Aldehyde, Ketone, Carboxylic Acid

1. (i) CHO aldehyde C

2
H
5
CHO (Propanal) but CHO gp attached with ring called
carbaldehyde
(ii) >C= Ketone CH
3
COC
2
H
5
Pentanone C
6
H
5
COC
6
H
5
Benzophenone

(iii)
(iv)CH
3
CH
2
COCl Propanoal chloride
(v) CH
3
COOC
2
H
5
ethyl ethanoate
(vi) CH
3
CH
2
CONH
2
Propanamide, CH
3
CONHCH
3
N-methyl ethanamide
(vii) High polarity of carbonyl gp is due to resonance
2. General methods of Preparation of CHO & >C=O
(i)By oxidation of 1
0
alcohol form CHO, 2
0
alcohol form >C=O
RCH
2
OH ------acidic K
2
Cr
2
O
7
, [O]----> RCHO + H
2
O
R
2
CHOH ---[O]------> R
2
=O + H
2
O
(ii)By dehydrogenation of alcohol 1
0
form CHO, 2
0
alcohol form >C=O
RCH
2
OH -----Cu, 573K-----> RCHO + H
2
R
2
CHO ----Cu,573K----> R
2
C=O + H
2
(iii) Ozonolysis

(iv) From alkyne only ethyne give CHO other give Ketone
Ethyne/ butyne + H
2
O CH
3
CHO / CH
3
CH
2
C(O)CH
3
3. Special method for preparation of -CHO
(i)Rosenmund Reduction
(ii) Stephen Reduction
(iii) Etard reaction
(iv) Gatterman koch reaction
4. Special method for preparation of ketone
(i)From acyl halide

(ii) From Grignard reagent
(iii) By friedel craft acylation
5. Physical Properties of CHO, >C=O
(i)Only HCHO gas other are liquid or solid
(ii) b.p -OH > -CHO > R-O-R > Alkane due to Hydrogen bonding
(iii) HCHO, CH
3
CHO, CH
3
COCH
3
are soluble in water other not due to H-bonding
6. Chemical Properties of aldehyde and ketone: - Due to weak and polar nature of C=O
nature
(i)Nucleophilic addition Reaction: - Nucleophile (:Nu) combine with C=O and convert
triangular planner structure to tetrahedral structure then react with H
+
to form addition
product. Addition of HCN, NaHSO
3
, RMgX, OH, NH
3
Aldehyde are more reactive than ketone due to less steric effect
(a)With HCN ->
(b) With NaHSO
3

