A Gram‐Scale Batch and Flow Total Synthesis of Perhydrohistrionicotoxin

The total synthesis of the spiropiperidine alkaloid (?)‐perhydrohistrionicotoxin (perhydro‐HTX) 2 has been accomplished on a gram scale by employing both conventional batch chemistry as well as microreactor techniques. (S)‐(?)‐6‐Pentyltetrahydro‐pyran‐2‐one 8 underwent nucleophilic ring opening to afford the alcohol 10 , which was elaborated to the nitrone 13 . Protection of the nitrone as the 1,3‐adduct of styrene and side‐chain extension to the unsaturated nitrile afforded a precursor 17 , which underwent dipolar cycloreversion and 1,3‐dipolar cycloaddition to give the core spirocyclic precursor 18 that was converted into perhydro‐HTX 2 . The principal steps to the spirocycle 18 have successfully been transferred into flow mode by using different types of microreactors and in a telescoped fashion, allowing for a more rapid access to the histrionicotoxins and their analogues by continuous processing.     

Photoprogrammable Organic Light‐Emitting Diodes

Enlightening the memory : The integration of a crosslinkable photochromic dithienylperfluorocyclopentene (DTE) into organic light‐emitting diodes (OLED) allows for the individualization of the emissive area of the OLED device, for example, for signage applications. The operation principle is based on switching the injection barrier for holes (positive charge carriers). Very large ON/OFF ratios of up to 3000 for current as well as electroluminescence have been achieved.

     

Sequencing mixed-model assembly lines: Survey,classification and model critique

Manufacturers in a wide range of industries nowadays face the challenge of providing a rich product variety at a very low cost. This typically requires the implementation of cost efficient, flexible production systems. Often, so called mixed-model assembly lines are employed, where setup operations are reduced to such an extent that various models of a common base product can be manufactured in intermixed sequences. However, the observed diversity of mixed-model lines makes a thorough sequence planning essential for exploiting the benefits of assembly line production. This paper reviews and discusses the three major planning approaches presented in the literature, mixed-model sequencing, car sequencing and level scheduling, and provides a hierarchical classification scheme to systematically record the academic efforts in each field and to deduce future research issues.     

Solving the car sequencing problem via Branch & Bound

In a mixed-model assembly line, varying models of the same basic product are to be produced in a facultative sequence. This results to a short-term planning problem where a sequence of models is sought which minimizes station overloads. In practice – e.g. the final assembly of cars – special sequencing rules are enforced which restrict the number of models possessing a certain optional feature k to r_k within a subsequence of s_k successive models. This problem is known as car sequencing. So far, employed solution techniques stem mainly from the field of Logic and Constraint Logic Programming. In this work, a special Branch & Bound algorithm is developed, which exploits the problem structure in order to reduce combinatorial complexity.     

Variation of S/G ratio and lignin content in a Populus family influences the release of xylose by dilute acid hydrolysis

Wood samples from second generation Populus cross were shown to have different lignin contents and S/G ratios (S: syringyl-like lignin structures; G: guaiacyl-like lignin structures). The lignin contents varied from 22.7% to 25.8% and the S/G ratio from 1.8 to 2.3. Selected samples spanning these ranges were hydrolyzed with dilute (1%) sulfuric acid to release fermentable sugars. The conditions were chosen for partial hydrolysis of the hemicellulosic fraction to maximize the expression of variation among samples. The results indicated that both lignin contents and S/G ratio significantly affected the yield of xylose. For example, the xylose yield of the 25.8% lignin and 2.3 S/G (hihg lignin, high S/G) sample produced 30% of the theoretical yield, whereas the xylose yield of the 22.7% lignin and 1.8 S/G (low lignin, low S/G) was 55% of the theoretical value. These results indicate that lignin content and composition among genetic variants within a single species can influence the hydrolyzability of the biomass.     

1,4‐Di(isopropyl)‐1,4‐diazabutadien als Abfangreagenz für monomere Bruchstücke des Tetragalliumclusters Ga4[C(SiMe3)3]4 – Bildung eines ungesättigten GaN2C2‐Heterocyclus und eines Oxidationsprodukts mit Ga‐O‐O‐Ga‐Gruppe

1,4‐Di(isopropyl)‐1,4‐diazabutadiene as a Reagent for the Trapping of Monomeric Fragments of the Tetragalliumcluster Ga₄[C(SiMe₃)₃]₄ – Formation of an Unsaturated GaN₂C₂ Heterocycle and an Oxidation Product Containing a Ga‐O‐O‐Ga Group The tetrahedral tetragallium cluster Ga₄[C(SiMe₃)₃]₄ ( 1 ) dissociates upon dissolution to yield the monomeric fragments Ga‐R [R = C(SiMe₃)₃]. These monomers could be trapped now by the treatment of their solutions with 1,4‐di(isopropyl)‐1,4‐diazabutadiene. The product of the cycloaddition reaction ( 2 ) possesses a five‐membered GaN₂C₂ heterocycle with a coordinatively unsaturated gallium atom and an endocyclic C=C double bond. 2 is rather sensitive towards oxidation by traces of air. The contact with oxygen yielded a digallium peroxide [(C₂N₂iPr₂)RGa‐O‐O‐GaR(C₂N₂iPr₂)] ( 3 ) which was isolated in a very low yield only and which has a gallium atom attached to each oxygen atom of the inner peroxo group. Both chelating ligands of 3 possess an unpaired electron.     

Selective propargylic C(sp3)–H activation of methyl-substituted alkynes versus [2 + 2] cycloaddition at a titanium imido template

The reaction of the titanium imido complex 1b with 2-butyne leads to the formation of the titanium azadiene complex 2a at ambient temperature instead of yielding the archetypical [2 + 2] cycloaddition product (titanaazacyclobutene) which is usually obtained by combining titanium imido complexes and internal alkynes. The formation of 2a is presumably caused by an initial propargylic C(sp³)–H activation step and quantum chemical calculations suggest that the outcome of this unexpected reactivity is thermodynamically favored. The previously reported titanaazacyclobutene I (which is obtained by reacting 1b with 1-phenyl-1-propyne) undergoes a rearrangement reaction at elevated temperature to give the corresponding five-membered titanium azadiene complex 2b.

An unexpected reactivity between a titanium imido complex and internal alkynes was unveiled yielding titanaazacyclobutenes instead of the expected [2 + 2] cycloaddition products.     

Determination of the neutron electric form factor in the D(e,e′n)p reaction and the influence of nuclear binding

The electric form factor of the neutron G _E,n has been determined at the Mainz Microtron MAMI at the low momentum transfer Q ²= 0.15 (GeV/c)² in a measurement of the recoil polarisation ratio P _x/P_z in the quasifree reaction D(e,e′n)p. At this Q ² the influence of the nuclear binding is strong. A purely kinematical model is used to get some insight into the effect of the initial Fermi momentum distribution of the neutron. The influence of the final state interaction is determined quantitatively by a model of Arenh?vel et al.. After the corresponding corrections a value of G _E,n(0.15 (GeV/c)²) = 0.0481±0.0065_stat±0.0053_syst is obtained. Received: 12 April 1999