spp., Habronema spp., Parabronema spp., Draschia spp. and Dracunculus spp.

From the order of the Filariida, for example Stephanofilaria spp., Parafilaria spp., Setaria spp., Loa spp., Dirofilaria spp., Litomosoides spp., Brugia spp., Wuchereria spp. and Onchocerca spp.

From the order of the Gigantorhynchida, for example Macraconthorhynchus spp. They have, for example, excellent activity against Trichinella spiralis and Nippostrongylus brasiliensis.

The useful animals, pets, laboratory animals or wild animals preferably include agriculturally useful animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chicken, turkeys, ducks, geese, bees.

The pets include, for example, dogs, cats, caged birds and aquarium fish.

The laboratory animals include, for example, hamsters, guinea pigs, rats and mice.

The wild animals preferably include wild animals which are kept like domestic animals, such as, for example, fallow deer, certain antelope species, ostriches, etc.

When controlling such arthropods or helminths, the active compounds according to the invention can be used both prophylactically and therapeutically. By controlling these arthropods or helminths, cases of death and reduction in productivity (for meat, milk, wool, hides, eggs, honey, etc.) should be prevented, so that more economic animal husbandry is possible by use of the active compounds according to the invention.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, such as, for example, by injection

(intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, by dermal use in the form of, for example, dipping or bathing, spraying, pouring on and spotting on, washing and powdering and also with the aid of moulded articles containing active compound, such as collars, earmarks, tailmarks, limb bands, halters, marking devices and the like. It has furthermore been found that the compounds of the formula (I), (II), (HI A) - (HI F), (TV) and (IV A) - (IV L) according to the invention also have a strong insecticidal action against insects which destroy industrial materials.

The following insects may be mentioned as examples and as prefeπed - but without a limitation:

Beetles, such as

Hylotrapes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis,

Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec.

Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus

Hymenopterons, such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur

Termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptoteπnes formosanus.

Bristletails, such as Lepisma saccarina.

Industrial materials in the present connection are to be understood as meaning nonliving materials, such as, preferably, plastics, adhesives, sizes, papers and cards, leather, wood and processed wood products and coating compositions.

Particularly preferably wood and processed wood products are the material to be protected from insect infestation. Wood and processed wood products which can be protected by the agent according to the invention or mixtures comprising this agent are to be understood as meaning, for example: building timber, wooden beams, railway sleepers, bridge components, boat jetties, wooden vehicles, boxes, pallets, containers, telegraph poles, wood panelling, wooden windows and doors, plywood, chipboard, joinery or wooden products which are used quite generally in house building or in building joinery.

The active compounds can be used as such, in the form of concentrates or in generally customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, a dispersing agent and/or binder or fixing agent, a water repellent, if appropriate siccatives and UV stabilizers and if appropriate dyestuffs and pigments, and also other processing auxiliaries.

The insecticidal compositions or concentrates used for the preservation of wood and timber materials comprise the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on the nature and occurrence of the insects and on the medium. The optimum amount employed can be determined during the use in each case by a series of tests. In general, however, it is sufficient to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solvent or solvent mixture and/or an oily or oil-like organic chemical solvent or solvent mixture of low volatility and/or a polar organic chemical solvent or solvent mixture and/or water, and if appropriate an emulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-like solvents having an evaporation number above 35 and a flash point above 30°C, preferably above 45°C. Substances which are used as these oily or oil-like water-insoluble solvents of low volatility are appropriate mineral oils or aromatic fractions thereof, or solvent mixtures containing mineral oils, preferably white spirit, petroleum and/or alky-benzene.

Mineral oils having a boiling range from 170 - 220°C, white spirit having a boiling range from 170 - 220°C, spindle oil having a boiling range from 250 - 350°C, petroleum and aromatics having a boiling range from 160 - 280°C, terpentine oil and the like, are advantageously employed.

