Reacl|ors ol prero

|
Alcohol can react with sodium to give off hydrogen,
but it is not acidic enough to neutralize NaOH.
2CH
3
O-H + 2Na 2CH
3
O
-
Na
+
+ H
2
Alkyl groups in alcohols push electrons toward the OH
group, so that the oxygen does not attract the electrons in
the O-H bond
CH
3
O-H CH
3
O
-
+ H
+
K
a
= 10
-17
mol dm
-3
The negative charge on the CH
3
O
-
is localized by
the electron-releasing effect from the CH
3
- group,
so that stabilization by charge delocalisation is not
possible.
Acidity oI phenols
!henol is acidic enough to react with both sodium
and sodium hydroxide. !henol easily loses a
proton to form the phenoxide ion, which is
stabilized by resonance. (mesomeric effect)
K
a
=0.1 mol dm
-3
OH
O
O
-
O
-
O
-
+
H
+
OH
+ NaOH
ONa
+
H
2
O
Acidity oI phenols
!henol is acidic due to two reasons:
Non bonded electrons on the oxygen atom become
partially incorporated in the delocalized system of the
benzene ring. This electron withdrawal from the O-atom
makes it slightly electron deficient, thus facilitating the
loss of a proton by weakening the O-H bond.
The phenoxide ion is stabilized relative to phenol by
delocalization of the negative charge throughout the
benzene ring. The presence of electron-withdrawing
-NO
2
group further stabilizes the phenoxide ion, making
nitrophenol a very acidic compound
!henol is, however, not acidic enough to neutralize
NaHCO
3
to give carbonic acid (CO
2
+ H
2
O).
OH
+
NaHCO
3
ONa
+ CO
2
+
H
2
O
$eparate acid-phenol mixture
!henols dissolve in aqueous sodium hydroxide by
neutralization whereas alcohols do not. This helps to
distinguish & separate between phenols & alcohols
Due to its weaker acidity, phenol does not react with
NaHCO
3
solution, whereas carboxylic acids react to
liberate carbon dioxide. NaHCO
3
(aq) offers a method
for distinguishing & separating most phenols from
carboxylic acids.
R-COOH ¹ HCO
3
-
R-COO
-
¹ H
2
O ¹ CO
2
$eparate an organic mixture
d+>f+l ¬¡¡ ÷fh÷r
f¬ ×÷f =l·¬h¬l
÷fh÷r÷=l l=·÷r
rh÷u¬l ¡+lf÷r÷d
¬vf
=cv÷¬v> l=·÷r
÷ H ´l
÷fh÷r÷=l l=·÷r
÷ \ =¤ H
d+>f+l ¬¡¡ ÷fh÷r
f¬ ×÷f 8·´¤ ¤ H
8·´¤ ¤ H f¬ ¦÷
÷xfr=·f÷d » +fh ÷fh÷r
=cv÷¬v> l=·÷r
÷ H ´l
÷fh÷r÷=l m +xfvr÷ ¬¡
^ ·+d·rh÷u¬l·=l·¬h¬l
÷ \ =H ´¤ `
Characteristic reactions oI phenols
The delocalization of electrons has strengthened the
C-O bond, the partial double bond character between
the carbon and oxygen is confirmed by its bond length
being shorter than that of normal C-O bonds.
As a result of this strengthening of C-O bond,
Displacement of the OH group is difficult
Oxidation does not give such breakdown products as acid,
alkanal, but form complex polymers
Formation of alkenes by dehydration is not possible
Delocalization of the lone pair in the oxygen atom with the
benzene ring makes the oxygen less readily available to
attack the electropositive carbon of the ÷COOH group of
carboxylic acids; esterification is slower than with alcohols
!rior change to the more reactive phenoxide ion will
help phenol esterify with the reactive acid derivatives
!henol Reactions
Aqueous solubility · 1 g cm
-3
, pH oI solution ÷ 4
Dissolves readily in NaOH(aq) but not in NaHCO
3
(aq)
Melts easily in hot water (m.p.÷42
o
C)
Na shows vigorous eIIervescence with phenol to give H
2
Adding Na
2
CO
3
, drop by drop, to neutralize FeCl
3
(aq)
until a trace oI the brown precipitate iust remains aIter
shaking; Violet coloration appears when a Iew drops oI the
neutralized FeCl
3
solution is added to a phenol solution.
