François-Xavier Garneau

PENTACYCLIC TRITERPENE CONSTITUENTS OF YELLOW BIRCH BARK FROM QUEBEC

ABSTRACT Birch bark represents an abundant, and currently under-utilized, natural resource. Yellow birch (Betula alleghaniensis), the emblem tree of Quebec, is commercially important and one of the most widespread birch species in the province, but the use of its bark is limited. It is only used as a low value fuel source in solid wood products industries. Yellow birch bark triterpene constituents such as lupeol, betulin and betulinic acid have been described to have high biological activity. The yellow birch bark triterpene constituents such as betulin and certain derivatives of this natural substance have demonstrated interesting therapeutic properties. For example, betulinic acid has been shown to possess anti-tumor activity against human melanoma cells both in vitro and in vivo models. Its mechanism of action consists in the induction of apoptosis or cellular suicide in the cancer cells without affecting healthy cells.[14] These natural products confer added value to this tree. In this study, we investigated the triterpenoid composition of the outer bark of B. alleghaniensis from three locations in Quebec: Saint-Damien de Bellechasse, Saint-Félix-d’Otis, and Duchesnay. Eight triterpenes not previously reported in the bark of yellow birch were detected in this research. The betulonic aldehyde was identified as a new yellow birch bark constituent in bark samples from all sites, while the betulinic aldehyde and the oleanane type triterpenes were only detected in the sample from Saint-Félix-d’Otis. To our knowledge, this is the first time that the oleanane-type triterpenes are identified in yellow birch bark. *This article is dedicated to the memory of Isaïe Habiyaremye, who passed away under tragic circumstances while the publication of this article was in progress.

Synthesis of betulin derivatives with solid supported reagents.

Betulin–allobetulin transformation is effected with ferric nitrate or ferric chloride adsorbed onto silica gel or alumina, in excellent yields. In addition, allobetulin can be converted to allobetulone with silica adsorbed ferric nitrate or to 19β,28- epoxy-A-neo-18α-olean-3(5)-ene and 19β,28-epoxy-A-neo-5β-methyl-25-nor-18α-olean-9-ene with silica or alumina adsorbed ferric chloride.

Chemical Differences Between the Wood Extracts of Jack Pine (Pinus Banksiana), Black Spruce (Picea Mariana) and Balsam Fir (Abies Balsamea) from Eastern Canada

Abstract Differences in the chemical composition of the wood of balsam fir (Abies balsamea (L.), jack pine (Pinus banksiana Lamb.) and black spruce (Picea mariana (Mill.)) were determined by GC analysis of their hexane extracts. Certain constituents such as juvabione, (E)-α-atlantone and α-cadinene were shown to be present only in the heartwood of balsam fir. Analysis of the sapwood of the three species also revealed the presence of certain constituents such as juvabione, dehydrojuvabione and (E)- α-atlantone, all found only in balsam fir and an unidentified compound found only in jack pine. The chromatograms of the hexane extracts of both sapwood and heartwood showed characteristic patterns for each of the three species of conifers.

Composition of the free, esterified and sulphated sterols of the sea cucumber Psolus fabricii

1. 1. The free, esterified and sulphated sterols from the sea cucumber Psolus fabricii were isolated and identified. 2. 2. The major free sterol (60–70%) was identified as 14α-methyl-5α-cholest-9(11)-en-3β-ol. It was accompanied by smaller amounts of C27, C28 and C29 Δ0- and Δ7-sterols. 3. 3. The esterified sterols had a similar composition to the free sterols except that they contained significantly more cholest-5-en-3β-ol. 4. 4. The steryl sulphates had a very different composition from the free sterols. 14α-Methyl-5α-cholest-9(11)-en-3β-ol comprised only 10% of the mixture. 5α-Cholestan-3β-ol was the major compound (56%) accompanied by other C27, C28, C29, Δ0 and Δ5-sterols. 5. 5. The main 4α-monomethyl sterol was identified as 4α,14α-dimethyl-5α-cholest-9(11)-en-3β-ol while trace quantities of 5α-lanost-9(11)-en-3β-ol and 5α-lanosta-9(11),24-dien-3β-ol were tentatively identified. 6. 6. The occurrence of the series of Δ9(11) -sterols in P. fabricii is discussed in relation to sterol and holothurin biosynthesis.

