Phenanthrene Derivatives Research Articles

ChemInform Abstract: Synthesis of Phenanthrene, Naphthothiazine, Naphthalene, and Benzothiazine Derivatives.

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Phenanthrene derivatives from the medullae of Juncus effusus

The medullae of Juncus effusus yielded two new phenanthrene derivatives, dehydroeffusol and dehydroeffusal. Their structures were determined by spectral data.

Pendulin, a polyoxygenated phenanthrene derivative from the orchid Cymbidium pendulum

From the orchid Cymbidium pendulum were isolated, besides the previously reported 3,7-dihydroxy-2,4,8-trimethoxyphenanthrene, a new phenanthrene derivative, pendulin. While the structure of the former was further confirmed by its 13C NMR spectral data, that of the latter was established as 3-hydroxy-2,4,6,7,8-pentamethoxyphenanthrene from spectroscopical chemical evidence.

ChemInform Abstract: Volucrin, a New Dimeric Phenanthrene Derivative from the Orchid Lusia volucris.

Abstract Volucrin, a new dimeric phenanthrene derivative, was isolated from the orchid Lusia Volucris which also afforded 3',4-dihydroxy-3, 5'-dimethoxy-bibenzyl ( 2 ) and the perfumery constituents methyl 2,4-dihydroxy-6-methyl benzoate ( 3a ) and methyl 2,4-dihydroxy-3,-6-dimethyl benzoate ( 3b ). Volucrin was shown to have the structure 1a mainly from spectral evidence.

Photoreaction of 1-(1-naphthyl)-1,3-butadiynes with methanol

Photolysis of 1-aryl-1,3-butadiynes ( 1 – 6) in methanol yields C1 protonated polar photoaddition (type B) and photoreduction products. The photoaddition ( 7, 10, 12, 14) and photoreduction products (cis form, undergo secondary photocyclization reaction to give phenanthrene derivatives on further irradiation. A plausible reaction mechanism involving both singlet and triplet excited states is proposed.

ChemInform Abstract: Synthesis of Some Phenanthrene Derivatives Structurally Related to Certain Analgesic and Antipyretic Drugs.

AbstractThe spiro compound (VII), which combines the moieties of phenanthrene and pyrazole, is synthesized in order to have an access to compounds which may possess a higher analgesic activity than phenanthrenes or pyrazoles.

The Carcinogenicity of Cyclopenta[a]phenanthrene and Chrysene Derivatives in the Sencar mouse

Abstract Fifteen cyclopenta[a]phenanthrenes and two chrysenes, previously tested for their ability to induce skin tumours in mice of the Theiler's Original (TO) strain, were retested in Sencar mice by the initiation/promotion regime. The five compounds found to be strong carcinogens in TO mice were approximately equally active in Sencar mice with latent periods not noticably shorter, as had been anticipated from the results of others with polycylic aromatic hydrocarbons such as benzo[a]pyrene. Ten compounds inactive in TO mice also failed to induce tumours in Sencar mice. Of the remaining two compounds, both ethyl derivatives, one was apparently more active in Sencar mice, whilst the other showed the opposite behaviour. Possible reasons for these results are tentatively discussed. Abbreviations DMBA 7-12-dimethylbenz[a]anthracene Unsubstituted-17-ketone 15,16-dihydrocyclo-penta[a]phenanthren-17-one 11-methyl-17-ketone 15,16-dihydro-11-methylcyclopenta[a]phenanthren-17-one; similar abbreviations are employ...

Identification of products formed during UV irradiation of tamoxifen and their use for fluorescence detection in high-performance liquid chromatography

During the UV irradiation of tamoxifen, isomerization of the trans to the cis isomer takes place and consequently corresponding highly fluorescent phenanthrene derivatives are formed. Their formation can be used for the sensitive and selective detection of tamoxifen in high-performance liquid chromatography (HPLC). The structure of photoproducts was identified by >1H NMR spectroscopy, HPLC, gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry. Owing to the variety of products formed and the higher selectivity and fluorescence response, on-line postcolumn photocyclization is preferred to the precolumn mode. A chromatographic system for the separation of isomers and photoproducts is suggested.

