Substituent Effects on NMR Spectroscopy of 2,2-Dimethylchroman-4-one Derivatives: Experimental and Theoretical Studies.

The attribution of 1H and 13C NMR signals of a library of 5-, 6- and 7-substituted 2,2-dimethylchroman-4-one derivatives is reported. Substituent effects were interpreted in terms of the Hammett equation, showing a good correlation for carbons para- to the substituent group, not for the meta- ones. Similarly, the Lynch correlation shows the additivity of the substituent chemical shifts in the case of both H and C nuclei, again with the exception of the carbons in the meta- position. Density Functional Theory (DFT)-predicted 1H and 13C chemical shifts correspond closely with experimentally observed values, with some exceptions for C NMR data; however, the correlation is valid only for the aromatic moiety and cannot be extended to the heterocyclic ring of the chroman-4-one scaffold.

Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, 15N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations.

Polymerization of benzoxazine resins is indicated by the disappearance of a 960-900 cm-1 band in infrared spectroscopy (IR). Historically, this band was assigned to the C-H out-of-plane bending of the benzene to which the oxazine ring is attached. This study shows that this band is a mixture of the O-C2 stretching of the oxazine ring and the phenolic ring vibrational modes. Vibrational frequencies of 3-phenyl-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-a) and 3-(tert-butyl)-3,4-dihydro-2H-benzo[e][1,3]oxazine (PH-t) are compared with isotope-exchanged and all-substituted compounds. Deuterated benzoxazine monomers, 15N-isotope exchanged benzoxazine monomers, and all-substituted benzoxazine monomers without aromatic C-H groups are synthesized and studied meticulously. The various isotopic-exchanges involved deuteration around the benzene ring of phenol, selective deuteration of each CH2 in the O-CH2-N (2) and N-CH2-Ar (4) positions on the oxazine ring, or simultaneous deuteration of both positions. The chemical structures were confirmed by 1H nuclear magnetic resonance spectroscopy (1H NMR). The IR and Raman spectra of each compound are compared. Further analysis of 15N isotope-exchanged PH-a indicates the influence of the nitrogen isotope on the band position, both experimentally and theoretically. This finding is important for polymerization studies of benzoxazines that utilize vibrational spectroscopy.

Photo-Fries rearrangement of aryl acetamides: regioselectivity induced by the aqueous micellar green environment.

Photochemical reactions tend to give more than one photoproduct. However, such a reaction can be a powerful synthetic tool when it is possible to conduct it in regioselective conditions yielding a single photoproduct. Water-surfactant solutions as reaction media can be considered as an approach in this context because they show products with different features than those from isotropic solutions. Here we describe results obtained from studying the effect on the prototypical photoreaction, known as the photo-Fries reaction of several substituted acetanilides and α-naphthyl acetamide within surfactant micelles (ionic and non-ionic micelles). This reaction involves homolytic cleavage of a C-N bond to yield a singlet radical pair. The surfactant micelles control the rotational and translational mobility of the radical pair, resulting in noticeable photoproduct selectivity.

Identification of Predictors of Metastatic Potential in Paragangliomas to Develop a Prognostic Score (PSPGL).

Context: Paragangliomas (PGLs) are rare tumors in adrenal and extra-adrenal locations. Metastasis are found in approximately 5% to 35% of PGLs, and there are no reliable predictors of metastatic disease. Objective: This work aimed to develop a prognostic score of metastatic potential in PGLs. Methods: A retrospective analysis was conducted of clinical data from a cohort with PGLs and tumor histological assessment. Patients were divided into metastatic PGL (presence of metastasis) and nonmetastatic PGL (absence of metastasis ≥96 months of follow-up) groups. Univariate and multivariable analysis were performed to identify predictors of metastatic potential. A prognostic score was developed based on coefficients of multivariable analysis. Kaplan-Meier curves were generated to estimate disease-specific survival (DSS). Results: Out of 263 patients, 35 patients had metastatic PGL and 110 patients had nonmetastatic PGL. In multivariable analysis, 4 features were independently related to metastatic disease and composed the Prognostic Score of Paragangliomas (PSPGL): presence of central or confluent necrosis (33 points), more than 3 mitosis/10 high-power field (HPF) (28 points), extension into adipose tissue (20 points), and extra-adrenal location (19 points). A PSPGL of 24 or greater showed similar sensitivity with higher specificity than the Pheochromocytoma of the Adrenal Gland Scaled Score (PASS) and Grading System for Adrenal Pheochromocytoma and Paraganglioma (GAPP). PSPGL less than or equal to 20 was associated with a risk of metastasis of approximately 10%, whereas a PSPGL of 40 or greater was associated with approximately 80%. The presence of metastasis and Ki-67 of 3% or greater were related to lower DSS. Conclusion: The PSPGL, composed of 4 easy-to-assess parameters, demonstrated good performance in predicting metastatic potential and good ability in estimating metastasis risk.

Design and Effects of the Cinnamic Acids Chemical Structures as Organocatalyst on the Polymerization of Benzoxazines.

This study focuses on the catalytic effect of the two geometric isomers of a cinnamic acid derivative, E and Z-forms of 3-methoxycinnamic acid (3OMeCA), analyzing the influence of their chemical structures. E and Z-3OMeCA isomers show very good catalytic effect in the polymerization of benzoxazines, decreasing by 40 and 55 °C, respectively, the polymerization temperatures, for catalyst contents of up to 10% w/w. Isothermal polymerizations show that polymerizations are easily realized and analyzed at temperatures as low as 130 °C and at much shorter times using Z-3OMeCA instead of E-3OMeCA. Thus, both cinnamic acids are good catalysts, with Z-3OMeCA being better. The molecular reasons for this difference and mechanistic implications in benzoxazine polymerizations are also presented.

Development of Hydrogen-Rich Benzoxazine Resins with Low Polymerization Temperature for Space Radiation Shielding.

A systematic study has been carried out to develop a material with significant protection properties from galactic cosmic radiation and solar energetic particles. The research focused on the development of hydrogen-rich benzoxazines, which are particularly effective for shielding against such radiation. Newly developed benzoxazine resin can be polymerized at 120 °C, which meets the low-temperature processing requirements for use with ultrahigh molecular weight polyethylene (UHMWPE) fiber, a hydrogen-rich composite reinforcement. This highly reactive benzoxazine resin also exhibits low viscosity and good shelf-life. The structure of the benzoxazine monomer is confirmed by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. Polymerization behavior and thermal properties are evaluated by differential scanning calorimetry and thermogravimetric analysis. Dynamic mechanical analysis is used to study chemorheological properties of the benzoxazine monomer, rheological properties of the cross-linked polybenzoxazine, and rheological properties of UHMWPE-reinforced polybenzoxazine composites. The theoretical radiation shielding capability of the composite is also evaluated using computer-based simulations.