Studies on the Flavors of Roast Barley (Mugi-Cha)

Five weakly acidic carbonyl compounds and two neutral carbonyl compounds were newly isolated as their 2,4-dinitrophenylhydrazones besides the previously reported compounds by using column and thin-layer chromatographies.

These compounds were characterized and identified by their IR, UV and MS spectra and the mixed melting points test.

The newly isolated and identified compounds were as follows; weakly acidic carbonyl compounds: 2-pyrrolealdehyde, vanillin, p-hydroxybenzaldehyde, syringaldehyde, proto-catechuic aldehyde, neutral carbonyl compounds: glyoxal, 5-hydroxymethylfurfural.

These compounds, particularly vanillin, protocatechuic aldehyde, 2-pyrrolealdehyde and 5-hydroxymethylfurfural, appeared to be concerned with the flavor of roast barley (Mugi-Cha).     

喜光花叶的化学成分研究(Ⅱ)

从喜光花Actephila merrilliana叶中分离得到12个化合物,通过理化方法和波谱数据分别鉴定为stigmas-tan-4-en-6β-ol-3-one(1)、东莨菪内酯(2)、萘(3)、对二甲氨基苯甲醛(4)、邻苯二甲酸-二(2-乙基-辛基)酯(5)、邻苯二甲酸二丁酯(6)、O-methylmoschatoline(7)、2-hydroxy-1-naphthaldehyde(8)、4-dimethylamino-pyri-dine(9)、D-甘露糖醇(10)、胆固醇(11)、邻苯二酚(12)。以上所有化合物均首次从该属植物中分离得到。     

Terpenoids constituents of Euphorbia sapinii

The investigation of an acetone extract of whole Euphorbia sapinii led to the isolation of eighteen terpenoids among which lanost-24-en-20-ol-3-tetradecanoate (1), euphorbol-7-one (2) are new while spectroscopic data of 30-nor-hopan-3β-ol-22-one (3) are reported for the first time. The structures of all compounds were determined using 1D, 2D NMR and MS techniques.     

Role of Neutral Metabolites in Microbial Conversion of 3β-Acetoxy-19-Hydroxycholest-5-Ene into Estrone

Biotransformation of 3β-acetoxy-19-hydroxycholest-5-ene (19-HCA, 6 g) by Moraxella sp. was studied. Estrone (712 mg) was the major metabolite formed. Minor metabolites identified were 5α-androst-1-en-19-ol-3,17-dione (33 mg), androst-4-en-19-ol-3,17-dione (58 mg), androst-4-en-9α,19-diol-3,17-dione (12 mg), and androstan-19-ol-3,17-dione (1 mg). Acidic metabolites were not formed. Time course experiments on the fermentation of 19-HCA indicated that androst-4-en-19-ol-3,17-dione was the major metabolite formed during the early stages of incubation. However, with continuing fermentation its level dropped, with a concomitant increase in estrone. Fermentation of 19-HCA in the presence of specific inhibitors or performing the fermentation for a shorter period (48 h) did not result in the formation of acidic metabolites. Resting-cell experiments carried out with 19-HCA (200 mg) in the presence of α,α′-bipyridyl led to the isolation of three additional metabolites, viz., cholestan-19-ol-3-one (2 mg), cholest-4-en-19-ol-3-one (10 mg), and cholest-5-en-3β,19-diol (12 mg). Similar results were also obtained when n-propanol was used instead of α,α′-bipyridyl. Resting cells grown on 19-HCA readily converted both 5α-androst-1-en-19-ol-3,17-dione and androst-4-en-19-ol-3,17-dione into estrone. Partially purified 1,2-dehydrogenase from steroid-induced Moraxella cells transformed androst-4-en-19-ol-3,17-dione into estrone and formaldehyde in the presence of phenazine methosulfate, an artificial electron acceptor. These results suggest that the degradation of the hydrocarbon side chain of 19-HCA does not proceed via C₂₂ phenolic acid intermediates and complete removal of the C₁₇ side chain takes place prior to the aromatization of the A ring in estrone. The mode of degradation of the sterol side chain appears to be through the fission of the C₁₇-C₂₀ bond. On the basis of these observations, a new pathway for the formation of estrone from 19-HCA in Moraxella sp. has been proposed.     

