DESCRIPTION Technical field The present invention relates to a composition comprising a gnawing inhibiting compound intended to be applied on conifer saplings, in particulr pine saplings in order to prevent pine weevil to attach the young stem, as well as gnawing inhibiting compounds.

The object of the present invention is to obtain a composition intended to be applied on conifer saplings in order to prevent damages caused by gnawing on the young plant stem caused by pine weevil (Hylobius abietis).

Background of the invention The pine weevil is the pest insect causing the most serious damages in Swedish forestry. Without any treatment of the newly planted pine and spruce saplings up to 80% of these young saplings can become killed by the weevil gnawing for feeding itself on the cortex. An estimated yearly cost of these damages is 0.5 to 2 billion Swedish Crowns only in Sweden depending on the amount and the concentration of weevils.

Today the saplings are protected using permethrin, a pyrethroid which is allowed for use on exemption up to 1999, inclusive, for different types of plants. Permethrin prevents the weevil to gnaw the cortex of the saplings. Pemethrin is, however, an environmental poisson having a high toxicity to aquatic organisms.

Normally, insects prefer to feed on one or a few plant species. The selection is often controlled by scent and taste substances. The positive ones, i. e. those that tempt gnawing are called stimulants, the negative ones, i. e. those that deter from gnawing are called"antifeedants".

The weevil is polyphag, i. e. it can feed on a number of plants species on a clearing but prefer conifer cortex. If one could direct the weevil away from the conifers large amounts of or large concentrations of weevil will not play any essential role.

The weevil is an insect living on the soil surface where it looks for feed gnaw. Normally, it does not climb the young saplings but gnawing takes place within the area, which the weevil reaches on the stem-and around the same-from the soil surface.

Another way of inhibiting the gnawing is to treat the plants using a wax. This means a mere mechanical protection. However, the wax is difficult to apply as it is required that the wax is liquid which leads to increased temperatures which in turn can be a risk to the young saplings..

Other mechanical protections, which have been proposed, are latex and different types of casings or tubes of polymers. All mechanical protections, however, suffer from the drawback that they require a complicated application and are connected with high costs.

In a number of plant-insect systems specific gnawing inhibitors have been described as an indispensable part of the natural defence provided by the plant. The most well known example is the tree Azadiractica indica, which was early known as active against many insects. More variants are available today and an extract of the seed capsules of the tree ("neem oil") is used in green houses.

Neem oil is, however, not equally active against all insects and has turned out to have a limited effect against Hylobius abietis and H. pales.

Anti gnawing agents have been proposed in order to prevent or inhibit the feed gnaw by weevils. The desire is hereby that the protection to the conifer saplings shall rest at least two seasons, until the young sapling has obtained a cortex thick enough to stand an attack. The requirements on such anti gnawing agents are that they shall be low volatile, have a high stability at temperatures of up to 70oC and to W-light as well as have a low toxicity to humans and animals.

A model compound which has been tested is carvon, which has turned out to be efficient against the weevil by inhibiting the feed gnaw. It has, however, turned out that the gnawing inhibiting effect is of short duration if the compound is brushed directly onto he sapling. The reason is that carvone is volatile at low temperatures and thus evaporates away from the saplings treated

Thus a problem exists to solve, viz. to obtain gnawing inhibiting compounds and then not only carvone, to remain on a treated saplings during two or more growing seasons and thereby stand climate strains such as precipitation, cold, heat and sun light (UV-light).

Description of the present invention It has now turned out possible to be able to solve this problem by means of the present invention which is characterized in that the gnawing inhibiting compound is present in a bound form to a substance of the group of zeolites, cyclodextrines, homogenous porous microspheres, spherical vesicles, hollow fibres, such as textile fibres (wool) capillaries of synthetic material (polymers), starch, and polymer films, optionally in combination with a carrier and/or adhering agent, whereby the gnawing inhibiting compound is present in an amount of 1 to 10 % by weight.

Further characteristics are evident from the accompanying claims.

By means of the present invention it is obtained that the gnawing inhibiting compound can be efficiently bound to the young sapling for a considerable time, such as two to three seasons. This means that the antagonistic compound, a gnawing inhibitor, is enclosed more or less in a tight casing.

With bound form is meant above, that the active compound is physically bound to the polymer or another substance according to the group above, either by a binding in or by inclusion. At zeolites the active compound is absorbed in to the zeolite skeleton, at cyclodextrine the active compound is bound or enclosed at a molecular level, at homogenous porous microspheres the active compound is present enclosed in a polymer casing (example of such microspheres is Dynospheres T-12). Dynospheres are compact particles manufactured of 98% of polystyrene, and 2% of divinyl benzene as a cross-linking agent and having a density of 1.05 g/cm3. At vesicles the active compound is enclosed in a casing.