Volucrin, a new dimeric phenanthrene derivative from the orchid lusia volucris

Volucrin, a new dimeric phenanthrene derivative, was isolated from the orchid Lusia Volucris which also afforded 3',4-dihydroxy-3, 5'-dimethoxy-bibenzyl ( 2) and the perfumery constituents methyl 2,4-dihydroxy-6-methyl benzoate ( 3a) and methyl 2,4-dihydroxy-3,-6-dimethyl benzoate ( 3b). Volucrin was shown to have the structure 1a mainly from spectral evidence.

Cirrhopetalanthrin, a dimeric phenanthrene derivative from the orchid Cirrhopetalum maculosum

Cirrhopetalanthrin, a new dimeric phenanthrene derivative, was isolated from the orchid Cirrhopetalum maculosum. Its structure was deduced from spectral and chemical evidence.

ChemInform Abstract: Synthesis of Some Fused Pyridine‐ and Oxazole‐Polycyclic Systems from 10‐(Methoxyimino)phenanthren‐9‐one.

AbstractThe reaction of the title phenanthrene derivative (I) with the alkyne (II) yields the (4 + 2) cycloadduct (IV).

Regiospecific photochemical transformations of 4, 5-diaryl-Δ4imidazolin-2-ones: ketai formation and cyclodehydrogenation

4,5-Diaryl-Δ4-imidazolin-2-ones undergo conversion to 2,2-dialkoxy-4,5-diaryl-Δ4-imidazolines by a characteristic solvent interaction of the carbonyl group on irradiation in alcoholic solvents. The photochemical oxidative cyclization of the stilbene system in these compounds to the corresponding phenanthrene derivatives does not occur under the usual conditions. Acidic conditions hinder the ketal formation of the carbonyl group and favour the oxidative dehydrocyclization reaction to the phenanthrene derivatives. These reactions have been found to be general to the 4,5-diaryl-Δ4-imidazolin-2-ones and plausible mechanistic pathways have been suggested for the two different selective reactions.

ChemInform Abstract: Steric Inhibition of Photochemical Reactions: The (2 + 2)Cycloaddition Reaction.

AbstractWhile irradiation of 1,2‐diphenylcyclobutene (I) at 350 nm in the presence of tetrachloroethylene (II) leads to the formation of the expected (2 + 2)cycloadduct (III), 1,2‐diphenyl‐3,3,4,4‐tetramethylcyclobutene (IV), 1,2‐diphenylcyclopentene (VIa), and 1,2‐diphenylcyclohexene (VIb) form the phenanthrene derivatives (V) and (VII) upon irradiation in the presence of tetrachloroethylene due to steric interaction.

The influence of substituents on the photocyclodehydrogenation of 1,2-diphenylcyclopentenes II: meta substituents

The photocyclodehydrogenation of several mono-meta-substituted 1,2-diphenylcyclopentenes into 2- and 4-substituted phenanthrene derivatives was investigated under various conditions (varying solvent, concentration of oxidant and temperature). As with the para-substituted isomers, the primary photocyclization step into a 4 a,4 b-dihydrophenanthrene (DHP) is not influenced by the substitutents. The two phenanthrenes are not always obtained in a ratio of 1:1. Depending on the substituent, solvent, oxidant and temperature the ratio can reach values larger than 50:1. Deviations from a ratio of 1:1 originate from the competition between oxidation and thermal ring opening of the DHPs which, in the cases studied, are formed in nearly equal amounts. The thermal ring opening of the DHPs is influenced by substituents: substituents at C2 raise the activation energy and those at C4 lower the activation energy. An isokinetic relationship is found for the thermal ring opening. The results are compared with those of substituted stilbenes and with the results of force field calculations.

