Steroid alcohols from the ascidianHalocynthia aurantium

The total sterols have been isolated fromHalocynthia aurantium by column chromatography on silica gel. The following steroid alcohols have been identified in it with the aid of GLC, GLC-MS, and¹H NMR: 5α-cholestan-3β-ol, 24ξ-methylcholestan-3β-ol, 24ξ-ethylcholestan-3β-ol, 4ξ-methyl-24ξ-ethyl-5α-cholestan-3β-ol, cholest-5-en-3β-ol, 24ξ-methylcholest-5-en-3β-ol, 24ξ-ethylcholes-5-en-3β-ol, 5α-cholest-22-en-3β-ol, 24-nor-5α-cholest-22-en-3β-ol, cholesta-5,22-dien-3β-ol, 24ξ-methylcholesta-5,22-dien-3β-ol, 24-norcholesta-5,22-dien-3β-ol, 24-ethylcholesta-5,24(28)-dien-3β-ol, and 24-methylcholesta-5,24(28)-dien-3β-ol.     

Use of n-lithioethylenediamine in the double bond isomerization and degradation of sterol side chains

Double bond isomerization of stigmasterol ((24S)-24-ethylcholesta-5,22-dien-3β-ol) with N-lithioethy-lenediamine produced stigmasta-5,17(20)-dien-3β-ol, stigmasta-5,20(22)-dien-3β-ol, stigmasta-5,23-dien-3β-ol and stigmasta-5,24-dien-3β-ol. Some starting material was also present in the isomerization mixture along with a small amount of stigmast-5-en-3β-ol. Similar treatment of 3α,5-cyclo-6β-methoxystigmast-22-en (stigmasterol i-methyl ether) followed by ozonization and removal of the ring A-protecting group yielded predominantly 3β-hydroxy-androst-5-en-17-one and 3β-hydroxypregn-5-en-20-one. The isomerization products of fucosterol (24-ethylcholesta- 5, 24(28)E-dien-3β-ol) and 23,24-bisnorchola-5,20-dien-3β-ol are also reported.     

Identification de stérols à chaînes latérales courtes dans l′éponge Damiriana hawaiiana

Identification of short side chain sterols in the sponge Damiriana hawaiiana The steroidal composition of the sponge Damiriana hawaiiana is examined. Twenty-seven components are identified. In addition to the C₂₆-C₂₉, Δ⁵-mono and diunsaturated sterols, the sponge contains sterols without side-chain: androsta-5, 16-dien-3β-ol( 1 ), androst-5-en-3β-ol( 2 ); sterols with a non-functionalized side-chain consisting of two, three, four, five and six carbon atoms: pregna-5, 20-dien-3β-ol( 5 ), pregn-5-en-3β-ol( 6 ), 23, 24-bisnor-chola-5, 20-dien-3β-ol( 7 ), 23, 24-bisnor-chol-5-en-3β-ol( 8 ), 24-nor-chol-5-en-3β-ol( 10 ), chol-5-en-3β-ol( 11 ), 26, 27-bisnor-cholest-5-en-3β-ol( 12 ), and sterols possessing a short oxygenated side-chain such as 3β-hydroxy-androst-5-en-17-one( 3 ), androst-5-en-3β, 17β-diol( 4 ) and 3β-hydroxy-26, 27-bisnor-22-trans-cholesta-5, 22-dien-24-one( 14 ). The probable biological or dietary origin rather than artifact production of these hitherto undescribed components from marine sources is supported by their relatively high concentration and their relative proportions, both very different from those expected for autoxidation.     

Isolation,Structure Determination and Synthesis of New Acetylenic Steroids from the Sponge Calyx nicaaensis

Two acetylenic steroids, cholest-5-en-23-yn-3β-ol ( 5 ) and 26,27-dinorcholest-5-en-23-yn-3β-ol ( 3 ), and another unsaturated steroidalcohol, stigmasta-5,23-dien-3β-ol ( 7 ), were isolated from the sponge Calyx nicaaensis. The structures of these two acetylenic steroids were established by synthesis. Several attempts to synthesize the marine steroids alcohol calysterol ( 1 ), with a cyclopropene-containing side chain, starting from cholest-5-en-23-yn-3β-ol are also recorded. Addition of ethyl-diazo-acetate to the triple bond was performed, but the reduction to the methyl derivative yielded decomposition products.     