In a prefeπed embodiment, liquid aliphatic hydrocarbons having a boiling range from 180 - 210°C or high-boiling mixtures of aroma-tic and aliphatic hydrocarbons having a boiling range from 180 - 220°C and/or spindle oil and/or mono- chloronaphthalene, preferably α-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have an evaporation number above 35 and a flash point above 30°C, preferably above 45°C, can be replaced in part by organic chemical solvents of high or medium volatility, providing that the solvent mixture likewise has an evaporation number above 35 and a flash point above 30°C, preferably above 45°C, and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemical solvent or solvent mixture or an aliphatic polar orgamc chemical solvent or solvent mixture is replaced. Aliphatic organic chemical solvents containing hydroxyl and/or ester and/or ether groups, such as, for example, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the present invention are the synthetic resins and/or binding drying oils which are known per se, are water- dilutable and/or soluble or dispersible or emulsifiable in the organic chemical solvents employed, in particular binders consisting of or comprising an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin, such as indene-coumarone resin, silicone resin, drying vegetable oils and/or drying oils and/or physically drying binders based on a natural and or synthetic resin.

The synthetic resin used as the binder can be employed in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances can also be used as binders in an amount of up to 10% by weight. Dyestuffs, pigments, water-repelling agents, odour correctants and inhibitors or anticoπosive agents and the like which are known per se can additionally be employed.

It is preferred according to the invention for the composition or concentrate to comprise, as the organic chemical binder, at least one alkyd resin or modified alkyd resin and/or one drying vegetable oil. Alkyd resins having an oil content of more than 45% by weight, preferably 50 - 68% by weight, are preferably used according to the invention.

All or some of the binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent evaporation of the active compounds and crystallization or precipitation. They preferably replace 0.01 to 30%) of the binder (based on 100% of the binder employed). The plasticizers originate from the chemical classes of phthalic acid esters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters, such as tributyl phosphate, adipic acid esters, such as di-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amyl stearate, oleates, such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, glycerol esters and p-toluenesulphonic acid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether or ketones, such as benzophenone or ethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, if appropriate as a mixture with one or more of the abovementioned organic chemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnation processes on a large industrial scale, for example vacuum, double vacuum or pressure processes.

The ready-to-use compositions can also comprise yet further insecticides, if appropriate, and also another one or more fungicides, if appropriate.

Possible additional mixing components are, preferably, the insecticides and fungicides mentioned in WO 94/29 268. The compounds mentioned in this document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned are insecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron, and also fungicides, such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propinyl butylcarbamate, N-ocryl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one. The compounds according to the invention can also be used for protecting against infestation of articles, especially ships hulls, screens, nets, constructions, quays and signalling equipment, which come into contact with seawater or brackish water.

Infestation by sessile Oligochaetae, such as Serpulidae, and by shellfish and species of the group Ledamorpha (goose barnacles), such as various Lepas and Scalpellum species, or by species of the group Balanomorpha (acom barnacles), such as Balanus or Pollicipes species, increases the frictional resistance of ships and leads as a result, through increased energy consumption and frequent spells in dry dock, to a marked increase in the operating costs.

In addition to infestation by algae, for example Ectocarpus sp. and Ceramium sp., particular importance is attached to infestation by sessile Entomostraca groups, which are comprised under the name Cirripedia (cirriped Crustacea).

Surprisingly, it has now been found that the compounds according to the invention, on their own or in combination with other active compounds, have a good antifouling (anti-infestation) effect.

By using compounds according to the invention on their own or in combination with other active compounds, it is possible to dispense with the use of heavy metals, such as, for example, in bis(trialkyltin) sulphides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride, tri-«-butyl(2-phenyl-4-chlorophenoxy)- tin, tributyltin oxide, molybdenum disulphide, antimony oxide, polymeric butyl titanate, phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride, manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisthio- carbamate, the zinc and copper salts of 2-pyridinethiol 1 -oxide, bisdimethyldithio- carbamoylzinc ethylenebisthiocarbamate, zinc oxide, copper(I) ethylene-bisdithio- carbamate, copper thiocyanate, copper naphthenate and tributyltin halides, or substantially to reduce the concentration of these compounds. If appropriate, the ready-to-use antifouling paints may comprise yet further active compounds, preferably algicides, fungicides, herbicides, moUuscicides or other active antifouling compounds.