Spherical vesicles can consist of spherical polymer particles, whereby the microspheres consist of a polymer shell which encloses a gas which gas at heating allows the polymer shell to expand more than 40 times and thereby allows enclosure of liquid or solid compound. Phospholipid vesicles can also be suitable as carrier of the active compound whereby the vesicles being filled with active compound are slurried in an aqueous phase such as a suspension provided with latex, where the latex has a binding capability to the treated sapling.

In the actual microspheres or vesicles the amount of active compound is very high and can be up to 90% by weight, more commonly up to 50 % by weight. In a formulation ready-to-use in composition being sprayable or brushable the active compound is normally 1 to 10 % by weight, but can reach 10 to 20 % by weight.

Test carried out shows that a micro-encapsulation having a diameter of 200 llm is eaten by the weevil and can pass the gastro-intestinal tract.

At use the composition is slurried in an aqueous medium ad is sprayed onto the saplings, alternatively the saplings can be dipped in such a slurry. Normally it is preferred spraying of the parts of the stem subject to the attack of the weevil in order to minimise the amount of foreign material on the plant, and to minimise the amount of active compound and binding polymer from a cost and environmental point of view.

The aqueous medium may suitably be provided with a latex emulsion, which has a binding ability to the stems of the young saplings in such a way that the active compound in its combination remains on the stem.

The active compound can also be oil bound such as bound in linseed oil, in particular raw linseed oil, which hardens or also in so called boiled linseed oil.

The antagonistic compound can also be incorporated in a polymer laminate which is wound around the conifer sapling, whereby, when the weevil bites through the outermost film meets the antagonistic compound and is restrained from further gnawing attempts in the area of the first bite. Encapsulation of active compound can thereby be carried out in simple way by having a layer of the laminate being provided with the active compound whereupon a second covering layer is added to the first layer and is adhered or heat sealed thereto. One of the layers can thereby have an adhering layer for the adhesion to a substrate such as the actual conifer sapling.

With active compound is meant herein every gnawing inhibiting compound that inhibits the feed gnaw of the weevil.

The present invention further relates to active, gnawing inhibiting compounds according to the set up below comprising three different basic structures.

Compound type I R1,R2 = O (epoxide) R1 = OH, OCH3, OCaHs or OCO (CH2) nCH3, wherein n = 0-3 R2 = H or, (CH2)nCH3, wherein n is 0 to 8, or Compound type II Rl = H or alkyl R2 can each independently be methoxy and/or two R2 groups in neighbouring positions can be together methylene dioxy. The n substituents can be localized in positions 1,2,3, and/or 4 n = 1 2,3, and/or 4 X = O, S, orNR3 R3 = either methyl, ethyl, isopropyl and/or butyl localized in positions 1,2 and/or 3 m= 1, 2 or 3 Compound type III 1X can be OH or CHO @R1, R2, R3, R4, R5 can each independently or simultaneously be H, methyl, ethyl, propyl, isopropyl, n-butyl, tert.-butyl, n-pentyl, or allyl, 3,3-dimethylallyl, or 1-propenyl, Rl, R2 can be the linking chain -CO-CH=CH-CO-;R1, R2, R3, R4 and/or R5 can be each independently o : simultaneously be OR", wherein R6 is H, methyl, ethyl, propyl and/or isopropyl; R'and R2, P and R3, R3 and R4, or R4 and 5 can, in pair, carry each their oxygen which are linked by a methylene bridge (viz.-O-CH-O- Compound type I Examples : Cn-epox DHCnOH B2

