İlker Ün

Structural investigations of phosphorus–nitrogen compounds. 7. Relationships between physical properties, electron densities, reaction mechanisms and hydrogen-bonding motifs of N3P3Cl(6 − n)(NHBut)n derivatives

A series of compounds of the N3P3Cl(6 - n)(NHBu(t))n family (where n = 0, 1, 2, 4 and 6) are presented, and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N3P3Cl5(NHBu(t)) and N3P3Cl2(NHBu(t))4 have been determined at 120 K, and those of N3P3Cl6 and N3P3Cl4(NHBu(t))2 have been redetermined at 120 K. These are compared with the known structure of N3P3(NHBu(t))6 studied at 150 K. Trends in molecular parameters [phosphazene ring, P-Cl and P-N(HBu(t)) distances, PCl2 angles, and endo- and exocyclic phosphazene ring parameters] across the series are observed. Hydrogen-bonding motifs are identified, characterized and compared. Both the molecular and the hydrogen-bonding parameters are related to the electron distribution in bonds and the derived basicities of the cyclophosphazene series of compounds. These findings provide evidence for a proposed mechanism for nucleophilic substitution at a phosphorus site bearing a PCl(NHBu(t)) group.

Octasolketal-substituted phthalocyanines: synthesis and systematic study of metal effect and substitution pattern on 13C NMR

A complete series of solketal octasubstituted phthalocyanines have been synthesized, with peripheral (β) or non-peripheral (α) substitution pattern. Their 13C NMR and UV-vis properties are compared relatively to this substitution pattern or the nature of the central metal (Ni, Zn or H2).

Phthalonitriles Functionalized for Click Chemistry. Design, Synthesis and Structural Characterization

AbstractTwo phthalonitriles complementarily functionalized by an azide and an alkyne function have been designed for the click Huisgen azide-alkyne dipolar addition reaction. Their synthesis and full structural characterization is presented here with a comparative approach.Graphical AbstractTwo phthalonitriles complementarily functionalized by an azide and an alkyne function and their full structural characterization is presented with a comparative approach..

Comparative structural analysis of 4,5- and 3,6-dialkylsulfanylphthalonitriles of different bulkiness

Phthalonitriles disubstituted by alkylsulfanyl moieties of different bulkiness (tert-butyl, adamantly, cyclohexyl and hexyl) and in 4,5- or 3,6-positions, respectively, set A and set B, have been prepared for comparative structural analyses. Miscellaneous parameters such as melting points and related polarity of the compounds are summarized. Substituents position and bulkiness effects on NMR and IR spectroscopy as well as refined X-ray structural data were examined.

The diverse behaviour of the P-Cl bonds in the spiro-cis-ansa spermidine derivative cyclotriphosphazene towards mono-functional nucleophilic reagents

A number of new spiro-ansa spermidine derivative cyclotriphosphazenes (2-10) is synthesized in order to provide insight into the reaction mechanism for nucleophilic substitution. The structures of the compounds were determined by elemental analysis, mass (MS), (1)H, (19)F (for 9) and (31)P NMR spectroscopies. Compounds (2-8) and 9, 10 can be formed by a proton abstraction-chloride elimination and both the S(N)(1) and S(N)(2) reaction mechanisms, respectively.

Analysis of olive oil for authentication and shelf life determination

AbstractHigh-field proton (1H) nuclear magnetic resonance (NMR) spectroscopy was applied for screening the fatty acyl contents of 33 olive oil samples from five different geographical regions of Turkey to do geographical discrimination analysis. The 1H NMR data were subjected to principal component analysis (PCA) and analysis of variance (ANOVA) to discriminate the origin of olive oils. The combination of discriminative screening by 1H NMR and ANOVA did not require further analysis of olive oil such as gas chromatography (GC). ANOVA was employed for samples from three regions separately: Marmara Region (MR), Aegean Region (AR), and Mediterranean Region (MeR). The best discriminative parameter was the 1H NMR signal of linoleoyl acyl content. Applying both quantitative NMR and statistical analysis indicated that samples from different provinces within each geographical region (MR, AR, and MeR) could be discriminated. Comparing the linoleoyl and oleoyl acyl contents of Turkish olive oils with these of some Mediterranean olive oils showed the possibility of distinguishing the Turkish olive oils. 1H NMR spectra of three olive oil samples with the production years of January 2013, January 2014, and January 2015 were acquired in 2016 for discussing shelf life of olive oil by quantifying fatty acyls content, and determining minor constituents and possible by-products during storage. The effects of altitude and soil quality on fatty acyl contents of olive oil samples from a small olive growing village in Northeastern Turkey were also tested.