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Alkane Alkanoic Acid (no 1 needed, since carboxylic acids are terminal groups) O
HO CH3
If carboxylic acid is attached to a ring, use the cycloalkane as the parent, and add the phrase carboxylic acid (note: -COOH or -CO2H is used as an abbreviation for a carboxylic acid) O
CO2H COOH OH
cyclohexane
Four carboxylic acids are so commonly encountered that they have accepted common names, which you should memorize. These may be used as parent carboxylic acids: O O
O H OH formic acid
OH
HO
O CH3
O HO OH carbonic acid
benzoic acid
acetic acid
In carboxylic acids that contain a ketone or aldehyde the carboxylic acid takes precedence and the aldehyde or ketone group is labeled as an oxo substituent. Diacids are called dioic acids. O
OH O O 3-methyl-2,4-dioxohexanoic acid
HO O O OH
3-methylpentanedioic acid
Carboxylate anion Two factors are important when discussing electronic effects: 1. Resonance (more important): rearrangement of electrons moves full + and charges 2. Induction (real, though less important than resonance): donation or withdrawal of electron density through bonds.
The Inductive Effect in Carboxylic Acids When a carboxylic acid undergoes deprotonation to form a carboxylate ion, electronegative atoms can withdraw electron density to help stabilize the carboxylate ion. A more stable carboxylate ion explains a stronger carboxylic acid.
CASE 1: The more electronegative the element, the more effective its electron withdrawal.
O OH -H O O
Br O OH -H Br O O
(the second reaction works better--electronegative bromine withdraws electron density, stabilizing the carboxylate ion)
CASE 2: Greater number of electronegative atoms provides more effective withdrawal of electrons from the carboxylate ion.
O F OH -H O F O
O F F F OH O -H F F F O
(the second reaction works better--three electronegative fluorines withdraw electron density more effectively than one)
CASE 3: The closer the electronegative atom is to the carboxylate end the more effective its electron withdrawing ability. An electronegative element several atoms away has almost no effect.
O Cl OH -H O Cl O
Cl O OH -H O Cl O
(first reaction works better-- electronegative atom closer to carboxylate is more effective at withdrawing electron density)
O
O OH F -H O O F
F O OH -H O O
OH -H
(first reaction works best-- electronegative atom closer to carboxylate is more effective at withdrawing electron density) (Note: pKa of benzoic acid is 4.2)