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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of organic chemistry 49 (1984), S. 5195-5197 
    ISSN: 1520-6904
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-879X
    Keywords: AlPO4 ; Al2O3 ; SiO2 ; 2,3‐dimethyl‐2,3‐butanediol conversion ; activity ; selectivity ; poisoning by bases ; pyridine ; 2,6‐dimethylpyridine ; hexamethyldisilazane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pinacol (2,3‐dimethyl‐2,3‐butanediol) conversion over AlPO4 (Al/P = 1) and γ‐Al2O3 catalysts proceeded in two parallel reaction pathways with formation of 2,3‐dimethyl‐1,3‐butadiene (by 1,2‐elimination) and 3,3‐dimethyl‐2‐butanone (by rearrangement), the latter being the main reaction product. The activity was in accordance with the surface acidity data as measured versus cyclohexene skeletal isomerization reaction. Thus, AlPO4 showed the highest activity (almost total conversion at 523 K). The 1,2‐elimination/rearrangement ratio depended on the type of catalyst used and diene formation increased with reaction temperature. Moreover, pinacolone was a reaction intermediate for diene production.
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  • 3
    ISSN: 1572-879X
    Keywords: chromium orthophosphate (CrPO4) ; CrPO4-AlPO4 ; surface acidity ; 2-propanol conversion ; activity ; selectivity ; poisoning by bases ; pyridine ; 2,6-dimethylpyridine ; hexamethyldisilazane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The catalytic conversion (dehydration/dehydrogenation) of 2-propanol on a series of CrPO4-AlPO4 (CrAlP) catalysts, which were differently prepared and thermally treated at 773–1073 K, has been studied by microcatalytic pulse reactor technique at different temperatures (473–573 K). Kinetic parameters for conversion of 2-propanol to propene have been obtained by analysis of the data through the Bassett-Habgood equation for first-order reaction processes. The influence of the reaction temperature upon alcohol conversion and product selectivities was also investigated. Catalytic performance was affected by the precipitation agent. Catalysts obtained in propylene oxide-aqueous ammonia showed the highest activity towards propene compared to other catalysts. Calcination at increasing temperatures caused a decrease in the activity due to the decrease in surface acid character. The results of dehydration to propene can be well interpreted through the differences in the number and strength of acid sites, which were gas-chromatographically measured using pyridine and 2,6-dimethylpyridine chemisorbed at different temperatures (573 and 673 K). Dehydrogenation to 2-propanone occurred to a small extent at all reaction temperatures and, besides, its conversion changed slightly with reaction temperature. Propene selectivity strongly increased with increasing reaction temperature.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Monatshefte für Chemie 116 (1985), S. 133-135 
    ISSN: 1434-4475
    Keywords: Basic catalyst ; Barium hydroxide catalyst ; Coumarin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Bei der Reaktion von Diethylmalonat und Cumarin, die mit einem aktivierten Bariumhydroxid-Katalysator (C-200) in einem Fest-Flüssig-System katalysiert wird, ergab sich eine ungewöhnliche Addition-Eliminierung an der laktonischen C=O-Bindung.
    Notes: Abstract In the reaction of diethylmalonate and coumarin catalyzed by an activated barium hydroxide catalyst (C-200) in a solid liquid system an unusual nucleophilic addition-elimination to the lactonic C=O bond occurs.
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  • 5
    ISSN: 1572-879X
    Keywords: AlPO4 ; AlPO4–cesium oxide ; 2,5‐hexanodione conversion ; activity ; selectivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Acetonylacetone underwent both acid‐ and base‐catalyzed intramolecular cyclizations to 2,5‐dimethylfuran and 3‐methyl‐2‐cyclopenten‐1‐one, respectively, on pure AlPO4, whereas its modification with increasing amounts of cesium oxide developed AlPO4‐based materials with increased basic properties and, hence, higher selectivities to the base‐catalyzed cyclization process. However, the poisoning of surface acid and base sites indicated that acetonylacetone conversion into 3‐methyl‐2‐cyclopenten‐1‐one can also be attributed to the joint participation of surface acid and base sites. So, acetonylacetone cannot be used for the simultaneous characterization of acidic and basic surface properties of acid–base heterogeneous catalysts.