Through delocalization oI the non-bonded electrons, the
OH group activates the benzene ring toward electrophilic
substitution. !henol rapidly decolorizes bromine water as
2,4,6-tribromophenol is Iormed Irom bromination at RT.
steriIication oI phenol
OH
RT
NaOH(aq)
O CH
3
COCl
O COCH
3
+
Cl
CH
3
CO-OCOCH
3
O
COCH
3
+
CH
3
CO
2
-
ethanoic acid anhydride
ethanoyl chloride
phenyl ethanoate (an ester)
!henols contain an active hydrogen, which can be replaced
by an acetvl group in a reaction called acetylation.
The acetylating agent is CH
3
COCl or CH
3
CO
2
-COCH
3
.
which can react with the compounds containing active
hydrogen such as phenol or amine (primary. secondary)
NHCH
3
+
Cl
COCH
3
NCH
3
COCH
3
+ HCl
Carbonyl Compounds
Aldehydes & ketones contain the carbonyl group.
R-C-H and R-C-R are the general structure of an
O O
aldehyde and a ketone respectively
R÷ H or an alkyl
or aryl group
R÷ alkyl or
aryl group
Both classes oI compounds show reactions
characteristic oI the carbonyl group
The carbonyl carbon is sp
2
hybridized, with its 3 attached
atoms lying in the same plane. The bond angles between
the three attached atoms are about 120
o
.(trigonal planar)
Within the carbonyl group, the electrons in the 9 and 6 bonds
are drawn toward the more electronegative oxygen atom.
The carbonyl oxygen thus bears a substantial partial negative
charge, whereas the carbonyl carbon bears a substantial
positive charge.
C O
0-

Naming alkanals and alkanones
CH
3
CH=CH-CH-
CH
3
CHO
2-methylpent-3-enaI
r
CHO
2-bromobenzaldehyde
O H
CHO
4-hydroxybenzaldehyde
CH
3
COCH
2
CH=CHCH
3
hex-4-en-2-one
CH
3
O
phenylethanone
O
CH
3
2-methylcyclohexanone
The reactions oI aldehydes and ketones include:
Nucleophilic Nucleophilic addition reactions
ddition-elimination (condensation) reactions
Oxidation and reduction
Triiodomethane reaction
Nucleophilic Addition Reactions
The carbonyl group is strongly polarized, with the
electrons in the 9 and 6 bonds shifted toward the
more electronegative oxygen atom. The carbonyl
carbon is thus electron-deficient or electrophilic,
whereas the oxygen is electron-rich or nucleophilic.
The carbonyl carbon is readily attacked by an
electron-rich nucleophile, and addition reactions of
nucleophiles at the carbonyl carbon dominate the
reactivity of carbonyl compounds.
Neutral/anionic nucleophiles offer the extra pair of
electrons for co-ordinating with the carbonyl carbon
Once a new bond is formed from the nucleophile to
the carbonyl carbon, the carbonyl oxygen gains an
unshared electron pair. This electron rich oxygen
can transfer its electron pair to a proton, completing
the overall addition of : :- -H H to the carbonyl group.
The Carbonyl Group: $tructure and Mechanism
Due to the higher electronegativity of the oxygen atom,
there exists an electropositive carbon in the carbonyl
group where an electron-rich nucleophile initiate an
attack on it. Despite the high electron density of the
carbonyl group, a nucleophile-induced addition occurs
HNu adds across the C÷O double bond in such a
way that the electron-rich nucleophile attacks
the electropositive carbon to Iorm a Nu-C bond,
and a H
¹
then attacks the intermediate anion to
Iorm the O-H bond.
O
:
-
Nu
O
Nu
O
H
H
+
0¹ 0-
Nucleophlic and lectrophilic Addition
The carbonyl carbon in the highly 5oIarized C=O
bond can act as an electron-deficient site to attract
electron-rich species (nucleophiles). Addtion to the
C=O bond is a nucleophilic addition, with the initial
attack from an nucleophiles, e.g.
