Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone

Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF₃CH₂, and n-C₆F₁₃CH₂CH₂ esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C₆F₁₃CH₂CH₂ esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d₆ and MeOH-d₄, with DBU in acetonitrile afforded deuterated MMA (MMA-d₈) in 70 % yield.     

Conjugacy relationship between M-convex and L-convex functions in continuous variables

By extracting combinatorial structures in well-solved nonlinear combinatorial optimization problems, Murota (1996,1998) introduced the concepts of M-convexity and L-convexity to functions defined over the integer lattice. Recently, Murota–Shioura (2000, 2001) extended these concepts to polyhedral convex functions and quadratic functions in continuous variables. In this paper, we consider a further extension to more general convex functions defined over the real space, and provide a proof for the conjugacy relationship between general M-convex and L-convex functions.Mathematics Subject Classification (1991): 90C10, 90C25, 90C27, 90C35This work is supported by Grant-in-Aid of the Ministry of Education, Culture, Sports, Science and Technology of Japan     

Phase Conjugation in Saturable Absorbing Dye Films by Degenerate Four-Wave Mixing and Holographic Processes Using Nanosecond Pulse and CW Lasers

We report on the simultaneous generation of phase-conjugate signals by degenerate four-wave mixing (DFWM) and holographic processes using a nanosecond pulse and a CW lasers in polyvinyl alcohol (PVA) films doped with four kinds of saturable absorbing dyes. For the pulse laser, of the four kinds of dye-doped PVA films, the erythrosine B-doped PVA and uranine doped-PVA films generate PC signals only by the DFWM process, while the other dye-doped PVA films generate PC signals simultaneously by not only the DFWM process but also the holographic process. Especially, the safranin T-doped PVA film generates strong PC signals by the holographic process. In contrast, all of the dye-doped PVA films generate the two types of PC signals for the CW laser. The fading of dye molecules is found to result in the generation of the holographic component of PC signals which governs the temporal behavior of the total PC signals.     

Fast Optical Switching Using Oriented Cyanine Dye-Doped Nematic Liquid Crystal

A cyanine dye, 2-[7-（1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene）-1,3,5-heptatrienyl]-1,3,3-trimethyl-3H-indolium iodide （NK-125）, is doped in 4-cyano-4＇-pentylbiphenyl （5 CB）, and the mixture is sandwiched between two pieces of rubbed glass plates. The third-order nonlinear optical properties of the oriented NK-125-SCB layers are measured by the resonant femtosecond degenerate four-wave mixing （DFWM） technique at 760 nm. The third-order nonlinear optical susceptibility of one of the present samples is 5.5×10^-8 esu. The slow DFWM response of the NK-125-SCB layers due to a population grating is accelerated by the increasing laser power because of amplified spontaneous emission （ASE）. On the other hand, we do not observe a similar phenomenon for NK-125- polyethylene glycol （PEG-400）. Oriented NK-125 molecules in nematic liquid crystals must have very high ASE efficiency. Hence the population grating in a DFWM signal disappears within about 4 ps. It is expected that NK-125-SCB can be used as a material for very fast all-optical switching.