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Isolation, Synthesis and Structure-Activity Relationships of Antifeedants against the Pine Weevil, Hylobius Abietis
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The large pine weevil, Hylobius abietis L., is a major insect pest on conifer seedlings in northern Europe. Due to its feeding newly planted trees get girdled, resulting in high seedling mortality (up to 80%). As a consequence great financial losses to the forest industry occur. Today the seedlings are protected with the pyrethroid insecticide cypermethrin. This insecticide is toxic to aquatic organisms and is, from 2010, prohibited for use in Sweden by the Swedish Chemicals Inspectorate. An alternative to insecticides is to protect the seedlings with antifeedants, compounds that, either through taste or smell or both, deter the weevils from feeding. This thesis describes the search for and the synthesis of such antifeedant compounds.

Bark extracts of several woody species, known to be non-palatable to the weevil, were prepared and found to display antifeedant activity against H. abietis. The major chemical constituents of the extracts were tested for antifeedant activity. Antifeedants such as eugenol, 2-phenylethanol and benzylalcohol, but also feeding stimulants such as β-sitosterol and linoleic acid, were identified. An extract of linden bark, Tilia cordata, was shown to contain nonanoic acid, a highly active antifeedant. Other aliphatic carboxylic acids were also found to display high antifeedant activities against the weevil, both in laboratory and in field tests.

The enantiomers of dihydropinidine, a piperidine alkaloid present in several conifer species, were prepared by dimethylzinc mediated allylation of 2- methyltetrahydropyridine-N-oxide. When tested in micro feeding assays, no difference in antifeedant activity was found for the enantiomers. In a field test high antifeedant activity, comparable with that of the presently used insecticide cypermethrin, was found for (±)-dihydropindine. Other naturally occurring piperidine alkaloids were synthesised and also found to display high antifeedant activities in laboratory tests.

Structure-activity relationships were evaluated for methoxy substituted benzaldehydes, benzoic acids and cinnamic aldehydes, -acids, -esters and -alcohols. While the carboxylic acids were inactive or even feeding stimulants, the aldehydes were the most active antifeedants

Place, publisher, year, edition, pages
Stockholm: KTH , 2006. , ix, 53 p.
Series
Trita-IOK, ISSN 1100-7974 ; 2006:101
Keyword [en]
Pine weevil, Hylobius abietis, semiochemicals, antifeedant, feeding deterrent, feeding stimulant, bark extract, carboxylic acid, piperidine alkaloids, structure-activity, cinnamic aldehyde, benzaldehyde
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-3919ISBN: 91-7178-301-6 (print)OAI: oai:DiVA.org:kth-3919DiVA: diva2:10021
Public defence
2006-04-28, Sal 0102, Åkroken, Mittuniversitetet, Sundsvall, 14:00
Opponent
Supervisors
Note
QC 20110124Available from: 2006-04-11 Created: 2006-04-11 Last updated: 2011-01-24Bibliographically approved
List of papers
1. Antifeedants against Hylobius abietis pine weevils: An active compound in extract of bark of Tilia cordata linden
Open this publication in new window or tab >>Antifeedants against Hylobius abietis pine weevils: An active compound in extract of bark of Tilia cordata linden
2005 (English)In: Journal of Chemical Ecology, ISSN 0098-0331, E-ISSN 1573-1561, Vol. 31, no 5, 989-1001 p.Article in journal (Refereed) Published
Abstract [en]

Linden (Tilia cordata) bark was shown to contain an antifeedant effective against the large pine weevil, Hylobius abietis. Soxhlet extraction of inner and outer bark resulted in an extract that showed antifeedant activity in a microfeeding assay. The extract was fractionated by chromatography on silica gel using gradient elution with solvents of increasing polarity. The content of the fractions obtained was monitored by thin layer- and gas chromatography. Fractions of similar chemical composition were merged. Two of the 17 fractions showed antifeedant activity in the microfeeding assay. Nonanoic acid was identified in both of these fractions. Subsequent testing in the microfeeding assay showed that nonanoic acid possessed strong antifeedant activity against H. abietis adults.

