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    'Staff publications' is the digital repository of Wageningen University & Research

    'Staff publications' contains references to publications authored by Wageningen University staff from 1976 onward.

    Publications authored by the staff of the Research Institutes are available from 1995 onwards.

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Record number 318393
Title Ambergris fragrance compounds from labdanolic acid and larixol
Author(s) Bolster, M.G.
Source Wageningen University. Promotor(en): Æ. de Groot; B.J.M. Jansen. - S.l. : S.n. - ISBN 9789058086662 - 214
Department(s) Laboratory for Organic Chemistry
EPS
Publication type Dissertation, internally prepared
Publication year 2002
Keyword(s) diterpenen - welriekendheid - aromatische verbindingen - biosynthese - chemische eigenschappen - oxidatie - biologische eigenschappen - diterpenes - fragrance - aromatic compounds - biosynthesis - chemical properties - oxidation - biological properties
Categories Organic Chemistry
Abstract <FONT FACE="Arial" SIZE=3><p>Since ancient times, ambergris has been one of the most highly valued perfumery materials. Ambergris is a metabolic product of the spermwhale ( <em>Physeter macrocephalus</em> L.), which accumulates as concretions in the gut. (-)-Ambrox<FONT FACE="Symbol">Ò</font>, the commercially most important constituent of natural ambergris, is recognized as the prototype of all ambergris odorants. For this reason, various synthetic routes to (-)-Ambrox<FONT FACE="Symbol">Ò</font>and its racemate have been developed, preferrably starting from cheap, abundantly available natural labdanes. Sclareol is nowadays the industrially used starting material for the preparation of (-)-Ambrox<FONT FACE="Symbol">Ò</font>. Labdanolic acid and larixol are both easily and abundantly available from labdanum gum of <em>Cistus ladaniferus L.</em> ("Rock-rose") and turpentine of the <em>Larix decidua</em> , respectively, but have found little use as starting material in syntheses of Ambergris odour compounds. In this thesis new chemistry in that field is described.</p><p>From the acetate of labdanolic acid short procedures are developed for the synthesis of Ambrox<FONT FACE="Symbol">Ò</font>. Also a standard method has been developed for the oxidation of the side chain of several labdanes. Generally good to high yields of single products can be obtained using anhydrous potassium permanganate in the presence of a phase-transfer catalyst. In this way larixol can be converted into suitable synthons for the synthesis of several Ambrox-like compounds. 6</font><FONT FACE="Symbol" SIZE=3>a</font><FONT FACE="Arial" SIZE=3>-hydroxy Ambrox can be considered to be a key intermediate in such syntheses and conversions of larixol into this intermediate are described. From 6</font><FONT FACE="Symbol" SIZE=3>a</font><FONT FACE="Arial" SIZE=3>-hydroxy Ambrox a number of simple Ambrox derivatives have been synthesized. By heating with acid a mixture was formed consisting of</font><FONT FACE="Symbol" SIZE=3>D</font><sup><FONT FACE="Arial" SIZE=3>5</SUP>- and</font><FONT FACE="Symbol" SIZE=3>D</font><sup><FONT FACE="Arial" SIZE=3>6</SUP>-Ambroxene, which both are pleasant smelling.</font><FONT FACE="Symbol" SIZE=3>D</font><sup><FONT FACE="Arial" SIZE=3>5</SUP>-Ambroxene was produced in a more selective way by elimination of methanesulfonic acid from the corresponding mesylate of 6</font><FONT FACE="Symbol" SIZE=3>a</font><FONT FACE="Arial" SIZE=3>-hydroxy Ambrox. A selective synthesis of</font><FONT FACE="Symbol" SIZE=3>D</font><sup><FONT FACE="Arial" SIZE=3>6</SUP>-Ambroxene proved to be more difficult and laborious. Several approaches were investigated, and ultimately the one <em>via</em> ringclosure of an allylic alcohol proved to give good results. It turned out that this new approach could not be extended to the <em>selective</em> synthesis of six-membered cyclic ethers, <em>e.g.</em><FONT FACE="Symbol">D</font><sup>6</SUP>-Ambra oxides. In the latter case, elimination of the 6<FONT FACE="Symbol">b</font>-hydroxyl group to the corresponding<FONT FACE="Symbol">D</font><sup>6,8</SUP>-dienes was observed as the major reaction.
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