Download - Chapter 4 carboxylic acid
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Chapter 4
CARBOXYLIC ACID Norfazrin Mohd Hanif
Faculty of Applied Science
UiTM Negeri Sembilan
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CHAPTER OUTLINE
General formula : RCOOH OR ArCOOH Nomenclature –IUPAC and common Physical properties of aldehyde : Boiling points and solubility Acidity Preparation
Oxidation of Primary Alcohols, Aldehydes, Alkenes And Alkyl Benzene
Carboxylation of Grignard reagent Hydrolysis of nitrile
Reactions Salt formation Reduction to alcohols Formation of Acyl Chlorides Formation of Esters Formation of Acid Anhydrides Formation of Amides
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The functional group of a carboxylic acid is a carboxyl group, which can be represented in any one of three ways:
, R-COOH, R-CO2H R COH
O
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Carboxylic acids named by replacing –e of the corresponding alkane name with –oic acid
–CO2H carbon atom is numbered C1
Compound containing multiple –COOH group, add di- or tri- to the suffix –oic acid
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Carboxylic acids containing two carboxyl groups are called dicarboxyl acids.
Their systematic names have the suffix ‘dioic’.
COOH
COOH
COOH
CH2
COOH
COOH
(CH2)4
COOHethanedioic acid
(oxalic acid)propanedioic acid
(malonic acid)
hexanedioic acid
(adipic acid)
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Cycloalkanes bonded to -COOH are named as cycloalkanecarboxylic acids.
Aromatic acids are named as benzoic acids.
C OH
O
COOH
OH
COOH
NO2benzoic acid 2-hydroxybenzoic acid 3-nitrobenzoic acid
12
3
45
6
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All common names of acid end in –ic acid. Positions of substituents on the chain are labeled
with Greek letters.
CH3CH2CHC
Cl
OH
O
-chlorobutyric acid
CH3CH2CH2CHCH2COOH
Ph
-phenylcaproic acid
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Boiling point (BP)
Carboxylic Acids have higher BP than other organic molecules with comparable MW.
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Higher boiling points than similar alcohols, due to dimer formation.
Acetic acid, b.p. 118C
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In the presence of water, hydrogen bond are formed between water molecules & individual molecules of acid.
Carboxylic acid with up to 4 Carbon completely miscible in water at room temperature.
Water solubility decreases with the length of the carbon chain.
δ+ δ-…………
H O
H Hydrogen bond with water.
R COH
O
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More soluble in water than comparable alcohols, ethers, aldehydes, and ketones
CH3COOH
CH3CH2CH2OH
CH3 CH2CHO
CH3 (CH2 ) 2COOH
CH3 (CH2 )3CH2OH
CH3 (CH2 ) 3CHO
acetic acid
1-propanol
propanal
60.5
60.1
58.1
118
97
48
16388.1butanoic acid
1-pentanol 88.1 137
103pentanal 86.1
Structure NameMolecular
Weight
Boiling Point
(°C)
Solubility
(g/100 mL H2O)
infinite
infinite
16
infinite
2.3
slight
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Carboxylic acids are acidic because of the hydrogen in the -COOH group.
Recall that acids are compounds which yield H+ ions in solution.
Carboxylic acids in solution dissociate into the following ions:
Carboxylate ion
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Carboxylic acids – stronger acids than ROH The pKa of ethanol is ~16, compared to ~5 for acetic
acid
Alkoxide ion (R-O-): negative charge is localized on O Carboxylate ion (COO-): negative charge is delocalized
over two equivalent O atoms: Resonance stabilization
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Oxidation of Alkyl benzene Alkene Alcohol Aldehyde
Carboxylation of Grignard reagent
Hydrolysis of nitrile
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KMnO4 ,
H+
R COOH
o General Formula:
o Example:
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+KMnO
4 ,H
3O+
R C
OH
O
CH CHR R' R C
OH
O
o General Formula:
o Example:
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o General Formula:
KMnO4 ,
H3O+
R C
OH
O
CH2OHR
o Example:
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o General Formula:
o Example:
KMnO4 ,
H3O+
R C
OH
O
CR
H
O
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R = alkyl, allyl, benzyl, aryl CO2 = dry ice or bubbling gaseous CO2
• nucleophilic addition - alkyl or aryl magnesium halide is added to a double bond C=O of CO2 to form carboxylate ion. • when treated with acid, carboxylic acid is formed
H3O+R MgX O C O R C
O
O- MgX+ R C
O
OH
o General Formula:
RMgX CO2 RCOOHH3O+
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o Example:
CH3CH2MgCl i) CO2
ii) H3O+CH3CH2COOH
MgCl COOH
i) CO2
ii) H3O+
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Alkyl halides react with NaCN to form nitriles which in turn undergo hydrolysis in acidic solution to produce carboxylic acid.
