Batch versus Flow Photochemistry: A Revealing Comparison of Yield and Productivity

The use of flow photochemistry and its apparent superiority over batch has been reported by a number of groups in recent years. To rigorously determine whether flow does indeed have an advantage over batch, a broad range of synthetic photochemical transformations were optimized in both reactor modes and their yields and productivities compared. Surprisingly, yields were essentially identical in all comparative cases. Even more revealing was the observation that the productivity of flow reactors varied very little to that of their batch counterparts when the key reaction parameters were matched. Those with a single layer of fluorinated ethylene propylene (FEP) had an average productivity 20 % lower than that of batch, whereas three‐layer reactors were 20 % more productive. Finally, the utility of flow chemistry was demonstrated in the scale‐up of the ring‐opening reaction of a potentially explosive [1.1.1] propellane with butane‐2,3‐dione.     

Diacetylenes and mesophases

During the past five years, over 600 papers have been published on research work carried out with diacetylenes. Far fewer papers can be found on diacetylene mesophase studies, and these are reviewed in this paper. Some new findings by the authors are also presented.     

Thermal and optical studies on hexa-2,4-diyne-1,6-diyl-bis(4-n-hexoxybenzoate)

As part of a programme investigating mesogenic diacetylenes a symmetrically disubstituted diacetylene has been synthesized and polymerized. Thermal, thermo-optical and IR studies have been carried out to investigate the different crystalline forms of the diacetylene.     

Experimental visualization of bubble formation from an orifice in microgravity in the presence of electric fields

 The formation of air bubbles injected into a stagnant, isothermal liquid in microgravity through an orifice was studied. The bubbles grew very large in microgravity. They attained a nearly spherical shape and showed pronounced affinity towards coalescence in the absence of electric fields and other perturbations. Under the influence of electric fields, periodic detachment was observed, with bubble sizes larger than in terrestrial conditions. The bubble shape was elongated. After detachment, the bubbles moved away from the electrode at which they formed without coalescing with other bubbles. Experimental data on bubble shape and size at detachment showed good agreement with models. Received: 26 March 2001 / Accepted: 16 August 2001     

A Palladium(II)‐Catalyzed C?H Activation Cascade Sequence for Polyheterocycle Formation

Polyheterocycles are found in many natural products and are useful moieties in functional materials and drug design. As part of a program towards the synthesis of Stemona alkaloids, a novel palladium(II)‐catalyzed C H activation strategy for the construction of such systems has been developed. Starting from simple 1,3‐dienyl‐substituted heterocycles, a large range of polycyclic systems containing pyrrole, indole, furan and thiophene moieties can be synthesized in a single step.     

The Synthesis, Polymerization and Second Order Non-Linear Optical Properties of Novel, Conjugated, Unsymmetrical Diacetylenes Showing Liquid Crystal Behaviour

A number of novel, conjugated, unsymmetrically disubstituted diphenyl-diacetylenes have been synthesized and polymerized in the liquid-crystalline phase to yield liquid-crystalline polymers. The efficiency of second harmonic generation is reported for both monomers and polymers.