GIAO/DFT evaluation of 13C NMR chemical shifts of selected acetals based on DFT optimized geometries

DFT/B3LYP calculations of the ground-state conformation of eight cyclic and acyclic acetals are presented and compared with experimental data. Results of single-point GIAO/DFT calculations at five different levels of theory show that isotropic shieldings need to be empirically scaled to achieve agreement with experimental chemical shifts. Statistical evaluation of data indicates that the most accurate prediction of 13C chemical shifts is achieved at the MPW1PW91/6-311G** level of theory. An empirical equation describing the relationship between delta values and shielding constants is postulated. This equation has been applied to the non-chair ground-state conformation of the six-membered acetonide and to the conformationally flexible benzodioxonine derivative. The agreement observed between the experimental and predicted chemical shifts shows that calculations at the MPW1PW91/6-311G** level of theory are adequate for addressing questions of conformation.     

Terreinol--a novel metabolite from Aspergillus terreus: structure and C labeling

A novel metabolite from Aspergillus terreus, named terreinol, was isolated and its biosynthetic origin was determined by NMR based on the incorporation of [1-¹³C]-d-glucose. The labeling pattern indicated a predominant polyketide biosynthetic origin for this metabolite.     

Comment on the assignments of some vibrational bands of oxalyl fluoride

In view of existing contradictory assignments of the symmetrical stretching vibrations associated with the formal C-C and C-F bonds of trans/cis oxalyl fluoride, an additional theoretical analysis of the corresponding calculated wavenumbers was preformed on trans-C₂O₂F₂ and cis-C₂O₂F₂ based on previously calculated ab initio scaled force fields at the HF/6-31G computational level and new force fields calculated at the MP2/aug-cc-pVTZ level. This novel analysis included computational data from the isotopic shifts brought about by incorporating ¹³C and ¹⁴C atoms into the structure. A detailed examination of the calculated wavenumbers made it possible to validate the assignments of the ν₂ and ν₃ wavenumbers in the trans-C₂O₂F₂ and cis-C₂O₂F₂ molecules as the formal C-C bond stretching and the formal C-F bond symmetrical stretching vibrations, respectively.     

Application of isotopic labeling,and gas chromatography mass spectrometry,to understanding degradation products and pathways in the thermal-oxidative aging of Nylon 6.6

Nylon 6.6 containing ¹³C isotopic labels at specific positions along the macromolecular backbone has been subjected to extensive thermal-oxidative aging at 138 °C for time periods up to 243 days. In complementary experiments, unlabeled Nylon 6.6 was subjected to the same aging conditions under an atmosphere of ¹⁸O₂. Volatile organic degradation products were analyzed by cryofocusing gas chromatography mass spectrometry (cryo-GC/MS) to identify the isotopic labeling. The labeling results, combined with basic considerations of free radical reaction chemistry, provided insights to the origin of degradation species, with respect to the macromolecular structure. A number of inferences on chemical mechanisms were drawn, based on 1) the presence (or absence) of the isotopic labels in the various products, 2) the location of the isotope within the product molecule, and 3) the relative abundance of products as indicated by large differences in peak intensities in the gas chromatogram. The overall degradation results can be understood in terms of free radical pathways originating from initial attacks on three different positions along the nylon chain which include hydrogen abstraction from: the (CH₂) group adjacent to the nitrogen atom, at the (CH₂) adjacent the carbonyl group, and direct radical attack on the carbonyl. Understanding the pathways which lead to Nylon 6.6 degradation ultimately provides new insight into changes that can be leveraged to detect and reduce early aging and minimize problems associated with material degradation.     

N-(4-(di-tert-butyl[F]fluorosilyl)benzyl)-2-hydroxy-N,N-dimethylethylammonium bromide ([F]SiFANBr): A novel lead compound for the development of hydrophilic SiFA-based prosthetic groups for F-labeling

¹⁸F-labeled compounds play a major role in the development of new in vivo imaging agents for Positron Emission Tomography (PET), a non invasive imaging modality depicting the biodistribution of radioactive compounds in humans. Recently we reported a new method for the introduction of fluorine-18 into a range of organic molecules exploiting the very fast ¹⁸F-¹⁹F isotope exchange of fluorosilanes (termed SiFA compounds). Here, we wish to report the labeling of the first charged SiFA molecule N-(4-(di-tert-butylfluorosilyl)benzyl)-2-hydroxy-N,N-dimethylethylammonium bromide (SiFAN⁺Br⁻) serving as a lead compound in the development of SiFA-based prosthetic groups of reduced lipophilicity for biomolecule labeling. Mild conditions for synthesis of [¹⁸F]SiFAN⁺Br⁻ and an easy purification procedure using simple C-18 solid phase cartridge have been developed yielding the [¹⁸F]SiFAN⁺Br⁻ in radiochemical yields of 34% (non-decay corrected) within 40 min. A series of kinetic experiments were performed that show high isotopic exchange rate constants. Low activation energy (15.7 kcal/mol) and a large preexponential factor (7.9 × 10¹³ M⁻¹ s⁻¹) were calculated for the isotopic exchange reaction from a corresponding Arrhenius plot. For comparison, the ¹⁸F-fluorination of ethyleneglycol-di-p-tosylate via the formation of a carbon-¹⁸F bond showed a 1.3 kcal/mol higher activation energy and a much lower preexponential factor of 2.9 × 10⁹ M⁻¹ s⁻¹. Moderate hydrophilicity (log D = 0.44), stability in aqueous media at pH up to 7.4 and a high specific activity of [¹⁸F]SiFAN⁺Br⁻ (SA = 20.4 GBq/μmol, 0.55 Ci/μmol) make this charged SiFA compound useful for the development of novel SiFA-based ¹⁸F-labeling synthons.     

