Crystal structure of the yellow 1:2 molecular complex lumiflavin–bisnaphthalene-2,3-diol

In the first molecular complex of the physiologically active neutral form of isoalloxazine studied, lumiflavin–bisnaphthalene-2,3-diol, each flavin is sandwiched between two naphthalenediol molecules with extensive overlap but a moderately large (3·44 Å) spacing, indicating at most weak charge-transfer interaction and in agreement with the yellow colour of the complex, nearly the same as that of the parent lumiflavin

Electronic effects on C-O-C ether bonds in 3-aryloxy derivatives of benzisothiazole 1,1-dioxides: rapid ethanolysis of 3-(4-nitrophenoxy)-1,2-benzisothiazole 1,1-dioxide, (1), to give 3-ethoxy-1,2-benzisothiazole 1,1-dioxide, (2)

The bond lengths in the central C-O-C ether linkage of title compound (1), C13H8N2O5S, are comparable with those found in earlier work on similar compounds. However, (1) was found to undergo very easy solvolysis with ethanol to give (2), C9H9NO3S, for which a structure was also determined, but 3-(4-methoxyphenoxy)-1,2-benzisothiazole 1,1-dioxide, (3), did not hydrolyse under the same conditions. If ground-state structures are important for solvolysis, these results suggest that there should be a difference in the corresponding C-O bond lengths for the ethers (1) and (3). Such differences are not observed. The results can be rationalized by supposing that transition-state energies for ethanolysis are more important factors than those of the ground state.info:eu-repo/semantics/publishedVersio

3-Hydroxy-2,6-dinitroacetophenone: an unusual substitution pattern resulting from nitration of 3-hydroxyacetophenone

Nitration of 3-hydroxyacetophenone gives 2,6-dinitro-3-hydroxyacetophenone, C8H6N206, in which the nitro groups have entered the sterically least favourable positions in the aromatic nucleus. None of the expected substitution in the 4-position was observed. The two nitro groups flanking the carbonyl side chain are different in that one is in the plane of the aryl ring but the other is twisted well out of the plane

Bond energy/eond order relationships for N-O linkages and a quantitative measure of ionicity: the rôle of nitro groups in hydrogen bonding

The nitro group is active in metabolic systems and can be found as an integral part of a number of useful curative drugs and many toxic substances. The basis for much of this activity is not fully understood. It is not necessarily caused directly by through-bond electronic effects but may also be due to direct H-bonding to nitro or to indirect interference by the nitro group with existing H-bonding. An unusual effect of a nitro substituent on kinetic results from urethane addition/elimination reactions (Scheme 1) has been ascribed to some form of self-association, which was neither specified nor quantified. To investigate self-association phenomena caused by a nitro group, a bond energy/bond order formula for N–O bonds has been developed and then used to interpret relative amounts of covalent and ionic contributions to total N–O bond energy. Calculated bond energies were then used to obtain enthalpies of formation for H-bonds to nitro groups in crystals and in solution. Similar results from solution data reveal that direct H-bonding to nitro is much weaker than in crystals, unless intramolecular H-bonding can occur. The results revealed that the 'self-association' effects observed for nitro substituents in urethanes (Scheme 1) were not caused by nitro participating directly in intermolecular bonding to NH of another urethane but by an indirect intramolecular action of the nitro group on pre-existing normal NH–O amide/amide type H-bonding

3-( E )-But-2-enoxy-1,2-benzisothiazole 1,1-dioxide: unusual C—O—C ether bond lengths and reactivity

Ethers such as the title compound, C~HIINO3S, (1), rearrange thermally to give N-allyl isomers, (2), in high yield. The X-ray structure determination of the title ether shows a central C--O--C linkage which has one very short (notional) C--O single bond and one exceptionally long single C--O bond. The thermal migration of allyl from the O to the N atom involves the breaking of one of the ether bonds in (1) and a shortening of the other as it becomes a formal carbonyl group in the product (2). The rearrangement is thus considerably assisted by the ground-state structure of the starting ether, in which the bond to be broken is already stretched and the one that is to form a carbonyl group is already a substantial partial double bond

Thermal rearrangement of 3-allyloxy-1,2-benzisothiazole 1,1-dioxides: an unusual inversion of products of sigmatropic [3,3]-shift to give the [1,3]-Isomers

3-Allyloxy-1,2-benzisothiazole 1,1-dioxides isomerize thermally to give [3,3]- and [1,3]-products 6 of sigmatropic shift, of which the former reacts further to give solely the [1,3]-isomer

Characterizing Van Kampen Squares via Descent Data

Categories in which cocones satisfy certain exactness conditions w.r.t. pullbacks are subject to current research activities in theoretical computer science. Usually, exactness is expressed in terms of properties of the pullback functor associated with the cocone. Even in the case of non-exactness, researchers in model semantics and rewriting theory inquire an elementary characterization of the image of this functor. In this paper we will investigate this question in the special case where the cocone is a cospan, i.e. part of a Van Kampen square. The use of Descent Data as the dominant categorical tool yields two main results: A simple condition which characterizes the reachable part of the above mentioned functor in terms of liftings of involved equivalence relations and (as a consequence) a necessary and sufficient condition for a pushout to be a Van Kampen square formulated in a purely algebraic manner.Comment: In Proceedings ACCAT 2012, arXiv:1208.430

Young Stellar Objects in the Gould Belt

We present the full catalog of Young Stellar Objects (YSOs) identified in the 18 molecular clouds surveyed by the Spitzer Space Telescope "cores to disks" (c2d) and "Gould Belt" (GB) Legacy surveys. Using standard techniques developed by the c2d project, we identify 3239 candidate YSOs in the 18 clouds, 2966 of which survive visual inspection and form our final catalog of YSOs in the Gould Belt. We compile extinction corrected SEDs for all 2966 YSOs and calculate and tabulate the infrared spectral index, bolometric luminosity, and bolometric temperature for each object. We find that 326 (11%), 210 (7%), 1248 (42%), and 1182 (40%) are classified as Class 0+I, Flat-spectrum, Class II, and Class III, respectively, and show that the Class III sample suffers from an overall contamination rate by background AGB stars between 25% and 90%. Adopting standard assumptions, we derive durations of 0.40-0.78 Myr for Class 0+I YSOs and 0.26-0.50 Myr for Flat-spectrum YSOs, where the ranges encompass uncertainties in the adopted assumptions. Including information from (sub)millimeter wavelengths, one-third of the Class 0+I sample is classified as Class 0, leading to durations of 0.13-0.26 Myr (Class 0) and 0.27-0.52 Myr (Class I). We revisit infrared color-color diagrams used in the literature to classify YSOs and propose minor revisions to classification boundaries in these diagrams. Finally, we show that the bolometric temperature is a poor discriminator between Class II and Class III YSOs.Comment: Accepted for publication in ApJS. 29 pages, 11 figures, 14 tables, 4 appendices. Full versions of data tables (to be published in machine-readable format by ApJS) available at the end of the latex source cod

Investigations into the mechanism of action of nitrobenzene as a mild dehydrogenating agent under acid-catalysed conditions

Protonated nitrobenzene can be used to dehydrogenate a range of hydrocarbons, which already possess at least one double bond. Kinetic and spectroscopic results, together with known electrode potentials, yield approximate limits within which protonated nitrobenzenes can be expected to effect dehydrogenation of hydroaromatic compounds. A high yielding synthesis of benzo[ j ]fluoranthene is described