Prefeπed co-components for the antifouling compositions according to the invention are: algicides such as

2-tert.-butylamino-4-cyclopropylamino-6-methylthio-l,3,5-triazine, dichlorophen, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;

fungicides such as

Cyclohexyl-benzo[b]thiophenecarboxamide S,S-dioxide, dichlofluanid, fluor-folpet, 3-iodo-2-propinyl butylcarbamate, tolylfluanid and azoles such as azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propi- conazole and tebuconazole;

moUuscicides such as fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and trimethacarb; or customary active antifouling compounds such as

4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethyl paratryl sulfone, 2-(N,N- dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinethiol 1 -oxide, pyridine triphenylborane, tetrabutyldistannoxane, 2,3,5,6- tetrachloro-4-(methylsulphonyl)-pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetra- methylthiuram disulphide and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound of the compositions according to the invention in a concentration of from 0.001 to 50% by weight, in particular from 0.01 to 20% by weight.

The antifouling compositions according to the invention furthermore comprise the customary components as described, for example, in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

In addition to the algicidal, fungicidal, molluscicidal and insecticidal active compounds according to the invention, antifouling coating compositions comprise, in particular, binders.

Examples of acknowledged binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system especially in an aqueous system, vinyl chloride/vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene/- styrene/acrylonitrile rubbers, drying oils, such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen, asphalt and also epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.

The coating compositions also optionally include inorganic pigments, organic pigments or dyestuffs, which are preferably insoluble in salt water. The coating compositions may also comprise materials such as rosin, for a controlled release of the active compounds. The coats may also include plasticizers, modifying agents which influence the rheological properties, and other conventional constituents. The compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems.

The active compounds are also suitable for controlling animal pests, in particular insects, arachnids and mites, which are encountered in closed rooms, such as, for example, flats, factory halls, offices, vehicle cabins and the like. They can be used on their own or in combination with other active compounds and auxiliaries in household insecticidal products for controlling these pests. They are active against sensitive and resistant species and against all development stages. These pests include: From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis,

Dermatophagoides pteronissimus, Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer,

Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus, Porcellio scaber. From the order of the Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp..

From the order of the Chilopoda, for example, Geophilus spp..

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp., Reticulitermes spp. From the order of the Psocoptera, for example, Lepinatus spp., Liposcelis spp.

From the order of the Coleptera, for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica,

Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

In the field of the household insecticides, they are used on their own or in combination with other suitable active compounds, such as phosphoric acid esters, carbamates, pyrethroids, growth regulators or active compounds from other known classes of insecticides.

Application is carried out in the form of aerosols, unpressurized sprays, for example pump and atomizer sprays, nebulizers, foggers, foams, gels, vaporizer products with vaporizer tablets made of cellulose or plastic, liquid vaporizers, gel and membrane vaporizers, propeller-operated vaporizers, energyless or passive vaporizer systems, moth papers, moth sachets and moth gels, as granules or dusts, in baits for scattering or bait stations.

The preparation and the use of the active compounds according to the invention is illustrated by the examples below.

Preparation Examples

Example 1 (process 1 or 2)

Taccalonolide N is isolated, for example, by the general process 1, 2 or 3. Taccalonolide N has the following physical data:

LC-MS (ESI neg.): m/z = 601 [M-H]^~

LC-MS (ESI pos.): m/z = 603 [M+H]⁺

HPLC:

R_t = 25.81 min [column material: Lichrospher C18; 5 μm; column dimension: 2 x 125 mm; mobile phase A: water + 25 mmol of NH^OAc; mobile phase B: MeOH + 25 mmol of NI^OAc; gradient: start 20% B; 30 min: 60% B; 31 min: 100% B;

40 min 100%) B; flow rate: 0.4 ml/min; detection at 210 nm) Η NMR data (500 MHz, CDC1₃), see also Figure 1 :

Example 2

Taccalonolide B is isolated, for example, by the general process 1, 2 or 3. Taccalonolide B has the following physical data:

LC-MS (ESI neg.): m/z = 719 [M-H+HOAc]-, 659 [M-H]^", 631 [M-H-CO]^" HPLC:

R_t = 24.51 min [column material: Lichrospher C18; 5 μm; column dimension: 2 x 125 mm; mobile phase A: water + 25 mmol of NK OAc; mobile phase B: MeOH + 25 mmol of NK_tOAc; gradient: start 20% B; 30 min: 60% B; 31 min: 100% B; 40 min 100% B; flow rate: 0.4 ml/min; detection at 210 nm)

1H and ¹³C NMR data, see also Fig. 2:

Example 3

Taccalonolide E is isolated, for example, by the general process 1 or 2. Taccalonolide E has the following physical data:

LC-MS (ESI neg.): m/z = 703 [M-H+HOAc]^", 643 [M-H]^", 601 [M-H-CO₂]^" HPLC:

R_t = 22.96 min [column material: Lichrospher C18; 5 μm; column dimension: 2 x 125 mm; mobile phase A: water + 25 mmol of NH₄OAc; mobile phase B: MeOH + 25 mmol of NI^OAc; gradient: start 20% B; 30 min: 60% B; 31 min: 100% B; 40 min 100% B; flow rate: 0.4 ml min; detection at 210 nm)

1H and ¹³C NMR data, see also Fig. 3:

Example 4

Taccalonolide A is isolated, for example, by the general process 1 or 2. Taccalonolide A has the following physical data:

LC-MS (ESI neg.): m/z = 761 [M-H+HOAc]^", 701 [M-H]^", 659 [M-H-CO₂]^"

HPLC:

R_t = 23.36 min [column material: Lichrospher C18; 5 μm; column dimension: 2 x 125 mm; mobile phase A: water + 25 mmol of NFL_tOAc; mobile phase B: MeOH + 25 mmol of NELjOAc; gradient: start 20% B; 30 min: 60% B; 31 min: 100% B; 40 min 100% B; flow rate: 0.4 ml/min; detection at 210 nm) H and 1¹3^JC NMR data, see also Fig. 4:

Example 5

Process for preparing taccalonolide B from taccalonolide A

At room temperature, 10 mg of taccalonolide A are stiπed in 2 ml of 0.05 molar sodium bicarbonate solution (pH = 8.2) and 1 ml of methanol for 44 h. The solvent is blown off and the residue is extracted three times with 2 ml of diethyl ether each time. Removal of the solvent leaves behind 6.7 mg of taccalonolide B as a colourless solid.

Example 6

Process for preparing taccalonolide N from taccalonolide E

At room temperature, 10 mg of taccalonolide E are stiπed in 2 ml of 0.05 molar sodium bicarbonate solution (pH = 8.2) and 1 ml of methanol for 44 h. The solvent is blown off and the residue is extracted three times with 2 ml of diethyl ether each time. Removal of the solvent leaves behind 6.7 mg of taccalonolide N as a colourless solid.

Example 7

Process for preparing taccalonolides O, Q, R, S and T

The isolation of taccalonolides O, Q, R, S and T can be done according to the isolation of taccalonolides N, B, and A as described in Example 1 - 4.

Example 8

Derivative 15

NaBILt (18 mg, 0.47 mmol) were added to a solution of derivative 16 (18 mg, 0.02 mmol) in methanol (1 mL) and stiπed at room temperature for 7 h. The reaction mixture was diluted with water (10 mL) an extracted with CHC1₃. The organic extracts were washed with brine, dried with sodium sulfate and evaporated to dryness. Chromatography on silica gel using methylene chloride/methanol 97:3 as eluent gave derivative 15 (15 mg, 89 %) as an oil: (-) ESI-MS m/e (relative intensity) 691 [M-H]^" (100).

Example 9

Derivative 16

Ethereal diazomethane was added to a cold (0 °C) stiπed solution of derivative 9

(58 mg, 0.08 mmol) in methanol (5 mL) until the yellow colour of the reagent persisted. The solution was allowed to stand at room temperature overnight.

Evaporation of the solvent and purification on silica gel using ethyl acetate/cyclohexane 1 : 1 as eluent gave derivative 16 (45 mg, 77 %) as an oil: 1H NMR δ 9.68 (d, 7-H), 5.95 (dd, 11-H), 5.25 (d, 12-H), 5.20 (dd, 15-H), 5.08 (d, 22- H), 4.80 (d, 1-H), 3.64 (s, CO₂CH₃), 3.49 (dd, 2-H).

Derivative 17 can be analogously obtained from derivative 14.

