Sex pheromone of **Plutella xylostella**

Abstract

To provide a composition that selectively attracts males of Spodoptera frugiperda.SOLUTION: The present invention provides a composition for attracting males of Spodoptera frugiperda and / or disrupting communication between males and females of Spodoptera frugiperda. This composition comprises (Z)-9-tetradecenyl acetate (Z9-14Ac), (Z)-7-dodecenyl acetate (Z7-12Ac), and (Z, E)-9,12-tetradecadienyl acetate (Z9E12-14Ac).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an attractant for male adults of Spodoptera frugiperda, and more specifically, to a composition for attracting male Spodoptera frugiperda, a composition for disturbing communication between male and female Spodoptera frugiperda, Loxostege sticticalis a composition for enhancing the attracting effect of an attractant for male, Loxostege sticticalis a capturing device for male, Loxostege sticticalis a method for attracting male, and Loxostege sticticalis a method for disturbing communication between male and female.

Background Art

[0002] Spodoptera frugiperda is considered to be native to Central and South America and is a pest native to Central and South America that damages various plants mainly in the Gramineae family such as corn and sugarcane. In recent years, its distribution range has been expanding globally, and its invasion was first confirmed in Japan in 2019. It is a pest with high flying ability, and damage is caused by adult insects flying in from home and abroad on air currents and laying eggs. Therefore, in order to predict and minimize the damage, it is necessary to accurately grasp its flight and occurrence.

[0003] As a means of monitoring the flight and occurrence of pests, traps using attractants such as sex pheromones are used. A sex pheromone is generally a chemical substance secreted by female adults and shows a species-specific and strong attracting effect on male adults of the same species. Therefore, if the chemical structure of the sex pheromone can be clarified and synthesized industrially to supply sex pheromone traps, the occurrence survey of pests can be carried out efficiently and simply (for example, Patent Document 1). It is also known that synthetic sex pheromones can be used as a preparation for disturbing information communication related to mating between male and female (for example, Patent Document 2), and pesticide registration is also in progress.

[0004] As sex pheromone components produced by female adults of Mythimna separata, (Z)-9-tetradecenyl acetate (Z9-14Ac), (Z)-7-dodecenyl acetate (Z7-12Ac), (Z)-11-hexadecenyl acetate (Z11-16Ac), and (Z)-9-dodecenyl acetate (Z9-12Ac) have been identified (for example, Non-Patent Document 1). Among these, even a mixture of only two components, Z9-14Ac and Z7-12Ac, can attract male adults, but a mixture containing all four of the above components has a higher attractiveness (for example, Non-Patent Document 2). However, in sex pheromone traps using a formulation containing the above four components as an attractant source, moths of the genera Mythimuna and Leucania are often misattracted (for example, Non-Patent Document 2), and in particular, it is known that Mythimna loreyi is mixed in (for example, Non-Patent Document 3). The mixing of different species significantly reduces the working efficiency of the occurrence survey using pheromone traps.

[0005] In addition, Non-Patent Documents 4 and 5 describe that synthetic (Z,E)-9,12-tetradecadienyl acetate (Z9E12-14Ac) was used in combination with Z9-14Ac for attracting male Mythimna separata, but it is not described that Z9E12-14Ac is secreted from female Mythimna separata, and the attractiveness (cross-activity) to Mythimna loreyi is also not described.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0007]

