Ethylene tetramerization: a new route to produce 1-octene in exceptionally high selectivities

Linear alpha-olefins, such as 1-hexene and 1-octene, are important comonomers in the production of linear low-density polyethylene (LLDPE). The conventional method of producing 1-hexene and 1-octene is by oligomerization of ethylene, which yields a wide spectrum of linear alpha-olefins (LAOs). While there exists several processes for producing 1-hexene via ethylene trimerization, a similar route for the selective production of 1-octene has so far been elusive. We now, for the first time, report an unprecedented ethylene tetramerization reaction that produces 1-octene in selectivities exceeding 70%, using an aluminoxane-activated chromium/((R2)2P)2NR1 catalyst system.     

Determination of carbendazim,thiabendazole, and<Emphasis Type="Italic"> o-</Emphasis>phenylphenol residues in lemons by HPLC following sample clean-up by ion-pairing

An efficient analytical method is presented involving effective sample clean-up with solid-phase extraction and HPLC-UV analysis for the simultaneous determination of carbendazim, thiabendazole, and o-phenylphenol residues in lemons. Sample preparation involves extraction with acetonitrile acidified with trifluoroacetic acid and an ethyl acetate/petroleum ether mixture. Purification of the crude extract was carried out with liquid–liquid partitioning after addition of an aqueous ammonia solution. Final clean-up was performed on polymeric reversed-phase cartridges pretreated with sodium dodecyl sulfate. Chromatographic analysis was performed on a reversed-phase HPLC column isocratically eluted with an acetonitrile/water/ammonia mixture and UV detection at 254 nm. The chromatographic method is repeatable, reproducible, and sensitive. Fungicide recoveries from lemon samples fortified at levels of 5 and 1 mg kg^–1 were 81–85% for carbendazim, 96–98% for thiabendazole, and 81–106% for o-phenylphenol with coefficients of variation of 2.5–7.4%. Detection limits for carbendazim, thiabendazole, and o-phenylphenol in lemons were 0.21, 0.27, and 0.51 mg kg^–1, respectively.     

New pyridine carboxamide ligands and their complexation to copper(II). X-Ray crystal structures of mono-, di, tri- and tetranuclear copper complexes

Seven new pyridine dicarboxamide ligands H2L(1-7) have been synthesised from condensation reactions involving pyridine-2,6-dicarboxylic acid (H2dipic), pyridine-2,6-dicarbonyl dichloride or 2,6-diaminopyridine with heterocyclic amine or carboxylic acid precursors. Crystallographic analyses of N,N'-bis(2-pyridyl)pyridine-2,6-dicarboxamide monohydrate (H2L8 x H2O), N,N'-bis[2-(2-pyridyl)methyl]pyridine-2,6-dicarboxamide and N,N'-bis[2-(2-pyridyl)ethyl]pyridine-2,6-dicarboxamide monohydrate revealed extensive intramolecular hydrogen bonding interactions. 2,6-Bis(pyrazine-2-carboxamido)pyridine (H2L6) and 2,6-bis(pyridine-2-carboxamido)pyridine (H2L7) reacted with copper(II) acetate monohydrate to give tricopper(II) complexes [Cu3(L)2(mu2-OAc)2]. X-Ray crystallography confirmed deprotonation of the amidic nitrogen atoms and that the (L6,7)2- ligands and acetate anions hold three copper(II) ions in approximately linear fashion. H2L8. Reacted with copper(II) tetrakis(pyridine) perchlorate to give [Cu(L8)(OH2)]2 x 2H2O, in which (L8)2- was tridentate through the nitrogen atoms of the central pyridine ring and the deprotonated carboxamide groups at one copper centre, with one of the terminal pyridyl rings coordinating to the other copper atom in the dimer. The corresponding reaction using H2L7 gave [Cu3(L7)2(py)2][ClO4]2, which transformed during an attempted recrystallisation from ethanol under aerobic conditions to a tetracopper(II) complex [Cu4(L7)2(L7-O)2].     

