82679-10-5Relevant academic research and scientific papers
Alkylation and acylation of basic salts of anthranilic acid
Wiklund, Per,Bergman, Jan
, p. 969 - 972 (2007/10/03)
The O-nucleophilicity of basic anthranilic acid salts was documented, analyzed, and utilized in synthesis. Specifically substitutions leading to esters instead of secondary amines, and formation of anthranilic acid anhydrides were studied.
Acylanthranils. 11. Reaction of Acylanthranils with Alcohols To Give the Corresponding Esters
Errede, L.A.,Ashley, P.E.,McBrady, J.J.,Yarian, D.R.
, p. 3825 - 3828 (2007/10/02)
Although the reactions of acetylanthranil (1, R = CH3) with nucleophilic molecules of the type HNu usually occur "abnormally" via nucleophilic attack at the less electropositive center, C-2 (pathway A, Scheme II), it was shown that reactions of 1 with the anion form, Nu(1-), always occur "normally" via nucleophilic attack at the more electropositive center, C-4 (pathway B, Scheme II).Thus, reaction of 1 with ROH in the presence of a small amount of RO(1-) gives the corresponding o-acetamidobenzoate ester 4 in very good yields, rather than the corresponding acetimidate 3.These results are consistent with the hypothesis that the "abnormal" selectivity is attributable to formation of a molecular complex, 1*(HNu)n, via hydrogen bonding with the heterocyclic nitrogen atom of 1, which favors subsequent nucleophilic attack at the adjacent electropositive center at C-2.Since Nu(1-) cannot be restrained by the tether of hydrogen bonding to the electron donating atoms of 1, reaction occurs "normally" via direct nucleophilic attack at C-4.
