Ritter Reaction of 1‐Aryl‐1‐Fluoro‐2‐Haloethanes

Fluorinated phenethyl bromides 1,2 , and 3 , prove to be totally inert under Ritter reaction conditions in the presence of either SnCl₄ or AgNO₃, due to the strong deactivation by the gem‐difluoro unit. Subjecting 2‐bromo‐1‐fluoro‐1‐phenylethane to SnCl₄ in MeCN at elevated temperatures led to formation of 2‐methyl‐4‐phenyl‐4,5‐dihydrooxazole.     

Analysis of particle-wall interactions during particle free fall

In this study, the vertical motion of a particle in a quiescent fluid falling toward a horizontal plane wall is analyzed, based on simplified models. Using the distance between the particle and wall as a parameter, the effects of various forces acting on the particle and the particle motion are examined. Without the colloidal and Brownian forces being included, the velocity of small particles is found to be approximately equal to the inverse of the drag force correction function used in this study as the particle approaches the near-wall region. Colloidal force is added to the particle equation of motion as the particle moves a distance comparable to its size. It is found that the particle might become suspended above or deposited onto the wall, depending on the Hamaker constant, the surface potentials of the particle and wall, and the thickness of the electrical double layer (EDL). For strong EDL repulsive force and weaker van der Waals (VDW) attractive force, the particle will become suspended above the wall at a distance at which the particle velocity is zero. This location is referred to as the equilibrium distance. The equilibrium distance is found to increase with increased in EDL thickness when a repulsive force barrier appears in the colloidal force interaction. For the weak EDL repulsive force and strong VDW attractive force case, the particle can become deposited onto the wall without the Brownian motion effect. The Brownian jump length was found to be very small. Many Brownian jumps would be required in a direction toward the wall for a suspended particle to become deposited.     

Total Synthesis of (+)‐β‐Himachalene

An enantioselective synthesis of (+)‐β‐himachalene ( 2 ) was accomplished starting from (1S,2R)‐1,2‐epoxy‐p‐menth‐8‐ene ( 3 ) in 15 or 16 steps with an overall yield of ca. 6% (Schemes 3, 5, and 6). Key transformations include an Ireland–Claisen rearrangement, a Corey oxidative cyclization, and a ring expansion.     

Lithiation of a Silyl Ether: Formation of an ortho‐Fries Hydroxyketone

A hydroxy‐directed alkylation of an N,N‐diethylarylamide using CIPE‐assisted α‐silyl carbanions (CIPE=complex‐induced proximity effect) has been developed using a simple reagent combination of LDA (lithium diisopropylamide) and chlorosilane. A study of the mechanism, and the application of the procedure to an anionic Snieckus–Fries rearrangement for a highly efficient synthesis of the potent phosphatidylinositol 3‐kinase (PI3K) inhibitor LY294002, are reported.     

Discovery of a Dual Function Cytochrome P450 that Catalyzes Enyne Formation in Cyclohexanoid Terpenoid Biosynthesis

The 1,3-enyne moiety is commonly found in cyclohexanoid natural products produced by endophytic and plant pathogenic fungi. Asperpentyn ( 1 ) is a 1,3-enyne-containing cyclohexanoid terpenoid isolated from Aspergillus and Pestalotiopsis. The genetic basis and biochemical mechanism of 1,3-enyne biosynthesis in 1 , and other natural products containing this motif, has remained enigmatic despite their potential ecological roles. Identified here is the biosynthetic gene cluster and characterization of two crucial enzymes in the biosynthesis of 1 . A P450 monooxygenase that has a dual function, to first catalyze dehydrogenation of the prenyl chain to generate a cis-diene intermediate and then serve as an acetylenase to yield an alkyne moiety, and thus the 1,3-enyne, was discovered. A UbiA prenyltransferase was also characterized and it is unusual in that it favors transferring a five-carbon prenyl chain, rather than a polyprenyl chain, to a p-hydroxybenzoic acid acceptor.     

Effects of vortex pairing on particle dispersion in turbulent shear flows

Particle dispersion in large-scale dominated turbulent shear flow is investigated numerically with special emphasis on the effects of the vortex-pairing phenomenon. The particle dispersion is visualized numerically by following the particle trajectories in a flow consisting of large vortices which are undergoing pairing interaction. The flow field is generated by a discrete vortex method. Important global and local fiow quantities from the numerical simulation compare reasonably well with experimental measurements.

For both cases of point sources with continuous particle release and an initially distributed line source, the particle dispersion results demonstrate that the extent of particle dispersion depends strongly on the Stokes number, the ratio of the particle aerodynamic response time to the characteristic time of the vortex-pairing flow field. Particles with relatively small Stokes numbers disperse laterally at approximately the saine rate as that of the fluid particles and particles with large Stokes numbers disperse much less than the fluid particles. Particles with intermediate Stokes numbers (0.5-5) may be dispersed laterally farther than the fiuid particles and may actually be flung out of the vortex structures. Due to the strong particie entrainment power, the flow during the vortex-pairing process seems to produce higher particle lateral dispersion than the pre-pairing and post-pairing flows.     

Intervention of phenonium ion in Ritter reactions

The transformation of phenylethyl chloride to 3,4-dihydroisoquinolines is shown to proceed via phenonium ion. The evidence comes from a study of dideuterated analogue 4, and the monomethylated and dimethylated compounds 2 and 3.     

Loops and the Lagrange Property

Let $\cal F$ be a family of finite loops closed under subloops and factor loops. Then every loop in $\cal F$ has the strong Lagrange property if and only if every simple loop in $\cal F$ has the weak Lagrange property. We exhibit several such families, and indicate how the Lagrange property enters into the problem of existence of finite simple loops.     

Evaluation of nanoparticle emission for TiO<Subscript>2</Subscript> nanopowder coating materials

In this study, nanoparticle emission of TiO₂ nanopowder coated on different substrates including wood, polymer, and tile, was evaluated in a simulation box and measured with a Scanning Mobility Particle Sizer (SMPS) for the first time. The coating process for the substrate followed the instructions given by the supply company. In the simulation box, UV light, a fan, and a rubber knife were used to simulate the sun light, wind, and human contacting conditions. Among the three selected substrates, tile coated with TiO₂ nanopowder was found to have the highest particle emission (22 #/cm³ at 55 nm) due to nanopowder separation during the simulation process. The UV light was shown to increase the release of particle below 200 nm from TiO₂ nanopowder coating materials. The results show that, under the conditions of UV lamps, a fan and scraping motion, particle number concentration or average emission rate decreases significantly after 60 and 90 min for TiO₂/polymer and TiO₂/wood, respectively. However, the emission rate continued to increase after 2 h of testing for TiO₂/tile. It is suggested that nanoparticle emission evaluation is necessary for products with nanopowder coating.