Direct conversion of phenols into amides and esters of benzoic acid

A process for the preparation of a benzoate having the Structure (I):

• wherein R1, R2, R3, R4, and R5 are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, an alkoxy, a cyano, an aryl, an aromatic heterocycle, an ester, an amino, a hydrazide, an amide, thioether, sulfone, sulfoxide, sulfonic esters, and sulfinic esters, a carboxylate, or a halide;
• any R1, R2, R3, R4, and R5 together with an adjacent R group and the atoms to which they are bonded may optionally form a cyclic moiety;
• and Ar′ is a substituted or unsubstituted aromatic moiety;
• the process comprising:
• contacting an aromatic alcohol reactant with a thiocarbonyl compound reactant to thereby form an intermediate thiocarbonate product, wherein said aromatic alcohol reactant has the Structure (II):
• wherein R1 through R5 are as defined above in connection with Structure (I);
• said thiocarbonyl compound has the Structure (III):
• wherein L1 and L2 are each leaving groups;
• and said thiocarbonate product has the Structure (IV):
• wherein R1 through R5 and Ar′ are as defined above in connection with Structure (I);
• and
• contacting the intermediate thiocarbonate product having Structure (IV) with a reactant that regioselectively reacts with sulfur, which contact causes an O-neophyl rearrangement, thereby forming the benzoate having the Structure (I).

A process for the preparation of a benzamide having the Structure (V):

• wherein R11, R12, R13, R14, and R15 are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, an alkoxy, a cyano, an aryl, an aromatic heterocycle, an ester, an amino, a hydrazide, an amide, thioether, sulfone, sulfoxide, sulfonic esters, and sulfinic esters, a carboxylate, or a halide;
• any R11, R12, R13, R14, and R15 together with an adjacent R group and the atoms to which they are bonded may optionally form a cyclic moiety;
• R16 is a hydrogen, a hydrocarbyl, or an aryl;
• and Ar is a substituted or unsubstituted aromatic moiety;
• the process comprising:
• contacting an aromatic alcohol reactant with a thiocarbonyl compound reactant to thereby form an intermediate product, wherein said aromatic alcohol reactant has the Structure (VI):
• wherein R11, R12, R13, R14, and R15 are as defined above in connection with Structure (V);
• said thiocarbonyl compound reactant has the Structure (VII):
• wherein L1 and L2 are each leaving groups, and said intermediate product has the Structure (VIII):
• wherein R11, R12, R13, R14, and R15 are as defined above in connection with Structure (V) and L2 is a leaving group;
• contacting the intermediate product having the Structure (VIII) with an aniline to thereby form a thiocarbamate product, wherein said aniline has the Structure (IX):
• wherein R16 is a hydrogen, a hydrocarbyl, or an aryl;
• R17, R18, R19, R20, and R21 are each independently a hydrogen, an alkyl, an alkenyl, an alkynyl, an alkoxy, a cyano, an aryl, an aromatic heterocycle, an ester, an amino, a hydrazide, an amide, thioether, sulfone, sulfoxide, sulfonic esters, and sulfinic esters, a carboxylate, or a halide, and any R17, R18, R19, R20, and R21 together with an adjacent R group and the atoms to which they are bonded may optionally form a cyclic moiety;
• and said thiocarbamate product has the Structure (X):
• wherein R11 through R16 are as defined above in connection with Structure (V);
• and R17 through R21 are as defined above in connection with Structure (IX);
• and
• contacting the thiocarbamate product having the Structure (X) with a reactant that regioselectively reacts with sulfur, which contact causes an O-neophyl rearrangement, thereby forming the benzamide having the Structure (V).