The C=C ond is non-polar and acts as an electron-
rich centre instigating an initial attack onto the
electron-deficient species, e.g.
O
CN
-
CN
O
CN
OH
The CN
-
serves as the attacking nucleophile for the electron-deficient carbonyl carbon
r--OH
r
+
r
OH
HO-
The Br
-
acts as the electrophile attacked by the electron rich C÷C bond
0¹H-CN0-
$tereochemical aspect oI nucleophilic addition
n the nucleophilic addition across the C=O bond,
nucleophilic attack can come from above or below
the planar carbonyl group, in order to minimize steric
hindrance. Since addition can occur at both sides of
the plane at equal rates, both enantiomers are
formed in exactly the same amount, resulting in a
racemic mixture of products.
R
Nu
OH
O
R
R' Nu
OH
Nu from
bottom
top
Nu from
R and R
'
áre different
R'
R
R'
!ropanone does not form a racemic mixture in its reaction with cyanide
Aldehydes have fewer bulky groups than ketones
Relative reactivities oI carbonyl compounds
The relative reactivities of aldehydes & ketones toward
nucleophilic addition reactions depend on 2 factors:
Electronic influence of the groups attached to the carbonyl
carbon - The higher the number of electron-releasing
groups, the less electron-deficient is the carbonyl carbon,
an the less reactive it is toward nucleophiles.
Steric hindrance of the groups.
Alkyl groups are electron-releasing relative to hydrogen
and are also much more bulky. Hence, for both eIectronic
and steric reasons, ketones with the carbonyl group
flanked by two aIkyI or aryI gro:5s, are generally
less reactive than aldehydes.
O
H
H
O
H
R
O
R
R
H
O
R
O
O
Delocalization of electrons from the ring reduces the electron deficiency of
the carbonyl carbon and makes it much less reactive.
Least
reactive
Addition oI hydrogen cyanide (KCN)
Hydrogen cyanide adds to the carbonyl groups of
aldehydes and most ketones to form 2-hydroxynitriles
HCN is never used for addition across the C=O bond
HCN is a dangerously toxic gas at RT
HCN itself is a poor nucleophile and a weak acid
CN
-
, being a stronger nucleophile than HCN, is able
to attack the carbonyl carbon very rapidly. As a weak
acid, it adds slowly. The reaction is base catalysed as
the base can increase the [CN
-
]
O
R R'
+
CN H
OH
CN
R
R'
R' = H or alkyl group
Nucleophilic addition with KCN(aq)
ts safer to replace HCN & OH
-
by CN
-
and acid. This
can be done by mixing the aldehyde or ketone with
aqueous NaCN and then slowly adding sulphuric acid to
the mixture. Even with this procedure, great care must be
taken the reaction must be done in fume cupboard.
Hydroxynitriles are useful intermediates in organic
syntheses, especially for preparing --hydroxyacids or
-,.-unsaturated acids: the CN
-
group being readily
hydrolysed to -COOH by refluxing with 70% sulphuric
acid or dilute alkaline solutions.
Formation of cyanohydrins offers a useful way of
making molecules with 2 functional groups and with a
longer carbon chain than the original reactant.
Hydroxyacids and unsaturated acids
When reacted with HCN, ketone/aldehyde gives
hydroxynitriles, which hydrolyzes to Iorm --
hydroxyacids. Then dehydration oI the acid with
conc. H
2
$O
4
gives -,.-unsaturated acids.
&pon nucleophilic addition, all aldehydes and
unsymmetrical ketones give a racemic mixture
of enantiomers, which cannot be separated by
careful distillation. HC adds preferentially to
the carbonyI gro:5, leaving other :nsat:rated
carbon centres intact.
CH
3
CH
2
COCH
3
HCN
CH
3
CH
2
C-CN
OH
CH
3
HCl
H
2
O, heat
CH
3
CH
2
C-CO
2
H
OH
CH
3
conc. H
2
SO
4
, heat
Dehydration,
Hydrolysis of CN group
CH
3
CH=C-CO
2
H
CH
3
Reactivity oI carbonyl compounds
Nucleophilic addition oI carbonyl compounds is aIIected by
electronic and steric Iactors.
