Tiiu Kailas

Composition of the Essential Oil from Achillea millefolium L. from Estonia

Abstract The essential oil obtained by simultaneous steam distillation and extraction (SDE) from air-dried aerial parts of plant species Achillea millefolium L. yarrow was analyzed by capillary GC and GC/MS. Sixty-six components were identified. The major constituents in the oil extracts were β-pinene (14.9–29.2%), sabinene (2.9–17.6%), 1,8-cineole (6.9–18.3%), β-caryophyllene (3.3–6.2%), (E)-nerolidol (0.5–6.4%), guaiol (0.3–11.8%) and chamazulene (0.1–13.3%). The monoterpene fraction represented 41–61% of the total oil. The increasing of distillation time from 0.5–3 h increased the yield of oil ca. two-fold, at the same time the chamazulene content increased ca. three-fold. The yield of oil after two hours distillation was 2–4 mg/g. The oil yield from the flowers was two times higher than from the leaves, while it was very low from the stems. The oil from the leaves and especially from the stems contained more oxygenated aliphatic compounds, diterpenoid compounds and other highboiling compounds, and less chamazulene and sesquiterpenes than oil from the yarrow flowers.

Composition of the Essential Oil of Levisticum Officinale W.D.J. Koch from Some European Countries

Abstract Variations in the essential oil composition of Leviticum officinale W.D.J. Koch from different European countries were determined using capillary GC and GC/MS methods. The oils were obtained in yields of 0.11–1.80% from dried cut roots and 0.09% from leaves. A total of 48 components were identified, representing over 87% of the total yield of oil. Ten compounds not earlier reported: trans-p-mentha-2,8-dien-1-ol, iso-thujyl alcohol, p-mentha-1,5-dien-8-ol, bicyclo[3.2.0]heptan-3-ol, 2-methylene-6,6-dimethyl, trans-carveol, perillaldehyde, sabinyl acetate, perillyl alcohol, methyl ester of methylpentadecate acid, and methyl hexadecadienate acid. The principal components in the oils of L. officinale roots were β-phellandrene (0.1–48.9%), pentylcyclohexadiene (0–12.3%), trans-sabinyl acetate (0–12.1%), α-terpinyl acetate (0–26.1%), (Z)-3-butylidene phthalide (0.1–31.2%), and (Z)-ligustilide (0.2–70.9%). Phthalide isomers were predominant (73.2–82.6%) in the oils from Estonia, France, and Belgium. The roots oil of L. officinale from Scotland was rich in β-phellandrene (48.9%) and phenylacetaldehyde (17.2%). Maximum content of trans-sabinyl and α-terpinyl acetates (total 38.2%) was found in the oil from Holland. Estonian L. officinale root oil contained in high quantities (E)-ligustilide (52.4–70.9%) and pentylcyclohexadiene (12.3%). The L. officinale leaf oil cultivated in Estonia contained in high amounts α-terpinyl acetate (55.8%) and β-phellandrene (11.3%). The content of (Z)-ligustilide (17.0%) in the leaf oil was smaller compared with the root oil.

Simultaneous Distillation, Extraction and Supercritical Fluid Extraction for Isolating Volatiles and Other Materials from Conifer Needles

Abstract Simultaneous distillation extraction (SDE) and supercritical fluid extraction (SFE) with CO2 of Estonian spruce and pine needles were applied with the aim to ensure complete extraction. The composition of the extract was measured for both extraction methods. SFE at used conditions did not exceed SDE in extraction of monoterpenes but was far better in extraction of oxygenated mono- and sesquiterpenoids and diterpenoids. Extract yields from pine needles was considerably higher than from spruce. Additionally, the SFE extracts of spruce needles contained semi-volatile compounds not obtained in SDE extracts. The use of organic modifiers in the C02 increased the yield in SFE.

Composition of the Essential Oil from Wild Marjoram (Origanum vulgare L.ssp. vulgare) Cultivated in Estonia

Abstract The differences between the composition of essential oils isolated from seven wild marjoram (Origanum vulgare L. ssp. vulgare) samples, gathered from different regions and cultivated in Estonia were investigated. Steam distillation was used for oil isolation and capillary GC/FID and GC/MS for oil analyses. Forty-eight compounds were identified, representing over 95% of the total oils. Different compositions of essential oils cultivated in Estonia were found. The major compounds of the oils were linalool (0.3–20.6%), β-caryophyllene (1.3–45.0%), germacrene D (0.7–21.0%), caryophyllene oxide (1.5–31.3%) and spathulenol (0.9–10.1%)

Organocatalytic asymmetric addition of malonates to unsaturated 1,4-diketones

Summary The organocatalytic Michael addition of malonates to symmetric unsaturated 1,4-diketones catalyzed by thiourea and squaramide derivatives with Cinchona alkaloids afforded the formation of a new C–C bond in high yields (up to 98%) and enantiomeric purities (up to 93%). The absolute configuration of the product was suggested from comparison of the experimental and calculated VCD spectra of the reaction product 3a.

