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Organic Chemistry · MCAT

MCAT Organic Chemistry: Amines and Nitrogen-Containing Compounds

Amine basicity, nomenclature, and characteristic reactions of nitrogen-containing organic compounds tested on the MCAT.

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What is a primary (1 degree) amine?
An amine with nitrogen bonded to one carbon group and two hydrogens.
What is a secondary (2 degree) amine?
An amine with nitrogen bonded to two carbon groups and one hydrogen.
What is a tertiary (3 degree) amine?
An amine with nitrogen bonded to three carbon groups and no hydrogens.
What is a quaternary ammonium salt?
A nitrogen bonded to four carbon groups, carrying a permanent positive charge.
Why are amines basic?
The nitrogen has a lone pair of electrons that can accept a proton.
What is the approximate pKa of a protonated aliphatic amine (R-NH3+)?
Around 10 to 11.
How does alkyl substitution on nitrogen affect amine basicity in the gas phase?
It increases basicity, because alkyl groups donate electron density inductively and stabilize the positive charge on the protonated amine.
In aqueous solution, why do tertiary amines often not follow the gas-phase basicity trend?
Steric hindrance and poor solvation of the bulky protonated ammonium ion reduce their basicity.
Is aniline more or less basic than cyclohexylamine?
Less basic.
Why is aniline less basic than an aliphatic amine?
The nitrogen lone pair delocalizes into the aromatic ring, making it less available to accept a proton.
How does an electron-withdrawing group like nitro on an aniline ring affect its basicity?
It decreases basicity by pulling electron density away from the nitrogen lone pair.
How does an electron-donating group like methoxy on an aniline ring affect its basicity?
It increases basicity by pushing electron density toward the nitrogen.
Are amides basic like amines?
No, amides are only very weakly basic.
Why is the nitrogen lone pair in an amide much less available than in an amine?
It is delocalized by resonance into the carbonyl group.
Why is pyridine basic?
Its nitrogen lone pair sits in an sp2 orbital in the plane of the ring, not part of the aromatic pi system, so it is free to accept a proton.

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