Constituents and Composition of Steam Volatile Aroma from Ceylon Tea

The constituents of steam volatile aroma, which were responsible for topnote of Ceylon tea aroma, were identified. A total of 57 compounds were identified, of which 10 (ter-pinolene, n-nonanal, trans-2-pentenal, trans-3-octen-2-one, 6-methyl-3,5-heptadien-2-one, n-nonanol, cis-3-hexenylbutyrate, cis-3-hexenylcaproate, α-terpinylacetate and nerylacetate) had not previously been reported as associated with aroma of black tea. Approximate composition of topnote aroma from Ceylon flavory tea was also determined.     

Flavor of Black Tea

Intermediate and high boiling neutral compounds in the aroma concentrate from black tea were isolated by fractional distillation, silica-gel column chromatography and gas chromatography.

Identification of the compounds was verified by the agreement of IR and mass spectra as well as gas chromatographic data with those of authentic compounds.

Eleven compounds; α-muurolene, δ-cadinene, furfuryl alcohol, methyl phenyl carbinol, cadinenol, geranial, pyrrole-2-aldehyde, benzyl formate, phenylethyl formate, cis-3-hexenyl benzoate and indole, were newly identified as constituents of black tea aroma and ten known components; α-terpineol, 3, 7-dimethyl-l, 5, 7-octatrien-3-ol, trans, trans-2, 4-decadienal, 2-phenyl-2-butenal, α- and β-ionone, cis-jasmone, theaspirone, lactone of 2-hydroxy-2, 6, 6-trimethylcyclohexylidene-l-acetic acid and phenylacetonitrile were confirmed. The geometric structure of theaspirone in tea aroma was determined as the cis-form.     

Volatile and Non-volatile Forms of Aroma Compounds in Tea Leaves and Their Changes due to Injury

Fresh tea leaves were homogenized in a chloroform-methanol mixture (1:1, v/v), and separated into chloroform-soluble and methanol-water-soluble fractions after addition of water. From the chloroform-soluble fraction, the volatile forms of the aroma compounds were obtained. The non-volatile forms of the aroma compounds were associated with the methanol-water-soluble fraction, and were converted to volatile forms by hydrolysis with dilute acid.

The amount of the aroma compounds in the free form, such as cis-3-pentenol, hexanol, cis-3-hexenol, trans-2-hexenol, linalool, linalool oxide (cis, 5-membered), linalool oxide (trans, 5-membered), linalool oxide (trans, 6-rnembered), linalool oxide (cis, 6-membered), nerol, geraniol, phenylmethanol, and 2-phenylethanol, markedly increased during black tea manufacture. However, those in the bound form, showed a slight decrease during the manufacture. The increases in the former were also brought about by maceration, or treatment of the tea leaves with monoiodoacetate or malonate.     

Aroma Components Characteristic of Spring Green Tea

To investigate the aroma components characteristic of spring green tea, analysis of the aroma concentrates of green tea and fresh tea-leaves was accomplished. The research on the changes in aroma constituents of spring green tea and the aroma concentrate from fresh tea-leaves during storage, showed that cis-3-hexenylhexanoate and cis-3-hexenyl-trans-2-hexenoate contributed to the typical fresh aroma of spring green tea. Twelve isomers of hexenol esters were synthesized for comparison of the fresh green note.     

Production of Odoriferous γ Lactones by Fusarium poae

Cultured malt broth of Fusarium poae has a strong fruity odor mainly due to lactones: γ penta-, γ hexa-, γ hepta-, γ octa-, γ nona-, γ deca-, γ undeca-, γ dodeca-, cis-6-dodecen-4-olide and δ decalactones. They were identified after gas chromatography and mass spectrometry by comparison of retention data and odors with those of authentic samples. cis-6-Dodecen-4-olide is the most abundant lactone (2 mg/liter) and is responsible for the predominant canned peach-like aroma.     

trans- and cis-Linalool 3,6-Oxide 6-O-β-d-Xylopyranosyl-β-d-glucopyranosides Isolated as Aroma Precursors from Leaves for Oolong Tea

New glycosidic aroma precursors (1 and 2) of the main volatile constituents, trans- and cis-linalool 3,6-oxides (linalool oxides I and II), were isolated from oolong tea leaves (Camellia sinensis var. sinensis cv. Maoxie). The isolation was guided by an enzymatic hydrolysis with acetone powder prepared from fresh tea leaves (cv. Yabukita) followed by GC or GC-MS analyses. Chromatographic purification of hot water extracts of the tea leaves on active charcoal, Amberlite XAD-2, and Sephadex LH-20 columns as well as HPLC gave two new glycosides, trans- and cis-linalool 3,6-oxide 6-O-β-d-xylopyranosyl-β-d-glucopyra-nosides (1 and 2).     

