On the Diastereoselectivity of the Aqueous-Acid-Catalyzed Intramolecular Aldol Condensation of 3-Oxocyclohexaneacetaldehydes

The factors responsible for the diastereoselective formation of the 6-endo-hydroxybicyclo[2.2.2]octan-2-one by acid-catalyzed intramolecular aldol reaction of 3-oxocyclohexaneacetaldehydes have been investigated. This study, carried out on (1SR,4RS,6RS)-6-hydroxybicyclo[2.2.2]octan-2-one 1a , (1SR,4RS,6SR)-6-hydroxybicyclo[2.2.2]octan-2-one 1b , and 3,3-(ethylenedioxy)cyclohexaneacetaldehyde 2a , allowed to demonstrate the absence of intramolecular H-bonding in 1a as a stabilizing factor, and to ascertain the presence of unfavorable steric interactions in 1b .     

Use of phase diagrams in the analysis of polymer network formation

A conversion - temperature - transformation (CTT) diagram was used to analyze several non-isothermal processes of polymer network formation: a) range of heating rates where reliable kinetic information can be obtained; b) a novel process involving part of the cure in the glassy state; c) phase separation in rubber-modified epoxies cured in heated molds.     

Synthesis of 2-(p-R-benzoylmethylene)-3-(p-R-phenyl)-1H-quinoxalines

The reaction of 1,2-diaminobenzenes with substituted 1,2-dibenzoyl-1,2-dibromoethanes constitutes a convenient synthetic route to the hitherto 2-(p-R-benzoylmethylene)-3-(p-R-phenyl)-1H-quinoxalines. Structures of all products were elucidated by ir, ¹H and ¹³C-nmr, mass spectra data. X-Ray crystallography data confirm assigned structures.     

Oxidation of 2,6-di-tert-butylphenol with polymer anchored molybdenyl and vanadyl complexes

The oxidation of 2,6-di-tert-butylphenol with tert-butylhydroperoxide (Bu^tO₂H) has been studied using polymer (XAD₄) anchored salicylaldoxime, 1,3-propylene-bis-salicylaldimine and o-phenylene-bis-salicylaldimine complexes of molybdenum and vanadium in acetonitrile. The predominant products formed in the oxidation reactions were 2,6-di-tert-butylbenzoquinone (BQ) and 3,3′-5,5′-tetra-tert-butyldiphenoquinone (dPQ), whereas with some only 2,6-di-tert-butylbenzoquinone was formed. This is the first reported use of polymer anchored molybdenyl and vanadyl complexes in selective oxidation of 2,6-di-tert-butylphenol. Solvent plays an important role in this reaction. The effects of varying the ligand, metal and the support on the catalytic activity in the oxidation of 2,6-di-tert-butylphenol have been studied. With polymer anchored MoO₂(salpen), 81% of 2,6-di-tert-butylbenzoquinone was formed from 2,6-di-tert-butylphenol.     

Polymers containing substituted 2-phenyl-benzoxazole side-chain groups: Synthesis and phase behavior

The synthesis of substituted 2-phenyl-benzoxazoles has been accomplished by ring closure of Schiff bases. The compounds have been used as precursors of acrylic derivatives displaying LC properties: Four comb-like homopolymers have been obtained by radical catalysis from the acrylic monomers. The polymers have been characterized by ¹H-NMR, DSC, x-ray diffraction, viscometry, and polarizing microscopy. Three of the polymers exhibit liquid crystalline properties of smectic type. © 1996 John Wiley & Sons, Inc.     

Supercritical fluid extraction of atrazine and its metabolites from soil

Soxhlet (methanol) and SFE extraction with carbon dioxide in the presence of modifiers at different temperatures (100–200°C) for the extraction of atrazine and its main metabolites from a soil sample were compared. The most effective extraction conditions for both atrazine and its metabolites (i.e. deethylatrazine and deisopropylatrazine) were Co₂ modified with 20% molar methanol-trifluoroacetic acid (MeOH-TFA) (TFA 0.65M in MeOH) at 100°C, leading to an extraction efficiency comparable with that of Soxhlet extraction with MeOH for atrazine and ca. 20% higher for its main metabolites. The relative standard deviation (RSD) of SFE was lower than that obtained by Soxhlet extraction, probably because of less interference in the cGC-NPD determination. All the other modifiers evaluated (acetone, triethylamine, and methanol) were less effective than MeOH-TFA for the extraction of atrazine and its metabolites from a soil sample, even at high molar concentrations (20%) and use of higher extraction temperatures (200°C). These results indicate the importance of matrix effects and the need of the selection of an appropriate modifier in order to obtain quantitative extractions by SFE.     

Der massenspektrometrische Verlust von Vinylalkohol aus 1-Amino-3-aryloxy-2-propanolen. 24. Mitteilung über das massenspektrometrische Verhalten von Stickstoffverbindungen

Loss of vinyl alcohol from 1-amino-3-aryloxy-2-propanols under electron impact Under electron impact compounds of type 1 (see Scheme 1) split off 44 mass units from the molecular ion. This unusual reaction was studied using derivatives and deuterium labelled compounds. It could be demonstrated that for this fragmentation reaction 16 is the important structural feature from which H₂(C3)?C(2)HOH (44 mass units) is lost. The preferred reaction mechanism involves a transition state in which four members of the side chain are involved (Scheme 2, mechanism 2).