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  • 6
    ISSN: 1572-879X
    Keywords: ethylbenzene oxydehydrogenation ; nitrobenzene as oxidant ; hydrogen transfer reaction ; amorphous AlPO4 ; supported nickel catalysts ; acid–base properties ; compensation effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Gas-phase catalytic hydrogen transfer reaction between ethylbenzene and nitrobenzene, to produce styrene and aniline, has been carried out at 360–460°C on amorphous AlPO4, SiO2, Al2O3, and on a natural sepiolite, as well as on the corresponding 20 wt% supported nickel catalysts. The influence of Cu as a second metal was also studied. Reactions were also carried out without nitrobenzene, under nonoxidative conditions. Catalytic activity under oxidative conditions was always comparatively higher than in nonoxidative conditions. In both cases, styrene yield and selectivity values obtained with support materials directly used as catalysts were better than those obtained with the corresponding Ni or Ni–Cu supported metal catalysts, with the only exception of SiO2. The best results were obtained when amorphous AlPO4 was used as the catalyst. The catalytic activity obtained in both oxidative and nonoxidative conditions, was closely associated to acid–base properties of the catalysts studied. Furthermore, a very similar linear correlation between A and E a known as “compensation effect” was obtained and a common dehydrogenation mechanism was considered for oxidative and nonoxidative conditions. However, without considering the catalyst, nitrobenzene plays an important role as hydrogen acceptor, not only shifting the ethylbenzene dehydrogenation equilibrium but also avoiding secondary reactions by lowering the level of available hydrogen, especially when supported metals are being used as catalysts.
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  • 7
    ISSN: 1572-879X
    Keywords: AlPO4 catalysts ; Diels-Alder reaction ; asymmetric induction ; heterogeneous cycloaddition reaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Different synthetic AlPO4 systems are effective yet mild acid catalysts for the heterogeneous cycloaddition reaction of cyclopentadiene with (-)-menthyl acrylate. The reaction proceeds selectively under mild conditions and in a relatively short reaction time with an almost total conversion, a high endo/exo ratio, and a reasonable asymmetric induction. When the reactions are carried out without solvent, some correlations are obtained between the number of acid sites, titrated with pyridine, and reaction yields, endo/exo and diastereofacial selectivities. The positive influence of surface area of catalysts is also determined. However, the lack of good correlations between reaction results and surface properties of the catalysts indicates the influence of some other factors.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1572-879X
    Keywords: liquid-phase phenylacetylene hydrogenation ; supported nickel catalysts ; metal–support interaction effects ; acid–base properties of supports ; structural defects of crystallites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The role of textural and acid–base properties of supports on metal–support interaction effects has been evaluated through the results obtained in the liquid-phase selective hydrogenation of phenylacetylene carried out on 20 wt% supported nickel catalysts. SiO2, Al2O3, AlPO4, active carbon and a natural sepiolite were used as supports. The effects of Ni–Cu alloying were also studied. The relative adsorption constants, K_T,D, and the relative reactivities, RT,D, obtained in the consecutive hydrogenation process, were used to follow the effects of any electron transfer between the nickel atoms and acid–basic sites on the support surface. Structural defects of supported nickel crystallites were determined by X-ray diffraction line broadening analysis and used for measuring the participation of geometric effects of supported nickel crystallites in the catalytic activity. Results obtained may be better explained within a framework of simultaneous electronic and structural metal–support interaction effects.
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  • 9
    ISSN: 1588-2837
    Keywords: AlPO4 ; AlPO4-cesium oxide ; 2-methyl-3-butyn-2-ol conversion ; activity ; selectivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 2-Methyl-3-butyn-2-ol underwent almost exclusively dehydration to 3-methyl-3-buten-1-yne (acid activity) on pure AlPO4, whereas its modification with cesium oxide developed AlPO4-based materials with increased basic properties and hence, high selectivities to the base-catalyzed cleavage of MBOH yielding acetone and acetylene. At the same conversion level, catalysts obtained from cesium chloride exhibit higher selectivities to the base-catalyzed process than those obtained from cesium acetate.
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  • 10
    ISSN: 1588-2837
    Keywords: AlPO4 ; AlPO4-cesium oxide ; structure ; texture
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract AlPO4-cesium oxide (20 wt.%) materials retain a low degree of crystallinity on calcination at 873 K for 3 h. After DTA measurements (1423 K), AlPO4 crystallizes (tridymite form). Furthermore, DRIFT spectroscopy shows that the P−OH stretching vibration (at 3670 cm−1) of AlPO4 support disappears upon cesium oxide loading. Moreover, Al and P atoms remain in tetrahedral coordination as in unmodified AlPO4. Furthermore, the incorporation of cesium oxide leads, simultaneously, to a progressive decrease in surface area and pore volume as well as to an increase in the most frequently occurring pore radius.
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