The nature of products in the diazotization of 1-amino-2-acetylenyl-9,10-anthraquinones strongly depends on the nature of substituents at both the alkyne and at the anthraquinone core. Donor substitution (NHAr, OH) at the fourth position stabilizes the diazonium salt at C1, decelerating electrophilic cyclization at the arylethynyl substituent at C2. This effect allows the replacement of the diazonium with azide group and subsequent closure into isoxazole ring with preservation of the alkyne. In contrast, electrophilic 5-exo-dig cyclizations to condensed pyrazoles is observed for the combination of donor substituents at the aryl alkyne moiety and an OAc substituent at C4. The latter process provides a new synthetic route to 3-ethynyl-[1,9-cd]isoxazol-6-ones that are difficult to access otherwise. DFT calculations suggest that donor substituents have only a minor effect on alkyne and diazonium polarization in the reactant but provide specific transition state stabilization by stabilizing the incipient vinyl cation. This analysis provides the first computational data on electrophilic 5-exo-dig cyclization in its parent form and the nucleophile-promoted version. This cyclization is a relatively fast but endothermic process that is rendered thermodynamically feasible by the enol-keto tautomerization with concomitant aromatization in the five-membered heteroaromatic ring. Computations suggest that the importance of nucleophilic assistance in the transition state for a relatively weak nucleophile such as water is minor because the energy gain due to the Lewis base coordination to the carbocationic center is more than compensated for by the unfavorable entropic term for the bimolecular proces.

Methods of absorption and fluorescent spectroscopy and fluorescent chronoscopy are used to investigate aqueous fluorescein solutions with pH values increasing from 1.79 to 11.67. For each method, the calibration curves are drawn for the fraction of dianion fluorescein species, quantum fluorescence yield, and amplitude dianion contribution to the fluorescence intensity on the pH values of aqueous solutions. The calibration curves allow the pH values of aqueous fluorescein solutions with gelatin (pH = 6.4 ± 0.1, 6.6 ± 0.2, and 6.6 ± 0.1), starch (pH = 6.3 ± 0.1, 6.3 ± 0.2, and 6.4 ± 0.1), and acid-soluble chitosan additions (pH = 5.4 ± 0.1, 5.6 ± 02, and 5.8 ± 0.1) to be estimated by these three methods. The pH values of biopolymer solutions obtained by the potentiometer method for starch (6.51) and gelatin (6.69) and by the three spectral and fluorescent methods are close; they are significantly underestimated (3.85) for chitosan solutions.

Amination O 0268Amination of 1,3-Dihalo-2-nitrosobenzenes. -Reaction of the title dihalonitrosobenzenes with amines gives previously unknown nitrosobenzene derivatives containing alkylamino groups in the 3-and 5-position. -(GORNOSTAEV, L. M.; BOCHAROVA, E. A.; GEETS, N. V.; Russ.

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By reactions of 4-amino-2,6-dihalonitrosobenzenes with sodium azide and 4,6-dihalo-2,1,3-benzoxadiazoles with amines a group of 2,1,3-benzoxadiazole aminoderivatives was prepared.