R X R CN R C
O
OH + NH4+NaCN H3O+
Formation of nitriles involves nucleophilic substitution.
Primary alkyl halides (Cl, Br, I) – SN2 substitution
Aromatic nitriles cannot be prepared through this method but still can hydrolysed to give aromatic carboxylic acids.
The nitrile is reflux with a dilute acid such as H2SO4 or HCl to form carboxylic acid.
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BrNaCN
CNH
+
H2O
COOH
o General Formula:
o Example:
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Salt formation
- neutralisation
- reactions with electropositive metals
Reduction to alcohols
Formation of Acyl Chlorides
Formation of Esters
Formation of Acid Anhydrides
Formation of Amides
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1) Neutralisation: - carboxylic acids undergo neutralisation reactions with strong
bases or some weak base such as NaOH, NaHCO3, Na2CO3, NH3 and amines to form carboxylate salts of carboxylic acids and water.
RCO2H + NaOH → RCO2
-Na+ + H2O RCO2H + NaHCO3 → RCO2
-Na+ + H2O + CO2
2RCO2H + Na2CO3 → 2RCO2-Na+ + H2O + CO2
RCO2H + NH3 → RCO2-NH4
+
* carboxylate salts are soluble in water
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Examples: CH3COOH (aq) + NaOH (aq) → CH3COONa (aq) + H2O (l)
sodium ethanoate
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COOH NaOH COO-Na
+ H2O
sodium benzoate
an aqueous solution of benzoic acid turns blue litmus paper to red.
Benzoic acids dissolves readily in alkalis to form salts (benzoates) and water.
Carboxylic acids react with carbonates and hydrogen carbonates to form CO2, water and salts of carboxylic acids.
Examples:
2HCOOH (aq) + Na2CO3 (aq) → 2HCOONa (aq) + CO2 (g) + H2O (l)
sodium methanoate
CH3CH2COOH(aq) + NaHCO3(aq) → CH3CH2COONa (aq) + CO2(g)+ H2O(l) sodium propanoate
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2) Reaction with electropositive metals - reactive metals (i.e. metals that are very
electropositive) react with carboxylic acids to form hydrogen gas and salts of carboxylic acids.
- examples of metals: calcium, magnesium, zinc and iron.
2CH3COOH (aq) + Mg → (CH3COO)2Mg(aq) + H2
(g) magnesium ethanoate
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RCO2H + Na RCO2-Na+ + H2(g)
1) Reaction with active metals
RCO2H + NaOH RCO2-Na+ + H2O
2) Reaction with base
3) Reaction with carbonate
RCO2H + NaHCO3 RCO2-Na+ + CO2 + H2O
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o General reaction
o Example
LiAlH4 ,
H3O+
CH3 CH2 OHCCH3 OH
O
LiAlH4 ,
H3O+
R CH2 OHCR OH
O
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Carboxylic acids reacts with phosphorus (v) chloride (PCl5) or sulphur dichloride oxide (thionyl chloride) or phosphorus trichloride (PCl3) at room temperature to form acyl chloride.
In the case of benzoic acid, the reaction mixture is heated.