B34 Compound type II Examples: H H OCH3 #56 CE8 O O O w H I W \ oCHC3H3 H3CO CH3 Y CH3 OCH3 OCH3 #54 CE7 CE10 O O OCH 3 o O ° W H H3CO CH3 H cl3 H3CO CH3 H3CO CH3 Y CH3 H3C0 OCH3 CE11 CE14 0 o Lu ruz O CH3 O O O '- CHs" CHs-CHs 0 0 0 #40 #55 Compound type III Examples: INDEX OF SUBSTANCES Structure Code name Soruce* AFI / ED 50 Compound type I E DHCnOH Synthesis 0.96 2.0 HOt no- Cn-epox Synthesis 1. 000. 52 » B2 Synthesis 0.82 O. xx Zu B34 Synthesis 0.59 " HC Compound type II #40 Synthesis 1. 00 Ou chu HO #54 Synthesis 1. 00 Me -OMe #55Synthesis0. 77 CE 14 Synthesis 0. 84 Mye MEON OMe Mer B5 alt. CE7 Synthesis l. 00 Mu CE8 Synthesis 1. 00 OMe , o CE10 Synthesis 0. 94 OMe OMe CE1 1 Synthesis 1. 00 Chu Me mye Compound type in OH #3 Commercial 1. 00 i 39, 082-8 #8 Commercial 1. 00 Me 16, 737-1 p. e #14 Commercial 0.74 MeQ. .. CHO Me », CHO 14,375-8 OH #18 Commercial 0. 74 'U"D4, 740-4 #19 Synthesis 0. 42 OH #22 Commercial 0. 87 E5, 179-1 #45 Commercial 1. 00 p ho P4,910-4. OH #47 Synthesis 0. 94 C OH » #51 Commercial 0. 83 T7, 650-3 OH cue Bll Commercial 1.00 me 10,962-2 *The commercial chemicals are bought from Aldrich. Denominations are their catalogue numbers from the 2000-2001 catalogue.

AFI in the table above has been determined in accordance with the following.

In order fulfil the need for testing small amounts of synthetic compounds and extracts a micro feeding test was developed. Alternative substrates for testing of gnawing inhibiting compounds with regard to weevil, Hylobius abietis, was searched for, as host plant-twigtest consumes too large amounts of compound for routine testing of series of synthetic compounds or extracts or their fractions.

Furthermore, the twig cortex consumption a long time for exposure and determination.

A simple set-up consisting of 5 x 5 mm pieces of thin layer chromatography plates was made. They were used in pair for the choice of biotest, attached to a strip of double adhesive tape in a 9 cm Petri dish. After application of 1.5 1 of 10 % solutions and evaporation of the solvent, each plate obtained a 5 gl amount of 1 M of succrose in water as feeding stimulant. A 1 day starvation which is enough for the twig test replaced a 6-7 days of starvation which gave a significant death prior to or after the test.

The test period is 4 hrs, the plates and the animals were kept at +25°C, 65% RH, 2000 lux and 20: 4 light: dark cycle. The correlation of biological non-eating activity with that of the twig test was excellent, which shows a good accuracy.

For a simple comparison between different types of feeding tests, AntiFeedantIndex, AFI, was used: Amount fed at Control-Amount fed at Treatment AFI = Amount fed at Control + Amount fed at Treatment An AFI = 1 indicates a total protection against feeding (feed intake) (maximal anti-gnaw effect), an AFI = 0 is no effect, while an AFI =-1 indicates perfect feed stimulation (i. e., gnawing).

EXPERIMENTAL PART-SYNTHESIS Commercially available chemicals have been used as delivered. Dry Et20 was obtained by distillation from LiAlH4 under argon atmosphere. Dry THF was obtained by distillation fiom a blue solution of K and bensophenone under an argon atmosphere. Preparative liquid chromatography (MPLC) aims at "straight-phase"chromatography on Si02 (230-400 mesh). Boiling points have not been corrected. lH och 13C NMR spectra derive from a Bruker Avance 250 instrument having 25 °C testtemperature, CDC13 as solvent and TMS as internal reference. FT-IR spectra was obtained using a Perkin Elmer 16 PC instrument. Mass spektrometry derives from a Varian 3800 GC connected to a Varian 2000 MS (ion trap detector) in EI or CI (CH3CN as chemical ionization gas) mode.

COMPOUND TYPE I

DHCnOH (5R)- (l-Hydroxy-l-methyl-ethyl)-2-methyl-cyclohex-2-enone. Prepared in accordance with the method described by : Buchi, G.; Wuest, H. J Org. Chem. 1979,44,546. Purified by means of bulb to bulb distillation, 155-160 °C (heating chamber)/0.3 mbar. Complementary data :'H NMR (250.13 MHz) 5 6.78 (m, 1 H), 2.62 (m, 1 H), 2.46 (m, 1 H), 1.97-2.32 (m, 3 H), 1.77 (m, 3 H), 1.24 (s, 3 H), 1.22 (s, 3 H); 13C NMR (62.9 MHz): 5 200.5,145.4,135.1,71.5,46.1,39.6,27.3,27.2,27.0,15.6; MS in accordance with: An, J.; Bagnell, L.; Cablewski, T.; Strauss, C. R.; Trainor, R. W. J.Org.Chem. 1997, 62, 2505.

