Klouwen, Marten Herman

English

In dit proefschrift is een poging gedaan bij een plant met schizogene oliegangen iets over de verhouding der terpenen in de olie in verschillende stadia te weten te komen. Als proefplant werd hiertoe Angelica archangelica L gekozen........... .... Zie: Samenvattin

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   University of GroningenDe vorming van monoterpenen en pentadekanolide in de vluchtige olie van angelicaarchangelica L.Klouwen, Marten HermanIMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite fromit. Please check the document version below.Document VersionPublisher's PDF, also known as Version of recordPublication date:1961Link to publication in University of Groningen/UMCG research databaseCitation for published version (APA):Klouwen, M. H. (1961). De vorming van monoterpenen en pentadekanolide in de vluchtige olie vanangelica archangelica L. s.n.CopyrightOther than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of theauthor(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons).The publication may also be distributed here under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license.More information can be found on the University of Groningen website: https://www.rug.nl/library/open-access/self-archiving-pure/taverne-amendment.Take-down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediatelyand investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons thenumber of authors shown on this cover page is limited to 10 maximum.Download date: 21-06-2022S A M E N V A T T I N G  Het doel van dit onderzoek was de samenstelling van de vluchtige olie uit de wortel van Angelica archangelica L. nader te onderzoeken en zo mogelijk uit de verhouding van de terpenen in verschillende ontwikkelingsstadia van de plant tot een hypothese over de vorming van deze bestanddelen te  komen. Na een historische inleiding over Angelica m c h q e l i c a  L. werden de plant, de teelt en de verwerking in het kort besproken. Hierna werd een literatuuroverzicht gegeven van de chemische samen- stelling de r  angelica-olie, waarin tevens andere soorten en varieteiten werden bet rokken. Vervolgens werden de toe te passen chemische methodieken bestudeerd. De kwalitatieve bepalingsmethode van de monoterpenen berust op het vast- stellen van relatieve retentievolumina t.0.v. limoneen op vijf stationaire fasen van verschillende polariteit. In verband met het mogelijke voorkomen in angelica-wortelolie werden van de volgende tweeentwintig terpenen de retentie- volumina bepaald; myrceen, cis-ocimeen, trans-ocimeen, cis-alloacimeen, trans-allobcimeen, a-terpineen, y-terpineen, a-fellandreen, f3-fellandreen, limoneen, terpinoleen, p-cymeen, a-pineen, f3-pineen, a-thujeen, sabineen, 3-careen, kamfeen, a-fencheen, f3-fencheen, santeen en tricycleen. De acyclische, monocyclische en bicyclische terpenen vertonen hierbij  een onderling afwijkend gaschromatografisch gedrag. Behalve de in de literatuur genoemde terpenen a-pineen en a-fellandreen konden verder  in angelica- wortelolie worden aangetoond: f3-fellandreen, 3-careen, limoneen, myrceen, c i s -  en trans-ocimeen, p-cymeen, terpinoleen, f3-pineen, sabineen, y-terpineen en kamfeen en/of a-fencheen. De kwalitatieve bepaling van deze terpenen berust op de interne stan- daardmethode, waarbij n-dekaan a l s  standaard fungeert. De waarde piekhoogte X retentietijd bleek in ons geval de beste maatstaf voor de hoeveelheid van de component. Omdat "slechts" veertien 5 vijftien monoterpenen in de olie voor- komen, kon het kwantitatieve onderzoek worden uitgevoerd op twee stationaire fasen, nl. carbowax-4000 en p ,  f.3' -0xydipropionitri1. De kwantitatieve bepaling van pentadekanolide werd uitgevoerd met het homologe hexadekanolide a l s  interne standaard. Hoewel niet tot het directe doel van dit onderzoek behorend, werden enkele zuurstofbevattende verbindingen gerdentificeerd, n. l. borne01 en carvacrol. Van de gevonden terpenen en pentadekanolide werden de absolute hoe- veelheden per  plant in de hoofdwortel en de bijwortels berekend. Het bleek, dat de vorming van vluchtige olie, die reeds in een zeer  vroeg stadium begint, vooral plaatsvond in de eers te  groeistadia, terwijl  de hoeveelheid aan het einde de r  onderzochte periode nagenoeg konstant was geworden. Op grond van verhoudingsgctallen tussen terpenen en terpeengroeperingen onderling kwam naar  voren, dat de groepen [myrceen, c i s -  en t rans-ocimeenl  [limoneen, terpinoleen en wpineen] en [3-careen, a- en  f3-fellandreen] onder- ling bijeenhorende terpenen bevatten. De eers te  groep van verbindingen kan men zich ontstaan denken uit het lynalylcarboniumion door protoneliminatie. De tweede groep vanterpenen kan men zich ontstaan denken uit het a-terpenyl- carboniumion, eveneens door protoneliminatie. De biogenetische vormings- wijzen van de, in kwantiteit belangrijkste, terpenen van de laatste groep week blijkens de resultaten van het onderzoek, af van die der beide eerste groepen. Een mogelijke vormingswijze van a-fellandreen - en eventueel 3-careen - uit. een "precursor" van cis-ocimeen werd overwogen. Voor de vorming van p-fellandreen kon met de huidige gegevens geen bevredigende formulering worden opgesteld. S U M M A R Y  The purpose of this investigation was to  further  examine the composition of the essential oil  from the root of Angelica archangelica L. and if possible to come to a hypothesis on the formation of the terpene-compounds from the proportion in the different stadia of development. A historical introduction on Angelica archangelica L. is followed by a short  description of the plant, i ts  cultivation and the working up. A review i s  given of the literature concerning the chemical composition of angelica-oil, together with other species and varieties. In chapter IV analytical methods a r e  studied. The monoterpenes a r e  determined qualitatively by their relative retentionvolumes with respect to limonene a s  found by gaschromatography on five stationary phases of different polarity. In connection with the possible occurrence in angelica- rootoil retentionvolumes of the following