A novel stereocontrolled synthesis of (z,z)-3,13-octadecadien-1-yl acetate,the sex pheromone of synanthedon species

Starting from 10-undecenoic acid, a stereocontrolled synthesis of (Z,Z)-3,13-octadecadien-1-yl acetate with high stereochemical purity was achieved by the use of Wittig-olefinations for the introductions of (Z)-double bonds.     

Matrix-assisted laser desorption/ionization and electrospray ionization mass spectrometric study of 2,3-dihydro-1,4-benzoxazepines

Fragmentations of the protonated adduct ions [M+H](+) of seven 1,4-benzoxazepine derivatives were studied using 'post-source decay' matrix-assisted laser desorption/ionization (PSD MALDI) and electrospray nozzle-skimmer collisionally induced dissociation (ESI-CID) mass spectrometric methods. It was found that both methods generated mainly product ions arising from the cross-ring cleavages of the benzoxazepine ring. Similar product ions were generated under MALDI and ESI conditions; however, it was observed that the loss of the alkylene unit from the N-substituted benzoxazepine, and the loss of a H(2)X molecule (where X = O or S), are more preferred under ESI conditions. Based on the experimental results a mechanism is also proposed for the fragmentation of the oxazepines studied.     

Fragmentation of enamides derived from 6,7-dimethoxy-4-methyl-2H-1,3-benzothiazin and 3,4-dihydro-6,7-dimethoxy-1-methylixopuinoline

The electron impact mass spectra of several enamides have been examined. The enamides were prepared by reaction of aroyl halides with 6,7-dimethoxy-4-methyl-1,3-benzothiazin, and with 3,4-dihydro-6,7-dimethoxy-l-methylisoquinoline. The fragmentation pathways that have been proposed are supported by ion composition determinations and by mass-analysed ion kinetic energy spectrometry experiments carried out on the molecular ions and major fragment ions. The spectra are characterized by a loss of carbon monoxide from the molecular ion of each compound, a process which is accompanied by migration of the aryl group.     

Electromechanical effects in ferroelectric liquid crystalline polymers

Electric fields can induce mechanical vibrations in planar aligned sandwich cells of ferroelectric liquid crystals. Measurements on a polysiloxane and a polyacrylate side chain polymer proved that the electromechanical effect also exists in ferroelectric liquid crystalline polymers. The main characteristics of the electromechanical responses of these polymers are described and compared to the response of low molecular weight ferroelectric liquid crystals. According to the proposed interpretation, the vibrations in the direction parallel to both the smectic layers and cell substrates are due to coupling between the director rotation and the flow, while the resonances in the vibrations normal to the plates are connected to layer deformations.     

Synthesis of 6H,8H-isoquino[2,3-c][1,3]benzothiazin-8-ones

6H,8H-Isoquino-1,3-benzothiazin-8-ones have been prepared by reaction of 6,7-dimethoxy-2H-1,3-benzo-thiazines with homophthalic anhydride and by photocyclization of 3-benzoyl-4-methylene-6,7-dimethoxy 2H-1,3-benzothiazine. The compounds are thia analogues of protoberberine alkaloids containing a sulfur atom at C-5 and a lactam function at C-8. The mass spectra of the title compounds are discussed.     

Synthesis of quinazolino-1,3-benzothiazine derivatives

The ring-closure reactions of N-(3,4-dimethoxyphenylthiomethyl)-2-nitrobenzamide derivatives 5a,b with phosphoryl chloride gave 4-(2-nitrophenyl)-2H1,3-benzothiazine derivatives 7a,b , which on reduction yielded 4-(2′-aminophenyl)-3,4-dihydro-2H-1,3-benzothiazines 8a,b. Reaction of these compounds with phosgene led to a new heterocyclic ring system, 6H,8H-quinazolino[3,4-c][1,3]benzothiazine derivatives 9a,b. The structures of the title compounds were proved via their ir and nmr (¹H, ¹³C) spectra.     

Synthesis of novel dihydro-2H-1,2,4-oxadiazin-5(6H)-ones

The title compounds 4 were synthesized via the acid-catalyzed reaction of α-(acylaminooxy)carboxylic acid amides 6 with carbonyl compounds, and controlled catalytic hydrogenation of the resulting 2-benzyloxy-carbonyldihydro-2H-1,2,4-oxadiazin-5(6H)-ones 7 (R⁶ = PhCH₂O).     

Investigation on the chemistry of berbans—VIII : Synthesis of “inside” depyrrolo-yohimbine analogues

Previously known ketonitrile 1 with phosponic acid ester 2 produced the two geometrical isomers 3 and 4 which upon reduction afforded 5b and 6b. By hydrolysis and subsequent esterification the two methyl esters 5a and 6a were obtained. Dieckmann condensation of 5a led to 7a and 7b. Reduction of the latter compounds yielded the corresponding “inside” yohimbine analogues 8a and 8b. Methyl ester 6a was converted into the ketoester 9. The stereochemistry of the isomers was proved by physical (H¹ NMR, IR, MS) and by chemical methods.     

Analysis of poly(amidoamine)-succinamic acid dendrimers by slab-gel electrophoresis and capillary zone electrophoresis

Ethylenediamine (EDA)-core poly(amidoamine) (PAMAM) succinamic acid dendrimers (Ex.SAH, where x refers to the generation) were synthesized and analyzed by polyacrylamide gel electrophoresis (PAGE), size-exclusion chromatography (SEC), potentiometric acid-base titration, and capillary zone electrophoresis (CZE). Various generations (E1.SAH-E7.SAH) PAMAMs and a succinamic acid terminated core-shell tecto(dendrimer) (E5(E3.SAH)(n)) were first analyzed by PAGE. PAGE results show that the relative mobilities of generation 2 to generation 7 dendrimers decreased with the increasing number of generations. The molecular mass of a generation 5 core generation 3 shell tecto(dendrimer) (denoted as E5(E3.SAH)(n)) was determined to be between the Mw of E6.SAH and E7.SAH. CZE analysis allowed the evaluation of electrophoretic properties of given-generation dendrimers. The electrophoretic mobilities of individual generations PAMAM polyanions are similar, indicating that the separation mainly depends on their approximately identical charge/mass ratio. The E5(E3.SAH)(n) tectodendrimer had a lower electrophoretic mobility, which was consistent with its lower charge/mass ratio. The combination of PAGE and CZE analysis provides an alternative and effective way to characterize this group of PAMAM-succinamic acid dendrimers.     

The Distribution of the Sojourn Time for the Brownian Excursion

The solutions of various problems in the theories of queuing processes, branching processes, random graphs and others require the determination of the distribution of the sojourn time (occupation time) for the Brownian excursion. However, no standard method is available to solve this problem. In this paper we approximate the Brownian excursion by a suitably chosen random walk process and determine the moments of the sojourn time explicitly. By using a limiting approach, we obtain the corresponding moments for the Brownian excursion. The moments uniquely determine the distribution, enabling us to derive an explicit formula.