NMAT REVIEWER © GIDEON A.

LEGASPI ORGANIC CHEMISTRY

1. FOUNDATIONAL CONCEPTS

A. ORGANIC COMPOUNDS – are carbon-based compounds that are formed by covalent bonding
(electron sharing) with other nonmetallic atoms such as O, N, P, S, and halogens.

 The properties of organic compounds are different from inorganic compounds as summarized in
the table below:
Properties Organic Compound Inorganic Compound
Bonding Covalent Ionic
Source Living system (many are also synthetic) Non-living systems
Solubility Mostly soluble in nonpolar solvents like Mostly soluble in polar solvent
hexane & ether typically water
Melting or Lower in contrast with comparable High
boiling point inorganic compounds
Conductivity Mostly non-conductors, some weak Good conductors because they form
conductors electrolytes in water
Combustibility Combustible, many highly flammable Usually non-combustible

B. ATOMIC ORBITAL AND HYBRIDIZATION

 Atomic orbital is the region in space about the nucleus where electrons are located. We cannot
pinpoint the exact location of electrons hence it’s best to represent these orbitals as electron
clouds.

 Two important atomic orbital in organic compounds are the s and p orbitals. The s orbital is
spherical in shape while the p orbitals are dumb bell shaped. The p orbitals have higher energy
than the s orbital but they themselves are in the same energy level hence they are said to be
degenerate.
py

px px py pz
pz
s
s orbital p orbitals Energy

 Hybridization is the “mixing” or “overlapping” of orbitals. There are two ways by which
orbitals hybridize. The head-to-head overlap forms a sigma bond () while the lateral or
sideways overlap form pi () bonds. Pi bond is weaker than sigma bond because of the
presence of node (region with zero electron density).

 The hybrid orbitals formed by carbon are summarized in the table below:

C-C Bond Type Hybridization Representation Shape, Bond Angle

C C
sp3 4  bonds Tetrahedral, 109.50

C C sp2 3  bonds, 1  bond Trigonal planar, 1200

C C
sp 2  bonds, 2  bonds Linear, 1800

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C. FUNCTIONAL GROUPS – are distinct atoms or groups of atoms that are responsible for the
physical and chemical properties of a particular kind of organic compounds

A. Hydrocarbons (C and H) D. Carbonyl Group (C=O)

Fn Group Formula Name Fn Group Formula Name
11. Aldehyde O -al
1. Alkane -C-C- -ane R C
H

12. Ketone O -one

2.Alkene -C=C- -ene C
R R

3.Alkyne -C≡C- -yne E. Carboxylic Acid and derivatives (-COOG)

13. Carboxylic O -oic acid
4.Aromatic benzene acid C
R OH

14. Acid O -oyl halide

5. Alkyl RX
-halide halide C
halide (X = F, Cl, Br, I) R X

B. Organic Derivative of H2O 15. Acid O O -oic anhydride

anhydride C C
6 .Alcohol R-OH -ol R O R'

OH 16. Ester O alkyl alkanoate

7. Phenol -phenol C
R OR'

-ether or
8. Ether R-O-R
alkoxy-
C. Sulfur containing group F. Nitrogen Containing
17. Amine R N -amine
9. Thiol R-SH -thiol

18. Amide O -amide

R C
10. Thioether R-S-R -thioether N

D. ORGANIC REACTIONS

 Electrophiles are atoms or chemical groups that are electron poor and thus “love electrons” to
fulfill this deficiency.
 Nucleophiles are atoms or chemical groups that are electron rich and thus “love protons” to
relieve this burden of extra electrons.
 Organic reactions in all their complexities can be summarized into several types. Pay attention
to these generalized reactions as they can help you a lot in your subsequent analysis.

