Novel reactions of phosphorus(III) azides and isocyanates: unusual modes of cycloaddition with dipolarophiles and an unexpected case of ring expansion

New modes of 1,3-dipolar cycloaddition are uncovered by the isolation of [CH2(6-t-Bu-4-Me-C6H2O)2]P(C(CO2Me)C(CO2Me)N[NP(N3)(OC6H2-6-t-Bu-4-Me)2CH2]N) (3) and [CH2(6-t-Bu-4-Me-C6H2O)2]P(C(CO2Me)C(CO2Me)C(O)N) (4) on treating [CH2(6-t-Bu-4-Me-C6H2O)2]P-X [X = N3 (1) and NCO (2)] with the dipolarophile MeO2CC identical to CCO2Me; compound 4 undergoes an unprecedented ring expansion upon addition of 2-(methylamino)ethanol to afford the spirocycle [CH2(6-t-Bu-4-Me-C6H2O)2]P(OCH2CH2N(Me)CH(CO2Me)CH(CO2Me)C(O)N) (5).     

Non-stoichiometry induced by differential oxygen/lone pair occupation in chiral bicyclic 1,1'-binaphthoxy cyclodiphosphazanes

Non-stoichiometry and isostructurality in a set of chiral phosphorus compounds as a result of lone pair/oxygen exchange, substantiated by the combined use of 31P NMR spectroscopy and X-ray crystallography, is described.     

Identification of statistical regimes and crossovers in coherent random laser emission

We measure intensity statistics and identify statistical regimes and crossovers in random lasers based on nonresonant feedback. A single parameter extracted from an α-stable Levy fit is used to characterize the intensity distributions in all regimes. Measurements made over a range of scattering strengths, excitation energies, and sample sizes enable us to demarcate three regimes of intensity statistics and the corresponding crossovers. An initial subthreshold Gaussian regime abruptly transits into a Levy regime at the random lasing threshold, which is followed by a continuous gradual crossover toward a second Gaussian regime. We find that the prominence of the Levy regime depends upon the sample size.     

Aerosol-based coherent random laser

We demonstrate coherent random lasing from an aerosol of dye-doped microdroplets in air. The aerosol is in the form of a linear array of polydisperse, arbitrarily shaped, and randomly spaced microdroplets with average dimensions of about 30 μm. Upon optical excitation, ultranarrow lasing modes were observed in the emission along the axis of the linear array, while the transverse emission exhibited intrascatterer resonance peaks. Direct spatiospectral imaging and lasing threshold studies confirmed the origin of the lasing peaks to be from spatial modes that extended over the array of the polydisperse microdroplets.     

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.     

Synthetic studies directed toward amphidinol 2: elucidation of the relative configuration of the C1-C10 fragment

Model compounds (11 and 12) for the C1-C10 tetrahydropyran fragment of amphidinol 2 were prepared from (2S)-benzyloxypropanal in 9 steps. The synthetic route relied on diastereoselective diene-aldehyde cycloaddition, stereoselective C-allylation, and reagent based enantioselective aldehyde allylation. Comparison of the NMR spectra for models 11 and 12 with that for amphidinol 2 indicated that the C1-C10 segment of the natural product possesses the 2R^∗,4R^∗,6R^∗,7S^∗,8R^∗,10S^∗relative configuration.     

Very strong C-H...O, N-H...O, and O-H...O hydrogen bonds involving a cyclic phosphate.

Very short C-H...O, N-H...O, and O-H...O hydrogen bonds have been generated utilizing the cyclic phosphate [CH2(6-t-Bu-4-Me-C6H2O)2]P(O)OH (1). X-ray structures of (i) 1 (unsolvated, two polymorphs), 1...EtOH, and 1...MeOH, (ii) [imidazolium](+)[CH2(6-t-Bu-4-Me-C6H2O)2PO2](-)...MeOH [2], (iii) [HNC5H4-N=N-C5H4NH](2+)[(CH2(6-t-Bu-4-Me-C6H2O)2PO2)2](2-)...4CH3CN...H2O [3], (v) [K, 18-crown-6](+)[(CH2(6-t-Bu-4-Me-C6H2O)2P(O)OH)(CH2(6-t-Bu-4-Me-C6H2O)2PO2)](-)...2THF [4], (vi) 1...cytosine...MeOH [5], (vii) 1...adenine...1/2MeOH [6], and (viii) 1...S-(-)-proline [7] have been determined. The phosphate 1 in both its forms is a hydrogen-bonded dimer with a short O-H...O distance of 2.481(2) [triclinic form] or 2.507(3) A [monoclinic form]. Compound 2 has a helical structure with a very short C-H...O hydrogen bond involving an imidazolyl C-H and methanol in addition to N-H...O hydrogen bonds. A helical motif is also seen in 5. In 3, an extremely short N-H...O hydrogen bond [N...O 2.558(4) A] is observed. Compounds 6 and 7 also exhibit short N-H...O hydrogen bonds. In 1...EtOH, a 12-membered hydrogen-bonded ring motif, with one of the shortest known O-H...O hydrogen bonds [O...O 2.368(4) A], is present. 1...MeOH is a similar dimer with a very short O(-H)...O bond [2.429(3) A]. In 4, the deprotonated phosphate (anion) and the parent acid are held together by a hydrogen bond on one side and a coordinate/covalent bond to potassium on the other; the O-H...O bond is symmetrical and very strong [O...O 2.397(3) A].     