Antifeedants against Locusta migratoria from the Japanese Cedar,Cryptomeria japonica

(1S,6R)-2,7(14),10-bisabolatrien-1-ol-4-one and (+)-7(14),10-bisaboladien-1-ol-4-one were isolated and identified from Cryptomeria japonica as antifeedants against Locusta migratoria L. which is well known as a serious pest to cereals throughout the world. These compounds strongly inhibited the feeding of L. migratoria only when they were combined, but each compound alone did not show any activity.     

Chemical syntheses of 5α-cholesta-6,8(14)-dien-3β-ol-15-one and related 15-oxygenated sterols

Hydroboration of 5α-cholesta-8,14-dien-3β-ol (I) gave 5α-cholest-8-en-3β,15α-diol (IV) in 89% yield. 5α-Cholest-7-en-3β,15α-diol (V) was prepared in 91% yield by hydroboration of 5α-cholesta-7,14-dien-3β-ol (II). Hydroboration of 27:63 mixture of I and II gave IV and V in 18% and 70% yields, respectively. 5α-Cholest-8-en-15α-ol-3-one and 5α-cholest-7-en-15α-ol-3-one were prepared in high yields from IV and V, respectively, by either selective oxidation with silver carbonate-celite or by enzymatic oxidation using cholesterol oxidase. 7α,8α-Epoxy-5α-cholestan-3β,15α-diol (VIII) was prepared in 93% yield by treatment of V with m-chloroperbenzoic acid. 5α-Cholest-8(14)-en-7α-ol-3,15-dione (IX) was prepared in 56% yield by oxidation of VIII with pyridinium chlorochromate followed by treatment of the crude product with acid. Compound IX was also obtained in 72% yield by selective chemical oxidation of 5α-cholest-8(14)-en-3β,7α,15α-triol. 5α-Cholesta-6,8(14)-dien-3,15-dione (X) was prepared in 89% yield by treatment of IX with p-toluenesulfonic acid under controlled conditions. Reduction of X with lithium tri-tert-butoxyaluminum hydride under controlled conditions gave 5α-cholesta-6,8(14)-dien-3β-ol-15-one in 84% yield.     

A rapid,sensitive method for simultaneous measurements of tissue levels of oxygenated derivatives of cholesterol

A mass spectrometric procedure which utilizes multiple selected ion monitoring (SIM) for measuring the tissue levels of cholest-5-en-3β,7α-diol, cholest-5-en-3β,7β-diol, cholest-5-en-3β,25-diol, and cholest-5-en-3β-ol-7-one is described. Trimethylsilyl ethers (TMS) of sterols in a lipid extract are analyzed directly by focusing the ions at $\text{m}\text{e}$ 546, 472, and 443. Endogenous cholesterol serves as an internal standard and its concentration is determined by gas chromatography. The sensitivity of this method has allowed measurement of 2 ng of oxygenated sterol which corresponded to the amount present in 1 mg of rat liver.     

Constituents of Cane Molasses

By gas chromatography the following eight phenolic compounds and benzoic acid were identified from a sample of cane final molasses using both polar and non-polar stationary phases: anisole, phenetole, phenol, m-cresol, salicylic acid, resorcinol, vanillic acid, and syringic acid. The peaks corresponding to p-coumaric acid and vanillin were also found using non-polar phase. The structures of four or five unidentified components were inferred from the relation between retention temperature and functional group number of the phenolic compounds.     

Inhibition of sterol synthesis in L cells by 14alpha-ethyl-5alpha-cholest-7-en-15alpha-ol-3-one at nanomolar concentrations

14α-Ethyl-5α-cholest-7-en-15α-ol-3-one was prepared in 85% yield by selective oxidation of the 3β-hydroxyl function of 14α-ethyl-5α-cholest-7-en-3β,15α-diol by cholesterol oxidase. 14α-Ethyl-5α-cholest-7-en-15α-ol-3-one caused a 50% inhibition of the incorporation of [1-¹⁴C]-acetate into digitonin-precipitable sterols at a concentration of 6 × 10^?9M in L cells and a 50% reduction in level of 3-hydroxy-3-methyl-glutaryl coenzyme A reductase activity in the same cells at a concentration of 4 × 10^?8 M.     