1. Addition – is the attachment of atom(s) or molecule(s) to a substrate. Addition reaction typically

involves the breakage of a double bond to accommodate the attached group, usually an electrophile
and a nucleophile.
E

A B + E Nu A B
Nu
2. Elimination – is the removal of atom(s) or molecule(s) from a substrate. Elimination of two
groups, usually an electrophile and a nucleophile, at adjacent carbon atoms leads to the formation of
a double bond. This is the opposite of addition reaction.

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NMAT REVIEWER © GIDEON A. LEGASPI ORGANIC CHEMISTRY

E
A B A B + E Nu
Nu
3. Condensation – is the joining of two molecules together with the elimination of small molecules
usually water. This usually involves a carboxylic acid and another functional group with reactive H
atom like alcohol and amine.
O O
C + HO R' C + H2O
R OH R O R'

acid alcohol ester water

4. Substitution – is the replacement of one atom or functional group in a substrate with another
atom or functional group.
A B + C A C + B

5. Oxidation – is the increase in bonding with oxygen atom and/or decrease in bonding with
hydrogen atom of a substrate. This is brought about by oxidizing agents (which are oxygen-rich
reagents) like KMnO4 (Bayer’s reagent), K2CrO4 or K2CrO3 (Jones reagent), and strong acids like
H2SO4 and HNO3. The oxidation series of hydrocarbons and oxygen-containing functional groups
are shown below.
[O] [O]
C C C C C C

Alkene Alkyne
Alkane
O
[O] [O]
C OH C O C
OH
Alcohol Carbonyl Carboxylic acid

6. Reduction – is the exact opposite of oxidation, that is, it involves decrease in bonding with
oxygen atom and/or increase in bonding with hydrogen atom of a substrate. This is brought about by
reducing agents (which are hydrogen-rich reagents) like H2 with metal catalyst, AlBH4 (aluminum
borohydride), and NaBH4 (sodium borohydride). Other reducing agents includes Wolff-Kishner
reagent (NH2NH2 in KOH) and Clemmensen reagent (zinc amalgam that is Zn/Hg in HCl)

2. HYDROCARBONS

 Hydrocarbons are composed solely of carbon and hydrogen atoms. They are nonpolar and
neutral in nature. The first three classes of hydrocarbons are alkane, alkene, and alkyne.

Gen.
Type Bonding Description
Formula
Alkane -C-C- CnH2n+2 Saturated hydrocarbon (aliphatic) due to maximum number of H atoms

Alkene -C=C- CnH2n Unsaturated hydrocarbon (olefinic) due to reduced number of H atoms

Alkyne -C≡C- CnH2n-2 Unsaturated hydrocarbon due to reduced number of H atoms

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A. ALKANE
1. Nomenclature
 The number of carbon atoms determine the name of a hydrocarbon chain, the following table
summarizes the respective name for each number of C atom:

#C atoms Name #C atoms Name #C atoms Name #C atoms Name

1 Meth- 4 But- 7 Hept- 10 Dec-
2 Eth- 5 Pent- 8 Oct- 11 Undec-
3 Prop- 6 Hex- 9 Non- 12 Dodec-

 Follow the following rules by the International Union of Pure and Applied Chemistry (IUPAC)
in naming hydrocarbons:

a. Identify and name the parent chain which is the longest continuous carbon chain. The rest of the
attached groups are called the substituents.
b. Number the parent chain in a way that gives the lowest number combination for substituents.
c. Name the substituents as alkyl chain and indicate their number or position of attachment on the
parent chain.
d. For substituents that occur at least twice, use the prefix di-, tri-, tetra-, penta-, etc. to indicate their
number.
e. List the substituents in alphabetical order (prefixes di-, tri- etc. do not affect alphabetical order!)
then the name of the parent chain.
NOTE: Halogen substituents are easily accommodated as F (fluoro-), Cl (chloro-), Br (bromo-) and I
(iodo-). Special alkyl substituents include:

Isopropyl Tert-butyl

Sample Exercise: Name the given alkane:

methyl
isopropyl
1 2
3 5 6
4
Cl 7
chloro 9
8 10
2-chloro-6-isopropyl-3-methyldecane

Practice Exercise: Draw the structure of 2,4-dimethyl-5-iodooctane

 Cycloalkanes have rings of carbon atoms and its general formula is C nH2n, making it a functional
isomer of alkenes. The prefix cyclo- is added to the alkyl root name and is also numbered to give
the lowest to substituents. As a substituent the term cycloakyl is used and the cyclo is used for
alphabetization.