Electrochemically switchable hydrogen-bonded molecular shuttles

A series of [2]rotaxanes containing succinamide and naphthalimide hydrogen-bonding stations for a benzylic amide macrocycle is described. Electrochemical reduction and oxidation of the naphthalimide group alters its ability to form hydrogen bonds to the macrocycle to such a degree that redox processes can be used to switch the relative macrocycle-binding affinities of the two stations in a rotaxane by over 8 orders of magnitude. The structure of the neutral [2]rotaxane in solution is established by (1)H NMR spectroscopy and shows that the macrocycle exhibits remarkable positional integrity for the succinamide station in a variety of solvents. Cyclic voltammetry experiments allow the simultaneous stimulation and observation of a redox-induced dynamic process in the rotaxane which is both reversible and cyclable. Model compounds in which various conformational and co-conformational changes are prohibited demonstrate unequivocally that the redox response is the result of shuttling of the macrocycle between the two stations. At room temperature in tetrahydrofuran the electrochemically induced movement of the macrocycle between the two stations takes approximately 50 micros.     

Surprising Homolytic Gas Phase Co−C Bond Dissociation Energies of Organometallic Aryl-Cobinamides Reveal Notable Non-Bonded Intramolecular Interactions

Aryl-cobalamins are a new class of organometallic structural mimics of vitamin B₁₂ designed as potential ‘antivitamins B₁₂’. Here, the first cationic aryl-cobinamides are described, which were synthesized using the newly developed diaryl-iodonium method. The aryl-cobinamides were obtained as pairs of organometallic coordination isomers, the stereo-structure of which was unambiguously assigned based on homo- and heteronuclear NMR spectra. The availability of isomers with axial attachment of the aryl group, either at the ‘beta’ or at the ‘alpha’ face of the cobalt-center allowed for an unprecedented comparison of the organometallic reactivity of such pairs. The homolytic gas-phase bond dissociation energies (BDEs) of the coordination-isomeric phenyl- and 4-ethylphenyl-cobinamides were determined by ESI-MS threshold CID experiments, furnishing (Co−C )-BDEs of 38.4 and 40.6 kcal mol⁻¹, respectively, for the two β-isomers, and the larger BDEs of 46.6 and 43.8 kcal mol⁻¹ for the corresponding α-isomers. Surprisingly, the observed (Co−C )-BDEs of the Co_β-aryl-cobinamides were smaller than the (Co−C )-BDE of Co_β-methyl-cobinamide. DFT studies and the magnitudes of the experimental (Co−C )-BDEs revealed relevant contributions of non-bonded interactions in aryl-cobinamides, notably steric strain between the aryl and the cobalt-corrin moieties and non-bonded interactions with and among the peripheral sidechains.     

The diazo route to diazonamide A: studies on the tyrosine-derived fragment

Various approaches to the tyrosine-derived fragment of the marine secondary metabolite diazonamide A are described. Initial efforts were focused on the originally proposed structure of the natural product, and a feasibility study established that a model 4-aryltryptamine could be readily prepared. Protected 4-bromotryptamine underwent Pd0-catalyzed coupling with the boronic acid derived from 2-bromophenyl allyl ether by Claisen rearrangement, O-methylation and lithiation-boration. The resulting biaryl was elaborated into an alpha-diazo-beta-ketoester, dirhodium(II)-catalyzed reaction of which with N-Z-valinamide gave the desired tryptamine-oxazole following cyclodehydration of the intermediate ketoamide. A potential precursor to the benzofuran ring of the original structure of diazonamide A was prepared in eight steps from N-Z-tyrosine tert-butyl ester. Iodination, O-protection and Stille coupling gave the cinnamyl alcohol 25, converted via the bromide into the allyl aryl ether 27. Subsequent Claisen rearrangement and oxidative cleavage of the alkene gave the lactol 29, converted into the desired benzofuranone 31. The revision in the structure of diazonamide A to 2 resulted in the targeting of an alternative tyrosine-derived model benzofuranone 41 synthesized in four steps from N-Z-tyrosine methyl ester 36 by a route involving Claisen rearrangement of cinnamyl ether 37. Poor yields in this sequence prompted an investigation into the intramolecular Heck reaction as a route to benzofuranone 50. Coupling of 3-iodotyrosine 44 with 2-phenylbutenoic acid 48 gave ester 49 that readily underwent intramolecular Heck reaction to give benzofuranone 50, albeit with poor stereocontrol.     