The presence of electron-withdrawing groups at the --
carbon of aldehyde/ketone makes the carbonyl carbon
more electron-deficient, thus increasing the reactivity of
the carbonyl compound. CH
3
COCHCl
2
is more reactive
than propanone toward nucleophilic addition by HCN.
The increased steric hindrance of Cl is less important in
affecting reactivity in this case.
Addition of HSO
3
-
is more prone to steric factors. With
more bulky groups attached to the carbonyl carbon,
ketones are less reactive than aldehydes.
Addition oI $odium bisulphite NaH$O
3
3,3-diethylpentan-2-one is unreactive toward
hydroxynitrile Iormation because
there are bulky substituents around the carbonyl group,
the 3 ethyl groups produce positive inductive eIIect,
reducing the electrophilic nature oI the carbonyl carbon
On shaking the aldehyde/ketone with excess 40%
aqueous sodium hydrogen sulphite at RT, colorless
crystals called bisulphite adducts bisulphite adducts are formed:
CH
3
H
O
-:SO
3
H
O
SO
3
H
H
C H
3
OH
SO
3
-
H
C H
3
t's a nucleophilic addition with the attack initiated by the
-
SO
3
H nucleophile
This reaction is very sensitive to steric hindrance and is limited to aIi5atic
aIdeydes and stericaIIy :nindered ketones (metyI ketones) onIy.
The reaction with NaHSO
3
helps distinguish aldehydes/ketones from others
!uriIication & separation oI aldehydes/methyl ketones
isulphite reaction is used for the separation and
purification of aldehydes and methyl ketones from
other compounds because these compounds can be
regenerated by treating the bisulphite adducts with
aqueous alkali or dilute acids, which reverse the
bisulphite equilibria to the left
A few derivatives of ammonia derivatives of ammonia (amine/hydroxylamine/
hydrazine/2,4-dinitrophenylhydrazine) serve as an
active nucleophile, initiating nucleophilic addition on
the carbonyl carbon of aldehydes/ketones. The
adduct formed is easily dehydrated to form a product
containing a -C=N group.
Addition-limination (Condensation)
The lone pair on the nitrogen atom of a derivative of
ammonia attacks the carbonyl carbon, forming an
unstable intermediate. This adduct then rapidly loses
a water molecule to form a condensation product.
R"-NH
2

O
R'
R
R"-N=C
R'
R
+
H
2
O
R"-NH
2

O
R'
R
R"-N--C
R'
R
OH
H
R"-N=C
R'
R
+
H
2
O
Aldehydes and ketones react with ydroxyIamine to form ydroxyIamine to form
oximes, oximes, known as aldoximes and ketoximes respectively.
Due to the high solubility of aliphatic oximes, careful
crystallization is required to get the crystalline oxime solid.
Condensation with ammonia derivatives
Aldehydes & ketones react with 2,4-dinitrophenylhydrazine
to form 2,4-dinitrophenylhydrazones. The condensation
products have sharp characteristic melting points and
is useful for identification of the original compounds.
O
R'
R
R'
R
N
H
R'
R
+
H
2
O
N
O H
H
H
:
O H
O H
HO-N==C
O
R'
R
O
2
N
NO
2
NH-NH
2
N-NH
R'
R
NO
2
O
2
N
+
OH
2
2,4-dinitrophenylhydrazone (an orange precipitate)
!urification of the condensation products is done by recrystallization from
ethanol. ts melting point is then determined after washing and drying the
crystals. The m.p. values can be compared with that from data book for
the purpose of identification of the original aldehyde or ketone.
dentiIication oI a carbonyl compound
2,4-dinitrophenylhydrazine, dissolved in ethanol, is mixed with a little
concentrated sulphuric acid to give an orange reagent commonly used
in the identification of aldehydes and ketones.
When it reacts with an aldehyde or ketone, the reagent gives an
orange-yellow solid of 2,4-dinitrophenylhydrazone. These
hydrazones can be isolated in relatively pure forms, which have
characteristic melting points.
