High yield method for preparation of dialkyl esters of polyhaloaromatic acids

A method for preparing esters of polyhaloaromatic carboxylic acids and anhydrides of the formula:

• ##STR62## wherein:
• (a) the aromatic rings can have all possible isomeric arrangements;
• (b) A is Br or Cl;
• (c) m is 3, 4, or 5;
• (d) q is an integer of 1 to 6;
• (e) R.sup.7 is
• (i) a substituted or unsubstituted, C.sub.1-30 alkyl or an aryl having up to 30 carbon atoms, and with a valence (v) which is an integer of 1 to 4;
• ##STR63## where:
• R.sup.3 is H or a substituted or unsubstituted C.sub.1-30 alkyl, or an aryl having up to 30 carbon atoms,
• R.sup.4 is, independently, H or CH.sub.3,
• p is an integer of 1 to 50, and
• t is an integer of 1 to 49;
• or ##STR64## where R.sup.5 is a substituted or unsubstituted, C.sub.1-30 alkyl or an aryl having up to 30 carbon atoms;
• and ##EQU2## q, m, and v being as defined above;
• which comprises reacting:
• (I) at least one polyhaloaromatic carboxylic acid or anhydride of the formulae ##STR65## wherein A and m are as defined above and n is 3 or 4;
• with (II) at least a stoichiometric quantity of alcohol or polyol of the formula
• R.sup.7 (OH).sub.v
• wherein R.sup.7 and v are as defined above;
• and
• (III) a catalytically effective amount of Ti(OR.sup.2).sub.4, wherein R.sup.2, independently, is a substituted or unsubstituted C.sub.1-30 alkyl or a substituted or unsubstituted C.sub.2-22 alkylene, in the absence of an alkali or alkaline salt.