Flavor of Black Tea

In comparing the aroma concentrates from various types of black tea by the use of gas chromatography (GLC), differences of aroma pattern were recognized among these black tea of Ceylon, India, Peru, Formosa and Japan.

One of the typical differences, by which the variety would be characterized, appeared in the proportion of linalool (include its oxides) to geraniol and phenylethanol. Furthermore the ratio of the total area of peaks before and after linalool seemed to have some relation with the variety of black tea.

Also, top note of black tea aroma was compared by head space vapor analyses.     

Reaction of Astaxanthin with Peroxynitrite

The in vitro reactivities of astaxanthin toward peroxynitrite were investigated and the reaction products after scavenging with peroxynitrite were analyzed in order to determine the complete mechanism of this reaction. A series of carotenoids, 13-apo-astaxanthinone (1), 12′-apo-15′-nitroastaxanthinal (2), 12′-apo-astaxanthinal (3), 10′-apo-astaxanthinal (4), 9-cis-14′-s-cis-15′-nitroastaxanthin (5), 14′-s-cis-15′-nitroastaxanthin (6), 13-cis-14′-s-cis-15′-nitroastaxanthin (7), 10′-s-cis-11′-cis-11′-nitroastaxanthin (8), 13,15,13′-tri-cis-15′-nitroastaxanthin (9), 9-cis-astaxanthin (10), and 13-cis-astaxanthin (11), were isolated from the reaction products of carotenoids with peroxynitrite. Our previous studies achieved for the first time the isolation of nitro derivatives from the reaction of astaxanthin with peroxynitrite. Here we identify the major remaining reaction products of this reaction and investigate the stabilities of the nitro astaxanthins.     

Flavor of Black Tea

The neutral fraction of the essential oils from three kinds of black tea (same samples as described in the previous paper,¹⁾ i.e., Assam, Shan and Benihomare) was separated into carbonyl and carbonyl-free fractions and analysed by gas chromatography. On the basis of relative retentions and aroma of effluents with the references of the chromatographic data obtained by the previous works,^2–4) the major alcohols were found to be cis-2-pentenol, n-hexanol, cis-3-hexen-1-ol, three isomers of linalooloxide, linalool, nerol, geraniol, benzylalcohol, and phenylethylalcohol. In the carbonyl fraction, phenylacetaldehyde was newly identified, and besides it, the presence of iso- and n-butyr-, iso- and n-valer- aldehyde, methylethylketone, trans-2-hexenal, benzaldehyde were recognized. There were no differences in the components among three kinds of black tea, but the relative quantity of each component in the essential oil was different among three varieties.     

Isolation of 2-Isopropyl-4,4-dimethyl-5-vinylidene-2-cyclopenten-1-one and 2-Isopropyl-3-isopentyl-maleic Anhydride from the Pyrolytic Products of 2-Isopropylmalic acid

(R)-[2-¹⁴C]-Mevalonic acid (MVA) lactone was incorporated into (-)-4′-hydroxy-y-ionylideneacetic acid (4?-hydroxy-y-acid), which was first isolated from the culture broth of Cercospora cruenta. 4?-Hydroxy-γ-acid was then metabolized to (+)-(2Z,4E)-4′-oxo-α-ionylideneacetic acid and (+)-(2Z,4E)-′14′-dihydroxy-γ-ionylideneacetic acid. The latter was converted to (+)-abscisic acid (ABA) with a high incorporation ratio by the fungus.     

A New Synthetic Method of Methyl Ketones

A simple and stereospecific method has been developed for the synthesis of cis-jasmone. 3-Methyl-2-cyclopentenone (V) was condensed with cis-2-pentenyl chloride, which was prepared from propargyl alcohol, by means of sodium amide in liquid ammonia to yield stereochemically pure cis-jasmone (VIb) in 39~40% yield. By the similar direct alkylation, trans-jasmone (VIc) and dihydrojasmone (VIa) were also synthesized in moderate yields.     

Occurrence of Free Base of Phytosphingosine in Candida intermedia (IFO 0761)

The aroma concentrates from Vietnamese green tea and lotus tea were prepared and analyzed. Characterization of the components were carried out using coupled gas chromatography and mass spectrometry and infrared spectrometry, besides gas chromatographic retention data.

Anethole and 1,4-dimethoxybenzene have been identified for the first time as the flavor constituents in green tea. Linalool, two linalooloxides (cis and trans, five membered), 3,7-dimethyl-1,5,7-octatriene-3-ol, 2,5 (or 2,6)-dimethylpyrazine and 1-ethyl-2-formylpyrrole were the predominant components in Vietnamese green tea.

