Process for the preparation of unsaturated carboxylic acids by carbonylation of allyl alcohols and their acylation products

A process for preparing a composition comprising at least one unsaturated carboxylic acid of the general formula (I)

• or a salt thereof, in which
• R1 is hydrogen, linear or branched C1-C24-alkyl, linear or branched C2-C24-alkenyl having 1, 2, 3 or more than 3 C—C double bonds, unsubstituted C5-C12-cycloalkyl or C5-C12-cycloalkyl substituted by 1, 2 or 3 C1-C6-alkyl radicals or unsubstituted aryl or aryl substituted by 1, 2 or 3 C1-C6-alkyl radicals,
• R2 is hydrogen, linear or branched C1-C24-alkyl or linear or branched C2-C24-alkenyl having 1, 2, 3 or more than 3 C—C double bonds, or
• R1 and R2 together with the carbon atom to which they are bonded are unsubstituted C5-C7-cycloalkyl or are C5-C7-cycloalkyl bearing 1, 2 or 3 linear or branched C1-C6-alkyl radicals,
• in which an allyl alcohol selected from compounds of the general formulae (II.1) and (II.2)
• is subjected to a carbonylation by reaction with carbon monoxide in the presence of a transition metal catalyst comprising at least one metal of groups 8, 9 and 10 of the Periodic Table of the Elements, wherein the reaction is additionally effected in the presence of at least one organic phosphorus compound as ligand and in the presence of a sub stoichiometric amount, based on the allyl alcohol, of a compound A) selected from anhydrides of aliphatic C1-C12-monocarboxylic acids, anhydrides of aliphatic C4-C2O-dicarboxylic acids, anhydrides of cycloaliphatic C7-C70-dicarboxylic acids, anhydrides of aromatic C8-C2O-dicarboxylic acids and acylated allyl alcohols of the formulae (III.1) and (III.2)
• in which
• R3 is hydrogen, linear or branched C1-C24-alkyl, linear or branched C2-C24-alkenyl having 1, 2, 3 or more than 3 C—C double bonds, unsubstituted C5-C12-cycloalkyl or C5-C12-cycloalkyl substituted by 1, 2 or 3 C1-C6-alkyl radicals or unsubstituted aryl or aryl substituted by 1, 2 or 3 C1-C6-alkyl radicals,
• R4 is hydrogen, linear or branched C1-C24-alkyl or linear or branched C2-C24-alkenyl having 1, 2, 3 or more than 3 C—C double bonds, or
• R3 and R4 together with the carbon atom to which they are bonded are unsubstituted C5-C7-cycloalkyl or are C5-C7-cycloalkyl bearing 1, 2 or 3 linear or branched C1-C6-alkyl radicals,
• R5 is C1-C5-alkyl,
• and wherein the reaction is effected at a temperature of not more than 100° C.

A process for preparing a composition comprising at least one unsaturated carboxylic acid of the general formula (I)

• or a salt thereof, in which
• R1 is hydrogen, linear or branched C1-C24-alkyl, linear or branched C2-C24-alkenyl having 1, 2, 3 or more than 3 C—C double bonds, unsubstituted C5-C12-cycloalkyl or C5-C12-cycloalkyl substituted by 1, 2 or 3 C1-C6-alkyl radicals or unsubstituted aryl or aryl substituted by 1, 2 or 3 C1-C6-alkyl radicals,
• R2 is hydrogen, linear or branched C1-C24-alkyl or linear or branched C2-C24-alkenyl having 1, 2, 3 or more than 3 C—C double bonds, or
• R1 and R2 together with the carbon atom to which they are bonded are unsubstituted C5-C7-cycloalkyl or are C5-C7-cycloalkyl bearing 1, 2 or 3 linear or branched C1-C6-alkyl radicals,
• in which an acylated allyl alcohol selected from compounds of the general formulae (IV.1) and (IV.2)
• in which R6 is C1-C5-alkyl,
• is subjected to a carbonylation by reaction with carbon monoxide in the presence of a transition metal catalyst comprising at least one metal of groups 8, 9 and 10 of the Periodic Table of the Elements, wherein the reaction is additionally effected in the presence of at least one organic phosphorus compound as ligand and in the presence of water and wherein the reaction is effected at a temperature of not more than 100° C.

A process for preparing a composition comprising at least one unsaturated carboxylic acid of the general formula (I)

• or a salt thereof, in which
• R1 is hydrogen, linear or branched C1-C24-alkyl, linear or branched C2-C24-alkenyl having 1, 2, 3 or more than 3 C—C double bonds, unsubstituted C5-C12-cycloalkyl or C5-C12-cycloalkyl substituted by 1, 2 or 3 C1-C6-alkyl radicals or unsubstituted aryl or aryl substituted by 1, 2 or 3 C1-C6-alkyl radicals,
• R2 is hydrogen, linear or branched C1-C24-alkyl or linear or branched C2-C24-alkenyl having 1, 2, 3 or more than 3 C—C double bonds, or
• R1 and R2 together with the carbon atom to which they are bonded are unsubstituted C5-C7-cycloalkyl or are C5-C7-cycloalkyl bearing 1, 2 or 3 linear or branched C1-C6-alkyl radicals,
• in which an allyl alcohol selected from compounds of the general formulae (II.1) and (II.2)
• is subjected to a carbonylation by reaction with carbon monoxide in the presence of a transition metal catalyst comprising at least one metal of groups 8, 9 and 10 of the Periodic Table of the Elements, wherein the reaction is additionally effected in the presence of at least one organic phosphorus compound as ligand and in the presence of a sub stoichiometric amount, based on the allyl alcohol, of a compound B)
• in which
• R10 and R11, independently of one another, are C1-C6-alkyl, C1-C6-fluoroalkyl or phenyl which is unsubstituted or substituted by a substituent selected from bromo, nitro and C1-C4-alkyl;
• and wherein the reaction is effected at a temperature of not more than 100° C.