Method of preparing phenoxy alkanoic, alkenoic, and alkynoic acids and salts thereof via a dicarboxylate intermediate

A method of preparing an alkylated phenoxy containing compound from a dicarboxylated phenoxy containing compound comprising the step of decarboxylating and hydrolyzing the dicarboxylated phenoxy containing compound to form the alkylated phenoxy containing compound, wherein the dicarboxylated phenoxy containing compound has the formula

• where
• R1, R2, R3, and R4 are independently H, —OH, halogen, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 alkoxy, —C(O)R12, —NO2, —NR9R10, or —N+R9R10R13 (R14)−;
• R5 is H, —OH, —NO2, halogen, —CF3, —R15R16, —N+R15R16R17 (R18)−, amide, C1-C12 alkoxy, C1-C12 alkyl, C2-C12 alkenyl, carbamate, carbonate, urea, or —C(O)R19;
• R7 is a linear or branched C1-C20 alkylene, C2-C20 alkenylene, or C2-C20 alkynylene;
• R7 is optionally substituted with C1-C4 alkyl, C1-C4 alkenyl, oxygen, nitrogen, sulfur, halogen, —OH, C1-C4 alkoxy, aryl, heteraryl, or vinyl;
• R7 is optionally interrupted with aryl, heteroaryl, vinyl, oxygen, nitrogen, or sulfur;
• R8 and R11 are independently C1-C4 alkyl or C1-C4 haloalkyl;
• R9, R10, and R13 are independently H or C1-C10 alkyl;
• R12 is H, C1-C4 alkyl, C2-C4 alkenyl, or —NH2;
• R14 and R18 are independently a halide, hydroxide, sulfate, tetrafluoroborate, or phosphate;
• R15, R16, and R17 are independently H, C1-C10 alkyl, C1-C10 alkyl substituted with —COOH, C2-C12 alkenyl, C2-C12 alkenyl substituted with —COOH, —C(O)R20;
• R19 is —H, C1-C6 alkyl, or C2-C12 alkenyl;
• and
• R20 is —OH, C1-C10 alkyl, or C2-C12 alkenyl,
• wherein at least one of R1, R2, R3, R4 and R5 is —OH or alkoxy.

A method of preparing an alkylated phenoxy containing compound from a phenoxy containing compound, the method comprises the steps of (a) alkylating the phenoxy containing compound with a dicarboxylate alkylating agent to form a dicarboxylated phenoxy containing compound, and (b) decarboxylating the dicarboxylated phenoxy containing compound to form the alkylated phenoxy containing compound,

• wherein the phenoxy containing compound has the formula
• wherein
• R1, R2, R3, and R4 are independently H, —OH, halogen, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 alkoxy, —C(O)R12, —NO2, —NR9R10, or —N+R9R10R13 (R14)−;
• R5 is H, —OH, —NO2, halogen, —CF3, —R15R16, —N+R15R16R17 (R18)−, amide, C1-C12 alkoxy, C1-C12 alkyl, C2-C12 alkenyl, carbamate, carbonate, urea, or —C(O)R19;
• R6 is a leaving group;
• R9, R10, and R13 are independently H or C1-C10 alkyl;
• R12 is H, C1-C4 alkyl, C2-C4 alkenyl, or —NH2;
• R14 and R18 are independently a halide, hydroxide, sulfate, tetrafluoroborate, or phosphate;
• R15, R16, and R17 are independently H, C1-C10alkyl, C1-C10 alkyl substituted with —COOH, C2-C12 alkenyl, C2-C12 alkenyl substituted with —COOH, —C(O)R20;
• R19 is —H, C1-C6 alkyl, or C2-C12 alkenyl;
• and
• R20 is —OH, C1-C10 alkyl, or C2-C12 alkenyl,
• wherein at least one of R1, R2, R3, R4 and R5 is —OH or alkoxy.