ChemInform Abstract: Photooxidative Set‐Initiated N‐Demethylation of N,N′‐Dimethylanilines (I): Mimicking the Cytochrome P‐450 Type Oxygenations.

Pandey, Ganesh; Rani, Kavita; Bhalerao, U. T.

doi:10.1002/chin.199045135

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“…Such a mechanism was first proposed in 1932 for the transformation of dialkylaminomethyl ethers in aqueous acidic solution at room temperature (33). A similar mechanism has been proposed for the loss of an N-methoxymethyl group from a tertiary aniline in basic methanol (34), the main difference being in the degree of protonation of the ether oxygen and, hence, the leaving group. The remaining chloroacetamides, possessing an N-alkoxyethyl moiety, were substantially more recalcitrant toward reaction in acidic solution.…”

Section: Resultsmentioning

confidence: 75%

Acid- and Base-Catalyzed Hydrolysis of Chloroacetamide Herbicides

Carlson

Than

Roberts

2006

J. Agric. Food Chem.

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Despite the prevalence of chloroacetamides as herbicides, little is known about the rates or products of acid- or base-catalyzed hydrolysis of these compounds. Mechanisms of acid-catalyzed reactions may parallel those catalyzed by (hydr)oxide minerals, while base-catalyzed processes have as important counterparts reactions with environmental nucleophiles (such as reduced sulfur species). The current study systematically investigates how the structure of nine chloroacetamides affects their reactivity in 2 N NaOH, 2 N HCl, or 6 N HCl at 25 or 85 degrees C. Base-catalyzed hydrolysis proceeds either through an intermolecular SN2 reaction to hydroxy-substituted derivatives or (in a few cases) through amide cleavage, while both amide and ether group cleavages are observed under acidic conditions. Our results reveal that subtle differences in chloroacetamide structure [notably the type of (alkoxy)alkyl substituent] can dramatically influence reactivity and reaction mechanism. Hydroxy-substituted, morpholinone, and secondary aniline derivatives were identified upon reaction for several years in deionized water at circumneutral pH.

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Section: Resultsmentioning

confidence: 75%