A cinnoline 2-oxide from 2-nitrosobenzophenone

Base catalyzed cyclization of the 2-methylazoxybenzophenone ( 4B ) obtained by condensation of the 2-nitrosobenzophenone ( 2a ) with methylhydroxylamine led to the cinnoline 2-oxide ( 7 ) which is the major product of the peracid oxidation of the corresponding cinnoline ( 5 ).     

Nucleophilic displacement of aromatic fluorine,Part III,indoloquinolines and benzofuranoquinolines

Variously substituted indolo[2,3-c]quinolines, benzofurano[2,3-c]quinolines and their positional isomers indolo[3,2-c]quinolines and benzofurano[3,2-c]quinolines respectively, were prepared from both indole and quinoline derivatives by intramolecular nucleophilic displacement of aromatic fluorine. The formation of an indolo[2,3-d]benzazepine was also observed.     

Controllable generation of partially coherent light pulses with direct space-to-time pulse shaper

We demonstrate the possibility of creating user-defined partially coherent light pulses by means of a slight modification of the direct space-to-time pulse shaper. Specifically, we generate a mutual coherence function that corresponds to the independent-elementary-pulse representation model. The theoretical limits in the parameter of global coherence and the efficiency of the system are studied. Our result opens the door to a new way of quantum control in laser-assisted chemical reactions, namely, control by partial coherence.     

Broadband focused waves with compensated spatial dispersion: transverse versus axial balance

We determine the constraints an ABCD optical system must verify to achieve, at the focal region, broadband waves with compensated spatial dispersion either along the optical axis, called on-axis isodiffracting fields, or in the lateral direction, here named in-plane isodiffracting beams. An optical configuration is identified for generating both types of achromatic broadband focused wave fields. An experimental verification is also provided.     

Synthesis of galactofuranose-containing acceptor substrates for mycobacterial galactofuranosyltransferases

The major structural component of the cell wall in Mycobacterium tuberculosis, infection by which causes tuberculosis, is the mycolyl-arabinogalactan (mAG) complex. This large glycoconjugates has at its core a backbone of approximately 30 D-galactofuranose (Gal(f)) residues that are linked to peptidoglycan by way of a linker disaccharide containing L-rhamnose and 2-acetamido-2-deoxy-D-glucose. Recent studies have supported a model of galactan biosynthesis in which the entire structure is assembled by the action of two bifunctional galactofuranosyltransferases. These biochemical investigations were made possible, in part, by access to a panel of oligosaccharide fragments of the mAG complex (1-12), the synthesis of which we describe here. An early key finding in this study was that the iodine-promoted cyclization of galactose diethyl dithioacetal (19) in the presence of an alcohol solvent led to the formation Gal(f) glycosides contaminated with no pyranoside isomer, thus allowing the efficient preparation of furanoside derivatives of this monosaccharide. The synthesis of disaccharide targets 1, 2, 11 and 12 proceeded without difficulty through the use of thioglycoside donors and octyl glycoside acceptors, both carrying benzoyl protection. In the synthesis of the tri- and tetrasaccharides 3-6, we explored routes in which the molecule was assembled from the reducing to nonreducing end, and the reverse. The latter approach was found to be preferable for the preparation of 6, and in the case of 3 and 4, this strategy allowed the development of efficient one-pot methods for their synthesis. We have also carried out the first synthesis of three mAG fragments (8-10) consisting of the linker disaccharide further elaborated with one, two or three Gal(f) residues. A key step in the synthesis of these target compounds was the coupling of a protected linker disaccharide derivative (58) with a mono-, di-, or trigalactofuranosyl thioglycoside (17, 54, or 53, respectively).     

Multibeam second-harmonic generation by spatiotemporal shaping of femtosecond pulses

We present a technique for efficient generation of the second-harmonic signal at several points of a nonlinear crystal simultaneously. Multispot operation is performed by using a diffractive optical element that splits the near-infrared light of a mode-locked Ti:sapphire laser into an arbitrary array of beams that are transformed into an array of foci at the nonlinear crystal. We show that, for pulse temporal durations under 100 fs, spatiotemporal shaping of the pulse is mandatory to overcome chromatic dispersion effects that spread both in space and time the foci showing a reduced peak intensity that prevents nonlinear phenomena. We experimentally demonstrate arbitrary irradiance patterns for the second-harmonic signal consisting of more than 100 spots with a multipass amplifier delivering 28 fs, 0.8 mJ pulses at 1 kHz repetition rate.     

Quinazolines and 1,4-benzodiazepines LXXXII. Reaction of 2-hydrazino-benzodiazepines with 1,3-diearbonyl compounds

The 2-hydrazinobenzodiazepines 1 were reacted with acelylacelone to form the hydroxy-pyrazolines 2 which were converted to the triazolobenzodiazcpines 6 and the 2-pyrazolyl-benzodiazepine 4 . Ring cleavage of the hydrazone 8 obtained from cyclohexane-1,3-dione and 1a led similarly to the 1-(4-oxopentyl)triazolol)enzodiazepine 12 .