Essential Oils from Bolivia. III. Asteraceae: Artemisia copa Philippi

Abstract The chemical composition of the essential oil obtained from Artemisia copa growing in the high valley region of Bolivia, Province of Cochabamba, was determined by a combination of GC and GC/MS measurements. The main constituents were β-thujone (42%), chamazulene (6.5%) and a homoterpene (6.0%) as well as limonene (5%) and α-pinene (4.8%).

The distribution of asterosaponins in various body components of the starfish Leptasterias polaris

Abstract 1. 1. Asterosaponins were isolated from the aboral body wall, oral body wall, stomach, and pyloric caecum of the starfish Leptasterias polaris . 2. 2. Low-pressure liquid chromatography in conjunction with thin layer chromatography were used to delineate the mixture of saponins. 3. 3. Reverse phase high performance liquid chromatography demonstrated the presence of distinctive mixtures of saponins in the different body components, although similarities were evident in the saponin mixtures from the aboral and oral body walls, and those from the stomach and gonad. 4. 4. The saponin content was determined for each of the body components. The quantity of the saponin in the stomach was significantly higher than in the other tissues which in turn were not significant different from each other. 5. 5. The sugar content and composition was determined for each saponin mixture. Quinovose was the main sugar in all body components except the pyloric caecum where xylose predominated. 6. 6. Asterone and iso-asterone were identified from the mixture of aglycones obtained by acid hydrolysis of the saponin mixture from whole specimens.

Aromas from Quebec. I. Composition of the essential oil of the rhizomes of Acorus calamus L.

Abstract The chemical composition of the essential oil obtained from the rhizomes of Acorus calamus (sweet flag) collected in the Grondines region, Province of Quebec, was determined by GC/FID and GC/MS analyses. Several components were isolated by liquid chromatography and were identified by various NMR experiments such as: 1H-NMR, 13C-NMR, HSQC, HMBC, and NOESY. The major compounds were identified as preisocalamenediol, acorenone, shyobunone, and cryptoacorone. The complete stereochemical structure of cryptoacorone was elucidated

Chemical Composition and Antimicrobial Activity of the Leaf Essential Oil of Argania spinosa L. Skeels

Abstract The essential oil, obtained by steam distillation of Argania spinosas leaves, an endemic tree of Morocco, was investigated by GC and GC/MS. The compounds were characterized by their mass spectra and retention indices. The oil was mainly composed of sesquiterpene alcohols and hydrocarbons. The principal constituent was 1,10-di-epi-cubenol (20.5%). The oil was shown to inhibit the growth of three strains of Gram positive and four strains of Gram negative bacteria as well as three strains of yeast and four strains of mold

Essential Oils from Bolivia. I. Asteraceae: Baccharis tricuneata (L.f.) Pers. var. ruiziana Cuatrecassas

Abstract The essential oil of the aerial parts of Baccharis tricuneata var. ruiziana (Asteraceae) from Bolivia was analyzed by GC and GC/MS. The oil is characterized by a high percentage of (E)-nerolidol (∼68%) and the presence of several minor constituents composed mainly of monoterpenes (∼16%), followed by sesquiterpene hydrocarbons (∼5%) and oxygenated sesquiterpenes (∼3%).

Leaf Oils of Three Eucalyptus Species from Benin: E. torelliana F. Muell., E. citriodora Hook, and E. tereticornis Smith

ABSTRACT The essential oils isolated by hydrodistillation from the leaves of Eucalyptus torelliana F. Muell., Eucalyptus citriodora Hook, and Eucalyptus tereticornis Smith were analyzed using Kovats indices and GC/MS. The main components identified in E. torelliana were α-pinene (19%), p-cymene (14%) and spathulenol (17%). The oil of E. citriodora could be an interesting natural source of citronellal (66%). The major components of the essential oil of E. tereticornis were the farnesol geometric isomers: (E,E)-farnesol (57%), (E,Z)-farnesol (13%) and (Z,Z)-farnesol (8%).