Process for manufacturing cyclocarbonates using a silver salt ca

Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...

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549229, C07D31712, C07D31714

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active

058178384

ABSTRACT:
A process for the manufacture of 4,4-disubstituted 5-methylene-1,3-dioxolan-2-ones ("cyclocarbonates") of the formula: ##STR1## wherein R.sup.1 and R.sup.2 each independently signify a saturated or olefinically-unsaturated aliphatic group or an aromatic group, or R.sup.1 and R.sup.2 together form tetra- or pentamethylene, by reacting a corresponding 3,3-disubstituted prop-1-yn-3-ol of the formula HC.tbd.C--C(R.sup.1)(R.sup.2)--OH (II) with carbon dioxide in the presence of a quaternary ammonium or phosphonium salt as the catalyst comprises using a silver salt as a further catalyst. An alkali metal or quaternary ammonium or phosphonium salt of a carboxylic acid can also be used to increase the catalytic performance of the silver salt catalyst. Moreover, the addition of triphenylphosphine serves to accelerate the reaction to some extent. The silver salts catalyze this process significantly better than the previously utilized copper salts. Advantageously, the process uses much smaller amounts of catalyst, significantly shortens reaction times, and mandates less drastic reaction conditions. Cyclocarbonates produced by this process are valuable intermediates for the production of polymerizates and other useful substances, such as dyestuffs and carotenoids.

REFERENCES:
Yanagihara et al., 52nd National Meeting of the Chemical Society of Japan, Kyoto, Abstract No. 4W 15 (1986).
Sasaki, Tetrahedron Letters, 27(14):1573-1574 (1986).
Inoue et al., The Chemical Society of Japan, 60(3):1204-1206 (1987).
Fournier et al., Tetrahedron Letters, 30(30):3981-3982 (1989).
Joumier et al., J. Chem. Soc. Perkin Trans 1, 3271-3274 (1991).
Marshall et al., J. Org. Chem., 60:5966-5968 (1995).
Ogawa et al., Synlett, 871-872 (1995).
Ogawa et al., Heterocycles 41(11):2587-2599 (1995).
Laas et al., Synthesis, 958-959 (1981).

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