Example 10

Derivative 20

To a stirred solution of sodium iodide (31 mg, 0.2 mmol) in anhydrous acetonitrile (1 mL) Me₃SiCl (11 mg, 0.1 mmol) was added dropwise under argon. After 5 min a solution of Taccalonolide A (25 mg, 0.035 mmol) in anhydrous acetonitrile (1 mL) was slowly added. Stirring was continued for 2 h, then 5 N sodium thiosulfate (5 mL) was added and the mixture extracted with ether. The ethereal layers were washed with brine and evaporated. The residual product was purified on silica gel using ethyl acetate/cyclohexane 1 : 1 as eluent to give pure derivative 20 (11 mg, 45 %) as an oil: 'H NMR δ 5.95 (m, 3-H), 5.86 (m, 2-H), 5,56 (dd, 15-H), 5.34 (dd, 11-H), 5.28 (d, 12-H), 5.08 (d, 22-H), 4.83 (d, 1-H), 4.08 (dd, 7-H). (-) ESI-MS m/e (relative intensity) 685 [M-H] (100).

Derivative 19 can be analogously obtained from taccalonolide E.

Table I A

Table I B

Use Examples

Example 1

Meloidogyne test (nematicidal action)

Solvent: 4 parts by weight of acetone Emulsifiers: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifiers, and the concentrate is diluted with water to the desired concentration.

Vessels are filled with sand, a solution of the active compound, Meloidogyne incognita-egg-larvae suspension and lettuce seeds. The lettuce seeds germinate, and the small plants develop. On the roots, the galls develop.

After the desired period of time, the nematicidal action is determined in % by the formation of galls. 100% means that no galls have been found; 0% action means that the number of galls on the treated plants coπesponds to that of the untreated control.

Active compounds, application rates and results are shown in the table below:

Active compound Kill in % at active Constitution compound concentration in ppm

according to the invention: taccalonolides A+E 20 ppm = 100 %

Example 2

Heterakis spumosa test (anthelmintic action)

The experiments were conducted using male mice of the strain SPF/CFW1 having a body weight of 16-18 g. The animals were kept in a Makrolon cage and received water and „Sniff ' rat feed, 13 cm pellets, ad libitum.

Heterakis spumosa eggs of female worms were isolated from the colon of infected mice 35 to 42 days after the infection. The eggs were subsequently incubated at 27°C for 3 weeks. The mice were infected with 90 embryonated H. spumosa eggs orally via a pharyngeal tube. Treatment with the taccalonolide (for the test, the taccalonolide mixture A/E was used) was carried out on day 46 after the infection. To this end, the test substance was dissolved or suspended in the solubilizer „Cremophor EL (0.2 ml), and 0.3 ml of water was then added. 0.5 ml of solution or suspension were then administered orally to the mouse. After a further 8 days, the mouse was sacrificed and the H. spumosa worms were isolated from the caecum/colon region.

Mice which had been infected in the same manner but received only Cremophor

EL/water instead of the taccalonolide served as control.

Evaluation and determination of the anthelmintic activity was carried out in accordance with the publication Plant et al. (1996) Pesticide Science 48, 351-358.

In the in vivo mouse model, the taccalonolide is fully effective against the intestinal nematode Heterakis spumosa when applied once orally at a dose of 100 mg/kg. Example 3

Phaedon larvae test (insecticidal action against plant-damaging insects)

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the mustard beetle (Phaedon cochleariae) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae has been killed.

In this test, for example, the following compound of the preparation examples shows good activity:

Active compounds Active compound Kill in % concentration in ppm after T

according to the invention: taccalonolides A+E 200 100 Example 4

Plutella test (insecticidal action against plant-damaging insects)

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the diamond back moth (Plutella xylostella) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars has been killed.

In this test, for example, the following compound of the preparation examples shows good activity:

Example 5

Spodoptera frugiperda test (insecticidal action against plant-damaging insects)

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the armyworm (Spodoptera frugiperda) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars has been killed.

In this test, for example, the following compound of the preparation examples shows good activity:

Active compounds Active compound Kill in % concentration in ppm after 7^d

according to the invention: taccalonolides A+E 200 100 Example 6

Spodoptera exigua test (insecticidal action against plant-damaging insects)

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of the active compound of the desired concentration and are populated with caterpillars of the armyworm (Spodoptera exigua) while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars has been killed.

In this test, for example, the following compound of the preparation examples shows good activity:

Active compounds Active compound Kill in % concentration in ppm after 7^d

according to the invention: taccalonolides A+E 200 100 Example 7

Heliothis virescens test (insecticidal action against plant-damaging insects)

Solvent: 30 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent emulsifier and the concentrate is diluted with emulsifier-containing water to the desired concentration.

