ALKANOIC ACID/CARBOXYLIC ACID

• Contains carboxyl functional group –COOH

• Two functional groups are contained in carboxyl- carbonyl (C=O)and hydroxyl (-OH)
• Saturated aliphatic alkanoic acids have general formula RCOOH (where R can be hydrogen
or alkyl)
• Higher members of alkanoic acids that occur in natural fat(ester) or oil are called fatty acids
e.g. palmitic acid, stearic acid, lauric acid etc
• Alkanoic acids that contain two carboxyl group in its molecule are called Alkanedioic acid or
dicarboxylic acid e.g. ethanedioic acid (oxalic acid), propane-1,3-dioic acid (malonic acid)
NOMECLATURE OF ALKANOIC ACID
• IUPAC naming system takes after the names of the appropriate alkane
• Replace the ending ‘-e’ in alkane with ‘-oic acid’
• Positions of the substitution are denoted by numbering the longest unbranched chain
containg the carboxyl group e.g. 2-methylpropanoic acid (CH3)2CHCOOH, 2-phenylethanoic
acid C6H5CH2COOH
• Names of aromatic acids are related to the appropriate hydrocarbon e.g. benzoic acid
C6H5COOH, toluic acid C6H4(CH3)COOH
PHYSICAL PROPERTIES OF ALKANOIC ACIDS
• Lower members are liquids which completely miscible with water due to hydrogen
bonding
• The higher members are waxy solids with decreasing water solubility
• The aromatic acids are crystalline solids sparing soluble in water but have higher
melting points than their aliphatic counterparts of comparable molecular weight
• They have higher boiling point and increased water solubility than alkanals because
its hydrogen bonding occurs with the hydroxyl group and the carbonyl group
• Boiling points of alkanoic acid increases as their molecular weight increases
Class discussion: EXPLAIN THE RESONANCE EFFECT IN ALKANOIC ACID (ACIDITY)
• PREPARATION OF ALKANOIC ACIDS
(A) Oxidation of alkanals and alkanals
(B) Hydrolysis of Cyanides/Nitrile
(C) Reaction of Grignard reagent with carbondioxide
CHEMICAL PROPERTIES OF ALKANOIC ACID
• (I). Esterification (II). Reduction with NaBH4 or LiAlH4 (iii). Decarboxylation (iv)Kolbe Electrolysis
DERIVATIVES OF ALKANOIC ACIDS
• Derivatives of alkanoic acid are formed by replacing the hydroxyl group (-OH) with
X giving a general formular RCOX where
X = OR for Alkanoates (Esters) X=NH2 for Amides X= halogen for
Acyl halides
X= -OOCR for anhydride
METHODS OF PREPARATION OF ALKANOIC ACID DERIVATIVES
• Acyl halides and esters are prepared directly from alkanoic acid but others are prepared preferably
from acyl halides by attacked of a nucleophile
(i) Acyl halides: prepared by reacting alkanoic acid with phosphorous halides (PX5, PX3, POX3)
and thionyl halide (SOX2)
RCOOH PX5 RCOX + POX3 + HX
(ii) Amides: prepared by reacting ammonia or amines with acyl halides. At times substituted
amides are also produced
RCOX + NH3 RCONH2 + HX
(III) Anhydrides: prepared by reacting two molecules of alkanoic acids with elimination of water
molecule RCOOH + HOOCR RCOOOCR + H2O (Theoretically)
or RCOONa + RCOX RCOOOCR + NaX (Practically)
(IV) Alkanoates: prepared by reacting alkanoic acid with alkanals in the presence of
concentrated mineral acids
RCOOH + R1OH HCl RCOOR1 + H2O
ALKANOATES / ESTERS
• Produce by esterification reaction.
• Name by replacing the ‘-ic’ from alkanoic acid by ‘-ate’ preceeding this the name of
the alkyl or aryl group of the appropriate alkanol or phenol
• Examples of natural ester are fats and oils
• Simple esters are colourless liquids possessing pleasant fruity odour and used in
scenting perfumes and flavouring food
• Ester of aliphatic carboxylic acids are soluble but their solubility decreases as
molecular weight increases
• Esters of aromatic carboxylic acids are insoluble.
PREPARATION OF ALKANOATES
• Fischer-Speier Esterification RCOOH + R1OH H+ RCOOR1 + H2O
• From Acid chloride or acid anhydride RCOCl + R1OH RCOOR1 + HCl
(RCO)2O + R1OH RCOOR1 + RCOOH
CHEMICAL PROPERTIES OF ALKANOATES
(I) Hydrolysis (II) Reduction using LiAlH4 and ether
(III) Ammonolysis (Amide formation) (IV) Reduction with Grignard Reagent
AMIDES
• Amides are amine derivatives of carboxylic acids.
• Compounds with functional group RCONH2 or RCONR2’‘’ where R and R’’ could be an
organic group (alkyl or phenyl) or hydrogen(H)
• Naming an amide, the term amide is added to the ending of the parent name. The
suffix ‘-ic’ of the related acid is removed and replaced by ‘amide’ e.g.
• Acetic acid Acetamide
• CH3COOH CH3CONH2
• Ethanoic acid Ethanamide
• The root name is based on the longest chain including the carbonyl group of the amide
group.
• A carboxylic acid contains the –COOH and in amide the –OH part of the carboxylic acid
is replaced by the –NH2 (amino) group so amide contain the -CONH2 group.
• Generally in IUPAC system of naming the final “ –e” of the alkane is replaced by “
amide”. The substituents on nitrogen are indicated by the same method as in the
common system. However, numbers are used for substituents on the parent chain e.g.
