By Jean-Roger Desmurs and Serge Ratton (Eds.)
The improvement of natural intermediates calls for excessive functionality and unique applied sciences. This booklet reports contemporary paintings on a few fifteen simple applied sciences in intermediates improvement together with; hydrogenation, fluorination, chlorination, nitration, enzymatic catalysis, hydroxylation, alkylation, carboxylation and the Friedel Crafts response. difficulties and business constraints eager about business improvement are highlighted from a examine standpoint and new applied sciences with capability to be used in undefined, fairly catalyst-based applied sciences fresh chemical strategies, are defined. A bankruptcy facing experiences on sodium amidure and polymerisation inhibitors is integrated.
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Han, S. Kobayashi, Chem. , 435, (1992) A. Kawada, S. Mitamura, S. Kobayashi, Synlett, 545, (1994) J. A. K. Nayyar, Tet. -P. Begu6, D. Bonnet-Delpon, Tetrahedron Report N ~ 290, Tetrahedron, 47, 3207, (1991) G. Harvey, G. M/ider, Collect. Czech. Chem. K. Kochi in "Metal-Catalyzed Oxidation of Organic Compounds" Academic Press, New York, pp. 120-133, (1981) D. P. 62, 69192 Saint-Fons, France b) Rh6ne-Poulenc Recherches, Centre de Recherches d'Aubervilliers, 52 rue de la Haie Coq, 93308 Aubervilliers Cedex, France ABSTRACT Vapor phase catalytic alkylation of phenols with methanol was carried out on various phosphates as catalysts.
B. c. Without solvent 9anisole / (RCO)20 = 4/1. Conversion toward the acid anhydride; 2 a,b / 3 a,b > 90/10. Temperature of the oil bath. Bismuth chloride is a good catalyst for veratrole acylation by RCOC1 (entries 1,2), but the crude product may contain about 5 % of an impurity idemified (GC-MS) as compound 6, which would arise from cleavage of an ether group by HC1. The reaction is more difficult with acid anhydrides (entries 4,5) relative to anisole (Table 4, entries 2,4). MeO M e O ~ c o R 22 Table 5.
On the other hand, more recently, i has been shown that : the BiC13 catalytic activity in these reactions could be considerably enhanced by addition of some metallic iodides (ref. 30) ; the coupling of aldolisation and halogenation reactions, giving 13-haloketones or -esters, is possible owing to these catalytic systems (ref. 31) ; these Bi (III) halide systems allow strong Lewis acid sensitive compounds to be used (furane cpds) (ref. 32). Moreover, BiC13 on its own acts as catalyst for the Knoevenagel reaction (ref.