| 1. |
|
|
| 2. |
|
|
| 3. |
|
|
| 4. |
- Schlyter, F, et al.
(författare)
-
Carvone and less volatile analogues as repellent and deterrent antifeedants against the pine weevil, Hylobius abietis
- 2004
-
Ingår i: Journal of applied entomology. - : Wiley. - 0931-2048 .- 1439-0418. ; 128:9-10, s. 610-619
-
Tidskriftsartikel (refereegranskat)abstract
- The monoterpenoid carvone (1) has been shown to have strong antifeedant effects on Hylobius spp. However, because of the high volatility of carvone, long-time protection of conifer seedlings in the field using this compound has not been possible. We demonstrate, in several bioassay steps, that less-volatile, heavier analogues retain their pre-ingestive feeding inhibition activity in the large pine weevil, Hylobius abietis (L.) for a longer time. The first step in the evaluation of the biological activity of 12 carvone analogues was a micro-assay, a choice test lasting 4 h. Compounds active at 100 nmol/cm(2) were further dose-response tested to give the effective dose needed to inhibit feeding by 50% (ED50). Of the 14 compounds tested, including both carvone enantiomers, seven heavier analogues were active at low doses (had low ED50 values). As expected from their lower vapour pressure compared with carvone, the heavier analogues proved more resistant to evaporation before testing. Thus, whereas the effect of 8-hydroxy-p-menth-en-6-one 4 declined after 2 days, some of the compounds with high molar masses, such as the alkylhydroxymenthenones 6 and 8, retained a stable activity for 4 days. The retained activity at 4 days was strongly correlated to molecular mass and boiling point. When tested on natural material (host Pinus sylvestris L. twig sections for 48 h), the heavier analogues showed a rather low activity. Probably, the activity of the more volatile compound carvone (1) is due to a repellent effect (olfactory mode) rather than the deterrent effects (gustatory mode) of the heavier compounds. In agreement with the relatively low activity on twigs in the laboratory, the hydroxymenthenone 4 was not active in the field when tested for 2 months as a 1 : 9 mixture with a polar wax.
|
|
| 5. |
- Smitt, Olof, et al.
(författare)
-
Chemoselective additions of thiophenol to carvone and perillaldehyde
- 2002
-
Ingår i: Journal of Chemical Research. Synopses. - 0308-2342. ; 2002:11, s. 527-528
-
Tidskriftsartikel (refereegranskat)abstract
- Depending on the reaction conditions addition of thiophenol can be directed to either of the two C=C-double bonds of the monoterpenes carvone and perillaldehyde.
|
|
| 6. |
- Smitt, Olof, et al.
(författare)
-
First Total Synthesis of (-)-1(10),5-Germacradien-4-ol
- 2002
-
Ingår i: Synlett. - : Georg Thieme Verlag KG. - 0936-5214 .- 1437-2096. ; 2002:8, s. 1273-1276
-
Tidskriftsartikel (refereegranskat)abstract
- This paper presents a total synthesis of (-)-1(10),5-germacradien-4-ol, a constituent of the needles of Scots pine and of the defence secretion from the larvae of the pine sawfly. The synthesis uses a strategy based on an intramolecular alkylation to form an unsaturated monocyclic 10-membered ring.
|
|
| 7. |
- Smitt, Olof, et al.
(författare)
-
Syntheses of a prenylbisabolane diterpene, a natural insecticide from Croton linearis, and of the bisabolane sesquiterpenes (-)-delobanone and (-)-epi-delobanone
- 2002
-
Ingår i: Tetrahedron. - 0040-4020. ; 58:38, s. 7691-7700
-
Tidskriftsartikel (refereegranskat)abstract
- An enantioselective first total synthesis of a constituent of Croton linearis, the (-)-7-hydroxy-3,10-prenylbisaboladien-2-one 1, is described as well as the syntheses of the 7-hydroxy-3,10-bisaboladien-2-ones (-)-epi-delobanone (14a) and (-)-delobanone (14b). The model compounds, 7-hydroxy-11-nor-methyl-3-bisabolen-2-one (8a), and 11,15-nor-dimethyl-7-hydroxy-3-bisabolen-2-one (8b), were successfully prepared by opening of the protected carvone epoxide derivative 6 with the appropriate organocuprates. An alternative approach was used for compounds 1 and 14. Thus, these were obtained from homogeranyllithium or homoprenyl Grignard reagent, which reacted successfully with a masked nor-carvone, ketone 11, prepared in four steps from (R)-carvone.
|
|
| 8. |
- Smitt, Olof, 1969-
(författare)
-
Syntheses of Allelochemicals for Insect Control
- 2002
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis describes the synthetic preparation of somecompounds, which can serve as chemical signals for use in thedevelopment of control methods for pest insects. The compoundssynthesised are of the isoprenoid type and of two kinds:carvone derivatives and germacranes. The derivatives of carvoneare based on modifications of this compound, by reactions ofeither its endocyclic or its exocyclic double bond. One type ofmodifications was accomplished by chemoselective additions ofthiophenol. The latter ones imply additions to the exocyclicdouble bond and seem to constitute general, previously rarelystudied reactions.In other modifications of its exocyclic side chain, carvoneafforded some sesqui- and diterpeniod natural products. Thefollowing compounds were synthesised in an enantioselectiveway: (-)-epi-delobanone, (-)-delobanone,(-)-7-hydroxy-3,10-prenylbisaboladien- 2-one (an insecticidalconstituent of Croton linearis) as well as its diastereomer andsome other compounds with similar structures. All of thesecompounds weretested for their antifeedant/feeding deterrentcapability against gnawing of the pine weevil, Hylobiusabietis.The germacranes prepared by means of enantioselective totalsyntheses are: (–)- 1(10),5-germacradien-4-ol and(–)-germacrene D. The former is a constituent of thedefence secretion (an allomone) from the larvae of the pinesawfly, and the needles of Scots pine. (–)-Germacrene D isa ubiquitous compound in nature. For example, it occurs in thepeels of apples and acts as one component of a lure (akairomone) to the apples, which attracts the codling moth,Cydia pomonella.The main problem in the total syntheses of the germacraneswas the formation of the unsaturated monocyclic 10-memberedring. This was achieved by intramolecular alkylation with asuitably functionalised/protected cyanohydrin derivative,which, after further elaboration, afforded a monocyclic10-membered enone, that was used in the syntheses of the twogermacranes mentioned above. In the initial steps in thesynthetic sequence the stereochemistry was established byalkylation of an amide enolate attached to a chiral auxiliary.This approach could most likely also readily furnish the(+)-enantiomers of these germacrenes (of the germacraneterpenoid class) using the opposite enantiomer of the chiralauxiliary in the initial steps.Keywords: isoprenoids, natural product synthesis,allelochemicals, kairomones, allomones, bisabolane terpenoids,Hylobius abietis, germacrane terpenoids, Neodiprion sertifer,stereoselective synthesis.
|
|