twenty two terpenes were determined: myrcene, cis-  and trans-ocimene, cis-  and trans-alloBcimene, a -  and y-  terpinene, a- and B-phellandrene, limonene, terpinolene, p-cymene, a- and f3-pinene, a-thuyene, sabinene, 3-carene, camphene, a- and p-fenchene, santene and tricyclene. The groups of the acyclic, monocyclic and bicyclic terpenes can be distinguished gaschromatographically. Beside the terpenes mentioned in the literature i.e. a-pinene and a-phellandrene, we found the following components in angelica-rootoil: p-phellandrene, 3-carene, limonene, myrcene, cis-  and trans-ocimene, p-cymene, terpinolene, p-pinene, sabinene, y-terpinene, together with camphene and/or a-fenchene. Quantitative determination of these terpenes i s  based on the internal standard method, with n-decane a s  a standard. We found that the product of peakheight and retention-time i s  the best quantitative measure for  each com- ponent. Because "only1' fourteen fo tifteen monoterpenes a r e  present in the oil, we were able to ca r ry  out the quantitative investigation on two stationary phases viz. carbowax-4000 and p, f3'oxydipropionitrile. Quantitative determination of pentadecanolide was car r ied  out with the homologous hexadecanolide a s  an internal standard. Thoughnot directly adhering to this investigation, some oxygen-containing compounds were identified viz. borne01 and carvacrol. F o r  a l l  constituents i. e. terpenes and pentadecanolide the absolute quantities per  plant in the main root and the s ide roots were calculated. It was shown that the amount of volatile oil, the formation of which s t a r t s  already at a very early stage, increased strongly particularly in the initial growth stages, while at  the end of the period under investigation, these amounts reached a constant level. On the strength of ratios between terpenes and terpene groups it could be shown that the groups [myrcene, cis-  and trans-ocirnene], [limonene, terpinolene and a-pinene] and [3-carene, a -  and p-phellandrene] contain "genetically" related terpenes. The f i r s t  group of compounds can formally be thought to a r i s e  f rom linalylcarbonium-ion by proton-elimination. The second group of terpenes can be formed through the a-terpenylcarbonium-ion, S U M M A R Y  , . The purpose of this investigation was to further examine the composition of the essential oil from the root of Angelica archangelica L. and if possible to come to a hypothesis on the formation of the terpene-compounds from the proportion in the different stadia of development. A historical introduction on Angelica archangelica L. i s  followed by a short description of the plant, i ts  cultivation and the working up. A review is  given of the literature concerning the chemical composition of angelica-oil, together with other species and varieties. In chapter IV analytical methods a r e  studied. The monoterpenes a re  determined qualitatively by their relative retentionvolumes with respect to limonene a s  found by gaschromatography on five stationary phases of different polarity. In connection with the possible occurrence in angelica- rootoil retentionvolumes of the following twenty two terpenes were determined: myrcene, c i s -  and trans-ocimene, cis-  and trans-allobcimene, a -  and y - terpinene, a- and p-phellandrene, limonene, terpinolene, p-cymene, a- and p-pinene, a-thuyene, sabinene, 3-carene, camphene, a -  and p-fenchene, santene and tricyclene. The groups of the acyclic, monocyclic and bicyclic terpenes can be distinguished gaschromatographically. Beside the terpenes mentioned in the literature i.e. a-pinene and a-phellandrene, we found the following components in angelica-rootoil: p-phellandrene, 3-carene, limonene, myrcene, cis-  and trans-ocimene, p-cymene, terpinolene, p-pinene, sabinene, y-terpinene, together with camphene and/or a-fenchene. Quantitative determination of these terpenes is based on the internal standard method, with n-decane a s  a standard. We found that the product of peakheight and retention-time is the best quantitative measure for  each com- ponent. Because "only1' fourteen fo tifteen monoterpenes a r e  present in the oil, we were able to ca r ry  out the quantitative investigation on two stationary phases viz. carbowax-4000 and p, p'oxydipropionitrile. Quantitative determination of pentadecanolide was carr ied out with the homologous hexadecanolide a s  an internal standard. Thoughnot directly adhering to this investigation, some oxygen-containing compounds were identified viz. borne01 and carvacrol. Fo r  al l  constituents i. e. terpenes and pentadecanolide the absolute . quantities per  plant in the main root and the side roots were calculated. It was shown that the amount of volatile oil, the formation of which s t a r t s  already at a very early stage, increased strongly particularly in the initial growth stages, while at  the end of the period under investigation, these amounts reached a constant level. On the strength of ratios between terpenes and terpene groups it could be shown that the groups [myrcene, cis-  and trans-ocimene], [limonene, terpinolene and a-pinene] and [S-carene, a-  and $-phellandrene] contain "genetically" related terpenes. The f irs t  group of compounds can formally be thought to a r i s e  from linalylcarbonium-ion by proton-elimination. The second group of terpenes can be formed through the a-terpenylcarbonium-ion, also by proton-elimination. According to our experimental results the bio- synthesis of the quantitatively most important terpenes of the last group differed from that of the f i r s t  two groups. A possible biosynthesis of a- phellandrene - and perhaps 3-carene - from a precursor  of c i s  -ocimene was taken into consideration. F o r  the formation of p -phellandrene no satisfactory route could a s  yet be suggested. 

De vorming van monoterpenen en pentadekanolide in de vluchtige olie van angelica archangelica L.

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De vorming van monoterpenen en pentadekanolide in de vluchtige olie van angelica archangelica L.

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