Cn-epox (5R)-2-Methyl-5-[(lR/æ-l-methyl-oxiranyl]-cyclohex-2-enone. Prepared in accordance with the method described by: Baldwin, J. E.; Broline, B. J Am. Cheiii. Soc. 1982,104,2865. Purified by means of distillation, bp 87-90 °C/0. 7 mbar. Isomer mixture was carried over to the next step without separation. Complementary data: IR (undiluted, KBr) 2975,2925,1675,1450,1435,1385,1365,1110 cm-1 ; 13C NMR (62.9 MHz) 8 198.9,198.8,144.1,143.9,135.7,135.6,58.0,57.9,53.0,52.4,41.4 , 40.8,40.4,40.0,27.9,27.8,19.1,18.4,15.7; MS (CI) m/z (rel. int.) 167 (M + H+, 10), 149 (40), 109 (100).

DHCnOH (lR/S, 5X2)-2-Methyl-5-[(lR/S)-l-methyl-oxiranyl]-cyclohex-2-enol. 3.11 g (18.7 mmol) of the epoxide (prepared as described above) were stirred into 25 ml MeOH and were then added (little by little) with an excess of NaBH4 under a 10 min period. The mixture was stirred for 2hrs at room temperature and was then added with 20 ml of ice water and 15 ml of 0.2 N HC1 (aq) and was extracted using 10 x 10 ml Et2O. The organic phase was dried using MgS04, evaporated, and purified (MPLC chromatography, 75 g Si02 with EtOAc/c-hexane as eluent) which gave 2.67 g (85%) of the isomers of the title as a weakly yellowish syrup (mixture of diastereomers). The isomer mixture was carried to the next step without further separation. lH NMR (250.13 MHz, main isomers) 5 5.45 (m, 1 H), 4.16 (m, 1 H), 2.52-2.70 (m, 2 H), 1.87-2.25 (m, 2 H), 1.74 (m, 3 H), 1.28 (2 # s, 2 # 3 H) ; 13C NMR (62.9 MHz, main isomers) 8 136.9,136.8,123.0,122.7,70.3,70.1,59.0,58.9,53.3,52.7,39.9, 39.2,35.2,35.1,27.8,27.6,19.0,18.9,18.6,17.9; MS (CI, main isomer) m/z (rel. int.) 151 (15), 93 (100).

Trimethyl-[(1R/S,5R)-2-methyl-5-{(1R/S)-1-methyl-oxiranyl }-cyclohex-2-eyloxy]-silane. 1.87 g (11.1 mmol) of the epoxy-alcohol (prepared as described above) were stirred in 35 ml of DMF and were then provided with 2.25 g (22.3 mmol) Et3N. 2.0 g (18 mmol) of TMSC1 were then added whereupon the mixture was stirred for 3 hrs (room temperature). 50 ml of H20 were then added to the reaction mixture which was extracted using 3 x 50 ml of Et2O, dried over Na2S04 and evaporated. The

resulting oil was purified using MPLC chromatography, 70 g of SiO2 and EtOAc/c-hexane as eluent, which provided 2.37 g (89%) of the above mentioned isomer as a weakly yellowish oil (diastereomer mixture). The mixture of isomers was brought to the next step without further separation. lH NMR (250.13 MHz, main isomers) 8 5.45 (m, 1 H), 4.19 (m, 1 H), 2.52-2.66 (m, 2 H), 1.85-2.14 (m, 2 H), 1.65 (s, br, 3 H), 1.27 (s, 3 H), 1.26, (s, 3 H), 0.15 (s, 9 H), 0.14 (s, 9 H) ; 13C NMR (62.9 MHz, main isomers) 8 137.0,136.9,123.0,122.7,70.9,70.7,58.8,58.7,53.6,52.6,40.3,3 9.3,35.5,35.3,27.8, 27.7,26.9,19.5,19.4,18.6,17.5,0.3 (2Cs) ; MS (CI, mainly isomer) m/z (rel. int.) 241 (M + H+, 5), 223 (5), 183 (20), 151 (50), 93 (100).

Trimethyl-[(lR/S, 5R)-2-methyl-5-{ (lR/S)-l-hydroxy-l-methyl-hexyl}-cyclohex-2-enyloxy]-silane.