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NMAT REVIEWER © GIDEON A. LEGASPI ORGANIC CHEMISTRY

Sample Exercise: Name the given alkane:

tert-butyl

1
6 methyl
2
5 3 Br bromo
methyl 4
3-bromo-1-tert-butyl-2,5-dimethyl-1- cyclohexane

Practice Exercise: Name the given alkane:

2. Properties and Classification

 Alkanes are nonpolar in nature hence are water-insoluble but soluble in organic solvents like
ether, hexane, and carbon tetrachloride. Their melting or boiling point increases with increasing
molecular weight. Linear alkanes have higher melting or boiling points that comparable
branched alkanes and cycloalkane due to increased van der Waal forces of attraction.

 The carbon atoms are classified as to primary (10), secondary (20), tertiary (30), or quaternary
(40) carbon atom if it is attached to one, two, three, or four other carbon atoms respectively.

3. Reactions

 Alkanes are relatively inert. They react only at extreme conditions.

1. Combustion – heating in presence of oxygen gas gives CO2 and H2O. For example,

2C6H14 + 19O2 ---> 12CO2 + 14H2O

2. Pyrolytic cracking – heating in the absence of oxygen gas fragments larger alkanes into smaller
ones. For example,

C6H14 ---> C4H10 + C2H4

3. Halogenation – addition of halogen (Cl2 or Br2) as catalyst by light (UV) which occur via a free
radical mechanism. The product is a mixture of various alkyl halides and the degree of
predominance is 3o > 20 > 10.

Cl 2 , UV + +
Cl
Cl
Cl
30 > 20 > 10

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NMAT REVIEWER © GIDEON A. LEGASPI ORGANIC CHEMISTRY

B. ALKENE
1. Nomenclature

 The same rules on naming alkane are applied but the suffix –ene is added to the root name of the
carbon atom(s). The number should give the lowest number to the double bond then to the
substituents. The prefixes di-, tri-, tetra- , etc. are added prior to –ene, to indicate the number of
double bonds in the structure. Cycloalkenes also follow the given rules.

Sample Exercise: Name the given alkane:

Practice Exercise: Name the given alkene:

2. Properties and Classification

 Alkenes are also nonpolar in nature hence are water-insoluble but soluble in organic solvents
like ether, hexane, and carbon tetrachloride. Their melting or boiling point increases with
increasing molecular weight.

 The hydrogen atoms on the doubly-bonded carbon atoms can be substituted with one, two, three,
or four alkyl groups to form monosubstituted, disubstituted, trisubstituted, and tetrasubstituted
alkenes respectively.

 Geometric isomerism is a type of isomerism wherein the bonded groups can exist id different
orientation in space or geometry. For disubstituted alkene, the term cis- and trans- is used to
designate whether the attached groups are located on the same or opposite sides respectively.
Trans-alkenes are more stable than cis- counterparts but cis-alkenes have higher boiling points
than trans- counterparts.

Sample Exercise: Name and determine the isomerism of the given pairs of alkenes. Which one
will have a higher boiling point?
H Cl Cl Cl
C C C C
Cl H H H
trans-1,2-dichloroethene cis-1,2-dichloroethene
Cis-alkene has a higher boiling point than trans-alkene

Practice Exercise: Draw the cis- and trans- isomers of 2-butene and determine which one will
be more stable.