13C NMR spectroscopy of aristolochic acids and aristololactams

AbstractThe 13C NMR spectra of more than 30 phenanthrene derivatives were recorded and their carbon shifts assigned. The compounds consisted of representative aristolochic acids and aristololactams, the phenanthrene alkaloid argen‐tinine and some derivatives. Assignments of the carbon resonances were carried out from chemical shifts, one‐bond and long‐range carbon‐hydrogen couplings and selective comparison of the phenanthrene derivatives with each other and with model compounds. The chemical shifts of the aromatic carbons were correlated with substituent effects. It was found that the shift changes on introduction of oxy functions in phenanthrenes parallel those reported for monosubstituted naphthalenes. Steric compression shifts observed in 3,4‐disubstituted and ring A polysubstituted phenanthrenes are discussed. Further evidence about the structures of the aristololactams CII, CIII, DII, DIII, enterocarpam‐I and enterocarpam‐II is provided, based on 13C NMR data. The substituent parameters found for phenanthrene derivatives proved to be additive and their use in signal assignments is described.

Triterpenoids and phenanthrenes from leaves of Bryophyllum pinnatum

From fresh leaves of Bryophyllum pinnatum three new constituents, bryophyllol, bryophollone and bryophollenone have been isolated and their structures elucidated by spectral and chemical studies. Three new compounds, bryophynol and two phenanthrene derivatives have also been identified in the mixture. 18α-Oleanane, ψ-taraxasterol, β-arnyrin acetate and a new sterol, reported earlier as a hydrolysed product, have also been obtained, along with a mixture of α- and β-amyrins and their acetates.

Benzylated phenanthrenes from Eulophi nuda

From the tubers of Eulophia nuda, further phenanthrene derivatives have been isolated: 9, 10-dihydro-1-(4′-hydroxybenzyl)-4,7-dimethoxyphenanthrene-2,8-diol, 1-(4′-hydroxybenzyl)-4,8-dimethoxyphenanthrene-2-7-diol. In addition, 3,4′-dihydroxy-3′,5,5′-trimethoxybibenzyl and bis(4-hydroxybenzyl) ether were obtained. The structures were assigned by spectroscopic methods. The structure of the penultimate compound mentioned above was also confirmed by synthesis.

Preparation and cyclisation reactions of 3‐Carboxy‐4‐naphthylbut‐3‐enoic Acids

AbstractThe condensation of naphthalene‐1‐ or 2‐carbaldehyde with dimethyl 2,2‐dimethyl‐succinate (Stobbe conditions) gives predominantly the (Z)‐hemiesters 3 and 11a. The hemiester 3 contains a small amount of the (E)‐isomer. Similar condensation of naphthalene‐2‐carbaldehyde with dimethyl‐2‐methylsuccinate gave the hemiester (E)‐12a. Their configuration and the ratios of the (Z:E)‐hemiesters, their derived acids, anhydrides, indenones and phenanthrene derivatives are inferred by high resolution 1H‐n.m.r. spectroscopy.

Improved enantiomeric separation of dihydrodiols of polycyclic aromatic hydrocarbons on chiral stationary phases by derivatization to O-methyl ethers

K-region trans-dihydrodiol derivatives of phenanthrene, 1-methylphenanthrene, 4,5-methylenephenanthrene, pyrene, 1-bromopyrene, chrysene, benzo[ c]-phenanthrene, benz[ aanthracene, 1-, 4-, 6-, 7-, 11- and 12-methylbenz[ a]anthracenes, 7,12-dimethylbenz[ a]anthracene, 3-methylcholanthrene, and benzo[ a]pyrene, and non- K-region trans-3,4-dihydrodiols of benz[ a]anthracene, chrysene, and 7,12-dimethylbenz[ a]anthracene are converted to O-methyl ethers. Enantiomers of these O-methyl ethers are generally more efficiently separated on Pirkle's chiral stationary phases than the enantiomers of underivatized dihydrodiols. O-Methyl ethers are substantially less polar than dihydrodiols, and O-methyl ethers are eluted with shorter retention times. Eluents of lower polarity can hence be used. This enhances chiral interactions between chiral stationary phase and solutes, allowing improved separation of enantiomers.

Electronic Structure Calculations on Phenanthrene and on a Chiral Phenanthrene Derivative

Electronic Structure Calculations on Phenanthrene and on a Chiral Phenanthrene Derivative