0.34 g (1. 8 mmol) of Cul in a dry round flask (argon atmosphere) were provided with 5 ml of dry THF, whereupon the stirred mixture was cooled to-72 °C (bath temp.). 12 ml of 1.6 M n-BuLi (19 mmol) were added dropwise to the flask for a 5 min period. After 5 min 3.45 g (14.4 mmol) of the silylether- epoxide (preparared as described above) were added to the solution whereupon the mixture was allowed to reach 0 °C in 2.5 hrs. The reaction mixture was quenched by adding 20 ml of NH4Cl (saturated, aq), 80 ml H20 were added and was extracted using 3 x 100 ml of Et2O. The organic phases were combined, washed sequentially using 75 ml of H20, 75 ml of saturated sodium chloride solution, dried using Na2S04 and was evaporated which provided 3.59 g of a weakly yellow oil which was brought to the next step without further purification. 1H. NMR (250.13 MHz, raw product, main isomers) 8 5.50 (m, 1 H), 4.21 (m, 1 H), 1.85-2.02 (m, 2 H), 1.69 (s, br, 3 H), 1.20-1.58 (m, 10 H), 1.16, (s, 3 H), 1.12 (s, 3 H), 0.89-0.99 (m, 4 H), 0.18 (s, 9 H); 13C NMR (62.9 MHz, raw product, main isomers) 5 136.6,136.3,123.8,123.6,73.8,73.7,71.4,42.3,41.7,40.3,39.3,3 4.4,33.8,32.5 (2Cs), 27.1,26.2,24.3,23.4,23.2,22.9,22.7 (2Cs), 19.5 (2Cs), 14.1 (2Cs), 0.3 (2Cs); MS (EI, main isomer) m/z (rel. int.) 298 (M+, 5), 280 (30), 209 (50), 181 (100), 137 (35).

Trimethyl-[(lR/S, 5R)-2-methyl-5-{ (lR/S)-l-hydroxy-l-methyl-decyl}-cyclohex-2-enyloxy]-silane.

A dry round flask (argon atmosphere) comtaining activated chips of magnesium was provided with 31 ml of dry Et2O. To this stirred mixture 15 g (78 mmol) of n-octyl bromide (dried K2C03, distilled prior to use) were added dropvwise simultaneously with refluxing the mixture gently. The Grignard reagens formed was then added dropwise to another round flask (argon atmosphere) containing a stirred solution of 1.1 g (5.8 mmol) of CuI in 77 ml of dry THF at-30 °C followed by addition of 10 g (42 mmol) the silylether-epoxide (prepared as described above). The resulting mixture was allowed to reach room temperature during 15 hrs stirring and was quenched by adding 400 rnl of NH4C1 (saturated, aq), 800 ml of H20 were then added and extracted using 3 x 250ml of Et20. The organic phases were combined, dried using Na2S04 and evaporated which provided 15.3 g of a weakly yellow oil which was brought to the next step without further purification.

(lu/5, 5R)-2-Methyl-5-[(lR/S)-l-hydroxy-l-methyl-heXyl]-cyclohex-2- enol. 3.59 g of the raw product (mono silylether protected diol prepared in accordance with above) were stirred in 60 ml of MeOH with 0.17 g (1.0 mmol) of TsOH at room temperature over night. After 15 hrs MeOH was evaporated and the resulting oil was purified using flash chromatography, 80 g Si02 with EtOAc/c- hexane, 30%, as eluent, which provided 2.47 g (76% for tvh steg) of a diastereomer mixture as a thick oil. An analytical sample was distilled bulb to bulb, 200 °C (heating chamber)/0.85 mbar. The isomer mixture was brought to the next step without further separation. lH NMR (250.13 MHz, main isomers) 8 5.49 (m, 1 H), 4.17 (m, 1 H), 1.88-2.26 (m, 3 H), 1.76 (s, br, 3 H), 1.20-1.55 (m, 10 H), 1.15 (s, 3 H), 1.12 (s, 3 H), 0.89 (t, 3 H, J= 7 Hz); 13C NMR (62.9 MHz, main isomers) 8 136.6,136.4,123.9,

123.7,74.0,79.9,71.0,42.0,41.8,40.2,39.7,34.3,33.8,32.5,32.4 ,27.0,26.3,24.3,23.6,23.3,23.0, 22.7 (2Cs), 18.8,14.1 (2Cs); MS (EI, main isomer) l/z (rel. int.) 193 (10), 137 (55), 115 (35), 109 (45), 93 (90), 79 (100).

(lR/S, 5R)-2-Methyl-5-[(lR/s)-l-hydroxy-l-methyl-decyl]-cyclohex-2- enol. Prepared using the same procedure as (lR/S, 5R)-2-Methyl-5-[(1R/S)-1-hydroxy-1-methyl-hexyl]-cyclohex-2- enol, descibed above.