Keyword
antifeedant, Curculionidae, Coleoptera, deterrent, extract, feeding, fractionation, Hylobius abietis, linden, nonanoic acid, outer bark, pelargonic acid, phloem, pine weevil, soxhlet, Tilia co
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-5598 (URN)10.1007/s10886-005-4243-3 (DOI)000230460700002 ()
Note
QC 20110124Available from: 2006-04-11 Created: 2006-04-11 Last updated: 2011-01-24Bibliographically approved
2. Nonanoic acid, other long-chain carboxylic acids and related compounds as antifeedants in Hylobius abietis pine weevils
Open this publication in new window or tab >>Nonanoic acid, other long-chain carboxylic acids and related compounds as antifeedants in Hylobius abietis pine weevils
2006 (English)In: Entomologia Experimentalis et Applicata, ISSN 0013-8703, E-ISSN 1570-8703, Vol. 121, no 3, 191-201 p.Article in journal (Refereed) Published
Abstract [en]

A medium-length, straight-chain alkanoic acid, nonanoic acid, is known from laboratory microassays to be an antifeedant in adults of the large pine weevil, Hylobius abietis (L.) (Coleoptera: Curculionidae). Our hypothesis was that we could find new, less volatile alkanoic acids or related compounds suitable for field application and with improved long-term duration. Alkanoic acids of varying chain lengths (C6-C13) were tested for antifeedant activity in H. abietis adults. Microassay choice tests showed that straight-chain (C6-C11) alkanoic acids were active. However, high activities were restricted to the (C6-C10) acids, with the C9 (nonanoic acid) at 4 mu mol cm(-2) being the most active one. In a no-choice test on pine twigs, the antifeedant effect of C10 acid was lower than that of the C8 and C9 acids. In microassays, less volatile methyl-branched alkanoic acids exhibited lower antifeedant activities than did the corresponding straight-chain ones. However, the most active of the methyl-branched acids, 2-methyldecanoic acid, had an activity similar to that of nonanoic acid. Compounds related to nonanoic acid were either active (1-nonanol), weakly active (nonanoic anhydride), or inactive (nonanal, sodium nonanoate). The anhydride was highly active in the microassay, but less active on twigs. The antifeedant effects of the straight chain (C8-C10) alkanoic acids against pine weevil feeding were tested in the field. In contrast to the results from the twig tests, the less volatile C10 acid was more active in the field for the protection of transplants on fresh clear cuts over a 3-month period than both the C8 and C9 acids. Phytotoxic effects of the alkanoic acids were observed both in the field and in laboratory studies. If a protective layer of paraffin was applied to the stem prior to application of the alkanoic acids, these undesired side effects were reduced.

Keyword
carboxylic acids, Coleoptera, Curculionidae, structure-activity, formulation, caproic acid, hexanoic acid, heptanoic acid, pelargonic acid, octanoic acid, decanoic acid, 2-methylalkanoic acids, repellent
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-5599 (URN)10.1111/j.1570-8703.2006.00481.x (DOI)000241954100001 ()
Note
QC 20110124Available from: 2006-04-11 Created: 2006-04-11 Last updated: 2011-01-24Bibliographically approved
3. Antifeedants and feeding stimulants in bark extracts of ten woody non-host species of the pine weevil, Hylobius abietis
Open this publication in new window or tab >>Antifeedants and feeding stimulants in bark extracts of ten woody non-host species of the pine weevil, Hylobius abietis
2008 (English)In: Journal of Chemical Ecology, ISSN 0098-0331, E-ISSN 1573-1561, Vol. 34, no 10, 1290-1297 p.Article in journal (Refereed) Published
Abstract [en]