Stereochemistry of planarchiral compounds,part X

2,7-Dibromo-1,6-methano[10]anulene (3) and 2,9-Dibromo-syn-1,6:8,13-diimino[14]anulene (9) were quantitatively separated into their enantiomers by chromatography on triacetylcellulose (TAC) in ethanol. X-ray structure analysis (Bijvoet technique) established the chiralities (+)(R)-3 and (+)(S)-9 for the dextrorotatory enantiomers.Comparison of the CD spectra allowed the configurational assignment to further optically active [10] and [14] anulenes which were also accessible by chromatography onTAC. Conversion of (+)(R)-2-bromo-1,6-methano[10]anulene (2) into the corresponding methylester (–)-4 confirmed its previously proposed chirality (–)(R).2,7-Dibromo-1,6-oxido[10]anulene (7) and 2,9-dibromo-syn-diimino[14]anulene (9) are in contrast to the 2,9-dibromo-syn-dioxido[14]anulene (10) optically stable until 250°C. Consequently their inversion barriers are higher than 42 kcal (176 kJ) mol^–1.The CD spectra of mono and disubstituted anulenes (with C₁ and C₂ symmetry, resp.) are compared: For the [10]anulenes theCotton effect around 330 nm seems to be specific for their configuration with a positive effect indicating (S)-chirality and vice versa. Some regularities concerning the chromatographic resolutions are discussed.

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Stereochemie planar chialer Verbindungen, 10. Mitt.: Röntgenkristallstruktur und absolute Chiralität überbrückter [10]- und [14] Anulene

Zusammenfassung 2,7-Dibrom-1,6-methano[10]anulen (3) und 2,9-Dibrom-syn-1,6:8,13-diimino[14]anulen (9) wurden durch Chromatographie an Triacetylcellulose (TAC) in Ethanol quantitativ in ihre Enantiomeren getrennt. Röntgenstruktur-analyse (Bijvoet-Technik) bewies für die rechtsdrehenden Enantiomeren die Chiralität (+)(R)-3 bzw. (+)(S)-9.Ein Vergleich der CD-Spektren ermöglichte die Konfigurationszuordnung weiterer optisch aktiver [10]- und [14]Anulene, die gleichfalls durch Chromato-graphie anTAC erhalten worden waren. Umwandlung von (+)(R)-2-Brom-1,6-methano[10]anulen (2) in den entsprechenden Methylester (–)-4 bestätigte dessen schon früher vorgeschlagene Chiralität (–)(R).Dibrom-1,6-oxido[10]anulen (7) und Dibrom-diimino[14]anulen (9) sind im Gegensatz zum Dioxido[14]anulen (10) bis 250°C optisch stabil. Ihre Inver-sionsbarrieren liegen somit über 42 kcal (176kJ) mol^–1.Die CD-Spektren von mono- und disubstituierten Anulenen (mit C₁ bzw. C₂-Symmetrie) werden verglichen: Für die [10]Anulene scheint derCottoneffekt um 330 nm konfigurationsspezifisch zu sein, wobei ein positiver Effekt (S)-Chiralität anzeigt — und vice versa. Einige Regelmäßigkeiten bezüglich der chromatographischen Enantiomerentrennung werden diskutiert.

