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Organic Chemistry · MCAT

MCAT Organic Chemistry: Carbonyl and Carboxylic Acid Chemistry

Nucleophilic addition and substitution mechanism steps for aldehydes, ketones, and carboxylic acid derivatives, distinct from the reagent-matching focus of the reactions and reagents deck.

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What is the geometry of a carbonyl carbon before a nucleophile attacks it?
sp2, trigonal planar.
What is the geometry of the carbonyl carbon after a nucleophile adds to it?
sp3, tetrahedral.
In base-catalyzed nucleophilic addition to a carbonyl, what happens in the first step?
The nucleophile attacks the electrophilic carbonyl carbon, and the pi electrons shift onto oxygen to form an alkoxide intermediate.
In base-catalyzed nucleophilic addition to a carbonyl, what happens in the second step?
The alkoxide intermediate is protonated to give the neutral alcohol product.
In acid-catalyzed nucleophilic addition to a carbonyl, what is the first mechanistic step?
Protonation of the carbonyl oxygen by the acid catalyst.
Why does protonating the carbonyl oxygen speed up nucleophilic addition?
It puts a full positive charge on the carbonyl group, making the carbon much more electrophilic.
Why do aldehydes generally react faster than ketones toward nucleophilic addition?
Aldehydes have only one alkyl or H group, so there is less steric hindrance and less electron donation to the carbonyl carbon than in ketones.
What is a hemiacetal?
The product of one equivalent of alcohol adding to an aldehyde or ketone carbonyl, bearing both an OH and an OR group on the same carbon.
What additional step converts a hemiacetal into a full acetal?
Acid-catalyzed loss of water followed by attack of a second equivalent of alcohol.
What cationic intermediate forms when water leaves the protonated hemiacetal during acetal formation?
A resonance-stabilized oxocarbenium ion.
In acetal formation, what attacks the oxocarbenium ion intermediate?
The second equivalent of alcohol.
What nucleophile attacks the carbonyl carbon in cyanohydrin formation?
Cyanide ion.
What is the product after the alkoxide intermediate is protonated in cyanohydrin formation?
A beta-hydroxy nitrile.
What is the first mechanistic step in imine formation from a primary amine and a carbonyl compound?
The amine nitrogen's lone pair attacks the carbonyl carbon, forming a tetrahedral carbinolamine (hemiaminal).
What is the final mechanistic step in imine formation after the carbinolamine forms?
Acid-catalyzed dehydration, protonating and eliminating water to form the C=N double bond.

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