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NMAT REVIEWER © GIDEON A. LEGASPI ORGANIC CHEMISTRY

 The E,Z designation is used in determining the geometric isomerism of tri- and
tetrasubstituted alkenes. In this scheme, the groups attached to the left and right sides of the
molecule is given a high or low priority according to higher molecular weight. If the high
priority groups on each side are at the same side, then it’s designated as Z isomer (German
“zusammen”, meaning together). Otherwise if they are opposite one another, it is designated as
E isomer (German “entgegen”, meaning opposite).

Sample Exercise: Name and determine whether the given alkene is a Z or E isomer.
high priority
H CH2CH3
C C
Br CH3
high priority
Since the high priority groups are opposite one another, it is therefore an E isomer:
E-1-bromo-2-methyl-1-butene

Pratice Exercise: Name and determine whether the given alkene is a Z or E isomer.
F Cl
C C
CH3 Br

3. Reactions

 Alkenes are reactive due to the presence of weaker pi bond. They undergo reduction, oxidation
and addition reactions aside from combustion.

1. Hydrogenation – is the addition of H (reduction) across the double bond to the corresponding
alkane. This requires one mole of H2 in nickel (Ni), palladium (Pd), or platinum (Pt) catalyst for
every mole of unsaturation.

H2, Pt

1,4-cyclohexadiene cyclohexane

2. Bayer’s test – is an oxidative test used for the detection of the presence of unsaturation. The deep
purple potassium permanganate (KMnO4) in base (NaOH) is used which fades and form brown
precipitates (MnO2) upon reaction. The alkene gives a cis-diol with this reagent.

OH
NaOH OH
+ KMnO 4 + MnO 2

2-pentene cis-2,3-pentadiol

3. Ozonolysis – is the oxidative cleavage of C=C to give carbonyl compounds (aldehydes or

ketones) by the use of ozone (O3) with zinc (Zn) and acid as catalysts. The technique is to cut the
double bond in half and give each half an oxygen atom:

O3, Zn/H+ O O
+
O O

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NMAT REVIEWER © GIDEON A. LEGASPI ORGANIC CHEMISTRY

4. Markovnikov addition – is the addition of unsymmetrical reagent (E-Nu) to an unsymmetrical

double bond. The electrophile (usually H) adds to the less substituted carbon while the nucleophile
adds to the more substituted. The reason for this is that the more substituted carbon gives a more
stable carbocation (C+) intermediate where the nucleophile attaches. The summary of various
Markovnikov addition is illustrated below:

more substituted C (3 0)

Nu
+ E Nu

less substituted C (2 0) E

Typical reagent are HX in hydrohalogenation (H is electrophile, X is the nucleophile) or H 2O in

hydration (H is the elctrophile, OH is the nucleophile) under acid catalysis.

Sample Exercise: Draw the structure of the product(s) formed for the given alkene.

H OH
KMnO4
OH
HBr
NaOH
Br
Hydrohalogenation Bayer's oxidation

Pratice Exercise: Draw the structure of the product(s) formed for the same alkene as above
when it is made to react with (a) O3, Zn/H+ (b) it is reacted H2O/H+ (c) H2, Pd.
(a) (b) (c)

C. ALKYNE
1. Nomenclature

 The same rules on naming alkane are applied but the suffix –yne is added to the root name of the
carbon atom(s). The number should give the lowest number to the triple double bond then to the
substituents. The prefixes di-, tri-, tetra- , etc. are added prior to –yne, to indicate the number of
triple bonds in the structure.

 In the presence of both a double bond and a triple bond (enyne), the double bind is named first
as –en then the triple bond as –yne. The lowest number is given to the first unsaturation but if
both the double and triple bonds have the same number, priority is given on the double bond.

Sample Exercise: Name the given alkyne:

7 5
6
4 3 2 1 7-methyl-5-hepten-2-yne
7-methyl
Practice Exercise: Name the given alkyne:
Br

Cl

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2. Properties and Classification

 Alkynes are also nonpolar in nature hence are water-insoluble but soluble in organic solvents
like ether, hexane, and carbon tetrachloride. Their melting or boiling point increases with
increasing molecular weight.

