The Five Monocarboxylic Acids of Phenanthrene<sup>1,2</sup>

Dixon, Joseph A.; Neiswender, D. D.

doi:10.1021/jo01074a004

Cited by 7 publications

(4 citation statements)

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“…Metabolites were identified based on matching GC retention times and mass spectral profiles with authentic standards, or by comparison with previously published mass spectra. Phenanthrene-2-carboxylic acid was synthesized by refluxing a mixture of 2-acetylphenanthrene (Sigma-Aldrich, St Louis, MO, USA) with a 5% solution of sodium hypochlorite for 24 h according to the procedure of Dixon and Neiswender (1960). Phenanthrene-4-carboxylic acid was a gift from Dr A Callaghan (Rutgers University) and originally supplied from Sigma Chemical Co. (Milwaukee, WI, USA).…”

Section: Phenanthrene Measurementsmentioning

confidence: 99%

Anaerobic phenanthrene mineralization by a carboxylating sulfate-reducing bacterial enrichment

et al. 2007

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Information on the susceptibility of higher molecular weight polynuclear aromatic hydrocarbons to anaerobic biodegradation is relatively rare. We obtained a sulfate-reducing bacterial enrichment capable of phenanthrene metabolism from a hydrocarbon-contaminated marine sediment. Phenanthrene degradation was in stoichiometric agreement with the theoretically expected amount of sulfate reduction and inhibited by molybdate. Mineralization of 14 C-phenanthrene by the enrichment was confirmed by the recovery of the expected amount of 14 CO 2 . Stable isotope studies with protonated or deuterated phenanthrene resulted in the detection of the correspondingly labeled phenanthrene carboxylic acid by gas chromatography-mass spectrometry. Comparison of the metabolite profile with a synthesized standard confirmed that the parent molecule was carboxylated at the C-2 position. Incorporation of 13 C-bicarbonate into the carboxyl group implicated a direct carboxylation of phenanthrene as a likely key initial reaction. Denaturing gradient gel electrophoresis analysis of the enrichment showed only two major bands and 16S rRNA sequences obtained by cloning clustered with known hydrocarbon-degrading sulfate-reducing d-proteobacteria, indicating their possible involvement in the anaerobic oxidation of phenanthrene via carboxylation as the initial activation reaction.

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Section: Phenanthrene Measurementsmentioning

confidence: 99%

Anaerobic phenanthrene mineralization by a carboxylating sulfate-reducing bacterial enrichment

et al. 2007

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“…Mp 96-97°C (lit. 13 96.7°C). 1 7.32 (1 H, t, J = 6.9 Hz, Ar), 7.46 (2 H, m, Ar), 7.69 (1 H,d,J = 8.4,Ar),7.80 (1 H,d,J = 9.3,Ar),8.02 (1 H,d,J = 8.7,Ar).…”

Section: Methodsmentioning

confidence: 95%

“…Flash chromatography in (4:1) petroleum ether-EtOAc afforded the product 3b as a colourless crystalline solid (65% (1 H,d,J = 8.1 Hz,Ar),7.32 (1 H,t,J = 6.9 Hz,Ar),7.46 (2 H,m,Ar),7.69 (1 H,d,J = 8.4,Ar),7.80 (1 H,d,J = 9.3,Ar),8.02 (1 H,d,J = 8.7,Ar). 13 C NMR (75.5 MHz, CDCl 3 ): d = 35. 5, 35.6, 42.5, 52.1, 52.4, 123.9, 125.7, 126.1, 126.7, 127.8, 128.1, 129.3, 132.1, 134.3, 134.6, 175.3, 172.6 …”

Section: Methodsmentioning

confidence: 99%

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Rhodium-Catalysed 1,4-Additions in Water: Synthesis of Succinic Esters and β²-Amino Acid Derivatives