Soja bean shoots (Glycine max) are treated by being dipped into the preparation of active compound of the desired concentration and populated with Heliothis virescens caterpillars while the leaves are still moist.

After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars has been killed.

In this test, for example, the following compound of the preparation examples shows good activity:

Active compounds Active compound Kill in % concentration in ppm after 7^d

according to the invention: taccalonolides A+E 200 100

Claims

Patent Claims

Use of compounds of the general formula (I)

in which

R¹ represents hydroxyl, hydrogen, C₁-C₄-alkoxy, Ci-Cg-alkylcarbonyl- oxy or hydroxyacetoxy,

R² represents hydroxyl, hydrogen, Cι-C₄-alkoxy, Ci-Cg-alkylcarbonyl- oxy or hydroxyacetoxy,

R³ represents hydroxyl, hydrogen, d-C₄-alkoxy, Ci-Cg-alkylcarbonyl- oxy or hydroxyacetoxy,

R represents hydrogen,

R ,5 represents hydrogen, or

R and R together represent a carbon bond,

R represents hydrogen, or R⁵ and R⁶ together with the carbon atom to which they are attached represent a carbonyl group, or

R⁶ and R⁷ together represent the group -OCOC(OH)(CH₃)-, where the oxygen is linked to the carbon atom carrying the R⁶ radical, or

R and R together represent the group -C(OH)(CH₃)COO-, where the carbon atom is linked to the carbon atom carrying the R⁷ radical, or

R⁸ represents hydroxyl, hydrogen, hydroxyacetoxy, C]-C₄-alkoxy, Ci-Cg- alkylcarbonyloxy or doubly attached oxygen,

R⁹ represents hydrogen,

R¹⁰ represents hydrogen, or

R⁹ and R¹⁰ together represent a carbon bond, forming a double bond

R¹¹ represents hydrogen, hydroxyacetoxy, d-C₄-alkoxy, Ci-Cg-alkyl- carbonyloxy or hydroxyl, or

R¹⁰ and R¹¹ together with the carbon atom to which they are attached represent a carbonyl group,

R¹² represents hydroxyl, hydrogen, hydroxyacetoxy, CrC₄-alkoxy, Ci-Cg- alkylcarbonyloxy or doubly attached oxygen, and

R¹³ represents hydroxyl, hydroxyacetoxy, Cι-C₄-alkoxy, Ci-Cg-alkyl- carbonyloxy or hydrogen, R¹⁴ represents hydrogen, hydroxyl, Q-d-alkoxy, Ci-Cg-alkylcarbonyl- oxy or halogen,

R¹⁵ represents hydrogen, hydroxyl, d-C₄-alkoxy, Ci-C^-alkylcarbonyl- oxy or halogen, or

R¹⁴ and R¹⁵ together represent oxygen, thus forming an epoxy group or represent a carbon bond, thus forming a double bond.

and all possible stereoisomeric forms of the compounds of the formula (I) for controlling pests.

2. Use of compounds according to Claim 1 for controlling pests, characterized in that

R¹ represents hydroxyl, methoxy, ethoxy,

or hydrogen,

R² represents hydroxyl, methoxy, hydrogen, acetoxy, ethylcarbonyloxy, n- or i-propylcarbonyloxy, n-, i-, s- or t-butylcarboyloxy or hydroxyacetoxy,

R represents acetoxy, hydroxyl, methoxy or hydrogen,

R represents hydroxyl, methoxy, acetoxy, ethylcarbonyloxy, n- or i- propylcarbonyloxy, n-, i-, s- or t-butylcarboyloxy, hydrogen or doubly attached oxygen,

Rⁿ represents methoxy, acetoxy, ethylcarbonyloxy, n- or i-propyl- carbonyloxy, n-, i-, s- or t-butylcarboyloxy or hydroxyl, R¹² represents acetoxy, hydroxyl, methoxy or doubly attached oxygen,

R¹³ represents hydroxyl, methoxy, acetoxy or hydrogen,

R¹⁴ represents hydrogen, hydroxyl, acetoxy, methoxy or chlorine, and

R¹⁵ represents hydrogen, hydroxyl, acetoxy, methoxy or chlorine.

R¹⁴ andR¹⁵ represent oxygen, thus forming an epoxy group.