Naryl-substituted anthranilamides with intramolecular hydrogen bonds

Hydrogen bonding interaction as one type of non-covalent force has proven itself to be highly efficient for constructing structurally unique artificial secondary structures. Here, the structure of N_aryl-substituted anthranilamide in solution is demonstrated by various NMR technique, the intramolecular hydrogen bonds between amide attached to arylamine of the same ring is proposed, which is supported by its crystal structure in the solid phase. The substituent on the nitrogen atom of arylamine plays an important role in forming the presence of intramolecular hydrogen bonds. The chemical shift of the N_aryl-H downfield changes obviously, due to the formation of intramolecular hydrogen bonds and the deshielding effect of oxygen, and the neighboring C–H is activated and shows downfield protonic signal too. The presence of intramolecular hydrogen bonds probably provides the explanation for the transformation from N_aryl-substituted anthranilamide to imine, which could be converted into 2-aryl quinazolinone finally.     

丙酮肟与某些芳烃相互作用的~1H核磁共振研究

Hatton和Richards通过对酰胺分子的~1H NMR谱溶剂效应的研究,提出了DMF与苯生成分子络合物的模型.如果络合物按1:1生成,那么将出现一个“饱和点”,在这点上甲基的芳香溶剂诱导位移(ASIS)的变化趋势或程度将出现一个明显的变化,事实上随着苯的摩尔分数从0到1逐渐增加时,化学位移总是有规则的逐渐移向高场.这就显示了分子络合物观点的局限性.它能被一些研究者所支持和接受,是因为它能够解释两个甲基共振峰先重合而后又分离的现象.     

Role of elemental fluorine in nuclear field

The preparation of fluorine gas by Henri Moissan by electrolysis of molten fluorides can be considered as one of the most important discoveries during the last centuries. Indeed, in addition to its use in many industrial fields (microelectronic, surface cleaning, pharmacology, medicine, …), fluorine gas is strongly involved in nuclear field for the preparation of UF₆. The latter allows the natural uranium enrichment via the gaseous diffusion process. Due to the increase of the energy demand in industrialised and emergent countries, the production of UF₆ and consequently of F₂ should increase drastically during the next decades. The aim of this paper is to summarise the evolution of the process to produce fluorine from its discovery to the present process. Few aspects on the researches done for a better understanding of the fluorine evolution reaction are presented. The use of fluorine in the nuclear field is also discussed.     

STUDIES ON ORGANOPHOSPHORUS COMPOUNDS XXX. MASS SPECTROSCOPIC INVESTIGATION OF 2-ALKYL-2-OXO-1,3,2-DIOXA-PHOSPHORINANE AND-PHOSPHEPANE

Abstract

The mass spectra of 2-alkyl-2-oxo-1,3,2-dioxa-phosphorinane and-phosphepane showed that the ring opening was in competition with the cleavage of the P[sbnd]C bond. According to the fragmentation pathway, which was dependent on the structure of exocyclic substituents on phosphorus, the 2-alkyl-2-oxo-1,3,2-di-oxa-phosphorinanes can be classified in two categories. The main process in category A was the ring opening and/or C[sbnd]C bond cleavage. While in category B the cleavage of P[sbnd]C bond was predominant. However, for 2-alkyl-2-oxo-1,3,2-dioxa-phosphepane. no matter how the structure of 2-alkyl group was, the ring opening was a dominant process.     

On the Constant Pressure Specific Heat CP of a Simple Fluid

Abstract

Calculation of C_P from a model soft-core equation of state reveals a line in the phase diagram on which C_P is equal to its zero pressure value C _{P 0} . This line commences on the temperature axis where the second virial coefficient has a point of inflexion. At higher temperatures (and pressures) C_P falls below C _{P 0} . The detailed behaviour of C_P is presented via contour maps, illustrating the effects of changing the exponent N(= 3/n, where n is the repulsive potential exponent) which parameterizes the model. For soft-core fluids at high temperatures C_P deviates only slightly from the ideal gas value over a wide range of temperature and density, in marked contrast to the behaviour of hard-core models.