Patent GB-932019-A (GB)
Title: Production of 4,4-disubstituted 5-alkylidene-1,3-dioxolane-2-ones
Inventor: DIMROTH PETER
IPC: C07D317/36
Filed: 1960-09-28
Abstract: Vitreous transparent polymers may be obtained by polymerizing compounds of the formula: <FORM:0932019/IV(a)/1> in which R1 and R2 represent saturated or unsaturated aliphatic hydrocarbon radicals with 1 to 16 carbon atoms, cycloaliphatic hydrocarbon radicals with 5 to 12 carbon atoms in the cycloaliphatic ring, aromatic hydrocarbon radicals of the benzene series, heterocyclic radicals of the pyridine series, alkyl radicals substituted by free hydroxyl groups, cycloalkyl radicals substituted by free hydroxyl groups, phenyl radicals substituted by free hydroxy groups alkyl radicals substituted by alkoxy groups derived from alcohols with 1 to 4 carbon atoms, phenyl radicals substituted by alkoxy groups derived from alcohols with 1 to 4 carbon atoms, alkyl radicals substituted by acetal groups derived from alcohols with 1 to 4 carbon atoms, alkyl radicals substituted by a dialkylamino group the alkyls of which have 1 to 4 carbon atoms, or alkyl radicals substituted by disubstituted amino groups the two substituents of which form with the nitrogen a 5- or 6-membered heterocyclic ring, or in which R1 and R2 together represent 4 to 11 methylene groups of a cycloaliphatic ring, and R3 represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an aromatic hydrocarbon radical of the benzene series, an alkyl group substituted by a free hydroxy group, an alkyl group substituted by an alkoxy group derived from an alcohol with 1 to 4 carbon atoms, an alkyl group substituted by an acetoxy group, an alkyl group substituted by a dialkylamino group the two alkyls of which have 1 to 4 carbon atoms, or an alkyl group substituted by a disubstituted amino group the two ubstituents of which forms together with the nitrogen a 5- or 6-membered heterocyclic ring. Specification 711,853 is referred to.ALSO:The invention comprises compounds of the formula: <FORM:0932019/IV(a)/1> in which R1 and R2 represent saturated or unsaturated aliphatic hydrocarbon radicals with 1 to 16 carbon atoms, cycloaliphatic hydrocarbon radicals with 5 to 12 carbon atoms in the cycloaliphatic ring, aromatic hydrocarbon radicals of the benzene series, heterocyclic radicals of the pyridine series, alkyl radicals substituted by free hydroxyl groups, cycloalkyl radicals substituted by free hydroxyl groups, phenyl radicals substituted by free hydroxy groups, alkyl radicals substituted by alkoxy groups derived from alcohols with 1 to 4 carbon atoms, phenyl radicals substituted by alkoxy groups derived from alcohols with 1 to 4 carbon atoms, alkyl radicals substituted by acetal groups derived from alcohols with 1 to 4 carbon atoms, alkyl radicals substituted by a dialkylamino group the alkyls of which have 1 to 4 carbon atoms, or alkyl radicals substituted by disubstituted amino groups the two substituents of which form with the nitrogen a 5- or 6-membered heterocyclic ring, or in which R1 and R2 together represent 4 to 11 methylene groups of a cycloaliphatic ring, and R3 represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an aromatic hydrocarbon radical of the benzene series, an alkyl group substituted by a free hydroxy group, an alkyl group substituted by an alkoxy group derived from an alcohol with 1 to 4 carbon atoms, an alkyl group substituted by an acetoxy group, an alkyl group substituted by a dialkylamino group the two alkyls of which have 1 to 4 carbon atoms, or an alkyl group substituted by a disubstituted amino group the two substituents of which form together with the nitrogen a 5- or 6-membered heterocyclic ring.  They are prepared by reacting an acetylenic alcohol R1R2C(OH)C ­ CR3 with carbon dioxide under pressure and at elevated temperature in the presence of a copper salt and an amount of 0.02 to 10% by weight based on the acetylenic alcohol of an amine having a dissociation constant of more than 10-5 in water. The temperature may be from 30 to 200 DEG  C. and the pressure from 3 to 100 atmospheres. A solvent may be used.  The process may be operated batchwise or continuously.  The products may be used as anti-icing agents or may be polymerized (see Group IV(a)).  In Example 36, 2-methyl-2-hydroxybutane-3-one, 3-methyl-3-hydroxy-4-pentanone and 1-acetylcyclohexanol-(1) are obtained by alkaline hydrolysis of 5-methylene-4,4-dimethyl-1,3-dioxolane-2-one, 5 - methylene - 4 - methyl-4-ethyl-1,3-dioxolane-2-one and 5-methylene - 4,4-pentamethylene-1,3-dioxolane-2-one respectively.  Specification 711,853 is referred to.