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One-pot synthesis of α-methylene-γ-butyrolactones from benzaldehydes and bromomethylacrylates. Bis-(cyclopentadienyl)-titanium dichloride alkylaluminum complexls acts as catalysts for the polymerization of ethylene. Polyethylene prepared with these catalysts. Complexes of aluminum chloride and methylaluminum dichloride with bis-(cyclopentadienyl)-titanium dichloride as catalysts for the polymerization of ethylene.
Wendell P. Long,; David S. Breslow. Polymerization of Ethylene with Bis-(cyclopentadienyl)-titanium Dichloride and Diethylaluminum Chloride. J. Am. Chem. Soc. 1960, 82 (8), 1953-1957.
Wendell P. Long. Complexes of Aluminum Chloride and Methylaluminum Dichloride with Bis-(cyclopentadienyl)-titanium Dichloride as Catalysts for the Polymerization of Ethylene . J. Am. Chem. Soc. 1959, 81 (20),5312-5316.
In combination with trimethyaluminum, generates an ylide (Tebbe reagent): J. Am. Chem. Soc., 100, 3611 (1978), which transfers a methylene group not only to aldehydes and ketones (cf Wittig reaction) but also to the carbonyl groups of esters and lactones: J. Am. Chem. Soc., 102, 3270 (1980):
A similar reagent can be prepared by reaction with the Simmons-Smith adduct (see Diiodomethane, A15457) and used for the methylenation of ketones in excellent yields: Tetrahedron Lett., 24, 2043 (1983).
Reacts with Grignard reagents with a ß-hydrogen atom (e.g. isobutyl or isopropyl) to form, in a catalytic cycle, a titanium hydride species, which reduces aldehydes, ketones and esters to alcohols: Tetrahedron Lett., 21, 2171, 2175 (1980). The same combination effects regioselective cis-hydromagnesation of alkynes to give alkenyl Grignard reagents: Tetrahedron Lett., 22, 85 (1981); J. Chem. Soc., Chem. Commun., 718 (1981). For application in a highly stereospecific synthesis of vinylsilanes in excellent yields, see: Tetrahedron Lett., 24, 1041 (1983):
For further examples of the hydroxymagnesation of alkynes, see: Org. Synth. Coll., 8, 507 (1993). Similarly π-allyl complexes with 1,3-dienes can be generated, which react regio-and stereo-selectively with aldehydes to give homoallylic alcohols: J. Chem. Soc., Chem. Commun., 621 (1984):
For use, in combination with Mg metal, in formation of titanocycle intermediates, see: J. Org. Chem., 63, 9285 (1998); for reaction scheme, see Triphosgene, A14932.
Gefahrenhinweise (EU): H302-H332-H315-H319-H341-H335
Harmful if swallowed. Harmful if inhaled. Causes skin irritation. Causes serious eye irritation. Suspected of causing genetic defects. May cause respiratory irritation.
Obtain special instructions before use. Avoid breathing dust/fume/gas/mist/vapours/spray. Wear protective gloves/protective clothing/eye protection/face protection. IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. Store locked up. Dispose of contents/container in accordance with local/regional/national/international regulations.