B2 (5R)-5-C (lR/S)-l-Hydroxy-l-methyl-hexyl]-2-methyl-cyclohex-2-enone. 1.1 g (4.9 mmol) of the diol (prepared as described above) were stirred in 10 ml of CH2CL2 with 7.1 g (74 mmol) of MnO2 (90%, dried at 140 °C, stored in an exicator) 2.5 days at room temperature. This resulted in a not fully completed turnover. The mixture was then filtered through a celite cake, evaporated, and the resulkting oil was purified using MPLC chromatography, 15 g of Si02 with EtOAc/c-hexane as eluent, and was finally distilled using bulb to bulb distillation. 175 °C (heating chamber)/0.6 mbar. This gave 0.52 g (47%) of the diastereomers (-l : 1 mixture) as a weakly yellow syrup. IR (undiluted, KBr) 3465,2935, 2870,1660,1450,1370 cm2 ; 1H NMR (250.13 MHz) 8 6.77 (m, 1 H), 2.57 (m, 1 H), 2.05-2.43 (m, 4 H), 1.78 (m, 3 H), 1.40-1.54 (m, 2 H), 1.20-1.40 (m, 6 H), 1.17 (s, 3 H), 1.16 (s, 3 H), 0.89 (t, 3 H, J= 7 Hz); 13C NMR (62.9 MHz) 8 200.5,200.3,145.4,145.1,135.2 (2Cs), 73.3 (2Cs), 44.0,43.9,40.2, 40.0,39.5,39.0,32.4 (2Cs), 27.1,26.7,24.2,24.1,22.6 (2Cs), 15.6 (2Cs), 14.0 (2Cs); MS (EI) m/z (rel. int.) 207 (5), 153 (10), 135 (10), 115 (40), 110 (100), 95 (70).

B34 (5R)-5-[(1R/S)-1-Hydroxy-1-methyl-decyl]-2-methyl-cyclohex-2 -enone. Prepared in accordance with the same procedure as (5R)-5-r (lR/æ-l-Hydroxy-l-methyl-hexyl]-2-methyl-cyclohex-2-enone, described above. It was distilled using bulb to bulb distillation, 220 °C (heating chamber)/0.4 mbar.

This provided the diastereomers (-1 : 1 mixture) as a weakly yelow syrup. IR (undiluted, KBr) 3470, 2925,2855,1665,1455,1370 cm-1; 1H NMR (250.13 MHz) 5 6.77 (m, 1 H), 2.56 (m, 1 H), 2.05-2.43 (m, 4 H), 1.77 (m, 3 H), 1.40-1.54 (m, 2 H), 1.18-1. 38 (m, 16 H), 1.16 (s, 3 H), 1.15 (s, 3 H), 0.88 (t, 3 H, J= 7 Hz) ; 13C NMR (62.9 MHz) b 200.6,200.5,145.6,145.3,135.1 (2Cs), 73.1 (2Cs), 44.1,44.0, 40.2,40.0,39.5,39.0,31.9 (2Cs), 30. 3 (2Cs), 29.6 (4Cs), 29.3 (2Cs), 27.2,26.7,24.1 (2Cs), 23.6 (2Cs), 22.7 (2Cs), 15.6 (2Cs), 14.1 (2Cs); MS (EI) only (rel. int.) 264 (5), 171 (20), 153 (5), 135 (5), 110 (100), 95 (45).

COMPOUND TYPE II Method A 1 mol of a suitable aromatic aldehyde was dissloved in 200 ml of ethanol (95%). 1.4 mol of propanal were charged to the solution. The solution was cooled to-10 °C and 1.25 mol of NaOH or KOH, alternatively, dissolved in 250 ml of ethanol and 250 ml of H20 were charged slowly at room temperature, during charging the temperature was never allowed to exceed 20 °C. The solution was allowed to stand in room temperature. The reaction was disrupted by neutralizing the reaction mixture using-200 ml 6 M of HCl and was extracted twice using ether, the organic phases were washed using NaHCO3, H20 and finally using a saturated salt solution and was dried using MgS04. The resulting oil

or crystals, alternatively, after filtration and roller evaporation was purified by means of distillation, chromatography or recrystallization, alternatively.