 Alkynes are classified as to terminal alkynes when the triple bond is located at the end or head
of the structure or as an internal alkyne when it is located internally.

3. Reactions

 Alkynes are more reactive than alkenes due to the presence of two pi bonds. They undergo the
same reactions as alkenes but require twice the amount of reagent because of the two pi bonds.

 Alkynes can also undergo ozonolysis but the products are carboxylic acids for internal alkynes
and carboxylic acid and carbon dioxide for terminal alkyne.

D. AROMATIC HYDROCARBON

1. Nomenclature

 The benzene ring (C6H6) is named as is as parent and as phenyl when a substituent. Many
compounds of benzene have well-established, nonsystematic names that are more often used
than their systematic names. The most important of these are given below:
O O
CH3 OH OCH3 NH2
C H C OH

Toluene Phenol Anisole Aniline

(Methylbenzene) (Hydroxybenzene) (Methoxybenzene) (Aminobenzene) Benzaldeyde Benzoic acid

 For disubstituted benzene, the designation ortho- (o), meta- (m), and para- (p) are used to
indicate the 1,2-, 1,3-, and 1,4- positions of the substituents attached on the ring. The priority for
determining the parent is: toluene<aniline<anisole,phenol<benzaldehyde<benzoic acid.

 The same priority is considered for higher substituted benzene and the parent is automatically
designated the number one.

Sample Exercise: Name the given aromatic compound:

4-methyl
3
CH3
2 4
1
p-methylaniline
NH2
higher priority
(aniline)

Practice Exercise: Name the given aromatic compounds:

HO

Br COOH

H 2N

CHO

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2. Properties and Classification

 Aromatic compound are stable compounds due to resonance-stabilization of the conjugated pi

system. They are highly nonpolar and are very persistent in the environment. Many of these
compounds give a fragrant odor hence the term aromatic.

 Many compounds of benzene are carcinogenic. Conjugated aromatic compounds like

benzo[a]pyrene is the carcinogen found in automobile exhaust and charbroiled foods. It is
metabolized in the liver into highly reactive epoxide that reacts with DNA and cause mutation.

3. Reactions

 Resonance-stabilization makes aromatic hydrocarbons less reactive and more resistant to various
chemical agents. Aromatic compounds typically react via electrophilic aromatic substitution
(EAS) under vigorous reaction conditions.

1. Electrophilic aromatic substitution (EAS) – is the replacement of H atom on the aromatic ring
by a strong electrophilic species. The general reaction is:
H E
+
+ E

Specific reactions include halogenation, nitration, sulfonation, Friedel-Crafts alkylation, and Friedel-
Crafts acylation.

EAS Rxn Reagent, Catalyst Product with Benzene

X
X2, FeX2
Halogenation
(X = Cl or Br)
NO 2
Nitration HNO3, H2SO4

SO 3H
Sulfonation SO3, H2SO4

R
Friedel-Crafts
RX, AlX3
Alkylation
O
Friedel-Crafts O CR

Acylation RCX, AlX3

 For EAS of monosubstituted benzene, the direction and speed of reaction is affected by the
attached group or moiety. Since the intermediate formed during the reaction is an carbocation
(C+), it is therefore activated by nucleophilic or electron donating group such as –OH, -OR, -
NH, and –R groups which also direct the product at ortho- or para- orientation.. Meanwhile,
electrophilic or electron withdrawing group such as –NO2, -CX, -COR, -CN, -COOH, and X
destabilizes the C+ hence deactivate the reaction. They also direct the product at meta- position.