Wadsworth

Wood

Chapman³

et al. 2004

Synlett

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The rhodium-catalysed addition of boronic acids to asubstituted activated alkenes proceeds smoothly in water resulting in a unique synthesis of both succinic esters and b 2 -amino acid derivatives.Since the first report by Hayashi and Miyaura in 1998, the rhodium-catalysed addition of aryl and alkenyl organometallic reagents to activated alkenes has emerged as important methodology for organic synthesis. 1 Although both Miyaura and Lautens have reported additions to both activated alkenes and heteroaromatic alkenes that proceed with water as solvent, in the majority of reported examples organic solvents are used either alone or as co-solvents. 2 In a previous study we have revealed an efficient rhodium-catalysed conjugate addition of boronic acids to a,b-dehydroamino acid derivatives using water as the only solvent. 3 In an ongoing programme of research we have sought to broaden the scope of this methodology to other a-substituted activated alkenes. In this paper, we wish to present preliminary results in the synthesis of 2-substituted succinic esters and b 2 -amino acid derivatives. The products from this process are of significant utility as peptidomimetics in the development of pharmaceutical and agrochemical intermediates. 4 The methodology described herein represents a unique alternative to the twostep condensation-hydrogenation approach conventionally employed. 5At the outset of this study we chose to investigate the coupling of arylboronic acid (2b) with dimethyl itaconate (1) using water as the reaction solvent. During preliminary optimisation, the catalyst [Rh(cod)Cl] 2 (cod = cyclocta-1,5-diene) was used with sodium dodecylsulfate (SDS) as a phase transfer agent affording a 55% yield of product 3b. In the absence of SDS the yield fell to less than 10%. The addition of two equivalents of sodium carbonate increased the yield to 81%. Under these optimised conditions a number substituted of substituted aryl and vinylboronic acids (2a-i) was tested and, pleasingly the reaction proceeded in good isolated yield to provide a useful synthetic approach to 2-substituted succinic esters (Scheme 1). 6 The addition of phosphine ligands did not appear to accelerate the conjugate addition under these conditions. It was useful to note that both electron-rich (3h) and electron-deficient aryl boronic acids (3c,g) could be successfully employed as well as different substitution patterns (3d-f). The incorporation of functional groups such as -Cl, -COMe, -NO 2 and -NMe 2 provide pharmacologically interesting products and present opportunities for further modification. Scheme 1Given the importance of b-amino acids and their derivatives the development of new synthetic methodology to prepare such compounds is of significant interest. 7 We were therefore driven to extend the described methodology to include the addition of boronic acids to b-amidoacrylates affording b 2 -amino acid derivatives. The orthogonally protected b-amidoacrylate substrate 4 can be prepared in good yield by the reaction of potassium phthalimide (KNPht) w...

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Synthesis and insecticidal activity of lipophilic amides. Part 7. Alternative aromatic groups for phenyl in 6‐phenylhexa‐2,4‐dienamides

et al. 1989

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Synthesis of a wide range of analogues of the lead compound, N-2methylpropyl-6-phenylhexa-2,4-dienamide, in which phenyl was replaced by other aromatic systems is reported. In cases where rearrangement rendered the N-2-methylpropyl compound less accessible, N-2,2-dimethylpropyl substitution was used, because rearrangement was then suppressed. Several of the groups examined, for instance 2-naphthyl, enhanced insecticidal activity, and when appropriately substituted, particularly with halogen, led to the most active compounds discovered in this series.

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The Five Monocarboxylic Acids of Phenanthrene^1,2

Cited by 7 publications

References 2 publications

Anaerobic phenanthrene mineralization by a carboxylating sulfate-reducing bacterial enrichment

Anaerobic phenanthrene mineralization by a carboxylating sulfate-reducing bacterial enrichment

Rhodium-Catalysed 1,4-Additions in Water: Synthesis of Succinic Esters and β²-Amino Acid Derivatives

Synthesis and insecticidal activity of lipophilic amides. Part 7. Alternative aromatic groups for phenyl in 6‐phenylhexa‐2,4‐dienamides

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The Five Monocarboxylic Acids of Phenanthrene1,2

Cited by 7 publications

References 2 publications

Anaerobic phenanthrene mineralization by a carboxylating sulfate-reducing bacterial enrichment

Anaerobic phenanthrene mineralization by a carboxylating sulfate-reducing bacterial enrichment

Rhodium-Catalysed 1,4-Additions in Water: Synthesis of Succinic Esters and β2-Amino Acid Derivatives

Synthesis and insecticidal activity of lipophilic amides. Part 7. Alternative aromatic groups for phenyl in 6‐phenylhexa‐2,4‐dienamides

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The Five Monocarboxylic Acids of Phenanthrene^1,2

Rhodium-Catalysed 1,4-Additions in Water: Synthesis of Succinic Esters and β²-Amino Acid Derivatives