Method B 1 mol of a suitable aromathic aldehyde dissolved in 200 ml of ethanol (95%). 1.25 mol NaOH or KOH dissolved in 250 ml of ethanol and 250 ml of H20 were charged to the solution. The solution was cooled-10 °C and 1.4 mol propanal or acetaldehyde, alternatively, were charged slowly at room temperature, during the charging the temperature was never allowed to exceed 20 °C. The solution was allowed to stand at room temperature. The reaction was disrupted by neutralizing the reaction mixture using-200 ml 6 M of HCl and was extracted twice using ether, the organic phases were washed with NaHCO3, H20 and finally with saturated salt solution and was dried using MgS04. The resulting oil or crystals, alternatively, after filtration, was purified by means of distillation and/or chromatography or recrystallization, alternatively.

#40 2-Methyl-3- (-2-furanyl-5-methyl)-propanal-2-ene. Prepared in accordance with method A using 5- methylfuranal, NaOH and propanal. The reaction was disrupted after 2 hrs when the charging of ~NaOH was finished. An oil having 96% GC-purity was obtained after distillation, bp 111-113 °C/3-4 mmHg (litt. 118 °C/10 nmHg)'.'H NMR (250.13 MHz) 8 9.46 (s, 1 H), 6.96 (s, 1 H), 6.69 (d, 1 H, J = 3.1 Hz), 6.19 (d, 1 H, J= 3.1 Hz), 2.39 (s, 3 H), 2.09 (s, 3 H) ; MS (EI) m/z (rel. int.) 150 (MF, 90), 135 (55), 121 (30), 77 (90).

#54 2-Methyl-3- (2-methoxyphenyl)-propanal-2-ene. Prepared in accordance with method A using 2- methoxybensaldehyde, NaOH and propanal. RThe reaction was disrupted after 5 hrs when the charging of NaOH was finished. An oil having 92% GC-purity was obtained after distillation, bp 94- 98 °C/0. 3 mbar (litt. 128 °C/4. 25 mmHg) 2. lHNMR (250.13 MHz) 8 9.62 (s, 1 H), 7.60 (s, br, 1 H), 7.35-7.48 (m, 2 H), 6.94-7.04 (m, 2 H), 3.89 (s, 3 H), 2.02 (d, 3 H, J= 0.6 Hz); MS (EI) m/z (rel. int.) 176 (M+, 25), 161 (10), 145 (100), 133 (15), 77 (20).

2-Methyl-3- (4-methoxyphenyl)-propanal-2-ene. Prepared in accordance with method B using 4- methoxybensaldehyde, NaOH and propanal. The reaction was disrupted after 1 hr when the charging of propanal was finished. An oil having 92 % GC-purity was obtained after distillation, bp 110-111 °C/0. 6 mbar (litt. 101-102 °C/0. 1 mmHg) 3. IR (undiluted, KBr) 2840, 1675,1620,1515,825 cm@ ;'H NMR (250.13 MHz) 8 9.59 (s, 1 H), 7.58 (m, 2 H), 7.24 (s, br, 1 H), 7.02 (m, 2 H), 3.92 (s, 3 H), 2.13 (d, 3 H, J=1.2 Hz) ; 13C NMR (62.9 MHz) 8 195.5,160.7,149.8,136.2,132.0,128.0 (2Cs), 114.2 (2Cs), 55.4,10.9; MS (EI) m/z (rel. int.) 176 (M+, 100), 161 (20), 145 (50), 133 (15), 108 (30), 78 (25).

3- (2-Methoxyphenyl)-propanal-2-ene. Prepared in accordance with method B using 2- methoxybensaldehyde, NaOH and distilled acetaldehyde. The reaction was disrupted 1 hr after finishing the charging of the acetaldehyde. Crystals having 96% GC-purity were obtained after distillation and MPLC chromatography using ether/pentane (1: 9), bp 101 °C/0. 5 mbar (litt. 128-130 °C/0. 6 mmHg) 4, mp 43-46 °C (litt. 45-46 oc) 5. IR (KBr) 3000,2840,1675,1485,1465,1135,750 cm-1; 1H NMR (250.13 MHz) 8 9.69 (d, 1 H, J= 7.8 Hz), 7.84 (d, 1 H, J= 15. 9 Hz), 7.56 (dd, 1 H, J= 7.5,1.3 Hz), 7.42 (m, 1 H), 6.99 (m, 2 H), 6.79 (dd, 1 H, J= 7.8,15.9 Hz), 3.92 (s, 3 H) ; 13C NMR (62.9 MHz) 8 194.6,158.3,148.2,132.7,129.1,128.9,123.0,120.9,111.3,55.6; MS (EI) m/z (rel. int.) 162 (M+, 30), 147 (15), 131 (100), 119 (35), 77 (20).