2,4-dinitrophenylhydrazine is preferred to hydroxylamine for the
formation of derivatives because 2,4-dinitrophenylhydrazones have higher
melting points and are less soluble.
The hydrazone solid is often much more soluble in ethanol near its
boiling point than at room temperature. oiling ethanol is thus added to
an impure hydrazone until just enough has been added to dissolve it all.
Any insoluble impurities can be removed by filtering with suction
The hot filtrate (hydrazone) collected is cooled slowly in an ice-water
mixture until crystals reappear. Since the solid derivative is much less
soluble at RT, it will precipitate out from the filtrate and can be removed
by further filtration. Any soluble impurities (such as unreacted aldehydes
or ketones, minerals), will remain dissolved in the solvent.
dentiIication oI a carbonyl compound (2)
The hydrazone is said to be purified by recrystaIIization. The
effectiveness of this method depends very much on the selection of a
suitable solvent in which the hydrazone is much more soluble at high
temperature than low temperature, thus regenerating purer product
crystals in good yield.
After recrystaIIization te derivative is f:rter wased :nder s:ction wit a few
dro5s of etanoI and ten dried by drawing air tro:g tem. Te crystaIs are
s5read on a dry watc gIass & Ieft overnigt for drying.
Pro5er recrystaIIization is vital because any impurities left will depress the m.p.
of the hydrazone, thus leading to a false identification.
A dilute solution of 2,4-dinitrophenylhydrazine is used because solid
2,4-dinitrophenylhydrazine easily precipitates out and the solid might
be mistaken as the hydrazone.
Ethanol in this case is chosen largely out of trial and error, careful tests
being made on small product samples with different solvents.
y comparing the measured m.p. with those in a data book, the particular
aldehyde or ketone can be identified. Further chemical tests (Tollen's test),
may be necessary to distinguish the aldehyde from the ketone if there are
two 2,4-dinitrophenylhydrazones with the same m.ps.
Triiodomethane Reaction
Ethanal and methyl ketones contain the CH
3
CO- group,
which would react with iodine in aqueous NaOH to give
yellow crystals of triiodomethane.
A small sample of ethanal or methyl ketone can be warmed
with NaOH(aq) and a large amount of iodine (2 drops of
propanone require ~1 g of iodine). !ale yellow crystalline
precipitates of triiodomethane appear on cooling.
CH
3
CH
2
OH reacts with
2
/NaOH to give ethanal and
thus ethanol also shows positive triiodomethane test.
O
R
H
H
H
+ 3NaOH +

2
3
C
3
R
O
+
3Na
+
3H
2
O
C
3
O
R
+
-OH
O
O
R
+
CH
3
A secondary alcohol
with the -OH group
at C-2 also shows
postive iodoform test
$tructural Determination
Result $tructural inIormation
!ositive 2,4-dinitrophenylhydrazine test
!ositive Triiodomethane CHCl
3
test
Ozonolysis gives ethanal
An aldehyde or a ketone
A methyl ketone
R-CR'CHCH
3
Deduction
R' = CH
3
C=O
R = H if the formula is C
5
H
8
O
The equations involved in the deduction:
O
R
H
H
H
+ +

2
3
3
-

+
3H
2
O
O
O
R
+
CH
3 4OH
-
+
Yellow precipitate
R
O
R'
H
2
N-NH
NO
2
O
2
N
NH
NO
2
O
2
N
N
R
R'
R
H
CH
3
R'
O
3
R
O
R'
+
CH
3
CHO
The possible structures for C
5
H
8
O are:
CH
3
O
CH
3
H
H
CH
3
O
H
CH
3
H
Oxidation and Reduction
Aldehydes are oxidized to carboxylic acids redily by a
number of oxidants such as acidified KMnO
4
, K
2
Cr
2
O
7
or even mild oxidant such as ammoniacal silver nitrate
and Fehlings solution.
&nlike aliphatic aldehydes, aromatic counterparts do
not undergo oxidation readily. (enaldehyde does not
change easily to benzoic acid)
Ketones do not undergo oxidation readily. t requires
more drastic conditions to bring about the cleavage of
the carbon-carbon single bond, forming 2 acids.
