Carboxylic Acid Derivatives I

1. Write appropriate IUPAC names for the following compounds.

a. b.

c. d.

e. f.

Solution:

- Recall the naming rules for carboxylic acids.

- Number C atom of carboxylic group as 1 and continue numbering other C atoms.
- Decide on the parent name based on the number of C atoms.
- Use suffix –(o)ic acid for straight chain carboxylic acids, while use the suffix -carboxylic acid if
carboxyl group is attached to a ring.
- For carboxyl groups attached to aromatic rings, they are considered derivatives of benzoic acid.
- Write the substituents in alphabetical order while writing the full name.

a. There are 4 C atoms in a chain, so the parent name is butanoic acid. As carboxyl C is numbered
as 1, the substituents are given numbers as 2 and 3. Hence, there is 2-bromo and 3-methyl groups.
Ordering the substituents alphabetically and with the parent name at the end, the compound is
named as 2-bromo-3-methylbutanoic acid.

b. Since this compound contains carboxyl group attached to aromatic ring, its parent name is
benzoic acid. As the C atom of aromatic ring bearing carboxyl group is numbered as 1, C
containing substituent ethyl is numbered as 2. Hence, the name of the compound is 2-
ethylbenzoic acid.

c. This compound contains 5 C atoms in a chain, and it has both carbonyl and carboxyl group. As
carboxyl group has priority over carbonyl group (or carboxylic acid has priority over as
 aldehydes and ketones), the parent name of the compound is pentanoic acid. The carbonyl group
when considered as substituent prefix oxo- along with the position of carbonyl C is used. In this
case, it is 4-oxo. The full name of compound is 4-oxopentanoic acid.

d. Carboxyl group is attached to a ring with 5 carbon atoms, hence suffix -carboxylic acid will be
used. Additionally, there are two double bonds in the ring which needed to be indicated in the
name. Starting numbering from C atom bearing carboxyl group, the double bonds should be
indicated by numbers 2 and 4. Hence, the name is 1-cyclopenta-2,4-dienecarboxylic acid.

e. Again this compound will have benzoic acid as parent name. The methyl substituent on the ring
is on the 4th C atom as number 1 is given to C bearing carboxyl group. Hence, the compound is
named as 4-methylbenzoic acid. This compound could also be named as p-methylbenzoic acid
or even as p-toluic acid as aromatic ring with methyl group is toluene.

f. There are 4 C atoms in the chain, hence the parent name is butanoic acid. It is necessary to
indicate the position of double bond in the name as well as the substituents. Methyl substituent
is on 2nd C while double bond is between 3rd and 4th C atoms and will be indicated by number 3.
Hence, the full name is 2-methylbut-3-enoic acid.

2. a. What is the structure of lactic acid?

b. What is the structure of pyruvic acid?
c. What is the structure of oxalic acid?
d. What is the structure of glyceric acid?

Solution:

- A list of carboxylic acid compounds with common names are given at page 8 of Lecture Notes 21,
the ones indicated by red boxes. Knowing only these 4 is enough though.

a. Lactic acid is represented as CH3CH(OH)COOH and its structure is as

b. Pyruvic acid is represented as CH3C=OCOOH and its structure is as

 c. Oxalic acid is represented as COOHCOOH and its structure is as

d. Oxalic acid is represented as OHCH2CH(OH)COOH and its structure is as

3. Compare the acidity of the compound pairs below.

a.

b.

c.

d.
 e.

Solution:

- Recall that electron withdrawing groups enhance acidity, and electron releasing groups reduce
acidity.
- Also, as the substituent with electron withdrawing effect gets closer to the carboxylic acid group,
it can stabilize the anion of carboxylic acid after the release of proton. This will make the
carboxylic acid anion more stable and hence the carboxylic acid itself will be more acidic.

a. In A, there is methyl substituent while in B there is ethyl substituent. As alkyl groups are
electron donating groups, they decrease the acidity and as the degree of alkyl groups increases,
the donation effect increase making the compound less acidic. Hence, A, i.e. acetic acid (or
named as ethanoic acid with systematic naming) is more acidic than B i.e. propanoic acid.

b. Realize that both substituents are para position to carboxyl group. But they have different
electron withdrawing or donating effects, as in A -CH3 group is electron donating while -NH2
group in B is electron withdrawing. Because of that, B is more acidic compared to A.

c. Two substituents in A and B are same distance away from the carboxyl group but they have
different electronegativity which affects their electron withdrawing ability. As F is more
electronegative than Cl, it is more electron withdrawing substituent. Hence, B with F substituent
is more acidic than A with Cl substituent.

d. Both compounds have -Cl as substituent while the numbers of C atoms in alkyl group are the
same. It is the position of Cl that affects the acidity; as this electron withdrawing group comes
closer to carboxyl group, the compound becomes more acidic. Hence, B is more acidic than A.

e. In this case, again same principle as in d is applicable; as Br, an electron withdrawing

substituent comes closer to carboxyl group, the compound becomes more acidic. Hence, A is
more acidic compared to B.

4. a. Reaction of Grignard reagents with CO2 produce which type of compounds?

b. Nitriles can be prepared from which organic compounds by SN2 reaction with CN-?

c. A nitrile is converted to a carboxylic acid via which type of reaction?

d. When nitriles are reduced, which type of compounds are generated?

e. Nitriles reacted with Grignard reagents produce which type of compounds?

Solution:

a. This is carboxylation of CO2 and carboxylic acids with one more C atom than initial Grignard
reagent are generated.

b. They can be prepared from primary or secondary alkyl halides by the mentioned method.

c. It is hydrolyzation reaction that converts a nitrile to a carboxylic acid with intermediate product
being an amide.

d. They are reduced to amines.

e. Ketones are generated.