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Sample Exercise: What will be the product(s) of toluene with (a) Br 2, FeBr2 (b) CH3Cl, AlCl3

CH3 CH3

Activating Br
Ortho-/para- director Br2, FeBr2
+
CH3 Bromination
o-bromotoluene p-bromotoluene
Br

CH3
CH3Cl, AlCl3 CH3
CH3
Alkylation
+
p-methyltoluene
o-methyltoluene CH3

Practice Exercise: What will be the product(s) of bromobenzene with (a) HNO3, H2SO4 (b)
CH3CH2COCl, AlCl3

3. ORGANIC DERIVATIVES OF WATER

A. ALCOHOL
1. Nomenclature
 Alcohols are named with the suffix –ol to indicate the hydroxyl group. The number should give
the lowest number to the –OH group then to the substituents. The prefixes di-, tri-, tetra- , etc.
are added prior to –ol, to indicate the number of -OH in the structure. Cyclic alcohols also
follow the given rules.

Sample exercise: Name the given alcohol.

OH Cl OH
1
1 3 7 2
5 6
2 4 4-cyclohexenol
6 3

5-chloro-4-methyl-3-hexanol 5 4

Sample exercise: Draw the structure of (a) isopopanol (b) 4-hepten-1,2-diol

(a) (b)

b. Properties and Classification

 Alcohol are polar in nature hence are water-soluble. The boiling point are higher than
comparable hydrocarbons because the –OH group are capable of forming H-bonds. The more

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OH group the higher is the polarity and boiling point. Meanwhile, increase in alkyl chain tends
to lower both properties.

 Alcohol are classified as to primary (10), secondary (20), tertiary (30) alcohol carbon
depending whether the –OH group is attached to a primary, secondary, or tertiary carbon.

R R

R CH2 OH R CH OH R C OH
R
Primary Secondary Tertiary
Alcohol Alcohol Alcohol

c. Reactions

 Alcohol undergoes oxidation, dehydration, and condensation reactions because the polar
hydroxyl group is reactive.

1. Oxidation – primary alcohols are oxidized first to carbonyl compounds then to carboxylic acids.
Secondary alcohols are oxidized to carbonyl compounds only while tertiary alcohols are unreactive
Strong oxidizing agents include Bayer’s reagent (KMnO4, NaOH), Jones reagent (CrO3, H2SO4),
and strong acids oxidize both 10 and 20 alcohols to carboxylic acids and ketones respectively.
Weaker oxidizing agent like Rosemund reagent (PCC or pyridinium chlorochromate) is more
selective for primary alcohol and oxidizes them to aldehyde. The oxidation series for alcohol is:

2. Dehydration – is the acid-catalayzed removal of water from an alcohol to form the more
substituted or stable alkene.

OH
H2SO 4
C C C C + H2O

H
3. Condensation – is the formation of new chemical bond with subsequent elimination of water. It
condenses with carboxylic acid to form ester which is discussed under the carboxylic acid section.

Sample exercise: What is the product of reaction of 2-methyl-2-pentanol with (a) Bayer’s
reagent and (b) aqueous sulfuric acid

Bayer's rgt
no reaction since it's a tertiaty alcohol
OH
H2SO4 (aq)

Practice Exercise: Draw and name the product of oxidation and dehydration of 2-butanol.

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4. CARBONYL COMPOUNDS

a. Nomenclature

 Aldehydes are named as –al while ketones as –one. Aldehyde is always terminal in nature so
there is no need to specify the position of the carbonyl (C=O) group unlike in ketones which
need to be specified by number. Ketone is named as a substituent (oxo-) in the presence of
aldehyde.

Sample exercise: Name the given carbonyl compounds.

O O
5 6 1
7 5 3 1 4 2
6 2 H 3
4 Br
5-methylheptanal 2-bromocyclohexanone

Sample exercise: Draw the structure of (a) p-hydroxybenzaldehyde (b) 2-oxo-4-propyloctanal

(a) (b)

b. Properties and Classification

 Aldehydes and ketones are quite polar and hence are appreciably soluble in water which
decreases as the alkyl chain becomes larger.
c. Reactions

 Carbonyl undergoes oxidation, reduction, and nucleophilic addition due to the polar nature of the
C=O group.