R
O
H
[O]
acidified KMnO
4
or
acidified K
2
Cr
2
O
7
R
O
OH
The $ilver Mirror Test (Tollens
reagent)
Mixing aqueous silver nitrate with aqueous ammonia
forms a solution known as Tollens reagent, a weak
oxidant but when heated gently in water it can oxidize
aldehydes to carboxylate ions, itself being reduced to
metallic silver which deposits on the wall of the test
tube as silver mirror.
The %ollens reagent is prepared by adding excess
aqueous ammonia solution to a clean test tube of silver
nitrate solution, drop by drop drop by drop, until the precipitate is just
dissolved. 2Ag
+
+ 2OH
-
Ag
2
O(s) + H
2
O
Ag
2
O + 4NH
3
+ H
2
O 2Ag(NH
3
)
2
OH
A few drops of aldehyde are then added to the reagent
and the tube placed in a beaker of warm water:
2
Ag(NH
3
)
2
OH
+ R
O
H
O
R
O
NH
4
+
+
2Ag +
H
2
O
+
3NH
3
Fehlings Test
Tollens reagent gives a negative result with all
ketones and thus can serve as a specific test for
distinguishing aldehydes from ketones.
A Fehlings reagent is an alkaline solution of
copper() tartrate (clear royal blue in color).
Aliphatic aldehydes reduce the copper() ion in
Fehlings reagent to the reddish-brown
copper() oxide precipitate.
Ketones and aromatic aldehydes give negative result to the
Fehlings test, so the reagent acts to distinguish alehydes & ketones.
O
H
R
+
2Cu
2+

+
R
O
O
+
3H
2
O
+
Cu
2
O(s)
red precipitate
5 OH
-
Fehlings reagent is a solution mixture of CuSO
4
& sodium potassium tartrate in excess NaOH
Reduction
Aldehydes & ketones are reduced to primary & secondary
alkanols respectively by the two reductants:
Lithium tetrahydridoaluminate (LiAlH
4
) in ethoxyethane solution
followed by addition of water, or
Sodium tetrahydridoborate (NaH
4
) in aqueous solution/ethanol
These reductants generate the nucleophile H
-
, te hydride
ion, which is attracted to the electropositive carbonyl carbon
The nucleophilic attack by the hydride ions gives alcohols
as the reduction product. The alcohol is released upon
hydrolysis of the addition intermediate.
A ketone gives a secondary alcohol
An aldehyde gives a primary alcohol
NaH
4
is used to reduce aldehydes (to minimize hazard).
However, LiALH
4
is a more versatile reductant.
H
O
R
R'
H
O
R
R'
H
OH
R
R'
H
+
from solvent
Reduction (2)
LiAlH
4
can reduce carboxylic acid, acid anhydride, ester and
acid chloride to alcohols whereas NaH
4
cannot.
LiAlH
4
and NaH
4
produce H
-
ion for their reducing action,
both of them cannot reduce carbon-carbon double, triple
bonds and aromatic rings to full saturation. The H
-
ions are
simply repelled by the non-polar and electron-rich 6 bonds
in the carbon-carbon double bond.
O
O
NaH
4
suspended in
aqueous ethanol
H
OH
OH
H
O H
O
O
LiAlH
4
/ethoxyethane
then H
3
O
+
O H
H
H
OH
H
Reduction (3)
LiAlH
4
must be used in dry ether because it reacts violently
with water to give hydrogen and an alkaline solution.
CH
3
O
O O
H
LiAlH
4
/ethoxyethane
then H
3
O
+
O H
H
H
O H
H
H
CHO
H
H
then H
3
O
+
LiAlH
4
/ethoxyethane
H
CH
2
OH
H
double bond
O
then H
3
O
+
LiAlH
4
/ethoxyethane
H
OH then H
3
O
+
LiAlH
4
/ethoxyethane
CH
3
CHO
CH
3
CH
2
OH
R $pectra oI the carbonyl compounds
The >C=O group shows a prominent dip at around 1700 cm
-1
as a result of C=O bond vibration. The dip is often strong &
sharp. n aldehydes it is at between 1720 and 1740 cm
-1
. n
ketones it is between 1705 and 1725 cm
-1
.