Variation in the Composition of the Essential Oil of Commercial Valeriana officinalis L. Roots from Different Countries

Abstract The volatile constituents from roots of Valeriana officinalis L. were investigated using GC and GC/MS methods. Valerianae radix samples were obtained from retail pharmacies of different European countries. The roots of 15 V. offcinalis samples yielded 0.19–1.16% essential oil on a dry weight basis. The basic oil components among the identified 86 compounds were bornyl acetate (2.9–33.7%), α-fenchene (0–28.3%), valerianol (0.2–18.2%), valerenal (tr-15.6%), isovaleric acid (0–13.1%), camphene (0–11.1%) and valeranone (0.5–10.9%). Bornyl acetate/valerenal chemotype was characteristic for 9 of the 15 samples of valerian roots from different European countries. Some samples did not contain α-fenchene and camphene (Germany, Czech), isovaleric acid (France, Moldova, Russia 2) and valerianic acid (Estonia, Ukraine 1, Scotland, Moldova, Russia 1). Valerian root oil from Estonia was rich in essential oil, bornyl acetate (33.7%), valerianol (16.8%) and valeranone (9.5%).

Chemical investigation of the essential oil from berries and needles of common juniper (Juniperus communis L.) growing wild in Estonia

The essential oils obtained by simultaneous distillation and extraction (SDE) from the fresh and dried needles and dried berries of Juniperus communis L. of Estonian origin were subjected to GC-FID and GC–MS analyses. The yields of the oils ranged between 0.2% and 0.6% from juniper berries and between 0.5% and 1.0% from needles (dried weight). A total of 87 compounds were identified, representing over 95% of the oil. The major compounds in the needle oil were monoterpenes α-pinene (33.3–45.6%), sabinene (0.2–15.4%), limonene (2.8–4.6%) and sesquiterpenes (E)-β-caryophyllene (0.8–10.3%), α-humulene (0.8–6.2%) and germacrene D (3.0–7.8%). The juniper berry oil was rich in α-pinene (53.6–62.3%), β-myrcene (6.5–6.9%) and germacrene D (4.5–6.1%). The main oxygenated terpenoids found in the needle oil were germacrene D-4-ol (0.4–4.0%) and α-cadinol (to 2.7%). The oil from fresh needles contained high amounts of (E)-2-hexenal (3.7–11.7%).

Composition of the Oil and Supercritical Fluid CO2 Extract of Sweet Gale (Myrica gale L.) Fruits

Abstract Volatile compounds were isolated from air-dried fruits of sweet gale (Myrica gale L.) using supercritical fluid extraction with CO2 (SFE) and simultaneous distillation and extraction (SDE) micromethod. Extracts were analyzed using GC/FID and GC/MS methods. Sixty compounds were identified representing over 90% of the oil, of which 1,8-cineole (25.7%) and α-pinene (20.6%) were the major components. Two flavonoid compounds were identified in SFE extracts. The composition of SFE extracts under mild conditions did not have great distinctions compared with SDE.

Volatile Constituents of Matricaria matricarioides (Less.) Port.

Abstract The volatile constituents of Matricaria matricarioides (Less.) Port, growing in Estonia were isolated by simultaneous distillation-extraction and analyzed by GC and GC/MS. Twenty-six constituents were identified. The major compounds were myrcene, limonene, en-yne-dicycloethers, geranyl isovalerate and (E)-β-farnesene. The results obtained showed quite large quantitative differences between the fresh and dried plants oils particularly in the amounts of myrcene and (E)-β-farnesene.

SYNTHESIS OF 5,5'-DISUBSTITUTED BIMORPHOLINES

A general method for the synthesis of 5,5′-disubstituted bimorpholines is proposed. According to the method, methyl-substituted and benzyl-substituted compounds were synthesized, starting from tartaric ester acetal. Target compounds were obtained in good yield and high enantiomeric purity.