Efficient and Convenient Method for Synthesis of Benzofuran-3-acetic Acids and Naphthafuran-acetic Acids

Herein, we report an efficient and convenient method for synthesis of benzofuran-3-acetic acids and naphthafuran-acetic acids 5a–p by the reaction of substituted-4-bromomethylcoumarins with aqueous sodium hydroxide at refluxing temperature. The obtained products are characterized by infrared, ¹H NMR, ¹³C NMR, and mass spectral data. Structures 5a and 5e are confirmed by their single x-ray diffraction studies. The advantages of this method are good yields, easy workup, and no chromatographic purifications.     

Convergent synthesis and preliminary biological evaluations of the stilbenolignan (+/-)-aiphanol and various congeners

Treatment of an equimolar mixture of stilbene 7 and cinnamyl alcohol 8 with silver carbonate in acetone-benzene afforded a ca. 2:1:2:1 mixture of the stilbenolignan (+/-)-aiphanol (1) and congeners 2-4 each of which show significant anti-angiogenic and COX-2 inhibitory properties.     

Symmetric binuclear complexes with an ‘end-off’ compartmental Schiff base ligand

Four binuclear transition metal(II) complexes: [Co₂L(-Cl)Cl₂] · 2H₂O, [Ni₂L(-Cl)Cl₂(H₂O)₂] · 2H₂O, [Cu₂L(-Cl)Cl₂] · 2H₂O and [Zn₂L(-Cl)Cl₂] · 2H₂O, where LH is the binucleating ligand 2,6-diformyl-4-methylphenol bis(2-hydrazino benzothiazole), were prepared. Based on the i.r. spectra, elemental analysis, conductivity measurements and thermal analysis, we propose that these complexes contain an endogenous phenoxide bridge and an exogenous chloride bridge. Magnetic and spectral data supports the existence of a weak antiferromagnetic interaction between the metal ions, and octahedral for Ni^II and a square pyramidal environment for remaining complexes. The compounds show significant growth inhibitory activity against the fungi, Aspergillus niger and Candida albicans, as compared to antibacterial activity against Bacillus cirroflagellosus and Pseudomonas auregenosa.     

Pentacoordinate phosphoranes with reversed apicophilicity as stable intermediates in a mitsunobu-type reaction

Diisopropyl azodicarboxylate (DIAD) undergoes a cycloaddition reaction with the cyclic phosphites CH(2)(6-t-Bu-4-Me-C(6)H(2)O)(2)PX (1) [X = NCS (a), N(3) (b), Cl (c), NHMe (d) and Ph (e)] to afford the novel pentacoordinate phosphoranes 2a-e as crystalline solids. This result is different from the reaction of PPh(3) with DIAD used in the well-known Mitsunobu reaction. X-ray crystallography of 2a, 2b, and 2d reveals that the nitrogen, rather than the oxygen, occupies an apical position of the trigonal bipyramidal phosphorus. This is in violation of the commonly accepted preferences for substituents in trigonal bipyramidal phosphorus. In 2e, although the oxygen of the five-membered ring occupies the expected apical position, the phenyl group also occupies (the other) apical position, forcing the more electronegative oxygen atoms of the eight-membered ring to span equatorial-equatorial positions. In contrast to the above, the isocyanato compound CH(2)(6-t-Bu-4-Me-C(6)H(2)O)(2)PNCO (1f), upon treatment with DIAD, affords compound 3 to which a tetracoordinate structure is assigned.     

Structure and properties of potential nonlinear optical materials

The synthesis, structure and properties of four ferrocene derivatives of 2-amino-1,2,3-triazole are reported. Solvatochromism is used as a screening process to assess the potential nonlinear optical behavior of these compounds. In general, this technique involves a number of assumptions, which may not be valid for organometallic complexes. Compound 3 crystallizes in space group P-1 with cell dimensions a = 5.771(2), b = 19.048(5), c = 19.343(5) Å and = 61.104(4), = 88.410(5), = 89.858(5)°; compound 5 crystallizes in space group P2₁/c with cell dimensions a = 12.545(2), b = 13.308(2), c = 20.513(4) Å and = 104.035(3)°; compound 9 crystallizes in space group P2₁/n with cell dimensions a = 12.599(4), b = 14.734(4), c = 13.619(5) Å, and = 107.63(2); compound 11 crystallizes in space group P-1 with cell dimensions a = 7.638(3), b = 9.619(4), c = 12.692(5) Å and = 77.588(7), = 78.416(7), = 71.357(7).     