The crystalline compound can be converted to original CHO/>C=O
Therefore, property used to separate and purify the aldehyde or ketone
(c) Grignard reagent: - To obtain higher alcohol
(d) Addition of alcohol: - monohydric alcohol form Hemiacetal, ketonketals
(e) CH
3
CH=O + NH
2
OH (oxime) CH
3
C=NOH ethanal oxime
(CH
3
)
2
C=O + NH
2
NH
2
(hydrazine) (CH
3
)
2
=NNH
2
Propanone hydrazine
+ NH
2
NHC
6
H
5
(phenyl hydrazine) (CH
3
)
2
C=NNHC
6
H
5
Propanone phenyl
hydrazine
+ NH
2
CONH
2
(Carbazine) (CH
3
)
2
C=NCONH
2
Propanone semi carbazine
(f) Reduction: - aldehyde form 1
0
alcohol ketone form 2
0
alcohol
RCHO + H
2
LiAlH
4
---> RCH
2
OH R
2
C=O + H
2
LiAlH4---> R
2
CHOH
Clemmensen reduction: - When aldehyde or Ketone reduce by Zn-Hg amalgam and
conc. HCl form alkane
Wolff-Kishner reduction: - When aldehyde or ketone reduce by hydrazine and then heat
with KOH and glycol form alkane
(g) Oxidation: - Aldehyde on mild oxidation with acidic KMnO
4
, K
2
Cr
2
O
7
, HNO
3
, Tollen
reagent, Fehling solution form carboxylic acid but ketone cannot easily oxidise [Reaction
used to distinguish aldehyde and ketone RCHO + O ----------> RCOOH]
Tollen reagent: - It is ammonical silver nitrate
AgNO
3
+ NH
4
OH AgOH + NH
4
NO
3
AgOH + NH
4
OH [Ag(NH
3
)
2
]OH (Tollen reagent) + 2H
2
O
RCHO + 2[Ag(NH
3
)
2
]OH RCOOH + 2Ag(silver mirror) + 4NH
3
+ H
2
O
Fehling solution: -
(h) Iodoform Test: - When alcohol (CH
3
CH
2
OH), aldehyde or ketone having -CH
3
gp
react with NaOH and I
2
form yellow ppt of iodoform CHI
3
CH
3
CH
2
OH + 4I
2
+ 6NaOH CHI
3
+ HCOONa + 5NaI
CH
3
CHO + 3I
2
+ NaOH/Na
2
CO
3
CHI
3
+ CH
3
COONa + NaI/CO
2
CH
3
COCH
3
+ 3I
2
+ 4NaOH CHI
3
+ CH
3
COONa + 3NaI
(i) Aldol condensation: - Aldehyde having at least one -Hydrogen when react with dil.
NaOH form hydroxyl aldehyde (Aldol)
CH
3
CHO + HCH
2
CHO ---NaOH---> CH
3
CH(OH)CH
2
CHO ---------> CH
3
CH=CHCHO
(j) Cross aldol condensation: - When two different aldehyde having -H atom react with
NaOH form four type of aldol [CH
3
CHO + CH
3
CH
2
CHO]
(i)CH
3
CHO + CH
3
CHO + NaOH CH
3
CH(CHO)CH
2
CHO
(ii) CH
3
CH
2
CHO + CH
3
CH
2
CHO CH
3
CH
2
CH(OH)CH(CH
3
)CHO
(iii) CH
3
CHO + CH
3
CH
3
CHO CH
3
CH(OH)CH(CH
3
)CHO
(iv)CH
3
CH
2
CHO + CH
3
CHO CH
3
CH
2
CH(OH)CH
2
CHO
(k) Cannizzaro reaction: - Aldehyde having -H atom react with NaOH form NaOH form
Sod. Salt of carboxylic acid and alcohol
(l) Electrophilic substitution reaction: - -CHO and >C=O gp are e
-
withdrawing gp.
Therefore, give m product
Uses of aldehyde and Ketone: -
(i) As solvent
(ii) 40% aq. HCHO called formalin used as preservative of biological species.
(iii) HCHO in Bakelite, urea formaldehyde glue
(iv) C
6
H
5
CHO in perfume industry
Carboxylic Acid RCOOH
HCOOH Formic acid, methanoic acid CH
3
COOH Acetic acid, Ethanoic acid
CH
3
CH
2
CH
2
COOH butyric acid (butter) butanoic acid
CH
3
CH
2
CH
2
CH
2
CH
2
COOH (Caproic acid) Capper (goat) Hexanoic Acid
In aq. exist as carboxylate ion
Preparation of Carboxylic acid:-
(i)By oxidation of 1
0
alcohol: -
(ii) By oxidation of alkyl benzene
(iii) From Nitrile of amide :- Hydrolysis of cyanide or amide
RCN/ArCN + H
2
O ----H
+
/OH
-
-----> R/ArCONH
2
----- H
+
/OH
-
+ H
2
O----> RCOOH/ArCOOH + NH
3
(iv)Form Grignard Reagent
(v)From acyhalide or anhydrous acid
(vi)By hydrolysis of ester
RCOOR + H
2
O ----H
+
---> RCOOH + ROH
Physical Properties of Carboxylic Acids
1. Upto 9 C atoms liquid and higher solid like wax
2. Boiling point COOH > -OH > -CHO > >C=O > R-O-R > Alkane due to strong H-Bonding.
Even in vapour phase exist as dimer.
Chemical Properties
1. In aq. acidic due to carboxylate ion
Alcohol give H
2
with Na, Phenol react with NaOH, but Carboxylic acid give effervence of
CO
2
with NaHCO
3
Acidic Nature FCH
2
COOH > ClCH
2
COOH > BrCH
2
COOH > ICH
2
COOh > CH
3
COOH due to I
effect.
Cl
3
CCOOH > Cl
2
CHCOOH > ClCH
2
COOH > CH
3
COOH
e
-
withdrawing group increases acidity Ph < I < Br < Cl < F < CN < NO
2
< CF
3
e
-
repelling group decrease acidity C
2
H
5
COOH < CH
3
COOH < HCOOH
2. On heating with P
2
O
5
/H
2
SO
4
form acid anhydride
3. Esterification
RCOOH + ROH ----H
+
-----> RCOOR + H
2
O
4. Reaction with PCl
5
, PCl
3
, SOCl
2
-------> RCOCl + POCl
3
/H
3
PO
3
/SO
2
+ HCl
5. Reaction with NH
3
form amide
CH
3
COOH + NH
3
--------> CH
3
CONH
2
+ H
2
O
6. Reduction form 1
0
alcohol
RCOOH ---------LiAlH
4
/B
2
H
6
------> RCH
2
OH
7. Decarboxylation :- When sodium salt of carboxylic acid react with sodalime form alkane
and Na
2
CO
3
8. Halogenation ( Hell volhard Zelinsky) HVZ reaction
When carboxylic acid having -H-atom are halogenated with Cl
2
/Br
2
in presence of Red
P4 form -halogenated carboxylic acid.
RCH
2
COOH + Cl
2
/Br
2
---Red P
4
----> RCXH-COOH [X = Cl
2
, Br
2
]
9. Electrophilic substitution reaction : give m product
10. Carboxylic acid does not undergoes friedel Craft reaction
(i)Since, -COOH gp is deactivating
(ii) AlCl
3
e
-
deficient react with carboxylic gp.