31603-49-3Relevant academic research and scientific papers
Process development and pilot plant synthesis of methyl 2-bromo-6-chlorobenzoate
Hickey, Matthew R.,Allwein, Shawn P.,Nelson, Todd D.,Kress, Michael H.,Sudah, Osama S.,Moment, Aaron J.,Rodgers, Stephen D.,Kaba, Mahmoud,Fernandez, Paul
, p. 764 - 767 (2005)
A scalable process for a pilot plant synthesis of methyl 2-bromo-6-chlorobenzoate (1) is described. The strategy employed for the synthesis hinged on the esterification of the sterically encumbered parent acid produced through an o-lithiation/ carboxylati
RAPID REDUCTIVE-CARBOXYLATION OF SECONDARY AMINES. ONE POT SYNTHESIS OF TERTIARY N-METHYLATED AMINES
Ram, Siya,Ehrenkaufer, Richard E.
, p. 5367 - 5370 (2007/10/02)
Various tertiary N-methylated amines were synthesized by using a new reductive-carboxylation approach.Secondary amines, on carboxylation with carbon dioxide under moderate reaction conditions, afforded their corresponding carbamate esters, which, on in situ lithium aluminum hydride reduction, gave desired tertiary N-methylated amines in high yield.
Model Studies on the Mechanism of Biotin-Dependent Carboxylations. 2. Site of Protonation vs. CO2 Transfer
Cravey, Melanie J.,Kohn, Harold
, p. 3928 - 3939 (2007/10/02)
Three irreversibly acidified model compounds (6-8) of N'-carboxybiotin (2) have been prepared to access the importance of proir protonation of the biotin ring system of the CO2-transfer potential of the N'-carboxy group.Substrates 6 and 7 can be considered model compounds of N'-carboxybiotin (2) in which protonation has occurred at the ureido carbonyl oxygen atom.Conversely, compound 8 was synthesized to evaluate the CO2-transfer potential of the N'-carboxy group, if protonation occurred at the N'-nitrogen atom.The reactivity of each substrate with nucleophiles has been evaluated.Of these three compounds, only 8 led to efficient transfer to the carbomethoxy group upon treatment with nitrogen-containing nucleophiles (morpholine, cyclohexylamine, and diisopropylamine).With smaller nucleophiles (i.e, water, methanol) reaction was centered at the ring C-2 position.Correspondingly, treatment of compound 6 with nucleophiles (i.e, alcohols, amines) led to products which can be explained in terms of two competing reactions.One pathway involves initial attack of the nucleophile at the C-2 position of the imidazolinium cation (an AAC2 process) to give a tetrahedral intermediate which then undergoes bond cleavage in either of two directions.The competing pathway observed was an irreversible SN2 displacement reactions (an AAL2 process) at the methylene position of the O-alkyl side chain.Factors are presented which account for the overall product distribution obtained from these reactions.Finally, the products obtained from the treatment of compound 7 with nucleophiles (i.e., alcohols, amines) could be accounted for solely by reactions which occurred at the C-2 position of the ring (an AAC2 process).The corresponding SN2 pathway is not a viably route for this substrate.The significance of these results to the mechanism of action of biotin is discussed.