• HCONH2 Methanamide CH3CONH2 Ethanamide
• CH3CH2CONH2 Propanamide CH3CH2CH2CONH2 Butanamide
CLASSIFICATION OF AMIDES
• Amides are classified as primary, secondary and tertiary
PRIMARY AMIDES
• This contains -NH2 in its structure RCONH2 (that there is two hydrogen attached
to N)
• They are named by changing the of the acid by dropping the “ –oic acid”or “ –ic
acid” and adding “-amide”
• The carbonyl carbon is given the first location number and it is not necessary to
include the location number in the name because it is assumed that the
functional group will be on the end of the parent chain
HCONH2 Methanamide (Formamide)
CH3CONH2 Ethanamide (Acetamide)
C6H5CONH2 Benzamide
SECONDARY AMIDES
• This contains -NH in its structure RCONHR’ (that there is one hydrogen attached to N)
• They are named by using an upper case N to designate that the alkyl group is on the
nitrogen
• Alkyl group attached to the nitrogen are named as substituents.The letter N used to
indicate that they are attached to nitrogen
• CH3CH2CONHCH3 N-methylpropanamide
• CH3CH2CONHC6H5 N-phenylpropanamide
TERTIARY AMIDES
• This contains -N in its structure RCONR’R’’ (that there is no hydrogen attached to N)
• They are named in the same way as secondary amides but two Ns
• RCONR1R2
• HCON(CH3)2 N, N-dimethylformamide or N, N-dimethylmethanamide
• CH3CON(CH3)C2H5 N-ethyl-N- methylethanamide
PREPARATION OF AMIDES
FROM AMMONIUM SALT OF CARBOXYLIC ACID
• The carboxylic acid is first converted into ammonium salt which is then produces amide
on heating
• The ammonium salt is formed by adding solid ammonium carbonate to an excess acid
CH3COOH + (NH4)2CO3 CH3COONH4 + H2O + CO2
• When the reaction is completed, the mixture is heated and the ammonium salt
dehydrates producing amide CH3COONH4 heat CH3CONH2 + H2O
• The excess ethanoic acid is there to prevent dissociation of the ammonium salt before
it dehydrates
FROM ACYL CHLORIDE
• Acylchloride is also known as acid chloride (RCOCl). The chlorine atom is very easily
replaced by other atom or group like -NH2 group to form an amide
• The acylchloride is added to a concentrated solution of ammonia in water but the
reaction is exothermic and violet CH3COCl + 2NH3 CH3CONH2 + NH4Cl
FROM ACID ANHYDRIDES
• An acid anhydride is obtained when a molecule of water is removed from two
carboxylic acid (-COOH group)
• The reaction of acid anhydrides are like those of acylchlorides except that a
molecule of carboxylic acid is produced e.g. if ethanoic anhydride is added to
concentrated ammonia solution, ethanamide and ammonium ethanoate is
formed
(CH3CO)2O + 2NH3 CH3CONH2 + CH3COONH4
CHEMICAL REACTIONS OF AMIDES
HYROLYSIS OF AMIDES
• This is a nucleophilic acyl substitution.
• Amides hydrolyse to the parent carboxylic acid and the appropriate amine using a
strong acid or base
RCONH2 H2O/heat RCOOH + NH3
DEHYDRATION OF AMIDES
• Amides are dehydrated to form nitrile group (-CN)
• The dehydration is done by heating a solid mixture of the amide with
phosphorus(V) oxide, P4O10 (P2O5)
RCONH2 H2O/heat RCN + H2O
REDUCTION REACTION
• Amides can be reduced to primary amines by reaction with
lithiumaluminiumhydride(LiAlH4) in dry ether at room temperature
• RCONH2 + 4[H] LiAlH4/dry ether RCH2NH2 + H2O
HOFMANN DEGRADATION
• This is a reaction between an amide and a mixture of bromine and sodium
hydroxide solution
• The amide group looses the –CO part and become a primary amine with one less
carbon atom than the original amide had
R-CONH2 + Br2 + 4NaOH R-NH2 + Na2CO3 + 2NaBr + 2H2O
REACTION WITH NITROUS ACID
• Amide react with nitrous acid to give carboxylic acids and nitrogen gas.
• Nitrous acid required is prepared in situ by reaction of sodium nitrite and
hydrochloric acid
NaNO2 + HCl NaCl + HNO2 (HONO)
CH3CONH2 + HNO2 CH3COOH + N2 + H2O
AMPHOTERIC CHARACTER OF AMIDES
• Amides are feeble bases but are amphoteric in nature (that is they can behave as
an acid and a base) due to resonance
• Acid character: 2CH3CONH2 + HgO (CH3CONH2)2Hg + H2O
• Base character: CH3CONH2 + HCl CH3COCl + NH3
USES OF AMIDES
• Amides are used widely in industries in producing plastic, rubber, paper, colour in
crayons, pencils and ink as well as in water and sewage treatment
• Acrylamide and polyacrylamide are the products most widely used in above
industries. However, acrylamide is a carcinogen so it can be used only if the
chemicals are not intended for consumption
I. Polyacrylamide is used in treatment of drinking water and sewage
II. Amides are used in paper industry, being used as a binder and for retention aid for
fibres. It also retains colour pigment on paper
III. Acrylamide is used:
a) To stabilize soil and help keep free sand able to flow so that it can fill mould
b) As a coating on many household appliances and can parts with thermosetting acrylics
c) In the cosmetic industry to prepare soap , hair products and preshave lotion
d) For explosive, adhensives, printing inks, latex thickness and emulsion stabilizers.