1. Oxidation – aldehyde is oxidized to carboxylic acid but not ketone.

Test Reagent Positive result
Silver nitrate in ammonia Formation of silver mirror (Ag deposit)
Tollen’s test
(AgNO3, NH3)
Basic cupric sulfate Formation of red (rust-colored) precipitates
Benedict’s test
(CuSO4,NaOH) (Cu2O)
Formation of red (rust-colored) precipitates
Fehling’s test Cupric sulfate in Rochelle salt
(Cu2O)

2. Reduction – aldehydes are reduced to primary alcohols while ketones are reduced to secondary
alcohols with the use of sodium borohydride (NaBH4), lithium aluminum hydride (LiAlH4), or
Grignard reagent (RMgX).

O H
[R]
C C OH

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3. Nucleophilic addition – is the addition of nucleophilic compound such as alcohol (ROH) on the
carbonyl group. Aldehyde and ketone gives hemiacetal and hemiketal with the addition of one
molecule of alcohol. Addition of another alcohol yields acetal and ketal respectively.

Sample exercise: Draw theOstructure of theOH

products of the givenOR
reactions:
ROH ROH
C C OR OC OR
O AgNO3, NH3
-
Aldehyde H Hemiacetal O + Ag
Acetal
or ketone or hemiketal or ketal

Sample exercise: Draw the structure of the product of the same carbonyl compound with (a)
CH3MgCl (b) one mole CH3CH2OH
(a) (b)

5. CARBOXYLIC ACID AND DERIVATIVES

A. CARBOXYLIC ACID
1. Nomenclature

 Carboxylic acids are of highest priority among the functional group. The suffix –oic acid is used
in naming and since it is always a terminal group, there is no need to specify its position as
carbon 1.

Sample exercise: Name the given carboxylic acids.

Cl O
5 COOH
2
4 3 1 3 1
6 2
OH
6
4 5
OH
3-chloro-4-hydroxyhexanoic acid 3-Cyclohexenoic acid

Sample exercise: Draw the structure of (a) 2-methyl-3-oxo-butanoic acid (b) 2-isopropyl-3-
methoxybenzoic acid
(a) (b)

2. Properties and Classification

 Carboxylic acids are polar hence are soluble in water. When dissolved in water, the proton (H +)
of the –COOH group is dissociated to form a carboxylate anion (-COO-). The strength of its
acidity is determined by the pKa. In general, electrophilic or electron withdrawing groups
(e.g.–NO2, -CX, -COR, -CN, -COOH, and X) tend to increase acidity by stabilizing the
carboxylate anion. Meanwhile, nucleophilic or electron donating groups (e.g. –OH, -OR, -
NH, and –R) tend to decrease acidity by destabilizing the carboxylate anion.

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3. Reactions

 Carboxylic acid typically undergoes condensation reaction with other organic compounds that
results to the formation of a new functional groups. Except for acid halide formation, the
reactions involve the elimination of water.

Reagent Product Illustration

O O
R C + R' OH R C + H2O
Alcohol (ROH) Ester H O R'
Carboxylic acid Alcohol Ester

O O
R C + R' NH2 R C + H2O
Amine (RNH2) Amide H NH R'
Carboxylic acid Amine Amide

O O
O O
Acid R C + R C R C O C R' + H2O
Carboxylic acid
anhydride H H
Carboxylic acid Carboxylic acid Acid anhydride

O O
Thionyl chloride Acid R C + SOCl2 R C
(SO2Cl) chloride H Cl
Carboxylic acid Thionyl chloride Acid chloride

B. ESTER
1. Nomenclature

 Esters are named as alkyl (from alcohol) alkanoate (from carboxylic acid). Sometimes in pace of
alkanoate the tem –ate is being used. Esters are quite water soluble. They are responsible for the
characteristic smell and flavor of many fruits.

Sample exercise: Name the given ester.

O

1 O 1 3 5 pentyl ethanoate
2 2 4
ethanoate pentyl
Sample exercise: Draw the structure of octyl ethanoate (orange flavor).

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