Non-Patent Document 1

Non-Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0008] If the male of Spodoptera cosmioides can be selectively attracted and the misattraction of Spodoptera litura can be suppressed, Spodoptera cosmioides can be efficiently monitored and controlled. Therefore, an object of the present invention is to provide a composition that selectively attracts male Spodoptera cosmioides.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors detected and identified trace amounts of Z9E12-14Ac from the sex pheromone gland extract of female adult Spodoptera cosmioides, and found that this compound enhances the attractiveness of male adult Spodoptera cosmioides by known sex pheromones and suppresses the misattraction of Spodoptera litura, thereby completing the present invention. That is, the present invention provides the following composition, trapping device, and method. [1] (Z)-9-tetradecenyl acetate (Z9-14Ac), (Z)-7-dodecenyl acetate (Z7-12Ac), (Z,E)-9,12-tetradecadienyl acetate (Z9E12-14Ac) and Loxostege sticticalis a composition for attracting males of Loxostege sticticalis and / or disturbing male-female communication of 〔2〕The content ratio of Z9-14Ac and Z9E12-14Ac is 1:0.2×10 -5 ~0.02 by mass, or The content ratios of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac are 1:0.1×10 -2 ~0.1:0.2×10 -5 ~0.02 by mass, The composition according to the above (1). 〔3〕The composition according to the above (2), further comprising (Z)-11-hexadecenyl acetate (Z11-16Ac) and / or (Z)-9-dodecenyl acetate (Z9-12Ac). 〔4〕The composition according to the above (1), further comprising Z11-16Ac and / or Z9-12Ac. 〔5〕The composition according to any one of the above (1) to (4), wherein the composition is in the form of a solution or an emulsion, or is in a form impregnated in a sustained-release carrier. 〔6〕 Loxostege sticticalis A composition containing Z9E12-14Ac for enhancing the attracting effect of the male attractant of wherein the attractant contains Z9-14Ac and Z7-12Ac. 〔7〕The composition according to the above (6), wherein the attractant further contains Z11-16Ac and / or Z9-12Ac. 〔8〕A male capture device containing Z9-14Ac, Z7-12Ac, and Z9E12-14Ac. Loxostege sticticalis 〔9〕The capture device according to the above (8), further comprising Z11-16Ac and / or Z9-12Ac. 〔10〕A method for attracting male of Loxostege sticticalis or disturbing the communication between male and female of Loxostege sticticalis including the step of applying a composition containing Z9-14Ac, Z7-12Ac, and Z9E12-14Ac to a place for attracting male of Loxostege sticticalis 〔11〕The method according to the above (10), wherein the composition further contains Z11-16Ac and / or Z9-12Ac.

Advantages of the Invention

[0010] According to the present invention, by using Z9E12-14Ac in combination with Z9-14Ac and Z7-12Ac, the attractiveness and species selectivity of male adults of Plutella xylostella can be improved. Therefore, it becomes possible to efficiently monitor and control Plutella xylostella.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, the present invention will be described in more detail. The composition of the present invention is (Z)-9-tetradecenyl acetate (Z9-14Ac), (Z)-7-dodecenyl acetate (Z7-12Ac), (Z,E)-9,12-tetradecadienyl acetate (Z9E12-14Ac) and contains. These compounds (hereinafter, the three compounds are collectively referred to as "core compounds") are components contained in the sex pheromone gland extract of female adults of the pest Loxostege sticticalis and function as sex pheromones released by the female adults. Therefore, the composition of the present invention can be used to attract Loxostege sticticalis males. Therefore, the composition can be used for the investigation of the occurrence of Plutella xylostella or for attracting and capturing (or attracting and killing).

[0012] In addition, if the sex pheromone released by female Plutella xylostella is artificially filled in its habitat or a place where its presence is suspected, male Plutella xylostella cannot distinguish the true habitat of the female and cannot reach the female. Therefore, the composition of the present invention can also be used to disrupt the communication between male and female Plutella xylostella.

[0013] The content ratio of the above core compounds is Loxostege sticticalis as long as it can attract males of Loxostege sticticalis or disrupt the communication between male and female of-5 ~ may be about 0.02, preferably about 1: about 0.1×10 -3 ~ about 0.01. Alternatively, the content ratios of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac are about 1: about 0.1×10 -2 ~ about 0.1: about 0.2×10 -5 ~ may be about 0.02, preferably about 1: about 0.5×10 -2 ~ about 0.05: about 0.1×10 -3 ~ about 0.01.

[0014] In one aspect, the composition of the present invention further comprises (Z)-11-hexadecenyl acetate (Z11-16Ac) and / or (Z)-9-dodecenyl acetate (Z9-12Ac). These additional compounds are also Loxostege sticticalis components contained in the sex pheromone gland extract of female adults of, and function as sex pheromones released by the female adults. The content ratio of the additional compound is not particularly limited. For example, the content ratio of Z9-14Ac and Z11-16Ac may be about 1: about 0.5×10 -2 ~ about 1, and the content ratio of Z9-14Ac and Z9-12Ac may be about 1: about 0.5×10 -3 ~ about 0.05.