Occurrence of Potential Brassinosteroid Precursor Steroids in Seeds of Wheat and Foxtail Millet

Triticum aestivum L.) and foxtail millet (Setaria italica Beauv.) were found by GC-MS to contain, in addition to bulk sterols, 4-en-3-one steroids including 24-ethylcholesta-4,24(28)Z- dien-3-one (a new steroid), 24-methylcholest-4-en-3-one, 24-ethylcholesta-4,22E-dien-3-one and 24-ethylcholest-4-en-3-one, as well as 5α-steroidal 3-one compounds including 24-methyl-5α-cholestan-3-one, 24-ethyl-5α-cholestan-3-one and 24-ethyl 5α-cholest-22E-en-3-one (in S. italica only). Analysis of free sterol and steryl ester fractions indicated that campestanol and sitostanol were present at high levels in both seeds. These results suggest that the seeds of T. aestivum and S. italica synthesize campestanol from campesterol via 24-methylcholest-4-en-3-one and 24-methyl-5α-cholestan-3-one as has already been demonstrated in Arabidopsis thaliana L., and also produce sitostanol from sitosterol via 24-ethylcholest-4-en-3-one and 24-ethyl-5α-chotestan-3-one. Biosynthetic relationships of campestanol and sitostanol with C₂₈ and C₂₉ brassinosteroids are discussed. Received 4 September 1998/ Accepted in revised form 26 November 1998     

Inhibitors of sterol biosynthesis. Syntheses of 14α-alkyl substituted 15-oxygenated sterols

The chemical syntheses of a number of 14α-alkyl substituted 15-oxygenated sterols have been pursued to permit evaluation of their activity in the inhibition of the biosynthesis of cholesterol and other biological effects. Described herein are the first chemical syntheses of 14α-ethyl-5α-cholest-7-en-3β-ol-15-one, bis-3β,15α-acetoxy-14α-ethyl-5α-cholest-7-ene, 3β-acetoxy-14α-ethyl-5α-cholest-7-en-15β-ol, 14α-ethyl-5α-cholest-7-en-3β,15β-diol, 14α-ethyl-5α-cholest-7-en-3β,15α-diol, 3β-hexadecanoyloxy-14α-ethyl-5α-cholest-7-en-15α-ol, 3β-hexadecanoyloxy-14α-ethyl-5α-cholest-7-en-15β-ol, bis-3β,15α-hexadecanoyloxy-14α-ethyl-5α-cholest-7-ene, 3β-hexadecanoyloxy-14α-ethyl-5α-cholest-7-en-15-one, 3α-benzoyloxy-14α-ethyl-5α-cholest-7-en-15-one, 14α-ethyl-5α-cholest-7-en-3α-ol-15-one, 14α-ethyl-5α-cholest-7-en-15-on-3β-yl pyridinium sulfate, 14α-ethyl-5α-cholest-7-en-15-on-3β-yl potassium sulfate (monohydrate), 14α-ethyl-5α-cholest-7-en-15-on-3α-yl pyridinium sulfate, 14α-ethyl-5α-cholest-7-en-15-on-3α-yl potassium sulfate (monohydrate), 3β-ethoxy-14α-ethyl-5α-cholest-7-en-15-one, 3β-acetoxy-14α-n-propyl-5α-cholest-7-en-15-one, 14α-n-propyl-5α-cholest-7-en-3β-ol-15-one, bis-3β, 15α-acetoxy-14α-n-propyl-5α-cholest-7-ene, 3β-acetoxy-14α-n-propyl-5α-cholest-7-en-15β-ol, 14α-n-propyl-5α-cholest-7-en-3β, 15α-diol, 14α-n-propyl-5α-cholest-7-en-3β, 15β-diol, 14α-n-butyl-5α-cholest-7-en-3β-ol-15-one, 3β-acetoxy-14-α-n-butyl-5α-cholest-7-en-15-one, bis-3β,15α-acetoxy-14α-n-butyl-5α-cholest-7-ene, 3β-acetoxy-14α-n-butyl-5α-cholest-7-en-15β-ol, 14α-n-butyl-5β-cholest-7-en-3β, 15β-diol, and 14α-n-butyl-5α-cholest-7-en-3β, 15α-diol.     