90
50
30
3400 3000 1700
1330
Wavenumber
cm
-1
C=O bond
stretch
C-H bond
stretch
Carboxylic acids
The carboxyl group ÷CO
2
H is a combination of the carbonyl
group and the hydroxyl group. These two groups modify the
behavior of each other, so that the chemistry of the acids
differs from that of aldehydes, ketones and alcohols.
2-chlorobutanoic acid
enzoic acid
3-hydroxy-5-methylhexanoic acid
!ropanedioic acid
enzene-1,2-dicarboxylic acid
Hex-4-enoic acid (cis, trans)
Aldehydes & ketones can be changed to --hydroxynitriles,
which hydrolyze to --hydroxycarboxylic acids.
Cl
OH
O
CO
2
H
CO
2
H
CO
2
H
OH
OH
CH
3
O
O
OH
H
H
H
O
OH
CH
3
H
Carboxylic acids (2)
Nitriles, precursors of carboxylic acids, can also be made
from haloalkanes by nucleophilic substitution with NaCN.
Only primary haloalkanes are useful in making the nitriles
useful for conversion into carboxylic acids. As CN
-
ion is a
relatively strong base, the use of secondary or tertiary
haloalkanes leads to elimination rather than substitution
R
O
R' /H
+
CN H
R
OH
CN
R/H
H
3
O
+
heat
R
OH
COOH
R/H
CN-
H
C H
3
H
X
S
N
2
H
C H
3
H
CN
H
3
O
+
heat
H
C H
3
H
COOH
+
NH
4
+
OH
-
/H
2
O
heat
H
C H
3
CO
2
-
H +
NH
3
Alkaline hydrolysis of nitriles produces
the acid salt and ammonia. !rolonged
reflux in acid solution produces the
carboxylic acid and ammonium salt.
r
r
NaCN
NC
CN
H
3
O
+
HO
2
C
CO
2
H
hexanedioic acid
hexanedinitrile
Oxidation of primary alcohols, aldehydes & alkylbenzenes
Strong oxidants such as K
2
Cr
2
O
7
or KMnO
4
oxidizes primary
alcohols to give carboxylic acids in fairly good yield. Since
aldehydes are formed as an intermediate in the course of
such oxidation, most aldehydes undergo oxidation to acids
under even milder conditions. RCHO + [O] RCOOH
RCH
2
OH + 2[O] RCOOH + H
2
O
The side chains of alkylbenzenes are always susceptible to
oxidation by strong oxidants such as hot alkaline KMnO
4
:
Alkylbenzenes with alkyl groups larger than methyl are also degraded to
benzoic acids. Since oxidation of side chain occurs at the phenylmethyl
Carbon, 2-methyl-2-phenylpropane is resistant to side chain oxidation.
CH
3
(1) KMnO
4
/OH
-
, heat
(2) H
3
O
+
CO
2
H
Dil
KMnO
4
Alkaline KMnO
4
, H
3
O
+
Oxidation oI methyl ketones and some alcohols
Methyl ketones, with the group COCH
3
or alcohols with the
group CH(OH)-CH
3
are liable to undergo iodoIorm reaction to
Iorm CH
3
as well as a carbon skeleton with a carboxylate group
O
CH
3
+ 3
2
+
4OH
-
O
O
+
CH
3
+
3
-
+
3H
2
O
The group to which the -COCH
3
or -CH(OH)CH
3
f:nction is attaced
can be aromatic, aIkyI or ydrogen. The resulting carboxyIate carboxyIate has
one carbon Iess tan te originaI carbon skeIeton.
y utilizing different oxidants, CH
3
-C
6
H
4
-COCH
3
can form different products
C H
3
O
CH
3
C H
3
O
OH
O
HO
2
C
OH

2
/OH
-
H
3
O
+
MnO
4
-
/OH
-
H
3
O
+
Acidity oI Carboxylic acids
Ethanoic acid, CH
3
COOH, is the key ingredient in vinegar.
t is the ÷COOH group in the molecule that is responsible
for its acidity. n water the molecule dissociates into ions:
The ethanoate ion is stabilized by the spreading of the
negative charges over a carbon and two oxygen atoms.
eing a weak acid, the acid dissociation constant is small.