Two new epoxysteroids from Helianthus tuberosus

Two new epoxy steroids, 5α,8α-epidioxy-22β,23β-epoxyergosta-6-en-3β-ol (1) and 5α,8α-epidioxy-22α,23α-epoxyergosta-6-en-3β-ol (2), and ten known steroids including (24R)-5α,8α-epidioxyergosta-6-en-3β-ol (3), (22E,24R)-5α,8α-epidioxyergosta-6,22-dien-3β-ol (4), (22E,24R)-5α,8α-epidioxyergosta-6,9(11),22-trien-3β-ol (5), β-sitosterol (6), sitost-5-en-3β-ol acetate (7), 7α-hydroxysitosterol (8), schleicheol 2 (9), (24R)-24-ethyl-5α-cholestane-3β,5α,6β-triol (10), 7α-hydroxystigmasterol (11), and stigmasterol (12) were isolated from Helianthus tuberosus grown in Laizhou salinized land of coastal zone of Bohai Sea, China. The structures of these compounds were unambiguously established by 1D, 2D NMR and mass spectroscopic techniques. The new compounds 1 and 2 exhibited weak antibacterial activity and no antifungal activity.     

Carbon-13 NMR spectra of some tetra- and pentacyclic triterpenoids

The carbon-13 NMR spectra of lanosta-8-en-3β-ol, lanosta-8, 24-dien-3β-ol, lanosta-7,9(11)-dien-3β-ol, lanostan-3β-ol, eupha-8-en-3β-ol, eupha-8,24-dien-3β-ol, ursa-12-en-3β-ol (α-amyrin) and oleana-12-en-3β-ol (β-amyrin) have been obtained and completely assigned. The results of this study provide chemical shift data for methyl, methylene, methine and quaternary carbon atoms in tetra- and pentacyclic triterpenoid spectra. The carbon-13 NMR spectrum of a triterpenoid provides a unique fingerprint for the molecule.     

Sterol sulfates from the Far Eastern holothurianCucumaria japonica

A chloroform-methanol extract of the musculocutaneous sac of the Far-Eastern holothurianC. japonica has yielded a fraction of sterol sulfates (13% of the weight of the extract, 0.8% of the weight of the dry biomass), the main components of which were derivatives of cholest-5-en-3β-ol, 24-methylene-, 24-ethyl-, and 24-ethylidenecholest-5-en-3β-ols, 5α-cholestan-3β-ol, and 24-methyl- and 24-methylene-5α-cholesten-3β-ol; among the minor components were found the sulfates of 24-ethyl-5α-cholestan-3β-ol of cholesta-5,22-dien-3β-ol, of a Δ⁵-C₃₀ sterol, and also of dienic and trienic C₂₆ sterols.     

Synthèse de l'hydroxy-3β-méthano-22,23-nor-24-cholestène-5 pour comparaison avec le cystostérol

Synthesis of 22,23-methano-24-nor-cholest-5-en-3β-ol and comparison with cystosterol 22,23-Methano-24-nor-cholest-5-en-3β-ol, a novel cyclopropane-containing sterol was synthesized from stigmasterol and found to be different from the isomeric, naturally occurring marine sterol cystosterol.     

Oxidation of Steroidal 5-En-3β-ol with Pyridinium Chlorochromate: Isolation of Key Intermediate,Steroidal 6β-Hydroxy-4-en-3-one

The PCC oxidation of 5-en-3β-ol steroids proceeds to 4-en-3,6-dione through the intermediate 5-en-3-one. The isolation of another key intermediate, steroidal 6β-hydroxy-4-en-3-one guides an understanding of the mechanism involved.     