云南割舌树的化学成分

从云南割舌树（Walsura yunnanensis C.Y.Wu.)树皮的乙醇提取物中分离鉴定了12个化合物,它们分别是walsurol(1),tocopherol(2),sitoindoside Ⅰ（3）,3β-stigmast-5-en-3-yl-β-D-xylopyranoside(4),stigmast-4-en-6β-ol-3-one(5),7-oxositosterol(6),3β-hydroxy-5α,8α-epidioxyergosta-6,22-diene(7),(-)epicatechin(8),3,5-dihydroxy-4-methoxylphenylethanol(9),间三甲氧基苯,（β－谷甾醇和胡萝卜甙,新化合物1命名为割舌醇（walsurol)。     

Role of neutral metabolites in microbial conversion of 3beta-acetoxy-19-hydroxycholest-5-ene into estrone

Biotransformation of 3beta-acetoxy-19-hydroxycholest-5-ene (19-HCA, 6 g) by Moraxella sp. was studied. Estrone (712 mg) was the major metabolite formed. Minor metabolites identified were 5alpha-androst-1-en-19-ol-3,17-dione (33 mg), androst-4-en-19-ol-3,17-dione (58 mg), androst-4-en-9alpha,19-diol-3,17-dione (12 mg), and androstan-19-ol-3,17-dione (1 mg). Acidic metabolites were not formed. Time course experiments on the fermentation of 19-HCA indicated that androst-4-en-19-ol-3,17-dione was the major metabolite formed during the early stages of incubation. However, with continuing fermentation its level dropped, with a concomitant increase in estrone. Fermentation of 19-HCA in the presence of specific inhibitors or performing the fermentation for a shorter period (48 h) did not result in the formation of acidic metabolites. Resting-cell experiments carried out with 19-HCA (200 mg) in the presence of alpha,alpha'-bipyridyl led to the isolation of three additional metabolites, viz., cholestan-19-ol-3-one (2 mg), cholest-4-en-19-ol-3-one (10 mg), and cholest-5-en-3beta,19-diol (12 mg). Similar results were also obtained when n-propanol was used instead of alpha,alpha'-bipyridyl. Resting cells grown on 19-HCA readily converted both 5alpha-androst-1-en-19-ol-3,17-dione and androst-4-en-19-ol-3,17-dione into estrone. Partially purified 1,2-dehydrogenase from steroid-induced Moraxella cells transformed androst-4-en-19-ol-3,17-dione into estrone and formaldehyde in the presence of phenazine methosulfate, an artificial electron acceptor. These results suggest that the degradation of the hydrocarbon side chain of 19-HCA does not proceed via C(22) phenolic acid intermediates and complete removal of the C(17) side chain takes place prior to the aromatization of the A ring in estrone. The mode of degradation of the sterol side chain appears to be through the fission of the C(17)-C(20) bond. On the basis of these observations, a new pathway for the formation of estrone from 19-HCA in Moraxella sp. has been proposed.     

Inhibition of hepatic sterol synthesis and reduction of serum cholesterol in rats by 5α-cholest-8(14)-en-3β-ol-15-one

The preparation of 5α-cholest-8(14)-en-3β-ol-15-one from 3β-benzoyloxy-5α-cholest-8(14)-en-15-one is described herein. Subcutaneous administration of the former compound (2 mg per day for 15 days) resulted in a significant depression of the incorporation of the label of [2-¹⁴C]-acetate, but not of [2-¹⁴C]-3RS-mevalonate, into digitonin-precipitable sterols in rat liver homogenate preparations. Subcutaneous administration of the inhibitor, 2 mg per day or 5 mg per day, for 3 days resulted in a 12% and 22% reduction of serum cholesterol levels, respectively.     

Inhibitors of sterol synthesis. Chemical syntheses and activities of new derivatives of 15-oxygenated sterols

The chemical syntheses of 5α-cholestane-3β,14α,15β-triol, 5α-cholestane-14α-ol-3,15-dione, 5α-cholestane-3β,14α-diol-15-one, 14α,15α-epoxy-5α-cholestan-3β-ol, and 5α-cholest-8(14)-en-3β-ol-15-one oxime are described. All of these compounds were found to be potent inhibitors of sterol synthesis in cultured mouse L cells. However, the former three compounds had little or no effect on the levels of 3-hydroxy-3-methylgutaryl (HMG)-CoA reductase in the same cells. In contrast, in the case of the latter two compounds, the concentrations required to cause a 50% inhibition of the synthesis of digitonin-precipitable sterols were comparable to those required to cause a 50% reduction in the levels of HMG-CoA reductase in the same cells. 5α-Cholest-8(14)-en-3β-ol-15-one oxime had no effect on serum cholesterol levels when administered to male rats at a level of 0.15% in a cholesterol-free diet.     