Short H· · ·H distances in norbornene derivatives

A short H···H intramolecular interaction was reported previously for an anhydride of syn-sesquinorbornene. The synthesis and structure of a such an anhydride with an additional five-membered dithiole ring has been investigated. While hydrogen atom positions are not accurately located, the 1.62 Å separation indicates this molecule is a candidate for the shortest H···H interaction. Two cycloadducts of norbornadiene, which literature suggests might exhibit additional short interactions, are reported also; however, the isomers with minimal intramolecular interactions are the isolated products. C₂₂H₂₀O₃S₂, 3, crystallizes in P with a = 10.881(4), b = 13.712(8), C = 6.548(8) Å, = 101.32(6), = 107.49(5), = 90.49(4)°, D _calc = 1.445 g cm^–3, and Z = 2, C₂₁H₂₀O₄Cl₈, 5, in P2₁/n with a = 8.168(2), b = 13.488(4), c = 23.500(6) Å, = 94.72(2)°, D _calc = 1.597 g cm^–3, and Z = 4, C₂₁H₂₈O₄, 6, in P> with a = 12.667(2), b = 12.792(2), c = 12.540(2) Å, = 113.51(1), = 98.18(1), = 74.39(1)°, D _calc = 1.276 g cm^–3, and Z = 4.     

Modeling the effect of crosslinking in methyl-pendant poly(p-phenylene benzobisthiazole)

Molecular mechanics and dynamics simulations have been performed on methyl-pendant PBZT to study the effects of intermolecular crosslinking. Several possible crosslinked structures were investigated. The effect of crosslinking was found to be strongly dependent upon crosslink type and, in some instances, crosslink density. A significant axial stress is predicted to occur upon the formation of phenyl-to-phenyl type crosslinks. This provides a reasonable explanation for the experimental observation of transverse cracks in the skin of crosslinked, MePBZT fiber. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3057–3064, 1998     

On the evidence of crosslinking in methyl pendent PBZT fiber

In order to influence the compressive strength of the rigid rod polymeric fibers, methyl pendent poly(p-phenylene benzobisthiazole) fibers have been heat treated in the 400 to 550°C temperature range in air and in nitrogen for varying times to achieve intermolecular crosslinking. These fibers have been examined using Fourier transform infrared (FTIR) spectroscopy, ¹³C solid-state nuclear magnetic resonance (NMR) swelling behavior, and scanning electron microscopy. ¹³C NMR has also been carried out on solutions of as-spun fibers. Fibers heat-treated at 400°C, both in nitrogen and in air, up to heat-treatment times of 60 min are insoluble in 99% chlorosulfonic acid, however no direct evidence of crosslinking has been obtained for these fibers using spectroscopic techniques, suggesting that in these fibers the degree of crosslinking must be very low. Evidence that methyl groups are precursors to certain crosslinks was first seen via a weak methylene resonance in ¹³C solid-state NMR, corresponding to about 2% of the original methyl intensity, in a sample heat-treated at 450°C in air. Fibers heat-treated in nitrogen at 550°C for 10 minutes do not exhibit any swelling in chlorosulfonic acid, are brittle, have lost most methyl groups; however, some CH₂ groups form. In this fiber, the carbon intensity for the CH₂ group in the ¹³C solid-state NMR is 18% of the intensity for the CH₃ group in the as-spun fiber. The fibers heat-treated at 400 and 450°C show a fibrillar morphology, while the fibrillar morphology is not observed in the fibers heat-treated at 550°C in nitrogen for 10 min. Based on this work, it is our judgment that if heat treatment of this material is to improve compressive strength, the heat treatment protocol of time and temperature will probably be critical and the highest temperatures of exposure will probably lie in the 450 to 550°C range. © 1996 John Wiley & Sons, Inc.     

Structural investigations on lewis acid mediated solubilization of poly(p-phenylenebenzobisthiazole) in an aprotic solvent

Investigations on aluminum chloride-mediated solubilization of poly(p-phenylenebenzo-bisthiazole), PBZT, in nitromethane revealed that, in general, dilute solutions of the polymer prepared in nitromethane with a large molar excess of the Lewis acid with respect to PBZT were relatively stable and thus suitable for processing into films and coatings via regeneration with hydroxylic nosolvents while polymer solutions with minimum stoichiometrically required (PBZT:AlCl₃ molar ratio 1:4) or marginal molar excess of AlCl₃ relative to PBZT tended to gel during handling. Structural studies on polymer–Lewis acid complex solutions were performed using ¹H and ²⁷Al NMR. ¹H NMR of the protonated structure of the model compound 2,6-diphenylbenzo [1,2-d:4,5-d′] bisthiazole was useful for confirming the ¹H NMR assignments of PBZT-AlCl₃ complex solution in CD₃NO₂. ²⁷Al NMR was particularly useful in probing the different tetrahedrally coordinated environments of the Al nucleus in the polymer solution, pointing to a complexation interaction between the polymer molecule and the Lewis acid and also between the solvent and the Lewis acid. Direct evidence in the solid state for the presence of a reversible electron donor–acceptor complex (EDA complex) was obtained from FTIR spectra of complexed films, isolated and handled in an inert atmosphere. The structural changes upon PBZT complexation caused significant frequencly shifts in both aromatic as well as heteroring stretching modes relative to PBZT itself, and intensity variations indicative of changes in the resonance configuration between the 1,4-phenylene moiety and the aromatic heterocyclic ring were also observed upon complexation. A preliminary comparison between the pristine PBZT fibers and regenerated PBZT by dilute solution viscometry indicates that the process results, to some extent, in polymer degradation leading to a decrease in the molecular weight of the polymer © 1993 John Wiley & Sons, Inc.