[0015] In one aspect, the composition of the present invention further comprises an organic solvent. As the organic solvent, those commonly used in the art can be adopted without particular limitation. For example, the organic solvent may be a hydrocarbon-based organic solvent such as pentane and hexane.

[0016] In one aspect, the composition of the present invention is in the form of a solution or an emulsion. The total concentration of the core compound in the composition of the present invention is not particularly limited as long as the intended effect is achieved. For example, when the purpose is to investigate the occurrence of the beet armyworm or to attract and capture (or attract and kill) it, it may be about 0.001 to about 100.0 mg / mL, preferably about 0.01 to about 10 mg / mL. When disturbing the communication between male and female beet armyworms, the total concentration of the core compound in the composition of the present invention may be, for example, about 0.1 to about 1000 mg / mL, preferably about 0.5 to about 500 mg / mL.

[0017] In one aspect, the composition of the present invention is in the form of being impregnated in a sustained-release carrier. As the sustained-release carrier, those commonly used in the art can be adopted without particular limitation. For example, the sustained-release carrier may be a container such as a cap (septum), a capillary tube, a laminated bag, and a capsule made of a material having a release amount control function such as rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, and polyvinyl chloride. Preferably, it is a septum or a capillary tube made of rubber or polyethylene.

[0018] The total impregnation amount of the core compound per the sustained-release carrier is not particularly limited as long as the intended effect is achieved. For example, when the purpose is to investigate the occurrence of the beet armyworm or to attract and capture (or attract and kill) it, it may be about 0.0001 to about 100 mg per about 1 cm 3 of the sustained-release carrier, preferably about 0.001 to about 10 mg. When disturbing the communication between male and female beet armyworms, the total impregnation amount of the core compound per the sustained-release carrier may be, for example, about 1.0 to about 1000 mg, preferably about 50 to about 500 mg.

[0019] The sustained-release carrier can be used in combination with (attached to) a trap for capturing pests. As the trap, those commonly used in the art can be adopted without particular limitation. For example, the trap may be an adhesive trap, a water pan trap, a suction trap, etc., and preferably an adhesive trap. The number of the sustained-release carriers attached to the trap is not particularly limited and may be appropriately adjusted according to the respective sizes and usage purposes. For example, about 1 to about 10 sustained-release carriers may be attached to the trap.

[0020] The composition of the present invention, particularly the composition in the form of being impregnated in the sustained-release carrier, may be installed outdoors. The installation density of the sustained-release carrier outdoors is not particularly limited. For example, when using 1 sustained-release carrier attached to the trap for the purpose of investigating the occurrence or attracting and capturing (or attracting and killing) of Spodoptera litura, it may be about 1 to about 1000 per 10 ares, preferably about 10 to about 500. The interval between the sustained-release carriers is not particularly limited. For example, it may be about 1 to about 100 m, preferably about 5 to about 15 m. When disturbing the communication between male and female of Spodoptera litura, the installation density of the sustained-release carrier outdoors may be, for example, about 50 to about 500 per 10 ares, and the interval between the sustained-release carriers may be, for example, about 0.5 to 100 m, preferably about 1.4 to about 10 m.

[0021] The installation position of the composition of the present invention, particularly the composition in the form of being impregnated in the sustained-release carrier, is not particularly limited. For example, it may be at a height of about 10 to about 200 cm above the ground, preferably at a height of about 30 to about 160 cm. Also, the installation time of the composition is not particularly limited. For example, it may be installed during the flying period of the adults of Spodoptera litura.

[0022] In one aspect, the composition of the present invention is in a form impregnated in agricultural materials such as nets and ropes or horticultural materials. If the materials impregnated with the composition of the present invention are widely installed in the field, it is particularly useful for disturbing the communication between male and female Spodoptera litura. The method of impregnating the materials is not particularly limited. For example, the composition in a solution state may be impregnated by spraying or applying it to the materials. The amount of the core compound to be sprayed or applied is not particularly limited as long as the intended effect is achieved. For example, when disturbing the communication between male and female Spodoptera litura, the total amount of the core compound impregnated in the materials when installed in the field may be an amount such that it is about 2.5 to about 250 g per are.