1,4-Dimethoxybenzene has been identified as the main component in lotus tea. The compound was also isolated from both dried and fresh lotus pollen.     

Studies on Abscisic Acid

Oxidation of methvl 2-trans-β-ionylideneacetate with X-bromosuccinimide afforded methyl 2-cis and trans-3′-hydroxy-β-ionylideneacetates. NaBH₄ reduction of methyl 2-cis-3′-keto-β-ionylideneacetate and ethyl 4′-keto-α-ionylideneacetate gave methyl 2-cis-3′-hydroxy-β-ionylideneacetate and ethyl 4′-hydroxy-α-ionyiideneacetate respectively. Further, methyl 4′-methoxy-epoxy-α-ionylideneacetate was prepared by epoxidation of methyl 4′-methoxy-α-ionylideneacetate. And then methyl 4′-hydroxy-l′, 2′-dihydro-β-ionylideneacetate was synthesized from ethyl 4-keto-α-cyclogeranate. Growth inhibitory activities of the above compounds on rich seedlings were examined.     

3-(4-Methyl-3-pentenyl)-2(5H)-furanone, alpha,alpha-acariolide and 4-(4-methyl-3-pentenyl)-2(5H)-furanone, alpha,beta-acariolide: new monoterpene lactones from the astigmatid mites, Schwiebea araujoae and Rhizoglyphus sp. (Astigmata: Acaridae)

A new monoterpene lactone from the acarid mite, Schwiebea araujoae, was elucidated without its isolation by GC/FT-IR and GC/MS analyses to be 3-(4-methyl-3-pentenyl)-2(5H)-furanone (1) and tentatively named as alpha,alpha-acariolide. The structure of 1 was identified by its synthesis from alpha-bromo-gamma-butyrolactone via 4 reaction steps. The synthesized compound gave the same GC/MS and GC/FT-IR spectra as those of the natural product. The other monoterpene lactone was likewise elucidated from the unidentified Rhizoglyphus mite to be 4-(4-methyl-3-pentenyl)-2(5H)-furanone (2) and named as alpha,beta-acariolide; it was also identified by its synthesis in 5 reaction steps from the same butyrolactone as the starting material. GC/MS and GC/FT-IR spectra of the preparation were identical to those of the natural product.     

Formation of 2-(5-Hyclroxymethyl-2-formylpyrrol-1-yl)alkyl Acid Lactones on Roasting Alkyl-α-amino Acid with d-Glucose

d-Glucose and several alkyl-α-amino acids (glycine, dl-α-alanine, dl-α-amino-n-butyric acid, l-valine, l-leucine and dl-α-amino-n-caproic acid) were roasted at 200°C or 250°C in a simple two components system. From the roasting products were newly isolated a series of 2-(5-hydroxymethyl-2-formylpyrrol-1-yl)alkyl acid lactones which were characterized by elementary analysis, UV, IR, MS (GC-MS) and NMR spectra.

These lactones have characteristic aroma which may contribute to the flavor produced by sugar-amino acid reaction. The subjective evaluation of aroma of the lactones obtained wrere as follows: 2-(5-hydroxymethyl-2-formyipyrrol-1-yl)propionic acid lactone, caramel and a little scorching; -n-butyric acid lactone, maple and strong sweet; isovaleric acid lactone and isocaproic acid lactone, miso, soy sauce and a little chocolate-like.     

Minor phenolics from Angelica keiskei and their proliferative effects on Hep3B cells

A new coumarin, (?)-cis-(3′R,4′R)-4′-O-angeloylkhellactone-3′-O-β-d-glucopyranoside (1) and two new chalcones, 3′-[(2E)-5-carboxy-3-methyl-2-pentenyl]-4,2′,4′-trihydroxychalcone (4) and (±)-4,2′,4′-trihydroxy-3′-{2-hydroxy-2-[tetrahydro-2-methyl-5-(1-methylethenyl)-2-furanyl]ethyl}chalcone (5) were isolated from the aerial parts of Angelica keiskei (Umbelliferae), together with six known compounds: (R)-O-isobutyroyllomatin (2), 3′-O-methylvaginol (3), (?)-jejuchalcone F (6), isoliquiritigenin (7), davidigenin (8), and (±)-liquiritigenin (9). The structures of the new compounds were determined by interpretation of their spectroscopic data including 1D and 2D NMR data. All known compounds (2, 3, and 6–9) were isolated as constituents of A. keiskei for the first time. To identify novel hepatocyte proliferation inducer for liver regeneration, 1–9 were evaluated for their cell proliferative effects using a Hep3B human hepatoma cell line. All isolates exhibited cell proliferative effects compared to untreated control (DMSO). Cytoprotective effects against oxidative stress induced by glucose oxidase were also examined on Hep3B cells and mouse fibroblast NIH3T3 cells and all compounds showed significant dose-dependent protection against oxidative stress.     