     

Detection of genetically modified corn (Bt176) in spiked cow blood samples by polymerase chain reaction and immunoassay methods

The fate of DNA and protein transgenic sequences in products derived from animals fed transgenic crops has recently raised public interest. Sensitive molecular tests targeting the Bt176 genetic construct and the transgenic Cry1Ab protein were developed to determine whether plant sequences, especially transgenic sequences, are present in animal products. A protocol for total DNA extraction and purification from cow whole blood samples was first drawn up and assessed by spiking with known amounts of DNA from Bt176 maize. The limit of detection for transgenic sequences (35S promoter and Bt176-specific junction sequence) was determined by both the polymerase chain reaction-enzyme-linked immunosorbent assay (PCR-ELISA) and the 5'-nuclease PCR assay. Four additional PCR systems were built to substantiate the results. The first detects a mono-copy maize-specific sequence (ADH promoter). Two others target multi-copy sequences from plant nucleus (26S rRNA gene) and chloroplast (psaB gene). The last one, used as a positive control, targets a mono-copy animal sequence (alpha(s1)-casein gene). Both methods detected a minimum spiking at 25 copies of Bt176 maize/mL in 10 mL whole blood samples. The sandwich ELISA kit used detected down to 1 ng transgenic Cry1Ab protein/mL spiked whole blood.     

Metabolite profiling in rat urine by liquid chromatography/electrospray ion trap mass spectrometry. Application to the study of heavy metal toxicity

This work reports the use of reverse-phase liquid chromatography coupled to electrospray ion trap (QIT) mass spectrometry for the analysis of the metabolome in rat urine. An injection of 20 microL of urine into the chromatographic system is followed by a slow gradient elution and mass spectrometric detection in the scanning mode from m/z 100-1000 in both positive and negative modes. Over a time scale of 90 min, 30 and 20 resolved peaks were observed in the positive and the negative modes, respectively, corresponding to the presence of a few hundred m/z ratios. By using a QIT analyzer, data-dependent tandem mass spectrometry of selected m/z ratios identified several compounds in rat urine and characterized various chemical families, including carboxylic acids, amines, sulfated compounds, glucuronides and glycosides, by the observation of characteristic fragment ions or neutral losses. The method has been applied to the investigation of the chronic toxicity of heavy metals in rat urine. A few tens of m/z ratios, differing in intensity more than threefold from control values, were observed in both positive and negative modes. The time variations for some selected ions suggest that LC/ESI-MS could allow selective characterization of biomarkers in response to specific toxic compounds.     

Synthesis and conformational studies of palladium(II) complexes containing [PhP(O)NP(E)Ph]− (E=S or Se)

The ligands [Ph₂P(O)NP(E)Ph₂]⁻ (E=S I; E=Se II) can readily be complexed to a range of palladium(II) starting materials affording new six-membered Pd–O–P–N–P–E palladacycles. Hence ligand substitution reaction of the chloride complexes [PdCl₂(bipy)] (bipy=2,2′-bipyridine), [{Pd(μ-Cl)(L–L)}₂] (HL–L=C₉H₁₃N or C₁₂H₁₃N), [{Pd(μ-Cl)Cl(PMe₂Ph)}₂] or [PdCl₂(PR₃)₂] [PR₃=PPh₃; 2PR₃=Ph₂PCH₂CH₂PPh₂or cis-Ph₂PCH=CHPPh₂] with either I (or II) in thf or CH₃OH gave [Pd{Ph₂P(O)NP(E)Ph₂-O,E}(bipy)]PF₆, [Pd{Ph₂P(O)NP(E)Ph₂-O,E}(L–L)], [Pd{Ph₂P(O)NP(E)Ph₂-O,E}Cl(PMe₂Ph)] or [Pd{Ph₂P(O)NP(E)Ph₂-O,E} (PR₃)₂]PF₆ in good yields. All compounds described have been characterised by a combination of multinuclear NMR [31 P{1 H} and 1 H] and IR spectroscopy and microanalysis. The molecular structures of five complexes containing the selenium ligand II have been determined by single-crystal X-ray crystallography. Three different ring conformations were observed, a pseudo-butterfly, hinge and in the case of all three PR₃ complexes, pseudo-boat conformations. Within the Pd–O–P–N–P–Se rings there is evidence for π-electron delocalisation.