CE10 2-Methyl-3- (3-methoxy phenyl)-propanal-2-ene. Prepared in accordance with method A using 3- methoxy bensaldehyde, NaOH and propanal. The reaction was disrupted 1 h after finishing the charging of NaOH. An oil having a 99% GC-purity was obtained after distillation and MPLC chromatography EtOAc/cyclohexane (1: 4), bp 104-106 °C/0. 6 mbar. IR (undiluted, KBr) 3000, 2960, 2835, 2715,1685,1595,1575,1380,1170,1160,785 cm-1; 1H NMR (250.13 MHz) 8 9.59 (s, 1 H), 7.37 (m, 1 H), 7.25 (s, br, 1 H), 7.13 (d, 1 H, J= 7. 5 Hz), 7.05 (m, 1 H), 6.95 (dd, 1 H, J= 8.1,2.5 Hz), 3.85 (s, 3 H), 2.08 (d, 3 H, J= 1. 2 Hz) ; 13C NMR (62.9 MHz) 8 195.6,159.6,149.7,138.6,136.4, 129.7,122.5,115.4,115.1,55.3,11.0; MS (EI) m/z (rel. int.) 176 (M+, 100), 159 (20), 145 (35), 133 (15), 77 (5).

CE11 2-Methyl-3- (2, 4-dimethoxy phenyl)-propanal-2-ene. Prepared in accordance with method B using 2,4-dimethoxy bensaldehyde, KOH and propanal. The reaction was disrupted 29 hrs after finishing the charging of the propanal. To the oil obtained after working up the reaction cyclohexane was added and the solution was allowed to stand at 5 °C for 2 h, after which time crystals had been formed which were purified by means of recrystrallisation from EtOH to 95% GC-purity. mp 85-87 °C. 1H NMR (250.13 MHz) 8 9.57 (s, 1 H), 7.56 (s, br, 1 H), 7.48 (d, 1 H, J= 8.8 Hz), 6.56 (dd, 1 H, J= 8.8,2.5 Hz), 6.50 (d, 1 H, J= 2.5 Hz), 3.88 (s, 3 H), 3.86 (s, 3 H), 2.03 (d, 3 H, J=1.2 Hz); 13C NMR (62.9 MHz) 8 195.9,162.4,159.3,144.6,136.2,131.2,117.2,104.6,98.3,55.6,55 .5,11.1; MS (EI) m/z (rel. int.) 206 (M+, 100), 191 (5), 175 (40), 138 (30), 77 (10).

CE14 2-Methyl-3- (3, 4-dimethoxy phenyl)-propanal-2-ene. Prepared in accordance with method B using 3,4-Dimethoxy bensaldehyde, KOH and propanal. The reaction was disrupted after 18 hrs after the charging of propanal was finished. Crystals of >99% GC-purity were obtained after distillation and recrystallisation from EtOH, mp 56-58 °C (litt. 59OC) 6. lH NMR (250.13 MHz) 5 9.55 (s, 1 H), 7.19 (m, 2 H), 7.09 (d, 1 H, J= 1. 9 Hz), 6.95 (d, 1 H, J= 8. 8 Hz), 3.95 (s, 3 H), 3.93 (s, 3 H), 2.11 (d, 3 H, J = 1. 2 Hz); 13C NMR (62.9 MHz) 8 195.4,150.4,150.1,148.9,136.4,128.2,124.1,113.0,111. 1,56.0 (2Cs), 11.0; MS (EI) only (rel. int.) 206 (M+, 100), 191 (25), 175 (30), 163 (30), 147 (10), 107 (25), 91 (25), 77 (20).

References 1. Francke, W.; Reith, W. Liebigs Ann. Chem. 1979,1.

2. Bogert, T.; Powell, G. 24m. Perfumer, 1930,25,617.

3. Rustmeier, K. ; Breitmeier, E. Angew. Chem. 1980,92,841.

5 4. Cignarella, G.; et al. J. Med. Chem. 1965,8; 326.

5. Bertram ; Kuersten, J. Prakt. Clzem. 1985,51; 316.

6. Dallacker, F. Glombitza, K-W., Lipp, M. Liebigs Ann. Chem. 1961,24,67.

COMPOUND TYPE m 10 15 #19 2,3-Dipropylhydroquinone. Prepared in accordance with the method described by: Högberg, H. E.

Acta Chem. Scand. 1972,26,2752.

20 25 #47 2-Propylhydroquinone. Prepared in accordance with the method described by: Cruickshank, Robinson, J. Chem. Soc. 1938; 2064,2070.