R C OH
O
carboxylic acids
PCl5 R C Cl
O
POCl3 HCl
acid chlorides
R C OH
O
SOCl2 R C Cl
O
SO2 HCl
carboxylic acids acid chlorides
R C OH
O
carboxylic acids
PCl3 R C Cl
O
H3PO3
acid chlorides
3 3
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Examples:
CH3 C OH
O
SOCl2
SOCl2C
O
OH
CH3 C Cl
O
C
O
Cl
SO2
SO2
HCl
HCl
ethanoic acid ethanoyl chloride
benzoic acid benzoyl chloride
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When a carboxylic acid is heated with an alcohol in the presence of a little concentrated sulphuric acid, an ester is formed.
Known as Fischer esterification.
Since the reaction is reversible, the mixture must be heated or reflux.
CH3 C OH
O
C
O
OH
ethanoic acid
benzoic acid
H OC2H5 CH3 C OC2H5
O
H2O
ethyl ethanoate
H OC2H5 C
O
OC2H5H2O
ethyl benzoate
H+
H+
heat or reflux
heat or reflux
H+ = H2SO4
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Preparation of acid anhydrides:
- reaction of carboxylic acid with an acid chloride in the presence of pyridine.
- pyridine, C5H5N (base) is added to neutralize the HCl formed in the reaction to prevent unnessary side reaction (if any).
R C OH
O
Cl C R'
O
CH3 C OH
O
Cl C CH3
O
CH3 C OH
O
Cl C
O
R C O
O
C
O
R'
CH3 C O
O
C
O
CH3
CH3 C O
O
C
O
HCl
acid chloride acid anhydrides
examples
ethanoyl chloride acetic anhydride
benzoyl chloride acetic benzoic anhydride
pyridine
HCl
HCl
pyridine
pyridine
carboxylic acid
acetic acid
acetic acid
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Symmetrical anhydride is formed when two carboxylic acid is heated with phosphorus pentoxide (P2O5) (dehydration reaction) or heating with ZnO.
CH3 C OH
O
HO C CH3
O
CH3 C O
O
C
O
CH3H2O
two molecules of acetic acids acetic anhydride
P2O5
or ZnO/heat
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Amides can be synthesised directly from carboxylic acids, but the yield is poor. A better method of synthesising amides is by using acid chlorides. When ammonium carboxylates are heated in the presence of the free acid,
dehydration occurs to form the primary amide. Ammonium carboxylates are obtained by the reaction of carboxylic acids with
ammonia (poor method).
RCOO-NH4
+ RCONH2 + H2O
1° amide
For example:
CH3COOH + NH3 → CH3COONH4 CH3CONH2 + H2O heat
ammonium ethanoate
ethanamide
Excess RCOOH
Heat (100-200 °C)
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Secondary and tertiary amides can be synthesised by using primary amines and secondary amines respectively.
R C OH
O
H N R'
H
heat (100-200 oC)
H2O1
o amine 2
o amide
R C N
O H
R'
examples:
CH3 C OH
O
H N CH3
H
heat (100-200 oC)
H2O
methylamine N-methylethanamide
CH3 C N
O H
CH3
R C OH
O
H N R'
R"
heat (100-200 oC)
H2O2
o amine 3
o amide
R C N
O R"
R'
examples:
CH3 C OH
O
H N CH3
CH3
heat (100-200 oC)
H2O
dimethylamine N,N-dimethylethanamide
CH3 C N
O CH3
CH3
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Other method: reaction of acid chloride with ammonia or amines
R C Cl
O
NH4+ Cl-R C NH2
O
examples:
CH3 C Cl
O
CH3 C NH2
O
ammonium chloride
2NH3
2NH3 NH4+ Cl-
amide
2CH3NH2 CH3NH3+ Cl-
R C Cl
O
RNH3+ Cl-R C N
O
ammonium chloride
2RNH2
secondary amide
H
R
R C Cl
O
R2NH2+ Cl-R C N
O
ammonium chloride
2R2NH
tertiary amide
R
R
ammonia
amine
secondary amine
CH3 C Cl
O
CH3 C N
O CH3
H
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Thank you…