Synthesis of Theaspirone

β-Ionone (I) was oxidized to 2,3-epoxy-/β-ionone (II), which was converted to 2,3-dihydroxy-β-ionone (III) by acid treatment. III was reduced to 4-(1,2-dihydroxy-2,6,6-trimethylcyclohexan-1-yl)-2-butanol (V), which was converted, by oxidation, to cis- and trans-theaspirone (1-oxa-8-oxo-2,6,10,10-tetramethyl spiro-(4,5)-6-decene) (VII-A), (VII-B) and dihydroactinidiolide (2-hydroxy-2,6,6-trimethylcyclohexyliden-1-acetic acid lactone) (IX).     

Relationship between Stereoisomerism and Biological Activity of Pyrethroids

(+)-trans-Homochrysanthemic acid, when boiled in dilute sulfuric acid, gives (+)-trans-ε-hydroxy-dihydrohomochrysanthemic acid, m.p. 176–7°, together with (+)-δ, δ-dimethyl-γ-isobutenyl-δ-valerolactone. The formation of optically active lactone from (+)-trans-homochrysanthemic acid provides another cogent evidence for the structure of the lactone previously deduced on the racemic compound.

The Arndt-Eistert reaction of the homo-acids give further higher homologues such as (±)-,(+)-trans-β-(3-isobutenyl-2, 2-dimethylcyclopropane-1)-propionic acids and (±)-cis-3-isobutenyl-2, 2 dimethylcyclobutane-1-acetic acid. Both trans-acids, in boiling dilute sulfuric acid, give the same (±)-γ-(1′, 1′, 4′-trimethyl-pent-2′-enyl)-butyrolactone together with the corresponding hydroxy-acids, optically inactive and active, respectively.

Complete resolution of (±)-trans-homochrysanthemic acid and (±)-trans-β-(3-isobutenyl-2, 2-dimethycyclopropane-1)-propionic acid was achieved by means of optically active α-phenylethylamine.     

Studies on Abscisic Acid

Oxidation of 2-cis-α-ionylidene-ethanol (II) with active MnO₂ afforded a mixture of 2-cis and 2-trans-α-ionylideneacetaldehydes (III and IV). Reduction of methyl epoxy-α- and -β-ionylideneacetates (Vb, Xb XXIb and XXIIb) with LiAlH₄ gave the diols (VI, XI, XXIII and XXIV). The Wittig reaction of the hydroxyketones (XIII and XVIII) with carbethoxymethylenetriphenylphosphorane, followed by alkaline hydrolysis, yielded 5-(1′-and 2′-hydroxy-2′,6′,6′-trimethyl-1′-cyclohexyl)-3-methylpentadienoic acids (XIVa, XVa, XIXa and XXa). The reaction of α-cyclocitrylideneacetaldehyde (XXVII) and dihydro-α-ionone (XXXIII) with carbethoxymethylenetriphenylphosphorane afforded ethyl 3-demethyl-α-ionyli-deneacetate (XXVIIIb) and ethyl dihydro-α-ionylideneacetates (XXXIVb and XXXVb). Physiological activities of the above synthesized compounds on rice seedlings were examined.     

Syntheses et Activites Biologiques de Nouvelles (E)-Alcenyl-5 Desoxy-2′ Uridines

Abstract

(E) 5-Alkenyl 2′-deoxyuridines were synthesized with moderate to high yields by the palladium catalyzed coupling of alkenyl-zirconium reagents with 0–3′, 5′-his (trimethylsilyl) deoxyuridine in T H F. Some of these 5-alkenyl-dUrd analogues, i.e. the 1-decenyl (5g) and 2- (1-hydroxycyclopentyl) ethenyl (5f) derivatives, inhibited murine L1210 cell growth at a concentration of about 4 μg/ml, whereas the 5-chloro-1-pentenyl (5c), 5-cyano-1-pentenyl (5d), 5-hexyn-1-enyl (5e) and 2-(1-hydroxycyclopentyl) ethenyl (5f) were inhibitory towards herpes simplex and vaccinia virus within the concentration range of 2–60 μg/ml. However, none of the newly synthesized 5-alkenyl-dUrd analogues proved selective in its antiviral action.