Bark of ten woody species, known to be rejected as a food source by the pine weevil, Hylobius abietis, were sequentially extracted by a Soxhlet apparatus with pentane followed by methanol. Species were alder (Alnus glutinosa), aspen (Populus tremula), beech (Fagus sylvatica), guelder rose (Viburnum opulus), holly (Ilex aquifolium), horse chestnut (Aesculus hippocastanum), lilac (Syringa vulgaris), spindle tree (Evonymus europaeus), walnut (Juglans regia), and yew (Taxus baccata). Bark of each species was collected in southern Scandinavia during the summer. Resulting extracts were tested for antifeedant activity against the pine weevil by a micro-feeding choice assay. At a dose corresponding to that in the bark, methanol extracts from Aesculus, Taxus, Ilex, and Populus were antifeedant active, while pentane extracts of Aesculus, Fagus, Syringa, and Viburnum were stimulatory. Four known antifeedants against H. abietis, the straight-chained carboxylic acids, hexanoic and nonanoic acid (C6 and C9), carvone, and carvacrol were identified by gas chromatography (GC)-mass spectrometry (MS) in several extracts. The major constituents were identified and tested for feeding deterrence. The aromatic compounds benzyl alcohol and 2-phenylethanol are new non-host plant-derived feeding deterrents for the pine weevil. Additionally, two feeding stimulants, beta-sitosterol and 5-(hydroxymethyl)-2-furaldehyde, were identified. One active methanol extract of Aesculus bark was sequentially fractionated by liquid chromatography, and major compounds were tentatively identified as branched alcohols and esters of hexanoic acid. Five commercially available hexanoate esters and two commercially available branched alcohols were identified as new active antifeedants. Both stimulatory and inhibiting compounds were found in the same extracts and co-eluted in the same or adjacent fractions. The mix of semiochemicals of opposite activity in each extract or fraction could explain the stimulatory-, inhibitory-, or sometimes neutral activity. Generally, such co-occurrence confounds the isolation of antifeedants.

Keyword
Phagostimulant, Carboxylic acid, Bark extract, Limonene, Carvone, Carvacrol, Eugenol, Benzyl alcohol, Benzoic acid, 2-Phenylethanol, beta-Sitosterol, Hexanoate esters, Branched alcohols
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-5600 (URN)10.1007/s10886-008-9525-0 (DOI)000259910800005 ()
Note
QC 20110124. Uppdaterad från manuskript till artikel(20110124)Available from: 2006-04-11 Created: 2006-04-11 Last updated: 2011-01-24Bibliographically approved
4. Synthesis of (+)- and (−)-dihydropinidine by diastereoselective dimethylzinc promoted allylation of 2-methyltetrahydropyridine-N-oxide with an allylboronic ester
Open this publication in new window or tab >>Synthesis of (+)- and (−)-dihydropinidine by diastereoselective dimethylzinc promoted allylation of 2-methyltetrahydropyridine-N-oxide with an allylboronic ester
2006 (English)In: Tetrahedron: asymmetry, ISSN 0957-4166, E-ISSN 1362-511X, Vol. 17, no 7, 1074-1080 p.Article in journal (Refereed) Published
Abstract [en]

The enantiomers of the naturally occurring alkaloid dihydropinidine 1, potential antifeedants against the pine weevil, Hylobius abietis, were prepared by diastereoselective, dimethylzinc mediated addition of pinacolyl 2-propenylboronate 14 to nitrones (R)- and (S)2-methyl tetrahydropyridine-N-oxide 3, prepared from D- and L-alanine, respectively.

Keyword
piperidine alkaloid content, asymmetric-synthesis, 2, 6-disubstituted piperidines, enantioselective synthesis, spruce, pine, reduction, route, (2s, 6r)-dihydropinidine, dihydropinidine
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-5601 (URN)10.1016/j.tetasy.2006.03.033 (DOI)000238279900011 ()
Note
QC 20110124. Uppdaterad från submitted till published(20110124)Available from: 2006-04-11 Created: 2006-04-11 Last updated: 2011-01-24Bibliographically approved
5. Benzaldehyde, cinnamic aldehyde and related compounds as antifeedants against the pine weevil, Hylobius abietis: A study of structure-activity relationships
Open this publication in new window or tab >>Benzaldehyde, cinnamic aldehyde and related compounds as antifeedants against the pine weevil, Hylobius abietis: A study of structure-activity relationships
(English)Manuscript (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-5602 (URN)
Note
QC 20110124Available from: 2006-04-11 Created: 2006-04-11 Last updated: 2011-01-24Bibliographically approved

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