[0023] The composition of the present invention may further contain any excipients and / or additives commonly used in the art as long as the object of the present invention is not impaired, and may further contain other active ingredients that attract moths, and / or other active ingredients that disturb the communication between male and female moths.

[0024] In another aspect, the present invention Loxostege sticticalis also relates to a composition containing Z9E12-14Ac for enhancing the attracting effect of the attractant for male [species name]. The attractant contains Z9-14Ac and Z7-12Ac, and may optionally further contain Z11-16Ac and / or Z9-12Ac. Z9E12-14Ac can selectively enhance the attractiveness of male [species name] without misattracting male Spodoptera exigua. The usage ratio of each compound is not particularly limited, Loxostege sticticalis and is as described above for the content ratio of each compound in the composition for attracting male [species name] or the composition for disturbing the communication between male and female [species name]. Loxostege sticticalis the composition for attracting male [species name] or Loxostege sticticalis the composition for disturbing the communication between male and female [species name].

[0025] In another aspect, the present invention relates to a composition containing Z9-14Ac, Z7-12Ac, and Z9E12-14Ac, Loxostege sticticalisIt also relates to a male trapping device. The trapping device can be used for the occurrence investigation or attraction trapping (or attraction killing) of the diamondback moth. The content ratios of the above three compounds are not particularly limited and are as described above for the composition of the present invention.

[0026] In one aspect, the trapping device of the present invention may further include the above-mentioned sustained-release carrier and / or the above-mentioned trap. The installation time of the trapping device of the present invention is not particularly limited. For example, it may be installed during the flying period of the adult diamondback moth. Also, in one aspect, the trapping device of the present invention further contains Z11-16Ac and / or Z9-12Ac. The content ratios of these additional compounds are not particularly limited and are as described above for the composition of the present invention.

[0027] In another aspect, the present invention relates to a method including the step of applying a composition containing Z9-14Ac, Z7-12Ac, and Z9E12-14Ac Loxostege sticticalis to a place for attracting males of Loxostege sticticalis or a method for disturbing the communication between males and females of Loxostege sticticalis . The composition used in the method of the present invention is the same as that described above for the composition of the present invention. The application method of the composition is not particularly limited. For example, it may be diluted in a solvent capable of uniformly dispersing the composition and sprayed at the target location, or the composition may be impregnated into the above-mentioned sustained-release carrier and installed at the target location.

[0028] Hereinafter, the present invention will be specifically described by way of examples, but the scope of the present invention is not limited to these examples.

Examples

[0029] 1. Analysis of the sex pheromone gland extract of female adult diamondback moths Adult female moths of the pink bollworm that had emerged were isolated from the adult males and fed a 10% aqueous honey solution at 23°C. The lighting in the rearing room was turned on at 6:00 am and turned off at 10:00 pm. Between 11:00 pm and 12:00 am on the 2nd to 4th days after emergence, the abdominal terminal segments containing the sex pheromone glands of 112 adult female moths were excised. These were immersed in approximately 4 mL of hexane for 30 minutes and then filtered to obtain a crude extract.

[0030] The obtained crude extract was concentrated to approximately 0.03 mL using a rotary evaporator and injected into a column chromatograph packed with silica gel (0.2 g). Then, hexane containing 0, 5, 15, or 50% diethyl ether was fractionated and eluted using 2 mL each time.

[0031] Tridecyl acetate (20 ng) was added as an internal standard substance to the 5% diethyl ether fraction, and it was reconcentrated to approximately 0.1 mL using a rotary evaporator. Of this, 0.003 mL was analyzed using a gas chromatograph - mass spectrometer (manufactured by Agilent Technologies) equipped with a DB - WAX column (inner diameter 0.25 mm, length 30 m). When analyzed under the condition of raising the temperature in the column oven from an initial temperature of 60°C (held for 1 minute) to 230°C at a rate of 10°C per minute, the known sex pheromone components Z9 - 14Ac, Z7 - 12Ac, Z11 - 16Ac, and Z9 - 12Ac were detected at 18.0 minutes, 15.4 minutes, 20.3 minutes, and 15.6 minutes, respectively. Furthermore, a trace component having an EI mass spectrum similar to these components was detected at 18.9 minutes. The content ratio of this trace component was approximately 0.2% in terms of the peak area ratio of the gas chromatogram with respect to Z9 - 14Ac, which had the highest content.