Experimental and numerical investigation of a cracked transversely graded plate subjected to in plane bending

The variation of stress intensity factor along the thickness in a cracked transversely graded plate subjected to in plane bending is investigated in this study. A transversely graded plate having elastic modulus varying continuously along the thickness was prepared by embedding glass beads in epoxy resin. An edge crack in this plate was subjected to in plane bending and the crack tip displacement field on the surfaces of the plate was measured using digital image correlation (DIC). Using the recently reported asymptotic displacement fields for cracked transversely graded plates (Wadgaonkar, S.C., Parameswaran, V., 2009. Structure of near tip stress field and variation of stress intensity factor for a crack in a transversely graded material, Journal of Applied Mechanics 76 (1), 011014), the stress intensity factor (SIF) on the surfaces of the plate was calculated from the experimental data. The results of this part of the study indicated that the extent of variation of the SIF across the plate thickness is nearly the same as that of the elastic modulus. An expression to calculate the variation of the SIF through the plate thickness was developed assuming simple bending of the plate. The predicted variation of SIF was verified through finite element calculations. Further, the behavior of the SIF near the intersection of the crack front and the plate surfaces, the extent of dominance of the corner singular field and the exponent of the corner singularity were also investigated in detail. Finally, the effect of gradation strength and gradation type on the SIF was also studied.     

Frequency behavior of coherent random lasing in diffusive resonant media

We investigate diffusive propagation of light and consequent random lasing in an amplifying medium comprising resonant spherical scatterers. A Monte-Carlo calculation based on photon propagation via three-dimensional random walks is employed to obtain the dwell-times of light in the system. We compare the inter-scatterer and intra-scatterer dwell-times for representative resonant and non-resonant wavelengths. Our results show that more efficient random lasing, with intense coherent modes, is obtained for a system with intra-scatterer gain. This is also coupled with a larger reduction in frequency fluctuations. We find that such a system can yield almost thresholdless random lasing. Inspired by these results, we discuss a possible practical situation, based on a monodisperse aerosol, wherein frequency controlled coherent random lasing can be obtained. Since our analysis essentially investigates transport of intensity, the results are relevant to coherent random lasers under nonresonant feedback.     

Chemistry of selected cyclic P(III) compounds possessing a P-Cl bond

The compounds [CH₂(6-t-Bu-4-Me-C₆H₂O)₂]PCl (1), (OCH₂CMe₂CH₂O)-PCl (2), and [ClPN(t-Bu)]₂ (3) have been utilized as precursors in the synthesis of (i) new pentacoordinate phosphorus compounds [e.g. CH₂(6-t-Bu-4-Me-C₆H₂O)₂ P(NRR′)(O₂C₆C1₄), CH₂(6-t-Bu-4-Me-C₆H₂O)₂PX[OC(O-i-Pr)N=N(C(O)O-i-Pr)],(ii) cyclic phosphates and their complexes [e.g. imidazolium⁺CH₂(6-t-Bu-4-Me-C₆H₂O)₂PO₂ ^-.MeOH], (iii) new cycloaddition products [e.g. CH₂(6-t-Bu-4-Me-C₆H₂O)₂PC(CO₂Me)C(CO₂Me)C(O)N, (iv) macrocyclic compounds [e.g. [(t-BuN)P]₂[-OCH₂CMe₂CH₂O-]_h2] and (v) phosphonates [e.g. (OCH₂CMe₂CH₂O)P (O)CH₂C(CN)=CHC₅H₄FeC₅H₅]. The synthetic and structural aspects of these new products are discussed.