Synthesis of steroidal extranucleo 1,3,4-oxadiazoles

Cholest-5en-3β-ol 1 , 3,3-ethylenedioxy-androst-4-en-17β-ol 2 and 17,17-ethylenedioxy-1,3,5(10)-estratrien-3β-ol 3 were converted into ethyl ester 1a, 2a and 3a by reaction with ethyl chloroacetate in the presence of potassium. The ethyl esters 1a, 2a and 3a on reaction with hydrazine gave hydrazides 1b, 2b and 3b , which on reaction with cyanogen bromide afforded 1,3,4-oxadiazoles 1c, 2c and 3c .     

Isolation ofΔ9(11)-sterols from the sea cucumber psolusfabricii. Implications for holothurin biosynthesis

- 14α-Methyl-5α-cholest-9(11)-en-3β-ol ($\text{2}$) and 4α,14α-dimethyl-5α-cholest-9(11)-en-3β-ol ($\text{3}$) have been isolated from the sea cucumber $\text{Psolus}$$\text{fabricii}$ and characterised by ¹H NMR, ¹³C NMR and mass spectrometry. Lanost-9(11)-en-3β-ol ($\text{4}$) has also been tentatively identified. The relevance of this series of Δ⁹⁽¹¹⁾-sterols to holothurin biosynthesis is briefly discussed.     

The Terpenoids of Maytenus boaria MOL. (Celastraceae)

The known triterpenoids β-amyrin (= olean-12-en-3β-ol; 22 ), lupeol (= lup-20(29)-en-3β-ol; 17 ), betulin (= lup-20(29)-ene-3β,28-diol; 18 ), lup-20(29)-ene-3β,30-diol ( 20 ), oleanolic acid (= 3β-hydroxyolean-12-en-28-oic acid; 21 ), and betulonic acid (= 3-oxolup-20(29)-en-28-oic acid; 19 ), together with epicatechol (= cis-2-(3,4-dihydroxyphenyl)-3,4-dihydro-2H-1-benzopyran-3,5,7-triol; 23 ), 5′-O-methylgallocatechol (= trans-2-(3,4-dihydroxy-5-methoxyphenyl)-3,4-dihydro-2H-1-benzopyran-3,5,7-triol; 24 ), and 4-hydroxybenzaldehyde were isolated from the aerial parts of Maytenus boaria (MOL. ). Additonally, the eight 4,C⁴-dihydro-β-agarofuran sesquiterpenoids 1–8 , one of them a diol with a (4R)-configuration, and compound 9 were present in the extract. The structures of these compounds were established by spectroscopic and chemical means.     

New chromone derivative from Evolvulus alsinoides Linn. aerial parts

Phytochemical investigation of the aerial parts of Evolvulus alsinoides Linn. (Convolvulacae) resulted in the isolation of a new chromone characterized as 6-hydroxy-5-nonadecanoxychroman-2-one (alsinoideschromone) along with hexatriacontane, octyl octadec-9-enoate, nonyl octadec-9-enoate, dodecanyl-octadec-9,12-dienoate, tetracosanyl hexadec-9-enoate, heptacosan-14-β-ol, stigmast-5, 22-dien-3β-ol and stigmata-5-en-3β-ol. The structure of all these phytoconstituents have been established on the basis of spectral data analysis and chemical reactions.     

Cyclopropane intermediates in the synthesis of chiral alcohols with methyl-branched carbon skeleton. Application in the synthesis of insect pheromones

Several chiral building blocks, (2R)-2-methylundec-10-en-1-ol, (3R)-3-methylheptan-1-ol, and (4R)-4-methyloctan-1-ol, have been synthesized using cyclopropane intermediate products. It has been shown that the obtained chiral alcohols can be used in the synthesis of insect pheromones.     

Stereospecific Reduction of 7-OXO Group in 3β-Acetoxycholest-5-en-7-one

The stereospecific synthesis of 3β-acetoxycholest-5-en-7β-ol from cholesterol is described.     