[0032] The EI mass spectrum [m / z (relative intensity%)] of the above - mentioned trace component was as follows. 43 (92.9), 55 (60.7), 67 (100), 81 (95.0), 95 (56.8), 107 (19.2), 121 (26.0), 135 (16.7), 149 (8.5), 163 (3.3), 192 (12.8), 252 (1.0) Since the spectrum and retention time in gas chromatography matched those of synthetic Z9E12-14Ac, the trace component was identified as Z9E12-14Ac.

[0033] 2. Attraction test 1 A 0.2 mL hexane solution (attractant) was prepared by mixing several compounds among Z9-14Ac, Z7-12Ac, Z11-16Ac, Z9-12Ac, and Z9E12-14Ac, and this attractant was impregnated into a rubber septum (test groups A to E). Then, one such rubber septum was attached as an attraction source to a commercially available SE trap (adhesive board; 24 cm × 30 cm) to fabricate a capture device. Fifteen of these capture devices were each installed outdoors and left for one week, and the numbers of male adults of Ostrinia furnacalis and male adults of Ostrinia scapulalis captured were counted. This test was repeated 6 times for 9 of the capture devices and 21 times for 6 of them. The composition (content of the above compounds) of each attractant and the results are shown in Table 1.

[0034]

Table 1

[0035] The conventional attractant containing Z9-14Ac, Z7-12Ac, Z11-16Ac, and Z9-12Ac (test group A) attracted more Ostrinia furnacalis than the attractant containing Z9-14Ac and Z7-12Ac (test group B), but at the same time, it also misattracted Ostrinia scapulalis. In contrast, as can be understood from the comparison between test group B and test group D, when Z9E12-14Ac was added, it was possible to improve only the attractiveness of Ostrinia furnacalis without increasing the attractiveness of Ostrinia scapulalis. Also, when comparing test group A and test group C, it was found that the addition of Z9E12-14Ac suppressed the attractiveness of Ostrinia scapulalis but increased the attractiveness of Ostrinia furnacalis.

[0036] 3. Attraction test 2 A trapping device was fabricated in the same manner as in Attraction Test 1, except that the attractants for Test Group D and attractants with different Z9E12-14Ac contents (Test Groups F to H) were used. Six of these trapping devices were installed outdoors and left for one week, and the test of measuring the number of male adults of Plutella xylostella and male adults of Agrotis segetum captured was repeated 8 times. The composition and results of each attractant are shown in Table 2.

[0037]

Table 2

[0038] In any of the test groups, Plutella xylostella could be attracted, and the misattraction of Agrotis segetum was suppressed. In particular, when the content of Z9E12-14Ac was 0.2% with respect to the content of Z9-14Ac, the attractiveness to Plutella xylostella was significantly high.

[0039] 4. Attraction Test 3 To confirm the contribution of each compound contained in the attractant, the attractiveness of the attractants of Test Groups B, D, and E, the attractant containing Z9-14Ac (Test Group I), and the attractant containing Z9-14Ac and Z9E12-14Ac (Test Group J) to Plutella xylostella was investigated using a wind tunnel in the laboratory. Specifically, air was flowed at a constant wind speed (0.25 cm per second) in a wind tunnel (length 66 cm × diameter 11.5 cm) installed in the laboratory, and one rubber septum impregnated with each attractant was placed as an attraction source on the upwind side, and the flight behavior was observed when male adults of Plutella xylostella were released on the downwind side. The composition and results of each attractant are shown in Table 3.