3. Use of compounds of the formula (I) according to Claim 1 or 2 for controlling pests, characterized in that

R¹ represents acetoxy, ethylcarbonyloxy, n- or i-propylcarbonyloxy, n-, i-, s- or t-butylcarboyloxy or hydroxyl,

R² represents acetoxy, hydroxyl, hydroxyacetoxy or hydrogen,

R³ represents acetoxy or hydroxyl,

R represents acetoxy, hydroxyl, hydrogen or doubly attached oxygen,

R¹ " represents acetoxy or hydroxyl,

R represents acetoxy, hydroxyl or doubly attached oxygen, and

R¹³ represents acetoxy, hydroxyl or hydrogen.

4. Use of compounds of the formula (I) according to any of Claims 1 to 3 for controlling pests, characterized in that R represents acetoxy, n- or i-propylcarbonyloxy or hydroxyl,

R2 represents acetoxy, hydroxyl or hydrogen,

R8 represents acetoxy or hydroxyl,

R »ιι represents hydroxyl,

R¹² represents hydroxyl or doubly attached oxygen, and

R¹³ represents hydroxyl or hydrogen.

Use of compounds of the formula (II)

for controlling pests,

in which

R and R are as defined in one of Claims 1 to 4.

6. Compounds of the formulae (III A) - (in F)

Use of compounds of the formula (IV)

in which

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹⁴ and R¹⁵ are as defined in one of Claims 1 to

5, and

R , 16 represents hydroxymethyl, formyl, carboxyl or carboxyl methyl ester, R , 17 represents formyl, carboxyl or carboxyl methyl ester, and

R represents hydrogen, acetoxy, hydroxyl or C_.-C₄-alkoxy,

and all possible stereoisomeric forms of the compounds of the formula (IV) for controlling pests.

8. Use of compounds of the formula (LV) according to Claim 7, wherein

R , 18 represents hydrogen, acetoxy, hydroxyl or methoxy.

Use of compounds of the formula (IVA)

for controlling pests.

10. Compounds of the formulae (TV B) - (IV-L)

(IV B)

(IV C)

(IV D)

(IV E)

(IV F)

(IV G)

(IV H)

(IV I)

(IV J)

(IV K)

(IV L)

11. Process for obtaining compounds of the formula (I), (II) and (III A) - (IH F) according to one of Claims 1 to 6, characterized in that

a) comminuted plant material of Tacca spec, is extracted with an optionally water-containing organic solvent, b) the extract is adsorbed on a solid carrier material, c) a vacuum liquid chromatography is carried out, d) a liquid-liquid partition is then carried out, and e) a liquid-chromatographic purification is carried out.

12. Process for obtaining compounds of the formula (I), (II) and (III A) - (III F) according to one of Claims 1 - 6, characterized in that

a) comminuted plant material of Tacca spec, is extracted with an optionally water-containing organic solvent, b) the extract is taken up in solvent-containing water, c) this mixture is extracted successively with water-immiscible solvents of increasing polarity, and d) a liquid-chromatographic purification is carried out.

13. Process for derivatizing taccalonolides from other taccalonolides, characterized in that taccalonolides are stiπed in weak alkaline solution.

14. Pesticides, characterized in that they comprise at least one of the compounds of the formula (I), (π), (in A) - (III F), (IV) or (IVA) - (IV L) according to one of Claims 1 to 9.

15. Pesticides comprising an extract of Tacca spec, which comprises at least one of the compounds of the formula (I), (π) or (in A) - (III F) according to one of Claims 1 to 6.

16. Pesticide comprising comminuted plant material of Tacca spec, characterized in that it comprises at least one of the compounds of the formulae (I), (Tl) or (πi A) - (III F) according to one of Claims 1 to 6.

17. Method for controlling pests, characterized in that compounds of the formulae

(I), (II), (III A) - (III F), (IV) or (IVA) - (IV L) according to one of Claims 1 to 10 are allowed to act on pests and/or their habitat.

18. Method for controlling pests, characterized in that extracts of Tacca spec. according to Claim 15 are allowed to act on pests and/or their habitat.

19. Process for preparing pesticides, characterized in that at least one of the compounds of the formula (I), (II), (III A) - (in F), (IV) or (IVA) - (IV L) according to one of Claims 1 to 10 is mixed with extenders and/or surfactants