Cytotoxic metabolites from Botryotinia fuckeliana A-S-3: An endophytic fungus from Ajuga decumbens

Available online from an cytotoxic endophytic fungus Botryotinia fuckeliana A-S-3, three cytochalasans phenochalasin B (4), [12]-cytochalasin (5) and one [1,3] dioxacyclotridecino (6), along with two new ent-eudesmane sesquiterpenes, 1-keto-4α,15-epoxyeudesm-11-ol (1), and ent-4(15)-eudesmen-5,6-ol-1-one (2), and one known ent-eudesmane sesquiterpene ent-4(15)-eudesmen-11-ol-1-one (3) were isolated. The structures of these compounds were elucidated by interpretation of spectroscopic data. Among these compounds, two cytotoxic constituents were identified.     

Studies on the Flavor of Green Tea

By continuing flavor analysis of green tea from a previous paper, further twenty seven compounds were newly identified. These compounds are limonene, α-cubebene, α-copaene, caryophyllene, α-humulene, α- and γ-muurolene, β-sesquiphellandrene, δ-cadinene, calamenene, cubenol, α-cadinol, α-terpineol, n-heptanol, n-nonanol, furfurylalcohol, n-nonanal, N-ethylformylpyrrole, pyrrylmethylketone, 6-methyl-trans-3,5-heptadien-2-one, 2′,2″-dihydro-α-ionone, 6,10,14-trimethyl-2-pentadecanone, cis-3-hexenylcaproate, cis-3-hexenylbenzoate, α-terpinylacetate, coumarin and diphenylamine.

Relative quantities of known compounds in intermediate- and high-boiling fraction were determined.     

New monoterpenes and benzylbutanoic acid from snowbell (Styrax japonica) honey and their quantitative analysis by LC-ESI-Q-TOF-MS/MS

Honey varies depending on plant origin and environmental conditions. Chemical constituents can be used to determine the origins, characteristics, and storage period of a specific honey. Styrax japonica (snowbell) honey has excellent flavor, but very few studies have been carried out on its chemical constituents. Therefore, the present study was aimed to identify chemical constituents containing in snowbell honey and to screen candidate marker compounds for predicting the storage period of snowbell honey using the identified compounds. Twelve compounds including three new compounds were purified and isolated from the snowbell honey. Three new compounds were elucidated as 1α,3β,5β-bornetriol, 7-hydroxy-2,2,6-trimethyl-1-oxaspiro[2.5]oct-5-en-4-one, and 2-benzyl-2,3-dihydroxybutanoic acid, based on ESI-MS and NMR experiments. 6,7-Dihydroxylinalool and 6,7-dihydroxygeraniol isolated as known compounds in this study were identified for the first time in snowbell honey as well as in other honeys. The isolated compounds were qualified and quantified by LC-ESI-Q-TOF-MS/MS analysis. All compounds were detected in snowbell honeys of different production years. The levels of tyrosol, 7-hydroxy-2,2,6-trimethyl-1-oxaspiro[2.5]oct-5-en-4-one, and (–)-dihydroxyphaseic acid were lower in snowbell honey with long storage period than in short storage period, which is suggested to be used as candidate marker compounds for predicting the storage period of snowbell honey.     

Repellents in the Japanese Cedar,Cryptomeria japonica,against the Pill-bug,Armadillidium vulgare

Sandaracopimarinol and (1S,6R)-2,7(14),10-bisabolatrien-1-ol-4-one were isolated and identified from Cryptomeria japonica as repellents against Armadillidium vulgare which is well known as an unpleasant pest in the house and as vegetable pest in Japan. These compounds strongly repelled A. vulgare when they were combined, although each compound alone did not show any activity.     

Further triterpenoids and 13C NMR spectra of oleanane derivatives from Phytolacca acinosa

In addition to five known triterpenoids, namely acinosolic acid, phytolaccagenin, phytolaccagenic acid, esculentic acid and jaligonic acid, three new oleanane derivatives, designated as phytolaccagenin A, acinosolic acid A and acinosolic acid B, have been isolated and characterized from the defatted berries of Phytolacca acinosa. The new compounds have been identified as 3β-acetoxy-3β-methyloleanate-12-en-2β,23α-diol-28β-oic acid, 3β-acetoxy-28β-methyloleanate-12-en-2β-ol-30β-oic acid and 2β-acetoxy-28β-methyloleanate-12-en-3β-ol-30β-oic acid, respectively.