[0040]

Table 3

[0041] Compared with the attractant of the negative control containing no compound (test group E), the upwind flight behavior was significantly activated only by the attractants containing the core compounds of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac (test group D). Among them, the upwind flight behavior was not significantly activated by combining only two of these components. The attractant of test group B attracted a certain number of Spodoptera litura in the outdoor attraction test 1, but in the wind tunnel test conducted in a limited space under the laboratory, it could not show a statistically significant difference compared with the reaction to the negative control (test group E), which was considered to be the result of random flight behavior. Despite such limitations, when the above core compounds were used simultaneously, a significant difference was observed in the attraction activity of male adults of Spodoptera litura. Therefore, the attraction effect of the combination of the three compounds constituting the core compound is remarkable and cannot be predicted from the prior art. In other words, it can be said that Z9E12-14Ac can significantly enhance the attraction effect of the attractant containing Z9-14Ac and Z7-12Ac.

[0042] From the above, it was found that by combining Z9E12-14Ac with Z9-14Ac and Z7-12Ac, the attractiveness and species selectivity of male adults of Spodoptera litura can be improved. Therefore, it becomes possible to efficiently monitor and control Spodoptera litura.

Claims

1. (Z)-9-tetradecenyl acetate (Z9-14Ac), (Z)-7-dodecenyl acetate (Z7-12Ac), (Z,E)-9,12-tetradecadienyl acetate (Z9E12-14Ac) and The content ratio of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac is 1:0.1×10-2 to 0.1:0.2×10-5 to 0.02 by mass ratio; A composition for attracting male fall armyworms and / or disrupting male-female mating of fall armyworms.

2. The content ratio of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac is 1:0.5×10-2 to 0.05:0.1×10-3 to 0.01 by mass ratio, The composition of claim 1.

3. The composition of claim 2, further comprising (Z)-11-hexadecenyl acetate (Z11-16Ac) and / or (Z)-9-dodecenyl acetate (Z9-12Ac).

4. The composition of claim 1 further comprising Z11-16Ac and / or Z9-12Ac.

5. The composition according to any one of claims 1 to 4, wherein the composition is in the form of a solution or emulsion, or is in the form of being impregnated in a sustained release carrier.

6. A composition for enhancing the attractant effect of an attractant for males of the fall armyworm, comprising Z9E12-14Ac, The attractant comprises Z9-14Ac and Z7-12Ac; and The composition, wherein the amount of Z9E12-14Ac relative to the attractant is such that the content ratio of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac is 1:0.1×10 −2 to 0.1:0.2×10 −5 to 0.02 by mass. **Claim 7**: The composition according to claim 6, wherein the amount of Z9E12-14Ac relative to the attractant is such that the content ratios of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac are 1:0.5×10-2 to 0.05:0.1×10-3 to 0.01 by mass ratio. **Claim 8** The composition according to claim 6 or 7, wherein the attractant further contains Z11-16Ac and / or Z9-12Ac. **Claim 9** A capturing device for male Plutella xylostella, comprising Z9-14Ac, Z7-12Ac, and Z9E12-14Ac, wherein the content ratios of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac are 1:0.1×10-2 to 0.1:0.2×10-5 to 0.02 by mass ratio. **Claim 10**: The capturing device according to claim 9, wherein the content ratios of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac are 1:0.5×10-2 to 0.05:0.1×10-3 to 0.01 by mass ratio. **Claim 11** The capturing device according to claim 9 or 10, further comprising Z11-16Ac and / or Z9-12Ac. **Claim 12** A method for attracting male Plutella xylostella or disturbing the communication between male and female Plutella xylostella, comprising the step of applying a composition containing Z9-14Ac, Z7-12Ac, and Z9E12-14Ac to a place for attracting male Plutella xylostella, wherein the content ratios of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac in the composition are 1:0.1×10-2 to 0.1:0.2×10-5 to 0.02 by mass ratio. **Claim 13**: The method according to claim 12, wherein the content ratios of Z9-14Ac, Z7-12Ac, and Z9E12-14Ac in the composition are 1:0.5×10-2 to 0.05:0.1×10-3 to 0.01 by mass ratio. **Claim 14** The method according to claim 12 or 13, wherein the composition further comprises Z11-16Ac and / or Z9-12Ac.

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