The smaller the pK
a
value, the greater is the acid strength
O
O
H
:O
H
H
O
O
--
+
O
H
H
H
+
ompound HH H
3
H l
2
HH l
3
H
pK
a
3.8 4.8 1.29 0.80
Electron releasing groups such as -CH
3
reduce the acid strength.
HCOOH is slightly more acidic than CH
3
CO
2
H as it has no -CH
3
.
Acidity oI carboxylic acids (2)
There are 3 factors affecting the acidity of organic acids:
the strength of the H-A bond
the electronegativity of A (electronic factor)
factors stabiIizing its conj:gate anion A
-
wit res5ect to HA
Since the O-atom is considerably more electronegative
than carbon, the O-H bond in methanol breaks more
readily than the C-H bond in methane. Also the resulting
conjugate anion, CH
3
O
-
is more stable than CH
3
-
.
The pK
a
of methanoic acid is 4. The electron-withdrawing >C=O group,
which enhances the electron affinity of the oxygen atom to which the
incipient proton is attached and weakens the O-H bond. Factor 3 is the
most important factor: the stabilization of the resulting conjugate anion
HCO
2
-
when compared with the methanoic acid molecule itself. n the
anion, negative charge is spread over 3 atoms and is thus stabilized.
nIluence oI substituents on acidity
Electron-withdrawing groups weakens the O-H bond and
helps spread out the negative charge on the resulting
carboxylate ion, thus raising the acidity of carboxylic acid.
The acidity of a carboxylic acid is greatly increased when
the number of electron-withdrawing chlorine attached to the
--carbon increases. The electron-withdrawing groups can
increase acid strength as the O-H bond is weakened and
the acid anion is stabilized. nductive effects are additive;
the more numerous the electron-withdrawing groups on
the --carbon, the stronger will then be the acid. The more
electronegative the --substituent, the stronger is the acid.
The nductive effect on acidity decreases rapidly when the
substitutents are placed farther away from the -CO
2
H group
nIluence oI substituents on acidity
The presence of electron-releasing group in the acid will
result in reduction of the acid strength for 2 reasons:
The electron-donating group pushes electrons toward the electron
deficient carbonyl carbon atom, thus reducing its charge. The
hydroyl oxygen will then have a better chance of attracting more
than its fair share of electrons in the C-O bond, thus strengthening
the O-H bond and consequently it will not break easily.
When dissociation has occurred, the electron-donating substituent
will push electrons toward the electron-rich -CO
2
-
group, thus
intensifying the negative charge and consequently destabilizes the
resulting anion.
Carboxylic acids are more acidic than phenols and they displace CO
2
from.
HCO
3
-
. Carboxylic acids react with ammonia to give ammonium salts, which
can be dehydrated by strong heating to give amides
CH
3
O
OH
+
NH
3
C H
3
O
O
NH
4
+
strong
heat NH
2
CH
3
O
+
H
2
O
ethamide
Acidity oI organic compounds
n the case of alcohols there is no delocalization of charge
stabilizing the alkoxide anion, RO
-
, with respect to alcohol
molecule itself. Alcohols are neutral.
n the case of phenol, there is also the stabilization of the
conjugate ion by the delocalization of its negative charge
through interaction with the 5 orbitaIs of the benzene ring
The negative charge spreads over the electropositive C-
atoms and the stability of the phenoxide ion is less stable
than the carboxylate as the negative charge in it is spread
over two highly electronegative oxygen atoms.
The order of stability follows the order of stability of their
conjugate anions:
O
OH
R
OH
R OH
> >
R $pectra oI the carbonyl compounds
The >C=O group shows a prominent dip at around 1700 cm
-1
as a result of C=O bond vibration. The dip is often strong &
sharp. n aldehydes it is at between 1720 and 1740 cm
-1
. n
ketones it is between 1705 and 1725 cm
-1
.
90
50
30
3400 3000 1700
1330
Wavenumber
cm
-1
C=O bond
stretch
C-H bond
stretch
L
L
L
L

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