Compound representatives of a new type of triterpenoid from Aglaia odorata

[structure: see text] A novel triterpenoid, 21,25-cyclodammar-20(22)-ene-3beta,24alpha-diol, has been isolated from Aglaia odorata. Its structure was elucidated on the basis of 1D- and 2D-NMR and MS spectra and then confirmed by X-ray diffraction. It represents a new type of natural five-membered-ring triterpenoid, named cyclodammarane. Its possible biopathway was that squalene-2,3;22,23-diepioxide was directly cyclized to form 24,25-epoxydammar-20(21)-en-3-ol, followed by protonation of the remaining 24,25-epoxide and the cation attacking 21(20) methylene to generate the E ring.     

Identification of phytobioconstituents present in Simmondsia chinensis L. seeds extract by GC-MS analysis

Simmondsia chinensis L. commonly called as Jojoba and belongs to family Simmondsiaceae. It has shown positive pharmacological activities of these compounds which include antidiabetic, antirheumatic, anthelminthic, antipsoriatic, antioxidant, antiepileptic, antigonorrheal, analgesic, anti-inflammatory, and pesticidal activity of jojoba. The multifaceted action of numerous bioactives existing in the seed extract with therapeutic activity have attracted great research interest by pharmaceutical industries. n-hexane extract of Simmondsia chinensis L. (SC) Seeds was analysed by gas chromatography-mass spectroscopy for identification and characterization of phytobioconstituents and its therapeutic claim by traditional system. The major compounds discovered in SC seeds extract are cis-9-octadecen-1-ol (24.85%), 9-octadecen-1-ol, (Z)- (18.24%), Stigmast-5-en-3-ol (14.10%), Ergost-5-en-3-ol, (3-β)-ol (5.26%), (Z)-14-tricosenyl formate (5.24%), Thiositosteroldisulfide (3.64%), Silane, Dimethyl (dimethylpentyloxysilyloxy) tetradecyloxy- (3.41%), Ergost-5-ene, 3-methoxy-, (3β,24R)- (2.55%), Ergosta-5,22-dien-3-ol (2.22%), 1,19-eicosadiene (2.17%), Pentacosane (2.02%), Stigmasta-5,22-dien-3-ol (1.64%), 1,19-eicosadiene (1.57%), 9-octadecen-1-ol, (Z)- (1.46%), 9,19-cyclo-9β-lanostan-3β-ol, 24-methylene- (1.14%), (9Z)-9-octadecenyl palmitate (1.50%), Hexadecanoic acid, 9-octadecenyl ester, (Z) (1.37%), 9Z)-9-octadecenyl (9Z)-9-hexadecenoate (1.01%). The hexane extract of Simmondsia chinensis seeds comprises various polar and nonpolar phytobioconstituents. These compounds were established qualitatively via GC-MS evaluation. GC-MS reports will be promising in pharmaceutical sector in identification of variety of Phytobioconstituents in distinct plant extracts, polyherbal extract and the standardization of particular plant materials.     

Terpenoids and related compounds—IX Molecular rearrangements involving glutenols

The molecular rearrangements of glutenols on treatment with phosphorus pentachloride and phosphorus oxychloride and pyridine as well as on solvolysis of the corresponding tosyl derivatives have been investigated. Glut-5-en-3β-ol (Ia) and glut-5(10)-en-3-ol (IId) gave diene A (III). Glut-5-en-3-ol (Id) gave diene B (VII) and glut-5(10)-en-3β-ol (IIa) gave diene C (XIII) by ring contraction.     

四氯苯醌与3β-甲氧基胆甾-5-烯电子转移光化学反应研究

四氯苯醌(Q)与3β-甲氧基胆甾-5-烯(1)在乙腈中光化学反应主要得到三个产物:氢醌与3β-甲氧基胆甾-5-烯在7位的偶合产物(2),3β-甲氧基胆甾-5-烯-7-醇(3)和四氯对苯二酚(QH₂).本文研究了溶剂对光反应的影响,并用ESR、UV等手段探讨了反应机理。本文认为光化学反应主要经历了电子转移过程。     

Revised structures of cymbopogone and cymbopogonol

The structures of cymbopogone and cymbopogonol were revised to D:A-friedo-18β,19αH-lupan-3-one and D:A-friedo-18β,19αH-lup-4(23)-en-3β-ol, respectively.